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G.J.SGOVETT (Editor)
VOLUME 5
Regolith Exploration Geochemistry
in Arctic and Temperate Terrains
KALEVI KAURANNE
Geological Survey of Finland, SF-02150 Espoo, Finland
with
Assisted by
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1. Geochemical p r o s p e c t i n g — S c a n d i n a v i a . 2. Geochemical
prospecting—Arctic regions. 3. S o i l chemistry—Scandinavia.
4. S o i l c h e m i s t r y — A r c t i c regions. 5. Geology, S t r a t i g r a p h i c -
-Quaternary. I . K a u r a n n e , L . K. I I . Salminen, Reijo.
I I I . E r i k s s o n , K a r i n , 1937- . IV. Series.
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EDITOR'S FOREWORD
G.J.S. GOVETT
Helsinki, Finland and Sydney, Australia
VII
ACKNOWLEDGEMENTS
KALEVI KAURANNE
IX
THE AUTHORS
Chapter 1
INTRODUCTION
"V**
TILL ON SLOPES
TILLY HILLS
SHALLOW BOGGY TERRAIN = JÄNKA = MUSKEG
Fig. 1-1. Different types of overburden formations and materials in arctic and temperate
glaciated terrain, (photo Peter Johansson)
History of soil geochemical prospecting 3
He also notes that water which in confined places takes on colour and
taste from the surrounding soil "reflects the metalliferous rock through
which it is running by its nasty taste and mean flavour," and as the final
test "kills the animals drinking it".
Daniel Tilas, another Finnish state geologist, reported in 1743 that ore
floats are situated to the southeast side of ore suboutcrops in Finland, so
hinting for the first time at the method of boulder tracing. This method
of exploration was taken to North America as early as 1747-1751 by Pehr
Kalm during his botanical excursions (Goldthwait, 1982). A century later
the direct correlation between the chemistry of the overburden and the
bedrock below was taken careful note of by Hjalmar Lundbohm (1887)
in his studies of Swedish marble formations and the Ca content of the
overlying soil.
It was not hard to guess at the origin of ore boulders in talus up on the
valley side. As early as 1802 Playfair deduced the activity of valley glaciers
in transporting boulders along the valley, and in 1832 Bernhardi traced the
source of the big porphyrite and granite erratics in northern Germany back
to Scandinavia (Goldthwait, 1982). Nils Nordenskiöld published his map
of glacial striae in Finland in 1863. Moving into our own century, boulder
tracing for glaciological (Helmersen, 1882; Hedström, 1894; Hausen, 1912)
and later for explorational purposes became popular and important not
only in Finland but in all northern countries including Canada and the
United States (Sauramo, 1924; Högbom, 1931; Lundqvist, 1948; Flint,
1947; Holmes, 1952; Grip, 1953; Aurola, 1955).
Minerals were sought and mined from sediments long before Agricola
— for example, by panning of gold and precious stones. Since the gold
rushes of last century, the heavy minerals in sediments have been studied
worldwide both for prospecting purposes and "mapping" of the underlaying
bedrock (e.g., Raeburn and Millner, 1927; Kivekäs, 1946; Mertie, 1954;
Theobald, 1957; Theobald and Thompson, 1959; Lee, 1971).
Mineralogical analysis is based on relatively few identified grains that
hopefully are typical. If thousands were counted the process would be too
time consuming and tedious. A sample of finer fraction analyzed chemically
gives more reliable results. The first attempts to use soil chemistry
specifically for prospecting were made in the Soviet Union in the 1920s by
Vernadskij, Vinogradov and Fersman; the method was called metallometry,
and according to the metal sought, cuprometry, ferrometry etc. (Sergeev
and Solovov, 1937).
With little delay the chemical method was applied in Norway (Gold-
schmidt, 1934; Vogt, 1939), Finland (Rankama, 1940; Kauranne, 1951),
Canada (Chisholm, 1950) and the United States (Hawkes and Lakin, 1949;
Huff, 1951). Rapidly pedogeochemistry, as it was called in the West, spread
throughout the world, being successfully applied in a variety of geological
environments.
General principles of element distribution 5
The northernmost parts of the Earth are still covered by ice and
surrounded by a zone of permafrost. Similar conditions are met with in the
southern hemisphere. A much larger part of the Earth was frozen and even
glaciated several times during the Pleistocene. The preglacial weathered
crust was abraded and is today found in situ only in isolated places such as
in areas of ancient ice divides and in bedrock depressions. Upon this regolith
were deposited vast amounts of glacial till and glacifluvial sediments, now
partially covered by postglacial mineral and organic formations similar
to those forming the overburden of the nonglaciated temperate zone.
The different materials of the overburden as a target for geochemical
exploration are shown in Fig. 1-2.
The distribution of elements in a material — its geochemical character
— depends on the origin and geological evolution of the material and is
specific for just that material. Without a sound understanding of this fact it
is impossible to interpret correctly the results of geochemical studies based
on the material. It cannot be emphasized too strongly that mixing of results
obtained from the assay of different materials leads to fatally erroneous
conclusions.
The primary dispersion of elements occurred during the magmatic dif-
ferentiation of the Earth, when major, minor and trace elements were
Fig. 1-2. The different materials of the overburden as a target for geochemical exploration.
10 Introduction
Chapter 2
GLACIGENIC DEPOSITS
The Pleistocene epoch, which began 2-3 million years ago, was dominated
by glaciations. Large parts of the northern and southern hemispheres, as
well as the highest mountain ranges were entirely covered by ice (Fig. 2-1)
(Flint, 1967; Lundqvist, 1980; Ehlers, 1982; Rogerson, 1982; Michelson et
a l , 1983).
Fig. 2-1. Areas of the northern hemisphere covered by the Pleistocene ice sheets.
MAXIMUM EXTENT OF THE PLEISTOCENE GLACJATIONS,
AREAS INUNDATED BY SEA OR LAKES AND 25>
8
500 km 3
ft*
•8
o
CO
Fig. 2-2. Areas in Europe covered by the Pleistocene glaciations and by water during deglaciation.
Glaciations and interglacials 15
Fig. 2-3. Maximum extent of Pleistocene glaciations in North America and areas of upheaval.
bodies. Likewise in the Himalayas, Alps, Cordilleras, Andes, and even the
Apennines the valleys were filled with glaciers while the highest tops were
left barren.
Glacial processes 17
PLEISTOCENE GLACIATIONS
CANADA FENNOSCANDIA EUROPE
(Shilts - 8 4 ) (Sibrava - 8 6 )
YEARS BP
PEAT and HUMUS BEDS
CENE
I HOLO-
MARINE ^GRAVED/SEDIMENT S
9000 TYRREL SEA
VARVES, GLACIAL LAKES
AGASSIZ etc.
WISCONSINAN
^/CLAY
^ ^ - ^ ^ ^ TILL WEICHSEL III Z>
KIPLING TILL ^"""^^ (VALDAI)^>
VARVED CLAY
FRIDAY CREEK (^GÖTAÄLV
SAALE
DARK GREY TILL (DNIEPR)
f "DÖMNITZ
SAND, GRAVEL, CLASTS
V (ROMNY)
DISCONTINUOUS VARVES FUHNE
(PRONYA)
DARK RED TILL S ^ HOLSTEIN
( (LIKHVIN)
LIGHT GREY TILL
ELSTER I&II
(OKA)
ζ^~ CROMER
^ ^ _ _ i g
HELME 1,11,III
(ILOVAI)
/ ^ ARTERN;
^^___ig
MENAPIAN
Fig. 2-4. Glaciations, interglacials and the corresponding formations in North America and
Europe. Compiled from Shilts (1984a) and Sibrava (1986).
18 Glacigenic deposits
Baltic Sea
clay
Litorina Sea
muddy clay
Ancylus Lake
stratified clay
Yoldia Sea
clayey silt
IVBED*OCI
Fig. 2-5. Late-glacial and postglacial formations at the bottom of the northern Baltic Sea.
GLACIAL PROCESSES
Erosion
Fig. 2-6. Roches moutonnees. If the rock is fine-grained and resistant to weathering, grooves,
striae, facets, trains of crescentic marks and traces of scratching and polishing will be visible
on the surface (photo Kalevi Kauranne).
Transport
Two types of ice flow have been distinguished: compressive and extend-
ing. In compressive flow the slip surfaces favour upward movement of
material, in extending flow downward movement. The former leads to long-
distance transport, the latter allows mixing of the supraglacial material
into local lodgement till.
Debris may be transported beneath or in the glacier, on the surface or in
front of it. The comminution, mixing and orienting of the material mainly
depend on where and how it is transported. The mode of transport is im-
printed into the lithology of different fractions, into grain size distribution,
into orientation of grains and into the form and texture of the formation.
20 Glacigenic deposits
Fig. 2-7. Glacier margin and glacigenic formations during the melting off.
Fig. 2-8. Ice marginal and glacifluvial deposits formed during deglaciation: till, esker gravel
and sand, beach sand, laminated silt and clay, annual moraines. Redrawn with permission from
Magnusson et al., 1949.
Glacial tills 21
Deposition
GLACIAL TILLS
Characteristics
DERIVATION
of
BY SUBGLACIAL PROCESSES BY E X T R A G L A C I A L PROCESSES
glacial debris
P o s i t i o n of d e b r i s
IN GLACIER
BENEATH
in TRANSPORT SUPRAGLACIAL
GLACIER
BASAL r ~ ^ ENGLACIAL
before deposition
DEPOSITION
SUPRAGLACIAL
SUBGLACIAL
place AND I C E - M A R G I N A L
a, primary
T
1 LODGEMENT | | J ~ ~ ~ MELTING-OUT ( AND SUBLIMATION )
DEFORMATION LIMITED
MASS
secondary AND F R E E FALL
TRANSLOCATION THROUGH WATER MOVEMENTS
G L A C I A L DEPOSITS
(GENETIC TERMS)
PRIMARY
OR ORTHO-TILLS
h t—r 3
SECONDARY
|| OR A L L O - T I L L S
SECONDARY
OR A L L O - T I L L S
PRIMARY
OR ORTHO-TILLS
n
SUB- MASS MASS
P LODGE- MELT- MOVE-
MELT-OUT
AQUATIC MOVEMENTS
b) specific MENT OUT
o MENT TILLS TILL
varieties MELT- TILLS
OUT -SUBAERIAL ( INCLUDING
or eg. -SUBAQUATIC
TILL TILL SUBLIMATION
la- FLOW e.g. TILL)
in
a TILL FLOW TILL
\, ————4J
Fig. 2-9. Formation of different types of tills. Reproduced with permission from Dreimanis,
1982.
Texture
Till consists of an unsorted mixture of rock and mineral fragments
from boulders to clay size. The particle size distribution depends on
the lithological composition and the amount of preglacial sediments or
weathered material intermixed. Rocks are rather easily broken down into
their natural mineral grain size, or "terminal grade", which commonly lies
in the sand or silt fraction (Fig. 2-10). Further comminution depends on the
abrasion resistance of the minerals; micas and sulphides are easily ground
to clay size, while quartz and feldspars are tougher and concentrated in the
sand fraction (Dreimanis and Vagners, 1971). Glacial milling thus results
in the differentiation of minerals and, simultaneously, the elements.
The grain-size distribution is often bi- or multimodal, with different max-
ima for rock fragments and the principal mineral grains. Short-transported
Glacial tills 23
0 10
Fig. 2-10. Terminal grain sizes (modes) of selected minerals in tills. Redrawn with permission
from Dreimanis and Vagners, 1971.
till contains more coarse fractions than till of remote origin. Mica-rich and
schistose rocks are more easily comminuted and generate more fine mate-
rial than quartz- or amphibole-rich igneous rocks. Classification of tills on
the basis of grain size distribution is done by sieving the material finer than
stones. Grain size distribution of the fines is analyzed by sedimentation
method.
The finer the material the more surface there is in a weight or volume
unit and the more opportunity for fixing of ions transported in ground-
water solution. The finer fractions of till may contain greater amounts of
heavy metals of hydromorphic origin than of glacigenic origin, whereas the
coarser fractions contain mainly clastically transported heavy metals.
Boulders freshly broken from bedrock are angular in shape. During
glacial transport the weaker parts are worn off and the boulders become
somewhat rounded. Clasts of finer grain lithologies are sometimes striated,
obtaining a bullet-like shape. If the material is transported in water it be-
comes rounded and polished and preserves this shape if again incorporated
in till and transported.
Structure
Most tills are homogeneous and massive, without layering or other
distinct structural features. The circumstances occurring during and even
after the deposition affect the structure, the grain size, the lithology and
thus the geochemistry of tills.
24 Glacigenic deposits
Fig. 2-11. Vertical movement of mineral material during periglacial time: an ice wedge in
a gravel deposit in southern Finland. This is analogous to a mudboil in till (photo Kalevi
Kauranne).
Glacial tills 25
ORIEN-
TYPE OF TILLS, TYPE AND AGE OF INTERLAYER
TATION
Fabric
During transport the elongated grains of till tend to be oriented in
the direction of ice movement, the very long ones transverse to it. The
orientation, the striation and the bullet shape of the clasts and stones are
due to the laminar movement of the stone/ice material. Stone orientation
is usual for lodgement tills and may be found in melt-out tills as well (Figs.
2-12 and 2-13). Flow of the till partly or totally reorients the material, so
that the predominant orientation of stones may be perpendicular to the
flow (Lundqvist, 1948; Virkkala, 1958; Kauranne, 1959).
Orientation can be determined by compass and clinometer in the field
(Glen, et. al, 1957; Haldorsen, 1983), under the microscope (Seifert, 1954) or
from the anisotropy of magnetic susceptibility (Puranen, 1977; Pulkkinen
et al., 1980). The long axes can be measured either in a plane or three-
dimensionally (Boulton, 1971). Usually the axes tilt gently upwards in the
direction of ice movement.
Lithology
The rock material of till is mainly of local origin, although some stones
and boulders may be transported several, even hundreds of kilometres
(Fig. 2-14). Among factors influencing the lithology of till are the variable
abrasion resistance of rocks, terrain forms, the thickness and velocity of
the ice and any preglacial materials included, especially at the till/bedrock
interface.
26 Glacigenic deposits
Stage
S t a g e II
youngest
»//>
NORWAY
mL0
* *J**i 'fe USSR
USSR
SWEDEN
Fig. 2-13. Flow directions of Weichselian and earlier glaciations in northern Finland. Reproduced
with permission from Hirvas et al., 1977.
Glacial tills 27
%
80-,
Fig. 2-14. Transport of basic volcanic rock material in different grain sizes. Redrawn with
permission from Perttunen, 1977.
The bottom part of a till sheet is somewhat coarser in average grain size
than the surficial part (Fig. 2-15) and the mineral material down there is
mainly local in both the fine and coarse fractions. Geochemically, therefore,
the bottom part is more inhomogeneous. The upper part of a till sheet,
representing mixed material of more remote origin is lithologically more
homogeneous (Hyvärinen et al., 1973) (Fig. 2-16).
Tills may contain material that was abraded, transported and even
sorted in some earlier glacial or glacifluvial process. Such material may
have been transported in different directions than the bulk of the till
material, complicating the interpretation of geochemical results.
Interpretation becomes especially difficult if the intermixed material
was previously sorted and enriched in heavy metals. Distinct leaching
and enriching may have occurred during weathering of the surface of the
bedrock or older soil deposits. Heavy minerals and metals may have been
enriched during transport by flowing water or by wave action, and heavy
metal ions in water solution may have attached themselves to the surfaces
of mineral grains. The "glacial mill" also separates minerals and elements
into different grain size fractions during transport.
Dreimanis (1983) summarizes the main characteristics of tills as follows:
— Tills are usually poorly sorted diamictons.
— They consist of a variety of rocks and minerals, some of them distantly
transported.
28 Glacigenic deposits
Fig. 2-15. Three difFerent till sheets superimposed. Note the distribution and roundness of the
stones (photo Robert Lagerbäck).
0 0
^ 0 0 0
0 0 Ü
0
0
% % c·
0 Ü
0
[äT 0 0
®
0
0
0
"% % 0
0 % % 0
0
0
%%
-[35
®
o 39 (61 0 o
[37 4θ1(6θ) 0
® % %
o 0 66)
0 % %
|ϊοο c
0
88 (12
•[57
® Δ Δ
Δ Δ
-[βδ1
0
•[TO
®
ΛΛ
I®
®
0
0
0
Δ Δ
Δ Δ
53
©
50 100 140 m
I _J
Fig. 2-16. Proportions of local and remote rock material in till at different depths, northern
Finland. Redrawn with permission from Hyvärinen et al., 1973.
Classification of tills
Tills can be divided into two main types — subglacial and supraglacial
till — according to their location in the glacier during transport and
deposition. This was for many years the preferred classification, although
earlier the names used were basal till and ablation till.
The INQUA Commission on the Genesis of Tills has more recently
recommended a new broader classification into primary and secondary till,
according to whether the till was deposited directly by or merely from the
glacier. The former is also known as ortho-till and the latter as allo-till
(Dreimanis, 1982). The terms primary and secondary till are used in the
following.
30 Glacigenic deposits
Primary tills
"Primary tills are deposited directly by glacier ice by lodgement, melting-
out, sublimation or subglacial deformation and traction without noticeable
disaggregation and resedimentation"(Dreimanis, 1982).
Lodgement till is characterized by its tight compaction and fissility
(lamination), its abraded, often striated clasts and its silty major matrix
fraction. Under the clasts in surficial parts there may be a fine sand bed
1-2 mm thick and on the surface of the bedrock a similar thin fine sand
layer, sometimes called rock flour. No other signs of sorting are seen. The
stone orientation is usually well developed and the clasts have obtained a
bullet-like stoss-lee shape. The material is mainly local.
Subglacial melt-out till is deposited from stagnant ice by melting and
closely resembles lodgement till. The fabric usually shows the earlier flow
direction and the degree of compaction is high. Fine lenses of sand or silt
are included, and clasts may be coated with fine sand. The material is
local or more remote depending on whether it was transported at the base
(subglacially) or higher up (englacially) in the glacier (Fig. 2-7).
Supraglacial melt-out till has been transported either englacially or at
the surface (supraglacially). In mountain valleys the material may even be
of extraglacial origin -talus material from mountain slopes. The lithology
is thus heterogeneous and stones are partly oriented parallel and partly
transverse to the direction of glacier movement. The clasts at the surface
are angular if not rounded by meltwater streams and are subrounded if
they have been transported englacially. The grain size is coarser on average
than in the other primary tills, and some sorted materials deriving from
meltwater washing activity are present.
Deformation till is folded, faulted and sometimes thrust off from its
place of sedimentation. The orientation of stones may be disturbed and a
new orientation emplaced. Deformation till might equally well be included
among the secondary tills.
Secondary tills
"Secondary tills are formed from glacial debris which has undergone
redeposition shortly after its release from glacier ice. They are deposited
from glacier ice rather than by glacier ice, in most cases by mass movement
or a short limited free fall of glacial debris subaerially or subaquatically,
with little or no sorting"(Dreimanis, 1982).
Subglacial subaquatic till (water laid till) is deposited by dropping of
mineral particles from the glacier sole through shallow water beneath
the glacier. Poorly sorted, it represents a transition between till and
glaciolacustrine sediments.
Subglacial flow till forms on the lee side of rocks occurring as obstruc-
tions, as in drumlin tails. Flow structures of sorted mineral material
inter layers are typical.
Morainic landforms 31
MORAINIC LANDFORMS
Fig. 2-17. Streamlined forms of tilly hills known as drumlins. Reproduced with permission from
Gluckert, 1976.
resemble ribbed moraines in form but are larger and include more single
ridges; they consist of lodgement till but also contain large rock slabs.
Probably they were formed in front of an oscillating ice lobe. Like that of
the parallel landforms the material of transverse landforms is suitable for
geochemical studies.
Unoriented landforms
The material of unoriented moraines has been deposited by lodging and
the geochemical anomalies found in them, as in the parallel and transverse
formations, are mainly glacigenic. The irregular shape is due to moulding
of the surficial part by freezing and thawing and the rise of boulders. In
submerged areas the surface may be washed poor in fines as well. Often
the main bed of lodgement till is covered by sorted melt-out till of irregular
thickness.
Cover moraine is a thin even layer of lodgement till following the surface
of the bedrock. Hummocky moraine forms a more irregular partly melt-out
till layer without orientation, with an average thickness of a few metres.
Till plain is a basal till formation, thicker in valleys and thinner above
bedrock surface elevations. Often it consists of multiple till beds from
several glaciations, which complicates its use for geochemical studies.
Ice-marginal landforms
Ice-marginal moraines are formed in the melting phase of the glaciation
at the ice front or at the sides of an ice lobe (Fig. 2-18). In summer
the ice edge retreats by melting, and in winter it may push forward a
little. Although the material was originally emplaced by the glacier as till,
meltwaters have manipulated part of it before deposition. Because of the
complex transport of the material, these formations are much less suitable
for geochemical prospecting than the other moraines.
The end moraines formed along the front of the retreating ice consist on
their stoss side of basal till lenses mixed with sorted material and on their
distal side of outwash layers of gravel, sand and silt. The annual moraines,
each formed during a single summer, are only a few decimetres in height.
Terminal moraine is formed at the edge of an ice lobe over a period of years.
Where the glacier paused longer, for tens of years as e.g., at Salpausselkä
near Lahti, Finland, deposits may exceed 100 m in thickness (Fig. 2-19).
Terminal moraines are often hummocky consisting of supraglacial melt-out
till and boulders.
Crescentic ridges of push moraine (thrust moraines) are formed of till
or sorted materials by the winter thrust of the ice edge. Käme moraines
are formed by the melting of dead ice, so that this kind of knob and kettle
terrain is partly covered by till and partly by sand and clasts.
34 Glacigenic deposits
\\ \ I (A ICE,LOBE
w \r&
scale km
Fig. 2-18. Eskers showing the directions of crevasses and tunnels in the glacier and ice-lobe
margins, usually almost parallel to the earlier directions of ice movement, and marginal deposits
showing the different positions of the glacier rand. Map from southern Finland with the great
Salpausselkä end moraines.
N
Proximal s
Distal
140
120
100
80
60
Fig. 2-19. Cross-section through Salpausselkä I end moraine at Lahti. Redrawn with permission
from Hyyppä, 1966.
Sorted glacial sediments 35
Lateral moraines are formed between ice lobes and grade into end
moraines at the ice front. They consist of lodgement till and sorted
material transported from either side of the formation. Crevasse fillings
consist mainly of sorted sediments and resemble radial eskers. Ablation
moraines are very similar to crevasse fillings but formed at the front of the
melting glacier or around melting dead ice lumps; they represent a gradual
transition to glacifluvial formations, and contain lenses of till and layers
of gravel, sand, silt and even clay Suppas, deep conical depressions in the
landscape, some still filled with water, mark the former sites of dead ice
lumps.
GLACIFLUVIAL PROCESSES
Erosion
Meltwater erosion is defined by the ice. Meltwater comes into contact
with bedrock and older overburden formations only at the sides of valley
glaciers, in front of land ice or at the bottom of crevasses and tunnels in the
ice. Mainly it erodes the mineral material already transported by the ice.
Characteristics
Texture
The narrow range of grain sizes is the most striking feature of sorted
sediments, though the degree of sorting varies widely, being highest in
coarse fractions and lowest in the finest fractions. Sorted sediments where
36 Glacigenic deposits
Fig. 2-20. The surface forms, grain size and sorting of glacifluvial sediments depend on whether
they were deposited above or under water, i.e. above or under the highest coast line.
one grain size dominates thus contrast sharply with till where all particle
sizes from boulders to clay flakes are represented. In glacifluvial and
glacilacustrine formations, layers of different grain sizes are superposed
one above another (Fig. 2-20).
The grains, especially clasts of sorted sediments, have characteristically
been rounded by running water or by wave action. Only the very finest
mineral particles are not rounded and polished. The roundness depends on
stream velocity or wave activity, length of time and distance of transport,
and the abrasion resistance of the rock.
Structure
Sediments formed in close contact with the rim of the retreating ice are
coarser than those sedimented farther from it. Beds of gravel, formed in
front of retreating ice typically lie under beds of sand, silt and clay, though
re-advancing of the ice may cause coarse material to be emplaced on top of
fine sediments. Boulders from floating and melting icebergs are sometimes
dropped and buried into the surficial clay of glacimarine and glacilacustrine
deposits.
In fresh and brackish water, the negative surface charge of silicate
minerals keeps the clay flakes apart from one another; silt sedimentates
rapidly but clay continues to sedimentate throughout the winter. In salty
water, the cations of the water "solution" become fixed on the surfaces
of grains and neutralize the repellent forces between mineral particles,
enabling them to flocculate and settle with greater speed.
The summer layer of glacilacustrine clays consists mainly of silt and is
thick, whereas the thinner and darker layer, deposited in winter when no
more material is entering the basin, consists solely of clay-size particles.
Formations of sorted sediments 37
The silts and clays of fresh and brackish water formations show graded
bedding, while those of salty water are massive.
Fabric
Elongated particles are typically oriented perpendicular to the wa-
ter movement, that is, transverse to the esker ridge or parallel to the
beach. Later processes, like mass movements or overriding glacier, may
re-orientate the particles as well as cause folding and faulting of the beds.
Lithology
Glacifluvial deposits are typically polymict, having obtained their mate-
rial both from the till in the ice and from older deposits under the ice. In
smaller formations the material tends to be local; in larger formations it
is of more remote origin. The finer materials have been transported longer
distances. Quartz and feldspars dominate in sand and silt layers, the micas
in clay layers. The great amount of fine materials in glaciated areas in
comparison to the coarser ones strongly suggests that a large part of the
clay originates from preglacial clay formations.
If formations of sorted sediments are sampled by drilling, the different
layers may become mixed and the sample till-like in appearance. The
chemical and lithological contents of sorted sediments are nevertheless
different from those of till from the same locality, owing to the different
transport and separation processes. Utmost care must thus be taken in
sampling formations where mixing of materials may happen.
Till should always be preferred over sorted sediments in geochemical
exploration. The provenance of sorted sediments is much more difficult
to find, because the transport has occurred by at least two means and in
two different directions with separation of original constituents from each
other. The use of sorted glacial sediments in geochemical exploration is still
very much at the experimental stage (Lee, 1965; Shilts, 1972; Kauranne
et al., 1977; Smee, 1983; Coker and DiLabio, 1989). The great economic
value of sorted sediments for other purposes has been evaluated in several
publications (e.g. Lüttig, 1990; Königsson, 1992).
Like the type of material, so the size and shape of glacifluvial formations
depend on the place of sedimentation. The sedimentation may occur inside,
in contact with or near by the glacier ice. Because the purpose of this book
is to assist in geochemical exploration, only the main types of formations
are described, and only to the extent necessary. Until now, assaying of
glacifluvial sediments for purposes of geochemical exploration has not given
encouraging results. They may be used in regional mapping but not in
target prospecting.
38 Glacigenic deposits
and käme deltas. All are difficult to use as material for geochemical
exploration.
CONCLUSIONS
from ice, and (2) glacifluvial deposits transported and sorted by water
and deposited either in running water (glacifluvial proper) or in standing
(glacilacustrine) fresh or brackish water.
Till consists of fresh or weathered rocks newly torn from bedrock and
mixed with earlier deposited materials of overburden. Till is a mixture of
all possible grain sizes and lithologies, where every grain size fraction has
its own lithological and geochemical character, varying with depth.
Till represents the lithologies of the bedrock beneath, having been trans-
ported on average only a few hundred metres. Material at the till-bedrock
interface is local, with the surficial parts representing further transported
material. Occasionally, distinctive lithologies have been identified as far
away as 1000 km from their source (Schuddebeurs, 1981). Grains gouged
out from an ore suboutcrop form a plumelike anomaly in till (Drake, 1983),
narrow and strong at the apex and widening and weakening with distance
from the source. Typically the anomaly touches the surface two or three
hundred metres from the mother lode (Kauranne, 1976a; Lehmuspelto,
1987). Metal concentrations are lower and more homogeneous at the sur-
face and highest close to the bedrock. Standard deviation is also greatest
and anomaly/background contrast strongest at the bedrock interface.
Glacifluvial deposits are stratified and characterized by a distinct layering
according to grain size. The coarse fractions consist of multimict lithology,
whereas the finer fractions are more monomineralic. The intensity of
fractionating has been proportional to the ratio of grain mass to water
velocity. Under favourable conditions, layers of ore minerals are formed.
If such a layer consists of an economically valuable mineral (garnet,
magnetite, cassiterite or native gold) it is called a placer deposit and is, of
course, geochemically highly anomalous. Silt and clay sedimented in fresh
water are distinctly laminated but are, if deposited in salty water, with no
annual layering.
Material of glacifluvial deposits has been transported several kilometres
on average, the larger clasts and heaviest minerals a shorter distance than
the clay-size particles of light minerals like mica. Tracing of clastically
transported grains in sand and gravel back to the source may be of utmost
difficulty but can be solved by sophisticated chemical, isotopic (Gulson and
Vaasjoki, 1987) and mathematic methods (Granath, 1983). There may be
considerable amounts of hydromorphically transported heavy metal ions
precipitated on the surfaces of silt and clay grains. Water moves very slowly
in these fine grained materials but given time may form strong anomalies.
The provenance of such anomalies may be tedious to discover, but easier
than for clastically formed anomalies in sorted sediments.
41
Chapter 3
NONGLACIAL OVERBURDEN
MINERAL FORMATIONS
Introduction
In the mountainous part of arctic and temperate regions rock expo-
sures are common but in flatter areas the bedrock is mostly covered by
overburden. The overburden consists of either regolith formed in situ or
transported mineral formations. Both may be covered by organic deposits
or water.
In nonglaciated areas the overburden is mainly formed by weathering in
situ and there is a gradual transition from the unconsolidated overburden
to the hard bedrock. The transported sediments have a similar distribution
to the postglacial sediments in glaciated terrain.
Even within glaciated terrain, however, there are considerable areas that
have never been worked over by glaciers and where no glacigenic drift
exists. The loose deposits found in the depressions on highest mountain
tops, which during glaciation appeared as nunataks, are mainly sorted
sediments, ranging from talus cones to stream gravels, and including of
course slabs and gravel of the in situ weathered crust. Isolated remnants
of the preglacial weathered crust are also preserved in glaciated lowlands
where ice abrasion was minimal, not only at the ice divide and in the
bottoms of valleys perpendicular to the ice movement, but almost anywhere
in depressions as thin patchy layers. Nonglacial formations can also be
found as inter layers between glacial or glacifluvial sediments.
Dune sand and loess silt, found both in and outside glaciated terrain gen-
erally have been derived from glacial deposits and are thus semiglacigenic.
During the glacial period or soon thereafter they were formed by the
action of strong winds on mineral deposits not yet sufficiently sheltered by
vegetation.
The geochemist assaying secondary materials needs to know how closely
the overburden resembles the bedrock beneath — whether till is a direct
crushing product of bedrock and whether sorted sediments have been
derived by direct sorting of till.
42 Nonglacial overburden
Weathering
Rocks formed deep down in the crust are labile and sensitive to the
attack of mechanical and chemical forces when brought to the surface.
Especially high up on mountains, barren, steep rock faces shatter under
the stress of rapid temperature changes. Temperature expands minerals
differently, setting up tensional stresses and causing the rock to crack along
mineral contacts or planes of weakness in the mineral lattice. The repeated
freezing and thawing of free water in joints and capillary water in pores
has the same effect.
Final products of the mechanical disintegration consist of monomineralic
grains, the size and form being characteristic of the mineral in question.
Material is then dispersed mechanically with separation of constituents
along the transport route, usually with the help of running water. Waves
and wind assist in the task. Finally, through sedimentation, the materials
are classified according to their physical characteristics. The parent rock,
topography and climate thus all have their effect on the course of this
evolution.
Physically weathered rock has much more surface available for chemical
interaction with water than has the sound original rock. Even rain water,
which is slightly acidic, reacts on contact with silicate surfaces, as shown
by the increase in pH of water absorbed by quartz (pH 6-7), micas (pH
Mineral formations 43
7-9), feldspars (pH 8-9), carbonates (pH 8-10) and amphiboles (pH 10-11).
The presence of carbon dioxide increases the leaching capacity of water;
calcite, for example, then goes totally into solution in the form of calcium
bicarbonate. The common ions from the minerals of granite are leached
during weathering in the order Ca, Mg, Na, Ba, K, Si, Fe, Mn, Ti, Al. Final
products of chemical disintegration are ions in water solution and secondary
minerals that are stable in surficial conditions, e.g., clay minerals.
A more common process of chemical weathering than by direct dissolu-
tion is hydrolysis, where in the reaction between water and mineral both
acid and base are formed. As an example of hydrolysis, the change of potash
feldspar occurs as follows:
2KAlSi 3 0 8 + 6 H 2 0 + C0 2 -> Al2Si205(OH)4 + 4SiO(OH) 2 + K 2 C0 3
Before hydrolysis some minerals become hydrated (e.g., CaS04 + H 2 0 —»
CaS04H 2 0, anhydrite is transformed to gypsum).
Yet another common weathering reaction is ion exchange, or replacement
of an ion in the mineral lattice by another ion from the interstitial water.
Minerals in the mica group readily exchange ions lying between silica oxide
tetrahedron and aluminium oxide octahedron layers. Plants may contribute
to this reaction.
The most striking changes of all take place in oxidation; in the case
of iron, for example, there is a drastic change of colourless ferrous iron
solution of ground water to brown red ferric iron limonite precipitate (Fig.
3-1). Sulphides are easily oxidized and leached away, and their space in the
rock is either left empty or filled with material such as limonite. Often the
products of oxidation and hydration are of greater volume than the original
minerals and produce stresses sufficient to disintegrate the rock (Rankama
and Sahama, 1950).
Plants and animals play their part in loosening the surface of the
overburden, creating pores for water and air to intrude. Organic tissue
usually decays by oxidation, with the production of new acidic compounds
able to attack minerals. Organisms also increase the C0 2 content of soil
water, and thereby its corrosivity Some weathering of organic matter also
occurs in reducing environments, e.g., through the activity of anaerobic
bacteria.
Dense and fine-grained, homogeneous, silica-rich, unoriented rocks are
more resistant against weathering than coarse, jointed and schistose,
multi-mineral, Fe- and Mg-rich rocks. In general, high physical strength
also means greater chemical resistivity
H
ACID P ALKALINE
Fig. 3-1. Solution and precipitation of the elements, e.g., iron, mainly depends on redox potential
(Eh) and hydrogen ion concentration (pH) of the solvent. Conditions in ground water of humid
and arid regions as well as in rain water are redrawn after Friedman and Sanders (1978).
surface of the Earth, which then precipitates down, filling streams and
piling up snow on glaciers. The bottom parts of a moving glacier are filled
with a mixture of stone material. Boulders transported by ice multiply its
abrasional force. Meltwater on a glacier carries material from nunataks
and wind blown dust (DiLabio and Shuts, 1978). Streams transport loose
material either in solution, in suspension or as bottom load. Stones dragged
along the stream add its erosional effect. Stone material is comminuted
in connection with transport by ice or running water. The sun also raises
the wind, which then carries fine particles, and waves which then remove,
crush and classify materials on beaches.
Gravity determines the predominant direction of flow On steep valley
sides material is continually rolling, slumping or creeping downwards.
Water flows down by the force of gravity whether on the surface or inside
the Earth. At the same time, independent water molecules in the voids
of overburden above the ground-water table strive upwards by capillarity.
Likewise water as steam, and radon, argon, helium, oxygen, nitrogen,
carbon dioxide, methane and the other soil gas molecules, "climb" upwards
in the soil, transporting up the heavy metal ions adhering to them.
Mineral formations 45
Sedimentation
Layers formed solely by gravitational transport are poorly classified; no
seasonal layering builds up, even though the slumping of material occurs
seasonally, in spring when the soil loses its strength, cohesion and inner
friction through melting of the frozen water in pores and joints, and in
autumn when the same thing occurs through oversaturation by infiltrating
rainwater.
When sedimentating again in unstratified deposits the different grain
sizes and lithologies of layers become intensively intermixed, although
geochemically each separate grain size fraction may be rather homogeneous.
Particles transported by surface water settle out along watercourses ac-
cording to weight, the coarsest fluvial sediments settling on the upper, hilly
part of the stream where gradients are steepest and the velocity greatest.
Destruction of primary bedding by new flood erosion and resedimentation
tends to lead to still greater order and sharper classification, but further
downriver vast areas are covered by mixed mineral and organic material.
The balance between erosion and sedimentation depends mainly on the
water velocity, as illustrated by the well-known Hjulström diagram (Fig.
3-2). Flood sediments, sometimes called "overbank sediments", can well be
used for regional geochemistry.
Mineral grains of sand size may be classified further according to their
density by waving water on beaches. In littoral sediments minerals like
magnetite and garnet form distinct layers between feldspar and quartz-rich
layers. The geochemical character of different layers varies distinctly.
The slower the water flows the smaller the particles settling, and in
fresh water the sharper the grain weight classification. Silt- and clay-sized
particles are sedimented in lake or sea where water is almost standing. In
fresh, cold water a few metres deep and close to glaciers, not only summer
and winter layers but day and night layers are formed and may later be
discriminated.
In sea water the natural negative charge of clay flakes, which keeps
other flakes away, is satiated by adsorbed positive cations or organic
colloids. The clay and silt particles are flocculated and no seasonal strat-
ification occurs. Geochemically salt water clays are rather homogeneous.
The chemical/physical character of marine clays depends on the type of
cations in it and the electrostatic forces strengthening the structure caused
by them — the cations can easily be exchanged, but if totally leached out
the structure collapses. Sedimentation may be disturbed and layers already
formed damaged by alternating or turbulent bottom currents.
Ground water carries material of colloidal and ion size. Sedimentation
of the material transported by ground water occurs when the chemi-
cal environment changes. For example, limonite and lime are precipitated
46 Nonglacial overburden
256
126
■64
32
16
TRANSPORT Hjulström
0.5
0
O.OCK 0.015 0.06 0.25 1 16 6Λ mm
Clay Silt Sand Gravel Stones
Fig. 3-2. Erosion of sediments, transport and sedimentation of suspended material depend on
grain size and the speed of water flow. The well-known Hjulström (1939) nomogram has been
improved by Sundborg (1956) and is presented here modified from Friedman and Sanders
(1978).
99.5
loess Kansas
dust Kansas
river sand
beach sand
stream sand
glacial till
2
0.004 0.015 0.06 0.25 16 64 mm
-99.5
-99
-95
-80
-60
-Λ0
-20
-5
-1
I-0.5
-2 0 10 0
64 16 4 1 0.25 0.06 0.015 0.004 0.001 mm
Fig. 3-4. Examples of grain-size composition of selected sediments presented in the European
way (A) and in the American way (B) on log/probability paper where the Gaussian distribution
curve of grain composition of a single crushing product forms a straight line. Modified from
Friedman and Sanders, 1978.
Mineral formations 49
In situ deposits
In situ deposits are on their original site; the rocks are physically and/or
chemically altered but not moved. Chemical composition of the secondary
material is not the same as that of the underlying primary source rock, since
concentrations of some elements have been increased and concentrations
of others diminished.
On the top of mountains the overburden typically consists of cobbles
and slabs loosened from the bedrock beneath. Exposed to great and rapid
temperature variations, the material has merely been broken loose and is
unchanged mineralogically or chemically, forming a type of resistate. More
common resistates are those formed by chemical alteration. In temperate
climates weathering leads to silica-rich products. When sulphides or other
easily soluble minerals have been leached out and transported away, rock
consisting of quartz or quartz-feldspar skeleton with open voids, sometimes
called "sugar rock" is formed. More often the voids are filled with limonite,
rich in lead, cobalt or other metals coprecipitated from sulphides. Such
weathered material easily collapses downslope, forming residual quartzose
or arkosic sand.
These limonitic fillings are in fact in situ oxidates. Though small in
amount they can form striking geochemical anomalies by absorbing heavy
metals. The limonite film around silicate grains acts similarly by capturing
heavy metals from the ground-water solution and is therefore important in
geochemical prospecting. Larger formations, where limonite is cementing
silicate grains are familiar as gossan or "iron cap".
The true clays formed in warm humid climate, even in the Nordic
countries during the Tertiary, are a product of partial leaching and re-
arrangement of crystal lattices. Enriched in aluminium, potassium and
sometimes iron, chemically they are hydrolysates. Their lattices are built up
of aluminium oxide octahedron and silicon tetrahedron layers with cation
interlayers. Some of them, like montmorillonite, expand, when they capture
water and large cations. Because of their heavy metal scavenging activity
they play a greater part in geochemistry than the other rock forming miner-
als. In places, considerable portions of such preglacial clays are intermixed
with till, causing "false" anomalies and confusion in the interpretation of
the mainly low glacigenic anomalies. The really false anomalies are caused
by either analytic error or contamination during the sampling.
Geochemical anomalies in the in situ soils lie almost directly above their
source, but the element contents may be higher or lower and certainly in
different ratios than those in the original rock. The type and magnitude
of anomaly does not directly indicate the type, grade or volume of the
mineralization beneath. Yet the concentrations of metals in overburden
have in some countries widely been used in predicting the ore potential of
the different types of regions (Solovov, 1987).
50 Nonglacial overburden
Transported deposits
Transported nonglacial deposits have been moved by gravity, water or
wind in one or more stages from their place of origin. The type of transport
must be known when tracing their source.
Gravitational deposits
The simplest transported formations are those formed by gravity. In
talus cones the material has been rolling almost directly down the hillside,
with slight sorting only according to size and form of the particles: the
smaller and more isometric are transported further down and the larger
and slablike a shorter distance. The size and form of particles depend to
some extent, of course, on the rock type.
Friction soils, especially in spring when waterlogged and underlain by
a frozen layer, tend to creep downslope by simple gravity, in a slow
process called solifluction. Originating in the repeated freezing and thawing,
solifluction destroys stratification, stone orientation and other original
textures.
Cohesive soils behave differently, they slump rapidly when the pore water
pressure exceeds the cohesion between particles and the stresses exceed the
shearing strength of the soil. The slumping of greater masses that takes
place along a concave shearing surface is called a landslide.
The geochemical anomalies found in these gravity formations all point
upwards. However the overburden material of the slopes often has earlier
been transported along the valley, so that the gravity anomalies do not
necessarily point to the original source of the material. Such anomalies
are thus "second generation". Since gravity anomalies are mainly formed
by relatively short mechanical transport and of clastic material it should
be easy to trace their source by combined geochemical, geological and
geophysical studies.
Fluvial deposits
Running water as transporting force and medium is the common de-
nominator for fluvial deposits, which may consist of pure mineral, pure
organic or mixed material. A separate volume of the Handbook deals with
these important materials of present watercourses. We nevertheless include
some mention of the geochemical character of fluvial deposits, because
ancient fluvial deposits are widely encountered and glacifluvial deposits in
particular cover large areas outside now existing rivers.
Present-day rivers transport 13,695 million tonnes of solid and 3,600
million tonnes of dissolved material down to the sea annually. By way
of comparison, 1,000-1,500 km 3 ice, containing on average 1.6% mineral
deposits and generating 35,000-50,000 million tonnes of sediment, melts
each year in the Antarctic (Friedman and Sanders, 1978; Fyfe, 1982). Thus
Mineral formations 51
TABLE 3-1
The effect of grain size on the geochemical properties of sediment, Bouma (1987)
fixing of heavy metals depend largely on grain size of the sediment but also
on its mineralogy and humus content of the fluvial sediments (Table 3-1).
Adsorption capacity increases in the order CaC0 3 (0.44), bentonite (44),
humic acid (842), amorphous Fe- and Al-oxides (1,190-1,300) and M n 0 2
(1,540) in /miole/g in CaC0 3 system (Brummer et al., 1983).
Fluvial deposits have been transported along at least two paths, first
by gravity or ice and then by water, and this makes it very difficult if
not impossible to interpret their provenance. The same can be said about
possible clast anomalies (placers) in them, which have later still been
reformed by solution and precipitation by ground water. Knowledge of the
mode of occurrence of the ore elements in the anomaly is of great help in
the difficult interpretation. Geochemical character of certain transported
minerals like garnet (Hyvärinen, 1969) or magnetite (Granath, 1983) may
guide the prospector to the source deposit.
Fig. 3-5. Formation of sulphur-rich black mud on the bottom of a partly closed basin. Resembles
the Baltic Sea and some of its haffes (semiclosed estuaries). Original figure by Ström (1937),
modified from Friedman and Sanders (1978).
Aeolian deposits
Abrasive wind action is strongest on vegetation-free beaches, mountains,
deserts, and in the proximity of glaciers. Wind erosion is continued until
the finer material is blown off and only the larger stones — typically worn
and polished "dreikanter" — are left in place, where they form a protective
pavement against further erosion. The blown material is sedimented in the
lee of the wind, in pits and grooves and behind trees, boulders, hills and
dunes.
The dunes, most eye-catching of the aeolian deposits, are found close to
present or ancient coastlines, in deserts like the Sahara and in areas of
ancient glaciation. Dunes are variously named according to their size, form
and geographical location but all consist of fine sand. Dunes eventually
become chained to the site by surface vegetation, but while bare they shift
slowly in the direction of the prevailing winds (Fig. 3-6).
The finer material is transported further to form the loess. One might
expect that such a soft transporting medium as air would effect a sharp
separation of size fractions. This is not the case, however; dust called loess
typically contains a wide range of grain sizes and mineral compositions
deposited together (Friedman and Sanders, 1978). The mineral particles of
loess are angular silt-size grains of quartz, feldspar, mica and calcite typi-
cally coated with iron oxyhydrate. The common concretions are cemented
with CaC0 3 precipitated from bicarbonate-rich capillary or hygroscopic
water.
The dusty material of aeolian deposits has been clastically transported.
