INSTITUTE OFINSTITUTE OF CHEMICAL TECHNOLOGYCHEMICAL TECHNOLOGYDepartment of Food ChemistryDepartment of Food Chemistry and Analysisand AnalysisTechnicka 3, 16628 Prague, Czech Technicka 3, 16628 Prague, Czech RRepublicepublicjana.hajslova@vscht.czjana.hajslova@vscht.cz

Jana HajslovaJana Hajslova, Lukas Vaclavik, Lukas Vaclavik, , Tomas Cajka, Jan Poustka, Ondrej Tomas Cajka, Jan Poustka, Ondrej Lacina, Lacina, Jakub SchurekJakub Schurek

Rapid Control of FoodRapid Control of Food / Environmental / Environmental Safety Safety:

NEW CHALLENGES IN MASS NEW CHALLENGES IN MASS SPECTROMETRYSPECTROMETRY

Ambient mass spectrometryAmbient mass spectrometry

Ambient mass spectrometryAmbient mass spectrometry provides solution provides solution!!

…….An awkward feature of mass .An awkward feature of mass spectrometry is that the sample must be spectrometry is that the sample must be introduced into introduced into vacuumvacuum or into an or into an inaccessible regioninaccessible region closely coupled to closely coupled to the vacuum system…..the vacuum system…..

the direct analysis of ordinary objects in the open atmosphere of the laboratory or in their natural environment is possible

DESI DESI Purdue Univ. Purdue Univ. USAUSA

DART DART JEOL, JEOL, USAUSA

Recent review

The ambient ionization methods retain the signature advantages of MS:

speedspeed

chemical specificitychemical specificity

low detection limitslow detection limits

moreover: no sample preparationis needed !!!

a Techniques where ESI mechanisms are mainly responsible for ionization.

b Methods where chemical ionization is responsible for ionization (photoionization - PI, ion evaporation - IE and electrical discharge)

AMBIENT DESORPTION IONIZATION METHODSAMBIENT DESORPTION IONIZATION METHODS

desorptiondesorption production of ionizing chemical reagentsproduction of ionizing chemical reagents

DESI ►

DART ▼

Spray and fluid velocity illustration. Droplets are black spheres eight times their actual size. Background color indicates velocity magnitude of surrounding fluid. The blue line shows the optimum collection angle from experiments (~ 10°)

DESI ▼

Because mass spectrometer orifice is continually bathed Because mass spectrometer orifice is continually bathed in hot inert gas, in hot inert gas, the DART source is remarkably resistant the DART source is remarkably resistant to contamination and sample carryoverto contamination and sample carryover..

Comparison of the intensities of the molecular ion of warfarin, [M + H]+ = 309, dissolved in different solvents after DART ionization at 250 C.

Objectives of study:

Optimization of conditions for triacylglycerols (TAG) dentification

Identification of oil type

Assessment of processing technology

Assessment of

DIRECT CHARACTERIZATION DIRECT CHARACTERIZATION OF EDIBLE OILS OF EDIBLE OILS

Case studyCase study no no.. 1 1

EXPERIMENTAL CONDITIONS

DART–TOFMS SETTINGS:Ion mode: POSITIVEGas: HELIUMGas temperature: 300°CNeedle voltage: 3000 VElectrode 1: 150 VElectrode 2: 250 VCone voltage: 20 VPeaks voltage: 1100 VMCP voltage: 2500 VInternal calib.: PEG 600

Neat oils were sampled with glass melting point tubes

A cotton swab dipped into diluted ammonium hydroxide was placed near the sampling gap to enhance formation of [M+NH4] ions from triACYLglycerides

AccuTOF-DARTTM system was operated under settings given below

MS[1];1.161..1.226;-1.0*MS[1];1.280..1.305; / ESI+ / 20080327_SMPL1

100 200 300 400 500 600 700 800 900 1000m/z

0

10

20

30

40

50

Intensity (53000)x103

902.80217

603.52369

876.78826

903.80598

577.50761

604.52704

300.28567904.81267

874.77212411.39026

428.41634409.37558283.25981

397.37614 605.53391

339.28483905.81777121.06356 850.77295460.40515

169.08399575.49223265.24844

638.56034

848.75652143.10375492.39474

918.79683639.56475493.39059932.83527

804.65857764.65900640.56840

VIRGIN OLIVE OIL – DART positive mass spectrum, 300°C, m/z 100 - 1000IN

TE

NS

ITY

m/z

FREE FATTY ACIDSDAGsDAGs

TAGsTAGs

SQUALENE

VIRGIN OLIVE OIL – DART positive mass spectrum, 300°CMS[1];1.161..1.226;-1.0*MS[1];1.280..1.305; / ESI+ / 20080327_SMPL1

