Vol. 10, No. 1 - Jan. -June 2007, 28-33 J. 8aqai Med. Univ.

Assessment of pollution status of fresh water lakes by metal ions and their hazards on the health of human being

1 3 T. A. Saqib *, M. Ahmed Azmi2, S.N.H. N aqvi , Kahkashan Akhtar4, Rehana Perveen5

ABSTRACT

Kalri and Haleji lakes of Sindh region, Pakistan, are the important and valuable sources of water supply for drinking and irrigation purposes. A study was done to determine the concentration of pollutants (metal ions) in water and in different organs of fish, Labeo rohita by atomic absorption spectrophotometry. The concentration of metal ions (in water) was higher during the months of March to July. The highest peak for lead was found in Kalri and Haleji lakes which were followed by iron, chromium and zinc. Ions such as cadmium and manganese were found in least concentration. Bioaccumulation of metal ions in different organs of fish Labeo rohita, was found highest in liver while minimum concentration was found in adipose tissues. Generally two peaks were observed i.e., one in April to August and the other in November. It was found that there is higher amount of metal ions in Haleji lake water and fish organs. Therefore, supply of drinking water has been stopped from Haleji lake, possibly due to hepatotoxic and nephrotoxic effects.

Keywords: Lakes, Pollutants, Labeo rohita, Environment, Sindh.

5 INTRODUCTION Nadi, India . Atomic absorption spectrophotometric determination of six heavy metals in fishes, as well as In the province of Sindh, Pakistan, the two lakes Kalri in river water has been reported in different regions of 2 2 6 (Kinjher-142.5 km ) and Haleji (16.9 km ) are fresh India • Determination of the concentration of six heavy water reservoirs situated on the left side of Karachi metals in the central drinking water supplies has also 7 Hyderabad National Highway. They are important and been done . valuable sources of water supply for drinking purpose. The farmers in this province also use these lakes for The relationship of mercury with aluminum, iron and irrigation. Haleji and now Kalri Lake is being used as manganese has been reported in the sediments from 8 water supply reservoir. The people of Karachi nine floodplain lakes in Pantanal, Brazil . Similarly the (population, about 15.2 millions), were using water of assessment of some elemental contaminants has also Haleji for drinking and farming. Haleji lake is facing been reported in water and fish samples from Aba River, 9 eutrophication and pollution which is alarming from Nigeria . Also the bioaccumulation of heavy metals in the health point of view, both for the human beings and the muscles of Masheer, Tor putitora as an evidence of for aquatic animals. The Kalri Lake, is aiso facing some pollution of heavy metals has been investigated in the eutrophication and pollution!). River Kabul, Pakistan! 0.

From the health point of view it was necessary to study Although much work has been done in this respect in the nature and extent of environmental pollutants such many countries, however little effort has been made so as heavy metals and pesticides3 in these lakes and also far in Pakistan. Therefore, the main object of the present in the body of fishes present in them, because the fishes study was to determine the concentration of some metal are used as food and the pollutants may enter the human ions in lake water and freshwater fishes that may be body via food chain. hazardous.

The presence of pollutants (metals etc.) in water and Materials and methods fish has been reported earlier. The concentration of Fresh water samples were collected from Haleji and metal ions in five species of fish has been observed from Kalri lakes. Fishes were collected from the lakes by net 4 the South Esk River, Northeastern Tasmania, Australia . having a mesh size of about 2 inches while water samples The distribution of heavy metals in the water, sediments, were collected by using a peristaltic pumpll. plants and fish samples has been collected from the Kali

1* Correspondhlg Author: Tasneem Ahmed"Saq;II, Ph.p. + . 1 .,"~,4 : Depl!rII!1~nt of Zoo;~y, 0rivarsity of ~ra'Ch i. Email: aZ!"i ~hmed @ h9ttirai ! : com 2.5:B~q~ 1 Medical University, KarachI-Pakistan. Vol. 10, No. 1 - Jan.-June 2007, 28-33 J. Baqai Med. Univ.

