32ND INTERNATIONAL GEOLOGICAL CONGRESS

FLORENCE, ITALY
20/08/04 to 28/08/04

Arsenic in a hard rock aquifer: multivariate optimisation of

the groundwater monitoring network

L.F. Molerio León

CESIGMA, S.A, P.O..Box 6219, CP 10600, Habana 6, Ciudad de La Habana, Cuba,
leslie@cesigma.com.cu
R. Toujague de la Rosa
Instituto de Geofísica y Astronomía, Calle 232 No. 19206, La Lisa, La Coronela, Ciudad de La Habana,
Cuba, toujague@yahoo.com

ABSTRACT: This paper describes the results of a geomathematical analysis of natural and arti-
ficially induced arsenic sources in groundwater in a hard rock aquifer. Data on chemical compo-
sition, ground water levels, and other physical variables were collected systematically but dis-
continuously between 1974 and 2001. A special survey was carried out in 2002 to clarify
several geologic settings. Geomathematical tools involved factor and cluster analysis, kriging
mapping techniques and information theory resources. Results allowed to assess the actual in-
formativity of the monitoring network and optimise its spatial distribution, operation frequency
and data collection structure, the improvement of the transit time of arsenic in groundwater, and
to separate artificial sources from natural sources of arsenic occurrence. Surface waters appears
to be contaminated by arsenic coming from lateral flow migration and leaching of concentrates
in zones close to the surface water divides.

INTRODUCTION
Water quality control and aquifer remediation in mining regions contaminated by toxic metals
as As, Pb, Hg, Cd, among others, particularly important were no other sources of water are
available for domestic consumption. Historically, several regions have been affected by con-
tamination from geologic sources, like Taiwan (Williams, 1997), Córdova, Argentina (Thor nton
et to the, 1997), Mexico (Cebrian et al., 1983) as well as west Bengal, India. This has been con-
sidered a case of world calamity due to aquifer contamination by arsenic (As) (Badal et al.,
1996). In these cases the contamination is associated to the pyrite oxidation.

Delita, a Cuban region linked to gold mineralization has shown problems of As contamina-
tion in ground and surface waters. The drinkable water is brought from other towns and the
identif ication and characterization of the generating sources of this contamination is not very
clear.

Delita mines has been exploited for gold since the XVI century. Secondary geochemical
anomalies of Ag, As, Pb among other elements contributes to the poor local water quality. De-
lita is part of the metamorphic belt of the Cuban Isle of Youth. Its mineralized body is com-
posed by mineralized quartz veins associated to apoterrigenous quartz-chlorine-sericít ic-
graphitic schists of the formation Cañada (K2 ). Veins contain gold-arsenopirite, sulfoantimoniets
and disseminated sulphurs, corresponding to the Au-Ag-As-Sb geochemical type. The preco-
cious generation of gold is associated to arsenopirite and the late one to Pb sulfoantimoniets Fig.
1).

According to EPA (2000), the arsenic in rocks is likely to occurr in its reduced form mineral
veins and as well as an oxide. The arsenate (AsO4 -3 ) appears in some minerals replacing phos-

1
phates in apatites. The arsenate species H2 AsO 4 - and HAsO4 -2 are the balanced forms in the pH
range of most of the natural waters. The HAsO4 -2 prevails with pH of 7,2 and H2 AsO4 - for lower
pH. In ambient reducing environments the form HasO2 (aq) can be present. Arsenite (As3+) is
present in aerobic conditions and arsenate in anaerobic conditions. Arsenic could also incorpo-
rate to the drinkable waters from wastes and from certain insecticides and herbicides. The bal-
anced arsenate ions concentration in water depends on the concentrations of the cation and on
the solubility of the different arsenates that could precipitate. The solubility products of the ars-
enates indicate that many of these compounds are not very soluble in terms of the anion AsO4 -3 .
This form only prevails at pH 11,5 and, in the normal range of natural waters, calcium or of
magnesium arsenate solubility is enough to allow that several dozens of milligrams of As can be
retained in solution. Other metals like Cu can limit the solubility from the As to few dozens of
mg/L. Probably the arsenate sorption in the precipitated ferric hydroxide or other active sur-
faces is an important factor restrictive in the solubility of As in natural waters. Local and re-
gional flow systems were described by Arellano et al, (1993, 1995) and Molerio (1993, 1994).

Fig. 1. Location map

MULTIVARIATE ANALYSIS FOR GROUNDWATERS

For the uni- and multivariate statistical analysis of ground waters an observational matrix
composed by a discrete and discontinuous series of 67 cases was available for the following
data:
Sampling depth (m) PROF_
Water temperature (ºC) TEMP
pH PH
Specific Electric Conductivity (MS/cm) SPC
Total iron concentration of (mg/l) FE
Arsenic concentration (mg/l) AS

Factorial decomposition methods were applied with extraction by Principal Components

(ACP) and Varimax Rotation of the observational matrix. The extraction of two factors, apply-
ing Kaiser´s Approach allowed explaining 72% of the total variance of the available time and
spatial series. This maximation of the correlations suggests that the variables involved in the

2
considered factors belong to the series but, however, it is necessary to include other complemen-
tary variables to explain the behaviour of the arsenic in the system.

