Talanta 183 (2018) 320–328

Contents lists available at ScienceDirect

Talanta
journal homepage: www.elsevier.com/locate/talanta

Assessment of infant formula quality and composition using Vis-NIR, MIR T

and Raman process analytical technologies
⁎
Xiao Wanga, Carlos Esquerrea, , Gerard Downeya,b, Lisa Henihana,c, Donal O’Callaghanc,
Colm O’Donnella
a
UCD School of Biosystems and Food Engineering, University College Dublin, Belfield, Dublin 4, Ireland
b
Food Chemistry and Technology Department, Teagasc Food Research Centre, Ashtown, Dublin 15, Ireland
c
Food Chemistry and Technology Department, Teagasc Food Research Centre, Moorepark, Fermoy, Co. Cork, Ireland

A R T I C L E I N F O A B S T R A C T

Keywords: In this study, visible and near-infrared (Vis-NIR), mid-infrared (MIR) and Raman process analytical technologies
Visible and near-infrared spectroscopy (Vis- were investigated for assessment of infant formula quality and compositional parameters namely preheat tem-
NIR) perature, storage temperature, storage time, fluorescence of advanced Maillard products and soluble tryptophan
Mid-infrared spectroscopy (MIR) (FAST) index, soluble protein, fat and surface free fat (SFF) content. PLS-DA models developed using spectral
Raman spectroscopy
data with appropriate data pre-treatment and significant variables selected using Martens’ uncertainty test had
Infant formula
Preheat temperature
good accuracy for the discrimination of preheat temperature (92.3–100%) and storage temperature
Storage (91.7–100%). The best PLS regression models developed yielded values for the ratio of prediction error to
deviation (RPD) of 3.6–6.1, 2.1–2.7, 1.7–2.9, 1.6–2.6 and 2.5–3.0 for storage time, FAST index, soluble protein,
fat and SFF content prediction respectively. Vis-NIR, MIR and Raman were demonstrated to be potential PAT
tools for process control and quality assurance applications in infant formula and dairy ingredient manufacture.

1. Introduction deterioration, as both physical transformations and chemical reactions

Infant formula comprises nutrients and bioactive ingredients de-
signed to fulfil the nutritional and health needs of infants and to be a
suitable alternative to breast milk when a mother cannot or chooses not
to breast-feed [1,2]. Infant formula manufacture involves several pro-
cessing steps, including blending of ingredients using water to achieve a
homogeneous solution followed by sufficient heat treatment or dehy-
dration to provide bacteriological safety [2]. Heat treatments typically
employed in infant formula manufacture include pasteurization (72 °C),
high-temperature short-time (HTST) heating, ultra-high temperature
(UHT) treatment (135–150 °C) and in-container sterilisation
(115–120 °C) [1–3]. However, thermal treatments may result in major
physicochemical changes in infant formula including protein dena-
turation and aggregation, lipid–protein and protein–protein interac-
tions, sugar isomerisation and Maillard browning reactions [1,3]. Infant
formula powder is commonly packaged using cans for shipping, storage
and distribution. Although milk powders generally have a long shelf life
at ambient temperature (12–24 months), infant formula powder which
is manufactured using vegetable oils or lipids rich in polyunsaturated
long chain fatty acids has lower storage stability [4,5]. Higher storage
temperature has been demonstrated to accelerate infant formula quality
in most cases increase at higher storage temperature [5]. The quality of
powder infant formula may deteriorate as a result of lactose crystal-
lisation, lipid oxidation and Maillard reactions [5]. Conventional
methods for investigating the effects of preheat treatments and storage
on infant formula powder generally measure changes in specific che-
mical or physical markers, such as moisture, water activity, Maillard
reactions, protein denaturation or lipid oxidation [1,4–6]. The fluor-
escence of advanced Maillard products and soluble tryptophan (FAST)
method was developed by Birlouez-Aragon, Nicolas, Metais, Marchond,
Grenier and Calvo [7] as a rapid fluorometric method to estimate the
heat treatment of liquid milk. It involves measurement of two com-
plementary heat-induced phenomena using fluorescence: (i) overall
whey protein denaturation, quantified by the fluorescence of trypto-
phan (Trp) and (ii) the Maillard reaction, globally quantified by fluor-
escence of the advanced Maillard products (AMP) [1,7]. Whey proteins
are heat sensitive and may become denatured due to heat-treatment
and form complex aggregates with caseins [6]. Levels of soluble protein
influence powder solubility which is a key infant formula quality
parameter [8]. Fat content is an important component in infant formula
and is highly regulated e.g. European Union Directives defines a reg-
ulatory limit of 4.4–6.0 g per 100 kcal for first-age infant formula [2].

