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Water Resources & Environmental Problems in Karst - CVIJIĆ 2005
499
HYDROCHEMICAL CHARACTERISTICS OF SOME
LITHOLOGICALY DIFFERENT KARST MASSIFS OF ALBANIA
Romeo Eftimi
ITA Consult, Tirana, Albania, eftimi@sanx.net
Abstract: The chemistry of 25 springs located at four karst areas of Albania with different
lithology shows a very clear relation of the karst water quality to the lithology of rocks. Most
indicative parameters characterizing the chemistry of karst springs result: water conductivity,
total hardness, ionic ratios rCa/rMg, rSO4/rMg, CO2 pressure and the indexes of calcite (Sic)
and dolomite saturation (Sid). Very useful for the attachment of the chemistry to the special
lithologic units results the graphic of rCa/rMg versus rCa/rMg, combined with SO4 content, as
well as the graphic of indexes of calcite saturation versus the indexes of dolomite saturation.
The water quality parameters are used also to characterize the karst flow system of carbonate
springs. The Blue Eye Spring, the biggest spring of Albania, which average discharge is about
18.5 m³/s has a diffuse-flow feeder–system.
Key words: Karst water chemistry, index of calcite saturation, index of dolomite saturation,
CO2 pressure, kasrt flow system.
INTRODUCTION
About one-fourth of Albania’s land surface is karstified and about two-third of the
groundwater resources of the country are karstic ones. This study was focused on four
karst areas with different lithology; pure limestone, mainly dolomite, limestone and
dolomite and limestone with gypsum. The main objectives of this investigation were
the same as those pointed out by Back and Zöetl (1975) for the geochemical studies:
to determine the stratigraphic and lithologic distribution of the chemical water type, to
determine the quality suitability of karst water and to understand the physics of the
karst systems.
Description of the study areas
The studied karst areas are situated in the central and in the southern part of Albania
(Fig. 1). Table 1 gives the main geological and hydrogeological data of the
investigated karst massifs. Morphologically the investigated karst massifs represent
high mountains of 1600 to more than 2000 m a.m.s.l., which dominate on the
surrounding low elevation eroded flysch areas. The sinkholes and karst poles are a
very common phenomenon on Mali me Gropa and Tomori massifs; they form karst
plateaus which appear as the main recharge area of the major springs. At the
remaining investigated karst massifs, while the sinkholes practically are missing, some
Water Resources & Environmental Problems in Karst - CVIJIĆ 2005
500
big karst caves are developed. The groundwater
flow direction is controlled mainly by the
hydraulic slope; sometimes the ground water
cross faults, folds and stratification beds.
Method of study
Physical and chemical data were collected at 25
mostly big springs. A total of 84 water samples
from these springs were analyzed for major
dissolved components. The frequency of
sampling varied; only two springs, the Blue Eye
and Pellumbas are sampled more systematically.
At each sample site was measured the water
temperature, ph and electrical conductivity (EC),
while the chemical parameters are determined in
the laboratory. Chemical analyses were
conducted within 4 days of sampling. From the
results of the chemical analyses ionic strength I,
calcite saturation index Sic, dolomite saturation
index Sid, the equilibrium of carbon dioxide
Fig. 1. Location of studied karst pressure PCO2, rCa/rMg and rCa+rMg, (r denotes
massifs: 1. Dajti; 2. Mali me Gropa the value is in e.p.m.) are calculated.
3. Tomori; 4. Mali i Gjere
Table 1. Main geological and hydrogeological data of the investigated karst massifs.
Nr.
