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Effect of calcium on white sugar turbidity

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Effect of calcium on white sugar turbidity
Einfluss von Calcium auf die Trübung von Weißzucker in Lösung
Barbara Rogé, Abdelfattah Bensouissi and Mohamed Mathlouthi
Sugar turbidity is routinely analyzed in French sugar factories. It
accounts for the presence of suspended particles in sugar solution
which display light diffusion in the analytical conditions. However,
the nature of such particles is not accurately known. It has been
described as high molecular mass colloidal particles associated
with micro-crystals of calcium salts (oxalate, sulfate, phosphate
and citrate).
Turbidity measurement is linked to that of solution color. Choice of
wavelength, filtration membrane pore diameter, and even the type
of spectrometer may affect the result. On the other hand, the ori-
gins of sugar turbidity are not easily correlated with the processing
conditions. It rather seems to be a multi-parameter origin in which
calcium salts play a preponderant role.
Recent work carried out at the ‘Laboratoire de Chimie Physique In-
dustrielle’ (Faculté des Sciences, Université de Reims, France) on
the evolution of stored beet syrup during the inter-campaign peri-
od, has made it possible to show the complexity of the mechanism
of turbidity formation. In all cases, an increase in syrup turbidity
yields an augmentation of sugar turbidity. Likewise, sugar color in-
creases as turbidity increases. Adding anti-scaling agents or filter-
ing the syrup does not seem to help. Besides calcium salts, there is
a need for macromolecules and colorants to ensure the repartition
of turbidity inside the sugar crystal.
Key words: sugar turbidity, calcium salts, color in solution, sugar
color
1 Introduction
White sugar quality was defined nearly 40 years ago by European
legislation in terms of points (“European Points”) specified by
the EU sugar market regime. According to legislation 1265/69 of
1 July 1969, the criteria adopted in order to determine points for
white sugar quality are three: color type of sugar as compared to
standards established by the Braunschweig Sugar Institute, color in
solution (50% sucrose content) and conductivity ash. To these cri-
teria, other complementary analyses are added such as polarimetric
sugar, invert sugar or water content.
However, it often happens that customers ask for further controls.
It is the case for grain size distribution (for baked goods or cham-
pagne wine), microbiology of sugar (for dairy or canned food).
Soft drink bottlers, who are important clients of the sugar factories,
often require non-foaming sugar without turbidity and insoluble
matter. The predominant industrials among these beverage proces-
sors have developed their own methods which they have imposed
on sugar suppliers. Other analyses such as odor, taste, apparent
170
In französischen Zuckerfabriken wird die Trübung von Zucker in
Lösung routinemäßig untersucht. Die Trübung wird durch das Vor-
handensein von Partikeln in der Suspension, die eine Lichtstreu-
ung unter den Analysebedingungen zeigen, hervorgerufen. Die
Zusammensetzung dieser Partikel ist nicht genau bekannt. Wahr-
scheinlich sind es hochmolekulare kolloidale Substanen, an die
Calciumsalz-Mikrokristalle (Oxalat, Sulfat, Phosphat und Citrat)
angelagert sind.
Die Messung der Trübung ist verbunden mit der der Farbe in Lö-
sung. Die Wahl der Wellenlänge, des Porendurchmessers der Fil-
trationsmembran sowie des Spektrometertyps können das Resultat
beeinflussen. Die Trübung kann nicht einfach mit den Prozessbe-
dingungen korreliert werden – sie scheint eher einen vielschich-
tigen Ursprung zu haben, bei dem Calciumsalze die wesentliche
Rolle spielen. Eine an der Faculté des Sciences, Université de
Reims (Frankreich), durchgeführte Untersuchung zur Veränderung
von außerhalb der Rübenverarbeitung gelagerten Rübenzuckersi-
rupen zeigte die Komplexität des Mechanismus der Trübungsbil-
dung. Je größer die Trübung des Sirups, desto höher ist auch die