Both water samples and fish collections were made from RESULTS the same spot simultaneously_The water samples were filtered through Whatman No. 40 paper as described Metal ions in wat~r of Kalri and Haleji lakes earlieriZ. The chilled fishes having a weight of 600 to Determination of metal ions (Cr, Cd, Cu, Fe, Mn, Pb 850 grams were taken immediately to the laboratory for and Zn) in the Kalri and Haleji lake water showed that removing stomach, liver, kidney, adipose tissues, gills the concentration of these ions were generally higher in and edible muscles. All the tissues were wrapped in summer season and highest in Haleji lake except zinc. aluminum foil separately and brought to complete The highest concentration of chromium was found in dryness by keeping in an oven at 40°-50°C upto constant the month of May in Kalri lake (0.39 ppm, Fig la). weight. The dried samples and water samples were then Generally the concentration of chromium was higher 13 subjected to acid digestion • in June, August and September and lowest during December in Kalri la)cce (0.016 ppm, Fig. la). The After digestion distilled water and HeI (1:1) were added concentration was higher in March, May, August, and the sample was again warmed to dissolve the residue. September and December in Haleji lake while lowest The walls of the beaker a:o.d watch glass were washed in April (0.013 ppm, Fig. Ib). with distilled water and the resultant sample was filtered to remove the silicate and other insoluble materials that Little variation was found in case of cadmium. The may clog the atomizer. Lastly before analysis, the volume highest concentration was found in the month of May was adjusted according to the concentration of expected (0.019 ppm, Fig. la) in Kalri lake, while in Haleji lake, metal ions. the highest being in the month of July (0.026 ppm) and lowest being in the month of December (0.011 ppm, Acid digestion of fish tissues was done according to the Fig. I b) during the whole season. method of Benton1 4. After digestion, the cover was removed from the beaker and heated on the hot plate In the case of copper, higher concentration was detected in fume chamber at 80°C till fumes of HCI04 in the months of May, November and December (as disappeared. The beaker was then removed from the shown in Fig. la) in Kalri lake. The highest was found hot plate and cooled. Distilled water was added to the in the month of May (0.046 ppm) and lowest in the sample to make up the volume to 10 mI. Both samples month of September (0.013 ppm). The' concentration (water and fish tissues) as well as stock standard solutions was higher in the months of May, July, November, and were then prepared for analysis. December and the highest being in December (0 .089 ppm) while lowest in the month of October (0.0126 2.1 Preparation of standard stock solutions ppm, in Haleji lake, Fig. Ib). Generally the concentration Stock standard solutions (1000 ppm) were prepared by of copper was higher in Haleji lake as compared to Kalri dissolving the required amount of following salts such lake. as in CrCb, CdClz, CUS04, FeCb, MnS04, Pb(N03)z and ZnS04 in deionized water. Quantitative determination of iron indicated slightly higher concentration during the months of May, June, Different dilutions of stock solutions were made to July, August and September in Kalri lake, water and the prepare working standards in the measuring ranges. highest being in July (0.124 ppm) and the lowest in January (0.011 ppm, Fig. la). In Haleji lake higher Concentration of metal ions may be calculated by using concentration of iron was found during the months of the following equation: February to August, while it was highest in May (0.1653 Cli Al = Czl Az Cl = CzAll Az ppm) and lowest in November and December (0 .016 Where: ppm, Fig. Ib). The values of iron concentration were Cz = Concentration of known solation found to be higher in Haleji lake as compared to Kalri Az = Absorbance of known solution lake. Cl = Concentration of unknown solution Al = Absorbance of unknown solution In the case of Manganese, higher concentration was found in the months of June, July and October in Kalri Analysis of each sample was done in duplicate and three lake. The highest was in the month of June and October times. Concentrations of each sample were expressed (0.27 ppm) while the lowest in January (0.011 ppm, in in ppm or f.lg g-I. Kalri lake, Fig. 1a). In Haleji lake, higher concentration was found in the months of May, June, September and Vol. 10, No . 1 - Jan.-June 2007, 28-33 J. 8aqai Med. Univ.

October, the highest concentration being in July (0.037 gills (0.137), stomach (0.098), edible muscles (0.072) ppm) while lowest in December (0.012 ppm, Fig, Ib). and adipose tissues (0.021) of Labeo rohita. A peak was There is higher concentration of manganese in Haleji observed in August while slightly higher peak also noted lake as compared to Kalri lake. in December (Fig. 2b).

