Journal of Geochemical Exploration, 3 (1974)43-51

© Elsevier Scientific Publishing Company, Amsterdam - Printed in The Netherlands

BIOGEOCHEMICAL EXPLORATION FOR TUNGSTEN AT BARRYTOWN,

NEW ZEALAND

B.E QUIN 1, R.R. BROOKS 1, C.R. BOSWELLl and J.A.C. PAINTER 2

Massey University, Palmerston North (New Zealand}
Carpentaria Exploration Co. Pry. Ltd., Hokitika (New Zealand}
(Accepted for publication July 12, 1973)

ABSTRACT

Quin, B.F., Brooks, R.R., Boswell, C.R. and Painter, J.A.C., 1973. Biogeochemieal exploration fox
tungsten at Barrytown, New Zealand. Z Geochem. Explor., 3: 43-51.

Biogeochemical prospecting for tungsten was carried out at a mineralised area near Barrytown,
New Zealand. The tungsten content of the ash of the shallow-rooted tree ferns Cyathea medullaris and
Dicksonia squarrosa correlated well with the concentrations of this element in the soil. Sampling of
these species therefore provides a possible method of detecting general soil anomalies and moreover
is considerably faster than soil sampling under local conditions.
Trend surface analysis of the concentrations of tungsten in the trunks of all species of common
large evergreen trees sampled on belt transects, could be used to delineate extensions of known tung-
sten mineralisation in bedrock, and was to some extent superior to soil geochemistry in this respect.

INTRODUC~ON

Except for a small amount o f Russian work (e.g. Kovalevsky, 1966), biogeochemical
exploration has rarely been applied to exploration for tungsten because o f difficulties
associated with the analysis o f the low concentrations o f this element normally found in
vegetation. Following the development o f a rapid and sensitive colorimetric m e t h o d
(Quin and Brooks, 1972), an investigation was carried out in an area o f tungsten mineraliza-
tion near Barrytown in Westland, New Zealand. The results of this investigation are re-
ported in this paper.

TEST AREA

The study area is shown in Fig. 1 and consists uniformly o f a granite mass o f approx-
imately 1.5 k m 2 which rises through rugged terrain from an altitude o f approximately
30 m at its western extremity to about 500 m in the east. It is surrounded to the north,
south and east by Precambrian hornfels and greywacke and the west by Recent sur-
ficial deposits, but the area shown in Fig.1 is essentially only granite.
The tungsten mineralisation, approximately 9 8 - 9 9 % scheelite and 1 - 2 % wolframite,
44

t~EY

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stream
'N'ql~- /* \ ~ ridge
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quartz vein

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ARRYTO~VN

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Fig. 1. Map of test area showing sampling sites.

exists in a series of quartz veins (see Fig.l) containing discrete crystals up to 0.5 cm
size and as scheelite disseminated in greisen veins and veinlets up to 2 - 3 cm in thickness.
The dimensions of the quartz are generally obscured, but appear to have a strike length
of 30--70 m, with a maximum vein size of 0.7 m, and tend to occur in swarms containing
10--40 veins over a width of 2 - 3 m.
The annual rainfall is high (approximately 280 cm) with maximum and minimum
 45

monthly averages of 35 cm and 10 cm in October and December, respectively. The

leaching resulting from this high rainfall, in cgmbination with the resistant parent rock,
has produced a soil poor in nutrients and of low pH. The soil consists of a dark-brown,
humus-rich, A horizon approximately 0.3 m in depth and a lighter-brown, B horizon
of extremely variable thickness and lower organic content. Both horizons contain many
rock fragments.
The overstorey vegetation in the region of ridges and spurs is predominantly the ever-
green trees Nothofagus truncata (hard beech) and lgeinmannia racemosa (kamahi) with
increasing dominance ofNothofagus menziesii (silver beech) at higher altitudes. The pale-
grey leached A2 soil horizon, characteristic of that derived from beech species, was
observed in many of the flatter areas. Chief understorey species include Quintinia acutifolia
and Myrsine salicina and much of the forest floor is covered in a dense growth of ferns such
as the ubiquitous Blechnum discolor (crown fern). The vegetation of the creek banks is
considerably more diverse, but is dominated by the tree ferns 6),athea medullaris (mamuka)
and Dicksonia squarrosa (wheki).

