1. Dr. Prashant P. Bhave
Sourabh M. Kulkarni
Water Quality In Mumbai: Chlorinated
Compounds In Potable Water
18 November 2013, AWWA University Forum, Juhu,
Maharashtra, India

2. INTRODUCTION

3. INTRODUCTION
 Safe Drinking water : Building block for sustainability
 More than 5 million people die each yearly due to diseases caused by unsafe
drinking water (WHO & Johannesburg Summit 2002)
 California think - 76 million children could die worldwide from water-borne
diseases by 2020 if adequate safeguards are not taken
 Delhi water supply- Carcinogenic substances in potable water five times higher
than WHO standards.
 Disinfection - Health point and to control the spread of diseases
 Chlorine- popular disinfectant (Good or Bad?) & Disinfection by- products (DBP’s)

4. OBJECTIVE
• To determine the concentration of selected parameters of chlorinated
compounds in drinking water with the help of spectrophotometer
• Free chlorine, Total chlorine, Monochloramine & Chlorine dioxide
• Comparing the obtained results with the standards given by Govt. of India,
WHO & USEPA.

5. Chlorine water reactions
Free available chlorine-
 Cl2 + H2O HOCl + H+ + Cl-
 HOCl H+ + OCl- (Hypochlorite ions)
Free available chlorine = Hypochlorous acid and Hypochlorite ions
Combined available chlorine
 Cl2 + H2O HOCl + HCl
 NH3 + HOCl NH2Cl + H2O (Monochloramine)
 NH2CL + HOCl NHCl2 + H2O (Dichloramine)
 NHCl2 + HOCl NCl3 + H2O (Trichloramine)
Source: CPHEEO Manual, 1999 & B K Bhole 2000
LITERATURE REVIEW

6. MATERIALS & METHODOLOGY

7. Equipment's & Materials
 (HACH) DR 2400 spectrophotometer and distilled water
 Chlorine demand free glassware.
 Pipettes for 0.1ml, 1ml and 10 ml capacity and conical flasks.
 Reagent bottles
 Analytical balance GF series GF 300 & Vensar make pH meter.
 Standard solutions

8. Chemicals or Raw Materials
Parameters Chemicals
Free Chlorine
Total Chlorine
Monochloramine
Chlorine Dioxide
Anhydrous sodium phosphate dibasic
Anhydrous pottassium phosphate monobasic
Disodium EDTA
Mercuric chloride
Anhydrous diethyl-p-phenylenediamine sulphate
Sulphuric acid 1N.
Std.ferrous ammonium sulphate powder (FAS)
Pottassium iodide crystals
Sodium arsenite powder
Thioacetamide crystals
Bariumdiphenylaminesulfonate powder
Phosphoric acid
Glycine powder
Sodium bicarbonate
Sulfuric acid solution
Source: Standard methods, DPD Method, APHA

9. DPD (N, N-diethyl-p-phenylenediamine) method
• Given by AWWA, APHA & 4500 Cl (G)
• Chlorine (hypochlorite ion, hypochlorous acid) and chloramines
stoichiometrically liberate iodine from potassium iodide at pH 6.2 to 6.5
• The liberated iodine reacts with N, N-diethyl-p phenylenediamine (DPD) to
produce a pink or red colored solution.
• Wavelength range 515 nm.
• Parameters Can be tested- Free, Combine & Total Chlorine.
Source: Standard methods, 4500 Cl , (G) and DPD Method, APHA, AWWA

10. Calibration of Spectrophotometer
 By the use of potassium permanganate solution as equivalent to Chlorine
 Standards are made by serial diluting (0.891 gm. to 1000 ml deionized water
[1000 mg /l as cl2])
 The color is produced by adding Buffer & DPD indicator
 Standards from 0.05 - 2 mg/l
-0.200
0.000
0.200
0.400
0.600
0.800
1.000
1.200
1.400
0.0 0.5 1.0 1.5 2.0 2.5
Absorbance
Concentration (mg/l)
Concentration Vs. Absorbance
Source: Standard methods, 4500 Cl (G), DPD Method, Calibration of Spectrophotometer, APHA, AWWA

