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Development and application of particle beam LC/MS on the quadrupole ion trap mass spectrometer

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Title:
Development and application of particle beam LC/MS on the quadrupole ion trap mass spectrometer
Creator:
Kleintop, Brent Lamar, 1966-
Publication Date:
Language:
English
Physical Description:
viii, 181 leaves : ill. ; 29 cm.

Subjects

Subjects / Keywords:
Calibration ( jstor )
Ion traps ( jstor )
Ionization ( jstor )
Ions ( jstor )
Mass spectra ( jstor )
Mass spectrometers ( jstor )
Mass spectroscopy ( jstor )
Momentum ( jstor )
Quadrupoles ( jstor )
Solvents ( jstor )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Liquid chromatography ( lcsh )
Mass spectrometry ( lcsh )
Particle beams ( lcsh )
Quadrupoles ( lcsh )
Genre:
bibliography ( marcgt )
non-fiction ( marcgt )

Notes

Thesis:
Thesis (Ph. D.)--University of Florida, 1993.
Bibliography:
Includes bibliographical references (leaves 172-180).
General Note:
Typescript.
General Note:
Vita.
Statement of Responsibility:
by Brent Lamar Kleintop.

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University of Florida
Holding Location:
University of Florida
Rights Management:
Copyright [name of dissertation author]. Permission granted to the University of Florida to digitize, archive and distribute this item for non-profit research and educational purposes. Any reuse of this item in excess of fair use or other copyright exemptions requires permission of the copyright holder.
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029909584 ( ALEPH )
29642207 ( OCLC )
AJW5916 ( NOTIS )

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Full Text







DEVELOPMENT


AND APPLICATION OF PARTICLE BEAM LC/MS


ON THE QUADRUPOLE


ON TRAP MASS SPECTROMETER


BRENT LAMAR KLEINTOP













A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL


OF THE UNIVERSITY OF FLORIDA


OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY

UNIVERSITY OF FLORIDA


N PARTIAL FULFILLMENT





























To Mom and Dad in appreciation for al


they've done.











ACKNOWLEDGEMENTS


wish to express my sincere gratitude to my advisor


Richard A.


Yost


for his


night and guidance throughout my graduate studies.


to acknowledge and thank the members of my


would also


graduate committee,


. Jim


Winefordner, Dr. Vanecia Young,


wish to acknowledge Dr


Dr. Jim Boncella, and Dr


Jodie Johnson


Joseph Delfino.


a valuable member of the


also


Yost group,


for many fruitful discussions,


both scientific and personal.


also wish to acknowledge those who provided funding for my research


salary which


prevented


me from


seeking


employment at


McDonald's


support myself.


This


includes the NASA Amtech Joint Agreement,


the Sandoz


Research


institute,


U.S.


Environmental


Protection


Agency/EMSL


Cincinnati


An extra thank you goes to Dr.


Thomas Behymer of the U


EPA/EMSL for his willingness to assist at any time.


have great difficulty finding the words to express the gratitude


have for


the many special friendships


have shared while at UF


. These include fellow Yost


group


members


Don


"The


Gecko


Eades,


Stacy


Rossi-Barshick,


Brad


"Smoothie" Coopersmith,


and Nate "Air Quaker" Yates


, as well as fellow graduate


students Kevin Kinter, Keith Palmer


and Larry "Moti Oti"


Villanueva.


would like


to make an extra acknowledgement of Don Eades, whom


thoroughly enjoyed






having as my coworker on this particle beam project, and Nate Yates, for always


knowing how to change the


trap software to suit my needs.


wish them and


everyone else too numerous to mention the best of


uck in their careers.


memories


we have shared will never be forgotten.


These were truly the


salad


days.


Finally and most


importantly,


express my sincerest


ove and thanks to my


family.


It is not possible to express enough thanks to my mother and father, who


have worked their entire life to provide me with whatever was necessary to help


me achieve my goals.


've never felt closer to my brother Gary whom


have


watched change careers,


attending Florida.


get married,


thank Gary,


and start (and expand) a family while


Nadine, Ryan,


was


and Jarrett for not letting the family


become boring wh


was away.


Although hundreds of miles have separated me


from my family during recent years,


have never felt closer to all of them.













TABLE OF CONTENTS


ACKNOWLEDGEMENTS


S S a S S S S ii


ABSTRACT


VII


CHAPTERS


INTRODUCTION


S. 1


The Quadrupole Io
Brief History


General Theory of


Trap Mass Spectrometer


. 2


SS 5 2


on Motion in the QITMS


Principles of Operation .
LC/MS using the QITMS .


The Particle Beam LC/MS


nterface.


Overview of Organization of Dissertation


CHARACTERIZATION OF


IMPORTANT PARTICLE BEAM


OPERATING PARAMETERS


Introduction
Experimental
Characterization Studies


* S S
* S S S


Nebulizing Helium Flow Rate


Desolvation Chamber


. S S S
* S S S S


Temperature


Desolvation Chamber Pressure


Target Temperature
Conclusions


EVALUATION OF STRATEGIES TO MINIMIZE ADVERSE


EFFECTS OF RESIDUAL SOLVENT


introduction


Experimental . .
Problems Caused by Residual Solvent


6
8







Strategies to Minimize Adverse Solvent Effects
Additional Stage of Momentum Separation
Elevation of rf Level .
Resonant Ejection of Single Ion Species


Compariso
Application to
Mixtures
Conclusions


in of Solvent 14
LC/PB/ITMSm


on Ejection Methods


Analyses
*. a .a .a a .a
* a a a a a .a


Simple


* a .a .a a a a
* a a a a a a a a a


Pesticide


* a a
* a a a


* a a
* a a a


APPLICATION OF LC/PB/ITMS TO ANALYSIS OF PESTICIDE
MIXTURES AND COMPARISON TO OTHER LC/PB/MS


SYSTEMS


introduction


Experimental .
Results and Discussion


El Mass Spectra .
Instrument Detection Limits
Instrument Calibration Curves
Precision of Peak Areas .
Alternating EI/CI Acquisitions
Conclusions .


IMPROVED QUANTITATION USING COELUTING


LABELED


SOTOPICALLY


INTERNAL STANDARDS


introduction


Experimental
Gas Chromatography/Mass


pectrometry


Benefits of Axial Modulation


Alternating M


ass-


Selective Storage Scans


Liquid Chromatography/Mass Spectrometry
Conclusions .


CONCLUSIONS


Conclusions
Suggestions


AND FUTURE WORK


for Future Work


REFERENCES


BIOGRAPHICAL SKETCH











Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy


DEVELOPMENT


AND APPLICATION OF PARTICLE BEAM-LC/MS ON THE


QUADRUPOLE


ON TRAP MASS


SPECTROMETER


Brent LaMar Kleintop


May


Chairperson: Richard A.


Yost


1993


Major Department: Chemistry


This dissertation presents results from


investigations of coupling a particle


beam (PB) interface for liquid chromatography/mass spectrometery (LC/MS) with


a quadrupole


on trap m


spectrometer (QITMS).


Unlike most other LC/MS


nterfaces


, PB interfaces are capable of producing


structural


information from


electron


onization (El) mass spectra which may allow identification of unknown


compounds.


Also,


the acknowledged sensitivity


and versatility


of the QITMS


might provide lower detection limits and provide the impetus for development of

future benchtop LC/MS/MS instrumentation.


Initially,


residual solvent introduced into the QITMS by the interface caused


space charging and a large degree of solvent-chemical ionization (CI).


The use


of an


additional


stage of momentum


separation


in the interface reduced the






amount of solvent which reached the interface; however


it was also necessary to


eject solvent ion


from within the trap prior to m


analysis.


Two modes of ion


trap


operation


implemented


with


standard


instrument


control


software


were


demonstrated to efficiently eject solvent ions.


El m


This allowed generation of classical


spectra of several pesticides which compared favorably to both library


spectra and spectra acquired from solid


probe/QITMS


analyses (i.e. a "solvent-


free" method) of pure compounds.


The ability to perform


both isocratic and gradient elution


LC/PB/QITMS


analyses of pesticide mixtures has been demonstrated.


The results obtained from


gradient


elution


LC/PB/QITMS


analyses


were


also


compared


to results


obtained


LC/PB/quadrupol


e-MS


system.


Both


system


provided


comparable


mits of detection and precision; however


n the relative intensities of fragment ions


of self-C


were observed


at large analyte concentrations was observed


some minor differences

i. Also, a larger degree

on the ion trap system.


Quantitation using coeluting isotopically labeled internal standards (IS) has


also been investigated.


selective storage scan


A new method of rapidly performing alternating m


has been demonstrated to provide excellent


ass-


nearity and


precision over four orders of magnitude


for gas chromatography/QITMS analyses.


coeluting


IS also


provided


linear


calibrations


using


LC/PB/QITMS.


improvements were largely


attributed to the coeluting


IS acting


as a


"carrier"


which improved analyte transport through the interface.











CHAPTER 1
INTRODUCTION


Since becoming commercially available in 1983,


the quadrupole ion trap


mass spectrometer (QITMS) has seen widespread use in both fundamental and


applied


mass spectrometric studies.


Although


introduced


commercially as a


benchtop mass spectrometric detector for gas chromatography (GC),


the QITMS


currently


seeing


increased


applications


liquid


chromatography/mass


spectrometry (LC/MS) systems.


In this dissertation


, results from


investigations


focused on coupling a particle beam (PB)


nterface for LC/MS


with a QITMS wil


be presented.


initially


problems were encountered which were caused by the


introduction


of residual


solvent into the QITMS by the


nterface.


Several


strategies were investigated to minimized these adverse solvent effects and allow


acquisition


classical


electron


ionization


mass


spectra


a variety


environmentally significant compounds which compared favorably with


brary El


spectra


acquired


more


traditional


mass


spectrometers


(e.g.


sector


quadrupole instruments).


The capabilities of the LC/PB/QITMS system were then


evaluated by applying it to the LC/MS analysis of pesticide mixtures.


Since al


commercially


available


systems


employ


quadrupole


mass


analyzers,


analytical figures of merit obtained on the LC/PB/QITMS system were compared


ft -- I *- 1 t I I a -


a CIA .-


*-l i








operational modes were


investigated to


improve quantitation using isotopically


labeled internal standards.


This


introductory chapter provides a historical perspective, as well as a


presentation of the operating principles of both the QITMS and the PB interface


for LC/MS


and also provides an overview of the organization of this dissertation.


The Quadrueole Ion


Trao M


Spectrometer


Brief History


A summary of the history of the development of the


QITMS


is provided


Table 1


The quadrupole


on trap was


initially described


n 1953 by Pau


coworkers


at the


University


Bonn


(Paul


Steinwedel


, 1953),


was


detailed


same


patent


described


operating


princip


quadrupole mass filter (Paul and Steinwedel,


1960).


The same


deas were also


proposed that same


year by Post and Heinrich (1953) and by Good (1953) at the


University of California,


mass


Berkeley.


spectrometer by Fischer (19


The quadrupole ion trap was first used as a

)59), who used mass-selective ion detection


using resonant absorption to produce a m


spectrum of krypton.


Detection via


resonant absorption involves the application of an auxi


ary alternating current (ac)


voltage of a particular frequency across the endcap electrodes of the ion trap.

An ion undergoes resonant absorption when its fundamental frequency of motion


!FI *lk a earvAn ae *ha #ranm aanr"ri *ha


IFIAAIIIAC Crnhr Ihnhu\


su. *r Irr~ ^ ** ___

















Table 1


Summary of the stages of development of the QITMS.


column


also depicts the time periods of each operational


ie third
mode


used during these stages of development.


1953


1959
1962


First disclosure (Paul and Steinwedel)
Use as a mass spectrometer (Fischer)


Storage


Mass-selective detection


of ions for rf spectroscopy


(Dehmelt and Major)


1968


Ejection of


ons to an external detector


(Dawson and Whetten)


1972


1980


Use of QUISTOR as ion source for
quadrupole mass filter (Todd et al.)


First use


Mass-selective storage


as GC detector (Armitage


March)


1984


1985


Disclosure of ion trap detector (ITDTM)
(Stafford et al.)
Ion trap mass spectrometer (ITMSTM)
(Kelley et al.)


ass-se


lective instability


1987


MS/MS, C
extension


ion injection


, mass-range


Th







applied potential


When this occurred


, ion signal was detected by measuring the


power absorbed by the ion from the resonant excitation circuit.


Many early applications of the ion trap


involved its use with a wide variety


of gas-phase rf


pectroscopic experiments


(Dehmelt,


1967


1969


Major


Dehmelt


the late


,1968).


The evolution of the ion trap as a mass spectrometer began in


1960s with the development of mass-selective storage


(Dawson


Whetten


, 1968a,b,


1969),


which is


milar to the operation of the quadrupole mass


filter.


n this mode, appropriate rf and direct current (dc) potentials were applied


to the electrodes such that only a very narrow mass range of ion


remained


trapped


small


Ions were detected by ejecting them from the


holes


trap through a series of


n one of the endcap electrodes to an external detector such as an


electron multiplier.


Although this method was usefu


for analysis over a fairly


narrow mass range,


it was cumbersome for acquiring a full m


spectrum,


which


required repeating the process of mass-selective storage for each mass over the

range of interest.


a result


of the


limitations


mass-selective


storage


mode


operation,


vast


majority


initial


experimental


applications


mass


spectrometric


studies


used


as a mass-selective


source


for the


quadrupole m


filter. For th


applications,


Todd and coworkers coined the


term


"_yadrupole ion store" or QUISTOR for the ion trap


(Lawson and Todd,


1971).


The QUISTOR/quadrupole combination was successfully used throughout








theoretical


(Todd


, 1980a)


aspects


trap,


develop


new


instrumentation (Kishore and Ghosh,


1979) and operational modes (Fulford and


March,


1978; Fulford et al.,


1980), and to study a variety of ionic processes such


as ion/molecule reactions


(Bonner et al.,


1973,


1974) and ion energetic


(Todd


et al.


,1980b).


capabilities


traps


have


dramatically


increased


with


development of the mass-selective instability mode of operation (Stafford et al.,


1984


Kelley et al


1985).


n this mode, ions covering a broad range of mass-to-


charge ratios (m/z) are trapped by application of an appropriate rf voltage to the


ring electrode.


A mass spectrum


is obtained by


nearly increasing the amplitude


of the rf voltage, which causes


ons of increasing m/z to be ejected through holes


in one of the endcap electrodes and detected by an external electron multiplier.

This new scan method provides a much simpler and more rapid approach for


acquisition


of mass spectra.


From


a single ionization


event


, an entire mass


spectrum can be obtained.


The development of the mass-selective instability scan was the impetu


ed to the commercial introduction of the ion trap detector (ITDTM) by Finnigan


MAT


n 1983 as a benchtop mass spectrometric detector for GC.


and sensitivity of the


analyses.


TDT resulted


1985 Finnigan MAT


The low cost


n widespread applications for routine GC


introduced the more versatile ion trap mass


spectrometer (ITM


STM) which allows both routine MS and more advanced MS








S/MS/MS, etc.).


Interest in ion trap technology increased dramatically after the


introduction


of the


TDM


TMS


a result,


instrumentation


operation of the QITMS have been the subject of several reviews (Cooks and


Kaiser


1990


Nourse and Cooks,


1990; Cooks et al.,


1991


March


1991


Todd,


1991


Todd and Penman


, 1991


March


, 1992).


A recent book also reviews the


fundamental


and applications of the quadrupole ion trap (March and Hughes,


1989).


General Theory of Ion Motion


n the QITMS


The QITMS


is operated by app


cation of an rf voltage to the ring electrode


which creates a three-dimensional electric field within the


electrode


surfaces.


Ions


are either trapped or ejected from the trap depending upon the m/z of the ion and


the applied electric fields.


The motion of an ion in a quadrupole electric field can


be described by equation


which is also known as the Mathieu


equation


(Dawson,


1976):


- 2 q cos 2) u


where u represents either the radial (r) or axial (z) axis,


voltage,


Jis the


and a. and q, are the Mathieu stability parameters.


phase of the rf


These parameters


are related to the


zero-to-peak


rf amplitude


amplitude


S .'


angular


S


+ (au


df









8eU


(1-2)


m ro Q2



4eV
mr02 2


(1-3)


Since ro and


are constant


, the


Mathieu


parameters can


be simplified


expressed as:


= U(m)
e


x const.


(1-4)


= V ()
e


x const.


(1-5)


From th


simplified equations,


it becomes


evident that the Mathieu parameter


q, is related to the rf potential applied to the ring electrode and that for a given


rf potential,


each m/z


has a unique value of q,.


Similarly


, au is related to the


applied dc potential and for a given dc potential,


each m/z


has a unique a. value.


values


determine


whether


solutions


Mathieu


equation


are stable,


through zero


meaning the displacement of an


(the center of the trap),


ion periodically passes


or whether the displacement


increases


= az








which yield stable solutions to the Mathieu equation,


it will be trapped and wi


process


within


trap


particular


secular


frequency.


Graphical


representations of stable solutions in a and q space are called stability diagrams.


The stability region which is relevant to the QITMS is shown in Figure 1


Ions


with values of a and q which


ie within the stab


ity diagram wi


be effectively


trapped.


The stability region is bounded by so called


so-pn


for .,


=0 or 1


a complex function of a. and q, and determines


the secular frequencies


of the


trapped ions.


The trajectories of ion


with the same l,,


value have the same


secular frequency


however


, the amplitude of the trajectories is governed by the


a and q values of each m/z.


The trajectory of an ion in the rz plane is illustrated


n Figure 1


It has the form of a


Lissajous figure composed of two secular


frequency components with a superimposed high frequency ripple resulting from


higher order harmon


of the ion's


secular frequ


Principles of Operation


quadrupole


trap


is the


three-dimensional


analog


of the more


iar quadrupole m


filter.


A schematic of the Finnigan


STM which was


used for most of these studies is


hown


in Figure 1-3.


It con


ists of a hyperbolic


ring electrode and two hyperbolic endcap electrodes,


radius of the ring electrode and


where ro represents the


is the half distance between the two endcap














0.20




0.00




-0.20


-0.40




-0.60




-0.80


iso-a 1.0
lines na o


0.0 0.2


0.00


0.0 q, eject = 0.908
0.2


0.4 rf-only
0.4
Yiso-p,
lines

0.6



0.8


0.40 0.80 1.20 1


Figure 1-1:


Stab


ity diagram for the quadrupole


on trap plotted


n a,q


pace.


with a,q parameters


ocated within the region of stability wil


ssess


stab


trajectories and be effectively trapped.








































Figure


plane.


Lissajous form of the trajectory of a trapped ion in the rz
'he figure is from a photograph of an illuminated charged


aluminum
trajectory


particle


spend


composed


in a quadrupole


lower


secular


uperimposed high frequency ripple (Todd,


ion trap.


frequency


with


1991)





















Filament


End Cap


Ring Electrode


Electron Multiplier Detector


End Cap


To Preamplifier
(Ion Signal)


Figure 1


Schematic diagram of the Finnigan ITMSTM used throughout these
studies.


I


J


Amplifier and
RF Generator,
Fundamental
RF Voltage


-


Scan Acquisition
Processor
(Computer)


Amplifier and
RF Generator,
Supplementary
RF Voltage








(Knight,


1983).


It has recently been disclosed however, that al


commercially sold


ion traps are actually "stretched" in the axial,


z, direction such that r


= 1.63zo2


(Louris et al.,


1992) where r,


1.000 cm and zo


= 0.783 cm.


The quadrupolar trapping field of the QITMS is generated by application


of an rf voltage to the ring electrode.


For the


TMST


, the frequency of the applied


rf signal is 1.1 MHz.


The generated field is actually not an ideal quadrupolar field,


but has contributions from higher order fields as we


Octapolar and dodecapolar


field contributions result from the "stretched" geometry of the electrode spacing.

Imperfections in the electrode surfaces and holes for injection of ionizing electrons


and ejection of ions


also


introduce hexapolar contributions to the trapping field.


Studying the effects of these nonlinear resonances has been the subject of many


recent


investigations (Guidugli et al.