100 200 300 400 500 600 700 800 900 1000m/z

0

10

20

30

40

50

Intensity (53000)x103

902.80217

603.52369

876.78826

903.80598

577.50761

604.52704

300.28567904.81267

874.77212411.39026

428.41634409.37558283.25981

397.37614 605.53391

339.28483905.81777121.06356 850.77295460.40515

169.08399575.49223265.24844

638.56034

848.75652143.10375492.39474

918.79683639.56475493.39059932.83527

804.65857764.65900640.56840

INT

EN

SIT

Y

m/z

MS[1];1.161..1.226;-1.0*MS[1];1.280..1.305; / ESI+ / 20080327_SMPL1

250 260 270 280 290 300 310m/z

0

2

4

6

8

10

12

14

16

18Intensity (18000)x10

3

300.28567

283.25981

298.27006

265.24844

301.28791

281.24361

263.23150261.25264 274.26920

284.26364259.24115

297.25313279.23295257.24114

302.29691266.25120 296.25205273.25029 285.26526255.22840

PALMITIC ACID[M+H]+

LINOLEIC ACID[M+H]+

PALMITIC ACID[M+NH4]+

LINOLEIC ACID[M+NH4]+

OLEIC ACID[M+NH4]+

zoom m/z 250 - 310

FFA are formed by heat-induced decomposition of

TAGs

OLEIC ACID[M+H]+

MS[1];1.161..1.226;-1.0*MS[1];1.280..1.305; / ESI+ / 20080327_SMPL1

100 200 300 400 500 600 700 800 900 1000m/z

0

10

20

30

40

50

Intensity (53000)x103

902.80217

603.52369

876.78826

903.80598

577.50761

604.52704

300.28567904.81267

874.77212411.39026

428.41634409.37558283.25981

397.37614 605.53391

339.28483905.81777121.06356 850.77295460.40515

169.08399575.49223265.24844

638.56034

848.75652143.10375492.39474

918.79683639.56475493.39059932.83527

804.65857764.65900640.56840

VIRGIN OLIVE OIL – DART positive mass spectrum

MS[1];1.161..1.226;-1.0*MS[1];1.280..1.305; / ESI+ / 20080327_SMPL1

830 840 850 860 870 880 890 900 910 920m/z

0

10

20

30

40

50

Intensity (53000)x103

902.80217

876.78826

903.80598

877.79200

904.81267

900.78660

874.77212

878.79777

905.81777850.77295

898.77137851.77835848.75652 872.75676 885.77583

918.79683906.82251886.77858857.74721

859.76004 892.78342 907.82448846.73857

PPL

zoom m/z 825 - 920

PPL

PLL

POL

POO

PSO

LLO

LOO

OOO

SOO

SSO

TAGs are detected as [M+NH4]+

m/z

MS[1];1.172..1.224;-1.0*MS[1];1.131..1.134; / ESI+ / 20080404_SMPL2

200 400 600 800 1000m/z

0

100

200

Intensity (250000)x103

902.82343900.80768

898.79193195.06811

903.82637

603.53673896.77583

904.83115874.79130159.10278212.09508 872.77618601.52033 604.53975141.09257 298.27530 916.80068397.38353

870.76074577.52025 605.54566 792.67815127.07741

AUTOOXIDATION OF RAPESEED OIL – DART POSITIVE SPECTRA, 300°C

MS[1];1.311..1.340;-1.0*MS[1];1.278..1.279; / ESI+ / 20080404_SMPL1

0

100

200

Intensity (250000)x103

195.06810

902.82547

898.79463

903.82940

212.09470896.77918 904.83495177.05622 603.53884

872.78018397.38522905.84028300.29173

431.38977 638.57692151.07533 577.52298 792.68308

FRESH SUNFLOWER OIL (PEROXIDE VALUE = 0.17)

SUNFLOWER OIL OXIDIZED IN MICROWAVE OVEN FOR 25´

(PEROXIDE VALUE = 27.31)

MS[1];1.560..1.606;-1.0*MS[1];1.651..1.659; / ESI+ / 20080401_SMPL2

0

100

200

Intensity (220000)x103

902.83503

903.83664876.81803

603.54516904.84198

874.80156

577.52839 604.54797905.84728409.39106

850.80103605.55584

339.29877918.82604575.51335460.42209191.18731

300.29606121.07013

804.68756

EXTRAVIRGIN (a) vs. POMACE OLIVE OIL (b), m/z 100 - 1000

MS[1];1.286..1.319;-1.0*MS[1];1.213..1.223; / ESI+ / 20080404_SMPL3

200 400 600 800 1000m/z

0

100

200

Intensity (220000)x103

896.77443

872.77526 900.80295

902.81763

601.51933903.82286870.75937397.38443

912.76939604.53931298.27594263.23981 846.74041431.38553 764.64615

(a)

(b)

MS[1];1.560..1.606;-1.0*MS[1];1.651..1.659; / ESI+ / 20080401_SMPL2

0

100

200

Intensity (220000)x103

902.83503

903.83664876.81803

877.82148 904.84198900.81646

874.80156

878.82606 905.84728850.80103898.80036

872.78615 918.82604906.84850879.82910 934.82643852.80730846.76452

MS[1];1.286..1.319;-1.0*MS[1];1.213..1.223; / ESI+ / 20080404_SMPL3

820 840 860 880 900 920 940m/z

0

100

200

Intensity (220000)x103

896.77443

872.77526900.80295

874.78857

902.81763894.75854

903.82286870.75937 877.80075848.77364912.76939855.74741 892.75319846.74041 928.82074

932.84465820.68615

EXTRAVIRGIN (a) vs. POMACE OLIVE OIL (b), m/z 820 - 950

(a)

(b)

DART positive mass spectra – various edible oils m/z 100-1000MS[1];1.161..1.226;-1.0*MS[1];1.280..1.305; / ESI+ / 20080327_SMPL1

