146 SAMPLE DISSOLUTION FOR ELEMENTAL ANALYSIS / Wet Digestion

1,3-dibromo-5,5-dimethylhydantoin (DBH). Part 1, oxy- Okamoto T, Isozaki A, and Nagashima H (1996) Deter-
gen flask combustion, Part 7. Fresenius Journal of mination of chloride, bromide and sulfate in color add-
Analytical Chemistry 360: 184–191. itives by ion chromatography on ceramic carbon column.
Kowalenko CG (2000) Influence of sulfur and nitrogen Bunseki Kagaku 45: 865–871.
fertilizer applications and within-season sampling time Soon YK, Kalra YP, and Abboud SA (1996) Comparison of
on measurement of total sulfur in orchardgrass by six some methods for the determination of total sulfur in
different methods. Communications in Soil Science and plant tissues. Communications in Soil Science and Plant
Plant Analysis 31: 345–354. Analysis 27: 809–818.
Kuboyama K, Sasaki N, Nakagome Y, Kataoka M, and Sun Y and Li H (2000) Determination of trace selenium
Tamura C (1996) Simultaneous microdetermination of flu- in human plasma and hair with ternary inclusion
orine, chlorine, bromine and sulfur in organic compounds compound-fluorescent spectrometry. Analyst 125:
by ion chromatography. Bunseki Kagaku 45: 71–76. 2326–2329.
Nagashima H and Kuboyama K (1996) Microdetermina- Woodget B (1995) Oxygen flask combustion. In: Townsh-
tion of phosphorus in organic compounds by ion chro- end A, Worsfold PJ, Haswell SJ, et al. (eds.) Encyclope-
matography. Bunseki Kagaku 45: 941–946. dia of Analytical Science, 1st edn., pp. 4495–4502.

Wet Digestion
R M Twyman, University of York, York, UK facilitate dissolution. Minerals and coal often have a
& 2005, Elsevier Ltd. All Rights Reserved. nonuniform distribution of elements, while fly ash is
very fine and is composed of metal silicates and ox-
This article is a revision of the previous-edition article by A D
ides. Both these types of sample are difficult to sol-
Sawant, pp. 4503–4510, & 1995, Elsevier Ltd.
ubilize. Similarly, alloys can be difficult to dissolve
because of the strong bonds between metal atoms
and their brittle nature. Solid and crystalline samples
Introduction may possess interstitial water and water of crystal-
lization, so thorough drying of samples is necessary
Wet digestion methods for elemental analysis involve before and after grinding.
the chemical degradation of sample matrices in solu- Biological samples must be processed with great
tion, usually with a combination of acids to increase care, since the dissolution and total decomposition of
solubility. The various acid and flux treatments are all organic matter is required for the release of trace
carried out at high temperatures in specially designed elements. However, the use of oxidizing acids to de-
vessels that help to minimize contamination of the compose organic matter can produce violent reac-
sample with substances in the air, the local environ- tions and the alternative procedure of dry ashing may
ment, and from the vessel walls. Losses from the be more suitable in some cases. Environmental and
sample may occur due to adsorption onto the vessel water samples often contain mixtures of organic and
walls, volatilization, and coextraction, but these can inorganic substances, so dissolution techniques need
be reduced by procedural modifications. The use of to be modified to take this composition into account.
closed systems, where the digestion reaction is com- In particular, water samples may contain dissolved
pletely isolated from the surroundings, may help to and suspended solids, colloids, and microorganisms.
reduce both contamination and sample loss. Elements embedded in such samples may be present
both in dissolved and solid forms. The nature of the
The Nature of the Sample Matrix sample matrix must be given special attention during
wet digestion.
Many techniques employed for elemental analysis
require the conversion of the sample matrix into a
solution form. The selection of an appropriate treat-
Extraction of the Analyte
ment for sample dissolution depends on the nature of Solid samples generally contain some adsorbed and/
the sample, and different approaches are required for or absorbed water. In the case of inorganic materials,
predominantly inorganic and predominantly organic drying is carried out in an oven at 105–1101C for a
matrices. Geological, geochemical, and soil samples few hours, although lower temperatures need to be
generally contain silicate, metal oxides, carbonates, used if the sample contains volatile components. On
and, in many cases, organic matter. Such samples the other hand, higher temperatures may be required
must be dried and ground to a fine powder to to remove water trapped within crystalline matrices.
 SAMPLE DISSOLUTION FOR ELEMENTAL ANALYSIS / Wet Digestion 147

