MICROCHEMICAL JOURNAL

ARTICLE NO.

56, 221228 (1997)

MJ961386

Determination of Cadmium in Wines Using Graphite Furnace

Atomic Absorption Spectrometry with Zeeman
Background Correction
JAMES JAGANATHAN,1 ALAN L. REISIG,

AND

SUMER M. DUGAR

Bureau of Alcohol, Tobacco and Firearms, Department of the Treasury, National Laboratory Center,
1401 Research Boulevard, Rockville, Maryland 20850
Received January 12, 1996; accepted May 5, 1996
A graphite furnace atomic absorption spectrometry method with Zeeman background correction
for the direct determination of cadmium in grape wines is described. Use of ammonium dihydrogen phosphate, magnesium nitrate, and palladium nitrate as matrix modifiers was investigated.
Palladium nitrate with 10% nitric acid was the most satisfactory matrix modifier. The methodological detection limit, calculated as 3s/slope of the calibration curve, was 0.03 mg/liter for cadmium
in wine. The sensitivity, calculated as the characteristic mass, was 0.4 pg. The use of palladium
nitrate as a matrix modifier also results in excellent reproducibility (10% RSD) at such low
levels. This method is readily applicable to the determination of cadmium in wines without any
sample preparation. q 1997 Academic Press

INTRODUCTION

Toxic metal contamination in foods and beverages has drawn significant attention.
In the past two decades or so, extensive studies on exposure to lead and lead contamination in foods and beverages were conducted. The Bureau of Alcohol, Tobacco and
Firearms (ATF) conducted the studies on lead contamination in alcoholic beverages,
particularly in wines. Toxicological studies led to the establishment of 300 ppb (mg/
liter) maximum tolerance for lead in table wine (1). Having done extensive testing of
lead in wine, ATF is now conducting a survey of another toxic contaminant, cadmium,
in wine. Many scientific papers have been published that describe analytical methods
for quantification of cadmium in wines. In most cases, cadmium was determined in
conjunction with other metals.
Andrey et al. monitored lead, cadmium, copper, and zinc in wines from 19 different
countries using nitric acid as a matrix modifier (2). Gu et al. (3) determined many
elements in diluted yellow rice wine with ICP-AES. Dilution was necessary to lower
the solid content. Zee et al. (4) carried out elemental analysis in Canadian, European,
and American wines by photon-induced X-ray fluorescence for the determination of
trace inorganic constituents in wines. Casetta (5) determined cadmium and lead in
several wine samples with graphite furnace atomic absorption spectrometry (GF-AAS)
using ammonium dihydrogen phosphate and magnesium nitrate as matrix modifiers.
Gennaro et al. (6) carried out a thorough study of cadmium and other toxic metals in
1

To whom correspondence should be addressed.

221
0026-265X/97 $25.00
Copyright q 1997 by Academic Press
All rights of reproduction in any form reserved.

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TABLE 1
GFAAS Heating Program for Cadmium
Step

Temperature (7C)
Ramp (s)
Hold (s)
Internal gas flow
(ml/min)

120
1
60

400
1
60

1300
0
5

2500
2
5

20
1
15

300

300

300

300

Note. Lamp current, 4 mA; wavelength, 228.8 nm; slitwidth, 0.7 nm; matrix modifier, 100 mg Pd/liter
in 10% nitric acid.

wines. They preconcentrated the toxic metals using iminodiacetic acid as the chelating
agent and determined their concentrations with a direct-current plasma emission spectrometer. The concentrations of cadmium in most wines were expected to be at parts
per billion levels. This study was undertaken to establish a routine method of analysis
for cadmium in wine with GF-AAS. The use of palladium nitrate containing 10%
HNO3 as a matrix modifier for quantifying cadmium in both red and white wines
affords good precision and accuracy at or above 0.03 mg/liter.
EXPERIMENTAL

