ECOLOGICAL STUDY OF THE MUNICIPAL SOLID WASTE DISPOSAL AREA IN HALABJA CITY – KURDISTAN REGION OF IRAQ A THESIS SUBMITTED TO THE COUNCIL OF FACULTY OF SCIENCE AND SCIENCE EDUCATION SCHOOL OF SCIENCE AT THE UNIVERSITY OF SULAIMANI IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE IN BIOLOGY ( ECOLOGY AND POLLUTION )
By SALAR HUSSEIN KARIM ( B.Sc. Biology ( 2004 ) , Salahaddin University – Erbil ) ( H.D. Biology ( 2010 ), Salahaddin University - Erbil )
Supervised By DR. SHERKO ALI MUHAMMAD LECTURER
Sarmawaz 2714 K.
Safer 1436 H.
November 2014 A.D.
( ) بسم اهلل الرمحن الرحيم " َ َ َ ْ َّ َ ْ اس ن ال ِي د ي أ ت ب س ك ا م ب ر ح ب ل ا و ر ب ال ِي ف د ا س ف ال ر ه ظ ُ َ ْ َ َ َ ِ ِ ْ َ َ ِّ َ ََ ِ " َض الَّذِي َع ِملُوا لَ َعلَّ ُه ْم َي ْر ِج ُعون َ لِ ُيذِي َق ُهم َب ْع
14:الروم “In The Name of Allah, the All-Merciful, the Ever-Merciful” Corruption has appeared In the Land and the Sea for what Mankind’s hands have earned, He may make them taste some (part) of that which they have done, that possibly they would return. Surratt AL-Rum :41
Supervisor Certification I certify that the preparation of thesis titled "Ecological Study of the Municipal Solid Waste Disposal Area in Halabja City - Kurdistan Region of Iraq" accomplished by ( Salar Hussein Karim ), was prepared under my supervision in
the School of Science, Faculty of Science and Science Education at the
University of Sulaimani, as partial fulfillment of the requirements for the degree of Master of Science in Biology.
Signature: Name: Dr. Sherko A. Muhammad Title: Lecturer Date: / / 2014
In view of the available recommendation, I forward this thesis for debate by the examining committee.
Signature: Name: Dr. Huner H. Arif The head of biology department Date:
/
/ 2014
Language Evaluation Certification This is to certify that I, Shilan Ali Hama Sur, have proofread this thesis entitled " Ecological study of the municipal solid waste disposal area in Halabja City - Kurdistan Region of Iraq" prepared by ( Salar Hussein Karim ). After marking and correcting the mistakes, the thesis was handed again to the researcher to make the corrections in this last copy.
Proofreader: Shilan A. Hama Sur Date: Sept. 4th , 2014 Department of English , School of Languages, Faculty of Humanities, University of Sulaimani
Examining Committee Certification We certify that we have read this thesis entitled "Ecological study of the municipal solid waste disposal area in Halabja City - Kurdistan Region of Iraq" prepared by ( Salar Hussein Karim), and as Examining Committee, examined the student in its content and in what is connected with it, and in our opinion it meets the basic requirements for the degree of Master of Science in Biology ".
Signature:
Signature:
Name: Dr. Yahya A. Shekha Title: Assist. Prof. Date:
/
/ 2014
( Chairman )
Signature:
Name: Dr. Trifa K. Jalal Title: Assist. Prof. Date:
/
/ 2014
( Member )
Signature:
Name: Dr. Rezan O. Rasheed
Name: Dr. Sherko A. Muhammad
Title: Assist. Prof.
Title: Lecturer
Date:
Date:
/ / 2014
( Member )
/ / 2014
( Supervisor ‐ Member )
Approved by the Dean of the Faculty of Science.
Signature: Name: Dr. Bakhtiar Kader Aziz Title: Professor Date:
/
/ 2014
( The Dean )
Dedication
To : The Soul of my father My Mother,brothers and sister My friends Those who have a special place in my heart….
Salar Salar husein
ACKNOWLEDGEMENTS
To begin with, I thank (Allah) for his blessing and making me able to complete and perform this study with success, My sincere thanks and appreciation to my supervisor, Dr. Sherko Ali Muhammad for his, encouragement and guidance throughout the work.
I would like to offer my thanks to the Deanery of the Faculty of Science;I’m no less thankful to Dr.Huner H. Arif, Head of the Biology Department for this great support and providing the facilities required for this research. I wish to express my deepest appreciation and gratefullness to Mr. Mohammed S. Rashid, Assist. Lecturer in Agriculture Technical College of Halabja, and all lecturers of the Technical institute of Halabja. My deepest gratitude, great respect and
particular thanks and
appreciations to his my friend Mr. Karzan muhummad Hawrami
for this
great help, encouragements and support. I am grateful to the Chemical analysis laboratory in the Directorate of Health Prevention in Sulaimani especially, Mr. Hiwa for his assistance in the sample analysis. I am also grateful to Mis. Laila, Mr. Nawzad, Mr. Kawa and Mr. Dler for their support and help over the period of this work. Finally,my thanks to all those I forgot them here to mention his /her name ; all who assisted me even by one useful scientific word directly or indirectly.
salar
I
Abstract Abstract Handling and disposal of solid waste can be a major environmental problem in developing countries. In Kurdistan region of Iraq solid waste is not treated and managed properly. It is only collected from the house holds and disposed on the outskirts of the cities as a pile of garbage nearby the agricultural areas, sometime it is burnt or partially dumped. The leachates can be clearly seen coming out from the sites flowing over the agricultural fields. An evaluation of the impact of long term (20 years) solid waste disposal on the soil and water physicochemical properties and environmental quality is conducted in Halabja province Kurdistan region of Iraq. Solid waste in Halabja including domestic, hospital and industrial and Agricultural wastes are being disposed of somewhere close to the city (5km from city center) where farmers are farming. Only in Halabja city, its population around 55764 Persons, approximately <1 kg per capita per day of solid waste is being produced and about 80 tons of waste is transferred by municipal vehicles ( dumper, tractors, trucks ) in to the solid waste disposal area. The main aim of this study is to assess the impact of long term solid waste disposal on water and soil physicochemical characteristics. The samples were collected monthly starting from May to December 2012 including ground and surface water, soil and wheat around the solid waste disposal area. The samples were analyzed for physicochemical characteristics and some trace heavy metal concentrations. Water temperature was measured directly in the field and ranged from (18.1 – 27 0C, 17.4 - 19.5 0C ) for both ground and surface water respectively. The results showed the ground and surface water to be characterized by alkalinity and the range of pH was consider ( 6.5 - 7.4, 7.5 - 7.9 ) respectively and the soil in the study area was calcareous in nature ( pH 7.9 - 8.25 ) and classified by silty loam, sandy and silty clay. Electrical conductivity ranged was ( 363 – 662.3 μs.cm-1 ) , (357.3- 406.7 μs.cm-1 ) for ground and surface water respectively, and did not exceed the WHO guideline Electrical conductivity in drinking water while the mean range ( 363.7 580.3 ms.cm-1) was recorded for soil in the study areas. The range of dissolved Oxygen was (5.8-7.3) and (7.2-7.8) mg.l-1 for ground and surface water respectively, whereas the range of Biological oxygen demand ( BOD5 ) was ( 2.8 - 3.6 ) and (4.1 -4.4 ) mg.l-1 suggesting that the water is safe to be consumed. Slightly higher values II
Abstract were found for total hardness ranging from ( 250 - 413.7 ) and ( 265.3 – 305.3 ) mg CaCO3.l-1 for both ground water and surface water respectively, while ( 61.7 – 147.3 ) and ( 37.3 - 77) mg CaCO3.l-1 were reported for calcium and magnesium hardness respectively in the groundwater and ( 55.3 – 74.3 ( and ( 42.3 – 57.7 ) mg CaCO3.l-1 were found for calcium and magnesium hardness respectively in surface water. The range of Alkalinity was ( 175 – 246 ) mg.l-1 and ( 194.3 – 271.3 ) mg.l-1 for ground and surface water respectively which is higher than the WHO desirable limit recommended for drinking water. As for Sodium and Potassium in both ground and surface water the values detected were below the WHO guideline for drinking water ( 4.3 - 8.7 and 5.5 – 10 ) mg.l-1 and ( 0.6 -1.6 and 1.1 - 2.8) mg.l-1 respectively. Similarly, chloride and Nitrate were found to be under the suggested values set by WHO for ground and surface water ( 70 – 195 and 55.7 – 63.7) mg.l-1 and ( 9.3 – 17 and 9.5 - 16.1 ) mg.l-1 respectively. Moreover, total Sulfer and Nitrogen was analysed for soil samples, using Carbon Nitrogen Sulfur ( CNS ) analyser, the results were ( 0.002 % - 0.030 % ) and ( 6.9 % - 3.9 % ) respectively and the results for essential elements Na, Mg, K and Ca were ( 2766 – 3805 ) mg/kg1
, ( 13326 – 18998 ) mg.kg-1 ,( 13193 – 15835 ) mg.kg-1 and ( 42489 – 75648 ) mg.kg-1 of soil
respectively. High concentrations of Ca in all soil samples was expected because the regional geology is calcareous. The rate of organic matter between ( 10.3 – 12.1 % ), and the rate of Calcium carbonate and Bicarbonate was ( 20.4 % – 29.2 % ) and ( 19 – 48.4 ) mg.kg-1 respectively. While the concentration of Available phosphorus was between ( 2.3–8.7 ) mg.kg-1 . Heavy metal and metalloid concentrations measured for Zn, As, Cd, Fe, Pb and Ni were ( 0.002 – 0.012 ) mg.l-1, ( 0.01 – 0.097 ) mg.l-1, ( 0.002 – 0.003 ) mg.l-1, ( 0.011- 0.079 ) mg.l-1, ( 0.035 – 0.051 ) mg.l-1 and ( 0.004 -0.015 ) mg.l-1 for ground water respectively, while (0.003 0.009 ) mg.l-1, ( 0.05 – 0.16 ) mg.l-1, ( 0.002 – 0.004 ) mg.l-1, ( 0.051 – 0.171 ) mg.l-1, ( 0.04 – 0.044 ) mg.l-1, ( 0.021 – 0.022 ) mg.l-1 for surface water respectively. However, As and Pb concentration were found to be higher than the permissible values recommended by WHO for drinking water quality while the rest were below the safe limits. The concentrations of heavy metals and metalloids were found in order of Mn> Zn>Cu >Ni> Pb>Cr>As> Cd ( 987 - 1187 mg.kg-1, 225.03 – 915.3 mg.kg-1, 232.8- 301.1 mg.kg-1, III
Abstract 150.4 – 192.2 mg.kg-1, 76.71 - 193.1 mg.kg-1, 142.2 – 173.1 mg.kg-1, 14.23 – 20.15 mg.kg-1 and 2.317 – 5.712 mg.kg-1 ) which exceed the European union standard for Ni, Zn, Cr, Cd, Mn, Cu, while Pb and As were found to be within the range of all trace elements for agricultural soils. The range for trace elements for wheat samples were 115 mg.kg-1 for Zn, 0.0313 mg.kg-1 for As, 1.2 mg.kg-1 for Cd, 2.1 mg.kg-1 for Pb, 1.19 mg.kg-1 for Ni and 0.058 mg.kg-1 for Cr. The concentration of As, Cd, Pb and Ni in wheat grown around the solid waste disposal area were constantly higher than the recommended values set by United Kingdom and WHO/EU limits. The mean of Water Quality Index for ground and surface water were 90.23 and 102.5 respectively during the study period, hence the water can be recognized as “good water” for ground water and “Poor water” for surface water according to water quality classification based on Water Quality Index . The values of combined HI (Hazard Indices) were lower than 1 for all heavy metals in ground and surface water samples, indicating no health risk for the local population from the drinking water in the area according to hazard index.
IV
List of contents Series
Subject
Page
Acknowledgements
I
Abstract
II
List of Content
V
List of Tables
X
List of Figures
XII
List of plate
XII
List of Abbreviations
XIII CHAPTER ONE
1.
Introduction
1 CHAPTER TWO
2.
Literature Review
3
2.1
Pollution
3
2.1.1
Environmental pollution in Iraq
3
2.2
Municipal solid waste
4
2.2.1
Effect of municipal waste disposal area on urban and peri urban agriculture
6
2.3
Physico - chemical studies of water
7
2.4
Physico - chemical studies of Soil
12
2.5
Heavy metal study in plants
18 CHAPTER THREE
3
Description of the study Area
21
3.1
A brief overview about Kurdistan Region of Iraq
21
3.2
Halabja and Social Aspects
21
3.3
Soil and Lithology Aspect
21
3.4
Climate
22
3.4.1
Temperature Aspect
22
V
3.4.2
Rainfall Aspect
22
3.5
Halabja open dump area description (HALW)
23
3.7
Population
27
3.8
Solid Waste Production
27
3.9
Description of studied sites around solid waste dumping area
27
CHAPTER FOUR 4
Materials and Methods:
29
4.1
Sample collection
29
4.1.1
Water sample collection
29
4.1.2
Soil samples collection
29
4.2
Field Analysis
30
4.2.1
Elevation from sea level (m)
30
4.2.2
Air and Water Temperature (°C)
30
4.2.3
Water Hydrogen ion potential (pH)
30
4.2.4
Electrical Conductivity (EC) in µs.cm-1
30
4.3
Water Laboratory Analysis
30
4.3.1
Determination of Biological Oxygen Demand concentration (BOD5) in mg.l-1
30
4.3.2
Water Hardness
31
4.3.2.1 Total Hardness (TH) in mg CaCO3.l-1
31
4.3.2.2 Calcium hardness
31
4.3.2.3 Magnesium hardness
31
4.3.3
Total Alkalinity mg.l-1
31
4.3.4
Nitrate Nitrogen (NO3ˉ) in mg-at-N-NO3.l-1
32
4.3.5
Major ions
32
4.3.5.1 Sodium
32
4.3.5.2 Potassium
32
4.3.5.3 Chloride (Cl-)
32
4.3.6
Water analysis for Trace heavy metals concentrations
33
4.4
Soil Laboratory Analysis
33
4.4.1
Soil pH and Electrical conductivity
33 VI
4.4.2
Loss on Ignition (LOI)
33
4.4.3
Soil Nitrogen and Sulfer content measurement:
34
4.4.4
Calcium Carbonate (CaCO3)
34
4.4.5
Bicarbonate mg.kg-1
34
4.4.6
Available Phosphorous
34
4.4.7
Soil analysis for total elemental (sodium, potassium, calcium ,magnesium and Trace heavy metals ) concentrations.
35
4.5
Preparation and Analysis of Plant Heavy metals.
36
4.6
Calculating of Water Quality Index ( WQI )
37
4.7
Calculation of Hazard Quotient (HQ) Indices
38
4.8
Statistical analysis
38
CHAPTE FIVE 5
RESULTS
39
5.1
Physico-chemical analysis for monthly water sample during the studied period
39
5.1.1
Water Temperature
39
5.1.2
Hydrogen ion concentration pH
39
5.1.3
Electrical conductivity ( EC ) µs.cm-1
41
5.1.4
Dissolved oxygen ( DO ) mg.l-1
41 1
5.1.5
Biological oxygen demand ( BOD ) mg.l-
43
5.1.6
Total Hardness ( TH ) mg CaCO3.l-1
43
5.1.7
Calcium Hardness mg CaCO3.l-1
45
5.1.8
Magnesium Hardness mg CaCO3.l-1
45
5.1.9
Total Alkalinity mg CaCO3.l-1
47
5.1.10
Chloride mg.l-1
47
5.1.11
Sodium(mg.l-1)
49
5.1.12
Potassium (mg.l-1)
49
5.1.13
Nitrate nitrogen (NO3ˉ) mg-at-N-NO3.l-1
51
5.2
Water heavy trace metals
51
-1
5.2.1
Zinc ( Zn ) mg.l
5.2.2
Arsenic(As) mg.l-1
51 53
VII
5.2.3
Cadmium (Cd) mg.l-1
53
5.2.4
Iron (Fe) mg.l-1
55
5.2.5
Lead (Pb) mg.l-1
55
5.2.6
Nickel (Ni) mg.l-1
57
5.3
Physico-chemical analysis for monthly Soil sample during the studied period
58
5.3.1
Soil pH
58
5.3.2
Soil Electrical conductivity (EC) µs.cm-1
58
5.3.3
Total Sulfur ( 100% )
60
5.3.4
Total Nitrogen ( % )
60
5.3.5
Organic matter ( LOI% )
62
5.3.6
Sodium concentration ( mg.kg-1 )
62
5.3.7
Magnesium concentration (mg.kg-1)
64
5.3.8
Potassium (K) mg.kg-1
64
5.3.9
Calcium (Ca) mg.kg-1
66
5.3.10
Calcium carbonate ( % )
66
5.3.11
Bicarbonate ( HCO3- ) mg.kg-1
68
5.3.12
Available phosphorus mg.kg-1
68
5.4
Soil Heavy Trace Metals:
70
5.4.1
5.4.1 Zinc ( Zn ) mg.kg-1
70
5.4.2
Arsenic ( As ) mg.kg-1
70
5.4.3
Cadmium ( Cd ) mg.kg-1
72
5.4.4
Lead ( Pb ) mg.kg-1
72
5.4.5
Nickle ( Ni ) mg.kg-1
74
5.4.6
Chrome ( Cr ) mg.kg-1
74 -1
5.4.7
Manganese ( Mn ) mg.kg
76
5.4.8
Copper ( Cu ) mg.kg-1
76
5.5
Trace Heavy Metals Concentration ( mg.kg-1 ) in wheat grain
78
5.6
Water Quality Index Via Ground Water
78
5.7
Water Quality Index Via Surface Water
78
5.8
Hazard Index Via Ground Water
80
5.9
Hazard Index Via Surface Water
80 VIII
Chapter six 6
Discussion
81
6.1
The analysis of Physical and chemical parameters
81
6.1.1
Water temperature
81
6.1.2
Water and soil hydrogen ion concentration ( pH )
81
6.1.3
Water and soil electrical conductivity ( EC )
83
6.1.4
Dissolve oxygen ( DO )
84
6.1.5
Biological oxygen demand ( BOD5 )
85
6.1.7
Total hardness ( TH )
86
6.1.8
Calcium and Magnesium Hardness
87
6.1.9
Alkalinity
88
6.1.10
Chloride ( Cl- )
89
6.1.11
Sodium ( Na+1 ) and Potassium ( K+ ) concentration
90
6.1.12
Nitrate ( NO3 )
91
6.1.13
Total sulfur in soil mg.kg-1
93
6.1.14
Total nitrogen in Soil ( % )
93
6.1.15
Soil Organic Matter ( OM ) %
94
6.1.16
Base elements ( Na+, K+, Mg+2 and Ca+2 )
95
6.1.17
Soil carbonate and bicarbonate mg.kg-1
96
6.1.18
Available Phosphorus in Soil
97
6.2
Heavy metal concentration in water and soil
98
6.2.1
Trace element concentrations in water samples
99
6.2.2
Trace element concentrations in soil samples
103
6.2.3
Accumulation of trace elements in the wheat grain
107
6.3
Water Quality index
109
6.4
Risk Assessment ( Hazard Indices )
110
Conclussion
111
Recommendation
112
Reference
113 IX
Summary in Kurdish
A-C
Summary in Arabic
E-F
List of Tables NO. 2.1 3.1 3.2 5.1 5.2 5.3 5.4 5.5
5.6 5.7 5.8 5.9 5.10 5.11 5.12 5.13 5.14
Page
List of Table Listed the average percentage composition of solid wastes for Halabja city during ( 2011 and 2012) years. The mean monthly Temperature and precipitation records for Halabja town, during the studied period (may to Dec.2012). Shows sites, coordinates and description of each soil, water and grain agricultural site. Temperature Concentration in Water (C o) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. (pH) concentration value in Water with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. Electrical Conductivity concentration in Water (μs.cm-1) at 25 0C with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. Dissolved oxygen Concentration value in Water (mg.l-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. Biological oxygen demand Concentration value in Water (mg.l-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. Total hardness concentration value in Water (mg.l-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. Calcium hardness Concentration value in Water (mg.l-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. Magnesium Hardness Concentration value in Water (mg.l-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December. Alkalinity Concentration value in Water (mg.l-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. Chloride Concentration value in Water (mg.l-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. Sodium Concentration value in Water (mg.l-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. Potassium Concentration value in Water (mg.l-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012 (Nitrate) Concentration value in Water (mg.l-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012 Zinc (Zn) Concentration value in Water (mg.l-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. X
5 22 28 40 40 42 42 44
44 46 46 48 48 50 50 52 52
5.15 5.16 5.17 5.18 5.19 5.20 5.21 5.22 5.23 5.24 5.25 5.26 5.27 5.28 5.29 5.30 5.31 5.32 5.33 5.34
Arsenic ( As ) Concentration value in Water (mg.l-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. Cadmium ( Cd ) Concentration value in Water (mg.l-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. Iron (Fe) Concentration value in Water (mg.l-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012 Lead ( Pb ) Concentration value in Water ( mg.l-1 ) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012 Nickel (Ni) Concentration value in Water (mg.l-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012 (pH) concentration in soil with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. (EC) concentration in soil (μs.cm-1) with mean and (±SD) at solid waste disposal area in Halabja City from May to December 2012 Total Sulfer concentration in soil (%) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012 Total Nitrogen concentration in soil (%) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. Organic matter concentration in soil ( LOI% ) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. Sodium (Na) concentration in soil (mg.kg-1) with mean and (±SD) at solid waste disposal area in Halabja City from May to December 2012 Magnesium (Mg) concentration in soil (mg.kg-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. Potassium (K) concentration in soil (mg.kg-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. Calcium (Ca) concentration in soil (mg.kg-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. (Calcium carbonate) concentration in soil (%) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. (Bicarbonate) concentration in soil (mg.kg-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. (Available phosphorus) concentration in soil (mg.kg-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. Zinc (Zn) concentration in soil (mg.kg-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. Arsenic (As) concentration in soil (mg.kg-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. Cadmium(Cd) concentration in soil (mg.kg-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. XI
54 54 56 56 57 59 59 61 61 63 63 65 65 67 67 69 69 71 71 73
5.35 5.36 5.37 5.38 5.39
5.40 5.41 5.42 5.43 5.44 6.1 6.2 6.3
Lead (Pb) concentration in soil (mg.kg-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. Nickle (Ni) concentration in soil (mg.kg-1) with mean and (±SD) a solid waste disposal area in Halabja city from May to December 2012. Chrome (Cr) concentration in soil (mg.kg-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. Manganese (Mn) concentration in soil (mg.kg-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. Copper ( Cu ) concentration in soil (mg.kg-1) with mean and (±SD) at solid waste disposal area in Halabja city from May to December 2012. Trace Heavy Metals Concentration (mg.kg-1) in wheat grain with mean and ( ±SD ) at Agricultural site in solid waste disposal area in Halabja city. Calculation of water quality index via ground water samples Calculation of water quality index via surface water samples Chronic daily intake (CDI) and Hazard quotient (HQ) indices of Heavy metals via ground water. Chronic daily intake (CDI) and Hazard quotient (HQ) indices of Heavy metals via surface water Classification of water quality depending on BOD5. Demonstrates water classification depending on Total hardness. Water quality classification based on WQI value
73 75 75 77 77
78 79 79 80 80 86 87 109
List of Figures NO. List of figure 3.1
Page
Map shows: 24 A- Kurdistan Region of Iraq, Halabja District is Blue Colored. B- Satellite imager map of Halabja Province showing locations of the studied area. C- Satellite imager showing locations of sample site area. List of plates
NO. 3.1 3.2 3.3
List of plate Site view of Halabja solid waste open dump area Site view of Halabja solid waste dump harbouring birds . Site view of surface water near open dump area
Page 25 25 26
3.4
Site view of well water near open dump area
26
3.5
Site view of Agricultural area near Halabja solid waste open dump site
27
XII
List of abbreviations ANOVA
Analysis of Varianc
APHA
American Public Health Association
As
Arsenic
BOD5
Biological Oxygen Demand
Ca
Calcium
Cd
Cadmium
CEC
Cation exchange capacity
Cr
Chrome
Cu
Copper
CNS
Carbon Nitrogen Sulfur analyser
DO
Dissolved Oxygen
DW
Distilled water
DWEL
Drinking Water Equivalency Level
EC
Electrical conductivity
EDTA
Ethylene diamine Tetra-acetic acid
EPA
Environmental Protection Agency
FAO
Food and Agriculture organization
Fe
Iron
HCl
Hydrochloric acid
HQ
Hazard Quotient
HI
Hzard Index
HM
Heavy metal
EU
European union
ICP-MS
Inductive Coupled Plasma Mass Spectrophotometer
K+
Potassium
MCLG
Maximum contaminant level goals
MSW
Municipal Solid waste management
m.a.s.l
Meter above the sea level
Ni
Nickle
XIII
N+
Nitrogen
NSDWQ
Nigerian Standard for Drinking Water Quality
OM
Organic matter
Pb
Lead
P
Plant
pH
Potential of Hydrogen Ion.
PTEs
potentially toxic elements
Ppm
Part per million
TDS
Total Dissolved Soil
TAG
Trace Analysis Grade
TH
Total Hardness
UK
United kingdom
W1
Well number 1
W2
Well number 2
W3
Well number 3
WHO
World Health Organization
WQI
Water Quality Index
Zn
Zinc
XIV
Chapter One
Introduction
Chapter One 1. Introduction Municipal Solid waste (MSW) constitutes a serious problem in many third World cities. Most cities do not collect the totality of wastes generated in a proper way, and of the wastes collected only a fraction receives proper disposal. The insufficient collection and inappropriate disposal of solid wastes represent a source of water, land and air pollution, and pose risks to human health and the environment. Over the next several decades, globalization, rapid urbanization and economic growth in the developing world tend to further deteriorate this situation. The environmental degradation caused by inadequate disposal of industrial and urban wastes generated by human activities can be expressed by the contamination of surface and groundwater through leachate, soil contamination through direct waste contact or leachate, air pollution by burning of wastes.Worth noting, solid waste can be classified as biodegradable or non-biodegradable, soluble or insoluble, organic or inorganic, liquid or solid, toxic or nontoxic (Ogbonna et al., 2009; Afolayan et al., 2012). In this study, physicochemical properties and distribution on soil have been detected using samples collected from the unregulated dumping site area in halabja/Kurdistan region. The dumping site investigated in this study is an unregulated dumping site that belongs to the Municipality of halabja. The dumping site receives nearly 80 tons/day of wastes generated in halabja (Halabja Municipality, 2012). There is a small stream, a number of small wells in the close vicinity of the area. The leachate has been percolated into these groundwater sources. In Halabja city, owing to the lack of awareness, all types of waste, especially solid waste including hazardous waste are often mixed with domestic wastes and disposed in an uncontrolled manner without any form of site management. These practices among others contaminate soil, water and air, and poses health risks to the animals living close to the dumping area. Rapid urbanization, industrialization, economic growth and population explosion in Kurdistan region has led to the migration of people from villages to cities, which generate thousands of tons of MSW daily ( Rashid, 2010). The major environmental problem experienced around the open dump site are the subsequent contamination of surface and groundwater via discharged leachate. When 1
Chapter One
Introduction
groundwater becomes polluted, the risk of surface water contamination also increases because groundwater recharges surface water more than any other source, including precipitation. Onthe other hand, Open dumpsites present a number of risks to soil due to its propensity to generate toxic chemicals, pathogens and alter the natural environment of the soil ( LAWMA, 2010; Amuno, 2011). Disposal of solid waste in to open dumps is the normal practices by municipalities of our country. During the rainy season leachate formation takes place from the wastes which enters near by water resources and penetrate deep down in to ground water. Leachates are composed of high concentration of organic substances, soluble salts and other constituents including toxic heavy metals (Obodo, 2001; Waheed et al., 2007; Dibakar et al., 2012). Dumping of solid wastes without proper separation increases the concentration of heavy metal such as Arsenic , Cadmium, Chromium, Copper, Lead , Mercury ,Nickle and Zinc. These heavy metals when present in solid waste, have been known to produce the major environmental impacts (He et al., 2006; Xiaoli et al., 2007; Ebong et al., 2007). Consequently, subsequent application of MSW composts rich in heavy metals to agricultural soils may cause heavy metals accumulation to toxic levels ( Hsu and Lo, 2001). With rains, they are percolated into the soil and are eventually translocated into plants and into human through consumption of these plants (Ideriah et al., 2010). Heavy metals are non biodegradable and they can be accumulated in living tissue causing various diseases and disorders (Wan Ngah and Hanafiah, 2008). Aims of the study can be summarised as follows: -
Study the environmental impact of open solid waste dump on the Dumping site area in Halabja.
-
To Evaluate some physico-chemical properties of the surface and ground water and soil around the open dump area, inorder to, know the suitable for human and animals consumption according to hazard index and water quality index.
-
To evaluate the pollution potential in soil and water due to heavy metals in the halabja open dump site.
-
To determine the causes of pollution of ground water, surface water and soil.
-
To identify and measure the concentration of some heavy metals in wheat crop agriculture around open dump site.
2
Chapter Two
Literature Review
Chapter Two 2. Literature Review 2.1 Pollution Pollution is defined as an undesirable change in the physical, chemical or biological characteristics of air, water and land that may be harmful to human life and other animals, living conditions, industrial processes and cultural assets, It can be natural or manmade ( singh, 2006 ). In addition pollution is the introduction of contaminants into a natural environment that causes instability, disorder, harm or discomfort to the ecosystem i.e. physical systems or living organisms; It is often classed as point source and nonpoint source pollution (WHO, 1998 and EPR , 2001 ). The agents that pollute are called pollutants; while a pollutant is a material or a type of energy which its introduction into environmental system leads to pollution (singh, 2006 and Rashid, 2010).
2.1.1: Environmental pollution in Iraq: The number of population and rapid urbanization has being increasing worldwide, especially in the developing countries, which had an annual urban growth rate of 3.6% between 1950 and 2005, versus only 1.4 % in developed countries ( Aubry et al., 2012). This surge has led to elevating demand for food, shelter and employment ( Nafiue et al., 2011). Population of Iraq has tripled since 1970, growing from 10 to 30 million, around 71% of which is living in urban areas. 47% of the urban people are currently living in slum-like conditions. It is expected that the population will increase to approximately 50 million by 2030 ( UNCTI, 2010 ). The Iraqi country faces a variety of environmental problems, such as, draught, desertification, oil refineries, factories, water pollution and shortage, discharges of sewage into rivers, fertilizer and pesticide contamination of the soil, air pollution in urban areas and inefficient solid waste management ( USEPA, 2004 ). UNCTI (2010) reported that 39% of the agricultural lands of Iraq suffers from decreasing in crop land. Consequently, a noticeable amount of heavy metals and other chemicals are released into the water, soil and air. Smoke from oil-well fires and burning oil trenches during the recent war caused localized soil and air contamination.
3
Chapter Two
Literature Review
2.2:Municipal solid waste: Municipal Solid Waste is useless unwanted material discharged as a result of human activity. Most commonly, they are solids, semi solids or liquids in containers thrown out of houses, commercial or industrial premises. Solid Waste varies in composition, and are influenced by many factors, such as culture affluence, location etc. Municipal Solid Waste management depends on the characteristic of the solid waste including the gross composition, moisture contents, average particle size, chemical composition and density; knowledge of which, usually helps in disposal plans. However disposal receives less attention: as much as 90 percent of the MSW collected in Asian cities end up in open dumps ( Zhu et al., 2008; Adefemi and Awokunmi, 2009 ). Nearly all human activities generate waste, and the way in which this is handled, stored, collected and disposed of, can pose risks to the environment and to public health ( Zhu et al., 2008; Rajkumar et al., 2010). Biodegradable wastes can be commonly found in municipal solid wastes ( MSW ) as green wastes, food wastes, paper wastes and slaughter house wastes. They are wastes typically originating from plant and animal sources which may be broken down by living organisms ( Chinyere et al., 2013 ). Disposal of hospital and other medical waste requires special attention since this can create major health hazards. The collection of clinical waste from hospitals and medical centers should be performed in specific ways and burned in special medical incinerator. More than 90% of the incinerators in Iraq’s hospitals’ are not functioning. Hence, clinical waste is being mixed with domestic waste and dumped in uncontrolled landfills. Landfills and open dumps are a common municipal solid waste management practice and one of the cheapest methods for organized waste management in many parts of the world ( WHO, 1997; Jhamnani and Singh, 2009 ). Landfill leachate may be characterized as a water based solution of four groups of contaminants; dissolved organic matter, inorganic macro components , heavy metals, and xenobiotic organics ( Charles and Okoro, 2012 ). Organic waste includes leaves, timber waste, vegetable extract, kitchen waste, household waste, hotels waste, fruits and juice centre residue etc. Paper waste includes paper dish, news paper, paper box, paper bags, wrapping materials (e.g. soap cover, tooth paste cover, match box cover) etc. Plastic waste includes plastic bags, broken plastic material (e.g. mug, bucket, pipes, plastic covers, plastic wrapping material). Metal waste includes screw, nut bolt, electronic parts,
4
Chapter Two
Literature Review
damage vehicle parts etc. Glass waste includes broken glass materials, bear bottle, glass lamp, bulb, tube lights. Miscellaneous waste includes all sanitary wastes ( Dhere and Pardeshi, 2008 ). Areas near landfills and municipal disposal sites have a greater possibility of ground water pollution because of the potential pollution source of leachate that originates from the decomposition of the organic wastes disposed at these sites and finally percolates into the local aquifers ( Ibtisam and Abdul, 2012 ). In Kurdistan region of Iraq, particularly in the present study area, solid wastes including domestic, hospital and industrial wastes all together are being disposed or some time partially dumped in places close to the cities, where people practice agriculture especially crop production. Only in Sulaymanyah city approximately 1.43 kg per capita per day of solid waste is being produced and about 1000 tonnes of wastes are transferred by the municipal vehicles (dumper, tractors, trucks) in to solid waste disposal areas ( Rashid, 2010 ). Abdullah ( 2005 ) reported that garbage produced for Duhok city and its peripheries per day per capita = 0.94 kg, while Shekha ( 2011 ) reprted that the solid waste production in Erbil city reached 0.420 kg capita.day-1. Also in halabja city approximately 1.296 kg per capita per day of solid waste is being produced and about 80 tonnes of wastes are transferred by the municipal vehicles into solid waste disposal area ( Halabja Municipality, 2012 ). The pile of waste in the waste disposal area is set on fire either by waste scavenger or by self-incinerating; consequently different gas pollutants may release into the air. Beside during the rainy seasons (winter and spring) the leachate from the disposal area flows in to the soil and surface water. Table ( 2.1 ): Listed the average percentage composition of solid wastes for Halabja city during ( 2011 and 2012) years. Component Of Food
Paper&
Solid waste
wastes
Carton
(%)
(%)
(%)
65.7
3.1
3.24
Percentage (%)
Plastics
Textiles
Glass
Wood
Metal
&Cloth (%)
3.44
rate(kg/day/ (%)
(%)
(%)
(%)
person
1.79
0.93
1.94
19.8
1.079
2011 year
2012 year
Nilon Estimated
7 76.23
5.082
2.39
3.89
*Halabja Municipality/Dept.of service. 5
2.09
2.99
2.69
4.63
1.296
Chapter Two
Literature Review
In Turkey the average daily solid waste quantity per capita was 1.34 kg in average ( Banar et al., 2009). Torabian et al., (2004) reported that the city of Tehran is producing a daily amount of 6000 tones of solid waste equivalent to 0.6 kg of solid waste per capita per day. Miller ( 1999 ) reported that the United States is responsible for creating 33% of the world's MSW and USA producing 2 to 3 times more garbage than other countries. In the United States, 243 million tons of MSW were generated in 2009, eight million tons less than generated in 2008 ( EPA, 2010). The per capita of MSW generated daily in India ranges from about 100 gm in small towns to 500 gm in large towns ( Kumar et al, 2010 ).
