Journal of Geochemical Exploration, 20 (1984) 101--135 101

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

USE OF PARTIAL DISSOLUTION TECHNIQUES IN GEOCHEMICAL

EXPLORATION

T.T. CHAO
U.S. Geological Survey, Box 25046, Federal Center, Denver, CO 80225 (U.S.A.)
(Received September 12, 1983; accepted for publication October 17, 1983)

ABSTRACT

Chao, T.T., 1984. Use of partial dissolution techniques in geochemical exploration.

J. Geochem. Explor., 20: 101--135.

Application of partial dissolution techniques to geochemical exploration has advanced

from an early empirical approach to an approach based on sound geochemical principles.
This advance assures a prominent future position for the use of these techniques in
geochemical exploration for concealed mineral deposits. Partial dissolution techniques
are classified as single dissolution or sequential multiple dissolution depending on the
number of steps taken in the procedure, or as "nonselective" extraction and as "selective"
extraction in terms of the relative specificity of the extraction. The choice of dissolution
techniques for use in geochemical exploration is dictated by the geology of the area,
the type and degree of weathering, and the expected chemical forms of the ore and of
the pathfinding elements. Case histories have illustrated many instances where partial
dissolution techniques exhibit advantages over conventional methods of chemical analysis
used in geochemical exploration.

INTRODUCTION

One of the major objectives of geochemical exploration is to detect in

geological sample media anomalous concentrations of elements that con-
stitute an expression of mineralization. Traditionally, the total concentration
of an element or elements is determined by complete consumption of the
sample. This is achieved either during ignition in an emission spectrograph,
or through decomposition by fusion or by digestion with mineral acids
followed by analysis. In recent years, increasing interest has been accorded
the use of partial dissolution techniques in geochemical exploration. This
has resulted from observations that ore elements, or associated pathfinding
elements, when released from buried sources to the sufficial environment
by hydromorphic means or by other transporting agents, are held in rela-
tively labile forms associated with various reaction sites. Reaction sites are
loci of chemical or physicochemical reaction where elements released during
weathering are held in place through various mechanisms. The relatively
labile forms can be brought into solution by extractions less drastic in
chemical action than total decomposition. This approach, though empirical,
has often resulted in greater geochemical contrasts between background

0375-6742/84/$03.00 © 1984 Elsevier Science Publishers B.V.

102

and anomalous values for elements in the sample with concomitant enhance-
ment of dispersion trains of the elements. Use of this approach has increased
the distance from the deposit at which mineralization can be detected.
With better understanding of geochemical principles, improvements in
chemical methodology and instrumentation, and acceptance of data handling
and statistical procedures, the partial dissolution techniques have become
relatively well established.
Partial dissolution techniques should be of most use with geological
samples collected from the weathering zone, because many recent successes
of exploration geochemistry have been credited to the use of weathering
products such as various types of soils and stream or lake sediments (Hawkes,
1979; Rose et al., 1979, p. 7). The relative importance of various sample
media may be reflected in the number and kinds of samples collected in a
period of time for purposes of mineral exploration. For example, of the
5.5 million geochemical samples taken throughout the world during 1975,
50% were soils, 20% stream and lake sediments, 20% rocks, 5% water, and
5% plants (Boyle, 1976). With the exception of rocks, these materials can
be considered to be weathering products.
The purpose of this paper is to review the conceptual and practical progress
of partial dissolution techniques in recent years, and to synthesize available
information in this regard, in terms of: (1) controls on dispersion of ele-
ments, especially metals, of geochemical significance in the weathering
environment; (2) basic requirements and limitations of the techniques;
(3) the nature and properties of the available chemical extractants and
procedures for partial dissolution; and (4) application of the techniques to
geochemical exploration for ore deposits.

CONTROLS ON DISPERSION OF ORE AND PATHFINDINGELEMENTS IN THE

WEATHERING ENVIRONMENT

Metal or nonmetal elements of geochemical interest that are released

from primary and secondary minerals through weathering processes move
in solution along hydromorphic channels of geological matrices. They tend
to partition into different chemical forms associated with various inorganic
and organic phases, depending on the chemical and geological environments.
Phases with strong adsorptive or retentive power will hold the elements
in place close to their surface through physicochemical bonding or incor-
porate the elements into their structure. The remainder of the elements
will distribute on a competitive basis into other phases with variable bond
strength. An element may shift from one phase to another over a period
of time.

R e a c t i o n sites as m a j o r controls

The major controls on the dispersion of ore and pathfinding elements in

the weathering environment are reaction sites in a complex chemical realm
 103

where geological materials undergo numerous chemical, physicochemical,

and biological transformations. The reaction sites are oxides of iron and
manganese, oxides of aluminum and silicon, organic matter, carbonates, and
secondary sulfides. The clay-size aluminosilicates, generally considered as
the most active fraction of softs and sediments because of their surface
properties, serve essentially as a vehicle for other reaction sites (Jenne, 1977).
Ore metals and related pathfinding elements mobilized through weathering
have to overcome various chemical barriers associated with the reaction
sites in order to disperse. Although the extremely complex nature of the
interactions defies precise description, important processes operating in
softs and sediments are: (1) adsorption and desorption; (2) precipitation and
solubilization; (3) surface complex formation; (4) ion exchange; (5) pene-
tration of the crystal structure of minerals; and (6) biological mobilization
and immobilization.

Importance o f iron and manganese oxides as reaction sites

Iron and manganese oxides are of paramount importance in exploration

geochemistry due to their ubiquitous occurrence and strong scavenging of
metal ions (Chao and Theobald, 1976). Iron and manganese oxides are in
general more important than aluminum and silicon oxides, because the iron
and manganese oxides have greater adsorption capacities, dissolve as the
redox potential decreases, and reprecipitate as the system becomes oxy-
genated (Jenne, 1977).
Alternate dissolution and precipitation tend to maintain the oxides of
iron and manganese in a highly active amorphous state or in a low degree
of crystallinity. A low degree of crystallinity facilitates the nonstoichiometric
incorporation of foreign elements, especially metals, into the oxides (Kuhnel
et al., 1975). Although manganese oxides may precipitate less rapidly than
iron oxides, isomorphic substitution and penetration by foreign ions into
the extremely complex mineralogical structure of manganese oxides is much
more extensive than in the iron oxides, and the oxidation state of the
manganese is highly variable (Chao and Theobald, 1976; Jenne, 1977).
Therefore, manganese oxides usually have greater scavenging capacity for
heavy metals than iron oxides on a equivalent weight basis (Chao and Theo-
bald, 1976).

Controls exerted by oxides o f aluminum and silicon

Additional controls on the movement of metals in the weathering processes

may be exerted by the oxides of aluminum and silicon. They have been
shown to possess adsorption capacities for metals (Jenne, 1977), but their
role as geochemical controls of metals has not been adequately evaluated
due to the lack of selective extractants for these two oxides.
104

Role o f organic matter

Organic matter in soils and sediments comprises a group of complex

chemical components of biological origin. The active functional groups can
form organometallic complexes and chelates by solubilizing metal com-
pounds or by precipitating metal ions, depending on the solubility of com-
plexes and chelates formed. Wherever organic matter accumulates in soils
and sediments, organic related metals provide a possible indication of miner-
alization. Wilhelm et al. (1979) suggested that if the organic carbon content
in softs and sediments is less than 5%, the metal-organic matter association
appears to be less important than other controls, especially the oxides of
iron and manganese. This statement can be applied only to the study area
of Wilhelm et al. and should not be projected to other areas without close
examination. For example, results obtained by Filipek et al. (1981) on
factors affecting the partitioning of Cu, Zn, and Pb in boulder coatings and
stream sediments emphasize the importance of organics as controls for ore
metals, even in an environment with high concentrations of manganese and
iron oxides. More research is needed on the role of organic matter in con-
trolling metal distribution in the weathering environment.

Secondary carbonate as reaction sites

Carbonates of calcium and/or magnesium accumulate in arid and semiarid

regions either in the surface horizon or at a certain depth in the soil profile
depending on the amount and distribution of rainfall. The control of metals
in soils or sediments by the secondary carbonates is brought a b o u t by
adsorption of metals on the surface, by coprecipitation, and by the for-
mation of insoluble metal hydroxides through the capacity of the prevailing
high pH to hydrolyze metal ions. The scavenging of metals by carbonates
is not as effective as that by iron and manganese oxides (Patchineelam,
1978). However, in arid and semiarid regions where accumulation of iron
and manganese oxides is not present, carbonates as controls of the distri-
bution of metals deserve due attention.

