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Water content of acacia honey determined by two established methods and by

optothermal window

Article  in  Acta Chimica Slovenica · January 2008

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 Acta Chim. Slov. 2008, 55, 273–276 273

Scientific paper

Water Content of Acacia Honey Determined

by Two Established Methods and
by Optothermal Window
Sándor Szopos,1 Ottó Dóka,1 Dane Bicanic2 and Zsolt Ajtony1
1
Faculty of Agricultural and Food Sciences. University of West Hungary.
Vár 2, H-9200 Mosonmagyaróvár, Hungary
2
Laboratory for Biophysics, Department of Agrotechnology and Food Sciences,
Wageningen University and Research Centre, Dreijenlaan 3, 6700 HA Wageningen, The Netherlands

* Corresponding author: E-mail: dokao@mtk.nyme.hu

Received: 12-12-2007

Abstract
The major objective of the research study described here was to explore the potential of the optothermal window (OW)
technique as a new approach towards a simple, rapid determination of water content in honey. Water, major component
of foods, influences their physical and chemical properties. Single mode RLT-1480-40G laser diode and the standard
addition method were used to calibrate the response of the OW detector at analytical wavelength of 1478 nm and to de-
termine water content of Acacia honey. The performance of the OW method was compared to that of well established
gravimetry and refractometry; the values obtained by the three different methods are practically the same.

Keywords: Gravimetry, refractive index, optothermal window, honey, water content

ter content.7 Likewise, determination of water content is

1. Introduction independent of honey’s botanical origin. Routinely, the
Water is one of the major components of foods and moisture content of unifloral or multifloral honeys is de-
raw food materials and influences their physico-chemical termined by Abbé refractometer.4 In determining the moi-
properties (i.e. colour, rheological and microbiological sture content the absolute error achievable by most met-
status, shelf-life etc.) and hence also the quality. Due to its hods (0.9-and 5.1 %) is inferior to that of a more accurate
abundance, water is the least expensive and most fre- Karl-Fischer method. The latter is however time consu-
quently added substance to various foods in an attempt of ming and also requires considerable skill and advanced la-
economic fraud. boratory equipment. On the other hand RI is widely used
The objective of research described here was to ex- due to its simplicity.
plore the potential of the optothermal window (OW) met- Depending on sort flowers used to produce honey,
hod as a new approach towards a simple, rapid and user RI values obtained by refractometer are either too low or
friendly determination of moisture content in honey. Moi- too high. The true moisture content can be determined by
sture content not only plays a paramount role in preser- Karl-Fisher (K-F) titration method6 that yields reprodu-
ving the quality of honey but it is also of importance for cible results for total moisture content.6 Drying by infra-
the characterization of unifloral honeys.1 red radiation is another method used to determine the
Measurement of refractive index (RI),2 Karl-Fischer moisture content. Resulting weight loss depends on selec-
titration method2–3 and oven drying4 are among the techni- ted parameters (drying period and drying temperatures)
ques commonly used to characterize unifloral honeys. and includes all volatile products.7 Since it is not possible
Although these methods yield reproducible results when to remove all water from the samples by drying, the asses-
used to characterize unifloral honeys,5 significant diffe- sed moisture content is usually lower than the true moistu-
rences have been observed when determining the total wa- re content.

Szopos et al.: Water Content of Acacia Honey Determined by Two Established Methods ...
274 Acta Chim. Slov. 2008, 55, 273–276

