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ANALYST. APRIL 1989. VOL. 114

355

Comparison of Some Wet Digestion and Dry Ashing Methods for

Voltammetric Trace Element Analysis

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Samuel B. Adeloju
Centre for Industrial Research and Advanced Technology, University of Western Sydney, Nepean,
Kings wood 2 750, Australia

Several wet digestion and dry ashing methods were compared for the precise and accurate determination of
some trace elements in biological and environmental materials. The wet digestion methods were generally
faster than the dry ashing methods, but required the use of large amounts of reagents and, therefore, gave
higher blank contributions for some elements. The main advantages of the dry ashing method were the lower
blank levels, improved (lower) background current and its ability to handle considerably larger amounts of
sample. However, careful dissolution of the sample ash in a suitable reagent was necessary. Under suitable
conditions, both decomposition methods allowed the reliable voltammetric determination of trace elements
in biological and environmental materials with relative standard deviations of between 1 and 3%. The ultimate
choice of decomposition method was influenced by the amount of sample available, the nature of the sample,
the sample matrix and the analysis time available.
Keywords: Digestion methods; trace elements; voltammetry; biological and environmental materials

The determination of inorganic elements in biological and

environmental materials at trace and ultra-trace levels has
now become a major aspect of various diagnostic and
monitoring programmes. For this reason, several analytical
techniques have been developed over the last two decades that
are capable of determining the elements reliably at these
levels. Such methods include numerous variants of electroanalytical methods. for example, anodic stripping voltammetry (ASV), cathodic stripping voltammetry (CSV), differential-pulse polarography (DPP). square-wave voltanimetry (SWV) and the more recent approach of adsorptive
cathodic stripping voltammetry (ACSV). These techniques
are now being used more in the determination of trace
elements in biological and environmental materials owing to
their simplicity, improved selectivity and high sensitivity. 1-11
Unfortunately, the direct determination of the elements in
these sample matrices is not feasible because of the enormous
matrix effect usually encountered at the trace and ultra-trace
concentrations of the analytes. In general. the accurate
voltammetric determination of trace elements in these sample
matrices requires a complete and thorough decomposition of
the organic matter, while also demanding quantitative retention of the analytes in states or forms amenable to quantification. 1.3-5
The two types of decomposition method commonly
employed for the determination of trace elements in biological
and environmental materials are wet digestion and dry ashing.
Although the latter is well accepted, the wet digestion method
is more commonly employed with most analytical techniques.
The preference for this type of decomposition method is based
on the reduced danger of losses at the lower operating
temperatures. On the other hand, the dry ashing method
requires the use of ashing aids and/or careful manipulation of
the ashing temperatures to minimise or prevent the loss of
analyte.3.11.12 Evidently, the use of various reagents, both as
ashing aids and for the sample ash dissolution, represents the
major source of contamination in this decomposition method.
Similarly. the use of relatively larger amounts of reagents in
the wet digestion methods represents an even greater source
of contamination.
Concern about the problems of contamination and loss of
elements associated with both types of decomposition method
led to the development of other methods based on closed
systems, such as wet decomposition in pressure bombs,
combustion in oxygen flasks, and in oxygen bombs and other
combustion systems, as well as direct dissolution with tetra-

alkylainmonium hydroxide. '3.14 However, none of these

methods have completely eliminated the associated blank
contributions resulting from the use of the reagents for either
the decomposition or the sample ash dissolution.
The suitability of wet digestion and dry ashing methods is
frequently investigated for various analytical techniques such
as atomic absorption spectrometry, neutron activation analysis, fluorimetry and spectrophotometry. Unfortunately.
similar investigations are rare for voltammetric trace element
analysis. Consequently, there have been increasing reports of
inconsistencies between voltammetric results and those of
other analytical techniques. In general, the demand for careful
and complete decomposition of biological and environmental
materials is more critical for voltammetric techniques owing to
their reliance on the presence of analytes in states or forms
that are suitable for accurate determination. In particular, the
possible inhibition of the electrode processes by the presence
of organic residues in the decomposed samples is of major
concern.
In this study, several wet digestion and dry ashing methods
have been compared for the voltammetric determination of
arsenic, bismuth, cadmium, cobalt, copper, lead, nickel,
selenium, vanadium and zinc in biological and environmental
materials. The methods considered are those readily accessible to most analytical laboratories: (i) direct dry ashing: (ii)
dry ashing with sulphuric acid a s an ashing aid; (iii) dry ashing
with nitric acid as an ashing aid; (iv) dry ashing with
magnesium nitrate as an ashing aid; (v) wet digestion with
nitric acid only; (vi) wet digestion with a mixture of nitric and
sulphuric acids: and (vii) wet digestion with a mixture of nitric
acid and potassium persulphate.
Animal Muscle, Bovine L,iver, Orchard Leaves and Oyster
Tissue were chosen as test materials because of the diversity of
their sample matrices. The influences of the nature of the
sample, the amount of sample available, the sample matrix
and the available analysis time on the choice of decomposition
method for the reliable voltammetric analysis of trace
elements were also examined.

