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Thai CCD, Doherty WOS Proc Aust Soc Sugar Cane Technol Vol 33 2011

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THE COMPOSITION OF SUGARCANE JUICES


DERIVED FROM BURNT CANE
AND WHOLE GREEN CANE CROP

By

CCD THAI, WOS DOHERTY

Sugar Research and Innovation,


Centre of Tropical Crops and Biocommodities,
Queensland University of Technology, Brisbane
caroline.thai@student.qut.edu.au

KEYWORDS: Whole Sugarcane Crop, Trash,


Juice Composition, Clarification,
Sugar Quality, Burnt Cane Juice.
Abstract
THERE HAS been substantial interest within the Australian sugar industry in product
diversification as a means to reduce its exposure to fluctuating raw sugar prices and in
order to increase its commercial viability. In particular, the industry is looking at fibrous
residues from sugarcane harvesting (trash) and from sugarcane milling (bagasse) for
cogeneration and the production of biocommodities, as these are complementary to the
core process of sugar production. A means of producing surplus residue (biomass) is to
process whole sugarcane crop. In this paper, the composition of different juices derived
from different harvesting methods, viz. burnt cane with all trash extracted (BE), green
cane with half of the trash extracted (GE), and green cane (whole sugarcane crop) with
trash unextracted (GU), were investigated and the results and comparison presented.
The determination of electrical conductivity, inorganic composition, and organic acids
indicate that both GU and GE cane juice contain a higher proportion of soluble
inorganic ions and ionisable organic acids, compared to BE cane juice. It is important to
note that there are considerably higher levels of Na ions and citric acid, but relatively
low P levels in the GU samples. A higher level of reducing sugars was analysed in the
GU samples than the BE samples due to the higher proportion of impurities found
naturally in sugarcane tops and leaves. The purity of the first expressed juice (FEJ) of
GU cane was on average higher than that of FEJ of BE cane. Results also show that GU
juices appear to contain higher levels of proteins and polysaccharides, with no
significant difference in starch levels.
Introduction
In the past few years, there has been interest in the development of diversification products
from bagasse and trash (sugarcane tops and leaves) (Abbasi and Abbasi, 2010; Goldemberg and
Guardabassi, 2010). Additional biomass from sugarcane trash will enhance diversification
opportunities for such products as cellulosic ethanol, platform chemicals, bio-oils, pulp and paper,
bioplastics and textiles. Thus, benefits associated with processing whole sugarcane crop (stalk and
trash) include the following:
• Reduced environmental pollution due to the elimination of cane burning;
• Additional biomass for cogeneration or diversification products;
• Additional sucrose recovered from juice extracted from trash. Research reported by
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Thai CCD, Doherty WOS Proc Aust Soc Sugar Cane Technol Vol 33 2011
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Gil and Saska (2005) indicated that one quarter of the sucrose currently derived from
the sugarcane stalk is present in discarded sugarcane trash. This additional sucrose is
expected to increase raw sugar yield if the level of impurities can be reduced through
an appropriate clarification strategy;
• Minimisation of sucrose losses during harvesting. The sources of sucrose loss during
harvesting are the cleaning system (6%–9%), choppers (4%), base cutters (2%) and
gathering system (1%) (Sandell and Agnew, 2002; Whiteing et al., 2002).
Many attempts to measure the quality parameters of sugarcane juice expressed from trash
were reported through laboratory (Ivin and Doyle, 1989; Qudsieh et al., 2001; Scott et al., 1978)
and factory trials (Bernhardt et al., 2000; Kent et al., 2010; Larrahondo A. et al., 1998; Moller et
al., 2010; Muir et al., 2009; Reid and Lionnet, 1989; Saska, 2008). However, little information has
been presented on the clarification process and physiochemical behaviour of such juices.
The effect of impurities and their proportions on the clarification process is not well
understood, neither are the intricacies of the physical interactions between impurities.
This paper is part of a program to identify clarification strategies for processing whole crop
juice. A comparative analysis is presented on the composition of sugarcane juices derived from
different harvesting methods, viz. burnt cane with all trash extracted (BE), whole crop with half of
the trash extracted (GE) and whole crop with trash unextracted (GU).
Experimental
Factory juices
Burnt and green sugarcane were harvested from different farm fields, which are identified
by the letters A to F in this paper. First expressed juice (FEJ) and primary juice (PJ) composite
samples for BE and GE, described in Table 1, were collected from the processing lines at Condong
Mill, NSW, Australia, during the crushing season in 2009 and 2010. The FEJ of GU cane was
obtained by harvesting whole crop in the field and expressed with a laboratory hammer mill.
Table 1—Details of sugarcane juice samples obtained from Condong Mill.

