JOURNAL OF

GEOCNEMIGAL
EKPLORATlON
ELSEVIER Journal of Geochemical Exploration 60 ( 1997) I S7- 17I

A catchment basin approach to the analysis of reconnaissance

geochemical-geological data from Albay Province, Philippines
Emmanuel John M. Carranza a-b.*, Martin Hale b

Received 11 February lYY7: accepted 2 July iYY7

Abstract

A systematic approach for identifying mineral exploration target areas from reconnaissance stream sediment data without
sufficient a-priori control information has been demonstrated in a portion of western Albay Province in the southern Bicol
Peninsula of the Philippines. The approach involved devising a rapid method of catchment basin mapping using a geographic
information system (GIS) so that the area1 influence of the catchment basins may be incorporated in the geochemical data
analysis. Area1 proportions of mapped rock units occurring in the sample catchment basins and observed Mn and Fe contents
in stream sediments are used as independent variables in multiple regression analysis to predict element contents in stream
sediments related to lithologic and chemical controls. The predicted element contents are filtered-out from the original data
to leave residuals in which the effects of other factors (e.g.. mineralization) may be seen. A simple correction for the effects
of downstream dilution is applied; this allows for the different sizes of the sample catchment basins so that positive
geochemical residuals are enhanced. The inter-relationship of the different positive residuals in ‘highly enriched’ samples are
investigated through principal components analysis to determine and quantify an ‘anomalous geochemical signature’. Lastly,
the ‘anomalous geochemical signature’ is integrated with ‘proximity’ to faults/fractures to determine favourable target
areas. For the test region, the lithologic controls explain between 80% and 1007~ of the variability in most of the elements
studied. Chemical controls account for generally less than 5% of the variability in the data. Most of the dilution-corrected
residuals reveal high relative enrichment in certain areas underlain by andesite and/or diorite. An anomalous Cu-Mg-Fe-Zn
geochemical signature is disclosed by the principal components analysis of the dilution-corrected residuals in ‘highly
enriched’ samples. Most sample catchment basins defined by this ‘anomalous geochemical signature’ pertain to areas
underlain by andesitic rocks. Integration of the ‘anomalous geochemical signature’ and ‘proximity’ to faults/fractures
reveals that some of these anomalous sample catchment basins are favourable target areas. These areas are interpreted to
contain andesite-hosted stockwork or stringer zones that once formed part of a complete stratigraphic sequence of a
volcanogenic massive sulphide occurrence. The results demonstrate the usefulness and ability of the procedures followed to
extract significant anomalies from the reconnaissance geochemical data without the benefit of sufficient a-priori control data
to aid in anomaly recognition. Similar procedures could also be applied elsewhere. 8 1997 Elsevier Science B.V.

Keywords: Mineral exploration; Stream sediment sampling: Catchment basin; Albay Province (Philippines)

’ Corresponding author.

