JOURNAL OF

CEOCNEMICAL
EHPUMATIllN zyxwvutsrqpo
ELSEVIER Journal of Geochemical Exploration 58 ( I YY7) 8 l-9 I

200 years of mining activities at La Paz/San Luis Potosi/Mexico

- Consequences for environment and geochemical exploration
Javier Castro-Larragoitia ‘, Utz Kramar “, Harald Puchelt h

Abstract

The Ag-Pb-Zn-G-Au mining district of Santa Maria de La Paz has been extensively exploited for approximately 200
years. Consequences of these activities are several deposits of tailings with high As and heavy metal concentrations, which
are completely unstable. The climate is semiarid and as the dumps have no protective cover, material from the dumps is
dispersed by strong winds. It is also washed out during seasonally heavy rainfalls. By these processes approximately 100
km’ of surrounding have been contaminated by dump material, The As and heavy metal content of the soils was determined
as well as their level in crops (Zea Maize) from agricultural lands in the vicinity of the dumps. In the direction of prevailing
winds concentrations up to 1000 ppm Zn, 400 ppm Pb, I6 ppm Cd, 550 ppm Cu and 300 As have been detected in top soils.
Using fuzzy cluster analysis the different contamination sources could be identified. Grains of corn from contaminated sites
showed no critical concentrations, but leaves which are also used for fodder. have As-concentrations up to 20 ppm.

Kt~~rds: environment: soil; heavy metals; arvznic: mine tailings: .Mexico

1. Introduction bonates. A N-S trending fault at the eastern fringe

of the Sierra de1 Fraile divides the deposit into two
The Ag-Pb-Zn-Cu.-Au mining district of Santa different bodies: the eastern part consists of hy-
Maria de La Paz is located approximately 500 km drothermal Ag-Pb-Zn veins and the western part of
NNW of Mexico City (Fig. 1) and 5 km west of the Cu-Au-skam mineralization.
small Town of Matehuala/San Luis Potosi (Fig. 2). The mine district of La Paz has been extensively
It occurs at the western margin of the Sierra Madre exploited for approximately 200 years. In 1992, work
Oriental on the eastern slopes of a small mountain on the eastern veins was ceased due to the low
range known as the Sierra de1 Fraile which is an market prices. The mines in the skam deposits (Cu-
overturned anticline. The deposits of La Paz are part Au) “Dolores” and “Cobriza” are still in produc-
of a 1600 km long NW-trending belt of carbonate- tion. For more than 60 years the ores have been
hosted high temperature (> 200°C) hydrothermal treated in the ore-dressing plant of La Paz. Until
mineralization (Megaw et al., 1988). The majority of approx. 1960, the ores were refined in a smelter at
these deposits, including the La Paz mineralization, the northern side of Matehuala (D4) (Fig. 2).
was emplaced in Jurassic-Cretaceous platform car- Consequences of all these activities are several

0375-6742/97/$17.00 Copyright 0 1997 Elsevier Science B.V. All rights reserved

PII SO37S-6742(96)00054-1
x2

Pacilic

m Sierra Cladre Ortental

0 Sierra Madre Occidental
m transmeucan I olcanic belt

Fig. I. Schematic map of Mexico with geographical IocA~n of the Ag-Pb-%n+Ctl- Au mining district of Santa Maria de Ln Pa/.

Sampling points 0
-”JVla‘tehL zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONML Conglomerate
cretac. Limestones
0 juras. Limestones
0 2 km Granodiorite

Fig. 2. Sketch map of the La Pa7 mining district showing Iociltions 01‘ tailing. Location> DI-D3 xc refered in the text
 Fig. 3. The “big dump” Sta. Maria de La Paz (DI).

deposits of tailings which are completely unstable.
The biggest of these dumps (Dl) (Fig. 2) has a
volume of 8 X IO6 t with As-concentrations of ap-
proximately 4000 ppm and is completely uncovered
(Fig. 3).
Since the climate is semiarid and the dumps have
no protective cover, material from the dumps is
dispersed by strong winds (Fig. 4). It is also washed
out during seasonally heavy rainfalls. By these pro-
cesses, dump material is dispersed in the environ-
ment resulting in a widespread contamination of the
surrounding soils. Most of the minewaters (4.5
m’/min; pH = 7-7.5) are used in the flotation plant
but some is used for agricultural irrigation without

