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Taste and odor in drinking water : originsand analysis

Dalel BENALI, Elise CORBI, David BENANOU, Jean CANTET

13th April 2006

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SUMMARYSUMMARY

Taste and Odor problems in water

Introduction to the SBSE technique

Method development & validation

Real Samples Analysis

Conclusion

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sumary

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REGULATIONREGULATION

Water quality criteria are established in order to guarantee the absence of health risk for humans and animals

Drinking water company must guarantee :

Water is safe for human health

Balance of mineral salts

Water is pleasant to drink

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BAD TASTE, GOOD TASTEBAD TASTE, GOOD TASTE

2004 : 42% OF COMPLAINTS CONCERNEDTHE BAD TASTE OF WATER

High level of residual chlorineOrganic or inorganic odorous compounds

Odorous compounds are present in water at very low levels

Not dangerous at such levels

Compounds well known: from algae, bacteria or waste

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Flavour Profile Analysis is more sensitivethan most analytical systems

>>

SENSITIVITY VERSUS SELECTIVITYSENSITIVITY VERSUS SELECTIVITY

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Reach human sensitivity (go beyond)with our analytical system

Provide an analytical tool for a preventivetreatment rather than a curative one

OUR GOALOUR GOAL

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Detection

liquid - liquid

SPE

Head-Space

Purge & TrapCLSA

SPME

Extraction-Enrichment

chromatography

ORGANIC MICROPOLLUTANTS ORGANIC MICROPOLLUTANTS ANALYSISANALYSIS

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liquid - liquid

SPE

Head-Space

Purge & Trap

CLSA

SPME

Extraction-Concentration

Detection

chromatography

ORGANIC MICROPOLLUTANTS ORGANIC MICROPOLLUTANTS EXTRACTIONEXTRACTION

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sumary

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THE TWISTERTHE TWISTERStirStir Bar Bar SorptiveSorptive ExtractionExtraction

Length Phase thickness Phase volume

10 mm 0,5 mm 24 µL

20 mm 0,5 mm 47 µL

Glass

Stir bar PDMS

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HOW DOES IT WORK ?HOW DOES IT WORK ?Introduce twister into water

Stirring extraction

Take twister out

Rinse it with distillated water

Dry it with clean wipes

Introduce into a desorption tube

Put the tube into autosampler

Thermic desorption

Analysis

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Thermic desorber

MS detector

Olfactometricdetector

autosampler

ANALYTICAL SYSTEM 1ANALYTICAL SYSTEM 1

1/3 2/3

CIS

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Gas Chromatograph

Mass spectrometer

Multi Purpose Sampler

ANALYTICAL SYSTEM 2ANALYTICAL SYSTEM 2

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METHOD DEVELOPMENT...METHOD DEVELOPMENT...

Optimization of sample volume

Optimization of extraction time

Incidence on twister storage after extraction

For quantification, use of labelled internal standards

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2-MIB(2-methyl isoborneol)

Geosmine)

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

2,3,6-TCA(2,4,6-trichloroanisole)

2,3,4-TCA(2,4,6-trichloroanisole)

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

0,1 - 2 ng/l

1 - 10 ng/l

5-10 ng/l

0,1 - 2 ng/l

0,2 - 2 ng/l

0,15 - 2 ng/l

Odorthreshold

ODOROUS COMPOUNDSODOROUS COMPOUNDS

musty

musty

earthy

musty

musty

musty

Odortype

212

182

152

212

212

346

Molecularmass

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RECOVERY VERSUS SAMPLE VOLUMERECOVERY VERSUS SAMPLE VOLUME

MIB Geosmine246 TCA

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

0 50 100 150 2000

0,05

0,1

0,15

0,2

0,25

0 50 100 150 200

Recovery Quantity extracted

Sample volume

0

200000

400000

600000

800000

1000000

1200000

1400000

1600000

1800000

2000000

0 30 60 90 120 150 180 210 240 270 3000

500000

1000000

1500000

2000000

2500000

0 30 60 90 120 150 180 210 240 270 300

0

500000

1000000

1500000

2000000

2500000

3000000

3500000

4000000

4500000

5000000

0 30 60 90 120 150 180 210 240 270 3000

500000

1000000

1500000

2000000

2500000

3000000

3500000

4000000

0 30 60 90 120 150 180 210 240 270 300

2,4,6-TCAMIB

GEOSMINE

120

120

120

120

2,4,6-TCAD5

OPTIMIZATION OF EXTRACTION TIMEOPTIMIZATION OF EXTRACTION TIME

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MIB

0

0,5

1

1,5

2

2,5

day1 Day2 day3 day4 day5 day8 day9 day10 day11 day12

Geosmine 246-TCA 236-TCA 234-TCA 246-TBA

INCIDENCE ON TWISTER STORAGEINCIDENCE ON TWISTER STORAGE

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2-MIB

Geosmine

2,4,6-TCA

2,3,6-TCA

2,3,4-TCA

2,4,6-TBA

LOQ(ng/l)

