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19/01/2015 1 14h00 - 17h15 : Part 1: Introduction & Fundamentals Part 2: Optimization of SBSE Coffee Break Part 3: Application Overview Part 4: Extending SBSE to more polar solutes Part 5: Newest developments & looking forward January 26, 2015 - SBSE Training program Frank DAVID, RIC “It is clear that errors made in sampling, sample preparation or sample introduction (injection) cannot be corrected by using the most advanced MS systems.”

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Page 1: January 26, 2015 - SBSE Training programsbseinternationalmeeting.com/2015/SBSE2015_Frank_David.pdf · 2015-04-06 · January 26, 2015 - SBSE Training program Frank DAVID, RIC “It

19/01/2015

1

14h00 -17h15 :

Part 1: Introduction & FundamentalsPart 2: Optimization of SBSECoffee BreakPart 3: Application OverviewPart 4: Extending SBSE to more polar solutesPart 5: Newest developments & looking forward

January 26, 2015 - SBSE Training program

Frank DAVID, RIC

“It is clear that errors made in sampling, sample

preparation or sample introduction (injection) cannot be

corrected by using the most advanced MS systems.”

Page 2: January 26, 2015 - SBSE Training programsbseinternationalmeeting.com/2015/SBSE2015_Frank_David.pdf · 2015-04-06 · January 26, 2015 - SBSE Training program Frank DAVID, RIC “It

19/01/2015

2

Part 1: Introduction & Fundamentals

• Origin of SBSE

• From SPME to SBSE

• How to calculate a theoretical recovery?

Why Sample Preparation ?(EXIT)

• Extraction: remove solutes from matrix

• Enrichment: concentrate solutes(enrichment factor X)

• Isolation: selective extraction / clean-up / purification

• Transformation:

– Derivatization

– Pyrolysis

Page 3: January 26, 2015 - SBSE Training programsbseinternationalmeeting.com/2015/SBSE2015_Frank_David.pdf · 2015-04-06 · January 26, 2015 - SBSE Training program Frank DAVID, RIC “It

19/01/2015

3

Why SBSE?

• Extraction: remove from matrix

• Enrichment: concentrate

• Isolation: selective extraction/purification

• Transformation:

– Combined with Derivatization (for extraction & analysis)

– Pyrolysis

State-of-the-Art Sample Prep

• Automation

• Miniaturization: small sample size

• “Solventless” (avoid contamination)

• “On-line”

– or On-site sampling or On-site Analysis ?

SBSE

Page 4: January 26, 2015 - SBSE Training programsbseinternationalmeeting.com/2015/SBSE2015_Frank_David.pdf · 2015-04-06 · January 26, 2015 - SBSE Training program Frank DAVID, RIC “It

19/01/2015

4

Open Tubular Trapping of Volatiles

Bicchi, D’Amato, David, SandraFFJ 1988

15 µm dfPDMS

2D-GCDim 1: desorbIntermediate trappingDim 2: analyze

Living

Harvested

Solid Phase Micro-Extraction (SPME)J. Pawliszyn, 1990

(Kfs = Kfa*Kas)

Page 5: January 26, 2015 - SBSE Training programsbseinternationalmeeting.com/2015/SBSE2015_Frank_David.pdf · 2015-04-06 · January 26, 2015 - SBSE Training program Frank DAVID, RIC “It

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5

• Origin: Publication on the SPME extraction of PCBs.

– Authors found very low recoveries for compounds with Ko/w values of up to 1010

– Repeating the SPME experiments :

• Similar SPME recoveries were obtained

• However, more than 80 % of the spiked analytes were adsorbed on the (Teflon) stir bar

• Idea: Extraction of aqueous samples with a PDMS coated stir bar

Stir Bar Sorptive ExtractionSandra, Baltussen and David [1999]

Magnetic Stir Bar Coated with SPME-type Material (PDMS)

PDMSl = 10 mm, df = 0.5 mm

df = 1.0 mml = 20 mm, df = 0.5 mm

df = 1.0 mm

24 µl63 µl47 µl

126 µl

SPME : max. 0.5 µl

Magnet Glass

Page 6: January 26, 2015 - SBSE Training programsbseinternationalmeeting.com/2015/SBSE2015_Frank_David.pdf · 2015-04-06 · January 26, 2015 - SBSE Training program Frank DAVID, RIC “It

19/01/2015

6

Stir Bar Sorptive Extraction (SBSE)

CH3

Si O

CH3 Best GC stationary phase (apolar)

Decomposition products very specific and not related with solutes of interest

PDMS/water distribution ~ octanol/water distribution, Ko/w values can be applied

(if not available log P can be calculated using KOWIN)

Retention indices available for a wide number of compounds

Best Sorptive Extraction Medium

PDMS

Page 7: January 26, 2015 - SBSE Training programsbseinternationalmeeting.com/2015/SBSE2015_Frank_David.pdf · 2015-04-06 · January 26, 2015 - SBSE Training program Frank DAVID, RIC “It

19/01/2015

7

CH3

Si O

CH3 Temperature range

Minimum (MiAOT) (see DSC – glass transition temp)

Maximum (MAOT) (see TGA: 1% loss is a lot!)

Diffusion Coefficients

Change of viscosity in function of temperature

Sorption or Adsorption

Alternatives for PDMS

Check-list

SBSE (SPME) - Theory

ow

w

SBSE

SBSE

w

w

SBSE

w

SBSE

Kxm

m

V

Vx

m

m

C

CK PDMS/w

Kow1

Kow

m

m

0

SBSE

Equilibrium

Recovery

mSBSE= amount on PDMS

m0= initial amount

Kow = octanol - water partitioning

= phase ratio

Page 8: January 26, 2015 - SBSE Training programsbseinternationalmeeting.com/2015/SBSE2015_Frank_David.pdf · 2015-04-06 · January 26, 2015 - SBSE Training program Frank DAVID, RIC “It

19/01/2015

8

0

10

20

30

40

50

60

70

80

90

100

1 10 100 1000 10000 100000

K(o/w)

Rec

ove

ry (

%)

SBSE SPME

SBSE - TheoryRecovery of SBSE vs. SPME as a function of analyte polarity.