Secondary sulfides

Another control of the dispersion of metals in the weathering environ-

ment is the formation of secondary sulfides through reaction between metal
ions and sulfide ions in a reducing environment. In geochemical exploration,
the identification of primary sulfide minerals as source materials of miner-
alization is more important than the u s e of secondary sulfides as a geo-
chemical control.
 105

Capacity and intensity of controls

Even though the chemical components which control the dispersion of

metals in softs and sediments are treated above as separate entities, in fact
they are intractably entwined in the materials used for geochemical samples.
Environmental conditions can affect the relative importance of the controls.
Nevertheless, each control tends to exercise its influence more or less on a
competitive basis involving both capacity and intensity. Capacity relates to
the quantity of a given control present; intensity is concerned with the
chemical activity of the given control. For example, a unit weight of iron
as amorphous iron oxide may be more effective in partitioning metals than
the same weight of iron as crystalline iron oxide. Therefore, a dissolution
technique is needed for geochemical exploration that will separate amorphous
iron oxide together with its associated metals from crystalline iron oxide
and its associated metals. The basic requirements and limitations of these
techniques are discussed below.

BASIC REQUIREMENTSAND LIMITATIONSOF PARTIAL DISSOLUTION

TECHNIQUES

The basic requirements of partial dissolution techniques are selective

extraction procedures that dissolve specific components of the weathering
products. In softs and sediments the reactions of the ore metals and asso-
ciated pathfinding elements released during weathering yield secondary
products containing a major part of the metals related to mineralization.
These secondary products can be dissolved by some mild extractants, bring-
ing into solution the metals in the secondary products while leaving more
or less intact the same metals tied up in primary rock materials and other
background media. By bringing the metals of only the secondary products
into solution instead of consuming the whole sample, the geochemical
contrasts can be significantly enhanced.
The chemical components related to metal distribution in soils and
sediments rarely exist as separate entities, as noted above. Any claim that
individual components can be isolated by partial dissolution techniques,
and that the metals released into the extract are genetically related to the
individual components, should be viewed with reservation. Many criticisms
have been expressed as to the specificity of selective extraction (Jenne and
Luoma, 1977; Webb and Thompson, 1977; Gatehouse et al., 1977; Slavek
et al., 1982). Side reactions that may occur during the extraction and affect
the extractability of certain metals in the ensuing steps of a sequential
multiple dissolution have been indicated (Rendell and Batley, 1980; Slavek
et al., 1982).
From the utilitarian standpoint, however, the close association of metals
and pathfinding elements with iron and manganese oxides has been con-
vincingly illustrated by electron microprobe analysis (Burns and Fuerstenau,
106

1966; Harris and Troup, 1969; Fordham and Norrish, 1974; Norrish, 1975;
McKenzie, 1975; Wilhelm et al., 1979), by statistical analysis of geochemical
data (Canney, 1966; Cronan, 1970; Nowlan, 1976), and by kinetic studies
of the release during extraction of iron and manganese in relation to other
metals (Ellis et al., 1967; Chao and Anderson, 1974; Malo, 1977; Warnant
et al., 1981). The association between metals and organic matter has been
demonstrated by Hoffman and Fletcher (1981) and by Filipek et al. (1981).
Despite the limitations, partial dissolutions remain one of the useful tools
available for the examination of metals associated with various components
in soil and sediment that serve as controls of dispersion (Jenne et al., 1974;
Gatehouse et al., 1977; Lion et al., 1982).
In applying partial dissolution techniques to the search for mineralization,
a compromise has to be made so that the use of the techniques for practical
purposes will not conflict with theoretical considerations of geochemical
principles. In the following discussions, the relations between metal distri-
bution and the chemical components or mineral phases of soils and sedi-
ments are often designated by expressions such as "associated with", "in
association with", or "related to." The true meaning of these expressions
is that metal associations determined by selective extractions are "extractant-
d e p e n d e n t " , "operationally defined" (Jenne, 1977), or "functionally de-
finable." With this practical obstacle recognized, the application and the
potential usefulness of partial dissolution techniques in geochemical ex-
ploration can be logically discussed.

PARTIAL DISSOLUTION TECHNIQUES

Partial dissolution techniques can be classified as single dissolution and

sequential multiple dissolution techniques. They can also be classified as
"nonselective" extraction and as "selective" extraction depending on the
degree of specificity of the extraction. The terms "nonselective" and "selec-
tive", as used here, are strictly relative. A partial extractant designed to
dissolve a certain chemical c o m p o n e n t may frequently fall short of specificity
in one way or another. For example, the sodium dithionite reagent long
used as an extractant for crystalline iron oxides also extracts aluminum
oxides (Saunders, 1959; Chao et al., 1962). Unless the co-extraction of
aluminum oxides is taken into account, interpretation of the dissolution
data could be in error.
A "nonselective" extraction under a given set of conditions can be made
relatively more "selective." For example, the a m m o n i u m citrate reagent
(Bloom, 1955) was originally designed to extract easily soluble metals
attached to various reaction sites of soils and sediments. Whitney (1981)
modified the reagent by lowering its pH and applied it to a special sample
medium, stream gravel coated with iron-manganese oxides, where the reagent
becomes relatively selective in dissolving the coatings and their associated
metals.
 107

In a review of partial dissolution techniques, separate factors, such as the

kinds of reagents used as extractants, the types of geological materials on
which the extractants have been successfully used, and the evolution of
fractionation schemes for sequential multiple extraction, must each be
considered. In single dissolution techniques the emphasis is first on the
reagent where "nonselective" extractions are discussed. In discussions of
the single dissolution technique where a single "selective" extraction in a
sequence of extractions is considered, the choice of reagent is determined
b y the c o m p o n e n t of the geological matrix that is sought by the extraction.
This technique is best reviewed, therefore, in a hierarchical ranking of extrac-
tability of the geological material with the most readily soluble c o m p o n e n t
considered first. For the evolved partial dissolution techniques employed in
sequential multiple extraction, the fractionation scheme involving several
extractants can best be addressed by a review of the scheme itself.

Methods o f single extraction

The single extraction discussed here consists either of the application of

an individual extractant or of applications where the single extractant
constitutes one step in a scheme of sequential multiple extraction. Thus,
the method of the single extraction may be either a "nonselective" extraction
-- the application of an individual extractant -- or a "selective" extraction --
the application of a single extraction as a step in successive multiple extrac-
tions.

"Nonselective" extraction
One group of chemical extractants that have been used in geochemical
exploration consists of inorganic acids and organic reagents. Their function
is to dissolve from the geological materials some vaguely defined fractions
of the total content of metals that have been influenced b y weathering.
Specificity of the extraction is undefined, and the extracted metals, usually
termed "cold-extractable" or "hot-extractable", may be derived from several
chemical forms or mineral phases. Underlying the use of "nonselective"
extraction is the theme that trace metals related to mineralization, or path-
finder elements, are likely to be introduced into the geological matrices
through hydromorphic movement or other processes of weathering, and that
secondarily concentrated metals are more easily solubilized by chemical
extractants than the same metals in crystal structures of silicates or of
other minerals resistant to weathering.

Inorganic acid. Varying concentrations of strong inorganic acids are com-

monly used as extractants in "nonselective" applications. For example,
hydrochloric acid of varying concentrations has been employed as an extrac-
tant in geochemical exploration (Canney and Hawkins, 1958; Maynard and
Fletcher, 1973; Bradshaw et al., 1974), and in studies of the chemical
108

leaching of rocks (Stendal, 1980) and of aquatic sediments (Agemian and

Chau, 1976; Malo, 1977). The efficiency of hydrochloric acid in extracting
metals depends on such operating conditions as the concentration of the
acid, the ratio of the amount of sample to the volume of solution, and the
duration and temperature of the extraction (Sorensen et al., 1971). Nitric
acid has been used in the preparation of geological materials for analysis
(Ward et al., 1969; Ukpong and Olade, 1979; Stendal, 1980). Extraction
with 4 N nitric acid is considered the most effective leach for use in geo-
chemical surveys to distinguish between anomalies resulting from back-
ground lead and zinc and anomalies caused by lead-zinc mineralization
(Ukpong and Olade, 1979). Aqua regia, a fresh mixture of hydrochloric
and nitric acid in the volume ratio of 3 to 1, is a chemically strong reagent
that attacks various inorganic and organic phases in softs and sediments;
nevertheless, it may be regarded as a "nonselective" extractant. Aqua regia
can dissolve metals associated with inorganic and organic colloids, oxide
precipitates and minerals, and sulfides (Mothersill, 1977). Through the use
of aqua regia, the extractable copper in rocks in the vicinity of an area of
copper mineralization was found to be much higher than in rocks unrelated
to mineralization (Warren and Delavault, 1959, 1969).

