Computers and Electronics in Agriculture 69 (2009) 24–32

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Computers and Electronics in Agriculture

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Instantaneous quantitative and qualitative assessment of pear quality using near

infrared spectroscopy
Patricia Paz a, María-Teresa Sánchez a,∗, Dolores Pérez-Marín b,∗, José Emilio Guerrero b, Ana Garrido-Varo b

a
Department of Bromathology and Food Technology, University of Cordoba, Campus Rabanales, Charles Darwin Building, 14071 Cordoba, Spain
b
Department of Animal Production, University of Cordoba, Campus Rabanales, 14071 Cordoba, Spain

a r t i c l e i n f o a b s t r a c t

Article history: A comparative study was made of the performance of different spectrophotometers as part of a research
Received 12 December 2008 into the potential of NIR reflectance spectroscopy as a non-destructive method for predicting soluble
Received in revised form 21 April 2009 solid content, firmness and postharvest shelf-storage time in intact pears. Three commercially available
Accepted 15 June 2009
spectrophotometers were used: a scanning monochromator (SM) of 400–2500 nm, a combination of diode
array and scanning monochromator (DASM) of 350–2500 nm and a diode array (DA) of 900–1700 nm. A
Keywords:
total of 332 pears (Pyrus communis L.) cv. ‘Blanquilla’ and ‘Conference’ were used to develop calibration
NIR spectroscopy
models in different spectral regions, using various spectral signal pretreatments. Models to predict soluble
Intact pear
Quality
solid content yielded coefficients of determination (r2 ) ranging from 0.39 to 0.76, and a standard error of
Non-destructive analysis cross-validation (SECV) of between 0.59 and 1.49 ◦ Brix, depending on the instrument used. Models for
Soluble solid content predicting firmness yielded r2 values of between 0.45 and 0.79 and SECVs ranging from 5.33 to 7.36 N.
Firmness Subsequently, the ability of these instruments to classify fruit as a function of postharvest shelf-storage
Shelf-storage time time (0, 6 and 8 days) was tested using partial least squares discriminant analysis (PLS-DA), which yielded
percentages of correctly classified samples (ratio of correctly classified samples to total samples) ranging
from 81.1 to 94.4%, depending on the instrument used. The results obtained highlight the potential of
these NIR instruments for assessing internal quality indices and predicting postharvest storage duration
in pears, particularly when the instruments SM and DASM were used.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction
The fresh fruit market is becoming increasingly demanding with
regard to product quality; this, in turn, governs fruit prices. Today,
one of the main aims of the fruit industry is to provide the consumer
with products meeting high internal quality standards, rather than
fruit which looks mouthwatering but actually tastes insipid or has
an undesirable texture.
Parameters such as soluble solid content (SSC) and, especially,
firmness are among the major quality attributes of pears (Nicolaï et
al., 2008). They must therefore be taken into account when deter-
mining the effect of postharvest storage time on product quality.
Good-quality pears develop a buttery, juicy texture, following soft-
ening related to changes in cell wall structure (Murayama et al.,
2006). Firmness is thus the best indicator of degree of ripening,
and must be measured at both the shipping and the retail stages
(Thompson and Crisosto, 2002; Valero et al., 2007). Charting firm-
∗ Corresponding authors. Tel.: +34 957 212576; fax: +34 957 212000.
E-mail addresses: teresa.sanchez@uco.es (M.-T. Sánchez), pa2pemad@uco.es
(D. Pérez-Marín).
ness and SSC as a function of postharvest storage time could provide
valuable information for commercial decision-making, since fruit
sold to the consumer must meet given quality standards based on
these two parameters.
At the same time, the consumer buying the product in the super-
market needs to be sure how long it will subsequently last. Shelf-life
can be seen as a synthesis of all the physical/chemical characteris-
tics of the product, and its prediction is therefore of great interest
to retailers.
The quality control of fruits and vegetables has traditionally been
based on destructive methods. As a result, only a small number of
control samples could be analysed per batch, giving rise to problems
caused by the individual variation between products in the same
batch (Galvis-Sánchez et al., 2004).
The fruit sector would benefit greatly from a non-destructive,
rapid, precise, low-cost, non-contaminant and versatile method
for quality control. NIRS technology would appear to be ideal for
this purpose, in that it meets all these requirements. It also yields,
instantly, a single spectral analysis which potentially provides
information on a whole range of parameters, including chemi-
cal attributes (e.g. soluble solid content), physical properties (e.g.
firmness) and a global index (shelf-life). This method is espe-

0168-1699/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.compag.2009.06.008
 P. Paz et al. / Computers and Electronics in Agriculture 69 (2009) 24–32 25

Table 1
Statistical analysis of the calibration and prediction sample sets, i.e. data range, mean and standard deviation (SD) and coefficient of variation (CV).

