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Major and Trace Elements in Different Types of Moroccan Honeys

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Forty-eight honey samples from different regions in Morocco were collected from beekeepers between 2005 and 2008. The levels of trace elements Mn, Cu, Ba, Ni, Cr, Co, Se, As, Ag and Be; major elements K, Na, Ca, Mg, Al, Fe and Zn; and toxic elements Cd and Pb were determined. Mg, K, Ca and Na were determined by atomic absorption spectrometry and the other mineral elements by inductively coupled plasma-mass spectrometry (ICP-MS) following acid digestion. Potassium was the most abundant element (71.22% of the total minerals), followed by sodium and calcium (15.64% and 7.24%, respectively). Ten honey types, Euphorbia echinus, Euphorbia resinifera, Ziziphus lotus, Citrus, Eucalyptus, rosemary, thyme, carob, lavender and honeydew were studied, and a statistical analysis was carried out using analysis of variance (ANOVA), Kruskal-Wallis test, principal component analysis (PCA) and discriminant analysis (DA) to classify them. PCA showed that the cumulative variance was 76.57%, and the DA analysis indicated that 73.3% of samples were correctly classified. Carob, rosemary and lavender honey were 100% classified. The mineral content of Euphorbia echinus, Ziziphus lotus, rosemary, carob and lavender Moroccan honey types has been determined for the first time.
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Australian Journal of Basic and Applied Sciences, 5(4): 223-231, 2011
ISSN 1991-8178
Major and Trace Elements in Different Types of Moroccan Honeys
1,3
Amina Chakir,
1
Abderrahmane Romane,
2
Nicoletta Barbagianni,
2
Donatella Bartoli,
3
Paola
Ferrazzi
1
Applied organic chemistry Laboratory, Faculty of Sciences Semlalia, Cadi Ayyad University,
Marrakech, Morocco
2
Regional Agency for the Environmental Protection (ARPA) UMBRIA, Perugia, Italy
3
DIVAPRA Entomology and Zoology applied to the Environment "Carlo Vidano, Faculty of
Agriculture, University of Turin, Italy
Abstract: Forty-eight honey samples from different regions in Morocco were collected from
beekeepers between 2005 and 2008. The levels of trace elements Mn, Cu, Ba, Ni, Cr, Co, Se, As,
Ag and Be; major elements K, Na, Ca, Mg, Al, Fe and Zn; and toxic elements Cd and Pb were
determined. Mg, K, Ca and Na were determined by atomic absorption spectrometry and the other
mineral elements by inductively coupled plasma-mass spectrometry (ICP-MS) following acid digestion.
Potassium was the most abundant element (71.22% of the total minerals), followed by sodium and
calcium (15.64% and 7.24%, respectively). Ten honey types, Euphorbia echinus, Euphorbia resinifera,
Ziziphus lotus, Citrus, Eucalyptus, rosemary, thyme, carob, lavender and honeydew were studied, and
a statistical analysis was carried out using analysis of variance (ANOVA), Kruskal-Wallis test,
principal component analysis (PCA) and discriminant analysis (DA) to classify them. PCA showed
that the cumulative variance was 76.57%, and the DA analysis indicated that 73.3% of samples were
correctly classified. Carob, rosemary and lavender honey were 100% classified.
The mineral content of Euphorbia echinus, Ziziphus lotus, rosemary, carob and lavender Moroccan
honey types has been determined for the first time.
Key words: ICP-MS; AAS; Morocco; Honey; Minerals; PCA; DA
INTRODUCTION
Honey is recognized as a biological indicator of environmental quality (Przybylowski & Wilczynska, 2001;
Rodríguez García et al., 2001) and floral biodiversity. It is intrinsically connected to the territory in which it
is produced and it is closely tied to the flora visited from the bees for its production. Pollen grains from the
flowers visited by bees collecting nectar occur naturally in honey, as well as trace elements that the plants
receive from the ground, water and air.
The average ash of honey is 0.17, with a range 0.02-1.03% (White, 1975). According to the EU honey
regulation (2002), the water-insoluble content in general is not more than 0.1 g/100 g. The content is higher
for honeydew and chestnut honeys (Persano Oddo et al., 1995).