⁎
Corresponding author.
E-mail address: carlos.esquerre@ucd.ie (C. Esquerre).

https://doi.org/10.1016/j.talanta.2018.02.080
Received 18 December 2017; Received in revised form 16 February 2018; Accepted 19 February 2018
0039-9140/ © 2018 Elsevier B.V. All rights reserved.
X. Wang et al.
Surface free fat (SSF) is free fat that is located on the powder particle
surface and in pores and capillaries created during the drying process; it
is influenced by product composition, homogenisation pressure, spray-
drying inlet/outlet temperatures and powder storage conditions [9].
Higher levels of SFF in infant formula reduce wettability and increase
the likelihood of lipid oxidation [10]. However current analytical
methods for the above parameters are time consuming and require
sample preparation steps such as reconstitution and filtration [1,6].
Thus there is a need in industry for the development and validation of
rapid and non-destructive methods for nutritional and quality assess-
ment of dairy ingredients and infant formula.
Process analytical technology (PAT) has been defined by the United
States Food and Drug Administration (FDA) as a mechanism to design,
analyse and control manufacturing processes through the measurement
of critical process parameters (CCPs) which affect Critical Quality
Attributes (CQAs) of raw and in-process materials and processes
[11,12]. PAT tools are extensively employed in the pharmaceutical and
chemical industries to facilitate the manufacture of products of con-
sistent quality with reduced waste and lower processing costs. How-
ever, PAT can also be employed in other process industries including
food manufacture [12]. There is a need to validate PAT tools which can
be used in dairy processing and infant formula manufacture.
Visible and near-infrared (Vis-NIR), mid-infrared (MIR) and Raman
process analytical tools have potential application in infant formula
manufacture [13–15]. In recent years many studies investigating Vis-
NIR [16–18], MIR [19,20] and Raman [21] spectroscopy in infant
formula applications have been reported. Applications of NIR, MIR and
Raman spectroscopy to detect melamine in infant formula and other
milk powders have been reported [22–24]. Melamine has strong and
distinctive absorptions in the NIR (at 1466 nm) and MIR (at
1650 cm−1) spectral regions and also has strong bands in Raman (at
676 cm−1) [22–24] which can be exploited for detection applications.
Liquid chromatography-triple-quadrupole tandem mass spectrometry
(LC-MS/MS) is the standard reference analytical method currently used
by FDA for melamine detection in infant formula [22]. It provides a
limit of detection (LOD) as low as 250 ppb, however sample preparation
and clean-up procedures are time consuming and labour-intensive [22].
NIR, MIR and Raman spectroscopy methods enable rapid, sensitive
(LOD < 1 ppm) and reliable detection of melamine in infant formula
powder [22–24]. Partial least squares regression (PLS) is one of the
most commonly used chemometric tools for prediction of dairy product
parameters using spectroscopic data [25,26]. Partial least squares dis-
criminant analysis (PLS-DA) is a classical PLS regression technique in
which the response variable is built by assigning arbitrary values to
each class e.g. 0 for one class and 1 for the other class [13,27].
The hypothesis of this study was that Vis-NIR, MIR and Raman
spectra can be used to develop chemometric models for prediction of
infant formula quality and compositional parameters. Vis-NIR, MIR and
Raman process analytical technologies coupled with chemometric
methods were evaluated for their potential to (i) discriminate infant
formula preheat and storage temperatures, and (ii) predict infant for-
mula storage time, FAST index, soluble protein, fat and SFF content.
2. Materials and methods
2.1. Infant formula ingredients
Skim milk powder (SMP) was produced from fresh raw milk ob-
tained from a dairy farm in Teagasc (Moorepark, Cork, Ireland),
skimmed at 50 °C, evaporated at 60 °C to 30% total solids (TS) and dried
in a single stage spray dryer with inlet and outlet temperatures of 180
and 95 °C respectively. Whey protein concentrate (WPC 35% w/w
protein) was obtained from Arrabawn Co-op Society Ltd. (Nenagh, Co.
Tipperary, Ireland). Vitamins and lactose were supplied by Glanbia
(Kilkenny, Ireland). Sunflower oil was procured from a local super-
market (Supervalu, Fermoy, Ireland).
321
Talanta 183 (2018) 320–328
2.2. Infant formula manufacture and storage
Model liquid infant formula mixes were manufactured using 4.1 kg
of SMP, 5.5 kg of WPC, 13.8 kg of lactose, 5.9 kg of sunflower oil,
0.301 g of vitamin A, 0.670 g of vitamin B and 60.7 kg of water. Model
liquid infant formula mixes were preheated at three different tem-
peratures (72, 95 and 115 °C) using a MicroThermics Lab heat ex-
changer (MicroThermics, North Carolina, USA) at a flow rate of
2 L min−1 with a holding time of 15 s. The preheated samples were then
homogenised at 65 °C using an in-line two stage valve-type homo-
geniser (150/50 PSI) (Model NS2006H, Niro Soavi, Parma, Italy).
Following overnight storage at 4 °C with gentle agitation, the samples
