Fresenius J Anal Chem (1997) 357 : 553557

Springer-Verlag 1997

O R I G I N A L PA P E R

G. Thiel K. Danzer

Direct analysis of mineral components in wine

by inductively coupled plasma optical emission spectrometry (ICP-OES)

Received: 30 May 1996 / Revised: 2 July 1996 / Accepted: 5 July 1996

Abstract A direct measuring method for the determination of 15 inorganic components in wine by ICP-OES was
developed. It was applied to 17 white wines from 6 German wine-growing regions. In these investigations 15 elements (B, V, Mn, Zn, Fe, Al, Cu, Sr, Ba, Rb, Na, P, Ca,
Mg and K) were involved. By using alcoholic calibration
solutions the results of the direct measuring method are
comparable with those of the control methods. Typical
patterns of elements obtained by the multicomponent
analyses can be evaluated by multivariate data analysis to
recognize the origin of the wines.

rect analysis. Accurate and precise analytical results are

required to make it possible to classify the wine according
to wine-growing region by means of their typical element
pattern [37].

2 Experimental
2.1 Samples
The investigation included 17 white wines from 6 German winegrowing regions. All information regarding the analysed samples
is summarized in Table 1.

1 Introduction

2.2 Apparatus

Several analytical methods can be used to determine the

mineral components in wine. In most methods extensive
sample preparation is involved. Therefore, these methods
are time-consuming and produce relatively imprecise results.
The ICP-OES is a multi-element method with very
good detection power and offers the right conditions for
reliably and rapidly determining the analytes. Due to the
high temperature of the plasma less matrix interference is
observed. Therefore the relatively complex organic matrix
of the wine should have no real influence on the measurements and the analysis of the samples should be possible
without pretreatment [1, 2].
The aim of this study was to develop an analytical
method for wine samples and to guarantee the trueness of
the measured values of the untreated samples. The results
of standard addition and measurement of decomposed
wine samples were compared with results taken from di-

The ICP-spectrometers Maxim I (Fisons Instruments) and Plasmaquant 110 (Carl Zeiss Jena GmbH) were used.
The Maxim I is equipped with an axially-viewed plasma
source. The instruments optical system comprises an argon-rinsed
echelle grating/prism spectrometer in double 0.5 m Czerny-Turner
mounting. The available wavelength range is from 174 nm to 800
nm. There are 67 lines of 51 elements. The dispersed radiation is
focused onto a mask with 67 exit slits, which are connected with a
light-conducting fibre. The Maxim I has 11 thermally stabilized
photomultipliers. Eight of these are joined with the light-conducting fibres by means of a shutter mechanism. The signals they carry
are sequentially registered. Three lines in VUV range are linked
together directly with a photomultiplier.
Unlike the Maxim I the Plasmaquant 110 has a vertically
aligned torch. It too has an echelle spectrometer, whose wavelength-range is from 193 nm to 852 nm. There are 138 lines of 74
elements. Each of the 12 photomultipliers can observe 5 of the 138
lines through lightconducting fibres linked to the focal plane. The
principle employed here allows the analyst to combine spectral
lines as required, and the problem of analysis is optimally addressed. The parameters of the analytical program and the wavelengths used can be found in Tables 2 and 3.
2.3 Sample preparation

Dedicated to Professor Dr. Rolf Borsdorf on the occasion

of his 65th birthday
G. Thiel K. Danzer (Y)
Friedrich-Schiller-Universitt Jena,
Institut fr Anorganische und Analytische Chemie,
Lessingstrasse 8, D-07 743 Jena, Germany

In order to be able to use aqueous calibration standards the organic

components of the wine, in particular the alcohol, must be removed from the samples. The wine samples were decomposed according to the following instructions: 50 mL volume of sample
with 30 mL of perhydrol are evaporated in a Kjeldahl flask for oxidation of the organic components. 1 mL of conc. sulphuric acid is

554
Table 1 Wine samples

Producer/region

Grape variety

Vintage

Abbreviation
used

Winzervereinigung Freyburg/Unstrut e. G.

