Emerging Interest in GC-Triple Quadrupole Mass Spectrometry for - - PowerPoint PPT Presentation

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Emerging Interest in GC-Triple Quadrupole Mass Spectrometry for - - PowerPoint PPT Presentation

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Emerging Interest in GC-Triple Quadrupole Mass Spectrometry for Environmental Analysis National Environmental Monitoring Conference August 18, 2011 Jason Cole, Product Manager GC/MS Presentation Overview What are the analytical strengths

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SLIDE 1

Emerging Interest in GC-Triple Quadrupole Mass Spectrometry for Environmental Analysis

National Environmental Monitoring Conference August 18, 2011 Jason Cole, Product Manager GC/MS

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SLIDE 2

Presentation Overview

  • What are the analytical strengths of GC/QqQ?
  • Example applications demonstrating strengths
  • Organotins in water
  • Organotins in water
  • PAH in rubber
  • Dioxins in food and feed

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SLIDE 3

Analytical Strengths of GC Triple Quadrupole

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SLIDE 4

Triple Quadrupole MS – Principle of Operation

Quantitation of target compounds in matrix samples

Select Fragment Detect rce

  • r

Ion Sour Detecto

Q1 selects the precursor ion TCDD ion: m/z 319 90 Q3 selects the product ion fragments to m/z 256 90

Argon Collision Gas 4

TCDD ion: m/z 319.90 fragments to m/z 256.90

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SLIDE 5

Analytical Strengths of Triple Quadrupole in SRM

Analytical Strength Analytical Reason Application Benefit

High sensitivity SRM has a high duty cycle Lowered LOQ’s/LOD’s g y g y y Hi h l ti it MS/MS li i t t L d LOQ’ /LOD’ High selectivity MS/MS eliminates most isobaric interferants Lowered LOQ’s/LOD’s Less sample prep Hi h d f l i High speed of analysis High specificity MS/MS eliminates most isobaric interferants Less false positives

SRM process offers opportunity for lowered LOQs, reduced sample prep, higher speed of analysis and less risk of false positives

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speed of analysis, and less risk of false positives

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SLIDE 6

Organotins in Drinking Water Organotins in Drinking Water

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SLIDE 7

Application Challenge and Approach

  • Lowered limits set by EU Water Directive
  • Maximum allowable concentration – 1.5 ng/L (ppt)
  • Maximum annual average – 0.2 ng/L (ppt)
  • Approach
  • Extraction
  • 400 ml of water at pH5
  • Extraction with pentane

E t d t 400 l

  • Evaporated to 400 µl
  • Derivatized with sodium tetra-ethyl borate
  • 3 µL injected into TSQ Quantum XLS GC triple quadrupole
  • 3 µL injected into TSQ Quantum XLS, GC triple quadrupole

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SLIDE 8

Customer Limits of Detection Using SIM

Compound LOD Using SIM Monobutyltin 10 ng/L Dibutyltin 5 ng/L Tributyltin 5 ng/L Triphenyltin 1 ng/L Triphenyltin 1 ng/L

Greater than order of magnitude improvement in detection limits needed

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detection limits needed

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SLIDE 9

Organotins at 0.5 ng/L

Injection of 0.2 pg absolute on column Corresponding with 0.05ng/L in water sample New EU directive: 0.2ng/L for tributyltin and here 0.05ng/l is shown

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SLIDE 10

PAHs in Rubber PAHs in Rubber

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SLIDE 11

The Case of the Problem Sample

  • Sample matrix: rubber
  • Looking for PAH’s that come from extender oils
  • Full sample prep applied to sample

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SLIDE 12

Comparison of Fullscan and SRM

Pyrene in rubber by fullscan Pyrene in rubber Pyrene in rubber by SRM Pyrene in Standard Pyrene in Standard by SRM

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SLIDE 13

Compounds Detected – SRM vs Fullscan

Compound SRM* Fullscan

Naphthalene

X X

Naphthalene

X X

Acenaphthylene

X

Acenaphthene

X

Anthracene

X

Anthracene

X

Phenanthrene

X

Pyrene

X

* All compounds confirmed with retention times and ion ratios (2)

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p ( )

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SLIDE 14

Benefits of Triple Quad for the Analysis

  • Less sample prep required
  • Ability to measure “worst case” samples

Ability to measure worst case samples

  • Greater confidence in confirmation

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SLIDE 15

Dioxins in Food and Feed Dioxins in Food and Feed

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SLIDE 16

Why GC-Triple Quad for Dioxins Analysis?

