Estimation of Some Heavy Metals in Water of Aski-Kalak/ Greater Zab River
Research Project
Submitted to the department of Fish Recourse and Aquatic Animals in partial fulfillment of the requirements for the degree of BSc.
By Chra Sabah Othman
Supervised by: Asst. Lec. Iman Sherzad Ali
April 2020 SUPERVISOR CERTIFICATE
This seminar has been written under my supervision and has been submitted for the award of degree of BSc. of Science in Fish Resource and Aquatic Animal\Fish Ecology with my approval as supervisor.
Signature: Supervisor: Asst. Lec. Iman Shirzad Ali
Date: /4/2021
I confirm that all requirements have been fulfilled.
Signature:
Name: Dr. Rebin Aswad Mirza
Head of Fish Resource and Aquatic Animal Department
Date: / 4 /2021
I Dedication
I dedicate to……
My lovely parents
My Brothers and Sisters
My friends who encourage and support me
Everyone helps me to do this work
Chra
II
ACKNOWLEDGMENTS
In the Name of Allah, I must acknowledge my limitless thanks to Allah, the Ever Thankful, for His helps and bless. I am totally sure that this work would have never become truth, without His guidance.
My deepest gratitude goes to my supervisor Iman Shirzad Ali, who’s worked hard with me from the beginning till the completion of the present research. A special thanks to Dr. Rebin Aswad Mirza the head of Fish Resource and Aquatic Animal Department for his continuous help during this study.
I also would like to express my wholehearted thanks to my family for their generous support they provided me throughout my entire life and particularly through the process of pursuing the BSc degree.
III ABSTRACT
Greater Zab River serves as a major source of drinking water, irrigation and fishing in Erbil, Kurdistan Region of Iraq. Heavy trace metals such as: copper, cadmium, lead, chromium and zinc were determined in water from Aski Kalak every two months from August 2015 until February 2016. In water, the heavy metals concentration was found to be in the order Zn > Cr > Cu, whereas, cadmium and lead not detected in studied water samples. All studied water samples during this investigation for Zn and Cr were above the desirable level for drinking, while in the safe side for fish life, while for Cr all studied water samples during this investigation were above the desirable quality and were in unsafe for drinking purposes and for fish life set by the WHO, CCME and unsafe for drinking purposes and for fish life.
IV CONTENTS List of Contents
Titles Pages Supervisor Certificate I Dedication II Acknowledgments III Abstract IV Contents V List of Contents V List of Figures V List of Tables VI List of Plate VI List of Abbreviations VI 1. Introduction 1 2. Materials and Methods 2-3 2.1. Description of Sampling Sites. 2 2.2. Water Sample Collection 3 3. Results and Discussion 4-6 3.1. Zinc (Zn+2) 4 3.2. Chromium (Cr) 5 3.3. Copper (Cu) 5 3.4. Lead (Pb+2) 6 3.5. Cadmium (Cd) 6 4. Conclusions and Recommendations 7 4. 1 Conclusions 7 4.2 Recommendations 7 References R8- 10
List of Figures
Figures Pages Figure 2.1: A- Map showing the lakes and river routes in Iraq. 2 Figure 2.2: B- Map of Greater Zab River with main branches. 2
V
List of Tables
Table Page Table (3.1): Monthly variation of heavy metals concentrations (µg.l-1) 6 at sampling site during the period of study
List of Plate
Plat2 Page Plate 1: Aski Kalak in Erbil Province 2
List of Abbreviations
Abbreviation Details APHA American Public Health Association CCME Canadian Council of Ministers of the Environment mg.l-1 Milligram Per Litter WHO World Health Organization
VI
Introduction
1. INTRODUCTION
River systems are being excessively contaminated with heavy metals released from domestic wastes, industrial effluents, and agricultural runoff (Adnano, 1986). According to Bauer and Velde (2014) metals are defined as the metallic chemical elements that have a relatively high density and are toxic or poisonous at low concentrations. They are at least five times denser than water, as such they are stable (meaning they cannot be metabolized by the body) and bio-accumulative. They are sometimes passed up the food chain to humans (Fergosson, 1990). A small number have an essential role in the metabolism of humans and animals in very trace amounts but their higher concentration may cause toxicity and health hazards (Sharma, 2015) .
There are basically three reservoirs of metals in the aquatic environment: water, sediment and biota (Jordan, 1981). Heavy metals from manmade pollution sources are continually released into aquatic systems, and they are a serious threat because of their toxicity, long persistence, bioaccumulation and bio-magnifications in the food chain (Eisler, 1988) .