100 200 300 400 500 600 700 800 900 1000m/z

0

10

20

30

40

50

Intensity (53000)x103

902.80217

603.52369

876.78826

903.80598

577.50761

604.52704

300.28567904.81267

874.77212411.39026

428.41634409.37558283.25981

397.37614 605.53391

339.28483905.81777121.06356 850.77295460.40515

169.08399575.49223265.24844

638.56034

848.75652143.10375492.39474

918.79683639.56475493.39059932.83527

804.65857764.65900640.56840

MS[1];0.610..0.652;-1.0*MS[1];0.062..0.066; / ESI+ / 20080327_SMPL3

100 200 300 400 500 600 700 800 900 1000m/z

0

20

40

60

80

100

120

140

160Intensity (160000)x10

3

879.72880

881.74263

601.50626

599.49132

153.12515

882.74659

603.52052

883.75598

855.72925575.49074

281.24387 397.37493

900.78217

298.27001263.23305

604.52489309.27406

157.11994 901.78684617.50059

902.79489398.37863311.28914

634.52834169.12084903.80213743.60614

171.11006491.36684

636.54304551.49032

854.71954939.81134

MS[1];1.469..1.541;-1.0*MS[1];0.165..0.185; / ESI+ / 20080327_SMPL4

100 200 300 400 500 600 700 800 900 1000m/z

0

10

20

30

40

50

60

70

80

90

100Intensity (100000)x10

3

181.09221

902.82082

283.26847

603.53756900.80590

300.29352

182.09330

125.09881

898.79058903.82543

281.25212601.52131

127.11396 604.54071397.38635

180.08298 279.23654 383.37015 876.80590904.83174265.25662

183.07936 301.29702 577.52114872.77673605.54709199.10315 398.38906

905.83666381.35436 575.50697257.24789

MS[1];0.796..0.831;-1.0*MS[1];0.703..0.719; / ESI+ / 20080327_SMPL5

100 200 300 400 500 600 700 800 900 1000m/z

0

10

20

30

40

50

60

70

80

90

100

Intensity (105000)x103

601.52197281.25286

263.24209

603.53783

575.50699

283.26760

881.76479

604.54081 879.75161

855.75044

883.77903

605.55088

898.78987153.13009 337.27897

355.28899617.51782

409.38352902.81983

257.24810413.37995 551.50623

245.23069618.52240

903.82521441.37543211.17217 503.37835848.77632

443.38779 634.54780905.83663783.63753743.62718

MS[1];0.650..0.710;-1.0*MS[1];0.589..0.595; / ESI+ / 20080327_SMPL6

100 200 300 400 500 600 700 800 900 1000m/z

0

10

20

30

40

50

Intensity (56000)x103

439.38271

495.44431

383.31999

467.41310411.35080

257.21719

551.50615

201.15896

523.47442

355.28853

577.52197313.27804145.12636

656.58649712.65161

600.52369

768.71592684.61872

794.73166173.13900

796.74525 850.79474

851.79839

OLIVE OILOLIVE OIL

SUNFLOWER OILSUNFLOWER OIL

RAPESEED OILRAPESEED OIL

PUMPKIN SEED OILPUMPKIN SEED OIL

COCONUT FATCOCONUT FAT

MS[1];1.161..1.226;-1.0*MS[1];1.280..1.305; / ESI+ / 20080327_SMPL1

830 840 850 860 870 880 890 900 910 920m/z

0

10

20

30

40

50

Intensity (53000)x103

902.80217

876.78826

903.80598

877.79200

904.81267

900.78660

874.77212

878.79777

905.81777850.77295

898.77137851.77835848.75652 872.75676 885.77583

918.79683906.82251886.77858857.74721

859.76004 892.78342 907.82448846.73857

DART+ various edible oils, m/z 820-920 - TRIACYLGLYCEROLS

MS[1];0.610..0.652;-1.0*MS[1];0.062..0.066; / ESI+ / 20080327_SMPL3

830 840 850 860 870 880 890 900 910 920m/z

0

20

40

60

80

100

120

140

160Intensity (160000)x10

3

879.72880

881.74263

882.74659

883.75598 898.76725

896.75293

855.72925

900.78217

884.76096856.73323

872.75512

857.74127901.78684

885.76879

902.79489

858.74550886.77352 903.80213 912.75370

914.76277854.71954 859.75183 893.71016825.64572 844.67120910.73942869.72303

MS[1];1.469..1.541;-1.0*MS[1];0.165..0.185; / ESI+ / 20080327_SMPL4

830 840 850 860 870 880 890 900 910 920m/z

0

5

10

15

20

25

30

35

40Intensity (40000)x10

3

902.82082

900.80590

898.79058

903.82543

876.80590904.83174

896.77559874.79093

881.76552

883.77924872.77673

885.79386905.83666

894.76138

MS[1];0.796..0.831;-1.0*MS[1];0.703..0.719; / ESI+ / 20080327_SMPL5

830 840 850 860 870 880 890 900 910 920m/z

0

5

10

15

20

25

30

35

40

Intensity (42000)x103

881.76479

879.75161

855.75044

883.77903

898.78987

900.80520

856.75556

872.77672

896.77488

884.78409

857.76372902.81983

885.79306

903.82521858.76881

904.83336886.79809

848.77632

859.77602895.74973

905.83663 914.79044870.75116 888.78756860.77843

MS[1];0.650..0.710;-1.0*MS[1];0.589..0.595; / ESI+ / 20080327_SMPL6

500 550 600 650 700 750 800 850 900m/z

0

2

4

6

8

10

12

14

16

18

20

22Intensity (22000)x10

3

551.50615

523.47442

577.52197

552.50939 656.58649

712.65161

600.52369

628.55516768.71592

524.47814 684.61872

740.68417 794.73166

738.66732601.52604549.49137 657.59133

796.74525850.79474

769.71843824.77723685.62166603.53763 629.55932

766.70029822.76262 851.79839682.60422

792.71651 876.80844820.74532 825.78153710.63577852.80343764.68368 877.81236

658.59326686.62526654.57094

OLIVE OILOLIVE OIL

SUNFLOWER OILSUNFLOWER OIL

RAPESEED OILRAPESEED OIL

PUMPKIN SEED OILPUMPKIN SEED OIL

COCONUT FATCOCONUT FAT

IS AUTHENTICATION BASED ON IS AUTHENTICATION BASED ON TGA TGA PROFILE PROFILE OBTAINED BOBTAINED BY DART POSSIBLE?Y DART POSSIBLE?

Principal Component Analysis (PCA)

STATISTICA v 7.0 software PARAMETERS: relative intensities of [M+NH4]+ ions corresponding to TAGs TAGs: PPL, PPS, LLL, POO

Ion intensity %

sample ID PPL PPS POO LLL SUM PPL PPS POO LLL

OLIV 1 20608 12846 322910 6332 362696 5,68 3,54 89,03 1,75

OLIV 2 41778 12029 533274 10115 597196 7,00 2,01 89,30 1,69

OLIV 3 69172 33729 1065457 21603 1189961 5,81 2,83 89,54 1,82

RAP 1 24840 4943 196722 228035 454540 5,46 1,09 43,28 50,17

RAP 2 33018 7790 297480 395044 733332 4,50 1,06 40,57 53,87

RAP 3 27831 7832 278630 410056 724349 3,84 1,08 38,47 56,61

SUN 1 24381 2948 68735 553008 649072 3,76 0,45 10,59 85,20

SUN 2 44120 4539 117577 846175 1012410 4,36 0,45 11,61 83,58

SUN 3 40267 3927 100578 560417 705189 5,71 0,56 14,26 79,47

PUM 1 109035 13410 351652 453755 927850 11,75 1,45 37,90 48,90

PUM 2 116889 12194 450107 555663 1134853 10,30 1,07 39,66 48,96

PUM 3 74094 7499 190976 240820 513390 14,43 1,46 37,20 46,91

COC 1 62659 46259 67906 3795 180619 34,69 25,61 37,60 2,10

COC 2 82780 73501 97024 7205 260510 31,78 28,21 37,24 2,77

COC 3 111532 86232 113997 8343 320104 34,84 26,94 35,61 2,61

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

Fa cto r 1 : 6 2 .7 1 %

-1 .5

-1 .0

-0 .5

0 .0

0 .5

1 .0

1 .5

2 .0

2 .5

Fa

ctor 2

: 36

.31

%

Principal Component Analysis (PCA)Principal Component Analysis (PCA)

