Applied Geochemistry 15 (2000) 531±550

Regional geochemical reconnaissance of the Cordillera

Occidental of Ecuador: economic and environmental
applications
T. Martin Williams a,*, Peter N. Dunkley a, Edgar Cruz b, Victor Acitimbay b,
Alina Gaibor b, Edgar Lopez b, Napoleon Baez b, John A. Aspden a
a
British Geological Survey, Keyworth, Nottingham NG12 5GG, UK
b
CorporacioÂn de Desarrollo e InvestigacioÂn GeoloÂgico, Minero, MetaluÂrgica (CODIGEM), Quito, Ecuador
Received 10 November 1998; accepted 24 May 1999
Editorial handling by O. Selinus

Abstract

A regional geochemical reconnaissance survey of the Cordillera Occidental of Ecuador was initiated in 1995 as a
sub-component of a wider Mining Development and Environmental Control Technical Assistance Project
(PRODEMINCA) in Ecuador. The 36,000 km2 survey area encompasses oceanic and continental-margin volcano-
sedimentary terranes with known occurrences of porphyry-style Cu-Mo, exhalative massive sulphide, epithermal Au
and mesothermal polymetallic mineralisation. A survey sample medium of <177 mm stream sediments was selected
following an orientation study in the vicinity of known porphyry Cu mineralisation. In the 2±48S sector of the
Cordillera Occidental for which data are presented, 4850 drainage samples were collected at an average density of 1
per 2.57 km2. All were analysed for 36 major and trace elements (Au, Ag, Cu, Pb, Zn, Mo, Ni, Co, Cd, Bi, As, Sb,
Fe, Hg, Mn, Te, Ba, Cr, V, Sn, W, La, Al, Mg, Ca, Na, K, Sr, Y, Ga, Li, Nb, Sc, Ta, Ti, Zr). A stringent quality-
control procedure included the systematic analysis of certi®ed reference samples, ®eld duplicates and replicates, data
for which were used to calculate analytical precision, temporal drift and practical detection limits. Results for this
part of the cordillera highlight the contrasting lithogeochemical signatures of the ocean-¯oor basalt terrane
(Pallatanga Unit), the island-arc terrane of the Macuchi Unit, the continental volcanics of the Saraguro Group and
the acid and intermediate lavas extruded from the Late Miocene to the Quaternary. Regional geochemical images
for Au and associated path®nder elements are dominated by anomalies relating to known mines and prospects. New
exploration targets, often inconspicuous at the regional scale, have however been identi®ed through the
normalisation of data for individual lithological units against their respective geochemical backgrounds. In addition
to mineral exploration, the drainage geochemical dataset for the Cordillera Occidental provides an unparalleled
environmental baseline against which the impacts of future anthropogenic activities (including mining) may be
assessed. A basis for the formulation of pragmatic sediment quality criteria and for the identi®cation of natural
geochemical hazards is also provided. # 2000 Elsevier Science Ltd. All rights reserved.

* Corresponding author. Fax: +593-2-254-643.

E-mail address: tmwilli@pi.pro.ec (T.M. Williams).

0883-2927/00/$ - see front matter # 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 8 8 3 - 2 9 2 7 ( 9 9 ) 0 0 0 5 9 - 1
532 T.M. Williams et al. / Applied Geochemistry 15 (2000) 531±550

1. Introduction ferous minerals sector. The dissemination of new

A regional geochemical reconnaissance survey of
the Cordillera Occidental (Western Cordillera) of
Ecuador was initiated in 1995 as a sub-component
of a national Mining Development and Environ-
mental Control Technical Assistance Project
(PRODEMINCA), funded by the World Bank and
the governments of the UK, Sweden and Ecuador.
Execution of the survey is the responsibility of the
MisioÂn GeoloÂgica BritaÂnica, incorporating consultants
from the British Geological Survey (BGS) and
the CorporacioÂn de Desarrollo e InvestigacioÂn
GeoloÂgico, Minero, MetaluÂrgica (CODIGEM). The
PRODEMINCA has the central objective of promot-
ing the sustainable development of Ecuador's metalli-
geochemical reconnaissance data may contribute sig-
ni®cantly to the achievement of this goal, providing a
stimulus to exploration investment through the
delineation of new Au and base metal targets. High
quality regional geochemical data are additionally
recognised under PRODEMINCA as a strategic
resource of relevance to natural hazard assessment,
land-use planning and the development of pragmatic
environmental quality criteria. This paper outlines the
methodology of the Cordillera Occidental survey and
provides an insight into its immediate economic and
environmental applications. All examples refer speci®-
cally to the 2±48S sector of the project area, data for
which were formally released by the Government of
Ecuador in 1998.

Fig. 1. Zone of coverage of the PRODEMINCA Cordillera Occidental drainage reconnaissance survey. The shaded area corre-
sponds to the 2±48S sector for which results are presented.
 T.M. Williams et al. / Applied Geochemistry 15 (2000) 531±550 533

Fig. 2. Principal settlements, drainage systems and documented mineral occurrences within the 2±48S sector of the Cordillera
Occidental of Ecuador.
 534
T.M. Williams et al. / Applied Geochemistry 15 (2000) 531±550