0375-h742/97/$17.00 0 1997 El\evier Science B.V. All right\ reserved

PII s0375-~74?~97~0003~-0
1. Introduction
The effective interpretation of geochemical data
requires that every available piece of information be
brought to bear on the problem, together with a
thorough understanding of the fundamental princi-
ples of exploration geochemistry as applied to a
specific area. Sufficient prior information is impor-
tant so that the recognition of significant geochemi-
cal anomalies is facilitated. Available geoscience
data that may be used as analogs (i.e., a-priori
thresholds from a geochemical orientation survey) or
those that allow the use of conditional probability
laws in the mapping of mineral potential (e.g., Bon-
ham-Carter et al., 1988) may be regarded as control
data. Any established geo-attributes of a mineralized
locality within a study area are thus regarded as
control data; the mineralized area(s) then form the
control location(s).
Reconnaissance stream sediment surveys may be
carried out: (a) in well-prospected mineralized re-
gions where control data are available: or (b) in
regions where there are no known mineral occur-
rences, i.e., control data or locations are unavailable.
In the former case, where the main objective is to
identify new target areas, the task of delineating
favourable grounds is facilitated in that geo-attri-
butes of every sample location can be compared with
those of the control locations. On the other hand, for
regions wherein control data or locations are unavail-
able, the task of distinguishing background samples
from anomalous samples remains difficult. This was
the case in the interpretation of stream sediment
geochemical data on 201 samples covering 225 km’
of western Albay Province in the Bicol Peninsula of
the Philippines, where there are no known metallic
mineral occurrences. Also, a geochemical orientation
survey had not been conducted prior to the recon-
naissance survey so that control data (e.g., a-priori
thresholds) are unavailable to facilitate recognition
of significant anomalies.
The conventional approach of establishing uni-
element thresholds in order to distinguish anomalous
samples from background samples and thereby iden-
tify target areas is considered inadequate because the
rather rare occurrence of mineralization is only one
of the geologic factors that causes variations in the
stream sediment geochemistry. A major factor that
influences the variations of element contents in
stream sediments is the average (background) com-
position of non-mineralized rocks within the catch-
ment basins. It is thus necessary to determine local
background (predicted values) appropriate for each
stream and remove this background from the ob-
served values in order to leave residuals from which
the effects of anomalous geological processes (e.g.,
mineralization) may be seen.
In this paper, we follow a catchment basin ap-
proach to eliminate the effects of lithologic controls
on the stream sediment element contents, similar to
that of Bonham-Carter et al. (1987). Area1 propor-
tions of mapped rock units occurring in the sample
catchment basins are used as independent variables
in multiple regression analysis to predict element
concentrations due to the rock units. These concen-
trations are then filtered-out from the original data.
The effects of chemical controls (e.g., scavenging
metal ions by oxides of Mn and Fe, etc.) in the
surficial environment are also removed using the
same technique. In order to enhance the positive
geochemical residuals, a simple correction for down-
stream dilution, following the relation suggested by
Hawkes (1976) is applied. Mapping of the positive
dilution-corrected residuals shows sample catchment
basins that are ‘highly enriched’ in any one of the
elements studied. A principal components analysis
on the dilution-corrected residuals in ‘highly en-
riched’ sample catchment basins is performed to
determine and quantify an ‘anomalous geochemical
signature’. Mapping of the ‘anomalous geochemical
signature’ scores indicates anomalous sample catch-
ment basins. Finally, the ‘anomalous geochemical
signature’ scores are integrated with ‘proximity’ to
(curvi)linear structures in the test region to determine
favourable target areas.
2. The test region
The test region is situated in the western part of
Albay Province in the Bicol Peninsula of southeast-
ern Luzon Island of the Philippine Archipelago in
the western Pacific (Fig. 1). The test region is a
portion of the Panganiran Quadrangle (Map Sheet
No. 3659 II) which was geologically mapped ini-
tially at 1 : SO.000 scale (Bureau of Mines and Geo-
 E,J..W Carran;a, M. Hale/Journal c?f Exploration 60 (1997)
Geochemical 157-171 159

A Quaternary volcanic centr

-Cretaceous, or oldc
metamorphic rock!

\\High-angle faul
5”

3’

Fig. I. Location of the test region. Geological features taken from Bureau of Mines and Geosciences (I 9X?).

sciences, 1985). The geological map shown in Fig. 2
is a modification by Carranza (1994).
Most of the test region is underlain by andesitic
and dioritic rocks belonging to the Early Oligocene
Ragay Volcanics and the Late Oligocene Panganiran
Diorite, respectively. Isolated inliers of thermally
metamorphosed Eocene Pantao Limestone occur
within the andesitic rocks. The diorite is intrusive
into the andesite and the limestone. Younger sedi-
mentary rocks, belonging to the Early-Middle
Miocene Bicol Formation and the Late Miocene-
Pliocene Albay Group, underlie the eastern parts of
the region, while pre-Tertiary Panganiran Ultra-
mafics, which form the basement rocks in Albay
Province, occur in the southeast.
Several northerly and northwesterly striking faults
and fractures, sympathetic to the Philippine Fault
Zone located more or less 25 km to the west (Fig. l),
dissect the test region. The known mineral deposits
of the region are only hydrothermal gypsum( + pyrite
+ clay). These have been mined in a small area in
the western part of the region. The deposits, which
are now almost depleted, occur as fracture fillings
along northwesterly trending fractures that cut al-
tered andesite.
A drainage geochemical survey of the test region
was carried out in 1991 (Carranza, 1992) by sam-
pling active stream sediments along second- and
third-order streams, resulting at an average sample
density of one per square kilometre. The minus
go-mesh fraction of the stream sediments was anal-
ysed for Cu, Pb, Zn, Ag, Ni, Cr, Li, Ca, Mg, Fe, Mn,
As and Sb. The geochemical data for Pb, Sb, and Ag
were of very poor analytical precision and were not
considered in the study.
3. Map data
A map of sample catchment basin outlines (Fig.
3) was generated automatically using ILWIS (In-
Fig. 2. Geological map of the test region (modified from Bureau of Mines and Geoscienux 1985). Key: alluvium = Rcccnt alluvium:
shale = Ligao Formation; siltstone = Albay Group: limestone = Albay Group: \and\tonc = B~col Formation: diorite = Pangamran Dlorite:
andesite = Ragay Volcanics: limestone = Pantao Limestone; ultramaficc = Pdnpaniran I~ltramafic\

