.

Journal of Geochemical Exploration 61 1998 173189

A comparison of selective extraction soil geochemistry and
biogeochemistry in the Cobar area, New South Wales
D.R. Cohen
a,)
, X.C. Shen
a
, A.C. Dunlop
a
, N.F. Rutherford
b
a
Department of Applied Geology, Uniersity of New South Wales, Sydney, NSW 2052, Australia
b
Rutherford Mineral Resource Consultants, 87 Brook St, Coogee, NSW 2034, Australia
Received 30 March 1997; accepted 18 November 1997
Abstract
.
In parts of the deeply weathered and semi-arid environments of the Cobar area NSW, Australia , detection of
mineralisation using conventional soil sampling and total metal analysis is impeded. This is due to the intense leaching of
trace elements within the weathered profile, discontinuous coverage of transported materials and the existence of diffuse
regional geochemical anomalies of ill-defined source. Selective chemical extractions, applied to various regolith compo-
nents, and biogeochemistry offer a means of isolating localised geochemical patterns related to recent dispersion of trace
.
elements through the overburden. Lag geochemical patterns across the McKinnons deposit Au and Mrangelli prospect
.
PbZnAs reflect mechanical dispersion processes and minor hydromorphic effects. Concentrations of more mobile
elements tend to be higher in the non-magnetic fraction, due to higher proportions of goethite and poorly crystalline hematite
than in the magnetic fraction. The subdued soil geochemical responses for metals extractable by cold 40% hydrochloric acid
.
CHX and for total element concentration reflect the leached nature of the residual profile, low grade of mineralisation,
dilution by aeolian components and disequilibrium of fine fractions with coarser, relict Fe-oxides. The stronger contrast for
CHX for most metals, compared with total extraction, indicates surface accumulation of trace elements derived from
underlying mineralisation. Enzyme leach element anomalies are intense but generally located directly over bedrock sources
or major structural breaks, irrespective of the nature of the overburden. Though mechanisms for the dispersion of trace
elements extracted by enzyme leaching are not well established, the lack of lateral transport suggests vertical migration of
.
volatile metal species atmimorphic dispersion . The strong, multi-element response to mineralisation in cypress pine needles
indicates significant metal recycling during the present erosional cycle. However, a comparison of the trace element
.
concentrations in vegetation cypress pine needles and selective extractions of soils indicates that recycling by the plants is
not the dominant mechanism for transportation of metals through the overburden. The vegetation may be responding to
hydromorphic dispersion patterns at depth. The use of selective extractions may be useful in detecting mineralisation through
deeply leached profiles, but offers even greater potential when integrated with biogeochemistry to detect targets buried by
significant thickness of transported cover. q1998 Elsevier Science B.V. All rights reserved.
Keywords: selective extraction; biogeochemistry; lag; enzyme leach; McKinnons
)
Corresponding author. E-mail: d.cohen@unsw.edu.au
0375-6742r98r$19.00 q 1998 Elsevier Science B.V. All rights reserved.
. PII S0375- 6742 97 00052- 6
( ) D.R. Cohen et al.rJournal of Geochemical Exploration 61 1998 173189 174
1. Introduction
Single step and sequential, selective chemical ex-
tractions are used in geochemical exploration to
characterise element dispersion mechanisms, to im-
prove geochemical contrast by screening out trace
element components not derived from local miner-
alised sources, and to detect subtle leakage haloes
emanating from deeply buried mineralisation. In
many geochemical terrains, weak geochemical dis-
persion haloes are actively forming in the top few
metres of overburden due to groundwater movement,
capillary action, diffusion of volatile compounds

1
.
atmimorphic dispersion , natural electrochemical
gradients, vegetation recycling and the action of
organisms. Metals transported by these mechanisms
would typically be associated with recently devel-
oped, transient and metastable secondary minerals,
such as amorphous Fe and Mn oxyhydroxides, espe-
cially metals that are not readily incorporated into
the crystalline mineral phases. Such element accumu-
lations may represent only a small fraction of the
total trace element content of the overburden; hence,
geochemical contrast would be suppressed if total
metal extractions were used.
In the absence of detailed mineralogical studies,
most extractions are, in effect, only operationally
.
defined Hall et al., 1997 , the amount of trace
elements released being dependent on the degree of
crystallinity and purity of the mineral phases present,
dissolution conditions and digestion time. The newly
developed enzyme leach appears to selectively dis-
solve amorphous manganese oxides and other solu-
ble phases, and yet is slow to attack crystalline
manganese oxides, amorphous or crystalline iron

oxides or carbonates Clark, 1993; Cohen et al., in

.
prep . In the early stages of reaction, strong solutions
.
of cold hydrochloric acid CHX primarily attack
manganese oxides and poorly crystalline Fe oxides,
rather than more crystalline Fe oxides. The latter,
including hematite, are more gradually attacked by
.
CHX Xie and Dunlop, 1998 .
Geochemical anomaly detection in the Cobar area
is impeded by the presence of transported overbur-
1
. From the Greek atmi n,f svapour.
den, truncation of weathered profiles, removal of
zones of trace element palaeo-accumulations and
development of diffuse regional geochemical haloes.
Although stream sediments and lag have been used

in regional reconnaissance surveys Dunlop et al.,

.
1983 , conventional sampling procedures have had to
be adapted to accommodate the problem of Quater-

nary and recent siltation of drainage channels in-

cluding augering to zones containing buried lag;
.
Schmidt, 1990 . At the prospect scale, various soil
fractions and regolith components have proven effec-
tive sampling media in erosional landforms domi-

nated by residual overburden Scott et al., 1991;

