International Dairy Journal 73 (2017) 63e67

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International Dairy Journal

journal homepage: www.elsevier.com/locate/idairyj

The effect of temperature on the development of browning of

amorphous and crystalline lactose
Helene Ranger a, Anthony H.J. Paterson b, *, Jeremy S. McLeod c
a
AgroSup, Dijon, France
b
School of Engineering and Advanced Technology, Massey University, Palmerston North 4442, New Zealand
c
Hilmar Cheese Company, CA. USA

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

Article history: When lactose crystals are dried in industrial driers the temperatures used can, when exposure time is too
Received 3 February 2017 long, cause the crystals to undergo non-enzymatic browning. This leads to a defect in the final product.
Received in revised form Understanding the kinetics allows driers to be designed to avoid this. To examine the non-enzymatic
26 May 2017
browning kinetics of amorphous and crystalline lactose, samples were heat treated for 2e120 min at
Accepted 29 May 2017
Available online 12 June 2017
110
C, 120
C, 130
C, 140
C and 150
C. The evolution of colour was followed by spectrophotometry at
420 nm and colorimetry (L* a* b*). The absorbance and the b* values increased while L* value decreased
with time and temperature. A first order reaction model with Arrhenius temperature dependence pro-
vided a good fit to the data. A difference was seen between crystalline and amorphous lactose, with the
latter having more intensive browning under the same conditions due to the increased surface area
available.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction The caramelisation reactions of many sugars, including lactose,

Industrially, after the crystallisation of lactose, the crystals are
separated from the remaining liquor by centrifugation and then
dried in a flash drier followed by a fluid bed drier. Drying needs to
occur quickly without altering the nutritional and organoleptic
qualities of the product (Schuck et al., 2004). To expedite the pro-
cess and to maximise drying capacity, it is possible to increase the
temperature, but only to a certain limit to avoid non-enzymatic
browning of the powder creating an undesirable coloration.
Non enzymatic browning is desired for foods like bakery prod-
ucts and coffee for flavour and colour production, but it is unde-
sirable in dried dairy products. The browning increases with
temperature, holding time and storage (Morales & van Boekel,
1998). The two most important non-enzymatic browning re-
actions are: (1) the Maillard reaction, where sugars react with
nitrogen-containing compounds, such as proteins, to form brown
pigments known as melanin and (2) the caramelisation reaction,
where sugars are heated in the absence of nitrogen-containing
compounds (Eskin, Ho, & Shahidi, 2013).
* Corresponding author. Tel.: þ64 6 951 7116.
E-mail address: A.Paterson@massey.ac.nz (A.H.J. Paterson).
have been studied, but mainly for the sugars in highly saturated
solutions (Buera, Chirife, Resnik, & Lozano, 1987a,b; Chen, Yang,
Chen, & Liu, 2009; Diaz & Clotet, 1995; Park, Kang, & Kim, 1998).
Buera et al. (1987a,b) showed that sugars follow zero to mixed
order kinetics with Arrhenius temperature dependence. Quintas,
Guimar~ aes, Baylina, Branda~o, and Silva (2007) used a multi-
response method to account for the effects of pH and tempera-
ture. Their model did not work when low moisture content (<3.2%)
sucrose was used. The probable reason for the discrepancy was a
change in the reaction pathway.
The work reported here has focused on the browning of dry
lactose crystals and dry amorphous lactose, (aW<0.3) similar to the
conditions that will be found in lactose dryers.
2. Methods
To avoid the need to understand the complex reactions involved
in caramelisation, a simple approach of measuring the colour
change by two methods and then fitting overall first order reaction
kinetics while simultaneously applying Arrhenius temperature ef-
fects on the fitted terms was taken. To predict lactose browning
with time and temperature, the Arrhenius model was applied: k0 is
the Arrhenius constant (s1), Ea is the activation energy (J mol1), R

http://dx.doi.org/10.1016/j.idairyj.2017.05.005
0958-6946/© 2017 Elsevier Ltd. All rights reserved.
64 H. Ranger et al. / International Dairy Journal 73 (2017) 63e67
is the constant R ¼ 8.3145 (J mol1 K1) and T is absolute tem-
perature (K), (Burdurlu & Karadeniz, 2003).


