Title of Thesis

Application Of Isotope & Hydrochemical Techniques To Address Marine Coastal Pollution Along Karachi Coast-Pakistan

Author(s)

AZHAR MASHIAT ULLAH

Abstract
In this study, stable isotopes of carbon (δ13C), sulfur (δ34S), oxygen (δ18O), hydrogen (δ2H), nitrogen (δ15N) and radioactive isotope of hydrogen (tritium) have been applied in combination with conventional techniques (physiochemical and biological) to investigate Karachi Coastal water pollution due to Layari and Malir rivers, which mainly carry Karachi Metropolitan domestic and industrial wastewater, and to determine the effect of seawater on the aquifer system of the area.
Physico-chemical (pH, electrical conductivity and turbidity), biological (fecal coliform), heavy metal and stable isotope (carbon and sulfur) characteristics of Layari and Malir rivers water, Karachi coastal waters and sea sediments showed that Karachi Metropolitan domestic sewage and industrial effluents were the main source of coastal water pollution, and coastal water of Manora Channel was heavily polluted as compared to water of southeast coastal area of Karachi. However, the northwest coastal water was marginally polluted. Turbidity and fecal coliform population levels in seawater of Manora Channel and some locations along southeast coast (Ghizri area and Ibrahim Haideri) were found above the WHO recommended threshold limits set for seawater bathing.
Heavy metal contents of Manora Channel and southeast coastal waters were higher than the Swedish guidelines for the quality of seawater. In contrary, heavy metal concentrations in coastal sediments were found to be significantly higher than that of seawater. Mn and Ni contents in sediments of entire coast (Manora Channel, southeast and northwest coast) were above USEPA guidelines except at Buleji site, whereas Cr, Zn and Cu levels only in Manora Channel sediments were higher than USEPA guidelines. The higher heavy metal contents of Manora Channel water and sediments can be attributed to an influx of a major portion of untreated industrial and/or domestic wastewater.
Layari and Malir rivers water was observed to be depleted in δ13C(TDIC) and δ34S which showed heavy influx of sewage into these rivers. Manora Channel water was also depleted in δ13CTDIC and δ34S during low tide environment showing a large scale domestic wastewater mixing with seawater. Southeast coastal water was found to be slightly enriched in δ13C(TDIC) and δ34S and exhibited mixing of relatively small quantity of sewage with the seawater as compared to Manora channel. δ13C(TDIC) and δ34S contents of northwest coastal water were close to the values meant for normal seawater.
δ13C and δ15N contents of Karachi coastal seaweed ranged from -31.1 to -4.9 ‰ PDB and 6.1 to 17.8 ‰ Air, respectively. Average δ15N values (10.2 ‰ Air) of Ulva spp. collected from non polluted northwest coast was higher as compared to average δ15N contents (8.0 ‰ Air) of Ulva from Manora Channel suggesting that nitrogen isotopic ratios of Ulva spp. could be a good indicator of sewage pollution.
The results of a two component isotope mass balance equation using δ13C and δ34S values for Layari and Malir rivers and coastal water indicated that tide conditions and distance of sampling site from the pollution source were the main factors to control transport and dissemination of Layari river pollution into Manora Channel. High tide environment slowed down the Layari river water mixing with seawater coupled with a gradual decrease in pollution levels from Layari river out fall zone to Manora Lighthouse.
Physico-chemical characteristics of groundwater showed that shallow aquifer system was not generally affected by seawater intrusion. Deep groundwater was observed to be moderately (chloride contents 1000- 2000 ppm) to highly saline (chloride contents > 2000 ppm). However, shallow and deep well located in vicinity of the Malir and Layari rivers showed fecal coliform contamination which rendered their water unfit for drinking.
An anion based piper diagram showed predomination of chloride and bicarbonate ions relative to sulfate (SO4-2) ions in coastal groundwater. It was inferred from Piper diagram that shallow aquifer system was predominantly replenished by freshwater (mainly Layari and Malir rivers basin), while salinity of deep aquifer owes to the seawater intrusion or entrapped salinity. The δ18O composition of groundwater and δ2H vs. δ18O relationship for groundwater of coastal aquifer also indicated that shallow aquifer system was predominantly recharged through fresh water sources. Salinity of deep aquifer seemed to originate from seawater intrusion and/or from entrapped salinity. These finding were strongly endorsed by anion and stable isotope interpretations such as Cl-concentration vs δ18O, Cl-/HCO3 -1 ratio vs δ18O values and SO4-2 contents against SO4-2/Cl- ratio of shallow and deep aquifers.
The present study has demonstrated that stable isotopes (δ13C, δ15N, δ34S, δ2H and δ18O) can be effectively used to monitor the marine pollution and to investigate origin of salinity in the coastal aquifer. This study may also provide a precise and accurate isotopic database for researchers interested in seawater pollution and its effect on benthic life.

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1.1 Photonic band gap materials

1.2 Coastal Areas of Pakistan
1.3 Description of Pollution Sources of Karachi Coast
1.4 Environmental Effects of Karachi Coast Pollution
1.5 Introduction to Isotope Techniques
1.6 Objectives of the Study
1.7 Layout of Dissertation

2.1 Stable Isotope Applications in Aquatic Pollution Monitoring

2.2 Application of Stable Isotopes in Marine Sediments
2.3 Previous Work on Coastal Water Pollution in Pakistan

3.1 Location of Sampling Sites

3.2 Sample Collection and Preservation
3.3 Physico-chemical Analysis
3.4 Coliform Analysis
3.5 Major Ion Analysis

3.6 Metal Analysis

3.7 Tritium Analysis
3.8 Stable Isotope Analysis

3.9 Determination of Polluted Water Mixing with Coastal Water

4.1 Physico-chemical and Biological Characteristics of Polluted Rivers and Coastal Waters

4.2 Chemical Characteristics of Coastal Water and Sediments

4.3 Stable Isotope Characteristic of Karachi Coastal Water, Sediments and Biota

4.4 Tritium Analysis

5.1 Computation of Polluted River Water Mixing into Karachi Coastal Water Using δ13C (TDIC)

5.2 Computation of Polluted River Water Mixing into Karachi Coastal Water Using δ34S Values
5.3 A Comparison of Mixing Computed Through δ13C and δ34S Values
5.4 Application of δ18O to Determine the Freshwater – Marine Water Mixing

6.1 Water Supply Sources of Karachi Metropolitan

6.2 Groundwater Recharge and Origin of Salinity
6.3 Application of δ13C to Predict Seawater Intrusion

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