Experimental
Reagents and Standard Solutions

All acids and the ammonia solution used were of Aristar grade
(BDH, Poole, Dorset, UK); all other reagents were of
analytical-reagent grade. The ammonia - ammonium chloride

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ANALYS'I'. APRIL 1989. VOL. 114

456
buffer solution, dimethylglyoxime (dmgH?), standards and
distilled, de-ionised water were prepared as described pre\ iously. i-h
Instrumentation
All experiments were performed by differential-pulse voltammetric methods on an E G &: G Princeton Applied Research
(Princeton, NJ, 1JSA) microprocessor-controlled instrument
as described previously.3--" A medium-size mercury drop
having a surface area of 0.015 cmz was used in all instances.

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Glassware
All glassware and polyethylene bottles were soaked in 2 M
nitric acid for at least 7 d , washed three times with distilled,
de-ionised water, soaked in distilled, de-ionised water and
finally soaked in 0.1 M hydrochloric acid until ready for use.
Biological Standard Reference Materials (SKMs)
Animal Muscle (IAEA RM M-4) was obtained from the
Analytical Quality Control Services of the International
Atomic Energy Agency (IAEA) in Vienna, Austria. Bovine
Liver (NBS SRM 1577a). Oyster Tissue (NBS SRM 1566a)
and Orchard Leaves (NBS SRM 1571) were obtained from the
US National Bureau of Standards (NBS), Washington, DC.
All materials were treated as recommended by the suppliers.
Digestion Methods
1. W e t digestion
(a) W i t h H N O j only ( W l ) . Transfer 0.3 g (or 10 ml) of
sample and 10 nil of nitric acid (65%) into a 125-ml
Erlenmeyer flask, insert a pre-cleaned glass funnel and heat
on a hot-plate at approximately 290 "C until nitrogen oxide
fumes are just given off. Repeat the digestion with two
separate additions of 10 ml of nitric acid, cooling the tlask for
about 2 min between each addition. With the final addition of
nitric acid, continue heating at the same temperature until the
nitrogen oxide fumes are completely evolved. Cool the flask
again for about 2 min and rinse the funnel with a small volume
o f distilled. de-ionised water into the flask. For the determination of selenium, add 3 ml of 37% hydrochloric acid (1 + l ) ,
replace the funnel and then heat the mixture at a temperature
setting of approximately 210 "C on the hot-plate for at least 30
min to convert all the selenium to selenium(1V). Cool to room
temperature, rinse the funnel again into the flask with water
and transfer the contents into a 25-ml calibrated flask, making
up to the mark with distilled, de-ionised water.
(b) W i t h H N 0 3 - H 2 S 0 4(W2).Transfer 0.3 g (or 10 ml) of
sample, 10 ml of nitric acid (6.5%) and 1 ml of sulphuric acid
(98%) into a 125-ml Erlenmeyer flask and carry out the
digestion a s described in (a) [including the treatment with HCI
for the conversion of selenium to selenium(IV)]. In this
instance, repeat the digestion with three separate additions of
nitric acid and continue heating after the final addition of
nitric acid until the nitrogen oxide fumes and the sulphite mist
have disappeared.
(c) With FINO3 - K2S2O8("3). Transfer 0.3 g (or 10 ml) of
sample. 10 ml of concentrated nitric acid and 4 ml of potassium
persulphate (10% mlV) into a 125-ml Erlenmeyer flask and
repeat the digestion as described in (a) [including the
treatment with HC1 for the conversion of selenium to
selenium(IV)].
In all of these wet digestion methods, care was taken to
avoid sample charring because this can result in reductive
conditions that might lead to the loss of selenium via the
formation of volatile hydrogen selenide. For the arsenic
determination, conversion of the element to arsenic(II1) was

carried out by the method described by Sadana7 after the

nitrogen oxide fumes (and sulphite mist) had disappeared.