Fig. 4. Wind blow out from the “big dump” Ste. Maria de La Paz (Dl).
any treatment. The mine is therefore the main source
for environmental pollution, although some nearby
industrial sources can not be neglected.
As a result of the mining and industrial activity a
variety of anomalies of different origin (geologic and
anthropogenic) exists in the area of La Paz:
- geologic from subsurface mineralization
_ anthropogenic-geologic from the recent and
abandoned mining activities
_ anthropogenic from ore dressing and the result-
ing dumps
- anthropogenic from ore refining and other in-
dustrial sources, e.g. recycling of Pb from batteries
The aim of this study was to discriminate between
the different types of anomalies and contaminants
and to estimate the consequences for geochemical
soil exploration and for food production in this re-
gion. It therefore represents a case study on the
effects of extensive mining in semiarid environ-
ments.
2. Sampling and sample preparation
More than 200 locations have been sampled in an
area of approximately 100 km’. The soil samples
were taken by an earth auger. At most of the loca-
tions, three horizons were sampled (A,, approx. O-20
cm: B,,/B,, approx. 20-50 cm and C,/C,, > SO
cm to the top of the calcrete layer). To study the
vertical transport in the soil column, some soil pro-
files were sampled in detail. The soils are in general
calcic to gypsic xerosols (FAO-nomenclature) con-
taining a “calcrete” horizon, which begins at a
depth of approximately 50-100 cm. Sample loca-
tions were selected with respect to prevailing wind
directions and drainage systems. The prevailing wind
direction in this area is SSE and the flow direction of
drainage systems is from Sierra de1 Fraile in the W
into the Matehuala valley. Groundwater flows from
the NW to the SE at a depth of 5 m in the middle of
the valley. In the La Paz area, the undisturbed
groundwater level occurs 120 m below surface. Due
to the mining activities, the level has been lowered to
a depth of about 850 m below surface in the immedi-
ate vicinity of the mine. Therefore contamination of
the groundwater is not apparent. Consequently, sam-
pling focused on the area N of the big dump Sta.
Maria de La Paz (DI 1 and S of this dump. where
mining waters are zyxwvutsrqponmlkjihgfedcbaZYXW
use d for agricultural irrigation.
Additionally the area N of the old refining plant (D4)
and the drainage system starting at the big dump into
the Matehuala valley were sampled. This area was
flooded during heavy rainfalls in 1990. by waters
containing tailings.
Background samples have been taken from the
eastern slope of Matehuala valley in an area not
affected by wind- or water transport of material from
dumps, mines or industrial activities. From agricul-
tural areas, samples of corn (Zru MU&J) and chili-
plants were also taken to estimate the transfer of
toxic elements into the food chain, Sampling points
are indicated in Fig. 2.
Soil samples were air dried and screened to < 2
mm. an aliquot of this material then being used for
pH determination, and the remainder was finely
ground for chemical analysis. The plant material zyxwvutsrqp
was
dried at 105°C and ground.
All soil samples were analysed by energy disper-
sive X-ray fluorescence (EDXRF) for I3 elements
including Cu. Zn. As. Cd. Sn. Sb and Pb. Foi
verification and to obtain information about addi-
tional elements including Au. 21 soil samples and 7
samples from the dump were analysed by instrumen-
tal neutron activation (INAA). Plant samples were
dissolved in HNO, by microwave digestion and
analysed by ICP/MS. Exchangeable heavy metals in
the O-20 cm horizon from 40 sample locations was
determined by I M NH,NO, extraction (E DIN
19730, 1993) and ICP/MS. Details of the analytical
procedures are given in Kramar, 1984; Kramar and
Puchelt, 1982 and Niiltner et al., 1990. The analyti-
cal data were then evaluated by fuzzy cluster analy-
sis (Kramar, 199.5) to discriminate between back-
ground, geologic and the different anthropogenic
anomalies.
2.2. Principles zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQ
of,fuzzy-cluster analysis
If the data structure present is not known a priori.
cluster analysis can be used to evaluate the geochem-
ical data. Iterative partitioning techniques intend to
group the data into a number of discrete clusters. If
 J Ctrstro-Lurrqoitiu et al. / Journal oj’Grochrmiccz1 Exploration 58 (IYY718lLYl 85