Sample Number of composites Type of juice Type of cane harvested


BE FEJ 3 First Expressed Juice Burnt cane
GU FEJ 4 First Expressed Juice Whole green cane crop
BE PJ 2 Primary Juice Burnt cane
Green cane crop with half of
GE PJ 1 Primary Juice
the trash extracted

All juices were stored at –20 °C and thawed prior to analysis. The brix of samples, at least in
duplicate, was measured at ambient room temperature using a Bellingham and Stanley RFM 342
Refractometer accurate to ±0.01°Brix. The electrical conductivity was measured in triplicate using a
TPS 900C Conductivity Meter and conductivity cell (glass probe, k=1.0) calibrated using KCl
standard solutions.
Double polarisation measurements
The determination of double pol was conducted by double polarisation measurements (in
triplicate) using a Schmidt and Haensch Polartronic Universal Polarimeter. Juice samples were
clarified using minimal lead acetate (dry lead) and the solution filtered for double pol
measurements. The dry substance test was conducted to determine the % total solids. Measurements
were taken in duplicate by drying for 18 h at 65±2 °C in a vacuum oven.
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Thai CCD, Doherty WOS Proc Aust Soc Sugar Cane Technol Vol 33 2011
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The purity was calculated using the following equation:

(1)

Chromatographic instrumentation
The separation and quantification of sugars, in duplicate, was conducted by high-
performance ion chromatography coupled with pulse amperometric detection (HPIC-PAD) based
on the ICUMSA Method GS7/8/7-24. Analyses were carried out on a Waters HPIC-PAD system
coupled to a Waters 2465 Electrochemical Detector.
The determination of organic acid concentration (measured in duplicate) was investigated
via cation exchange high-performance liquid chromatography (HPLC) using dual BioRad Aminex
HPX-87Hx columns (300 mm × 7.8 mm I.D.) connected in series and equilibrated to 35 °C and
85 °C respectively (Blake et al., 1987).
Spectroscopic instrumentation
Starch analysis was conducted based on the ICUMSA VSI Method 3 (2007) iodometric
method with modifications and measurements obtained in duplicate. Starch concentrations were
determined using a Cintra 40 double-beam UV-visible absorption spectrometer with the absorbance
measured at 570 nm.
Total polysaccharides were determined from triplicate measurements using the SPRI (Sugar
Processing Research Institute) procedure (Roberts, 1981). Soluble polysaccharides in sugarcane
juice were precipitated by absolute ethanol with the aid of celite. The precipitate was treated with
1% (w/v) phenol and concentrated sulphuric acid prior to analysis using a Cintra 40 double-beam
UV-visible absorption spectrometer at 485 nm.
The colorimetric detection and quantification of protein was conducted using the
bicinchoninic acid (BCA) Protein Assay Kit (Pierce, Bonn, Germany); 25 μL sample/200 μL BCA
working reagent; 37 °C for 30 min; 562 nm, based on the manufacturer’s instructions. The
quantification (in triplicate) of protein in sugarcane juice was carried out on a Beckman AD
200 UV/VIS Plate Reader.
Inorganic components
Inorganic components (soluble Al, Ca, Cl, Fe, K, Mg, Na, P, S and Si), measured in
triplicate, were determined by inductively coupled argon plasma optical emission spectrometry
(ICPOES, Varian Vista-MPX equipped with a simultaneous charge coupled device detector).

Results and discussion


The analytical results obtained stand by the analysis of unrelated juice samples. The data
provided, however, will provide useful information on impurity removal strategies during
clarification of juice from whole sugarcane crop.
Quality parameters
On the basis of the quality parameters presented in Table 2, GU FEJ, in contrast to BE FEJ,
is higher in purity and moisture by 15% and 6.6% respectively and lower in both brix and pol by
87% and 91% respectively. Comparing the BE PJ and the GE PJ samples, GE is higher in both
purity and moisture by 1.2% and 2.1% respectively and lower in both brix and pol by 88% and 91%
respectively. The results obtained from Table 2 are in agreement with the work published by Scott
et al. (1978) who reported an increase in moisture content and purity with a decrease in pol of the
juice expressed from cane tops alone.
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Table 2—Quality parameters (on dry solids) of different sugarcane juices.

