June 2011, Volume 2, No.

3
International Journal of Chemical and Environmental Engineering


Investigation of Recent Changes in Urmia Salt Lake

Sima Rezvantalab
1,*
, Mohammad H. Amrollahi
2
1
Department of Chemical Engineering, Urmia University of Technology, Urmia, I.R. Iran
2
Department of Electrical Engineering, Urmia University of Technology, Urmia, I.R. Iran
*Corresponding author: sima_rezvan@yahoo.com

Abstract
Lake Urmia is a salt lake in northwestern Iran near Turkey. In recent years, the water level has been decreased. To predict the mineral
precipitation in water, Single ion activity coefficients of major ions in Urmia Salt Lake have calculated using Pitzer approach. Using
the results, saturation index for mineral calculated. Urmia Salt Lake brines have shown increase in saturation indices during the last 20
years.

Keywords: Urmia salt lake, Pitzer model, activity coefficient, saturation index

1. Introduction
A.Background and Significance
Urmia Lake is a salt lake in northwestern Iran near
Turkey. The lake is between the provinces of East
Azerbaijan and West Azerbaijan. The lake is divided into
north and south parts separated by a causeway, visible in
figure 1 as a line across the center of the lake. The lake is
the largest permanent water basin in Western Asia,
situated west of the Iranian Plateau. The Urmia Lake
National Park is one of the richest, most attractive natural
fauna habitats in Iran, second only to the Anzali lagoon.
At present, the Lake Urmia wildlife consists of 27 species
of mammals, 212 species of birds, 41 species of reptiles, 7
species of amphibians and 26 species of fish.




















Figure1. Satellite image of Urmia Salt Lake

The lake is marked by 102 islands, all of which have
been registered as World Biosphere Reserves by the
UNESCO. Ashk Island is the natural habitat for an array
of magnificent migratory birds including flamingos and
shelducks, as well as some animal species such as the
famous Iranian yellow deer [1].
Generally, Urmia Salt Lake is classified as oceanic;
being of the sodium- chloride- sulfate type. The main
cations in the lake water include Na
+
, K
+
, Ca
2+
, and Mg
2+
,
while Cl
-
, SO
4
2-
, HCO
3-
are the main anions [2]. Li
+
, F
-

and Br
-
are the other main elements in the lake. Sodium
ion is at slightly higher concentration in the south
compared to the north of the lake, which could result from
the shallower depth in the south, and a higher net
evaporation rate. K and Mg could be elements worth
production in addition to the NaCl currently being
produced from the lake. Br, F, Li and B in the limit of
<50 ppm don't look to be in the economical range. From
drilling in the lake bed the presence of the following
minerals was observed:
- 16 m of black to green silt and marns containing
quartz, calcite, plagioclase and kaolinite.
- Aragonite is one of the main minerals in the lake bed
forming thin, acicular and twin blades. Calcite is
another mineral mainly transported by rivers and
partially formed in-situ.
- Dolomite identified during the drilling has formed
two distinct layers of about 50 cm.
- Gypsum is observed among the sediments forming
thin clean prisms, equant blades up to two mm in
length and some coarse-twined gypsum up to 5 cm
long. Gypsum formation lowers the Ca and SO4
associated with high K moles. In the banks, remnants
of volcanic rocks, quartz, dolomite, carbonates, and
Investigation of Recent Changes in Urmia Salt Lake

169

mica form most of the soft, black muddy sediments
[3].
The precipitation of aragonite, rather than calcite, reflects
the high Mg/Ca ratio in lake water (molar ratio 28:1) [4].

2. Water Level Variation
In general, Urmia Salt Lake has been shrinking for a
long time, so its depth has decreased significantly during
recent years. Due to years of progressive dry climate and
increased demands for agricultural water in the area, the
water level has decreased. Therefore salinity of the lake
has risen to more than 300 g/L during recent years, and
large areas of the lake bed have been desiccated. Because
of recent decrease in lake water, there is a real danger to
the future of the lake as a world class natural resource.
Fig.2 shows water level change in recent years [2].

Figure2. Water-level fluctuation curve for the Urmia Salt Lake
for the period of 1993-2010 [5]

Martyr Kalantari highway which constructed across
Urmia Lake to facilitate communication between Tabriz
in the east and Urmia in the west, divides the lake into
south and north arms. Most rivers flow into the lake from
the south, and there is a continuous water flow from south
to north. Major ions are distributed homogenously
throughout the lake due to the strong currents, despite the
presence of the causeway across the lake [2].
Because of fluctuating water-levels, all values vary
seasonally as well as secularly [4]. Table 2 presents lake
composition at different years.

