The Science of the Total Enuironment, 60 (1987) l-16 1

Elsevier Science Publishers B.V., Amsterdam ~ Printed in The Netherlands

APPLICATION OF DIFFERENTIAL PULSE ANODIC STRIPPING

VOLTAMMETRY TO THE DETERMINATION OF HEAVY METALS
IN ENVIRONMENTAL SAMPLES*

I’. OSTAPCZUK, P. VALENTA, H. RUTZEL and H.W. NURNBERG

Institute of Applied Physical Chemistry, Nuclear Research Center (KFA) Jiilich, P.O. Box 1913,
D-51 70 Jiilich (Federal Republic of Germany)

(Received May 13th, 1986; accepted June 12th, 1986)

ABSTRACT

A reliable procedure for the determination of the trace metals Cd, Cu, Ni, Pb and Zn in liquid
and solid environmental samples by an advanced voltammetric method has been developed. A
convenient method of sample pretreatment is wet digestion in a HNO,/HClO, mixture. The
simultaneous voltammetric determination of Cd, Cu, Pb and Zn is made at pH 2 by differential pulse
anodic stripping voltammetry (DPASV); the simultaneous determination of Ni and Co at pH 9 after
adsorptive accumulation of the respective complex with dimethylglyoxime at the electrode is made
by adsorption differential pulse voltammetry (ADPV). The particular advantages, of the vol-
tametric approach in food control for heavy metals are high sensitivity, good precision and
accuracy, the possibilities for the simultaneous determination of groups of metals and low cost
instrumentation.

INTRODUCTION

Reliable, sensitive and convenient analytical methods are an essential prere-

quisite for tasks in research and in routine consumer protection. Until now the
analytical determination of toxic metals in food has been in the (domain of
atomic absorption spectroscopy (AAS) with flame, or at lower trace metal
levels using the electrothermal mode (ETAAS) [l-4]. Voltammetry has been
used comparatively rarely in food analysis. However, the high sensitivity and
selectivity of the electrochemical approach, combined with inexpensive instru-
mentation (Table 1) and the possibility of the simultaneous determination of
several metals make it eminently suited for this task. Because of the low
concentrations often encountered, differential pulse anodic stripping voltam-
metry (DPASV), or, for Ni and Co, adsorption voltammetry (AV) or adsorption
differential pulse voltammetry (ADPV), will usually be the voltammetric meth-
ods of choice [l-9]. For the determination of heavy metals in drinking water,
sample pretreatment is limited to filtration and an acidification procedure [I’/].
Only for water samples with a high level of dissolved organic matter (DOM) is
efficient photolytic decomposition of inert metal complexes by UV irradiation

*Dedicated to the memory of Professor Dr Hans Wolfgang Niirnberg.

004%9697/87/$03.50 0 1987 Elsevier Science Publishers B.V.

TABLE 1

Comparison of equipment costs and determination time for voltammetry and electrothermal
atomic absorption spectroscopy

Analytical Equipment costa Analysis time

method (DM) (min)

ETAAS Basic equipment 5-7 x 104

Complete equipment
with Zeeman compensation 12-17 x lo4 206
DPP/DPASV/ADPV Basic equipment 1.52.5 x lo4 4oc
DPASV Microprocessor controlled
ADPV polarographic analyzer 5.5 x 104 2oc
swv

al$ U.S. = 2.50DM; 1DM = 0.43 $ US. = SO.29

b Determination of one element.
‘Determination of four elements.

necessary [lo]. All stages of water sample pretreatment in the laboratory

(filtration, acidification, UV irradiation) can be included in a fully automated
photodigestion device [ll]. For wine and certain fruit juices with low sugar
content, photolytic decomposition of dissolved organic material by UV irradia-
tion from a mercury lamp (150 W, 254 nm) with addition of H,O, is sufficient [8].
This digestion procedure has the special advantage that it introduces no
analytical contamination risk. For all other types of food, complete digestion
is usually necessary. Various digestion techniques are used to mineralize the
organic matrix in food samples. Wet digestion with various acid mixtures is a
cheap, practical and widely applicable method for all laboratories [6, 7, 9, 121.
The main aim of this work was to establish a reliable, routine voltammetric
analytical procedure for the determination of heavy metals in food. An in-
dependent, convenient and versatile alternative for heavy metal trace analysis
in food is thereby provided enabling either analytical quality control of AAS
data or to be used as a routine method. A universally applicable digestion
procedure for all food types, adapted for subsequent voltammetric determina-
tion of the trace metals Cd, Co, Cu, Ni, Pb and Zn, was developed and evaluated
by application to a large variety of important constituents of the food basket.

