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A Review on the Applications of Portable Near-


Infrared Spectrometers in the Agro-Food
Industry

Article in Applied Spectroscopy November 2013


DOI: 10.1366/13-07228 Source: PubMed

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focal point review
CLAUDIA A. TEIXEIRA DOS SANTOS, MIGUEL LOPO,
RICARDO N.M.J. PASCOA, JOAO A. LOPES
UNIVERSIDADE DO PORTO, REQUIMTE,
DEPARTAMENTO DE CIENCIAS QUIMICAS, FACULDADE DE FARMACIA,

RUA DE JORGE VITERBO FERREIRA, 228, 4050-313 PORTO, PORTUGAL

A Review on the Applications


of Portable Near-Infrared
Spectrometers in the Agro-Food
Industry
Industry has created the need for a cost- involving regression techniques coupled with the development of nondestructive
effective and nondestructive quality-control spectral preprocessing) are therefore required methods such as spectroscopic tech-
analysis system. This requirement has in- to extract the information hidden in the niques. Several studies have been pub-
creased interest in near-infrared (NIR) spec- spectra. This work reviews the evolution of lished concerning the application of
troscopy, leading to the development and the use of portable near-infrared spectrometers
these techniques to the agro-food indus-
marketing of handheld devices that enable in the agro-food industry.
new applications that can be implemented in
try.2 Near-infrared (NIR) spectroscopy
situ. Portable NIR spectrometers are powerful
Index Headings: Near-infrared spectroscopy; has received particular attention since
instruments offering several advantages for
NIR; Portable instruments; Agro-food indus- the pioneering work of Norris and Hart,3
nondestructive, online, or in situ analysis: small
try; In situ analysis; Chemometrics. and the contributions of Williams,4
size, low cost, robustness, simplicity of analysis, McClure et al.,5 and Norris et al.6
sample user interface, portability, and ergo- Several studies emerged from Karl
nomic design. Several studies of on-site NIR INTRODUCTION Norriss work, applying NIR spectros-
applications are presented: characterization of copy to the rapid analysis of the

T
internal and external parameters of fruits and he agro-food industry has a
moisture, protein, and fat content of a
vegetables; conservation state and fat content significant role in the world
wide range of agricultural and food
of meat and fish; distinguishing among and economy. In the last decades, it
products.7,8 Early applications of this
quality evaluation of beverages and dairy has followed this revolution to meet technique included determinations of
products; protein content of cereals; evaluation increasing consumer needs and expecta-
of grape ripeness in vineyards; and soil
dry matter content in onions,9 soluble
tions concerning quality, convenience, solids content (SSC) in apples,10 and
analysis. Chemometrics is an essential part of diversity, and health. Simultaneously,
NIR spectroscopy manipulation because wave- water content in mushrooms.11 This
there is a need to meet health and safety technique was also used to perform
length-dependent scattering effects, instrumen-
tal noise, ambient effects, and other sources of requirements; increasingly demanding microstructural measurements of stiff-
variability may complicate the spectra. As a environmental legislation; and security, ness,12 internal damage,13,14 and even
consequence, it is difficult to assign specific ethics, and sustainable production re- sensory attributes.15 Numerous studies
absorption bands to specific functional groups. quirements. The quality of agricultural have been published involving NIR
To achieve useful and meaningful results, and food products is classified according spectroscopy and its usefulness in the
multivariate statistical techniques (essentially to internal and external parameters.1 agro-food industry.2,1618
However, several analytical techniques Recently, considerable attention has
Received 19 July 2013; accepted 27 August have been applied to assess those been given to the miniaturization and
2013. parameters; the invasive, destructive, portability of spectroscopic devices.19
* Author to whom correspondence should be
sent. E-mail: joaolopes@ff.up.pt. and time-consuming nature of the refer- The use of portable instruments for in-
DOI: 10.1366/13-07228 ence methods has spurred efforts toward field measurements offers interesting

APPLIED SPECTROSCOPY OA 1215


focal point review
TABLE I. Specifications of the most commonly found literature reported portable NIR instruments.a

Commercial Resolution
name Manufacturer Models available Spectral range (nm) (nm) Light source Signal to noise

AgriSpec ASD Not applicable 3502500 3 at 700; 10 at Halogen 14 500 S/N at 1400 nm
1400/2100
FieldSpec4 ASD a. FieldSpec4 Standard- a, b, c, 3502500 a, d, 3 at 700; 10 Halogen Not specified
Res d, 3251075 at 1400/2100
b. FieldSpec4 Hi-Res b, 3 at 700; 8 at
c. FieldSpec4 Wide-Res 1400/2100
d. FieldSpec Handheld 2 c, 3 at 700; 30 at
1400/2100
LabSpec4 ASD e. LabSpec4 Standard- 3502500 e, 3 at 700; 10 at Halogen Vis-NIR 9000:1 at 700 nm
Res 1400/2100 SWIR 1 9000:1 at 1400 nm
f. LabSpec4 Hi-Res f, 3 at 700; 6 at SWIR 2 4000:1 at 2100 nm
1400/2100
AvaSpec Avantes Not applicable 2001100 0.0520 Not specified 200:1
Luminar 5030 Brimrose Not applicable 6001100, 8501700, 210 Not specified Not specified
9001800, 11002300
microPHAZIR Thermo Not applicable 16002400 Not specified Tungsten light bulb Not specified
Scientific
Phazir Polychromix g. DTS-Phazir-1016 g, 10001600 Not specified Tungsten light bulb g, 8 nm
h. DTS-Phazir-1624 h, 16002400 h, 12 nm
USB Ocean Optics USB 4000 VIS-NIR Grating dependent ~1.5 Tungsten light bulb 300:1 (at full signal)
a
AC/DC, alternating current/direct current; SWIR, short wave infrared; USB universal serial bus.

possibilities by allowing direct measure- broad and superimposed.22 The funda- measurement, and high performance
ment of important parameters. These mentals of vibrational spectroscopy reliability. Another important character-
devices have several advantages, includ- provide the theory necessary to interpret istic to be taken into account is instru-
ing reduced cost, increased safety for the this characteristic spectrum.23 The typi- ment design. An ergonomic design
environment and operators, and the cally observed bands in NIR spectra should make these portable devices
improved accuracy of the method by correspond to bonds containing the handheld, thus enhancing their ease of
preserving the sample and avoiding its hydrogen atom, such as CH, NH, use. While some devices are sold as
transport. In recent years, several efforts OH, and SH, that are frequently closed instruments (and cannot be
have been made to apply this technique present in most organic and some adapted), others offer the possibility of
to solid-sample analysis. Salvador Gar- inorganic compounds.17 A NIR spec- interchanging measurement accessories
rigues and Miguel de la Guardia recently trum is essentially composed of over- so that the same instrument can be used
summarized studies using portable in- tones and combination bands containing for different sample requirements.25
struments and their wide use in a vast useful chemical and even physical Several portable NIR spectrometers are
field of applications.2 information. The literature on NIR currently available in the marketplace,
This study provides an overview of spectroscopy and its applications in varying in cost and purpose. Table I lists
the more recent applications of portable different fields is extensive and can be some of the most important specifica-
NIR instruments in the agro-food sector. found elsewhere.17 tions of the portable NIR instruments
These applications have been divided Portable Near-Infrared Spectrom- most commonly found in the literature
into fruits and vegetables, meat and fish, eters. Industrial applications created the with reported applications in the agro-
beverages and dairy, cereals and feed- need for a cost-effective and nonde- food industry.
stock, soils and manures, and viticulture structive quality-control system. This Near-Infrared Spectral Processing.
and olive growing. Descriptions of the requirement increased the interest in Chemometrics, usually described as the
applications are provided, highlighting NIR spectroscopy, leading to the trans- application of mathematics, multivari-
the potential of this method in terms of formation of large, stationary analytical ate statistics, and computer science,18
its versatility. instruments into lightweight tools that plays a fundamental role in the extrac-
enabled new applications to be imple- tion of all-important relevant informa-
NEAR-INFRARED mented in situ at an industrial level.24 tion hidden in NIR spectra. Because a
SPECTROSCOPY Although these portable NIR spectrom- NIR spectrum consists of weak and
Near-infrared radiation ranges from eters offer several advantages, such as broad absorption bands, a straightfor-
780 to 2500 nm of the electromagnetic nondestructive and in situ analyses, their ward interpretation is often not possi-
spectrum.20,21 The measurement of the development must consider some critical ble. Furthermore, there are several other
interaction between this radiation and a factors, such as cost, size, weight, power factors that increase the complexity of
sample results in a spectrum character- consumption, robustness, safety, user- the spectra: water absorption bands,
ized by weak absorption bands that are friendliness, durability, accuracy of scattering effects, instrumental noise,

1216 Volume 67, Number 11, 2013


TABLE I. Extended.