0.9975

0.9972

0.9992

0.9991

0.9988

0.9985

correlationcoefficient RSD

1

0,5

0,1

0,1

0,2

0,2

VALIDATIONVALIDATION

13%

14%

4%

5%

13%

15%

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DETECTION : GC/MS EI DETECTION : GC/MS EI SimultaneousSimultaneous SIM/SCANSIM/SCAN

11.00 11.50 12.00 12.50 13.00 13.50 14.00 14.50 15.00 15.50 16.00 16.50

0

10000

20000

30000

40000

50000

60000

70000

80000

MIB

Ion 95 qualifier : 108

2,4,6-TBA

Ion 346 qualifier : 344

2,4,6-TCA

2,3,6-TCA2,3,4-TCA

Ion 212 qualifier : 210GeosmineIon 112 qualifier : 120

Tap water spiked with 2 ng/l

11.00 11.50 12.00 12.50 13.00 13.50 14.00 14.50 15.00 15.50 16.00 16.50

0

5000

10000

15000

20000

25000

30000

35000

40000

45000

50000

55000

2,3,6-TCA : 0.1 ng/l

2,4,6-TCA : 0.1 ng/l

MIB : 1ng/l

Geosmine : 0.5 ng/l

2,3,4-TCA : 0.2 ng/l2,3,6-TBA : 0.2 ng/l

Mineral water spiked with LOQ

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OFFOFF--FLAVOUR PRECURSORSFLAVOUR PRECURSORSC

CH

CHCH

CH

CH

OH

phenol

CCH

CHC

CH

CH

OH

Cl

CCH

CHCH

C

CH

OH

Cl

CCH

CHCH

CH

C

OHCl

2-MCP 3-MCP 4-MCP

CC

CHCH

CH

C

OHCl Cl C

CH

CHC

CH

C

OHCl

Cl

CCH

CCH

CH

C

OHCl

Cl

CCH

CCH

C

CH

OH

ClCl

CCH

CHCH

C

C

OH

Cl

Cl CCH

CHC

C

CH

OH

Cl

Cl26-DCP 24-DCP 25-DCP 35-DCP 26-DCP 34-DCP

CC

CHC

CH

C

OH

Cl

Cl Cl CC

CHCH

C

C

OHCl Cl

Cl

CCH

CCH

C

C

OHCl

Cl Cl

CCH

CC

CH

C

OHCl

Cl

Cl

CCH

CHC

C

C

OHCl

Cl

Cl

236-TCP246-TCP 235-TCP 245-TCP 234-TCP

CC

CCH

C

C

OHCl

Cl

Cl

Cl2356-TeCP246-TBrP

CC

CHC

CH

C

OHBr Br

Br TCP

CC

CC

C

C

OHCl

Cl

Cl

Cl

Cl

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RECOVERY VERSUS SAMPLE VOLUME

0,E+00

2,E+06

4,E+06

6,E+06

8,E+06

1,E+07

1,E+07

1,E+07

2,E+07

2,E+07

10 20 50 100 200

Sample volume (ml)

0,E+00

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

10 20 50 100 200

Recovery Quantity extracted

phenol 4-CPhenol 23diCphenol 246triCphenol PCP

OPTIMIZATION OF EXTRACTION TIME

0,E+00

1,E+06

2,E+06

3,E+06

0 50 100 150 200 250 300 350 400

0,E+00

1,E+06

2,E+06

3,E+06

4,E+06

0 50 100 150 200 250 300 350 4000,E+00

1,E+06

2,E+06

3,E+06

4,E+06

0 50 100 150 200 250 300 350 400

0,E+00

2,E+06

4,E+06

6,E+06

8,E+06

0 50 100 150 200 250 300 350 400

4-CPhenol

23diCphenol

246triCphenolPCP

60 min

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INCIDENCE ON TWISTER STORAGEINCIDENCE ON TWISTER STORAGE

0,E+00

5,E-01

1,E+00

2,E+00

2,E+00

3,E+00

3,E+00

Day 1 Day 2 Day 4 Day 5 Day 8 Day 9 Day 10 Day 11 Day 12

Are

a ra

tio

phenol 4-CPhenol 23diCphenol 246triCphenol PCP

8%5%2%1%2%

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9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00 17.00 18.00 19.00