Name of
the area
Lithology
Surface
km²
Yearly
precipitation
mm
Yearly
infiltration
mm
Main springs and the
average discharge
l/s
1
Dajti
Cretaceous dolomites
and less Eocene
limestone
80
1800
700
Pellumbas, 500
Buvilla, 390
Gryka e Buvilles, 30
Gjorm, 15
2
Mali me
Gropa
Triassic pure
limestone
165
2100
1150
Selita, 510
Shemria, 1100
Guri Bardhe, 700
3
Tomori
Cretaceous dolomite
and Eocene limestone
145
1365
650
Kerpica, 725
Bogova, 1350
Guaku, 1500
4
Mali Gjere
Mesozoic and
Paleogene limestone
with siliceous rocks
340
2260
1175
Blue Eye, 18.500
Viroi, 0-35.000
Vrisi, 90
Kardhikaqi, 250
Water Resources & Environmental Problems in Karst - CVIJIĆ 2005
501
Sic and Sid are defined (Garrels and Christ, 1965, Thrailkill, 1976) as
Sic = (Ca2+). (CO32-) / Kc (1)
Sid = (Ca2+). (Mg2+). (CO32-)2 / Kd (2)
PCO2 = H2CO3 / KCO2
(3)
Where the brackets indicate activities of the ions; Kc, Kd and KCO2 are the respective
equilibrium constants of calcite dolomite and of carbon dioxide. Ionic strength (I) is
then calculated. Once I is known, the activity of ions Ca2+, Mg2+ and CO32- are
calculated using the Debye-Hückel equation (Garrels and Christ, 1965). The values of
the equilibrium constants used in this study are those given by Langmuir (1971),
Thrailkill (1972, 1976), Drever (1983) and others. The most important uncertainty
among measured values is in the pH. The total uncertainty in calculated values of Sic
and Sid is about ±0.15 units. We therefore assume that all values of indices within
±0.15 units of zero are saturated with respect to the carbonate in question.
Results and discussion
Hydrogeological data and chemical parameters and computed Sic and Sid and
equilibrium CO2 pressures values for the spring waters are generalized in Table 2 and
in the graphics of rCa/rMg versus rCa+rMg (Fig. 2) and of Sic versus Sid (Fig. 3).
Essential differences in chemistry exist between spring waters of different karst
massifs.
The spring waters of pure limestone of Mali me Gropa massif have low hardness, low
SO42- concentrations, and therefore also a low EC. In these waters, the ratio rCa/rMg
has high value, and in opposite of this the ratio rSO4/rMg has lower values. Similar
characteristics have also the spring waters of Tomori massif where the dominant rocks
are also the limestone.
Dolomite waters of Dajti massif are hard; they have relative high SO42- concentrations,
and high EC. The sulfate may come from the oxidation of the trace pyrite and
marcasite and of trace gypsum, which are present in dolomites of Dajti massif.
The water of Blue Eye spring in Mali Gjere massif is hard; the concentration of SO42-
is about 135 mg/l and EC is relatively high. The spring water is saturated with respect
to calcite and is near saturated with respect to dolomite. The main SO42- source for the
Blue Eye spring water seems to be the sulfate waters of nearby Drinos Valley that
recharge this spring. This contributes also to the increase of rSO4/rMg ratio of Blue
Eye spring water up to 5.4.
It is already known that rCa/rMg ratio in groundwater has a clear geochemical
implication; their values are usually lower in dolomite and higher in limestone
(Langmuir, 1971, Zötel, 1974). Zojer and Stichler (1988) have used the graphic of
Water Resources & Environmental Problems in Karst - CVIJIĆ 2005
502
rCa/rMg versus rCa+rMg to attach hydrochemically differing waters to special
lithologic unites. The same is demonstrated in Fig. 2.