2.2.1: Effect of municipal waste disposal area on urban and peri urban agriculture (UPA): Handling and disposal of solid waste can be considered a major environmental problem in many countries. Most of the waste throughout the world is produced in urban areas ( Pasquini and Alexander, 2004 ) and they approximated that about third and half of this waste is not treated properly. Domestic solid waste cane be consider a source of high levels of potentially toxic elements ( PTEs ) as it contains main sources of them , for instance, household chemicals, food packaging, batteries and electronic components, ceramics, paints, automotive components and oil, plastics, inks, construction debris and hospital waste ( Nabulo et al., 2012 ). As a result of indiscriminate disposal, dumping of solid waste may likely lead to spreading diseases, accumulate PTEs and other pollutant in soils, changes in soil physical and chemical properties and distort interaction among biological, chemical and physical soil functions (Anikwe and Nwobodo, 2002, Pasquini and Alexander, 2004, Adjia et al., 2008). Former researches have revealed that food crops and vegetables grown in or nearby waste disposal areas contain higher concentrations of PTEs than those grown in clean soils ( Qadir et al.,2000; Anikwe and Nwobodo, 2002; Nabulo et al., 2010; Lente et al., 2012 ). Within some limits, the organic portion of municipal waste, for example, raw kitchen waste performed in the preparation and consumption of diet (food leftovers, rotten fruit, vegetables, leaves, crop residues, animal excreta and bones ( Asomani-Boateng and Murray, 1999; Adjia et al., 2008 ) can improve soil fertility in urban farming and develop the physical property of the soil ( Anikwe and Nwobodo, 2002 ). The production of compost from organic parts of domestic waste and its utilization in UPA may have a significant role in soil organic matter improvement ( 6
Chapter Two
Literature Review
Gigliotti et al., 1996 ), and maintain physical and biochemical criteria of impoverish soil. On the other hand, high concentrations of PTEs in composting materials and technique has been reported ( Kaschl et al., 2002 and Baldantoni et al., 2010 ) which may lead to trace metal contamination. It can accumulate in the surface soil and may pose long term environmental hazards as they could be absorbed by plants and passing through food webs or leach through the soil thus contaminate ground water ( Karaca, 2004; Smith, 2009 ), moreever, colloidal and dissolved organic matter in compost structure may lead to bioavailability and mobility of trace elements ( Kaschal et al., 2002; Baldantoni et al., 2010 ). Crop and vegetable fields in urban and peri urban areas are generally faced with a higher level of contaminants including PTEs and other organic and inorganic pollutants compared to crops and vegetables from rural areas ( Clark et al., 2006 ), because of various anthropogenic activities, particularly motor vehicle emissions and domestic waste dumping and incineration close to or around the fields ( Alloway, 2004 ). 2.3:Physicochemical Studies of Water: Water can be polluted from different sources, the main source of water pollution are industrial (chemical, physical, organic, and thermal wastes), municipal, and agricultural pollutants ( EPA, 2000 ). The disposal of solid wastes creates an important source of surface and ground-water pollution. The possible sources of water include precipitation, surface water infiltration, percolating water from adjacent land and ground water in contact with the fill. A major concern with ground - water pollution is the fact that it may persist underground for years, decades or even centuries. This is in marked contrast to surface water pollution ( Jeevan Rao and Shantaram, 1995 and 2003 ). Environmental impact of land filling of MSW can usually result from the run-off of the toxic compounds into surface water and groundwater, which eventually lead to water pollution as a result of percolation of leachate ( Rajkumar et al., 2010 ). However the mobility of the pollutants in soil largely depends on chemical, physical and biological reactions ( Jeevan Rao and Shantaram, 2003). The limnological studies on the water quality in Iraqi Kurdistan region started at Sulaimani province by Maulood and Hinton (1978), with fluctuation of ± 1 C˚ around the mean temperature of 17.7 C˚, alkaline pH 7.3, and having hard water.
7
Chapter Two
Literature Review
World Health Organization and Minestry of Health ( 1998 ) conducted a survey on physico-chemical and bacteriological drinking water source in Hawler governorate, the potential hydrogen values were always above ( 7.0 ), while concentrations of calcium, sodium, potassium and total dissolved solid ions ranged between ( 18 - 55 mg.l-1 ), ( 3.0-33.5 mg.l-1 ), (0.6-3.0 mg.l-1 ) and ( 100 - 424 mg.l-1 ) respectively. Another study carried out by Mustafa ( 2006 ) on the impact of wastewater on the Tanjaro environment concluded that generally Tanjaro River, Qliasan stream and ground water are polluted with sulfate, nitrate, nitrite, ammonia, ammonium and heavy metals ( Cadmium, Copper, Nickel, Lead and Zinc ). Mustafa and Ahmad ( 2008 ) on the other hand, concluded that the majority of the water wells ( 63% of the groundwater in Sulaimaniyah city ) is polluted with NO3, in which nitrate is more than 10 mg NO3.l-1. Muhammed ( 2008 ) conducted a study on drinking water quality in Halabja City. His results showed that the water temperature ranged from ( 13.60 °C-24.4°C ), ( pH ) values ranged from neutral to slightly alkaline ( 7.08 – 7.83 ) and EC (242.45- 635.57 μs.cm-1) respectively; while the Alkalinity ranging from (16.40 mg. l-1 to 29.20 mg.l-1) respectively. An overall mean sodium and potassium cation concentrations recorded was ( 1.13 mg.l-1 and 2.12 mg.l-1 ) respectively. The minimum total hardness, calcium hardness, magnesium hardness and chloride values were ranging from ( 178.84 to 636.46 mg.CaCO3.l-1 ) , ( 144.52 to 516.95 mg.CaCO3.l-1 ) , ( 5.56 to 158.97 mg.CaCO3.l-1 ) and (1.42 to 25.16 mg.l-1 ) respectively. Calcium levels were always higher than that of magnesium. Different ranges of heavy metals including: Cobalt, Copper, Chromium, Nickel, and Lead were calculated, they were ranging from ( 1.17 to 2.74 mg.l-1 ), ( 0.52 to 0.98 mg.l-1 ), ( 1.43 to 2.87 mg.l-1 ), ( 0.05 to 0.60mg.l-1 ), ( 0.12 to 0.91 mg.l-1 ) and ( 0.03 to 0.91 mg.l-1 ) respectively. On the other hand, Hawrami ( 2010 ) study on drinking water quality in Duhok Province revealed the metals (Cd, Pb and Ni) were higher than the permissible limit, according to the WHO guide line, while chromium was lower than the permissible limit, therefore, the water is not safe for drinking and causes adverse health effect on population. Rashid ( 2010 ) investigated the assessment of the physico-chemical status of water samples from Tanjaro waste disposal site in the city of Sulaimani. In all different sources, the potential of mean hydrogen ion ranged between 7.8 and 8.2 in Tanjaro River standing and well 8
Chapter Two
Literature Review
water samples respectively; Electrical Conductivity (EC), total hardness , BOD5 and DO mean values was 876.4, 781.9 and 1125 µs/cm-1, 224.7, 233.8 mg.CaCO3.l-1 and 90.2 mg.CaCO3.l-1 , 3.7, 2.4 and 1.1 mg.l-1 and 4.43, 4.16 and 2.65 mg.l-1 for standing and running Tanjaro River, and well water samples respectively. The average mean concentration values of Sodium, Potassium and Magnesium were 53.6, 84.5, 5144.3 and 120.92 mg.l-1, 29.4, 20.73, 1861.5 and 1.18 mg.l-1 and 22.6, 20.77, 354.2 and 17.3 mg.l-1 in Tanjaro river standing, running leachate and well water respectively. The average mean concentration values of Chlore was 35.4, 24.48, 3459.4 and 17.42
mg.l-1 for Tanjaro river standing, running , leachate and well waters
respectively. On the other hand the most of the studied samples from the river showed pollution by heavy metals (except Zn, Cu, Al and Fe) which exceeded permissible recommended values due to impact of sewage waste water from Sulaimani city, location of landfill site adjacent to the river, and anthropogenic activities. Levels of heavy metals were relatively high in well water adjacent to landfill sites. Nearly all well water samples were exceeding the permissible recommended values for drinking purpose except Fe, Mn and Al. Murray et al. ( 1981 ) observed severe contamination of ground water near sanitary landfill operations at Missouri, USA and concluded the landfill to be the principal source of water pollution. Tester and Harker ( 1982 ) investigated ground water pollution at three domestic refuse sites and concluded that pollution zones around domestic landfills is beneficial in ameliorating the effect of landfill leachate on ground water quality. A study by Ikem et al. ( 2002 ) in Nigeria indicated that the leachate collected from two dumpsites had appreciably high levels of dissolved solids, chloride, ammonia,, Pb, Fe, Cu and Mn, the ground water samples were polluted with Al, Pb, Cd, Fe, Cr, Ni. However, Adefemi et al. ( 2007 ) investigated the assessment of the physico-chemical status of water samples from four major dumps in Ekiti state, Nigeria. They concluded that a critical look at the physicochemical parameters of the water samples from all the dams in comparison to the World Health Organaziation ( WHO ) standard indicate that the water samples still fall within the stipulated range of acceptability and hence the water can be treated for domestic purposes. Moreover, a study by Flavia et al. ( 2008 ) on heavy metals in municipal solid waste landfills in southern Brazil revealed that the concentration of some metals such as Pb and Ni are above the maximum values allowed, while Cr and Cd are below the detection limit of the methods used. 9
Chapter Two
Literature Review
Another study conducted by Raman and Narayanan ( 2008 ) reveled that the pH of water samples in dump sites areas varied from 5.24 to 6.59; total alkalinity values varied from 40 to 260 mg.l-1 ; hardness of water sample varied from the 450 mg.l-1 to 669 mg.l-1. Calcium concentration varied from 107 to 169 mg.l-1 and magnesium concentration varied from 22.5 to 60.1 mg.l-1. The Nitrate and phosphate concentration varied from 22.35 to 26.37 mg.l-1 and 0.11 to 0.16 mg.l-1 respectively. Several physico-chemical characteristics of surface water including magnesium, sodium and calcium
concentrations were 120 ppm and 300 pm, 200 ppm
respectively. BOD ranged between 5 to 10 mg.l-1, also Alkalinity ranged between 40 to 80 mg.l-1 ( Kassenga and Mbuligwe, 2009 ). While, Ololade et al. ( 2009 ) studied some physico-chemical parameters in waters near solid waste disposal areas from various sources. The mean ground water pH was 6.54 but the mean surface water pH was 6.79; nitrate ranged from 7.40 – 8.80 mg.l-1 and 8.04–10.2 mg.l-1 in samples from ground and surface water respectively. The concentrations of chloride ranged from 202 - 304 mg.l-1 and 143–190 mg.-1, the concentration of sulphate ranged from 75-130 mg.-1 and 63-71 mg.-1 in samples from ground and surface water respectively. Rajkumar et al. ( 2010 ) studied the physicochemical analysis of ground water near erode municipal solid waste disposal areas. They found the values of water pH, EC, total dissolved solids and alkalinity to be 7.1 to 8.2, 410 to 3830 μs.cm-1 , 267 to 2345 mg.l-1, 210 to 675 mg.l-1 respectively; sodium and potassium concentrations ranged between 0 to 437 mg.l-1, 4 to 76 mg.l-1 respectively; calcium and magnesium concentrations were 28 to 188 mg.l-1, 5 to 209 mg.-1 respectively; while chlorides concentration ranged between 28 to 759 mg.l-1. Amadi ( 2011 ) conducted a study on the chemical status of ground water in aladimma dumpsite areas;The mean ground water pH was 6.45; the EC ranged from 212 to 4633 μs.cm-1, the BOD5 ranged from 16.4 to 325.5 mg.l-1, the Na ranged from 0.59 to 53.04 mg.l-1, the Cl, Ca, Pb, Cu ranged between 11.68 to 31.08 mg.l-1, 6.38- 38.75 mg.l-1, 0.039 to 0.256 mg.l-1 and 0.015 - 0.52 mg.l-1 respectively. This study found the concentration of electrical conductivity (EC) and the total dissolved solid (TDS) falls below the maximum allowable limit for drinking water recommended by the Nigerian Standard for drinking water quality ( NSDWQ, 2007 ), while the pH values indicated that the water is slightly acidic. The concentration of major cations ( sodium, potassium, magnesium, and calcium ) and anions ( sulfate, chloride and nitrate ) in the groundwater located the permissible limits according to the Nigerian Standard for Drinking 10
Chapter Two
Literature Review
Water Quality ( NSDWQ, 2007 ) except for nitrate. While the mean concentrations of manganese, iron, copper, chromium and zinc were slightly higher than the permissible limit of Nigerian Standard for Drinking Water Quality ( NSDWQ, 2007 ), while the mean concentration of lead, and arsenic were within the maximum permissible limits recommended by Nigerian Standard for Drinking Water Quality ( NSDWQ, 2007 ). Their high concentration in groundwater can be as a result of leachate migration from the dumpsite to the shallow. Abdurafiu et al. ( 2011 ) investigated the quality assessment of ground water in the vicinity of dump sites in Ifo and Lagos, Southwestern Nigeria. They found that the mean values of water temperature, pH, EC, total dissolved solids, alkalinity and total hardness were 28.75 0C , 6.67, 1.01 ms.cm-1, 474.25 mg.l-1, 135.46 mg.l-1 and 97.1 mg.l-1 respectively; while chloride, sodium magnesium concentrations were ranged between 92.78 to 162.07 mg.l-1, 39.92 to 308.78 mg.l-1, 4.72 to 192.24 mg.l-1 respectively; but Pb, Fe, Cu, Cd, Zn concentration ranged between 0.001 to 0.003 mg.l-1, 2.06 to 2.27 mg.l-1, 0.02 to 0.012 mg.l-1, 0.01 to 0.005 mg.l-1, 0.14 to 2.43 mg.l-1 respectively. However, Beyene and Banerjee ( 2011 ) found out that the pH ranged from 5.68 to 5.72 which is acidic and indicated the presence of metals in the samples particularly toxic metals. Their study was to assess the distribution of heavy metals profile in groundwater system at solid waste disposal site in Malaysia revealed that heavy metals like Pb, Mn, Zn, Fe and Cd are found in significantly high levels exceeding the maximum permissible concentration as specified by the World Health Organization ( WHO, 2007 ) standards for drinking water. This also lead to increased uptake of metals by some test crops although their transfer ratios differed from crop to crop. Onthe other hand, Aderemi et al. ( 2011 ), investigated the assessment of ground water contamination by leachate. In all the wells, the mean hydrogen ion value of 4.2 was recorded, thus the groundwater investigated in this study was below the WHO permissible limits for potable water. The Na ranged between ( 15.73 to 325 mg.l-1 ). In addition, to heavy metals, the concentration of Fe in groundwater samples varied from 0.18 to 0.91 mg.l-1 which was above the WHO tolerance levels in 75% of the samples, but Zn was also observed in the water samples with concentrations ranging from ND to 0.02mg.l-1 which is far below the WHO permissible while Pb and Cd were not detected in any of the groundwater samples. Akinbile et al. ( 2011 ) studied the assessed the groundwater quality near a municipal landfill in Akure - Nigeria. The parameters determined included; pH ranging from 5.7 to 6.8 and 11
Chapter Two
Literature Review
indicating toxic pollution; temperature, ranging from 26.5 to 27.50 °C; concentrations of iron, nitrate, nitrite and calcium, ranging from 0.9 to 1.4 mg.l-1, 30 to 61 mg.l-1, 0.7 to 0.9 mg.l-1 and 17 to 122 mg.l-1 respectively. For heavy metals, zinc ranged between 0.3 and 2.3 mg.l-1 and lead ranged from 1.1 to 1.2 mg.l-1. But a study by Anuar Ithnin et al. ( 2012 ) revealed that the Concentration of pH, DO, BOD, Nitrogen-ammonia and Phosphate ranged from 6.77 to 7.27, 0.58 to 4.27 mg.l-1, 4.3 to 170.6 mg.l-1, 0.24 to 8.91 mg.l-1 and 0.16 to 2.55 mg.l-1 respectively. Shanthi and Meenambal ( 2012 ) studied the physicochemical analysis of ground water near Coimbatore dumping sites. They found the values of water temperature, pH, EC, total dissolved solids, dissolved oxygen and BOD were 25.12 0C to 27.18 0C, 7.03 to 7.89, 512 μs/cm-1 to 951 μs/cm-1, 545 mg.l-1 to 996 mg.l-1, 3.78 mg.l-1 to 6.43 mg.l-1, 1.1 mg.l-1 to 3.7 mg.l-1 respectively. Calcium and magnesium concentrations were 108-264 mg.l-1 and 34-67 mg.l-1 respectively. Alkalinity, chlorides, total hardness were 78 to 187 mg.l-1,114 to 287 mg.l-1,149 to 305 mg.l-1 respectively; while Nitrate concentration was up to 20.1 mg.l-1. On the other hand, In a study conducted by Afolayan et al. ( 2012 ) revealed the temperature of the groundwater samples ranged from 24.8 0C to 26.7 0C. The pH, EC and dissolved oxygen of the groundwater samples was ranged between 5.98 to 12.19, 0.17 to 9.94 us.cm-1 and 3.18mg.l-1 to 4.41 mg.l-1 respectively. While total hardness and concentration of CI- ranged between 6 to 126 mg.l-1 and 5 mg.1-1 to 474 mg.1-1 respectively. Nitrate was generally less than the WHO standard limit. While according to a study conducted by Dibakar et al. ( 2012 ) revealed the pH and electrical conductance and total hardness were within the permissible limit declared by WHO. Several physicochemical characteristics of water including total hardness and BOD ranged from 96 – 552 mg.l-1 and 2.2 to 2.6 mg.l-1 respectively, the Chloride content ranged from 14.97 to 182.56 mg.l-1, the average of total alkalinity varied from 18.20 to 142 mg.l-1 and nitrate concentration was found to be in the range of 4.2 to 24.18 mg.l-1, Chloride ranged between 1174.2 to 135.6 mg.l-1 ( Jhamnani and Singh, 2009, Rashmi shah et al., 2013). 2.4: Physicochemical Studies of Soil “Soil is a fundamental and irreplaceable natural resource playing a role in food production, climate regulation and maintenance of biodiversity; it is the essential link between the geosphere, hydrosphere and atmosphere”. Soil is a key component of natural and agricultural environment, and plays a significant role in growing, decomposing and recycling of all biological communities 12
Chapter Two
Literature Review
( Alloway, 2004 ). Potentially toxic elements ( PTEs ) are considered the significant most hazardous materials in soil and water contamination. They can be passed to, dispersed through and accumulated in biological organisms and then may be transported through the food chain to human population as a final consumer ( Ju-Yong kim et al., 2005 ). As it is known, that trace elements are present in soil in various chemical forms with difference solubility and bioavailability. Although some trace metals including Cu, Zn, Fe and Mn, are essential for all living organisms on earth, some others, As, Cd and Pb, not only have unknown function in plants, animals and human but also are toxic for biological organisms ( Peijnenburg et al., 2007). Municipal solid waste has been found to contain appreciable quantities of heavy metals, such as Cd, Zn, Pb, and Cu, all of which may eventually end up in the soil and are leached down the profile ( Alloway and Ayres, 1997 ). Dumpsites are potential sources of soil contamination as a result of the migration and proliferation of leachate produced through the decomposition of municipal solid wastes (Amuno, 2011). Municipal landfill leachate are highly concentrated complex effluents which contain dissolved organic matters; inorganic compounds such as ammonium, calcium, magnesium, sodium, potassium, iron, sulphates, chlorides and heavy metals such as cadmium, chromium, copper, lead, zinc, nickel; and xenobiotic organic substances ( Christensen et al., 2001and Aderemi et al., 2011 ). Different Sources such as electronic goods, painting waste, used batteries, etc., when dumped with municipal solid wastes, raise heavy metals in dumpsites and dumping devoid of the separation of hazardous waste can further elevate noxious environmental effects ( Rajkumar et al., 2010 ). Some of the most common soil contaminants are chlorinated hydrocarbons, heavy metals such as chromium, and cadmium found in rechargeable batteries and lead found in lead paint, and aviation fuel still used in some countries. Lead and copper release from old pluming water system, and municipal landfills are the source of many chemical substances entering the soil environment ( Rashid, 2010 ). Municipal waste compost and its leachate increases the amounts of soil organic matter , available macro- nutrients (N, P, K) and micronutrients ( Fe, Mn, Cd, Cu, Pb, Zn, and Ni ) in soil, while soil CaCO3 decreases due to leachate acidic pH which in turn decreases soil productivity and crop yield. Municipal waste leachate has been reported to affect soil physical and chemical properties ( Roghanian et al., 2012 ). It promots soil aggregation, 13
Chapter Two
Literature Review
reduced surface crusting, reduces pH in calcareous soils, and increases soil organic matter. With adding leachate to soil, the amount of soil Cl, soluble sulfate and soluble bicarbonate increases and leaching and time passing decreases their amount. According to physical-chemical and mineralogical characteristics, soils can have great capacity to retain ions and compounds through absorption and complexation reactions on particles surfaces. Organic matter, Fe and Mn oxides and clay minerals are able to form complexes and adsorb several metals due to the surface charge of these materials ( Langmuir, 1997; Costa et al., 2004 ). Surface reactive phases of soils and aquifers, comprised of phyllosilicate and metal oxohydroxide minerals along with humic substances, play a critical role in the regulation of contaminant fate and transport ( Flávia et al., 2008 ). Muhammad ( 2008 ) conducted an ecological study on the tasluja cement plant and mining site, Sulaimani-Kurdistan region of Iraq. The results of physiochemical parameter were as follow: the mean soil temperature was 23.45 oC, pH values was ranging from7.4 and 9.2, EC values was ranging from ( 12 and 125 µs.cm-1 ), sulphate concentration value was ranging between (128 to 680 mg.kg-1), while Fe, Zn, Cu, Mn, Co, Ni, Cd and Pb were estimated for soil systems, trace metals were showed in different modes during the study period. While a study by ( Muhamed, 2008 ) in halabja city revealed that the available phosphorus ranged between ( 3 mg/kg-1 and 8 mg/kg-1 ), while the amount of total phosphorus ranged between ( 176.65 mg/Kg-1 and 415.49 mg/kg-1 ). Total calcium carbonate ranged between ( 23.19 - 34.48 % ) which indicates that all soils were considered to be calcarious soils. Generally, soil samples varied in organic matter contents which ranged from ( 0.41 - 2.37 % ), but pH value of the soil samples ranged between ( 7.41 - 7.81 ), and the soil was located between slightly to moderately alkaline. More dominant soluble cations which can be ordered were ( Ca+2 > Mg+2 > Na+ > K+), but the most dominant soluble aninon was ( HCO3- ) which resulted from dissolving ( CaCO3 ) followed by ( Cl- ). Chemical and physical characteristics of two study soils show that these
soils
contained higher amounts of calcium carbonate of more than 10%, while the electrical conductivity of these soils were less than 1.2 ds.m-1. The pH of these two study soils is more than 7.2. The soils available phosphate were 10.62 and 9.02 µg.g-1 in Darbandikhan and Arbat locations ( Rashid, 2010 ).Inaddition, a study by Mohamed ( 2013 ) revealed the
high
concentration of Ca in all soil samples was expected because it was characterized as highly calcareous and the concentration of PTEs was found to be Mn> Fe> Sr> Ni > Zn > Cr > V > Cu 14
Chapter Two
Literature Review
> Pb > Co > U > Se > Mo > Cd. Although relatively high concentrations of Ni and Cr were found at all sampling areas, yet they were close to threshold level, mean concentrations of trace elements in the soil samples in the different studied areas were all below the soil guideline value. Hoertling ( 1989 ) reported that all trace metal concentrations increased considerably below the dump at municipal waste disposal site at Pangui Tung, China. Also a study by Esakku et al. ( 2003 ) on heavy metals in a municipal solid waste dumpsite in India revealed that the concentrations of Hg, Cr and Pb exceeded the limits set by the Government of India. Organic matter levels were very high in the dump sites compared to the non-dump sites. Results show that organic matter percent ranged betweeen15.3 % to 22.0 %, N content ranged between 0.76 % to 0.97 % . These represent increases in N content of 646% to 750 % ( Anikwe and Nwobodo, 2002 ). Krishna and Govil ( 2004 ) revealed that the levels of metals in soils around the industrial areas were found to be significantly higher than their normal concentration in soil. On the other hand, the study done by Rashad and Shalaby ( 2007 ) on the dispersion and deposition of heavy metals around municipal solid waste dumpsite showed that the mean pH value, EC, organic matter, Ca, Mg, Na and Cl were (7.9,4.8 ds.m-1, 2.8%,4.5 meq.l-1, 3 meq.l-1, 11.8 meq.l-1 and 7.3 meq.l-1) respectively; while mean concentration of Cd, Cu, Ni, Cr and Zn were (5.1μg g 1
, 97.11 μg.g -1, 12.21 μg.g -1, 11.2, 1 μg.g -1 and 1101 μg.g -1) respectively. A study done by Raman and Narayanan ( 2008 ) revealed that pH, EC, Pb, Cd, Cu, Mn,
Cr, Ni and Hg value in the soil were varied between (6.3-7), (180.2 - 622 μmhos.cm-1), (7.4351.52 mg.Kg-1), (0.17-0.40 mg.Kg-1), (25.28 - 43.08 mg.Kg-1), (32.74 - 110.8 mg.Kg-1), (6.50 44.28 mg.Kg-1), (4.68-9.52 mg.Kg-1) and (0.029-0.20 mg.Kg-1) respectively. While a study done by Oyedele et al.(2008), investigated that the mean value of pH, organic matter, potassium, sodium, calcium, magnesium were 7.5,3 mg.kg-1, 2 mg.kg-1, 0.57 mg.kg-1, 12.3 mg.kg-1, 6.4 mg.kg-1 respectively. Lead for instance increased with depth from 37.9 ug.g-1 to 102.1 μg.g-1. The concentrations of Cu and Zn however decreased with increasing soil depth which is an indication of their low mobility. Soil organic matter ( SOM ) content of the surface soil ranged from 3.0 to 6.2% in the dry season and from 2.7 to 4.2% in the wet season. While the soils of the dump sites were found to be enriched with heavy metals ( Zn, Cu and Cd ) more than the adjacent soils but were still within tolerable /critical level with the exception of Pb which had a high value of 109.7 ug.g-1 above the critical value of 100 ug.g-1. While, singh et al. ( 2008 ) 15
Chapter Two
Literature Review
assesssed the impact of municipal solid waste; the result showed that the pH of all MSW samples ranged between 7 to 7.5; the percentage of organic matter was between 6 to 19 % , chlorides and sodium 1
in MSW varied between 0.02 to 0.4 mg.g-1 and 0.02 to 0.1 mg.g-
respectively, Calcium and nitrate content of soil samples was in the range of 0.11 to 0.1 mg.g-1
and 0.08 to 0.092 mg/g respectively. Sulphate, potassium and phosphate of soil samples were within a range of 0.085 to 0.11 mg.g-1, 0.1 to 0.95 mg.g-1 and 0.0016 to 0.004 mg.g-1 respectively. A study by Flávia et al. ( 2008 ) on heavy metals in municipal solid waste landfills in southern Brazil, investigated the average concentration of Pb, Cu,Cr, Cd, Ni, Zn, Hg and found it to be 20 mg.kg-1, 120 mg.kg-1, 113 mg.kg-1, 0.2 mg.kg-1, 97 mg.kg-1, 72 mg.kg-1,0.02 mg.kg-1. While the average concentration of pH and total organic carbon were 6.1% and 0.2% respectively. Also Adefemi and Awokunmi ( 2009 ) studied the impact of municipal solid waste disposal; high concentrations of Cu, Mn, Fe, Pb, and Zn were found in the soil samples. Whereas Adjia et al. ( 2008 ), revealed these levels to be were out of the critical level for agricultur for the high concentrations of Pb and Zn, Cd, Cu and Zn, but the levels of Ni in urban wastes from all sites ware lower than the critical level; the level of Ca ranged from 12.59 to18.45 g/100 g whereas the levels of Mg ranged from 2.80 to 3.5 g/100 g. Banar et al. ( 2009 ) conducted a study on soil heavy metal pollution and distribution from the unregulated dumping site area in Eskisehir/Turkey. They found out that the average concentrations of As, Cr, Pb exceeded the threshold and natural background values, whereas the upmost concentrations of Cu, Ni and Zn exceeded the prescribed threshold limit. Soil pH varied from 5.7 to 8.9 and was acidic to near neutral and alkaline in nature. Likewase, Ogbonna et al. ( 2009 ), illustrated that the soils were moderately acidic and the results of the heavy metal concentration in all the locations of the waste dumpsites were above permissible limits. A study conducted by Awokunmil et al. ( 2010 ) investigated the ranges of concentrations of cobalt, chromium, copper, iron, lead, manganese, nickel and zinc which between 105 – 810 mg.kg-1, 900 – 2000 mg.kg-1, 18.00 - 133.10 mg.kg-1, 1100-10,920 mg.kg-1, 3500–6860 mg.kg1
,20 – 2210 mg.kg-1, 18 – 335 mg.kg-1 and 350 – 3052 mg.kg-1 in all locations on all dump sites.