Parameter Item Blanquilla Conference Blanquilla + Conference

C1 C12 V C2 C22 V C3 C32 V

SSC (◦ Brix) Number 168 146 22 164 142 22 332 288 44

Minimum 10.70 10.70 11.90 11.10 11.35 11.10 10.70 10.70 11.40
Maximum 17.70 17.70 15.40 21.95 21.95 20.30 21.95 21.95 17.70
Mean 13.89 13.89 13.90 15.13 15.15 15.03 14.50 14.57 14.08
SD 1.20 1.23 1.00 2.10 2.05 2.43 1.81 1.86 1.42
CV (%) 8.65 8.88 7.18 13.86 13.53 16.17 12.50 12.73 10.12

Firmness (N) Number 168 146 22 164 142 22 332 288 44

Minimum 2.37 2.37 4.47 3.16 3.16 3.97 2.37 2.37 3.19
Maximum 47.54 47.54 33.53 54.31 54.31 51.29 54.31 54.31 47.97
Mean 15.09 15.11 14.94 14.31 13.70 18.22 14.70 14.48 16.21
SD 9.71 9.92 8.36 13.90 13.35 16.89 11.95 11.47 14.81
CV (%) 64.34 65.65 55.96 97.17 97.43 92.71 81.30 79.19 91.36

cially valuable for predicting complex parameters such as shelf-life,
which is governed by multifactorial changes (Camps et al., 2007)
and thus requires the information provided by the spectrum as a
whole.
Recent advances in NIR instrumentation include an increased
use of diode-array equipment varying in wavelength resolution,
detector type, and electronic stability. This has enabled NIRS to
be used for on-site and on-line product testing, although much
research is still required before this can be achieved on industrial
level.
Several published papers report on the use of NIRS technology
for the quality control of fruit and vegetable products, as discussed
in a number of specific reviews (Nicolaï et al., 2007; Saranwong and
Kawano, 2007). The application of NIRS technology to the study of
pears has focussed on the use of NIRS to predict internal damage in
Chinese pears (Han et al., 2006), to identify varieties (Fu et al., 2007),
to predict physical/chemical parameters such as pectin constituents
in Japanese pears (Sirisomboon et al., 2007), sugar content, titrable
acidity and pH (Ying and Liu, 2008) and soluble solid content and/or
firmness (Fu et al., 2006; Liu et al., 2007; Tsai et al., 2007; Nicolaï
et al., 2008). Few studies have sought to compare NIRS instruments
differing in terms of cost, optical design, and suitability for on-site
use. No hitherto-published research has dealt with the prediction
of shelf-life in pears, despite the commercial importance of this
parameter.
This study aimed to compare the performance of three commer-
cially available NIR instruments in providing models predicting SSC
and firmness in pears, and subsequently to evaluate the ability of
NIRS technology to measure changes taking place in pears during
postharvest storage, using discriminant analysis.
2. Materials and methods
2.1. Fruits
A total of 336 pears (Pyrus communis L.) cv. ‘Blanquilla’ and ‘Con-
ference’, were received by our laboratories between March and
April 2007; for each variety, 14 batches of 12 pears each were
received. Four ‘Conference’ pears were discarded for failing to meet
established quality standards, leaving a total of 332 pears.
In order to determine pear storage time, batches were arranged
on shelves at 20 ◦ C and 70% relative humidity. The product was
kept under these conditions throughout the trial period, with sam-
ples drawn for analysis at 6- and 8-day intervals. The raw material
sample (0 days’ storage) served as control.
variety or two: C1 (168 ‘Blanquilla’ pears for SSC and firmness), C2
(164 ‘Conference’ pears for SSC and firmness) and C3 (332 pears for
SSC and firmness).
Once the two best instruments, signal pretreatments and spec-
tral ranges had been selected for each calibration set and analytical
parameter, new NIRS calibration models were developed and
validated with an external set (not used in the calibration devel-
opment). After elimination of outlier spectra (i.e. wrong spectra or
spectra belong to fruits with external damages), calibration and
validation samples were selected solely on the basis of spectral
data, following the method proposed by Shenk and Westerhaus
(1991), using the Center algorithm included in the WinISI II soft-
ware package version 1.50 (Infrasoft International, Port Matilda, PA,
USA) (ISI, 2000). This algorithm performs a principal component
analysis, reducing the original spectral information (log 1/R values)
to a small number of linearly independent variables, thus facilitat-
ing the calculation of spectral distances. These new variables were
used to calculate the centre of the spectral population and the dis-
tance (expressed as the Mahalanobis distance) of each sample in
the calibration set from that centre. Having ordered the sample set
by spectral distances (from smallest to greatest distance to the cen-
tre), the 22 samples forming the validation set for the single-variety
models were selected by taking one sample out of every seven in the
initial set. After this procedure, the new calibration and validation
sets thus comprised the samples shown in Table 1.
2.3. Reference data
Firmness was measured based on the resistance of the fruit flesh
to penetration by the puncture probe. The Magness–Taylor (M–T)
technique was used to measure firmness. Skin from opposite cheeks
of each fruit was removed with a knife for M–T measurements.
Firmness of all individual fruit was measured at two positions
around the equator, approximately 180◦ apart, and perpendicular to
the stem–calyx axis. Measurements were carried out with a Univer-
sal Testing Machine (Model 3343 Single Column, Instron, Norwood,
MA, USA) with a 8 mm diameter probe mounted on a 1000 N load
cell with a crosshead speed of 0.0016 m/s (100 mm/min) and pene-
trating the fruit to 10 mm. Flesh firmness was calculated as an aver-
age of two measurements per fruit and expressed in Newtons (N).
Soluble solid content (SSC) were taken by removing two longitu-
dinal wedges (from stem end to calyx end) from each fruit, pressing
through cheesecloth, and the SSC of the juice was measured with a
temperature-compensated refractometer (model ATC-1, Atago Co.,
Tokyo, Japan).