Potassium is the most abundant element in honeys. Sodium, iron, copper, manganese, silicon, calcium, and
magnesium are all present in honey (White, 1975; Belouali et al., 2008; Pisani et al., 2008; Downey et al.,
2005; Rashed & Soltan, 2004; Sulbaran de Ferrer et al., 2004, Terrab et al., 2003; Nanda et al., 2003). There
is great variability in the mineral content of honeys, due to botanical origin rather than geographical and
environmental exposition of nectar sources (Bogdanov et al., 2007). To verify the relationship between the
botanical and geographic origin and mineral content in honey, many authors have used the principal component
analysis (PCA) (Seif Eldin & Elfadil 2010; Pisani et al., 2008; Fernández-Torres et al., 2005; Terrab et al.,
2003).
In Morocco the honey is widely used in traditional medicine, therefore it is necessary to preserve it from
adulterations and contaminations. Moroccan honeys coming from various floral origins were examined by
means of melissopalynological and some physicochemical analyses (Díez et al. 2004, Terrab et al. 2003a,
2003b, 2003c); mineral contents of some honeys from Northwest and East Morocco have been studied (Terrab
et al., 2003; Belouali et al., 2008).
The goal of this study was to determine major, trace and toxic elements in honey samples produced in
Corresponding Author: Abderrahmane Romane, Applied organic chemistry Laboratory, Faculty of Sciences Semlalia, Cadi
Ayyad University, Marrakech, Morocco
Tel.: +212524434649. fax: +212524437408.
E-mail: a.romane@gmail.com
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Aust. J. Basic & Appl. Sci., 5(4): 223-231, 2011
different regions of Morocco, considering also new kinds of melliferous productions never investigated before,
as Euphorbia echinus, Ziziphus lotus, rosemary, carob and lavender. The PCA and DA were applied to evaluate
the possibility of differentiating Moroccan honeys from different botanical origin according to mineral content
and to choose the elements with a higher discriminant power.
MATERIALS AND METHODS
Honey Samples:
The present study analyzed forty-eight honey samples collected from beekeepers in different regions of
South, Center-South and East Morocco between 2005 and 2008. These samples included nine types of unifloral
honey, 2 from Euphorbia echinus, 10 from Euphorbia resinifera, 3 from Ziziphus lotus, 11 from Citrus, 6 from
Eucalyptus, 2 from rosemary, 3 from thyme, 3 from carob and 2 from lavender, honeydew and multifloral
honeys. The honey samples were stored at 4 °C until analysis.
Sample Preparation:
Mineral Content:
One gram of the sample was dissolved in 10 mL of analytical-reagent grade concentrated nitric acid
(HNO
3
, 65%). Samples were evaporated at 100-120° C to almost complete dryness. Then, 10 mL of nitric acid
was added, and the volume was brought to 25 mL with Milli-Q water.
Statistical Analysis:
Statistical Package for Social Science (SPSS 17.0) was used to establish the difference between the ten
honey types by mean of their mineral content. The results are expressed as mean values, minimum (Min),
maximum (Max) and standard deviation (SD). In order to check if the correlation matrix can be presumed to
correspond, Bartlett test of sphericity and the KMO test (Kaiser-Meyer-Olkin) were performed. We proceeded
to carry out a study of the bivariate correlations among all the variables, detecting which of them were
significant. Using Kruskal-Wallis test only elements which differences were statistically significant were used.
With the aim of evaluating which of these main identified factors will explain most of the variability, the data
matrix was submitted to the principal component analysis (PCA), using the covariance matrix. A discriminant
analysis (DA) technique was performed in attempt to classify the honey samples.
Apparatus:
ICP-MS:
The analytical method is based on UNI EN ISO 17294:2005. An Agilent 7500c ICP-MS system was used.
The solution was introduced into a radiofrequency plasma equipped with a pneumatic nebulizer, atomised and
ionised. The instrumental conditions are presented in Table 1.
Table 1: Instrumental characteristics and settings for ICP-MS.
