TAJ MUHAMMAD JAHANGIR J.et al.,Chem. Soc. Pak., Vol. 35, No.3, J.Chem.Soc.Pak.,Vol. 2013 35, No.3, 2013 1004

Water Quality Assessment of Haleji Lake (Sindh, Pakistan) A Ramsar Recognized Site

1,2TAJ MUHAMMAD JAHANGIR, 2, 1MUHAMMAD YAR KHUHAWAR, 3,1SULTAN MEHMOOD LEGHARI, 3MUKHTIAR AHMED MAHAR AND 4 MUHAMMAD SAEED BALUCH 1Institute of Advanced Research Studies in Chemical Sciences, University of Sindh, Jamshoro. 2Dr. M.A.Kazi, Institute of Chemistry, University of Sindh, Jamshoro. 3Department of Freshwater Biology and Fisheries, University of Sindh, Jamshoro. 4 Government of Sindh Wildlife Department, Hyderabad Division [email protected]*

(Received on 5th July 2012, accepted in revised form 7th March 2013)

Summary: The present survey is an assessment of water quality, sediments, flora and fauna of Haleji Lake. A number of variables were selected for 12 stations for a period of 4 months from May to August 2008. Multivariate statistical techniques were applied to identify characteristics of water quality in the studied stations. Four factors were extracted by principal component analysis and explain 86.82% of the total variation. The first factor (PC1) loaded with variables of TDS, Na, K, Cl, DO, hardness, Ca, Mg, sulphate and orthophosphate. Factor second (PC2) is related with COD, total acid hydrolysable phosphate. The third factor (PC3) associated with pH and fluoride. Thus fourth factor (PC4) to its total eigen-value of 1.605 were significantly positive correlated with BOD and bicarbonate and negatively correlated with ammonia and nitrate. The majority of mean values for lake water were higher than minimum permissible levels for drinking water when compared with its source of riverine water. The pH was indicated slightly alkaline, biological oxygen demand staged at the maximum permissible limit by WHO for drinking water. The parameters of chemical oxygen demand, fluoride and potassium were found above the permissible limits of WHO for drinking water. In sediments, the calcium and hardness was in higher concentration than water. However chloride and alkalinity indicated lower in sediment than that of water. The lake was identified rich in primary productivity and showed the Typha domigensis, Phragmites karka, Nelumbo nucifera and Potamogeton pectinatus forming beads to become food for herbivorous fishes and migratory birds. The excess growth of phytoplankton especially Microcysts species M.aeruginosa, M. flosaqua, M.pulverea, Oscillatoria prolfica, O. planktonica, Pediastrum simplex, & P. simplex Var duodenarium, Botryococus braunii were identified. The fishes were recorded Channa striatus, Notopterus notopterus, Xenenthodon canclia, Oreochromous mossambicus, Oreochromous niloticus, Gudisia chapra, Chanda ranga and Chela laubuca. The studies explained conveniently by correlation coefficient, principal component analysis and surfer diagram.

Keywords: Chemical assessment, Haleji lake, Water, Sediments, Biota, Ramsar site.

Introduction

Water is an essential component for life on distance of about 15 Km west-northwest of Thatta earth, which contains minerals that are extremely city and 85 Km east of Karachi. The lake is on the important in human nutrition [1]. The chemistry of link road from Gujo village located on national lakes varies markedly both temporally and spatially highway with the covering distance of about 2-4Km. [2], eutrophication or nutrient enrichment are serious The source of water to Haleji is Kalri Baghar feeder problems in lakes has been extensively documented via Jam branch carrying water from Keenjhar Lake [3-7]. The Pakistan has 55 important lakes of which and natural streams entering from the hills in rainy only 12 have status of sanctuaries with area covering season, a second canal in the southeast corner of the approximately 7800 Km2 of the total area 803941 lake is Kalri Baghar feeder via Gujo functioning as Km2. The Haleji Lake is gazetted wild life sanctuary inlet or outlet. A large rest house is located at the of Pakistan, and Ramsar site 101 from July 23, 1976 entrance of lake with three sides in water. It is not under article-2 of Ramsar convention as waters of advisable to swim in the lake due to the presence of international importance for water fowl refuge [8]. crocodile in the lake and is natural hatchery for local The lake attracts for recreation of large number of birds and animals [8]. The lake is covered around visitors from Karachi and Hyderabad. The lake is at with stone pitched embankments, and a narrow the altitude of 40 feet from the sea level, it is located muddy track for plying car under the cover of trees. at the latitude of 24’.50” and at the longitude of The lake is artificial perennial freshwater formed in 67’.45” in the Sindh province. It is artificially 1930 converting natural lagoon to fresh water extended in 12 square miles (1704 hectare) with reservoir of maximum depth 5-6m to fulfill the needs cubical shape and supporting embankments. It is at a of water of Karachi a metropolitan city. Since last 8