  • Screening
  • Higher quality of screening results
  • TEQs can be calculated from results of screen [1]
  • Congener specific - Results depend on PCDD/F and PCB congener

profile Impro ement of screening sensiti it for false negati e res lts belo 1%

  • Improvement of screening sensitivity for false negative results below 1%
  • Could result in a improved specificity, thus affecting the overall cost. [2]

C fi ti

  • Confirmation
  • Lower upfront cost
  • More versitile approach
  • References:
  • [1] Kotz, Malisch 2010, Dioxon Conference
  • [2] Fochi Brambilla 2008

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  • [2] Fochi, Brambilla 2008
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SLIDE 17

Maximum Allowed Levels

Commission Regulation (EC) No. 1881/2006 Commission Directive 2006/13/EC) Commission Directive 2006/13/EC)

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SLIDE 18

TSQ Quantum XLS TSQ Quantum XLS - TCDD in Buffalo Milk Samples

Blank Blank (GC (GC-

  • MS/MS)

MS/MS) Buffalo Milk (GC Buffalo Milk (GC-

  • MS/MS)

MS/MS) Buffalo Milk (GC Buffalo Milk (GC-

  • HRMS)

HRMS)

TCDD

0.17 pg/g fat

2,3,7,8-T

2,3,7,8

  • TCDD

STD Labeled IS

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SLIDE 19

Buffalo Milk Sample, HxCDD

GC-MS/MS (5 µl injection PTV solv. split )  GC-HRMS 1/10 concentration GC MS/MS GC HRMS

RT: 30.33 - 32.83 SM: 5G 60 80 100 RT: 31.50 AA: 82403

NL: 1.69E4 TIC F: + c EI SRM ms2 389.816 [326.802-326.902] MS ICIS BuffaloMilkA_Diox RT: 25.25 - 27.74 SM: 5G 60 80 100 RT: 26.44 AA: 2188 RT: 26.71 MA: 783 RT: 26.32 AA: 839

NL: 4.85E2 m/z= 389.7160- 389.9160 MS 100819_25956 A_16

GC-MS/MS GC-HRMS

80 100 ndance 20 40 RT: 31.31 AA: 14899 RT: 31.99 AA: 18515 RT: 31.51 AA: 53857

NL: 9.42E3 TIC F: + c EI SRM ms2 391.813 [328.799-328.899] MS ICIS 80 100 dance 20 40 AA: 839 25.46 25.57 26.09 27.32 27.00 27.62 25.90 RT: 26.43 AA: 1638 RT: 26.70

NL: 4.19E2 m/z= 391.7130- 391.9130 MS ICIS

100 20 40 60 Relative Abun RT: 31.98 AA: 11221 RT: 31.33 AA: 5188 RT: 31.97 AA: 13708676

BuffaloMilkA_Diox NL: 2.57E6 TIC F: + c EI SRM ms2 401.856 [337 839 337 939] MS 100 20 40 60 Relative Abun RT: 26.70 AA: 631 RT: 26.32 AA: 628 RT: 26.69 AA: 304546

ICIS 100819_25956 A_16 NL: 6.00E4 m/z= 401 7560-

20 40 60 80 RT: 31.48 AA: 3508171 RT: 32.26 AA: 49104 RT: 31.97 AA: 8797425

[337.839-337.939] MS ICIS BuffaloMilkA_Diox NL: 1.65E6 TIC F: + c EI SRM 20 40 60 80 RT: 26.43 AA: 76282 RT: 26.69 AA: 242407