1992; Eades and Yost,


1992)


Electron


onization


most


commonly


used


method


production of positive ions


n mass spectrometry (Duckworth et al


1986).


In the


ITMST


, ionizing electrons are created from a heated rhenium filament located


outside one of the endcap electrodes.


Electrons enter the trap by gating an


entrance


ens at


180 V for a period of time equivalent to the ionization time


(typically 1 ms) and ionize the neutral


present within the trap.


Ions are effectively


trapped in the


TMST when the values of their az and q, parameters fall within the


stability diagram (Figure 1


When operated


in the rf-only mode (az


= 0),


ions


with q, values less than q,


= 0.908 wil


be effectively trapped and stored.








pressure of a light buffer gas,


typically


mtorr of helium.


Collisions between


ions and helium atoms serve to kinetically "cool" the ions, which causes the ions


to migrate toward the center of the trap.


This results


n dramatic increases


sensitivity and resolution (Stafford et al.,


1984).


ITMSTM


acquires


a mass


spectrum


using


mass-selective


instability scan method (Stafford et aL


1984).


During the mass-selective instability


scan there is no dc potential


= 0)


applied to the trap


such that all ions


possess values of q, which lie along the qz axis of the stability diagram.


Since q,


inversely proportional to m/z


(Equation


1-5),


ions of lower m/z are located


towards the right of the q, axis.


Ions are "moved" along the q, axis by


nearly


ramping the rf potential,


*, (qz = Vfrom Equation 1-5) until they become unstable


at the stability boundary


where q,


= 0.908.


This results


n sequential ejection of


ions of


increasing


m/z from the trap where they are detected


by an external


electron multiplier


of 180 psec/u.


. Mass spectra are recorded on the


Typically during


TMSM using a scan rate


mass analysis, an additional axial modulation


signal


is applied across the endcap


electrodes.


This supplemental


signal


applied at slightly less than half the rf drive signal at approximately 6 Vp.


Just


prior to ejection,


the ion


come into resonance with the axial modulation signal,


which increases the amplitude of the


on's trajectory in the


z direction.


This


results in the ions being more tightly bunched upon ejection,


resolution and detection efficiency (Weber-Grabau et al.


yielding increased


1988).







simultaneous dc, rf,


and ac voltages.


For example, isolation of a single m/z


or a


narrow range of m/z's


n the trap can be accomplished


by application of an


appropriate combination of rf and dc voltages such that the m/z of interest is near


the apex of the stability diagram (Figure


-1) at q,


= 0.78, az


= 0.15 (Weber-


Grabau


, 1987).


Alternatively


, a "two-step"


isolation


method


been


described where higher mass ions are ejected at a working point along the $z


0 stability edge and lower mass ion


are ejected at a working point along the $z


stability edge (Gronowska et al.,


1990;


Yates et a/.


, 1991).


Tandem mass spectrometry (MS/MS) experiments are performed by first


mass-selecting a particular precursor ion.


supplemental resonant excitation


potential


is then


applied


across the endcaps at the secular frequency


of the


precursor


Resonance


excitation


kinetically


excites


causing


increase


n the amplitude of its trajectory


in the z-direction.


The amplitude of the


resonant excitation voltage,


however


, is kept low enough to avoid losses due to


resonant


ejection.


The kinetically excited precursor ion


undergoes


energetic


collisions


with


helium


buffer


which


can


result


collisionally


activated


dissociation (CAD).


Studies have demonstrated up to 10059


CAD efficiency and


overall


MS/MS


efficiencies approximately 14 times


higher than triple quadrupole


instruments which suggests that 'the ion trap may be


the most sensitive MS/MS


instrument


ever"


(Johnson


, 1990,


2172).


Multiple


stages


mass


spectrometry


(MS",


n>2)


experiments can be performed


by mass-selecting a








experiments up to MS12 have been successfully demonstrated


on the


TMSTM


(Louris et al.


1990).


LC/MS usina the QITMS


The combination of high-performance liquid chromatography (HPLC) with


mass


spectrometry


been


widely


recognized


as possessing


enormous


potential for analyzing a wide variety of compounds. Although HPLC does not

provide the chromatographic efficiency of capillary GC, analytes remain in the


condensed


phase


ambient


temperature


during


separation,


thermal


decomposition is not a problem.


This makes HPLC-based methods an appealing


choice for the analysis of a wide variety of thermally labile, nonvolatile, and polar

compounds which are either not amenable to GC or require derivatization for GC


analysis.


Indeed


, it has been estimated that only about 20% of al


known organic


compounds are amenable to GC and GC/MS analyses and that HPLC-based

methods should be capable of analyzing the vast majority of the remaining 80%


(Budde et al.


1990).


The major challenge involved with using a mass


detector is the design of a suitable


spectrometer as an HPLC


nterface which can convert the high pressure


mobile


phase


flow


phase,


maintain


typical


operating


conditions.


Vaporizing this quantity of liquid generates a volume of gas that must


be substantially reduced to maintain the high vacuum (typically 1


x 10.5 torr) of








direct liquid


introduction


(Baldwin


McLafferty,


1973),


interfaces


represented the first successful LC/MS interfaces.


However, the moving belt was


mechanically complex and subject to memory effects, while DLI required splitting


a large portion of the LC eluent which limited the sensitivity of the technique.


1980s


, the development of a "new generation" of improved aerosol-based


LC/MS


interfaces


including


thermospray


(Blakley et al.,


1980),


particle beam


(Willoughby and Browner,


1984),


and electrospray (Fenn etal.


1989) dramatically


broadened the applicability of LC/M


Although


majority


LC/MS


research


been


performed


using


quadrupole


instruments


, ion traps are seeing


increased use


n LC/MS


systems.


initial attempts to


nterface the widely used thermospray (TSP)


nterface with an


TMSTM


(Kaiser


et al.


, 1991)


exhibited


good sensitivity;


however,


high


solvent


background


pressures


caused


significant


peak


broadening


poor


mass


resolution).


performance


TSP/ITMS


system


was


significantly


improved using a differentially pumped ion source (Bier etal.,


1991).


Electrospray


(ESP) interfaces have seen the greatest number of LC/ITMST applications


n the


literature


(Van


Berkel et aL


, 1990,


McLuckey


et al.


, 1991)


. Since ESP yields


multiply charged ion


, even high molecular weight biological compounds are well


within the working mass range of the


TMSTM (m/zm,


= 650 u).


Ion trap systems


coupled with


TSP and ESP require the use of an ion injection system because


ions are generated within the interfaces,


external to the trap.








A number of features of the


TMST make it particularly attractive as a mass


analyzer for


TSP and ESP generated ions.


These include high sensitivity


ability to perform MS" experiments with high CAD efficiency,


perform kinetic measurements.


and the ability to


Since TSP and ESP are known as "soft" ionization


techniques which produce predominantly molecular ion


the capability to obtain


structural information from MS" experiments is particularly appealing.


The Particle Beam LC/MS


Interface


interface


represents


another


of the


new


generation


LC/MS


nterfaces based upon aerosol formation.


aerosol-based LC/MS


The primary advantage of using an


nterface is that solvent can evaporate far more rapidly from


droplets than from bulk solutions because of the


much higher surface area-to-


volume ratio (Browner et a.,


1986).


The original design was disclosed in 1984


and was named MAGIC for monodisperse aerosol generation interface for
---- 0 vww ^^^w


iquid


chromatography (Willoughby and Browner,


1984).


As variations based on MAGIC


became commercially


available


(Apffel


Nordman


1987


Willoughby


Poeppel,


1987),


they became simply known as particle beam


nterfaces.


Although differences exist between various commercial PB interfaces, all


consist of a nebulizer and some type of desolvation chamber


momentum


coupled with a


separator which removes solvent vapor from the beam of largely


desolvated particles. A schematic of the prototype


interface used


n these studies










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19
employs an additional third stage of pumping in the momentum separation region

to further reduce the amount of solvent which reaches the ion trap.


The interface works by first converting the LC


effluent into an


aerosol


having a narrow range of droplet diameters.

the liquid with a high concentric flow of heliu


The nebulizer in this interface shears

m. The droplets then travel through


a heated desolvation chamber where volatile solvent is vaporized resulting in a


mixture


of solvent vapor


, helium


, and


largely


desolvated


particles


containing


analyte.


This mixture then passes through a beam collimator which form


particle


beam


which


then


travels


through


momentum


separator


momentum separator


n this


nterface consists of three stages of pumping which


are separated by a series of skimmers.


Solvent and helium are pumped away


the momentum separator while the more massive and higher momentum analyte


particles


are transported


through


momentum


separator


region.


These


particles are transported through a transfer probe


nto the mass spectrometer


source region.


The transfer probe was


inserted


nto the


TMST via a


/2" o.d.


transfer line probe which allowed insertion and removal without disturbing the


high vacuum of the ITMSTM


The beam of particles is "flash" vaporized when it


collides with the hyperbolic surface of the filament endcap upon


entering the


TMST analyzer cavity.


The resulting vapor then travel


toward the center of the


trap where it is ionized


alternatively


by chemical


ionization


ion/molecule reaction


with reagent ions produced from a reagent gas.


Typical






20
operating parameters and optimization of the interface will be described in greater


detail


n Chapter


Particle beam interfaces have generated recent widespread interest largely


because of their ability to produce classical El m


spectra for a wide variety of


relatively


involatile


thermally


labile


compounds


environmental


biological interest (Behymer et al.


1990,


Voyksner et al.,


1990).


The generation


of El spectra is advantageou


because the fragmentation patterns found


n these


spectra


reveal


structural


information


which


affords


ability to


identify


unknown compounds,


a typical goal of many LC/MS


analyses.


El spectra also


can be compared to existing library spectra for the identification and confirmation


of unknown compounds.


TSP and ESP interfaces produce spectra unique to the


nterface which yield predominantly molecular weight


information.


This typically


mits th


techniques


targeted


compound


analysis,


although


use of


tandem mass spectrometry for obtaining structural


information has been reported


(Smith et al.


1990


Van Berkel et al.


, 1990).


Coupling a PB interface with a QITMS would appear to be an appealing


choice for many applications employing LC/MS.


The ability of PB to generate El


spectra affords the


identification of unknown compounds,


a typical goal of many


types of analyses, while the


sensitivity of the


QITMS


should also provide


ow limits


of detection.


mass


Currently,


all commercially available PB systems employ quadrupole


analyzers due to their ruggedness and low cost.


Although the coupling of








ions from an external ion source (Bier et al.,


1991) has been demonstrated,


rigorous studies have been performed which thoroughly evaluate the analytical

capabilities of a PB/QITMS system.


Overview of Oraanization of Dissertation


In this dissertation, results from investigations of coupling LC with a QITMS

via a PB interface are presented. A historical perspective and a review of the

basic operating principles of the QITMS and the PB interface are provided in this


introductory chapter.


The optimization of important PB operating parameters and


instrumental modifications are discussed in Chapter


Chapter 3 presents results


of several methods investigated to minimize adverse effects of residual solvent.


Application


of the PB/ITMSTM


system to the analyses of pesticide mixtures


presented


Chapter


Chapter


4 also


compares


performance


of the


PB/ITMSTM system with a PB system which employs a quadruple mass analyzer.


investigations of several ion trap operational modes to


improve quantitation using


isotopically labeled


internal


analyses are discussed


standards for both GC/ITMS


n Chapter 5.


Finally,


LC/PB/ITMS


conclusions and perspectives for


future work are presented in Chapter 6.











CHAPTER 2


CHARACTERIZATION OF


IMPORTANT PARTICLE BEAM


OPERATING PARAMETERS



Introduction


As discussed


n Chapter 1


particle beam (PB)


nterfaces have attracted


widespread


interest


recently


because


they


allow


generation


classical


electron


ionization


mass


spectra


a wide


variety


compounds


environmental (Brown et al.


1990) and biological interest (Voyksner et al.,


1990).


Generation


spectra


is advantageous


because they typically


exhibit rich


fragmentation patterns which can reveal structural information.


patterns of th


The fragmentation


spectra can then be compared to reference spectra using readily


available computer library spectral searches for the identification and confirmation

of unknown compounds, a typical goal of many LC/MS analyses.


Although the important PB operating parameters are well known (Voyksner


et al.


, 1990),


variation


between commercially available PB


nterfaces and MS


system


necessitate the need to characterize th


parameters for each system


n order to intelligently develop effective LC/MS methods.


chapter describes


and characterizes the important PB operating parameters for the LC/PB/ITMS


system


used


throughout


these


studies.


order


improve


performance,








modifications were made to both the interface and the analyzer.


and the results of these modifications wil


A description


also be discussed.


Experimental


instrumentation


Two HPLC systems were used for these characterization studies.


The first


was


ISCO


(Lincoln,


LC-2600


syringe


pump


which


used


a Valco


(Springfield,


NJ) 6-port manual injection valve with a 10 pL sample loop.


second


HPLC


system


was


a Hewlett-Packard


(Palo


, CA)


1090L


liquid


chromatograph fitted with a Rheodyne (Cotati,


CA) manual


injection valve with a


5 pL sample loop.


Solvent compositions and flow rates used are indicated in the


text.


characterization studies


were performed using flow injection analysis


(FIA) of analytes.


The LC/MS


interface was a prototype Finnigan MAT (San Jose, CA) particle


beam


interface


(Figure


1-4).


This


prototype


differs


from


commercially


available interface in that it employs three stages of pumping in the momentum

separator region to further reduce the amount of solvent which reaches the ion


trap.


Supplemental helium was added to the third stage of momentum separation


to prevent backstreaming of pump oil from the mechanical pumps caused by low


pressures.


Typical pressures in the three stages of the momentum separator


were


5-10


mtorr,


mtorr


(adjusted


addition





24
TMSTM via a V1/ probe lock which allowed insertion and removal of the interface


without disturbing the high vacuum of the mass spectrometer.


The probe tip was


positioned


- 14" away from the


on trap entrance to prevent high pressures inside


the trap.


The Rulone fitting normally


inserted


n the entrance hole to electrically


isolate a probe from the endcap was removed so a larger entrance


nto the ion


trap would be present.

The mass spectrometer used in these experiments was a Finnigan MAT


(San Jose, CA)


TMSTM


The vacuum chamber was maintained at 100C for al


experiments.


El was performed within the ion trap; detection was accomplished


with an electron multiplier set to yield


gain


and with


a single conversion


dynode at 0V.


No dynode voltage was used because the dynodes caused high


noise problems on the


STM at the time th


experiments were performed.


Partial pressures of residual solvent were typically


- 1 X 106 torr (uncorrected) as


measured by a Bayard-Alpert ionization gauge (Granville-Phillips,


Boulder,


CO)


mounted on the vacuum chamber.


Helium was added into the


STM vacuum


chamber to produce typical operating pressures of 1


Five microscans were averaged on the


X 104 torr (uncorrected).


Sm and returned to the data system


as a single scan.


Axial modulation (Weber-Grabau et al.


1987) was employed at


530 kHz and 6Vpp during the mass-selective instability scan to improve mass

resolution and sensitivity.








Samples and Reaaents


The structures of the standards used throughout these characterization


studies are shown in Figure 2-1.


Also shown are molecular weights and the


fragmentation which yields the base peak of each compound's


El mass spectrum.


Carbaryl


diuron


were


obtained


from


U.S.


Environmental


Protection


Agency (Pesticide Chemical Repository,


Research


Triangle Park,


NC); caffeine


and rotenone were purchased from Sigma (St. Louis,


MO).


All standards were


used without further purification. HPLC g

obtained from Fisher Scientific (Pittsburgh,


;rade methanol and acetonitrile were

PA) and reagent water was obtained


from a Milli-Q water purification system.


Characterization Studies


main


operating


parameters


interface


which


affect


performance


nebulizing


helium


flow


rate,


desolvation


chamber


temperature, desolvation chamber pressure, and source target temperature.


of these parameters were


investigated to determine what effects they have on


sensitivity


performance


system.


These


parameters


were


investigated with various commonly used LC mobile phases, including methanol,


acetonitrile


, and acetonitrile/reagent water mixtures and different flow rates.


assistance of Mr. Donald Eades during these characterization studies is gratefully























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Nebulizina Helium Flow Rate


The nebulizer used in the PB interface was a glass Meinhard (Santa Ana,


CA) nebulizer which consists of a pair of concentric tubes.


While the position of


the inner capillary tube is adjustable on other commercial interfaces (Apffel and


Nordman


,1987),


its position is fixed in the Meinhard nebulizer


. The nebulizer was


installed onto the desolvation chamber through a Cajon fitting which ensured

a vacuum-tight seal.

The HPLC eluant entered the nebulizer by passing through a length of 0.1


deactivated fused silica capillary column,


which was


inserted into the


inner tube of the nebulizer


. A high flow (


-0.6 L/min.)


of He was


introduced


through a gas port and flowed through the outer tube.


the inner capillary,


As the


iquid flow exited


the concentric flow of He dispersed the liquid flow


nto an


aerosol consisting of a distribution of micron-sized droplets (Browner et al.


1986).


The aerosol was then swept into the desolvation chamber by the flow of He.


The flow of He into the nebulizer was controlled


pressure of the regulator on the He supply.


by varying the


The plots in Figure


head


show how


varying the head


pressure


of the


He (nebulizing


flow)


affected the signal


different mobile phase compositions.


The data points represent the average peak


areas obtained from triplicate injections of 20 ng diuron.


The peak areas were


calculated from the extracted ion profile of the base peak (m/z 72) of the El mass


spectrum of diuron.


The curves are asymmetric and show that Door sianal


were


,













500000


400000

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200000


100000




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- 100
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CH3CN
CH3CN/H20
CH3CN/H20O


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Regu


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60


ig)


Figure


Plots of peak area vs.


nebulizing gas


mobile phase compositions.


triplicate


injections


standard deviation.


head pressure for different


Data points


diuron.


represent


Error


bars


averages
indicate


I IIIIIIII


) 80


I


IIIIII lilllllIl IlllIlllIl ii








primarily composed of low velocity drops with


arge mean diameters which are


difficult to desolvate.


high


pressures,


smaller


, high


velocity


droplets


formed.


Significant transport losses result from surface impact, turbulence, and


evaporation when the aerosol droplets are either too large or too small


et a.


(Browner


, 1982).


The plots also show that, as the percentage of water in the mobile phase

increases, a higher pressure (flow) of helium is required to produce optimum


performance.


This trend


related to the surface tension and viscosity of the


mobile phase.


Aerosol


are generated


because the


gas jet causes frictional


interactions with the liquid surface.


The main forces opposing aerosol generation


are the surface tension and the viscosity of the liquid phase.


much higher surface tension and is more viscou


Since water has a


than organic solvents, more


energy (hence higher gas flow) is required to efficiently nebulize aqueous solvents


(Browner et aL


1986).


It also appears that sensitivity decreases as the percentage of water in the


mobile phase is


increased.


Even at optimum conditions for each mobile phase


composition,


phase.


the peak areas were greatest when using a pure organic mobile


This observation can be explained by considering both the nebulization


desolvation


processes.


Similar studies


involving


characterization


of the


desolvation


chamber


temperature


showed


sensitivity


decreased


as the


percentage of water


n the mobile phase increased.


Since water has a much








phase


(Browner


, 1986).


Desolvation


aerosols


comprised


larger


aqueous droplets is more difficult because the aerosol has less surface area and

water also has a higher heat capacity and AH- than other common LC solvents


(Weast,


1982).


Indeed


other studies have demonstrated that the observed order


of sensitivity for different mobile phases is inversely related to the energy to heat


and vaporize the solvent (Voyksner et al.


1990).


It does not appear for this PB interface that the flow rate of the mobile

phase affects the optimum nebulizing gas flow as much as the mobile phase


composition.


Figure 2-3


shows nebulizing gas optimization curves for different


flow rates of 100% acetonitrile.


All curves indicate optimum conditions at 30-35


psig


head


pressure.


Although


optimum


conditions


vary


significantly


the best sensitivity was observed at lower mobile phase flow rates.


It was also


observed


that the


optimum


nebulizing


flow rate was


largely


compound-independent.


