water quality and its impact on tilapia zilli (case study) qarun lake-egypt

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WATER QUALITY AND ITS IMPACT ON TILAPIA ZILLI (CASE STUDY) QARUN LAKE-EGYPT Lubna A. Ibrahim1 and Enas M. Ramzy2 1

Researcher, Chemistry Dept., Central Laboratory for Environmental Quality Monitoring (CLEQM ), National Water Research Center (NWRC), Cairo. Corresponding Author: [email protected] 2 Researcher, Biological Indicators Dept., Central Laboratory for Environmental Quality Monitoring (CLEQM), National Water Research Center (NWRC), Cairo, Egypt. [email protected]

ABSTRACT Aquatic environment is subjected to different types of pollutants via intrusion of industrial, agricultural and domestic waste water. The study was conducted to throw light on water pollution and evaluate the quality of Tilapia Zilli at the north eastern part of Lake Qarun during the summer season. In addition to study the relationship between the activity of trace elements in water samples and their total concentrations in fish tissues (muscles, liver and brain). The physiochemical parameters of water samples were determined. Trace elements, species (metabolites) of organophosphorus pesticides (OPPs) and organochlorine pesticides (OCPs) were determined in the muscles, liver and brain of Tilapia Zilli and water samples collected. The results indicated that the studied water samples were saline and the abundance of trace elements followed the order: Fe> Mn> Cu> Cd> Zn> Pb. The total dissolved concentrations of Cd, Cu, Pb and Fe were higher than the permissible limit, but their active concentration still less than the permissible limit. The highest accumulations of trace elements were recorded in the liver and brain while the lowest were recorded in the muscles. All metal levels detected in tissues were not safe for human consumption, except manganese was within the limits for fish proposed by World Health Organization (WHO). Regression equation showed that the total element concentration in fish tissues depend on the activity of that element in water samples. OCPs are higher than OPPs with respect to each sample. The concentrations of α-BHC, γ-BH C, hepta-epoxide, cadusaphos, Di-Syston, pirimiphos, fenitrothion, and profenofos in liver are depending on their concentration in water samples. Bioaccumulation Factor (BAF) of trace element, OCPs and OPPs were in low to medium concentration. Cadmium, copper, iron, manganese, lead, OCPs and OPPs were safe and didn’t constitute threaten to human health compared to Organization for Economic Cooperation and Development (OECD) guidance, while Zinc was hazard ranking. The study recommends treating wastewater before discharge into Lake and there is a need for continuous monitoring for water quality of Qarun Lake since the Lake serves as source of fish for local inhabitants in that area.

Keywords: Water Quality, Qarun Lake, Tilapia Zilli, Organophosphorus and Organochlorine Pesticides 1. INTRODUCTION Lake Qarun is a closed water lake, which originated from a fresh water lake called Mories. The lake receives annually about 400 million cubic meters of agricultural wastewater drainage (Egyptian Company for Salts and Minerals [1]). M any factors affecting Lake Qarun ecosystem include the climatic conditions, amount of discharged wastewater, seepage from the surrounding cultivated land and geological aspects (Abdel-Satar et al., [2]). Lake Qarun has many drastic changes that affect the potential economic role as a site for living natural resources. The main reason came from gradually increasing salinity over the last century. The increase of salinity depends on the input of drainage water (controlled by irrigation practices) and the subtropical climate of the lake leading to high temperature and seasonal fluctuations in rate of water evaporation (Anwar et al., [3]). 170