Although in theory it should thus be possible to discover the mother lode
of ore mineral grains, in practice it is exceedingly difficult to trace back the
long route of transport, even where prevailing wind directions are known.
Occasionally, rare earth element spectrum analysis has successfully been
used for tracing the region of provenance of loess, e.g. in China. The
ORIGINAL SURFACE
Chemical deposits
Chemical deposits can be classified into oxidates, redusates, precipitates
and evaporates according to the reaction leading to their sedimentation
from water solution (Rankama and Sahama, 1950). Water percolating in soil
brings elements into the soil; some of them become fixated in humus and
in other superficial layers, while others go deeper, together with elements
washed out from upper layers (Soveri, 1985).
Most typical of the recent chemical sediments are oxidates precipitated
from metal-rich solutions. Deeper down in water-saturated overburden,
reducing conditions prevail and the iron there is in readily soluble ferrous
state. Seeping into ditches or lakes, this ferrous ion is oxidized into ferric
state and settles out as water-rich red limonite gel. Later, when the water
content diminishes, the limonite hardens as a goethite crust on the bottom
(Blain and Andrew, 1977).
Limonite material transported by ground water to the surface from a
mineralization beneath cements the mineral grains of drift or of in situ
weathered material into deposits of gossan (Wilhelm et al., 1979; Wilhelm
and Kosakevitch, 1979). Through measurement of the isotopic composition
of lead it can be decided whether or not the parent rock of the gossan
represents an economic type of deposit (Vaasjoki and Gulson, 1985, see
Table 3-II). If the isotopic ratios in the gossan coincide with those of known
economic ore deposits in the region, follow-up studies, including diamond
drilling, can be recommended. The same isotopic method can be used for
identification of the source of lead-bearing erratics, soil and ground water.
A similar dissolution/precipitation process occurs in podsol profile: heavy
metals are leached from the A-horizon and precipitated to the B-horizon
56 Nonglacial overburden
TABLE 3-Π
Isotopic composition of lead of ore mineralization and gossan at Lady Loretta, Australia
(Vaasjoki and Gulson, 1985)
where pores become filled with rust. Often rust forms a compact layer (iron
pan) at the surface of the ground-water table, too.
Sizeable deposits of nickel-rich, manganiferous rust nodules are formed
on the sea bottom at levels where redox conditions are favourable. Rust
from lake bottoms was once exploited as iron ore in central Finland. Some
of the nodules may contain economic contents of other base metals besides
iron. Sulphur from sulphide rich mud rises by capillary action up to the
surface and white aluminium sulphate is precipitated.
Reducing conditions encourage the formation of sediments rich in iron,
sulphur and carbon. Such redusates form in closed ponds or at the bottom
of depressions in the sea (e.g., the Gotland Deep in the Baltic Sea). The
postglacial muddy clays contain large amounts of black iron sulphide, which
is easily oxidized to sulphate if exposed, e.g., by ditching, and the surface
waters become acidified.
Uranium minerals are easily dissolved in oxidizing environments such
as found on hillsides. The uranium is then carried by ground water to
valley bottoms where deeper down in the overburden the conditions are
reducing and uranium is fixed to form anomalies (Väänänen, 1976). During
transport the uranium will usually be separated from its daughter elements,
so that in individual samples the correlation is poor between gamma- or
alpha-intensity and the uranium concentrations.
The term precipitate is used for minerals such as Si0 2 and CaCOa sinter
(chert and travertine) precipitating on the Earth's surface or in the pores
of overburden from warm water springs. Also siderite (FeC0 3 ), vivianite
(Fe3(P0 4 )2-8H 2 0) and dopplerite (humus) layers in bogs belong to this
category, and the silt concretions in loess and glacial clays cemented with
calcium carbonate or marcasite (FeS2).
Evaporites are formed when an oversaturated solution of salts (brine) is
evaporated and Ca, Na, K and Mg sulphates, chlorides or carbonates are
left behind. Some brines, and the corresponding evaporites, are rich enough
in heavy metals to be exploited as ores.
The various chemical sediments themselves can be said to be hydromor-
phic anomalies. Although the volume and areal distribution of chemical
sediments are insignificant compared with other sediments, their impor-
tance for geochemical exploration is considerable.
Mineral formations 57
The percolating rainwater leaches minerals of the soil and carries the
dissolved elements deeper into the overburden along the ground-water
stream, towards valleys. When such happens in a material bearing a clastic
anomaly, superimposed geochemical anomalies will be formed. In certain
conditions the clastic and hydromorphic transports may even occur in
opposite directions (Paskolahti, Fig. 3-7).
LEAD IN TILL
0 . 0 6 mm 7.25 M N H 0 3
PASKOLAHTI BAY
KIIHTELYSVAARA
S a m p l i n g point
Pb in t i l l , ppm
^ Boundary of g l a c i -
morphic Pb anomaly
200
Fig. 3-7. Dispersion of lead (1) clastically by glacial transport uphill towards SE and (2)
hydromorphically in ground water solution downhill back to the shore and over the suboutcrop
of the Pb mineralization. Reproduced with permission from Mäkinen and Lestinen (1990).
58 Nonglacial overburden
ORGANIC FORMATIONS
than others: for example the stems of coral, mussel shells, the skeletons of
diatoms, plant pollen, insect shards and the bones of animals. Soft parts
of the tissue will be preserved only in favourable reducing conditions such
as found in peat bogs. For deposits to form it is necessary that the growth
of tissue be abundant and that the tissue not be totally decayed after the
death of the plant or animal consumed.
Plant residue
Humus
Lichen, grass, leaves of trees, chitinozoan parts of insects and other
remnants of living organisms are constantly accumulating on the surface
of the overburden. Nevertheless organic material decays at such a rate
that the thickness of the topsoil remains almost constant through the
years. The slow oxidation and disintegration of the organic compounds
is called humification and the mature material humus. The nature and
constituents of humus depend on the vegetation, which in turn depends on
the conditions set by the climate and the overburden.
Organic material has been found to enrich heavy metals by binding them
in chelates and other complex salts of humic and fulvic acids (Tenhola,
1988). Humus concentrates different amounts of heavy metals according
to the type of forest (Fig. 3-8). Part of the heavy metal content of humus,
maybe that part which is bound to fulvic acids, is in dynamic equilibrium
with the surroundings (Fig. 3-9); metals enriched during the dry season are
leached off by rains but perhaps fixed in the B-horizon below.
B bog peat
C conifer humus
D deciduous tree humus
Fig. 3-8. Distribution of bulk contents of extractable heavy metals determined by dithizone
titration in different types of forest humus. Reproduced from Kauranne (1967).
60 Nonglacial overburden
ppm Ni
200
m,ca mafic intrusion
(V\YI | x x j
(mineralized)
I \ \ \\ gneiss
150 f
| Δ Δ | till W$M sand
| O Q | boulder layer
Sampling
Fig. 3-9. Seasonal variation in nickel content in humus over mineralized bedrock and country
rock at Enonkoski Ni deposit. The sand interlayer may cut off the capillary rise. Redrawn with
permission from Salminen and Kokkola (1984).
06 FULVIC ACIDS
0 _i I i_ , I i ■ I L_. I . , I . i
04 I
0.8 %
03
HUMIC ACIDS
02
01
04-1
0.8 %
03-
HUMATES
02
01
1 1 i I 1 1 1 1 .1
3i HCL e x t r a c t
0 i 1 i i 1 , II 1 1 1111 1i1 i 1 i 1 i
100τ
TOTAL Zn in PEAT
50
rfrf77777* τζππτπ.
k AT "7 T X X
^ "
Fig. 3-10. The amount of zinc occurring in different modes in peat, modified after Antropova
(1975) and Lukashev (1983). The greatest contrast between anomaly and background is found
in humates. Antropova recommends the leaching out and analysis only of humates in humus
geochemistry.
the result of metal uptake by tree roots and concentration into the falling
leaves (see also Vogt and Bergh, 1943). There are great variations in the
heavy metal contents between different parts of the plant and still greater
between different species. It has been noticed, for example that some plants
(e.g., "copper plant", Viscaria alpina) tolerate much higher concentrations
62 Nonglacial overburden
Till 0 - 0 . 0 6 mm Humus C x H m
Cg§\ magn.anom.
i:':'y':'i 1 9 0 - 2 3 5 ppm 4 - 5 ml
^ ^ Ni ore exp.
fT:--:-::l
Ιϊ<<<>>^ > 2 3 5 ppm > 6 ml Ni boulder
Fig. 3-11. Anomalous contents of bulk cxHm in humus correlate positively with nickel anomaly
in the fines of till, but do not lie directly above the anomaly in till. Reproduced Kauranne
(1976b).
of toxic elements than others, whereas other plants even have a repelling
mechanism towards toxic elements (Figs. 3-14 and 3-15). As an example of
selective intake (Duchaufour, 1982, p. 93) notes needles of conifers growing
on dune sand which displayed an Al: Fe ratio of 8-10, while the ratio in the
sand underneath was less than 1.
Organic formations 63
Skarn with
scheelite
Fig. 3-12. A method lying between boulder tracing and geochemical prospecting is the tracing of
heavy minerals. The method is suitable for tungsten exploration, for example, because scheelite
and wolframite are easily concentrated by panning and amounts can be semi-quantitively
determined by the unaided eye under ultraviolet light. The anomaly in humus shows the
difference in mode of origin — glacigenic and hydromorphic transport. Reproduced with
permission from Toverud (1984).
' / / DIFFUSION \ \ \
CLAV
♦ */ ^ \ Mi
\ΤΤΤ TILL
Δ Λ "^" //// Δ
~Γ X WEATHERE
SUBEXPOSURE \ \
Fig. 3-13. Processes causing upward dispersion of heavy metals from the suboutcrop of
mineralization into humus.
TABLE 3-III
Mean concentrations of zinc and nickel in rock, soil (ppm) and in plants (ppm in ash) growing
on them (Lounamaa, 1967)
1000
100
10000
Fig. 3-14. Relation between element contents of plants and soils. Plants growing above
mineralized bedrock contain anomalous amounts of the bedrock elements. The elevated
concentrations of metals in the substratum are reflected as elevated concentrations in plants,
in some without obvious limitations, in some only to a certain maximum. Kovalevskii (1984)
classified plants into four groups according to their ability to restrict metal uptake. Some plants
die if the concentrations of toxic metals increase above a certain limit. Others are not affected,
or even flourish with an extra supply. Viscaria alpina, for example, tolerates copper and is used
as a Cu-indicator plant. Modified after Kovalevskii (1984).
C o n c e n t r a t i o n in solution
Fig. 3-15. Plant metabolism depends on certain elements and suffers when others are present.
Kabata-Pendias and Pendias (1984) observed that plants selectively uptake elements from water
solution. Boron and also zinc in small amounts are good for plants, whereas lead and cadmium
are poisonous. Reproduced with permission from Kabata-Pendias and Pendias (1984).
Peat deposits
In regions of arctic climate, flat moist areas are widely covered by the
peat-forming plants of moss, sedge and horsetail. In peat all pores are water-
filled, no air is circulating and oxidation is not possible; the environment
66 Nonglacial overburden
diapiric ribbon-type
anomaly anomaly plume
favours very slow decomposition of tissues instead. Boggy flat areas called
muskeg by North American Indians and jänkä by the Lapps cover extensive
regions of the Arctic. There are countless types of peaty formations — bog,
fen, marsh, mire, moor, quagmire, slough, swamp, etc.; their differences are
not discussed here as the geochemical behavior is affected in only a minor
way by the type of plants forming the peat. Geologically a peat deposit is
called a bog when the thickness of the humified peat layer exceeds 50 cm.
In the tropics the peat layer may be as much as 40 to 60 m in thickness, in
temperate region it rarely exceeds 10 m and in the arctic 1 m.
As determined by 14C and palynological studies the Finnish raised bogs
were growing at a rate of 0.5 mm a year during the warm period about
6,000 years ago, and have grown some less a year since then. The same
is true of Canada where growth rates of 0.7 mm to 0.3 mm have been
reported (DiLabio and Coker, 1982; Ovenden, 1989). Age determinations of
peat bogs have also been established with the uranium-thorium and amino
acid methods.
Three types of bogs can be differentiated on the basis of their water
balance and corresponding vegetation: (1) raised bogs, in plain areas with
only rainwater supply; (2) slope bogs, on sloping ground or beach with
down-seeping ground water; and (3) floating bogs, which are ponds, bays
or rivers overgrown by moss with continuous water supply from beneath.
Raised bogs, which are the thickest, are built up primarily of Sphagnum
moss. Sedge (Carex) is the usual peat-forming plant in floating bogs, which
also may be of considerable thickness, especially if the bottom mud is
included. Slope bogs tend to be rather thin and have a varying vegetation
of moss, grass, bush and small sized pine or spruce trees.
The degree of humification and the amounts of humic and fulvic com-
pounds depend somewhat on the original vegetation, i.e. on the type of
bog. Geochemically, mature peats behave about the same whatever their
original plant composition and fibrous structure. Ore metal anomalies tend
Organic formations 67
Fig. 3-17. Distribution of metals and ore float in till and peat. Ground water seeps into a peat
bog from the mineral drift on hillsides, transporting heavy metals which are fixed in peat
as organometallic complexes. Easily sampled peat from the bog rim can be used in regional
prospecting. Redrawn with permission from Eriksson and Eriksson (1976).
exploration target areas vary considerably. Table 3-IV gives an idea of the
enriching factors of different materials.
The heavy metal binding capacity of organic material is so great that
the detection of anomalies is possible even with simple chemical meth-
ods. A portion of the heavy metal content in peat is loosely bound
and in dynamic equilibrium with water solution, in which the concen-
Organic formations 69
Fig. 3-18. Distribution of Mo in till and peat. Heavy metal transport in peat occurs both laterally
and vertically as shown by a molybdenum anomaly in peat over a glacigenic molybdenum
anomaly in till. Compiled after Smith and Gallagher (1975).
TABLE 3-IV
Average and maximum concentrations (ppm) of Mo, Cu, Zn and Co in humus, peat, till and
bedrock at Aittojärvi (Kokkola and Penttilä, 1976)
Mo Cu Zn Co
Humus:
mean 14 97 335 22
maximum 613 338 1520 263
Peat:
mean 67 79 153 35
maximum 1732 347 1103 579
Till:
mean 9 36 41 n.a.
maximum 78 128 104 n.a.
Bedrock:
mean 54 47 52 20
maximum 2382 346 1230 71
O Fe,Ti,V-ore suboutcrops
Fig. 3-19. Differential dispersion of metals in peat. Heavy metals in peat behave like ions in
a Chromatographie column — some are concentrated near the top, some near the bottom. An
example from titaniferous iron ore. Redrawn with permission of Salmi (1967).
Diatomaceous earth
Muddy deposits (gyttja) often contain large amounts of diatom frustules.
Though areally and by volume small, these deposits of diatomaceous earth
are geochemically important because of their pure siliceous composition
but unusually great capacity for absorption of e.g., heavy metals.
Animal residue
Shell deposits
Clam, mussel and mollusc shell layers are virtually the only fossiliferous
(animal) formations forming in arctic and temperate climate. Commonly
they occur as pocket-like deposits in ancient basins in areas of land
Organic formations 71
V NiCrCu
0.1
a
Φ
Ό
0.5
1.0
ppm ppm
125 175 Ni V 150 250 350 Zn
150 250 Cu Cr 30 50 70 Pb
60 95 Co
Fig. 3-20. A statistical study of heavy metals in peat throughout Finnish Lapland shows how
most metals are concentrated near the bottom whereas lead is concentrated at the surface.
Redrawn with permission from Tanskanen (1976).
Cu
[ppm]
1000
OO O ·
•
#· · · · •
500
o ° # · · • •
oo •
o o° · · ·
ο<%^ q? °o · ·
1000 2000 Ni [ppm]
Fig. 3-21. Illustration of the strong relation of heavy metal contents between peat and underlying
bedrock lithology in Lapland. Redrawn with permission of Tanskanen (1976).
Human impact
Human cultures have affected the environment as long as they have
existed, changing the trace element contents of the soil.
Older polluted formations, like the lake sediments in central Sweden
polluted by mine smelters during the seventeenth to nineteenth centuries
(Vuorinen, et al, 1988), have in places been buried by younger sediments,
and could mislead the unwary geochemist working in such areas. The
present pollution by agriculture, settlements, traffic, industry and especially
ore smelting pervasively affects the topsoil and water sediments (Fig. 3-22).
A prospector assessing topsoil and water sediments must thus be constantly
alert to the possible effects of pollution on the results (Ek et a l , 1988; Table
3-V).
Buried bones form a relatively open system with the surrounding soil
so that part of the lead content of bones may have originated from the
surrounding soil or alternatively a part may have been leached away. The
probable source of the highly anomalous lead accumulated in e.g., mediaeval
man or soil was water pipes, glaze on earthenware pots, and lead added as
"spice" to wine (Table 3-VI).
Qvarfort (1977) reports that wind-blown dust from 400-year-old dumps
of exhausted lead mines polluted the soil only within a 350 m radius
and only down to the B-horizon (50 cm) in till. The pollution of lake
and stream sediments in the same area was much worse and extended
several kilometres along watercourses below the old waste heaps (Table
3-VII). In Finland such pollution, depending on the metal, extends as
TABLE 3-V
Average concentrations of lead in garden soil, house dust and in hair of children 2-4 years old,
in a village near by a closed lead mine in Derbyshire (Thornton, 1988)
Fig. 3-22. Distribution of lead in lake sediments. Lead concentrations in lake sediments have
been found highest beside highways and in boat harbours. Improvements in motors and fuel
show a trend towards decreasing pollution. Reproduced with permission from Pirttisalo and
Räisänen (1988).
TABLE 3-VI
Relative exposure to lead in Britain (Waldron, 1988). Lead content of neolithic bones taken as
standard
Neolithic 1 Mediaeval 13
Iron Age 3.5 18-19th century 10
Roman-British 7.0 Present day 4
74 Nonglaeial overburden
TABLE 3-VII
Heavy metals (kg/year) leached by rain-water from waste heaps (Qvarfort, 1979)
Mine Cu Pb Zn Cd
Bersbo 5,000 55 30,000 40
Falun 15,000 400 433,000 300
Garpenberg 375 125 26,010 35
Saxberget 595 120 14,255 25
CONCLUSIONS
What are the experiences obtained from the use of sorted mineral
sediments and organic deposits for geochemical exploration? Gravel is so
coarse grained that it is difficult to get a representative sample for analysis.
Sand is sorted both by grain size and mineralogically, and it consists
mainly of quartz and feldspars. It is highly permeable but its capillarity
Conclusions 75
Fig. 3-23. The distribution of the zinc concentrations in the Pihlajanneva mire shows both
the location of the zinc mineralization as well as that of the clastic zinc anomaly in till. With
permission from Virtanen (1991).
76 Nonglacial overburden
Chapter 4
SOIL TYPES
SOIL FORMATION
Soil in the narrow sense used here is the chemically differentiated upper
layer of the overburden, typically a black humus surface layer underlain by
a pale A-horizon deficient in Al, Fe and clay, a brown B-horizon enriched in
Al, Fe and Mn, and a C-horizon of unconsolidated parent mineral material.
Soil-forming processes influence the secondary dispersion of metals, shaping
anew the anomalies and making their interpretation more difficult.
Soils are the product of weathering — the physical, chemical and
biological forces which begin their disintegrating and discriminating work
immediately fresh mineral material is exposed. The longer the time for
development, the more extreme the temperature variations, the higher the
humidity, the more profuse the organic life, the greater the porosity of the
parent mineral formation and the weaker the minerals, the deeper will
be the weathering effect and the more distinct the soil horizons that are
developed.
The global zoning of vegetation follows both the latitude and the height
above sea level (Figs. 4-1 and 4-2). Local factors affecting the vegetation
include warmth and water and the time elapsed, but also the mineral
composition and looseness of drift, exposure to winds and surficial water
streams, and human activity.
In a warm dry climate the capillary rise of water is greater than the
downward seeping of seasonal rainwater, and alkali and other soluble salts
move up to the surface and are precipitated. When soil is alkaline, clays
with high base-exchange capacity, rich in montmorillonite, are formed.
Such clay minerals tend to capture and enrich heavy metals from the
ground-water solution.
By contrast, the humid climate of arctic and temperate latitudes favours
the formation of acid soils. Clays with low base-exchange capacity minerals
like kaolinite through illite are developed. Although they adsorb heavy
metals, their scavenging ability is weaker than that of the expanding clay
minerals. However, the organic colloids in the soil enrich heavy metals by
00
Fig. 4-1. Distribution of the main forest zones of the world. Vegetation reflects the temperature and humidity as well as grain size S
composition and nutritive state of the overburden, all important factors in soil formation and the secondary dispersion of elements. The Q-
type and thickness of the important organic top layer Ao of the overburden depend on the vegetation. ^
Soil formation 79
ZONES VEGETATION
Fig. 4-2. Relation between vegetation and altitude. The height above sea level has almost the
same effect on vegetation, and thereby on soil formations, as does latitude. Redrawn with
permission from Duchaufour (1982).
capturing them into insoluble chelates. The most common types of soil in
arctic and temperate regions are podsol and chernosem. Both exhibit a
distinct and prominent zoning if the parent material is permeable enough.
In places of impeded drainage, lack of aeration prevents the oxidation
required for normal soil formation and gley — a bluish-grey horizon with
ferrous iron — is produced instead. A fluctuating water table may cause
formation of rusty concretions or streaks in the gley Deeper down in porous
sediments, at the surface of the ground water, an almost impermeable hard
iron pan is sometimes precipitated.
In the high Arctic the permafrost hinders drainage and soil formation.
Close to glaciers the surface of the overburden is newly exposed and
immature and the soil profile is very thin. The same is true of high
mountains and in arid deserts where the lack of water delays or prevents
soil formation.
As soils mature a distinct layering tends to develop. From bottom to top
the main layers of the idealized soil profile (Fig. 4-3) are: the unaltered
C-horizon containing fresh mineral material; the B-horizon, brownish due
to precipitated ferric iron and containing oxides of Mn and Al; the ashy pale
A-horizon where an overall weathering of minerals and leaching of elements
other than Si has occurred; and uppermost, a brownish black A0-horizon of
humified organic material, which supports the living vegetation.
The upper parts of the B-horizon also contain some downward trans-
ported clay particles, kaolinite or montmorillonite, which through hydroxyl-
groups bind Fe leached from the more weathered A-surface. The B-horizon
can thus be divided into a lower Bs-horizon containing complex salts of
fulvic acids, a middle B h -horizon containing the complex salts of larger
molecular humic acids (Duchaufour, 1982, p. 318), and an uppermost
Bfhorizon rich in clay. The A-horizon can also be subdivided: into the
deeper mineralic A2-horizon, which forms a rather sharp boundary with
80 Soil types
A2
B,
Bh
Bs
Fig. 4-3. Schematic podsol profile. The most characteristic soil profile for arctic and temperate
zones is podsol.
the B-horizon, but changes gradually upwards, and the Ax-horizon, which
contains abundant organic material and is therefore dark or greyish in
colour.
The above-described idealized soil profile is called podsol and tends to be
acidic. The lowest pH is measured at the top and differences are significant
between the various horizons, which demonstrates that there is some
buffer capacity in soil layers in calcareous and even in granitic areas (see
e.g., Nuotio et al., 1985; Vuorinen and Lahermo, 1986). Acid rain easily
breaks it down, however, causing fixed ions like Al to go into solution,
with toxic effects on vegetation. Typical examples of pH and heavy metal
concentrations in different layers of the podsol profile are shown in Table
4-1, for till with a soil profile 60 cm thick and silt with a profile 5 cm thick.
The rate of humification, decaying of the plant tissue and producing
organic acids for the weathering of minerals and development of the soil
TABLE 4-1
pH and heavy metal concentrations (ppm, determined from a 25% HNO3 leach), in different
horizons of podsol profile in till and silt of the background area in Viitasaari, Finland (Kauranne,
1967)
SPRUCE
TTTTTTi
mm PINE
νΤΤΤΐΎΤΤΊ^ΤΆ BIRCH
Fig. 4-4. Relative distribution of genera in Finnish forests over the last 10,000 years. The
development of Finnish forests after melting of the continental ice, as studied by pollen analysis,
reflects the variations in climate, weathering and the composition of clay, mud and peat deposits.
Reproduced with permission from Alhonen (1988).
82 Soil types
SOIL DIFFERENTIATION
Soil science, or pedology, has been developed mainly for the needs of
agriculture, as cultivation practices depend heavily on the type of soil.
Though factors affecting the development of soils may be few, their local
and seasonal variations lead to so many different soil varieties grading into
one another that, as yet, no single internationally accepted classification of
soils exists.
The weathering processes causing soil formation, varying in intensity
according to climate and other factors, include dissolution, hydration,
hydrolysis, oxidation, reduction and carbonation. Organic and mineral
material is added and removed, translocated and transformed, resulting in
vertical discrimination and horizontal layering. The processes are partly
reversible and a dynamic balance is established, depending on the changes
in climatic and chemical conditions (Figs. 4-5 and 4-6) leading to a type of
horizontal layering, the soil profile.
Geochemical exploration proceeds through chemical analysis of natural
materials in which the mineralizations of bedrock are reflected as anoma-
lously high contents. These anomalies are only discoverable, however, from
samples that are entirely comparable. Within one study, samples absolutely
must be taken from the same material — and in the case of soil from the
same soil horizon.
There is no need for the exploration geochemist to have a thorough
knowledge of all soil types — it is sufficient to know what happens to
Fig. 4-5. Variation of different properties of soil in the vertical (podsol) profile. Reproduced with
permission from Hawkes and Webb (1962).
Soil differentiation 83
FeQ(OH) ■
s^f^^^^ä
Fe2 +
PERMA
Ca rich layer
FROST
C O L D T E M P E R A T E
Fig. 4-6. Weathering and vegetation both modify and change the overburden, producing
different soil types. The commonest soil types in the arctic and temperate zones are podsol and
chernosem.
the elemental concentrations of the parent rock during the process of soil
formation, and what is the best horizon to assay if the virgin C-horizon is
not accessible or available.
Concentrations are nearest to the original in the C-horizon and anomalies
found there are easiest to interpret. There may of course be great variation
between the upper and lower parts of the C-horizon depending on the
type of formation and the level of ground-water table. The A-horizon is
depleted in most of the heavy metals; only lead tends to be enriched. The
B-horizon is enriched in most of the heavy metals, especially those that are
coprecipitated or adsorbed by sesquioxides, as are Co and Zn. Humus (A0)
is enriched in almost all the heavy metals, but especially in those like Sb,
Co, Ni, Cu and Cr which have a great affinity for organic compounds.
In the following section the properties of podsolic and chernosem soils
— the soils most common in arctic and temperate regions — are described
and a few other less common types are briefly characterized. In the main,
the classification is that proposed by Duchaufour (1982). Soil zones of the
world according to Simonson (Hawkes and Webb, 1962) are presented in
Fig. 4-7.
Soil types
Immature soils are encountered where climatic and biologic forces have
not operated long enough for soil development. In newly formed deposits
like sandurs or dunes, submerged areas recently exposed by land upheaval
and areas released from melting glaciers, vegetation has not had time to
OO
g>
Fig. 4-7. Distribution of the most common soil types after Simonson (1957) in Hawkes and Webb (1962).
Soil differentiation 85
grow, decay and alter the mineral material of the surface of the regolith.
In very arid or very cold environments vegetation has been too sparse
and weathering too slow for the development of a soil profile during the
Quaternary.
Erosion by water, wind and landslide in places cuts into older deposits,
exposing new surfaces and burying or dispersing the layers of the old soil
profile. The development of a new soil profile requires time.
Immature soils are typical in the Arctic and on high mountains (Figs. 4-1
and 4-2). According to the FAO/UNESCO soil map of the world, immature
soils occupy 12.50% of the total land area of the world (Kabata-Pendias and
Pendias, 1984). This map differs somewhat from that of Simonson (Hawkes
and Webb, 1962) in Fig. 4-7. In immature soils no secondary processes have
affected the clastically formed geochemical anomalies, also the formation of
hydromorphic anomalies is delayed, making these soils simple to sample,
analyze and interpret.
The aluminium- and iron-rich soils are sometimes collectively called
pedalfer and the calcium-rich ones pedocal. The most important of the
mature aluminium- and iron-rich soils of the arctic and temperate regions
is podsol. Cool boreal climate, but also a permeable surface and quartzose
parent material, favour its formation. Typically the forest of this zone is
coniferous or coniferous mixed with deciduous trees. Podsol is also the main
soil at high altitudes in alpine and subalpine climate and is locally very
common in humid atlantic climate. On limestone bedrock the development
of podsol is delayed by the buffering capacity of calcium carbonate.
Podsol consists of distinct layers, which in till from the top downwards
are as follows: Ao is a mor type of humus (mor is a poor and mull is a rich
type of humus), biologically it is not very active but releases abundantly
chemically active, water-soluble compounds when rainwater penetrates it
(Fig. 4-9). It varies in thickness between 1 and 10 cm. Ai is a grey horizon
of mixed organic and mineral matter 1 to 5 cm thick. A2 is the ashy
white layer that has given its name to this soil type. Consisting mainly
of fine and friable quartz grains and varying in thickness from 1 to 10
cm, it grades upwards gradually and downwards rather sharply, unlike the
A2-horizon in brunisol, another soil variety met with in temperate climate.
Further down, the Bh-layer is sometimes well developed as a black horizon
several centimetres thick with an aggregate structure rich in flocculated
amorphous humic salts. The material changes gradually downwards to the
Bs-horizon, which is a spodic accumulation 5 to 30 cm or more thick, often
rich in red-brown ferric iron, and sometimes forming a hard iron pan. In
its deeper parts there occur colourless or pale fulvic salts of aluminium
and other metals. In atlantic climate a clay-rich B t -horizon sometimes
accumulates below this, but more often clay is accumulated above the Bh-
layer. The boundary of the B-horizon towards the virgin C-horizon below
is transitional. The total thickness of the podsol profile varies according to
86 Soil types
HUMIC ACIDS
FULVIC A C I D S
ALTERED MINERALS
CLAY A C C U M U L A T I O N
—* OXIDE PRECIPITATION
Fig. 4-8. Soil formation involves the differentiation of elements in the surncial part of the
overburden. This leads to chemically different horizontal layers. Reproduced with permission
from Duchaufour (1982).
0.8
Mn
0.6 \
\ Mn
\
o
\
2+ \ Fe3 +
HI Fe 2 + \
0.2 \
\
\
5 6 7
* pH
Fig. 4-9. Effect of Eh and pH on ionic species of iron and manganese. Because of their amount
and strong colours the modes of occurrence of iron and manganese are the most conspicuous
in the soil profile. Reproduced with permission from Duchaufour (1982).
CaCOß
Fig. 4-10. There are variations in structure and chemical composition of all soil types, mainly
due to the lithology and porosity of the parent sediment. Here two types of chernosem are
presented.
above a streaky C-horizon rich in calcium carbonate. There may or may not
be a weakly developed clay-rich B-horizon (Fig. 4-10). The slight differences
in geochemistry of podsol and chernosem profiles are shown in Table 4-IL
The black cotton soil of tropical latitudes resembles chernosem. In more
arid areas where the soil is not so black and not so thick it is called
burosem and in semi-deserts its grey salty variety is known as sierosem.
In somewhat warmer and more humid prairie and pampa the soil has a
thinner A-horizon (due to repeated fires), a little better developed argillic
B-horizon and, unlike chernosem soils, white CaC0 3 precipitations are not
found in the C-horizon.
All the different horizons of the soil profiles mentioned have been
successfully assayed for geochemical exploration; a vast literature exists on
TABLE 4-II
Trace elements in organic material of soils (in ppm dry weight), according to Stepanova, 1976
(Kabata-Pendias and Pendias, 1984)
all of them. The concentrations of the common base metals are highest in
humus, Ao, on average, but vary seasonally (Salminen and Kokkola, 1984)
(see Fig. 3-9); they are lowest in Ai, but in B concentrations usually are
somewhat higher than in C (Kauranne, 1967).
The composition of humus varies with the type of soil; either small
molecular fulvic acids or large molecular humic acids prevail.
The calcimagnesian soils with only A- and C-horizons, most notably the
rendsinas, are typical for grasslands over calcareous bedrock. Under the
crumb structured "stony", humus-rich A-horizon is a pale calcium-rich
C-horizon. In areas with trees the B-horizon is developed as well, and the
soil is then described as brunified.
Bog is here considered to be an organic overburden deposit consisting of
peat. Bog could well be classified as a type of soil too. Peat bogs are formed
in perpetually wet places from slowly decaying plant rests, the deeper parts
of the deposit being more humified, the surface layer still fibrous like the
living plants (Fig. 4-11).
Brown soil with biologically active mull humus occurs in atlantic and
semi-continental climate. In theory, gravitational water and the water rising
by capillarity carry equal amounts of sesquioxides up and down so that
the A- and B-horizons are mixed. Brown soils have an ABtC-profile, where
the clay-rich B-horizon is light in colour because of its calcite content.
These soils are common in central Europe and other temperate areas with
deciduous forests. Luvisols are clay-rich brown soils.
Hydromorphic soils called gleys are found in lowlands where the water
table is high, the environment is reducing and iron is in ferro-form. In the
typical case there are in gleys only a brownish black Ai-horizon and bluish
grey sticky A2-horizon with possible rusty patches due to seasonal lowering
of the water table.
Saline soils, with sodium and calcium chloride or sulphate accumulations
due to evaporation of ground water, and black, iron sulphide-rich marine
mud deposits below, occur along marshy coasts, as on raised beaches of the
Baltic sea.
CONCLUSIONS
The most common soil types of arctic and temperate regions are podsol
and chernosem. In these, as well as in other soil types, horizontal lay-
ering has developed through leaching and precipitation; iron, aluminium,
calcium, manganese and other cations and organic complexes and clay min-
erals have removed from one depth layer and accumulated in another. The
physical as well as the chemical characteristics vary between the horizons.
The order and number of the horizons depend on moisture, direction of
water movement and the lithology of the overburden.
Conclusions 89
Fig. 4-11. Profile of a drained peatbog in Ireland, utilized as fuel peat. The top layer is raw,
while the deeper part is mature, strongly humified peat mass (photo L.K. Kauranne).
Under the topmost layer of plant litter there is the organic black
humus layer in which usually high concentration of heavy metals are met
with. Concentrations vary greatly according to the season. Humus covers
almost the entire area, it is easily sampled and therefore very much used
in geochemical research. Sometimes only the humic compound of it is
analyzed (Lukashev, 1983).
Underlying the dark humus layer is the ashy mineralic horizon Αχ, which
90 Soil types
is rich in organic material and has large ion exchange capacity. Lead tends
to concentrate here. The Ai-horizon is sensitive to pollution. Colorimetric
analysis of it is hampered by the presence of colloids. The seasonal variation
of heavy metal concentrations is strong, but sampling is easy. The pale A2
is not particularly rich in organic materials or heavy metals. Very often it is
impossible to discriminate the different A-horizons. Assessing of A-horizon
has also been popular in geochemistry.
In the rusty B-horizon many of the base metals are coprecipitated with
iron or aluminium or scavenged by clay minerals or organic complexes. Two
or three different B-horizons can be delineated in well-developed mature
soil. Anomaly/background ratios tend to be highest here. The enrichment
factor of the heavy metals varies widely. The B-horizon is easily sampled,
P b i n B n o r i z o n tj|1
• sampling point \ striae
A^ jllfllll 110-250 ppm
llllllllllllllll 250- ppm
0 500 m
Fig. 4-12. Distribution of lead in B- and C-horizons of till in Ireland. Compiled after Miller and
Cazalet (1979).
Conclusions 91
and therefore it has been perhaps the most popular sampling medium
in explorational geochemistry. Pollution sometimes reaches B-horizon and
colorimetric analysis is often hampered by colloids. As an example of the
assay of the B-horizon see Fig. 4-12, lead in B- and C-horizons of till in
Ireland (Miller and Cazalet, 1979).
The C-horizon is untouched by soil forming processes and constituents
are almost in their original state, especially below the ground-water table.
Elements like copper and nickel usually appear in highest concentrations
here. In water permeable formations the C-horizon is deep down, but in
less permeable formations it is usually accessible at a depth of 0.5-2.0 m.
It is very seldom polluted by human activity. It is widely used both in
geochemical mapping as well as in geochemical exploration.
Opinions about the suitability of different horizons of soil for geochemical
studies vary. All horizons reflect somehow the chemistry of the underlying
bedrock: "the vertical distribution in the overburden profile does not
appear to be significantly affected by soil processes" (Lahti, 1971, in
extreme, says for Canada). The topmost horizons Ai and A2 are better used
for environmental monitoring than for geochemical exploration, but the
Ao-horizon (humus) is better for exploration. The rusty B-horizon consists
of several sub horizons with varying enrichment factors, and is not ideal for
geochemical exploration either. The almost virgin C-horizon soil material,
especially if samples can be taken under the ground-water table, is strongly
recommended for geochemical exploration
Trace element concentrations gradually increase towards depth in C-
horizon if it consists of only one single bed. If there are several intercalated
beds above each other the case is more complex and must be studied more
closely before deciding which layer in the C-horizon of overburden should
be assayed.
93
Chapter 5
INTRODUCTION
Primary dispersion
Primary geochemical dispersion is usually associated with high temper-
atures and pressures (Rose et al., 1979; Beus and Grigorian, 1977) and
involves crystallization from magma and hydrothermal liquids and the
metasomatic migration of elements. The zone formed as a result of primary
dispersion and within which the content of valuable elements diminishes
to background values is called the primary halo or aureole. The width of
94 Geochemical dispersion in the secondary environment
the aureole varies with factors such as lithology, tectonics, P-T conditions,
availability of water and the particular element involved.
There may have been several successive stages in the primary dis-
persion. The differentiation of materials and dispersion of elements that
happened long ago during weathering and transport and during sedimen-
tation of recent sedimentary and metamorphic rocks gave rise to fossil
secondary dispersion patterns, which form a transition between primary
and secondary dispersion patterns.
Secondary dispersion
Secondary dispersion commences when rock begins to disintegrate by
weathering. The constituents of the rock, either as mineral grains or in
aqueous solution, are transported by ice, air and water seeking to reduce
differences in gravity or electrochemical potential. The relevant factors in
the secondary dispersion of elements are thus the type of material, the
transporting agent and the mode of dispersion, all of which are closely
interrelated (Kauranne, 1976a).
Weathering is the process of changing of mineral material at or near the
earth's surface to products that, in the prevailing chemical and physical
conditions, are in better equilibrium with their environment. The forces
influencing the weathering process are, in principal, physical or chemical
and very often a combination of the two. Even weathering processes
that seem to be very complicated usually prove to be based on a simple
conformity of physical or chemical laws (Oilier, 1969).
Physical weathering is mechanical comminution of rocks and minerals
caused by several separate processes — partly originating from the rock
itself, partly depending on the physicochemical conditions prevailing in
the surroundings. The most important processes are fracturing caused by
tension forces in the rock and freezing and melting of water in the fissures;
even changes in temperature may cause the rock to break mechanically.
Typically the first stage in the weathering process, physical weathering
facilitates the progression of chemical weathering by enlarging the total
surface of rocks and minerals.
Chemical weathering can be defined as the chemical reactions between
rocks and minerals and constituents of air and water at or near the
earth's surface. In this environment oxygen, carbon dioxide and water
are abundant, and temperatures and pressures are low in comparison
with the conditions of the deep-seated primary environment. Rocks and
minerals that were stable in the primary environment are unstable in the
secondary environment, and chemical changes occur in their attempt to
reach equilibrium. As a result, elements bound together in rock forming
minerals may become separated in the secondary environment because
their behaviour is now governed by an entirely new set of parameters, or by
Introduction 95
1 1 1 1 1 1
Soluble
cations
•Cs
• Rb
. K • Ba
Elements of
hydrolysates
• Sr
'fRare .Th
•Na • ca y earths •u
• M n / • Sc • Zr
. Fe • Nb, Ta
• Li . Fe • Ti
y Mg * Ga
• Mn
" Λ1
_'Si
• P .S
/ • Be
Soluble complex
• B
• C . N anions
1 1 1 1 1 1
0 1 2 3 ^ 5 6 7
Ionic charge
Fig. 5-1. Geochemical separation of some important elements on the basis of their ionic
potential. Reproduced with permission from Mason (1966).
CLASTIC DISPERSION
General
Clastic dispersion in glaciated terrain is the transporting of physically
weathered or crushed material by glacier (Fig. 5-2), and, to a lesser extent
by water, wind and gravity. Chemical alteration of the material is minor,
and the main part of the material is transported in the form of rock
fragments and minerals.
Clastic dispersion 97
and the chemical changes that took place in the rock at that time. The
imprint of these processes is often still visible in present day till.
In areas covered by thick waterlain stratified unconsolidated sediments
before the glaciation, the influence of those sediments on the geochemistry
of the till is dominant, even where glacial erosion was strong. Correspond-
ingly, the bedrock is reflected more weakly in the till compared with areas
where sediment layers were thin or absent.
The influence of factors prevailing before glaciation on metal contents of
the finest fractions of till is illustrated in Table 5-1. Deposits of preglacial
weathered bedrock tens of metres thick can be found under the till in
Finnish Lapland in the area of the last ice divide where glacial erosion
was very weak. The till cover is thin and itself contains abundant material
from the weathered bedrock. The metal contents of the till are high
and in some cases even higher than in the unweathered rock beneath
due to ionic dispersion and enrichment during the weathering process.
Large amounts of preglacial fine-grained waterlain sediments were mixed
with the till in western Finland, so that the proportions of the finest
fractions of till are greater than average there. During development of
these waterlain sediments in a number of successive stages, many metals
were concentrated or leached and transported away, causing higher or
lower metal concentrations in the till than in the source rock. The original,
unaltered material from bedrock comprises the main part of the till in
eastern Finland. The dissolving and sorting influence of glacifluvial and
TABLE 5-1
Some average metal concentrations of till in areas, where the material of till differs by its
preglacial state. Analyzed by I CAP after Aqua Regia leach
fluvial waters has had little effect and the chemical composition of the till
is similar to that of the underlying bedrock.
Fig. 5-3. Radial streamlines of flow in the marginal part of a glacier lobe, seen in ground plan
showing: a, direction of streamline when lobe, A, is fully extended; 6, streamline when lobe,
B, is shrinking, Sets of striations formed parallel with such streamlines would have different
trends. Modified after Flint (1967).
the direction of ice movement and the direction of the source of the till can
be determined from the orientation of stones. When till is in motion, the
long axes of the most contained stones align themselves in the direction
of the transport. As long as postglacial processes (such as frost heave or
solifluction) have not disturbed the orientation, counts of pebble alignment
can provide a statistical direction for the ice movement.
Information about the transport direction of till needed to interpret the
results of a geochemical till study must always be obtained from the same
till bed and for the depth at which samples will be taken.
4 km
Percentage of s c h i s t s Bedroc k
n stones of t i l l
111 >40 %
■
Archean granitoids
30 - 40 % AmphiboJite
•'.\·.·'.■'.·
25 - 30 % Mica schist
4 km
Zn in till
Fig. 5-4. The percentage of schists in the 0.8-2.0 cm till fraction (upper figure) and the zinc
content in the <0.06 mm till fraction (lower figure) in Parissavaara, Ilomantsi, Finland. The
direction of ice movement is from left to right (320°). Modified after Salminen and Hartikainen
(1985).
the till blanket, the greater is the difference in transport distances between
the surface and the bottom. This means that the transport distance must
be measured from the particular till bed and depth that will be sampled
during the geochemical study. Moreover, since the transport distance of
different fractions may vary as well, measurement should be made for the
102 Geochemical dispersion in the secondary environment
actual fraction that will be used in geochemical analysis. Only in this way
can the optimal cost effective sampling grid be designed to provide the
desired scientific results.
According to the transport distance, tills can roughly be divided into two
groups: (1) those transported a long distance (1 km or more) and (2) those
transported a short distance (tens or hundreds of metres). Tills transported
a short distance are common in areas where the glacier was relatively
inactive during the deglaciation. Correspondingly, tills transported a long
distance are common where the glacier was active during the deglaciation
(the marks of active ice lobes are usually recognizable). Tills transported
long and short distances may exist side by side, often with a sharp boundary.
In areas of active ice lobes the transport distance of till and the length of a
geochemical anomaly may be several kilometres. The transport distance of
individual mineral grains or boulders will sometimes be much longer than
the average, however. Boulders derived from the Outokumpu ore eastern
Finland, for example, have been detected at a distances of more than 100
km from the deposit.
Between the active ice lobes, where there are wide areas of passive ice,
the till is local and strongly reflects the underlying bedrock. In most cases
the transport distance is only some tens or hundreds of metres, and the
lithological composition of the till is more or less homogeneous. Areas like
this, where long and complex glacial transport does not complicate the
interpretation of results, are ideal for geochemical studies.
The partition into areas of active and passive ice is equally seen in the
lengths of geochemical anomalies. Of 34 geochemical anomalies reported
from Canada (Bradshaw, 1975) and Scandinavia (Kauranne, 1976a), 14
were less than 400 m in length (Fig. 5-5). The secondary maximum in the
frequency distribution of the lengths of these 34 anomalies, lying between
1.2 and 1.5 km, reflects the distant transported tills.
Few geochemical anomalies have been reported for tills in areas of active
ice; this is apparently because, in the course of extended transport, material
from different bedrock types has been added and mixed into the till making
the results more difficult to interpret. The metal ratios change and contents
are strongly diluted along the anomaly, and other kinds of changes may
occur as well, depending on the circumstances and particular metals.
n Scandinavia
Canada
800 1600
j
2400
400 1200 2000 2800 3 2 °° m
Fig. 5-5. The length of geochemical anomalies in Scandinavia (Kauranne, 1976a) and in Canada.
