as mentioned by Riley and Chester (1971) are; uptake by phytoplankton, bacterial activity, and oxidation - reduction processes. The seasonal variations of Nitrite ...
ﺟــــﺎﻣﻌﺔ اﻻزھــــﺮ ﻛـﻠـﯿــﺔ اﻟـﻌـــﻠـــﻮم ﻗـﺴــﻢ اﻟﻜـــﯿﻤﯿـــﺎء ************
ﺑﻌﺾ اﻟﺪراﺳﺎت اﻟﺒﯿﺌﯿﺔ وﺗﻘﺪﯾﺮ ﺑﻌﺾ اﻟﻌﻨﺎﺻﺮ اﻟﺜﻘﯿﻠﺔ ﻟﻤﯿﺎة وﺟﻮف اﻟﻨﯿﻞ ﻓﻰ اﻟﻤﻨﻄﻘﺔ اﻟﺼﻨﺎﻋﯿﺔ ﺑﺤﻠﻮان رﺳﺎﻟﺔ ﻣﻘﺪﻣﺔ ﻣﻦ
اﺣـﻤـﺪ ﻋـﺜﻤـﺎن ﺳﻌﯿـﺪ ﻋـﺒـﺪاﻟـﻠـﮫ ﺑﻜﺎﻟﻮرﯾﻮس اﻟﻌﻠﻮم – ﻗﺴﻢ اﻟﻜﯿﻤﯿﺎء اﻟﺨﺎﺻﺔ –ﺟﺎﻣﻌﺔ اﻻزھﺮ ﺑﺎﺣﺚ ﻛﯿﻤﯿﺎﺋﻰ ﺑﺸﺮﻛﺔ ﻣﯿﺎة اﻟﻘﺎھﺮة اﻟﻜﺒﺮى
ﺗﺤﺖ اﺷﺮاف ا.د /ﻋﻠﻰ ﻣﺼﻄﻔﻰ ﻋﻠﻰ ﺣﺴﻦ
ا.د /ﻋﺒﺪ اﻟﺴﻤﯿﻊ ﻋﺒﺪ اﻟﺤﻤﯿﺪ ﻋﻠﯿﻮة
اﺳﺘﺎذ اﻟﻜﯿﻤﯿﺎء اﻟﻐﯿﺮ ﻋﻀﻮﯾﺔ
اﺳﺘﺎذ اﻟﻜﯿﻤﯿﺎء اﻟﺒﯿﺌﯿﺔ واﻟﺘﺤﻠﯿﻠﯿﺔ
ﻛﻠﯿﺔ اﻟﻌﻠﻮم –ﺟﺎﻣﻌﺔ اﻻزھﺮ
ﺑﺎﻟﻤﻌﮭﺪ اﻟﻘﻮﻣﻰ ﻟﻌﻠﻮم اﻟﺒﺤﺎر
د /ﻋﺒﺪ اﻟﻨﺎﺻﺮ ﻣﺤﻤﺪ اﺣﻤﺪ
د /ﯾﺴﺮى ﻋﺒﺪ اﻟﻌﺰﯾﺰ ﺳﻠﯿﻤﺎن
ﻣﺪرس اﻟﻜﯿﻤﯿﺎء اﻟﻐﯿﺮ ﻋﻀﻮﯾﺔ
اﺳﺘﺎذ ﻣﺴﺎﻋﺪ ﺑﻤﻌﮭﺪ ﻋﻠـﻮم اﻟﺒﺤـﺎر ﺑﺎﻟﺴﻮﯾﺲ
ﻛﻠﯿﺔ اﻟﻌﻠﻮم – ﺟﺎﻣﻌﺔ اﻻزھﺮ
۲۰۱۰
Al Azhar University Faculty of Science Chemistry Department
Some environmental studies and determination of some heavy metals on water and sediment of River Nile in front of the industrial area of Helwan province THESIS Submitted for partial fulfillment for the Degree of Master of Science
by
Ahmed Osman Said Abd- Allah Under supervisor of
Prof. Dr / Ali Mustafa Ali Hassan
Prof.Dr/ Abd El Samie Elewa
Prof. of inorganic chemistry Al-Azhar university
Prof.of environmental & inorganic chemistry
Dr / Yousry Abd El-Aziz Soliman
Dr/ Abdel-Nasser Mohamed Ahmed
Assistant Prof/ at the Institute of Marine Sciences, Suez
Lecturer of inorganic chemistry Al-Azhar university
National Institute of Oceanography& Fisheries
Egypt 2010
ﺑﺳم ﷲ اﻟرﺣﻣن اﻟرﺣﯾم َظ َﮭ َر ا ْﻟ َﻔ َﺳﺎ ُد ﻓِﻲ ا ْﻟ َﺑ ﱢر َوا ْﻟ َﺑ ْﺣ ِر ِﺑ َﻣﺎ َﻛ َﺳ َﺑ ْ ﺎس ﻟِ ُﯾذِﯾ َﻘ ُﮭم ت أَ ْﯾدِي اﻟ ﱠﻧ ِ ض اﻟﱠذِي َﻋ ِﻣﻠُوا ﻟَ َﻌﻠﱠ ُﮭ ْم َﯾ ْر ِﺟ ُﻌونَ َﺑ ْﻌ َ ﺻدق ﷲ اﻟﻌظﯾم
Acknowledgement First and foremost thanks are due to God, the most beneficent, unlimited and continuous blessing on me and for all gifts He gave me. I wish to express my deepest gratitude and great thanks to Prof.Dr. Ali Mustafa Ali Hassan Prof. of Inorganic Chemistry, AL Azhar university for his supervision, invaluable support, encouragement, and advice throughout the study period. No words can be sufficient to express my deepest gratitude to Prof.Dr. Abd El Samie Elewa Prof. of analytical and environmental chemistry, National Institute of Oceanography and Fisheries, for planning the subject, the facilities he offered me through this work . Special words of thanks and gratefulness to Dr/ Abdel-Nasser Mohamed Ahmed Lecturer of Inorganic Chemistry, AL Azhar university, and Dr/ Yousry Abd El- Aziz Soliman Assistant prof. at the Institute of marine sciences for their supervision, helpful guidance and support during this work. I wish also to express my deepest gratitude to Prof.Dr. Atef ElHaddad Chairman Department of Chemistry, Faculty of science, AlAzhar University, and all colleagues and staff members of Chemistry Department. The author Ahmed Osman Said
CONTENTS
Acknowledgement
page
Aim of the work …………………………………………...
1
Chapter I: Introduction
2
Literature Review …………………………………………
4
Water researches …………………………………………
5
Sediment researches ………………………………………
29
Chapter II: Material and Methods
38
1- Sampling area ………………………………….............
43
2- Sampling collection ………… .……………………….
44
3- Methods of analysis …………………………………...
44
A- Water analysis
44
1- Physical parameters
44
i- Temperature …………………………………………….
44
ii- Turbidity .. ...…………………………………………..
45
iii- Electrical Conductivity …………………………….…..
45
iv –Solids ( TS , TDS ,TSS )
45
……………………………
2- Chemical parameters
46
i- Hydrogen Ion concentration pH ..……………………..
46
ii- Dissolved oxygen D.O … .. …………………………..
47
iii- Biochemical oxygen demand B.O.D ………………….
48
iv- chemical oxygen demand C.O.D ……………………..
48
i
v- Major Anions
49
a- Carbonate Alkalinity………………………………
49
b- Bicarbonate Alkalinity ………………………………
50
Vi – Sulphate…………………………………………….
50
vii - Chloride …………………………………………….
51
Viii - Fluoride ……………………………………………
51
ix- Major Cation
52
a- Sodium and potassium ……………………………..
52
b- Calcium …………………………………………….
52
c- Magnesium ………………………………………….
53
d- Aluminum …………………………………………...
53
X – Nutrient salts
54
a- Ammonia …………………………………………….
54
b- Nitrate ……………………………………………….
55
c- Nitrite………………………………………………...
55
d- Reactive Silicate……………………………………..
56
e- Total Reactive Phosphorus TRP……………………...
56
Xi- Trace Metals ………………………………………….
57
B- sediment analysis
59
i- Organic matter OM% ……………………………………
59
ii- Carbonate ………………………………………………
60
iii- Metals ………………………………………………….
60
ii
Chapter III: Results and Discussion
62
Part 1 – Water analysis
62
A- Physical parameters
62
1- Temperature …………………………………………….
62
2- Turbidity ………………………………………………..
65
3- Electrical conductivity EC ……………………………...
66
4- Total Solids ……………….……………………………
72
5- Total Dissolved Solids …………………………………
75
6- Total Suspended Solids …………………………………
78
B- Chemical parameters
81
1- Hydrogen ion concentration pH …………………………
81
2- Dissolved Oxygen ………………………………………
82
3- Biochemical Oxygen Demand ………………………….
88
4- Chemical Oxygen Demand ……………………………..
91
5- pollution load …………………………………………...
94
C- Major anion
97
1- Alkalinity ……………………………………………….
97
1.a Carbonate alkalinity ……………………………….
97
1.b Bicarbonate alkalinity ……………………………..
100
2- Chloride …………………………………………………
104
3- Fluoride …………………………………………………
107
4- Sulphate ………………………………………………..
107
iii
D- Major Cation
113
1- Calcium …………………………………………………
113
2- Magnesium ……………………………………………..
117
3- Sodium …………………………………………………
121
4- Potassium ………………………………………………
124
5- Aluminum ………………………………………………
127
6- Basic Ratio M/D ………………………………………...
128
E- Nutrient Salts
131
1- Nitrite…………………………………………………….
134
2- Nitrate …………………………………………………...
138
3- Ammonia ………………………………………………..
139
4- Reactive Silicate ………………………………………...
146
5- Phosphorus ………………………………………………
149
F – Heavy Metal
153
1- Iron ……………………………………………………..
154
2- Manganese ……………………………………………..
158
3- Zinc …………………………………………………….
161
4- Copper …………………………………………………
165
5- Lead ……………………………………………………
169
6- Cadmium ………………………………………………
173
7- Chromium ………………………………………………
176
8- Nickel …………………………………………………..
180
iv
Part II –Sediment analysis
184
A- Organic Matter OM% …………………………………..
184
B- Carbonate Content ………………………………………
185
C- Major cation …………………………………………….
186
1- Sodium ………………………………………………….
186
2- potassium ………………………………………………..
188
D- Heavy Metals …………………………………………..
189
1- Iron …………………………………………………….
189
2- Manganese …….……………………………………….
191
3- Zinc ……………………………………………………
192
4- Copper …………………………………………………
194
5- Lead ……………………………………………………
195
6- Cadmium ……………………………………………….
197
7- Nickel …………………………………………………..
198
8- Chromium ……………………………………………
199
Comparison between ICP-OES and Spectrophotometer for determination of Fe , Al …………………………………..
201
1- Iron analysis …………………………………………….
202
2- Aluminum analysis ……………………………………..
203
Chapter IV: DATA analysis
204
1- correlation Coefficient ( r ) ……………………………..
204
Assessment of water quality ………………………………
209
v- Summary and conclusion
216
VI- References
231
v
List of Tables Table Table ( 1 ) Table ( 2 ) Table ( 3 ) Table ( 4 ) Table ( 5 ) Table ( 6 ) Table ( 7 ) Table ( 8 ) Table ( 9 ) Table ( 10 ) Table ( 11 ) Table ( 12 ) Table ( 13) Table ( 14 ) Table ( 15 ) Table ( 16 ) Table ( 17 ) Table ( 18 ) Table ( 19 )
page (Co)
Seasonal variations of water temperature in the investigated area during 2008 Seasonal variation of Turbidity (NTU) in the investigated area during 2008 Seasonal variation of Electrical Conductivity ( µS/cm) in investigated area during 2008 Seasonal variation of total solids (mg/l ) in the investigated area during 2008 Seasonal variation of total dissolved solids T.D.S ( mg/l ) in investigated area during 2008 seasonal variation of total suspended solids (mg/l) in investigated area during 2008 Seasonal variation of Hydrogen ion Concentration (pH) in investigated area during 2008 Seasonal variation of Dissolved oxygen D.O ( mg/l ) in investigated area during 2008 Seasonal variation of Biochemical oxygen demand BOD ( mg/l ) in investigated area during 2008 Seasonal variation of Chemical oxygen demand COD ( mg/l ) in investigated area during 2008 Seasonal variation of Biotic Oxygen Consumption BOC ( % ) in investigated area during 2008 Seasonal variation of Carbonate Alkalinity ( mg/l ) in investigated area during 2008 Seasonal variation of Bicarbonate Alkalinity (mg/l) in investigated area during 2008 Seasonal variation of Chloride Cl- ( mg/l ) in investigated area during 2008 Seasonal variation of Fluoride F- ( mg/l ) in investigated area during 2008 Seasonal variations of Sulphate - SO4 2- ( mg/l ) in investigated area during 2008 Seasonal variation of Calcium Ca ( mg/l ) in investigated area during 2008 Seasonal variation of Magnesium Mg ( mg/l ) in investigated area during 2008 Seasonal variation of Sodium Na ( mg/l ) in investigated area during 2008
63 67 70 73 76 79 83 86 89 92 95 98 101 105 108 111 115 119 122
Table ( 20 ) Table ( 21 ) Table ( 22 ) Table ( 23 ) Table ( 24 ) Table ( 25 ) Table ( 26 ) Table ( 27 ) Table ( 28 ) Table ( 29 ) Table ( 30 ) Table ( 31 ) Table ( 32 ) Table ( 33) Table ( 34 ) Table ( 35 ) Table ( 36 ) Table ( 37 ) Table ( 38 )
Table ( 39 )
Table ( 40 )
Seasonal variation of Potassium - K ( mg/l ) in investigated area during 2008 Seasonal variation of Aluminum Al ( mg/l )in investigated area during 2008 Seasonal variation of Basic Ratio (Na+ + K+/Ca+2 + Mg+2)in investigated area during 2008 Seasonal variations of Nitrite NO 2 - ( mg/l ) in investigated area during 2008 Seasonal variation of Nitrate NO 3 - ( mg/l ) in investigated area during 2008 Seasonal variation of Ammonia NH 3 (mg/l ) in investigated area during 2008 Seasonal variation of Reactive Silicate ( mg/l ) in investigated area during 2008 Seasonal variation of Phosphate PO4 -3 ( mg/l ) in investigated area during 2008 Seasonal variation of Iron Fe ( mg/l ) in investigated area during 2008 Seasonal variation of Manganese Mn ( mg/l ) in investigated area during 2008 Seasonal variation of Zinc Zn ( µg/l ) in investigated area during 2008 Seasonal variation of Copper Cu ( µg/l ) in investigated area during 2008 Seasonal variation of Lead Pb ( µg/l ) in investigated area during 2008 Seasonal variation of Cadmium Cd ( µg/l ) in investigated area during 2008 Seasonal variation of Chromium Cr ( µg/l ) in investigated area during 2008 Seasonal variation of Nickel Ni ( µg/l ) in investigated area during 2008 OM (% ) of the Nile sediments in the studied area at different stations, during winter season Carbonate content (%) of the Nile sediments at different stations, during winter season Sodium concentration in the sediment and subsurface water at different stations, during January 2009 Potassium concentration in sediment and subsurface water at different stations, during January 2009 Iron concentration in the sediment and subsurface water at different stations, during January 2009
125 129 132 136 140 144 147 151 155 159 163 167 170 174 178 181 184 186 187
188
190
Table ( 41 )
Table ( 42 ) Table ( 43 )
Table ( 44 ) Table ( 45) Table ( 46 ) Table ( 47 )
Table ( 48 )
Table ( 49 )
Table ( 50 )
Table ( 51 )
Table ( 52 )
Table ( 53 )
Table ( 54 )
Table ( 55 )
Manganese concentration in sediment and subsurface water at different stations, during January 2009 Zinc concentration in sediment and subsurface water at different stations, during winter season Copper concentration in the sediment and subsurface water at different stations, during January 2009 Lead concentration in sediment and subsurface water at different stations, during January 2009 Cadmium concentration in sediment and subsurface water at different stations during January 2009 Nickel concentration in the sediment and subsurface water at different stations, during January 2009 Chromium concentration in sediment and subsurface water at different stations, during January 2009 Iron concentration in subsurface water at different stations, during winter season by using ICP-OES and spectrophotometer technique Aluminum concentration in subsurface water at different stations, during winter season by using ICP-OES and spectrophotometer technique correlation coefficient matrix of physicochemical parameter of water during spring in the studied area 2008-2009 correlation coefficient matrix of physicochemical parameter of water during summer in the studied area 2008-2009 correlation coefficient matrix of physicochemical parameter of water during autumn in the studied area 2008-2009 correlation coefficient matrix of physicochemical parameter of water during winter in the studied area 2008-2009 correlation coefficient matrix of physicochemical parameter of sediment during January 2009 at studied area standard limits ( maximum permissible limits ) of drinking water parameters according to different criteria
191
193 194
196 197 198 199
202
203
210
211
212
213
214
215
List of Figures Figure ( 1 ) Figure ( 2 ) Figure ( 3 ) Figure ( 4 ) Figure ( 5 ) Figure ( 6 ) Figure ( 7 ) Figure ( 8 ) Figure ( 9 ) Figure ( 10 ) Figure ( 11 ) Figure ( 12 ) Figure ( 13 ) Figure ( 14 ) Figure ( 15 ) Figure ( 16 ) Figure ( 17 ) Figure ( 18 ) Figure ( 19 ) Figure ( 20 ) Figure ( 21 ) Figure ( 22 ) Figure ( 23 )
Figure
page
The Sludge Judge Sampler ICP-OES Varian Liberty Series II UV/VIS Spectrophotometer Jenway 6505 Turbidity Meter Hack 2100 N pH Meter Jenway 3510 Conductivity Meter Jenway 4510 Area of investigation extended along a distance of 40 km From El-Saaf ( I ) to El-Roda ( VII ) Sequential Type ICP-OES water temperature of River Nile at Helwan area during 2008 (a) annual average (b) seasonal average annual and seasonal average values of water Turbidity NTU annual and seasonal average values of water Electrical Conductivity (µS/cm) annual and seasonal average values of Total solids (mg/l) of River Nile during 2008 annual and seasonal average values of Total dissolved solids (mg/l) annual and seasonal average values of Total suspended solids (mg/l) Annual and seasonal average values of Ion hydrogen concentration pH annual and seasonal average values of Dissolved Oxygen DO (mg/l) annual and seasonal average values of Biochemical Oxygen demand BOD (mg/l) annual and seasonal average values of Chemical Oxygen demand COD (mg/l) annual and seasonal average values of Biotic Oxygen Consumption BOC ( % ) annual and seasonal average values of Carbonate Alkalinity (mg/l) annual and seasonal average values of Bicarbonate Alkalinity (mg/l) annual and seasonal average values of Chloride concentration (mg/l) annual and seasonal average values of Fluoride concentration (mg/l)
39 40 41 41 41 41 42 58 64 68 71 74 77 80 84 87 90 93 96 99 102 106 109
Figure ( 24 )
annual and seasonal average values of Sulphate (mg/l)
112
Figure ( 25 )
annual and seasonal average values of Calcium (mg/l) annual and seasonal average values of Magnesium (mg/l) annual and seasonal average values of Sodium (mg/l) annual and seasonal average values of Potassium (mg/l) annual and seasonal average values of Aluminum (mg/l) annual and seasonal average values of Basic Ratio annual and seasonal average values of Nitrite (mg/l) annual and seasonal average values of Nitrate (mg/l) annual and seasonal average values of Ammonia (mg/l) annual and seasonal average values of Reactive Silicate (mg/l) annual and seasonal average values of TRP (mg/l) annual and seasonal average values of Iron (mg/l) annual and seasonal average values of Manganese (mg/l) annual and seasonal average values of Zinc (µg/l) annual and seasonal average values of Copper (µg/l) annual and seasonal average values of Lead (µg/l) annual and seasonal average values of Cadmium (µg/l) annual and seasonal average values of Chromium (µg/l) annual and seasonal average values of Nickel (µg/l) Sodium concentration in water and sediment during winter season Potassium concentration in water and sediment during winter season Iron concentration in water and sediment during winter season Manganese concentration in water and sediment during winter season
116
Figure ( 26 ) Figure ( 27 ) Figure ( 28 ) Figure ( 29 ) Figure ( 30 ) Figure ( 31 ) Figure ( 32 ) Figure ( 33 ) Figure ( 34 ) Figure ( 35 ) Figure ( 36 ) Figure ( 37 ) Figure ( 38 ) Figure ( 39 ) Figure ( 40 ) Figure ( 41 ) Figure ( 42 ) Figure ( 43 ) Figure ( 44 ) Figure ( 45 ) Figure ( 46 ) Figure ( 47 )
120 123 126 130 133 137 141 145 148 152 156 160 164 168 171 175 179 182 187 188 190 191
Figure ( 48 ) Figure ( 49 ) Figure ( 50 ) Figure ( 51 ) Figure ( 52 ) Figure ( 53 ) Figure ( 54 )
Figure ( 55 )
Zinc concentration in water and sediment during winter season Copper concentration in water and sediment during winter season lead concentration in water and sediment during winter season Cadmium concentration in water and sediment during winter season Nickel concentration in water and sediment during winter season Chromium concentration in water and sediment during winter season Iron concentration in subsurface water at different stations, during winter season by using ICP-OES and spectrophotometer technique Aluminum concentration in subsurface water at different stations, during winter season by using ICP-OES and spectrophotometer technique
193 194 196 197 199 200 202
203
…………………………………….……………………... Materials and methods
List of Abbreviations
E.C. TS TDS TSS pH D.O BOD COD BOC TP D.W. N.E.D E.B.T. E.D.T.A Ph.Ph. M.O ICP-OES NTU EPA WHO ECS APHA
: Electrical Conductivity. : Total Solids. : Total Dissolved Solids. : Total Suspended Solids. : Hydrogen Ion Concentration : Dissolved oxygen. : Biological oxygen demand. : Chemical oxygen demand. : Biotic Oxygen Consumption : Total phosphorus. : Distilled water . : 1 Naphthyl Ethylene Diamine Dihydrochloride. : Eriochrome black T indicator. : Ethylenediaminetetraacetic acid. : Phenolphthalein indicator. : Methyl orange indicator. : inductively coupled plasma - optical emission spectrometer : Nephelometric Turbidity Units : Environmental Protecting Agency : World Health Organization. : Egyptian Chemical Standards. : American Public Health Association
…………………………………………….………………. …Aim of the work
AIM OF THE WORK The aim of this study is to gather detailed information on the aquatic ecosystem of the River Nile at the industrial area of Helwan province in the area extended from El-Saaf to El-Roda island. Such information is needed to identify damaging and irreversibility effects due to Iron and Steel industrial wastes.
Some areas were selected at the most drinking water stations in the south of Cairo, El-Tebeen, Kafr-Elawe, North Helwan, EL-Maadi, El-Roda drinking water stations. Also El-Saaf which is located in the south of the iron and steel plant. It is considered as a reference point. Consequently, the main goals of the present study is to find out the present status of the water quality in River Nile
and to what extent its
ecosystem has been affected by the recent development of industries and their effluents which are discharged in the River . In order to achieve these goals, the present study included the follow up of seasonal changes in the water quality of River Nile as follows.
(A) Water analysis: 1- Physical parameters: water temperature, electrical conductivity, turbidity, dissolved, suspended and total solids . 2-
Chemical parameter: - These parameters included, pH, dissolved oxygen DO , biochemical oxygen demand BOD , chemical oxygen demand COD, carbonate, bicarbonate, chloride, fluoride, sulphate , sodium, potassium, calcium, magnesium, aluminum, nutrient salts (nitrite, nitrate, and ammonia), total reactive phosphorus
and silicate. Also some trace
elements such as iron, manganese, zinc, copper, cadmium, nickel, chromium and lead will be estimated.
(B) Sediment analysis: Included: organic matter, carbonate, , sodium, potassium, and some trace elements e.g. Fe, Al, Mn, Zn, Cu, Cd, Ni, Cr and Pb.
۱
CHAPTER I
…………………………………………………..………………. …Introduction
INTRODUCTION The River Nile is the main source of surface water in Egypt, and therefore is the artery of life in Egypt. The River Nile is one of the longest rivers in the world, measuring 6670 km from the head waters of the Kagera River in Rwanda-Tanzania, to the shores of Mediterranean Sea in Egypt with surface over .about 2,978,000 km2. (Mancy and Hafez 1977).The River Nile flow northward until it pours water into the Mediterranean Sea by two branches namely Rossetta and Demitta branches. The last 1200 km of the 6800 km long Nile lie in Egypt north of the first cataract, and for its entire course in Egypt the river receives no perennial tributaries. In ancient times Egypt was divided into Lower and Upper Egypt, with Lower Egypt being the delta region and Upper Egypt being the region from the delta to the first cataract at Aswan. Even though the Nile flows only 170 km through the delta, this contains about twice as much agricultural land (about 22,000 km2) as lies in Upper Egypt (about 12,000 km2).
The River Nile at south of Cairo is considered as fresh water, which is used for drinking, industrial and fishing purposes in Cairo. Many drinking water stations at investigation area product over 3.500.000 m3 per day , many sources of pollution are poured into river at investigated area , one of them which is the most dangerous; Iron and steel drain
Many of the factories in this industrial zone , Victory for the manufacture of coke and chemicals, Iron and steel plant, Helwan plant of chemical fertilizers , this factories beside iron and steel drain , also Helwan for cement ACEC beside Kafr – Al-awe drain. This work was carried out and covered the River Nile at south of Cairo in the area extended from El-Saaf city to El-Roda Island within the distance of 40 km. The study included the investigation of physical and chemical properties of water and sediment.
.
2
……………………………………..….…………………………... Introduction
Sediment The composition of bottom sediment as biological processes have been given a lot of attention over the past years as reported by (Mannio et al.,1995; Bortoli et al., 1998; Gray et al.,2000; Klavins et al., 2000; Groshava et al, 2000; and Rashed 2001). All the above mentioned authors and others studied the heavy metals in sediment in addition to physical and geochemical characteristic of the sediment. Sediments are important sinks for various pollutants like pesticides and heavy metals and play significant role in the remobilization of contaminants in aquatic systems under favorable condition and in interactions between water and sediment to organisms is now considered to be major route of exposure for many species (Zaumis et al, 2001) .
The release of trace metals from sediments into fresh water body and consequently to fish will depend on speciation of metals and other factors such as pH of sediment, physical and chemical characteristics of aquatic system (Morgan and Stumm, 1998).
Metals may be distributed in sediment as exchangeable carbonate bound, iron manganese oxide bound, organic matter bound and residual bound species. The speciation of metal can be evaluated by carefully choosing the extracting solutions and digestion condition (Ikem, 2003).
Concentration of heavy metals in sediments deposited during flood on flood plans is related to their contact in transported and accumulated sediment in river channel in the period, which immediately proceeds as flood. As a result, changes of heavy metals concentration in vertical profiles of over bank sediments reflect changes of river pollution in the period of sediments deposited.
Metallic pollutants have a great ecological significant due to their toxicity and they are not biodegradable contrary to most pollutants. Knowledge of the
3
……………………………………..….…………………………... Introduction metallic pollutants concentrations in sediments and of their evolution is interest because they act as traps, catching pollutants. (Digeretal, 1992). They can also be considered as reservoir capable of solubilizing some of their constituents under certain physicochemical condition so that analysis of sediments is good indicator of water quality. The contamination of soil, sediments, water resource and biota by heavy metals is one of major concern especially in many industrialized countries because of their toxicity persistence and bioaccumulative (Ikem et al,2003). Correlation of heavy metal concentration peaks in deposits with production fluctuations recorded in the economic history of a catchments area makes it possible to determine the age of deposited sediments (Knox, 1999 and Cizewski, 2003) The physicochemical characteristics of sediments determine the bioavailability of metals. The transfer of metals from water to sediments depends on both pH. and redox conditions of lake. Frenet, 1981; showed that, the bottom water loses its metals content more ready by adsorption on the suspended matter giving the sediments on high metals content and having the water with a low one.
Literature review The polluted water discharged into the River Nile is attributed to two sources , the first one is the sewage discharged from cities and from neighboring village, the second to the small drainage canals contain agricultural runoff. To prevent adverse environmental effects of developed onto river system, the implication of an integrated environmental management plan is considered as most effective approach to insurance sustainable use of water sources and protection of river system. So in this part of study, a light will be thrown on the published works that aim the same goals of our work. Several studies have been carried out on the effect of different environmental conditions of the Nile water, on the water chemistry; among them the following studies may be mentioned.
4
………………………..……………….…………………………... Introduction
1-Water researches Mancy and Hafez (1977) studied the water quality of River Nile. They showed that, the main factors which affect water quality characteristics of the River Nile include, upstream changes south of Lake Nasser, changes in Lake Nasser, and localized changes in the River Nile basin. Furthermore, they showed Nile receives increasing amounts of wastes discharging from point and non point sources as the River travels northward. However, the discharge of waste effluents was usually accompanied by localized effects of water quality deterioration, immediately down stream from the water outfall.
Lasheen et al. (1979) studied the trace elements in water samples collected along River Nile. They showed that River Nile water contains concentration of trace elements (Cd, Pb, Cu and Zn) in levels for below limits of U.S. environmental protection agency. The concentration of these elements ranged between 0.02 -2, 0.04 7.8 and 0.66- 36 µg/l for Cd, Cu, and Zn, respectively.
El Sheikh (1980) studied some factors such as chemical parameters of water and trace elements in water of River Nile .The water resources were investigated of the River Nile and its main branches from Aswan to the Mediterranean Sea,The trace elements concentrations of zinc, Iron, Manganese, nickel, copper, lead, and Barium were measured and were found to be generally within the permissible limits for drinking water specification.
El Falaky (1981) studied the effect of industrial wastes with heavy metals on the quality of the River Nile at Helwan industrial area. It was found that the source of Mn was the coke industry, where its outlet contained 680 µg/l Mn. Mey back (1982) studied the nitrate in water samples collected from Switzerland River .He showed that , the concentration of nitrate in range between 8 to 17 µg/l.
5
………………………..……………….…………………………... Introduction Tada and Suzuki (1982) studied the heavy metals in bottom mud of urban rivers. They reported that, the main factor controlling the adsorption of metals was organic matter, since the adsorbed metals decreased remarkably due to the destruction of organic matter from the fine bottom mud.
Fischer et al(1983) studied the levels of major cations (Na, K, Mg, and Ca) and anions Cl-, SO 4 2-, and S 2- ) and some heavy metals (Hg, Cd, Pb ,Cu and Be) in Seine River in France. He showed that, the danger of mercury and beryllium poisoning were increased by the fact that certain organisms led to concentrate these ions. Siliem (1984) reported that, the pollution of the Damietta branch of River Nile below Faraskour Dam was due to an impoundment and continuous input of dissolved and solid materials, washed down by the drainage runoff and by domestic waste water outfalls. The channel is anoxic below a very thin photic zone, its bottom layer is abnormal in its ionic composition, its high bicarbonate alkalinity, high ammonia, and high hydrogen sulfide contents. Such conditions in addition to poor oxygen content during stagnation periods had bad effect on fish causing mass mortality and health hazards to the population. De Breuck (1985) studied the physical and chemical parameters in Ghant canal in Belgium and the ground water in its surrounding. He showed that, the concentrations of Ca, Mg, SO 4 , Na, CI, F, NH 3 and heavy metals during years 1970 and 1982 were high according to EU standard.
Guatavsson et al (1985) studied some heavy metals in Goeta River (Sweden) .They pointed out that, the water contains slightly enhanced concentrations of Hg and Cu they added that, the sewage treatment of Hg and Cd discharges have marginal effect on the river .In addition to both Pb and Cd were somewhat higher than normal along the western of river while all other metals concentrations were normal during 1980-1984.