Trübung des daraus kristallisierten Zuckers (in Lösung). Gleicher-
maßen nahm auch die Zuckerfarbe mit steigender Trübung des Si-
rups zu. Die Zugabe von Belagverhinderern oder Filtrierung des
Sirups scheint nicht zu helfen. Neben Calciumsalzen sind Makro-
moleküle und Farbstoffe verantwortlich für die Trübungsverteilung
innerhalb der Kristalle.
Stichwörter: Zuckertrübung, Calciumsalze, Farbe in Lösung
density, sulfur content, ... are sometimes required by some custom-
ers e.g. syrup and liquor processors.
Measurement of turbidity is usually associated with that of solu-
tion color. This type of analysis has been found important for a
long time as evidenced by the review published in ‘Advances in
Carbohydrate Chemistry’ in 1954 [1]. Questions posed by this type
of analysis dealt with the nature of the quantity measured. Was
it the color or the visual aspect of sample as may be compared
to a standard which is measured and how to account for all types
of colorants which have their maxima of absorbance at different
wavelengths from that retained for the method (caramel at 228 nm,
HADP (hexose alkaline degradation products) at 280 nm and mela-
noidins at 330 nm)? Does the presence of solid impurities affect
the result of color and turbidity? Is the settling of particles during
measurement important for the final result? Is it necessary to filter?
What effect has the filtration on the color measurement? What is
the optimal wavelength to adopt? Observation of the general shape
of curve as a function of wavelength shows a decrease of absorb-
ance between 300 and 750 nm. The wavelength widely used and
Sugar Industry / Zuckerindustrie 132 (2007) No. 3, 170–174
adopted in ICUMSA is 420 nm, situated in the middle of absorb-
ance curve.
Apart from the questions on the nature of the quantity measured,
the validity of the method for turbidity measurement was also dis-
cussed. This was the case at the annual meeting of G.T.S. (Groupe-
ment Technique de Sucreries) in 1963 [2]. Discussion concerned
the most appropriate type of signal, extinction or attenuation. If
filtration is needed, what should be the diameter of filter pore? In
the US, after using a method without filtration, based on the differ-
ence in attenuation between 420 and 720 nm, a harmonization is
now accepted by ISBT (International Society for Beverage Tech-
nologists) and the method agreed involves a filtration [3]. Other
parameters such as cell length or type of spectrophotometer may
have an influence on the result. Specific tests established by soft
drink processors such as filtration with an 8 µm filter are possible.
Nevertheless, the most widely used method for color and turbidity
is the ICUMSA (GS 2/3-10) method which involves a filtration
on 0.45 µm filter and the measurement of absorbance of a 50%
sucrose content unfiltered solution at 420 nm.
2 Turbidity and crystallization
Even though the measurement of turbidity is questionable, it is
however an important criteria of white sugar quality, worthy of
interest. This is the aim of the present work which consisted in
controlling the effect of turbidity on white sugar quality using a
pilot evaporating crystallizer. Results of this work were partially
published previously [4]. Turbidity used in that work came from
the stored syrup during the 1996 and 1997 campaigns. Analysis
of calcium salts in stored syrups show (Fig. 1) a good correlation
between turbidity and calcium concentration.
Fig. 1: Relationship between turbidity (European
Points*) and calcium salt content in stored syrups
during the 1996 and 1997 campaigns
Fig. 3: FTIR spectra of sugars containing different amounts of turbidity in Euro-
pean Points*
Fig. 2: Relationship between calcium in sugar
(mg/kg ds) and turbidity in European Points*
Sugar Industry / Zuckerindustrie 132 (2007) No. 3, 170–174
Table 1: Influence of the addition of calcium (free or bound)
on sugar turbidity
Sample Mean aperture Sugar turbidity
[mm] [points]
Syrup 96 0.62 1.50
Syrup 96 + 250 mg/L CaO 0.64 1.50
Pure syrup (Sugar Q1*) – 0.30
Pure syrup + 0.75% saccharate 0.62 3.30
