LC-MS/MS Technology and Applications: Transform your ... › sites › production › files ›...

1

LC-MSMS Technology and Applicationsldquo Transform your routine science rdquo

Jonathan Beck PhD Marketing Scientist Environmental amp Food Safety October 20th 2015

The world leader in serving science

Outline

bull High Resolution Accurate Mass for Environmental Analysis bull EQuan MAX Plus online sample preconcentration and

cleanup bull New Triple Quadrupole developments from Thermo Scientific

bull Project with Duke University for Emerging contaminants

2

Pharmaceuticals Pesticides Endocrine Disruptors Personal Care Products

N

OF

OH

Cl NH

N

N

N

Cl

OH

OH

NH

NH

I

I

O

I

OH

O

O

OH N

N

O

O

O O

OH

OH

O

O

O

O

OO

O

OH

OH

O

O

O

O OH

N

O

What is Environmental Analysis Challenge

bull Analysis of thousands of pollutants bull High diversity of chemical

characteristics bull Different matrices bull Screening Workflows with QuanQual

capabilities needed bull New issues Hydraulic fracturing bull Regulatory

bull EU Water Framework Directive bull

Contamination of ground and drinking water is a risk for

human health

Emerging Contaminants in The Environment ndash USGS study

3

Whatrsquos in our water supplies

Pharmaceuticals Personal Care Products Pesticides

Image from National Geographic April 2010 4

Sample preparationanalyte detection strategy

Clean-up efficiency Detection selectivity

MSMS

HRAM-MSMS

HPLC-UV

HPLC-FLD

Simple extraction

SPE

Dispersive SPE LC-MS

GC-MS ECD

GPC

LLE

5

Major Challenges in EFS Analysis

Low Concentration

High throughput for routine labs

Identifying low abundance analytes obscured by high abundance compounds

Matrix Complexity

Getting the most accurate information from precious samples

Small Sample Volumes

Being able to detect and identify trace level analytes in simple or complex samples

Large Sample Numbers

6

Analytical Challenges for Traditional Mass Spectrometry

Detect and identify isobaric compounds

Isolate compounds from matrix components

High Resolution High mass accuracy (HRAM) MS

can do the job

Searching for unknowns

Here targeted data acquisition (SIM SRMhellip)

fails

Large number of compounds

7

Resolution (resolving power)

bull Resolutio n

mR m

m (FWHM)

m 10

m 500 bull Quadrupole MS R 833

m 06

m 500bull Orbitrap MS R 100000

m 0005

8

Detection of analytes in heavy matrix

Pesticide in Matrix

23900 23905 23910 23915 23920 239250

20

40

60

80

100

Rel

ativ

e A

bund

ance

23915181 C 11 H 19 O 2 N 4

650 ppm

R = 17500 Error = 650 ppm

23900 23905 23910 23915 23920 23925 0

20

40

60

80

100

Rel

ativ

e A

bund

ance

H O

Pirimicarb

mzmz

23915033 C 11 H 19 O 2 N 4

032 ppm

R = 70000 Error = 032 ppm

9

35

40

45

50

55

60

65

Rel

ative

Abu

ndan

ce

Resolution influence (17500 vs 70000) Resolution_17_5K 1823 RT 230 AV 1 NL 160E6 Resolution_70K 123 RT 054

100

95

90

85

80

75

70

65

60

55

50

45

40

35

30

25

20

15

10

5

0 22200 22205 22210 22215 22220 22225

T FTMS + p ESI Full ms [12000-100000] 2221263

2221463

2221838

AV 1 NL 180E6 T FTMS + p ESI Full ms [12000-100000]

0

5

10

15

20

25

30

70

75

80

85

90

95

100 2221238

2221129

2221465

2221854

Name Molecular Formula M+H

Carbofuran C12H15NO3 2221125

Formetanate C11H15N3O2 2221237

2220 2221 2222 2223 mz mz

Relative Abu

ndan

ce

10

Mass accuracy

Mass accuracy

m mmeas truem z 106

mtrue

50015000bull Quadrupole MS m z 106 200ppm500

5001031450010214bull Orbitrap MS m z 106 2ppmTOF MS 50010314

11

Selectivity increases with higher mass accuracy

Beer extract T-2 toxin 5 microgL R

elat

ive

Rel

ativ

e

RT 845 NL 120E5100

2 ppm

72 74 76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106 Time (min)

30

40 50 60

Abu

ndan

ce

855799749 791776767 1061741726 105010311016946

mz=48425313-90 48425507 F FTMS 10 + p APCI Full 80 ms [30000-85000]

70 MS pivo_5_UH

20 10 0

RT 845 NL 120E5100

20 ppm 72 74 76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106

Time (min)

30

40 50 60

Abu

ndan

ce

821762 785759740737 825781 792 799 861730726 10611050888 1031867 911 10161009946


70 MS pivo_5_UH

20 10 0

Rel

ativ

e

RT 845 NL 125E5100

30

40 50

Abu

ndan

ce

929872867 899878

911821785

1009 1016 1034100 ppm883813762759 781 810 835738

733 727 946 950 964 10611050


70 MS pivo_5_UH

60

20 10 0

72 7 7 78 8 8 8 8 8 9 9 9 9 9 100 102 104 106 4 6 0 2 4 6 8Time (min) 0 2 4 6 8

Zachariasova M et al Anal Chim Acta 12

2880441 C9H21O2P1S3 Terbufos

2880949 C13H21O3P1S1 Iprobenfos

2881142 C15H17N4Cl1 Myclobutanil

2881256 C11H20N4O3S1 Epronaz

2881351 C11H21N4O3P1 Pirimethaphos

2881474 C16H20N2O3 Imazamethabenz

28900 28905 28910 28915 28920mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891314

2890513 2891022

2891215

2891329 2891424

28900 28905 28910 28915 28920mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891390

28910212890514

2891215

28913292891424

Detection of Isobaric Compounds in mixtures

Element Exact Mass H 1007825 C 12000000 N 14003074 O 15994915

Is a simultaneous measurement possible

01033 amu

28900 28905 28910 28915 28920 mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891424 289154728913292891022

2890514

2891215 R = 140000

13

The Exactive Plus Orbitrap LCMS system

14

Q Exactive Orbitrap MSMS system

Higher ion transmission with rugged optics Increased sensitivity selectivity true MSMS Directly interfaced to HCD increases spectrum quality Multiple fills for spectrum multiplexing increases duty cycle Predictive automatic gain control for parallel filling amp detection brings more speed Advanced signal processing brings more resolution at same speed

15

Caffeine

What do we gain by using the quadrupole

1950876 N=24840281 NL 194E8100

[15000-200000]

NL 112E8

Full MS SN = 745

Lowest detected

250330

80

signalscan60

40

20

0 1950877 N=2074158100

Rel

ativ

e A

bund

ance

SN

(spe

ctrum) 4000

3000

2000

1000

0 195082 195084 195086 195088 19509 195092 195094

SN (FMS) SN (SIM10)

Sensitivity gain 5 ndash 10 x with SIM mode

80

60

40

20

0

[19010-20010]

Lowest detectedSIM (10amu) Gain in sensitivity (7x) signalscan SN = 5400 28240 6000

5000

16

Data dependent MSMS confirmation 1589762

Diuron

Azoxystrobin

Fluridone

Benoxacor

Fenamidone

Desmedipham

Imazalil

2 4 6 8 10 12 14 Time (min)

0

50

100 0

50

100 0

50

100 0

50

100

Rel

ativ

e Ab

unda

nce

0

50

100 0

50

100 0

50

100 696

735

735

744

755

758

780

NL 198E7 mz= 2970541-2970571 F FTMS + p ESI Full ms [5000-75000] MS 4xloq_02







0

50

100 0

50

100 0

50

Rel

ativ

e Ab

unda

nce

100 0

50

100 2970551690455 2009867

25500821090763

3161774 720451

0

2330241 11908561591165

3070625100

50

1399895 2710859343039211203951650904 1490834

50

0 100

26002361200445 1880704

590500

2817393 3441026

37209743290791

316107821606551720391 4052731810705 920500

2361180

10305461650481 26709513121149

100 200 300 400 mz

17

Q Exactive ndash ldquoQuanfirmationrdquo what is it

bull High performance HRAM Quantitation and Confirmation bench top LCMS system capable of

bull Multi-residue quan performance similar to mid-high end Triples bull Ideal for targeted and general unknown screening bull Highest confidence confirmation with R = 140K and MSMS bull UHPLC compatible bull Letlsquos use the QExactive to combine these 2 experiments into one

18

Outline

bull What is EQuan MAX Plus bull EQuan MAX Plus

bull How can EQuan MAX Plus help your workflow

bull Customer testimonials bull Who uses EQuan MAX Plus

19

Low Sample Concentration

Challenge TSQ Quantiva

Demanding assays which require the absolute lowest limit of detection

Powered by AIM technology the TSQ Quantiva MS is the worldrsquos most sensitive triple quadrupoleMS detecting compounds at the ppt level

20

Environmental Analysis (Water)

EQuan MAX Plus

For targeted quantitation (TSQ) or

Targetednon-targeted screening and quantitation using High Resolution Accurate Mass (Orbitrap platform)

21

EQuan MAX Plus What is it

bull Turnkey method for assaying environmental water samples (pesticides antibiotics etc) at low ppt levels bull On-line sample clean-up and

preconcentration bull 2 Columns Loading and

Analytical bull 2 pumps

bull High injection volumes bull 1mL-20mL

bull Standard injection volumes bull 1-100 uL

22

EQuan MAX Plus Targeted Quantitation

bull Couple EQuan MAX Plus with any TSQ Quantum from Thermo Scientific for the most sensitive and selective experiments

bull Fast Positive Negative Switching

bull TraceFinder Software bull Built in SRM parameters bull Built in EQuan Methods

bull Quantum Access MAX bull Quantum Endura bull Quantum Quantiva

23

EQuan MAX Plus Non-targeted screening and Quantitation

bull Couple EQuan MAX Plus with the Exactive Orbitrap instruments (Exactive Plus or Q-Exactive)

bull High Resolution Accurate Mass (HRAM)

bull All ions are collected in every experiment bull Re-interrogate your data at a

later time bull Quantitation and screening

methods are easy to set up since there are no compound dependant parameters to optimize

24

SPE - standard enrichment procedure

7 Detection

LC-M

S

LC-MSMS

1 Sample preparation 1L samplefiltration

internal StdFiltr

atio

n

6 Elution

5 Drying

4 Washing

3 Extraction

2 Conditioning

Enr

ichm

ent

MeOH H2O

60mg Oasis

H2OMeOH (955)

air

MeOH

40 samples ~ 5h

~ 2d

~ 2d

25 Slide Courtsey Heinz Singer ndasheawag Zurich Switzerland

EQuan MAX Plus Solution ndash Gain Vs Conventional Injections

T r ia z in e P e s t M ix _ 1 0 p p t _ 1 0 0 0 u l_ 0 4 3 2 4 2 0 0 5 1 1 0 0 1 A M