Factor 1:Factor 1: PPL, PPS, LLL PPL, PPS, LLLFactor 2:Factor 2: POO POO

OLIVE OILOLIVE OIL

SUNFLOWER OILSUNFLOWER OIL

RAPESEED OILRAPESEED OIL

PUMPKIN SEED OILPUMPKIN SEED OIL

COCONUT FATCOCONUT FAT

MS[1];0.695..0.706;-1.0*MS[1];0.664..0.669; / ESI+ / 20080401_SMPL9

100 200 300 400 500 600 700 800 900 1000m/z

-10

0

10

20

30

40

50

60

70

80

Intensity (88423)x103

898.81927

896.80575

210.07359900.83415

634.56481

872.80574

901.83941636.57957

397.39989

903.85342601.54131193.04613 638.59615431.40718

298.28782

575.52424 904.86402337.28885848.80411639.59896211.07496 432.41506175.03349 905.86880

640.60845 790.68947

MS[1];0.695..0.706;-1.0*MS[1];0.664..0.669; / ESI+ / 20080401_SMPL9

850 860 870 880 890 900 910 920 930 940m/z

0

10

20

30

40

50

60

70

80

Intensity (88423)x103

898.81927

896.80575

900.83415

872.80574

874.81975901.83941

875.82287903.85342

904.86402877.83940

878.82974905.86880

850.81640 914.81604883.80391 906.87476856.77843 870.78378

Sunflower oil TAG

MS[1];0.244..0.255;-1.0*MS[1];0.212..0.217; / ESI+ / 20080406_OILS2

100 200 300 400 500 600 700 800 900 1000m/z

0

20

40

60

80

100

120

140

160

180

200

220

240

Intensity (243699)x103

298.29240

153.08585

299.29325

279.24784 431.40900

166.09705

124.04826 397.40278300.30438205.11117

372.33056

118.09509432.41414 634.57022

636.58514 898.82846617.54326112.05967 433.41619 638.60008 872.81238

MS[1];0.346..0.366;-1.0*MS[1];0.388..0.395; / ESI+ / 20080406_OILS2

850 860 870 880 890 900 910 920 930 940m/z

0

1000

2000

3000

4000

5000

6000

7000

8000

Intensity (8598)

898.84522

896.82024

899.85888

900.86054

901.85258

872.82932

873.83176

928.85559916.84721902.84705

930.86190902.90921918.85595914.84642

Sunflower seeds - direct sampling

TAG

Matrix components

Case studyCase study nno.o. 2 2

Traceability Traceability of honey origin of honey origin

GCxGC/TOF MS

DARTDART: : comparisoncomparison of of two two honey sampleshoney samples

Different origin

Different origin

Processing of measured data is not easy…..Processing of measured data is not easy…..Name Meas. Calc. Diff(u) Abund. GBL 85.0294 85.0290 0.0005 23.1410 Pyruvic_acid 87.0129 87.0082 0.0047 28.4476 Lactic_acid 89.0241 89.0239 0.0002 12.2362 Cresol 107.0463 107.0497 -0.0034 3.4462 Uracil 111.0156 111.0195 -0.0038 19.2750 Creatinine 112.0506 112.0511 -0.0004 71.6850 Succinic/fumaric/maleic acid 115.0058 115.0031 0.0026 39.3193 Methylmalonic_acid 117.0225 117.0187 0.0038 13.1083

Computer Computer analysisanalysis

STROBILURIN FUNGICIDES IN STROBILURIN FUNGICIDES IN GRAINSGRAINS

Case study no.Case study no. 33

Extraction time:

Maximum of 3 hours for 20 samplesMaximum of 3 hours for 20 samples

Working characteristics:

LODs<0.05 mg/kg (LOQs < 0.1 mg/kg)LODs<0.05 mg/kg (LOQs < 0.1 mg/kg)

Repeatability - %CV <40 Repeatability - %CV <40

WP6 Pesticides: target values for Strobilurin SPR bioassay

Can be these parameters also achieved by DART?

CONCLUSIONSCONCLUSIONS

The total time needed for analysis of one sample by novel The total time needed for analysis of one sample by novel

validated approach (SLE extraction) is 8 min.validated approach (SLE extraction) is 8 min.

The screening of strobilurins direct in milled wheat grains is The screening of strobilurins direct in milled wheat grains is

possible by analysis employing AccuTOF™DART™. possible by analysis employing AccuTOF™DART™.

All target strobilurins can be determined by novel, simple All target strobilurins can be determined by novel, simple

and fast approach at concentration levels below LODs inand fast approach at concentration levels below LODs in

Case study no. 4Case study no. 4

DART AccuTOFDART AccuTOF LC-plus system LC-plus system withwith LEAP HTC PAL LEAP HTC PAL auautosamplertosampler (1) (1) Sample is placed in sampling hole, Sample is placed in sampling hole, DIP-itDIP-itTMTM

sampler sticks are used for sample transfersampler sticks are used for sample transfer(1b)

(1a)

(2)(2)

(2) (2) Sampling stick is immersed into the Sampling stick is immersed into the samplesample for 4sfor 4s

(3)(3)

(3)(3) Sampling stick is transferred between the DART ion source and MS inlet, mass spectra are acquired for 7s

(4)(4)

(4)(4) Used stick Used stick disposeddisposed

TOTAL RUN TIME: TOTAL RUN TIME: 35 35 ss

GAS BEAM TEMPERATURE 250250°C°CDART-POSITIVE MASS SPECTRA OF COLA BEVERAGESDART-POSITIVE MASS SPECTRA OF COLA BEVERAGES

MS[1];0.369..0.395; / ESI+ / 20080128_SMPL1

150 200 250 300 350 400m/z

0

50

100

Intensity (149227)x103

195.10521

196.09934127.04490

180.09511

MS[1];0.211..0.220; / ESI+ / 20080128_SMPL2

100 150 200 250 300 350 400m/z

0

50

100

Intensity (130000)x103

195.10296

137.13850196.09896

133.07056

MS[1];0.809..0.846; / ESI+ / 20080125_SMPL4

100 150 200 250 300 350 400m/z

0

20

40

60

80

100

120

Intensity (130000)x103

195.10037

196.09272177.11370275.11599

151.07775

123.09333

MS[1];0.669..0.693; / ESI+ / 20080125_SMPL3

100 150 200 250 300 350 400m/z

0

20

40

60

80

100

120

Intensity (130000)x103

195.09563

275.11509

196.09207

123.09278

137.10625

COCA-COLACOCA-COLA COCA-COLA COCA-COLA LIGHTLIGHT

PEPSI-COLAPEPSI-COLA PEPSI-COLA LIGHTPEPSI-COLA LIGHT

? ?

caffeine caffeine

COCA marker?