Chaffee and Scott, 1995; Cairns et al., 1995; Cohen
.
et al., 1996 . In many cases, sampling has focussed
on an ill-defined B-horizon, developed in the mas-
sive red soils of the region, with the objective of
detecting metals suspected to be accumulating under
the present cycle of weathering. Selective extraction

on soils by weak hydroxylamine hydrochloride Chao

.
and Zhou, 1983 has provided interpretable patterns,
particularly for Au, near mineralisation at McKin-
.
nons Rugless and Elliot, 1995 . Although such ap-
proaches have proven effective over some truncated
profiles and in areas with thin transported cover, it is
less certain that such an approach will delineate
metal sources under thick transported cover.
An alternative to regolith sampling is the analysis
.
of groundwater Giblin, 1995 . This, however, is
dependent on the availability of water bores, which
are sparse in the Cobar area. Another alternative to
regolith sampling is biogeochemistry. Phreatophytes
assimilate trace metals from large volumes of soil
and weathered bedrock, via interaction between their
extensive root systems and groundwater or contact
with soil particles. Biogeochemistry has been able to
delineate mineralisation in various Australian ter-

rains Baker, 1986; Cohen et al., 1995; Lintern et al.,

.
1995; Marshall and Lintern, 1995 , in some cases in
the absence of strong anomalies in adjacent soils
.
Smith and Keele, 1984 .
This study compares the response of a relict
.
medium lags with that of vegetation and the total,
CHX and enzyme leach soil geochemistry over the
.
McKinnons deposit Au and the Mrangelli prospect
.
AsPbZn . This provides a basis for discussion of
the nature and extent of dispersion processes, and
future planning and interpreting geochemical surveys
( ) D.R. Cohen et al.rJournal of Geochemical Exploration 61 1998 173189 175
in areas of transported cover in regions with charac-
teristics similar to those of the Cobar area.
2. Site descriptions
The Cobar area is part of an extensive palaeo-plain
in southeastern Australia, which evolved while Aus-

tralia was part of the Gondwana supercontinent Ol-

.
lier and Pain, 1994 . This feature is known locally as
the Cobar Pediplain and its antiquity is indicated by
the presence of remnant olivineleucitite flows, 14
16 Ma in age, which extruded subsequent to deep
.
weathering Byrnes, 1993 . Humid conditions ex-
.
tended until the Mid Miocene Martin, 1991 , fol-
lowed by more arid conditions during the Late
Miocene and MidLate Pliocene. Dissection of the
Cobar Pediplain weathering surface has produced a
gradation from relict, erosional domains to deposi-
.
tional domains Senior, 1992 . Although the timing
of the onset of this dissection is poorly constrained,
widespread climatic change elsewhere to a more arid
regime and mild tectonism suggests a Mid-Miocene
age, with further adjustments during the Pliocene and
Pleistocene.
The area has low topographic relief. Local zones
of silicification, associated with mineralised struc-

tures or more resistant lithologies sandstones and

.
conglomerates form topographic highs. Deep weath-
ering may extend below 100 m, and has generally
produced a quartzkaolinitemuscovitesaprolite as-
semblage. Ferruginous, residual cappings are not
widely developed, although heterogeneous ferricretes
of detrital character are common on or near the
surface.
A veneer of lag, of diverse origin and morphol-

ogy, is widespread in the erosional domains Alipour

.
et al., 1996 . The transformation of surface Fe-oxides
to maghemite, attributed to bushfire activity by Fitz-
.
patrick 1988 , probably dates from the Late
Miocene. In localised, depositional domains along
more densely vegetated drainage lines and adjacent
plains, colluvial and alluvial mantles rest on trun-
cated weathering profiles. The alluvium may be more
than 50 m thick and contain interfingering silts and
gravels. The character of the gravels is comparable
with the adjacent lag, and typically includes a signif-
icant proportion of maghemite-rich clasts.