R T 5 9 8 - 8 0 0 N L 8 1 0 E 4

1 0 0

10 ul injection

T I C F + c E S I si d = -1 0 0 0 S R M m s2 2 1 6 1 3 -1 8 0 0 [ 9 5 1 7 4 0 0 ] M S t r i a z i n e p e st m i x _ 1 0 p p t _

9 0 1 0 u l _ 0 5

8 5

8 0

7 5

7 0

6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0

R T 5 9 8 - 8 0 2 R T 6 9 1 N L 8 1 0 E 4 A A 3 1 9 9 9 9 T I C F + c E S I si d = -1 0 0 0 S N 1 1 6 R M S S R M m s2 2 1 6 1 3 -1 8 0 0

1 0 0 [ 1 7 4 0 0 ] M S I C I S T r i a z i n e P e st M i x _ 1 0 p p t _ 1

9 5 0 0 0 u l _ 0 4

9 0

8 5

8 0

7 5

7 0

1000 ul injection6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0

4 5 4 5

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 6 0 6 5 7 0

T i m e (m

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 7 5 8 0 6 0 6 5 7 0 7 5 8 0

i n ) T i m e (m i n )

10 ppt Atrazine in ground water

26

Sensitivity Speed amp Robustness for EFS high throughput laboratories

27

TSQ Endura Extreme quantitative value bull Designed for non-stop operation

bull For scientist who need to run routine samples day in and day out

TSQ Quantiva Extreme quantitative performance bull Designed for the most challenging

assays

bull For scientists needing to stay at the forefront of analytical technology

TSQ Quantiva TSQ Endura Mass Range 10-1850 10-3400

Max SRM Number 30000 SRMs 30000 SRMs

SRMSec 500 SRMssec 500 SRMssec

Ion Optics Active Ion Management (AIM)

bull Ion Max NG source bull Electrodynamic ion

funnel bull ion beam guide with

neutral blocker bull 6 mm HyperQuad

quadrupoles with asymmetric RF drive

S- LENS with Beam Blocker Technology

Quadrupole Design 4mm Quadrupoles with Asymetric RF

Reserpine Specification

100000 1 SN for 1 pg Reserpine


elostrade

From Identification

28

Challenge Orbitrap V MS Confidently identify unknownemerging contaminantshelliphelliphelliphellip

High-Resolution Accurate Mass for identification of unknown emerging contaminants

To Routine Quantitation

Challenge EQuan MAX Plus and TSQ Quantivatrade MS

Followed by routine quantitation Online sample prep LCMS forquantitation of emergingcontaminants identified by the Orbitrap Velos

29

Analysis of Targeted and Non-targeted Contaminants in Storm Water Retention Ponds Emerging Contaminants from ID to Quantitation The Total Thermo Scientific Solution

Gordon Getzinger ndash Duke University Jonathan Beck PhD ndash Thermo Fisher Scientific

UHPLC-HRMS An Emerging Technique for ldquoHelping Contaminants Emergerdquo bull Target screening ― Monitor known contaminants using reference standards

bull Suspect screening ― Screen high-resolution accurate-mass data against

molecular databases of suspected contaminants bull Non-target screening ― Assign molecular and structural formula to

chromatographic features without previous knowledge of contaminant presence or identity

Krauss et al LC-high resolution MS in environmental analysis from target screening to the identification of unknowns (2010) Anal Bioanal Chem 397 [3]

31

Emerging Contaminant ID to Quantitation Workflow

bull Reclaimed waste water used for irrigation on a golf course for emerging contaminants (PPCPs) bull Lee Ferguson and Gordon Getzinger Environmental Chemistry Duke University USA

Acquire Fast Identify Develop Routine HRAM Data Contaminants Quantitative Quantitation

Assay

ExactFinder Software

Etofenprox Benzotriazole

Propanamide Acephate Allethrin

32

Kiawah Island SC USA

WWTPLand application of WW for golf course irrigation

Question Which microcontaminants are entering the aquatic environment as a result of wastewater reuse practices

33

Typical Sampling Site

34

Variety of Sampling Sites

Sample Site Inputs

Pond 5 Golf course runoff


Pond 43 Residential stormwater

Wastewater lagoon Treated municpal wastewater

Wastewater Composite 24hr composite effluent

Well 1 Infiltration from pond 25


35

Quantitation of Samples

bull Use a triple quad for quantitation bull Analyze samples directly no offline SPE to save time and

money bull Remove variables and sources of experimental error by

automated extraction and preconcentration bull An ideal solution for this challenge ishellip

36

What Did We Want to See in the Quantitation Experiment

bull Quantitative results at low concentrationshellip low and sub PPT levels

bull Calibration range bull 006 pgmL ndash 1000 pgmL

RT 400-1357

bull With a 1mL injection thatrsquos 60 fg ndash 1000 pg on column 968 NL 107E6 100

90

80

70

60

TIC of 175 pgmL injected standard 50

175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37

Calibration range 006-1000 pgmL - Flutolanil

60fg On Column 45 orders of magnitudeIon Ratio overlay

38

Results of Compounds Detected in a WWTP Sample

39

Identification of Emerging Contaminants

Data Analysis Workflow

Target screening

Are compounds x y amp z present in this sample

Non-target screening

Which compounds are present in this sample

Suspect screening

Which compounds of a defined list are present in this sample

40

LCMS Workflows for Environmental and Food Safety

41

Tools to Develop methods for Known and Emerging contaminants

Raw Sample bull Accelerated Solvent Extraction (ASE)

Dionex ASE

Dionex UHPLC 3000

EQuan MAX Plus bull Equan MAX Plus online sample prep LCMS

Customized Reporting

bull Custom software to meet the needs of your workflow

bull TraceFinder SIEVE mzCloud

TSQ Quantiva TSQ Endura

bull TSQ Series Mass Spectrometers triple stage quadrupole LC-MSMS and GC MSMS for high sensitivity quantitation

bull Exactive Plus and Q Exactive Mass Spectrometers High Resolution Accurate Mass to identify quantify and confirm

Orbitrap HRAM

Orbitrap Fusion

42

Transform Your Science

Outline

bull High Resolution Accurate Mass for Environmental Analysis bull EQuan MAX Plus online sample preconcentration and

cleanup bull New Triple Quadrupole developments from Thermo Scientific

bull Project with Duke University for Emerging contaminants

2


N

OF

OH

Cl NH

N

N

N

Cl

OH

OH

NH

NH

I

I

O

I

OH

O

O

OH N

N

O

O

O O

OH

OH

O

O

O

O

OO

O

OH

OH

O

O

O

O OH

N

O







human health


3






MSMS

HRAM-MSMS

HPLC-UV

HPLC-FLD

Simple extraction

SPE


GC-MS ECD

GPC

LLE

5


Low Concentration



Matrix Complexity





6





can do the job



fails


7


bull Resolutio n

mR m

m (FWHM)

m 10


m 06


m 0005

8


Pesticide in Matrix

23900 23905 23910 23915 23920 239250

20

40

60

80

100

Rel

ativ

e A

bund

ance

23915181 C 11 H 19 O 2 N 4

650 ppm

R = 17500 Error = 650 ppm

23900 23905 23910 23915 23920 23925 0

20

40

60

80

100

Rel

ativ

e A

bund

ance

H O

Pirimicarb

mzmz

23915033 C 11 H 19 O 2 N 4

032 ppm

R = 70000 Error = 032 ppm

9

35

40

45

50

55

60

65

Rel

ative

Abu

ndan

ce


100

95

90

85

80

75

70

65

60

55

50

45

40

35

30

25

20

15

10

5

0 22200 22205 22210 22215 22220 22225


2221463

2221838


0

5

10

15

20

25

30

70

75

80

85

90

95

100 2221238

2221129

2221465

2221854




2220 2221 2222 2223 mz mz

Relative Abu

ndan

ce

10

Mass accuracy

Mass accuracy

m mmeas truem z 106

mtrue



11



elat

ive

Rel

ativ

e

RT 845 NL 120E5100

2 ppm

72 74 76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106 Time (min)

30

40 50 60

Abu

ndan

ce

855799749 791776767 1061741726 105010311016946


70 MS pivo_5_UH

20 10 0

RT 845 NL 120E5100

20 ppm 72 74 76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106

Time (min)

30

40 50 60

Abu

ndan

ce

821762 785759740737 825781 792 799 861730726 10611050888 1031867 911 10161009946


70 MS pivo_5_UH

20 10 0

Rel

ativ

e

RT 845 NL 125E5100

30

40 50

Abu

ndan

ce

929872867 899878

911821785

1009 1016 1034100 ppm883813762759 781 810 835738

733 727 946 950 964 10611050


70 MS pivo_5_UH

60

20 10 0

72 7 7 78 8 8 8 8 8 9 9 9 9 9 100 102 104 106 4 6 0 2 4 6 8Time (min) 0 2 4 6 8








28900 28905 28910 28915 28920mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891314

2890513 2891022

2891215

2891329 2891424

28900 28905 28910 28915 28920mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891390

28910212890514

2891215

28913292891424




01033 amu

28900 28905 28910 28915 28920 mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891424 289154728913292891022

2890514

2891215 R = 140000

13


14



15

Caffeine


1950876 N=24840281 NL 194E8100

[15000-200000]

NL 112E8

Full MS SN = 745

Lowest detected

250330

80

signalscan60

40

20

0 1950877 N=2074158100

Rel

ativ

e A

bund

ance

SN

(spe

ctrum) 4000

3000

2000

1000

0 195082 195084 195086 195088 19509 195092 195094

SN (FMS) SN (SIM10)


80

60

40

20

0

[19010-20010]


5000

16


Diuron

Azoxystrobin

Fluridone

Benoxacor

Fenamidone

Desmedipham

Imazalil

2 4 6 8 10 12 14 Time (min)