2. Dry ushirig
(a) Direct dry ushing without an ashing nid ( 0 1 ) . Accurately weigh 0.5 g of sample into a pre-cleaned silica dish and
heat gently on a hot-plate to volatilise as much moisture and
organic matter as possible. From time to time, spread the
sample out with a pre-cleaned silica rod to accelerate drying.
When the sample is fairly dry (30-60 min) transfer the dish to a
temperature-controlled muffle furnace at 450 "C. Leave in the
furnace for 8 h (or overnight) to complete the decomposition
step. Remove from the furnace, leave to cool and add 3 ml of
6 M hydrochloric acid. Warm gently on a hot-plate to dissolve
the sample ash and to extract the elements from any insoluble
residue. Transfer the contents quantitatively into a 10-ml
calibrated tlask by washing the dish with distilled, de-ionised
water and mix thoroughly to ensure homogeneity.
(b) With sulphuric acid as a n ushing aid ( 0 2 ) . Accurately
weigh 0.5 g of sample into a pre-cleaned silica dish and add
5 ml of 20% V/V sulphuric acid (3.6 &I). Heat gently on a
water-bath for 30 min and transfer to a hot-plate, heating until
the white fumes cease to be evolved and the residue is
completely dry. Transfer the dish to the muffle furnace at
500 "C and leave overnight or for at least X h to complete the
decomposition. Dissolve the residue and make up the solution
as described in 2(a). If the sample contains carbonaceous
residue, leave it to settle before removing an aliquot for
analysis.
(c) Wirh nitric acid us a n ushing aid ( 0 3 ) . The procedure
was similar to that in 2(b) except that 5% VIV nitric acid was
added instead of sulphuric acid and the ashing was carried out
at 4.50 "C.
(d) With magnesium nitrate as a n ushing aid ( 0 4 ) . The
procedure was similar to that in 2(b) except that the sample
was first digested with nitric acid and 5 ml of 80% miV
magnesium nitrate solution before dry ashing in the muffle
furnace at 500 "C for 30 min as described previously by
Holak.8 The ashed sample was dissolved accordingly.
Voltammetric Determinations
The determinations of arsenic, cadmium, cobalt, copper,
lead, nickel, selenium and zinc were performed as de5cribed
previously by the author and co-workers.'.'
Bismuth and
vanadium were determined as described by Velghe and
Claeysg and van den Berg and Huang.10 respectively.
Working Area
This work was carried out in clean air conditions controlled at
a temperature of 22.5 k 0.5 "C. All sample preparations were
performed in a class-100 clean room, and the analytical
measurements in a class-1000 clean room.

Results and Discussion

Nature of Sample Material
The results summarised in Table 1 indicate that the suitability
of either the wet digestion or dry ashing methods for the
voltammetric determination of the trace elements in biological
and environmental materials was dependent on both the
nature of the sample material and the element(s) of interest.
Although no single method was ideal for all sample materials,
the physical state of the sample was an important consideration in the selection of a suitable digestion method. For
example, the decomposition of liquid samples could only be
performed adequately by wet digestion, except in the
instances for which the initial freeze-drying of the liquid
samples permitted the use of the dry ashing methods.

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ANALYST. APRIL_ 19x9. VOL. 114

Table 1. Suitability of direct decomposition methods for the voltammetric determination of tracc elements in biological and environmental
materials

Decomposition
Sample
Elemental
Vo I t a m me t r i c
t YPe
state
technique'
method
Liquid
..
W 2 > W3 > W1
DPCSV at
HMDE
Solid
W2 = D4
DPASV at
..
..
Liquid
W 2 > WI = W3
Bismuth
HMDE
Solid
Dl-D2-D3=W2
Liquid
DPASV at
..
..
W2>W1=W3
Cad m i u m
HMDE
Solid
W 2 = D 2 > D1= D3
..
..
DPACSV, DPP at
Liquid
W2 > w3 > w1
Cobalt . .
HMDEiDME
Solid
D 1 > D3 = D2 > W2
DPASV at
Liquid
..
. .
W2 > W 1 = W3
Copper. .
HMDE
Solid
D1 > D2 = D3, W2
Liquid
Lead . .
..
..
DPASV at
w2 > W3 > W1
D 2 > Dl = D 3 , W2
HMDE
Solid
..
..
DPACSV. DPP at
W2>W3>W1
Liquid
Nickel . .
HMDEIDME
Solid
D l > D3 = D2 > W2
DPCSV at
Liquid
..
..
W2 > w3 > W1
Selenium
IIMDE
Solid
W2 = D3
DPACSV, DPP at
Liquid
W2 > W3 > W1
Vanadium
..
..
HMDEiDME
Solid
W2 = D2
. .
..
DPASV at
Liquid
Zinc
..
W2 > W 1 = W3
HMDE
Solid
W 2 = D 2 > D 1 = D3
* DPCSV = differential-pulse cathodic stripping voltammetry; DPASV = differential-pulse anodic stripping voltammetry; DPACSV =
diffcrential-pulse adsorptive cathodic stripping voltammetry; DPP = differential-pulse polarography; H M D E = hanging mercury drop electrode;
and D M E = dropping mercury electrode.