*To whom all correspondence should be addressed. TAJ MUHAMMAD JAHANGIR et al., J.Chem.Soc.Pak.,Vol. 35, No.3, 2013 1005

years water is scarce in this lake as similarly faced in or international organizations. It was found that total over 1.5 million people of Kathmandu, Napal only dissolved solids, hardness, chloride; alkalinity, 140 million liters per day (MLD) being supplied in sulphate, sodium, calcium and magnesium were rainy season and 90 MLD during the dry season, within the maximum permissible limits for drinking however with average demand of 180 MLD [9]. The water guidelines set by World Health Organization human activities are a major factor in determining the (WHO) [14]. The most of average values of present quality of the surface and groundwater through studies indicated higher than the minimum atmospheric pollution, effluent discharges, use of contamination level for drinking water when agricultural chemicals, eroded soil, and land use [10]. compared with its source of riverine water. The pH It was reported [11] that the lake was rich of was indicated slightly alkaline (7.71-8.75±0.35) (Fig. phytoplankton due to high temperature, concentration 3, Table-1) with average value of 8.2 and this lake of nutrients and favorable pH. The amount of water resembles with communal land reservoirs, nitrogen and phosphorus was found in low Insiza, Zambabwe [15], biological oxygen demand concentrations and carbon dioxide was adequate. The staged at the maximum permissible limit by WHO for pH ranged 6.9-8, dissolved oxygen1.8-7.3 mg/L and drinking water (Fig. 4) is in agreement with Nansi silica 2-35 mg/L and suggested lake was in eutrophic lake, China [16]. The chemical oxygen demand (29- condition. The limnological conditions of Haleji lake 205±115mg/L) with mean value 115mg/L (Fig. 5), was examined, birds management studies for increase has indicated similar results reported earlier from of fish production, population of zooplankton and Hulun lake, china, [17], fluoride (0.8-3.0±1.9mg/L) seasonal variation of physicochemical parameters of with average 1.9mg/L (Fig. 6) and potassium (5.5- water. It was reported that dissolved oxygen and 23±16mg/L) with mean 16 mg/L (Fig. 7) and the dissolved carbon dioxide increased in winter and values were consistent with others study [18]. It was inversely in summer. The Haleji lake supported the observed that the values of COD, F and K were found abundant growth of zooplankton and the water was above the permissible limits of WHO for drinking highly polluted with organic matter resulting from water. The levels of phosphate (7-16.5±12µg/L) (Fig. decay of plants and animals [12]. Another studies 8) classified the lake as oligiotrophic to mesotrophic, reported [13] water salinity 0.1-0.2g/L, pH 7.15-8, whereas the presence of nitrogen as ammonia (18- TDS 204-393 mg/L, chloride 35-106 mg/L, M- 263±135µg/L) (Fig. 9), lake had trophically stated Alkalinity 11-52 mg/L , hardness 82-120 mg/L, silica mesotrophic to eutrophic as earlier indicated from 1-10 mg/L, dissolved oxygen 7.6-8.6 mg/L, total Fuxianhu and Dianchi lakes of China [19]. phosphate 0.05-0.29 mg/L and ortho phosphate 10-38 µg/L. The concentration of metal ions were detected Present studies indicated higher values of for Na 23-106 mg/L, K 3-26 mg/L, Ca 29-61 mg/L pH (7.71-8.75±0.35), total dissolved solids (256- and Mg 8-35 mg/L and the data showed the quality 848±641mg/L) averages 641mg/L (Fig. 10), salinity of Haleji lake was within the permissible limits by (0.2-0.7g/L), chloride (42-218±58mg/L) with mean WHO standards for drinking water [14]. The Physico- 171mg/L (Fig. 11) and hardness (133-253±218) with chemical and biological characteristics of water mean 218mg/L (Fig. 12,Table-2). The values of K quality of Haleji lake is important to report and to (5.5-23±16mg/L), Mg (9-32±24mg/L) averages draw baseline data for planning and decisions making 24mg/L (Fig. 13) and Na (26-116±28) with average in future. 79mg/L (Fig. 14) were rather higher than the studies reported in 2001 for Haleji lake (Table-3) [13, 20]. Results and Discussion The colour of lake tarnished from transparent to yellowish green which resembles with water ponds of A number of variables were assessed Hungary [21] and this may become difficult for day including pH, temperature, conductance, total light penetration for the sustenance of aquatic life of dissolved solids, salinity, odour, transparency, BOD, lake. The addition of water remained variable and COD, DO, fluoride, chloride, bicarbonate, hardness, less amount of water is added occasionally. The water sulphate, nitrate, orthophosphate, total phosphate, of lake has remained stagnant since 8-10 years and ammonia, sodium, potassium, calcium and deterioration of water quality has resulted. The magnesium from water samples collected from 12 concentration of the salts within the lake has selected stations from Haleji lake (Fig. 1 and 2). The increased due to the evaporation of the water from sampling was carried out for the period of four the surface and leaving salts within the lake. The months from May to August 2008 and analysis was water is not used for drinking by the inhabitants. carried out at sampling site and laboratory. The data Haleji lake is rich in primary productivity [22] and obtained through the experimental findings were showed aquatic plants, unicellular, colonial algae, and matched with drinking water criteria set by national phytoplankton, submerged and emergent aquatic TAJ MUHAMMAD JAHANGIR et al., J.Chem.Soc.Pak.,Vol. 35, No.3, 2013 1006