Field Sample Brix Moisture Purity Pol


BE FEJ 22.37 75.7 75.6 18.38
A
GU FEJ 21.00 80.4 103.4 20.26
BE FEJ 21.00 72.1 65.7 18.32
B
GU FEJ 19.99 72.4 59.3 16.38
BE FEJ 22.29 69.3 59.8 18.35
C
GU FEJ 20.36 71.7 57.6 16.31
D GU FEJ 15.12 84.4 88.8 13.86
BE PJ 15.57 84.1 80.6 12.81
E
BE PJ 14.94 83.5 81.2 13.40
F GE PJ 13.41 85.6 81.9 11.87
BE FEJ 21.89±0.77 72.4±3.2 67.0±8.0 18.35±0.03
Average ±SD GU FEJ 19.12±2.70 77.2±6.2 77.3±22.6 16.70±2.65
BE PJ 15.26±0.45 83.8±0.4 80.9±0.4 13.11±0.42

Concentration of soluble ions


Ash in sugarcane juice is an important aspect that refers to the soluble inorganic salts
contained in sugarcane juice. Jackson et al. (2008) reported that a high ash/reducing sugars ratio
would increase the probability of sucrose loss to molasses and effectively affect raw sugar yield and
quality. The level of ash correlates with the electrical conductivity (EC) of the juice. The EC
depends on the concentrations of ions and their mobility in solution and therefore is associated with
the viscosity and brix of sugarcane juice (Jackson et al., 2008). The EC in sugarcane juices have
been determined previously by a number of workers (Jackson et al., 2008; Kingston, 1982; Olson,
2002).
As shown in Table 3, the EC of the GU FEJ analysed was 4% higher than BE FEJ,
consistent with the findings of Saska (2008) who reported that the conductivity of tops was three
times higher than cane stalk. The results from Table 3 also indicate that GU FEJ contains a higher
proportion of soluble inorganic and ionisable organic acids than BE.

Table 3—Average electrical conductivity of juices.


Electrical conductivity
Field Sample
(µS/cm on dry solids)
BE FEJ 9 589
A
GU FEJ 13 881
BE FEJ 14 024
B
GU FEJ 14 407
BE FEJ 15 119
C
GU FEJ 22 397
D GU FEJ 16 448
BE PJ 19 332
E
BE PJ 20 880
F GE PJ 20 880
BE FEJ 12 911±2928
Average ±SD GU FEJ 13 427±3903
BE PJ 20 106±1095

The concentrations of inorganic components in FEJ and PJ are shown in Tables 4 and 5. The
concentration of the inorganic components are relatively higher in the PJ samples analysed than in
the FEJ samples, corresponding to the EC results. The concentrations of various inorganic
components are detrimental to the quality of clarified juice as soluble metal ions may become
concentrated during subsequent processing. During clarification, Ca, P, Mg and Si are partially
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Thai CCD, Doherty WOS Proc Aust Soc Sugar Cane Technol Vol 33 2011
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removed (Clarke, 1993). It is important to note K contributes to ~51% of the total inorganic
composition in sugarcane juices (Tables 4 and 5) and the level of K is dependent on cane variety
and soil type. The presence of inorganic components, in particular K, in subsequent processing
streams such as molasses, increases sucrose retention and therefore losses to raw sugar yield
(Clarke, 1993).
For the FEJ samples, higher concentrations of Al, Ca, Cl, Fe, K, Mg Na, S and Si were
determined in the GU juice samples. Furthermore, GU FEJ contained higher levels of Na ions,
which would encourage particle dispersion (Zhang et al., 2006) during clarification i.e. high
turbidity of clarified juice.
The higher proportion of P in juices would generally result in better juice clarification,
because a larger proportion of calcium phosphate precipitate would form, improving adsorption of
suspended solids and sweep flocculation.
Table 4—Concentration of inorganic components (ppm on dry solids) determined by ICPOES.
Field Sample Ca P Mg Si K
BE FEJ 545 750 1195 115 3950
A
GU FEJ 665 720 1365 151 5050
BE FEJ 515 1948 1220 107 5700
B
GU FEJ 665 1504 1270 143 5600
BE FEJ 890 615 1325 96 5800
C
GU FEJ 1335 465 1730 100 7900
D GU FEJ 685 451 915 218 5950
BE PJ 1060 670 1325 294 7800
E
BE PJ 1290 930 1280 311 6700
F GE PJ 1005 930 1655 274 6450
BE FEJ 650±208 1104±734 1247±69 106±10 5150±1040
Average
GU FEJ 918±321 905±442 1505±222 167±75 6250±1242
±SD
BE PJ 873±265 560±115 1120±290 256±54 6875±1308

Table 5—Concentration of inorganic components (ppm on dry solids) determined by ICPOES.