ANALYTICAL PROCEDURE

The usual analytical procedure consists of three stages: sample pretreat-

ment, adapted to the respective food type, wet digestion and the simultaneous
voltammetric determination of Cd, Cu, Pb and Zn by DPASV and Ni and Co by
linear scan or, at low heavy metal levels, adsorption differential pulse voltam-
metry (AV or ADPV). According to recent assessments [13], of particular
advantage for the determination of heavy metals at levels normally found in
food is the application of the square wave mode instead of the differential pulse
 3

mode. This mode is, however, only incorporated in some of the more recent and
expensive microprocessor-controlled instruments (see Table 1).

Sample preparation

Before digestion, an aliquot of the sample has to be taken in such a way so

as to avoid any risk of heavy metal contamination. Manipulations are carried
out using plastic implements, e.g. knives and pincettes with Teflon-covered
pincers [9, 121. Dry food is crushed between dry polyethylene foil to prepare a
sample for digestion (no significant Zn contamination was observed). Other dry
food types, such as rice and flour, are weighed directly into quartz digestion
dishes. For food samples with high water contents, e.g. vegetables and fruits,
and also liquid food, e.g. juices, beer and milk, prior drying is recommended by
heating in a quartz dish between 100 and 15O’C for 3660 min until constant dry
weight (DW) is obtained. The drying has the advantage that, in the subsequent
wet digestion, the necessary amount of HCIO, can be reduced to O.lml for
samples having originally 0.24.5 g fresh weight (FW). The 24 h freeze-dried
sample can then be homogenized by grinding between dry polyethylene foil. All
these pretreatment manipulations before digestion should be carried out using
a clean bench with controlled and filtered laminar air flow. The operator
should wear precleaned protective polyethylene gloves.
The chemicals and reagents used have to meet the following quality con-
ditions. All acids were Merck “Suprapur” substances. Standard solutions
containing 1 g 1-l of metals were prepared from Merck, Titrisol, and deionized
water from a Milli-Q-Purification System. For nickel and cobalt determination,
2M ammonia buffer of pH9.2-9.4 was prepared by weighing appropriate
amounts of 25% NH, (Merck, Suprapur), 30% HCl and deionized water into a
polyethylene bottle. Dimethylglyoxime (DMG) (0.1 M stock solution) was
prepared by dissolving appropriate amounts in 96% ethanol (both of purity
p.a.).

