Escolar Documentos
Profissional Documentos
Cultura Documentos
INFLUÊNCIA DO PROCESSO E
DO TEMPO DE ARMAZENAMENTO
Recife
2012
Caldas, Celso Silva
Escurecimento do açúcar branco: influência do processo e
do tempo de armazenamento / Celso Silva Caldas. – Recife: O
Autor, 2012.
90 folhas: il., fig.; 30 cm.
Inclui bibliografia.
UFPE
664 CDD (20.ed.) CCS2012-043
Celso Silva Caldas
Recife
2012
À esposa Abigail e aos filhos Amadeus e Aman,
pelo incentivo e compreensão dos momentos
de ausência em nosso Lar.
Agradecimentos
• À Profa Nonete Barbosa Guerra, que acreditou neste projeto e com sua sabedoria e
dedicação fez com que alcançássemos os objetivos desta pesquisa.
The browning during storage of sugar causes high economic losses to producers and
the country. This finding motivated this research to identify the precursors of browning,
evaluate the influence of process and storage time on changing the color of white sugar.
The material consisted of two lots, both containing 2,000 bags of cristal sugar and refined,
produced by two plants located in the state of Alagoas - Brazil and stored in storage under
average temperature of 26.5 ° C and 80% relative humidity. The samples collected at
random, after assembly of lots (day 1) and at intervals of 30 days during 04 months of
storage were analyzed by official methods validated for the physico-chemical quality and
browning precursors. The sugars differ significantly among themselves as to the parameters
evaluated, especially ICUMSA color and iron content in the crystal that reached values
higher than the refined, demonstrating the ineffectiveness of sulfitation sugar crystal in
color reduction. A progressive darkening of the sugar occurred during storage, and phenolic
compounds as precursors. The results enabled the establishment of regression equations
with the values of ICUMSA color and reflectance (color vision) that allow to predict, in
conditions in which this research was conducted, the degree of color variation of sugar
depending on storage time.
1. Apresentação 12
2. Revisão da Literatura 14
2.1 Produção de açúcar 14
2.1.1 Matéria-prima: constituição e composição química 14
2.1.2 Processo industrial de fabricação de açúcar: fluxograma
operações unitárias, equipamentos e armazenamento 18
2.1.2.1 Processo tradicional para produção de açúcar branco
tipo cristal 19
2.1.2.1.1 Limpeza e preparo da cana 19
2.1.2.1.2 Extração 19
2.1.2.1.3 Tratamento do caldo: aquecimento e clarificação 20
2.1.2.1.4 Evaporação 21
2.1.2.1.5 Cristalização e centrifugação 22
2.1.2.1.6 Secagem 23
2.1.2.2 Processo de refino 23
2.1.2.3 Embalagem e armazenamento 23
2.2 Precursores do escurecimento do açúcar 24
2.2.1Tipos e mecanismos de ação 24
2.2.2 Avaliação da natureza dos corantes 26
2.3 Conclusão 29
3. Métodos 31
3.1 Delineamento experimental 31
3.2 Métodos analíticos 33
3.2.1 Parâmetros de qualidade 33
3.2.2 Parâmetros relacionados ao estudo do escurecimento 34
3.3 Validação dos métodos analíticos 36
3.4 Métodos para análise estatística 36
4. Resultados 37
Artigo 01: Influence of the Fabrication Process on Characteristics of
Crystal and Refined White Sugar 37
Revista Química Nova: Submissão temporária – tmp 9560 58
Artigo 02: The Effect of Storage Time on Browning of
White Sugar: Crystal and Refined 59
Revista Química Nova: Submissão temporária – tmp 9561 83
5. Considerações finais 84
Referências 85
12
1. APRESENTAÇÃO
1
First in, first out
13
2. REVISÃO DA LITERATURA
Substâncias Porcentagem
Água 74,5 (65,0 – 75,0)
Açúcares 14,0 (12,0 – 18,0)
Sacarose 12,5 (11,0 – 18,0)
Glicose 0,9 (0,2 – 1,0)
Levulose 0,6 (0,0 – 0,6)
Fibras 10,0 (8,0 – 14,0)
Celulose 5,5
Lignina 2,0
Pentosana (Xilana) 2,0
Goma da Cana (Arabana) 0,5
Cinzas 0,50 (0,40 – 0,80)
SiO2 0,26
K2O 0,12
P 2O 5 0,07
CaO 0,02
SO3 0,02
Na2O 0,01
MgO 0,01
Cl Traços
Fe2O3 Traços
Matérias Nitrogenadas 0,40 (0,30 – 0,60)
Aminoácidos (como ácido aspártico) 0,20
Albuminóides 0,12
Amidas (como asparagina) 0,07
Ácido Nítrico 0,01
Amonfaco Traços
Corpos Xânticos Traços
Gorduras e Ceras 0,20 (0,15 – 0,25)
Substâncias Pépticas, gomas e muscilagens 0,20 (0,15 – 0,25)
Ácidos Combinados 0,12 (0,10 – 0,15)
Málico
Succínico etc.
FONTE: IPT, 1990
18
Os açúcares tipo cristal e tipo refinado são obtidos pelos processos tradicionais de
industrialização da cana de açúcar e refino de açúcar escuro, conforme esquemas mostrados
nas figuras 3 e 4 respectivamente.
AÇÚCAR
Cozimento Cristalização Centrifugação Secagem
CRISTAL
AÇÚCAR
Centrifugação Secagem
REFINADO
Neste processo, após pesagem da cana para obtenção de dados que permitam
calcular as eficiências industriais e a remuneração do fornecedor de cana, são efetuadas
coletas de amostras para serem analisadas em laboratório quanto aos parâmetros de
qualidade. O parâmetro mais utilizado para cálculo das eficiências e também para o
sistema de pagamento de cana é o ART – açúcares redutores totais, ou seja, parâmetro que
contempla a sacarose invertida, glicose e frutose (FERNANDES, 2011).
