Republic of Iraq Ministry of Higher Education and Scientific Research University of Baghdad Effect of domestic sewage on water quality of Al-Gharraf River in AlHaay city A Thesis Submitted to the University of Baghdad, College of Science, Biology Department in partial fulfillment of the requirements for the Degree of Master of Science in Ecology and Pollution By Wisam Thamer Jabbar Al-Mayah B.Sc. Microbiology- 2009 University of Wasit Supervised by Prof. Dr. Muhammed Nafea Ali Al-Azzawi Tho Al-Huja 1434 October 2013 ِ ﺖ ﺒ ﺴ ﻛ ﺎ ﻤ َ )ﻇَ َﻬ َﺮ اﻟﻔَ َﺴ ُ ﺎد ﻓﻲ اﻟﺒَ ﱢﺮ واﻟﺒَ ْﺤﺮِ ﺑ َ َ َ ْ أَﻳﺪي اﻟﻨـﱠﺎِ س ﻟﻴ ِﺬﻳﻘَﻬﻢ ﺑﻌﺾ اﻟَ ِﺬي ﻋَ ِ ِ ﻠﻮا ﻤ ُ ُ ُ ْ َْ َ ِ ﱠ ﻮن ( ﻌ ﺟ ﺮ ﻳ ﻢ ﻬ ﻟَ َﻌﻠ ُ ْ َ ْ ُ َ & ﺻﺪق اﷲ اﻟﻌﻠﻲ اﻟﻌﻈﻴﻢ اﻟﺮوم )(٤١ Supervisor's certification We certify that this thesis was prepared under our supervision at the Department of Biology, College of Science, University of Baghdad for the degree of Master in Biology / Ecology and Pollution. Signature: Supervisor: Dr. Muhammed Nafea Ali Al-Azzawi Scientific degree: Professor Address: University of Baghdad - College of Science Department. of Biology. Date: 1/ 9 /2013 Certification of the head of Biology Department In view of the available recommendations of the supervision, I found this thesis for discussion by the examining committee. Signature: Name: Dr. Sabah N. Alwachi Scientific degree: Professor Address: University of Baghdad - College of Science Head of Biology Department. Date: 1/ 9 /2013 Certification I certify that the thesis entitled "Effect of Discharging Sewage of Al-Haay City on the Water Quality of Al-Gharraf River" was prepared by Wisam Thamer Jabber has been evaluated. It was written in a good English language therefore, it is accepted for debate by scientific committee. Dr. Sedik Ahmed Kasim Reviewer Environmental Researches Center University of Technolog , Baghdad, Iraq. Committee certification We the Examining committee, certify that we have read this thesis entitled " Effect of domestic sewage on the water quality of Al-Gharraf River in Al-Haay city " and as examined committee we examined the thesis of the student (Wisam Thamer Jabbar Al-Mayah) in its context and that in our opinion it is adequate for awarding the degree of Master in Biology / Environmental and Pollution. Signature: Name: Dr. Khalid A. Rasheed Scientific degree: Assistant Professor Address: University of Al-Nahrain – Biotechnology Researches Center Date: 17 /11 /2013 Chairman Signature: Name: Dr. Hashim H. Kareem Scientific degree: lecturer Address: University of Wasit College of Agriculture Date: 19 /11 /2013 Member Signature: Name: Dr. Adel M. Rabee Scientific degree: Assistant Professor Address: University of Baghdad - College of Science Date: 17 /11/2013 Member Signature: Name: Dr. Muhammed N. Ali Al-Azzawi Scientific degree: Professor Address: University of Baghdad - College of Science Date: 17/11/2013 Member Advisor Approved by the College Committee of post graduate studies. Signature: Name: Dr. Saleh M. Ali Scientific degree: Professor. Dean of College of Science. Date: / /2013 Dedication I dedicate all my efforts to…… Whom I worship……...For my merciful Allah The leader of my Life..…Prophet Mohammed And his family Mohammed…… To my life love……..…..……….My parents The candles those I honor….…...My Brothers To everyone help me to do this work…… I introduce my work with respects Wisam Al-Mayah 2013 Acknowledgement Praising to Allah who gave me health, strength, and facilitated the way for me to accomplish this work. Sincerely, I would like to thank my advisor Dr. Muhammad Nafea Ali Al-Azzawi for their continuous confidence, advice, patience, and for their encouragement. My real gratitude and special thanks to Dr. Ahmed J. Al-Azawi and Dr. Adel M. Rabee for providing me valuable advices and right guidance along all the study years. I extend warm thanks to Dr. Nabeel Raheem and Dr. Nasr Noori for his assistance in statistical analysis of the data and encouragement in completing this work. Finally, I would like to express my gratitude to the all teams and individuals who supported me throughout this study: · College of Science and Department of Biology Stuff for their cooperation and practical help, specially my friend, the PhD student Ali Kareem, Mahmood Basil and Salam Al-Helaly. · College of Science and Department of Chemistry Stuff, specially Miss Munira K. Ahmed. · The central environmental laboratory Stuff in the Ministry of Environmental, especially Mrs Siham Ibraheem. · The water laboratory Stuff in Directorate Wasite of Water. · Last but not least, I gratefully acknowledge the encouragement of all my friends, and other people who are not mentioned here, my deepest gratitude goes to my beloved parents and brothers for their love, moral support, invariable care and encouragement throughout the study period. Wisam Thamer Al-Mahay [email protected] Summary… The aim of the present study is to know the effect of raw sewage from the Al-Haay city on some of the chemical, physical and bacteriological properties of Al-Gharraf River. The Al-Gharraf River located in the south-eastern sector of Iraq and surrounded by vast and agricultural lands. The river receives most of the wastewater coming from many activities including industrial, agricultural, and domestic wastewater. Associated with the development of the area, the increase of pollutants into the river has been a recent cause for alarm. Five sampling stations were selected along the Al-Gharraf River .The first is located at 2 km of AL-Haay City as a control. The second is situated at a distance of 2 km away from the first and represented sewage discharge station.The Station 3 was about 2 km from station 2 represented the raw water uptake of AL-Bashaer station for drinking water.The station 4 was about 4 km from station 2 and the last station is located at 8 km apart from the second station. Monthly sampling was carried out from October 2012 till July 2013,two samples were taken each month . The results obtained showed that the values of turbidity , Electrical conductivity, salinity, total dissolved solid, total suspended solid, dissolved oxygen , biological oxygen demand , total Hardness , chlorides, sulphate , nitrate, phosphate , total bacterial count, total coliform bacteria, Faecal coliform, total Streptococcus and faecal Streptococcus in the river were found to be higher at autumn and winter and lower at spring and summer. I This study has found that: Air and water temperature values varied from 16-42 and 11-31 0 C respectively. Also,water current values were varied from 0.37-0.81 m/sec, electrical conductivity values varied from 825-1450 µs/cm with Salinity 0.52-0.93 ppt, The total dissolved solid 545.3 – 957 mg / L, Total suspended solid values ranging from 38-278 mg / L with turbidity 30-177 NTU. It was found that the waters of Al-Gharraf River is alkalinity with pH ranged between 7.03 - 8.3 with a reasonable ventilation as the oxygen values recorded varied monthly at winter months 6.3-10.38 mg / L . The biological oxygen demand values were found to be higher at some stations 1 -7.01 mg / L . The total hardness ranged between 306- 496 mg/L, The chlorides values varied from 89-184.6 mg / L, the sulphate values ranged between 172.42 - 360 mg/L. Nitrate values varied from 5.7 -15. 76 mg/L, and the phosphate values ranged between 0.50 -0.13 mg/L. The study results also showed that the heavy metals concentrations (cadmium, lead and zinc) were 0.001-0.099 ppm, 0.004- 0.32 ppm and 0.025- 1.1 ppm, respectively. Concentrations of these metals of Al-Gharraf River showed seasonal variations during the study period and they are exceeding permissible limits for Iraqi standard specifications and WHO standard for drinking water except Zn . This study has shown that the highest total bacterial count was recorded at the fifth station during winter 2013 was 75000 cell/1ml , whereas the lowest value was found during summer 2013 was 100 cfu/1ml. Total Coliform and Fecal Coliform bacterial counts were ranged between 290-34000 cfu /100 ml and 220-33000 cfu/100 ml , respectively. However, total streptococcus and faecal streptococcus counts were 230 -32600 cfu/100 ml and 200-21000 cfu/100 ml , respectively. II List of contents No. 1.1. 1.2. 1.3. 1.3.1. 1.3.2. 1.3.2.1. 1.3.2.2. 1.3.2.3. 1.3.2.4. 1.3.3. 1.3.4. 1.3.4.1. 1.3.4.2. 1.3.5. 1.3.5.1. 1.3.5.2. 1.3.5.3. 1.3.5.4. 1.3.5.5. 1.3.6. 1.3.6.1. 1.3.6.2. 1.3.6.3. 1.3.6.4. 1.3.6.5. Title Summary List of contents List of figures List of tables List of appendices List of abbreviation Chapter One Introduction and literatures review Introduction Aims of the study Literatures review Water pollutants Types of water pollutants Domestic Sewage Industrial waste Agricultural waste Other pollutants Organic Pollution in the Rivers Domestic Sewage General Concept Chemical structure of raw sewage Heavy Metals General Concepts Heavy Metals in Aquatic Systems Cadmium (Cd) Lead (Pb) Zinc (Zn) Bacteriological Indicators of Fecal Contamination General Concepts Total Bacterial Count (TBC) Total Coliform (TC) Fecal coliforms (FC) Total Streptococci(TS) and Fecal Streptococci(FC) III Page I III VI VIII IX IX 1 2 3 3 3 3 3 4 4 4 5 5 7 9 9 10 11 12 13 14 14 15 15 16 17 No. 2.1. 2.1.1. 2.1.2. 2.1.3. 2.1.3.1. 2.1.3.2. 2.1.3.3. 2.1.3.4. 2.1.3.5. 2.2. 2.2.1. 2.2.2. 2.2.3. 2.2.4. 2.3. 2.3.1. 2.3.2. 2.3.2.1. 2.3.2.2. 2.3.2.3. 2.3.2.4. 2.3.2.5. 2.3.3. 2.3.3.1. 2.3.3.2. 2.3.3.3. 2.3.3.4. 2.3.3.5. 2.3.3.6. 2.3.3.7. 2.3.3.8. 2.3.3.9. 2.3.3.10. 2.3.3.11. 2.3.4. 2.3.4.1. Chapter Two Materials and methods Study Area AL-Haay City Al-Gharraf River Sampling stations First station Second station Third station Forth station Fifth station Materials Apparatus and Instruments Chemical Material Culture Media Reagents Methods Sample collection Field measurement Air and Water temperature Water Currents Hydrogen ion concentration Electrical conductivity (EC) Dissolved oxygen (DO) Laboratory measurement Biochemical oxygen demand (BOD5) Salinity Turbidity Total Dissolved Solids (TDS) Total Suspended Solids (TSS) Total Hardness(T.H) Chloride ion (Cl-) Sulphates (SO4) Nitrate (NO3) Reactive Phosphate (PO4) Heavy metals tests Microbial Tests Total Bacterial Count(TBC) IV Page 18 18 18 20 21 22 23 23 24 25 25 26 26 27 28 28 29 29 29 29 29 29 30 30 30 31 31 31 31 32 32 32 33 33 33 33 2.3.4. 2. 2.3.4.3. 2.3.4.4. 2.3.5. No. 3.1. 3.1.1. 3.1.2. 3.1.3. 3.1.4. 3.1.5. 3.1.6. 3.1.7. 3.2. 3.2.1. 3.2.2. 3.2.3. 3.2.4. 3.2.5. 3.2.6. 3.2.7. 3.2.8. 3.2.8.1. 3.2.8.2. 3.2.8.3. 3.3. 3.3.1. 3.3.2. 3.3.3. 3.3.4. 3.3.5. Total Coliform count(TC) Thermotolerant (Faecal) Coliform Bacteria(FC) Streptococci and Faecal Streptococci(TS & FS) Statistical analysis. Chapter Three Results and discussions Physical Characteristics . Air and Water Temperature. Water Currents. Electrical Conductivity E.C. and Salinity. Total Dissolved Solids (TDS). Turbidity. Total Suspended Solids (TSS). Hydrogen ion concentration (pH). Chemical Characteristics. Dissolved Oxygen (DO). Biochemical Oxygen Demand (BOD5). Total hardness (TH). Chlorides (Cl-). Sulphate (SO4). Nitrate(NO3-2). Phosphate (PO4-3). Heavy metals. Cadmium (Cd). Lead (Pb). Zinc (Zn). Bactriological Characteristics. Total Bacterial Count (T.B.C). Total Coliform (TC). Faecal Coliform (FC). Total Streptococcus (TS). Faecal Streptococcus (FS). Conclusions and Recommendations Conclusions Recommendations References Appendices V 34 34 34 34 Page 35 35 39 40 42 44 46 47 49 49 51 53 55 57 59 61 63 63 66 68 70 70 73 75 77 79 81 82 84 119 List of figures No. Title Page 1 Map of Al-Gharraf River in Haay city . 20 2 Sampling stations on Gharraf Rive at Haay city. 21 2-a Station 1. 21 2-b Station 2. 22 2-c Station 3. 23 2-d Station 4. 24 2-e Station 5. 24 Seasonal variation of air temperature (oC) in AL-Gharraf 3 36 River during study period. Seasonal variation of water temperature (oC) in AL-Gharraf 4 River during study period. 36 Seasonal variation of water currents in AL-Gharraf River 5 40 during study period. Seasonal variation of electrical conductivity in AL-Gharraf 6 7 42 River during study period. Seasonal variation of salinity in AL-Gharraf River during 42 study period. 8 Seasonal variation of total dissolved solids in AL-Gharraf 44 River during study period. 9 Seasonal variation of turbidity in AL-Gharraf River during 45 study period. Seasonal variation of total suspended solids in AL-Gharraf 10 47 River during study period. Seasonal variation of pH values in AL-Gharraf River during 11 49 study period. VI 12 Seasonal variation of dissolved oxygen in AL-Gharraf River 51 study period. Seasonal variation of biochemical oxygen demand in AL13 53 Gharraf River during study period. Seasonal variation of total hardness in AL-Gharraf River 14 55 during study period. Seasonal variation of chloride ions in AL-Gharraf River 15 16 57 during study period. Seasonal variation of sulphate ions in AL-Gharraf River 59 during study period. Seasonal variation of NO3 in AL-Gharraf 17 River during 61 study period. Seasonal variation of PO4 in AL-Gharraf River during study 18 63 period. Seasonal variation of cadmium in AL-Gharraf River during 19 65 study period. Seasonal variation of lead in AL-Gharraf River during study 20 68 period. Seasonal variation of zinc in AL-Gharraf River during study 21 70 period. Seasonal variation of total bacterial count in AL-Gharraf 22 72 River during study period. Seasonal variation of total coliform in AL-Gharraf River 23 75 during study period. Seasonal variation of faecal coliform in AL-Gharraf River 24 77 during study period. Seasonal variation of total streptococcus in AL-Gharraf 78 25 River during study period. 26 Seasonal variation in faecal streptococcus in AL-Gharraf VII 80 River during study period. List of tables No. Title Page 1 The percentage for the household waters uses. 8 2 A list of instruments that were used in field and lab work 25 3 A list of chemical material that were used in lab work. 26 4 A list of culture media that were used in lab work. 27 5 A list of reagents that were used in lab work. 27 6 Minimum and maximum ( First Line), mean and standard 37 deviation ( Second Line), for physical and chemical characteristics at study stations during 2012-2013. 7 The correlation among water parameters. 38 8 Minimum and maximum (First Line), mean and standard 65 deviation (Second Line), for heavy metals studied (Cd, Pb, and Zn) at study stations during 2012-2013. 9 The correlation among some water parameters and heavy 66 metals. 10 Minimum and maximum (First Line), mean and standard deviation (Second Line), for Bacteriological characteristics at study stations during 2012-2013. 72 11 The correlation among some water parameters and bacteria number. 73 VIII List of appendices No. Title Page 1 Comparison between some water quality parameters of AlGharraf River with the Iraqi and international standards. Comparison between some water quality parameters of AlGharraf River with the local and international Rivers . Water Quality according to United State stander (ASCE) for raw water quality . Comparison between concentrations of dissolved heavy metals in Al- Gharraf River water with world and Iraqi standards by ppm unit. Comparison between concentrations of dissolved heavy metals in Al- Gharraf River with local and international Rivers by ppm unit (ND: Not Detected ) . Comparison between bacteriological characteristics of AlGharraf River with with local and international Rivers. 119 2 3 4 5 6 120 122 122 123 124 List of abbreviations Acronyms Meaning ACS American Cancer Society APHA American Public Health Association APEGBC Association of Professional Engineers and Geoscientists British Columbia CFU Colony forming unit EPA Environmental Protection Agency EEA European Environment Agency EQS Environmental Quality Standards USEPA United States Environmental Protection Agency USGS United States Geological Survey UNEP United Nations Environmental Programme WHO World Health Organization WASC Waterwatch Australia Steering Committee IX Chapter one Introduction and Literature Review Chapter one Introduction and Literature Review 1.1. Introduction. Water is the most important natural resource and essential for life, as it provides habitat for diverse type’s of aquatic life in rive rs, lakes and oceans, and it covered about 70% of the earth surface. It constitutes more than 2.5 times that of the earth main land. Also it is known the water constitutes about 70% of the human body. Availability of water resources in countries is a principal factor for the development. Therefore, it is necessary to protect it from the pollution problems and manage it uses. (Cheepi, 2012; Ahmed and Kheder, 2009) Approximately, 20% of the world’s population lacks safe drinking water and nearly half the world population lacks adequate sanitation. This problem is acute in many developing countries, which discharge an estimated 95% of their untreated urban sewage directly into surface waters. Iraq which is one of the nine middle eastern countries have insufficient fresh water (Pimental et al., 2004). Surface water bodies are affected because they received water from wastewater (point source), irrigated drainage and runoff (non-point source). Impacts depend on the extent that wastewater has been in contact with soil, on that type of water body, and their use, as well as the hydraulic retention time and the part played within the ecosystems (Jimenez, 2006). The unscientific disposal of the wastewater (sewage) has caused immense environmental problems not only to the aquatic environment but also to human beings world wide. This problem started long back but intensified during the last few decades, and now the situation has become alarming in Iraq (Mohammed et al., 2012). During the past three decades, 1 Chapter one Introduction and Literature Review the effects of municipal sewage and effluents, the point source pollution, on the water quality of canals, streams and rivers have received some attention but very little has been reported about the temporal effects of the sewage on the water quality of the receiving water bodies (Kumar and Reddy, 2009). The term "sewage" means gray water that generated by man activities in the process of meeting his various living requirements. The sewage can be described as wastewater from a community. Wastewater refers to spent or used water containing dissolved or suspended matter. Wastewater from residential areas is referred to as domestic sewage (Porteous, 2000; EPA, 2012; Kamusoko and Musasa, 2012). It consists of pollutants such as human wastes (faeces and urine) and sludge. The term sludge refers to wastes arising from food preparation and cleaning of kitchen utensils, laundry and floor drain wastes. Sewage from various homes and institutions (private and public) in a community constitute municipal sewage (Girija et al. 2007; Uwidia and Ademoroti, 2011). 