Wet digestion procedure

To a solid or liquid sample of 0.245 g or 0.5 ml, respectively, when no prior

treatment is necessary, or to a sample from the drying procedure, 0.1-0.5ml
70% HClO, and O&l.Oml65% HNO, are added in a quartz dish (10ml volume)
covered with a quartz watch glass. The amount of digestion acid is adjusted
within the stated ranges according to sample type and weight. The amount of
65% HNO, needed also depends upon the digestion time. The first stage of the
digestion procedure consists of gentle heating to 100°C; the sample dissolves
with foaming, the extent of which depends on the type of sample; the color of
the solution becomes dark green to brown. Rapid heating will require more
HNO, and may cause foaming problems. When foaming has finished and the
dissolution of the sample is complete, heating at 2OO“C is continued until
evolution of nitric oxides ceases and a light yellow or colorless liquid is formed.
If the solution is dark brown, or black, further addition of HNO, is necessary.
This HNO, addition has to be repeated until a colorless solution results.
The digestion of fats (butter, margarine, vegetable oils) follows in principle
the same pattern, but is more difficult and requires more HClO,, e.g. 1-2 ml for
a 0.2 g sample. The temperature has to be controlled and must not exceed 200°C,
as the oxidation by HClO, is rather vigorous. If the temperature becomes too
high and the HClO, level is too low the sample can become carbonized. With
fats a dark brown or black solution is formed and the above treatment, by
addition of appropriate amounts of HNO,, has to be applied until a colorless
solution is obtained.
Only if the trace metal level in the sample is < 10 pg kg ’FW is the digestion
solution to be evaporated to dryness. The resulting white crystalline residue is
then dissolved in 2 ml of water and 5 ~1 of 70% HClO,. For samples with higher
metal contents the colorless digestion solution is transferred with some water
into a 10ml volumetric flask and diluted with additional water.
Due to the small amount of HClO, required this digestion procedure is
without risk of an explosion. Nevertheless, it should be carried out in a fume
hood behind a protective glass screen. The HClO, containing vapour has to be
suctioned off by a water pump to avoid damage to the plastic parts and interior
of the fume hood. This wet digestion procedure is suitable for all types of food
and biological material [7, 9, 141when voltammetry is to be applied for heavy
metal determination. This digestion procedure ensures the necessary complete
mineralization and excludes interference by organic substances which remain
dissolved in the analyte. This is not the case with pressurized wet digestion,
which is frequently applied to the AAS determination of heavy metals, as it
leaves dissolved organic break-down products in the analyte. This constitutes
no problem for AAS, but if voltammetry is to be applied, the solution resulting
from pressurized digestion has to be treated subsequently by UV irradiation or
by heating with HClO, to decompose the dissolved organic digestion products
[15]. A simpler digestion approach for wines and fruit juices with low sugar
content using UV irradiation has been described [8].

Voltammetric determination

Voltammograms were recorded in the differential pulse mode [lo] with a

PAR 174 A Polarographic Analyzer connected to a Metrohm cell (EA 875-20).
Potentiostatic control of the electrode potential was established by means of
the three electrode system consisting of a hanging mercury drop electrode
(HMDE, Metrohm E 410, area 2.2mm”) as the working electrode, a coiled
Pt-wire as the counter electrode and an Ag/AgCl electrode as reference elec-
trode connected to the analyte by a salt bridge.
In the voltammetric cell, 20 ml of deionized water, 0.04 ml of 70% HClO,, as
supporting electrolyte, and 0.5 ml of analyte solution resulting from the HClO,/
HNO, wet digestion procedure are de-aerated for 10 min with purified nitrogen
(99.999%). Cadmium, Cu, Pb and Zn are determined simultaneously by DPASV.
 H :D
YU uk ,‘C”

0 10 20 NG co
10 2c NC PB
50 !OO NL NI
500 1000 NC cu
5000 fi 1nooo N‘ ZN

1 A/
-I -F1--l, ,
4.7 -1.2
E/V
IN= lOJ,LIYG/KGCO=14&JG/KG Cu=9,5hnc/nr NI=~QJG/KG
PB=SJ,tk/KG

NI = 100 NG

!0.5~
A

-1.2 0.8 0.2 0.7 E/V '.2

Fig. 1. Determination of heavy metals in wheat bran. Sample weight, 0.0582g; DPASV, pulse
height = 25mV. scan rate 5mVs-‘, clock time = 0.5 s; deposition time: Zn, 20 s (Ed = 1.2 V); Cd,
Pb and Cu, 180 s (Ed = - 0.8V); Ni 60s (Ead = - 0.7 V). (1) Sample curve; (2)‘second standard
addition curve.
6