6
………………………..……………….…………………………... Introduction
Musa and Ali (1985) determined the concentration of heavy metals (Cu, Ca, Pb, Ni and Zn )in Tigris River discharged from textile factory .They showed that, in most sites the concentration of Cu, Cd and Pb exceeded the permitted levels and the Levels of Ni showed some seasonal fluctuations but the Concentration of Zn was generally low at most sites.
Williams and Rebort (1985) showed that unionized ammonia in water of Elbe River was toxic to fish and aquatic invertebrates. They added that, the unionized ammonia and ammonium ion fractions in water were controlled by pH and temperature. Also they showed that with increasing pH and temperature an increase of total ammonia was observed as unionized ammonia. Dumont, (1986) studied the physical and chemical parameters in the River Nile, White Nile, Blue Nile, Sobat, Atbara and Joint Nile. He showed that, the conductivities range between 140-350 ms/cm, except in Bahr El Ghazal (40-50 ms/ cm) total ionic content range between 3-7 mg/ml and the pH in alkaline side (7.9- 9.1) except in Bahr EL Ghazal was acidic . Fytianons et al. (1986) studied the heavy metals in Axion River , Nestos River ,Vistonis Lake and Noirami Lake (northern Greece). They showed that, the Axion River had the highest concentration of Pb, Cd and Cu whereas the Nestos River was relatively moderate while Vistonis Lake was heavily polluted whereas Noirami Lake was considered unpolluted. They reported that, the domestic and industrial waste water discharges into these rivers and lakes were the main source for heavy metals. Motassen et al. (1986) studied water quality in the River Nile starting from High Dam to the Mediterranean Sea during the period 1976 to 1986. They measured (Nitrate, Nitrite, temperature, pH, BOD, DO, COD, PO 4 ---, TDS ,C1- and NH 3 ). They showed that for drainage canals at location up and down river stream the results were increased with time and the levels were high than standards.
7
………………………..……………….…………………………... Introduction Borg (1987) studied the Physical and chemical parameters in fresh lakes in Sweden (pH, water color, conductivity and major ions) as well as the heavy metals (Fe, Mn, Al, Cu, Pb, Cd, Ni, Cr and Co). He showed that, the lakes water was generally soft, with low levels of electrolytes. In addition to the pH values increased and the sulfate concentrations decreased from south to north. However, pH and water color were the major important for the distribution of trace metals. Also, he added that ,Mn, Al and Zn were negatively correlated to pH , Fe, Mn, Al and Pb were positively correlated to water color. The concentrations of metals were found to be around two folds higher in winter than summer. Abd El Aal et al. (1988) studied the water quality of River Nile at Helwan. The samples were analyzed for soluble heavy metals, suspended matter and salts. The liquid wastes discharged by industrial complex at Helwan contained high amounts of heavy metals mainly iron, Mn, and Zn and high concentration of soluble salts. Also they add that the dumping of these industrial wastes into El- Hager and Khashab canal were much higher than that in the Nile water by about 4 to 7 times.
Elewa and Latif, (1988) Studied the physico-chemical parameters in Aswan High dam Reservoir. They showed that, the dissolved oxygen in Aswan High Dam Reservoir increased during the cold seasons due to income flood and the water become oxygenated ,this beside the thickness of upper oxygenation layer increased in autumn which result in the complete oxygenation of the lake in cold seasons particularly in winter .
Elewa and Mahdi (1988). Studied regional variation of some physical and chemical conditions in the River Nile water at Cairo in the area (Roud EL farag, el Roda and Helwan) during the period from July 1985 to April 1986 . They investigated (temperature transparency, electrical conductivity, dissolved oxygen, biochemical oxygen demand, chemical oxygen demand, Ca, Mg, alkalinity and chlorosily).
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………………………..……………….…………………………... Introduction Kunishi (1988) studied the source of nitrogen and phosphorous in the Wye River. He measured the nutrients concentration (NO 2 , NO 3 and reactive P) in relation to sampling sites, sample salinity and times of year. He showed that, the fresh water entering river from the watershed contained consistently high concentration of NO 3 about (4 mg/l) and low concentration of PO 4 (about 40 ug/l) .Also, he showed that once these nutrients entered the river, the concentration of NO 3 decrease to low levels within a short distance (500- 700m) from the point of river discharge. El Dardier et al. (1989) studied the water quality of water of Aswan High Dam Reservoir . They analyzed (HCO 3 , CO 3 , SO 4 , CI, K, Na, Mg, Ca, and some trace elements). They reported that, the pH values were exceeded the highest desirable levels. Also, they added that, the concentrations of trace elements and major constituents lied under or within the permissible levels given by the World Health Organization WHO . Kudou et al.(1989) studied the water quality of the Isushiba and Aka Rivers in Japan. They showed that, the suspended solids concentration increased in the thawing season, whereas BOD, COD and total P increased during summer and autumn .Also he added that, the loading of nutrients salts increased in the thawing season. Turk and Movinie (1989) studied the concentrations of NH 3 Nondage Lake, New Yourk, USA. They showed that, the concentration of NH 3 in the upper waters of lake well below the threshold of inhibition for first stage of nitrification and exceeded the threshold for second stage on only several occasions. Further accumulation of nitrite oxidizers to NO 3 has been reported. Brooks (1990) studied the distribution of nitrogen species in Onondage Lake, USA. He reported that, the water quality problems in the Lake related to the prevailing high concentrations of N species including potential toxicity effects and severe lake depletion during flood period. Dang et al. (1990) studied some heavy metals like ( Ni, Cd, Zn, Pb). They showed that ,the effect of cadmium, nickel, lead and Zinc on growth and chemical composition of anion They showed that, the toxicity of heavy metals in the order: Cd> Ni> Pb>Zn.
9
………………………..……………….…………………………... Introduction Lopez (1990) studied the chemical parameters composition in order to identify the main process controlling the concentration of major ions (HCO 3 , CI, SO 4 , Mg, Na and K) in the water. He showed that, the Na was the only ion that can be considered dependent on the proportion of sea water alone. SO 4 , Mg, K were also greatly influenced by marine inputs, but their concentrations were modified by geological and biological factors. Srivastava (1990) investigate the adsorption and desorbtion behavior of Zinc (II) at iron (III) hydroxide-aqueous solution interface as influenced by pH and temperature. He concluded that at 15 and 30 °C Zn , (II) adsorption on Fe (OH)
3
increased with an increase in pH. Ahler et al. (1991) studied in the Manuherikia River (New Zeeland) the distribution of the dissolved trace metals Cu, Ni, Cd, Zn and Pb in parallel with the major elements Na, K, Mg and Ca and electrical conductivity. He showed that all trace metals exhibited the same spatial trends as the major ions.
Deai et al. (1991) studied the amounts of nitrogenous pollutants on the Lee River (China). They stated that, in the Lee River, NH 4 + is the dominant pollutant and the oxygen consumption caused by the oxidation of nitrogenous compounds plays an important role in the depletion of dissolved oxygen.
Saad et al.(1991) studied the physical and chemical parameters in the Rosetta branch . They reported that, the Rosetta estuary of the Nile is isolated from the Rosetta branch by Edfina Barrage which control the Nile water discharge into the sea. The maximum discharge occurs in January and the minimum discharge is during April-November. The total nitrogen (TN) and total phosphorus (TP) were studied during 1987 - 1988 to investigate the effect of the estuarine water on the vertical, regional and seasonal distribution of TN and TP compounds in coastal region.
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………………………..……………….…………………………... Introduction They showed that, the distribution patterns of TN and TP were controlled with phytoplankton uptake, standing crop of autotrophic organisms, changes of water column, variations in the adsorption and desorption process in abundance of suspended matter, decomposition of organic matter, and finally on the direct influence of land-based sources of phosphorus and nitrogen on the estuary and increased salinity on the coastal sea water.
Abdel Hamid et al. (1992) studied the water quality of the River Nile. They reported that, the concentrations of phosphorus, nitrogen, total dissolved salts, total hardness, chlorides, biological oxygen demand, copper, lead, zinc and iron increase significantly as proceed from up to downstream cites. They added that, the River Nile receive high amount of wastes discharges from point and non point sources as it flows northward to Mediterranean Sea. Kadam (1992) studied the chemical parameters of Thana River. Chlorides, BOD, turbidity, salinity and hydrogen ion concentration were measured. He showed that , the river received effluents from domestic wastes channels and also from dyes, chemical pesticide and insecticide industries .He added that due to disposal of large amounts of wastes the levels of BOD, turbidity and heavy metals exceed the standards limits. Also ,he added that because of increase in organic load, the dissolved oxygen was utilized in the process of biodegradation. Rabia (1992) studied water quality of Nile River at Helwan area. He measured (temperature, pH, conductivity, DO, turbidity ,nutrients salts, major ions and organic pollutants ). And some heavy metals (Pb Cr, Cd). He reported that, the heavy elements in water were found to be within the permitted international limits. Abdel Halim (1993) pointed out that ,the total dissolved solids of River Nile water varied between 48 - 600 mg /l , where the Nile was below the standard limits. He showed that, the chloride and sulfate increased on going to north along the River Nile and varied in the ranges of 4 - 32 and 0.7- 8.5ug/l respectively. The nitrate and silica decreased in the north direction and fluctuated in the range of 28 - 860 ug/1 and 1.38 - 12.33 mg/l respectively.
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………………………..……………….…………………………... Introduction Awad (1993) studied the distribution dynamic of trace elements in the River Nile during the year 1991. He pointed out that, the metals arranged in descending order Fe > Mn > Zn> Cu. Also, he added that, the trace elements accumulate higher in eastern bank compared to the western bank of the Nile due to the effect of pollution where the major factories besides cultivated lands were concentrated at eastern bank of River Nile.
Dessoki et al. (1993) studied some environmental parameters in Demitta branch of river Nile. They showed that, the electrical conductivity varied in range of (11.6 - 41.8 mmhos cm-1) and chlorosity (8 - 21.6) mg/l. Also they showed that, the concentration of nutrient salts showed a wide fluctuation and abrupt change due to irregular influxes of different wastes. High concentration of ammonia, nitrate, organic nitrogen and phosphorus were found. Zhang and Hung (1993) studied the concentrations of dissolved trace metals (Cd, Co, Cu, Ni, Fe, Mn, Zn, and Pb) in Huonghe River,China . They showed that , the trace metals occur at level lower than frequently reported in china. Also, they showed that, there were correlation between the metals and major elements in the river indicating the significant of weathering in controlling water chemistry. Lin and Li (1994) studied the changes of heavy metals in Lean River- Poyang Lake, China during the period 1989- 1993. They showed that,the concentrations of the copper in the permissible levels in the lake, but high concentrations of the copper appears in the tributary mouth regions especially in the mouth of Lean River .Also, they measured lead, zinc and cadmium in the down stream part of the River and the inlet of Poyang Lake .They found that ,their concentration were in the permissible levels. Massoud et al. (1994) measured the water samples of the River Nile. They showed that, the concentrations of the trace metals were increased from south to north direction. Also they showed that, the distribution of the trace metals in the Nile water affected by physico-chemical parameters such as pH, dissolved oxygen, transparency, carbonate, phosphate and suspended matter. Statistical analysis indicated that, the concentration of different metal ions was found to be in order Fe>Mn>Zn>Cu.
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………………………..……………….…………………………... Introduction Lin and Li (1994) studied the Physical and chemical parameters of Ill River at Alsace in north-eastern France. They showed that, the Ill River had highly concentrations of organic matter, phosphate, ammonium from effluents of waste water treatment plants or organic effluents. Also they showed that, the despite contamination of the river water. Elewa (1995) studied the physical and chemical parameters of Rivers Nile water. He found that, the water transparency of the Nile increased in the southern direction. On the other hand, the minimum values of dissolved oxygen and pH values were recorded in the northern region at Helwan and El Kanater El khyria however high values were observed in the south. He added that, the nutrient salts in the Nile water depend mainly on the abundance of phytoplankton. Also ,the effect of temperature, pH and dissolved oxygen in the water was exist on the distribution of these salts along the River Nile. Elewa et al (1995) studied the changes of major anions and cations of the River Nile water at El-Kanater El-Khyria region during 1993. They showed that the area opposite the soap factory was more affected by direct exposure to its drainage, and the refluxes of water used inside the factory for cooling. This led to changes which were clear in the analysis obtained. Also, they added that such changes were represented in a great fluctuation in the concentration of anions such as CI, CO 3 , and HCO 3 in addition to cations such as Na. The Ca concentration reached its lowest level during winter season at the area opposite to the soap factory due to its precipitation on the sediment under influence of pH changes. Shehata et al. (1995) studied some physico-chemical characteristics of the River Nile at El Kanater El Khyria region. They showed hat, this area has been greatly affected by many substances drained from the adjacent Soap plant. They concluded that manufacturing process at the area of investigation has produced a very wide variety of chemical waste products that were not valuable enough to collect and reuse. The toxicity of them contaminated the aquatic environment and some of them may be accumulated on the bottom of the River Nile and poison it.
13
………………………..……………….…………………………... Introduction
Elewa et al (1995) studied the changes of major anions and cations of the River Nile water at El-Kanater El-Khyria region during 1993. They showed that the area opposite the soap factory was more affected by direct exposure to its drainage, and the refluxes of water used inside the factory for cooling. This led to changes which were clear in the analysis obtained. Also, they added that such changes were represented in a great fluctuation in the concentration of anions such as CI, CO 3 , and HCO 3 in addition to cations such as Na. The Ca concentration reached its lowest level during winter season at the area opposite to the soap factory due to its precipitation on the sediment under influence of pH changes.
Shehata et al. (1995) studied some physico-chemical characteristics of the River Nile at El Kanater El Khyria region. They showed hat, this area has been greatly affected by many substances drained from the adjacent Soap plant. They concluded that manufacturing process at the area of investigation has produced a very wide variety of chemical waste products that were not valuable enough to collect and reuse. The toxicity of them contaminated the aquatic environment and some of them may be accumulated on the bottom of the River Nile and poison it.
Shehata et al. (1995) a studied the seasonal variations in phytoplankton diversity and the change of the physico-chemical parameters of the River Nile. The results showed that the temperature varied in the range of 14 to 27°C. They showed that, the high temperature value influence the photosynthetic activity of phytoplankton especially during summer and fall season. The turbidity measurement was low. Also, they showed that, the dissolved oxygen concentration decrease down river at El Kanater which was 7.0 mg/l. super saturation was recorded at Helwan sites (11.4 mg/l). Also, they showed that, the metals accumulated at high concentration and increased in the following order Zn> Cr> Ni> Cu> Pb.
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………………………..……………….…………………………... Introduction Soltan and Awadallah(1995) reported that ,the inorganic nonmetals, pH values, trace metals (Al, Ca, Cd, Fe, K, Li, Mg, Na, Ni, Pb, and Zn), and physical parameters were determined during 1993 in River Nile water from different areas from Aswan, Qena, Sohag, Assiut, El-Menya, Beni Suef, Giza, Cairo, Mansoura, Damietta, Kafr El-Zayat, and Edfina (from the middle of the main stream and from the two branches of the Nile i.e. Damietta and Rosetta). The results indicated that the Nile water characteristics were within the allowed and desired safety baseline levels, except those collected from Damietta which exhibit dangerously high levels. This may be attributed to industrial wastewater effluents from (pickled herring making, tanning, dyeing, and textile, soap making, fertilizers, and cheese making factories, domestic sewage, and agricultural discharges drained directly into the Nile.
Bakry (1996) studied the physical and chemical parameters in Demietta and Rosetta branches. He showed that, the two branches received heavy loads of dissolved solids, nutrients, organic matter, heavy metals, organic pollutants and organo chlorine pesticides from the different sources of pollutions. He showed that, the COD, BOD, oil and grease concentration reached 4375, 1380 and 450 mg/1 with an average value of 1495,589 and 197 mg/1 respectively. The Super phosphate Company discharged about 20,000 m3/day waste water to Rosetta branch which was normally acidic.
Abd EI Azym, (1996) reported that In Ismailia canal, the lead and iron concentrations were higher than maximum contaminating levels. However, the concentration of other parameters such as nitrate and phosphate were in the permissible contaminant levels.
Elewa et al. (1996) studied the River Nile water. They showed that the distribution pattern of Fe, Mn, Cu, Zn, and Cd in the water of the River Nile are mainly affected by the amount of industrial domestic and agricultural effluent in the River .Also, they showed that, the concentrations of different metals were found to be in the order Fe>Mn>Cd>Cu.
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………………………..……………….…………………………... Introduction El Gamal et at. (1996) studied the physical and chemical parameters in the River Nile and their effect on quality of water. They demonstrated that the total volume of liquid wastes discharging to the Nile between Aswan and Cairo is about 3882 million m3/y of which about 312 million m3/y was industrial wastewater. They showed that the most serious discharges which tend to raise the BOD levels of the river water were those of Sugar industries .Also, they showed that some metals such as Zn and Cu detected in some of the industrial wastes especially near the industrial area south of Cairo.
Hassoun ( 1 9 9 6 ) studied the physical and chemical parameters in the River Nile .He showed that, the area under investigation received a heavy load of industrial wastes especially at the northern area resulting in the increase of the metals and non metals concentrations. Also he showed that, the different elements concentrations could be arranged in descending order as follows: for water Fe > Mn > Zn > Cd > Cu. And for sediments Fe > Mn > Cu > Zn > Cd > Ni > V > Pb > Co >Ag. He found that Cu, Zn and Cd were mainly accumulated in sediments due to precipitation of organic material which were concentrated by these elements.
Nelson et al. (1996) studied the nitrogen, phosphorus and organic carbon in streams drainage in Australia. They showed that, the high concentration of N, P and organic carbon in water cause problems such as excessive eutrophication and bacterial growth.
Paul (1996) studied the physical and chemical parameters in Abd Lake. He pointed out that, the nitrification rates for this lake was extremely low because of relatively low concentrations of nitrifier biomass. Also He pointed out that essentially no nitrification in samples collected in summer but measured rather high rates for the sediment water interface in deep strafed portions of the lake. The nitrification in lake was localized at sediments was supported by nitrifying bacteria .
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………………………..……………….…………………………... Introduction Siver et al. (1996) studied the chemical and physical conditions of 42 lakes, between three times periods, the late 1930s, the mid to lat 1970s and the early 1990s on average. The authors showed that the lakes have decreased in Secchi depth by 1.2 m and doubled in total phosphorus concentration. Also, they showed that, increasing in sodium was generally coupled with increase in chloride ions, and they showed increase in alkalinity. Issa and Elewa (1997) studied the physical and chemical parameters in River Nile at great Cairo. The authors declared that, the distributions pattern of the major elements (Na, K, Ca and Mg) and trace metals (Fe, Mn, Zn and Cu). T hey showed that, the high concentrations of the studied elements were measured in the cold period in both areas and affected by industrial effluent at Helwan and sewage effluents in front of El Rahway. Also, they added that, the physical and chemical characteristic in the water body of Nile environment effected the distribution of elements and the order of elements concentrations were in order Ca> Na> Mg> K> Fe> Mn > Zn > Cu.
Mahrous (1997) studied the physical and chemical parameters in the River Nile water and evaluated its effect on the water quality. The results of physical ,chemical and biological characteristics of the river water showed the distance from 800 km to 940 km along the greater Cairo received huge amount of industrial complex. The total liquid wastes discharged reached to about 700 million m3 / year. The result showed that the BOD, COD, chloride, sulfate, alkalinity, and total hardness increased and reached high value at different sites of this part. Abdo (1998) studied the water quality of the River Nile in front of industrial area of Shoubra El Khauma and Ismailia canal. The study showed changes in the physical and chemical characteristic of the Nile water which are strongly affected by the thermal pollution of Electric power station. On the other hand there was an adverse effect of industrial wastes on the chemical characteristics of the Ismailia canal water, these effect leading to an increase in the nutrients, in addition to some cations and anions. Concerning the heavy metals, which were studied in the Ismailia canal water such as Fe, Mn, Cu and Zn, he found that the industrial pollution leading to an increase in concentration of these metals. the order of increase of Fe > Mn > Cu > Zn.
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………………………..……………….…………………………... Introduction Ali, (1998) studied the physical and chemical parameters in the River Nile at Damietta branch region. The results showed an increase in most parameters in northward. This may be due to extensive industrial agricultural and sewage wastes which pour in the northern region. Sayed (1998) studied the chemical and physical changes of Demitta branch water at area extends from Fraskour Barrage to Ras El Bar. The results showed that, this area is considered eutrophic, highly enriched with nutrients salts brought down by the agriculture run off or resulting from the decomposition of organic domestic wastes. He measured the six heavy metal (Fe, Mn, Cu, Zn, Pb, and Cd). The author showed that the concentration values of there metals depend on the season quality and kinds of different effluents that pour in the investigated area. Also pointed that the heavy metals concentrations were extremely variable in different organisms depending on geochemical background.
Wall et al. (1998) studied the physical and chemical parameters in the water in Canajoharie River in Creek. The results showed that, the nitrate and silica concentrations were depending on seasonal and spatial variations. They showed that, these nutrients were dominated by biological processes practicality uptake by phytoplankton. Also, they showed that the nitrite and silica concentrations in river were significantly lower from April through November than during winter.
Gelda et al (1999) studied the nitrite concentration in Onondage lake in New Yourk, USA. They showed that ,the nitrite concentrations in the upper waters of N polluted Onondage lake were documented for the April through October interval for a 10 yr (1989- 1998) periods. In put of NO 2 from domestics waste treatment to the- lake were quantifies for four years (1991- 1994).The results showed that, the NO 2 concentrations reached the highest levels, and these levels represent severe violations of toxicity standards.
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………………………..……………….…………………………... Introduction Gahin, (2000) studied the physical and chemical characteristics of River Nile at Qlubia Governorate and Ismailia canal .He measured physical parameters electrical conductivity ,total dissolved solids, chemical parameters pH, alkalinity ,hardness ,some cations like ( Na, K ) ,Nutrient salts (NO 3 , NO 2 SO 4 , PO 4 ), in addition to some heavy metals were measured also (Cd, Cu, Mn, Al ,Fe ,Cr and Pb). He reported that the Ismailia canal was slightly polluted. Also, he showed that, the water fromdrains could be classified as high salinity hazard and low alkalinity , while Ismailia canal water was classified as moderate salinity hazard and low alkalinity hazard.
Abdel Satar and Elewa (2001) investigated the water quality and environmental assessment of the River Nile at Rosetta branch. They studied the accumulation of some trace metals Fe, Mn, Zn, Cu, Pb, and Cd in both water and sediment of the branch. The obtained results revealed that, the concentration of the studied metals were found to be in the order of Fe > Mn> Zn> Cu> Pb> Cd. Elewa et al. (2001) studied the effect of thermal pollution of Shoubra El Khema Electric Station on the river Nile water quality. The study concerned with seasonal variations of the physical and chemical parameters in both surface and bottom water .The results revealed that ,the point discharged of electric station with the River Nile was highly polluted. The concentrations of heavy metals were Fe (0.88-13.7 mg/1) ,Mn(44.1-770 ug/l), Zn (101-667.4 mg/1), Cu (8.8-183 ng/1), Cd (5-150ug/l) and Pb (10-180 ug/l).Also, they added that, the thermal pollution effects lead to an increase in the concentrations of most chemical parameters which can create very complicated environmental problem in the River Nile.
Magdaleno et al. (2001) studied the water quality conditions throughout the main channel of the Matanza - Riachvelo River, Argentina from December 1996 to November 1997. He showed that, the dissolved oxygen, nutrients, suspended matter and heavy metals concentrations exceeded the national guide levels.
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………………………..……………….…………………………... Introduction Olajire and Imeokparia (2001) studied some of ions (Na, Ca, NH 4 , NO 3 and PO 4 ) on water samples of Osan River in Nigeria. They measured pH, temperature, electrical conductivity, and total dissolved solid, total hardness. The results showed higher levels of phosphate, Nitrate and ammonia ions.
Sabae and Abd El Satar (2001) studied the water quality and distribution of trace metals in El Salam canal. They measured (Fe, Mn, Zn, Cu, and Pb). They Showed That the concentrations of Fe, Mn, Zn, Cu, and Pb varied in the range of 0.331-4.76 mg-1, 27.06 -223.36,
6.92-56.71,
2.98-54.56 and 12.94-53.06 ug-1
respectively. They revealed that the increase in all the elements studied from up to down stream in the canal water. Also, they added that the distribution of trace metals in the aquatic environment depends on many factor such as: the physical and chemical characteristics of the aqueous phase and the availability of both inorganic and organic complexing agents.
Williams et al. (2001) studied the physical and chemical parameters from 1995 to 1988 in Piracieaba River South east Brazil. They showed that ,the inputs of N and C were responsible for degradation of water quality at down river sampling sites of Piracieaba River drainage.
Abdo (2002) studied the water quality along a distance of 125 km from ElKanater El-khyria to Kafr El- Zayat city on the River Nile at Rosetta branch. He showed that, there was an increase in the nutrient salts, the major anions and cations of all investigated areas during the months of summer and autumn (flood period).
Franklin (2002) studied the distribution of inorganic nitrogen and phosphorous concentrations biweekly from sites located on creek and from 18 sites located on green brier creek. Also, He analyzed ammonium nitrate and dissolved reactive phosphorus concentrations.
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………………………..……………….…………………………... Introduction Fytiaons et al,(2002) studied the physical and chemical parameters in Pinois River . They did not show significant difference neither between sampling sites nor sampling periods. However, they pointed out that, the nutrients (nitrogen and phosphorus compounds) showed temporal variations probably caused by seasonal variations in run off nutrient from weather events. They determined some heavy metals (Pb, Cd, Cr, Ca and Ni). Statistical analysis of most important chemical parameters and heavy metals showed significant variation between sampling periods but insignificant ones between sampling sites.
Laureano and Navar (2002) studied water quality of Rio San Juan River in north eastern in Mexico. They determined concentrations of chemical and physical parameters on water samples. Constituents concentration in 18.7% of all samples exceeded water quality standard. They showed that, the concentration of sulfate, dissolved solids, Al, Ba, Cr , Fe and Cd exceed the water quality standards.
Xia et al. (2002) studied the nitrogen contamination in yellow River, China, in years 1980, 1990, 1997 and 1999. They showed that the nitrogen concentration in tributaries increase from the upper to the lower basin, intern led to increase in the nitrogen concentration of the main stream from the upper to lower basin. Also, they added that the ammonium and total inorganic nitrogen content of the river increased significantly in the main stream and tributaries during 1980- 1990 period. Ali et al. (2003) studied the biological and chemical characteristic of River Nile to evaluate the trophic and autrophic state of the River Nile. They used the biological indices especially phytoplankton as indicator of pollution and the relation between some chemical variables revealed that, the River Nile has poor quality water and light pollution conditions. The statistical analysis between some bacterial and chemical variables indicated significant relation between each other. Also, they measured chemical parameters such as temperature pH, DO, total dissolved solid, total alkalinity Mg, Ca and Fe.
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………………………..……………….…………………………... Introduction Lajire (2003) studied the physical and chemical parameters in Osun River, they measured (Na, Ca, NH 4 , CI, NO 3 CN, PO4, pH, temperature, electrical conductivity, total dissolved solids (TDS), total hardness) to asses the chemical status. They reported that the higher values of certain parameters with respect to the acceptable standard limits for drinking water in river water. Also, they showed that, the river had high levels of phosphate, nitrate and ammonium ions.
Cizewski (2003) studied the concentrations of heavy metals in Odra River in southwest Poland. He showed that, the changes of heavy metals concentrations in investigated area were associated with changes of copper and lead. The concentrations were correlated with maximal emission of these elements and their largest content in wastewater discharge in the area. Also, they reported that, there was decrease of Zn concentrations in the sediments that may be associated with decrease of Zn pollution in surface water in the upper and middle Odra River. Das (2003) studied the concentration of some trace metals like Fe, Mn, Cu, Pb, Zn and Co in ground water of Cuttack city, India. He reported that, the Fe from all other trace metal within the maximum permissible limits set by WHO for drinking water. Also, he added that, the factor analysis of trace elements data suggested that Fe, Mn and Cr were correlated with each other. Haiyan and Stuanes (2003) studied the heavy metal in Xiang River The study showed that heavy metal within the Zhuzhou section of Xiang River come from the same pollution sources with similar pollution channels and removal patterns in the water bodies. Also, he added that the maximum heavy metal observed divided by acceptable level was in order of Cd > Pb > Cu >Zn.
Rogora et al. (2003) Studied the changes of physical and chemical parameters of Alpine lakes. They evaluated that, the possible effect of these processes on long term changes in the chemistry of Alpine lakes. They showed climate changes affecting on the study area were investigated. also, he studied chemical data of 35 lakes located in the Ossda and Sesia valleys.
22
………………………..……………….…………………………... Introduction Rosodory et al. (2003) studied the water quality in Sweden. They reported that, the great differences in nutrient compositions depending on acid or alkaline origin. Also, they reported that the high values of Cu observed at pH around 6, while the highest concentration of nutrient appeared at pH 7- 8 in addition to the low levels of Ca and Mg ions and some micro-nutrients in acid water. Sampson (2003) studied nutrient concentrations in Rock Lake USA. They reported that, the surface water concentration of ammonium, Nitrate, soluble reactive phosphate in pH lower than 6 were high, but total nitrogen was lower at pH 5.6 Also, they added that the decrease was attributed to lower dissolved organic N. Also they showed that, the dissolved silica concentrations increased slightly at pH 4.7.
Santos and Navor (2003) studied the distribution of Zn, Cd, Pb and Cu metals. They pointed out that the river has received heavy metals from two different sources industrial wastes and intensive agricultural activity. They showed that in 1998 the accidental release in the river of a bout 6 million m3of acid water and sludge. The main polluting agents were heavy metals. Also they added there was a direct association
between
the
physico-chemical
speciation
of
an
element
and
bioavailability.
Sayed (2003) studied the River Nile Rosetta branch and Kafr El Zayat, the study showed that there were three source of pollution which potentially affected and threaten the water quality of this branch, El Rahway drain, Kafr El Zayat industrial area and small agricultural drains. The study showed that the nutrient salts like ammonia, nitrite, nitrate and total phosphate increased over bottom waters. For cations study showed that the penetration of salts from Mediterranean Sea water, which were rich in cations particularly without addition of fresh water through, gets of Edfina Barrage increased the concentration.
23
………………………..……………….…………………………... Introduction
Shuxayu (2003) studied the water quality of Songha River northeast china. Several independent water quality indices were used to consider the effects of pollutants on water quality in this area for instance, heavy metals in this area based on the environmental data. They showed that the main pollutants had changed to nitrogenous pollutants.
Stewart and Skousen (2003) studied the water quality in Deckers River (Greek) during the period from 1974 and 1999- 2000. Water samples were analyzed for P, acidity, alkalinity, Fe and Cd at both times. They showed that the all the parameters in permissible levels. Also, they added that the most of sampling stations showed lower acidity and metals contents in 1999- 2000 compared with 1974.
Kwang (2003) studied heavy metals in Zhuzbou section of the Xiang River. He pointed out that, the significant positive correlations between some pairs of heavy metal (total Cd- Hg) (total Cu- Pb) which indicated that they may came from the same pollution source with similar pollution channels and removal patterns in the water bodies . Also, they added that, the heavy metals levels were in order of Cd > Pb> Cu> Zn. EI Bassat et al. (2004) studied contaminated water of Ismailia canal for the chemical parameters and different pathogenos. They reported that the value of hydrogen ion concentration lied at the alkaline side with a value of 7.5 and the value of dissolved oxygen concentration 8.2 mg/1 .while values of nitrate and total phosphorus were 0.23 mg/1 and 0.054mg/l respectively.