Fig. 3. Simpli®ed geology of the 2±48S sector of the Cordillera Occidental of Ecuador.
 T.M. Williams et al. / Applied Geochemistry 15 (2000) 531±550
2. Survey area
2.1. Location and physiography
The Cordillera Occidental geochemical survey area
extends between latitudes 18N and 48S (Fig. 1), encom-
passing approximately 36,000 km2. The 2±48S sector
(Fig. 2) for which data are presented covers 12,500
km2. Altitudes within this area range 150±4500 m.
Drainage extends westward to the Paci®c via the
Chanchan, CanÄar, Chaucha and Jubones river systems
and eastward to the Amazon basin via the RõÂ o Paute.
2.2. Geological setting
2.2.1. Regional geology
Ecuador is divided geologically and physiographi-
cally into the contrasting terranes of the Oriente
(upper Amazon basin), the Sierra (Andean region) and
the Costa (coastal plain). The Oriente is a low-lying
Mesozoic to Cenozoic sedimentary basin, dominated
by a carbonate platform sequence overlying cratonic
basement. The sequence is intruded by large granitoid
batholiths along a complex sub-Andean zone of fold-
ing and thrusting. The Sierra comprises two sub-paral-
lel mountain chains, each with peaks exceeding 5000 m
in altitude, separated along much of their length by
the Inter-Andean Depression. The Cordillera Real
(Eastern Cordillera) is dominated by linear meta-
morphic belts, intruded by early Mesozoic granitoids
and capped by continental volcanic sequences of
Cenozoic age. The Cordillera Occidental (Western
Cordillera) comprises accreted Late Mesozoic to Early
Cenozoic oceanic basalts, island arc volcanics and as-
sociated turbidites, intruded by Mid-Late Tertiary
granitoids and extensively overlain by continental-mar-
gin calc-alkaline volcanics. The Costa is dominated by
a broad expanse of Quaternary alluvial cover.
2.2.2. Area of data coverage
Geological maps (1:200,000 scale) of the 2±38S and
3±48S sectors of Cordillera Occidental have been pub-
lished by BGS-CODIGEM (1997a, b). Detailed lithos-
tratigraphic descriptions of these areas are provided by
Dunkley and Gaibor (1997) and Pratt et al. (1997). A
simpli®ed geological map is shown in Fig. 3.
Basement rocks in the Cordillera Occidental of cen-
tral-southern Ecuador comprise predominantly low-
grade metasediments, against which the oceanic basalt
terrane of the Pallatanga Unit was accreted in the Late
Cretaceous. In the 2±48S sector the Pallatanga Unit
outcrop has a total strike-length of 120 km. Island-arc
basalts and basaltic andesites of the Macuchi Unit and
silicic marginal basin facies of the Angamarca Group
were thrust against the continental margin during the
Late Eocene and are widely exposed in the northwest
535
of the area. Calc-alkaline continental-margin volcanism
commenced in the Late Eocene producing, over a
period of ca. 30 m.y., the predominantly dacitic and
andesitic lithologies of the Saraguro Group and
Sacapalca Unit which outcrop over more than 50% of
the 2±48S area. Fluvio-marine sediments of the
Ayancay and Turi Formations were deposited in a
series of inter-montane basins in the Late Miocene.
These are partially capped by Late Miocene andesites
of the Quimsacocha Formation north of San Fernando
and the CisaraÂn Formation around AlausõÂ in the
northeast (Fig. 2).
The metamorphic basement, the Saraguro Group
and the Sacapalca Unit are extensively intruded by
diorites, tonalites and granodiorites the most extensive
of which, the Chaucha and Paccha batholiths, have
been dated by K/Ar methods to between 9 and 16 m.y.
(Muhler-Kahle and Damon, 1970; Pratt et al., 1997).
Sub-volcanic rhyolite and porphyritic andesite com-
plexes are common within the Saraguro Group and
later formations.
Regional structures trend predominantly northeast
and de®ne the major lithotectonic units of the study
area.
2.3. Metalliferous mineralisation
The 2±48 sector of the Western Cordillera hosts a
diversity of prospective settings for Au and base metal
mineralisation (Fig. 2). A porphyry-style Cu-Mo
deposit at Chaucha (UNDP, 1969) has an estimated
ore reserve of 55 million tons grading 0.57% Cu and
0.3% Mo. At Gaby (Gemuts et al., 1992; Paladines
and Rosero, 1996) a Cu-Au porphyry and stockwork
system holds a mineable Au reserve possibly exceeding
two million ounces. Several epithermal Au prospects of
predominantly low-sulphidation character (e.g.
CanÄaribamba, GanÄarin, Pachagmama, Quimsacocha)
occur in the GanÄarin Belt, a NNE trending regional
fracture extending some 90 km from the Zaruma
District to Quimsacocha. Mesothermal polymetallic
(Au-Ag-Pb-Zn-Cu-Cd-As-Sb-Bi) mineralisation has
been reported in variably tourmalinised breccias at
Angas (Van Thournout and Guzmann, 1989), Tres
Chorreras, La Playa and Paccha (Pratt et al., 1997). At
Cerro Pelado, Au and base metal mineralisation in
rhyodacitic rocks of the Saraguro Group occurs in
zones of brecciation and shearing. At Bella Rica,
mesothermal quartz veins hosted within the Pallatanga
Unit have been exploited by artisanal miners since the
1980's, yielding over two tons of Au annually. In the
Zaruma-Portovelo area, mesothermal polymetallic
veins with later epithermal overprints have been inter-
preted by Van Thournout et al. (1991) as the pre- and
post-caldera phases of mineralisation associated with
an Oligocene eruptive centre. Exhalative massive sul-
536 T.M. Williams et al. / Applied Geochemistry 15 (2000) 531±550

Fig. 4. Junin orientation survey sampling sites and downstream dispersion patterns for selected elements in di€erent size fractions
of sediments from the Rio Junin and tributary drainage. All sub 1mm classes are classi®ed by BSI mesh size. Data for the ÿ60 BSI
fraction are quoted following milling for 60 seconds (A) and 120 seconds (C). All data relate to samples digested in aqua-regia.

phides occur in the Saraguro Group north of San
Fernando (UNDP, 1969).
3. Orientation survey
Prior to the BGS-CODIGEM survey, drainage sedi-
ments were identi®ed as the most practical medium for
multi-purpose geochemical mapping of the Cordillera
Occidental at the desired resolution of 1 sample per 3
km2. An orientation study was, however, undertaken
in the vicinity of known Cu-Mo porphyry mineralis-
ation at Junin, 100 km north of Quito, to determine
the optimum sediment size fraction, sample prep-
aration procedure and analytical method for systematic
use. The Junin setting was selected on account of its
relatively pristine state, thus avoiding interpretive com-
plexities associated with historical or ongoing mining
activity. Mineralisation occurs as stockworks and
vuggy ®lls in a Miocene granodiorite stock. The assem-
blage comprises pyrite, chalcopyrite, bornite, molyb-
denite, haematite, trace Sb, As, Sn and W phases, Cu
sulphosalts and other supergene alteration products.
Sediment samples of approximately 20 kg were
recovered from 8 RõÂ o Junin sites along an 11 km chan-
nel section downstream from the Junin prospect. Three
control sites located on unmineralised tributaries were
also sampled (Fig. 4). All samples were divided at site
into <1 mm, <60 BSI (250 mm), <80 BSI (177 mm)
and <100 BSI (150 mm) size classes by wet-screening
through plastic sieves. In the laboratory, each fraction
was air dried (at <408C), ri‚ed and split into multiple
aliquots. Prior to digestion, the <80 and <100 BSI
fractions were disaggregated using a pestle and mortar,
independent aliquots of <60 BSI material were milled
in an agate tema for 1 and 2 min respectively and <1
 T.M. Williams et al. / Applied Geochemistry 15 (2000) 531±550 537

Table 1
Peak to background ratios for selected elements of importance for mineral reconnaissance in di€erent sediment size fractions from
the Rio Junin orientation study area. All values relate to samples digested in aqua regia. Background values re¯ect the mean of
sediment determinations for unmineralised Rio Junin tributaries