Desolvation Chamber


Temperature


Once


aerosol


generated,


droplets


are swept


a heated


desolvation chamber.


The main function of the desolvation chamber is to remove


the volatile solvent molecules from the


aerosol droplets.


Solvent evaporation is


achieved by the transfer of heat from the chamber walls to the


drops.


Any analyte


molecules which are present are typically less volatile and remain as particles.













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400000


200000




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Figure 2-3:


A*a6a 0.3


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20


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mL/min.
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$ \ I


30
Regu


Plots of peak area vs.
mobile phase flow rates.


ator


Pre


nebulizing gas


head


70


80


ig)


pressure for different


Data points represent averages of triplicate


injections of 20 ng diuron.


iiiiiiniTTlililllnillllllltii








The desolvation chamber in this interface was an 8" long,


hollow


nickel-


coated aluminum


block


(Figure


1-4).


It was heated


by two 300 W


cartridge


heaters inserted


nto the chamber block.


The temperature of the desolvation


chamber was


controlled


an extemal


Ogden


(model


ETR


9080,


Arlington


Heights,


L) feedback temperature controller which used a thermocouple to sense


the chamber temperature.


Figure 2-4 illustrates the


effects of desolvation chamber temperature and


mobile phase composition on the signal obtained for 20 ng of diuron.


The data


points represent the average areas obtained from triplicate FIA injections.


plots reveal that the optimum temperature of the desolvation chamber depends


on the composition of the mobile phase. Thb

the percentage of water in the mobile phase


heat capacity and AH, than organic solvents,


e optimum temperature


increased.


increased as


Since water has a larger


more energy is con


umed during


vaporization.


Thus, higher temperatures are needed to replace the heat lost from


adiabatic expansion due to solvent evaporation to maintain efficient desolvation.


The plots also show that signal


decreases as the percentage of water in the


mobile phase increased.


As mentioned previously,


this trend is probably a result


of both the nebulization and desolvation processes.


appears


from


plots


Figures


optimizing


desolvation chamber temperature was not as critical as optimizing the flow of


nebulizing gas.


While the signal obtained at non-optimum desolvation chamber












900000


800000


700000


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200000


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/


50/50


I I I I I1 II


Deso


30 40 50


Chamber


Temp


CH3CN/H20


60
(c)


Figure 2-4:


Plots illustrating the effect of desolvation chamber temperature on
peak areas obtained for FIA of 20 ng diuron at various mobile phase
compositions.









nebulizing g

(Figure 2-2).


las flow rates resulted


n as much as an 80% decrease in signal


However, this was not true for all the test compounds used.


Figure


2-5 shows desolvation temperature optimization curves for diuron and carbaryl.

Each curve was normalized with respect to its largest data point to better illustrate


the loss of signal at non-optimum conditions.


Although the peak areas for diuron


not vary by more than


20%,


peak areas for


carbaryl


at higher,


non-


optimum desolvation chamber temperatures decreased by as much as 80% with


respect to the maximum peak area.


Since carbaryl is more volatile than diuron,


at higher temperatures carbaryl was probably being vaporized in the desolvation

chamber and pumped away in the momentum separator region of the interface.


Although of a limited test set, Figure


chamber temperature is largely compound


also illustrates that optimum desolvation


independent as both curves exhibit


maximum signal at the same temperature.


Desolvation Chamber Pressure


The pressure in the desolvation chamber is largely determined by the flow


nebulizing


mobile


phase


flow


rate.


optimum


nebulization conditions


, the pressure in the desolvation chamber is typically 200


torr.


pressure


regime,


imiting


process


influencing


solvent


evaporation is the


rate of heat transport from the


surrounding gas to the


surface


of the aerosol droo


(Rrnwner


19R86


Helium


is used


WIiW *W I V* I I Y -


as the nebulizina


2-M













1.0



( 0.8



0
0Y


I
20


Desolv.


Diuron
(m/z 72)


Carbaryl
(m/z 144)


I I II I I I I I I I I 1 1 II
30 40 50


Chamber


Temp.


I I I I I III
60
(c)


Figure 2-5:


Normalized desolvation chamber temperature optimization curves
for diuron (m/z 72) and carbaryl (m/z 144) using a 100% acetonitrile
solvent at a flow rate of 0.3 mL/min.








aerosol


drops.


order


provide


a better


thermally


conductive


environment, supplemental He was added to the desolvation chamber to enhance


solvent


vaporization.


Helium


was


introduced


a Negretti


(Southampton,


England) fine metering valve through a Swagelok (Jax Valve, Jacksonville,


installed on the desolvation chamber


. A pressure gauge (Omega, Stamford,


CT) was also added to monitor the pressure of the desolvation chamber (Figure

1-4).


Figure 2-6 shows the effect of adding


supplemental He


to the desolvation


chamber.


The mobile phase for th


studies was 100% acetonitrile; the data


points represent the average peak areas obtained from either 20 ng caffeine or


100 ng carbaryl.


Optimization of the nebulization process accomplished prior to


these studies resulted in a desolvation chamber pressure of


210 torr.


The plots


indicate that a two-to-threefold increase in signal was obtained by


pressure in the desolvation chamber by approximately 120 torr


plateau was observed for both compounds.


increasing the


at which point a


These results are consistent with


those observed by other laboratories (Browner,


1986).


interesting to note that


commercially available


supplemental He


nterfaces of similar design do not utilize the addition of


n the desolvation chamber.


Target Temperature


After travelling through the momentum separator


, the analyte-containing



























Figure 2-6:


Plots illustrating affect of adding supplemental He to the desolvation
chamber for FIA of (a) 20 ng caffeine and (b) 100 ng carbaryl.










Desolv.


Chamber


Pressure


(torr)


80000

+
'*70000


V60000


50000


40000


30000


Amount He Added (torr)


Desolv.


Chamber


Pressure


(torr)


210
100000 J


90000


80000

70000

60000

50000

40000

30000


r-


210
900004^








particles


enter the ion trap where they strike the hyperbolic surface of one of the


endcap electrodes which served as the PB target.


The collis


on with the endcap


causes the particles to undergo a rapid flash vaporization.


This results in the


production of predominantly


ntact gas-phase analyte molecules.


The analyte


molecules are then ionized by E


, or alternately,


byC


with the


introduction of a


reagent gas.


The temperature of the PB target (endcap) plays an


important role


n the


signal obtained for PB analyses.


The flash vaporization process must be efficient


to prevent peak tailing,


which requires sufficiently high temperatures.


However,


thermal degradation of some compounds can occur if too high temperatures are


utilized.


Typical target temperatures used for PB analyses are between 250 and


3000C.


initially


the temperature of target endcap was maintained by radiatively


heating the entire


SM vacuum chamber


, including the ion trap and electron


multiplier, with the standard quartz heaters mounted


In order to prevent damage to the electron multiple


inside the vacuum chamber.

ier, temperatures were not


raised above 140C.


This resulted


n bad sensitivity and a large degree of peak


tailing even for FIA because these


ow temperatures yielded an


efficient flash


vaporization process.


n order to permit the use of typical PB target temperatures,


modifications


were made to the filament endcap electrode which served as the target.


Two


large holes were drilled into the body of the endcap to insert two 10W cartridge









to sense the endcap temperature.


The temperature of the endcap was controlled


by an external feedback Omega (model CN-2012,


Stamford


, CT) temperature


controller.


These modifications allowed the endcap to be heated to typical PB


operating temperatures of up to 290C while maintaining the electron multiplier
mounted within the vacuum chamber at normal operating temperatures of 1000C.


improvements these modifications brought


about are illustrated


Figure 2-7


. Shown


are mass chromatograms


of m/z


from triplicate FIA


injection of 200 ng carbaryl at endcap temperatures of 125 and 2500C.


temperatures,


the peaks exhibited a significant degree of peak tailing caused by


inefficient flash vaporization of the particle beam.


At higher temperatures,


peak


shapes were dramatically


observed.


The signal intensities


improved and little evidence of peak tailing was


hown in the figure also show that there was an


approximate three-fold


increase in peak height at the higher temperature.


Studies


characterizing


target


temperature


also


indicated


optimum temperature was largely compound-dependent.


Optimization curves for


the FIA of 100 ng carbaryl and 75 ng rotenone are shown


n Figure 2-8.


The plots


are normalized with respect to the maximum peak area in each data set for clarity


Data


points


represent


average


ion peak


areas


obtained


from


triplicate


injections.


While


maximum


response


carbaryl


occurs


at temperature


200oC


290C.


rotenone exhibits a maximum


at much higher target temperatures of


Rotenone is much less volatile than carbaryl,


so it is not surprising that






























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04-'
10 $



0 0
Og


(00L.



00 (
4-
Ef


Sc~a

SQ)
0)0
.-5

^-a
(0 (0

WO
Sa
[d L

(0-
eQQ





























cl--
0
Cl)


Ai!sueiul

















0
( 0.8
L.



( 0.6


-o
N 0.4


180


Carbaryl
(m/z 144)


Rotenone


(m/z


200


192)


'''l220ll
220


End cap


Il Ill' II


240


II II II I


26(


I I
0


Temperature


I 111111 II
280
(c)


300


Figure 2-8:


Target temperature optimization curves for carbaryl (m/z


144) and


rotenone


(m/z


192).


different


maxima


curves


exhibit


indicate that the optimum target temperature is largely compound-
dependent.


^*-






44

The carbaryl optimization curve illustrates that higher temperatures are not


optimum for all compounds.


This is because thermal decomposition of some


compounds


can


occur


high


target temperatures.


carbaryl,


best


response


of the 1 44 fragment ion (base peak) occurred at 200 C and decreased


by approximately 50% at target temperatures of 290C (Figure


2-8).


However, it


was observed that the total ion current signal


increased by approximately 20%


when the target temperature was increased from 200 C to 290 OC.


This indicated


carbaryl


likely underwent


some


degree of thermal


decomposition


which


limited the sensitivity of the m/z


144E


fragment ion at high target temperatures.


Conclusion


studies demonstrate the need for


optimization


of important


operating


parameters to


intelligently


develop effective


LC/MS


methods.


nebulizing gas flow rate, desolvation chamber temperature,


desolvation chamber


pressure,


and target temperature have al


been shown to affect the


sensitivity of


the LC/PB/ITMSTM system.


Most of th


interface parameters were found to be


largely mobile phase dependent; however,


some compound dependance was


observed


, most notably for the source target temperature.


mobile phase


dependance wil


make it difficult to optimize interface parameters for gradient


elution analyses because the mobile phase composition will change during the


analysis


Modifications to the ion trap endcap electrode were necessary to allow











CHAPTER 3
EVALUATION OF STRATEGIES TO MINIMIZE ADVERSE
EFFECTS OF RESIDUAL SOLVENT


introduction


Although ion traps are noted for their sensitivity


versatility


and potential


cost,


benchtop


currently


instrumentation


LC/MS


(including


, most


those


mass


using


spectrometric


interfaces)


systems


employ


quadrupole mass analyzers.


primarily


Ion traps have seen limited use


because of the large amount of solvent introduced


n LC/MS systems

by most LC/MS


nterfaces.


Excess solvent ions and neutrals typically cause space charging and


undesired


on/molecule reactions,


resulting in


poor mass resolution and poor


overall spectral quality.


n this chapter are reported several strategies which were evaluated,


aimed


at minimizing adverse effects caused by introduction of residual solvent from a PB


nterface.


These strategies


included one method which reduced the


amount of


solvent which reached the trap.


The versatility of the


ST also allowed the


creation of customized scan functions which ejected unwanted solvent ion


from


within the ion trap prior to mass analysis, while efficiently storing analyte ions of


interest.


Although the coupling of PB with an ion trap using both direct coupling








1991


, 1992),


currently


no information


appears


in the


literature


comparing


operational modes of the ion trap which minimize space charging by ejecting


residual LC solvent ions prior to mass analysis.


determine the best way to operate the


The goal of this work was to


STM to produce quality El spectra from


analytes


introduced via LC.


El spectra obtained from isocratic LC/PB/ITMSTM


analyses of simple pesticide mixtures (


_3 components) are compared to library


El spectra and


El spectra obtained from solids probe/ITMSTM


"solvent-free" method) of pure compounds.


Also


analyses


instrument calibration curves


and limits of detection (LOD) obtained from these isocratic LC/MS analyses on

this system are reported.


Experimental


instrumentation


Liauid


Chromatoaraphv.


Two


LC pumping


system


were employed


studies.


Solvent ejection studies utilized an ISCO (Lincoln,


NE) LC-2600


syringe pump.


Chromatographic separations were performed using a Hewlett-


Packard


(Palo


Alto


, CA)


1090L


high-performance


liquid


chromatograph.


Separations were performed on a 100


x 4.6 mm Hewlett-Packard octadecasily


column


, packed with 5 pm particles.


Separations were accomplished isocratically


with a mobile-phase composition of 80/20 acetonitrile/reagent water at a flow rate


of 0.3 mL/min.


The analytical column was thoroughly conditioned by pumping






47

a 50/50 acetonitrile/reagent water mixture through the column overnight to remove

residual impurities and column bleed.


nterface.


The LC/MS interface was a prototype Finnigan MAT


(San


Jose,


three-stage


particle


beam


interface


(Figure


1-4).


operating


princip


optimization


of the interface are described


greater


detail


Chapter 2.


important PB operating parameters including desolvation chamber


temperature and nebulizing


sensitivity.


He flow rate were optimized to provide maximum


The desolvation chamber pressure was optimized by addition of He


increase


pressure


approximately


400 torr


probe


was


positioned about /4" away from the


on trap entrance to prevent high pressures


inside the trap.


Spectrometer


. The mass spectrometer used


experiments


was a Finnigan MAT (San Jose, CA) ITMS


Fundamentals of ion trap operation,


theory


and ion motion are described in greater detail in Chapter 1


. The


TMS


vacuum chamber was maintained at 100C for all experiments.


Chapter


As described in


, the filament endcap of the ion trap was modified to allow insertion of


10W heater cartridges which were controlled by


an external temperature


controller (Omega Engineering


Model CN 2012,


Stamford


, CT).


This endcap


served as the particle beam target and was operated at temperatures of 250-


290 C.


Electron


ionization was employed within the ion trap;


detection was


.. a








typically


x 10 torr (uncorrected) as measured by a Bayard-Alpert ionization


gauge (Granville-Phillips, Boulder, CO) mounted on the vacuum chamber. Helium

was added into the vacuum chamber to produce typical operating pressures of


x 10" torr (uncorrected).


TMST was repeatedly scanned from 55 to 500


amu to check for formation of dimers and ion/molecule reaction products


Axial


modulation


(Weber-Grabau et al.,


1987)


at 530 kHz and 6V


was employed


during the analytical scan in al


studies to reduce the effects of space charge and


improve sensitivity.


Samples


and Reaaents


Methomyl and


nuron were obtained from AccuStandard (New Haven, CT),


caffeine from Sigma (St. Louis,


MO); al


other pesticide standards were obtained


from the U


Environmental Protection Agency (Pesticide Chemical Repository,


Research Triangle Park, NC)


All standards were used without further purification.


The structures of the standards used in these studies are shown


in Figure 3-1.


Also shown are molecular weights and the El fragmentation which yields the


base


peak of each compound's


mass spectrum.


Structures


, molecular weights and El


fragmentation for carbaryl,


rotenone, and diuron were shown previously in Figure


HPLC grade methanol and acetonitrile were obtained from Fisher


ientific


(Pittsburgh,


PA);


reagent water was obtained from


a Milli-Q water purification


system.












I
Z-I


sVwwvw^


WVWVV W


m-.1-


O r
(ho

< s


nc
(O~
--
**
Q.


.- U)
* o

I
("1
0) ^
t0U)


I
Z-I
I
o= -
'O -
gvwvvwuw
GD 0


.c *
E C
05 -


Z-- I


swCvVvw^
+


o 0=0

Z-I


CO
Da3
0)


I

II
0 I
If
0-0


JVw/VVwV


0=c =








Problems Caused by Residual Solvent


The major challenge encountered when interfacing LC directly with the ion

trap was minimizing adverse effects caused by the introduction of residual solvent


from the interface.


Solvent molecules (S) in the trap are ionized by El:


-* S+'


resulting


a large


population


solvent


ions


which


caused


space


charge


conditions.


Space charge results when the density of ion


n the trap becomes


large enough that ion-ion interactions become significant.


This can distort the


trajectories


of trapped


ions


resulting


spectral


quality with


poor


mass


resolution and


correct mass assignments.


In the ion trap,


ions and neutrals are present within a confined space for


a period of time prior to ejection/detection.


As a result,


a large population of


solvent ion


and molecules can also cause undesired ion/molecule reactions to


occur


Most notably


a large degree of solvent-C


of analyte neutral


can occur


as illustrated below:


(S + H)+


(S + H)+


-H)


(M + H)+


These equations show that a solvent radical ion


(S+) can react with a neutral


a a a. S a ..1 -1 .t-a


^ -* -1


1 rl ~ 1 .








proton transfer will occur and a protonated molecule, (M+H)+


forms.


This is


typically


a "soft"'


ionization


process,


meaning


that the


(M+H)+


ions


typically


undergo little fragmentation as compared to the M'*"


ions initially formed by El.


Since the primary advantage of using PB is the ability to acquire El mass spectra,

these adverse effects of residual solvent must be minimized.

These adverse effects are illustrated in the profile mass spectrum shown


n Figure 3-2.


The mass spectrum was acquired from FIA of


-100 ng of carbary


n 100% methanol mobile phase.


The spectrum shown is an expansion of the m/z


25-150 mass range to better illustrate the resolution between adjacent masses;


the abundance of the M'

abundance of methanol


' ion at m/z 201 was

solvent ions centered


<5% relative to


around


145*


m/z 33 caus


The large

ed space


charging which resulted in poor mass resolution between adjacent low masses.


Notice that resolution


improved at higher masses.


nset


Figure 3-2 is


provided to better illustrate the mass resolution between


144


145


. As


discussed


Chapter


TMSM


generates


mass


spectra by


sequentially


ejecting trapped ion


in solvent ions being


from low to high mass (Stafford et al.


ejected/detected


1984).


This results


before higher mass ions during


mass


analysis,


reducing space charging when higher mass


are detected.


144*/145+


ratio in this spectrum


also indicated


a large degree of


solvent-C


occurred.


The base peaks of the El and Cl mass spectra of carbaryl


are 144+


(M-57)*


and 145* (M+H-57)*


, respectively.


Although some 145" from































0
t 0)
a o
(0 C
0 0


U-
O 0)

< Q)
U- Sc


a)






O
C





O
O)
0






O
15





or
c-
a+
0
0








6 -




O c
I -
+'
05 (


0w
a -
---r ^


*o

(O


i -

Wo E













































I -7

_ .-


I--b


-IS
-4^









-04


-ai
a^


:CO
-r ~


_I


r


! I


(Qsi)


Aiisueiul


CI
=r


-----


.--_-_


&


I~


W








carbaryl (11 % relative to 144"),


the figure shows the intensity of 145+ being about


three times greater than


that of 144k


The abundant methanol


solvent ion


evidently


caused


a large amount


of solvent-C


to occur


ndeed


the use of


residual solvent ions to perform solvent-CI analyses of pesticides with the same


LC/PB/ITM


Sm system has been demonstrated (Eades et aL,


1992).


However,


here the large degree of solvent-CI was undesirable since the goal of this work


was to produce quality El spectra.


prior to mass analysis to minimize


This figure illustrates the


need to eiect solvent


space charging and solvent-C


to obtain


good quality El m


Stratea


spectra.


to Minimize Adverse Solvent Effects


different types


adverse effects of residual


strategy


which


solvent are illustrated


used


in the


block


to minimize


diagram of the


LC/PB/ITM


STM system


analyte molecu


in Figure 3-3.


(S and A


The block diagram shows that solvent and


, respectively) elute from the


HPLC and pass through


the PB


nterface


into the ion trap where solvent and analyte ions (S+


and A+) are


formed by E


The number of solvent molecules which reach the trap could be


reduced


by using


various


nstrumentation-based


approaches


before the trap.