Commercial Sampling Scanning Communications Operating


name mode time (ms) interface Power supply temperature (8C) Weight (kg) Size (mm)

AgriSpec Customizable 100 Ethernet, RJ-45, AC/DC, battery 040 5.4 127 3 368 3 292
Wifi (2 h)
FieldSpec4 Customizable a, b, c, 100 a, b, c, Ethernet, a, b, c, AC/DC, 040 a, b, c, 5.44 a, b, c, 127 3 368 3
d, Not specified Wifi battery (6 h) d, 1.2 292
d, USB d, AC/DC, battery d, 90 3 140 3 215
(1.55 h)

LabSpec4 Customizable 100 Ethernet, Wifi AC/DC, battery 040 5.44 127 3 368 3 292

AvaSpec Customizable 1.8 USB, RS-232 USB, AC/DC Not specified 0.716 175 3 110 3 44
Luminar 5030 Diffuse reflectance 16 000 Ethernet AC/DC Not specified Not specified Not specified
wavelength/s
microPHAZIR Diffuse reflectance ~1 min USB Battery (3 h) 550 1.8 266 3 109 3 251

Phazir Diffuse reflectance 12 s USB Battery (58 h) 545 1.7 254 3 292 3 152

USB Customizable .5 ms USB AC/DC Not specified 0.190 89.1 3 63.3 3 34.3

sample complexity, and matrix/environ- developed to unlock spectral data and prediction (RMSEP) or root mean
mental effects.16 Therefore, multivari- enhance the robustness and predictive square error of cross-validation
ate analysis methods coupled with ability of the calibration model.22 Che- (RMSECV) as indicators of NIR-based
spectral preprocessing techniques are mometric methods most commonly used model accuracy. The equation for root
the fundamentals of chemometrics for to process NIR spectral information and mean square error (RMSE) is
the appropriate treatment of analytical build calibrations are available in the v
literature and are not developed u 2
information contained in NIR spectra.26 uX in
here.18,32,33 In terms of their purposes u
Essentially, spectral information cap- u y i -^ y i
tured with portable instruments is and their algorithms or computational t i1
procedures, the most commonly used RMSE 1
processed using standard chemometric n
methods that have been thoroughly multivariate analysis methods are listed
described in the literature.27 Reducing in Table II. The results presented here where ^yi is the prediction value of the ith
instrumental noise or background infor- use the root mean square error of observation, yi is the measured value of
mation is usually performed using the observation, and n is the number of
smoothing techniques. A detrending the observations. Equation 1 can be used
TABLE II. Classification of the major quali- to compute the root mean square error of
preprocessing technique is sometimes tative and quantitative multivariate-analysis
used to remove the effects of accumu- calibration (RMSEC), RMSECV, and
methods used in NIR spectroscopy applied to
lating data sets from a trend, so that the agro-food industry.17,a RMSEP.27
only the absolute changes are shown.28
Derivatives are a common method used Quantitative APPLICATIONS IN THE AGRO-
to eliminate unimportant baseline sig- Non-linear methods FOOD INDUSTRY
Linear methods
nals from samples.29 Orthogonal signal ANN, non-linear PLS In the following sections a full
correction (OSC) was developed to MLR, PCR, PLS, LS-SVM description is given of the applications
reduce light-scattering effects, among Qualitative of portable NIR spectrometers in the
other general types of interference (not Unsupervised methods agro-food industry including the type of
Supervised methods
interfering with the correlation with Cluster analysis, ANN (e.g., Kohonen sample and its attributes, and, when
reference values). Path length effects, networks), PCA available, the spectrometer used, its
scattering effects, source or detector FDA, KNN, LDA, SIMCA acquisition mode, and its spectral range
variations, and other general instrument a
FDA, Fisher discriminant analysis; KNN, k- (in most studies the visible spectral
sensitivity effects are usually cor- nearest neighbor; LDA, linear discriminant analy- region was also included). This review
rected using normalization preprocess- sis; LS-SVM, least squares support vector ma- considers the application of portable
ing methods, such as standard normal chines; MLR, multiple linear regression; PCA, NIR instruments in the agro-food indus-
principal component analysis; PCR, principal
variate (SNV)28 and multiplicative sig- component regression; PLS, partial least squares; try independently of the application
nal correction (MSC).30,31 Consequent- SIMCA, soft independent modeling of class conditions. It is clear that the great
ly, preprocessing techniques, have been analogy. advantage of these systems is the

APPLIED SPECTROSCOPY OA 1217


focal point review
TABLE III. Reported applications of portable NIR instruments for fruit and vegetable analysis.a

Spectrometer, Multivariate
spectral range (nm), analytical
Species Attributes acquisition mode methods Results Reference

Mandarin Firmness (N) Phazir 2400 MPLS RMSECV = 2.96


MPF (N) (Polychromix), 1600 RMSECV = 8.07
Pericarp thickness (mm) 2400, reflectance RMSECV = 0.53
Juice weight (g) RMSECV = 14.15
Juice content (%) RMSECV = 5.45
SSC (%) RMSECV = 0.76
pH RMSECV = 0.09
TA (% of citric acid) RMSECV = 0.14
Maturity index RMSECV = 1.16
Weight (g) RMSECV = 24.31
Equatorial diameter (mm) RMSECV = 5.63
Axial diameter (mm) RMSECV = 3.21
Color index RMSECV = 2.62
Apricot (on tree) SSC (%) Phazir (Polychromix), PLS RMSEP = 7.4 48
Firmness (%) 9401797, reflectance RMSEP = 7.7
TA (%) RMSEP = 13.2
Color (%) RMSEP = 11.6
Tomato SSC (%) I.N.A., 6901700, I.N.A. PLS RMSECV , 0.4 49
Firmness (DI) RMSECV = 5.9
Color RMSECV = 2.26
Orange SSC (8Bx) I.N.A., 2001100, I.N.A. LS-SVR RMSEP = 0.321 50
Orange SSC (8Bx) I.N.A., 3502500, PCR, PLS RMSEP = 0.47 51
TA (g malic acid/L) transmittance RMSEP = 0.25%
Apple (Golden SSC (8Bx) AvaSpec 2048 (Avantes), PLS RMSECV = 6.2% 52
delicious) TA (g malic acid/L) 450-980, reflectance RMSECV = 6.6%
Firmness (N) RMSECV = 9.1%
Chlorophyll (nmol/cm2) RMSECV = 17.2%
Ascorbic acid (mg/100 g) RMSECV = 15.5%
Carotenoids (nmol/cm2) RMSECV = 10.6%
Total phenols (mg catechin/g) RMSECV = 20.0%
Apple (Stark Red SSC (8Bx) RMSECV = 6.9%
Delicious) TA (g malic acid/L) RMSECV = 4.2%
Firmness (N) RMSECV = 7.9%
Chlorophyll (nmol/cm2) RMSECV = 9.4%
Ascorbic acid (mg/100 g) RMSECV = 18.4%
Carotenoids (nmol/cm2) RMSECV = 7.7%
Total phenols (mg catechin /g) RMSECV = 1.8%
Total anthocyanins (mg RMSECV = 35.3%
malvidin/g)
Total flavonoids (mg catechin/g) RMSECV = 5.0%
Non-anthocyanic flavonoids (mg RMSECV = 6.3%
catechin/g)
Apple Acidity (g H2SO4/L) I.N.A., 6001100, I.N.A. GRNN RMSEP = 0.0558 53
Ascorbic acid (mg/100 g) RMSEP = 4.0431
Mandarin (Page) SSC (8Bx) I.N.A., 3101100, PLS RMSECV = 0.45 37
TA (g malic acid/L) reflectance RMSECV = 0.09
Mandarin (Miho) SSC (8Bx) RMSECV = 0.59
TA (g malic acid/L) RMSECV = 0.07
Nectarine Weight (g/fruit) Phazir 2400 MPLS RMSECV = 31.34 54
Diameter (cm) (Polychromix), 1600 RMSECV = 0.63
SSC (%) 2400, reflectance RMSECV = 0.69
Firmness (N) RMSECV = 13.45
Pear SSC (8Bx) VISNIR USB 4000, PLS , MLR, 0.48 , RMSEP , 0.67b 38
(Ocean Optics), 800 LS-SVM
950, diffuse reflectance
Orange SSC (8Bx) LabSpec (ASD), 500 PLS RMSEP = 0.87 55
Acidity (g H2SO4/L) 2300, reflectance RMSEP = 0.13
TA (g malic acid/L) RMSEP = 2.47
Maturity index RMSEP = 1.54
Firmness (N) RMSEP = 1.82
Juice volume (mL) RMSEP = 8.38
Fruit weight (g) RMSEP = 43.51
Rind weight (g) RMSEP = 16.07
Fruit color index RMSEP = 6.48
Juice color index RMSEP = 55.69

1218 Volume 67, Number 11, 2013


TABLE III. Continued.