Element < 1 mm < 60 BSI (1 min) < 60 BSI (2 min) < 80 BSI < 100 BSI

Zn 1.95 1.78 1.86 1.92 1.87

Cu 44.9 41.0 41.3 45.4 30.7
Mo 2.7 1.6 1.7 2.2 2.33
As 4.9 9.6 10.4 11.6 8.9
Sb 10.8 16.4 18.2 19.7 11.4

mm samples were milled for 2 min. The 5 sub-samples
produced for each station were then further ri‚ed and
split into two aliquots for independent aqua-regia and
HF+HClO4+HCl+HNO3 digestion.
Dispersion-train signatures for selected elements in
the RõÂ o Junin locality are shown in Fig. 4. Strong
enrichment of Cu (>200 mg/kg) was recorded in all
analysed size fractions, with no pronounced variability
of downstream dispersion pattern. For As, Sb and
Mo, peak concentrations and dispersion distances
were, however, found to be systematically higher in ®n-
est (<80 BSI and <100 BSI) fractions. With respect
to Zn, Cu, As and Sb, <80 BSI fractions produced
high anomaly/background ratios relative to <60 BSI
or <100 BSI sediments (Table 1), thus favouring the
adoption of this fraction for systematic use.
Data for replicate samples digested in aqua-regia
and HF+HClO4+HCl+HNO3 (Table 2) showed the
former to yield lower trace metal values by factors of
0.6±2.5 within the background concentration range
(i.e. for unmineralised tributary samples), but to yield
more closely analogous values for strongly anomalous
stations. The former digestion procedure was accord-
ingly adopted for subsequent use because of the higher
anomaly/background ratios produced.
4. Sampling and analytical procedures
A random numbering system (Plant, 1973) was
Table 2
Peak and background (BG) concentrations (mg/kg) deter-
mined for Zn, Cu and Mo in the Rio Junin orientation study
sample suite following digestion of sediments in aqua-regia
(AR) and HF+HClO4+HCl+HNO3 (TOT). All data relate
to <80 BSI (177 mm) sediment fractions
Element Peak (AR) Peak (TOT) BG (AR) BG (TOT)
Zn 107 149 55 127
Cu 909 1106 20 32
Mo 14 23 6 14
deployed throughout the BGS-CODIGEM survey to
preclude analytically-induced campaign boundaries
and/or the generation of spurious multiple-sample
anomalies. Drainage sediment samples were collected
by two sampling teams, each comprising 8 prospectors.
A total of 4850 samples was collected from a 12,500
km2 area, representing an average sampling density of
1 per 2.57 km2. Emphasis was placed on the sampling
of ®rst or second order rivers, thus constraining the
e€ective provenance area.
Procedures for the collection of sediment samples
followed Plant and Moore (1979), with appropriate
modi®cation for the Cordilleran environment based on
the results of the orientation survey. At each site sev-
eral kilograms of active channel detritus were collected
following the removal of the hydrous-oxide enriched
interfacial horizon. The alluvium was then wet-
screened through a 80 BSI mesh (177 mm) sieve using a
minimal volume of water to avoid the loss of ®ne silt
and clay fractions. Following a settling period of ca.
20 min, the clear water overlying the sediment was dec-
anted and the remaining sediment-water mixture trans-
ferred to a pre-numbered kraft bag.
In the laboratory, all samples were air-dried at 408C
and disaggregated with a pre-washed ceramic pestle
and mortar to yield a ®ne homogeneous powder. This
was coned-and-quartered to produce a 65 g aliquot for
multi-element analysis. Gold was determined by ®re-
assay of 30 g aliquots with subsequent analysis of the
fused product by atomic absorption spectrophotometry
(AAS). A suite of 32 major and trace cations (Ag, Cu,
Pb, Zn, Mo, Ni, Co, Cd, Bi, Fe, Mn, Te, Ba, Cr, V,
Sn, W, La, Al, Mg, Ca, Na, K, Sr, Y, Ga, Li, Nb, Sc,
Ta, Ti, Zr) was analysed by inductively-coupled
plasma emission spectrometry (ICP-ES) following the
digestion of 1.0 g aliquots in 100 ml of aqua-regia
(ARISTAR). The metalloid elements As and Sb were
analysed by hydride-generation AAS. Mercury was
determined by cold-vapour AAS following aqua-regia
digestion of 1.0 g sub-samples under hot-re¯ux. All
analyses were performed in the Vancouver laboratories
of Bondar Clegg Ltd.
538 T.M. Williams et al. / Applied Geochemistry 15 (2000) 531±550

Table 3 Table 4
Within-site variance of selected elements analysed in the Analytical detection limits reported by Bondar Clegg Ltd and
Cordillera Occidental drainage survey calculated using the `variation of standard deviation' method
of Thompson and Howarth (1978). All values are quoted in
Element % variance mg/kg unless otherwise indicated

Ag 7.1 Element Bondar Clegg Variation of S.D.

Cu 3.1
Pb 7.1 Ag 0.2 1.0
Zn 4.7 Au 0.05 ±
Mo 25.0 As 1 6.1
Ni 12.4 Ba 1 5.4
Co 3.5 Bi 5 6.0
Cd 4.2 Cd 0.2 0.7
Sn 15.2 Cr 1 3.7
W 21.7 Co 1 2.6
La 4.3 Cu 1 4.5
Al 3.6 Fe 0.01% 0.3%
Mg 7.1 Hg 0.01 0.04
Ca 12.5 Li 1 1.2
Na 12.2 Mn 1 34.0
K 9.4 Mo 1 1.35
As 3.1 Ni 1 3.3
Sb 6.9 Pb 2 4.0
Fe 6.6 Sb 0.2 1.9
Mn 7.1 Zn 1 5.0
Bi 17.5
Ba 3.2
Cr 9.3 deviation across an empirically-de®ned concentration
V 4.9 range (Thompson and Howarth, 1978) and the second
Ga 11.6 based on control charts on which 90th and 99th per-
Y 21.2
centile concordance lines were plotted for one or more
Nb 15.4
Sc 16.0
pre-determined precision levels.
Ti 4.4 Three of the 6 project control standards used during
Zr 12.1 the survey were characterised at the UK laboratories
Hg 21.7 of the BGS by a combination of ICP-ES, ICP mass
spectrometry (ICP-MS) and X-ray ¯uorescence (XRF)
methods. The results were subsequently used to assess
5. Quality control instrumental accuracy within the ®eld dataset.
Practical limits of detection (LODs, Table 4) for all
Statistical variance attributable to at-site sediment analysed elements were determined through the repli-
heterogeneity and/or sampling bias was calculated cate analysis of reference samples over a range of con-
using a modi®ed analysis of variance (ANOVA) tech- centrations and the regression of the standard
nique (Plant et al., 1975). Duplicate sediment samples deviation against the mean concentration for each
acquired through repeat sampling of drainage sites at a value to yield a value of standard deviation at zero
frequency of 2 per 100 were analysed and the results concentration (S0). A LOD of 3S0 was then calculated
used to determine sampling variance using a sum of in conventional fashion.
squares technique (Bolviken and Sinding-Larsen, 1973;
Table 3).
Two sub-samples of each of 3 or more independent 6. Results
control standards were analysed in blind fashion with
each batch of 120 ®eld samples and the results utilised 6.1. Summary statistics
for evaluating instrumental precision and temporal
analytical drift (Fig. 5). A total of 6 control standards Summary statistics and Pearson correlation coe-
derived from ¯uvial sediments within the Cordillera cients (R ) for drainage geochemical data from the 2±
Occidental was used for this purpose. Precision was 48S sector of the Cordillera Occidental are presented in
determined using two statistical methods, the ®rst Tables 5 and 6. The correlation matrix, produced fol-
entailing calculation of the variation of the standard lowing data log-normalisation, highlights signi®cant
 T.M. Williams et al. / Applied Geochemistry 15 (2000) 531±550 539