tegrated Land and Water Information System), a
computer-based geographic information system (GIS)
developed by the International Institute for Aerospace
Survey and Earth Sciences, Delft. The map was
produced in raster format, using 30 m X 30 m pixels
on a UTM projection. Each basin segment corre-
sponds to the area upstream and/or upslope of each
sampling site, terminating at the location of the next
sample site and at the top of the drainage divides.
Each pixel in the raster map of the sample catchment

Table I
Elementary statistics of the original data and skewness of the log,,-transformed data

Element Minimum Maximum Mean Std. De\. Skewness Skewness (loge)

Cu (ppm) 23 9x 51 II 0.62 - 0. IX
Zn (ppm) 23 360 4Y 33 5.7x I .s I
Ni (ppm) I9 1370 9x 193 5.03 3.1x
Cr (ppm) I3 670 72 xz 5.02 0.94
A\ (ppm) 0. I 7.8 I .4 I .5 I .x7 ~ 0.03
Li (ppm) 0.7 73.Y s.2 4.x I .79 0.5 I
Mn (ppm) I60 2780 543 351 3.06 0.70
Fe (a,) I .3 10.8 3.7 1.2 I .69 -0.19
Mg (“/c) 0.47 1.35 1.25 0.57 2.34 0.63
Ca (So) 0.3 13.2 I .Y 2.1 2.s7 0.6Y
 E.J.M. Carranza, M. Hale/ Journal of Geochemical E.rploration 60 (1997) 157-171
Fig. 3. Streams (lines), sample localities
basins is labelled according to the sample number.
The boundaries of mapped lithologic units in Fig. 2
were also digitized and rasterised using a pixel size
of 30 m X 30 m on a UTM projection. The resulting
image is thus identical in size and location to the
catchment basin image. From these steps we pro-
duced a database containing information about the
chemical composition of each sample catchment
basin, the sample catchment basin area, and the area1
proportions of each rock type in the associated basin.
4. Elementary statistics and data transformation
Table 1 contains the summary statistics of the
analytical data of the ten elements under study. As
indicated by their skewness coefficients, all element
distributions are positively skewed. Some maximum
values are large, over five standard deviations from
the mean, and such large values have a dominant
(circles). and sample catchmentbasins (polygons)for the test region
effect on the results of the statistical analysis. The
decision, therefore, was to work with the natural
logarithms (log,) of the data instead of the raw
values. This transformation is used to alleviate the
problems caused by the large values and is not a
judgment of a possible log-normal distribution of the
data; a square root transformation might have served
equally well. Using this logarithmic transformation,
asymmetry of the distribution is effectively reduced
(Table 1).
5. Regression analysis
Given the observed stream sediment element con-
tents Y, at locality i, and the area1 proportions. XLj,
of the jth rock unit in the ith sample catchment
basin attached to locality i, the stream sediment
element contents, ?,, due to lithology are predicted
162 E.J.M. Carranza, M. Hale/Journal of Geochemical Exploration 60 (1997)157-l 71