Soils are typically massive red earths Walker,

.
1978 which show little profile differentiation and
are interpreted to have a significant aeolian compo-
nent. Recent deflation of interfluve areas has con-
tributed large quantities of silty colluvium along the
present drainage lines. Thin, discontinuous, surface
.
calcrete zones nodules and cements occur at the
base of slope and along drainage lines, with some
deeper lenses in transported cover observed in over-
burden drill samples. The calcrete is probably devel-
oped as a result of evapotranspiration.
The southern Cobar area is dominated by the
.
association of bimble box Eucalyptus populnea
.
and white cypress pine Callitris columellaris Cun-
.
ningham et al., 1981 . Cypress pine is the most
uniformly distributed species, forming dense stands
along drainages, and is the first tree to recolonise
cleared land.
2.1. McKinnons
The McKinnons gold deposit is located 37 km
south west of Cobar and was the first deposit discov-
ered on the western edge of the Cobar Basin. In this
study, soil, lag and vegetation samples were col-
lected, at 100 to 200 m spacing, from two 8-km
.
traverses: line A 79600N which passes 400 m to
.
the north of the mine and line B 76000N which
.
passes 3 km to the south Fig. 1 .
The general area was targeted for follow-up ex-
ploration on the basis of anomalous Au, Ag, As, Sb
and Pb contents in -180 mm stream sediments,
although streams adjacent to the deposit display
background metal values. The deposit was discov-
ered in 1988 by Norgold Ltd., through rock chip
sampling of a quartz-veined, silicified outcrop. Min-
eralisation is hosted by weakly metamorphosed, sili-
cified and brecciated, laminated to massive siltstones

and fine sandstones of the Amphitheatre Group part

.
of the early Devonian Cobar Supergroup . The min-
eralisation appears to follow the axial trace of the

northwesterly trending Nullawarra Anticline Rug-

.
less and Elliot, 1995 which is intersected around
20000E on line A. The mineralisation assemblage
commences with Au near-surface and progresses to
an AuAg assemblage at depth; PbZnAg mineral-
isation is common at depths greater than 80 m
.
Bywater et al., 1996 . The deposit had an original
( ) D.R. Cohen et al.rJournal of Geochemical Exploration 61 1998 173189 176
F
i
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.
1
.
M
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.
( ) D.R. Cohen et al.rJournal of Geochemical Exploration 61 1998 173189 177
ore reserve of 2.2 mt at 1.91 grt Au, which is now
mined out. An intersection of 20 m at 1 grt along
line A indicates an extension of the mineralised
structure some hundreds of metres to the north of the
.
pit Maxey, 1995 . This structure appears to extend
to the south of the pit.
The pre-existing profile has been strongly trun-
cated, with only the lower saprolite zone preserved.
Contact between the saprolite and fresh bedrock is at
a depth of about 60 m. The area is gently sloping to
undulating, with a thin cover of residual and collu-
vial soil. Interspersed drainages contain a basal layer
of mixed residual soil, colluvium and alluvium, over-

lain by up to 15 m of transported material mainly

.
silts . Outcrop in the area is rare. Lithic and pisoid
lags are common in the erosional landforms. To-
wards drainage channels, the abundance and size of
lag decrease, whereas the quartz content and propor-
tion of magnetic to non-magnetic lag increase.
2.2. Mrangelli
The Mrangelli prospect is located 25 km west of
Cobar at the western end of the eastwest trending
Amphitheatre Dome. Soil, lag and vegetation sam-
.
ples were collected along line C 9400N , at 100 m
.
sample spacing Fig. 2 .
The area is dominated by silicified, resistant ridges

of Biddibirra Formation sandstone with local eleva-

.
tion up to 50 m . Mineralisation is composed of clots
of disseminated pyrite, galena and sphalerite, hosted
by strongly silicified sandstone and a quartz-veined
fault zone. Coincident PbAs lag and rotary air blast
.
drill RAB geochemical anomalies were delineated
by Dominion Mining above weathered CSA Silt-
stone. Peak lag values of 2000 ppm As and 500 ppm
.
Pb above respective backgrounds of 50 ppm occur
near outcropping mineralisation.
The lower slopes are dominated by variably
weathered siltstone. Intense weathering of the profile
up to 10 m depth is observed in RAB holes, but well
developed mottling and local ferruginisation may
extend to 20 m below surface. Pisoid lags are abun-
dant, whereas lithic, silicified and subangular peb-
bles of sandstone increase in abundance towards the
elevated outcrops. Pedogenic calcrete is common at
the edge of the erosional landforms and in stream
beds.
3. Sampling and analysis
Lag samples were collected at intervals of 100 to
200 m and obtained by sweeping the ground surface
at a number of locations within 10 m of the nominal
site. The samples were sieved to the 211 mm size
range. The magnetic and non-magnetic components
were separated and a large proportion of the quartz
content removed from the non-magnetic fraction by
.
hand. Representative portions 50 to 100 g of each
fraction were milled to -75 mm.
Soils were collected from 1020 cm depth to
avoid the more recent transported material. Samples
for the CHX digestion and total extraction were
collected at 100-m intervals and composited to pro-
vide 200-m spacings. Soil samples used for the
enzyme leach work were collected from the same
sites as those for lag and vegetation. Soils were
sieved to -180 mm for total extraction and enzyme
leach, and to -75 mm for CHX extraction.
Cypress pine needles were selected as the princi-
pal biogeochemical sampling medium due to their
strong response to mineralisation compared with
.
other species Pahlow, 1995 , limited seasonal vari-