Compiled from Bradshaw (1975).
distance causes dilution of the ore material in till because material from
other rock types over a wider area is intermixed. Although the anomaly
can still be detected far away from the source area, it is weak and no
longer reflects the source well (Fig. 5-6). The extensive dilution of the
anomalous material places special demands on sampling (samples should
be homogeneous and sufficiently representative) and on the sensitivity of
assaying methods.
The width of the ore suboutcrop (or of rock formation, or mineralization)
in the direction of ice movement has a decisive influence on the shape and
size of the anomaly pattern. The wider the source area the more a glacier
can abrade it, and hence the greater the amount of anomalous material
that can move up into the glacier, where it enjoys longer transport than
at the bottom of the glacier. The anomalies derived from the serpentinites
in the Outokumpu region provide a good example of this (Fig. 5-7).
The serpentinites lie in the bedrock as folded bands 0.5-2 km wide and
hundreds of kilometres long. In the Kokka and Losomäki areas where the
bands are oriented in the direction of the ice movement, the glacier has
abraded the serpentinites over a range of 7-8 km, and the resultant Ni
anomaly is clearly detectable 20 km from the distal contact. In Outokumpu,
on the other hand, the band-like serpentinite lies transverse to the ice
movement, and the abrading action of the glacier has been effective over
1 km only; here the Ni anomaly disappears into the background 5-6 km
from the distal contact of the serpentinite. A few kilometres to the north
104 Geochemical dispersion in the secondary environment
Fig. 5-6. The summed percentage of mica schist, serpentinite and skarn at different depths
(upper figure) and the content of nickel (ppm) in the <0.06 mm till fraction (lower figure)
in the pits at Miihkali, eastern Finland. The direction of ice movement is from left to right.
Reproduced from Salminen and Hartikainen (1985).
east near Horsmanaho the same band becomes still narrower, and the
Ni anomaly shortens to about one kilometre. The surface areas of these
serpentinite outcrops are much greater than those of most ore outcrops,
but the relationship between the width in the direction of ice flow and
the length of the anomaly is the same. Roughly it can be said that the
detectable length of a metal anomaly in the fine fractions of till is 2-4 times
the width of the source area in the direction of ice movement.
In addition to the width of the suboutcrop, weathering and the resistance
to abrasion of the bedrock influence the anomaly/background contrast. The
glacier is able to loosen more material from softer and more weathered
bedrock than from hard and unweathered bedrock. The host rock of the
Outokumpu Cu ore is quartzite, a rock type resistant to abrasion, and a
common ore mineral is pyrite, a mineral harder to weather than many other
sulphides. Although the copper content of the ore is 3.8%, the anomaly in
till derived from the ore does not differ appreciably from the anomalies
Clastic dispersion
£} High Ni anomaly
I Boundary between
long and short
Fig. 5-7. The anomaly pattern of Ni in the <0.06 mm till fraction, Losomäki-Outokumpu
area, eastern Finland. The anomaly is caused mainly by the serpentinites of the Outokumpu
association. The difference between the areas of long and short transport distance is clearly
visible.
derived from the nearby black schists which have a Cu content only one-
hundredth of that of the ore (Fig. 5-8). This is because the width of the
black schist layer in the ice movement direction is 2-3 times the width
of the ore outcrop, and the black schist is much softer and more easily
weathered than the ore.
The grain size of the original bedrock has a further effect on the
formation of an anomaly. In the case of two rock types having the same
weathering properties and resistance to abrasion, more material from the
fine-grained than from the coarser-grained bedrock gets into the finest
fractions of till typically analyzed in geochemical prospecting. Material
is easily ground to its original grain size (Dreimanis and Vagners, 1971;
Haldorsen, 1983). So it is possible — and in fact quite common — that a
geochemical anomaly in till derived from a rock type with low metal content
but occupying a large area is as high as the anomaly derived from a rich
but small ore outcrop.
106 Geochemical dispersion in the secondary environment
Fig. 5-8. The anomaly pattern of Cu near by the Outokumpu ore outcrop, Outokumpu, Finland.
of ground, and again the anomaly pattern will be modified. A steep ridge
in the bedrock tens of metres high causes till to pile up in front of the
ridge, while only a little (most of it very local) is deposited on the ridge
itself. More till is again deposited behind the ridge, but it is now intermixed
with material from the proximal side of the ridge transported inside the
glacier (long transport, Fig. 5-9). The same rules hold for all fractions of
till — the geochemical anomaly pattern detected in the finest fractions is
often interrupted directly above the threshold of the ridge but is again
strengthened on the distal side (Fig. 5-10).
In places multiple transport of till has occurred, caused by two or more
separate ice flows during the oscillation of the ice margin. Often a later ice
40 b \^
20-
I I
Fig. 5-9. Distribution of surface stones in Viesimo. Reproduced from Salminen and Hartikainen
(1985). (a) Topography of the study line, (b) Percentage of Karelidic rocks along the study line,
(c) Percentage of different rock groups along the study line.
108 Geochemical dispersion in the secondary environment
i l l Mica schist [jwÄ) Black schist [%%] Quartzite f£§) Rocks of Outokumpu- ~^" Sampling site
association (tractor excavator)
Fig. 5-10. Nickel content in the <0.06 mm till fraction in Petäinen, Finland. Reproduced from
Salminen and Hartikainen (1985).
flow will have abraded the till and totally obliterated the marks of an earlier
flow. But in some cases the marks of separate ice flows are still discernable,
especially if the directions of the ice movement differed. The anomaly
pattern in till is the cumulative effect of successive periods of transport and
is elongated in accordance with the separate ice flow directions. Usually,
however, the erosion of the last ice movement was so strong that it renewed
the anomaly pattern totally; at least this can be assumed if only one till bed
is found in the study area.
Boulders strongly resistant to glacial erosion have often been transported
by more than one ice flow. This can be recognized in the shape of boulder
fans or in the location of a boulder from a known ore that cannot be
explained by a single transport direction. More commonly boulders lying
on the surface of a till bed have been involved in complex transport, in
which case a thorough study of the glaciation history of the study area is
needed.
in area compared with till-covered areas, although they may also occur
as a thin layer covering the till. In most cases the material of these
water- and wind-transported formations originated from till and as such
represents a secondary geochemical environment of second generation.
Tracing the source of geochemical anomalies in this kind of material is in
most cases impossible. The anomalies studied in glacifluvial material are
usually mineral anomalies — not anomalies of a single element.
Sulphide grains and other easily weather able minerals will seldom be
found in glacifluvial material. However, certain resistant minerals such as
cassiterite, magnetite and gold may even be concentrated by glacifluvial
processes, to the extent of forming economic mineral deposits (placer
deposits).
As most glacifluvial material has come from till, two different transport
mechanisms have had their effect on the dispersion of the material. The
total transport distance may be some kilometres or even tens of kilometres,
and to discover the actual transport route is difficult.
Silts and other fine-grained waterlain sediments which were deposited in
ice margin lakes or in the sea in front of the terminus of the continental
ice cover a much wider area than other glacifluvial deposits. This kind of
material has not found much use in geochemical prospecting. Although
it is quite possible to find geochemical anomalies in clay sediments, it is
virtually impossible to trace them back to the bedrock and particularly to a
specific ore deposit in the bedrock.
Transport by waves takes place along the coastline, restricted to the
depth of the wave action. Concentrations of heavy minerals, like magnetite
and garnet, occur along both present and ancient lake and sea coasts. The
material of beach sand may be derived from the drift or rock exposure on
the shoreline or transported to the coast by streams.
Boulders found on ancient shorelines in places where glaciers could
not possibly have deposited them may have been transported by icebergs.
Famous examples are the Finnish rapakivi boulders which have been found
as far away as in Germany and Czechoslovakia — a distance of more than
1,000 km.
Single boulders caught up in the bottom of an iceberg and deposited
on the sea bottom are called dropstones. In fine-grained sediments these
stones are easily recognized as transported by an iceberg, but proving an
iceberg transport mechanism for an ore boulder found at the surface of till
bed, amid glacially transported boulders, presents a challenge.
The wind carries mineral material over barren areas, and in the process
separates minerals according to their abrasion resistance and specific
gravity. Anomaly patterns created by wind have been reported in the Sahara
and Kalahari Deserts (Rose et al., 1979), but it would be unreasonable to
seek wind-created geochemical anomalies in areas of glaciated terrain. Even
if they were found, it would be exceedingly difficult to interpret them.
110 Geochemical dispersion in the secondary environment
talus anomaly is found upslope where bare rocks are often outcropping.
The transportation of material may be complicated by later movements,
however, making results difficult to interpret.
CHEMICAL DISPERSION
General
Chemical dispersion is transport of material in ionic or molecular form,
mainly in water solution (Fig. 5-12). Gaseous dispersion and dispersion due
to electrochemical forces are special forms of chemical dispersion. The usual
prerequisite for chemical dispersion is weathering of the rocks. The main
factors controlling the dispersion are the acidity and redox potential of the
environment, the solubility of the minerals and other chemical compounds
in the rock, and the adsorption of ions and ion exchange on colloidal
particles. In the course of the dispersion the elements are released from
the primary minerals and transported in water solution, in aerosol form or
by electrochemical forces. Fixation of elements by chemical reaction into
112 Geoehemical dispersion in the secondary environment
Ice flow
(
Chemical dispersion
a) BY GROUND WATER Glacigenic clastic
b) ELECTROCHEMICALLY dispersion
C) POSTGLACIAL WEATHERING
<\
Ground water Jx_.<0 '/L· . '^Α ό O
T
Λ
flow ^<^^>j.\:vV/# ^
"7" M — X ^ X X
Bedrock
Fig. 5-12. Schematic illustration of chemical and clastic dispersion in the overburden.
the mineral grains in drift and in weathered bedrock are much more
vulnerable to leaching than those of the barren bedrock or outcrops because
of the greater surface area. Hence, except in mountainous areas, the main
part of the elements dissolved in water have probably been derived from
drift and the weathered bedrock rather than from the unaltered bedrock.
Because the weathered crust in situ is much thinner in glaciated areas
than elsewhere, the common geochemical rules of chemical equilibrium in
weathering processes must be applied for the special environment of glacial
overburden.
TABLE 5-II
The average contents (ppm) of selected metals in the <60 urn fraction of till above (A) and
below (B) the water table. Analyzed by atomic absorption method after Aqua Regia leach. Data
from 14 pits in Polvijärvi, eastern Finland
Co Cu Mn Ni Pb Zn Fe Number of
samples
A 7.2 27.1 80 16.9 5.5 22.1 7400 59
B 8.0 37.6 114 20.2 6.2 31.7 9300 39
1.8 i \- i.e
0 1 2 3 U 5 6 7 8 9 10 11 12 13 14
pH
Fig. 5-13. Behaviour of the reduction-oxidation potential (Eh) of several valencies of the
elements arsenic, iron, cobalt, manganese, nickel and vanadium as a function of the hydrogen
ion concentration (pH) at normal conditions (298.16°K, 1 atm). Modified after Rosier and
Lange (1972).
-0.8
-1.0
10 U
pH
Fig. 5-14. Approximate position of some natural environments as characterized by Eh and pH.
Reproduced with permission from Garrels and Christ (1965).
Cu
Kaasila Maaselkä Talvivaara
(0 10.0 "i
(0 ·\Λ·
υ
(A ;:-
• / I · ·/· ·
o
*/ ·
Φ 1.0 •V • ·
c
o ^7>
Ü
Φ
(0
£ o.i _
2000 500 64 <2 2000 500 64 <2 2000 500 64 <2 |im
Zn
Kaasila Maaselkä Talvivaara
W 10.0
• #
(0
•/
•*··/.
o
(0
J· ·
0)
o ·/·.·
•
k
c
<D 1.0 %·* -S—**£ *· ·
•*.v··
c
.·:#·.·'
o
o • •
Φ
•(0>
~
2 o.i
2000 500 64 2000 500 64 <2 2000 500 64 <2 μπΐ
Fig. 5-15. Relative Cu and Zn contents in different grain-size fractions compared with the
content of the total till sample. In Talvivaara only three samples contained enough clay for
analysis. Reproduced with permission from Nikkarinen et al. (1984).
(5) In more complex cases, the activity of other ions competing for the
sites.
Geologically, glacial till is a very young material and many of the
processes described above have not had time enough to reach a chemical
equilibrium. It should be emphasized, therefore, that the rules described in
textbooks will not work at all times and in all places.
Electrochemical dispersion
Within and around an orebody with high electrical conductivity, an
electrical potential field is created by the different states of oxidation in
the environment of its upper and lower parts. The orebody and the ground
water of the surrounding country rock could thus be considered as a
galvanic cell through which electrical currents flow, carried by electrons
within the ore and by ions in the ground water (Fig. 5-16). These currents
Chemical dispersion 119
Oxidation
of ore
Fig. 5-16. Schematic model of the upper part of a sulphide ore body outcropping under glacial
till. Thin lines: equipotential surfaces. Heavy lines with arrows: current direction of positive
electricity (H + ) in the electrolyte. p&, ρψ, Ρτ> Ρο>: electrical resistivity in country rock, oxidized
zone, glacial till and ore, respectively. Upper curves indicate paths to be expected from various
dispersion mechanisms in the ground water of the overburden samples close to the bedrock.
Modified after Bölviken and Logn (1975).
Surface
Surface
Surface self.
Surface
Surface
^Λθ<Τ
Fig. 5-17. Schematic illustration of conceptual electrochemical model and current distribution
around conducting sulphide body, and resulting distribution of H + and organic carbon in surface
soils. Reproduced with permission from Govett and Chork (1977).
Gaseous dispersion
Cu ppm Cu/C
25 0.025
15 + 0.015
Cu
Cu/C
OlO
Fe% Fe/C
4.5 + 18
2.5110 Fe/C
Fe
OlO
mV
450+
225
SP profile
-75
Ia Δ l Overburden
ffltitti Monzonite
I I Skarn and amphibolite
I■:■: I Quartzite
I H Mineralization
\ Drill hole
0 200 m
Fig. 5-18. Some metal concentrations and metal/carbon ratio in humus samples along a
study line over a sulphide mineralization, Laurinoja, Finland. Modified after Nuutilainen and
Peuraniemi (1977).
and hydrocarbons, and a wide range of sulphur gases. Metal ions are
liberated from certain types of ores and are dispersed in the vicinity of
the orebody as far as conditions and time allow. What is occurring, in fact,
is chemical dispersion in the gaseous phase. It can be supposed that the
oxidation of sulphides to sulphates is the chemical reaction producing a
122 Geochemical dispersion in the secondary environment
Anomaly formed by
gaseous dispersion
Fracture
zones
Fig. 5-19. The formation of a geochemical anomaly in the overburden by gaseous dispersion.
Although the methods are technically well developed and easily applied,
wet soil and rainfall will reduce their effectiveness or even prevent their
application. Gas geochemistry is treated in detail in another volume of this
series, Volatile Elements in Mineral Exploration. A short description was
included here because the possible transport of heavy metals by carrier
gases must be taken into account when tracing the source of an anomaly in
soil.
CONCLUSIONS
Because they are broader, secondary aureoles often are easier than
primary aureoles, as targets of geochemical exploration. Where ore material
has been dispersed by several different agents, there will be hints of the ore
over a much wider area than the area of the orebody itself.
Of the several different agents causing dispersion of ore material in
the secondary environment, the most important in glaciated terrain is
glacigenic dispersion. If the Quaternary geological features of the study
area are sufficiently well known, both the direction and distance of the
glacial dispersion can be determined. Then also the source of a geochemical
anomaly — the ore deposit — is easy to locate. Likewise, anomalies due
to gravity, though uncommon, are easy to trace back to their source. The
effect of other agents — like wind and water — is much more difficult to
interpret.
There are two main types of geochemical dispersion in the secondary en-
vironment: clastic and chemical. In areas of glaciated terrain, geochemical
Conclusions 125
anomalies are usually the product of both of these but with the glacigenic
clastic dispersion dominant. Outside of glaciated terrain in temperate zone
chemical dispersion is more important.
The amount, direction and distance of chemical dispersion depend on a
variety of factors — pH, Eh, solubility of ore material, grain size, adsorption
properties, ion exchange capacity, etc. — which means that the task of the
exploration geochemist is more difficult in areas of anomalies formed by
chemical dispersion than by clastic dispersion. Some lesser known types
of dispersion such as electrochemical dispersion and dispersion in gaseous
phase are closely connected with chemical dispersion.
As a rule one needs to know the chemical and clastic contributions to
the anomaly and to have a fair knowledge of the Quaternary and glacial
geology of the study area, to be able to interpret the results correctly and
locate the source of the anomaly — the orebody.
127
Chapter 6
INTRODUCTION
y = yo e **
Frequency distribution parameters 129
D i r e c t i o n of g l a c i a l f l o w
x x
\ o (km) —
\ proximal contact
Fig. 6-1. Determination of the frequency distribution parameters K, MD and a for indicator
particles. The provenance rock is shown in black and the dots indicate the frequency of indicator
particles in stone counts.
tors (Krumbein, 1937; Gillberg, 1965, 1967; Perttunen, 1977), the most
important being the abrasion resistance of the rocks and minerals to com-
minution, the topography and the mode of transport. The parameter is
thus understood as an index of the comminution process. During the glacial
transport the particles are crushed and fractured, their number increases
and, down to the terminal grade, their size and the percentage decrease.
The crushing of large fragments during glacial transport changes the size
distribution. In other words, till becomes more mature during the transport,
and the characteristic terminal grades for each lithologic type are reached
(Dreimanis and Vagners, 1971). There is a typical mode representing rock
fragments (usually granules of 2-4 mm in diameter) and another for single
mineral particles (0 < 0.06 mm). Hence the value of a decreases with
decreasing particle size (and the half-distance value increases).
To summarize, the factors controlling the frequency distribution parame-
ters of coarse grained till fragments are grain-size effect, bedrock lithology,
size of the source area, mixing with older deposits and mode of glacial
behaviour. These factors are briefly discussed in the sections that follow.
Grain-size effect
The transport distance of clasts varies with their size. The distances
of transport for different grain fractions have been studied by Szabo et
al. (1975), Perttunen (1977) and Salminen and Hartikainen (1985). It has
been shown that the contribution of the underlying bedrock to the stone
count greatly depends on the size fraction examined. In studies in New
Brunswick, Canada, Szabo et al. (1975) found a contribution of 90% at
about 13 km from the contact in the 1.9-3.8 cm fraction, but within 3 km
in the 0 > 5.1 cm fraction. Boulders from the underlying bedrock have
been found to constitute as much as 80% of the total count just a short
distance from the proximal contact (see also Dreimanis and Vagners, 1971).
Szabo et al. (1975) argued that investigation of the distribution of
indicator pebbles in drift provides the quickest and easiest way to determine
the general pattern of the transport. Earlier Repo (1957) found that the
pebble fraction reflects most clearly the general lithologic variability of the
underlying bedrock.
Boulton (1975) has described how the preferential transport occurs in
response to different debris sizes. When particles are smaller than 0.008
mm, regelation flow occurs around the individual particles, resulting in only
limited entrainment. At the opposite extreme, when particles are greater
than 16 mm in diameter, plastic deformation of ice may begin to operate,
which means that large particles will not be significantly entrained either.
On that basis, Eyles and Menzies (1983) concluded that debris ranging in
size from silt to pebbles is actively transported, and that the finest till
fraction has only a short glacial transport and reflects the local bedrock
Frequency distribution parameters 131
more clearly than the other fractions. This has also been demonstrated in
field observations. Salminen (1980) emphasizes that when the location of a
mineralization causing an anomaly is being estimated, the investigation of
the transport distance must always be conducted on the fine fraction rather
than the pebbles of the till.
Salminen and Hartikainen (1985) found further that boulders on the
surface of till blanket have been transported farther than the finer fractions
of till, which means that the source area of a surface ore boulder is usually
harder to find than that of a geochemical anomaly. However, in the core
areas of the last continental ice sheets, surface boulders in hummocky and
Rogen moraine areas have a close relationship with the underlying bedrock
(Minell, 1980; Bouchard, 1986; Salonen, 1986).
The different fractions of till thus reflect the system of glacial transport
in different ways. Geochemical anomalies best reflect the local variations
in the transport system. The length of the anomaly not only shows the
length of glacial transport but the combined dilution effect of the mixed
lithologies by comminution. Surface boulders will have been transported a
short or long distance depending on the behaviour of the glacier at that
place during deglaciation. And finally, the general lithologic variability of
the glacial transport is best preserved in the sand (mineralogic) or pebble
(lithologic) fraction.
Lithologic effect
Studies on the effect of bedrock type on till lithology (Gillberg, 1967;
Linden, 1975; Perttunen, 1977; Bouchard et al. 1984; Salonen, 1986) show
that the average length of half-distance in the pebble-boulder fraction
varies with the rock type. Limestones and quartzites have the longest
average values of half-distance, and gabbros and mica schists the shortest.
The lithologic effect in boulder transport has been verified in numerous
field studies. Holmes (1952) observed how weak black shales were abraded
to smaller size so that no fragments of pebble or larger size were observed
more than 6.4 km from the outcrop. On the other hand, the decrease
in the amount of quartzitic rocks was so gradual that they constituted a
conspicuous element in glacial drift as far as 130 km from the outcrop.
The quartzites were the toughest of the abundant drift materials. Gillberg
(1965) noted that a dilution by softer rocks, e.g., Cambro-Silurian limestone
and shale, in till will result in a lower value of (a) for more resistant rocks,
e.g., sandstone and dolerite, than for the same rocks within a gneiss-granitic
till.
In laboratory tests designed to study the abrasion and impact strength of
different rock types, Kauranne (1970) demonstrated that the most brittle
rocks are limestone, pegmatite, quartzite and rapakivi granite. According
to Swedish impact tests, the impact resistant rocks are phyllite, leptite,
132 Glacigenic dispersion of coarse till fragments
ROCK TYPE
Gabbros I · 1 (n-3)
Metavolcanics · 1 (n = 8)
Granitoides · , (n = 18)
Sandstones l · 1 (n-3)
Limestones i · 1 (n-3)
Quartzites . · , (n = 7)
5 10 15 20 25 30 km
HALF-DISTANCE VALUE
Fig. 6-2. Half-distance values of different indicator rocks based on data from Gillberg (1967),
Linden (1975), Perttunen (1977), Bouchard et al. (1984) and Salonen (1986). The circle indicates
the mean value and the bar its standard deviation. Fraction: cobbles-boulders.
diabase, greenstone and amphibolite. Thus, as Fig. 6-2 shows, the impact
resistant rocks tend to have the shortest transport distances, and the most
brittle rocks, quartzites and limestones, the longest.
The observations above reveal a relationship with glacial processes.
According to Drewry (1986), hard brittle rocks such as granites and certain
metamorphic rocks are particularly susceptible to crushing, fracturing
and abrasion. Softer strata, exemplified by shales, thin bedded sandstones
and some volcanic rocks, are readily abraded and also fractured and
crushed. Very soft, argillaceous rocks like limestones, marls and slates are
dominantly eroded by the ploughing component of abrasion and hardly
affected by fracture.
Lithologic factors are important in controlling the length of glacial
transport, and, as Shuts (1976) points out, dispersion curves should always
be defined for particular rock and mineral types. The wide variation within
a single lithology (Fig. 6-2, standard deviations), particularly for granitoids
and volcanic rocks, should be noted, however.
Fig. 6-3. Relation between the width of the bedrock area and the half-distance value. Fraction:
cobbles-boulders. Data as in Fig. 6-2.
versus the logarithmic diameter of the outcrop (Fig. 6-3). The correlation is
quite poor: the regression function explains only 32% of the total variance.
Clearly, the larger the provenance outcrop is, the greater the value of
the half-distance can be expected to be. However, this relation is not alone
sufficient. Besides the gross length of the outcrop there are other important
physical factors relating to the provenance outcrop — factors such as the
direction of fracture systems in the bedrock in relation to the direction of
glacial flow and the topographic setting of the source area (see Chapter 5,
this volume).
Topography
The temperature of the basal ice plays a key role in determining the
erosional capacity of glaciers. The thermal boundary conditions at the
ice-bedrock interface are some of the most important in the whole of glacial
geology (Boulton, 1974). If the basal ice is cold, below the pressure melting
point, erosion and sedimentation processes may be severely affected or
totally inhibited. Under cold basal conditions, low velocities reduce the
outward flux of entrained sediments in traction of the bed or higher
level transport. In a warm-based wet glacier, on the other hand, debris
is deposited, underlying strata are abraded, and particles are crushed and
sheared.
Where the surface of the bedrock is uneven, a mosaic of secondary,
deflecting ice movements may develop at the bottom of the ice sheet, result-
ing in small-scale variations in basal temperatures. On the downstream,
freezing-on side of a bed protuberance, clastic material is entrained through
a quarrying-type of bedrock erosion. Melting occurs on the upstream side
of hummocks, leading to net deposition of debris. This process is at work
134 Glacigenic dispersion of coarse till fragments
M - 4 . 1 0 km
n = 52
0.5 1 2 3 4 5 10 20 3040 50 km
VALUE OF H A L F - D I S T A N C E
Fig. 6-4. Frequency distribution of half-distance transport for cobble and boulder fractions. The
half-distance varies from 0.2 to 50 km.
DISPERSAL TRAINS
beds originate from lower parts of the terrain. In the study of the pattern
of dispersal of granite blocks in Gaspe, Quebec, David and Bedard (1986)
observed that those lithologies that formed positive relief and projected
well above the general level of the surrounding ground surface were eroded
most and transported farthest.
Dispersal trains are typically finger- or ribbon-shaped (Shuts, 1976).
They are narrow, and often long in mountainous areas and where ice flow
has occupied tectonic trough valleys. Fan shapes may result where trains
are formed with radical spreading in lowlands or near an ice front. Multiple
transport also tends to create wide-angled boulder fans. Dispersal trains
are commonly narrow and short close to the marginal zone of the retreating
glacier.
Boulder fans characteristically coincide in orientation with the last or
most pronounced direction of glacial flow, occupying a sector of approxi-
mately 10°. But this angle may be considerably wider if the fan is a product
of a number of ice flows of varying directions; fans opening up to angles
as much as 90° have been described (Hyvärinen et al., 1973). Close to
ice divide zones, as in Finnish Lapland (Tanner, 1915) and in the Gaspe
Peninsula, Canada (David and Bedard, 1986), the dispersal is often the
combined result of many shifting consecutive glacial phases.
Boulder fans are normally some 1-5 km in length, but variation is wide.
The longest examples described to date measure 50-100 km, though some
individual boulders appear to have been carried as much as several hundred
kilometres from their place of origin by glacial action. At the other extreme,
one finds local boulder trains that are only some tens or hundreds of metres
in length.
Transport distance distributions 137
In 1961 Matisto determined lateral limits for each bedrock type up ice
with respect to glacial flow and with this technique discussed the effects of
complex transport. Salonen (1986) discerned a negative exponential func-
tion (Fig. 6-1) in the form of cumulative frequency curves. In this transport
distance distribution (TDD) method, a sample of boulders comprising many
lithologies is investigated, rather than a single indicator rock type, and the
transport distance is measured in the opposite way than in the half-distance
method. In the TDD method the many lithologies of one sample are con-
nected with up-ice bedrock sources, whereas in the half-distance method,
many samples of the same lithology are identified and located downstream
in the glacial flow (Fig. 6-6).
138 Glacigenic dispersion of coarse till fragments
- 1 0 1 2 log km
x - a x i s : Distance to provenances
Fig. 6-6. Method of estimating the transport distance statistics GM (geometric mean) and SD
(standard deviation) using log-normal probability paper.
between 0.8 and 10.0 km in cover moraine areas. For the surface boulders
of drumlins, the geometric mean was 5-17 km.
Mixed transport populations have been encountered in areas of thick till
beds especially in northern Finland. Typically the deposits consist of one
or more lodgement till beds. Rock material may have been transported by
several glacial cycles and the transport distance (GM) of surface boulders
may vary within a wide range (1-25 km) (Salonen, 1986).
The observations on the transport distance distributions of surface
boulders show that there are two major glacial processes whose possible
existence needs to be kept in mind when studying the length of boulder
transport: the till renewal process and the intermixing of materials from
earlier deposits. The first is important when the ice sheet behaves as
a slow-moving conveyor system, eroding the bedrock during deglaciation
and transferring it. The process is controlled by lobate flow, in which
rests of the ice sheet and various flow regimes are interchanging. In
this situation, boulders tend to form short and narrow indicator trains.
A variable proportion (approximately 1-20%) of boulders is indicative of
the second process — intermixing of materials of earlier glacial cycles.
These boulders may have a long and complicated transport history which
is difficult to unravel. Multistage transport is common especially in areas
where the ice was stagnant during the deglaciation (Punkari, 1984), and
where till stratigraphy tends to be complex (Hirvas and Nenonen, 1987).
There is information on almost 500 boulder trains in Finland, and,
boulder transport has been measured in 41 half-distance traverses and 111
TTD determinations (Salonen, 1986). On the basis of these data, the known
areal variability of glacial deposition (Kujansuu and Niemelä 1984) and
general trends in till stratigraphy (Hirvas and Nenonen, 1987), it is possible
to summarize the dispersion for the boulder fraction as shown in Fig. 6-7.
In the dark grey areas boulder trains tend to be short and narrow. These
areas are most suitable for indicator tracing. In the light grey areas the
lobate flow pattern predominates in clast transport and boulder trains may
be long, but narrow, and strictly follow the direction of glacial flow. In the
white areas with short average transport distance local material dominates
in surface boulders, but part of them may have been transported by earlier
glacial flows. In Finland, this kind of transport distribution is mostly found
in the north, where it is associated with the ice divide zone. White areas with
long average transport distance are those of complicated boulder transport
Complex stratigraphy with multistage glacial transport characterizes the
till material. Boulder tracing is difficult and many valuable ore boulders
have never been connected to their mother lode. In several cases a follow-up
study with geochemical and mineralogical methods has led to a positive
result (e.g. Hyvärinen, 1969).
140 Glacigenic dispersion of coarse nil fragments
LEGEND
0 50 100 km
Fig. 6-7. Prediction of the average length and dispersion (mixing rate) for boulder transport in
Finland based on transport distance parameters.
Conclusions 141
CONCLUSIONS
Chapter 7
GENERAL
SAMPLING MATERIAL
SAMPLING DENSITY
REGIONAL PHASE
LOCAL PHASE
DETAILED PHASE
SAMPLING GRID
Fig. 7-2. Distribution of aqua regia soluble barium concentrations in the <0.06 mm till fraction,
Finland. Reproduced from the Geochemical Atlas of Finland.
Sampling grid 147
Fig. 7-3. The three-dimensional shape of an anomaly resembling a smoke plume in the
overburden. Reproduced with permission from Drake (1983).
a few kilometres). Such conditions are met in areas where ice lobes were
active during the deglaciation. However, there are many areas where
anomalies have no clearly defined length, e.g., areas where the glacial
erosion was weak and the transport of material slight. Anomalies are then
local, and it is more reasonable to use a sampling grid that is regular in
every direction.
148 Scale of geochemical surveys
The transport distance is shorter at the bottom of a till bed than at the
surface. Also, the metal and mineral concentrations derived from an ore
suboutcrop increase in the deeper parts of the overburden. Thus a sampling
grid regular in every direction will be preferable for deep sampling.
The design of the sampling grid will be more complicated when two or
more glaciers have transported the till. If the transport directions have
differed and if separate till beds have been laid down, sampling must be
done from different depths at every sampling site. Chemical dispersion
in the till may also reform the anomaly. In cases like these, preliminary
studies are necessary before the final form of the sampling grid can be
decided upon.
Besides the way in which an anomaly was created and the conditions
prevailing where it was formed, the scale of the study has a decisive
influence on the sampling grid. In regional-scale geochemical mapping
(Fig. 7-1) there is no reason to use sampling lines. The distance between
two neighbouring lines would, in any event, be so great that even the
longest glacigenic anomalies would fit between the lines. Also, for reasons
of economy, the sampling sites should be located in accessible places such
as along roads. In regional-scale studies, the optimum sampling grid is an
irregular one (Fig. 7-5A) with variable distances between sites.
REGIONAL PHASE
B
\
Road
\ \
X
V^
, χ
I
x""
1 km
/
Fig. 7-5. Sampling patterns in regional phase geochemical studies. (A) Irregular sampling grid;
(B) irregular sampling, where the sampling density is controlled by the 4 km 2 grid.
Regional geochemical mapping 149
100 km
Y
I I I I 1 I I I
$4:
N
.p». 01 σ> - i ontog O
Y (ppm)
/·♦ ·
fi · · ·
mm · . .
,#···.
>ß · · · # ·
• ·. · · · £ * · · .
§· *···♦· · · ···>
i ············· ·· ·^ ·· ·ν
Fig. 7-6. Distribution of yttrium in the <0.06 mm fraction of till, sampling density 1/300 km 2 ,
Finland. The highest yttrium anomalies reflect areas of rapakivi granite. (From the Geochemical
Atlas of Finland.)
152 Scale of geochemical surveys
Because samples will usually be taken from the surface layer of till which
has been transported a longer distance, and where the metal concentrations
will be considerably diluted the range of concentrations is smaller than
in the bedrock of the source area. The analytical method should therefore
be sensitive, accurate and precise enough to detect the relatively weak
contrast between the anomaly and the background. The aim of regional
mapping is not to search for a specific type of mineralization but for all
potential mineralized areas and targets, and to determine the variations in
the regional distribution of elements. Thus, the analytical method should
allow measurement of as wide an elemental spectrum as possible: major,
minor and trace elements — reasonably 30-40 elements from every sample.
Often more than one analytical method must be used, with a consequent
high analytical cost per sample; this is offset, however, by the relatively
small number of samples. Hence the analytical cost per km 2 is modest.
In addition to ore elements, the most useful elements to determine in
regional geochemical mapping are pathfinder elements occurring in close
association with the elements of interest but more easily found because
they form a broader halo and are more readily detected by analytical
methods. Examples are arsenic for gold and sulphur for sulphide ores.
Another group of elements important to assay in the regional phase are
key elements or key element parageneses, which are typical for certain
ore types. Their concentrations are high in association with ore bodies but
elsewhere quite low; their dispersion halo may be wider than that of the
metal being sought and their range in the sampling material is usually
quite wide. Unfortunately many of them are quite difficult to analyze at the
concentration level in which they occur in drift. Most important of these
key elements are boron, barium, bismuth, antimony and phosphorus.
llomantsi
Au in till
f r a c t i o n - 0 . 0 6 mm
GAAS-analysis
■ 1 ^ i '
Au ppb
·····# ··
'..... 1.0
·..... 2.0
. · · '...._ 8.0
: . . ; · . · •--16.0
• · · . •....32.0
a-.:·::; · · · · _64.0
7m. KUJTT.ILA .
:fc ■..■:.:
• Pulkir^arkat
5 km
31 10'
llomantsi
Au in till
f r a c t i o n - 0 . 0 6 mm
AAS-analysis
Γ
3 1 " 10'
Fig. 7-7. A. A geochemical map with concentrations divided into different levels and each level
indicated by a dot. B. Same data as in A, but the interpolated data are presented as grey tones.
Local scale studies 155
LOCAL-SCALE STUDIES
sampling can then be effectively designed on the basis of these data, and
on any information on the bedrock, information from earlier geochemical
studies, and geophysical measurements.
The main aim of the local-scale geochemical study is to identify areas
where the occurrence of ore deposits is a strong possibility. Areas to be
delineated are usually of several hundred metres wide. Follow-up studies
— further geochemical sampling, digging of traverses or diamond drilling
— can then be concentrated in these areas.
In addition to the analytical data, stone counts in the coarser fraction
(e.g., >4 mm grains) of the samples easily provide information about the
lithology of the bedrock; they may even give evidence of ore minerals and
ore mineral associations (Fig. 7-8). The heavy mineral study of soil is often
combined with this local-scale phase of geochemical study.
If the surface of the bedrock and the material of the overburden are
not too strongly weathered, a good picture of the lithology and structure
of the underlying bedrock is obtained on the basis of the analytical and
mineralogical data of the overburden. In principle, all the chemical changes
that have occurred in the bedrock are reflected in the overburden. Further,
transport of the material either mechanically or chemically in solution will
have diluted element contents and changed the original element ratios.
However, if the samples are taken from the bottom part of the overburden
— as they should be in local surveys — the contents will not be excessively
diluted nor will the material be mixed too much.
The anomaly patterns of local phase studies mainly reflect the lithology of
the bedrock (Fig. 7-9A and C), but quite commonly they also extend across
the contacts of different rock types. Some anomalies may be associated
with fracture zones where metal ions are easily able to migrate as fluids,
in water solution or in gas bubbles, up the contacts. Others may be due to
metasomatically altered aureoles around ore bodies (Fig. 7-9B). In this way,
information is obtained not only about the surface of the bedrock but about
deeper parts, and about the chemical changes that have occurred there.
The best results in local-scale geochemical studies are obtained by com-
bining geochemical, geophysical and geological methods in the particular
manner the case demands.
Fig. 7-8. The percentage of schist pebbles in the 2-20 mm till fraction in the Korentovaara study
area, Ilomantsi, Finland compared with the lithology of the bedrock. Bedrock after Lavikainen
(1973). Modified after Salminen and Hartikainen (1985).
158 Scale of geochemical surveys
•S·*.·»«
Ilomantsi
ih Ni p p m
;iir;;:-;:-;ji
fe-sa?-···*··:·:
A ··::*:::::,
• · ·· ■ · · · · ·
62°_
45' ::::i:?:::::
::·.:·::·.::*:
■ Α * ; ; : : Λ : : : Ϊ : Ϊ : Ϊ : · " : :.'::?:·: 3 km
31° 1 0 '
Ilomantsi
:::?::?:::: : · : : : : ! Μ Ι
?ϋ:>::?1? ·.: K in till
!Ü f r a c t i o n < 0 . 0 6 mm
OES-analysi s
? K
■:.:.'.:::::fi!:· ····■··■ ··■·· ·
:."!".;r.t i"; # . . · . · · · · · · β ·.·· ·
. . . . . . ·· . ; .· ^ . . · . . . ·: . :. · . ; ; · ■ · . ·· . : ; , . : . :
r.S"-.- ··■.■.·.::::::::. : : ^ : : : : : : J
i· ■ · ^^ ..." ;* e r . . . . . . . 1
aktaL·* ..·:'.·:
•F·•'W"·· ·· ■·.·"·· ·
.:..·;.:.--- i
" . : ·:· :·■. ;· ·: : · .'.*·'.;
- ' - > · · · ■ * · · · · . ·· · ·· . · · · ·«
i · · · · ! · « · · . . · · . · · ··.···■;.·■:::·:
•v:sfei3iti»>Kv;v;·;*:;^
■ * ■ · ··
62°-
45'
:
·::·:Λ::·.: τϊ: ϊ:
*as
»r·:*· 3 km
;*!:
Ί
31° 1 0 '
Fig. 7-9. A. Nickel contents of till fraction <0.06 mm, sampling density 16/km2. The Ni
anomalies reflect the schist belts (see Fig. 7-9C). B. A metasomatic halo shown by K anomalies
in <0.06 mm till fraction, sampling density 16/km2. Lithology of the bedrock is shown in Fig.
7-9C.
Local scale studies 159
C x ^
X X X X
x ^ x x
χ X X 1 x/ X X X
x
x
x x/
As
if X x x
x / ' X
x XY/ Y X
\f
X X
X X
X X
Wj Y 7
X V\\ f x x
x x
x\ X YYT X
X X
X X X
X
x
Kx
/ x
/ x
X
X
X
X
X
0
1
II x
γ 3
χΛ X X X km x
' X
x K\
x / \ Granitic and granodioritic r o c k s
Y Tonalite
Archaean s c h i s t s , mainly g r a y w a c k e s
Iron f o r m a t i o n
Fig. 7-9 (continued). C. The main lithologic features of the area presented in Figs. 7-9A and B.
Sampling
• sites
# ·
Ice flow · * #
■* * · i ·
direction · ·
Fig. 7-10. A schematic presentation of a sampling grid to be used in areas of long glacial
transport of drift.
the bottom part of the drift the material more closely resembles the
underlying bedrock because of the shorter transport. According to recent
studies in Scandinavia, the material derived from a smaller ore suboutcrop
is detectable by chemical and mathematical methods available today only
within a distance of a few hundred metres. The sampling interval selected
should thus be less than the distance over which the anomaly is detectable.
Light drilling equipment is usually sufficient in regional mapping, but
heavier drilling machines are necessary in the local phase. Portable percus-
sion drills are adequate if the average thickness of the overburden is less
than 10 m. Thicker overburden demands heavier hydraulic or pneumatic
machines. Because the samples are taken from the bottom part of the
overburden, one must be careful that bedrock material — weathered or
unweathered — does not get mixed with the till or other material in the
overburden. The bedrock sample from beneath the overburden is valuable
in itself, but combining the results from different sampling materials is
never permissible in geochemical studies. A sample from the overburden,
especially a till sample, gives information from a much wider area than a
single sample from the bedrock.
the sampling point relative to the water table. These can vary much over
the target area, affecting concentrations and ratios of elements, so that
the results from separate sampling sites differ in a way that sophisticated
statistical methods cannot tolerate. If the variation in the geological na-
ture of the target area is not known and the area cannot be divided into
sub-areas that are statistically homogeneous, the mathematical results that
are obtained may be meaningless or misleading. In such cases the easily
controlled, simple parameters like metal ratios are very useful. In inter-
preting results it is essential to keep in mind the type of ore being sought
and how this type of ore is typically reflected in the metal concentrations
of the overburden. Whereas use of statistical methods and a computer has
obvious benefits, common sense must prevail in their application. In these
days of the widespread availability of specific statistical software packages,
the temptation to mindlessly feed geochemical data into a computer for
commercial routine methods of processing must be overcome.
DETAILED STUDIES
sampling done, and direct observations can be made of the bedrock. The
representativeness of a sample becomes very important in this phase. In
the lower density sampling, when samples are taken from the overburden,
and especially from the surface layer of the overburden, even a very small
sample is homogeneous and representative enough. But for detailed study
a single sample from the bottom of the overburden, and especially from the
bedrock under the overburden, is not representative enough. The quality
can be improved by using composite samples from the till or taking large
(> 1 kg) samples from the bedrock.
In areas of thicker (>5 m) overburden, where the bedrock cannot
be reached by excavator, heavy drilling machines must be used. The
equipment should be large enough to allow penetration of as much as 30
m of overburden, and to sample the bedrock underneath. There is one
big difficulty in bedrock sampling through the overburden: the sample
could unknowingly be from a narrow vein or unrepresentative type of
bedrock. Caution about the representativeness of samples needs to be
exercised at all times. It would be helpful to take a sample from the
bottom part of the overburden as well, since it reflects — especially in
glaciated terrain — bedrock from a wider area than the sample from a
point in the bedrock. The representativeness can also be improved by
taking a core sample a few metres long by diamond drill. Unfortunately, the
sample from the overburden, the sample from the surface of the bedrock
(crushed or powdered) and the core sample all require a different type of
sampler; taking all types of sample may be very expensive despite modern
drilling machines that make it possible to use the same engine for different
samplers.
The computer plays a less important role in processing the data and
results of the detailed study phase than in the regional and local-scale
studies. Usually mineralogical studies account for a substantial share of
the data interpretation at this stage. Multivariate statistical methods are
not required, because trends in elemental concentrations and their internal
relations will suffice. Often the raw data will be sufficient for the geologist.
If the number of samples is less than a hundred, or at most a few hundred,
as often is the case, it may also be more economical to prepare the maps
and diagrams for the report by hand.
In contrast to the regional and local-scale studies, what is important at
this stage is that the geologist in charge be constantly in close touch with
the work in field, laboratory and office. Things usually happen fast and
interpretations and decisions need to be made promptly if the operation is
to be cost effective.
CONCLUSIONS
The scale of a geochemical study depends on the aim of the study and,
according to the aim, geochemical studies are divided into three groups: (1)
regional, (2) local, and (3) detailed.
In regional-scale studies (i.e., regional geochemical mapping), geochem-
ical provinces several tens of square kilometres in area are delineated. A
study of this scale is cheap because of the low sampling density (1.0-0.01
sites/km 2 ) and easy sampling (samples are taken close to the surface of the
overburden). The result is broad and reasonably reliable information about
the geochemistry of the study area. It is also possible, on the basis of the
regional-scale study, to evaluate whether geochemical prospecting methods
are practical in the study area. Analysis for as many elements as possible
and interpretation of the results by multivariate statistical methods are
typical in this phase.
In local-scale studies, zones some hundreds of metres wide, which
are critical for prospecting, are delineated. The sampling density varies
between 4 and 40 samples/km 2 . The best sampling material is basal till,
typically transported some tens or hundreds of metres by glacier. This
till represents a fairly wide source area. As a rule, the ore type sought
is sufficiently well known that analytical methods can be selected on that
basis. Fewer elements than in regional-scale studies need to be analyzed.
However, sampling depth needs to be greater, which makes the sampling
more expensive and limits the feasible area of study to a maximum, say
100 km 2 . The results are used for planning the next phase (detailed) of
geochemical studies and sometimes even diamond drilling.
164 Scale of geochemical surveys
The goal of the detailed studies is finally to locate the ore outcrop or to
indicate sites for diamond drilling. The sampling density is tens or even
hundreds of samples/km 2 . Samples should be taken from the bottom of the
overburden close to the bedrock. These studies are expensive and must
be restricted to small areas only. Optimally they are used together with
geophysical and geological methods.
A geochemical study proceeding step by step from regional mapping via
local-scale studies to detailed geochemical prospecting is very useful in
areas where geological knowledge is scant. It is then possible to proceed
from large geochemical provinces via ore critical zones to the final locating
of an ore body.
165
Chapter 8
FIELD METHODS
INTRODUCTION
Fig. 8-1. A portable computer is recommended for recording the field data. Photo Pekka
Virtanen.
staking out lines at the sampling target and tying the sampling points to
them.