FIELD WORK

Soil sampling and preparation

Samples of soils (500 g) were taken from the upper B horizon at selected sites in the
study area (see Fig. 1). The samples were stored in plastic bags until arrival at the laboratory,
then air dried, lightly ground to separate aggregated particles, and the minus 100-mesh
fraction (nylon sieve) was removed for analysis.

Vegetation sampling and preparation

Samples of trunk wood, twigs (2 year old) and leaves were collected from trees growing
near soil sampling sites on the ridges. Trunk samples were taken with a machete, a small
slice being removed from the outer trunk at chest height and after separation of the bark.
Twig samples were kept to approximately uniform size (1 cm diameter) and were taken
from various points around the tree to ensure a representative sample. Leaves were also
taken from various points on the tree and were selected in such a manner that they included
representative numbers of leaves of different ages in order to compensate for variations in
tungsten concentrations which might be caused by these age variations.
The tree ferns on the creek banks were sampled by removing portions of fronds from
different points on the plant at sites close to where the soils were sampled.
All plant samples were stored in plastic bags until arrival at the laboratory, then washed
in running water, air dried and finally ashed at 450°C in a muffle furnace with adequate
admission of air.
Plant sampling was restricted to the commonest species on the ridges; N. truncata,
N. menziesii, W. racemosa, Q, acunfolia and M. salicina. On the creek banks, the tree ferns;
 46

C medullaris and D. squarrosa were sampled. Samples were taken if the chosen species
was found growing within 3 m of a previously-selected soil sampling site. Sites were
situated at 30-m intervals along ridges and creek banks. No trunk samples were taken from
Q acunfolia and M. salicina because of their relatively small size. The great height of the
Nothofagus and Weinmannia species prevented collection of leaves or twigs in many cases.

STATISTICALANALYSIS

Correlation analysis

The significance of plant-soil associations for tungsten was determined by computing

Pearson product-moment correlation coefficients (r) for the concentrations of this element
in plants and soils. Data were transformed to logarithmic values because the concentrations
were log-normally distributed. Values o f r were obtained via an IBM 162011 computer and
significances were established from the probability levels. Conventions used (Brookes et al.,
1966) were: S** (very-highly significant, p < 0.001); S (significant, p = 0.05-0.01); NS
(not significant, p > 0.10)

Trend surface analysis

An IBM 1120 computer was used to apply trend surface analysis to data obtained by
analysing tungsten levels in tree trunks sampled over two belt transects over an area of
suspected mineralisation. The program was used to plot isoconcentration contours for
the original data, the trend surface and the residuals. Plotting was performed on a
Calcomp plotter.

CHEMICALANALYSIS

Tungsten in soils and plant ash was determined by the dithiol colorimetric method
(Quin and Brooks, 1972). This method consists of fusion of soils with potassium
hydrogen sulfate, leaching the melt with 10M hydrochloric acid, reduction of the molyb-
denum with stannous chloride and addition of dithiol dissolved in isoamyl acetate. The
complex extracts into the solvent layer and its absorbance is measured at 630 nm.
Plant material was analysed by dissolving the ash in 10M hydrochloric acid and proceeding
as above.

RESULTS AND DISCUSSION

Plant-soil relationships for tungsten

The analytical data for tungsten in the tree species (Table I) show that the mean
tungsten concentrations decrease in the order: trunks, leaves, twigs. Tungsten was detected
 47

TABLE I

Tungsten in soils and ashed vegetation

Material Locality No. Tungsten content (p.p.m.) Significance of

plant-soil relationship
geome~c range
mean

Soils creek banks 94 98 4 - 1800

ridges 124 44 3 - 620
C medullaris creek banks
leaves 65 7.3 0.2- 85
D. squarrosa creek banks S**
leaves 12 5.6 3.0- 60
M saltcina ridges
leaves 42 2.8 0.1- 50 S
twigs 41 0.2 <0.1- 24 NS
N. menziesii ridges
leaves 6 2.2 0.5- 7.0 NS
twigs 5 1.3 0.6- 7.0 NS
trunks 27 8.4 0.2- 275 NS
N. truncata ridges
trunks 56 6.6 0.4- 300 NS
Q acutifolia ridges
leaves 30 3.0 0.7- 7.0 NS
twigs 28 0.7 <0.1- 15 S
I¢. racemosa ridges
leaves 40 2.2 0.4- 12 NS
twigs 37 0.9 <0.1- 13 NS
trunks 79 5.8 0.6- 100 NS