2.2. Definition of calibration and validation sets 2.4. Spectra collection

Three different calibration sets were used to obtain NIRS predic- For collecting NIR spectra, three NIR-instruments – working in
tion models, depending on the use of sets that comprised an unique reflectance mode (log 1/R) and differing mainly in the wavelength
26 P. Paz et al. / Computers and Electronics in Agriculture 69 (2009) 24–32
Table 2
Basic technical features of three spectrophotometers: scanning monochromator (SM: FNS-6500), diode array and scanning monochromator (DASM: LabSpec® Pro A108310)
and diode array (DA: NIR-512).
Properties Instruments
SM: FNS-6500
Detector type Silicon, 400–1100 nm. Lead sulphide,
1100–2500 nm
Wavelength range (nm) 400–2500
Spectral bandpass 10 ± 1 nm in reflectance
Spectral data rate 1.8 scans/s
Dispersion Pre
Light source Full spectrum
Analysis mode Reflectance
range used and the measuring principle involved – were used. The
main features of these instruments are shown in Table 2.
The FNS-6500 (FOSS NIRSystems, Silver Spring, MD, USA) scan-
ning monochromator (SM) was interfaced to a remote reflectance
fiber optic probe (NR-6539-A) with a 43 × 43 mm window. In order
to shield the detector assembly, a dark perspex compartment
(340 mm × 238 mm × 222 mm) was used. Each fruit was placed in
the probe with the stem–calyx axis horizontal, so that the desired
fruit location was centred on, and in direct contact with, the probe.
The optical absorption spectrum from 400 to 2500 nm in 2 nm steps
was measured at two different locations. The first measurement
was collected at a random location around the circumference, and
the next at approximately 180◦ rotation from the initial site. The
two spectra were averaged to provide a mean spectrum for each
pear. NIR spectra data were collected using the WinISI II software
package version 1.50 (Infrasoft International, Port Matilda, PA, USA).
The LabSpec® Pro A108310 (Analytical Spectral Device, ASD, Inc.,
Boulder, Colorado, USA), a diode array scanning monochroma-
tor (DASM), spectrophotometer, was equipped with a fiber-optic
contact probe, working in reflectance mode in the spectral range
350–2500 nm, at 1 nm intervals. Pears were placed steadily upon
the fruit holder, with the stem–calyx axis horizontal. On each pear,
a reflectance spectrum was measured on two opposite, equatorial
positions and the averaged spectrum per fruit was used for analysis.
The NIR-512 (Ocean Optics, Inc., Dunedin, FL, USA) diode array
(DA), instrument was equipped with a 2 mm-diameter angled
reflection probe, using a 30◦ window to remove specular reflec-
tion effects, working in reflectance mode in the spectral range
900–1700 nm. Spectra were captured using the same method as
for the LabSpec® Pro A108310.
For the latter two instruments, the signal was captured using
IndicoTM Pro (ASD, Inc., Boulder, Colorado, USA) and Spectra Suite
packages (Ocean Optics, Inc., Dunedin, FL, USA), respectively, and
subsequently pretreated using the Unscrambler version 7.5 pro-
gram (CAMO, ASA, Oslo, Norway).
2.5. Chemometric data treatment
Spectra data were processing using the WinISI II software pack-
age version 1.50 (Infrasoft International, Port Matilda, PA, USA) (ISI,
2000). Before developing NIRS calibrations, the structure and spec-
tral variability of the sample population was determined using the
Center algorithm included in the WinISI II software. This program
performs an initial principal component analysis (PCA) to calculate
the centre of the population and the distance of samples from that
centre in an n-dimensional space, using the Mahalanobis distance;
samples with a statistical distance greater than 3 were considered
outliers or anomalous spectra (Shenk and Westerhaus, 1991, 1995a).
Quantitative calibrations were obtained for predicting soluble
solid content (SSC) and firmness in intact pears, using modified
DASM: LabSpec® Pro A108310 DA: NIR-512
Modular silicon array and two Peltier 512 element InGaAs. Linear array
cooled InGaAs detectors
350–2500 900–1700
3 nm at 700 nm. 10 nm at 3 nm
1400–2100 nm
0.1 s 0.1–3 s
Post Post
Full spectrum Full spectrum
Reflectance Reflectance
partial least squares (MPLS) as regression method (Shenk and
Westerhaus, 1995a). Shenk and Westerhaus (1995a) indicated that
MPLS is often more stable and accurate than the standard PLS
algorithm for agriculture applications. In MPLS, the NIR residuals
at each wavelength, obtained after each factor is calculated, are
standardized (divided by the standard deviations of the residuals
at a wavelength) before calculating the next factor. When devel-
oping MPLS equations, cross-validation is recommended to select
the optimal number of factors and to avoid overfitting (Shenk and
Westerhaus, 1995a). For cross-validation, the calibration set was
partitioned in four groups; each group was then predicted using
a calibration developed on the other samples. Finally, validation
errors were combined to obtain a standard error of cross-validation
(SECV).
All multivariate regression equations were obtained using the
standard normal variate and detrending methods for scatter correc-
tion (Barnes et al., 1989). Moreover, four derivative mathematical
treatments were tested in the development of NIRS calibrations:
1,5,5,1; 2,5,5,1; 1,10,5,1 and 2,10,5,1 (the first digit is the order of the
derivative, the second is the gap over which the derivative is calcu-
lated, the third is the number of data points in a running average
or smoothing, and the fourth is the second smoothing) (Shenk and
Westerhaus, 1995b).
For calibration of both quality indices a number of spectral
regions were used. For the NIR-512 instrument all measurements
were made over 900–1700 nm. The other two instruments were
each tried at 800–2200, 900–1700, and 1100–2200 nm.
The statistics used to select the best equations were: standard
error of calibration (SEC), coefficient of determination for calibra-
tion (R2 ), standard error of cross-validation (SECV), coefficient of
determination for cross-validation (r2 ), RPD or ratio of the standard
deviation of the original data (SD) to SECV, and the CV (coefficient
of variation) or ratio of the SECV to the mean value of the reference
data for the training set. This last statistic enables SECV to be stan-
dardized, facilitating comparison of the results obtained with sets
of different means (Williams, 2001).
The best-fitting equations, as selected by the above statisti-
cal criteria particularly taking into account the lowest SECV and
the highest RPD, were subsequently evaluated by external valida-
tion, a procedure determining the predictive ability of an equation
based on a sample set which has not been used in the calibration
procedures. This statistical process is based on the determination
of a known significant error, termed “bias”, and an unexplained
significant error, termed SEP(c) (standard error of performance,
bias-corrected) (Windham et al., 1989).
Generally, for calibration groups comprising 100 or more sam-
ples, and validation groups containing nine or more samples,
assuming a confidence level of 90%, the following control limits are
assumed (Shenk et al., 1989; Shenk and Westerhaus, 1996): limit
control SEP(c) < 1.30 × SEC; limit control bias < ±0.60 × SEC.
 P. Paz et al. / Computers and Electronics in Agriculture 69 (2009) 24–32 27