The need to stake out lines beforehand to obtain the location data
greatly increases the total cost of sampling. Often, however, the same line
system can be used for other studies, such as geophysical ground surveys
and geological observations, thus reducing geochemistry's share of the
total expenses. Once automatic locating satellite systems are available at a
reasonable price, as they soon will be, determining the location and storage
of the data will be considerably more rapid, easy and accurate.
168 Field methods
SAMPLING EQUIPMENT
The wide range of sampling equipment on the market puts the planner
of a survey project in quite a quandary, at least in theory. Sampling
(the whole field stage) accounts for 50-80% of geochemical survey costs.
Thus it is not just the survey strategy but also the funds available that
decisively affect the choice of sampling method and sampling equipment.
The sampling equipment used for till and residual sediments can be divided
into two groups with very different rates and depths of penetration: (1)
sampling without flushing, and (2) sampling with drills provided with air
or water flushing. Drills with flushing can penetrate tens of metres of
minerogenic overburden; the best units even permit sampling of underlying
fresh bedrock. Without flushing, in contrast, the sampling depth in till of
light drills is no more than a few metres. Flushing, of course, tends to
remove the finer grain size fractions.
Fig. 8-2. Sampling from a pit dug by a tractor excavator is often the most cost-effective
procedure. Photo Peter Johansson.
Sampling equipment 169
Fig. 8-3. Blasting of the sample from bedrock gives samples with a fully satisfactory size and
representativeness. Photo Pekka Virtanen.
Fig. 8-4. A simple hand-held auger drill guarantees a sampling depth of about 2 m provided the
conditions are good. Photo Martti Kokkola.
good. The sample is obtained with an open auger bit. A manual impact
tube (Irish) sampler is still better. With these samplers there is always a
danger of contamination, therefore particular caution should be exercised
during sampling. The method has the advantage that the equipment is
light-weight and can be taken anywhere accessible to the sample taker.
Portable percussion drills (mechanical or hydraulic) driven by combus-
tion engines are a more advanced and efficient type of drill (Fig. 8-5). The
hydraulic ones, mounted on sledge, have shown to be very effective. They
penetrate more than 10 m in mineral soils. The stoniness and boulders
hamper the use of this equipment. Nevertheless, samples can be taken from
substantially greater depths than with the above sampling techniques, and
contamination can be avoided by using an appropriate sampler. Although
in principle the equipment is portable, so many rods and other accessories
have to be taken along that its transport by human force is not economical.
A snowmobile is a convenient transport vehicle in winter and a crawler in
summer.
Drilling techniques that make use of flushing are notably more effective
than those that do not. The flushing can be done with compressed air
or water or even with both together. In either case the sampling unit is
a complex, heavy and awkward piece of equipment to move around (Fig.
8-6). The primary requirement for the application of water flushing is, of
course, that sufficient water be available and that a supplementary pump
Sampling equipment
Fig. 8-5. A portable percussion drill driven by a combustion engine is a more advanced and
efficient type of drill. Photo Pekka Virtanen.
and water line be installed at the sampling site. Indeed, the method tends
to be so costly that it is seldom used for till and soil sampling and is
better reserved for bedrock sampling through the overburden, and even
then mainly for delineating a formation already discovered. In terms of
cost, this type of sampling approaches that of diamond drilling, which it
also resembles technically although the hard metal crowned drilling bits
are cheaper. Under difficult conditions, it may turn out to be even more
costly.
Drilling equipment relying on compressed air flushing can usually be
mounted on a self-propelled base, which makes for easy mobility (Fig. 8-7).
However, the unit is large and clumsy, requires fairly passable terrain and
is often useless on boulder-strewn terrain or steep slopes. In operating cost
172 Field methods
Fig. 8-6. A drilling machine using water flushing is effective but so costly and so difficult to
move from one sampling site to another that it is seldom used for till and soil sampling. Photo
Pekka Virtanen.
it does not differ significantly from water-flushed drills, and when very
thick overburden (several tens of metres) is being drilled the penetration
capacity is not quite as good as that of water-flushed drills. On the other
hand, the higher mobility of the equipment permits sampling on a coarser
grid, provided, however, that the terrain is not too rough for the heavy unit.
The usual procedure in both water-flush and compressed-air flush drilling
is that, once the desired depth has been reached, the drill bit is replaced by a
special sampling bit. This requires hoisting up the string of rods. Although
this means extra work, the risk of sample contamination is nonexistent
and, in general, the sample obtained is of good quality and the right size.
Reverse circulation drilling (e.g., Strauss et al., 1989) permits continuous
Sampling equipment 173
Fig. 8-7. Drilling equipment relying on compressed air flushing is fairly mobile, but the unit is
large and clumsy and requires fairly passable terrain. Photo Martti Kokkola.
sampling without rod hoisting and bit changing. In this procedure, the
flushing water is returned to the surface along with the loosened till or
soil. Collecting the sludge gives a continuous sample large enough for most
purposes. Although some of the finest material is lost with the flushing
water, experience indicates that sample mixing is very slight and that the
depth information is unbiased. Like the other drilling units with flushing,
174 Field methods
Rods
The drilling method and the source of power it requires generally
determine the type of rod. Given the large selection of rods available,
there is some danger of choosing an inappropriate one. It is normally the
rods close to the coupling sleeves that fail. Therefore both the rods and
coupling sleeves must be of strong enough material to withstand the blows
associated with drilling. Even so, metal fatigue is inevitable and the rods
will deteriorate in operation. (When the drill stem is extended the oldest
and weakest rods should be placed lowermost, because fewer rods will then
be lost if the stem breaks and remains partly embedded in soil). Steel is
the most common material. The aluminium rods employed in diamond core
drilling are no good in soil sampling, not even if flushing is used, because
they are soft and easily damaged in stony soil.
Solid rods can be used in lighter drilling units. These need external
coupling sleeves when the stem is extended, however, and this hampers not
only the penetration of the rods but in particular their hoisting.
The heavier drilling units, which use thicker and stronger rods, usually
employ hollow rods with internal coupling. The drill stem is then smooth
and does not resist penetration.
Samplers
A number of samplers have been developed for soil studies, most of
which have also been tested for geochemical soil sampling. Experience has
taught, however, that to work reliably in hard and stony soil the sampler
must be as simple as possible. Piston and rod type drills or the like are
thus out of the question. Three types of sampler have established their
position: the tube sampler operating on a flow-through principle, the closed
tube sampler and the open auger bit. The closed tube sampler (Fig. 8-8) is
used mainly in drilling by flushing. Sometimes (mainly when compressed
air flushing is used) the sampler is attached to the rods only for the actual
taking of samples; a different cutting head is used for penetrating the soil
layers.
The auger bit (Fig. 8-9) facilitates penetration of the drill stem and is
often used without percussion merely by rotating the drill. However, the
recovery of a sample with an open bit is not very good, and in dry soil
Sampling equipment 175
Fig. 8-8. The closed tube sampler is used mainly with water-flushed drills. Photo Martti
Kokkola.
the sample tends to slip off the bit before it reaches the surface. The risk
of contamination from the upper layers is also considerable. It is often
possible, however, to use fairly wide bits. The size of the sample is then
big enough for most purposes, and the internal parts of the thread contain
material from the desired depth.
The tube bit operating on the flow-through principle (Fig. 8-10) has
turned out to be reliable and easy to handle. However, when the bit is
176 Field methods
Fig. 8-9. The auger bit is usually merely rotated when it penetrates the fine-grained overburden
fairly well, but the recovery of the sample with an open bit is not very good, especially in dry
soil. Photo Martti Kokkola.
coupled to a hand held percussive drill the size of the sample will be small
and usually only sufficient for chemical analysis; it is definitely too small
for mineralogical and lithological studies. In quality, however, the sample
is good and rarely contaminated. This type of bit is not only the cheapest
possible sampler but is simple in construction and therefore reliable.
Sampling equipment 111
Fig. 8-10. The tube bit (Irish type) operating on the flow-through principlehas proved to be
reliable and easy to handle. Photo Martti Kokkola.
Transport vehicles
The choice of transport vehicles used in sampling depends on many
factors. The sampling sites are often far from roads, at least during
the final stages. Only regional geochemical mapping can rely on roads.
Transport by car is then fast and fairly cheap, and sampling units, samples
and other supplies can easily be carried.
178 Field methods
Fig. 8-11. A cross-country motor bike is often useful for moving outside the road network.
Photo Henry Vallius.
In areas of flat topography and not too lush vegetation it is often possible
to move outside the road network with all-purpose vehicles or at least
with cross-country motor bikes or various amphibious and other all-terrain
vehicles (Fig. 8-11). Heavy sampling units cannot be transported by motor
bike, however. Special logistics are required for the heavier equipment
required in detailed studies.
An unbroken cover of snow in winter makes it easier to move and
transport drilling units of all kinds. Pulled by motor sledges or heavier
crawler-based vehicles (Fig. 8-12), even the heaviest drilling units can
rapidly be moved over quagmires and lakes to take the shortest route to
the sampling site. Likewise, daily trips from the sampling site to the road
are feasible, even from distances of tens of kilometres. Deep snow prevents
the freezing of ground, deep frost hampers sampling by drilling.
In summer, use can be made of the waterways in otherwise inaccessible
terrain, although transport of the heaviest drilling units by boat may be
laborious and even dangerous (Fig. 8-13).
Aircraft, and helicopters in particular, make the transport of drilling
equipment feasible to practically any site. Expensive though it may be, use
of aircraft is often the only way to undertake studies economically at targets
Sampling equipment 179
^i 4
Fig. 8-12. Snow in winter makes it easy to move and transport drilling equipment by motor
sledge. Photo Jari Nenonen.
Fig. 8-13. Boats can be used for transporting drilling units through waterways in otherwise
inaccessible terrain. Rock geochemical sampling with portable diamond drill. Photo Tapani
Taipale.
180 Field methods
Fig. 8-14. Use of aircraft is often the only way to reach targets in the trackless wilderness
economically. Photo Pekka Virtanen.
FIELD MEASUREMENTS
Physical measurements
Chemical dispersion that takes place in the gaseous state can be mea-
sured with counters, spectrometers and photographic films (Dyck, 1969a;
McCorkell et al., 1981). The measurement data are then instantly available
in the field, or at least in the field laboratory. Measurements have been
made of radon, helium, hydrocarbons and gaseous mercury. Gases also
carry heavy metal ions. Ions migrating in the pore solutions of soil can be
collected by allowing them to accumulate in filters, ion-exchange resins, ion
traps, etc. for a given period — generally a few weeks — before analysis.
The analyses often must be made in more sophisticated laboratories than
those applicable in the field, however.
Some purely physical methods, such as the self-potential method and
determination of magnetic susceptibility, can be used in conjunction with
geochemical studies. Under certain conditions these are useful, particularly
because the measurement data are available instantly without the lag of up
to several weeks with laboratory procedures. Susceptibility values permit
rapid determination of the variation in magnetite abundances at the study
target. The use of self-potential measurements, though, requires not only
sound knowledge of the measuring technique and its underlying principles
but also sufficient information about the type of target being sought. Only
then can the right conclusions be drawn from the survey data describing
the target's potential field.
It is often important to know the thickness of the overburden, particu-
larly in glaciated areas, as this is vital for the interpretation of geochemical
data. If the available sampling equipment is heavy enough the information
about the thickness of the overburden can be obtained directly in the course
of sampling. When lighter-weight equipment is used, however, the thickness
data must be obtained by other methods. An accurate method is seismic
sounding, but its high operational costs mean that it is rarely applied in
geochemical studies. A markedly cheaper approach is ground-penetrating
radar. True, it too has its limitations, particularly when the stratigraphy is
complex, but it can often be used successfully and even cost-effectively.
Chemical measurements
Earlier, and particularly in locations far from population centres, anal-
yses were made for many elements right in the field. These included
element-specific spot-test analyses, one of which was the qualitative de-
termination of nickel with dimethylglyoxime. With the improvement of
182 Field methods
Mineralogical studies
Several heavy-mineral separation methods, which are mainly applicable
to field operations, are in use, particularly in gold exploration. Should
the gold occur as coarse enough nuggets (grain size over 30 μιη), these
methods would often give a more reliable result than chemical analysis.
Several mechanical explorational devices have been developed to separate
gold. However, if the gold is very fine-grained, as it unfortunately often is,
the numerous and complex devices whose operation is based on the density
difference between grains are not satisfactory. The devises all require the
hand of a skilled user if satisfactory results are to be achieved.
CONCLUSIONS
secondary factors: what is available at the moment and how large the
budget is.
Besides sampling, a variety of observations and measurements can be
made during geochemical studies in the field. Observations such as of the
location (coordinates) of the sampling site are essential. But several other
observations appropriate to the aim and scale of the study can be made
as well. Naturally, the most important of these deal with the geology of
the bedrock and overburden. Studies concerning the character, amount and
direction of geochemical dispersion are particularly useful.
Measurements of radiation are used in prospecting for radioactive ele-
ments. Some indicator and also ore elements can be studied in gaseous
phase by special measuring equipment. Purely physical measurements such
as the measurement of the self-potential field are sometimes made in the
course of ordinary geochemical studies.
Certain laboratory work can be done, and in remote places even should be
done, in field conditions. Simpler analyses and certain mineralogical studies,
especially in heavy mineral investigations, are appropriately carried out in
field laboratories.
185
Chapter 9
ANALYTICAL METHODS
INTRODUCTION
General
Informed selection of analytical procedures is essential to a successful
geochemical study Until recently, the selection of procedures largely de-
pended on experience and intuition, but today demonstrated performance
is the only acceptable criterion. The problem is to identify the procedure
or procedures that correspond best to the exigencies of the application.
It is well enough known how "poor quality" analyses may undermine
the objectives of a study. But it is often forgotten that choosing proce-
dures on the criteria of greatest precision, lowest limits of detection, etc.,
may lead to such low throughput and high costs that the study becomes
prohibitively expensive. Ensuring the economic viability of an extensive
mapping programme involves a very delicate balancing of diverse criteria.
In general, the performance characteristics (or "figures of merit") of
an analytical procedure can be divided into technical characteristics and
economic considerations. The technical characteristics comprise precision,
accuracy, reliability, sensitivity, limit of detection, selectivity and informa-
tion capacity, while the economic considerations involve cost and time, viz.,
throughput and turnaround. Most of these factors have been discussed in
detail by Massart et al. (1978). In the following each is touched upon briefly
from the point of view of exploration geochemistry. The characteristics are
considerably interrelated, and optimization with respect to one parameter
may weaken another. For example, improving the precision by a factor n
may increase the costs of an element determination by the same factor. In
this case the interrelation is straightforward; but most often it is obscure
(Fig. 9-1).
Technical characteristics
Precision is a measure of random errors and is by definition closely
related to repeatability, reproducibility and laboratory bias (interlaboratory
Performance of analytical methods 187
RELIABILITY
SENSITIVITY SELECTIVITY
ACCURACY
COSTS
— EFFICIENCY
STAFF
y L L
blank decision "-detection determination y
Fig. 9-2. Illustration of normally distributed blank, signals with increasing confidence and
critical limits. Shaded areas represent errors of the second type (/?), that is, a decision that the
signal (element) is absent when it is present. Beta has been given here a value of 0.5 at the
decision limit and a value of 0.05 at the detection limit. The standard deviations a b j a n k and
^signal are considered to be equal, which is the case for small concentrations.
where ah\&nk represents the standard deviation of the blank. The choice of k
is arbitrary and depends on the confidence required to answer the question
whether the analyte component is present (decision), can be detected or can
be determined (Fig. 9-2). For detection limit, many authors have chosen a
value of 3 for k. The three-sigma detection limits are obtained in practice by
taking the noise on the background as sigma. However, in some analytical
techniques, as in atomic absorption, the background noise is comparable to
the noise of the analyte signal, whereas in others as in plasma emission, it
is much lower. Thus 3σ limits are not more than indicative for elements
in geosamples measured by plasma emission spectrometry. The real limits
of detection are much higher. A more useful approach may be to define
the limit of detection as the concentration where the relative standard
deviation of the result reaches, say, 50% without regard to the blank or
background noise at all (Thompson and Howarth, 1978).
Very low detection limits are typically required for the study of elements
like Au, most of its pathfinder elements, and PGE, Ag, Mo and Pb.
Too high detection limits and imprecision show up as an absence of
any clearly delineated pattern on geochemical maps. Detection limits
are typically lowered by implementing preconcentration and separation
procedures before measurement.
The selectivity of an analytical method is related to how free the cal-
ibration function, y = f(c), is from interfering influences of concomitant
190 Analytical methods
Economic considerations
Costs encompass the monetary value of labour, instruments, materials
and housing for all functions of the laboratory Unit prices should be
estimated for all operations from sample logistics and pretreatment to
reporting of the results, and include the R&D required to bring a procedure
into service. Cost-benefit analyses are seldom done explicitly, but are
usually involved implicitly in evaluations such as "cost-effective" and
"adequate". Labour is by far the most important cost-determining factor in
laboratories, and the following generalizations can be made about costs per
analysis.
When classical methods, cheap instruments and much labour are used,
the cost per determination is largely independent of the number of deter-
minations carried out. But with automated instruments, determinations
Performance of analytical methods 191
TABLE 9-1
Estimated costs of analysis (U.S.$) at different daily throughputs. Aqua regia soluble contents
of some 30 elements measured by simultaneous plasma emission spectrometer (ICP-AES) at
the Geological Survey of Finland
are produced at an almost constant price per time unit, so that up to the
maximum throughput of the instrument the unit price of determination
or analysis decreases (Table 9-1). The cost criterion is relevant for almost
all technical features of a method. High throughput of services is a nor-
mal requirement of an applied geochemical laboratory and purchase of
automated and simultaneous instruments with high information capacity
is often economically justified. Sometimes, however, non-economic criteria,
like extreme requirements for detection limit, will necessitate the use of
costly procedures.
Maximum throughput or production capacity is a desirable characteristic
of an exploration analytical procedure. In general, and unlike assaying
laboratories, exploration geochemical laboratories should be organized for
high productivity. High throughput can be achieved by attention to the
following:
— Rationalizing the pretreatment of samples (use of manifold sieve
shakers and grinding equipment, etc.).
— Rapid methods of sample decomposition (typically partial leaches in
test tubes).
— Avoidance of chemical preconcentrations (low dilution factors, instru-
ments capable of low detection limits).
— Rapid determination of elements (simultaneous or "multichannel"
instruments with autosamplers instead of sequential ones).
— Computerized laboratory information management systems (LIMS)
including uniform identification of samples and rapid data retrieval.
— Close cooperation between laboratory staff, those who submit the
samples and those responsible for the interpretation, to allow efficient
scheduling of analytical requests.
Cooperation is the most effective means of reducing dead time of samples
in the field and data in the files. The achievement of maximum throughput
is a matter of proper laboratory management and R&D methods. Too often,
192 Analytical methods
PRETREATMENT OF SAMPLES
TABLE 9-II
DECOMPOSITION OF SAMPLES
General
Total decomposition
Total methods of decomposition are used at least as a preliminary step
in determinations of the main components of silicates and some minor
and trace elements occurring in more resistant minerals. Two practical,
essentially total methods are (in order of effectiveness) fusion with borates
and digestion with hydrofluoric acid (HF) mixed with strongly oxidizing
acids.
Borate solutions are advantageous for atomic absorption and plasma
emission spectrometries, for example, lithium metaborate (LiB0 2 ) is a
powerful alkaline flux that forms solid solutions with most minerals, and
the solidified melt is easily dissolved in dilute nitric acid. The procedure
allows the use of rapid automated "fluxer" devices, but the costs of
operation are considerable because of the platinum crucibles required.
A typical fusion procedure as used in the GSF laboratory involves
weighing 100 mg of sample powder and 500 mg of LiB0 2 , homogenizing the
mixture, fusing for 5 minutes in the fluxer flame and then pouring the melt
into a beaker with 5% H N 0 3 solution. The melt is dissolved by mixing for
15 minutes and the solution is diluted with water to 250 ml (total dilution
196 Analytical methods
Partial extractions
TABLE 9-III
Association of trace elements with different phases of overburden samples and typical extraction
agents used
^ ^ ^ ^ ^ ^ ^ ^ ^ ^ W \ |
H^^^^^^M^fi^^^^^ 9 ·H·· · · . ·
RΑ Ν Ι Τ Ε
[iVc ^:-^^Ζνά\ ''T<'& Y?-£v\? ς/
ρ Ι Ι β ^ Ι Ι ^ ·· ' ■
•• ·· · .· * · *
f iVJMICA SCHlSJ^'^^y^^^Y · · ·
^$S^^$00^M · j ^ / # . · · · ·
• · ·
^^^^^00M^0ips. · · RAPAKIVI# A
•
^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ > A *
e
Ky^/^^^^^^^^GRANODIORiTE^^^e · . Ä · LAPI#ÄRV*
, · · ·
• · ·
\///////////// · • • ·
WMMMMMMM: ■
·
•
i^^^^^e^' ·
•
•
• . · · · . *
10 km
. ·
^GRANITEx
#
b~JMICA SCHIST -V^-'c''/V^7>-^Ä/ · * #
RAPAKIVI
; GRANODIORITE
LAPINJÄRVt
1 0 km
Fig. 9-4. Aqua-regia soluble concentration of Ba in the same samples and area as in Fig 9-3.
High Ba is associated with the mica schist area because Fe-rich biotite — the major source
of Ba — is very abundant in the schist and easily soluble in aqua regia. Here Ba contents in
the rapakivi area are relatively low due to very poor solubility of K-feldspar in aqua regia. Of
course there are small amounts of biotite in rapakivi and microcline in mica schist.
with the analysis of trace elements are largely separated into the insoluble
residue. Traditionally, partial extraction data have been sought for elements
forming sulphides; however, main component data for silicates may give
useful background information for interpretation (Noras and Kontas,
1989). Essentially total (HF/aqua regia decomposed) and partial (aqua
regia extracted) concentrations of barium are compared in Figs. 9-3 and
9-4. The aqua regia extraction has proved to be a useful (and "universal")
method for many purposes and sample types. The efficiencies of different
acid digestion procedures for the extraction of elements from silicates are
discussed in Foster (1974).
As applied in the GSF laboratory, the aqua regia procedure involves
weighing 500 mg of sample powder into a test tube, adding 2 ml of cone.
HC1 and 1 ml of cone. HN0 3 , digesting at 90°C for 2 h with frequent
agitation, and diluting to 20 ml with water. The element determinations
are done by flame atomic absorption (Ag, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni,
Pb and Zn) or plasma emission (the above elements plus Al, As, Ba, Ca, K,
La, Li, Mg, Na, I? Sc, Sr, S, Th, Ti, V and Y). A daily output of 150 sample
solutions per operator is achievable.
200 Analytical methods
DETERMINATION OF ELEMENTS
General
TABLE 9-IV
Evaluation of capital outlays (thousands of U.S.$; "other" includes sample preparation equip-
ment, etc.) for acquiring different analytical techniques, annual throughputs (thousands of
element determinations) and unit prices (U.S.$) of commercial services
touched upon here are used for measurements of fluoride, chloride and
pH (ion-selective electrode measurement), and sulphur, carbon and water
(combustion-infrared absorption measurement). Microbeam and surface
analytical techniques such as electron microprobe, ion probe (SIMS), laser
probe and particle induced X-ray emission (PIXE) are used in special cir-
cumstances only and likewise are not included in this overview. Except for
ICP-MS, the use of mass spectrometric techniques is still far too expensive
to have any practical role in the analysis of exploration samples.
Principles
Since most colorimetry indicators are non-specific for a particular el-
ement, much effort must be directed to minimizing interferences from
matrix elements. Sample solution cells for instruments are of interchange-
able type or fixed flow cells, the latter being recommended for large batches
of samples or when several procedures are used. Relatively broad molecular
absorption bands are measured, which means that high optical resolution
is not required of the instruments. Spectrophotometric procedures involve
seven steps: decomposition of the sample, transfer of an aliquot of the
sample solution, addition of a buffering agent, addition of a masking agent,
addition of a colorimetric indicator, extraction of the coloured compound
and measurement of the intensity of colour (colorimetry) or the absorbance
of its complementary colour (spectrophotometry). The element concentra-
tions are obtained by comparing the colour intensity against a series of
standards (colorimetry) or by applying Beer's law (spectrophotometry).
Applications
Relative to the capabilities of other instrumental methods, spectrophoto-
metric procedures continue to be useful for certain elements as summarized
in Table 9-V
Fluorometry measures the intensity of fluorescence emitted by some an-
alyte compounds after their exposure to UV radiation. The only important
application of fluorometry in exploration geochemistry is the determination
of uranium. Neutron activation with delayed neutron counting for U is less
sensitive to matrix effects and should be more cost-effective, if available.
Determination of elements 203
TABLE 9-V
Principle
All free, ground state atoms are capable of absorbing energies of charac-
teristic optical wavelengths. The AAS instrument basically comprises (a) a
204 Analytical methods
modulated light source, usually a hollow cathode lamp, which emits light of
characteristic wavelengths; (b) an atomizer which releases free atoms from
sample solutions; (c) a monochromator which isolates the resonant wave-
lengths and (d) a detector (photomultiplier) which measures the absorption,
proportional to the concentration of an element (Beer's law). A notable
technical limitation of the method is the need to use an individual light
source with characteristic spectral lines for each element to be determined.
The availability of a continuum light source, still not completely solved,
would make the AAS a multi-element method.
Three types of atomizers are in general use: the gas flame, the hydride
generation cell and the graphite furnace.
Applications
Flame atomic absorption spectrometry (FAAS) is a widely used funda-
mental method. Based on solution injection into a laminar flow nebulizer
and atomizing in a gaseous flame, the flame techniques are straightforward
to apply, though not the ideal means of atomizing. The initial cost of
the instrumentation is relatively low, and simply prepared solutions can
be used for important ranges of elements (most of the sulphide-forming
elements and all of the main silicate-forming elements). Two applications
are of special interest for overburden samples.
(1) Hot, strong mineral acid leaching of samples (e.g., aqua regia) enables
daily batches of up to 100 sample solutions with determinations of Ag,
Cd, Co, Cu, Fe, Mn, Ni, Pb and Zn in an air-acetylene flame, and of Cr
and Mo in a nitrogen oxide-acetylene flame. All are easily detected at their
normal levels of background in till samples, excepting Ag (detection limit
1.5 ppm), Cd (1 ppm), Pb (15 ppm) and Mo (1 ppm). Unfortunately, these
latter elements are also prone to interferences in emission spectroscopy
(2) Hydrofluoric and boric acid solutions, as described in the section
"Total decomposition", provide a useful matrix for determinations of Si, Al,
Ti, Fe, Mg, Ca, Sr and Ba in nitrogen oxide-acetylene flame (Sr in emission
measurement mode) and Mn, Na, K, Li and Rb in air-acetylene flame.
As compared with ICP-AES determination of these elements from similar
solutions, the FAAS shows better precision for Si and the alkali metals.
Expanding the use of the flame methods to other elements generally calls
for chemical separations and enrichment, most conveniently by solvent
extraction. Methyl isobutyl ketone (MIBK) has proved by far the most
useful organic extractant for applied geochemical analysis. O'Leary and
Viets (1986), for example, have presented a group separation approach
involving a hydrochloric acid-hydrogen peroxide leach and extraction into
Aliquat 336-MIBK. Then, up to nine elements are determined in the
organic phase by FAAS, viz. Ag, Cd (detection limit 0.05 ppm); Mo, Cu,
Pb, Zn (0.5 ppm); Sb, Bi (1 ppm) and As (5 ppm). Gold is determined (0.2
ppm) in samples large enough to be representative (10 g or more) after
Determination of elements 205
digestion with aqua regia-KBrOß and extraction into MIBK (Noras, 1992).
The determination of Au in MIBK can be done by graphite furnace AAS
to achieve a detection limit of below 0.001 ppm, as presented by Meier
(1980). Other well-established procedures making use of MIBK have been
presented for In, Te, Tl (detection limit 0.2 ppm) and Au (0.1 ppm) in aqua
regia solution (Hubert and Chao, 1985), and for Sn (2 ppm) in MIBK-TOPO
phase after condensation with ammonium iodide (Welsh and Chao, 1976).
Hydride generation atomic absorption spectrometry (HGAAS) can be
applied for volatile, covalent hydride-forming elements (viz. Ge, As, Sb,
Bi, Se, Te, Sn and Pb) that are only sparingly soluble in water. Use of a
hydride generation cell involves the selective separation of elements and an
efficient means of atomizing compared with normal nebulizing. Attractive
lower limits of detection are offered in a typical range of 0.05-0.5 ppm. Un-
fortunately, the generation reactions (usually with sodium borohydride) are
prone to interference from many transition group elements which suppress
the yield. Hydride generation is used for preconcentrating of Se prior to
determination by graphite furnace AAS (Willie et al., 1986). The HGAAS
method (and HGICP-AES) allows automation and implementation of flow
injection techniques which are sure to become important in the future.
Guo et al. (1989) have used hydride generation prior to determinations by
atomic fluorescence spectrometry (HGAFS). Mercury has been determined
after reduction to non-volatile form by several well-established flameless
methods closely resembling HGAAS. A review of these procedures is pre-
sented in Ure (1975). Portable Hg determinators are available for field use
(Scintrex Ltd, Concord, Ont., Canada).
Graphite furnace, or electrothermal atomic absorption spectrometry
(GFAAS), has gained attention for attaining lower detection limits, often
by one or two orders of magnitude, than those attainable by FAAS and
other commonly used techniques in exploration geochemistry. The essence
of GFAAS is total vaporization of a small quantity of sample solution
into an electrothermal furnace atomizer. Transient absorption signals are
measured rather than constant signals as in FAAS. Direct injection of multi-
element solutions is typical for FAAS, whereas GFAAS usually requires
prior separations and preconcentratings for single elements. Interferences
arise mainly from non-isothermal atomization and are due to matrix
elements. Overcoming of interferences typically requires spike calibration,
matrix modification, special treatment of graphite, platform technique
(i.e., isothermal atomization) and/or the use of integrated (peak area)
absorbances. Thus, working with GFAAS calls for more professional skill,
and the operating and capital costs are higher.
In view of the other methods available, the elements most usefully
determined by GFAAS for exploration purposes would appear to be Au, Pd,
Se and Te. Kontas (1981) has presented a powerful procedure based on
relatively simple aqua regia digestion and coprecipitation of the analytes
206 Analytical methods
with SnCl2-Hg for Au (detection limit 0.0001 ppm). The method is rapid —
daily throughput can be up to 100 determinations — and it has successfully
been applied to more than 200,000 till samples in the Nordic countries. The
procedure has recently been modified to allow measurements of trace levels
of Ag, Pd, Pt, Rh, Se and Te (Niskavaara and Kontas, 1990). Selenium
(detection limit 0.05 ppm) can be determined after nitric, perchloric and
hydrofluoric acid decomposition and extraction into toluene (Sanzalone
and Chao, 1981); and Te (detection limit 0.004 ppm) can be determined
by hydrobromic acid-bromium digestion prior to extraction with MIBK
(Chao et al., 1978). Other useful single element procedures have recently
been reported for Ga (Anderson et al., 1985) and In (Zhou et al., 1984).
Many separation and preconcentration procedures developed for FAAS are
applicable for GFAAS, too. The separation and preconcentration methods
are reviewed in the textbooks of Stary (1964) and Minczewski et al. (1982);
practical procedures for geological samples are given in Stoch and Dixon
(1983).
Slavin (1984) has published a comprehensive source book on GFAAS
methods. Complete bibliographies and state of the art developments,
including all AAS techniques, are presented in the Atomic Spectroscopy
handbook (published by Perkin-Elmer Corp., Norwalk, CT, U.S.A.).
Emission spectrometry
Optical emission methods with excitation of atoms in a direct current arc,
have been applied for a wide range of geochemical materials over the past
four decades. As a replacement for the traditional photographic recording
of spectra (optical emission spectrography, OES), convenient direct reading
spectrometers with several photomultiplier "channels" were introduced in
the late 1960's. Then, in the late 1970's the electrical arc/spark sources of
emission gave way to plasma sources (either inductively coupled or direct
current plasmas). In larger geochemical laboratories today the commonest
workhorse among instruments is the inductively coupled plasma atomic
emission spectrometer (ICP-AES) which is much preferred to the direct
current plasma spectrometer (DCP-AES).
Emission spectroscopy, from spectrography to plasma spectrometry, offers
a rapid, virtually simultaneous multi-element technique — highly valuable
for a geo-analytical instrument. Extra cost effectiveness is provided by the
minimal requirement for sample preparation, though this does not always
apply to plasma AES.
Principles
Atomic absorption and atomic emission involve changes in the energy
levels of an atom's outer electrons. In the emission spectrometer, ground
state electrons of an atom are excited in the source to higher energy
Determination of elements 207
TABLE 9-VI
Common sources for atomization and excitation in atomic spectroscopy, abbreviations, and
epithets of instrumental arrangements used
Applications
The DC arc spectrography (DC arc OES) system comprises a gitter
spectrograph, photograph processing facilities and a microdensitometer for
measuring line intensities. For rapid, semiquantitative analysis, lines can
be visually compared with those of standard films or plates. Owing to poor
total cost effectiveness, poorer limits of detection, small size of sample
analyzed and non-manageable spectral and matrix interferences, the DC
arc OES does not compete with recently available techniques. With direct
excitation of geosamples, reasonable limits of detection (2-5 ppm) are
achieved for Be, Sc, V, Cr, Co, Ni, Cu, Ga, Rb, Y, Ag, Sn, Yb and Pb. Without
special procedures the method fails in determining important elements like
F, Zn, As, Mo, Cd, Sb, La, W, Bi and U at their background levels. The DC
arc OES is especially used for determining certain elements associated with
resistant minerals, e.g., Be, B, Nb and Sn. Spectrography is still frequently
used in the the former U.S.S.R. Much of the geochemical mapping carried
208 Analytical methods
the main components, especially Al. Most important, any nebulizer design
still suffers from blockage and salting-up problems which are difficult to
overcome.
Simultaneous ICP-AES instruments, which readily allow multi-element
analyses and high sample throughput, are most appropriate for the explo-
ration laboratory.
A typical polychromator assembly, as employed in the GSF laboratory,
comprises channels for 33 elements: Ag, Al, As, Ba, B, Ca, Cd, Co, Cr,
Cu, Fe, K, La, Li, Mg, Mn, Mo, Na, Ni, P, Pb, Sb, Sc, Si, Sr, Th, U, V, W,
Y, Yb, Zn and Zr, and one scanning channel. Sulphur can be determined,
but a vacuum path spectrometer is then required instead of the normal,
air path instrument. Although not a full response to client demand, the
33 channels were installed because they exploit most technical capabilities
of the spectrometer in direct analysis of samples. The two methods of
sample preparation comprise HF-aqua regia-B(OH)3 decomposition (which
is essentially total) and aqua regia extraction. By the latter procedure, most
of the interfering matrix elements in ICP-AES (e.g., Al, Ca and Fe) are
avoided, since they are largely left in the insoluble residue. Recently, there
has been much interest in extractability data such as ratios of aqua regia
soluble content to total content of an element, which are easily obtainable
by simultaneous ICP-AES but with difficulty by any other instrumental
technique.
Sequential ICP-AES is slower, mechanically more complex and requires
more computing time than the simultaneous instrument; but it enables
flexible measurement of an unlimited number of spectral lines and thus
any element. Sequential ICP-AES may be the choice of smaller and less
production-oriented laboratories (or for owners of a simultaneous unit) that
deal with widely varying geochemical problems.
Direct analysis of solutions by ICP-AES is a well established method;
current developments include new methods to separate and preconcenträte
low abundance elements. Above all, procedures designed to separate groups
of elements are invaluable for ICP-AES. Useful procedures have been
presented for hydride-forming elements (Thompson et al., 1978; Halicz
and Rüssel, 1986), for REEs (Walsh et al., 1981) and for PGEs plus Ag,
Ta, Th and U (Barnes and Diallo, 1985). Some of the separation and
preconcentration procedures developed for AAS can be applied as such or
modified for ICP-AES, too.
A comprehensive ICP Handbook with emphasis on geochemical samples
has been published by Thompson and Walsh (1983). Complete annual
bibliographies and state of the art developments are presented in the ICP
Information Newsletter (edited by R.M. Barnes).
210 Analytical methods
Plasma-mass spectrometry
The first inductively coupled plasma-mass spectrometer (ICP-MS) was
brought to a reliable operating state by Date and Gray in 1983. The
technique is considered to be an invaluable alternative to such conventional
techniques as AAS and AES, which are prone to the common interferences
in all atomic optical spectra. As a multi-element, wide dynamic range
method, ICP-MS resembles ICP-AES, but in providing very low detection
limits it approaches some capabilities of GFAAS, and of INAA in particular.
The sample changeover of about one sample/minute is as rapid as in
ICP-AES. The mass analyzer enables for the first time "affordable" access
to isotope ratios. Many larger geochemical laboratories that today rely
on multi-channel ICP-AES, extensive use of GFAAS and contracted INAA
services will be equipped with ICP-MS during the 1990's even if it still is
rather expensive. Changing over from AAS through ICP-AES to ICP-MS is
logical and relatively easy because the sample pretreatment and preparation
requirements are similar for all three techniques. Some applications of ICP-
MS, however, call for clean room arrangements.
Principles
The ICP is not only an efficient source of photons as in ICP-AES,
but also a highly useful ionization source. In the ICP-MS, subsequent
to nebulizing of sample solutions, ions are extracted from the central
channel of the plasma through a sampling aperture into a quadrupole
mass analyzer. Ions are separated by their mass-to-charge ratios prior to
detection by an electron multiplier and accumulation in a multi-channel
analyzer. In contrast to atomic optical spectra, mass spectra are relatively
simple because most ions occur only as singly charged and mono-atomic.
However, interference due to polyatomic ions generated from solution
chemicals or plasma gases, or by formation of refractory oxides is possible.
Doubly charged ions are observed only for elements with low second
ionization potentials. Most interferences are manageable by appropriate
data processing.
Applications
Comparison of approximate detection limits obtainable with other major
analytical techniques shows that ICP-MS may be a very competitive
alternative, especially for geochemical background levels of Sb, Bi, B, Cd,
Ga, Ge, Hf, I, In, Mo, Pb, Nb, Rb, Ag, Ta, Te, Th, Tl, Sn, W and U.
For direct determination of the complete REE group and Y, the ICP-MS
method is straightforward down to 10 times chondrite abundances. With
well-established separation and preconcentration by ion exchange, levels
down to 0.01 times chondrite can be achieved (Jarvis, 1988). Gold and PGE
can be determined by using lead or nickel sulphide as collector. Using a Pb
Determination of elements 211
button, Denoyer et al. (1989) have obtained detection limits as follows: Au,
Ru and Rh (1 ppb), Pt and Pd (0.1-1 ppb) and Ir (0.2 ppb).
Applications to isotope ratio studies have been presented for B, Os and
Pb, and also for Sm, Sr, Tl, U and Zn. Determination of isotope ratios
for Pb has attracted most interest (Longerich et al., 1987). In addition,
isotope dilution procedures offer the best way of calibrating ICP-MS (Hall
et al., 1987). Nevertheless, the precision of isotope ratio measurements
does not usually rival thermal ionization mass spectrometry (TIMS) used
in geochronological studies.
As with ICP-AES, the efficiency of sample introduction into the ICP is the
critical factor in the performance of ICP-MS. Thus, mainly to achieve lower
detection limits, alternative methods of sample introduction — electrother-
mal vaporization, laser ablation, arc nebulization, direct sample insertion
and nebulization of slurries — are being developed (Riddle et al., (1988).
The methodology of ICP-MS for geochemical application has been re-
viewed by Riddle et al. (1988), but being at a stage of development new
methods are continually being published.
Principles
The X-ray fluorescence phenomenon results when the analyte is irradi-
ated with X-rays (primary radiation), which are resonantly absorbed by an
atom, causing transitions in its inner electron shells. An amount of energy
equal to the difference between the original and final states of the electrons
is released as fluorescent X-ray energies or wavelengths (secondary radi-
ation) which are characteristic of the particular element. The intensities
of the secondary lines are proportional to the element concentration. The
primary radiation is produced by an X-ray tube, a radioisotopic source or
electrons (electron microprobe). The spectrometer separates the secondary
radiation on the basis of its wavelength (analyzing crystal) or energy (e.g.,
Li-drifted Si detector). The intensity of the secondary radiation is measured
by a detector or as the amount of energy stored in a multichannel analyzer.
212 Analytical methods
Flat analyzing crystals are used in sequential XRF (two changeable detec-
tors), and focusing crystals in simultaneous XRF (up to 30 fixed detectors).
Wavelength dispersive spectrometers (WD-XRF) are mechanically more
delicate, expensive and less compact than energy dispersive spectrometers
(ED-XRF), but they give better resolution of lines and lower detection than
ED-XRF.
The penetration of X-rays into the analyte is typically a fraction of a
millimetre, which requires high representativeness of the prepared sur-
face (compared with solution analyte techniques and neutron activation).
Quantitative analyses require the comparison of fluorescent intensities of
the sample with those of similar standard materials. By using multiple re-
gression for matrix corrections, the number of these comparative materials
can be considerably diminished. As the physical phenomena in the XRF
analysis are easily predicted, the concentrations can be calculated merely
by theory without use of standards (i.e., fundamental parameters method).
This is a significant advantage of the XRF technique.
Applications
Despite its limitations, simultaneous WD-XRF is an efficient multi-
element instrument for systematic long-term surveys. For most elements
the lower limit of detection ranges from 5 to 20 ppm — always much higher
for light elements, and somewhat higher for simultaneous than sequen-
tial instruments because of the limited possibility for matrix correction in
"fixed channel" mode. Today, the more flexible sequential spectrometers are
approaching the speed of simultaneous instruments; "hybrid" units (com-
bined simultaneous/sequential) have been developed, too. Pressed pellets
with wax binding or sample powders (5-50 g) are used for exploration ap-
plications; better accuracy and precision but poorer detection are achieved
by using fused beads (e.g. solid solutions with borates). The relatively
large sample weight compensates for the shallow penetration of X-rays
into the sample. In comparison with other instrumental techniques, the
non-destructive feature of WD-XRF is advantageous for determining Cr,
La, Nb, Sn, Ta, V, W and Zr which tend to be found in resistant minerals.
Low detection limits may be an asset for Cl, (Nb, Ta) and U. Simultaneous
determination of other elements (e.g., As, Br, Cu, Co, Cs, Mo, Ni, Pb,
Rb, S, Sb, Sr, Th, Y and Zn) is convenient but possible only at non-trace
level. Some serious interferences that reduce the quality of trace element
determinations in AES methods are not a problem in the XRF method.
As most of the above elements represent higher atomic numbers and can
be determined with the ED-XRF (Ag tube), this instrument may be a
cost-effective alternative to simultaneous or sequential WD-XRF (Potts et
a l , 1985).
XRF allows extensive automation from sample preparations to data
readout and can easily be operated unattended, which decreases running
Determination of elements 213
Principles
Neutrons interact with the nucleus of an element to produce a beta
decayable radioactive isotope. Following the beta decay the residual nucleus
is in an excited state, which then collapses by emitting characteristic
gamma ray energies. The measurement of these energies is based on
gamma spectrometry using Ge(Li) or low energy photon detectors and
multichannel analyzers for storing the information. Different irradiation
times, decay and counting intervals are used for particular groups of
elements. The two analytically important energy ranges of the fission
neutron energy spectrum are the thermal (below 0.5 eV) and the epithermal
(0.5 eV-0.01 MeV). As both neutrons and gamma rays (100-3,000 keV) are
highly penetrating, representativeness of the analyte is achieved with less
effort than in XRF methods.
Applications
With the sequential, relatively expensive and slow procedures of thermal
INAA, it is possible to determine up to 30-35 elements in exploration
samples. Laboratories typically offer analyses in element packages, the
composition of which is determined by measurement practices. Because of
the expense, a need for only one or two of the elements included in the
package rarely justifies the use of an INAA method.
214 Analytical methods
FUTURE NEEDS
RECOMMENDATIONS
Chapter 10
INTRODUCTION
it is assumed that the user has a good statistical education and does not
fail in selecting the right method. A few supervising and guiding statistical
expert system programs already exist. But still the user has to be an expert
himself.
Modern user-friendly programs have removed the barrier between the
geologist and the computer. Moderate prices of powerful PCs have made
the computer an everyday tool for the geologist. Very large data sets still
require processing on a mainframe computer, especially in production-
type work like map drawing. The question of which geochemical data
analysis can be done on PCs and which on mainframe computers must
be answered specifically for every organization and type of investigation.
The answer should be based at least on (1) the general computing policy
of the organization, (2) the available resources (qualified staff, computers,
programs, data bases, auxiliary files, etc.), (3) the size and life-time of
the data set to be created and treated, and (4) the importance the data
set may have for later use. These aspects are only briefly discussed here;
some recent comments about geochemical data processing can be found in
Garrett and Leymarie (1989).
Basic statistical concepts are not defined here but can be looked up in
the referenced books. No attempt is made to present the statistical methods
completely.
(Concentration
Horizontal line
Fig. 10-1. Simulated variation of sampled element concentrations around the "natural" level
(black curve) caused by randomness of sampling (dark grey) and analysis (light grey).
Sampling grid
In the planning of the sampling strategy the objectives and aims of the
investigation are considered, and the resources available for the sampling.
Any preliminary information giving a clue to the heterogeneity of the area
should be utilized in designing the density and interval of the sampling
points. If the grid, or sampling scheme, is too sparse then few points
will hit anomalies of the desired size. On the other hand, if the grid
is overly dense money will be wasted on the collection of superfluous
information. A sampling grid can be optimal only in relation to the aims of
the investigation and the available auxiliary information. Universal rules
for grid design therefore cannot be stated.