2.1.2.1.2 - Extração
Uma grande parte das impurezas no caldo (areia, palha, pedaços de cana, bagaço) é
eliminada através de peneiramento (tamização) originando um caldo de melhor qualidade.
O caldo peneirado segue para uma coluna de sulfitação onde em contracorrente é
borbulhado o dióxido de enxofre (SO2), que devido à sua propriedade redutora tem ação
descorante (IPT, 1990). Como esta operação o pH do caldo baixa para 3,8 a 4,3 (HONIG,
1974), procede-se a caleação (adição de leite de cal) para elevá-lo para 7,0. O caldo
neutralizado é então aquecido a 100º-105ºC e enviado ao decantador (HUGOT, 1969).
Estas etapas de peneiramento, sulfitação, caleação e decantação estão no esquema da figura
6, que ainda mostra a recuperação de caldo existente no lodo do decantador, que depois de
filtrado é chamado de torta de filtro e segue para o campo como adubo orgânico.
21
2.1.2.1.4 - Evaporação
2.1.2.1.6 - Secagem
devido a formação de quelatos (SMITH & HALL, 1972). Os ácidos fenólicos esterificados
com polissacarídeos quando envolvidos em reações de escurecimento enzimático podem
formar ligações cruzadas, resultando complexos de cor muito escura e de elevado peso
molecular. As ligações entre os ácidos ferúlicos e polissacarídeos são de difícil hidrólise e
fazem com que estes compostos persistam durante todo o processo de fabricação do açúcar
(CLARKE, et al,1985 ). Ademais, os derivados do ácido cinâmico são de difícil remoção
durante a extração e refino, motivo pelo qual alcançam o produto final, a exemplo do ácido
clorogênico (FARBER & CARPENTER, 1972).
Neste contexto, tem-se a pesquisa efetuada por Faber e Carpenter (1972), que
identificaram vinte um composto fenólico na cana de açúcar. Em 1985, Smith e Paton
destacaram, entre os fenólicos presentes no caldo, os flavonóides, e dentre estes as
antocianinas, flavonas, flavonóis (catequinas), flavonols e as chalconas que se encontram
quimicamente relacionadas a estes compostos, cujas estruturas apresentam em comum a
seqüência carbônica C 6-C3-C6. Em contraposição, Bertrand Payet, Alayn Sing e Jacqueline
Smadja (2006), constataram que os ácidos fenólicos eram os principais componentes dos
materiais em processo e do açúcar (Tabela 2), ao utilizarem cromatografia líquida acoplada
com espectrofotômetro de massa (LC-MS) que permite a detecção simultânea de diversas
classes de polifenóis, e que as catequinas e outros flavonóides não foram achados nos
extratos avaliados.
Nas duas últimas décadas alguns autores têm utilizado sistemas modelos de corantes
direcionados a uma ou outra reação de escurecimento para obter informações mais precisas
sobre a natureza desses corantes. Em 1994, Javad Keramat e Harry Nursten compararam os
compostos coloridos do caldo prensado da cana de açúcar com os formados pela reação de
28
Maillard (sistemas: alanina e glicose, alanina e frutose), pela degradação alcalina destes
monossacarídeos e pela caramelização da sacarose, sob condições que simulavam às
obtidas na carbonatação. Os resultados demonstraram que todos eles, principalmente os da
reação de Maillard, se assemelhavam aos compostos coloridos do caldo prensado. Neste
mesmo ano, Carolin Buchelli e Simon Robinson evidenciaram que a polifenoloxidase
(PPO) contribui, significativamente, para o escurecimento enzimático do caldo da cana de
açúcar.
Estudo conduzido por Dorrit Baunsgaad, Lars Norgaard e Mary An Godshall
(2001), para elucidar a natureza dos componentes da cor no xarope de cana de açúcar e de
beterraba utilizaram uma série de modelos de corantes preparados sob condições alcalinas
leves, capazes de reproduzirem os tipos de corantes formados durante o processamento do
açúcar. A avaliação de desenvolvimento da cor foi realizada por cromatografia líquida de
alta eficiência (CLAE) e fluorescência. Os resultados, obtidos por este último método em
ultravioleta (UV) demonstraram que os corantes fluorescentes do xarope da cana situaram-
se no comprimento de onda mais elevado, indicando presença de corantes muito escuros,
cuja formação foi atribuída ao elevado nível de açúcares invertidos durante o
processamento da cana. Em revisão sobre componentes de cor formados no processamento
do açúcar de beterraba, Monica Coca et al, (2004), recomendam a cromatografia de “gel
permeation” (GPA) como uma técnica analítica sensível para separar os corantes do caldos
da cana de açúcar e para determinar seus pesos moleculares. Os compostos coloridos da
beterraba podem ser caracterizados por seu espectro ultravioleta – visível (UV-Vis) com
detector de fotodiodo. De acordo com estes autores, antes da descoloração do caldo, foram
identificadas pela análise espectral substâncias corantes com peso molecular que varia de
400 a valores maiores do que 100.000 Da (Dalton), as quais foram confirmadas como
melanoidinas, e produtos de degradação de hexoses (HADPs).
Ademais, a literatura apresenta resultados de pesquisas sobre a influência de
processos de descoloração sobre o peso molecular e distribuição dos corantes do açúcar
durante o processo de refino; sobre compostos de elevados pesos moleculares e formação
de cor no açúcar e no caldo a partir da carbonatação, por meio de cromatografia em gel,
realizadas por Bento (1999), e Bento e Sá (1998). Resultados preliminares e apresentados
por B. Barker e S Davis (2002) demonstram que a aplicação do processo SPARAC, um tipo
de processo de remoção de cor com carbono ativo granulado, ficou abaixo do esperado.
29
2.3 – Conclusão
produzido em Alagoas - BR, tendo em vista obter dados que permitam o desenvolvimento
de tecnologias apropriadas à sua remoção e reduzir riscos de sua formação nas etapas
subseqüentes.