5.00 7.50 10.00 12.50 14.000

2000

4000

6000

8000

10000

Abundance

04000080000

120000160000200000240000

5.00 7.50 10.00 12.50 14.00Time (min)

1

3 5

6427

8

13 5 6

42

78

SBSE

SPME100 fold concentration

SBSE - Extraction of PAHs

Page 9: January 26, 2015 - SBSE Training programsbseinternationalmeeting.com/2015/SBSE2015_Frank_David.pdf · 2015-04-06 · January 26, 2015 - SBSE Training program Frank DAVID, RIC “It

19/01/2015

9

Recovery prediction

100

1

100(%)Recovery0

xKow

Kow

xm

mSBSE

EXCEL sheet 1

Gerstel Twister calculator

Estimation of Recovery : Thiobencarb

Sample volume: 10 mLLog Ko/w 3.8971 → Ko/w = 103.8971 = 7890

SBSE

Twister:24 μL PDMS

1/β:0.0024

0.0024×7890×100

0.0024×7890 + 1

95 %

SPME

Fiber:0.5 μL PDMS

1/β:0.00005

0.00005×7890×100

0.00005×7890 + 1

28 %

Page 10: January 26, 2015 - SBSE Training programsbseinternationalmeeting.com/2015/SBSE2015_Frank_David.pdf · 2015-04-06 · January 26, 2015 - SBSE Training program Frank DAVID, RIC “It

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10

Comparison of recovery: SBSE vs SPME

0102030405060708090

100

1 10 100 1000 10000 100000

K(o/w)

Re

cove

ry (

%)

SBSE SPME

Thiobencarb

Thiobencarb

Sample volume: 10 mL

SBSE: advantages & limitations

• Extraction and concentration:

– Extremely high enrichment factor possible

– In TD-GC: “what is in coating can go to detector”

• Purification (Selectivity)

• Multi-residue analysis possible

– Sample capacity depends on mass (not surface)

• Polar solutes?

– No/little enrichment on PDMS – solutions ???

Page 11: January 26, 2015 - SBSE Training programsbseinternationalmeeting.com/2015/SBSE2015_Frank_David.pdf · 2015-04-06 · January 26, 2015 - SBSE Training program Frank DAVID, RIC “It

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11

Part 2: SBSE optimization

• Extraction:

– Sample volume

– Stir bar volume

– Extraction time

– Sample adjustment: pH, salt, organic modifier

• Desorption: thermal or liquid?

• Conditioning and re-use of stir bars

A

C D

B

Extr

acti

on

Page 12: January 26, 2015 - SBSE Training programsbseinternationalmeeting.com/2015/SBSE2015_Frank_David.pdf · 2015-04-06 · January 26, 2015 - SBSE Training program Frank DAVID, RIC “It

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12

Optimization of Extraction (1)

• What is maximum recovery (%) under equilibrium conditions?

– Sample Volume

– Stir bar volume

– Log P (Kow)

• More volume = more extracted ? EXCEL sheet 2

EXCEL sheet 1

Optimization of Extraction (2)

• Real recovery < (<<) maximum recovery (%) under equilibrium conditions.

• Kinetics: extraction timedepends on

– Sample Volume

– Solutes (K)

– stirring, vessel type,…

EXCEL sheet 3 & 4

Page 13: January 26, 2015 - SBSE Training programsbseinternationalmeeting.com/2015/SBSE2015_Frank_David.pdf · 2015-04-06 · January 26, 2015 - SBSE Training program Frank DAVID, RIC “It

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13

Extraction efficiency = fie (time)

)1.(.0,

t

phaset ekCC

FwFwFs

wFsFFs

VVKMVVM

VMMVKMMSk

...2..

)......(.2

EXCEL sheet 3 & 4

k: uptake/elimination constant; S: area; Vw: volume water; Vf: volume PDMS; K =Kow; Ms: mass transfer in water; Mf: mass transfer in PDMS

0

20

40

60

80

100

120

0 1 2 5 10 15 30 60 90 120 240 480

Desorption

Page 14: January 26, 2015 - SBSE Training programsbseinternationalmeeting.com/2015/SBSE2015_Frank_David.pdf · 2015-04-06 · January 26, 2015 - SBSE Training program Frank DAVID, RIC “It

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Optimization of Desorption

• Thermal desorption: best choice

– Combined with GC

– High enrichment = high sensitivity

– Desorption = “gas chromatography on PDMS”tR = t0 (1+k), VR=V0 (1+K/)

• Liquid desorption: similar to liquid-liquid extraction and SPE

– Enrichment factor?

Pneumatics – TD splitless / CIS solvent vent

HOT

COLD

Page 15: January 26, 2015 - SBSE Training programsbseinternationalmeeting.com/2015/SBSE2015_Frank_David.pdf · 2015-04-06 · January 26, 2015 - SBSE Training program Frank DAVID, RIC “It

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15

Pneumatics – CIS Splitless injectionRoom temp

HOT

Optimization of SBSE

• Back-calculation:

– Detection: IDL (instrument detection limit)?

– Injection: split or splitless? (CIS PTV)

– Extraction recovery (Kow)?

– Sample volume/stir bar volume (dimensions)?

• Optimization of pH, salt addition, organic modifier

• Optimization of extraction time

Page 16: January 26, 2015 - SBSE Training programsbseinternationalmeeting.com/2015/SBSE2015_Frank_David.pdf · 2015-04-06 · January 26, 2015 - SBSE Training program Frank DAVID, RIC “It

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16

0

20

40

60

80

100

1.70 2.35 2.79 3.24 3.86 4.24 5.18 5.87 6.18 6.76 7.43

Pirimicarb

Fensulfothion

Fenobucarb

Metolachlor

Diazinon

Terbufos

Pendimethalin

p,p-DDD

Deltamethrin

Fenvalerate 1,2

Permethrin 1,2

Rec

over

y (

%)

0 % NaCl

5 % NaCl

10 % NaCl

20 % NaCl

30 % NaCl

Influence of salt addition (NaCl 0-30 %) on quantity extracted of representative pesticides with various octanol-water partitioning coefficients (Kow) obtained for a spiked water at 5 ng mL-1 level

log Kow / compound

Influence of Salt Addition (NaCl)N. Ochiai , K. Sasamoto, H. Kanda, S. Nakamura,

J. Chromatogr. A, 1130 (2006) 83.

Recovery of Test Mix with or without Salt Addition (spiked water at 100 ng/mL)