0

50

100 0

50

100 0

50

100 0

50

100

Rel

ativ

e Ab

unda

nce

0

50

100 0

50

100 0

50

100 696

735

735

744

755

758

780








0

50

100 0

50

100 0

50

Rel

ativ

e Ab

unda

nce

100 0

50

100 2970551690455 2009867

25500821090763

3161774 720451

0

2330241 11908561591165

3070625100

50

1399895 2710859343039211203951650904 1490834

50

0 100

26002361200445 1880704

590500

2817393 3441026

37209743290791

316107821606551720391 4052731810705 920500

2361180

10305461650481 26709513121149

100 200 300 400 mz

17




18

Outline




19





20


EQuan MAX Plus



21







22






23







24


7 Detection

LC-M

S

LC-MSMS


internal StdFiltr

atio

n

6 Elution

5 Drying

4 Washing

3 Extraction

2 Conditioning

Enr

ichm

ent

MeOH H2O

60mg Oasis

H2OMeOH (955)

air

MeOH

40 samples ~ 5h

~ 2d

~ 2d




R T 5 9 8 - 8 0 0 N L 8 1 0 E 4

1 0 0

10 ul injection


9 0 1 0 u l _ 0 5

8 5

8 0

7 5

7 0

6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0



9 5 0 0 0 u l _ 0 4

9 0

8 5

8 0

7 5

7 0


6 0

Rel

ativ

e A

bund

ance

5 5

5 0

4 5 4 5

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 6 0 6 5 7 0

T i m e (m

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 7 5 8 0 6 0 6 5 7 0 7 5 8 0



26


27




assays















elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42



N

OF

OH

Cl NH

N

N

N

Cl

OH

OH

NH

NH

I

I

O

I

OH

O

O

OH N

N

O

O

O O

OH

OH

O

O

O

O

OO

O

OH

OH

O

O

O

O OH

N

O







human health


3






MSMS

HRAM-MSMS

HPLC-UV

HPLC-FLD

Simple extraction

SPE


GC-MS ECD

GPC

LLE

5


Low Concentration



Matrix Complexity





6





can do the job



fails


7


bull Resolutio n

mR m

m (FWHM)

m 10


m 06


m 0005

8


Pesticide in Matrix

23900 23905 23910 23915 23920 239250

20

40

60

80

100

Rel

ativ

e A

bund

ance

23915181 C 11 H 19 O 2 N 4

650 ppm

R = 17500 Error = 650 ppm

23900 23905 23910 23915 23920 23925 0

20

40

60

80

100

Rel

ativ

e A

bund

ance

H O

Pirimicarb

mzmz

23915033 C 11 H 19 O 2 N 4

032 ppm

R = 70000 Error = 032 ppm

9

35

40

45

50

55

60

65

Rel

ative

Abu

ndan

ce


100

95

90

85

80

75

70

65

60

55

50

45

40

35

30

25

20

15

10

5

0 22200 22205 22210 22215 22220 22225


2221463

2221838


0

5

10

15

20

25

30

70

75

80

85

90

95

100 2221238

2221129

2221465

2221854




2220 2221 2222 2223 mz mz

Relative Abu

ndan

ce

10

Mass accuracy

Mass accuracy

m mmeas truem z 106

mtrue



11



elat

ive

Rel

ativ

e

RT 845 NL 120E5100

2 ppm

72 74 76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106 Time (min)

30

40 50 60

Abu

ndan

ce

855799749 791776767 1061741726 105010311016946


70 MS pivo_5_UH

20 10 0

RT 845 NL 120E5100

20 ppm 72 74 76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106

Time (min)

30

40 50 60

Abu

ndan

ce

821762 785759740737 825781 792 799 861730726 10611050888 1031867 911 10161009946


70 MS pivo_5_UH

20 10 0

Rel

ativ

e

RT 845 NL 125E5100

30

40 50

Abu

ndan

ce

929872867 899878

911821785

1009 1016 1034100 ppm883813762759 781 810 835738

733 727 946 950 964 10611050


70 MS pivo_5_UH

60

20 10 0

72 7 7 78 8 8 8 8 8 9 9 9 9 9 100 102 104 106 4 6 0 2 4 6 8Time (min) 0 2 4 6 8








28900 28905 28910 28915 28920mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891314

2890513 2891022

2891215

2891329 2891424

28900 28905 28910 28915 28920mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891390

28910212890514

2891215

28913292891424




01033 amu

28900 28905 28910 28915 28920 mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891424 289154728913292891022

2890514

2891215 R = 140000

13


14



15

Caffeine


1950876 N=24840281 NL 194E8100

[15000-200000]

NL 112E8

Full MS SN = 745

Lowest detected

250330

80

signalscan60

40

20

0 1950877 N=2074158100

Rel

ativ

e A

bund

ance

SN

(spe

ctrum) 4000

3000

2000

1000

0 195082 195084 195086 195088 19509 195092 195094

SN (FMS) SN (SIM10)


80

60

40

20

0

[19010-20010]


5000

16


Diuron

Azoxystrobin

Fluridone

Benoxacor

Fenamidone

Desmedipham

Imazalil

2 4 6 8 10 12 14 Time (min)

0

50

100 0

50

100 0

50

100 0

50

100

Rel

ativ

e Ab

unda

nce

0

50

100 0

50

100 0

50

100 696

735

735

744

755

758

780








0

50

100 0

50

100 0

50

Rel

ativ

e Ab

unda

nce

100 0

50

100 2970551690455 2009867

25500821090763

3161774 720451

0

2330241 11908561591165

3070625100

50

1399895 2710859343039211203951650904 1490834

50

0 100

26002361200445 1880704

590500

2817393 3441026

37209743290791

316107821606551720391 4052731810705 920500

2361180

10305461650481 26709513121149

100 200 300 400 mz

17




18

Outline




19





20


EQuan MAX Plus



21







22






23







24


7 Detection

LC-M

S

LC-MSMS


internal StdFiltr

atio

n

6 Elution

5 Drying

4 Washing

3 Extraction

2 Conditioning

Enr

ichm

ent

MeOH H2O

60mg Oasis

H2OMeOH (955)

air

MeOH

40 samples ~ 5h

~ 2d

~ 2d




R T 5 9 8 - 8 0 0 N L 8 1 0 E 4

1 0 0

10 ul injection


9 0 1 0 u l _ 0 5

8 5

8 0

7 5

7 0

6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0



9 5 0 0 0 u l _ 0 4

9 0

8 5

8 0

7 5

7 0


6 0

Rel

ativ

e A

bund

ance

5 5

5 0

4 5 4 5

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 6 0 6 5 7 0

T i m e (m

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 7 5 8 0 6 0 6 5 7 0 7 5 8 0



26


27




assays















elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42







MSMS

HRAM-MSMS

HPLC-UV

HPLC-FLD

Simple extraction

SPE


GC-MS ECD

GPC

LLE

5


Low Concentration



Matrix Complexity





6





can do the job



fails


7


bull Resolutio n

mR m

m (FWHM)

m 10


m 06


m 0005

8


Pesticide in Matrix

23900 23905 23910 23915 23920 239250

20

40

60

80

100

Rel

ativ

e A

bund

ance

23915181 C 11 H 19 O 2 N 4

650 ppm

R = 17500 Error = 650 ppm

23900 23905 23910 23915 23920 23925 0

20

40

60

80

100

Rel

ativ

e A

bund

ance

H O

Pirimicarb

mzmz

23915033 C 11 H 19 O 2 N 4

032 ppm

R = 70000 Error = 032 ppm

9

35

40

45

50

55

60

65

Rel

ative

Abu

ndan

ce


100

95

90

85

80

75

70

65

60

55

50

45

40

35

30

25

20

15

10

5

0 22200 22205 22210 22215 22220 22225


2221463

2221838


0

5

10

15

20

25

30

70

75

80

85

90

95

100 2221238

2221129

2221465

2221854




2220 2221 2222 2223 mz mz

Relative Abu

ndan

ce

10

Mass accuracy

Mass accuracy

m mmeas truem z 106

mtrue



11



elat

ive

Rel

ativ

e

RT 845 NL 120E5100

2 ppm

72 74 76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106 Time (min)

30

40 50 60

Abu

ndan

ce

855799749 791776767 1061741726 105010311016946


70 MS pivo_5_UH

20 10 0

RT 845 NL 120E5100

20 ppm 72 74 76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106

Time (min)

30

40 50 60

Abu

ndan

ce

821762 785759740737 825781 792 799 861730726 10611050888 1031867 911 10161009946


70 MS pivo_5_UH

20 10 0

Rel

ativ

e

RT 845 NL 125E5100

30

40 50

Abu

ndan

ce

929872867 899878

911821785

1009 1016 1034100 ppm883813762759 781 810 835738

733 727 946 950 964 10611050


70 MS pivo_5_UH

60

20 10 0

72 7 7 78 8 8 8 8 8 9 9 9 9 9 100 102 104 106 4 6 0 2 4 6 8Time (min) 0 2 4 6 8








28900 28905 28910 28915 28920mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891314

2890513 2891022

2891215

2891329 2891424

28900 28905 28910 28915 28920mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891390

28910212890514

2891215

28913292891424




01033 amu

28900 28905 28910 28915 28920 mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891424 289154728913292891022

2890514

2891215 R = 140000

13


14



15

Caffeine


1950876 N=24840281 NL 194E8100

[15000-200000]

NL 112E8

Full MS SN = 745

Lowest detected

250330

80

signalscan60

40

20

0 1950877 N=2074158100

Rel

ativ

e A

bund

ance

SN

(spe

ctrum) 4000

3000

2000

1000

0 195082 195084 195086 195088 19509 195092 195094

SN (FMS) SN (SIM10)


80

60

40

20

0

[19010-20010]


5000

16


Diuron

Azoxystrobin

Fluridone

Benoxacor

Fenamidone

Desmedipham

Imazalil

2 4 6 8 10 12 14 Time (min)

0

50

100 0

50

100 0

50

100 0

50

100

Rel

ativ

e Ab

unda

nce

0

50

100 0

50

100 0

50

100 696

735

735

744

755

758

780








0

50

100 0

50

100 0

50

Rel

ativ

e Ab

unda

nce

100 0

50

100 2970551690455 2009867

25500821090763

3161774 720451

0

2330241 11908561591165

3070625100

50

1399895 2710859343039211203951650904 1490834

50

0 100

26002361200445 1880704

590500

2817393 3441026

37209743290791

316107821606551720391 4052731810705 920500

2361180

10305461650481 26709513121149

100 200 300 400 mz

17




18

Outline




19





20


EQuan MAX Plus



21







22






23







24


7 Detection

LC-M

S

LC-MSMS


internal StdFiltr

atio

n

6 Elution

5 Drying

4 Washing

3 Extraction

2 Conditioning

Enr

ichm

ent

MeOH H2O

60mg Oasis

H2OMeOH (955)

air

MeOH

40 samples ~ 5h

~ 2d

~ 2d




R T 5 9 8 - 8 0 0 N L 8 1 0 E 4

1 0 0

10 ul injection


9 0 1 0 u l _ 0 5

8 5

8 0

7 5

7 0

6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0



9 5 0 0 0 u l _ 0 4

9 0

8 5

8 0

7 5

7 0


6 0

Rel

ativ

e A

bund

ance

5 5

5 0

4 5 4 5

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 6 0 6 5 7 0

T i m e (m

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 7 5 8 0 6 0 6 5 7 0 7 5 8 0