31
3. MÉTODOS
• Pol
Este parâmetro define a concentração de sacarose em ºZ (graus zucker), expressa em
percentagem em massa, cujos valores para os tipos de açúcar branco (cristal e refinado) são
sempre maiores do que 99,7ºZ. Açúcares utilizados como matéria-prima para posterior
refino apresentam resultados de pol inferiores a 99,5ºZ, exceto o açúcar mascavo que tem
valores ainda menores. Este parâmetro é determinado pela técnica da polarimetria a partir
de uma solução com concentração de açúcar igual a 26g/100cm 3 (ICUMSA GS 2/3-1,
2005).
• Umidade
Indica a quantidade de água existente no açúcar e se torna um item de grande
importância para qualidade do açúcar, já que açúcares úmidos não têm a preferência de
consumidores. Açúcares destinados ao consumo direto apresentam resultados menores do
que 0,05%m/m, sendo este parâmetro determinado por gravimetria através de secagem, com
resultados expressos em %m/m (ICUMSA GS 2/1/3-15, 2005).
• Cinzas Condutimétricas
Determina indiretamente a quantidade de substâncias inorgânicas no açúcar. No método
analítico é medida a resistividade elétrica de uma solução de açúcar com concentração igual
a 28g/100g, cujos resultados em %m/m expressam o teor de sais dissociados no açúcar, ou
cinzas condutimétricas (ICUMSA GS 2/3-17, 2005).
• Cor ICUMSA
Este é o principal parâmetro de qualidade do açúcar, cujo resultado é obtido de uma
equação matemática estabelecida pela International Commission for Uniform Methods of
34
• Sulfitos
Este parâmetro está relacionado ao uso do enxofre como agente de clarificação do caldo
da cana durante a produção do açúcar, embora haja atualmente uma preocupação ou
tendência para sua eliminação devido ao seu efeito alérgico, sentido por uma pequena
parcela da população. Por este motivo existem movimentos internacionais para reduzir o
atual teor máximo de sulfito em açúcar branco de 15 mg.kg-1 SO2. O método usado para sua
determinação foi do reagente pararosalina, ou fucsina básica, com leitura em
espectrofotômetro a 560nm e resultados expressos em mg.kg-1 (ICUMSA GS 2/1/7-33,
2009).
• Ferro
O ferro participa de reações secundárias de amarelecimento do açúcar, sendo um
reagente bastante ativo nas reações com compostos fenólicos, formando quelatos coloridos.
É um dos parâmetros solicitados por consumidores de açúcar para produção de bebidas
transparentes ou aqueles que têm na ausência de cor o seu marketing. Foi usado o método
35
• pH
O pH é uma importante medida no estudo do escurecimento do açúcar, pois os
precursores de cor variam de sensibilidade em diferentes pH. Seus resultados são
adimensionais e para esta determinação foram preparadas soluções aquosas de açúcar com
concentrações de 50g/100g (ICUMSA GS 1/2/3/4/7/8 – 23, 2005).
4. RESULTADOS
ARTIGO 01
Universidade Federal de Viçosa, Av. Peter Henry Rolfs, s/n, 36570-000 Viçosa – MG,
Brasil
39
resulting in financial losses to producers and national industry. This study was performed to
obtain knowledge on the compounds involved and to evaluate the influence of the
production processes on browning. The study material consisted of samples of crystal and
refined white sugar produced in the state of Alagoas - Brazil. The sugars differed
significantly, especially with regards to ICUMSA color and iron. Results obtained allowed
for establishment of linear regression equations to estimate the visual color and ICUMSA
browning.
INTRODUCTION
The most common form of sugar is sucrose in its solid, crystal state, with characteristic
odor and flavor, and white color.1 Two types of white sugar are industrially manufactured:
crystal, produced directly for consumption, and refined produced from a darker sugar.
begins in the extraction of juice and proceeds until sugar crystallization, resulting in a lower
quality product that does not meet the requirements of various consumers.2
The chemical compounds responsible for browning of the sugar can be found in the
sugarcane itself (extremely variable raw material due to the considerable territorial extent
of the planted regions and the diversity of climate, soils and topography) or originate from
the production processes.3 Therefore, increased browning during processing depends not
only on the quality of raw material, but the unit operations and the types of colorants in the
juice. Knowledge of its origin, formation, destruction and removal during sugar processing
To meet the maximum and minimum requirements of the consumer market, the
employed by crystal sugar producing plants in the Brazilian northeast to reduce this
alteration. According to Davis 5, this process is more effective for the formation of color
than discoloration. In a review of the browning of sugar during processing, Bento4 cited the
results of the action of sulfur dioxide to inhibit the formation of caramels and melanoidins,
and bisulfite to inhibit formation of flavonoids, which are considered precursors of this
alteration. However, in practice it appears that despite sulfitation, crystal sugar browns
Other alternatives for clarification of sugarcane juice are used industrially, such as
ozonation and double carbonation, however these methods include higher costs, operational
generally preferred.6
option often used in sugar production, especially to meet the most demanding classes of
consumers and food industries that use sugar in its original state. However, refining
increases production costs by introducing new unit operations and consumption of chemical
Given the lack of information and the problems that browning has on the marketability
of sugar, generating financial losses for producers and national industry, this study was
developed to evaluate the influence of production processes on the quality of white sugar –
crystal and refined, and obtain better understanding of the compounds involved in
browning.