Parameters and instrumental characteristics
Spectrometer Quadrupole
Nebulizer Babington
Interface Sampling Cone, Skimmer Cone
RF generator (MHz) 27.12
Argon flows (mL/min) 15.0
Nebulizer pump (rps) 0.10
Scanning condition 2-260 amu
Internal standards Li , Sc, Ge, In, Tb, Bi
He gas flow rate (mL/min) 4.2
Integration time from 0.30 to 1.5 seconds
RF power (W) 1500
Sampling depth (mm) 8.5
Carrier gas flow rate (Ar) (L/min) 1.1
Auxiliary gas flow rate (Ar) (L/min) 0.9
Acquisition mode Nogas and He
Number of replicates 3
Quadruple bias (V) - 4.0
Flame atomic absorption spectrometry (AAS)
The AAS determinations were conducted using an AAnalyst 100 (Perkin Elmer) atomic absorption
spectrometer equipped with a flame to atomize the sample; the operating parameters are presented in Table
2. The main advantages of atomic absorption spectrometry are relatively inexpensive costs, ease of using the
method and reasonably good analytical performance. Flame atomic absorption spectrometry is used to determine
the concentration of alkaline and earth alkaline elements.
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Aust. J. Basic & Appl. Sci., 5(4): 223-231, 2011
Table 2: Operating parameters for AAS.
Ion Wavelength (nm) Lamp intensity (mA) Split (nm)
Na 589.0 12 0.2
K 766.5 12 0.7
Ca 422.7 15 0.7
Mg 285.2 15 0.7
Reagents and Solutions:
All solutions were prepared using high-purity deionized water obtained from a Milli-Q water (resistivity
18 MO cm
-1
) purification system (Millipore); Standard solutions were prepared from 1 g L
!1
stock solutions.
RESULTS AND DISCUSSION
Mineral Content:
Nineteen minerals were quantified for each honey (K, Na, Ca, Mg, Al, Fe, Zn, Mn, Cu, Ba, Ni, Pb, Cr,
Co, Se, Cd, As, Ag and Be). Table 3 and Table 3 (continued) show the mean, maximum, minimum and
standard deviation of the mineral content in honey samples.
Table 3: Major elements (mg kg
!1
) in different types of honey from Morocco
Honey type K Na Ca Mg Al Fe Zn
Citrus Mean 458.20 78.59 38.40 8.59 10.23 2.20 3.63
Min 180 47 28 6.50 7.53 1.30 0.42
Max 850 160 56 12 14.14 2.95 10.78
SD 239.93 34.31 8.85 2.40 1.84 0.47 2.99
Eucalyptus Mean 695.83 308 103.33 29.42 13.32 3.82 4.18
Min 450 181.50 50 20.50 6.91 1.97 0.66
Max 950 488.50 196 40.50 20.30 5.37 9.27
SD 232.60 113.36 67.70 7.45 4.72 1.42 3.67
Carob Mean 749.17 223.67 135.33 67.83 21.45 4.86 3.05
Min 500 170 106 56.50 9.84 4.36 2.09
Max 997.50 312.50 170 75 41.83 5.63 4.92
SD 248.75 77.49 32.33 9.93 17.71 0.68 1.62
Thyme Mean 554.17 153.17 68.33 22.50 17.60 7.84 3.91
Min 325 73 65 10 12.08 4.43 2.76
Max 700 205 70 38.50 27.70 13.95 4.81
SD 200.91 70.41 2.89 14.57 8.76 5.30 1.05
E. resinifera Mean 641 127.40 71.80 32.60 17.95 6.55 2.41
Min 190 5 30 15 3.11 3.37 0.47
Max 1900 176 180 48.50 31.45 9.76 7.07
SD 474.59 46.57 48.86 12.49 7.09 2.18 1.87