plants. However the filamentous green algae and free and P. simplex var duodenarium and Botryococus floating aquatic plants were found absent in the lake. braunii belonging to Chlorophyta were bloom Haleji lake is a eutorphic lake in terms of full of the producing algae. During the survey period 8 species aquatic plants [23]. Typha domogensis, Phragmites of fishes were recorded Channa striatus, Notopterus vollatoria are the emergent plants, Nelumbo nucifera notopterus and Xenenthodon canclia are the are attached floating plant and Potamogeton Carnivorous fishes and Oreochromous mossambicus, pectinatus are submerged forming beads and become Oreochromous niloticus are Omnivorous and Gudisia food for fishes and migratory birds. Lake water chapra, Chanda ranga and Chela laubuca are the possesses excess growth of phytoplankton especially planktivorous fishes. A group of Cyprinid Carp fishes Microcysts species M.aeruginosa, M. flosaqua, M. are the planktivour and found absent in the Haleji pulverea, Oscillatoria prolfica, O. planktonica lake. belonging to class Cyanophyta. Pediastrum simplex

Fig. 1: Sampling locations 1.Steel Mill Colony, 2.Steel Mill bridge, 3.KWSB bridge Inlet/Outlet supply, 4.Sanctuary, 5.Phyio I, 6.Phyio II, 7.Back of Sanctuary (west side), 8.Near village Ali Muhammad Samoo, 9.Center of lake, 10. Bhutyon, 11. North mid point of Sanctuary, 12. K.B. Feeder bridge Inlet supply.

Table-1: Statistical Analysis of Haleji lake water (n=4), Thatta Sindh; May-August 2008. Average Maximum Minimum Deviation WHO,PLDW pH 8.2 8.75 7.71 0.35 8.5 TDS mgL-1 641 848 256 177 1000 Cl- mgL-1 171 218 42 58 250 -1 SO4 mgL 15.3 19 5 5 250 -1 HCO3 mgL 129 146 88 15 200 Hardness mgL-1 218 253 133 40 500 -1 O-PO4 µgL 2.1 4.7 0 1.4 30 -1 T-PO 4 µgL 12 16.5 7 2.9 300 -1 NO3 mgL 0.76 1.8 0.13 0.46 5 F mgL-1 1.9 3 0.8 0.7 1.5 -1 NH4 µgL 135 263 18 60 5 Na mgL-1 79 116 26 28 200 K mgL-1 16 23 5.5 5.5 12 Ca mgL-1 34 42 21 6.4 200 Mg mgL-1 24 32 9 7 50 COD mgL-1 115 205 29 52 35 BOD mgL-1 5 8 2.15 1.4 5 DO mgL-1 8.4 9.5 7.1 0.7 4.5 PLDW =Maximum Permissible limits for drinking water TAJ MUHAMMAD JAHANGIR et al., J.Chem.Soc.Pak.,Vol. 35, No.3, 2013 1007

Table-2: Chemical Assessment of Haleji lake water (n=4) Thatta Sindh, May-August 2008. Parameters Sampling Stations - pH •TDS •Cl •SO4 •HCO3 •Hardness •COD •BOD •DO St.1 Steel M Colony 8.56 729.8 208.25 19 139.5 230 154 5.45 8.93 St.2 Steel M Bridge 8.2 691 185 16.75 135.5 232.5 141.8 4.4 7.88 St.3 KWSB in/outlet 7.77 303 63.3 7.2 129.67 133.3 103.3 6 8.2 St.4 Sanctuary 8.34 649 169 16.58 124.5 208.8 134.75 5.3 7.88 St.5 Phyio-I 8.08 747.8 202.5 18.35 145.67 231.25 178.75 7.8 8.6 St.6 Phyio-II 7.71 848 218 18 114 252.5 205 5.65 8.4 St.7 Back Sanctuary west side 8.23 653 180.3 18.6 133 240 61 4.37 9.2 St.8 Vil.Ali M Samoo 8.75 709 212 18.95 120 242.5 150 2.15 8.85 St.9 Center of lake 8.71 754.8 205.5 16.25 133 230 91.75 3.38 8.9 St.10 Bhutyon 8.39 765.5 205 18.28 135 245 80.25 4.9 9.47 St.11 North-west of lake 8.7 692.5 198.5 15.25 145.5 245 115.5 6.5 7.5 St.12 Inlet KB Feeder 7.98 255.5 41.5 5 87.5 132.5 46.5 3.7 7.1 Key information n= mean, • =mg l-1