The material in this study consisted of two types of white sugar – crystalized and
industrial units randomly selected from the members of the Regional Cooperative of Sugar
Sulphitatio Pretreatment of
Evaporation Decanting Liming
n the juice
CRYSTAL
Cooking Crystallization Centrifugation Drying SUGAR
REFINED
Centrifugation Drying
SUGAR
Sample size was established according to the general rule of sampling, i.e., equivalent
to √(n+1), where “n” is the number of sacks of sugar on each pallet that resulted in a total
of forty-four sacks and were randomly selected as follows: 4 sacks from the center of the
pallet, 8 sacks from each of the sides and the top. 8,9
43
Assuming that most of the samples showed the same characteristics, from each sack
sub-samples of 100g were removed for the composition of the different sugar types. The
individual samples were homogenized and reduced using a Jones splitter to obtain a
composite sample of 2 kg for each sugar type, which were then sent to a laboratory
accredited by the Ministry of Agriculture, Livestock and Food Supply – MAPA which met
the requirements of the ISO 9001/2008, to perform analytical testing related to the quality
Official validated methods were used for chemical analyses of the following variables:
POL - equivalent to the amount of sucrose, determined by the polarimetry technique using
a sugar solution with concentration equal to 26g/100cm3 and the international scale of sugar
whose results are expressed in %w/w or °Z (ICUMSA GS 2/3-1, 2005); moisture content,
determined by drying, with results expressed as %w/w10, conductivity ash, whose results in
%w/w express the content of dissociated salt in a sugar solution with a concentration equal to
28g/100g10; ICUMSA color, where the result obtained from a mathematical equation
to 560nm, using the reagent pararosaniline or basic fuchsin, with results expressed in
mg.kg-1;11 iron (Fe), determined by the spectrophotometric method with the 1,10-
with results expressed in mg.kg-1;10 pH, determined in aqueous sugar solutions with
determined by the Knight and Allen method with EDTA. The results were expressed in
%w/w reducing sugars;10 reflectance, indirectly indicates the visual color of the sugar, in
44
which the dimensionless results express the degree of light scattering when focused on a
650 nm using the Folin-Ciocalteau reagent and the results are expressed in mg.kg -1,
according to the protocol of the Bureau of Sugar Experiment Stations; 13 indicator value
(IV), indicates a relationship between the ICUMSA colors at pH 9.0 and pH 4.0 according
different types of coloring of the sugar (Table 1); and polyphenols determined by high
performance liquid chromatography - HPLC, with results in mg.kg-1. The HPLC was
equipped with a refractive index detector and sample volumes of 20μL were injected.
Standards used were of the following phenolic acids: benzoic, vanillic, p-coumaric,
chlorogenic, caffeic, and gallic aconite. Also used were catechin and vanillin.
Sugar Analysis – ICUMSA are validated with regards to precision by repeatability and
phenolic compounds (TFH) and polyphenols were validated by linearity of the coefficient
of determination (R2).15
The following methods were used for statistical analysis: Student’s test, Pearson’s
Source15
(*)16
45
two types of white sugar, as detailed in Table 2, clearly demonstrate the influence of
Of the parameters assessed that which stands out is the ICUMSA color index, in which
the crystal sugar was three times high than refined sugar. Although the nature of the
colorants in the sugar is not informed, this analysis is considered the key measure of its
product purity.17 This parameter has a great influence on the decision to purchase of the
consumer.18
The fact that crystal sugar has a greater honey film surrounding the sucrose structures
explains the difference in moisture content in relation to the refined sugar, which in turn has
a higher POL content since the refining process increases its purity. Because this process
removes almost all impurities from the sugar cane juice, it was expected that it present
significantly lower levels of iron and conductivity ash than crystal sugar. Iron levels
presented by both sugars were 3-4 times higher than 0.5 mg.kg-1, considered critical for the
browning of sugar by Smith & Hall,19 due to formation of insoluble complexes. Moreover
the presence of iron catalyzes the formation of hexose alkaline degradation products
(HADP).20
The presence of sulfite in crystal sugar is due to sulfitation, commonly applied for
treatment of the juice. This operation is followed by neutralization, known as liming, which
neutralizes the medium and leads to the formation of calcium sulfite, an insoluble salt that
absorbs impurities and colored compounds of the juice, forming flakes which are then
decanted.21 This explains the fact that the pH of crystal sugar is slightly more basic than
refined sugar.
As for the formation of color during processing, it is known to vary with conditions of
the medium, temperature, concentration and presence of precursors and impurities that act
during the processing of sugar originate from browning reactions - enzymatic and non-
heating and various reagents: N, OH and Fe compounds. The products of these reactions
tend to remain in the sugar crystals during crystallization, which negatively affects the
Processing also influences the precursors to browning of white sugar (Table 3). The
significant differences between the results obtained for the parameters related to this
47
alteration demonstrate that the crystal sugar had the highest concentrations of reducing
sugars and total phenolics, while the refined sugar exhibited the highest reflectance and
indicator values. In a study on the precursors and colorants in beet and sugarcane liquor,
Clacker & Legendre23 and Baunsgaard et al24 reported that the latter contains a higher
amount of invert sugar, a characteristic that could favor the alkaline degradation of sugars
and explain the formation of very dark colors during the processing of sugarcane. Sucrose
and invert sugars can react during the process of sugar extraction and refining.4
darker sugars. The difference registered (11.32%) between sugars with regards to this
parameter corroborate with the results of ICUMSA color for crystal sugar (Table 2), where
Results of the indicator value point to phenolic compounds as the main precursors to
browning, independent of the sugar type (Table 1). The total content of these compounds
(Table 3) in the final product was higher than that found by Payet et al, 25 who reported an
chromatography coupled with mass spectrometer (LC-MS), these authors found that
48
phenolic acids were the main components of the extracts and that p-coumaric and ferulic
acid were predominant. In the sugars of the present study only vanillic and p-coumaric
acids were identified and quantified (Table 4 and Figure 3). The presence of these acids in
the final product corroborates with Faber and Carpenter 26 with regard to the difficulty for
their removal during extraction and refining. Normally these acids are linked to other
they are not removed in the majority of manufacturing and refining processes, appear in
white sugar.14 These compounds reduce the efficiency of the refining process, increase
A
B
C D
Figure 3 – (A) vanillic acid standard; (B) p-coumaric acid standard; (C) results of the
crystal sugar, and (D) results of the refined sugar
and form complexes with iron.4 These complexes cause an increase in the yellowing of the
sugar crystals, affecting its color. Although Smith & Paton 16 and Riffer 27 referred to phenol
concentrations greater than 50 mg.kg-1 causing the yellowing of sugar, in the present study
elevated correlation were observed between high iron content and ICUMSA color (Table
5), probably due to the formation of iron/phenol complexes, and also between the
Moisture 1 NS NS NS NS NS NS NS NS NS NS
Pol 1 NS NS NS NS NS NS NS NS NS
Cond. Ash 1 NS NS NS NS NS NS NS NS
ICUMSA Color 1 NS 1 NS NS NS NS NS
Sulfite 1 NS NS NS NS NS NS
Iron 1 NS NS NS NS NS
pH 1 NS NS NS NS
RS 1 NS NS NS
Reflectance 1 NS 1
TPH 1 NS
IV 1
of determination (R2) equal to 0.973 for the iron and ICUMSA color, and 0.987 for
reflectance and the indicator value according to Figure 4, respectively. These results allow
for predicting the ICUMSA color from the iron concentration using the following equation:
ICUMSA Color = 34.108 + 81.08 x iron, and also of visual color - reflectance - from the
A B
Figure 4 – Correlations for crystal sugar between: (A) iron and ICUMSA color and (B)
indicator value (IV) and reflectance
When referring to the parameters of refined sugar, the results of the Pearson correlation
(Table 6) showed significance (0.97) only between reflectance and the IV. Calculation of
indicating a perfect correlation between the reflectance and the indicator value (Figure 5).
