®

Comparison of Two-Dimensional Gas Chromatography and Tandem Mass Spectrometry for Pesticide

Analysis of Herbal Teas

Michelle Misselwitz, Julie Kowalski, Jack Cochran

®

Herbal Teas – Ancient Medicine Nettle - Remedies for an assortment of ailments including anemia, high blood

pressure, rheumatism, arthritis, coughs and colds, congestion, urinary tract infections, and kidney and bladder problems.

Chamomile Tea - Soothes the stomach and relieves bloating and indigestion. Calms the mind and helps people relax and deal better with their stresses.

Ginger Tea - Stimulates and soothes the digestive system. Ginger has been known to aid people experiencing nausea.

Peppermint Tea - Helps you digest foods better and also reduces flatulence and digestive issues. Eases nausea and vomiting, especially if you suffer motion sickness.

Hibiscus Flower Tea (Sorrel) - Lower blood pressure, reduce high cholesterol and strengthen the immune system (it’s rich in Vitamin C.

Lemon Balm Tea - Effective tonic to calm nerves and anxiety.

Green Tea - the ‘wonder herb’ lowers cancer risk and contains potent antioxidants. Green tea also lowers blood pressure, prevents and fights tooth decay and dental

issues, and inhibits different viruses from causing illnesses.

®

Organochlorine

Organonitrogen

Pyrethroid

Triazole

Fungicide

Insecticide Herbicide

Synergist Acaricide

Plant Growth Regulator

Organophosphorus

®

Herbal Teas Targeted Pesticide Analysis

Wild Berry Zinger Ingredients: Hibiscus, rosehips, roasted chicory, orange peel,

blackberry leaves, natural flavors of black raspberries, strawberries, blueberries, red raspberries, cranberries and

cherries

Pau d’Arco A Traditional South American Herbal Tea

Contains: Pau d’Arco bark

Red Tea – Cinnamon Orange Ingredients: Rooibos, cinnamon, orange peel, natural cinnamon

and orange flavors

Everyday Detox Ingredients: roasted chicory root, dandelion root, schisandra fruit, lycium fruit, lycium fruit, licorice root, ginger rhizome, star anise

fruit, kukicha twig (85% Certified Organic Ingredients)

®

QuEChERS Performance Standards Mix A

Acephate Diazinon

Dichlorvos Dimethoate Malathion

Methamidophos Mevinphos Omethoate Chlorpyrifos Coumaphos

Fenthion Pirimiphos methyl Azinphos methyl

Mix C Carbaryl

Methiocarb Iprodione Metalaxyl Vinclozolin

Captan Myclobutanil Deltamethrin

Bifenthrin cis-Permethrin

Imazalil trans-Permethrin

Cyprodinil Fenpropathrin

Folpet Thiabendazole

Fenhexamid

Mix B Chlorothalonil

4,4'-DDT Dichlofluanid

Dicofol Endrin

o-Phenylphenol Propargite

Endosulfan sulfate Phosalone

gamma-BHC

Red = Tea leaves Purple = Hibiscus Teal = Citrus Italics = Chicory Blue = Ginger

®

QuEChERS – Extraction 1 g ground tea

+ 10 mL H2O

Soak 30 min

+ 10 mL Acetonitrile

+ QuEChERS GC/MS Internal Standard

+ Pesticide spike mix

Vortex 30 min

Add EN Buffer Salts 4 g magnesium sulfate

1 g sodium chloride 1 g trisodium citrate dihydrate 0.5 g disodium hydrogencitrate

sesquihydrate

Shake 1 min

Centrifuge 5 min

®

500 pg ISTD

Complex Samples

®

% Recoveries of Fortified Tea at 1000 ng/g (100 pg on-column) quantified using GC-MS