GAS BEAM TEMPERATURE 335050°C

MS[1];0.210..0.233; / ESI+ / 20080128_SMPL5

100 150 200 250 300 350 400m/z

0

20

40

60

80

100

120

Intensity (130000)x103

127.05653 195.11132

253.08700271.09443

235.07288

189.06424289.10344

196.09976

145.05599

207.07497

126.05657 223.06992 321.13180

163.06619325.12490 379.11801

290.10722

MS[1];0.546..0.571; / ESI+ / 20080128_SMPL6

100 150 200 250 300 350 400m/z

0

20

40

60

80

100

120

Intensity (130000)x103

195.10699

295.14051196.10005

137.13847

133.07005 164.00806

296.14362

MS[1];0.467..0.508; / ESI+ / 20080128_SMPL7

100 150 200 250 300 350 400m/z

0

20

40

60

80

100

120

Intensity (130000)x103

195.10982

253.08413

271.09405127.04574235.07317

196.10000 289.10440

189.06384

137.13910 343.09721321.13282 379.12005

MS[1];0.501..0.511;-1.0*MS[1];0.522..0.523; / ESI+ / 20080128_SMPL8

100 150 200 250 300 350 400m/z

0

20

40

60

80

100

120

Intensity (130000)x103

195.10988

196.10091

295.14109

180.10949

164.00862

127.04567

COCA-COLACOCA-COLA COCA-COLA LIGHT

PEPSI-COLAPEPSI-COLA PEPSI-COLA PEPSI-COLA LIGHTLIGHT

HIGH S

UGAR CONTENT (~

100g/L)

SUGAR CONTENT IS

VERY L

OW (<

0.1g/L)