Determination of water by means of spectrophoto- netration depth 1/β must exceed the thermal diffusion
metric methods relies on the availability of broad NIR ab- length (β–1 > µ). As the generated heat is directly propor-
sorption features associated with the overtones and com- tional to the intensity of radiation source, it is necessary to
bination bands. The spectrum features four peaks found at normalize H. To do so one first records, under identical
970 nm, 1190 nm, 1450 nm and 1940 nm. These peaks are experimental conditions, the OW signal C (µV) from the
associated with the second overtone of OH stretching empty disc; the difference H–C represents the net OW sig-
band (3ν1,3), the combination of the first overtone of the nal (µV) from honey. As a next step, one measures, again
O–H stretching and the OH-bending band (2ν1,3+ ν2), under the same circumstances, the OW signal (µV) B
first overtone of the OH-stretching band (2ν1,3) and the from a strongly absorbing reference (such as a black dra-
combination of OH-stretching and O–H bending bands wing ink) and corrects it (B–C) to obtain the net OW (µV)
(2ν1,3+ν2), respectively.8 signal from the ink. The normalization step implies the di-
The OW method proposed here as a new approach vision of the net OW signals obtained from the experi-
towards determination of moisture content of honey ma- mentally measured signals H, B and C:
kes use of the 40 mW NIR laser diode emitting at 1478
nm wavelength that coincides with a strong absorption li-
(2)
ne of water molecule. The suitability of the proposed met-
hod was evaluated by comparing its overall performance
to that achieved by two traditional techniques. where Sn is the normalized (dimensionless) OW signal for
honey at a given wavelength and a given incident power.
As the magnitude of the OW signal in general de-
2. Basic Concepts of the OW Method pends in a complex manner on optical and thermal proper-
ties of the test sample, parameters µ and β are expected to
The OW technique is a variant of photoacoustic appear in the theoretical relationship for the normalized
(PA) spectroscopy.9,10 The heat generated in honey by se- OW signal Sn. When the relationship µ < β–1 < L is being
lective absorption (at a given wavelength optical absorp- satisfied for honey, one can obtain the normalized OW
tion coefficient of sample per unit length is β (m–1)) of ra- signal using the relationship:9, 11
diation that is periodically modulated at a frequency f
(s–1), diffuses into a disk (it has large thermal expansion
(3)
coefficient) loaded with the test sample. Good thermal
contact between honey and the disc is an impetus. The pe-
riodic expansion and contraction of disk produces an The Eq. 3 can be solved for µβ and one obtains:
acoustic wave which is detected (OW signal) by means of
the piezoelectric transducer. In general, the magnitude of
(4)
the OW signal decreases for higher frequencies; the sensi-
tivity of the sensor follows the same trend. Next to β,
another physical parameter that plays a decisive role in The product µβ is related to the more familiar absor-
generation of OW signal is sample’s thermal diffusion bance A since:
length µ (m) defined as:
(5)
(1)
or

with α (m2s–1) being the thermal diffusivity of the test A= ε (c/M) µ (6)
sample.
Physically, µ is a distance in honey across which the where ε, c and M are extinction coefficient (lit mol–1 cm–1)
amplitude of the generated thermal wave reduces to e–1 of at a given wavelength, the concentration (g lit–1) and the
its initial value. Only the heat that originates from a honey molecular weight (g mol–1) respectively.
layer one thermal diffusion length thick is detected by the
piezoelectric transducer. If the physical thickness L of ho-
ney is larger than its thermal diffusion length µ, the sam- 3. Experimental
ple is referred to as „thermally thick”.
Recording, at a given modulation frequency f, the Figure 1 shows the experimental arrangement used
magnitude H (µV) of the OW signal from honey while in this study. The 1478 nm radiation from a single mode
varying the wavelength of the incident radiation enables RLT-1480-40G laser diode emitting 40 mW cw output po-
one to obtain the OW spectrum. For OW spectrum to cor- wer at 170 mA was modulated at 30 Hz by a mechanical
respond with the true absorption spectrum, the optical pe- chopper (HMS Light Beam Chopper 220). About 0.25

Szopos et al.: Water Content of Acacia Honey Determined by Two Established Methods ...
 Acta Chim. Slov. 2008, 55, 273–276 275

cm3 of the honey under investigation is deposited directly 5. 2. Refractometry

onto a surface of a sapphire disc (0.3 mm thin and 13 mm
in diameter) the rear face of which is means of a thermal- Using refractive index (RI) values measured (at 20
ly conducting glue fixed to a ring made of PbZrx Ti1–x O3 °C) by Abbé refractometer it is possible to assess the moi-
(lead zirconium titanate, abbreviated PZT), an inexpen- sture content either by an empirical formula or by using
sive piezoelectric material. Besides its large thermal ex- the ššconversion’’ tables. For above quoted Acacia honey,
pansion coefficient, sapphire disc is highly transparent at RI = 1.4961 which is an average of three independent
1478 nm. measurements and corresponds to 16.24 ±0.10%.moisture
content.

5. 3. Optothermal Window
The outcome of the OW study is shown in Fig 2.
The relationship between the percentage of added water
(x) and the net OW signal (y) obtained from the experi-
ment is linear: the equation of the fitted line reads: y =
0.1949x + 3.1498 with R2 = 0.999.

Figure 1: Schematic diagram of the experimental set-up.

Results obtained by the OW method were compared

to data collected by gravimetry and refractometry. As to
the gravimetric measurements, honey sample was kept in
oven maintained at 100 ±2 °C (according to Hungarian
norm4) until its weight reached a constant value. Refracti-
ve index of honey4 at 20 °C was measured by Abbé refrac-
tometer from Zeiss.
Figure 2: Net OW signal plotted versus the amount of water added
to Acacia honey. This ššcalibration” line allows for determination
4. Materials of the honey’s moisture content.