Table 1 shows the eigenvalues and accumulated variance of the series of superficial waters.

Table 2 shows the factorial loads, considering significant those = 0,6.

Table 1. Eigenvalues
% total Cu mulative % Cumulative
Factors Eigenvalues variance eigenvalue variance
1 2,313 46,262 2,313 46,262
2 1,293 25,863 3,606 72,126

Table 2. Factorial load

Factor 1 Factor 2
PROF_ 0,12449277 -0,66307455
TEMP 0,03044848 0,85446284
PH 0,90609084 0,19418257
SPC -0,68627405 0,40934475
AS -0,94722028 0,1601521
Expl.Var 2,2056245 1,40069331
Prp.Totl 0,4411249 0,28013866

The standardized lineal components (SLC) has the following structure:

Factor 1 = -0,95 AS + 0,91 PH 87 - 0,68 SPC

Factor 2 = 0,85 TEMP + 0,66 PROF

The first factor explains 45% of the total variance by three variable of which, the higher
weight is the own As, closely associated to the pH, but in the same plane of the SPC (Fig. 2).
For SPC role a fully satisfactory explanation should account for a mixture of waters of different
origins in the sample. The control of temperature is more clearly because of its effect on the
solubility patterns and the oxidation reduction potential of the system, in particular, to the de-
velopment of aerobic or anaerobic conditions in the sampling station. The observed communa l-
ities and the scores are presented in the Tables 3 and 4.

Table 3. Observed communalities

From Factor1 From 2 Factor Multiple- R2
PROF_ 0,01549845 0,45516632 0,1853549
TEMP 0,00092711 0,73103386 0,20762012
PH 0,82100061 0,85870748 0,7191284
SPC 0,47097207 0,63853519 0,49564815
AS 0,89722626 0,92287495 0,80444712

Table 4. Factorial Scores (Varimax normalized rotation)

Factor 1 Factor 2
Bodega89 0,2495568 -0,34984548
SMina90 -2,8535261 0,48556295
PArroyo89 0,34720938 -0,17369291
PRuben90 0,39549939 -0,51957945
PMalva89 -0,32094627 -0,08376767
V-1389 0,75079285 0,2199185
Cpipas89 0,11522884 -1,74158065
PEsperanza -0,09909391 -0,81171584

3
 MijailI89 0,78955606 1,80317804
MijailII8 0,24511565 1,49588604
S-789 0,38060732 -0,32436353

To identify the associations among the ground waters sampling stations, numerical classific a-
tion based on non-supervised patterns was applied. An object (cases) dendrogram was built by
simple connection with Ward´s measure of distance (Fig. 3).

Factor Loadings, Factor 1

Rotation: Varimax normalized
Extraction: Principal components
1
TEMP

0.8

0.6
SPC
0.4
PH
AS
0.2
Factor 2

-0.2

-0.4

-0.6 PROF_

-0.8
-1.2 -0.8 -0.4 0 0.4 0.8 1.2
Factor 1

Fig. 2. Factorial plane

Four perfectly differentiated groups could be identified. One includes Mikhail's stations, Bo-
dega 89 and V13 89; another PRubén 90, S 7 89, CPipas and PEsperan. A third group to SMIna
and PMalva89 and a fourth group, independent and exclusive, integrated by the station PArroyo.
In all these cases, waters of different origin and geochemical evolution are present and, there-
fore, should be evaluated in a different way in all the cases. Mapped scores are presented in Fig.
3 showing an interesting distribution of the orthogonally crossed factors indicating those points
where controlling factors coincide. The relationship among the source points of Factors 1 and 2,
SMina and Mikha il, indicates the strong contribution of the discharge points to local contamina-
tion. The point of minimum convergence of scores is associated to the station PArroyo 89 which
deserves special attention for the inflection and the abrupt change of slope of the isolines.

4
Fig. 3. Dendrogram

5
 Fig 4. Factorial scores

SCORES FACTORIALES PARA LOS DOS PRIMEROS FACTORES EN LAS AGUAS SUBTERRANEAS

Bodega89 PRuben90

216500
SMina90

216000

215500 PArroyo89

215000

214500

214000

213500

213000

MijailI89
MijailII8

291000 291500 292000 292500 293000

0 1000 2000

Factor 2
Factor 1

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IDENTIFICATION OF THE CONTAMINATION SOURCES AND THEIR AREA OF
INFLUENCE

The solution of the transport equation was expressed in the construction of a combined map
of interpolation by means of kriging sustained on spherical variograms of the historical maxi-
mum and minimum concentration (Fig. 4. shows the map for maximum concentration). The
isolines allows to identify the area of influence of the contamination and, consequently, the
reach of risk scenarios defined, in this case, by the 0,05 mg/l isoline that represents the Accept-
able Maximum Concentration of arsenic in the drinkable waters according to Cuban Standards.

