Product Specifications Thermo Scientiﬁc Pesticide Analyzer … · 2020. 11. 23. · to quantitate...

Product Specifications

Pesticide Analyzer ReferenceThe analysis of pesticides poses greaterchallenges on the operator and instrumentthan any other analysis. This reference provides information for the operator thatallows them to become productive quickly.It provides the necessary information toimplement new methods quickly and easily.

The NeedThere are approximately 600 pesticides thatcan be analyzed by a GC/MS system. Thematrices that are tested vary from fruits andvegetables to soil and water. The pesticideshave a wide range of chemistries that mustbe taken into account. The challenge is totest for as many pesticides as possible inthe shortest period of time while being ableto quantitate below the maximum residuelevels (MRL).

The SolutionThe Thermo Scientific Pesticide AnalyzerReference provides information for thedevelopment of methods that can analyzeapproximately 600 pesticides. The informationwill allow the operator to develop methodson the TSQ Quantum GC triple quadrupolequickly. This information can be easily customized and imported directly into theinstrument method saving large amount oftime on method development. A procedureis also provided for extracting samples usinga quechers technique. All of the consumablesthat are required for the extraction andanalyses are listed with part number. Thecombination of the extractions, instrumentparameters, and consumables provides theability to avoid the most time consumingparts of the method development process.

Thermo ScientificPesticide Analyzer ReferenceMethod development for the longest listof pesticides

The Thermo Scientific PesticideAnalyzer Reference provides information on extractions andmultiple reaction monitoring (MRM)of pesticides in any matrix. It allowsfor fast method development fornew pesticide methods

Part of Thermo Fisher Scientific

c h r o m a t o g r a p h y


PS10307_E 07/09M

Specifications

• A reference guide and CD that provides MRM parameters forapproximately 600 compounds.

• Step by step procedure to follow for the extraction of pesticidesand other contaminants using a quechers extraction technique

• Part numbers for all the materials needed for the quechers extractions

• Consumable information that has proven to work across broad classes of pesticides

Thermo Fisher Scientific, Austin, TX USA is ISO Certified.©2009 Thermo Fisher Scientific Inc. All rights reserved. All trademarks are the property of Thermo Fisher Scientific Inc. and its subsidiaries.

Specifications, terms and pricing are subject to change. Not all products are available in all countries. Please consult your local sales representative for details.


Africa-Other +27 11 570 1840Australia +61 2 8844 9500Austria +43 1 333 50 34 0Belgium +32 2 482 30 30Canada +1 800 530 8447China +86 10 8419 3588

Denmark +45 70 23 62 60Europe-Other +43 1 333 50 34 0Finland / Norway / Sweden

+46 8 556 468 00France +33 1 60 92 48 00Germany +49 6103 408 1014

India +91 22 6742 9434Italy +39 02 950 591Japan +81 45 453 9100Latin America +1 608 276 5659Middle East +43 1 333 50 34 0Netherlands +31 76 579 55 55

South Africa +27 11 570 1840Spain +34 914 845 965Switzerland +41 61 716 77 00UK +44 1442 233555USA +1 800 532 4752www.thermo.com

The Next Evolution in GC Triple Quadrupoles


Thermo ScientificTSQ Quantum GC™ TripleQuadrupole GC-MS/MS

Excellent selectivity, even in the dirtiest samples

Fast acquisition rate for optimal productivity

Simultaneous quantitation andconfirmation (QED-MS/MS)

Convertible between GC/MS and LC/MS


TSQ Q

uantum G

C

2

THERMO SCIENTIFIC TSQ QUANTUM GC

The TSQ Quantum GC is the next evolutionin GC triple quadrupole mass spectrometry, offering unique features including Highly Selective Reaction Monitoring (H-SRM), which enables increased analyte selectivity in complex matrices, and Quantitation-Enhanced Data-Dependent MS/MS (QED-MS/MS),which provides simultaneous quantitationand structural confirmation.

In addition, the option to switch between GC and LC modes or to change from EI to CI provides an extremely flexible system to meet your mass spectrometry needs.

Continuing over 25 years of triple quadrupole GC/MS technology

leadership, Thermo Fisher Scientific introduces the TSQ Quantum GC,

a high-performance GC-MS/MS system that offers class-leading

features and specifications that match your most demanding

quantitative needs.

History of the TSQ Quantum

Signature Benefits

• Multi-residue screening – quantitatehundreds of compounds in a singlerun with 1 ms dwell time

• Higher selectivity and more confidencewith H-SRM

• Simultaneous quantitation and structuralconfirmation with QED-MS/MS

• Eliminate false positives with Zero Cross-Talk Collision Cell

• 21 CFR Part 11 enabled softwarefor regulatory compliance

3

TSQ Quantum GC key benefits:

• Highest selectivity (H-SRM)

• Lowest limits of quantitation

• Simultaneous quantitation and structuralconfirmation with QED-MS/MS

• High-speed data acquisition for multi-component analysis

• Structure-Selective Detection (SSD) using MS/MS

• Unique zero cross-talk collision cell

TSQ Quantum GC versatility:

• Exchangeable ion volumes for EI and CIwithout breaking vacuum

• Combination ion volume for automated EI/CIoperation

• Convertible between GC/MS and LC/MS

• Mass range up to m/z 3000

• Scan speeds up to 5000 u/s

• Specify up to 3000 SRM transitions per run

• Digital reagent gas control

• PPINICI™ – pulsed positive ion negative ionchemical ionization for sample screening

• DEP and DIP solid probe inlets

Fast analysis of 170 pesticides using SRM and H-SRM

Selected Reaction Monitoring (SRM)is the primary technique used with atriple quadrupole mass spectrometerfor quantitative analysis. However,selection of a precursor ion at a normal unit resolution often sufferschemical noise interferences fromendogenous biological and environ-mental matrices.

Highly Selective Reaction Monitoring(H-SRM) allows the user to have morestringent tolerance for precursor ion selection in Q1, which leads toincreased analyte selectivity. Thiscan result in lower limits of detection,and improved precision and accuracyat the LOD.

Our high-precision hyperbolicquadrupoles are the only quadrupoleson the market capable of such massselectivity without a significant lossin transmission.

HIGHLY SELECTIVE REACTION MONITORING (H-SRM)–CLASS-LEADING SELECTIVITY

Reduce false positives with high transmission

at enhanced resolution

TSQ Q

uantum G

C

4

Comparison of chromatograms for residueanalysis of Parathion in green pepper at 1 pg/μL. Left shows unit resolution (SRM) andright shows H-SRM with enhanced resolution.

SENSITIVITY FOR THE MOST DEMANDING ASSAYS

Excellent sensitivity, vital for routine quantitation in every laboratory

Chromatograms of pentafluorobenzoyl and MSTFA derivatized estradiol (55 fg injected on column,2.5 pg/mL sample concentration) and its d4 analogue (as internal standard) extracted from plasmasample (Sample provided by Taylor Technology, Inc.)

Detection of endogenous estrogenssuch as estradiol in biological fluidshas wide applications. The hormoneis suspected to be an indicator ofdisease states. The analytical methodfor estradiol is often compromisedas a result of interferences from theendogenous biological matrices.

The TSQ Quantum GC offers ahighly selective, sensitive androbust method for analyzing thesecompounds using negative CI andselected reaction monitoring. Figureat right illustrates a representativechromatogram of low-level estradiolin plasma samples.

Quantitation-Enhanced Data-Dependent MS/MS (QED-MS/MS)

SIMULTANEOUS QUANTITATION AND CONFIRMATIONIN A SINGLE RUN

This innovative scanning mode,available as a standard feature onthe TSQ Quantum GC, providessimultaneous quantitation (H-SRM)

and structural confirmation (MS/MSproduct ion spectra). The feature is extremely beneficial for multi-residue screening experiments.

With enhanced resolution, the higher quality MS/MS spectra areeasily searchable against spectrallibraries for added structural confirmation.

MS/MS Confirmation(Scan Event 2)

SRM Quantitation(Scan Event 1)

QED-MS/MS of Pesticidesin Green PepperScan Event 1 shows multi-residueanalysis of pesticides at 10 pg/μL.Scan event 2 confirms the structuresof Diazinon (left) and Parathion-methyl (right) at the same concen-tration. QED-MS/MS provides simultaneous quantitation and structural confirmation in metaboliteidentification or multi-residue screens.

Beneficios exclusivos

• Análisis multiresiduales: cuantifica cientos de compuestos en un solo barrido con un tiempo de permanencia de 1 ms

• Mayor selectividad y más confiabilidad con H-SRM

• Confirmación de estructuras y cuantificaciónsimultáneas con QED-MS/MS

• Elimina los positivos falsos gracias a la celda de colisión de cero “crosstalk”

• Software preparado para el cumplimiento de lanorma 21 CFR Parte 11

6

7

EASY-TO-USE ADVANCED GC-MS/MS TECHNOLOGY

High performance and high throughput – maximum value

for your GC-MS/MS instrument investment

Thermo Scientific TRACE GC Ultra™

The process of GC-MS/MS beginswith the gas chromatograph. TheThermo Scientific TRACE GC Ultra is a versatile laboratory GC with afull range of detectors and injectorsdesigned to dramatically increasesample throughput, making theTRACE GC Ultra the ideal partner forthe TSQ Quantum GC. Automatedfeatures result in a tremendousincrease in sample throughput, withanalyses performed up to 30 timesfaster than before, without compro-mising precision.

• Exceptional system usability,automation, and speed of analyses

• Industry-leading Split/Splitless,PTV, and Cold On-column injectors,all also available in Large Volumemodes to maximize sensitivity

• Proprietary Automatic ColumnCharacterization (ACC) and leakcheck functions improve ease ofuse and reduce column-to-columnand instrument-to-instrumentvariations

• Direct coupling of the TSQQuantum GC ion source to theGC/MS interface provides uniformtemperature distribution and precise temperature control up to 350 °C

• Integrated control of TSQ QuantumGC, TRACE GC Ultra, injector andinterface temperatures, and valvetiming using the Thermo ScientificXcalibur™ data system

Thermo Scientific Autosamplers –Flexible Sampling SolutionsAutomate routine sample injectionsand improve productivity with theThermo Scientific AI/AS 3000 Series IIliquid autosampler. Or, experience theflexible Thermo Scientific TriPlus™

autosampler as the ideal partner for your TSQ Quantum GC system.

AI/AS 3000 Series II• Easy setup and simple self-

alignment

• AI 3000 II with switchable sampletrays for routine injections

• AS 3000 II with 105-vial sampletray increases productivity

• Four rinsing stations virtuallyeliminate carryover and cross-contamination

TriPlus• TriPlus AS for versatile liquid

injections

• TriPlus HS for syringe-basedheadspace analyses

• TriPlus Duo to easily change fromliquid to headspace mode

• TriPlus SPME* for automatedsample prep using solid phasemicroextraction

• Cooled/heated tray option for thehandling of very volatile solventsand very viscous samples atambient temperature

Thermo Scientific Direct SampleProbe – Switch to probe in under

three minutes, leaving the GC interface undisturbed. Available intwo styles: Direct Exposure Probe(DEP) with rapid-heating filament,

or Direct Insertion Probe (DIP) withslower volatilization for bulk

samples and mixture analysis.

