OFF-FLAVOR ODOROUS COMPOUNDS IN WATER:

DETERMINATION, FORMATION AND CONTROL

Lifeng Zhang
Water Quality Office, PUB, Singapore, 608576

PUB-JWRC Symposium, 05 July, 2012

1

INTRODUCTION

Surface water supplies are more likely to be affected by substances causing
undesirable tastes and odors, the largest single class of consumer complaints
submitted to water utilities (Levallois, et al., 1999).

Objectionable taste and odor in tap water will compromise public confidence in
the water quality

INTRODUCTION

For drinking water, objectionable taste and odor in highly treated water is a serious
concern because it could undermine consumer confidence.

Water treatment plants utilize chemicals or adsorbents to control these problems.

The earthy-musty odors are especially troublesome because they are particularly
unpleasant and often encountered in water (Suffet et al, 1996).

Earthy-musty smell is associated with the presence of geosmin, MIB and
haloanisoles (Mallevialle et al., 1987; Jensen et al., 1994 and Bruchet et al., 1999).

Figure 1.
Taste and Odor
Wheel 2000 (Suffet
et al. 1999)

OFF-FLAVOR COMPOUNDS IN ODOR WHEEL --- (Burlingame et al. 2004)

Earthy/Musty/Moldy

Ammonia/fishy

Sulfide/cabbage/garlic

Rancid/putric

Solvent/hydrocarbon

Geosmin

ammonia

Dimethyltrissulfide

2-Hexenal

Thiophene

2-Methylisoborneol

Butyl amine

Dimethyldisulfide

2,4-Decadienal

1,2-Cyclohexanedione

2,3-Diethylpyrazine

N-Butyl amine

Dimethylsulfide

Amylmercaptan

Cresols

Trichloroanisole

Trimethyl amine

Carbon disulfide

Butanoic acid

Naphthalene

2-Ethyl-1-hexanol

Isopropylamine

Hydrogen sulfide

Butyraldehyde

Methylallyltrisulfide

Grassy/Woody

Pyridine

Diethyl sulfide

Decanoic acid

Methylmethacrylate

-Cyclocitral

Trimethylamine

Diallylsulfide

Dimethylamine

Benzene

Cis-3-Hexen-1-ol

Dimethylamine

Diphenylsulfide

Heptanal

Tetrachloroethylene

Cis-3-Hexenyl-1-ol acetate

Dibutylamine

Thiophene

Hexanoic acid

Trichloroethylene

Hexanal

Methylamine

Methyl mercaptan

Iso-valeric acid

Toluene

Furfural

Diisopropylamine

Allyl mercaptan

Methyl thiobutyrate

Cumene

1,2-Nonenal

Triethylamine

Phenyl mercaptan

Methylamine

M-Xylene

Fornaldehyde

Heptanal

Ethyk mercaptan

Phenylmercaptan

Styrene

Soapy/detergent

2,4-Decadienal

Crotyl mercaptan

Propyl butyrate

Indene

1-Dodecanal

2,4-Heptadienal

T-Butyl mercaptan

Pyridine

Heptane

Acetaldehyde

Hexylamine

Furfuryl mercaptan

Thiophenol

Octane

Ethyl Acetate

Medicinal/alcohol

Acrylonitrile

Trimethylamine

T-Butyl toluene

Isopropyl acetate

N-Butanol

Thiocresol

Valeric acid

Toluene

Isovaleraldehyde

p/m-Cresol

Oxidant/Chlorinous

Fecal/sewery

Methylisobutylketone

Isobutyraldehyde

Chlorophenols

Hypochlorous acid

Indole

P-Dichlorobenzene

D-Limonene

Bromophenols

Monochloramine

Skatole

Naphthalene

Hexanal

Cyclohexanol

Dichloroamine

Iso-Valeric acid

Cumene

Valeric acid

Anisole

1-Hexanol
phenol

1-Butanol

Iodoform

Pyridine

SOURCES OF OFF-FLAVOR COMPOUNDS

1) Algae, cyanobacteria and microorganism
e.g. geosmin, MIB

2) Chlorination
e.g. mono-, di-and tri-chlorophenols

ANALYTICAL METHODS
Sensory Method ------

Threshold Odor Numbers (TON)

the greatest dilution of sample with odor-free water yielding a definitely perceptible odor.
the temperatures of the samples to be tested should all be standardized, a water bath is to be used and 60o C
is an accepted value for analysis.
TON:

Threshold Odor Numbers Corresponding to Various Dilutions

USEPA Secondary Drinking Water Standards

Contaminant

Odor

Secondary
Standard
3 threshold odor
number

ANALYTICAL METHODS


Sensory Method ------ Flavor Profile Analysis (FPA)

FPA is a technique for identifying sample odou(s).