Apparatus
A PerkinElmer Model 5100PC atomic absorption spectrophotometer with Zeeman
background correction (PerkinElmer Corp., Norwalk, CT) was used for this study.
The spectrometer was equipped with an AS-60 autosampler and an HGA-600 furnace.
Graphite platforms (PerkinElmer platforms, Part No. B300-1256) were inserted into
pyrolytically coated graphite tubes (PerkinElmer, Part No. B300-1254). Zeeman
background correction was necessary to minimize interference caused by the complex
wine matrices. A single-element, hollow cathode lamp (PerkinElmer, Part No. N0661244) was operated at 4 mA. The slitwidth was 0.7 nm and measurements were made
at the 228.8-nm wavelength. The integration time was 5 s for all measurements. Pure

TABLE 2
Recovery Data for Cadmium in Wines (mg/liter)
Sample

Present

Added

Found

% Recovery

% RSDa

1
2
3
4

0.44
0.91
0.15
0.31

0.10
0.10
0.10
0.10

0.56
1.00
0.24
0.39

103.70
99.01
96.00
95.12

1.85
2.44
7.71
7.34

Each value is an average of five measurements.

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223

FIG. 1. Absorption peak profile of cadmium in a standard containing 0.1 mg/liter.

argon (99.99%) was used for purging. The instrumental parameters for furnace analysis
are listed in Table 1.
Reagents
The following reagents were used in this study:
1. Ammonium dihydrogen phosphate, analytical grade (J. T. Baker Chemical Co.,
Phillipsburg, NJ).
2. Cadmium standard stock solution, 1000 mg/liter (Fisher Scientific Co., Fair Lawn,
NJ). This was diluted to prepare a 0.5 mg/liter main standard. The calibration standards
0.1, 0.2, and 0.4 mg/liter were prepared in situ by the autosampler.
3. Magnesium nitrate, analytical grade (BDH Chemicals Ltd., Poole, England).
4. Nitric acid, ultrapure quality (J. T. Baker Chemical Co.).
5. Palladium nitrate, analytical grade (Sigma Chemical Co., St. Louis, MO).
RESULTS AND DISCUSSION

Matrix Modification
The analysis was first carried out without any matrix modifier. The precision and
analyte recoveries were too low, and the background absorption was very high. To
reduce the background absorption and to improve the analyte recoveries, a matrix
modifier was necessary. Magnesium nitrate and ammonium dihydrogen phosphate
were used separately and then in combination as matrix modifiers. The results showed
slight improvement in the precision but the recoveries were less than 50%. When the
experiment was repeated with 5 ml palladium nitrate containing 100 mg Pd/liter in
10% nitric acid, the results showed high precision and reduced background signals,
with recoveries in excess of 95% (Table 2).

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JAGANATHAN, REISIG, AND DUGAR

FIG. 2. Absorption peak profiles of cadmium in a red wine without matrix modifier (A) and with palladium
nitrate modifier (B).

GF-AAS Program Optimization

The furnace program was finalized after optimization of drying, charring, and atomization temperatures for aqueous standards. Palladium nitrate was selected as the
matrix modifier, and 5 ml 100 mg Pd/liter was added to provide a total of 500 ng Pd/
sample. Charring temperature studies were conducted at temperatures ranging from
400 to 7007C for 30 s, without matrix modifiers. Though the background absorbance
was decreased at increasing temperatures, the reduction was not significant. The studies
were repeated by keeping the charring time for 60 s. The background absorbance
decreased with increasing temperature. But, analyte loss was observed at temperatures
at and above 4007C. Using Pd as the matrix modifier the optimization was carried
out. The results showed that the background absorbance was significantly reduced at

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TABLE 3
Cadmium Concentrations in Various Imported Wines
Country of
origin
Argentina
Australia
Brazil
Bulgaria
Chile
China
Czech Republic
France
Greece
Hungary
Israel
Italy
Portugal
Romania
Spain

Type

Cd concentration
(mg/liter)a

Red
White
Red
White
Red
White
Red
White
Red
White
Red
White
Red
White
Red
White
Red
White
Red
White
Red
White
Red
White
Red
White
Red
White
Red
White