HEAT-INDUCED HEAT-INDUCED SUGAR FRAGMENTATION IN NORMAL COLASSUGAR FRAGMENTATION IN NORMAL COLAS

MS[1];0.467..0.508; / ESI+ / 20080128_SMPL7

100 150 200 250 300 350 400m/z

0

20

40

60

80

100

120

Intensity (130000)x103

195.10982

253.08413

271.09405127.04574235.07317

196.10000 289.10440

189.06384

137.13910 343.09721321.13282 379.12005

DETECTION AND IDENTIFICATION OF ASPARTAME IN “LIGHT” PRODUCTSMS[1];0.210..0.233; / ESI+ / 20080128_SMPL5

100 150 200 250 300 350 400m/z

0

20

40

60

80

100

120

Intensity (130000)x103

127.05653 195.11132

253.08700271.09443

235.07288

189.06424289.10344

196.09976

145.05599

207.07497

126.05657 223.06992 321.13180

163.06619325.12490 379.11801

290.10722

MS[1];0.546..0.571; / ESI+ / 20080128_SMPL6

100 150 200 250 300 350 400m/z

0

20

40

60

80

100

120

Intensity (130000)x103

195.10699

295.14051196.10005

137.13847

133.07005 164.00806

296.14362

MS[1];0.501..0.511;-1.0*MS[1];0.522..0.523; / ESI+ / 20080128_SMPL8

100 150 200 250 300 350 400m/z

0

20

40

60

80

100

120

Intensity (130000)x103

195.10988

196.10091

295.14109

180.10949

164.00862

127.04567

COCA-COLA COCA-COLA LIGHT

PEPSI-COLA PEPSI-COLA LIGHT

277.11741

GAS BEAM TEMPERATURE 335050°C

MS[1];0.467..0.508; / ESI+ / 20080128_SMPL7

100 150 200 250 300 350 400m/z

0

20

40

60

80

100

120

Intensity (130000)x103

195.10982

253.08413

271.09405127.04574235.07317

196.10000 289.10440

189.06384

137.13910 343.09721321.13282 379.12005

MS[1];0.210..0.233; / ESI+ / 20080128_SMPL5

100 150 200 250 300 350 400m/z

0

20

40

60

80

100

120

Intensity (130000)x103

127.05653 195.11132

253.08700271.09443

235.07288

189.06424289.10344

196.09976

145.05599

207.07497

126.05657 223.06992 321.13180

163.06619325.12490 379.11801

290.10722

MS[1];0.546..0.571; / ESI+ / 20080128_SMPL6

100 150 200 250 300 350 400m/z

0

20

40

60

80

100

120

Intensity (130000)x103

195.10699

295.14051196.10005

137.13847

133.07005 164.00806

296.14362

MS[1];0.501..0.511;-1.0*MS[1];0.522..0.523; / ESI+ / 20080128_SMPL8

100 150 200 250 300 350 400m/z

0

20

40

60

80

100

120

Intensity (130000)x103

195.10988

196.10091

295.14109

180.10949

164.00862

127.04567

COCA-COLA COCA-COLA LIGHT

PEPSI-COLA PEPSI-COLA LIGHT

277.11741

DETECTION AND IDENTIFICATION OF ASPARTAME IN “LIGHT” PRODUCTS

GAS BEAM TEMPERATURE 335050°C

MS[1];0.467..0.508; / ESI+ / 20080128_SMPL7

100 150 200 250 300 350 400m/z

0

20

40

60

80

100

120

Intensity (130000)x103

195.10982

253.08413

271.09405127.04574235.07317

196.10000 289.10440

189.06384

137.13910 343.09721321.13282 379.12005

MS[1];0.210..0.233; / ESI+ / 20080128_SMPL5

100 150 200 250 300 350 400m/z

0

20

40

60

80

100

120

Intensity (130000)x103

127.05653 195.11132

253.08700271.09443

235.07288

189.06424289.10344

196.09976

145.05599

207.07497

126.05657 223.06992 321.13180

163.06619325.12490 379.11801

290.10722

MS[1];0.546..0.571; / ESI+ / 20080128_SMPL6

100 150 200 250 300 350 400m/z

0

20

40

60

80

100

120

Intensity (130000)x103

195.10699

295.14051196.10005

137.13847

133.07005 164.00806

296.14362

MS[1];0.501..0.511;-1.0*MS[1];0.522..0.523; / ESI+ / 20080128_SMPL8

100 150 200 250 300 350 400m/z

0

20

40

60

80

100

120

Intensity (130000)x103

195.10988

196.10091

295.14109

180.10949

164.00862

127.04567

COCA-COLA COCA-COLA LIGHT

PEPSI-COLA PEPSI-COLA LIGHT

MS[1];0.329..0.344; / ESI+ / 20080129_SMPL1

270 280 290 300 310m/z

0

100

200

300

400

Area (486304)x103

295.12968

296.13086

277.11741

278.10914

MS[1];0.321..0.348; / ESI+ / 20080129_SMPL1

270 280 290 300 310m/z

0

100

200

300

400

Area (497691)x103

295.12984

296.13114

277.11726

278.10806

295.12984

277.11726

277.11741

295.12968

ASPARTAME E951

meas. mass 295.1298

calc. mass 295.1294

difference +1.51ppm

[M-H2O+H]+

[M+H]+

[M+H]+

MS[1];0.865..0.895; / ESI+ / 20080128_SMPL12

100 150 200 250 300 350 400m/z

0

20

40

60

80

100

120

Intensity (130000)x103

195.11482

196.10203

127.04609

295.14354164.00930

MS[1];0.421..0.502;-1.0*MS[1];0.503..0.504; / ESI+ / 20080128_SMPL11

100 150 200 250 300 350 400m/z

0

20

40

60

Intensity (76789)x103

195.10382

127.04821

253.08425

271.09503235.07264

189.06482289.10535145.05699

315.10421173.09991 361.11046

MS[1];0.555..0.607; / ESI+ / 20080128_SMPL10

100 150 200 250 300 350 400m/z

0

20

40

60

80

100

120

Intensity (130000)x103

195.10356

295.14244

196.10049164.00913

137.13920

MS[1];0.311..0.333; / ESI+ / 20080128_SMPL9

100 150 200 250 300 350 400m/z

0

20

40

60

80

100

120

Intensity (130000)x103

195.11695127.04968253.09184

271.09562

235.07846

189.06506

289.10397

343.09629

361.10677315.09898

145.05639 173.09947

COCA-COLA COCA-COLA LIGHT

PEPSI-COLA PEPSI-COLA LIGHT

ASPARTAME

ASPARTAME

GAS BEAM TEMPERATURE 445050°C

Coffee - qualityCoffee - quality,, authenticity authenticity

Example no Example no 33

MS[1];0.597..0.608; / ESI+ / 20080125_SMPL4

260 280 300 320 340 360 380 400m/z

0

2

4

6

8

10

12

14

16

18

20

22

24

Intensity (24939)x103

275.11657

327.20489 389.17218

283.17693

371.23050

255.12331

257.24976390.17652

MS[1];0.679..0.690; / ESI+ / 20080125_SMPL3

260 280 300 320 340 360 380 400m/z

2

4

6

8

10

12

14

16

18

20

22

24

Intensity (24961)x103

275.11501

276.11924

389.17114279.16366

283.17493255.12275 327.20298361.27811

321.14738

MS[1];0.597..0.608; / ESI+ / 20080125_SMPL4

260 280 300 320 340 360 380 400m/z

0

2

4

6

8

10

12

14

16

18

20

22

24

Intensity (24939)x103

275.11657

327.20489 389.17218

283.17693

371.23050

255.12331

257.24976390.17652

Arabica Roasted

Robusta Roasted Robusta Roasted(Douwe Egberts)

reference match

No match

SPME preconcentration – SPME preconcentration – another challenge!!!another challenge!!!

MS[1];1.923..1.976; / ESI+ / 20080129_SMPL4

100 150 200 250 300 350 400 450 500 550m/z

0

10

20

30

40

50

60

70

Intensity (70000)x103

89.06596

75.08532

90.06969 371.12527223.08086117.10025 445.14986177.12490

373.11881297.10207355.09426225.07013

Blank SPME fiber (PDMS/CX/DVB, Supelco)

Bleed: siloxans

WHAWHATT ABOUT USING SPME FOR ABOUT USING SPME FOR SAMPLE FLAVOUR COMPONENTS SAMPLE FLAVOUR COMPONENTS COLLECTION / PRE.CONCENTRATION??COLLECTION / PRE.CONCENTRATION??

MS[1];0.259..0.279; / ESI+ / 20080129_SMPL3

100 150 200 250 300 350 400 450 500 550m/z

0

10

20

30

40

50

60

70

Intensity (70300)x103

81.03992

98.10317

127.04709

161.07056

100.11893

160.08553

175.09728189.11335

190.10231

204.11824 371.12327

236.14312 275.13111 445.14831372.12754

Coffee (Nescafe Gold) 1g of matrix, HS-SPME (40°C, 60 min, PDMS/CX/DVB)

bleed

coffee volatiles

MS[1];0.264..0.293; / ESI+ / 20080129_SMPL3

80 100 120 140 160 180 200 220 240m/z

0

10

20

30

40

50

60

70

Intensity (70000)x103

81.04171 127.04733

96.05144

98.10277

161.07101

109.08318

95.06595

100.11877160.08558

113.06757175.09743123.09897

189.1133985.03399

129.06215

139.09329176.08793 190.10163148.08532 165.10705

156.11213122.07035 203.12821195.10213

180.13511166.10736 205.10902 219.12607 231.12856

Coffee (Nescafe Gold) ZOOM (m/z 75-245) 1g of matrix, HS-SPME (40°C, 60 min, PDMS/CX/DVB)

pyrazine

methylpyrazine

caffeine

2-(2-furfuryl)pyrazine

2-acetylpyrrole

BEERS PROFILINGBEERS PROFILING

Example no Example no 55

MS[1];0.726..0.731; / ESI- / 20080205_SMPL6

50 100 150 200 250 300 350 400 450 500m/z

0

10

20

30

40

50

60

70

80

90

100

Intensity (100000)x103

89.02437

128.03245

117.01644

161.04149101.02213 269.08043179.05180

129.0212887.00621215.02673 308.08797 361.19237

181.06682 347.17585271.09602 395.10908251.07498

DART-DART- (350°C, 2400V, PV 600V)(350°C, 2400V, PV 600V)

m/z 250400

MS[1];0.638..0.644; / ESI- / 20080205_SMPL7

50 100 150 200 250 300 350 400 450 500m/z

0

10

20

30

40

50

60

70

80

90

100

Intensity (100000)x103

89.03210

269.08242

179.05216

117.01670

128.03203101.02187

71.01034

143.10480

270.08372

308.08983215.02771347.17636

361.19118

PRIMATOR: Light beer – porter (alc 9% vol.)