Pure syrup + 0.5% milk of lime 0.61 3.30
* European Points Grade 1
Other constituents from stored syrup were tested for their effect
on sugar turbidity. Hence, high molecular mass macromolecules
obtained by ultrafiltration were added to pure sucrose syrup and
their effect on turbidity of white sugar crystals determined after
centrifuging and washing of massecuite. It was found that the frac-
tions of ultrafiltration retentates which were the most harmful for
crystals were the fractions with molar masses above 10,000 amu
(1 amu [atomic mass unit] = 1 Dalton) and above 300,000 amu.
Therefore, apart from calcium salts, turbidity seems to depend on
the size of the macromolecular impurity.
Moreover, analysis of the composition of the turbidity fraction in a
sugar shows a good correlation between the calcium ion concentra-
tion and white sugar turbidity (Fig. 2).
What was the form of calcium in the syrup yielding by crystalliza-
tion a turbid sugar? To answer this question, the crystallization of
stored syrup from 1996 campaign was preceded by the addition of
milk of lime. Likewise, calcium saccharates or milk of lime were
added to pure sugar syrup. Such an addition of calcium ions re-
sulted in an increase of sugar turbidity after crystallization of the
supplemented syrup (Table 1).
If calcium is bound to sucrose to form saccharates, this might
be identified from the structure of the sucrose molecule. This is
what was observed on the analysis of crystalline sucrose contain-
* Turbidity in European Points is obtained as the ratio of difference in optical
density before and after filtration on 0.45 mm membrane by 7.5 (Turbidity
(E.P.) = (D OD.)/7.5). The difference between ICUMSA and European Points
is that in E.P. determination ICUMSA points are divided by 7.5.
171
ing different proportions of turbidity. The sample of sucrose with Depending on crystal size, analysis of turbidity in fractions of sug-
the highest amount of turbidity shows an FTIR (Fourier Transform ar retained by screens between 0.1 and 1 mm shows that the finer
Infrared) spectrum different from other spectra (Fig. 3) very likely the sugar crystals, the higher their turbidity (Fig. 5). The observed
because of a modification of sucrose structure after chelating of augmentation of turbidity for large crystals is a sign of the pres-
calcium to form a saccharate complex or because of the interfer- ence of micro-crystals of calcium oxalates on the surface of the
ence of a calcium oxalate spectrum.
Another important parameter in crystallization is the rate of growth
of crystals. This rate was measured using the “end-to-end” method
[4] for crystals having an initial size of 0.86 mm. It was observed
that turbidity in syrup provokes a decrease in growth rate which
increases with the turbidity value. Likewise, determination of the
crystal dimensions after growth in the presence of turbid impurities
shows a change in the sucrose crystal morphology. Elongation of
face c is significant and such a phenomenon increases with syrup
turbidity.
The method of successive washing of sucrose crystals was applied
to localize the turbidity and determine its origin in turbid sugar.
While a first wash, decreasing the average size of crystals from
0.62 to 0.52 mm, shows a decrease in turbidity and color in sugar,
the second wash shows an increase in turbidity and a decrease in
color. Turbidity does not seem to be localized at the surface of crys-
tals. As is shown later, part of the turbidity (micro-crystals of cal-
cium oxalates) is fixed at the surface of the sucrose crystals while Fig. 5: Differences in turbidity according to crystal size for a turbid
macromolecules complexing calcium are very likely present as in- white sugar
clusions inside the crystals (Table 2).
A recent study of the localization of turbidity in crystals with sizes
above 0.8 mm shows that most of turbidity is localized at the sur-
face of crystals. However, after 4 washings, the turbidity was ho-
mogeneously distributed inside the crystals, very likely in the form
of macromolecular inclusions (Fig. 4).