Spectrometer, Multivariate
spectral range (nm), analytical
Species Attributes acquisition mode methods Results Reference

SSC (8Bx) Luminar 5030 RMSEP = 1.12


Acidity (g H2SO4/L) (Brimrose), 1100 RMSEP = 0.40
TA (g malic acid/L) 2300, reflectance RMSEP = 2.07
Maturity index RMSEP = 2.57
Firmness (N) RMSEP = 1.53
Juice volume (mL) RMSEP = 12.13
Fruit weight (g) RMSEP = 32.63
Rind weight (g) RMSEP = 14.71
Plum SSC (8Bx) Phazir 2400 PLS-DA RMSECV = 1.39 56
Firmness (N) (Polychromix), 1600 RMSECV =2.76
Correct classification according 2400, reflectance 96.5%
to the variety
Apple SSC (8Bx) I.N.A., I.N.A., I.N.A. LS-SVM RMSEP = 0.82 57
Orange (Gannan navel) SSC (8Bx) I.N.A., 551950, I.N.A. LS-SVM RMSEP = 0.55 39
Mandarin (Nanfeng) SSC (8Bx) VISNIR USB 4000 SVM, BPNN, 0.64 , RMSEP , 0.65b 40
TA (g malic acid/L) (Ocean Optics), 400 PLS RMSEP = 0.09b
Ascorbic acid (mg/100 g) 1040, transmittance 2.7 , RMSEP , 2.8b
Surface color (DE) 0.81 , RMSEP , 0.82b
Apricot (Bergaroug, SSC (8Bx) S-2000 (Ocean Optics), PLS 5.7 , RMSECV , 9.3%c 58
Harostar, Kioto) TA (g malic acid/L) 6501200, reflectance 7.1 , RMSECV , 17.7%c
Firmness (N) 6.2 , RMSECV , 24.1%c
Bergarouge Correct classification according FDA 86%
Harostar to variety 97%
Kioto, 1st harvest 96%
Kioto, 2nd harvest 92%
Blueberry SSC (8Bx) D.N.I., 450980, PLS RMSECV = 0.79 34
Total anthocyanins (mg reflectance RMSECV = 0.31
malvidin/g)
Total flavonoids (mg catechin/g) RMSECV = 0.37
Total polyphenols (mg catechin/ RMSECV = 0.20
g)
Ascorbic acid (mg/100 g) RMSECV = 1.02
Mango SSC (8Bx) Fruit Tester 20 (Fantec), PLS RMSEP = 0.40 59
8501000, interactance
Apple SSC (8Bx) D.N.I., 2001000, diffuse Multiple RMSEP = 0.52 35
reflectance regression
analysis
Apples SSC (8Bx) SD-1000 (Ocean Optics), MLR RMSEP = 1.14 41
Golden Delicious SSC (8Bx) 350999, reflectance RMSEP = 1.10
Jonagold SSC (8Bx) RMSEP = 1.18
Strawberry Firmness (N) Phazir 2400 MPLS RMSECV = 0.17 60
MPF (N) (Polychromix), 1600 RMSECV = 0.48
SSC (%) 2400, reflectance RMSECV = 0.66
TA (% citric acid) RMSECV = 0.07
pH RMSECV = 0.09
Antilla Fnm Correct classification according PLS-DA 78%
Camarosa to variety (%) 57%
Coral 68%
Florida Fortuna 67%
Primoris Fnm 75%
Orange Acidity I.N.A., I.N.A., I.N.A. I.N.A. RMSEP = 0.08165 66
Tomato (after harvesting) Firmness (MPa) FQ-NIRGUN (Fantec), PLS RMSEP = 0.0989 67
Lycopene (mg/g) 6001100, I.N.A. RMSEP = 0.0835
Firmness (MPa) PCR RMSEP = 0.0999
Lycopene (mg/g) RMSEP = 0.0833
Tomato (on vine) Firmness (MPa) PLS RMSEP = 0.0998
Lycopene (mg/g) RMSEP = 0.0827
Firmness (MPa) PCR RMSEP = 0.1011
Lycopene (mg/g) RMSEP = 0.0827
Pear Firmness (N) I.N.A., I.N.A., diffused PLS, MLR 7.74 , RMSEP , 8.08b 42
transmittance
Nectarine, 1st harvest Full irrigation (correct Phazir 2400 PLS2-DA 96.3% 68
classification) (%) (Polychromix), 1600
Regulated deficit irrigation 2400, reflectance 91.6%
(correct classification) (%)

APPLIED SPECTROSCOPY OA 1219


focal point review
TABLE III. Continued.

Spectrometer, Multivariate
spectral range (nm), analytical
Species Attributes acquisition mode methods Results Reference

Nectarine, 2nd harvest Full irrigation (correct 85.6%


classification) (%)
Regulated deficit irrigation 92.4%
(correct classification) (%)
Tomato leaf Nitrogen concentration I.N.A., 3101100, PLS RMSECV = 0.5120 69
reflectance
Orange leaf N I.N.A., 3101100, PLS RMSECV = 0.129 70
P reflectance RMSECV = 0.010
K RMSECV = 0.144
Ca RMSECV = 6.709
Mg RMSECV = 0.101
Fe RMSECV = 9.675
Mn RMSECV = 3.449
Zn RMSECV = 2.873
Pear SSC (8Bx) S-2000 (Ocean Optics), PLS, MLR, 0.54 , RMSEP , 0.64b 71
620, 850, 880, 940, ANN
diffuse reflectance
Blueberry Correct classification according I.N.A., 445970, diffuse PCA .93% 61
to ripeness stage reflectance
Tomato Dry matter (% w/w) (results MMS1 (Zeiss), 305 PLS 0.34 , RMSEP , 0.57 72
depend on the tomato position 1100, interactance
or combination of positions)
a
BPNN, back-propagation neural network; DI, Durofel index; D.N.I., development of a new instrument; FDA, Fisher discriminant analysis; GRNN, generalized
regression neural network; H2SO4, sulfuric acid; I.N.A., information not available; LS-SVM, least squares support vector machines; LS-SVR, least squares support
vector regression; MLR, multiple linear regression; MPF, maximum penetration force; MPLS, multiblock partial least squares; PCA, principal component analysis;
PCR, principal component regression; PLS, partial least squares; PLS-DA, partial least squares discriminant analysis; SSC, soluble solids content; TA, titratable
acidity.
b
Results vary according to the calibration method
c
Results vary according to the species