Pau d'Arco Tea Zinger Tea Red Tea Detox Tea

Acephate ND ND ND ND

o-Phenylphenol 86 84 87 89

Omethoate 120 ND ND ND Diazinone 93 79 91 94 Chlorothalonil 62 72 82 79

Vinclozoline 88 81 87 87 Carbaryl 94 80 91 95

Metalaxyl 84 84 86 91

Methiocarb 91 79 92 96

Malathion 100 80 89 93

Fenthion 87 81 89 89

Chlorpyrifos 88 76 90 88 Cyprodinil 80 59 82 80

Thiabendazole 44 54 48 ND Captan 97 86 100 120

Imazalil 81 82 84 100

Endosulfan sulfate 110 76 81 93 Propargite 94 73 101 ND

Iprodione 89 76 94 100 Bifenthrin 86 68 83 87

Fenpropathrin 100 76 90 89 cis-Permethrin 87 67 82 ND

Deltamethrin 92 71 95 110

®

Cartridge SPE Cleanup

1 mL extract

Combo SPE Cartridge, 6mL/500mg Carboprep®,

90/500mg PSA

Add MgSO4 to tube

Elute 15mL acetone: toluene (3:1)

®

Cartridge SPE Cleanup

1 mL extract

MgSO4

500 mg GCB

500 mg PSA

Elute 15 mL 3:1 Acetone:Toluene

Concentrate to1 mL

®

Dispersive SPE (dSPE cleanup)

1 mL extract

Shake 2 min

Centrifuge 5 min

Q252 Q213

Guide to Sorbents

Removes Sugars and fatty acids Primary secondary amine (PSA)

Sorbent

Octadecyl (C18) Lipids

Pigments and sterols Graphitized carbon black (GCB)

dSPE Cleanup

150 mg MgSO4, 50 mg PSA, 50 mg C18, 7.5 mg GCB

®

GCxGC vs GC-MS/MS

Chromatographic Separation Resolution!

Full Spectral Information!

Mass Spectrometer Separation Selectivity! Sensitivity!

®

GCxGC Schematic

Modulator

1st Dimension 2nd Dimension

From Injector

To Detector

Focuses effluent from primary column (cold jet) and “injects” this effluent

(hot jet) to secondary column

Fast detector to record 50-500 ms wide peaks

Orthogonal GC column stationary phases means two independent separation mechanisms

®

Modulator

1st Column 2nd

Column

Inlet

Detector

Linear Chromatogram

2n

d C

olu

mn

Fundamentals of GCxGC

Surface Plot Contour Plot

®

+ +

+

+

+ +

time m/z

110

245 89

+

+

+

+ +

+ +

+

+ +

+

+

+

+

+

Q1

+ + +

+

+

+

+ +

+ +

m/z

99

133

68

+ + +

+

+

+

+

+ + +

Q3 Q2

Fragment Ions

+

Triple Quadrupole

®

MSn for Signal-to-Noise Improvement

0 1 2 3 4 5 6

Stages of Analysis

Inte

nsi

ty

Signal

Noise

S/N

Sensitivity

®

GC X GC Conditions Injection

Temp: 250°C Injection:1 µL fast, splitless (1.0 min) Liner: Sky Single Taper

Column

Rxi Guard 1.0 m x 0.25 mm Rxi-5ms 30 m x 0.25 mm x 0.25 µm Rtx-200 1.0 m x 0.25 mm x 0.25 µm Column connector: SGE SilTite µ-Union

Conditions Oven: 70°C (1 min), 8°C/min to 330°C (6.5 min) Secondary Oven Offset: + 5°C Carrier: He, constant flow 1.4 mL/min Modulator Temperature Offset: 20°C Modulation Time: 2 sec

LECO Pegasus®

TOFMS Conditions

Transfer Line Temperature: 320°C

Source Temperature: 225°C

Electron Ionization: 70 eV

Stored Mass Range: 45 to 550 u

Acquisition Rate: 100 spectra/sec

GCxGC-TOFMS Conditions

®

GC-MS/MS Conditions GC Conditions

Injection

Temp: 250°C Injection:1 µL fast, splitless (1.0 min) Liner: Sky Single Taper with wool

Column

Rxi-5ms 30 m x 0.25 mm x 0.25 µm

Conditions Oven: 70°C (1 min), 8.7°C/min to 330°C (5 min) Carrier: He, constant flow 1.4 mL/min

Thermo TSQ 8000 GC-MS/MS

Transfer Line Temperature: 280°C

Source Temperature: 250°C

Electron Ionization: 70 eV

Acquisition: SRM, 3 per analyte

Total Scan Time: 0.150 sec

®

Liner choice : wool or no wool?