The heavy metals are preconcentrated simultaneously at the HMDE by deposi-

tion as amalgams. This is achieved by adjusting the deposition potential of
_ 1.2V for 26min and stirring the solution with a magnetic stirrer (700rpm)
to enhance mass transfer to the HMDE. After turning off the stirrer, and a rest
period of 30s anodic stripping is performed in the differential pulse mode
(DPASV) with the following parameters: pulse height, 50mV; pulse duration,
56ms; time, 0.5 s; and scan rate, 5 mV s I. If necessary, the sensitivity of the
instrument can be altered so that the different responses between zinc and
cadmium and between lead and copper can be detected. The measurement is
repeated once before adding small volumes (50-150~1) of standard solution.
Two standard additions are sufficient to determine the concentration. The
concentrations of the metals are calculated from the intercept of the linear
regression lines with the x-axis. An example is given in Fig. 1.
Nickel (and cobalt) determination is performed subsequently by adsorption
voltammetry (AV) [6, 71 in the same solution after addition of 0.5ml of 2M
ammonia buffer to adjust the pH to 9.2 and 50 ~1 of a 0.1 M solution of di-
methylglyoxime in ethanol. The nickel- and cobalt-dimethylglyoxime com-
plexes which are formed are at first accumulated by adsorption of the HMDE
surface at a potential of - 0.7 V. The adsorbed Ni and Co complexes are then
reduced by scanning (scan rate 20 mV s -‘) with a linear voltage scan to more
negative potentials. At very low nickel and cobalt concentrations
( < 10 ~1 kg ‘) the differential pulse mode has to be applied with the parameters
given above, i.e. by adsorption differential pulse voltammetry (ADPV). Figure
1 shows an example of the simultaneous determination of all treated heavy
metals.

RESULTS AND DISCUSSION

Accuracy

The accuracy of the described digestion and determination procedure was

tested by analysis of NBS standard reference materials. The values determined
‘are in good agreement with the certified values (Table 2).

Determination of sensitivity and precision

The determination of the sensitivity of the voltammetric procedure after wet

digestion is not limited by the methodological potential of the voltammetric
methods themselves, but by the digestion blanks values which vary with the
amount of acid used. In 1 ml of digestion mixture (HClO,/HNO,, 1:2) the blank
values were: long Zn, 0.1 ng Cd, 0.3 ng Pb and 0.08ng Ni, with a day-to-day
fluctuation of < 20%. For many types of food the trace metal concentrations
are > 1OOpg kg-’ and therefore the digestion blank value is negligible.
TABLE 2

Determination of Zn, Cd, Pb, Cu and Ni in NBS Standard Reference Materials

Samplea Element Found values Certified values

(mgW’) (mgW’)

Orchard Leaves Zn 24.7 i 0.7 25 * 3

NBS 1571 Cd 0.11 i 0.01 0.11 + 0.01
(n = 5) Pb 44.4 * 1.7 45 + 3
CU 11.1 t 0.4 12 -t 1
Ni 1.28 + 0.17 1.3 + 0.2

Bovine Liver Zn 126.6 + 7.0 130 i 10

NBS 1577 Cd 0.31 k 0.02 0.27 i 0.04
(n = 6) Pb 0.28 i 0.03 0.34 ? 0.08
cu 197.6 k 7.6 193 + 10
Ni 0.15 i 0.01 0.155 (22)

Spinach Zn 49.1 ? 0.7 50 * 2

NBS 1570 Cd 1.58 k 0.06 (1, 5)
(n = 6) Pb 1.29 & 0.08 1.2 k 0.2
cu 11.1 * 0.4 12 * 2
Ni 5.78 k 0.20 (6)

an = number of independent determinations.

APPLICATIONS

The developed, and extensively tested analytical procedure with vol-

tammetric determination has been applied to a large number of food types.
Although the number of specimens investigated of each food type is rather
limited, the data presented provide an estimate of the magnitude of heavy metal
levels to be expected in the food types studied and show that in this respect
different food groups can be distinguished. The number (n) of specimens inves-
tigated is given in the tables; three independent samples from each specimen
were analyzed.

Cereals and cereal products

Table 3 contains the results for cereals and cereal products, except rice for
which the results are listed in Table 4. Levels of Cd are comparatively high in
wheat grain and wheat products including noodles. A particularly high Cd
level is observed in wheat bran. In rice (Table 4) the Cd levels are usually an
order of magnitude lower, except for rice from the U.S.A. This is either a
consequence of intensive fertilizer application or due to higher Cd pollution in
the rice growing area. In Japan the Cd level in rice is about 0.1 mg kg-‘. Only
the Cu content of wheat bran is significantly higher, while the rice from
north-east Brazil contains rather low concentrations of Cu (see Tables 3 and 4).
The Pb-level in bread is more than double that in wheat grain and flour and
is probably caused by some contamination during baking. The levels of Cd and
8