Table1. Ion concentrations in Urmia Salt Lake and their ionic
strength at different periods of time [3,6,7]

Ion 1994 2000 2009
Na 1.692 5.204 4.9000
K 0.0184 0.0383 0.0050
Mg 0.1422 0.369 0.04613
Ca 0.00985 0.0410 0.0156
Cl 2.136 5.867 5.4000
Br 0.00099 0.000027 0.00625
SO
4
0.0711 0.201 0.1813
HCO
3
0.0165 0.0077 0.0098
3. Pitzer Ionic Interaction Approach
The ion interaction approach developed by Pitzers
scientific school presents a very valuable tool for the
theoretical prediction for various aspects of geochemical
development of natural hypersaline brines. It can be
emphasized that the intensive developments of numerous
branches of geochemistry were catalyzed by the
application of physico-chemical approaches developed by
Pitzer for concentrated electrolyte solutions [7].
To estimate the seawater activity potential function, it is
necessary to calculate the osmotic coefficient () and the
activity coefficients () of individual species. In the Pitzer
approach, the osmotic coefficient is given by [8]:

+ =
i
i
I I A m ) 2 . 1 1 /( ( 2 ) 1 (
2 / 1 2 / 3 o
o

= =
+ +
C a
N
c
N
a
ca ca a c
ZC B m m
1 1
) (
o

= + =
'
=
' '
+ u +
1
1 1 1
) (
C
N
c
Nc
c c
a c c
Na
a
a c c c c
m m m v
o

= + =
'
=
'
+ u +
1
1 1 1
) (
a
N
a
Na
a a
c a a
Nc
a
c a a a a
m m m v
o
(1)

The activity coefficient for a cation M is given by:

=
+ + =
a
N
a
Ma Ma a M M
ZC B m F Z
1
2
) 2 ( ln

= =
+ u +
C
N
c
Mca
Na
a
a Mc c
m m
1 1
) 2 ( v

= + =
+
1
1 1
a
N
a
Na
a a
aaM a a
m m v

= =
+
Nc
c
Na
a
ca a c M
C m m Z
1 1

(2)
Similarly, the activity coefficient for an anion X is
given by:

=
+ + =
C
N
c
cX cX c X X
ZC B m F Z
1
2
) 2 ( ln

= =
+ u +
a
N
a
Xac
Nc
c
c Xa a
m m
1 1
) 2 ( v

= + =
+
1
1 1
c
N
c
Nc
c c
ccX c c
m m v

= =
+
Nc
c
Na
a
ca a c X
C m m Z
1 1

(3)

In these equations, F is defined as:
|
|
.
|

\
|
+ +
+
= ) 2 . 1 1 ln(
2 . 1
2
2 . 1 1
2 / 1
2 / 1
2 / 1
I
I
I
A F
o


= + =
' '
= =
u + +
1
1 1
'
1 1
'
C C a
N
c
Nc
c c
c c c c
N
c
N
a
ca a c
m m B m m
Investigation of Recent Changes in Urmia Salt Lake

170

= + =
'
u +
1
1 1
'
Na
a
Na
a a
a a a a
m m
(4)

Z is defined as:

=
i
i i
m Z Z



(5)
2 / 1
2 /
X M MX MX
Z Z C C
o
=

(6)
I
MX
I aMX
MX MX MX
e e B
12 ) 2 ( ) 1 ( ) 0 (
+ + = | | |
o

(7)
) 12 ( ) (
) 2 ( ) 1 ( ) 0 (
I g I a g B
MX MX MX MX MX
| | | + + =

(8)

2 ' ) 2 ( ' ) 1 ( '
/ ) 12 ( / ) ( x I g I I a g B
MX MX MX MX
| | + =

(9)

2
/ ) ) 1 ( 1 ( 2 ) ( x e x x g
x
+ =
(10)
2
2
/ ) exp(
2
1 1 2 ) ( x x
x
x x g
|
|
.
|

\
|

|
|
.
|

\
|
+ + = '

(11)
I x
MX
o = I x 12 =
(12)
) ( exp ) ( exp
'
I I I
ij ij ij ij
u u u
o
+ + = u
(13)
) ( exp
'
I
ij ij
u = u'
(14)
); ( exp I
ij ij ij
u u + = u
(15)

And I (ionic strength) is defined:

=
2
5 . 0
i i
z m I
(16)

In these equations, c and a refer to cation and anion
species, A is the DebyeHuckel parameter and B, C, ,
, and are interaction parameters among the various
solutes. For the specific interaction parameters actually
used in the implementation of the Pitzer approach [8, 9].








