water quality and its impact on tilapia zilli (case...

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Internatio na l Wat er T ec hno logy Jo ur na l, IWTJ Vol. 3, No. 4, D ec ember 20 13

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. [email protected] Corresponding Author:

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]).

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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.

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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 mid-point 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-BHC, β-BHC, α-chlordan, 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 <2 before analyses according to standard methods (APHA, [39]). The pH was measured at 25˚C using pH meter InoLab WTW level 1, transparency (cm) by Secchi disc. Dissolved oxygen (DO) concentration was determined titrimetrically according to the modified Winkler, full bottle technique (EPA, [40]). Electrical conductivity was measured at 25˚C using conductivity meter, model InoLab. cond level 1.

Carbonate (CO32-

) and bicarbonates (HCO3-) ions were determined titrimetrically against 0.1 N–HCl,

using phenolphthalein and bromo-phenol indicators, respectively. Total suspended salt for filtrated water samples was determined gravimetrically at 105 oC. Total dissolved solids (TDS) were determined by weighing the solid residue obtained by evaporating a measured volume of filtered water sample to dryness at 103-105 oC. Turbidimeter Thermo Orion AQ 4500 was used to measure the turbidity of the water samples using purchased calibration solutions of 0.1, 15 and 100 NTU. Concentrations of ammonia and orthophosphate (ortho-P) in water were determined using the calorimetric techniques with formation of phenate and stannous chloride reduction, respectively. Total phosphorus (total-P) was measured as reactive phosphate after persulphate digestion. Major anions; chloride (Cl-), sulfate (SO4

2-), nitrate (NO3-),

phosphate (PO43-

) and fluoride (F-) were measured using Ion Chromatography (IC), Dionex product, model

DX5000. Major cations; calcium (Ca2+

), potassium (K+), magnesium (Mg

2+) and sodium (Na

+) were

measured by inductively coupled plasma-optical emission spectrometry (ICP-OES) Perkin-Elmer product, model Optima 5300 DV. Dissolved organic carbon (DOC) was measured using DC-190 TOC analyzer, Tekmar Dohrmann with non-dispersive infrared detector (NDIR).

Trace elements (Cd, Cu, Fe, Mn, Pb and Zn) concentrations were determined in water and fish samples. The fish samples were prepared by the methods of the Association Official Analytical Chemists (AOAC, 1995). Fish samples were prepared as muscles, liver and brain parts prior to analyses. Trace elements (Cd, Cu, Fe, Mn, Pb and Zn) were measured in water and fish parts by using the inductively coupled plasma-mass spectrometry (ICP-MS), Perkin-Elmer product model SCIEX Elan 9000.

2.5. Pesticide Analyses in Water and Fish Tissues

Sample preparation, extraction, and clean-up were performed using the methods of the Association of Official Analytical Chemists [41]. In fish analysis, tissue parts were separated and processed individually.

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Water samples (1 liter) were extracted with 15% methylene chloride in n-hexane (v/v) and separating funnel was vigorously shaken for 2 min after it was left to separate layers. The aqueous layer (lower layer) was transferred into another separating funnel and extracted two times with the same solvent mixture .The combined methylene chloride/n-hexane layers passed through anhydrous sodium sulfate and the elution was evaporated in a rotary evaporator to dryness. The dried film was rinsed with 2 ml of n-hexane. This extract was cleaned up using Florisil column (400x22 mm) topped with 2 cm sodium sulfate anhydrous. Before placing the extract on the top of column; it was washed with 15 ml n-hexane followed by 200 ml 6, 15, 50% diethyl ether in petroleum ether (v/v). Residues analysis carried out using GLC according to method of AOAC [41].

About 50 g of fish tissues were mixed into a high speed blender with sodium sulfate anhydrous in the presence of 150 ml of petroleum ether (40-60 oC) for two min. The extract was decanted through Buchner funnel. The residue in the blender cup was extracted two times with petroleum ether and combined with first extract .The combined extract was passed on sodium sulfate anhydrous and the elution was evaporated in a rotary evaporator to dryness then defatting of the extract was performed using hexane/acetonitrile saturated with hexane1:2 (v/v) .The later extract was transferred to florisil column and eluted with solvent system 6, 15, 50% diethyether in petroleum ether (v/v).

