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OVERVIEW: PRINCIPLES AND COMPARISONS OF LEACHES FOR DEEP EXPLORATION

Eion M. Cameron

Nature of Anomalies
The composition of soils is dominated by endogenic components, which were present in
the parent material for the soil. In the clay soils of the Abitibi, elements are contained in
finely ground rock fragments and primary minerals from sedimentary, igneous and
metamorphic rocks. Similarly for the piedmont gravels of Chile, but here the range of
grain sizes if vastly different. Soil-forming processes cause the modification or destruc-
tion of primary minerals and the creation of secondary minerals into which the en-
dogenic element components are redistributed. Secondary minerals include Fe and Mn
oxyhydroxides, carbonates and organic compounds.
Superimposed on these endogenic components are elements of exogenic origin added
to the soil. These may be from a buried mineral deposit. Introduction may be continu-
ous, as is likely for elements migrating up through clay cover in the Abitibi, or episodic,
as in seismic pumping of mineralized groundwaters in Chile. After introduction into the
soil these exogenic components participate in soil-forming processes and the elements
enter the same secondary minerals as elements of endogenic origin. Thus anomalies
are accretive, with a given batch of elements of exogenic origin going through a pro-
gressive evolution in terms of their incorporation into secondary minerals. At any stage
in the development of an anomaly the exogenic components are represented by mate-
rial that has been fixed in secondary minerals and by material, usually much smaller in
amount, that has yet to be fixed, the precursor phase.

Objective of Leaches used for Deep Exploration

The objective of leaches is to exclude, to as great an extent as possible, the endogenic
element component, in order to maximise the signal from elements that have been intro-
duced from the mineral deposit. The term selective leach has been widely used to de-
scribe leach solutions that are designed to dissolve specific secondary minerals that
may host indicator elements. However, as discussed above, secondary minerals are
likely to contain a mixture of endogenic and exogenic components. Depending on the
relative contribution of the two components, selective leaching may be more or less suc-
cessful. An alternative approach is to dissolve elements of exogene origin before they
participate in the soil-forming process and enter secondary minerals; i.e., the precursor
phase. To distinguish these from selective leaches, the term precursor leach is intro-
duced here. Finally, strong leaches, such as aqua regia, tend to dissolve most of the
mineral components of the soil, both primary and secondary.

Comparisons of Leaches
In this section we compare the amounts of elements extracted by leaches from 61 soil
samples at the Spence deposit. The Spence results were chosen, in part, because there
are data for six leaches used to extract the same set of samples: the minus 80 mesh
fraction of soils collected at a depth of 10-20 cm. Also, sufficient detailed work has been
carried out at Spence in Chile and Cross Lake in the Abitibi, so we have at least the be-
ginning of an understanding on the formation of the anomalies. Details on the analytical
methods have been given by Cameron and Hall (2001). The leaches are deionised wa-
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ter, Enzyme Leach, MMI-A, ammonium acetate at pH 5, cold 0.1M hydroxylamine with
0.01M HNO3, and aqua regia. All methods use a ICP-MS finish and five of the methods
report a wide range of major and trace elements, 40 elements or more. MMI-A provides
results for Cu, Zn, Cd, Pb and Au. Results are shown in a series of figures, which dis-
play the concentration ranges extracted by the different leaches.
Figure 1 shows the amounts of Al extracted by all methods except MMI-A. This figure
provides an index of the selectivity of the leaches, since, other than aqua regia, none of
the methods attempt to dissolve aluminosilicate minerals. Very small amounts are dis-
solved by deionised water and Enzyme Leach and there is a progressive increase in Al
extracted by ammonium acetate, hydroxylamine, and aqua regia. Since ammonium ace-
tate is designed to dissolve carbonate minerals and hydroxylamine to dissolve Mn ox-
ides, the results indicate that they are not fully selective.
Ranges for Mn are shown in Figure 2. Enzyme Leach is designed to dissolve reactive
Mn oxides (Clark, 1993). The amounts extracted by this leach are small and the range
overlaps that of deionised water. Ammonium acetate extracts more and there is a sharp
increase in Mn extracted by hydroxylamine.
For Fe (Figure 3), ranges for deionised water and Enzyme Leach overlap at low concen-
tration and ammonium acetate and hydroxylamine overlap in a somewhat higher range.
Aqua regia extracts ~3 orders of magnitude more than the latter.
Ammonium acetate is a reagent specifically for the dissolution of carbonate, which is an
important minor constituent of the Spence soils. The hydroxylamine leach, with a start-
ing pH of 1.5, also dissolves carbonate. The amounts of Ca dissolved by these two
leaches is similar (Figure 4). Aqua regia dissolves carbonate plus silicates containing
Ca. The amount of Ca dissolved by deionised water and Enzyme Leach is small and the
ranges overlap. There is slight dissolution of Ca by Enzyme Leach (Cameron et al.,
2000), since this solution is weakly acidic, with a starting pH of 3.5.
Two elements, Na and S, have been introduced into the soil in groundwater, the former
as NaCl and the latter as sulphate. These are readily soluble, so that the concentration
ranges extracted by all leaches, from deionised water to aqua regia, overlap (Figures 5
and 6).
As described in several of the reports, Cu is the critical indicator element for Spence,
since it occurs in anomalous amounts only in the soils over the ore body. After reaching
the surface in mineralized groundwater, it is involved in soil-forming processes and is
substantially redistributed into carbonate minerals. Thus extraction of this major portion
of the exogene Cu phase requires dissolution of carbonate. Both ammonium acetate
and hydroxylamine dissolve carbonate and extract substantial amounts of Cu (Figure 7).
Also, MMI-A is sufficiently acidic, with a starting pH of ~2.5, to dissolve carbonate, so
that it too extracts Cu. Lesser quantities are dissolved by Enzyme Leach and deionised
water.
Arsenic is another indicator element that has been substantially fixed in carbonate min-
erals, requiring the dissolution of the latter phase. This is shown by the strong extraction
of As by ammonium acetate and hydroxylamine (Figure 8). Less is removed by deion-
ised water and Enzyme Leach.
Molybdenum behaves differently, since the exogene fraction is largely converted by soil-
forming processes into a form that is only dissolved by aqua regia (Hall and Cameron,
2001). There is overlap in the amounts of Mo extracted by deionised water, Enzyme
Leach, ammonium acetate and hydroxylamine, whereas much higher amounts are re-
moved by aqua regia (Figure 9).
For comparison with the Spence plots, ranges are shown for the amounts of Al, Mn and
Cu extracted by leaches from B-horizon soils collected in the Abitibi program in 1999
(Figures 10 to 12). The Abitibi samples differ substantially from those at Spence. Only
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Aqua Regia