Organic acids and salts. Solutions of organic acids and salts are less common-
ly used as extractants than inorganic acids. However, a technique employing
acetic acid adjusted to pH 5.5 with ammonia as an extractant for partial
chemical analysis of altered rock was reported (Lovering et al., 1948) to have
delineated metal anomalies indicative of underlying mineralization where
standard chemical and spectrographic analyses of the same altered rocks
failed to indicate the anomaly.
EDTA (ethylenediaminetetracetic acid) is a weak organic acid with com-
plexing and chelating ability to sequester divalent and trivalent cations
(Viro, 1955a; Borggaard, 1976a). It has commonly been used in soil analysis
to determine plant-available micronutrients, especially copper, iron, manga-
nese, and zinc (Viro, 1955b; Borggaard, 1976a). It extracts metals on ex-
change sites of both inorganic and organic complexes in soils and sediments
without attack on the crystal structure of silicate minerals (Viro, 1955a;
Timperly and Allan, 1974; Aoyama et al., 1982), and releases metals asso-
ciated with hydromorphically moved materials (Bradshaw et al., 1974). In
addition, EDTA can dissolve calcareous materials through complexation
of calcium and magnesium (Viro, 1955a; Glover, 1961; Bodine and FernaUd,
1973; Borggaard, 1976a).
The use of mild EDTA for the detection of mineralization has been
recommended (Bradshaw et al., 1974) because stronger extractants, such as
perchloric acid, tend to attack rock fragments as well as secondary products.
Consequently, the stronger extractants reduce the effect of mineralization.
Maynard and Fletcher (1973) compared total and partial extractable copper
in samples of peat having anomalous and background contents of copper.
 109

Greater geochemical contrast for copper was found between anomalous

and background samples by using nitric-perchloric acid digestion than by
extracting with 0.05 M EDTA (pH 4.8), even though the EDTA removed
70 to 75% of the total copper. If the pH of the EDTA extractant had been
raised to 9.0, greater amounts of copper would have been released from
anomalous samples (Viro, 1955a), and the geochemical contrasts obtained
by the EDTA extraction could have been enhanced.
EDTA as a partial extractant for anomaly accentuation deserves further
study in geochemical exploration.
An extraction with a solution containing ammonium citrate and hydrox-
ylamine hydrochloride at pH 8.5 was devised by Bloom (1955) as a field
chemical test for the determination of cold-extractable metals in softs and
sediments to aid in °revealing mineralization. Hydroxylamine hydrochloride
in the reagent was originally intended as an anti-oxidant to protect the
coloring agent dithizone (Hawkes, 1963), but it also has' the ability to
dissolve manganese oxides and associated metals (Dion et al., 1947; Canney
and Nowlan, 1964). Citrate in the extracting solution serves as a chelating
agent to prevent the released metals from precipitating at the prevailing
high pH. The method using ammonium citrate-hydroxylamine hydrochloride
reagent for cold-extractable metals has long enjoyed popularity among
mining geologists and prospectors, mainly because of its simplicity and
sensitivity. Lately, the ammonium citrate reagent and operating conditions
of the method have been modified (Whitney, 1975, 1981), as noted above,
to render it more selective in dissolving iron-manganese oxides and asso-
ciated metals in stream sediments and in coatings on gravel.

"Selective" extraction

Water-soluble fractions and exchangeable metals. The water-soluble fractions

of softs and sediments are the first portion to be brought into solution by
any partial dissolution technique. Normally, this portion is minimal or
negligible in the geological material, especially for heavy metals, unless the
sample is from the vicinity of strong mineralization in an environment where
prevailing weathering conditions promote the formation of water soluble
salts of ore elements. Soluble fractions can dominate where evaporites are
present.
Electrical conductivity of soil slurries, and hydrogen-ion concentration
and soluble cations of water extracts of soil and rock samples have recently
been shown to be a means to detect buried sulfide deposits (Govett, 1974,
1975, 1976; B~blviken and Logn, 1975; Govett et al., 1976; Goodfellow
and Wahl, 1976). The theoretical basis of this approach is an electrochemical
mechanism whereby the secondary dispersion of metals into rocks or over-
burden can be explained as a response to the development of electrical
potentials around sulfide ore bodies.
110

Exchangeable metals are the next to be extracted after the water-soluble

fractions. These metals are held through electrostatic attraction on exchange
sites on the surface and interface of negatively charged inorganic and organic
complexes of softs and sediments. Alkali and alkaline earth metals as ex-
changeable cations are readily replaced by an excess of a neutral salt solution
containing a different cation, i.e., Ca 2÷ replacing Mg2÷, K ÷, and Na ÷. In this
respect they differ from such heavy metals of geochemical interest as iron,
manganese, copper, lead, zinc, cobalt, nickel, and others, because retention
of heavy metals occurs through specific adsorption even in the presence
of an excess of a neutral salt, such as CaC12, in solution (Hodgson, 1960).
Neutral salts commonly used for replacing exchangeable metals are
NH4Ac, CaC12, MgC12, BaCI~, and others (Jackson, 1958). Exchangeable
heavy metals normally constitute only a small proportion of the total amount
of metals in soils and sediments (Rose and Suhr, 1971; McLaren and Craw-
ford, 1973; Dijkstra et al., 1979). Reducing conditions are necessary for
appreciable amounts of iron and manganese to exist as exchangeable metals.
Measured quantities of exchangeable heavy metals have yet to be demon-
strated to help identify mineralization.

Carbonates. Carbonates may be present in soils and sediments in variable

chemical composition, degree of crystallinity, and particle size. The model
carbonate minerals are calcite, dolomite, and magnesite, with intermediate
members of diverse cationic composition. Under arid and semiarid climatic
conditions, the carbonate may form caliche coatings on pebbles and cobbles
in alluvium (Erickson and Marranzino, 1960) or may accumulate as lime
nodules or concretions at certain depth in the profile in response to local
rainfall.
Trace-metal elements may coprecipitate with carbonates both inorganically
and biogenetically. These elements may undergo isomorphous exchange
with calcium or magnesium situated at the surfaces of the carbonate minerals,
or may be adsorbed by iron and manganese oxides which have precipitated
onto the carbonates (Jenne, 1977). The compatibility of Zn 2÷ with magnesite
(MgCO3) crystal lattice has been suggested as the reason for the strong
interaction of zinc with dolomite {CaMg(CO3)2) and Ca-magnesite, relative
to calcite (CaCO3) (Jurinak and Bauer, 1956).
Reagents commonly used for the dissolution of carbonates are 25%
acetic acid (Ray et al., 1957; Hirst and Nicholls, 1958; Chester, 1965;
Barker, 1974), 1 N acetic acid (Gupta and Chen, 1975; Filipek and Theobald,
1981), and sodium acetate-acetic acid buffer solutions (Jackson, 1956; Rose
and Suhr, 1971; Le Riche, 1977; Openlender, 1979; Tessier et al., 1979;
Wakefield, 1980). The acetic acid-acetate buffer treatment removes metals
held in carbonates and those electrostatically associated with exchange
sites on clays and organic matter in soils and sediments. This treatment
apparently does not attack the resistant iron and manganese oxide minerals
to any great extent (Loring, 1976) and leaves the lattice structure of silicate
minerals intact.
 III

Bodine and Fernalld (1973) reported a method utilizing boiling 0.2 M

EDTA at pH 10--12 for dissolving Ca-Mg carbonates, gypsum, and anhydrite.
A strong acid ion-exchange resin has been used for the separation of clay
minerals from limestones (Lloyd, 1954) and for the selective extraction of
carbonate-associated metals from lacustrine sediments (Deurer et al., 1978).
This technique has the advantage of no free hydrogen ions to attack other
mineral species.