26


27




assays















elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42




MSMS

HRAM-MSMS

HPLC-UV

HPLC-FLD

Simple extraction

SPE


GC-MS ECD

GPC

LLE

5


Low Concentration



Matrix Complexity





6





can do the job



fails


7


bull Resolutio n

mR m

m (FWHM)

m 10


m 06


m 0005

8


Pesticide in Matrix

23900 23905 23910 23915 23920 239250

20

40

60

80

100

Rel

ativ

e A

bund

ance

23915181 C 11 H 19 O 2 N 4

650 ppm

R = 17500 Error = 650 ppm

23900 23905 23910 23915 23920 23925 0

20

40

60

80

100

Rel

ativ

e A

bund

ance

H O

Pirimicarb

mzmz

23915033 C 11 H 19 O 2 N 4

032 ppm

R = 70000 Error = 032 ppm

9

35

40

45

50

55

60

65

Rel

ative

Abu

ndan

ce


100

95

90

85

80

75

70

65

60

55

50

45

40

35

30

25

20

15

10

5

0 22200 22205 22210 22215 22220 22225


2221463

2221838


0

5

10

15

20

25

30

70

75

80

85

90

95

100 2221238

2221129

2221465

2221854




2220 2221 2222 2223 mz mz

Relative Abu

ndan

ce

10

Mass accuracy

Mass accuracy

m mmeas truem z 106

mtrue



11



elat

ive

Rel

ativ

e

RT 845 NL 120E5100

2 ppm

72 74 76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106 Time (min)

30

40 50 60

Abu

ndan

ce

855799749 791776767 1061741726 105010311016946


70 MS pivo_5_UH

20 10 0

RT 845 NL 120E5100

20 ppm 72 74 76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106

Time (min)

30

40 50 60

Abu

ndan

ce

821762 785759740737 825781 792 799 861730726 10611050888 1031867 911 10161009946


70 MS pivo_5_UH

20 10 0

Rel

ativ

e

RT 845 NL 125E5100

30

40 50

Abu

ndan

ce

929872867 899878

911821785

1009 1016 1034100 ppm883813762759 781 810 835738

733 727 946 950 964 10611050


70 MS pivo_5_UH

60

20 10 0

72 7 7 78 8 8 8 8 8 9 9 9 9 9 100 102 104 106 4 6 0 2 4 6 8Time (min) 0 2 4 6 8








28900 28905 28910 28915 28920mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891314

2890513 2891022

2891215

2891329 2891424

28900 28905 28910 28915 28920mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891390

28910212890514

2891215

28913292891424




01033 amu

28900 28905 28910 28915 28920 mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891424 289154728913292891022

2890514

2891215 R = 140000

13


14



15

Caffeine


1950876 N=24840281 NL 194E8100

[15000-200000]

NL 112E8

Full MS SN = 745

Lowest detected

250330

80

signalscan60

40

20

0 1950877 N=2074158100

Rel

ativ

e A

bund

ance

SN

(spe

ctrum) 4000

3000

2000

1000

0 195082 195084 195086 195088 19509 195092 195094

SN (FMS) SN (SIM10)


80

60

40

20

0

[19010-20010]


5000

16


Diuron

Azoxystrobin

Fluridone

Benoxacor

Fenamidone

Desmedipham

Imazalil

2 4 6 8 10 12 14 Time (min)

0

50

100 0

50

100 0

50

100 0

50

100

Rel

ativ

e Ab

unda

nce

0

50

100 0

50

100 0

50

100 696

735

735

744

755

758

780








0

50

100 0

50

100 0

50

Rel

ativ

e Ab

unda

nce

100 0

50

100 2970551690455 2009867

25500821090763

3161774 720451

0

2330241 11908561591165

3070625100

50

1399895 2710859343039211203951650904 1490834

50

0 100

26002361200445 1880704

590500

2817393 3441026

37209743290791

316107821606551720391 4052731810705 920500

2361180

10305461650481 26709513121149

100 200 300 400 mz

17




18

Outline




19





20


EQuan MAX Plus



21







22






23







24


7 Detection

LC-M

S

LC-MSMS


internal StdFiltr

atio

n

6 Elution

5 Drying

4 Washing

3 Extraction

2 Conditioning

Enr

ichm

ent

MeOH H2O

60mg Oasis

H2OMeOH (955)

air

MeOH

40 samples ~ 5h

~ 2d

~ 2d




R T 5 9 8 - 8 0 0 N L 8 1 0 E 4

1 0 0

10 ul injection


9 0 1 0 u l _ 0 5

8 5

8 0

7 5

7 0

6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0



9 5 0 0 0 u l _ 0 4

9 0

8 5

8 0

7 5

7 0


6 0

Rel

ativ

e A

bund

ance

5 5

5 0

4 5 4 5

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 6 0 6 5 7 0

T i m e (m

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 7 5 8 0 6 0 6 5 7 0 7 5 8 0



26


27




assays















elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42



Low Concentration



Matrix Complexity





6





can do the job



fails


7


bull Resolutio n

mR m

m (FWHM)

m 10


m 06


m 0005

8


Pesticide in Matrix

23900 23905 23910 23915 23920 239250

20

40

60

80

100

Rel

ativ

e A

bund

ance

23915181 C 11 H 19 O 2 N 4

650 ppm

R = 17500 Error = 650 ppm

23900 23905 23910 23915 23920 23925 0

20

40

60

80

100

Rel

ativ

e A

bund

ance

H O

Pirimicarb

mzmz

23915033 C 11 H 19 O 2 N 4

032 ppm

R = 70000 Error = 032 ppm

9

35

40

45

50

55

60

65

Rel

ative

Abu

ndan

ce


100

95

90

85

80

75

70

65

60

55

50

45

40

35

30

25

20

15

10

5

0 22200 22205 22210 22215 22220 22225


2221463

2221838


0

5

10

15

20

25

30

70

75

80

85

90

95

100 2221238

2221129

2221465

2221854




2220 2221 2222 2223 mz mz

Relative Abu

ndan

ce

10

Mass accuracy

Mass accuracy

m mmeas truem z 106

mtrue



11



elat

ive

Rel

ativ

e

RT 845 NL 120E5100

2 ppm

72 74 76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106 Time (min)

30

40 50 60

Abu

ndan

ce

855799749 791776767 1061741726 105010311016946


70 MS pivo_5_UH

20 10 0

RT 845 NL 120E5100

20 ppm 72 74 76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106

Time (min)

30

40 50 60

Abu

ndan

ce

821762 785759740737 825781 792 799 861730726 10611050888 1031867 911 10161009946


70 MS pivo_5_UH

20 10 0

Rel

ativ

e

RT 845 NL 125E5100

30

40 50

Abu

ndan

ce

929872867 899878

911821785

1009 1016 1034100 ppm883813762759 781 810 835738

733 727 946 950 964 10611050


70 MS pivo_5_UH

60

20 10 0

72 7 7 78 8 8 8 8 8 9 9 9 9 9 100 102 104 106 4 6 0 2 4 6 8Time (min) 0 2 4 6 8








28900 28905 28910 28915 28920mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891314

2890513 2891022

2891215

2891329 2891424

28900 28905 28910 28915 28920mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891390

28910212890514

2891215

28913292891424




01033 amu

28900 28905 28910 28915 28920 mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891424 289154728913292891022

2890514

2891215 R = 140000

13


14



15

Caffeine


1950876 N=24840281 NL 194E8100

[15000-200000]

NL 112E8

Full MS SN = 745

Lowest detected

250330

80

signalscan60

40

20

0 1950877 N=2074158100

Rel

ativ

e A

bund

ance

SN

(spe

ctrum) 4000

3000

2000

1000

0 195082 195084 195086 195088 19509 195092 195094

SN (FMS) SN (SIM10)


80

60

40

20

0

[19010-20010]


5000

16


Diuron

Azoxystrobin

Fluridone

Benoxacor

Fenamidone

Desmedipham

Imazalil

2 4 6 8 10 12 14 Time (min)

0

50

100 0

50

100 0

50

100 0

50

100

Rel

ativ

e Ab

unda

nce

0

50

100 0

50

100 0

50

100 696

735

735

744

755

758

780








0

50

100 0

50

100 0

50

Rel

ativ

e Ab

unda

nce

100 0

50

100 2970551690455 2009867

25500821090763

3161774 720451

0

2330241 11908561591165

3070625100

50

1399895 2710859343039211203951650904 1490834

50

0 100

26002361200445 1880704

590500

2817393 3441026

37209743290791

316107821606551720391 4052731810705 920500

2361180

10305461650481 26709513121149

100 200 300 400 mz

17




18

Outline




19





20


EQuan MAX Plus



21







22






23







24


7 Detection

LC-M

S

LC-MSMS


internal StdFiltr

atio

n

6 Elution

5 Drying

4 Washing

3 Extraction

2 Conditioning

Enr

ichm

ent

MeOH H2O

60mg Oasis

H2OMeOH (955)

air

MeOH

40 samples ~ 5h

~ 2d

~ 2d




R T 5 9 8 - 8 0 0 N L 8 1 0 E 4

1 0 0

10 ul injection


9 0 1 0 u l _ 0 5

8 5

8 0

7 5

7 0

6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0



9 5 0 0 0 u l _ 0 4

9 0

8 5

8 0

7 5

7 0


6 0

Rel

ativ

e A

bund

ance

5 5

5 0

4 5 4 5

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 6 0 6 5 7 0

T i m e (m

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 7 5 8 0 6 0 6 5 7 0 7 5 8 0



26


27




assays















elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42






can do the job



fails


7


bull Resolutio n

mR m

m (FWHM)

m 10


m 06


m 0005

8


Pesticide in Matrix

23900 23905 23910 23915 23920 239250

20

40

60

80

100

Rel

ativ

e A

bund

ance

23915181 C 11 H 19 O 2 N 4

650 ppm

R = 17500 Error = 650 ppm

23900 23905 23910 23915 23920 23925 0

20

40

60

80

100

Rel

ativ

e A

bund

ance

H O

Pirimicarb

mzmz

23915033 C 11 H 19 O 2 N 4

032 ppm

R = 70000 Error = 032 ppm

9

35

40

45

50

55

60

65

Rel

ative

Abu

ndan

ce


100

95

90

85

80

75

70

65

60

55

50

45

40

35

30

25

20

15

10

5

0 22200 22205 22210 22215 22220 22225


2221463

2221838


0

5

10

15

20

25

30

70

75

80

85

90

95

100 2221238

2221129

2221465

2221854




2220 2221 2222 2223 mz mz

Relative Abu

ndan

ce

10

Mass accuracy

Mass accuracy

m mmeas truem z 106

mtrue



11



elat

ive

Rel

ativ

e

RT 845 NL 120E5100

2 ppm

72 74 76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106 Time (min)