Recovery (%)

30 % NaCl

wo/Salt

0 20 40 60 80 100 120

Citronellol (logKow: 3.56)

Linalool (logKow: 3.38)

Nonanal (logKow: 3.27)

Ethyl hexanoate (logKow: 2.83)

Phenethyl acetate (logKow: 2.57)

γ-Nonalactone (logKow: 2.08)

Hexanol (logKow: 1.82)

Hexanal (logKow: 1.80)

cis-3-Hexenol (logKow: 1.61)

Phenethyl alcohol (logKow: 1.57)

Guaiacol (logKow: 1.34)

Page 17: January 26, 2015 - SBSE Training programsbseinternationalmeeting.com/2015/SBSE2015_Frank_David.pdf · 2015-04-06 · January 26, 2015 - SBSE Training program Frank DAVID, RIC “It

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17

Influence of pH

• To obtain high extraction efficiency, the solutes should be in non-ionized form.

• This was clearly illustrated for the analysis of preservatives such as benzoic acid, sorbic acid and parabens in beverages.

• For benzoic acid (pKa=4.21), the sample was adjusted to low pH (pH=2).

• At pH > pKa, the ionic form results in very low recoveries (log Ko/w < 0 for benzoic acid in ionic form).

• At pH < pKa, the compounds are in acidic form, having higher Kow (log Ko/w = 1.87 for benzoic acid in acidic form) and are extracted more efficiently.

Matrix Effects - Role of Organic modifier

• Observation: calibration of pesticides in white wine≠ red wine

• Samples containing high concentrations of ethanol, acids, polyphenols, etc. should be diluted before extraction. Based on our experience, a maximum of 10% ethanol content is a good starting point. Whiskey samples, for instance, are diluted 1/4 - 1/5.

• Fatty samples (milk, yoghurt, emulsions) are also diluted to a maximum of 3% fat.

• For the extraction of highly apolar solutes, such as PAHs and PCBs from water samples, it is recommended to add an organic modifier (methanol, ethanol, acetonitrile) to minimize wall adsorption.

Page 18: January 26, 2015 - SBSE Training programsbseinternationalmeeting.com/2015/SBSE2015_Frank_David.pdf · 2015-04-06 · January 26, 2015 - SBSE Training program Frank DAVID, RIC “It

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18

Multiple Extraction – Single desorption

• Increased sensitivity (alternative to increased volume)• Broad polarity (log Ko/w ) range (multiresidue analysis of

pesticides): dual (“multi-shot”) extractions • For apolar pesticides, a high content of organic modifier

(acetonitrile, methanol) is recommended to reduce wall adsorption and matrix effects.

• For polar pesticides, high modifier content will lower recovery. • From the extracts from fruit and vegetables:

– two aliquots: 50% and 20% methanol. – parallel extraction – single (combined) desorption

• Water analysis:– 20 mL sample containing 30% NaCl (for log Ko/w < 3.5)– 20 mL sample without modifier (for log Ko/w > 3.5).

Can Twisters be re-used?

• Yes (they are also too expensive for single use)• How many times?

– Depends on sample type– Importance of rinsing before desorption.–Water analysis: re-use > 50 times

• Recondition: solvent + thermal– Beware of swelling, PDMS + O2 = death

• Keep track!!!– Complex (highy loaded) samples versus clean

water samples

Page 19: January 26, 2015 - SBSE Training programsbseinternationalmeeting.com/2015/SBSE2015_Frank_David.pdf · 2015-04-06 · January 26, 2015 - SBSE Training program Frank DAVID, RIC “It

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19

Method Development summary (1)

• Verification of analyte log Kow: Based on literature data or using a Kowin calculator, the log Kow for the target solutes can be checked. If log Kow>2, SBSE on PDMS can be used. For lower log Kow values, in-situ derivatization, salt addition or another stir bar coating might be needed.

• The (maximum) extraction efficiency can be calculated. Sample volume and stir bar dimensions can be selected for optimal recovery and enrichment.

Method Development summary (2)• Thermal desorption-GC-MS suitability test: If TD-GC-

MS is used, a tube can be spiked with the target solutes and thermal desorption, cryo-trapping, injection and analysis can be performed. In this way, the suitability of the analytical equipment is checked and thermal desorption, GC and MS parameters can be optimized. At this stage, it can also be checked if the solutes are thermostable (for thermal desorption and GC analysis), if they are well focused, etc.

• Measurement of practical extraction efficiency in function of time: A series of spiked samples are analysed with increasing extraction times and the response for the target solutes is measured.

Page 20: January 26, 2015 - SBSE Training programsbseinternationalmeeting.com/2015/SBSE2015_Frank_David.pdf · 2015-04-06 · January 26, 2015 - SBSE Training program Frank DAVID, RIC “It

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20

Method Development summary (3)

• Finally the method can be optimized and validated using different spiking levels. Linearity, limit of detection and repeatability can be measured.

• Recently some papers described the use of experimental design in SBSE method development

Experimental design

- A. Prieto, O. Zuloaga, A. Usobiaga, N. Etxebarria, L.A. Fernández, Use of experimental design in the optimisation of stir bar sorptiveextraction followed by thermal desorption for the determination of brominated flame retardants in water samplesAnalytical and Bioanalytical Chemistry, 390 (2) (2008) pp. 739-748.

- K. MacNamara, R. Leardi, F. McGuigan,Comprehensive investigation and optimisation of the main experimental variables in stir-bar sorptive extraction (SBSE)-thermal desorption-capillary gas chromatography (TD-CGC)Analytica Chimica Acta, 636 (2) (2009) pp. 190-197.