This result allows for the prediction of reflectance (visual color) using the following
equation: Reflectance = 11.2511 x indicator value – 10.1589. The low levels of iron
color.
Considering that this study involves a set of multivariate data, a Principal Component
Analysis (PCA) was performed whose projections are shown in Figure 6. Upon analysis of
the first principal component that reproduces 92.00% of the total variability, it appears that
the pol, reflectance index (RI) and indicator value (IV) with positive scores characterize the
refined sugar, while the moisture, ash, ICUMSA color, sulfide, iron, pH and reducing
sugars with negative scores, characterize the crystal sugar. This analysis clearly confirms
the interference of the processes on parameters of quality and browning precursors of white
sugar.
52
Pol 1 NS NS NS NS NS NS NS NS NS NS
Cond. Ash 1 NS NS NS NS NS NS NS NS NS
ICUMSA Color 1 NS NS NS NS NS NS NS NS
Sulfite 1 NS NS NS NS NS NS NS
Iron 1 NS NS NS NS NS NS
pH 1 NS NS NS NS NS
RS 1 NS NS NS NS
Reflectance 1 NS NS NS
TPH 1 NS 0,97
IV 1 NS
Pol 1
Figure 5 – Correlation between the indicator value and reflectance for refined sugar
53
Figure 6 – Projection of the sugar samples and parameters of quality related to the
browning of sugar in the two first principal components. AC: crystal sugar; AR: refined
sugar; RE: Reflectance; CF: phenolic compounds; VI: Indicator value; ARE: reducing
sugar.
CONCLUSIONS
browning of the two types of white sugar demonstrates the influence of processes used in
its production. Correlations obtained from the results of this study allow us to predict the
visual color and ICUMSA color of these types of sugars. Establishment of the importance
of phenolic compounds, especially the acids as precursors to browning of sugar and the
production and refining of white sugar, considering the importance of color on sugar
quality.
54
REFERENCES
3.CLARKE, M.A. & LEGENDRE, B.L. Sugarcane quality: impacto sugar yield and quality
factors. The south African sugar Tecnologist Ass. Durban, 1996. Proceedings, n. 70, p.16-
19, 1996.
4.BENTO, L. S. Colourants through cane sugar production and refining.. Proc. SPRI Conf.,
2008.
13.BSES - Bureau of Sugar Experiment Stations. The Standart Manual for Australian Sugar
Mills. Brisbane, 1991.
16.SMITH, P & PATON, N. H. Sugar cane flavonois. Sugar Industry Reviews, v. 12, n. 2-
3, p. 117-142, 1985.
19.SMITH, P. & HALL, P. Sugar cane anthocyanins as colour precursors and phytoalexins.
International Society of Sugar Cane Technologist Congress, 14, Louisiana, Proceedings.
Louisiana, 1972, p. 1139-1146.
20.KORT, M. J. Colour in the Sugar Industry, in Sugar. Science and Technology, Ed. G. G.
Birch, K, J. Parker, Applied Science Pub. Ltd., London, 1978.
21.COCA, M., GARCIA, M. T., GONZÁLEZ, G., PENA, M. & GARCIA, J. A. Study of
coloured components formed in sugar beet processing. Food Chem., 2004.
23.CLARKE, M.A. & LEGENDRE, B.L. Sugarcane quality: impacto sugar yield and
quality factors. The south African sugar Tecnologist Ass. Durban, 1996. Proceedings, n. 70,
p.16-19, 1996.
Obrigado por submeter seu manuscrito "Influence of the Fabrication Process on Characteristics
of Crystal and Refined White Sugar " para publicação na Química Nova, QN.
Assim que o seu arquivo PDF for verificado, o seu manuscrito será inserido no sistema, e você
receberá um outro e-mail com o NÚMERO DE REFERÊNCIA, confirmando assim a
submissão.
Caso você tenha alguma outra dúvida a respeito desta submissão, por favor, entre em contato
com a Gerente Editorial da QN no e-mail: sbqedit@iq.usp.br.