1.2. Aims of the study. The current study was designed to achieve the following objectives: 1. Determination the effect discharge of sewage of the Al-Haay city on physical, chemical and biological characteristics of Al-Gharraf River. 2. Determination of some bacteria numbers included Total Bacterial Count, Total Coliforms, Fecal Coliform, Total streptococci and Fecal streptococci) as indicators for water pollution of Al-Gharraf River. 3. Determination of some heavy metals levels (cadmium, lead, and zinc) as indicators for water pollution of Al-Gharraf River by heavy metals. 4. According to determined above parameters complete evolution of river pollution. 2 Chapter one Introduction and Literature Review 1.3. Literature Review. 1.3.1.Water pollutants. Aquatic environment exposed to various types of pollutants such as heavy metals , pesticides, detergents, petroleum products , and other materials, in additional to industrial, agricultural and medical wastes may lead to a negative impact on public health and biodiversity (Maitera et al.,2010; Osibanjo et al.,2011). The danger of industrial waste being substances toxic to humans and other organisms , and lve made many studies identify toxic these residues using methods used in Environmental toxicology , which deals study the harmful effects of pollutants and knowledge effects chemicals in environmental regulations and the reasons and magnitude of these affects to take preventive and remedial measures possible (Kanu and Achi, 2011; Kenneth and William, 2012 ). World health organization (WHO), has reported that 2.3 billion people in 2025 would suffer from an acute shortage of potable water unless significant steps have to be considered at least reduce water pollution (WHO, 1996a; WHO, 2004). 1.3.2.Types of water pollutants. 1.3.2.1. Domestic sewage wastes. This type of wastewater originates from residential locations and other municipal activities such as water are heavily contaminated with various organic and inorganic pollutants (Reddy et al.,2011; Geetu and Surinderjit, 2012 ). 1.3.2.2. Industrial wastes. This type of wastewater including different types of pollutants which are : 3 Chapter one v Introduction and Literature Review Physical contaminants, such as some remnants of paper mills, dyes, tanning and textiles which cause change in color of water (ICIMOD, 2007; Kenneth & William, 2012). v Chemical contaminants, such as solid waste, hydrocarbons, oil products and inorganic chemicals such as heavy metals and dissolved gases which affect on values of hydrogen ion (pH) and biochemical oxygen demand (BOD5) in water (Jay and Keely, 2005; Sultana et al.,2013). 1.3.2.3. Agricultural wastes. This type of wastewater includeing nutrients, chemical fertilizers and organic pesticides which reach into rivers and lakes through irrigation and drainage water in soils adjacent to water bodies (Bradl , 2005; Sada, 2010). 1.3.2.4. Other pollutants. There are other types of pollutants as radioactive pollutants and thermal pollutants and acid and alkaline pollutants and gases pollutants as chlorine and ammonia and negative ion as fluorides and sulfate (EEA, 2012). 1.3.3. Organic pollution in the rivers. The term "Organic pollution" refers to the pollution that is happening to the water and resulting from organic materials biodegradable naturally by microorganisms, and which can pose serious environmental health problems (Al-sarwi, 2008; Uwidia and Ademoroti, 2011). Natural organic matter (NOM) found in all the surface water such as aromatic and large allophatic compounds. These materials differ due to weather changes, water system and a number of other environmental factors (Young and Ulrich, 2008; Matilainen and Sillanpaa , 2010). 4 Chapter one Introduction and Literature Review The most important source of organic matter in the water is municipal sewage due to human biological activity and other organic household wastes such as detergents and wash liquids releasing various nutrients (Goel, 2008) . High nutrients concentration leads to eutrophication,a condition characterized by significant diurnal variation in dissolved oxygen concentration and excessive algal growth (Sengupta, 2006; Wang et al.,2013). Studies indicate that most of the world rivers are contaminated , but to varying degrees. For example the Rhine River becomes polluted even called the longest stream of dirty water in the world (Cited inAlHaidarey, 2003). Many millions more suffer from frequent and debilitating water borne diseases. About half of the inhabitants of developing countries do not have access to safe drinking water and 73% have no sanitation, some of their wastes eventually contaminate their drinking water supply leading to a high level of risks (Maitera et al., 2010 ; Charity et al., 2012). In Iraq proved study Al-Mayaly (2000) and Al-Rubai'y (2007) that the Diyala River has significant effect on Tigris River due to high levels of organic pollution introduced from sewage station such as Al-Rustumiya station and Al-Jaish canal. 1.3.4.Domestic Sewage. 1.3.4.1.General Concept. The impact of sewage disposed on the environment has become a threat to the existence of plant, animals and ultimately human life. Pollution is causing widespread concern and has become an important area of interest in the field of modern research (Longe and Ogundipe, 2010; Mishra, 2012 ). 5 Chapter one Introduction and Literature Review Discharge of untreated sewage water into water body is a common practice in many countries. This is the common cause for pollution of surface and groundwater due to lack of proper wastewater plants in Iraq. In general, the municipal wastewater is a combination of the water and carried wastes removed from residential, institutional and commercial establishments together with infiltration of water, surface water and runoff water(Gautam et al.,2012; APEGBC, 2013). The domestic sewage contains a large variety of inorganic and organic impurities and pathogens bacteria and viruses resulting in waterborne diseases. Water is organically polluted by high molecular weight compounds such as sugars, fats, oils, proteins released from domestic and industrial wastes and causing unpleasant odor, color, taste and algal growth (Chavan and Dhulap, 2012 ; Puerari et al., 2012). Sewage effluents are often the main factors responsible for deterioration of water quality as they have a major impact on the chemical loads received by surface water bodies ( Drolc et al., 2007; Picot et al., 2009). High levels of nitrogen and phosphorus are generally found in sewage effluents, and contribute to high eutrophication levels and reduce river functionalities (David et al., 2012). Discharge points of industrial and municipal wastewater are continuous sources of pollution for rivers, where making the rivers not always able to absorb them and, compromising their quality. Since flow discharges vary with the hydrological conditions, the dilution may or may not occur. This is important because the dry season can last several months in arid and semi-arid areas and intermittent rivers and sewage effluents can contribute up to 100 % of the inflow during dry periods (David et al., 2011; Garcia et al., 2012). 6 Chapter one Introduction and Literature Review 1.3.4.2. Chemical structure of raw sewage. It means the water previously used or resulting from population centers and industrially , are not suitable for consumption and classified according to their source :wastewater ,domestic, industrial and agricultural( Kumar et al., 2012). Agricultural wastewater is chemical fertilizers and organic used in agriculture such as pesticide spraying and fertilizer application, which arrive to rivers through drainage. Also, detergents consist of different chemical components such as surfactants, soaps, bleaches and enzymes that reach rivers through sewage (Geetu and Surinderjit, 2012; Zelenakova et al., 2013). Industrial processes are causing the production of large amounts of toxic and stable pollutants, which are all collected into the water out coming from the plant. The disposal of these contaminated effluents into receiving waters can cause environmental damages, directly influencing the aquatic ecosystem and even human being (Spina et al., 2012; Sultana et al., 2013). Also, textile and pharmaceutical effluents are usually recalcitrant to the standard biological treatments, due to the complex aromatic compounds, the extreme chemico-physical parameters and the presence of an autochthonous bacterial microflora (Hai et al., 2008; Rosales et al., 2011). The domestic and municipal wastewater are composed of 99.9 % water and remaining 0.1 % suspended, colloidal and dissolved solids (EPA, 2005; Gautam et al.,2012). These contaminants consist of solids is 30% inorganic materials and 70% of organic materials include 65% proteins and 25% carbohydrate and 10% fat (Amer , 2006) . These components vary depending on the purpose of the water uses, as in the following table (Al-Saadi , 2006): 7 Chapter one Introduction and Literature Review Table (1): The percentage of the household water uses. No. Use type Percentage 1. Drinking 1% 2. Food cooking 3% 3. Clothes wash 13% 4. Dishes wash 13% 5. Toilet 30% 6. Bathes 40% Domestic sewage contains on a number of pollutants causing bacterial diseases such as cholera, salmonella, shigellas ; viral diseases such as hepatitis, enteroviruses, poliovirus, and other parasites diseases such as protozoan's, helminthes. All these diseases lead to physiological and even psychological problems that may lead to death in some cases (Kahun and Yardley , 2007; Adingra et al., 2012). Also domestic sewage may contain phosphorus and nitrogen which allows the growth of some undesirable algae species particularly in locations where water static terms lead to the formation of a layer of the algae on the surface of the water emit unpleasant odors and change the taste of water , as well as lead its growth to increased demand for oxygen and therefore reduce its concentration in the water (EPA 2012a; Loe et al. 2012) . However, sewage may contain heavy metals at considerable levels which gives rise to toxic concentrations in the body. Some of these metals such as arsenic, cadmium and chromium may act as carcinogens while such as mercury and lead are associated with developmental abnormalities in children (Adekunle et al., 2012; Preeti and Fazal, 2013). 8 Chapter one Introduction and Literature Review 1.3.5. Heavy Metals. 1.3.5.1. General Concepts. The term "heavy metals" refers to any metallic element that has a relatively high density and is toxic or poisonous even at low concentration (Duruibe et al., 2007) also “Heavy metals” are defined as all metals of atomic weight greater than sodium with specific gravity of more than 5.0 g/cm3 (Beasley & Kneale, 2007; Rahimi et al., 2013). The presence of heavy metals in the aquatic environment has been of great concern because of their toxicity at lower concentrations (Uba et al., 2009; Nasrabadi et al., 2010). According to Richardson & Niebaer (1980), these metals can be divided into three main groups (Raikwar et al. , 2008): · Macro elements, which includes a group of elements that are needed by living organisms for catalyzing their biological systems and represent as important factors for metabolism, such as calcium (Ca), sodium (Na), potassium (K), magnesium (Mg), chloride (Cl), and phosphor (P). · Essential elements, which includes a group of elements that are needed by living organisms in trace amounts and play significant roles in the biological systems but have toxic effects if they one present in concentrations more than organisms needing, such as chromium (Cr), zinc (Zn)، iron (Fe), manganese (Mn), copper (Cu), cobalt (Co), and selenium (Se). · Non-essential elements, which includes a group of elements haven’t exact roles in biological systems and consider as toxic agents, such as arsenic (Ar), barium (Ba), cadmium (Cd), lead (Pb), lithium (Li), mercury (Hg), and nickel (Ni). 9 Chapter one Introduction and Literature Review In case of toxicity, these metals can be classified into three groups according to Neis (1999): · Low toxic elements, which include molybdenum (Mo), iron (Fe), and manganese (Mn). · Middle toxic elements, which include zinc (Zn), nickel (Ni), chromium (Cr), copper (Cu), cobalt (Co), vanadium (V), as well as tungsten (W). · High toxic elements, which include mercury (Hg), lead (Pb), cadmium (Cd), arsenic (As), silver (Ag), antimony (Sb), and uranium (U). 1.3.5.2. Heavy metals in aquatic systems. Heavy metals in aquatic system can be in the following forms (Valois et al., 2010; Idriss and Ahmad, 2012): 1. Dissolving form. This form of metals in case of free ionic, organic, or non-organic, and can pass through the filters with pouring equal to 0.45 micron. 2. Suspending form. This form of metal with diameter more than 0.45 microns and it may be biotic such as Zooplankton or Phytoplankton or abiotic such as organic or non organic compounds.and can be divided to follow: v Residual metals. Including elements which be within silica parts such as silver and mercury . v Exchangeable metals. Including undissolved heavy metals and not be within silica parts. 10 Chapter one Introduction and Literature Review 1.3.5.3. Cadmium(Cd). Cadmium (Cd) is a soft, silver-white metal, and is always associated with zinc. It has number is 48, atomic weight 112.411, density quality 8.64 g/cm3, melting point 320.9°C and boiling point 765°C. It is usually found as a mineral combined with other elements such as oxygen (cadmium oxide), chlorine (cadmium chloride), or sulphur (cadmium sulphate, cadmium sulphide) ( Raikwar et al. , 2008; Lawrence and Alex, 2012 ). Cadmium was used firstly as a fungicide for golf courses and home lawns, after that it has been used widely by many industries such as pigments, metal coatings, paints, plastics, as well as fertilizers which is used to grow food that may contain cadmium. In addition to all of these industries, the manufacture of nickel-cadmium batteries represents the most frequently used of cadmium (Faulkner and Schwartz, 2009; AbdulTalib et al., 2013). Inhaling high levels of cadmium can cause irritation, with shortness of breath, cough, chest pain, abdominal pain or a choking sensation and severe lung damage as well as a buildup of fluid in the lungs (Toman et al. ,2005; Harber et al., 2010). On the other hand, ingested cadmium at high levels in foods or water, can cause stomach irritation, nausea, vomiting, high blood-pressure, diarrhea, convulsions, liver disease, brain damage, headache, fever, weakness, and kidney problems which can be fatal, and sometimes death (Mascilak, 2011; Lawrence and Alex, 2012) In Japan the discharge of wastewater into Jintsu River in Toyama city from fluxing and mining factory and used the river water in irrigation rice fields lead to increase Cd in 1947 causing Itai itai disease and mortality for more than hundred people late in 1965 and syndromes appeared in bones (Al -Saadi, 2006) 11 Chapter one Introduction and Literature Review 1.3.5.4. Lead (Pb). Lead (Pb) is a bluish or silvery grey soft metal with atomic number 82 ; atomic weight 207.19; specific gravity 11.34, melting point 327.5 °C and boiling point 1749°C. It is the most common industrial metal that has become widespread in air, water, soil and food. Lead is slightly soluble in water and is transported mainly through the atmosphere. It behaves like calcium in the body and accumulates in bone, liver, kidney and other tissues ( Raikwar et al. , 2008; Singh et al., 2012). Lead can be considered as one of the four metals represent extreme seriousness on human health. It has been used in various industries such as paints, ceramics, shots, water pipes, food storage cans, solders, gasoline, electrical batteries, and cosmetics such as kohl. Lead was also used in pesticides before the 1950s. The half-life of lead differs in each organ, ranging from 25–40 days in erythrocytes, 40 days in soft tissues, and along half-life in the bone reach to 28 years (Hocking, 2005 ; Faulkner and Schwartz, 2009). Lead is a cumulative tissue poison and gets stored in different parts of the body especially in bones, liver, kidney and brain. Besides, direct ingestion of lead leading to increased blood levels, vomiting, higher blood pressure, headache, weakness, and coma. Accumulated lead in the body also acts as a significant source of blood lead burden. Lead may cause irreversible neurological damage, renal disease, cardiovascular effects, and reproductive system toxicity (Swarup et al., 2005; Yen et al., 2010). Recently, there are evidences that lead is carcinogenic. In addition to all these effects, lead may cause changes in gene expression if child has been exposed to it as well as other health problems for the later in life (ASC, 2010; Dekhil et al., 2011) 12 Chapter one Introduction and Literature Review 1.3.5.5. Zinc (Zn). Zinc (Zn) is the metallic element bluish-white in color ,subject to form when heated,, its atomic number (30), atomic weight 65.409, density 7.14, melting point 419.53°C, boiling point 907°C, a white or blue in color (Trunk et al, 2011). It is one of the most elements prevalent on soil, air and water. Also it may necessary in food being an essential element and small amount would be required for human beings to organize biological physiology. Also, it is used in the process of making protein a catalyst for many of the enzymes that regulate cell growth and the level of hormones , and also contributes to the regulation of gene expression (Dimirkou , 2007 ). Health and environmental impacts of zinc toxicity are very common such as nausea, vomiting and damaging of the pancreas. However, toxicity of zinc becomes more severe when present with other heavy metals, such as cadmium, in water because it has synergistic effect with these metals (Hussoun, 2006; EPA, 2012). The main sources of zinc are mining operations, secondary metal production, plastics, coal combustion, ceramic, batteries, rubber tire wear and phosphate fertilizers, also enters in some alloys such as bronze , pesticides and cosmetics protection against sunburn and inhibitors sweating and some types of medicines (Salim et al., 2003; Solberg, 2009). 13 Chapter one Introduction and Literature Review 1.3.6.Bacteriological Indicators of Fecal Contamination. 