30

40 50 60

Abu

ndan

ce

855799749 791776767 1061741726 105010311016946


70 MS pivo_5_UH

20 10 0

RT 845 NL 120E5100

20 ppm 72 74 76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106

Time (min)

30

40 50 60

Abu

ndan

ce

821762 785759740737 825781 792 799 861730726 10611050888 1031867 911 10161009946


70 MS pivo_5_UH

20 10 0

Rel

ativ

e

RT 845 NL 125E5100

30

40 50

Abu

ndan

ce

929872867 899878

911821785

1009 1016 1034100 ppm883813762759 781 810 835738

733 727 946 950 964 10611050


70 MS pivo_5_UH

60

20 10 0

72 7 7 78 8 8 8 8 8 9 9 9 9 9 100 102 104 106 4 6 0 2 4 6 8Time (min) 0 2 4 6 8








28900 28905 28910 28915 28920mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891314

2890513 2891022

2891215

2891329 2891424

28900 28905 28910 28915 28920mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891390

28910212890514

2891215

28913292891424




01033 amu

28900 28905 28910 28915 28920 mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891424 289154728913292891022

2890514

2891215 R = 140000

13


14



15

Caffeine


1950876 N=24840281 NL 194E8100

[15000-200000]

NL 112E8

Full MS SN = 745

Lowest detected

250330

80

signalscan60

40

20

0 1950877 N=2074158100

Rel

ativ

e A

bund

ance

SN

(spe

ctrum) 4000

3000

2000

1000

0 195082 195084 195086 195088 19509 195092 195094

SN (FMS) SN (SIM10)


80

60

40

20

0

[19010-20010]


5000

16


Diuron

Azoxystrobin

Fluridone

Benoxacor

Fenamidone

Desmedipham

Imazalil

2 4 6 8 10 12 14 Time (min)

0

50

100 0

50

100 0

50

100 0

50

100

Rel

ativ

e Ab

unda

nce

0

50

100 0

50

100 0

50

100 696

735

735

744

755

758

780








0

50

100 0

50

100 0

50

Rel

ativ

e Ab

unda

nce

100 0

50

100 2970551690455 2009867

25500821090763

3161774 720451

0

2330241 11908561591165

3070625100

50

1399895 2710859343039211203951650904 1490834

50

0 100

26002361200445 1880704

590500

2817393 3441026

37209743290791

316107821606551720391 4052731810705 920500

2361180

10305461650481 26709513121149

100 200 300 400 mz

17




18

Outline




19





20


EQuan MAX Plus



21







22






23







24


7 Detection

LC-M

S

LC-MSMS


internal StdFiltr

atio

n

6 Elution

5 Drying

4 Washing

3 Extraction

2 Conditioning

Enr

ichm

ent

MeOH H2O

60mg Oasis

H2OMeOH (955)

air

MeOH

40 samples ~ 5h

~ 2d

~ 2d




R T 5 9 8 - 8 0 0 N L 8 1 0 E 4

1 0 0

10 ul injection


9 0 1 0 u l _ 0 5

8 5

8 0

7 5

7 0

6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0



9 5 0 0 0 u l _ 0 4

9 0

8 5

8 0

7 5

7 0


6 0

Rel

ativ

e A

bund

ance

5 5

5 0

4 5 4 5

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 6 0 6 5 7 0

T i m e (m

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 7 5 8 0 6 0 6 5 7 0 7 5 8 0



26


27




assays















elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42



bull Resolutio n

mR m

m (FWHM)

m 10


m 06


m 0005

8


Pesticide in Matrix

23900 23905 23910 23915 23920 239250

20

40

60

80

100

Rel

ativ

e A

bund

ance

23915181 C 11 H 19 O 2 N 4

650 ppm

R = 17500 Error = 650 ppm

23900 23905 23910 23915 23920 23925 0

20

40

60

80

100

Rel

ativ

e A

bund

ance

H O

Pirimicarb

mzmz

23915033 C 11 H 19 O 2 N 4

032 ppm

R = 70000 Error = 032 ppm

9

35

40

45

50

55

60

65

Rel

ative

Abu

ndan

ce


100

95

90

85

80

75

70

65

60

55

50

45

40

35

30

25

20

15

10

5

0 22200 22205 22210 22215 22220 22225


2221463

2221838


0

5

10

15

20

25

30

70

75

80

85

90

95

100 2221238

2221129

2221465

2221854




2220 2221 2222 2223 mz mz

Relative Abu

ndan

ce

10

Mass accuracy

Mass accuracy

m mmeas truem z 106

mtrue



11



elat

ive

Rel

ativ

e

RT 845 NL 120E5100

2 ppm

72 74 76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106 Time (min)

30

40 50 60

Abu

ndan

ce

855799749 791776767 1061741726 105010311016946


70 MS pivo_5_UH

20 10 0

RT 845 NL 120E5100

20 ppm 72 74 76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106

Time (min)

30

40 50 60

Abu

ndan

ce

821762 785759740737 825781 792 799 861730726 10611050888 1031867 911 10161009946


70 MS pivo_5_UH

20 10 0

Rel

ativ

e

RT 845 NL 125E5100

30

40 50

Abu

ndan

ce

929872867 899878

911821785

1009 1016 1034100 ppm883813762759 781 810 835738

733 727 946 950 964 10611050


70 MS pivo_5_UH

60

20 10 0

72 7 7 78 8 8 8 8 8 9 9 9 9 9 100 102 104 106 4 6 0 2 4 6 8Time (min) 0 2 4 6 8








28900 28905 28910 28915 28920mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891314

2890513 2891022

2891215

2891329 2891424

28900 28905 28910 28915 28920mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891390

28910212890514

2891215

28913292891424




01033 amu

28900 28905 28910 28915 28920 mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891424 289154728913292891022

2890514

2891215 R = 140000

13


14



15

Caffeine


1950876 N=24840281 NL 194E8100

[15000-200000]

NL 112E8

Full MS SN = 745

Lowest detected

250330

80

signalscan60

40

20

0 1950877 N=2074158100

Rel

ativ

e A

bund

ance

SN

(spe

ctrum) 4000

3000

2000

1000

0 195082 195084 195086 195088 19509 195092 195094

SN (FMS) SN (SIM10)


80

60

40

20

0

[19010-20010]


5000

16


Diuron

Azoxystrobin

Fluridone

Benoxacor

Fenamidone

Desmedipham

Imazalil

2 4 6 8 10 12 14 Time (min)

0

50

100 0

50

100 0

50

100 0

50

100

Rel

ativ

e Ab

unda

nce

0

50

100 0

50

100 0

50

100 696

735

735

744

755

758

780








0

50

100 0

50

100 0

50

Rel

ativ

e Ab

unda

nce

100 0

50

100 2970551690455 2009867

25500821090763

3161774 720451

0

2330241 11908561591165

3070625100

50

1399895 2710859343039211203951650904 1490834

50

0 100

26002361200445 1880704

590500

2817393 3441026

37209743290791

316107821606551720391 4052731810705 920500

2361180

10305461650481 26709513121149

100 200 300 400 mz

17




18

Outline




19





20


EQuan MAX Plus



21







22






23







24


7 Detection

LC-M

S

LC-MSMS


internal StdFiltr

atio

n

6 Elution

5 Drying

4 Washing

3 Extraction

2 Conditioning

Enr

ichm

ent

MeOH H2O

60mg Oasis

H2OMeOH (955)

air

MeOH

40 samples ~ 5h

~ 2d

~ 2d




R T 5 9 8 - 8 0 0 N L 8 1 0 E 4

1 0 0

10 ul injection


9 0 1 0 u l _ 0 5

8 5

8 0

7 5

7 0

6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0



9 5 0 0 0 u l _ 0 4

9 0

8 5

8 0

7 5

7 0


6 0

Rel

ativ

e A

bund

ance

5 5

5 0

4 5 4 5

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 6 0 6 5 7 0

T i m e (m

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 7 5 8 0 6 0 6 5 7 0 7 5 8 0



26


27




assays















elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42



Pesticide in Matrix

23900 23905 23910 23915 23920 239250

20

40

60

80

100

Rel

ativ

e A

bund

ance

23915181 C 11 H 19 O 2 N 4

650 ppm

R = 17500 Error = 650 ppm

23900 23905 23910 23915 23920 23925 0

20

40

60

80

100

Rel

ativ

e A

bund

ance

H O

Pirimicarb

mzmz

23915033 C 11 H 19 O 2 N 4

032 ppm

R = 70000 Error = 032 ppm

9

35

40

45

50

55

60

65

Rel

ative

Abu

ndan

ce


100

95

90

85

80

75

70

65

60

55

50

45

40

35

30

25

20

15

10

5

0 22200 22205 22210 22215 22220 22225


2221463

2221838


0

5

10

15

20

25

30

70

75

80

85

90

95

100 2221238

2221129

2221465

2221854




2220 2221 2222 2223 mz mz

Relative Abu

ndan

ce

10

Mass accuracy

Mass accuracy

m mmeas truem z 106

mtrue



11



elat

ive

Rel

ativ

e

RT 845 NL 120E5100

2 ppm

72 74 76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106 Time (min)

30

40 50 60

Abu

ndan

ce

855799749 791776767 1061741726 105010311016946


70 MS pivo_5_UH

20 10 0

RT 845 NL 120E5100

20 ppm 72 74 76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106

Time (min)

30

40 50 60

Abu

ndan

ce

821762 785759740737 825781 792 799 861730726 10611050888 1031867 911 10161009946


70 MS pivo_5_UH

20 10 0

Rel

ativ

e

RT 845 NL 125E5100

30

40 50

Abu

ndan

ce

929872867 899878

911821785

1009 1016 1034100 ppm883813762759 781 810 835738

733 727 946 950 964 10611050


70 MS pivo_5_UH

60

20 10 0

72 7 7 78 8 8 8 8 8 9 9 9 9 9 100 102 104 106 4 6 0 2 4 6 8Time (min) 0 2 4 6 8








28900 28905 28910 28915 28920mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891314

2890513 2891022

2891215

2891329 2891424

28900 28905 28910 28915 28920mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891390

28910212890514

2891215

28913292891424




01033 amu

28900 28905 28910 28915 28920 mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891424 289154728913292891022

2890514

2891215 R = 140000

13


14



15

Caffeine


1950876 N=24840281 NL 194E8100

[15000-200000]

NL 112E8

Full MS SN = 745

Lowest detected

250330

80

signalscan60

40

20

0 1950877 N=2074158100

Rel

ativ

e A

bund

ance

SN

(spe

ctrum) 4000

3000

2000

1000

0 195082 195084 195086 195088 19509 195092 195094

SN (FMS) SN (SIM10)


80

60

40

20

0

[19010-20010]


5000

16


Diuron

Azoxystrobin

Fluridone

Benoxacor

Fenamidone

Desmedipham

Imazalil

2 4 6 8 10 12 14 Time (min)