using a simple regression model as follows:
f; = h, + f h,Xi,
.j=
1 additive
with s,,=m ,X,j = 1.0 for J = 1,2,. . . , m rock units in
sample catchment basin i; b, and bj are the regres-
sion coefficients. Estimation of the element concen-
trations is 2ccomplished by minimizing the quantity
C/i ,(Y. - Yi) using the least squares regression pro-
cedure.
It is assumed that the predicted element contents
are a result of mixing of weathering products of the
rock units (i.e., an additive mixing model); that is,
setting b, = 0 and interpreting as the mean element
contents of the jth rock unit. Because of the signifi-
cant positive skewness of the element distributions,
the values of Y are log,-transformed. Having taken
the natural logarithms, however, the model becomes
multiplicative with respect to the raw data, and the
(‘1
mixing hypothesis is not modelled
(Bonham-Carter et al., 1987). Nonetheless, the log,
transforms of the original data are used and b,, is
forced through the origin so that the b,‘s are usually
positive and easy to interpret (e.g., Bonham-Carter
and Goodfellow, 1986).
In order to evaluate the relative contribution of
the area1 proportions of rock units and their ability to
account for the total variation in the data, a forward
and forced simultaneous inclusion of the independent
variables into the regression equation is performed.
Thus, not simply the most significant variables are
searched and included in the final regression equa-
tions according to a statistical criterion; rather all

Fig. 4. Sample catchment basins shaded according to the groupings of the geochemical data on which Feparate regression experiments are
performed.
 E.J.M. Carranza, M. Hale/Journal of Geochemical Exploration 60 (1997) 157-171 163

variables are included in the final regression equa-
tions. In order, however, for the results of the regres-
sion analysis to be significant, separate regression
analyses are performed on three groups of the geo-
chemical data (Fig. 4) based on threshold values
determined by examining the probability graphs of
the uni-element data (not shown here; Sinclair, 1974).
The data grouping, which shows conformity to the
geology (Fig. 2) was deemed necessary so that the
problem of mixed populations is more or less avoided
(Howarth and Sinding-Larsen, 1983). The element
contents of samples in the different groups are re-
gressed only against the area1 proportions of those
rock units that occur in the associated sample catch-
ment basins.
Besides area1 proportions of rock units, Mn and
Fe contents are also used as independent variables in
combination with the area1 proportions of rock units.
Hence, two sets of regression experiments are per-
formed on the three groups of the geochemical data:
(1) regression against area1 proportions of rock units;
and (2) regression against area1 proportions of rock
units, Mn and Fe contents. In the second set of
regression experiments b, is set to 0 just as in the
first set of regression experiments and a forward and
forced simultaneous inclusions of the independent
variables in the regression equations is performed. In
the first set of regression experiments the variation
of the dependent variables are attributed to lithologic
controls (i.e., area1 proportions of rock units) while
in the second set of regression experiments the addi-
tional contributions of Mn and Fe to the explained
variability of the dependent variables are attributed
to chemical controls (e.g., scavenging by Fe-Mn
oxides, trace element contents related to mafic min-
erals, etc.).
The effectiveness of the independent variables in
accounting for the variation of the dependent vari-
ables can be characterized using R2 (expressed as a
percentage), the ratio of the sum of squares ex-
plained by the regression to the total sum of squares.
Bonham-Carter et al. (1987) pointed out that statisti-
cal tests of significance of the regression are consid-
ered inappropriate if the individual sample points
exhibit some degree of autocorrelation and thus are
not independent. In this study, because of the rela-
tively high sampling density, the individual sample
points are expected to be autocorrelated so that
statistical tests of significance of the regression ex-
periments were not carried out.
5.1. Results of regression experiments
The results of the regression experiments are sum-
marized in Table 2. For all elements except As, Mg
and Ca, the lithologic controls explain between 80%
and 100% of the variations in the geochemical data,
depending on the element and group examined. The
lithologic controls account for only 8-30% of the
variations in As, Mg and Ca in the low and interme-
diate groups and for 65-80% in the high group. For
most elements, the chemical controls generally ac-

Table 2
Summary of results of regression analyses
Dependent variables % Variation due to independent variables (R*)