2.6. Discriminant models

Discriminant models were built, for each variety, to classify

pears in terms of postharvest shelf-storage time as an approach for
shelf-life estimation, using the PLS2 discriminant analysis (Naes et
al., 2002) included in the WINISI II version 1.50 software package.
PLS discriminant analysis uses a training set to develop a qualita-
tive prediction or calibration model which may subsequently be
applied for the classification of new unknown samples. This model
seeks to correlate spectral variations (X) with defined classes (Y),
attempting to maximize the covariance between the two types of
variable. In this type of approach, the Y variables used are not con-
tinuous, as they are in quantitative analysis, but rather categorical
“dummy” variables created by assigning different values to the dif-
ferent classes to be discriminated.
Three categories or classes were established for each cultivar:
day 0 or baseline and two storage intervals (6 and 8 days). For each of
the three storage times, 56 pears were taken for each variety, except
on day 8 of storage for the ‘Conference’ variety, when 52 pears were
analyzed, thus giving a total of 332 pears (168 ‘Blanquilla’ and 164
‘Conference’).
Two spectral regions were used for the development of the
classification models: 900–1700 nm for the three instruments
tested and 800–2200 nm for the FNS-6500 and LabSpec® Pro
A108310 instruments. Spectra were pre-treated with standard nor-
mal variate and detrending methods for scatter correction and
four derivative mathematical treatments (1,5,5,1; 2,5,5,1; 1,10,5,1;
2,10,5,1).
The following statistical parameters were used to evaluate the
predictive capacity of the models: the SECV and the percentage of
correctly classified samples.

3. Results and discussion

3.1. Calibration database composition

The main characteristics of the three calibration sets used, i.e. the
number of samples analyzed for each variety, together with mean,
Fig. 1. Changes in quality parameters during on-shelf storage. Vertical bars represent
range, standard deviation (SD) and variation coefficient (CV) for the
SD (n = 56 except for ‘Conference’ pears on day 8, n = 52).
reference values, are shown in Table 1.

Table 3
Calibration statistics for the equations obtained for the prediction of soluble solid content (SSC, ◦ Brix) for the different instruments and spectral ranges studied.