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Extensive water evaporation from such closed ecosystem increases concentration of salts, trace elements, pesticides and other pollutants is expected to change their quality and affect their food web. Consequently, this changes water quality and affects biology of the lake (Ali et al., [4]). Fish are located at the end of the aquatic food chain and may accumulate metals and pass them to human beings through consumption causing chronic or acute diseases (Al-Yousuf et al., [5]). El-Gheit et al., [6] revealed that there are three factors causing massive mortalities of fishes in Qarun Lake, namely blooming phenomenon, poor water quality (trace metals & physico-chemical parameters) and microbial pathogens in the aquatic environment. Mansour et al. [7] concluded that the physicochemical characteristics of the Lake Qarun water are mainly due to the discharges of different drains into the lake. When subsurface irrigation drainage water is discharged into a wetland, a variety of serious impacts can occur (Lemly, [8]; Lemly, Finger, & Nelson, [9]; Micklin, [10]; van Schilfgaarde, [11]; Zahm [12]. Such water is usually characterized by alkaline pH, elevated concentrations of salts, trace elements, and nitrogenous compounds, but low concentrations of pesticides (Fujii, [13]; Neil, [14]. Saad and Hemeda [15] stated that the high nutrient concentrations coincided mainly with spreading of the nutrient enriched drainage water over the dense lake bottom water. The distribution of trace elements showed irregular patterns in the lake as a result of interference between several factors such as surrounding environment, closed basin and climatic effects (Abdel-Satar et al., [2]). Sabae and Ali [16] showed that the distribution of denitrifying bacteria was controlled by the effect of drainage water via El-Batts and El-Wadi Drains, which are loaded with nutrients. Trace elements are of particular concern, due to their potential toxic effect and ability to bioaccumulate in aquatic ecosystems (Censi et al., [17]). When fish are exposed to elevated levels of metals in a polluted aquatic ecosystem, they tend to take these metals up from their direct environment (Framobi et al., [18]). Transport of metals in fish occurs through blood and the metals are brought into contact with the organs and the tissues of the fish and consequently accumulated to different extents (Kalay & Canli, [19]). Prolonged exposures to trace elements even in very low concentrations have been reported to induce morphological, histological and biochemical alterations in the tissues that may critically influence fish quality (Kaoud and El-Dahshan, [20]). Birungi et al., [21], found that accumulation of trace elements in a tissue is mainly dependent upon concentrations of metals; besides other environmental factors such as salinity, pH, hardness, and temperature. Pesticides use has increased substantially throughout the world for protection of crops from insect infestation and to achieve higher crop yields with better quality (Zia et al., [22]). An estimated quantity of 2.5 million tons of pesticides is used in the world annually with continuous increases (Pimentel, [23]).The group of pesticide compounds includes chloroorganic insecticides used to eliminate human and animal parasites and fight agricultural pests. The organochlorine pesticides(OCPs) are among the major types of pesticides, notorious for their high toxicity, their persistence in the physical environment and their ability to enter the food chain (Ntow, [24]). Researchers have detected pesticides residues in heptachlor, endosulfan, aldrin, DDT and PCBs in water and many of these pesticides have also been detected in sediment, aquatic plants, and fish (Osibanjo et al., [25]). Organophosphorus compounds are quickly degradable in aquatic environment where the alkaline media accelerates their degradation (Saad et al., [26]). The OCPs, unlike OPPs are more resistant to microbial degradation and have a propensity to concentrate in lipid rich tissues of Aquatic organisms (Essumanget al.,[27]). There are many factors which may affect the contamination levels of organophosphrous in drainage water such as the presence of most minerals and salts (Schlauch, [28]), photosensitizers, temperature, pH, radiation and metal cations (Brust, [29]; Mortland and Raman [30]; Smith, [31]; Schaefer and Dupras, [32]; Meikle and Youngson, [33]), as well as micro-organisms (Haven and Rase [34]). The deterioration of water resources in the lake during the summer season is considered as a serious threat to the aquatic life (Mansour and Sidky, [35]; Fathi and Flower, [36]). Ali and Fishar [37] mentioned that the eastern part of the lake was generally highly contaminated (concerning trace elements in water, sediment, benthic invertebrate and fish) in compared with the western one. 171


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The increasing pollution of water resources in Qarun Lake and the consequent effects on aquatic environment and human health is an issue of great concern. This work aims at highlighting the problem of water pollution in the North eastern part of Qarun Lake with special emphasis on major pollutants species, evaluation of Tilpia zilli fish with respect to pesticide residue and bioaccumulation of some important trace elements in muscles, liver and brain in summer season, study the relationship between the activity of metals ion in water samples and their total concentrations in fish samples were also discussed, and test the relationship between different types of OCPs and OPPs in water and fish parts.

2. MATERIAL AND METHODS 2.1. Study Area Lake Qarun is a closed saline lake lying in the western Egyptian desert and lies 83 km southwest of Cairo. The lake is located between longitudes of 300 24` & 300 49` E and latitude of 290 24` & 290 33` N in the lowest part of Fayoum depression. It is bordered from its northern side by the desert and by cultivated land from its south and southeastern side (Abdel-Satar et al., [38]). The lake is shallow, with mean depth of 4.2 m and most of the lake area has a depth ranging between 5 to 8 meters. The lake has an area about 40 Km2 with an irregular shape of about 40 Km length and 6 Km mean width. The water level of the lake fluctuated between 5 to 8 meters (Sabae and Ali, [16]). The lake receives the agricultural and sewage drainage water from the surrounding cultivated land through a system of twelve drains. The drainage water reaches the lake by two huge drains, El-Batts drain (at the northeast corner) and El-Wadi drain (near midpoint of the southern shore).