Fig. 5. Temporal instrumental variation of Zn and As, inferred from the analysis of duplicate aliquots of homogeneous sediment
standards J1, M1 and PE in conjunction with each of up to 64 batches of ®eld samples from the Cordillera Occidental 2±48S sec-
tor. Error corrections were applied to the empirical data only when values for both aliquots of one or more control standards sim-
ultaneously deviated from the mean by more than 2 standard deviations, as exempli®ed by the Zn data for standard J1 in
analytical batches 22 and 23.
540 T.M. Williams et al. / Applied Geochemistry 15 (2000) 531±550

Table 5 (Williams et al., 1997), thus suggesting that the utility

Descriptive statistics for stream sediment data acquired for of metalloids as Au path®nders in the cordillera is
the Cordillera Occidental of Ecuador, sector 2±48S. All values widely variable. A strong correlation between Cu and
are quoted in mg/kg unless otherwise indicated Mo (R = 0.770) re¯ects the simultaneous enrichment
of both elements in porphyry deposits and zones of
Mean S.D. Min Max Median
mineralised hydrothermal brecciation. The strictly lim-
Au (mg/kg) 87.7 528 3.33 10,000.0a 3.3 ited in¯uence of hydrous oxides on sediment signatures
Ag 0.89 2.6 0.66 87.00 0.6 is signi®ed by a lack of statistically signi®cant covaria-
Cu 82.7 593 3.00 20,000.0a 25 tion between Mn and most ®rst row transition el-
Pb 25.8 139 2.66 6732.0 13 ements and/or metalloids.
Zn 102.9 216 3.33 8516.0 76
Mo 5.33 96 0.90 4458.0 0.9
Ni 18.9 35 2.20 850.5 11 6.2. Lithogeochemical terranes
Co 14.6 13 1.73 462.0 12
Cd 0.82 3.5 0.46 137.1 0.4 Gridded geochemical images portraying the distri-
Bi 4.73 5.3 4.00 203.5 4.0 bution of a range of elements across the 2±48S sector
Fe (%) 4.28 1.8 0.01 10.0a 3.9 of the Cordillera Occidental (e.g. Fig. 6) were gener-
Mn 820.2 717 22.7 18,661.0 711 ated using an inverse-distance-weighting (IDW) algor-
Te 7.06 3.9 6.66 169.5 6.6
ithm in the geochemical exploration software package
Ba 134.4 90 3.00 1333.0 115
Cr 36.2 38 2.46 854.5 27
Interdex2. On account of the limited extent of super-
V 109.1 75 0.66 747.5 88 gene alteration of the cordilleran environment, an
Sn 13.5 1.6 13.3 56.0 13 extremely strong spatial correlation between bedrock
W 13.9 19 13.3 844.5 13 lithology and sediment geochemistry is retained. The
La 10.3 7.3 0.66 129.0 9. principal lithogeochemical terranes highlighted are
Al (%) 2.63 1.1 0.01 9.5 2.4 summarised below:
Mg (%) 0.72 0.4 0.01 4.9 0.6
Ca (%) 0.62 0.6 0.01 10.0a 0.4 1. Tholeiitic basalts of the Pallatanga Unit display
Na (%) 0.03 0.03 0.01 0.40 0.02 enrichment of Cr, Co, Ca, Cu, Mg and Ni to aver-
K (%) 0.11 0.08 0.01 1.14 0.09 age levels exceeding the 80th percentile of the data-
Sr 41.2 36 ÿ1.0 308.0 32 set for the entire mapped area. Background
Y 6.6 3.5 0.66 78.0 6.0 abundances of Ba and K are characteristically low.
Ga 4.76 3.5 1.33 36.0 4.0 2. In the northwest of the area, accreted island-arc vol-
Li 12.8 8.5 0.80 66.0 11 canics of the Macuchi Unit show enrichment in an
Nb 2.45 3.2 0.66 51.0 1.0 analogous element suite to that of the Pallatanga
Sc 5.87 4.2 3.33 39.0 3.3
Unit, but markedly higher ratios of Cu/Cr and Cu/
Ta 6.98 4.2 6.66 146.3 6.6
Ni re¯ect a greater andesitic component.
Ti 0.10 0.07 0.01 0.63 0.09
Zr 3.91 4.07 0.66 37.0 2.0 3. Dacitic and rhyodacitic components of the Saraguro
As 47.2 384 2.66 10000.0a 9.5 Group (notably in the central and southeastern
Sb 3.45 32 1.26 2000.00a 1.2 parts of the mapped area) yield a Cu, Cr, Co, Ni,
Hg 0.18 1.5 0.03 50.00a 0.05 V-poor signature, most values falling below the 30th
percentile of the dataset.
a
Upper reporting limit. 4. Andesitic facies of the Saraguro Group south of the
38S line produce typically high Mg/Ca ratios, with
high background abundances (>50th percentile) of
spatial covariation (R > 0.24 at the 99% con®dence Cr and Zn. Over the Santa Isabel Formation, south
level for a population of N > 4800) between elements and southwest of San Fernando (Fig. 2), intensely
characteristically enriched in ma®c and/or ultrama®c calcite-veined andesites yield values of Ca, Sr, Mg
lithologies (Cr, Ni, Co, Fe, V, Mg). Gold is strongly and V generally in excess of the 90th percentile of
correlated with Ag (R=0.602), several base metals the entire dataset, with some attendant enrichment
(Cu, Zn, Pb; R = 0.311±0.634) and As and Sb of Cr.
(R=0.504±0.630). Independent statistical analysis of 5. Miocene andesites of the CisaraÂn Formation and
data for the 2±38S and 3±48S areas (Williams et al., later acid volcanics in the northeast of the mapped
1997; 1998) has, however, shown this relationship to area are di€erentiated from all other volcanic units
be primarily con®ned to the latter, in which highest Au by extremely high ratios of Sr/K. Low backgrounds
values typically occur in polymetallic mesothermal of As, Pb, Mn, Hg and Zn prevail relative to all
assemblages. North of the 38S line, the correlation other non-intrusive lithologies.
coecient for Au against As is reduced to 0.19 6. The metamorphic basement to the south of the Rõ o
Table 6
Pearson correlation matrix for stream sediment data acquired for the Cordillera Occidental of Ecuador, sector 2±48Sa