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Element
..
Arsenic

However, with solid sample materials, both types of digestion

method were generally suitable for the decomposition without
the need for any prior treatment. In terms of the voltammetric
analysis. the criteria used for determining the suitability of the
digestion methods was based on the completeness of the
decomposition, as determined by the presence of the residual
organic matrix and the recovery of the trace elements. The
order of preference indicated for the different digestion
methods in Table 1 represents 95-100"%, 9(&95"/0, 85-90%
and 70-85"/0 recovery of the elements for the first, second,
third and fourth preferences, respectively. On the basis of this
information the two preferred decomposition methods for
the reliable voltammetric determination of trace elements in
liquid and solid biologicalienvironmental materials were the
wet digestion with H N 0 3 - H2S03 and the direct dry ashing
without an ashing aid.
~

Digestion Time

An important consideration for the selection of digestion

methods for the determination of trace elements in biological
and environmental materials is the required digestion time. As
expected, the wet digestion methods were considerably more
rapid, requiring about 2-3 h compared with at least 8 h for
complete decomposition by the dry ashing methods. Generally, the required decomposition time for both types of
decomposition method increased with increasing amount of
sample digested. Hence, the analysis time available was a
major factor influencing the choice of a particular decomposition method for the reliable determination of trace elements
by voltammetry or other analytical techniques.3.4 Iowever,
the preference for a particular method might be influenced by
the extent of the blank contributions that may result from the
digestion. In situations where the extent of the blank
contribution was not considered to be a limitation and the
analysis time available was short, preference was given to the
wet digestion methods. This, in some instances, had serious
consequences on the reliability of the voltammetric analysis,
particularly with respect to the completeness of the sample
decomposition and the resulting background currents associated with the residual acid from the wet digestion methods.
Nevertheless, it is worth noting that these effects were reduced
considerably when wet digestion of the samples was carried
out over a longer period (8-10 h).

Blank Contributions
Generally, the extent of contamination from the sample
decomposition process was greater for the wet digestion
methods in terms of the number and amounts of reagents used
than for dry ashing. particularly if the decomposition was
performed under conventional laboratory conditions.
However, this did not cause a major problem under clean
laboratory conditions because the blank contributions were
easily maintained at very low and constant levels. In this
regard, an attractive feature of the dry ashing methods was
their ability to decompose relatively larger amounts of sample
(up to 10 g) compared with wet digestion, without significant
increases in the decomposition time and the blank contributions. The decomposition of such large amounts of sample by
dry ashing proved useful in reducing the effect of the higher
and variable blank contributions obtained in a conventional
laboratory. Nevertheless, stringent control and maintenance
of the furnace was required in order to avoid or reduce the
irregular and variable blank contributions. This control and
maintenance required an initial firing of the furnace up to
800 "Con a regular basis to remove any residual trace elements
from the digestion chamber, prior to the introduction of the
sample for decomposition at lower temperatures. Table 2
gives the typical residual blank contributions which resulted
before and after furnace conditioning. Evidently, prior
conditioning of the furnace was effective in reducing the blank
contributions significantly and was used prior to all the dry
ashing methods discussed in this paper. In comparison, the
blank contributions from the wet digestion methods given in
Table 3 were generally higher. As can be seen from these data
the blank contributions for these digestion methods increased
with the amounts and number of reagents used for the sample
decomposition.
Determination of Volatile Trace Elements

Selenium and arsenic are two of the highly volatile trace

elements that were studied. Owing to their volatility, the use
of magnesium nitrate as an ashing aid for the dry ashing of the
samples for their determination was mandatory. 11.12 In its
absence, considerable losses of these elements were experienced and the approach was considered unsuitable in terms of