possibility of using them under real tential of NIR spectroscopy as applied the goal of predicting whether the fruit
production conditions; however, many to fruit and vegetables16 and about was ready to be harvested. Most
of the studies considered here were enhancing its use as a rapid and studies in this area model parameters
actually performed under laboratory nondestructive analytical technique commonly used as maturity indicators,
conditions (involving sampling and useful for determining internal and such as soluble solids content
transportation of the samples to the external characteristics, either quantita- (SSC),34,35,3741,4365 titratable acidi-
laboratory). Therefore, these studies do tive or qualitatively. However, the fruit ty, 3 7 , 4 0 , 4 8 , 5 1 5 3 , 5 5 , 5 8 , 6 0 , 6 2 , 6 4 , 6 6 and
not actually assess the performance of and vegetable sector demands field pH.55,60,62 External quality parameters
the systems under real production con- NIR spectroscopy equipment capable were also investigated, with special
ditions and are not examples of taking of performing in situ analyses to allow attention given to color;40,44,48,49,62,67
direct in situ measurements under the producers to establish the most suitable weight,44,62 and size.54,62 Among the physi-
uncontrolled conditions typical of pro- harvest dates, consequently ensuring cal parameters considered, firmness was
duction sites. the best possible crop quality, while the most common,42,44,4749,52,54,56,62,67
Fruits and Vegetables. Most of the avoiding waste and loss. Table III with some attention also paid to juice
studies in this area were performed in summarizes portable NIR spectroscopy content and juice weight,62 pericarp
the laboratory, applying NIR spectro- applications to fruit. Promising results thickness,58,62 and maximum penetra-
scopic instruments to intact harvested have been achieved when portable NIR tion force.62 In addition, Beghi et al.52
fruits (in some cases, spectra were spectroscopy has been applied in this and Guidetti et al.34 explored some
collected from the same fruit in more sector, indicating the successful use of nutraceutical parameters: total anthocy-
than one position or using spinning NIR spectroscopic measurements in anin, total phenol, total flavonoid, non-
accessories). There are, however, a nondestructively evaluating and moni- anthocyanic flavonoid, carotenoid, chlo-
significant number of applications in- toring fruit-quality parameters. 3436 rophyll, and ascorbic acid content.
volving the direct use of the equipment The potential of this technique has The correlation of the measured
in the field, where measurements were been highlighted for assessing the chemical and physical parameters with
made directly of on-tree fruits under internal quality of fruits nondestruc- the environmental conditions to which
varying weather conditions. There are tively in the field under different fruits were exposed was often evaluat-
numerous studies highlighting the po- weather conditions,3747 usually with ed. 65,68 Environmental factors are

1220 Volume 67, Number 11, 2013


TABLE IV. Reported applications of portable NIR devices for meat and fish product analysis.a

Spectrometer, Multivariate
spectral range (nm), analytical
Species Attributes acquisition mode methods Results Reference

Swordfish Correct classification MMS1 (Zeiss), 380 PLS-DA, PCA 96.7% correctly 81
according to the 1080, reflectance classified
preservation status
Pork meat in gas Ab Am (log cfu/g) Phazir 2400 PLS, MPLS RMSECV = 1.063 73
En (log cfu/g) (Polychromix), 1600 RMSECV = 1.198
Lab (log cfu/g) 2400, reflectance RMSECV = 1.256
pH RMSECV = 0.100
Pork meat in gas Bc Am (log cfu/g) RMSECV = 1.079
En (log cfu/g) RMSECV = 1.153
Lab (log cfu/g) RMSECV = 1.296
pH RMSECV = 0.117
Pork meat in gas Ab gas Bc Am (log cfu/g) RMSECV = 0.817
En (log cfu/g) RMSECV = 0.342
Lab (log cfu/g) RMSECV = 0.982
pH RMSECV = 0.039
Duroc pork and Iberian pork M. masseter muscle (correct FieldSpec (ASD), 350 ANN 95 % 74
classification of different 2500, reflectance
breeds of pork)
Rabbit In vivo, live rabbits LabSpec-Pro (ASD), Cluster R2 = 0.316 77
False flax seeds: LD muscle (in ethanol) 3502500, reflectance hierarchical R2 = 0.374
0% (C) Fatty acids (perirenal fat) analysis R2 = 0.86 (M vs. C)
10% (M) R2 = 0.90 (H vs. C)
15% (H) R2 = 0.29 (M vs. H)
Tuna Fat content (%), frozen, Fruit Tester 20 (Fantec), PLS 5.14 , RMSEP , 9.42d 79
glazed tuna 6001000
Fat content (%), frozen, transmittance 3.23 , RMSEP , 5.08d
nonglazed tuna
Fat content (%) , thawed 2.09 , RMSEP , 3.80d
tuna
Fat content (%) (with 3.18 , RMSEP , 4.72d
temperature compensation)
Skipjack fish Fat content (%) Fruit Tester 20 (Fantec), PLS 1.06 , RMSEP , 3.42d 80
6001000, I.N.A.
Meat Fat (%) Phazir 1624 MPLS RMSEP = 4.34 82
Moisture (%) (Polychromix), 1600 RMSEP = 0.63
Protein (%) 2400, reflectance RMSEP = 2.57
Pig Intact carcass fat; correct Phazir 1624 PLS2-DA 60.6 , 93.9 , 96.4 75
classification according to (Polychromix), 1600
feeding regimes (%) 2400, reflectance
a
Am, aerobic mesophiles; ANN, artificial neural networks; cfu, colony-forming units; En, Enterobacteriaceae; INA, information not available; Lab, lactic acid
bacteria; LD, longissimus dorsi; MPLS, multiblock partial least squares; PCA, principal component analysis; PLS, partial least squares; PLS-DA, partial least squares
discriminant analysis.
b
FreshlineTM 3MIX (30:40:30 O2/CO2/N2).
c
FreshlineTM 3MIX 20/5 (5:20:75 O2/CO2/N2).
d
Results vary according to the measured portion and/or wavelength selection.

known to be greatly responsible for harvested fruit and on the loss of quality portable devices are comparable to those
variability in fruit quality. Portable during storage.56,68 Research was also achieved using bench-top spectrome-
NIR spectroscopy could be a solution focused on the plant leaves, not just the ters.52,55,56,59,68 Cayuela and Weiland
to the problem of fruit selection, assess- fruit. There the nutritional status of a compared the performance of two dif-
ing the individual quality characteristics plant was mainly determined as a ferent portable NIR spectrometers and
of the fruits to match them to the function of its concentration of nitro- found that the success of this technique
required internal quality standards. One gen69 and other chemical elements, such is related to the selection of the most
of the main concerns of fruit growers as P, K, Ca, Mg, Fe, Zn, and Mn.70 The suitable instrument for a particular
and distributors is fruit quality after studies showed that NIR spectroscopy is parameter.55 Some of the weaknesses
harvest. The shelf-life and storage con- highly efficient for determining nitrogen of the NIR spectroscopy method include
ditions of various fruit were evaluated to concentration. the need to find a proper calibration
understand the influence of such crop The performance of different types of method and the constant need to keep it
practices as irrigation, fertilization, thin- spectrometers was also tested, determin- updated (especially when the samples
ning, and pruning on the quality of the ing that the results obtained using involved may be subject to periodical or

APPLIED SPECTROSCOPY OA 1221


focal point review
TABLE V. Reported applications of portable NIR devices for beverage and dairy-product analysis.a

Spectrometer, Multivariate
spectral range (nm), analytical
Species Attributes acquisition mode methods Results Reference

Milk (with adulterants: tap water, Fluid milk (% v/v) MicroPHAZIR PLS RMSEP = 4.74 89
whey, synthetic milk, synthetic (Polychromix), 1600
urine, urea, H2O2) 2400, diffuse
reflectance
Milk Fat (%) INA, 6001100, diffuse PLS RMSEP = 0.187 88
Protein (%) reflectance RMSEP = 0.120
DM (%) RMSEP = 0.296
Milk Fat (%) INA, 8001080 PLS 0.066 , RMSECV , 3.62b) 90
Protein (%) DNI, 10501650, 0.078 , RMSECV , 1.87b
Lactose (%) transflectance, RMSECV = 0.081b
Moisture (%) reflectance 0.09 , RMSECV , 0.25b
Temperature (%) 3.01 , RMSECV , 3.30b
Rice wine Alcohol (%) DNI, 11002150, PLS RMSEP = 0.259 86
Nonsugar solids (%) reflectance RMSEP = 0.0134
Tea drinks Tea polyphenols DNI, 11002150, PLS RMSECV = 0.059 85
Free amino acids reflectance RMSECV = 0.005
Beer Bitterness (IBU) PlaScan-SH (OPT MLR R2 = 0.67 83
Total polyphenol (mg/L) Research Inc.), 1200 R2 = 0.64
Total nitrogen (%) 2400, diffuse R2 = 0.69
pH reflectance R2 = 0.64
Beer color (EBC) R2 = 0.34
Apparent extract (%) R2 = 0.53
Alcohol (%) R2 = 0.76
Beer distinction PCA Beers were clustered into three groups
a
DM, dry matter; DNI, development of a new instrument; EBC, European Brewing Convention; H2O2, hydorgen peroxide; IBU, international bitterness unit; INA,
information not available; MLR, multiple linear regression; PCA, principal component analysis; PLS, partial least squares.
b
Results vary according to the type of spectrometer used.