Acacia honey was selected as the test sample to test

the feasibility of OW method for determining moisture The uncertainties in values of the slope and the inter-
content. A series of calibrating standard solutions (0, 5.11, cept are 0.0027 and 0.0501 respectively. The equation of
10.07, 15.17, 19.89, 25.18 and 30.05% (g/g)) was prepa- the fitted line intersects positive Y-axis at y = 3.1498 µV;
red by adding water to honey- the mixer was used to ho- obviously this value is associated with the moisture con-
mogenize all honey/water mixtures. tent of honey with no water added. If the moisture is remo-
ved from honey, fitted line must intersect the vertical axis
at y = 0. Taking in account the uncertainties and the propa-
5. Results gation of errors, the original moisture content of Acacia
honey determined by OW method is 16.16 ± 0.35 %.
5. 1. Gravimetry From the experimentally obtained net OW signals,
Two samples of Acacia honey were taken; the cor- one has calculated βµ for all samples studied. As it can be
responding weights were 9.78 g and 9.85 g. After a two seen in Fig. 3, calculated βµ values depend linearly on the
days long drying period, the loss of weight measured for moisture content of the samples.
these two samples was 1.603 g and 1.636 g respectively. Substituting y = 0 into the equation of the calibra-
The corresponding moisture contents are 1.603/9.78 = tion line (Fig. 3) allows for the calculation of honey’s
0.1639 and 1.636/9.85 = 0.1661 from which the average moisture content. The value obtained 16.42 ± 1.12% is
moisture content of 16.50 ± 0.16% is obtained. very close to data found by other two methods as well as

Szopos et al.: Water Content of Acacia Honey Determined by Two Established Methods ...
276 Acta Chim. Slov. 2008, 55, 273–276

sensitivity of the method. The most common approach is

that of Standard Addition (also known as a “Known Addi-
tion”) that involves adding a small volume of concentrated
standard to a much larger volume of sample. The combi-
nation of the standard addition method and OW technique
yields the same results as the established techniques such
as gravimetry and refractometry. The OW method might
emerge as a more suitable technique for applications in
practice. The intrinsic precision (better than that of RI ap-
proach), reasonably high speed (considerably faster than
drying oven) and the fact that it is a total amount of water
in honey that is being measured, are the most important
pros of the newly proposed method.

Figure 3: Calculated βµ values plotted versus the amount of water 7. References

added to honey.

1. L. Persano Oddo, S. Bogdanov, Apidologie 2004, 35, S2–S3.

2. K. Zürcher, H. Hadorn, Mitt.Geb.Lebensmitteluntersuch.
to the outcome provided by OW method when the net OW Hyg. 1980, 71, 396–403.
signals were used in calculations. Based on the obtained 3. S. Bogdanov, K Ruoff, L. Persano Oddo, Apidologie 2004,
results one can state that various methods for determina- 35, S4–S17.
tion of water content in Acacia honey produce practically 4. MSZ 6943/1–79. Méz kémiai és fizikai vizsgálata [Hunga-
the same results. rian Standard No 6943/1–79. Chemical and physical investi-
gation of honey.]
5. L. Persano Oddo, R. Piro, Apidologie 2004, 35, S38–S81.
6. Summary and Conclusions 6. H. -D. Isengard, D. Schultheiß, Food Chem. 2003, 82,
151–154.
The OW method with a single mode RLT-1480-40G 7. H. -D. Isengard, D. Schultheiß, B. Radovi}, E. Anklam, Food
laser diode used as the radiation source was applied here Contr. 2001, 12, 459–466.
for quantitative, direct determination of moisture content 8. W. A. P. Luck, in W. A. P. Luck (Ed.): Structure of water and
in unifloral, realistic and liquid (sugar has not yet crystal- aqueous solutions, Verlag Chemie, Weinheim, Germany,
lized) honeys. In a case of creamy honey (product that has 1974, pp. 248–284.
crystallized before it is being measured), the measurement 9. P. Helander, Meas. Sci. Technol. 1993, 4, 178–185.
can be carried out by heating which may result in a loss of 10. M. Defernez, H. Tapp, E. K. Kemsley, R. H. Wilson, Am.
water. The comparison to liquid honey is therefore diffi- Lab. 2002, 34, 34–38.
cult to make. Standard addition method must be used 11. P. Poulet, J. Chambron, R. Unterreiner, J. Appl. Phys. 1980,
whenever the sample’s matrix influences the analytical 51, 1738–1742.

Povzetek
Glavni cilj opisanih raziskav je bil prou~iti mo`nosti za uporabo tehnike optotermi~nega okna (OW) pri razvoju nove
enostavne in hitre metode za dolo~evanje koncentracije vode v medu. Za umeritev instrumenta OW, ki je bil opremljen
z diodnim laserjem RTL-1480-40G, smo uporabili metodo standardnega dodatka. Koncentracijo vode v akacijevem me-
du smo dolo~evali z meritvami odziva OW pri valovni dol`ini 1478 nm. Metodo OW smo primerjali z `e uveljavljenimi
metodami za dolo~evanje vode, kot sta gravimetrija in refraktometrija, dobljeni rezultati pa so pokazali dobro ujemanje.

Szopos et al.: Water Content of Acacia Honey Determined by Two Established Methods ...

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