w A
7'
the partitioning into a predetermined number of clus- 10
ters is appropriate, K-means clustering is the tech- 25 A w :
nique most widely used. Each sample is then as- 40 A IIC 1
signed to the clusters (groups) to which it is most -z 55
,c-l_
similar. In geological sense. each cluster will repre- 5 70
% A 0
sent one geological unit or a group of anomalous
u 85
samples. One sample can only be assigned to one 100 ; vo .
l /,
cluster. zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFEDCBA
115 .
In stream sediment and soil surveys, the samples
130
will be a mixture of components derived from differ-
1 10 100 1000 10000
ent geological environments. Such mixed samples
will be misclassified when using conventional rcu Zn *As - Sr ACd Pb
“hard” cluster methods. Fuzzy-c-means (FCM) Fig. 5. Elemental concentrations in a soil profile with surface
clustering (Bezdek et al., 1984) avoids these prob- contamination taken from an area N of dump D4.
lems of misclassification. In FCM, each sample is
allowed to belong to several clusters. The amount of
an element explainable by cluster contributions and 1 (identical) (Fig. 5). The sum of membership values
its residual can then be calculated. of each sample is equal to 1. Outliers are distributed
The concept of fuzziness, introduced by Zadeh equally between all clusters. Details of the FCM
(1965), is a new approach to consider inaccuracies in method used in this paper are given in Kramar
cluster data analysis. Such inaccuracies are caused (1995).
by stochastic scattering and by samples composed of
several components. In fuzzy-c-means cluster analy-
sis, some fuzziness in cluster assignment is tolerated. 3. Results and discussion
Whereas the assignment probability of a sample to a
specific cluster is no longer of interest, the relative 3.1. Tailings
part of a sample that belongs to a specific cluster is
calculated (Bezdek, 198 1). Tailings of Sta. Maria de La Paz (Dl) can be
In FCM, overlapping of the different groups is regarded as the greatest potential contaminant in the
allowed (Fig. 5). This makes FCM-clustering more La Paz area. Samples taken from different locations
appropriate for the analysis of geochemical data sets at the dump show average concentrations of 400
than conventional hard cluster methods, in which one ppm Cu. 2000 ppm Zn, 4000 ppm As, 30 ppm Cd,
sample can only be assigned to one cluster. The 3000 ppm Pb and 0.7 ppm Au (Table I>. The
similarity of a sample to a cluster centroid (CZ) is mineral composition of tailings from the Ag-Pb-Zn
described by a continuous membership function with mines of La Paz is dominated by calcite and to a
values varying between 0 (completely different) and minor extend quartz. The most important sulfides of