1.010 { 0.003
Not detected
0.046 { 0.004
0.072 { 0.003
0.205 { 0.002
0.178 { 0.012
Not detected
0.120 { 0.003
Not detected
0.086 { 0.006
0.043 { 0.004
Not detected
Not detected
0.328 { 0.007
0.093 { 0.008
0.283 { 0.009
0.340 { 0.013
0.045 { 0.002
Not detected
0.073 { 0.005
Not detected
0.193 { 0.006
0.166 { 0.002
0.104 { 0.001
0.101 { 0.007
0.340 { 0.017
0.059 { 0.005
0.161 { 0.001
0.096 { 0.007
0.259 { 0.016

Uncertainties represent {1 SD (n 3).

4007C for 60 s without any analyte loss. The reduction in background absorbance was
gradual without analyte loss up to 7007C. The charring temperature for this study
was kept at the minimum of 4007C to prolong the tube life. Similarly, atomization
temperatures were investigated from 1300 to 17007C. The minimum temperature
required to atomize the analyte in the standard was 13007C. It was found that these
operating conditions were appropriate for the wine matrices and were used for the
rest of this investigation. Figure 1 shows the resultant absorbance-vs-time plots under
these conditions. The background absorbance is greatly reduced by the matrix modifier
and the peak profiles are comparable to those of the aqueous standards. Figure 2
illustrates the effect of palladium nitrate on the matrices of wines. The background
absorbances are greatly reduced, resulting in improved peak symmetries.

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JAGANATHAN, REISIG, AND DUGAR

TABLE 4
Cadmium Concentrations in Some Wines Produced in
the United States

Origin

Type

Cd concentration
(mg/liter)a

Arkansas

Red
White
Red
White
Red
White
Red
White
Red
White
Red
White
Red
White
Red
White
Red
White
Red
White
Red
White
Red
White
Red
White
Red
White

0.274 { 0.005
Not detected
0.083 { 0.004
0.298 { 0.008
0.136 { 0.004
0.092 { 0.007
0.142 { 0.008
0.318 { 0.004
0.266 { 0.001
0.348 { 0.011
0.058 { 0.004
0.246 { 0.004
0.049 { 0.001
0.216 { 0.014
0.212 { 0.005
0.113 { 0.009
0.077 { 0.006
0.319 { 0.014
0.075 { 0.003
0.114 { 0.001
0.104 { 0.004
0.108 { 0.001
0.306 { 0.018
0.072 { 0.003
0.051 { 0.002
0.056 { 0.004
Not detected
0.344 { 0.018

Colorado
Georgia
Idaho
Indiana
Maryland
Michigan
Missouri
New York
Oregon
Texas
Virginia
Washington
Wisconsin

Uncertainties represent {1 SD (n 3).

Calibration and Detection Limit

An early report on the determination of cadmium in wines by Amerine et al. (7)
listed a linear concentration range from 0.0013 to 0.0041 mg/liter. Eschnauer (8)
found cadmium at 0.001 mg/liter levels in several wines. Casetta (5) used pulsedfield Zeeman spectrometry to quantify cadmium at 0.0015 mg/liter levels in red and
white wines. As the focus of this study was on quantifying cadmium at ultratrace
levels (1 mg/liter), calibration standards ranging from 0.1 to 0.4 mg/liter were used.
Throughout the study, the sensitivity, the correlation coefficient, and the detection
limit were regularly monitored. The sensitivity is calculated as the characteristic mass
(m0) and is defined as that amount of analyte required to produce an integrated absorbance measurement of 0.0044. The m0 was typically 0.4 pg. This is consistent with
the manufacturers specification for cadmium (0.35 pg). The correlation coefficients

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TABLE 5
Cadmium Concentrations in California Wines

Sample

Type

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20

Red
Red
Red
Red
Red
Red
Red
Red
Red
Red
White
White
White
White
White
White
White
White
White
White