Greater Zab River is the most important river in Kurdistan Region of Iraq that provides water supply for drinking, irrigation and fishery. In aquatic environments, industrial and domestic wastes are discharged without being treated. The pollution of the aquatic environment with heavy metals has become a worldwide problem during recent years, because they are indestructible and most of them have toxic effects on organisms (Sharma, 2006; Ramkumar, 2013). Thus, this study is carried out to determine levels of some toxic heavy metals (Cr, Cd, Pb, Zn and Cu) in Aski-Kalak water to determine the source of pollutants in Aski-Kalak/Greater Zab River .
1
Materials and Methods
2. MATERIALS AND METHODS
2.1. Description of Sampling Sites.
Aski Kalak is located on the main Geater Zab River at sub-district center behind sand quarries close to the old bridge with an elevation of 238.1 m.a.s.l. (Plate 1 and Figure 2.1). This site is located at south western part of the Khabat district and agriculture activities are dominant near this site. The water level is high in winter and low in dry season. Water samples was collected for the purpose of analysis.
Plate 1: Aski Kalak in Erbil Province
Figure 2.1: A- Map showing the lakes and river routes in Iraq. B- Map of Greater Zab River with main branches. (Nelson, 2003). 2
Materials and Methods
2.2. Water Sample Collection
For meeting the requirements of this work, water samples from Aski-Kalak were collected every two months from August 2015 to the end of March 2016. Surface water samples were analyzed every two months for heavy trace metal. Water samples were acidified adding concentrated HNO3 in acid pre washed polyethylene container and stored at 4 °C for trace metal determination purposes (APHA, 1998) and sent to the international laboratory (Austrian Laboratory Services) in Czech Republic for heavy trace metal analysis by ICP-OES (Inductively Coupled Plasma Optical Emission Spectroscopy) according to procedures US EPA 200.7, ISO 11885, CSN EN 12506, US EPA 6010, and SM 312
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Results and Discussion
3. RESULTS and DISCUSSION The heavy metal concentration at sampling site followed the order Zn > Cr > Cu, while Pb and Cd was not detectable.
3.1. Zinc (Zn+2)
In this study, higher mean values of zinc were recorded during February 2016 (27 µg.l- 1), while lower values were recorded during August 2015 (3.9 µg.l-1) . Increase in mean concentration of Zn during February 2016 may be ascribed to high rain and erosion during rainfall season in the study area which gives rise to flow of the water in the river. Due to the turbulence created by increase of flow, some sediments and heavy metals are displaced and carried away from the river bed as has been obtained by Shanbehzadeh et al. (2014) on Tembi River Chapter Five Results and Discussion 61 in Iran.
The average concentration of Zn was 13 µg.l-1, the maximum acceptable concentration of Zn in drinking water was 3 mg.l-1 as stated by WHO (2006) guidelines, while for fish was 30 µg.l-1(CCME, 2012) guidelines. Accordingly, all studied water samples during this investigation were above the desirable for drinking, while in the safe side for fish life.
Results of Zn in current study agreed with results of Balasim (2013) on Tigris River in Iraq, Tiwari and Dwivedi (2014) on Gomti River, India and Ivanović et al. (2016) on Danube River, Serbia. Furthermore, dissolved zinc in present study considered low if compared with the study of Al-Lami and Al-Jaberi (2002) in upper region of Tigris River, Iraq, Khdhir et al. (2011) on Greater Zab River in Iraq.
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Results and Discussion
3.2. Chromium (Cr)
Chromium concentrations in all studied sites are shown in Table (3.1). The highest chromium concentration 3.6 µg.l-1 was noted during October 2015 and February 2016, while the lowest value 1.4 µg.l-1 was recorded during August 2015 with an average mean 2.9 µg.l-1.
Higher levels of Cr in water samples during autumn may be attributed to the possible rainfall during autumn and may occur frequently; where pollutants washed down into the adjacent aquatic systems, moreover, same results obtained by Khallaf et al. (1994) who worked on a Nile drainage canal.
The maximum acceptable concentration of Cr in drinking water was 0.05 mg.l-1 as stated by WHO (2011) guidelines, while for fish life was 0.01 mg.l-1 (CCME, 2007). Accordingly, all studied water samples during this investigation were above the desirable quality and were in unsafe for drinking purposes and for fish life.