were evaporated in recirculation mode at 65 °C to 50% TS using a
single-effect falling film evaporator (Anhydro F1 Lab; Copenhagen,
Denmark), before spray drying using an Anhydro 3-stage drier with
fines return to the top of the drier (SPX Flow Technology, Soeborg,
Denmark). Inlet/outlet temperatures of the spray dryer were set at 175/
90 °C respectively.
Infant formula samples were initially analysed after manufacture (0-
month storage) at room temperature (~ 20 °C), and subsequently split
for storage at two different temperatures, namely 15 ± 2 °C and
37 ± 2 °C for up to one year. Aliquots of samples from each storage
regime were analysed at months 3, 6 and 12 after production. Two
replicates were analysed to give an experimental design of 2 replicates
× 3 preheat temperatures × (0-month storage + (2 storage tempera-
tures × 3 storage times)) (n = 42). Approximately 60 g of infant for-
mula powder was used for Vis-NIR, MIR and Raman spectral mea-
surements.
2.3. Process analytical technologies
2.3.1. Vis-NIR spectroscopy
Vis-NIR spectra were collected on an NIRSystems 6500 spectrometer
(NIRSystems. Inc., Maryland, USA). Infant formula samples were filled
into a ring cup (7.5 cm diameter and 1.5 cm depth) with an optical
window diameter of 5.5 cm and sealed with a screw-on lid. Logarithmic
transformed reflectance spectra (log(1/R)) were acquired and recorded
over the spectral range 400–2498 nm at 2 nm steps. Two sub-samples
were scanned for each sample; all samples were scanned in random
order at room temperature (~ 20 °C). Spectral acquisition and file
conversion were performed using WINISI software (version 1.04;
Infrasoft International, Port Matilda, USA). Spectra were exported from
WINSI software as JDX files. The mean of 2 replicate scans for each
sample was used in subsequent chemometric analysis.
2.3.2. MIR spectroscopy
MIR spectra were collected on a Bio-rad Excalibur series FTS 3000
FT-IR spectrometer (Analytica Ltd. Dublin, Ireland). Infant formula
samples were placed on a Silver Gate Evolution single reflection atte-
nuated total reflectance (ATR) accessory with a ZnSe recessed crystal
plate (Specac Ltd., Kent, UK). A single beam spectrum of each sample
was collected and corrected using air as a background. Scans (n = 128)
were co-added over the spectral range 600–4000 cm−1 at a nominal
resolution of 4 cm−1. Two sub-samples and triplicate scans were col-
lected for each sample in random order at room temperature (~ 20 °C).
Instrument control, spectral acquisition and file conversion were per-
formed using WIN-IR Pro (v. 3.0; ThermoGalactic, Salem, MA, USA)
software supplied by the instrument manufacturer. The mean of 6 re-
plicate spectra for each sample was used in subsequent chemometric
analysis.
2.3.3. Raman spectroscopy
Raman spectra were collected on a DXR SmartRaman spectrometer
(ThermoFisher Scientific UK Ltd., Loughborough, UK) using a 780 nm
diode laser and a charge-coupled device (CCD) detector operating at
− 50 °C. For spectra collection, approximately 30 g infant formula
X. Wang et al.
powder was filled into a sealed, clear plastic sample bag and placed
over the aperture of the universal platform sampling accessory. Spectra
of each sample were accumulated for 500 s (i.e. 10 s exposure time ×
50 exposures) using a 120 mW laser. Raman intensity counts per second
(cps) were recorded over the spectral range 23–3397 cm−1 at 1 cm−1
intervals. Samples were scanned twice in random order at room tem-
perature (~ 20 °C). Cosmic ray spike removal and fluorescence cor-
rection of spectra were performed automatically using OMNIC software
(v 9.2.98; Thermo Fisher Scientific Inc., USA). Instrument control and
spectral acquisition were also performed using OMNIC software.
Spectra were exported as GRAMS files. The mean of two duplicate
spectra of each sample was used in subsequent chemometric analysis.
2.4. Selected quality and compositional parameters
2.4.1. FAST method
The FAST method was carried out as described by Guan, Liu, Ye and
Yang [28]. 0.5 mL of rehydrated infant formula (at 13% TS) was added
to 24.5 mL of sodium acetate buffer (pH 4.6); the mixture was shaken
vigorously and left for 5 min at room temperature (~ 20 °C). After fil-
tration through a nylon filter (0.45 µm pore size), the filtrate was
transferred into a standard fluorescence quartz cuvette (10 × 10 mm)
for spectral measurement using a Cary Eclipse fluorescence spectro-
fluorimeter (Varian Inc., Palo Alto, CA, USA). Fluorescence of trypto-
phan (FTrp) and advanced Maillard products (FAMP) were measured at
340 nm (excitation at 290 nm) and 420 nm (excitation at 330 nm) re-
spectively. Each infant formula sample was analysed in triplicate at
room temperature (~ 20 °C). The FAST index was calculated as:
FASTindex = 100 × (FAMP/FTrp)
2.4.2. Soluble protein
Soluble protein analysis (expressed as g/100 g powder) was carried
out at 6 and 12 months storage (n = 24 samples) using an Amaltheys
analyser II (Spectralys Innovation, Romainville, France) as described by
Lacotte, Gomez, Bardeau, Muller, Acharid, Quervel, Trossat and
Birlouez-Aragon [6]. The Amaltheys analyser II is a compact and por-