Mabrok (2004) studied the effect of pollution by drainage, industrial, agricultural and urban sewage on the physico-chemical characteristics of water (temperature, chlorosity, pH, EC, DO, BOD, COD, nutrient salts and heavy metals) and the accumulation of the selected heavy metals (Fe, Cu, Mn, Zn, Pb and Cd) in the commercial fish Liza ramada in Manzala lake.
24
………………………..……………….…………………………... Introduction Elewa et al. (2004) the heavy metals concentrations, Fe, Mn, Cu, Zn, Pb, Cd, Cr, Co, Ni, give small variations between all stations in the different seasons. Most of the higher values are recorded at the stations, which receive drain water. Organic matter, carbonate, phosphate, calcium, magnesium, and the heavy metals were analyzed in sediments. The contents of organic matter are of irregular trend affected by both agriculture and domestic effluents. The carbonate percent is increased in spring as a result of increasing photosynthesis. The phosphorous concentrations are affected by the sources of drain, agriculture effluents, phosphate fertilizers and organic matter precipitated in the surface sediment. Zinc and iron are of high concentrations in spring and autumn seasons. Manganese concentrations show its maximum in spring and its minimum in winter. Copper is of high content in summer and spring near drain. Cobalt is precipitated as cobalt carbonate as a result of lake water alkalinity. The distribution of lead concentration is of irregular trend. The average concentration of cadmium points to drain water is of high level. The behavior of chromium and nickel was explained from its adsorption on the surface of iron and manganese oxides due to existence of higher values of Cr and Ni with higher values of Fe and Mn. The high content of Cr was recorded in spring season. Abdo, M.H. (2005) studied The detailed information on the distribution and concentration levels of some heavy metals (Fe, Mn, Zn, Cu, Pb & Cd), major cations (Ca, Mg, Na & K), in addition to organic matter in the Bardawil lagoon sediments during four successive seasons during (2001-2002). The different metals concentrations could be arranged in descending order as follows:
Ca> Na> Fe> Mg> K> Mn> Cu> Zn> Pb> Cd Mohamed, (2005) studied the physical and chemical characteristics of the water of Abu Za'baal Ponds. Determination of physical parameters (air and water temperatures, transparency, electrical conductivity, salinity, total solids, total dissolved solids and total suspended solids) and chemical parameters (pH, DO, BOD, COD, HCO 3 -, CO 3 --, Cl- , SO 4 --,Ca2+, Mg2+, Na+, K+, NO 2 -, NO 3 -, NH 3 , PO 4 ---, TP and SiO 2 -)
were
carried out to identify the nature and quality of the water
of Abu Za'baal Ponds. The present results reveal that the values of most physical and chemical parameters were higher than those of freshwater, lower than those of saline water and in the same range of the brackish water. Thus, the water of Abu Za'baal Ponds can be classified as brackish water. 25
………………………..……………….…………………………... Introduction Rifaat, A.E (2005) studied The sediment samples collected during R/V CHAIN 1975 cruise to the southeastern Mediterranean have been used to determine the major controls of metals distribution. The sediment samples were analyzed mineralogically, chemically and texturally. The parameters measured included carbonate minerals, total carbonate, organic carbon, iron, manganese, copper, zinc, chromium, lead, nickel, cobalt, vanadium, calcium, magnesium, strontium, sand, silt and clay. The statistical analysis of data showed that four major factors control the distribution of metals in sediments of the Nile cone; These are terrigenous mudcalcareous sand; Aragonite mud-terrigenous sand; Algal sand; and Aragonite. The percentages of terrigenous sand, mud and calcareous components of the Nile cone sediments greatly affect the elements spatial distribution. In addition to that, minor controls such as precipitation and co precipitation may affect the elemental distribution. The distributions of iron, manganese, copper, zinc, chromium, lead, nickel, cobalt, and vanadium are associated mainly with the terrigenous mud fraction of the sediment whereas, calcium and strontium are mainly related to calcareous sands. Iron, copper, cobalt, lead and vanadium are partially related to montmorillonite. Lead is associated with acid feldspars and chromium is mainly controlled by terrigenous sand. The distribution of calcium and strontium is controlled by the coarsecalcareous fraction of sediments. Magnesium and manganese are associate with algal sand. The aragonite and calcite minerals are forming the majority of carbonate mud, which controls partially the
distribution of calcium,
strontium, lead and copper.
Amaal M. Abd El-Satar (2005) Water quality of the River Nile from Idfo to Cairo and trace elements of the Nile water were seasonally investigated from autumn 2000 to summer 2001. Eleven sites were selected along the main channel of the River Nile. In addition, six stations in front of some shore-line activities were also sampled to study the man's impact on the water quality of the Nile. The distribution of major cations and anions possessed the highest values in cold seasons and the lowest during the hot high-flow period. In addition, EC, TS, TDS, COD, NH 4 +, orthophosphate, total phosphorus, Fe, Mn and Cu showed a steady increase from south to north. Point and non-point sources of pollution exerted negative local effects on the water quality of the receiving waters. The multiple correlation analysis showed a pattern of interrelationships between physical and chemical parameters.
26
………………………..……………….…………………………... Introduction Elewa et al. (2006) pointed out that El Rahaway drain lies at 30 Km, North to Cairo at El-Kanater El-Khyria area, Egypt. The drain receive domestic and agriculture wastes from Giza city and pour its effluents into the Nile water of Rosetta branch. This part of the study has been performed to follow the seasonal variation of pH; dissolved oxygen; trace metals (Fe; Zn; Cd; and Pb) and major cation in surface and bottom water of El Rahaway drain; at the point of its discharge with the Nile water and also before and after the discharge point; and comparison with five selected locations along the River Nile at the bifurcation. This is to evaluate the effect of these effluents on the quality of the river water. The results showed that the discharged effluents decreased the pH by 0.5 unit , while decreased the dissolved oxygen to low values. Also high concentration values of all elements studied were observed which render the water not suitable neither for domestic use nor irrigation and expected to kill most biota in the water at the discharge point especially in autumn. This bad effect generally continues till 300 meter after the discharge point. Fe; Pb; and Cd concentration exceeds the upper limit of standard at most sites along the River Nile especially in summer. The order of the major cations was found to be: Na>K>Mg>Ca. According to the calculated SAR (sodium adsorption ratios), the water quality of River Nile for irrigation was lower at many sites along the River Nile especially in summer and autumn. Generally it can be concluded that the river is a soft water polluted with Fe Cd and high level of Pb. According to Mimoza Milovanovic (2006), The Axios/Vardar River, an interboundary river located in the Balkan Peninsula, drains the region of southern Serbia, almost 80% of the Former Yugoslav Republic of Macedonia territory and some parts of northern Greece. This study is based upon long-term data (1979–2003) of nitrate, nitrite, ammonium, total phosphorous, BOD5, Cd, Cr, Zn, Pb and water discharge from 22 sampling stations along the Axios/Vardar River collected on a monthly basis. The quality of the river water is affected by heavy metal pollution from smelter and fertilizer plants in Veles, Ferro-alloys plant in Jegunovce, the disposal of their solid waste near the river bed and also by the untreated industrial wastewater discharge deriving from the industries located in the watershed. The agricultural runoff from cultivated areas of Tetovo, Veles and Koufalia is a significant source of nutrient pollution.
27
………………………..……………….…………………………... Introduction The untreated domestic wastewaters discharged directly into Axios/Vardar River constitute point sources of pollution, as well as the illegal landfills contaminating the surface water and groundwater.
Abd El-Hady (2007) The objective of this study is to compare the effect of pollution in the El-Saff soils irrigated from El-Khashab canal which is a mixture of domestic and industrial effluents and Nile water which is taken for comparison. Samples of water, soils and plants were collected from two sites of El-Khashab canal and site of Nile water. Results showed that salinity levels, pH and heavy metals were in the permissible level in all water and soils samples. It was noticed that values of NO in El-Khashab - canal was higher than that in Nile water, which due to the disposal of domestic and industrial effluents in El-Khashab canal. The values of heavy metals (Fe, Mn, Co, Zn, Cu, Ni, Pb and Cd) in water and extractable soil samples were lower than the maximum permissible limits. The data revealed large different between trace elements content in different soils. The highest content of trace elements (Fe, Mn, Co, Zn, Cu, Ni, Pb and Cd) in El-Khashab sites compared to that of Nile site. In soils irrigated with El-Khashab canal water, the average content of these elements was 80.8, 33.8, 0.19, 22.5, 6.39, 14.6, 23.2 and 0.26 ppm, respectively. On the other hand, the irrigated soils with Nile water, contains 2.8, 8.7, 0.09, 3.44, 2.78, 0.63, 2.3 and 0.03 ppm of Fe, Mn, Co, Zn, Cu, Ni, Pb and Cd, respectively.
Omer Abd Alrahim (2007) studied the water quality of the River Nile around the city Khartoum in Khartoum State, Sudan Republic, and investigates eventual influences of the city on the River Nile by analysis of temperature, pH, and conductivity, and Absorbable Organic Halogen (AOX), cadmium (Cd), lead (Pb), chromium (Cr), Total Organic Carbon(TOC) and Nitrate (NO 3 − ). It was concluded that the city Khartoum added small but legible concentrations of cadmium, lead, chromium and TOC to the river Nile. However, the resulting concentrations were all within acceptable levels. Also, the observed results showed that the Blue and White Nile, which merge together upstream on the outskirts of Khartoum, had concentrations of AOX resp. chromium, which were not suitable for drinking water.
28
………………………..……………….…………………………... Introduction Tawfik, (2008) evaluate the impact of sources of water pollution on water supplies in Helwan vicinities area on cultivated adjacent farms. The industrial complex at Helwan produces large wastes. In addition, the disposal of sanitary wastewater to agricultural canals disturbs in the areas the environmental balance. This study was based on the evaluation of water and soil chemistry as affected by pollution considering major ions, soluble heavy metals (Fe, Cu, Zn and Mn) as well as plant growth and chemical analysis criteria. The results reviled that water, soil and plants in the area were variably polluted from the different sources. Pollution reduced plant photosynthetic pigments and plants grown in farms receiving industrial wastes exhibited higher values of heavy metals than the limit universally permitted. Crop farming under similar conditions is legally prohibited.
Elewa et al. (2009) Eighteen water samples were collected during the seasons of the year 2003, from 9 stations which represented 2 bifurcated branches and 4 canals of the River Nile at most of Delta Barrage. More than 5 x 108 m3 daily effluents which include domestic and agricultural wastes are discharged from ElRahawy drain into Rosetta branch. The drain lies 30 km north to Cairo at El-Kanater El-Khyria, Egypt. The impacts of this effluents was found to be exist to about 2 km in high concentration as recorded for suspended and dissolved solids, COD, BOD, HCO 3 -, CO 3 --, CI-, SO 4 --, S--, NO 2 -, NO 3 -, NH 4 +, SiO 2 , TP and PO 4 3- With the exception of the above, mentioned area the water of the River Nile at Delta Barrage showed good water quality without any harmful risk as shown by its safe human usage.
II- Sediment researches
Sakai (1986) studied the distribution of Mn, Zn, and Cd in the sediment and the water of Togohina River Japan. He showed that the concentrations of heavy metals were almost the same for water and sediment samples taken from the main stream of which was polluted by. Municipal industrial a mining effluents.
29
………………………..……………….…………………………... Introduction Skaccel (1987) studied the heavy metals distribution in sediment and water . He measured (Fe, Cd, Mn, Cu and Pb).They showed that the concentration of heavy metals in sediment higher than the concentration the water.
Abd El Maoti and Dowidar (1988) studied the heavy metals ( Al, Fe, Mn, Zn, Pb, Ni, Cu, Co and Cd )in the surficial sediments of Lake Manzalah ( the largest northern Delta Lake in Egypt) . They showed that the relatively abundance of studied element was Al> Fe much greater than Mn> Zn>Pb. Ni> Cu> Co much greater than Cd. Also, they made comparison with other Nile Delta Lakes indicates the enrichment of Cu, Pb, Cd and Co in the sediments of Manzalah lake.
Elewa et al. (1990) studied the distribution of some parameters in lake Nasser and River Nile sediment at Aswan .They found that ,the Mn, Zn and Cu were varied in the range of 160-l440 µg/g , 12-315 µg/g and 4 - 141 µg/g respectively . They added that, Mn, Zn and Cu were concentrated in the clay sediments rather than in the silt and sand with a positive correlation between these metals in comparison with down stream of River Nile. Abou Elela and El Bahrawy . (1993 ) studied some trace metals associated with sediment components (carbonate, organic matter, Fe, and Mn oxides). The study indicated that the order of release metals from sediments were Cd> Cr> Pb> Cu> Zn >Ni> Mn >Fe and order ( adsorption characteristics of most mobile metals fraction was Fe/Mn oxides> organic > clay. Anmor et al. (1993) studied the concentrations of Cd, Cu, Co, Fe, and Mn in water, suspended solid and surficial sediments of the River Tigris, Iraq. They reported that the high concentration of heavy metals during April and low during July. The recorded concentrations in water were significantly lower than Iraq River water standards. Also ,they showed that the concentration of the most of the examined elements in surficial sediments was lower than those in suspended solid.
30
………………………..……………….…………………………... Introduction
Elewa (1993) studied the distribution of Mn, Cu, Zn and Cd in water , sediment in River Nile and Aswan reservoir. He reported that, heavy metals were quantified in water and sediment in river Nile and Aswan reservoir and down stream of River Nile at Aswan. He showed that the area of investigation received a heavy load of sewage and industrial wastes which resulted in the increase of the metals concentrations .Also He showed that, the rate of accumulation depends up on the physico-chemical conditions of the environment and the metals concentrations in sediment were relatively higher than in water.
Ingle et al. (1993)
studied some heavy metals in water and sediment of
different sites of River patalganga Muharashra, India from October 1988 to September 1989. Cd, Co, Cu, Fe, Mn, Pb and Zn were detected in all the sampling sites of the river. He showed that, the concentrations of these metal were found in the order Fe> Mn> Cu> Zn> Pb> Co> Cd in water and Fe> Mn> Ni> Zn> Cu> Co> Pb> Cd in the sediment.
Joseph and Srivastava (1993) studied the water and sediment of Adyar, Ennore, and Lake pulical (India) .They showed that the comparative studies conducted on bottom sediment and water of Adyar, Ennore, and Lake pulical (India) in the presence of Hg, Zn, Pb, Cu, Cr, Ni, and Cd in the first two estuaries, whereas Lake Pulicat remained free from heavy metals pollution.
Muller and futter (1994) studied the concentrations of heavy metals in sediments of Elbe River. They reported that for Co ,Ni and Cr, the concentrations were from zero to moderate, Moderate to high for Pb and Cu and high to very high for Hg, Cd and Zn along the river. In the river the concentration of heavy metals in sediments significantly decrease due to the decreasing of the Hamburg Harbor.
31
………………………..……………….…………………………... Introduction Yahya and Song (1994) studied the distribution of heavy metal in sediments and pore water of Lean River at Caitiawan (China) to identify the geochemical reactions which influence release or accumulation of heavy metals in sediments and to identify the environmental factors that control these reactions. The concentrations of Fe, Mn, Cd, Zn, Pb and Cu in sediment cores were determined. They reported that ,these heavy metals were presented in relation to dissolved NO 3 , NH 3 , Fe, Mn and SO 4 . The study showed that there was no significant mobilization of heavy metals from the sediments based on the Pore water profiles. Williams et al. (1994) studied the concentrations of Cu and Zn in the sediment and pore water of high elevation alkaline lake east Arizon USA. Selective sequential extraction of metals from lake sediment showed different binding mechanisms for Cu and Zn. The former most strongly associated with organic complex.
Mushrifah et al. (1995) studied the levels of heavy metals in sediment of Terengyanu River. The authors showed that the concentrations of heavy metals in sediment were low mainly due to anthorgnic activates, Also they added that this river was still unpolluted with heavy metals ,also showed that the heavy metals detected in each sampling station was varies with pH and organic carbon percentage.
Auer et al.(1996) studied the physical and chemical characterization of sediments of Ononaga Lake, New York, USA. Seventy samples were analyzed for a suit of parameters: particle size, moisture content, volatile soil, calcium carbonate, nitrogen, and phosphate, chemical oxygen demand, inorganic and organic carbon. The result showed that Lake sediments were enriched in calcium carbonate due to an industrial discharge of Ca also showed that the location of tributary and point source inputs and Lake predominant circulation pattern also influence the distribution of P. deep water and sediments rich in N, P and organic matter.
32
………………………..……………….…………………………... Introduction Awadallah et al. (1996) studied the heavy metals (Cd, Co, Cr, Cu, Fe, Mn, Ni and Zn)in mud sediments taken from the bottom of main stream of River Nile at Seven locations between Aswan and Giza. The results of analysis showed irregular distribution of metals ions in sediment samples along the distance of Aswan and Giza. They reported that this might be attributed to the inputs from industrial effluents and domestic waste water rained directly into the Nile Hassoun(1996) studied the, sediment chemistry in the River Nile in Egypt from Aswan to Helwan . He found that, the area under investigation receives a heavy load of industrial wastes especially at the northern area resulting in an increase of the levels of the metals and non metals concentrations. The bottom sediments as well as the aquatic plants and invertebrates act as a sink for these metals. He showed that The different elements concentration could be arranged in descending order as follow: (i)
Fe > Mn > Zn > Cd > Ni > V > Pb > Co > Ag
(ii)
Ca > Mg > P
Issa et al. (1996) studied the distribution of some heavy metals in the sediments of River Nile. The analysis of River Nile sediments indicated that the concentration of the trace metals varied in the direction of south to north. He revealed that the sediments were the major carriers for many toxic materials or nutrient. Concerning aquatic environments the levels found for all metal ions in the sediments of the River Nile were below the permissible limits set by unite states EPA as harmless to aquatic life.
Mendoza (1996) studied the heavy metals in sediments of Mexico. The results showed that heavy metals were not biodegraded and presented in the environment for long time. Also showed that the increasing levels of Cadmium and Lead during July, while cobalt had its highest level in March. Finally chromium data presented an irregular pattern during whole year.
33
………………………..……………….…………………………... Introduction Elewa et al. (1997) studied the accumulation of chemical elements in sediment of the River Nile at Great Cairo from Helwan to El Kanater El khyria region. They showed that ,the metals concentrations could be arranged in descending order as follows Na>Zn>Cu>Pb>Cd. They also reported that ,the rate of accumulation of the above metals independent on the physical and chemical conditions of the water body as well as the amount of industrial and sewage effluents flow to the River Nile.
Abd El Satar (1998) studied the distribution of some chemical elements in the water and sediments of River Nile from Helwan to El-kanater El-khyria region. He reported that the great increase in Fe, Mn and Zn concentrations during different seasons were observed in front of Iron and Steal factory and in the area in front of El-Rahway drain.
Goher (1998). Studied factors affecting the precipitation and dissolution of some chemical elements in River Nile at Damitta branch. He measured the major cations, organic matter, carbonate and total phosphuros in the sediment. The degree of deposition of studied metals were in the order of Fe>Mn>Cd>Zn>Cu>Pb>K>Na>Ca>Mg. Also, he showed that the deposition of heavy metals to the sediment depending on several factors as pH
values, dissolved oxygen, redox potential, organic matter, salinity and types of the sediment. The organic matter deposition from the above water increases the precipitation of heavy metals, while the decomposition of Organic matter in the sediment liberates phosphorus and the trace metals into the water.
Ranjbar (1998) studied the concentrations of Cd, Pb, Cu, Zn, and Ni in surficial sediments from eleven sampling sites in Anzali wetland, Iran. He showed that there were statistically significant differences among the accumulation of the metals in sediments .Also he added that one of the sampling sites showed the lowest similarity compared to others. with respect to the data on metal concentrations in surficial sediments of fresh water
bodies in various region of the world,
He
concluded that the levels of the all selected heavy metals in this study were relatively high.
34
………………………..……………….…………………………... Introduction Ghallab(2000) studied some physical and chemical changes in the water and sediment of the River Nile down stream of Delta Barrage at El Rahawy drain. The water body in the drain was anoxic in the surface and bottom in which there was a high toxic concentration contents such as NH4+ , H2S, CI, Na, Ca, and Mg as well as high concentrations values of the heavy metals such as: Fe, Mn, Zn, Cu, Cd and Pb. Also, the high
content
of carbonate in the sediments was recorded due to
precipitation of Ca and Mg carbonate during hot seasons. Bolalek and frankowski (2003) studied the water and sediments of southern Baltic. They measured nutrients (ammonia and phosphate), sulfate and total iron. Redox potential, pH, humidity and organic matter content were determined in bottom sediments from these regions. The results showed that reduction processes were more advanced and
rich in organic matter and evidenced by lower values of redox
potential.
Ikem et al. (2003) studied the concentration of trace elements in water, sediments from Tuskegee Lake located in southeastern United States. They reported that the lake water quality characteristics were mostly below recommended water standards by United States except for aluminum, iron, and manganese, in addition to the average values of Cr, Zn and Cl in water samples analyzed were higher than respective reference values for fresh water. Also, they showed that the Mn and Pb followed by Zn, Cu and Co posed the highest risk to water contaminations.
Kruppam et al. (2003) studied the distribution of trace metals and organic matter in the sediments of Godavari east of India. They showed that the enhanced metal concentration in the sediments was localized and was accompanied by marked enrichment in organic carbon, nitrogen. Also they added that the high concentrations of organic matter observed near the river side sampling stations. Also relatively high
organic carbon
content
was observed in pre monsoon compared to post
monsoon seasons which could be attributed to the higher productivity to upwelling in land run off .Also they found that the trace metals in the sediments were found to be in the following order of their abundance
Fe > Mn > Zn > Pt > Cu in monsoon
season relatively high levels of trace metals were reported in surface sediment.
35
………………………..……………….…………………………... Introduction
Santos and Navor (2003) studied the distribution of Zn, Cd, Pb and Cu metals. They pointed out that the river has received heavy metals from two different sources ,industrial wastes and intensive agricultural activity. they showed that in 1998 the accidental release in the river of a bout 6 million m3 of acid water and sludge. The main polluting agents were heavy metals. Also they added there was a direct association between the physico chemical speciation of an element and bioavailability
Saeed and Shaker ( 2005 ) studied The heavy metals concentrations (Fe, Zn, Cu, Mn, Cd and Pb) in water, sediment as well as their presence in Oreochromis niloticus organs (muscle, gills and liver) in the River Nile northern Delta lakes (Edku, Borollus and Manzala) to assess the man-made impact on their environment. Water, sediments and fish organs from Lake Manzalla showed greater concentrations of most studied metals than those from Lake Edku and Lake Borollus. Fe, Mn, Cd and Pb in Lake Manzala and Mn and Pb in Lake Borollus recorded levels above the international permissible limits in water. In sediment samples Mn in Lake Edku and Cd in Lake Manzala recorded higher values than the sediment quality guidelines. Gills and Liver of
O.niloticus contained the highest concentration of most the
detected heavy metals, while muscles appeared to be the last preferred site for the bioaccumulation of metals. This study showed that fish organs contained high levels of heavy metals which are higher than the permissible international limits values. .
The edible part of O. niloticus showed higher levels of Cd in Lake Edku and Manzalla and Pb in Lake Manzalla. So, this fish species caught from the two lakes may pose health hazards for consumers. This was attributed to the lakes received large quantities of industrial, agricultural and sewage effluents especially Lake Manzala. A recommendation is given to forbid fishing from that area of Lake Manzala
36
………………………..……………….…………………………... Introduction
El-Bahy et al. (2006) studied the application of Atomic absorption spectroscopic method was identification of trace elements, namely, Cd, Co, Cr, Cu, Pb, Sn and Zn in the river Nile sediments. The method was applied to a standard sediment (SRM 2704) for certifications. The method includes, optimization of flame parameters, burner height, fuel and oxidant ratio. The effect of moving the impact device upon the sample uptake was also studied. Matrix effects on each element were studied. The results showed that, matrix matching is important to avoid its effect upon the samples under analysis. Increasing the burner height up to 16 mm resulted to an increase in flame temperature. Adjusting the distance of the impact device directly affects the atomization of the samples, hence achieving the maximum sensitivity of the measurements. The Nile sediment was surveyed, and the recorded major elements are Al, Fe, Ca, Mg and Mn with, 8, 7, 3, 2 and 1%, respectively. The absorbance of Cd, Co, Cr, Pb, Sn and Zn were increased as the Al concentration increased. Furthermore, it was found that each element is characterized by specific analytical conditions.
Iwegbue et al. (2007) studied the assessment of Ase River, in dry and wet season of 2006, which the sediment samples were collected at five locations to determine spatial variation of anthropogenic pollutants. Heavy metal levels (mg kg-1) in the sediment were Cd 2.89±2.97, Pb 7.00±10.04, Cr 2.34±2.53, Cu 3.32±2.37, Mn 24.27±9.92, Ni 7.04±7.49, Fe 110.53±101.54 and Zn 12.46±4.56 for dry reason and Cd 2.35±2.71, Pb 6.42±9.03, Cr 21.16±2.19, Cu 3.38±1.72, Mn 21.58±14.93, Ni 5.62±4.22, Fe 86.93±88.36 and Zn 5.63±4.22 for wet season. The results revealed significant spatial and temporal variation in the characteristic levels of heavy metals in the sediments.
The variance results from changes in contaminants supply, rate of deposition and erosion as well as seasonal variability in physicochemical conditions. The accumulation pattern of heavy metals in the sediment follows the order Fe> Mn >Zn >Ni >Pb >Cu >Cd >Cr. The levels of heavy metals were similar to levels found in unpolluted sediments and continental crust system is at risk of cadmium pollution.
37
except
for Cd.
Such sediment
………………………..……………….…………………………... Introduction
Lasheen and Ammar ( 2008 ) investigate the mobility and the availability of metals in sediments from different sites along the Nile River in Cairo district using sequential chemical extraction technique. The speciation data showed that most metals were associated with organic/sulfide and residual fractions. The order of total metal concentrations in sediment samples was found to be Fe > Mn > Zn > Ni > Cu ≥ Cr > Pb > Cd.
38
CHAPTER II
…………………………………….……………………... Materials and methods
Fig (1). The Sludge Judge: sludge samplers are designed to take accurate readings of settled solids, 5% or less.
39
…………………………………….……………………... Materials and methods
Fig (2). ICP-OES Varian Liberty Series II , is a fast multi-element technique with a dynamic linear range and moderate-low detection limits (0.2-100 ppb).
40
Fig (5). pH Meter Jenway 3510
Fig (3). UV/VIS Spectrophotometer Jenway 6505
Fig ( 6 ).Conductivity Meter Jenway 4510
Fig (4). Turbidity Meter Hack 2100 N
…………………………………….……………………... Materials and methods
El –Roda ( VII ) El- Maadi ( VI )
North- Helwan ( V )
Kafr – Elewa ( IV ) Saqqara
EL Tebeen( III ) Iron & steel co.
Helwan Bridge
Iron & steel drain ( II )
El- Saaf ( I )
Fig ( 7 ) Area of investigation extended along a distance of 40 km From El-Saaf ( I ) to El-Roda ( VII )
42
…………………………………….……………………... Materials and methods
Material and Methods 1- Sampling Area Area of investigation extended along a distance of 40 km from El-Saaf south of giza governorate to El-Roda island on the River Nile in front of the industrial area of Helwan province Fig (7). The selection of the sampling stations depend mainly on the industrial waste water at iron and steel company and it is effect up stream of River Nile water and El-Saaf station as a reference point.
Seven stations were selected for collection water and sediment samples, the stations are: Station ( I ) : El-Saaf city Which is located in the south of the iron and steel plant at Helwan. It is considered as a reference point.
Station ( II ) : Iron and Steel which is located in front of iron and steel drain wastewater Station ( III ) : El-Tebeen zoon which is situated up stream iron and steel drain beside El-Tebeen drinking water station. Station ( IV ) : Kafr- Elawe area which is situated beside Kafr-Elawe drinking water plant station. Station ( V ) : North-Helwan which is situated beside North-Helwan drinking water station. Station ( VI ) : El-Maadi city which is situated beside El-Maadi drinking water station. Station (VII ) : El-Roda area which is situated beside Kafr-Elawe El-Roda drinking water station.
43
…………………………………….……………………... Materials and methods
2- Sampling collection A – Water samples During period from spring 2008 to winter 2009, water samples where collected seasonally from subsurface layer selected from different sites along the extent of 40 Km in the main channel of the River Nile. The samples are collected in three types of bottles. B.O.D Bottle (Glass Stoppard bottles) for determining dissolved oxygen and biochemical oxygen demand, ICP Bottle for metals determination , This bottle made from autoclavable plastic ( capacity 0.5 L ) , and we must be acidify the sample to pH < 2 with using very pure nitric acid, 2 ml for 0.5 L and stored in a refrigerator. For spectrophotometer, wet chemistry, physical parameters using dried plastic bottle (capacity 2 L).
B – Sediment samples Sediment samples were collected by the sludge judge Fig ( 1 ) from the same stations, sediment samples were kept in polyethylene plastic bottles, then dried for analysis.
3- Methods of Analysis ◌A ِ - Water Analysis The physical and chemical parameters of water sample were determined according to the standard methods (APHA, 1995). I- Physical Parameters i - Temperature Water's temperature was measured by using digital thermometer (-10 -105 °C), (CE Jenway 4510)
44
…………………………………….……………………... Materials and methods
ii - Turbidity Turbidity measures the degree to which the water looses its transparency due to the presence of suspended particulates. Turbidity is also considered as a good measure of the water quality. and was measured by using Hack Turbidity meter 2100 N Fig ( 4 ), Turbidity is commonly measured in (Nephelometric Turbidity Units )(NTU).
iii - Electrical Conductivity The electrical conductance of water samples was measured by using conductivity meter model ( Jenway 4510) Fig ( 6 ) and expressed in ( µS).
iv - Solids Analysis Solids analysis is important in the control of biological and physical wastewater treatment processes and for assessing compliance with regulatory agency waste water effluent limitations (APHA, 1995).
* Total Solids (TS) Principle: A well-mixed sample is evaporated in a dry weighed dish and dried to constant weight in an Oven at 105 °C. The increase in weight over that of the empty dish represents the total solids and expressed in (mg/L).
Procedure: * heat the dish to remove moisture. * weight the dish as soon as it has completely cooled. * pipette a measured volume of well-mixed sample to a pre-weighed dry dish and evaporate to dryness at 105 °C in a drying Oven. * weight the dish as soon as it has completely cooled. * The difference in weight of the evaporating dish and before drying corresponding to (total solids).
Calculations: TS (mg/L) = (A - B) X 1000 / ml of sample A: weight of dried residue + dish in (mg) B: weight of empty dish in (mg).
45
…………………………………….……………………... Materials and methods
* Total Dissolved Solids (T.D.S) Principle: A well-mixed sample is filtrated through a standard glass fiber filter, (GF/C) and the filtrate is evaporated to dryness in a dry weighed dish and dried to constant weight in an oven at 180 °C. The increase in weight represents the total dissolved solids.
Procedure: Filter a portion of the sample through ( glass fiber filter GF/C 47 mm). Repeat the procedure outlined in the (T.S) method. Record the increase in weight over empty dish as (total dissolved solids) on drying at 180 °C in unit (g/1).
Calculation: TDS (g/l) = (A - B) X 1000 / ml of sample A: weight of dried residue + dish in (g) B: weight of empty dish in (g).
* Total Suspended Solids (T.S.S.) Principle: The difference between the total solids and total dissolved solid may provide an estimated the total suspended solids.
Calculation: TSS (g/l) = "TS" (g/1) - "TDS" (g/1)
2- Chemical Parameters i- Hydrogen Ion Concentration "pH" Principle: The basic principle of electrometric pH measurements is the determination of the activity of hydrogen ions by using a standard hydrogen electrode "Glass electrode" and a reference electrode.
