0010 This preparation can be omitted in some samples,
especially in beverages, such as tap water or wine,
where, in the latter, a simple dilution of the sample
can be sufficient. Nevertheless, in most food and
beverage samples, the destruction of the organic
matter is necessary to a greater or lesser degree,
depending on the technique of analysis to be applied.
0011 The sample preparation is a critical step in trace-
element analysis. The classic standard methods for
organic-matter destruction are: wet digestion by
conductive heating (hot plate, digestion block) or
dry ashing (muffle furnace) at a defined temperature.
Wet-digestion methods are generally more rapid than
dry digestion methods. The disadvantages are that
only fairly small samples can be used and also
that the digests normally have to be heavily diluted
before the analysis, resulting in poor detection limits.
These techniques usually use mineral acids, oxidants,
and ashing aids. Wet digestions can be carried out
with a concentrated acid or mixture of acids, in
open or closed systems. Since 1975, microwave-
assisted sample digestion has been increasingly used
for sample preparation in trace-element determin-
ation in food samples.
0012 The advantages of microwave digestion over con-
ventional sample preparation techniques are: a reduc-
tion in the time needed for the sample preparation and
also of the amounts of acids used for digestion,
and the possibility of controlling pressure/tempera-
ture, automation, and flexibility in sample prepar-
ation. Two types of microwave digestion systems are
now available for wet digestions: closed-vessel micro-
wave and open-vessel focused microwave.
0013 Each of these techniques offers specific advantages.
Closed systems can be used to prepare samples under
controlled digestion conditions with a minimal volume
of acid and a reduced risk of contamination. Nitric,
hydrochloric, and hydrofluoric acids and their
mixtures are the most widely used with closed digestion
vessels. Nitric acid is usually added due to its antioxi-
dant properties, and hydrofluoric acid is used when
siliceous matter is present. The addition of hydrogen
peroxide to nitric acid is also recommended.
0014 Automated focused open-vessel microwave systems
operate at ambient pressure and offer flexibility in
digestion conditions, with vessels and reflux columns
available in borosilicate glass, Teflon perfluoralkoxy,
and quartz. These systems can be used to prepare
samples sequentially with minimal attended operation,
since digestion reagents are added automatically in
programmed volumes and dispensing rates. To minim-
ize analyte losses, a ramped, multistage heating pro-
gram can be used in addition to reflux columns with the
digestion vessels. When compared with the closed
vessel system, the open-vessel system can process
large samples, which leads to lower detection limits.
High-pressure and high-temperature conditions are not
required to obtain a complete digestion when an instru-
mental technique such as ETAAS is used for trace-
element analysis.
0015Precautions should be adopted in all wet-digestion
procedures when strong acids and strong oxidizing
agents are used. The formation of explosive nitro
compounds has been reported when fat-rich samples
have been digested with nitric acid. Whichever wet
digestion procedure is applied, the digests are left to
cool and diluted with water.
0016Dry digestion or ashing procedures are also widely
used to destroy organic matter. The main problems
with these procedures are the possible losses of ana-
lyte by volatilization or by retention on crucible walls
during dry ashing. Although several studies strongly
indicate that ashing at temperatures up to 450
Cis
free of losses by volatilization or retention, it is rec-
ommended that the temperature be increased grad-
ually up to 400–500
C and maintained until white
ashes are obtained. Dry ashing is time-consuming,
usually taking a day or more, although it requires
very little attention from the analyst. The resulting
ash can be dissolved in a small amount of solvent, and
contamination through reagents is scarce.
0017To eliminate potential losses and/or to speed up the
ashing procedure, ashing aids and matrix modifiers
can be used. This, however, always increases the risk
of contamination and worsens detection limits. Ashes
are usually dissolved in diluted HCl or HNO
3
and it is
sometimes necessary to heat them with concentrated
HNO
3
and HClO
4
until no more fumes are produced,
in order to complete the destruction of the organic
matter. In some cases, organic-matter destruction can
be replaced by acid extractions of the food product.
Hydrochloric acid, nitric acid, or a mixture is used as
the extractant, and the use of an ultrasonic bath
facilitates the extraction.
0018Some analytical techniques that are useful for
copper determination, such as ETAAS, do not require
organic-matter destruction in some kinds of food.
Nevertheless, even when this is not the case, a com-
plete digestion, minimizing residual carbon content,
is not required. The suppression of the digestion step
will reduce the time needed for the analysis and the
risk of losses and contaminations. Organic-matter
destruction and dilution or dissolution of the residue
can be replaced by:
.
0019direct injection of the sample (water) or after the
appropriate dilution (wine);
.
0020dissolution of the sample in an adequate solvent,
e.g., butter in the mixture composed of butylamin/
water/tetrahydrofuran (48/12/40);
COPPER/Properties and Determination 1635