ability and resistance to dust contamination Cohen

.
et al., 1996 . In July 1995, samples of needles were
collected from the lower branches of three to five
individual trees at each site. Samples were dried and
macerated, but left unashed. Seasonal variation test
sites have since been established above mineralised
and background sites at McKinnons.
Total metal contents of the lag and soil were
determined by a combination of INAA and
HFrHClO rHNO digestion followed by AAS anal-
4 3
ysis. The CHX extractions for soils were performed
by a commercial laboratory. Samples of 4 g were
digested at room temperature for 4 h in 10 ml of a
40% HCl solution, with occasional mixing. Analysis
was performed using ICPMS. A 1-h enzyme leach
was also performed by a commercial laboratory and
the solutions centrifuged. For the selective extrac-
tions, solutions were analysed by ICPMS, cali-
brated against in-house reference materials. For the
vegetation, 10-g samples were encapsulated in poly-
thene vials and analysed by INAA. Vegetation sub-
samples from Mrangelli were also digested in aqua
.
regia 10 g in 100 ml and analysed by AAS for Pb
and Zn.
( ) D.R. Cohen et al.rJournal of Geochemical Exploration 61 1998 173189 178
F
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.
( ) D.R. Cohen et al.rJournal of Geochemical Exploration 61 1998 173189 179
Table 1
. Analytical detection limits ppm
Element Soils and lag Vegetation
INAA AAS ICPMS Enzyme leachrICPMS INAA AAS
As 1 0.2 0.005 0.05
Au 0.005 0.0001 0.0001 0.0003
Cu 1 1 0.005 1
Fe 500 500 200 200 200
La 0.5 0.001 0.01
Pb 1 0.2 0.001 1
Sb 0.2 0.1 0.001 0.01
Zn 2 0.3 0.01 1
Analytical quality control was monitored using
primary and secondary reference materials and sub-
sample duplicates. Combined sub-sample and analyt-
ical variance was less than 10% at concentrations

above three times the analytical detection limits Ta-

.
ble 1 .
4. Results
4.1. McKinnons
On lines A and B, both magnetic and non-mag-

netic lag display a series of spot Au anomalies 710

.
ppb , extending east from the main northeast-trend-
.
ing mineralised zone Fig. 3 . A similar pattern is
observed in the total Au contents of the adjacent
soils, though anomalies on line A are restricted to the
zone of mineralisation and adjacent drainage. On line
A there is a contiguous set of CHX-Au anomalies
.
0.30.7 ppb , extending 250 m either side of the
projection of the structure hosting the mineralisation.
CHX-Au values are slightly elevated in the drainage
on the eastern end of the line, and in general, appear
to be slightly elevated across the alluvium filled
channels. A spot enzyme leach anomaly of 1.2 ppb
occurs above the trend of mineralisation, with a
subsidiary peak in the adjacent drainage. A consis-
tent, 2 km wide Au anomaly is observed in the
cypress pine needles. Concentration peaks at 4.2 ppb
.
above a background of 0.8 ppb and the anomaly is
centred on the projection of the McKinnons mineral-
isation. The Au spike in the needles at 23400E,
located at the top of a low ridge, cannot be related to
known mineralisation.
Well developed and consistent Au anomalies are
not observed in the soils on line B for either the
partial or the total extractions. The exception is the
12 ppb anomaly above a background of -2 ppb for
the total extraction and 0.25 ppb above a background

of 0.15 ppb for CHX at 22200E with a weak

.
anomaly in the needles . In the cypress pine needles,
the most prominent feature is a group of five low-
contrast anomalous sites spanning an alluvium-filled
channel between 19400E and 20000E, reaching 1.0
3.0 ppb. More subdued features reaching 1.2 ppb,
situated near 18000E and 22000E, are associated
with marginally elevated Au contents in CHX and
total soil extractions. Several of these anomalies are
related to fold hinge zones and quartz veining near
18000E. Between 20400E and 20800E, thin, residual
soils partially cover an antiform hinge zone associ-
ated with a persistent zone of en-echelon, narrow