TABLE VI. Reported applications of portable NIR instruments for cereal and feedstock analysis.a

Spectrometer, Multivariate
spectral range (nm), analytical
Species Attributes acquisition mode methods Results Reference

Wheat leaf Nitrogen content (fresh leaves) FieldSpec (ASD), 350 PLS RMSECV = 0.372 97
(% DM) 2500, reflectance
Nitrogen content (dried leaves) RMSECV = 0.268
(% DM)
Nitrogen content (all leaves) RMSECV = 0.352
(% DM)
LMA (g/m2) RMSECV = 6.300
Maize silage DM (%) INA, 9601700, I.N.A. MPLS RMSECV = 0.97 100
CP (%) RMSECV = 0.12
NDF (%) RMSECV = 0.40
Noodle wheat flours (whole Moisture (%) PlaScan-SH (OPT PLS RMSEP = 0.351 99
noodles) Protein (%) Research Inc.), 1200 RMSEP = 0.526
Ash (%) 2400, diffuse RMSEP = 0.397
Fat (%) reflectance RMSEP = 0.087
Carbohydrate (%) RMSEP = 0.681
Noodle wheat flours Moisture (%) RMSEP = 0.321
(powder) Protein (%) RMSEP = 0.426
Ash (%) RMSEP = 0.402
Fat (%) RMSEP = 0.091
Carbohydrate (%) RMSEP = 0.458
Rice Low-level cadmium-polluted INA, 12002400, diffuse CDA 86.7% 96
Medium-level cadmium-polluted reflectance 83.9%
High-level cadmium-polluted 87.5%
Overall correct classification rate 85.2%
Rice Protein content (%) INA, INA, transmittance PLS RMSEP = 0.279 95
Amylose content (%) RMSEP = 0.52
a
CDA, canonical discriminant analysis; CP, coat protein; DM, dry matter; INA, information not available; LMA, leaf mass per unit area; MPLS, multiblock partial
least squares; NDF, neutral detergent fibers; PLS, partial least squares.

1222 Volume 67, Number 11, 2013


seasonal changes). Consequently, some analyzed as well as on the sampling when spectroscopy was used to analyze
studies focused on finding the calibra- conditions.79,80 A portable visible NIR milk for fat protein and dry matter
tion models, testing and comparing (Vis-NIR) device was determined to content,88 as well as to detect and
several different preprocessing tech- efficiently distinguish between fresh quantify adulterated milk samples. The
niques, and optimizing regression meth- and frozen fish samples.81 research suggested that this method
ods.50,54,58,71,72 The problem of calibration is usually could potentially be used as an alterna-
Meat and Fish. Almost all the meat considered one of the biggest weakness- tive to traditional analysis methods
analyses in this sector were performed es of NIR spectroscopy. However, an because of its simplicity, sensitivity,
on slaughtered animals. Fish analyses interesting study proved that the suc- low energy cost, and portability. Never-
were normally performed on frozen cessful transfer of calibration models theless, the studies also revealed that
samples. Spectra were collected in from large, previously collected data- portable mid-infrared (mid-IR) systems
reflectance mode from different sections bases to new devices more suitable for have better discriminant power and
of the body. The published research in in situ analysis is possible.82 reliability of predictions than the NIR
this field indicates that the NIR spec- Beverages and Dairy. In studies of systems tested.89 Analyses of milk-
troscopy technique could work as an the beverages sector, NIR spectra were powder samples were also made, which
analytical sensor, establishing the state usually collected in transmittance or compared the results using two different
of meat conservation, although further transflectance mode. The samples were types of portable NIR and Vis-NIR
work remains to be done to develop placed in specifically designed sample spectrometers. Once again, the success
more robust models (Table IV).73 The chambers or in common quartz cells to of the technique was determined to be
potential of this technique to distinguish be read by the equipment. In some cases, closely related to the selection of the
between pork from different pig breeds the analyses were executed using dis- most suitable instrument.90
confirms that it is a rapid and objective persive handheld NIR equipment Cereals and Feedstock. In this area,
method for identification and authenti- equipped with a liquids adaptor or the included spectroscopy studies have
cation.74 A portable NIR device was accessory. Portable NIR devices have mainly been of wheat, rice, and corn, with
also tested as a way to make in situ been applied to the analysis of beverages the protein concentration being the pa-
classifications of individual pig carcass- and dairy products, and several success- rameter that was most often investigated
es as a function of the pigs feeding ful applications have been reported (Table VI). The studies demonstrated that
regimes. The portable device enabled (Table V). Portable devices seemed to portable NIR spectroscopy is suitable for
individual in situ inspections and suc- be a promising technique for distin- performing nondestructive, in-field mea-
cessfully classified Iberian pig carcasses guishing between types of beer and for surements of the protein content of
into three commercial categories. To evaluating beer quality in terms of total wheat,9194 corn,91 and rice.95 In-field
achieve these results, some instrumental polyphenols and total nitrogen. The NIR spectroscopy also proved to be
optimizations were required, especially differences in raw material and produc- useful as a rapid, nondestructive, and
in the wavelength range, the spectral tion processes seemed to be the most convenient analytical method for the
resolution, and the sampling area. Ad- common source of variability among primary screening and detection of cad-
ditional recommendations for new in- beers.83 Similar results were achieved mium-polluted rice.96 The investigation
strumental designs to be used in the when NIR spectroscopy was applied to of wheat-plant leaves to determine the
meat sector were also proposed.75 A Japanese sake. This technique enabled nitrogen content or the leaf mass showed
similar experiment was tried using lamb researchers to distinguish among differ- promising results as well. Consequently,
carcasses, but despite the correct classi- ent samples and could be a tool for the this technique represents a solution to the
fication of more than 90% of the improvement of Japanese sake quality.84 problem of finding a required rapid and
samples, researchers rated the perfor- In tea drinks, polyphenols and free nondestructive method that can be ap-
mance of the equipment as low.76 amino acids were shown to be the most plied during plant-growing cycle.97
Masoero et al. applied this technique important quality indicators, and porta- A portable NIR spectrometer was also
not only to rabbit meat but also to live ble NIR spectroscopy proved to be a fast used to predict the water content of rice
rabbits, showing that the feeding regime and reliable technique for testing the crackers, in an attempt to understand
produced real differences in groups of quality of tea drinks.85 Rice wine was their hygroscopic behavior.98 It was also
experimental live rabbits and in rabbit also the target of NIR spectroscopy used to determine the moisture content
meat samples. Correlations between the applications for determining the concen- of noodles.99 The texture of noodles is
rabbit samples and their feeding regimen trations of alcohol and non-sugar solids. dependent on the type of wheat flour as
were obtained, although with limited A portable NIR rice-wine analyzer was well as on mixing ratios used to make
success.77,78 successfully developed. The results of them, while another study used spec-
Portable NIR spectrophotometers these studies suggest that this portable troscopy to discriminate between noodle
were also used for the analysis of fish apparatus (which is user friendly and flours by describing the relationship
samples. Most of these studies were pollution-free) could be an efficient, fast, between the NIR spectra and the chem-
aimed at determining fish fat content. and reliable alternative way to analyze ical-analysis data.98
Results showed that this technique is rice-wine quality.86,87 Feedstock has also been analyzed
dependent on the fish-body section Good calibrations were also found using NIR spectroscopy. Animal health

APPLIED SPECTROSCOPY OA 1223


focal point review
TABLE VII. Reported applications of portable NIR devices for soil and manure analysis.a

Spectrometer, Multivariate
spectral range (nm), analytical
Species Attributes acquisition mode methods Results Reference