46
…………………………………….……………………... Materials and methods Procedure: The pH values of the water samples were measured using "pH meter" model Jenway 3510 Fig ( 5 ) after calibration with standard pH buffer of 4, 7 and 10.
ii- Dissolved Oxygen (DO) Determination of dissolved oxygen was carried out by using Winkler method (1952) according to standard methods.
Principle: Addition of a divalent manganese salt to test water, it precipitates as Mn(OH) 2 , on addition of caustic soda solution containing KI, Mn(OH) 2 is oxidized quantitatively into higher manganese hydroxide by the dissolved oxygen. The addition of concentrated H 2 SO 4 initiates the oxidation of iodide with higher manganese hydroxides and lead to liberation of equivalent iodine. The liberated iodine was titrated against standard thiosulphate solution and using starch as indicator , the concentration of iodine equivalent to dissolved oxygen and express in (mg/l).
Procedure: To a water sample collected in (250-300 ml) D.O bottle add 1 ml MnSO 4 solution, followed by 1 ml of alkaline iodide solution. Stopper carefully to exclude air bubbles, Mix well by inverting bottle several times, then add 2 ml Conc. H 2 SO 4 . Titrate the liberated iodine against using starch as an indicator.
standard
thiosulphate
Calculation: D.O mg/1 = N X V X 8 X 1000 / ml of sample N = normality of sodium thiosulphate "0.025N" V = volume of standard sodium thiosulphate 8 = equivalent weight of O 2
47
(0.025 N)
…………………………………….……………………... Materials and methods
iii- Biochemical Oxygen Demand (B.O.D) This method is called " 5-Days B.O.D Test "
Principle: This method consists of filling with samples to overflowing an airtight bottle of the specified size and incubating it at specified temperature for 5 days. DO is measured initially and after incubation, and the BOD is computed from the difference between initial and final DO.
Procedure: * Two identical water samples were placed in Stopperd BOD bottles. * the dissolved oxygen concentration was measured immediately after collection of the sample as "blank", while the other sample was incubated at 25 °C for 5 days in the dark. * at the end of the 5 days period, the second bottle is removed from the incubator and the remaining DO concentration is measured. * The BOD of the water sample, is the difference between the two DO measurements,
Calculation: BOD mg/1 = (A-B)X N X 8 X 1000 / ml of sample A = volume consumed of standard thiosulphate solution in determining immediate DO B = volume consumed of standard thiosulphate solution in determining DO after 5 days N = normality of sodium thiosulphate "0.025N" 8 = equivalent weight of O 2
iv- Chemical Oxygen Demand (C.O.D) Determination of COD was carried out by using potassium permanganate method according to standard methods.
48
…………………………………….……………………... Materials and methods
The chemical oxygen demand (C.O.D) is used as a measure of the oxygen equivalent of the organic matter content of a sample that is susceptible to oxidation by a strong chemical oxidant, for samples from specific source, COD can be related empirically to BOD, organic matter, KMnO 4 is used as a good oxidizing agent in this method.
Procedure: Heat to boiling 100 ml of water sample after addition of 5 ml KMnO 4 solution ( 0.I N) , Leave the sample for 1 hr. at low temperature, Cool, and add 5ml of KI (10%) solution and 10ml of H2SO 4 (4N).
Calculation: COD mg/1 = α - β X N X 8 X 1000 / ml of sample α = volume of standard thiosulphate solution consumed with blank sample ( bidistilled water). β = volume of standard thiosulphate solution consumed with water sample. N = normality of sodium thiosulphate "0.1N" 8 = equivalent weight of O 2 .
v- Major Anions: a- Carbonate Alkalinity Principle: Alkalinity of water is its acid-neutralizing capacity. It is the sum of all the titrable bases. The measured value may vary significantly with the end point, pH used.
Procedure: To 50 ml sample, add three drops of phenolphthalein indicator, titrate against H 2 S0 4 (0.02N) until the pink colour disappear.
49
…………………………………….……………………... Materials and methods Calculation: CO 3 - - (mg/l) = A X N X 50 X 1000 / ml of sample A = volume of standard H 2 SO 4 N = normality of standard H 2 SO 4 (0.02N) 50 = equivalent weight of CaCO 3 .
b- Bicarbonate Alkalinity Procedure: To determine bicarbonate for the same sample, add three drops of Methyl Orange indicator, then titrate against H 2 SO 4 ( 0.025N ) until the end point ( win red coloure ).
Calculation: HCO 3 - - (mg/1) = (2A - B) X N X 81 X 1000 / ml of sample A = volume of standard H 2 SO 4 in case of phenolphthalein indicator. B = total volume of standard H 2 SO 4 after added of Methyl Orange. N = normality of standard H 2 SO 4 (0.025N) 81 = equivalent weight.
vi- Sulphate. Sulphate concentration in the water samples were determined by (Turbidimetric method).
Principle: Sulphate ion is precipitated in HC1 medium with BaCl 2 To form barium sulphate BaSO 4 crystals of uniform size. Light absorbance of BaSO 4 suspension measured by Turbidimeter Hack 2100 N. And compare the value with standard sulphate solutions values.
50
…………………………………….……………………... Materials and methods Procedure: To 100 ml of sample , add 10 ml condition salt solution ( NaCl + ethyl alcohol + HCL + glycerol + D.W ) and mix well in stirring apparatus, during stirring add 1 g from BaCl 2 , stirring for 2 minutes at constant speed Wait 1 minute, measure the turbidity, compare the value standard sulphate turbidity ( NTU ) curve.
of
turbidity by
vii- Chloride Chloride in the water samples determined by using (Argentometric method)
Principle: In a neutral or slightly alkaline solution, potassium chromate K 2 CrO 4 can indicate the end point of the silver nitrate titration with chloride. Silver chloride is precipitated quantitatively before red silver chromate is formed.
Procedure: To 50 ml sample, add three drops of potassium chromate indicator, than titrate against AgNO 3 (0.0141 N).
Calculation: CI - (mg/l) = A X N X 35.45 X 1000 / ml of sample A = ml added of AgN0 3 ( 0.0128N ) . N = normality of AgNO 3 ( 0.0128N). 35.45 = atomic weight of CI -
viii- Fluoride Spadns colorimetric method is used to determine the amount of fluorides dissolved in water ranged from 0 – 0.3 mg/l.
Principle: The Spadns colorimetric method is based on the reaction between fluoride and a zirconium-dye lake. Fluoride reacts with the dye lake, dissociating a portion of it into colorless complex anion (ZrF 6 2-); and the dye. As the amount of fluoride increases, the color produced becomes progressively lighter.
51
…………………………………….……………………... Materials and methods
Procedure: To 50 ml add 10 ml of the acid- zirconyl –spadns solution ( red dye ) , mix well , after 10 minutes the colour has developed and can be measured in the spectrophotometer at a wavelength ( 570 nm ) against a blank sample of distilled water treated by Spadns dye and standard fluoride solution.
Calculation: Cs/C unknown = A unknown/As Cs, As = concentration and absorbance of standard fluoride sample C unknown, A unknown = concentration and absorbance of unknown sample
ix- Major Cations: a- Sodium and Potassium Sodium and potassium are determined by using the ICP-OES model Varian Liberty Series II Fig (2)
b- calcium Calcium and magnesium can be determined by using Copleximetric Method
Principle: Ethylenediaminetetraacetic acid and its sodium salts (EDTA ) form a chelated soluble complex when added to a solution of certain metals cations. If a small amount of a dye such as Eriochrom Black T or Mureoxide is added to an aqueous solution containing calcium and magnesium ions at pH of 10.0 ± 0.1, the solution becomes wine red if EDTA is added as a titrant, the calcium and magnesium will be complexed and when all of the magnesium and calcium have been complexed the solution turns from wine red to blue, marking the end point of the titration.
Procedure: To 50 ml of sample, add 4 ml of NaOH solution 1 N, then add 0.1 gm "Mureoxide" as an indicator and titrate against EDTA (0.01 M) or EDTA salt standard solution.
52
…………………………………….……………………... Materials and methods Calculation: Ca++ (mg/1) = V X N X 40.08 X 1000 / ml of sample V = ml added of EDTA N = Normality of EDTA titrant (0.01 M). 40.08 = molecular weight of Calcium.
c- Magnesium Principle: Total hardness = the sum of the concentrations of the calcium and magnesium ions expressed in mg/L The total hardness can be determined by the titration with 0.01 M EDA solution using EBT as indicator.
Procedure: To 50 ml of sample, add 2 ml of buffer solution (pH = 10), than add 0.1 gm EBT as indicator, than titrate against EDTA (0.01 M). In this case the volume of EDTA is equivalent to Ca ++ and Mg ++ .
Calculation: Mg ++( mg/l) = (V' – V) X N X 24.4 X1000/ml of sample V' = volume of EDTA in case EBT indicator. V = volume of EDTA in case mureoxide indicator. N = Normality of EDTA titrant (0.01 M). 24.4 = molecular weight of magnesium.
d- Aluminum Two methods can be used to determine Aluminum ion concentration First, by using ICP – OES according to APHA 3500 –Al C, Second by using Eriochrome cyanine R method APHA 3500-Al D
Principle: With Eriochrome cyanine R dye, Dilute aluminum solutions buffered to a pH of 6.0 produce a red to pink complex that exhibits maximum absorption at 535 nm. The intensity of the developed color is influenced by the aluminum concentration, reaction time, temperature, pH, alkalinity, and concentration of other ions in the sample. To compensate for color and turbidity, the aluminum in one portion of sample is complexed with EDTA to provide a blank.
53
…………………………………….……………………... Materials and methods Procedure: To 25 ml of sample, add H 2 SO 4 (N/50) to remove total alkalinity + 1ml ascorbic acid +10 ml of sodium acetate buffer reagent + 5 ml of working Eriochrome cyanine R dye , then measure against standard aluminum solution was treated by the same procedure.
Calculation: Cs/C unknown = As/A unknown Cs, As = concentration, absorbance of standard Aluminum C unknown, A unknown = concentration, absorbance of unknown sample
x- Nutrient Salts a- Ammonia Ammonia in fresh and drinking (Nessler method).
water can be determined by using
Principle: When Nessler reagent K 2 [HgI 4 ] is added to a diluted ammonia solution the liberated ammonia reacts with the reagent fairly rapidly but not intaneously to form an organ brown product, which remains in colloidal solution. The yellowish brown color absorbs at wavelength of 405 nm.
Procedure: *
To 50
ml sample, add
one drop of Rochell salt (sodium-potassium
tartrate) reagent as buffer, then add 1 ml of Nessler reagent.
Stand for 10
minutes. Measure the absorbance of the yellow color spectrophotometrically at wavelength of 420nm. * construct a standard calibration curve with
serial dilutions of
standard
ammonia solution. * To calculate the unknown concentration of
ammonia in
water
sample,
compare the absorbance reading with the standard calibration curve readings.
54
…………………………………….……………………... Materials and methods
b- Nitrate Principle: Nitrate forms with potassium- sodium tartrate a yellowish complex that can be spectrophotometrically measured at a wavelength of 420 nm.
Procedure: Pipet 20 ml of sample or a suitable portion diluted to 20 ml in a beaker and add 1 ml of the sodium salicylate solution. Evaporate the sample slowly at 105 oC in a drying oven. The residue will be cooled before adding 2 ml of H 2 SO 4 conc. After 10 min. add first 15 ml distilled water then 15 ml of potassium – sodium tartrate solution and wait 10 min. until the color has fully developed.
Calculation: Construct a standard calibration curve with serial dilutions of nitrate solution by using potassium nitrate salt.
standard
To calculate the unknown concentration of nitrate in water sample, compare the absorbance reading with the standard calibration curve readings.
c. Nitrite Principle: Nitrite is determined through formation of a reddish purple azo dye produced at pH 2.0 to 2.5 by coupling diazotized sulfanilamide with N-(1naphthyl)-ethylenediamine dihydrochloride (NED dihydrochloride).
Procedure: To 50 ml sample, added one ml of acidifies sulphanilide solution and one ml of NED solution. After 10 minutes the color obtained was measured spectrophotometrically at wavelength 543 nm Standard solution of sodium nitrite was used for preparing the calibration curve and then finds out the concentration of unknown sample.
55
…………………………………….……………………... Materials and methods
d. Reactive Silicate Reactive silicate determined by "molybdosilicate method"
Principle: Ammonium molybdate reacts with silica and any present phosphate at pH 1.2 to produce heteropoly acids. Oxalic acid is added to destroy the molybdophosphoric acid but not molybdo silicic acid. The intensity of the yellow color is proportional to the concentration of "molybdate – reactive" silicate.
Procedure: To 50 ml sample, add
in rapid
succession 1 ml HC1 "1: 1" and 1 ml
ammonium molybdate reagent. Mix well by inverting at least six times and stand for 5-10 minutes. Add 1ml oxalic acid reagent and mix-thoroughly. Measure the absorbance of the yellow green color after 2 minutes but before 15 minutes at wave length of 410 nm.
Construct a standard calibration curve through preparation of series of silica concentrations. To calculate the unknown concentration of the water samples compare the absorbance value with that of standard calibration curve.
e. Total Reactive phosphorus (TRP) Direct colorimetry determination of phosphorus as orthophosphate by using "stannous chloride method", this give total reactive phosphorus
Principle: Determination of all phosphorus forms "total reactive phosphorus, total dissolved phosphorus, total phosphorus and dissolved reactive phosphorus" depend on that molybdophosphoric acid is formed after the addition of ammonium molybdate and reduced by stannous chloride to intensely colored molybdenum blue.
56
…………………………………….……………………... Materials and methods Procedure: To 50 ml sample, add 2 ml of ammonium molybdate reagent, followed by the addition of three drops of stannous chloride, after 2 minutes with well mixing but before 12 minute, measure the blue color spectrophotometrically at wavelength of 690 nm. Calculate the total reactive phosphorus concentration of the water samples from the standard calibration curve.
xi - Trace metals Iron, manganese, zinc, copper, nickel, chromium, cadmium and lead were measure by using ICP-OES Model Varian lab Liberty Series II Fig ( 2 ).
Principle: ICP, abbreviation for Inductively Coupled Plasma, is one method
of
optical emission spectrometry. When plasma energy is given to an analysis sample from outside, the component elements (atoms) are excited. When the excited atoms return to low energy position, emission rays (spectrum rays) are released and the emission rays that correspond to the photon wavelength are measured. The element type is determined based on the position of the photon rays, and the content of each element is determined based on the rays' intensity.
To generate plasma, first, Argon gas is supplied to torch coil, and high frequency electric current is applied to the work coil at the tip of the torch tube. Using the electromagnetic field created in the torch tube by the high frequency current, Argon gas is ionized and plasma is generated. This plasma has high electron density and temperature (10000K) and this energy is used in the excitationemission of the sample. Solution samples are introduced into the plasma in an atomized state through the narrow tube in the center of the torch tube.
57
…………………………………….……………………... Materials and methods
Equipment for ICP optical emission spectrometry consists of a light source unit, a spectrometer, a detector and a data processing unit. There are several types of equipment based on differences in the spectrometer and the detector. The most common type is shown in the following fig ( 8 ).
Sequential Type ICP-OES
Preservation and preparation of the samples: 1- Preserve sample immediately after collection by acidifying concentrated HNO 3 to pH < 2, Use 5ml nitric acid for 1 Liter sample.
with
2. After acidify store preferably in refrigerator at 4°C or deep freezer to prevent change in volume due to evaporation. 3. to extract trace elements from water sample, nitric acid digestion method were used as follows: mix well 500 ml sample in beaker on hot plate, add 10ml of conc. HNO3 bring slow boil, evaporate, till volume be lowest volume possible 200-100 ml before precipitation occur, continue heating, add another 10 ml of HNO3 until the volume reduced to 80-100ml. Transfer to 100ml volumetric flask with 10ml distilled water, dilute to the mark. Mix thoroughly and filter if necessary. Take a portion of this solution for required determination. Also we can measure Iron concentration spectrophotometrically by using 1,10 phenanthroline method.
58
…………………………………….……………………... Materials and methods Principle: Iron is brought into solution, reduced to the ferrous state by boiling with acid and hydroxylamine, and treated with 1, 10-phenanthroline at pH 3.2 to 3.3. Three molecules of phenanthroline chelate each atom of ferrous iron to form an orange-red complex. The colored solution obeys Beer’s law; its intensity is independent of pH from 3 to 9. A pH between 2.9 and 3.5 insures rapid color development in the presence of an excess of phenanthroline. Color standards are stable for at least 6 months.
Procedure: To 50 ml add 2 ml HCl (1:1) "containing less than 0.5 ppm iron ". and 1 ml hydroxylamine , evaporate , till volume be lowest 20 ml , add 10 ml ammonium acetate buffer solution, and 1 ml phenanthroline solution. Complete to 50 ml by distilled water, then measure against standard ferrous iron solution was treated by the same procedure.
B- Sediment analysis i- Organic matter "OM" % Organic matter was determined by (loss on ignition method) according to (Hanna, 1965). The sediment sample was dried in an Oven at 105 °C to exclude any moisture content and finally reached to constant weight. Then 0.5g of dried samples was transferred to a weighed porcelain curcible in an electric muffle at 700 °C, hold at this temperature for 30 minute. Then put in desiccator , and weight. Report percentage loss weight as "loss on ignition"
Calculation: OM % = loss on ignition / weight of sample X100
59
…………………………………….……………………... Materials and methods
ii- Carbonate Carbonate content of sediment was determined by the method described by Alexjev, (1971). 0.5g of the
sediment samples was mixed
with 10ml of HC1
(0.5N) in an 100ml conical flask. The conical flask covered and boiled gently for 5 minutes, left to cool. Then, 50 ml of distilled water was added and the sample was filtered through Whatman filter paper. Titrate against NaOH (0.25N) using phenolphthalein indicator. Blank was made using 0.5g dry pure CaCO 3 The amount of acid used was determined.
Calculation: The carbonate percentage was calculated according to the following Carbonate percentage as CaCO 3 = (A X M 1 XI00) / (B X M 2 )
Where: A: the amount of unused acid for sediment sample B: the amount of unused acid for sediment blank M 1 : Molecular weight of CO 3 - M 2 : Molecular weight of CaCO 3
iii- metals Determination of cations ( Na+ and K+) and heavy metals (Fe, Al, Mn, Cu, Zn, Cr ,Ni, Pb and Cd) in sediment samples depend on the completely digestion of sediments. Digestion was done according to Kouadio and Trefry (1987). The steps of completely digestion can be summarized as following:
1- 10 ml concentrated nitric acid and 10ml hydrofluoric acid were added to 0.5 g of the finely powdered sediment material into Teflon bottles. the Teflon bottles were covered and set a side for overnight.
2- 5 ml perchloric acid was added and the bottles were heated in sand bath on hot plate and evaporated to about 3ml.
60
…………………………………….……………………... Materials and methods
3- the bottles were cooled and washed down the side with a little deionized water then add 5ml HC1O 4 and evaporate just to dryness.
4- add 10ml of concentrated HCI and the bottles were placed back on the hot plate until the solution were clear and the fumes ceased.
5- The digest material was filtered and the residue was washed several Times with deionized water.
6- The filtrate was then diluted by deionized water to 100ml in volumetric.
Analysis of cations ( Na+ and K+) and heavy metals (Fe, Mn, Cu, Zn, Cr ,Ni, Pb and Cd) was carried out using ICP-OES varian Liberty series II.
61
CHAPTER III
…………………………………….…………..…………... Results and discussion
Results and discussion In this chapter , physical and chemical characteristics of Nile water include major cations , major anions , nutrient salts and trace metals as will as trace metals in sediment were cited during the study period from spring 2008 to winter 2009
Part I – water analysis A – Physical parameters 1-Temperature Temperature is one of the most important characteristics of water environment. both atmospheric deposition and climate play a dominate role in determining the chemical characteristic of water ( Machetto , and molleon 1995) On the other hand, temperature factor affects phase equilibrium and influencing the rate of biochemical processes which cause the changes of concentration and the content of organic and mineral substance. Moreover, biological activity in the environment in enhanced by higher temperature up to about 60 oC. The growth and death of micro-organisms and biological oxygen demand are regulated to some extent by temperature which plays a vital role in chemical and biological reactions, the rate of oxidation of organic matter is much greater during summer than during winter. The shifting of various dynamic equilibrium such as concentration of carbonates , sulfides or degree of alkalinity is effected by temperature ( Wright & Schinder , 1995 and Skjekvale & Wright 1988 ).
The seasonal variations of water temperature of River Nile in front of the industrial area of Helwan province is recorded in table ( 1 ) and represented graphically in fig ( ۹ ). The values of water temperature fluctuated between 26.3 -27.1, 29.8 - 30.2, 24 - 25.2, 19.9 -23.5 oC during spring, summer, autumn, winter respectively.
The minimum water temperature recorded during winter was 19.9 oC at station ( IV ) , while the maximum value was 30.2 oC measured during summer at stations ( V & VII ) .
62
Seasons stations El-Saaf Iron-Steel El- Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda
Seasonal avr.
spring
30 29.9 30 29.8 30.2 30.1 30.2 30.0
summer
25.2 24.1 24.9 24.8 24.9 24.8 24.0 24.7
Autumn
23.5 23.2 23.2 19.9 22.2 22.1 22.3 22.2
winter
26.4 26.1 26.2 25.2 26.0 25.8 25.5 ----
Annual average
Table (1) Seasonal variations of water temperature (oC) in the investigated area during 2008
26.8 27.1 26.7 26.4 26.5 26.3 26.5 26.6
…………………………………….…………..…………... Results and discussion
Fig : 9 water temperature oC of River Nile at Helwan area during 2008 (a) annual average (b) seasonal average
a : annual average. o
C
26.6 26.4 26.2 26 25.8 25.6 25.4 25.2 25 24.8 24.6 24.4
annual aver.
i
ii
iii
iv
v
vi
vii
Stations
b: seasonal average. o
C
35 30 25 20 seasonal aver. 15 10 5 0
Seasons Spring
Summer
Autumn
64
Winter
…………………………………….…………..…………... Results and discussion On the whole, the decrease or increase in water temperature of the River Nile depends mainly on the climatic conditions , sampling time , the number of sunshine hours and also affected by specific characteristics of water environment such as turbidity , wind force , plant cover and humidity ( Mahmoued , 2002 and Tayel 2002 ) . Again the seasonal average values varied in the range of 22.2 - 30 0C during winter and summer with, no great variation between different stations along the investigated area during the year round.
Patrick (1953 ) and Bourd (1953 ) ; showed that , there was relationship between fish survival and temperature for example roach were not able to stand for long periods if water temperature become greater than 27 0C, and also, rainbow trout died when the water temperature was much above 18 – 19 0C, also sudden change in temperature of more than 2 0C cause harmful to American sunfish . furthermore, temperature rise may have adverse effects on hatching of eggs, the temperature value affects the survival of fish and the rate of growth and reproduction.
On other side Welch ( 1952 ) ; showed the affect of temperature on bacteria in which increase of temperature facilitates the growth and multiplication , while the number of bacteria may be reduced by low temperature . thus , for regional average , winter time show minimum value of 26.5 0C .
2 –Turbidity Turbidity measures the degree to which the water looses its transparency due to the presence of suspended particulates. Turbidity is considered as a good measure of the water quality. and commonly measured in ( Nephelometric Turbidity uints ) NTU, which measures the intensity of light scattered at 90 degrees as a beam of light passes through a water sample. The World Health Organization , establishes that the turbidity of drinking water shouldn't be more than 5 NTU, and should ideally be below 1 NTU.
65
…………………………………….…………..…………... Results and discussion on the reverse transparency is great influenced by both turbidity of water and abundance of phytoplankton, zooplankton and other aquatic microorganisms in water column; thus, the transparent water indicates an absence of plankton, while turbid water signified of plankton and/ or suspended particles ( DeJince , 1992) The seasonal variations of water turbidity of River Nile in front of the industrial area of Helwan province is recorded in table (2) and represented graphically in Figure (10). The turbidity values were varied in the ranges of 4.7 – 21.8, 4.7 – 24.1, 5.3 – 14.1 and 7.9 – 16.5
NTU
during spring, summer
autumn and winter , respectively. The lowest values 4.7 NTU recorded at station III and I during spring and summer, respectively, on the other side, the highest turbidity values 24.1 NTU was recorded at station II during summer beside iron and steel drain. Thus highest values of transparency were showed during spring and summer season this may be attributed to the uptaking of suspended matter by phytoplankton. Also it may by attributed to the increase of intensity of solar radiation penetrated the surface water as well as settling out or suspended to the bottom sediment (Olsen and Summerfield, 1977). On the other side, the lowest transparency values were showed during summer and autumn seasons, this may be attributed to the effect of
the
prevailing wind which facilitate the mixing of water and stirring up with the bottom sediment as mention by (Saad, 1978).
3 -Electrical conductivity (E.C) According to (APAH, 1995), the electrical conductivity is a measure of the ability of aqueous solution to carry an electric current. This ability depends on the presence of ions, their total concentration, temperature of the medium.
66
mobility,
valence and
the
Season station El-Saaf Iron-Steel El- Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda
Seasonal avr.
spring 4.7 24.1 5.9 5.1 5.4 6.6 5.8 8.2
summer
9.6 14.1 10.6 10.1 9.1 8.6 5.3 9.6
Autumn
9.2 16.5 7.9 12.9 7.9 8.3 8.7 10.2
winter
7.4 19.1 7.3 9 7.4 7.6 6.4 ----
Annual average
Table ( 2 ): seasonal variation of Turbidity (NTU) In investigated area during 2008
6.1 21.8 4.7 7.7 7 7 5.6 8.6
…………………………………….…………..…………... Results and discussion
Fig 10 (a) annual and (b) seasonal average values of water Turbidity NTU.
a: annual avrage. NTU 25 20 15 annual avr. 10 5
Station
0 i
ii
iii
iV
V
Vi
Vii
b : Season avrage.
NTU 12 10 8 6
Season avr.
4 2
Seasons
0 spring
summer
autumn
68
winter
…………………………………….…………..…………... Results and discussion Thus the Solutions of most inorganic compounds are relatively good conductors Conversely, molecules of organic compounds that don't dissociate in aqueous solution conduct current very poorly. Thus, the more abundant the ions, the higher is the conductivity and vice versa. The seasonal electrical conductivity variations were given in Table (3) and represented graphically in Figure (11) respectively. The values of electrical conductivity in the area under investigation varied in ranges of 336 – 1155, 304 - 796, 360 – 782 and 403 – 1236 µS/cm for subsurface layer during, spring, summer autumn and winter respectively.
The lowest values of 304 µS/cm recorded at station I during summer On the other side, the highest electrical conductivity values 1236 µS/cm was recorded at station II during summer beside iron and steel drain Increasing of the values during winter season may be attributed to the decreasing on the water level of river Nile during drought period. in the summer, E.C. values were decreased may be attributed to the dilution effect caused by more water comes from south lake Nasser and increasing on the water level. Generally, the electrical conductivity of fresh water varies between 50 to 1500 µS/cm but in some polluted water reached to 10000 µS/cm while in sea water reached to 35000 µS/ cm (Boyd and Tucker, 1979). According to Talling and Talling (1965): there are three main groups of E.C values are distinguished. Waters with conductivity below 600 µS/cm. Water between 600 to 6000 µS/cm and waters beyond 6000 µ.S/cm waters with low conductivity are found in marshland areas, they are usually of dark color and have high concentration of organic matter, in particular humic matter. Waters with intermediate conductivities
contain mainly sodium
chlorides
and
bicarbonate ions. Water with high conductivities result from high evaporation rates and salts concentration.
69
Season station 336 1155 382 355 350 379 354 473
spring
304 796 321 313 313 307 310 381
summer
360 782 385 385 414 380 379 441
Autumn
403 1236 450 429 437 427 422 543
winter
350.8 992.3 384.5 370.5 378.5 373.3 366.3 ---
Annual average
Table ( 3 ) : seasonal variation of Electrical Conductivity ( µS/cm) In investigated area during 2008
El-Saaf Iron-Steel El- Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda
Seasonal avr.
…………………………………….…………..…………... Results and discussion
Fig 11 (a) annual and (b) seasonal average values of water Electrical Conductivity (µS/cm)
a: annual avrage.
µS/cm 1200 1000 800 600
annual avr.
400 200
Station
0 i
ii
iii
iV
V
Vi
Vii
b: Season avrage.
µS/cm 600 500 400 300
Season avr.
200 100
Seasons
0 spring
summer
autumn
71
winter
…………………………………….…………..…………... Results and discussion
4 - Total solids. The total solids is very useful parameters describing the chemical constituents of water and can be considered as general measure of edaphic relationships that contribute to productivity within the water body( Sayed 2003 ) The seasonal variation of total solids in the subsurface water of investigated area are given in table ( 4 ) and represented graphically in fig. ( 12 ). The values of total solids in the subsurface water at investigated area at the River Nile varied in the range of 265 – 952 , 220 – 653 , 286 -540 , 310 – 898 mg/l during spring ,summer , autumn , winter respectively. The above mentioned results declared that , the total solids increased which showed a regional seasonal variation ( winter and Spring ) and decreased in hot seasons ( Autumn , summer ) . The higher values during winter may be due to the presence of high content of the anions and cations during drought period (Abdo, 2002) The decrease in the total solids during summer may be due to the dilution effect , which causes decrease of total solids and to precipitation to the bottom sediments by rise of water temperature. Also, the relative decrease in Autumn is may be due to the uptake of dissolve solids by phytoplankton . Nour El Din ( 1985 ); showed that before the construction of high dam a typical Nile flood used to have high concentration of suspended matters and low values of dissolved salts. In contrast the post dam River condition exhibit consistent low levels of suspended matter and relatively high values of dissolved Salts. On other hand , the highest value of total solids at the River Nile was recorded during spring at stations II this due to industrial wastes . in the reverses the lowest value of total solids recorded during summer at station IV. On the whole, the seasonal average values as reported in table ( 4 ) and fig (12) Show the minimum value of 220 mg/l is recorded during summer and maximum value of 952 mg/l is recorded during spring.
72
Season station El-Saaf Iron-Steel El- Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda
Seasonal avr.
spring
233 653 228 220 224 221 227 292
summer
286 540 328 300 326 314 304 343
Autumn
346 898 346 358 326 310 338 417
winter
280 761 301 289 286 286 284 ----
Annual average
Table (4): seasonal variation of total solids (mg/l ) In investigated area during 2008
265 952 302 278 266 297 267 375
…………………………………….…………..…………... Results and discussion
Fig 12 : (a) annual average and b: seasonal average values of Total solids (mg/l) of River Nile during 2008
a : annual average .
mg/l 800 700 600 500 annual aver.
400 300 200 100
Stations
0 i
ii
iii
iv
v
vi
vii
b: seasonal average .
mg/ l 450 400 350 300 250
seasonal aver.
200 150 100 50
Seasons
0 Spring
Summer
autumn
74
winter
…………………………………….…………..…………... Results and discussion
5 - Total dissolved solids. According to (APHA, 1995) dissolved solids is the portion of solides that passes through a filter of 2.0 mm (or smaller) nominal pore size under specified conditions.
The total dissolved solids (TDS) are the total amount of dissolved species in water (Peavy et al, 1986 and Hem, 1989). TDS causes the change of physical and chemical nature of water. High concentration of TDS tends to accelerate corrosion and can also exert osmotic pressure in aquatic life (Edumund, l978). The seasonal variation of total dissolved solids in the subsurface water of investigated area are given in table ( 5 ) and represented graphically in fig. (13 ). The values of total dissolved solids in the subsurface water at investigated area at the River Nile varied in the range of 222 – 874 , 201 – 569 , 237 -516 , 281 – 682 mg/l during spring, summer, autumn, winter respectively. The results declared that, the TDS increased in winter and decreased in summer.