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Table 2. Typical blank contributions from dry ashing in a muffle

furnace based on method D1 and sample dissolution with 0.1 M HCI

Blank contribution'/ Blank contributionti

Element
Llg I - '
1-181-'
Arsenic . . . . . .
<0.05
<0.05
Bismuth . . . . . .
0.11
0.07
Cadmium . . . . . .
0.04
0.01
Cobalt
. . . . . .
0.2s
0.006
Copper
. . . . . .
4.80
0.C)S
Lead
. . . . . .
12.20
0.02
Nickel
. . . . . .
3 .M
0. r)OS
Selenium . . . . . .
<0.01
<0.01
Vanadium
. . . .
0.92
0.03
Zinc . . . . . . . .
0.05
9.65
' Ashing conditions: after several months of idleness and without
initial conditioning of the furnace.
-;. Ashing conditions: with initial conditioning of the furnace at
SO0 "C for >3 h.
Table 3. Typical blank contributions from wet digestion with various
acid mixtures

Blank contributionipg 1
Element
Arsenic . .
Bismuth . .
Cadmium
Cobalt
. .
Copper . .
Lead
. .
Nickel
.
Selenium . ,
Vanadium
Zinc
. .

HNO,
<0.05
0.13
0.042
0.012
0.20
0.33
0.01s
<0.01
0.05
0.20

. .
. .
..
. .
. .
. .
..
..
..

. .

HNO,-I,SOI HNOI-KZS20,
<0.05
<o. 05
0.15
0.48
0.049
0. 1 I3
0.022
0.104
0.26
6.84
0.31
2.35
0.030
0.85
<0.01
<0.01
0.06
0.09
0.52
7.08

0.025 UA

c-'

21
~

0.50

0.3
-

0.4

0.5

0.55

0.75

0.35

0.55

E.'V
Fig. 2. Effect of ( a ) incomplete and ( h ) complete wet digestion on
the determination of Se in Orchard Leaves by DPCSV. ( a ) Samplc
(1 g) plus 50 ng of Se'V. ( h ) Sample (1 g) plus 1.0; 2. 1; and 3 , 2 pg 1 - 1
of SeV'. Final volume = SO ml. Other conditions as in Fig. 1
-

Table 4. Concentrations of selenium found in urine samples by

DPCSV using the proposed digestion procedures

(a:

0.35

0.35

0.6

E!V

Fig. 1. Elfect of ( u ) incomplete and ( h ) complete wet digestion on

the dctcrminntion ot Se in Animal Muscle by DPCSV. ( u ) 1.0; 2, 1;
.3. +2. m d 4, + 4 iig 1 - 1 of SeIb ( b ) 1. 0; 2, + 2 ; m d 3, +4 pg 1 01
Sel\ Electrol>u\ time ( t , ) - 180 s; m i n rate, 2 mV \ I

precision and accuracy. In addition to its role as an ashing aid

for selenium and arsenic, magnesium nitrate was uscd
satisfactorily for the dry ashing of the sample prior to the
voltammetric determination of copper, lead, cadmium, zinc,
nickel and cobalt. The only obvious limitation of this approach
u.as the need to purify the magnesium nitrate in order to
prevent. or reduce the possibility of, sample contamination by
the reagent. Although purification can be accomplished by
controlled potential electrolysis for >24 h , the use of wet
digestion methods would be the preferred approach.
HoLvever. some consideration had to be given to the nature
of the sample when wet digestion methods were used because

Selenium found * /
ng ml- 1
HN03
. . . . . . . . . . . . . . . . 5.2kO.6
HNO, - HZSO, . . . . . . . . . . . . . . 6.9 i 0.3
HNO, - K,SZO, . . . . . . . . . . . . . . 7.2 k 0.3
. . . . 7.0 k 0.5
Dry ashing-l with Mg(NO,)? as ashing aid
* Based on triplicate determinations (+ mean deviation).
t The sample was freeze-dried before ashing.
Digestion mixture