Organic matter. Three common reagents have been used to oxidize or to

extract organic matter with resulting release of its associated metals from
geological materials: hydrogen peroxide, sodium hypochlorite, and alkali
pyrophosphate. Each has its particular uses, but each also has restrictions
in its effectiveness as an extractant.
Hydrogen peroxide (H202): The hydrogen peroxide treatment (Robin-
son, 1927) is one of the early methods for destroying organic matter in
earthy materials, and has become the standard procedure to aid in the dis-
persion of soil particles prior to mechanical analysis (Jackson, 1956). How-
ever, such treatment is not completely effective; appreciable amounts of
organic matter may still remain after peroxidation (Farmer and Mitchell,
1963). The effectiveness of the hydrogen peroxide treatment can be sig-
nificantly increased by the presence of 0.1 M sodium pyrophosphate at pH
7 in the reaction media (Sequi and Aringhieri, 1977). After this treatment
the residual carbon of various soils was reduced as much as 20 times com-
pared to conventional peroxidation.
Hydrogen peroxide has been used in various sequential extraction schemes
to release metals associated with organic matter in soils and sediments
(Rose and Suhr, 1971; Gupta and Chen, 1975; Tessier et al., 1979; Filipek
and Theobald, 1981). The hydrogen peroxide treatment should follow the
removal of reducible manganese oxides to avoid complications caused by
the simultaneous solubilization of the oxides (Robinson, 1929). Hydrogen
peroxide can also dissolve several sulfide minerals that may be present in
soils and sediments (Chao and Sanzolone, 1977).
Possible formation of oxalate as a result of the hydrogen peroxide treat-
ment of soils has been reported by Martin (1954) and by Farmer and Mitchell
(1963). The oxalate may dissolve oxides of iron and manganese (Williams
et al., 1958; Lavkulich and Wiens, 1970) in a manner similar to the action
of Tamm's reagent (Farmer and Mitchell, 1963). The release of trace metals
along with the dissolution of oxides may adversely affect the fractionation
scheme of both single and sequential extractions.
If the hydrogen peroxide treatment is used for the release of metals
associated with organic matter from soils and sediments, attention should be
paid to the side effects of the treatment on manganese oxides and sulfide
minerals as well as to its incomplete oxidation of organic matter.
112

Sodium hypochlorite (NaOCl): Sodium hypochlorite solution (pH

9.5) was first employed by Anderson (1963) as a pretreatment for mineral-
ogical analysis of softs to oxidize organic matter, following its use by Cassidy
and Mankin (1960) to remove organic matter from shale. Sodium hypo-
chlorite was found by Lavkulich and Wiens (1970) to destroy the organic
matter of softs with less solution of the oxides of iron and manganese than
was caused by hydrogen peroxide. In 16 samples of soil, up to 98% of the
oxidizable organic carbon was removed by three successive extractions
with sodium hypochlorite. The lesser attack on the oxides of iron and
manganese by the sodium hypochlorite compared to the results of treat-
ment with hydrogen peroxide is attributable to the freedom from the
formation of oxalate when sodium hypochlorite is used for oxidation.
Sodium hypochlorite has been used by Gibbs (1973, 1977) to study
the mechanisms of trace-metal transport in rivers, and by Hoffman and
Fletcher (1979, 1981) to study the scavenging of metals by organic matter
in softs and sediments. The procedure followed by Hoffman and Fletcher
is relatively slow and entails prolonged homogenization of samples with
the alkaline sodium hypochlorite solution, which is in contrast to the rela-
tively simple and short method of Anderson (1963) and of Lavkulich and
Wiens (1970). The effect of sodium hypochlorite at pH 9.5 on the mineral
phases and chemical composition of soils and sediments, especially in a
prolonged treatment, requires further study (Lavkulich and Wiens, 1970).
The sodium hypochlorite treatment of softs and sediments does not
appear to dissolve manganese oxides (Rose, 1975), but it may cause the
release of the manganous ion from organic matter to form permanganate
during oxidation (Anderson and O'Connor, 1972). Treatment of soils and
sediments with sodium hypochlorite, however, will attack sulfides that may
be present in the sample (Rose, 1975; Hoffman and Fletcher, 1979).
Alkali pyrophosphate (Na4P207 or K4P207): Organic matter in soils
and sediments is stabilized by calcium, iron, aluminum, and probably by
some other metal cations. Solutions containing anions which can remove
these stabilizing metals by precipitation or by the formation of chelates or
coordination complexes are very effective in the extraction of humic ma-
terials (Bremner and Lees, 1949). One of these anions is pyrophosphate.
It has been used to extract organic-chelated iron, aluminum, and other
metals along with organic carbon in studies of the genesis of soils and the
development of soil profiles (McKeague, 1967; Bascomb, 1968; Ball and
Beaumont, 1972; Tan, 1978). The effectiveness of this anion is modified
by several factors including the pH and the concentration of the pyrophos-
phate solution, the time and temperature of extraction, and the frequency
of extraction (Bremner and Lees, 1949; Evans, 1959; Tinsley and Salam,
1961). The most important factor is the pH of the pyrophosphate solution,
which is commonly 7 or 10. A pH of 7 tends to decrease the eXtraction
of organic matter (Bremner and Lees, 1949; Evans, 1959) and to increase
 113

the extraction of "aged" amorphous hydrous oxides of iron (Bascomb,

1968). This latter effect is particularly important in geochemical exploration
when pyrophosphate is used as a selective extractant to remove organic-
chelated metals. At pH 10, 0.1 M sodium pyrophosphate does not dissolve
amorphous or crystalline iron oxides (McKeague, 1967). At this pH and
concentration, sodium pyrophosphate has been utilized to differentiate
forms of extractable iron and aluminum in soils (McKeague et al., 1971).
Bascomb and Thanigasalam (1978) reported that pyrophosphate solution
was more suitable than aqueous acetylacetone for the selective extraction
of iron-organic complexes from soils containing amorphous or poorly
crystalline iron oxides of high specific surface area.
Pyrophosphate also extracts organically bound metals other than iron
and aluminum. In a sequential fractionation of copper in soils, McLaren
and Crawford (1973) determined the copper associated with organic matter
by treating the sample with 1.0 M potassium pyrophosphate, following
the removal of other copper fractions in previous extractions. Geographic
variations in the amounts of manganese, copper, zinc, cobalt, nickel, and
iron extractable by sodium pyrophosphate from sediments have been used
as indications of the sources of these metals and of estuarine processes
which have affected their concentrations (Eaton, 1979).
The host phases of metals in samples of softs and stream sediments were
successively extracted with pyrophosphate to determine the association of
metals and organic matter (Wilhelm et al., 1979). These investigators found
that the percentage of metals released from sulfides during weathering which
were later trapped by humified materials was always less than the percentage
of metals linked to iron oxides. At porphyry copper districts in Puerto Rico,
the partitioning of copper among selected phases of active stream sediments
was investigated by a sequential dissolution technique (Chao and Theobald,
1976; Learned et al., 1981). The organic chelated copper extractable with
pyrophosphate was found to amount to only 4% of the total copper. This
sparseness can be explained by the fact that weathering conditions in Puerto
Rico are not conducive to the accumulation of organic matter.
Extraction with pyrophosphate does not attack sulfides nor does it seem
to dissolve significant amounts of amorphous iron oxides. However, its
action on various species of poorly crystallized iron oxides in different
types of soils and sediments is not well understood and should be reexamined.
Because of the highly dispersive state of the suspension resulting from treat-
ment with pyrophosphate at pH 10, strong centrifugation is necessary to
separate the supernatant solution (McKeagne, 1967). The fact that sus-
pended ferruginous particles may occur in these pyrophosphate extracts
(Jeanroy and Guillet, 1981) can complicate the extraction, thus the proce-
dure should receive further study.