The highest value during winter was recorded at station II 874 mg/l behind iron and steel company , while, the lowest value 201 mg/1 was recorded during summer at station I . The increase of total dissolved solids during winter may be attributed to the decrease in the water level during drought period this causes the anions and cations to be concentrated. The lowest value of total dissolved solids during summer may be due to dilution effect or may be due to accumulation of lime in derived from precipitation by dead plants and certain organic processes (Siliem, 1988)
75
222 874 252 234 231 250 234 328
spring
201 569 212 207 207 203 205 258
summer
237 516 255 255 273 287 250 296
Autumn
306 813 290 287 287 281 281 364
winter
242 693 252 246 250 246 243 ---
Annual average
Table ( 5 ) : seasonal variation of total dissolved solids T.D.S ( mg/l ) In investigated area during 2008
Season station El-Saaf Iron-Steel El- Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda
Seasonal avr.
…………………………………….…………..…………... Results and discussion
Fig 13 : (a) annual average and b: seasonal average values of Total dissolved solids (mg/l)
a: annual avrage.
mg/l 800 700 600 500 annual avr.
400 300 200 100
Stations
0 i
ii
iii
iV
V
Vi
Vii
b: Season avrage.
mg/l 400 350 300 250 200
Season avr.
150 100 50
Seasons
0 spring
summer
autumn
77
winter
…………………………………….…………..…………... Results and discussion
6 - Total suspended solids (TSS). According to (APHA, 1995) suspended solids is the portion of solids that retained on the filter paper after filtration of water by 2.0 mm (or smaller) nominal pore size under specified conditions. According to (APHA, 1992) Total suspended solids is the portion of solids remnant after the filtration includes an organic residues . Sackett (1975) reported that the detrital and authigenic origin are the main sources of suspended solid in aquatic environments. The detrital suspensoids include terrigenous particles transported by land runoff or winds, resuspended materials and particles resulting from under water eruptions. Authigenic suspensoids are those organic and inorganic particles produced by biological or inorganic chemical process. These include bacteria living nanoplankton, fecal pellets and other derived organic agglomerates together with in organic particles. On the other hand, organic detritus compounds play an important role in the aquatic environment that can adsorb the trace elements upon its active surfaces therefore, the suspended solid plays an important role in the distribution and the mechanisms of the trace metals in water body (Abdel Satar, 1998) The seasonal variation of total suspended solids in the subsurface water of investigated area are given in table ( 6 ) and represented graphically in fig. ( 14 ). The values of total suspended solids in the subsurface water at investigated area at the River Nile varied in the range of 33 – 78 , 16 – 84 , 24 -73 , 29– 85 mg/l during spring , summer , autumn , winter respectively. The results declared that, the TSS increased in winter and decreased in summer. The highest value during winter was recorded at station II 85 mg/l behind iron and steel company , while, the lowest value 16 mg/1 was recorded during summer at station III.
78
station
Season El-Saaf Iron-Steel El- Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda
Seasonal avr.
spring
22 84 16 13 17 18 22 27
summer
49 24 73 45 53 64 54 52
Autumn
38 79 49 43 36 40 42 54
winter
39 68 49 43 36 40 42 --
Annual average
Table (6): seasonal variation of total suspended solids (mg/l) In investigated area during 2008
43 78 50 44 35 47 33 47
…………………………………….…………..…………... Results and discussion
Fig 14 : (a) annual average and b: seasonal average values of Total suspended solids (mg/l)
a: annual avrage.
mg/l 80 70 60 50 annual avr.
40 30 20 10
Stations
0 i
ii
iii
iV
V
Vi
Vii
b: Season avrage.
mg/l 60 50 40 Season avr.
30 20 10 0 spring
summer
autumn
80
winter
Seasons
…………………………………….…………..…………... Results and discussion
B - Chemical parameters 1- Hydrogen Ion Concentration " pH " Pure water dissociates weakly to [H+] and [OH −] ions. The dissociation constant is very small (10−14), however, and the amounts of [H+] and [OH−] present are 10−7 g-ions per liter. Natural waters are, not pure and salt, acids and bases contribute to the [H+] and [OH−] ions in varying ways, depending on the individual circumstances. The dissociation constant of water is fixed, addition of one ion will result in a decreases of the other. The pH is usually defined as the logarithm of the reciprocal of the concentration of free hydrogen ions (Wetzel, 1983). By definition, pH values can't be averaged arithmetically, but the average must be estimated from the logarithm of the reciprocals (Kondo et al, 1989; Hashitani et ah, 1989). The biological activity in water sample and loss of gases can change pH. Also, dissolved mineral substance pick up aerosols and dust from the air and supports photosynthetic organisms which effect pH. Highly acidic or highly alkaline water undesirable because of corrosion hazards and treatment difficulties the pH measurements must be immediately because the value may be differ by virtue of reactions that can influence a delayed result like oxidation, hydrolysis interaction with the sediment loss of dissolved gases, absorption of laboratory fumes and deposition of CaCO 3 . Generally, the ability of aquatic organisms to complete a life cycle greatly diminishes as pH becomes > 9.0 or < 0.5 (Goel, 1947). The pH values are governed, to a large extent, by the interaction of H+ ions arising from the dissociation of H 2 CO 3 and from OH− ions produced during the hydrolysis of bicarbonate. The pH of natural water ranges between the extremes of < 2 to 12. Nearly all waters with pH values less than 4 occur in volcanic regions that receive strong mineral acids, particularly sulphuric acid (Likens etai, 1972).
81
…………………………………….…………..…………... Results and discussion
Generally, the range of pH values of rivers is between 6 and 9. Most of these river are the "bicarbonate type" i.e. they contain varying amounts of carbonate and are regulated by the CO 2 , HCO 3
−
, CO 3 - - buffering system.
The seasonal variations of pH values were recorded in Table (7) and represented graphically in Figure (15) respectively. The values of pH varied in the range of 7.61 - 8.3 , 7.41 – 7.83 , 7.65 – 8.21 and 7.65 - 8.06 during spring, summer autumn and winter respectively These indicated there is no observed variation. The relative increase of pH values during spring may be due to growth of algae and microorganism and photosynthetic activity (Abdo, 1998) Mason (1967) showed that pH of medium is particularly signify in controlling the transportation of alumna and silica in solution and ultimate redeposition.
2 – Dissolved Oxygen (DO) Dissolved oxygen (DO) is one of the key factors of the life. Moreover, DO is much more important to aquatic ecosystems than to terrestrial life as oxygen has a low solubility in water and is often a limiting factor for life in water. Oxygen is also needed for all oxidation, nitrification and decomposition processes and is controlled by three factors; photosynthesis, respiration and exchange at the air water interface (Krom et al, 1989 a, b; Erez et al, 1990).
Dissolved oxygen is obviously essential to the metabolism of all aerobic aquatic organisms. Hence, the solubility and dynamics of oxygen distribution in lakes are basic to understanding of the distribution, behavior and growth of aquatic organisms (Wetzel, 1983).
82
Season 7.9 7.61 8.3 8.15 8.1 8 8.15
spring
7.7 7.41 7.75 7.75 7.8 7.83 7.8
summer
7.75 7.65 8.21 8.14 7.95 8.13 8.1
Autumn
7.9 7.65 8.03 8.06 7.91 8 8.02
winter
Table ( 7 ): seasonal variation of Hydrogen ion Concentration (pH) In investigated area during 2008
station El-Saaf Iron-Steel El- Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda
…………………………………….…………..…………... Results and discussion
Fig 15 : (a) annual average and b: seasonal average values of Ion hydrogen concentration pH
a: annual avrage. 8.2 8.1 8 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2
annual avr.
Station i
ii
iii
iV
V
Vi
Vii
b: Season avrage. 8.1 8.05 8 7.95 7.9 7.85 7.8 7.75 7.7 7.65 7.6 7.55
Season avr.
Seasons spring
summer
autumn
84
winter
…………………………………….…………..…………... Results and discussion
The seasonal variations of dissolved oxygen values were recorded in Table ( 8 ) and represented graphically in Fig. ( 16 ) respectively, thus: The values of dissolved oxygen varied in the range of 3.9 – 7.9 , 4.2 – 6.7 , 3.3 – 6.2 and 4.5 – 7.4 mg/l
during spring, summer, autumn, and winter
respectively . The highest values of DO 7.9 mg/1 recorded during spring at the subsurface water of station IV. On the other side, the lowest value, 3.3 mg/1 was recorded during autumn at the subsurface water of station II behind iron and steel drain. The relative increase in DO concentration during winter, may be related to the decrease in temperature which reached to 19.9 °C , leading to an increase of the solubility of the atmospheric oxygen. But the decrease in water levels during the drought period, leads to a part of dissolved oxygen is used in the oxidation of organic and microorganisms, therefore the increase in DO values during this season was limited. This result agreed with that reported by Attia 2002.
The relative decrease in DO concentration during autumn which reached to 3.3 mg/l at station II in subsurface water, may be attributed to the dilution effect which depend on the flood in this season. This result agreed with that reported by (Ghallab 2000). The second reason may be related to that a part of dissolved oxygen used in the oxidation of organic matter constituent in the flood period in which the water are rich in organic matter. Generally, the dissolved oxygen concentration in water ecosystem is one of the most important parameters and is influenced by many factors. also, oxygen is a very important factor in controlling or affecting the fish movements, fish usually prefers warmer areas with high dissolved oxygen and here they also feed better. Under dissolved oxygen conditions, fishes are subjected to stress and their movements are restricted (Bowling, 1976; Wilson, 1975 and Garalles and Thompson, 1962).
85
station 6.6 3.9 6.8 7.9 6.9 7.4 6.4 6.6
spring 6.7 4.2 6.5 6.5 5.7 6.3 5.8 6
summer
6.2 3.3 5.5 5.3 5.6 5.8 6.1 5.4
Autumn
7.4 4.5 6.3 7.2 7.1 6.8 6.9 6.6
winter
6.7 4 6.3 6.7 6.3 6.6 6.3 ----
Annual average
Table ( 8 ) : seasonal variation of Dissolved oxygen D.O ( mg/l ) In investigated area during 2008
Season El-Saaf Iron-Steel El- Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda
Seasonal avr.
…………………………………….…………..…………... Results and discussion
Fig 16 : (a) annual average and b: seasonal average values of Dissolved Oxygen DO (mg/l)
a: annual avrage.
mg/l 8 7 6 5 annual avr.
4 3 2 1 0 i
ii
iii
iV
V
Vi
Vii
Stations
b: Season avrage. mg/l 7.00 6.00 5.00 4.00 Season avr. 3.00 2.00 1.00
Seasons
0.00 spring
summer
autumn
87
winter
…………………………………….…………..…………... Results and discussion
3 – Biochemical Oxygen Demand (BOD) The BOD is the amount of oxygen required for the oxidation of waste by bacteria, therefore a measure of the concentration of organic matter in a waste that can be oxidized by bacteria. In general, the BOD of waste water was lower than COD, because more compound can chemically oxidized than can be biologically oxidized (Clark and Michael, 1972). Presence of organic matter either dissolved organic matter (DOM) or particulate organic matter (POM) in water considered a big problem associated with water quality control. This organic matter is normally biologically oxidized and microorganisms involved utilized either aerobic or anaerobic oxidation system (Sayed, 1998). The biological oxygen demand depends upon the respiration of plankton and bacteria. Magnitude of BOD values depend on temperature, density of phytoplankton, concentration of organic matter and other \related factors.
The seasonal variations of biological oxygen demand recorded varied in the range of 1.9 – 3.9 , 2.1 – 4.2 , 1.8 – 3.3 and 1.1 – 2.8 mg/l during spring, summer autumn and winter respectively ( Table 9 , Fig 17 ) The higher BOD values recorded during summer and spring may be attributed to the photosynthetic activity and the abundance of phytoplankton leading to an increase of DO therefore BOD will increase. The minimum values of BOD were recorded during winter, this explained basically due to the drought period during this season. This is agreed with that reported by (Ghallab, 2000). On the contrary, the relative decrease of BOD values were recorded during autumn which reached to 1.8 mg/l at station V this may be attributed to the lower values of dissolved oxygen content during this season and the low activity of microorganisms (Abdo 2002).
88
2.4 3.9 1.9 3.6 2.3 3 2.3 2.8
spring
3.1 4.2 3.5 3.1 2.5 3.4 2.1 3.1
summer
2.9 3.3 2.4 2.2 1.8 2.3 3 2.6
Autumn
2.8 1.5 1.7 1.1 1.4 1.8 2.4 1.8
winter
2.8 3.2 2.4 2.5 2 2.6 2.5 ----
Annual average
Table ( 9 ) : seasonal variation of Biochemical oxygen demand BOD ( mg/l ) In investigated area during 2008
Season station El-Saaf Iron-Steel El- Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda
Seasonal avr.
…………………………………….…………..…………... Results and discussion
Fig 17 : (a) annual average and b: seasonal average values of Biochemical Oxygen demand BOD (mg/l) a: annual avrage.
mg/l 3.5 3 2.5 2 annual avr. 1.5 1 0.5
Stations
0 i
ii
iii
iV
V
Vi
Vii
b: Season avrage. mg/l 3.50 3.00 2.50 2.00 Season avr. 1.50 1.00 0.50
Seasons
0.00 spring
summer
autumn
90
winter
…………………………………….…………..…………... Results and discussion
4 – Chemical Oxygen Demand (COD)
The chemical oxygen demand is the total amount of oxygen required to oxidize all the organic matter completely to CO 2 and H 2 O (Tayel et al, 1996). Over the years a number of different tests have been developed to determine the organic content of freshwater and wastewater (Clark and Micheal, 1972). Organic substances in the area under investigation are mainly produced by the decomposition of domestic wastes, planktonic organisms and particulate organic matter discharged through the drain. The seasonal variations of chemical oxygen demand values were recorded in Table (10) and represented graphically in Figure (18) respectively, The values of COD varied in the range of 3.6 – 6.1 , 3.8 – 7.3 , 4.2 – 7.1 and 3.4 – 5.1 mg/l during spring, summer autumn and winter respectively.
The results of the seasonal average values of COD during spring, summer in addition to winter seasons have approximately the same values, in contrast the lighter value is visualized during autumn season this is may be attributed to the low value of dissolved oxygen ( 5.4 mg/l) recorded during this season this indicate that ,most value of D.O in the water samples are consume during the oxidation of the oxidizable organic matter in the River Nile During this season (Elawa el al 2009 ).
As classified by Beger (1942 ) water to be of good quality when it contains not more than 12 mg/l of organic matter expressed as oxygen consumed by permanganate , So that , COD values of the area under study in all cases , were significantly higher than this value. It meant that, the water of River Nile had a good water quality.
91
station 3.6 6.1 3.9 4.1 4 5 4.5 4.5
spring
3.8 7.3 4.2 4.1 3.7 4.5 3.9 4.5
summer
5.2 7.1 4.2 5.2 4.5 5.4 4.8 5.2
Autumn
3.4 4.2 4.9 5.1 3.8 4.2 5 4.4
winter
4 6.2 4.3 4.6 4 4.7 4.6 ----
Annual average
Table ( 10) : seasonal variation of Chemical oxygen demand COD ( mg/l ) In investigated area during 2008
Season El-Saaf Iron-Steel El- Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda
Seasonal avr.
…………………………………….…………..…………... Results and discussion
Fig 18 : (a) annual average and b: seasonal average values of Chemical Oxygen demand COD (mg/l)
a: annual avrage.
mg/l 7 6 5 4 annual avr. 3 2 1
Stations
0 i
ii
iii
iV
V
Vi
Vii
b: Season avrage. mg/l 5.40 5.20 5.00 4.80 4.60
Season avr.
4.40 4.20 4.00
Seasons
3.80 spring
summer
autumn
93
winter
…………………………………….…………..…………... Results and discussion
5 – Pollution Load To study the pollution load in the aquatic environment of river Nile at the investigated area ,
the
amount
of the
Biotic Oxygen Consumption (BOC)
was calculated, through the oxidation of organic matter and the oxidation of ammonia into nitrogen oxide NO 2 - and to NO 3 - this gives indication of the possible oxygen consumption by mineralization of organic substances ( Liao and Lean, 1978). As given in the following formula.
BOC =
Biochemical oxygen Demand (BOD) --------------------------------------------------- X 100 Dissolved oxygen (DO)
Our results revealed that, the maximum values were recorded during summer 54 % then autumn 50.4 % and decreased during winter 27.8 % and relative decrease during spring 42.7 % season. The ranges of BOC were varied between 15.84 - 100, 36.2 - 100, 32.14 - 100 and 15.27 – 37.83 % in subsurface water, during, spring, summer , autumn and winter respectively Table (11) and Figure (19 ). Thus the maximum values of BOC were recorded in the stations exposed to the strong effect of pollution loading by organic matter e.g. sewage, industrial wastes and other agricultural wastes. However, at the station ii behind iron and steel drain the values of BOC were reached to the maximum value 83.33 % This indicate that, the aquatic body of river at iron and steel drain is heavy loaded by organic pollution. Again , seasonally variations reveal that The maximum values recorded during summer and autumn season indicate that the aquatic body of river is heavy loaded by organic pollution and diluted during winter and spring season with the minimum values This is agreed with that reported by (Attia 2002).
94
15.84 100 27.94 45.56 33.33 40.45 35.93 42.73
spring
42.26 100 53.84 47.69 43.85 35.96 36.2 53.97
summer
46.77 100 43.63 41.5 32.14 39.65 49.18 50.41
Autumn
37.83 33.33 26.98 15.27 19.71 26.47 34.87 27.77
winter
38.68 38.33 38.1 37.5 32.26 40.16 39.02 ----
Annual average
Table ( 11 ) : seasonal variation of Biotic Oxygen Consumption BOC ( % ) In investigated area during 2008
Season station El-Saaf Iron-Steel El- Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda
Seasonal avr.
…………………………………….…………..…………... Results and discussion
Fig 19 : (a) annual average and b: seasonal average values of Biotic Oxygen Consumption BOC ( % )
a: annual avrage. BOC % 90 80 70 60 50
annual avr.
40 30 20 10
Stations
0 i
ii
iii
iV
V
Vi
Vii
b: Season avrage. BOC % 60.00 50.00 40.00 30.00
Season avr.
20.00 10.00
Seasons
0.00 spring
summer
autumn
96
winter
…………………………………….…………..…………... Results and discussion
C – major anion 1- Alkalinity. Alkalinity of water is a measure of its acid-neutralizing capacity. The titrable bases that contribute to the total alkalinity of a sample are generally the hydroxides, carbonates, and bicarbonates. However, other bases such as phosphates, and silicates can also contribute to the total alkalinity. The alkalinity value depends on the pH end point. When the alkalinity is determined to pH 8.3, it is termed phenolphthalein alkalinity. While, the titration of sample to pH 4.5, is termed methyl orange alkalinity (Strikland and parsons, 1965; Patnaik, 1997). The hydrolysis reactions of carbonic systems is assumed to be due to the system. CO 3 - - + H +
HCO 3 − + H+
H 2 CO 3
The level of alkalinity is critical in establishing solubility of some metals toxicity. And the alkaline water is not harmful ,The alkalinity makes water tasteful and helps in coagulation and does not affect pipes. However, excessive alkalinity interferes with coagulation as reported by (Hassoun, 1996).
1.a - Carbonate Alkalinity. The seasonal variations of carbonate in subsurface water values were recorded in Table (12) and represented graphically in Fig. (20). values of carbonate varied in the range of 2-12, 0 – 6 , 2 -12 and 2 - 16 mg/1 during spring, summer autumn and winter respectively. The maximum value of 16 mg/1 was recorded during spring at station IV while the minimum value of 0.0 mg/1 was recorded during summer measured at station II behind iron and steel drain.
97
Season station El-Saaf Iron-Steel El- Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda
Seasonal avr.
spring
4 0 4 4 4 6 6 4
summer
4 2 12 10 8 10 8 7.71
Autumn
8 2 8 16 10 12 12 9.71
winter
6 1.5 9 10 7.5 9 9.5 ----
Annual average
Table ( 12 ) : seasonal variation of Carbonate Alkalinity ( mg/l ) In investigated area during 2008
8 2 12 10 8 8 12 8.57
…………………………………….…………..…………... Results and discussion
Fig 20 : (a) annual average and b: seasonal average values of Carbonate Alkalinity (mg/l)
a: annual avrage.
mg/l 12 10 8 6
annual avr.
4 2 0
Stations i
ii
iii
iV
V
Vi
Vii
b: Season avrage.
mg/l 12.00 10.00 8.00 6.00
Season avr.
4.00 2.00
Seasons
0.00 spring
summer
autumn
99
winter
…………………………………….…………..…………... Results and discussion The values of carbonate increased during winter may be attributed to decaying and decomposition of phytoplankton microorganisms and organic matter leading to the liberation of CO 2 (Abdo,1998 ) This is agreed with that reported by ( El-Hadad, 2005 ). The slight increase of carbonate during spring may be due to the increase in respiration processes leading to liberation of CO 2 , which is converted into carbonate (Abdo, 2002 – El-Hadad, 2005 ). While the decreasing of carbonate values during summer may be attributed to elevation of water temperature during summer helped precipitation of calcium carbonate onto the overlying sediment and or may be converting to bicarbonate according the equation:-
CO 3 - - + H + + «-----------»
HCO 3 − ( Spotte, 1979)
1. b - Bicarbonate alkalinity Bicarbonate is the one of the most important anion in natural water ecosystem having two important functions, the first one provides the main buffer system for resulting pH of water while the second provides the carbon dioxide necessary for the photosynthetic process of phytoplankton (Golterman, 1975) The seasonal variations of bicarbonate alkalinity values were recorded in Table (13) and represented graphically in Figure (21) respectively. The values of bicarbonate varied in the range of 140 -260, 128 -170, 142 -178 and 146- 198 mg/1 during spring, summer, autumn and winter respectively. The maximum value of 260 mg/1 was recorded during spring at station II behind iron and steel drain while the minimum value of 128 mg/l was recorded during summer at stations VI .
100
Season station El-Saaf Iron-Steel El- Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda
Seasonal avr.
spring
132 170 132 130 132 128 130 136.3
summer
146 178 142 146 144 146 142 149.1
Autumn
152 198 150 154 146 156 154 158.6
winter
144.5 201.5 142.5 143.5 140.5 145 144.5 --
Annual average
Table ( 13 ) : seasonal variation of Bicarbonate Alkalinity ( mg/l ) In investigated area during 2008
148 260 146 144 140 150 152 162.9
…………………………………….…………..…………... Results and discussion
Fig 21 : (a) annual average and b: seasonal average values of Bicarbonate Alkalinity (mg/l)
a: annual avrage.
mg/l 210 200 190 180 170 160 150 140 130 120
annual avr.
Stations i
ii
iii
iV
V
Vi
Vii
b: Season avrage.
mg/l 165.0 160.0 155.0 150.0 145.0
Season avr.
140.0 135.0 130.0 125.0
Seasons
120.0 spring
summer
autumn
102
winter
…………………………………….…………..…………... Results and discussion The above mentioned results declared that, the bicarbonate values increase during spring and decrease during summer. At the same time the increase of bicarbonate during spring may be due to increase the decomposition rate of organic matter (Kilhem, 1982 , El-Hadad 2005 ). Also may be enhancing the anaerobic processes which increases carbon dioxide in the water column (Elewa, 1993 ). The decrease of bicarbonate during summer may be due to the decrease of water level because of low discharged amount of drainage water and high rate of evaporation ( Banoub and Whaby 1960 , Gomaa 2002 ). Also, may be due to the high rate of evaporation which decreases the total alkalinity especially that accompanied with increasing of water temperature (Ali , 2002).
Generally, the determination of water alkalinity is very important to predict its biodegradable or not for fish life, because waters of low alkalinity value are biologically less productive than those with high values (Lagler, 1959; Siliem, 1984). Alkalinity is represented in natural water by calcium salts of bicarbonate and carbonate. It is established that its values are usually proportional to productivity of aquatic ecosystems (Siliem, 1995). The water of low alkalinity said to be soft water while the water of high alkalinity (120 - 168) mg/l can be considered as hard water (Siliem, 1974). In addition to that the hard water more productive than the soft one.
Boyd (1979) cited that, alkalinity level for natural water may range less than 5 mg/l to several hundred mg/l . In addition, when total alkalinity values are greater than 75 mg/l this indicates that water is eutrophic condition (Moss, 1972; 1973). Hereinabove we can concluded that the River Nile water was eutrophic , hard water type.
103
…………………………………….…………..…………... Results and discussion
2- Chloride Chloride Cl‾ is one of the most commonly occurring anions in the environment. In natural water, it result from the leaching of chloride containing rocks and soils which the water comes in contact, and in coastal areas, from salt water intrusion. In additions agricultural, industrial and domestic wastewater discharged to the surface water are sources of chlorides (Clark, and Micheal, 1972). Chloride ion impacts a salty taste to water. The limit for domestic purposes is fixed at 250 mg/1 (EPA, 1989). The seasonal variations of Chloride values were recorded in Table (14) and represented graphically in Figure (22) respectively. The values of chloride varied in the range of 16 -141, 13 -85, 17 - 86 and 26- 157 mg/1 during spring, summer, autumn and winter respectively. The maximum value of 157 mg/1 was recorded during winter at station II behind iron and steel drain while, the minimum value of 13 mg/1 was recorded during summer at stations ( I, VI). Increasing of the Chloride values during winter season may be attributed to the decreasing on the water level of river Nile during drought period. but in the summer, Chloride values were decreased may be attributed to the dilution effect caused by more water comes from Nasser lake behind high dam and increasing on the water level. Generally, Chloride ion is an essential element for photosynthesis process, for photolysis of water to release oxygen, for ATP formation and phosphorylation reactions (Oser, 1979). It is the chief anion of the gastric juice, which derived from blood and is normally released during the later stages of digestion. Chloride is also concerned in osmotic pressure regulation, making up two thirds of the total anions of r-cellular fluids (Welch, 1952).
104
Season station El-Saaf Iron-Steel El- Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda
Seasonal avr.
spring
13 85 17 18 14 13 14 24.9
summer
17 86 23 21 27 21 21 30.9
Autumn
26 157 35 30 33 29 30 48.6
winter
18 117.3 25 22.3 23 21.5 20.8 ----
Annual average
Table (14) : seasonal variation of Chloride Cl - ( mg/l ) In investigated area during 2008
16 141 25 20 18 23 18 37.3
…………………………………….…………..…………... Results and discussion
Fig 22 : (a) annual average and b: seasonal average values of Chloride concentration (mg/l)
a: annual avrage.
mg/l 140 120 100 80 annual avr. 60 40 20
Stations
0 i
ii
iii
iV
V
Vi
Vii
b: Season avrage.
mg/l 50.00 45.00 40.00 35.00
Season avr.
30.00 25.00
Seasons
20.00 spring
summer
autumn
106
winter
…………………………………….…………..…………... Results and discussion
3- Fluoride Fluoride element is found in the environment and constitutes 0.06 - 0.09 % of die earth's crust. It is present in water, foods and air. Fluoride is commonly associated with volcanic activity and gases emitted from the earth's crust. Thermal waters, especially those of high pH, are also rich in fluoride. Fluoride has various uses in many industries including toothpaste, ceramics, tiles, bricks, etc. Fluoride is not found naturally in the air in large quantities. Average concentrations of fluoride found in the air are in the magnitude of 0.5 mg/l (WHO, 2004). The seasonal variations of Fluoride values were recorded in Table (15) and represented graphically in Figure (23) respectively. The values of fluoride varied in the range of 0.218 -0.473, 0.235 -1.4, 0.21 – 0.72 and 0.229- 2.01 mg/1 during spring, summer, autumn and winter respectively. The maximum value of 2.01 mg/1 was recorded during winter at station II behind iron and steel drain while, the minimum value of 0.21 mg/1 was recorded during autumn at stations ( I, V). Increasing of the Fluoride values during winter season may be attributed to the decreasing on the water level of River Nile during drought period, but in the spring , Fluoride values were decreased may be attributed to the flourishing of phytoplankton and zooplankton uptake of the fluoride ion therefore fluoride will decrease .
٤- Sulphate Sulphur is one of the six major elements of living matter. It is appears in the amino acids, cystine, cysteine and methionine therefore, present in all proteins. It is also part of some co-enzymes. It is abundant in water and soil and makes up 7.8 % of the solutes in water. The sulphate ion is soluble and therefore is the most common form it absorbed by plants, thus entering the cellular metabolism (Delince, 1992).
107
Season station El-Saaf Iron-Steel El- Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda
Seasonal avr.
spring
0.26 1.4 0.473 0.3 0.235 0.352 0.26 0.47
summer
0.21 0.72 0.22 0.24 0.21 0.34 0.3 0.32
Autumn
0.229 2.01 0.264 0.23 0.64 0.44 0.261 0.58
winter
0.233 1.15 0.294 0.25 0.326 0.34 0.264 ----
Annual average
Table (15) : seasonal variation of Fluoride F - ( mg/l ) In investigated area during 2008
0.232 0.473 0.218 0.23 0.22 0.226 0.236 0.26
…………………………………….…………..…………... Results and discussion
Fig 23 : (a) annual average and b: seasonal average values of Fluoride (mg/l)
a: annual avrage.
mg/l 1.4 1.2 1 0.8 annual avr. 0.6 0.4 0.2
Stations
0 i
ii
iii
iV
V
Vi
Vii
b: Season avrage .
mg/l 0.60 0.55 0.50 0.45 0.40
Season avr.
0.35 0.30 0.25
Seasons
0.20 spring
summer
autumn
109
winter
…………………………………….…………..…………... Results and discussion The sources of sulphur compounds to natural waters include rocks, fertilizers, and atmospheric precipitation and dry deposition. The atmospheric sources augmented greatly by combustion products of industry, dominate all other sources. Sulphate is released during geochemical weathering of rocks and soils containing sulphides or free sulphur, which are oxidized in the presence of water to from sulphuric acid. (ZoBell, 1973)
2FeS 2 (Pyrite)+ 7O 2 + 2H 2 O ------------------►
2FeSO 4 + 2H 2 SO 4
2S + 3O 2 + 2H 2 O ------------------► 2H 2 SO 4
The seasonal variations of sulphate values were recorded in Table (16) and represented graphically in Figure (24) respectively. The values of sulphate varied in the range of 21 -147.3, 16.8 -121.8, 22.5 -110.4 and 35.3- 255.6 mg/1 during spring, summer, autumn and winter respectively. The maximum value of 255.6 mg/1 was recorded during spring at station II behind iron and steel drain while the minimum value of 16.8 mg/l was recorded during summer at stations V . Increasing of the sulphate values during winter season may be attributed to death microorganisms and decomposition of aquatic plant or may be due to the oxidation of sulfur into sulfate due to high concentration of dissolved oxygen during this season ( Abdo , 2002 , El-Hadad 2005 ) , Also may be attributed to the decreasing on the water level of river Nile during drought period. On the other hand, the lower SO 4 - - values were recorded during summer may be attributed to the elevation temperature during this season leading to, two processes takes place, (1). Sulphate will reduced directly by the action of sulphate reducing active bacteria into sulphide or (2).Deposition of SO 4 - to
the sediment as Na 2 SO 4 . The above mentioned conclusion coincided with
that reported by (Abd El-Satar, 1998).