Field Sample Cl S Fe Na Al
BE FEJ 1359 1777 35 142 45
A
GU FEJ 3916 2334 68 200 106
BE FEJ 2089 1285 22 112 28
B
GU FEJ 3294 1328 56 107 97
BE FEJ 3247 1237 47 82 55
C
GU FEJ 5147 1801 78 94 84
D GU FEJ 4686 2741 18 227 29
BE PJ 2269 1552 32 250 44
E
BE PJ 4390 2232 38 595 49
F GE PJ 3796 2019 45 220 89
BE FEJ 2232±952 1433±299 35±13 112±30 42±14
Average
GU FEJ 4261±820 2051±617 61±14 155±64 94±10
±SD
BE PJ 3329±1500 1892±481 25±10 238±16 36±11
Sugar analysis
The reducing sugars are generally a higher proportion of juice extracted from trash than that
from billeted cane stalk (Ivin and Doyle, 1989). The significantly higher level of reducing sugars in
whole crop juices (Table 6) implies higher sucrose recovery from burnt cane.
This observation was not obtained from recent factory trials by Moller et al. (2010), who
reported a 30% increase in purity of final molasses from whole crop. As is well established, the
solubility of sucrose is dependent on the level of ash and reducing sugars, where the former
increases the solubility, and the latter decreases the solubility (Jackson et al., 2008).
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Thai CCD, Doherty WOS Proc Aust Soc Sugar Cane Technol Vol 33 2011
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Table 6—Average % glucose, % fructose and % sucrose (on dry solids).


Field Sample % Glucose % Fructose % Sucrose
BE FEJ 1.74 1.48 83.7
A
GU FEJ 2.10 2.05 70.0
BE FEJ 1.38 1.29 85.76
B
GU FEJ 2.80 2.35 81.24
BE FEJ 2.38 2.24 80.57
C
GU FEJ 4.22 3.49 77.06
D GU FEJ 3.97 4.10 73.55
BE PJ 1.28 1.35 76.62
E
BE PJ 1.54 1.67 88.15
F GE PJ 1.19 1.27 86.65
BE FEJ 1.83±0.51 1.67±0.50 83.3±2.6
Average ±SD GU FEJ 3.27±1.00 3.00±0.96 75.5±4.8
BE PJ 1.41±0.18 1.51±0.23 82.4±8.2

Soluble non-sucrose impurities


The organic acid concentrations of sugarcane juices are primarily responsible for the pH
level of the juice as well as the quantity of lime added during clarification. On the basis of the
concentrations of the organic acids identified in sugarcane juices (Table 7), the concentration of
trans-aconitic acid largely contributes to the bulk organic acid content.
Trans-aconitic, citric, malic and oxalic acid are associated with the formation of scale on
factory heating surfaces, where the latter is the major organic acid contributor (Walford and
Walthew, 1996). Citric acid is present in higher proportions in the GU and the GE samples than the
BE juice sample.
The solubility of citric acid is higher than oxalic acid and aconitic acid, whose calcium salts
are prevalent as scale components in evaporators and pans. Citric acid is expected to remain in the
sugar process streams through to final molasses. In sugar process streams, citric acid would remain
highly associated with calcium, possibly influencing sugar recovery.

Table 7—Average organic acid concentration (ppm on dry solids).


Trans- Cis-
Citric D- L(+)-
Field Sample aconitic L-malic Oxalic aconitic Succinic
acid gluconic Lactic
acid acid
BE FEJ 1868 447 122 254 260 168 116 68
A
GU FEJ 2506 481 83 298 314 225 119 68