Instrument Set Spectral range (nm) Mathematical treatment Mean SD SEC R2 SECV r2 RPD CV (%)

FNS-6500 C1 800–2200 2,10,5,1 13.81 1.10 0.57 0.73 0.71 0.59 1.55 5.14
C1 900–1700 2,5,5,1 13.85 1.08 0.49 0.80 0.59 0.71 1.83 4.26b
C1 1100–2200 2,10,5,1 13.80 1.10 0.56 0.74 0.75 0.55 1.47 5.43
C2 800–2200 2,10,5,1 15.04 1.86 0.94 0.74 1.16 0.62 1.60 7.71
C2 900–1700 2,10,5,1 14.99 1.89 0.99 0.72 1.16 0.63 1.63 7.74a
C2 1100–2200 1,5,5,1 15.06 1.87 1.05 0.68 1.16 0.62 1.61 7.70
C3 800–2200 2,10,5,1 14.40 1.67 0.77 0.78 0.88 0.72 1.90 6.10
C3 900–1700 2,10,5,1 14.42 1.67 0.77 0.78 0.82 0.76 2.04 5.69b
C3 1100–2200 1,5,5,1 14.37 1.66 0.85 0.74 0.93 0.69 1.78 6.47

LabSpec® Pro A108310 C1 800–2200 1,10,5,1 13.90 1.14 0.54 0.78 0.74 0.58 1.54 5.32a
C1 900–1700 1,5,5,1 13.90 1.14 0.59 0.73 0.76 0.55 1.50 5.47
C1 1100–2200 1,5,5,1 13.90 1.13 0.61 0.71 0.82 0.48 1.38 5.90
C2 800–2200 1,10,5,1 14.90 1.99 1.09 0.70 1.21 0.63 1.64 8.12
C2 900–1700 1,10,5,1 14.90 1.99 1.02 0.74 1.13 0.68 1.76 7.58b
C2 1100–2200 1,10,5,1 14.85 1.92 1.04 0.70 1.20 0.61 1.60 8.08
C3 800–2200 1,5,5,1 14.33 1.59 0.77 0.77 1.00 0.61 1.59 6.98
C3 900–1700 1,10,5,1 14.43 1.62 0.74 0.79 0.89 0.70 1.82 6.17a
C3 1100–2200 1,10,5,1 14.39 1.70 1.05 0.61 1.17 0.52 1.45 8.13

NIR-512 C1 900–1700 1,5,5,1 13.92 1.20 0.77 0.59 0.94 0.39 1.28 6.75a
C2 900–1700 2,5,5,1 15.13 2.05 1.18 0.67 1.49 0.47 1.38 9.85a
C3 900–1700 1,5,5,1 14.41 1.61 1.09 0.54 1.21 0.44 1.33 8.40a

Mean: mean of the calibration set. SD: standard deviation. SEC: standard error of calibration. R2 : coefficient of determination of calibration. SECV: standard error of cross-
validation. R2 : coefficient of determination of cross-validation. RDP: SD/SECV. CV: coefficient of variation.
a
Best equation.
b
The best of the best equations for each calibration set.
28 P. Paz et al. / Computers and Electronics in Agriculture 69 (2009) 24–32

Table 4
Calibration statistics for the equations obtained for the prediction of firmness (N) for the different instruments and spectral ranges studied.

Instrument Set Spectral range (nm) Mathematical treatment Mean SD SEC R2 SECV r2 RPD CV (%)

FNS-6500 C1 800–2200 2,10,5,1 13.89 7.91 4.79 0.63 5.50 0.52 1.44 39.60a
C1 900–1700 2,10,5,1 14.03 8.32 5.33 0.59 5.76 0.52 1.44 41.05
C1 1100–2200 1,5,5,1 13.56 7.60 5.17 0.54 5.66 0.45 1.34 41.74
C2 800–2200 2,10,5,1 13.45 13.16 4.55 0.88 6.35 0.77 2.07 47.21a
C2 900–1700 1,5,5,1 12.22 11.79 6.21 0.72 6.63 0.68 1.78 54.26
C2 1100–2200 2,10,5,1 13.35 13.20 5.70 0.81 7.35 0.69 1.80 55.06
C3 800–2200 2,10,5,1 13.93 11.22 5.37 0.77 6.78 0.63 1.65 48.67a
C3 900–1700 2,5,5,1 13.49 10.60 5.58 0.72 6.53 0.62 1.62 48.41
C3 1100–2200 1,10,5,1 13.50 10.58 6.37 0.64 6.92 0.57 1.53 51.26

LabSpec® Pro A108310 C1 800–2200 1,5,5,1 14.46 9.72 4.45 0.79 5.99 0.62 1.62 41.42
C1 900–1700 1,5,5,1 14.20 9.08 3.49 0.85 5.33 0.65 1.70 37.54b
C1 1100–2200 1,5,5,1 14.61 9.57 4.27 0.80 5.93 0.61 1.61 40.59
C2 800–2200 1,5,5,1 14.55 14.17 3.27 0.95 6.45 0.79 2.20 44.33
C2 900–1700 1,10,5,1 15.38 14.90 4.66 0.90 6.81 0.79 2.19 44.28b
C2 1100–2200 1,5,5,1 14.66 14.44 4.65 0.90 7.36 0.74 1.96 50.20
C3 800–2200 1,5,5,1 14.67 12.12 4.50 0.86 6.75 0.69 1.80 46.01
C3 900–1700 1,10,5,1 15.16 12.71 5.39 0.82 6.80 0.72 1.87 44.85b
C3 1100–2200 1,10,5,1 14.40 11.86 5.36 0.80 6.89 0.67 1.72 47.85