Avantages Signature

• Analyse multi-résidus - quantification de centaines de composés en une seule acquisition avec une vitesse de balayage de 1 ms

• Sélectivité et fiabilité plus élevées en mode H-SRM

• Quantification et confirmation structurale simultanées en mode QED-MS/MS

• Élimine les faux positifs avec la cellule de collision sans effet cross-talk

• Logiciel prêt pour la conformité aux normes 21 CFR Part 11

* Sold under license from Supelco®

The Thermo Scientific TSQ Quantum GC is ideal for challengingGC-MS/MS applications fromresearch to routine. Thermo ScientificLab Forms software packages provideoptimal productivity and complementroutine applications. Lab Forms

packages offer standard featuresthat streamline your workflows.Innovative new Method Forge provides an automated pathway togenerating full scan methods. Wizardsand templates make programmingdaily batches straightforward, greatlyreducing the time needed to queuesamples and begin acquiring data.

Where the Lab Forms softwarepackages truly redefine workflows is with a revolutionary approach todata review and reporting. Throughpowerful Smart Reporting, datareview and data reporting aredynamically linked, allowing forreal-time changes to reports based onchanges to the data. For example, ifthe Active Report shows an out-of-range ion ratio, simply double-clickthe result to go straight to that com-pound, for that sample. Review the

integration – if it’s as simple as re-drawing the peak integration, thenthis change can be made within DataReview. Return to the active reportand the new integration is immedi-ately reflected – no reprocessing,no re-analyzing the data.

The Lab Forms packages includegeneral purpose software, ThermoScientific QuanLab™ Forms, ideal forGC/MS quantitation across a widerange of applications. ThermoScientific EnviroLab™ Forms providesreporting options that facilitateworkflows for routine environmentalGC/MS applications. ThermoScientific ToxLab™ Forms includesreport styles and quality control settings that suit the needs offorensic and toxicology laboratories.

Xcalibur is the most powerful and robust data system available,delivering a unique combination of functionality, system control, and ease of use. The software is designed to guide the userthrough daily analytical tasks. This powerful simplicity combinedwith the advanced features of theMicrosoft® Windows® operatingsystem and Microsoft Office productivity tools provides an analytical platform that’s second to none.

THERMO SCIENTIFIC XCALIBUR–A UNIFIED SOFTWARE PLATFORM

One intuitive platform for GC/MS, LC/MS, and Advanced MS

instruments provides confident control from method

development to reporting.

TSQ Q

uantum G

C

8

Xcalibur’s home page (left) offerseasy navigation through the processof instrument setup, sequence setup,and data acquisition. Data can bereviewed in three browsers: QualBrowser, Quan Browser, and LibraryBrowser.

Workflow-oriented applications make routine GC-MS/MSanalyses easier and more productive.

Caratteristiche esclusive

• Dosaggio multi-residuo - Determinazione quantitativa di centinaia di composti in una singola analisi con tempo di scansione (dwell time) di 1 ms

• Migliore selettività e più sicurezza con H-SRM

• Determinazione quantitativa e simultanea conferma strutturale con QED-MS/MS

• Eliminazione dei falsi positivi grazie alla cella di collisione con eliminazione totale delle interferenze (Zero Cross-Talk)

• Programma software conforme ai requisiti della norma 21 CFR Parte 11

POWERFUL SOFTWARE PACKAGES FOLLOW LABORATORY

WORKFLOWS FOR MAXIMUM PRODUCTIVITY

Xcalibur provides complete control of the TSQ QuantumGC, the TRACE GC Ultra, and the TriPlus or AI/AS 3000autosampler, as well as other devices. Xcalibur contains abuilt-in audit trail to ensure compliance with a laboratory’sSOPs and quality programs. Xcalibur also lays the solidfoundation for a set of layered applications, which offertailored approaches to routine quantitative workflows.

Entscheidende Vorteile

• Multikomponenten-Screening - Quantifizieren SieHunderte von Verbindungen in einem einzigen Lauf mit einer „Dwell Time“ von 1 ms

• Höhere Selektivität und mehr Vertrauen mit H-SRM

• Simultane Quantifizierung und Strukturbestätigung mit QED-MS/MS

• Eliminieren Sie falsch-positive Ergebnisse mit derKollisionszelle ohne „Cross-Talk”

• Die Software unterstützt die im Regelwerk der „21 CFR Part 11“ festgelegten Anforderungen derQualitätssicherung

9

ToxLab FormsToxLab Forms is designed to offer an intuitive, work-flow oriented approach to GC/MS acquisition, analysis,and reporting in the clinical or forensic toxicologylaboratory. ToxLab Forms streamlines the path fromunknown sample to known result in a manner that issecure, defensible and aligned with your lab’s specificneeds. Enhancements specific to your toxicology lab’sneeds are built into the system, including standardreport formats to simplify reporting. ToxLab Formsprovides automated spectral library searching onnon-target peaks and report semi-quantitative results.

QuanLab FormsQuanLab Forms provides a powerful productivity tool forquantitative and semi-quantitative GC/MS experimentsacross a broad range of applications. QuanLab Forms provides an integrated, workflow-oriented approach toGC/MS data analysis and reporting. A wide selection ofstandard reports allows for easily reporting data in a stylethat suits your lab’s needs. Generate reports in real timeduring sample acquisition, or review and report datathrough the intuitive Data Review screen. QuanLab Formsis ideally suited for applications where management oflong lists of target compounds is critical.

Data Review in Lab Forms packages

Innovative Method Forge simplifies method creation

Clearly display and review peak integrations

EnviroLab FormsToday’s environmental labs must balance high productivity and throughput with stringent qualitycontrol protocols. EnviroLab Forms has been designedto follow environmental laboratory workflows, fromsample to result. EnviroLab Forms features a widerange of report options tailored to the needs of environmental laboratories.

BR10276_E 12/08M

Thermo Fisher Scientific,San Jose, CA USA is ISO Certified.

©2008 Thermo Fisher Scientific Inc. All rights reserved.Microsoft and Windows are registered trademarks ofMicrosoft Corporation, Supelco is a registered trademarkof Sigma-Aldrich, Inc. All other trademarks are the prop-erty of Thermo Fisher Scientific Inc. and its subsidiaries.

Specifications, terms and pricing are subject to change.Not all products are available in all countries. Pleaseconsult your local sales representative for details.

Tap our expertise throughout the life of your instrument. Thermo Scientific Services

extends its support throughout our worldwide network of highly trained and certified

engineers who are experts in laboratory technologies and applications. Put our team

of experts to work for you in a range of disciplines – from system installation, training

and technical support, to complete asset management and regulatory compliance

consulting. Improve your productivity and lower the cost of instrument ownership

through our product support services. Maximize uptime while eliminating the

uncontrollable cost of unplanned maintenance and repairs. When it’s time to

enhance your system, we also offer certified parts and a range of accessories and

consumables suited to your application.

To learn more about our products and comprehensive service offerings,

visit us at www.thermo.com.

Laboratory Solutions Backed by Worldwide Service and Support In addition to these offices, ThermoFisher Scientific maintains a network of representative organizationsthroughout the world.

Africa-Other+27 11 570 1840 • [email protected]

Australia+61 2 8844 9500 • [email protected]

Austria+43 1 333 50 34 0 • [email protected]

Belgium+32 2 482 30 30 • [email protected]

Canada+1 800 530 8447 • [email protected]

China+86 10 8419 3588 • [email protected]

Denmark+45 70 23 62 60 • [email protected]

Europe -Other+43 1 333 50 34 0 • [email protected]

Finland / Norway / Sweden+46 8 556 468 00 • [email protected]

France+33 1 60 92 48 00 • [email protected]

Germany+49 6103 408 1014 • [email protected]

India+91 22 6742 9434 • [email protected]

Italy+39 02 950 591 • [email protected]

Japan+81 45 453 9100 • [email protected]

Latin America+1 608 276 5659 • [email protected]

Middle East+43 1 333 50 34 0 • [email protected]

Netherlands+31 76 579 55 55 • [email protected]

South Africa+27 11 570 1840 • [email protected]

Spain+34 914 845 965 • [email protected]

Switzerland+41 61 716 77 00 • [email protected]

UK+44 1442 233555 • [email protected]

USA+1 800 532 4752 • [email protected]

www.thermo.com


With the TSQ Quantum GC™ Thermo FisherScientific continues the successful and well-known TSQ™ triple quadrupole mass spectrometer series, now combined withthe power, performance and flexibility of the Thermo Scientific TRACE GC Ultra gas chromatograph.

The TSQ Quantum GC delivers unsurpassed performance, even in complexmatrix, through the incorporation of thefield-proven DuraBrite™ ion source, precisionhyperbolic quadrupoles, highest ion trans-mission and innovative detection technology.The TSQ Quantum GC is the most selectiveand sensitive GC-triple quadrupole massspectrometer available today.

State-of-the-art electronics and comprehensive diagnostics are hallmarks ofour instruments. You have total instrumentcontrol at your fingertips through the easy-to-use Thermo Scientific Xcalibur software.

With these industry-leading features, theTSQ Quantum GC defines the new standardof excellence in GC-MS/MS analysis.

Thermo ScientificTSQ Quantum GCThe Next Evolution in GC-MS/MS Systems

The Thermo Scientific TSQQuantum GC defines a new standard of excellence in GC-MS/MS for multi-componenttarget compound analysis in environmental, food safety, pharmaceutical, toxiological, andclinical research laboratories.