Table 2.Chemical data of the investigated karst springs; the numbers in the upper line show
the range and the number in the lower line shows the average value
Parameters
Unity
Karst massifs
Dajti
Mali me
Gropa
Tomori
Mali Gjere
Lithology
Dolomite
Limestone
Limestone
and less
dolomite
Limestone with
gypsum
Nr. of springs
15
5
7
Blue Eye Spring
Nr. of analyses
20
15
8
35
Chemical type
HCO3-SO4-
Mg
HCO3 – Ca
HCO3 – Ca
SO4 – Ca
Temperature
° C
11.7 – 18.8
14.4
5.8 – 8.1
6.6
8.5 – 11.5
9.4
12.2 – 12.4
12.3
pH
7.20 - 7.70
7.45
7.42 - -7.88
7.60
7.43 – 8.72
7.98
7.60 – 7.67
7.64
SO42-
mg/l
10.6 – 309.0
83.0
5.4 – 12.4
8.2
5.8 – 26.3
10.6
118.6 – 135.7
131.1
Electric
Conductivity-EC
μS/cm
347 – 863
542
145 – 222
207
224 – 391
271
535 – 594
574
TDS
mg/l
230 – 682
355
109 – 153
138
135 – 234
168
370 – 399
390
Total hardness
mg/eqv/
l
3.86 – 9 56
5.5
1.47 – 2.77
2.2
2.40 – 4.11
2.9
5.57 – 5.94
5.80
rCa/rMg
1.2 – 3.4
2.1
7.2 – 13.8
11.8
2.4 – 9.0
5.6
4.9 – 5.7
5.4
rSO4/rMg
1.6 – 11 9
0.95
0.6 – 2.0
1.1
0.5 – 1.7
0.9
5.1 – 6.6
5.8
Log PCO2
10xatm
-1.92 - -2.41
-2.1
-2.38 - -2.81
-2.6
-2.32 - -3.06
-2.80
-2.53 - - 3.28
-2.40
Sic
0.37 - -0.08
0.09
-0.46 - -0.04
-0.29
-0.28 - -0.09
0.10
-0.26 - -0.29
+2.28
Sid
-0.26 - -0.125
-0.07
-0.68 - -1.0
-0.90
-0.65 - -0.04
-0.20
-0.13 - -0.09
-0.11
For the investigated dolomite and limestone waters there exists an indirect correlation
between the rCa/rMg ratios and the sums of rCa+rMg, while the sulfate waters are
“displaced” from the “correlation” curve. The log PCO2 in the atmosphere is about -3.5
(Garrels and Christ, 1965) but the investigated spring waters contain in average an
order of magnitude more CO2 than they would if they were in equilibrium with the
atmosphere.
Water Resources & Environmental Problems in Karst - CVIJIĆ 2005
503
Fig. 2. investigated karst springs g. 2.
rCa/rMg versus rCa+rMg for the
Fig. 3. Sic versus Sid for the investigated
karst springs
The CO2 source is the humus material at recharge areas of springs where the
infiltration of the precipitation occurs. The introduction of CO2 into the water allows
solution of the carbonate rocks.
The data indicate that although most of limestone springs are undersaturated with
respect to calcite and dolomite, the amount of undersaturation with respect to dolomite
is much greater than that with respect to calcite (Fig. 3). This is explained with the
higher solution kinetics of calcite in comparison with dolomite (Thrailkill, 1977,
Appelo and Postma, 1999). Less saturated with respect to both, calcite and dolomite
are the spring waters of Mali me Gropa massif dominated by highly karstified pure
limestone. The dolomite spring waters of Dajti massif are saturated or nearly saturated
with respect to calcite and some of the spring waters are saturated with respect to
dolomite. The sulfate waters of the big Blue Eye spring results saturated with respect
to calcite and nearly saturated with respect to dolomite (Fig. 3).
Characterizing the physical aspect of karst aquifers
There are at least two end member types of the groundwater flow in karst aquifers:
conduit flow and diffuse flow. The variation of the physical and chemical
characteristics of the springs could be used to characterize physical behavior of the
karst aquifers (Shuster and White, 1971, Jacobson and Langmuir, 1974), but this could
be done estimating also the limitations (Scanlon and Thrailkill, 1987). Most valuable
arameters to be applied for this purpose seem to be the temperature, the hardness and
electrical conductivity. The coefficient of variation – CV %, which equals 100 times
Water Resources & Environmental Problems in Karst - CVIJIĆ 2005
504
Table 3. Coefficient of variation for the springs Pellumbas and Blue Eye
Variable
Conduit type*
Diffusive type*
Spring
Pellumbas
Blue Eye
Temperature
1.4
26.9
4.2
0.6
Total hardness
3.6-4.8
18.6-26.0
13.4
7.0
EC – μ
<10
10-20
7.2
5.0
* Shuster and White (1971) and Jacobson and Langmuir (1974)
the standard deviation divided by the mean, may describe the changes in water
chemistry. The coefficients of variation result grater for the conduit flow springs and
least for diffuse flow springs. Table 3 shows coefficients of variation for some
variables measured in Pellumbas and Blue Eye spring compared with some literature
data. Coefficients of variation of temperature, total hardness and EC suggest that both
springs are diffuse flow springs. The evaluation of all field hydrogeological evidences
supports the same conclusion.
Conclusions
The main factors controlling the formation of chemical composition of the
investigated karst massifs are their lithology, the solution of carbonates by the
introduction of CO2 into the water and the calcite and dolomite saturation conditions.
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