shear zones possibly an extension of the Fence

.
Shear . These are also located adjacent to prominent,
coarse-grained, quartzose sandstone-grit units, within
which intermittent, narrow quartz veins, increased
cleavage development and adjacent silicification are
common. Previous work by Burdekin Resources in-
dicates broad, regional, low-level As and Sb anoma-
lies to be derived from this structure.
Arsenic, Sb and La values in soils and lags on
.
line A Figs. 3 and 4 are much more subdued than
Au, with no obvious reflection of the McKinnons
mineralisation. At the edge of the eastern drainage
line, near 23500E, lags contain 80240 ppm As and
2040 ppm Sb in the non-magnetic fraction and soils
( ) D.R. Cohen et al.rJournal of Geochemical Exploration 61 1998 173189 180
. Fig. 3. Comparison between Au and As contents of lags, soils total, CHX- and enzyme-extractable components and cypress pine needles
along lines A and B, McKinnons. The profile is based on surface mapping, RAB drill holes and the projected location of mineralization
from the pit.
display a low-amplitude feature of 810 ppm total
As and 11.6 ppm Sb. Elevated CHX-Sb concentra-
.
tions 0.350.50 ppm overlap the total extraction
feature, and correspond with a peak in the otherwise
ragged pattern of enzyme leach-As values. Although
the area of elevated As and Sb at the eastern end of
the line is covered by soil and alluvium, it is situated
along the northward projection of the OwlOsterly
Fault and regional anticlinal axis, along which other
soil and drainage sediment geochemical anomalies
occur. The prominent enzyme leach-La anomalies
tend to occur at the edge of drainages either side of
the ridge containing the projected zone of mineralisa-
tion, though there is some suggestion of the rabbit
ears style of anomaly on both lines for La, Cu and
Zn. Arsenic and Sb patterns in cypress pine needles
( ) D.R. Cohen et al.rJournal of Geochemical Exploration 61 1998 173189 181
closely follow the trend for Au in the needles and the
projection of the main structure hosting Au minerali-
sation at McKinnons mine 400 m to the south, with
strongly elevated values between 20000E and

21500E. The zone of anomalous La values and

.
other REEs in the needles is displaced from the Au
anomalies, commencing above mineralisation at
20800E and extending across the adjacent drainage
to 19500E.
On line B a prominent AsSb anomaly in nearly

all media is situated at 20400E20800E Figs. 3 and

.
4 , with a subsidiary peak at 21400E, associated with
the Fence Shear. Arsenic and Sb patterns are almost
identical for the various media; however, the anoma-
lous zone tends to be broader for the CHX extraction
than the total values. In lags, the main anomaly
reaches 130250 ppm As and 2565 ppm Sb in the

magnetic fraction compared with 75 ppm As and 20

.
ppm Sb background , whereas the non-magnetic
fraction reaches 100500 ppm As and 2045 ppm
Sb. In the soils, a distinct, relatively high-contrast
feature for the total metal contents of 2045 ppm As
. Fig. 4. Comparison between Sb and La contents of lags, soils total, CHX- and enzyme-extractable components and cypress pine needles
along lines A and B, McKinnons.
( ) D.R. Cohen et al.rJournal of Geochemical Exploration 61 1998 173189 182
and 24 ppm Sb is located above the projected
mineralisation. This feature is repeated as a 0.40.9
ppm As-CHX anomaly, but is not repeated for Sb.
Beyond the strong enzyme leach anomaly of 1540
ppb As, a number of single point anomalies above a
background of 1020 ppb extend east as far as
24000E. The pattern for As in cypress pine needles
is subdued, but there are a number of peaks up to 0.1

ppm though contrast is restricted by the 0.05 ppm

.
detection limit .
Despite the presence of CuPbZn-bearing sul-
phide zones in the base of the mine pit, there is no
observable Cu response in any media and the only
.
Zn response is in the lag on line A Fig. 5 . On line
B, there is a series of Cu and Zn anomalies in the
non-magnetic lag, east of the projected zone of
mineralisation. Narrow zones of anomalous concen-
trations of CHX-Zn and total-Cu also occur in the
soil zones near 20800E, and broadly correspond with
the lag anomalies. Despite high local variability,
low-contrast Zn anomalies for total and CHX extrac-
tions are observed between 18000E and 19000E.
These may relate to the Nullawarra Anticline, west
of McKinnons. Rabbit-ear enzyme leach anomalies
appear to have developed for Cu, Zn and Pb about
the projected zone of mineralisation on both lines,
. Fig. 5. Comparison between Cu and Zn contents of lags and soils total and enzyme-extractable components along lines A and B,
McKinnons.
( ) D.R. Cohen et al.rJournal of Geochemical Exploration 61 1998 173189 183
but the response is somewhat erratic. Most enzyme
leach and CHX peaks correspond with the edges of
the erosional landforms at which groundwater seep-
age and surface accumulation of carbonate is com-
mon.
With the exception of the halogens and some
metals which are mobile as oxyanions, the enzyme
leach patterns are nearly identical for the remaining
42 elements. For the majority of these elements,
most analyses were below detection limits. However,
intense, multi-element enzyme leach spot anomalies
occur directly above mineralised zones, prominent
structural discontinuities and the edges of the larger
drainages. Other features not indicated in the figures
are the large series of anomalous trace element con-
tents, including the REEs, in the cypress pine nee-
dles corresponding to the main section of Au anoma-
lies on line A.
4.2. Mrangelli
A series of 50200 m wide zones between 9400E

and 10350E, displaying elevated As levels 50270

.
ppm at ;6 m depth in RAB holes, were defined by
Dominion Mining. Although RAB data indicate no
significant Au component to the mineralisation at
Mrangelli, 3 ppb Au and 3 ppm Sb soil anomalies
are coincident with weak cypress pine needle Au