11. Flow sheet for determination of free chlorine by spectrophoometer
0.5 ml phosphate buffer to
10 ml cuvette.
0.5 ml N, N Diethyl-p-
phynelenediamine
indicator cuvette.
10 ml water sample to the
cuvette and mix.
10 ml water sample to the
cuvette as a blank with no
addition of reagents.
Development of Colour

12. Flow sheet for determination of Total chlorine by spectrophotometer
Add 0.5 ml phosphate buffer to 10 ml cuvette to adjust the pH
to 6.2 -6.5
Add 0.5 ml N, N Diethyl-p-phynelenediamine [DPD] indicator
to the spectrophotometer cuvette.
Add 0.1 gm. Potassium iodide or KI crystals to the cuvette.
Place10 ml water sample to the cuvette. Mix well & Wait for 2
min.
Fill another 10 ml sample as a blank with no addition of
reagents.

13. Add 0.5 ml phosphate buffer to 10 ml cuvette to adjust the
pH to 6.2 -6.5
Add 0.5 ml N, N Diethyl-p-phynelenediamine [DPD]
indicator to the spectrophotometer cuvette.
Place10 ml water sample to the cuvette. Mix well & Wait
for 2 min. Fill another 10 ml sample as a blank with no
addition of reagents
Read the reading for blank as 0.00mg/l. Place the prepared
sample in the spectrophotometer and read concentration of
free chlorine
Continue by adding the 0.1 mg Potassium Iodide or KI
crystal. Read the reading for blank as 0.00mg/l and read
the concentration of Monochloramine
Flow sheet for determination of Monochloramine by spectrophotometer

14. DPD (N, N-diethyl-p-phenylenediamine) method for
Chlorine dioxide
• Given by AWWA, APHA & 4500 ClO2 (D)
• Chlorine dioxide reacts with DPD (N, N-diethyl-p-phenylenediamine) to
the extent of one-fifth of its total available chlorine content corresponding
to reduction of chlorine dioxide to chlorite to form a pink colour.
• The colour intensity is proportional to the ClO2 in the sample.
• Chlorine interference is eliminated by adding glycine, which converts free
chlorine to chloroaminoacetic acid, but has no effect on chlorine dioxide at
the test pH.
• Wavelength range 515 nm
Source: Standard methods, 4500 ClO2 (D), DPD Method , APHA, AWWA

15. Flow sheet for determination of Chlorine dioxide by spectrophotometer
Add 10 ml water sample to the cuvette and
add 0.2ml glycine then mix.
Add 0.5 ml phosphate buffer and DPD
indicator to another the cuvette and mix well.
Add glycine treated sample to the buffer/
indicator cuvette and mix well. Wait for 30
sec for proper mixing and colour
development
Fill another cuvette with the 10 ml sample as
a blank with no addition of reagents. &
Read blank sample.

16. Sampling of Potable Water
 Random Collection
 Area under Greater Mumbai Municipal Corporation
 Standard sampling procedure [CPHEEO, 1999]
 Brown amber 350 ml glass sampling bottles
3 samples from each station
 Sample no.1- Residential areas
 Sample no.2 - Commercial areas
 Sample no 3 - Public places (Railway stations)

17. RESULTS AND DISCUSSION
Sampling location Sample No. 1 Sample No. 2 Sample No.3
CST 0.05 0.05 0.05
Masjid Bunder 0.09 0.10 0.07
Sandhrust Road
0.11 0.11 0.11
Byculla 0.11 0.11 0.12
Curry road 0.10 0.10 0.10
Matunga 0.13 0.13 0.13
Sion 0.15 0.15 0.16
Vidyavihar 0.15 0.16 0.16
Ghatkopar 0.16 0.17 0.17
Kanjurmarg 0.18 0.18 0.20
Bhandup 0.20 0.21 0.21
Nahur 0.19 0.19 0.21
Mulund 0.20 0.19 0.19
Charchgate 0.07 0.08 0.07
Marine lines 0.08 0.08 0.08
Charni road 0.08 0.10 0.08
Grant road 0.09 0.10 0.10
FREE CHLORINE (mg/l)