TABLE 3

Heavy metals in cereals and cereal products

Specimen n Metal (pgkg ‘)

Zn Cd Pb CU Ni

Wheat grain 19300 54 12 3000 570

Wholemeal bread 12100 26 27 1540
Wheat/rye mixed
bread 18600 29 43 2140 113
Wheat bread 19500 50 46 2160
Wheat flour 3860 39 19 840
Wheat bran
Full 107400 148 58 9560 640
Diet 73800 66 37 13300 590
With milk sugar 84300 52 28 10800 1010
Noodles 11300 62 22 4650 44

Pb in cereals and cereal products should be considered in the context of the

average daily intake allowed in the WHO recommendations. For adults with a
typical body weight of 70 kg a daily intake of 70 ,ug Cd and 430 pg Pb is recom-
mended; for children the recommended intake is lower.

Vegetables

Table 5 presents data on vegetables, together with data for grass, clover,
sugar beet and sugar. Vegetables, as well as grass and clover for comparison,
were collected from gardens in a heavily Pb- and Cd-polluted area close to a
lead smelter at Stolberg and from an unpolluted agricultural area at Jiilich
which exhibits, like many other rural regions, the lowest heavy metal deposi-
tion from the atmosphere in the Federal Republic of Germany. In general, the
data reflect the potential of some vegetables to accumulate heavy metals and
show that, at locations with severe heavy metal pollution through deposition
from the atmosphere, the heavy metal levels in vegetables can be orders of

TABLE 4

Heavy metals in rice

Cultivation n Metal (pg kg- ‘)

area
Zn Cd Pb CU Ni

North-east
Brazil 1 10800 2.3 15.5 945 200
France, Camarque 1 14000 1.7 11.6 1700 120
Bali 1 11300 5.1 17.4 1800 160
U.S.A. 1 9000 21.6 14.6 1200 340
 9

TABLE 5

Influence of environmental burden of heavy metals on their contents in vegetables and plants

$ pecimen”
L n Metal (pgkg-‘)

Zn Cd Pb CU Ni

F’otatoes (a) 3 11000 210 18 1500 118

(b) 3 1590 8 3 330 66
Rhubarb (a) 3 1520 68 296 164 18
(b) 3 1220 2 13 105 14
Leek (a) 3 6570 136 290 402 65
Parsley (b) 2 12600 42 425 5350 380
Lettuce, garden (b) 1 3370 46 68 611 38
greenhouse 1 4150 69 5 285 59
Tomato, greenhouse 1 770 9 1 231 17
Grass (a) 17 19300 172 6200 2680 183
(b) 3 14300 18 230 1960 170
Clover (a) 20 18000 164 5600 2000 175
(b) 3 13800 21 250 780 93
Sugar beet (b) 3 3290 39 36 503 23
Sugar 1 105 1 65 55 12

(a) = sample collected near a lead smelter at Stolberg.

(b) = sample collected in Jiilich.

magnitude higher, which is apparent in plants with large leaf surfaces, e.g. lead
in garden lettuce is higher than in greenhouse lettuce (see Table 5). The
Federal Health Office has recommended tolerable levels of 1.2 mg Pb kg-’ and
0.1 mg Cd kg-l in vegetable leaves [l]. Only the Cd concentrations in leek from
polluted areas are higher (Table 5). For potatoes the recommended values are
0.2mgPbkg-’ [l]. In Cd-polluted areas this metal accumulates in potatoes.
Generally, it can be stated that the consumption of vegetables from Cd- and
Pb-polluted areas, especially without careful mshing, results in an un-
necessarily high intake of both metals.
The same applies with respect to Cd and Pb in grass and clover. Both plant
species show a remarkable accumulation potential for Pb (see Table 5).
A comparison of the heavy metal concentrations in sugar and s’ugar beet
shows only low lead contamination during sugar production (see Table 5). The
levels of the other elements are lower in sugar than in sugar beet.