• Highest selectivity even in complexsamples with enhanced resolution(H-SRM)

• Analyze more than 1000 compoundsper run, with two transitions each

• Simultaneous quantitation andconfirmation with QED-MS/MS

• Mass range up to m/z 3000

• Scan speeds: up to 5000 u/s

• PPINICI™ – pulsed positive ionnegative ion chemical ionizationfor sample screening

• Convertible between GC/MS andLC/MS



Hardware Features

DuraBrite Source• DuraBrite source allows detection of low-

level analytes in challenging matrices andprovides unparalleled high uptime alongwith increased sensitivity

• No tools required for routine source maintenance

• Durable materials guarantee long life and simple maintenance

• Exchange ion volumes in minutes withoutbreaking system vacuum

• Standard EI, CI, CEI or EI/CI ion volumes,maximizing performance in EI, positiveion CI, and negative ion CI

• Computer-controlled CI reagent gas flowcontrol for high quantitative accuracyand day-to-day calibration stability

• Unique electron lens isolates filamentfrom contaminants of the source,increases lifetime, and improvesionization efficiency

• Electron beam collimating magnetsfurther increase ionization efficiency

• Electron energy adjustable between0 and 140 eV

• Emission current up to 1000 μA• Independently controlled heating from

125 – 300 °C for stable operation andsuperior chromatographic integrity

• GC interface temperature up to 350 °C

Triple Quadrupole Mass Analyzer• Mass range of m/z 10 – 3000• Patented HyperQuad™ mass analyzers

provide superior and unique combinationof resolution and sensitivity

• Highest compound selectivity with H-SRM at 0.4 Da peak width (FWHM)

• Multi-compound detection with up to3000 SRM transitions in one run

• Fast scan speed of more than 300 SRM/s• 90° high-efficiency square quadrupole

collision cell with noise-reducing geometry• CID gas pressure programmable through

the software• Variable peak width selection in all

scan modes• Scan rate of 5,000 u per second

Vacuum System• Unique close-coupled triple inlet turbo

molecular pumping 270 L/s• Two stages of pumping provide optimal

vacuum throughout GC/MS/MS analyzer• Single mechanical pump 30 L/min,

floorstanding

Inlet/Vacuum Interlock • Allows easy exchange of ion volumes for

fast switching from EI to CI, from GC toprobe analysis, and for routine sourcemaintenance without breaking vacuum

Detection System• Patented detection system uses a fast

switching (< 95 ms) post-acceleration conversion dynode with ±15 kV appliedvoltage

• Off-axis continuous dynode electron multiplier with increased dynamic range

• System integrated electron multipliereliminates field emission and microphonicnoise

• Centroid or profile data acquisition modes• PPINICI mode to acquire positive ion CI and

negative ion CI spectra in alternating scans

Scan Functions• Highly sensitive Full-Scan MS in Q1 or Q3• Selected Ion Monitoring (SIM) in Q1 or Q3• Selected Reaction Monitoring (SRM) for

demanding quantitative assays• Highly Selective Reaction Monitoring

(H-SRM) for optimal selectivity• Product Ion Scan• Precursor Ion Scan• Neutral Loss Scan

Advanced Data-Dependent™

Experiments• Available from all scan functions• Dynamic Exclusion™ allows acquisition

of MS/MS spectra from lower intensity ion species

• Polarity switching capabilities• AutoSIM• Quantitation-enhanced Data-dependent

MS/MS (QED-MS/MS) for simultaneouscompound confirmation and quantitation

• Reverse Energy Ramp MS/MS spectra(RER) gives information rich MS/MSspectra for solid compound identification

TRACE GC Ultra Gas ChromatographSee the TRACE GC Ultra™ product specificationfor additional specifications for the gaschromatograph.• Multi-level temperature program with

seven ramps and eight levels settablefrom 0.1– 120 °C/min

• Eight independent, heated zones for individual control of injectors and detectors plus auxiliary zones

• Capillary split/splitless injectors withDigital Pressure and Flow Control (DPFC)including gas saver

• Maximum oven temperature 450 °C • Superior oven cool-down for increased

sample productivity, from 450 °C – 50 °Cin 250 seconds

GC Options• Broad range of GC options for maximum

versatility• Sub-ambient cooling to -99 °C with LN2

or -55 °C with CO2

• Optimized Geometry Split/splitlessinjector (SSL), temperature range 50 °Cto 400 °C in 1 °C increments. Standardwith large volume splitless capability for injection volumes up to 50 μL withconcurrent solvent recondensation.

• B.E.S.T. PTV cold injection system for split/splitless, large volume and automated on-column injections, heating rate: up to14.5 °C/sec (870 °C/min). Programmability:3 ramps/4 plateaus. Air-cooled down tofew degrees above ambient temperature.Sub-ambient: -50 °C with liquid N2, -30 °Cwith CO2 options.

• AI/AS 3000 Series II autosampler idealfor routine liquid sample injections

• TriPlus autosampler for liquid, headspaceand solid phase microextraction (SPME*)sampling capabilities

• Purge and Trap, thermal desorption andother autosampler options available

Direct Probe System Option• Quick, simple method for sample

introduction directly into the ion source• Direct Inlet Probe (DIP) for using

aluminum crucibles, max. temp. 350 °C• Direct Exposure Probe (DEP/DCI) analysis of

highly polar, thermally labile, or suspendedsolid compounds using fast heating filamentwith max. temp. ca. 1600 °C

• Powerful screening techniques that arecompatible with all modes of ionizationand mass analysis

• Switch to probe in under three minuteswith GC interface undisturbed

LC-MS Options• Convertible to LC-MS mode by replacing

EI/CI source with an optional dedicatedLC-MS source

• Interchangeable ESI and APCI ionizationprobes

• Ion Max™ API source• Enhanced sensitivity and ruggedness• Sweep gas reduces chemical noise• Optimal 60-degree spray angle for best

sensitivity and ruggedness• APPI/APCI combination probe• Removable ion transfer tube provides

vent-free maintenance• High temperature, self-cleaning APCI

heater employing state-of-the-art ceramicheater technology

• X, Y, and Z probe positioning adjustmentsfor all ionization probes

• Automatic source recognition for easeof use and simplified data logging


• Automated valve for making manual loopinjections or diverting LC flow stream to waste

• Automated infusion with syringe pump • Automated loop injection from syringe

pump for analyte optimization

* Sold under license from Supelco ®

System Control• Embedded computer with Motorola

PowerPC processor• Integrated Serial Peripheral Interconnect

(SPI) bus• I/O coprocessor with nonvolatile memory• AD SHARC digital signal processor (DSP)

for dedicated instrument control • 100BASE-T Ethernet port for instrument

data system communications

Data Acquisition • Real-time, high-speed, digital signal

processing with dedicated AD SHARC DSP• Digital sampling rate up to 195,000

samples per second• High-resolution centroiding

Instrument Diagnostics• Graphical diagnostics for all power supplies,

electronic circuits and pumping system• Remote access allows Thermo Fisher

Scientific engineers to troubleshoot via modem

• Electronic logbook of diagnostic results

Data System• Xcalibur™ processing and instrument con-

trol software• Autotune• Autocalibration• Data system control of GC, MS and

autosamplers• Superior comprehensive instrument

diagnostics • QuanLab™ Forms 2.5 software for routine

data analysis and reporting• Automated optimization of all instrument

parameters including gas pressures andcollision energy within an experiment

• High performance PC with Intel® Core™ 2Duo and Microsoft® Windows® operatingsystem

• 19-inch viewable ultra sharp flat-screendisplay monitor

Optional Application-Specific Software• ToxLab™ Forms and EnviroLab™ Forms are

ideal for toxicology and environmentalapplications

• LCQUAN™ quantitation software supports21 CFR Part 11 compliance

• MetWorks™ – automated metaboliteidentification using spectral trees

• Mass Frontier™ – spectral interpretationand classification software to identifyunknowns

• NIST library, now including MS/MS spectra• Wiley library• Maurer-Weber-Pfleger library• Pesticide library

Performance Specifications

GC/MS SpecificationsAll evaluations performed using a TRACE™

TR-5MS SQC, 15 m x 0.25 mm ID (0.25 micronfilm thickness) fused silica capillary column.

Installation Specifications

Electron Ionization SRM

Hot splitless injection of 1μL of a 100 fg/μLstandard of octafluoronaphthalene (OFN) iniso-octane will produce a minimum signal-to-noise ratio of 500:1 for the transition ofm/z 272 to the product ion of m/z 241 whenoperated in selected reaction monitoringmode (SRM) at five scans per second, usingresolution of 0.7 Da FWHM.

Positive Chemical Ionization SRM

Hot splitless injection of 1μL of a 100 fg/μLstandard of benzophenone (BZP) in n-heptanewill produce a minimum signal-to-noise ratioof 150:1 for the transition of the protonatedmolecular ion at m/z 183 to the fragmention at m/z 105 when operated in selectedreaction monitoring mode (SRM) at fivescans per second with resolution set to 0.7 Da FWHM and methane as reagent gas.

Typical Specifications

Electron Ionization Full Scan

Hot splitless injection of 1μL of a 1pg/μLstandard of octafluoronaphthalene (OFN) iniso-octane will produce a minimum signal-to-noise of 400:1 for m/z 272 when scanningfrom 200 – 300 Da at five scans per second.

Electron Ionization SIM

Hot splitless injection of 1μL of a 50 fg/μLstandard of octafluoronaphthalene (OFN) iniso-octane will produce a minimum signal-to-noise of 50:1 for m/z 272 when operated inselected ion monitoring mode (SIM) at fivescans per second, with resolution set to 0.7 Da FWHM.

Positive Chemical Ionization Full Scan

Hot splitless injection of 1 μL of a 10 pg/μLstandard of benzophenone in n-heptane willproduce a minimum signal-to-noise of 25:1for the protonated molecular ion at m/z 183when scanning from 80 – 230 Da at 2 scansper second with methane as reagent gas.

Negative Chemical Ionization Full Scan

Hot splitless injection of 1 μL of a 1 pg/μLstandard of OFN in iso-octane will producea minimum signal-to-noise of 5000:1 for m/z 272 when scanning from 200–300 Da at five scans per second with methane asthe reagent gas.

Negative Chemical Ionization SIM

Hot splitless injection of 1 μL of a 10 fg/μLstandard of OFN in iso-octane will produce aminimum signal-to-noise of 150:1 for m/z 272when operated in selected ion monitoringmode (SIM) at five scans per second, withresolution set to 0.7 Da FWHM andmethane as reagent gas.

Optional LC/MS Specifications

Electrospray (ESI)

A 5 μL loop injection of a 2 pg/μL (3.250 fmol/μL) reserpine solution at a flow rate of 400 μL/min 50/50 IPA/waterwill produce a minimum signal-to-noiseratio of 100:1 for the transition of the protonated molecular ion at m/z 609.3 to the fragment ion at m/z 195.1 when operated in selected reaction monitoringmode (SRM) with Q1 and Q3 resolution set to 0.7 Da FWHM.

Atmospheric Pressure ChemicalIonization (APCI) and AtmosphericPressure Photoionization (APPI)

A 5 μL loop injection of a 2 pg/μL (3.250fmol/μL) reserpine solution at a flow rate of1 mL/min 50/50 IPA/water will produce aminimum signal-to-noise ratio of 100:1 forthe transition of the protonated molecularion at m/z 609.3 to the fragment ion at m/z 195.1 when operated in selected reactionmonitoring mode (SRM) with Q1 and Q3 resolution set to 0.7 Da FWHM.


Africa-Other +27 11 570 1840Australia +61 2 8844 9500Austria +43 1 333 50 34 0Belgium +32 2 482 30 30Canada +1 800 530 8447China +86 10 8419 3588

Denmark +45 70 23 62 60Europe-Other +43 1 333 50 34 0Finland / Norway / Sweden

+46 8 556 468 00France +33 1 60 92 48 00Germany +49 6103 408 1014

India +91 22 6742 9434Italy +39 02 950 591Japan +81 45 453 9100Latin America +1 608 276 5659Middle East +43 1 333 50 34 0Netherlands +31 76 579 55 55

South Africa +27 11 570 1840Spain +34 914 845 965Switzerland +41 61 716 77 00UK +44 1442 233555USA +1 800 532 4752www.thermo.com

©2007, 2008 Thermo Fisher Scientific Inc. All rights reserved. Intel is a registered trademark, and Core is a trademark of Intel Corporation; Microsoft andWindows are registered trademarks of Microsoft Corporation; Mass Frontier is a trademark of HighChem, Ltd; Supelco is a registered trademark of Sigma-Aldrich, Inc. All other trademarks are the property of Thermo Fisher Scientific Inc. and its subsidiaries. Specifications, terms and pricing are subject to change. Not all products are available in all countries. Please consult your local sales representative for details.