Wool No Wool

Better response for thermal labile pesticides

Better response for more active pesticides

Controlled sample introduction

Protects GC column from non-volatile residue

®

Complex Samples

After 28 tea injections!

Use wool in your splitless liner to protect

your GC column from non-volatile dirt

®

Methamidophos

Dichlorvos

No retention

gap

1 m retention

gap

No Wool - Retention Gap - better solvent focusing

®

Pau d’Arco A Traditional South American Herbal Tea

Contains: Pau d’Arco bark

1.0

m x

0.2

5 m

m x

0.2

5 µ

m R

tx-2

00

1.0 m x 0.25 mm Rxi Guard + 30 m x 0.25 mm x 0.25 µm Rxi-5ms

®

RT: 0.0 - 28.9

0 5 10 15 20 25

Time (min)

0

50

100

0

50

100

0

50

100

0

50

100

0

50

100

Relative

Abunda

nce 0

50

100

0

50

100

0

50

10011.2

11.0

12.2

12.3

16.3

16.416.2

17.1

17.017.2

17.7

17.9

22.8

22.922.6

25.0

25.2

25.3

16.915.8

17.7 21.7

22.418.412.228.611.18.0

NL: 6.94E4

m/z= 42.10-286.00 F: + c EI SRM ms2 136.000@cid8.00 [42.095-42.105] MS Pau_d_Arco_Spike_10ppbDUP_inj7

NL: 1.84E6

m/z= 42.10-286.00 F: + c EI SRM ms2 141.000@cid13.00 [115.095-115.105] MS Pau_d_Arco_Spike_10ppbDUP_inj7

NL: 3.04E4

m/z= 42.10-286.00 F: + c EI SRM ms2 263.900@cid39.00 [132.995-133.005] MS Pau_d_Arco_Spike_10ppbDUP_inj7

NL: 5.09E4

m/z= 42.10-286.00 F: + c EI SRM ms2 186.800@cid20.00 [123.995-124.005] MS Pau_d_Arco_Spike_10ppbDUP_inj7

NL: 2.56E5

m/z= 42.10-286.00 F: + c EI SRM ms2 168.100@cid10.00 [153.095-153.105] MS Pau_d_Arco_Spike_10ppbDUP_inj7

NL: 2.59E4

m/z= 42.10-286.00 F: + c EI SRM ms2 314.000@cid10.00 [244.995-245.005] MS Pau_d_Arco_Spike_10ppbDUP_inj7

NL: 1.30E5

m/z= 42.10-286.00 F: + c EI SRM ms2 183.100@cid10.00 [168.095-168.105] MS Pau_d_Arco_Spike_10ppbDUP_inj7

NL: 1.67E7

TIC MS Pau_d_Arco_Spike_10ppbDUP_inj7

Pau d’Arco A Traditional South American Herbal Tea

Contains: Pau d’Arco bark

30 m x 0.25 mm x 0.25 µm Rxi-5ms

®

% Recoveries of Spiked Pesticides in Pau d’Arco Tea (n=2)

Pesticide 1000 ng/g 100 ng/g

GC-MS/MS GCxGC-TOFMS GC-MS/MS GCxGC-TOFMS

Acephate 100 90 78 65

o-Phenylphenol 101 87 77 100

Omethoate 88 96 76 58

Diazinon 101 99 94 99

Chlorothalonil 56 71 65 58

Vinclozolin 96 90 92 84

Carbaryl 61 98 80 65

Metalaxyl 99 100 83 97

Methiocarb 72 100 94 73

Malathion 102 100 86 91

Fenthion 98 100 88 90

Chlorpyrifos 94 91 81 87

Cyprodinil 85 86 75 66

Thiabendazole 68 58 66 39

Captan 73 110 90 72

Imazalil 101 80 78 80

Endosulfan sulfate 88 95 87 82

Propargite 89 99 84 70

Iprodione 92 120 92 27

Bifenthrin 92 91 83 77

Fenpropathrin 96 96 93 85

cis-Permethrin 93 100 87 78

Deltamethrin 85 94 94 45

®

o-Phenylphenol

GCxGC - Spectral Deconvolution

50 100 150 200 250 300 350 400 450 500 550

200

400

600

800

1000 135

152

77

63

107

121 169 434 285 399 357 231

Caliper - sample "Pau d'Arco Tea extract:1", 786 , 0.790 sec , sec to 786 , 0.790 sec , sec - 150 , 0.000 sec , sec to 150 , 0.000 sec , sec