Results of present study were higher than those observed by Hassan et al. (2010) on Euphrate River in Iraq. Also, the results of Cr in current study were lowest than results of Salah et al. (2015) on Euphrate River in Iraq.
3.3. Copper (Cu)
Results of present study showed that highest value of Cu 3.6 µg.l-1 was measured during October 2015, whereas the lowest value 1.8 µg.l-1 was measured during December 2015 with an average mean of 2.8 µg.l-1 (Table 3.1). The lower mean values of Cu during December 2015 may be related to the dilution factor followed rainfall; similar results were obtained by Balasim et al. (2013) on Tigris River in Iraq.
On the other hand, the maximum acceptable concentration of copper in drinking water according to WHO (2011) was 2 mg.l-1, while for fish was 4 µg.l-1 according to CCME (2012). Accordingly, all studied water samples during this investigation were within
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Results and Discussion the desirable quality and were in the unsafe side for drinking purposes, while safe for fish life.
The results of present study agreed with results of Ivanović et al. (2016) on Danube River, Serbia, while the ecosystem of the two rivers is different and lower than results of Khdhir et al. (2011) on Greater Zab River in Iraq, Al-Alem et al. (2013) on Greater Zab River, Iraq.
3.4. Lead (Pb+2)
In the present study the concentrations of Pb in water samples at all sampling sites were found to be below detection limits. This is may be the result of adsorption of metals by suspended solids (Chapman, 1996). Generally, results of Pb in current study agreed with results of Fahad (2006) on the Al-Garaf River in Iraq and Ivanović et al. (2016) on Danube River in Serbia, which was not detected in their studies.
3.5. Cadmium (Cd)
In the present study the concentrations of Cd were low and not detected in all sites during the studying period. This may be due to adsorption of metals by suspended solids (Chapman, 1996). Results of Cd in present study agreed with results of Hussein et al. (2014) on the Al-Hilla River in Iraq and Ivanović et al. (2016) on Danube River in Serbia, which were not detected in their studies.
Table (3.1): Monthly variation of heavy metals concentrations (µg.l-1) at sampling site during the period of study Heavy 2015 2016 Mean SD Metals Aug. Oct. Dec. Feb. Zn+2 3.9 13.2 7.9 27 13 10.1 Cr 1.4 3.6 2.8 3.6 2.9 1 Cu+2 2.5 3.6 1.8 3.1 2.8 0.8 Pb+2 ND ND ND ND ND Cd ND ND ND ND ND Mean 2.6 6.8 4.1 11.2 6.2
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Conclusions and Recommendations
4. CONCLUSIONS and RECOMMENDATIONS
4.1 Conclusions
It was concluded from the present study that:
1) The trend of studied heavy metals concentrations were: Zn > Cr > Cu for water, while Pb and Cd was not detectable. 2) All studied water samples during this investigation for Zn and Cr were above the desirable level for drinking, while in the safe side for fish life, while for Cr all studied water samples during this investigation were above the desirable quality and were in unsafe for drinking purposes and for fish life set by the WHO, CCME and unsafe for drinking purposes and for fish life.
4.2 Recommendations It was recommended from the present study that:
1) The monthly study is the most effective than every two months study, where changes in heavy metals of water appear clearly through the month of the year. 2) Restriction of untreated domestic wastes, industrial and agricultural wastes from activities to discharges into the river and prevent throwing solid waste close to river. 3) Analyzing heavy metals in fish tissues, sediment and algae.
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References
REFERENCES
Adnano, D. C. (1986) Trace metals in the terrestrial environment. Springer-Verlag, New York. p. 24. Al-Alem, L. S., Khdhir, N. S. and Abdullah, S. M. A. (2013) Detection of Copper and Cadmium Concentrations in some Local Fishes from Greater Zab River, Iraq. J. Koya Univ. 26. p. 75-84. Al-Lami, A. A. and Al-Jaberi, H. H. (2002) Heavy metals in water, suspended particles and sediment of the upper-mid region of Tigris River, Iraq. Proceedings of Inter. Symposium on Env. Pol. Control and Waste Management 7-10 Jan. 2002, Tunis, p.97- 102.97. American Public Health Association (APHA) (1998) Standard methods for the examination of water and wastewater. 20th Edition, American Public Health Association, Washington, DC. p. 2671. Balasim, H. M. (2013) Assessment of some heavy metals pollution in water, sediments and Barbus xanthopterus (Heckel, 1843) in Tigris River at Baghdad city. M.Sc. Thesis, University of Baghdad, College of Science. p. 159. Bauer, A. and Velde, B. D. (2014) Geochemistry at the Earth’s Surface: Movement of Chemical Elements. Springer, Berlin. p. 315. Canadian Council of Ministers of The Environment (CCME) (2007) A Protocol for the Derivation of Water Quality Guidelines for the Protection of Aquatic Life. In: Canadian Environmental Quality Guidelines, 1999. Canadian Council of Ministers of the Environment. Winnipeg. Canadian Council of Ministries of The Environment (CCME) (2012) Scientific Criteria Document for the Development of the Canadian Water Quality Guidelines for the Protection of Aquatic Life. http://ceqg-rcqe.ccme.ca/.