table right-angle fluorometer which measures the natural fluorescence
of peptidic Trp to assess sample protein concentration [6]. For analysis,
a scoop (ca. 0.5 mL) of infant formula was weighed, reconstituted with
10 mL Milli-Q water and held for 30 min. 1 mL of reconstituted infant
formula was mixed with 50 mL sodium acetate buffer (pH 4.55; Spec-
tralys Innovation, Romainville, France). Precipitation of caseins and
denatured whey proteins occurred within 3 min, after which the su-
pernatant was filtered using a 0.45 µm nylon filter in a 4-face optical
acrylic cuvette. Triplicate analyses of each sample were carried out at
room temperature (~ 20 °C).
2.4.3. Fat content
Fat content of infant formula (%, w/w of powder) was analysed
with a Smart Trac analyser (CEM SMART Trac™ Fat and Moisture
Analyser, CEM Corporation, Matthews, USA).
2.4.4. SFF content
SFF content of infant formula (%, w/w of powder) was determined
using the GEA Niro analytical method GEA [29].
2.5. Chemometric analysis
For chemometric analysis, the acquired Vis-NIR, MIR and Raman
spectra were imported directly into The Unscrambler software (v9.7;
Camo, Trondheim, Norway). For model development, selected Vis-NIR
(400–2498 nm, 1100–2498 nm, 700–1098 nm), MIR (800–3500 cm−1,
800–1800 cm−1, 2800–3500 cm−1) and Raman (800–3100 cm−1,
800–1800 cm−1, 2800–3100 cm−1) spectral ranges were used.
Principal component analysis (PCA) was used to identify and, if
322
Talanta 183 (2018) 320–328
necessary, eliminate spectral outliers using a T2 Hotelling 95% con-
fidence threshold [30]. PLS-DA models were developed to discriminate
preheat and storage temperatures. For preheat temperature dis-
criminant analysis, each preheat temperature was discriminated from
the other two temperatures separately. A discrimination threshold of
0.5 was used. PLS regression models were built using storage time,
FAST index, soluble protein, fat and SFF content (y variables) and infant
formula Vis-NIR, MIR and Raman spectra (X variables). Models were
constructed using raw (non-treated) and pre-treated (standard normal
variate (SNV) transformation or linear baseline correction) spectral
data. Pre-treatments were employed to remove baseline shifts, slope
changes and multiplicative scatter effects related to particle size and
powder compression. The Martens’ uncertainty test was used to select
significant variables. This test uses a jack-knifing procedure to calculate
statistics for the regression coefficients of all variables and identify
significant variables using these statistics [31]. The selected variables
were used to developed new PLS-DA and PLS models. Root mean square
error of leave-one-out (full) cross-validation (RMSECV) was used to
select the optimal number of latent variables (LV) in each model.
Performance of the PLS-DA models was evaluated in terms of cor-
rect identification (i.e. the % of correctly predicted samples in both
classes) [13,27]. Assessment of PLS model performance was carried out
by evaluating RMSECV, determination coefficient (R2) and the ratio of
prediction error to deviation (RPD) values. RPD was calculated by di-
viding the standard deviation of the reference data by RMSECV [32]. In
PLS regression, five levels of prediction accuracy were considered based
on the RPD values. Models having a value of RPD below 1.5 are con-
sidered to be unsuitable for deployment, models with an RPD value
between 1.5 and 2.0 may only be used to distinguish between low and
high values. RPD values between 2.0 and 2.5 indicate the possibility for
approximate quantitative prediction while models with RPD values
between 2.5 and 3.0, and above 3.0 are considered as good and ex-
cellent prediction models, respectively [32,33].
3. Results and discussion
Table 1 lists the summary statistics of infant formula quality and
compositional parameters investigated. Additional information on in-
fant formula sample preheat temperature, storage temperature, storage
time, FAST index, soluble protein, fat and SFF content studied are
presented as Supplementary materials (Table S1, Figs. S1, S2 and S3).
3.1. Vis-NIR, MIR and Raman spectra
Raw Vis-NIR, MIR and Raman spectra of infant formula samples are
shown in Fig. 1. The main vibrational bands observed in Vis-NIR, MIR
and Raman spectra and their tentative assignments reported in the
literature are shown Table 2 [21,34–41]. PCA analysis was performed
on Vis-NIR, MIR and Raman data collected to detect outliers and vi-
sually explore sample distribution and clustering (Fig. 2) in a multi-
variate space. T2 Hotelling values of individual sample spectra were
calculated to detect outliers using a 95% confidence threshold (num-
bered spectra in Fig. 1). A total of three Vis-NIR (sample no. 6, 32 and
33), two MIR (sample no. 32 and 33) and three Raman (sample no. 24,
Table 1
Summary statistics of infant formula quality and compositional parameters investigated.
FAST Soluble protein Fat content SFF
index (g/100 g (% w/w) content
powder) (% w/w)
Maximum 21.54 5.29 28.65 2.60
Minimum 1.88 0.77 24.94 0.02
Mean 7.06 2.83 27.03 1.12
Standard deviation 4.62 1.64 0.91 0.65
X. Wang et al. Talanta 183 (2018) 320–328