Table-2 continued: Chemical Assessment of Haleji lake water (n=4) Thatta Sindh, May-August 2008. Parameters Sampling Stations + + ++ ++ ^O-PO4 ^T-PO4 •NO3 •F ^NH4 •Na •K •Ca •Mg St.1 Steel M colony 2.23 13.4 0.13 2.25 113.5 103.75 20.25 33.5 26.25 St.2 Steel M bridge 2.1 12.95 1.48 2.5 90.5 100.67 20.3 31 24 St.3 KWSB in/outlet 2 10.67 0.53 1 18 33.5 10 24.5 12.75 St.4 Sanctuary 1.53 11.63 0.74 2.25 125 75.25 12.75 34 27.25 St.5 Phyio-I 1.76 14.5 0.76 2.25 108 75.5 22.75 34.75 26.5 St.6 Phyio-II 2.8 16 0.63 2 111.5 115.5 21.25 38.25 32.25 St.7 Back Sanctuary west side 2.8 8.67 0.72 0.83 172 86.67 15.3 41.3 31.67 St.8 Vil.Ali M Samoo 3.95 16.5 1.8 2.5 218 69.5 16.5 42 27 St.9 Center of lake 2.73 7.58 0.37 2 141.5 96.75 19.5 37.25 27.25 St.10 Bhutyon 4.7 11.3 0.89 2 161 100 17.25 38 24.75 St.11 North-west of lake B.D 13 0.37 3 127 69 9 29 24 St.12 Inlet KB Feeder B.D 7 0.46 0.8 263 26 5.5 21 9 Key information n= mean, B.D= Below Detection, • =mg l-1 , ^=µg l-1

Fig. 2: Map of Sindh indicating Haleji Lake.

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Table-3: Comparative chemical assessment of Haleji lake water. Present studies Sindh Wildlife Department- University of Sindh, Parameters Baqui et al 1970-74 Jahangir et al 2001 Baseline survey documents/report at Haleji lake, Wild life Sanctuary, District Thatta Sindh, Pakistan 2008 Air oC 27 27-34 30- 44 Water oC 19-20 18-30 28.6-38.8 Salinity g/L * 0.1-0.2 0.2-0.7 Conductivity µS/cm 320-578 315-615 358-1490 pH 7.9-7.97 7.15-80 7.71-8.75 TDS mg/L 218-393 204-393 255-848 Chloride mg/L 3.9-10.65 35-106 41-218 M.Alkalinity mg/L 100-110 11-52 87-145 Na in mg/L 26-70 23-106 26-115 K in mg/L 12-26 3-26 5-22

Ca in mg/L 26-28 21-41 29-61 Mg in mg/L 38-64 8-35 9-32 Silica mg/L 38-80 1-10 * Hardness mg/L * 8.2-120 132-252 Sulphate mg/L * * 5-19 COD mg/L * * 46-205 DO mg/L * 7.6-8.6 7.1-9.2 T-PO4 mg/L * 0.05-0.29 0.007-0.016 O-PO4 mg/L * 0.010-0.038 0.0-0.005

Fig. 3: pH of lake water with global coordinates Fig. 5: COD in mg/L of lake water

Fig. 6: Fluoride in mg/L of lake water. Fig. 4: BOD in mg/L of lake water with coordinates. TAJ MUHAMMAD JAHANGIR et al., J.Chem.Soc.Pak.,Vol. 35, No.3, 2013 1009

Fig. 7: Potassium in mg/L of lake water. Fig. 10: TDS in mg/L of lake water.

Fig. 8: Total phosphate in µg/L of lake water. Fig. 11: Distribution of chloride in mg/L of lake water.

Fig. 9: Ammonia in µg/L of lake water. Fig. 12: Hardness in mg/L of lake water.

TAJ MUHAMMAD JAHANGIR et al., J.Chem.Soc.Pak.,Vol. 35, No.3, 2013 1010

negative relation with bicarbonate. The bicarbonate behaved negative relation with nitrate, ammonia and calcium and positive with orthophosphate. Chloride and sulphate also indicated negative coefficient of correlation with ammonia and total acid hydrolysable phosphate. The correlation coefficient of chloride was negative with bicarbonate, ammonia, total acid hydrolysable phosphate, nitrate and calcium. The nitrate, ammonia, orthophosphate and fluoride showed negative correlation in their groups with all respective parameters in periods. Sodium indicated negative relation with calcium and positive with potassium. Potassium indicated negative relation with calcium and positive with magnesium. The calcium showed positive relation with magnesium. The correlation coefficient for 15 variables was examined against each other to report possible relationship between them in the lake during 2008. The pH

Fig. 13: Magnesium in mg/L of lake water. showed positive relationship with all parameters except total phosphate. Out of 14 variables only 3

showed negative relation with TDS, they were M.alkalinity, nitrate and ammonia. The elements grouped in major cations (Na,K,Ca,Mg) and anions (HCO3, SO4,Cl) were inserted to worksheet for to draw piper (Triangular) diagram and found the nature of lake water of Na+K+Cl and inlets as source of water indicated Na+K+HCO3.