Soil Total N content (%) DNI, 940, 1050, 1100, BPNN RMSEP = 0.019 91
1200, 1300, and 1550,
reflectance
Soil Soil moisture content (%) DNI, 1450, INA Linear regression RMSEP = 0.85 109
method
Soil Total N content (%) DNI, 940, 1050, 1100, BPNN RMSEP = 0.043 110, 111
1200, 1300, and 1550,
reflectance
Soil Total N DNI, 8002500, PLS R2 = 0.8324 103
Total organic matter reflectance R2 = 0.8833
Soil Organic matter (%) Luminar 5030 PLS RMSEP = 13.353 104
pH (Brimrose), 1100 RMSEP = 1.1126
Ammonium nitrogen 2300, reflectance RMSEP = 23.2595
Nitric nitrogen RMSEP = 106.285
Total kalium RMSEP = 10.1516
Soil Organic C (%) DNI, 16003100, PLS, SMLR 0.18 , RMSEP , 0.27b 105
Moisture content (%) reflectance 1.7 , RMSEP , 1.9b
Clay content (%) 3.6 , RMSEP , 4.4b
Soils Organic C (%) DNI, 16402640, PLS 0.23 , RMSEP , 0.28c 106
Cation exchange capacity reflectance 3.59 , RMSEP , 3.91c
(mEq/100 g)
Moisture content (%) 1.59 , RMSEP , 1.88c
Cattle manure Total C (mg/g) INA, 3601690, INA PCA/PLS RMSEP = 23.4 115
Organic C (mg/g) RMSEP = 0.91
Total N (mg/g) RMSEP = 0.74
C:N (mg/g) RMSEP = 0.87
K (mg/g) RMSEP = 0.83
S (mg/g) RMSEP = 0.73
P (mg/g) RMSEP = 0.61
pH RMSEP = 0.89
Compost (moist) Organic matter (%) AgriSpec (ASD), 350 PLS, PCR 10.1 , RMSECV , 25.7b 116
Compost (oven-dried) 2500, diffuse
reflectance
a
BPNN, back-propagation neural network; DNI, development of a new instrument; INA, information not available; MLR, multiple linear regression; PCA, principal
component analysis; PCR, principal component regression; PLS, partial least squares; SMLR, stepwise multiple linear regression.
b
Results vary according to the calibration method.
c
Results vary according to the data set and moisture content.

is directly related to diet. Therefore, to small size) provided a low-cost solution ucts. Soil organic matter is one of the
meet the requirements of animals and for to the problem of determining wheat and most studied parameters.102108 Some
maximum production, diets must be corn quality in complex environ- experiments using spectroscopy showed
optimized. A study on the performance ments.91,92,94,101 a good correlation between the spectral
of portable NIR spectroscopy instru- Soils and Manures. Studies of soil data and data obtained using standard
ments when applied to the analyses of samples have also used NIR spectros- chemical methods, whereas others sug-
maize silage. The accuracy of the results copy (Table VII). Soil samples for these gested the need for further verification of
was very close to that obtained using a studies were usually collected at the results over a wider range of soil
laboratory NIR instrument.100 Once surface or at known depths. In those samples. Gomez et al. exposed for the
again, a comparison was made of situations, samples were first sieved and/ first time the potential of satellite hyper-
various regression techniques used dur- or dried (either oven- or air-dried) and spectral data for the prediction of the
ing the cereal analysis, and the results then analyzed. Different types of soils organic carbon content of soil. They
favored the artificial neural networks were investigated and compared. Some demonstrated good accuracy of the
(ANN) technique.93 Studies of the reports have been made of researchers model no matter what number or range
development of new portable NIR attempting in-field soil analyses using of soil samples used.108 Soil moisture
spectroscopy devices were also done specific contact probes. The measure- was also a commonly studied parame-
on cereals. It was concluded that the ment and control of soil characteristics ter,105,106,109 and one of these studies
portable equipment (which had a simple are particularly important for the proper used spectroscopy to generate spatial
structure, low-power consumption, and development of the agricultural prod- distribution maps.109 Total nitrogen

1224 Volume 67, Number 11, 2013


TABLE VIII. Reported applications of portable NIR devices in viticulture and olive oil production.a

Spectrometer, Multivariate
spectral range (nm), analytical
Species Attributes acquisition mode methods Results Reference

Grapes (fresh berries) SSC (8Bx) AvaSpec-2048 (Avantes), PLS RMSEP = 1.48 117
TA (g tartaric acid/dm3) 4001000, reflectance RMSEP = 1.48
pH RMSEP = 0.15
PA (mg/dm3) RMSEP = 133.90
EA (mg/dm3) RMSEP = 81.87
Grapes (homogenized samples) SSC (8Bx) RMSEP = 0.95
TA (g tartaric acid/dm3) RMSEP = 1.12
pH RMSEP = 0.13
PA (mg/dm3) RMSEP = 129.00
EA (mg/dm3) RMSEP = 77.70
Grapes (fresh berries) SSC (8Bx) PLS-DA 77.1%
TA (g tartaric acid/dm3) 68.6%
Grapes (homogenized samples) SSC (8Bx) 88.7%
TA (g tartaric acid/dm3) 83.1%
Grapevine leaf (Syrah, Merlot, Water potential Luminar 5030 PLS RMSECV = 1.48 126
Cabernet Sauvignon) (Brimrose), 11002300
Grapevine leaf (Cabernet transmittance RMSECV = 1.08
Sauvignon)
Grapes (Cabernet Sauvignon) SSC (8Bx) INA, 5901090, INA PLS 0.61 , RMSECV , 1.15b 118
Grapes (Cabernet Sauvignon, TA (g tartaric acid/dm3) INA, 4001000, PLS 0.2 , RMSEP , 0.4b 119
Sangiovese, Merlot) Maturity index (sugar/acidity reflectance 2.8 , RMSEP , 6.0b
ratio)
PA (mg/L) 101.3 , RMSEP , 125.7b
pH 0.0 , RMSEP , 0.1b
Reductant sugars (g/L) 6.6 , RMSEP , 12.2b
Grapes (Cabernet Sauvignon, SSC (8Bx) USB 2000 (Ocean PLS 1.010 , RMSEP , 1.267c 120
Carmene`re, Merlot, Pinot pH Optics), 6401300, 0.088 , RMSEP , 0.159c
Noir, Chardonnay) Anthocyanin concentration INA 0.183 , RMSEP , 0.315c
(mg/g)
Grapes SSC (8Bx) Luminar (Brimrose), PLS RMSECV = 1.9 121
pH 11002300, RMSECV = 0.16
TA (g/L) transmittance RMSECV = 1.89
Anthocyanin concentration RMSECV = 0.11
(mg/g)
Grapes SSC (8Bx) INA, 4001100, MLR RMSECV = 1.12 127
Acidity (g H2SO4/L) interactance RMSECV = 1.35
Water content (%) RMSECV = 1.89
Olives (Moraiolo, Dolce di Total phenols Luminar 5030 PLS 0.451 , RMSECV , 1.672c 128
Andria, Nocellara Etnea) Verbascoside (Brimrose), 1100 0.074 , RMSECV , 0.210c
Oleuropein 2300, transmittance 0.175 , RMSECV , 0.365c
3,4 DHPEA-EDA 0.237 , RMSECV , 1.138c
Olives (Arbequina, Picual, Oil content (%) Luminar 5030 PLS 1.52 , RMSECV , 1.99c 129
Verdial de Huevar, Manzanilla Moisture (%) (Brimrose), 1100 1.65 , RMSECV , 2.26c
de Sevilla) 2300, transmittance
Olives Fruit moisture (%) LabSpec (ASD), 350 PLS RMSECV = 1.741 130
DM (%) 2500, reflectance RMSECV = 1.710
Oil content (fresh weight) RMSECV = 0.901
(%)
Oil content (DM) (%) RMSECV = 1.619
Fruit maturity index (%) RMSECV = 0.465
Oil-free acidity (%) RMSECV = 0.030
a
DM, dry matter; 3,4 DHPEA-EDA, 3,4-dihydroxyphenolethanol-elenolic acid di-aldehyde; EA, extractable anthocyanins; H2SO4, sulfuric acid; INA, information
not available; MLR, multiple linear regression; PA, potential anthocyanins; PLS, partial least squares; PLS-DA, partial least squares discriminant analysis; SSC,
soluble solids content; TA, titratable acidity.
b
Results vary according to the calibration method.
c
Results vary according to the species.