2.2. Sampling Water and fish samples were collected in triplicates from the studied site in various containers specialized to suit the nature of tested parameter according to Standard Methods for Examination of Water and Wastewater (APHA, [39]). The present investigation was started with samples collection in May, July and September 2012 in each month, three samples were collected for water and Tilpia zilli fish from three sites in the north eastern part of the Lake as shown in Fig. 1. Sampling procedures as well as analytical methods for both physical and chemical determinations were carried out according to Standard Methods for Examination of Water and Wastewater. Water samples were taken from surf ace water into a polyethylene bottle. Fish samples, Tilpia zilli, were collected from the lake at least (2 Kg) and kept in iceboxes during transportation. All collected samples were stored in an iced cooler box laboratory and kept at -4 Co and delivered immediately to the laboratory, where they were analyzed.

2.3. Reagents All reagents used were of analytical grade. Deionized water was used for all the prepared reagent solutions. Stock standard solutions of cadmium (Cd), copper (Cu), iron (Fe), lead (Pb), manganese (Mn) and zinc (Zn), were obtained from Merck in concentrations of 1000 mg/L (Merck, Darmstadt, Germany). A mixture of pesticide calibration standards containing hexachlorobenzene (HCB), lindane, aldrin, heptachlor, heptachlor epoxide, dieldrin, endrin, dichloro diphenyl trichloroethane (pp-DDT), pp-DDT analogues (e.g. op-DDT, op-DDE, pp-DDE, op-DDD, pp-DDD), malathion, parathion, methyl parathion, dimethoate, pirimiphos-methyl, profenofos, and diazinon, were provided by the Environmental Protection Agency (EPA). A mixture calibration standards of organochlorine pesticides (for EPA Methods - Contract Laboratory Standard, CLP-226B) containing Aldrin, α -benzene hexachloride (α -BHC), γ -BH C, β - BHC, α -chlor da n, γ -chlordan, heptachlorepoxide, decachlorobiphenyl, pp-DDE, endrin ketone, endrin aldehyde, endosulf an II, endosulfan sulphate and 2,4,5,6-tetrachloro-m-xylene were provided by Ultra Scientific (Lab Tech). Mixture calibration standards of organophosphorus pesticides were supplied by the Central Agricultural Pesticides Laboratory, Giza, Egypt.

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Fig. 1: Map of Qarun Lake showing the sampling location.

2.4. Water and Fish Analyses The physical and chemical parameters were analysed according to standard methods for examination of water and wastewater (APHA, 2005). For major cations and trace elements, the samples filtered by filtration system through membrane filter of pore size 0.45 µ and acidified with nitric acid to pH Ca >K . Chloride and sulphate concentrations ranged from 10.33-14.80 (mean 11.95±1.33) g/L and 4.19-6.15 (5.30±0.66) g/L, 2respectively. The major anions exhibited as the following order; Cl >SO4 . Sulphate was found to be higher than the permissible limit (200 mg/L), this return to the intrusion of drainage and agricultural wastewater together with modifications observed in environment and climate (Edwards and Withers, [48]). Applying Hydrogen32 program to water samples; the output data indicated that the salts which composed the TDS in the studied samples were NaCl (72.06±2.22%), MgSO4 (16.91±0.52%), Na2SO4 (4.79±2.95%), CaSO4 (3.62±2.19%), Ca(HCO3)2+CaCO3 (1.34±1.06%), KCl (1.27±0.11%) and others (0.1%). On the same line, Mansour et al., [7] found that the salts composing the TDS in lake water were NaCl (61%), MgSO4 (17.9%), Na2SO4 (12.4%), CaSO4 (3.6%), Ca(HCO3)2, CaCO3 (0.2%) and others (1.8%).