Manganese oxides. Manganese oxides under normal aerated conditions are

widespread in soils and stream sediments and have been credited with
114

scavenging heavy metals of geochemical significance (Jenne, 1968; Chao

and Theobald, 1976). The mineralogical identity and chemical activity of
manganese oxides are extremely complex. Their mineralogical structure
and chemical reactions are controlled by various factors, the most important
one of which is the oxidation-reduction condition of the environment
(Sherman and Harmer, 1943; Leeper, 1947).
A neutral 1 N a m m o n i u m acetate solution containing 0.2% hydroquinone
(Sherman et al., 1942) has been used to extract easily reducible manganese
oxides and associated metals in sediments to determine patterns of multi-
element distribution in the secondary environment (Nichol et al., 1967;
Horsnail et al., 1969). For the extraction of active manganese oxides from
softs and clays, other investigators resorted to the dithionite reaction (Daniels
et al., 1962; Biswas and Gawande, 1964; Anderson and Jenne, 1970), or
to acid ammonium oxalate solution (Le Riche and Weir, 1963; Blume and
Schwertmann, 1969; Williams et al., 1971). Both dithionite and acid ammo-
nium oxalate solutions were originally designed for the dissolution of free
iron oxides. The manganese-iron oxide phases of a ferromanganese nodule
were extracted by treating the sample with various concentrations of hydrox-
ylamine hydrochloride in 25% acetic acid at r o o m or hot-water temperature
(Chester and Hughes, 1967). None of these methods mentioned can be
considered as selective because both manganese and iron oxides are dis-
solved. Taylor and McKenzie (1966) reported utilizing a prolonged treat-
ment with 10% hydrogen peroxide in 0.001 N nitric acid to remove manga-
nese oxides from soils. However, it has been shown that hydrogen peroxide
will dissolve sulfides that may be present in the sample (Chao and Sanzolone,
1977).
The ability of hydroxylamine hydrochloride to dissolve manganese
oxides has been well d o c u m e n t e d (Dion et al., 1947; Canney and Nowlan,
1964; White, 1969). A method was developed by Chao (1972) for the
selective dissolution of manganese oxides from softs and sediments. Briefly,
the sample is extracted with 0.1 M hydroxylamine hydrochloride in 0.01
M HNO3 on a mechanical shaker for 30 minutes at a solution : sample ratio
of at least 50. The hydroxylamine solution has a pH of 2 and is itself poorly
buffered. However, if the sample does not contain a large amount of car-
bonates, the low pH and the wide solution : sample ratio both tend to
maintain the reaction of the solution on the acid side thus preventing as
much as possible the hydrolysis of the released metals.
The action of the hydroxylamine solution under the above operating
conditions is specific on manganese oxides. Most manganese oxides in soils
and sediments can be brought into solution in 30 minutes. Crystalline iron
oxides such as goethite, hematite, and magnetite do not dissolve in the
solution, whereas freshly prepared amorphous hydrous iron oxide dissolves
to the extent of a few percent of its total iron. This method has since been
adopted widely for single or sequential extraction schemes involving manga-
nese oxides and associated metals in studies related to exploration geo-
 115

chemistry, soil and aquatic chemistry, marine geochemistry, and environ-

mental science.

Iron oxides. Iron oxides in various mineralogical forms and degrees of

fineness resulting from chemical weathering of iron-containing minerals
are present in soils and sediments (Oades, 1963; Schwertmann and Taylor,
1977). These oxides play an important role in determining the chemical
reactivity of soils and sediments in the weathering environment. The minera-
logical structure of iron oxides ranges from highly crystalline through
cryptocrystalline to amorphous in a continuum sequence (Schwertmann,
1973). A selective dissolution technique for these materials, in order to be
useful for geochemical exploration, should be able to differentiate between
amorphous and crystalline iron oxides.
Amorphous iron oxides: The acid ammonium oxalate solution (0.175
M (NH4)2C204-0.100 M H2C204), commonly known as the Tamm's reagent,
has been extensively used in studies of soil genesis and development (McKeague
and Day, 1966; Blume and Schwertmann, 1969) and in exploration geo-
chemistry as a selective extractant to dissolve amorphous iron oxides when
reacting in darkness. In exploration geochemistry, the acid oxalate solution
has been employed to extract amorphous iron oxides in a sequential dis-
solution scheme (Hoffman and Fletcher, 1979; Sondag, 1981) in order to
understand the mode of occurrence of associated metals of geochemical
interest and in an attempt to enhance metal anomalies for the detection of
mineralization.
Although hematite and goethite dissolve only sparingly in the acid oxalate
solution (McKeague and Day, 1966; Chao and Zhou, 1983), magnetite
(Baril and Bitton, 1967; Gamble and Daniels, 1972; Rhoton et al., 1981;
Chao and Zhou, 1983) and lepidocrocite (Schwertmann, 1973) can release
significant amounts of iron into the solution. The inclusion of products
from the solution of crystalline iron oxides such as magnetite and lepido-
crocite with products extracted from amorphous iron oxides can confound
the interpretation of the partitioning of metal into different mineral phases
or chemical forms, especially where magnetite is present, because the mineral
is noted for containing a host of trace metals (Theobald et al., 1967; Over-
street et al., 1978; Pan et al., 1980).
A method utilizing an acidified hydroxylamine hydrochloride (0.25 M
NH~OH.HC1-0.25 M HC1) to extract soil or sediment samples at 70°C in a
shaker bath for 30 minutes was first developed to dissolve amorphous iron
oxides for fractionation of copper in soil or sediment (Chao and Theobald,
1976; Learned et al., 1981). The combined solution has since been applied
to geochemical work in the formulation of sequential dissolution techniques
(Learned et al., 1981; Bogle and Nichol, 1981). Chao and Zhou (1983)
improved the method by reducing the temperature of reaction from 70 ° to
50°C. By the improved method the percent dissolution of iron from natural
116

and synthetic amorphous iron oxides, and from a variety of geological

materials, is nearly identical with that dissolved by the Tamm's reagent, and
the percent dissolution of iron from all crystalline iron oxides tested is
reduced to less than 1% (Chao and Zhou, 1983). It is expected that the
improved m e t h o d will have wide application in geochemical exploration
as a selective technique to extract metals associated with amorphous iron
oxides.
In a series of papers, Borggaard (1976b, 1979, 1981, 1982) reported a
selective extraction technique to dissolve amorphous iron oxides from soils
by using 0.02 to 0.1 M EDTA at pH 8 to 10.5 with time of extraction
varying from a few days to several months. The time-consuming procedure
would exhibit its application to geochemical exploration. However, the
EDTA technique may serve as a reference method for the determination
of amorphous iron oxides in soils.
A selective extraction of the amorphous A1, Fe, and Si oxides using an
alkaline medium of 0.1 M tiron buffered at pH 10.5, an extraction tempera-
ture of 80°C, and an extraction time of 1 hour was reported b y Biermans
and Baert (1977). This method has not been tested as an exploration tool.
Crystalline iron oxides: Several extracting solutions have been em-
ployed to dissolve un-defined iron oxides. Hydrochloric acid of different
concentrations has been used to extract acid-soluble or cold-extractable
metals from soils and sediments to enhance metal anomalies (Canney and
Hawkins, 1958; Bradshaw et al., 1974; Malo, 1977). The implication is
that some of the metals extracted may have been associated with iron
oxides. In a two-step extraction procedure, Carpenter et al. {1978) used
20% hydrochloric acid to dissolve iron oxides and associated metals from
boulder coatings after removal of the manganese-oxide phase. Hydrochloric
acid can dissolve iron oxides of varying degree of crystallinity, depending
on the concentration of the acid and the temperature of reaction (Chao and
Zhou, 1983). At elevated temperatures hydrochloric acid can attack primary
silicate minerals as well as clays. Also, the acid will dissolve carbonate
minerals and replace metal ions adsorbed on inorganic and organic colloids.
The combined solution of hydroxylamine hydrochloride and acetic acid
(0.02--1 M NH2OH.HCl-25% HOAc) was initially devised by Chester and
Hughes (1967) to investigate the partitioning of trace metals in pelagic
sediments. Filipek and Theobald (1981) used the acid reducing solution to
extract moderately reducible hydrous iron oxides from sediments. This
solution tends to effect an overestimation of amorphous iron oxides because
of some attack on crystalline iron oxides (Chao and Zhou, 1983). Iron
oxides extracted in this fashion may be intermediate in crystallinity between
amorphous iron oxides and crystalline iron oxides in the iron-oxide continuum
described by Schwertmann (1973).
Another chemical reagent c o m m o n l y used to dissolve iron oxides from
soils and sediments is oxalic acid. It is a weak organic acid capable of dis-
solving weathering products, including hydrous oxides of iron, manganese,
 117