E. echinus Mean 575 92 51 24 15.67 5.92 4.02
Min 450 82.50 38 18.50 12.34 5.46 1.20
Max 700 101.50 64 29.50 19 6.37 6.85
SD 176.78 13.44 18.38 7.78 4.71 0.65 4
Lavender Mean 605 243.25 65 32 13.64 3.27 3.17
Min 425 240 48 20 11.13 3.21 3.15
Max 785 246.50 82 44 16.15 3.33 3.18
SD 254.56 4.60 24.04 16.97 3.55 0.09 0.02
Ziziphus Mean 1268.33 146.17 63.33 30.17 22.80 9.34 2.48
Min 450 112 42 19.50 16.51 2.64 1.08
Max 2305 196.50 76 43 30 13.19 3.72
SD 946.58 44.51 18.58 11.90 6.79 5.83 1.33
Rosemary Mean 375 45 24 10 8.66 1.42 2.46
Min 350 40 20 4 6.38 1.14 0.82
Max 400 50 28 16 10.93 1.71 4.10
SD 35.36 7.07 5.66 8.49 3.22 0.41 2.32
Honeydew Mean 1298 122.67 74.33 45.17 22.81 7.71 2.49
Min 740 101 32 19.50 12.52 5.67 2.09
Max 2250 142.50 135 69 41.08 11.33 3.05
SD 828.52 20.81 53.89 24.80 15.86 3.14 0.50
Multifloral Mean 317.33 63 39.33 15.33 11.27 4 2.28
Min 300 6.50 26 15 2.40 3.62 1.37
Max 335 102 54 16 16.91 4.55 3.32
SD 17.50 50.10 14.05 0.58 7.77 0.49 0.98
Total Mean 652.01 143.19 66.30 26.50 15.33 4.90 3.15
Min 180 5 20 4 2.40 1.14 0.42
Max 2305 488.50 196 75 41.83 13.95 10.78
SD 454.78 94.96 44.48 18.16 8.15 3.12 2.29
SD: Standard Deviation, Min: Minimum, Max: Maximum, E. resinifera: Euphorbia resinifera,
E. echinus: Euphorbia echinus
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Aust. J. Basic & Appl. Sci., 5(4): 223-231, 2011
Table 3: (continued) Minor elements (mg kg
!1
) in different types of honey from Morocco
Honey type Mn Cu Ba Ni Pb Cr Co As Se Ag Cd Be
Citrus Mean 0.190 0.890 0.242 0.358 0.107 0.077 0.133 0.005 0.030 0 0.003 0.004
Min0.1060.18500.0110.0460.031000000
Max 0.491 1.863 0.608 1.239 0.164 0.262 1.435 0.033 0.234 0 0.018 0.036
SD 0.112 0.592 0.146 0.341 0.039 0.066 0.432 0.011 0.069 0 0.006 0.011
Eucalyptus Mean 4.168 0.370 0.410 0.118 0.086 0.048 0.003 0.008 0.036 0 0.003 0
Min0.9030.0500.1400.0580.0250000000
Max 9.375 0.619 0.853 0.271 0.142 0.098 0.014 0.045 0.081 0 0.016 0
SD 3.687 0.196 0.255 0.079 0.044 0.041 0.006 0.018 0.040 0 0.006 0
Carob Mean 2.410 1.677 0.508 0.536 0.204 0.063 0.061 0.019 0.027 0 0.001 0
Min1.9990.2940.2830.2950.0540.048000000
Max 2.875 3.108 0.945 0.764 0.451 0.086 0.176 0.032 0.081 0 0.002 0
SD 0.441 1.407 0.378 0.235 0.215 0.020 0.100 0.017 0.047 0 0.001 0
Thyme Mean 3.043 0.599 0.417 0.155 0.115 0.080 0.048 0 0.021 0 0.003 0
Min0.8640.4560.2840.0270.0950.059000000
Max 6.690 0.775 0.524 0.240 0.133 0.091 0.094 0 0.035 0 0.008 0
SD 3.178 0.162 0.123 0.113 0.019 0.018 0.047 0 0.019 0 0.005 0
E. resinifera Mean 1.156 0.584 0.279 0.321 0.127 0.051 0.057 0.007 0.030 0.007 0.006 0
Min 0.572 0.162 0 0.058 0.042 0 0.032 0 0 0 0 0
Max 1.998 1.080 0.400 1.158 0.196 0.083 0.106 0.041 0.095 0.073 0.031 0
SD 0.397 0.317 0.107 0.377 0.046 0.025 0.025 0.015 0.034 0.023 0.010 0
E. echinus Mean 1.025 1.232 0.255 0.092 0.122 0.047 0.053 0.017 0.022 0.020 0 0