PS10296_E 12/08M

System Dimensions/WeightsComplete GC/MS system requires 2.5 mof workbench space. Optional LC willrequire additional workbench space.

TSQ Quantum GC (height x width x depth)69 x 56 x 79 cm (27 x 22 x 31 in)Weight: 118 kg (260 lbs)

TRACE GC Ultra44 x 61 x 65 cm (17 x 24 x 26 in)Weight: 55 kg (121 lbs)

Minitower Computer48 x 18 x 43 cm (19 x 7 x 17 in)Weight: 14 kg (31 lbs)

Monitor41 x 41 x 43 cm (16 x 16 x 17 in)Weight: 5 kg (11 lbs)

Forepump30 x 20 x 64 cm (12 x 8 x 25 in)Weight: 34 kg (75 lbs)

Laser Printer20 x 41 x 46 cm (8 x 16 x 18 in)Weight: 7 kg (15 lbs)

Installation Requirements

Power

TSQ Quantum GC System• One 230 V AC ± 10% at 30 amps, 50/60 Hz,

single phase, with earth ground, dedicatedto the instrument

Data System• 120 V AC at 10 amps or 230 V AC at

5 amps, single phase, with earth ground

Optional Liquid Chromatograph**• 120 V AC at 10 amps or 230 V AC at

5 amps, single phase, with earth ground• Stable voltage, free of spikes** Values are for the Thermo Scientific Accela system.

Other LC systems will vary.

Gas• Collision gas: 99.995% pure Argon• Helium: purity 99.999% with less than

one ppm each of water, oxygen, and totalhydrocarbons

• Collision gas pressure: 135 ± 70 kPa(20 ± 10 psig)

• CI reagent gases: methane, isobutane,ammonia or carbon dioxide with purity99.99%

• One high-purity (99% pure) nitrogen gassupply for the API source (optional).Required pressure is 690 ± 140 kPa (100 ± 20 psi). Maximum consumption of nitrogen gas is 20 L/min (56 SCFH).(Optional, for LC/MS)

Environment• System averages 4,420 W (15,380 Btu/h)

output when considering air conditioningneeds. Operating environment must be15 – 27 °C (59 – 81 °F) and relative humiditymust be 40 – 80% with no condensation.

• Optimum operating temperature is 18 – 21 °C (65 – 70 °F)

• Functional temperature range: 15 – 27 °C(59 – 81 °F)

• Optimal temperature range: 18– 21 °C(65 – 70 °F)

• Particulate matter: < 100,000 particles of > 5 μm diameter per cubic foot of air (< 3,500,000 particles per cubic meter of air)

• Relative humidity: 20 – 80%, without condensation

• Floors must be free of vibration

Multi-residue Analysis of Pesticides in Foodusing GC/MS/MS with the TSQ Quantum GCKuniyo Sugitate, Michiko Kanai, Thermo Fisher Scientific, Yokohama, JapanMasahiro Okihashi, Division of Food Chemistry, Osaka Prefectural Institute of Public Health, Osaka, Japan Dipankar Ghosh, Thermo Fisher Scientific, San Jose, CA, USA

ApplicationNote: 387

Key Words

• TSQ Quantum GC

• H-SRM

• PesticideResidues in Food

• Positive ListSystem

• QED

• SRM

Introduction

Food safety concerns are on the rise amongst consumersworldwide. In 2006, sweeping changes were made to theFood Hygiene Law in Japan regarding residues of agricul-tural chemicals, including pesticides, in foods. As a result,standard residue values were established for approximately800 pesticides. All food items produced in or importedinto Japan are required to meet the standards establishedby this law. If pesticide residues in any food items exceedthese standards, then the distribution and sale of the foodis prohibited. This Positive List System has had a significanteffect not only on the Japanese domestic production, butalso on much of the food exported to Japan from variousforeign countries such as China, the United States, and Taiwan.

There are numerous types of pesticides regularly used inthe agricultural industry, including insecticides, fungicides,herbicides, and growth regulators. Because each type hasdifferent physicochemical properties, there are limitationson simultaneous analysis. Among the pesticides for whichstandard values are currently set, GC/MS/MS can analyzeapproximately 300 compounds. The superior selectivity ofthis technique allows interference-free quantification, evenwith peak coelution, and provides positive confirmation ofvarious pesticides in a single analytical run.

To accurately monitor pesticide residues, a highthroughput multi-residue screening method that can quantitate a large number of pesticide residues during asingle analytical run is needed.

GoalTo simultaneously analyze 103 pesticides using the TSQ Quantum™ GC system, using SRM and H-SRM.Additionally, to show the utility of QED MS/MS for structural confirmation of the analytes undergoing quantification.

Experimental Conditions

Sample Preparation

Green pepper, carrot, grapefruit and banana samples wereprepared for analysis using a method based on the simpleand quick QuEChERS approach.1 A 10 g sample of foodwas homogenized in a food processor and placed in apolypropylene centrifuge tube. The sample was extractedwith 20 mL of acetonitrile in a homogenizer. Then, 4 g ofanhydrous magnesium sulfate and 1 g of sodium chloridewere added and the resulting mixture was centrifuged.After centrifugation, the supernatant was loaded onto a

graphite carbon/PSA dual layer solid phase extraction column and eluted with 50 mL of acetonitrile/toluene (3:1).After the eluate was concentrated under reduced pressure, it was dissolved (1 g/mL) in 10 mL of acetone/n-hexane togive the test solution.

GC

GC analysis was performed using the TRACE GC Ultra™

System (Thermo Fisher Scientific, Milan, Italy). The GCconditions were as follows:

Column: Rxi-5MS 30 m x 0.25 mm I.D.,0.25 m df (Restek Corp., Bellefonte, PA)

Injection mode: Splitless with surge injection(200 kPa, 1 min)

Injection temperature: 240 °C Oven temperature: 80 °C (1 min) – 20 °C/min – 180 °C –

5 °C/min – 280 °C (10 min)Flow rate: Constant flow 1.2 mL/minTransfer line temperature: 280 °C

AS

The samples were injected through the TriPlus™ autosampler(Thermo Fisher Scientific, Milan, Italy). The autosamplerconditions were as follows:

Injection volume: 1 μLInjection mode: Hot needle Syringe: 80 mm

MS

MS analysis was carried out on a TSQ Quantum GCtriple stage quadrupole mass spectrometer. (Thermo FisherScientific, San Jose, CA). The MS conditions were as follows:

Ionization mode: EI positive ion Ion volume: Closed EI Emission current: 25 μAIon source temperature: 220 °CScan type: SRM and H-SRMScan width: 0.002 a.m.u. Scan time: 0.01 sPeak width: Q1, 0.7 Da; Q3, 0.7 Da FWHMPeak width for H-SRM: Q1, 0.4 Da; Q3, 0.7 Da FWHMCollision gas (Ar) pressure: 1.2 mTorr

A total of 103 pesticides were analyzed to determinethe product ion to be used for quantitation. Table 1 liststhe SRM transitions and the optimum collision energy foreach of the compounds and a summary of the calibrationrange, linearity, and the reproducibility of each individualcompound at 5 ppb (ng/mL).

