Microwave-Assisted Sample

Digestion
Nabil Bader
 Microwave-Assisted Sample
Digestion
As in the case 0f extraction, microwaves are
applied to heat the solvent above its boiling point,
as well as to accelerate the digestion of sample for
AAS, ICP-AES, or ICP-MS determination of
inorganic content in solid samples.
"Microwave sample preparation reduces the
environmental exposure as the sample retains
the clean environment, excludes additional
environmental sources of contamination, and
makes isolation more feasible."— Microwave-
Enhanced Chemistry,
Kingston H.M., Haswell S.J. Eds.
American Chemical Society, Washington D.C.
1997
Closed-vessel microwave decomposition offers the following
benefits:
• The environment in which the reaction takes place is clean,
closed, and controlled
• The amount of acid is diminished to stoichiometric quantities
of the reagents, further reducing contamination
• ppb, ppt sensitivities
• Shorter reaction time and improved digestion due to higher
temperatures (far above the normal boiling point of the
reagents)
• Easy-to-use control software for reproducible results
• No loss of volatile elements
Improved Trace-Level Results
Comparison of analytical blank results obtained from hot
plate and microwave digestion of a certified reference soil.
Concentration expressed as μg/g.

Certified Value Microwave Hot Plate Analyte

17.7 ± 0.8 17.6 ± 0.9 12.3 ± 2.27 As

0.38 ± 0.01 0.41 ± 0.06 0.31 ± 0.09 Cd
130 ± 4 123 ± 3 68.8 ± 7.5 Cr
34.6 ± 0.7 33.5 ± 1.2 23.8 ± 2.7 Cu
18.9 ± 0.5 17.5 ± 1.1 10.8 ± 1.3 Pb
1.40 ± 0.08 1.42 ± 0.10 0.97 ± 0.14 Hg
88 ± 5 83.2 ± 3.0 63.4 ± 3.9 Ni
1.57 ± 0.08 1.54 ± 0.33 1.61 ± 0.34 Se
0.74 ± 0.05 0.63 ± 0.02 0.29 ± 0.05 Tl
112 ± 5 119 ± 6 65.6 ± 8.8 V
106 ± 3 102 ± 6.1 113 ± 13.5 Zn
Complete Analyte Recovery with Microwave
Evaporation

In addition to its utility for sample digestion,

microwave energy can also be used for post-
digestion processing, of which the most common
step is evaporation. This is done to concentrate the
sample when the initial analyte levels are below the
instrument limit of detection, or because the matrix is
incompatible with the detection method.
• The use of traditional hot-plate evaporation methods can lead to
losses of volatile analytes, because the sample is overheated as it
approaches dryness. In contrast, the unique heating mechanism
exclusive to microwave heating allows the temperature to decrease as
the sample approaches dryness, preventing the loss of volatile
elements.
GENERAL SAFETY CONSIDERATIONS

1. All vessel components must be dry and free from

particulate matter.

2. Never heat liquids in a sealed vessel or container that is

not equipped with a pressure relief device.

3. Never attempt to digest samples larger than 0.5 grams if

the organic content or the composition is unknown.
4. When working with an unknown sample, always
perform a pre-digestion step in an unsealed, open
vessel, allowing a minimum of 15 minutes for the
reaction of volatile or easily oxidised compounds to
subside before sealing the vessel and microwave
heating.

5. Do not heat high boiling point acids ( concentrated

sulphuric or phosphoric acids) inside microwave
digestion vessels. These acids will heat to temperatures
beyond the melting point of the polymeric materials used
in the construction of the digestion vessels.
 Microwave-Assisted Solvent
Extraction (MWE)
Samples submitted for organic analysis can rarely be
used in their raw state, and require pre-treatment.
The principal step in sample pre-treatment is
extraction of the analytes of interest from the sample
matrix. This is the least evolved (many people still use
the Soxhlet method invented in 1879), most error-
prone step in the analytical procedure.
The use of laboratory microwave ovens for organic
extraction elevates sample preparation to the same
level of sophistication as sample analysis.
 Benefits of Microwave-Assisted Solvent Extraction
(MWE)

• Speed. Microwave extractions can be completed within minutes—a

fraction of the time, compared to older methods.
• Economy. Lower solvent usage reduces the costs of solvent purchase
and disposal.
• Effectiveness. Microwave extraction produces higher analyte
recoveries than older methods.
• Simplicity. Use polar or non-polar solvents; no need to modify your
existing chemistry.
 Ultrasonic Extraction
• Ultrasonic extraction can be used with many solvents.
• Sample preparation is simple. Thus, the solid sample is deposited in a
suitable vial, extracted for 15-30 minutes, and the extract is separated
from the solid residue.
• Potential problems are re-adsorption of the analyte
onto the solid, heat of the sample and thus loss of the
extraction solvent, and decomposition of the analyte
due to zones of high energy
Sample-to-sample cross-
contamination
Sample-to-sample cross-contamination can be a
problem when microwave vessels and other clean
chemistry accessories are not cleaned and stored
properly.
Sample Size Reduction
􀂄 Finely divided state: Homogeneous
􀂄􀂄 -Secondary sampling can be performed with
greater precision and accuracy
􀂄􀂄 -Easily dissolved and extracted
􀂄􀂄 Hard materials
-Grinding with a mortar or pestle, and
pulverizing
􀂄􀂄 Soft materials (meat, vegetable)
-Milling, mincing, homogenizing, macerating,
crushing and blending