Also Okeyode And Rufai (2011) revealed that levels of the metals in soils around the dumpsite area were significantly higher than their normal concentration in soil. In addition, a study 16
Chapter Two
Literature Review
conducted by ( Rashad et al., 2011 ) showed relatively high pH and CaCO3 content and low organic matter content at the soil surface. Amadi ( 2011 ) assessing the effects of aladimma dumpsite on soil, revealed that the (pH) values ranged from neutral to acidification ( 4.70-7.40 ) and EC (38 -198 μs.cm-1). The overall mean sodium, potassium and calcium cation concentrations recorded were ( 321.08 mg.kg-1, 456.5 mg.kg-1 and 98.65 mg.kg-1 ) respectively. The mean concentration of chloride, sulfate, bicarbonate, nitrate during this investigation were (178.22 mg.kg-1, 110.24 mg.kg-1, 56.34 mg.kg1
, 336.26 mg.kg-1). A study done by Amuno ( 2011 ), showed some degrees of contamination with metals like
Pb, Zn, Ba, Sr, Se; while the concentrations of , Mn, and Cu were lower compared to their respective average shale contents and thus showing no enrichment of any kind. In adittion, the study conducted by Partha et al. ( 2011 ) revealed that soils in the downstream and vicinity of Hyderabad city dumpsite were considerably contaminated by metals with their concentrations beyond threshold values. The soil-pH was acidic to alkaline which is one of the major factors affecting mobility/solubility of metals in soil environment. The average concentrations of As, Cr, Pb was found to exceed the threshold and natural background values, whereas the upmost concentrations of Cu, Ni and Zn exceeded the prescribed threshold limit. Soil pH varied from 5.7 to 8.9 and was acidic to near neutral and alkaline in nature. Worth nothing soil pH significantly affects the solubility and mobility of these metals as most of the metals are soluble in acidic soils than in neutral or slightly basic soil. A study by Beyene and Banerjee ( 2011 ) on trace element in a solid waste disposal site in Addis Ababa city revealed that the concentration of heavy metals zinc , chromium , nickel, cobalt and lead in the soil samples of the dumpsite and nearby open land were found to be higher than the internationally acceptable limit for the soil. A medical evaluation of the children and adolescents living and schooling near a dumpsite in Kenya indicated a high incidence of diseases associated with high levels of exposure to these metal pollutants ( Beyene and Banerjee, 2011 ). Chinyere et al. ( 2013 ), assessed the quality of soil in the Njoku Sawmill wasted dumpsite. They found out the mean values of Soil temperature was 33.6 0C, pH of the heavily polluted points was 7.3, organic matter and nitrate were 6.47 % and 18.82 mg/kg-1 respectively; while sulphur and phosphate were 158.48 mg.kg-1 and 9.61 mg.kg-1 respectively. On the other 17
Chapter Two
Literature Review
hand, Calcium, magnesium, sodium and potassium were 13.01mg.100g, 10.41 mg.100g, 130 mg.100g and 23 mg.100 gm respectively; soil heavy metals such as Cu, Mn, Fe and Zn were 506 µg.g-1, 3.23 mg.100 g-1, 304.03 mg.g-1 and 145.20 µg.g-1 resectively. All the exchangeable cations and trace metals concentrations investigated were higher than control levels. 2.5: Heavy Metal Study in Plants: Heavy metal accumulation in soils is of concern in agricultural production due to the adverse effects on food quality, crop growth and environmental health. Consequently, subsequent application of MSW composts rich in heavy metals to agricultural soils may cause heavy metal accumulations to toxic levels ( Bilos et al., 2001 and Veeken and hamelers, 2002 ). Soil characteristics which include pH and organic matter content affect heavy metal adsorption in soil, and however heavy metal content in the soil is not an indicator for heavy metals in plants because accumulation of heavy metals in plants is specific ( Jones, 1991 ). Plants absorb and accumulate heavy metals from the soil and water, which up to certain levels are essential for their growth and development. Heavy metals are mobile and can be taken up easily by the plants. The mobility depends on their speciation in the soil, which in turn depends on parameters such as organic matter, mineral composition and pH of the soil. Although some of the heavy metals such as Zn, Mn, Ni and Cu act as micro-nutrients at lower concentrations, they become toxic at higher concentrations; while Non-nutrient heavy metals such as cadmium, arsenic, lead, and mercury, are harmful for both plants and humans ( Muchuweti et al., 2006; Mori et al., 2009; Si et al., 2010 and Savvasa et al., 2010 ). Crop and vegetable fields in urban and peri urban areas are generally faced with higher levels of contaminants including PTEs and other organic and inorganic pollutants compared to crops and vegetables from rural areas ( Clark et al., 2006 ), because of various anthropogenic activities, particularly motor vehicle emissions and domestic waste dumping and incineration close to or around the fields ( Alloway, 2004 ). Several previous studies have demonstrated that agricultural plants cultivated in contaminated soils may contain higher levels of trace elements compared to those grown in uncontaminated soils ( Guttormsen el al., 1995; Dowdy and Larson, 1995; Gigliotti et al., 1996; Allaway, 2004; Nabulo et al., 2006; Nabulo et al., 2010; Lente et al., 2012 ). The impact of metals on plants grown in compost amended soils depends not only on the concentration of 18
Chapter Two
Literature Review
metals, but also on soil properties such as pH, organic content and cation exchange capacity ( Woodbury, 1993 ). Acidic soils tend to increase uptake and accumulation of the cationic metals such as cadmium, copper, mercury, nickel, lead and zinc, while uptake and accumulation of the anionic elements like arsenic, molybdenum and selenium is reduced ( Preer et al., 1995 ). The addition of organic matter to soil in the form of compost can therefore markedly reduce cationic metal uptake by plants ( Farfel et al., 2005; Narwal and Singh, 1998 ). Many kinds and sources of hazardous discharges in urban areas become a serious concern with UPA. They may cause multiple exposure through both direct and indirect routes ( Leake et al., 2009 ). For example, some potentially toxic elements ( PTEs ), which can transfer through environmental compartments such as Cd, is released into air, accumulated in soil for many years and could be accumulated by vegetables and crops subsequently, and may lead to various chronic diseases for consumers ( Lente et al., 2012 ). Some chemicals can also bio-magnify through species in food chains a then culminate in higher concentrations in specific tropic levels ( Cole et al., 2006 ). A study by Mohammed ( 2009 ) on some heavy metals and organic acids in some fruit tress grown,adjacent to the serpentine soil in Kunjirin village of Iraqi Kurdistan revealed that the highest total of heavy metal concentration were found in the leaves of pomegranate, fig, grape and peach. Heavy metals ( Pb, Cu, Fe and Zn ) increased by 214% and 2040% in dump site soils relative to non-dump site soils. Which may lead to increased uptake of metals by some test crops although their transfer ratios differ from crop to crop. Increased heavy metal content of the soil can lead to increased plant uptake of metals that may be injurious to human and animal health ( Anikwe and Nwobodo, 2002 ). However, Amusan et al. ( 1999 ) found that leaves of waterleaf plants grown in dump site soils contained 29.20 mg.kg-1 Cu which was well within the critical range found in plant tissues ( 20–100 mg.kg-1). In contrast, leaves of waterleaf plants grown on non-dump soils were within the normal range in plant ( 5–20 mg.kg-1). A study conducted by Barazani et al. ( 2004 ) in Israel
found out
that Zn was
accumulated in plants grown in contaminated soil ( 531 mg.kg-1 ) in significantly higher concentrations than in plants grown in non-contaminated soil (56 mg.kg-1), while no significant differences were found in Cu accumulation. Analysis of plant samples from the contaminated 19
Chapter Two
Literature Review
site in comparison to plants from a control site showed significantly higher concentration of all the analyzed heavy metals. In important study on dispersion and deposition of heavy metals around municipal solid waste dumpsites carried out by ( Rashad and Shalaby , 2007 ) in Alexandria- Egypt revealed that the mean average values of heavy metals such as Cd, Cu, Ni, Cr and Zn in the root of tomato plant were ( 0.18 μg.g-1, 21.6 μg.g-1, 1.8 μg.g-1, 1.88 μg.g-1 and 22.6 μg.g-1 ) respectively, while the mean average value in its leaves were ( 0.12 μg.g-1, 12.7 μg.g-1, 0.81 μg.g-1, 0.90 μg.g-1 and 11.3 μg.g-1 ) respectively. The uptake of Pb by cocoyam on the waste dump sites was the highest compared to other heavy metals analyzed; this ranged from 0.52 μg.g1
in control site to 85 μg.g-1 in the 10 years old dump site. The least uptake of Zn by cocoyam (
0.52 μg.g-1 ) was observed on the 10 year old dump site. There were also significant differences in the uptake of Cd among the sites. There was no significant difference in the uptake of Cd in the control site and the 4 years old dump site which had the least uptake, while the highest Cd uptake was again obtained from the 7 year old dump site. The uptake of Cu was the least on the control site and highest on the 10 year old dump site ( Oyedele et al., 2008 ). Another, the study conducted by Adefemi and Awokunmi ( 2009 ) assessed that the mean concentration of heavy metals, such as Cu, Mn, Fe, Cr, Pb, Co, Zn and Ni, in the roots and leaves of plant from Igbaletere dump site to be 21.05 mg.g-1, 245.94 mg.g-1, 341.94 mg.g-1, 12.02 mg.g1
, 185.31 mg.g-1, ND, 185.07 mg.g-1 and 1.18 mg.g-1 respectively. In the plant sample,
concentrations of Fe was found to be the highest in the root, while concentrations of Mn were the highest in the leaves. A study by Akan et al. ( 2010 ) on some physiochemical parameters in soil and vegetable samples from Gongulon agricultural site revealed that, in all the vegetable samples, the concentrations of heavy metal, like Cr ranged from 0.12 to 1.02 mg.kg-1; 0.11 to 0.72 mg.kg-1 Mn; 0.33 to 3.21 mg.kg-1 Fe; 0.11 to 1.21 mg.kg-1 Cu; 0.11 to 0.53 mg.kg-1 As; 0.11 to 2.04 mg.kg-1 Ni; 0.11 to 0.39 mg.kg-1 Pb; 0.11 to 1.44 mg.kg-1 Zn and 0.11 to 0.66 mg.kg-1 Cd. The concentrations of heavy metals in all the vegetable samples analysed were higher than the FAO/WHO guideline values. Also a study by Fagbote and Olanipekun ( 2010 ) revealed the mean concentration of heavy metals in plants ranged between 0.10±0.01ppm and 44.80±3.31 ppm. Concentrations of the metals were lower in plants than in soil apart from Cd which showed biomagnifications.
20
Chapter Three
Descreption of the study area
Chapter Three 3. Description of the study area 3.1 A brief overview about Kurdistan Region of Iraq In general, Kurdistan region of Iraq is a mountainous region. It borders Syria to the west, Iran to the east and Turkey to the north, where fertile plains meet the Zagros Mountains. Kurdistan region boundaries extend from longitude 42° 15 E to 47° 30 E and from latitude 34° 25 N to 37° 50 N. It covers an area of approximately 165000 Km2. The Kurdistan Region currently comprises the four governorates of Erbil, Sulaymania, Duhok and Halabja.
3.2 Halabja and its social aspects : Halabja city, with an area about 1258.74 km2 ,is located in Kurdistan region of Iraq, about 80 kilometers from southeastern of Sulaimanya city, 241 km northeast of the capital city Baghdad and about 16 km away from the Iraq- Iran border. Geographically, Halabja lies within 35004′22.5ʺ and 35020′29.7ʺ latitudes and 45037′39.4ʺ and 46007′10ʺ E longitude. Topographically, it lies in southeastern Sharazur plain, surrounded by Hawraman and Balambo mountains to the north and south respectively ( Al-doski, 2013 ). The city is regarded as one of the cities in the world which was attacked by chemical and biological weapons, and is known as the city of ( 5000 ) victims (Hilterman, 2008 ). Halabja is composed of five quarters with a total population of ( 90177 ) according to the (2009) census.
3.3 Soil and Lithology Aspect: Brown mountains and hill soils are prevalent in Iraqi Kurdistan region showing the effect of higher precipitation and eroded material of rocks; modified by the richer plant cover, these brown soils are fertile Rzoska. As a whole the soil of Iraqi Kurdistan region is calcareous because it is originated from limestone and dolomite of various formations ( FAO, 2001 ). The soil of Halabja belongs to silty vertic calcixerolls family, with an admixture of skeletal parts, mixed, carbonate. These soils formed from alluvial deposits, are moderately deep and occur in a slightly undulated area. Their surface is slightly stony, and fissures occur commonly ( Muhammed, 2008).
21
Chapter Three
Descreption of the study area
3.4 Climate : The climate of Halabja is similar to that of other parts of Iraqi Kurdistan region of Iraq which is semi-arid and is characterized by hot and dry summers and a moderately rainy cold winter while it has moderate climate in other season ( FAO, 2001 ). The high altitude parts of the area have a colder winter and receives more precipitation than the area in lower elevation.
3.4.1 Aspects of Tempreture The mean annual temperature in Kurdistan region vary sharply with elevation and season (between summer and winter). Iraqi Kurdistan is situated in the warm zone which has a mean annual temperature of ( 20-25 °C). During summer it exceeds (40 °C), while it falls below freezing point in winter ( Muhammmed, 2008; Al-doski, 2013 ). The average mean values of temperature recorded during the ( 2012 ) year from the meterological station of Halabja are between ( 6.8 0C – 36 0C ).
3.4.2 Rainfall Aspect Two factors,(rainfall and humidity) play a big role on the climate all together beside temperature. Halabja had a relatively annual rainfall of ( 692.27 mm.year-1) for the period (20102012) and the range was between (654.2 to 725.5 mm.year-1); moreover, in summer months precipitation became very rare and often absent.
Table (3.1): The mean monthly temperature and precipitation recorded for Halabja City, during the studied period ( May to Dec. 2012).
Climate
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Air Temp. ( 0C )
27.2
33.3
36
34.7
30.3
24.2
15.8
10.1
Soil Temp.(Co)
27.5
33.9
36.5
36.8
32.8
26.3
17
10.5
Rainfall (mm)
8.3
zero
zero
zero
zero
30.9
171.4
114.3
From: General Directorate of Agriculture department of Agro-meteorological station in Halabja
22
Chapter Three
Descreption of the study area
3.5 Halabja Open Dump Area Description A field survey was conducted in Halabja City - Kurdistan region of Iraq in 2012 ( map of the city shows survey sites).The site is situated in the north west of Halabja city, in the longitude 45°56'57.65"E and latitude 35°12'28.08"N. The main aim of this survey was to evaluate some physiochemical parameters in solid waste dumping sites in Halabja city. The area is used by Halabja city council as a disposal and dumping place for the municipal, hospital and industrial wastes. As well as, many kinds of recyclable and hazardous waste including plastic, glass, metal waste and batteries. Offensive odours at Halabja dumping site may emanate from a number of sources including, organic decomposed waste, landfill gas, agriculture, old waste disturbed by digging, malodorous wastes, and leachates. Several kinds of fruits, and root vegetables are produced for commercial and subsistence purposes in this area. In addition, the area is very close to municipal waste disposal and dumping place of the city. It is overlooking the fields, which results in its washing into the farming field during the rainy seasons. The site does not meet the minimum technical and operational local or international standards. Halabja dumping site has been used by Halabja Municipality since 1992. It is an open dump area for all of wastes (domestic, commercial, industry, and wastes from hospitals) without any segregation before dumping. The selected sites are described below.
23
Chapter Three
Descreption of the study area
A
B
C
Figure(3.1) Map shows: A- Kurdistan Region of Iraq, Halabja District is Blue Colored. B- Satellite imager map of Halabja Province showing locations of the studied area C- Satellite imager showing locations of sample site area * S for soil sample
*W for water samples
*W4 for surface water 24
*P for grain samples.
Chapter Three
Descreption of the study area
Plate (3.1) View of Halabja solid waste open dump area: The collected wastes are transported by compacters, dumper, tractors, trucks, etc…
Plate (3.2) View of Halabja solid waste dump harbouring birds .
25
Chapter Three
Descreption of the study area
Plate ( 3.3 ) Site view of surface water near open dump area
Plate ( 3.4 ) Site view of well water near open dump area
26
Chapter Three
Descreption of the study area
Plate ( 3.5) Site view of Agricultural area near Halabja solid waste open dump site.
3.6 Population: Data obtained from the Directorate of Statistic in Halabja city shows that the population of Halabja in the city center for 2009 was ( 55764 ) while for the city of Halabja was 90177. The Director of Halabja Municipality reported that Halabja consists of (4) districts and (124) villages.
3.7 Solid Waste Production: As previously mentioned, Halabja is one of the fast growing city in Kurdistan Region. As the population require food, water, accommodation, etc…on daily bases; huge amounts of solid waste are produced and finally dumped into Halabja dumping site. It is assumed that solid waste producing rate equalled nearly 1.078 kg per capita per day in 2011 and around 1.296 kg per capita in 2012. According to the report announced by the municipality of Halabja, the municipality transfers nearly about ( 80 tones ) of MSW to Halabja solid waste dumping site daily ( Halabja Municipality, 2012). 3.8 Description of studied sites around solid waste dumping area Sampling was carried out from May 2012 to December 2012 in order to get information on some of the physical, and chemical properties of water and soil in the area as follows: A. Six soil sites sample B. Four water sites sample C. Two wheat grain sites sample 27
Chapter Three
Descreption of the study area
Table ( 3-2 ) Sites, Coordinates and Description of each soil, water and grain sites
Sample
Latitude
Longitude
Elevation
Site description
Soil site 1
35.204703° 45.954147°
606 M
Located 150 m Up ward of dumping site
Soil site 2
35.205099° 45.953325°
598 M
Located 20 m Inside dumping site
Soil site 3
35.205099° 45.953325°
590 M
Located 75 m Up word of dumping site.
Soil site 4
35.206767° 45.953490°
586 M
Located 50 m Down word of dumping site
Soil site 5
35.206388° 45.949843°
591 M
Located 100 Down word of dumping site
Soil site 6
35.206373° 45.949838°
582 M
Located 200 m Down word of dumping site
586 M
Located 150 m at the lateral side on the dumping drilled at 2007 with a depth of 90 m
587 M
Located 155 m on the lateral side of the dumping drilled at 2008 with depth of 100 m
Site 3 ground water 35.205715° 45.954435°
588 M
Located 175 m on the lateral side of the dumping drilled at 2006 with a depth of 85 m
Site 4 surface water 35.206745° 45.953479°
585 M
Located 25 m at the lateral down word of the dumping side
Grain sample site 1
35.205721° 45.954437°
591 M
Located 50 m up word of dumping side
Grain sample site 2
35.206499° 45.949733°
604 M
Located 20 m at the down word of dumping side
Site 1 ground water 35.205709° 45.954448°
Site 2 ground water
35.205720° 45.954436°
28
Chapter four
Materials and methods Chapter Four
4. Materials and Methods: In the present study, monthly sampling was carried out around the Halabja municipal solid waste dumping sites; ten sites were selected in order to determine some physical, and chemical properties of water, and soil, and two sites were selected to determine the level of heavy metals in grain plant samples. 4.1 Sample collection Water and Soil samples were regularly collected from 10 sites and 2 grain sample sites around and within the solid waste dumping area within Halabja city Kurdistan region. 4.1.1 Water sample collection Water samples were taken with a polythene bucket, all sample containers and laboratory glasses used in analytical processes were washed with hot water and soaked with 10% HCl solution followed by twice rinsing with distilled water, samples were transferred in a cool box when the temperature was more than 25 0C and transferred to the laboratory as soon as possible ( Smith, 1997 ). Water samples were transported to the laboratories of Directorate of Health Prevention in Sulaimani city for analysis of some parameters. The samples were acidified with 1:1HNO3/D.W for heavy metals detection to minimize the precipitation and adsorption to the container wall were acidified with concentration HNO3 to bring pH < 2, and stored in refrigerators for later determination (APHA, 2005).
4.1.2 Soil sample collection Sampling was carried out from May to December 2012 on monthly basis in which soil collected from (0 to 20) cm depth from surface for detecting some chemical, and physical properties. Soil samples were collected using a clean stainless steel trowel or auger and were sealed in plastic bags for transport. The samples were air dried in aluminum trays, gently disaggregated using a pestle and sieved to obtain a <2 mm fraction. A portion of each sample was finely grained using an agate ball mill (Retsch, Model PM400), and then stored in polyethylene
bags
in
preparation
for
chemical,
92
physical
and
elemental
analysis.
Chapter four
Materials and methods
4.2 Field Analysis The elevation, air and water temperatures, hydrogen ion concentration (pH) and dissolved oxygen (DO) were measured in the field according to the methods described by (APHA, 2005; Bartram and Balance, 1996). 4.2.1 Elevation from Sea Level ( m ): It was recorded using Geographical Position System (GPS) model Garmin etrex 10 GPS 2.2-inch TFT, and it is expressed in meter above sea level (m.a.s.l.) according to (APHA, 2005 ). 4.2.2 Water Temperature ( °C ): water temperature were measured by using a clean mercury thermometer with scale marked from (0 to 100 °C) graduated up to 0.1 °C. water temperature was measured by immersing the thermometer in the water for a few minutes to obtain a constant reading. The thermometer was rinsed with distilled water after every use (APHA, 1999 and APHA, 2005). 4.2.3 Water Hydrogen Ion Potential ( pH ): The hydrogen ion potential of the water samples was measured immediately in the field using portable pH meter model (Hanna pH-209 pH meter ) which has been calibrated before use by standard buffers (4,7 and 9) as describe by (APHA, 2005). 4.2.4 Electrical Conductivity ( EC ) in µs.cm-1: EC was recorded using a portable EC-meter (LF318/SET- WTW Company-Germany) directly in the field as mentioned in (APHA, 2005). Before each sampling, the calibration of the instrument was done by specific standard solutions (0.1N KCl) given by the manufacturing company. Final results corrected at (25Cº) and expressed in (μS.cm-1). 4.2.5 Determination of Dissolved Oxygen Concentration ( DO ) in mg.l-1: Dissolved oxygen was measured directly in the field using a special oxygen-sensitive membrane electrode (HANA instrument, HI 9142 German company) as described by (APHA, 2005) final results are expressed as mg.l-1.
4.3 Water Laboratory Analysis: 4.3.1 Determination of Biological Oxygen Demand Concentration ( BOD5 ) in mg.l-1: The main principle underlying the determination of ( BOD5 ) is the measurment of oxygen content before and after incubation for five days ( 20 °C ) as described in APHA (1999 ). 03
Chapter four
Materials and methods
When the dissolved oxygen content of the initial sample is DO0 mg O2.l-1 and after the incubation is DO5 mg O2.l-1, then BOD5 is: BOD5 = DOo – DO5 mg O2.l-1
4.3.2 Water Hardness 4.3.2.1 Total Hardness ( TH ) in mg.CaCO3.l-1 EDTA– titrimetric method was used for the determination of total hardness as described by (APHA, 1999). The titration was carried out against 0.01M EDTA (di-sodium salt) solution using buffer solution of pH 10 and Eriochrom Black –T indicator. Results were expressed as mg CaCO3.l-1 using the following equation: Total hardness (mg CaCO3.l-1) = A× B×1000/ ml. of sample Where: A=Volume of EDTA titrant B=mg. CaCO3 equivalent to 1 ml. EDTA 4.3.2.2 Calcium Hardness: Calcium (Ca) hardness was determined in the present study using EDTA- titrimetric method as described by APHA (1999) using buffer solution of pH 12 and Murexide as indicator. Results were expressed in mg CaCO3.l-1 using the following equation: Calcium (mg CaCO3.l-1) = A*B * 1000/ml of sample Where: A = volume of EDTA titrant. B = mg CaCO3 equivalent to 1.00 ml EDTA titrant at the calcium indicator end point. 4.3.2.3 Magnesium Hardness: As described by APHA (1999), magnesium hardness in mg CaCO3.l-1 was calculated by the following equation: Mg hardness (mg CaCO3.l-1) =Total hardness as (mg CaCO3.l-1) – Calcium hardness as (mg CaCO3.l-1). 4.3.3 Total Alkalinity mg.l-1: According to (APHA, 2005) alkalinity was determined by titration method by adding (5) drops of methyl orange to 50 ml of water samples to make titration with H2SO4 (0.01N). Results were represented as mg.l-1 using the following equation: 03
Chapter four
Materials and methods
Alkalinity as mg CaCO3.l-1 = A×B×5000/ ml of sample Where: A=ml of H2SO4 titrant B= Normality of H2SO4 4.3.4 Nitrate Nitrogen ( NO3ˉ ) in mg-at-N-NO3.l-1: The concentration of nitrate nitrogen was determined on the bases of ultraviolet spectrophotometer screening method as described by (APHA, 1999).
4.3.5 Major Ions: 4.3.5.1 Sodium ( Na+ ): Sodium cations were determined in the present study by (Flame Emission Photometric Method) as described by APHA ( 2005 ). Standard solutions (0, 10, 20, 30, 40, 50, 60, 70, 80, 90 and 100 mg.l-1of Na+) from sodium chloride were prepared for the calibration of the instrument, and creation of a standard curve. Results were expressed in mg.l-1. 4.3.5.2 Potassium ( K +): Photometric method (Flame photometric method) was used for the determination of K+ cat ions as described in APHA (1999) in a precisely similar manner to that described for Na+, except for that standard potassium chloride solutions of (0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 mg.l-1 K+) were used for the calibration of the instrument and for obtaining the standard curve. Results were expressed in mg.l-1. 4.3.5.3 Chloride ( Cl- ) In the present work, agentometric method (Mohor Method) was used for the determination of chloride content in the water samples. Silver nitrate solution ( AgNO3 ) as a titrant and potassium chromate ( K2CrO4 ) as an indicator were used as described by Sawyer and Mc Carthy ( 1978 ). Chloride ( mg Cl. l-1 ) = ( V1 – V2) × N × 35450 / Volume of sample Where : V1 = Volume of silver nitrate required by the sample (ml). V2 = Volume of silver nitrate required by the blank (ml). N = Normality of silver nitrare. 35.45 Molecular weight of Cl-. 09
Chapter four
Materials and methods
4.3.6 Water Analysis for Trace Heavy Metals Concentrations Water trace elemental analysis was undertaken by ICP-OES ( Inductively Coupled Plasma-Ootical Emission Spectroscopy) model 2100 Perkin Elmer in ‘collision cell mode’(7% hydrogen in helium) to reduce polyatomic interferences. Samples were introduced from an autosampler ( Cetac ASX-520 with 4 x 60-place sample racks ) through a concentric glass venturi nebuliser (Thermo-Fisher Scientific; 1 ml.min-1). Internal standards were introduced to the sample stream via a T-piece and included Sc (100 ng mL-1), Rh (20 ng mL-1) and Ir (10 ng mL-1) in 2% TEG HNO3. External multi-element calibration standards (Claritas-PPT grade CLMS-2, Certiprep/Fisher) included Al, As, Ca, Cd, Co, Cr, Cs, Cu, Fe, Mn, Mo, Ni, Pb and Zn, all in the preferred range of 0-100 µg.1-1. Sample processing was undertaken using Plasma lab software (version 2.5.4; Thermo-Fisher Scientific) set to employ separate calibration blocks and internal cross-calibration where required ( Nabulo et al., 2012).
4.4 Soil Laboratory Analysis 4.4.1 Soil pH and Electrical Conductivity The pH and EC was determined for soil samples at the laboratory of the Technical Agricultural Institute of Halabja. To measure the pH exactly, 5g of 2 mm sieved air-dry soil was put in centrifuge tubes and suspended in 12.5 ml of distilled water (suspensions 1:2.5 ratio). The suspension was shaken on orbital shaker model SLM-INC-OS-16 at 40 rpm for 30 minutes to equilibrate and the pH was measured on the resulting slurry. The pH and EC was measured using a Hanna pH-209 portable pH meter and a combined glass electrode (Ag/AgCl; PHE 1004), allowing 5 minutes for the reading to stabilize. The pH meter was calibrated using pH 7.0 buffer consisting of 3.9 g.l-1 NaHPO4 and 2.72 g.l-1 KH2PO4.
4.4.2 Soil organic matter ( Loss on Ignition) (LOI %) The standard method for loss of ignition was used to measure the percentage of organic carbon in the samples. A known weight of <2mm oven-dried soil in a weighted silica crucible was placed in muffle furnace (Gallenkamp size 3, Weiss-Gallenkamp, UK) for overnight at 550oC to ignite organic matter. The crucibles and soil were then placed in desiccators to cool without gaining moisture from the atmosphere. The weight loss is expressed as a percentage of soil organic matter as follows (Rahi et al, 1991): 00
Chapter four
Materials and methods
Mass oven dry soil (gm) - mass ignited soil (g) % LoI= 100* ------------------------------------------------------------Mass oven dry soil (g)
4.4.3 Soil Nitrogen and Sulfur Content Measurement Approximately 15-20 mg of dry, finely ground soil, including certified soil reference standards, were weighed into tin capsules and approximately 5 mg of vanadium pentoxide was added. Capsules were carefully crimped, using tweezers, to avoid spillage. A capsule containing only vanadium pentoxide was used as a blank and certified soil standards were used as a calibration standard. Sandy and peat certified soil standards were provided by Elemental Microanalysis; product codes B2180 and B2176, respectively. Analysis was undertaken using a CNS analyser (Flash EA1112; CE Instruments); samples were introduced from a MAS200 autosampler. Sample capsules were dropped into a combustion tube packed with approximately 25 g copper oxide and 70 g electrolytic copper, and heated to 900 0C. The resulting gas was passed through an absorption filter containing magnesium perchlorate to remove water before passing through a PTFE separation column and to a thermal conductivity detector. Helium was used as the carrier gas ( Rowell, 1996 ). .
4.4.4 Calcium Carbonate ( CaCO3 ) Calcium carbonate was determined by acid neutralization method titremetric method with ( NaOH 0.1N ) according to Richards as described in ( Rowell, 1996). 4.4.5 Bicarbonate mg.kg-1: Bicarbonate ( HCO3- ) was measured using ( 0.1M ) HCl till the pH of the solution reached 4.3 according to the following equation (mg.kg-1 of HCO3- ) can be calculated: 1 ml (0.1M) HCl=61.02 mg.kg-1 HCO3- according to ( Baruah and Barthakur, 1997).
4.4.6 Available Phosphorous Available phosphorous was determined using Olsen procedure as described in Ryan et al., 1985 ).
03
Chapter four
Materials and methods
4.4.7 Soil analysis for Total Elemental ( Sodium, Potassium, Calcium , Magnesium and Trace heavy metals) Concentrations: A pproximately, 250 mg of finely ground soil was digested using 70 % hydrofluoric acid, nitric acid and perchloric acid ( Trace Element Grade (TEG); Fisher Scientific, UK) in a tefloncoated graphite block digestor ( Analysco, UK) containing places for 48 PFA digestion vessels. The digested samples were diluted to 50 m.l-1 using Milli-Q water (18.3 MΩcm) and stored unrefrigerated in universal sample bottles ( 5% HNO3) pending elemental analysis. All digests were diluted to 1 in 10 with Milli-Q water using a compudil –D auto diluter (Hook and Tucker Instruments) immediately prior to analysis.
.
Multi-element analysis was undertaken by ICP-MS ( Inductive Coupled Plasma Mass Spectrophotometer) ( Model X-SeriesII ,Thermo-Fisher Scientific, Bremen, Germany ) in ‘collision cell mode’(7% hydrogen in helium) to reduce polyatomic interferences. Samples were introduced from an autosampler ( Cetac ASX-520 with 4 x 60-place sample racks ) through a concentric glass venturi nebuliser ( Thermo-Fisher Scientific; 1 ml.min-1 ). Internal standards were introduced to the sample stream via a T-piece and included Sc (100 ng.ml-1), Rh (20 ng.ml1
) and Ir (10 ng.ml-1) in 2% TEG HNO3. External multi-elemen calibration standards ( Claritas-
PPT grade CLMS-2, Certiprep/ Fisher ) included Al, As, Ba, Bi, Ca, Cd, Co, Cr, Cs, Cu, Fe, K, Mg, Mn, Na, Ni, Pb and Zn, all in the preferred range of 0-100 µg.l-1. Sample processing was undertaken using Plasma lab software (version 2.5.4; Thermo-Fisher Scientific) set to employ separate calibration blocks and internal cross-calibration where required.
.
For each digestion batch, data was corrected using two blank digestions and quality control was assessed with two samples of a reference material ( Standard Reference Material ( SRM ) 2711, Montana Soil) from the National Institute of Standards and Technology (NIST). All elemental concentrations were converted to mg.kg-1 dw (equation 2.1). ( Csoil – Cblank ) × Vol CSoil = ……………………………………..
Eq 2.1
WSoil Csoil is the elemental concentration (mg.kg-1) in the soil; Csol and Cblank are the concentrations ( µg.l-1 ) in the soil and blank digests, corrected for dilution, Vol is the digest volume ( 50 ml ) and Wsoil is the mass of soil digested (c. 200 mg) ( Nabulo et al., 2012). 03
Chapter four
Materials and methods
4.5: Preparation And Analysis of Plant Heavy Metals: Following harvest, Crop wheat plant samples by weight were washed with tap water to remove dust particles, in distilled water to remove surface contamination, then rinsed in deionised water and dried at 60 oC for 48 h before weighting. All samples were ground in an Ultra-centrifugal mill (Retch, Model ZM200, Germany) fitted with a 0.5 mm titanium screen to avoid contamination from Cr and Fe. The finely ground material ( 200 mg ) was then digested in pressurised PFA vessels in 6.0 ml of 70 % Fisher Trace Analysis Grade (TAG) HNO3 with microwave heating ( Anton Paar ‘Multiwave’ fitted with a 48-place carousel). Digested samples were diluted to 20 ml using milli-Q water (18.2 MΩ cm) and stored un-refrigerated (30 % HNO3) pending elemental analysis. Immediately before analysis, samples were diluted 1-in-10 with milli-Q water using a Compudil-D (Hook and Tucker Zenyx Ltd (HTZ, UK). Multi-element analysis was undertaken using an ICPMS system (Model X-Series II, Thermo-Fisher Scientific, Germany) with a ‘hexapole collision cell’ ( 7 % hydrogen in helium) upstream of the analytical quadrupole. Samples were introduced from a covered autosampler ( Cetac ASX-520 with 4 x 60-place sample racks) through a concentric glass venturi nebuliser ( Thermo-Fisher Scientific, Germany; 1 ml.min-1). Internal standards were introduced to the sample stream via a T-piece and included Sc (100 ng.ml-1), Rh ( 20 ng.ml-1 ) and Ir (10 ng. ml-1) in 2% TAG HNO3. External multi-element calibration standards (Claritas-PPT grade CLMS-2, Certiprep/ Fisher) included Al, As, Cd, Cr, Cu, Fe, Mn, Mo, Ni, Pb, and Zn, all in the preferred range of 0-100 µg L-1. Sample processing was undertaken using Plasma lab. software (version 2.5.4; Thermo-Fisher Scientific) set to employ separate calibration blocks and internal crosscalibration where required. The values obtained for each digestion batch (48 samples) were corrected using two blank digestions. Quality control was assessed using two samples of reference material. Elemental concentrations were expressed in units of mg.kg-1 dw (Eq. 2.2). ( Cplant – Cblank ) × Vol Cplant = ……………………………………..
Eq 2.2
Wplant where Cplant represents the elemental concentration ( mg.kg-1) in plant tissue, Csol and Cblank are the concentrations (µg.l-1) in the plant and blank digests, corrected for dilution, Vol denotes the digest volume ( 20 ml ) and Wplant is the mass of plant tissue digested (c. 200 mg).
03
Chapter four
Materials and methods
4.6: Calculation of Water Quality Index (WQI): Calculating water quality index is to turn complex water quality data into information that is understandable and useable by the public. Therefore, water Quality Index (WQI) is a very useful and efficient method which can provide a simple indicator of water quality and is based on some very important parameters ( Khwakaram et al., 2012 ). In the current study, Water Quality Index (WQI) was calculated by using the Weighted Arithmetic Index method as described by ( Cude, 2001). In this model, different water quality components are multiplied by a weighting factor and are then aggregated using simple arithmetic mean. The steps for Water quality index (WQI) are: The quality rating scale for each parameter qi was calculated by using this expression: qi = ( Ci / Si ) × 100. A quality rating scale (qi) for each parameter is assigned by dividing its concentration ( Ci ) in each water sample by its respective standard ( Si ) and the result multiplied by 100. Then, after calculating the quality rating scale (Qi), the Relative (unit) weight (Wi) was calculated by a value inversely proportional to the recommended standard (Si) for the corresponding parameter using the following expression; • Wi = 1/ Si Where, • Wi = Relative (unit) weight for nth parameter • Si= Standard permissible value for nth parameter • I = Proportionality constant. That means, the Relative (unit) weight (WI) to various water Quality parameters are inversely proportional to the recommended standards for the corresponding parameters. Finally, the overall WQI was calculated by aggregating the quality rating with the unit weight linearly using the following equation: • WQi = ΣQiWi/ Σ Wi Where, • Qi = Quality rating • Wi = Relative weight
03
Chapter four
Materials and methods
In general, WQI is defined for a specific and intended use of water. In this study the WQI was considered for human consumption or uses and the maximum permissible WQI for the drinking water was taken as 100 score ( Khwakaram et al., 2012, Toma, 2012).
4.7: Calculation of Hazard Quotient ( HQ ) Indices : The HQ for non-carcinogenic risk can be calculated by the following equation ( USEPA,1999 ): HQ= CDI / RfD
(1)
CDI= C × DI
(2)
Where, CDI and BW represent the concentration of Potential toxic elements ( PTE ) in water (μg/l-1), average daily intake rate (2 L/day) and body weight ( 72 kg ), respectively (Muhammad et al., 2010). According to USEPA database the oral toxicity reference dose values ( RfD ) are 3.0E−04, 3.00E-04 , 9.00E-03, 2.0E−02, 4.00E-04 , 3.0E−01 mg.kg -1.day for Cd, As,Fe, Ni, Pb and Zn, respectively ( USEPA,2004 ). The values of HQ were below <1 for all Heavy metals in drinking water samples indicate no health risk ( Muhammad et al., 2011 ).
4.8: Statistical analysis: Statistical package for the social science (SPSS), version 17 programs were used for analyzing the results. Monthly collected data were treated with the Analysis of Variance ( ANOVA ). Duncan multiple range tests was employed to examine statistically significant differences in the mean concentration of heavy metals among locations, and months; the significant differences at the probability (1 % and 5 % ) of each data were calculated ( Al-Rawi and Abdul Al-Aziz, 1985 ).
03
Chapter Five
Result
Chapter Five 5. RESULTS 5.1 Physico - Chemical Analysis For Monthly Water Samples During the Studied Period: 5.1.1 Water Temperature Temporal variations of water temperature were observed during sample collection among the studied sites; water temperature value at different sites and during the sampling period is shown in Table ( 5.1 ). The minimum temperature for well water was ( 18.1oC ) recorded in W2 during November and December, on the other hand the maximum was ( 27 oC ) recorded at W1 during July with the overall average mean of 21.5 oC. The statistical analysis show that the minimum mean of the studying month was (18.5 oC) during December, while the maximum was recorded during July ( 26.7 oC ), significant differences at (P<0.05) was revealed among different months except August. Surface water temperature ranged between 17.4 - 19.5 oC recorded during December and June respectively. 5.1.2 Hydrogen Ion Concentration pH: Generally, hydrogen ion concentrations of the well water ranged from 6.5 to 7.4, minimum recorded at W2 during June, while the maximum was recorded at W 1 and W2 during August as shown in Table (5.2), with the overall mean of 7.03. Statistical analysis for the studying months showed that the minimum mean (6.6) was recorded at October while the maximum mean 7.4 was recorded at August. Results revealed no significant differences at (P<0.05) among all different months. While in the studied well water sites, the minimum mean value (7 ) was obtained at W1 and W2 , while the maximum mean ( 7.1 ) was recorded at W3 which revealed no significant difference ( P <0.05 ) between the studied station wells. Surface water results varied from 7.5 during December to 7.9 during May as minimum and maximum value respectively.