low group intermediate group high group

lithology lithology + Mn + Fe lithology lithology + Mn + Fe lithology lithology + Mn + Fe
CU 99.82 99.83 99.60 99.66 99.75 99.88
Zn 99.40 99.66 99.11 99.21 99.81 99.86
Ni 99.23 99.34 99.12 99.32 99.14 99.65
Cr 98.63 98.73 98.42 98.44 98.93 99.52
AS 37.4 45.79 8.76 38.13 85.26 89.29
Li 82.38 86.08 87.73 91.60 97.21 98.19
Mn 99.71 99.73 99.36 99.59 99.75 99.81
Fe 95.96 96.22 86.34 91.26 98.10 98.54
Mg 10.59 25.06 24.69 45.48 67.80 81.29
Ca 12.83 15.49 28.29 68.18 72.10 89.64
164 E.J.M. Carranza, M. Hule/.lournal
count for less than 1% in explained variation over
that already explained by the lithologic controls. For
As, Mg and Ca, the chemical controls account for at
least 5% additional variability, depending on the
group examined.
6. Filtration of the effects of lithologic and chemi-
cal controls
The results of the second set of regression experi-
ments are used to predict element concentrations, pj,
for sample i that are due to the lithologic and
chemical controls according to the equation:
< =
where: b,, b,, and b,, are the regression coeffi-
cients of the lithologic and chemical controls; X,,
are area1 proportions of j = 1,2,. . . ,m rock units in
sample catchment basin i; and Mn and Fe are log,-
transformed concentrations of these elements for
sample i. Filtration of the predicted values from the
observed data (i.e., Y. - t.) would result in residuals
related to the effects of other factors. Because filtra-
tion of the effects of lithologic and chemical controls
are based on different regression equations (i.e., for
the three groups of the geochemical data represent-
ing the different geological-geochemical conditions
in the test region), the residuals are standardized into
z-scores in order for these values to be comparable
(Howarth and Sinding-Larsen, 1983).
7. Correction for effects of dilution
Where positive geochemical residuals result from
the filtration of predicted element contents from the
observed element contents, these could be considered
as enrichment due to the effects of anomaly sources,
one of which might be mineralization. However, the
magnitude of the geochemical residuals is controlled
by downstream dilution by mixing of sediments from
non-anomalous sources, which in turn is a function
of the drainage catchment area. In correcting for
dilution, Bonham-Carter and Goodfellow (1984,
1986) used the following formula based on the rela-
oj’Geochemica1 Exploration 60 (19971 157-171
tion developed by Hawkes (1976):
A,,,(&,; =A,( Y - t) +A,,,< (3)
where: A,,,, = area of anomaly source in catchment
basin attached to sample i; Y,, = stream sediment
element contents due to anomaly source in catch-
ment basin i; A, = area of catchment basin attached
to sample i; and Y,, t = observed, predicted stream
sediment element contents for sample i.
With the assumption that a unit area of exposed
mineralization (i.e., A,n, = 1 km’) is contributing to
the stream sediments, Bonham-Carter and Goodfel-
low (1984, 1986) considered the term A,,,Y,,, as a
‘mineralization rating’ that permits positive geo-
chemical residuals to be classified according to im-
portance. However, using the above formula to cor-
rect for dilution, the ‘unwanted’ predicted element
contents due to lithologic and chemical controls are
‘added’ back by virtue of the term A,,?;. Rose et al.
(1979, p. 399) pointed out that the term A,, f, can
be neglected if the catchment area is large relati!e to
the mineralized area. We neglect the term A,,,Y, by
assuming a unit area of 1 ha (or 0.01 km’) of
exposed anomaly source that is contributing to the
stream. This assumed area of anomaly source is
10 X to 200 X smaller compared with the area of
the smallest to the largest sample catchment basins.
Thus, the term A,,,it. is neglected and the dilution
formula becomes:
0.01 Y,, = A!( Y; - f;) (4)
which is equivalent to
v,,,, = 100 A, ( Y, - f, ) (5)
This latter formula is used to correct the positive
geochemical residuals for the effects of dilution.
Although the actual area of exposed anomaly source
is unknown and since there are no known metallic
mineralization in the region, the assumption of a unit
area of exposed anomaly source enables the dilution
correction to work in this particular case so that
possibly enriched catchment basins are highlighted.
The units for Y,, are dilution-corrected residuals in a
sample catchment basin as if the positive geochemi-
cal residuals were wholly due to an exposed anomaly
source over an area of 1 ha. It is also assumed that
contributions from alluvial river bank material can
 E. J.M. Carranza, M, Hale/Journal ofGeochemical Explorarion 60 (1997) 157- 171 165