Page 21: January 26, 2015 - SBSE Training programsbseinternationalmeeting.com/2015/SBSE2015_Frank_David.pdf · 2015-04-06 · January 26, 2015 - SBSE Training program Frank DAVID, RIC “It

19/01/2015

21

Part 3: Applications

• Environmental: semi-volatiles (GC amenable)

– Water > air > soil/sediment

• Food: flavor & fragrance, wine, off-odours, contaminants,…

• Consumer products: allergens, leachables,…

• Life Science: biological fluids, target & non-target (metabolomics) mode

Musty odour in Drinking Water(each 100 ppq:6 pg/60 mL,240 min stirring)

11.00 12.00 13.00 14.00 15.00 16.00 17.00 18.00

050

100150200250300350400450500550600650700750800850900950

1000

Time-->

m/z 95

m/z 197

m/z 112

2,4,6-TCAm/z 197

Geosminm/z 112

2-MIB, m/z 95

Page 22: January 26, 2015 - SBSE Training programsbseinternationalmeeting.com/2015/SBSE2015_Frank_David.pdf · 2015-04-06 · January 26, 2015 - SBSE Training program Frank DAVID, RIC “It

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22

D. Benanou, presented at 27th ISCC, Riva del Garda, Italy, May 2004

TCA in Water

1,0

1,2

1,4

1,6

1,8

2,0

2,2

2 3 4 5 6 7 80 1

DAYS of STORAGE

Co

ncen

trati

on

(n

g/l)

stored in vials at 4 ºC

On-site SBSE !

SBSE-TD-GC-MS - On-site SBSED. Benanou, presented at 27th ISCC, Riva del Garda, Italy, May 2004

Page 23: January 26, 2015 - SBSE Training programsbseinternationalmeeting.com/2015/SBSE2015_Frank_David.pdf · 2015-04-06 · January 26, 2015 - SBSE Training program Frank DAVID, RIC “It

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23

Determination of Tributyltin in Water Samples at the Quantification Level Set by

the European Union (0.2 ng/L)

QQQ

2DGC

TDU

SBSE

C. Devos, F. David, P. Sandra, J. Chromatography A, 1261 (2012) 151–157

GC-MS/MS: Interference Detected @ TBT

Abundance (x 101)

13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8 13.9 Time, min

2

4

6

8

10

12

TBT

TBT (d27) Blank

1

2

3

4

5

6

7

8

13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8 13.9

TBT

2 ppt

Time, min

13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8 13.9 Time, min

2

4

6

8

10

12

0.2 ppt

Page 24: January 26, 2015 - SBSE Training programsbseinternationalmeeting.com/2015/SBSE2015_Frank_David.pdf · 2015-04-06 · January 26, 2015 - SBSE Training program Frank DAVID, RIC “It

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GC-GC-MS/MS: TBT resolved from interferences – LOQ < 0.05 ppt

Abundance (x 102)

1

2

3

4

5

1

2

3

4

5

1

2

3

4

5

interference

TBT

2 ppt

0.2 ppt

blank

31.7 32.1 32.5 32.9 33.3 33.7 34.1 34.5 34.9 Time, min

0.2 ppt

TBT

1

2

3

4

5

32.6 32.8 33 33.2 33.4 33.6 33.8 Time, min

Abundance (x 101)

20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00 60.00 65.00

500000

1000000

1500000

2000000

2500000

3000000

3500000

4000000

Abundance

Time -->

1000

2000

3000

4000

5000

6000

7000

8000

9000

Abundance

10 20 30 40 50 60 70 80 90 100 110 120 130m/z -->

107

12277

9139 6551

2715

10000

Wine Analysis using SBSE-GC-MS

Multi-residue methods

N

O

O

O

Cl

Cl

Vinclozoline

N

Cl Cl

Cl OP

O

SO

Chlorpyriphos

• 2010 : Pesticide residues

• 2010 : Markers of wine aroma (fruity)

C13-norisoprenoides and lactones

Prof De Revel, Céline FrancUniv Bordeaux

• 2007 : Off-flavours

IBMP, EP, EG, TCA, TeCA, PCA, TBA, Géosmine

Page 25: January 26, 2015 - SBSE Training programsbseinternationalmeeting.com/2015/SBSE2015_Frank_David.pdf · 2015-04-06 · January 26, 2015 - SBSE Training program Frank DAVID, RIC “It

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Multiresidue Analysis of Wine DefectsCéline Franc, Frank David, Gilles de Revel , JCA 2009

24.00 25.00 26.00 27.000

1000000

2000000

2500000

Time-->

Abundance

EP

126 µg/L

24.50 24.70 24.90

0

0

05000

8500

Abundance

IBMP-d3

IBMP

22.3 ng/L

31.00 33.00 35.00 37.00 39.00

EG-d5

EG

56 µg/L 33.40 34.00 34.60

2500

5500

Abundance

TCA-d5

TCA

5.4 ng/L

38.00 38.40 38.80 39.20 39.60

15000

30000

Abundance

Geo-d5

Geosmin

46.4 ng/L

44.00 45.00 46.00 47.00 48.00

44.00 45.00 46.00 47.00 48.00

5000

10000

12000

Abundance

TBA

9.9 ng/L

TeCA

10.3 ng/L

PCA

29.0 ng/L

24.00 25.00 26.00 27.000

1000000

2000000

2500000

Time-->

Abundance

EP

126 µg/L

24.00 25.00 26.00 27.000

1000000

2000000

2500000

Time-->

Abundance

24.00 25.00 26.00 27.000

1000000

2000000

2500000

Time--> 24.00 25.00 26.00 27.000

1000000

2000000

2500000

Time-->

Abundance

EP

126 µg/L

24.50 24.70 24.90

0

0

05000

8500

Abundance

IBMP-d3

IBMP

22.3 ng/L

24.50 24.70 24.90

0

0

05000

8500

Abundance

24.50 24.70 24.90

0

0

0

24.50 24.70 24.90

0

0

05000

8500

Abundance

IBMP-d3

IBMP

22.3 ng/L

31.00 33.00 35.00 37.00 39.00

EG-d5

EG

56 µg/L

31.00 33.00 35.00 37.00 39.0031.00 33.00 35.00 37.00 39.00

EG-d5

EG

56 µg/L 33.40 34.00 34.60

2500

5500

Abundance

TCA-d5

TCA

5.4 ng/L

33.40 34.00 34.60

2500

5500

Abundance

33.40 34.00 34.60

2500

5500

Abundance

TCA-d5

TCA

5.4 ng/L

38.00 38.40 38.80 39.20 39.60

15000

30000

Abundance

Geo-d5

Geosmin

46.4 ng/L

38.00 38.40 38.80 39.20 39.60

15000

30000

Abundance

38.00 38.40 38.80 39.20 39.60

15000

30000

Abundance

Geo-d5

Geosmin

46.4 ng/L

44.00 45.00 46.00 47.00 48.00

44.00 45.00 46.00 47.00 48.00

5000

10000

12000

Abundance

TBA

9.9 ng/L

TeCA

10.3 ng/L

PCA

29.0 ng/L

44.00 45.00 46.00 47.00 48.0044.00 45.00 46.00 47.00 48.0044.00 45.00 46.00 47.00 48.00