selenium and arsenic are bound more strongly to organic

matrices than are other trace elements. For this reason, some
experimentation was necessary to ensure that the samples
were decomposed sufficiently for the voltammetric determination of these elements. Fig. 1 shows that the digestion of
Animal ,Muscle with only two further additions of nitric acid
(method W l ) gave a broad and less sensitive voltammetric
response for selenium [Fig. l(a)] than did a sample digested
further as described in method W2 [Fig. l(h)]. Similarly. the
digestion of Orchard Leaves with {NO3 - H2S04, which
produced a slightly yellow clear solution, gave a broad peak at
about -0.66 V [Fig. 2 ( a ) ] and was not useful for the
quantification of selenium. In contrast, further digestion of
the sample to a clear colourless solution produced a well
defined peak which increased with increasing additions of
selenium to the solution [Fig. 2(b)]. In this instance, the
selenium peak appeared at about -0.60 V , which was more
positive than the peak observed for the incompletely digested
sample. Also, the sensitivity of the measurement for the
completely digested sample decreased considerably [Fig.
2(h)], possibly owing to the removal of organic substances that
may have been present in the incompletely digested sample
and which subsequently catalysed or enhanced the electrode
process [Fig. 2 ( a ) ] . The 60-mV difference in peak potential
measured in each instance clearly indicated that the electrode
processes for the second peak appearing in Fig. 2 ( a ) and ( h )
are different. However, the result of 0.078 -t 0.004 pg g-1
obtained using thc second peak at -0.60 V [Fig. 2 ( h ) ]for the
quantification of selenium in completely digested Orchard
Leaves compared favourably with the certified value of 0.08 2
0.01 ug g-1. Evidently, the wet digestion of biological and
Gnuironmental materials for the voltammetric determination
of selenium and arsenic should be considered incomplete until
a clear, colourless solution is obtained. The additional peak in
Fig. 2 at about -0.45 V was due to the presence of excessive
amounts of lead in the Orchard Leaves sample. According to
the certified values, the sample contained 45 k 3 pg g-1 of
lead, which was equivalent to 900 ug 1-1 in the final solution.

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bl

t
4-

2
3

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0.8

1.o

1.2

1.o

0.8

1.2 0.8

0.9

1.0

1.1

-EN

Fig. 3. Comparison of ( a ) direct dry ashing without an ashing aid

with ( b ) wet digestion with HNO, and (c) wet digestion with HNO, K2S20, for the determination of Ni and Co in Oyster Tissue by
DPACSV. ( a ) 1,O; 2, +6 pg 1 - 1 of Niplus 3 pg I - ' of Co; 3, +12 pgl I
of Ni plus6 pg1 I of Co. ( b )and (c) 1 , O ; 2, + 2 pgl-1 of Niplus 1 pgl-1
of Co; 3, + 4 pg 1 - 1 of Ni plus 2 pg 1-1 of Co; 4, +6 pg 1 - l of Ni plus 3
pg 1 I of Co. Accumulation time (t',) = 60 s; scan rate, 4 mV s-l;
[dmgH2], 2 x 10-1 M ; 0.3 g of sample in 50 ml

The requirement for the complete decomposition of biological and environmental materials for the cathodic stripping
voltammetric determination of selenium and arsenic is further
demonstrated by the results given in Table 4. It can be seen
that the selenium concentrations obtained for the urine
sample by wet digestion with the H N 0 3 - H2S04 and H N 0 3 K2S208 mixtures and by dry ashing with Mg(N03)2 as an
ashing aid were comparable. The lower selenium concentration obtained by wet digestion with H N 0 3 only was due to the
incomplete decomposition of some of the organic matrix.
Similar observations have been made by Neve et a1.15 who
found that wet digestion with H N 0 3 only gave erroneous
results for the determination of selenium by atomic absorption
spectrometry because of the incomplete mineralisation of
some organic selenium compounds including selenium derivatives, which are the main metabolites of the element in urine.
With voltammetric techniques, the adsorption of the incompletely digested organic matrix inhibits the electrode process
and distorts the response due to the catalysis of the evolution
of hydrogen. The complete destruction of the organic matrix
by wet digestion with HNO? only seems to be limited by the
low boiling-point of this acid. Repeated digestion of the urine
sample with additional nitric acid did not improve the recovery
or precision of the wet digestion procedure for the voltammetric determination of selenium.

Determination of Other Elements

Of all the digestion methods investigated, the direct dry ashing
method without an ashing aid proved to be the most suitable
for the accurate determination of bismuth, cadmium, cobalt,
copper, lead, nickel, vanadium and zinc. This method was
particularly advantageous in reducing the extraneous additions that result from the use of reagents as ashing aids or for
wet digestion. Complete recovery of thcse elements was
accomplished at an ashing temperature of 450 "C. Although
the other dry ashing and wet digestion methods were also
adequate, careful control of the analytical blank variability
was necessary to ensure that the results were reliable. The
data given in Table 3 indicate that the blank contributions
from the wet digestion with acid mixtures were generally

0.8

1.o

1.2

-EN

Fig. 4. Determination of Ni and Co in Orchard Leaves by DPACSV

after decomposition by direct dry ashing without an ashing aid. 1,O; 2.
+2.5 pg 1-1 of Ni plus 0.5 pg 1 1 of Co; 3, +S.0 pg 1 I of Ni plus 1.0
pg 1 - I of Co; 4, +7.5 pg 1 - 1 of Ni plus 1.5 pg 1 - 1 of Co; [drngH,], 1 X
10 4 M ; 0.2 g of sample in 50 ml. Other conditions as in Fig. 3