Frequently, the sample is not soluble in water and by nonoxidizing acids is a process of hydrogen re-
must be treated with acids or mixtures of acids to placement.
facilitate solubilization. The type of acid treatment Hydrochloric acid will dissolve metals above the
must be given careful consideration, since particular standard reduction potential of hydrogen, salts of
acids may or may not oxidize the sample, and may be weak acids, and many oxides. Dilute sulfuric and
incompatible with certain elements. For example, perchloric acids are useful for metals above the
sulfuric acid cannot be used to dissolve samples con- standard reduction potential of hydrogen. Hot, con-
taining barium, while hydrochloric acid cannot be centrated sulfuric acid will often dissolve metals be-
used to dissolve silver or samples containing lead and low the standard reduction potential of hydrogen.
lead compounds. The choice of acid is also restricted The most potent oxidizing conditions are obtained
by sample volatilization, e.g., hydrochloric acid using hot concentrated perchloric acid, which will
should be avoided in samples containing arsenic dissolve all common metals. Concentrated hydro-
since this is more volatile as a trichloride. chloric acid is an excellent solvent for many metal
Naturally occurring inorganic materials, such as oxides as well as those metals that are more easily
ores, must be given special treatments to facilitate oxidized than hydrogen. In addition, it is often a
solubilization. The two most common methods em- better solvent for oxides than the oxidizing acids.
ployed in dissolving samples are treatments with hy- Hot, concentrated nitric acid will dissolve all com-
drochloric, hydrofluoric, nitric, sulfuric, or perfluoric mon metals with the exception of aluminum and
acids (or various combinations thereof) and fusion chromium, which are passive to the reagent as a result
with an acidic or basic flux followed by treatment of surface oxide formation. Hot nitric acid also readily
with water or an acid. Organic materials are usually oxidizes many organic substances. Hot, concentrated
decomposed by wet digestion with a boiling ox- sulfuric acid can be used to decompose and dissolve
idizing acid or acid mixture, ultimately producing many substances in part because of its high boiling
carbon dioxide, water, and other volatile compounds point (3401C), and it is particularly useful for the de-
that are driven off to leave behind salts or acids of hydration and oxidation of organic samples. Most
the inorganic constituents of the sample. Wet digest- metals and alloys are also attacked by this hot acid.
ions may be performed in open beakers on hot plates, Perchloric acid is a potent oxidizing agent that
but Kjeldahl flasks or specially designed containment leads to the formation of highly soluble perchlorate
vessels give results that are more satisfactory. salts. As with sulfuric acid, perchloric acid dehy-
drates and oxidizes organic samples very efficiently.
Wet Digestion with Single Acids It also attacks iron alloys and stainless steel, which
are resistant to other mineral acids. Care is required
The solvent action of an acid depends on several when using perchloric acid because it is explosive in
factors: contact with certain organic compounds and easily
oxidized inorganic materials. Special chemical hoods
1. The reduction of hydrogen ions by metals that are are recommended. Perchloric acid, as a 72–74%
more active than hydrogen, for example: solution, boils at 2031C.
Zn(s) þ 2 H þ -Zn2 þ þ H2(g). Hydrofluoric acid is a weak, nonoxidizing acid
2. The combination of hydrogen ions with anions of that is particularly useful for dissolving silicate sam-
a weak acid, for example: CaCO3(s) þ 2 H þ ples since it removes the silicon quantitatively as
-Ca2 þ þ H2O þ CO2(g). volatile SiF4. In many cases, hydrofluoric acid disso-
3. The oxidizing properties of the acid anion, for lution can be achieved by adding sodium fluoride to
example: 3Cu(s)þ2NO3 þ8 H þ-3NO(g)þ4H2O. samples treated with hydrochloric acid.
4. The tendency of the acid anion to form soluble
Wet Digestion with Acid Mixtures
complexes with the sample cation, for example:
Fe3 þ þ Cl -FeCl2 þ . Acids in combination are preferred for certain
inorganic matrices and are generally more advanta-
Ideally, the chosen reagent should cause the com- geous for the decomposition of organic compounds.
plete dissolution of the sample. As a general guide it Wet digestion procedures using acid mixtures can be
is useful to classify the more common acid treatments divided into four types:
according to whether they oxidize the sample or not.
The nonoxidizing acids include dilute hydrochloric, 1. Total decomposition, usually with hydrofluoric
hydrofluoric, sulfuric, and perchloric acids, whereas acid and another mineral acid.
the oxidizing acids include hot, concentrated nitric, 2. Strong attacks, for routine analysis but leaving
sulfuric, and perchloric acids. Dissolution of metals a residue of certain minerals, particularly
148 SAMPLE DISSOLUTION FOR ELEMENTAL ANALYSIS / Wet Digestion