Page 1of 6

Precursor Product Collision CV(%)R.T. Ion (m/z) Ion (m/z) Energy R2 Range n=5

Mevinphos 6.44 192 127 10 0.9999 0.1-100 4.03

XMC 7.52 122 107 10 0.9999 0.1-100 2.55

Tecnazene 8.03 261 203 15 0.9996 0.1-100 5.41

Ethoprpphos 8.22 200 114 10 0.9981 0.1-100 7.91

Ethalfluralin 8.42 316 276 10 0.9997 0.1-100 4.14

Benfluralin 8.62 292 264 10 0.9989 0.1-100 1.86

Monocrotophos 8.62 192 127 10 0.9754 5-100 19.47

α-BHC 9.03 219 183 15 0.9999 0.1-100 4.51

Dicloran 9.25 206 176 10 0.9994 0.1-100 2.30

Simazine 9.30 201 172 10 0.9999 0.1-100 4.33

Propazine 9.50 214 172 10 0.9998 0.1-100 1.99

β-BHC 9.57 219 183 15 1.0000 0.1-100 3.51

γ -BHC 9.73 219 183 15 0.9998 0.1-100 6.57

Cyanophos 9.78 243 109 10 0.9996 0.1-100 3.56

Pyroquilon 9.90 173 130 20 0.9996 0.1-100 2.95

Diazinon 4.94 304 179 15 0.9995 0.1-100 4.40

Phosphamidon-1 10.06 264 127 10 0.9989 0.1-100 10.31

Prohydrojasmon-1 10.12 184 83 20 0.9992 0.1-100 7.39

δ-BHC 10.26 219 183 15 0.9994 0.1-100 5.17

Prohydrojasmon-2 10.66 264 127 10 0.9972 0.1-100 17.11

Benoxacor 10.7 259 120 15 0.9999 0.1-100 3.30

Propanil 10.95 262 202 10 0.9993 0.1-100 3.65

Phosphamidon-2 10.97 264 127 10 0.9970 0.1-100 8.77

Dichlofenthion 10.99 279 223 15 0.9994 0.1-100 2.21

Dimethenamid 11.06 230 154 10 0.9996 0.1-100 2.51

Bromobutide 11.09 232 176 10 0.9990 0.1-100 5.91

Paration-methyl 11.24 263 109 10 0.9982 0.1-100 3.74

Tolclofos-methyl 11.38 265 250 15 0.9998 0.1-100 2.52

Ametryn 11.43 227 170 10 0.9999 0.1-100 0.90

Mefenoxam 11.57 249 190 10 0.9995 0.1-100 5.81

Bromacil 11.98 205 188 15 0.9988 0.1-100 3.87

Pirimiphos-methyl 12.00 305 276 10 0.9995 0.1-100 4.08

Quinoclamine 12.18 207 172 10 0.9989 0.1-100 4.24

Diethofencarb 12.34 225 125 15 0.9985 0.1-100 4.64

Cyanazine 12.52 225 189 10 0.9994 0.1-100 3.41

Chlorpyrifos 12.57 314 258 15 0.9991 0.1-100 3.37

Parathion 12.59 291 109 15 0.9962 0.1-100 9.76

Triadimefon 12.67 208 111 25 0.9986 0.1-100 6.10

Chlorthal-dimethyl 12.73 301 223 20 1.0000 0.1-100 1.23

Nitrothal-isopropyl 12.78 236 148 15 0.9974 0.1-100 5.53

Fthalide 13.04 272 243 10 0.9993 0.1-100 4.32

Fosthiazate 13.05 195 103 10 0.9956 5-100 6.29 13.12

Diphenamid 13.1 239 167 10 0.9997 0.1-100 4.67

Pyrifenox-Z 13.64 262 200 15 0.9979 0.2-100 4.54

Fipronil 13.79 367 213 25 0.9991 0.1-100 3.49

Allethrin 13.67 123 81 10 0.9991 5-100 3.79

Dimepiperate 13.87 145 112 10 0.9987 0.1-100 3.74

Phenthoate 13.87 274 121 10 0.9987 0.1-100 1.82

Quinalphos 13.88 146 118 10 0.9984 0.1-100 1.96

Paclobutrazol 14.45 236 125 15 0.9961 0.1-100 7.41

Endosulfan-α 14.67 241 206 15 0.9996 0.1-100 4.54

Butachlor 14.73 237 160 10 0.9998 0.1-100 5.26

Imazamethabenz- 14.81 256 144 20 0.9932 2-100 12.09methyl

Butamifos 15.00 286 202 15 0.9958 0.1-100 4.66

Napropamide 15.01 271 128 5 0.9989 0.1-100 8.96

Precursor Product Collision CV(%)R.T. Ion (m/z) Ion (m/z) Energy R2 Range n=5

Flutlanil 15.06 173 145 15 0.9986 0.1-100 1.93

Hexaconazole 15.06 214 172 15 0.9924 0.1-100 8.98

Profenofos 15.28 337 267 15 0.9968 0.1-100 6.61

Uniconazole-P 15.38 234 137 15 0.9966 0.1-100 11.37

Pretilachlor 15.37 162 132 15 0.9982 0.1-100 6.72

Flamprop-methyl 15.66 276 105 10 0.9986 0.1-100 3.93

Oxyfluorfen 15.69 361 300 10 0.9980 0.5-100 6.07

Azaconazole 15.79 217 173 15 0.9981 0.1-100 7.07

Bupirimate 15.82 316 208 10 0.9982 0.1-100 4.65

Thifluzamide 15.84 449 429 10 0.9972 0.1-100 2.75

Fenoxanil 16.25 293 155 20 0.9989 0.1-100 3.73

Chlorbenzilate 16.43 251 139 15 0.9976 0.1-100 0.81

Pyriminobac- 16.76 302 256 15 0.9986 0.1-100 2.70methyl-Z

Oxadixyl 16.86 163 132 10 0.9998 0.1-100 3.72

Triazophos 17.30 257 162 10 0.9941 0.2-100 6.72

Fluacrypyrim 17.38 189 129 10 0.9988 0.1-100 2.15

Edifenphos 17.72 310 173 10 0.9927 0.1-100 7.95

Quinoxyfen 17.74 272 237 10 0.9993 0.1-100 4.50

Lenacil 17.78 153 136 15 0.9979 0.1-100 5.19

Trifloxystrobin 18.01 222 162 10 0.9966 0.1-100 8.47

Pyriminobac- 18.19 302 256 15 0.9982 0.1-100 2.12methyl-E

Tebuconazole 18.39 250 125 20 0.9907 0.2-100 13.03

Diclofop-methyl 18.51 253 162 15 0.9991 0.1-100 2.14

Mefenpyr-diethyl 19.15 253 189 20 0.9992 0.1-100 3.35

Pyributicarb 19.24 165 108 10 0.9973 0.1-100 2.00

Pyridafenthion 19.46 340 199 10 0.9940 0.2-100 4.71

Acetamiprid 19.39 152 116 20 1.0000 50-100 –

Bromopropylate 19.64 341 185 15 0.9956 0.1-100 3.72

Piperophos 19.84 320 122 10 0.9939 0.2-100 7.51

Fenpropathrin 19.98 265 210 10 0.9973 0.1-100 6.87

Etoxazole 20.06 300 270 20 0.9969 0.1-100 8.84

Tebufenpyrad 20.10 333 171 20 0.9978 0.5-100 13.35

Anilofos 20.31 226 157 15 0.9948 0.2-100 5.56

Phenothrin-1 20.49 183 165 10 0.9967 5-100 16.13

Tetradifon 20.54 356 229 10 0.9998 0.2-100 4.17

Phenothrin-2 20.66 183 165 10 0.9968 0.1-100 3.79

Mefenacet 21.22 192 136 15 0.9955 0.1-100 4.90

Cyhalofop-buthyl 21.23 357 229 10 0.9967 0.1-100 5.52

Cyhalothrin-1 21.30 181 152 20 0.9975 0.2-100 3.21

Cyhalothrin-2 21.66 181 152 20 0.9984 0.2-100 6.67

Pyrazophos 22.06 373 232 10 0.9963 0.1-100 10.46

Bitertanol 22.80 170 141 20 0.9873 0.1-100 6.76 22.97

Pyridaben 23.18 147 117 20 0.9958 0.1-100 1.29

Cafenstrole 24.03 100 72 5 0.9958 0.1-100 9.77

Cypermethrin-1 24.72 181 152 20 0.9983 2-100 9.29

Halfenprox 24.79 263 235 15 0.9979 0.1-100 10.25

Cypermethrin-2 24.92 181 152 20 0.9982 2-100 6.91

Cypermethrin-3 25.06 181 152 20 0.9985 2-100 16.27

Cypermethrin-4 25.13 181 152 20 0.9948 2-100 13.79

Fenvalerate-1 26.47 167 125 10 0.9977 0.1-100 3.11

Flumioxazin 26.50 354 176 20 0.9937 0.1-100 9.66

Fenvarelate-2 26.91 167 125 10 0.9979 0.1-100 3.26

Deltamethrin+ 28.15 181 152 20 0.9967 0.2-100 8.20 Tralomethrin

Tolfenpyrad 29.11 383 171 20 0.9968 2-100 4.84

Imibenconazole 30.35 375 260 15 1.0000 50-100 –

Table 1: Retention times, SRM conditions, calibration range, linearity, and the reproducibility of each individual pesticide residue compound

Page 2 of 6

Results and Discussion

Figure 1 shows an example calibration curve for Propazine at 0.1-100 ppb with a corresponding chromatogram at 1 ppb, showingexcellent reproducibility (r2 = 0.9998).

Figure 2 shows examples of GC/MS/MS chromatograms of variouspesticides in which 1 ppb of each pesticide was added to green pepper.Even at this extremely low concentration (1/10 of the uniform standardvalue for pesticides), it was possible to make measurements withremarkably high sensitivity with the TSQ Quantum GC.

Figure 3 shows the chromatograms for cypermethrin, fenvalerateand deltamethrin (+ tralomethrin). Cypermethrin is a syntheticpyrethroid compound with a high detection ratio in agricultural produce. In addition to having a slow elution time in the GC, it has 4 peaks that are due to different isomers that must be resolved.As the chromatograms show, measurements with good sensitivitywere obtained even at the low concentration of 5 ppb.

Figure 1: Calibration curve (0.1-100 ppb) and SRM chromatogram (1 ppb) for Propazine

Figure 2: GC/MS/MS chromatograms of various pesticides at 1 ppb in green pepper samplesPage 3 of 6

Figure 3: Chromatograms for cypermethrin, fenvalerate and deltamethrin

Figure 4: Comparison of SRM Mode with H-SRM Mode. (a) Flamprop-methyl in grapefruit (1 ppb). (b) Parathion in green-pepper (1 ppb).Page 4 of 6

Figure 5: Chromatogram from a carrot test sample (upper row) and the MS/MS spectrum obtained with QED (lower row)

Advantages of H-SRMH-SRM is an acronym for Highly-Selective ReactionMonitoring, which is a more advanced form of SelectiveReaction Monitoring (SRM). H-SRM can eliminatechemical noise, lower detection limits, and reduce thelikelihood of generating false positives. For many pesti-cides that are subject to matrix-dependent interference,the measurements can be successfully carried out usingthe H-SRM mode. With H-SRM, the precursor ion isselected with a smaller peak width. The more stringenttolerance accounts for the higher selectivity, which canlower LOQs and increase precision and accuracy at thelimits of detection. The effects of H-SRM over SRM areillustrated for flamprop-methyl in grapefruit andparathion in green-pepper in Figure 4.

Structural Confirmation with QEDQED MS/MS stands for Quantification Enhanced by DataDependant™ MS/MS. A QED scan on a triple quadrupoleinstrument delivers an information rich mass spectrumthat can be used for structural confirmation of analyteswhile undergoing quantification by SRM (or H-SRM). Thespecificity provided by H-SRM followed by QED MS/MSprovides uncompromised quantitation performance atlow levels followed by a fast, highly-specific full MS/MSscan for confirmation. Figure 5 shows the QED scanresults obtained from a carrot test sample spiked with 10 ppb diazinon.

Page 5 of 6

Zero Cross-talkCross-talk can potentially occur when fragment ions fromone SRM transition remain in the collision cell while asecond SRM transition takes place. This can cause signalartifacts in the second SRM transition’s chromatogram. It can be especially problematic when different SRM eventshave the same product ions formed from different precursorions. However, the orthogonal design of the collision cellin the TSQ Quantum eliminates cross-talk. Figure 6 showsthe absence of cross-talk between two different SRM transitions of paclobutrazol and thifluzamide. Both yield aproduct ion of m/z 125, but no artifacts are seen in eitherchromatogram with a scan time of 10 ms. Similarly, theSRM transitions of triszophos and diclofop-methyl 5 alsoshow no evidence of cross talk, even though they bothyield product ions at m/z 162.

ConclusionSimultaneous analysis was carried out on multi-componentpesticide residues in food products using a quadrupoleGC/MS/MS system, the TSQ Quantum GC. Results obtainedindicated excellent sensitivity (0.1 ppb), reproducibility(10% at 5 ppb) and linearity (R2 > 0.995) in the range of0.1-100 ppb. No cross-talk was observed for the analysisof closely eluting multi-component mixtures. Using H-SRM,interferences from the sample matrix background weresubstantially reduced, leading to improved LOQs. In addition, QED provided MS/MS structural confirmationof the analytes undergoing quantification.

References1. Okihashi, M.; Kitagawa, Y.; Akutsu, K.; Obana, H.; Tanaka, Y. “Rapid

method for the determination of 180 pesticide residues in foods by gaschromatography/mass spectrometry and flame photometric detection”; J Pestic Sci 2005, 30(4), 368-77.

2. The Japanese Ministry of Health, Labour, and Welfare:www.mhlw.go.jp/english/topics/foodsafety/positivelist060228/index.html (English)www.mhlw.go.jp/topics/bukyoku/iyaku/syoku-anzen/zanryu2/index.html(Japanese)

In addition to these

offices, Thermo Fisher

Scientific maintains

a network of represen-

tative organizations

throughout the world.

Africa+43 1 333 5034 127Australia+61 2 8844 9500Austria+43 1 333 50340Belgium+32 2 482 30 30Canada+1 800 530 8447China+86 10 8419 3588Denmark+45 70 23 62 60 Europe-Other+43 1 333 5034 127France+33 1 60 92 48 00Germany+49 6103 408 1014India+91 22 6742 9434Italy+39 02 950 591Japan +81 45 453 9100Latin America+1 608 276 5659Middle East+43 1 333 5034 127Netherlands+31 76 579 55 55South Africa+27 11 570 1840Spain +34 914 845 965Sweden / Norway /Finland+46 8 556 468 00Switzerland+41 61 48784 00UK +44 1442 233555USA +1 800 532 4752

www.thermo.com

AN387_E 02/08M


Figure 6: No cross-talk was observed in the SRM transitions of paclobutrazol and thifluzamide or in the SRM transitions of triszophos and diclofop-methyl.