NIR-512 C1 900–1700 2,5,5,1 14.74 9.34 3.88 0.83 5.67 0.63 1.65 38.28a
C2 900–1700 1,5,5,1 13.77 13.63 5.84 0.82 7.22 0.73 1.89 52.43a
C3 900–1700 1,10,5,1 13.72 10.98 6.09 0.69 6.85 0.61 1.60 49.93a

Mean: mean of the calibration set. SD: standard deviation. SEC: standard error of calibration. R2 : coefficient of determination of calibration. SECV: standard error of cross-
validation. r2 : coefficient of determination of cross-validation. RDP: SD/SECV. CV: coefficient of variation.
a
Best equation.
b
The best of the best equations for each calibration set.

It can be observed that set C2 (‘Conference’), displayed the great-
est variation for both parameters (for SSC, CV = 13.86% versus 8.65%
and 12.50% for sets C1 and C3, respectively; for firmness, CV = 97.17%
versus 64.34 and 81.30% for sets C1 and C3, respectively), even
though C2 contained a single variety whilst C3 contained both vari-
eties.
Changes and evolution in SSC and firmness for ‘Blanquilla’ and
‘Conference’ pears during shelf-storage are shown in Fig. 1. It can
be reported that no evolution is observed in SSC during the shelf-
storage time. Nevertheless, firmness declined markedly throughout
postharvest storage. This decrease is observed for the two varieties
of pear from day 0 to day 6, and also continues for the day 8.
At the start of measurements (day 0) mean firmness values,
around 25 N for ‘Blanquilla’ pears and around 31 N for ‘Conference’
pears, could be considered as “ready to buy” for the first variety and
“ripe” for ‘Conference’ (Gorny et al., 2000). During on shelf-storage,
for ‘Blanquilla’ pears, firmness values fell to 11 N at day 6, lying in
the range considered as edible firmness or optimum (Murayama et
al., 1998) whilst at day 8 the firmness fell to 8 N. For ‘Conference’
pears, the loss of firmness was very pronounced, and on day 6, the
reached firmness was lower than the optimum target, with values
around 5 N, being considered as too soft.
3.2. Soluble solid content
The statistics for the best-fitting equations to predict SSC,
obtained with each calibration set tested and for the three NIR
instruments studied are presented in Table 3.
For the FNS-6500, the best calibration results were obtained
using D2 log(1/R) for the three calibration sets analyzed, whilst
using the LabSpec® Pro A108310, the best results were obtained
using D1 log(1/R) for all three sets. Using the NIR-512, the best
results for the ‘Blanquilla’ set and the mixed-variety set were
obtained with D1 log(1/R), whilst the best equations for the ‘Con-
ference’ set were obtained using D2 log(1/R).
Regarding the spectral range, it seems that in general the best
results were obtained using the region 900–1700 nm, except for
set C1 on the LabSpec® Pro A108310. Nevertheless, in this case the
improvement of use the large range (800–2200 nm) is not very
important. This is interesting since the price of the NIR equipments
is highly correlated with its spectral range. Specially, for the diode-
array instruments working at wavelengths above 1700 nm is still
economically unviable.
The results displayed in Table 3 show differences in SSC
prediction accuracy between all three instruments. Thus, the
FNS-6500 displayed the greatest predictive capacity (r2 = 0.76;
SECV = 0.82 ◦ Brix; RPD = 2.04), with results similar to those pro-
vided by the LabSpec® Pro A108310 (r2 = 0.70; SECV = 0.89 ◦ Brix;
RPD = 1.82), whilst the NIR 512 displayed the lowest predictive
capacity (r2 = 0.44; SECV = 1.21 ◦ Brix; RPD = 1.33). This may be due
to the small probe diameter (2 mm) on the NIR-512, giving a smaller
area of analysis.
Other authors (Tsai et al., 2007; Nicolaï et al., 2008; Ying and
Liu, 2008) working with single-variety sets of Japanese pears, Euro-
pean ‘Conference’ pears and Chinese pears obtained calibrations for
determining SSC with higher predictive capacity, with r2 ranging
from 0.60 to 0.85 and SEP values of between 0.40 and 0.62 ◦ Brix.
3.3. Firmness
The statistics for the best-fitting equations to determine firm-
ness in intact pears, for each spectral range assayed and for the
three NIRS instruments and calibration sets used, are displayed in
Table 4.
Using the FNS-6500, the best models were obtained with
D2 log(1/R) and a spectral window of 800–2200 nm, although for
set C3 the differences between the statistics obtained at 800–2200
and 900–1700 nm were minimal. Using the LabSpec® Pro A108310,
the best calibration equations were achieved with D1 log(1/R) and
a spectral window of 900–1700 nm. For the NIR-512, the best equa-
tions were obtained with D2 log(1/R) in the ‘Blanquilla’ set, and with
D1 log(1/R) in both the ‘Conference’ set and the mixed-variety set.
Slight differences in accuracy were noted for the firmness mod-
els between all three instruments. The best calibration statistics
for the FNS-6500 were r2 = 0.77, SECV = 6.35 N, RPD = 2.07; for the
LabSpec® Pro A108310 the best values were r2 = 0.79, SECV = 6.81 N,
RPD = 2.19; and for the NIR-512 r2 = 0.73, SECV = 7.22 N, RPD = 1.89. In
all three instruments, the best calibration statistics were recorded
 P. Paz et al. / Computers and Electronics in Agriculture 69 (2009) 24–32 29