Atenciosamente,
Pricila Gil
SBQ - gerente editorial
Caixa Postal: 26037
05513-970 São Paulo - SP
Tel.: +55.11.30322299
Fax.: +55.11.38143602
web: http://quimicanova.sbq.org.br/
e-mail : sbqedit@iq.usp.br
59
ARTIGO 02
The Effect of Storage Time on Browning of White Sugar: Crystal and Refined
Universidade Federal de Viçosa, Av. Peter Henry Rolfs, s/n, 36570-000 Viçosa – MG,
Brasil
2
*e-mail: celso@centralanalitica.com.br
61
The Effect of Storage Time on Browning of White Sugar: Crystal and Refined
Abstract - The browning of white sugar during storage causes considerable economic losses
to producers and the country. To evaluate the effect of storage time on browning and
establish equations able to predict this change, this research was conducted with two types
of white sugar, refined and crystallized, produced in the state of Alagoas - Brazil. The
results showed significant differences between the qualities of sugars and showed a
establish linear regression equations that permit prediction of ICUMSA color and visual
INTRODUCTION
The increase in color intensity of sugar during storage, also referred to as browning,
causes serious economic problems to the individual sugar producers and national sugar
production due to elevated costs for refining of raw sugar, and also has negative effects on
marketing of white sugar since products with lighter color are preferred by consumers.1,2
The colorants involved in this alteration originate from the sugarcane itself -
hexoses. The first, with the exception of phenolic compounds given their insolubility in
water, are easily removed by decantation during the juice clarification process. Soluble
phenolic compounds, which are incorporated to the juice through enzymatic and non-
enzymatic reactions with other compounds such as N, OH, and Fe upon heating, form dark
pigments of different molecular weights during sugar processing.3 Upon identification and
spectrometry (LC-MS), Payet,4 found that phenolic acids were the main components of the
extracts. Usually these acids are found linked to other phenols or polysaccharides by ester
bonds, forming molecular complexes that are not removed as the majority of production
and refining processes, thus appearing in white sugar.5 The products of these reactions,
according to Coca,6 tend to remain in the sugar crystals during crystallization, depreciating
According to Clarke5 & Dorrit,7 the increase in color during evaporation and
crystallization, and its development after storage originates from non-enzymatic reactions,
caused by thermal degradation of the sugar with or without the participation of amino acids.
and/or various precursors, special care must be taken with respect to temperature and
63
relative humidity inside warehouses. In addition to this change, the sugar may present
hardened clods during storage due to supersaturation of sucrose present in the honey film
that surrounds the crystal, caused by loss of water to the inter-crystalline medium or the
atmosphere.8 Climatic conditions of the Atlantic Forest in the Brazilian Northeast during
summer present average temperature and relative humidity of 28ºC and 52%, 9 which is the
period of harvest and processing of sugar cane. Sugar warehouses, large buildings with
areas typically between 5,000 and 10,000 m2, should present adequate internal conditions
for preserving the characteristics of this product, especially concerning ventilation that
prevents excessive increases in temperature, and allows for FIFO - first in, first out, which
reduces the product storage period. Such conditions are not always verified due to
inadequate design and use of warehouses originally built for storage of other products,
Northeast and the lack of information on minimization of product browning, this study was
conducted to assess the alterations in color of white sugar - refined and crystallized, as a
function of storage time. Another objective of this study was also to establish linear
regression equations for prediction of increased ICUMSA color and visual color
(reflectance) during the storage period, in order to ensure product quality at the time of
marketing.
The material for this study consisted of two lots3 of white sugar, each with 2,000 sacks
weighing 50kg each. One of crystal sugar and the other refined sugar, produced by two
plants located in the state of Alagoas, Brazil. The lots (Figure 1) were setup inside a typical
sugar warehouse belonging to the Regional Cooperative of Sugar and Alcohol Producers of
Sample size was determined according to the general sampling rule, i.e., collecting a
experimental unit.10 Considering the lot with 2,000 sacks, from each a total of 44 (forty
four) sacks were randomly collected, including 04 (four) from the interior, 08 from each
side and 08 (eight) from the top. This number is in accordance with Standard Method No.
13 of the Ministry of Agriculture, Livestock and Supply. 11 Samples were collected at the
moment the lots were setup (day 1) and at monthly intervals for a period of 06 (six)
months.
Based on the assumption that most units contain the studied phenomenon, from each
bag individual sugar samples of 100g (one hundred grams) were removed to prepare a
composite sample.10 The individual samples were homogenized and reduced in a Jones
splitter to obtain 2 kg composite samples which were sent to the Central Analytical
Agriculture, Livestock and Supply - MAPA and certified by the BRTUV Quality Control
LTDA according to the standard ISO 9001:2008, where analytical tests were performed
regarding quality and browning of sugar as follows: POL, equivalent to the quantity of
sucrose, determined by the polarimetry technique using a sugar solution with concentration
3
The lot is understood as sacks of the product manufactured under essentially the same process
conditions and manufacture time.
2
. Conselho Regional de Química (Regional Chemistry Council)
65
equal to 26g/100cm3 and the international scale of sugar whose results are expressed in
results expressed as %w/w (ICUMSA GS 2/1/3-15, 2005); Conductivity ash, whose results
in %w/w express the content of dissociated salt in a sugar solution with a concentration equal
correction to 7.0,12 Reflectance index (RI), whose dimensionless results express the degree
dimensionless;12 Reducing Sugars (RS), were determined by the Knight and Allen method
with EDTA. Results were expressed in grams of reducing sugars per 100 grams of the
using the Folin-Ciocalteau reagent. Results are expressed in mg.kg -1;15-17 and finally the
Indicator Value (IV) which provides a relationship between the ICUMSA color in
ICUMSA were validated for accuracy by tests of repeatability and reproducibility for each
analysis. The method used for quantification of total phenolic compounds (TPH) was
Statistical analyses included the Duncan test, Students test, Pearson correlation, linear
Monitoring of relative humidity and temperature inside the warehouse was performed
using a digital hygrometer, brand TEXT, whose readings were stored every 30 minutes.
The data obtained during this study are summarized in Figure 2 which also shows the
respective trend lines - increase in relative humidity of the air and decrease in temperature
along the experimental period – typical of the end of summer and early winter in the
Brazilian Northeast.