0

50

100 0

50

100 0

50

100 0

50

100

Rel

ativ

e Ab

unda

nce

0

50

100 0

50

100 0

50

100 696

735

735

744

755

758

780








0

50

100 0

50

100 0

50

Rel

ativ

e Ab

unda

nce

100 0

50

100 2970551690455 2009867

25500821090763

3161774 720451

0

2330241 11908561591165

3070625100

50

1399895 2710859343039211203951650904 1490834

50

0 100

26002361200445 1880704

590500

2817393 3441026

37209743290791

316107821606551720391 4052731810705 920500

2361180

10305461650481 26709513121149

100 200 300 400 mz

17




18

Outline




19





20


EQuan MAX Plus



21







22






23







24


7 Detection

LC-M

S

LC-MSMS


internal StdFiltr

atio

n

6 Elution

5 Drying

4 Washing

3 Extraction

2 Conditioning

Enr

ichm

ent

MeOH H2O

60mg Oasis

H2OMeOH (955)

air

MeOH

40 samples ~ 5h

~ 2d

~ 2d




R T 5 9 8 - 8 0 0 N L 8 1 0 E 4

1 0 0

10 ul injection


9 0 1 0 u l _ 0 5

8 5

8 0

7 5

7 0

6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0



9 5 0 0 0 u l _ 0 4

9 0

8 5

8 0

7 5

7 0


6 0

Rel

ativ

e A

bund

ance

5 5

5 0

4 5 4 5

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 6 0 6 5 7 0

T i m e (m

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 7 5 8 0 6 0 6 5 7 0 7 5 8 0



26


27




assays















elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42


35

40

45

50

55

60

65

Rel

ative

Abu

ndan

ce


100

95

90

85

80

75

70

65

60

55

50

45

40

35

30

25

20

15

10

5

0 22200 22205 22210 22215 22220 22225


2221463

2221838


0

5

10

15

20

25

30

70

75

80

85

90

95

100 2221238

2221129

2221465

2221854




2220 2221 2222 2223 mz mz

Relative Abu

ndan

ce

10

Mass accuracy

Mass accuracy

m mmeas truem z 106

mtrue



11



elat

ive

Rel

ativ

e

RT 845 NL 120E5100

2 ppm

72 74 76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106 Time (min)

30

40 50 60

Abu

ndan

ce

855799749 791776767 1061741726 105010311016946


70 MS pivo_5_UH

20 10 0

RT 845 NL 120E5100

20 ppm 72 74 76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106

Time (min)

30

40 50 60

Abu

ndan

ce

821762 785759740737 825781 792 799 861730726 10611050888 1031867 911 10161009946


70 MS pivo_5_UH

20 10 0

Rel

ativ

e

RT 845 NL 125E5100

30

40 50

Abu

ndan

ce

929872867 899878

911821785

1009 1016 1034100 ppm883813762759 781 810 835738

733 727 946 950 964 10611050


70 MS pivo_5_UH

60

20 10 0

72 7 7 78 8 8 8 8 8 9 9 9 9 9 100 102 104 106 4 6 0 2 4 6 8Time (min) 0 2 4 6 8








28900 28905 28910 28915 28920mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891314

2890513 2891022

2891215

2891329 2891424

28900 28905 28910 28915 28920mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891390

28910212890514

2891215

28913292891424




01033 amu

28900 28905 28910 28915 28920 mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891424 289154728913292891022

2890514

2891215 R = 140000

13


14



15

Caffeine


1950876 N=24840281 NL 194E8100

[15000-200000]

NL 112E8

Full MS SN = 745

Lowest detected

250330

80

signalscan60

40

20

0 1950877 N=2074158100

Rel

ativ

e A

bund

ance

SN

(spe

ctrum) 4000

3000

2000

1000

0 195082 195084 195086 195088 19509 195092 195094

SN (FMS) SN (SIM10)


80

60

40

20

0

[19010-20010]


5000

16


Diuron

Azoxystrobin

Fluridone

Benoxacor

Fenamidone

Desmedipham

Imazalil

2 4 6 8 10 12 14 Time (min)

0

50

100 0

50

100 0

50

100 0

50

100

Rel

ativ

e Ab

unda

nce

0

50

100 0

50

100 0

50

100 696

735

735

744

755

758

780








0

50

100 0

50

100 0

50

Rel

ativ

e Ab

unda

nce

100 0

50

100 2970551690455 2009867

25500821090763

3161774 720451

0

2330241 11908561591165

3070625100

50

1399895 2710859343039211203951650904 1490834

50

0 100

26002361200445 1880704

590500

2817393 3441026

37209743290791

316107821606551720391 4052731810705 920500

2361180

10305461650481 26709513121149

100 200 300 400 mz

17




18

Outline




19





20


EQuan MAX Plus



21







22






23







24


7 Detection

LC-M

S

LC-MSMS


internal StdFiltr

atio

n

6 Elution

5 Drying

4 Washing

3 Extraction

2 Conditioning

Enr

ichm

ent

MeOH H2O

60mg Oasis

H2OMeOH (955)

air

MeOH

40 samples ~ 5h

~ 2d

~ 2d




R T 5 9 8 - 8 0 0 N L 8 1 0 E 4

1 0 0

10 ul injection


9 0 1 0 u l _ 0 5

8 5

8 0

7 5

7 0

6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0



9 5 0 0 0 u l _ 0 4

9 0

8 5

8 0

7 5

7 0


6 0

Rel

ativ

e A

bund

ance

5 5

5 0

4 5 4 5

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 6 0 6 5 7 0

T i m e (m

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 7 5 8 0 6 0 6 5 7 0 7 5 8 0



26


27




assays















elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42


Mass accuracy

Mass accuracy

m mmeas truem z 106

mtrue



11



elat

ive

Rel

ativ

e

RT 845 NL 120E5100

2 ppm

72 74 76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106 Time (min)

30

40 50 60

Abu

ndan

ce

855799749 791776767 1061741726 105010311016946


70 MS pivo_5_UH

20 10 0

RT 845 NL 120E5100

20 ppm 72 74 76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106

Time (min)

30

40 50 60

Abu

ndan

ce

821762 785759740737 825781 792 799 861730726 10611050888 1031867 911 10161009946


70 MS pivo_5_UH

20 10 0

Rel

ativ

e

RT 845 NL 125E5100

30

40 50

Abu

ndan

ce

929872867 899878

911821785

1009 1016 1034100 ppm883813762759 781 810 835738

733 727 946 950 964 10611050


70 MS pivo_5_UH

60

20 10 0

72 7 7 78 8 8 8 8 8 9 9 9 9 9 100 102 104 106 4 6 0 2 4 6 8Time (min) 0 2 4 6 8








28900 28905 28910 28915 28920mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891314

2890513 2891022

2891215

2891329 2891424

28900 28905 28910 28915 28920mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891390

28910212890514

2891215

28913292891424




01033 amu

28900 28905 28910 28915 28920 mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891424 289154728913292891022

2890514

2891215 R = 140000

13


14



15

Caffeine


1950876 N=24840281 NL 194E8100

[15000-200000]

NL 112E8

Full MS SN = 745

Lowest detected

250330

80

signalscan60

40

20

0 1950877 N=2074158100

Rel

ativ

e A

bund

ance

SN

(spe

ctrum) 4000

3000

2000

1000

0 195082 195084 195086 195088 19509 195092 195094

SN (FMS) SN (SIM10)


80

60

40

20

0

[19010-20010]


5000

16


Diuron

Azoxystrobin

Fluridone

Benoxacor

Fenamidone

Desmedipham

Imazalil

2 4 6 8 10 12 14 Time (min)

0

50

100 0

50

100 0

50

100 0

50

100

Rel

ativ

e Ab

unda

nce

0

50

100 0

50

100 0

50

100 696

735

735

744

755

758

780








0

50

100 0

50

100 0

50

Rel

ativ

e Ab

unda

nce

100 0

50

100 2970551690455 2009867

25500821090763

3161774 720451

0

2330241 11908561591165

3070625100

50

1399895 2710859343039211203951650904 1490834

50

0 100

26002361200445 1880704

590500

2817393 3441026

37209743290791

316107821606551720391 4052731810705 920500

2361180

10305461650481 26709513121149

100 200 300 400 mz

17




18

Outline




19





20


EQuan MAX Plus



21







22






23







24


7 Detection

LC-M

S

LC-MSMS


internal StdFiltr

atio

n

6 Elution

5 Drying

4 Washing

3 Extraction

2 Conditioning

Enr

ichm

ent

MeOH H2O

60mg Oasis

H2OMeOH (955)

air

MeOH

40 samples ~ 5h

~ 2d

~ 2d




R T 5 9 8 - 8 0 0 N L 8 1 0 E 4

1 0 0

10 ul injection


9 0 1 0 u l _ 0 5

8 5

8 0

7 5

7 0

6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0



9 5 0 0 0 u l _ 0 4

9 0

8 5

8 0

7 5

7 0


6 0

Rel

ativ

e A

bund

ance

5 5

5 0

4 5 4 5

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 6 0 6 5 7 0

T i m e (m

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 7 5 8 0 6 0 6 5 7 0 7 5 8 0



26


27




assays















elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42




elat

ive

Rel

ativ

e

RT 845 NL 120E5100

2 ppm

72 74 76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106 Time (min)

30

40 50 60

Abu

ndan

ce

855799749 791776767 1061741726 105010311016946


70 MS pivo_5_UH

20 10 0

RT 845 NL 120E5100

20 ppm 72 74 76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106

Time (min)

30

40 50 60

Abu

ndan

ce

821762 785759740737 825781 792 799 861730726 10611050888 1031867 911 10161009946


70 MS pivo_5_UH

20 10 0

Rel

ativ

e

RT 845 NL 125E5100

30

40 50

Abu

ndan

ce

929872867 899878

911821785

1009 1016 1034100 ppm883813762759 781 810 835738

733 727 946 950 964 10611050


70 MS pivo_5_UH

60

20 10 0

72 7 7 78 8 8 8 8 8 9 9 9 9 9 100 102 104 106 4 6 0 2 4 6 8Time (min) 0 2 4 6 8








28900 28905 28910 28915 28920mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891314

2890513 2891022

2891215

2891329 2891424

28900 28905 28910 28915 28920mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891390

28910212890514

2891215

28913292891424




01033 amu

28900 28905 28910 28915 28920 mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891424 289154728913292891022

2890514

2891215 R = 140000

13


14



15

Caffeine


1950876 N=24840281 NL 194E8100

[15000-200000]

NL 112E8

Full MS SN = 745

Lowest detected

250330

80

signalscan60

40

20

0 1950877 N=2074158100

Rel

ativ

e A

bund

ance

SN

(spe

ctrum) 4000

3000

2000

1000

0 195082 195084 195086 195088 19509 195092 195094

SN (FMS) SN (SIM10)