Alternately


the trap could be operated such that solvent ions are ejected from


within the trap prior to m


analysis.


By employing these strategies,


ideally only


analyte ions of interest eventually reach the detector




















+
O)














0
(4


(Ac
ID>
>6
Vy)
Cu
I.-


ci
'U


E N .0-,
oE .
N I-
o a
E3
o
.2 2


S-


a )
*1 s
CO C
w rc
o .w


a)

30
)1:
(U"
WI


Eut
-0~



O-
s c
0-
Ama


O



c,,








As mentioned previously, the


nterface used in these studies employs an


additional


third


stage


momentum


separation.


additional


stage


momentum


separation


is an


example of one strategy


aimed


at reducing the


number of solvent molecules which reach the trap.


The amount of solvent which


reaches the trap could also be reduced by employing a membrane drier


n place


of the desolvation chamber.


In the membrane


volatile solvent diffu


through


membrane


pumped


away


while


involatile


analyte


particles


transferred to the momentum separator.


The commercially available Universal


nterface from Vestec is based on this operating principle (Vestal et al.,


1990).


Solvent


molecules


also


prevented


from


reaching


trap


using


injection of ions created


n an external ion source.


been demonstrated using both on-axis (Louri


et al.


Previously


injection has


,1989) and off-axi


(Pedder


et al.


, 1989) ion sources.


Different


TMSTM


operational


modes can


also


implemented to


eject


solvent ions


from within the trap.


Previous


research


our labs


here at UF


investigated method


for mass-selective ionization in the quadrupole ion trap to


eliminate undesired ion


of a range of mass/charge (m/z) values


(Eades et al.,


1991).


These


included the use of resonant


excitation


employing


waveform


comprised of multiple frequencies.


However


, implementation of th


methods


required modifications to the


ion trap operation


STM source code.


implemented with standard


In this chapter, two modes of


TMST software are evaluated for






57

analysis: 1) elevation of rf voltages to eject ions below a chosen m/z ratio (i.e.

impose a low mass cutoff) and 2) application of a supplemental rf signal to eject


a single solvent ion species.


Both methods were evaluated when applied either


during ionization or during an ion storage period following ionization.


A summary


of strategies which may minimize adverse solvent effects is shown below in Table


Table 3-1


Summary of Strategies to Minimize Adverse Solvent Effects.


Remove Solvent Molecules Before the


Trap


. Membrane Drier prior to Momentum Separator
. Additional Third Stage of Momentum Separation in


External Source and Ion


nterface


injection


On-Axis
Off-Axis


Eject Solvent Ions within the Ion


Trap


Elevate rf Voltage (Impose Low Mass Cutoff)


During


onization Step


b. During Ion Storage
Resonant Ejection of Single I
a. During Ionization Step
b. During Ion Storage


Species (Notch Filter)








Additional Staae of Momentum Separation


The same PB interface was used to determine the benefits of using the

additional third stage of momentum separation to reduce the amount of solvent


which reached the trap.


The interface was converted to a two-stage interface by


removing the third skimmer and third stage roughing pump from the interface.

Pressures in the momentum separator region were approximately 5-10 torr and


400-500 mtorr is stage one and stage two,


respectively.


pressures are not


significantly


different


than


those


observed


when


employing


three


stages


momentum separation.

Figure 3-5 illustrates that the additional stage of pumping does reduce the


amount


solvent


which


reaches


trap.


Shown


are the


ntensities


protonated acetonitr


e (m/z 42) at different flow rates of 100% acetonitrile mobile


phase.


figure


demonstrates


solvent


intensity


increased


with


increased flow rate and that about four times


less solvent ions were formed when


using


three stages of pumping.


Table 3-2


ists the ion


gauge pressures for


various


solvent compositions for both configurations.


obtained at a flow rate of 0.3 mL/min.


and with no


pressures were


supplemental He added to the


desolvation chamber


STM vacuum chamber, or third stage of the momentum


separator


pressures


were


read


directly


from


gauge,


with


correction factors


used.


The table indicates that the partial


pressures


of the














1400

1200


1000

800

600

400

200

0


0.1 0.3 0.5


Flow Rate (mL/min)


Figure 3-5:


Comparison


various


flow


of intensities


rates


using


of acetonitrile


both


(M+H)+


a two-stage


solvent ions
three-stage


interface.


I 3-Stage 2-Stage









Table 3-2:


Comparison


gauge


pressures


various


solvent


compositions using two and three stages


of momentum separation


Ion Gauge Pressure (torr)


100%
CHOCN


2-stage

3-stage


1.9 X1 0i

5.8 X 10


75/25
CHCCN/H,_O
19X 10


1.9 X 104

5.7 X 106


50/50
CHCN/H1O


2.8 X 104

5.7 X 104


25/75
ChLCN/HO


3.2 X 104

3.5 X 10-5s


All pressures obtained at solvent flow rate of 0.3 mL/min. and no


He added to desolvation chamber


supplemental


. Pressures were read directly from the ion


gauge meter with no correction factor used.


The performance of both configurations was evaluated by comparing the

El spectra obtained for FIA of 20 ng caffeine in 100% acetonitrile mobile phase.


The spectra are presented


n Figure 3-6.


spectrum obtained from a computer


Also


brary


shown is a library reference El


included with the


TMST software.


spectrum


obtained


using


three


stage


nterface


shows


excellent


comparison with the


library spectrum with respect to both fragmentation pattern


and relative


ntensities of the m


peaks.


The spectrum obtained using two


stages,


however, does not compare favorably with the library spectrum.


. .. N


-8 S C a 8


f 8


- -


- -. .Y -LL~ .;- -r 1 r -. a a a -l a ar a~ a* *l aC a a a sa ;- ~ au C fl S














I- -0
V
mC
ap
-on

CO
00


Q Q-

'=CO
a)
L 0
So
t

*" .


S0)
E


'CO
10
*6^


st
O5 *
C
(uIJ, *-

) WO
0- i
wn n


0 0) LI.




E -

* m
w0<
Oma 0.

CO
Sa>


cm


cv,
0)
























_^Y
~cmn
'-4


N



SD--


*\T I 1
'-4

(p


O -


N-
03-


(D --


SI I I I I


-Co





-N



-03


+


+a)
S^-


r"


-. "


-CM
-NC\
-1


a,
O -


-to
-0
- 7"


-0
CO


cN
0--


_ I
CD


I 1 1 1 1


-LO
-N
-(N

L0
-0
-CN


-Lo
-0L




-CD
- r



- ft


10
-CN
-1 cU


NC)

tLO
-0






cx,



1CD




it )
4






63

activated dissociation (CAD) to occur from collisions with background solvent


molecules.


Also


, the most abundant molecular ion peak was the (M+H)+


peak


at m/z 195 which


indicated a


arge degree of solvent-C


occurred.


These figures


illustrate


that


additional


third


stage


momentum


separation


removed


significant amounts of solvent and improved the performance of the LC/PB/ITMST

system.


Elevation of rf Level


One method


of solvent ion ejection studied


involved elevation of the rf


voltage applied to ring electrode to eject ions below a chosen m/


to impose


a low mass cutoff.


In this mode, the ion trap was operated


n the


rf-only mode


with


Mathieu


parameter


=0).


Since


Mathieu


parameter


proportional to the rf voltage (Equation 1-5),


elevation of the rf voltage increased


the q, values


of trapped ions.


In the rf-only mode, ions with values of q, greater


than 0.908 wi


(z) direction.


follow unstable trajectories


and be ejected from the trap


Since q, is inversely proportional to m/z


(Equation 1-5),


n the axial

ions from


low molecular weight LC solvents (e.g.


CH3OH,


CH3CN,


H20) were ejected at a


properly


chosen


low rf potential while analyte ions of higher m/z


remained


stored.


In this mode, the ion trap was basically operating as a high-pass mass


filter.


The effect of elevating the rf voltage upon both solvent and analyte ions is












oa cm
OtC T



O-S -




CL.q
oo, c
cDCS 0 I

*n~ y) J





t o.2
O r


maga
Eo
N-En C-

4~- 4-'


e-
- tf **o -5







Ew D t
S- -*









-ces
O -
|^%S
C*-






a $ iO



^.^ w m~
1(8. O S *-


-, cl
N-. CU


E w o
N3 0'CV.



.. o c ca
C O0 0)L.
E-4-'-



#ce

o- a), 4
* ~o Ci
-Ct



cowoc
-._ S' wE'






>5 (0c-ja
+*g 0- T0
^ mo -s
u *B > *B

CO O O>4a

---CS
* U)- 0
0) 0)1 aStfl





-
4-' 0 -
Rests' s
4- ...

+* O *


0
L.

















0
0

%- 0


00


Cn

C_



O-
O

o


6D 1jOA Op


aO




0+

OL








solvent (m/z


42) and the most abundant fragment ion of diuron (m/z


Note


here that the stability diagrams are plotted in terms of actual rf and dc voltage


applied to the electrodes, rather than a,q space.


rf-only mode, the rf voltage determines the


Since the trap is operated


ow mass cutoff of the trap,


n the


which is


also shown.


At an rf level corresponding to point A in the figure, both the solvent


and analyte ion will be trapped because this point is located within the stability


diagram of both ions.


Point B is located outside the solvent


but is still within the stability diagram of the analyte.


on stability diagram


At this rf level


the solvent


on wil


be ejected while the analyte ion will remain effectively trapped.


This mode of operation was investigated when applied both during the


ionization event and afterwards


, during ion storage.


The effect of raising the rf


level (low mass cutoff) upon the ion intensity of some commonly used LC solvents


is shown


n the plots of Figure 3-8.


As expected,


as the instrument's


low mass


cutoff


approached


each


solvent


species,


solvent


ions


were


efficiently (100%) ejected from the ion trap.


These plots were created by raising


the rf level after ionization


, during ion storage.


Although not shown,


similar plots


were obtained by elevating the rf during ionization.


Figure 3-9


Ilustrates how the


intensity of the carbaryl analyte ion (144+)


was affected by elevating the rf


evel (q,) both during


onization and during ion


storage.


These plots were obtained by varying either the ionization or storage


values of q, with a constant amount of carbary


(2 ng/p4L yielding 10 ng/s


at 0.3

















19+
H30O


33+


CH3OH2


42+
CH3CNH+


0 10 20 30 40 50


Low


Ma


Cutoff


Figure 3-8:


Plots of normalized solvent


on intensities


vs. rf


evel (expressed as


low mass cutoff) during ion storage illustrating efficient ejection of


common LC solvent


ons.


m/












0.00
' 1


0.20


I I. I I I I I


0.40


III III IIII


0.60


I iiIIIII


0.80


I lJ III II


IaI III III


+
4 0.8


Elevate rf
\ During Ion
vI Storage

1i


Elevate


During


onization


S.-


I I I I I I I I I


Low


I I I I I I I I 1 I
bco


Ma


Cutoff


I I I I I I I I I 50
150


(m/


Figure 3-9:


Plots


intensity


144+


fragment


carbaryl


rf level


(expressed
ion storage.


as low mass cutoff) both during ionization and during








signal


was


relatively


unaffected


storage


until


stability


limit was


exceeded


, signal decreased significantly with increasing ionization q,.


As the


value


q, increases,


so does the


initial


kinetic


energy


of the


ions formed,


resulting in large initial velocities and ion losses due to quasi-unstable trajectories


(Dawson,


1976).


These losses occur when the magnitude of an ion's


oscillation


exceeds


ntemal


dimensions


of the


trap


even


though


mathematical


conditions for stability still exist.


Although raising an ion's


q, value during ion


storage also increases its kinetic energy,


the ions are already effectively trapped


so ion


losses


are minimal


until


ions


become


unstable


when


qz=0.908.


Elevating the


onization value of q,


of an ion also decreases the


initial ionization


volume which limits the region


n which ions can be created and remain stable


(Dawson,


1976).


The observed decreases


n intensity could also be the result of


decreased ionization cross-sections due to high electron energies at elevated rf


levels.


Preliminary studies investigating the effects of ionization rf level (q2) of n-


butylbenzene ions also showed decreased ion


(Pedder et al.


ntensities at higher values of q,


1992)


There were also some differences


n the extent


of solvent-C


between


spectra obtained by ejecting solvent during


ionization and during ion storage.


Figure 3-10


shows how the ratio of 144+ (El fragment) to 145


fragment plus


'"C isotope of 144+)


is affected by elevating the rf


during


ionization and


storage for carbaryl


n 100% methanol.


The rf level where the methanol solvent












Eject


+


0
--+- 2.0
CD


Solvent
Ions:


Elevate rf during
ionization




Elevate rf during
Ion Storage


III IIII I III IIIII II


SI I II II I I I I I I I I I I I I I I I I I I
) 40 50 60


'I l70l
) 70


Low


Ma


Cutoff


Figure 3-10:


Plots of ratio of 144'


(expressed as


(El fragment) to 145+


ow mass


cutoff) both during


ion storage for carbaryl in 100% methanol.


fragment) vs. rf level
onization and during


Dashed


indicates rf


level where methanol solvent ions are efficiently ejected from the
trap.


m/








in the figure.


In a "pure" El spectrum,


144+/145+


intensity ratio would be


expected to be 9.0,


based on the natural abundance of 'C isotopes of 144'


.The


low ratios obtained at low rf levels resulted from solvent ions causing a


arge


degree of solvent-CI.


Ejection


of solvent ions


decreased


the amount


of CI


resulting in increased 144C/145* ratios; the inability to achieve the expected ratio


for a pure El spectrum indicated that some solvent-CI still


occurred in the time


before solvent ions were ejected.


Also


lower ratios were observed when the rf


was elevated during ion storage.


the ionization time,


This is because solvent ions were stored during


which allowed more time for solvent-CI to occur before the


solvent ions were ejected.


Resonant Election of Sinale Ion Species


The other method of solvent ion ejection studied involved resonant ejection


of a single m/z


solvent ion species by applying a notch filter (Kelley et al.


1985).


This was accompli


hed by


applying


a supplemental


gnal


(resonant


excitation voltage) across the endcap electrodes to kinetically excite a particular


solvent ion m/z species


such that it was ejected from the trap.


The trajectories


of trapped ions of a particular m/z are generally characterized by their unique

secular frequencies, wz, which are a complex function of the Mathieu parameters


az and q,, and 8z,


which relates to the frequency of the oscillation of the ions.


Application of the resonant excitation voltage at the wz of a particular solvent ion


6V p








oscillations.


The excited ion can then undergo CAD with residual buffer gas


molecules.


Alternatively,


and of relevance to this discussion,


the excited ion


species can also be ejected from the trap if sufficient power is absorbed such that


the amplitude of the oscillations become larger than the trap's


dimensions.


use of resonant ejection was investigated because it permitted ionization to be


performed


lower


values


which


may


result


better


sensitivity


compounds whose El mass spectra have low m/z base peaks.


As with elevating the rf amplitude, the use of a notch filter was


investigated


when


applied


either


during


ionization


or ion storage.


Figure 3-11


illustrates


resonant ejection of the m/z 42 ion of acetonitrile solvent both during ionization


and afterwards


, during ion storage.


The figure shows that m/z 42 was efficiently


100%) ejected when resonant ejection was applied during ion storage.


Since


ions of different m/z p

signal were observed.


'ossess different secular frequencies,


no losses in analyte


This process was not nearly as efficient, however


when


applied during


the ionization


pulse.


In this case only about one-third


of the


solvent ions were ejected.


This is because the ionization and ejection of ions


were acting


as competing


processes.


Ions were constantly being


produced


during the ionization event; those created towards the end of the ionization period


were only resonated for a very short period of time,


and thus were not efficiently


ejected.


Furthermore


onization


times


were


typically


only


This


represents the maximum amount of time an ion was resonated during ionization.













(M+H)


1277










C-)


35 40 45 50 55


Resonant Excitation Voltage
OFF


Resonant Excitation Voltage
ON







-M -h. sAJL v-tt


1' "41!I
i 4G


* I V I j


I TTTI I II I"
0 708


80


mass/charge


Figure 3-11:


a) Profile mass spectra
(M+H) + solvent ions (n


illustrating resonant ejection of acetonitrile
i/z 42) during ion storage.













(M +H)+


Resonant Excitation Voltage
OFF


35 40 45 50 55 60 65 70 75 8B


iViA


Resonant Excitation Voltage
ON





A -A. 4'


35 40 45 50 55 60 65 70 75 80


mass/charge


Figure 3-11:


(continued) b) Profi
acetonitrile (M+ H)+


mass


spectra


solvent ions


ustrating resonant ejection of
42) during ionization.


13B1







ComParison of Solvent Ion Election Methods


The analyte signal obtained for methods which efficiently eject solvent ions


are compared in Figure 3-12.


These plots were obtained by varying the ionization


time with a constant amount of diuron (1 ng/pL yielding 5 ng/s at 0.3 mL/min.) in


100% methanol flowing through the


nterface.


Illustrated


n Figure


base peak of the El spectrum of diuron occurs at m/z 72; its


intensity is plotted


in Figure 3-1


evels were elevated such that al


below m/z 45 were


ejected for methods involving elevated rf leve


For the notch filter mode, the


resonant excitation signal was set to eject the (M+H) ion of methanol solvent


(m/z 33) for 10 ms during ion storage. As expected,


increasing the ionization time


resulted in


inear increases in signal for al


methods unti


space charge develops


due to too many analyte ions being trapped, at which point the plots begin to


level off. The plots also reveal that methods which involved ejection of solvent

ions during ion storage produce about two times greater signal than ejection


during ionization.


As discussed previously


we believe this to be because of ion


osses due to quasi-unstable trajectories


and smaller ionization volumes


at higher


values of qz during


ionization


(Dawson,


1976).


It should


be noted that these


effects might not be as significant for compounds whose El mass spectral base


peaks are at higher m/z values.


Similar studies


monitoring m/z


144 (qz


=0.28) of


carbaryl show less than two times difference


n signal between these operational


modes.


This


was not further


investigated


because the


mass spectra of the













2500


2000


Elevate


Storage


during


I


0 1500


1000


Resonant
during lo


Elevate r
Ioniozation


Ejection
n Storage





luring


500


0-,r
0.0


I I i I I I I I I


on


1.0
on


1.5
me


(m


I I I I I I
2.5


Figure 3-1


Plots


diuron


comparing


analyte


methods


ion signal


described


vs. i


the text which


onization


efficiently


time
eject


solvent ions.


I I I I II II I I I I I I I I I I I I I I I








To obtain maximum sensitivity,


all subsequent studies ejected solvent ions


by elevating the rf level after ionization, during ion storage. Although resonant

ejection during ion storage yielded essentially the same sensitivity, elevation of the


rf amplitude ejected all solvent ion species,


as well as background


ions


water


, column bleed, etc.),


below the chosen m/z.


Also,


with standard


TMSTM


software, ejection of more than one m/z solvent ion species by resonant excitation


would require multiple resonant ejection events.


Although not all solvent ion


species require


10 ms for efficient ejection,


multiple resonant ejection events


would allow more time for undesired ion-molecule reactions to occur.


Multiple


resonant ejection events would be necessary for LC/PB/ITMSTM analyses which

would employ gradient elution or isocratic solvent mixtures.


ADDlication to LC/PB/ITMSTM


Analyses of Simple Pesticide Mixtures


The capabilities of the LC/PB/ITMSTM


system were


initially evaluated by


performing


isocratic


LC/MS


analyses


simple


pesticide


mixtures


components).


The El


mass spectral quality,


estimated LODs


and instrument


calibration


curves


were


used


evaluate


performance


under


realistic


conditions.


Ionization was performed at an rf level corresponding to a low mass


cutoff


of m/z


20 for


ms; solvent ions


were ejected


during


storage


elevating the rf level to eject all ions below m/z 55.


LC/PB/ITMS


analysis


a mixture


of three


pesticides


using




























Figure 3-13:


Total ion chromatogram (TIC), mass chromatogram


and amounts


analyzed


from


LC/PB/ITMS


analysis


a three-pesticide


mixture using LC conditions described in the text.