anomalies of 0.30.5 ppb above -0.1 ppb back-

.
ground to the east of the Biddibirra Fault at 8500E
.
Figs. 2 and 6 . A series of irregular, 150300 ppm
As peaks extend from 9200E to 11000E in the
magnetic fraction and 120660 ppm As from 9400E

to 10200E in the non-magnetic fraction compared

.
with ;100 ppm background in both lag fractions .
These broadly coincide with the highest RAB values.
The sub-crop positions and the relative strength of
. Fig. 6. Comparison between Au, As, Sb, Pb, Zn and La contents of lags, soils total and enzyme-extractable components and cypress pine
needles along line C, Mrangelli. The profile is based on surface mapping and RAB drill hole data.
( ) D.R. Cohen et al.rJournal of Geochemical Exploration 61 1998 173189 184
RAB geochemical features cannot readily be deter-
mined. The adjacent lag values of about 100 ppm
should be considered anomalous in a regional con-
text, suggesting a broad, mechanical dispersion halo
in both lag fractions. Total As levels in soils define a
subtle, but distinct anomaly of 1040 ppm between
9500E and 10200E. Enzyme leach patterns are simi-
lar to the soils near the strongest RAB As feature
near 10000E, with values peaking at 6090 ppb,
compared with 2030 ppb background. Marginally
enhanced As values extend west to the vicinity of the
Biddibirra Fault. In cypress pine needles, a promi-

nent peak of 0.100.15 ppm above a background of

.
-0.05 ppm is situated between 10100E and
10700E, and is offset 250 m to the west of the
sub-outcrop of the strongest zone as defined by the
As RAB geochemistry.
The pattern for Pb in lags shows prominent peaks
of 300500 ppm at 9700E and 10100E in the non-
magnetic fraction. In the magnetic fraction more
. . Fig. 7. Plots of Au, As, Pb and Zn versus Fe in lags total analysis and soils total, CHX- and enzyme leach-extractable components for the
combined McKinnons and Mrangelli data sets.
( ) D.R. Cohen et al.rJournal of Geochemical Exploration 61 1998 173189 185
subdued peaks of 180200 ppm occur at the same
.
locations. Shoulders to these peaks 100120 ppm ,
over the interval 8800E11600E, form a broad halo
about the mineralised zone. These main peaks coin-
cide with the strongest base-of-hole RAB Pb fea-
tures. In both enzyme leach- and total-Pb soil con-
tents, a single point feature of 110 ppb and 90 ppm,
respectively, is situated at 10100E. This reflects the
broadest zone of RAB Pb features of 150200 m at
230 to 500 ppm Pb, as compared with a 50 m zone
with 1701100 ppm at 9700E. The pattern of Pb in
cypress pines is somewhat irregular, with local peaks
of 22.6 ppm as compared to a background of
0.82.0 ppm. A prominent, low-contrast feature
reaching 2.6 ppm at 10300E10500E is offset 250 m
to the west of the most extensive RAB Pb geochemi-
cal feature.
There is an irregular distribution of Zn peaks
around the mineralised zone. In the magnetic lag
fraction, values reach 270430 ppm and 570620
ppm in the non-magnetic fraction compared with
4080 ppm background. The main peak in both the
magnetic and non-magnetic fractions at 9700E coin-
cides with the highest RAB Pb values, and with Zn
levels above 500 ppm in the upper part of the
underlying RAB holes. The broadest zone of high
RAB Pb values is one of marked Zn depletion in
both magnetic and non-magnetic lag values. Soil
patterns are somewhat similar, with an enzyme leach
single point feature of 150 ppb at 10100E coincident
with the previously mentioned RAB Pb peak. Total
Zn in soil shows a low-amplitude feature of 8085
.
ppm compared with -50 ppm situated over the
Biddibirra Fault. The Zn content of cypress pine
needles ranges from 8 to 15 ppm without discernible
anomalies. As with McKinnons, the CHX soil
anomalies tend to be slightly broader than the total
soil anomalies, or have elevated shoulder values
adjacent to the peak anomalous values.
4.3. Iron controls
The relationship between Fe content and the Au,
As, Pb and Zn concentration of the magnetic and
non-magnetic lags, total and CHX-extractable soils
.
vary among the elements examined Fig. 7 . There is
no correlation between Au and Fe in lags or total
soils, and a very weak correlation between CHX-ex-
tractable Au and Fe. Apart from a few anomalous
samples, the As contents are correlated with Fe in
the lags and total soils but not correlated strongly for
CHX. Lead is also strongly correlated with Fe in the
lags and follows the trends observed at Mrangelli
.
and other sites in the region by Alipour et al. 1997 .
Zinc is weakly correlated with Fe in lags, more
strongly correlated in the total soils, but uncorrelated
for the CHX extraction.
Median element concentrations for samples from
McKinnons and the CHXrtotal metal ratios are pre-
sented in Table 2. The proportion of total trace
elements released by CHX extraction of the amor-
phous Fe-oxides varied markedly between elements.
Though a median of 6.1% of the total Fe content was