401.7560 401.9560 MS ICIS 100819_25956 A_16 NL: 4.88E4

20 40 60 80 100 AA: 8797425 RT: 31.49 AA: 2309415 RT: 32.26 AA: 33481

TIC F: c EI SRM ms2 403.853 [339.836-339.936] MS ICIS BuffaloMilkA_Diox 20 40 60 80 100 AA: 242407 RT: 26.43 AA: 59305 RT: 26.96 AA: 2074

m/z= 403.7530- 403.9530 MS ICIS 100819_25956 A_16

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30.5 31.0 31.5 32.0 32.5 Time (min)

25.5 26.0 26.5 27.0 27.5 Time (min)

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SLIDE 20

TSQ Quantum XLS TSQ Quantum XLS vs. GC-HRMS of Certified Material

1 80 2.00 TSQ HRMS CERTIFIED LOQs 1.40 1.60 1.80

Results in [pg TEQ/g fat] TSQ 3,22 (5% RSD) HRMS 3 23 (2% RSD)

0.80 1.00 1.20

HRMS 3.23 (2% RSD)

0 20 0.40 0.60 0.00 0.20 2 , 3 , 7 , 8

  • T

C D D 2 , 3 , 7 , 8

  • P

e C D D 3 , 4 , 7 , 8

  • H

x C D D 3 , 6 , 7 , 8

  • H

x C D D 3 , 7 , 8 , 9

  • H

x C D D 4 , 6 , 7 , 8

  • H

p C D D O C D D 2 , 3 , 7 , 8

  • T

C D F 1 2 , 3 , 7 , 8

  • P

e C D F 2 3 , 4 , 7 , 8

  • P

e C D F 3 , 4 , 7 , 8

  • H

x C D F 3 , 6 , 7 , 8

  • H

x C D F 3 , 7 , 8 , 9

  • H

x C D F 4 , 6 , 7 , 8

  • H

x C D F 4 , 6 , 7 , 8

  • H

p C D F 4 , 7 , 8 , 9

  • H

p C D F O C D F

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2 1 , 2 , 1 , 2 , 3 , 4 1 , 2 , 3 , 1 , 2 , 3 , 1 , 2 , 3 , 4 , 1 , 2 2 , 3 1 , 2 , 3 , 1 , 2 , 3 , 1 , 2 , 3 , 2 , 3 , 4 , 1 , 2 , 3 , 4 , 1 , 2 , 3 , 4 ,

Courtesy N. Iacovella, G. Brambilla, ISS, Rome, Italy

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SLIDE 21

TSQ Quantum XLS Ultra – Food Dioxin Screening

  • Courtesy Alexander Kotz, EURL Freiburg, Germany
  • Presented at the 6th POPs Users Meeting, Niagara-on-the-Lake, Canada, Apr 28/29, 2011

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Deviation of MS/MS

40 60 80

  • f HRMS

Food Samples Deviation of MS/MS from HRMS

[%]

20 20 1 2 3 4 5 6 7 8 9 10 MS/MS results o

  • 60
  • 40
  • 20

Deviation of M

Measurement of same extracts

  • 100
  • 80

WHO-PCDD/F-TEQ [pg/g fat]

Measurement of same extracts using DFS GC-HRMS and TSQ Quantum XLS Ultra GC-MS/MS

Butter, Eggs, Meat and Fat EU Maximum Levels 21

Butter Eggs Fat Meat Human milk

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SLIDE 22

Conclusion From Webinar by Dr. Kotz

  • GC-MS/MS systems in principle applicable for PCDD/F and DL-PCB

analysis in food and feed samples

  • Sensitive enough to check for dioxins at maximum allowed levels
  • GC/HRMS still preferred at lower concentration

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SLIDE 23

Presenation Summary

  • Laboratories are showing increasing interest in GC triple quad

technology because of inherent advantages in the technology:

  • Low LOQ’s from combination of high selectivity with high sensitivity

Q g y g y

  • High specificity for more confident results
  • Examples of application of technology
  • Examples of application of technology
  • Organotins in drinking water for reduced LOQ’s
  • PAH in rubber for confident detection in worst case matrix scenario
  • Dioxins in food and feed for higher sensitivity/specificity screening

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SLIDE 24

Thank you very much for Thank you very much for your attention!

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