content,103,104,110,111 pH,104 soil color spectra and laboratory-collected spectra al. simultaneously investigated the spec-
and mineral composition,112 and clay (after drying the samples). Surprisingly, tral properties of soil and wheat, with the
content have also been predicted.105,112 and contrary to what was expected, the aim of discriminating between conven-
Viscarra Rossel et al. compared models field-collected spectra provided better tional and conservation agricultural
for clay content using field-collected predictions of clay content.112 Hache et practices. The soil spectra were useful

APPLIED SPECTROSCOPY OA 1225


focal point review
in discriminating among tillage practic- eters such as the concentration of Leon-Moreno; he concluded that porta-
es, whereas the wheat spectra were more anthocyanins117,119121,123 and polyphe- ble NIR spectroscopy could be used to
suitable for discriminating among nutri- nols117 were also studied. evaluate oil content and moisture during
ent sources.113 In the detection of The viticulture studies concluded that different selection steps of olive-breed-
cyanide concentrations, portable NIR Vis-NIR portable devices could be ing programs, providing accurate results
spectrometers were considered to be suitable, rapid, and nondestructive tools for the selection of genotypes.131 Nev-
reliable instruments. Although spec- for assessing and monitoring grape ertheless, researchers suggested that
trometers could not replace traditional ripeness directly in the field. Sethura- further work was necessary to develop
laboratory analysis because of their masamyraja et al. used a portable NIR the calibration of the devices and, thus,
limited detection in this instance, they spectrometer for measuring anthocyanin to make the models more robust.
could be very useful in the detection of and Brix parameters in a geo-referenced Other Applications. Other applica-
contaminated areas.114 Portable soil field of wine grapes. Those quality tions of portable NIR spectroscopy
analytical instruments based on NIR indicators were then subjected to geo- included studies of several plants or
spectroscopy have also been developed. spatial modeling, resulting in the spatial plant leaves. Portable NIR instruments
Those systems presented several advan- distribution of wine quality variability were developed and employed to deter-
tages, such as stable performance and across the field (anthocyanin-content mine leaf water content 132134 and
high precision. Nevertheless, soil mois- data were used to form a quality zone, chlorophyll content.133,134 They were
ture seemed to influence the accuracy of whereas the Brix data set facilitated the also used to determine the total nitrogen
the detector, and measurement correc- prediction of the harvest timing).123 The content of fresh tea leaves, to monitor
tions were required.103,105,107,109111 influence of bunch position and orienta- plant growth, and to manage fertiliza-
Manures and composts are also in- tion on grape ripeness was also investi- tion.135 Portable NIR instruments are
cluded in this section. However, even gated to allow the selective harvesting of still being evaluated for possible use in
though the analyses done in the studies grape bunches depending on the type of collecting signature spectra from vege-
were performed using portable NIR- wine to be made.122 Susceptibility of the tation.136
based devices, the experiments were grapevines to disease was a factor of Some recent papers described results
done in the laboratory. Nevertheless, great concern; Calcante et al. tested comparing the performance of different
studies have concluded that field-porta- spectroscopy as a way to detect different NIR spectrometers when applied to the
ble NIR spectroscopy is suitable for levels of grapevine downy mildew same problem. Rotbart et al. compared
manure and compost analysis and that, symptoms.124,125 Laboratory and field the performance of three different NIR
despite the influence that environmental tests of grapevine leaves demonstrated spectrometers, including portable instru-
changes may have on instrument perfor- that NIR spectroscopy can be used to ments, in determining the nitrogen
mance, the devices would be more quantify the water potential of grapevine content of olive tree leaves.137
useful applied in the field.115,116 A leaves, revealing that the best predictive Other applications include the differ-
detailed list of these applications is models are those specific to the variety entiation of some plastics and foodstuffs
provided in Table VII. and maturity phase.126 In this area, once using portable NIR spectroscopy instru-
Viticulture and Olive Growing. again, the performance of different ments, relying not only on a statistical
Viticulture is one of the sectors that spectrophotometers 125 and modeling and mathematical approach but also on a
has been studied most using portable techniques118 was compared. A low-cost chemical interpretation of the NIR
NIR devices (Table VIII). These exper- portable apparatus was designed and spectra. Researchers intended to contin-
iments were done using samples in built with the aim of accurately measur- ue the basic interpretation of NIR
several ways, both in the field and in ing the ripeness parameters (previously spectra by focusing on various food-
the laboratory. While some researchers mentioned) under in situ conditions. stuffs and, thus, to provide a useful
analyzed grapes by the bunch (usually Researchers used spectral preprocessing analytical technique for many industrial
divided into sections), others focused on techniques to diminish the effects of needs.138
individual berries. Other studies com- error sources, such as temperature and
pared whole berries to homogenized humidity, thus achieving the desired PORTABLE VERSUS
samples. Picked grapevine leaves were robustness of the model.127 LABORATORY NEAR-
also analyzed. Conversely, studies of The quality of olive oil depends INFRARED INSTRUMENTS
olives were performed on the intact fruit directly on the quality of the olives. Portable instruments have been re-
on the tree. The parameters analyzed Among the studied parameters of olives ported as having some limitations when
were similar to those employed for fruits were the predicted phenol compound compared with state-of-the-art lab
and vegetables, with the aim being to content, 128 oil and moisture con- bench-top NIR instruments, which are
determine the stage of maturity. The tents,129131 dry matter, and oil-free often equipped with interferometers and
parameters considered most often were acidity.126 The studies demonstrated that better optical properties (e.g., better
the SSC (in degrees Brix [8Bx]) and portable NIR instruments were feasible signal-to-noise ratio, sensitivity, and
pH,117123 titratable acidity,117,121,122 tools for in situ, nondestructive mea- optical resolution). Essentially, labora-
reducing sugars,119,122 and tartaric and surements of total phenols in olives. The tory instruments with interferometers
malic acids.122 Phenol ripening param- same parameters were also studied by (e.g., the Michelson interferometer) have

1226 Volume 67, Number 11, 2013


Portable instruments have the obvious
advantage of possible field-use because
of an absence of moving parts. Techno-
logical innovations in dispersive porta-
ble instruments have been reducing the
advantages of laboratory instruments.
Figure 1 compares the performance of
a laboratory Fourier transform (FT)-NIR
instrument (FTLA2000, ABB) to a
dispersive portable NIR instrument
(FieldSpec 4, ASD) when measuring
grapes (Fig. 1a) and grapevine leaves
(Fig. 1b) using approximately the same
8 cm -1 resolution. As shown, the
performance of the two devices is
comparable under the same measure-
ment conditions. Nevertheless, depend-
ing on the measurement conditions and
sample characteristics, the field opera-
tion of NIR spectrometers may encoun-
ter additional problems inherent to the in
situ measurements, which may introduce
unwanted variability into the spectra,.
Several authors in the area of agro-
food products have compared the figures
of merit of calibration models using
portable and laboratory instruments. All
these comparisons show that some
limitations exist, mainly related to the
sampling accessory used to measure the
samples. For instance, the optical path
lengths in transmittance measurements
and illumination areas in reflectance
mode are often different. Saranwong et
al. compared the performance of a
portable NIR instrument Fruit Tester
20 (Fantec, Kosai-city, Japan) with a
research-type Foss NIRSystems Model
6500 (Metrohm AG, Switzerland) in
measuring the sugar content (in degrees
Brix) of mango fruits in diffuse reflec-
tance mode. The two instruments shared
roughly the same wavelength range,
measuring-head size, and detector type,
and the instruments showed similar
levels of accuracy (standard error of
prediction [SEP], 0.40 8Bx), despite the
fact that the spectra of same sample
produced using the two instruments
appeared to be considerably different.59
FIG. 1. Comparison of NIR spectrum obtained on a NIR portable instrument (FieldSpec 4,
ASD, USA) and a NIR bench-top instrument (FTLA2000,ABB, USA). (A) For grape berries. The main conclusion here was that a
(B) For grapevine leaves. Black line, portable instrument; gray dotted line, bench-top portable device was recommended for
instrument. the in situ analysis of fruits similar to
mangos. A similar comparison study of
several advantages over dispersive in- gratings): the optical throughput advan- these two instruments, measuring fat
struments based on different technolo- tage (Jacquinot advantage), the multi- content in frozen skipjack, showed the
gies (e.g., interference filters, diffraction plexing advantage (Fellgett advantage), Foss instrument to have the superior
grating, and acousto-optical diffraction and resolution (Connes advantage).19 performance.80