50 100 150 200 250 300 350 400 450 500 550

200

400

600

800

1000 65

169

141

115

87

47 434 285 356

Peak True - sample "Pau d'Arco Tea extract:1", peak 292, at 786 , 0.790 sec , sec

50 100 150 200 250 300 350 400 450 500 550

200

400

600

800

1000 170

115 141

63 89 39

155

Library Hit - similarity 948, "o-Phenylphenol"

Caliper

Peak True

Library Hit

®

0.72786

0.74786

0.76786

0.78786

0.8786

0.82786

0

1000

2000

3000

4000

5000

6000

7000

1st Time (s)2nd Time (s)

170 135

GCxGC - Spectral Deconvolution

50 100 150 200 250 300 350 400 450 500 550

200

400

600

800

1000 135

152

77

63

107

121 169 434 285 399 357 231

Caliper - sample "Pau d'Arco Tea extract:1", 786 , 0.790 sec , sec to 786 , 0.790 sec , sec - 150 , 0.000 sec , sec to 150 , 0.000 sec , sec

50 100 150 200 250 300 350 400 450 500 550

200

400

600

800

1000 65

169

141

115

105 87

434 285 356

Peak True - sample "Pau d'Arco Tea extract:1", peak 292, at 786 , 0.790 sec , sec

50 100 150 200 250 300 350 400 450 500 550

200

400

600

800

1000 170

115

141

63

89 74

102 155

Reference Spectrum - Calibration "QuEChERS Perf AB 500", Analyte "o-Phenylphenol"

Caliper

Peak True

Reference Spectrum

o-P

hen

ylp

hen

ol

un

kno

wn

®

MS/MS Selectivity

141 > 115.1 m/z 169.7 > 115.1 m/z 169.7 > 141.3 m/z

(mainlib) o-Hydroxybiphenyl

20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 1800

50

100

27

39 51

52 5558

62

63

65 7077 87

89

91 98102

115

126 131

141

151 155

170

OH

o-phenylphenol

®

Pau d’Arco

A Traditional South American Herbal Tea Contains: Pau d’Arco bark

Average % Recovery for ALL target pesticides

Spike GC-MS/MS GCxGC-TOFMS

1000 ng/g 93% (± 15) 92% (± 14)

100 ng/g 87% (± 12) 81% (± 17)

10 ng/g 84% (± 24) NA

GCxGC-TOFMS Thiabendazole (130) Fenpropathrin (43)

Incurred Pesticides (ng/g):

GC-MS/MS Thiabendazole (16)

Imazalil (13)

®

Wild Berry Zinger Ingredients: Hibiscus, rosehips, roasted chicory, orange peel, blackberry leaves, natural flavors…

®

% Recoveries of Spiked Pesticides in Wild Berry Zinger Tea

Pesticide 1000 ng/g 100 ng/g

GC-MS/MS GCxGC-TOFMS GC-MS/MS GCxGC-TOFMS

Acephate 76 88 88 81

o-Phenylphenol 86 92 113 95

Omethoate 81 78 101 88

Diazinon 85 93 86 95

Chlorothalonil 72 79 74 100

Vinclozolin 84 99 89 91

Carbaryl 98 94 89 91

Metalaxyl 86 96 84 90

Methiocarb 84 90 85 89

Malathion 91 95 96 94

Fenthion 84 88 85 98

Chlorpyrifos 84 93 84 88

Cyprodinil 65 71 66 73

Thiabendazole 65 62 86 77

Captan 86 99 102 180

Imazalil 86 91 102 91

Endosulfan sulfate 86 95 87 100

Propargite 85 96 84 110

Iprodione 88 99 85 74

Bifenthrin 76 86 77 82

Fenpropathrin 85 93 97 93

cis-Permethrin 78 88 78 70

Deltamethrin 83 88 74 78

®

Ingredients: Hibiscus, rosehips, roasted chicory, orange peel, blackberry leaves, natural flavors…