PRIMATOR: Dark beer – porter (alc 10.5% vol.)

MS[1];1.410..1.424; / ESI- / 20080205_SMPL8

50 100 150 200 250 300 350 400 450 500m/z

-0

10

20

30

40

50

60

70

80

90

100

Intensity (100000)x103

89.02559

128.03345

124.03546

117.01740

114.05311361.19282

91.03758

87.00634 347.17748

101.02231 143.10428

269.08269179.05367

362.1966973.02556181.06814

329.22502308.09338210.07305271.09830

240.08128377.18773

PRIMATOR: Light beer – lager (alc 5% vol.)

MS[1];0.716..0.766; / ESI+ / 20080204_SMPL6

60 80 100 120 140 160 180 200 220 240m/z

0

10

20

30

40

50

60

Intensity (60000)x103

116.07892

89.06748 130.05354

145.05138

93.09751

105.07718

216.1229881.04271

73.07489

166.09312200.12530

70.07551 176.09215146.07910 218.12376 248.12142

MS[1];0.720..0.773; / ESI+ / 20080204_SMPL7

60 80 100 120 140 160 180 200 220 240m/z

0

10

20

30

40

50

60

Intensity (60000)x103

127.04469 145.0520573.07541

85.03718

97.03636

103.08255

216.12366

130.05368

105.07718

158.08384

219.08789180.09805

163.06178 200.12550

214.1391672.09100 232.14016191.09152

MS[1];0.334..0.387; / ESI+ / 20080204_SMPL8

60 80 100 120 140 160 180 200 220 240m/z

0

10

20

30

40

Intensity (40000)x103

89.06791

103.08311

73.07509

75.05402 116.07663

130.05376145.05178

76.0501481.04312

173.15371

70.07590 166.09237 180.10244 201.16460 216.12735 234.11630

MS[1];1.298..1.347; / ESI+ / 20080204_SMPL10

60 80 100 120 140 160 180 200 220 240m/z

0

10

20

30

40

50

60

Intensity (60000)x103

116.07703

127.04348

105.07864

130.05383

145.05203

81.04274

89.0663599.05199

162.0920075.05384 176.09296

152.0750570.07582 216.12354

180.09280 231.11132242.10964

PORTER (Dark)PORTER (Dark) LAGERLAGER

TRAPISTICTRAPISTICPORTER (Light)PORTER (Light)

DART-DART- (350°C, 2400V, PV 600V)(350°C, 2400V, PV 600V)

MS[1];0.975..0.983; / ESI- / 20080205_SMPL9

260 280 300 320 340 360 380 400m/z

0

10

20

30

40

50

60

70

Intensity (70000)x103

361.19161

347.17587

269.08120

362.19504

348.18026 377.18612

271.09680 363.18539317.16471379.19882359.17667

MS[1];1.554..1.567; / ESI- / 20080205_SMPL10

260 280 300 320 340 360 380 400m/z

0

10

20

30

40

50

60

70

Intensity (70000)x103

361.19296

347.17745

308.09119

362.19636329.22430

269.08160

379.20236348.18020

267.08339 310.10606 365.19053330.22771294.11268

271.09744 306.08436 380.20385327.21002

MS[1];0.334..0.387; / ESI+ / 20080204_SMPL8

60 80 100 120 140 160 180 200 220 240m/z

0

10

20

30

40

Intensity (40000)x103

89.06791

103.08311

73.07509

75.05402 116.07663

130.05376145.05178

76.0501481.04312

173.15371

70.07590 166.09237 180.10244 201.16460 216.12735 234.11630

MS[1];1.298..1.347; / ESI+ / 20080204_SMPL10

60 80 100 120 140 160 180 200 220 240m/z

0

10

20

30

40

50

60

Intensity (60000)x103

116.07703

127.04348

105.07864

130.05383

145.05203

81.04274

89.0663599.05199

162.0920075.05384 176.09296

152.0750570.07582 216.12354

180.09280 231.11132242.10964

Switching operation mode enables higher degree of confirmation.

LAGERDART+

TRAPISTICDART+

LAGERDART-

TRAPISTICDART-

Head Space SPME(DVB/CX/PDMS)

45 minutes at 75°C(pre-incubation 5 minutes)

Direct SPME(DVB/CX/PDMS)

45 minutes at 75°C(pre-incubation 10 minutes)

Analytical scheme - volatiles profiling

DART+ (250°C, 2400V, PV 600V)

3 ml of beer 9 ml of beer

MS[1];0.175..0.237;-1.0*MS[1];0.098..0.133; / ESI+ / 20080404_js2

50 100 150 200 250 300 350 400 450 500m/z

0

50

100

Intensity (120000)x103

363.20446349.18569

364.20315

105.06545

339.23757

223.08841

401.24879

293.12643173.14639 415.26074331.17933199.16142 467.25615

365.20457145.11585 281.12652 431.25678

275.15962 453.24218224.09233 468.2589993.08679

81.02993

MS[1];0.211..0.239;-1.0*MS[1];0.183..0.202; / ESI+ / 20080402_js4

0

20

40

60

80

100

120Intensity (120000)x10

3

105.08000 199.18571173.16689

89.06691

145.13326

205.21080

106.0819581.04239 277.23627

174.17037137.14140 209.15276 305.26865163.14559267.19377 371.12599345.32437 445.14792

DART+ (250°C, 2400V, PV 600V)Westmalle: trapistic beer (alc 9.5% vol.)