Table 2: Localization of turbidity in sugar crystals grown in

stored turbid syrup after 2 washings
Sugar sample Mean Color Color in Turbidity
aperture type solution
[mm] [points]

Initial crystals 0.60 1.60 2.31 7.70

After a first wash 0.52 1.60 2.04 5.40
After a second wash 0.44 1.60 1.78 8.50

Fig. 6 A: SEM picture of the surface of a single sucrose crystal

Fig. 4: Changes in turbidity as a function of the number of wash- before washing
ings in an undersaturated sucrose solution (s = 0.95) for crystals Fig. 6 B: SEM picture of the surface of a single sucrose crystal
> 0.8 mm after washing in an undersaturated sucrose solution (s = 0.95)

172 Sugar Industry / Zuckerindustrie 132 (2007) No. 3, 170–174

sucrose crystals. This is clearly evidenced by the observation of
SEM (Scanning Electron Microscopy) pictures of sucrose crystals
before and after washing (Fig. 6 A before and Fig. 6 B after).
3 Origin of white sugar turbidity
White sugar turbidity is constituted of solid particles associated in
some cases with macromolecules. The evidence of the solid state
of turbid particles is given by the good correlation between the
clogging index of a 0.45 µm membrane and the turbidity of sugar
(Fig. 7). The clogging index is obtained by application of a method
established by the French Sugar Union (SNFS) which defines this
index as the ratio of filtrate volume difference between the start and
the end of filtration to the final volume.
The nature the of solid particles at the origin of turbidity was ana-
lyzed using the comparison of FTIR spectra of a turbid sugar and
the spectrum of calcium oxalate monohydrate (COM). This com-
parison showed that turbid particles are comparable to calcium
oxalate dihydrate (COD) especially as two characteristic infrared
absorption bands (1643 cm–1 and 1322 cm–1) are present (Fig. 8) in
both the turbid sugar and COD spectra. These COD spectra very
Fig. 7: Relationship between membrane clogging index and sugar
turbidity
Fig. 8: FTIR spectra of calcium oxalate monohydrate obtained from
equimolar reaction between calcium chloride and sodium oxalate
at 85 °C and of the retained fraction on a 0.45 µm membrane filter
from an aqueous solution (50% sucrose content) of turbid sugar
Sugar Industry / Zuckerindustrie 132 (2007) No. 3, 170–174
Fig. 9: FTIR spectra of pure COD and oxalate crystals obtained in
the presence of sucrose (according to Yu et al. [2004]): FTIR spec-
tra of calcium oxalate obtained at initial calcium oxalate concen-
tration of 130 mg/kg in sugar solution at 10% ds (A); 25% ds (B);
40% ds (C) and composites obtained from sugar solutions at initial
concentration of calcium oxalate 44 mg/kg (D) and 130 mg/kg (E)
likely correspond to that of particles adhering at sucrose crystals
surface as suggested from the SEM pictures.
The presence of COD in concentrated sucrose solution was ob-
served by an Australian team [5] from a comparison of the FTIR
spectra (Fig. 9) of pure COD and oxalate crystals obtained in the
presence of 40% sucrose in solution.
4 Reduction of turbidity
As calcium oxalates seem to be the major constituents of turbidity
in white sugar, addition of anti-scaling agents in the evaporating
crystallizer is sought to be the solution to prevent the precipitation
of calcium oxalate crystals. This was tested in a micro-evaporating
crystallizer for syrups with high turbidity [4]. Such an addition of
anti-scaling agent was found to be inefficient. There was no de-
crease in sugar turbidity when crystallization was achieved in pres-
ence of the anti-scaling agent.
Another attempt to reduce sugar turbidity consisted in syrup filtra-
tion at the level of a sugar factory. Using filters with pore diam-
eters varying between 1 and 25 µm, it was impossible to achieve
filtration because membranes clogged rapidly. Even after dilution
of syrup and filtration on a 1.3 µm membrane in the laboratory, the
reduction of turbidity was only 15%. This solution consisting in
Fig. 10: Relationship between calcium salt content (mg/100 g ds)
and turbidity (2004/05 campaign)
–––––– average; -------- upper and lower limits
173
the filtration of syrup to reduce sugar turbidity seems difficult to
achieve and should be rejected.
As already remarked, turbidity is linked to the presence of calcium
ions in the syrup. Therefore, decalcification of thin juice seems one
of the best means for the reduction of white sugar turbidity. This
can be deduced from Figure 10 which shows a relatively good cor-
relation between thin juice calcium salt content and white sugar
turbidity. For turbidity as for other problems, prevention seems
more efficient than healing. In this case, decalcification of thin
juice appears as a good means of turbidity prevention.
5 Conclusion
– Turbidity in white sugar seems related to the presence of cal-
cium ions in the syrup as well as to high molecular mass macro-
molecules, especially fractions with molar masses above 10,000
and above 300,000 amu. Turbidity is localized at the surface
of sucrose crystals in the form of micro-crystals of calcium
oxalates. Inside sugar crystals, complexes of calcium oxalates
and macromolecules might be at the origin of turbidity. The
preponderant polymorph of calcium oxalate present in turbidity
