Pollutants of Emerging Concern

in Asian Megacities such as Karachi HEINRICH HÜHNERFUSS1*, MARKUS SCHEURELL1, RAZA M. SHAH2

1Institute of Organic Chemistry, University of Hamburg, Martin-Luther-King-Pl. 6,

20146 Hamburg, Germany 2HEJ Research Institute of Chemistry, University of Karachi, Karachi, Pakistan

1. Concept of the Study

2. Experimental

3. Results

4. Conclusion

Karachi: The helpless mother of a two-year-old boy despairingly watches her son loose his grip on life. There is nothing the doctors can do to lessen her grief. As the hospital staff turn their focus on the next emergency, the death of the two-year-old becomes just another number added to

the death toll due to the water contamination crisis in Landhi.

Karachi: Landhi town, a large industrial town in the eastern part of Karachi: dramatic poisoning of about 200 children in Sept. 2005 due to drinking water contamination

September 29, 2005 Thursday Sha'aban 24, 1426

1. Concept of our Study

Final goal

Analysis of potential Water Resources for clean Drinking Water in

Megacities in third world countries

Based on these results development of strategies for cleaning natural water

resources

In this presentation I will confine myself to the outcome of the analytical

part of this study carried out in Karachi and in Sindh/Belutschistan, the

southern counties of Pakistan

A.) Sampling Area:

Karachi

Sindh

Baluchistan

A.) Sampling area and Strategy

Map of Karachi showing the rivers and the draining system, sampling locations

are marked (●)

1

20

16

15

21 23

24

28

41

3

2

13

14

22

17

18,19

40

44

1

20

16

15

21 23

24

28

41

1

20

16

15

21 23

24

28

41

3

2

13

14

22

17

18,19

40

44

Sample 1: Malir River

Sample 2: Tube Water Clifton

Sample 3 in the mangrove

lagoon, part of Karachi harbor

Samples 4, 5, 6 and 8 from an

open drainage canal system

(Korangi drain)

The analyses included different potential water resources as follows:

Landhi Pollution Area Malir River Korangi Drain Canals

Orangi Awami Tank Tube in a Factory Indus River at Kotri Barrage

Water Extracts

Fractionation

Chemical Analysis

Biotest directed Analysis

B.) Expectation at the start of the study:

Dominating impact of Halogenated Pollutants such as pesticides of the first

generations

But, now the surprise ……..

Results

The by far dominating classes of compounds were Pharmaceutical Compounds

and Industrial Chemicals

As an example this will be illustrated for

Dichlofenac and its Metabolites

Concentrations of Diclofenac and Metabolites

Compound

Sample/concentrations in [µg/L])

1 2 3 4 5 6 7 8 9

diclofenac 5.3 2.8 0.1 10 1.7 1.1 0.8 2.5 1.2

Metabolit 1

Metabolit 2

Metabolit 3

Metabolit 4

Metabolit 5

? ? ? ? ? ? ?

?

? ?

? ? ? ? ? ? ? ?

? ? ? ? ? ? ? ? ?

? ? ? ? ? ? ? ?

? ? ? ? ? ? ? ? ?

Fate of pollutants in the Environment

?

O

OH

Synthesis of Ibuprofen-OH I

Br

O

OH

O

OH

O

O

OH

O

O

O H

H

O

O

OH

H

NBS LiBr

M-CPBA K O-tert-Bu

H2

Pd/C

Ibuprofen II

Ibuprofen-OH I

III

IV V

VI

Compound Sample/concentrations in [µg/L])

1 2 3 4 5 6 7 8 9

diclofenac 5.3 2.8 0.1 10 1.7 1.1 0.8 2.5 1.2

8-chlorocarbazole-1-yl-

ethanoic acid

0.3 n.d. n.d. 0.4 n.d. 0.04 0.2 0.07 0.05

3´-hydroxydiclofenac 0.2 0.3 n.d. 0.3 0.2 0.2 0.1 0.2 0.08

4´-hydroxydiclofenac 0.8 1.7 n.d. 1.8 0.6 1.7 0.5 0.6 0.4

5-hydroxydiclofenac 0.07 0.3 n.d. n.d. n.d. 0.1 0.01 n.d. n.d.

1-(2,6-dichlorophenyl)

indolin-2-one

0.09 n.d. n.d. 0.2 n.d. 0.2 n.d. n.d. 0.2

Concentrations of Diclofenac and its Metabolites

NH

Cl O

O

NH

Cl O

O

Mass spectra of 8-chlorocarbazole-1-yl-ethanoic acid as ester derivative; above: external standard; below: sample 1 extract.

Sample 1

Standard

Dichlofenac Metabolites Example 1

NH

O

Cl

Cl

OO

O

O

NH

O

Cl

Cl

OO

O

O

Mass spectra of 4´-hydroxyl diclofenac as MCM derivative; above external standard; below: sample 15 extract. 3´-hydroxy diclofenac exhibits an identical mass spectrum

Standard

Sample 15

Dichlofenac Metabolites Example 1

NH

OH

O

Cl Cl

N

O

Cl

Cl

NH

OH

O

Cl

NH

OH

O

Cl Cl

R´´

R´´´

R´

- H2O

photolysis

artefact

- HCl

photolysis

R´ : OH, R´´,R´´´: H: 5-Hydroxydiclofenac

R´´ : OH, R´,R´´´ : H: 4´-HydroxydiclofenacR´´´ : OH, R´,R´´ : H: 3´-Hydroxydiclofenac

1-(2,6-dichloro-phenyl)

indoline-2-one

8-Chlorocarbazole-

1-ethanoic acid

hydroxylation

pathway

Transformation Products of Diclofenac in the Aquatic Environment

First Take Home Message:

Without a synthesis of not commercially available standards – no verification of the metabolites !

Second Take Home Message

Taking into account the high Concentrations,

Discrimination between Biotic and Abiotic

Transformation Processes is possible

applying Enantioselective Chromatography

(not presented in this talk)

Third Take Home Message:

Taking into account the high concentrations, toxicological measurements

allow applications of relatively easy risk assessments

such as the Luminescent Bacteria Test or several Bioassy Tests

(not presented in this talk)

Thank You !

Complete Sampling Area in Southern Pakistan

1-3

4,5

6

7

8 9

10

11

12

13,14

15

17-19

Kotri

Lanhdi

Hub dam

Kinjhar Lake Orangi

Clifton