Min 0.825 1.038 0.248 0.028 0.101 0.044 0.035 0 0 0 0 0
Max 1.226 1.426 0.263 0.156 0.144 0.050 0.072 0.034 0.045 0.040 0 0
SD 0.284 0.274 0.010 0.091 0.031 0.005 0.026 0.024 0.032 0.028 0 0
Lavender Mean 4.615 0.706 0.542 0.377 0.097 0.049 0 0.020 0.039 0 0 0
Min4.5750.5530.5320.1380.0900.047000000
Max 4.655 0.860 0.553 0.615 0.104 0.051 0 0.039 0.078 0 0 0
SD 0.057 0.217 0.015 0.337 0.010 0.003 0 0.028 0.055 0 0 0
Ziziphus Mean 0.772 1.667 0.392 0.233 0.146 0.072 0.037 0.010 0.018 0.023 0.013 0
Min0.4561.0030.2860.1450.1220.049000000
Max 1.023 2.638 0.469 0.282 0.192 0.104 0.085 0.030 0.054 0.034 0.026 0
SD 0.289 0.860 0.095 0.077 0.040 0.028 0.043 0.018 0.031 0.020 0.013 0
Honeydew Mean 0.733 1.387 0.313 0.293 0.133 0.068 0.089 0 0 0 0.097 0
Min 0.669 0.859 0.263 0.230 0.102 0.036 0.017 0 0 0 0.006 0
Max 0.835 1.848 0.374 0.411 0.194 0.097 0.211 0 0 0 0.276 0
SD 0.089 0.498 0.056 0.103 0.053 0.030 0.106 0 0 0 0.155 0
Rosemary Mean 0.128 0.464 0.193 0.120 0.087 0.027 0 0 0.030 0 0 0
Min0.1060.2870.1570.0900.0860000.027000
Max 0.149 0.641 0.230 0.149 0.088 0.054 0 0 0.034 0 0 0
SD 0.030 0.250 0.052 0.042 0.001 0.038 0 0 0.005 0 0 0
Multifloral Mean 0.423 0.593 0.220 0.255 0.101 0.061 0.005 0 0.030 0 0.001 0
Min0.3030.2330.1270.0780.0470.057000000
Max 0.609 0.878 0.284 0.420 0.129 0.068 0.014 0 0.064 0 0.004 0
SD 0.164 0.329 0.083 0.171 0.046 0.006 0.008 0 0.032 0 0.002 0
Total Mean 1.507 0.842 0.322 0.280 0.118 0.061 0.060 0.007 0.028 0.004 0.010 0.001
Min0.1060.05000.0110.0250000000
Max 9.375 3.108 0.945 1.239 0.451 0.262 1.435 0.045 0.234 0.073 0.276 0.036
SD 2.028 0.636 0.176 0.271 0.063 0.039 0.208 0.014 0.042 0.013 0.040 0.005
SD: Standard Deviation, Min: Minimum, Max: Maximum, E. resinifera: Euphorbia resinifera, E. echinus: Euphorbia echinus
The first group was formed by the major elements. The most abundant was potassium (71.22% of the total
minerals), which agrees with other studies indicating that potassium is the most common element in honeys
(Belouali et al., 2008; Pisani et al., 2008; Downey et al., 2005; Rashed & Soltan, 2004, Sulbaran de Ferrer
et al., 2004; Terrab et al., 2003; Nanda et al., 2009). Sodium and calcium were the next most common
elements (15.64% and 7.03%), followed by magnesium, aluminium, iron and zinc (2.89% and 1.67%
respectively).
The second group was formed by the minor elements present in all samples: Mn, Cu, Ba, Ni, Pb and Cr,
with average content of 1.5, 0.84, 0.32, 0.28, 0.12 and 0.06 mg/kg, respectively.
The third group was formed by other, low-concentration elements such as Be, Ag, As, Se, Cd and Co,
their average content ranged between 0.0009 and 0.059 mg/kg. Values of Se found by Tuzen et al. (2007) in
Turkish honey (range: 0.038-0.113 mg/kg) were within those found in the present study, while values of Cd
were lower (0.0009-0.0179 mg/kg).