Table 5
Main calibration, validation statistics and control limits for predicting soluble solid content (◦ Brix) and firmness (N) in intact pears.

Parameter Instrument Set Calibration Prediction Control limits

2 2 2
R SEC r SECV r SEP SEP(c) Bias SEP(c) Bias

SSC (◦ Brix) FNS-6500 B 0.70 0.61 0.52 0.80 0.78 0.58 0.59 −0.08 0.79 ±0.37
C 0.50 1.37 0.45 1.42 0.62 1.08 1.08 0.20 1.78 ±0.82
B+C 0.78 0.79 0.73 0.87 0.74 0.83 0.83 0.08 1.03 ±0.47
LabSpec® Pro A108310 B 0.76 0.57 0.55 0.79 0.45 0.65 0.66 −0.11 0.74 ±0.34
C 0.77 0.91 0.66 1.13 0.75 1.10 1.12 0.07 1.18 ±0.55
B+C 0.81 0.76 0.73 0.90 0.72 0.74 0.75 0.03 0.99 ±0.46

Firmness (N) FNS-6500 B 0.49 6.55 0.42 7.02 0.48 5.64 5.78 −0.07 8.52 ±3.93
C 0.87 4.69 0.77 6.17 0.81 5.75 5.88 0.22 6.10 ±2.81
B+C 0.78 4.93 0.69 5.83 0.64 6.29 6.35 −0.34 6.41 ±2.96
LabSpec® Pro A108310 B 0.85 3.67 0.56 6.31 0.46 6.43 6.55 0.66 4.77 ±2.20
C 0.88 4.75 0.79 6.41 0.61 6.74 6.95 −0.21 6.18 ±2.85
B+C 0.82 5.01 0.72 6.28 0.80 6.01 6.00 −1.01 6.51 ±3.01

R2 : coefficient of determination of calibration. SEC: standard error of calibration. r2 : coefficient of determination of cross-validation. SECV: standard error of cross-validation.
r2 : coefficient of determination of prediction. SEP: standard error of prediction. SEP(c) : standard error of prediction bias-corrected. B: Blanquilla. C: Conference. B + C:
Blanquilla + Conference.

Fig. 2. Reference measured data versus NIRS predicted data for the validation set for SSC (◦ Brix) and firmness (N) using the best models obtained for the plurivarietal calibration
set.

for the single-variety ‘Conference’ set (C2), probably due to greater
variability in firmness in this set (see Table 1).
Generally speaking, calibrations displayed acceptable predictive
capacity for the physical firmness parameter; indeed, results were
better than those reported by Nicolaï et al. (2008), who considered
the results obtained by NIRS unsatisfactory for modelling firmness
predictions.
3.4. External validation
The two instruments providing the best results (FNS-6500 and
LabSpec® Pro A108310) were used for external validation, using
a sample set not included in the calibration (see Table 1), in
order to have an independent assessment of the equation accuracy
(Windham et al., 1989).
The validation of the best calibration models obtained with
each calibration set were performed using sets comprising 22 pear
samples for the single-variety sets and 44 for the mixed-variety
set (Table 1). The validation set was obtained as described under
Section 2, and the remaining samples were used to generate new
calibration models (C12 for ‘Blanquilla’, C22 for ‘Conference’, C32 for
‘Blanquilla’ + ‘Conference’), using the optimum pretreatment and
spectral range selected with the results displayed in Tables 3 and 4.
The cross-validation and validation statistics for the prediction
of SSC and firmness, together with the control limits are presented
in Table 5. It can be appreciated that the values obtained for SECV
30 P. Paz et al. / Computers and Electronics in Agriculture 69 (2009) 24–32
Fig. 3. D1 log(1/R) spectra for intact pear cv. ‘Blanquilla’ and ‘Conference’ during postharvest shelf-storage.
and SEP were very similar, confirming the suitability of the cross
validation method for estimating prediction statistics. According
with the validation procedure outlined by Shenk et al. (1989), for
the two parameters studied, both the SEP(c) and the bias were
below confidence limits, thus ensuring accurate predictions, except
for the SEP(c) for firmness in the two single-variety sets using the
LabSpec® Pro A108310. Graphically, the NIRS predicted data versus
the reference values for the best models developed using the pluri-
varietal calibration set (i.e. ‘Blanquilla’ + ‘Conference’) with the two
instruments selected, can be observed in Fig. 2.
3.5. Prediction of postharvest shelf-storage time
In order to determine the influence of variety during posthar-
vest shelf-storage time, prediction models were developed using
training sets for the two cultivars both separately and together.
Fig. 3 provides the typical D1 log(1/R) spectra for intact ‘Blan-
quilla’ and ‘Conference’ pears during shelf-storage. In the visible
region, variations in absorption bands were attributable to differ-
ences in skin and flesh colour between shelf-storage times; this
was particularly true of bands at 570–590 and 630–690 nm, whilst
in the NIR region, areas of variation were observed at around 950,
1450 and 1900 nm, corresponding to water-absorption bands, thus
allowing shelf-storage times to be distinguished on the basis of
differences in free water content due to changes occurring during
postharvest storage. Sugar-related peaks were observed at around
1100, 1390 and 2000 nm.
This work assesses the NIRS prediction of shelf-storage time
in pears as an approach for estimating the shelf-life of the prod-
uct, following the request of the company collaborator, which is
based on the demand of the supermarket chain that distributes
their fruits. This chain used to remove the product from the shelf
after 6 days, and they were interested in having an instantaneous
and non-destructive tool that would permit them to confirm the
shelf-storage time, to guarantee the shelf-life of the product to the
consumer.
 P. Paz et al. / Computers and Electronics in Agriculture 69 (2009) 24–32 31