and aluminum, and clays together with a host of associated metals. Its ability
to dissolve metals from soils and sediments is related to the reduction of
oxides of iron and manganese, and to complexation of the released metals
rather than to protonation, as is true with strong inorganic acids s u c h a s
hydrochloric acid. Oxalic acid has been used as an extractant in studies of
soil weathering (Gallagher and Walsh, 1943; Ball and Beaumont, 1972) and
geochemical exploration (Alminas and Mosier, 1976; Carpenter and Hayes,
1979). Oxalic acid has also been shown to dissolve organic matter (Gallagher
and Walsh, 1943) and to a certain extent to dissolve primary minerals in-
cluding sulfides, and elemental metals (Baker, 1973).
Oxalic acid is very effective in dissolving both amorphous and crystalline
iron oxides (Taylor and Schwertmann, 1974; Chao and Zhou, 1983), espe-
cially at the boiling-water temperature commonly used. Among the crystal-
line iron oxides, oxalic acid is particularly effective in bringing about the
dissolution of magnetites (Chao and Zhou, 1983). The lack of specificity
in differentiating between iron-oxide minerals makes oxalic acid an in-
appropriate extractant for either amorphous or crystalline iron oxides.
However, if information on the nonspecific association of metals with
chemical components in noncalcareous soils and sediments is needed for
geochemical exploration, oxalic acid serves the purpose.
Gatehouse et al. (1977) reported using a hydrazine chloride solution
(pH 4.5) to dissolve crystalline iron oxide in a sequential analysis. No data
were given to permit evaluation of the effectiveness of the extraction.
The dissolution of crystalline iron oxides requires chemical reduction of
ferric iron as the initial step (Oades, 1963). The most extensively used
reagent is sodium dithionite (Na2S204). Deb (1950) introduced this reagent
to soil work and found it superior to several other reagents in terms of
efficient removal of the oxides and less destructive effect on clay minerals.
Different versions of the sodium-dithionite method have been reported
since its introduction by Deb (Aguilera and Jackson, 1953; Mitchell and
Mackenzie, 1954; Mehra and Jackson, 1960; Kilmer, 1960; Coffin, 1963;
Holmgren, 1967; Mitchell et al., 1971). The variations involved are: (1)
pH and temperature of the reaction medium; (2) presence of chelating and
buffering agents; (3) single or multiple treatments; (4) length of reaction;
(5) the form (solution vs. solid) and amounts of sodium dithionite added;
and (6) use of ultrasonic agitation.
The sodium-dithionite solution dissolves iron oxide sol-gel completely;
hematite and goethite partially, as much as 20 to 40 percent or higher;
and maghemite, magnetite, and ilmenite only slightly (Aguilera and Jackson,
1953; Coffin, 1963; McKeague et al., 1971; Taylor and Schwertmann,
1974). The iron-containing clay mineral nontronite can be deferrated by
sodium dithionite, but pyrite is not affected (Coffin, 1963). The degree
of dissolution of the two crystalline iron oxides, hematite and goethite, is
related to the crystallinity and to the fineness of grinding of the oxides
(Oades, 1963; McKeague and Day, 1966; McKeague et al., 1971). The
1,18

highly crystalline iron oxides occurring as sand- or silt-sized particles in soils

are less soluble than fine-grained crystalline oxides. In order to obtain
complete dissolution of crystalline iron oxides, the sample must be finely
ground, and multiple extractions may be required.
In using sodium dithionite to extract metals associated with crystalline
iron oxides, it is important to note that the available dithionite reagent
contains metal impurities, especially zinc, which can be as high as 400 ppm
(Jenne et al., 1974). In addition, the possibility exists for the precipitation
of iron sulfide, which may hold back some of the released metals. This
precipitate can be dissolved by acid washing (Deb, 1950), or precipitation
can be prevented by the addition to the reaction medium of citrate as a
chelating agent (Aguilera and Jackson, 1953; Mehra and Jackson, 1960).
Because of difficulties experienced with sodium dithionite, an alternative
should be sought. Tamm's reagent (0.175 M (NH4)2C204-0.100 M H2C204,
pH 3.3) has been shown to dissolve crystalline iron oxides (de Endredy,
1963; Le Riche and Weir, 1963) under proper ultraviolet irradiation. With
experimentation, a combination of standard ultraviolet intensity, time of
reaction, and fineness to which the sample must be ground can be deter-
mined to effect dissolution of crystalline iron oxides. One additional advan-
tage is the fact that both ammonium oxalate and oxalic acid can be obtained
in high purity.
A recent report by Shuman (1982) indicates that a combined solution
of ammonium oxalate (0.2 M)-oxalic acid {0.2 M) in 0.1 M ascorbic acid
can be used to dissolve crystalline iron oxides from soils. However, the much
greater dissolution of aluminum by this combined solution than by the
dithionite reagent needs further study.

Sulfides. Both primary and secondary sulfide minerals in soils and sediments
contain an array of trace metals (Jenne, 1977). Many of the ore-forming
metals are major constituents of sulfide minerals. A knowledge of the type
and concentration of trace metals in sulfides may help identify the metals
of mineralization and can enhance geochemical contrasts between mineralized
and barren bedrocks (Olade and Fletcher, 1974). The distribution of sul-
fides in soils and sediments and the change of concentration of trace metals
contained therein may indicate the direction of, and the distance from,
mineralization.
A hydrogen peroxide-ascorbic acid leach for the selective extraction of
sulfides and associated metals from rocks was described by Lynch (1971)
from procedures originally developed by Simirnova et al. (1968). The
reagent will not attack other mineral phases such as silicates. However,
partial decomposition of manganese oxides and organic matter may be
expected if they are not removed first. Peachey and Allen (1977) modified
the hydrogen peroxide-ascorbic acid leach by treating the residue after the
leach with a warm solution of ammonium acetate in order to dissolve any
Pb804 precipitated during the oxidation of galena by hydrogen peroxide.
 119

In a comparative study on chemical dissolution of nine common sulfide

minerals, Chao and Sanzolone (1977) found that galena, chalcopyrite,
cinnabar, molybdenite, pyrite, sphalerite, and tetrahydrite were decomposed
to the extent of 43 to 66 percent of the total sulfur content by the hydrogen
peroxide-ascorbic acid leach, but orpiment and stibnite were only slightly
attacked by the leach.
Several chemical reagents stronger than the hydrogen peroxide-ascorbic
acid leach have been used for the decomposition of sulfide minerals prior
to chemical analysis, including aqua regia (Stanton, 1966), nitric and tartaric
acid (Rubeska, 1968), water-bromine (Czamanske and Ingamells, 1970),
and a solution of bromine in carbon tetrachloride (Hubert and Lakin, 1973).
A potassium chlorate-hydrochloric acid method (Dolezal et al., 1968) was
evaluated by Olade and Fletcher (1974) in comparison to aqua regia and the
hydrogen peroxide-ascorbic acid leach. They found that the potassium
chlorate-hydrochloric acid procedure was most selective to sulfides and least
damaging to silicates. The potassium chlorate-hydrochloric acid method
can be reinforced by an additional gentle boiling of the residue in 4 N nitric
acid for 20 minutes to dissolve completely the nine sulfide minerals dis-
cussed by Chao and Sanzolone (1977).
In using the above stronger chemical treatments, metals in weaker chemical
bonding in mineral phases and organic matter than those in sulfides should
be first removed.

Residue. After removal of the above chemical phases from the geochemical
sample, the residue consists of silicates and some other resistant mineral
species. The residue can be decomposed by digestion with hydrofluoric
acid in combination with other mineral acids such as sulfuric, nitric, per-
chloric, and hydrochloric acid; or by fusion with alkali fluxes such as sodium
carbonate, lithium metaborate, and lithium tetraborate. However, metals
in the residue are less important if the partial dissolution study is directed
toward weathering products than if the study is related to rock geochemistry.

Methods of sequential multiple extractions

Sequential multiple extraction techniques are used to partition metals

into different chemical phases of the material sampled. Chemical extractants
of various types are applied sequentially to the sample of soil or sediment,
each successive treatment being more drastic in chemical action or of a
different nature than the previous one.
Metals or nonmetals can be expected to partition into several chemical
forms or phases in relation to the solid phases of soil and sediment: water-
soluble fraction little affected by solid surfaces; metals or nonmetals held
onto surfaces but exchangeable with other metal or nonmetal ions; metals
or nonmetals closely associated with or residing in carbonates, organic matter,
manganese oxides, amorphous iron oxides, crystalline iron oxides, and
120