Unexpected technical restraints may be so limiting that a planned
optimal grid cannot be used. For example, if till sampling is performed and
significant areas are without till then the regional optimization is weak.
A grid for stream sediments must be designed with respect to the pattern
of streams, and the data are not then areally equally representative. In
the case of stream sediment samples collected in the lower courses of
Statistical aspects of quality control 221
triangles and the grid points are located at corners of the triangles, than
with a hexagonal or quadratic design (Yfantis et al., 1987).
Variation of sampling density in regional investigations should be avoided
whatever interpretation method is applied. Otherwise the interpretation
and final conclusions will not necessarily hold for the entire area.
The effect of local heterogeneity, or sampling error, can be reduced by
clustered sampling in which several samples are taken near or at the
same site and composited to a single sample. Composite samples reflect the
local average level of element contents better than single samples and are
consequently locally more representative. This procedure is recommended
particularly for regional investigations, where large scale anomaly patterns
shown on a sparse grid are of interest. Compared with simple sampling,
compositing reduces the need for analyses without drastic increase in
sampling costs or significant loss in information. Compositing has been
studied theoretically and with simulation models by Garrett and Sinding-
Larsen (1983).
Measures of quality
As mentioned earlier, many factors at different stages of sample treat-
ment from sampling to analytical procedures and data processing, may
distort the quality of the final data. Not all can be measured or controlled,
because some are unknown or not observable. Average effects can be es-
timated by statistical methods, but then additional information must be
gathered at each stage. Single sample analyses are not sufficient for quality
control and estimation of variation components. The quality of measure-
ments is characterized by statistical parameters indicating reproducibility
or stability and these parameters are usually computed from replicates
obtained from the various stages of treatment. Some characteristic pa-
rameters are specific for a method or an instrument and do not need to
be computed separately for each batch. The detection limit of an atomic
absorption spectrophotometer, for instance, is the same for a particular
element irrespective of what samples are analyzed. But the detection limit
of measurements done by neutron activation analysis varies from sample
to sample and is usually separately estimated for each sample.
Statistical aspects of quality control 225
SAMPLE
PHASE 1
PHASE 2
ANALYSIS Ö
Fig. 10-3. Unbalanced twofold nested design of replicates with sufficient information and
niinimal costs for monitoring variation at sampling and analysis.
The replicates also should be analyzed in random order within the batch.
Otherwise trends and systematic variation in analyses may cause too
good estimates of reproducibility! If, for example, replicates of a sample
are analyzed one after the other and the instrument tends to produce
exceptionally high values that day, then the replicates capture only the
random not the total variation.
To avoid spurious dependence between measurements caused by system-
atic variation in analysis, it is recommended that even the unreplicated
samples be analyzed in random order. Randomization spreads the sys-
Statistical aspects of quality control 227
tematic error throughout the investigation area, and thereby reduces the
probability of getting false regional anomalies raised by that error type.
The randomization is tedious because the sampling units must be reordered
physically. The randomized analytical order of samples within the batch
can of course be generated by computer, but the manual work is difficult to
eliminate.
It is almost impossible to randomize and analyze in one batch samples
collected in large projects spanning several years. Usually the samples are
grouped into smaller batches, which can then be randomized internally,
but systematic errors between batches will remain. Such between-batch
discordance is sometimes appalling on maps that cover large data sets.
Such a map would scarcely gain the confidence of the critical user. One way
of avoiding between-batch discordance is to make the map presentation
sufficiently coarse to hide the systematic variation along batch borders.
Unfortunately this method also deletes low-contrast features within batches
that might just be correct.
Systematic variation is nowadays reduced, at least to some extent, by
frequent calibration and monitoring in the laboratory. If the laboratory
from time to time can provide unbiased data then the randomization
process is less important and can be ignored. Despite good laboratory
practice and modern techniques, however, some kind of bias may slip in due
to minor changes in the analytical procedure (new electronic components,
new calibration programs, adjustments of calibration curves, calibration
samples replaced by new ones, etc.). The distortion of new data relative to
old can be very difficult to estimate. So, since the analytical bias hardly
can be completely avoided, it is important to inform the geochemical
investigator how serious the bias is and what means are available to
reduce it.
The number of replicates at the various stages can be optimized within
the economic restraints, but in practice the number of replicate sites in
the field will be roughly proportional to the size of the investigation area
and the number of sampling sites. A relatively dense grid easily offers
representative sites for replicates. But if the area is large and the grid
sparse, the proportion of replicates should be high. Clearly, too, the number
of replicate sites will depend on the geochemical complexity of the area
(much variation requires dense sampling and a dense grid of replicates) and
on the goals of the investigation (is the interest details or large zones?). The
more details one desires, the more samples and replicates must be taken to
catch them and evaluate their significance. Universal rules of thumb are
difficult to recommend.
The regional geochemical till sampling programme at the Geological
Survey of Finland is being carried out with 1 sample/4 km 2 . The whole
country (338,000 km 2 ) was covered within a few years. The samples
were treated in batches of 4,800 samples each (19,200 km 2 ). Replicates
228 Recognition of anomaly patterns in regional geochemical investigations
were taken at every 30th sampling site, yielding about 160 replicates for
each batch. The cheapest twofold unbalanced design (Fig. 10-3) has given
satisfactory results for monitoring of quality. This scheme reduces the "net
analytical capacity" by only 7% compared with no replicates at all (and no
information about quality).
Replicates require considerable practical organization (e.g., marking
samples) and systematic treatment, but the result will be invaluable
information about the data set.
The data gained through replicates can be viewed in scatter diagrams
and the error components can be tested by significance tests by analysis
of variance. From now on, only the simplest twofold unbalanced replicate
design is considered (Fig. 10-3).
Replicate samples» Cu
1000
Fig. 10-4. Scatter diagram of replicate samples (3.4% of samples duplicate). Concentrations in
ppm.
Rep 1 i c a U RNRLYSES, Cu
#
·*
1
··
i*
:
ß
iff- ·
x
■
β
""
■
j . 1
10 100 1000
Fig. 10-5. Scatter diagram of replicate analyses (each duplicate sample re-analyzed). Concentra-
tions in ppm.
Analysis of variance
The analysis of variance is a statistical method often employed for
statistical quality control and, in particular, as a test of the significance
of the error components. Traditionally, various forms of the analysis of
variance have been used in manufacturing quality control, to test the
variation in product quality over time. The analysis of variance is usually
based on replicate sampling or measurements arranged according to a
scheme suitable for the problem.
The simplest analysis of variance scheme or design is the one-way design,
where all samples (measurements) are grouped into disjoint classes and
each class contains one or more measurements. The one-way analysis of
variance consists of testing the significance of differences between the
classes relative to the variation of repeated measurements within the
classes.
In all its forms, the analysis of variance is based on the assumption
that the distributions of measurements within classes are normal or
transformed to normal and, rigorously, their variances should be equal.
The significance test measures the spread of the means of the classes in
relation to the average width of within class distributions. Closely located
means imply equal distributions, but even one clearly deviating mean
implies unequal distributions. It is very important to note that narrow
distributions may imply significantly different means, but the same means
can be insignificantly different for wider distributions. In short, separation
of small differences requires narrow distributions!
The expression for the one-way analysis of variance model (with fixed
effects between classes) is:
xy = μ + at + €ij, i = 1, . . . , /i; j = 1, nt (1)
where xy is measurement number j of class number i, μ the expectation
(population mean) of all classes, oti the deviation of the expectation of class
number i from μ, and ey the deviation of measurement j in class i from
the within class expectation /i + ftj, ni is the number of measurements
within class i. Here μι are assumed fixed (fixed effects model) and ey are
assumed to be normally distributed. The F-test is used to find out whether
the variation of the α^ is significant in relation to the variation of the
€ij. This simple one-way analysis of variance is useful in situations where
the difference between clearly defined classes (analytical methods, devices,
sample types, etc.) is investigated and where replicate measurements are
available. This model is also applicable to homogeneity tests of large bulk
samples, which are divided into subsamples, which in turn are repeatedly
232 Recognition of anomaly patterns in regional geochemical investigations
Perhaps the best known graphical tool for presenting the frequency
distribution of measured values is the histogram. The histogram shows the
frequency distribution as a sequence of bars, or frequency classes, where
the height corresponds to the frequency and the width to the class width.
In such a figure the background and anomaly ideally appear as distinct
modes or "hills" or as excessive positive skewness (stretched upper tail).
Again, the reasoning must be based on certain premisses:
(1) If the lognormal (or normal) distribution law is satisfied then modes
or skewness should be detected for distinct anomalies.
(2) If the distribution law is not satisfied then very little can be said, at
least about the meaning of skewness.
Clearly a histogram presentation is useful for viewing the data, but one
should not forget that the class width, number of classes and scale of
presentation are subjectively chosen. Different class widths and numbers
of classes would result in far different histograms of the same data. It is
also sometimes hard to judge whether one bar is significantly higher than
another and an anomaly threshold, visually estimated between the two hills
of background and anomaly, may therefore be very uncertain.
The cumulative frequency curve (probability plot) provides a more objec-
tive presentation of the distribution of measured values than the histogram,
because it shows the distribution unclassified and with the precision of a
single value. The curve can also be drawn for classified data, but the unclas-
sified more objective version should be preferred. Often the curve is drawn
The univariate approach to anomaly recognition 237
C u m u l a t i v e f r e q u e n c y for Zn (511P)
i «**\ 99.7
.:::::
; ip"" O
97 C
95 g
90 £
po
::? ao a
70 t
60 H,
40 £
30 C
: : :· ■ CD
20 tJ
.::;="" o
10^
4 3
.:!="' 2
S 0.7
0.4
0.2
_J_ 0.1
Ca <l CD <£>>-*
o
o o o og o
ppm
by Rodionov (1971) and Crow and Shimizu (1988). But arguments for the
normal law have been presented as well (cf. Gubac's, 1986, discussion of the
physical grounds). The fans of lognormality draw their graphs on log-scales
and the doubters use the arithmetic scale. A compromise is to draw a
dual scale plot showing both curves on the same frequency scale and then
select the one behaving more linearly (or piecewise linearly) for further
inspection.
Much attention has been paid to the graphical presentation of the
cumulative frequency distribution curve, especially on probability paper.
Lepeltier (1969) has asked whether the values should be cumulative from
the smallest towards the highest or the other way around. This is a
relevant question because the highest value cannot directly be presented
on the Gaussian scale (100% is at infinity). If the greatest value must be
presented then one solution is to cumulate backward from the greatest to
the lowest value and miss the lowest one on the plot. Another alternative is
slightly to adjust the cumulative frequency of each value by the expression:
F(xi) = (i- 0.375)/(n + 0.25) (4)
where xi is the ith. observed value in ascending order, F{%i) is the cumulative
frequency function at x^ and n is the number of observations (Everitt,
1978). In fact, in some sense, this formula (4) yields optimal estimates of
the frequencies for graphical estimation.
In practice the greatest value is not necessarily the most important one
if the data set is large and regional anomalies are of interest. One should
also bear in mind that the quality of extreme values usually is low because
they tend to be far away from the range where the measurements are tuned
to be good both absolutely and relatively. Again, when using cumulative
graphs and drawing conclusions about data behaviour, the detection limit
should be considered. Data below the detection limit do not necessarily
follow the distribution law of good data and thus cause distortion of the
curve. Special care is required when the detection limit is relatively high
and a large portion of the values fall below it. Then the low values falsely
may be interpreted as the background and the background as the anomaly.
Cumulative frequency curves often show gradually changing slopes when
passing the detection limit, which indicates that the change of quality is not
abrupt and illustrates the nature of the subjectively determined detection
limit (Fig. 10-8). Low values are stretched on the logarithmic scale, which
may also cause odd behaviour of the cumulative frequency curve as a whole.
The most serious problem in the interpretation of cumulative frequency
curves is the inherent effect of the Gaussian scale. If neither normality
nor lognormality is satisfied then the curves are likely to behave in an
unpredictable manner. Different subpopulations may follow different laws
and sometimes the subpopulations are so many and overlapping that no
distinct thresholds can be found. Regional geochemical data is typically
The univariate approach to anomaly recognition 239
_99.7
;:: -w
o
A·' _97 £
-95 3
£ „90 E
.80 £
-70 Jj
-60 „,
_40J?
.30 C
_soS
O
.10^
A. Ϊ*.
:::::■'
. . . : : =: : : ■
Jt
o oo o o
en ^
ppm
Fig. 10-8. Cumulative frequency distribution curve when most measurements are below the
detection limit ( « 2 0 ppm).
population or not. The outliers can be grouped and the significance of the
group can be tested but this must be done under the same assumptions.
It is important that outliers be identified, and they should be treated with
care in later stages of interpretation. If one wants to wash off the effect
of "dirty" outliers in the statistical parameters describing the distribution,
then one of several adjustments can be applied. Such adjustments make the
parameters more stable and less sensitive to errors due to extreme values.
One method is trimming where an equal number of values is simply omitted
from both tails of the distribution. A more gentle method is symmetrical
winsorizing where the extremes are replaced by upper and lower threshold
values. In this case extremes are not dropped but replaced with less extreme
values. The formula for the winsorized average is
Background Anomaly
ppm
b o o
0 · · • o
·
0 · , 0 0 Oo
°o OO,
0
0
· ·
°0
• °° P *°
One large anomaly
\ · 1Γ · 1
Many small Single points
Fig. 10-9. This bimodal frequency curve may be the result of three different regional anomaly
patterns.
Univariate maps
Detection and evaluation of anomalies from maps is a visual process,
which relies on experience. The map should display the variation of
concentration levels forming large and small scale patterns of interest to
the geochemist. The patterns can be at low or high concentration levels
and their contrast with the surrounding is not necessarily high. Here the
242 Recognition of anomaly patterns in regional geochemical investigations
Geokemiallinen kartta
MOREENI
Zn
Esikäsittely: seulonta
Analyyailajite (pro): —62
Iiuotus: kuuma HNOa+HCl
Analyysilaite: ICP
Laboratorio; GTK
Näytteenottovuosi: 19B3
Analyyaivuosi: 1985
Pistelukumäära: 2061
Symbolikoko pitoisuusarvojen
funktiona (^—) ja pitoisuuksien
kumulatiivinen jakauma ( «ass»)
Fig. 10-10. A dot map of Zn in till with dot size expressed as a continuous function of concentration; measurements of duplicate samples are
shown on the scatter diagram.
The univariate approach to anomaly recognition 245
interpolation. The points are weighted according to their distance from the
window centre; typically high weights are given to points near the window
centre and low weights to points at the periphery. The weighting function
can be tailored according to the particular effects being sought.
Besides the weighted average, a weighted median can be computed
within the window (Björklund and Lummaa, 1983). The weighted median
is especially suitable for noisy geochemical data because it is insensitive to
outliers and the values obtain a just representation in the final result as
the weighting affects the frequencies not the values. Briefly, the method
delivers votes to every value within the window, where the vote is the
computed distance-dependent weight. The value that has the same number
of votes above and below is the weighted median. The result is influenced
by many control parameters, such as window size, point density, shape
of weighting function etc. These control parameters must be adjusted
purposely for each data set. Most maps in the Geochemical Atlas of Finland
have been computed using the moving weighted median.
Recommendations for plotting coloured surface maps are difficult to state
concisely. But a couple of things are clear. First, the final pixel size (the grid
square) should not exceed 1 mm 2 ; otherwise the chess board effect becomes
too disturbing. Secondly, as in dot maps, the quality of the data must be
considered and the colour scale must be tied to the concentration scale in a
meaningful way. The colour scale must be easy to use and visually decisive.
The most common and possibly the most natural colour scale is the one
picking up colours of the rainbow, where low values are associated with blue
and high values with red (cold-warm —> low-high). Many colour classes
should be used on regional geochemical maps and adjacent colours need
not differ drastically from each other. Soft fuzzy effects are then achieved
and the anomalies are not sharply outlined by contours that might lead the
reader astray.
Large-scale anomalies, and low contrast anomalies in particular, are
usually easier to detect from coloured surface maps than dot maps. There
is a risk nevertheless that an anomaly pattern becomes hidden within a
single colour class. When this is likely to happen, features can be visualized
by employing hill-shading as a complementary method. Hill-shading is a
method where each pixel is presented as if illuminated by a directed light
beam and the pixel reflects the light with an intensity dependent on its
slopes towards the source and the viewer. Shades are very powerful for
detecting features that depend only on slopes (changes) and not on absolute
concentration level. Combining a coloured surface map and a hill-shading
map offers a visually clear presentation of a complicated concentration
surface. Such maps (Koljonen et al., 1989) are strikingly informative.
Geochemical data that has been transformed to a regular dense grid
can also be treated by image processing methods. The traditional image
processing methods are filtering techniques: low-pass filters remove high-
246 Recognition of anomaly patterns in regional geochemical investigations
Methods can often be mechanically applied to data that does not satisfy
the requirements of the method, and in that case the output may well be
nonsense. Any worker intending to use multivariate methods in a serious
way is certainly advised to improve his or her knowledge through study. For
the more casual user, commercial programs already exist — expert systems
— advising on the selection of methods, both uni- and multivariate, given
the type of data and the goal of the study (Brent, 1989). Such guidance
is valuable even for the professional statistician, who does not always
remember the pitfalls.
Fig. 10-11. Bivariate point patterns that could result in spurious correlation; D indicates the
detection limit.
putting the values below the limit into the first rank, classifying the
rest of the data into reasonably many classes, and using rank correlation
coefficients: Spearmans p, Kendall's r, etc. (Maritz, 1981). Ranking causes
loss of information (interdistances between values), but may be the only
way to go in extreme cases. Rank correlations can be used as input into some
multivariate methods, but ranked data cannot be subjected to arithmetic
operations, and this is an important caution when using methods that
try to reproduce the original values. Cases (1) to (3) may be displayed in
simple scatter diagrams and univariate distributions. If each variable is
plotted against all others then n{n — l)/2 scatter diagrams must be drawn
for n variables. It is not unusual to have 20 variables in a geochemical
investigation and if all pairs are inspected 190 diagrams will be required!
The alternative to a large number of scatter diagrams is a multivariate
graphical presentation of all variables and samples on a single plot,
showing grouping and single multivariate outliers in a satisfactory way.
The plot displays the Andrews' curves (Andrews, 1973), which describe
each sampling unit as a trigonometric polynomial where the coefficients
correspond to element concentrations. Each sampling unit is represented
by a wrinkled curve where each element appears as the amplitude at a
given wave length. The formula for an Andrews' curve is:
F(t) = Xijy/2 + x2 sin(i) + x3 cos(i) + x 4 sin(2£) + x 5 cos(2£) + · · ·, (6)
0 < t < 2π
Formula (6) represents the curve of one sampling unit, where xj is the
value of the jth. variable. Unique combinations of element concentrations
give unique curves. Grouped samples appear as a uniform band of curves
for each group and single outliers appear as "wild" curves with no similarity
to any band. Dominating wavelengths of a band can be used to identify
the dominating elements in the group. The element concentrations must
be standardized (subtracted by mean and divided by standard deviation)
to obtain comparable scales of amplitude. Like all graphical presentations
the Andrews' plot has some drawbacks. A large amount of data can cause a
virtual mess of curves impossible to distinguish. The effect of elements on
the curve depends on the order of the elements. A new ordering of elements
will result in new shapes of curves, though the bands will normally be
preserved. The first elements of expression (6) are more influential because
they cause longer waves than those at the end of the polynomial. Despite
these disadvantages the Andrews' plot has the advantage of being fast to
compute and easier to handle than a host of scatter diagrams. Figure 10-12
shows a typical set of Andrews' curves with clusters as bands and outliers
as wild curves. Each curve can be identified from the sample label plotted
at the edge of the plot.
The data structure of multivariate data can be examined in two ways: in
terms of (1) the interdependence between variables using factor analysis,
250 Recognition of anomaly patterns in regional geochemical investigations
Fig. 10-12. Typical Andrews' curves showing clustering and single outliers in the multivariate
data.
Factor analysis
(oblique factor models) factors are applied instead. Uncorrelated factors are
easier to interpret than the correlated ones and they possess nice statistical
features that are advantageous if the factors are input to other procedures.
Factor analysis does not assume the normal law if no hypothesis tests
are performed. It must be noticed that the correlation coefficients reflect
only linear dependence and thus the factors can in turn explain only linear
dependencies. Nonlinearly dependent variables should be transformed to
yield linear dependence, mostly possible. The initial settings must be
carefully checked because, although factor analysis can almost always be
carried out, the result can be relied upon only if the conditions are satisfied.
There are many variants of FA and here only the most commonly used
method is briefly introduced from a practical point of view. FA is based
on a correlation matrix that is invariant to scales of variates, unlike PCA,
which starts from the covariance matrix, and depends on original scaling.
The FA model includes factors that are unique to a variate, while the PCA
model contains common components only. The FA model is linear and can
be expressed as:
*i = anFi + a12F2 + alsF3 + · · · 4- almFm + diUx
x2 = a2\Fi + a22F2 + a2SFs + · · · + a2mFm + d2U2
(7)
:
Xn = amFi + a>n2F2 + anSF3 + · · · + anmFm + dnUn
where X{ is the ith original standardized variate, Fj is the jth common
factor, t/fc is the unique factor of the ith variate, ay and d{ are loadings
reflecting the dependence between the variates and factors, n is the number
of variates and m is the number of common factors. The factors are by
definition standardized variates with mean 0 and standard deviation 1.
The loadings can be interpreted as correlation coefficients between variates
and factors (not true for PCA). The loadings are subject to interpretation
and the combination of elements with high loadings on a factor can give a
clue as to what natural process is explained by that factor. The degree of
explanation for each variate is the communality expressed by loadings as:
m
^= E4 1
<8>
The communalities are always < 1 , because m < n and the variates are
standardized (Var(xj) = 1). Sometimes the communality is multiplied by
100 to obtain a percentage. The rest of the variation 1 — hi is explained by
the unique factor. The proportion of variation explained by a single factor
can be computed from the eigenvalues of the FA problem. The eigenvalue
corresponds to the variance of a factor and the sum of eigenvalues
corresponds to the total amount of variance explained by the whole factor
252 Recognition of anomaly patterns in regional geochemical investigations
relevant factors is 1, i.e., all factors having an eigenvalue < 1 are skipped;
in general one should avoid interpreting factors with smaller eigenvalues
because they tend to reflect noise.
(3) If the correlations between variates are all close to 0 only one common
factor will be found per variate; the factor model does not then provide
the interpreter with new information. Almost equal eigenvalues indicate
the same situation. Some programs include a sphericity test to detect this
situation before the attempt is made to fit a meaningless model.
(4) The goodness-of-fit of the model expressed by communalities should
always be checked for each element; low communality, <0.5 say, reveals
that the variate is not explained by the factor model and is mainly explained
by the unique factor.
(5) If only a low proportion of the variation is explained by a factor, the
factor may be reflecting only less important variation — noise perhaps —
and should be interpreted with caution; low proportion does not necessarily
mean a bad factor, because the measure is relative and the less important
factors have already been dropped at the dimensionality choice.
Multivariate classification
Grouping or clustering of data can be investigated by graphical tools
(Andrews' plots or biplots, see above) or by some statistical classification
procedure. The statistical classification methods can be divided into un-
supervised and supervised methods depending on what initial conditions
are set. Unsupervised methods cluster the data points into homogeneous
classes which are unknown beforehand and the result is a classification of
all points into those classes. The classification is then based only on the
interdistance between points and the decision algorithm telling whether a
point belongs to a class or not. Supervised classification methods classify
data points into classes that are known or described beforehand.
Unsupervised methods are usually employed when unknown structures
are searched for. A geochemical example could be the classification of till
samples taken over an area from which very little bedrock information
is available. Then the objective of the classification could be to find any
clustering in the data to identify geochemically homogeneous lithologic
blocks or provinces in the area, aiding, e.g. the geological mapping.
Supervised methods are used when one wants to see which data points
fit known cases and which ones are different. For example, supervised
classification is a powerful approach if one wants to classify unknown
geochemical data using a well-known data bank of anomalies. The result
would show whether or not the data points match any known anomalies,
where they reside and which anomaly they match. The supervising can be
done through training data so that each class is assigned a representative
set of training samples, which are analyzed in the same way as those to be
254 Recognition of anomaly patterns in regional geochemical investigations
Quantitative Classification
Methods
* Classification rules
and criteria
* Distance measures
Fig. 10-13. Schematic view over quantitative classification methods. Variants of methods are
generated by diverse distance measures and classification criteria.
classified. The computer "learns" from these training data what features
are characteristic to each class, e.g. for Sudbury type of mineralisations.
The classification methods can also be divided into categories depending
on what distance measure, classification criterion (agglomerative or devi-
sive), hierarchic or non-hierarchic structure and estimation method are
used. A schematic view of these methods is shown in Fig. 10-13.
Unsupervised classification
points be to existing clusters to be included into one of them and how is the
"nearest cluster" defined?
This list is not complete and the investigator must be very familiar
with his method to avoid blind working and uncontrolled results. Once the
method is selected, the results of the analysis can be viewed as maps where
each sampling point is represented by coloured dot or symbol to indicate
the class index. Hierarchic clustering can be viewed as a dendrogram
showing all divisions from the lowest level where each sample is a single
cluster to the highest level where all samples belong to the same cluster. In
geochemistry a classification map often is the only way of interpreting the
meaning of clusters. Nevertheless, cluster analysis methods are not often
applied in geochemistry, possibly because the geochemical data set tends
to be large and the distance matrices involved require enormous computer
memories. The number of variables can be reduced by factor analysis (R-
mode), but the size of the distance matrix is still the same. Cluster analysis
for geologists is discussed in Davis (1973). Various clustering methods are
described in Anderberg (1973), Duda and Hart (1973), and Späth (1980).
Factor analysis can be used for classification of samples if places of
samples and variables in the raw data matrix are changed. This Q-mode FA
starts with correlation between samples and results in factors that indicate
groups of samples.
Supervised classification
Linear discriminant analysis appears to be the most popular of the
supervised classification methods. One simple reason for this is that it
is included in almost all commercial statistical program packages. The
method is also computationally very effective. Linear discriminant analysis
assumes multinormal distributions within classes and equal covariance
matrices for all classes, and to work properly it requires linearly separable
point patterns in the space spanned by the variables. This means that
the patterns should be separable by hyperplanes (lines in two dimensions
and planes in three dimensions). These assumptions are very restrictive,
however, and prohibit a proper application in many practical cases. At least
the assumptions are tedious to verify and a battery of significance tests
must be employed.
More flexibility and fewer restrictions are offered by the method of
empirical discriminant analysis introduced to geochemistry by Howarth
(1973). Empirical discriminant analysis is a statistical multivariate method
for supervised classification of objects into classes where each is defined
by a representative sample — training data. The variates observed on the
model objects and the unknown objects must have a measurement scale
that allows measurement of distance between points or samples. Thus the
method is not applicable to nominal variables such as rock type. Because
256 Recognition of anomaly patterns in regional geochemical investigations
the model objects — the training data that supervise the classification —
need not be "naturally" clustered in the variable space, the method is more
powerful than most other classification methods in situations where shapes
of classes are complicated. Though not a recent method in geochemistry
(it has been used at least since 1973 at Imperial College, London), it has
only infrequently been applied, probably because of the extended and high
precision computing required. Now that computers are drastically more
powerful and cheaper it becomes highly attractive.
Supervised classification by empirical discriminant analysis encompasses
the following steps:
(1) Learning of classes from a sample of model objects from each class
(the training set) and estimation of class-conditional frequency distribution
functions
(2) Definition of the current decision rule with subjective prior probabil-
ities and a loss (cost on misclassification) function
(3) Testing of the quality of the learning by classifying a known test
set of objects not included in the training set; if the test result is
unsatisfactory the training set must be adjusted and the quality of the
variables reconsidered
(4) Classification of the unknown objects into the learned classes by a
classification rule and display of the obtained results.
The estimation of the class-conditional frequency distribution functions
is nonparametric and no assumptions concerning the distribution law of the
variables need be made. These functions can be estimated using Parzen's
window method in which the error of measurement can be tolerated and
taken into account. The nonparametric feature of the method makes it
safe and flexible in situations where little or nothing is known about the
behaviour of the variables.
The classification rule is usually based on Bayes' decision rule, which
operates on class-conditional frequencies, prior probabilities, and a value
of loss for each class measuring the cost of misclassification. This rule is
optimal in the sense that it minimizes the average overall loss. The rule
can be simplified by the introduction of equal a priori probabilities and
equal values of loss for all classes. A threshold can be employed to screen
out those samples that do not significantly belong to any of the given
classes and should therefore be considered as outliers or unknowns. The
classification results consist of the empirical probabilities of the classes and
the index of the selected class for each object (Gustavsson, 1983).
The results of the classification are shown as maps of various types
presenting the regional distribution of the class labels or probabilities of
individual samples. A case history of this method applied to a large data set
with resultant maps has been presented by Gustavsson and Kontio (1990).
Most classification methods need a distance measure between items.
Various types of multivariate distance measures have been designed, but
The multivariate approach 257
Data compression
If the number of variables in the data set is too large to be handled by a
multivariate interpretation procedure, some kind of data compression be-
comes necessary. Typically this situation occurs when there are restrictions
in the employed computer program; numerical problems may result when
there are a lot of variables, say more than 100. Data compression is also
sometimes important when efficient classification rules have been designed
and redundant information is undesired.
One way of compressing data is to fit a factor analysis model to them
and use the most significant factors as new variables representing the
whole data set. Not all variation of the original variables is described by
the factors of course, and some information is inevitably lost. One must
remember that the factor analysis model is optimal for the whole data set
only on average: statistically minor features do not influence the model
and may be lost in the compression. If desired, some of these original
features can be preserved by including the Mahalanobis' distance with the
factors. This measures the multivariate distance (generalized distance) of
a sample to the average sample (Everitt, 1978) and, varying with the
covariance or, alternatively, the correlation matrix of the data set, measures
the rarity of the single sample relative to the data set. Single values
of the Mahalanobis' distance are not easy to interpret, however, because
geochemically different samples may have the same Mahalanobis' distance.
258 Recognition of anomaly patterns in regional geochemical investigations
Multivariate maps
Visually clear and readily informative multivariate maps are difficult
to design. Attempts have been made to display several variables simulta-
neously in the form of complex symbols. In such maps the multivariate
information is explicitly included in each symbol but the regional features
are hard to distinguish. Examples of multivariate symbols are Kleiner-
Hartigan trees (branches indicating element and their length indicating
content), polygons or stars (prongs indicating contents), whiskers (length
of whiskers indicating content) and ChernofFs faces (nose length, position
of eyebrows, and shape of mouth as indicators). Colours can be added
to improve the readibility of the symbols, but still the regional features
are difficult to grasp. Advantages and disadvantages of these multivariate
displays are discussed by Tukey and Tukey, (1981).
The regional aspect of the display can be enhanced by using compound
variables instead of displaying many variables. Factors and the Maha-
lanobis' distance are variables that carry multivariate information and can
easily be presented as coloured surface maps or dot maps.
If certain paragenetic combinations of a few elements are desired on the
map, shaded dots (size indicates one variable and the grey-tone another)
can be overlayed on a coloured surface map by the raster technique.
Experiences with such combination maps are reported by Björklund and
Gustavsson (1985).
260 Recognition of anomaly patterns in regional geochemical investigations
Design
sampling
lines
perpe'ndicula
to anomalies
Fig. 10-14. Alternative routes through the various stages of regional geochemical data processing
are shown in the diagram.
The multivariate approach 261
Smoothen the
data slightly Compute a
factor
model and
factor scores
i
Draw factor
score maps
and interpret
Smoc then the data Draw colored mpare to relevant the factors
surface and/or her information;
filts hill-shaded
median) to sho maps to show ng tools if
large features details liable
Compress data
(usually needed if
many variables) by
selecting important
factors and
possibly the
Skip variables w Mahalanobis
low quality (low
reproducibility or
high detection
limit) OR rank ALL
variables to
prepare for
methods
Select an
V Unknown unsupervised method
(cluster analysis)
with an appropriate
distance measure
N. requested? /
structure
No
Detect multivariate
outliers in the
data using
Mahalanobis
distance and
chi-square plots
1
Prepare the final
Remove outliers report incl
temporarily and descriptions of
compute the data base and data
2
product-moment
correlation matrix
\ / quality (not
interpretation
results only)
As has been mentioned frequently, the goals of the investigation and the
quality of data must be kept in mind when selecting statistical methods
to summarize and illustrate the geochemical information. Guidance for the
selection of mathematical methods of analysis in geology has been presented
in the form of a diagram by Agterberg (1974). Decision trees for steps within
a single complicated and multistage method (factor analysis, for example)
can also be found in the litterature. Figure 10-14 suggests statistical and
graphical methods for geochemical investigation, from sampling through
analysis to data display. While this guidance will be of little use to the
experienced geochemist, it encourages the novice to consider the ways
how to benefit from statistics, which, when collecting, analyzing, assessing,
interpreting and storing huge sets of samples and data, forms a crucial part
of the geochemical investigation process.
263
Chapter 11
TABLE 11-1
Average heavy metal concentration (ppm) in different grain size fractions of weathered rock
samples
Fraction Ni Co Cu Zn Pb Mo
-0.06 mm X 1979.9 142.5 145.5 233.4 105.1 23.7
s 1217.3 114.3 162.5 466.0 241.6 60.6
+2 mm X 1025.2 57.2 115.4 208.3 34.9 10.7
s 532.0 25.0 204.0 516.9 98.9 27.2
TABLE 11-11
Average metal concentrations in different sampling materials. All metal contents are given as
ppm in dry material
Material Cr Ni Co Cu Zn Pb Mo
Humus X 2.6 9.4 2.8 6.2 43.5 15.6 0.4
s 5.2 30.0 4.6 5.6 28.5 14.9 0.8
Peat X 6.1 27.8 4.3 8.0 27.2 7.5 3.4
s 12.6 91.7 6.9 13.4 86.8 7.9 8.6
Surface till X n.d. 13.6 6.6 11.6 14.9 8.5 0.6
s n.d. 10.4 3.6 15.3 7.3 3.3 0.5
Bottom material X 480.7 189.2 31.8 69.7 58.8 17.9 3.8
s 677.8 572.0 43.1 71.4 105.9 39.6 12.3
heavy metal ions from water solution. Both clay and limonite are found in
the fine fraction after sieving. The easily friable minerals have been ground
to fine sizes in the till formation process. Bottom samples contained much
higher concentrations of heavy metals than surficial till samples.
Till usually represents all the lithologies of the bedrock beneath. The
surficial parts contain more far-transported material and heavy metal con-
centrations are more dilute than in the bottom parts where concentrations
are higher and variations stronger. The standard deviation of concentra-
tions in weathered bedrock samples is very large in comparison to that in
till. Mafic lithologies and rocks rich in sulphides are easily weathered and
therefore over-represented in the sampled material, with the result that av-
erage metal concentrations of weathered rock samples may be erroneously
high.
Because of these great differences in chemical composition between till
and weathered bedrock the results should have been presented on different
maps, rather than the maximum values for each sampling point being
plotted on the same maps (see Fig. 11-1A and B).
The best anomaly/background contrast was obtained in weathered rock
analysis; anomalies were strong and coherent. The Ni and Cr anomalies in
bottom samples indicated serpentinites containing sulphide mineralization.
Weathered rock seems to be a good material for geochemical exploration if
it covers the area of interest widely, even if every sample of weathered rock
represents only itself.
Geochemical investigations of weathered rock make use of the fact
that different lithologies are characterized by their own heavy metal
associations. Serpentinite bodies can be rather sharply delineated on maps
by plotting the bulk sum of Cr+Ni+Co concentrations and the Ni/Zn ratio.
993
Ni concentrations Cr concentrations
in bottom samples in bottom samples
1 /
1 / Serpentinite
1 / '////
sdjduivxd uopvuojdxd lOoxxudxpod^
Fig. 11-1. Distribution of (A) nickel and (B) chromium in the <0.07 mm fraction of drift (maximum values ppm at each point either in till
■1 t i l ^ ... - j . - . . ; „ n n4- T ,,4-„~1 TV - I T Λ i
Lutsokuru: Ni and Cr in weathered rock in humid hilly environment 267
If the ratio in a till or bottom material sample is over 20 the sample clearly
represents serpentinite, but if the ratio is over 40 and simultaneously the
Cr/Ni ratio is under 2, a nickel mineralization is indicated (see Fig. 11-2).
The usefulness of weathered rock in geochemical exploration can thus be
improved by mathematical treatment of the results. Factor analysis gave
three factors: Cr+Ni, Zn+Cu and Mo. The factor score maps were not so
clear as the maps of simple element ratios.
Cherty quartzite is characterized by the bulk sum of Cu+Zn+Pb+Mo
concentrations. Granite is characterized by low concentrations of all other
heavy metals determined except Mo.
to
00
^sokuru
rtJ rw
Striae
Striae and till
and till orientation
orientation
O CK ^
£>
- ^ Diamond
°* drill hole Diamond ©
O
drill hole
8
Cr concentrations Ni concentrations o
in dry humus 3
in dry humus
Serpentinite
Serpentinite body Ö body 1
4.1 8.6 53.2 ppm
1.4 3.8 ppm
o
Fig. 11-3. Distribution of (A) nickel and (B) chromium in humus (ppm in dry matter) at Lutsokuru, Finnish Lapland.
Mäkärärova: Au in weathered bedrock in humid hilly environment 269
The same rules do not apply to peat. Mo, Cu, Ni and Cr were found to
be absorbed and enriched at the rim of the peat bog, while Co was first
captured further into the bog. What was amazing was that peat as well as
humus also gave a very distinct response to the elemental concentrations
of the bedrock. As seen from the maps (Fig. 11-3A and B) both Ni and Cr
concentrations of humus and peat indicate the southern mineralized end
of the largest serpentinite body, but fail to indicate the southern cluster
of serpentinite bodies. Still, organic materials could be recommended for
geochemical exploration.
Presentation of the assay results for different materials on the same map
is confusing and may lead to erroneous conclusions. This is true for the
organic materials, but still more so for till and weathered rock, especially
when the concentrations in weathered rock are distinctly higher than in
till.
Although the HNO3 leach used in base metal analysis is best in explo-
ration for sulphides and the total content determination best for exploration
of most oxide ores, it would have been good, for reasons of comparison of
different materials, also to have analyzed all materials for all elements with
one and the same method. Vertical profile sampling should have been done
across the anomalies to check the metal distribution in the third dimension
and find out whether the anomalies point to a suboutcrop of ore.
^- 0 1 km
Fig. 11-4. Gold concentrations in weathered rock and till consisting of weathered rock material
at Mäkärärova, Finnish Lapland.
known veins, but some new gold-bearing veins were discovered as well.
Some of the anomalies even point to sources outside the study area. The
continuation of the veinlet towards the northwest and southeast could also
be deduced from the results of the preceding geochemical mapping and of
low altitude airborne geophysical mapping.
Gold occurs in such small quantities and so irregularly in overburden
that normal geochemical search by direct Au analysis can seldom succeed.
The extra sensitive method for analysis employed here, as well as the
usually high Au concentrations in the weathered bedrock, made the study
successful and the method can be recommended for exploration in similar
circumstances.
The report tells nothing about the distribution of the other elements,
such as Cu, Zn, Pb or Ag, nor about the usual pathfinder elements S,
As, Sb or Bi. In this case even the distribution of Fe could have pointed
the way towards promising follow-up targets. Kontas combined the results
of two totally different sampling materials — till and weathered rock.
Although such combination usually leads to fatally erroneous conclusions,
272 Geochemical exploration examples
\ Joutensuo
_D CtO— r. m - n - m A ππΐππ
ii
M
jjsi
L 200 m
10 ppm
L Mo in till 5 / Mo
0
Martti Kokkola
5^—
Ni - CONCENTRATION
IN TILL (ppm)
U > 8703
O 135-8703
o 47 - 135
26-47
0-26
c) o Areas of
.<^§)) low magnetic
anomalies
0 100 m
Oi w
<0
o
o ^ -
(
0
c<:3 •
o
o o o
o O
o
LD ))
\\^^^%y o
Cu - CONCENTRATION
IN TILL (ppm)
rT&^ o °
U > 4352
o O 322 - 4352
o 41 - 322
22-41
0-22
c) β Areas of
^^^) low magnetic
anomalies
oi9
0 100 m
0
o
o ^ -
(
/fCZ_°) ■ςφ
o
0
O
c<=3 °
o
o o
o o
o
<ό >>
Si® °
o
ο-σ=
older bed of bluish grey, dense, more stony gravelly till. Sand layers are
sometimes found between these two till beds. From till fabric analyses and
numerous striae observations, it was deduced that the older ice flow was
from about 320°, and the younger flow more from the west, about 285°.
Sampling was carried out across anomalies classified as interesting in an
earlier magnetic study. The intention was that samples should represent
the source of the anomaly as well as possible. The sample lines were
10-30 m apart and the sample site interval was 5-20 m. The samples were
collected from the bottom part of the till bed, close to the bedrock surface,
by a gas-powered Cobra percussion drill equipped with a flow-through type
sampler and extension rods. As a result, the sample consisted not only of
till but of weathered bedrock material. In this way the glacigenic feature of
an anomaly possibly present higher in the soil cover in the two till beds was
eliminated. The average thickness of the soil cover at the sampling sites
was 2.7 m and the maximum thickness 8.2 m.
276 Geochemical exploration exampU
Cr - CONCENTRATION
IN TILL (ppm)
W > 2000
O 1000 - 2000
o 500 - 1000
o 200 - 500
0 - 200
CD
Areas of
<X<y) low magnetic
anomalies
Of
Ό <§>
Ä
<tD
The low metal contents in the more northerly magnetic anomaly may
mean that the source of the anomaly does not outcrop or that the sampler
was prevented by stones in the till from penetrating to the surface of the
bedrock. In any event, even the low magnetite content of the graphite
gneiss is sufficient explanation of the magnetic anomaly. However, the
percussion drill-method that was used does have its limitations, as noted
above, so that the till study was able to confirm only the more southerly
anomaly as related to mineralization, while the explanation of the more
northerly anomaly remains in some doubt.
Till sampling was done with a light percussion drill, Partner M 100.
The through-flow pit was used as a sampler. The study area was 1.4 x 1.8
km. The interval between the sampling lines was 100 m and the interval
between the sampling points was 20 m. At places of interest the grid was
made denser, with intervals of 50 m and 5 m.
The samples were dried and sieved into three grain size fractions: <0.06
mm, 0.06-0.25 mm and >0.25 mm. The finest fraction was dissolved in
a mixture of perchloric, hydrochloric, nitric and hydrofluoric acids and
analyzed by AAS. The medium, sand (0.06-0.25 mm) and coarse (>0.25
mm) fractions of some anomalous samples were also analyzed, so that the
relationship between metal content and grain size of glacial sediments
could be evaluated. The sand fractions of some anomalous samples were
separated in tetrabromo-ethane (density 2.96 g/cm3). The heavy fraction
was studied under a stereomicroscope, and a number of scheelite grains
were counted in UV-light. Some heavy fractions were mounted in Epofix,
made into polished sections and studied with a polarizing microscope. Some
heavy fractions were also studied with a scanning electron microscope and
by X-ray diffraction and chemical analysis
The statistical distributions of tungsten, tin, copper and zinc according
to sediment type are listed in Table ll-III. The average concentrations of
tungsten and tin were higher in till than in sorted sediments. This is easy
to understand if the tungsten and tin occur in residual minerals and we
take into account that till is the first, sand the second and clay/silt the
third derivative of the bedrock.
TABLE ll-III
The statistical parameters of tungsten, tin, copper and zinc in glacial sediments at Hieronmäki
X M s c n
W (ppm) till 2.3 1.0 13.5 6.0 1773
sand 1.2 1.0 0.8 0.7 53
clay/silt 1.6 1.0 3.1 2.0 198
Sn (ppm) tiU 1.4 1.0 1.5 1.1 1009
sand 1.0 0.5 1.1 1.1 27
clay/silt 0.6 0.5 0.9 0.9 20
Cu (ppm) till 67 60 34 0.5 1773
sand 40 38 21 0.5 53
clay/silt 71 53 40 0.6 198
Zn (ppm) tiU 91 81 36 0.4 1773
sand 73 72 39 0.5 53
clay/silt 113 125 41 0.4 198
TABLE 11-IV
The distribution of tungsten, tin, copper and zinc according to the grain size
Min Max X n
W (ppm) <0.06 mm 0 370 13.8 91
0.06-0.25 mm 0 199 9.3 60
>0.25 mm 0 1028 70.1 53
Sn (ppm) <0.06 mm 0 14 2.0 90
0.06-0.25 mm 0 10 1.7 60
>0.25 mm 0 20 3.0 53
Cu (ppm) <0.06 mm 25 354 74 91
0.06-0.25 mm 8 96 33 60
>0.25 mm 6 253 37 53
Zn (ppm) <0.06 mm 37 381 100 91
0.06-0.25 mm 25 160 67 60
>0.25 mm 5 800 90 53
TABLE 11-V
Composition of fine (<0.06 mm) and medium (0.06-0.25 mm) fractions of seven till samples
chalcopyrite, sphalerite, pyrite and pyrrhotite were all found in the samples.
The anomalous contents of tin are so low that it would be very difficult
to find grains of tin-bearing minerals. Some copper and zinc anomalous
samples contained goethite and lepidocrocite, which have been generated
as weathering products of the sulphides. The other minerals detected in the
till samples were mica, amphibole, chlorite, almandite, plagioclase, quartz,
microcline, apatite and tourmaline.