Hydroxylamine

Ammonium Acetate

Enzyme Leach

Deionised Water

Figure 1. Ranges of Al extracted by five

leaches for 61 Spence soils collected at 10-
1 10 100 1000 10000 100000 20 cm depth.
Al, ppm

Aqua Regia

Hydroxylamine

Ammonium Acetate

Enzyme Leach

Deionised Water

Figure 2. Ranges of Mn extracted by five

leaches for 61 Spence soils collected at 10-
0.1 1 10 100 1000 20 cm depth.
Mn, ppm

Aqua Regia

Hydroxylamine

Ammonium Acetate

Enzyme Leach

Deionised Water
Figure 3. Ranges of Fe extracted by five
leaches for 61 Spence soils collected at 10-
0.1 1 10 100 1000 10000 100000 1000000
20 cm depth.
Fe, ppm
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Aqua Regia

Hydroxylamine

Ammonium Acetate

Enzyme Leach

Deionised Water

Figure 4. Ranges of Ca extracted by five

leaches for 61 Spence soils collected at 10-
10 100 1000 10000 100000 1000000
Ca, ppm
20 cm depth.

Aqua Regia

Hydroxylamine

Enzyme Leach

Deionised Water

Figure 5. Ranges of Na extracted by four

leaches for 61 Spence soils collected at 10-
1 10 100 1000 10000 100000
Na, ppm 20 cm depth.

Aqua Regia

Enzyme Leach

Deionised Water

Figure 6. Ranges of S extracted by three

10 100 1000 10000 leaches for 61 Spence soils collected at 10-
S, ppm 20 cm depth.
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Aqua Regia

Hydroxylamine

Ammonium Acetate

MMI

Enzyme Leach

Deionised Water Figure 7. Ranges of Cu ex-

tracted by six leaches for 61
1 10 100 1000 10000 100000 1000000 Spence soils collected at 10-
Cu, ppb 20 cm depth.

Aqua Regia

Hydroxylamine

Ammonium Acetate

Enzyme Leach

Deionised Water Figure 8. Ranges of As ex-

tracted by five leaches for 61
10 100 1000 10000 100000 Spence soils collected at 10-
As, ppb 20 cm depth.