particles is calcium oxalate dihydrate.
– Syrup turbidity leads to a decrease in the sucrose crystallization
rate and a change in crystal morphology. The smaller the sugar
crystals the more the calcium oxalate is concentrated and the
turbidity is high.
– To reduce white sugar turbidity, decalcification of thin juice
seems to be the most efficient procedure. Adding anti-scaling
agents during the evaporation step protects the evaporator tube
from scale formation, but delays the problem as the turbidity
is concentrated in the syrup, especially in the case of storage.
Other methods such as syrup filtration or thin juice filtration
were proposed with more or less efficiency.
References
1 Liggett, R.W.; Deitz, V.R. (1954): Color and turbidity of sugar products. In:
Wolfrom, M.L. (ed.): Advances in Carbohydrate Chemistry, 247–284
2 Compte Rendu Réunion annuelle du G.T.S. (1963) pp E1 – E12 et F1 – F7
3 Godshall, M.A. (2006): The quality of white sugar required for the beverage
industry. Proceedings of the XIIIth AVH Symposium, 44–49
4 Cosmeur, A.; Mathlouthi, M. (1999): Etude en microcuite de l’effet de cer-
taines impuretés sur la qualité du sucre blanc de betteraves. Comptes rendus
du 6ème Symposium AVH, 45–57
5 Yu, H.; Sheikholeslami, R.; Doherty, W.O.S. (2004): The effect of silica
and sugar on the crystallographic and morphological properties of calcium
oxalate. J. Crystal Growth 265, 592–603
Effet du calcium sur le trouble du sucre blanc (Résu-
mé)
Le trouble du sucre est une analyse de routine dans les sucreries
françaises. Elle vise à rendre compte de la présence de particules
en suspension dans la solution de sucre qui diffuseraient la lumière.
Cependant, la nature de ces particules n’est pas connue avec pré-
cision. Il s’agit de «colloïdes» de haut poids moléculaire souvent
associés à des microcristaux de sels de calcium (oxalate, sulfate,
phosphate, citrate).
La mesure du trouble est effectuée en même temps que la colo-
ration en solution. Le choix de la longueur d’onde, du diamètre
174
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des pores de la membrane de filtration de la solution, et même du
spectrophotomètre peut influencer le résultat. Par ailleurs, les cau-
ses d’apparition ou d’augmentation du trouble ne sont pas toujours
expliquées par des variations de paramètres du process. Cela sem-
ble être plutôt un phénomène multifactoriel dans lequel les sels de
calcium jouent un rôle prépondérant.
Une étude que nous avions menée, il y a quelques années sur l’évo-
lution de la qualité du sirop stocké pendant l’inter-campagne nous
a permis de montrer la complexité du phénomène de formation du
trouble. Dans tous les cas, l’augmentation du trouble dans le sirop
entraîne une augmentation du trouble dans le sucre. De même, la
coloration augmente parallèlement au trouble. L’addition d’anti-
tartre ou la filtration du sirop ne semblent pas avoir d’effet sur le
trouble du sucre qui nécessite en plus des sels de calcium la pré-
sence de macromolécules et de colorants qui favorisent sa réparti-
tion dans le cristal.
Dans cette présentation, nous nous proposons de rappeler les
travaux antérieurs sur le trouble dans le sucre notamment ceux
concernant la nature des particules le constituant. De même, nous
évoquerons les problèmes d’analyse de trouble et d’insolubles et
leur utilité.
El efecto de calcio sobre la turbidez de azúcar blanco
(Resumen)
En fábricas de azúcar francesas se analiza con regularidad la tur-
bidez de azúcar blanco en solución. La turbidez se debe a la pre-
sencia de partículas en la suspensión que, bajo las condiciones del
análisis, muestran una difusión de la luz. Actualmente no se cono-
ce exactamente la composición de las partículas - parece que son
sustancias coloidales de alto peso molecular con microcristales de
sales de calcio asociados (oxalato, sulfato, fosfato y citrato).
La medida de la turbidez está acoplada a la medida del color en la
solución. La selección de la longitud de onda, del diámetro de los
poros de la membrana de filtración y del espectrómetro pueden
influir el resultado. Entre la turbidez y las condiciones del proceso
no hay una correlación simple – la turbidez más bien parece ser
de origen múltiple en el que las sales de alcio tienen un papel muy
importante.
En la Facultad de Ciencias de la Universidad de Reims (Francia) se
estudió la transformación de jarabes de remolachas almacenados
con toda la complejidad del mecanismo de la formación de turbi-
dez. Cuanto más turbio es el jarabe tanto más turbio también es el
azúcar cristalizado (en solución). Con una mayor turbidez del jara-
be también aumenta el color del azúcar. La filtración del jarabe o la
adición de agentes contra incrustaciones no parecen tener mucho
efecto. Las sales de calcio junto con macromoléculas y colorantes
son responsables para la distribución de la turbidez dentro de los
cristales.
Authors’ address: Barbara Rogé, Abdelfattah Bensouissi,
Mohamed Mathlouthi, Laboratoire de Chimie Physique Indus-
trielle, UMR A 614, Fractionnement des Agroressources et
Emballage, INRA, Université de Reims Champagne-Ardennes,
B.P. 1039, F-51687 Reims Cedex, France: e-mail: mohamed.
mathlouthi@univ-reims.fr
Sugar Industry / Zuckerindustrie 132 (2007) No. 3, 170–174