extracted by CHX indicating a low proportion of

.
poorly crystalline Fe-oxides in the soils only 4.1%
of the As appears to be bound up in the amorphous
Fe-oxides. Conversely, over 20% of Cu, Pb and Sb
appear bound up in this component.
Table 2
Median concentrations of Au, As, Sb, Ba, Cu, Pb, Zn and Fe in lags and soils from McKinnons
. . . . . Element Magnetic lag total ppm Non-magnetic lag total ppm Soil CHX ppm Soil total ppm Soil CHXrtotal %
As 60 58 0.25 6.05 4.1
. Fe % 39 22 0.21 3.45 6.1
Zn 45 92 1.70 25.00 6.8
. Au ppb 1 1 0.12 1.4 8.6
Ba 430 480 29 300 9.7
Cu 22 22 4 20 20.0
Pb 76 51 4.0 18.0 21.2
Sb 17 13 0.28 1.13 24.8
ns110.
( ) D.R. Cohen et al.rJournal of Geochemical Exploration 61 1998 173189 186
5. Discussion
Geochemical features in the Cobar area are devel-
oped over a thick, relict weathering profile, dating
from the early Tertiary. Most deposits discovered by
exploration geochemistry have been located in ero-
sional regimes where anomalies can be detected in a
wide range of geochemical sampling media. Geo-
chemical anomalies related to mineralised structures
within the three antiforms in the vicinity of the
.
McKinnons deposit AuAs"Sb"Zn"Pb , and a
weakly mineralised zone of silicification at Mrangelli
.
PbZnAs , have been detected by a range of
media and extraction techniques.
The patterns for Au in the lags at McKinnons are
erratic and reflect relict dispersion patterns. The
existence of a series of spot Au anomalies in lag to

the east of mineralisation at McKinnons 21000E to

.
25000E , in the absence of soil or vegetation anoma-
lies, and scattered patches of gravels, suggests topo-
graphic inversion has altered the drainage trend from
eastwards to northwards. The response in both lag
fractions is consistent with the Au being particulate
and most likely derived from local quartz vein-hosted
mineralisation and silicified wall rocks.
Except for sites directly over projected miner-
alised zones in erosional regimes, geochemical con-
trast in total and CHX-extractable soil components is
.
subdued in the order of 2 to 20 . Potential causes for
this include the leached nature of the relict profile,
the low grades of mineralisation, dilution by aeolian
components and disequilibrium of fine fractions with
coarser relict Fe-oxide-rich fragments. The generally
poor correlation between trace element patterns in
the non-magnetic lag and total extraction for soils at