< 45
45 - 90
> 90

Fig. 5. Maps showing observed Zn contents (upper panel) and dilution-corrected Zn residuals (lower panel).
166 E. J.M. Carranza, M. Hale/Journal of Geochemical Exploration 60 (1997) 157- 171

be neglected, that no feedback between sediment and Table 3

water occurs, and that erosion is uniform within each Principal components analysis of a subset of 84 samples contain-
ing > 80 percentile dilution-corrected residuals for at least one of
catchment basin.
the ten elements
Although the model clearly will not apply univer-
Principal components loadings
sally, Hawkes (1976) shows reasonable agreement
between theory and prediction of four porphyry cop- PC1 PC2 PC3

per deposits. Considering the differences in the sizes CU 0.116 - 0. I29 0.842
Zn 0.593 0.014 0.550
of the sample catchment basins (not shown here), we
Ni - 0.671 0.602 0.089
feel that dilution correction is warranted despite the
Cr ~ 0.686 0.481 - 0.021
limitations of the method. AS 0.639 0.581 0.002
The uni-element dilution-corrected residuals re- Li 0.565 0.533 0.098
veal that original intermediate to high anomalous Mn 0.181 0.25 I -0.111
Fe 0.115 -0.313 0.319
values of single elements are either downgraded of
Mg - 0.416 0.424 0.599
upgraded. For example, the spatial distribution of
Ca 0.621 0.377 ~ 0.326
observed Zn contents (Fig. 5, upper panel) indicates % of var. 26.1 II 17.159 16.078
intermediate values over the sedimentary rocks in the Cum. 8 of Var. 26.117 43.336 59.414
eastern part of the region and over andesitic and
ltalicised coefficients indicate significant variables.
dioritic rocks north- and south-central parts of the
region, and anomalous values over the andesite in
northeast-central part of the region. On the other
hand, the spatial distribution of the Zn dilution-cor- principal components analysis. Log-transformation
rected residuals (Fig. 5, lower panel) has: (a) reduced of the data to alleviate the effects of these factors is
the importance of some portions of the observed not possible due to the presence of negative residuals
anomalous zone; (b) upgraded the significance of in the data. It was thus decided to perform a simple
some intermediate background areas over the north- rank-ordering approach, i.e., assigning ascending
and south-central parts of the region; and (c) down- ranks of 84 through 1 to the descending values of
graded much of the intermediate Zn values. each variable (tied ranks are averaged), and compute
the Spearman rank correlation coefficients for all
possible pairs of variables. Principal components
8. Multi-element classification of the dilution-cor- analysis is carried out on the rank correlation matrix
rected residuals (George and B on h am-Carter, 1989) and the results
are presented in Table 3.
The inter-relationships inherent in the dilution- The first three principal components account for
corrected residuals of the ten elements are investi- some 60% of the total variability of the rank-trans-
gated through principal components analysis. Be- formed data and represent different element associa-
cause this procedure tends to be dominated by non- tions that are more or less interpretable. The other
anomalous element associations, a subset of 84 principal components are not readily interpretable
‘highly enriched’ samples containing > 80 per- and are not discussed further.
centile positive dilution-corrected residuals for at The first principal component (PCl) accounts for
least one of the ten elements was selected so that at least 25% of the variance, including most of the
anomalous element associations would be enhanced. variations in As, Ca, Zn, Li, Cr, Ni and Mg. The
However, histograms of the dilution-corrected resid- strong positive and negative loadings represent two
uals (not shown here) in the ‘highly enriched’ sam- associations, As-Ca-Zn-Li and Cr-Ni-Mg, that
ples reveal the presence of multiple populations, are inversely related, i.e., an enrichment in one
extremely high and low values, and probably non- association corresponds to a depletion in the other
normal distribution of these data. These factors un- and vice versa. The As-Ca-Zn-Li association is
dermine a reliable estimate of the Pearson correlation interpreted as modelling secondary enrichment due
matrix which is used as the starting point of the to adsorption by clay minerals because Ca and Li are
 E.J.M. Carranza, M. Hale/Journal of Geochemical Exploration 60 (1997) 157-171 167

Fig. 6. Map showing sample catchment basins characterized by an anomalous Cu-Mg-Zn-Fe geochemical signature represented by > 80
percentile PC3 scores.