residue composed of silicates, sulfides, and other resistant minerals. Each

phase may be further divided into subphases by using more refined analytical
techniques if such division is warranted; however, not all chemical forms
of an element are of use in geochemical exploration under a given geological
setting. For example, iron and manganese oxides of varying degree of crystal-
linity and hydration are the foremost sites of residence for metals and non-
metals, rather than the carbonates and organic matter, in soils and sediments
from a tropical region where oxidative weathering and intensive leaching
prevail.
If the single extraction methods discussed above are arranged in proper
sequence, a sequential multiple dissolution technique is formulated. The
purposes of selective sequential extractions in geochemical exploration
are: (1) to elucidate the mode of occurrence of trace elements in soils and
sediments (Rose, 1975; Webb and Thompson, 1977; Tessier et al., 1979);
(2) to enhance geochemical contrasts between mineralized and background
areas (Hoffman and Fletcher, 1979); and (3) to differentiate between
lithological and environmental effects related to mineralization (Bradshaw,
1979). The function of selective sequential extractions in geochemical
exploration has been expanded by Chao and Theobald (1976). They ob-
served that a knowledge of the distribution of metals among different solid
phases, determined by sequential extractions, provides information that is
valuable at two levels of the geochemical exploration process: (1) during the
orientation stage, to provide a proper selection of sample media and extrac-
tion procedure; and (2) during the follow-up stage, to help evaluate and
interpret the significance of metal anomalies in regard to degree of weathering,
element association, and ore genesis. Interest in selective sequential extrac-
tions in different disciplinary areas of geoscience has grown since Le Riche
and Weir {1963)recognized various chemically bound forms of trace elements
in soils, Rose and Suhr {1971) applied an extraction technique to stream-
sediment geochemical exploration, and McLaren and Crawford {1973)
made a systematic study on the fractionation of soil copper using selective
chemical extractants.
The fractionation schemes that have been used in geochemical work are
reviewed below in chronological order to put the extracting techniques in
perspective and to identify the sources. The phase extracted in each step is
followed by the extractant shown in parentheses, and phases are numbered
in the sequence of the extractants. Metals released from each fraction are
defined as related to that fraction.

Procedure o f Rose and Suhr (1971) for use with stream sediments
By using the scheme below and regression analysis of trace-metal con-
tents (Co, Cu, Ni, and Zn) against major elements, Rose and Suhr (1971)
were able to reduce the background variation in stream-sediment geochemical
exploration. Their fractionation scheme is:
(1) Soluble, exchangeable, and carbonates (NaOAc buffered at pH 5).
 121

(2) Organic matter, manganese oxides, and sulfides (H202).

(3) Iron oxides (Na dithionite-citrate-bicarbonate).
(4) Residue (segregated into sand, silt and clay, and each size fraction ana-
lyzed by atomic emission spectroscopy).

Technique o f Chao and Theobald (1976) employed under conditions o f

intensive weathering
The technique summarized below for fractionation of Cu in soils and
sediments (Chao and Theobald, 1976) was applied to soils and active stream
sediments from Puerto Rico (Learned et al., 1981) where intensive chemical
weathering has resulted in leaching of soluble and exchangeable metal ions,
destruction of organic matter, and accumulation of iron oxides.
(1) Manganese oxides and "reactive" iron oxides (0.1 M NH2OH'HC1-0.01
M HNO3).
(2) Amorphous iron oxides (0.25 M NH2OH'HC1-0.25 M HC1).
(3) Crystalline iron oxides (Na dithionite-citrate).
(4) Sulfides and resistant iron minerals (KC103-HC1 and HNO3).
(5) Silicate residue (HF-HNO3).
Using this scheme to fractionate the soil copper, Learned et al. (1981)
were able to interpret the results both in terms of the degree of chemical
weathering and in terms of the enhancement of the geochemical contrast of
copper. The partitioning of copper among secondary oxide fractions proved
to be especially diagnostic of the geochemical environment. In strongly
leached soils, crystalline iron oxides fix the highest percentages of the oxide-
related copper, and the total copper content is much lower than in weakly
leached soils. In weakly leached soils, amorphous iron oxides fix the highest
percentages of the oxide-related copper. Although the magnitude of geo-
chemical contrast varies widely among the fractions, at least one fraction of
the oxide-related copper provides stronger contrast than the total copper
in the bulk sample. Copper related to amorphous iron oxides provides
optimal contrast for soils on a weakly leached capping, whereas copper
related to crystalline iron oxides provides optimal contrast for soils on a
strongly leached capping. These results serve as a clear testimony to the
statement made by Chao and Theobald (1976) regarding the function of
sequential extractions in the selection of sample media and extraction
procedure as well as in the interpretation of geochemical data in relation
to the degree of weathering.

Fractionation scheme o f Gatehouse, Russell, and Van Moort (1977)applied

to soils
Application of the fractionation scheme for Cu, Pb, Zn, Fe, and Mn (given
below) of Gatehouse et al. (1977) to the profiles of Tasmanian soils disclosed
much stronger scavenging effect of iron oxides on transition metals than was
generally recognized.
(1) Water-soluble fraction (distilled H20).
122

(2) Exchangeable and some carbonates (1 M NH4OAc-HOAc, pH 4.5).

(3) Manganese oxides (0.1 M NH2OH'HCI-1 M NH4OAc, pH 4.5).
(4) Organic matter and sulfides (H202 and 1 M NH4OAc).
(5) Hydrous iron oxides (NH2NH2 ° HC1 and HC1, pH 4.5).
(6) Silt and clay in residue treated with HF.
The quantitative expression of the scavenging effect of various components
aids in differentiating between true and false anomalies. Because the nature
of soils varies in different climates and at different localities, Gatehouse
et al. (1977) concluded that an initial complete sequential extraction of
soil samples is valuable in early stages of geochemical exploration.

Selective extraction technique of Hoffman and Fletcher (1979)

Distribution of metals (Cu, Zn, Fe, Mn, and Mo) in various mineral phases
revealed by the selective sequential extraction technique of Hoffman and
Fletcher (1979) outlined below has practical application in mineral explora-
tion because the distribution indicates the mode of occurrence of metals
and is valuable in the interpretation of the genesis of geochemical anomalies:
(1) Organic matter (NaOC1 at pH 9.5).
(2) Manganese oxides (0.1 M NH2OH.HC1, pH 2.5).
(3) Amorphous iron oxides (0.175 M (NH4)2C204-0.100 M H:C:O4, pH
3.5).
(4) Crystalline iron oxides (Na dithionite-citrate-bicarbonate, pH 7).
(5) Residue (HC104 and HNO3).
The retention of trace metals by the material in the residue after the
extractions follows the order: soils>stream sediments>lake sediments, and
appears to be a function of the degree of weathering of the medium.

Procedure of Filipek and Theobald (1981) for use in arid regions

The application of a sequential dissolution technique to a porphyry
copper deposit in the Basin and Range province in Arizona followed the
scheme given below (Filipek and Theobald, 1981) for Fe, Mn, Cu, Zn, and
Pb:
(1) Exchangeable and carbonates (1 M HOAc).
(2) Manganese oxides (0.1 M HN2OH'HC1-0.01 M HNO3).
(3) Organic matter and sulfides (H202 and NH4OAc in 6% HNO3).
(4) Hydrous iron oxides (0.25 M NH2OH'HC1-25% HOAc).
(5) Residual crystalline fraction (HF, HNO3, and HC1).
The results of these sequential extractions showed that in the semiarid
and arid environments, where mechanical dispersion predominates, uncritical
assignment of unique phases, such as manganese oxides or organic materials,
to a given extraction scheme could lead to false interpretations of weathering
processes and the migration of metals. The relative proportions of copper
dissolved from jarosite and chrysocolla in each step of the fractionation
scheme can be used as a "fingerprint" for recognition of the presence of
these two minerals. Whereasjarosite releases its copper mainly in the hydrous
 123

iron oxide and residue fractions, chrysocolla releases copper gradually in

each step of the fractionation in proportion to the duration of the first four
extractions due to the mildly acid condition of the extractants used. The
acetic acid extraction is most effective for precisely identifying areas of
mineralization. The residue has the longest dispersion train. The important
interpretation of this observation is that total metal concentrations are most
effective in arid environment for reconnaissance surveys.
A modification of this scheme, with the acetic acid extraction eliminated,
has been applied to partition copper, zinc, and lead in boulder coatings and
stream sediments from the vicinity of a polymetallic sulfide deposit (Filipek
et al., 1981). This study showed that organic matter is an important scavenger
of heavy metals on boulder coatings, adding to their usual accumulation in
oxides.