The anomaly maps of tungsten (Fig. 11-9) and tin (Fig. 11-10) in
the <0.06 mm fraction have been drawn by using the moving average
technique. The size of the window for tungsten was 80 m x 80 m and for
tin 100 m x 100 m. Two tungsten mineralizations (I and III) have been
found in the outcrops before the geochemical sampling was done. Each is
indicated by a clear and intensive W-Sn anomaly in till. Besides these, two
new anomalies were detected. The southerly one was drilled and a new
mineralization (II) was found.
The anomalies of the metals analyzed in this area are mainly clastic and
quite local. The dispersion length has mostly been from nil to some tens of
metres. Perhaps the main reason for short dispersion has been the elevated
location of the survey area.
The geochemistry of glacial sediments was studied in the area of a
scheelite mineralization in southern Finland. On average tungsten and tin
contents were higher in till than in sorted sediments. The mean contents
of copper and zinc were higher in clay/silt than in till and sand. The
distribution of metals according to grain size was bimodal, high values
occurring in both coarse and fine fractions. The anomaly contrast is
strongest in the fine fraction. Dispersion in the area has been mainly
clastic. The anomalies are quite local and therefore a dense sampling grid is
needed. As a result of the geochemical study a new scheelite mineralization
was found.
Hieronmäki: W, Sn, Cu and Zn concentrations near a scheelite mineralization 281
W ppm
+
< 3
* 3 - 4
Ο 5 - Β
Φ 7 - 10
On > 10
^ DRILL HOLE
+
τ+
♦ ♦ ♦ ♦ τ
ττ! +
+ + + + + +
+ + Φ
+ + 4
+ +
+ + +
Φ ♦ ♦ + Φ « *
Φ ♦ + + * Φ ♦
- | - 6774 750 + + Φ Φ +
+ +
<« Φ
♦ Φ + Ο
+ Φ Φ ♦
100 500m
+ Φ *
+ + Φ
♦ + Φ
Fig. 11-9. Tungsten anomaly map. I-III denote the sites of the scheelite mineralizations.
282 Geochemical exploration examples
Sn ppm
+ < 1
o o 1 - 1
o
O 2 - 2
O o 3 - 5
O
o OB > 5
o DRILL HOLE
s*
o
o
O
O
o o o o + ► ■ ♦ ♦
o o - * * -
o O O ♦ ♦ T ♦ ♦ i ♦ ♦ ♦ ♦ ♦ ♦
O o o * ♦ o * * ♦ ♦ ♦ ■♦· · ♦ ♦ *
;
o ^ ♦o o o φθ * ♦ + · ■· · ■♦ *
o o ♦ ♦ 9 J ? ♦ ♦ ♦ ♦ o * *
♦ ♦ ♦ ♦ T | * T * ♦ * ♦ o ♦ -
«■ + + + + + + +
o o *
* * ♦ r ♦ ♦ *
* o o -
♦ ♦ ♦ ♦
* o o OO o o o
♦
+
♦ · ♦ ■ ♦ ♦ ♦
* · SWS!o 0
OO
♦ * o oto
+ 6774.750
100 500m
Pekka Lestinen
Fig. 11-11. Cu concentration in the <0.06 mm till fraction at Kissanloso based on regional
geochemical mapping of eastern Finland. The background lithological map is based on the
bedrock map by Nykänen (1971a).
284 Geochemical exploration examples
Cu ppm
o < 22.0
O 22.0 - 3 6 . 0
MVS
Q 36.0 - 5 0 . 0
• 50.0 - 7 2 . 0
• 79 >72.0
{ 1 km |
GG ARCHEAN
GG Gneissic granitoid
GR I Cataclastic granite
|[s/|\/S| Metavolcanite and
' ' -sediment
PROTEROZOIC
GG KD Metadiabase
Γ210
_W_
GR
90^°° GR
310
Fig. 11-12. Cu concentration in the dry matter of organic stream sediment at Kissanloso. The
lithological map by Nykänen (1971a).
Cu ppm
Δ < 100
+ 100 - 129
□ 130 - 149
U 150 - 188
■ 189 - 208
■ 210 > 208
• Not determined
0.5 km
* Maximum content
in the upper or
middle level of
the till blanket
++ 0-*.+ Ά^Τ
Fig. 11-13. Cu concentration in the <0.06 mm till fraction (maximum concentration at each
sampling point). The classification of the data is based on the values of the 60th, 80th, 90th,
95th and 98th percentiles of the cumulative frequency distribution.
the study area are concentrated south of Elessiinlampi (Fig. 11-13), where
they form a large and coherent anomaly about 1.5 km long, up to 400 m
wide and trending 290°. Vertically the anomaly is distributed so that its
southern margin, excluding the very western end (line 4), is at the base
of the till cover. Towards the northern margin, anomalous values are also
occasionally encountered in the middle and upper layers of the till cover.
The values are highest in the middle of the anomaly, where the copper
Kissanloso: use oflithology and Cu-Mo concentrations of till 287
Fig. 11-14. Mo concentrations in the <0.06 mm till fraction (maximum concentration at each
sampling point). The classification of the data is based on the values of the 60th, 80th, 90th,
95th and 98th percentiles of frequency distribution.
contents reach 450 ppm. Another anomalous zone lies parallel to this zone
and immediately to the south. It is composed of two separate anomalies, of
which the eastern one is in the upper part of the till cover. Elsewhere the
Cu anomaly is less coherent.
The Mo concentrations in the fine till fraction are modest (Fig. 11-14),
the maximum value being 5.7 ppm. However, a well-defined, fairly large
anomalous area occurs southwest of Elessiinlampi. At its southeastern
end the anomalous concentrations are often in the upper part of the till
blanket. As not all the sampling lines in the southeast of the study area
288 Geochemical exploration examples
were analyzed for Mo (lines 5, 7, 9 and 11), it is not easy to compare the
anomaly patterns of molybdenum and copper. It appears, however, that
although the anomalies overlap to some extent, the patterns differ from
each other.
In the 2-20 mm fraction the bedrock fragments show a clear systematic
variation in lithology. In the area southeast of sampling line 5 (Fig. 11-15),
granite and metadiabase predominate, whereas in the northwest gneissic
Fig. 11-15. Metadiabse fragments in the 2-20 mm till fraction. Each sampling point is
represented by the sample with the highest Cu concentration in the <0.06 mm fraction.
Numbers in parentheses refer to samples analyzed for copper (see Table 11-VI).
Kissanloso: use oflithology and Cu-Mo concentrations of till 289
TABLE 11-VI
Cu concentration of the <0.06 mm fraction and metadiabase fragments in some till sample
from the Kissanloso study area
Martti Kokkola
with woodland (90-100 m above sea level). The height variations are only
a few metres. Exposed bedrock makes up a small proportion of the area.
Information about the bedrock is based principally on drilling results
and on information obtained from Kylmäkoski mine. The bedrock consists
mainly of mica gneiss. The mica gneiss is cut by granites and pegmatites,
and in places there are smaller horizons of amphibolites and ultramafic
rocks. The Kylmäkoski ore is a Ni mineralization associated with differen-
tiated ultramafic rock.
Two till beds of different ages have been identified in the vicinity of
the study area. The younger one, caused by the due westerly flow of the
continental ice sheet, was generally more prominent in the exploration
as the boulder fans were oriented in the same direction (270-285°). The
thickness of the younger bed ranges between 1 and 5 m. Striae etched
by the older ice sheet flowing from a more northern direction (325°) were
encountered, but till beds deposited by it were less commonly identified and
the variations in their thickness are not known.
The study was spurred by the mafic ore boulders found southeast of
the Kylmäkoski mine. Their source from a direction of 280° had not been
proved. As a result of excavator pitting and careful boulder tracing in the
area, nearly 300 different types of ore boulders were found. The till cover
proved to be very thick (more than 7 m) and tightly compacted and to
contain large boulders. On the basis of the structure of the till and stone
counts the deposition was classified as a Rogen moraine. Careful stone
counts were done on the material excavated from the pits and on the
surface stones of the area. By comparing results of the counts with the
bedrock data it was concluded that the transport distance was not more
than 1-2 km.
A total rock analysis by XRF was made for more than 200 separate boul-
ders found in the field and for typical samples taken from the Kylmäkoski
ore. The analytical data were interpreted by discriminant analysis.
The results indicated that the boulders, which even macroscopically
could be divided into types resembling those occurring in the Kylmäkoski
ore, were so closely similar in chemical composition to the ore that, to
a high degree of probability, they could be regarded as derived from this
known ore (Fig. 11-16).
The longitudinal orientation of the Kylmäkoski ore differs only slightly
from the more northern flow direction of the ice sheet. Striae caused
by the flows of the ice sheet from both directions are found on the
surfaces of roches mountonnees occurring close by the open mine pit. These
indicate that the ore outcrop could have been eroded by flows from both
directions.
The results of the study suggest that the Kylmäkoski ore was eroded by
two different flows of the ice sheet. The older one, from the direction 325°,
was able to act on the ore over a longer distance, because the flow direction
292 Geochemical exploration examples
was about the same as the longitudinal orientation of the ore. Consequently
this flow, the erosional effect of which was also stronger, was able to quarry
a great many boulders from the ore. These were transported approximately
one kilometre towards the southeast. By contrast, the younger flow of
the ice sheet from 280° crossed the ore transversely. Unfortunately, the
land on the eastern side of the ore has been fairly extensively cultivated,
making the comparison more difficult. However, fewer boulders have been
associated with the younger than with the older boulder fan. How a till
Laukunkangas: Ni, Co and Cu concentrations of till at a mafic intrusion 293
formation deposited by the older flow (325°) of the ice and not covered by
younger till could be preserved as a relict on the southeastern side of the
ore is a mystery. The geochemical study of tills had helped in solving the
question.
Ni
in < 0 . 0 6 mm till fraction
X ore outcrop
Cu
in < 0 . 0 6 mm till fraction
ppm
-19
o 19-48
O 48-100
O100-
X ore outcrop
o o
°Vo°o»v;o0o
o
o o
Co
in < 0 . 0 6 mm till fraction
ppm
o°o.°„ . -7
r.°„°.°o
olio 0 °o°qrCh°o°o ° o 7-16
O 16-26
θ 2 6 -
of the overburden. Farther to the north where the till cover is 20-30 m
thick, the mineralization is not detected in the till despite the higher metal
contents there. Evidently it is effectively concealed by the thick till deposit.
Moreover, if a glacigenic anomaly of the mineralization did exist it would
lie — because of the more northern flow of the ice sheet — in the same
area as the glacigenic anomaly caused by the younger ice sheet.
A similar till study with a sparser sampling coverage of 200 x 50 m
was carried out earlier in the area. At that time, however, the lines
were disadvantageously located, with the sampling sites nearest to the
mineralization located in the up-ice direction. No anomaly due to the
mineralization was detected there, nor at the nearest down-ice sites,
approximately 200 m away from the mineralization.
It should be mentioned that the Laukunkangas mineralization had
already been localized by other geological methods (drilling, etc.) and the
study described here was carried out for the purpose of clarifying the nature
of the till anomaly by geochemical means. Subsequent drilling based on
integrated use of different prospecting methods, till geochemistry among
others, in 1984 led to the discovery of the economic orebody.
296 Geochemical exploration examples
Maaselkä lies near the northern border of the Karelidic schist belt. The
bedrock is overlain by 0.5-10 m thick glacial drift, mostly till. Preglacial
weathering crust covers the surface of the bedrock, because the area lies in
the ancient ice-divide zone of Central Lapland.
The geochemical investigations were carried out in several stages. In the
reconnaissance stage till and organic stream sediments were used. In the
regional stage till samples were taken at a higher density. In the detailed
stage till and weathered bedrock samples were taken from geochemically
interesting targets and finally the anomalous areas were investigated by
trenching and diamond drilling. As a result a copper-cobalt mineralization
was found.
Maaselkä is situated 170 km northeast of Rovaniemi in northern Finland
(Fig. 11-20). This area lies near the northern contact of the Karelidic
schist belt, in the eastern part of the Central Lapland greenstone belt.
The bedrock of the study area is composed of metasediments: quartzites,
graywacke schist-phyllite and black schist and ultramafic komatiitic vul-
canite (Mutanen, 1976). The rock types are striking in E-W direction and
dipping 10-30° to the north and they are penetrated by gabbro sills.
Maaselkä belongs to the Central Lapland peneplain with elevations
of 280-300 m. The area forms a watershed which is gently sloping to
the south. The ground-water discharges as large springs in the southern
seepage zone of the canyon.
150 km
(*) Maaselkä
•
• • • ill
φβ28
• • • •
• • · • . |I • II
• · • · •
• • • · · •
M a a s e•j k a· •
1 φΐ220 ' ·*« Maaselkä •
#
A 254 · • • •
1<-φ -
• • • •
• • • · •
Copper (ppm) in till Cobalt (ppm) in till
• •
• φ2βθ·
(fraction -0.06 mm) • • (fraction -0.06 mm)
•
• •• • < 88 • < 21
• 88 - 137 • 21 - 29
• •
• • 138 - 175
• · • 30 - 33
• • • 176 - 250 • 34 4 0
• •
φΐ220 > 250 I
o • > 40 o
• · 7520-I #52« · 7520-J
I I Area in the regional sampling stage
Fig. 11-21. The distribution of copper and cobalt in till, sampling density one sample per 4 km 2 .
Till covers the whole area and rock exposures are scarce. The 0.5 to 10
m thick glacial drift consists of local till where it is thin. Two till beds with
a cemented gravel interlayer occur in places with thick drift. In places the
surface of the bedrock is weathered both physically and chemically down
to a depth of 30 m. This preglacial weathering crust is common in the
ice-divide zone of Central Lapland (Penttilä, 1963). The glacial erosion was
rather weak in the Maaselkä area. The transport direction of the youngest
glaciation was from north to south (Hirvas, 1977).
Till, organic stream sediments and weathered bedrock were sampled in
the geochemical investigations. In the reconnaissance stage till samples
were taken with a light percussion drill at a density of one sample per
4 km 2 from an irregular grid (Fig. 11-21). The cemented gravel bed was
unpenetratable for the drill. The stream sediment samples were collected
at 250 m intervals along the streams (Fig. 11-22). In the regional stage till
samples were taken with the drill along lines at a density of 12 samples per
km 2 (Fig. 11-23). In the detailed stage samples of till and weathered bedrock
were taken from geochemically interesting targets with light percussion
and heavy pneumatic drills and also from trenches. These samples were
taken along lines and trenches spaced 50-100 m apart at 1-20 m horizontal
and 0.5 m vertical intervals (Figs. 11-24 and 11-25). After location of the
source of the highest copper and cobalt anomalies, rock samples were taken
with a diamond drill (Fig. 11-26).
298 Geochemical exploration examples
1 * L •
L s
% • : Copper, ppm Cobalt, ppm
< 6 < 21
1
'
11
' :
6-15
16-30
>30
t •
•
21 - 1 4 0
141-200
'■ v ··..* · II
'' . ■·
«
· ·« · .
• >200
•
- " ■ * .'
A->,
1 ·
f *
λ^
*
9 4
c
..··/ * */* t
[/_
Φ
V O o
l" M
m
Li
Ift
J
7520 7520 J
I I Area In the regional sampling stage
Fig. 11-22. The distribution of copper and cobalt in organic stream sediment, sampling density
one sample per 0.5 km 2 .
Till and weathered bedrock samples were sieved and the <0.06 mm
fraction was analyzed. Organic stream sediment samples were ashed. The
till samples from the first two stages were analyzed by optical emission
spectrometry for 17 elements. The organic stream sediment samples and
all samples from the final stages were analyzed by AAS for 7 elements after
leaching in 6 M HC1 and 7 M HN0 3 , respectively (Gustavsson et al., 1979).
Average concentrations of copper and cobalt in till in the Central Lapland
schist belt around the study area are 105 ppm Cu and 34 ppm Co and in
weathered bedrock 176 ppm Cu and 32 ppm Co (Kauranne et a l , 1977).
In the reconnaissance stage of this study the maximum contents of the
trace metals in till were high, but high values did not form homogeneous
anomalies (Fig. 11-21).
The concentrations of the trace metals in the organic stream sediments
were based on dry weight. The arithmetic mean of the distribution of
copper was 8.53 ppm and the standard deviation is 8.25; for cobalt the
values were 50.8 ppm and 69.8, respectively. The number of samples was
REGIONAL SAMPLING STAGE
*Maas*elkä > t «
? i » Maas'.elkä · 3r-
? :
l i t ! !
ii». J i !
i
i- X.
-783I i- - 7532 - J
Γ Η Area in the detailed sampling stage
! i 2 km 9
&
Fig. 11-23. The distribution of copper and cobalt in till, sampling density 12 samples per 1 km 2 .
3
DETAILED SAMPLING STAGE
Fig. 11-24. The distribution of copper and cobalt in till, varying sampling density. Each symbol represents the mean concentration of the
metals in an area 50 x 50 m.
o
: i · i 11: t i I : · ! :
• • t
. t · :
I »
•
•
? : • TO
o
TO
1
-7533.0- -7533.0-
TO
A__J Diamond drilling profile ' Northern edge of komatilte layer 1km
Fig. 11-25. The distribution of copper and cobalt in weathered bedrock, varying sampling density. Each symbol represents the mean
concentration of the metals in an area 50 x 50 m. -8
o
3
O
3
I
Maaselkä: discovery of a Co-Cu mineralization by till geochemical study 301
Co ppm
DIAMOND DRILLING PROFILE r300 Tfll
200 □ Woetherod bedrock
Greywacke schist-phyllite
Black schist
Arkosic quartzite, keratophyre
Gabbro
Komatllte
2SS Cu 0.1 -0.5 %
Cu 0.5 · 7.0 %
\ Co 0.02-0.15%
Sulphides are disintegrated
by weathering
Diamond drilling hole
* Stratigraphic bottom
Fig. 11-26. The distribution of copper and cobalt in the mineral deposit of Maaselkä (lower
part) and in the overlying till and weathered bedrock (upper part).
TABLE 11-VII
Statistical parameters describing the distribution of copper and cobalt in till and weathered
bedrock
Cu a Co a Cu b Co b Cu c Co c
Arithmetic mean 148 43 392 35 1980 52
Median 134 29 140 26 389 35
Standard deviation 259 30 829 83 5030 52
Range 32- 6530 12-162 13- 14,000 2- 24 1- 70,260 1-430
Number of samples 542 542 966 966 689 689
a
Regional stage (till fraction <0.06 mm).
b
Detailed stage (till fraction <0.06 mm).
c
Detailed stage (weathered bedrock, fraction <0.06 mm).
metals together form four anomalies but the anomalous contents of the
metals separately do not necessarily coincide. With increasing sampling
density and higher threshold level the cobalt anomalies tend to indicate
mineralized areas in the metasediments north of the ultramafic vulcanite.
The anomalous patterns in weathered bedrock are reflected in till with
the exception that the most significant copper anomaly now stretches
eastward under the cemented gravel bed in the eastern part (Fig. 11-26).
To investigate the significance of the eastern anomaly a diamond drilling
program was carried out along the profile A-B (Fig. 11-26). The maximum
copper content in the bedrock increases in places to 7% and the cobalt
content to 0.15%, but the low mean content of the metals and the small
size of the mineralization do not make it an economic ore.
This case study shows that the geochemistry from a low density sampling
grid of surficial materials brings out anomalous areas especially when both
till and organic stream sediments are used. During a follow-up study a
copper-cobalt deposit was found at Maaselkä.
Terho Koivisto
30°
1 5 0 km
(x) Metsola
Fig. 11-28. Bedrock of the survey area according to Peuraniemi (1982) and Perttunen (1989).
origin is seen above a diabase dike in the southeastern part of the area (Fig.
11-28).
At Petäjäskoski, 5 km southeast of Metsola, there is a Cu-Fe formation
associated with the contact of albite diabase and quartzite (Peuraniemi,
304 Geochemical exploration examples
Jb__
/ ■ <: ■
Polar circle 2 5*30
Rovanie mi Bp" '""""~
v· ^ >''···>
^ -m
( A '· /^·
V- •·
χ·^β^~
(
N
SWEDEN
i.·
\ ' *f* ' *
• V
Φ/
J.
·
'
· /
7 FINLAND «
Ί· '
\
?v ·/·'''''·
i —\
'
11 ^*^ - ^ K e r n i
Cu
iPPm> jn tMI
1
cf^-o * < 68
li \Λ
\
· 68-106
· 107-168
3 0 km
' Φ >168
Fig. 11-30. The distribution of copper. Sampling density is one sample per 30 km 2 , fraction
<0.06 mm. The Peräpohjola schist area is bordered with a dashed line.
The till cover consists of two beds of different age, with a boulder pave-
ment between. During the deposition of the older till bed the continental
ice flowed from the northwest, and during the deposition of the younger till
bed from the west (Korpela, 1969; Koivisto and Manner, 1981). Within the
study area the older till bed occurs only in deeper depressions and on the
distal sides of bedrock hills. According to fabric analyses of till stones, the
transport direction was 240°-270° (Koivisto and Manner, 1981).
Sampling was carried out stage by stage using a progressively denser
network. The sampling material at every stage was till. The sampling and
analysis of the reconnaissance stage were done as part of the Nordkalott
project. Till samples were then taken by spade from a depth of 0.5 m at
a sampling density at about 1/30 km 2 . Till samples of the reconnaissance
stage were not analyzed for Au. The Cu content map in Fig. 11-30 has been
simplified from the data of the Nordkalott project.
At the regional geochemical mapping stage the samples were taken with
a percussion drill at intervals of two kilometres. The sampling density was
thus 0.25/km2. At each site the samples were taken at depth intervals of 1
m to the greatest possible depth.
The detailed survey consisted of two different stages and included
lithogeochemical sampling with a lightweight compressed air drill. In the
306 Geochemical exploration examples
Cu (ppm) in till
< 85
• 85-120
• 121-181
• 182-283
φ 284-462
A 5 0 0 >462
Area of detailed
geochemical survey 1
10 km
-7340 « ■-
Au (ppb) in till
< 4
• 4-7
• 8-15
φ 16-31
^A >31
h- 1
1 0 km
Fig. 11-31. The distribution of copper and gold. Sampling density is one sample per 4 km 2 .
308 Geochemical exploration examples
I I A r e a of d e t a i l e d g e o c h e m i c a l s u r v e y 2 A r e a of d e t a i l e d g e o c h e m i c a l s u r v e y 2
Au (ppb) in till Au ( p p b ) in t i l l
f
< 4 < 4
4- 7 . ' · ■ · ' 4· - 7
••
• 8-15 8-15
:T3 S,B II
• 16-31 16-31
• >31 • >31
Fig. 11-32. Copper and gold concentrations of the fine fraction of till in deep samples (left) and
shallow samples (right).
lower levels (average depth 4.2 m). From the difference it is inferred that
the last transport direction of the continental ice sheet in the study area
was from west to east and that the transport distance of the fine fraction
of till was at least 200 m. Cu contents of the lowest samples indicate a
mineralized zone that seems to continue northeastward.
Although more dispersed, the anomalous pattern of Au is not unlike
that of Cu. The highest Au content of the lower samples occurs in the
Cu anomaly zone. The anomaly is stronger (highest content 2100 ppb) in
upper level samples. The dispersion of Au seems to have occurred over a
shorter distance and the direction is more towards the southeast, than that
of obviously more homogeneous and reliable Cu in till.
The anomaly patterns discovered at the second stage of the survey
(detailed geochemical survey 2) directly point out a Cu-Au mineralization in
the local bedrock, since the sampling network is very dense and samples are
taken from near the bedrock surface (Fig. 11-33). Although the anomalies
in till extend beyond the eastern margin, the mineralization apparently
lies within the sampling area. The results of the lithogeochemical sampling
Metsola: discovery of a Cu-Au mineralization by till geochemical study 309
. . . . . . . · Al
. . . . . . 0 A.
. . · · ·· ·
• ······· . . ^
T . . .· . . . ·. . . Ä . .
*
. . .·«·.·
· · · · · · · · · ' :: *m.' . . . . •
ν:*::;β?
»··· · · · · · · w ·:::::■··■. 4 %
··· · • · · · · · ·· ·
···
Λ · . «Ä· ··
w *w ^ · ·
- 7355.84 · ' · · -
Cu (ppm) at the bedrock-till interface Au (ppb) at the bedrock-till interface
<150 · 500- 999
< 8 • 3 1 - 60
• 150-299 · 1000-1999 ,
50 m 8-15 • 61-110
• 300-499 φ >1999 >110 50 m
16-30
Fig. 11-33. The distribution of copper and gold at the bedrock/till interface.
Cu ppm Au ppb
1100
500
Fig. 11-34. Copper and gold concentrations of the samples from the drilling line A-B (see Fig.
11-32) over the mineralized zone.
310 Geochemical exploration examples
with a compressed air drill provide evidence of this (Fig. 11-34). Figures
11-32 and 11-33 show that the sampling line of the compressed air drill
holes does not run over the strongest part of the anomaly but about 50
m to the north. The results nevertheless confirm that the most strongly
mineralized zone lies in the middle part of the albite diabase. As Fig. 11-33
shows, there are again clear similarities in the anomaly patterns of Cu and
Au, although the gold anomaly seems to be more widely dispersed and less
coherent.
1
Pallastunturi*.*.
I I Basement «
»)))))))] Sedimentary r o c k s '
P ^ H Volcanic rocks \
Intrusive r o c k s
» I I Granite
_ ■ Geophysical
^ ™ conductive zone
Fig. 11-35. A simplified bedrock map of the Pallastunturi area, northern Finland. Nickel
mineralizations are marked 1-4.
o o
o Grey or greyish
(i) ~ ^^ b - brown lamellar
o „ « Cc sandy till
j o>V^
Q> ^ ^. r \
£>
o
° -A
I 0
o Grey or brownish
o grey sandy till
(II)
o> o.
Λ
^ o
o c ^
X X X XX Bedrock
5-
(m)
Direction of
ice flow
(measured in till)
Glacial striae
from top to bottom two till units, a sorted sediment layer and a third till
unit.
The orientation of flow of the surface till unit is 160-200° and that of
the other till 170-200° (Fig. 11-37). The general direction of ice flow was
from the south, the orientation of most of the observed glacial striae being
170-180°. No study was made of the transport distance, but observations
in other places in northern Finland have shown the fine matter of till to be
very local.
The sampling lines of the regional investigation were perpendicular to
the strike of country rocks and to the direction of ice flow; the lines were
2 km apart and the distance between sampling points along the lines was
1 km. The samples — till, sorted sediments and weathered bedrock if
available — were taken by light percussion drill. The sampling interval in
vertical direction was 1 m to the depth attainable. In the local investigation
the lines were 200 m apart and the distance between sampling points was
50 m; one sample, from the basal till, was taken at each sampling point.
After drying, the till samples were sieved into three fractions: fine <0.06
mm, middle 0.06-0.25 mm and stone >0.25 mm. The stone fraction of
the deepest till samples and/or weathered bedrock was washed and the
lithologies of rocks were identified.
The fine fraction of till was analyzed with an optical emission quantome-
ter (OEQ: Mg, Cr, Ni, Cu, Co, Zn) and an atomic absorption spectropho-
tometer (AAS: Ni, Cu, Co, Zn). For the AAS analysis, samples were leached
with nitric acid and the atomizing flame was air-acetylene. In the local
investigation, chromium was analyzed by XRF and Ni, Cu, Co and Zn by
AAS.
£
o
o
<*}
§
o
55-
I
I'
a.
CO
I-1
CO
Fig. 11-38. Concentrations of magnesium in the fines of till. The shaded areas are anomalous.
314
Geochemical exploration examples
+ Δ + Δ Δ + Δ H+fr 3
Δ Δ + Δ 4^ + + + D 3
+
Ι' ^
φ + Δ + Δ Δ + + +
•3
1
+ Δ + Δ Δ + Δ Δ +++ +D
Ο
ο
δ'
<^>
ο
ο
55-
+ + + Δ Δ A 3
ppm ε.
Α < 5 0 3
+ Δ + Δ Δ + Δ Δ Δ + (
+ 50-205 ν^. + + + + + I
D 205-280 ΔΔ Δ Δ + ++ + + +
ϋ 280-305
I'
Δ Δ 0
■ 305-615 Δ Δ + Δ + + + + + + + + ? + + + + + + ++++
677Β >615 Δ
5 km Δ + Δ + Δ ϋ Δ + Δ + + + + + + + + D D +^0) + + + + + + + + D + CO
en
The results of the regional investigation show that, even with a sparse
sampling network like this (1 sample/2 km 2 ), the ore critical zone, in which
the known mineralization are situated (Fig. 11-35), clearly shows up as
metal anomalies in the till. The area of volcanic rocks in the eastern part
of the study area is also clearly reflected in the till and one can reasonably
assume that there may be mineralization there, too. The metal anomalies
in till in the study area — Mg, Cr and Ni together — are good indicators for
the mafites and ultramafites carrying nickel mineralizations (Figs. 11-38,
11-39 and 11-40).
The local geochemical investigations of Ni and Cr in till provided an es-
sentially more accurate picture than the regional investigations. Due to the
intense alteration of country rocks, the pattern for samples of basal till is
also a good alternative sampling material. The investigations were directed
to prospecting for Ni mineralization, indications of which were sought
not only by till geochemistry but also by stream sediment investigations.
Several mineralized zones were indicated also by geochemical anomalies in
stream sediments and by outcrops in rivers.
According to the anomaly patterns, the occurrence of ultramafites is no-
ticeably sporadic. In the area with few outcrops the Cr and Ni anomalies in
till suggested the locations of several different serpentinites (Fig. 11-41) and
JkuUk
A A
,Λ,,Λ,,Ι,,Μ
a_uur
U m T i A I
* i
Ni + Cr > lOOOppm
I ▲ = lOOOppm
A A 200m
Fig. 11-42. Ni/Cr ratios. The shaded area: the ore-critical serpentinites in this area.
the real occurrence of most of these was later verified by diamond drilling.
Ore-critical serpentinites were differentiated from other serpentinites
on the basis of their high Ni/Cr ratio (Fig. 11-42, shaded area). High Ni
concentrations also originate outside of the ultramafic rock formations.
However, this Ni-anomaly group can be differentiated by means of the Ni/
Cu + Zn + Co ratio, so that only the highest values of the ratio indicate Ni-
critical serpentinites (Fig. 11-43). The high Ni concentrations originating
outside of ultramafites are due to the Ni-rich schists, which are not really
Ni critical.
The group of Ni-critical serpentinites located in the above-described man-
ner was investigated in detail by diamond drilling and the interpretation
was shown to be correct. Pyrrhotite and pentlandite were present in small
amount in many of the drilled serpentinites. There may be economically
interesting ores in the area. The maps should be equipped with fixed points
to allow the reader to make comparisons/interpretations, now it is difficult.
Cr
20
1C
/ 90
/ X \eo
3o/
\70
40/X \ 60
i50
\40
X
6 0 X
/*Χχ><
\ 30
*oJ$g^ X
\20
90/^^x7 X
A10
Ni ^ - * — * — * — * ■ J2L_ l i 1£_
—*—*—^ Cu + Z n + Co
10 20 30 40 50 60 70 80 90
Fig. 11-43. Ni/Cu + Zn + Co ratios. The shaded areas: Ni-critical serpentinites in the area.
318 Geochemical exploration examples
Esko Kontas
The study area is located in western Finland near the town of Seinäjoki.
The topography is gently sloping. In the rather flat area there are some
elevations of 10 m.
The study area is situated in the centre of a wide schist area where
the main rocks are biotite-plagioclase-gneiss, pegmatites and pegmatite-
granites (Neuvonen, 1961). Plagioclase-porphyrites are found together with
more acidic volcanites. Many mineralized occurrences have been found
in the quartz-bearing fractured contact zone of the volcanites, the most
common ore minerals being metallic Sb, Sb 2 S 3 and FeSb2S2, and less
common ones FeS, FeAsS, FeAs2, FeSbS and NiSb (Pääkkönen, 1966; Aho,
1980; Oivanen, 1982). Mineralization contains small amounts of gold: in
drill core analyses the contents generally range between 0.1 and 1.0 ppm
and at maximum reach 2-4 ppm. In the Sb-rich zones of Kalliosalo (Fig.
11-44) gold occurs at least partly as aurostibite, and in the arsenic-bearing
zones of Marttalanniemi as very fine-grained metallic gold (Aho, 1980).
The basal till cover is unevenly distributed. In hill areas it covers the
bedrock only thinly, but becomes thicker in depressions of the basement
(bedrock) and in drumlin-like tails on the distal side of the bedrock hills
(Hirvas, 1980a). The till contains a notable amount of preglacial sand
(Kauranne, 1960b). Regional mapping of surficial deposits (Mölder and
Salmi, 1954) did not reveal any preglacial weatherings in the Seinäjoki
area. However, weathered bedrock as much as 1 m thick was encountered
at Kallionsalo during till geochemical study.
The latest flow of the ice sheet in the area was from 350-360° as indicated
by the orientation of drumlins, striae and moraine. Also the basal till, and
with it ore boulders, was transported mainly by this flow from the north
(Hirvas, 1980a). According to stone counts carried out near the study area,
90% of the boulders are local rocks and the rest transported from further
away (Pääkkönen, 1966).
Samples were taken with a percussion drill at an interval of 10 m along
lines 100 m apart. At each sample site about 200 g material was taken at a
vertical interval of 1 m and, where possible, the deepest sample was taken
right at the surface of the bedrock (till/bedrock interface). The thickness
of overburden varied between 0.5 and 10 m. The two deepest samples
regardless of the material were analyzed for gold. From the samples
analyzed, 470 were classified in the field as till and 250 as weathered
bedrock or as mixed samples of those materials.
After drying, the <0.05 mm fraction was sieved from the till samples for
analysis, and the weathered bedrock/till samples were ground whole.
Seinäjoki: Au in till in an Sb zone within Archaean supracrustic rocks 319
125m
Fig. 11-44. Gold concentrations in the fine fraction of glacial till (numbers left of the line)
and weathered bedrock (numbers right of the line) in the Kallionsalo-Marttalaniemi target,
Seinäjoki. The curve delimits the Sb anomaly in weathered bedrock.
Gold was digested with HC1—H2O2 and separated from the matrix by
reductive coprecipitation using SnCl2 as reducing agent and Hg as collector.
The Hg-Au precipitate was dissolved in HC1-H 2 0 2 . The measurement
was carried out by atomic absorption spectrometry, using a graphite
furnace atomizer, a deuterium-background correction unit and a plotter.
The detection limit was 1-2 ppb (Kontas, 1981).
Because even very low gold concentration in pedogeochemical sample
materials can be significant (Brown and Hilchey, 1975), the lower limit
for a gold anomaly was set at 4 ppb for both the fine fraction of till and
weathered bedrock till. The following justification can be given for this
anomaly threshold:
(1) The average total gold content of crustal rocks is 3.5 ppb (Li and Yio,
1966).
(2) In analytical measurements the signal of 4 ppb is distinct and
320 Geochemical exploration examples
target areas, Kuukkeli and Oriselkä, on the basis of both Li intensities and
a microscopic study of the earlier till samples.
The Tohmajärvi area is situated in Karelia in eastern Finland, about 60
km southeast of Joensuu. The two target areas lie about 10 km southwest
of the centre of Tohmajärvi. At Oriselkä the terrain is characterized by low
hills and bogs, while at Kuukkeli the relief is gently sloping from north to
south, with a variation in elevation of about 15 m. Both areas lie about 120
m above sea level.
The target area is situated within the Karelian schist belt. In the
Kuukkeli target area the bedrock consists of mica schist and phyllite,
while at Oriselkä amphibolite, black schist and pegmatites are encountered
as well (Fig. 11-45). The pegmatites are thought to be related to the
large granite massive lying south of the target areas (Nykänen, 1968).
I I mica schist
amfibolite
| = | quartzite
χ known lithium-
pegmatite outcrops
Oriselkä
Fig. 11-45. Bedrock of the target area and the sampling sites of the soil samples.
322 Geochemical exploration examples
fraction (over 2 mm) was visually investigated and the number of pegmatite
fragments counted.
Anomalous Li contents in till (0.06-0.5 mm fraction) are most abundant
in the southern part of the Oriselkä area (Fig. ll-46a). Some high Li
contents were also found in the Kuukkeli area, where pegmatites have
not previously been encountered. The highest Li contents were found in
weathered bedrock samples (Fig. ll-46b) whose rock type is mica schist in
the area.
In the mineralogical investigation (0.06-0.5 mm fraction) spodumene
was found in a few samples, but in each case the number of grains was
less than 5. Montebrasite was observed in three samples from the Oriselkä
area, but only 1-2 grains in each (Fig. 11-47). Lepidolite was not verified
in any sample. Instead the samples contained abundant biotite amounting
to 70-90% of the heavy fraction (d > 2.89 g/cm3). A concentrated biotite
fraction from one sample contained 1020 ppm Li, which was almost 4 times
the content of the total 0.06-0.5 mm fraction.
Visual observation of the 2-25 mm fraction of till revealed pegmatite
fragments in samples from the southern part of Oriselkä (Fig. 11-47).
However, no Li mineral was observed in these fragments. The Li contents
of the pegmatite fragments and of selected fresh and weathered mica schist
fragments are collected in Table 11-VIII.
In all likelihood the strongest uniform Li anomaly in the southern part
of Oriselkä does not originate from the known Li pegmatites; for the
nearest known pegmatite does not lie in the direction of prominent ice
movement, and the transport distance from the other known pegmatite is
twice the prevailing transport distance in the area. Evidently the anomaly
originates from an unknown local source. But there is little hint of
economic Li minerals. The samples of highest Li concentration did not
contain spodumene, montebrasite or lepidolite. More likely it is triphylite,
the main host of Li in the known Li pegmatites, which is responsible for
the high Li contents in till. Triphylite was not observed microscopically,
but it is easily weathered and, in till, Li originally fixed in triphylite would
likely be fixed in minerals like micas. High Li contents of one separated
mica fraction indicated the importance of mica as a secondary host of Li.
The enrichment of Li in micas and other clay minerals in the weathering
TABLE 11-VIII
Li contents (ppm) of rock fragments in till (2-25 mm fraction)
16
83
70
55
RP 33
·«« 61
. 180 &5 0RP
$0 67RP 6^.RP
• 110RP b
200 6
^ 10
U
< ^ - > ^ 16
26 7
16RP £.1
31
67 RP
Oriselkä ·
3«6110RP
• 68RP ^ <*6
3*5 69RP ^ £β g2
β 20 . 35 g8
17 2
. A.200RP ^
67
. -ΛJ 37
Li-pegmatite *,o . 44
Λ . 1 "°
5
28
" ·,13
Ό 20 1 °RP ,-Q .
63
• 2% . 37
39
öiRP - 572 5 iu
UU
. Jg 88 RP 36
73
. .RlfcS 33 35
10*0 28 £2 iu
70
& . 33 .
80 67
& . 53§1RP β100
?
βλ^Λο37 δ3
9*1 *6<* 50
. & 75 δ3
& v,380RP .
57
.^ÖRP . & ,
1 81
1Λ 3°7° · 270 . &
120 100 60
71 3*2 ξθ
JU
#1 3 0 61 « <0
52 6 1
•r · $
U8 Φ *° 6fifton"»
890
55 66^° 66 I
Fig. 11-46. Li contents (ppm) in till samples and in weathered bedrock samples (RP).
Visasaari and Vuonelonoja: use of magnetic susceptibility data 325
Oriselkä
Fig. 11-47. The observed Li minerals in the 0.06-0.5 mm fraction and pegmatite fragments in
the 2-25 mm fraction. S = the sample containing 1-5 grains spodumene; M = the sample
containing 1-2 grains montabrasite; ruled area: zone of the samples containing over 70%
granite or pegmatite fragments in the 2-20 mm fraction.
• • · I* / o
/ • o l · ·
• L °· · • o —-^# A
w #
° o" · φ o o o o · # o
w
o ° o o o ·
• • •
• Cr ppm Cu ppm
•
Fe % Mn ppm
• <357 • <80 • <10.0 • <1228
# O 357-611 A O 80-89 A O 10.0-1 1.8 A 0 1228-1440
W
O · >89 • . · >11.8 • 0 · <1440
/ • V O
• / ° o
o • / #. ° . / ° o \ o . . /° · \ · ·
• /. * · ·
• • / i ^ · ° • Λ·^ ° * *
o °
• o · · • r#· o · • o ° '
• • o · ' 500 m W
0 ΙΊ
o o
Fig. 11-48. Dispersion of magnetic susceptibility in the 0.06-0.5 mm (Kk) and <0.06 mm (ÜCP)
fractions of glacial drift and dispersion of magnesium (Mg), calcium (Ca), chromium (Cr), copper
(Cu), iron (Fe) and manganese (Mn) in the <0.06 fraction of glacial drift in the Visasaari area.
Number of samples per sampling site varies from 2 to 10. The dashed line outlines the source
area.
1'
o o 8
1i * 1
o o
|
§
8
^ 8 o • : ■ 8 °
I
Mn ppm Mg % Cr ppm
• <646 • <1.6 • «413
O 646-877 O 1.6-2.1 O 413-693
• >877 • >2.1 • >693 II
1 §# if
o #
I •
I
o O
o O
i
o
! '* I
° /#* ° •• o
o T i o o
•• •
• o
o o
* *
o • o o o §
8 • 500 m o
Fig. 11-49. Dispersion of magnetic susceptibility in the 0.06-0.5 mm (2fk) and <0.06 mm (K?)
fractions of glacial drift and dispersion of iron (Fe), manganese (Mn), magnesium (Mg) and
chromium (Cr) in the <0.06 mm fraction of glacial drift in the Vuonelonoja area. Additional
explanations as in Fig. 11-48.
From: Miller, J.K., 1979. Geochemical dispersion over massive sulphides within the con-
tinuous permafrost zone, Bathurst Norsemines, Canada. In: Prospecting in Areas of
Glaciated Terrain, Dublin, 1979. Institution of Mining and Metallurgy, London, pp.
101-109.
The Camp Lake area is located in the Bathurst mine area in northern
Canada, 480 km northeast of Yellowknife. Flat and swampy lowlands and
gently rolling hills create a subdued topographical relief (20-50 m). The
mean annual temperature of — 12°C and average precipitation of 280 mm a
year are typical of cold desert. Vegetation is sparse: dwarf birch and willow,
grass, moss and lichens. Permafrost reaches down to 500 m, but the surface
is thawed to 2 m depth in summer.
Bedrock consists of Archaean metasediments, silty schists and tuffitic
metavolcanites. Underlying an assemblage of about 1500 m thick epiclastic
metaturbidites is a sequence of calcareous and argillaceous rhyolitic tuffs
with massive stratabound sulphide mineralization, and under these are a
set of andesitic and rhyolitic flows, tuffs, pyroclasts and breccias.
The glacigenic overburden consists of till of perhaps more than one
glaciation, eskers, outwash deposits, kames, drumlins and numerous of
erratics. The two transport directions are towards west-northwest and
southwest. Soil development has been disturbed by cryoturbation: frost
heave, boulder circles, solifluction, mud boils, etc. On the surface there is
a 1-5 cm thick humus layer (referred to as LFH in abbreviation of litter,
fermentation, humification) and under it poorly developed brunisol, regosol
or gleysol.
The purpose of the study was to determine the suitability of geochemical
methods for prospecting in a permafrost area, where permafrost, according
to earlier assumption, prevents hydromorphic transport of metals.
Samples were collected over a 120 x 30 m grid from humus-rich surface
soil and from mineral materials at 0-35 cm depth (layer 1) and 35-64 cm
depth (layer 2). Lake sediments were collected along the watershed. In
addition, a number of profile samples were taken from pits, 5 cm vertical
intervals down to the frost table level. Ground water seeping into pits,
snow meltwater running on the surface and lake water were collected as
well. Samples of humus and the -0.18 mm fraction of the different mineral
Camp Lake: heavy metals in sediments of a dry permafrost area 329
TABLE 11-IX
Fig. 11-50. Lead (ppm) in the <177 μηι grain size fraction: (A) of surface soil, (B) at depth of
35-64 cm at Camp Lake, Canada.
TABLE 11-X
Zn Cu Pb
Z n , Cu and Pb in lake sediment p - ^ ^ 1998/1462/47
2000/1500/50 ppm
^ " " \ Β α η α η α ^ ν . 647/285/15 κ1
V
/y' -^Jake^i6r ΓΚ 1113/420/9
Zn and Cu in lake water
-^J WZn 18, \ \(Zn<7,
(70, 10) ppb
' \ Cu 2) 742/722/3C\ · I Cu <2)
Bat lake\
^xg) massive sulphides \A32m) | . \2321/653/36
,498/685/182
6264/883/30^ ^£
g, 392/794/20
*
4 8 3 5 / 1 5 1 1 / 2 5 6 / C a mp
§ } 309/808/13
3396/2260/286" Λ χ· l a | < e *\\
642/1421 /302\v l\U m ^y 370/925/9
558/887/239\.
551/637/185^ N . 430/524/179
226/356/46 I *
> / \ ^ (Zn 65, Cu 8)
(Zn 72, CuS^ \~"^^419/241/31
Sunken ^ - ^ - — ^ \
lakesx^x/\i75/59/3
®
(Zn 2 β Ν θ \ v
Cu 2) XN,
(Zn 85, Cu<5)
| 0 1 km
^
Fig. 11-51. Copper, lead and zinc (ppm) in lake sediment and zinc and copper (ppb) in lake
water at Camp Lake, Canada.
had destroyed all the original sulphides in surface soil. Experiments show-
that lead is easily extracted from humus, e.g. by EDTA, but copper and
especially zinc are not.
332 Geochemical exploration examples
This excellent study shows that extensive clastic dispersion trains and
primarily glacigenic geochemical anomalies are formed in the Arctic. Later,
they may be reformed by seeping ground water, weathering and further
hydromorphic transport. During the transport from lake to lake, elements
in water solution have been gradually separated from one another, as seen
in the change of ratios of element concentrations.