among the elements commonly adsorbed by clays in as related to clay adsorption, enrichment in the Cu-
the weathering environment. The Cr-Ni-Mg associ- Mg-Zn-Fe association is probably un-related to clay
ation is interpreted to reflect unmapped erosional adsorption. The Cu-Mg-Zn-Fe association is inter-
remnants of the ultramafic rocks. These associations preted to be an anomalous multi-element geochemi-
are considered to be non-anomalous. cal signature that probably represents mineralization
The second principal component (PC2) accounts in the test region.
for at least 17% of the total variance and has high The PC3 scores for the rank-transformed data are
positive loadings on Ni, As, Li, Cr, Mg and Ca. It is calculated according to the formula (George and
also interpreted to represent a multi-element associa- Bonham-Carter, 1989):
tion that models secondary enrichment due to ad-
10
sorption by clays, This association is also considered
Sci = c Icj’ij for i = 1,2,. , . ,84 samples (6)
non-anomalous. j= f
The third principal component (PC3) accounts for
at least 16% of the total variance and is associated where: S,i = score for i on component c; lcj =
mainly with Cu, Mg, Zn, Fe and Ca. The high loading of variable j on component c; and Y,~= rank
positive loadings on Cu, Mg, Zn and Fe and the high of variable j for sample i. The PC3 scores are
negative loading on Ca imply an antipathetic relation classified into five percentile classes (O-75, 75-80,
of the former four elements with the last. Because 80-90,90-95 and 95-100) in order to determine the
enrichment in Ca (and associated elements in the 1st anomalous sample catchment basins.
and 2nd principal components) is already interpreted The map of PC3 scores (Fig. 6) highlights adjoin-
168 E.J.M. Carran;a. M. Ha/e/Journal of Grochemicd Explorrrtion 60 C19971 157-I 71

ing anomalous sample catchment basins (i.e.. with Table 4

> 80 percentile PC3 scores) in the northeast-central Classification of ‘proximity’ to (curvi)linear features and per-
centile classes of ‘anomalous geochemical signature’ into pixel
part of the region and also reveals other isolated
values
anomalous sample catchment basins. Some of the
‘Proximity’ to faults/fractures ‘Anomalous geochemical
sample catchment basins with anomalous Zn dilu-
signature’
tion-corrected residuals (Fig. 5, lower panel) are
Distances Pixel Percentile Pixel
downgraded in the PC3 map while other sample
(km) value Cl&\ value
catchment basins with non-anomalous Zn dilution-
> 2.00 0 samples not ‘PC- 0
corrected residuals are nevertheless characterized by analysed’
anomalous geochemical signature. Unshaded sample I so-2.00 60 O& 7s 375
catchment basins in Fig. 6 represent samples with I .OO- I.50 80 7s x0 775
non-anomalous (i.e., < 80 percentile) dilution-cor- oso- I .oo I30 80- 90 850
0.25-0.X) 270 YO- YS 925
rected residuals for all ten elements.
0.00-0.25 x00 95-100 915

9. ‘Proximity’ to (curvihinear features

deposits whose element contents find their way into
Faults/fractures play an important role in the the streams by weathering and erosion; and (b) these
localization of stream sediment anomalies because: structures provide channelways for the upward mi-
(a) these structures are common loci of mineral gration of groundwater that have come in contact

Fig. 7. Map showing relative distances to faultv/fractures.