silicates. Carried out with various mixtures of fumes appear. There is little danger of perchloric acid
sulfuric, nitric, and perchloric acids. explosions as long as sufficient nitric acid is present
3. Moderate attacks, using weaker acid mixtures. to decompose the bulk of the organic matter, and as
4. Partial digestions (acid leaching). long as sulfuric acid remains after the perchloric acid
has evaporated to prevent the sample becoming dry.
Both (3) and (4) are typically employed for environ- Perchloric acid should never be added directly to an
mental analysis where complete dissolution is either organic sample. A mixture of nitric and perchloric
not required or is undesirable and the goal is to acid may also be used.
determine the presence of certain trace elements. The availability of strong hydrogen peroxide so-
For geochemical samples containing silicates, the lutions allows a combination of sulfuric acid and
matrix is decomposed by heating with hydrofluoric hydrogen peroxide to be used for the decomposition
acid in combination with either nitric or perchloric of organic matter. Hydrogen peroxide is a vigorous
acid, each of which has a higher boiling point than oxidizing agent and is particularly useful for the
hydrofluoric acid. The presence of the second acid degradation of resistant plastics. There is little
with a higher boiling point ensures that, once the danger of explosion if sulfuric acid is present in ex-
hydrofluoric acid has been boiled off and the dry cess. Most elements can be recovered quantitatively
sample redissolved, sparingly soluble metal fluorides in this procedure, with the exceptions of ruthenium,
are converted to salts that are more soluble. As stated osmium, germanium, arsenic, and selenium. In the
above, however, caution should be exercised with the case of germanium and arsenic, loss is attributable to
use of perchloric acid if the sample has a significant volatilization of chlorides. Additionally, precipitated
organic component. Perchloric acid is also more calcium sulfate may retain lead and silver if not sol-
expensive than nitric acid, and can introduce chlo- ubilized. After decomposition, the sulfuric acid solu-
ride ions as contaminants. tion should be diluted and boiled gently for 10 min to
For organic samples, a widely used mixture is aqua destroy any remaining hydrogen peroxide.
regia (1:3 nitric acid–hydrochloric acid). The nitric The recovery of trace elements after wet digestion
acid acts as the oxidizing agent, while the hydro- using the methods described above is compared in
chloric acid provides the complexing properties. Tables 1 and 2.
The addition of bromine or hydrogen peroxide can
sometimes increase the solubilizing power of mineral
acids. Wet digestion is generally carried out in open
flasks, covered loosely to avoid atmospheric conta- Table 1 Recovery of trace elements after wet digestion of
mination. However, it is becoming increasingly cocoa
common to use closed vessels, such as polytetraflu- Element Recovery a (%)
oroethylene (PTFE)-lined containers or ultrapure
quartz vessels, especially for small samples. HNO3 HNO3, HClO4 HNO3 HNO3
& HClO4 & H2SO4 & H2SO4
A 1:4 mixture of sulfuric and nitric acids is also
widely employed for organic samples. The nitric acid Ag 91 99 100 95
decomposes the bulk of the organic matter but does As 99 99 98 91, 98
Cd 101 102 102 99
not reach a temperature sufficient to destroy the last
Co 98 99 101 100
traces. However, as the nitric acid boils off, the sulf- Cr 100 101 100 101
uric acid is left behind. Dense SO3 fumes evolve and Cu 100 99 100 100
begin to reflux in the flask, making the solution very Fe 99 99 102 97
hot and allowing the hot sulfuric acid to decompose Hg 79 89 93 –
Mo 97 98 101 98
the remaining organic matter. Because of the fumes
Pb 100 99, 93 90, 93 100
produced in this method, it must be carried out under Sb 99, 94 100 100 97
a fume hood. More nitric acid may be added to Se 101 101 79 1
prolong the digestion and eliminate any stubborn Sr 100 97 98 95
organic material. Zn 99 101, 94 100 99
A very efficient acid mixture is nitric, sulfuric, and a
Oxidation mixtures respectively as follows:
perchloric acid in a volume ratio of B3:1:1. For a 15 ml concentrated HNO3, 10 ml 60% HClO4.
typical 10 g sample of tissue or blood, 10 ml of this 15 ml concentrated HNO3, 5 ml conc. H2SO4, 10 ml 60% HClO4.
15 ml concentrated HNO3, 10 ml conc. H2SO4.
solution is sufficient for complete dissolution. The
Concentrated and fuming HNO3.
samples are heated until the nitric acid boils off and 500 ml flask used for 2 g cocoa sample.
perchloric acid fumes begin to appear. Heating con- Radioactive nuclides were used to determine recovery of
tinues until the perchloric acid boils off and SO3 1–10 mg kg 1 level.
 SAMPLE DISSOLUTION FOR ELEMENTAL ANALYSIS / Wet Digestion 149