When analyzing the influence of climatic variations on sugar quality (Table 1), it
appears that different from the pol and conductivity ash, moisture content showed no
significant differences between sugars types. The evolution of this quality parameter during
storage, although significant in the crystal sugar after 57 days and at 92 days in the refined
sugar, was not sufficient to cause appearance of hardened clods. Regarding the differences
between samples, the refined sugar presented higher and lower values of pol and
conductivity ash, respectfully, due to its greater purity. It should be noted that both the pol
value of the crystal sugar and levels of conductivity ash of the refined sugar remained
stable during the experimental period. From an analytical point of view, the variations of
these parameters are within the limits for validation of the methods and the results are in
accordance with the standards for production plants, not compromising sugar quality during
storage.
With respect to the parameters involved in the browning of sugar, the results are
presented in Tables 2, 3 and 4. The progressive and significant increase in ICUMSA color
storage time on browning and also demonstrates a tendency to stabilize. Upon analyzing the
67
results it is verified that despite presenting a smaller color increase (15 IU) during storage,
the percentage of browning in refined sugar (20,92%) during storage was higher than that
of crystal sugar.
This lower percentage of browning in crystal sugar may be explained by the presence
of sulfide (Table 2), a residue of sulphitation performed during the clarification of the juice
from this type of sugar; however, according to Davis,19 sulfitation is actually increases
color more than it contributes to clarification. Additionally, the 8.8% reduction of this
compound after the first month of storage may have been due to its volatilization because it
is a volatile oxide.
Although the reflectance index did not present significant alteration as a function of
time, the slight decrease observed indicates a tendency that these sugars are visually darker.
It should be noted that because the difference in sugar types (mean of 12%) is greater than
The pH values presented in Table 3 demonstrate that both sugars have a slightly acidic
character, which together with a slight increase in moisture content disfavor the formation
of melanoidins, after the formation of sucrose crystals. Moreover, the reducing sugar
concentration that differed (p <0.05) between sugar types remained stable up to 92 days
after storage.
Considering that sugar color intensity is a function of pH and its changes are not linear,
and also considering sensitivity as well as the participation of each precursor in colored
simple method to estimate the nature and contribution of the various types of precursors to
sugar browning. The average results – 5.84 and 7.19 – shown in Table 4, although not
evaluated in function of the storage time, differed significantly between samples of crystal
and refined sugars, respectively, and indicated that phenolic compounds are the main
68
precursors of browning observed in this study. These low molecular weight compounds
(<2,500 Dalton) which include flavonoids, phenolic acids, other monomeric compounds
and reaction products of polyphenols with iron,20 have high indicator values that can exceed
30.21 This table also reports the levels of phenolic compounds which increased by 88,16%
and 74,65%, respectively, during storage of both sugar types. This increase may result from
the chemical affinities between flavonoids and glycosides, as in the case of flavones which
when associated with sucrose tend to be included in the sugar crystals. Similarly, phenolic
acids were difficult to remove during extraction and crystallization, and when present in the
final product can contribute to enhance browning of white sugar. These acids can also react
with iron to form highly stable dark soluble complexes, such as the complex of iron with
catechol, considered responsible for the green halos in browned sugars 22 Results of the IV
obtained in this study are consistent with characteristics of white sugar - low water activity,
acidic pH and increased reducing sugars, as well as sucrose concentrations above 99.80%
(Table 1) which do not favor the formation the other types of precursors such as
Results of the parameters involved in the browning of both sugars were submitted to
predicting the browning of the sugar during a determined storage period. The results
expressed in Tables 5 and 6 show highly significant correlations obtained between days of
storage and both reflectance and ICUMSA color for the crystal sugar of -0.99 and 0.98, and
Based on these results, the corresponding equations relating ICUMSA color and
reflectance index to days of storage were determined for both sugar types. The equations
69
obtained showed high correlation coefficients for predicting the browning of sugar in
• Crystal sugar
• Refined sugar
Figures 3 and 4 show the correlations for ICUMSA color and reflectance index with the
Of the other correlations obtained, with respect to crystal and refined sugar, also
highlighted is that between ICUMSA color and phenolic compounds with values of 0.96
and 0.93 for the crystal and refined sugars, respectfully. Figure 5 shows the graphs of these
correlations for crystal sugar (A) and refined sugar (B), where good coefficients (r2) are
observed equal to 0.9221 and 0.8627, respectively. The equations for predicting the
ICUMSA color from the concentration of phenolic compounds, the main factor responsible
utmost importance for the marketing of sugar, since they provide an indication of browning
intensity within the acceptable limits of color for domestic consumption and/or exports at
To verify the influence of storage time, the data was subjected to a multivariate
analysis technique – the principal component analysis (PCA). The two types of sugar were
70
clearly separated by principal components one (PC1) and two (PC2), shown in figure 6
which explain 97.82% of the variability in the parameters used. By analyzing PC1 which
reproduced the majority (82.73%) of the total variance, it appears that the crystal sugar with
higher positive scores was best represented by the ICUMSA color, phenolic compounds
(PC), sulfite and reducing sugar (RS) parameters which, with the exception of sulfite,
increased during storage. Refined sugar with negative scores was best represented by the
indicator value (IV) and reflectance index (RI) with different patterns of evolution -
CONCLUSION
The results of this study demonstrate the existence of close correlation between storage
time and browning of white sugar, an alteration in which phenolic compounds act as
precursors. Equations established from these results allow for predicting the level of
browning in crystal and refined sugars, measured using the ICUMSA color and reflectance
index in the various time intervals. From these equations the maximum storage time of
white sugar can be calculated, without causing quality losses for domestic consumption and
exportation.
ACKNOWLEDGMENTS
Institute of Education, Science and Technology of Alagoas) and the Cooperativa Regional
Alcohol Producers of Alagoas) for providing the white sugar and a warehouse for
REFERENCES
11p. 1987.
2. Dias, M.C.; Fernandes, L.G.V.; Braga, C.M.P.; Florido, F.G.; Borges, M.T.M.R;
Conference 2008.
constituents in cane sugar manufacturing products with their antioxidant activities. J. Agric.
refina ry process. Sugar Industry Technologist Annual Meeting, 44, Saint John, 1985.
colorants in beet and cane sugar liquors in relation to model colorants using
spectrofluorometry evaluated by HPLC and multiway data analysis. J. Agric. Food Chem.