18. • The water is supplied to the Mumbai is from the Bhandup water treatment
plant
• The capacity of Bhandup water treatment plant is about 1950 MLD
• The free chlorine concentration is go on continuously decreasing as the
water passes through water treatment plant to the distribution system
• The chlorine concentration is higher in the Bhandup, Mulund, Kanjurmarg
area and after it is go on decreasing up to CST Mumbai

19. TOTAL (FREE+COMBINE) CHLORINE
(mg/l)
Sampling location Sample No. 1 Sample No. 2 Sample No.3
CST 0.48 0.50 0.53
Masjid Bunder 0.45 0.45 0.44
Sandhrust road 0.51 0.51 0.53
Byculla 0.45 0.47 0.48
Curry road 0.67 0.68 0.68
Matunga 0.44 0.44 0.43
Sion 0.48 0.47 0.47
Vidyavihar 0.48 0.53 0.56
Ghatkopar 0.55 0.42 0.44
Kanjurmarg 0.45 0.51 0.45
Bhandup 0.40 0.42 0.42
Nahur 0.44 0.45 0.44
Mulund 0.42 0.43 0.51
Charchgate 0.33 0.32 0.36
Marine lines 0.35 0.35 0.36
Charni road 0.38 0.39 0.43
Grant road 0.44 0.50 0.43

20. Sampling location Sample No.1 Sample No. 2 Sample No. 3
CST 0.10 0.11 0.11
Masjid Bunder 0.08 0.08 0.09
Sandhrust road 0.09 0.09 0.10
Byculla 0.07 0.09 0.08
Curry road 0.12 0.12 0.13
Matunga 0.07 0.06 0.08
Sion 0.07 0.09 0.10
Vidyavihar 0.11 0.10 0.11
Ghatkopar 0.07 0.09 0.08
Kanjurmarg 0.03 0.06 0.04
Bhandup 0.02 0.02 0.03
Nahur 0.03 0.03 0.03
Mulund 0.02 0.03 0.08
Charchgate 0.04 0.03 0.04
Marine lines 0.04 0.04 0.04
Charni road 0.02 0.03 0.05
Grant road 0.07 0.08 0.07
MONOCHLORAMINE (mg/l)

21. • The Bhandup water treatment plant(WTP) is using chlorine for disinfection
• The water supply pipelines in Mumbai are very old age and there are
leakages in the water supply pipelines and are increasing day by day
• There are chances of leakages in the water distribution system which
causes the contamination of organic matter through it & chances of
ammonia formation are there
• Hence chances of formation of Monochloramines in the water cannot be
ignored.

22. CHLORINE DIOXIDE
Sampling location Sample No.1 Sample No. 2 Sample No.3
CST 0.04 0.05 0.04
Masjid Bunder 0.06 0.05 0.06
Sandhrust road 0.03 0.04 0.06
Byculla 0.05 0.05 0.06
Curry road 0.03 0.04 0.06
Matunga 0.04 0.05 0.05
Sion 0.06 0.05 0.06
Vidyavihar 0.06 0.05 0.04
Ghatkopar 0.04 0.06 0.03
Kanjurmarg 0.06 0.03 0.06
Bhandup 0.06 0.06 0.06
Nahur 0.03 0.06 0.04
Mulund 0.03 0.06 0.06
Charchgate 0.04 0.06 0.04
Marine lines 0.06 0.03 0.05
Charni road 0.06 0.06 0.03
Grant road 0.04 0.04 0.04

23. VALIDATION
 Performance comparison
Parameter Concentration as per
HACH reagents (mg/l)
Concentration as per
Prepared reagents (mg/l)
Free Chlorine 0.10 0.16
Total Chlorine 0.40 0.47
Monochloramine 0.02 0.09
Chlorine Dioixide 0.01 0.06
 Cost comparison for prepared and HACH reagents
(Cost of analysis per sample)
Parameter HACH Reagents (Rs.) Prepared reagents (Rs.)
Free Chlorine 21/- 1.20/-
Total Chlorine 21/- 1.30/-
Monochloramine 104/- 1.30/-
Chlorine Dioixide 35/- 1.50/-