Technique of Sondag (1981) for use in areas contaminated, by old mine

dumps
Sondag (1981) applied selective extraction procedures to geochemical
prospecting in an area contaminated by old mine dumps, according to the
following scheme of fractionation of Pb:
(1) Water soluble, exchangeable, and some carbonates (1 M NH4OAc, pH
4.5).
(2) Manganese oxides (0.1 M NH2OH.HC1, pH 4,5).
(3) Organic matter (35% H202).
(4) Amorphous iron oxides (0.175 M (NH4)2C204-0.100 M H2C204, pH 3.3).
(5) Crystalline iron oxides (the same reagent as in (4) under ultraviolet
light).
(6) Clay and silt residue (HF and HC1).
The results of these selective extractions showed that the geochemical
contrast between anomalous and background values for Pb is highest for the
hydroxylamine hydrochloride extraction and is about the same for all other
dissolution steps. Only the final acid digestion produced anomalous values
in the contaminated samples. This observation was interpreted to show that
contamination of the sample adds metals in the form of resistant phases
which require strong acids for dissolution.

Fractionation scheme of Bogle and Nichol (1981) applied to organic-rich

alluvium
Studies of metal transport, partition, and fixation in drainage sediments
were conducted by Bogle and Nichol (1981) using the fractionation scheme
for Cu, Pb, Zn, Fe, and Mn as follows:
(1) Organic matter, exchangeable and sulfides (NaOC1).
(2) Manganese oxides (0.1 M NH2OH.HC1).
(3) Hydrous iron oxides (0.25 M NH2OH'HC1-0.25 M HC1).
(4) Crystalline iron oxides (1.0 M NH2OH.HC1-25% HOAc).
(5) Residue (HNO3).
124

Results showed that the accumulation of lead and zinc by amorphous iron
oxides, combined with the adsorbing and chelating action of organic matter
on lead and zinc, makes organic-rich sediments from swampy areas of the
drainage system an excellent sample medium for reflecting local mineraliza-
tion. Down-drainage anomalies of metals can be accentuated by selective
analysis of the amorphous iron oxide phase.

APPLICATION OF PARTIAL DISSOLUTIONTECHNIQUESTO GEOCHEMICAL

EXPLORATION FOR ORE BODIES

Advantages over bulk analysis

An optimistic appraisal of the use in exploration geochemistry of partial

dissolution techniques recently has been expressed by Bradshaw (1979).
He regarded the techniques as a most significant contribution, because
exploration geochemists, through an understanding and application of
selective and specific extractions, can differentiate between effects on metal
distribution caused by mineralization, and those resulting from lithological
and environmental factors. The advantages of applying sequential dissolution
techniques to geochemical exploration, as derived from the case histories
enumerated above, can be summarized as: (1) understanding the mode of
occurrence of elements of geochemical interest; (2) helping choose proper
sample media and extraction procedures for analytical work; (3) enhancing
geochemical contrast above what can be accomplished by the bulk analysis;
(4) showing features related to the degree of weathering not apparent by
the use of other chemical means; and (5) aiding the interpretation of chemi-
cal data in relation to the broad geochemical environment.

Use with oxide coatings as the geochemical sample medium

Partial dissolution techniques have been shown in the above discussion

to be advantageous over the conventional bulk analysis in geochemical
prospecting. Of the solid phases that can be selectively extracted, iron and
manganese oxides and hydrous oxides deserve special attention, because they
exert tremendous physicochemical influence on other mineral species or
organic materials that is far out of proportion to their concentration (Jenne,
1968). Under normal aerated conditions, iron and manganese oxides occur
in the weathering environment in the form of coatings, concretions, nodules,
or discrete particles of colloidal dimensions (Jenne, 1968; Chao, 1972).
Coatings of iron and manganese oxides are found both in the humid regions
and arid environments. In arid and semiarid regions, these oxides form desert
varnish (Hunt, 1954; Engel and Sharp, 1958; Bauman, 1976; Potter and
Rossman, 1979). The general mode of occurrence of these oxides as coatings,
their chemical reactivity, and their strong ability to scavenge ore elements
make them an attractive sample medium for exploration geochemists (Canney,
 125

1966; Chao and Theobald, 1976; Nowlan, 1976; Gatehouse et al., 1977).
An additional attractive feature for use in geochemical exploration is that
coatings of iron and manganese oxides can be selectively extracted by chemi-
cal dissolution or separated by mechanical means for analysis.
The merit of iron-manganese oxide coating as a sample medium in stream-
sediment geochemical surveys in the vicinity of known mineralization has
been evaluated by Carpenter et al. (1975, 1979), and Carpenter and Hays
(1979). The extractants used were 0.1 M hydroxylamine hydrochloride-0.01
M nitric acid (Chao, 1972) for manganese oxides and 3% oxalic acid or 20%
hydrochloric acid for both iron and manganese oxides. The contents of
metals (Cu, Pb, Zn, Co, and Ni) were normalized by weight, surface area,
or ratios with manganese and/or iron to facilitate comparison of background
and anomalous values. The results of the analytical data indicated that
geochemical contrasts and downstream detectability of mineralization were
markedly higher in oxide coatings than in the conventional minus-80-mesh
fraction of stream sediments.
The results from analyses of secondary iron-manganese oxides in rock
coatings extractable by hot oxalic acid solution were compared with the
results from analyses of heavy-mineral concentrates from alluvium in a semi-
arid area of New Mexico (Watts et al., 1981). The conclusion reached was
that both media show generally similar patterns of anomalous metal dis-
persion.
An evaluation of the analytical data from samples of iron-rich fracture
coatings separated mechanically from six disseminated gold deposits in
Nevada disclosed a significant geochemical enhancement over that from
standard lithogeochemistry (Larson et al., 1981;Crone, 1982). Joint coatings
were found to contain much higher amounts of gold, arsenic, antimony,
copper, zinc, and mercury than the conventional sample media. Geochemical
contrasts were higher where fracture coatings were used than the contrasts
obtained by analysis of samples of soft, sediment, and rock chips. As a result,
larger exploration targets were outlined by use of the iron-rich coatings than
by other media. Anomalous concentrations of mercury in the parts per
million range found for iron-rich coatings on rock surfaces are of particular
interest to the exploration geochemist, because the high temperature and
strong desiccation in an arid region seemingly would tend to cause the loss
of a volatile element such as mercury.
Use has also been made of iron-manganese coatings on soil and sediment
particles as well as on stream boulders and pebbles for studies indirectly
related to geochemical exploration. These include: (1) heavy-metal association
with oxide coatings in relation to grain size of stream sediments (Whitney,
1975), and heavy-metal association affected by geology and land use (Whitney,
1981); (2) factors influencing the partitioning of heavy metals in boulder
coatings and stream sediments (Carpenter et al., 1978; Filipek et al., 1981);
and (3) trace-metal adsorption characteristics of oxide coatings (Robinson,
1981; Lion et al., 1982; Cerling and Turner, 1982).
126

The above examples from recent studies demonstrate that additional

significant geochemical information related to areas of known mineralization
can be derived by utilizing oxide coatings as sample media and various partial
dissolution techniques in preparation for analysis.

Other applications

The popularity enjoyed by sequential dissolution techniques in geo-

chemical exploration has been extended to other disciplinary areas of earth
science; i.e., geochemical studies of river and lake sediments (Gibbs, 1977;
Filipek and Owen, 1979; Tessier et al., 1979), nearshore deposits (Presley
et al., 1972; Gupta and Chen, 1975; Kitano and Fujiyoshi, 1980; Filipek
and Owen, 1981; Lindau and Hassner, 1982; Lion et al., 1982) and offshore
marine sediments (Nissembaum, 1972; F6rstner and Stoffers, 1981), soils
(McKeague et al., 1971; McLaren and Crawford, 1973; Wakasuki et al.,
1977; Simes and Patrick, 1978; Shuman, 1979; Iyengar et al., 1981), and
environmental quality (Kaback and Runnells, 1980; Gambrell et al., 1980;
Khalid et al., 1981);

CONCLUDING REMARKS

The use of partial dissolution techniques in geochemical exploration has

reached a stage of vigorous development. Because of the variety of proce-
dures and extractants available, each serving different purposes, the choice
of technique is open to suit the geological setting, the type and degree of
weathering, and the mode of occurrence and chemical forms of ore and
pathfinding elements. Further development of these techniques and con-
comitant demonstration of their ability to delineate areas of mineralization
and to identify mineral deposits will lead to their fuller utilization by the
exploration community. Partial dissolution techniques can be expected to
play a prominent role in the search for concealed ore bodies in the years
to come.

ACKNOWLEDGMENTS

The author thanks William C. Overstreet, Richard F. Sanzolone, Lorraine

G. Filipek, and Theodore Botinelly of the U.S. Geological Survey and
Everett E. Jenne of the Barrette Pacific Northwest Laboratories for their
constructive criticisms and suggestions for improvements of the paper.

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