Table I
Average concentrations of samples from the “big dump” Sta. Maria de La Paz (Dl)
Element Concentration hulk Concentration < 63 km Concentration 63-200 km Concentration 200-600 p_m
Img/kgl lmg/kgl 1%/&l [m&/kg1
CU 400 415 330 510
Zn 2,000 2,220 I.754 1,470
AS 4,000 41,000 2.500 890
Cd 30 21 33 21
Ph 3,000 710 420 332
AU 0.7 2,s 0.8 0.4
the La Paz mining district are pyrite, araenopyrite.
sphalerite. galena. chalcopyrite and bornite. Most
sulfides in this older parts of the dump are oxidized.
Arsenic released by the oxidation process can be
adsorbed by Fe-hyrdoxides produced by sulfide oxi-
dation (Pierce and Moore, 1980: Goldberg and
Glaubig. 1988: Davis et al.. 1989). Tailings of the
Cobriza mines (Cu-Au). which were deposited re-
cently. consist mainly of quartz and pyroxene (di- 1 .*. 1
opside-hedenbergitel with minor wollastonite and 0 1000 2000 3000 4000 5000 6000
calcite. From the sulfides contained in this material distance fromDl [m]
only a minor amount has been oxidised by chemical
weathering.
Whereas Cu. Zn. Cd. and Pb are approximately
equally distributed within the different grain size
fractions (200-600 km, E-200 pm and < 63 pm).
As is greatly enriched in the finest fraction with
concentrations of up to 5%. Due to the high concen- calcrete layer is reflected in the Sr content of the
trations in the fine fraction and its greater mobility profile. The contamination by tailings material can
under oxidizing and neutral to slightly basic condi- be traced down to the top of this layer. Due to its
tions, As can be more easily released from the sandy high mobility under these environmental conditions
dump material as compared with the heavy metals. (Boyle and Jonasson, 1973: Brookins. 1988) As is
In water elution tests of the tailings material As was enriched at the top of the calcrete layer. which acts
released as arsenate (Riide and Puchelt. 1994). as an infiltration barrier.
Residual Fe-salts (Fe-sulfates/arsenates] at the base The soil samples of the surroundings of the big
of the dump showed As-concentrations in the order dump (D I ) show greatly increased values for heavy
of 10%. metals and A\ in the upper horizons. Along a N-S
traverse (Fig. 6) starting 200 m N of the big dump.
3.2. zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFEDCBA
Soils the concentrations for Zn. Pb and Cd decrease ap-
proximately exponentially with distance from the
3.2.1. Lu Pa,- distric,t dump. Zinc decreased from > 1000 ppm to 200 ppm
Mineralogically the calcic to gypsic xerosols in at a distance of 4 km downwind from the dump and
the vicinity of La Paz are dominated by calcite and to 100 ppm at 5 km distance. Lead decreases from
gypsum. The amount of quartz and clay minerals is 390 ppm to 30 ppm and Cd from I6 to - 1 ppm.
generally < 5%. Top soils from agricultural lands Copper and As show a completely different pattern.
contain up to 5% organic C and pH is neutral to Up to 2 km distance from the dump the behaviour 01
slightly basic pH (7.58). Adsorption of heavy met- Cu and As concentrations is equivalent to Zn, Pb and
als and As in soils is mainly controlled by soil-pH. Cd. Then Cu and As concentrations increase again to
clay minerals. Fe- and Mn-hydroxides. and organic 550 ppm and 300 ppm respectively. At this point, the
matter. Due to their low concentrations in the soils traverse crosses the slope of Sierra del Fraile drain-
from the vicinity of La Paz, clay minerals are less ing the area of the Cobriza Cu-Au mine. Water
important. transported material from this mine was assumed to
Fig. 5 shows the element concentrations of a soil be the origin of this anomaly. This was verified by
profile taken from surface contaminated soils north results of Fuzzy-cluster analysis. The investigated
of dump D4. The heavy metals decrease with depth area can be characterized by 3 of 9 Clusters: slightly
and the pattern of heavy metals and As i\ character- contaminated soils (CLO2). highly contaminated soils
istic for tailings from the La Paz mine. This can be from the surroundings of the dumps (CL081 and
used as indication for surface contamination. The zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFE
gypsum-rich soils (CLO7). The spatial distribution ot
contribution values for the three most characteristic
clusters together with elemental residuals of Fe and
the product (Cu Sn) are given in Fig. 7.
Extremely highly contaminated samples are char-
acterized by their own clusters, which are typical of
the different dumps. With those clusters high contri-
bution values occur only in the very close vicinity of
these dumps.
The residual values (i.e. the difference between
bulk and cluster concentrations) (Cu . Sn) and Fe
show high values in the northern part of the N-S
traverse. This elemental association is characteristic

Fig. 7. Maps of contribution values to clusters CLO2. CL07 and CL08 together with elemental residual of Fe and the residual product
cu Sn.