Legal Notices©2008 Thermo Fisher Scientific Inc. All rights reserved. All trademarks are the property of Thermo Fisher Scientific Inc. and its subsidiaries. This information is presented as an example of the capabilities of Thermo Fisher Scientific Inc. products. It is not intended to encourage use of these products in any manners that might infringe the intellectual property rights of others. Specifications, terms and pricing are subject to change. Not all products are available in all countries. Please consult your local sales representative for details.

Analysis of PCBs in Food and BiologicalSamples Using GC Triple Quadrupole GC-MS/MSDirk Krumwiede, Hans-Joachim Huebschmann, Thermo Fisher Scientific, Bremen, Germany

IntroductionPolychlorinated biphenyls (PCBs) are a class of extremelypersistent industrial chemicals manufactured for use inelectrical transformers, capacitors, inks, paints, pesticides,dust control or insulating fluids. Estimates have put thetotal global production of PCBs on the order of 1.5 milliontons. Between 1930 and 1977, the United States was thesingle largest producer with over 600,000 tons produced.The European region follows with nearly 450,000 tonsthrough 1984.1,2

PCBs include 209 distinct chemical forms (congeners),each having different health effects. Although productionof PCBs was banned in the United States in 1977, PCBproducts are still in use. Because of their persistence in theenvironment, they have been transported around the globevia wind and air currents. PCBs contaminate the bodies ofevery animal and human being on earth.

The international Stockholm Convention on PersistentOrganic Pollutants (POPs) recognizes PCBs among twelveof the world’s most dangerous chemicals known to bedetrimental to human health and the environment. In spiteof the slow but steady decrease of dioxin body burdens,which shows the results of the combined efforts to preventfurther distribution, levels of PCBs are expected to stayunaffected globally (Dioxin Conference 2007 Tokyo).3

Monitoring PCB levels as a part of ongoing programs forthe Stockholm Convention will continue for years, withnumerous sample requests, particularly for dangerous dioxin-like (dl) PCBs. In particular, coplanar dl-PCBs –non-ortho-substituted PCBs – are the focus of food safetycontrols due to having a toxicity similar to 2,3,7,8-TCDD.dl-PCBs also contribute significantly to the sample toxicequivalents (TEQ) value.

This application details a fast, reliable and highlyselective trace level screening method for the quantitationof PCBs in environmental, food and biological samples,using triple stage quadrupole mass spectrometry with theThermo Scientific TSQ Quantum GC™. The analyticalstrategy is analogous to the well-established United StatesEnvironmental Protection Agency (USEPA) Method 1668A.4

Due to the different analytical response, eachchlorination degree is measured against its own isotopicallylabeled internal standard. This allows for optimal analyticalprecision and compound similarity. The internal standardcompounds are labeled with 13C on the biphenyl backbone,for a total of 12 labels on the biphenyls. The 13C-labeledPCBs are spiked into each sample, which enables accurateidentification and correction for the concentration of thenative (unlabeled) compounds in the analytical process.This is generally termed “Isotope Dilution Quantitation.”A suffix of “L” behind the IUPAC congener number isused to denote the labeled compound; for example, 101Lindicates the labeled analogue of the pentachlorobiphenylcongener 101.

ExperimentalConditions

InstrumentConfigurationSample analyses werecarried out using theThermo ScientificTSQ Quantum GCGC-MS/MS system,equipped with aThermo ScientificTRACE GC Ultra™

gas chromatograph.The TRACE GCUltra was configuredwith split/splitless injector, and sample introduction wasperformed using the Thermo Scientific TriPlus™ AS liquidautosampler. The capillary column was a Thermo ScientificTRACE™ TR-Dioxin 5MS column (5% phenyl film) of 30 m length, 0.25 mm inner diameter and 0.10 μm filmthickness. Table 1 describes selected instrumental conditionsfor the GC, autosampler, and mass spectrometer.

TRACE GC Ultra

Injector: Split/splitless, 260 °C, 1.2 min splitlessCarrier: He, constant flow, 0.8 mL/minTemp. Program: 90 °C, 4 min

15 °C/min, 160 °C4 °C/min, 225 °C7 °C/min, 290 °C

Total Run Time: 32.00 minTransfer Line: 260 °C

TriPlus Autosampler

Injection Volume: 1.0 μLPre-Injection Delay (s): 0.2Post-Injection Delay (s): 0.2

TSQ Quantum GC

Source Temp: 240 °CIonization: EI, 40 eVEmission Current: 100 μAQ1 Resolution: 0.7 DaQ3 Resolution: 0.7 DaCollision Gas: Argon, 2.0 mTorrCollision Gas Energy: 22 eV

Table 1: Selected instrument settings for the TSQ Quantum GC, TRACE GCUltra, and TriPlus Autosampler

Key Words

• TSQ Quantum GC

• dl-PCBs

• Food Safety

• Isotope Dilution

• PCBs

• SRM

• WHO-PCBs

Application Note: 10262

Sample Measurements

USEPA Method 1668 describes a method for thedetermination of PCB congeners.

…[Method 1668] was developed by the U.S.Environmental Protection Agency’s (EPA’s) Office of Science and Technology for congener-specificdetermination of the polychlorinated biphenyl (PCB)congeners designated as toxic by the World HealthOrganization. Revision A of Method 1668 has beenexpanded to include congener-specific determination ofmore than 150 chlorinated biphenyl (CB) congeners.The toxic PCBs and the beginning and ending level-of-chlorination CBs are determined by isotope dilutionhigh resolution gas chromatography/high resolutionmass spectrometry (HRGC/HRMS). The remaining CBsare determined by internal standard HRGC/HRMS.Method 1668A is applicable to aqueous, solid, tissue,and multi-phase matrices.4

Commercially available EPA 1668 standards(Wellington, Guelph, ON, Canada) were employed for thisapplication. 68A-CVS is a series of calibration solutionstypically used for USEPA Method 1668, Rev. A forHRGC/HRMS. All internal standards (ISTD) were the 12-fold 13C labeled analogues for each PCB chlorinationdegree. The treatment of samples, internal standards andanalytical strategy complied fully with EPA Method 1668A.

TSQ Quantum GC SRM Settings

While USEPA Method 1668 requires the analytes to be“…separated by the GC and detected by a high-resolution(R 10,000) mass spectrometer, [with] two exact m/z values…monitored at each level of chlorination (LOC) throughouta pre-determined retention time window”, the methoddescribed in this application employs a triple quadrupolemass spectrometer equipped with hyperbolic quadrupolerods for increased selectivity, as an alternative approach to HRMS.4 According to the EU Commission Directive96/23/EC concerning the performance ranking of analyticalmethods, the number of identification points of GC-MS/MSmethods can be similar or even superior to HRMS, especiallyfor MS/MS techniques using independent product iontransitions (Table 2).5

According to the EU Commission Directive 96/23/EC,suitable confirmatory methods for organic residues orcontaminants are required to be either full scan techniquesor methods that use “…at least 4 identification points(PCBs, dioxins, furans) for techniques that do not recordthe full mass spectra”, which are the common

target compound multiple ion detection (MID) methods.5

By using MS/MS transitions from two PCB precursor ionsand detecting individual product ions for each chlorinationdegree, the measurement scheme in this application followsthe EU Commission Directive 96/23/EC and provides fiveidentification points for each PCB. The monitored iontransitions are based on the molecular precursor ions(12C12H10-x

35Clx) relative to the mono 37Cl isotopes thereof(12C12 H10-x

35Clx-137Cl) to form the product ions with a

loss of 2 chlorine during the collision induced dissociation(CID) fragmentation process (Table 3). The internal standardsfollow the same scheme; however, they show a shift of 12 Da due to the 12-fold 13C-labeling.

When choosing precursor ions it should be noted thatonly the molecular ion M+, e.g. m/z 357.80 C12H4

35Cl6 ofthe monoisotopic HxCB, gives rise to a unique product ion.The next ion of the isotope cluster, m/z 359.80, carriesone 37Cl which statistically leads to two product ions, one of which gets the 37Cl substitution. This isotope effectleads to lower product ion intensities as the chlorination degree increases.

The analysis sequence in selected reaction monitoring(SRM) mode uses six (6) retention time windows withoverlapping masses for all 10 levels of chlorination (LOC).Except for Segment 1, two chlorination degrees werealways monitored in parallel. This is due to the staggeredelution order of the individual PCB congeners withadjacent chlorine substitution. The high number of massestaken into each SRM analysis segment demonstrates thespeed and capacity of the TSQ Quantum GC for parallelmulti-component detection. Tables 4 and 5 detail the SRM segments and settings.

Page 2 of 6

Technique Number of Ions Identification Points

GC-MS (EI or CI) n nGC-MS (EI and CI) 2 (EI) + 2 (CI) 4GC-MS/MS 1 precursor and 2 product ions 4GC-MS/MS* 2 precursor ions, each 5

with 1 product ionHRMS n 2n

Table 2: Examples of the number of identification points earned for analyticalGC/MS techniques, (n = integer).3

* denotes method described here.

Precursor 1 Precursor 2 Product 1 Product 2 PCB m/z m/z m/z m/z

MoCB 188.04 190.04 153.04 153.04MoCB ISTD 200.08 202.08 165.10 165.10DiCB 222.00 224.00 152.06 152.06DiCB ISTD 234.04 236.04 164.10 164.10TrCB 255.96 257.96 186.02 186.02TrCB ISTD 268.00 270.00 198.02 198.02TeCB 289.92 291.92 219.98 219.98TeCB ISTD 301.96 303.96 232.02 232.02PeCB 323.90 325.90 253.95 255.95PeCB ISTD 335.92 337.92 265.99 267.99HxCB 357.80 359.80 287.90 289.95HxCB ISTD 369.90 371.90 299.51 301.95HpCB 391.80 393.80 321.90 323.90HpCB ISTD 403.80 405.80 333.90 335.90OcCB 427.80 429.80 357.80 357.80OcCB ISTD 439.80 441.80 369.90 369.90NoCB 461.70 463.70 391.80 393.80NoCB ISTD 473.80 475.80 403.80 405.80DeCB 495.70 497.70 425.80 427.80DeCB ISTD 507.70 509.70 437.80 439.80

Table 3: SRM data acquisition scheme for PCBs using one precursor ion withthe MID detection of two product ions each. The PCB nomenclature is fromEPA Method 1668 and reflects level of chlorination.