39
Chapter Five
Result
Table (5.1): ( Water Temperature ) ( C o) With Mean and (±SD) value at Solid waste Disposal Area in Halabja City from May to December 2012. Studied sites
May
Jun
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
±SD
27 26.5 26.7 26.7c 0.25
26 25.6 25.5 25.7c 0.24
22.1 21.7 21.8 21.9b 0.2
19.1 18.2 18.4 18.6a 0.44
19.2 18.1 18.3 18.6a 0.86
19.1 18.2 18.3 18.5a 0.47
21.9a 21.2a 21.4a 21.5 3.19
3.1 3.33 3.2 3.1 0.29
-
-
-
-
17.8 17.8 0.2
17.4 17.4 0.1
18.2 18.2 0.9
0.9 0.9 0.9
Well water Well 1 Well 2 Well 3 Mean ±SD
19 23.2 18.9 22.5 19.5 22.6 19.1a 22.8bc 0.29 0.36
Surface water Stations 1 Mean ±SD
18.2 18.2 0.2
19.5 19.5 0.2
- Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different.
Table (5.2): (pH) Concentration value in Water with mean and (±SD) at Solid Waste Disposal Area in Halabja City from May to December 2012. Studied sites
May
June
July
August
Sept.
Oct.
Nov.
Dec.
Mean ±SD
6.8 7.2 7.3 7.1a 0.27
6.8 6.5 6.8 6.7a 0.17
7.2 7.3 7.3 7.2a 0.07
7.4 7.4 7.3 7.4a 0.09
7.3 7.3 7.3 7.3a 0.08
6.6 6.6 6.7 6.6a 0.16
6.7 6.8 6.8 6.8a 0.1
7.1 7.1 7.2 7.1a 0.1
7.0a 7.0a 7.1a 7.03 0.31
0.3 0.35 0.26 0.31 0.31
7.9 7.9 0.1
7.8 7.8 0.2
-
-
-
-
7.7 7.7 0.1
7.5 7.5 0.1
7.8 7.8 0.2
0.2 0.2 0.2
Well water Well 1 Well 2 Well 3 Mean ±SD Surface water Stations 1 Mean ±SD
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different. -Maximum Allowable Limit is (6.5-8.5) According to the WHO (2003) and EU drinking water standards.
40
Chapter Five
Result
5.1.3 Electrical conductivity (EC) µs.cm-1: According to the results obtained during the studied period which is presented in Table (5.3) well water data revealed variations ranged between (363.0 - 662.3 µs.cm-1) minimum level recorded at W2 during May, while the maximum level was recorded at W1 during August. Statistical analysis for the studied months show minimum mean (460.4 µs.cm-1) during July that show no significant differences with the other months except October, while the maximum mean (509.9 µs.cm-1) was recorded during October that show significant differences with the other months except November, while for the investigated well sites, minimum mean was observed in W2 (385.4 µs.cm-1) and the maximum mean was obtained in W1 (633.8 µs.cm1
) which show significant differences with all other sites . The results revealed significant
differences (P<0.05) among some months and the studied station wells. On the other hand, surface water EC ranged between minimum of (357.3 µs.cm-1) recorded during May, while the maximum level (406.7 µs.cm-1) was recorded during November.
5.1.4 Dissolved Oxygen (DO) mg.l-1: Variations of dissolved oxygen concentration are shown in Table ( 5.4 ).The minimum value of dissolved oxygen for well water was ( 5.8 mg.l-1 ) which was measured at W3 during August while the maximum level of dissolved oxygen ( 7.3 mg.l-1 ) was determined at W1 during May with the overall average mean of ( 6.4 mg.l-1 ). Well water analysis in the study sites revealed a minimum mean of ( 6.2 mg.l-1 ) for the studying sites recorded at W3 and maximum mean ( 6.7 mg.l-1 ) recorded at W1 which show no significant difference ( P<0.05 ) between each sites. While for the investigated months, the minimum mean was observed during August and October and the maximum mean was obtained during May which show significant differences with all other months except November and December. Surface water samples level ranged between ( 7.2 - 7.8 mg.l-1 ) during November and May respectively, and the overall mean recorded was 7.5 mg.l-1.
41
Chapter Five
Result
Table ( 5.3 ): ( Electrical Conductivity ) value in Water ( μs.cm-1 ) at 25 0C with Mean and (±SD) at Solid Waste Disposal area in Halabja City from May to December 2012. Studied sites
May
June
662 363 383.3 469.5a 144.7
660.3 364 384.7 469.7a 143.28
357.3 357.3 1.5
366.7 366.7 1.5
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
±SD
621 392.3 394 479.4a 129.43
652 428 480.7 509.9b 86.41
611.7 395 475 493.9ab 94.9
590.7 392.7 422 468.4a 92.56
633.8c 385.4a 415.6b 478.3 115.2
27.2 20.6 38.5 115.2 115.2
-
-
406.7 406.7 1.5
381 381 1
377.9 377.9 19.5
19.5 19.5 19.5
Well water Well 1 Well 2 Well 3
Mean ±SD
610.7 662.3 375.7 372.3 395 390.3 a 460.4 474.9a 112.99 140.56
Surface water Station 1
Mean ±SD
-
-
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different. -Maximum Allowable Limit is ( 700 μS.cm-1 )According to the WHO drinking water standards. - Maximum Allowable Limit is (2500 μS.cm-1 ) According to the EU drinking water standard. Table (5.4): (Dissolved oxygen) value in Water (mg.l-1) with Mean and ( ±SD ) at Solid Waste Disposal Area in Halabja City from May to December 2012. Studied sites
May
June
July
7.3
6.4
6.3
Aug. Sept.
Oct.
Nov.
Dec.
Mean
6.2
7.2
7.2
6.7
±SD
Well water Well 1 Well 2 Well 3 Mean ±SD
7.2
6.2
6.2
6.3
6.3
6.3
6.2
5.9
6.5
5.9
6.1
5.8
6.1
6.2
b
a
a
a
a
a
6.3 6.4
6.2 6.2
a
0.46
a
0.38
a
0.24
0.3 0.3 0.3
6.3
7.0 0.39
6.2 0.24
6.2 0.14
6.1 0.26
6.2 0.11
6.1 0.18
6.6 0.42
6.5 0.51
6.2 6.4 0.42
7.8 7.8 0.1
7.4 7.4 0.2
-
-
-
-
7.2 7.2 0.1
7.6 7.6 0.2
7.5 7.5 0.3
ab
ab
0.42 0.42
Surface water Stations 1 Mean ±SD
-Value with different letters are significantly different at p>0.05, but values with same letters are not significantly different. -Maximum Allowable Limit is ( 5 mg.l-1 ) According to the WHO and EU drinking water standards. 42
Chapter Five
Result
5.1.5 Biological oxygen demand ( BOD5 ) mg.l-1: In the presented study and according to the results showed in Table (5.5), well water BOD5 value ranged between ( 2.8 - 3.6 mg.l-1 ) as minimum and maximum during May for Well 2 and July for Well 1 respectively. In the studied well water sites, the minimum mean value ( 3.1 mg.l-1 ) was obtained at W2, while the maximum mean (3.3 mg.l-1) was recorded at W1 which revealed significant differences from the other sites except W3. In the studying months, the minimum mean of (3 mg.l-1) was recorded during May and that shows significant differences with other months except June, August and December, while the maximum mean (3.4 mg.l-1) was recorded during July and November that show significant differences with the other months except October. Surface water samples level ranged between (4.1 - 4.4 mg.l-1) during June and May respectively, and the overall mean recorded was 4.2 mg.l-1. 5.1.6 Total Hardness ( TH ) mg CaCO3.l-1: The total hardness value recorded in the studied period, shown in Table (5.6), for well waters ranged between ( 250 - 413.7 mg CaCO3.l-1). The maximum value was obtained during July at W 1, while W 3 in May showed the minimum value for hardness. The overall mean value for total hardness was ( 301.5 mg CaCO3.l-1 ) during the entire studied period. The minimum mean value of the studied sites was (255.7 mg CaCO3.l-1) obtained at W3 which shows significant difference from W1 but not significant differences with W2, while the maximum mean value was (392.8 mg CaCO3.l-1 ) at W 1 which is significantly different with other studied sites. In the studied months, October shows the minimum mean value (287.7 mg CaCO3.l-1) which is significantly different from the other months except with December, while the maximum mean (309.7 mg CaCO3.L-1 ) was recorded during November which is not significant different from all month except with October. Surface water sample ranged between (265.3 - 305.3 mg CaCO3.l-1); the minimum data was recorded during November, while the maximum was recorded during May.
43
Chapter Five
Result
Table (5.5): (Biological oxygen demand) value in Water (mg.l-1) with Mean and (±SD) at Solid Waste Disposal area in Halabja City from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
±SD
3.1
3.2
3.6
3.1
3.2
3.4
3.4
3.2
3.3b
0.19
2.9
a
0.24
3.2
ab
0.18
Well water Well 1 Well 2
3.1
2.8
3.4
3
3.2
3.3
3.3
3.1
Well 3
3
3.1
3.3
3.3
3.3
3.3
3.4
3.2
Mean ±SD
3.0a 0.16
3.1ab 0.12
3.4c 0.12
3.1ab 0.17
3.2b 0.1
3.3bc 0.12
3.4c 0.17
3.1ab 0.19
3.2 0.22
0.22 0.22
4.4 4.2 0.1
4.1 4.1 0.1
-
-
-
-
4.2 4.4 0.1
4.2 4.2 0.1
4.2 4.2 0.1
0.1 0.1 0.1
Surface water Stations 1 Mean ±SD
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different. Table ( 5.6 ) : ( Total hardness ) concentration value in Water (mgCaCO3.l-1 ) with mean and (±SD ) at Solid Waste Disposal Area in Halabja City from May to December 2012. Studied site
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
±SD
Well 1
403.0
411.7
413.7
400.3
401.0
361.7
372.0
379.3
392.8
b
18.5
Well 2
257.3
256.0
251.7
251.0
253.0
250.3
269.0
259.0
255.9
a
6.0
a
20.8
16.9 16.9 16.9
Well water
Well 3 Mean ±SD
250.0
251.0
253.7
250.3
251.0
251.0
288.0
303.4 74.8
b
306.2 79.1
b
b
b
b
a
b
305.3 305.3 1.5
298.3 298.3 1.5
306.3 80.5
300.5 74.9
301.7 74.5
-
-
-
250.7
287.7 55.5
309.7 55.2
296.3 62.4
255.7 301.5 67.0
-
265.3 265.3 1.5
276.3 276.3 1.5
286.3 286.3 16.9
ab
67.0 67.0
Surface water Stations 1 Mean ±SD
- Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different. -Maximum acceptable level of total hardness in drinking water according to the guidelines of WHO ( 2006 ) was 500 mgCaCO3.l-1 . 44
Chapter Five
Result
5.1.7 Calcium Hardness mg CaCO3.l-1: The Calcium hardness value in the studied period, shown in Table ( 5.8 ), for well waters ranged between (61.7 - 147.3 mg CaCO3.l-1). The maximum value was obtained during August at W1, while W3 in July showed the minimum value for Calcium hardness. The overall mean value recorded for Calcium hardness was ( 94.6 mg CaCO3.l-1 ) during the entire studied period. The minimum mean value of the studied sites was (82.2 mg CaCO3.l-1) obtained at W3 that shows significantly differente from W1only, while the maximum mean value was ( 118.4 mg CaCO3.l-1 ) at W1 which is significantly different with other studied sites. In the studied months, July showed the minimum mean value (83 mg CaCO3.l-1) that is no significantly different from other months except with August, September and December, while the maximum mean ( 119.4 mg CaCO3.L-1 ) was observed during September that significantly different from all other months except August. Surface water sample ranged between (55.3 - 74.3 mg CaCO3.l-1). The minimum data recorded during December, while the maximum recorded during June. 5.1.8 Magnesium Hardness mg CaCO3.l-1: The overall mean value recorded for magnesium hardness was (49.6 mg CaCO3.l-1) during the entire studied period which shown in Table ( 5.8 ). The minimum value was ( 37.3 mg CaCO3.l-1 ) noted at W3 during September, while, the highest value was observed was (77 mg CaCO3.l-¹) at W1 during May. In the studied months, October showed the minimum mean value ( 43.6 mg CaCO3.l-1 ) that is significantly different from the May, November and December, while the maximum mean ( 54.7 mg CaCO3.l-1 ) was noted during May and November and significantly differ with October only. The minimum mean value of the studied sites was ( 42.5 mg CaCO3.l-1 ) obtained at W3 that is significantly different with site W1 only , while the maximum mean value was ( 61.5 mg CaCO3.l-1 ) at W1 which is significantly different with W3 only. Surface water samples level ranged between ( 42.3 - 57.7 mg.l-1 ) during November and May respectively, and the overall mean recorded was ( 49.3 mg.l-1).
45
Chapter Five
Result
Table ( 5.7 ): ( Calcium hardness ) Concentration value in Water (mgCaCO3.l-1) with Mean and (±SD) at Solid Waste Disposal Area in Halabja City from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
±SD
98
121
116.3
147.3
147
110.3
104
103.3
118.4
b
18.4
Well water Well 1
76.3
Well 2 Well 3
90
Mean ±SD
88.1 9.5 66 66 1
ab
65.7
71
77
106
63.3
61.7
105
83.3 28.3
a
83.0 25.4
a
109.8 40.5
74.3 74.3 1.5
-
bc
91
86
105.3
72.3
c
91.2 16.5
86.3 15.2
95.3 6.1
-
64 64 1
119.4 20.7
ab
69
92
ab
a
20
a
83.1
90.7
82.2
17.1
b
94.6 25
25 25
55.3 55.3 1.5
64.9 64.9 7.1
7.1 7.1 7.1
Surface water Stations1 Mean ±SD
-
-
Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different. -Maximum desirable guideline Limit is 200 mg.l-1 According to the WHO drinking water standard. Table ( 5.8 ): (Magnesium Hardness ) Concentration value in Water (mgCaCO3.l-1 ) with Mean and (±SD) at Solid Waste Disposal area in Halabja City from May to December 2012. Studied site
May
June
July
77 45.7 41.3 54.7b 16.9
67.3 37.4 40 48.3ab 14.4
63.3 40 41 48.1ab 11.5
57.7 57.7 1.5
51.7 51.7 0.6
-
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
±SD
58.7 59 45.3 45.3 42.3 42 39.7 37.3 43.3 ab 47.9 46.2ab 43.6a 8.6 9.9 1.9
63.7 53 47.3 54.7b 7.3
58 51 50.3 53.1b 3.8
61.5b 44.6ab 42.5a 49.6 10.6
8.7 5.2 4.3 10.6 10.6
42.3 42.3 1.5
45.7 45.7 1.5
49.3 49.3 6.2
6.2 6.2 6.2
Well water Well 1 Well 2 Well 3
Mean ±SD Surface water Stations 1 Mean ±SD
-
-
-
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different. -Maximum desirable guideline Limit is 50 mg.l-1 According to the WHO ( 2004 ) drinking water standards. 46
Chapter Five
Result
5.1.9 Total Alkalinity mg CaCO3.l-1 : Generally, the range of Alkalinity concentration was ranging between minimum value of (175 mg CaCO3.l-1 ), observed at W3 during November, and the maximum value of ( 246mg CaCO3.l-1) noted at W1 during October. However, an overall mean of (212.8 mg CaCO3.l-1) was registered during all the studied period, which shown in Table ( 5.9 ) . The minimum mean value of the studied sites was (210.8 mg CaCO3.l-1) obtained at W3; that shows a significant difference with site W1 only, while the maximum mean value was ( 215 mg CaCO3.l-1 ) at W1 which is significantly difference with site W3 only. In the studied months, June showed the minimum mean value (184.7 mg CaCO3.l-1) that was significantly different from other months except November, while the maximum mean (239 mg CaCO3.l-1 ) was during October and was no significantly different from all other months except with June, November and December. Surface water samples ranged between (194.3 -271.3 mg CaCO3.l-1), the minimum data was recorded during May while the maximum recorded during December. 5.1.10 Chloride ( mg.l-1 ) Results showed in Table ( 5.10 ) that the overall mean of Chloride in all studied stations was ( 97.5 mg.l-1). The maximum observed value of Chloride was (195 mg.l-1 ) at Well 1 during September, while the minimum value of ( 70 mg.l-1 ) was noted at Well 3 during November. The minimum mean value of the studied site was ( 76.3 mg.l-1 ) obtained at W2; which showed significant difference from well 1 only. While the maximum mean value was ( 138.2 mg.l-1 ) at W1 which is significantly different from the other studied sites. In the studied months, December shows the minimum mean value ( 79.9 mg.l-1 ) that was significantly different from the other months except for November and October. While the maximum mean ( 119.2 mg.l-1 ) was noted during September which was significantly different from all months except for May, July and August. Surface water samples level ranged between ( 55.7 - 63.7 mg.l-1 ) during May and June respectively, and overall mean recorded was 60.9 mg.l-1.
47
Chapter Five
Result
Table ( 5.9 ): ( Alkalinity ) Concentration value in Water ( mg.l-1 ) with Mean and (±SD) at Solid Waste Disposal area in Halabja City from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
±SD
181.7 221.3 230.7 211.2bc 22.57
188 181 185 184.7a 3.16
216 205 211 210.7bc 4.85
234 231 231.7 232.2c 1.72
235 231 231 232.3c 2.18
246 245 226 239.0c 9.8
226 182.7 175 194.6ab 23.84
193 204.3 196.3 197.9b 5.18
215.0b 212.7ab 210.8a 212.8 22.2
23.3 22.4 21.8 22.2 22.2
194.3 194.3 1.5
205.3 205.3 1.5
-
-
-
-
265.3 265.3 1.5
271.3 271.3 1.5
234.1 234.1 36.1
36.1 36.1 36.1
Well water Well 1 Well 2 Well 3 Mean ±SD Surface water Stations 1 Mean ±SD
-Values with different letters are significantly different at p>0.05, but values with same letters are no significantly different. -Maximum desirable guideline Limit is 200 mg.l-1 According to the WHO drinking water standards. Table ( 5.10 ): (Chloride) Concentration value in Water ( mg.l-1 ) with mean and (±SD) at Solid Waste Disposal area in Halabja City from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
±SD
140
117.3
189
170
195
106
97
91
138.2
b
39.9
a
3.7
a
Well water Well 1 Well 2
Well 3
75
75.3
72
81
81
76.3
79
71
76.3
80
80.3
75
83
81.7
77
70
77.7
78.1
1.5
bc
b
c
c
98.3 31.3
91.0 19.9
112.0 57.8
111.3 44
119.2 56.8
Stations 1
55.7
63.7
Mean
55.7
63.7
±SD
1.5
1.5
-
-
-
Mean ±SD
c
86.4 14.7
ab
82.0 11.9
a
79.9 8.9
a
97.5 36.9
36.9 36.9
-
62.7
61.7
60.9
3.5
62.7
61.7
60.9
3.5
1.5
1.5
3.5
3.5
Surface water
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different. . -1 -Maximum desirable guideline Limit is ( 250 mg.l ) According to the WHO ( 2006 ) and EU drinking water standards. 48
Chapter Five
Result
5.1.11 Sodium ( mg.l-1 ): The Sodium value recorded in the studied period, shown in Table (5.11), for well waters ranged between ( 4.3 - 8.7 mg.l-1 ). The maximum value was obtained during May at W1, while W3 in August showed the minimum value for Sodium concentration. The overall mean value for Sodium concentration was ( 5.8 mg.l-1 ) during the entire studied period. The minimum mean value of the studied sites was (5.1 mg. l-1) obtained at W3 and W2 which was show significantly different from W1, while the maximum mean value was (7.3 mg.l1
) at W1 which was significantly different from the other studied sites. During the period of the study, October showed the minimum mean value (4.9 mg.l-1) that
was significantly different from other months except for November, while the maximum mean ( 7.1 mg.l-1 ) was recorded stated during May and the difference was significant from all other months except for June and December. Surface water sample ranged between ( 5.5 - 10 mg.l-1 ); the minimum data was recorded during May, while the maximum recorded during December, with overall mean recorded was 7.8 mg.l-1. 5.1.12: Potassium ( mg.l-1 ): The Potassium value in the studied period, shown in Table ( 5.12 ), for well waters ranged between ( 0.6 - 1.6 mg.l-1 ); the maximum value obtained during May at W 1, while W2 showed the minimum value for Potassium concentration in September. The overall mean value for Potassium concentration was ( 0.9 mg.l-1 ) during the entire studied period. The minimum mean value of the studied sites was ( 0.8 mg.l-1) obtained at W2 and that showed a significant difference from W1 but no significant difference from W3, while the maximum mean value was ( 1.0 mg.l-1 ) at W1 which is significantly different with the W2 site only. In the studied months, August, September and October showed the minimum mean value (0.7 mg.l-1 ) and were significantly different from other months except July and November, while the maximum mean ( 1.3 mg.l-1 ) was noted during May and was significant difference from all other months except December. Surface water samples range between ( 1.1 - 2.8 mg.l-1), the minimum data was recorded during December, while the maximum recorded during June. 49
Chapter Five
Result
Table ( 5.11 ): ( Sodium ) Concentration value in Water ( mg.l-1 ) with Mean and (±SD) at Solid Waste Disposal area in Halabja City from May to December 2012. Studied sites
May June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
±SD
8.7 6.3 6.2 7.1c 1.2
8.2 5.2 5 6.2bc 1.6
7.7 4.5 4.6 5.6b 1.6
7.4 4.7 4.3 5.5b 1.5
7.5 4.5 4.6 5.5b 1.5
5.2 4.4 5 4.9a 0.4
5.5 4.9 4.9 5.1a 0.3
8.2 6.2 6.3 6.9c 1
7.3b 5.1a 5.1a 5.8 1.4
1.2 0.7 0.7 1.4 1.4
5.5 5.5 0.15
6.2 6.2 0.1
-
-
-
-
9.4 9.4 0.15
10 10 0.25
7.8 7.8 2.04
2.04 2.04 2.04
Well water Well 1 Well 2 Well 3 Mean ±SD Surface water Stations 1 Mean ±SD
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different. . -Maximum permissible concentration Limit is 200 mg.l-1 According to the WHO ( 2006 ) drinking water standards. Table ( 5.12 ): ( Potassium ) Concentration value in Water ( mg.l-1 ) with Mean and ( ±SD ) at Solid Waste Disposal area in Halabja city from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
1.6
1.2
0.9
0.8
0.8
0.75
0.75
1.3
1.0
±SD
Well water Well 1
b
0.3
a
0.2
ab
0.2
Well 2
1.2
0.8
0.72
0.7
0.6
0.8
0.8
1.1
0.8
Well 3
1.2
0.73
0.75
0.7
0.8
0.65
0.9
1.2
0.9
Mean ±SD
c
1.3 0.2
b
0.9 0.2
ab
0.8 0.1
a
0.7 0.1
a
0.7 0.1
a
0.7 0.1
0.8 0.1
1.2 0.1
0.9 0.3
0.3 0.3
Stations 1
2.5
2.8
0.68
1.8
1.1
2.1
0.68
±SD
0.15
0.15
-
2.1
2.8
-
1.1
2.5
-
1.8
Mean
-
0.1
0.15
0.68
0.68
ab
bc
Surface water
- Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different. . -1 - Maximum desirable guideline Limit is 10-12 mg.l According to the WHO ( 2006 ) drinking water standards. 50
Chapter Five
Result
5.1.13: Nitrate nitrogen ( NO3ˉ ) mg-at-N-NO3.l-1: Nitrate levels showed many fluctuations throughout the studied period. However, the total mean of (13.3 mg.l-1) was recorded in the entire sampling period, shown in Table ( 5.13 ), According to the results, the lower concentration (9.3 mg.l-1) was recorded for W2 during May, while the higher concentration 17 mg.l-1 was determined at W1 during May. In the studied months, July showed the minimum mean value (12.6 mg.l-1) that was significantly different from the other months except for May, June, August and December, while the maximum mean (14 mg.l-1) noted during November was no significantly different from all months except June, July and December. The minimum mean value of the studied sites was (12 mg/ l-1) obtained at W2 which showed no significant difference from others study sites, while the maximum mean value was (15.3 mg.l-1 ) at W1 which is no significantly different with other studied sites. Surface water sample ranged between (9.5 – 16.1 mg.l-1); the minimum data was recorded during May, while the maximum recorded during December, with overall mean recorded was 12.6 mg.l-1. 5.2: Water Heavy Trace Metals: 5.2.1: Zinc ( Zn ) mg.l-1: In the study period Zn concentration in all sites was as shown in Table ( 5.14 ). The minimum value for well water was ( 0.002 mg.l-1 ) recorded at W3 during August, September, October, while the maximum value ( 0.012 mg.l-1 ) was recorded at W1 during July. The overall mean value recorded for Zinc was ( 0.004 mg.l-1 ) during the entire studied period. During the studied months, November showed the minimum mean value ( 0.002 mg.l-1 ) that was significantly different from May, June, July and August, while the maximum mean ( 0.006 mg.l-1 ) was noted during June and July and significantly different from all other months except with August. The minimum mean value of the studied sites was ( 0.003 mg.l-1 ) obtained at W2 and W3 and showed a significant difference from W1, while the maximum mean value was ( 0.006 mg.l-1 ) at W1 which was significantly different with other studied sites. Surface water sample ranged between ( 0.003 - 0.009 mg.l-1 ) the minimum data recorded during May, while the maximum recorded during December. 51
Chapter Five
Result
Table ( 5.13 ): ( Nitrate ) Concentration value in Water (mg.l-1) with Mean and (±SD) at Solid Waste Disposal area in Halabja city from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
±SD
17 9.3 14 ab 13.4 3.5
14 12 12.3 a 12.8 1.4
15.3 11.3 11 a 12.6 2.4
15 12 12.7 ab 13.2 1.7
14 12.3 14.7 b 13.7 1.4
15.7 13 12.3 b 13.7 1.9
16 14 12 b 14.0 1.9
15 12.3 11.2 a 12.8 1.9
15.3 b 12.0 b 12.5 13.3 2.1
1.4 1.6 1.6 2.1 2.1
Stations 1
9.5
12.2
2.5
12.6
16.1
12.6
2.5
±SD
0.5
0.8
-
12.6
12.2
-
16.1
9.5
-
12.6
Mean
-
0.6
0.4
2.5
2.5
Well water Well 1 Well 2 Well 3
Mean ±SD
ab
Surface water
- Values with different letters are significantly different at p<0.05,but values with same letters are not significantly different. -Maximum acceptable level of Nitrate in drinking water according to the guidelines of WHO (2006) and EU was ≥ 50 mg.l-1. Table ( 5.14 ): Zinc ( Zn ) Concentration in Water ( mg.l-1 ) with Mean and (±SD) Waste Disposal area in Halabja city from May to December 2012. Studied sites May June July Aug. Sept. Oct. Nov. Dec. Well water 0.004 0.01 0.009 0.004 0.003 0.0022 0.004 Well 1 0.012 0.003 0.004 0.004 0.004 0.0025 0.0022 0.0025 0.003 Well 2 0.004 0.004 0.003 Well 3 0.002 0.002 0.002 0.0022 0.004 b c c bc ab a a ab Mean 0.004 0.006 0.006 0.005 0.003 0.0024 0.002 0.003 0.0003 0.0031 0.0042 0.0031 0.0009 0.0005 0.0005 0.001 ±SD Surface water Stations 1
0.003
0.004
Mean
0.003
0.004
±SD
0.0001 0.0001
-
-
-
-
at Solid Mean 0.006 a 0.003 a 0.003 0.004 0.0026
b
0.0008 0.0037 0.0008 0.0026 0.0026
0.006
0.009
0.005
0.0023
0.006
0.009
0.005
0.0023
0
0.0001
0.0023
0.0023
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different. -Maximum Allowable Limit is ( 3 mg.l-1 ) According to the WHO ( 2006 ) drinking water standards. 52
±SD
Chapter Five
Result
5.2.2: Arsenic ( As ) mg.l-1: The As concentration in all sites for the study period is shown in Table ( 5.15 ). The minimum value for well water was ( 0.01 mg.l-1 ) observed at W1 during May, while the maximum value of ( 0.097 mg.l-1 ) was observed at W3 during November. The overall mean value recorded for Arsenic was ( 0.036 mg.l-1 ) during the entire studied period. Among the studied months, June showed the minimum mean value of ( 0.013 mg.l-1 ) that was significantly different from other months except December, while the maximum mean of ( 0.078 mg.l-1 ) observed during October was significantly different from all other months. The minimum mean value of all the studied sites was ( 0.032 mg.l-1 ) obtained at W1 and was significantly different from the other wells, while the maximum mean value was ( 0.039 mg.l-1 ) at W2 which is significantly different from the other studied wells. Surface water sample ranged between ( 0.05 - 0.16 mg.l-1 ); the minimum data was recorded during May, while the maximum recorded during December, with overall mean recorded was 0.1 mg.l-1. 5.2.3: Cadmium ( Cd ) mg.l-1: The overall mean value recorded for Cadmium concentration was ( 0.0025 mg.l-1). However, it ranged from a maximum value of 0.0034 mg.l-1 at W1 during December, to the lowest value 0.002 mg.l-1 at W3 during June and July, which shown in Table ( 5.16 ). In the studied months, July showed the minimum mean value ( 0.002 mg.l-1 ) that was significantly different from other months except for June and August, while the maximum mean was ( 0.003 mg.l-1 ) stated during May, September, October, November and December respectively, which was significantly different from others months. The minimum mean value in the studied sites was ( 0.002 mg.l-1 ) obtained at W2 showing significant difference from both other wells, while the maximum mean value was (0.003 mg.l-1 ) at W1 and W3 which is significantly different from W2. Surface water sample ranged between ( 0.002 - 0.0035 mg.l-1 ); the minimum data was recorded during June, while the maximum recorded during December, with overall mean recorded was 0.0025 mg.l-1. 53
Chapter Five
Result
Table ( 5.15 ):Arsenic ( As ) Concentration in Water ( mg.l-1 ) with Mean and (±SD) at Solid Waste Disposal area in Halabja city from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
0.01
0.011
0.016
0.045
0.052
0.093
0.013
0.014
0.032
±SD
Well water Well 1 Well 2 Well 3 Mean ±SD
0.016
0.014
0.02
0.016
0.061
0.073
0.014 0.013 0.019 0.015 0.059 b a c d e 0.014 0.013 0.019 0.026 0.057 0.003 0.002 0.002 0.015 0.004
0.096
0.013
a
0.028
c
0.039
0.032
b
0.068 f 0.078 0.012
0.097 g 0.069 0.042
0.014 ab 0.0135 0.002
0.037
0.036 0.03
0.03 0.03
-
0.13 0.13 0.002
0.16 0.16 0.001
0.1 0.1 0.05
0.05 0.05 0.05
0.032
Surface water Stations 1 Mean ±SD
0.05 0.05 0.001
0.06 0.06 0.001
-
-
-
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different. -Maximum Allowable Limit is 0.01 mg.l-1 According to the WHO drinking water standards. Table ( 5.16 ): Cadmium ( Cd ) Concentration in Water ( mg.l-1 ) with Mean and (±SD) at Solid Waste Disposal area in Halabja city from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
0.003
0.0026
0.0023
0.0022
0.003
0.003
0.0025
0.003
0.003
±SD
Well water Well 1 Well 2 Well 3 Mean ±SD
0.0027
0.0022
0.0029 0.002 b a 0.003 0.0022 0.0004 0.0002
0.0022
0.0021
0.002 0.0025 a a 0.002 0.0022 0.0003 0.0005
0.0025
0.0023
0.0022
0.0025
b a
0.002 0.003
b
0.0005 0.0005
0.0029 b 0.003 0.0004
0.0029 b 0.003 0.0005
0.0025 b 0.003 0.0002
0.0028 b 0.003 0.0003
0.0004
0.003 0.0005
0.0005 0.0005
-
-
0.0025 0.0025 0.0001
0.004 0.0035 0.0001
0.0025 0.003 0.0003
0.0003 0.0003 0.0003
Surface water Stations 1 Mean ±SD
0.003 0.003 0.0005
0.002 0.002 0.0001
-
-
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different. -Maximum Allowable Limit is 0.003 mg.l-1 According to the WHO drinking water standards. - Maximum Allowable Limit is 0.005 mg.l-1 according to the EU drinking water standards. 54
Chapter Five
Result
5.2.4: Iron ( Fe ) mg.l-1: The overall mean value recorded for Iron concentration was (0.039 mg.l-1). However, it ranged from a maximum value of 0.079 mg.l-1 at W2 during September, to the lowest value 0.011 mg.l-1 at W2 during July, which shown in Table ( 5.17 ). In the studied months, June showed the minimum mean value ( 0.014 mg.l-1 ) that was significantly different from the other months except for July, while the maximum mean of ( 0.078 mg.l-1 ) was noted during September that differed significantly from all other months. The minimum mean value of the studied sites was ( 0.035 mg.l-1 ) obtained at W3 showing significant difference with site W1 only, while the maximum mean value was ( 0.046 mg.l-1 ) at W1 which was significantly different with W 3 only. Surface water sample ranged between ( 0.051 - 0.171 mg.l-1 ) the minimum data recorded during May, while the maximum recorded during December, with overall mean recorded was 0.099 mg.l-1. 5.2.5 Lead ( Pb ) mg.l-1 Results of lead concentration showed in Table ( 5.18 ) an overall average mean value ( 0.040 mg.l-1 ). The highest value was ( 0.051 mg.l-1 ) recorded at W1 during May, while the lowest value was 0.035 mg.l-1 observed at W1 during August. Among the studied months, October showed the minimum mean value ( 0.038 mg.l-1 ) that was significantly different from May, June and July only, while the maximum mean ( 0.048 mg.l-1 ) was recorded during May that differed significantly from the other months. The minimum mean value of the studied sites was ( 0.039 mg.l-1 ) obtained at W1 showing significant difference from both other wells, while the maximum mean value was ( 0.041 mg.l-1 ) at W2 and W3 respectively which is significantly different with W1. Surface water sample ranged between ( 0.040 - 0.044 mg.l-1 ); the minimum data recorded during June, while the maximum recorded during December, with overall mean recorded was 0.042 mg.l-1.
55
Chapter Five
Result
Table ( 5.17 ): Iron (Fe) Concentration in Water (mg.l-1) with Mean and (±SD) at Solid Waste disposal Area in Halabja city from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
±SD
0.032
0.013
0.023
0.069
0.078
0.052
0.049
0.052
0.046
b
0.021
ab
0.021
a
Well water Well 1 Well 2 Well 3
0.012
0.016
0.011
0.067
0.079
0.036
0.036
0.027
0.036
0.013
0.015
0.012
0.064
0.076
0.038
0.038
0.028
0.035
0.023
b
a
0.015
a
0.067
f
0.078
e
0.042
d
0.041
d
0.036
c
0.039
0.023
Mean
0.019
0.014
±SD
0.01
0.001
0.006
0.002
0.001
0.008
0.006
0.012
0.023
0.023
0.051 0.051 0.0006
0.076 0.076 0.0006
-
-
-
-
0.096 0.096 0.0006
0.171 0.171 0.0006
0.099 0.099 0.0468
0.0468 0.0468 0.0468
Surface water Stations 1 Mean ±SD
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different. - Maximum Allowable Limit is 0.3 mg.l-1 According to the WHO ( 2006 ) drinking water standards. - Maximum Allowable Limit is 0.2 mg.l-1 according to the EU drinking water standards.