1.3.6.1.General Concepts. Fecal indicator bacteria are used to assess the microbiological quality of water. Although these bacteria are not typically disease causing, they are associated with fecal contamination and the possible presence of waterborne pathogens. The density of indicator bacteria1 is a measure of water safety for body-contact recreation or for consumption. Fecal material from warm-blooded animals may contain a variety of intestinal microorganisms such as bacteria, viruses, and protozoa that are pathogenic to humans resulting in several types of diseases including gastroenteritis, typhoid fever, cholera, hepatitis and dysentery (Myers et al., 2007; WHO, 2010). Bacteriological tests for specific indicator bacteria are used to assess the sanitary quality of water and sediments and the potential public health risk from gastrointestinal pathogens carried by water. The suitability of indicator organisms for fecal contamination in water is ranked according to a specific set of criteria, described below (Bitton,2005; Zheng et al.,2013): 1. It should be a member of the intestinal microflora of warm-blooded animals. 2. It should be present only when pathogens are present, and absent in uncontaminated samples. 3. It should be present in greater numbers than the pathogen, and densities correlated with fecal contamination. 4. It should be at least equally resistant as the pathogen to environmental factors and to disinfection in water and wastewater treatment plants. 5. It should be survives as long as, or longer than, pathogens. 14 Chapter one Introduction and Literature Review 1.3.6.2. Total Bacterial Count (TBC). The total bacterial count represent the content of the bacteria generally in the waters, but does not clarify the presence of all species of bacteria in the waters except the able to growth, and producing the clear colonies in the culture media under suitable examining circumstances included time and temperature (WHO, 2004). Usually account the number of colonies after the incubation period at temperature 22 °C and 37 ° C for 24 hours to assessment the numbers of the bacteria presence naturaly in water and that is not related to fecal contamination, and the bacteria derived from human and warm-blooded animals(Olutiola et al.,2010), therefore account the numbers of bacteria at temperature 22 °C are to have little health importance but useful in evaluating the efficiency of water treatment, while the numbers of bacteria growing at temperature 37 C° represents an early indicator of pollution, because the organisms growing in this degree to the external source (WHO, 1996; Al-Fatlawy, 2007). 1.3.6.3.Total Coliform (TC). The term “coliform bacteria” refers to the bacterial species in the family Enterobacteriaceae genera such as Escherichia, Klebsiella, Enterobacter and Citrobacter that live in the intestines of warm-blooded vertebrates (mammals and birds), (WHO,2008). They are including the aerobic and facultative anaerobic, gramnegative, non-spore forming, rod-shaped bacteria that ferment lactose with gas production within 48 hours at 35 ºC (Oliver et al., 2012 ; Nzung’a et al., 2013). Therefore, total coliform counts are not necessarily a measure of fecal pollution but useful for determining the quality of potable water, shellfish harvesting waters, and recreational waters(WHO,2008; Christensen, et al., 2013) 15 Chapter one Introduction and Literature Review 1.3.6.4. Faecal coliforms (FC). Faecal coliform is a subgroup of total coliforms that include all coliforms that ferment lactose and produce gas at 44.5 °C within 24 hours. This group comprises thermotolerant strains such as Escherichia, Klebsiella and Citrobacter (Gilpin and Devan, 2003). Faecal coliforms are usually associated only with human or animal waste.The enteric bacterium Escherichia coli, is the member of this subgroup most commonly cited as an exclusive indicator of faecal contamination ( Gilpin and Devan, 2003). The presence of faecal coliforms indicates the presence of fecal material from warm-blooded animals. Outside of a warm-blooded host, faecal coliforms are short-lived compared to the coliform bacteria that are free-living and not associated with the digestive tract of man or animals ( Bitton,2005). A high faecal coliform counts have been positively related to urban development, agriculture, and the amount of erodible soils (Mehaffey et al., 2005). Faecal coliforms is considered as an index of fecal contamination and therefore contaminated with pathogenic organisms (Sankararamakrishnan and Guo, 2005; Bastholm et al.,2008). Faecal coliform concentrations are not evenly distributed in surface waters. Their densities vary in relation to season, climate, tidal cycles, and other environmental factors such as temperature, pH, salinity, turbidity, nutrients, and solar radiation intensity. Faecal coliforms in surface waters are peaked after a rain event. Subsequently, they decrease or disappear from the water column with time, through death and sedimentation processes, but may concentrate in sediments at high densities. Coliform bacteria in sediments can be resuspended in shallow waters by tidal movements and winds, dredging, storm surge, increased 16 Chapter one Introduction and Literature Review stream flow, and recreational activities such as boating(Nollet,2007; Jolley et al., 2008). 1.3.6.5.Total Streptococci(TS) and Faecal Streptococci(FC). This group are Gram-positive, catalase-negative, non spore forming cocci that to grow at 6.5% NaCl, high pH (pH=9.6) and high temperature (45°C), and includes many species of bacteria in the genus Streptococcus such as, S. faecalis, S. bovis, S. equines, S. avium, S. faceium, and S. gallinarum (Abbas et al., 2007 ; WHO, 2008). Faecal streptococci are considered as Streptococcus spp. that normally occur in faecal matter, were used instead of Faecal Coliform because Faecal streptococci survive well in the environment and are found in all potential pollution sources such as composted poultry litter (Wiggins,1999 ; Abbas et al , 2007). Faecal streptococci have been used as indicators of water faecal contamination in water due to presence consistently in the feces of all warm-blooded animals and in the environment associated with animal discharges (APHA,2005). Members of this group survive longer than other bacterial indicators but do not reproduce in the environment (Bitton,2005). 17 Chapter two Materials and methods Chapter two Materials and Methods 2.1. Study Area. 2.1.1.AL-Haay City. AL-Haay is Iraqi city and center of distract in Wasit province. It is a large city ancient there is one of the most followers of the Ahl AlBayt (peace be upon them) Saeed bin Jubair AL-Asudai, and there lot of families ancient and home to a group of Iraqi tribes originally located on the both sides of AL-Gharraf river, which divides the city into the state and Karrada in term of the orchards and fruit , is located in the southern province of wasit and mediates AL-Haay city among the cities of Al-Kut from the north and the Qalat Sukkar from the south, and away from the for the Kut city (Wasit province) with 45 km and from Qalat Sukkar (Dhi Qar province) at 35 km and from Baghdad by 220 Km and area 111 square km and population number about (125000) people (DWS, 2009). 2.1.2.Al-Gharraf River. Historically, the Al-Gharraf river is an artificial canal built during Urnamekina the King of Lagash (2395- 2425 BC). Its name in Arabic means that it has much water taken from Tigris; it had other names like the Red river for the much silt during spring flooding (AlHaidary, 2006). It is the largest branch of the Tigris River, and was thus derives its properties from the Tigris River. It branches at north of the Al-Kut city towards the south passes through these cities: Al-Muafakiah, AlHaay (study area), Al-Basha'er in the Wasit and Al-Fajer, Qalaat Sekar, Al-Refaee, Al-Naser then Al-Bada'a district in 18 where it Chapter two Materials and methods branched to Al-Bada'a river and Al-Shatrah river in the Dhi-Qar (AlGizzy, 2005), (Figure 1). Al-Gharraf river is the main water source for agriculture and public requirements and has impacts certain on the socio-economic aspects of that area. The river receives most of the wastewater from many cities including industrial, agricultural, and domestic wastewater. Associated with the development of the area, the increase of pollutants into the river has been a recent cause for alarm (ALZamili, 2007). The length of the main river is about 230 km, 50- 90 m width and 7-13 m depth, the river sector in this study is about 165 km extending from Al-Kut city to Al-Bada'a north of Al-Shatrah . Its basin populated by more than million people using about 432000 m³ /year of refined water and passing through an agricultural area of about 215019 ha in the south west of Iraq within the sediment plain (MOA&I, 1991; Jawad, et al. 2009). Considered Gharraf rivers mission in Iraq, where exploits the river for agricultural purposes and the generation of electric power and a source of water supply for treatment drinking water plant. The geographical position lies between the north latitude (32  27 º - 31  2 º) and east longitude (45  45 º - 46  4 º). This position gives the area climate features like ; the high rate of sun radiation, high temperature, few rain occasions , low moisture, and high rate of evaporation ( Swady , 2005). 19 Chapter two Materials and methods Figure (1): Map of Al-Gharraf River in Haay city 2.1.3.Sampling stations. The study area divided into five main stations in the area between the north latitude (32  11 º - 32  07 º) and east longitude (46  01 º - 46  10 º) and along approximately 8 km before entering the river to AL-Haay city and even leaving them, according to population density and the possibility of contamination, the positions of stations were determined by the Global Positioning System (GPS) (Figure 2) . 20 Chapter two Materials and methods Figure (2): Sampling stations on Gharraf Rive at Haay city 2.1.3.1. First station. Represents the control station and located before entering the River to AL-Haay city before bridge No.1distance 1km in the north latitude (32  º 11) and east longitude (46  º 01), and the river is characterized in this area by little growing plants on its banks and large width and high water level (Figure, 2-a) . Figure (2-a): Al-Gharraf River at the first station 21 Chapter two Materials and methods 2.1.3.2. Second station. This is located at 500 m away from the bridge No.1 at the north latitude (32  º 10) and east longitude (46  º 01), and represents discharge point untreated sewage transformed by 9 pipelines with the rate operation of 8 h/day. Also, this site is recived a significant quantity of solid and liquid wastes either directly or indirectly (Figure 2-b) . Figure (2-b): Al-Gharraf River at the second station 22 Chapter two Materials and methods 2.1.3.3. Third station. This location is about 2km of second station in the north latitude (32  º 09) and east longitude (46  º 02). This station characterizes by large population density and represents a raw water uptake of AL-Bashaer station its belong to directorate AL-Haay of Water that give drinking water to AL-Haay city and their distracts for the number of large population of this and the river is characterized in this region by growing plants on the both side of the river, and it occurred under the influence of human activity (Figure 2-c) . Figure (2-c): Al-Gharraf River at the third station 2.1.3.4. Forth station. It is about 4km of second station in the north latitude (32  º 08) and east longitude (46  º 02). This station characterized by large of population density and groves of orange and other citrus trees as well as dense aquatic plants such as Phragmites australis and Typha sp. and Ceratophyllum demersum on the banks of the river and is a good area for fishing (Figure 2-d) . 23 Chapter two Materials and methods Figure (2-d): Al-Gharraf River at the fourth station 2.1.3.5. Fifth station. It is about 8km of the first station in the north latitude (32  º 07) and east longitude (46  º 10). This station characterizes by agricultural fields and villages on the banks of the river and also features river in this area with increased the width and presence of some small stream this get the waste from the around agricultural fields (Figure 2-e) . Figure (2-e): Al-Gharraf River at the fifth station 24 Chapter two Materials and methods 2.2. Materials. 2.2.1. Apparatus and Instruments. The following apparatus and instruments that were used in the experiments of the study. Table (2): Apparatuses and equipments used in the study. No. Apparatus & Instruments Company 1 2 3 4 5 Atomic Absorption Spectrophotometer Autoclave Colony Counter Distillation system Electrical oven Perkin-Elmer (USA ) Retsch (Germany) Memmert (Germany) Difco (USA) Gallenkamp (England) 6 7 8 Flow meter EC meter Global Positioning System (GPS) General Oceanic WTW (Germany) Garmin Ltd (Taiwan) 9 10 Glass bottles Hot plate Volaca (England) Retsch ( Germany) 11 12 13 14 15 Incubator Micro Filter paper Magnetic Stirrer Micropipette Muffle Furance Memmert ( Germany) Whatman (England) Gallenkamp (England) Volaca (England) Hobersal (Espania) 16 17 18 polyethylene bottles pH Meter Refrigerator Volaca (England) WTW (Germany) Ishtar (Iraq) 19 Sensitive electronic balance Kern (Germany) 20 21 Turbidity meter Thermometer HACH (USA ) Zeal (England) 22 UV Spectrophotometer Optima (Japan) 23 24 Winkler bottles Water bath Volaca (England) Tafesa (Germany) 25 Chapter two Materials and methods 2.2.2. Chemical Material. The following list includes all the chemical materials that have been used in the methods and protocols of this study. Table (3): Chemical materials used in the study. No. Chemical Materials Company 1 Ascorbic acid BDH(England) 2 Azid sodium ( NaN3) BDH(England) 3 4 5 6 7 8 9 10 11 12 13 14 15 Ammonium molybdate (NH4)6MO7O24.4H2O Ammonium-nitrogen (NH4+) Barium chloride ( BaCl2) Dihydrogen manganese sulfate(MnSO4.4H2O) Deionized water Distalled water Ethanol Hydrochloric acid (HCl) Sodium hydroxide (NaOH) Sodium chloride ( NaCl) Silver nitrate ( Ag NO3) Sulfuric acid (H2So4) Nitric Acid ( HNO3) BDH(England) BDH(England) BDH(England) BDH (England) Local Local BDH (England) BDH (England) BDH (England) Sigma (USA) Fluka (Switz.) BDH (England) BDH (England) 2.2.3. Culture Media. The following ready cultural medias used in present study Table (4), were prepared according to the instructions of proper company, which are fixed on the container of the media. Each one of these culture media has been sterilized by autoclave (121 °C for 15 min at 15 bar / in2) and incubated at 37 °C for 18-24hours to ensure their sterilization, then kept at 4°C until used. all the cultural medias were prepared according to the standard protocols (Atlas, 2005; APHA, 2005; Einasri et al., 2012). 26 Chapter two Materials and methods Table (4): Ready cultural medias used in the study. No. Culture media Company 1 Azide Dextrose Broth Bio life (Italy) 2 Briliant Green Bile Lactose Broth Merck (Germany ) 3 EC media Merck (Germany ) 4 Lauryl Tryptose Broth Merck (Germany ) 5 Macconkey Broth Bio life (Italy) 6 Nutrient Broth Himedia (India) 7 Pfizer selective Enterococcus Agar Himedia (India) 2.2.4. Reagents. The following Reagents and solutions used in present study (Table, 5), were prepared and sterilized by autoclave at 121 °C for 15 min at 15 bar/in2, while the other reagents and solutions which may be destroyed by high temperature were sterilized by filtration with milipore filter (0.22) μm. All the reagents and solutions were prepared according to the standard protocols (WHO, 1996b; AOAC,2005; AL- Fatlawy, 2007). Table (5): Reagents used in present study No. Reagent & Solutions Company 1 Dichromate Potassium (K2Cr2O7) BDH (England) 2 Dilution Buffer Solution BDH (England) 3 EDTA (0.1M) Solution Fluka (Switz.) 4 Eriochrom Black-T(EBT) Merck (Germany ) 5 Phenol Phthalen Reagent BDH (England) 6 Sodium Thiosulfate Solution BDH (England) 7 Starch Solution BDH (England) 27 Chapter two Materials and methods 2.3. Methods. 2.3.1.Sample collection. Sampling of physical, chemical and biological variables was performed from five sites at monthly was carried out from October 2012 till July 2013, to represent all seasons by rate two sample each month from each site. Sampling usually started at 9 am and was completed at 2pm . v The samples were taken from mid of the river about 35m from the shore line. v Water sample for physical, chemical analysis collected in polyethylene containers with a volume of 5 litters under water surface about (20-40) cm after punning the container with water sample twice before filling, then kept at 15oC in refrigerator (WHO, 1996b ; Anitha and Sugirtha, 2013). v Water samples for dissolved oxygen (DO) and biological oxygen demand (BOD5) were collected in sterile dark Winkler bottles 250 ml, they were washed and sterile by placing them in the oven for 4hr at 200oC. Oxygen fixation was done at field by adding 2ml of magnesium sulfate, iodide azide and 2ml of sulphuric acid (APHA, 1998; Rajiv et al. 2012). v Water sample for biological analysis were collected in closed glass bottles, washed with distilled water and sterile by placing them in the oven for 4hr at 200oc, then kept in Cool box till carrying to a laboratory for examination (APHA, 2005; Ell-Amin et al., 2012) . 28 Chapter two Materials and methods 2.3.2. Field measurement. 2.3.2.1. Air and water temperature. Air and water temperature were measured in the field with a mercury thermometer (0-50 oC) graduated up to 0.1 intervals, at the depth 20cm. The measurement was taken after temperature stabilizing for a few minutes according to APHA (1998). The results expressed as Celsius degrees 2.3.2.2. Water currents. Water current was measured directly in the field according to ALZurfi ( 2007), by using Flow meter (General Oceanic).The results were expressed as m/sec. 2.3.2.3. pH degree. It was measured directly in the field according to (AOAC, 2005) by using portable pH-meter model (WTW pH. 720). The instrument was calibrated before each sampling with standard buffer solution (pH: 4, 7 and 10). 2.3.2.4. Electrical conductivity (EC). Electrical conductivity of water was measured directly in the field by using portable EC-meter (WTW EC. 720). The instrument was supplied with an automatic temperature corrector. The results were expressed as µs.cm-1 according to APHA (2003). 2.3.2.5. Dissolved oxygen (DO). It was determined by using azide modification of Winkler method as described by (USEPA,1986; APHA, 1998), which summarized by fixing oxygen in field, and then added 2 ml of H2SO4 and bottle was shake thoroughly to dissolve the precipitate. Then was titrated against (0.0125 N) Na2S2O3.5H2O (sodium thiosulphate solution) using 2 drops 29 Chapter two Materials and methods of starch solution as an indicator. The results were expressed as mg.l-1. DO values were calculated according to the equation: DO mg/l= (V2 x 8000 x 0.0125) / (V1-1.3) V2: volume of titrate V1: volume of sample 2.3.3.Laboratory measurement. 