Determination of pesticide residues was performed using Hewlett-Packard gas chromatograph model 5890 II, equipped with 63Ni electron capture detector (ECD) and HP 5970 mass selective detector, fitted with HP-1 capillary column (cross-linked methyl silicon gum; 30 m × 0.25 mm × 0.25 mm film thickness) according to method of AOAC, 1995. The column oven temperature was programmed from 80 to 160 oC at a rate of 3 oC/min, held 2 min, increased to 220 oC at a rate of 5 oC/min, and then held for 20 min. Injection and detector temperatures were adjusted to 220 and 300 oC, respectively. Compounds were identified by comparing their retention times (RT) with those of authentic standards, and the residues were quantitated by means of a HP 3395 computing integrator coupled to the GC, based on the peak areas given. Under the earlier mentioned conditions, the detection limit for quantitation of chlorinated hydrocarbon pesticides (e.g. BHC, lindane, aldrin, heptachlor, DDT isomers) is approximately 0.01 ppb, and 0.10 ppb for the organophosphorus pesticides (e.g. malathion, pirimiphos- methyl, profenofos).at the following conditions, Table 1.

Table 1: Operating condition

The column oven temperature was programmed for 160 oC at rate of 5 oC/min, held for 10 min increased to 240 oC at rate of 5 oC/min then hold for 20 min. Injection and detector temperature were adjusted at Co. Flow rate of hydrogen, air and nitrogen were at 75.0, 100.0, 11.7 ml/min, respectively. Compounds were identified by comparing their retention time (RT) with those of authentic standards.

2.6. Program used during study

SPSS, ver. 15, 2006, statistical software was used to calculate minimum, maximum, mean values of all parameters measured through the studied months and discuss the correlation between studied parameter in order to perform better data interpretation.

Visual M INTEQ program was used for geochemical speciation of trace elements (Gustafsson, [42]). The data of water samples including temperature, pH, DOC, cations, anions and trace elements were inserted in the database of the geochemical equilibrium modeling program Visual M INTEQ version 3, in order to form input files.

1. ECD(Ni63) to detect organochlorine pesticides. 2. F.P.D. to detect organophosphorus.

Column A Column B Name PAS-5 PAS-1701 Film thickness 0.25 µM 0.25 µM Film thickness 30 m 30 m Column ID 032 mm- OP 032 mm- OC

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Hygrogen32 program was used to calculate the salt composed TDS. The pH, TDS, cations and anions were inserted to the program to form the input files.

3. RESULT AND DISCUSSION

Samples collected from three locations (9 samples collected from three locations during three months) at the north eastern part of Qarun Lake. The samples were analyzed in triplicates and the relative standard deviation was less than 5%. The statistical analyses of physico-chemical parameter of Qarun Lake were summarized in Table 2. The results of physicochemical parameters were compared to the permissible limits of the Egyptian law 48/1982 regarding the protection of River Nile and water ways from pollution.

3.1. Water Quality

The water lakes proved to be slightly alkaline with a mean pH value 8.10±0.32, where in all cases it falls within the permissible limits (6.5 – 8.5). In general, Tilapia can survive at pH ranging between 5 and 10, but it do best in a pH range from 6 to 9 (Popma and Masser, [43]), so that the water at the studied sites is suitable for Tilapia. This change in pH from 8.10 to 7.35 was probably due to the stirring effect of the incoming flood from the El-Bat drain that converged towards the lake resulting in the mixing of the poorly alkaline or acidic bottom water with alkaline surface water to reduce pH.

Carbonate (CO32-

) ions were detected at concentration lower than bicarbonates (HCO3-) ions. (HCO3

-)

ions ranged from 143.40 to 433.90 mg/L with a median value 176.50 mg/L, while Carbonate (CO32-

) range from <0.2 to 25.70 with a median value 19.50 mg/L. Total alkalinity of Lake water ranged from 168.70 to 433.90 mg/L with a median value 196.00 mg/L. higher than the permissible limit. The increase of water alkalinity may be due to the bacterial decomposition of organic substrates.