80

60

40

20

0

[19010-20010]


5000

16


Diuron

Azoxystrobin

Fluridone

Benoxacor

Fenamidone

Desmedipham

Imazalil

2 4 6 8 10 12 14 Time (min)

0

50

100 0

50

100 0

50

100 0

50

100

Rel

ativ

e Ab

unda

nce

0

50

100 0

50

100 0

50

100 696

735

735

744

755

758

780








0

50

100 0

50

100 0

50

Rel

ativ

e Ab

unda

nce

100 0

50

100 2970551690455 2009867

25500821090763

3161774 720451

0

2330241 11908561591165

3070625100

50

1399895 2710859343039211203951650904 1490834

50

0 100

26002361200445 1880704

590500

2817393 3441026

37209743290791

316107821606551720391 4052731810705 920500

2361180

10305461650481 26709513121149

100 200 300 400 mz

17




18

Outline




19





20


EQuan MAX Plus



21







22






23







24


7 Detection

LC-M

S

LC-MSMS


internal StdFiltr

atio

n

6 Elution

5 Drying

4 Washing

3 Extraction

2 Conditioning

Enr

ichm

ent

MeOH H2O

60mg Oasis

H2OMeOH (955)

air

MeOH

40 samples ~ 5h

~ 2d

~ 2d




R T 5 9 8 - 8 0 0 N L 8 1 0 E 4

1 0 0

10 ul injection


9 0 1 0 u l _ 0 5

8 5

8 0

7 5

7 0

6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0



9 5 0 0 0 u l _ 0 4

9 0

8 5

8 0

7 5

7 0


6 0

Rel

ativ

e A

bund

ance

5 5

5 0

4 5 4 5

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 6 0 6 5 7 0

T i m e (m

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 7 5 8 0 6 0 6 5 7 0 7 5 8 0



26


27




assays















elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42








28900 28905 28910 28915 28920mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891314

2890513 2891022

2891215

2891329 2891424

28900 28905 28910 28915 28920mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891390

28910212890514

2891215

28913292891424




01033 amu

28900 28905 28910 28915 28920 mz

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

2891424 289154728913292891022

2890514

2891215 R = 140000

13


14



15

Caffeine


1950876 N=24840281 NL 194E8100

[15000-200000]

NL 112E8

Full MS SN = 745

Lowest detected

250330

80

signalscan60

40

20

0 1950877 N=2074158100

Rel

ativ

e A

bund

ance

SN

(spe

ctrum) 4000

3000

2000

1000

0 195082 195084 195086 195088 19509 195092 195094

SN (FMS) SN (SIM10)


80

60

40

20

0

[19010-20010]


5000

16


Diuron

Azoxystrobin

Fluridone

Benoxacor

Fenamidone

Desmedipham

Imazalil

2 4 6 8 10 12 14 Time (min)

0

50

100 0

50

100 0

50

100 0

50

100

Rel

ativ

e Ab

unda

nce

0

50

100 0

50

100 0

50

100 696

735

735

744

755

758

780








0

50

100 0

50

100 0

50

Rel

ativ

e Ab

unda

nce

100 0

50

100 2970551690455 2009867

25500821090763

3161774 720451

0

2330241 11908561591165

3070625100

50

1399895 2710859343039211203951650904 1490834

50

0 100

26002361200445 1880704

590500

2817393 3441026

37209743290791

316107821606551720391 4052731810705 920500

2361180

10305461650481 26709513121149

100 200 300 400 mz

17




18

Outline




19





20


EQuan MAX Plus



21







22






23







24


7 Detection

LC-M

S

LC-MSMS


internal StdFiltr

atio

n

6 Elution

5 Drying

4 Washing

3 Extraction

2 Conditioning

Enr

ichm

ent

MeOH H2O

60mg Oasis

H2OMeOH (955)

air

MeOH

40 samples ~ 5h

~ 2d

~ 2d




R T 5 9 8 - 8 0 0 N L 8 1 0 E 4

1 0 0

10 ul injection


9 0 1 0 u l _ 0 5

8 5

8 0

7 5

7 0

6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0



9 5 0 0 0 u l _ 0 4

9 0

8 5

8 0

7 5

7 0


6 0

Rel

ativ

e A

bund

ance

5 5

5 0

4 5 4 5

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 6 0 6 5 7 0

T i m e (m

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 7 5 8 0 6 0 6 5 7 0 7 5 8 0



26


27




assays















elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42



14



15

Caffeine


1950876 N=24840281 NL 194E8100

[15000-200000]

NL 112E8

Full MS SN = 745

Lowest detected

250330

80

signalscan60

40

20

0 1950877 N=2074158100

Rel

ativ

e A

bund

ance

SN

(spe

ctrum) 4000

3000

2000

1000

0 195082 195084 195086 195088 19509 195092 195094

SN (FMS) SN (SIM10)


80

60

40

20

0

[19010-20010]


5000

16


Diuron

Azoxystrobin

Fluridone

Benoxacor

Fenamidone

Desmedipham

Imazalil

2 4 6 8 10 12 14 Time (min)

0

50

100 0

50

100 0

50

100 0

50

100

Rel

ativ

e Ab

unda

nce

0

50

100 0

50

100 0

50

100 696

735

735

744

755

758

780








0

50

100 0

50

100 0

50

Rel

ativ

e Ab

unda

nce

100 0

50

100 2970551690455 2009867

25500821090763

3161774 720451

0

2330241 11908561591165

3070625100

50

1399895 2710859343039211203951650904 1490834

50

0 100

26002361200445 1880704

590500

2817393 3441026

37209743290791

316107821606551720391 4052731810705 920500

2361180

10305461650481 26709513121149

100 200 300 400 mz

17




18

Outline




19





20


EQuan MAX Plus



21







22






23







24


7 Detection

LC-M

S

LC-MSMS


internal StdFiltr

atio

n

6 Elution

5 Drying

4 Washing

3 Extraction

2 Conditioning

Enr

ichm

ent

MeOH H2O

60mg Oasis

H2OMeOH (955)

air

MeOH

40 samples ~ 5h

~ 2d

~ 2d




R T 5 9 8 - 8 0 0 N L 8 1 0 E 4

1 0 0

10 ul injection


9 0 1 0 u l _ 0 5

8 5

8 0

7 5

7 0

6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0



9 5 0 0 0 u l _ 0 4

9 0

8 5

8 0

7 5

7 0


6 0

Rel

ativ

e A

bund

ance

5 5

5 0

4 5 4 5

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 6 0 6 5 7 0

T i m e (m

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 7 5 8 0 6 0 6 5 7 0 7 5 8 0



26


27




assays















elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42




15

Caffeine


1950876 N=24840281 NL 194E8100

[15000-200000]

NL 112E8

Full MS SN = 745

Lowest detected

250330

80

signalscan60

40

20

0 1950877 N=2074158100

Rel

ativ

e A

bund

ance

SN

(spe

ctrum) 4000

3000

2000

1000

0 195082 195084 195086 195088 19509 195092 195094

SN (FMS) SN (SIM10)


80

60

40

20

0

[19010-20010]


5000

16


Diuron

Azoxystrobin

Fluridone

Benoxacor

Fenamidone

Desmedipham

Imazalil

2 4 6 8 10 12 14 Time (min)

0

50

100 0

50

100 0

50

100 0

50

100

Rel

ativ

e Ab

unda

nce

0

50

100 0

50

100 0

50

100 696

735

735

744

755

758

780








0

50

100 0

50

100 0

50

Rel

ativ

e Ab

unda

nce

100 0

50

100 2970551690455 2009867

25500821090763

3161774 720451

0

2330241 11908561591165

3070625100

50

1399895 2710859343039211203951650904 1490834

50

0 100

26002361200445 1880704

590500

2817393 3441026

37209743290791

316107821606551720391 4052731810705 920500

2361180

10305461650481 26709513121149

100 200 300 400 mz

17




18

Outline




19





20


EQuan MAX Plus



21







22






23







24


7 Detection

LC-M

S

LC-MSMS


internal StdFiltr

atio

n

6 Elution

5 Drying

4 Washing

3 Extraction

2 Conditioning

Enr

ichm

ent

MeOH H2O

60mg Oasis

H2OMeOH (955)

air

MeOH

40 samples ~ 5h

~ 2d

~ 2d




R T 5 9 8 - 8 0 0 N L 8 1 0 E 4

1 0 0

10 ul injection


9 0 1 0 u l _ 0 5

8 5

8 0

7 5

7 0

6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0



9 5 0 0 0 u l _ 0 4

9 0

8 5

8 0

7 5

7 0


6 0

Rel

ativ

e A

bund

ance

5 5

5 0

4 5 4 5

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 6 0 6 5 7 0

T i m e (m

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 7 5 8 0 6 0 6 5 7 0 7 5 8 0



26


27




assays















elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42


Caffeine


1950876 N=24840281 NL 194E8100

[15000-200000]

NL 112E8

Full MS SN = 745

Lowest detected

250330

80

signalscan60

40

20

0 1950877 N=2074158100

Rel

ativ

e A

bund

ance

SN

(spe

ctrum) 4000

3000

2000

1000

0 195082 195084 195086 195088 19509 195092 195094

SN (FMS) SN (SIM10)


80

60

40

20

0

[19010-20010]


5000

16


Diuron

Azoxystrobin

Fluridone

Benoxacor

Fenamidone

Desmedipham

Imazalil

2 4 6 8 10 12 14 Time (min)

0

50

100 0

50

100 0

50

100 0

50

100

Rel

ativ

e Ab

unda

nce

0

50

100 0

50

100 0

50

100 696

735

735

744

755

758

780








0

50

100 0

50

100 0

50

Rel

ativ

e Ab

unda

nce

100 0

50

100 2970551690455 2009867

25500821090763

3161774 720451

0

2330241 11908561591165

3070625100

50

1399895 2710859343039211203951650904 1490834

50

0 100

26002361200445 1880704

590500

2817393 3441026

37209743290791

316107821606551720391 4052731810705 920500

2361180

10305461650481 26709513121149

100 200 300 400 mz

17




18

Outline




19





20


EQuan MAX Plus



21







22






23







24


7 Detection

LC-M

S

LC-MSMS


internal StdFiltr

atio

n

6 Elution

5 Drying

4 Washing

3 Extraction

2 Conditioning

Enr

ichm

ent

MeOH H2O

60mg Oasis

H2OMeOH (955)

air

MeOH

40 samples ~ 5h

~ 2d

~ 2d




R T 5 9 8 - 8 0 0 N L 8 1 0 E 4

1 0 0

10 ul injection


9 0 1 0 u l _ 0 5

8 5

8 0

7 5

7 0

6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0



9 5 0 0 0 u l _ 0 4

9 0

8 5

8 0

7 5

7 0


6 0

Rel

ativ

e A

bund

ance

5 5

5 0

4 5 4 5

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 6 0 6 5 7 0

T i m e (m

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 7 5 8 0 6 0 6 5 7 0 7 5 8 0