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References
Chapman, D. (1996) Water Quality Assessments: A Guide to the Use of Biota, Sediments and Water Environmental monitoring. 2nd Edition, Chapman & Hall, London. p. 609. Eisler, R. (1988) Lead Hazards to Fish, Wildlife, and Invertebrates: A Synoptic Review. United States fish and wildlife service Biological report. p. 94. Fahad, K. (2006) Ecological survey for southern sector of Al-Geraf River, Southern Iraq. PhD. Thesis, College of Agricultural University of Basrah. p. 103. Fergosson, J. E. (1990) The Heavy Elements Chemistry, Environmental Impact and Health. Pergamon Press, Oxford. p. 621. Hassan, F., Saleh, M. and Salman, J. (2010) A study of physicochemical parameters and nine heavy metals in the Euphrates River, Iraq. E-J. Chem. 7 (3). p. 685-692. Hussein, F., Baqir, S. and Karam, F. (2014) Seasonal Variation in Heavy Metals Contamination in Surface Water of Shatt Al-Hilla River, Babylon, Iraq. Asian J. Chem. 26. p. 207- 210. Ivanović, J., Janjić, J., Baltić, M., Milanov, R., Bošković, M., Marković, R. V. and Glamočlija, N. (2016) Metal concentrations in water, sediment and three fish species from the Danube River, Serbia: a cause for environmental concern. Environ. Sci. Pollut. Res. DOI 10.1007/s11356-016-6875-y. Jordan, C. F. (1981) Tropical Ecology. Hutchinson Ross Publishing Company, London. p. 357. Khallaf, E. A., Galal, M. and Authman, M. (1994) A study of pesticides residues in Oreochromis niloticus (L.) muscles from a Nile drainage canal. J. Egypt. Ger. Soc. Zool. 15 (A). p. 491-508. Khdhir, N. S., AL-Alim, L. S. and Abdullah, S. M. A. (2011) Bioaccumulation of some heavy metals in the tissues of two fish species (Barbus luteus & Cyprinion macrostomum) in Greater Zab river-Iraq. J. Duhok Univ. Pure Eng. Sci. 14(1). p. 71- 77. R9
References
Ramkumar, M. (2013) On a Sustainable Future of the Earth's Natural Resources. Springer Science & Business Media, Berlin. p. 554. Salah, E. A., Al-Hiti, I. KH. and Alessawi, KH. A. (2015) Assessment of Heavy Metals Pollution in Euphrates River Water, Amiriyah Fallujah, Iraq. J. Environ. Earth Sci. 5 (15). p. 59-70. Shanbehzadeh, S., Dastjerdi, M. V., Hassanzadeh, A. and Kiyanizadeh, T. (2014) Heavy Metals in Water and Sediment: A Case Study of Tembi River. J. Environ. Public Health. p. 1-5. Sharma, B. K. (2006) Environmental Chemistry.10th ed. Goel publishing house, Meerut, Delhi. p. 1380. Sharma, S. K. (2015) Heavy Metals in Water Presence, Removal and Safety. Royal Society of Chemistry, London. p. 380. Tiwari, A. and Dwivedi, A. CH. (2014) Assessment of heavy metals bioaccumulation in alien fish species, Cyprinus carpio from the Gomti River, India. Eur. J. Exp. Biol. 4(6). p. 112-117. World Health Organization (WHO) (2006) Guidelines for Drinking–Water Quality. 3rd Edition. Recommendations, Geneva Switzerland. p. 515. World Health Organization (WHO) (2011) Guidelines for drinking water quality. 4th Ed. NML. Classification: WA. P. 675. 541.
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