Au Ag Cu Pb Zn Mo Mn Cr V W Mg Ca K Sr As Sb Hg

Au 1.000 0.602 0.634 0.352 0.311 0.443 0.015 0.052 ÿ0.004 0.151 0.024 4.685Eÿ4 ÿ0.020 ÿ0.086 0.630 0.504 0.154
Ag 0.602 1.000 0.762 0.769 0.714 0.490 0.027 ÿ0.029 ÿ0.048 0.210 ÿ0.033 ±0.039 ÿ0.011 ÿ0.065 0.401 0.515 0.075
Cu 0.634 0.762 1.000 0.498 0.431 0.770 0.021 0.001 ÿ0.011 0.174 0.002 ÿ0.022 ÿ0.005 ÿ0.065 0.402 0.411 0.075
Pb 0.352 0.769 0.498 1.000 0.895 0.094 0.049 ÿ0.032 ÿ0.047 0.017 ÿ0.026 ÿ0.048 ÿ0.019 ÿ0.061 0.420 0.167 0.053
Zn 0.311 0.714 0.431 0.895 1.000 0.023 0.209 ÿ0.031 ÿ0.027 0.005 0.014 ÿ0.032 ÿ0.032 ÿ0.058 0.336 0.132 0.049
Mo 0.443 0.490 0.770 0.094 0.023 1.000 0.010 ÿ0.029 ÿ0.033 0.108 ÿ0.043 ÿ0.018 0.007 ÿ0.033 0.106 0.632 0.062
Mn 0.015 0.027 0.021 0.049 0.209 0.010 1.000 ÿ0.028 2.597Eÿ4 ÿ0.008 0.083 0.112 ÿ0.099 0.034 0.014 0.017 0.003
Cr 0.052 ÿ0.029 0.001 ÿ0.032 ÿ0.31 ÿ0.029 ÿ0.028 1.000 0.396 ÿ0.016 0.641 0.131 0.024 ÿ0.115 0.036 ÿ0.006 0.027
V ÿ0.004 ÿ0.048 ÿ0.011 ÿ0.047 ÿ0.027 ÿ0.033 2.597Eÿ4 0.396 1.000 ÿ0.009 0.218 0.173 ÿ0.081 0.067 ÿ0.016 ÿ0.030 ÿ0.012
W 0.151 0.210 0.174 0.017 0.005 0.108 ÿ0.008 ÿ0.016 ÿ0.009 1.000 ÿ0.008 ÿ0.023 0.025 ÿ0.025 0.040 0.089 0.004
Mg 0.024 ÿ0.033 0.002 ÿ0.026 0.014 ÿ0.043 0.083 0.641 0.218 ÿ0.008 1.000 0.418 0.043 0.026 0.041 ÿ0.010 0.003
Ca 4.685Eÿ4 ÿ0.039 ÿ0.022 ÿ0.048 ÿ0.032 ÿ0.018 0.112 0.131 0.173 ÿ0.023 0.418 1.000 ÿ0.078 0.427 0.017 ÿ0.003 ÿ0.010
K ÿ0.020 ÿ0.011 ÿ0.005 ÿ0.019 ÿ0.032 0.007 ÿ0.099 0.024 ÿ0.081 0.025 0.043 ÿ0.078 1.000 0.004 ÿ0.024 0.004 ÿ0.043
Sr ÿ0.086 ÿ0.065 ÿ0.065 ÿ0.061 ÿ0.058 ÿ0.033 0.034 ÿ0.115 0.067 ÿ0.025 0.026 0.427 0.004 1.000 ÿ0.062 ÿ0.042 ÿ4.469Eÿ4
As 0.630 0.401 0.402 0.420 0.336 0.106 0.014 0.036 ÿ0.016 0.040 0.041 0.017 ÿ0.024 ÿ0.062 1.000 0.291 0.065
Sb 0.504 0.515 0.411 0.167 0.132 0.632 0.017 ÿ0.006 ÿ0.030 0.089 ÿ0.010 ÿ0.003 0.004 ÿ0.042 0.291 1.000 0.062
Hg 0.154 0.075 0.075 0.053 0.049 0.62 0.003 0.027 ÿ0.012 0.004 0.003 ÿ0.010 ÿ0.043 ÿ4.469Eÿ4 0.065 0.062 1.000
T.M. Williams et al. / Applied Geochemistry 15 (2000) 531±550

a
4846 Observations were used in this computation.
541
542 T.M. Williams et al. / Applied Geochemistry 15 (2000) 531±550

Fig. 6. Inverse distance weighted grids showing the distributions of Cu, Cr, Sr and K within the 2±48S sector of the Cordillera
Occidental. (LG=light grey, MG=mid-grey, DG=dark grey, BL=black).
 T.M. Williams et al. / Applied Geochemistry 15 (2000) 531±550 543

Fig. 7. Inverse distance weighted grids showing the distributions of Au, As, Sb and Hg within the 2±48S sector of the Cordillera
Occidental. (LG=light grey, MG=mid grey, DG=dark grey, BL=black).
544 T.M. Williams et al. / Applied Geochemistry 15 (2000) 531±550

Table 7
Gold anomalies identi®ed through simultaneous cumulative probability analysis of the Cordillera Occidental 2±48S geochemical
reconnaissance dataset. All occurrences yield Au values in excess of the 97th percentile

Terrane Location UTM ref. Au (ppb) Element association Mineralisation

Pallatanga U. Rio Pijili 6688 97715 4989 none Structurally controlled veins
Diorite Q. el Llanto 6700 96700 2524 Cu±Pb±Zn±Cd±Bi±As±Sb Zone of brecciation
Basement Dumari 6438 96190 1454 Pb±As±Sb±Cu Mesothermal veins
Basement Rio Santa Rosa 6257 96039 1835 Cu±Bi±Ag±As±Sb Unknown source
Pallatanga U. Gaby 6428 96620 9351 Ag±Cu±Pb±Bi±As±Sb Porhyry and stockwork
Pallatanga U. Bella Rica 6417 96587 8000 As±Sb±Cu±Pb±Ag Mesothermal veins
Pallatanga U. San Gerardo 6514 96666 8675 As±Sb±Cd Epi/mesothermal veins
Saraguro Gp. Zaruma±Portovelo 6945 95980 9446 Ag±Cu±Pb±Zn±As±Cd±Bi Epi/mesothermal veins
Saraguro Gp. Tres Chorreras 6637 96505 9561 Cu±Mo±As±Sb±Bi Tourmaline breccias
Saraguro Gp. Gigantones 6602 96447 3837 Cu±Mo Tourmaline breccias
Saraguro Gp. La Playa 6520 96430 2140 W±Cu±Mo±Bi±As±Sb Tourmaline breccias
Saraguro Gp. Mollepungu 6514 96371 3415 Ag±W±Cu±Mo±As±Sb Tourmaline breccias
Saraguro Gp. Canaribamba 6882 96449 3046 Ag Low sulphidation epithermal
St. Isabel Fm. Ganarin 6806 96352 1045 None Low sulphidation epithermal
Granodiorite Paccha 6488 96045 5749 Ag±Pb±Cu±Zn±Cd±Bi±Sn±As±Sb Tourmaline breccias
Saraguro Gp. Cerro Pelado 6230 96140 10000 As±Sb Mesothermal veins
Granodiorite R. Byron 6261 96120 3747 As, Sb, Cu, Pb Tourm. breccias