Fruits

Rather low heavy metal levels are to be expected in fruits, as Table 6 reflects.
The differences in the heavy metal content between the skin and pulp of grapes
are exceptional; the heavy metal levels in grape pulp correspond in magnitude
to the average levels found in wines [5]. An exception is Pb which, on average,
has significantly higher levels (by about 2 orders of magnitude) in wine than in
10

TABLE 6

Heavy metals in fruits

Fruit n Metal (pgkg ‘)

Zn Cd Pb cu Ni

Apples
New Zealand 3 178 0.5 5.1 138 8.8
Apples, France 3 89 0.5 0.7 212 8.2
Apples, Germany 3 189 2.4 3.3 169 32.6
Pears, Italy 3 326 0.9 3.7 445 75.7
Grapes, Italy
Skin 1 6160 1.1 23.0 5640 24.5
Pulp 1 1120 0.12 0.86 1023 8.1
Orange juice 2 223 1.0 1.76 180

grape pulp and, typically, about a factor of ten or more than in the grape skin.
According to our extensive investigations [3] the typical average levels in wine
are (pgl-l): Cd, 1.5; Pb, 130; Cu, 400 (but can be up to 4000); and Ni, 60. Heavy
metal levels in beer are rather low. The investigation of a number of different
German beers yielded the following ranges (pglll): Zn, 540; Cd, 0.4-1.7; Pb,
0.7-5.5; Cu, 555; and Ni, 2.510. Although these ranges are low, only their
lower values overlap with the respective heavy metal levels in drinking water.

Food types of animal origin

Table 7 provides an estimate of the heavy metal levels in some common food
types of animal origin. For comparison margarine has also been included as an
important type of fat in the food basket of man. Generally the heavy metal
levels are rather low, particularly in milk, due to the very small transfer factors
from cattle fodder, grass and clover, into milk.
The same is true for meat, as shown by a recent study on beef and veal [9].
Only for the detoxification and storage organs, i.e. the liver and kidney, have
high heavy metal levels been found. This seems to be a common feature for very
different kinds of animals, as extended studies on pelagic and benthic fish [12]
and recently on mussels and oysters have shown [16]. In the muscle of fish, Hg
is usually present, > 90% of which is in the form of methylmercury, which, in
toxicological terms, plays a significant role. The Hg burden of large fish such
as tuna and swordfish is particularly high [12, 171. The other heavy metals,
among them the toxic Cd and Pb, reach elevated levels in the liver and kidneys
[12]. Similar findings have been established for mussels and oysters, although
it must be taken into account that specimens of these sea foods are consumed
whole.
From the data for fats in Table 7, compared with milk the levels of Cd and
Pb are somewhat higher in butter, whereas the content of Zn and Cu is lower
 11

TABLE 7

Heavy metals in common food types of animal origin

_
Specimen n Metal (pg kg-’ )

Zn Cd Pb Cu Ni

Milk 3.5% fat 10 3730 0.1 1.83 40.3 4.4

Milk 0.3% fat 10 3940 0.1 5.50 49.4 10.7
Butter 3 309 2.27 9.84 3.36 11.6
Margarine 3 1270 42.0 164.1 58.0 610
Smoke-dried 1 13350 1.97 11.3 380 6.3
ham
Pork 1 0.27 7.1 300 4.3

by an order of magnitude. Noticeably higher levels of Cd, Pb and Ni .are found

in margarine, than in butter. For Ni, and possibly for Cd and Pb, the levels in
margarine are probably associated with input during the production process.

Mushrooms

Substantial levels of Cd, Pb and Cu are contained in wild mushrooms picked

from forests and fields, as shown in Table 8. Mushrooms are potent heavy metal
accumulators [18, 191. There are remarkable differences between the heavy
metal contents of the stem and the cap, which amount, for example for BoEetus
edulis, to a 5-fold higher heavy metal enrichment in the cap compared with the
stem. The most frequently consumed cultivated mushroom (champignons) have

TABLE 8

Heavy metals in mushrooms (FW)

Specimen n Metal (pg kg-‘)

Zn Cd Pb cu Ni

Yellow bolete
(Boletus edulis) 30600 440 200 13500 440
Stem 19200 1920 320 4800 105
Cap 27706 3010 580 6200 174
Gill 45400 11600 1730 20600 240
Chanterelle
(Cantharellus
cibarius) 1 16706 680 406 5300 660
Field mushroom
(Agaricus Camp.) 3 6100 150 41 3000 60
Cultivated
champignons
Fresh 3 2800 15 6 1500 5
Canned 3 3406 8 7 1500 9
12