Wild Berry Zinger

Average % Recovery for ALL target pesticides

Spike GC-MS/MS GCxGC-TOFMS

1000 ng/g 79% (± 10) 90% (± 11)

100 ng/g 83% (± 12) 94% (± 33)

10 ng/g 88% (± 19) NA

GCxGC-TOFMS Carbaryl (10)

Chlorpyrifos (16) Imazalil (727)

Thiabendazole (429) o-Phenylphenol (22)

Incurred Pesticides (ng/g):

GC-MS/MS Carbaryl (23)

Chlorpyrifos (18) Imazalil (470)

Thiabendazole (240) Fenhexamid (2)

4’4-DDT (1)

®

Red Tea – Cinnamon Orange Ingredients: Rooibos, cinnamon, orange

peel, natural cinnamon and orange flavors

®

% Recoveries of Spiked Pesticides in Red Tea

Pesticide 1000 ng/g 100 ng/g

GC-MS/MS GCxGC-TOFMS GC-MS/MS GCxGC-TOFMS

Acephate 69 110 74 80

o-Phenylphenol 86 98 83 96

Omethoate 58 120 66 100

Diazinon 84 99 94 88

Chlorothalonil 69 110 71 71

Vinclozolin 85 100 88 83

Carbaryl 83 110 82 85

Metalaxyl 85 110 84 87

Methiocarb 83 120 90 102

Malathion 85 110 93 77

Fenthion 83 110 84 91

Chlorpyrifos 81 100 88 90

Cyprodinil 75 97 78 79

Thiabendazole 52 87 51 75

Captan 89 140 76 160

Imazalil 73 120 76 88

Endosulfan sulfate 80 120 80 84

Propargite 78 110 89 92

Iprodione 82 120 89 92

Bifenthrin 74 98 78 85

Fenpropathrin 80 110 74 76

cis-Permethrin 74 99 76 92

Deltamethrin 77 120 93 120

®

Rooibos, cinnamon, orange peel, natural cinnamon and orange flavors

Spike GC-MS/MS GCxGC-TOFMS

1000 ng/g 83% (± 8) 110% (± 13)

100 ng/g 87% (± 12) 91% (± 14)*

10 ng/g 90% (± 15) NA

GCxGC-TOFMS o-Phenylphenol (25)

Incurred Pesticides (ng/g):

GC-MS/MS o-Phenylphenol (20)

Endosulfan sulfate (2) Iprodione (2) Imazalil (2)

Thiabendazole (8)

Red Tea – Cinnamon Orange

®

Red Tea – Cinnamon Orange Incurred Imazalil

2 ng/g = 0.2 pg on-column

Quant peak 215 > 173 m/z

Confirming Ion Ratio ± 20% 3 SRM transitions

®

Everyday Detox Ingredients: roasted chicory root, dandelion root, schisandra fruit, lycium fruit, licorice root, ginger

rhizome, star anise fruit, kukicha twig

®

GCxGC Resolution

Acephate m/z 136

®

Acephate MS/MS Selectivity

Quant peak 136 > 42.1 m/z

100 pg on-column

10 pg on-column

Corruption of peak from

interferences

Confirming ions 94 > 64 m/z

136 > 94 m/z

®

Acephate has a “skinny” mass spectrum. There is not a lot of high abundance, high m/z values for more “selective” fragmentation

®

% Recoveries of Spiked Pesticides in Everyday Detox Tea

Pesticide 1000 ng/g 100 ng/g

GC-MS/MS GCxGC-TOFMS GC-MS/MS GCxGC-TOFMS

Acephate 75 88 81 89

o-Phenylphenol 85 88 81 100

Omethoate 66 85 95 93

Diazinon 87 88 78 96

Chlorothalonil 73 74 71 99

Vinclozolin 84 93 83 110

Carbaryl 86 97 74 100

Metalaxyl 85 100 76 88

Methiocarb 86 96 78 120

Malathion 86 98 75 67

Fenthion 87 98 81 100

Chlorpyrifos 85 88 84 110

Cyprodinil 75 83 69 81

Thiabendazole 62 75 37 86

Captan 82 100 82 100

Imazalil 84 75 63 72

Endosulfan sulfate 87 99 77 100

Propargite 89 90 83 83

Iprodione 91 90 81 100

Bifenthrin 81 85 75 84

Fenpropathrin 88 90 83 100

cis-Permethrin 80 87 67 97

Deltamethrin 86 90 89 93

®

roasted chicory root, dandelion root, schisandra fruit, lycium fruit, licorice root, ginger rhizome, star anise

fruit, kukicha twig

Spike GC-MS/MS GCxGC-TOFMS

1000 ng/g 85% (± 28) 89% (± 10)