Dissolved oxygen is an important parameter for identification of different water masses. Tilapia can survive acute at low DO concentrations (less than 0.3 mg/L) for several hours, considerably below the tolerance limits for most other cultured fish. When DO falls below 1 mg/L for prolonged periods, Tilapia metabolism, growth and disease resistance are depressed (Popma and Masser, [43]). The oxygen content of the investigated lake water ranged from 6.59 to 8.68 mg /L with a mean value 8.68±1.12 mg/L, these values (>5 mg/L) favor for good growth of Tilapias, reproduction and health (El-Sayed, [44]). The relatively high concentration of dissolved oxygen recorded could be attributed to light intensity rather than photosynthetic activity of phytoplankton and reduced turbidity during dry month.

Ammonia begins to depress food consumption at concentrations as low as 0.08 mg/L, while the prolonged exposures to 0.2 mg/L of ammonia concentration are found to be detrimental to fish (Popma and Masser, [43]). In the present study ammonia concentration ranged from 0.22 to 0.73 mg/L with a mean values 0.35±0.16 mg/L higher than the permissible limit (o.5 mg/L) and for fish (0.2 mg/L). This refer to the Tilapia Zilli acclimated to lethal dosage in the presence of adequate amount of dissolved oxygen. The increase of ammonia in water to 0.73 mg/L and decrease of dissolved oxygen to 6.59 mg/L can be attributed to the increase of oxygen consumption of the decomposing organic matter and the oxidation of chemical constituents (Boyd, [45]).

Nitrate is relatively non-toxic to Tilapias. However, a prolonged exposure to elevated levels of nitrate may decrease the immune response and induce mortality (Plumb, [46]). Inversely, nitrite is highly toxic to Tilapias because it disturbs the physiological function of the fish and leads to growth retardation (El-Sayed, [44]). Nitrite is toxic to many fish because it makes the hemoglobin less capable of transporting oxygen. Nitrite concentration for fresh water culture should be kept below 27 mg/L as nitrite (Popma and Masser, [43]). Nitrite showed very low levels (10.0 – 20.0 μg/l) than the corresponding values of nitrate (30.0 – 60.0 μg/l) due to the fast conversion of NO2

- to NO3

- ions by nitrifying bacteria (Abdel-Satar et al., [38]).

NO2- and NO3

- are within permissible limits of for fish.

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The PO43-

and total phosphorus (TP) concentrations ranged between 0.040-0.150 and 0.33-0.98 mg/L with mean values 0.092 and 0.584 mg/L, respectively. The PO4

3- and total phosphorus (TP) concentrations

showed lower rates than that measured in the same lake by Abdel-Satar et al., [38] and ranged between (0.235–1.074 and 0.743–2.925 mg/L) respectively. This reflects the indirect negative effect of algal blooming on the food web by decreasing the amount of edible phytoplankton that zooplankton and other primary consumer need to survive on (NOAA, [47]).

Table 2: Represent the physico-chemical parameters of studied water samples (n=9).

Minimum Maximum Mean ± S.E. Minimum Maximum Mean ± S.E.