APPLIED SPECTROSCOPY OA 1227


focal point review
Two other studies, by Perez-Marn at
al., compared the performance of a
handheld micro-electro-mechanical sys-
tem (MEMS) spectrophotometer (Phazir
2400, Polychromix Inc., Wilmington,
MA), with a diode-array Vis-NIR spec-
trophotometer (Perten DA-7000, Perten
Instruments) in analyzing different pa-
rameters in plums44 and nectarines.68
The measurements were also performed
in diffuse reflectance mode. In brief, the
studies concluded that, although slightly
better results were obtained for the
diode-array instrument (for the plum
and nectarine parameters), the handheld
proved to be a more convenient tool for
analyzing samples because it afforded
the additional advantages of portability
and low cost. A similar conclusion was
reached by Zamora-Rojas et al. when
they compared a handheld MEMS-based
spectrometer (16002400 nm) with a
high-resolution NIR spectroscopy
monochromator (4002500 nm) for the FIG. 2. Number of scientic papers involving the use of portable NIR spectrometers in the
agro-food industry since 2003.
classification of individual Iberian pig
carcasses into different commercial cat-
egories.75 Although most comparison
studies reported that the portable instru- the low cost of most portable instru- tion ability than the NIR systems
ments had lower performance scores ments compared to laboratory instru- tested.89 Attempts were made to transfer
than the laboratory instruments, the ments (note that the costs of some calibrations from high-performance at-
main conclusions were that their flexi- portable instruments are still comparable line NIR spectrometers to portable
bility and possibility of field-use were to laboratory instruments), efforts to devices, and this was successful, as
major advantages that made the portable further reduce the costs of the instru- reported by Zamora-Rojas et al., for
options the best solution. ments have been reported, especially by calibrations of fat, moisture, and protein
The selection of the most suitable adapting instruments to specific tasks. in meat products.82 The successful
portable spectrometer was also investi- Kalinin et al. described the performance transfer of a previously existing calibra-
gated. Cayuela and Weiland compared of a specially designed instrument tions database to a portable device
two commercially available portable (designated by BIKAN-K) for measur- allows a new approach for fast, low-
spectrometers: a Labspec (Analytical ing fat, protein, and lactose in restored cost, online/in situ analysis of agro-food
Spectral Devices Inc., Boulder, CO) milk.89 This equipment is able to products.
and a Luminar 5030 (Brimrose Corp., measure liquid samples with a 12 mm-
MD).55 The calibration used four orange thickness in the range 8001080 nm. PROSPECTIVE
varieties, and the parameters studied are Reported results were comparable to DEVELOPMENTS
listed in Table III. According to their those obtained using commercial equip- A survey of scientific papers pub-
RMSEP values, the prediction accuracy ment; in this case, the tested equipment lished in the last decade (Fig. 2) shows a
of the two spectrometers was similar for was the MC-75 grating spectrometer steady increase in the number of re-
most of the fruit-quality parameters equipped with a Si linear sensor search and development studies being
determined. However, the Labspec de- (ILX511). conducted using these types of portable
vice presented slightly better results for A recent paper compared the feasibil- spectrometers. They are used not only
some physical parameters such as the ity of using portable and handheld IR by companies to ensure process and
fruit weight, rind weight, and flesh (both NIR and mid-IR) spectrometers product quality control but also by
firmness. The authors suggested that for monitoring milk adulteration by tap researchers, demonstrating the evolution
the larger contact probe of the Labspec water, whey, synthetic milk, synthetic of these devices in terms of hardware
unit (with a light source of 20 mm, urine, urea, and hydrogen peroxide. The and optical systems/detector specifica-
versus the 8 mm of the Luminar 5030) portable and handheld mid-IR systems tions. The number of scientific studies
allowed the exploration of a larger allowed the development of classifica- using this technology is expected to
portion of the fruit, consequently ex- tion and quantification models with increase substantially over the coming
plaining the observed results.55 Despite better discrimination power and predic- years. In addition, the major develop-

1228 Volume 67, Number 11, 2013


ments in this area are expected to be in portable instruments, it is absolutely Ligne de la Qualite des Fruits et Legumes.
clear that there is still much work to be [Ph.D. Thesis]. Toulouse, France: lInstitut
manufacturing science. The major trends National Polytechnique de Toulouse, 1992.
are toward miniaturization, increasing done to make these instruments easily 11. S. Roy, R.C. Anantheswaran, J.S. Shenk,
the specifications quality while reducing usable in the field under production M.O. Westerhaus, R.B. Beelman. Determi-
the cost of the devices. One example of conditions. Because many of the appli- nation of Moisture Content of Mushrooms by
this is an increase in the range of cations surveyed here were actually Vis-NIR Spectroscopy. J. Sci. Food Agr.
1993. 63(3): 355-360.
miniaturized MicroNIRt spectrometers performed under laboratory conditions, 12. J. Lammertyn, B. Nicola, K. Ooms, V. De
(JDS Uniphase [JDSU] Corporation, it is therefore not possible at the present Smedt, J. De Baerdemaeker. Non-Destruc-
Milpitas, CA), which weigh less than time to evaluate the real performance of tive Measurement of Acidity, Soluble Solids,
60 g, allow measurements from 850 to portable NIR devices under production and Firmness of Jonagold Apples Using
NIR-Spectroscopy. Trans. ASAE. 1998.
2450 nm, and have the option of conditions. 41(4): 1089-1094.
interchanging different sampling acces- 13. C.J. Clark, V.A. McGlone, R.B. Jordan.
ACKNOWLEDGMENTS
sories.139 As new technology is imple- Detection of Brownheart in Braeburn
mented in these devices, they will CS, ML, and RP acknowledge FCT-MEC Apple by Transmission NIR Spectroscopy.
(Fundacao para a Ciencia e Tecnologia) for the Postharvest Biol. Technol. 2003. 28(1):
become more stable, more reliable, and grants SFRH/BD/91419/2012, SFRH/BD/91521/ 87-96.
better able to produce results that are 2012, and SFRH/BPD/81384/2011, respectively. 14. C.J. Clark, V.A. McGlone, C. Requejo-
comparable to the bench-top FT spec- JL thanks FSE (Fundo Social Europeu) and MEC Tapia, A. White, A.B. Woolf. Dry Matter
trometers. Another important develop- (Ministe rio da Educac a o e Cie ncia) for the Determination in Hass Avocado by NIR
financial support through the POPH-QREN pro- Spectroscopy. Postharvest Biol. Technol.
ment is the reduction in the gram. The authors also acknowledge FCT-MEC 2003. 29(3): 300-307.
manufacturing costs and subsequent for the financial support through the strategic 15. E. Mehinagic, G. Royer, R. Symoneaux, D.
market prices of the spectrometers project PEst-C/EQB/LA0006/2011. Bertrand, F. Jourjon. Prediction of the
overall. It is already possible to find Sensory Quality of Apples by Physical
portable NIR devices that sell for less Measurements. Postharvest Biol. Technol.
1. K.H. Choi, K.J. Lee, G. Kim. Nondestruc- 2004. 34(3): 257-269.
than $10 000 and allow full NIR tive Quality Evaluation Technology for 16. B.M. Nicola, K. Beullens, E. Bobelyn, A.
spectral-region scanning, which con- Fruits and Vegetables Using Near-Infrared Peirs, W. Saeys, K.I. Theron, J. Lammertyn.
trasts with the situation a few years ago. Spectroscopy. Paper presented at: Interna- Nondestructive Measurement of Fruit and
tional Seminar on Enhancing Export Com- Vegetable Quality by Means of NIR Spec-
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CONCLUSION Thailand; May 18-19, 2006. Technol. 2007. 46(2): 99-118.
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py. Part B: Intact Fruit Studies. J. Near 75. E. Zamora-Rojas, D. Perez-Marin, E. De 86. L. Jiang, H. Chen, B. Cai. Development of a
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