Table ( 5.18 ): Lead ( Pb ) Concentration in Water (mg.l-1) with Mean and ( ±SD ) at Solid waste Disposal area in Halabja city from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
±SD
0.051 0.046 0.045 0.048c 0.003
0.037 0.043 0.043 0.041b 0.004
0.036 0.042 0.041 0.040b 0.003
0.035 0.04 0.042 0.039ab 0.003
0.038 0.039 0.039 0.039ab 0.001
0.039 0.037 0.038 0.038a 0.001
0.038 0.039 0.039 0.039ab 0.001
0.039 0.039 0.038 0.039ab 0.001
0.039a 0.041b 0.041b 0.04 0.004
0.005 0.003 0.003 0.004 0.004
0.042 0.042 0.0005
0.04 0.04 0.0003
-
-
-
-
0.041 0.041 0.0013
0.044 0.044 0.0012
0.04 0.042 0.0016
0.0016 0.0016 0.0016
Well water Well 1 Well 2 Well 3 Mean ±SD Surface water Stations 1 Mean ±SD
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different. -Maximum Allowable Limit is 0.01 mg.l-1 According to the WHO ( 2006 ) and EU ( European Union ) drinking water standard. 56
Chapter Five
Result
5.2.6: Nickel ( Ni ) mg.l-1: Nickel concentration in all sites for the study period is shown in table ( 5.19 ). The maximum value for well water was ( 0.015 mg.l-1 ) observed at W1 and W2 during June, while the minimum value ( 0.004 mg.l-1 ) was recorded at W3 during August. The overall mean value recorded was ( 0.008 mg.l-1 ) during the entire studied period. Among the studied months, August showed the minimum mean value ( 0.005 mg.l-1 ) that was significantly different from other months, while the maximum mean ( 0.013 mg.L-1 ) was noted during June showing significant difference from all other months. The minimum mean value in the studied sites was ( 0.007 mg.l-1 ) obtained at W3 showing significant difference from W2 only, while the maximum mean value was (0.009 mg.l-1 ) at W2 which is significantly different with W3 only. Surface water sample ranged between ( 0.021 - 0.022 mg.l-1 ); the minimum data recorded during May, while the maximum recorded during December, with overall mean recorded was 0.021 mg.l-1. Table ( 5.19 ): Nickel ( Ni ) Concentration in Water ( mg.l-1 ) with Mean and (±SD) at Solid Waste Disposal area in Halabja city from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
0.006
0.015
0.008
0.007
0.007
0.007
0.008
0.009
Mean
±SD
Well water Well 1 Well 2 Well 3 Mean ±SD
0.008
0.015
0.013
0.005
0.0068
0.008
0.006
0.007
ab
0.008
b
0.009
a
0.003 0.004
0.008 b 0.007 0.001
0.009 c 0.013 0.003
0.008 b 0.010 0.003
0.004 a 0.005 0.001
0.007 b 0.007 0.001
0.006 b 0.007 0.001
0.007 b 0.007 0.001
0.006 b 0.007 0.001
0.007
0.002
0.008 0.003
0.003 0.003
0.021 0.021 0.0032
0.022 0.022 0.0006
-
-
-
-
0.021 0.021 0.0006
0.022 0.022 0.0025
0.021 0.021 0.0023
0.0023 0.0023 0.0023
Surface water Stations 1 Mean ±SD
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different -Maximum Allowable Limit is 0.02 mg.l-1 According to the WHO drinking water standards.
57
Chapter Five
Result
5.3 Physico - Chemical analysis for monthly Soil sample during the studied period:
5.3.1 Soil pH: The results obtained during the study period ranged between ( 7.9 - 8.25 ); the minimum data was observed at station 3 during June, while the maximum value was observed at station 1 during June, as shown in table ( 5.20 ). The overall mean value of hydrogen ion concentration ( pH ) value recorded for all soil samples was 8.08. The minimum mean value ( 7.94 ) was recorded at station 4, while the maximum mean value ( 8.11) was recorded at station 5 which was no significant differences from the other studied stations. A minimum and maximum value ranging from ( 8.06 - 8.19 ) was observed during October and August respectively. The minimum value was significantly different from all other months except May, while maximum value was significantly different from all other months except for July, September, November and December. 5.3.2 Soil Electrical conductivity ( EC ) µs.cm-1: The results obtained during the studying period ranged between (363.7-580.3 µs.cm-1 ). The minimum value was observed at station 5 during July, while the maximum value was observed at station 1 during November, as show in table ( 5.21 ). The overall mean value recorded for all the soil samples was ( 461.0 µs.cm-1 ). The minimum mean value ( 397 µs.cm-1 ) was recorded at station 5 which show only a significant difference from station 1, while the maximum mean value of the studying stations was ( 498.3 µs.cm-1 ) recorded at station 1 which was significantly different from all other studied stations. While the months under investigation showed a minimum and maximum value ranging from ( 404.2- 506.2 µs.cm-1 ) during July and October respectively. The minimum value was significantly different from all other months, while maximum value was significantly different from all other months except with November.
58
Chapter Five
Result
Table ( 5.20 ): ( pH ) Concentration in Soil with Mean and (±SD) at Solid Waste Disposal area in Halabja City from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
±SD
Station 1
8.09
8.25
8.19
8.08
8.07
8
8.18
8.23
8.09
a
0.11
Station 2
8.1
8.09
8.13
8.07
8.07
8.1
8.15
8.15
8.10
ab
0.07
ab
Station 3
8.1
7.9
8.01
8.2
8.2
8.05
8.17
8.18
8.10
Station 4
7.94
8.08
8.12
8.6
8.12
8.04
8.15
8.18
7.94
Station 5
8.11
8.16
8.15
8.07
8.15
8.1
8.13
8.16
8.11
Station 6 Mean ±SD
8.14 ab
8.08 0.1
8.13
8.1
b
8.11
bc
8.11 0.14
8.13 0.09
8.1
c
8.19 0.2
8.02
bc
8.14 0.08
8.12
a
ab
8.11
bc
8.06 0.09
8.17 0.07
0.2
ab
0.06
ab
0.07
8.10
c
8.15 0.07
0.12
8.08
0.12
0.12
0.12
-Values with different letters are significantly different at p>0.05, but values with same letters are
not significantly different. Table ( 5.21 ): ( EC ) Concentration in Soil (μs.cm-1) with Mean and ( ±SD ) at Solid Waste Disposal area in Halabja City from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
±SD
Station 1
557
420
424
433.3
461.7
566
580.3
543.7
498.3
c
67.9
Station 2
412.3
395.7
415
480
450.7
560
504
498
464.5
b
54.6
Station 3
411.3
566
394
413.7
475
445
481.7
441.7
453.5
a
52.8
Station 4
405
503.3
425
434.3
560
536.3
571.7
498.3
491.8
b
61.5
ab
19.6
ab
Station 5
409
379
363.7
412.7
391.7
418
406.7
395.7
397.0
Station 6
436.3
503.3
403.7
424.7
487.3
511.7
455.3
463
460.7
37.4
461
60.4
60.4
60.4
bc
Mean
438.5
461.2
±SD
56.1
69.9
c
a
b
cd
404.2
433.1
471.1
24.4
24.8
51.8
e
de
506.2
499.9
473.4
59.1
63.8
49.4
d
-Values with different letters are significantly different at p>0.05, but values with same letters
are not significantly different.
59
Chapter Five
Result
5.3.3 Total Sulfur ( % ): Results of soil total sulfur in the studied stations during the studied period, an illustrated in Table ( 5.22 ), showed that the minimum value ( 0.002 % ) was recorded at site 1 during June, while the maximum value (0.03 %) was recorded at station 5 during November. The overall mean value recorded for all the soil samples was ( 0.018 % ). The statistical analysis for the studied stations showed that the minimum value ( 0.014 % ) was recorded at station 1,which show a significant difference from all other stations except station 6.
While ( 0.021% ) was the maximum mean value recorded at station 4 and 5
respectively and showed a significant difference from all other stations. Significant differences were observed among the results obtained during the period under investigation, as the maximum value ( 0.023% ) was recorded during August show a significant difference from the other months except November, while the minimum value ( 0.013% ) recorded during May showed significant difference from all other studying months except June, July and October. 5.3.4 Total Nitrogen ( % ): Nitrogen content of the studying station during the studying period was ranging between the minimum value ( 3.9 % ) observed at station1 during May to the maximum value ( 6.9 % ) at station 5 during May, as in Table ( 5.23 ). The overall mean value recorded for all the soil samples was ( 5.3 % ). Statistical analysis of data from the studying stations showed that the minimum mean value ( 4.6 % ) was recorded at station 1 showing no significant difference with the other stations, while the maximum mean value ( 6 % ) was determined at station 5 which showed a significant difference with the other stations except station 1. Among the studied months the minimum mean value ( 5 % ) was recorded during October, which was significantly different with August only, on the other hand, the maximum value ( 5.6% ) was noted during August which showed significant difference from May, October and December only .
60
Chapter Five
Result
Table ( 5.22 ): ( Total Sulfer ) Concentration in Soil (%) with Mean and (±SD) at Solid Waste Disposal area in Halabja City from May to December 2012.
Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
Station 1
0.012
0.002
0.003
0.024
0.02
0.009
0.016
0.016
0.014
Station 2
0.014
0.005
0.011
0.027
0.015
0.017
0.028
0.02
0.017
±SD
a
0.1
b
0.08
b
0.04
c
0.04
c
0.08
ab
Station 3
0.02
0.022
0.02
0.018
0.014
0.013
0.013
0.019
0.017
Station 4
0.013
0.022
0.021
0.029
0.021
0.02
0.021
0.022
0.021
Station 5
0.006
0.018
0.018
0.02
0.022
0.029
0.03
0.028
0.021
Station 6
0.015
0.019
0.018
0.016
0.018
0.018
0.009
0.01
0.015
0.04
d
b
0.018
0.07
0.07
0.07
Mean ±SD
a
ab
0.013 0.05
0.015 0.09
ab
0.015 0.07
0.023 0.07
0.018 0.04
ab
0.018 0.07
cd
0.020 0.08
0.019 0.06
c
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different.
Table ( 5.23 ): ( Total Nitrogen ) Concentration in Soil ( % ) with mean and (±SD) at Solid Waste Disposal area in Halabja City from May to December 2012.
Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Station 1
3.9
4.6
4.7
4.7
4.6
4.8
5.4
4.4
Station 2 Station 3 Station 4
5.5 4.6 5.2
5.1 4.9 5.7
4.8 5.1 5.5
5.1
4.6
6.3
5.6
5.5
5.7
4.6 4.7 5.5
5.1 5.3 5.6
5.2 5.8 5.8
Mean
±SD
abc
0.5
a
0.3
ab
0.6
ab
0.2
c
0.6
4.6
5.0 5.3 5.6
Station 5
6.9
6.2
6
6.5
6.1
5.2
5.5
5.4
6.0
Station 6
5.2
5.6
5.5
5.7
5.4
5.1
4.8
4.7
5.2
a
0.4
5.3
0.6
0.6
0.6
Mean ±SD
5.2 1
a
ab
5.4 0.6
ab
5.3 0.5
b
5.6 0.7
ab
5.3 0.6
a
5.0 0.4
ab
5.3 0.3
a
5.2 0.6
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different.
61
Chapter Five
Result
5.3.5 Organic matter ( LOI % ): Results of soil total organic matter analysis in the studied stations during the studied period is illustrated in Table ( 5.24 ), which shows that the minimum value ( 10.3% ) was recorded at station 6 during November, while the maximum value (12.1 %) recorded at station 4 during May. The overall mean values recorded for all the soil samples was ( 11.2 % ). Statistical analysis for the studied stations showed that the minimum value ( 10.8% ) was recorded at station 6 which was no significantly different from other stations except stations 1 and 4, while ( 11.6 % ) was the maximum mean value recorded at station 4 and showed a significant difference from all the other stations except for station 1. While in the studied months the minimum mean value ( 11.0 % ) was recorded during September and October, which was only significantly different from May, on the other hand the maximum value ( 11.6% ) was noted during May which showed significantly difference from other months except for July. 5.3.6 Sodium concentration ( Na+ ) ( mg.kg-1 ): The minimum level of Sodium in the studying stations during the entire period ( 2766 mg.kg-1) was at station 1 during July, while the maximum level was reached during December at station 4 ( 3805 mg.kg-1 ), as presented in Table ( 5.25 ). The overall mean values recorded for all the soil samples was (3195 mg.kg-1). The mean value of Sodium concentration for the studying stations ranged between (3133 mg.kg-1 - 3345 mg.kg-1), the minimum value was at station 1 with a significant difference from the station 4, station 5 and station 6 only, and the maximum value was at station 4 with a significant difference among the other studied stations. Among the study months, the minimum mean value ( 3082 mg.kg-1 ) was recorded during July which was significantly different from other months except for June and August, while (3343 mg.kg-1 ) was the maximum mean value recorded during December showing significant difference with the other studied months except November.
62
Chapter Five
Result
Table ( 5.24 ): ( Organic matter ) Concentration in Soil ( LOI% ) with Mean and ( ±SD ) at Solid Waste Disposal area in Halabja City from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
±SD
Station 1
11.5
11.6
11.6
11.4
11.6
11.6
11.2
11.4
11.5
b
0.38
Station 2
12
11.1
11.5
11.3
10.8
10.6
10.9
11.2
11.2
a
0.49
Station 3
11.1
11.2
11.7
11
10.6
10.5
11.3
11.6
11.1
a
0.45
b
0.32
a
0.28
Station 4
12.1
11.1
11.7
11.8
11.3
11.6
11.5
11.8
11.6
Station 5
11.6
11.5
11.5
11.4
11.1
11.4
11
11.3
11.3
Station 6
11.1
10.8
11.1
10.7
11
10.5
10.3
10.7
10.8
a
0.28
b
a
a
a
a
11.2
0.44
0.44
0.44
Mean ±SD
11.6 0.47
11.3 0.38
ab
11.5 0.27
a
11.2 0.37
a
11.0 0.37
11.0 0.54
11.1 0.37
11.3 0.37
-Values with different letters are significantly different at p>0.05, but values with same letters
are not significantly different.
Table ( 5.25 ): Sodium ( Na+ ) Concentration in Soil (mg.kg-1) with Mean and (±SD) at Solid Waste Disposal area in Halabja City from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
±SD
Station 1
3440
3290
2766
2880
3167
3140
3238
3145
3133
a
219
Station 2
2808
3117
3094
3028
3173
3213
3382
3392
3151
ab
207
a
118
d
259
c
191
Station 3
3337
3046
3144
3084
3071
3027
3245
3121
3134
Station 4
3229
3079
3075
3337
3322
3337
3577
3805
3345
Station 5
3021
3117
3147
3072
3221
3439
3385
3335
3217
Station 6
3132
3192
3263
3153
3086
3225
3210
3259
3190
b
83
a
a
3195
200
200
200
Mean ±SD
3161 217
b
ab
3140 104
3082 162
3092 157
3173 94
bc
3230 159
c
cd
3339 234
3343 251
d
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different.
63
Chapter Five
Result
5.3.7 Magnesium Concentration ( mg.kg-1 ): Magnesium content of the studying station during the studying period ranged between the maximum value ( 18998 mg.kg-1 ) observed at station 3 during May to the minimum value (13326 mg.kg-1) at station 1 during December, as in Table ( 5.26 ). The overall mean value recorded for all the soil samples was (15511 mg.kg-1). Statistical Analysis for the studying stations, shows that the minimum mean value (14841 mg.kg-1) was recorded at station 1 showing no significant difference from the other stations except for station 3 and station 4, while the maximum mean value ( 16121 mg.kg-1 ) determined at station 3 showing a significant difference from all other stations. Among the studied months, the minimum mean value (14867 mg.kg-1) was recorded during June which significantly differs from all other months except July and August, on the other hand, the maximum value (16742 mg.kg-1 ) was noted during May show a significant difference from all other months. 5.3.8 Potassium ( K+ ) mg.kg-1: Samples from all different stations taken during the period of this investigation showed variation in potassium concentration as in Table ( 5.27 ). The minimum level ( 13193 mg.kg-1) was observed at station 6 during June, while the maximum level reached was (15835 mg.kg-1) at station 5 during November. The overall mean value recorded for all the soil samples was (14260 mg.kg-1). Among the studied months, the minimum mean value was (14066 mg.kg-1) recorded during August, which was only significantly different from October, whereas the maximum value (14372 mg.kg-1) was observed during October showing only a significant difference with August. Station 1 showed the minimum rate of potassium mean concentration (13962 mg.l-1) that was significantly different from the other stations, but the maximum mean concentration (14593 mg.l-1) was reached at station 5 which was significantly different from all the other stations.
64
Chapter Five
Result
Table ( 5.26 ): Magnesium ( Mg+2 ) Concentration in Soil ( mg.kg-1 ) with Mean and ( ±SD ) at Solid Waste Disposal area in Halabja City from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
Station 1
15624
15175
14943
14510
15880
15551
13720
13326
14841
Station 2
17038
14449
15056
15947
13914
13660
15810
14322
15025
Station 3
18998
15364
15857
15643
14817
15088
16476
16723
16121
Station 4
18188
15154
14203
14474
15563
17198
16083
16497
15920
Station 5
14959
13871
15205
16135
16139
17073
15982
16096
15683
Station 6
15646
15188
15136
14724
15536
15115
16175
16308
15478
Mean
16742
14867
±SD
1529
725
d
a
ab
15067
15239
531
797
ab
15308
b
786
15614
bc
15708
1384
c
15545
979
±SD
a
987
a
1172
c
1317
b
c
1315
1325
ab
981
ab
582
15511
1166
1166
1166
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different. Table ( 5.27 ): Potassium ( K+ ) Concentration in Soil ( mg.kg-1 ) with Mean and ( ±SD ) at Solid Waste Disposal area in Halabja City from May to December 2012. Studied sites
May
June
July
Aug.
Sept
Oct.
Nov.
Dec.
Mean
Station 1
13956
14675
14175
13701
13916
14284
13372
13619
13962
Station 2
13753
14327
13952
14225
14253
13573
15460
14466
14251
Station 3
14650
14787
14383
14752
14106
13618
13535
13905
14217
Station 4
14429
14787
15052
13879
14126
14545
13372
13822
14252
Station 5
14653
13708
13569
13879
14790
15358
15835
15466
14593
Station 6
14333
13193
14595
13960
14403
14855
14188
14224
14283
Mean ±SD
ab
14296
14246
388
681
ab
ab
14288 525
14066
a
469
14265 358
ab
14372 758
b
14293
ab
1056
14250 662
ab
b b b c
b
415 606 548 573 986 424
14260
638
638
638
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different. 65
a
±SD
Chapter Five
Result
5.3.9 Calcium ( Ca+2 ) mg.kg-1: Calcium content of the studying stations during the study period ranged between the minimum value of (42489 mg.kg-1) observed at station 1 during June to the maximum value ( 75648 mg.kg-1 ) at station 5 during June, as in table ( 5.28 ). The overall mean value recorded for the all the soil samples was ( 60871 mg.kg-1). Statistical analysis for the studying sites, showed a minimum mean value of (49782 mg.kg-1) recorded at site 1 was showing significant difference with the all other stations, while the maximum mean value (68835 mg.kg-1 ) was determined at station 4 showing significant difference from the station 1 and 2 . Among the studied months the minimum mean value ( 55043 mg.kg-1 ) was recorded during June, which significantly differed from the all other months, while the maximum value was noted (64991 mg.kg-1) stated during October which was significantly different from the all other months. 5.3.10 Calcium carbonate ( % ): Samples from all different stations taken during the period of this investigation showed variation in the calcium carbonate concentration, as in Table ( 5.29 ). The minimum level (20.4 % ) was observed at station 2 during October , while the maximum level recorded was (29.2 %) at station 4 during December. The overall mean value recorded for all the soil samples was ( 24.9% ). Station 2 showed minimum rate of calcium carbonate mean concentration of ( 21.6% ) that showed a significant difference from all the other stations, but the maximum mean concentration of ( 26.7% ) was obtained at station 4 showed significant difference from all other stations except station 3 and 4 respectively. Among the studied months the minimum mean value (22.5%) was recorded during June which was a significant difference from the all other months except May and July while the maximum value recorded was ( 26.4 %) during December revealing significant differences with the other months except for September, October and November .
66
Chapter Five
Result
Table ( 5.28 ): Calcium ( Ca+2 ) Concentration in Soil ( mg.kg-1 ) with Mean and (±SD) at Solid Waste Disposal area in Halabja City from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
±SD
Station 1
54981
42489
46455
54714
48913
47806
50564
52329
49782
a
4286
Station 2
57573
47006
58469
58381
66831
65806
57923
63412
59425
b
6674
bc
6611
c
5776
bc
6617
61209
bc
4287
60871
8270
8270
8270
Station 3
57573
47006
54997
66631
64928
67139
60531
62340
60143
Station 4
69548
54956
68753
70623
70894
71506
73123
71275
68835
Station 5
61498
75648
62976
56048
66017
71706
65048
67735
65834
Station 6 Mean ±SD
56174
63151
56598
57650
63532
65985
59823
c
a
b
d
f
g
e
59558 5426
55043 11874
58041 7210
60674 6283
63519 7181
64991 8602
61169 8182
66761 ef
63975 6233
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different. Table ( 5.29 ): ( Calcium carbonate ) Concentration in Soil ( % ) with Mean and ( ±SD ) at Solid Waste Disposal area in Halabja City from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
Station 1
24.5
21.7
23.7
26.7
25.7
26.4
27.1
28.8
25.6
Station 2
21.7
20.8
22.6
21.8
21.1
20.4
21.1
23.5
21.6
Station 3
24.6
24.8
25.8
24.6
25
27.6
28.9
28
26.2
±SD
c
2.2
a
1.1
cd
1.7
d
2.2
Station 4
26.4
23.3
24.4
24.8
27.8
28.8
28.7
29.2
26.7
Station 5
24.3
23.4
25.2
26.8
28.6
29.1
25.5
25.6
26.0
Station 6
21.9
20.5
21.7
22.8
23.8
25.1
25.2
23.4
23.0
b
1.6
c
c
c
24.9
2.6
2.6
2.6
Mean ±SD
ab
23.9 1.7
a
22.5 1.6
ab
23.9 1.5
b
bc
24.6 1.9
25.3 2.6
26.2 3.1
26.0 2.8
26.4 2.5
cd
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different.
67
1.9
Chapter Five
Result
5.3.11 Bicarbonate ( HCO3- ) mg.kg-1: Bicarbonate concentration in all stations during the period of the study is presented in Table ( 5.30 ). The table which shows that the minimum value (19 mg.kg-1) recorded at station 6 during June, while the maximum value of ( 48.4 mg.kg-1) was recorded at station 5 during August. The overall mean value recorded for all the soil samples was ( 32.6 mg.kg-1). Statistical analysis for the study stations showed that the minimum mean value ( 22.4 mg.kg-1) was recorded at station 6 that revealed a significant difference from the other stations, while the maximum mean value ( 38.3 mg.kg-1 ) was recorded at station 5 which was significantly different from all the other studied stations. On the other hand, the studying months showed significant difference in the recorded data. The minimum mean value of (23.7 mg.kg-1) was recorded during June showing a significant difference with all the other months, while the maximum level was observed during August ( 38.9 mg.kg-1 ) and show significant difference from all the other sites except September. 5.3.12 Available phosphorus mg.kg-1: Samples from all different sites taken during the period of this investigation showed variation in the available phosphorus concentration, as in Table (5.31). The minimum level (2.3 mg.kg-1) was observed at station 6 during August and November, while the maximum level reached was (8.7 mg.kg-1) at station 4 during November. The overall mean value recorded for all the soil samples was (5.3 mg.kg-1). During the period of the study, the minimum mean value (5.2 mg.kg-1) was recorded during July and August, which was only significantly different from September and October, while the maximum value (5.5 mg.kg-1) was notes during September and October showing significant difference from the all other months. Station 6, showed the minimum rate of available phosphorus mean concentration (2.5 mg.kg-1) that is significantly different from the all other stations , but the maximum mean concentration ( 8.5 mg.kg-1 ) was reached at station 4 that showed a significant difference from all the other stations except station 5.
68
Chapter Five
Result
Table ( 5.30 ): ( Bicarbonate ) Concentration in Soil ( mg.kg-1 ) with Mean and ( ±SD ) at Solid Waste Disposal area in Halabja City from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean ±SD
Station 1
22.6
24.7
30.5
35.9
39.1
47.5
46.1
42.1
36.1
Station 2
24.7
21.8
24.3
41.4
45.1
40.5
24.7
36.9
32.4
Station 3
24.7
24.9
35.7
38.3
36.3
33.8
35.7
30.8
32.5
d
9
b
9
b
5
c
7.1
e
10.1
a
Station 4
27.9
27.7
42.1
44.9
39
33.8
27.6
25.9
33.6
Station 5
24.9
23.9
36.4
48.4
45.8
31.3
47.8
48.1
38.3
Station 6
21.2
19
21.2
24.4
21.8
24.9
21.8
25.1
22.4
2.1
Mean
24.3
23.7
31.7
38.9
37.8
35.3
34.0
34.8
32.6
9
±SD
2.2
2.8
7.5
7.9
8.2
7.4
10.4
8.7
9
9
b
a
c
f
ef
e
d
d
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different. Table ( 5.31 ): ( Available phosphorus ) Concentration in Soil ( mg.kg-1 ) with Mean and ( ±SD ) at Solid Waste Disposal area in Halabja City from May to December 2012.
Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
Station 1
3.2
3.7
3.8
3.5
4.2
4.2
4
3.9
3.8
b
0.4
bc
0.3
c
0.3
d
0.2
cd
0.5
2.5
a
0.2
5.3
1.9
1.9
1.9
Station 2
5.8
5.3
5.1
5
5.1
5.1
5.8
5.4
5.3
Station 3
5.6
5.4
5.5
5.5
5.8
5.9
5.3
5.8
5.5
Station 4
8.6
8.6
8.3
8.3
8.6
8.4
8.7
8.4
8.5
Station 5
6.3
6.1
6.3
6.7
6.3
6.5
6
5.4
6.2
Station 6
2.5
Mean
5.3 2.13
±SD
a
2.7 a
5.3 1.92
2.5 a
5.2 1.88
2.3 a
5.2 2.08
2.7 b
5.5 1.87
2.9 b
5.5 1.8
2.3 a
5.3 2.02
2.7 a
5.3 1.86
±SD
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different.
69
Chapter Five
Result
5.4: Soil Heavy Trace Metals: 5.4.1 Zinc ( Zn ) mg.kg-1: Concentration of zinc in all sites during the studying period are presented in Table (5.32). The table shows that the minimum value (225.03 mg.kg-1) was recorded at station 6 during November, while the maximum value ( 915.22 mg.kg-1) was recorded at station 3 during November. The overall mean value recorded for all the soil samples was ( 445.67 mg.kg-1 ). Statistical analysis for the studying stations showed that the minimum mean value (268.22 mg.kg-1) was recorded at station 6 that revealed a significant difference from the other stations, while the maximum mean value (668.57 mg.kg-1) was recorded at station 3 which was significantly different from all other studied stations. In the studied months the minimum mean value (403.97 mg.kg-1) was recorded during May, which was significantly different from all the other months except for July, while the maximum value (534.95 mg.kg-1) was stated during November which showed a significant difference from all the other months. 5.4.2 Arsenic ( As ) mg.kg-1: Concentration of Arsenic in all stations during the studying period are presented in Table (5.33), which shows that the minimum value (14.23 mg.kg-1) was recorded at station 5 during June, while the maximum value ( 20.15 mg.kg-1 ) was recorded at station 3 during October. The overall mean value recorded for all the soil samples was (16.45 mg.kg-1). Statistical analysis for the studying stations showed that the minimum mean value (14.77 mg.kg-1) recorded at station 6 revealed a significant difference from the all other stations, while the maximum mean value (17.75 mg.kg-1) recorded at station 3 which was significantly different from all the other studied stations. In the studied months the minimum mean value (15.59 mg.kg-1) was recorded during November , which was significantly different from all the other months except May and December, while the maximum value (17.17 mg.kg-1) was stated during August and September which showed a significant difference from all the other months except for October.
70
Chapter Five
Result
Table ( 5.32 ): Zinc (Zn) Concentration in Soil ( mg.kg-1 ) with Mean and (±SD) at Solid Waste Disposal area in Halabja City from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
Station 1
527.34
432.01
356.61
356.61
411.15
418.52
413.01
444.79
420.00
Station 2 Station 3 Station 4 Station 5 Station 6 Mean ±SD
397.57 370.99 425.27 403.43 299.21 a
403.97 70.1
379.24 607.51 527.86 356.61
363.58 661.31 397.11 415.59
360.74
371.79
862.12
616.43
357.75 421.27
277.69
283.76
a
c
411.98 123.73
440.38 198.39
433.84 113.01
355.84
225
d
458.38 132.81
627.57
370
282.73
bc
686.39
915.2
366.07
275.77
371.95
915.34
628.45
403.11
b
370.97
628.45
524.78
260.32 427.26 121.81
426.05
e
534.95 283.72
±SD
c
51.7
b
20.99
f
160.28
d
173.2
b
27.23
a
380.24
668.57 550.52 386.49
241.29
268.22
23.61
d
445.7 162.95
162.95 51.7
454.64 160.44
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different. - Maximum Allowable Limit is ( 150 - 300 mg.kg-1 ) According to the European union ( EU). Table ( 5.33 ): Arsenic ( As ) Concentration in Soil ( mg.kg-1 ) with Mean and ( ±SD ) at Solid Waste Disposal area in Halabja City from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
±SD
Station 1
14.25
17.72
16.32
17.04
17.4
17.26
14.75
15.82
16.32
c
1.27
Station 2
15.94
17.52
17.27
18.73
18.09
17.26
16.67
16.82
17.29
d
1.15
Station 3
16.61
16.68
18.1
18.81
19.32
20.15
16.09
16.25
17.75
e
1.54
c
0.9
b
1
Station 4
15.8
17.71
17.54
17.02
16.66
16.69
15.33
16.03
16.60
Station 5
16.63
14.23
16.04
16.99
16.63
15.65
15.96
15.54
15.96
Station 6
14.8
15.16
14.43
14.43
14.93
15.09
14.74
14.58
14.77
a
0.34
Mean
15.67
16.50
16.62
17.17
17.17
17.02
15.59
15.84
16.45
1.45
±SD
0.95
1.47
1.28
1.57
1.42
1.72
1.2
0.81
1.45
1.45
a
b
b
c
c
c
a
a
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different. -Maximum Acceptable Limit is ( 20 mg.kg-1 ) According to the European union ( EU).
71
Chapter Five
Result
5.4.3 Cadmium ( Cd ) mg.kg-1: Soil samples collected during the studying period showed variation in Cadmium concentration as illustrated in Table ( 5.34 ). The data varied from the minimum value ( 2.317 mg.kg-1) at station 5 during November to the maximum value (5.712 mg.kg-1) recorded at station 3 during October. The overall mean value recorded for all the soil samples was ( 3.495 mg.kg-1 ). Statistical analysis for the studying stations showed that the minimum mean value (3.060 mg.kg-1) recorded at station 6 revealed a significant difference from the other stations except for station 5, while the maximum mean value (4.388 mg.kg-1) recorded at station 4 was significantly different from all the other studied stations . In the studied months the minimum mean value (3.002 mg.kg-1) was recorded during November , which was significantly different from all the other months, while the maximum value ( 4.198 mg.kg-1 ) observed during October showed a significant difference with all the other months except for July, August and September. 5.4.4 Lead ( Pb ) mg.kg-1: Soil samples during the studying period showed variation in Lead concentration, as illustrated in Table ( 5.35 ). The data varied from minimum value ( 76.71 mg.kg-1 ) at station 6 during November to the maximum value ( 193.14 mg.kg-1 ) recorded at station 3 during June. The overall mean value recorded for all the soil samples was ( 121.91 mg.kg-1 ). Statistical analysis for the studying stations showed that the minimum mean value (83.18 mg.kg-1) was recorded at station 6 and was significantly different from the other stations, while the maximum mean value (161.99 mg.kg-1) was recorded at station 3 which was significantly different from all other studied stations. In the studied months the minimum mean value (107.40 mg.kg-1) was recorded during August, which was significantly different from all other months, while the maximum value ( 133.96 mg.kg-1 ) observed during May showed a significant difference from all the other months.
72
Chapter Five
Result
Table ( 5.34 ): Cadmium ( Cd ) Concentration in Soil ( mg.kg-1 ) with Mean and (±SD) at Solid Waste Disposal area in Halabja City from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
Station 1
3.218
3.325
3.104
3.165
3.353
3.189
3.511
3.442
3.288
Station 2
3.211
3.17
3.347
3.162
3.482
4.379
2.516
3.251
3.315
±SD
b
0.225
b
0.529
c
0.529
d
1.024
a
0.333
Station 3
3.15
3.961
3.554
4.021
3.555
5.712
3.511
3.321
3.848
Station 4
5.708
3.157
4.157
4.811
4.498
5.642
3.511
3.622
4.388
Station 5
3.219
3.327
3.265
3.166
3.091
3.093
2.317
3.009
3.069
Station 6
3.16
3.204
3.18
3.112
3.082
3.173
2.642
2.986
3.060
a
0.201
a
b
3.495
0.368
0.657
0.51
Mean ±SD
e
3.611d 0.966
e
3.357 0.347
cd
3.434 0.403
de
3.573 0.968
c
cd
3.511 0.514
4.198 1.179
3.002 0.564
3.271 0.315
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different. - Maximum Allowable Limit is ( 1-3 mg.kg-1 ) According to the European union ( EU ). Table ( 5.35 ): Lead ( Pb ) Concentration in Soil ( mg.kg-1 ) with Mean and ( ±SD ) at Solid Waste Disposal area in Halabja City from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
Station 1
162.64
167.99
113.03
90.83
96.55
93.91
109.97
96.28
116.40
Station 2
122.53
118.63
107.4
97.24
98.54
192.86
117.33
103.88
119.80
Station 3
119.23
193.1
173.12
142.38
180.35
142.23
179.76
165.71
161.99
±SD
c
29.82
d
30.08
f
24.06
e
20.15
Station 4
168.56
118.89
124.5
141.2
139.05
148.53
179.76
156.9
147.17
Station 5
145.85
99.79
85.83
90.83
91.14
118.2
93.59
97.91
102.89
b
19.05
Station 6
84.94
84.77
86.94
81.91
83.55
85.72
76.71
80.91
83.18
a
3.19
121.9
29.82
34.67
32.3
Mean ±SD
133.96 29.53
e
130.53 39.05
d
115.14 30.28
b
a
107.40 25.45
114.86 35.21
b
130.24 37.22
d
126.19 41.8
c
116.93 33.18
b
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different. - Maximum Allowable Limit is ( 10 - 300 mg.kg-1 ) According to the European union ( EU ). 73
Chapter Five
Result
5.4.5 Nickle ( Ni ) mg.kg-1: The soil samples during the studying period showed variation in Nickle concentration, as illustrated in Table ( 5.36 ). The data varied from the minimum value ( 150.41 mg.kg-1 ) at station 6 during June to the maximum value ( 192.24 mg.kg-1 ) recorded at station 4 during June. The overall mean value recorded for all the soil samples was (175.33 mg.kg-1 ). Statistical analysis for the study stations showed that the minimum mean value ( 170.49 -1
mg.kg ) was recorded at station 6 which revealed a significant difference from all other stations except station 1, while the maximum mean value (183.89 mg.kg-1) was recorded at station 3 which was significantly different from all other studied stations. In the studied months, the minimum mean value ( 168.8 mg.kg-1 ) was recorded during May which was significantly different from all other months, while the maximum value ( 177.82 mg.kg-1 ) was noted during November which showed no significant difference from the all other months except for May. 5.4.6 Chrome ( Cr ) mg.kg-1: Soil samples collected during the studying period showed variation in Cr concentration, as illustrated in table ( 5.37 ). The data varied from the minimum value (142.22 mg.kg-1) at station 6 during June to the maximum value (173.07 mg.kg-1) recorded at station 3 during August. The overall mean value recorded for all the soil samples was (160.23 mg.kg-1). Statistical analysis for the studying stations showed that the minimum mean value (154.14 mg.kg-1) recorded at station 6 revealed a significant difference from the other stations, while the maximum mean value (167.33 mg.kg-1) recorded at station 3 was significantly different from all the other studied stations. In the studied months the minimum mean value (151.96 mg.kg-1) was recorded during May and was significantly different from all the other months, while the maximum value was (163.98 mg.kg-1) observed during November and showing a significantly difference from all the other months except August, September, October and December.