Cd concentration
(mg/liter)a
0.060
0.126
0.100
0.427
0.141
0.101
0.382
0.295
0.130
0.141
0.271
0.116
0.252
0.266
0.128
0.092
0.172
0.260
0.142
0.075

{
{
{
{
{
{
{
{
{
{
{
{
{
{
{
{
{
{
{
{

0.003
0.005
0.004
0.012
0.009
0.006
0.001
0.015
0.011
0.011
0.010
0.007
0.019
0.006
0.003
0.006
0.010
0.003
0.002
0.003

Uncertainties represent {1 SD (n 3).

ranged from 0.9995 to 0.9999. The calculation of the detection limit was based on
3.00 s/slope of the calibration curve. The average detection limit was 0.03 mg/liter.
The solids content of table wines ranges between 3 and 6% (w/v). Beary and Paulsen
(9) reported the detection limit for cadmium as 0.001 mg/liter by ICP-MS in samples
containing 0.1% solids. Thus, it may require 30- to 60-fold dilution to bring solids
0.1%. The proposed GF-AAS method with Pd (NO3)2 matrix modifier affords direct
determination of cadmium in wines. The detection limit achieved by this technique
is equal to or better than that claimed for ICP-MS with reference to the original wines.
Standard addition method was used to verify the results of two white wines and two
red wines. The results were in good agreement, within {5%.
Applications
The GF-AAS method described here was used to determine cadmium in imported
as well as domestic table wines. Samples analyzed were 1988 or later vintages and each
sample was from a different producer. Data on cadmium in various wines surveyed are
presented in Tables 3, 4, and 5. Table 3 lists cadmium in several imported wines.
Table 4 lists cadmium in U.S. wines from different parts of the United States, and
Table 5 lists the cadmium levels found in wines from various producers in the state
of California. With the exception of one wine from Argentina, all wines tested were
found to contain cadmium at sub-ppb levels (1 mg/liter).

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JAGANATHAN, REISIG, AND DUGAR

CONCLUSIONS

The reported method has an average detection limit of 0.03 mg/liter, which is equal
to or better than the detection limit of other sensitive techniques such as ICP-MS.
Such low detection levels were feasible due to the direct sample injection (without
any sample preparation or dilution) with the use of palladium nitrate matrix modifier.
Analysis of 78 table wines from 16 different countries revealed that cadmium in wines
is likely to be less than 1 ppb (mg/liter). Such levels of cadmium in wines are significantly lower than the current U.S. Environmental Protection Agency (EPA) established
tolerance of 5 mg/liter in drinking water (10).
REFERENCES
1. Industry Circular No. 91-11. Bureau of Alcohol, Tobacco, and Firearms, Department of the Treasury,
Washington, DC, 1991.
2. Andrey, D.; Beuggert, H.; Ceschi, M.; Corvi, C.; De-Rossa, M.; Herrmann, A.; Klein, B.; ProbstHensch, N. Mitt. Geb. Lebensmittelunters Hyg. 1992, 83(6), 711.
3. Gu, L.; Zhou, Z.; Shen, R.; Shi, H. Fenxi-Huaxe 1987, 15(12), 1140.
4. Zee, J. A.; Szoghy, I. M.; Simard, R. E.; Tremblay, J. Am. J. Enol. Vitic. 1983, 34(3), 152.
5. Casetta, B. Boll. Chim. Igien. 1985, 36, 287.
6. Gennaro, M. C.; Mentasti, E.; Sarzanini, C.; Pesticcio, A. Food Chem. 1986, 19, 93.
7. Amerine, M. A.; Joslyn, M. A., Table Wines. The Technology of Winemaking. Avi, Westport, CT,
1971.
8. Eschnauer, H. Naturwissenschaften 1986, 73(6), 281.
9. Beary, E. S.; Paulsen, P. J. Anal. Chem. 1993, 65, 1602.
10. Drinking Water Regulations and Health Advisories. U.S. Environmental Protection Agency, Washington, DC, May 1995.

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