44.00 45.00 46.00 47.00 48.00

5000

10000

12000

Abundance

TBA

9.9 ng/L

TeCA

10.3 ng/L

PCA

29.0 ng/L

44.00 45.00 46.00 47.00 48.00

5000

10000

12000

Abundance

44.00 45.00 46.00 47.00 48.0044.00 45.00 46.00 47.00 48.00

5000

10000

12000

Abundance

TBA

9.9 ng/L

TeCA

10.3 ng/L

PCA

29.0 ng/L

Transfer of SBSE-GC-MS methodsinto 8 laboratories

20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00 60.00 65.00

500000

1000000

1500000

2000000

2500000

3000000

3500000

4000000

Abundance

Time -->

1000

2000

3000

4000

5000

6000

7000

8000

9000

Abundance

10 20 30 40 50 60 70 80 90 100 110 120 130m/z -->

107

12277

9139 6551

2715

10000 • 2007 :

Off-flavours

• 2010 :

Pesticides

• method transfer

• training by l’ISVV

• Validation by Round Robin tests

Fronsac

Cenon

Floirac

Pauillac

Saint-Laurent-du-Médoc

Blanquefort

ISVV – Villenave d’Ornon

Cestas

Martillac

RIC lab. / Agilent Tech.

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26

Application : Round-Robin testSBSE-GC-MS « off-flavors"

20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00 60.00 65.00

500000

1000000

1500000

2000000

2500000

3000000

3500000

4000000

Abundance

Time -->

1000

2000

3000

4000

5000

6000

7000

8000

9000

Abundance

10 20 30 40 50 60 70 80 90 100 110 120 130m/z -->

107

12277

9139 6551

2715

10000

2009 : inter-laboratory test, 8 compounds – 9 laboratoires

nombre de laboratoires retenus : 9

valeur assignée m : 187,6

écart-type s* : 34,4

limites de surveillance : 118,8 ; 256,4

limites d'action : 84,4 , 290,8

Répartition des résultats des laboratoires

50,0

84,4

118,8

153,2

187,6

222,0

256,4

290,8

325,2

1 2 3 4 5 6 7 8 9

N° du laboratoire

Co

nce

ntr

atio

n

Action

Action

Surveillance

Surveillance

m

Volatile phenols

CONFIDENCE in RESULTS

Château Léoville Las Cases

2d Cru Classé - Saint Julien

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0

15

30

45

60

75

90

5-juil. 15-juil. 25-juil. 4-août 14-août 24-août 3-sept. 13-sept. 23-sept. 3-oct.

ng

/l

Seuil de perception

Cabernet SauvignonMerlotCabernet Franc

Application: IBMP in grapes (2008)

- Augmentation de l’IBMP entre la fermeture de grappe (début juillet) et la véraison (début août).

- Ensuite, dégradation plus ou moins rapide lors de la maturation du raisin en fonction des conditions climatiques du millésime.

QC on solid material2 extraction methods

1- « Passive Extraction » :

10 corks – leaching during 24h

in 500ml wine simulant (10 % Ethanol)

Leaching of Haloanisoles

SBSE extraction for leachable haloanisoles:- 100ml « extract (10 % Ethanol) »- IS: TCA-d5 (10ng/l),- 2 h extraction with 20 mm x 0.5 mm stir bar

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SBSE for Total haloanisoles & halophenols: - ASE extract (Acetone/Methanol)- IS : TCA-d5 (10ng/l) forhaloanisoles,

TCP-d2 (200 ng/l) for halophenols.- In-situ derivatization with acetic anhydride- 2 h extraction with 20 mm x 0.5 mm stir bar

2- « Active Extraction » by ASE (Dionex) : Cork + wood (for barrels)

Solvent extraction (Acetone/Methanol) at high pressure (100 bars) and

tempearture (max 180°C)

Total haloanisoles and halophenols

QC on solid material2 extraction methods

SBSE procedure for vegetables and fruit

Ultra-Turrax + ultrason (15 min)

SBSE: 60 min

1 mL extract

+ 10 mL water

TD-RTL-CGC-MS

15 g sample + 15 mL ACN

P. Sandra, B. Tienpont and F. DavidJ. Chromatogr., 1000 (2003) 299-309

Modified ratio water/organicMulti-Twister extractionN. Ochiai, K. Sasamoto, H. Kanda, T. Yamagami, F. David, B. Tienpont and P. SandraJ. Sep. Sci 28 (2005) 1083-1092

(=QuEChERS)

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Comparison of Sensitivity of

QuEChERS – SBSE

QQQ (MRM) Conc 10 x (LVI)

SCAN (50 pg)

5 pg OC

SIM (SQ)

Inject 1 µL

6 mL + salt

1 mL + d-SPE

QuEChERS

5 ng

SCAN

TD + INJ

1 mL

Dilute in 10 mL

SBSE

15 g sample

15 mL ACN

10 µg/kg

= 150 ng / 30 mL = 5 ng/mL

Even with 10% recovery, sensitivity SBSE > QuEChERS

Analysis of Baby Food by SBSE-TD-GC-MSD (mixed vegetables, rice, chicken).Detection of piperonylbutoxide

Time (min)

Abundance (*10-1)

5.00 7.00 9.00 11.00 13.00 15.00 17.00 19.00 21.00 23.00 25.00 27.00 29.00

0

400

200

600

800

1000

1200

31.00 33.00 35.00

1

1(00

A O

O

OO

O

Non-spiked

Spiked - 2 ppb

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30

SBSE for solid samples?

• YES !!!

