Page 1

OVERVIEW: DETECTING MINERALIZATION BENEATH CLAY COVER

Eion M. Cameron

Overview
The basis for a model for the dispersion of elements through clay cover (Figure 1)
comes from the measurements of ORP and pH on drill core by Stew Hamilton. The
most complete results are from Line 6SE at Cross Lake, where a 20 m thick, sphalerite-
rich VMS lens is overlain by 30 m of clay and silt.
There is a dispersion of reduced materials, including transition metals, that rise from the
oxidising sulphide body to the surface, forming a reduced column in the clay. Above the
water table, there is a source of oxygen that reacts with the reduced material generating
acid (Hamilton et al, 2001):
2+ +
2Fe + O2 + 4H2O → 2Fe(OH)3(S) + 2H
Earlier work showed a SP low over the VMS lens (Figure 2), suggesting that it is oxidiz-
ing and thus able to liberate metal ions.

Figure 1. Model, based on field observations, for the dispersion of reduced materials from a sulphide body through
clay cover. Modified from Hamilton et al. (2001)
 Page 2

SP mv, Moving Average of Three 7

4
50 100 150 200 250 300 350

Figure 2. SP survey, Line 6SE, Cross Lake. Horizontal scale in meters. Red rectangle: subcrop of
VMS. SP results in mv are a moving average of three points.

300

250
Zn Enzyme Leach, ppb

200

150

100

50

0
50 100 150 200 250 300 350

Figure 3. Zinc by Enzyme Leach in B-horizon soils above VMS mineralization covered by 30 m of
clay. Red line: top 10 cm of B-horizon, blue line 10-20 cm interval depth in B-horizon. Line 6SE,
Cross Lake. Horizontal scale in meters. Red rectangle: subcrop of VMS.

Sampling of conventional B-horizon soils in 1999 failed to identify an anomaly in Zn over

the mineralized zone on Line 6SE, whereas analyses of samples collected at a constant
depth of 10-25 cm below the base of the Ao-horizon and analysed by MMI did find a dis-
tinct anomaly in Zn. The 1999 B-horizon samples were generally from an interval whose
average depth was greater than 25 cm from the Ao. In 2000 the portion of the line near
the mineralization was resampled, taking samples from (a) the top 10 cm of the B-
horizon and (b) the 10-20 cm interval of the B-horizon. The results for Zn (Figures 3 and
4) show a clear anomaly in the upper B-horizon samples, but a flat response from the
lower samples. Why this pronounced depth effect?
In Figure 5, the pH of both the upper and lower B-horizon samples have been plotted as
 Page 3

2000

1500
Zn MMI, ppb

1000

500

0
50 100 150 200 250 300 350
South, m

Figure 4. Zinc by MMI in B-horizon soils above VMS mineralization covered by 30 m of clay. Red
line: top 10 cm of B-horizon, blue line 10-20 cm interval depth in B-horizon. Line 6SE, Cross Lake.
Horizontal scale in meters. Red rectangle: subcrop of VMS.

8
pH of B-Horizon soils

5
50 100 150 200 250 300 350

Figure 5. Polynomial regression for pH of B-horizon soils above VMS mineralization covered by 30
m of clay. Red curve: top 10 cm of B-horizon, blue curve 10-20 cm interval depth in B-horizon. Line
6SE, Cross Lake. Horizontal scale in meters. Red rectangle: subcrop of VMS.

polynomial regressions, which most clearly reveals their inter-relationship. Both curves
show a pronounced low over the mineralization, with the upper B-horizon samples hav-
ing lower pH values than the interval 10 cm below. The pH affects the carbonate content
of the soils, dissolving the carbonate in the lower pH areas, with the Ca moving laterally
to precipitate in flanking zones of higher pH. The plot for Ca as carbonate (Figure 6)
shows the same inter-relationship between the layers as does pH: more carbonate has
been removed from the upper B-horizon than the lower.
In September, 2001 we paid a final project visit to Cross Lake and had a backhoe dig a
trench that extended 100 m on either side of the mineralized zone. Soil profile samples
were collected along the trench for follow-on projects. Examination of the trench gave a
 Page 4

15000
Ca Hydroxylamine, ppm

10000

5000

0
50 100 150 200 250 300 350

Figure 6. Polynomial regression for Ca by hydroxylamine, representing CaCO3, in B-horizon soils

above VMS mineralization covered by 30 m of clay. Red curve: top 10 cm of B-horizon, blue curve
10-20 cm interval depth in B-horizon. Line 6SE, Cross Lake. Horizontal scale in meters. Red rectan-
gle: subcrop of VMS.

Figure 7. Soil profile above VMS mineralization on Line 6SE. The top of the B-horizon is orange-
brown, changing at depth to light or dark brown, without the orange cast. There is an intermedi-
ate zone of mottled brown surrounded by weakly-orange brown, which is taken to represent an
intermediate stage in the oxidation of the clay and silt.
 Page 5

Fe Ammonium Acetate, ppm 350

300

250

200

150

100

50

0
50 100 150 200 250 300 350

Figure 8. Iron by ammonium acetate at pH 5 in B-horizon soils above VMS mineralization covered
by 30 m of clay. Red line: top 10 cm of B-horizon, blue line 10-20 cm interval depth in B-horizon.
Line 6SE, Cross Lake. Horizontal scale in meters. Red rectangle: subcrop of VMS.
perspective on the nature of the clay soil that was less apparent when viewing soil pits.
A typical soil profile is shown in Figure 7. Below the A-horizon the soil is an orange-
brown colour. Down-profile, the orange colour gradually disappears and the soil is in
various shades of light to dark brown. There is an intermediate zone where the soil is
mottled orange brown and brown, reflecting non-uniform oxidation. From place to place
along the trench, there was marked variation in the development of the B-horizon, i.e.
an upper zone of soil with an orange cast.
Soils below the A-horizon are “tight”, with very limited permeability and the appearance
of the soils in profile is that oxygen has been very slow to permeate. Thus the top of the
B-horizon has become a reaction zone (Figure 7) between oxygen that can move
through the more permeable A-horizon and reduced materials that are moving from be-
low. Within this reaction zone, redox-sensitive ions will precipitate, much as they do
along redox fronts in roll-front uranium deposits. When redox-sensitive ions, such as
2+ 2+
Fe and Mn , precipitate, they will co-precipitate other metals. Preferential precipita-
2+
tion of Fe in the top 10 cm of the B-horizon is suggested by the plot shown in Figure 8.
2+ 2+
Precipitation of Fe can co-precipitate Zn .
Another interpretation was also considered: that vegetation is cycling elements to the
surface, which fall and become organic litter. Decomposition of the litter might then
cause elements to be released and fixed near the top of the B-horizon. However, analy-
ses of humus and tree organs, reported elsewhere on this CD, show no particular en-
hancement in Zn over the mineralized zone on Line 6. Moreover, this could not account
for the pronounced increase in Fe directly over the mineralization shown in Figure 8.
Sampling at 10 cm intervals is too crude to map the behaviour of elements at a redox
front. In a future project it may be worthwhile to resample these soils at finer resolution.

References
• Hamilton, S., Cameron, E.M., McClenaghan, B. and Hall, G.E.M., 2001. Deep-Penetrating Geo-
chemistry: Cross Lake final report. CAMIRO Deep-Penetrating Geochemistry report. 73 pp