2.3.3.1. Biochemical Oxygen Demand (BOD5). It was determined as recommended by EPA (2006), after five days incubation at 20 oC. in dark bottle then measured using Winkler method. The results were expressed as mg.l-1. BOD5 values were calculated according to the equation: BOD5= DO1- DO2 Where: DO1= dissolved oxygen (mg.l-1) on the first day DO2= dissolved oxygen (mg.l-1) of sample after 5 days incubation Whereas, BOD5 for diluted samples were calculated as follows: BOD5 (mg.l-1) = DO1- DO2 / P Where: DO1 = initial DO of the diluted wastewater sample about 15 minute after preparation. DO2 = final DO of the diluted wastewater sample after five days. P = decimal dilution factor. 2.3.3.2. Salinity. Measurements of salinity depended on EC value (Richards, 1954) according to the following equation: Salinity ppt= EC x 0.64 / 1000 30 Chapter two Materials and methods 2.3.3.3. Turbidity. Measured by using turbidity meter ( HACH.2100N.).The instrument was calibrated before each sampling with standard solutions. The results expressed as NTU (Nephelometric Turbidity Unit), according to APHA (1998). 2.3.3.4. Total Dissolved Solids (TDS). Total Dissolved Solids were measured according to EPA (2001) by the following equation, depending on E.C. value: TDS mg/l= E.C. μS/cm X (2/3) 2.3.3.5. Total Suspended Solids (TSS). APHA (1998) method was used to determine the suspended particulate matter by washing millipore filter paper 0.45μm then oven dried at 105oc for one hour, then cooled and weight. Filter 100ml of sample and returned again to the oven and cooled then weight and used the following equation: TSS mg/l= (A – B) × 1000 / mL of sample A: weight of filter paper with residue mg B: weight of filter paper 2.3.3.6. Total Hardness(T.H). The method described by Lind (1979), was used for the purpose of measuring the values of total hardness, by taking 10 ml of the sample and diluted to 50 ml with distilled water, then added one ml of ammonia regulator solution where the pH is10. After the addition of a few of dry indicator (Erichrom black T) use as reagents and titrated against EDTA solution Normaly 0.05, and calculated values often by the following equation: Total hardness as CaCO3 = A × B × 1000/ml of sample Where: A = number of titration moles 31 Chapter two Materials and methods B = number of grams of calcium carbonate equivalent 100 ml of EDTA titrated. 2.3.3.7. Chloride ion (Cl-). Chloride ion concentration was measured in water samples in a manner titration using silver nitrate according to APHA (1998) , where 10 ml of the sample diluted to 100 ml using distilled water, and 1 ml of potassium chromate solution as indicator was added, the sample titrated against silver nitrate solution of 0.041normal until convert the colour from yellow to orange , results expressed as mg /l, then the calculate the concentration of chloride ion from formula follows: Cl- mg/l = (A-B) (N) × 35450 / ml of sample Where A = first reading of the sample B = first reading of the Blanck N = normality of silver nitrate. 2.3.3.8. Sulphates (SO4). The method described by APHA (1985), where 5 ml of the sample diluted to 100 ml of distilled water, 5 ml of Conditioning Reagent (HCl, NaCl, Glycerol, alcohol, Distil water) was added to the sample, ,and 0.15 mg of powder of barium chloride BaCl2 is added, then the absorption is determined by using UV-spectrophotometer at wave length 420nm, then the absorption is read on the above mentioned wavelength which makes the barium sulphate minutes stuck, the amount of sulphates is calculated from the difference between the two readings after making a trend of calibration from standard sulphuric acid solution (H2SO4) .The results are expressed in units of mg /l. 2.3.3.9. Nitrate (NO3). Nitrate ions was measured according to APHA (1999) by using 2ml HCl (1N) added to the diluted sample (5ml of sample to 50ml deionized water), then measured by UV-spectrophotometer at wave length 220nm. Results were recorded in unit mg/l. 32 Chapter two Materials and methods 2.3.3.10. Reactive Phosphate (PO4-3). Reactive phosphate is measured by using ascorbic acid method by adding 8ml of combined reagents (H2SO4 5N + Potassium antimony tartrate + ammonium molybdate + ascorbic acid) was added then shacked and stand for 30min then measured after blue color developed by a spectrophotometer at wave length 860nm. Blank is zero (APHA, 1999). 2.3.3.11. Heavy metals tests. The sample preparation was done according to Abbawi and Hassan (1990),was used by taking 100 ml of water sample in a clean Beaker glass with distilled water and water sample, and added 5 ml of nitric acid, then it was evaporated by using a hot plate without boil at 85° C until the volume had been reduced to approximately 10 mL. The sample allowed to cool and transferred to a 50-mL volumetric flack, diluted to volume with de-ionized water and let settle overnight to remove insoluble materials. The solutions were kept in a clean polyethylene flasks, and stored in a refrigerator until later analysis for the measurement by using Atomic absorption spectrophotometer , and then the following equation was applied: Concentration (mg / L) = reading of device × the volume of the sample after Concentration / volume of the sample. 2.3.4. Microbial Tests. 2.3.4.1. Total Bacterial Count(TBC). The pour plate count method used as described by APHA (2005) and Adam & Allaahmed (2012), by means of Nutrient agar as cultivated medium. Plates were incubated at 37oC for 24 hrs. Results expressed as CFU/1ml. 33 Chapter two Materials and methods 2.3.4. 2.Total Coliform count(TC). Most Probable Number (MPN) procedure used as described by APHA (2005) and Ell-Amin et al (2012) using MacConkey broth as cultivated medium. Tubes incubated at 37±0.5oC for 24 hrs. The results expressed as CFU /100ml. 2.3.4.3. Thermotolerant (Faecal) Coliform Bacteria(FC). MPN procedure used as described by APHA (2005) and Ell-Amin et al (2012), using EC media broth as cultivated medium. Tubes incubated at 44.5±0.25oC for 24 hrs. The results expressed as cell/100ml. 2.3.4.4. Total Streptococci (TS) and Faecal Streptococci (FS). MPN procedure used as described by APHA (2005) and Sati et al.(2013), was followed using Glucose Azide broth and Pfizer Selective Enterococcus Agar for both streptococci and faecal streptococci bacteria respectively as cultivated medium. Tubes incubated at 37±0.5oC and 44.5±0.25oC respectively for 24-48 hrs. The results expressed as CFU/100ml. 2.3.5.Statistical analysis. All obtained data were subjected to proper biometrical (statistical) analyses were performed by using SPSS software (Ozdamar, 2005), was used to show effect of different factors (Station & Season) in study parameters. Least significant difference (LSD) test was used to significant compare between means of this study. 34 Chapter three Results and Discussion Chapter three Results and Discussion. 3.1. Physical Characteristics . 3.1. 1. Air and Water Temperature. Temperature plays a important role in the physico-chemical and physiological behavior of biotic components of aquatic ecosystem (Sawant et al., 2010), and is one of the most important physical factors that influence species distribution on earth (Krohne,2000). Water temperature affects the rate of many of the river’s biological and chemical processes (i.e. self-purification). It affects on dissolved oxygen (DO) and biological oxygen demand (BOD), the rate of plant growth, and the metabolic rate of aquatic organisms(Jurgelėnaitė et al., 2012). The fluctuation in river water temperature usually depends on the season, geographic location, sampling time and temperature of effluent entering the stream (Ahipathy, 2006). The air temperature values in this study were varied from the lowest value 16 °C which was recorded at station 4 in winter 2013 and the highest value 42 °C was observed in summer 2013 at station 5. While the water temperature values were varied from lowest value 11°C at station 2, in winter 2013 and the highest value was 31 °C at station 4 and 5 in summer 2013 (Figs. 3&4 and Table 6). The statistical analysis showed that there was a significant differences in air and water temperature between seasons, while no significant differences among stations (P˃0.05) in the same season (Table 6). The significant positive correlation between air and water temperature (r = 0.983) was observed in present study (Table 7). The negative correlation was observed between temperature and all the 35 Chapter three Results and Discussion parameters except pH and concentrations of studied heavy metals (Table 7 and 9 respectively). The data of air and water temperature in this study were supported by the results of Fahad (2006) regarding to the variation of temperature of air and water were 13-38 °C and 12-36.5 °C, respectively. Wahab (2010) has reported similar findings for both air and water were 15-40 °C and 11-30 °C, respectively. Hassan, et. al. (2010) found the air and water temperature values were ranged between 6-40 °C and 10-34 °C, respectively (Appendix 2). Mean Air Temperature (oC) 40 35 30 St.1 25 St.2 20 St.3 15 St.4 10 St.5 5 0 Autumn Winter Spring Summer Figure (3): Seasonal variation of air temperature (oC) in AL-Gharraf River during study period. Mean Water Temperature (oC) 35 30 25 St.1 20 St.2 15 St.3 10 St.4 St.5 5 0 Autumn Winter Spring Summer Figure (4): Seasonal variation of water temperature (oC) in AL-Gharraf River during study period. 36 Chapter three Results and Discussion Table (6): Minimum and maximum ( First Line), mean and standard deviation ( Second Line), for physical and chemical characteristics at study stations during 2012-2013. Stations St.1 St.2 St. 3 St.4 St.5 16.5 – 38 27.92 ± 6.964 a 16 – 39 28.42 ± 7.821 a 17 – 39 28.67 ± 7.240 a 16 – 41 29 ± 7.932 a 17 – 42 28.75 ± 8.114 a 11.5 – 29 22.38 ± 5.540 a 11 – 28 21.38 ± 5.820 a 13 – 30 22.29 ± 5.651 a 12 – 31 22.67 ± 6.461 a 12 – 31 22.33 ± 6.213 a 0.41 – 0.81 0.523 ± 0.131 a 825 – 1345 1061 ± 160.4 b 0.52 – 0.86 0.681 ± 0.104 b 545.3 - 887.7 704 ± 106.3 a 30 – 161 56.5 ± 36.23 a 0.37 – 0.67 0.466 ± 0.096 a 888 – 1450 1166 ± 172.2 a 0.57 – 0.93 0.752 ± 0.110 a 586.08 – 957 773 ± 114.7 a 57 – 177 81.8 ± 41.31 a 0.40 – 0.69 0.495 ± 0.087 a 854 – 1385 1076 ± 182.8 a 0.55 – 0.89 0.691 ± 0.118 a 563.64 – 914.1 713 ± 121.2 a 41 – 154 66.8 ± 36.49 a 0.40 – 0.69 0.502 ± 0.085 a 827 – 1369 1068 ± 177 a 0.53 – 0.88 0.686 ± 0.116 a 545.82 - 903.54 708 ± 118.1 a 40 – 163.5 63.3 ± 36.14 a 0.41 – 0.66 0.472 ± 0.073 a 837 – 1340 1066 ± 168.1 a 0.54 – 0.86 0.684 ± 0.110 a 552.42 – 884.8 707 ± 111.8 a 41 – 65.5 65.9 ± 36.01 a 38 – 233 80.8 ± 51.70 a 7.38 – 8.3 7.782 ± 0.366 a 7.1 – 10.38 8.565 ± 1.151 a 1 – 2.5 1.739 ± 0.498 d 310.08 – 430 359.9 ± 46.06 b 89 - 134.9 105.9 ± 18.47 b 86 – 287 114.9 ± 56.53 a 7.03 – 8.0 7.416 ± 0.374 b 6.3 – 8.44 7.255 ± 0.705 c 4.5 – 7.01 5.970 ± 0.806 a 350.88- 496 405.5 ± 37.82 a 103.07 – 184.6 129.3 ± 25.16 a 190.53 – 360 269.7 ± 56.74 a 6.2 – 15.76 9.86 ± 3.742 a 50 – 216 86.8 ± 43.61 a 7.04 – 8.1 7.584 ± 0.392 a 6.8 – 10.31 7.762 ± 1.032 b 1.5 – 5.1 3.509 ± 1.054 b 318 – 432.5 372.4 ± 45.52 b 93.7 – 139 113 ± 18.37 b 52 – 255 97.7 ± 51.98 a 7.07 – 8.2 7.646 ± 0.387 a 7.1 – 9.57 7.55 ± 0.725 b 1.2 – 4.12 2.875 ± 0.850 c 326.4 – 437.5 373.4 ± 43.70 b 90.3 – 139 109 ± 18.36 b 73 – 251 95.1 ± 50.33 a 7.07 – 8.1 7.701 ± 0.330 a 7.2 – 10.11 8.359 ± 0.793 a 1.4 – 3.15 2.076 ± 0.680 d 306 – 407 353.4 ± 39.44 b 90.3 – 132.5 107.4 ± 16.44 b 185.15 – 330.9 264 ± 61.46 a 6.0 – 14.56 8.94 ± 3.336 a 172.42 – 340 244.8 ± 69.24 a 5.7 – 15.69 8.61 ± 3.356 a 174.42 – 320 248.1 ± 60.92 a 6.2 – 12.94 8.09 ± 2.473 a Parameters Air Temperature ◦ C Water Temperature ◦ C Water Current m/sec E.C. µS/cm Salinity ppt TDS mg/L Turbidity NTU TSS mg/L pH D.O mg/L BOD mg/L T.H. mg/L Cl- mg/L SO4 mg/L NO3= mg/L 183.5 – 320 260.1 ± 55.06 a 5.7 – 15.09 8.18 ± 3.275 a 37 Chapter three Results and Discussion 0.13 – 0.35 0.26 ± 0.0771 bc PO4 mg/L 0.19 – 0.50 0.41 ± 0.097 a 0.27 – 0.40 0.34 ± 0.0605 ab 0.23 – 0.39 0.34 ± 0.0673 ab 0.22 – 0.45 0.37 ± 0.0695 a *Station that carrying similar character were no any significant difference between them. Table (7):The correlation(r) among studid water parameters. Air Temp. Water Temp. Sali. DO BOD Turbid. TDS TSS TH ClSO4 NO3 PO4 Water curr. pH E.C. Sal. DO BOD Turbi. TDS TSS TH Cl- SO4 NO3 ** 0.983 Water ** current -0.643 NS pH 0.423 EC Water Temp. ** -0.649 NS 0.412 * * -0.452 -0.559 NS 0.203 NS 0.332 NS -0.092 * ** -0.586 NS 0.340 NS -0.129 ** -0.481 ** ** ** -0.774 -0.752 0.718 NS 0.028 NS 0.343 NS -0.107 NS -0.183 NS -0.256 -0.64 ** ** -0.558 -0.603 NS 0.047 -0.488 NS -0.422 * -0.529 NS 0.324 NS -0.075 ** ** -0.638 -0.716 NS 0.346 NS -0.307 ** ** * -0.691 -0.766 0.438 -0.403 ** ** -0.732 -0.783 NS 0.297 -0.468 * ** -0.519 -0.578 NS 0.184 NS -0.211 NS -0.196 NS -0.155 * -0.477 NS -0.056 NS -0.094 NS -0.071 ** 0.999 NS 0.355 * * 0.479 0.491 ** ** 0.771 0.782 ** ** 0.997 0.994 ** ** 0.753 0.762 ** ** 0.747 0.766 ** ** 0.832 NS -0.387 NS 0.289 ** NS 0.323 * ** 0.48 0.763 NS 0.34 * ** ** 0.485 0.665 0.736 NS 0.356 ** ** ** ** 0.595 0.738 0.737 0.847 NS 0.408 ** ** ** ** ** 0.847 0.6 0.925 0.818 0.801 0.869 ** ** * ** ** * ** ** 0.785 0.789 0.442 NS 0.299 0.832 0.786 0.489 0.616 0.797 NS 0.202 NS 0.218 NS -0.032 * * 0.662 NS 0.144 NS 0.218 * 0.449 NS 0.201 * -0.588 0.501 0.54 NS -0.334 NS -0.073 NS -0.063 NS -0.333 * NS 0.069 NS -0.102 NS 0.209 NS 0.199 NS 0.078 NS -0.31 * ** 0.626 0.469 **= Significant correlation at P<0.01. *= Significant correlation at P<0.05. NS= Non-significant correlation. 38 NS -0.22 Chapter three Results and Discussion 3.1. 2. Water Currents. Flow is defined as the volume of fluid (e.g. water) that passes through a passage of a given section in a unit of time ((USGS, 2007). Flow affects the dilution properties of a river, an important measurement for the quantitative analysis of pollution problems. Discharge of many rivers is often related to seasonality (Mary and Macrina, 2012). Measurement of surface water flow is an important component of most water quality monitoring projects. Flooding, stream geomorphology, and aquatic life support are all directly influenced by stream flow, and runoff and stream flow drive the generation, transport, and delivery of many nonpoint sources (NPS) pollutants. Calculation of pollutant loads requires knowledge of water flow (USEPA,1993). The results of this study showed that the high value of water current in winter was 0.81 m/sec at station 1, while the lower value was in autumn which was 0.37 m/sec at stations 2 (Fig.5; Table 6). The increase in water flow value in Al-Gharraf River in winter is probably due to the rainfall that increases the water column and the wind that increases water movement, may cause high water flow during winter, while the flow during spring and summer is relatively –moderate, perhaps due to the increase of aquatic vegetation (WASC, 2002). The flow in surface waters is a function of many factors including precipitation, surface runoff, and inters flow, seasonal variations of these factors have strong effects on flow rates and on the concentration of pollutants in surface water (Davies et al., 2008). The statistical analysis showed that there was a significant differences in water current among seasons, while no significant differences among stations (P˂0.05) in the same season. (Table 6). 39 Chapter three Results and Discussion The results of present study conflicted with that of Alzurfi (2005), about Kufa River and Al-Haidarey (2009) on Al-Hawizeh Marsh and Ahmed (2012) on Tigris River. But in agreement other those reported by Al-Obaidi (2006) on Abu Zirig Marsh , Al-Ghanemi (2011) on the Euphrates and Al-Kuraishi (2011) on Tigris River (Appendix 2). Mean Water current (m/sec) 0.8 0.7 0.6 St.1 0.5 St.2 0.4 St.3 0.3 St.4 0.2 St.5 0.1 0 Autumn Winter Spring Summer Figure (5): Seasonal variation of water currents in AL-Gharraf River during study period. 3.1. 3. Electrical Conductivity E.C. and Salinity. Electrical Conductivity is a measure of the ability of water to carry electric current and it is sensitive to variations in dissolved solids, mostly mineral salts ( Ezzat, et. al. 2012). The determination of electrical conductivity helps in estimating the concentration of electrolytes. Its ability is dependent upon the presence of ions in solution and its measurement is an excellent indicator of the total dissolved solid in a matter (Adejuwon and Adelakun, 2012). Salinity is a dynamic indicator of the nature of the exchange system. It is expressed as the total concentration of electrically charged ions in water in part per thousand (ppt) (UNESCO&WHO, 1992). The obtained results showed that the lowest conductivity value 825 µS/cm with salinity 0.52 ppt was recorded at station 1 in spring, while 40 Chapter three Results and Discussion the highest value 1450 µS/cm with salinity 0.93 ppt was recorded at station 2 in winter (Figs.6&7 ; Table 6). These values are similar to those recorded in this river by other studies, but are lower than those recorded in the Euphrates and kufa rivers(Al-Lami et al, 1998 and Alzurfi et al.,2010) (Appendix 2). The statistical analysis showed a significant differences among seasons for E.C. and salinity at (P˂0.05), but no any significant differences among stations was observed except with station 1 (Table 6). Conductivity and salinity showed positive correlation with all the parameters except PO4 and concentrations of studied heavy metals (Cd, Pb & Zn), (Table 7and 9 respectively). Increasing levels of conductivity and salinity in winter and decrease in spring due to the products of decomposition and mineralization of organic materials (UNEP, 2006). As well as the rain fall and increasing of water level and river discharge, which revealed an inverse correlation between E.C. and water temperature (r=-0.559), while the correlation between salinity and water temperature was also inverse correlation (r= -0.586) (Table 7). Anthropogenic increases in salinity and E.C. in surface water are larger due to agriculture, urbanization, and industrial activities (AlNaqshbandi, 2002). The results of E.C and salinity value for Al-Gharraf river came in accordance with the known EC values for Iraqi inland waters ( Al-Lami et al, 1999). Current results are backed by those of Salman (2006) on Euphrates river and Sabah and Fadhel (2011) on Al-Gharraf river and Khalik et al.(2013) on Bertam river in Malaysia but not agree with those of Fahad (2001) on Euphrates river and Al-Helaly (2010) on Al-Gharraf river and Vaishali and Punita (2013) on Mini river in India (Appendix 2). 