26


27




assays















elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42



Diuron

Azoxystrobin

Fluridone

Benoxacor

Fenamidone

Desmedipham

Imazalil

2 4 6 8 10 12 14 Time (min)

0

50

100 0

50

100 0

50

100 0

50

100

Rel

ativ

e Ab

unda

nce

0

50

100 0

50

100 0

50

100 696

735

735

744

755

758

780








0

50

100 0

50

100 0

50

Rel

ativ

e Ab

unda

nce

100 0

50

100 2970551690455 2009867

25500821090763

3161774 720451

0

2330241 11908561591165

3070625100

50

1399895 2710859343039211203951650904 1490834

50

0 100

26002361200445 1880704

590500

2817393 3441026

37209743290791

316107821606551720391 4052731810705 920500

2361180

10305461650481 26709513121149

100 200 300 400 mz

17




18

Outline




19





20


EQuan MAX Plus



21







22






23







24


7 Detection

LC-M

S

LC-MSMS


internal StdFiltr

atio

n

6 Elution

5 Drying

4 Washing

3 Extraction

2 Conditioning

Enr

ichm

ent

MeOH H2O

60mg Oasis

H2OMeOH (955)

air

MeOH

40 samples ~ 5h

~ 2d

~ 2d




R T 5 9 8 - 8 0 0 N L 8 1 0 E 4

1 0 0

10 ul injection


9 0 1 0 u l _ 0 5

8 5

8 0

7 5

7 0

6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0



9 5 0 0 0 u l _ 0 4

9 0

8 5

8 0

7 5

7 0


6 0

Rel

ativ

e A

bund

ance

5 5

5 0

4 5 4 5

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 6 0 6 5 7 0

T i m e (m

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 7 5 8 0 6 0 6 5 7 0 7 5 8 0



26


27




assays















elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42





18

Outline




19





20


EQuan MAX Plus



21







22






23







24


7 Detection

LC-M

S

LC-MSMS


internal StdFiltr

atio

n

6 Elution

5 Drying

4 Washing

3 Extraction

2 Conditioning

Enr

ichm

ent

MeOH H2O

60mg Oasis

H2OMeOH (955)

air

MeOH

40 samples ~ 5h

~ 2d

~ 2d




R T 5 9 8 - 8 0 0 N L 8 1 0 E 4

1 0 0

10 ul injection


9 0 1 0 u l _ 0 5

8 5

8 0

7 5

7 0

6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0



9 5 0 0 0 u l _ 0 4

9 0

8 5

8 0

7 5

7 0


6 0

Rel

ativ

e A

bund

ance

5 5

5 0

4 5 4 5

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 6 0 6 5 7 0

T i m e (m

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 7 5 8 0 6 0 6 5 7 0 7 5 8 0



26


27




assays















elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42


Outline




19





20


EQuan MAX Plus



21







22






23







24


7 Detection

LC-M

S

LC-MSMS


internal StdFiltr

atio

n

6 Elution

5 Drying

4 Washing

3 Extraction

2 Conditioning

Enr

ichm

ent

MeOH H2O

60mg Oasis

H2OMeOH (955)

air

MeOH

40 samples ~ 5h

~ 2d

~ 2d




R T 5 9 8 - 8 0 0 N L 8 1 0 E 4

1 0 0

10 ul injection


9 0 1 0 u l _ 0 5

8 5

8 0

7 5

7 0

6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0



9 5 0 0 0 u l _ 0 4

9 0

8 5

8 0

7 5

7 0


6 0

Rel

ativ

e A

bund

ance

5 5

5 0

4 5 4 5

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 6 0 6 5 7 0

T i m e (m

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 7 5 8 0 6 0 6 5 7 0 7 5 8 0



26


27




assays















elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42






20


EQuan MAX Plus



21







22






23







24


7 Detection

LC-M

S

LC-MSMS


internal StdFiltr

atio

n

6 Elution

5 Drying

4 Washing

3 Extraction

2 Conditioning

Enr

ichm

ent

MeOH H2O

60mg Oasis

H2OMeOH (955)

air

MeOH

40 samples ~ 5h

~ 2d

~ 2d




R T 5 9 8 - 8 0 0 N L 8 1 0 E 4

1 0 0

10 ul injection


9 0 1 0 u l _ 0 5

8 5

8 0

7 5

7 0

6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0



9 5 0 0 0 u l _ 0 4

9 0

8 5

8 0

7 5

7 0


6 0

Rel

ativ

e A

bund

ance

5 5

5 0

4 5 4 5

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 6 0 6 5 7 0

T i m e (m

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 7 5 8 0 6 0 6 5 7 0 7 5 8 0



26


27




assays















elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42



EQuan MAX Plus



21







22






23







24


7 Detection

LC-M

S

LC-MSMS


internal StdFiltr

atio

n

6 Elution

5 Drying

4 Washing

3 Extraction

2 Conditioning

Enr

ichm

ent

MeOH H2O

60mg Oasis

H2OMeOH (955)

air

MeOH

40 samples ~ 5h

~ 2d

~ 2d




R T 5 9 8 - 8 0 0 N L 8 1 0 E 4

1 0 0

10 ul injection


9 0 1 0 u l _ 0 5

8 5

8 0

7 5

7 0

6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0



9 5 0 0 0 u l _ 0 4

9 0

8 5

8 0

7 5

7 0


6 0

Rel

ativ

e A

bund

ance

5 5

5 0

4 5 4 5

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 6 0 6 5 7 0

T i m e (m

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 7 5 8 0 6 0 6 5 7 0 7 5 8 0



26


27




assays















elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42








22






23







24


7 Detection

LC-M

S

LC-MSMS


internal StdFiltr

atio

n

6 Elution

5 Drying

4 Washing

3 Extraction

2 Conditioning

Enr

ichm

ent

MeOH H2O

60mg Oasis

H2OMeOH (955)

air

MeOH

40 samples ~ 5h

~ 2d

~ 2d




R T 5 9 8 - 8 0 0 N L 8 1 0 E 4

1 0 0

10 ul injection


9 0 1 0 u l _ 0 5

8 5

8 0

7 5

7 0

6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0



9 5 0 0 0 u l _ 0 4

9 0

8 5

8 0

7 5

7 0


6 0

Rel

ativ

e A

bund

ance

5 5

5 0

4 5 4 5

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 6 0 6 5 7 0

T i m e (m

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 7 5 8 0 6 0 6 5 7 0 7 5 8 0



26


27




assays















elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42







23







24


7 Detection

LC-M

S

LC-MSMS


internal StdFiltr

atio

n

6 Elution

5 Drying

4 Washing

3 Extraction

2 Conditioning

Enr

ichm

ent

MeOH H2O

60mg Oasis

H2OMeOH (955)

air

MeOH

40 samples ~ 5h

~ 2d

~ 2d




R T 5 9 8 - 8 0 0 N L 8 1 0 E 4

1 0 0

10 ul injection


9 0 1 0 u l _ 0 5

8 5

8 0

7 5

7 0

6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0



9 5 0 0 0 u l _ 0 4

9 0

8 5

8 0

7 5

7 0


6 0

Rel

ativ

e A

bund

ance

5 5

5 0

4 5 4 5

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 6 0 6 5 7 0

T i m e (m

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 7 5 8 0 6 0 6 5 7 0 7 5 8 0



26


27




assays















elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42








24


7 Detection

LC-M

S

LC-MSMS


internal StdFiltr

atio

n

6 Elution

5 Drying

4 Washing

3 Extraction

2 Conditioning

Enr

ichm

ent

MeOH H2O

60mg Oasis

H2OMeOH (955)

air

MeOH

40 samples ~ 5h

~ 2d

~ 2d




R T 5 9 8 - 8 0 0 N L 8 1 0 E 4

1 0 0

10 ul injection


9 0 1 0 u l _ 0 5

8 5

8 0

7 5

7 0

6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0



9 5 0 0 0 u l _ 0 4

9 0

8 5

8 0

7 5

7 0


6 0

Rel

ativ

e A

bund

ance

5 5

5 0

4 5 4 5

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 6 0 6 5 7 0

T i m e (m

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 7 5 8 0 6 0 6 5 7 0 7 5 8 0



26


27




assays















elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42



7 Detection

LC-M

S

LC-MSMS


internal StdFiltr

atio

n

6 Elution

5 Drying

4 Washing

3 Extraction

2 Conditioning

Enr

ichm

ent

MeOH H2O

60mg Oasis

H2OMeOH (955)

air

MeOH

40 samples ~ 5h

~ 2d

~ 2d




R T 5 9 8 - 8 0 0 N L 8 1 0 E 4

1 0 0

10 ul injection


9 0 1 0 u l _ 0 5

8 5

8 0

7 5

7 0

6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0



9 5 0 0 0 u l _ 0 4

9 0

8 5

8 0

7 5

7 0


6 0

Rel

ativ

e A

bund

ance

5 5

5 0

4 5 4 5

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 6 0 6 5 7 0

T i m e (m

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 7 5 8 0 6 0 6 5 7 0 7 5 8 0



26


27




assays















elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42




R T 5 9 8 - 8 0 0 N L 8 1 0 E 4

1 0 0

10 ul injection


9 0 1 0 u l _ 0 5

8 5

8 0

7 5

7 0

6 5

6 0

Rel

ativ

e A

bund

ance

5 5

5 0



9 5 0 0 0 u l _ 0 4

9 0

8 5

8 0

7 5

7 0


6 0

Rel

ativ

e A

bund

ance

5 5

5 0

4 5 4 5

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 6 0 6 5 7 0

T i m e (m

4 0

3 5

3 0

2 5

2 0

1 5

1 0

5

0 7 5 8 0 6 0 6 5 7 0 7 5 8 0



26


27




assays















elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42



27




assays















elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42


elostrade

From Identification

28






29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42





29








31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42









31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42







31




Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42





Assay




32




33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42





33


34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42



34


Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42



Sample Site Inputs








35





36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42






36




RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42





RT 400-1357


90

80

70

60


175 pg on column 40

30

20

10

0

979

1026 687 1037

1126 946

817 785 663 1151 601 1242 584 434

4 5 6 7 8 9 10 11 12 13

TIC MS 175pgmL

Rel

ativ

e A

bund

uanc

e

Time (min)

37



38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42




38


39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42



39



Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42




Target screening




Suspect screening


40


41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42



41



Dionex ASE

Dionex UHPLC 3000








Orbitrap HRAM

Orbitrap Fusion

42


42


Date post:	10-Jun-2020
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