Comparison Analysis of Haleji Lake and Source of Inlets

Haleji lake water is divided into two groups, group 1 comprises ten sampling stations, covering different parts of lake and group 2 indicated two sources of inlet (St.3, 12) of riverine water close to lake. The comparison of variables of group 1 with group 2 for TDS, chloride and sulphate (Fig. 15) indicated following the mean, values of maximum- Fig. 14: Sodium in mg/L of lake water. minimum along with standard deviation in parenthesis 706 (848-536± 80) mg/L, 192 (218- Correlation Coefficient studies of Haleji Lake water 131±25) mg/L, 17(19-11±2.3) mg/L and group 2, 280 (303-255±33) mg/L, 52.4(63-41±15) mg/L and The highest correlation was observed 6.1(7.2-5±1.5) mg/L respectively. pH, Bicarbonate between TDS and chloride with a correlation (Fig. 16) and hardness indicated for group 1, coefficient of 0.99 (Table-4). A positive correlation 8.33(8.75-7.71±0.33), 132(145-114±9.8) mg/L and coefficient was also observed for sulphate 0.880, 233(252-207±14) mg/L as compared with group 2 magnesium 0.830 and sodium 0.810 against TDS. (riverine water inlets), 7.87(7.98-7.77±0.14), The correlation coefficient of chloride was observed 108(129-87.5±29.8) mg/L and 132.9(133.3- with maximum with sulphate (0.89), magnesium 132.5±0.56) mg/L respectively. The COD, BOD and 0.74, sodium 0.73 and potassium 0.53, these may DO (Fig. 17) for group 1 indicated 121(205-61±52.5) indicate common sources. The hardness showed mg/L, 4.9(7.8-2.15±1.5) mg/L and 8.5(9.4-7.5±0.6) negative correlation with ammonia but highest mg/L. and group 2 comprised 75(103-46±40) mg/L, positive relation with calcium, sodium and fluoride. 4.85(6-3.7±1.6) mg/L and 7.65(8.2-7.1±0.7) mg/L pH showed negative correlation with total acid respectively. The nutrients ortho phosphate (Fig. 18), hydrolysable phosphate and highest for hardness total phosphate, nitrate (Fig. 19) and ammonia 0.165. The TDS, chloride and sulphate indicated showed for group 1, 2.27(4.7-0±1.38) µg/L, TAJ MUHAMMAD JAHANGIR et al., J.Chem.Soc.Pak.,Vol. 35, No.3, 2013 1011

12.3(16.5-7.58±2.8) µg/L, 0.81(1.8-0.13±0.486) mg/L and 134(218-90.5±36.5) µg/L as compared to group 2, 1.38(2-0±1.4) µg/L, 8.8(10.67-7±2.59) µg/L, 0.495(0.53-0.46±0.049) mg/L and 140.5(263-18±173) µg/L respectively. Metal ions of sodium, potassium, calcium (Fig. 20) and magnesium for group 1 found were 89.2(115-69±16) mg/L, 17.4(22.7-9±4.2) mg/L, 36(42-29±4.2) mg/L and 27(32-24±2.85) mg/L when matched with 29.75(33.5-26±5.3) mg/L, 7.75(10- 5.5±3.1) mg/L, 22.75(24.5-21±2.47) mg/L and 10.87(12.8-9±2.65) mg/L respectively. The comparison of groups 1, 2 concluded that the source of inlets possess less amount of salts load than the remaining part of lake. The amount of ammonia contributed pollution from inlet source of lake at once during sampling but minimum range of ammonia is still high in the lake than the source of inlets. Fig. 17: Dissolved oxygen in mg/L of lake water

Fig. 15: Sulphate in mg/L present in lake water. Fig. 18: Ortho phosphate in µg/L in lake water.

Fig. 16: Alkalinity in mg/L of lake water Fig. 19: Nitrate in mg/L of lake water.

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Table-4: Correlation of coefficient determination for water in different parameters recorded at Haleji lake (n=4) during May-August 2008.

pH TDS Cl SO4 HCO3 NO3 Hard. NH4 T.PO4 O.PO4 F Na K Ca Mg pH 1 TDS 0.100 1 Cl 0.115 0.948 1 SO4 0.112 0.880 0.89 1 HCO3 0.150 -2.43 -3.7 -2.65 1 NO3 0.013 -.030 -.04 0.058 -.057 1 Hard. 0.165 0.687 0.37 0.536 0.285 -6.9 1 NH4 0.049 -0.46 -0.6 -0.46 -0.38 -1.0 -0.2 1 T.PO4 -.016 0.037 -.17 -.035 0.037 -2.8 0.23 -3.3 1 O.PO4 0.018 0.246 0.25 0.038 0.343 -.02 0.20 -.45 0.051 1 F 0.122 0.450 0.47 0.303 0.244 -1.6 0.42 -1.6 0.435 -2.0 1 Na 0.043 0.810 0.73 0.714 0.187 -2.2 0.63 -1.8 0.011 -0.87 -.7 1 K 0.003 0.630 0.53 0.593 0.208 -1.8 0.45 -2.0 0.176 -0.78 -.2 0.64 1 Ca 0.120 0.220 -.16 0.342 -.001 -6.2 0.63 -4.2 -0.75 -3.97 -2. -.62 -.76 1 Mg 0.072 0.830 0.74 0.857 0.218 -3.1 0.11 -2.4 -.004 -1.93 -.4 0.57 0.26 0.75 1

Merismopedia, Coelosphaerium Gomphosphaeria, Oscillatoria, Spirulina, Lyngbya, Anabaena, Aphanizomenon and Raphidiopsis.