(A) Vis-NIR Table 2

0.9 Reported attributions for vibrational bands observed in infant formula NIR, MIR and
Raman spectra.
Log (1/R)

0.6 32 & 33 Wavelength / Bands assignment Attribution

Wavenumber

0.3 NIR spectra (nm)

1215 ν C-H second overtone protein [34]
6 1483 ν N-H first overtone protein [34]
1570 ν N-H first overtone protein [34]
0
1725 ν C-H first overtone fat [34]
400 900 1400 1900 2400
1765 ν C-H first overtone fat [34]
Wavelengths (nm)
1940 ν O-H + δ O-H H2O [34]
(B) MIR 2110 νs N-H + amide III protein [34]
2310 ν C-H + δ C-H fat [34]
0.4 2347 νs CH2 +δ=CH2 protein [34]
32 & 33
2488 ν C-H + ν C-C carbohydrate [34]
Absorption

MIR spectra (cm−1)

0.25
700 δ N-H protein [35]
769 δ C-C-O + δ C-C-H carbohydrate [36]
1034 ν C-O carbohydrate [37]
0.1
1252 ν C-N protein [35]
1392 δ O-H + δ C-O-H + δ C-C-H carbohydrate [36]
-0.05 1533 ν C-N + δ N-H protein [38]
600 1100 1600 2100 2600 3100 3600 1646 ν C˭O + δ N-H protein [38]
1740 ν C˭O fat [35]
Wavenumbers (cm-1)
2845 νas CH2 fat mainly [35]
(C) Raman 2918 νs CH2 fat mainly [35]
Raman spectra (cm−1)
250 24 354 – carbohydrate [39]
443 δ C-C-C + τ C-O carbohydrate [40]
Instensity

646 δ C-C-O carbohydrate [40]

150 880 δ C-C-H + δ C-O-C carbohydrate [40]
946 δ C-O-C + δ C-O-H + ν C-O carbohydrate [40]
50 1130 ν C-O + ν C-C + δ C-O-H carbohydrate [39]
1296 τ C-H protein [41]
1438 δ C-H protein [39]
32 & 35
-50 1656 ν C˭C; ν C˭O protein [21]
0 500 1000 1500 2000 2500 3000 2884 νs CH3 fat (mainly) and
Wavenumbers (cm-1) carbohydrate [40]

Fig. 1. Non-treated spectra of model infant formula (A) Vis-NIR, (B) MIR and (C) Raman. ν-stretching, δ-deformation, τ-twisting, s-symmetric, as-asymmetric.
Numbered spectra were identified as outliers using a T2 Hotelling 95% confidence
threshold.

2800–3100 cm−1, non-treated spectra over the range of

32 and 35) spectra were identified as outliers in this way and removed
prior to PLS-DA and PLS modelling. Sample 32 was identified as an
outlier in all three spectral datasets. The moisture content of sample 32
increased during storage (> 4% compared to ca. 2% for other sam-
ples). This may have been caused by damage to the integrity of the
sample container storing this sample. The remaining infant formula
samples had similar Vis-NIR, MIR and Raman spectra.
3.2. Discrimination of preheat temperature
The performance of the best PLS-DA preheat temperature dis-
crimination models developed using Vis-NIR, MIR and Raman data
acquired over selected spectral ranges is shown in Table 3A, B and C.
Plots of estimated class values of the best PLS-DA models for preheat
temperature discrimination are presented as Supplementary materials
(Figs. S4, S5 and S6). In general, infant formula preheat temperature
discrimination models developed using Vis-NIR had better discrimina-
tion performance than MIR or Raman i.e. 100% correct identification
for each preheat temperature (3–4 LV). The best PLS-DA models de-
veloped using MIR had correct identification rates of 97.4% (2 LV) for
72 °C preheated samples and 100% (4 LV) for both 95 and 115 °C
preheated samples. These models were developed using non-treated
MIR spectral data (2800–3100 cm−1), linear baseline treated spectral
data (800–3500 cm−1) and linear baseline treated spectral data
(800–1800 cm−1) respectively. For Raman spectra, PLS-DA models
developed using non-treated spectra over the range of
250–3100 cm−1 and SNV-treated spectra over the range of
800–1800 cm−1 had the best discrimination performance for 72 °C
(97.4% correct identification, 4 LV), 95 °C (92.3% correct identifica-
tion, 5 LV) and 115 °C (92.3% correct identification, 2 LV) preheated
samples respectively.
Fig. 3A shows the regression coefficients of the best overall PLS-DA
model developed for discrimination of 72 °C preheated samples (model
D1, 4 LV). Large regression coefficients were observed at 2172, 2264
and 2494 nm. The absorption at 2172 nm can be attributed to amide I
and amide III, while the absorptions at 2264 and 2494 nm can both be
attributed to carbohydrate [34]. Although both Vis-NIR and MIR
models discriminated all 95 and 115 °C preheated samples, models D5
(4 LV) and D7 (3 LV) used lower number of LV compared to models D4
(5 LV) and D8 (4 LV) respectively. Models D5 and D7 were the best
overall discrimination models developed for 95 and 115 °C preheated
samples. Large regression coefficients were observed at 1503, 1738 and
2845 cm−1 (Fig. 3B) for discrimination model D5. The absorption at
1503 cm−1 can be attributed to protein [42], while the absorption
bands observed at 1738 and 2845 cm−1 are both related to fat and can
be attributed to C˭O stretching and symmetrical CH2 stretching re-
spectively [35]. Large regression coefficients were observed at 618,
1546 and 1814 nm for the best 115 °C discrimination model (D7;
Fig. 3C). The absorption at 1546 nm can be attributed to O-H stretching
first overtone, whereas the absorption at 1814 nm can be attributed to a
combination of C-H and C-C stretching [34].

323
X. Wang et al. Talanta 183 (2018) 320–328

(A) spectroscopic techniques. Plots of estimated class values for the best
32 Vis-NIR
0.6 33 6 Vis-NIR, MIR and Raman models developed are shown as
31
0.4 Supplementary materials (Fig. S7). The best overall storage tempera-
PC-2 (8.5%)

35 19
0.2 20
ture discrimination model (100% correct identification) was developed
0
34 2435
23
42 41 38
37
25
using non-treated NIR data in the 1100–2498 nm spectral range (model
26
14 113
7
22 40 12 11 82
2110
39
30
28 18 51729 D10, 6 LV). Large regression coefficients were observed at 1410, 1434
-0.2 4
2716
3
9 15 and 1878 nm (Fig. 3D). Absorptions at 1410 and 1434 nm can both be
-0.4
attributed to O-H stretching first overtone, while absorption at 1878 nm
-0.6
can be attributed to a combination of O-H and C-O stretching [34]. The
-2.5 -1.5 -0.5 0.5 1.5 2.5
PC-1 (87.7%) best MIR model developed (91.2% correct identification, 3 LV) was
obtained using linear baseline treated spectral data (800–1800 cm−1)
(B)
0.3
MIR while the best Raman model developed (97.0% correct identification, 3
32
LV) was obtained using SNV-treated spectral data (250–3100 cm−1).
0.2
PC-2 (2.3%)