Jubones (Fig. 2) and the large granodiorite intru-
sions of Chaucha and Paccha (Fig. 3) form positive
regional features with respect to K, values typically
lying above the 75th percentile of the dataset.
6.3. Metalliferous mineral potential
6.3.1. Constraints on data interpretation
The regional geochemical dataset described for the
Cordillera Occidental, while providing a powerful tool
for the evaluation of metalliferous mineral potential,
requires interpretation subject to the recognition of a
number of inherent constraints. At the resolution of
sampling undertaken, potentially signi®cant explora-
tion targets may be resolved by no more than a single
anomalous sample, as exempli®ed with respect to sev-
eral known prospects including GanÄarin and
CanÄaribamba (Fig. 2). In the higher sectors of the pro-
ject area (>3500 m) drainage geochemical signatures
are controlled by physical rather than hydromorphic
processes. Peak to background ratios for Au, metal-
loids and ®rst-row transition metals are thus generally
low and responses to mineralisation extremely subtle.
In areas of past or current mining activity, notably
around Bella Rica and Zaruma-Portovelo (Fig. 2),
natural drainage geochemical signatures have been
substantially modi®ed by contaminant metals mobi-
lised during ore extraction, bene®ciation and waste dis-
posal. The precise derivation of sources or geological
controls on drainage anomalies is thus often proble-
matic.
6.3.2. Principal gold occurrences
Greyscale geochemical images produced using
Interdex2 for Au and the path®nder elements As, Sb
and Hg within the 2±48S sector of the Cordillera
Occidental are shown in Fig. 7. Strongly anomalous
values, in all cases exceeding the 97th percentile for the
entire dataset, were de®ned on the basis of cumulative
probability analysis. For Au, the regional background
determined by this method was found to be below 50
mg/kg (73rd percentile). A conspicuous threshold was
identi®ed at 460 mg/kg (95th percentile), with strongly
anomalous outliers exceeding 1195 mg/kg (97th percen-
tile). Table 7 provides a synopsis of such anomalies,
virtually all of which relate to documented mines or
prospects. The most extensive lie within 4 mining dis-
tricts in the southern half of the mapped area:
1. At Bella Rica over 40 artisanal adit operations
exploit polymetallic veins hosted in basalts of the
Pallatanga Unit. The Estero Guanache river, drain-
ing both the Gaby porphyry deposit (Fig. 2 and
Fig. 7 ref. 6428 96620) and the northern ¯ank of the
Bella Rica concession, yields several Au values in
excess of 3000 mg/kg with coincident enrichment of
Ag (17.3 mg/kg), Cu (4264 mg/kg), Pb (1832 mg/
kg), Bi (105 mg/kg), As (>10,000 mg/kg) and Sb
(113 mg/kg). The San Gerardo mining district a few
kilometres to the north (Fig. 7 ref. 6514 96666)
hosts anomalous Au values up to 8675 mg/kg Au.
Here, a distinctly lower-temperature auriferous
assemblage is signi®ed by relatively low base-metal
concentrations and strong enrichment of Sb (>300
mg/kg).
 T.M. Williams et al. / Applied Geochemistry 15 (2000) 531±550 545

Table 8
Summary statistics and background Au concentrations (mg/kg) in stream sediments from litho-stratigraphic units de®ned for the
Cordillera Occidental of Ecuador, sector 2±38S (after Dunkley and Gaibor, 1997). For each lithology the upper limit of back-
ground variation was determined by cumulative probability analysis. All units and formations with the sux SG are components
of the Saraguro Group

Unit/formation Mean Min Max Median Background

Pallatanga Unit 74 3 4989 1.99 < 100

Macuchi Unit 24 3 451 7 < 60
Angamarca Group 26 3 1028 7 < 37
Ocana Formation SG 48 3 1540 6 < 56
Chulo Unit SG 95 3 3127 3 < 80
Filo Cajas Unit SG 136 3 782 11 < 90
Tomebamba Unit SG 41 3 739 3 < 80
Chanlud Formation SG 22 3 522 3 < 50
Rio Blanco Formation SG 45 3 940 8 < 60
Soldados Formation SG 72 3 706 3 < 50
Plancharumi Formation SG 85 3 1182 3 < 75
Punay Unit 6 3 95 3 < 11
Cisaran Formation 9 3 322 3 < 15
Granodiorite intrusions 19 3 981 3 < 50
Diorite intrusions 72 3 2524 16 < 170

2. The Zaruma±Portovelo district (Fig. 2) yields some
20 anomalous Au values with attendant enrichment
of Ag (>40 mg/kg), Pb (>650 mg/kg), Cu (>5000
mg/kg), Cd (>20 mg/kg), Bi (>100 mg/kg) and As
(>500 mg/kg). Values of Hg in the range 2±50 mg/
kg in this area occur primarily as a consequence of
contamination from Au bene®ciation activities.
3. A N-NE trending zone of Au enrichment highlights
several prospects and artisanal mining operations
north of Uzchurrumi (Fig. 2). Obvious sources,
including the deposits of La Playa (Fig. 2. and Fig.
7 ref. 6520 96430) and Tres Chorreras (Fig. 2 and
Fig. 7 ref. 6637 96505), are typically associated with
zones of intense tourmaline brecciation within or at
the margins of minor intrusive stocks. Strong
anomalies are also recorded with respect to Cu (to
2%), Mo (>4000 mg/kg) and, notably at La Playa,
W (>750 mg/kg).
4. Several Au values to 10,000 mg/kg overlie the Cerro
Pelado mining district (Fig. 2 and Fig. 7 ref. 6230
96140) in the extreme southwest of the mapped
area.
Less extensive Au anomalies, variably accompanied
by enrichment in As and Sb, occur over the Quebrada
el Llanto and Carmen de Pijili prospects south of
Chaucha (Fig. 7 ref. 6700 96700) and a formerly undo-
cumented Saraguro Group setting near San Antonio
(Fig. 7 ref. 7000 97230). Values of around 1000 mg/kg
also occur over the GanÄarin Belt Au prospects of
CanÄaribamba and GanÄarin.
6.3.3. Principal base-metal anomalies
Values in excess of 100 mg/kg Cu occur widely in
non-mineralised ocean-¯oor basalts and island-arc
basaltic andesites of the Pallatanga and Macuchi Units
(Fig. 6). Anomalous values de®ned by cumulative
probability analysis of the entire dataset thus exceed
200 mg/kg. In the northern and central sectors of the
2±48S area, the most conspicuous base-metal anomaly
of possible economic signi®cance extends between
longitudes 6730±6750 and latitudes 96740±96780. Here
some 20 sites yield Cu values of 300±2000 mg/kg with
attendant enrichment of Mo to 141 mg/kg. This fea-
ture, highlighting the Chaucha porphyry Cu±Mo sys-
tem (UNDP, 1969), is bounded by two parallel N-E
trending structures approx. 4 km apart, within which a
halo of weakly or moderately propylitized granodior-
ites surrounds a core of intense potassic alteration.
Abundant pyrite and chalcopyrite occurs in dissemina-
tions and fracture ®llings.
In the southern half of the mapped area, Cu, Mo,
Pb and Zn anomalies are typically associated with aur-
iferous mesothermal mineralisation. Values of Cu
above the 97th percentile of the population thus occur
in drainage on the southern ¯ank of the Bella Rica
mining ®eld, southwest of the Gaby Cu±Au porphyry,
in the Zaruma±Portovelo area and in mineralised tour-
maline breccias at Tres Chorreras, La Tigrera (Fig. 6
ref. 6512 96446), Paccha (Fig. 2 and Fig. 6 ref. 6488
96045) and Cerro Pelado. In the southwest of the
region, a postulated Cu porphyry occurrence at Fierro
546 T.M. Williams et al. / Applied Geochemistry 15 (2000) 531±550

Fig. 8. Gold anomalies resolved by cumulative probability analysis and subsequent image processing in Interdex2 of data for the
Plancharumi Formation (Saraguro Group). An epithermal target is resolved by values of approx. 700 mg/kg (ppb), above a
threshold of ca. 75 mg/kg.