100 ng/g 79% (± 13) 97% (± 24)

10 ng/g 87% (± 19) NA

GCxGC-TOFMS None Found

Incurred Pesticides (ng/g):

GC-MS/MS gamma-BHC (1) Methiocarb (6)

Everyday Detox

®

GCxGC TOFMS Benefits/Drawbacks

+ Non- target screening possible

+ High identification confidence: 2 retention times and full mass spectrum

+ Interferences: simple reprocessing of data with different quant ion

- More difficult GCxGC hardware setup and method development

- Higher detection limits

- Large data files and slower data processing

®

GC-MS/MS Benefits / Drawbacks

+ Lower Detection Limits – most compounds easily detected at 1 pg on-column

+ Faster data processing/smaller file sizes

+ Easier hardware setup

- Targeted screening only

- More difficult compound identification (management of ion ratios and allowable deviation)

- Less identification confidence: one retention time and limited mass spectral information

- Time consuming MS method development

®

Conclusions

• A QuEChERS extraction and dSPE cleanup of herbal teas resulted in good recoveries of target pesticides.

• Using GC-MS/MS allowed detection of target pesticides at 10 ng/g.

• Non-target screening of active ingredients is possible with GCxGC-TOFMS.

• Average percent recoveries were similar for both instrument platforms.

®

Non-Target Analysis

Maté Lemon Ingredients: Yerba maté, lemon myrtle, green tea

“Its stimulating effect evokes a cheerful mental lucidity”

Sceletium & Honeybush Tea Ingredients: Sceletium and african honeybush

“The cup that cheers”

elev8 Ingredients: Zembrin 25 mg, equivalent to 50 mg

Sceletium tortuosum above ground herb

®

Maté Lemon Ingredients: Yerba maté, lemon

myrtle, green tea

®

Peak Find, Spectral Deconvolution, Library Search

Set S/N, automatic deconvolution

®

Sort by Similarity for Qualitative Review

®

Maté Lemon Ingredients: Yerba maté, lemon

myrtle, green tea

1425 peaks S/N ≥ 100

®

Some names are easily recognized.

Qualitative Review

100 200 300 400 500

1000 67

194

Caliper - sample "Mate Lemon Tea extract:1", 1206 , 1.190 sec , sec to 1206 , 1.190 sec , sec - 400 , 0.000 sec , sec to 400 , 0.000 sec , sec

100 200 300 400 500

500

1000 67

194

Peak True - sample "Mate Lemon Tea extract:1", peak 931, at 1206 , 1.190 sec , sec

100 200 300 400 500

500

1000 194

109

55

Library Hit - similarity 941, "Caffeine"

Caffeine

®

Others may need further investigation.

Qualitative Review

50 100 150 200 250 300 350 400 450 500 550

200

400

600

800

1000 78

51

122

106

94

Caliper - sample "Mate Lemon Tea extract:1", 610 , 1.420 sec , sec to 610 , 1.420 sec , sec - 400 , 0.000 sec , sec to 400 , 0.000 sec , sec

50 100 150 200 250 300 350 400 450 500 550

200

400

600

800

1000 78

51

122

106

94 67

Peak True - sample "Mate Lemon Tea extract:1", peak 559, at 610 , 1.420 sec , sec

50 100 150 200 250 300 350 400 450 500 550

200

400

600

800

1000 122

78

106

51

94 66

Library Hit - similarity 912, "Niacinamide"

Niacinamide is part of the vitamin

B group. It has anti-inflammatory,

anti-anxiety properties.

Be critical with NIST library matches. Is it real? More unique

spectrum with abundant high m/z

ions gives better confidence in match.

®

Recognizing chemical names can sometimes be difficult. Using the synonym list is helpful. “Pyridine, 2-chloro-6-(2-furanylmethoxy)-4-

(trichloromethyl)-” is also known as Pyroxyfur, a fungicide.