S** = very-highly significant (p < 0.001)

S = significant (p = 0.01-0.05)
NS = not significant (p > 0.10)

in 348 (90%) o f the tree samples collected. Those that were below the detection limit o f
0.1 p.p.m. (ash weight) were all twig samples.
The concentration o f tungsten in the ash o f tree-fern leaves from stream banks showed a
very-highly-significant correlation with that o f the soil (Table I). The data a r e shown as
profdes in Fig.2. Since the significance o f the p l a n t - s o i l correlation was the same for b o t h
species o f tree ferns, the two species were treated together throughout and classified
merely as "tree ferns".
Fox samples from ridges, no very-highly-significant (S**) correlations were found between
tungsten in soils and in a n y organs o f the overstorey trees (Table I). However, significant
(S) correlations were observed for the understorey shrubs Q. acuttfolia and M. salicina. The
data are shown as profiles in Fig.3.
48

400[
t G.AN~TI
~o,~.
CRr~K

o_ 20

i 1°
c, O I

~ L~TTL~ G~A~ITE ¢Ref~

~ ,
1000 '~---~

o~~ ~/~~

O 500 1000
DISTANCE ALONG STREAM 8AN~- ( r'n )

Fig.2. Concentration prof'lles of tungsten in tree ferns (Cyathea medullaris + Dicksonia squarrosa) and
soils along creek banks. Profiles shown as L0-L1 and G 0 - G 1 in Fig.1.

OU~NTINIA ACUTIPOL~A TWl0S

MyItSlNt SALICINA L~AVeS

0 200 400 600 800 I000 1200 1400

DISTANCe ALONO llOOt • ( m )

Fig. 3. Concentration prof'fle of tungsten in understorey shrubs and soils along Ridge A. Profile shown
as R 0 - R 1 in Fig. 1.
 49

The usefulness of the vegetation in predicting the concentrations of tungsten in the soil,
decreases in the order: tree ferns, shrubs, large trees. The reason for this order is probably
primarily a function of their different root systems. Tree ferns (Q, athea medullaris and
Dicksonia squarrosa) have a shallow and localised root system and they would therefore
obtain their nutrients from the same depth as the soil samples (0.2-0.6 m). The trees,
however, particularly the larger Weinmannia and Nothofagus species, have root systems
which are far more extensive both laterally and vertically. Their roots therefore sample
a larger volume of soil (and possibly bedrock) in which the tungsten concentration may
vary greatly. A particular soil sample may therefore not be representative of this volume
especially if leached.

Trend analysis of tungsten concentrations in tree trunks

A major problem encountered in prospecting for tungsten, was the difficulty in tracing
scheelite-bearing veins between outcrops. Because of the landsliding and leaching resulting
from the rugged topography and high rainfall, the soil-bedrock relationship was often
obscure. As the root systems of the larger tree species can extend considerable depths
and possibly penetrate and therefore "sample" bedrock, an investigation was carried out
to determine the success of plant sampling in this application.
It has been shown above, that the concentration of tungsten was higher in the trunks
than in the leaves and twigs of trees and therefore only trunk samples were taken. Also,
because the major species had similar mean concentrations of tungsten in their trunks
(Table I), all species were grouped together for this investigation.
Two trunk-sampling belt transects measuring 10 m X 24 m, were carried out over an
area of suspected mineralisation (see Fig. 1) perpendicular to the inferred strike of the
vein (north-south). All large trees (irrespective of their genus) within the transects were
sampled and labelled according to their X- and Y-coordinates. Approximately 50 trees
were included in each transect. Fig.4 shows the data for the two transects (A and B)
expressed as original data (Fig.4a), trend surfaces (Fig.4b), and residuals (Fig.4c).
In transect A, the residuals show a high positive anomaly at Y = 6 m (also shown in
the plot of the original data), indicating the presence of a scheelite-containing vein with
a rich pocket at X = 4 m. The smaller anomaly at Y = 14 m possibly indicates the presence
of an offshoot of the main vein.
The residuals plot in transect B show positive anomalies at Y = 11 m and Y = 12 m. Only
the latter is indicated on the plot of the original data.
To determine whether these anomalies corresponded with the position of the bedrock
rnineralisation, trenches were dug across the centre of both transects and samples were
taken from the highly-weathered upper bedrock. B-horizon soil samples were taken at
corresponding points. The positions of the trenches are shown by line CD in transect A
and by EF in transect B (see Fig.4). The rock and soil data are also plotted in Fig.4d. In
both line transects, the position of the highest value for the rock samples, coincided exactly
with the Y-coordinate of the plant anomalies in the plot of the residuals. The soil values,
50