74
Chapter Five
Result
Table ( 5.36 ): Nickle ( Ni ) Concentration in Soil ( mg.kg-1 ) with Mean and ( ±SD ) at Solid Waste Disposal area in Halabja City from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
±SD
Station 1
158.9
186.85
171.03
171.16
174.17
174.53
184.73
162.56
172.99ab
9.44
Station 2
160.47
190.27
180.39
179.4
169.83
168.54
181.73
172.93
175.45b
10.67
Station 3
175.38
180.97
183.35
190.71
185.14
185.7
184.74
185.16
183.89c
5.49
Station 4
171.17
192.2
172.53
172.06
171.94
175.21
172.67
176.23
175.50b
7.81
Station 5
179.62
166.14
173.84
175.29
181.68
173.85
174.86
179.94
173.68b
10.92
172.18
170.49
a
4.1
Station 6
167.24
150.4
172.13
170.25
175.65
Mean
168.80a
177.81b
175.55b 176.48b
176.40b 175.00b
177.82b 174.83b
175.3
9.32
±SD
158.9
186.85
171.03
174.17
184.73
172.99
91.2
171.16
172.18
174.53
168.13
162.56
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different. - Maximum Allowable Limit is ( 30 -75 mg.kg-1 ) According to the European union ( EU ). Table ( 5.37 ): Chrome ( Cr ) Concentration in Soil ( mg.kg-1 ) with Mean and ( ±SD ) at Solid Waste Disposal area in Halabja City from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
±SD
Station 1
146.22
166.49
153.69
151.44
161.48
165.88
167.3
161.17
159.20bc
7.96
Station 2
142.88
170.06
165.14
163.53
163.65
157.79
170.28
164.89
162.27d
9.81
Station 3
157.57
162.38
167.66
173.1
170.56
171.48
167.3
168.62
167.33e
6.05
Station 4
155.79
169.6
160.8
157.95
157.95
160.64
161.82
161.21
160.72cd
5.88
Station 5
155.79
148.5
155.5
162.71
160.46
160.54
163
161.38
157.70b
8.56
a
Station 6
153.52
142.2
152.39
155.28
154.46
157.16
154.2
157.61
154.14
3.68
Mean
151.96a
159.88b
159.20b
160.6bc
161.43bc
162.25bc
163.98c
162.48bc
160.2
3.43
±SD
6.06
11.6
6.4
8.4
5.51
6.78
9.8
3.87
7.3
5.37
-Values with different letters are significantly different at p>0.05, but values with same letters
are not significantly different. - Maximum Allowable Limit is ( 100-150 mg.kg-1 ) According to the European union ( EU). 75
Chapter Five
Result
5.4.7 Manganese ( Mn ) mg.kg-1: Soil samples showed variation between the data from a minimum of (987 mg.kg-1) at station 6 during June to the maximum value of (1187 mg.kg-1) at station 3 during August, as in Table ( 5.38 ). The overall mean value recorded for all the soil samples was (1085 mg.kg-1). Statistical analysis for the study stations revealed that the minimum mean value (1078 mg.l1
) recorded at station 6 showed no significant difference with all the other stations, while the
maximum mean (1107 mg.l-1) recorded at station 3 was no significantly different from all the other studied stations. In the studied months, the minimum mean value was (1033 mg.kg-1) recorded during November, and was significantly different from all the other months except September and December, while the maximum value ( 1131 mg.kg-1 ) observed during August showed a significantly difference from September and November only. 5.4.8 Copper ( Cu ) mg.kg-1: Soil samples showed variation in the data from a minimum of ( 232.81 mg.kg-1 ) at station 1 during November to a maximum value of (301.09 mg.kg-1) at station 3 during August, as in Table ( 5.39 ). The overall mean value recorded for all the soil samples was ( 286.4 mg.kg-1 ). Statistical analysis for the study stations revealed that the minimum mean value ( 280.02 mg.l-1) mentioned at station 1 showed significant difference with all the other stations except station 3, while the maximum mean ( 294.33 mg.l-1 ) recorded at station 5 was significantly different from all the other study stations. In the studied month, the minimum mean value ( 262.04 mg.kg-1 ) was recorded during November, and was significantly different from all the other months, while the maximum value ( 297.12 mg.kg-1 ) was recorded during June showing significant difference from all the other months except May and August.
76
Chapter Five
Result
Table ( 5.38 ): Manganese ( Mn ) Concentration in Soil ( mg.kg-1 ) with Mean and (±SD) at Solid Waste Disposal area in Halabja City from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
Station 1
1108
1109
1095
1092
1074
1066
1027
1074
1080
Station 2 Station 3 Station 4
1121 1135 1141
1110 1070 1110
1098
1180
1098
1187
1092 1109
1133
1094
1015
1098 1152 1118
1021 1027 1061
1047
±SD
a
35
a
68
a
58
a
208
a
64
1098
1075
1107
1033
1084
Station 5
1139
1063
1034
1113
1088
1106
1054
1091
1084
Station 6
1107
987
1070
1115
1105
1071
1014
1082
1078
a
35
Mean
1125 40
a
1101
c
1033
1085
78
43
35
68
73
±SD
c
abc
abc
bc
1074
1083
1131
1050
63
38
50
237
a
1067
ab
44
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different - Maximum Allowable Limit is ( 20-1000 mg.kg-1 ) According to the European union( EU). Table ( 5.39 ): Copper ( Cu ) Concentration in Soil ( mg.kg-1 ) with mean and ( ±SD ) at Solid Waste Disposal area in Halabja City from May to December 2012. Studied sites
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
Mean
Station 1
298.53
297.14
293.19
291.41
286.99
291.89
232.8
248.21
280.02
Station 2
290.65
299.14
290.39
292.89
287.97
293.38
293.94
250.91
a
24.37
c
14.84
ab
23.72
b
21.1
d
6.85
c
287.40
Station 3
293.6
294.46
295.11
301.1
292.26
295.83
238.81
260.22
284.17
Station 4
293.37
297.72
292.49
295.39
290.52
291.94
235.81
276.91
283.89
Station 5 Station 6
299.1 290.53
Mean
294.29
±SD
4.42
de
301.01
294.22
297.09
292.56
293.26
289.47
290.31
289.63
e
cd
de
c
297.12 5.07
292.4
294.7
3.97
6.57
289.99 3.75
293.41 290.88 cd
292.89 3.8
292.42
284.84
294.33
287.49
285.32
289.61
3.21
a
b
286.4
15.68
9.41
12.55
262.04
267.73
31.04
16.66
-Values with different letters are significantly different at p>0.05, but values with same letters are not significantly different. - Maximum Allowable Limit is ( 50 - 140 mg.kg-1 ) According to the European union ( EU).
77
±SD
Chapter Five
Result
5.5 Trace Heavy Metals Concentration ( mg.kg-1 ) in Wheat Grain: Table ( 5.40 ) shows heavy metal concentrations in wheat grain grown around dump sites in Halabja city. The levels of Zinc, Lead, Cadmium, Nickel, Chrome and Arsenic in wheat grain were ( 115 mg.kg-1 , 2.1 mg.kg-1 , 1.2 mg.kg-1, 1.19 mg.kg-1 , 0.058 mg.kg-1 and 0.0313 mg.kg-1 ) respectively. It was found that the concentration of this heavy metals were far upper than the permissible limits recommended by WHO/FAO and UK for metals in foods and normal range of metals in plants except for Zinc an Chrome . Table ( 5.40 ): Trace heavy metals concentration ( mg.kg-1 ) in wheat grain with mean and (±SD) at agricultural site in solid waste disposal area in Halabja city. Studied site
Ni
Zn
As
Cd
Cr
Pb
Station 1
1.255
111
0.0345
1.45
0.085
2.93
Station 2
1.125
119
0.028
0.95
0.03
1.27
Mean
1.19b
115e
0.0313 a
1.2d
0.058c
2.1bc
±SD
0.21
6.69
0.115
1.40
0.665
0.98
5.6: Water Quality Index Via Ground Water: Calculating water quality index is to turn complex water quality data into information that is understandable and useable by the public. The mean values of eleven physicochemical parameters of ground water around the dumping sites for calculation of water quality index are presented in Table ( 5.41 ). The computed overall WQI was 90.23 during the studied period and therefore can be categorized as “good water” according to the water quality classification based on WQI.
5.7: Water Quality Index Via Surface Water: The mean values of various physicochemical parameters of surface water around the dumping sites for calculation of water quality index are presented in Table ( 5.42 ). The computed overall WQI was 102.5 during the studied period and therefore can be categorized as “ poor water ” according to the water quality classification based on WQI.
78
Chapter Five
Result
Table ( 5.41 ): Calculation of water quality index via ground water samples
Parameters
Unit
Actual measured value
pH EC DO Total hardness Calcium hardness Magnesium Alkalinity Sodium Potassium Chloride Nitrate
μs.cm-1 mg.l-1 mg.l-1 mg.l-1 mg.l-1 mg.l-1 mg.l-1 mg.l-1 mg.l-1 mg.l-1
7.03 478.3 6.4 301.5 94.6 49.6 212.8 5.8 0.9 97.5 13.3
WQ standard value ( Si )
Relative Quality ( Wi (
6.5 - 8.5 1000 5 100 100 30 200 20 10 250 50
0.133 0.001 0.2 0.01 0.01 0.033 0.005 0.05 0.1 0.004 0.02
Weight Rating ( Qi )
Weighted Value ( QiWi )
93.7 47.83 128 301.5 94.6 165.3 106.4 29 9 39 26.6
∑ Wi = 0.566
12.46 0.048 25.6 3.02 0.95 5.45 0.53 1.45 0.9 0.16 0.53
∑QiWi= 51.098
Water quality index ( WQI ) = 90.23 Table ( 5.42 ): Calculation of water quality index via surface water samples.
Parameters
Unit
Actual measured value
pH EC DO Total hardness Calcium hardness Magnesium Alkalinity Sodium Potassium Chloride Nitrate
μs.cm-1 mg.l-1 mg.l-1 mg.l-1 mg.l-1 mg.l-1 mg.l-1 mg.l-1 mg.l-1 mg.l-1
7.8 377.9 7.5 286.3 64.9 49.3 235.1 7.8 2.1 60.9 12.6
WQ standard value ( Si )
6.5 - 8.5 1000 5 100 100 30 200 20 10 250 50
Relative Weight Quality Rating ( Wi ) ( Qi )
0.133 0.001 0.2 0.01 0.01 0.033 0.005 0.05 0.1 0.004 0.02 ∑ Wi = 0.566
104 37.79 150 286.3 64.9 164.3 117.5 39 21 24.36 25.2
Weighted Value ( QiWi )
13.83 0.038 30 2.86 0.65 5.42 0.59 1.95 2.1 0.097 0.5
∑QiWi= 58.04
Water quality index ( WQI ) = 102.5 5.8 Hazard index Via ground water: Table ( 5.43 ) summarizes the calculated chronic daily intake ( CDI ), hazard quotient ( HQ ) and hazard index ( HI ) for consumption of ground drinking water. CDI indices for heavy metal ( 79
Chapter Five
Result
HM ) in the study area were found to be in the order Pb > Fe > Ni > As > Zn > Cd. The mean HQ index value for Zn, As, Cd, Fe, Pb and Ni for ground water were 0.00037, 0.2, 0.138889, 0.000181, 0.030864 and 0.011111 respectively. While the Hazard index was equal to (0.38142) which was lower <1 for all studied HM in ground drinking water samples indicating no health risk. while an HI of <1.0 is considered acceptable . Table ( 5.43 ): Chronic daily intake ( CDI ) and Hazard quotient ( HQ ) indices of Heavy metals via ground water. Heavy metals
Mean (mg.l-1)
CDI (mg.day)
HQ (Hazard Quotient)
Zn As Cd Fe Pb Ni
0.004 0.036 0.0025 0.039 0.04 0.008
0.00011 0.001 0.00006 0.00108 0.00111 0.00022
0.00037 0.2 0.13889 0.00018 0.03086 0.01111
HI ( Hazard Index )
0.38142
5.9 Hazard index Via surface water Table ( 5.44 ) summarizes the calculated Chronic daily intake ( CDI ), Hazard Quotient ( HQ ) and Hazard index ( HI ) for consumption of surface water. CDI indices for HM in the study area were found to be in the order of Cd > As > Pb > Fe > Ni > Zn. The mean HQ index value for Zn, As, Cd, Fe, Pb and Ni for ground water were 0.000463, 0.555556, 0.111111, 0.000181, 0.030864 and 0.029167 respectively. While the Hazard index was equal to ( 0.72734 ) and was lower < 1 for all studied HM in the surface water samples indicating no health risk, while an HI of < 1.0 is considered acceptable . Table ( 5.44 ):Chronic daily intake ( CDI ) and Hazard quotient ( HQ ) indices of Heavy metals via surface water. Heavy metals
Mean ( mg.l-1 )
CDI ( mg.day )
HQ ( Hazard Quotient )
Zn As Cd Fe Pb Ni
0.005 0.1 0.002 0.039 0.04 0.021
0.00014 0.00278 0.00565 0.00108 0.00111 0.00058
0.00046 0.55556 0.11111 0.00018 0.03086 0.02917
HI ( Hazard Index )
0.72734
80
Chapter six
Discussion
Chapter six 6. Discussion 6.1 The analysis of Physical and chemical parameters:
6.1.1 Water temperature: Water temperature is one of the important factors, which impacts the acceptability of a number of inorganic constituents and chemical contaminants (WHO, 2006). However, water temperature is used to determine the residence time of water in an aquifer, and the depth to which ground water has traveled (Champion and Stark, 2001). Temperature fluctuates naturally both daily and seasonally. It also varies seasonally with air temperature, probably due to many environmental factors, among them solar radiation and Gale wind (Ganjo et al., 2006). The water temperature measured over the period of the study ranged from 18.1- 27 0C, 17.4-19.5 0C for well and surface water respectively, revealing slight spatial and temporal variation between months and the study sites. No abnormal temperature value was recorded during the study period. Generally, the water temperature of all the study sites ( wells and wastewater ) during the entire period of sampling showed a clear monthly variation; the maximum temperature was noted during hot and the minimum during coled months. Variation in water temperature affected by seasonal fluctuation and air temperature was obvious throughout the present study. The same results was obtained by (Ganjo et al., 2006; Ahmad et al., 2007; Muhamed, 2008; Rashid, 2010; Abdurafiu et al., 2011, Anuar Ithnin et al., 2012; Pushpendra et al., 2012 ).
6.1.2 Water and soil hydrogen ion concentration (pH): pH is an important variable that determines the availability of water for different perpuses, including suitability to human, plants and animals ( Ahiphathy and puttaiah, 2006 ). pH refers to the level of acidity; it is a measure of the concentration of hydrogen ( H+ ) ions that are in system in water. Any increase or decrease in the pH rate lead to disturbance in the chemical balance of water that affect the biological activity of the aquatic ecosystem ( Hantoush, 2006 ). Low pH values increase concentrations of some dissolved metals in the water and increase the toxicity of these metals ( Atubi, 2011 ).
18
Chapter six
Discussion
pH value in the current study lies in the slightly acidic to slightly alkaline. The pH value ranged from ( 6.5-7.4 ) with the average mean of ( 7.03 ),and a maximum pH observed in August as 7.4 and 6.5 as minimum value in June in all the well waters. The low pH of some water sources could have been a consequence of carbon dioxide saturation in the groundwater ( Nduka and Orisakwe, 2009). The decrease of pH values, may be due to the release of carbonate and bicarbonate in the water by the action of precipitation or filtration ( Goher, 2002 ). While pH was found to be slightly alkaline in surface water was ranging between ( 7.5-7.9 ). A Comparison of the present ( pH ) values to the guideline values recommended by (WHO, 2006), (EU, 2006), and ( Canada, 2006) for drinking water standards, and irrigation ( Patel et al., 2004 ) shown that the ( pH ) values of all investigated waters during the studied period would not adversely affected its use for domestic uses. The same result was supported by ( Muhamed , 2008; Ololade et al. 2009; Rajkumar et al., 2010; Amadi, 2011; Nkwocha et al., 2011; Abdurafiu et al., 2011; Anuar Ithnin et al., 2012; Shanthi and Meenambal , 2012; Dibakar et al., 2012 ). Soil pH and organic matter are considered the significant factors to control trace element mobility, accumulation and bioavailability. At high pH the liability and bioavailability of trace elements decrease due to precipitation of carbonate and hydroxides or insoluble organic complexe formation, while their mobility become more noticeable when the pH decreases ( Smith and Giller, 1992, Xu et al., 2010). Soil pH is an important parameter that directly influences sorption/desorption, precipitation/ dissolution, complex formation and oxidation reduction reaction. Soil pH significantly affects the solubility and mobility of these metals, as most of the metals are soluble in acid soils than in neutral or slightly basic soils ( Oyedele et al., 2008, Partha et al , 2011). Alkaline soils have pH 7.5-8.5 while a acidic soils have pH 4-6.5 (Kadhum and Hussain, 2011). The results of soil pH analysis of the study sites during the studied period ranged from ( 7.9-8.25 ). The minimum value was recorded during June at station three and the maximum during June at station one . The observed pH values of the study area were slightly basic, which may be due to the geological formation of the study area because the soil is characterized as alkaline; it is calcareous in nature and is classified by silty loam, sandy and silty clay (Rashid, 2010). This alkalinity can be ascribed to the high content of calcium carbonate gravel and CaCO3 ( Rashid, 1993). 18
Chapter six
Discussion
These results were also obtained by ( Muhammad, 2008; Rashad and Shalaby, 2007; Adjia et al., 2008; Oyedele et al., 2008; Singh et al., 2008; Beyene and Banerjee, 2011; Rashad et al., 2011; Chinyere et al. , 2013 ).
6.1.3 Water and soil electrical conductivity (EC): Scater ( 2003 ) stated that specific conductivity is the measure of the ability of water or soil to conduct an electrical current, This ability depends on the presence of ions and is highly dependent on the amount of dissolved solids ( such as salt ), mobility, and temperature (APHA, 1998 ). EC is also an important factor to determine the total soluble salts in the ground water ( Sheet, 2012 ). However, electrical conductivity values more than 500 µs.cm-1 in a given aquatic system considered to be hard water (Goldman and Horne, 1983). The wide range over the study period is probably related to differences in climate lithology, and geological formation. The conductivity of surface water can vary depending upon the type of rock or soil that the water has come in contact with. Other natural variations in surface water conductivity can be caused by the type or amount of biological activity in surface water (Copertino et al., 1998). Pollutants that enter surface water through runoff may raise or lower the conductivity of surface water (Elbag and Mark, 2006). Electrical conductivity levels recorded in the present study ranged from (363 µs.cm-1) at (W2) during May to ( 662.3 µs.cm-1 ) at W1 during August for ground water and ranged between (357.3 µs.cm-1 ) during May to ( 406.7 µs.cm-1 ) during November for surface water. These high conductivity values obtained at W1 closest to open dump indicate the effect of landfill on water quality in form of leachate seepage and inorganic pollution at this specific site (Ibtisam and Abdul 2012 ). The wide range over the study period a probably related to diffrences in climate, lithology, and geological formations. Wetzel (1975) and Goldman and Horne ( 1983 ) reported that the value of electrical conductivity is related to climate, soil and geological origin of the area, the effect of input and output as well as evaporation. Similar observations were made by ( Muhamed , 2008; Rajkumar et al., 2010; Amadi, 2011; Saidu, 2011; Bundela et al., 2012; Shanthi and Meenambal, 2012; Pushpendra et al., 2012). On the other hand, the maximum acceptable level of conductivity as indicated by ( WHO, 2004 ) is ( 700 µs.cm-1 ), accordingly all studied well and surface waters were within the permissible range for drinking purposes. 18
Chapter six
Discussion
The studied soil EC ranged from ( 363.7 to 580.3 µs.cm-1 ) the minimum value in site 5 was recorded during July, while the maximum value in site 1 during November. This may be due to changes in the climate and concentration of the soil containing elements (Al-Ameri, 2011). This value is slightly higher than those obtained by ( Muhammad, 2008; Amadi, 2011), but lower than those obtained by ( Rashad and Shalaby, 2007). While similar observations were made by ( Raman and Narayanan, 2008; Rashid, 2010 ). The hazard caused due to solid wastes is most often encountered because of the high total salt and sodium content level which can be studied by conductivity measurement. Conductivity value of less than 0.5 ms.cm-1 is perfectly safe and it does not have any negative effect on plant growth. High value of EC can be toxic to plants and may prevent them from obtaining water from the soil. The presence of large amounts of ionic substances and soluble salts have resulted in an increased value of EC in the MSW surrounding the soil samples. Conductivity is a measure of the current carrying capacity, thus gives the idea of soluble salts present in the soil ( Goswami and Sarma, 2008; Tripathi and Misra,2012).
6.1.4 Dissolve oxygen ( DO ): Oxygen is the most important element in limiting water quality, the dissovled oxygen concentration depends on the physical, chemical, and biochemical activities in water body, and its measurment is a good indication of water quality. The level of dissolved oxygen is affected by many other factors as temperature, salinity, photosynthesis , organism respiration, and oxygen gas exchange between air and water. Changes in dissolved oxygen concentrations can be an early indication of changing conditions in the water body (WHO, 1996; Bartram and Balance, 1996). Dissolved oxygen concentration in well water samples ranged from ( 5.8-7.3 mg.l-1 ). An overall mean of dissolved oxygen concentration recorded for the study period during the entire sampling time was ( 6.4 mg.l-1 ) . Surface water dissolved oxygen ranged between (7.2-7.8 mg.l-1) with an average mean of 7.5. These results agreed with those of ( Muhamed, 2008; Nkwocha et al., 2011; Shanthi and Meenambal, 2012), While differed from many studies such as (Rashid, 2010; Anuar Ithnin et al., 2012; Pushpendra et al., 2012; Afolayan et al., 2012; Bundela et al.,
2012 ) for water
concentration. The effect of a waste discharge on water resources is largely determined by oxygen balance of the system. Also, seasonal oscillations in dissolved oxygen might be attributed to 18
Chapter six
Discussion
several other reasons; water temperature, dissolved salts, partial pressure of the gas, wind, as well as inputs of organic matter and process of organic matter degradation ( Morgan, et al.,1993; and Wetzel and Likens, 2000; Tebbuti and Savo, 2001 and Nasir, 2007). Oxygen depletion during August in W3 is coincident with high water temperature as well as high microorganism's densities that created anaerobic condition as a result of organic matter decomposition ( Benerji, 1997 ). However, ( Khopkar, 2004 ) stated that the rate of dissolved oxygen in polluted water was much less than in pure water. DO levels can provide information on the concentration of oxygen demanding pollutants that may be entering surface water via point and non-point sources. Oxygen is consumed by microorganisms as they degrade organic matter in water, as a result the DO concentration decreases (Elbag and Mark, 2006).
6.1.5 Biological oxygen demand ( BOD5 ): Biological oxygen demand is defined as the amount of oxygen required by decomposers while stabilizing decomposable organic matter under aerobic condition. Biodegradable organic material creates biological oxygen demand (BOD5) which can cause low dissolved oxygen, which in turn creates taste and odor problems in well water, and cause leaching of metals from soil and rock into ground water and surface waters ( APHA, 1999 and Khopkar, 2004). BOD5 is an indicator for the amount of organic matter in a given water system and it is the delayed mirror image of dissolved oxygen profile ( Hammer, 1986 ). The results of this study showed that a wide range of BOD5 values were recorded during the study period. Well water samples have values ranging between ( 2.8 - 3.6 mg.l-1 ) with average mean of 3.2 mg.l-1, but surface water value ranged between ( 4.1- 4.4 mg.l-1 ) with average mean of 4.2 mg.l-1. This rate was higher than those obtained by ( Muhammed, 2008; Rashid, 2010; Afolayan et al., 2012; Pushpendra et al., 2012; Shanthi and Meenambal, 2012; Bundela et al., 2012). While lower than that obtained by ( Mustafa , 2006; Amadi, 2011; Nkwocha et al., 2011; Anuar Ithnin et al., 2012 ). This is probably linked to the amount of rainfall that washes down all pollutants from different areas and bring it to surface water supported by the data reported by Anber ( 1984 ). These values corresponds with the high level of BOD recorded in all the samples which actually indicate the presence of microorganisms. This phenomena could also be attributed to the 18
Chapter six
Discussion
microbial demand for oxygen, because ( BOD5 ) is the amount of dissolved oxygen required by bacteria while stabilizing decomposable organic matter ( Sawyer and Mc Carthy , 1978). In months with high temperature, the amount of BOD5 increased, which may be due to the increasing activity of microorganisms that consume DO in oxidation processes (Awange and Ong'ang'a, 2006; Al-Mousawi, et al., 1995). Hynes (1974) indicated that water quality depending on BOD5 values as shown in table ( 6.1 ): Table (6.1) Classification of water quality depending on BOD5. BOD5 ( mg.l-1)
Water quality
1
Very clean
2
Clean
3
Fairly clean
5
Doubtful
≥ 10
Bad
Accordingly, All wells water can be classified as fairly clean but surface water classified as doubtful water quality. Leachates from landfills change the biological properties of the aquatic systems. Due to a high input of organic matter, the growth of bacteria is stimulated. This excess of bacteria causes a rise in the biological oxygen demand ( BOD ) which may end up in a depletion of oxygen in the water system ( Schwarzbauer et al., 2002 ).
6.1.6 Total Hardness ( TH ): Total hardness is a measure of the concentration of calcium & Magnesium and /or iron in water and its usually expressed as the equivalent to CaCO3 concentration ( Bartram and Balance, 1996 ). When water is referred to as 'hard' it means that it contains more minerals than ordinary water. It is better to avoid hard water for drinking as according to Al - Manharawi and Hafiz ( 1997 ) increased water hardness has health effects, like precipitation of salts in vessels, formation of stone and pre-mature aging.
18
Chapter six
Discussion
Table ( 6.2 ): Demonstrates water classification depending on Total Hardness. Spellman ( 2003 ). Total hardness
Al - Manharawi and Hafiz ( 1997 ) Water types
mg.l-1 of CaCO3
Total hardness
Water types
mg.l-1 of CaCO3
0-51
Soft
0 -60
Soft
51 - 151
Moderately hard
60 – 120
Medium hard
151– 300
hard
120 – 180
Hard
Greater than 300
Very hard
>180
Very hard
In the present study, the value of well water hardness ranged between 250 - 413.7 mg CaCO3.l-1 with an average mean of 301.5 mg CaCO3.l-1 . On the other hand, the value of surface water ranged between 265.3-305.3 with an average mean of 286.3 mg CaCO3.l-1 . The results of the present investigation is closely related to the observations obtained by ( Muhammed, 2008; Rashid, 2010; Jhamnani and Singh, 2009; Shanthi and Meenambal, 2012; Pushpendra et al., 2012; Rashmi shah et al., 2013) but differ from those recorded by ( Raman and Narayanan, 2008; Omofonmwan and Eseigbe 2009; Abdurafiu et al., 2011; Nkwocha et al., 2011; Aderemi; 2011 ). These results showed different values of total hardness which may be due to the source and type of water sources, and the geological and soil properties of the studied area. The data was classified as hard to very hard water according to Al - Manharawi and Hafiz ( 1997 ) and Spellman ( 2003 ) . The results of all water sample relating to the total hardness as CaCO3 are, however, within the permissible limits recommended by WHO ( 2006 ) 500 mg.l-1 and IQS ( 2001 ) 500 mg.l-1 .
6.1.7 Calcium and Magnesium Hardness: Cations in natural waters are generally dominated by calcium followed by magnesium, sodium and potassium according to their decreasing order of concentration ( Reid, 1961 ). Magnesium is usually less abundant in waters than calcium, which is easy to understand since magnesium is found in the earth’s crust in much lower amounts as compared with calcium. In common underground and surface waters the Ca to Mg ratio is about 4 ( Pitter, 1999 ). Calcium is presented in groundwater as a material of suspension where calcium bicarbonate is the prime
18
Chapter six
Discussion
cause for the hardness in water. In groundwater the calcium content generally exceeds the magnesium content ( CGWB, 2005 ). In contrast calcium hardness was more than magnesium hardness in this study where well water Calcium hardness ranged between ( 61.7 - 147.3 mg CaCO3.l-1 ) with an average mean of ( 94.6 mg CaCO3.l-1 ), while magnesium hardness ranged between 37.3 – 77.0 mg CaCO3.l-1 with an average mean of ( 49.6 mg CaCO3.l-1 ). On the other hand, the value of surface water Calcium hardness ranged between ( 55.3 – 74.3 mg CaCO3.l-1 ) with average mean of ( 64.9 mg CaCO3.l-1 ), while magnesium hardness ranged between ( 42.3 - 57.7 mg CaCO3.l-1 ) with an average mean of ( 49.3 mg CaCO3.l-1 ) . According to WHO standards for drinking purpose, the maximum desirable concentration level of calcium is 75 mg CaCO3.l-1 and the permissible concentration level is 200 mg CaCO3.l-1 while the high desirable level of magnesium concentration is 50 mg.l-1 and the permissible level of Mg concentration is 150 mg.l-1 WHO (1996) and EU ( 2004 ) which indicate that the concentration of Ca and Mg hardness for all wells & surface water in the studied areas lie within this limit and is considered safe for drinking purposes. The dominance of calcium ion on magnesium ion recorded in all stations during the present study is an aggrement with the result obtained by ( Mustafa, 2006; Muhammed, 2008; Raman and Narayanan, 2008; Rajkumar et al., 2010; Nkwocha et al., 2011; Shanthi and Meenambal, 2012 ). The rate of Ca concentration been more than Mg in this investigation may be attributed to the geological formation of the study area which is composed mainly of limestone and that solubility of calcite rocks which is abundant in the area, is more rapidly than dolomite ( Ali, 2002 ); and may be possibly due to the degree of the ability of cations to precipitate as carbonate compounds ( Golterman, 1975), or various bicarbonate and carbonate compounds, originating from dissolution of sedimentary rocks. On the other hand, the excess in calcium concentration may result from the mixing of water and leachate effluents.
6.1.8 Alkalinity: Alkalinity is a measure of water's capacity to neutralize an acid. Total alkalinity is generally associated with the presence of carbonates, bicarbonates and hydroxides and some less significant constituents. High alkalinity in water is undesirable because it causes excessive hardness and can result in high concentrations of salts. Acceptable limits have been established 11
Chapter six
Discussion
to alleviate corrosive or encrusting properties and eliminate human health problems such as gastrointestinal (stomach) irritation (AL-Aswad et al., 1978 and Carr et al., 2008). It is an important characteristic of natural and polluted water, in which measurement of potential hydrogen differentiates between their alkalinity or acidity (Hem, 1985). Well water samples have alkalinity values higher than the acceptable level in drinking water which is ( 200 ppm ) according to ( WHO, 2006 ).The mean value was 234.1 mg.l-1 for surface water, while it was 212.8 mg.l-1 for well water samples which can mainly be contributed to OH, CO3, HCO3 ions. The same results were indicated by many other researcher as ( Mustafa, 2006; Pushpendra et al., 2012; Rajkumar et al., 2010 ) and results are higher than those recorded by (Muhamed, 2008; Raman and Narayanan, 2008; Nkwocha et al., 2011; Shanthi and Meenambal, 2012; Pushpendra et al., 2012; Rashmi shah et al., 2013 ). The high alkalinity level in some of the studied wells may be due to the action of carbonate on the basic materials in the soil which gives unpleasant test to the water. Also, alkalinity is strongly related to the amount of carbon dioxide present in water and the geological properties of the area which is composed mainly of CaCO3, microorganism activities, and hydrolysis of bicarbonate ions. On the basis of seasonal variation, the alkalinity of water increases in the rainy seasons ( Champion and Starks, 2001; Swarna, and Rao, 2010 and Amro, 2004 ). 5.1.9 Chloride ( Cl- ): Chloride ions are usually present in natural water. Chloride occurs in high concentrations in waters that have been in contact with chloride containing geological formations. It is found mainly in the earth’s as salts of sodium ( NaCl ), potassium ( KCl ), and calcium ( CaCl2 ) ( Wetzel, 1975; Weast, 1989; Schauss, 1996; Bartram and Balance, 1996; Al-Manharawi and Hafiz, 1997 ). The concentration of chloride ion in well and surface water adjacent to solid waste dumping sites ranged between 70 mg.l-1 to 195 mg.l-1 with the average mean value of 97.5 mg.l-1 and 55.7 mg.l-1 to 63.7 mg.l-1 with the average mean value of 60.9 mgL-1 . According to ( WHO, 2006 ) the maximum desirable value is ( 250 mg.l-1 ) thus, all investigated wells and surface water contain desirable chloride concentrations . These results came in agreement with ( Mustafa, 2006; Muhammed, 2008; Omofonmwan and Eseigbe , 2009; Jhamnani and Singh, 2009; Rashid, 2010; Rajkumar et al., 2010; Amadi, 18
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2011; Nkwocha et al., 2011; Abdurafiu et al., 2011; Pushpendra et al., 2012; Rashmi shah et al., 2013), while the results obtained by this study are lower than those obtained by Shanthi and Meenambal ( 2012 ). The department of Health and Welfare Canada ( 1987 ), reported that chloride in ground water may result from both natural and anthropogenic sources such as run-off containing salts, the use of inorganic fertilizers, landfill leachates, animal feeds, industrial effluents, irrigation drainage and seawater intrusion in coastal areas. In addition agricultural, industrial and domestic waste waters discharged to surface waters are also a source of chloride. Chlorides can travel a great distance in groundwater, It can get into groundwater from solid wastes when it comes in contact with rainwater and then gain entrance into aquifer ( Omofonmwan and Eseigbe , 2009). According to Al- Hassany, ( 2003 ) report, high chloride concentration in groundwater of ALDora in Baghdad city may be due to domestic rather than agricultural. High chloride levels in groundwater can contribute significantly to infiltration by sewage and leachates ( Bocangra et al., 2001 ). 5.1.10 Sodium ( Na+1 ) and Potassium ( K+ ) concentration: Sodium and potassium are relatively unaffected by biological activities ( Owen et al., 1972 ). Potassium is slightly less common than sodium and more abundant in sedimentary rocks. Sources of potassium are the principal potassium minerals of silicate rocks, such as mica, microcline, and felds pathiod leucite ( Hem, 1985 ). It is well known that potassium concentration is less than that of sodium in natural waters, and the ratio of Potassium to sodium cation is often 1:10 or 1:20 ( Davis and Dewiest, 1966 and Golterman, 1975, Khopkar, 2004 ). Sodium salts are generally highly soluble in water and are leached from the terrestrial environment to the ground water and surface water (WHO, 2004). Potassium is an alkali metal and the seventh most common element on earth (Lewis, 1997). It has a crystal structure, and has high thermal and electrical conductivities ( Burkhardt and Brüning, 2002 ). Potassium cation occurs in ground waters as a result of mineral dissolution, from decomposing plant material, and from agricultural runoff. However, saline intrusion, mineral deposits, and sewage effluents, industrial wastes can all contribute significant quantities of sodium to water (APHA, 1999, Foster, 2001 and WHO, 2006).