Aqua Regia

Hydroxylamine

Ammonium Acetate

Enzyme Leach

Deionised Water Figure 9. Ranges of Mo ex-

tracted by five leaches for 61
1 10 100 1000 10000 Spence soils collected at 10-
Mo, ppb 20 cm depth.
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Aqua Regia

Hydroxylamine

Enzyme Leach

Deionised Water
Figure 10. Ranges of Al extracted by
four leaches for 129 B-horizon soils
1 10 100 1000 10000 100000 from the Abitibi.
Al, ppm

Aqua Regia

Hydroxylamine

Enzyme Leach

Deionised Water
Figure 11. Ranges of Mn extracted by
four leaches for 129 B-horizon soils
0.01 0.1 1 10 100 1000 from the Abitibi.
Mn, ppm

Aqua Regia

Hydroxylamine

MMI

Enzyme Leach

Deionised Water

Figure 12. Ranges of Cu extracted by

five leaches for 129 B-horizon soils
1 10 100 1000 10000 100000 1000000 from the Abitibi.
Cu, ppb
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~10,000 years have past since the ice sheets melted, giving limited time for soil-forming
processes and for the migration of material from mineralization to form anomalies. Clay-
sized particles of primary minerals are more susceptible to leaching than the silt and fine
sand particles forming the minus 80 mesh material for the Spence samples. Thus the
extraction of endogenic components by even weak leaches is likely to be greater. This
effect is shown by Al, where more Al is removed by the weaker leaches from the Abitibi
samples than those from Spence. For all three elements shown there is a greater de-
gree of overlap in the concentration ranges extracted by the different leaches.

Considerations in Using Selective Leaches

Only two of the six leaches employed at Spence can be considered selective leaches:
ammonium acetate for carbonate and hydroxylamine for Mn oxides. However, neither
are truly “selective” since the former dissolves some aluminosilicates and hydroxylamine
dissolves both aluminosilicates and carbonates. These leaches are not exceptional in
this respect; most, if not all, selective leaches dissolve minerals other than the target
mineral.
Two features reduce the effectiveness of selective leaches. First, although it is desirable
to measure the exogene phase of several indicator elements, these may be partitioned
into different secondary minerals. At Spence for example, Mo has been mainly parti-
tioned into a resistant mineral phase that is dissolved only by aqua regia, whereas Cu
and As have been partitioned into carbonates.
The second feature, discussed earlier, is that secondary minerals contain elements of
endogenic as well as exogenic origin. Selective extraction will be more or less effective
depending on the relative amounts of endogenic and exogenic components in the target
mineral. This may be illustrated by the plot for the extraction of Cu by ammonium ace-
tate at Spence (Figure 13). The ammonium acetate dissolves the carbonate hosting the
Cu. This carbonate has a low content of Cu of endogenic origin, so that the anomaly to
background contrast is high. Similarly, MMI-A is sufficiently acidic to dissolve carbonate
and this leach, too, gives a good anomaly contrast. Hydroxylamine dissolves not only
carbonate, but Mn oxides. Anomaly contrast is lower, because the latter mineral must
contain a higher proportion of endogenic Cu, which is added to the leach solution.
Whereas carbonate at Spence has a high ratio of exogenic to endogenic Cu, the con-
verse is true for As. Ammonium acetate extracts have a high background concentration
of As, which leads to poor anomaly/background contrast (Figure 14).

Considerations in Using Precursor Leaches

As defined earlier, precursor leaches attempt to extract the elements introduced from
mineralization, before these become involved in soil-forming processes and are fixed in
secondary minerals. In most cases, the precursor phases in anomaly formation will be in
water-soluble form or weakly adsorbed on minerals. The most simple of these leaches
is water. Another is the Enzyme Leach. As shown in the preceding figures, there is sub-
stantial overlap between the amounts of major and trace elements extracted by deion-
ised water and Enzyme Leach. Given that Enzyme Leach is weakly acidic, there is
some dissolution of carbonate (Cameron et al., 2000). Whether MMI should be classi-
fied as a precursor or selective leach is uncertain. Little information has been published
on the nature of the leach solutions and since major elements are not measured, it is
not possible to judge to what extent secondary minerals in the soil are dissolved.
Figure 15, showing Cu by Enzyme Leach at Spence should be compared with Figure 13
that shows the extraction of this element by ammonium acetate. As noted above, pre-
cursor phases will usually be smaller in amount than those that have been incorporated
into secondary minerals to form the principal mass of the anomaly. The background
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25000

20000
C u A m m onium A cetate, ppb

Contrast Ratio = 5.9

15000

10000

5000

0
473500 474000 474500 475000 475500 476000
East
Figure 13. Plot of Cu by ammonium acetate in soils across the Spence deposit with deposit indicated by a yel-
low bar and median value by the interrupted line. Copper in Spence soils is mainly hosted by carbonate, which
is dissolved by this leach.
60000

Contrast Ratio = 1.2

A s A m m onium Acetate, ppb

40000

20000

0
473500 474000 474500 475000 475500 476000
East
Figure 14. Plot of As by ammonium acetate in soils across the Spence deposit with deposit indicated by a yel-
low bar and median value by the interrupted line. Arsenic in Spence soils is also mainly hosted by carbonate,
which is dissolved by this leach.
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500

400

Contrast Ratio = 3.1

C u E nzym e Leach, ppb

300

200

100

0
473500 474000 474500 475000 475500 476000
East
Figure 15. Plot of Cu by Enzyme Leach in soils across the Spence deposit with deposit indicated by a yellow
bar and median value by the interrupted line.