The report recommends analysis of lake sediments for regional studies
and analysis of till for detailed exploration. A general conclusion of the
study was that the effects of permafrost on geochemical programmes
are minimal; hydromorphic and clastic dispersion patterns may be even
better developed than in the temperate zone. It was unfortunate that the
sampling of overburden could not be extended deeper than 2 m, the level of
permafrost.
From: Andrews, M.J., Bibby, J.M., Fuge, R. and Johnson, C.C., 1984. The distribution of
iodine and chlorine in soils over lead-zinc mineralization, east of Glogfawr, Mid-Wales.
J. Geochem. Explor., 20: 19-32.
76 76
0 500 m 0 500 m
Fig. 11-52. The distribution of total and water soluble iodine (ppm) in the -120 mesh crushed
fraction of drift at Glogfawr, Wales.
the strike of the mineralized zone. The samples were dried, disaggregated
and sieved. The <200-mesh fraction was analyzed for total iodine from
the water solution of a sample fused with K 2 C0 3 , Na 2 C0 3 and MgO by
the automated catalytic/photometric method of Fuge and Andrews (1985).
Water-soluble iodine was determined after leaching of the sample with
distilled water, shaking and centrifuging. Also F, Cl, As, Pb, Zn, Cu, LOI
and pH were determined by different methods.
Both the total and the water-soluble iodine distribution curves show
distinct populations (Fig. 11-52). The arithmetical mean of background
population concentrations is 5.8 ppm for total I and 0.1 ppm for water
soluble I. Corresponding values for the anomaly populations are Itot 47 ppm
and I aq 1.7 ppm. About 30% of the samples belong to the log normally
distributed background population, the rest to the log normal "anomaly"
population.
Both iodine and chlorine anomalies pick out the known mineralization.
The strongest anomalies lie directly above the suboutcrop of the dissem-
inated zone, and also upon the possible continuation of it towards SSW.
Among the metals Zn seems to be correlated with pH and thus dependent
on drainage, but Pb and Cu pick out the area of known mineralization
(Fig. 11-53).
The highest concentration of total iodine (149 ppm) is found at the
same site as the highest concentration of total chlorine (520 ppm) and the
highest Cu and Pb concentrations. The water-soluble I and especially the
Cl anomalies are elongated towards the southeast. The authors suppose
334 Geochemical exploration examples
50 75 100 50 75 100
" ' i 1
0 500 m 0 500 m
Fig. 11-53. The distribution of lead and zinc (ppm) in the -120 mesh crushed fraction of drift
at Glogfawr, Wales.
that the extremely high I and Cl concentrations have been formed by the
enriching absorption of clay minerals and they do not attach importance to
the organic matter; even if there was a marked positive correlation both
between the total halogens and loss on ignition. The small concentrations
of halogens leached into water show that they are fairly strongly bound.
Anomalous iodine and chlorine concentrations were also found some 200
m east of the main anomaly zone. Glacial transport of drift cannot explain
these anomalies because it parallels the direction of the fracture zone
and the long axis of the main anomaly. Possibly there is another parallel
mineralized zone, as the VLF curves would suggest as well.
There is a strong and wide Pb anomaly and anomalous concentrations
of Cu, I and Cl as well to the west of the "main" anomaly. These were
not investigated more closely but considered to be "false" by the authors
because they had no geophysical equivalent.
The study showed iodine and chlorine to occur in soil in this area in
truly anomalous amounts. The average halogen concentrations in the ores
of Mid-Wales are only 138 ppm Cl and 2.5 ppm I in galena and 290 ppm Cl
and 1.5 ppm I in sphalerite. Maybe in this type of breccia there are iodine-
and chlorine-rich fluid inclusions both in ore and in gangue minerals.
In any case the halogens, as well as the ore metals themselves, formed
geochemical anomalies on the surface of drift above the known disseminated
mineralization 3-5 m below. It would seem that a simple method of
determining water-soluble halogens could be useful in soil geochemical
exploration for base metals.
Hiendelaencina: elements in a mixed sandy and in situ weathered overburden 335
The sampling lines should have been plotted on the maps. The method of
visualizing the results by classifying and generalizing the data into different
concentration classes makes for clarity but does not allow the reader to
draw his or her own conclusions.
It is unfortunate that the different sampling materials and their con-
centration distributions were not discriminated, because the reader cannot
really know now whether any of the conclusions are right — so great,
usually, are the differences between the heavy metal concentrations in till,
sorted sediments and peat. It is regrettable, too, that samples were not
taken vertically through the overburden at some sites to detect possible
movement of materials. Glogfawr is a fine example of experimenting in
geochemical exploration with the determination of exotic elements — some-
thing not often done, but which seems to have succeeded positively in this
case.
From: De Vos, W and Viaene, W, 1980. Geochemical study of soils and metallogenic
implications at Hiendelaencina, Guadalajara, Spain. Mineral. Deposita 15: 87-99.
and especially to see whether the newly discovered continuation of the vein
at a depth of 300-500 m would show up. The study was simultaneously a
follow-up stage to a regional stream sediment survey which had discovered,
besides anomalies caused by contamination from the old tailings, As
anomalies with no obvious interpretation.
Soil sampling was done along lines approximately perpendicular to the
vein and 100 m apart. The sampling interval was about 50 m and the depth
of sampling 5-20 cm beneath the organic rich topsoil. Samples were dried
and sieved, and the <0.18 mm fraction, after digestion with a mixture of
HC1 + H N 0 3 + HF and evaporation to dryness from a water solution, was
analyzed by AAS for Mn, Fe, Ni, Co, Cu, Zn, Pb, Ag and Ba. As and Sb were
determined by AAS with a hydride generator.
The results visualized on the maps were classified according to the
populations discovered from the frequency distribution curve. Filon Rico is
clearly indicated by a 50-100 m wide anomaly which varies longitudinally.
The distribution patterns of Pb, Zn and Cu resemble each other closely.
Highest Mn and Fe concentrations are found at the western end of Filon
Rico, above the limonitized vein. The distributions of Ag and Sb resemble
that of As: there are anomalies above Filon Rico, high anomalies around
old tailing heaps, and large anomalies some 400 m south of Filon Rico
(Fig. 11-54A and B). These last anomalies are perhaps better shown in the
nonclassified concentrations plotted on a N-S directed line (Fig. 11-55);
the abruptness of the Filon Rico anomaly and the width of the southern
anomaly show up particularly well.
" ' 1 I · · 1 1 1
0 100 200 m . o 100 200 m
Fig. 11-54. Distribution of (A) lead and (B) arsenic in drift (in Rana = a mixture of gravel, sand,
clay and weathered bedrock material) <0.18 mm fraction at Hiendelaencina, central Spain.
Hiendelaencina: elements in a mixed sandy and in situ weathered overburden 337
o Ί~ 500
Slope
1000 m
Filon Rico
Fig. 11-55. Distribution of lead, zinc, arsenic and silver in the <0.18 mm fraction of drift along
a line crossing the Filon Rico mineralized vein at Hiendelaencina, central Spain.
It seems that above Filon Rico the overburden is very local; only the
Ag anomaly is slightly shifted to the south. The northern border of
the southern anomaly is sharp indicating, as the authors state, a linear
structure, possibly a mineralized vein. Slightly decreasing concentrations
towards the south in anomaly indicate the width of the source in bedrock
but also suggest soil creeping along the slope. The transport of elements by
groundwater seems unlikely.
It is a pity that no sampling in the overburden was done in the vertical
direction. Even though the layer of loose material, in the area is thin such
an investigation could have been informative about the redistribution of
the elements during weathering and the formation of rana. Mineralogical
and chemical studies of the mode of occurrence of the metals in overburden
could have helped in the interpretation. The source of the southern anomaly
could have been detected simply by digging through the thin overburden
and one wonders why that was not done. The extension of Filon Rico was
338 Geochemical exploration examples
studied in that way and a vein, although sterile at the rock surface, was
detected.
The results were manipulated by statistical methods after removal of
extreme values. Treatment was made difficult by the fact that many of
the Ag concentrations are the same as the detection limit. There is a
high positive correlation between Pb and Zn and between As and Sb, and
the latter exhibits a good correlation with Ag as well. Zinc, in turn, is
clearly correlated with Mn. Factor analysis strengthened the assumption
that the original paragenetic relations in ore have been much altered in the
formation of soil. Geochemical analysis of residual soil and of the sorted
materials originating from it revealed that both are very local and suitable
for exploration use.
From: Laville-Timsit, L. and Wilhelm, E., 1979. Comportement supergene des metaux
autour du gite sulfure* de Porte-aux-Moines (Cotes-du-Nord). Application ä la prospec-
tion geochimique. Bull. BRGM, Sect. II, 2-3: 195-228.
Laville-Timsit, L., 1986. Neoformation de sulfures de fer et de zinc en milieu reducteur
en aval du gisement Pb, Zn, Cu, Ag de Porte-aux-Moines (Cötes-du-Nord): l'anomalie
geochemique Pb-Zn des sols de Kerouran. Sei. Geol. Bull., 39 (3): 263-275.
Fig. 11-56. Distribution of (a) lead and (b) zinc (ppm) in surface soil at Porte aux Monies,
mid-Bretagne.
L
H^
7ΠΓΧ LÜ!
I
I
oo ' oo
ooo oo
ooo oo oo
C9 T- CO i - CO I CM(0
ppm +- ppm 111111 p p m
3H loo o oo IOOO
ooo 10 O
ooo
i-iOO i-*C0
CM
Pb Zn Mn
Fig. 11-57. Concentrations of Pb, Zn and Mn (ppm) in overburden along a 72 m long N-S
directed vertical profile across the lead and zinc anomalies at Porte aux Moines, mid-Bretagne.
concentration
10 100 1000
Fig. 11-58. Concentrations of Pb and Zn (ppm) and Fe (%) in a drill hole through gossan at
Porte aux Moines, mid-Bretagne.
Grudie Burn: Mo in peat of temperate moist hilly terrain 343
TABLE 11-XI
Average total contents of important metals in assayed materials at Porte aux Moines
From: Smith, R.T. and Gallagher, M.J., 1975. Geochemical dispersion through till and
peat from metalliferous mineralization in Sutherland, Scotland. In: Prospecting in
Areas of Glaciated Terrain, Edinburgh, 1975. Institution of Mining and Metallurgy,
London, pp. 134-148.
The Grudie Burn West target area lies in the eastern Highlands of
Scotland. The region is hilly and mostly freely drained. The elevation of
the more or less even valley flank west of Grudie Burn stream ranges from
200 to 360 m a.s.l. The climate is coolish and moist. Vegetation consists of
conifers, heath, grass and, upon thicker peat bogs, Sphagnum moss.
The bedrock of the area is Precambrian micaceous metamorphosed sand-
stone with some mica schist intruded by Caledonian granite. Molybdenite
occurs sparsely over a larger area, both in sandstone and granite, with
pyrite and fluorite. Rock exposure is poor. In the exposed mineralization,
molybdenum occurs with pyrite in the quartz veins cutting the platy mica
schist.
The average thickness of overburden is 4.3 m, but in places till exceeds
15 m and peat 3 m in thickness. Peat on average 0.8 m thick, covers
the sandy lodgement till with a gleyed podsol soil profile over the entire
area. Some mineralized boulders have been found south of the exposed
Mo mineralization. The correlation between the location of mineralized
erratics and mineralization in bedrock is not clear. The valley glaciers
moved generally towards the south east — in Grudie Burn valley along the
contour lines.
344 Geochemical exploration examples
(a)
- Sampling point
Mo in peat ash
6 21 150 PPm
§
(b)
HJ
Sampling point
Mo in till fines
20 35 70 PPm
w 1000 m
Fig. 11-59. Distribution of molybdenum in (a) peat (ppm, in ash) and (b) till <0.15 mm fraction
(ppm) at Grudie Burn, Scottish Highlands.
Fig. 11-60. Vertical distribution of Mo, Cu, U, Mn and Fe in a drill hole through peat, till and
weathered rock down to bedrock at Grudie Burn, Scottish Highlands.
From: Nieminen, K. and Yliruokanen, I., 1976. Kitee: the copper-nickel anomalies of
Lietsonsuo peat bog. J. Geochem. Explor., 5: 248-253.
Lietsonsuo bog lies in southeastern Finland close to the border with East
Karelia. The undulating topography allows fairly free drainage except in
the silt-paved depressions. Climate is coolish and humid. The forest is a
mixture of deciduous trees and conifers with the common Vaccinium-type
undergrowth. A sparse growth of stunted spruce and pine characterizes
the bog surface. The bog was originally mainly the floating type, but has
developed into raised bog with Sphagnum moss as the main plant.
Bedrock is Proterozoic gneissose mica schist surrounded by pegmatitic
granites. The overburden consists of till, covered by glacial varved clays in
flat areas and bordered by a ridge of coarser glacifluvial formations in the
east. Two transport directions are known, the older from NNW and the
younger from WNW Soils are podsolic. No ore mineralizations have been
discovered.
The purpose of the study was to find whether heavy-metal-rich peat
layers could be mined as ore and to search for the source of the metals in
bedrock.
Lietsonsuo: Cu and Ni in peat of humid coolish plain terrain 347
500-
Ni concentrations
in peat ash
500
fflffls
Cu co ppm co Ni
Fig. 11-61. Distribution of copper and nickel in peat (maximum concentrations in the bog, ppm
in peat ash) and vertical distribution of copper and nickel along a typical line (ppm, in peat
ash) in Lietsonsuo bog, eastern Finland.
The bog was sampled at 100 m intervals along lines 200 m apart; samples
were taken vertically, one every metre from top down to hard bottom. The
peat was dried, ashed at 550°C and analyzed by XRF for copper, nickel,
zinc, lead and uranium.
According to the report the distributions of Cu and Ni are very similar.
The maximum concentrations at every point are presented in map form in
Fig. 11-61. The concentration contour lines are very similar for the two
metals, with highest concentrations approximately at the centre of the bog.
Figure 11-61 also shows the vertical distribution of Cu and Ni along one of
the east-west directed lines.
The concentrations of Cu and Ni are low in the surface and bottom
samples, although most heavy metals tend to concentrate close to the
348 Geochemical exploration examples
bottom (see Salmi, 1967). The highest concentrations in ashed samples from
the middle of the bog are over 2000 ppm for Cu and over 3000 ppm for Ni.
Unfortunately, the report says nothing about the distribution of zinc, lead
and uranium. From other investigations we know that lead and usually also
iron and molybdenum are concentrated in the surficial layers of peat, while
uranium, like titanium and vanadium, has a tendency to concentrate near
the bottom. Zinc resembles copper and nickel in being more indifferent.
It is further regrettable that clay/silt under the peat was not sampled at
all, and that till was sampled only along two lines, with results presented
very unclearly The few samples taken from till revealed weak anomalies
of about 130 ppm Cu and 120 ppm Ni at the place where a rise in the till
surface penetrates the clay bottom paving of the peat layer. The highest
concentrations in peat occur at about the same height level as the surface
of this till elevation.
Although the heavy metal concentrations in mineral formations are
much lower than those in dried peat and especially those in peat ash,
the element distribution pattern in till have been informative about the
transport direction. The heavy metal spectrum of till might also reveal
the type of source mineralization. In peat the original internal ratios
of elements have been distorted and cannot be used as a "fingerprint"
of the mineralization. Peat study can be recommended for regional and
semi-detailed base metal geochemical exploration but, judging from this
example, not for target studies.
From: Armands, G., 1967. Geochemical prospecting of a uraniferous bog deposit at Ma-
sugnsbyn, northern Sweden. In: A. Kvalheim (Editor), Geochemical Prospecting in
Fennoscandia. Interscience, London, pp. 127-154.
hummocky ablation till occur on either side of the bog. Numerous magnetite
and sulphide ore erratics, but no boulders with marked radioactivity, have
been found. Because the area lies on the ancient ice divide, glacial transport
has been short. Glacial striae point in two distinct directions: the older
towards east-southeast (from 300°) and the younger towards northeast
(from 225°).
The waters and peat are radon and uranium rich. The anomalous area
was found during car-borne scintillation counting on the Kiruna road in
1958. The purpose of the geochemical study was to find the source of the
anomalies.
The highest uranium content in water (1800 /zg/1) was found in one of
the bore holes getting water from fractures in the bedrock. Ground water
in till contained 2-3 /ig/1; natural springs in depressions showed an average
of 6 /ig/1, but some had contents of more than 700 /ig/1. Such a spring would
produce about 6 kg uranium annually. Uranium concentration in streams
varied from 0.2 to 7.2 /^g/l.
Observations made on vegetation showed variable uranium concentra-
tions in different species and in different parts of plants. Amounts were
highest in willow (ppm in ash): twigs 680, leaves 450 and fruit 450. The
activity of willow (Salix) twigs was 2.5-fold that of willow leaves, while the
corresponding value for alder (Alnus) was 1.9, for dwarf birch (Betulanana)
2.5 and for birch (Betula alba) 3.9. The radioactivity measurement shows
how geophysical methods can give good though vague results in uranium
exploration.
No systematic study was made of the uranium concentrations in till, but
there was a positive correlation between the uranium concentrations in till
and in water. There was also a correlation between uranium content of
the water in peat and that of the peat material itself. As expected, neither
the uranium or radon concentrations nor the activity in waters or in peat
were in equilibrium with each other. The correlation between the uranium
concentrations of surface peat and surface vegetation is not at all clear,
although one would think that the only way bushes can get their uranium
is via water from the peat.
Peat, like humus, is a strong concentrator of heavy metals. The highest
uranium concentration found at Masugnsbyn was 3.1% in dry peat; the
average amount in 445 samples was 600 ppm U in dry material. Peat was
impure: 33% of its dry weight was mineral grains. The enriching factor
if attributed to organic material was thus 9000. According to laboratory
experiments done by Szalay (1958), the enriching factor for uranyl ions
between a dilute water system and a peat system could reach 10,000.
Uranium is easily leached from granite or its ores by HCO3-rich water of
pH about 7.5. It is precipitated with manganese at pH 7.4-7.9 and fixed in
peat between pH 3 and 7.
At the surface of the peat bog the uranium anomaly is branched into
350 Geochemical exploration examples
U concentration
in dry peat
100 m
Fig. 11-62. Distribution of uranium in surface peat (ppm, in dry peat) at Masugnsbyn, Swedish
Lapland.
Fig. 11-63. The acidity of peat in a vertical profile through the bog, the distribution of uranium
in peat layer and the radioactivity of surface peat at Masugnsbyn, Swedish Lapland.
Masugnsbyn: U in peat in humid arctic hilly terrain 351
Rn
1000 (emans) 2000
Fig. 11-64. Uranium concentration in peat and in peat water as well as 7-radiation on the
surface of the bog along the N-S profile at Masugnsbyn, Swedish Lapland.
two parts, possibly reflecting the movement of water in the peat layer. The
longer branch is broken by background concentrations (Fig. 11-62). The
highest concentrations at the surface are well over 4000 ppm (0.4% U, in
dry peat). As is very often the case, the highest heavy metal concentrations
occur in the bottom layers of the peat, (Fig. 11-63), although one 1%
U-content in the N-S profile was found at the surface south of the ditch.
The measured radiation (7-activity) on the peat surface does not follow the
distribution of uranium in either peat or peat water (Fig. 11-64).
In the Masugnsbyn case, a very thorough investigation was made of the
uranium in peat and the factors affecting it. The concentrations of U, Rn, Ra
and the radioactivity were measured — however, conclusions could not be
drawn about the partitioning and the causes of imbalance of the daughter
elements of U and Th. Factors affecting the solubility and precipitation of
uranium — acidity (pH), redox potential (Eh), degree of humification (H),
amount of mineral material (ash%) and concentration of manganese (Mn)
— were studied and internal correlations calculated. It was found that
neither pH or Eh could explain the variation of uranium concentrations,
but that Mn and especially the ash% affected the precipitation and fixation.
It was concluded that uranium is leached from bedrock by ground waters,
which seep out to the overburden from several fractures, enriching uranium
in the organic material.
352 Geochemical exploration examples
One very important medium was not properly explored — the mineral
overburden under the peat. Test sampling revealed variation in uranium
concentrations in the till. A fuller picture of the distribution of uranium
in till could have given valuable information on the places where ground
water is seeping into overburden from the fissures of the rock and perhaps
on where the richest mineralizations are located in the bedrock.
Analysis of peat is a useful tool for regional or semi-detailed uranium
exploration, but it cannot be recommended for target studies with which
sampling of bedrock (diamond drill holes) must be planned.
From: Toverud, Ö., 1979. Humus: a new sampling medium in geochemical prospecting
for tungsten in Sweden. In: Prospecting in Areas of Glaciated Terrain, Dublin, 1979.
Institution of Mining and Metallurgy, London, pp. 74-79.
The Allebuouda prospect lies a little south of the Arctic Circle in northern
Sweden, where the climate is cold and moist. The Allebuouda fell, rising
180 m above the surface of lake Björnträsk, is typical of the rounded,
well-drained hills characterizing the region. Vegetation consists of dwarf
birch, juniper, heath, grass and moss.
Bedrock of the study area consists of Precambrian metavolcanites and
granite intruded by aplite and pegmatite veins. Scheelite mineralization
with some molybdenite occurs in tuffaceous skarn close to the northern rim
of a granite dome.
The overburden varies in thickness up to a maximum of 10 m, disappear-
ing in the western and northwestern parts of the area where rocks outcrop
on the top of fells. Glacial till with a podsolic soil profile on top is covered in
the southeastern corner of the area by peat. A 1 km long scheelite-bearing
garnet-skarn boulder fan curves round the flanks of the Allebuouda fell
towards the southeast at the apex about 320°, at the tail 350°. Glacial striae
are oriented between 320° and 335°, but there is also an older direction
from 300°.
The purpose of the study at this fairly well-known prospect was to
compare the results of a chemical analysis of humus with the results of an
analysis of the heavy fraction of till to assess the suitability of humus as an
exploration material for tungsten. Counting of scheelite (and wolframite)
grains under ultraviolet light from a panned heavy mineral concentrate of
till has long been considered a sensitive and reliable exploration method for
tungsten, whereas to determine tungsten chemically has been tedious.
Samples were collected from the C-horizon of till at about 50 cm depth
on a 100 x 200 m grid. After drying and sieving of the samples, the heavy
metal concentrate of the 0.5-5 mm fraction was analyzed for selected
metals by X-ray fluorescence. Humus, which in the area is 2-5 cm thick,
Allebuouda: W in humus of humid mountainous environment 353
Fig. 11-65. Distribution of tungsten in the heavy mineral concentrate of the 0.5-5 mm fraction
of till (ppm) at Allebuouda, Swedish Lapland.
was sampled from the same grid, ashed at 450°C and analyzed for metals
by ICP spectrometry
Tungsten concentrations of the till samples are not high even though
the material analyzed was enriched by panning; neither is the anomaly/
background contrast strong. The anomaly in heavies of till has clearly been
derived from the ore suboutcrop in the bedrock. Its failure to coincide
with the ore boulder fan, though not usual, requires an explanation.
Separation due to solifluctional creeping of surface till rich in boulders
seems improbable. In fact, there are two anomalies in till, separated
by a 200 m wide gap (Fig. 11-65). If these represent the same source,
the material lying to the southeast must have been transported by an
older ice movement and then may be pushed a little towards the southeast
354 Geochemical exploration examples
Fig. 11-66. Distribution of tungsten in ashed humus (ppm) at Allebuouda, Swedish Lapland.
The report does not tell about the overburden above the ore suboutcrop,
nor what results were obtained in the analysis of the - 0 . 1 mm till fraction.
It would have been important to investigate the occurrence of tungsten
deeper down in the till, at the apex of the anomaly. What is the relation
between the anomaly and the suboutcrop of the mineralization? Deeper
sampling of till at the gap between anomalies might have revealed the
reason for the gap.
There is in the report a mention of a mineralogical study of the till and
the identification of scheelite and wolframite by XRD. Presenting of the
results of the scheelite grain count of the heavy fraction of till would have
assisted the reader in the evaluation of the suitability of humus analysis
for tungsten exploration.
As an assessment of the usefulness of humus analysis in tungsten
exploration, the investigation perhaps was good enough. In the case of
real exploration, the sampling network should have been larger and, in
the second stage, denser in the central area to verify the preliminary
interpretation. Some deeper pits should have been dug northwest of the
apex of the till anomaly and sampled at different depths to follow the
anomaly in vertical direction.
Geochemical study of humus is not accurate enough to allow location
of diamond drill holes that will hit an ore and allow inventory of the
mineralization.
Cu Cu/C
ppm
15 0.015
— i i 1 1 1
500 1000 1300r
FeyFe/C
2.5 10
0-L0
1300 m
SP
mV
300H
150
OH
1300m
-75
200m ^Μο/}ζοη]}9/
Fig. 11-67. Copper and iron contents of humus and their ratio to carbon contents as well as self
potential along a line crossing the Laurinoja ore deposit at Hannukainen, North Finland.
the 1-5 cm thick humus were taken at 50 m intervals along E-W directed
lines 200 m apart. In depressions where there was a thin peat layer, this
was sampled instead of humus. By way of comparison, the suitability of till
geochemistry was investigated as well.
Samples of upper till were taken from a depth of 2 m, at 100 m intervals
along lines (NW-SE, perpendicular to glacial transport) 1 km apart. Some
of the drill holes were driven down to the bottom of the overburden and
sampled every metre.
Till samples were dried and sieved. The 0.06-0.25 mm fraction was
reserved for mineralogical studies while the —0.06 mm fraction was divided
into three parts. Total contents of Cu, Ni, Co, Zn, Mo and Fe were
determined in one part by optical emission spectrography, and the other
two parts were digested, one in a hot HC1 + H2O2 mixture and the other in
diluted cold HC1 before analysis by AAS for the same heavy metals.
Humus and peat samples were dried, ashed at 500°C, digested in hot
(1:1) HC1 and analyzed by AAS. Results were calculated back to dry mass.
The mean concentrations of the metals in about 450 till, 500 humus and 90
peat samples are presented in Table 11-XII.
Amounts of magnetite determined by susceptibility from the 0.06-0.25
mm fraction of mineral materials were highest in the tills, whereas the
sand bedded between them was poor in magnetite. The same pattern was
mostly true for the heavy metals too. Copper showed highest average
concentrations in the lower till.
Immediately east of the largest ore outcrop (Kuervaara) the copper
content in the upper till is highly anomalous: hot leach copper concentration
350 ppm, compared with a concentration of 1000 ppm in the ore below. The
distribution pattern of the heavy metals in the upper till is very peculiar:
namely, the anomalies partly lie to the southwest of the suboutcrops of
the ore bodies, on the "wrong" side to what one would expect from the
glacial transport. Anomalies in humus show the same feature near the ore
suboutcrops (Fig. 11-68). The most distinctive anomalous areas of the cold
TABLE 11-XII
Average metal concentrations in till, humus and peat in the Hannukainen area
&-'·?
rtJ \ Λ fV«'
Jfifi'''
Cu concentrations
f
in fines of till
acid soluble
> 28 ppm
V ; \»"i
Fig. 11-68. Distribution of copper concentrations in humus and till at Hannukainen, North
Finland.
leach copper concentrations in till are to the west of the second outcropping
ore body (Laurinoja).
The maximum total concentrations of copper in till are found on the
northern side of the long "blind" orebody (Vuopio). The maximum total
concentration of Cu in the upper till determined by optical emission
spectrography is 1050 ppm, compared with 600 ppm in hot leach and 180
ppm in cold leach. The maximum total copper concentration in the lower
till is 1770 ppm. There are very high levels of copper in the sand between
the tills too: maximum total concentration is 1450 ppm.
Petalax: heavy metals in humus of humid temperate climate, plain terrain 359
The Petalax study area is located in the low-lying western coastal zone
of Finland. The area appears to be fairly freely drained, although the
topographical variation is small. The target lies on a low crest between two
360 Geochemical exploration examples
TABLE 11-XIII
The average total, mineralic acid-soluble and exchangeable Ni and Cu of till in Petalax
Fig. 11-69. A. Distribution of cold citrate extractable heavy metals (ex Hm) (Ni + Cu + Zn
+ Pb) in humus (ml of dithizone consumed). B. Distribution of the Ni + Cu + Zn + Pb
concentration (ppm) in the fines of till at 1 m depth, at Petalax, western Finland.
ore suboutcrop. In the present case the higher concentration in surficial till
in the southern part of the study area, 300 m south from the deposit, may
be the first real expression of the ore in the down-ice direction and the till
anomaly just begins to show up.
Maybe the ore-bearing tillmaterial at the apex of the anomaly is situated
close to the bedrock surface and was not reached by the 1 m sampling.
The anomaly in humus may reflect that material and maybe the weak sum
anomaly in till above it has hygroscopically climbed up from that deeply
situated material. Analysis of the hydromorphically transported part of
the heavy metal concentrations in till should have been performed. This
case was not studied properly and even the classification of the metal
concentrations in till and their presentation with class symbols on the map
prevents readers from drawing their own conclusions.
363
Chapter 12
PRINCIPLES OF GEOCHEMISTRY
ANOMALIES
Every element has a certain average concentration (clarke) with its spe-
cific standard deviation in any particular material. A standard composition
for every material can thus be defined and used in identification of that ma-
terial from a group of samples. Deviations from the standard composition
are called anomalies.
In exploration geochemistry it is usual to consider concentrations greater
than the areal average plus 2 standard deviations to be anomalous. This
simple definition of anomalies is suitable for small area/high density
sampling studies. Sometimes anomalies are true, sometimes "false" (Ra-
manamurthy, 1983), sometimes strong, and sometimes so weak that only
368 Focal aspects of geochemistry applied in arctic and temperate regions
[-100%
Cr NiCuPb 80
f 60
40
h20
+ %
Averages
Cr 232 ppm
Ni 102 - -
Cu 90 - -
Pb 31 - -
Fig. 12-1. Residual anomalies showing copper and lead, chromium and nickel and lead-rich
bedrock horizons on the northeast side of Levi fell, Finnish Lapland.
SCALE
in two or three successive phases. The same final procedure has been used
by Horsnail (1975), who recommends for Ireland rectangular sampling on
250 x 125 m and 50 x 50 m nets.
In work at scales greater than 10 samples/km 2 , maximal results will
be achieved with minimum cost if the following factors are taken into
account in planning the sampling grid: strike of bedrock formations (see,
e.g., Savinskii, 1965; De Geoffroy and Wu, 1970), the stratigraphy of
sampled material and its transport directions (e.g., DiLabio, 1989; Hirvas
and Nenonen, 1987; Shuts and Smith, 1986; Stea et al., 1986), grain size
and inhomogeneity of material (Gleeson et al., 1988; Nichol, 1986; Shuts,
1973; Xie and Zheng, 1983) and pollution (Qvarfort, 1979).
SAMPLING MATERIAL
Transported drift
The geochemical character of transported overburden formations de-
pends on the type of transport and mode of occurrence of their constituents.
Disintegration of rocks and the separation of minerals and chemical ele-
ments from each other depend on the transporting medium, whether this
be gravity, pushing glacier, flowing water or air, as described in Chapter
3. To a large extent transport occurs mechanically as grains, but in water
also as ions or molecules. To understand fully the geochemical character of
a material and the provenance of anomalies in it, the way in which it has
been formed needs to be known. Thus Chapters 2, 3 and 4 of this volume
have presented a broad description of the formation of glacigenic and other
types of overburden deposits and soils.
Talus represents the original bedrock, which has simply been loosened
mechanically and transported freely by gravity down along the mountain
flanks. Only some separation of rock types according to form and size of
the fragments occurs during the rolling and sliding of the material.
Most glacial till is likewise chemically fresh, although preglacial materials
— chemically altered crust, sorted sediments and even organic deposits
— may be intermixed. During glacial transport minerals are comminuted
and elements differentiated into different grain sizes and lithologies are
described by Eriksson in Chapter 2 and by Salminen in Chapter 5 (see also
Andrews et al., 1983; DiLabio, 1982; Hyvärinen et al., 1973; Minell, 1980;
Peuraniemi, 1989; Saarnisto and Taipale, 1985; Salminen, 1980; Shuts,
1975; Shuts and Smith, 1989; Toverud, 1984).
The main mass of till has typically been transported only some hundred
metres (Kauranne, 1976b), but an identifiable part may have been trans-
ported tens (Batterson, 1989; Perttunen, 1977) or even hundreds (Shuts,
Sampling material 375
Organic material
Typically a thin layer of organic material is found in dry places and
a thicker layer in moist places at the surface of the overburden. After
decaying of the organic tissue such material turns into humus or peat as
described in Chapter 3. The C/N ratio in plants is over 15, whereas it is in
humus under 12, showing the trend of the alteration.
Humus consists of fresh and decomposed organic litter, mainly plant
remnants, but also contains resistant relics of insects or other animals
and living micro-organisms like microbes, fungi mychorriza and chrysales.
The totally humified part of humus consists of humic and fulvic acids
and their salts and chelates in which the heavy metals are fixed and
enriched. Humic acids and their salts are high molecular weight, base-
soluble compounds of large ion exchange capacity. Fulvic acids are smaller
molecular weight water-soluble compounds, which have a clay clumping
and water retention capacity important for agriculture. Antropova (1975)
claims that humic acids are the main collectors of heavy metals and that
378 Focal aspects of geochemistry applied in arctic and temperate regions
Soil profile
During weathering and soil formation, minerals are decomposed and
part of their elements are dissolved and transported down by percolating
rain water (or up by hygroscopic water). Some of the metals are almost
immediately precipitated, while others get caught in resistant primary
or secondary minerals. The various layers in the soil profile are thus
impoverished or enriched in some elements (Chapter 4).
The humus in podsol and certain other soil types is usually directly
underlain by a bleached mineral horizon A, which is enriched in silica and,
in warmer climates, in aluminium. Lead appears to be enriched as well
(Kauranne, 1967). No enrichment of Pb or Zn seems to occur (Horsnail,
Sampling material 379
TABLE 12-1
Layer pH aq pH ba Al Fe Mn Cu Zn Cd Pb Cr Ni
(%) (%) (%) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
Humus 4.17 3.15 18.9 4.4 10.1 7.4 54.7 0.47 33.8 9.4 5.1
0- 5 cm 4.35 3.45 22.7 2.0 0.30 3.3 22.9 0.24 16.7 12.9 0.04
5-20 cm 4.94 3.76 9.3 0.49 0.18 4.0 28.1 0.32 20.6 19.9 0.13
20-40 cm 5.25 3.76 3.9 0.10 0.05 5.9 24.0 0.32 18.7 21.5 0.70
60-70 cm 5.56 3.76 1.7 0.05 0.01 7.8 19.0 0.28 14.2 18.3 0.72
1975) directly under humus in brown earth soil profile. The A-horizon
has been used experimentally for geochemical exploration, but evidently
without much success since it has not become popular in spite of easy
and inexpensive sampling. The great deviation in results probably depends
on the varying content of organic compounds and the thinness of the
A-horizon.
The boundary of the A-horizon towards the rusty B-horizon is usually
well developed. The B-horizon can be divided into subhorizons too, though
this is not necessary for purposes of geochemical prospecting. The B-horizon
is clearly enriched in Fe, Mn, Co, Zn and Al with minor enrichment of
many other elements. In temperate zones it has become a very popular
material for geochemical exploration since it is easily sampled from about
0.5 m depth and easily recognized by its colour. Thickness varies according
to grain size: in clay it may be a few centimetres, in sand as much as a
couple of metres thick. The border towards the C-horizon is transitional.
No real C-horizon is found in residual soils because the material is
weathered down to bedrock. A virgin C-horizon occurs in transported
mineral soils, where the minerals, even sulphide grains, are fresh in
the ground-water regime. An iron pad layer cemented with limonite is
sometimes encountered at the level of the ground-water table. Above this,
sulphides are weathered, metals soluted and precipitated, clastically and
hydromorphically transported anomalies are superimposed.
Table 12-1 shows the variation of concentrations of the easily BaCl2-
leachable metals with depth in the soils of southern Finland (Tamminen
and Starr, 1990).
Although sampling of the C-horizon is more tedious than that of the
B, it is nevertheless the most popular sampling medium for geochemical
exploration in glaciated terrain. In detailed target exploration it is advisable
to analyze several soil horizons and to take some vertical sample series
through the whole overburden down to the surface of the bedrock.
380 Focal aspects ofgeochemistry applied in arctic and temperate regions
Density
A sparse shallow sampling of till or other widely distributed overburden
materials is sufficient in regional and areal scale geochemical mapping, but
denser and deeper sampling is required in local and especially in target
exploration (see Chapter 7). The smaller the target sought, the denser
the sampling must be and the weaker the signal (anomaly) given by the
target, the larger (or more homogeneous) the samples should be. The
representativeness of the samples can be improved by combining several
subsamples, and the interpretation improved by analyzing a whole set of
related elements (Björklund and Gustavsson, 1987).
As a rule of thumb, in regional (over 100,000 km 2 ) reconnaissance
work one composite sample (consisting of five subsamples from an area of
perhaps 400 m 2 ) per 100-500 km 2 is sufficient. A widely distributed mixture
of bedrock materials — stream sediment or till (e.g., the B-horizon) — can
be recommended as material. In areal (1000-10,000 km 2 ) geochemistry one
composite sample of the above materials or peat or humus per 1-10 km 2
can be recommended.
For local scale (10-100 km2) exploration a denser grid of samples, say
5-50 samples per 1 km 2 , is needed. A short-transported nonsorted sediment
or residual mineral material or humus may be recommended. If till is used
it should be sampled from the C-horizon — from a depth of about 1 m
if there is only one till bed in the area. If there are several till beds, the
stratigraphy, the transport direction and length may decide which is the
optimal bed to be sampled.
Still denser sampling is needed for detailed target exploration (<1 km 2 ).
Both till, bedrock and weathered rock samples can be recommended. Some
samples of every target should be taken as a series through the whole
overburden to permit explanation of the shape and mode of origin of the
anomalies and pinpointing of the drilling target.
Depth
The chemical composition of the surficial layer of residual soils, even if
adjusted for any differences between the possible soil profile layers, does not
necessarily resemble that of the unweathered rock beneath. If the region
happens to be anthropogenically altered by acidic precipitation, fertilizers
or other pollutants, the chemistry of the surface layer may be very different
from that of the underlying bedrock. But the deeper one goes, the closer is
the chemical connection with the fresh rock.
The same is true of relatively short-transported formations like till.
The deeper one goes, the closer one is to the bedrock both physically and
Sampling density and depth 381
t pt
• VIHANTI
MINE
·
' ■ · ·,·
Y
f ►
\ Zn in
ORGANIC MATTER
· · · . under 43 ppm
0 ^ 5km 1 i ^ 43-83 ppm
y ES3 over 83 ppm
Fig. 12-2. High zinc concentrations in stream sediments in the Vihanti river due to contamination
from a flotation waste pond. Redrawn with permission from L-M. Kauranne (1979).
chemically until at the till/rock interface the material is the same, if one
doesn't count the thin layer of quartz-rich "rock flour" often encountered
at the interface (Chapter 2).
Contamination transported by wind as sulphide mineral dust has been
traced down to a depth of 0.5 m in till (Qvarfort, 1977) in villages
where mining and smeltering was done 200-400 years ago. In stream
and lake sediments, traces may be found many kilometres away (30 km,
L-M. Kauranne, 1977; 10 km, Salminen, 1981; 5 km, Qvarfort, 1977). For
example, in the Vihanti river the contamination from a flotation waste
basin could be traced over 30 km in analysis for zinc; the other heavy
metals became fixed more quickly (Fig. 12-2).
Some element concentrations appear to vary with sampling depth even if
the overburden is formed of only one layer of till. In central Finland, in the
overburden above mica schist bedrock, there is a slight increase of average
Mn, \ζ Cu and Zn contents downwards, while the concentrations of Cr, Co
and Ni seem to have no correlation with depth (Kauranne et al., 1977).
By contrast, Pb tends to be highest close to the surface. These patterns
may indicate that the upper horizons are somewhat diluted with granitic
material. In northern Finland concentrations of all these elements increase
strongly downwards in till, not only above basic but above granitic rocks
as well. Possibly in northern Finland there is more preglacial weathered
material intermixed in the till deeper down. See the following Table 12-IIA.
Approximately the same thing applies to sorted sediments (Table 12-IIB).
In central Finland the variation of element concentrations with depth is
very slight, whereas in northern Finland it is marked. In more detailed
geochemical surveys it is important to study the relationship between
concentration and depth to be able to choose the optimal sampling depth
and to interpret the obtained results.
382 Focal aspects of geochemistry applied in arctic and temperate regions
TABLE 12-11
Average total concentrations (ppm) of geochemical samples taken over different lithologies
Depth (m) N Mn V Cr Co Ni Cu Zn
A In till at different depths
Central Finland
Mica schist <1 327 676 372 184 25 106 115 24
1-2 430 781 392 191 30 132 128 36
2-3 19 902 427 197 35 151 132 46
>3 10 847 349 186 28 114 135 72
Northern Finland
Granite <1 238 553 284 371 22 141 49 9
1-2 183 821 374 560 31 238 86 20
2-3 65 882 442 691 37 296 107 32
>3 76 783 478 744 38 320 119 33
Gabbro <1 281 548 301 424 26 177 55 4
1-2 292 625 282 654 37 319 119 10
2-3 101 639 300 740 40 360 179 15
>3 99 690 300 791 42 364 123 18
B. In sorted sediments at different depths
Central Finland
Mica schist <1 18 846 299 153 20 78 73 19
1-2 66 833 333 171 26 97 121 27
2-3 23 728 338 179 20 81 110 32
>3 19 681 336 183 22 111 87 53
Northern Finland
Granite <1 116 551 254 394 22 142 48 11
1-2 51 654 293 485 26 184 58 16
2-3 5 602 470 724 31 249 102 37
>3 4 786 447 826 35 353 105 26
Gabbro <1 11 634 301 364 23 150 64 7
1-2 26 805 300 458 29 186 98 17
2-3 15 594 298 514 32 220 264 29
>3 33 650 349 580 38 237 176 33
C. At the surface of weathered rock under varying thickness of overburden
Central Finland
Granodiorite <1 2 943 285 147 75 83 91 33
1-2 3 947 247 147 43 102 62 39
2-3 1 1300 162 642 28 279 12 106
Northern Finland
Granite <1 18 510 134 126 15 54 24 9
1-2 6 814 145 253 24 96 66 16
2-3 7 1046 269 373 32 145 59 19
>3 5 1035 116 127 21 60 34 14
Gabbro <1 42 638 268 772 35 323 119 4
1-2 109 596 217 634 34 293 132 6
2-3 55 715 292 602 34 229 170 10
>3 64 725 223 607 38 274 174 11
Sample preparation and analysis 383
Sample preparation
The elements of interest may occur in the assayed material in many
forms. To achieve the highest concentration together with the greatest
anomaly/background contrast and most easily interpretable results, one
must consider which mode of occurrence of the sought metal is best for
analysis and on that basis choose the most suitable way of preparing
samples. The most common modes of occurrence of elements are in their
own primary mineral grains, in their own secondary minerals, as coating on
other mineral grains, absorbed in colloids, in organic tissue or in pore water
solution. It is also important to study how the elements in the material
occur to know how it has been transported from the mineralization to
the point of sampling (Nikkarinen et al., 1984). Depending on the method
of preparation, the modes are either separated or mixed homogeneously
together before chemical analysis.
Usually samples are dried by warming before weighing them for analysis.
Elements in solution then become fixed onto the surfaces of grains or
absorbed into colloids. In dry matter from which water has been evaporated,
the elements are rather uniformly distributed. Drying can also be done by
other methods, e.g., centrifuging, which removes the main part of water
along with the elements in solution.
Materials rich in organic material are ashed. Most elements become
oxidized and water soluble, though some of the lighter elements are partly
lost to the air. Hard mineral grains are weakened or broken. Degradation
of organic material can also be achieved by wet oxidation, but the process
tends to be tedious and time-consuming.
384 Focal aspects of geochemistry applied in arctic and temperate regions
Analysis
(AAS), which established its reputation in the 1960's. With its various
modifications — flame, graphite furnace, hydride generation — most
elements can be determined in a wide range of concentrations, in any
material, accurately, rapidly and cheaply. Samples must be in solution.
For easier operation, instruments can be equipped with automatic sample
changers, lamp exchangers and readout. AAS is universal and it can be
warmly recommended for any geochemical laboratory.
Another good analytical method for many elements is optical emission
spectrometry (OES). For this technique, buffer powder and internal stan-
dard are added usually to the finely ground sample to avoid any errors
due to the inhomogeneity of samples and interference of other elements.
The fastest and cheapest version of the optical emission spectrometer has
fixed channels with semiautomatic sample feed and allows the use of fine
mineral powder as such. It is only a pity that this otherwise fine method
does not always give good quality results because of the great variation in
sample matrices.
X-ray fluorescence is also popular, and the latest instrumentation and
improved methods of correction for matrix and interelement effects allow
the analysis of minor and even trace elements. The best results are obtained
using samples that have been finely ground and then homogenized by
fluxing.
Neutron activation analysis (NAA) is a good method for the determina-
tion of uranium, the noble metals and especially the rare earths. Studies
of the rare earths have become popular as a means of investigating the
origin of geological formations, and could perhaps be used in identifying
the source of geochemical anomalies in the same way that determinations
of sulphur and lead isotopes are used.
Small single-mineral grains can be identified and analyzed by scanning
electron microscopy (SEM) with a coupled energy dispersive X-ray analyzer
(EDX). The latest development for isotope analysis of single grains is the
secondary ion mass spectrometer (SHRIMP) — very sophisticated and very
expensive.
The most versatile instrument for today's high level geochemical labo-
ratory is the inductively coupled plasma excitation optical emission quan-
tometer (ICP). Although the requirement for dissolution of the sample
makes it a slower method than semiquantitative OES, it has the invaluable
feature of combining the sensitivity and repeatability of flameless AAS with
the versatility of NAA.