H=cHx
x Pb-A
xw
-wx
PX
10 100 1000
wk
Fig. X. Variation of Cu. Zn. As and Pb in O-20 cm and > 50 cm
horizons from agricultural fields S of dump DI
for the Cobriza Cu-Au mineralization, located uphill
to the W from this point.
Approximately 100 m N of the small dump (D3) a
Pb-recycling plant was running for several years.
Soils from the vicinity of this plant show clearly
elevated values for Cu. Zn, As and Pb. Compared
with material from the dump the concentration of Pb
has increased relative to Zn, As and Cu. This pattern
can be interpreted as a mixture from these two
potential contaminants.
North of Matehuala two types of contamination
can be observed: run-off-water and material from the
dumps washed out during heavy rainfalls flooding
the area N and E of Matehuala in 1988. The runoff
waters had entered the central Matehuala valley E of
the town Matehuala. Drainage sediments contain up
to 10% As. Soils of this area are contaminated with
several hundred ppm As, Cu, Zn and Pb.
The halo due to emanations from the smelter (D4)
can be traced several kilometres to the N by concen-
trations in soils at up to several hundred ppm Cu. Zn.
As and Pb (at approx. 3 km distance from the
smelter - IS0 ppm Cu, 250 ppm Zn. 200 ppm As
and 400 ppm Pb). At 6 km distance the concentra-
tions of these element have decreased
levels. The area directly N of the smelter was flooded
by runoff waters from the big dump and therefore up
to 500 m distance to the N concentrations of Cu. Zn.
Fig. 9. Spatial distribution of As. Cd. Cu. Sn, Sr and Zn concentration\ in horiaxh
S of dumps DI and DZ.
As and Pb in soil5 fluctuate between 200 and 2000
Pb-C
ppm each.
The area S of the big dump (DI) is used for
As-C
domestic purposes and agriculture. Contamination ot
X As-A this area can be expected by wind transported mate-
Zn-C rial from the dump and from mine waters which arc
Zn-A used for irrigation. The mine waters carry approx.
cu-c 700 kg/l As. SO mg/l Cd. 30-200 kg/l Pb, 1500
CL-A kg/l Zn and 2000 mg/l SOS
Statistical parameters for Cu, Zn, As and Pb in
10000 the three soil horizons O-20 cm (A) and the > 50
cm (C) horizon of the sampling grid from the area S
of DI are summarized in Fig. 8 as notched box-plots,
minimum and maximum values.
Zinc, As and Pb are enriched in the top soils with
up to 5000 ppm Zn, 6600 ppm As and 2700 ppm Pb.
These high values can not be explained by contami-
nation with dump material alone. Especially at greater
distances from the dump the ratio As:Zn:Pb is shifted
in favour of As and Zn. Since Pb is nearly immobile
under oxidizing and neutral to slightly basic pH
conditions (Brookins, 1988), its transport in mine
waters is limited. and thus the ratio shift can be used
as an indication for contamination by mine waters.
3.2.2. Agricultural areus
The major part of the Zn and Cd (Fig. 9) contami-
nation in this area can be traced back to the big
dump Sta. Maria de La Paz (Dl). Copper and As
contamination originates equally at both dumps D I
and D2. whereas the main source of Sn is from dump
D2. Strontium shows a completely different be-
haviour and can used as indication of the develop-
ment of calcrete horizons. For a part of the soil
profiles. Cu shows the same general trend as Pb. but
at several locations Cu and Sn concentrations also
increase with the depth (Fig. 9). This increase can be
regarded as an indicator for geologic anomalies.
to background
Plants sampled from agricultural lands in the
vicinity of the dumps show increased levels of heavy
O-70 cm. 10-50 cm and > 50 cm of agricultural fields
 ............... ...................... ............... ..........................
~\~l~c;.x;;~~ p~~~~~ / \,,t)
:::i;iiiiii::i
............. 1 jj:~:~~:~:~:~:::~:~:.::~~~.~~:, .....:..,...........; ..................................
.... , .
..i..
...___
. ... ... ....... ..: .~i.~i.~i..i.~:..i.~;..~..;..i..~.~~
;.
yr