There are no specific MRL (Maximum Residue Levels) values for honeys, but values of 0.1 mg/kg for
Cd and 1 mg/kg for Pb have been suggested by the European Union (Byrne, 2000; Bogdanov et al., 2007).
The average concentration of the toxic elements Pb and Cd (0.12, 0.01 mg/kg respectively) were below the
Maximum Residue Levels (MRL).
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Aust. J. Basic & Appl. Sci., 5(4): 223-231, 2011
Table 4: Major and trace mineral content (mg kg
!1
) in honey samples from some Mediterranean countries
KMg NaCaFe MnCu
Present study 652 26.5 143.1 66.3 4.89 1.5 0.84
Northwest Morocco
a,b
13-2388 3.79-230 - - 1.33-34 - -
East Morocco
c
511.2 26.83 - 102.9 13.52 1.41 1.32
Spain
a,d
639-1845 13.26-74.38 11.69-218.5 111-257 - 0.133-7.825 -
Italy
e
- - - - 1,65 1,62 0,58
Italy
f
1195 56.7 96.6 257 3.07 1.54 0.906
Turkey
g
296 33 118 51 6.6 1 1.8
Turkey
h
- 10.45 - - 0.36 - 0.01
Egypt
a,i
213-1500 102-300 378-478 - 58-202 0.5-1.70 1-1.75
Portugal
j
1150 35.57 261.4 53.88
Saudi Arabia
a,k
- 18.3-23.2 - - 0.31-3.19 0.18-0.37 0.2-0.38
a
Range,
b
Terrab et al. (2003),
c
Belouali et al. (2008),
d
Fernández-Torres et al. (2005),
e
Porrini et al. (2002),
f
Pisani et al. (2008),
g
Yilmaz
et al. (1999),
h
Erbilir et al. (2005),
i
Rashed & Soltan (2004),
j
Silva et al (2009),
k
Osman et al. (2007).
Table 4: (continued) Toxic elements (mg kg
!1
) in honey samples from some Mediterranean countries
Pb Ni Cd Co Zn
Present study 0.118 0.28 0.01 0.06 3.14
Northwest Morocco
a,b
---- -
East Morocco
c
0.34 - 0.005 0.31
Spain
a,d
- - - - 1.33-7.82
Italy
e
0.013 0.1 - - 1.44
Italy
f
0.076 0.308 0.0039 0.011 1.8
Turkey
g
4.2-6.3 1.25-4.1 0.01-0.5 1.75-2.52 5-9.3
Turkey
h
---1.02.7
Egypt
a,i
---- -
Portugal
j
---- -
Saudi Arabia
a,k
0.038-0.08 - 0.002-0.037 - 0.2-0.74
a
Range,
b
Terrab et al. (2003),
c
Belouali et al. (2008),
d
Fernández-Torres et al. (2005),
e
Porrini et al. (2002),
f
Pisani et al. (2008),
g
Yilmaz
et al. (1999),
h
Erbilir et al. (2005),
i
Rashed & Soltan (2004),
j
Silva et al (2009),
k
Osman et al. (2007).
Belouali et al. (2008) reported that Zn and Cd concentrations in East Morocco honeys were lower
(averages: 0.31 and 0.005 mg/kg respectively) than those found in the present study. On the other hand, Pd
was present at higher concentrations (0.34 mg/kg) than were found in this study.
In this research, carob honey contained higher levels of Ca, Mg, Na, Ni, Cu and Pb than the other
samples.
The average concentrations of Mg, Mn, Fe and Cu in honeydew honey were within those found by Üren
et al. (1998) in the same type of Turkish honey, and lower than the levels found by Terrab et al. (2003).
Honeydew honey contained the highest level of Al (22.81 mg/kg), as reported by Madejczyk &
Baralkiewicz (2008) in Polish honeydew honey (0.3-35.1 mg/kg); while Terrab et al. (2003) found in honeydew
honey the highest concentration of iron. Al with a mean value of 14.3 mg/kg was found in Czech honeydew
honey (Lachman et al., 2007). While high values of Al were found also in Z. Lotus and carob honeys. This
element is not detected in all honeys; Al was found in 41% of analysed French honey samples (Devillers et
al., 2002) with values ranging between 0.18 and 9.72 mg/kg and lower than those of the present study.