2728285
0.1 15
17
16
93
25
30
22
26
23 614
7218
3.4. Prediction of storage time
21 10 8
0 33 11
401214
20 13
24
37
38
39
-0.1 42
1941 Vis-NIR, MIR and Raman spectra of all infant formula samples, re-
34
-0.2 36 gardless of preheat and storage temperatures, were used to develop PLS
3135
-0.3 regression models for storage time prediction. The best PLS models for
-4 -3 -2 -1 0 1 2 storage time, which were all developed using linear baseline treated
PC-1 (97.1%) spectra, had low RMSECV, high R2 and RPD values (Table 4A). The best
(C) overall storage time prediction model was developed using Vis-NIR
Raman
150 spectra (700–1098 nm; Fig. 4A). This model (P1, 6 LV, RMSECV 0.7
100 1
33
16 20
34 223811
months) had an RPD value of 6.1 (R2 = 0.97). Large regression coef-
12 26
3941 2 ficients were observed at 802, 1034 and 1036 nm (Fig. 4B). Absorption
PC-2 (4.6%)

50 9 23 24
31 42
17 29 5
0 36
18 40 at 802 nm can be attributed to N-H stretching third overtone, while
4
-50 8
15
6 1928
30
14 3
13 37
absorptions at 1034 and 1036 nm can be attributed to N-H stretching
10 32
-100 21 25 second overtone and a combination of C-H stretching, C-H deformation
-150 27 7 and CH2 [34]. The best MIR storage prediction model (P2, 6 LV) was
-200
35
developed using the 800–3500 cm−1 spectral range (R2 = 0.92,
-1000 -500 0 500 1000 RPD = 3.6), and the best Raman model (P3, 5 LV) was developed using
PC-1 (92.3%)
the 250–3100 cm−1 spectral range (R2 = 0.96, RPD = 4.8).
Fig. 2. Score plots of PC1 vs PC2 of model infant formula based on full range (A) Vis-NIR,
(B) MIR and (C) Raman spectral data. The ellipses in each case correspond to a T2
3.5. Prediction of FAST index
Hotelling 95% confidence threshold. Numbers refer to sample no.

Table 4B lists the best FAST index prediction models developed for
3.3. Discrimination of storage temperature each of the spectroscopic techniques and selected spectral ranges in-
vestigated. The best PLS prediction models for the three spectroscopic
Table 3D shows the performance of the best PLS-DA models de- techniques were developed using non-treated Vis-NIR spectra
veloped for storage temperature discrimination using the three (400–2498 nm), linear baseline treated MIR spectra (800–3500 cm−1)

Table 3
Discrimination performance of the best full cross-validation PLS-DA models developed for preheat temperature discrimination of (A) 72 °C, (B) 95 °C and (C) 115 °C, and (D) storage
temperature discrimination using selected Vis-NIR, MIR and Raman spectral data.

Spectra Spectral ranges Model Data pre-treatment No. of Variables No. of Samples No. of correctly identified Overall correct identification LV

Class 0 Class 1

(A) Preheat temperature (72 °C)

72 °C 95 + 115 °C
NIR 1100–2498 nm D1 SNV 72 39 14/14 25/25 100.0% 4
MIR 2800–3500 cm−1 D2 Linear 211 40 13/14 26/26 97.5% 2
Raman 800–1800 cm−1 D3 Non-treated 43 39 13/14 25/25 97.4% 4
(B) Preheat temperature (95 °C)
95 °C 72 + 115 °C
Vis-NIR 700–1098 nm D4 SNV 23 39 13/13 26/26 100.0% 5
MIR 800–3500 cm−1 D5 Linear 20 40 13/13 27/27 100.0% 4
−1
Raman 250–3100 cm D6 Non-treated 150 39 11/12 25/27 92.3% 5
(C) Preheat temperature (115 °C)
115 °C 72 + 95 °C
Vis-NIR 400–2498 nm D7 SNV 37 39 12/12 27/27 100.0% 3
MIR 800–1800 cm−1 D8 Linear 19 40 13/13 27/27 100.0% 4
Raman 800–1800 cm−1 D9 SNV 23 39 10/13 26/26 92.3% 2
(D) Storage temperature
15 °C 37 °C
NIR 1100–2498 nm D10 Non-treated 67 34 16/16 18/18 100% 6
MIR 800–1800 cm−1 D11 Linear 74 34 14/16 17/18 91.2% 3
Raman 800–1800 cm−1 D12 SNV 55 33 14/15 18/18 97.0% 3

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X. Wang et al. Talanta 183 (2018) 320–328

(A) (B)
NIR MIR
12 1738
2264 50 2845
Regression Coefficients

Regression Coefficients
7 30

2 10
-10
-3
-30
-8 -50
2172 2494 1503
-13 -70
1100 1500 1900 2300 800 1283 1765 2247 2926 3408
Wavelength (nm) Wavenumber (cm-1)