12. ICUMSA, International Commission for Uniform Methods of Sugar Analysis. Methods
13. ICUMSA, International Commission for Uniform Methods of Sugar Analysis. Methods
14. ICUMSA, International Commission for Uniform Methods of Sugar Analysis. Methods
15. SPRI, Sugar Processing Research Institute. Color Components in Sugar Refinery
16. IAL – Instituto Adolfo Lutz. Métodos Físico-químicos para Análises de Alimentos. IV
17. BSES - Bureau of Sugar Experiment Stations. The Standart Manual for Australian
19. Davis, S. B. The chemistry of colour removal: a processing perspective. Proc. South
21. Paton, N. H; Duong, M. Sugar Cana Phenolics and First Expressed Juice Colour. Part
III. Role of Chlorogenic Acid and Flavonoids in Enzymic Browning of Cane Juice.
22. Riffer, R. The Nature of Colorants in Sugarcane and Cane Sugar Manufacture.
Chemistry and Processing of Sugar Beet and Sugarcane. In: CLARKE, m. a.; Godshall, M.
A. (Eds), Elsevier Science Publishers, New York, Cap 13, p. 186-207, 1988.
75
TABLE 5 – Pearson correlation between the quality parameters of the crystal sugar
Color Sulfite RS PC IV Reflectance Days
Color 1.00 NS 0.99 0.96 NS -0.99 0.98
Sulfite 1.00 NS NS NS NS NS
RS 1.00 0.97 NS -0.99 0.98
PC 1.00 NS -0.98 0.99
IV 1.00 NS NS
Reflectance 1.00 -0.99
Days 1.00
NS: non-significant at 5% significance. PF: phenolic compounds; RS: reducing sugars; IV:
indicator value.
TABELA 6 - Pearson correlation between the quality parameters of the refined sugar
Color Sulfite RS PC IV Reflectance Days
Color 1.00 NS NS 0.93 NS -0.94 0.93
Sulfite 1.00 NS NS NS NS NS
RS 1.00 NS NS NS NS
PC 1.00 NS -0.97 0.99
IV 1.00 NS NS
Reflectance 1.00 -0.96
Days 1.00
NS: non-significant at 5% significance. PF: phenolic compounds; RS: reducing sugars; IV:
indicator value.
80
FIGURE 3 – Correlations for ICUMSA color (A) and Reflectance index (B) with days of
storage for crystal sugar
FIGURA 4 – Correlations for ICUMSA color (A) and Reflectance index (B) with days of
storage for refined sugar
FIGURE 5 – Correlation between ICUMSA color and phenolic compounds for crystal
sugar (A) and refined sugar (B)
82
Obrigado por submeter seu manuscrito "The Effect of Storage Time on Browning of White
Sugar: Crystal and Refined" para publicação na Química Nova, QN.
Assim que o seu arquivo PDF for verificado, o seu manuscrito será inserido no sistema, e você
receberá um outro e-mail com o NÚMERO DE REFERÊNCIA, confirmando assim a
submissão.
Caso você tenha alguma outra dúvida a respeito desta submissão, por favor, entre em contato
com a Gerente Editorial da QN no e-mail: sbqedit@iq.usp.br.
Atenciosamente,
Pricila Gil
SBQ - gerente editorial
Caixa Postal: 26037
05513-970 São Paulo - SP
Tel.: +55.11.30322299
Fax.: +55.11.38143602
web: http://quimicanova.sbq.org.br/
e-mail : sbqedit@iq.usp.br
84
5. CONSIDERAÇÕES FINAIS
REFERÊNCIAS
BENTO, L. S. Colourants through cane sugar production and refining.. Proc. SPRI
Conf., 2008.
http://www.sugarcanecrops.com/p/introduction/
MEAD, G.P. & CHEN, J.C.P. Cane Sugar Handbook. John Wiley & Sons, Inc: Canada.
13 ed., 947p. 1977.
HUGOT, Emile. Manual da Engenharia Açucareira. Editora Mestre Jou. São Paulo,
1969.
KORT, M. J. Colour in the Sugar Industry, in Sugar. Science and Technology, Ed. G. G.
Birch, K, J. Parker, Applied Science Pub. Ltd., London, 1978.
LAROQUE, D.; INISAN, C.; BERGER, C.; VOULAND, E & DUFOSSÉ, L. Kinetic
study on the Maillard reaction. Consideration of sugar reactivity. . Food Chemistry, n.
111, p. 1032 – 1042, 2007.
PATON, N. H. & DUONG, M. Sugar cana phenolics and first expressed juice colour.
Part III. Role of chlorogenic acid and flavonoids in enzymic browing of cane juice.
International Sugar Journal, v. 94, n. 1124, p. 170-176, 1992.
88
TU, J. C., A, KONDO, & E, SLOANE. The role of high and low molecular weight
colorants in sugar color. Proc. of ISSCT Conf., Manufact., 1393 – 1400, 1977.
VICKERS, J.E. GROF, C.P.L.; BONNETT, G.D.; JACKSON, P.A.; KNIGHT,D.P.; S.E.
ROBERTS & ROBINSON, S.P. Overexpression of Polyphenol Oxidase in Transgenic
Sugarcane Results in Darker Juice and Raw Sugar. Crop Science. Vol.45, p. 354-362,
2005.
89
SMITH, P & PATON, N. H. Sugar cane flavonois. Sugar Industry Reviews, v. 12, n. 2-3,
p. 117-142, 1985.
COCA, M., GARCIA, M. T., GONZÁLEZ, G., PENA, M. & GARCIA, J. A. Study of
coloured components formed in sugar beet processing. Food Chem., 2004.
BARKER, B., & DAVIS, S. B. Colour removal with the SPARAC process - Preliminar
results. Proc. Of South S. African Sugar Tec. Assoc., 490 – 494, 2002.
BSES - Bureau of Sugar Experiment Stations. The Standart Manual for Australian Sugar
Mills. Brisbane, 1991