pH 7.35 8.35 8.10±0.32 Ammonium (mg/L) 0.22 0.73 0.35±0.16

HCO3-(mg/L) 143.1 433.9 213.06±99.48 Calcium ( g/L) 0.3 0.55 0.43±0.07

CO3-2(mg/L) <0.20 25.7 16.61±10.36 Potassium ( g/L) 0.16 0.2 0.18±0.01

Alkalinity (mg/L) 168.7 433.9 229.67±89.88 Magnesium ( g/L) 0.67 1.42 1.04±0.25

DO (mg/L) 6.59 10.22 8.68±1.12 Sodium ( g/L) 5.55 7.68 6.4±0.75

Transparency (cm) 49.03 63 55.51±4.36 Chloride ( g/L) 10.33 14.8 11.95±1.33

EC (mmhos/Cm) 33.6 48.28 40.69±5.07 Nitrite (μg/L) 10 20 12.0±4.0

TS ( g/L) 33.38 42.06 37.92±2.87 Nitrate (μg/L) 30 60 41.0±10.0

TDS ( g/L) 30 38.62 34.70±2.80 PO43- (mg/L) 0.04 0.15 0.092±0.028

TSS ( g/L) 2.44 4.14 3.22±5.66 TP (mg/L) 0.33 0.98 0.584±0.233

Salinity (‰) 34 43 37.67±2.92 Sulfate (g/L) 4.19 6.15 5.30±0.66

Transparency, The water lake was turbid due to the Secchi disk < 70; Secchi disc levels (49.03-63.00 cm) corresponding to total suspend solid varied from 2.44 to 4.14 g/L with a mean values 3.22±5.66 g/L. The increase of total dissolved solids (TDS) is related the increased to the electrical conductivity (EC) and were found higher than the permissible limits 500 mg/L for TDS value. This may be attributed to the evaporation rate, the intrusion of drainage water and consumption of lake salts by EMISAL Company as mentioned by Abdel-Satar et al. [38]. Tilapias are tolerant to brackish water. The Nile Tilapia is the least tolerant of the commercially important species, but grows well at salinities up to 15 ppt. The Tilapia Zilli is the most tolerant of all Tilapia species, tolerating as high as 40% NaCl; the salinity of the water samples varied from 34 to 43 ‰ with a mean value 37.67±2.92‰; this means that Tilapia Zilli has ability to withstand this salinity and do well at the environment.

Calcium, potassium, magnesium and sodium concentrations ranged between 0.30-0.55, 0.16-0.20, 0.67-1.42 and 5.55-7.68 g/L with mean values 0.43±0.07, 0.18±0.01, 1.04±0.25 and 6.40±0.75, respectively. The major cations exhibited as the following order; Na

+>Mg

2+>Ca

2+>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, respectively. The major anions exhibited as the following order; Cl

->SO4

2-. 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).

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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 fat-content 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<0.01) for Cd (liver), Cu (liver), Fe (muscles and liver), Mn (muscles and liver), Pb (muscles and liver) and Zn (muscles and liver) with total metals in fish parts. The coefficients of activity of metals are significant (P<0.05) for Cd in muscles and Pb in brain. These data indicated that there is a tendency for the Tilapia Zilli to equilibrate with the water of Qarun Lake under given physico-chemical conditions prevailing in the media.

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Table 3: Regression equation between activity of trace elements in water samples and their total concentration in fish tissues.

Muscles log Cdtotal = 0.67 - 0.06 CdActivity in water - 0.04 pH R2= 0.73

log Mntotal = 3.74 + 0.14 MnActivity in water - 0.19 pH R2= 0.97

log Pbtotal = 1.86 + 0.16 PbActivity in water- 0.07 pH R2= 0.81

log Zntotal = 2.39 + 0.1 ZnActivity in water R2= 0.37

Liver

log Cd total = 1.148 + 0.12 CdActivity in water - 0.025 pH R2= 0.72

log Cutotal = 2.09 + 0.017 CuActivity in water - 0.057 pH R2= 0.97

log Fetotal =1.98 + 0.0011 FeActivity in water - 0.0261 pH R2= 0.98

log Mntotal = 2.24 + 0.01 MnActivity in water - 0.07 pH R2= 0.95

log Pbtotal =1.42 + 0.006 PbActivity in water - 0.13 pH R2= 0.87

log Zntotal = 2.27 + 0.7 ZnActivity in water R2= 0.87

Brain

log Pbtotal = 2.07 - 0.21 PbActivity in water R2= 0.56

3.3. Pesticides Residue in Water and Fish

The results of recovery experiment range from 85.1 to 99.3 % in water, the analytical procedures outlined for OCPs assessment in this study are adjudged reliable, reproducible and efficient. The range of response factors of 0.657 to 1.892 showed the separation efficiency of the GCECD equipment used for the identification and quantification of OCPs. The limit of detection (LOD) values for the OCPs ranged from 0.056 to 2.107 μg/L. The percentage relative standard deviation (%RSD) values for the recoveries of OCPs in water ranged from 2.63 to 5.59 %. These values showed that precision was better than 10 % RSD. The average recovery percentages of OPPs for fortified samples were determined and calculated for all OPPs. The overall mean of recovery percentages were found to be 85.6%, and 89.2% for water, and fish samples, respectively. All data were corrected according to the recovery percentage values.