24. • Difference - due to the presence of interfering agent
• The prepared reagents- obtaining a rough idea about the presence of
parameters
• Reasonable accuracy of the results with the great saving in cost
• Periodic calibration of the prepared reagents is important for accuracy of
result
 laboratory results are acceptable

25. CONCLUSION
 Chlorine compounds or disinfection by-products levels less than the
Central Public Health and Environmental Engineering Organisation
(CPHEEO), World health organisation (WHO) and US Environmental
protection agency (USEPA) standards.
 Quality of potable water from central suburbs are comparatively better than
western suburbs.
 The amount of free chlorine reduces as the distance from Bhandup water
treatment plant increases.
 Laboratory chemicals as given by the standard methods are fairly accurate.
 The cost of sample analysis for prepared reagents is much lower.

26. REFERENCES
 The water we drink, an international comparison on drinking water of drinking water quality and
standards, David Suzuki foundation, Nov 2006.
 Y.P Gupta, India's cities: Challenge for survival, The Brunei times Sunday August 5, 2007 and
Y.P.Gupta, Poor water quality-a serious threat, Deccan Halard 2005.
 Arnaud Florentin, Alexis Hautemanière, Philippe Hartemann,Health effects of disinfection by-
products in chlorinated swimming pools, International Journal of Hygiene and Environmental
Health, vol. 214, 461-469, 2011.
 WHO, disinfectants and disinfectant by-products, Environmental health criteria 216, Geneva, 2000.
 Rosalam HJ. Sarbatly and DudukuKrishnaiah, Free chlorine residual content within the drinking
water distribution system, International Journal of Physical Sciences Vol. 2 (8), pp. 196-201, 2007.
 Huang Junli, Wang Li, RenNanqi , Ma Fang and Juli, Disinfection effect of chlorine dioxide on
bacteria in water, Journal of Water Resource, vol. 31,607-613, 1996.
 CPHEEO, Manual on water supply and treatment, Ministry of urban development, New Delhi , May
1999
 A.G.Bhole, design of water treatment plants, Indian water works association, Nagpur.
• A.G.Bhole, design of water treatment plants, Indian water works association, Nagpur.
• White, G.C., Handbook of Chlorination, Van Nostran Reinhold, New York, 1972.
• Lokeshkumar, Chlorine demand- A pollution load test, Journal of Indian water works association,
vol.44, 20-24, Oct- Dec 2012.
• Standard methods for the examination of water and wastewater, American Public Health
Association,edition 19th 1995.

27. CONTINUE….
• DR/2400, Portable Spectrophotometer instrument manual, Hach Company, USA, 2004.
• Karin carlsson, ludvigmoberg, bokarlberg, the miniaturisation of the standard method based on
the n,n'-diethyl p-phenylenediamine (dpd) reagent for the determination of free or combined
chlorine, Journal of Wat. Res. Vol. 33, 375-380, 1999.
• LudvigMoberg, Bo Karlberg, An improved N,N-diethyl-pphenylenediamine (DPD) method for the
determination of free chlorine based on multiple wavelength detection, Jurnal of
AnalyticaChimicaActa , Vol. 407, 127-133, 1999.
• Hach,DR 2400 spectrophotometer procedure manual, method no. 8021, USA, 2004.
• Hach,DR 2400 spectrophotometer procedure manual, method no. 8167, USA, 2004.
• Hach,DR 2400 spectrophotometer procedure manual, method no.10126, USA, 2004.
• Hach,DR 2400 spectrophotometer procedure manual, method no.10171, USA, 2004.
• Reetika Subramanian,60% rise in complaints of leaks in water pipelines, Kurla worst-hit, Hindustan
times,Mumbai, 22 April 2013.
• Sandipashar, your tap water is not safe for consumption, dna, Mumbai, 16 May 2009.
• WHO, Guidelines for drinking water quality, fourth edition 2011.
• USEPA, National Primary Drinking Water Regulations: Disinfectants and Disinfection By products
rules and regulations, vol. 63, 1998.

28. Standard Potassium Permanganate Solution (Equivalent to
Chlorine) Concentrations
B 0.2
mg/l
0.4
mg/l
0.8
mg/l

29. THANK YOU