Wet Digestion with Fluxes (e.g., lithium metaborate, typically used at a 3:1
flux–sample ratio, introduces lithium and boron),
Some materials are particularly resistant to acid
loss of materials by volatilization, and the enc-
digestion, e.g., certain rocks, mineral oxides, phos-
ouragement of sample contamination from the vessel
phates, and some iron alloys. For these samples,
walls, which also become solubilized. The properties
high-temperature fusion with an acidic or basic flux
of some useful fluxes are summarized in Table 3.
such as lithium metaborate (LiBO3) in the molten
state can be used to render such materials soluble in
water or dilute acid. Fusion decompositions are the Dissolution Techniques
most rigorous methods available and all silicate ma-
terials, including refractory substances like zircon Depending on the nature, origin, sample quantity,
and cassiterite, can be dissolved completely when elements of interest, and concentration range, a
fused with an appropriate flux. However, there are variety of different techniques for sample dissolution
several disadvantages to this method including the can be used. Dissolution assemblies such as the
introduction of additional salts into the final solution Kjeldahl flask, Parr bomb, crucible, quartz and plat-
inum vessels, PTFE containers, and specially de-
signed apparatus can be used for wet digestion
(Figures 1 and 2). Many suitable small vessels and
Table 2 Recovery of metals from various biomaterials after wet
devices for sample heating and filtering are available.
digestion
In the case of classical milliliter, microliter, and
Element Recovery (%) nanoliter methods, solution concentrations are gene-
Blood Urine Leaves Animal Reflux rally 40.01 mol l 1. The quantities of the decom-
tissue condenser position reagents and the decomposition vessels are
As 93 94 97 92 101
adjusted to the smaller sample weights.
Au 77 100 77 65 100 Inorganic materials subjected for trace metal ana-
Fe 98 92 95 85 100 lysis are generally decomposed and solubilized by
Hg 24 84 45 30 100 treatment with mineral acids or by fusion with fluxes.
Sb 99 95 94 94 100 Some inorganic samples, e.g., soils, may also contain
Ag, Co, Cr, Cu, Mn, Mo, Pb, V, Zn: 98–102% for all samples. considerable amounts of organic material, which can
Samples: 5 ml horse blood; 250 mg sugar beat leaves; 10 ml also be solubilized by acid treatment. Faster and
urine; 1.5 g animal tissue. more efficient decompositions of both organic and
Digested for 1.5 h with 5 ml of a mixture of 98% H2SO4, 70%
inorganic materials is possible using closed reaction
HClO4, and 66% HNO3 in the volume ratio 1:1:3 in a micro-
Kjeldahl flask. vessels (bombs) that allow higher temperatures and
Amount of metal present was 0.05–0.3 mg. pressures to be applied. For example, bombs have
Urine was digested with concentrated HNO3 only. been designed for the decomposition of silicates with