0

200000

400000

600000

800000

1000000

1200000

1400000

1600000

1800000

phén

ol

chlo

roph

énol

chlo

roph

énol

chlo

roph

énol 24

6-tr

ibro

mop

héno

l

2356

-tet

rach

loro

phén

ol

pent

achl

orop

héno

l246-

tric

hlor

ophé

nol

236-

tric

hlor

ophé

nol

l24

5-tr

ichl

orop

héno

l

235-

tric

hlor

ophé

nol

8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00 17.00

0

10000

20000

30000

40000

50000

60000

phén

ol

chlo

roph

énol

chlo

roph

énol

chlo

roph

énol

246-

trib

rom

ophé

nol

2356

-tet

rach

loro

phén

ol

pent

achl

orop

héno

l

26-d

ichl

orop

héno

l26

+25-

dich

loro

phén

ol35

-dic

hlor

ophé

nol

34-d

ichl

orop

héno

l

246-

tric

hlor

ophé

nol

236-

tric

hlor

ophé

nol

245-

tric

hlor

ophé

nol

235-

tric

hlor

ophé

nolQuantification limit :

5 ng/l

DETECTION : GC/MS EI DETECTION : GC/MS EI SimultaneousSimultaneous SIM/SCANSIM/SCAN

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sumary

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SAMPLINGSAMPLING

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TAP WATER ANALYSISTAP WATER ANALYSISOFF FLAVOR EPISODE IOFF FLAVOR EPISODE I

10.50 11.00 11.50 12.00 12.50 13.00 13.50 14.00 14.50 15.00 15.50 16.00 16.50

MSdetection

sniffingdetection

Geosmine : 1.5 ng/l

Pencilmusty

?

Isolongifolène

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2810.50 11.00 11.50 12.00 12.50 13.00 13.50 14.00 14.50 15.00 15.50 16.00 16.50

MSdetection

sniffingdetection

2,4,6-trichloroanisole : 1.0 ng/l

Geosmine : 1.5 ng/l

Earthy, undergrowthmusty

TAP WATER ANALYSISTAP WATER ANALYSISOFF FLAVOR EPISODE IIOFF FLAVOR EPISODE II

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MSdetection

sniffingdetection Earthy

Earthyundergrowth

2,4,6-trichloroanisole : 5.0 ng/l

MIB : 2 ng/l

MushroomGeranium

??

TAP WATER ANALYSISTAP WATER ANALYSISOFF FLAVOR EPISODE IIIOFF FLAVOR EPISODE III

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2-8

1

12, 13, 1510

16

119

SAMPLINGTAP WATER ANALYSISTAP WATER ANALYSISOFF FLAVOR EPISODE IVOFF FLAVOR EPISODE IV

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MSdetection

sniffingdetection

8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00 17.00

Phenolic

2,4,6-tribromoanisole :5.6 ng/l

phenol

PhenolicPhenolic

2,4,6-trichlorophenol

246-tribromophenol

Musty

bromodichloroanisol

dibromochloroanisol

CC

CHC

CH

CBr

Cl

Cl

OCH3

CC

CHC

CH

CBr

Br

Cl

OCH3

TAP WATER ANALYSISTAP WATER ANALYSISOFF FLAVOR EPISODE IVOFF FLAVOR EPISODE IV

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NEXT INVESTIGATIONS :NEXT INVESTIGATIONS : ODOR CATCHERODOR CATCHER......

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NEXT INVESTIGATIONS...NEXT INVESTIGATIONS...

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sumary

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CONCLUSIONCONCLUSION

Simple and fast : up to 100 samples per day

Very sensitive : low ppq in SIM mode

Possibility of making « in situ » extraction

Reuse of Twister 100 times without loss of efficiency

Good reproductibility : 4% - 15%

Unambiguous results because of dual detection

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THANK YOU FOR YOUR ATTENTION !!!