RT
Ea
k ¼ k0 e
Browning depends on the k factor and difference between L*
and L*∞. This equation is the same for the spectrophotometer
values (A420) and colorimeter values (L*, a*, b*).
dL*  
¼ k L*  L*∞
dt
In this equation, k is a first order rate constant (s1), which
varied according to a temperature dependence that is described by
the Arrhenius equation (1), t is time (s).
ZL* Zt
dL*
  ¼ k dt
L*  L*∞
L*0 0 (Fig. 2). The a* value, representing the red and green colours, was
0 1
L*  L*∞
ln@ A ¼ kt
L*0  L*∞
    browning had occurred at 120
C after 40 min for both the crys-
L* predicted ¼ L*  L*0  L*∞  1  ekt
The L*0 and L*∞ are the initial and infinity values of the lightness
value. L*∞, k0 and Ea were fitted to all data simultaneously by
minimising the residual sum of squared error by non-linear
regression with excel, Microsoft Office 2003 similar to the
method used by Rajchasom (2014).
To compare the k values, the kref values at a reference temper-
ature of 130
C, the mean temperature of the range used, were
calculated.
The crystalline alpha lactose monohydrate (ALM) used was
pharmaceutical grade (USP) obtained from Fonterra and the
amorphous lactose was made by dissolving ALM in deionised water
and then spray-drying it using the method of Clark, Paterson, Joe,
and McLeod (2016).
For the browning experiments, 5 g of powder was placed ho-
mogeneously in an aluminium cup. To prevent direct radiation
from the oven element a stainless steel plate was placed on the
bottom element and each sample was covered with an aluminium
cup.
Amorphous and crystalline lactose samples were heat treated
for from 2 to 120 min at 110
C, 120
C, 130
C, 140
C and 150
C in a
Breville BOV550 model (230e240 V, 50 Hz, 1350e1500 W) oven
that was controlled by a PID temperature controller (CAL3300
Autotune Temperature Controllers) to within ±1
C. The evolution
of colour was followed by colorimetry (L* a* b*) using a tristimulus
Fig. 1. Picture of lactose browning after 40 min at five different temperatures.
colorimeter and collecting 3 repeat measurements over different
parts of the sample. Absorbance measurements were also made
using a PG Instruments Ltd, T60U, UV/V spectrophotometer at
420 nm (Morales & van Boekel, 1998) after dissolving one g of
(1) lactose in 9 mL of deionised water.
3. Results and discussion
With the increase of temperature and time, the crystalline and
amorphous lactose samples became darker. The top row of Fig. 1 is
(2)
the amorphous lactose and the bottom row is crystalline lactose.
They show the colour change after 40 min at different tempera-
tures, starting from the left at 150
C with 10
C drops while the
sample on the right is the control at ambient temperature. Visually,
the colour change is noticeable. This visual observation corre-
sponds to an increase of absorbance and b* value, representing the
yellow/blue colour range, with blue at the negative limit and yellow
(3)
at the positive limit of the scale, but also an L* value decrease
not used in this study because there was no systematic change in its
value as the lactose powders browned.
In Fig. 2, the fitted models are represented by the lines. When
(4)
measured by spectrophotometry, b* or L* only a little browning was
found for both types of lactose at 110
C. Noticeable levels of
(5) talline and amorphous lactose. The level of intensity of change for
the amorphous lactose was greater than for the crystalline lactose
by all techniques. This is shown by the time infinity values recorded
in Table 1. These results are consistent with the visual observations
(Fig. 1) where the browning was more pronounced for amorphous
lactose than crystalline lactose. This is attributed to the large sur-
face area available for reaction in the amorphous lactose structure
meaning more lactose will have reacted in a given time, although
the rate of change, as evidenced by the time it takes to get to the
final values, is similar. The experimental data was well represented
by a first order browning kinetic model with Arrhenius tempera-
ture dependence for all three colour measurement techniques.
For the amorphous lactose at 130
C, 140
C and 150
C many of
the results after 50 min do not follow the model. This can be
explained by the crystallisation of the amorphous lactose. Under
these conditions the amorphous lactose can crystallise (Clark et al.,
2016) into an anhydrous crystal form. The b* and L* measured
values then become a composite of the browned amorphous
lactose and a contribution from the lactose crystals and the rate will
depend on how much of the amorphous lactose crystallised and the
type of crystal formed. The scatter in the data at each temperature
reflects that this was different for each sample.
At 140
C the crystallisation is more visible than that at 130
C.
This is expected because the crystallisation occurs faster at higher
temperatures (Clark et al., 2016). At 150
C there is evidence of
crystallisation occurring from 40 min onwards, but there is
 H. Ranger et al. / International Dairy Journal 73 (2017) 63e67 65

Fig. 2. Fitted profile of the first order kinetic model with the experimental data points of the various methods used to measure colour change at five different temperatures. The top
row is by absorbance values (A420), the second row by b* values (yellow colour) and the bottom row by L* values (lightness). The left hand column is crystal lactose and the right
hand column is the amorphous lactose results. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