Pesticide residues in different components out of 26 pesticides subjected to identification and determination in water and fish samples collected from the studied ecosystems. OC pesticides are higher than OP pesticides with respect to each water sample; Fig. 3 (A, B, C and D), because OC pesticides are resistant to microbial and photolytic degradation, and are therefore persistent in the environment (soil and water) where they are applied, while the OP pesticides are readily deactivated and degraded by microbial activities. This is consistent with Saad et al., [26] they found that organophosphorus compounds are quickly degradable in aquatic environment where the alkaline media accelerates their degradation.

Thirteen different OCPs were found in water, muscles, liver and brain; the highest average level belonged to β-BHC (14.89±0.57 µg/L), PP-DDD (62.71±8.95 µg/kg), endrin (52.82±2.59 µg/kg) and endrin (102.88±3.42 µg/kg) and the lowest were aldrin (0.29±0.04 µg/L), aldrin (< 0.1 µg/kg), aldrin (0.76±0.10 µg/kg), and aldrin (0.44±0.04 µg/kg), respectively.

OC pesticides found in Lake Qarun water, Fig. 3 (A), are α-BHC, γ-BHC, β-BHC, -BHC, heptachlor, aldrin, hepta-epoxide, γ-Chlordane, pp-DDE, endrin, PP-DDD, OP-DDT and PP-DDT at a mean concentration values are 1.39, 6.21, 14.89, 1.00, 3.27, 1.02, 0.29, 0.84, 1.52, 3.37, 0.92, 10.81, 1.23 and 2.40 µg/L, respectively. The order of OC pesticides concentration in water samples is β-BHC> PP-DDD> γ-BHC>-BHC> PP-DDT> γ-Chlordan> α-BHC> OP-DDT> Heptachlor> Endrin> Hepta-epoxide > Aldrin.

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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, <0.1, 9.31, 25.26, 40.17, 51.43, 62.71, 36.83 and <0.1 µg/kg, while in liver. Fig. 3(C) are 13.25, 13.34, 42.59, 16.37, 7.74, 0.76, 12.08, 28.59, 52.82, 94.75, 84.55, 62.11 and 1.07 µg/kg and in brain, Fig. 3(D), are 10.19, 15.84, 49.37, 13.39, 9.11, 0.44, 12.72, 35.38, 57.80, 102.88, 81.34, 46.57 and 0.72 µg/kg. The total OCPs were higher in liver and brain of fish samples than that which was in the water samples; that is as result of the higher pollution level in that lake and, therefore, leading to a higher bio-accumulation of pesticides in the fish samples, Fig. 3. The difference in patterns of these contaminants in brain, liver and muscles tissue may reflect difference in contaminant metabolism, content and composition of lipids, or the degree of blood perfusion in the various tissues (Metcalfe et al., [64]). Aldrin, dieldrin, chlordane, DDT, TDE, DDE, heptachlor, heptachlor epoxide in fish were lower than the permissible limit 0.3, 0.3, 0.3, 5, 5, 5, 0.3, 0.3 mg/kg recommended by Food Advisory Committee FDA and EPA, [65].

OP pesticides in water and fish tissue: OP pesticides such as cadusaphos, ethoprophos, Di-Syston, chlorpyrifos methyl, pirimiphos methyl, chlorpyrifos, phenthoate, fenitrothion and profenofos are found in water samples at concentration 2.12, 0.3, 0.83, 1.31, 2.85, 0.04, 0.83, 0.20 and 3.24 µg/L, respectively, Fig. 4 (A). While methamidophos, phorate diazinon, and triazophos showed undetectable concentrations of the analysed OP pesticides. The order of OPPs concentration in water samples was profenofos> pirimiphos methyl> 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<0.01) for α-BHC and hepta-epoxide and significant (p<0.05) for γ-BHC, with their concentrations in liver samples. For OPPs, correlation matrixes were recorded for cadusaphos, Di-Syston, pirimiphos methyl, fenitrothion, and profenofos between their concentration in water and liver tissue. The coefficient of activity of OPPs in water is highly significant (P<0.01) for pirimiphos methyl and significant (p<0.05) for Di-Syston, Fenitrothion, and Profenofos, with their concentrations in liver samples. These mean that cadusaphos, Di-Syston, pirimiphos, fenitrothion, and profenofos are strongly correlated with the same OPPs in water and fish liver and it shares a common origin with them in water and liver.