Page 3 of 6


Method Development

All PCB congeners at each chlorination degree were detectedusing two independent SRM transitions. Each transitionused a different precursor ion from the chlorine isotopecluster of the molecular ion region. Data acquisition wasperformed using the detailed SRM settings described inTables 4 and 5. MS/MS results for the TSQ Quantum GCare shown in Figures 1 and 2. Figure 1 illustrates chlorinationdegrees from mono- to pentachloro-biphenyls, whileFigure 2 displays the hexa- to decachloro-biphenylchlorination range. These results were generated using the SRM transitions as described in Table 3. The masschromatograms in Figures 1 and 2 use the most intenseprecursor ion for each compound to show the sequence of chlorination degrees. All congeners can be detected at a high response for each SRM transition. The observeddecrease in intensity is due to the statistical decrease of the individual isomer concentration as a part of themolecular PCB cluster when injected at 1 pg on-column.

Figure 3 compares the two independent SRM transitionsfor one chlorination degree. The upper mass chromatogramsrepresent precursors m/z 323.90 and m/z 325.90 from thenative pentachloro-PCB congeners, while the bottom masschromatograms show the labeled internal standard(precursors of m/z 335.92 and 337.92). This comparisondemonstrates the excellent consistency between the SRMtraces, which allows for confident confirmations of the PCBs.

These SRM mass chromatograms from the TSQQuantum GC triple quadrupole MS operated in standardresolution mode (0.7 Da peak width) show very goodcorrelation to data achieved using gas chromatographyand high resolution mass spectrometry (GC-HRMS). With two independent transitions based on two differentprecursor ions, the TSQ Quantum GC method meets thehigh certainty required by the EU directives, as shown forthe pentachloro-PCBs in Figure 3. The high speed of theTSQ Quantum GC analyzer also provides an average of 6 to 8 data points across a chromatographic peak, evenwhile monitoring two chlorination degrees in each SRMwindow. This allows for reliable peak integration andquantitation.

Figure 1: Extracted ion chromatogram showing the congeners with chlorinationdegrees of mono to penta PCB of a PCB standard (1 pg on-column)

Figure 3: Pentachloro-PCB congeners in standard using two independentSRM transitions each for native (top) and labeled (bottom) PCB congeners104, 123, 118, 114, 105, 126. The ISTD traces also show the components101L, 111L.

Figure 2: Extracted ion chromatogram showing the congeners with chlorinationdegrees of hexa to deca PCB of a PCB standard (1 pg on-column)

Figure 7: dl-Pentachloro-PCBs in green cabbage

Page 4 of 6

Performance with Complex Matrices

To test the chromatographic and mass acquisition methodswith matrix samples, a number of challenging sample typeswere prepared. The TSQ Quantum GC demonstratedexcellent sensitivity, selectivity and robustness with thesesamples, as shown in Figures 4 through 7. These resultsallow for comparison of the results achieved for thepentachloro-PCBs in matrices covering blood, milk, eggyolk and green cabbage. The TSQ Quantum GC providedclean and background-free mass traces for all types ofmatrix studied. This selectivity is particularly evident whencomparing the matrix samples to the standard samplesshown in Figures 1 through 3. Even in very complex samplessuch as blood (Figure 4) and green cabbage (Figure 7), no increase in the level of background can be observed.

Compared to the standard runs, the PCB concentrationsin sample range from a mid-femtogram (fg) to the lowpicogram (pg) level. PCB concentrations were measured at0.2 and 1.0 pg/μL for native PCBs and at 100 pg/μL for alladded 13C-labeled internal standards. The selectivity of theTSQ Quantum GC virtually eliminates matrix interference,allowing for low detection limits, enhanced confidence inquantitative results, and accurate identification of thesecompounds.

Figure 4: dl-Pentachloro-PCBs in a blood sample

Figure 5: dl-Pentachloro-PCBs in milk

Figure 6: dl-Pentachloro-PCBs in egg yolk

Conclusion

The Thermo Scientific TSQ Quantum GC facilitates thescreening and quantitation of PCBs at low levels in difficultmatrix samples and provides results with high certainty.The analytical setup complies with USEPA Method 1668A,following an isotope dilution quantitation protocol. Theadded 13C-labeled internal standard components weredetected with high reliability as demonstrated in differentsamples with complex matrix background.

Confirmatory methods provide information on thechemical structure of the analyte. The TSQ Quantum GCwith its unique hyperbolic quadrupole technology offerssuperior and uniform selectivity for low level PCB samplesin different complex matrices including egg, milk, cabbageand blood. Using the TSQ Quantum GC in H-SRM mode,the PCB pattern that is typical when using high resolutionmass spectrometry, such as magnetic sector, can be detected.

The proposed MS/MS measurement scheme using twoprecursor ions and SRM detection of individual productions is a valuable solution for screening for PCBs in variouscomplex matrices at the relevant levels. For the fast controlof food samples, GC-MS/MS with the TSQ Quantum GCexceeds the current EU directives for a minimum of four (4)identification points, in that the method described hereoffers five (5) identification points.

For contract and governmental control labs, the TSQQuantum GC provides a high productivity solution withincreased sample throughput even for complex matrixsamples. The TSQ Quantum GC delivers ultimateperformance in PCB trace analysis with the added economicadvantage of using reduced clean-up methods.

References1. General information about PCBs, see www.wikipedia.org

2. Fiedler, H., Polychlorinated Biphenyls (PCBs): Uses and EnvironmentalReleases, UNEP Persistent Organic Pollutants.www.chem.unep.ch/pops/POPs_Inc/proceedings/bangkok/FIEDLER1.html

3. Turner, W.E.; Welch, S.M.; et al., Instrumental approaches for improvingthe detection limit for selected PCDD congeners in samples from thegeneral U.S. population as background levels continue to decline,Proceedings of the Dioxin Conference, Oslo 2006.

4. Method 1668, Revision A: Chlorinated Biphenyl Congeners in Water, Soil,Sediment, and Tissue by HRGC/HRMS, United States EnvironmentalProtection Agency, Office of Water, EPA No. EPA-821-R-00-002,December 1999

5. EU Commission Directive 96/23/EC concerning the performance ofanalytical methods and the interpretation of results, 12 August 2002, see http://eur-lex.europa.eu

Note

The following abbreviations were used in thisapplication note:

MoCB = Monochlorobiphenyl

DiCB = Dichlorobiphenyl

TrCB = Trichlorobiphenyl

TeCB = Tetrachlorobiphenyl

PeCB = Pentachlorobiphenyl

HxCB = Hexachlorobiphenyl

HpCB = Heptachlorobiphenyl

OcCB = Octachlorobiphenyl

NoCB = Nonachlorobiphenyl

DeCB = Decachlorobiphenyl

A suffix “L” following the congener number indicatesa labeled compound.

Page 5 of 6








www.thermo.com


AN10262_E 07/08M

Thermo Fisher Scientific, Austin, TX USA is ISO Certified.

Legal Notices©2008 Thermo Fisher Scientific Inc. All rights reserved. All trademarks are the property of Thermo Fisher Scientific Inc. and its subsidiaries. This information is presented as an example of the capabilities of Thermo Fisher Scientific Inc. products. It is not intended to encourage use of these productsin any manners that might infringe the intellectual property rights of others. Specifications, terms and pricing are subject to change. Not all products are available in all countries. Please consult your local sales representative for details.

Segment 1: Precursor (m/z) Product (m/z) Width (m/z) Time (s)

188.04 153.04 0.002 0.150 190.04 153.04 0.002 0.150 200.08 165.10 0.002 0.030 202.08 165.10 0.002 0.030


222.00 152.06 0.002 0.080224.00 152.06 0.002 0.080 234.04 164.10 0.002 0.030 236.04 164.10 0.002 0.030 255.96 186.02 0.002 0.080 257.96 186.02 0.002 0.080 268.00 198.02 0.002 0.030 270.00 198.02 0.002 0.030


255.96 186.02 0.002 0.080 257.96 186.02 0.002 0.080 268.00 198.02 0.002 0.030 270.00 198.02 0.002 0.030 289.92 219.98 0.002 0.080 291.92 219.98 0.002 0.080 301.96 232.02 0.002 0.030 303.96 232.02 0.002 0.030 323.90 253.95 0.002 0.080 325.90 255.95 0.002 0.080 335.92 265.99 0.002 0.030 337.92 267.99 0.002 0.030


289.92 219.98 0.002 0.080 291.92 219.98 0.002 0.080 301.96 232.02 0.002 0.030 303.96 232.02 0.002 0.030 323.90 253.95 0.002 0.080 325.90 255.95 0.002 0.080 335.92 265.99 0.002 0.030 337.92 267.99 0.002 0.030 357.80 287.90 0.002 0.080 359.80 289.90 0.002 0.080 369.90 299.95 0.002 0.030 371.90 301.95 0.002 0.030


323.90 253.95 0.002 0.070 325.90 255.95 0.002 0.070 335.92 265.99 0.002 0.030 337.92 267.99 0.002 0.030 357.80 287.90 0.002 0.070 359.80 289.90 0.002 0.070 369.90 299.95 0.002 0.030 371.90 301.95 0.002 0.030 391.80 321.90 0.002 0.070 393.80 323.90 0.002 0.070 403.80 333.90 0.002 0.030 405.80 335.90 0.002 0.030 427.80 357.80 0.002 0.070 429.80 357.80 0.002 0.070 439.80 369.90 0.002 0.030 441.80 369.90 0.002 0.030


391.80 321.90 0.002 0.070 393.80 323.90 0.002 0.070 403.80 333.90 0.002 0.030 405.80 335.90 0.002 0.030 427.80 357.80 0.002 0.070 429.80 357.80 0.002 0.070 439.80 369.90 0.002 0.030 441.80 369.90 0.002 0.030 461.70 391.80 0.002 0.070 463.70 393.80 0.002 0.070 473.80 403.80 0.002 0.030 475.80 405.80 0.002 0.030 495.70 425.80 0.002 0.070 497.70 427.80 0.002 0.070 507.70 437.80 0.002 0.030 509.70 439.80 0.002 0.030

Table 5: Individual SRM descriptors for acquisition segments 1 through 6

Segment 1 2 3 4 5 6Duration (min) 9.85 2.60 3.30 4.33 6.03 5.89Start Time (min) 0 9.85 12.65 15.75 20.08 26.11

Table 4: TSQ Quantum GC H-SRM analysis segments

Introduction

International regulations on the maximum residue levelsof pesticides in food (MRLs) cover hundreds of individualcomponents at very low maximum residue limits – in therange of 10 ppb or lower.1 Currently, more than 300 regulatedpesticides can be analyzed by gas chromatography/massspectrometry (GC/MS) while a large group of highly polarpesticides is covered by liquid chromatography/massspectrometry (LC/MS) methods.2 GC/MS analysis of thatmany pesticides at the MRL becomes an increasing challengefor quality and governmental control strategies. Thisapplication note provides the analytical methodology for afast multi-residue pesticide determination using the uniquecapabilities of the Thermo Scientific TSQ Quantum™ GCtriple quadrupole mass spectrometer for quantitation andconfirmation of positive results.

A particular challenge in the detection and quantificationof a large number of pesticides in one run derives from the complex elution situation. Because many compoundspartially or completely coelute, a high speed analyzer isrequired to generate a sufficient number of data points.This ensures reliable integration of overlappingchromatographic peaks.