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The mean Sodium concentration value recorded in this study was 5.8 and 7.8 mg.l-1 for wells and surface waters adjacent to the solid waste dumping sites which was below the maximum recommended levels and standards of water quality recommended by WHO (2006) 200-250 mg.l-1 , EU (2004), 200 mg.l-1 and Canada ( 2006 ) 200 mg.l-1. Whereas, the mean potassium concentration value was 0.9 mg.l-1 and 2.1 mg.l-1 for wells and surface water adjacent to solid waste dumping sites which was below the maximum recommended levels and standards of water quality recommended by WHO ( 2006 ) and EU ( 2004 ), 10-12 mg.l-1, and permissible limits recommended by Langmuir ( 1997 ) who reported that concentration of potassium in surface water is equal to 2.3 mg.l-1 . These results agree with those reported by ( Lee et al., 2005; Mustafa, 2006; Muhammed ,2008; Raman and Narayanan, 200; Rashid, 2010; Amadi, 2011; Aderemi, 2011). While differ with those reported by ( Kassenga and Mbuligwe, 2009; Rajkumar et al., 2010; Abdurafiu et al., 2011; Aderemi et al., 2011 ). According to ( USEPA, 2004 ) all studied groundwater samples investigated during this study were within the desirable concentrations and were in the safe side for drinking purposes. The occurrence of sodium high levels in well and surface water closest to the landfill is an indication of possible leachate flow into ground and surface water and agrees with previous report by Loizidou and Kapetanios ( 1993 ). It is recommended by USEPA that sodium levels in drinking water should not exceed 20 mg.l-1 for individuals on no salt diets ( UME/USEPA, 2007, Aderemi, 2011).
5.1.11 Nitrate ( NO3- ): Nitrate is the most highly oxidized form of nitrogen compounds; it is commonly present in surface and ground water since it is the final product of the aerobic decomposition of organic nitrogenous matter (Bartram and Balance, 1996). Nitrate is an important nutrient for aquatic plants. The balance of nitrate in a water system is strongly depending upon biological processes such as ; nitrification, nitrate reduction, denitrification, and autotrophic assimilation (Golterman, 1975; Tebbutt, 1977; Brown, 1989, House et al. 1994; and Mackenzie, 2003 ). The main sources of nitrate are due to either natural or anthropogenic activities-rainfall and dry fall out, soil nitrogen , nitrate deposit , sewage , septic tank and animal waste , manure or compost , green manure and plant residues , atmospheric nitrogen fixation ,fertilized nitrogen 88
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from irrigated overflow water outlets and industrial effluent ( Ternamch , 1991). Unpolluted natural water only contain minute amount of nitrate , their concentration in the ground and surface water is normally low but can reach high levels as a result of leaching or runoff from agriculture or contamination from human and animal waste as a consequence of the oxidation of ammonia and similar sources ( WHO, 2006 ). Well water and surface water nitrate ranged between (9.3 - 17mg.l-1) with average mean (13.3 mg.l-1) and ( 9.5 - 16.1 mg.l-1) with average mean ( 12.6 mg.l-1). The maximum value was recorded at W1, the reason of the increase in nitrate may be related to its closeness to the dumping site. These findings are higher than those reported by ( Ololade, 2009; Jhamnani and Singh, 2009; Amadi, 2011; Nkwocha et al., 2011; Afolayan et al., 2012) but lower than those reported by (Mustafa, 2006; Raman and Narayanan, 2008; Rashid, 2010; Akinbile et al., 2011;Shanthi and Meenambal , 2012). It is noted that high nitrate concentration was more in W1 which is close to the landfill site. Manure which is high in nitrate is used as a fertilizer hence large amounts of nitrates find their way into the ground water. While, the source of nitrate pollution in surface waters may be related to dumping leachate disposal and to some extent agricultural activities ( Rashid, 2010 ). The MCLG (Maximum contaminant level goals) for nitrate in drinking water is 10 mg.l-1, although nitrate concentration greater than ( 5ppm ) reflects unsanitary condition ( WHO, 2005 ). While a permissible nitrate standard suggested by Hammer (1986) for surface water is near l0 mg.l-1. Higher concentration often indicate nitrogen-containing fertilizers since the nitrate ion is only poorly absorbed in soil and easily reaches the ground water ( Rump, 1999 ). According to WHO ( 2004 ) and EU ( 2004 ) guideline, the value of nitrate recommended is 50 mg at NO3-N.l-1 was recommended; accordingly all wells and surface water lie within the recommended level of nitrate-nitrogen for drinking purposes. Nitrate in groundwater originates primarily from fertilizers, septic systems, and manure storage or spreading operations. The fact is that contaminants generated within the waste dump during decomposition of the biodegradable components of the waste enter into the water body affecting its quality and ecological health of the surface water ( Llamas and Bharti, 2001; Okeocha, 1995 ). 6.1.12 Total sulfur in soil mg.kg-1: Sulfur in nature is derived from minerals in rocks from which soils are formed ( Evangelou, 1998 ); its present in the soil in different forms, among them the organic form is that 88
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making the largest percent of the total sulfur in soil ( Rahi et al.,1991 ). Sulphur (S) is an essential element for growing plants, being a component of plant-proteins and having an important role in the synthesis of chlorophyll ( Rajendram et al., 1998). The presence of sulfur in soil can present potential risks of harm to human health and the environment, the elevated levels of sulfur can create high levels of acidity in water runoff, causing detrimental effects on the natural habitat and environment ( Kostecki et al., 2008 ). In this study, the concentration of sulfur in the soil ranged between ( 0.002-0.03% ) with the mean overall average concentration ( 0.018% ) that seem to be high in comparison with the total sulfur content in the soil which is between ( 0.002 - 0.02 mg.kg-1 ) as stated by ( Kostecki et al, 2008 ; Amadi, 2011 and Chinyere et al., 2013 ). These elevated level of Sulfer content may be related to the dumping leachate discharge, as concluded by ( Pansu and Gautheyrou, 2006 ) who stated that industrial and
refinery activities contribute to soil enrichment in sulfur
compounds or caused by organic sulphur containing remains of plant and animal wastes. However inorganic sulphur contribution to this dumpsite soil sulphur ion may likely be from industrial wastes dumped within the dumpsite environment. All these sulphur will be transformed to sulphate and assimilated through the sulphate assimilation pathway by plants ( Ma et al., 2001 ).
6.1.14 Total nitrogen in Soil ( % ) : Nitrogen ( N ) is one of the major nutrients found in soil. The total amount of ( N ) present in soil, nearly 95-99 % as organic form and the 1-5% as inorganic form ( ammonia and nitrate ). The total ( N ) is an indicator of the soil potential for the element (Baruah and Barthakur, 1997). It is the most important macro essential nutrient, limiting plant growth and production, and is required for plant growth in most soils of the world ( Seastedt and Suding, 2007 ). Total nitrogen concentration of dumping site samples ranged between (3.9-6.9 %),with overall mean ( 5.3% ) were higher in comparison to other works that done by ( Anikwe and Nwobodo, 2002; Esakku et al., 2003 ) who recorded (0.76% to 0.97%), ( 0.76% to 0.97% ), ( 0.14%-0,72% ) respectively. The surface layer of most of the Iraqi soil contain about (0.06-0.5% ) total nitrogen ( Black et al, 1965 ) . Results obtained in this study is higher than this level and this may be due to that municipal waste compost and its leachate increased the amounts of soil organic matter available macro- (N, P, K) ( Roghanian et al.,2012). The high N content of the 88
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dump site soils may be responsible for the high amount of green vegetation observed at the dump sites ( Woomer et al., 1994 ). The minimum rate of nitrogen was detected during October and December, this agrees with the results obtained by ( Walworth et al., 2007 ) who suggested that nitrogen level decreases in cold regions and cold times of the year, while the maximum rate is recorded during May which may be attributed to the nitrogenous bearing fertilizers ( Nkeng et al., 2012).
6.1.15 Soil Organic Matter ( OM ) %: Soil organic matter comprises an accumulation of partially disintegrated and decomposed plant and animal residues and other organic compounds synthesized by the soil microbes as decay occurs. It comprises all living soil organisms and the remains of previous living organisms in their various degrees of decomposition. Soil organic matter plays a major role in maintaining soil quality (Baruah and Barthakur, 1997) and can drastically modify the physical, chemical, and biological properties of the soil ( Brady, 1990 ). Organic matter of soils immobilizes heavy metals at strongly acidic conditions and mobilizes metals at weakly acidic to alkaline reactions by forming insoluble or soluble organic metal complexes, respectively ( Aloysius et al., 2013 ). The high levels of organic matter present at the upper horizon of the dump sites were attributable to the use of the sites for dumping municipal wastes. Organic matter is a reservoir of essential and non-essential mineral elements for plant growth and development, hence increased organic matter content may lead to increased soil productivity ( Enwezor et al., 1998 ). Increased soil organic matter improves soil properties, enhances soil quality, and reduces soil erosion, and increases plant productivity. When soil organic matter content of the soil is low, agricultural use of organic compost is recommended for increasing soil organic matter content and consequently to improve and maintain soil quality; an attractive alternative to recycling such wastes, is composting. Composting is a stabilization process through aerobic decomposition of waste, which has been widely used for different types of wastes ( Roghanian et al., 2012 ). The organic matter of the soil samples ranged between ( 10.3 - 12.1% ), with an average mean of (11.2 % ). The organic matter content in the soil samples was high in comparison to studies done by (Rashad and Shalaby, 2007; Muhammed, 2008; Oyedele et al., 2008; Chinyere et al., 2013 ) who recorded ( 2.8% ), ( 0.41-2.37% ), ( 3-6.2% ),and ( 6.47% ) respectively, while values recorded in this study were lower than recorded by ( Esakku et al., 2003; Singh et al., 88
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2008) who recorded ( 15.3% to 22.0%) and (6 to 19% ) respectively. Soil are consider to be low in organic matter if the rate was 1-1.5%, moderate 2-2.2%, and high 3-3.5% ( Rahi et al., 1991 ). The maximum rate of organic matter was detected in dry season because of the lower soil moisture contents during the dry season which retards the activities of the microorganisms involved in the organic matter decomposition there by accumulating more organic matter in the dry season ( Oyedele et al., 2008). Anikwe and Nwobodo ( 2002 ) recorded high organic matter in dump sites compared to non dump site. In addition, waste water application for agricultural purposes release more organic matter to soil than rain or clean water. Municipal waste compost and its leachate are rich in plant nutrients and OM and are acidic; therefore, they may be used as solid and liquid fertilizers especially in calcareous and low organic matter soils ( Roghanian et al, 2012 ). Rashid ( 1993 ) reported that organic matter content in the north part of Iraq ( Kurdistan Region) ranged between 0.17 % for Qaradag to 2.39 % for Akra. 6.1.16 Base elements: (Na+, K+, Mg+2 and Ca+2): The application of municipal solid waste increases the availability of soil organic matter, N, P,K.Ca and stable aggregates from amended soils. The results show a positive response of plant growth to application of municipal solid waste compost in soils ( Roghanian et al., 2012 ). Major elements such as Na, K, Mg and Ca, are the crucial elements of plant nutrition. It is occasionally found in plants in higher concentration because of their essentiality. Most of the agricultural plants, under optimal production condition, would take up a considerable amount of these metals. Higher percent base saturation of the dump sites were a result of increased release of Na, K, Ca and Mg by decomposing municipal wastes. Higher percent base saturation in the dump site soils relative to non-dump site soils imply that the dump site soils have more exchangeable cations which is a positive productivity indicator ( Woomer et al., 1994 ). The results obtained during the current study they are presented as mean of total concentration of the base elements ( Ca, Mg, K and Na ) were ( 60871 mg.kg-1, 15511 mg.kg-1, 14260 mg.kg-1, and 3195 mg.kg-1 ) respectively in soil sample at the dumping study areas. In general, the order was observed for the mean concentration of major elements in soil samples was Ca > Mg> K> Na. The concentrations of these major elements in the studied area are higher compared to the other trace elements in the soil because of the essentiality of these elements for living organisms. 88
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In all the studied areas, calcium is the most abundant elements and higher than the other base elements with the average concentration of ( 60871 mg.kg-1 ) among all investigated areas while the lowest elements throughout all studied fields is Na with an average concentration of 3195 mg.kg-1. This result showed that the type of soil with high calcium concentration has a very good association with soil mineral composition of primary and secondary minerals bearing calcium, for example, calcite, dolomite, plagioclas, smectite and mixed-layer-silicates ( Jakovljea et al., 2003). 6.1.17 Soil carbonate and bicarbonate mg.kg-1: Calcium carbonate, a major component of calcareous soils, ranges from a few percent in slightly calcareous soils to more than 80 percent in some extremely calcareous soils. Dissolution of limestone is the primary source of calcium carbonate and bicarbonate in the soil. The dissolved ions are removed from the soil profile by surface runoff or downward infiltration, in drier climate carbonate, bicarbonate and other bases are accumulated near the surface making the soil neutral or slightly alkaline, they are readily lost from the soil by leaching ( Boyd, 1995 ). The alkalinity in MSW has been attributed to the presence of CO3, HCO3, Na+, K+ and other alkaline material in varying concentration. The application of MSW increased the availability of P contents of soil ( Goswami and Sarma, 2008). In the current study, calcium carbonate in analyzed soil vary from (20.4 to 29.2), with the overall mean concentration ( 24.9 % ). This indicates that all soils were considered to be calcarious soils. This difference between the locations may be the result of the various parent material and leaching processes ( Muhammed, 2008 ). While the bicarbonate content in the analyzed soil vary between ( 19-48.4 mg.kg-1 ), with an overall mean concentration ( 32.6 mg.kg1
). This result was lower than values recorded by ( Muhammed, 2008; Rashid, 2010; Meuser et
al.,2011; Amadi, 2011 ). But higher than values recorded by ( Rahid, 2010; Roghanian et al., 2012). A study by Rashad et al. ( 2011 ) showed relatively high pH and CaCO3 content at the soil surface around dumping sites. Gohil ( 1989 ) stated that bicarbonates are generally present in the contaminated area in relatively large quantities; Their concentration in the soil during runoff and wet months is low ( Boyd, 1995 ). 88
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Goswami and Sarma ( 2008 ) revealed that the content of calcium carbonate increased upto a maximum value of 196 g kg-1, whereas for control sample, the maximum value was found to be 18 g kg-1. It is evident that the application of MSW had attributed to the increase of calcium carbonate content in the solid waste treated soil of the dumping ground.The content of CaCO3 is influenced largely by the presence of fine earth and ash in the MSW. Kamees (1979 ) reported that soils in Sulaimani governorate area are classified as alkaline soils; they are strongly calcic with CaCO3 reaching 30%. Rashid ( 1993 ) reported that CaCO3 in the north part of Iraq Kurdistan Region ranged from 3.8% for Halabja to 65% for Akra from the same reference percentage sand content ranging from 1.18% for Bakrajo to 84.92% for AskiKalak, while percentage silt content ranged from 3.79 for Aski- Kalak to 73.7 for Kala Diza. Rashid (2010) revealed the amount of calcium carbonate to be more than 10% in the soil of Darbankhan and Arbat area.
6.1.18 Available Phosphorus in Soil : Phosphorus is an essential element for plant growth, additional fertilizer P if high crop yields are desired and soil test P levels are low. In soil, phosphorus (P) exists mostly in organic and inorganic forms both of which are important sources of phosphorus for plant and microbial uptake ( Li et al., 2002 ). The organic forms exists as phosphates mostly in humus and other organic materials while inorganic P are in various combinations of Al, Fe, Mg, Ca and other elements ( Chinyere et al., 2013 ). These are probable sources of the high phosphate concentration observed in the heavily polluted areas of this dumpsite. The amount of available phosphorus removed from soil by ( NaHCO3 ) extraction ranged between (2.3 mg.Kg-1 to 8.7 mg.Kg-1) with an overall mean of ( 5.3 mg.Kg-1 ). The results obtained that lower than values recorded by ( Rashid, 2010; Roghanian et al. 2012; Wided et al., 2014 ). That recording (10.62 and 9.02µg.g-1 , 24 mg kg-1 and 20-73 mg.kg-1) respectively, while they were similar to results obtained by ( Muhammed, 2008) who recorded ( 3-8 mg.kg-1 ). Similar study by Agyarkol et al. (2010) revealed the refuse dump soils were observed to have higher levels of organic matter, available phosphorus (phosphates) and exchangeable cations such as Calcium and Magnessium.
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Calcareous soils are often low in available phosphorus for plants. This is mainly due to the reactions of soluble phosphate with calcium forming calcium-phosphate of various solubility and to adsorption and precipitation of phosphate by calcium carbonate ( Lindsay et al., 1959).
6.2 Heavy Metal Concentration in Water and Soil: Heavy metals are metallic elements that have specific gravity (density) greater than 5 g.cm-3 and can be hazardous at elevated concentration. Heavy metals are dangerous because they tend to bioaccumulate. Heavy metals are natural components of the earth’s crust and they can enter the water and food cycles through a variety of chemical and geochemical Processes ( Gbaruke and Friday, 2007). The contaminations of soil, water and air with heavy metals even at low concentrations are known to have potential impact on environmental quality and human health; these metals also pose a long-term risk to groundwater and ecosystems in general ( Cecilia and Christian, 2008 ). Many elements listed as environmental hazards ( arsenic, cadmium, lead, mercury, etc.) are also essential dietary trace elements required for normal growth and development of plants, animals and human beings. The lines of demarcation between essential and toxic levels are rather arbitrary: (a) Essential at trace levels for sustenance of life processes (b) Deficient at lower levels than (a) causing malnutrition; (c) Toxic at levels higher than (a) causing system disorder and on occasions, fatal effects. Environmental impact of open dump of MSW can usually result from the run-off of the toxic compounds into surface water and groundwater, which eventually lead to water pollution as a result of percolation of leachate ( Beaven and Walker, 1997; Rajkumar et al., 2010 ). The occurrence of various heavy metals such as Mn, As, Cr, Cd, Ni, Zn, Co, Cu, pb and Fe in MSW dumpsites was reported by many researchers ( Amusan et al., 2005; Esakku et al., 2003; Hoffmann et al., 1991; Ogundiran and Osibanjo, 2008, Tripathi and Misra, 2012 ). Municipal solid waste has been found to contain appreciable quantity of heavy metals such as Cd, Zn, Pb, and Cu, all of which may eventually end - up in the soil and are leached down the profile ( Oyedele et al., 2008 ). The contaminations of soil and water with heavy metals even at low concentrations are known to have potential impact on environmental quality and human health; these metals also 81
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pose a long-term risk to groundwater and ecosystems in general ( Beyene and Banerjee, 2011 ). A study by Esakku et al. ( 2003) on heavy metals in a municipal solid waste dumpsite in India revealed that the concentrations of Cr and Pb exceed the limits set by the standards set up by the Government of India. Another study by Mehreteab and Silke ( 2009 ) at Asmara landfill, in Eritrea revealed that except for Hg, all the analyzed heavy metals in the landfill site showed values above the permissible limits ( Mehreteab and Silke, 2009 ). Another study in Nigeria indicated that heavy metals ( Pb, Cu, Fe and Zn ) increased by between 214% and 2040% in the soils of the dump sites via a soils from non dump sites ( Anikwe and Nwobodo, 2002 ). A study to assess the distribution of heavy metals profile in groundwater system at solid waste disposal sites in Malaysia revealed that the heavy metals like Pb, Mn, Zn, Fe and Cd were found in significantly high levels exceeding the maximum permissible concentration as specified by the World Health Organization standards for drinking water ( Kamarudin et al., 2009 ). These may lead to increased uptake of metals by some test crops although their transfer ratios differ from crop to crop. A study by Ikem et al. ( 2002 ) in Nigeria indicated that the leachate collected from two dumpsites had appreciably high levels of Pb, Fe and Mn and ground water samples were polluted with Pb, Cd, Fe, Cr, Ni. A medical evaluation of the children and adolescents living and schooling near a dumpsite in Kenya indicated a high incidence of diseases that are associated with high exposure levels to these metal pollutants and about 50% of the children examined had blood levels of Pb in blood which are either equaled or exceeded internationally accepted toxic levels, while 30% had size and staining abnormalities of their red blood cells, confirming high exposure to heavy metal poisoning ( Kimani, 2007 ).
6.2.1 Trace Element Concentrations in Water Samples: Metals appear in the municipal solid waste stream from a variety of sources. Batteries, consumer electronics, ceramics, light bulbs, house dust and paint chips, lead foils such as wine bottle closures, used motor oils, plastics, and some inks and glass can all introduce metal contaminants into the solid waste stream. Composts made from the organic material in solid waste will inevitably contain these elements, although at low concentrations after most contaminants have been removed ( Flavia et al, 2008 ). 88
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Metals also have a high affinity for humic acids, organic clays, and oxides coated with organic matter ( Elliot et al., 1986 ). The solubility of the metals in soils and groundwater is predominantly controlled by pH ( Henry, 2000 and Ogbona et al., 2009), amount of metal and cation exchange capacity ( Martinez and Motto, 2000), organic carbon content ( Elliot et al., 1986) and the oxidation state of mineral components as well as the redox potential of the system (Ogbona et al., 2009). Krishna and Govil ( 2004 ) reported, that high levels of zinc in environment means zinc pollution, the main sources being smelting, application of dumping site to land, using levels of agrochemicals such as fertilizer, pesticides in agriculture practices, and other anthropogenic processes. The impacts of a solid waste disposal site on environmental pollution were investigated; pollution was found to occur mostly through migration of leachate ( Kassenga and Mbuligwe, 2009). The World Health Organization recommends that the iron content of drinking water should not be greater than 0.3 mg.l-1 ( Deutsch, 2003 ). The permissible limit for cadmium is 0.01 mg.l-1, beyond this the water becomes toxic. It was also remarked that the formation of blue baby syndrome in babies and goitre in adults were results of consumption of water with quantity of iron above the specified values ( Akinbile and Yusoff , 2011). Cadmium is a non-essential element and it is both bioavailable and toxic. It interferes with metabolic processes in plants and can bioaccumulate in aquatic organisms and enters the food chain ( Muwanga, 2006 ). Arsenic is one of the less abundant metal in the earth’s crust. In addition to its natural occurrence, more than 80 % of all the ( As ) are produced by the human. Human activities have substantially altered the natural distribution of this metal in the environment, because it has been used in an environmentally dissipative manner – as herbicides, insecticides, feed additives, wood preservative, chemical warfare agent, constituents of organic and inorganic pigments and drugs, as well as an alloying element ( Lubin et al., 2007 ). WHO ( 2006 ) considers that lead is toxic for both central and peripheral nervous system, including subencephalopathic neurological and behavioral effects. In other hand Cadmium (Cd) is a widespread pollutant and one of the most toxic heavy metals in the environment due to its high mobility and toxicity at low concentration ( Moustakas et al., 2011). In addition, the usage of chemical fertilizer and agro-chemicals also increased heavy metals pollution in the farmland. It was reported that there was 2-3 mg.kg-1 ( Cd ) in the phosphorous fertilizer (He and Hu 1991). Because fertilizers are not sufficiently purified during the process of manufacture, for economic reasons, they contain impurities, 800
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among them heavy metals. Also Cd, Pb and Ni are often forming a part of the active compound of pesticide ( Cheng, 2003). Pollution of groundwater in the studied area may result from leakage of pollutants towards groundwater. In particular, some cadmium compounds are able to leach through soil to ground water ( EPA, 2004). The average concentrations of zinc in well waters ranged between 0.002 to 0.012 mg.l-1 and 0.004 mg.l-1 as mean, while surface water value ranged between 0.003 to 0.009 mg.l-1 with the mean value 0.005 mg.l-1. The mean average concentrations of zinc in well waters were below those that are recommended by WHO ( 2006 ), and EPA ( 2004 ) level of 3 mg.l-1 for portable use. The mean average concentrations of arsenic in well waters ranged between 0.010 -0.097 mg.l-1 and 0.036 mg.l-1 as mean, while surface water value ranged between 0.05-0.16 mg.l-1 with the mean value of 0.10 mg.l-1. The mean average concentrations of arsenic in well waters exceeded those that are recommended by WHO (2006), and EPA (2004) level of 0.01 mgL-1 for portable use. This may be due contribute to either natural process such as ,Weathering of rocks and sediment, wind-blown dust, and gaseous forms through water and air, or to human activity such as agricultural application of pesticides and fertilizer, High traffic rate, disposal and incineration of solid waste and Atmospheric deposition ( Nriagu and Pacyna,1988 ). While for well waters, Cadmium concentration values ranged from 0.002 to 0.0034 mg.l-1 and 0.0025 mg.l-1 as mean value, while for surface water values it ranged from 0.002 to 0.0035 and 0.0028 mg.l-1 as mean. Cadmium concentration values for well water was below the permissible level 0.003 and 0.005 mg.l-1 according to WHO (2006), IQS (2001), EPA (2004), Canadian ( 2004 ). The mean average concentrations of iron in well waters ranged between 0.011 to 0.079 mg.l-1, with the mean value 0.039 mg.l-1. while surface water value ranged between 0.051 to 0.171 mg.l-1 with the mean value 0.099 mg.l-1. The mean average concentrations of iron in well waters were below the detection limit recommended by WHO (2006), and EPA (2004) level of 0.3 mg.l-1 for portable uses. According to Diagomanlin et al. (2004), and Berry et al. (1980) may be the source of heavy metal (iron) in groundwater include raw household wastewater which may contain metals such as pharmaceutical, paint, battery and also vegetable matter and human excreta. On the other hand, the Lead concentration value for well waters ranged from 0.035 mg.l-1 as minimum, 0.051 mg.l-1 as maximum with the mean value of 0.04 mg.l-1, while for surface water 808
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ranged from 0.04 to 0.044 mg.l-1 with the mean value of 0.04 mg.l-1. Lead concentration values in all well water samples exceeded those that are recommended by WHO (2006), EU (2006), Canadian standard ( 2006 ), IQS ( 2001 ) which is equal to 0.01 mg.l-1, while for surface water, its 0.003 mg.l-1 from different references (Langmuir 1997, WHO 2006, EU 2004) .This very high concentration level of lead in well waters illustrates the impact of solid waste landfill leachate which penetrates soil profile towards groundwater ( Rashid, 2010 ). Nickle concentration values for well waters ranged from 0.004 mg.l-1 as minimum, 0.015 mg.l-1 as maximum with the mean value of 0.008 mg.l-1, while for surface water it ranged from 0.021 to 0.022 mg.l-1 with the mean value of 0.021 mg.l-1. Nickle concentration values in all well water samples were below or in surface water equal to those that are recommended by WHO (2006), Canadian standard (2006), all studied water samples show high pollution by nickel, which exceed permissible level 0.02 mg.l-1. Surface water pollution by nickel is greater than ground water pollution, this may be related to the fact that surface water is more exposed to anthropogenic pollution than ground water, such as effluent of leachate water, atmospheric deposition and disposal municipal waste around the water sources then runoff during rainy season into the water body ( leung and Jiao, 2006). The results agreed with results obtained by (Marijan et al., 1998; Ikem et al., 2002; Mustafa, 2006; Kimani, 2007; Flavia et al.,2008; Singh et al., 2008; Kassenga and Mbuligwe, 2009; Jhamnani and Singh, 2009; Ololade et al., 2009; Rajkumar et al., 2010; Rashid,2010; Akinbile et al., 2011; Amadi, 2011; Beyene and Banerjee ; Partha et al., 2011; Dibakar et al.,2012 and Afolayan et al., 2012). Focusing on the review of published works and efforts of researcher in Kurdistan region, other parts of Iraq and in different parts of the world had been conducted on the water pollution by heavy metals. A study to assess the distribution of heavy metals profile in groundwater system at solid waste disposal sites in malaysia revealed that heavy metals like Pb, Mn, Zn, Fe and Cd were found in significantly high levels, which exceeded the maximum permissible concentration as specified by the World Health Organization, WHO Standards for Drinking Water ( Kamarudin et al., 2009 ). A study by Rashid ( 2010 ) in a dumpsite are in sulaimani city revealed that the mean concentration values of heavy metals in Tanjaro river showed lower values. Most of the studied samples from the river showed pollution by heavy metals (except Zn, Cu, Al and Fe) which 808
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exceeded permissible recommended values due to impact of sewage waste water from Sulaimani city, location of landfill site adjacent to river, and anthropogenic activities. Levels of heavy metals were relatively high in well water adjacent to landfill site. Anuar Ithnin et al. (2012) studied the effect of leachates from old dumping site on water quality of sungai datu revealed that the concentration of lead, cadmium, arsenic, zinc, manganese and copper were mainly higher than permissible limit of WHO. Waste disposal techniques have created subtle and yet serious environmental pollution and ecological deterioration in many developing countries. Amadi ( 2011 ) revealed that heavy metals concentrations vary as follows: Fe > Zn > Cu > Mn > Cr > Pb > As. This may be attributed to high precipitation and subsequent weathering and leaching of metallic objects from the dumpsite into the shallow groundwater table. The elevated level of metals in the surface water further implicates the magnitude of metal input from effluent/leacheates resulting from wastes which are indiscriminately dumped into the stream ( Ololade et al., 2009). Leachate migration from waste sites or landfills and the release of pollutants from sediments (under certain condition) pose a high risk to ground water resource if not adequately managed ( Ikem et al., 2002).
6.2.2 Trace Element Concentrations in Soil Samples: Trace elements in soils can be divided into water soluble, exchangeable, oxide bound, carbonate-bound, organic matter-bound, and residual that is occluded in the resistant minerals and non extractable ( Shuman, 1991 ). In general, heavy metals may react with particular species, change oxidation states and precipitation, which may increase or decrease mobility. The transport mechanisms of heavy metals through soil has long presented a great interest to both environmental and soil scientists because of the possibility of ground water contamination through metal leaching ( Dube, 2000). Migration of contaminants from waste disposal sites to surrounding ecosystems is a complex process and involves various geochemical activities due to magnification of trace heavy metals. These metals can bio-magnify in plants and animals eventually making their way to humans through the food chain ( Abrahams, 2002 ). Iron, manganese and lead have low to very low mobility at pH < 7 and thus would be enriched in soil. Nickel, copper and zinc have high mobility under acidic conditions and due to formation of sparingly soluble metal sulphides with very low mobility under reducing conditions, these metals in soils can either be enriched or 808
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depleted relative to parent material depending on the dominant factors that exist in the weathering environment ( Tripathi and Misra, 2012 ). It is also revealed that there is an obvious gradual reduction in the concentration of heavy metals as we move few meters away from the center of the dump site of a particular location. Disposal of municipal solid wastes and household hazardous wastes including batteries, paint residue, ash, treated woods and electronic wastes increase heavy metals in soil ( Pare et al., 1999, Macki Aleagha et al, 2009 ). Cr, Pb, Ni, Cd and As are the chief heavy metals of MSW ( Williams, 2005). Roels et al. (1997) reported that Cd and Ni encountered in industries dealing with pigment, metal plating, some plastic and batteries. Heavy metals release naturally by erosion of rocks, volcanic activity, forest fire and artificially by many industries, paper mills, vehicles and human activities and it can release in large quantities directly affecting the flora, fauna as well as human population ( Martin and Griswold, 2009 ). Dumping of solid wastes without proper separation increases the concentration of heavy metals such as Arsenic (As), Cadmium (Cd), Chromium (Cr), Copper (Cu), Lead (Pb), Nickle (Ni) and Zinc (Zn). These heavy metals, when present in solid waste, have been known to produce major environmental impacts ( Beyene and Banerjee, 2011 ). Behaviour of all heavy metals in soil all depends on the soil pH, properties of metals, soil chemistry, organic matter content, clay content, cation exchange capacity and soluble ligands in the surrounding fluid. Heavy metals are generally more mobile in the soil in the acidic pH range (Cavallaro and McBride, 1978 and Alloway and Ayres, 1997). The potential hazards associated with the heavymetal contamination of soils tend to increase with time. This may be caused by a decrease in soil pH, especially when the nitrogen and sulphur contents of the waste products are high and the lime content low ( Roghanian et al., 2012). Soil pH affects the speciation and adsorption of heavy metals in soil, determining the mobility, bioavailability and toxicity of the metal (Yin et al., 2002). Anthropogenic sources of heavy metal in soils are mainly hazardous/solid waste disposal and combustion processes in industry and transportation. Long-term and extensive use of agricultural land with frequent application of pesticides will result in heavy metals such as nickel, zinc and cadmium accumulating in the top soil ( Banar et al., 2009 ).Contamination of soils by heavy metals can be caused by many factors such as metal-enriched parent materials, industrial activities, non point sources of metals, especially automotive emission, and use of 808
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metal-enriched materials, including chemical fertilizers, farm manures and waste water irrigation. However, soil contamination by heavy metals and toxic elements due to parent materials or point sources often occurs on a limited area and is easy to identify (He et al., 2005 ). Among significant variables that control the mobility, distribution and enrichment of heavy metals in soils are pH of soil, grain size of the soil, amount of organic matter in the soil, cation exchange capacity of the soil, clay content and ion competition ( Elliot et al., 1986; Yong et al., 1992; Fahhar and Pickering, 1997; Weber et al., 1997; Huang and Lin, 2003 and Amadi and Nwankwoala, 2013 ). Depending on the pH, some metals show a greater or lesser solubility, which may lead to precipitation or not ( Raij, 1997; Costa et al., 2004). Organic matter, Fe and Mn oxides and clay minerals are able to form complexes and adsorb several metal due to the surface charge of these materials ( Langmuir, 1997; Costa et al., 2004 ). Different sources such as electronic goods, painting waste, used batteries, etc., when dumped with municipal solid wastes raise heavy metals in dumpsites and dumping devoid of the separation of hazardous waste can further elevate noxious environmental effects ( Rajkumar et al., 2010 ). Similar observations have been reported by Beyene and Banerjee ( 2011) who revealed that the maximum concentration of Cr in the dumpsites was (561 ppm) and (513 ppm) respectively. The mean concentration of Cr (243 ppm) was found to be in an elevated concentration than the typical concentration of MSW compost in the United States (Flavia et al., 2008). Though of low phytotoxicity, lead may become mobile at lower pH and enter the food chain from the numerous agricultural activities that use the stream water poising health risks to consumers of the agricultural products ( Nabulo et al., 2010 ). Similar studies in Egypt by Rashad and Shalaby (2007) and Kenya by Njoroge ( 2007 ) indicated that land surfaces surrounding dumpsites have been contaminated with high levels of metals. Trace element accumulation in soil of the dump site may lead to increased uptake by plants although their transfer ratios differ from crop to crop. Cadmium metal is used as an anticorrosive, electroplated on steel, also commonly used as pigments in plastics, batteries and in various electronic components. They are thrown into the dump as waste, during decomposition, the Cd component is leached into the surrounding soil and over time gets accumulated in the soil (Che et al., 2003; Gorenc et al., 2004; Amadi and Nwankwoala, 2013 ). Manganese dioxide and other manganese compounds are used in products such as batteries, glass and fireworks, fertilizer, fungicides and as livestock feeding supplements (Huang & Lin, 2003; Aboud & Nandini, 2009). Copper is widely used in electrical wiring, 808
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roofing, various alloys, pigments, cooking utensils, piping and in the chemical industries (Aboud & Nandini, 2009).