Table 3 Common fluxes

Flux Melting point ( 1C) Type of crucible/dish for Type of substance decomposed
of fusion

Na2CO3 851 Pt For silicates and silica containing samples; alumina-

containing samples; sparingly soluble phosphates and
sulfates
Na2CO3 þ an oxidizing 318 Pt (not with Na2O2), Ni For samples requiring an oxidizing environment; that is,
agent such as KNO3, samples containing S, As, Sb, Cr, etc.
KClO3, or Na2O2
NaOH or KOH 380 Au, Ag, Ni Powerful basic fluxes for silicates, silicon carbide, and certain
minerals; main limitation: purity of reagents
Na2O2 Decomposes Fe, Ni Powerful basic oxidizing flux for sulphides; acid insoluble
alloys of Fe, Ni, Cr, Mo, W and Li; platinum alloys, Cr, Sn,
Zr minerals
K2S2O7 300 Pt, porcelain Acid flux for slightly soluble oxides and oxide-containing
samples
B2O3 577 Pt Acid flux for decomposition of silicates and oxides where alkali
metals are to be determined
CaCO3 þ NH4Cl Ni Upon heating the flux, a mixture of CaO and CaCl2 produced;
used to decompose silicates for the determination of the
alkali metals
150 SAMPLE DISSOLUTION FOR ELEMENTAL ANALYSIS / Wet Digestion

Contamination and Loss of Analyte

Contamination
The introduction of foreign substances during wet
185 mm digestion and sample processing may have serious
consequences in elemental analysis, and sources of
contamination and their likely impact should be an-
ticipated in order to minimize the resulting errors.
Airborne contaminants, in the form of dust, cor-
rosion products, and residues from paints, etc., can
introduce many different elements into a sample,
e.g., sodium, potassium, calcium, magnesium, and
aluminum. This is a significant threat where open
reaction vessels are used, and can be avoided by
235 mm simple precautionary measures such as covering the
dissolution vessel with a dish or beaker equipped
with a side arm through which a stream of filtered air
250 ml or gas is passed. More stringent measures include the
use of a clean air room kept under positive pressure,
with the reaction itself carried out under a laminar
flow hood. Gaseous contaminants can be eliminated
Figure 1 Reaction flask with asbestos-jacketed air condenser. from the reaction vessel’s air supply using appropri-
The flask is a 250 ml borosilicate volumetric flask. A condenser is ate adsorption filters.
made from ST 19/38 ground glass joint, with a jacket of woven Another significant source of contamination is the
asbestos tubing held in place by wrapping with PTFE sealing
tape. (Reproduced with permission from Feldman C (1974) An-
vessels used for reagent storage and decomposition.
alytical Chemistry 46: 1607; & American Chemical Society.) There is no such thing as a completely inert vessel,
although the choice of an appropriate vessel that is
the least reactive under the chosen storage or de-
composition conditions is recommended. Table 4
shows the elemental composition of four materials
commonly used in decomposition and storage ves-
sels, therefore revealing likely contaminants and the
proportions in which they would be found. Dissolu-
tion vessels of Pyrex and quartz can introduce con-
tamination from many elements, but ultrapure
quartz can reduce the level of contamination from
trace elements by up to 1000-fold as long as the sur-
faces are scrupulously cleaned before use. Polypro-
pylene bottles, which are often used for the storage of
acids, become brown after some time indicating the
dissolution of the vessel’s organic material. Even
platinum vessels, which are required for fusions,
contain small amounts of contaminating iron that
can dissolve in contact with an acidic solution.
As well as the reaction and storage vessels, con-
Figure 2 Apparatus for wet oxidation of organic material. Stop- tamination may also arise from other stages of sam-
cock, having three positions, allows (1) refluxing, (2) distillation,
ple processing. Filter paper can contaminate samples
(3) removal of distillate. (Taken from Bethge PO (1954) Analytica
Chimica Acta 10: 317; and Gorsuch TT (1959) Analyst 84: 147. with aluminum, barium, calcium, chromium, copper,
Copyright by the Chemical Society.) iron, germanium, potassium, manganese, magne-
sium, sodium, antimony, gold, titanium, vanadium,
hydrofluoric acid at temperatures up to 1501C and zinc, zirconium, and rare earth metals. It is best to
pressures in excess of 8000 kPa. In the milligram use filter media other than paper and carry out ex-
range, the Parr bomb using metallic sodium or the tensive preliminary washing with the operating
Wurzschmitt bomb using sodium peroxide can be solutions. Ultrapure water should be used as dis-
used to decompose refractory substances. tilled water contains trace amounts of several
 SAMPLE DISSOLUTION FOR ELEMENTAL ANALYSIS / Wet Digestion 151