0.85

0.65

0.45

-EN

Fig. 5. Determination of Cd and P b in Oyster Tissue bv DPASV

after decomposition by wet digestion with HNO, - H2S04.1,O; 2, +2;
3, +4 pg 1-1; f, = 120 s; scan rate, 4 mV s-1; 0.3 g of sample in 250 ml

higher than for dry ashing in the muffle furnace (Table 2).
Further, the resulting sensitivities and background currents
for the voltammetric determination of the elements were
dependent on the nature of the chosen decomposition
method. Fig. 3 shows that the background current for the
determination of nickel and cobalt in Oyster Tissue digested
by the direct dry ashing technique without an ashing aid was
considerably lower than those obtained with the wet digestion
methods. Such high background currents can affect the
accuracy of the voltammetric peak measurements and, hence,
reduce the reliability of the method. However, unlike wet
digestion with H N 0 3 only [Fig. 3(b)] the inclusion of
potassium persulphate in the digestion mixture [Fig. 3(c)]
reduced the background current in the region of positive
potential. Such a reduction in the background current is
undoubtedly due to improved decomposition with the H N 0 3 K2S20Xmixture, as is already evident from the selenium
results in Table 4. Further, previous evidencelh.17 has indi-

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460
Table 5 . Comparison of the wet digestion method using H N 0 3 H,SOI with the direct ashing method without an ashing aid for the
voltatnmetric determination of Cd. Pb, Co and Ni in Oyster Tissue

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Wet
Certified
Voltammetric digestion/ Dry ashing*/ value-i./
Element
technique
pg gPgg-
ELsg
3 . 1 4 k 0 . 1 2 3 . 2 2 k 0 . 1 7 3.5 kO.3
DPASV
Cadmium . .
0.51 10.02 0.50 k 0.05 0.48 t 0.04
DPASV
Lead . . . .
0.4$
0.32 k 0.04 0.37 k 0.04
Cobalt
. . DPACSV
1.12 2 0.05 1.10 i 0.04 1.03 k 0.19
Nickel
. . DPACSV
Triplicate determinations (imean deviation)
f The error is the standard deviation.
Non-certified value.
Table 6. Comparison between open and closed wet digestion
procedures using HNOi - H,S04 for the CSV determination o f
se I e n i u in
Animal Muscle/ Bovine Liver/
Mode of digestion
pgg IofSe
p g g IofSe
Closed
..
..
..
0.273 t 0.005
1.08 2 0.0 1
Open . . . . . .
..
0.288 -t 0.002
1.13 k 0.03
Certified values+ . . . .
0.28 k 0.03
1 . 1 50.1
* The error is the mean deviation based on triplicate determinations.
f The error is the standard deviation based on the results obtained
by various inst r u me n t a1 tech n i q ues .

cated that the adsorption of organic residues might inhibit the

electrode process and distort the response due to the catalysis
of hydrogen evolution. Hence, the effects of the catalysed
hydrogen evolution would be expected to be more pronounced in samples with high residual acids. Generally,
incomplete sample decomposition would result in the retention of unused acids, in addition to undigested soluble organic
residues.
Fig. 3 also shows that the sensitivities obtained for nickel
and cobalt were generally much improved for the sample of
Oyster Tissue digested by the direct dry ashing method
without an ashing aid. The lower sensitivity obtained with wet
digestion with H N 0 3 only was due partly to incomplete
decomposition and, possibly, partly to the presence of residual
acid in the sample solution which required neutralisation with
higher concentrations of ammonia buffer. Previously, it was
demonstrated that the sensitivities of nickel and cobalt are
affected by such high concentrations of ammonia buffer. The
completeness of the decomposition by wet digestion was
improved with the use of the H N 0 3 - K2S208mixture. Similar
effects on the sensitivities of the voltammetric determination
of bismuth. copper, lead, vanadium and zinc in biological and
environmental materials were observed for the different
digestion methods. The dry ashing method was, therefore,
more suited for the voltammetric determination of bismuth,
cobalt, copper, lead, nickel, vanadium and zinc in these
materials in terms of sensitivity, background current, completeness of sample decomposition and reliability of the
results. Fig. 4 shows that the dry ashing method was also
adequate for the voltammetric determination of nickel and
cobalt in Orchard Leaves.
The anodic stripping voltammetric determination of cadmium in biological and environmental materials showed the
least dependence on the type of decomposition method used.
Generally, the wet digestion and dry ashing methods were
equally adequate for the determination of this element,
indicating that cadmium is not as strongly bound to the organic
matrix as are selenium, arsenic or zinc. However, for dry
ashing, careful dissolution of the sample in a suitable acid was
necessary to obtain reliable results by the voltammetric
technique. In this regard, the dissolution of the ash in
hydrochloric acid was more satisfactory than that in nitric acid
in terms of peak resolution, sensitivity and reliability of the