BE FEJ 2518 523 58 277 355 184 144 27


B
GU FEJ 2531 502 124 282 253 231 147 16

BE FEJ 2723 640 153 209 1300 167 117 22


C
GU FEJ 2785 632 161 245 1296 173 124 15

D GU FEJ 1671 670 240 391 1024 505 111 110

BE PJ 2779 735 135 490 583 330 156 436


E
BE PJ 3170 796 133 531 600 322 163 420

F GE PJ 2079 788 234 413 866 376 162 301

BE FEJ 2370±446 537±97 111±48 247±35 638±575 173±9 126±16 39±26


Average
GU FEJ 2373±485 571±94 152±67 304±62 722±519 284±150 126±15 52±46
±SD
BE PJ 2974±772 765±6 134±71 551±83 591±189 326±39 159±1 428±84
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Due to the more polar nature of polysaccharides (e.g. arabinogalactans-gums and


hemicellulose) and proteins, and from evidence that shows sucrose in solution has a solubilising
effect on proteins, it is likely that proteins and polysaccharides are less strongly adsorbed and
therefore form the major boundary between the particle and the bulk phase of the juice (Bennett,
1957). Proteins, polysaccharides and starch contribute to the increased viscosity of syrup, lower
throughput rates and also produce colour-forming compounds (Clarke et al., 1980). In essence, high
grade pans are severely affected by low evaporation rates, poor circulation and slow boil-on rates
for feed liquor containing high levels of starch, proteins and polysaccharides.
Table 8 shows that polysaccharides are relatively higher in the GE sample (and to a lesser
extent GU) compared to BE. Moreover, Table 8 also shows that GE has significantly higher starch
than BE PJ. The starch levels of the juices are significantly lower than those of polysaccharides,
which are in agreement with the data reported by Eggleston et al. (2009).

Table 8—The concentrations of protein, polysaccharides and starch


(ppm on dry solids) of different sugarcane juices.

Field Sample Protein Polysaccharides Starch


BE FEJ 4908 8529 505
A
GU FEJ 5154 6857 638
BE FEJ 5468 7029 1324
B
GU FEJ 6076 11346 705
BE FEJ 4771 6218 552
C
GU FEJ 5393 9460 776
D GU FEJ 10467 7738 966
BE PJ 3616 7861 565
E
BE PJ 4874 8795 636
F GE PJ 5843 10872 1126
BE FEJ 5049±369 7259±1172 794±460
Average ±SD GU FEJ 6773±2494 8850±1984 771±142
BE PJ 4245±890 8328±660 601±50

Sugarcane juice contains significantly higher concentrations of sugars than proteins.


Therefore, the analysis of proteins by UV-visible spectrometry resulted in inaccurate estimation due
to the interference of sugars (Eggleston, 1999). The separation of sugars and amino acids of food
samples have been attempted by ion exchange chromatography (Thiele et al., 2002) and gel
filtration (Hagel, 1989) and protein quantification using the BCA (Krieg et al., 2005). This
approach was used in this study, which was previously used by a number of workers to determine
proteins in juice (Lee et al., 2010).
A comparison between burnt cane juice and whole crop juice from FEJ and PJ (Table 8)
suggests whole crop juices (GE and GE) contain relatively higher protein and polysaccharide levels.
Higher protein levels such as that obtained from the GE sample implies that the juice would contain
increasing higher proportions of amino acids during processing which would be available for the
Maillard reaction with reducing sugars (Painter, 1998). Proteins are denatured by heat and are
known to adhere to the surface of the clarifier tank and immobilise the stainless steel sweepers. This
occurrence may be more prevalent when processing whole crop juice because of the higher protein
content.
Conclusion
Juices from burnt sugarcane and whole sugarcane crop have been analysed in order to give
an indication of the effect of trash on juice composition. There are significant differences between
the juices. The inclusion of cane tops and trash in whole crop juices (GU FEJ and GE PJ) appeared
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to result in lower brix and pol and higher purity and moisture content than burnt cane juices.
Relatively higher concentrations of Al, Ca, Cl, Fe, K, Mg, Na, S and Si were detected in GU FEJ
than BE FEJ samples.
This trend of higher inorganic components in GU FEJ juice was consistent with the data
obtained from EC measurements. In addition, whole crop juices (GU and GE) were also higher in
reducing sugars, protein, starch and polysaccharides. The inability experienced by previous workers
to effectively clarify whole crop juice may in part be related not to one juice constituent, but a
combination of juice constituents interacting with one another. Impurities removal strategies can be
investigated by determining the behaviour of impurities during clarification.
Future work on juice composition is continuing in order to determine other monosaccharides
and disaccharides, and oligosaccharides present in sugar juice. The zeta potential (net particle
charge) of juices and the interacting effects of liming techniques are also currently being
investigated.
Acknowledgements
The authors sincerely thank Sugar Research Development Corporation (SRDC), Sugar
Research Limited (SRL) and Queensland University of Technology for funding this project. The
authors wish to thank the management and production staff at Condong Mill.
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