110
Season station El-Saaf Iron-Steel El- Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda
Seasonal avr.
spring
17.1 121.8 18.8 17.9 16.8 17.2 17.9 32.5
summer
22.5 110.4 26.5 26.8 36.4 25.6 24 38.9
Autumn
36.9 255.6 42.1 41.6 38.7 35.3 35.3 69.4
winter
24.4 158.8 29.3 28 29.6 26.9 25.8 ----
Annual average
Table ( 16 ) : seasonal variations of Sulphate - SO 4 - - ( mg/l ) In investigated area during 2008
21 147.3 29.7 25.8 26.3 29.4 25.8 43.6
…………………………………….…………..…………... Results and discussion
Fig 24 : (a) annual average and b: seasonal average values of Sulphate (mg/l)
a: annual avrage.
mg/l 180 160 140 120 100
annual avr.
80 60 40 20 0
Stations i
ii
iii
iV
V
Vi
Vii
b: Season avrage.
mg/l 75.00 70.00 65.00 60.00 55.00 50.00 45.00 40.00 35.00 30.00 25.00
Season avr.
Seasons spring
summer
autumn
112
winter
…………………………………….…………..…………... Results and discussion Also may be attributed to the dilution effect caused by more water comes from Nasser lake and increasing on the water level. Also may be due to the sulfur bacteria which reduced sulfate to sulfur (Cole 1979) CaSO 4 +2C —► CaS + 2CO 2
During spring, the SO 4 -- contents were found in high concentrations compared with other seasons, this occur due the high values of DO during this season, but were relatively decreased. The depletion in SO 4 -- contents during these seasons may be attributed to the uptaking of SO 4 -- by the aquatic organisms (Nour El-Din, 1985, Abdo 2002).
Finally sulphur is very important for protein structure but nearly limits the growth or distribution of the aquatic biota. This is due to the abundance of the element especially in its most energetically stable from. Sulphate is the complex three dimensional structure of enzymes and other proteins is partially to bridge between two sulphur atoms that stabilize the geometry of the enzymes. This is main utilization of sulphur in all living cells, but group plays a vital role in other metabolic process such as cell division (Goldman and Home, 1983).
D -major Cation 1- Calcium Calcium is one of the alkaline earth metals. It is more abundant constituent of natural water than any other aquatic septum but its behavior is differing in the sea water. Calcium is often lumped together with magnesium in water analysis, as both contribute to the hardness of water. The presence of calcium in water supplies results from passage through deposits of limestone, dolomite, gypsum, gypsiferrous shale, and normally present in natural waters in dissociated forms as the bivalent ion (Ca+2) (APHA, 1992).
113
…………………………………….…………..…………... Results and discussion Generally calcium is essential elements for metabolic processes in all living microorganisms where relaxation and contraction of animal muscles depend on depolarization of cell membrane by inflow of calcium ions. (Sader, 1991). According to Weninger (1985) in humid tropical areas, water is commonly dominated by calcium and bicarbonate ions. Where in the areas, with soil erosion the dominant ions are magnesium and bicarbonate. The importance of calcium largely in relation to pH and the carbonate-bicarbonate buffer system and microbial processes (Lund, 1985). The seasonal variations of calcium values were recorded in Table (17) and represented graphically in Figure (25) respectively. The values of calcium varied in the range of 32 -66.8, 26.4-49.6, 32.8 -54.4 and 33.6- 72 mg/1 during spring, summer, autumn and winter respectively. The maximum value of 72 mg/1 was recorded during winter at station II behind iron and steel drain while the minimum value of 26.4 mg/l was recorded during summer at stations VI . The results
declared
that,
the high values of Ca+2 contents at the
different stations were recorded during winter, this may be attributed to low water level through the drought period, or to the decaying and decomposing of phytoplankton and other microorganisms and liberated Ca+2 in different forms, or it is due to some redissolution of organisms and calcium compounds in the presence of CO 2 (Abdo, 1998). This agreed with that reported by (Ghallab, 2000 , Abdo 2002). On the other side, the low Ca+2 contents recorded during summer, mainly attributed to, the decrease of CaCO 3 solubility as a result of increase temperature and loss of CO 2 according to the following equation (Abdo 2002)
Ca(HCO 3 ) 2
CaCO 3 + H 2 O + CO 2
114
Season station El-Saaf Iron-Steel El- Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda
Seasonal avr.
spring
28.8 49.6 28.8 28.8 28 26.4 28 31.2
summer
32.8 54.4 32.8 35.2 34.4 32.8 33.6 36.6
Autumn
33.6 72 36 36.8 33.6 35.2 36 40.5
winter
32 60.7 33.2 33.6 32 31.8 32.4 ----
Annual average
Table ( 17 ) : seasonal variation of Calcium Ca ( mg/l ) In investigated area during 2008
32.8 66.8 35.2 33.6 32 32.8 32 37.9
…………………………………….…………..…………... Results and discussion
Fig 25 : (a) annual average and b: seasonal average values of Calcium (mg/l)
a: annual avrage.
mg/l 65 60 55 50 45
annual avr.
40 35 30 25
Stations
20 i
ii
iii
iV
V
Vi
Vii
b: Season avrage.
mg/l 43.0 41.0 39.0 37.0 35.0
Season avr.
33.0 31.0 29.0 27.0
Seasons
25.0 spring
summer
autumn
116
winter
…………………………………….…………..…………... Results and discussion Also may be attributed to the dilution effect caused by more water comes from Nasser lake behind high dam and increasing on the water level. Or due to its uptake by microorganisms and fishes living the water branch photosynthesis, carbohydrates metabolism, fatty acids, amino acids, proteins, alcohols, phenols and chlorophyll ( Nour El-Din, 1985).
On the other hand, the relative decrease of Ca+2 contents were noted during autumn may be attributed to aquatic plants and macrophytes which decreased the calcium content in the water through adsorption of calcium salts onto its roots and / or onto the clayey particles which suspended around immersed and submersed macrophytes i.e. macrophytes acts as a trap for most cations (Diaz et al, 1998) Another explanation seem to be acceptable for decreasing the calcium content, that adsorption of gypsum (CaSO/O and dolomite (CaMg (003)2) on the organic matter found in large quantities during these season and precipitate on the sediment in process called decalcification of the epilimnion (Stewart and Wetzel, 1981; El- Sarraf et al., 2001) the other side, the relative increase of Ca+2 content notable during spring could be explained on the
basis of its uptake by aquatic microorganisms and
fishes or due to adsorption on many semi hydroxides ( Wetzel 1983). Generally the increase of calcium concentration in the aquatic environment induced the reduction of heavy metals toxicity. (Ali et al., 1992)
2- Magnesium Magnesium ranks eighth among the elements in order of abundance and is a common constituent of natural water. Important contributors to the hardness of water, magnesium salts break down when heated forming scales in boilers. Concentrations greater than 125 mg/1 also can have cathartic effect.
117
and
diuretic
…………………………………….…………..…………... Results and discussion Chemical
softening,
reverse osmosis, electrodialysis or ion exchange
reduces the magnesium and associated hardness to acceptable levels. The magnesium concentration may vary from zero to several hundred milligram per liter depending on the source and treatment of the water (APHA, 1995). Magnesium is required universally by chlorophyilous plants for the magnesium
prophyrin
component
of
chlorophyll
molecules,
and
as
macronutrients in enzymatic transformation, especially in transphosphorylation by algae, fungi, and bacteria. The demands for magnesium in metabolism are minor in comparison to quantities generally available in waters (Wetzel, 1983). Moreover, magnesium compounds are much more soluble than their calcium counterparts. As a result, significant amounts of magnesium rarely precipitate. The carbonates of hard waters are usually > 95 % CaCO 3 under ordinary CO 2 pressure. MgCO 3 and Mg (OH) 2 precipitate significantly only at high pH values (>10) under most natural conditions. Consequently, the concentrations of magnesium are extremely high in closed saline basins (Wetzel and Otsuki, 1974). Magnesium is important clement and needed by all biological living cells for phosphate transfer involving Adenosine Triphosphate (ATP) and Adenosine Diphosphate (ADP) (Stumm and Morgan, 1970) ATP + Mg ++ ------------ ► ADP + P + energy
The
seasonal
variations
of magnesium
values
were
recorded
in
Table (18) and represented graphically in Figure (26) respectively. The values of Magnesium varied in the range of 11 - 25.9, 8.6 - 20.2, 10.6 -20.6 and 13- 30.7 mg/1 during spring, summer, autumn and winter respectively. The maximum value of 30.7 mg/1 was recorded during winter at station II behind iron and steel drain while the minimum value of 8.6 mg/l was recorded during summer at stations I .
118
Season station El-Saaf Iron-Steel El- Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda
Seasonal avr.
spring
8.6 20.2 10.1 9.1 9.6 12 10.1 11.4
summer
11 20.6 12.5 10.6 12 10.6 12 12.8
Autumn
13.4 30.7 13.4 13.4 13.9 13.4 13 15.9
winter
11.1 24.4 12 11 11.9 12.1 11.9 ----
Annual average
Table ( 18 ) : seasonal variation of Magnesium Mg ( mg/l ) In investigated area during 2008
11.5 25.9 12 11 12 12.5 12.5 13.9
…………………………………….…………..…………... Results and discussion
Fig 26 (a) annual average and b: seasonal average values of Magnesium (mg/l)
a: annual avrage.
mg/l 26 24 22 20 18
annual avr.
16 14 12 10
Stations
8 i
ii
iii
iV
V
Vi
Vii
b: Season avrage.
mg/l 17.0 16.0 15.0 14.0 Season avr. 13.0 12.0 11.0
Seasons
10.0 spring
summer
autumn
120
winter
…………………………………….…………..…………... Results and discussion Increasing of the values Magnesium during winter season may be attributed to the decreasing on the water level of river Nile during drought period. in the summer, Magnesium values were decreased may be attributed to the dilution effect caused by more water comes from Nasser lake behind high dam and increasing on the water level (Elewa et al, 2009).
3- Sodium Sodium is the sixth most abundant in the Lithosphere. This alkali metal is very reactive and soluble; when leached from the rocks, its compounds tend to remain in solution. For this reason, it is at least the third most abundant metal in river and lakes and in many instance it ranks first (Cole, 1979 ). Sodium is derived mainly from weathering of sodium rich feldspars and to some extent clay minerals (Davis, 1972). Other sources of sodium in natural water include rainwater, soil leaches and atmospheric precipitation (Wu and Gibson, 1996 ). The seasonal variations of Sodium values were recorded in Table (19) and represented graphically in Figure (27) respectively. The values of Sodium varied in the range of 21.29 – 119.7, 19.2 – 51.56, 27.8 -87.9 and 38.25126.3 mg/1 during spring, summer, autumn and winter respectively. The maximum value of 126.3 mg/1 was recorded during winter at station II behind iron and steel drain while the minimum value of 19.2 mg/l was recorded during summer at stations I .
The results showed that, the high amounts of Na+ content were recorded during winter which may be attributed to the release of sodium from sediment into the overlying water (Elewa, 1993). also due to the effect of the drought period however the decrease of water levels may lead to the decomposition and decay of dead organisms and phytoplankton this is a leading to facilitate Na+ release to overlying water. This results agreed with that reported by (Ghallab, 2000 , Abdo 2002).
121
Season station El-Saaf Iron-Steel El- Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda
Seasonal avr.
spring
19.21 51.57 23.49 20.52 19.32 19.99 20.31 24.9
summer
27.8 87.9 32.65 31.37 35.05 30.32 31.3 39.5
Autumn
38.25 126.3 43.03 43.89 42.42 39.63 42.47 53.7
winter
26.64 97.4 31.6 29.8 34 28.6 29.2 ----
Annual average
Table ( 19 ) : seasonal variation of Sodium - Na ( mg/l ) In investigated area during 2008
21.29 119.7 27.37 23.42 39.27 24.64 22.63 39.8
…………………………………….…………..…………... Results and discussion
Fig 27 : (a) annual average and b: seasonal average values of Sodium (mg/l)
a: annual avrage. mg/ l 110 100 90 80 70
annual avr.
60 50 40 30 20
Stations i
ii
iii
iV
V
Vi
Vii
b: Season avrage.
mg/l 60 55 50 45 40
Season avr.
35 30 25
Seasons
20 spring
summer
autumn
123
winter
…………………………………….…………..…………... Results and discussion Also, the decrease of Na+ content during summer, may be attributed to, the dilution effect of flood period and/or precipitation of Na+ as NaCO 3 under high temperature. Generally sodium elements occurs in water as positive ions facilitating its permeability through the cell and maintains the osmolarity of the intracellular and extracellular fluids which is the principle of the contraction of the muscles and as well as the nerves. (EI-Awag, 1999).
4- Potassium Potassium ranks seventh among the elements in order of abundance in the earth crust. It is usually the fourth ranking cation in natural water. It is weathered from various feldspars that have the formula KAlSi 3 O 8 but does remain in solution so well as sodium. It recombines easily with other products of weathering, being removed from solution by adsorption on clay, so potassium rarer in water than sodium. The elements essential in plant nutrition and both extracellular and intracellular fluids that contain an excess of potassium (EPA, 1989).
The
seasonal
variations
of Potassium
values
were
recorded
in
Table (20) and represented graphically in Figure (28) respectively. The values of Potassium varied in the range of 4.81 – 10.46, 4.57 – 12.73, 5.55 -14.75 and 5.9713.41 mg/1 during spring, summer, autumn and winter respectively. The maximum value of 14.75 mg/1 was recorded during autumn at station II behind iron and steel drain while the minimum value of 4.57 mg/l was recorded during summer at stations I . The results showed that, the high amounts of K+ content were recorded during winter and autumn which may be attributed to the drought period however the decrease of water levels may lead to the decomposition and decay of dead organisms and phytoplankton this is a leading to facilitate K+ release to overlying water .
124
Season station El-Saaf Iron-Steel El- Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda
Seasonal avr.
spring
4.72 12.73 5.28 4.81 4.57 4.75 4.78 5.95
summer
5.55 14.75 5.79 5.71 5.97 5.63 5.85 7.04
Autumn
5.97 13.41 6.12 6.45 6.37 6.01 6.41 7.25
winter
7.28 12.83 5.62 5.5 6.3 5.3 5.47 ----
Annual average
Table (20) : seasonal variation of Potassium - K ( mg/l ) In investigated area during 2008
4.9 10.46 5.29 5.01 8.29 4.81 4.83 6.23
…………………………………….…………..…………... Results and discussion
Fig 28 : (a) annual average and b: seasonal average values of Potassium (mg/l)
a: annual avrage.
mg/l 14 13 12 11 10 9 8 7 6 5 4
annual avr.
Stations i
ii
iii
iV
V
Vi
Vii
b: Season avrage.
mg/l 7.5 7 6.5 Season avr. 6 5.5
Seasons
5 spring
summer
autumn
126
winter
…………………………………….…………..…………... Results and discussion Potassium contents showed a relative decrease during spring may be due to flourishing of phytoplankton and zooplankton that may feed on potassium ion. Besides the uptake of potassium by aquatic organisms and its massive utilization in the various biological activities lead to decrease the quantity of potassium in the surrounding media (Ali, 1998).
in the summer, Potassium values were decreased may be attributed to the dilution effect caused by more water comes from Nasser lake behind high dam and increasing on the water level. Generally, potassium is the most important light elements in fresh water, because its uptake as essential element in phytoplankton, aquatic animal and plants growth (Abdo, 1998).
5- Aluminum Aluminum makes up around 8% of the Earth’s surface, making it the third most common element. It is often used in cooking utensils, containers, appliances and building materials, as well as in the production of glass, paints, rubber and ceramics. Aluminum is used in several forms, such as aluminum hydroxide (in antacids), aluminum chlorohydrate (in deodorants), and the most common form, aluminum sulphate (in treating drinking water).
At low levels, aluminum in food, air, and water is not likely harmful to your health. However, at high concentrations there is evidence linking aluminum to effects on the nervous system, with possible connections to several diseases, such as Parkinson’s, Alzheimer’s, and Lou Gehrig’s disease. Patients suffering from these diseases tend to have high levels of aluminum in some areas of their brains. It is not known if aluminum is causing these diseases or if the aluminum starts accumulating in people that already have the diseases. There is also some concern that aluminum may cause skeletal problems. There is no evidence to suggest that aluminum affects reproduction, or that it causes cancer.
127
…………………………………….…………..…………... Results and discussion The
seasonal
variations
of Aluminum values
were
recorded
in
Table (21) and represented graphically in Figure (29) respectively. The values of Aluminum varied in the range of 0.346 – 2.11, 0.247 – 1.266, 0.2 -0.82 and 0.2141.524 mg/1 during spring, summer, autumn and winter respectively. The maximum value of 2.112 mg/1 was recorded during spring at station II behind iron and steel drain while the minimum value of 0.2 mg/l was recorded during autumn at stations VII .
in the summer, Aluminum values were decreased may be attributed to the dilution effect caused by more water comes from Nasser lake behind high dam and increasing on the water level. Increasing of the Aluminum values during winter season may be attributed to the drought period and decrease of water levels.
6- Basic Ratio (Na+ + K+ / Ca +2 + Mg+2 ) M/D The ratio of sodium and potassium to calcium and magnesium known as the ratio of monovalent to divalent ions M/D which has, for a long time, been considered useful for predicting the phytoplankton assemblage in given water body (Pearsall, 1924). M/D ratio below 1 was favorable for diatoms and blue green algae while M/D ratio above 1 suitable for desmids (Shoesmith & Brookt 1983).
This ratio can't explain the dynamics of phytoplankton; ions, such as nitrate,
phosphate
Importance
of M/D
correlation between
and ratio
silicate
must be
considered
individually
is difficult to disentangle from the usual_a
increasing the M/D ratio values and decrease-amount of
phosphate, nitrate and ammonium salts (Lund, 1965).
128
Season station El-Saaf Iron-Steel El- Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda
Seasonal avr.
spring 0.24 1.33 0.23 0.24 0.25 0.27 0.29 0.41
summer
0.69 2.64 0.93 0.67 1.33 0.62 0.62 1.07
Autumn
0.43 0.87 0.54 0.62 0.54 0.41 0.67 0.58
winter
0.48 1.89 0.63 0.62 0.78 0.41 0.48 ----
Annual average
Table ( 21 ) : seasonal variation of Aluminum Al ( mg/l ) In investigated area during 2008
0.55 2.72 0.81 0.94 0.99 0.35 0.36 0.96
…………………………………….…………..…………... Results and discussion
Fig 29: (a) annual average and b: seasonal average values of Aluminum (mg/l)
a: annual avrage. mg/l 2 1.8 1.6 1.4 annual avr.
1.2 1 0.8 0.6
Stations
0.4 i
ii
iii
iV
V
Vi
Vii
b: Season avrage.
mg/l 1.20 1.10 1.00 0.90 0.80
Season avr.
0.70 0.60 0.50 0.40
Seasons
0.30 spring
summer
autumn
130
winter
…………………………………….…………..…………... Results and discussion The
results of recent basic ratio showed that an increase in this ratio
during winter and autumn than spring and summer seasons. This may be attributed to the flourishing of phytoplankton during spring and summer seasons which leading to uptake of Na+ and K+ elements therefore, basic ratio decrease. This results agreed with that reported by (Ali, 1998) on the Damietta branch (Tables, 42, 43) and also agreed with that reported by ( Abdo, 2002 ) on the Rosetta branch .
The
seasonal
variations
of Basic Ratio values
were
recorded
in
Table (22) and represented graphically in Figure (30) respectively. The values of Basic Ratio varied in the range of 0.591 – 1.4, 0.635 – 0.92, 0.761 -1.37 and 0.9391.36 during spring, summer, autumn and winter respectively.
The maximum value of 1.4 was recorded during spring at station II behind iron and steel drain while the minimum value of 0.591 was recorded during spring at stations VII . Overall according to classification of (Shoesmith & Brooke, 1983) the values of M/D below 1 indicate oligotrophy, values from 0.1 to 0.3 dystrophy and the values above 1 indicate eutrophic conditions.
Thus the stations from ( I, III , IV , V , VI , VII )
are oligotrophy and
station II behind iron and steel drain is eutrophic conditions.
E - Nutrient Salts The nutrient salts include compounds that contain nitrogen, phosphorus or silicate in different forms either in available or non-available forms. The availability of nutrient salts for autotrophic producers considered as a limiting factor to productivity of water body, while the non-available forms considered as useless in the productivity processes.
131
0.591 1.4 0.692 0.637 1.08 0.65 0.62 0.81
spring
0.639 0.92 0.739 0.668 0.635 0.644 0.658 0.7
summer
0.761 1.37 0.848 0.809 0.884 0.828 0.814 0.902
Autumn
0.941 1.36 0.995 1.002 1.027 0.939 0.997 10.37
winter
0.733 1.26 0.818 0.779 0.906 0.765 0.772 ----
Annual average
Table (22): seasonal variation of Basic Ratio (Na+ + K+/Ca+2 + Mg+2) In investigated area during 2008
Season station El-Saaf Iron-Steel El- Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda
Seasonal avr.
…………………………………….…………..…………... Results and discussion
Fig 30: (a) annual average and b: seasonal average values of Basic Ratio
a: annual avrage. 1.3 1.2 1.1 1 annual avr. 0.9 0.8 0.7
Stations
0.6 i
ii
iii
iV
V
Vi
Vii
Season avr. 1.1 1 0.9 Season avr. 0.8
Seasons
0.7 0.6 spring
summer
autumn
133
winter
…………………………………….…..…………………... Results and discussion In water and wastewater the existed forms of nitrogen of greatest interest, in order of decreasing oxidation state are, nitrate, nitrite, ammonia and inorganic nitrogen. All these forms of nitrogen, as well as. N 2 gas, are biochemically interconvertible and are components of the nitrogen cycle. They are of interest for many reasons (APHA, 1995). Nutrient salts considered as very important compounds essential for the living organisms in natural waters, this importance similar to that of the dissolved oxygen, temperature and pH (Nour El-Din, 1985). Also, nutrients represent the fertility of the water, on which primary productivity and ultimately, fish production depends. The amount of autotrophic produces is a function of the concentrations of the various nutrients. This relation has often been considered as the sole determinant of the dynamics of aquatic systems and persisting presence of algae in great numbers. (Foy and Fistzsimoms, 1987). Generally, the high level of nutrient loading (N and P) causes eutrophication in natural waters and coastal zones (Owens, 1993 ; Van Dijk et al, 1995 ; De Wit, 2000). The determination and analysis of nutrient fluxes from all sources (agricultural, atmospheric deposition, households and industry) can help the policy makers to take most effective decisions to overcoming the eutrophication problem and improving the water quality. (De Wit and Behreradt, 1999).
1 – Nitrite Nitrite is an intermediate oxidation state of nitrogen, both in the oxidation of ammonia to nitrate and in the reduction of nitrate. Such oxidation and reduction occur in wastewater treatment plants, water distribution systems, and natural waters. Nitrite can enter a water supply system through its use as a corrosion inhibition in industrial water process. Nitrite is the actual etiologic agent of methanoglobinemia (APHA, 1995).
134
…………………………………….…..…………………... Results and discussion
Resistance to toxic effect of nitrite is enhanced by the presence of chloride or increased water hardness. The variation in its toxicity to different natural water fishes to be due to their ability to concentrate or exclude nitrite from their blood plasma (Tamasso, 1986). Generally, the main factors controlling the nitrite level in aquatic ecosystem as mentioned by Riley and Chester (1971) are; uptake by phytoplankton, bacterial activity, and oxidation - reduction processes. The seasonal variations of Nitrite values were recorded in Table (23) and represented graphically in Figure (31) respectively. The values of Nitrite varied in the range of 0 – 0.15 , 0.007 – 0.18, 0.01 - 0.29 and 0.006- 0.18 mg/ l during spring, summer, autumn and winter respectively. The maximum value of 0.29 mg/l was recorded during autumn at station II behind iron and steel drain while the minimum value of 0 mg/l was recorded during spring at stations I , VI . The above mentioned results declared that, the levels of nitrite showed a regular seasonal fluctuation, but increased during cold seasons ( winter and autumn), but decreased in hot seasons (spring and summer). This reservation can be explained on the basis of oxidation of ammonia in the presence of oxygen as follow: NH 4 + + 1.5O 2
---------► 2H+ + H 2 O + NO 2 -
The decrease of the levels of nitrite during spring and summer mainly attributed to biologically uptake of nitrite into cellular amino acid by photosynthetic activities of plankton and action of transamins enzyme which decrease the nitrite value ( El-Hadad, 2005 ).
135
Season station 0.0 0.15 0.01 0.007 0.003 0.0 0.007 0.025
spring
0.008 0.18 0.007 0.018 0.009 0.012 0.013 0.035
summer
0.013 0.29 0.02 0.015 0.012 0.01 0.01 0.053
Autumn
0.007 0.22 0.007 0.009 0.006 0.009 0.01 0.038
winter
0.007 0.21 0.011 0.012 0.008 0.008 0.01 ----
Annual average
Table ( 23 ) : seasonal variations of Nitrite NO 2 - ( mg/l ) In investigated area during 2008
El-saaf Iron-Steel El-Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda Seasonal avr.
…………………………………….…..…………………... Results and discussion
Fig 31 : (a) annual average and b: seasonal average values of Nitrite (mg/l)
a: annual avrage.
mg/l 0.25 0.2 0.15 annual avr. 0.1 0.05
Stations
0 i
ii
iii
iV
V
Vi
Vii
Season avr.
mg/l 0.0550 0.0500 0.0450 0.0400 Season avr. 0.0350 0.0300 0.0250
Seasons
0.0200 spring
summer
autumn
137
winter
…………………………………….…..…………………... Results and discussion The results were in agreement with that reported by Ali 1998 and 2002 who showed that the average nitrite values in Qarun Lake increase during cold seasons and decrease in hot one. European Economic Community Standards (EPA, 1976) has set 100 µg/1 as a maximum admissible limit for nitrite in natural water and here in all cases, River Nile at area under investigation not reached the alarm case of nitrite toxicity except station II behind iron and steel drain, nitrite levels exceed the admissible levels by several times. Nitrite poisoning cause fish mortality resulting in converting hemoglobin to form methemoglobin as indicated by Boyd (1979).
2 – Nitrate Nitrate is the final oxidation product of nitrogen compound in aquatic environment. At the same time, nitrate is generally considered the only thermodynamically stable form of nitrogenous compounds in absence of oxygen (Horna, 1972). Also, nitrate is the major nitrogenous compound in the aquatic environment. The behaviour of nitrate is important in the nitrogen metabolism in natural water (Seike et ai, 1990). Nitrate is a prime plant nutrient and raising in its concentrations might be expected to increase the eutrophication of waters. Nitrates concentrate are depended on the type of agricultural runoff. Most metal nitrates are soluble in water and occur in trace amounts in surface and ground waters. In the areas where nitrate is derived from organic pollution, the high nitrate may be accompanied by high chloride concentration. Anoxic layers of sediments are the primary sites of dentirification which may reduce both nitrate diffusing from the overlying water column and nitrate produced by nitrification in the oxic layers. Furthermore, the dentrification rates are associated with factors such as nitrate concentration, dissolved oxygen of bottom waters, redox potential, temperature, irrigation capacity of macrobenthic communities and other factors (Flemer et al; 1998).
138
…………………………………….…..…………………... Results and discussion The seasonal variations of Nitrite values were recorded in Table (24) and represented graphically in Figure (32) respectively. The values of Nitrite varied in the range of 0.06 – 0.48, 0.04 – 1.06, 0.02 - 0.31 and 0.08- 0.26 mg/l during spring, summer, autumn and winter respectively. The maximum value of 1.06 mg/l was recorded during summer at station II behind iron and steel drain while the minimum value of 0.02 mg/l was recorded during autumn at stations V, VII . The notable increase in NO 3 - contents during summer season may be Related to the evaporation which is due to elevation in temperature leading To concentration of the different ions. ( Abdo,2002 ), on the reverse the minimum values of NO 3 - during autumn may be attributed to denitrification of NO 3 into NO 2 - and NH 3 by denitrifying bacteria (Merck, 1980) Generally, nitrate occurs in trace quantities in the surface water and may attain in high levels in some groundwater. In excessive amounts, it contributes to the illness known as methamoglobinemia in infants. A limit of 10 mg nitrate as nitrogen/L has been imposed on drinking water to prevent this disorder. Nitrate is found only in small amounts in fresh domestic waste water but in the effluents of nitrifying biological treatment plants nitrate may be found in concentration of up to 30 as nitrogen/L. It is essential nutrient for many photosynthetic autotrophs and in some cases has been identified as the growth limiting nutrient (APHA, 1995).
3- Ammonia Nitrogen occurs in natural waters in numerous forms: dissolved molecular N 2 , a large number of organic compounds form amino acids, amines to proteins and refractory organic compounds of low nitrogen content, ammonia, nitrite, and Nitrate.
139
Season station 0.21 0.48 0.1 0.07 0.06 0.08 0.11 0.159
spring
0.07 1.06 0.11 0.14 0.1 0.08 0.04 0.229
summer
0.04 0.31 0.07 0.013 0.02 0.04 0.02 0.09
Autumn
0.08 0.26 0.1 0.225 0.12 0.1 0.12 0.144
winter
0.1 0.53 0.095 0.141 0.075 0.075 0.073 ----
Annual average
Table ( 24 ) : seasonal variation of Nitrate NO 3 -( mg/l ) In investigated area during 2008
El-saaf Iron-Steel El-Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda Seasonal avr.
…………………………………….…..…………………... Results and discussion
Fig 32 : (a) annual average and b: seasonal average values of Nitrate (mg/l)
a: annual avrage. mg/l 0.6 0.5 0.4 0.3
annual avr.
0.2 0.1
Stations
0 i
ii
iii
iV
V
Vi
Vii
b: Season avrage. mg/l 0.250 0.200 0.150 Season avr. 0.100 0.050
Seasons
0.000 spring
summer
autumn
141
winter
…………………………………….…..…………………... Results and discussion Ammonia nitrogen exists in aqueous solution either as ammonium ion [NH 4 +] or ammonia [NH 3 ] depending on the pH of the solution, in accordance with the following equilibrium reaction:NH 3 + H 2 O NH 4 + + OHAt pH above 7, the equilibrium is displaced to the left, at pH < 7, ammonium ion is predominant. However the increase in the concentration of ammonia
[NH 3 ] lead to toxicity and death for fishes and other aquatic
organisms but ammonium ion [NH 4 +] have no effect on aquatic organisms or fishes, therefore ammonia is considered one of the most important parameters must be studied in the water ecosystem (Elewa et al., 2001). Ammonia is generated by heterotrophic bacteria as a primary end product of decomposition of organic matter, either directly from proteins or from other nitrogenous organic compounds. Intermediate nitrogen compounds are formed in the progressive degradation of organic material, but rarely accumulate, because deamination by bacteria proceeds rapidly. Although ammonia is a major excretory product of aquatic animals, this nitrogen source is quantitatively minor in comparison to that generated by bacterial decomposition (Wetzel, 1983). Ammonia in water present primarily as NH 4 + and as undissociated NH 4 OH, the latter being highly toxic to many organisms, especially fish (Trussei, 1972). The proportions of NH 4 + to NH 4 OH are dependent on the dissociation dynamics which are governed by pH and temperature. The approximate ratios of NH 4 + to NH 4 OH are as follows (Hutchinson, 1957) pH
Ratio
6
3000:1
7
300:1
8
30:1
9.5
1:1
142
…………………………………….…..…………………... Results and discussion The seasonal variations of ammonia values were recorded in Table (25) and represented graphically in Figure (33) respectively. The values of ammonia varied in the range of 0 – 0.9 , 0 – 0.84, 0 – 0.24 and 0- 0.29 mg/ l during spring, summer, autumn and winter respectively. The maximum value of 0.9 mg/l was recorded during spring at station II behind iron and steel drain while the minimum value of 0 mg/l was recorded during all season. The high values of NH 3 recorded during hot seasons may be due the high evaporation rates depending on the elevated temperature, addition to the denitrification process by the reduction of NO 2 - and NO 3 - to NH 3 under lower pH values and DO (Elewa et al., 2001). The pronounced increase in NH 3 content during winter season especially at surface water, may be attributed to the decomposed organic matter, also may be
due
to dying off of algal blooms resulted in increasing of ammonia
concentration (Jana et al; 1983) and (Krotn et al; 1989). Reid ( 1961) state that ammonia in excess of 1 mg/l has been given as an indicator of organic pollution and can be toxic to aquatic species in concentration over 2.5 mg/l.