I , I I
Tahlc 2 Since spraying is not used in the irrigation pro-
Concenrr;ltlon range of As, Cd. Pb and Zn in different parts 0lZea
cess, the most probable sources for toxic elements in
Maize in comparision with German gnidelines for allowable CW-
centrations for corn grains and fruits
the plants arc soil ~ plant transfer. dust particles
adherent on leaves and uptake of soluble dust com-
Part 211 As ’ Cd
01’ [mz/kgl lmg/kgl lmg/kgl Fig/kg] ponents through the leaves. To avoid contamination
plant by adherent dust particles, the plants had been thor
oughly cleaned. From several plants lower and uppct
stern 9.63-400 0.28-3.9 0.02-0.66 < 0. I I-2.8
h\C\ 2X.7-200 2.1-33.1 0.13-1.75 2.4-58.8
leaves and stems were sampled. In most of these
grain\ X0-82 0.050.55 0.008--0.0x7 < 0.02-0.37 plants concentrations of toxic elements (As. Ph)
decrease from bottom to top. In these case\ uptake
from the soil can be regarded to be the prevailing
process. Overall. there is a good correlation fog- the
As, Cd and Pb concentrations in soil and the differ-
” t%r As no valid guidelines exist. The older value of 0.5 mg/kg ent plant parts. This correlation is more significant
(BGA. 1977) has been withdrawn.
than that for the NH,NO, extraction (readily cs-
changeable cations).
metals and As compared with those from uncontami- For some plants the concentrations in leacej rc-
nated areas. Concentration ranges for As, Cd, Pb and main nearly constant from bottom to top. In these
Zn in different parts of Zea maize together with cases uptake through the leaves has to be considered
German guidelines for allowable concentrations are to be as important as uptake by soil.
compiled in Table 2. In the corn grains concentra-
tions up to 0.6 ppm As, 0.09 ppm Cd and 0.27 ppm 4. Conclusions
Pb were found. The maximum concentrations ob-
served in the grains are slightly below the guidelines In the vicinity of the La Paz mining district. an
for allowable concentrations, but the leaves from arca of approximately 100 km’ has been affected by
these plants showed concentrations up to 20 ppm As. tnining activities. The multielement data set pro-
I .7S ppm Cd, and 49 ppm Pb (Fig. IO) and these duced by multielement analytical techniques in con
leaves are also used for fodder. Chili pods showed junction with methods of fuzzy cluster analysis used
concentrations of up to 3 ppm each for As and Cd in this paper, are able to discriminate between differ-
and 1.5 ppm Pb (i.e. 60 times the allowable Cd ent contamination sources and geologic anomalies at
most of
concentrations for fruits). zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFEDCBA the locations. By far the most important
contaminant source is the big tailings dump of Sta.
Maria de La Paz. Water transported material from
100
these tailings cause significant contamination of soils
in the central Matehuala valley up to IO km distance.
Windblown material can be traced for mom than 5
km to the N and to a lesser extent, to the S.
Contamination with material from mining activities
occurs in the top soils down to SO-100 cm below
surface. Therefore geologic anomalies in top soils
from the vicinity of the mines and dumps are masked.
predominantly by contamination with tailings materi-
als. The contamination effect decreases with the
100 1000
total sods [mg/kg]
depth, thus the concentration gradient can be used to
stem A leaves = grain
n
discriminate between geologic anomalies and anthro-
Pi<> IO. Al-\enic concentrations in leaves. stem ‘md gminr of Zea
pogenic anomalies.
M&s ;I\; 8 function of total soil content\ from agricultural fields S The most critical effects on the food chain OCCUI-
01 dump DI and D2. in those areas. irrigated by mine waters. Overall.