results.i This did not create any problems with the wet
digestion methods, provided that thc sample was digested
carefully as described in this paper. Nevertheless, the background currents of the sample decomposed by wet digestion
were very high as shown in Fig. 5 for the determination of
cadmium and lead in the sample of Oyster Tissue. In
comparison, the background currents for samples decomposed by the dry ashing methods were generally much lower,
as demonstrated previously.-? The data given in Table 5
provide a more direct comparison between the two preferred
decomposition methods for the reliable voltammetric determination of cadmium, lead, nickel and cobalt in the Oyster
Tissue sample. Both sets of results agree favourably with the
certified values and hence verify their suitability for the
voltammetric determination of these elements in similar
biological and environmental materials.

Decomposition of a Complex Sample Matrix

One of the complex sample matrices encountered i n this study

was that of a sediment sample containing a highly siliceous
component. Neither the wet digestion nor the dry ashing
methods described here allowed complete decomposition to a
form suitable for the voltammetric determination of the trace
elements. It was necessary with both types of digestion
method to decompose the sample further with small aliquots
(1-2 ml) of hydrofluoric acid. For the dry ashing methods, it
was necessary to add some nitric acid (2-5 ml) in addition to
the hydrofluoric acid to allow adequate dissolution of the ash.
This additional step proved successful for the reliable quantification of the trace elements in the sediment sample by
voltammetric techniques with both types of digestion.
However, it was necessary, for both methods of decomposition, to perform the dissolution step in a PTFE vessel at
200 C in order to avoid reaction between the acid and the
digestion vessel. This precaution also avoided serious contamination of the sample resulting from such a reaction.

Modes of Wet Digestion

Typically, the wet digestion of a sample can be performed in
one of two modes, namely, in an open system, as in this
study, or in a closed system, which usually involves carrying
out the digestion under refluxing conditions or in pressure
bombs. For ubiquitous elements such as copper, lead and zinc,
the closed mode of wet digestion was beneficial in reducing
atmospheric contamination and minimising the use of
reagents. However, for non-ubiquitous elements such as
selenium and arsenic. the benefit of the closed mode over the
open mode was marginal. This is supported by the results
given in Table 6, which compares the wet digestion of some
biological materials with the H N 0 3 - HzSOj mixture in the
open and closed mode for the cathodic stripping voltammetric
determination of selenium. Evidently, both modes of wet
digestion were equally suitable for reliable determination of
the element. The significant difference between the two
modes was that the amount of reagent used in the closed
system was about half that used in the open mode, which
represents a significant decrease in the reported blank
contributions (Table 3), particularly for the ubiquitous elements. Nevertheless, the time required for the complete
decomposition of the samples in the closed system for the
voltammetric determinations of the trace elements was at least
twice that required for the open system, depending on the
amount of sample used. Ultimately, the critical factors
influencing the choice of mode in real situations were the
analysis time available and the concentrations of the elements
to be determined in the sample, particularly with regard to the
extent of blank contributions that can be tolerated.

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46 1

ANALYST. APRIL 1989. VOL. 113

Conclusion

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Published on 01 January 1989 on http://pubs.rsc.org | doi:10.1039/AN9891400455

The reliable voltammetric determination of trace elements in

biological and environmental materials require5 careful consideration of the choice of decomposition method. In particular, factors such as the nature of the sample, the sample
matrix, the amount of sample, the analysis time available,
blank contributions, the resulting sensitivity and the background current must be given due consideration. For the two
most suitable decomposition methods in this study, namely
wet digestion with HNO? - H2S04 and direct dry ashing
without an ashing aid, the precision for the voltammetric
determination in liquid and solid samples was in the range
1-3%.
The author is grateful to the Graduate Studies and Research
Committee at Deakin University for providing the research
grant for this work and he acknowledges the use of the
U n i ve r si t y s CIe an Labor at or y Com p 1ex.

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Paper 8103122C
Received August l s t , 1988
Accepted October 31st, I988