FPA Analysis Laboratory

FPA Analysis Work Sheet

FPA Analysis Results

ANALYTICAL METHODS
Instrumentation
GC-MS
Closed Loop Gas Stripping GC-MS
Thermo-desorption GC-MS
Stirring Bar GC-MS
P&T GC-MS

..

CHALLENGES IN ANALYTICAL METHODS TO OFF-FLAVOR COMPOUNDS

Name/ Abbreviation

Taste

Odor Threshold (ng/l)

2-Methylisoborneol (MIB)

Earthy

5-10

Geosmin (GSM)

Camphor

1-10

2,4,6-Trichloroanisole (2,4,6-TCA)

Musty

0.1-2

2,3,6-Trichloroanisole (2,3,6-TCA)

Musty

0.1-2

2,3,4-Trichloroanisole (2,3,4-TCA)

Musty

0.2-2

2,4,6-Tribromoanisole (2,4,6-TBA)

Musty

0.15-10

2-isopropyl-3-methoxypyrazine

Green, floral, decay

0.2-16

2-isobutyl-3-methoxypyrazine

Green pepper

1.0-16

-ionone

Violet, woody

2-bromophenol

medicinal

30

2,6-dibromophenol

Medicinal, hospital

0.5

10

ANALYSIS OF OFF-FLAVOR COMPOUNDS

11

ANALYSIS OF OFF-FLAVOR COMPOUNDS

Traditionally, the analysis of odourants and
measurement of odours are performed separately.
Olfactometry GC-MS enables
the identification and linking of odourant
compounds and human sensory perception.

Olfactometry GC-MS
12

Target Odorants in Reservoir Waters

R1
R8

R2

R3

R4

R5

R6

R7

DOMINANT Geosmin and 2-MIB detected

MINOR

IPMP and 26DBP occasionally detected

13

Target Odorants in Treated Water

A
G

DOMINANT

MINOR

Only 2-MIB occasionally

26DBP randomly detected due to chlorination

No other target compounds were detected above the odor
threshold in treated water.

14

Ratio [Conc/OTCmin]

Target Analytes in Reclaimed Water

26DBP
246TBA

2MIB

geosmin

246TCA

secondary effluent samples

Dominant

246TCA and geosmin

Minor

2MIB, 26DBP, 246TBA, IPMP, IBMP, -ionone, 234TCA

15

Anisole Formation in WWTP

raw sewage

2o effluent

raw sewage

2o effluent

product

precursor

Decrease of known precursor 2,4,6-trichlorophenol

was consistently observed along with formation of 2,4,6trichloroanisole.
16

Anisole Formation in WWTP

activated
sludge
MW: 197.45 + 6
RT: 16.709 min
Target ion: m/z 202, 204

MW: 212.45 + 6
RT: 16.303 min
Target ion: m/z 201, 203

17

Treatment of Off-flavor Compounds

3

Dil 0x
3
3

Dil 2x
3
3

Dil 4x
3
2

Dil 16x
2
1

Dil 64x
0
0

4
4

4
3

3
4

3
2

3
4

4
4

2
2

2
3

1
2

2
1

0
0

1
0

0
0

0
0

0
0

2
4
2
4
4
OZONATIO
3
2
3
3
3
2
2 N2
3
3
3
4
4

0
3

2
0

2
2

4
2

4
2

4
2

0
2

2
3

0
2

0
0

0
0

0
0

0
0

1
0

0
0

4
3

4
4

4
4

4
4

4
4

3
4

3
3

3
3

2
3

2
2

3
3

2
2

0
0

0
0

0
0

Inlet
3
2
4

3
2
3

4
3
4

4
4

3
2

4
4

3
1

3
0

4
0

3
2
0
3

2
2
2
0

3
3
2
2

4
4
2
1

3
2
0
4

3
4
0
3

2
0
4
3
4
2

4
4
4
4
4
3

3
3
4
4
4
2

3
4
3
2
2
4

2
0
4
4
3
2

2
0
3
2
3
4

Stripping
0
2
0
0
3
3

3
0
4
4
4
3
2
0
3
2
0
4
3
4
2

2
3
4
4
3
3
2
2
3
3
4
4
4
2

0
3
2
4
0
1
0
0
0
1
0
2
0
1

0
3
3
3
1
2
0
0
0
0
0
2
0
0

0
3
2
4
2
1
0
0
0
1
0
1
0
0

4
3
4
4
4
2
2
3
2
3
0
2
3
0
2

Maybe

Fluence 500
3
3
3
3
3
2
4
3
2
4
3
3
2
3
3
2
2
2
3
2
3
3
3
3
3
3
3
3
3
3
4
3
3
4
2
3
3
3
3
3
3
3
3
2
3