Table2. Values of ion interaction parameters at 25C for major ions
of natural water [8].

o
MX
C
) 2 (
MX
|
) 1 (
MX
|
) 0 (
MX
|
Salt
0.00127 - 0.2664 0.0765 NaCl
-0.00084 - 0.2122 0.04835 KCl
0.00519 - 1.6815 0.32235 MgCl2
-0.00034 - 1.6140 0.3159 CaCl
2
0.00116 - 0.2791 0.0973 NaBr
-0.0018 - 0.02212 0.0569 KBr
0.00312 - 1.75275 0.043268 MgBr
2

-0.00257 - 1.61325 0.3816 CaBr2
0.00497 - 1.113 0.01958 Na
2
SO
4
- - 0.77925 0.04995 K2SO4
0.025 -37.23 3.343 0.2210 MgSO
4

- - 55.7 2.650 0.200 CaSO
4
- - 0.0411 0.0277 NaHCO3

The final results of the conventional single Ion
activity coefficients of major ions in Urmia Lake water
have been calculated by equations 2 and 3 are presented
in Table 3.

Table3. Single-ion activity coefficients in Urmia Salt Lake at
different periods of time

Ion 1994 2000 2009
Na 0.63791 0.92802 0.8586
K 0.49542 0.44864 0.4326
Mg 0.28267 1.7290 1.2476
Ca 0.22775 0.96377 0.7212
Cl 0.71828 1.1336 1.1552
Br 0.80731 1.5362 1.5688
SO
4
0.04137 0.02009 0.02260
HCO3
0.50065 0.37782 0.39128
I 2.512 6.781 6.467

4. Conclusion

The problem of activity and activity coefficient
determination for various salts brines is very important,
since it can provide relationship between water
evaporation and mineral participation.
The logarithm of the quotient of the ion activity
product (IAP) and solubility product constant (K
SP
) is
called the saturation index (SI). The IAP is calculated
Investigation of Recent Changes in Urmia Salt Lake

171

from activities that are calculated from analytically
determined concentrations by considering the ionic
strength, the temperature, and complex formation. The
solubility product is derived in a similar manner as the
IAP but using equilibrium solubility data corrected to the
appropriate water temperature [10].
SI=log (IAP/Ksp) (17)
If the determined SI value is below -0.2 the solution is
understood to be undersaturated in relation to the
corresponding mineral, if SI exceeds +0.2 the water is
assumed to be supersaturated with respect to this mineral
[10]. Calculated values for mineral SIs are presented in
table 4.

Table4. SI values for some minerals in Urmia Salt Lake water.
Mineral Formula 1994 2000 2009
Aragonite CaCO3 0.61 0.64 1.09
Calcite CaCO
3
0.79 0.83 1.28
Dolomite CaMg(CO3)2 3.11 3.13 4.54
Gypsum CaSO
4
:2H
2
O -0.67 0.54 0.02
Halite NaCl -1.29 -0.06 -0.15
Magnesite MgCO3 1.47 1.46 2.42

The results obtained show that Lake Urmia waters are
oversaturated with respect to Dolomite and Magnesite and
the saturation index has been increasing during the last 20
years.

ACKNOWLEDGMENT
The authors thank the Dean of Urmia University of
Technology, Dr. I. Mirzai, for his support and
encouragement.



























REFERENCES
[1] http://www.bari.ir/bari/en/tours/jazebeha/orumiehd/

[2] A. Eimanifar, and F. Mohebbi, Urmia Lake (Northwest Iran): a
brief review, Saline Systems, 3:5 (2007) 1-8.

[3] S. Alipour, Hydrogeochemistry of seasonal variation of Urmia
Salt Lake, Iran, Saline Systems, 2:9 (2006) 1-19

[4] John K. Warren, Evaporites : Sediments, Resources and
Hydrocarbons Springer-Verlag , Berlin , 2006

[5] http://www.pecad.fas.usda.gov/cropexplorer/

[6] Touloie J., Hydrogeochemistry of Urmia Lake The First
Oceanology, Conference of Iran 1998:20-23.J.

[7] N. Heidari, M. Roudgar, N. Ebrahimpour, Thermodynamic
quantities and Urmia Sea water evaporation, Saline Systems, 6:3
(2010) 1-6

[8] B. Krumgalz, Application of the Pitzer ion interaction model to
natural hypersaline brines, J. Molecular Liquids, 91 (2001) 3-19

[9] B. Krumgalz, J. Millero, Physico-Chemical Study of the DEAD
SEA Waters, I. Activity Coefficients of Major Ions in Dead Sea
Water, Marine Chemistry, 11, (1982) 209-222

[10] B. J. Merkel, B.P. Friedrich, Groundwater Geochemistry A
Practical Guide to Modeling of Natural and Contaminated
Aquatic Systems, Springer Berlin Heidelberg New York, 2002,
pp. 8-17.