The concentration of lead was higher during the months Copper of May to August in Kalri lake. The highest concentration In case of copper in Kalri lake fishes, the highest quantity was found in July (0.209 ppm) and lowest in January was found in liver (0.373) then in kidney (0.247), gills (0.0113 ppm, Fig. la). In Haleji lake, the higher (0.196), edible muscles (0.165), stomach (0.115) and concentration was found in the months of March, April, lowest in the adipose tissues (0.066) of Labeo rohita. June, July, August and September but the highest Generally two peaks were noted i.e. MayJune and also concentration of lead was noted in June (0.222 ppm) in NovemberDecember (Fig. 3a). while the lowest in December (0.0136 ppm, Fig. lb). Generally the concentration of lead was found slightly At Haleji lake, the maximum concentration of copper higher in Haleji lake as compared to Kalri lake. was noted in liver (1.823) followed by stomach (1 .206) and then in gills 0.(958), edible muscles (0.865), kidney Lastly, the concentration of zinc was found higher during (0.605) and minimum in adipose tissues (0.302) of the the months of May, August, September and October in fish. Generally one peak was noted in July and second Kalri lake. The highest concentration was in the month in November-December (Fig. 3b). of August (0.085 ppm) while the lowest in January (0.025 ppm, Fig. la). In Haleji lake, the concentration DISCUSSION was higher in the months of March, April, June, July, A. Metal ions in water August and September. The highest concentration was The metal ions such as Cr, Cd, Cu, Fe, Mn, Pb and Zn in the month of July (0.085 ppm) while the lowest was determined in the Kalri and Haleji lake water showed in November (0.016 ppm, Fig. 1b). As compared to that the concentration of these ions were higher during Kalri lake, the concentration of zinc was higher in Haleji the months of March to July and in most cases one or lake. more peaks were observed in different months. A higher concentration of these ions could be due to a usual Metal ions in fish (Labeo rohita) shower of rain in late February and early March. More Regarding metal ion determination in water and fish flow of water into lakes may be the cause of increased variations in concentration were noted during the months concentration of polluting ions. During the months of of January-December. This has been presented in case April to June and in early July, the seasons are hot and of metal ions in water (Fig. 1a-I b) and those of cadmium due to evaporation of water, concentration of ions may and copper in fish organs (2a-3b). Similar pattern has increase further. However, late July and August are rainy been observed in other cases where the values of season that increase the total water content of the lakes concentration of metal ions such as chromium, iron, that makes the concentration of ions lower. In November, manganese, lead and zinc have been reported as the December and January the season is cold and exerts highest level in Ilg g-l only in parenthesis. low effect on the ions. Amongst all, highest peak of lead was found in both lakes which was followed by Fe, Cr Cadmium and Zn. Ions such as Cd and Mn were found in least The concentration of cadmium in Kalri Lake in different concentration. Higher uptake of Cd, Zn and Cu has tissues of Labeo rohita was noted at the highest level in been observed by the liver of five fishes found in liver (0.126) and then in gills (0.082), edible muscles Tasmania4. The distribution of metal ions such as Cd, (0.097), stomach (0.068), kidney (0.051) and adipose Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn from Yamuna River tissues (0.019) in decreasing order Fig. 2a. The from Delhi to Allahabad, India has been studied 15 . The concentration of cadmium in edible muscles was found results showed wide variations in different samples with greater than that of gills only in August while from the present study. The concentration of metal ions in January to July and September it was lesser than that water from N.W.F.P. province such has been determined found in gills. Whereas in October to December it was and the feasibility of the water for human consumption l6 lesser than that of gills and kidney. Generally one peak has also been discussed . was observed in the month of August (Fig. 2a). In Haleji lake, the highest concentration of cadmium Similarly the quality of water has been assessed by was noted in liver (0.205) followed by kidneys (0.198), estimating the concentration of metal ions in the spring Vol. 10, No. 1 - Jan.