Cr It is used in alloys, electroplating, pigments, paints manufacture,
fungicides, photography, glass and leather tanning industries. Chromium is carcinogenic by inhalation and corrosive to tissue (Lin et al., 2002; Aboud & Nandini, 2009). Nickel is used mainly as alloys, stainless steels, non-ferrous alloys and super alloys, nickel-cadmium batteries, welding and electronic products ( Amadi, 2011 ). lead is essential in the production of lead acid batteries, solder, alloys, cable sheathing, pigments, ammunition, glass and plastic stabilizers ( McAllister et al., 2005). It is possible that these levels of Pb is elevated by the amount of waste oil, presence of automobile emissions, and expired motor batteries indiscriminately dumped by battery charger in the surrounding areas ( Aloysius, 2013). Zinc is used in making alloys of brass and bronze, batteries, fungicides, pigments, pesticides, galvanizing steel and iron products. Excessive concentration of Zn in soil leads to phyto-toxicity as it is a weed killer ( Aboud & Nandini, 2009 ). When these products are thrown into the dumpsite, these elements are leached away and accumulate at the top soil where they are adsorbed because of affinity for metals by organic matter ( Odero et al., 2000; Amadi, 2011). Trace element concentrations in dumping sites soils collected from six locations showed a wide range of trace element concentrations across the studied area found in order of Mn> Zn >Cu> Ni> Pb>Cr>As> Cd (1187-987 mg.kg-1, 915.3-225.03 mg.kg-1, 301.1-232.8 mg.kg-1, 192.24-150.41 mg.kg-1,193.1-76.71 mg.kg-1, 173.1-142.2 mg.kg-1, 20.15-14.23 mg.kg-1 and 5.712-2.317 mg.kg-1). The mean concentration of Ni, Zn, Cd, Cr , Mn and Cu were exceeding European union standards ( EU, 2006 ), while the mean value of As and Pb were below the European union standard ( EU, 2006 ). Ni, Zn, Cd, Cr and Cu were available in very high levels as it is very close to the municipal waste disposal and dumping place of the city. It overlooks the fields and, during rainy seasons, runoff is washed into farming fields and flying ash generated by waste incineration precipitates on the surrounding waste disposal fields. Higher concentrations of toxic elements were found, this is very probably due to the irregular dumping site, irrigation of the farms by water discharges and may be due to the precipitation of strong industrial dust and fly ashes generated by incineration of solid waste into near by the agricultural fields. It’s known that the bioavailability of metals in soil depend on pH, organic matter and total metal content (Adjia et al., 2008). 808
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Heavy metals concentration at Halabja disposal waste area at many sampling points were considerably high; this is because those sampling sites were relatively close to the solid waste pile therefore this high concentration may referred to the effect of the waste pile. In general, Cu and Zn contamination of soil is derived from the application of agricultural materials particularly fungicides, such as, Bordeaux mixture and the atmospheric deposition from industrial activities (Maas et al., 2010). It can be noted that, the concentration of Cu and Zn were relatively higher at solid disposal area compared to other areas. In most developing countries including Iraq, leaded gasoline is sill widely used, for example in Kurdistan region more than 82% of the gasoline consumption is leaded ( Rashid, 2010 ). The result is supported by values obtained by other researcher such as ( Esakku et al., 2003; Krishna et al., 2004; Oyedele et al., 2008; Flávia et al., 2008; Adjia et al., 2008; Ogbonna and Youdeowei, 2009; Awokunmil et al., 2010; Amuno, 2011; Partha et al., 2011 and Chinyere et al.., 2013).
6.2.3 Accumulation of Trace Elements in The Wheat Grain: Heavy metal pollution not only affects water bodies, but also influences the production and quality of crops, atmosphere and threatens the health and life of animals and human beings by way of the food chain. Those contaminants accumulate in plants, especially in foods, and bring toxicity and diseases of geological and environmental origin to human beings. Most severe is that this kind of pollution is covert, long-term and non-reversible. Therefore, humans should be careful with heavy metal polluted water and food. In conclusion, many studies have shown that heavy metal is hazardous at high concentration; it is obvious that soil and plant will constitute a serious threat to the health of people living around such areas. This can be controlled by adopting a good waste management approach to the waste disposal ( Nabulo et al., 2008 ). Heavy metal accumulation in soils is of concern in agricultural production due to the adverse effects on food quality, crop growth and environmental health. Consequently, subsequent application of MSW composts rich in heavy metals to agricultural soils may cause heavy metal accumulation to toxic levels ( Bilos et al., 2001,Veeken and hamelers, 2002 ). Plants absorb and accumulate heavy metals from the soil and water, which up to certain level are essential for their growth and development. Heavy metals in soils are mobile and can be taken up easily by the plants ( Mori et al. 2009 ). Cadmium is a highly mobile metal, easily absorbed by 808
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the plants through root surface and moves to wood tissue and transfers to upper parts of plants growing on dumpsites ( Olufunmilayo, et al., 2014 ). However, predicting exposure to potentially toxic metals from consumption of food crops is more complicated because uptake of metals by plants depends on soil properties and plant physiologic factors ( Chinese Department of Preventive Medicine, 1995 ). Heavy metals contained in biosolids are easily immobilisable by plants, because of their strong association with organic matter in the biosolids ( Silveira et al, 2003 ). The uptake and bioaccumulation of heavy metals in plants is influenced by many factors such as atmospheric depositions, climate, the concentrations of heavy metals in soils, the nature of soil and the degree of maturity of the plants at the time of the harvest (Olufunmilayo, et al., 2014 ). The range for trace elements for wheat samples were 115 mg.kg-1 for Zn, 0.0313 mg.kg-1 for As,1.2 mg.kg-1 for Cd, 2.1 mg.kg-1 for Pb, 1.19 mg.kg-1 for Ni and 0.058 mg.kg-1 for Cr. The concentrations of all metals except Zn and Cr in wheat crops around the open dump waste disposal area were constantly higher than the recommended value set by ( UK food standard agency, 2009 and WHO/FAO, 2007) standard limits. They variation were found in the order of Zn>Pb>Ni>Cd>Cr>As . Wheat contamination with high levels of Ni, Cd, and Cu content at all sites might refer to the presence of Ni and Cu rich rocks in the areas, and increasing heavy metals in soil due to the dumping site. The concentration of As in the wheat, at solid waste dumping area because they are being influenced by the municipal waste dump near the sampling sites. By contrast, higher pb concentration was found at the open dump solid waste area, this was due to anthropogenic source of contaminations in the area such as soil waste disposal and industrial outcomes, rather than using waste/industrial water for irrigation purposes. On the other hand the comparatively high level of lead in grain at study area station could be as a result of physical contact with air-borne materials from vehicular emissions ( Ideriah et al., 2010) . Similar study by Igbozuruike et al. ( 2009) revealed that accumulation of Zn, Pb, Cd and Ni increased in the dump site cassava tuber relative to non- dumpsite. Also same study by Magji (2012) was revealed that the concentrations of heavy metals in all the samples cultivated around the dumpsite are higher than those from the control site.
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Discussion
This finding was in agreement with the studies conducted in different countries ( Amusan et al.,1999; Anikwe and Nwobodo, 2002; Barazani et al., 2004; Rashad and Shalaby, 2007; Adefemi and Awokunmi, 2009 and Fagbote and Olanipekun, 2010 ).
6.3: Water Quality index: Water quality index in the historical and the present study is established from important various physicochemical parameters in different seasons. Application of Water Quality Index (WQI) in this study has been found useful in assessing the overall quality of water and to get ride of judgments on the quality of the water. This method appears to be more systematic and gives a comparative evaluation of the water quality of the sampling stations. It is also helpful for the public to understand the quality of water as well as being a useful tool in many ways in the field of water quality management. Table (6.3): Water quality classification based on WQI value (Ramakrishnaiah et al., 2009).
Description
Water Quality Index levels
Excellent
<50
Good water
50-100
Poor water
100-200
Very poor (bad) water
200-300
Unsuitable (unifit) for drinking
>300
Application of Water Quality Index ( WQI ) in this study has been found useful in assessing the overall quality of water and to get ride of judgment on the quality of the water. This method appears to be more systematic and gives a comparative evaluation of the water quality of sampling stations ( Khwakaram et al., 2012, Toma, 2012 ). The mean of WQI for ground and surface water were 90.23 and 102.5 respectively during the studied period, hence, the water can be recognized as “good water” for ground water and “Poor water” for surface water according to water quality classification based on WQI.
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Discussion
6.4: Risk Assessment ( Hazard Indices ): The values of combined HQ ( Hazard Quotient ) were lower than 1 for all heavy metals in ground and surface water samples indicating no health risk for the local population from using the drinking water in the area. Chronic daily intake (CDI), hazard quotient (HQ) and hazard index (HI) for consumption of ground drinking water. CDI indices for HM in the study area were found in the order of Pb>Fe>Ni>As>Zn>Cd. The mean HQ index value for Zn, As, Cd, Fe, Pb and Ni for ground water were 0.00037,0.2, 0.138889, 0.000181, 0.030864 and 0.011111 respectively, while the hazard index was equal to (0.38142) which is lower <1 for all studied heavy metals in ground drinking water samples indicating no health risk. While an HI of <1.0 is considered acceptable ( Muhammad et al., 2011). While Chronic daily intake (CDI), hazard quotient ( HQ ) and hazard index ( HI ) for consumption of surface water. CDI indices for heavy metals in the study area were found in the order of Cd>As>Pb>Fe>Ni>Zn. The mean HQ index value for Zn, As, Cd, Fe, Pb and Ni for ground water were 0.000463, 0.555556,0.111111, 0.000181, 0.030864 and 0.029167 respectively, while the Hazard index is equal to (0.72734) which is lower <1 for all studied heavy metals in study surface water samples indicating no health risk. while an HI of <1.0 is considered acceptable ( Muhammad et al., 2010 and Muhammad et al, 2011).
880
Conclusion
Conclusion 1- Open dump area are considered a serious threat to their surrounding urban environments and a great source of pollution. Pollutants discharged from the open dumping leachate are responsible for alterations of water and soil physico-chemical properties and the majority of water, soil and wheat samples are polluted by heavy metals. 2- The effect of open dump pollution causes an increase in organic matter in soils around the area. 3- Results show that the waste dump has significant effects on the water quality, although the mean values of many parameters analyzed fell below WHO and EU standards for drinking water. 4-The results of the study revealed that soils around the dumpsite are considerably contaminated by metals with their concentrations beyond threshold values according to EU.
5-The long term result of open waste disposal is a considerable amount of heavy metals and metalloid accumulated in the agricultural fields and consequently in plants grown on these fields such as wheat.
6-The health risk assessments like Hazard indices for heavy metals indicated that the drinking water no health risk for human consumption.
7-The application of WQI suggests that the groundwater around the open dumpsite is good water in quality, while surface water is poor water in quality.
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Recommendation
Recommendations 1-Solid waste should be carefully reduce, refuse, recycle, reuse and sorted out to recyclable , organic and hazardous substances,. The toxic substances must be removed and landfilled hence ensuring the safety of the agricultural fields around the disposal areas.
2-Refrain from disposing waste in and around agricultural fields because it may pose potential health risk to the local consumers, as well as burning waste near the city will result in toxic emissions that are liberated directly in to the atmosphere consequently leading to possible health hazards to the residence.
3-Systematic investigation on the local environmental pollution, particularly agricultural soil contamination, is strongly recommended because it may decrease the level of contamination and improve human health in the area.
4-Conducting more studies for more other characteristics in water and soil in details and time interval are necessary. Eapecially Focus on future studies about Arsenic and Lead .
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حلومةتى يةزيَمى كوزدستاى وةشازةتى خويَهدنى باآلو تويَريهةوةى شانستى شانلؤى سويَمانى – سلوهَى شانست
هيَلوَهَيهةوةيةكى ذيهطةشانى هةسةز ناوضةى ويَستطةى فسيدانى خاشان هة شازي يةهَةجبة – يةزيَمى كوزدستانى عيَساق نامةيةكة ثيَصلةش كساوة بة ئةجنومةنى فاكوَتى شانست وثةزوةزدةى شانستةكاى سلوهَى شانست هة شانلؤي سويَمانى وةن بةشيَم هة ثيَداويستيةكانى بةدةستًيَهانى بسِوانامةى ماستةزى شانست هة شيهدةوةزشانى – ذيهطة وثيسبووى هة اليةى ساالز حسني كةزيم بةكاهوزيؤس هة بوازى شيهدةوةزشانى – شانلؤى سةالحةدديو 0222 دبوؤمى باهَا هة بوازى شيهدةوةزشانى – شانلؤى سةالحةدديو 0202 هة ذيَس سةزثةزشيت د .شيَسكؤ عوى حممد ماموستا سةزماوةش ( 0102كوزدى)
سةفةز ( 0216كؤ ضى)
تصسيهى دووةم ( 0202شايهى)
ثوختة ويانىويوةاى ي اواوديـى بةهؤى زياد بوونى ذمارةى دانيشتوان و زياد بووونى اواى ى و ووةو ثيووةوونةى مـ خووو خود ـدنى ثيس بوون بووةاة واريشةية ى هةنوو ةيى .ية يك دةو هؤ ارانةى ة اريطةريان دةسةر ثيوةوونى ذينطة هةيوة زيواد بوون و ؤ ـدمةوةى خؤل و خاشا ة بةشيوةية ى نا زانوتى . وةىووة بووة دورى ن يلووةى 5يلؤمووةاـ دووة وينةوةيووة دووة ناواووةى ؤ ـدنووةوةى خاشوواة وووةةال دراوة دووة هةد وووةل ديلؤد سةنتةرى شارةوة . وةىووة ن يلووةى ( )66755ووةد دةبوور و رن ذانووة وى 9002دانيشووتوانى سووةنتةرى شووارى هةد بووةثيى وامارة ووانى سوواد ن يلةى ( )00اؤن دة خاشاة بةرهوةل دةهيونر .دااا وان دةسوةر بنوةماى موانك ؤ ـاوةاوةوة دوةماوةى موانطى وايوار اوا موانطى انوونى ية ةل 9009ى خايانىووة ي دةوانةش منوونة دة واوى ذيـ زةوى وااوة ووةو باانوة و وواوى سوةر زةوى وةن يلر دوة وى دةورووبةرى شوينى فـنيىاني خاشا ة ة وةرطااوة بةمةبةستى شويلارى في يواوى و شوينى فـنيىانى خاشا ة ةوة وةخؤد وطوة انى شووينة ة وةرطوااوة بوة مةبةسوتى شويلارى هةنوى دوة يميايي و ان ا قورسة ان .وة هةروةها منوونةى طةمنى يل اومخة قورسة ان . بةهاى ثةيتى اـشةدؤ ى ) )pHدةنيوان ( )75-7.9 , 6.5-7.4داية دةناو وواوى ذيوـ زةوى و سوةر زةوى يوةة دوةدواى وينةوةى ايىا وةةال دراوة هاواا بؤ افتى مال ناوةنى ثيشان دةدات ي دة اايلىا يةة ي دااا ؤ ـاوة ان دةو شوينةى وةل ديلؤد بةهاى ثةيتى اـشة دؤ ى ( )pHدةنيوان ( )7.9-82دة خا ىا ة افتى مامناوةنى ثيشان دةدات .ناوةنىى ثلوةى طوةرماى وواو دةنيوان( )7.4-19.5 , 18.1-270 0cبووة دة واوى ذيـ زةوى و واوى سةر زةويىا يةة دة دواى يةة طةيانوىنى
ارةبوا دوةناوواو دوةنيوان ( )363-662 µs.cm-1وة (µs.cm-1
)357.3-406.7بوؤ هوةردوو وواوى بوا و
ووواوى سووةرزةوى يووةة دووةدواى يووةة .ووة ووةم دووة ايل وـناى ب وةرزى بووةهاى طةيانووىنى ارةبووا بووةثيى رنيلنووـاوى اةنىروسووتى جيهانى ثيشان دةدات .دةىية ى اـةوة طةيانىنى ارةبايى بؤ خا ى ناواة
ة دةنيوان (µs .cm-1
)363.1-580.3داية .
رنيذةى وؤ وجينى اواوة دةنيوان ( )5.8- 7.3ملغم/دي 0-وة ()7.8-7.2ملغم/دي 0-بوو ي دة وواوى ذيوـ زةوى و وواوى سةر زةويىا يةة دةدواى يةة .دة اايلىا ناوةنىى ثيويوتى وؤ وجني دة نيوان ( )3.6-2.8وة ( )4.4-4.1ملغم /دي 0-بووو ي بةمةش بة واوى ثاة يان ثا يلى مال ناوةنى ثؤدينلـاوة . ووؤى طشووتى ناسووازى ووواو دووة نيوووان ( )413.7-250ملغووم/دووي 0-وة ( )305.3-265.3ملغووم /CaCo3دووي
0-
ووة
بةواوى نيمضة يان اارنادةيةة ناساز دادةنـيت .دة اايلىا ناسازى بةهؤى وايؤنوااى اديوويؤمى و ناسوازى بوةهؤى وايؤنوااى مةطنيويؤمى واو دوة نيووان ( )147.3-63.3ملغوم /CaCo3دوي 0-وة ( )77-37.3ملغوم /CaCo3دوي 0-بوؤ وواوى ذيوـ زةوى
A
يةة دوةدواى يوةة وة ( 74.5-55.3ملغوم /CaCo3دوي )0-وة ( 57.7-42.5ملغوم /CaCo3دوي ) 0-بوؤ وواوى سوةرزةوى يوةة دةدواى يةة. دةىية ى اـةوة رنيذةى افتيتى دةنيوان ( )246-181ملغم /دي 0-وة ( )271.3-194.3ملغم /دي 0-بوو هةرية وة دوة واوى باة ان و واوى سةر زةوى يةة دةدواى يةة ة اارنادةيةة دة سةروو ثيووةرى رنيطوة ثيوىراو بووو بوؤ وواوى خواردنوةوة بوة ثيى رنيلنـاوى اةنىروستى جيهانى . بووةهاى خةسووتى ؤووؤديؤل بـيتووى بوووو دووة ()8.7-4.3ملغووم /دووي 0-وة ( )10-5.5ملغووم /دووي 0-وة بووةهاى خةسووتى ثؤااسيؤل دةنيوان ( )1.6-0.7ملغوم /دوي 0-وة ( )2.8-1.1ملغوم /دوي
0-
بوؤ هةرية وة دوة وواوى باة وان و وواوى سوةر زةوى
يةة دةدواى يةة ة بةها ان دة واستى رنيطة ثيىراو دا بوون بة ثي ى ستانىاردة ثةسةنى ـاوة ان . بةهاى خةستى هةرية ة دة لؤر و ناي يوت دوةنيوان ( )195-70ملغوم /دوي 0-و ( )16.1-9.5ملغوم /دوي 0-بوؤ وواوى سةر زةوى يةة دة دواى يةة ي ة واوة ان بـنى خةستى لؤر و ناي يت دة سنوورى رنيطة ثيىراو ثيشان دةدةن . بةهاى خةستى ان ا قورسة ان بؤ هةرية ة دوة ووايؤنى (زينوك و زةرنوي و وادميؤل و واسور و قورنقوشوم و نيلو ) دوة نيوووان ( )0.012-0.002ملغ وم /دووي 0-وة ( )0.097-0.051ملغووم /دووي 0-وة ( )0.0034-0.002ملغووم /دووي 0-وة (0.079- )0.011ملغووم /دووي 0-وة ( )0.051-0.035ملغووم /دووي 0-وة ( )0.015-0.005ملغووم /دووي 0-بووؤ ووواوى باة ووان وة (0.009- )0.001ملغوووم /دوووي 0-ي ( )0.16-0.05ملغوووم /دوووي 0-ي ( )0.0035-0.002ملغوووم /دوووي 0-ي ( )0.17-0.05ملغوووم /دوووي 0-ي ( )0.044-0.04ملغم /دي 0-ي ( )0.022-0.021ملغم /دي 0-بؤ واوى سةر زةوى يةة دةدواى يةة . بةهاى خةستى ان ا ان جطة دة قورنقوشم و زةرني هةموويان دة اوارايوةى بةهاى ثةسةنى وـاو رنيطوة ثيوىراو دان بؤ واوى باة ان و واوى سةر زةوى يةة دةدواى يةة . رنيذةى خةستى ربيت و ناي
جني دة خا ى وةرطااو دةنيوان ( )6.9-3.9( ,)0.030-0.002دة سةدا بوو ي دةىية ى
اـةوة رنيذةى خةستى ؤؤديؤل و مةطنيويؤل و ثؤااسيؤل و اديويؤل دة منوونوةى خوا ى وةرطوااو دوةنيوان ()3805-2766 ملغم /غم ي ( )18998-13326ملغم /غم ي ( )15835-13193ملغم /غم وة ( )75648-42489ملغم /غم دا بوون . بةآلل رنيذةى ماددةى وةنىامى دوةنيوان ()12.1-10.3دوة سوةد ا بووو وة خةسوتى بيلاربؤنوات و اديوويؤمى اربؤنوااى خاة دة نيوان ()48.4-19ملغم /غم دا بوون . بةهاى خةستى ان ا اورسة ان دة منوونةى خا ى وةرطااو بؤ هةريةة دة وايؤنوة انى (زينوك و زةرنوي و وادميؤل و قورنقوشم و نيلو و وـن ل و مةنطوةني و موس ) بـيتوى بووون دوة Mn> Cu>Zn> Pb>Ni>Cr>As> Cdدوةنيوان (15.34- )225.03ملغووووم /غووووم 0-ي ( )19.32-14.25ملغووووم /غووووم ي ( )5.12-2.317ملغووووم /غووووم ي ( )193.14-76.7ملغووووم /غووووم ي ( )192.24-150.41ملغووم /غووم ي ( )173.0-142.226ملغووم /غووم ي ( )118-987ملغووم /غووم ي ( )301.01-232.81ملغووم /
B
غووم دايووة ووة بووةهاى خةسووتى وووةل ان ايانووة جطووة دووة قورنقوشووم و زةرنووي دووة ز ربووةى منوونووة وةرطااوة ووانى خا ة ووةدا دووة سةرووى بةهاى رنيط ة ثيىراوة بةثي ى بةهاى دياريلـاو دةىيةن ية يتى وةوروثاوة ( . )European union وة ةبوونى اومخة قورسة ان دة منوونةى طةمنى وةرطوااو بوؤ هةرية وة دوة دةىية ى اـةوة ايلـناى بةهاى خةستى ةد (زينك و زةرني و ادميؤل و قورنقوشم و ـن ل و نيلأل ) بـيتية دة )115( :ملغم /غم ي ( )0.0313ملغم /غوم ( )1.2ملغوم /غوم ي ( )2.1ملغم /غم ي ( )0.058ملغم /غم ي ( )1.125ملغم /غم دا بوون .بةهاى خةستى هةموو اومخة ان جطوة زينوك و وـن ل دوة دةرةوةى اوووووار اوووويوةى بووووةهاى ثةسووووةنى ـاوة ووووان بووووة ثووووي ى رنيلنووووـاوى اةنىروسووووتى و خووووؤرا ى جيهووووانى (
/
FAO
)WHOو(.(United kingdom UK دوة ىيوة ى اوـةوة بوة ثىوى بوةهاى ثيووانى ثوا يتى ووواويبوـى ( )WQIبوؤ هةرية وة دوة وواوى ذيوـ زةوى بـيتوى بووون دووة( ) 90.23و واوى سةر زةوى ( )102.5ة بة ثىى ستانىاردى( )WQIواوى ذيـ زةوى بة واوى باش و واوى سةر زةوى بة واوى هوةذار دادةنـيوت.وة هوةروةها بوـى Hazard indexدوة يوةة وةم ة بؤسوةرجةمى اومخوة قورسوة ان ثيلوةوة دوة منونوةى وواوى وةرطووااودا ,بةمووةش دةردة ووةويت ووة هوويك يشووةيةة و مةاـسووية ى اةنىروسووتى نيووة بووو مةبةسووتى خواردنووةوة بووة ث و . Hazard
C
index
اخلصالة بسبب زيادة عدد السكان و كذلك نشاطاتها و تلوث التى سببها االنسان ,تكون رقاب التلوث مشكل حتمي و من االسباب التى هلا تاثري على تلوث البيئ هي زيادة النفايات والبقايات فى مدن بصورة غري علمي والرتاكمها. استنادا على احصائيات السن 9002كانت عدد سكان مركز مدين احللبج هى ما يقارب ( )66755النسم وينتجون ما يقارب 00طن من النفايات يوميا .اخذ البيانات شهريا و مت من شهر االيار اىل شهر الكانون االول سن .9009مت اخذ مناذج املاء من االبار و مصادر املياه السطحي قريب من اماكن جتمع النفايات و كذالك مت اخذ النماذج الرتب من اطرا اماكن النفايات لغرض التحليصالت الفيزيائي و الكيميائي واملعادن الثقيل . درج احلموض كانت ما بني ( ) 7.5 -5.6 , 7.2-7.6للمياه اجلوفي او االبار واملياة السطحي على التواىل .البيانات التى مت اخذها من املكان التى اجريت بها الدراس هو يعادل درج احلموض املتعادل و شبه املتعادل ,يف حني قيم احلموض بني ( )0.9-7.2يف الرتب هو يدل على قاعدى متوسط.و تراوحت متوسط درج احلرارة ما بني ( 02.6-07.5س 997.00 -00.0 , 0س )0للماء اجلوفي و السطحي على التواىل. اما بنسب اىل قيم التوةيل الكهربائي مابني ( )559-353ما يكروموز/سم و ( )505.7 -367.3مايكروموز/سم للمياة اجلوفي و السطحي على التوالي .و هو اقل من معدل قيم القياسي للتوةيل الكهربائي ملنظم الصح العاملي و من جه اخرى توةيل الكهربائي لرتب املنطق هي بني ( )600.3 -353.0ما يكروموز \سم. وتراوحت قيم االوكسجني املذاب بني ( )-6.0 -3.7ملغم\ليرت
0-
و ( )7.9 -7.0ملغم\ليرت 0-للمياة اجلوفي و السطحي على التوالي.يف 0-
حني ان معدل االوكسجني الضروري هوبني ( )9.0-3.5و ( )5.0-5.5ملغم\ ليرت .بهذا ينصف باملاء مفرد او شبه مفردة. وكذالك معدل الكلي لعسرة املاء هي بني ()960 -503.7ملغم\ ليرت
0-
و ( )956.3 -306.3ملغم \ ليرت
0-
وينصف باملياه شبه
العسرة.و عسرة املياه لقود اىل ايونات الكالسيوم و املغنسيوم والتى تراوحت فيها ما بني ()53.3 -057.3ملغم\ ليرت )37.3ملغم\ ليرت 0-للمياه االبار على التوالي و ( )66.3 -75.6ملغم\ ليرت التوالي .اما بالنسب اىل القاعدي هي بني ( )00.0-955ملغم\ ليرت
0-
0-
0-
و (-77
و ( )59.6-67.7ملغم\ ليرت 0-للماء السطحي على
و ( )025.3 -970.3ملغم\ ليرت
0-
لكل منا مياه االبار و
السطحي على التوالي وهذا القيم اكثر من قيم املسموح للمياه الشرب حسب املنظم الصح العاملي . وقيم تركيز الصوديوم هي بني ()5.3 -0.7ملغم\ ليرت
0-
و ( )6.6-00ملغم\ ليرت
0-
و قيم الرتكيز البوتاسيوم مابني ()7.0-0.5
ملغم\ و ( )0.0 -9.0ملغم\ ليرت 0-للماه االبار وامليه السطحي على التوالي و وهذه القيم حتت املستوى القياسي مسموح بها اسنادا على قيم القياسي العاملي .و قيم تركيز الكلور و النايرتيت هي بني ( )70-026ملغم\ ليرت
0-
و ( )2.6 -05.0ملغم\ ليرت
0-
للمياه االبار و املياه
السطحي علي التوالي و هذة القيم فى حدود القيم مسموح بها عامليا. واضهرت من النتائج ان قيم الرتكيز املعادن الثقيل و كذالك االيونات(الزنك ,الزرنيخ ,الكادميوم,احلديد,النيكل والرةاص) هي بني ( )0.009 -0.009ملغم\ ليرت ليرت
0-
0-
)0.060 -0.027( ,ملغم\ ليرت
)0.036-0.060( ,ملغم\ ليرت
0-
0-
)0.009 -0.035( ,ملغم\ ليرت
و ( )0.006 -0.006ملغم\ ليرت E
0-
0-
)0.000 -0.072( ,ملغم\
للمياه االبار و ( )0.000 -0.002ملغم\ ليرت
0-
)0.06 -0.05(,ملغم\ ليرت ليرت
0-
0-
)0.009 -0.0036( ,ملغم\ ليرت
و ( )0.090-0.099ملغم\ ليرت
0-
0-
)0.06 -0.007( ,ملغم\ ليرت
0-
)0.05 -0.055( ,ملغم\
للمياه السطحي على التوالي.قيم املعادن هو من ضمن قيم املسموح عامليا ماعدى قيم
الزرنيخ و الرةاص للماء االبار واملاء السطحي . اما بالنسب اىل تركيز الكربيت و النيرتوجني يف الرتب بلغت بني ( )%0.009 -0.030و ( )%3.2 -5.2و نسب الرتكيز الصوديوم واملغنسيوم و البوتاسيوم والكالسيوم للنماذج الرتب بلغت بني ( )9755 -3006ملغم\كغم )03395-00220(, 0-ملغم\كغم, 0- ()03023-06036ملغم\كغم 0-و ( )59502 -76550ملغم\كغم0-على تواىل .ولكن نسب املادة العضوي تراوحت ما بني (- 09.0 )00.3ملغم\كغم .وكذالك تركيزاملعادن الثقيل للنماذج الرتب كانت كما لتاىل (الزينك ,الزرنيخ ,الكادميوم ,الرةاص ,النيكل, الكروم ,املنغنيز و االلنحاس) كانت ما بني ( )996.03 -006.35ملغم\ كغم)05.96 -02.39( ,0-ملغم\ كغم)9.307-6.09( , 0- ملغم\ كغم )75.7 -023.05( ,0-ملغم\كغم )060.50 -029.95( , 0-ملغم\كغم )059.995 -073.0( , 0-ملغم\كغم 0-و (-000 )207ملغم\كغم. 0-و اظهرت هذه النتائج بان تراكز املعادن اكثر من القيم املسموح بها اسنادا على القيم التابع لصالحتاد االوروبي ما عدى قيم الرةاص والزرنيخ .ومن جه اخرى معدل قيم الرتاكيز املرتاكم لصاليونات الثقيل مناذج فى القمح (الزينك ,الزرنيخ, الكادميوم ,الرةاص ,الكروم ,النيكل) كانت ( ) 006ملغم\كغم )0.0303( ,ملغم\كغم )0.9( ,0-ملغم\كغم )9.0( ,0-ملغم\كغم,0- ( )0.060ملغم\كغم 0-و ( )0.096ملغم\كغم0-على تواىل مجيع االيونات هو خارج ضمن قيم املسموح بها اسنادا على املنظم الصح العاملي و املنظم الغذاء العاملى و قيم بريطاني ما عدى قيم الزينك و الكروم . وقد كان معدل ال ) (WQIللمياه اجلوفي و السطحي 90.23و 102.5على التواىل,و لذالك ميكن تصنيف هذه املياه اجلوفي كمياه جيد للشرب و املياه السطحي كمياه غري جيد للشرب حبسب تصنيف نوعي املياه اعتمادا على (. )WQIو كان قيم ال ( ) HIاملركب اقل من 0لكل انواع املعادن الثقيل فى مجيع النماذج املاخوذة من املياه اجلوفي و السطحي داال على خصالء املاء من املخاطر الصحي لصالستهصالك البشرى فى املنطق .و يستنتج بان كل من املياه اجلوفي و السطحي مازال ةاحلا للشرب .
F
حلومة إقليه كوردستان وزارة التعليه العالي والبحث العلني جامعة السلينانية– كلية العلوم
دراسة بيئية حول مناطق رمي النفايات الصلبة يف مدينة حلبجة– اقليه كردستان العراق رصبنت مقدمت انى مجهش فبكهتى انعهىو و انتربيت انعهميت صكىل انعهىو فى جبمعت انضهيمبنيت كجزء من متطهببث نيم شهبدة مبجضتير عهىو في عهىو انحيبة -انبيئت وانتهىث من قبل
ساالر حسني كريه (بكالوريوس فى علوم احلياة /جامعة صالح الدين )4002/ (دبلوم عالي فى علوم احلياة /جامعة صالح الدين ) 4000/
بأشراف
د .شيركى عهي محمد مدرس سةرماوةز ( 4102كوردى)
صفر ( 0216هجري)
تشرين الثاني ( 4002ميالدى)
List of content
CHAPTER ONE
INTRODUCTION
CHAPTER TWO
LITERATURE REVIEW
CHAPTER THREE
DESCRIPTION OF THE Study AREA
CHAPTER FOUR
MATERIALS AND METHODS
CHAPTER FIVE
RESULTS
CHAPTER SIX
DISCUSSION
CONCLUSION & RECOMMENDATION
references