• Preliminary extraction with water miscible solvent

• Dilute with water

• SBSE

– Good recovery

– Selective (extraction + clean-up)

PAHs in sediment• Wet sample: 15 g or Dry sample (lyophylized): 3 g + 12 g water

• Add 15 mL acetonitrile

• Add “Quechers Salt” (MgSO4) + Shake/centrifuge

• Test 1: QuEChERS clean up + GC-QQQ

– Clean-up on PSA (QuEChERS step 2)

– Centrifuge

– Inject 1 µL

• Test 2: SBSE + TD-GC-QQQ

– 100 µL + 900 µL acetone (dilute 1/10)

– 10 µL in 10 mL water (sama amount as liquid injection)

– SBSE + TD-GC-MS

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31

Sample 1 (wet) MRM 252-250 (benzofluoranthenes, benzo(a)pyrene)

SBSEliquid

Sample 2 (dry) MRM 252-250 (benzofluoranthenes, benzo(a)pyrene)

SBSEliquid

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32

Determination of PAHs in Sea Food

Weigh 3g fish tissue into 50mL centrifuge tube

Add IS, 12mL water, vortex 1 min

Add 15mL acetonitrile, vortex 1 min

Add Agilent QuEChERS salt packet, cap and shake P/N 5982-5755

Centrifuge @4700 RPM 5 min

Transfer 1 mL of ACN layer for cleanup step

dSPE cleanup, centrifuge SBSE cleanup and concentration

Transfer to vial, GC/MS Transfer Twister to tube, GC/MS

E. Pfannkoch, Gerstel US

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33

Part 4: Analysis of Polar Solutes

• Derivatization (increase extraction efficiency)– In-situ (in aqueous matrix)

– Post-extraction (during thermal desorption) (improve analysis & detection)

• Sequential SBSE– Several extractions using different

conditions/phases

– Combined desorption

• New phases

Derivatisation in Aqueous Media

• Acylation (acetic anhydride + K2CO3)– Phenols

• Oximation with pentafluorobenzylhydroxylamine (PFBHA)– Aldehydes and ketones

• Acylation with ethylchloroformate (ECF) (or hexylCF)– Alcohols (acylation), Amines (N-acetyl), Ccids (ethyl esters)

• Alkylation with NaBEt4– Organotin (tetra-alkyl Sn)

• Derivatization of thiols with alkylpropiolate

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34

Analysis of chlorophenols• 10 mL water sample• 0.5 g K2CO3 and 0.5 mL acetic anhydride• SBSE using a 10 mm x 0.5 mm df PDMS stir bar • TD in splitless mode + GC-MS:

– 30 m x 0.25 mm i.d. x 0.25 µm df HP-5MS – MS in selected ion monitoring (SIM) mode.

• mono-chlorophenols (as acetates) (ion 128, 3 isomers), • dichlorophenols (ion 164, 6 isomers, 2 isomers not separated),• trichlorophenols (ion 196, 5 isomers), • tetrachlorophenol (ion 232, 1 isomer)• pentachlorophenol (ion 266).

• Same for: hydroxyl-PAHs, bisphenol A …

Analysis of chlorophenols (10 ppt in water)

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Acetylated OH-PAH in urine of a fireman

Time (min)

4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00 28.00 30.00

0

0

100

200

400

600

800

Abundance (*10-3)

OH-PAH

OH-pyrene

1

2

3

4

5

R2 = 0,999

0

5000000

10000000

15000000

20000000

0 20 40 60 80 100

concentration (µg/L)

peak area

1 1-hydroxypyrene

2 1-naphthol

3 2-naphthol

4 3-methylnaphthol

5 5,7-dimethyl-1-naphthol.

EIC: m/z 218, 144, 158, 172

+ C = O

R1

R2

CH2 O NH2

FF

F

F F

CH2 O N = C

FF

F

F F

R1 or R2

R2 or R1

Carbonyl compounds

O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine

(PFBHA)

PFBHA derivative isomers

SBSE or HSSE of aldehydes/ketones

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36

Derivatization in HSSE with pentafluorobenzylhydroxylamine (PFBHA) - BEER

19.00 20.00 21.00 22.00 23.00 24.00 25.00

800

1600

2400

3200

4000

4800

5600

6400

Time, min

Abundance

BLANK

SPIKED

1 ppb

. . . ...

2-Octenal

(150 ppt)

2-Nonenal

(+/-75 ppt) 2,4-Decadienal

(25 ppt)

Nonanal

(+/-550 ppt)

SBSE procedures for biological samples

Urine 5 (1) mL Blood/bile 1mL, 1g stomach content

Acetylation:

0.5 g K2CO3 + 0.5 mL AA

1mL NH4OAc + 10 µL -glucuronidase, 90 min @ 37°C

Ethylchloroformate:

2.5 mL EtOH/PYR (2:1) + 0.1 mL ECF

+ 10 mL water

SBSE: 60 min

TD-CGC-MS

+ 1 mL MeOH+ 10 mL water

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8 . 0 0 1 0 . 0 0 1 2 . 0 0 1 4 . 0 0 1 6 . 0 0 1 8 . 0 0 2 0 . 0 0 2 2 . 0 0 2 4 . 0 0 2 6 . 0 0

1 0 0 0 0 0

2 0 0 0 0 0

3 0 0 0 0 0

4 0 0 0 0 0

5 0 0 0 0 0

6 0 0 0 0 0

7 0 0 0 0 0

8 0 0 0 0 0

9 0 0 0 0 0

1 0 0 0 0 0 0

1 1 0 0 0 0 0

1 2 0 0 0 0 0

1 3 0 0 0 0 0

1 4 0 0 0 0 0

1 5 0 0 0 0 0

T i m e - - >

A b u n d a n c e

T I C : 1 0 0 9 0 8 _ u r i n e _ b l a n k . D \ d a t a . m s

No glucuronidase

• Analysis of 1 mL urine

SBSE in metabolomics

8 . 0 0 1 0 . 0 0 1 2 . 0 0 1 4 . 0 0 1 6 . 0 0 1 8 . 0 0 2 0 . 0 0 2 2 . 0 0 2 4 . 0 0 2 6 . 0 0

0

1 0 0 0 0 0

2 0 0 0 0 0

3 0 0 0 0 0

4 0 0 0 0 0

5 0 0 0 0 0

6 0 0 0 0 0

7 0 0 0 0 0

8 0 0 0 0 0

9 0 0 0 0 0

1 0 0 0 0 0 0

1 1 0 0 0 0 0

1 2 0 0 0 0 0

1 3 0 0 0 0 0

1 4 0 0 0 0 0

1 5 0 0 0 0 0

T i m e - - >

A b u n d a n c e

T I C : 1 0 0 9 0 8 _ u r i n e _ b l a n k . D \ d a t a . m s

T I C : 1 0 0 9 0 8 _ u r i n e _ g l u c u r o n i d a s e _ 2 0 u L . D \ d a t a . m s ( * )

With glucuronidase

Analysis of Thiols (wine, beer,...)