Silvaner
Riesling
Mller-Thurgau
Weiburgunder
Riesling
Silvaner
Gewrztraminer
Silvaner
Riesling
Riesling
Kerner
Gewrztraminer
Mller-Thurgau
Riesling

1993
1993
1993
1993
1993
1993
1993
1993
1993
1993
1993
1993
1994
1994

FS
FR
FM
GW
GR
GS
BG
BS
BR
DR
DK
DG
NM
NR

Silvaner
Mller-Thurgau
Riesling

1994
1994
1994

OS
OM
OR

Weingut Forschungsanstalt Geisenheim

Staatliches Weinbauinstitut Freiburg i. Br.

Versuchs- und Lehrgut Blankenhornsberg
Staatliches Weinbauinstitut Freiburg i. Br.
Versuchsrebgut Durbach
Chemisches Untersuchungsamt Mainz
Staatliche Lehr- und Versuchsanstalt Oppenheim
(Gemarkung Nierstein)
Chemisches Untersuchungsamt Mainz
Staatliche Lehr- und Versuchsanstalt Oppenheim
(Gemarkung Oppenheim)

Table 2 Operating conditions

a Only the trace elements of

decomposition solutions were
measured using 1 s integration
time
b Variable parameter depending on line-type

Parameter

Maxim I

Plasmaquant 110

Delay time

30 s transport time of sample

10 s pre-integration time for signal
stabilization
1
3
3s
13 L/min
1.2 L/min
0.48 L/min
1250 W
3 mL/min
Meinhard nebulizer

30 s transport time of sample

30 s stabilization time after power
regulation
3
3
3 sa
12 L/min
1 L/min
200 kPa
670 W bis 1210 Wb
1.6 mL/min
Cross-Flow nebulizer

Off-peak integration
On-peak integration
Integration time
Coolant gas flow
Auxiliary gas flow
Carrier gas flow
Power
Pump speed
Nebulizer

Table 3 Analytes and wavelengths

Analyte

Wavelength (nm)

Boron
Vanadium
Manganese
Zinc
Iron
Aluminium
Copper
Strontium
Barium
Rubidium
Sodium
Calcium
Magnesium
Phosphorus
Potassium

249.6
292.4, 309.3a, 310.2b
257.6
206.2, 213.8
259.9
308.2, 396.1
324.7
407.7a, 430.5b
233.5, 455.3a, 493.4b
780.0
589.0
317.9
279.0
214.9
766.4

a
b

Only on Maxim I
Only on Plasmaquant 110

added to the sample to ensure that the residue does not evaporate
to dryness. The remaining residue is mixed with bidistilled water
up to its starting volume. These solutions are analyzed with the
ICP-OES [8, 9].
Using the direct measuring method the samples are analyzed
without any pretreatment. However the calibration standard matrix
must be matched to the samples using ethanol, in order to compensate for intensity differences caused by viscosity influences of
the organic components during sample nebulization. This results in
standard solutions of analytes, which contain 12% or in the case of
mineral elements 1.2% ethanol. In both methods the calibration
range is from 0 to 10 mg/L, for the mineral elements to 50 mg/L
and for the more highly concentrated element potassium to 100
mg/L.
The standard addition method involves two standards. The addition of the first standard should double the concentration of the
analytes in the sample and the other should triple it. The required
concentration of the standard solutions is estimated with the help
of the results taken from the calibrated methods. The analytes are
added to the samples to be treated in alternating concentrations.
After adding the standard solution the original sample and the
treated samples have an equal final volume.
To determine the mineral elements, the sample solutions must
be diluted independent of the applied method, in order to work
within the linear calibration range. To determine the alkali metal

FS
FR
FM
GW
GR
GS
BG
BS
BR
DR
DK
DG
NM
NR
OS
OM
OR

2.02.8
2.83.4
2.93.2
3.64.0
2.73.1
2.32.5
6.06.8
2.63.1
3.24.4
3.44.3
3.44.1
3.54.7
4.34.5
3.94.5
3.94.5
3.84.5
4.95.8