1
Table 4 Average content (in mg kg ) of current elements in the materials most commonly used for decomposition and storage
vessels

Element PTFE a Ultrapure quartz Quartz Pyrex glass

Al 100 30 000 Main constituent

As 0.1 50 500–20 000
B 10 100 Main constituent
Ca 100 500–3000 1 000 000
Cd 0.1 10 1000
Co 1 1 1 100
Cr 20 2 5 3000
Cu 10 10 50 1000
Fe 10 100 1000 100 000
Hg 10b 1 1 10–100
Mg 10 10 500 000
Mn 10 10 5000
Na 25 000 10 1000 Main constituent
Ni 2000
Sb 0.5 1 2 10 000
Si Main constituent Main constituent Main constituent
Ti 100 1000 3000
Zn 50 50 3000
a
Isostatic molded polytetrafluoroethylene.
b
Strongly dependent on cleaning conditions.
From Buldini PL, Ricci L, and Sharma JL (2002) Recent applications of sample preparation techniques in food analysis. Journal of
Chromatography A 975: 47–70.

Table 5 Illustrative contents of some trace elements in reagent grade and extra purity acids
1
Element Content (mg l )

HCl HClO4 HF HNO3 H2SO4

Amax B Amax B Amax B Amax B Amax B

Al 8 5 700 400 5 10 8
As 10 o1 50 5 50 10 1 500 o1
Ca 20 1000 7 10
Cd 10
Co o1 5 o1 o1
Cr 2
Cu 500, 50 2 200 5 100 10 100 3, 10 500 3
Fe 100 7 500 100 1000 500 200 5 200 10, 3
Hg o10 o10 o10 o10
Mg 4
Mn 1 500 5 1 1, 5 1, 5 1
Ni 500 o1 2 20 100 o1 500 1, 7
Pb 50 o1 100 5 20 2 5
Zn 100 o1 40 o1 o1

A ¼ analytical reagent, B ¼ extra purity reagent (‘electronic grade’), maximum content indicated by max; otherwise actual analysis.

inorganic compounds, resulting in contamination least reduce them to undetectable levels, by several
with copper, zinc, iron, nickel, aluminum, lead, and rounds of distillation.
others.
Contaminants originating in the mineral acids
Losses
used for digestion are also a significant source of
error. Table 5 shows the contaminants present in During wet digestion, certain components of the
reagent grade and extra-pure mineral acids available sample can be lost, leading to the underestimation of
from standard laboratory suppliers. Extra-pure acids particular elemental contents. Trace elements can be
have low levels of contaminants but are very ex- lost by adsorption to the vessel walls, volatilization,
pensive. It may be possible to eliminate many of the coprecipitation, and coextraction. Although the
trace contaminants from reagent grade acids, or at exact nature of adsorption losses is unclear, it may
152 SAMPLE DISSOLUTION FOR ELEMENTAL ANALYSIS / Wet Digestion