18Bx





TIC


TIC


250 ng
m/z 88 Methomyl


m/z 72


100 ng
Diuron


m/z 61


250 ng
Linuron


1B8 288 388


A J0


4- A1


m _


wl


I


10~








figure displays the total ion chromatogram


(TIC),


mass chromatograms of the


base peaks of the El mass spectra of each component,


and amounts of each


component injected.


Structures and E


fragmentation of each component were


shown previously in Figure 2-1


and 3-1


These chromatogram


illustrate better


than baseline separation of the compounds was achieved


ess than 6 mm.


The background-subtracted mass spectrum of 80 ng of diuron (m.w. =232


amu)


obtained


from


these


analyses


compared


with


both


a reference


spectrum


(Hites,


1985)


mass


spectrum


obtained


from


solids


probe/ITMSTM analysis


n Figure 3-14.


The spectra are quite similar with respect


to both fragmentation patterns and


relative fragment ion


ntensities.


The low


abundance of the (M+1)+ ion


n the LC/PB/ITMSTM spectra indicated that only


a small


amount of Cl occurred


spectral quality.


, and did not significantly degrade the overall


The spectra of the other compounds


n the test mixture also


compared favorably with reference and solids probe/ITM


instrument calibration curve for diuron


STM El spectra.


is shown in Figure 3-15.


calibration


curves were constructed


by plotting the


integrated


ion abundance


(peak


area)


of the


quantitation


as a function


amount


injected.


quantitation ion for each compound was the base peak of its fu


spectrum.


-scan El mass


It appears from the figure that a linear calibration was obtained from


diuron.


which better


The inset of the figure is an expansion of the region from


ustrates the linearity at the low end.


10-100 ng


The value of the correlation






























Figure 3-14:


El m.
solid


pr


spectra of diuron obtained from (a) library (Hites, 1985), (b)
robe/ITMSTM analysis, and (c) LC/PB/ITMS analysis of 80


ng diuron (background-subtracted).


w
















100


M+*
232


187


60 80 100 120 140 160 180 200 220 240


10wx


63
- n il-


124133


159 187 215


60 88 180 120 140 160 180 200 220 240


100%


81597
159


-^- *^k e n- rr'ia


80 100 120 140 160 180 200 220 240


M +

















- c
c Cc




0a
Om


C a

Im


irn



La




































SI 1 1 1 1 1 1 i I I I II i i I | | i i i I I
3 0 0 0
3 0 0 0
S0 0 0
- r0
'5y) +DZ aJV


O
.o


O


C




: *D
O
: o

-CM





--O
0


CO
cof



Q0


E

0<
0






0
OI





O


0 0 0


L 1








analyzed.


The non-linearities at the ends of the calibration curve are presumably


due to particle beam transport problems at the low end (Bellar et al.


1990) and


the onset of space charging caused by too many analyte ions at the high end.

Although diuron here shows linear behavior, nonlinear calibration curves, like that


obtained for linuron in Figure 3-16,


are far more prevalent


n LC/PB/MS.


nonlinear behavior of PB has been attributed to transport losses through the


momentum separator region of the


nterface.


This has been observed by several


other laboratories as a limitation of PB/LC/MS


for quantitative analyses (Doerge


Miles,


1991


, Brown


Draper


, 1991).


The use of isotopically labelled


ntemal standards has been suggested as a possible solution to this problem and


has been the topic of several recent reports (Ho et al.,


1992, Doerge et al.


1992).


Quantitation using PB and the carrier effect will be discussed


n greater detai


Chapter


instrument


detection


limits


were estimated


selecting


a sample


concentration which reliably yielded a 3:1 signal/noise ratio for each compound's


quantitation


full-scan


mass


spectrum.


Figure


3-17


illustrates


estimated detection limits routinely obtained on this system for several carbamate


and urea-based pesticides.


The LOD's


are typically in the low ng range and are


comparable to LOD's


reported for PB systems which employ quadrupole mass


analyzers (Behymer et al.


1990).


The LOD reported here for


inuron is 10 times


lower than previously reported (Behymer et aL,


1990) because the base peak of













400000





300000


0
a 200000
<


100000


III1111111I
200


I II IIII


Amt.


111111111 ll


400


111111 1


600


I I I I I II ll


800
(ng)


1000


SlIll200
1200


Figure 3-16


Linuron
Dashed


instrument calibration curve from PB/LC/ITMS


analysis.


ne represents region where the onset of space charging


occurred.


injected

























(d
0
0)
cl-
Q


--O
oI


C
0
Ow
L.
*S
0


Figure 3-17:


Estimated
Pesticides


detection
routinely


mits for several carbamate and


obtained


PB/ITMSTM


urea-based


isocratic


anal


described


n the experimental


section.


'4-


I.-
L.
0.
0


m n1








report to eliminate interference from using


ammonium acetate in the mobile


phase,


which


necessitated


a less


intense


(M+', m/z 248)


quantitation.

These LODs were obtained from the calibration runs and are not intended


to be


presented


as the


lowest


LODs


possible


each


compound


on the


LC/PB/ITMST system.


Note that there are a number of options offered by the


LC/PB/ITM


ionization


STM system that could further


times


improve th


, higher multiplier voltages,


LOD'


of a high


, including longer


voltage conversion


dynode, and addition of mobile phase additives such as ammonium acetate to


improve


analyte


transport


through


interface.


Automatic


variation


of the


ionization time using automatic gain control,


AGC (Stafford et al.


1987


Yost et


, 1987),


might lower detection limits and extend the linear dynamic range as


well.


Conclusions


successful


coupling


a PB


nterface


with


an I


TMSTM


been


demonstrated


n this chapter


When directly coupling


a PB


nterface with an


TMST


, it was necessary to eject solvent ion


to minimize space charging and


prevent a significant degree of solvent-C


from occurring.


The additional third


stage of momentum separation has been demonstrated to reduce the amount of


solvent which reached the trap.


Ejection of solvent ion


prior to m


analysis


:








spectra and El spectra obtained by solids probe/ITM


STM analyses. Although linear


instrument


calibration


curves


were


observed


, nonlinear


behavior


was


more


prevalent for LC/PB/ITMSTM determinations of several pesticides.


for several pesticides have been estimated to be


Typical LODs


n the low ng range.











CHAPTER 4
APPLICATION OF LC/PB/ITMS TO ANALYSIS OF PESTICIDE MIXTURES


AND COMPARISON TO OTHER LC/PB/MS


SYSTEMS


Introduction


The analytical utility


of PB relies on the ability to generate classical El


spectra


wide


variety


environmentally


biologically


significant


compounds introduced via LC.


The vast majority of PB/LC/MS system


currently


n use employ quadrupole mass analyzers due to their widespread availability, low


cost, and tolerance of relatively high operating pressures.


mited use


Ion traps have seen


n LC/MS systems primarily because of the large amount of solvent


introduced by most LC/MS


interfaces.


n the previous chapter


several strategies


were investigated which minimized adverse solvent effects and allowed acquisition


mass


spectra


from


isocratic


LC/PB/ITMS


analyses


which


compared


favorably to reference library spectra.

Although isocratic separations are well suited for individual applications


which require simple separation strategies,


they are limited for the analysis of


complex mixtures


with


components


having


a wide


range


retention


times.


Isocratic separations of multicomponent mixtures typically exhibit poor resolution


of early eluting components,


bad peak shape of late eluting components,








complex mixtures


require the use of gradient elution,


which


analogous to


temperature programming for GC.


n gradient elution,


the composition of the


mobile phase is changed throughout the analysis to


increase its eluent strength.


An optimized gradient affords the ability to efficiently analyze a


arge number of


components in a minimum amount of time.

This chapter will report the application of the LC/PB/ITMST system for the


analysis of a ten-component pesticide mixture.


The pesticide mixture required the


use of gradient elution to achieve adequate separation of the components.


performance of this system for gradient elution analyses wil


be compared to that


an LC/PB/MS


system


regards to detection


limits,


which


employed


calibration


a quadrupole


curves


mass


, precision,


analyzer with


overall


spectral


quality.


Finally, the capability of the ion trap to acquire both El and Cl spectra in


alternate scans over the course of an LC peak will be demonstrated.


ExDerimental


Liauid ChromatoaraDhv


Chromatographic separations were performed using


a Hewlett-Packard


(Palo


Alto,


1090L


high-performance


iquid


chromatograph


fitted


with


Rheodyne


(Cotati,


manual


injection


valve


with


a 5 upL


sample


loop.


Separations were performed on a Waters (Milford,


a I -


MA) Nova-Pak 150 mm


-I a a' .,,,,,, ....... ..:L Xt.. S-1 -1- -1- ..... ...- S


* J 11 ii __K


- L






92

through the column overnight to remove residual impurities and column bleed.

The mobile phase used for these studies was an acetonitrile/0.01M ammonium


acetate in


reagent water mixture at a flow rate of 0.3


mL/min.


Post-column


addition


was


used


increase


percent


organic


phase


through


interface.


SCO


(Lincoln,


LC-2600 syringe pump was used for post-


column addition of 100% acetonitrile at a flow rate of 0.1


mL/min,


resulting in a


total mobile phase flow rate of 0.4 mL/min.


through the interface.


nterface


The LC/MS interface was a prototype Finnigan MAT (San Jose, CA) three-


stage particle beam interface (Figure 1-4).


nterface is described


n greater


detai


Chapters


Important


parameters


including


desolvation


chamber temperature, pressure, and nebulizing He flow rate were optimized by

making several injections of the test mixture under different conditions to provide


maximum s

Optimization


sensitivity


more


a majority


difficult


gradient


compounds in thl

elution analyses


mixture.


because


composition of the mobile phase changes throughout the course of the analysis.

Chapter 2 revealed that most PB parameters are largely mobile phase dependant.


Typical pressures


in the three stages of the momentum separator were 5-10 torr,


300 mtorr, and 100 mtorr (adjusted by addition of He),


respectively.


nterface


was inserted into the mass spectrometers via a /" o.d. transfer line probe through




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FILES



DEVELOPMENT AND APPLICATION OF PARTICLE BEAM LC/MS
ON THE QUADRUPOLE ION TRAP MASS SPECTROMETER
By
BRENT LAMAR KLEINTOP
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1993

To Mom and Dad in appreciation for all they’ve done.

ACKNOWLEDGEMENTS
I wish to express my sincere gratitude to my advisor, Dr. Richard A. Yost
for his insight and guidance throughout my graduate studies. I would also like
to acknowledge and thank the members of my graduate committee, Dr. Jim
Winefordner, Dr. Vanecia Young, Dr. Jim Boncella, and Dr. Joseph Delfino. I also
wish to acknowledge Dr. Jodie Johnson, a valuable member of the Yost group,
for many fruitful discussions, both scientific and personal.
I also wish to acknowledge those who provided funding for my research
and salary which prevented me from seeking employment at McDonald’s to
support myself. This includes the NASA Amtech Joint Agreement, the Sandoz
Research Institute, and the U.S. Environmental Protection Agency/EMSL in
Cincinnati, OH. An extra thank you goes to Dr. Thomas Behymer of the U.S.
EPA/EMSL for his willingness to assist at any time.
I have great difficulty finding the words to express the gratitude I have for
the many special friendships I have shared while at UF. These include fellow Yost
group members Don "The Gecko Kid" Eades, Stacy Rossi-Barshick, Brad
"Smoothie" Coopersmith, and Nate "Air Quaker" Yates, as well as fellow graduate
students Kevin Kinter, Keith Palmer, and Larry "Moti Oti" Villanueva. I would like
to make an extra acknowledgement of Don Eades, whom I thoroughly enjoyed

having as my coworker on this particle beam project, and Nate Yates, for always
knowing how to change the trap software to suit my needs. I wish them and
everyone else too numerous to mention the best of luck in their careers. The
memories we have shared will never be forgotten. These were truly the salad
days.
Finally and most importantly, I express my sincerest love and thanks to my
family. It is not possible to express enough thanks to my mother and father, who
have worked their entire life to provide me with whatever was necessary to help
me achieve my goals. I’ve never felt closer to my brother Gary whom I have
watched change careers, get married, and start (and expand) a family while I was
attending Florida. I thank Gary, Nadine, Ryan, and Jarrett for not letting the family
become boring while I was away. Although hundreds of miles have separated me
from my family during recent years, I have never felt closer to all of them.
IV

TABLE OF CONTENTS
ACKNOWLEDGEMENTS iii
ABSTRACT vii
CHAPTERS
1 INTRODUCTION 1
The Quadrupole Ion Trap Mass Spectrometer 2
Brief History 2
General Theory of Ion Motion in the QITMS 6
Principles of Operation 8
LC/MS using the QITMS 15
The Particle Beam LC/MS Interface 17
Overview of Organization of Dissertation 21
2 CHARACTERIZATION OF IMPORTANT PARTICLE BEAM
OPERATING PARAMETERS 22
Introduction 22
Experimental 23
Characterization Studies 25
Nebulizing Helium Flow Rate 27
Desolvation Chamber Temperature 30
Desolvation Chamber Pressure 34
Target Temperature 36
Conclusions 44
3 EVALUATION OF STRATEGIES TO MINIMIZE ADVERSE
EFFECTS OF RESIDUAL SOLVENT 45
Introduction 45
Experimental 46
Problems Caused by Residual Solvent 50
v

Strategies to Minimize Adverse Solvent Effects 54
Additional Stage of Momentum Separation 58
Elevation of rf Level 63
Resonant Ejection of Single Ion Species 71
Comparison of Solvent Ion Ejection Methods 75
Application to LC/PB/ITMSâ„¢ Analyses of Simple Pesticide
Mixtures 77
Conclusions 88
4 APPLICATION OF LC/PB/ITMS TO ANALYSIS OF PESTICIDE
MIXTURES AND COMPARISON TO OTHER LC/PB/MS
SYSTEMS 90
Introduction 90
Experimental 91
Results and Discussion 95
El Mass Spectra 103
Instrument Detection Limits 110
Instrument Calibration Curves 113
Precision of Peak Areas 116
Alternating El/Cl Acquisitions 118
Conclusions 123
5 IMPROVED QUANTITATION USING COELUTING ISOTOPICALLY
LABELED INTERNAL STANDARDS 127
Introduction 127
Experimental 130
Gas Chromatography/Mass Spectrometry 134
Benefits of Axial Modulation 134
Alternating Mass-Selective Storage Scans 140
Liquid Chromatography/Mass Spectrometry 149
Conclusions 163
6 CONCLUSIONS AND FUTURE WORK 165
Conclusions 165
Suggestions for Future Work 168
REFERENCES 172
BIOGRAPHICAL SKETCH 181
VI

Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
DEVELOPMENT AND APPLICATION OF PARTICLE BEAM-LC/MS ON THE
QUADRUPOLE ION TRAP MASS SPECTROMETER
By
Brent LaMar Kleintop
May, 1993
Chairperson: Richard A. Yost
Major Department: Chemistry
This dissertation presents results from investigations of coupling a particle
beam (PB) interface for liquid chromatography/mass spectrometery (LC/MS) with
a quadrupole ion trap mass spectrometer (QITMS). Unlike most other LC/MS
interfaces, PB interfaces are capable of producing structural information from
electron ionization (El) mass spectra which may allow identification of unknown
compounds. Also, the acknowledged sensitivity and versatility of the QITMS
might provide lower detection limits and provide the impetus for development of
future benchtop LC/MS/MS instrumentation.
Initially, residual solvent introduced into the QITMS by the interface caused
space charging and a large degree of solvent-chemical ionization (Cl). The use
of an additional stage of momentum separation in the interface reduced the

amount of solvent which reached the interface; however, it was also necessary to
eject solvent ions from within the trap prior to mass analysis. Two modes of ion
trap operation implemented with standard instrument control software were
demonstrated to efficiently eject solvent ions. This allowed generation of classical
El mass spectra of several pesticides which compared favorably to both library
spectra and spectra acquired from solids probe/QITMS analyses (i.e. a "solvent-
free" method) of pure compounds.
The ability to perform both isocratic and gradient elution LC/PB/QITMS
analyses of pesticide mixtures has been demonstrated. The results obtained from
the gradient elution LC/PB/QITMS analyses were also compared to results
obtained on an LC/PB/quadrupole-MS system. Both systems provided
comparable limits of detection and precision; however, some minor differences
in the relative intensities of fragment ions were observed. Also, a larger degree
of self-CI at large analyte concentrations was observed on the ion trap system.
Quantitation using coeluting isotopically labeled internal standards (IS) has
also been investigated. A new method of rapidly performing alternating mass-
selective storage scans has been demonstrated to provide excellent linearity and
precision over four orders of magnitude for gas chromatography/QITMS analyses.
The coeluting IS also provided linear calibrations using LC/PB/QITMS. The
improvements were largely attributed to the coeluting IS acting as a "carrier"
which improved analyte transport through the interface.
viii

CHAPTER 1
INTRODUCTION
Since becoming commercially available in 1983, the quadrupole ion trap
mass spectrometer (QITMS) has seen widespread use in both fundamental and
applied mass spectrometric studies. Although introduced commercially as a
benchtop mass spectrometric detector for gas chromatography (GC), the QITMS
is currently seeing increased applications in liquid chromatography/mass
spectrometry (LC/MS) systems. In this dissertation, results from investigations
focussed on coupling a particle beam (PB) interface for LC/MS with a QITMS will
be presented. Initially, problems were encountered which were caused by the
introduction of residual solvent into the QITMS by the PB interface. Several
strategies were investigated to minimized these adverse solvent effects and allow
acquisition of classical electron ionization (El) mass spectra for a variety of
environmentally significant compounds which compared favorably with library El
spectra acquired by more traditional mass spectrometers (e.g. sector and
quadrupole instruments). The capabilities of the LC/PB/QITMS system were then
evaluated by applying it to the LC/MS analysis of pesticide mixtures. Since all
commercially available PB systems employ quadrupole mass analyzers, the
analytical figures of merit obtained on the LC/PB/QITMS system were compared
to those obtained using a PB/quadrupole MS system. Finally, several QITMS
1

2
operational modes were investigated to improve quantitation using isotopically
labeled internal standards.
This introductory chapter provides a historical perspective, as well as a
presentation of the operating principles of both the QITMS and the PB interface
for LC/MS and also provides an overview of the organization of this dissertation.
The Quadrupole Ion Trap Mass Spectrometer
Brief History
A summary of the history of the development of the QITMS is provided in
Table 1-1. The quadrupole ion trap was initially described in 1953 by Paul and
coworkers at the University of Bonn (Paul and Steinwedel, 1953), and was
detailed in the same patent that described the operating principles of the
quadrupole mass filter (Paul and Steinwedel, 1960). The same ideas were also
proposed that same year by Post and Heinrich (1953) and by Good (1953) at the
University of California, Berkeley. The quadrupole ion trap was first used as a
mass spectrometer by Fischer (1959), who used mass-selective ion detection
using resonant absorption to produce a mass spectrum of krypton. Detection via
resonant absorption involves the application of an auxiliary alternating current (ac)
voltage of a particular frequency across the endcap electrodes of the ion trap.
An ion undergoes resonant absorption when its fundamental frequency of motion
in the axial direction (secular frequency) is the same as the frequency of the

3
Table 1-1: Summary of the stages of development of the QITMS. The third
column also depicts the time periods of each operational mode
used during these stages of development.
1953
First disclosure (Paul and Steinwedel)
1959
Use as a mass spectrometer (Fischer)
Mass-selective detection
1962
Storage of ions for rf spectroscopy
(Dehmelt and Major)
1968
Ejection of ions to an external detector
(Dawson and Whetten)
1972
Use of QUISTOR as ion source for
quadrupole mass filter (Todd et al.)
Mass-selective storage
1980
First use as GC detector (Armitage and
March)
1984
Disclosure of ion trap detector (ITDâ„¢)
(Stafford et al.)
1985
Ion trap mass spectrometer (ITMSâ„¢)
(Kelley et al.)
Mass-selective instability
1987
MS/MS, Cl, ion injection, mass-range
extension, etc.