Some species of Chlorophyta such as phytoplankton. Ankistrodesmus, Botryococces, Colastrum, Crucigena, Oocystis, Pediastrum, Teteradron, Scendesmus Schroedera, Selanstarum was observed in planktonic form in the lake. Two species Botoryococcus branui and Pediastrum simplex var. duoderinum were recorded in abundance Fig. 20: Calcium in mg/L of lake water. with association of Microcystis species. It was interesting to observe that green filamentous algae Comparative Analysis of Sediments with Water were not recorded during sampling period. The most (Haleji Lake) common algal species belonging to phylla were Bacillarophyta, Melosira, Cyclotella, Cocconies, The mean values of sediment were also Gyrosigama, Amphora and Cymbella attached with compared with quality of water at Haleji lake. The the leaves and stem of submerged plants such as amount of sediment hardness indicated two fold Lotus, Phragmits and Typha species. The algal higher than water hardness; the calcium blooms can be controlled by introducing the duck concentration in sediments showed three fold higher weed, Lemna minor, Marsilea minuta formed the than water. The values of chloride found in water by shad on the planktonic algae. Alternatively four fold higher than sediment and M.alkalinity of phytoplankton feeder and grass eater fish, cyprinus water found three fold higher than sediment. The pH carpio. (Gulfam) Hypophalmichthys molitrix (Silver of sediments found 0.5 units less than water (Table- carp), Ctenopharyngodon Idella (grass carp), labeo 5). The amount of sediment hardness indicated 437 rohita, Catela catela and cirrhinus mrigala should be mg/L and calcium 108 mg/L, Water hardness showed introduced in the lake to control the excess growth of 218 mg/L and calcium 34 mg/L. The amount of phytoplankton and toxic enzymatic producing algal chloride in sediment indicated 44 mg/L and 171 mg/L species. in water, alkalinity of sediment found 39 mg/L and 129 mg/L in water. Interestingly it was observed that Zooplankton calcium and hardness found in higher concentration in sediment than water, thus chloride and M.alkalinity Zooplanktons are important link in the food indicated in amount lower in sediment than water. chain of aquatic ecosystem. These are dependent upon the phytoplankton for their survival. Almost all Phytoplankton the zooplankton and fingerling fishes feed upon the In Haleji Lake, total 73 species of phytoplankton plankton in early stage i.e. Gadusa chapra which are were recorded with 53.84% of Cynophyta, 33% of planktivorous inhabit only two major groups of Chlorophyta and 13.84% of Bacillariophyta. zooplankton (Rotifer and Copepods) were found Cyanophyta are represented by bloom forming dominant qualitatively and quantitatively [12]. species belonging to the genus Microcysts, sampling stations were selected in the littoral zone, from which surface zooplankton were collected. 19 TAJ MUHAMMAD JAHANGIR et al., J.Chem.Soc.Pak.,Vol. 35, No.3, 2013 1013

species of zooplankton were identified from the shallow and moist soil. It grows best in high nutrient various parts of the lake, majority of these belongs to levels and may form very large stands. In earlier the phylum Rotifera represented by 15 species. Six reports [12-13] Lemna minor, Pista sp. and species belonging to genus Brachionus were found Eichorinia crassipes were also present in the dominant throughout the lake. The Filinia, Lecane reservoir. Typha domingensis and Pharagmite and Monostyla were present with 2 species each. vollatria marshy and Nelumbo nelumbo were present Philodina and Keraletla were present with one as rooted and floating in mat formation on the species. 3 species of copepods and one species of substratum in the lake. The shallow areas were cladocera belonging to phylum Arthropod were also completely covered with the major portion of recorded from the Haleji Lake. vegetation of aquatic plants. At present Haleji lake is feed through Jam Branch and from lower K.B. Fishes Feeder, but due to the scarcity of water submerged and emergent plants die and decay with release of Fish fauna of lake was very poor, Only 8 considerable amount of nutrient in water. The species of three different groups were recorded nutrients may increase the primary productivity of during present investigations in 2008 (Table-6). The water in terms of increased phytoplankton and Oreochromous niloticus, O.mossambicus and zooplankton. In surrounding of lake a number of Gudusia chapra were dominant species in the lake. lagoon/ponds are present which can be utilized for The fish caught through the Sein net of size 10 sq.ft the artificial culture for the growth fishes, as Fish provided 3-7 fish per attempt. hatchery on the side of Lake Finger lings of Major carp, Common carp, and Grass carp will be very Macrophyte successful for the productivity of reservoir and can control the growth of aquatic plant and The lake is protected by the land which phytoplankton. possesses old natural flora above the water level and on dry place. On the side of the lake some flora was Principal Cluster Analysis observed to flourish on moist water logged soil and swampy ground along the margins of water. Ipomea Multivariate statistical techniques were aqutica, Cyprus sp., scripus sp., Phragmits vallaotria applied to identify characteristics of water quality in and Typha domogensis were present in excess in the the studied stations (Fig. 21). Four factors were surrounding of the lake. Some rooted submerged extracted by principal component analysis (Fig. 22) plants i.e Najas minor, Meriophyllum verticilatum and explain 86.82% of the total variation (Table-7, Potamogeton natans were found in the form of 8). The factor one (PC1) loaded with variables of patches in the lake along with their seeds. The seeds TDS, Na, K, Cl, DO, hardness, Ca, Mg, sulphate and and some parts of such plants become favourable orthophosphate. Factor two (PC2) is related with food for the local and migratory birds. The broader COD, total acid hydrolysable phosphate. The third leaves of Nelumbo nelumbo floating on the surface factor (PC3) associated with pH and fluoride. Thus of water provide shelter shed, habitat and sprawling fourth factor (PC4) to its total eigen value of 1.605 ground to caterpillar and many terrestrial insects, were significantly correlated with BOD and mollusk, fish fingerling and birds. bicarbonate and negatively with ammonia and nitrate In the Haleji Lake only Salvinia molesta (free floating plant) was present on the west side in