The higher content of aluminum in Moroccan honeys may be due to beekeeping activities and materials
used, e.g. storage containers, as presumed for some Chilean honeys (Fredes & Montenegro, 2006).
The highest concentration of Cr was found in thyme honey. The amount of iron was high, and agreed with
the concentrations found in Turkish thyme honey (Juszczak et al., 2009). This type of honey has similar levels
of Ca, Mg, Na, K and Zn to those found by González-Miret et al. (2005) in Spanish honeys (69.18, 27.43,
175.93, 484.83 and 4.2 mg/kg respectively). However values of Ca, K, Mg and Na in the present study were
lower than those found by Terrab et al. (2004) in Spanish honeys (185, 716, 78 and 388 mg/kg respectively).
Lavender honey is rich in Mn and Ba and González-Miret et al. (2005) found similar amounts of Fe to
the value found in the present study. On the other hand, the concentrations of Ca, Mg, Na, K, Al, Mn, Cu
and Zn found by the last authors were lower than those measured in the present study.
The highest levels of Fe and Cu were found in Ziziphus lotus honey; while Indian Ziziphus mauritiana
honey (Nanda et al., 2009) showed slightly similar values of Fe (6.89 mg/kg) and Cu (1.93 mg/kg). However
Ziziphus Honeydew and Z. lotus honeys contained the highest amount of potassium, with average
concentrations of 1300 and 1268 mg/kg respectively. These results agree with Pisani et al. (2008) and Terrab
et al. (2003), who found the highest concentration of potassium in honeydew honey (3440 and 1882 mg/kg
respectively).
The levels of Ca, K and Ni were higher in E. resinifera than in E. echinus honeys.
Eucalyptus honey contained higher levels of Zn than the other honeys. Ca, Mg, Mn and Zn concentrations
were similar to those found by González-Miret et al. (2005), but K and Cu levels were lower than those found
by the last author and by Terrab et al. (2003).
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Aust. J. Basic & Appl. Sci., 5(4): 223-231, 2011
Rosemary and Citrus honeys contained the lowest elements concentrations. In fact, these types of honey
have a light colour (26 and 39.5 mm Pfund, respectively). This result agrees with Ankalm (1998). In rosemary
Spanish honey González-Miret et al. (2005) found similar amounts of Mg, Cu and Zn (14.32, 0.42 and 2.4
mg/kg respectively).
The concentrations of K, Mn and Zn in Citrus honey were similar to the amounts found in the same type
of Spanish honey (Fernàndez-Torres et al., 2005). On the other hand, the concentrations of Ca ranged between
42.59 and 89.6 mg/kg. Mg concentrations were between 13.26 and 42.34 mg/kg, and were higher than those
in the present study. Terrab et al. (2003) found lower levels of K (285 mg/kg), Cu (0.58 mg/kg) and Zn (1.91
mg/kg). The amounts of Mg, Mn and Fe were lower than those found by the last authors (Terrab et al., 2003)
as were Mg (21.01 mg/kg), Mn (0.45 mg/kg) and Fe (9.82 mg/kg) and than those found by Rashed & Soltan
(2004) in Egyptian Citrus honey, as were Mg (225 mg/kg), Mn (0.5 mg/kg) and Fe (80 mg/kg). The
concentration of K was similar to that reported by the same authors (Terrab et al., 2003; Rashed & Soltan,
2004), and higher than that found by Nanda et al. (2009) in Indian Citrus honey.
Statistical Analysis:
In order to check the accuracy of the complete correlation matrix, the Kaiser-Meyer-Olkin measure of
sampling accuracy was examined (KMO 0.613). In an attempt to establish the relationship between mineral
content and honey type, statistical methods such as CA, PCA and DA were applied. From principal component
analysis (PCA), it can be concluded that 77.73% of the variation existing in the data can be explained by four
factors.
Using Kruskal-Wallis test elements (Ca, Mg, Na, Al, Mn, Fe, Co, Cu, Ag and Ba) witch the difference
was statistically significant were used in the PCA and DA procedures. The Table 5 summarizes the percentage
of the variance explained by each factor.