4
applied potential. When this occurred, ion signal was detected by measuring the
power absorbed by the ion from the resonant excitation circuit.
Many early applications of the ion trap involved its use with a wide variety
of gas-phase rf spectroscopic experiments (Dehmelt, 1967, 1969; Major and
Dehmelt, 1968). The evolution of the ion trap as a mass spectrometer began in
the late 1960s with the development of mass-selective storage (Dawson and
Whetten, 1968a,b, 1969), which is similar to the operation ofthequadrupole mass
filter. In this mode, appropriate rf and direct current (dc) potentials were applied
to the electrodes such that only a very narrow mass range of ions remained
trapped. Ions were detected by ejecting them from the trap through a series of
small holes in one of the endcap electrodes to an external detector such as an
electron multiplier. Although this method was useful for analysis over a fairly
narrow mass range, it was cumbersome for acquiring a full mass spectrum, which
required repeating the process of mass-selective storage for each mass over the
range of interest.
As a result of the limitations of the mass-selective storage mode of
operation, the vast majority of initial experimental applications for mass
spectrometric studies used the ion trap as a mass-selective source for the
quadrupole mass filter. For these applications, Todd and coworkers coined the
term "quadrupole ion store" or QUISTOR for the ion trap (Lawson and Todd,
1971). The QUISTOR/quadrupole combination was successfully used throughout
the 1970s to study the physical (Lawson et al., 1973; Todd et al., 1980c) and

5
theoretical (Todd et al., 1980a) aspects of the ion trap, to develop new
instrumentation (Kishore and Ghosh, 1979) and operational modes (Fulford and
March, 1978; Fulford et al., 1980), and to study a variety of ionic processes such
as ion/molecule reactions (Bonner et al., 1973, 1974) and ion energetics (Todd
etai, 1980b).
The capabilities of ion traps have dramatically increased with the
development of the mass-selective instability mode of operation (Stafford et al.,
1984; Kelley et al., 1985). In this mode, ions covering a broad range of mass-to-
charge ratios (m/z) are trapped by application of an appropriate rf voltage to the
ring electrode. A mass spectrum is obtained by linearly increasing the amplitude
of the rf voltage, which causes ions of increasing m/z to be ejected through holes
in one of the endcap electrodes and detected by an external electron multiplier.
This new scan method provides a much simpler and more rapid approach for
acquisition of mass spectra. From a single ionization event, an entire mass
spectrum can be obtained.
The development of the mass-selective instability scan was the impetus that
led to the commercial introduction of the ion trap detector (ITDâ„¢) by Finnigan
MAT in 1983 as a benchtop mass spectrometric detector for GC. The low cost
and sensitivity of the ITDâ„¢ resulted in widespread applications for routine GC
analyses. In 1985 Finnigan MAT introduced the more versatile ion trap mass
spectrometer (ITMSâ„¢) which allows both routine MS and more advanced MS
analyses such as mass-selective storage (rf/dc operation) and MSn (i.e. MS/MS,

6
MS/MS/MS, etc.). Interest in ion trap technology increased dramatically after the
introduction of the ITDâ„¢ and ITMSâ„¢. As a result, the instrumentation and
operation of the QITMS have been the subject of several reviews (Cooks and
Kaiser, 1990; Nourse and Cooks, 1990; Cooks etai, 1991; March, 1991; Todd,
1991; Todd and Penman, 1991; March, 1992). A recent book also reviews the
fundamentals and applications of the quadrupole ion trap (March and Hughes,
1989).
General Theory of Ion Motion in the QITMS
The QITMS is operated by application of an rf voltage to the ring electrode
which creates a three-dimensional electric field within the electrode surfaces. Ions
are either trapped or ejected from the trap depending upon the m/z of the ion and
the applied electric fields. The motion of an ion in a quadrupole electric field can
be described by equation 1-1, which is also known as the Mathieu equation
(Dawson, 1976):
d2u
dF
2 <7ücos2f) u = 0
(1-1)
where u represents either the radial (r) or axial (z) axis, f is the phase of the rf
voltage, and au and qu are the Mathieu stability parameters. These parameters
are related to the zero-to-peak rf amplitude (V), dc amplitude (U), angular
frequency of the rf potential (Q), and m/z by equations 1-2 and 1-3:

7
(1-2)
(1-3)
Since r0 and Q are constant, the Mathieu parameters can be simplified and
expressed as:
a = U (—) x const,
e
(1-4)
qu = V {—) x const.
(1-5)
e
From these simplified equations, it becomes evident that the Mathieu parameter
qu is related to the rf potential applied to the ring electrode and that for a given
rf potential, each m/z has a unique value of qu. Similarly, au is related to the
applied dc potential and for a given dc potential, each m/z has a unique au value.
The values of au and qu determine whether solutions to the Mathieu
equation are stable, meaning the displacement of an ion periodically passes
through zero (the center of the trap), or whether the displacement increases
without limit to infinity, with the ion being lost. When an ion has au and qu values

8
which yield stable solutions to the Mathieu equation, it will be trapped and will
precess within the trap at a particular secular frequency. Graphical
representations of stable solutions in a and q space are called stability diagrams.
The stability region which is relevant to the QITMS is shown in Figure 1-1. Ions
with values of a and q which lie within the stability diagram will be effectively
trapped.
The stability region is bounded by so called \so-f}u lines for /3U=0 or 1. /3U
is a complex function of au and qu and determines the secular frequencies of the
trapped ions. The trajectories of ions with the same fiu value have the same
secular frequency; however, the amplitude of the trajectories is governed by the
a and q values of each m/z. The trajectory of an ion in the rz plane is illustrated
in Figure 1-2. It has the form of a 2:1 Lissajous figure composed of two secular
frequency components with a superimposed high frequency ripple resulting from
higher order harmonics of the ion’s secular frequency.
Principles of Operation
The quadrupole ion trap is the three-dimensional analog of the more
familiar quadrupole mass filter. A schematic of the Finnigan ITMSâ„¢ which was
used for most of these studies is shown in Figure 1-3. It consists of a hyperbolic
ring electrode and two hyperbolic endcap electrodes, where r0 represents the
radius of the ring electrode and z0 is the half distance between the two endcap
electrodes. For a "theoretical" quadrupole ion trap, z0 is related to r0 by r02 = 2z/

9
qz
Figure 1-1: Stability diagram for the quadrupole ion trap plotted in a,q space.
Ions with a,q parameters located within the region of stability will
possess stable trajectories and be effectively trapped.

10
Figure 1-2: The 2:1 Llssajous form of the trajectory of a trapped ion in the rz
plane. The figure is from a photograph of an illuminated charged
aluminum particle suspended in a quadrupole ion trap. The
trajectory is composed of a lower secular frequency with a
superimposed high frequency ripple (Todd, 1991).

11
Figure 1-3: Schematic diagram of the Finnigan ITMSâ„¢ used throughout these
studies.

12
(Knight, 1983). It has recently been disclosed however, that all commercially sold
ion traps are actually "stretched" in the axial, z, direction such that r02 = 1.63z/
(Louris et at., 1992) where r0 = 1.000 cm and z0 = 0.783 cm.
The quadrupolar trapping field of the QITMS is generated by application
of an rf voltage to the ring electrode. For the ITMSâ„¢, the frequency of the applied
rf signal is 1.1 MHz. The generated field is actually not an ideal quadrupolar field,
but has contributions from higher order fields as well. Octapolar and dodecapolar
field contributions result from the "stretched" geometry of the electrode spacing.
Imperfections in the electrode surfaces and holes for injection of ionizing electrons
and ejection of ions also introduce hexapolar contributions to the trapping field.
Studying the effects of these nonlinear resonances has been the subject of many
recent investigations (Guidugli etal., 1992; Eades and Yost, 1992)
Electron ionization (El) is the most commonly used method for the
production of positive ions in mass spectrometry (Duckworth et al., 1986). In the
ITMSâ„¢, ionizing electrons are created from a heated rhenium filament located
outside one of the endcap electrodes. Electrons enter the trap by gating an
entrance lens at ± 180 V for a period of time equivalent to the ionization time
(typically 1 ms) and ionize the neutrals present within the trap. Ions are effectively
trapped in the ITMSâ„¢ when the values of their az and qz parameters fall within the
stability diagram (Figure 1-1). When operated in the rf-only mode (az = 0), ions
with qz values less than qz = 0.908 will be effectively trapped and stored. The
ITMSâ„¢ is typically operated with the presence of a significant background

13
pressure of a light buffer gas, typically ~ 1 mtorr of helium. Collisions between
ions and helium atoms serve to kinetically "cool" the ions, which causes the ions
to migrate toward the center of the trap. This results in dramatic increases in
sensitivity and resolution (Stafford et al., 1984).
The ITMSâ„¢ acquires a mass spectrum by using the mass-selective
instability scan method (Stafford et al., 1984). During the mass-selective instability
scan there is no dc potential (az = 0) applied to the trap such that all ions
possess values of qz which lie along the qz axis of the stability diagram. Since qz
is inversely proportional to m/z (Equation 1-5), ions of lower m/z are located
towards the right of the qz axis. Ions are "moved" along the qz axis by linearly
ramping the rf potential, V, (qz « Vfrom Equation 1-5) until they become unstable
at the stability boundary, where qz = 0.908. This results in sequential ejection of
ions of increasing m/z from the trap where they are detected by an external
electron multiplier. Mass spectra are recorded on the ITMSâ„¢ using a scan rate
of 180 jjsec/u. Typically during mass analysis, an additional axial modulation
signal is applied across the endcap electrodes. This supplemental signal is
applied at slightly less than half the rf drive signal at approximately 6 Vp.p. Just
prior to ejection, the ions come into resonance with the axial modulation signal,
which increases the amplitude of the ion’s trajectory in the z direction. This
results in the ions being more tightly bunched upon ejection, yielding increased
resolution and detection efficiency (Weber-Grabau et al., 1988).
An impressive feature of the ITMSâ„¢ is that the population of ions stored in
the ion trap can be manipulated via application of various sequential or

14
simultaneous dc, rf, and ac voltages. For example, isolation of a single m/z or a
narrow range of m/z’s in the trap can be accomplished by application of an
appropriate combination of rf and dc voltages such that the m/z of interest is near
the apex of the stability diagram (Figure 1-1) at qz = 0.78, az = 0.15 (Weber-
Grabau et a/., 1987). Alternatively, a "two-step" isolation method has been
described where higher mass ions are ejected at a working point along the f}z =
0 stability edge and lower mass ions are ejected at a working point along the /?z
= 1 stability edge (Gronowska et al., 1990; Yates et a/., 1991).
Tandem mass spectrometry (MS/MS) experiments are performed by first
mass-selecting a particular precursor ion. A supplemental resonant excitation
potential is then applied across the endcaps at the secular frequency of the
precursor ion. Resonance excitation kinetically excites the ion causing an
increase in the amplitude of its trajectory in the z-direction. The amplitude of the
resonant excitation voltage, however, is kept low enough to avoid losses due to
resonant ejection. The kinetically excited precursor ion undergoes energetic
collisions with helium buffer gas which can result in collisionally activated
dissociation (CAD). Studies have demonstrated up to 100% CAD efficiency and
overall MS/MS efficiencies approximately 14 times higher than triple quadrupole
instruments which suggests that "the ion trap may be the most sensitive MS/MS
instrument ever" (Johnson et al., 1990, 2172). Multiple stages of mass
spectrometry (MSn, n>2) experiments can be performed by mass-selecting a
particular daughter ion and repeating the resonant excitation step. Indeed, MSn

15
experiments up to MS12 have been successfully demonstrated on the ITMSâ„¢
(Louris et al., 1990).
LC/MS using the QITMS
The combination of high-performance liquid chromatography (HPLC) with
mass spectrometry has been widely recognized as possessing enormous
potential for analyzing a wide variety of compounds. Although HPLC does not
provide the chromatographic efficiency of capillary GC, analytes remain in the
condensed phase at ambient temperature during separation, so thermal
decomposition is not a problem. This makes HPLC-based methods an appealing
choice for the analysis of a wide variety of thermally labile, nonvolatile, and polar
compounds which are either not amenable to GC or require derivatization for GC
analysis. Indeed, it has been estimated that only about 20% of all known organic
compounds are amenable to GC and GC/MS analyses and that HPLC-based
methods should be capable of analyzing the vast majority of the remaining 80%
(Budde et al., 1990).
The major challenge involved with using a mass spectrometer as an HPLC
detector is the design of a suitable interface which can convert the high pressure
mobile phase flow into the gas phase, yet maintain typical MS operating
conditions. Vaporizing this quantity of liquid generates a volume of gas that must
be substantially reduced to maintain the high vacuum (typically 1 x 105 torr) of
the mass spectrometer. In the 1970s, the moving belt (McFadden et al., 1976)

16
and direct liquid introduction, DLI (Baldwin and McLafferty, 1973), interfaces
represented the first successful LC/MS interfaces. However, the moving belt was
mechanically complex and subject to memory effects, while DLI required splitting
a large portion of the LC eluent which limited the sensitivity of the technique. In
the 1980s, the development of a "new generation" of improved aerosol-based
LC/MS interfaces including thermospray (Blakley et al., 1980), particle beam
(Willoughby and Browner, 1984), and electrospray (Fenn etal., 1989) dramatically
broadened the applicability of LC/MS.
Although the majority of LC/MS research has been performed using
quadrupole instruments, ion traps are seeing increased use in LC/MS systems.
Initial attempts to interface the widely used thermospray (TSP) interface with an
ITMSâ„¢ (Kaiser et al., 1991) exhibited good sensitivity; however, high solvent
background pressures caused significant peak broadening (i.e. poor mass
resolution). The performance of the TSP/ITMSâ„¢ system was significantly
improved using a differentially pumped ion source (Bier etal., 1991). Electrospray
(ESP) interfaces have seen the greatest number of LC/ITMSâ„¢ applications in the
literature (Van Berkel et al., 1990, McLuckey et al., 1991). Since ESP yields
multiply charged ions, even high molecular weight biological compounds are well
within the working mass range of the ITMSâ„¢ (m/zmax = 650 u). Ion trap systems
coupled with TSP and ESP require the use of an ion injection system because
ions are generated within the interfaces, external to the trap.

17
A number of features of the ITMSâ„¢ make it particularly attractive as a mass
analyzer for TSP and ESP generated ions. These include high sensitivity, the
ability to perform MS" experiments with high CAD efficiency, and the ability to
perform kinetic measurements. Since TSP and ESP are known as "soft" ionization
techniques which produce predominantly molecular ions, the capability to obtain
structural information from MSn experiments is particularly appealing.
The Particle Beam LC/MS Interface
The PB interface represents another of the new generation of LC/MS
interfaces based upon aerosol formation. The primary advantage of using an
aerosol-based LC/MS interface is that solvent can evaporate far more rapidly from
droplets than from bulk solutions because of the much higher surface area-to-
volume ratio (Browner et a/., 1986). The original design was disclosed in 1984
and was named MAGIC for monodisperse aerosol generation interface for liquid
chromatography (Willoughby and Browner, 1984). As variations based on MAGIC
became commercially available (Apffel and Nordman, 1987, Willoughby and
Poeppel, 1987), they became simply known as particle beam interfaces.
Although differences exist between various commercial PB interfaces, all
consist of a nebulizer and some type of desolvation chamber, coupled with a
momentum separator which removes solvent vapor from the beam of largely
desolvated particles. A schematic of the prototype interface used in these studies
is shown in Figure 1-4. It differs from commercially available interfaces in that it

PB
QITMS
Nebulizer
Momentum Separator
_ j.
He
i i i
Vacuum Pumps
Heated
* Endcap
Filament ^ r
Endcap
RF
Ring
f
Electron Multiplier
Figure 1-4: Schematic (not to scale) of the LC/PB/QITMS system used throughout these studies.
CD

19
employs an additional third stage of pumping in the momentum separation region
to further reduce the amount of solvent which reaches the ion trap.
The interface works by first converting the LC effluent into an aerosol
having a narrow range of droplet diameters. The nebulizer in this interface shears
the liquid with a high concentric flow of helium. The droplets then travel through
a heated desolvation chamber where volatile solvent is vaporized resulting in a
mixture of solvent vapor, helium, and largely desolvated particles containing
analyte. This mixture then passes through a beam collimator which forms the
particle beam which then travels through the momentum separator. The
momentum separator in this interface consists of three stages of pumping which
are separated by a series of skimmers. Solvent and helium are pumped away in
the momentum separator while the more massive and higher momentum analyte
particles are transported through the momentum separator region. These
particles are transported through a transfer probe into the mass spectrometer
source region. The transfer probe was inserted into the ITMSâ„¢ via a Vfe" o.d.
transfer line probe which allowed insertion and removal without disturbing the
high vacuum of the ITMSâ„¢. The beam of particles is ,lflash" vaporized when it
collides with the hyperbolic surface of the filament endcap upon entering the
ITMSâ„¢ analyzer cavity. The resulting vapor then travels toward the center of the
trap where it is ionized by El or, alternatively, by chemical ionization (Cl) via
ion/molecule reactions with reagent ions produced from a reagent gas. Typical

20
operating parameters and optimization of the interface will be described in greater
detail in Chapter 2.
Particle beam interfaces have generated recent widespread interest largely
because of their ability to produce classical El mass spectra for a wide variety of
relatively involatile and thermally labile compounds of environmental and
biological interest (Behymer et al., 1990, Voyksner et al., 1990). The generation
of El spectra is advantageous because the fragmentation patterns found in these
spectra can reveal structural information which affords the ability to identify
unknown compounds, a typical goal of many LC/MS analyses. El spectra also
can be compared to existing library spectra for the identification and confirmation
of unknown compounds. TSP and ESP interfaces produce spectra unique to the
interface which yield predominantly molecular weight information. This typically
limits these techniques to targeted compound analysis, although the use of
tandem mass spectrometry for obtaining structural information has been reported
(Smith et al., 1990; Van Berkel et al., 1990).
Coupling a PB interface with a QITMS would appear to be an appealing
choice for many applications employing LC/MS. The ability of PB to generate El
spectra affords the identification of unknown compounds, a typical goal of many
types of analyses, while the sensitivity of the QITMS should also provide low limits
of detection. Currently, all commercially available PB systems employ quadrupole
mass analyzers due to their ruggedness and low cost. Although the coupling of
PB with a QITMS using both direct coupling (Bier et al., 1992) and injection of

21
ions from an external ion source (Bier et al., 1991) has been demonstrated, no
rigorous studies have been performed which thoroughly evaluate the analytical
capabilities of a PB/QITMS system.
Overview of Organization of Dissertation
In this dissertation, results from investigations of coupling LC with a QITMS
via a PB interface are presented. A historical perspective and a review of the
basic operating principles of the QITMS and the PB interface are provided in this
introductory chapter. The optimization of important PB operating parameters and
instrumental modifications are discussed in Chapter 2. Chapter 3 presents results
of several methods investigated to minimize adverse effects of residual solvent.
Application of the PB/ITMSâ„¢ system to the analyses of pesticide mixtures is
presented in Chapter 4. Chapter 4 also compares the performance of the
PB/ITMSâ„¢ system with a PB system which employs a quadrupole mass analyzer.
Investigations of several ion trap operational modes to improve quantitation using
isotopically labeled internal standards for both GC/ITMSâ„¢ and LC/PB/ITMSâ„¢
analyses are discussed in Chapter 5. Finally, conclusions and perspectives for
future work are presented in Chapter 6.