41 Chapter three Results and Discussion 0.9 0.8 Mean E.C. (µS/cm) 0.7 0.6 St.1 0.5 St.2 0.4 St.3 0.3 St.4 0.2 St.5 0.1 0 Autumn Winter Spring Summer Figure (6): Seasonal variation of electrical conductivity in AL-Gharraf River during study period. 0.9 0.8 Mean Salinity ppt. 0.7 0.6 St.1 0.5 St.2 0.4 St.3 0.3 St.4 0.2 St.5 0.1 0 Autumn Winter Spring Summer Figure (7): Seasonal variation of salinity in AL-Gharraf River during study period. 3.1. 4.Total Dissolved Solids (TDS). TDS is the term used to describe the inorganic salts and small amounts of organic matter present in solution in water. The principal constituents are usually calcium, magnesium, sodium, and potassium cations and carbonate, hydrogen carbonate, chloride, sulfate, and nitrate anions (WHO, 1996b). The concentration and composition of TDS in natural waters are determined by the geology of the drainage, atmospheric precipitation and the water precipitation) (Phyllis and Lawrence, 2007) 42 balance (evaporation- Chapter three Results and Discussion The present study results showed that the maximum value of TDS 957 mg/L was found at station 2 in winter 2013, while the minimum value 545.3 mg/L was found at station 1 in spring 2013(Fig.8;Table 6). The statistical analysis showed a significant differences among seasons at (P˂0.05), but no any significant differences among stations (Table 6). The negative correlation was observed between TDS and each of air and water temperature (r = -0.422 for air temp. and r = -0.529 for water temp.) (Table 7). The results of TDS values in this study within the range of Iraqi standards for drinking water in 1998 and WHO water quality standards in 2003 that maximum value was 1500 mg/L (Appendix 1). High value of TDS recorded during winter period could be related to increase in the load of soluble salts, mud, increase in the urban and fertilizer runoff, wastewater, septic effluent, decaying plants, animals and erosion of river banks. Lower value of TDS recorded in spring period might be due to dilution factor and sedimentation of suspended solids and slow decomposition rate during spring period (Imnatoshi and Sharif, 2012). The study findings are coincided with other results of Al-Saadi et al.(1999) on Tigris and Euphrates river, Hassan et. al.(20108) on Euphrates river, Sabah and Fadhel (2011) on Al-Gharraf river, Ezzat et. al.(2012) on Nile river in Egypt and Saksena et. al.(2008) on Chambal river in India (Appendix2). 43 Chapter three Results and Discussion 1000 Mean T.D.S. (mg/l) 800 St.1 600 St.2 St.3 400 St.4 St.5 200 0 Autumn Winter Spring Summer Figure (8): Seasonal variation of total dissolved solids in AL-Gharraf River during 2012/2013 3.1.5.Turbidity. Water turbidity is the measure of fine suspended matter in water, mostly caused by colloidal particles such as clay, silt, non-living organic particulates, plankton and other microscopic organisms, in addition to suspended organic and inorganic matter. The turbidity degree of stream water is an approximate measure of pollution intensity (Siliem, 1995; Lako, et al. 2012). Turbidity in water has public health implications due to the possibilities of pathogenic bacteria encased in the particles and thus escaping disinfection processes. Turbidity interferes with water treatment (filtration), and affects aquatic life (UNEP, 2008). In this study the highest value of turbidity recorded in winter season at station 2 which was 177 NTU while the lowest value of turbidity was recorded in spring season at station 1 which was 30 NTU (Fig.9 ; Table 6). The statistical analysis showed a significant differences among seasons at (P˂0.05), but no any significant differences among stations (Table 6). The results of present study showed positive correlation between turbidity and total suspended solids and water current (r= 0.665 and r= 0.047 respectively) (Table7). 44 Chapter three Results and Discussion The increased turbidity during rainy seasons was attributed to soil erosion in the nearby catchment and massive contribution of suspended solids from sewage. Surface runoffs and domestic wastes mainly contribute to the increased turbidity (Gangwara et al., 2012 ). High turbidity can decrease the amount of available sunlight, limiting the production of algae and macrophytes. Turbid waters may also damage fish directly by irritating or scouring their gills, also harm some benthic macroinvertebrates (Owens et al., 2005) Generally, turbidity is widely concerned as an important parameter for drinking water. However, the observed value were higher than the permissible level recommended by the Iraq, WHO and CCME for drinking water for all seasons according to (Al-Janabi et al., 2012). These results didn't correspond with those of Al-Lami et. al. (1996b) ; Sabri et. al. (1997) and Al-Kuraishi (2011) studies in Iraq and Manjare et al. (2010) and Srivastava et al.(2011) and Vaishali and Punita (2013) studies in Indi (Appendix 2). 120 Mean Turbidity (NTU) 100 St.1 80 St.2 60 St.3 40 St.4 St.5 20 0 Autumn Winter Spring Summer Figure(9): Seasonal variation of turbidity in AL-Gharraf River during study period. 45 Chapter three Results and Discussion 3.1. 6.Total Suspended Solids (TSS). The term “total suspended solids” (TSS) applies to the dry weight of the material that is removed from a measured volume of water sample by filtration through a standard filter (UNEP&WHO, 1996). The total suspended solids may be organic and inorganic, that are suspended in the water. These would include silt, plankton and industrial wastes. Source of total suspended solids include erosion from urban runoff and agricultural land, industrial wastes, bank erosion, bottom feeders, algae growth or wastewater discharges (Bamakanta et al., 2013). Present study findings showed that maximum value of TSS recorded was in winter season at station 2 which was 287 mg/L while the minimum value was recorded in spring season at station 1 which was 38 mg/L (Fig.10; Table 6). The statistical analysis showed a significant differences among seasons at (P˂0.05), but no any significant differences among stations (Table 6 ). A negative correlation with air and water temperature (r=-0.638 and r=-0.716 respectively) also was finding, while found a positive correlation with water currents was also found (r=0.346), (Table 7). High concentrations of suspended solids may alter water quality by absorbing light. Waters then become warmer and lessen the ability of the water to hold oxygen necessary for aquatic life. Because aquatic plants also receive less light, photosynthesis decreases and less oxygen is produced. (Lawson, 2011). Also high TSS in a water body can often mean higher concentrations of bacteria, nutrients, pesticides, and metals in the water because suspended particles provide attachment places for these other pollutants (Health Canada, 2012). Also, these results showed clear increase in TSS values in winter season and decrease in spring season may be due to increase in water level, soil erosion and rainfall, as well as, other matters such as algae and organic matter . 46 Chapter three Results and Discussion These results however, agrees with those of local studies of Al-Saadi et al. (1989), Al-Lami et al. (2001), Hassan (2004) and Al-Nimrawee (2005) and international studies of Mary & Macrina (2012), Gangwara et al.(2012) and Khalik et al. (2013) (Appendix 2) . 160 140 Mean T.S.S. (mg/L) 120 St.1 100 St.2 80 St.3 60 St.4 40 St.5 20 0 Autumn Winter Spring Summer Figure (10): Seasonal variation of total suspended solids in AL-Gharraf River during study period. 3.1. 7. pH degree. The pH value represents the instantaneous hydrogen ion activity and affects biological and chemical reactions in a water body (Friedl et al., 2004; Lawson, 2011). The increase in pH in the rivers could be related to photosynthesis and growth of aquatic plants, where photosynthesis consumes CO2 leads to a arise in the pH values (Yousry et al., 2009). Generally, optimal pH range for sustainable aquatic life is pH 6.5-8.2. pH of an aquatic system is an important indicator of the water quality and the extent pollution in the watershed areas. (Kumar et al., 2011). The pH values of Al-Gharraf river stationes never fall below 7, it ranged from 7.03 in station 1 during autumn 2012 to a maximum value of 8.3 in station 1 during summer 2013 (Fig.11; Table 6). The statistical analysis showed a significant differences among seasons for pH at (P˂0.05), but no 47 Chapter three Results and Discussion any significant differences among stations was observed except with station 2 (Table 6).The positive correlation between pH and air and water temperature (r= 0.423 and r= 0.412 respectively) was observed in present study (Table 7). Ezekiel et al. (2011) associated low pH value to the rise of CO2 production and humic acid formation with bacterial respiration in decomposition of organic matter. This study agrees with the results of Attee (2004) on Shatt Al-Arab river, Muath and Muna (2007) on Tigris river and Sabah and Fadhel (2011) on Al-Gharraf river (Appendix 2). pH higher than 7 but lower than 8.5 according to Abowei (2010) is ideal for biological productivity, but pH at <4 is detrimental to aquatic life. pH may be affected by total alkalinity and acidity, run off from surrounding rocks and water discharges. pH values in Iraqi inland water lay in the alkaline condition as it known phenomenon for the due to the presence of carbonate and bicarbonate (Maulood et al. 1980 and Hassan, 1997). Some aquatic organisms in the river are sensitive to changes in pH because most of their metabolic activities are pH dependent and some of them may not be able to tolerate the changes. Decline in pH can cause toxicity to many fish and may result to death. For example, a pH of 4 or less cannot be tolerated by a fish in the river. Low pH can also increase the amount of heavy metals (Al-Saadi, 1994). The pH values were within the permissible level set by WHO (1993) and EEC 464/76 stander for surface water quality (Tebbutt, 1998 ), which were between 6.5-8.5 (Appendix,1). The present study results coincided with other international studies of Shraddha et al. on Narmada river (2011), Adejuwon & Adelakun (2012) on Agodo river and Munna et al. (2013) on Surma river (Appendix 2). 48 Chapter three Results and Discussion 8.5 Mean pH value 8 St.1 7.5 St.2 St.3 7 St.4 St.5 6.5 6 Autumn Winter Spring Summer Figure (11): Seasonal variation of pH values in AL-Gharraf River during study period. 3.2. Chemical Characteristics. 3.2. 1. Dissolved Oxygen (DO). Dissolved oxygen is one of the most important parameters in water quality assessment and reflects the physical and biological processes prevailing in the water (UNEP&WHO,1996; Bhattacharya et al., 2012). The value of dissolved oxygen is remarkable in determining the water quality criteria of an aquatic system. In the system where the rates of respiration and organic decomposition are high, the DO values usually remain lower than those of the system, where the rate of photosynthesis is high (Mishra et al., 2009). When the water is polluted with large amount of organic matter, a amount of dissolved oxygen would be rapidly consumed in the biological aerobic decay which would affect the water quality; the decreased dissolved oxygen in water would affect the aquatic lives (Chhatwal, 2011). Data of DO at the present study area are shown in Figure (12) and listed in Table (6). The lowest value was 6.3 mg/L in summer 2013 recorded at station 2, whereas the highest value was 10.38 mg/L in winter 2013 recorded at station 1. 49 Chapter three Results and Discussion The statistical analysis revealed significant differences (P˂0.05) in DO among seasons and the significant differences (P≤0.05) found among stations except station 1 with 5 and station 3 with 4 (Table 6). A positive correlation between DO and water current was found (r=0.718), while negative correlation was found between DO and water temperature; BOD5; NO3 and PO4 (r= -0.752; -0.387 ; -0.032 and -0.333 respectively) (Table 7). This variation in DO values from stations 2 to 4 may be mainly attributed to the consumption of DO in the oxidation of organic matter from the domestic waste discharged of the Al-Haay city on the bank of the river. As there was no more discharge of waste after station 5, the DO values improved due to atmospheric reaeration. Based on the above results it can be said that the dissolved oxygen content is within the limits of standards of WHO(2004) suggested the standard of DO is more than 5mg/L (Appendix 1). Decrease in the dissolved oxygen content during summer season could also be attributed to increase in temperature will result in a decrease in the concentration of dissolved oxygen, photosynthesis and aquatic organisms respiration also play an important role with fluctuations of dissolved oxygen concentration in water because self-purification occur when the decomposing organisms use the dissolved oxygen to degrade the organic matter (Dallas & Day, 2004 and Toma, 2013). Increasing levels of DO in Al-Gharraf river due to the self-purification mechanism, good mixing, and larger water volume (Al-Saadi, 2006). The results of present study are in agreement with those of Al- Nimrawee (2005) who found that DO values between 6.8-12 mg/L in Tigris River, Hassan, et. al.(2008) who recorded in his study DO values was ranged between 7.1-8.4 mg/l in Shatt Al-Hilla River and Hussein & Fahad ( 2008) recorded DO values varied between 6.2-9.5 mg/L in Al-Gharraf River (Appendix 2). 50 Chapter three Results and Discussion 12 Mean D.O. (mg/L) 10 8 St.1 St.2 6 St.3 St.4 4 St.5 2 0 Autumn Winter Spring Summer Figure (12): Seasonal variation of dissolved oxygen in AL-Gharraf River during study period. 3.2. 2. Biological Oxygen Demand (BOD5). The BOD5 is a measure of the oxygen in the water that is required by the aerobic organisms (Chapman, 1996). The biodegradation of organic materials exerts oxygen tension in the water and increases the biochemical oxygen demand (Shivayogimath et al., 2012). BOD5 tests measures only biodegradable fraction of the total potential DO consumption of a water sample. High BOD5 levels indicates decline in DO, because the oxygen that is available in the water is being consumed by the bacteria leading to the inability of fish and other aquatic organisms to survive in the river (Vaishali and Punita 2013). The obtained BOD5 data showed that the maximum value was recorded in autumn season at station 2 which was 7.01 mg/L while the minimum value was found in spring season at station 1 which was 1.0 mg/L (Fig.13; Table 6). The results of statistical analysis refer that significant different (P˂0.05) between seasons and the significant differences (P˂0.05) between stations except between station 1 and 5 (Table 6). The increase in BOD5 value in station 2, returned to due to the effluent discharged enriched with organic matter from Al-Haay city which leading to 51 Chapter three Results and Discussion decrease in DO value. This phenomenon was found by Al-Mayaly (2000), Hussein (2002) and Al-Tameemi (2004). The concentration of BOD5 for most the study stations was exceed the permissible limit for both Iraqi standards for water quality 1998, which was less than 5 mg/L, and exceed the WHO standards (2004), which was less than 3 mg/L. The high BOD5 value during autumn and winter, was probably linked to the level of organic matter load from sewage, industrial or urban discharges as reported by Chapman (1992). On the other hand, BOD revealed high positive correlations with all bacteriological parameters (P<0.05) (Table 11), and a no significant negative correlation to water temperature (r = -0.184), pH and DO (r = -0.635 and r = -0.387 respectively ) (Table 7) , mainly due to removal of free oxygen by bacteria during decomposition of organic matter particularly in winter season. The results of this study were higher than that reported by Fahad (2006) who registered BOD5 value ranged 1.1- 6.1 mg/L in Al-Garraf river ; AlNimrawee (2005) found the range for BOD5 was 0.9-3.5 mg/L in Tigris river and Aziz (2006) found the range for BOD5 was 1.3-4.6 mg/L in Greater Zab river, whereas it was lower than that reported by Al-Rubaiy (2007) found the range for BOD5 was 1.80-10.41 mg/L in Diyala river, Abed Al-Razzaq (2011) with a range of 0.006-640 mg/L in Tigris river and Shekha (2008) found the range for BOD5 was 0.4-38.8mg/L in Greater Zab river (Appendix2). Also, present study coincided with international studies of Ezekiel et al. (2011) on Sombreiro River in Nigeria, El Bouraie et al.(2011) on Nile delta in Egypt and Dhakyanaika and Kumara (2010) on Krishni river in India but disagree with Abdo, et. al.(2010) on Nile river in Egypt ; Shivayogimath et al. (2012) on Ghataprabha River in India and Khalik et al. (2013) on Bertam river in Malaysia (Appendix 2). 52 Chapter three Results and Discussion 8 Mean value BOD5(mg/L) 7 6 St.1 5 St.2 4 St.3 3 St.4 2 St.5 1 0 Autumn Winter Spring Summer Figure (13): Seasonal variation of biological oxygen demand in AL-Gharraf River during study peroid. 3.2. 3. Total hardness (TH). Hardness is one of the important chemical characteristics to determine the suitability of water for domestic drinking and industrial purposes. Hardness is caused principally due to the dissolved contents of carbonates and sulphates of calcium and magnesium; at times to a lesser degree, presence of chlorides, nitrates and sometimes iron and aluminum is effective in causing hardness. It is expressed as ppm in terms of calcium carbonate (Cheepi, 2012; Anhwange et al. 2012). The calcium occurs in water due to presence of lime stone, gypsum, dolomite and gypsiferrous matters. Calcium and magnesium are the major scale forming constituents in raw water. Calcium is an essential element for Human and for plant growth. Magnesium is an essential element for human beings, but higher levels of magnesium are harmful as they act as cathartics and diuretics in man (Bamakanta et al., 2013). The values of total hardness in Al-Gharraf river are shown in Figure (14) and listed in Table (6). The lowest value was 306 mg/L in summer 2013 recorded at station 5, whereas the highest value was 496 mg/L in winter 2013 53 Chapter three Results and Discussion recorded at station 2. The statistical analysis showed a significant differences among seasons for T.H at (P˂0.05), but no any significant differences among stations was observed except with station 2 (Table 6). The positive correlation between T.H and E.C. and salinity (r= 0.747 and r= 0.766 respectively),while the negative correlation between T.H and air and water temperature (r= -0. 