Table 5: Component matrix
Components
--------------------------------------------------------------------------------------------------------------------------------
12 3 4
Ca 0.82 -0.16 -0.07 -0.02
Mn 0.76 -0.5 0.01 0.13
Na 0.76 -0.54 0.02 0.12
Ba 0.72 0.05 0.47 0.05
Mg 0.63 0.08 -0.35 -0.25
Cu 0.18 0.74 0.03 -0.1
Al 0.54 0.74 -0.06 0
Fe 0.48 0.64 -0.18 0.02
Co 0.04 0.16 0.89 -0.12
Ag -0.05 0.24 -0.01 0.94
The variables that load highly to the first factor are based on Ca, Mn, Na, Ba and Mg. The variables that
correlate highly with the second factor are Cu, Al and Fe. The third and fourth factors are associated with Co
and Ag respectively.
From Table 6, it can be concluded that the variables selected by discriminant analysis were Mg, Na, Mn,
Fe and Cu. This result is corroborated by the significance of the Wilks test (p<0.001). The ten samples were
73.3 % correctly classified.
Table 6: Discriminant analysis (DA) of mineral content
Parameters Wilks' lambda F statistic P significance level
Ca 0.61 2.52 0.02
Mg 0.28 9.78 0.00
Na 0.31 8.75 0.00
Al 0.68 1.8 0.10
Mn 0.48 4.26 0.00
Fe 0.44 4.94 0.00
Co 0.95 0.19 0.99
Cu 0.58 2.83 0.01
Ag 0.75 1.31 0.27
Ba 0.7 1.66 0.14
Conclusion:
This study presents the concentrations of major, trace and toxic elements in nine types of unifloral honeys
(i.e. Euphorbia echinus, Euphorbia resinifera, Ziziphus lotus, Citrus, Eucalyptus, rosemary, thyme, carob and
lavender), honeydew honey and multifloral honeys from South, Center-South and East Morocco.
228
Aust. J. Basic & Appl. Sci., 5(4): 223-231, 2011
The present study investigated for the first time the mineral content of Moroccan honeys from five
botanical origins: Euphorbia echinus, Ziziphus lotus, rosemary, carob and lavender honey, and these results are
reported.
Potassium, sodium, calcium, and magnesium accounted for 96.81% of the total minerals present in honeys
produced in Morocco. Potassium was the most abundant element. Honeydew honey was characterised by
highest potassium concentrations.
Fe, Zn, Mn, Cu, Ba, Ni, Pb and Cr were present at low levels, with average concentrations between 4.9
and 0.06 mg/kg. Be, Ag, As, Se, Cd and Co were present at very low levels, with average concentrations
ranging from 0.001 to 0.06 mg/kg.
Toxic elements such as Pb and Cd were not present at levels above those allowed by the Codex
Alimentarius; therefore, it can be concluded that the honeys analysed present a good level for quality and the
area in which the honeys were produced is free of these contaminants, which concords with results found by
Seif Eldin & Elfadil (2009) and Nasiruddin Khan et al. (2006).
From principal component analysis (PCA), it can be concluded that 77.73% of the variation existing in
the data can be explained by four factors. The variables selected by discriminant analysis were Mg, Na, K,
Mn and Fe; and the ten sample types (including the honeydew honey) were 73.3% correctly classified. This
concurs with the results obtained by Terrab et al. (2004) in Spanish thyme honey and in Canadian honeys
(Féller-Demalsy et al., 1989), showing that the analysis of mineral content is insufficient to determine the floral
origin.
Melissopalynological analyses, together with both physicochemical and sensorial analyses, are usually
carried out to determine honey botanical and geographical origin and to get their characterization (Louveaux
et al. 1978; Ferrazzi et al. 1997).
ACKNOWLEDGMENTS
The authors would like to thank FELCOS UMBRIA (Umbrian Fund of Local Administrations for
Decentralized Cooperation and Sustainable Human Development), and especially director Massimo Porzi and
Dr. Alberto Micheli director of the Provincial Department of Perugia (ARPA UBRIA) for their assistance with
the present work.
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