TABLE 9

Heavy metals in baby food

Specimen n Metal (pgkg ‘)

Zn Cd Pb CU Ni

Instant milk
powder 2 11800 0.13 11.7 160 43.1
Instant baby
food
Banana 1 7280 15 42.3 1450 71.4
Fruits 1 11 21 910
Semolina 1 33 12 1300
Orange 1 36 4 1300
Rusk 1 31 27 2000
Pear 1 14 320 640
Whole milk food
Caramel 1 22 28 1400
Chocolate 1 26 27 2500
Fruits 1 38 34 1400
Carrot flakes 1 115 100 3600

rather low contents of Cd and Pb, as they are grown on unpolluted soil in
greenhouses where no input of heavy metals by deposition from the atmosphere
is possible. The consumption of not more than 20s250g of wild mushrooms
weekly is recommended by the Federal Health Office. This recommendation is
based on the preliminary permissible intake of cadmium published by WHO
(5OOpg week-‘), for which an absorption of 5% of the consumed Cd by the
digestive tract is assumed.

Baby food

A special food type is instant baby food preparations. Heavy metal levels
found in four types are given in Table 9. The concentration of Cd is remarkably
high, except for instant milk powder, because cereals (see Table 9) are a basic
constituent of instant baby foods. This would explain the elevated levels in the
various fruit preparations compared with the Cd content of fresh fruit (Table
6). The Cu levels are also comparable with those in cereals and cereal products
(Table 2) and in many cases, the same applies to the Pb levels.
The instant baby food containing pears has a rather high Pb level which
indicates that Pb contamination has possibly taken place during production.
In general, the levels of Cd found in the randomly selected baby food samples
seem to be undesirably high. In this context it should be borne in mind that the
WHO recommendation for a tolerable average daily intake of 70mg Cd refers
to an adult of 70 kg body weight. Taking into account the lower body weight
of babies the tolerable average daily Cd intake is also correspondingly lower.
The Cd content of some of the baby food products investigated is such that a
baby would ingest the tolerable lower levels of Cd with a daily consumption of
200 g of baby food.
TABLE 10

Heavy metals in pipe and cigarette tobacco

Specimen n Metal (mg kg-‘)

Zn Cd Pb CU Ni co

Pipe tobacco
I 3 33.4 * 1.1 0.70 * 0.04 1.33 + 0.19 15.2 i 0.5 4.62 + 0.36 1.03 i 0.03
II 3 33.6 + 1.7 0.49 * 0.04 0.75 * 0.04 6.26 & 0.19 1.60 t 0.11 0.53 f 0.04
III 3 18.4 -t 3.1 0.22 * 0.05 0.58 f 0.01 5.86 + 0.32 1.43 + 0.28 0.93 +_ 0.09
Cigarette tobacco
I 3 41.0 * 3.7 1.03 z!z0.11 1.91 * 0.14 9.35 + 0.70 2.24 i 0.95 0.56 i 0.07
II 3 29.8 ? 0.6 1.43 t 0.06 2.20 i 0.07 10.9 & 0.3 3.36 -t 0.20 0.79 i- 0.03
III 3 47.8 f 3.1 1.29 + 0.01 2.03 ?r 0.37 21.0 + 1.8 3.67 + 0.16 0.60 i 0.08
 Y

TABLE 11

Heavy metals in tea, coffee and cocoa

Specimen n Metal (mgkg-I)

Zn Cd Pb cu Ni co

Tea
I 3 41.0 i 2.2 0.028 * 0.003 0.81 i 0.07 22.9 + 1.7 8.67 _+ 0.62 0.67 ? 0.10
II 3 27.0 + 1.5 0.032 ? 0.002 0.83 ? 0.05 20.4 -c 1.0 6.62 -t 0.66 0.28 i 0.02
III 3 24.0 f 1.4 0.012 i 0.001 0.52 i 0.07 30.6 ? 1.9 5.57 * 0.53 0.18 i- 0.01