691 and r= -0.766 respectively) was observed in present study (Table 7). Higher values of total hardness in Al-Gharraf river at station 2 and 3 due to the major increase occurred after receiving the domestic sewage and industrial waste of Al-Haay city. The increase levels hardness value in winter and decrease in spring and summer due to the dilution in salts concentration in flood period (Al-Lami et al., 1998). Kevin (1999) had divided water sample into four types depending on total hardness as: The concentration less than 50mg/L calcium carbonate as nonhard water, the water has values ranged from 50 to 100 mg/L is moderate hard water, values from 100 to 200 mg/L is hardness water, and more than 200 mg/L calcium carbonate as a very hard water, according to present study finding, it can be classify Al-Gharraf river water as a hard to very hard water, but within the permissible limit of Iraqi standards for drinking water No.417 in 1989 and WHO water quality standards in 2003 that maximum value was 500 mg/L (Appendix 1). These results were supported by those of Taj Al-Deen, 2001 on Al-Hilla river and Al-Nimrawee (2005) on Tigris river, Hassan et al. (2010) on Euphrates river, Sabah & Fadhel (2011) on Al-Gharraf river in Iraq and Khalik et al.(2013) on Bertam river in Malaysia and Bamakanta et al (2013) on Nagavali River in India but no agreed with the studies of Fahad (2001) on Euphrates river, AL-Zamili (2007) on Al-Gharraf river, Al-Kuraishi (2011) on Tigris river in Iraq and Saksena et. al.(2008) on Chambal river and Vaishali & Punita (2013) on Mini river in India (Appendix 2) . 54 Chapter three Results and Discussion 450 400 Mean T.H. (mg/L) 350 300 St.1 250 St.2 200 St.3 150 St.4 100 St.5 50 0 Autumn Winter Spring Summer Figure (14): Seasonal variation of total hardness in AL-Gharraf River during study period. 3.2. 4. Chlorides (Cl-). Chloride exists in all natural waters, the concentrations varying very widely and reaching a maximum in sea water (up to 35,000 mg/l). In fresh waters the sources include soil and rock formations, sea spray and waste discharges. Sewage contains large amounts of chloride, as do some industrial effluents (Ezeribe et al., 2012). In natural water chloride occurs in widely varying concentration. Abnormal chloride concentration may result due to pollution of sewerage waste and leaching of saline residues in the soil. Its desirable limit is 200-250 mg/L beyond this limit, taste, corrosion and palatability are affected; and deficiency of chloride also an influence of the productivity of the agriculture. Excess presence of chloride in water leads to gastrointestinal, diarrhea , and skin allergies (Cheepi, 2012) . The range of chloride ions values was 89 to 184.6 mg/L (Fig.15 ; Table 6). The minimum value of Chloride (89 mg/L) was recorded at station 1 during spring 2013, while the maximum value (184.6 mg/L) was found in station 2 during winter 2013. The statistical analysis revealed significant differences (P<0.05) in Cl- among seasons but no any significant differences 55 Chapter three Results and Discussion among stations was observed except with station 2 (Table 6).The positive correlation between Cl- and E.C. and salinity (r= 0.832 and r= 0.847 respectively),while the negative correlation between Cl-and air and water temperature (r= -0. 732 and r= -0.783 respectively) was observed in present study (Table 7). The increase of Cl- value in station 2 and 3, indicates to pollution by sewage in the waters of Al-Gharraf river due to the discharged sewage from the Al-Haay city enriched with organic matter, this phenomenon was proved by Chapman (1996), Al-Sarraf (2006) and Abd Al-Razzaq (2011). Many researchers reported that rainfall add chloride directly. It is low in summer as compared to rainy season and occupying the intermediate position in winter (Kalwale and Savale 2012), this agrees with the study findings which revealed the highest value of Cl- in winter, while lowest value in spring and summer. The results of present study agreed with those of Al-Lami et al (1996a) who found that Cl- values between 73-183 mg/L in Tigris River, Zaidan et al. (2009) recorded Cl- values varied between 20-189.5 mg/L in Euphrates River and Sabah & Fadhel (2011) who recorded in his study Cl- values were ranged between 95-160 mg/L in in Al-Gharraf River. But was lower than that reported by Al-Tameemi (2004), who recorded in his study Cl- values was ranged between 298-648 mg/L in Dyalah river, ALZamili (2007) who recorded in his study Cl- values was ranged between 355-755 mg/l in in Al-Gharraf River and Abed Al-Razzaq (2011), recorded Cl- values varied between 27.28-237.85 mg/L in Tigris river (Appendix 2).The minimum concentration and the mean concentration of Cl- were within the permissible limit for both Iraqi standards river water 1967 No. (25), which was 2000 mg/L, and within WHO standards (1993), which was 250 mg/L (Appendix 1). 56 Chapter three Results and Discussion 160 Mean Chloride ion (mg/l) 140 120 St.1 100 St.2 80 St.3 60 St.4 40 St.5 20 0 Autumn Winter Spring Summer Figure (15): Seasonal variation of chloride ions in AL-Gharraf River during study period. 3.2. 5. Sulphate (SO4-2). Sulphates exist in nearly all natural waters, the concentrations varying according to the nature of the terrain through which they flow. They are often derived from the sulphides of heavy metals (iron, nickel, copper and lead). Iron sulphides are present in sedimentary rocks from which they can be oxidised to sulphate in humid climates; the latter may then leach into watercourses so that ground waters are often excessively high in sulphates. As magnesium and sodium are present in many waters their combination with sulphate will have an enhanced laxative effect of greater or lesser magnitude depending on concentration (EPA, 2001). Al-Gharraf river stations showed variation in sulphate value (Fig.16 ; Table 6).The minimum value was 172.42 mg/L in station 4 during spring 2013, and the maximum value of 360 mg/L in station 2 during winter 2013. The statistical analysis showed a significant differences among seasons at (P˂0.05), but no any significant differences among stations (Table 6). Slightly higher concentrations of sulphate were detected at study area in station 2 and 3, and this may be due to untreated domestic sewage of the AlHaay city. 57 Chapter three Results and Discussion The increase in sulphate value in winter and decrease in spring generally due to discharge of the domestic sewage and agricultural runoff, these ions can produced from decompositions of organic matters or using chemical fertilizers in agriculture (Imarah and Munther, 1993; Grasby et al., 1997). Sulphates are formed due to the decomposition of various sulphur containing substances present in water bodies. The sulphate ions (SO4)-2 occur naturally in most water supplies and hence are also present in well waters (Ezeribe et al., 2012). The values obtained for each of the locations in Al-Gharraf river are exceed the permissible limit for both Iraqi standards for drinking water (Abbawi & Mohsen, 1990), which was 2000 mg/L, and within WHO standards drinking water (2004), which was 250 mg/L (Appendix 1). The sulphate values recorded in the present study is coincided with findings of Salih & Jafer (2003), found the sulphate value between 240-300 in AL-Hindia river, Al-Gizzy (2005), found the sulphate value between 231383 in Al-Gharraf river, AL-Zamili (2007), found the sulphate value between 142.35-312.1 in Al-Gharraf river , Al-Fatlawey (2007), found the sulphate value between 197.3-309.3 in Tigris river and Al-Ghanemi (2011) found the sulphate value between 19.84-340.6 in Euphrates river. Also agree with international studies of Abdo et. al.(2010) on Nile river in Egypt , Munna et al. (2013) on Surma river in Bangladesh and Ramesh & Selvanayagam (2013) on Kolavoi Lake in India (Appendix 2). 58 Chapter three Results and Discussion 350 Mean SO4 (mg/L) 300 250 St.1 200 St.2 150 St.3 St.4 100 St.5 50 0 Autumn Winter Spring Summer Figure (16): Seasonal variation of sulphate ions in AL-Gharraf River during study period. 3.2. 6. Nitrate(NO3-2). Nitrate is the most highly oxidized form of nitrogen compounds commonly present in natural waters. Significant sources of nitrate are chemical fertilizers, decayed vegetable and animal matter, domestic effluents, sewage sludge disposal to land, industrial discharge, leachates from refuse dumps and atmospheric washout. Depending on the situation, these sources can contaminate streams, rivers, lakes and ground water. Unpolluted natural water contains minute amounts of nitrate (Foglar, 2013). High nitrate levels in waters to be used for drinking will render them hazardous to infants as they induce the "blue baby" syndrome (methaemoglobinaemia).The nitrate itself is not a direct toxicant but is a health hazard because of its conversion to nitrite which reacts with blood haemoglobin to cause methaemoglobinaemia (Robert, 2006; EPA, 2013). Nitrate values are presented in Figure (17) and Table (6). The highest concentration of NO3 ions was recorded in autumn 2012 at station 2 which was 15.76 mg/L, while the lowest value was recorded in spring 2013 at station 1and 4 which was 5.7 mg/L. The statistical analysis revealed significant differences (P<0.05) in NO3 among seasons but no any significant 59 Chapter three Results and Discussion differences among stations was observed (Table 6 ).The positive correlation between NO3 and BOD5 and turbidity (r= 0.449 and 0.662 ),while the no significant negative correlation with DO (r= -0. 032) was observed in present study (Table 7). Increase in nitrate content in station 2 and 3 could be related to the the impact of Al-Haay city sewage effluent. High nitrate level in AL-Gharraf river during autumn and winter is due to the rainfall and fertilizer runoff as well as bacterial activity which convert nitrite to nitrate and the decomposition of organic compounds, but the decreasing of nitrate in spring may be due to the dilution factor and consumption of nitrate by phytoplankton growth and reduction of nitrate to nitrite in the bottom (Allen, 2011; Salman and Hussain, 2012). The results of this study were higher than those observed by Al-Saadi et al. (1996) who found NO3 values ranging from 0.010-0.13 mg/l in Qarmat Ali river, Al-Fatlawy (2005) that found the NO3 values ranged between 0.0015-0.360 mg/l in Euphrates river, and Sabah and Fadhel (2011) ) that found the range between 1.4-2.5 mg/L in Al-Gharraf river, whereas it was lower than that reported by AL-Zamili (2007) found the range for NO3 was 3.2-16.41 mg/L in Al-Gharraf river and Abed Al-Razzaq (2011) with a range of between 0.58-49.551mg/L in Tigris river (Appendix 2). But this study findings coincided with previous studies of Hassan (1997) on Hilla river, Kathy (2008) on Al-Gharraf river, Hashim (2010) on Tigris and Salman (2006) on Euphrates river (Appendix,2). The values of NO3 for all water samples from selected sites are within the permissible limit for both Iraqi standards river water 1967 No.(25) and WHO standards drinking water (2004), which was 50 mg/L (Appendix 2). 60 Chapter three Results and Discussion 16 Mean NO3 (mg/L) 14 12 St.1 10 St.2 8 St.3 6 St.4 4 St.5 2 0 Autumn Winter Spring Summer Figure (17): Seasonal variation of NO3 in AL-Gharraf River during study period. 3.2. 7. Phosphate (PO4-3). Phosphorus is present in natural waters primarily as phosphates. Phosphates can enter aquatic environments from the natural weathering of minerals in the drainage basin, from biological decomposition, and as runoff from human activities in urban and agricultural areas (UNEPA, 2008; Flores and Zafaralla, 2012). Phosphorus is the principal growth-limiting nutrient for macroplankton and phytoplankton growth in freshwater rivers and lakes and is the main cause of eutrophication in rivers and lakes . Additional phosphorus encourages algal growth beyond the natural levels. This growth depletes the dissolved oxygen in the water, causes algal blooms in lakes and fish kills in rivers (EPA, 2013) The phosphate concentration in Al-Gharraf river ranged from 0.13-0.50 mg/L (Figure 18 and Table 6). The minimum value was 0.13 mg/L in station 1 during autumn 2012, and the maximum value was 0.50 mg/L in station 2 during spring 2013. The statistical analysis showed a significant differences among seasons at (P˂0.05) and significant differences among stations except station 2 with 5 and station 3 with 4 (Table 6). 61 Chapter three Results and Discussion The negative correlation between PO4 and DO (r= -0.333), while the positive correlation with BOD5 (r= 0.469) was observed in present study (Table,7). Increasing levels of PO4 in Al-Gharraf river may be due to high concentration of detergents in sewage, in addition to the high density of agricultural areas, the phosphate fertilizers raised with high percentage as result of increased agricultural activity that might be the cause of high concentrations of phosphate. Hassan (2001) reported that increase in phosphate concentration during spring season may be related to rainfall and death of aquatic plants and lesser consumed phosphate by phytoplankton, while the decline during autumn due to consumed by plants and phytoplankton in photosynthesis and increase soil particles adsorption (Lind, 1979). The values of phosphate for most selected sites are exceed the permissible limit for both Iraqi standards river water 1967 No.(25) ), which was 0.4 mg/L, and WHO standards drinking water (2004), which was 0.1 mg/L (Appendix 1). These results agrees with the studies of Hussein & Fahad (2008) found the phosphate value between 0.03-0.52 mg/L in AL-Gharraf river, Ali (2010) found the phosphate value between 0.195-0.558 mg/L Greater Zab river and Al-Kuraishi (2011) found the phosphate value between 0.03-0.97 mg/L in Tigris river (Appendix 2). Also these data agree with other international studies of Imnatoshi and Sharif (2012) found the phosphate value ranging from 0.01-0.5 mg/L on Doyang river in Nagaland, Kalwale and Savale (2012) on Deoli Bhorus Dam in India and Ramesh and Selvanayagam (2013) found the phosphate value between 0.07-0.6 on Kolavoi Lake in India (Appendix 2). 62 Chapter three Results and Discussion 0.5 Mean PO4 (mg/L) 0.4 St.1 0.3 St.2 St.3 0.2 St.4 St.5 0.1 0 Autumn Winter Spring Summer Figure (18): Seasonal variation of PO4 in AL-Gharraf River during study period. 3.2. 8. Heavy metals. The Pollution of aquatic ecosystem by heavy metals has assumed serious proportions due to their toxicity and accumulative behavior. Unlike organic pollutants, natural processes of decomposition do not remove heavy metals. Metals are introduced into the aquatic system as a result of weathering of rocks and soils in addition to industrial wastewater discharges, sewage as well as from atmospheric deposition (Leena et al., 2012). 3.2. 8.1.Cadmium (Cd). Cadmium occurs in sulphide minerals that also contain zinc, lead or copper, is usually associated with zinc. Cadmium is highly toxic and has been implicated in some cases of poisoning through food. Minute quantities of cadmium are suspected of being responsible for adverse changes in arteries of human kidneys, also causes cancer for human and laboratory animals . A cadmium concentration of 0.2mg/L is toxic to certain fishes. Cadmium may enter water as a result the domestic sewage and industrial discharges. The maximum level for cadmium for drinking water standard is 0.005 mg/L (EPA, 2002; Raikwar et al 2008) 63 Chapter three Results and Discussion The obtained results showed that the maximum value of Cd recorded in summer 2013 at station 2 which was 0.099 ppm, while the minimum value of Cd was recorded in winter 2013 at station 1 which was 0.001 ppm (Fig.19 ; Table 8). The statistical analysis of the data showed significant differences among season at (P≤0.05) and significant differences among stations except station 1 with 2 and station 2 with 4 & 5 (Table 8). The significant positive correlation with Pb, Zn and water temperature (r=0.835; r=0.603and r=0.593 respectively) (Taple 9).The cadmium is very strongly adsorbed on muds, humus and organic matter, leading to the possibility 'of entry to the food chain via fish and fish food, and subsequent accumulation in tissue (EPA, 2001). The increase of the concentration of Cd during summer season and decrease during winter due to increased discharge of domestic sewage especialy at station 2 and urban storm-water runoff containing Cd-laden materials. Also, using of fertilizer and pesticides that is added to agricultural lands which causes increase the rate of cadmium in the soil and therefore it transfers into the river water because of irrigations and the dusty storms (Lawson, 2011; Ogunfowokan, et al., 2013) . The study results agreed with those of different works of Al-Khafaji (1996) on Shatt Al-Arab river, Al-Saadi et al. (2001) on Diyala river, Salman (2006) on Euphrates river, Hussein & Fahad (2008) on Al-Gharraf river, Hashim (2010) on Tigris river in Iraq and Rahman (2005) on Shitalakhya river in Bangladesh, Danazumi & Bichi (2010) on Challawa river in Nigeria, Amadi (2012) on Aba river in Nigeria, Kumwenda et. al.(2012) on Mudi river in Malawi and Bamakanta et al. (2013) on Nagavali River in India. All these were summarized in Appendix (5). Generally, the values of Cd for all selected sites are exceed the permissible limit for both Iraqi standards river water 1967 No.(25) ), which 64 Chapter three Results and Discussion was 0.005 ppm, and WHO standards drinking water (2006), which was 0.003 ppm (Appendix 4). 0.08 0.07 Mean Cd (ppm) 0.06 St.1 0.05 St.2 0.04 St.3 0.03 St.4 0.02 St.5 0.01 0 Autumn Winter Spring Summer Figure (19): Seasonal variation of cadmium in AL-Gharraf River during study period. Table (8): Minimum and maximum ( First Line), mean and standard deviation ( Second Line), for heavy metals studied (Cd, Pb, and Zn) at study stations during 2012-2013. Stations St.1 St.2 St. 3 St.4 St.5 Cadmium ppm 0.001- 0.011 0.0044 ± 0.0032 ab 0.002 - 0.099 0.0323 ± 0.0408 a 0.004 – 0.095 0.0191 ± 0.0288 a 0.006 – 0.087 0.0190 ± 0.0246 a Lead ppm 0.004 – 0.05 0.0157 ± 0.0172 d 0.01 – 0.32 0.1593 ± 0.137 a 0.003 – 0.097 0.0104 ± 0.0310 ab 0.015 - 0. 19 0.090 6 ± 0.0644 0.025 – 0.099 0.0651 ± 0.0247 c 0.03 - 0.087 0.0543 ± 0.0207 c 0.025 – 0.07 0.0473 ± 0.0133 d 0.03 – 1.1 0.4674 ± 0.417 a 0.045 – 0.50 0.1871 ± 0.17 c 0.05 – 0. 