Maps show that the contributing sources are the same for surface and groundwater and are
concentrated on the mine’s area. The shape of the isolines forms a lobe with its center at PMina
sampling station and derives in South-North direction toward Mijail Station marking the histor i-
cal limit of the mine’s influence area on ground waters. The zero isoline marks the contour of a
risk scenario of danger, approximately limited by a rectangle of about 21 km2 .

Towards the East, in the centre of the triangle formed by the points PRubén, Mikhail and
PAmer, second scenario appears, and a plateau that is not conserved in the map of min imum
values constituting a local effect, maybe associated to uncontrolled and non-monitored dis-
charges.

A third risk danger scenario is associated to arsenic transport in surface, as a result of migra-
tion and discharge of the ground waters and by discharges in the surface waters. Such a scenario
becomes defined by the 0,01 mg/l isoline and covers the whole area between the mine and the
Los Indios Dam, establishing an influence area of about 42 km2 .

The eventual influence area toward the West could not be defined with the available informa-
tion.

CONCLUSIONS

? The Monitoring network currently in operation shows a very low informativity due to
its inadequate composition, surface distribution, monitoring frequency and selected data
acquisition during monitoring. The information that it returns is of very low efficiency
(8% for the Superficial Net and 60% for the underground one)
? The arsenic concentration shows tendency to increase in ground waters except in Cala
Itabo. The reason of this is not clear, as long as during decades mine has not been ex-
ploited, but it can be associated to the low transit time of ground waters..
? The source of the most important arsenic contamination of waters comes from the min-
ing industry. All the identified focus, in surface and ground waters are associated to the
mining facilities.
? The area of influence of the contamination, at the West of the mine, could not be identi-
fied, for lack of sampling points. To the North, South and East, it could be identified un-
til a radius of 7 kilometres from the mine.

The surface waters can appear contaminated by two causes, by the underground migration of
pollutants, by means of lateral flow, and by lixiviation of deposits concentrated close to recharge
areas of aquifer or by surface drainage from mine wastes.

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Fig. 5. Isolines of maximum recorded As concentration in terrestrial waters .

CONCENTRACIONES MAXIMAS DE As (mg/l) EN LAS AGUAS TERRESTRES

Blan00

219000
Eliseo86

218000

MinaPozo79
Bodega89 PRuben74
Geodesia74
217000 PAlberto74
Terra 274
PMina79
Pmina75
SMina86
Mina74

216000
PMaestro74 Manantia01
PaPlanta79
PArroyo89
PArroyo74

215000

214000 Indios01
Indios00
Indios74
V-1279
P1274

213000 CIndios86
Mijail
Mijail86
II89

PAmer89
212000

Terra 174

289000 290000 291000 292000 293000 294000 295000 296000 297000

0 1000 2000 3000 4000 5000

As en las aguas subterráneas As en las aguas superficiales

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 REFERENCES
Arellano Acosta, Daniela M.; B. Degournay; J. GutiérrezDíaz; L.F. Molerio León; O. Ascanio & A.
Santos (1993): Isotope Hydrogeochemistry in the Study of Saline Aquifers. Case of Study-Isle of Youth,
Cuba. Symp. Isotope Tech. in the Study of Past and Current Environmental Changes in the Hydrosphere
and the Atmosphere, IAEA, Vienna, Paper IAEA -SM-329/27P,:514-516

Arellano Acosta, D. M.; L.F. Mole rio León & A. Santos (1995): Dinámica del Flujo Regional en el
Macizo Metamórfico de la Isla de la Juventud, Cuba. IAEA TEC-DOC -835: Estudios de Hidrología Iso-
tópica en América Latina 1994, Org. Internac. Energía Atómica, Viena :139-174

Badal K. 1996: Arsenic in groundwater in seven district of West Bengal, India – The biggest arsenic ca-
lamity in the world. Current Science, vol.70. No. 11, June.pp:976-986.

Cebrian M. E. 1983: Human Toxicol., 2, 121-133.

EPA 2000: Federal Register. Part II. National Primary Drinking Water Regulations: Arsenic and Clarifi-
cations to Compliance and New Source Contaminants Proposed Rule. Fed. Reg. Vol 65 (121), June 22,
2000, 97:

Molerio León, L.F. 1993: Dinámica del Flujo Regional en el Macizo Metamórfico de la Isla de la Juven-
tud. Taller sobre Aplicación de Técnicas Isotópicas en el Estudio de los Recursos y la Contaminación
de las Aguas, OIEA, Maracaibo, Venezuela, 14:

Molerio León, L.F. 1994: Isotopic and Geochemical Regionalization of a Tropical Karst Aquifer. Inter-
natl. Symp. isotopes in Water Resources Management; OIEA, Vienna, Austria, Paper IAEA -SM-
336/88P, 6:

Thornton, I, M. Farago (1997): The Geochemistry of arsenic. In Albernathy, C. O.; Calderon, R.L.; Chap-
pell, W. R (eds.) Arsenic exposure and health effects. Chapman & Hall, London, pp: 1-16

Williams, M. (1997): Mining - related srsenic hazards: Thailand case-study Summary Report. Key worth,
Nottingham, UK. British Geological Survey, 36 .