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Fig. 4: Minimum, maximum and mean values of different OPPs in water samples (n=9); where A: in water, B in muscle, C in liver and D in Brain.

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Table 4: Regression equation between OCPs and OPPs in water and liver tissue.

OCPs

α-BHC liver = 8.54 + 3.38 α-BHC water R2= 0.74

γ-BHC liver = -8.66 + 3.55 γ-BHC water R2= 0.46

Hepta-epoxide liver = 5.69 + 7.64 Hepta-epoxide water R2= 0.62

OPPs

Cadusaphosliver = -7.4 + 10 Cadusaphos water R2= 0.43

Di-Systonliver = 29.6 + 54.0 Di-Syston water R2= 0.55

Pirimiphosliver = 12.4 + 7.50 Pirimiphos water R2= 0.77

Fenitrothionliver = -1.65+ 59.17 Fenitrothion water R2= 0.44

Profenofosliver = 12.44 + 7.3 Profenofos water R2= 0.38

3.4. Bioaccumulation Factor (BAF):

Bioaccumulation factor (BAF) gives an indication about the accumulation efficiency for any particular pollutant in any fish organ. BAF is the ratio between the accumulated concentration of a given pollutant in any organ and its dissolved concentration in water and it was calculated according to Neuhauser et al., [66]; AbdAllah and Moustafa [67]; Authman and Abbas [68] using the following formula:

퐵퐴퐹 =퐶ℎ푒푚푖푐푎푙푐표푛푐푒푛푡푟푎푡푖표푛푖푛푓푖푠ℎ표푟푔푎푛

퐶ℎ푒푚푖푐푎푙푐표푛푐푒푛푡푟푎푡푖표푛푖푛푤푎푡푒푟

The Waste Minimization Prioritization Tool (WMPT) is a scoring system that was developed to rank chemicals based on their persistence (P), bioaccumulation potential (B), and human (HT) and ecological toxicity (ET). Chemicals are given a score of 1 (low concern), 2 (medium concern), or 3 (high concern) for P, B, and HT or ET. A score of 1 is assigned to BCF or BAF values less that 250; a score of 2 is assigned for BCF or BAF values from 250 to 1000; and a score of 3 is assigned for BCF or BAF values exceeding 1000 (Drexler et al., [69]). BAF values for trace elements in fish muscles, brain and liver were calculated using the above equation then compared to WMPT scoring system.

The bioaccumulation factor (BAF) of the studied metals, OCPs and OPPs showed that, the muscles of the studied fish maintained the lowest values. However, the highest values of BAF were found in the liver and brain, Fig. 5 (A, B and C).

The mean values for BAF in muscle were 8, 229, 67, 185, 34, 605, 0.61, 1.17, 2.4, 2.85, 6.97, 10.22, 14.39, 11.6, 64.11, 64.11, 6.00, 34.74, 4.55, 46.4, 44.44, 4.21, 8.29, 20.75, 27.77, 44.7 and 10.02 for cadmium, copper, iron, manganese, lead, zinc, α-BHC, γ-BHC, β-BHC, -BHC, heptachlor, hepta-epoxide, γ-Chlordane, pp-DDE, endrin, PP-DDD, OP-DDT and PP-DDT, cadusaphos, ethoprophos, Di-Syston, chlorpyrifos methyl, pirimiphos methyl, chlorpyrifos, phenthoate, fenitrothion and profenofos. In Liver, the mean values for BAF were 11, 320, 85, 300, 59, 738, 8.74, 2.11, 2.81, 4.79, 7.8, 2.57, 14.31, 16.22, 15.03, 103.63, 7.91, 59.57, 0.47, 6.66, 49.03, 86.01, 10.80, 11.82, 52.50, 27.44, 52.85 and 10.92 and in brain were 11, 424, 98, 203, 54, 650, 6.76, 2.5, 3.57, 3.95, 9.13, 1.47, 14.34, 20, 16.78, 114.04, 7.62, 0.3, 6.76, 55.87, 88.3, 13.04, 7.98, 125.00, 29.22, 86.7 and 12.65 for α-BHC, γ-BHC, β-BHC, -BHC, heptachlor, aldrin, hepta-epoxide, γ-Chlordane, pp-DDE, endrin, PP-DDD, OP-DDT and PP-DDT, cadusaphos, ethoprophos, Di-Syston, chlorpyrifos methyl, pirimiphos methyl, chlorpyrifos, phenthoate, fenitrothion and profenofos, respectively.