39 0.1703 ± 0.127 c Heavy metals Zinc ppm b 0.036 – 0.8 0.3022 ± 0.289 b *Station that carrying similar character were no any significant difference between them. 65 Chapter three Results and Discussion Table (9):The correlation (r) among some water parameters and heavy metals. Water pH Temp. pH EC Salinity TDS TH Cl SO4 Cd Pb Zn NS 0.412 ** -0.559 ** -0.586 * -0.529 ** -0.766 ** -0.783 ** -0.578 ** 0.593 NS 0.354 NS 0.171 NS -0.091 NS -0.129 NS -0.075 NS -0.403 * -0.468 NS -0.211 NS 0.134 NS -0.176 NS -0.319 EC Sal. TDS TH Cl SO4 Cd Pb ** 0.999 ** 0.997 ** 0.747 ** 0.832 ** 0.785 NS -0.105 NS -0.239 NS -0.351 ** 0.994 ** 0.766 ** 0.847 ** 0.789 NS -0.132 NS -0.243 NS -0.338 ** 0.737 ** 0.818 ** 0.786 NS -0.081 NS -0.232 NS -0.352 ** 0.869 ** 0.616 NS -0.215 NS 0.012 NS 0.06 ** 0.797 NS -0.361 NS -0.288 NS -0.279 NS -0.355 NS -0.419 ** -0.516 ** 0.835 ** 0.603 ** 0.897 **= Significant correlation at P<0.01. *= Significant correlation at P<0.05. NS= Non-significant correlation. 3.2. 8.2. Lead (Pb). Lead is one of the very toxic heavy metals that not only accumulate in individual but also have the ability to affect the entire food chain and disrupt the health system of human beings, animals and phytoplanktons (David et al., 2003). The lead reaches the water system through urban runoff or discharges such as sewage treatment plants and industrial plants. Industrial production processes and their emissions, mining operation, smelting, combustion sources and solid waste incinerators are the primary sources of lead. Another source of Pb is lead paint, batteries, lead piping used in water distribution system (Singh et al. 2012). 66 Chapter three Results and Discussion Al-Gharraf river water samples of all stations showed variation in Pb value (Fig.20 ; Table 8).The lowest value was 0.004 ppm in station 1 during winter 2013, and the highest value was 0.32 ppm in station 2 during spring 2013. The statistical analysis of the data showed significant differences among season at (P≤0.05) and significant differences among the stations except between station 4 and 5 (Table 8 ). The positive correlation with Zn and water temperature (r=0.354 and r=0.897 respectively), whereas the no significant negative correlation with pH (r= -0.176), (Table 9). The pH affects solubility of metal (Pb, Cd and Zn) hydroxide, and most metals hydroxide has very low solubility under pH conditions in natural water .Because hydroxide ion activity is directly related to pH, the solubility of metals hydroxide increases with decreasing pH, and more dissolved metals become potentially available for incorporation in biological processes as pH decreases pH (6-7) stimulate metals dissolution and complex formation (Al-Haidarey , 2009) . The recorded concentrations of Pb in Al-Gharraf River in all the stations as a result of the passage of the river through agricultural lands that used different chemicals that contains Pb , which are used in product of agricultural crops, these compounds contained which accumulate in the agricultural soils and find their way to the streams during the raining seasons or as a result of the erosion of soils (Fahad, 2006). The concentration of Pb for most the study stations was exceed the permissible limit for Iraqi standards river water 1967 No.(25), which was 0.005 ppm, and WHO standards drinking water (1993), which was 0.01 ppm and EQA standards water pollution (2001), which was 0.01 ppm (Appendix 4). The results of this study were higher than those observed by Al-Lami & AlJaberi (2002) on Tigris river, Salman (2006) on Euphrates river, Al- Awady (2011) on Al-Masab Alamm and Al-Khafaji (1996) on Shatt Al-Arab river, while coinciding with Al-Saadi et al. (2001) on Diyala river, Al-Imarah (2002) 67 Chapter three Results and Discussion on Shatt Al-Hilla, Farhood (2012) on Euphrates river and Akbar & AL-Khazali (2012) on Al-Gharraf river (Appendix 5). Also the results of Pb in current study was lowest than the results of the international studies of Rahman (2005) on Shitalakhya river, Danazumi & Bichi (2010) on Challawa river, Idriss and Ahmad (2012) on Juru river and Kumwenda et. al.(2012) on Mudi river (Appendix 5). 0.35 0.3 Mean Pb (ppm) 0.25 St.1 0.2 St.2 0.15 St.3 St.4 0.1 St.5 0.05 0 Autumn Winter Spring Summer Figure (20): Seasonal variation of lead in AL-Gharraf River during 2012/2013 3.2. 8.3. Zinc (Zn). Zinc, in small concentrations, is an essential element for living organisms. It is essential for the enzymes required for forming red blood cells in living organisms. It is also essential for plants because it takes part in the biosynthesis of nucleus acids and polypeptides required for plants. On the other hand, when concentration of zinc increases above certain a limit, it becomes toxic to man, animals and plant life (Dojlido and Best, 1993; EPA, 2001). Toxicity of zinc becomes more severe when present with other heavy metals, such as cadmium, in water because it has synergistic effect with these metals. The main sources of zinc to the environment are mining operations, secondary metal production, coal combustion, rubber tire wear and phosphate fertilizers (Salim et al., 2003). 68 Chapter three Results and Discussion Znic values are presented in Figure (21) and Table (8). The highest concentration of Zn was recorded in spring 2013 at station 2 which was 1.1 ppm, while the lowest value of Zn was recorded in winter 2013 at station 1 which was 0.025 ppm. The statistical analysis revealed significant differences (P≤0.05) in Zn among seasons and significant differences among stations except among station 4 and 5 (Table,8).The positive correlation between Zn and water temperature (r= 0.171), while the negative correlation with pH (r= 0. 319), (Table 9). The increase of the concentration of Zn during spring season might be resulted from the increase of discharge of domestic sewage especially at station 2 and agricultural and industrial discharge along the Al-Gharrafriver as well as the different population densities as suggested by (Alloway& Ayres, 1997; WHO, 2006), whereas lowest values during winter may be due to the dilution factor followed rainfall (Al-Taee, 1999). The average concentration of Zn for all selected sites in the Al-Gharraf River were in the permissible range of values reported by the Iraqi standards river water 1967 No.(25) ), which was 0.5 ppm, and WHO standards drinking water (2006), which was 3 ppm. While, the mean concentration of Zn was above the USEPA (2007) recommended maximum values (0.015 ppm). The results of this study were higher than those found by Al-Khafaji (1996 ) on Shatt Al-Arab, Salman (2006) on Euphrates River, Al-Helaly (2010) on Al-Gharraf River, Shukri, et al.(2011) on Tigris river in Iraq and Chavez et. al. (2006) on Laguna dy Bay River in Philippines, Levkov & Krstic(2002) on Vardar river in Macedonia (Appendix 5). On the other hand, these data were much lower than those reported by AlSaadi et al. (2001) on Diyala river, Al-Imarah (2002) on Al-Masab Alamm river in Iraq and Rahman (2005) on Shitalakhya in Bangladesh, Danazumi & Bichi (2010) on Challawa river, Nigeria, Salati and Moore (2010) on Khoshk river in Iran, Idriss & Ahmad (2012) on Juru river in Malaysia (Appendix 5). 69 Chapter three Results and Discussion In generally, the results of Zn in current study coincided with the results of the study of Hussein and Fahad (2008) on the Al-Gharraf River in Iraq, Samir and Ibrahim (2008) on Nile River in Egypt and Kumwenda et. al.(2012) on Mudi River in Malawi (Appendix 5). 1.2 Mean Zn (ppm) 1 St.1 0.8 St.2 0.6 St.3 St.4 0.4 St.5 0.2 0 Autumn Winter Spring Summer Figure (21): Seasonal variation of zinc in AL-Gharraf River during 2012/2013 3.3.Bactriological Characteristics. Bacteria are ideal sensors for microbial pollution of surface water because of their fast response to environmental (Kavka and Poetsch, 2002). The use of bacteria as water quality indicators can be viewed in two ways, which were suggested by Baghed et al. (2005) as the presence of such bacteria can be taken as an indication of fecal contamination of water and an indication of potential danger of health risks. 3.3. 1. Total Bacterial Count (T.B.C). The total bacterial includes all of the bacterial species that are capable of growing in or on a nutrient rich solid agar medium. The incubation temperature and time used were 37°C for 24 hours to encourage the growth of bacteria derived from humans and warm- blooded animals (APHA, 1998; WHO, 2004). The distribution and seasonal variation of the Total Bacterial Count in AlGharraf river are shown in the Figure (22) and Table (10). The highest 70 Chapter three Results and Discussion number of total bacterial count was recorded in winter 2013 at station 2 which was 75000 CFU/1ml, while the lowest number of total bacterial count was recorded in summer 2013 at station 1 which was 100 CFU/1ml. These results exceeded local and international guidelines ranges . The statistical analysis revealed significant differences (P≤0.05) in TBC among seasons but no any significant differences among stations was found except among station 2 (Table 10).The positive correlation between TBC and other bacterial number (Table 11), and the positive correlation with BOD5 and salinity (r= 0.533 and 0.447) respectively, while the negative correlation with DO and water temperature (r= -0. 096 and r= -0. 395), (Table 11). High number of TBC in Al-Gharraf river was recorded during autumn and winter ,which might be the consequence of the high level of suspended solid and nutrients in the drainage water which affected the survival of aquatic microflora (Hader et al., 1998), also it may be because the high numbers of bacterial level of the Al-Gharraf River due to receiving the large amounts of sewage especially in Al-Haay city, as wall as increase the agricultural activities have led to increase bacteria number in the waters of the river (Adams and Kolo, 2006). On the other hand, low number of bacteria during spring and summer may be due to flood period which dilutes the organic matter which used as food for the bacteria, as well as high temperature that caused kill of large number from the bacteria (Davies et al.,1999; Abdo, et. al. 2010), this results agree with the results of Mashcor (1986) and Sabae & Rabeh (2006). In general, present data coincided with those of Mayaly (2000) on Tigris and Dyalah river, Sabri et al.(2001) on Euphrates river, and Al-Jebouri & Edham (2012) on Lower Al-Zab river, while disagree with studies of Niewolak, (1998) on Czarna Haricza river in Poland, AL-Rahbi (2002) on AL-Habania & AL-Tharthar reservoirs and Ibrahim, et al. (2013) on Tigris river in Iraq (Appendix 6). 71 Chapter three Results and Discussion 60000 T.B.C cfu/1ml 50000 St.1 40000 St.2 30000 St.3 20000 St.4 10000 St.5 0 Autumn Winter Spring Summer Figure (22): Seasonal variation of total bacterial count in AL-Gharraf River during study period. Table (10): Minimum and maximum ( First Line), mean and standard deviation ( Second Line), for Bacteriological characteristics at study stations during 2012-2013. Stations Parameters Total Bacterial Count CFU/1ml Total Coliform CFU /100ml Faecal Coliform CFU /100ml Total Streptococcus CFU /100 Faeal Streptococcus CFU /100 St.1 St.2 St. 3 St.4 St.5 100 – 490 211 ± 159.4 b 740 – 75000 17613 ± 27615 170-1600 757 ± 614.1 b 230-1500 720 ± 390.5 b 130- 1705 645 ± 502.0 b 2300-24000 10921 ± 733 b 2300-18000 7979 ± 5378 b 300-16000 4708 ± 5244 bc 290-5400 1259 ± 1930 bc a 19600 -34000 25475 ± 5657 a 220-2300 678 ± 797.4 d 19600-33000 24767 ± 4742 a 2100-22500 10679 ± 699 b 2200-17200 6979 ± 5783 c 260-16000 4195 ± 4873 c 230-3500 1246 ± 1162 d 13500-32600 19883 ± 4816 a 9000-25100 11950 ± 567 b 1500-16000 6625 ± 5807 c 260-5400 1694 ± 1877 d 200-1700 673 ± 681.0 cd 3500-21000 12092 ± 6142 a 5100-9200 5005 ± 2934 b 240-16000 4276 ± 5318 b 230-5400 1027 ± 1544 c *Station that carrying similar character were no any significant difference between them. 72 Chapter three Results and Discussion Table (11):The correlation (r) among some water parameters and bacterial number. Water Current pH Salinity DO BOD T.B.C T.C F.C T.S F.S Water Temperature Water Current ** -0.649 NS 0.412 ** -0.586 ** -0.752 NS -0.184 NS -0.365 pH Salinity DO BOD5 T.B.C T.C NS 0.203 NS 0.339 ** 0.718 NS -0.256 NS 0.139 NS -0.129 NS 0.028 ** -0.635 NS -0.275 NS 0.355 NS 0.491 NS 0.447 NS -0.387 NS -0.096 * 0.533 NS -0.325 NS -0.295 NS -0.111 NS -0.147 ** -0.641 ** -0.627 NS 0.414 NS 0.425 NS -0.313 NS -0.343 ** 0.909 ** 0.908 ** 0.723 ** 0.697 ** 0.982 NS -0.263 NS -0.243 NS -0.045 NS -0.169 ** -0.624 * -0.525 NS 0.324 NS 0.395 NS -0.348 NS -0.307 ** 0.829 ** 0.784 ** 0.638 ** 0.738 ** 0.917 ** 0.813 F.C T.S ** 0.889 ** 0.791 ** 0.749 **= Significant correlation at P<0.01. *= Significant correlation at P<0.05. NS= Non-significant correlation. 3.3. 2. Total Coliform (TC). Coliform bacteria had been used historically to assess the microbial quality of drinking water. Also no consider as indicators of faecal contamination, but their presence indicates that your water supply may be vulnerable to contamination by more harmful microorganisms. Some coliform bacteria may be part of the natural bacterial flora in the water and intestines of human and warm-blooded animals. Coliforms are also considered useful for monitoring treatment processes and assessing the disinfection of new or repaired mains (WHO, 2003). 73 Chapter three Results and Discussion As shown in the Figure ( 23) and Table (10), the minimum value of T.C was recorded in summer 2013 at station 1 which was 290 CFU/100ml, while the maximum value of T.C was found in winter 2013 at station 2 which was 34000 CFU/100ml. The statistical analysis revealed significant differences (P≤0.05) in T.C between seasons and significant differences between stations except between station 1 with 5 and 3 with 4 (Table 10). The sudden increase in numbers of TC in station 2 may be due to the effluent discharged enriched with organic matter from Al-Haay city which leading to increase them . The results revealed positive correlation between T.C and BOD5 and salinity (r= 0.909, 0.414) respectively, while the negative correlation with DO and water temperature (r= -0. 313 and r= -0. 325), (Table 11). On the other hand, the number of total coliforms for all the study stations was exceed the permissible limit for both India standards for water quality (1975), which was1 per 100ml, and exceed the WHO standards (1993), which was 10 per 100ml. Al-khafaji et al. (2012 ) has found that the highest value was 3550 but much lower those values found in this study. This may be due to the increased the concentrations of nutrients as nitrogen and phosphorus from domestic sewage and pollution sources on the riverbanks which agrees with Al-Abadi (2011). Olapade, (2012 ) suggested that nature, ratio and degree of pollution by coliform bacteria in water depend on many factors such as suitable of temperatures for growth , activity of microorganisms , increased the concentrations of nutrients from organic materials and salts in surface water sources and the impact of dust storms that have encouraged to increase biomass in the water. The obtained results in this study were higher than those of previous studies such as Al-Azzawi (2004) who found the mean for T.C was 900 74 Chapter three Results and Discussion CFU/100 in Euphrates river and Ibrahim et al., (2013) found the mean for T.C was 1600 CFU/100 in Tigris river, while Mayaly (2000) found the mean for T.C was 230600 CFU/100 in Tigris river and Mohammad (2012) found the mean for T.C was 100085 CFU/100 in Uosifea river, which higher than of present study. Also the results coincided with international studies of Hamzah et al. (2011) on Coastal Water in Malaysia and Anukool & Shivani(2011) on Gomti river and Firozia & Sanal (2013) on Pamba river in India(Appendix 6). 35000 30000 T.C cfu/100ml 25000 St.1 20000 St.2 15000 St.3 St.4 10000 St.5 5000 0 Autumn Winter Spring Summer Figure (23): Seasonal variation of total coliform in AL-Gharraf River during study period. 3.3. 3. Faecal Coliform (FC). The presence of faecal coliform bacteria in aquatic environments indicates that the water has been contaminated with the fecal material of man or other animals. At the time this occurred, the source water may have been contaminated by pathogens or disease producing bacteria or viruses, which can also exist in fecal material. The presence of fecal contamination is an indicator that a potential health risk exists for individuals exposed to this water. Fecal coliform bacteria may occur in ambient water as a result of the overflow of domestic sewage or nonpoint sources of human and animal waste (Shivayogimath et al., 2012). 75 Chapter three Results and Discussion Current results revealed high value of F.C recorded in winter 2013 at station 2 which was 33000 CFU/100ml, while the lowest value of F.C was recorded in spring 2013 at station 1 which was 220 CFU/100ml (Fig.24 ; Table 10). The statistical analysis revealed significant differences (P<0.05) in F.C between seasons and significant differences between stations except between station 4 with 5 (Table 10). The increase in numbers of FC in station 2 and 3 may be due to the effluent discharged enriched with organic matter from Al-Haay city which leading to increase in BOD5 value agrees with Rahbi (2002). The positive correlation between F.C and BOD5 and salinity (r= 0.908 and 0.425 respectively ), while the negative correlation with DO and water temperature (r= -0. 343 and r= -0. 295), (Table 11). The values of FC for all selected sites are exceed the permissible limit for US-EPA (2011) which established FC concentration limit of (200 CFU/100mL) in the water for recreational and contact usages and equal to (0 CFU/100mL) for drinking water. Byamukama et al. (2005) attributed a gradual increase of faecal coliform bacteria in water during winter season to higher survival and growth at suitable temperature. Fecal coliforms are the best indicators for the assessment of recent fecal pollution, mainly caused by raw and treated sewage, and diffuse impacts from the farmland and pasture (Kavka and Poetsch, 2002). In this study fecal indicator bacteria abundance were measured in samples collected in river located in Al-Haay city. Results showed that this river which flowing through urban areas was more contaminated than those rivers which flowing through agricultural areas. This study coincided with previous studies of Sabri et al.(2001) on Euphrates river, Al-Fatlawy (2007) on Tigris river and Al-Abadi (2011) on Abu-Zariq Marsh , also agree with international studies of Hamzah et al. 76 Chapter three Results and Discussion (2011) on Coastal Water in Malaysia and Anukool & Shivani (2011) on Gomti river in India. But disagree with studies of Maghrebi et al.(2010) on Jajrood river in Iran, Christensen et al. (2013) on Drinking Water in Switzerland and AL- Tameemi (2004), Al-Aney (2012) and Ibrahim,et al. (2013) on Tigris river in Iraq (Appendix 6). 35000 F.C cfu/100ml 30000 25000 St.1 20000 St.2 15000 St.3 10000 St.4 St.5 5000 0 Autumn Winter Spring Summer Figure (24): Seasonal Variation of faecal coliform in AL-Gharraf River during study period. 