TRANSECT A TRANSECT B

,, >, . . / , . - -

. \, ,
\- ~

soils I~
d ~ bedrock d II

• i

I ,
6 8 IO 12 14 16 18 20 22 0 2 4 6 fl l0 12 14 16 18 20 22 24

DISTANCE y (m)

Fig.4. Trend analysis of tungsten in mixed tree species sampled in belt transects across suspected
tungsten anomalies in bedrock: (a) isoconcentration contours of original data; (b) trend surface
contours; (c) residuals; and (d) profiles of soil and bedrock data for line transects C-D and E - E

however, pinpointed the highest rock values in transect B only. The high concentration
of tungsten in the soil relative to that in the rock, suggests that the scheelite may be
fairly readily leached from the weathered bedrock and precipitated in the soil downslope.
The plant values, in addition to pinpointing the Y-coordinate of the mineralisation
more accurately than the soil data, have indicated the positions of the richest mineralisa-
tion in the veins: i.e. at X = 4 m in transect A and at X = 2 m and X = 8 m in transect B.
The 50 plant samples collected in each transect were collected in a time comparable to
that required to collect the dozen soil samples, due to the thick layer of humus and tree
roots whose presence impedes the rate of soil sampling.

CONCLUSIONS

It is concluded that the tungsten content of leaves of the tree ferns, Dicksonia squarrosa
and Q;athea medullaris is a good indicator of the tungsten content of the soil. Under New
Zealand conditions, the dense forest and thick humus in many areas renders soil sampling
a slow and tedious operation so that sampling of tree ferns can be a speedier method of
detection of tungsten anomalies in soils.
 51

The larger tree species did not give significant correlations with tungsten in the soil,
possibly because their extensive root systems penetrate a large volume of soil in which
the tungsten concentrations can vary greatly. Although being of limited use for detecting
tungsten anomalies in soils, the larger trees by virtue of their extensive and deep root
systems, could be used to detect tungsten mineralisation in bedrock in cases where this
could not always be achieved by soil sampling alone. The detection procedure involved
the use of trend surface analysis but was hardly applicable to widespread regional re-
connaissance because of the high sampling density involved. The technique may, however,
be useful in delineating extensions of known mineralisation.
The current investigations will be extended to areas of different geological, vegetational,
topographical and climatic environments, to determine whether the methods are suitable
for general application in prospecting for tungsten in New Zealand.

ACKNOWLEDGEMENTS

This paper is published with the permission of Carpentaria Exploration Co. Pty. Ltd. The
authors gratefully acknowledge assistance from the staff of this organisation, particularly
Mr. R.M.S. Lee. Thanks are also due to the Mineral Resources Sub-Committee of the New
Zealand University Grants Committee for financial support.

REFERENCES

Brookes, C.J., Betteley, I:G. and Loxston, C.M., 1966. Mathematics and Statistics for Chemists. Wiley,
New York, N.Y., 418 pp.
Kovalevsky, A.L, 1966. Biogeochemistryof tungsten in plants. Geokhimiya, 6:737-744 (in Russian).
Quin, B.F., 1972. Analytical and Biogeochemical Studies o f Tungsten. M.Sc. Thesis, MasseyUniv.,
Palmerston North, 125 pp.
Quin, B.F. and Brooks, R.IL, 1972. The rapid determination of tungsten in soils, rocks and vegetation.
Anal. Chim Acta, 58: 301-309.