Wine B

Mn

0.91.2
0.81.0
0.80.9
0.91.1
0.60.8
0.50.7
0.81.1
0.91.1
0.60.8
1.21.5
1.11.3
0.81.1
0.81.0
0.81.1
1.01.2
0.91.1
1.01.2

n.n.
n.n.
n.n.
0.03
n.n.
n.n.
0.060.07
0.060.14
0.040.11
0.06
0.03
0.050.07
n.n.
0.01
0.02
0.02
0.01

0.30.5
0.70.9
0.91.1
0.70.8
0.70.9
0.50.6
0.70.9
0.70.9
0.91.2
1.01.2
0.91.2
0.81.1
0.40.5
1.21.5
0.91.2
1.01.2
0.91.2

Zn

Cu
0.170.24
0.060.10
0.160.20
0.06
0.020.03
0.030.05
0.100.16
0.110.18
0.060.11
0.300.46
0.500.71
0.400.63
0.050.09
0.200.32
0.360.50
0.050.10
0.040.11

Al
1.11.8
1.01.5
0.60.9
1.42.2
1.21.7
1.32.1
1.52.5
1.42.1
0.81.2
1.52.4
1.01.5
1.93.0
1.11.7
1.82.5
1.92.6
2.53.4
1.31.9

Fe
1.41.9
2.33.0
2.32.5
1.51.9
1.21.5
1.21.7
0.91.3
1.11.4
0.50.6
0.50.6
0.50.7
0.40.6
1.01.5
2.53.1
2.12.4
3.54.2
1.72.2

Table 4 Analytical results (minimum and maximum value in mg/L)

0.961.28
0.550.74
0.570.68
0.380.48
0.340.45
0.190.30
0.210.33
0.170.31
0.280.44
0.240.38
0.120.19
0.150.26
0.200.34
0.460.59
0.440.56
0.480.61
0.320.43

Sr

Rb
1.41.6
1.1
1.2
1.6
1.1
1.1
1.5
1.52.6
1.82.9
1.8
1.0
1.3
1.2
1.4
1.4
1.0
1.2

Ba
0.060.09
0.040.07
0.030.05
0.110.18
0.080.11
0.070.11
0.100.23
0.080.18
0.080.14
0.150.26
0.100.18
0.120.31
0.070.11
0.070.10
0.080.11
0.090.15
0.050.09

1013
1015
6 9
1419
1012
1113
1113
1012
7 9
8 9
810
1114
8 9
1825
1114
1215
1013

Na

Ca
119137
75 93
75 98
92112
68 87
65 75
67 85
60 71
74 91
162200
58 81
61 74
93108
104128
102135
77 93
84105

P
29 36
62 80
59 77
75 93
59 75
58 70
119145
57 72
76 92
252286
155174
261290
96102
87112
71 88
93111
56 68

62 78
67 87
57 76
68 89
70 92
60 73
56 72
62 78
62 79
82104
64 81
68 82
63 76
83105
69 88
72 89
67 87

Mg
820 860
540 730
780 870
830 900
590 740
660 710
9101090
590 790
490 650
9401110
840 970
15901860
840 920
510 610
8601020
690 800
480 650

555

contents, lanthanum is used as an ionization buffer. This step was

necessary, because only arc lines can be used for determining these
elements. Their sensitivity at the high temperatures observed in
plasma is relatively low; the alkali elements are strongly inclined
to ionization. Therefore the ICP-OES is not the best method for determining these elements.
When the wine is decomposed, orthoboric acid is lost. In order
to examine the measured values using the direct method, another independent method must therefore be applied. A sensitive analytical
method already employed in the analysis of wine is the spectrophotometric determination of orthoboric acid by chelate extraction with
2-ethyl-1,3-hexanediol, and by using protonated curcumin [1012].
In an acidic environment the orthoboric acid with curcumin forms a
red substance, whose extinction is measured at 555 nm.