3.3. 4. Total Streptococcus (TS). Streptococcus spp. that normally occurs in faecal matter, were used instead of Fecal Coliform because Fecal streptococci survive well in the environment. Presence of Streptococcus faecalis in the all selected locations confirms faecal pollution of the river water. The sources of effluents in AlGharraf river include herbicides and pesticide application by farmers around and near the river and human and animal faeces, sewage and industries waste from mechanic workshops (Wiggins,1996; Abbas et al , 2007). The total streptococcus average in Al-Gharraf river ranged from 124619883 CFU/100ml (Fig.25 and Table 10). The minimum value was 230 CFU/100ml in station 1 during spring 2013, and the maximum value was 32600 CFU/100ml in station 2 during winter 2013. According to WHO (1996a) this results exceeded local and international guidelines ranges .The 77 Chapter three Results and Discussion statistical analysis showed a significant differences among seasons at (P˂0.05) and significant differences among stations except station 1 with 5 (Table 10). The results revealed the negative correlation between T.S and water temperature & DO (r= -0.263 & r= -0.348 respectively),while the positive correlation with BOD5 and salinity (r= 0.324 and r= 0.829 respectively) was observed in present study (Table 11). Al-Gharraf River vary considerably concentration because of selfpurification mechanism, good mixing, and larger water volume. The increase in numbers of TS during winter especially at station 2 and 3, may be due to the organic matter which enters in large quantities to the station 2 and low water temperature which act on survival of the bacteria for longer period (Atlas et al., 1996). Niewolak (1998) found that the average value for T.S on Czarna Haricza river in Poland was 77501.5 CFU/100ml in winter, while Al-Mayaly (2000) found the average value for T.S in Tigris River was 230003.5 CFU/100ml in winter, all the studies revealed higher T.S number than present study. Also this studies agree with Sabri et al.(2001) on Euphrates river , Al-khafaji et al. (2012 ) on Abu-Zariq Marsh in Iraq and Hamzah et al. (2011) on Coastal Water in Malaysia and Firozia & Sanal (20138b) on Pamba river in India (Appendix 6). 30000 T.S cfu/100ml 25000 St.1 20000 St.2 15000 St.3 10000 St.4 5000 St.5 0 Autumn Winter Spring Summer Figure (25): Seasonal variation of total streptococcus in AL-Gharraf River during study period. 78 Chapter three Results and Discussion 3.3. 4. Faecal Streptococcus (FS). There are several studies demonstrated that faecal streptococci have been considered to be useful indicators of faecal contamination of water resources (Mwakalobo et al., 2013). The presence of faecal streptococci is evidence of faecal contamination. Faecal streptococci tend to persist longer in the environment than total or faecal coliforms and are highly resistant to drying (UNEP/WHO, 1996) . As shown in Figures (26) and Table (10) the number of Feaecal streptococcus in Al-Gharraf River. The results revealed high value of F.S was recorded in winter 2013 at station 2 which was 21000 CFU/100ml, while the lowest value of F.S was recorded in spring 2013 at station 1 which was 200 CFUl/100ml. The statistical analysis revealed significant differences (P<0.05) in F.S between seasons and significant differences between stations except station 3 with 4 (Table 10). According to WHO (1996a) this results exceeded local and international guidelines ranges . Negative correlation recorded between F.S and water temperature & DO (r= -0.243 & r= -0.307 respectively), while the positive correlation with BOD5, and salinity (r= 0.734 and r= 0.395 respectively) was observed in the present study (Table 11). The results showed that the high variability in levels and number of faecal streptococcus in Al-Gharraf River may be due to the variation of environmental conditions such as solar radiation, turbidity, temperature, salinity, dissolved oxygen and organic matter (Yehia and Sabae, 2011). The minimum values` of the faecal streptococcus were recorded in the warmer seasons, which might be attributed to the rapid die-off with increasing of solar radiation and high temperature as well as flood period which dilutes the organic matter which used as food for the bacteria (El-Shenawy, 2005). 79 Chapter three Results and Discussion This study comes in accordance with the studies of Al-Mayaly (2000) on Tigris River, Al-khafaji et al. (2012 ) on Abu-Zariq Marsh and Al-Jebouri & Edham (2012) on Lower Al-Zab river, whereas disagree with studies of ALRahbi (2002) on AL-Habania & AL-Tharthar reservoirs, AL- Tameemi (2004) on Diyala & Tigris River and Al-Aney (2012) on Tigris River (Appendix 6). The current results were less than the international study of Anukool & Shivani (2011) on Gomti River in India who found F.S number (917707.5 CFU/100ml) and also less than the study of Hamzah et al. (2011) on Coastal Water in Malaysia, who recorded the value for F.S number (1250750 CFU/100ml). While, the present results were higher than results of Sati et al. (2011) on Ganges River in India, who recorded the value for F.S number (16.0 CFU/100ml) and also higher than the study of Mwakalobo et al. (2013 ) on Coastal Waters in Tanzania., who recorded the value for F.S number (39.0 CFU/100ml) (Appendix 6). 16000 14000 F.S cfu/100ml 12000 St.1 10000 St.2 8000 St.3 6000 St.4 4000 St.5 2000 0 Autumn Winter Spring Summer Figure (26): Seasonal variation of faecal streptococcus in AL-Gharraf River during study period. 80 Conclusions Conclusions … 1. It seems clearly that Al-Gharraf river was contaminated by domestic sewage. 2. The seasonal study is the most effective than monthly study where changes is in the physical, chemical and biological properties of water appear clearly through the seasons of the year. 3. The BOD5 values affected clearly by excreta untreated wastewater because they decrease in non contaminated sites and increase in the contaminated sites. 4. The station 2 It is most polluted site being subjected to the influences of city sewage which is discharged directly into the river. 5. The study indicated to spatial and temporal variations in all characteristics of water studied. 6. Increasing levels of heavy metals in Al-Gharraf river where exceed the permissible limit except zinc may give a hint of water pollution by heavy metals.. 7. The organic and bacterial pollution levels were high at the center of the city and the adopted measures to control is weak and almost non-existent. 81 Recommendation Recommendation… 1. There must be a clipart responsible administrative authority for controlling industries and people to be ensuring continuously the raises of material in water and compared components of water with local and international parameters and make sure that treatment plants are working correctly. 2. There is urgent need to drainage and sewage water to not discharge in the river by created units to address what poses remnants of household, agricultural and industrial to use these wastes in several ways like organic fertilizer or use for irrigation purposes as long as the agricultural soils are considered candidates efficient to remove contaminants from wastewater. 3. Continued follow up the case of the river in terms of bacterial contamination and other potential contaminants such as hydrocarbon compounds, pesticides and examine their residuals to clarify its health effects on humans and animals after what can be done to reduce this pollution. 4. Determine the important hotbeds pollution sources that cause higher pollution for the purpose of monitoring and find appropriate solutions. 5. Support of the laboratories activities and the assurance of the application of the laws and regulations for the assessment of waste water and obliging all institutions relationship that to apply before being discharged into rivers and cooperation to support their application. 82 Recommendation 6. The attention by environmental sensitization and publications, programs and courses that transport environmental awareness and preserving on the environment and maintaining through the rationalization of consumption of pesticides and detergents. 83 References References … v -AAbbas, N.; Baig, I. A. and Shakoori, A. R.(2007). Faecal contamination of drinking water from deep aquifers in Multan, Pakistan. Pakistan J. Zool., vol. 39(5): 271-277. v Abbawi, S. A. and Hassan, M. S. (1990). Environmental Engineering, water analysis. Dar Al-Hekma for printing and publishing, Mosul. v Abbawi, S.A. and Mohsen, M.S., (1990). "Environmental Practical EngineeringWater Testing". 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Illinois State Water Survey Final Report for Midwest Technology Assistance Center (MTAC), UrbanaChampaign,IL. 118 Appendix Appendix… Appendix(1): Comparison between some water quality parameters of Al-Gharraf River with the Iraqi and international standards. Parameter WHO standards for drinking water in 2004 Iraqi standards for water quality in 1998 6.5- 8.5 EEC 464/76 stander for surface water quality (Tebbutt, 1998 ) 6.5- 8.5 pH TDS mg/L 500-1500 500-1500 1000 Turbidity NTU DO mg/L 0-50 0-25 25 >5 >5 >5 BOD5 mg/L >3 >5 >3 T.H mg/L 100 - 500 100-500 - Cl- mg/L 200 200 – 600 200 SO4 mg/L 200 200 - 400 150 - 250 NO3- mg/L 0 – 45 0 – 40 25 –50 PO4 mg/L 0.1 0.4 0.4 119 6.5- 8.5 Present study Minimum & Maximum 7.03 - 8.72 545.3 – 957 30-177 6.3-10.38 1 -7.01 306- 496 89-184.6 172.42 - 360 5.7 -15. 76 0.50 -0.13 Appendix Appendix(2): Comparison between physical and chemical characteristics of AlGharraf River with with local and international Rivers . River Tigris Iraq Tigris Iraq Euphrates Iraq Euphrates Iraq Shatt AlHilla- Iraq AlGharraf Iraq AlGharraf Iraq Nile Egypt Nile Egypt Bertam Malaysia Chambal India Mananga Philippine Noyyal India Al – Gharraf Water Temp. C˚ physical and chemical characteristics Water pH EC DO BOD5 Turbi. Current µS/cm mg/L mg/L NTU m/sec. - - 7.6 530.5 6.55 40.45 9.5 22.5 0.78 7.8 1125 8.35 3.55 61.5 Muath and Muna (2007) Al-Kuraishi (2011) 23 - 8.05 750 8.05 4.1 - Hassan, et. al. (2010) 22 0.175 8.05 605 8.5 3.5 - 24.65 - 7.75 1225 6 - - Al –Ghanemi ( 2011) Hassan, et. al. (2008) 24.25 - 7.2 - 7.85 3.6 47 Fahad ( 2006) - - 7.632 1137.7 - - - Sabah and Fadhel (2011) 26.6 - 7.33 1213.25 4.25 28.75 17.25 Ezzat, et. al. (2012) 24.95 - 7.95 387 11 3.4 - Abdo, et. al. (2010) 17.35 - 6.54 174.5 6.395 1.815 - Khalik, et al. (2013) - - 8.465 514.8 9.725 3.135 89.5 Saksena, et. al. (2008) 27 0.32 8.45 - 6.0 4.9 - 24.67 - 7.81 - 3.77 9.55 - Mary and Macrina (2012) Usharani, et. al. (2010) 0.59 7.875 1137.5 8.34 4.005 103.5 Present study 21 120 Reference Appendix Appendix table (2) River physical and chemical characteristics – = Reference = -3 TDS mg/L TSS mg/L T.H mg/L Cl mg/L SO4 mg/L NO3 mg/L PO4 mg/L Tigris Iraq Tigris Iraq Euphrates Iraq Euphrates Iraq Shatt AlHilla- Iraq Al-Gharraf Iraq 482.5 67.5 360 59.3 105.5 0.045 0.04 591.5 144.5 341.5 67.5 230.5 5.3 0.5 837.5 29.35 215 - 912.85 0.0655 0.0035 1139.5 33.76 566.5 - 180.22 0.1808 0.00385 808.5 - 700 - 903.3 0.254 0.034 - - 320 - - 0.041 0.0027 Al-Gharraf Iraq Nile Egypt Nile Egypt Bertam Malaysia Chambal India Mananga Philippines Noyyal India Al – Gharraf 607 - 443.83 124 139.83 1.88 0.20 386 - - 51.5 57.1 21.43 0.2 255.42 - - - 34.65 0.0207 0.0747 50 260.57 - - - 0.825 1.155 380 - 91 48.28 24.25 0.0165 0.027 - 82 - - - 9.103 4.819 302.22 132.22 226.66 76.5 - 2.04 1.58 751.15 158 401 136.8 121 266.21 10.73 0.315 Muath and Muna (2007) Al-Kuraishi (2011) Hassan, et. al. (2010) Al –Ghanemi ( 2011) Hassan, et. al. (2008) Fahad ( 2006) Sabah and Fadhel (2011) Ezzat, et. al. (2012) Abdo, et. al. (2010) Khalik, et al. (2013) Saksena, et. al. (2008) Mary and Macrina (2012) Usharani, et. al. (2010) Present study Appendix Appendix(3): Water Quality according to United State stander (ASCE) for raw water quality (Smehturst,1997) Parameter Excellent source 0.75-1.5 Good source 1.5-2.5 Poor source 2.5-4 Rejectable source >4 Coliform CFU/100 pH 50-100 100-5000 5000-20 000 > 20 000 6-8.5 Chlorides mg/L Fluorides mg/L < 50 5-6 8.5-9 50-250 3.8-5 9-10.3 250-600 < 3.8 > 10.3 > 600 < 1.5 1.5-3 >3 - BOD5 mg/L Appendix(4): Comparison between concentrations of heavy metals in Al- Gharraf River water with world and Iraqi standards by ppm unit. Heavy metals ppm WHO standards for drinking water in 2006 Iraqi Present regulation for study public water (Abbawi,1990) 0.003 EEC 464/76 stander for surface water quality (Tebbutt, 1998 ) 0.005 Cd 0.005 0.049 Pb 0.01 0.05 - 0.172 Zn 3 3 0.05 0.5625 122 Appendix Appendix(5): Comparison between concentrations of dissolved heavy metals in AlGharraf River with local and international Rivers by ppm unit (ND: Not Detected ) . Metal concentration ppm River Cadmium (Cd) Lead (Pb) Zin (Zn) Tigris Iraq Tigris Iraq Euphrates Iraq Euphrates Iraq Shatt AlArab Iraq Diyala Iraq Shatt Al-Hilla Iraq 0.002 0.0092 0.0891 - ND ND 0.00214 0.0001 0.0105 0.0022 0.022 0.010 0.00019 0.00023 0.00082 0.025 0.21 1.13 0.239 0.095 1.364 Al-Masab Alamm Al –Gharraf Iraq Nile Egypt Khoshk Iran Juru Malaysia Challawa Nigeria Aba Nigeria Shitalakhya Bangladesh Laguna Bay Philippines Mudi Malawi Vardar Macedonia Al –Gharraf 0.00005 0.00035 0.0121 0.0263 - 0.166 0.044 0.099 0.4636 0.001 - 1.4 0.155 1.175 52.915 - 1.051 2.986 0.002 0.012 3.360 0.06 0.74 2.46 ND 0.01 0.100 0.02 0. 57 0.115 0.00002 0.01231 0.00692 0.049 0.172 0.5625 Iraq 123 Reference Al-Lami and AlJaberi(2002) Shukri,et al., (2011 ) Salman (2006) Farhood (2012 ) Al-Khafaji (1996) Al-Saadi et al. (2001) Al-Imarah (2002) Al- Awady ( 2011) Sadek and Kamel (2008) Samir and Ibrahim (2008) Salati and Moore (2010) Idriss and Ahmad (2012) Danazumi and Bichi (2010) Amadi A. N. (2012) Rahman, Md. D. (2005) Chavez et. al.(2006) Kumwenda et. al. (2012) Levkov and Krstic (2002) Present study Appendix Appendix(6): Comparison between Bacteriological characteristics of Al-Gharraf River with with local and international Rivers. River Tigris Iraq Tigris Iraq Diyala Iraq ALHabania &ALTharthar Reservoirs Iraq Abu-Zariq Marsh Iraq Coastal Waters Tanzania Jajrood Iran Coastal Water Malaysia Ganges India Gomti India Lake Kivu Rwanda Czarna Haricza Poland Al – Gharraf Bacterial Number Reference T.B.C T.C CFU/1ml CFU/100 7507500 230600 F.C CFU/100 230011.5 5064 950 863 8505500 35023000 8505500 2280 7700 1300 - 3550 3000 - 9500 Al-khafaji et al. (2012 ) - 86.0 56.5 - 39.0 Mwakalobo et al. (2013 ) - 80085 27010 - - - 750125 10075 - 1250750 Maghrebi et al. (2010) Hamzah, et al., (2011) 16200 167 85.1 - 16 - 958627.7 1108627.7 - 917707.5 108900 67948.333 16683.666 - 220.2667 2600.1 25000.35 8300.15 77501.5 - 37550 17145 11610 16415 10600 124 T.S F.S CFU/100 CFU/100 230003.5 120002 Mayaly (2000) Ibrahim et al., (2013 ) AL- Tameemi ( 2004) 8100 600 AL-Rahbi ( 2002) Sati, et al. (2011) Anukool and Shivani (2011) Olapade (2012) Niewolak (1998) Present study ﺍﻟﺨﻼﺻﺔ... ﺃﺟﺮﻳﺖ ﻫﺬﻩ ﺍﻟﺪﺭﺍﺳﺔ ﻣﻦ ﺃﺟﻞ ﺗﺤﺪﻳﺪ ﺗﺄﺛﻴﺮ ﻣﻴﺎﻩ ﺍﻟﻤﺠﺎﺭﻱ ﺍﻟﻤﺤﻠﻴﻪ ﻓﻲ ﻣﺪﻳﻨﻪ ﺍﻟﺤﻲ /ﻣﺤﺎﻓﻈﺔ ﻭﺍﺳﻂ ﻋﻠﻰ ﺑﻌﺾ ﺍﻟﺨﺼﺎﺋﺺ ﺍﻟﻔﻴﺰﻳﺎﺋﻴﺔ ﻭﺍﻟﻜﻴﻤﻴﺎﺋﻴﺔ ﻭ ﺍﻟﺒﻜﺘﻴﺮﻳﻮﻟﻮﺟﻴﺔ ﻟﻨﻬﺮ ﺍﻟﻐﺮﺍﻑ .ﻳﻘﻊ ﻧﻬﺮ ﺍﻟﻐﺮﺍﻑ ﻓﻲ ﺍﻟﺠﺰء ﺍﻟﺠﻨﻮﺑﻲ ﺍﻟﺸﺮﻗﻲ ﻣﻦ ﺕ ِﻣ ْﻦ ﺍﻟﻌﺪﻳﺪ ﺍﻟﻌﺮﺍﻕ ﻭ ﺗﺤﻴﻂ ﻓﻴﻪ ﻣﺴﺎﺣﺎﺕ ﺷﺎﺳﻌﺔ ﻭﺧﺼﺒﺔ ﻣﻦ ﺍﻷﺭﺍﺿﻲ ﺍﻟﺰﺭﺍﻋﻴﺔ .ﻳَﺴﺘﻠ ُﻢ ﺍﻟﻨﻬ ُﺮ ﺃﻏﻠﺐ ﻣﻴﺎﻩ ﺍﻟﻔﻀﻼ ِ ﺑﺘﻄﻮﺭ ﺍﻟﻤﻨﻄﻘﺔ ﻓﺄﻥ ﺯﻳﺎﺩﺓ ﺗﺴﺮﺏ ﺕ ﺍﻟﻤﺤﻠﻴ ِﺔ ﻭﺍﻟﺰﺭﺍﻋﻴ ِﺔ ﻭﺍﻟﺼﻨﺎﻋﻴ ِﺔ .ﻭﺍﺭﺗﺒﺎﻁﺎ ﺪﻥ ﺑﻀﻤﻨﻬﺎ ﻣﻴﺎﻩ ﺍﻟﻔﻀﻼ ِ ِﻣ ْﻦ ﺍﻟ ُﻤ ِ ِ ﺍﻟﻤﻠﻮﺛﺎﺕ ﺇﻟﻰ ﺍﻟﻨﻬﺮ َﻛ ْ ﺎﻧﺖ ﺳﺒﺒﺎ ﻟﻠﻘﻠﻖ ﻓﻲ ﺍﻟﻔﺘﺮﺓ ﺍﻷﺧﻴﺮﺓ. ﺃﺧﺘﻴﺮﺕ ﺧﻤﺴﺔ ﻣﺤﻄﺎﺕ ﻟﻠﺪﺭﺍﺳﺔ ﻋﻠﻰ ﻧﻬﺮ ﺍﻟﻐﺮﺍﻑ ،ﺗﻘﻊ ﺍﻟﻤﺤﻄﺔ ﺍﻷﻭﻟﻰ ﻋﻠﻰ ﺑﻌﺪ ۲ﻛﻢ ﻣﻦ ﻣﺪﻳﻨﺔ ﺍﻟﺤﻲ ﻟﺘﻜﻮﻥ ﻣﺤﻄﺔ ﺍﻟﺴﻴﻄﺮﺓ ،ﻭﺗﻘﻊ ﺍﻟﻤﺤﻄﺔ ﺍﻟﺜﺎﻧﻴﺔ ﻋﻠﻰ ﺑﻌﺪ ۲ﻛﻢ ﻣﻦ ﺍﻟﻤﺤﻄﺔ ﺍﻷﻭﻟﻰ ﺗﻤﺜﻞ ﻁﺮﺡ ﻣﻴﺎﻩ ﺍﻟﻤﺠﺎﺭﻱ ﺍﻟﺨﺎﻡ ﻭﺗﻘﻊ ﺍﻟﻤﺤﻄﺔ ﺍﻟﺜﺎﻟﺜﺔ ﻋﻠﻰ ﺑﻌﺪ ۲ﻛﻢ ﻣﻦ ﺍﻟﻤﺤﻄﺔ ﺍﻟﺜﺎﻧﻴﺔ ﻭﺗﻣﺛﻝ ﻣﺄﺧﺫ ﺍﻟﻣﺎء ﺍﻟﺧﺎﻡ ﻟﻣﺣﻁﺔ ﺍﻟﺑﺷﺎﺋﺭ ﻟﻣﻳﺎﻩ ﺍﻷﺳﺎﻟﺔ .ﻭﺗﻘﻊ ﺍﻟﺮﺍﺑﻌﺔ ﻋﻠﻰ ﺑﻌﺪ٤ﻛﻢ ﻣﻦ ﺍﻟﻤﺤﻄﺔ ﺍﻟﺜﺎﻧﻴﺔ .ﺃﻣﺎ ﺍﻟﻤﺤﻄﺔ ﺍﻟﺨﺎﻣﺴﺔ ﺗﻘﻊ ﻋﻠﻰ ﺑﻌﺪ ۸ﻛﻢ ﻣﻦ ﺍﻟﻤﺤﻄﺔ ﺍﻟﺜﺎﻧﻴﺔ ﺑﻌﺪ ﺍﺟﺘﻴﺎﺯ ﺍﻟﻨﻬﺮ ﻟﻤﺪﻳﻨﺔ ﺍﻟﺤﻲ .ﺃﺧﺬﺕ ﺍﻟﻌﻴﻨﺎﺕ ﺷﻬﺮﻳﺂ ﺍﺑﺘﺪﺍءﺍّ ﻣﻦ ﺷﻬﺮ ﺗﺸﺮﻳﻦ ﺍﻻﻭﻝ ۲۰۱۲ﺍﻟﻰ ﺷﻬﺮ ﺗﻤﻮﺯ ۲۰۱۳ﻭﺑﻮﺍﻗﻊ ﻧﻤﻮﺫﺟﻴﻦ ﻟﻜﻞ ﺷﻬﺮ. ﺃﻅﻬﺮﺕ ﻧﺘﺎﺋﺞ ﺍﻟﺪﺭﺍﺳﺔ ﺇﺭﺗﻔﺎﻉ ﺗﺮﺍﻛﻴﺰ ﻛﻞ ﻣﻦ ﺍﻟﻌﻜﻮﺭﺓ ،ﻭﺍﻟﺘﻮﺻﻴﻠﻴﺔ ﺍﻟﻜﻬﺮﺑﺎﺋﻴﺔ ،ﻭﺍﻟﻤﻠﻮﺣﺔ ،ﻭﺍﻟﻤﻮﺍﺩ ﺍﻟﺬﺍﺋﺒﺔ ﺍﻟﻜﻠﻴﺔ ،ﻭﺍﻟﻤﻮﺍﺩ ﺍﻟﻌﺎﻟﻘﺔ ﺍﻟﻜﻠﻴﺔ ،ﻭﺍﻷﻭﻛﺴﺠﻴﻦ ﺍﻟﻤﺬﺍﺏ ،ﻭﺍﻟﻤﺘﻄﻠﺐ ﺍﻟﺤﻴﻮﻱ ﻟﻸﻭﻛﺴﺠﻴﻦ ،ﻭﺍﻟﻌﺴﺮﺓ ﺍﻟﻜﻠﻴﺔ ،ﻭﺍﻟﻜﻠﻮﺭﻳﺪﺍﺕ ،ﺍﻟﻜﺒﺮﻳﺘﺎﺕ ،ﻭﺍﻟﻔﻮﺳﻔﺎﺕ ،ﻭﺍﻟﻨﺘﺮﺍﺕ ،ﻭﺍﻷﻋﺪﺍﺩ ﺍﻟﻜﻠﻴﺔ ﻟﻠﺒﻜﺘﺮﻳﺎ ،ﻭﺃﻋﺪﺍﺩ ﺑﻜﺘﺮﻳﺎ ﺍﻟﻘﻮﻟﻮﻥ ،ﻭﺍﻟﻘﻮﻟﻮﻥ ﺍﻟﺒﺮﺍﺯﻳﺔ ﻭﺑﻜﺘﺮﻳﺎ ﺍﻟﻤﺴﺒﺤﻴﺎﺕ ،ﺍﻟﻤﺴﺒﺤﻴﺎﺕ ﺍﻟﺒﺮﺍﺯﻳﺔ ﻓﻲ ﺍﻟﺸﺘﺎء ﻭﺇﻧﺨﻔﺎﺽ ﺗﺮﺍﻛﻴﺰﻫﺎ ﻓﻲ ﺍﻟﺼﻴﻒ . ﺟﺎءﺕ ﻗﻴﻢ ﺩﺭﺟﺎﺕ ﺣﺮﺍﺭﺓ ﺍﻟﻬﻮﺍء ﻭﺍﻟﻤﺎء ﺑﻴﻦ ٤۲ – ۱٦ﻭْ ۳۱-۱۱ﻡ ﻋﻠﻰ ﺍﻟﺘﻮﺍﻟﻲ ،ﻭﻛﺎﻧﺖ ﺳﺮﻋﺔ ﺍﻟﺠﺮﻳﺎﻥ ﺑﻴﻦ ۰.۸۱ –۰.۳۷ﻡ/ﺛﺎ ،ﻭﻗﻴﻢ ﺍﻟﻌﻜﻮﺭﺓ ﺗﺮﺍﻭﺣﺖ ﺑﻴﻦ ۱۷۷ – ۳۰ﻧﻔﺜﺎﻟﻴﻦ ﻭﺣﺪﺓ ﻛﺪﺭﺓ ،ﺃﻣﺎ ﻗﻴﻢ ﺍﻟﺘﻮﺻﻴﻞ ﺍﻟﻜﻬﺮﺑﺎﺋﻲ ﻛﺎﻧﺖ ﺑﻴﻦ ۱٤٥۰ – ۸۲٥ﻣﺎﻳﻜﺮﻭ ﺳﻴﻤﻨﺰ /ﺳﻢ ،ﻭﻗﻴﻢ ﺍﻟﻤﻠﻮﺣﺔ ﻛﺎﻧﺖ ﺑﻴﻦ ۰.۹۳ – ۰.٥۲ﺟﺰء ﺑﺎﻷﻑ .ﺃﻣﺎﻗﻴﻢ ﺍﻟﻤﻮﺍﺩ ﺍﻟﺬﺍﺋﺒﺔ ﺍﻟﻜﻠﻴﺔ ﻓﺘﺮﺍﻭﺣﺖ ﺑﻴﻦ ۹٥۷ – ٥٤٥,۳ﻣﻠﻐﻢ /ﻟﺘﺮ ،ﻭﻗﻴﻢ ﺍﻟﻤﻮﺍﺩ ﺍﻟﻌﺎﻟﻘﺔ ﺍﻟﻜﻠﻴﺔ ﻛﺎﻧﺖ ﺑﻴﻦ .۲۷۸ – ۳۸ﺇﻥ ﻣﻴﺎﻩ ﻧﻬﺮ ﺍﻟﻐﺮﺍﻑ ﻛﺎﻧﺖ ﻗﺎﻋﺪﻳﺔ ﺧﻔﻴﻔﺔ ﺣﻴﺚ ﺳﺠﻠﺖ ﻗﻴﻢ ﺍﻵﺱ ﺍﻟﻬﻴﺪﺭﻭﺟﻴﻨﻲ ﺑﻴﻦ ۸.۷ – ۷.۰۳ﻭﻛﺎﻧﺖ ﺫﺍﺕ ﺗﻬﻮﻳﺔ ﺟﻴﺪﺓ ﺇﺫ ﺃ ﺃﻥ ﻗﻴﻢ ﺍﻷﻭﻛﺴﺠﻴﻦ ﻛﺎﻧﺖ ﻋﺎﻟﻴﺔ ﻓﻲ ﺃﺷﻬﺮ ﺍﻟﺸﺘﺎء ﻣﺴﺠﻠﺔ ﺗﻐﺎﻳﺮﺍً ﺷﻬﺮﻳﺎ ً ﻭﺍﺿﺤﺎ ً ﺇﺫ ﺗﺮﺍﻭﺣﺖ ﺑﻴﻦ ۱۰,۳۸ – ٦.۳ﻣﻠﻐﻢ /ﻟﺘﺮ ،ﻭﺍﺭﺗﻔﻌﺖ ﻗﻴﻢ ﺍﻟﻤﺘﻄﻠﺐ ﺍﻟﺤﻴﻮﻱ ﻟﻸﻭﻛﺴﺠﻴﻦ ﻓﻲ ﺑﻌﺾ ﺍﻟﻤﺤﻄﺎﺕ ﻭﻗﺪ ﻛﺎﻧﺖ ﻗﻴﻤﻬﺎ ﺑﻴﻦ ۷.۰۱ – ۱ﻣﻠﻐﻢ /ﻟﺘﺮ، ﻭﻭﺟﺪ ﺃﻥ ﻣﻴﺎﻩ ﺍﻟﻨﻬﺮ ﻋﺴﺮﺓ ﺟﺪﺍً ﺇﺫ ﺃﻥ ﻗﻴﻢ ﺍﻟﻌﺴﺮﺓ ﺍﻟﻜﻠﻴﺔ ﻗﺪ ﺗﺮﺍﻭﺣﺖ ﺑﻴﻦ ٤۹٦ – ۳۰٦ﻣﻠﻐﻢ /ﻟﺘﺮ .ﺃﻣﺎ ﺑﺎﻟﻨﺴﺒﺔ ﻟﻘﻴﻢ ﺍﻟﻜﻠﻮﺭﻳﺪ ﻓﻘﺪ ﺗﺮﺍﻭﺣﺖ ﺑﻴﻦ ۱۸٤,٦ – ۸۹ﻣﻠﻐﻢ /ﻟﺘﺮ ،ﻭﻗﻴﻢ ﺍﻟﻜﺒﺮﻳﺘﺎﺕ ﺗﺮﺍﻭﺣﺖ ﺑﻴﻦ ۳٦۰ – ۱۷۲,٤۲ﻣﻠﻐﻢ /ﻟﺘﺮ. ﺍﻣﺎ ﺍﻟﻤﻐﺬﻳﺎﺕ ﻓﻘﺪ ﺳﺠﻠﺖ ﻗﻴﻢ ﺍﻟﻨﺘﺮﺍﺕ ﺑﻴﻦ ۱٥,۷ – ٥,۷ﻣﻠﻐﻢ /ﻭﺳﺠﻠﺖ ﺍﻟﻔﻮﺳﻔﺎﺕ ﻗﻴﻤﺎ ً ﺗﺮﺍﻭﺣﺖ ﺑﻴﻦ – ۰.۱۳ ۰.٥۰ﻣﻠﻐﻢ /ﻟﺘﺮ .ﺍﻅﻬﺮﺕ ﺍﻟﻨﺘﺎﺋﺞ ﺍﻥ ﻣﻌﻈﻢ ﻣﺆﺷﺮﺍﺕ ﺍﻟﻤﺎء ﺗﺠﺎﻭﺯﺕ ﺍﻟﻤﺤﺪﺩﺍﺕ ﺍﻟﻌﺮﺍﻗﻴﺔ ﻟﻤﻴﺎﻩ ﺍﻻﻧﻬﺎﺭ ﻭ ﻣﻨﻈﻤﺔ ﺍﻟﺼﺤﺔ ﺍﻟﻌﺎﻟﻤﻴﺔ ﻟﻤﺎء ﺍﻟﺸﺮﺏ. ﺃﻣﺎ ﺑﺎﻟﻨﺴﺒﺔ ﻟﻘﻴﻢ ﺍﻟﻤﻌﺎﺩﻥ ﺍﻟﺜﻘﻴﻠﻪ ﻓﻘﺪ ﺗﺮﺍﻭﺣﺖ ﻗﻴﻢ ﺍﻟﻜﺎﺩﻣﻴﻮﻡ ﺑﻴﻦ ۰.۰۹۹ – ۰.۰۰۱ﺟﺰء ﻣﻦ ﺍﻟﻤﻠﻴﻮﻥ ،ﻭﻗﻴﻢ ﺍﻟﺮﺻﺎﺹ ۰.۳۲ – ۰.۰۰٤ﺟﺰء ﻣﻦ ﺍﻟﻤﻠﻴﻮﻥ ،ﻭﻗﻴﻢ ﺍﻟﺰﻧﻚ ﻛﺎﻧﺖ ﺑﻴﻦ ۱.۱ – ۰.۰۲٥ﺟﺰء ﻣﻦ ﺍﻟﻤﻠﻴﻮﻥ .ﻭﺃﻅﻬﺮﺕ ﺗﺮﺍﻛﻴﺰ ﺍﻟﻤﻌﺎﺩﻥ ﺍﻟﻤﺪﺭﻭﺳﺔ ﻓﻲ ﻣﻴﺎﻩ ﺍﻟﻐﺮﺍﻑ ﺗﻐﻴﺮﺍﺕ ﻓﺼﻠﻴﺔ ﺧﻼﻝ ﻓﺘﺮﺓ ﺍﻟﺪﺭﺍﺳﺔ ،ﻭﺗﺠﺎﻭﺯﺕ ﺍﻟﺤﺪﻭﺩ ﺍﻟﻤﺴﻤﻮﺡ ﺑﻬﺎ ﻣﻦ ﻗﺒﻞ ﺍﻟﻤﺤﺪﺩﺍﺕ ﺍﻟﻌﺮﺍﻗﻴﺔ ﻟﻨﻈﺎﻡ ﺻﻴﺎﻧﺔ ﺍﻷﻧﻬﺎﺭ. ﺃﻣﺎ ﺑﺎﻟﻨﺴﺒﺔ ﻟﺪﺭﺍﺳﺔ ﺍﻟﻌﻮﺍﻣﻞ ﺍﻟﺒﺎﻳﻮﻟﻮﺟﻴﺔ ﻓﻘﺪ ﻅﻬﺮﺕ ﻧﺘﺎﺋﺞ ﺃﻋﻠﻰ ﺍﻟﻤﻌﺪﻻﺕ ﻟﻸﻋﺪﺍﺩ ﺍﻟﻜﻠﻴﺔ ﻟﻠﺒﻜﺘﺮﻳﺎ ﻓﻲ ﺍﻟﻤﺤﻄﺔ ﺍﻟﺜﺎﻧﻴﺔ ﺧﻼﻝ ﻓﺼﻞ ﺍﻟﺸﺘﺎء ۲۰۱۳ﺣﻴﺚ ﺑﻠﻐﺖ ۷٥۰۰۰ﺧﻠﻴﺔ ۱ /ﻣﻞ ،ﻭﺍﺩﻧﻰ ﺍﻟﻤﻌﺪﻻﺕ ﻓﻲ ﺍﻟﻤﺤﻄﺔ ﺍﻻﻭﻟﻰ ﺧﻼﻝ ﻓﺼﻞ ﺍﻟﺼﻴﻒ ۲۰۱۳ﻭﻛﺎﻧﺖ ۱۰۰ﺧﻠﻴﺔ ۱/ﻣﻞ .ﺑﻴﻨﻤﺎ ﺗﺮﺍﻭﺣﺖ ﺃﻋﺪﺍﺩ ﺑﻜﺘﺮﻳﺎ ﺍﻟﻘﻮﻟﻮﻥ ﻭﺍﻟﻘﻮﻟﻮﻥ ﺍﻟﺒﺮﺍﺯﻳﺔ ﺑﻴﻦ ۲۹۰ – ۳٤۰۰۰ﻭ ۳۳۰۰۰-۲۲۰ﺧﻠﻴﺔ ۱۰۰ /ﻋﻠﻰ ﺍﻟﺘﻮﺍﻟﻲ .ﺃﻣﺎ ﺑﺎﻟﻨﺴﺒﺔ ﻷﻋﺪﺍﺩ ﺑﻜﺘﺮﻳﺎ ﺍﻟﻤﺴﺒﺤﻴﺎﺕ ﻭﺍﻟﻤﺴﺒﺤﻴﺎﺕ ﺍﻟﺒﺮﺍﺯﻳﺔ ﻓﺘﺮﺍﻭﺣﺖ ﺑﻴﻦ ۳۲٦۰۰ – ۲۳۰ﻭ ۲۱۰۰۰-۲۰۰ﺧﻠﻴﺔ ۱۰۰ /ﻋﻠﻰ ﺍﻟﺘﻮﺍﻟﻲ .ﻭﺑﺬﻟﻚ ﺗﺠﺎﻭﺯﺕ ﺍﻟﻤﺤﺪﺩﺍﺕ ﺍﻟﻌﺮﺍﻗﻴﺔ ﻟﻤﻴﺎﻩ ﺍﻟﺸﺮﺏ ﻭﺍﻻﻧﻬﺎﺭ ﻭ ﻣﻨﻈﻤﺔ ﺍﻟﺼﺤﺔ ﺍﻟﻌﺎﻟﻤﻴﺔ. ﺏ ﺟﻤهﻮﺭ�ﺔ ﺍﻟﻌﺮﺍﻕ ﻭﺯﺍﺭﺓ ﺍﻟﺘﻌﻠﻴﻢ ﺍﻟﻌﺎ�� ﻭﺍﻟﺒﺤﺚ ﺍﻟﻌﻠﻤﻲ ﺟﺎﻣﻌﺔ �ﻐﺪﺍﺩ � /ﻠﻴﺔ ﺍﻟﻌﻠﻮﻡ ﺗﺄﺛ�� ﻣﻴﺎﻩ ﺍﳌﺠﺎﺭﻱ ﺍﳌﺤﻠﻴﻪ ﻋ�� ﻧﻮﻋﻴﺔ ﻣﻴﺎﻩ ��ﺮ ﺍﻟﻐﺮﺍﻑ �� ﻣﺪﻳﻨﺔ ﺍﻟ�� ﺭﺳﺎﻟﺔ ﻣﻘﺪﻣﺔ ﺍ�� ﻣﺠﻠﺲ �ﻠﻴﺔ ﺍﻟﻌﻠﻮﻡ -ﺟﺎﻣﻌﺔ �ﻐﺪﺍﺩ ﻭ�� ﺟﺰﺀ ﻣﻦ ﻣﺘﻄﻠﺒﺎﺕ ﻧﻴﻞ ﺩﺭﺟﺔ ﺍﳌﺎﺟﺴﺘ�� �� ﻋﻠﻮﻡ ﺍ�ﺡﻴﺎﺓ /ﻋﻠﻢ ﺍﻟﺒﻱﺌﺔ ﻭﺍﻟﺘﻠﻮﺙ ﻣﻦ ﻗﺒﻞ ﻭﺳﺎﻡ ﺛﺎﻣﺮ ﺟﺒﺎﺭ ﺍﳌﻴﺎﺡ ﺑ�ﻠﻮﺭ�ﻮﺱ ﻋﻠﻮﻡ ﺍ�ﺡﻴﺎﺓ /ﺍﺣﻴﺎﺀ ﻣﺠهﺮ�ﺔ – ﺟﺎﻣﻌﺔ ﻭﺍﺳﻂ ٢٠٠٩ ﺑﺈﺷﺮﺍﻑ Ï .Ãﻤﺤﻤد ﻨﺎﻓﻊ ﻋﻠﻲ اﻟﻌزاوي ﺫﻭ ﺍﻟﺤﺠﺔ ۱٤۳٤ ﺗﺸﺮﻳﻦ ﺍﻻﻭﻝ ۲۰۱۳
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