Urcu (Pratt et al., 1997; Fig. 6 ref. 6855 95920) is high-
lighted by Cu values of 366±419 mg/kg.
6.3.4. Lithogeochemical normalisation
Due to the contrasting lithogeochemical terranes
present within the Cordillera Occidental, many poten-
tial exploration targets which are anomalous only
within the context of their speci®c lithological setting
are not resolved by simultaneous statistical or image
analysis of the entire regional dataset. For the 2±38S
area, Williams et al. (1997) have produced summary
statistics for 15 discrete lithostratigraphic units (Table
8) which, with respect to Au, show between-unit back-
ground variations of up to an order of magnitude.
Anomaly maps constructed for Au and path®nder
elements such as As and Sb following normalisation
against background values for individual lithological
units (Williams et al., 1997) have elucidated Au targets
with values of only a few hundred mg/kg which, while
inconspicuous at the regional scale (Fig. 7; Table 7),
are of potential economic signi®cance. Examples
include low sulphidation epithermal Au prospects at
Llano Largo near Molleturo (Fig. 7 ref. 6803 96855)
and Cerro Plancharumi near Soldados (Fig. 7 ref. 6968
96712). In the former case, silici®ed andesitic tu€s of
the RõÂ o Blanco Formation (Saraguro Group) have
been con®rmed by diamond drilling to host structu-
rally-controlled multiple-phase mineralisation with Au
concentrations locally in excess of 100 g/ton. In the lat-
ter, lithologically normalised maps for the Plancharumi
Formation (Saraguro Group, Fig. 8) have elucidated
locally elevated Au values of up to 706 mg/kg in an
area subsequently con®rmed to display subtle propyli-
tic alteration and from which coarse particulate Au
has been recovered from surface drainage (Williams et
al., 1997). Dunkley and Gaibor (1997) have suggested
a volcano-lacustrine setting for the dacitic lavas and
tu€s of the Plancharumi Formation, with coarse
monomictic rhyolite breccias over Cerro Plancharumi
indicating possible proximity to one or more domes. A
metallogenic model bearing some analogy to that of
Yanacocha, Peru, has therefore been proposed.
6.3.5. Role of mercury in regional Au reconnaissance
While several epithermal prospects in the mapped
area, including Cerro Plancharumi, Quimsacocha,
CanÄaribamba and GanÄarin show poor drainage geo-
chemical responses for Au, all are characterised by Hg
enrichment. Regional Hg data thus constitute a poten-
tially valuable exploration tool in the Cordillera
 T.M. Williams et al. / Applied Geochemistry 15 (2000) 531±550
Table 9
Canadian sediment quality criteria (mg/kg) for the protection
of aquatic life (Environment Canada, 1992; in: MacDonald,
1994)
Element No e€ect Minimal e€ect Toxic e€ect threshold
(TET)
As 3 7 17
Cd 0.2 0.9 3 sediment quality in Ecuador, the Philippines and
Cu 28 28 86
Pb 23 53 170
Hg 0.05 0.2 1 Union Draft Sediment Criteria Document (Van Veen
Zn 100 150 540
Occidental, particularly for low sulphidation epither-
mal systems which often lack any other conspicuous
geochemical expression. It is notable, however, that in
each of the above cases the Hg anomalies are displaced
by up to several kilometres from the main economic
target. At Quimsacocha, values of 20±50 mg/kg Hg
some 10 km from the caldera wall (Fig. 7 ref. 7120
96600) may be related to palaeo-spring emanations at
the margins of the lava pile (Williams et al., 1997).
The outcrops which constitute sources for these periph-
eral anomalies are preserved due to their low elevation,
while the highest, typically Hg-enriched, levels of the
epithermal system within the caldera have been
removed by erosion. Such trends provide a basis for
interpretating the numerous strong Hg anomalies
which occur in the absence of Au or base-metal enrich-
ment in other parts of the mapped area. A Hg
anomaly of 14.6 mg/kg near Chilla (Fig. 2 and Fig. 7;
ref. 6669 96098) is considered to represent the periph-
eral expression of a hydrothermal system associated
with the structurally controlled emplacement of a rhyo-
lite intrusion within the GanÄarin Belt fracture system.
6.4. Environmental applications
6.4.1. Rationale
Drainage geochemistry data, although generated
almost exclusively for metalliferous mineral exploration
prior to the 1980's, are now recognised as a valuable
resource for environmental auditing, land-use planning
and risk assessment at scales ranging from site-speci®c
to global (e.g. Darnley et al., 1995). Within the context
of the Ecuadorian Cordillera Occidental, high-quality
geochemical reconnaissance data o€er particular po-
tential for long-term environmental monitoring as the
survey has, in many localities, preceded major human
perturbation. A quantitative environmental baseline is
thus available, against which the impacts of future ac-
tivities, including mining, can be appraised.
547
6.4.2. Development of sediment quality criteria
The development of statutory sediment quality
guidelines has been slow relative to those now interna-
tionally established for the monitoring and protection
of fresh and marine waters (mostly derived from US-
Environmental Protection Agency and World Health
Organisation directives). In recent studies of the en-
vironmental impacts of mining and urbanisation on
Kenya, Appleton et al. (1996) and Williams et al.
(1996a, b) have used guidelines from the European
and Strotelder, 1988) and the Canadian Sediment
Quality Criteria for the Protection of Aquatic Life
'Toxic E€ects Thresholds' (TETs, MacDonald, 1994)
for the provision of an interpretive context. The former
are, however, based solely on the statistical analysis of
sediment data and thus have no speci®c human or eco-
toxicological signi®cance. The latter (Table 9), while
based on modelled and experimental dose-response re-
lationships, assume 100% bioavailability for sediment-
bound contaminants with the result that action
thresholds are possibly over-cautionary.
The application of a single suite of chemical quality
standards to soils or sediments in widely di€ering geo-
logical settings is now widely recognised as inappropri-
ate (Darnley et al., 1995). Within the context of the 2±
48S sector of the Cordillera Occidental, the potential
problems arising from this approach are exempli®ed
by the application of the Canadian TET for As (Table
9) to selected lithostratigraphic units. Many, including
the Macuchi Unit, the Cisaran Formation and the
Quimsacocha Formation display median As values a
factor of 4 below the TET, while median values of ca.
20 mg/kg for the major andesitic formations of the
Saraguro Group (Dunkley and Gaibor, 1997) are natu-
rally in excess of this threshold.
An alternative approach to the assessment of sedi-
ment contamination may involve the derivation of a
lithologically-normalised background, above which
critical or actionable thresholds can be established.
Such a procedure is, however, dependent on the exist-