-June 2007, 28-33 J. Baqai Med. Univ. water of Azad Kashmir for human consumption 17. order of accumulation of Cu ions. Our observations are These results are almost in line with the present findings in agreement with those25 who reported that liver confirming the above results. Determination and uptake accumulated higher amount of Cu and other metals of metal ions such as Zn, Cu, Cd and Pb has been followed by kidney and gills in Labeo species. Analysis carried out in the water of Yamuna River6. They also of metal ions such as As, Cd, Cr, Cu, Fe, Mn, Pb and reported the uptake of metals by fish similar to that of Zn in eleven species of fishes from Tarbela and Indus present study. The concentration of Pb, Cd, Cr, Cu and . River has also been determined26. The different fishes Mn in central drinking water supply from hygienic point accumulated differently possibly due to local or specific in 1169 samples has also been discussed7. The pollution environmental conditions. The elevated levels of As, status of Chanab, Ravi and Indus rivers in Pakistan by Cd, Cr, Cu, Fe, Mn, Pb and Zn in the muscles of six metal contaminants has also been studiedI8,19 . commercial fishes has also been reported27 as in the present case the sequence is almost same. The Pollution caused by metals and chemicals in rivers in concentration of As, Cd, Cr, Cu, Fe, Mn, Pb and Zn in North Western Frontier Province (N.W.F.P.) of Pakistan Labeo rohita from Rawallake has been done and the has made its water not fit for drinking purpose because maximum concentration was found in the case of Zn bioaccumulation of these via food chain is dangerous (4.807 flg g-l) and minimum for Cd (0.003 flg g-l) has and may produce hepatotoxic and nephrotoxic effects20,21 . been reported28 . In the present case Labeo rohita also accumulated seven ions i.e. Cr, Cd, Cu, Fe, Mn, Pb, Zn Metal ion contamination on the functional capacity of carp gill cells with antioxidant interactions has been Our observations on gills and liver are in agreement investigated by an in vitro study22. A ferritin reaction with those who reported29 the accumulation of ions in study for its capacity to trap various heavy metal ions the sequence of gills, liver, blood, skin and muscles. in flowing seawater to diminish their effect has also been Analysis in 10 species of fishes from Rawallake including studied23. Labeo rohita for Cu, Fe, Pb and Zn has been examined and found that accumulation of these ions depended B. Metal ions in fishes on bioecological conditions of the lake as evident from Bioaccumulation of metal ions in different organs of the data of Kalri and Haleji lake30. The concentration Labeo rohita indicated the highest concentration from of Cu, Zn and Pb in fish from Hong Kong Harbour has Kalri lake in the liver followed by gills, edible muscles, been estimated and concluded that Cu" Zn and Pb were stomach and kidney and the minimum in adipose tissues. lowest in muscles which may and due to different Generally two peaks were observed i.e., first in April to ecological condition. However, in the present study the August and second in November. In Haleji lake the lowest concentration of ions was found in adipose tissue. sequence was some what different i.e. , liver, kidney, The data32 for gills of Oreochromis mossambicus is stomach, gills, edible muscles and adipose tissues. almost similar to that our study but for liver it is different. However the concentration in Haleji lakes is higher. Our The present study showed that liver contain highest observations are in agreement with those who also concentration of Cr followed by gills, this difference reported maximum accumulation of of Cd, Zn and Cu may be either due to lake / river or some higher by liver in five species of fishes in Tasmania4. metabolism in the liver of Oreochromis mossambicus. Bioaccumulation of heavy metals in different organs of The distribution and the sequence of bioaccumulation some of the common edible fishes of Kharkai River, of heavy metals in fishes from Kali N adi India has been Jamshedpur, India has been analyzed33 and they also reported. However, the distribution and sequence is reported that this river is considered as one of the most slightly different from the present study. The polluted river que to the accumulation of heavy metals concentration of heavy metals such as Mn, Zn, Fe, Cu, such as Fe, Zn, Pb, Co, Cu, Cr and Ni contents. The Cr, Ni, Pb, Hg, Cd and As has been estimated in edible present study also indicates similar effect for Haleji lake. muscles of 17 species of fishes and the positive correlation The concentration of three non-essential elements namely between the concentration of Zn and As in fish-muscle Cd, Hg and Ph in sediment and fish from several locations and water has been reportedl6. In the present study the in Alaska and California has also been determined34 but muscles are in the order of number three for they analyzed different tissues liver, muscle, gills and accumulation of metal ions. A significant increase of stomach contents and reported that Cd in fish liver Cu concentration in the gills, liver, brain and muscles exhibited a negative correlation with sediment of Labeo rohita has also studied24 after exposure to Cu concentrations and no such correlations were found for concentration as in the present case, gills are second in Hg and Pb when fish liver and sediment were compared. Vol. 10, No. 1 - Jan. -June 2007, 28-33 J. 8aqai Med. Univ.

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