Head Space SPME(DVB/CX/PDMS)

Direct SPME(DVB/CX/PDMS)

MS[1];0.252..0.279;-1.0*MS[1];0.209..0.232; / ESI+ / 20080404_js5

50 100 150 200 250 300 350 400 450 500m/z

0

50

100

Intensity (120000)x103

363.22505349.20735

364.22515

339.25833223.10198

399.25728417.26766

293.14379

307.15943

173.15701151.07810105.07244116.07386 281.14987 431.28235

331.19629145.12497 365.22654265.10630180.10462

433.28140 467.28351319.21285235.09834104.07325 489.32066

MS[1];0.194..0.238;-1.0*MS[1];0.125..0.163; / ESI+ / 20080402_js8

0

20

40

60

80

100

120Intensity (120000)x10

3

173.16326

145.12983

105.07624

201.19569

199.18014

205.2060489.06322

174.16566111.12304 229.22855127.11801 163.14107 371.11744

279.17331 445.13845267.18518 345.31537

81.05659 372.11967305.25959

DART+ (250°C, 2400V, PV 600V)Plzeň: lager (alc 4,4 % vol.)

Head Space SPME(DVB/CX/PDMS)

Direct SPME(DVB/CX/PDMS)

SPME beer profiling enables production origin differentiation!

MS[1];0.186..0.226;-1.0*MS[1];0.095..0.138; / ESI+ / 20080404_js1

0

20

40

60

80

100

120Intensity (120000)x10

3

127.03703

145.04750

85.02635173.15136

105.06835

363.20966

163.05826201.18094

349.19503

198.09668 216.12015 401.26002116.06910 265.0945781.03144 289.15372 317.19085

415.27301364.2127475.07693 231.10119

417.25724241.17586 399.24451307.13460447.26349

MS[1];0.175..0.237;-1.0*MS[1];0.098..0.133; / ESI+ / 20080404_js2

50 100 150 200 250 300 350 400 450 500m/z

0

50

100

Intensity (120000)x103

363.20446349.18569

364.20315

105.06545

339.23757

223.08841

401.24879

293.12643173.14639 415.26074331.17933199.16142 467.25615

365.20457145.11585 281.12652 431.25678

275.15962 453.24218224.09233 468.2589993.08679

81.02993

Chimay: trapistic beer (alc 8% vol.)

Westmalle: trapistic beer (alc 9.5% vol.)

SPME beer profiling enables production origin differentiation!

MS[1];0.252..0.279;-1.0*MS[1];0.209..0.232; / ESI+ / 20080404_js5

50 100 150 200 250 300 350 400 450 500m/z

0

50

100

Intensity (120000)x103

363.22505349.20735

364.22515

339.25833223.10198

399.25728417.26766

293.14379

307.15943

173.15701151.07810105.07244116.07386 281.14987 431.28235

331.19629145.12497 365.22654265.10630180.10462

433.28140 467.28351319.21285235.09834104.07325 489.32066

Plzeň: lager (alc 4,4 % vol.)

MS[1];0.302..0.331;-1.0*MS[1];0.261..0.285; / ESI+ / 20080404_js6

50 100 150 200 250 300 350 400 450 500m/z

0

50

100

Intensity (120000)x103

363.22795

105.07420

349.21056

173.15934

151.08021

364.22852

339.26110

145.12681

367.26019223.10325293.14674201.19082 417.27145

331.1994489.06019 281.17487 467.28731127.04327 431.28419399.2609481.03626 379.22266

265.12441 471.31706

Staropramen: lager (alc 5 % vol.)

MS[1];0.221..0.256;-1.0*MS[1];0.162..0.195; / ESI+ / 20080404_js3

0

20

40

60

80

100

120Intensity (120000)x10

3

363.20630105.06749

339.24246

127.03552

145.04577 417.24984

349.1917397.02554

151.07139 295.21722

364.2084685.02551

399.24004431.26129

173.14891 447.25779279.22254 375.20605297.23250

163.05729277.20570116.06830 216.11739 467.26316

331.1840275.07758180.09274

235.10151 479.25888

Budvar: lager (alc 5 % vol.)

Same technology.Different producers.

MS[1];0.302..0.331;-1.0*MS[1];0.261..0.285; / ESI+ / 20080404_js6

50 100 150 200 250 300 350 400 450 500m/z

0

50

100

Intensity (120000)x103

363.22795

105.07420

349.21056

173.15934

151.08021

364.22852

339.26110

145.12681

367.26019223.10325293.14674201.19082 417.27145

331.1994489.06019 281.17487 467.28731127.04327 431.28419399.2609481.03626 379.22266

265.12441 471.31706

MS[1];0.660..0.676;-1.0*MS[1];0.636..0.646; / ESI+ / 20080404_js4

0

20

40

60

80

100

120

Intensity (120000)x103

105.07144

127.04022

97.02970 151.07684 363.21773

339.2554585.02915 279.23259417.26347

297.24412 399.25374163.0654181.03375 431.27651173.15487 277.11613219.06643

465.26905

MS[1];0.175..0.237;-1.0*MS[1];0.098..0.133; / ESI+ / 20080404_js2

50 100 150 200 250 300 350 400 450 500m/z

0

50

100

Intensity (120000)x103

363.20446349.18569

364.20315

105.06545

339.23757

223.08841

401.24879

293.12643173.14639 415.26074331.17933199.16142 467.25615

365.20457145.11585 281.12652 431.25678

275.15962 453.24218224.09233 468.2589993.08679

81.02993

SPME beer profiling enables production technology differentiation!

LAGER

TRAPISTIC

LIGHT beer

Co

st of b

eer

DART is primarily a DART is primarily a small-moleculesmall-moleculess analysis technique analysis technique (with some exceptions)

SUMMARYSUMMARY

No sample preparation and No sample preparation and components separation neededcomponents separation needed

In situIn situ degradation (pyrolysis) of degradation (pyrolysis) of sample components may provide sample components may provide matrix-characteristic profilesmatrix-characteristic profiles

DARTDART is a dry technique and is a dry technique and DESIDESI is not is not

DESIDESI has proved to be very valuable with peptides and has proved to be very valuable with peptides and

proteins. proteins. DESI DESI forms multiple-charge ions and alkaline forms multiple-charge ions and alkaline

metal ions of these materials, metal ions of these materials, DDARTART does not. does not.

DART DART has not been very effective in producing even has not been very effective in producing even

single-charge ion peptides. Although it is still premature single-charge ion peptides. Although it is still premature

to say, it appears that to say, it appears that DESI DESI may suffer from some of the may suffer from some of the

ion suppression problems that have come to be ion suppression problems that have come to be

associated with electrospray ionisation.associated with electrospray ionisation.

DART DART versusversus DESI DESI ??

... concerns exist about MS contamination problem when using DESI

Thank you for your kind attention Thank you for your kind attention