(C) NIR (D) NIR

10 618 2500 1410
Regression Coefficients

Regression Coefficients
1814
6 1500
4
2 500
0
-500
-2
-4
-1500
-6
1546 1434 1878
-8 -2500
400 800 1200 1600 2000 2400 1100 1500 1900 2300
Wavelength (nm) Wavelength (nm)
Fig. 3. Regression coefficients of the best overall PLS-DA models developed for preheat temperature discrimination of (A) 72 °C (SNV-treated NIR, 1100–2498 nm; model D1), (B) 95 °C
(linear baseline treated Vis-NIR, 700–1098 nm; model D5) and (C) 115 °C SNV-treated Vis-NIR, 400–2498 nm; D7), and (D) storage temperature discrimination (non-treated NIR,
1100–2498 nm; model D10).

and SNV-treated Raman spectra (800–1800 cm−1). The best overall
model (P5, 4LV, RMSECV 1.72) which was developed using MIR data
had an RPD value of 2.7 (R2 = 0.87) indicating good prediction per-
formance (Fig. 5A). The largest regression coefficient was observed at
1024 cm−1 (Fig. 5B), absorption at this band can be attributed to car-
bohydrate C-O stretching [27]. Although the FAST method is relatively
rapid and sensitive, numerous sample preparation steps (e.g. rehydra-
tion, precipitation of casein and filtration) are required for analysis of
powder samples. Use of the rapid spectroscopic techniques investigated
in this study would enable FAST index prediction without these sample
preparation steps.
3.6. Prediction of soluble protein
Table 4C lists the performance of the best PLS models developed for
soluble protein prediction for each of the three spectroscopic techni-
ques and selected spectral ranges investigated. The best NIR model
(model P7, 6 LV) was developed using non-treated spectra
(1100–2498 nm) and had an R2 value of 0.86 and an RPD value of 2.6.
The best overall model (P8, 3 LV, RMSECV 0.57 g/100 g powder) was
developed using MIR non-treated spectra (800–1800 cm−1) and had an
R2 value of 0.89 and an RPD value of 2.9 (Fig. 6A). The largest re-
gression coefficient was observed at 1642 cm−1 (Fig. 6B), absorption at

Table 4
Prediction performance of the best full cross-validation PLS models developed for prediction of (A) storage time (B) FAST index, (C) soluble protein, (D) fat content and (E) SFF content
using selected Vis-NIR, MIR and Raman spectral data.

Spectra Spectral ranges Model Data pre-treatment No. of Variables No.of Samples RMSECV R2 RPD LV

(A) Storage time

Vis-NIR 700–1098 nm P1 Linear 9 39 0.7 0.97 6.1 6
MIR 800–3500 cm−1 P2 Linear 87 40 1.2 0.92 3.6 6
Raman 250–3100 cm−1 P3 Linear 43 39 0.9 0.96 4.8 5
(B) FAST index
Vis-NIR 400–2498 nm P4 Non-treated 95 39 2.21 0.78 2.1 5
MIR 800–3500 cm−1 P5 Linear 185 40 1.72 0.87 2.7 4
Raman 800–1800 cm−1 P6 SNV 30 39 1.89 0.85 2.5 5
(C) Soluble protein
NIR 1100–2498 nm P7 Non-treated 38 22 0.63 0.86 2.6 6
MIR 800–1800 cm−1 P8 Non-treated 22 22 0.57 0.89 2.9 3
Raman 800–1800 cm−1 P9 Non-treated 14 21 0.96 0.69 1.7 3
(D) Fat content
Vis-NIR 400–2498 nm P10 SNV 29 39 0.56 0.74 1.6 2
MIR 800–3500 cm−1 P11 SNV 22 40 0.35 0.86 2.6 4
Raman 250–3100 cm−1 P12 SNV 59 39 0.44 0.76 2.1 3
(E) SFF content
Vis-NIR 400–2498 nm P13 Linear 224 39 0.23 0.88 2.8 6
MIR 2800–3500 cm−1 P14 SNV 20 40 0.22 0.90 3.0 3
Raman 800–1800 cm−1 P15 SNV 78 39 0.26 0.84 2.5 4

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X. Wang et al. Talanta 183 (2018) 320–328

(A) (A)
RMSECV = 0.7 Vis-NIR RMSECV = 0.57 MIR
R2 = 0.97 R2 = 0.89
Predicted storage time (month)

Predicted soluble protein

RPD = 6.14 RPD = 2.87
11 4.5

(g/100g powder)
5 2.5

-1 0.5
-1 5 11 0.5 2.5 4.5
Measured storage time (month) Measured soluble protein (g/100g powder)
(B)
1036 Vis-NIR (B)
802 MIR
60000
Regression Coefficients