2
4
3
2
2
2
2
0
4
4
4
4
4
3

REVERSE OSMOSIS

UV
Fluence 0
3
3
2
2
4
3
3
4
2
4
2
3
2
3
2
2
0
2
4
3
4
3
4
4
4
4
4
4
3
2

0
4
4
3
3
2
0
3
2
0
4
3
4
2

Maybe Good

AERATION
3
0
4

UV peroxide

OZONATI
Inlet
Ozonated
ON
3
3
3
0
0
0

DILUTION

Feed
4
0
4
4
3
3
4
3
4
4
3
3
3
4
4

3
0
3
3
4
3
2
4
3
3
2
4
4
2
2

2
0
1
3
2
2
2
1
2
3
0
2
2
3
1

Permeate
3
0
3
0
1
0
3
3
3
1
2
1
1
3
2
0
2
3
3
3
2
3
2
2
3
1
1
2
0
0

Maybe

C*T 0

C*T 200

3
0
4
4
4
3
2
0
3
2
0
4
3
4
2

Inlet
3
2
4
3
2
2
2
2
0
4
4
4
4
4
3

2
3

Limited Limited
2

Fluence 2000
0
1
2

3
0
4
4

Inlet
3
2
4
3

3
2
3
4

3
3
2
0
3
2
0
4
3
4
2

2
2
2
2
0
4
4
4
4
4
3

4
3
3
2
2
3
3
4
4
4
2

Pre-O3 & BAC

0
0
0
0
0
0
1
0
0
2
1
2
0
0
0
0
0
0
2
1
0
0
1

0
0
0
1
0
0
0
0
1
0
3

0
0
0
1
0
0
0
0
1
0

Good Good
2

no-O3 & BAC

0
1
1
0
1
0
2
3
3
2
3
3
2
1
2
2
1
1
0
2
2
0
1
1
2
2
3
0
0
0
2
2
2
1
1
2
1
1
2
1
1
2
2
2
2

3
2
3
4
4
3
3
2
2
3
3
4
4
4
2

Maybe

CHLORAMINATION

C*T 1000

Fluence 500
2
2
2

BIOLOGICAL A.C.

CHLORINATION
Fluence 1000
4
2
3
3
3
3
3
4
3
2
1
4
2
4
3
2
4
2
2
4
3
2
2
2
2
0
3
2
2
0
3
3
4
2
0
2
3
3
3
1
0
2
3
1
2

Fluence 0
0
3

O3 & BAC

1
3
4
4
4
3
2
3
4
3
2
4
3
3
4

C*T 0
2
0
2
3
3
3
3
4
3
3
2
3
3
3
4
4
1
4
4

4
3
2
3
3
4
2
4
2
3
4

2
2
4
3
3
3
3
3
4
2
4
4
3
4
4

C*T 200
3
3
2
1
4
4
3
4
4
2
3
2
2
3
3
4
4
4
4

4
2
4
3
3
2
3
4
2
4
4

C*T 1000
1
2
3
3
2
3
3
3
3
3
4
4
2
2
2
2
2
2
3
3
4
3
3

3
2
3
2
2
3
3
4
2
2
4

Environmental Science
&Technology, 2011, 24(21),
9347-9355

4
4
2
3
4
4
4
4
3
3
4

Poor

18

Conclusions
2-MIB and geosmin are the dominant off-flavor compounds in reservoir
waters;
To the second effluent waters, 246-TCA is the major off-flavor compound,
which could be formed during wastewater treatment process;
Ozonation, UV/peroxide and ozonation/BAC have been proven to be efficient
techniques to remove the off-flavor compounds in water

19

Acknowledgement
Prof. David Sedlak, UC Berkeley
Dr. Eva Agus, UC Berkeley
Dr. Lim Mong Hoo, WQO/PUB
Qian Xiaoqing, WQO/PUB
Hu Ruaikang, WQO/PUB
Emily See, WQO/PUB
Dr. Wu Jingming, WQO/PUB
Dr. Yue Junqi, WQO/PUB
Lu Qinglin, WSP/PUB

20

21