ence of high quality regional or national-scale geologi-
cal and multi-element geochemical data which depict
the natural lithological spectrum. In this respect, the
geochemical reconnaissance survey described, coupled
with the detailed geological mapping of the 2±48S sec-
tor of the Cordillera Occidental recently completed
under PRODEMINCA, may directly underpin the
development of improved national environmental legis-
lation in Ecuador.
6.4.3. Assessment and prediction of mining impacts
The impact of mining on human health and environ-
mental quality in Ecuadors principal centres of Au
production has been subject to considerable debate
548 T.M. Williams et al. / Applied Geochemistry 15 (2000) 531±550
(e.g. Appleton, 1998) and, since 1994, has formed the
focus of a speci®c PRODEMINCA sub-component
(3.1: Monitoring Pollution Related to Mining).
Particular concern has centred on Ponce Enriquez,
where economically important shell®sh and banana
industries occupy the catchment area downstream of
the principal extractive and mineral processing oper-
ations. In conjunction with reconnaissance datasets
generated during the 1970's (Bergey, 1979) data com-
piled during the present survey facilitate tentative
quanti®cation of the extent of perturbation at such
sites. With respect to Cu and As, there is evidence that
concentrations in sediments may have increased locally
by up to an order of magnitude, notably within 2 km
of the Bella Rica adits. The downstream concentration
gradients depicted by the more recent data are, how-
ever, relatively acute, with the e€ect that values for the
two datasets become more closely comparable ca. 10
km downstream.
In addition to the delineation of new exploration
targets, the multi-element reconnaissance data com-
piled for the Cordillera Occidental provide some
insight into the metallic mineralogy of such occur-
rences, of direct relevance to post-extractive hazard
prediction and Environmental Impact Assessment.
Fundamental contrasts may, for example, be drawn
between the regions low sulphidation epithermal Au
prospects (e.g. Cerro Plancharumi, GanÄarin,
CanÄaribamba) which have characteristically low ca-
pacities for acid rock drainage (ARD) generation and
toxic metal liberation, and the mesothermal assem-
blages of Bella Rica, Tres Chorreras and La Playa in
which inherent hazards associated with sulphide oxi-
dation are compounded by high concentrations of As
and Sb, which form stable oxyanions that are mobile
across a wide pH range.
6.4.4. Natural geochemical hazards
The importance of environmental geochemistry in
the aetiology of numerous trace element-related dis-
eases has been emphasised by Mills (1996).
Lithologically-controlled variations in the environmen-
tal abundance of P, I, Se, Cu, Co and other trace el-
ements exert a ®rst-order control on the distribution of
numerous animal and/or human diseases related to
micro-nutrient de®ciency, of which goitre and cretinism
related to I-de®ciency (e.g Fuge, 1996) and Se-respon-
sive cardiomyopathic diseases (e.g. Mills, 1996) are
best documented. Darnley et al. (1995) have shown
extensive regions of the world to have natural levels of
essential trace elements well below those recommended
for agricultural soils and pasture. Chronic toxicity pro-
blems (in humans and/or livestock) associated with
natural exposure to F (notably East Africa), As (India,
Bangladesh, Thailand, Argentina, Mexico, Chile,
Uruguay) and Se (China, USA) are also widely known
(e.g. Plant et al., 1996). Potentially signi®cant natural
environmental geochemical features of the area of cur-
rent investigation include a zone of intense Mo enrich-
ment (to 100  average upper crustal abundance)
associated with the Chaucha porphyry deposit and
localised Hg enrichment (to approx. 500  average
upper crustal abundance) in the Quimsacocha area.
High environmental Mo levels are a potential cause of
secondary Cu de®ciency through the inhibition of Cu
assimilation in ruminants (Mills, 1996). The in¯uence
is strongly pH-dependent and risks cannot be fully
appraised without further characterisation of local
physico-chemical conditions. With respect to Hg, natu-
ral enrichment of sediments to levels in excess of 50
mg/kg in the vicinity of palaeo-spring exhalations at
the margins of the Quimsacocha lava pile exceed the
maxima reported for the major Ecuadorian Au mining
®elds of Nambija (Williams and Orbea, 1997), Ponce
Enriquez (Appleton, 1996) and Zaruma (Williams et
al., 1998), where anthropogenic Hg contamination has
been suggested to constitute a signi®cant environmen-
tal hazard (e.g. Carrasco and Frederikson, 1998).
7. Conclusions
This regional geochemical survey, initiated in the
Cordillera Occidental of Ecuador as a sub-component
of the World Bank funded PRODEMINCA pro-
gramme, has con®rmed the utility of drainage recon-
naissance methods for multi-purpose geochemical
mapping in the Andean environment. Drainage geo-
chemical signatures appear to provide a reliable surro-
gate for bedrock lithogeochemistry within the area
studied and clearly elucidate it's principal lithotectonic
components in a manner which should assist consider-
ably in the development and validation of a regional
evolutionary model. The metallogenic potential of the
area has also been con®rmed by the regional recon-
naissance data. In addition to Au and base-metal
anomalies relating to known mines and prospects,
lithologically normalised Au and path®nder element
data signify the presence of formerly undocumented
exploration targets, primarily associated with low sul-
phidation epithermal systems.
Several environmental applications for the
Cordillera Occidental regional reconnaissance dataset
may be recognised. For much of the cordillera, the
compilation of multi-element data ahead of any signi®-
cant anthropogenic perturbation has provided a base-
line against which the environmental (geochemical)
impacts of all future developments can be appraised.
The data also provide a foundation for the develop-
ment of pragmatic sediment quality criteria and a
mechanism for the identi®cation of natural hazards
arising from locally or regionally excessive concen-
 T.M. Williams et al. / Applied Geochemistry 15 (2000) 531±550
trations of toxic trace elements, or de®ciencies with
respect to vital macro- and micro-nutrients.
Acknowledgements
All aspects of the regional geochemical reconnais-
sance survey described in this paper were carried out
under the Mining Development and Environmental
Control Technical Assistance Programme
(PRODEMINCA), sub-component 3.4 (Thematic
Mapping). Funding for this work was provided by the
World Bank, the UK Department for International
Development (DFID) and the Government of
Ecuador, Ministry of Energy and Mines (MEM). T.M.
Williams, P.N. Dunkley and J.A. Aspden publish with
the permission of the Director of the British
Geological Survey.
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