Table-5: Physico chemical assessment of sediments of Haleji Lake, May-August 2008. Center Steel Mills Bridge Back Sampling Stations/ Parameters Sanctuary Phyio-I Phyio-II Vil. A.M Samoo lake Bhutyon Sanctuary

Temperature of water ºC 29.4 29.4 29.3 29.5 29.0 29.0 29.3 29.6 Conductivity µS cm-1 1975 1555 1346 1368 595 1829 1250 563 Total dissolved solids mgL-1 1264 995 861 875 380 1170 800 360 Salinity gL-1 1.0 0.8 0.7 0.7 0.3 0.9 0.45 0.3 Total residue in mgL-1 on 104˚C 6.825 36.296 16.189 18.2 62.278 20.075 19.607 26.076 Volatile residue in mgL-1 on 550˚C 0.442 6.759 1.152 1.25 1.984 1.9780 0.857 2.6169 Fixed residue in mgL-1 on 550˚C 6.383 29.537 15.037 16.95 60.293 18.097 18.750 23.4591 pH 7.92 7.91 7.80 7.94 7.99 7.62 7.89 8.02 Chloride mgL-1 23 96 85 90 44 39 18 6 Total hardness mgL-1 223 1100 585 570 300 267 300 148 Ca mg/L 150 220 135 150 65 44 65 37 M.Alkalinity mgL-1 40 30 47 50 30 35 52 30

TAJ MUHAMMAD JAHANGIR et al., J.Chem.Soc.Pak.,Vol. 35, No.3, 2013 1014

Table-6: Classification of Fishes, species and size. Class species Quantity or size Channa striatus Carnivorous Notopterus notopterus The measurement of this group of fishes was present in small size. Xenenthodon canclia Oreochromous These were found in good number and majority of the fishes were of size 6 – 9 inchs with weight Omnivorous mossambicus of 300-900 gm. Oreochromous niloticus Gudisia chapra Planktivorous This group was present in less numbers and in small size, except Gudusia chapra which was Chanda ranga Fishes present in good number. A group of Cyprinid Carp fishes was unfortunately found absent. Chela laubuca

Table-7: Total Variance Explained of water. Initial Eigenvalues Extraction Sums of Squared Loadings Rotation Sums of Squared Loadings Component Total % of Variance Cumulative % Total % of Variance Cumulative % Total % of Variance Cumulative % 1 9.375 52.083 52.083 9.375 52.083 52.083 6.750 37.501 37.501 2 2.897 16.093 68.176 2.897 16.093 68.176 3.196 17.753 55.254 3 1.752 9.732 77.908 1.752 9.732 77.908 3.045 16.918 72.171 4 1.605 8.919 86.827 1.605 8.919 86.827 2.638 14.655 86.827 5 .953 5.295 92.121 6 .456 2.536 94.657 7 .382 2.120 96.777 8 .255 1.418 98.195 9 .210 1.165 99.360 10 .074 .412 99.773 11 .041 .227 100.000 Extraction Method: Principal Component Analysis.

Table-8: Rotated Component Matrix of water quality. Component Parameters 1 2 3 4 DO .927* -.174 -.022 -.012 Ca .892* .163 .232 -.224 O.PO4 .856* .073 -.169 -.289 SO4 .792* .330 .471 .054 Mg .785* .275 .383 .092 Na .783* .244 .309 .177 K .775* .405 .056 .217 TDS .732* .378 .503 .135 Cl .715* .363 .581 .090 Hard. .698* .328 .581 .030 T.PO4 .224 .903* .134 .078 COD .229 .875* .053 .312 pH .172 -.160 .860* -.280 F .090 .596 .741* .126 BOD -.128 .193 -.030 .893* NH3 -.089 -.227 .200 -.801* NO3 .207 .538 -.055 -.613* HCO3 .402 .051 .460 .613* Extraction Method: Principal Component Analysis. Rotation Method: Varimax with Kaiser Normalization a. Rotation converged in 8 iterations

Fig. 22: Scree plot, Eigen value along with Fig. 21: Factor analysis, parametric contribution with component number, Haleji lake water. in each component, Haleji lake water.