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3.2. Trace Elements in Water and Fish Tissues The results of trace elements in water samples were compared with US EPA, [49] (United States Environmental Protection Agency); National recommended water Quality Criteria, while in fish samples were compared with WHO, [50]; Evaluation of certain food additives and contaminates. Trace elements in natural water occur in particulate or soluble form. Soluble species include labile and non-labile fractions. The labile metal compounds are the most dangerous to fish. The presence of trace elements inside the fish tissues is often affected by many external and internal factors. Metals concentration is correlated with ambient metals level in the surrounding environment, the available metal form in water, the structure of the target organ as well as the interaction between the metal and this organ (EL-Naggar et al., [51]). Generally, the higher metal concentration in the environment, the more may be taken up and accumulated by fish. The metal level is related to its waterborne concentration only if metal is taken up by the fish. The mean concentrations of the tested trace elements in the water and fish tissues of studied samples are presented in Fig. 2. Metal concentrations in the water of the lake followed an abundance of: Fe> Mn> Cu>Cd>Zn>Pb. Metal levels in muscles follow the ranking: Zn>Fe>Cu>Mn>Pb>Cd, while in liver follow the ranking: Zn>Fe>Mn>Cu>Pb>Cd, and in brain follow the ranking: Fe>Zn>Cu>Mn>Pb>Cd.

Fig. 2: Concentrations of trace elements in water and fish parts from studied sites.

The presence of trace elements in Lake Qarun is mainly of allochthonous origin due to either agricultural influx, wastes of fish farms or sewage via surrounding cultivated lands (Ali and Fishar, [52]). The obtained mean values of Cd (0.0968 mg/L), Cu (0.0969 mg/L), Fe (0.6256 mg/L), Mn (0.1118 mg/L), Pb (0.106 mg/L) and Zn (0.085 mg/L) in water samples were higher than a previous study obtained by Abdel-Satar et al., [38] (average respectively 0.02, 0.03, 0.40, 0.07, 0.086 and 0.04 mg/L). These results reflect that the anthropogenic influences rather than natural environment of the water may be the main reasons (WasimAktar et al., [53]). Cd, Cu, Mn and Pb mean values were higher than the permissible limits (0.01, 0.09, 0.1 and 0.1 mg/L) of (US EPA, [49]), but Fe and Zn were within that permissible limit (1.00 and 0.12 mg/L). 177


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Speciation of trace metals using Visual MINTEQ program showed that 0.005 to 0.008 mg/L of Cd is present as free ions, while from 0.00001 to 0.00007 mg/L as inorganic species and from 0.074 to 0.100 mg/L as organic species. Cu free ion ranged from 0.003 to 0.011 mg/L, inorganic species ranged from 0.0004 to 0.0038 mg/L and organic species ranged from 0.080 to 0.104 mg/L. Mn free ions ranged from 0.048 to 0.087 mg/L, inorganic species ranged from 0.035 to 0.064 mg/L and organic species at less than 0.00001. Pb free ions ranged from 0.002 to 0.014 mg/L, inorganic species ranged from 0.050 to 0.154 mg/L and organic species ranged from 0.001 to 0.01 mg/L. This showed that the highest concentration of Cd, Cu, Mn and Pb are present in water in non-toxic form, so that these elements don't show any toxic effect on fish tissues. The higher concentrations of trace elements were found in fish tissues than the surrounding environment (water), Fig. 2; according to McCarthy and Shugart, [54] was due to fish may absorb dissolved elements and then accumulate them in various tissues in significant amounts above those found in their environment, thus exhibiting elicited toxicological effects. Similarly Chale, [55] recorded that concentrations of trace elements in fish tissues were always higher than that of water. The lower concentrations of Cd, Cu, Fe, Mn, Pb and Zn were recorded in the fish muscles, while the higher values were in the liver or brain, Fig. 2. These finding are in agreement with those obtained by Dural et al. [56] and Alhas et al. [57]. The accumulation of metals in fish tissues (muscles, liver and brain) may be due to the fact that ,the lake receives heavy load of organic and non-organic pollutants’ via several agricultural drains, domestic and waste water in addition to the industrial effluents. On the other hand, this bioaccumulation might be correlated with fat-content in tissues and its great affinity to combine with trace elements. The lowest concentrations of metals were found in muscle tissues than liver and brain; this may due to the little blood supply to the muscular tissue (Shenouda et al., [58]) and related to lower metabolic activities of muscle. The muscles showed considerable amounts of metals. This may be correlated with fatcontent in muscle tissues and its great affinity to combine with heavy metals (Shenouda et al. [58]). High concentrations of metals as Cd, Cu, Mn, and Zn in the liver are related to detoxification processes that take place in this organ (Celechovska et al., [59]) and related to its role as storage organ (Satsmadjis et al., [60]). The highest value of Pb was found in the brain tissue; lead have a special affinity for brain as lead accumulation is high in this tissue (Tulasi et al., [61]; Allen et al., [62]). Lead was found to inhibit the acetyl cholinesterase in fish on the other hand, cadmium affected on enzyme activities and membrane integrity (Cicik et al., [63]). In muscles and liver, the concentrations of Cd, Cu, Fe and Zn are higher than the permissible level for Cd (0.5 mg/kg), Cu (5 mg/kg), Fe (5 mg/kg) and Zn (40 mg/kg), while in brain Cd, Cu, Fe, Pb (>2 mg/kg) and Zn are higher than the permissible limit recommended by WHO, [50]. Mn concentrations in muscles, liver and brain are within the recommended limit 100 mg/kg (WHO, [50]). The presence of trace elements inside the fish tissues is often affected by many external and internal factors. Metals concentration is correlated with ambient metals level in the surrounding environment, the available metal form in water, the structure of the target. In the present study, regression equation between total metal contents in fish tissues (muscles, liver and brain) and activity of metal in water samples are shown in Table 3. Levels of metals in fish parts (muscles, liver and brain) were highly comparable with those of water; activities of metal concentrations in water are the major factor, being correlated positively with metals in fish parts, Table 3. In addition, water pH, correlated negatively with metals in fish muscles for Cd, Cu, Mn and Pb, liver for Cd, Cu, Fe, Mn and Pb, played an important role in governing metal uptake by fish tissues. The coefficient of activity of metal in water is highly significant (P γ-BHC>-BHC> PP-DDT> γ-Chlordan> α-BHC> OP-DDT> Heptachlor> Endrin> Hepta-epoxide > Aldrin. 179