CHAPTER 2
CHARACTERIZATION OF IMPORTANT PARTICLE BEAM
OPERATING PARAMETERS
Introduction
As discussed in Chapter 1, particle beam (PB) interfaces have attracted
widespread interest recently because they allow the generation of classical
electron ionization (El) mass spectra of a wide variety of compounds of
environmental (Brown etal., 1990) and biological interest (Voyksner etal., 1990).
Generation of El spectra is advantageous because they typically exhibit rich
fragmentation patterns which can reveal structural information. The fragmentation
patterns of these spectra can then be compared to reference spectra using readily
available computer library spectral searches for the identification and confirmation
of unknown compounds, a typical goal of many LC/MS analyses.
Although the important PB operating parameters are well known (Voyksner
et a/., 1990), variations between commercially available PB interfaces and MS
systems necessitate the need to characterize these parameters for each system
in order to intelligently develop effective LC/MS methods. This chapter describes
and characterizes the important PB operating parameters for the LC/PB/ITMSâ„¢
system used throughout these studies. In order to improve performance,
22

23
modifications were made to both the interface and the analyzer. A description
and the results of these modifications will also be discussed.
Experimental
Instrumentation
Two HPLC systems were used for these characterization studies. The first
was an ISCO (Lincoln, NE) LC-2600 syringe pump which used a Valeo
(Springfield, NJ) 6-port manual injection valve with a 10 /jL sample loop. The
second HPLC system was a Hewlett-Packard (Palo Alto, CA) 1090L liquid
chromatograph fitted with a Rheodyne (Cotati, CA) manual injection valve with a
5 ¡jL sample loop. Solvent compositions and flow rates used are indicated in the
text. All characterization studies were performed using flow injection analysis
(FIA) of analytes.
The LC/MS interface was a prototype Finnigan MAT (San Jose, CA) particle
beam interface (Figure 1-4). This prototype differs from the commercially
available interface in that it employs three stages of pumping in the momentum
separator region to further reduce the amount of solvent which reaches the ion
trap. Supplemental helium was added to the third stage of momentum separation
to prevent backstreaming of pump oil from the mechanical pumps caused by low
pressures. Typical pressures in the three stages of the momentum separator
were 5-10 torr, 300 mtorr, and 100 mtorr (adjusted by addition of He),
respectively. The interface, fitted with a Vfc" o.d. transfer line, was inserted into the

24
ITMSâ„¢ via a Vfe" probe lock which allowed insertion and removal of the interface
without disturbing the high vacuum of the mass spectrometer. The probe tip was
positioned ~ W away from the ion trap entrance to prevent high pressures inside
the trap. The Rulon® fitting normally inserted in the entrace hole to electrically
isolate a probe from the endcap was removed so a larger entrance into the ion
trap would be present.
The mass spectrometer used in these experiments was a Finnigan MAT
(San Jose, CA) ITMS™. The vacuum chamber was maintained at 100°C for all
experiments. El was performed within the ion trap; detection was accomplished
with an electron multiplier set to yield 105 gain and with a single conversion
dynode at 0V. No dynode voltage was used because the dynodes caused high
noise problems on the ITMSâ„¢ at the time these experiments were performed.
Partial pressures of residual solvent were typically ~ 1 X 10'6 torr (uncorrected) as
measured by a Bayard-Alpert ionization gauge (Granville-Phillips, Boulder, CO)
mounted on the vacuum chamber. Helium was added into the ITMSâ„¢ vacuum
chamber to produce typical operating pressures of 1 X 104 torr (uncorrected).
Five microscans were averaged on the ITMSâ„¢ and returned to the data system
as a single scan. Axial modulation (Weber-Grabau etal., 1987) was employed at
530 kHz and 6Vp p during the mass-selective instability scan to improve mass
resolution and sensitivity.

25
Samples and Reagents
The structures of the standards used throughout these characterization
studies are shown in Figure 2-1. Also shown are molecular weights and the
fragmentation which yields the base peak of each compound’s El mass spectrum.
Carbaryl and diuron were obtained from the U.S. Environmental Protection
Agency (Pesticide Chemical Repository, Research Triangle Park, NC); caffeine
and rotenone were purchased from Sigma (St. Louis, MO). All standards were
used without further purification. HPLC grade methanol and acetonitrile were
obtained from Fisher Scientific (Pittsburgh, PA) and reagent water was obtained
from a Milli-Q water purification system.
Characterization Studies
The main operating parameters of the PB interface which affect
performance are the nebulizing helium flow rate, desolvation chamber
temperature, desolvation chamber pressure, and source target temperature. All
of these parameters were investigated to determine what effects they have on
sensitivity and performance for this PB system. These parameters were
investigated with various commonly used LC mobile phases, including methanol,
acetonitrile, and acetonitrile/reagent water mixtures and different flow rates. The
assistance of Mr. Donald Eades during these characterization studies is gratefully
acknowledged.

72
O
O
Cl ¿ /> N-?-C—N
A / r '
H
CH,
CH3
cr
Diuron
M.W. = 232 u
A.
ch2
ch3
H,C.
\
/
CH,
194+'
N‘
O
A
N"
â–  N
/
â– N
CHi
Caffeine
M.W. = 194 u
N—CH3
I
H
Carbarvi
M.W. = 201 u
Figure 2-1: Structures of compounds used in these characterization studies. Also shown are molecular
weights and the El fragmentation which yields the base peak of each compound’s El mass
spectrum. ^
O)

27
Nebulizing Helium Flow Rate
The nebulizer used in the PB interface was a glass Meinhard (Santa Ana,
CA) nebulizer which consists of a pair of concentric tubes. While the position of
the inner capillary tube is adjustable on other commercial interfaces (Apffel and
Nordman, 1987), its position is fixed in the Meinhard nebulizer. The nebulizer was
installed onto the desolvation chamber through a W Cajon® fitting which ensured
a vacuum-tight seal.
The HPLC eluant entered the nebulizer by passing through a length of 0.1
mm i.d. deactivated fused silica capillary column, which was inserted into the
inner tube of the nebulizer. A high flow (~0.6 L/min.) of He was introduced
through a gas port and flowed through the outer tube. As the liquid flow exited
the inner capillary, the concentric flow of He dispersed the liquid flow into an
aerosol consisting of a distribution of micron-sized droplets (Browner ef a/., 1986).
The aerosol was then swept into the desolvation chamber by the flow of He.
The flow of He into the nebulizer was controlled by varying the head
pressure of the regulator on the He supply. The plots in Figure 2-2 show how
varying the head pressure of the He (nebulizing flow) affected the signal for
different mobile phase compositions. The data points represent the average peak
areas obtained from triplicate injections of 20 ng diuron. The peak areas were
calculated from the extracted ion profile of the base peak (m/z 72) of the El mass
spectrum of diuron. The curves are asymmetric and show that poor signals were
obtained at low and high He head pressures. At low pressures, the aerosol is

Peak Area 72
28
Figure 2-2: Plots of peak area vs. nebulizing gas head pressure for different
mobile phase compositions. Data points represent averages of
triplicate injections of 20 ng diuron. Error bars indicate ±1
standard deviation.

29
primarily composed of low velocity drops with large mean diameters which are
difficult to desolvate. At high pressures, smaller, high velocity droplets are
formed. Significant transport losses result from surface impact, turbulence, and
evaporation when the aerosol droplets are either too large or too small (Browner
etal., 1982).
The plots also show that, as the percentage of water in the mobile phase
increases, a higher pressure (flow) of helium is required to produce optimum
performance. This trend is related to the surface tension and viscosity of the
mobile phase. Aerosols are generated because the gas jet causes frictional
interactions with the liquid surface. The main forces opposing aerosol generation
are the surface tension and the viscosity of the liquid phase. Since water has a
much higher surface tension and is more viscous than organic solvents, more
energy (hence higher gas flow) is required to efficiently nebulize aqueous solvents
(Browner et al., 1986).
It also appears that sensitivity decreases as the percentage of water in the
mobile phase is increased. Even at optimum conditions for each mobile phase
composition, the peak areas were greatest when using a pure organic mobile
phase. This observation can be explained by considering both the nebulization
and desolvation processes. Similar studies involving characterization of the
desolvation chamber temperature showed that sensitivity decreased as the
percentage of water in the mobile phase increased. Since water has a much
higher surface tension, it forms larger aerosol drops than a pure organic mobile

30
phase (Browner et al., 1986). Desolvation of aerosols comprised of larger
aqueous droplets is more difficult because the aerosol has less surface area and
water also has a higher heat capacity and AHvap than other common LC solvents
(Weast, 1982). Indeed, other studies have demonstrated that the observed order
of sensitivity for different mobile phases is inversely related to the energy to heat
and vaporize the solvent (Voyksner et al., 1990).
It does not appear for this PB interface that the flow rate of the mobile
phase affects the optimum nebulizing gas flow as much as the mobile phase
composition. Figure 2-3 shows nebulizing gas optimization curves for different
flow rates of 100% acetonitrile. All curves indicate optimum conditions at 30-35
psig He head pressure. Although the optimum conditions did not vary
significantly, the best sensitivity was observed at lower mobile phase flow rates.
It was also observed that the optimum nebulizing gas flow rate was largely
compound-independent.
Desolvation Chamber Temperature
Once the aerosol is generated, the droplets are swept into a heated
desolvation chamber. The main function of the desolvation chamber is to remove
the volatile solvent molecules from the aerosol droplets. Solvent evaporation is
achieved by the transfer of heat from the chamber walls to the drops. Any analyte
molecules which are present are typically less volatile and remain as particles.

Peak Area 72
31
Figure 2-3: Plots of peak area vs. nebulizing gas head pressure for different
mobile phase flow rates. Data points represent averages of triplicate
injections of 20 ng diuron.

32
The desolvation chamber in this interface was an 8" long, hollow, nickel-
coated aluminum block (Figure 1-4). It was heated by two 300 W cartridge
heaters inserted into the chamber block. The temperature of the desolvation
chamber was controlled by an external Ogden (model ETR 9080, Arlington
Heights, IL) feedback temperature controller which used a thermocouple to sense
the chamber temperature.
Figure 2-4 illustrates the effects of desolvation chamber temperature and
mobile phase composition on the signal obtained for 20 ng of diuron. The data
points represent the average areas obtained from triplicate FIA injections. The
plots reveal that the optimum temperature of the desolvation chamber depends
on the composition of the mobile phase. The optimum temperature increased as
the percentage of water in the mobile phase increased. Since water has a larger
heat capacity and AHvap than organic solvents, more energy is consumed during
vaporization. Thus, higher temperatures are needed to replace the heat lost from
adiabatic expansion due to solvent evaporation to maintain efficient desolvation.
The plots also show that signal decreases as the percentage of water in the
mobile phase increased. As mentioned previously, this trend is probably a result
of both the nebulization and desolvation processes.
It appears from the plots of Figures 2-2 and 2-4 that optimizing the
desolvation chamber temperature was not as critical as optimizing the flow of
nebulizing gas. While the signal obtained at non-optimum desolvation chamber
temperatures did not degrade the signal by more than 20%, using non-optimum

Peak Area 72
33
Figure 2-4: Plots illustrating the effect of desolvation chamber temperature on
peak areas obtained for FIA of 20 ng diuron at various mobile phase
compositions.

34
nebulizing gas flow rates resulted in as much as an 80% decrease in signal
(Figure 2-2). However, this was not true for all the test compounds used. Figure
2-5 shows desolvation temperature optimization curves for diuron and carbaryl.
Each curve was normalized with respect to its largest data point to better illustrate
the loss of signal at non-optimum conditions. Although the peak areas for diuron
did not vary by more than 20%, the peak areas for carbaryl at higher, non¬
optimum desolvation chamber temperatures decreased by as much as 80% with
respect to the maximum peak area. Since carbaryl is more volatile than diuron,
at higher temperatures carbaryl was probably being vaporized in the desolvation
chamber and pumped away in the momentum separator region of the interface.
Although of a limited test set, Figure 2-5 also illustrates that optimum desolvation
chamber temperature is largely compound independent as both curves exhibit
maximum signal at the same temperature.
Desolvation Chamber Pressure
The pressure in the desolvation chamber is largely determined by the flow
rate of the nebulizing gas and the mobile phase flow rate. At optimum
nebulization conditions, the pressure in the desolvation chamber is typically 200
torr. In this pressure regime, the rate limiting process influencing solvent
evaporation is the rate of heat transport from the surrounding gas to the surface
of the aerosol drop (Browner, 1986). Helium is used as the nebulizing gas
primarily because it has a high thermal conductivity which enhances heat transfer

Normalized Peak Area
35
Figure 2-5: Normalized desolvation chamber temperature optimization curves
for diuron (m/z 72) and carbaryl (m/z 144) using a 100% acetonitrile
solvent at a flow rate of 0.3 mL/min.

36
to the aerosol drops. In order to provide a better thermally conductive
environment, supplemental He was added to the desolvation chamber to enhance
solvent vaporization. Helium was introduced via a Negretti (Southampton,
England) fine metering valve through a Swagelok® (Jax Valve, Jacksonville, FL)
tee installed on the desolvation chamber. A pressure gauge (Omega, Stamford,
CT) was also added to monitor the pressure of the desolvation chamber (Figure
1-4).
Figure 2-6 shows the effect of adding supplemental He to the desolvation
chamber. The mobile phase for these studies was 100% acetonitrile; the data
points represent the average peak areas obtained from either 20 ng caffeine or
100 ng carbaryl. Optimization of the nebulization process accomplished prior to
these studies resulted in a desolvation chamber pressure of 210 torr. The plots
indicate that a two-to-threefold increase in signal was obtained by increasing the
pressure in the desolvation chamber by approximately 120 torr, at which point a
plateau was observed for both compounds. These results are consistent with
those observed by other laboratories (Browner, 1986). It is interesting to note that
commercially available interfaces of similar design do not utilize the addition of
supplemental He in the desolvation chamber.
Target Temperature
After travelling through the momentum separator, the analyte-containing
particles enter the mass spectrometer through a Vfe" o.d. transfer line probe. The

Figure 2-6: Plots illustrating affect of adding supplemental He to the desolvation
chamber for FIA of (a) 20 ng caffeine and (b) 100 ng carbaryl.

Peak Area 144 Peak Area 194
Desolv. Chamber Pressure (torr)
Desolv. Chamber Pressure (torr)

39
particles enter the ion trap where they strike the hyperbolic surface of one of the
endcap electrodes which served as the PB target. The collision with the endcap
causes the particles to undergo a rapid flash vaporization. This results in the
production of predominantly intact gas-phase analyte molecules. The analyte
molecules are then ionized by El, or alternately, by Cl, with the introduction of a
reagent gas.
The temperature of the PB target (endcap) plays an important role in the
signal obtained for PB analyses. The flash vaporization process must be efficient
to prevent peak tailing, which requires sufficiently high temperatures. However,
thermal degradation of some compounds can occur if too high temperatures are
utilized. Typical target temperatures used for PB analyses are between 250 and
300°C. Initially, the temperature of target endcap was maintained by radiatively
heating the entire ITMSâ„¢ vacuum chamber, including the ion trap and electron
multiplier, with the standard quartz heaters mounted inside the vacuum chamber.
In order to prevent damage to the electron multiplier, temperatures were not
raised above 140°C. This resulted in bad sensitivity and a large degree of peak
tailing even for FIA because these low temperatures yielded an inefficient flash
vaporization process.
In order to permit the use of typical PB target temperatures, modifications
were made to the filament endcap electrode which served as the target. Two
large holes were drilled into the body of the endcap to insert two 10W cartridge
heaters to independently heat the endcap. A small hole was also drilled near the
ion trap entrance hole on the endcap to insert a platinum resistance thermometer

40
to sense the endcap temperature. The temperature of the endcap was controlled
by an external feedback Omega (model CN-2012, Stamford, CT) temperature
controller. These modifications allowed the endcap to be heated to typical PB
operating temperatures of up to 290°C while maintaining the electron multiplier
mounted within the vacuum chamber at normal operating temperatures of 100 °C.
The improvements these modifications brought about are illustrated in
Figure 2-7. Shown are mass chromatograms of m/z 144 from triplicate FIA
injection of 200 ng carbaryl at endcap temperatures of 125 and 250°C. At low
temperatures, the peaks exhibited a significant degree of peak tailing caused by
inefficient flash vaporization of the particle beam. At higher temperatures, the
peak shapes were dramatically improved and little evidence of peak tailing was
observed. The signal intensities shown in the figure also show that there was an
approximate three-fold increase in peak height at the higher temperature.
Studies characterizing the target temperature also indicated that the
optimum temperature was largely compound-dependent. Optimization curves for
the FIA of 100 ng carbaryl and 75 ng rotenone are shown in Figure 2-8. The plots
are normalized with respect to the maximum peak area in each data set for clarity.
Data points represent the average ion peak areas obtained from triplicate
injections. While maximum response for carbaryl occurs at temperature of
200°C, rotenone exhibits a maximum at much higher target temperatures of
290°C. Rotenone is much less volatile than carbaryl, so it is not surprising that
the best response was obtained at high target temperatures.

Figure 2-7: Mass chromatograms of m/z 144 of carbaryl from FIA (triplicate injections) of 200
ng carbaryl at target temperatures of (a) 125° C and (b) 250° C, illustrating
improved peak shape at higher target temperatures.

Intensity
50211
Target (Endcap) = 125° C
a)
b)
14832
50 100 150
0:55 1:48 2:41
Target (Endcap) = 250° C
Scan Number
Time
N>

Normalized Peak Area
43
1.0
0.8
0.6
0.4
0.2
0.0
Figure 2-8:
Target temperature optimization curves for carbaryl (m/z 144) and
rotenone (m/z 192). The different maxima the curves exhibit
indicate that the optimum target temperature is largely compound-
dependent.

44
The carbaryl optimization curve illustrates that higher temperatures are not
optimum for all compounds. This is because thermal decomposition of some
compounds can occur at high target temperatures. For carbaryl, the best
response of the 144+ fragment ion (base peak) occurred at 200°C and decreased
by approximately 50% at target temperatures of 290°C (Figure 2-8). However, it
was observed that the total ion current signal increased by approximately 20%
when the target temperature was increased from 200°C to 290°C. This indicated
that carbaryl likely underwent some degree of thermal decomposition which
limited the sensitivity of the m/z 144 El fragment ion at high target temperatures.
Conclusions
These studies demonstrate the need for optimization of important PB
operating parameters to intelligently develop effective LC/MS methods. The
nebulizing gas flow rate, desolvation chamber temperature, desolvation chamber
pressure, and target temperature have all been shown to affect the sensitivity of
the LC/PB/ITMSâ„¢ system. Most of these interface parameters were found to be
largely mobile phase dependent; however, some compound dependance was
observed, most notably for the source target temperature. The mobile phase
dependance will make it difficult to optimize interface parameters for gradient
elution analyses because the mobile phase composition will change during the
analysis. Modifications to the ion trap endcap electrode were necessary to allow
normal target temperature (250° to 300°C) to be utilized. These modifications
were shown to yield dramatically improved peak shape and better sensitivity.