Mrangelli given the magnitude of the lag trace

.
element values may be attributed to the highly
siliceous nature of the non-magnetic lag that would
limit the loss of trace elements to soil. The weak-to-
moderate spatial correlation between the trace ele-
ment contents of the non-magnetic lags and the
CHX-extractable soils at McKinnons and the slight
broadening of the anomalous zones for CHX com-
pared with the totals for soils around the main
.
anomalies also observed in the Fe-contents , sug-
gests that a portion of the amorphous Fe may be
derived from the degradation of adjacent lags and
subsequent dispersion in surface soils. In most in-
stants, CHX geochemical anomalies developed above
mineralised zones are more extensive than those
displayed by the total metal contents of the soils.
The comparatively high CHXrtotal metal ratio
for Cu and Pb in the soils, compared with As and Sb,
may be attributed to stronger retention of Cu and Pb
in the poorly crystalline Fe-oxides. These patterns
are consistent with the dissolution patterns for vari-
ous elements in lags from Mrangelli and nearby
.
Yarrawonga, reported by Alipour et al. 1997 . The
poor-to-insignificant correlation between trace ele-
ments and Fe in both total and CHX extracts pre-
cludes direct application of regression against Fe to
enhance anomaly patterns. Extensive hydromorphic
dispersion and multi-stage lag development are the
likely causes of the low-level As, Bi, Sb and Zn
anomalies which are present in the soils and lags of
drainage systems surrounding discrete sources in the
Cobar area, including drainage lines peripheral to the
weakly mineralised antiforms in the McKinnons area,
.
Elura Schmidt, 1990 and Wagga Tank Scott et al.,
.
1991 .
The distinct multi-element response to mineralisa-
tion in the cypress pine needles downslope from
mineralised sites indicates significant metal recycling
during the present erosion cycle. However, the rela-
tive positions of the vegetation, enzyme leach and
total element concentration peaks indicate that recy-
cling by the plants is not the dominant mechanism
for introduction of metals at surface. In many in-
stances, trace element anomalies in the vegetation or
the limit of vegetation anomalies is displaced 200 to
600 m downslope from equivalent features in the
soils or lag. The vegetation may be responding to the
present or palaeo-hydromorphic dispersion patterns
that have been defined at depth by RAB and auger
sampling. Elevated trace element contents in refrac-
tory Fe-oxide-rich lag are not generally reflected by
either soils or vegetation, though this may relate to
the small proportion of the total profile volume
contributed by lag. The lack of correlation between
the vegetation and CHX soil patterns indicates that
the metals released into the skeletal A-horizon
through the shedding of needles, twigs and bark or
direct plant exudations are being rapidly flushed into
drainages and are not adsorbing to the Fe-oxides in
the upper B-horizon soils.
Enzyme leach anomalies tend to be of the apical
( ) D.R. Cohen et al.rJournal of Geochemical Exploration 61 1998 173189 187
or rabbit-ear types, with the most intense anomalies
occurring directly above potential sources, such as
mineralisation or major structural discontinuities.
There is no indication of the lateral or down-slope
displacement of anomalies evident in the adjacent
vegetation, soils or lag geochemistry. This feature
has also been observed in transported overburden
near the CSA mine and in a variety of other terrains
.
Clark and Cohen, 1995 .
Although no sites were available with defined
mineralised sources covered by thick, transported
overburden without lateral contributions from ex-
posed mineralisation, the geochemical patterns ob-
served may have some implication for exploration in
areas of thick cover in the Cobar and similar dis-
tricts. The relatively narrow and discrete vegetation
As peaks associated with drainage lines on line B at
McKinnons suggest that dispersion is predominantly
down-drainage, whereas on line A, the 1.42.2 km
wide AuAsSbBaLa feature in the needles indi-
cates that a broad hydromorphic fan at depth is being
tapped. Some geochemical dispersion may be de-
rived from palaeo-clastic dispersion of lags and soils
along broad drainage lines, but the lack of correla-
tion between vegetation and lag patterns, together
with the results over PbZnSb features in palaeo-
drainage lines suggests the metals may be in a
relatively refractory form not released to vegetation.
6. Conclusions
The strong, multi-element biogeochemical re-
sponse to mineralisation, with a consistent zone of
anomalies extending up to 1 km either side of the
projected zone of mineralisation at McKinnons, is
indicative of substantial sub-surface hydromorphic
dispersion and biological transport of metals to sur-
face. The lack of correlation between trace elements
and Fe in both the total or CHX soil extracts and the
weaker response to mineralisation in soils than in the
vegetation indicate either lateral hydromorphic dis-
persion does not extend into the upper soil horizons,
or dilution by transported materials.
The dissection and modification of the weathering
profile has generated lag in which geochemical pat-
terns are consistent with predominantly mechanical
dispersion and minor hydromorphic effects. The dif-
ferences between the trace element contents of the
magnetic and non-magnetic lag fractions may be
accounted for by the retention characteristics of the
mineral phases present and the provenance of the lag
.
Alipour et al., 1997 . Patterns relating to poorly

crystalline Fe-oxides operationally defined by the

.
CHX leach , compared with total element contents of
near surface soils, suggest some metal mobility in
the present cycle of weathering, perhaps related to
the same evapo-transpiration processes which are
producing calcrete.
Although some apical enzyme leach metal anoma-
lies have developed directly over major structures or
mineralised zones, some patterns appear to be of the
rabbit-ears type. This pattern is ascribed by Clark
.
1993 to the effect of electrochemical cells related
to oxidizing mineralisation. Although mechanisms
for the dispersion of trace elements extracted by
enzyme leaching are not well established, the vertical
alignment of multi-element enzyme leach anomalies
with major structures or mineralised zones, the lack
of detectable lateral dispersion for Au, and the lack
of correlation with the patterns for the biogeochemi-
cal anomalies suggest the possibility that vertical

migration of trace elements that are subsequently

.
trapped by transient, amorphous Mn-oxides could

include a component of vapour transport atmimor-

.
phic dispersion .
In the erosional regimes, even with thin veneers
of transported material, total analysis of various re-
golith components appears to provide as strong a
response to mineralisation as the vegetation. In areas
with deeper cover of transported material, it is con-
cluded that, although the use of partial digestions
may be an effective means of detecting mineralisa-
tion, they may offer even greater potential when
integrated with biogeochemistry to detect targets
buried by significant thickness of transported cover.
The added analytical costs for exploration programs
are likely to be outweighed by the increased proba-
bility of detecting weak dispersion haloes in regional
surveys and improvements to the interpretation of
geochemical anomaly patterns. One possible sam-
pling strategy in areas of deep, transported cover is
alternate lines of cypress pine needles and either
CHX or enzyme leach extractions from shallow soils,
collected as composites over widely spaced intervals
.
200400 m . The strong geochemical contrast of
( ) D.R. Cohen et al.rJournal of Geochemical Exploration 61 1998 173189 188
enzyme leach anomalies would allow compositing
over a number of sites.
Acknowledgements
The authors thank Burdekin Resources, Cobar
Mines, Dominion Mining and CRA Exploration for
their support and permission to publish the data.
Analyses were provided by Activation Laboratories
. .
Denver and Becquerel Laboratories Sydney . Part
of this project was funded by a grant to DRC from
the Australian Research Council.
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