concentration of toxic elements in corn grains does Bezdek, C.J., Ehrlich, R. and Full, W.. 1983, FCM: the fuzzy
c-means clustering algorithm. Comput. Geosci.. IO: 191-203.
not exceed the allowable concentrations, but concen-
Boyle. R.W. and Jonasson. I.R.. 1973. The geochemistry of
trations in leaves exceed the allowable concentra- arsenic and its use as an indicator element in geochemical
tions for vegetable up to 20 times for Cd and up to prospecting. J. Geochem. Explor., 2: 25 I-296.
50 times for Pb. The leaves are used for live stock BCA (Bundehgesundtheitsamt), 1977. Richtwerte ‘76 iiher Arsen-,
fodder. This seems to be the most important way the Blei-. Cadmitm- und Quecksilbergehalte in Lehenamitteln.
Bundesgesundheitsblatt. 20: 76.
toxic elements enter the food chain for humans. On
BGA (Bundesgewndtheitsamt), 1993. Richtwerte liir Schadstoffe
the effect to humans and live stock no clinical in Lebensmitteln. Bundesgewndheitsblatt. 5/93: 2 IO.
studies for this region have been made. Probably Brookins, D.G.. 198X. E,-pH Diagram\ for Geochemistry.
critical concentrations of heavy metals and As occur Springer. Berlin. Heidelberg. New York, London. Paris. Tokyo,
in meat of live stock. The concentrations of several II6 pp.
Davis, J.A. Fuller. C.C. and Cook, A.D..lYXY. Sorption and
toxic elements in maize grains are close to the
coprecipitation of arsenate by ferrihydrite. In: Miles (Editor),
allowable concentrations. Thus a further increase of
Proceedings of the 6th International Symposium on Water-
environmental pollution can not be tolerated. Rock Interaction. Balkema. Rotterdam. pp. I87- I XY.
It is therefore highly recommended to avoid the E DIN IY730. 1903. Ammoniumnitratextraktionen ,ur Bestim-
use of maize leaves for fodder and additionally to mung Mobiler Spurenelemente in Minrralbtiden. Beuth, Berlin.
Goldberg. S. and Glaubig, R.A.. lY88. Anion sorption on a
cover at least the biggest dump in order to minimize
calcareoua. montmorillonitic soil - arsenic. Soil Sci. Sot.
the contamination by wind-blown material. The use .4m.. 52: 1297~1300.
of untreated mining waters for irrigation has to be Kramar, U., 198-L First experience with a tube excited rnergy-dis-
abandoned to avoid salinization and further increase persive X-ray fluorescence in field laboratories. J. Geochem.
of the level of toxic elements in agricultural used Explor.. 2 I: 373-383.
Krnmar. U.. 1905. Application of limited fuzzy cluster\ to anomaly
soils.
recognition in complex geological environments. J. Geochem.
Explor.. 55: X1-97.
Kramar. U. and Puchelt. H.. 1982. Reproducibility tehts for INAA
Acknowledgements determinations with AGV-I. BCR-I and GSP-I and new data
for 17 geochemical reference materials. Geostand. Newsl.. 6:
72 I -227.
The authors wish to thank the Negociaci6n Min- Megaw. P.K.M.. Rulr. J. and Titley. S., 198X. High-temperature,
era de Sta Man’s de La Paz especially Ing. L.H. carbonate-hosted Ag-Pb-Zn-(Cu) deposits of Northern
Cajero for supporting these investigations on site. Z. M&co. Econ. Geol.. 83: 1856-1855.
Bemer. D. Meyer and J. Stummeyer carried out the Niiltner, T.. Maisenhacher. P. and Puchelt. H.. IOYO. Microwave
acid digestion of geological and biological standard reference
ICP-MS investigations.
material\ for trace clement analysis with ICP-MS. Spectrosc.
We also wish to thank W. Salomons and G.F. Int.. S(q): 10%S3.
Taylor for helpful comments on the manuscript. Pierce. M.L and Moore. C.B.. 1980. Adsorption of Arhenite on
Amorpous Iron Hydroxide from dilute Aqueous Solution.
Environ. Sci. Technol., 14: 311-216.
Riide. T.R. and Puchelt. H.. l9Y4. Development of an automated
References techmque fro the speciation of arsenic using flow injection
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