Coffee
I
(instant) 3 2.91 i 0.19 0.005 * 0.001 0.053 + 0.007 0.23 _t 0.01 0.75 F 0.07 0.31 * 0.04
II 3 3.83 ?r 0.11 0.004 f 0.001 0.071 * 0.002 10.9 ? 0.8 0.47 + 0.07 0.11 + 0.02
III 3 5.34 f 0.11 0.005 i 0.001 0.041 t 0.003 13.2 + 0.05 0.32 i 0.01 0.14 * 0.01

Cocoa
I 3 58.1 i 5.5 0.16 ? 0.005 0.29 * 0.02 31.6 i 0.7 10.6 + 0.7 1.31 * 0.09
 A permanent control of the levels of toxic heavy metals in baby food
products by reliable and convenient analytical methods is therefore urgently
needed.

Tobacco, cigarettes, coffee and tea

Heavy metal contents of pipe-tobacco and cigarettes are shown in Table 10.
The high Cd level results in a large cadmium concentration in the blood, urine,
liver and kidneys of smokers than non-smokers [20, 211.
Nickel compounds can be toxic; a large number of insoluble inorganic Ni
compounds cause lung and nasal cancers [22]. The very high Ni level i-n tobacco
smoke, caused by reducing conditions and elevated temperatures dur:ing smok-
ing, can be a hazard to long-term smokers, but more investigations on this
subject are necessary. The highest level of Ni, and all other metals, was found
in cocoa (see Table ll), which may reflect the natural elemental composition
of cocoa beans or may be a consequence of enrichment in preparative stages.
The Ni levels in tea are about 20-100 time larger than in other plants (Tables
5 and 11); the Cd and Pb levels in tea are similar to those observed in various
common vegetable samples. Even lower cadmium and lead concentrations are
found in coffee. In instant coffee (Table 11) the Cu level is 50 times lower than
in coffee grain, but for Ni and Co a slight enrichment was observed. The
concentration of heavy metals in tea leaves and coffee grain cannot provide
information about the intake of these metals by drinking tea and coffee. Table
12 shows the heavy metal concentrations in a normally prepared water extract
of tea and coffee. The concentrations of all the metals in the water phase, with
the exception of nickel in tea, are lower than the tolerable limits for the metals
in drinking water [23]. The nickel components in tea leaves are soluble in water
(see Table 12) unlike those in coffee grains. Similar concentration relationships
in extracts of tea and coffee were found for Zn and Cu. Cadmium and lead
concentrations in drinks are very low, lower than the concentrations in some
drinking water samples [24].

TABLE 12

Water extract of heavy metals from tea and coffee

Element Tea IV Coffee IV

Raw Solution % of total Raw Solution % of total

material 4.94 g tea in amounts in material 10.7 g coffee in amounts in
(mgkg-‘) 250 ml water solution (mgkg-‘1 100 ml water solution
(mgkg-‘) (mg kg-‘)

Zn 26.0 0.283 55.0 3.55 0.197 51.5

Cd 0.034 0.0001 17.4 0.002 0.00008 46.9
Pb 0.708 0.002 15.4 0.056 0.030 53.8
cu 23.0 0.083 18.3 11.2 0.218 18.1
NI 6.52 0.106 82.2 0.481 0.016 32.0
CO 0.192 0.0015 40.3 0.159 0.0075 60.7
16

Relatively high Zn and Cu levels were found in all the food samples inves-
tigated. The daily requirement for an adult is 15mg of Zn and 5mg of Cu [22]
and food is the fundamental source of these essential heavy metals.

CONCLUSIONS

The voltammetric approach to the determination of heavy metals in food

samples after wet digestion is a very reliable, sensitive and accurate method.
Simple sample pretreatment, the low cost of the electrochemical equipment
(see Table 1) and the possibility of simultaneous determination of metal groups
are the greatest advantages of voltammetry. The rapid progress in microcom-
puter techniques has enabled the construction of fully automated voltammetric
equipment which reduces the determination procedure for four elements (Zn,
Cd, Pb and Cu) to about 20min (see Table 1).

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