E: 900–1700 nm
The best classification results obtained for predicting pear shelf-
storage time (all instruments and training sets), using PSL2-DA, are
shown in Table 6. A high rate of classification of pear samples as a

D: 1,5,5,1
A: 92.1%
NIR-512

B: 0.28
function of storage time was noted: over 80% of samples were cor-

99.2%

70.0%
91.8%
C: 15
rectly classified in all cases. The three instruments proved suitable
for this application, although the LabSpec® Pro A108310 yielded the

LabSpec® Pro A108310

highest overall percentage of correctly classified samples—over 77%
for all sets, both for global and for partial classification.

E: 900–1700 nm
Although classification accuracy seemed to be good for the three
shelf-storage times analyzed, the highest percentage of correctly

D: 1,5,5,1
A: 93.7%
B: 0.27 classified samples was obtained on the first day of study, for all

96.2%
77.5%
97.4%
C: 15 instruments and sample sets. Models proved to be less able to
distinguish between samples by days 6 and 8 of storage, due to phys-
E: 900–1700 nm
iological changes taking place in the fruit, particularly the decrease
in firmness, as illustrated in Fig. 1.
Conference

D: 2,10,5,1
FNS-6500

A: 83.0%

Generally speaking, the best discriminant models were obtained

B: 0.33

46.9%
99.0%
76.2%
using D1 log(1/R) except for the ‘Blanquilla’ set on the NIR-512
C: 8

and the ‘Conference’ set on the FNS-6500, where the best dis-
criminant models were obtained using D2 log(1/R). In all cases, the
E: 900–1700 nm

best results were recorded in the wavelength range 900–1700 nm.

A: percentage of samples correctly classified training samples after cross validation. B: model SECV. C: number of factors. D: math treatment. E: spectral range.

This indicates that higher wavelengths do not significantly enhance

D: 2,5,5,1
A: 91.0%
NIR-512

B: 0.27

pear classification on the basis of changes taking place throughout

94.6%
92.7%
77.3%
C: 14

postharvest shelf-storage (20 ◦ C, 70 RH). Cheaper equipment can

therefore safely be used for this type of application.
LabSpec® Pro A108310

No published studies have addressed the use of NIR-

spectroscopy models for classifying pears as a function of
E: 900–1700 nm

postharvest shelf-storage time. The percentage of correctly classi-

fied samples in this study was higher to that reported by Camps et al.
D: 1,5,5,1
A: 94.0%
B: 0.25

(2007) in apples, that with mixed-variety sets obtained a 75–83% of

92.9%
80.0%
100%
C: 12

correctly classified fruits stored according to storage time; increas-

ing, as in the present work, until 98% when a single-variety set was
E: 900–1700 nm

used.
D: 1,10,5,1
Blanquilla

FNS-6500
Cultivars

A: 85.0%

4. Conclusions
B: 0.30

56.4%
83.1%
97.2%
C: 13

The results show that NIRS technology is an useful non-

destructive sensor for the assessment of intact pears by internal
E: 900–1700 nm

quality – soluble solids content, firmness and postharvest stor-

age time – allowing increased sampling and control of the whole
D: 1,5,5,1
A: 87.6%
NIR-512

B: 0.28

production. The results obtained suggest that the SM and DASM

64.3%
84.6%
97.3%
C: 15

provide similar results for physicochemical composition, being bet-

ter the SM for shelf-life prediction. The DA instrument provided less
LabSpec® Pro A108310

precision and accuracy in all cases.

E: 900–1700 nm

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