In this study ,ammonia in the River Nile not
reachea to harmful concentration. Generally, ammonia toxicity causes osmoregulatory imbalance, kidney failure, suppressed excretion of endogenous ammonia, resulting in neurological and cytological failure and damage to the gill epithelium leading to suffocation. Various factors affect ammonia toxicity, including urea, amine and amine oxide derivatives, creatine, creatinine, uric acid, carbon dioxide and dissolved oxygen concentrations (Meade, 1985). Finally, it would seem that, ammonia acts on fish as true internal poison, entering the body by way of the gills, and seems to be strictly correlated with the permeability of gills for the toxic molecules. The toxicity of ammonia on fish varies with the values of dissolved oxygen and CO 2 (Yacoob, 1994; 2000).
143
Season station 0.02 0.9 0.0 0.0 0.11 0.03 0.04 0.157
spring
0.06 0.84 0.08 0.07 0.1 0.0 0.16 0.187
summer
0.22 0.0 0.13 0.24 0.24 0.05 0.0 0.126
Autumn
0.12 0.29 0.11 0.01 0.23 0.0 0.3 0.151
winter
0.105 0.51 0.08 0.08 0.17 0.02 0.125 ----
Annual average
Table (25): seasonal variation of Ammonia NH 3 (mg/l ) In investigated area during 2008
El-saaf Iron-Steel El-Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda Seasonal avr.
…………………………………….…..…………………... Results and discussion
Fig 33 : (a) annual average and b: seasonal average values of Ammonia (mg/l)
a: annual avrage. mg/l 0.6 0.5 0.4 0.3
annual avr.
0.2 0.1
Stations
0 i
ii
iii
iV
V
Vi
Vii
Season avr.
mg/l 0.200 0.190 0.180 0.170 0.160 0.150 0.140 0.130 0.120 0.110 0.100
Season avr.
Seasons spring
summer
autumn
145
winter
…………………………………….…..…………………... Results and discussion
4- Reactive Silicate Silicon is a non metallic element present in the valves and cell wall of diatoms, representing 10 to 30% of their dry weight. These diatoms are an important phytoplankton group with regarded to primary productivity and natural food for some fish species. As diatoms are the organisms, which make most use of silicon, their biology is closely linked to the cycling of this element. On the whole, silicon present in water as orthosilicic acid, Si(OH) 4 and hydrated from of silica, SiO 2 .The transformation of dissolved silicic acid into amorphous silica and backs by organisms from the core of the biological silicon cycle (Paasche, 1980).
The silica content of drainage to natural waters is less variable than many of the other major inorganic constituent. The world average is about 13 mg SiO 2 1-1, with relatively little variation among the continents; the average of groundwater is somewhat higher than that of surface drainage (Wetzel, 1983). The major source of silica is from the degradation of aluminosilicate minerals.
The seasonal variations of Silicate values were recorded in Table (26) and represented graphically in Figure (34) respectively. The values of Silicate varied in the range of 2.5 – 7.26, 4.6 – 11.4, 0.81 – 5.76 and 1.54- 6.91 mg/l during spring, summer, autumn and winter respectively. The maximum value of 11.4 mg/l was recorded during summer at station II behind iron and steel drain while the minimum value of 0.81 mg/l was recorded during autumn at stations VII . During summer, the increase of silicate contents may be attributed to the increasing in solubility of silicon with elevation of temperature or may be due to degradation of dead diatoms (Sommer and Stable, 1983, Abdo 2002).
The relative increase of silicate values during spring may be due to higher of primary production and increase of alga biomass (Wall et al; 1998, Engy 2005).
146
Season station 3.93 7.26 4.65 3.77 2.5 4.1 3.62 4.26
spring
5 11.4 4.9 4.8 5.1 4.8 4.6 5.8
summer
1.54 5.76 1.17 1.04 1.42 1.07 0.81 1.83
Autumn
1.73 6.91 1.62 1.57 1.8 1.84 1.54 2.43
winter
3.05 7.83 3.09 2.8 2.7 2.95 2.64 ----
Annual average
Table (26): seasonal variation of Reactive Silicate ( mg/l ) In investigated area during 2008
El-saaf Iron-Steel El-Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda Seasonal avr.
…………………………………….…..…………………... Results and discussion
Fig 34 : (a) annual average and b: seasonal average values of Reactive Silicate (mg/l)
a: annual avrage. mg/l 9 8 7 6 5
annual avr.
4 3 2 1 0
Stations i
ii
iii
iV
V
Vi
Vii
b: Season avrage. mg/l 7.00 6.00 5.00 4.00
Season avr.
3.00 2.00 1.00
Seasons spring
summer
autumn
148
winter
…………………………………….…..…………………... Results and discussion In addition to the decay of diatoms, fungi, fish and decomposition of organic matter (Dickson, 1975; Awadallah et al; 1996 and Nather Khamr et al 1991).
The decrease values of silicate during autumn may be due to the uptake of silica by diatoms, fungi, and fish (Ahler et al; 1991 and Elewa et al; 1995), or due to the uptake by microorganisms and aquatic plants.
The decrease in size of the diatoms cells may be related to the decrease of silicate concentration in water. When silicate concentrations are low limiting effect of phosphate on growth is more pronounced.
5- Phosphorus as Phosphate Phosphorus occurs in natural waters and in wastewater almost solely as phosphates. These are classified as orthophosphate, condensed phosphates pyro-, meta-, and other polyphosphates, and organically bound phosphates. They occur in solution, in particles or detritus, or in the bodies of aquatic organisms.
Phosphorus is essential to the growth of organisms and can be the nutrient that
limits the primary productivity of a body of water. In instances where
phosphate is a growth limiting nutrient, the discharge of raw or treated waste water, agricultural drainage or certain industrial wastes to that water may stimulate the growth of photosynthetic aquatic micro-and macro organisms in nuisance quantities (APHA, 1995).
Of the
three
major
elements,
phosphorus
is considered most
frequently limiting because its concentrations in water are often low at the cellular level, phosphorus is contained in ATP and ADP, in RNA and in numerous enzymes. In animals, phosphorus combined with calcium forms bone, teeth and scales. The phosphorus needs of animals are met through their food. (Senft, 1978).
149
…………………………………….…..…………………... Results and discussion
Total Reactive Phosphorus (TRP) Total reactive phosphorus TRP, its direct colorimetry without filtration of the water samples (APHA, 1995). It is measured as total orthophosphate. The orthophosphate represent the major content of dissolved phosphorus in the aquatic environment. The various in phosphorus species are not well soluble and their solubility is pH dependent. Their successive dissociations are as follows:
H 3 PO 4
H+ + H 2 PO 4 -
K 1 = 10 -2.13
H 3 PO 4
H+ + HPO 4 --
K 2 = 10 -7.21
H 3 PO 4
H+ + PO 4 ---
K 3 = 10 -12.36
H 2 PO 4
-
and HPO 4 --
concentration, are maximum at pH 4.67 and 9.78
respectively (Brobergand Peisson, 1988). The seasonal variations of TRP values were recorded in Table (27) and represented graphically in Figure (35) respectively. The values of TRP varied in the range of 0 – 0.017 , 0.003 - 0.023 and 0 - 0.008 mg/l during spring, autumn and winter respectively and no TRP recorded during summer . The maximum value of 0.017 mg/l was recorded during spring at station ii behind iron and steel drain while the TRP not recorded during spring and winter at many stations and summer at all stations . The higher values of TRP were recorded during autumn, may be attributed to, the flood period in which leaching the rocks containing phosphate and which facilitate the release of PO 4 -3 from sediment to the above water. As well as the release of adsorbed phosphate on the silt and clay particles into the free water at the favourable conditions and the excretion of large amounts of phosphate by zooplankton and fish as reported by (Elewa et al, 2001, Abdo 2002).
150
Season station 0.01 0.017 0.004 0.006 0.0 0.007 0.0 0.01
spring
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
summer
0.023 0.008 0.005 0.003 0.005 0.005 0.004 0.008
Autumn
0.0 0.008 0.005 0.0 0.002 0.0 0.0 0.002
winter
0.008 0.008 0.004 0.002 0.002 0.003 0.001 ----
Annual average
Table ( 27 ) : seasonal variation of Phosphate PO 4 -3 ( mg/l ) In investigated area during 2008
El-saaf Iron-Steel El-Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda Seasonal avr.
…………………………………….…..…………………... Results and discussion
Fig 35 : (a) annual average and b: seasonal average values of TRP (mg/l)
a: annual avrage. mg/l 0.009 0.008 0.007 0.006 0.005
annual avr.
0.004 0.003 0.002 0.001 0
Stations i
ii
iii
iV
V
Vi
Vii
b: Season avrage.
mg/l 0.008 0.007 0.006 0.005 0.004
Season avr.
0.003 0.002 0.001
Seasons
0 spring
summer
autumn
152
winter
…………………………………….…..…………………... Results and discussion On the other hand, the absent TRP values were recorded during summer may be attributed to the dilution effect caused by more water comes from Nasser lake behind high dam and increasing on the water level.
Nitrogen and phosphorus exist in variety forms in water and often associate with each other and with suspended mineral particles and cause turbidity, which is undesirable for drinking water (Gilliam et al; 1985 and ,paul.l996).
F – Heavy metal Trace metals such as manganese and iron are considered to be essential elements in the growth of plankton and thus play an important role in the geobiochemical cycle of the aquatic environment (Stumm d Morgan, 1970).
Trace metals such as manganese, copper, cobalt and zinc play a biochemical role in the life processes of some aquatic plants and animals, when it is presence in trace amounts. However, when it is presence at light concentrations they become toxic.
Heavy metals enter river and lakes from a variety of sources. The rocks and soils directly exposed to surface water are the largest natural sources. Dead and decomposed vegetation and animal matter, contribute small
amounts
of
metals to adjacent waters, wet and dry fallout of atmospheric particulate matter arrived from natural sources as well as man's activities can introduce large quantities of metals to rivers and lakes. In addition to the discharge of various treated and untreated liquid wastes to the water body can introduce a large amount of trace metals to rivers and lakes (Stumm and Morgan, 1970).
The important role of determination and speciation heavy metals pollution of heavy metals is a primary target in environmental research today (Bores, 1991).
153
…………………………………….…..…………………... Results and discussion Iron, Manganese, Zinc, Lead, Copper, Cadmium Chromium and Nickel metals, were detected seasonally in the period of the study.
1- Iron The role of iron in the body is almost exclusively confined to the processes of cellular respiration. Iron prophyrin (heme) groups are essential components of hemoglobin, myoglobin, the cytochromes, and the enzymes catalse and peroxidase. The remainder of the iron in the body (nonheme iron) is almost entirely peotein-bound. These forms include the intracellular iron containing flavoproteins (NADH) dehydrogenase and succinate dehydrogenase and iron sulfur proteins as well as storage and transport, forms of the mineral. (Harper et al., 1977).
The need for iron in the human diet varies greatly at different ages and under different circumstances. It is determined by the requirements for tissue growth and hemoglobin synthesis and the replacement needs due to iron losses in urine, feces, and sweat, and in the female, the additional losses in menstruation, gestation and lactation. The need for iron is greatest during the first 2 years of life, during the period of rapid growth and hemoglobin increase in adolescence, and throughout the childbearing period in women. (Harper et al., 1977).
The seasonal variations of iron values were recorded in Table (28) and represented graphically in Figure (36) respectively. The values of iron varied in the range of 0.332 – 2.11, 0.25 – 1.27, 0.2 – 0.82 and 0.214- 1.524 mg/l during spring, summer, autumn and winter respectively. The maximum value of 2.112 mg/l was recorded during spring at station II behind iron and steel drain while the minimum value of 0.2 mg/l was recorded during autumn at station VII .
154
Season station 0.44 2.11 0.33 0.73 0.43 0.37 0.36 0.68
spring
0.27 1.27 0.26 0.27 0.26 0.29 0.25 0.41
summer
0.51 0.82 0.71 0.5 0.48 0.43 0.2 0.52
Autumn
0.3 1.52 0.27 0.4 0.22 0.21 0.29 0.46
winter
0.38 1.43 0.39 0.48 0.38 0.33 0.28 ----
Annual average
Table ( 28 ) : seasonal variation of Iron Fe ( mg/l ) In investigated area during 2008
El-saaf Iron-Steel El-Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda Seasonal avr.
…………………………………….…..…………………... Results and discussion
Fig 36 : (a) annual average and b: seasonal average values of Iron (mg/l)
a: annual avrage. mg/l 1.6 1.4 1.2 1 annual avr. 0.8 0.6 0.4
Stations
0.2 i
ii
iii
iV
V
Vi
Vii
b: Season avrage. mg/l 0.700 0.650 0.600 0.550 0.500
Season avr.
0.450 0.400 0.350
Seasons
0.300 spring
summer
autumn
156
winter
…………………………………….…..…………………... Results and discussion The minimum values of iron were recorded during summer. This may be attributed to the iron adsorbed by clayey minerals, suspended matter, surface microorganisms, and metals oxide as iron oxide under high
temperature
(Hassouna, 1989, Abdo 2002). On the other side, the relative decrease in iron concentrations during winter may be due to the oxidation of Fe+2 to Fe+3 and precipitated as hydroxide at high pH value in presence of high dissolved oxygen according to the following equations:-
Fe+2 + H 2 O ------- ►
Fe+3 + H 2 O + (-e)
Fe+3 + 3H 2 O -----►
Fe (OH) 3 + 3H+ (Ruttner, 1963).
During autumn the relative increase of iron recorded may be related to the flood period, which leads to the leaching of iron from the banks of River Nile result in the great amount of fine grains and suspended particles containing iron element. Increasing of iron concentrations during spring, may be attributed to the dissolution of sediments and release of iron to the overlying water.
Generally, the distribution dynamics of iron in water ecosystem depend on the dissolved oxygen and present as insoluble Fe(OH) 3 or ferric oxide. The ferrous form can only exist in the absence of oxygen and the ferric forms are almost completely insoluble, in other words, in oxygenated water, iron is precipitated as ferric salts (Ruttner, 1953).
Iron can be also occur in organic compound as humic acid and as colloid. These organic iron are much more stable than the inorganic iron. Also Fe+2 can compete successfully with Ca+2 and Mg+2 for organic chelating agents (Ruttner, 1963).
157
…………………………………….…..…………………... Results and discussion
2-Manganese Manganese is essential for normal bone structure, reproduction, and normal functioning of the central nervous system. The total body content of manganese is 12-20 mg. The kidney and liver are the chief storage organs for manganese, mitochondria are the principal intracellular sites of manganese uptake. In blood, values of 4-20 µg/dl have been reported. Most of the manganese is excreted onto the intestine by way of the bile. Very little manganese usually occurs in the urine. An evident deficiency of manganese is not known in man, suggesting that the average daily dietary intake of 2.5 - 7 mg is adequate (Harper et al, 1977). The seasonal variations of manganese values were recorded in Table (29) and represented graphically in Figure (37) respectively. The values of manganese varied in the range of 0.028 – 0.348, 0.031 – 0.169, 0.028 – 0.125 and 0.049- 0.365 mg/l during spring, summer, autumn and winter respectively. The maximum value of 0.365 mg/l was recorded during winter at station II behind iron and steel drain while the minimum value of 0.028 mg/l was recorded during spring at stations I, VI and during autumn at station VII . The results of manganese concentrations revealed that, the high values were recorded during winter and spring seasons, this may be attributed to the effect of the drought period. However, the low water level and the water current would facilitate in the excretion aquatic plants
of manganese
slow motion of from
death
in addition to dissolution of sediment manganese and release to
water during spring (Abdo, 1998 and Abdo 2002).
The lower values of manganese during summer and autumn may be attributed to the removal of manganese from aqueous phase to solid phase during precipitation of Mn as MnO 2 or by adsorption on suspended particles during summer as well as the dilution effect of the flood period during autumn (Goher, 1998 and Abdo 2002).
158
Season station 0.028 0.348 0.031 0.039 0.034 0.028 0.029 0.077
spring
0.032 0.169 0.031 0.032 0.031 0.032 0.032 0.051
summer
0.049 0.125 0.063 0.054 0.059 0.044 0.028 0.060
Autumn
0.049 0.365 0.059 0.06 0.058 0.055 0.052 0.1
winter
0.04 0.252 0.046 0.046 0.046 0.04 0.035 ----
Annual average
Table ( 29 ) : seasonal variation of Manganese Mn ( mg/l ) In investigated area during 2008
El-saaf Iron-Steel El-Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda Seasonal avr.
…………………………………….…..…………………... Results and discussion
Fig 37 : (a) annual average and b: seasonal average values of Manganese (mg/l)
a: annual avrage. mg/l 0.3 0.25 0.2 0.15
annual avr.
0.1 0.05
Stations
0 i
ii
iii
iV
V
Vi
Vii
b: Season avrage. mg/l 0.110 0.100 0.090 0.080 Season avr. 0.070 0.060 0.050
Seasons
0.040 spring
summer
autumn
160
winter
…………………………………….…..…………………... Results and discussion Generally at low oxygen content, the solubility of Mn (II) increase may be occur by following processes: a) a decrease in pH will shift the exchange-adsorption equilibrium in such a way as to adsorb Mn(II) from higher valence manganese oxides and from ferric oxide, (b) reduction of ferric oxide release sorbed Mn(II), and (c) ferrous iron and other reductance (S--, organic matter) can reduce manganese oxides and render them soluble (Hassouna, 1989). On the whole, manganese is necessary nutrient element for plants and animals. It stimulates plankton growth perhaps by activating enzyme system and by having at least some effects on the vitamin and amine. Very close to iron in the economy of lakes and behaving in much the same manner is the heavy metal manganese, has four valence states and it alternates between reduced soluble and oxidized " less soluble " ; conditions. It is abundance in the igneous rocks and is perhaps no greater than 0.5 % but this amount seems adequate and manganese deficiencies are rare (Ruttner, 1983).
3-Zinc Zinc is a trace metal, essential for marine life. It is involved in various physiological mechanisms growth, vision, sexual maturity, spowning, and various organic functions. It is known, but not elucidated that the increase concentration of zinc makes it toxic for sensitive species. Its sublethel action is complex and depends on different factors (Houvet et al, 1989).
Zinc has low human toxicity but relative high toxicity to fish, therefore, water having up to 5 mg Zn/L, would be highly toxic to most fish species. The toxicity of zinc is modified by environmental factors as hardness, temperature, dissolved oxygen and presence of suspended solids or organic matter (Hodson and Sprague, 1975)
161
…………………………………….…..…………………... Results and discussion Zinc is essential for the normal growth, reproduction, and life expectancy of animals and has a beneficial effect on the processes of tissue repair and wound healing. Zinc is widely distributed in the tissues of the body. The human body is estimated to contain 1.4 - 2.3 g of zinc. About 20% of the total body zinc is present in the skin (Harper et al., 1977)
The seasonal variations of zinc values were recorded in Table (30) and represented graphically in Figure (38) respectively. The values of zinc varied in the range of 5.97 – 75.29, 23.6 – 96.98, 15.07– 31.8 and 6.23- 34.6 µg/l during spring, summer, autumn and winter respectively.
The maximum value of 96.98 µg/l was recorded during summer at station II behind iron and steel drain while the minimum value of 5.97 µg/l was recorded during spring at stations VII. Increasing of Zn during hot seasons (summer and spring) more than cold seasons (autumn and winter) this is due to the high rate of evaporation during summer, Besides the influence of aquatic organisms especially macrophytes.
Decreasing of zinc values during autumn and winter may be attributed to its uptake by macrophytes or due to its adsorption into the clayey particles and sedimentation to the underlying sediments. Generally, zinc most commonly enters the domestic water supply from deterioration of galvanized iron and dezinicfication of brass. In such cases lead and cadmium may be present because the impurities of the zinc used in galvanized. On the other hand, zinc
is a common pollutant in fresh water and
occurs from industrial waste pollution and other sources. It often accompanied by iron, copper and other heavy metals and affects Fresh water fisheries, presumably mainly by its direct effect on fish but possibly too on some fish food organisms such as mayflies and daphnia (Hassouna, 1989).
162
Season station 17.04 75.29 18.17 35.54 15.54 14.7 5.97 26.04
spring
39.76 96.98 29.45 28.71 23.6 38.24 30.15 40.98
summer
17.4 31.81 15.07 27.67 16.15 21.08 15.3 20.64
Autumn
15.66 34.6 8.69 17.99 9.69 6.23 13.53 15.20
winter
22.47 59.67 17.85 27.48 16.24 20.06 16.24 ----
Annual average
Table ( 30 ): seasonal variation of Zinc Zn ( µg/l ) In investigated area during 2008
El-saaf Iron-Steel El-Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda Seasonal avr.
…………………………………….…..…………………... Results and discussion
Fig 38 : (a) annual average and b: seasonal average values of
Zinc
(µg/l)
a: annual avrage.
µg/l 70 60 50 40
annual avr.
30 20
Stations
10 i
ii
iii
iV
V
Vi
Vii
b: Season avrage .
µg/l 45.00 40.00 35.00 30.00
Season avr.
25.00 20.00 15.00
Seasons spring
summer
autumn
164
winter
…………………………………….…..…………………... Results and discussion Biochemistry, zinc is very important to the living system, which is one of metal dehydrogenases constituents, it required to photosynthesis as agent in hydrogen transfer, Another metabolic role of zinc in the synthesis of protein. It precipitate to the sediment as sulphide and co-precipitate with CaCO 3 and Fe(OH) 3 (Abdo, 1998).
4-Copper Copper is an essential constituent of several proteins metalloenzymes, and some naturally occurring pigments. It is essential for hemoglobin synthesis, normal bone formation, and the maintenance of myelin within the nervous system. Hemocyanin is a copper-protein complex in the blood of certain invertebrates, where it functions like hemoglobin as an oxygen carrier (Harper et al, 1977).
The adult human body contains 100 - 150 mg of copper; about 64 mg are found in the muscles, 23 mg in the bones, and 18 mg in the liver, which contains a higher concentration of copper than that of any of the other organs studied. It is of interest that the concentration of copper in the fetal livers is 5 - 10 times higher than that in the liver of an adult. Both the blood cells and serum contain copper; but the copper content of the red blood cell is constant, while that of the serum is highly variable averaging about 90 µg/dl (Harper et al, 1977)
The human requirement for copper has been studied by balance experiments. A daily allowance of 2.5 mg has been suggested for adults; infants and children require about 0.05 µg/1 body weight. This is easily supplied in average diets, which contain 2.5 - 5 mg of copper. (Harper et al., 1977)
165
…………………………………….…..…………………... Results and discussion The seasonal variations of copper values were recorded in Table (31) and represented graphically in Figure (39) respectively. The values of copper varied in the range of 3.18 – 6.79, 4.88 – 5.79, 9.74– 16.76 and 5.47- 28.62 µg/l during spring, summer, autumn and winter respectively. The maximum value of 28.62 µg/l was recorded during winter at station II behind iron and steel drain while the minimum value of 3.18 µg/l was recorded during spring at stations VI.
The results showed that, the copper increased in cold season (winter and autumn) and decreased in hot seasons (summer and spring). The increase values of copper in cold seasons may be due to adsorption of copper by humic material (Abd El Satar, 1998 and El-Hadad 2005).
On other hand, the decrease values of copper during hot seasons may be due to the removal of copper from water by the uptake by phytoplankton or may be due to adsorption on the suspended matter making complexation with organic matter leaving the water to sediment (Abd El Satar, 1998 and El-Hadad 2005).
From the stand point of human health, copper is relatively low in toxicity compared to the other metals like mercury, lead and cadmium (Anon, 1978). In the drinking water the limit of 1 mg/l copper is based on consideration of taste rather than hazards to health (Masoud et al., 1994). Although prolonged consumption of large doses has been known to cause emcees and liver damage in humans (National Academy of Science 1973) On the other hand, copper is an essential and beneficial element in human metabolism, and it is known that a deficiency in copper results nutritional anemia in infants (Massoud et al, 1994). It is doubtful that even the highest content of copper concentrated by fish could harm human consumers because copper is low in toxicity to humans and dose tend to accumulation the edible tissues of fishes (Hassouna, 1989).
166
Season station 3.9 6.79 4.28 5.8 10.15 3.18 4.31 5.49
spring
5.48 5.79 4.88 5.6 4.91 5.81 4.96 5.35
summer
11.18 9.74 16.76 14.56 12.49 12.03 10.6 12.48
Autumn
6.88 28.63 7.01 7.39 10.62 5.47 7.74 10.53
winter
6.86 12.74 8.23 8.34 9.54 6.62 6.9 ----
Annual average
Table ( 31 ) : seasonal variation of Copper Cu ( µg/l ) In investigated area during 2008
El-saaf Iron-Steel El-Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda Seasonal avr.
…………………………………….…..…………………... Results and discussion
Fig 39 : (a) annual average and b: seasonal average values of
Copper (µg/l)
a: annual avrage.
µg/l 14 13 12 11 10 9 8 7 6 5 4
annual avr.
Stations i
ii
iii
iV
V
Vi
Vii
b: Season avrage.
µg/l 14.00 12.00 10.00 8.00
Season avr.
6.00 4.00
Seasons
2.00 spring
summer
autumn
168
winter
…………………………………….…..…………………... Results and discussion
5- Lead Lead, occurring chiefly as the sulphide , galena, is the most abundant of the heavy metals found in the earth's crust. The principal causes of environmental lead contamination in recent times arise from its use in lead storage batteries and as gasoline antiknock additives. Lead containing pesticides have been also used but this use has decreased in recent years. Very high levels of lead could occur in the wine from the combined practices of using lead- lined vessels for wine storage and consumption, and by the use of lead- tainted syrup in wine preparation. (Shibamoto and Bjeldanes, 1993) Lead has been detected in all foods examined, even those grown for from industrialization areas. Recent analyses suggest a natural level of lead to be on order of 0.3 ppb in wide ranging marine fish. These fish are comparatively free of geographically localized contamination and are considered good indicators of general environmental contamination levels considerably in excess of this limit, (Shibamoto and Bjeldanes, 1993). Lead usually causes chronic poisoning because of its nature, where it is absorbed and even more slowly excreted. It is cumulative, being stored in the tissues, especially the bones, and symptoms of poisoning may follow years of such storage and occur as the immediate consequence of release into general circulation (Stewart and Stolman, 1960) Lead, a contaminant found in many water supplies across the country, is a major public health concern. Because of this concern, the U.S. Environmental Protection Agency (EPA) recently established a new National Primary' Drinking Water regulation for lead, reducing the accepted lead level from 50 parts per billion 15 ppb.
The seasonal variations of lead values were recorded in Table (32) and represented graphically in Figure (٤۰).
169
Season station 0.023 3.858 0.0 0.149 0.436 0.158 1.432 0.87
spring
2.068 5.152 1.44 2.396 0.94 1.85 1.6 2.21
summer
3.86 2.36 4.12 4.38 5.16 3.61 3.23 3.82
Autumn
8.23 5.13 3.41 7.96 4.51 2.83 9.74 5.97
winter
3.55 4.13 2.24 3.72 2.76 2.11 4.0 ----
Annual average
Table ( 32 ) : seasonal variation of Lead Pb ( µg/l ) In investigated area during 2008
El-saaf Iron-Steel El-Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda Seasonal avr.
…………………………………….…..…………………... Results and discussion
Fig 40: (a) annual average and b: seasonal average values of
Lead
(µg/l)
a : annual avrage. µg/l 4.5 4 3.5 3
annual avr.
2.5 2
Stations
1.5 1
2
3
4
5
6
7
b: Season avrage. µg/l 7.00 6.00 5.00 4.00 Season avr.
3.00 2.00 1.00
Seasons
0.00 spring
summer
autumn
171
winter
…………………………………….…..…………………... Results and discussion The values of lead varied in the range of 0 – 3.868, 0.94 – 5.15, 2.36– 5.16 and 2.82- 9.74 µg/l during spring, summer, autumn and winter respectively. The maximum value of 9.738 µg/l was recorded during winter at station VII while the value reach to 0 µg/l was during spring at stations III. These
results
revealed
that,
the
values of lead concentrations
increased during cold seasons (winter and autumn) and decreased during seasons (summer and spring). The lower values
of lead content during hot seasons, may be attributed
to the precipitation of lead salts under high pH and temperature values most of this salts may be present in the forms of lead carbonate agreed with reported by (Ghallab, 2000 and Abdo 2002 ), Also The decreasing of lead during spring and summer attributed to adsorption of lead onto organic matter which descending to the bottom sediment especially with high temperature (Berg et al; 1995 and Gomaa 2002 ).
The
higher
values of lead concentrations were observed during winter
may be attributed to the drought period, whereas, the water levels decreased and the degradation of the most aquatic organisms and organic matter would be increased. This result in release of the lead to the above water layers due to the microbial activities (Abdo, 1998). Or may be attributed to the high amount of agricultural runoff whereas (Gomaa, 2002).
The relative increased of lead concentrations during autumn , may be attributed to the flood period, leading to leaching of lead rocks and dissolution of sediment containing lead
which facilitate the mobilization of lead from
sediment into the above water layers. Generally, lead is a serious accumulative body poisons. Thus, the acceptable level of lead the body can safely tolerant has not been established. It is known
172
…………………………………….…..…………………... Results and discussion that lead in excess of the quantity can be exerted is accumulative and, in the advanced stages of lead poisoning, results in construction, anemia, abdominal pains, and gradual paralysis, particularly in the arm muscles (Anon, 1978).
6- Cadmium Cadmium may entry water as a result of industrial discharge or the deterioration of galvanized pipe (APHA, 1995). Concentration of Cd in River Nile depending on the quantity of sewage discharge, agricultural discharges, domestic wastes and industrial discharges inflow to the rive (Issa et al., 1996). The most important difference between Cd and Pb in waters system, is the strong direct effect of pH on Cd, indicating that, the particle bond Cd is mobilized to the water phase by acidification, in other words, Cd is Sorbed to sedimentary organic matter and the binding intensity is very Sensitive to pH variation (Tessier et al., 1973). The seasonal variations of cadmium values were recorded in Table (33) and represented graphically in Figure (41) respectively. The values of cadmium varied in the range of 0 – 0.096, 0 – 0.146, 0.11– 0.25 and 0- 0.101 µg/l during spring, summer, autumn and winter respectively. The maximum value of 0.25 µg/l was recorded during autumn at station vii while the value reach to 0 µg/l was during all season except autumn. The lower values of cadmium content during hot seasons, may be attributed to the precipitation of cadmium salts under high pH and temperature values most of this salts may be present in the forms of cadmium carbonate , The higher values of cadmium concentrations during autumn , may be attributed to the flood period, leading to leaching of cadmium rocks and dissolution of sediment containing cadmium which facilitate the mobilization of lead from sediment into the above water layers
173
Season station 0.044 0.096 0.0 0.0 0.061 0.0 0.0 0.029
spring
0.0 0.146 0.0 0.0 0.0 0.0 0.0 0.021
summer
0.11 0.14 0.157 0.157 0.22 0.21 0.25 0.178
Autumn
0.041 0.101 0.082 0.048 0.021 0.0 0.014 0.044
winter
0.049 0.12 0.06 0.051 0.076 0.053 0.066 ----
Annual average
Table ( 33 ): seasonal variation of Cadmium Cd ( µg/l ) In investigated area during 2008
El-saaf Iron-Steel El-Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda Seasonal avr.