 E.J.M. Curran;u. M. Hole / Jountnl
with buried mineral deposits. This suggests that zones
with an anomalous geochemical signature that are
proximal to fracture zones may deserve additional
attention.
A map showing distances to faults/fractures in
the test region was generated in ILWIS (Fig. 7).
These faults and fractures are derived from existing
geological maps and from linear patterns interpreted
from air-photographs. In order to integrate the
‘anomalous geochemical signature’ and the ‘proxim-
ity’ to linear features, the raster map of each data set
is re-classified in such a way that high pixel values
indicate high ‘anomalous geochemical signature’ and
high ‘proximity’ to structures. The re-classification
of the raster maps of the ‘proximity’ and ‘anomalous
geochemical signature’ is summarized in Table 4.
For the ‘proximity’ raster map, each corridor is
classified with a pixel value equal to one hundred
times the inverse of the mean relative ‘proximity’
range. For the ‘anomalous geochemical signature’
raster map, each percentile class is classified with a
of Grochemicd Expiorurion 60 (1997) 157- I71 169
pixel value equal to ten times the mean of the
percentile range. The multipliers (i.e., 10 and 100)
are arbitrary and used only to avoid decimals for
simplicity in the numerical operations.
The re-classified raster maps of the ‘proximity’
and ‘anomalous geochemical signature’ are then
multiplied; the products of these variables are then
referred to as ‘favourability’ scores. The mean
‘favourability’ scores in the individual sample catch-
ment basins are then scaled into the same percentile
classes for the PC3 scores. Sample catchment basins
with ‘favourability’ scores > 80th percentile are re-
garded as favourable target areas (Fig. 8; unshaded
sample catchment basins in this illustration represent
samples with non-anomalous dilution-corrected
residuals for all ten elements).
Favourable target basins (Fig. 8) are those previ-
ously classified as anomalous on the basis of PC3
scores and those defined by high but non-anomalous
PC3 scores (Fig. 61. The integration of the ‘anoma-
lous geochemical signature’ and the ‘proximity’ to
170 E.J.M. Carranza, M. Hale/ Journal of Geochemical Exploration 60 (19971 157-I 71
structures has either upgraded or downgraded the
favourability of some of these basins. Since most of
the favourable target basins are isolated from one
another, those adjoining basins in the northeast-
central part of the region and underlain by the an-
desitic rocks are considered to be the most favourable.
These clustered favourable sample catchment basins
are interpreted as reflecting a possible andesite-hosted
stockwork or vein-type sulphide mineralization that
probably once formed part of a complete strati-
graphic sequence of a volcanogenic massive sulphide
(VMS) occurrence. This part of the test region now
requires further exploration.
10. Conclusions
(1) The main objective of this study was to devise
a systematic approach to the analysis of reconnais-
sance geochemical data from areas wherein a-priori
control data are unavailable. The results of the study
demonstrate that significant geochemical anomalies
may be extracted from the reconnaissance stream
sediment data through a 5stage process that in-
volves: (a) filtering of the effects of factors irrelevant
to mineralization through multiple regression analy-
sis; (b) correcting the residual data for the effects of
dilution using a formula modified from Hawkes
(1976); (c) mapping of highly enriched sample
catchment basins based on the dilution-corrected
residuals; (d) determining and quantifying an
‘anomalous geochemical signature’ based on the
highly enriched samples through principal compo-
nents analysis; and (e) integrating the ‘anomalous
geochemical signature’ and ‘proximity’ to structural
features.
(2) Consideration of the area of influence for the
individual sample sites, i.e., the sample catchment
basin, permits the effective integration of mapped
geological data with stream sediment geochemical
data in order to extract more significant anomalies.
(3) A geographic information system, such as
ILWIS, is an excellent computing platform for build-
ing a database that allows mapped geological data to
be integrated with the stream sediment geochemical
data for effective interpretation of geochemical
anomalies.
(4) Filtering out effects of factors irrelevant to
mineralization is of prime importance in exploration
geochemistry. Through multiple regression analysis,
the dominant effects of lithologic and chemical con-
trols can be filtered-out from the geochemical data
and allowing attention to be focused on the positive
geochemical residuals. This latter feature may be of
particular benefit in the interpretation of the recon-
naissance geochemical data as mineralization, being
a relatively rare phenomenon, will normally con-
tribute only a (very) minor component of the total
variability in the data.
(5) Correcting or normalizing for the geochemical
residuals for the effects of downstream dilution en-
ables the enhancement of positive residuals. Catch-
ment basin geochemical maps of dilution-corrected
residuals reveal areas that are not readily recogniz-
able or only partly recognizable in the catchment
basin geochemical maps of the original data.
(6) Further filtration of the effects of other factors
irrelevant to mineralization can be performed through
a principal components analysis of the dilution-cor-
rected residuals. For the test region, this has revealed
an anomalous Cu-Mg-Zn-Fe association and by
mapping of the ‘anomalous geochemical signature’
scores the multi-element geochemical data were re-
duced into a single derived geochemical map that
shows the distributions of anomalous areas.
(7) Integration of the ‘proximity’ to structures
enhances the delineation of favourable target areas.
Acknowledgements
This paper form part of E.J. Carranza’s MSc
research at ITC with financial support from the
Netherlands Fellowships Programme. We thank K.
Fletcher and D. Wright for critical review of the
manuscript.
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