The latest development in the ICP area is the coupled ICP-MS, which
is even capable of separating some isotopes. The technique is a good tool
for identifying the source of an anomaly and can be used for elements like
lanthanides, tantalum, tungsten and the whole group of platinum metals,
which are otherwise difficult to measure. It is useful both for geochemical
exploration and for environmental research.
Interpretation of results 387
INTERPRETATION OF RESULTS
Geochemical research mainly deals with weak and highly varying con-
centrations of trace elements; sets of these elements are determined in
every sample and many samples are collected from every target. Thus
enormous amounts of data must be evaluated and interpreted. As described
in Chapter 10 by Gustavsson, methods of statistical analysis are indispens-
able in the task. The leap forward in computer technology has allowed
the automation of analytical equipment and, together with improved data
processing methods, has opened the way for large scale use of geochemistry.
Despite the remarkable advances in geological theory and skills and
improved geophysical techniques, geochemistry fills many specific needs
that other methods cannot. Not only is it suited for the mapping of large
unexposed regions and for delineating of ore potential areas, but it can
reveal the site and chemical nature of hidden mineralization. Geochemistry
has been successfully applied in both trackless wilderness and industrialized
countries and vast amounts of data have been gathered.
High concentrations of a single element do not necessarily point to an
ore; and sometimes a weak anomaly is more indicative than a strong one,
but unfortunately it can be interpreted as natural variation, due to the
388 Focal aspects of geochemistry applied in arctic and temperate regions
FOLLOW-UP
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REFERENCES INDEX
Ilvonen, E., 310 Kontas, E., 193, 199, 205, 206, 270, 271, 306,
Isohanni, M., 6, 407 318, 319, 403, 407
Isokangas, P., 304, 410 Kontio, M., 256, 370, 394, 399
Korpela, K., 15, 58, 305, 375, 403
James, C.H., 93, 401 Kosakevitch, A., 55, 388, 416
Jarvis, K.E, 210, 401 Kovalevskii, A.L., 65, 403
Jenkins, R., 213, 401 Koveshnikova, T.A., 190, 392
Jenny, E.A., 279, 402 Kristiansson, K, 63, 120, 150, 405
Joensuu, 0., 5 Krumbein, W.C., 127, 128, 130, 403
Johansson, P., 2, 168 Krylova, L.Ya., 332, 403
Johnson, C.C., 332, 391 Kujansuu, R., 139, 403
Johnson, WM, 186, 402 Kukkonen, LT., 407
Juntunen, R., 404 Kuznetsov, V, 409
Juopperi, H., 412 Kvalheim, A., 5, 31, 37, 348, 404
Jöreskog, K.G., 250, 402 Kämäri, J., 407
Königsson, L.-K., 37, 404
Körner, R., 365, 367, 404
Kabata-Pendias, A., 65, 85, 87, 402
Kahma, A., 122, 152, 402 Lagerbäck, R., 28
Kallio, E., 407 Lahermo, P, 80, 370, 404, 407, 416
Kalm, P, 4 Lahti, H.R., 91, 404
Kankainen, T., 25, 366 Lajtai, E.Z., 414
Kaszycki, CA., 377, 402, 412 Lakanen, E., 387, 388, 396, 412
Katskov, A., 409 Lakin, H.W, 4, 400, 416
Kaufman, L., 405 Lalonde, J.P, 53, 404
Kauranne, L.K., 4, 5, 10, 25, 31, 37, 40, 42, Lambe, R.N., 406
59, 62, 74, 76, 80, 88, 94, 102, 103, 127, Lange, H., 115, 411
131, 134, 145, 150, 279, 298, 318, 344, Larkin, S., 413
359, 360, 370, 374, 375, 377, 378, 381, Larsson, J.O., 393
385, 401, 402, 403 Lavikainen, S., 157, 404
Kauranne, L-M., 5, 73, 381, 403 Laville-Timsit, L., 338, 339, 366, 376, 404,
Kettles, I.M., 367, 412 405, 416
Kinealy, K., 279, 403 Lawley, D.N, 252, 404
Kinnunen, K, 53, 369, 375, 403 Lawson, A., 365, 404
Kirkbright, G.R, 415 Leake, R.C., 412
Kitaev, N.A., 409 Lecomte, P., 405
Kivekäs, E.J., 4, 403 Lee, H.A., 4, 37, 129, 404
Kivekäs, L., 129, 409 Legkova, O.E., 404
Klassen, R.A., 375, 403, 412 Legkova, VG., 366, 404
Klovan, J.E., 402 Lehmuspelto, P., 40, 325, 404, 409
Knox, K.S., 396 Lehtonen, M., 412
Kobayashi, J., 73, 74, 403 Leleu, M., 416
Koivisto, T, 302, 305, 403 Lepeltier, C, 238, 404
Kokko, J., 263, 403 Lestinen, P., 57, 283, 406, 407
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Koksoy, M., 122, 393 Lewis, T, 239, 392
Koljonen, T, 245, 370, 403 Leymarie, P, 219, 398
Konstantinova, I.M., 409 Li, S., 417
References index 423
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Van Grieken, R.E., 213, 405 410, 416
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van Praag, H., 395 Wennervirta, H., 51, 143, 416
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Voipio, A., 51, 411 Wintz, P, 246, 398
Volden, T, 394 Wu, S.M., 371, 395
Vuorela, I., 416
Vuorinen, A., 72, 76, 80, 416 Xie, X., 332, 369, 371,427
Väänänen, J., 412
Väänänen, P., 56, 416 Yang, M, 399
Yfantis, E.A., 222,417
Waldron, T., 73, 416 Yio, C-L., 319, 404
Walker, J.L., 393 Yletyinen, V, 401
Walsh, J.N., 209, 415, 416 Yliruokanen, I., 346, 407
Walton, S.J., 415
Ward, EN., 203, 416 Zhang, J., 399, 417
Warnant, P., 405 Zheng, K, 369, 371, 417
Warren, H.V, 5, 416 Zhou, Di, 240, 417
Watson, J.S., 409 Zhou, L, 206, 417
427
SUBJECT INDEX
A-horizon, 55, 58, 77, 79, 83, 86-88, 90, 373, alpine, 85
379 alteration zone, 338
AAS, 64, 195, 196, 200, 203, 204, 206-210, amblygonite, 322
216, 264, 264, 270, 276, 278, 293, 298, ammonia, 112
306, 312, 322, 329, 336, 357, 386 ammonium iodide, 205
ablation moraine, 35 amphibole, 43, 279, 280
ablation tiU, 29, 97, 97, 349 amphiboHte, 132, 263, 269, 272, 291, 310, 321
abrasion, 39, 41, 42, 99, 104, 105, 131, 132, amphibolitic, 355
270, 374 anaerobic bacteria, 43
abrasion resistance, 22, 25, 36, 109, 128, 130 analysis of variance, 187, 225, 228, 231-233
absorbance, 202, 205 analytical method, 100, 124, 143, 153, 160,
absorption, 70, 114, 188, 189, 195, 201, 202, 163, 186, 187, 189, 195, 200, 208, 215,
204-207, 224, 228, 312, 334, 385 218, 223, 225, 231, 369, 386
accuracy, 99, 166, 186-188, 212, 224, 369 analytical performance, 185, 187
acid digestion, 199 analytical precision, 187
acid soil, 77 analytical result, 270, 343, 367
acidity, 96, 111, 112, 350, 351; see also pH analyzing crystal, 211, 212
adsorption, 51, 52, 111, 112, 116, 117, 125 Andrews' curve, 249, 250, 258
aeolian, 46, 54; see also loess; dune angle of climb, 137, 141
Ag, 3, 189, 196, 199, 200, 204, 206-210, 214, anglesite, 340
271, 335-339, 343, 385 annual moraine, 20, 33
age determination, 66, 366, 375 annual precipitation, 338
aggressive reagent, 197 anomaly, 5-8, 11, 12, 20, 31, 33, 40, 42, 49,
air-acetylene flame, 204 50-53, 55-58, 60-62, 63, 66-69, 74-77,
Aittojärvi, 69, 273 82, 83, 85, 90, 100, 102-111, 119, 122-
Al, 43, 62, 77, 79, 80, 86, 98, 193, 196, 197, 125, 127, 129, 131, 135, 138, 141, 143-
199, 204, 209, 339, 340, 379 145, 147-150, 152, 153, 156, 160, 185,
alkali, 77, 113 187, 197, 215-218, 220-222, 224, 226-
alkali metal, 196, 204 228, 230, 232-248, 250, 252-254, 256,
alkaline, 77, 113, 115, 195, 198, 387 258-260, 262, 265, 269-271, 275-277,
alkaline earth element, 113 280-284, 286-288, 290, 293, 295, 297,
alkaline soil, 77 298, 301, 302, 306, 308, 310, 316, 319,
Allebuouda, 352-354 320, 323, 32^-329, 332-334, 336, 337,
allo-till, 21, 29 339, 341-346, 348, 349, 353-355, 359,
aluminium 43, 49, 56, 85, 88, 90, 174, 373, 361-364, 366-370, 372-380, 383, 384,
378;, see also Al 386-389
almandite, 280 anomaly pattern, 102, 103, 105-109, 119,
428 Subject index
135, 152, 156, 187, 197, 218, 220, 222, Ba, 43, 98, 193, 196, 198-200, 204, 209, 336,
224, 226, 228, 230, 232, 234, 236, 238, 340
240-242, 244-246, 248, 250, 252, 254, background shift, 208
256, 258, 260, 262, 288, 308, 310, 316 ball mill, 194
anomaly-background contrast, 242, 388 Baltic Sea, 15, 18, 39, 53, 56, 88, 277
antimony, 153, 320, see also Sb barium, 146, 153, 199; see also Ba
apatite, 280 baryte, 335
apex, 40, 352, 355, 362 basal till, 29, 33, 97, 137, 163, 312, 316, 318
apical boulder, 135, 137 base-exchange capacity, 77
aquaregia, 98, 114, 146, 191, 195, 196, 199, base metal, 51, 56, 88, 90, 165, 269, 334, 338,
204, 205, 209, 387 348, 360, 361, 385
arc nebulization, 211 Bayes' decision rule, 256
Ar, 44 Be, 200, 207, 325
Archaean basement, 284, 285, 290 beach sand, 20, 53, 109, 376
arctic region, 11 beaded esker, 38
Arctic Circle, 263, 269, 325, 348, 352, 355 Beer's law, 202, 204
areal average, 367 Bersbo, 74
argillic, 87 beryllium, see Be
argon, see Ar beta decay, 213
arithmetic mean, 135, 264, 278, 279, 298, 302 Bi, 200, 204, 205, 207, 208, 210, 271
arsenic, 115, 153, 336, 337, 385; see also As bias, 186, 224, 227, 232, 233, 248
As, 196, 199, 204, 205, 207-209, 212, 214, bimodal, 236, 241, 280
271, 333, 335, 336, 338, 343 binding capacity, 68
ash layer, 67 binocular microscope, 285
assaying method, 103 biogeochemistry, 9, 116
atlantic, 81, 85, 88 biplots, 253
atmogeochemistry, 9, 365 bismuth, 153; see also Bi
atmosphere, 113, 114, 364 black cotton soil, 87
atomic absorption, 385 black schist, 105, 296, 321, 338, 363
atomic absorption spectrometer, 201 bog, 56, 59, 66-68, 76, 88, 263, 264, 269, 272,
atomic absorption spectrometry (AAS), 195, 293, 310, 321, 325, 332, 338, 339, 343,
202, 203, 205, 319 346-351, 360, 366, 372, 378
atomic emission spectrometry (AES), 200, bogs on slope, 67
203, 206, 210, 212 bones of animals, 59
Au, 187, 189, 196, 200, 205, 206, 211, 214, boreal, 81, 85
269, 271, 302, 305, 306, 308, 310, 318, boric acid, 196, 204
385 boron, 153; see also B
auger bit, 170, 174, 176 bottom sediment, 51, 52, 67, 196, 372
auger driU, 170, 344 boulder, 4, 5, 11, 21-25, 32, 33, 36, 44, 46,
aureole, 6, 93, 94, 96, 124, 156, 364, 371 51, 54, 67, 102, 108, 109, 122, 127-133,
Australia, 56 135-141, 170, 270, 276, 291, 292, 305,
automatic locating satellite system, 167 318, 343, 349, 353, 360, 375
autosampler, 191 boulder circle, 328
boulder fan, 108, 128, 136, 291, 292, 352, 353
B, 207, 209-211, 214 boulder tracing, 4, 63, 122, 127, 139, 141,
B-horizon, 55, 59, 72, 77, 79, 80, 83, 85, 87, 291, 378
88, 90, 91, 117, 264, 332, 333, 372, 379, Box-Cox power transformation, 232
380 Br, 196, 200, 212, 214
Subject index 429
breccia, 277, 328, 332, 334 China, 46, 54, 55, 208, 332
bromium, 206; see also Br chitinozoan, 59
bromoform, 322 chloride, 56, 88, 112, 202, 203
brown soil, 88 chlorine, see Cl
brunined, 88 chromium, 193, 266-268, 312, 314, 327, 368,
brunisol, 85, 328 385; see also Cr
buffer capacity, 80 Cl, 212, 332-334
buffering agent, 202 classification criterion, 254
bulk analysis, 64, 182, 385 classification tree, 257
bullet shape, 25 clast, 23-25, 28, 30, 31, 33, 36, 40, 52, 127,
burosem, 87 130, 139
14
clastic, 8, 53, 57, 66, 75, 96, 100, 102, 123-
C-age determination, 375 125, 127, 141, 247, 280, 320, 344, 359,
C-horizon, 77, 79, 83, 85, 87, 88, 90, 91, 285, 364, 371, 377
329, 352, 372, 379, 380 clastic anomaly, 57, 58, 93, 102, 123, 124, 377
Ca, 4, 43, 56, 193, 196, 197, 199, 204, 209, clastic dispersion, 96, 97, 110-112, 125, 128,
326, 327, 339 145, 326, 332
cadmium, 65; see also Cd
clastic material, 50, 133
calc-silicate mineral, 279
clastic sediment, 372
calcimagnesian soil, 88
clastic transport, 11, 51, 58, 96, 123
calcium, 43, 56, 71, 85, 87, 88, 327; see aho
clay, 3, 15, 20-22, 35-40, 42, 45, 49, 51-53,
Ca
55, 56, 72, 74, 76, 77, 79, 81, 85, 86,
calibration, 188, 189, 205, 224, 227, 230
109, 110, 116-118, 265, 274, 277-280,
Camp Lake, 328-331
335, 336, 346, 348, 373, 376-379, 384,
Canada, 4, 66, 91, 102, 103, 130, 136, 150,
387
205, 328, 330, 331
clay mineral, 43, 76, 77, 88, 90, 96, 117, 264,
Canadian Shield, 15
capillary rise, 11, 55, 60, 63, 77, 82 279, 323, 334, 372, 373, 387
capture, 49, 77, 226 closed tube sampler, 174, 175
carbon dioxide, 43, 44, 94, 112 C/N ratio, 81
carbonaceous material, 114 Co, 69, 83, 114, 117, 193, 196, 199, 200, 204,
carbonation, 82 207, 209, 212, 264, 265, 269, 276, 285,
carrier gase, 123 293, 296, 298, 302, 310, 312, 317, 336,
cassiterite, 40, 53, 109, 196, 385 357, 376, 379, 381, 382
Cd, 74, 193, 199, 200, 204, 207-210, 214, 379 coarse fraction, 23, 27, 35, 40, 165, 279, 322,
central Lapland peneplain, 296 376
cesium, see Cs coating, 24, 51, 117, 373, 383
chalcopyrite, 269, 280, 289, 290, 293, 304 cobalt, 49, 115, 293, 297-301, 302, 373, 376;
characteristic optical wavelength, 203 also see Co
chelate, 59, 79, 377 Cobra percussion drill, 272, 275
chemical alteration, 49, 96, 373 coefficient of variation, 278
chemical anomaly, 8, 55, 123, 123, 364 cohesive soil, 50
chemical dispersion, 96, 111, 112, 121, 123- cold base glacier, 19
125, 145, 148, 150, 152, 181, 326 cold extraction heavy metals (ex HM), 360,
chemical transport, 11, 371 361
chemical weathering, 43, 94-96, 106, 112, colloid, 7, 45, 51, 58, 77, 90, 91, 96, 112, 116,
279, 330 117, 270, 373, 383, 384, 387
chernosem, 11, 79, 83, 86-88 colloidal, 45, 51, 67, 111, 116, 117
cherty quartzite, 263, 267 colorimetric, 90, 91, 202, 203, 216
430 Subject index
direct current plasma atomic emission spec- electrochemical force, 111, 119
trometer (DCP-AES), 206 electrochemical potential, 94, 359, 376
direct reading spectrometer, 206 electron microprobe, 202, 211
direct sample insertion, 211 electrostatic attraction, 117
direction of ice movement, 18, 25, 32, 99-104, electrothermal atomic absorption spectrome-
145, 270, 322, 344 try, 205
discriminant analysis, 155, 160, 291 electrothermal furnace atomizer, 205
dispersal train, 128, 135-137, 141, 375 electrothermal vaporization, 211
dispersion parameter, 132, 135 Elessiinlampi, 284, 286, 287, 290
dispersion type, 123 Elster, 15
dissolution, 51, 55, 69, 76, 82, 124, 198, 219, emission spectra, 207
322, 367, 373, 386 emission spectrometry, 189, 190, 194, 195,
dissolved material, 50, 51 200, 201
distal side, 33, 107, 134, 145, 305, 318 emission wavelength, 207
distance measure, 254, 256, 257 empirical discriminant analysis, 255, 256
dithiol, 203, 272 end moraine, 33-35
dogs, 7, 122 energy dispersive X-ray analyzer (EDX), 386
dot map, 243-245, 259
energy-dispersive X-ray fluorescence spec-
drift, 1, 3, 7, 11, 41, 54, 55, 60, 66, 68, 77, 96,
trometer (ED-XRF), 212
97, 108-110, 113, 123, 130, 131, 153,
englacial, 137
159, 160, 188, 208, 224, 266, 297, 310,
engorged esker, 38
311, 322, 326-328, 333, 334, 336, 337,
enrichment, 90, 91, 98, 117, 204, 214, 323,
346, 363, 372, 375
376, 378, 379
drift formation, 108
epithermal neutron activation analysis
drill, 162, 165, 168-172, 174-176, 179, 269,
(ENAA), 214
297, 305, 306, 310, 318, 339, 340, 342-
epithermal neutron flux, 214
344, 346, 352, 355, 357, 389
epofix, 278
drilling equipment, 160, 171, 173, 178, 179,
182 equilibrium, 94, 95, 113, 114, 116-118, 349
drilling machine, 155, 160, 162, 172, 182 erosion, 21, 31, 35, 38, 43, 45, 46, 54, 58, 85,
dropstone, 109 106, 108, 129, 133, 322, 366, 367, 369
drumlin, 18, 30-32, 134, 137, 139, 293, 318, erratic, 4, 55, 141, 155, 328, 343, 349, 363
328 esker, 20, 21, 34, 35, 37, 38, 74, 110, 270, 328
drumlinoid, 31, 32 esker chain, 38
dry ashing, 196 Estonia, 15
drying, 192-194, 264, 293, 312, 318, 352, 383, Europe, 3, 15, 17, 81, 88, 149
384 evaporates, 43, 55
dune, 41, 46, 54, 55, 62, 83, 110, 376 evaporation, 82, 88, 329, 336
duplicate sample, 166, 230, 244 excavator, 134, 161, 162, 168, 169
dynamic equilibrium, 59, 68 excavator pitting, 291
experimental mean, 187
economic viability, 186 expert system, 219, 247
Eh, 10, 11, 44, 86, 113-116, 125, 182, 346, exploration, 3-7, 9, 12, 21, 31, 32, 37, 39,
351, 373, 376 53, 56, 63, 67, 68, 74, 76, 82, 87, 91,
eigenvalue, 251, 253 110, 122, 124, 125, 127-129, 138, 144,
electrical charge, 117 145, 155, 161, 165, 169, 174, 180, 182,
electrical conductivity, 118 186, 188, 190-192, 194, 197, 202, 203,
electrical potential field, 118 205, 208, 209, 212-217, 221, 240, 242,
electrochemical dispersion, 119, 125 263-272, 274, 276, 278, 280, 282, 284,
432 Subject index
286, 288, 290-292, 294, 296, 298, 300, "fixed channel", 212, 386
302, 304, 306, 308, 310, 312, 314, 316, fixed charge, 117
318, 320, 322, 324, 326, 328, 330, 332, fixed flow cell, 202
334-336, 338, 340-342, 344, 346, 348- fixed surface potential, 117
350, 352, 354-356, 358-362, 364-367, flame atomic absorption, 199
370-373, 375-380, 383-389 flame atomic absorption spectrometry (FAAS),
exploratory data analysis (EDA), 240 204-207, 285
extending flow, 19 flameless atomic absorption spectrometry, 200
extraction agent, 185, 198 flame-mode AAS, 203
floating bog, 66, 67
F, 200, 333 flood deposits, 39, 51
fabric, 24, 28, 30, 275, 305 flow-injection analysis (FIA), 203
factor analysis, 155, 160, 190, 249-251, 255, flow-till, 22, 31
257, 258, 262, 267, 338, 388 fluoride, 202
factor matrix, 252 fluorine, 203; see also F
factor scores, 252 fluorimetry, 385
"false" anomaly, 49, 367 fluorite, 343
Falun, 3, 74 flushing, 168, 170-174
faulting, 24, 37, 38 fluting, 31, 32
Fe, 43, 62, 67, 77, 79, 86, 98, 113, 114, 117, fluvial, 45, 50-52, 99, 137
190, 193, 196-199, 204, 209, 271, 326, flux, 133, 137, 195, 214, 387
327, 336, 339, 340, 342-344, 346, 357, folding, 24, 37
379 fossil secondary pattern, 93
Fe-Mn coating, 117 fracture zones, 122, 156
feldspar, 10, 22, 37, 43, 45, 54, 74, 76, 279, friction soil, 50
355, 376 frost heave, 100, 110, 328
Fennoscandia, 15, 81, 150, 348, 370 frost wedge, 24
Fennoscandian Shield, 15 fulvic acid, 59, 79, 88, 377, 387
fermentation, 328 fulvic salt, 85
ferric iron, 43, 79, 85 fusion, 195, 196, 198, 344, 383, 387
ferri-oxyhydrate, 47 Fuzzy-set theory, 257
ferrous iron, 43
field laboratory, 181 Ga, 200, 206, 207, 210
Filon Rico, 335-337 gabbro, 131, 296, 310, 382
fine fraction, 42, 97, 104, 129, 131, 135, 141, gallium, see Ga
165, 193, 194, 208, 222, 264, 265, 270, galvanic cell, 118
279, 280, 285, 290, 308, 312, 319, 320, gamma emitter, 214
322, 325, 344, 359, 377, 384 gamma ray, 213
fingerprint, 6, 53, 258, 259, 348, 363, 367 gamma spectrometry, 7, 213
Finland, 4, 5, 24, 26, 29, 33, 34, 42, 53, 56, 67, gangue, 338
74, 80, 81, 98, 101, 102, 104-106, 108, gangue minerals, 124, 334
121, 122, 128, 134, 137, 139, 140, 144, garnet, 10, 40, 45, 52, 53, 109, 269, 385
146, 150-152, 157, 198, 272, 277, 279, gas anomaly, 122
280, 283, 290, 293, 296, 302, 310-312, gas flame, 204
318, 321, 346, 347, 355, 356, 358, 359, gas geochemistry, 9, 122, 123
361, 370, 377, 379, 381 gaseous dispersion, 111, 122
fissility, 24, 30 gaseous mercury, 181
fission neutron energy spectrum, 213 gaseous phase, 121, 125, 183
fissure, 94, 122, 348, 352 Gaussian scale, 238
Subject index 433
Ge, 196, 200, 205, 210 glacilacustrine, 20, 36, 39, 40, 377
genesis of till, 21, 29, 97 glacimarine, 20, 36, 39
geochemical cycle, 93 gley, 79, 88
geochemical data, 144, 155, 161, 181, 186, gleysol, 328
187, 190, 219, 223, 224, 233, 237, 238, gliding mean, 160
243, 245, 246, 253, 255, 260 global zoning, 77
geochemical dispersion, 1, 93, 124, 183, 328, Glogfawr, 332-335
343 gneissic granite, 285, 288, 289
geochemical prospecting, 33, 49, 51, 58, 63, goethite, 55, 269, 270, 280, 340
74, 96, 105, 109, 112, 114, 115, 163, 164, gold, 4, 7, 40, 60, 76, 109, 153, 165, 182,
348, 352, 379 193, 204, 210, 222, 269-271, 307-310,
geochemical province, 163, 164, 363, 369, 372 318-320, 376, 384, 385; see also Au
geochemical relief, 187, 218, 220, 221, 232, gold ring, 193
233 goodness-of-fit, 253
Geochemical Atlas of Finland, 144, 146, 151 good laboratory practice (GLP), 215, 227
Geological Survey of Finland, 185, 193, 217, gossan, 49, 55, 56, 216, 338-340, 342, 363,
227, 285 366, 373, 376, 377, 388
germanium, see Ge grain size, 8, 10, 15, 19, 21-23, 27, 30-32, 35,
Germany, 4, 109 36, 40, 42, 45, 46, 52, 54, 74, 78, 105,
glacial drift, 113, 131, 187, 296, 297, 325-327 117, 125, 134, 141, 165, 166, 168, 182,
glacial erosion, 97-99, 108, 147, 160, 297, 193, 194, 197, 222, 264, 278-280, 328,
326, 366 330, 341, 344, 370, 371, 374, 375, 379,
glacial lobe, 99, 141 384
"glacial miü", 375 granite, 4, 7, 42, 43, 131, 132, 136, 151, 263,
glacial overburden, 5, 96, 102, 113, 193, 200 267, 269, 272, 284, 285, 288-291, 310,
glacial till, 1, 8-10, 39, 96, 114, 115, 117-119, 321, 325, 326, 343, 346, 348, 349, 352,
263, 319, 352 355, 372, 382
glacial transport, 23, 57, 58, 96, 100, 102, graphite, 204, 205, 207, 270, 276, 277, 306,
127-132, 134, 135, 137-139, 141, 145, 319, 386
149, 155, 159, 272, 326, 332, 334, 349, graphite furnace atomic absorption (GFAAS),
357, 374 205
glaciated terrain, 2, 5, 21, 41, 58, 96, 99, grass, 59, 66, 81, 263, 269, 328, 332, 343, 352,
108-110, 122, 124, 125, 141, 144, 145, 360
149, 150, 162, 296, 328, 343, 352, 366, gravity, 10, 43, 44, 50, 52, 94, 96, 110, 111,
374, 379 123, 124, 129, 371, 374
glaciation, 13, 15-17, 20, 21, 24, 26, 33, 41, gravity differentiation, 93
42, 46, 54, 55, 81, 86, 96-99, 108, 114, graywacke, 296
115, 123, 128, 145, 297, 310, 326, 328, Great Britain, 72
374, 375 Great Lakes, 15
glacier, 4, 15, 19-21, 28-30, 33-35, 37-39, greenstone, 132, 263, 296, 302, 304
41, 44-46, 54, 79, 83, 96, 97, 99, 100, grinding, 10, 32, 191-194, 383, 384
102-104, 107, 109, 110, 123, 127, 131, groove, 19, 54, 99
133, 134, 136, 145, 148, 156, 163, 279, ground-penetrating radar, 181
322, 343, 374 ground water, 43-45, 51, 52, 55-58, 66-68,
glacifluvial formation, 1, 35, 37, 277, 346 72, 79, 88, 112, 115, 117, 118, 123, 326,
glacifluvial process, 27 328, 332, 340, 349, 351, 352, 370, 373,
glacigenic anomaly, 49, 110, 148, 295, 326 376
glacigenic dispersion, 124, 127, 141, 320 ground-water table, 44, 56, 83, 91, 113, 152,
434 Subject index
interface, 19, 25, 40, 133, 270, 309, 318, 345, Kraft paper, 193
381 Kriging interpolation, 243
interference, 190, 202, 204, 205, 207, 208, Kylmäkoski, 291, 292
210, 212, 214, 386
interglacial, 13, 15, 17, 31, 42, 375 La, 199, 207, 209, 212, 214
international quality system standard, 215 laboratory information management system,
interstadial, 15 191
iodine, 332-334; see also I labour-intensive, 192, 195
ion exchange, 90, 111, 116, 125, 210, 377 Lady Loretta, 56
ion probe (SIMS), 202 lake sediment, 1, 8, 9, 72, 73, 110, 215, 328,
ion-selective electrode, 202 329, 331, 332, 363, 366, 372, 381
ion size, 45 laminae, 24, 71
ionic diffusion, 371 laminar movement, 25
ionic dispersion, 98 lamination, 30
ionic potential, 95 land uplift, 15, 38
ionization, 117, 210, 211 landscape, 366
Ir, 211 landslide, 85, 110, 123, 366
iridium, see Ir lanthanides, 386; see also La; rare earth ele-
Ireland, 89-91, 371 ments
iron, 3, 10, 43, 44, 49, 51, 53, 54, 55, 56, Lapland, 71, 98, 136, 263, 266-269, 271, 296-
67, 70, 79, 85, 86, 88, 90, 115, 198, 264, 298, 325, 350, 351, 353, 354, 360, 368
289, 326, 327, 338, 339, 348, 355, 356, laser ablation, 208, 211
359, 373, 376, 379; see Fe laser probe, 202
iron cap, 49, 373 lateral diffusion, 67
iron pan, 47, 56, 85, 373 lateral moraine, 33
Iron Age, 73 laterite, 388
irradiation, 213, 214 Laukunkangas, 293, 295
lead, 3, 49, 55-58, 65, 67, 71-73, 76, 83, 90,
jarosite, 340 91, 122, 329-331, 334, 336, 337, 339,
Jatulian, 302, 304 340, 342, 347, 348, 368, 369, 378, 387,
jaw crusher, 42, 194 388; see also Pb
leaves of trees, 59
K, 43, 56, 95, 158, 193, 196, 198, 199, 204, lee, 4, 30, 32, 37, 54, 129, 374
209, 339, 340 lee-side cone, 31, 32
Kajaani, 272 lepidocrocite, 280
Kalahari Desert, 109 lepidolite, 322, 323
käme, 38, 39, 328 Li, 193, 196, 199, 204, 209, 320-325
käme delta, 39 lichen, 59, 76, 269, 328
käme moraine, 33 Lietsonsuo, 346, 347
käme plateau, 38 lime, 45, 85, 131, 132, 138, 378
käme terrace, 38 limit of detection, 186, 188, 189, 212
Kansan, 15 limonite, 43, 45, 47, 49, 53, 55, 265, 270, 335,
kaolinite, 77, 79 373, 379
Karelian schist belt, 321 linear discriminant analysis, 255
key element, 153 lithium, 195, 322; see also Li
key element paragenese, 153 lithogeochemistry, 5, 9, 222, 365
Kissanloso, 283, 284, 289, 290 lithological composition, 22, 102
knob and kettle, 33 lithology, 6, 10, 19, 21, 23, 25, 30, 31, 40,
Kokka, 103 45, 71, 87, 88, 94, 127-132, 135-137,
436 Subject index
oxidation state, 113 pH, 10, 42-44, 51, 80, 86, 95, 113-117, 125,
oxide, 7, 10, 43, 49, 51, 79, 95, 113, 114, 116, 182, 202, 333, 346, 349, 351, 360, 373,
117, 185, 190, 193, 197, 198, 210, 269, 376, 379
279, 289, 338, 384, 387 phosphates, 196, 340
oxidizing acid, 195, 196 phosphorus, 153; see also P
oxidizing agent, 113, 196 photographic film, 181
oxy ions, 115 photographic recording, 206
oxygen, 11, 44, 58, 72, 94, 112, 113 photomultiplier, 204, 206, 208
oxyhydrates, 47, 338, 372 phyUite, 131, 321, 348
physical methods, 181
ί 193, 199, 207, 209, 340, 388 physical weathering, 94, 95
palladium, see Pd pilot study, 225, 364
Pallastunturi, 310, 311 placer deposit, 40, 53, 76, 109
panning, 4, 7, 63, 353, 385 plagioclase, 280
paragenetic element, 7, 246, 368 plant pollen, 59
partial extraction, 195, 197, 199, 203, 216 plasma emission, 188, 189, 191, 195, 199
partial leach, 6, 215 plasma-mass spectrometry (ICP-MS), 190,
particle induced X-ray emission (PIXE), 202 200, 201, 208
passive ice, 102 plasma source, 206
pathfinder element, 153, 185, 189, 271 plasma source spectrometry, 195
Pb, 57, 74, 80, 114, 189, 193, 196, 199, 200,
platinum, 195, 385, 386; see also Pt
204, 205, 207-336, 338-340, 342, 343,
platinum crucible, 195
357, 360, 361, 378, 379, 381, 385, 388
platinum group of elements (PGE), 189, 200,
Pd, 205,206,211
209, 210, 214
Pearson coefficient of correlation, 247, 377
Pleistocene, 9, 13, 16, 46, 81, 86, 128
Pearson product moment correlation coeffi-
plumbogummite, 340
cient, 247
pneumatic drill, 297
peat, 8, 58, 59, 61, 65-71, 76, 81, 88, 89, 93,
podsol, 11, 55, 79, 80, 82, 83, 85-88, 117, 264,
196, 263-265, 269, 272, 274, 293, 304,
332, 335, 338, 339, 343-352, 357, 360, 343, 378
363, 366, 372, 376-378, 380 polarizing microscope, 278, 322
peat geochemistry, 9 pollution, 49, 55, 67, 72-74, 76, 90, 364, 371,
pebble, 51, 54, 100, 117, 128, 130, 131, 141, 388
157, 285, 290 polychromator, 207-209
pedalfer, 85 polyethylene bottel, 196
pedocal, 85 pore water, 50, 373, 376, 383
pedogeochemistry, 4, 9, 31, 365 Pori, 274
pedology, 82 porosity, 55, 77, 87, 122
pentlandite, 263, 293, 317 portable Hg determinator, 205
perchloric acid, 329 portable XRF analyzer, 182
percussion drill, 160, 170, 171, 264, 270, 272, Porte aux Moines, 338, 340, 342, 372
275, 278, 285, 293, 297, 305, 306, 312, postglacial, 9, 15, 18, 21, 39, 41, 53, 56, 58,
318, 322, 360 99, 100, 150, 152, 304, 326, 366
perennial, 110 postglacial clay, 38
periglacial, 24, 110 potassium, 49, 198, 373; see also K
permafrost, 9, 24, 67, 79, 328, 329, 331, 332, powder, 195, 196, 199, 208, 211, 212, 214,
366 264, 386
permeability, 52, 55, 76, 81, 86 Precambrian, 335, 343, 352
Petalax, 359-361, 372 precipitate, 43, 44, 55, 95, 113, 117, 123, 319
Subject index 439
sample contamination, 172 sediment, 1, 4, 8-11, 15, 20-22, 24, 30, 31,
sample decomposition, 191 35-42, 45, 46, 48, 50-53, 55, 56, 58, 67,
sample logistics, 185, 190, 215 72-74, 76, 79, 87, 97, 98, 109, 110, 114,
sample size, 165, 222 116, 127, 133, 150, 168, 169, 193, 196,
sampler, 38, 162, 170, 174-176, 264, 270, 272, 215, 270, 278, 280, 285, 304, 310, 312,
275-278, 285, 360, 383 320, 328, 329, 331, 332, 335, 341, 363,
sampling density, 143-145,148-152, 155,158, 365, 366, 372, 374-377, 382
163, 164, 166, 221, 222, 297-300, 302, sedimentation, 10, 20, 23, 30, 37-39, 42, 45,
305, 307, 369 46, 55, 93, 94, 96, 97, 133, 137, 367, 384
sampling depth, 143, 149, 159, 163, 165, 166, Seinäjoki, 318, 319
168-170, 277, 306, 378, 381 seismic sounding, 152, 181
sampling equipment, 143, 165, 168, 169, 180- selective extraction, 197, 215, 340
182, 192 selectivity, 186, 188, 190, 197
sampling error, 187, 222 selenium, see Se
sampling grid, 102, 145, 147-149, 152, 159, self potential, 356
161, 165, 219, 220, 222, 234, 280, 302, semiquantitative analysis, 207
354, 370, 371 semiquantitative method, 160, 385
sampling interval, 156, 160, 293, 312, 336 sensitivity, 7, 100, 103, 186, 188, 369, 384,
sampling method, 165, 166, 168, 218, 370 386
sampling variance, 187 separation, 10, 32, 37, 39, 42, 54, 95, 189,
sand, 3, 20-22, 24, 25, 28, 30, 33, 35-42, 45, 190, 201, 203-206, 209, 210, 214, 231,
49, 51-55, 60, 62, 74, 76, 81, 86, 93, 353, 374, 384, 385
110, 117, 124, 131, 197, 270, 274, 275, sequential analysis, 364, 373, 376
277-280, 293, 318, 335, 336, 356-359, sequential extraction, 197
361, 373, 376, 377, 379, 384, 387 sequential XRF, 212
sandstone, 131, 132, 343 serpentinite, 103-105, 263, 265, 267, 269,
sandur, 39, 83 310, 316, 317
saturation, 96, 114, 326, 364 sesquioxides, 83, 88
Sb, 83, 193, 196, 200, 204, 205, 207-210, 212, shifting, 136
214, 271, 318, 319, 336, 338 Si, 43, 79, 193, 196, 204, 209, 211
Sc, 199, 200, 207, 209, 214 Sierra Leone, 370
Scandinavia, 4, 5, 102, 103, 128, 144, 160 sieve shaker, 191
scandium, see Sc sieving, 23, 192-194, 265, 276, 352, 383, 384
scanning electron microscopy (SEM), 386 silica, 43, 116, 373, 378; see also Si
scatter diagram, 228-230, 233, 243, 244, 247, silicate, 7, 36, 42, 49, 95, 185, 195, 196, 198,
249, 252 199, 376, 387
scavenge, 77, 96, 117, 373 silicate-forming element, 204
scheelite, 63, 277-281, 352, 355, 385 silt, 20-22, 30, 33, 35-41, 45, 52, 53, 56, 74,
Scotland, 143 76, 80, 109, 110, 130, 277-280, 332, 348,
Scottish Highlands, 345, 346 360, 376, 377, 385
Se, 196, 200, 205, 206 Silurian, 332, 335
secondary dispersion, 77, 78, 93, 94, 96, 339, silver, 3, 335, 337; see aho Ag
341 silver halogenide, 335
secondary halo, 93 simultaneous spectrometer, 208, 213
secondary mineral, 43, 95, 162, 216, 372, 378, simultaneous XRF, 212
383 single element anomaly, 234
secondary radiation, 211 skarn, 104, 263, 277, 352, 355
secondary till, 29, 30 slip, 19, 110, 175,227
Subject index 441
surface area, 42, 51, 102, 104, 106, 113, 192 Tohmajärvi, 320-322
surface erosion, 110 toluene, 206
surface water, 56, 112, 113, 123, 339, 364 topography, 42, 58, 99, 107, 130, 141, 143,
survey strategy, 165, 166, 168 152, 166, 178, 246, 277, 293, 318, 346,
susceptibility, 181, 357, 385 366
suspension, 44, 384 total analysis, 124, 291
Svecokarelian orogenic belt, 277 total decomposition, 197, 204
Sweden, 3, 72, 150, 152, 348, 352, 370 tourmaline, 280
swing mill, 194 trace element, 6, 9, 12, 71, 72, 74, 114, 116,
symbol map, 242, 243 153, 160, 195, 196, 198, 199, 200, 201,
212, 215, 368, 377, 386, 387
Ta, 193, 200, 209, 210, 212, 214, 325 training data, 253-256
talus cone, 41, 50, 110 transition element, 113
Tampere, 290 translocation, 21
tantalum, 386; see also Ta transport, 6, 10, 19, 21, 25, 27, 29, 32, 33,
Te, 196, 200, 205, 206, 210 35-37, 39, 42-44, 46, 47, 50, 51, 54,
tectonics, 94, 363 56-58, 63, 69, 94-96, 99, 100, 102, 103,
tellurium, see Te 106-111, 123, 124, 128, 130, 131, 133,
tephra, 46 135, 137-180, 270, 272, 320, 326, 328,
terminal grade, 22, 128, 130 329, 332, 337, 338, 344-346, 356, 359,
terminal moraine, 33 367, 369, 370, 372, 374, 375, 384, 388
Th, 199, 200, 209, 210, 212, 214, 325, 351 transport direction, 11, 99, 100, 108, 110,
thallium, see Tl 123, 145, 148, 297, 305, 308, 328, 346,
thermal, 133, 134, 211, 213, 214 348, 371, 380
thermal ionization mass spectrometry (TIMS), transport distance, 100-102, 105, 106, 109,
211 123, 127-132, 134, 135, 137-141, 145,
thorium, see Th 148, 277, 291, 308, 312, 323, 359
throughput, 186, 191, 192, 196, 201-203, 206, transport distance (TDD) method, 128, 137,
209, 213, 215 138, 141
Ti, 43, 193, 196, 199, 204, 388 transported drift, 373
till, 5, 10, 11, 15, 19-25, 27-33, 35-42, 49, 53, transport mechanism, 1, 109, 123
55, 58, 62, 68, 69, 72, 74-76, 80, 81, 85, trimming, 240
90, 91, 93, 96-110, 113-115, 117-119, triphylite, 322, 323
127-132, 134-141, 143, 144, 146, 148- "true value", 242
153, 155, 157-163, 165, 166, 168, 169, tungsten, 7, 63, 193, 278, 279, 280, 352, 353,
171-173, 188, 190, 193, 194, 197, 198, 354, 355, 384, 386; see also W
204, 206, 208, 215, 216, 220, 222, 227, turnaround, 186, 192
228, 244, 253, 257, 264-267, 269-280, two-peaked "rabbit ear" anomaly, 119
283, 285-299, 301, 302, 304-306, 308- two-vector dispersion, 371
310, 312, 313, 316, 318-326, 328, 329, twofold unbalanced design, 225, 228
332, 335, 343-346, 348, 349, 352-363,
366, 370, 372, 374-378, 380-382, 384, U, 67, 98, 200, 202, 207-212, 214, 346, 348,
385 349, 351, 377, 385
till blanket, 100, 101, 117, 131, 152, 285, 287, ultramafite, 310, 316, 317
322 ultrasonic sieving, 194
time-dependent shift, 188 ultraviolet (UV), 7, 63, 352, 385
tin, 3, 203, 277-280, 282, 354; see also Sn unconsolidated, 1, 11, 41, 77, 98, 155
titanium, 67, 348; see also Ti United Kingdom, 149
Tl, 200, 205, 210, 211 unsupervised method, 253
Subject index 443
uranium, 51, 56, 58, 122, 137, 202, 203, 347, weathering, 1, 7, 10, 11, 19, 27, 31, 41, 43,
348, 349, 350, 351, 352, 377, 385, 386; 49, 58, 77, 79-83, 85, 93-99, 104-106,
see also U 110-113, 123, 160, 216, 280, 290, 318,
UV radiation, 202 323, 326, 329, 332, 337, 338, 365, 367,
371-373, 375, 378
y 196, 199, 200, 207, 209, 212, 381, 382, 388 weathering crust, 42, 296, 297, 326
vacuum path, 209 Weichsel, 15
valence, 113 weighted median, 245
vanadium, 115, 348; see also V wet ashing, 196
vaporization, 205 white spirit, 194
Visasaari, 325-327 winsorized average, 240
void, 44, 49, 55, 81, 373, 376 winsorizing, 240
volatile, 123, 205, 384 Wisconsin, 15
volcanite, 277, 279, 301, 306, 318 wolframite, 63, 352, 355, 385
volcano, 46, 348, 367 Wurm, 15
Vuonelonoja, 325-327
X-ray fluorescence, 187, 190, 194, 201, 211,
W, 187, 193, 200, 207-210, 212, 277-280, 352, 352, 386
385 X-ray fluorescence spectrometry (XRF), 188,
Wales, 333, 334 190, 195, 198, 200, 201, 211-213, 264,
warm base glacier, 19 276, 291, 312, 347
washboard moraine, 32 Y, 199, 200, 207, 209, 210, 212
water, 1, 3, 4, 8, 10, 11, 15, 20, 21, 23, 27, Yb, 207, 209
30-32, 35-46, 49-53, 55, 56, 58, 65-68, ytterbium, see Yb
72, 73, 77, 79, 81, 82, 85, 88, 91, 94-97, yttrium, 151; see also Y
99, 108, 110-114, 117, 123, 124, 156,
168, 170-173, 182, 194, 195, 198, 199, Zambia, 370
202, 205, 216, 222, 265, 296, 328, 329, zinc, 61, 64, 65, 75, 101, 122, 267, 278, 279,
331-378, 383-385, 387 280, 329, 330, 331, 334, 337-340, 342,
water table, 79, 88, 113, 114, 117, 161 347, 348, 376, 381, 387; see also Zn
wave action, 27, 35, 36, 52, 109 zirconium, see Zr
weak acid, 124 Zn, 51, 64, 69, 74, 80, 83, 114, 117, 118, 193,
weak agent, 124 196, 199, 204, 207, 209, 211, 212, 244,
weathered bedrock, 1, 93, 96-98, 104, 113, 264, 265, 267, 271, 276-280, 310, 312,
116, 117, 122, 143, 160, 162, 216, 264- 317, 329, 331-333, 335, 336, 338, 339,
267, 269-273, 275, 285, 296-298, 300- 342, 343, 357, 360, 361, 378, 379, 381,
302, 306, 312, 318-320, 322-326, 336, 382, 385, 388
339, 373, 374, 383 Zr, 193, 196, 200, 209, 212