By taking advantage of the unique fast acquisition rateprovided by the TSQ Quantum GC, the rapid analysis ofmulti-pesticide residues becomes routine in modern foodsafety testing labs and addresses the main challenges forthis type of analysis:

a. Narrow GC peaks require fast MS acquisition rate togive sufficient data points for qualitative andquantitative analysis.

b. With multi-component methods the partial or completecoelution of components needs to be considered. TheSRM transition speed needs to be fast enough to monitormany coeluting components while providing enoughdata points for reliable peak integration.

c. The multi-component method should include as manysubstances as possible, which requires the MS be capableof acquiring several hundred SRM transitions in single run.

d. The MS method should require as few acquisitionsegments as possible for multiple targets due to thesmall changes in retention time that may occur in heavymatrix samples. This means the MS must be able tomeasure as many transitions as possible in one segmentwindow without losing sensitivity.

e. Under these conditions, it is necessary to use short SRMdwell times and a very short interscan time.

f. When using short dwell and interscan times for targetsgenerating the same product ions, “cross talk” must besafely prevented. “Cross talk” can lead to false positiveresults in sample analyses.

Experimental Conditions

The purpose of this multi-residue target compoundmethod is to improve analytical productivity in terms ofincreased sample throughput and through reduction in thetime required to review and report for multiple pesticidesanalysis. Despite the large number of pesticides covered in this method a short capillary column was used to speedup the chromatography for high sample throughput. Thedata acquisition method includes a total of 175 SRMtransitions in a single 20-minute run using the TSQQuantum GC. The run was divided into 11 retention timewindows (acquisition segments) with up to 25 SRMtransitions in each. Dwell times of 25 ms were used toobtain good sensitivity and data rate for the quantificationof the targets. Cross talk was not observed even in thewindow containing 25 SRM transitions.

The Thermo Scientific TRACE GC Ultra™ gaschromatograph was used to provide fast chromatography,and the Thermo Scientific TriPlus™ autosampler configuredfor liquid injection was used for automated, productivesample introduction. A Thermo Scientific TRACE™ TR-5MSanalytical column was used for chromatographic separation.The short column length (15 m) contributed to the fastGC run time and improved sample throughput. Table 1lists selected instrument parameters for the GC, autosamplerand mass spectrometer.

Fast Multi-Residue Pesticide Analysis Using Triple Quadrupole GC-MS/MSWeiguo Zhang, Lin Lu, Thermo Fisher Scientific, Shanghai, China Hans-Joachim Huebschmann, Thermo Fisher Scientific, Bremen, Germany

Key Words

• QuanLab FormsSoftware

• TSQ Quantum GC

• Fast GC

• Food Safety

• Maximum ResidueLevels (MRL)

• Selected ReactionMonitoring SRM

• Target CompoundAnalysis

ApplicationNote: 10263

Table 1: Selected instrument conditions for the TRACE GC Ultra, TriPlusAutosampler and TSQ Quantum GC mass spectrometer

To streamline the data review and reporting processfor multiple pesticides analysis, Thermo ScientificQuanLab™ Forms 2.5 software was used to provideproductivity enhancements tailored to the workflow demandsof the pesticides analysis laboratory. QuanLab Formsincludes an integrated user interface for the managementof the total list of pesticides, automated data review,customizable views, and versatile reporting formats.


A complete chromatogram demonstrating the complexityof the elution profile of 170 pesticides at 50 pg/μL isshown in Figure 1. The last peak elutes at 20 minutes. Thepesticides cover multiple compound classes; organochlorine,organophosphorus, carbamates, pyrethroids as well astriazine pesticides were analyzed using 175 correspondingSRM transitions.

The SRM acquisition segments were primarily chosento ensure that each window provided a comfortable setupof the compound list, with each component having atransition dwell time of 25 ms. Table 2 uses the retentiontime window from 5.97 to 8.27 min as an example, witha total of 25 SRM transitions for 27 pesticides.

Pesticide RT Precusor Product CID Dwell Time(min) Ion Ion (V) (ms)

Omethoate 6.16 156 110 10 25Fenobucarb 6.31 121 93 15 25Propachlor 6.33 120 92 15 25Propoxur 6.33 152 110 10 25Demeton-S-methyl 6.4 142 79 10 25Diphenylamine 6.41 169 141 20 25Ethorprofos 6.52 200 158 8 25Chlorpropham 6.71 127 65 20 25Methabenzthiazuron 6.91 164 136 12 25Trifluralin 7.01 306 264 15 25Cadusafos 7.05 213 185 15 25Monocrotophos 7.06 127 109 20 25Phorate 7.11 260 231 8 25α-BHC 7.18 219 183 15 25Hexachlorobenzene 7.31 284 249 20 25Dichloran 7.5 176 148 15 25Dimethoate 7.54 125 79 10 25Carbofuran 7.68 164 149 8 25β-BHC 7.74 219 183 15 25γ-BHC 7.88 219 183 15 25Quintozene 7.99 237 143 25 25Phenanthrene-D10 8.02 188 160 20 25Terbufos 8.04 231 203 10 25Fonofos 8.09 137 109 10 25Propyzamide 8.14 254 226 15 25Pyrimethanil 8.25 198 183 20 25Diazinon* 8.40 304 179 8 25

Table 2: A total of 27 pesticide target compounds (out of the total number of170 compounds) with SRM transitions covered in a single segment coveringthe retention time window from 5.97 to 8.27 min. *Diazinon included in thissegment and that from 8.27-10.17 due to overlap in RT windows.

Figure 1: Total ion chromatogram of 170 pesticides under GC-MS/MS

GC Parameters – TRACE GC Ultra

Injector Split/splitless injector, 220 °CInjection Splitless, 1 min Carrier Gas He, 1.0 mL/min, constant flowColumn TRACE TR-5MS,

15 m x 0.25 mm x 0.25 μmOven Temp. Program 70 °C, 1 min

25 °C/min to 130 °C15 °C/min to 160 °C5 °C/min to 210 °C25 °C/min to 280 °C, 5 min

MS Transfer Line Temp. 280 °C

Autosampler Parameters – TriPlus AS

Sample Volume 1.0 μLInjection Mode Hot needleViscous Sample Yes

MS Parameters – TSQ Quantum GC

Ionization EI, positive ionSource Temp (°C) 220Emission Current 50 μAScan Type SRM (Selective Reaction Monitoring),

H-SRM mode (Highly-SelectiveReaction Monitoring)

Collision Gas Pressure 1.5 mTorrSegment Windows 11Segment (3-5.97min) 10 transitionsSegment (-8.27min) 25 transitionsSegment (-10.17min) 24 transitionsSegment (-11.27min) 17 transitionsSegment (-13min) 24 transitionsSegment (-14.6min) 22 transitionsSegment (-15.6min) 8 transitionsSegment (-16.8min) 16 transitionsSegment (-17.95min) 17 transitionsSegment (-19.2min) 7 transitionsSegment (-22min) 5 transitionsScan Width 0.002 amuScan Time 0.025 s

Zero “Cross Talk”

“Cross talk” is described as a memory effect of the collisioncell in a triple quadrupole mass spectrometer. In cases ofcross talk, a signal for a pesticide compound not actuallypresent in the sample would be seen as a false positive.With a total of 25 SRM transitions in the segment windowfrom 5.97 to 8.27 min, the dwell times and interscan timesare very short, which requires a fast scanning sequencewith active cleaning of the collision cell before acquiringthe next data set. Zero cross talk on the TSQ Quantum GCwas demonstrated by acquiring two different SRMtransitions of Monocrotophos (m/z 127→109) andFonofos (m/z 137→109) which yields the same product ionof m/z 109 in same the segment window (Figure 2). A similarsituation appears in the case of BHC (m/z 219→183) andpyrimethanil (m/z 198 →183). The TSQ Quantum GCshows the clear absence of cross talk, providing absolutecertainty in the data with no false positive results.

Data Review and Reporting

For target compound quantitation, the QuanLab Formssoftware package provides a natural workflow orientationfrom method and sequence set-up to data reviewing andreporting. The total list of pesticide components in themulti-component method is maintained with the results ofthe peak integration and quantitative calibration (Figure 3).In this example, a chive sample was spiked with 10 ppb ofa pesticides cocktail. The integrated peak is displayed at themaximum residue level (MRL). QuanLab Forms providesquick data review for samples, standards, quality controls(QCs), blanks and % of recovery. Figure 4 shows anexample of a high density quantification report fromQuanLab Forms. This type of report is useful for reportinglong lists of compounds on fewer sheets of paper.

Figure 2: Cross talk is absent in the fast SRM acquisition sequence fromMonocrotophos (m/z 127→109) at 8.09 min (bottom trace) to Fonofos (m/z 137→109) (upper trace) even at high concentration

Fonofos (m/z 137→109)

Monocrotophos (m/z 127→109)

Figure 3: QuanLab Forms Data Review of a chive sample spiked with 10 ppbpesticides at the MRL level

Figure 4: An example of a high-density peak integration report generated byQuanLab Forms. These are results at the 10 ppb MRL level for pesticides spikedinto a chive sample and analyzed using TSQ Quantum GC in H-SRM mode.

Conclusions

The Thermo Scientific TSQ Quantum GC provides highest productivity for multi-residue pesticide analysis for effective control at the international MRL levels.

High sample throughput is demonstrated using a fastGC method. A total of 170 pesticide components werescreened with high sensitivity on a TSQ Quantum GC in a single injection with an analysis time of only 20 minutes.Excellent sensitivity, selectivity and flexibility were givenby using up to 25 transitions in 11 retention time windows.False positive results due to cross talk were safelyexcluded even under fast acquisition cycles. The TSQQuantum GC offers the potential to even further reducedwell times without sacrificing the overall sensitivity,which would then allow the addition of more targetpesticides as necessary. QuanLab Forms software providesa workflow-oriented format that allows analysts to easilycreate and manage methods, acquire samples, reviewresults and print reports.

References1. EU Commission Directives 91/414/EEC, 86/362/EEC, 86/363/EEC,

90/642/EEC, Regulation (EC) N. 396/2005 and subsequent amendments.

2. Ministry of Health, Labour and Welfare Japan, Department of FoodSafety, The Positive List System for Agricultural Chemical Residues inFoods, June 2006, see: http://www.mhlw.go.jp

Legal Notices©2008 Thermo Fisher Scientific Inc. All rights reserved. All trademarks are the property of Thermo Fisher Scientific Inc. and its subsidiaries. This information is presented as an example of the capabilities of Thermo Fisher Scientific Inc. products. It is not intended to encourage use of these productsin any manners that might infringe the intellectual property rights of others. Specifications, terms and pricing are subject to change. Not all products areavailable in all countries. Please consult your local sales representative for details.








www.thermo.com

AN10263_E 04/08M


Thermo Fisher Scientific, Austin,TX USA is ISO Certified.

Date post:	01-Jan-2021
Category:	Documents
Upload:	others
View:	3 times
Download:	0 times

Product Specifications Thermo Scientiﬁc Pesticide Analyzer … · 2020. 11. 23. · to quantitate...

Documents