• Polyfunctional thiols [3-mercaptohexan-1-ol (3MH), 3-mercaptohexyl acetate (3MHA) and 4-mercapto-4-methylpentan-2-one (4MMP)] are important aroma compounds. Current methods lack specificity and sensitivity.

• Derivatization with alkyl propiolate (ethyl propriolate) can be performed in-situ and, combined with SBSE, high sensitivity and good selectivity are obtained for the detection of the thioacrylates.

• See: N. Ochiai et al, in press

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38

Post-extraction derivatization

functional group

-NH2

-NHR

-COOH

-CHO, -CO

reagent

o-Phthalaldehyde

9-Fluorenylmethylchloroformate (FMOC)

p-Bromophenylacyl bromide2-Naphthacyl bromide

-OH Phenylisocyanate

2,4-Dinitrophenylhydrazine

• Silylation: during desorption

• After liquid desorption : all derivatization methods

• HPLC derivatization methods

Desorption / derivatization

BSTFA(volatile)

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PDMS phase = Ko/w driven enrichment

PDMS: 24 µL

Sample: 10 mL

una

0

20

40

60

80

100

120

LogKow

Rec

over

y (

%)

2.00 4.00 6.00 8.00 10.000

LogKow > 4.0

PDMS: 24 µL

Sample: 5 mL

TheoreticalRecovery (%)

LogKow < 4.0

Sequential Stir Bar Sorptive Extraction

N. Ochiai et al, J. Chromatography 1200 (2008) 72.

SBSE has a limitation for recovery of hydrophilic compounds because SBSE is basedon distribution between PDMS and water.

Salt addition allows to improve recovery ofhydrophilic compounds.

⇒ Negative effect for recovery of hydrophobic compounds ….. 0

20

40

60

80

100

120

LogKow

Rec

over

y (

%)

2.00 4.00 6.00 8.00 10.000

Theoretical recovery

Recovery of 88 pesticides by SBSE

NaCl 30 %

Sequential SBSE!

Sequential Stir Bar Sorptive Extraction

N. Ochiai et al, J. Chromatography 1200 (2008) 72.

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Sequential SBSE Procedure

SBSE 1h@1500 rpm SBSE 1h@1500 rpm

30% NaCl

Solutes: LogKow > 4 Solutes: LogKow < 4

Two Twisters are

Simultaneously

desorbed

Sequential SBSE for Multi-residue pesticide analysis

Theoretical recovery

0

20

40

60

80

100

120

LogKow

Rec

over

y (

%)

2.00 4.00 6.00 8.00 10.000

Recovery of 88 pesticides by SBSERecovery of 88 pesticides by Sequential SBSE

LogKow > 2.5

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New phases for coating

• SPME: different fibers available(PDMS, PDMS/carbon, DVB, CW, acrylate)

What about SBSE?

• Thermal desorption or liquid desorption ?

• Immersion or Headspace sampling ?

• More material = bleeding more critical

• Attempts: polyacrylate, polyurethane, carbon, sol-gel, monoliths, MIPs, RAM,…

New phases for coating - criteria

• Should be used with thermal desorption

– Low bleed

– Bleed does not interfere with solutes

• Liquid desorption = SPE

– Compare enrichment factor!!!

• Should be significantly better than PDMS (and compared to it)

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Development of New Phase Twister

Development of Ethylene glycol modified silicone

“EG Silicon Twister”

Comparison between EG Silicon Twister and PDMS Twister for HSSE of coffee powder

EG Silicon TwisterHSSE 1h @60ºC

PDMS TwisterHSSE 1h@60ºC

Furf

ury

lalc

oh

ol

Me

thyl

pyr

azin

e

2,5

-Dim

eth

yl p

yraz

ine

2-Et

hyl

-6-m

eth

yl p

yraz

ine

Gu

aiac

ol

p-V

inyl

guai

aco

l

4-V

inyp

hen

ol

2-fo

rmyl

pyr

role

Mal

to2-

ace

tyl p

yrro

le

5-m

eth

yl fu

rfu

ral

Furf

ury

lace

tate

Ace

tola

ceta

te

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43

19/01/2015 SBSE Technical Meeting 85

SBSE & polar compounds – New phases

• Extraction efficiency for selected compounds in whiskey

• Compound log Kow Extracted (ng)

PDMS PDMS-EG

• Vanillin 1,05 14 400 (x 29)

• Guaiacol 1,34 45 340 (x 8)

• Phenethyl alcohol 1,57 380 3700 (x 10)

• 1-Hexanol 1,82 25 110 (x 4)

• 2-Methyl phenol 2,06 110 1500 (x14)

• 4-Ethyl guaiacol 2,38 210 550 (x 2,6)

• Phenethyl acetate 2,57 1800 2200 (x1,2)

• Ethyl hexanoate 2,83 640 640 (x1,0)

• Ethyl octanoate 3,81 4600 4400 (x0,96)

SBSE 1h@800 rpm SBSE 1h@800 rpm

30% NaCl

Pyridine, Pyrazine,Oxazole, etc…

Phenol, Pyrrole,Alcohol (aromatic,Heterocyclic), etc…

Sequential SBSE for odor analysis

N. Ochiai et al, J. Chromatography 1200 (2008) 72.

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Comparison of TICs for coffee sampleSBSE vs Seq SBSE (PDMS-PDMS) vs Seq SBSE (PDMS-EGS)

Furf

ura

l

5-M

ethy

lfu

rfu

ral

Furf

ury

lmet

hyl d

isu

lfid

e

Gu

aiac

ol

2-ac

etyl

pyr

role

Furf

ury

leth

er

Ethy

l mal

tol

Vu

nylm

eth

oxy

ph

eno

l

SBSEPDMS (2 h)