3 Results and discussion

3.1 Interpretation of the results

The ICP-OES was employed to determine 15 elements

(B, V, Mn, Zn, Fe, Al, Cu, Sr, Ba, Rb, Na, P, Ca, Mg
and K) in wine. The results for 17 wines are summarized in Table 4. Ten measurements were ascertained
for the different methods. The minimum and maximum
values have been given. In Figs. 1 to 3 the results for the
Boron

Samples

Fig. 1 Comparison of the results of the applied methods for boron;

spectrophotometric method,
directly measured on Plasmaquant 110,
directly measured on Maxim I,
standard addition method on Plasmaquant 110

Phosphorus

Samples

Fig. 2 Comparison of the results of the applied methods for phosphorus;

measured after decomposition on Plasmaquant 110,
measured after decomposition on Maxim I,
directly measured on Plasmaquant 110,
directly measured on Maxim I,
standard addition method on Plasmaquant 110

556
Potassium

Samples

Fig. 3 Comparison of the results of the applied methods for potassium;

measured after decomposition on Plasmaquant 110,
measured after decomposition on Maxim I,
directly measured on Plasmaquant 110,
directly measured on Maxim I,
standard addition method on Plasmaquant 110

elements boron, phosphorus and potassium are given

graphically as examples. They have been selected to
cover all magnitudes of the evaluated contents. Measuring the decomposed wines provides a wide variability
and altogether lower values caused by losses during oxidation and evaporation in the Kjeldahl flask, viscosity
influences by the sulphuric acid during nebulization and
contamination by the instruments and chemicals. These
effects have also been observed in other investigations
[13]. When using the direct method, apparent differences in intensity, caused by the influence of the organic components in the sample nebulization and measurement process, could be compensated by adding
ethanol, the main organic component of wine, to the
calibration standards.
In some cases, especially when measuring trace elements with contents below 10 mg/L, the standard addition
method provides noticeably higher values than the other
methods. However, previous investigations gave no clear

Table 5 Validation of the direct method by means of regression coefficients

B
V
Mn
Zn 206
Zn 213
Fe
Al 308
Al 396
Cu
Sr
Ba
Rb
Na
P
Ca
Mg
K

information about the reasons for this observation or

whether these results are reliable. The analysis results
were evaluated by investigating whether the methods used
achieved the same results within the scope of measurement accuracy. One way of displaying the relation between the results of the methods employed is linear regression. The mathematical equation corresponding to the
bias function y = b x + a can be compared with the ideal
function y = x. In this way systematic errors can be recognized by calculating the confidence interval of the regression coefficients a and b.
Table 5 shows the regression coefficients a and b as
well as their confidence intervals as results of the comparisons between direct measurement values and those of the
decomposed samples and between direct and standard addition measurement values. It can be seen from this table
that there are significant differences in the results of the
methods compared first for 11 analytical lines. Comparing
the direct measurement values with results of standard addition there are even significant differences for 14 analytical lines. Particularly great differences were observed, in
the first case for barium, and in the second for copper.
These elements appear in very low quantities in all wines
so that the resulting errors in measurement cause such discrepancies. Furthermore, the evaluation of measurements
of alkali elements gives unsatisfactory results. As already
stated, the ICP-OES is fairly unsuitable to determine these
analytes, because the high temperature of the plasma reduces the sensitivity of the arc lines for these easily ionized elements.
With some elements the differences, although significant, can be considered less so. In a concentration of 1 mg/L
and lower, the differences are tolerable from roughly
15%. Furthermore, the direct method is applicable, because its results occur mainly between those of the comparative methods. Therefore the significant differences
could also be traced back to systematic errors in the comparative methods.

b(D;A)

a(D;A)

b(D;S)

a(D;S)