184


Fig. 5: Bioaccumulation factor for trace elements (A), organochlorine pesticides (B) and organophosphorus pesticides (C).

Comparing the data outlined in Fig. 5 for BAF with WMPT tool it shows that manganese (muscles and brain), lead (muscles, liver and brain), cadmium (muscles, liver and brain), iron (muscles, liver and brain), copper (muscles) were given score 1 since their BAF values were less than 250, while Mn (liver), zinc

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(muscles, liver and brain) and copper (liver and brain) were given score 2; it’s BAF values fall between 250 and 1000. These result indicated that the affinity of various metals to fish organs may differ. All different types of OC and OP pesticides were given score 1 because their BAF values were less than 250.

Organization for Economic Cooperation and Development (OECD) published guidance for classifying chemicals, which are hazardous to aquatic environments (OECD, [70]). The hazard classification schemes presented in the guidance incorporate, among other parameters, evidence of bioaccumulation value greater than or equal to 500 in fish as a basis for hazard ranking. Comparing the data in Fig. 5 with OECD ranking; the result refer to cadmium, copper, manganese, lead, iron, OCPs and OPPs are safe ranking, while zinc is considered hazard ranking.

4. CONCLUSION

The study of physical and chemical characteristics of water gives a considerable insight on water quality and on Tilapia Zilli quality for human use. The Lake was turbid, saline and salts composed the TDS of water Lake 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%). Visual MINTEQ showed that the studied trace elements were found in non-toxic form.

Trace elements concentration in Tilapia Zilli, generally higher levels were found in liver and brain and lower levels were recorded in muscles. The BAF indicated that the studied trace elements, OPPs and OCPs were in low to medium concentration in fish tissues. Cadmium, copper, iron, manganese, lead, OCPs and OPPs are safe compared to Organization for Economic Cooperation and Development (OECD), while zinc is hazard ranking.

This study also examined the use of a linear regression method as a technique for finding the dominant factors affecting metal uptake by fish tissues, and for predicting metal concentrations in fish tissues. The results showed activity of metal in water is the dominant factor influencing metal levels in muscles, liver and brain (only for Pb). Other factor as pH is contributed to the prediction of concentration in some cases. For OCPs (α-BHC, γ-BHC and hepta-epoxide) and OPPs (cadusaphos, Di-Syston, pirimiphos, fenitrothion, and profenofos) their concentration in liver depends on their concentration in water sample. These data indicated that there is a tendency for the Tilapia Zilli to equilibrate with the water of Qarun Lake under given physico-chemical conditions prevailing in the media.

5. RECOMMENDATIONS

The results of this study recommended implementation of all articles of the law regarding the protection of lakes and aquatic environment from pollution and treatment of wastewater before discharge to Qarun Lake. There is a need for constant monitoring for water quality of Qarun Lake in order to record any change in the quality and mitigate the outbreak of health problems and the adverse impact on the aquatic ecosystem since the Lake serve as source of fish for local inhabitants in that area

ACKNOWLEDGMENT: The authors are sincerely thankful to Prof. Dr. M. Mokhtar, director of Central Laboratory for Environmental Quality Monitoring (CLEQM), National Water Research Center for her helpful comments in water quality during this work. Many thanks also to Prof. Dr. Mostafa Abdel-Aly Nasef, Professor at Soils, Water and Environmental Res. Inst. Agric. Res. Center, Giza, Egypt for their help, facilities and encouragement during executing this work.

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REFERENCES

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