Sequential SBSEPDMS - PDMS (20 % NaCl)

Sequential SBSEPDMS - EGS (20 % NaCl)

From: N. Ochiai et al, Gerstel KK

Comparison of recovery of phenolic compounds between EG Silicon, PDMS and Seq-SBSE

0 2 4 6 8

p-Vinyl phenol (logKow: 2.41)

p-Vinyl guaiacol (logKow: 2.24)

p-cresol (logKow: 2.06)

Phenol (logKow: 1.51)

Guaiacol (logKow: 1.34)

Vanillin (logKow: 1.05) (x 10)

EGS

PDMS

Intensity (x 106)

PDMS-EGS

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Comparison of recovery of nitrogen hetrocycliccompounds between EG Silicon, PDMS and Seq-SBSE

0 1 2 3 4

Indole (logKow: 2.05)

2,4,5-trimethyl oxazole (logKow: 1.86)

5-Methyl pyrazine (logKow: 1.53)

3,4-Dimethyl isoxazole (logKow: 1.31) x10

4,5-Dimethyl oxazole (logKow: 1.31) x10

2,5-Dimethyl pyrazine (logKow: 1.03)

Pyridine (logKow: 0.80)

2-Formyl pyrrole (logKow: 0.60)

2-Acetyl pyrrole (logKow: 0.56)

Methyl pyrazine (logKow: 0.49)

Intensity (x 106)

EGS

PDMS

PDMS-EGS

Comparison of recovery of alcoholsbetween EG Silicon, PDMS and Seq-SBSE

0 2 4 6

Linalool (logKow: 3.38) x100

Benzyl alcohol (logKow: 1.08)

Furfuryl alcohol (logKow: 0.45)

Intensity (x 106)

EGS

PDMS

PDMS-EGS

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EG Silicone Twister in routine

Although the EG-Silicone stir bar showed good performance in SBSE, when re-used several times, increased bleeding from the decomposed phase and decreased repeatability were observed. For those EG-Silicone stir bars, numerous scratches were observed on the surface of the grid by using microscopy and tiny exposed metal surfaces appeared.

Bleeding

Robustness:

PDMS stir bar

EG Silicone stir bar

Magnetic clip

(a) (b)

mSBSE using different coatingsN. Ochiai et al, HTSP, 2014

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EG-Silicone stir bar

PDMS stir bar

mSBSE

Comparison of TICs of the roasted green tea by single SBSE and mSBSE

Other new materials ???

• Sol-Gel (PDMS, PVA): no stable coating at useful film thickness

• Monoliths (acrylate, vinylpyrrolidone): mostly similar to PDMS ( no significant improvement for polar solutes)

• Polyurethane: liquid desorption

• Poly(phthalazine ether sulfone ketone) (PPESK): Guan et al, JCA 1177 (2008) 28

• Carbon materials???

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Newest Developments & looking forward

• Google: “SBSE”, from 2015: 35 articles!!!

• New phases (> 300 articles since 2011, mostly on new phases)

• New applications: SBSE-DART-MS

– K. Brooks-Loftin, Univ Florida

– Bridoux et al (CEA, Arpajon), Analysis of phosphoric acid esters by SBSE-DART-Orbitrap

• Passive sampling: SPMD, POCSIS

DEVELOPMENT OF NOVEL DART™ TOFMS ANALYTICAL TECHNIQUES FOR THEIDENTIFICATION OF ORGANIC CONTAMINATION ON SPACEFLIGHT-RELATED

SUBSTRATES AND AQUEOUS MEDIAKATHLEEN BROOKS LOFTIN, University of Central Florida, Orlando

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Conclusions (1)• SBSE is a mature sample preparation technique:

automated – miniaturized – solventless

• High enrichment factor

• Reduced risk of contamination

• On-site sampling/extraction

• Wide application area: QC – contaminants –metabolomics

Conclusions (2)• Complementary to SPME

(immersion versus headspace)

• “My toolbox”

– Static headspace (SHS)

– HS-SPME (headspace)

– Dynamic Headspace (DHS) – Full evaporation DHS (FEDHS) – Multi Volatile Method (MVM)

– SBSE

– SPE

• Still looking for new phases / new applications

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Reviews- E. Baltussen, P. Sandra, F. David, C.A. Cramers,

J. Microcol. Sep. 11 (1999) 737. (1009 citations on Jan 18, 2015)

- F. David, P. Sandra, Stir bar sorptive extraction for trace analysisJournal of Chromatography A, 1152 (1-2) (2007), pp. 54-69.

- F. Sánchez-Rojas, C. Bosch-Ojeda, J.M. Cano-Pavón, A review of stir bar sorptive extractionChromatographia, 69 (SUPPL. 1), (2009) pp. S79-S94

- A. Prieto et alStir-bar sorptive extraction: A view on method optimization, novel applications, limitations and potential solutionsJournal of Chromatography A, 1217 (16),(2010) pp. 2642-2666.

Reviews- M. Kawagushi, R. Ito, H. Nakazawa, A.Takatsu,

Applications of SBSE to food analysis, Trends in Analytical Chemistry 45 (2013) 280-293

- F.J. Camino-Sanchez et alStir bar sorptive extraction: Recent applications, limitations and future trends,Talanta 130 (2014) 388-399

- N. Gilart, R.M. Marcé, F. Borrull, N. Fontanals, New coatings for stir-bar sorptive extraction of polar emerging organic contaminants, Trends in Analytical Chemistry 54 (2014) 11–23

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• From David, F.; In Comprehensive Sampling and Sample Preparation,

• Volume 4; Pawliszyn, J.; Mondello, L.; Dugo, P.; Eds; Elsevier, Academic Press: Oxford,

• UK, pp 473–493, 2012.• ISBN: 9780123813732• © 2012 Elsevier Inc. All

rights reserved.• Academic Press

Relevant Websites• http://www.sbsetechnicalmeeting.com/ (website

of technical meeting on SBSE, also includes presentations)

• http://logkow.cisti.nrc.ca/logkow/index.jsp (log Kow database)

• http://epa.gov/oppt/exposure/pubs/episuite.htm (to download log Kow calculator)

• http://www.gerstel.com/en/index_e.htm (commercial information on SBSE & equipment, also application notes)