Table 1 considerable scatter in the data, suggesting that the crystallisation

Kinetic parameters for crystal and amorphous lactose browning.
was not always present. This may be because the amorphous
Parameter Crystal Amorphous lactose that had undergone the browning reaction had decom-
Spectrophotometer posed before crystallisation was possible and that these regions
A4200 0 0.057 continued to brown as amorphous lactose while other areas crys-
A420∞ 0.387 1.029 tallised. The effect needs further study as it was inconsistent in the
kref (s1) 2.95E-04 1.12E-04
results seen here. The data from the samples that had obviously
Ea (kJ mol1) 157.9 198.9
Colorimeter L* crystallised were excluded from the kinetic model parameter fitting
L *0 96.98 98.77 procedure.
L *∞ 85.10 61.04 At temperatures above 100
C the a-lactose monohydrate
kref (s1) 1.79E-03 5.08E-04 gradually loses its water of crystallisation. At temperatures as high
Ea (kJ mol1) 127.2 159.4
as 140
C, all the water of crystallisation will be removed
Colorimeter b*
b* 0 0.457 5.07 completely if given enough time (DFEpharma, 2011). The loss of
b* ∞ 14.81 30.18 water of crystallisation is accompanied by a change of the crystal-
kref (s1) 3.1E-03 1.52E-03 line structure of the lactose. The lactose becomes anhydrous.
Ea (kJ mol1) 123 159.5
Further heating of lactose to higher temperatures causes lactose
66 H. Ranger et al. / International Dairy Journal 73 (2017) 63e67
Fig. 3. Lost weight plot for crystalline lactose after ( ) 90 and (-) 120 min at each
temperature.
decomposition. The primary reaction products of pyrolysis tend to
polymerise, resulting in brown and black coloured macromole-
cules. Eventually the lactose becomes black on heating
(DFEpharma, 2011).
To complete the interpretation of this change of state, the
weight loss was considered. Due to the water of crystallisation the
normal water content of a-lactose monohydrate is around 5%. Fig. 3
shows progressive loss of the water of crystallisation with time and
temperature. The a-lactose monohydrate crystals are becoming
anhydrous. The amorphous lactose (Fig. 4) showed a progressive
decrease in weight with increasing temperature. Amorphous
lactose is very hydroscopic and has a large ability to hold water
(Bronlund & Paterson, 2004). The increased weight loss is probably
due to the loss of water with the increase losses corresponding to
removing water that was progressively more bound. Decomposi-
tion of the lactose due to the browning reaction is also a possibility.
The kinetic parameters that were obtained in this study by
fitting all the data from the samples that had not crystallised during
the experimentation are given in Table 1.
Fig. 4. Lost weight plot for amorphous lactose after ( ) 90 and (-) 120 min at each
temperature.
The amorphous lactose gives a more intensive colour change
with the infinity values of all three methods being darker than the
crystal form. The literature gives values of Ea (kJ mol1) in the range
of 65e190 kJ mol1 for non-enzymatic browning, which agrees
well for the values found here which ranged from 123 to
199 kJ mol1 (Fox, 2009; Heldman & Lund, 1992; Roos, 2009; Villota
& Hawkes, 1992). Their results were for dairy powders with protein
as well as lactose present, so there will have been Maillard
browning occurring as well as the caramelisation reactions that
have been measured in this work.
A small difference was found between the reaction kinetics for
crystalline and amorphous lactose. The Ea values from all methods
(Table 1) show that the activation energy for the amorphous lactose
is higher than for the crystal reaction, indicating that the amor-
phous lactose browning reaction is more sensitive to temperature
than the browning reaction of crystalline lactose. The kref values at
130
C for amorphous lactose are about half of the values for the
crystal reaction indicating that the amorphous lactose reacts slower
than the crystalline lactose, although they are similar. This is
important in the context of driers because the flash drying process
used in the production of crystalline lactose usually creates amor-
phous lactose on the surface of the crystals. The degree to which
this happens is dependent on the conditions used for drying and
the free moisture content of the lactose exiting the centrifuge. The
results in this work show that as amorphous lactose browns more
slowly than crystalline lactose the surface of the lactose crystals
with amorphous lactose formed during the initial drying steps will
be less sensitive to browning later in the process.
4. Conclusion
It was concluded that first order kinetics with Arrhenius tem-
perature dependence adequately describe the browning of both
amorphous and crystalline alpha lactose monohydrate for all three
methods of measuring the colour change and that amorphous
lactose reacts slower than crystalline lactose, but results in a more
intensive colour due to the higher surface area available for
reaction.
Acknowledgements
This work was completed with funding provided by Hilmar
Cheese Company and this is gratefully acknowledged. This paper
was first presented by Ranger, Paterson, and McLeod (2014) at the
15th TSAE National Conference and the 7th International Conference,
in Thailand and a version is published on the CD of the proceedings.
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