Conc (µg/kg)

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Fig. 3: Minimum, maximum and mean values of different OCPs in water samples (n=9); where A: in water, B in muscle, C in liver and D in Brain.


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OC pesticides found in muscles, Fig. 3(B) are α-BHC, γ-BHC, β-BHC, -BHC, heptachlor, aldrin, hepta-epoxide, γ-Chlordane, pp-DDE, Aldrin, PP-DDD, OP-DDT and PP-DDT with mean values are 0.90. 7.35, 38.49, 9.96, 7.01, cadusaphos> chlorpyrifos methyl> phenthoate> Di-Syston> ethoprophos> fenitrothion> chlorpyrifos. In fish tissues, Fig. 4(B, C and D), OPPs found are methamidophos, cadusaphos, ethoprophos, phorate, diazinon, triazophos, Di-Syston, chlorpyrifos methyl, pirimiphos methyl, chlorpyrifos, phenthoate, fenitrothion and profenofos at a mean value 6.38, 9.25, 14.02, 12.83, 3.28, 103.20, 38.01, 5.45, 23.27, 0.81, 24.36, 8.54 and 33.13 µg/kg, respectively, in muscles. The order of OP pesticides concentration in muscles was triazophos > Di-Syston > profenofos > phenthoate > pirimiphos methyl > ethoprophos > cadusaphos > fenitrothion > methamidophos > chlorpyrifos methyl > diazinon > chlorpyrifos. In liver the concentrations of methamidophos, cadusaphos, ethoprophos, phorate, diazinon, triazophos, Di-Syston, chlorpyrifos methyl, pirimiphos methyl, chlorpyrifos, phenthoate, fenitrothion and profenofos are 11.48, 14.16, 14.57, 15.252, 11.21, 342.46, 74.27, 14.34, 33.72, 2.25, 24.16, 10.38 and 36.13 µg/kg, respectively. The order of OP pesticides concentration in liver was triazophos > Di-Syston > profenofos > pirimiphos methyl> phenthoate > phorate > ethoprophos > chlorpyrifos methyl > cadusaphos > methamidophos > diazinon> fenitrothion > chlorpyrifos. While in brain the concentrations of methamidophos, cadusaphos, ethoprophos, phorate, diazinon, triazophos, Di-Syston, chlorpyrifos methyl, pirimiphos methyl, chlorpyrifos, phenthoate, fenitrothion and profenofos are 13.94, 14.62, 16.43, 17.81, 12.19, 339.67, 74.25, 17.06, 22.04, 5.06, 25.96, 16.64 and 41.82 µg/kg, respectively. The order of OP pesticides concentration in brain was triazophos > Di-Syston>profenofos > phenthoate > pirimiphos methyl > phorate > chlorpyrifos methyl > fenitrothion >ethoprophos> cadusaphos > methamidophos > diazinon > chlorpyrifos. Linear regression data on multiple OCPs relationships in water and liver were recorded in Table 4. No correlations were significant between different types of OCPs in water and muscles and brain. The coefficient of activity of OCPs in water is highly significant (P