0.963 0.106
0.930 0.428
0.872 0.075
1.024 0.053
0.947 0.063
0.943 0.031
0.897 0.051
0.868 0.051
0.890 0.278
0.913 0.047
0.421 0.082
0.780 0.113
0.536 0.055
0.972 0.028
0.771 0.043
0.775 0.082
1.192 0.076

0.152 0.427
0.056 0.050
0.033 0.072
0.039 0.045
0.020 0.045
0.089 0.057
0.003 0.082
0.047 0.092
0.022 0.007
0.030 0.023
0.024 0.012
0.645 0.127
6.115 0.683
11.766 3.107
6.512 4.664
3.775 6.908
147.349 64.942

0.993 0.053
1.141 0.074
0.996 0.080
1.184 0.051
1.166 0.049
1.099 0.031
1.238 0.130
1.143 0.075
1.286 0.047
1.394 0.105
1.158 0.038
1.035 0.392
0.450 0.068
0.881 0.016
0.858 0.043
0.874 0.097
0.759 0.070

0.255 0.264
0.008 0.007
0.134 0.077
0.012 0.043
0.003 0.043
0.034 0.056
0.115 0.211
0.107 0.135
0.024 0.012
0.191 0.052
0.009 0.006
0.096 0.439
5.654 0.846
5.688 2.224
11.058 4.711
7.630 8.213
220.259 59.915

557

4 Conclusion

Fig. 4 Representation of wine groups in the discriminant plane; p

Freyburg/Unstrut, Geisenheim, -- Blankenhornsberg, G Durbach,
M Nierstein, + Oppenheim

3.2 Evaluation and interpretation of the results

by multivariate statistics
In this study a methodical basis is established to investigate the wines, which by means of their element patterns
could give information as to their origins. The evaluation
of the results by multivariate data analysis provided initial
indications as to the distinction of origin. To achieve this,
pattern recognition methods such as discriminant analysis
were used. To differentiate between the wines from the 6
different wine-growing regions, up to 5 discriminant functions can be calculated. The two with the greatest discrimination power have been used in Fig. 4. The wines
from Durbach are proven to differ significantly from the
rest. The wines from the Saale-Unstrut region and from
Blankenhornsberg are also clearly distinguishable. The
samples from Geisenheim, Nierstein and Oppenheim
were not fully separated by these two discriminant functions. Phosphorus, iron, strontium and copper are the most
efficient elements in group separation. These results,
however, should only be considered preliminary. Due to
the small data set available, they are not fully representative. Moreover, the discrepancies with enological findings
show that it is not clear from the size of this data set,
whether the elements considered significant by the classification methods give indications of the structure of the
population, that is to say of the whole region of origin, or
only of the random samples taken. It follows then that in
taking a greater number of wine samples one can discover
which element contents are reproducibly influenced by
the wine growing and the wine making process and which
are not influenced at all. This knowledge would make it
possible to judge more effectively the origins of the wines.
This point will be investigated further.

The investigation undertaken has shown that direct analysis of mineral and trace elements in wine using ICP-OES
is possible in spite of some problems. This is proven particularly by the short time necessary for sample pretreatment and the high level of measurement precision. One
requirement, however, is that calibration be achieved with
standard solutions containing ethanol. By doing this, intensity differences caused by viscosity influence of the organic components during sample nebulization can be
compensated. In some cases it is possible to explain systematic differences between the direct method under evaluation and the established reference methods. The applicability of the direct method becomes clear in that the results achieved in this way are mostly between those of the
comparative methods.
Acknowledgements The authors would like to thank Prof. Dr. H.
Eschnauer for his assistance in obtaining the samples. We especially thank Winzervereinigung Freyburg/Unstrut e.G., Forschungsanstalt Geisenheim, Staatliches Weinbauinstitut Freiburg i.
Br., and Chemisches Untersuchungsamt Mainz, who supported our
work by supplying the wine samples. We are also grateful to Dr.
C.-J. Ntzold, Dr. V. Jngel and K. Weniger from the firm Carl
Zeiss Jena GmbH for making it possible for us to use the ICPspectrometer Plasmaquant 110.

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