…………………………………….…..…………………... Results and discussion
Fig 41 : (a) annual average and b: seasonal average values of
Cadmium
(µg/l)
a: annual avrage. µg/l 0.13 0.12 0.11 0.1 0.09
annual avr.
0.08 0.07 0.06 0.05
Stations
0.04 i
ii
iii
iV
V
Vi
Vii
b: Season avrage.
µg/l 0.200 0.180 0.160 0.140 0.120 0.100 0.080 0.060 0.040 0.020 0.000
Season avr.
Seasons spring
summer
autumn
175
winter
…………………………………….…..…………………... Results and discussion Generally, Cd concentration in the river depending on the quantity of sewage
discharge, agricultural discharges domestic wastes
and industrial
discharges inflow to the river (Issa et al., 1996). On the whole, cadmium is highly toxic and has been implicated in some cases containing through food. Minute quantities of Cd are responsible for adverse change in arteries of kidneys and livers. Cd, also causes generalized cancers in animals and has been linked epidemiologicaly with human cancers (APHA, 1992).
Since cadmium tends to concentrate in the liver, kidneys, pancreas, and thyroid of human and animals, it has resulted in a number of death. Once it entry the body it is likely to remain and there is no evidence that cadmium is biologically essential or beneficial (Anon, 1978).
7- Chromium Chromium is ubiquitous in the environment, occurring naturally in the air, water, rocks and soil. It is used in stainless steel, electroplating of chrome, dyes, leather tanning and wood preservatives. It occurs in several forms, or oxidation states. The two most common are chromium VI and chromium III. The form depends on pH. Natural sources of water contain very low concentrations of chromium. It is a micronutrient (or essential trace element). High doses of chromium VI have been associated with birth defects and cancer; however, chromium III is not associated with these effects. Plants and animals do not bioaccumulate chromium; therefore, the potential impact of high chromium levels in the environment is acute toxicity to plants and animals. In animals and humans this toxicity may be expressed as skin lesions or rashes and kidney and liver damage.
The criteria for total chromium in a domestic water supply is 0.05 mg/l The aquatic life criteria is less than 0.011 mg/L for chromium VI and less than 0.207 mg/L for chromium III. (The second value is based on a formula involving hardness).
176
…………………………………….…..…………………... Results and discussion The seasonal variations of chromium values were recorded in Table (3٤) and represented graphically in Figure (42) respectively. The values of chromium varied in the range of 0.099 – 5.84, 0.863 – 3.46, 0.79– 4.49 and 1.023.13 µg/l during spring, summer, autumn and winter respectively.
The maximum value of 5.84 µg/l was recorded during spring at station II behind iron and steel drain while the minimum value of 0.099 µg/l was recorded during spring at stations VI.
These results revealed that, the values of chromium concentrations increased during cold seasons (winter and autumn) and decreased during seasons (summer and spring). The relative increased of chromium concentrations during winter may be attributed to the drought period, whereas, the water levels decreased and the degradation of the most aquatic organisms and organic matter would be increased. This result in release of the chromium to the above water layers due to the microbial activities. Or may be attributed to the high amount of agricultural runoff whereas The
higher
values of chromium concentrations were observed during
autumn may be attributed to the flood period, leading to leaching of chromium rocks and dissolution of sediment containing chromium which facilitate the mobilization of chromium from sediment into the above water layers.
Short-term: EPA has found chromium to potentially cause the following health effects when people are exposed to it at levels above the Maximum Contaminant Level (MCL) for relatively short periods of time: skin irritation or ulceration. Long-term: Chromium has the potential to cause the following effects from a lifetime exposure at levels above the MCL: damage to liver, kidney circulatory and nerve tissues, skin irritation.
177
station
Season El-saaf Iron-Steel El-Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda Seasonal avr.
spring
1.02 3.46 1.65 0.87 0.88 1.02 0.86 1.4
summer
1.03 4.49 1.64 1.35 1.48 1.23 0.79 1.72
Autumn
1.25 3.13 1.19 1.37 1.55 1.02 1.57 1.58
winter
1.02 4.23 1.28 1.18 1.16 0.84 1.12 ----
Annual average
Table ( 34 ) : seasonal variation of Chromium Cr ( µg/l ) In investigated area during 2008
0.79 5.84 0.64 1.14 0.72 0.1 1.25 1.5
…………………………………….…..…………………... Results and discussion
Fig 42 : (a) annual average and b: seasonal average values of
Chromium (µg/l) a: annual avrage.
µg/l 4.5 4 3.5 3 2.5
annual avr.
2 1.5 1 0.5
Stations
0 i
ii
iii
iV
V
Vi
Vii
b: Season avrage.
µg/l 1.80 1.70 1.60 1.50
Season avr.
1.40 1.30
seasons
1.20 spring
summer
autumn
179
winter
…………………………………….…..…………………... Results and discussion
8- Nickel Nickel usually has two valence electrons, but oxidation states of +1, +3, or +4 may also exist. Metallic nickel is not affected by water but is slowly attacked by dilute hydrochloric or sulfuric acid and is readily attacked by nitric acid. Fused alkali hydroxides do not attack nickel. Several nickel salts, such as the acetate, chloride, nitrate, and sulfate, are soluble in water, whereas carbonates and hydroxides are far less soluble and sulfides, disulfides, subsulfides, and oxides are practically insoluble in water. Alloys of nickel containing more than 13% chromium are to a high degree protected from corrosion in many media by the presence of a surface film consisting mainly of chromium oxide (Morgan & Flint, 1989; Haudrechy et al., 1994).
Nickel concentrations in groundwater depend on the soil use, pH, and depth of sampling. The average concentration in groundwater in the Netherlands ranges from 7.9 µg/l (urban areas) to 16.6 µg/l (rural areas). Acid rain increases the mobility of nickel in the soil and thus might increase nickel concentrations in groundwater (IPCS, 1991). In groundwater with a pH below 6.2, nickel concentrations up to 980 µg/l have been measured (RIVM, 1994). The seasonal variations of nickel values were recorded in Table (35) and represented graphically in Figure (43) respectively. The values of nickel varied in the range of 0.108 – 3.581, 1.211 – 2.535, 1.6– 3.07 and 1.554- 4.053 µg/l during spring, summer, autumn and winter respectively. The maximum value of 4.053 µg/l was recorded during winter at station II behind iron and steel drain while the minimum value of 0.108 µg/l was recorded during spring at stations VI. These results revealed that, the values of nickel concentrations increased during cold seasons (winter and autumn) and decreased during seasons (summer and spring).
180
Season station 0.59 3.58 0.39 0.49 0.37 0.11 0.69 0.89
spring
2.37 2.56 1.62 1.57 1.21 1.34 1.47 1.73
summer
2.07 3.07 2.16 2.02 1.65 1.62 1.6 2.03
Autumn
2.26 4.05 2.24 3.21 1.55 2.25 2.08 2.52
winter
1.82 3.31 1.6 1.82 1.2 1.33 1.45 ----
Annual average
Table ( 35 ) : seasonal variation of Nickel Ni ( µg/l ) In investigated area during 2008
El-saaf Iron-Steel El-Tebeen Kafr-elawe North-Helwan El-Maadi El-Roda Seasonal avr.
…………………………………….…..…………………... Results and discussion
Fig 43 : (a) annual average and b: seasonal average values of
Nickel (µg/l) a: annual avrage. µg/l 3.5 3 2.5 annual avr. 2 1.5
Stations
1 i
ii
iii
iV
V
Vi
Vii
b: Season avrage. µg/l 3.00 2.50 2.00 1.50
Season avr.
1.00 0.50
Seasons
0.00 spring
summer
autumn
182
winter
…………………………………….…..…………………... Results and discussion Increasing of nickel concentrations during winter may be attributed to the drought period, whereas, the water levels decreased and the degradation of the most aquatic organisms and organic matter would be increased. This result in release of the chromium to the above water layers due to the microbial activities. Or may be attributed to the high amount of agricultural runoff whereas The relative increased of nickel concentrations during autumn, may be attributed to the flood period, leading to leaching of nickel rocks and dissolution of sediment containing nickel which facilitate the mobilization of nickel from sediment into the above water layers. On the other hand, the relative decrease were recorded during summer may be attributed to the dilution effect caused by more water comes from Nasser lake behind high dam and increasing on the water level.
General toxicity value may not be sufficiently protective of individuals sensitized to nickel, for whom a sufficiently high oral challenge has been shown to elicit an eczematous reaction. The guideline value for nickel in drinking-water is therefore derived using the (lowest-observed-adverse-effect-level) LOAEL of 12 µg/kg of body weight established after provocation of fasted patients with an empty stomach (Nielsen et al., 1999).
The human body contains approximately 10 mg nickel. Nickel is a dietary requirement for a number of organisms; therefore it might be of significance to humans. The human dietary need is estimated at only 5 μg, which is the result of a 150 μg intake. Nickel probably has a function in urea to ammonia conversion by the urease enzyme. Nickel cannot be resorbed in the digestive gland, unless it is complexed. Nickel inhalation poses a greater risk than nickel in water. This may cause lung cancer, or nasal tumors. Nickel carcinogenity is probably caused by nickel replacing zinc and magnesium ions on DNA-polymerase.
183
…………………………………….…………..…………... Results and discussion
Part II – Sediment analysis The aquatic chemistry of metal in the natural environment is dependent on the distribution dynamics of these metals and on the type of interactions between the metals and their aquatic environment. The organic matter associated with sediment particles largely responsible for the ability of sediment to adsorb uncharged organic compounds. Pollutant concentration in sediments usually increases with decreasing particles size (Kotickhoff, 1983).
Recently, a number studies have been reported on the presence of trace metals in the rivers and lakes sediments around the world where the sediments act as accumulator for these metals and the rate of accumulation depends mainly on the environmental parameters (Shehata et al, 1995 & Gomaa, 1995). Thereafter, the analysis of sediment included, organic matter, carbonate percentage, major cations, Na+, K+, Al as well as heavy metals; Fe, Mn, Zn , Cu, Cd, Ni ,Cr and Pb.
A – Organic Matter (OM%) The organic matter content of the sediment is a result of contribution of teragenous materials and the decomposition of plants and animals by the action of bacteria (Issa et al, 1996). The composition of organic matter are varying depends on the origin and geological history in the marine environment, phytoplankton, zooplankton and other microorganisms which are the most abundance sources of organic matter in sediment (Kotickhoff, 1983).
OM (% ) of the Nile sediments in the studied area at different stations, during winter season are presented in this Table ( 36 ).
stations
I
II
III
IV
V
VI
VII
Organic matter %
0.8
8.9
6.3
6.9
8.1
7
4.1
184
…………………………………….…………..…………... Results and discussion The maximum value of organic matter in the Nile sediments in the studied area was 8.9 (%) recorded at station II behind iron and steel drain while the minimum value of 0.8 % was recorded at stations I. According to (Kotickhoff, 1983), the sediment particles are largely responsible for
the ability of sediment to adsorb uncharged organic compounds.
The
pollutant concentration in the sediment usually increases with decreasing of particle sizes. Thus the small particle size of clay sediment at iron and steel drain contribute to the presence of high organic matter content.
Generally, the organic matter content in the sediments is affected by the geological and morphology of the river basins, type of sediment, domestic sewage and industrial waste, also pH and dissolved oxygen may affect on the organic matter content (Hassouna, 1989).
As a whole, the quantitative of organic matter in the Nile sediment depends principally upon some factors (Awad, 1993). These factors are:1- The allchthonous organic load entering into the Nile with sewage and industrial wastes 2- The autochthonous organic production of the Nile sediments. 3- Rate of decomposition of organic matter 4- Particle composition of the sediments
B- Carbonate content According to Serruya, (1971) calcium carbonate precipitation is controlled by photosynthesis in the upper layer of water column and the principle constituent of carbonate have been precipitate directly from water column. In the present studied The maximum value of 18.4 (%) was recorded at station II behind iron and steel drain while the minimum value of 2.4 (%) was recorded at stations VI.
185
…………………………………….…………..…………... Results and discussion Carbonate content (%) at different stations, during January 2009 are presented in this Table ( 37 ).
stations
I
II
III
IV
V
VI
VII
Carbonate content %
14.1
18.4
5.4
7.4
11.3
2.4
15.2
Generally, carbonate content in the sediment is affected by the type of the sediment and with the alkalinity of overlying water and the temperature. (Sayer, 1966) suggested that, CaCO 3 precipitation is controlled by photosynthesis in Lake Kinneret and Constance. Inorganically, the higher water temperature of shallow water depth favore precipitation through decreased solubility of both CaCO 3 and CO 2
C- Major cations 1 – Sodium Sodium is the sixth most abundant elements in the lithosphere. It is very reactive and soluble when
leached from the rocks. Its compounds tend to
remain in solution and for this reason, it is the third most abundant metals in lakes and streams and in many instances it ranks first (Cole, 1979 ).
Under certain conditions sodium may precipitate and it replaces other cations in clay minerals or other elements. In more parts where chemical weathering is practically nonexistent, the ionic composition of lake water is determined by the occasional precipitation. Sodium chloride is predominant. The present results reveal that, the maximum value of 19.344 mg/g was recorded at station VII while the minimum value of 9.65 mg/g was recorded at stations I.
186
…………………………………….…………..…………... Results and discussion Sodium concentration in the sediment and subsurface water at different stations, during January 2009 is presented in this Table ( 38 ).
stations Sodium in dry sed. (mg/g)
Sodium in water (mg/l)
I
II
III
IV
V
VI
VII
9.65
14.26
12.42
16.5
16.81
17.5
19.34
38.25
126.3 43.3
43.98
42.42
39.63
42.47
140 120 100 80 60 40 20 0 i
ii
iii
iV
V
Vi
Vii
Stations sediment mg/ g
water mg/l
Fig: 44 Sodium concentration in water and sediment during winter season
At the reference station ( I ) the minimum value of sodium concentration ware recorded in the sediment and water , At iron and steel drain ( II ) the fact that the highest value in water and normal range in the sediment may be attributed to sodium salts is present in the soluble state in water system . Generally, the present results of (Na+) distribution in the Nile were found less than reported by (Goher 1998) on the Damietta branch, this may be returned to the different pollution sources situated .
187
…………………………………….…………..…………... Results and discussion
2 – Potassium Potassium is considered of the most active cations in the aquatic environments. Certain plants such as "Kelp" can concentrated potassium to level that it constitutes up to 15 (% ) of its dry weight (Davis, 1972). Potassium is a close relative of sodium but does not remain in solution as well as sodium (Cole, 1979). As reported in the following Table maximum value of 17.456 (mg/g) was recorded at station IV while the minimum value of 7.55 ( mg/g) was recorded at stations I. Comparison of Potassium concentration in sediment and subsurface water at different stations, during January 2009 is presented
in this Table ( 39 )
Fig ( 45 ).
stations
I
II
III
IV
V
VI
VII
potassium in dry sed.( mg/g)
7.55
12.04
10.66
17.46
15.27
16.64
17.23
potassium in water (mg/l)
5.97
13.41
6.12
6.45
6.37
6.01
6.41
20 18 16 14 12 10 8 6 4 2 0 i
ii
iii
iV
sediment mg/ g
188
V
Vi
water mg/l
Vii
Stations
…………………………………….…………..…………... Results and discussion At the reference station ( I ) the minimum values of Potassium concentration are recorded in the sediment and water compared with that , at iron and steel drain ( II ) in which the highest value recorded in water and relative decreasing in the sediment .
D- Heavy Metals According to (Forstner and Wittman, 1979), the sediment existing at the bottom of the water column play a major role in the pollution scheme of the river system by heavy metals. They reflect the current quality of the water system and can be used to detect the presence of contamination that don't remain a soluble after discharge into water. Recently, a number of studies have been analyzed and reported on the presence of trace metals in the sediment of the rivers and lakes in the world. Where the bottom sediment act as accumulator for these metals and the rate of accumulation depends mainly on the environmental parameters such as pH, temperature, salinity, hardness, dissolved oxygen... etc. (Elewa et al, 1990 and Soltan, 1994).
1 – Iron The distribution of iron in water system depend on dissolved oxygen and is usually present as insoluble Fe(OH) 3 or ferric oxide. The ferrous form can only exist in the absence of oxygen
(Hassouna, 1989) and (Goher, 1998), i.e. at
oxygenated water, the iron is precipitated to the bottom sediments as ferric form.
The present studies in the Nile reveal that sediments during January 2009 The maximum value of 5.141 (mg/g) was recorded at station VI while the minimum value of 1.963 (mg/g ) was recorded at stations II behind iron and steel drain.
189
…………………………………….…………..…………... Results and discussion Iron concentration in the sediment and subsurface water at different stations, during January 2009 is presented in Table ( 40 ) Fig ( 46) .
stations
I
II
III
IV
V
VI
VII
Iron in dry sed. mg/g
2.88
1.96
4.92
4.95
4.9
5.14
5.07
Iron in water mg/l
0.296
1.52
0.267
0.404
0.219
0.214
0.249
6 5 4 3 2 1 0 i
ii
iii
iV
sediment mg/g
V
Vi
water mg/l
Vii
Stations
Thus at iron and steel drain Station ( II ) the highest value of iron in water and the lowest value in the sediment may be attributed to that the ferrous form more soluble present .
Generally, the course of oxidation mainly influenced by other factors for understanding of the relation of iron in natural water Among them, pH has a particularly strong effect. Thus, at pH 7, ferrous bicarbonate can only exist when the water contain no more (0.5 mg/1) of oxygen. If oxygen content is higher or the reaction more alkaline, Fe(OH) 3 is almost instantaneously precipitated (Goher, 1998).
190
…………………………………….…………..…………... Results and discussion According to Sayed 2003, the sediment acts as a sink for pollutant in the aquatic environment where the suspended particles settle the adsorbed pollutants to be removed from the water column. In Edku, the relatively high value of iron of 36.29 and 35.8 g/ kg are due to increase in clay.
2- Manganese Manganese exist in the soil principally as MnO 2 which is very insoluble in water under reducing conditions, The manganese in the dioxide form is reduced from valence 4 to 2 and solution occurs as with ferric oxide (Sawary and Mecarty, 1967). The maximum value of 0.41 mg/g was recorded at station V while the minimum value of 0.08 mg/g was recorded at stations II behind iron and steel drain. Comparison between Manganese concentration in sediment and subsurface water at different stations, January 2009 is presented in this Table ( 41 ) Fig ( 47).
stations
I
II
III
IV
V
VI
VII
manganese in dry sed. mg/g
0.11
0.08
0.396
0.32
0.41
0.36
0.34
manganese in water mg/l
0.049
0.365
0.059
0.06
0.058
0.055
0.052
0.45 0.4 0.35 0.3 0.25 0.2 0.15 0.1 0.05 0 i
ii
iii
iV
sediment mg/ g
191
V
Vi
water mg/l
Vii
Stations
…………………………………….…………..…………... Results and discussion At iron and steel drain Station ( II ) the highest value in water and lowest value in the sediment may be attributed to low value of pH 7.65 and dissolved oxygen 4.5 mg/l , or may be attributed to fresh manganese comes from iron and steel drain.
Generally, manganese is easy associated with carbonates in the form of Mn II and its relative stability depending on, pH, dissolved oxygen and Eh in the particles at high contents of CaCO 3 (Ahlers et al., 1991). The element occurs usually naturally either in carbonate rocks or in soils in concentrations comparable with those detected in dust-fall. For instance, its average content in limestone rocks is 0.04% (Rankoma and Shama,1950), while its terrestrial abundance in soils ranges from 0.02 - 0.5 % (Day, 1963). The manganese concentration is very high in the oxidized upper most layer of off shore sediment (Takamatsu et al, 1985). According to (Yagi, 1996) explained the steps of precipitation of Mn into sediment in the oxic and anoxic layers as follows: 1- Dissolved Mn supply from vertical eddy diffusion 2- Manganese reduction by Mn-reducing bacteria 3- Chemical reduction of manganese 4- Particulation of manganese dioxide by dissolved oxygen 5- Sinking of Mn particulate.
3- Zinc Zinc is essential and beneficial element in human growth. Also, it is plant micronutrient, being an important constituent in the formation of enzymes and nucleic acid synthesis (Kouadiol and Terfry, 1987). On the whole , Zinc may occur in the sediment as the zinc carbonate, zinc oxide and zinc sulphide (Anon, 1978). Also, the organic matter enrichment in the sediment increase the deposition of sediment (Elewa et al, 1990).
192
…………………………………….…………..…………... Results and discussion The maximum value of 494.5 µg/g was recorded at stations II behind iron and steel drain while the minimum value of 12.89 µg/g was recorded at stations I . Zinc concentration in sediment and subsurface water at different stations, during winter season is presented in this Table ( 42 ) Fig ( 48 ).
stations
I
II
III
Zinc in sediment µg/g
12.89
494.5
29.1
Zinc in water µg/l
15.66
34.6
8.69
IV
V
VI
VII
29.26 36.47
27.39
30.91
17.99
6.23
13.52
9.69
500 450 400 350 300 250 200 150 100 50 0 i
ii
iii
iV
sediment ug/ g
V
Vi
water ug/l
Vii
Stations
At iron and steel drain (II) the highest value in water and very high value in the sediment may be attributed to fresh Zinc comes from iron and steel drain and very fast deposition under low dissolved oxygen and low pH. Jenve (1968) showed that, the zinc has strongly association with Fe-Mn oxides and accumulate within clay.
193
4- Copper Copper is a micronutrient element fundamental to all forms of life. In excessive amounts, it may become toxic to organisms by inducing a reduction in enzymes activity or a random rearrangement of structural proteins (Bowen, 1979). On the other hand, copper concentrations of 0.1 to 1.0 mg/1 in nutrient solutions have been shown to be toxic to a large number of plants. Toxicity levels in nutrient solutions and limited data in soil suggest a maximum concentration of 0.2 mg/1 for use of all soils (National Academy of Science, 1972). The present results reveals that, the maximum value of 53.12 µg/g was recorded at stations V while the minimum value of 16.85 µg/g was recorded at stations I. Copper concentration in the sediment and subsurface water at different stations, during January 2009 is presented in this Table ( 43 ) Fig ( 49 ).
stations
I
II
III
IV
V
VI
VII
Copper in dry sed. µg/g
16.85
38.03
34.36
50.24
53.12
35.05
34.1
Copper in water µg/l
6.88
28.63
7.01
7.388
10.62
5.47
7.74
60 50 40 30 20 10 0 i
ii
iii
iV
sediment ug/g
194
V
Vi
water ug/l
Vii
Stations
…………………………………….…………..…………... Results and discussion At iron and steel drain ( II ) the highest value in water and relative increase occur in the sediment and the highest value in sediment where recorded at station V . Generally, the increase in copper content in the sediment of different stations and drains may be attributed to the removal of copper from the water column mediated by the decay of the plankton or due to adsorption on the suspended matter or the complexation with organic matter leaving the water body to the sediment as reported in Muse River flowing through France, Belgium and Holland (NatherKhan and Lim, 1991).
Also,
the
major contribution of element to air-bone particulate matter
are: 1- crust materials, such as argillaceous sediments, which are often enriched with metal copper, and 2- man made sources, such as fossil fuel combustion, metallurgical industries and agricultural processes through the use of some copper compounds as inorganic pesticides ( El -Ghandour et al, 1982).
5- Lead Lead is considered as one of the most toxic elements to human and animals, and the toxicity of lead is largely depend on its solubility. If it present in form of PbSO 4 it is much soluble than PbCO 3 and has a great toxicity. While in the form of PbS it has very low solubility and low toxicity. Lead enters the aquatic environment throughout precipitation of lead dust fall out, leaching soil and industrial wastes discharge (U.S. EPA, 1976). The maximum value of Pb in the Nile sediments was 67.08 µg/g recorded at stations II behind iron and steel drain while the minimum value of 2.66 µg/g was recorded at station I , in the following table ( 44 ) Fig ( 50 ) show a comparison of Lead concentration in sediment and subsurface water at different stations, during January 2009 .
195
…………………………………….…………..…………... Results and discussion
stations
I
II
III
IV
V
VI
VII
Lead in dry sed. µg/g
2.66
67.08
7.14
10.55
10.43
5.98
7.41
Lead in water µg/l
8.23
5.13
3.41
7.961
4.51
2.83
9.74
80 70 60 50 40 30 20 10 0 i
ii
iii
iV
V
Vi
Vii
station sediment ug/ g
At
water ug/l
iron and steel drain station( II ) the highest value in the sediment and
normal range occur in the water. Generally, lead complex rapidly with organic matter and therefore closely connected to the carbon cycle of the lakes (Santssh, 1988). For metals, with strong affinity to humic matter but not easily mobilized by acidification may reinforce the effect of increased atmospheric deposition on sediment concentration (Field e al., 1994). Bergkvist et al (1989) and (Johansson et al 1991), in Sweden and Germany ecosystem, they show a major part of atmospherically deposited lead (70 - 95%) to be accumulated in soils, whereas the release to the aquatic environment is largely controlled by the amount of dissolved humic matter, therefore pictures affecting input of humic matter and carbon cycle within lakes will inevitably influence sediment concentration of Pb.
196
…………………………………….…………..…………... Results and discussion
6- Cadmium Cadmium precipitates as CdCO 3 co-precipitation similar to lead (Borg, 1984). It associated with organic fraction in the sediments but to a lesser extent than Pb (Fjeld et al, 1994). The most important difference between Cd and Pb in waters system, is the strong direct effect of pH on Cd, indicating that, the particle bond Cd is mobilized to the water phase by acidification. In other words, Cd is mobilized to the water phase by acidification in other words Cd is sorbed to sedimentary organic matter and the binding intensity is very sensitive to pH variation (VosIIikiotis et al., 1990 ) in the present studies Cd distribution shows, The maximum value of 1.156 µg/g was recorded at stations II behind iron and steel drain while the minimum value of 0.095 µg/g was recorded at station I as shown in the following table ( 45 ) Fig (51). Cadmium concentration in sediment and subsurface water at different stations during January 2009
stations
I
II
III
IV
V
VI
VII
Cadmium in dry sed. µg/g
0.095
1.156
0.142
0.116
0.188
0.142
0.145
Cadmium in water µg/l
0.041
0.101
0.082
0.048
0.021
0
0.014
1.2 1 0.8 0.6 0.4 0.2 0 -0.2
i
ii
iii
iV
V
Vi
Vii
stations sediment ug/ g
197
water ug/l
…………………………………….…………..…………... Results and discussion At iron and steel drain station (II) the highest value of cdrecorded in water and very high value in the sediment may be attributed to fresh cadmium comes from iron and steel drain and very fast deposition. Generally, the metals
adsorbed
by
sediments
can
be held by
complexation with weakly acidic functional groups or by ion exchange of metal ions. A multisite binding model, which incorporates the effect of pH, has been applied to describe the adsorption of cadmium onto sediment. The model has been used satisfactorily to predict the extent of adsorption over the pH range of 4.5 - 7.0 (Krauskopf, 1979). Most of the cadmium has been precipitated as carbonate instead of hydroxide when the pH was below 8.5 (Abu EI-Ela, 1989). The major proportion of cadmium was associated with organic/sulphide fraction at very low concentrations in more labile phase. Also, cadmium is non-essential highly toxic element, which accumulates in the kidneys of mammals and can cause kidney disfunction and damage (U.S. EPA, 1972).
7- Nickel Exposure to nickel metal and soluble compounds should not exceed 0.05 mg/cm³ in nickel equivalents per 40-hour work week. Nickel sulfide fume and dust is believed to be carcinogenic, and various other nickel compounds In this present studies , Ni concentration shows , the maximum value of 26.11 µg/g was recorded at stations VI while the minimum value of 12.79 µg/g was recorded at station I . Nickel concentration in the sediment and subsurface water at different stations, during January 2009 are presented in this Table ( 46 ) Fig ( 52). stations
I
II
III
IV
V
VI
VII
Nickel in sediment µg/g
12.79
14.63
24.07
22.14
24.62
26.11
24.28
Nickel in water µg/l
2.258
4.053
2.235
3.214
1.554
2.245
2.083
198
…………………………………….…………..…………... Results and discussion
30 25 20 15 10 5 0 i
ii
iii
iV
V
sediment ug/ g
Vi
Vii
water ug/l
At iron and steel drain station ( II ) the highest value in water and relative decrease occur in the sediment .
8- Chromium Chromium compounds were used in dyes and paints and the tanning of leather, these compounds are often found in soil and groundwater at abundant industrial sites, now needing environmental cleanup and remediation per the treatment of brownfield land. Primer paint containing hexavalent chromium is still widely used for aerospace and automobile refinishing applications. (Wikipedia, 2009). in the present studies , the Nile sediment show The maximum value of Cr 37.89 µg/g was recorded at stations II behind iron and steel drain while the minimum value of 14.38 µg/g was recorded at station I, As given in the following table ( 47 ) Fig ( 53 ). Chromium concentration in sediment and subsurface water at different stations, during January 2009 station
I
II
III
IV
V
VI
VII
Chromium in sediment µg/g
14.38
37.89
26.73
26.61
35.96
31.65
27.42
Chromium in water µg/l
1.252
3.132
1.189
1.369
1.545
1.024
1.566
199
…………………………………….…………..…………... Results and discussion
40 35 30 25 20 15 10 5 0 i
ii
iii
iV
sediment ug/ g
V water ug/l
Vi
Vii
stations
At iron and steel drain stations ( II ) the highest value of Cr recorded in water and very high value in the sediment may be attributed to the inflow of fresh chromium comes from iron and steel drain .
200
…………………………………….…………..…………... Results and discussion
Comparison between Inductively coupled plasma (ICP-OES) and spectrophotometer for determination of iron and aluminum concentration A- Principle Methodology : is frequently used when "method" would be more accurate Methodology includes the following concepts as they relate to a particular discipline or field of inquiry 1- a collection of theories, concepts or ideas 2- comparative study of different approaches 3- critique of the individual methods
Inductively Coupled Plasma (ICP) is an analytical technique used for the detection of trace metals in environmental samples. The primary goal of ICP is to get elements to emit characteristic wavelength specific light which can then be measured. The technology for the ICP method was first employed in the early 1960's with the intention of improving upon crystal growing techniques.
Spectrophotometer is a photometer (a device for measuring light intensity) that can measure intensity as a function of the color, or more specifically, the wavelength of light.
Type of metals in water samples according to APHA 1995 1- Dissolved metals: Those metals in an unacidified sample that pass through a 0.45-µm membrane filter. 2. Suspended metals: Those metals in an unacidified sample that are retained by a 0.45-µm membrane filter. 3. Total metals: The concentration of metals determined in an unfiltered sample after vigorous digestion, or the sum of the concentrations of metals in the dissolved and suspended fractions. 4. Acid-extractable metals: The concentration of metals in solution after treatment of an unfiltered sample with hot dilute mineral acid to determine either dissolved or suspended metals.
201
…………………………………….…………..…………... Results and discussion
1- Iron analysis Iron concentration in subsurface water at different stations, during winter season by using ICP-OES and spectrophotometer technique is
presented
in
this Table ( 48 ) Fig ( 54 ):
station
I
II
III
IV
V
VI
VII
ICP-OES analysis
0.296
1.524
0.267
0.404
0.219
0.214
0.294
Spectrophotometer analysis
0.39
0.84
0.28
0.48
0.44
0.36
0.22
1.8 1.6 1.4 1.2 1 0.8 0.6 0.4 0.2 0 i
ii
iii
iv
v
vi
vii
spectrophotometer ( 1.10 phenanthroline method) inductively coupled plasma
At iron and steel drain (ii) the highest gap between ICP-OES and spectrophotometer technique may be attributed to Acid-extractable metals more present at drain station and ICP samples must be acidify with 5 ml concentrated nitric acid (HNO 3 ) to pH