be due to molecular and ionic interactions. Metal sulfuric acid should not be carried out if the aim is to
cations exchange with alkali or alkaline earth ions at determine levels of arsenic. The ammonium salt of
the glass–solution interface and are replaced by H þ ethylenediaminetetraacetic acid is often used as a
ions. Anion exchange may also occur, e.g., AuCl4 matrix modifier for the dissolution of sediments and
for RSiOH groups on the glass surface. Vigorous other geological samples with hydrofluoric, sulfuric,
shaking of the solution may bring some of the ab- and perchloric acids.
sorbed species back into solution. Polyethylene and Digestion with a mixture of nitric, sulfuric, and
polypropylene also adsorb inorganic and molecular perchloric acids is more efficient when a small
species but to a lesser extent and a mature acid amount of molybdenum(IV) catalyst is added. As
strength of 10% is recommended in stored solutions. soon as water and nitric acid have evaporated, ox-
Solutions of 0.1 mol l 1 or stronger in mineral acid idation proceeds vigorously with foaming and is
stored in polyethylene, Pyrex, or similar borosilicate completed in a few seconds. To avoid the loss of
glass bottles remain stable for weeks. Plastic bottles mercury from a digestion, volatile mercury com-
may be preferred because of reduced leaching of pounds can be reduced to the metal with copper(I)
trace elements. Sample solutions of water should be and hydroxylammonium chloride at room tempera-
acidified to prevent or minimize the adsorption of ture, while organic matter is degraded by potassium
metals. Mercury concentrations in 1 mol l 1 nitric permanganate. The mercury can then be dissolved
acid in borosilicate glass do not show any loss over a and the analysis completed. Nitrogen-containing
period of months. Loss of analyte also occurs when compounds are commonly digested with sulfuric ac-
filtered through paper, sintered glass, or glass wool id and potassium sulfate to increase the boiling
due to adsorption. Centrifugation is therefore pref- point of the acid and thus the efficiency of the
erable to filtration. reaction. Proteins can be removed from organic
Volatile metals are less likely to be lost from basic samples by precipitation using trichloroacetic acid,
solutions than from acidic ones. Metals with higher tungstic acid with barium hydroxide, or zinc
oxidation states tend to form volatile oxides and sulfate.
halides, e.g., OsO4, RuO4, Re2O7, GeCl4, AsCl3, For the decomposition of inorganic samples by
SbCl3, CrOCl2, SnCl4, and TiF4. A few metals can be soda ash in platinum crucibles, the resistance of
lost from solutions by volatilization at room temper- platinum is increased in an atmosphere of carbon
ature, particularly OsO4 and RuO4. Losses associat- dioxide. In a nitrogen atmosphere, platinum is cor-
ed with the reaction of samples with silica glass, roded less by alkali metals. Peroxide bombs are good
porcelain, and platinum at higher temperatures may for wet ashing to destroy the organic matter in sam-
also take place. ples like coal. The PTFE acid digestion bomb
prevents contamination and insures no losses by
volatilization. Samples like coal can be analyzed in
Matrix Effects and Modifiers
quantities of 50 mg or less.
Many samples with inorganic or organic matrices In the fusion methods, cesium iodide is often add-
pose serious problems in elemental analysis due to ed to the fusion mixture as a nonwetting agent to
their composition and nature. It may therefore be prevent the molten flux from adhering to the walls of
necessary to add certain modifiers to the mixture to the vessel, as well as to prevent incomplete transfer
facilitate dissolution. In addition, dissolution assem- of the bead to the acid solution. In wet digestion of
blies may need to be modified. The use of hydrogen coal and fly ash using the Parr bomb, boric acid is
peroxide, a nonacidic modifier, has already been de- added after digestion and the sample is heated for a
scribed. This can be used in conjunction with suitable further time on a water bath allowing the removal of
acids for effective oxidation, and decomposition of unburned carbon.
organic matter usually proceeds without the danger No method of wet digestion is ideal, and both
of an explosion in a mixture of nitric and sulfuric contamination and losses will occur to a greater or
acids at atmospheric pressure. One common modi- lesser degree whichever method is used. The task of
fication of dissolution assemblies is the fitting of a the analytical chemist is to choose a procedure that
condenser, to prevent the loss of volatile mercury, will minimize interference from contaminants, re-
osmium, and ruthenium species. If excessive frothing duce losses as much as possible, and therefore
occurs during wet digestion, a small amount of 2- bring errors within acceptable limits. At all
octanol may be added or the preliminary treatment times, blank reagents and spiked recovery experi-
may be carried out in a beaker with glass beads to ments are required to establish the degree of
prevent bumping. With some organic materials, e.g., analyte contamination and loss from the dissolution
rubbers, coated fibers, and polymers, wet digestion in process.