1642
150

Regression Coefficients
40000
20000 100

0 50
-20000 0
-40000 - 50
-60000
- 100
-80000 1034
700 800 900 1000 - 150
800 1186 1572
Wavelength (nm)
Wavenumber (cm-1)
Fig. 4. PLS regression model for storage time prediction developed using linear baseline
Fig. 6. PLS regression model for soluble protein prediction developed using non-treated
treated Vis-NIR spectra (700–1098 nm; model P1): (A) predicted versus measured storage
MIR spectra (800–1800 cm−1, model P8): (A) predicted versus measured soluble protein,
time, (B) regression coefficients.
(B) regression coefficients.
0-month storage (○), 15 °C storage (+ ), 37 °C storage (◇), 72 °C (blue), 95 °C (green)
and 115 °C (red). (For interpretation of the references to color in this figure legend, the
reader is referred to the web version of this article.) 3.7. Prediction of fat content

this band can be attributed to protein C-N stretching and N-H de- The performance of the best PLS models developed for fat content
formation [38]. The best Raman model (model P9, 3 LV) was developed using each spectroscopic technique investigated is shown in Table 4D.
using non-treated spectra (800–1800 cm−1) and had an R2 value of The best PLS models were developed using SNV-treated Vis-NIR, MIR
0.69 and an RPD value of 1.7. The low RPD value of this Raman model and Raman spectra in the ranges of 400–2498 nm, 800–3500 cm−1 and
limits its utility to distinguish between samples of low and high soluble 250–3100 cm−1 respectively. The best Vis-NIR prediction model (P10,
protein values. 2 LV) had an R2 value of 0.74 and an RPD value of 1.6, indicating it may
(A) only be used to distinguish between low and high fat content samples.
RMSECV = 1.72 MIR The best overall model (P11, 4 LV, RMSECV 0.35%) was developed
R2 = 0.87
using MIR data and had an R2 value of 0.859 and an RD value of 2.6
RPD = 2.69
Predicted FAST index

20 (Fig. 7A). Large regression coefficients were observed at 1740 and

2918 cm−1 (Fig. 7B), absorption at these bands can be attributed to C-O
stretching and symmetrical CH2 stretching respectively and are asso-
ciated with fat in milk powder [35]. The best Raman prediction model
10 (P12, 3 LV) had limited ability to predict infant formula fat content (R2
= 0.76, RPD = 2.1).

3.8. Prediction of SFF content

0
0 5 10 15 20 25
Measured FAST index The performance of the best PLS models developed for SFF content
(B) is summarised in Table 4E. The best overall model (P14, 3 LV, RMSECV
MIR 0.22%) was developed using SNV-treated MIR spectra
200 1746 (2800–3500 cm−1) and had an RPD value of 3.0 (Fig. 8A). Large re-
Regression Coefficients

gression coefficients were observed at 2845 and 2920 cm−1 (Fig. 8B),
100 absorption band at 2845 cm−1 can be attributed to asymmetrical CH2
stretching of fat, while the absorption band at 2920 cm−1 can be at-
0 tributed to symmetrical CH2 stretching [38]. The best SFF prediction
models using Vis-NIR (P13, 6 LV) and Raman (P15, 4 LV) were obtained
-100
using linear baseline treated Vis-NIR spectra (400–2498 nm) and SNV-
-200 treated Raman spectra (800–1800 cm−1) respectively. Both models had
1024 high R2 values (0.84–0.88) and RPD values (2.5–2.8), and can be
-300 considered as good prediction models for SFF content.
800 1283 1765 2247 2926 3408
Wavenumber (cm-1)
4. Conclusions
Fig. 5. PLS regression model for FAST index prediction developed using linear baseline
treated MIR spectra (800–3500 cm−1; model P5): (A) predicted versus measured FAST The feasibility of Vis-NIR, MIR and Raman spectroscopic techniques
index, (B) regression coefficients.
coupled with chemometric tools for qualitative and quantitative

326
X. Wang et al. Talanta 183 (2018) 320–328

(A) for (i) discrimination of infant formula preheat and storage tempera-
RMSECV = 0.35 MIR
R2 = 0.86 tures, and (ii) prediction of infant formula storage time, FAST index,
28.5 RPD = 2.59 soluble protein, fat content and SFF content. Validation of the devel-
Predicted fat content

oped chemometric models using a larger sample size is necessary to

confirm model robustness. This study shows the potential of Vis-NIR,
(% w/w)

MIR and Raman PAT tools for quality assessment and control of infant
26.5 formula and dairy ingredient manufacturing processes.

Acknowledgments

24.5 Xiao Wang's Ph.D study was financially supported by the Chinese
24.5 26.5 28.5 Scholarship Council (201308300003).
Measured fat content (% w/w)
Funding information
(B)
2 1740 MIR
This project was supported by the Irish Department of Agriculture,
1.5
Food and the Marine through the Food Institutional Research Measure
Regression Coefficients

1
(FIRM) (Project Reference No: 11/F/052).
0.5
0
Conflict of interest
-0.5
-1
Xiao Wang declares that he has no conflict of interest. Carlos
-1.5
Esquerre declares that he has no conflict of interest. Gerard Downey
-2
declares that he has no conflict of interest. Lisa Henihan declares that
-2.5 2918 she has no conflict of interest. Donal O’Callaghan declares that he has
-3
no conflict of interest. Colm O’Donnell declares that he has no conflict
800 1283 1765 2247 2926 3408
of interest.
Wavenumber (cm-1)
Fig. 7. PLS regression model for fat content prediction developed using SNV-treated MIR Ethical approval
spectra (800–3500 cm−1; model P11): (A) predicted versus measured fat content, (B)
regression coefficients.
This article does not contain any studies with human participants or
animals performed by any of the authors.
(A)
RMSECV = 0.22 MIR
R2 = 0.90 Appendix A. Supporting information
2.2 RPD = 2.97
Predicted surface free fat

Supplementary data associated with this article can be found in the

content (% w/w)

online version at http://dx.doi.org/10.1016/j.talanta.2018.02.080.

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