(median) concentration of Cu by Enzyme Leach is 66 ppb, whereas it is 1060 ppb for

ammonium acetate that dissolves carbonate hosting most of the Cu. Maximum values
for the two leaches are 469 ppb and 23900 ppb respectively: the Enzyme Leach anom-
aly maximum is only 2% that of ammonium acetate. Nevertheless, since the background
concentration by Enzyme Leach is also low, this precursor phase gives a clear anomaly.
The median and maximum amounts of Cu by deionised water, at 27 ppb and 241 ppb
respectively, are in the same range as Enzyme Leach, the higher contents by the latter
leach being accounted for by its partial dissolution of carbonate.
Figure 16 shows plots of Zn by different extraction methods for B-horizon clay soils over
VMS mineralization at Cross Lake. Zinc by Enzyme Leach shows a distinct, single peak
anomaly directly over the mineralization. The absolute amounts of Zn are low, inter-
preted to be largely water-soluble element and representative of the precursor phase
prior to incorporation in secondary minerals. Zinc by ammonium acetate represents the
element present in carbonate minerals. The amounts of Zn are higher and show a dou-
ble peak anomaly on either side of the mineralization. The pH of the soils is low above
the mineralization; in these soils carbonate has been dissolved. The topography falls
from the surface above the mineralization, to a stream at 275 m South. The dissolved
Ca plus Zn has migrated down slope in the soils and carbonate containing Zn has pre-
cipitated in an area of higher pH at 240-250 m South to form one of the twin peaks of
the ammonium acetate anomaly. The hydroxylamine data show a further stage in the
evolution of the anomaly; Zn that has migrated down slope has been fixed in Mn oxides
as well as carbonates, both of which are dissolved by hydroxylamine, which gives the
highest values for Zn. MMI-A leach dissolves more carbonate than Enzyme Leach, but
less than ammonium acetate and may represent an intermediate stage between these
two leaches in terms of the Zn response.
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300 2000

A B
1600
Zn Enzyme Leach, ppb

200

Zn MMI, ppb
1200

800
100

400

0 0
100 150 200 250 300 350 100 150 200 250 300 350
South, m South, m
3000 5000

C D
2500
4000
Zn Ammonium Acetate, ppb

Zn, Hydroxylamine, ppb

2000
3000

1500

2000
1000

1000
500

0 0
100 150 200 250 300 350 100 150 200 250 300 350
South, m South, m

Figure 16. Plots of Zn extracted from soils taken from the upper 10 cm of B-horizon clay soils on Line 6 at Cross Lake,
near Timmins. VMS lens at 29 m depth subcrop shown by yellow rectangle. A Zn by Enzyme Leach, B Zn by MMI, C Zn
by ammonium acetate, pH 5, D Zn by hydroxylamine.
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Considerations in Using Strong Leaches

Whatever precursor or selective leach is used, it is desirable to supplement this with an
analysis by aqua regia extraction. Aqua regia—ICP-MS analyses are relatively inexpen-
sive and can give results of high precision for up to sixty elements. This provides infor-
mation on the bulk composition of the sample, which is invaluable for interpreting the
data for the other leaches. Mistakes in interpreting data from precursor or selective
leaches can be caused simply by comparing samples of different bulk composition.
Some anomalies are mature, having undergone an extended period of development,
with conversion of the exogene element phase into chemically resistant secondary min-
erals. For such anomalies, aqua regia may give the best anomaly/background contrast.
Such seems to apply to some of the elements forming anomalies at Mike, Nevada
(Jackson, 2000; Cameron and Doherty, 2001).

References
• Cameron, E.M., Hall, G.E.M., McClenaghan, B. and Hamilton, S., 2000. Effects of Carbonate in
Samples on Selective Extraction by Enzyme, Hydroxylamine and MMI Leaches. CAMIRO Deep-
Penetrating Geochemistry Report 11 pp.
• Cameron, E.M. and Doherty, M.E., 2001. Geochemical Data from a Soil Traverse across the Mike
Gold-Copper Deposit, Carlin, Nevada. CAMIRO Deep-Penetrating Geochemistry Report 22 pp.
• Clark, J.R., 1993. Enzyme-induced leaching of B-horizon soils for mineral exploration in areas of
glacial overburden. Trans. Inst. Min. Metall. 102: B19– B29.
• Hall, G.E.M. and Cameron, E.M., 2001. Comparison of Selective Extractions in Soils over the
Spence Deposit, Chile. Part A: Sequential Extractions of a Soil Profile. CAMIRO Deep-Penetrating
Geochemistry Report 15 pp.
• Jackson, R.G., 2000. Mobile Ion Geochemistry, Mike Epithermal Gold Deposit, Nevada, USA.
CAMIRO Deep-Penetrating Geochemistry Report 17 pp.