Qualitative Review

®

Qualitative Review

50 100 150 200 250 300 350 400 450 500 550

200

400

600

800

1000 81

53

107 71

Caliper - sample "Mate Lemon Tea extract:1", 514 , 1.110 sec , sec to 514 , 1.110 sec , sec - 400 , 0.000 sec , sec to 400 , 0.000 sec , sec

50 100 150 200 250 300 350 400 450 500 550

200

400

600

800

1000 81

53

107

Peak True - sample "Mate Lemon Tea extract:1", peak 462, at 514 , 1.110 sec , sec

50 100 150 200 250 300 350 400 450 500 550

200

400

600

800

1000 81

53

Library Hit - similarity 910, "Pyroxyfur"

Pyroxyfur is a pyridine fungicide.

With less spectral information it is difficult to assign a positive match.

®

50 100 150 200 250 300 350 400 450 500 550

200

400

600

800

1000 81

53

107 71

Caliper - sample "Mate Lemon Tea extract:1", 514 , 1.110 sec , sec to 514 , 1.110 sec , sec - 786 , 0.708 sec , sec to 786 , 0.708 sec , sec

45 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120 125

200

400

600

800

1000 81

53

51 107 55

Peak True - sample "Mate Lemon Tea extract:1", peak 462, at 514 , 1.110 sec , sec

45 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120 125

200

400

600

800

1000 81

53

51

Library Hit - similarity 910, "Pyridine, 2-chloro-6-(2-furanylmethoxy)-4-(trichloromethyl)-"

Peak True matches Library Hit at low m/z values

Peak True

Library Hit

®

Qualitative Review

50 100 150 200 250 300 350 400 450 500 550

200

400

600

800

1000 81

53

107 71

Caliper - sample "Mate Lemon Tea extract:1", 514 , 1.110 sec , sec to 514 , 1.110 sec , sec - 400 , 0.000 sec , sec to 400 , 0.000 sec , sec

50 100 150 200 250 300 350 400 450 500 550

200

400

600

800

1000 81

53

107

Peak True - sample "Mate Lemon Tea extract:1", peak 462, at 514 , 1.110 sec , sec

50 100 150 200 250 300 350 400 450 500 550

200

400

600

800

1000 81

53

Library Hit - similarity 910, "Pyroxyfur"

With less spectral information it is difficult to assign a positive match.

®

305 310 315 320 325 330 335 340 345 350

200

400

600

800

1000

Caliper - sample "Mate Lemon Tea extract:1", 514 , 1.110 sec , sec to 514 , 1.110 sec , sec - 786 , 0.708 sec , sec to 786 , 0.708 sec , sec

305 310 315 320 325 330 335 340 345 350

5

10

15

20

Peak True - sample "Mate Lemon Tea extract:1", peak 462, at 514 , 1.110 sec , sec

305 310 315 320 325 330 335 340 345 350

5

10

15

20

Library Hit - similarity 910, "Pyridine, 2-chloro-6-(2-furanylmethoxy)-4-(trichloromethyl)-"

No molecular weight ion in Peak True spectrum

Pyroxyfur MW = 325

Peak True

Library Hit

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Flavonoids – polyphenolic compounds that may reduce

the risk of certain cancers.

Structured Chromatograms Sceletium & Honeybush

Tea

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Phytosterols – may help reduce blood cholesterol

levels.

Structured Chromatograms Sceletium & Honeybush

Tea

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β-Sitosterol

Stigmasterol Campesterol

Structured Chromatograms

Phytosterols Sceletium & Honeybush

Tea

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The South African Sceletium tortuosum herb has been extracted for the medicinally relevant mesembrine-type alkaloids.

Mesembranol Mesembrine Mesembrenol Mesembrenone

The mesebrine-type alkaloids have shown to elevate mood, reduce stress

and promote a sense of calm

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m/z 204, 218, 289

Mesembrine-type alkaloids elev8TM

“elevates mood, assists in coping with stress”

Sceletium and Honeybush Tea

“The Cup that Cheers”

The minor mesembrine alkaloid mesembranol was not detected in the tea sample, however many other beneficial compounds (phytosterols, flavonoids) that were present

in the tea were not in the tablet.