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Experimental determined by turbidimetric method using barium chloride as precipitating agent and gelatin for The 12 sampling sites were selected for colloidal solution at the wavelength of 420nm. regular observations of water quality of Haleji Lake Dissolved oxygen was determined by Wrinkler during May through August 2008. The lake location method, the water sample was preserved in field by and sampling sites are indicated in Fig. 1 and 2 manganese sulphate and alkali iodide. The dissolved respectively. The sampling stations in lake were oxygen was determined by titration with standard reached through boat and water samples were sodium thiosulphate and starch as indicator. The collected from subsurface at the depth of 1feet chemical oxygen demand was determined by approximately, after the engine of boat stopped for a refluxing the sample in the chromic acid using few minutes. The lake bottom was fairly flat with the ferrous ammonium sulphate as titrant and ferrin as depth of 2.5-12ft, Almost high wind velocity indicator. The metals sodium, potassium, calcium and homogenized the water layers during study period. magnesium were determined by air acetylene atomic Water samples were collected in precleaned bottles absorption spectrometer (Varian Spectr AA20) at the and rinsed during sampling with lake water to avoid conditions recommended by the manufacturer of the any possible contamination in analyte. The samples wavelengths 589, 766.5, 422.7 and 285.2nm were quickly transferred and analyzed in the respectively in triplicate, with delay time 3 seconds. laboratory. The number of cation, anion, dissolved gases, hydrogen ion concentration, organic matter, Acknowledgement estimation of oxygen consumed by biomass was determined. The methods of analysis were followed We are thankful to Sindh Wildlife as described [24-26] for the pH measurement was Department for providing project financial and staff conducted by Orion 420 pH meter by dipping support. electrode in the water sample. The measurement of conductivity and total dissolved solids (TDS) was References conducted by WTW conductivity meter by inserting electrode in liquid sample. Argentometric method 1. A. Versari, G. P. Parpinello and S. Galassi, was used for the determination; in this method Journal of Food Composition and Analysis, 15, chloride was titrated with silver nitrate within pH 251 (2002). range 7-10 using potassium chromate as indicator. 2. R. G. Wetzel, Earth Science Reviews, 19, 88 The determination of fluoride from water samples (1983). was carried out by addition of equal ratio of total 3. N. V. de Jonge, M. Elliott and E. Orive, ionic strength adjustment buffer (TISAB II) blended Hydrobiologia, 1, 1 (2002). with 1,2-Cyclohexane diaminetetraacetic acid by 4. D. Harper, Hydrobiologia, 232, 65 (1992). manufacturer and measurement was made with Orion 5. D. W. Sutcliffe and J. G. Jones, Eutrophication: 5 Star Benchtop (Thermo Scientific USA) coupled Research and application to water supply, with ion selective electrode. The hardness was Freshwater Biological Association. The Ferry estimated by compleximetric titration at pH 10 House, Far Sawrey, Ambleside, Cumbria LA22 adjusted with ammonical solution. The titration is OLP and International Water Supply carried out with disodium ethylenediamine tetraacetic Association, 1 Queen Anne's Gate, London acid (Na2 EDTA) in the presence of Erichrome black SW1H 9BT, p. 4 (1992). T indicator [3-Hydroxy-4-(1-hydroxy-2-napthyl) azo- 6. S. O. Ryding, and W. Rast, The control of 7-nitro-1-napthlenesulphonic acid, sodium salt].The eutrophication of lakes and reservoirs, New end point was indicated by the change of color from Jersey: Parthenon (1989). wine-red to blue. The phenolphthalein or methyl 7. J. Skei, P. Larsson, R. Rosenberg, P. Jonsson, M. orange alkalinity is change of color from pink to Olsson and D. Broman, Ambio, 29, 184 (2000). colorless or yellow to reddish respectively at the end 8. http:/cda/en/ramsar-documents-list-anno- of reaction with use of hydrochloric acid as titrant. pakistan/main/ramsar/1-31- 18^16123_4000_0__ The Phosphorus was determined to form phospho- 9. A. D. Bank, Melamchi Water Supply Project, molybdate complex and reduced by ascorbic acid to Annual Report on Environmental and Social yield colored molybdenum blue at 880nm. Nitrate Activities for the year 2002 to 2003; Melamchi was determined by brucine sulfate to give yellow Water Supply Development Board (2003). color at 410nm. The ammonia was determined by 10. M. Sillanpaa, R. M. Hulkkonen, and A. blue colored compound of indo phenol is formed by Manderscheid, Rangifer, 15, 47 (2004). the reaction of ammonia and hypochlorite with 11. S. Nazneen, Int. Revue ges. Hydrobiol. 65, 269 phenol at known wave length (630nm). Sulphate was (1980). TAJ MUHAMMAD JAHANGIR et al., J.Chem.Soc.Pak.,Vol. 35, No.3, 2013 1016

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