CHAPTER 3
EVALUATION OF STRATEGIES TO MINIMIZE ADVERSE
EFFECTS OF RESIDUAL SOLVENT
Introduction
Although Ion traps are noted for their sensitivity, versatility, and potential
for low cost, benchtop instrumentation, most mass spectrometric systems
currently in use for LC/MS (including those using PB interfaces) employ
quadrupole mass analyzers. Ion traps have seen limited use in LC/MS systems
primarily because of the large amount of solvent introduced by most LC/MS
interfaces. Excess solvent ions and neutrals typically cause space charging and
undesired ion/molecule reactions, resulting in poor mass resolution and poor
overall spectral quality.
In this chapter are reported several strategies which were evaluated, aimed
at minimizing adverse effects caused by introduction of residual solvent from a PB
interface. These strategies included one method which reduced the amount of
solvent which reached the trap. The versatility of the ITMSâ„¢ also allowed the
creation of customized scan functions which ejected unwanted solvent ions from
within the ion trap prior to mass analysis, while efficiently storing analyte ions of
interest. Although the coupling of PB with an ion trap using both direct coupling
and injection of ions from an external ion source has been reported (Bier et a/.,
45

46
1991, 1992), currently no information appears in the literature comparing
operational modes of the ion trap which minimize space charging by ejecting
residual LC solvent ions prior to mass analysis. The goal of this work was to
determine the best way to operate the ITMSâ„¢ to produce quality El spectra from
analytes introduced via LC. El spectra obtained from isocratic LC/PB/ITMSâ„¢
analyses of simple pesticide mixtures (<3 components) are compared to library
El spectra and El spectra obtained from solids probe/ITMSâ„¢ analyses (i.e. a
"solvent-free" method) of pure compounds. Also, instrument calibration curves
and limits of detection (LOD) obtained from these isocratic LC/MS analyses on
this system are reported.
Experimental
Instrumentation
Liquid Chromatography. Two LC pumping systems were employed in
these studies. Solvent ejection studies utilized an ISCO (Lincoln, NE) LC-2600
syringe pump. Chromatographic separations were performed using a Hewlett-
Packard (Palo Alto, CA) 1090L high-performance liquid chromatograph.
Separations were performed on a 100 x 4.6 mm Hewlett-Packard octadecasilyl
column, packed with 5 ¡jm particles. Separations were accomplished isocratically
with a mobile-phase composition of 80/20 acetonitrile/reagent water at a flow rate
of 0.3 mL/min. The analytical column was thoroughly conditioned by pumping

47
a 50/50 acetonitrile/reagent water mixture through the column overnight to remove
residual impurities and column bleed.
PB Interface. The LC/MS interface was a prototype Finnigan MAT (San
Jose, CA) three-stage particle beam interface (Figure 1-4). The operating
principles and optimization of the interface are described in greater detail in
Chapter 2. Important PB operating parameters including desolvation chamber
temperature and nebulizing He flow rate were optimized to provide maximum
sensitivity. The desolvation chamber pressure was optimized by addition of He
to increase the pressure to approximately 400 torr. The PB probe tip was
positioned about W away from the ion trap entrance to prevent high pressures
inside the trap.
Mass Spectrometer. The mass spectrometer used in these experiments
was a Finnigan MAT (San Jose, CA) ITMSâ„¢. Fundamentals of ion trap operation,
theory, and ion motion are described in greater detail in Chapter 1. The ITMSâ„¢
vacuum chamber was maintained at 100°C for all experiments. As described in
Chapter 2, the filament endcap of the ion trap was modified to allow insertion of
two 10W heater cartridges which were controlled by an external temperature
controller (Omega Engineering Model CN 2012, Stamford, CT). This endcap
served as the particle beam target and was operated at temperatures of 250-
290°C. Electron ionization was employed within the ion trap; detection was
accomplished with an electron multiplier voltage set to yield 105 gain and with the
single conversion dynode at 0V. Partial pressures of residual solvent were

48
typically ~5 x 10"6 torr (uncorrected) as measured by a Bayard-Alpert ionization
gauge (Granville-Phillips, Boulder, CO) mounted on the vacuum chamber. Helium
was added into the vacuum chamber to produce typical operating pressures of
1 x 10'4 torr (uncorrected). The ITMSâ„¢ was repeatedly scanned from 55 to 500
amu to check for formation of dimers and ion/molecule reaction products. Axial
modulation (Weber-Grabau et al., 1987) at 530 kHz and 6Vp.p was employed
during the analytical scan in all studies to reduce the effects of space charge and
improve sensitivity.
Samples and Reagents
Methomyl and linuron were obtained from AccuStandard (New Haven, CT),
caffeine from Sigma (St. Louis, MO); all other pesticide standards were obtained
from the U.S. Environmental Protection Agency (Pesticide Chemical Repository,
Research Triangle Park, NC). All standards were used without further purification.
The structures of the standards used in these studies are shown in Figure 3-1.
Also shown are molecular weights and the El fragmentation which yields the base
peak of each compound’s mass spectrum. Structures, molecular weights and El
fragmentation for carbaryl, rotenone, and diuron were shown previously in Figure
2-1. HPLC grade methanol and acetonitrile were obtained from Fisher Scientific
(Pittsburgh, PA); reagent water was obtained from a Milli-Q water purification
system.

61
Monuron
M.W. = 198 u
168+
O
v II
0^-C-N-CH3
> I
— H
Linuron
M.W. = 249 u
86+<
O l CH3
O
H3C—C=N—O:? c-n-ch3
I H \ 1
O CH3 ^ H
Methiocarb
M.W. = 225 u
105+<
O
, H
H3C—C=N-0:§-C—
I
SCH,
N—CH3
I
H
Aldicarb Sulfone Methomvl
M.W. = 222 u M.W. = 162 u
Figure 3-1: Structures of compounds (not previously shown in Figure 2-1) used in these studies. Also
shown are molecular weights and fragmentation which yields the base peak of each
compound’s El mass spectrum.

50
Problems Caused by Residual Solvent
The major challenge encountered when interfacing LC directly with the ion
trap was minimizing adverse effects caused by the introduction of residual solvent
from the interface. Solvent molecules (S) in the trap are ionized by El:
S + e_ -* S+" + 2e~
resulting in a large population of solvent ions which caused space charge
conditions. Space charge results when the density of ions in the trap becomes
large enough that ion-ion interactions become significant. This can distort the
trajectories of trapped ions resulting in bad spectral quality with poor mass
resolution and incorrect mass assignments.
In the ion trap, ions and neutrals are present within a confined space for
a period of time prior to ejection/detection. As a result, a large population of
solvent ions and molecules can also cause undesired ion/molecule reactions to
occur. Most notably, a large degree of solvent-CI of analyte neutrals can occur
as illustrated below:
S+‘ + S -» (S + H)+ + (S - H)
(S + H)+ + M - (M + H)+ + S.
These equations show that a solvent radical ion (S+) can react with a neutral
solvent molecule to form a Cl reagent ion, (S+H)+. If the proton affinity of an
analyte neutral molecule (M) is greater than that of the Cl reagent neutral(s),

51
proton transfer will occur and a protonated molecule, (M+H)+, forms. This is
typically a "soft" ionization process, meaning that the (M+H)+ ions typically
undergo little fragmentation as compared to the M+‘ ions initially formed by El.
Since the primary advantage of using PB is the ability to acquire El mass spectra,
these adverse effects of residual solvent must be minimized.
These adverse effects are illustrated in the profile mass spectrum shown
in Figure 3-2. The mass spectrum was acquired from FIA of -100 ng of carbaryl
in 100% methanol mobile phase. The spectrum shown is an expansion of the m/z
25-150 mass range to better illustrate the resolution between adjacent masses;
the abundance of the M+' ion at m/z 201 was <5% relative to 145+. The large
abundance of methanol solvent ions centered around m/z 33 caused space
charging which resulted in poor mass resolution between adjacent low masses.
Notice that resolution improved at higher masses. The inset in Figure 3-2 is
provided to better illustrate the mass resolution between 144+ and 145+. As
discussed in Chapter 1, the ITMSâ„¢ generates mass spectra by sequentially
ejecting trapped ions from low to high mass (Stafford et ai, 1984). This results
in solvent ions being ejected/detected before higher mass ions during mass
analysis, reducing space charging when higher mass ions are detected.
The 144+/145+ ratio in this spectrum also indicated a large degree of
solvent-CI occurred. The base peaks of the El and Cl mass spectra of carbaryl
are 144+ (M-57)+ and 145+ (M + H-57)+, respectively. Although some 145+ from
the 13C isotopes of 144+ (C10H8O)+ would be expected in the El spectrum of

Figure 3-2: Profile mass spectrum acquired from FIA of ~ 100 ng carbaryl in 100% methanol mobile phase
illustrating adverse solvent effects. The large abundance of methanol solvent ions centered
around m/z 33 caused space charging and a large degree of solvent-CI to occur, as evidenced
by the 144+/145+ ratio. The inset is a blowup of the m/z 140-150 region to better illustrate the
mass resolution and to compare the intensities of 144+ and 145+.

Intensity (cts.)
cn
co

54
carbaryl (11 % relative to 144+), the figure shows the intensity of 145+ being about
three times greater than that of 144+. The abundant methanol solvent ions
evidently caused a large amount of solvent-CI to occur. Indeed, the use of
residual solvent ions to perform solvent-CI analyses of pesticides with the same
LC/PB/ITMSâ„¢ system has been demonstrated (Eades ef a/., 1992). However,
here the large degree of solvent-CI was undesirable since the goal of this work
was to produce quality El spectra. This figure illustrates the need to eject solvent
ions prior to mass analysis to minimize space charging and solvent-CI to obtain
good quality El mass spectra.
Strategies to Minimize Adverse Solvent Effects
The two different types of strategies which can be used to minimize
adverse effects of residual solvent are illustrated in the block diagram of the
LC/PB/ITMSâ„¢ system in Figure 3-3. The block diagram shows that solvent and
analyte molecules (S° and A0, respectively) elute from the HPLC and pass through
the PB interface into the ion trap where solvent and analyte ions (S+ and A+) are
formed by El. The number of solvent molecules which reach the trap could be
reduced by using various instrumentation-based approaches before the trap.
Alternately, the trap could be operated such that solvent ions are ejected from
within the trap prior to mass analysis. By employing these strategies, ideally only
analyte ions of interest eventually reach the detector.

s
t
+
S° A°
HPLC
S° A°
PB Interface
Jl
S° A°
S+ A+
Ion Trap
A+
Detector
Figure 3-3: Block diagram of LC/PB/ITMSâ„¢ system illustrating possible strategies to minimize adverse
solvent effects. Strategies were investigated which either reduced the number of solvent
molecules (S°) which reached the trap or ejected solvent ions (S+) from within the trap.
cn
tn

56
As mentioned previously, the interface used in these studies employs an
additional third stage of momentum separation. The additional stage of
momentum separation is an example of one strategy aimed at reducing the
number of solvent molecules which reach the trap. The amount of solvent which
reaches the trap could also be reduced by employing a membrane drier in place
of the desolvation chamber. In the membrane, volatile solvent diffuses through
the membrane and is pumped away while involatile analyte particles are
transferred to the momentum separator. The commercially available Universal
Interface from Vestec is based on this operating principle (Vestal et al., 1990).
Solvent molecules can also be prevented from reaching the trap by using
injection of ions created in an external ion source. Previously, ion injection has
been demonstrated using both on-axis (Louris et al., 1989) and off-axis (Pedder
etai, 1989) ion sources.
Different ITMSâ„¢ operational modes can also be implemented to eject
solvent ions from within the trap. Previous research in our labs here at UF
investigated methods for mass-selective ionization in the quadrupole ion trap to
eliminate undesired ions of a range of mass/charge (m/z) values (Eades et al.,
1991). These included the use of resonant excitation employing waveforms
comprised of multiple frequencies. However, implementation of these methods
required modifications to the ITMSâ„¢ source code. In this chapter, two modes of
ion trap operation implemented with standard ITMSâ„¢ software are evaluated for
LC/PB/MS which eject residual solvent ions from the ion trap prior to mass

57
analysis: 1) elevation of rf voltages to eject ions below a chosen m/z ratio (i.e.
impose a low mass cutoff) and 2) application of a supplemental rf signal to eject
a single solvent ion species. Both methods were evaluated when applied either
during ionization or during an ion storage period following ionization. A summary
of strategies which may minimize adverse solvent effects is shown below in Table
3-1.
Table 3-1: Summary of Strategies to Minimize Adverse Solvent Effects.
A. Remove Solvent Molecules Before the Ion Trap
1. Membrane Drier prior to Momentum Separator
2. Additional Third Stage of Momentum Separation in Interface
3. External Source and Ion Injection
a. On-Axis
b. Off-Axis
B. Eject Solvent Ions within the Ion Trap
1. Elevate rf Voltage (Impose Low Mass Cutoff)
a. During Ionization Step
b. During Ion Storage
2. Resonant Ejection of Single Ion Species (Notch Filter)
a. During Ionization Step
b. During Ion Storage

58
Additional Stage of Momentum Separation
The same PB interface was used to determine the benefits of using the
additional third stage of momentum separation to reduce the amount of solvent
which reached the trap. The interface was converted to a two-stage interface by
removing the third skimmer and third stage roughing pump from the interface.
Pressures in the momentum separator region were approximately 5-10 torr and
400-500 mtorr is stage one and stage two, respectively. These pressures are not
significantly different than those observed when employing three stages of
momentum separation.
Figure 3-5 illustrates that the additional stage of pumping does reduce the
amount of solvent which reaches the trap. Shown are the intensities of
protonated acetonitrile (m/z 42) at different flow rates of 100% acetonitrile mobile
phase. The figure demonstrates that solvent ion intensity increased with
increased flow rate and that about four times less solvent ions were formed when
using three stages of pumping. Table 3-2 lists the ion gauge pressures for
various solvent compositions for both configurations. These pressures were
obtained at a flow rate of 0.3 mL/min. and with no supplemental He added to the
desolvation chamber, ITMSâ„¢ vacuum chamber, or third stage of the momentum
separator. The pressures were read directly from the ion gauge, with no
correction factors used. The table indicates that the partial pressures of the
solvent were typically 10-30X lower when using the additional third stage of
pumping.

59
3-Stage WM 2-Stage
Figure 3-5: Comparison of intensities of acetonitrile (M+H)+ solvent ions at
various flow rates using both a two-stage and three-stage PB
interface.

60
Table 3-2: Comparison of ion gauge pressures for various solvent
compositions using two and three stages of momentum separation
Ion Gauge Pressure (torr)*
100%
75/25
50/50
25/75
CHXN
CH.CN/H.0
CHXN/HX
CHXN/HX
2-stage
1.9 X 10-4
1.9 X 10"1
2.8 X 10-4
3.2 X 10"*
3-stage
5.8 X IQ’6
5.7 X 106
5.7 X 106
3.5 X 10‘5
‘All pressures obtained at solvent flow rate of 0.3 mL/min. and no supplemental
He added to desolvation chamber. Pressures were read directly from the ion
gauge meter with no correction factor used.
The performance of both configurations was evaluated by comparing the
El spectra obtained for FIA of 20 ng caffeine in 100% acetonitrile mobile phase.
The spectra are presented in Figure 3-6. Also shown is a library reference El
spectrum obtained from a computer library included with the ITMSâ„¢ software.
The spectrum obtained using the three stage interface shows excellent
comparison with the library spectrum with respect to both fragmentation pattern
and relative intensities of the mass peaks. The spectrum obtained using two
stages, however, does not compare favorably with the library spectrum. The
spectrum exhibits m/z 67 as the base peak instead of the M+' ion at m/z 194.
The high pressure of solvent probably caused a significant amount of collisionally

Figure 3-6: Comparison of El mass spectra of caffeine obtained from (a) reference library and PB/ITMSâ„¢
analysis using a (b) three-stage interface and (c) two stage interface. Spectra obtained from
PB are from FIA of 20 ng caffeine.

Relative Intensity
a)
1 my.
M+*
194
109
67
82
ii . . '
i * i 1 r 1 i 1 i r
60 80 100
137
165
' I 1 I' ”r I—1—I—1—1—r '"1 i ] r
120 140 160 180
I 1 I 1 I 1
200 220
1 1
M'
194
c)
CD
N>

63
activated dissociation (CAD) to occur from collisions with background solvent
molecules. Also, the most abundant molecular ion peak was the (M+H)+ peak
at m/z 195 which indicated a large degree of solvent-CI occurred. These figures
illustrate that the additional third stage of momentum separation removed
significant amounts of solvent and improved the performance of the LC/PB/ITMSâ„¢
system.
Elevation of rf Level
One method of solvent ion ejection studied involved elevation of the rf
voltage applied to ring electrode to eject ions below a chosen m/z, i.e. to impose
a low mass cutoff. In this mode, the ion trap was operated in the rf-only mode
(i.e. with the Mathieu parameter az=0). Since the Mathieu parameter qz is
proportional to the rf voltage (Equation 1-5), elevation of the rf voltage increased
the qz values of trapped ions. In the rf-only mode, ions with values of qz greater
than 0.908 will follow unstable trajectories and be ejected from the trap in the axial
(z) direction. Since qz is inversely proportional to m/z (Equation 1-5), ions from
low molecular weight LC solvents (e.g. CH3OH, CH3CN, H20) were ejected at a
properly chosen low rf potential while analyte ions of higher m/z’s remained
stored. In this mode, the ion trap was basically operating as a high-pass mass
filter.
The effect of elevating the rf voltage upon both solvent and analyte ions is
illustrated in Figure 3-7. Shown are stability diagrams for protonated acetonitrile

Figure 3-7: Stability diagrams of a solvent ion (m/z 42) and analyte ion (m/72) plotted in terms of rf and dc
voltage illustrating elevation of rf voltage to eject solvent ions while storing the analyte ions of
interest. At point A, both the solvent and analyte ion species will be efficiently stored. Elevation
of the rf voltage to a level corresponding to point B, will result in solvent ions being ejected
while analyte ions will remain stored.

dc Voltage
Low Mass Cutoff (u)
0 20 40 60 80 100

66
solvent (m/z 42) and the most abundant fragment ion of diuron (m/z 72). Note
here that the stability diagrams are plotted in terms of actual rf and dc voltage
applied to the electrodes, rather than a,q space. Since the trap is operated in the
rf-only mode, the rf voltage determines the low mass cutoff of the trap, which is
also shown. At an rf level corresponding to point A in the figure, both the solvent
and analyte ion will be trapped because this point is located within the stability
diagram of both ions. Point B is located outside the solvent ion stability diagram
but is still within the stability diagram of the analyte. At this rf level, the solvent
ion will be ejected while the analyte ion will remain effectively trapped.
This mode of operation was investigated when applied both during the
ionization event and afterwards, during ion storage. The effect of raising the rf
level (low mass cutoff) upon the ion intensity of some commonly used LC solvents
is shown in the plots of Figure 3-8. As expected, as the instrument’s low mass
cutoff approached the m/z of each solvent ion species, solvent ions were
efficiently (100%) ejected from the ion trap. These plots were created by raising
the rf level after ionization, during ion storage. Although not shown, similar plots
were obtained by elevating the rf during ionization.
Figure 3-9 illustrates how the intensity of the carbaryl analyte ion (144+)
was affected by elevating the rf level (qz) both during ionization and during ion
storage. These plots were obtained by varying either the ionization or storage
values of qz with a constant amount of carbaryl (2 ng///L yielding 10 ng/s at 0.3
mL/min.) in 100% methanol flowing through the interface. Although the analyte

Normalized Ion Intensity
67
Low Mass Cutoff (m/z)
Figure 3-8: Plots of normalized solvent ion intensities vs. rf level (expressed as
low mass cutoff) during ion storage illustrating efficient ejection of
common LC solvent ions.

68
0.00 0.20 0.40 0.60
0.80
1.00
Low Mass Cutoff (m/z)
Figure 3-9: Plots of intensity of 144+ fragment ion of carbaryl vs. rf level
(expressed as low mass cutoff) both during ionization and during
ion storage.

69
ion signal was relatively unaffected by storage qz until its stability limit was
exceeded, signal decreased significantly with increasing ionization qz. As the
value of qz increases, so does the initial kinetic energy of the ions formed,
resulting in large initial velocities and ion losses due to quasi-unstable trajectories
(Dawson, 1976). These losses occur when the magnitude of an ion’s oscillation
exceeds the internal dimensions of the ion trap even though mathematical
conditions for stability still exist. Although raising an ion’s qz value during ion
storage also increases its kinetic energy, the ions are already effectively trapped
so ion losses are minimal until the ions become unstable when qz= 0.908.
Elevating the ionization value of qz of an ion also decreases the initial ionization
volume which limits the region in which ions can be created and remain stable
(Dawson, 1976). The observed decreases in intensity could also be the result of
decreased ionization cross-sections due to high electron energies at elevated rf
levels. Preliminary studies investigating the effects of ionization rf level (qz) of n-
butylbenzene ions also showed decreased ion intensities at higher values of qz
(Pedder et ai, 1992)
There were also some differences in the extent of solvent-CI between
spectra obtained by ejecting solvent during ionization and during ion storage.
Figure 3-10 shows how the ratio of 144+ (El fragment) to 145+ (Cl fragment plus
13C isotope of 144+) is affected by elevating the rf level during ionization and
storage for carbaryl in 100% methanol. The rf level where the methanol solvent
ions (m/z 33) were efficiently ejected from the trap is indicated by the dashed line

Ratio 1 44+/1 45
70
Low Mass Cutoff (m/z)
Figure 3-10: Plots of ratio of 144+ (El fragment) to 145+ (Cl fragment) vs. rf level
(expressed as low mass cutoff) both during ionization and during
ion storage for carbaryl in 100% methanol. Dashed line indicates rf
level where methanol solvent ions are efficiently ejected from the
trap.

71
in the figure. In a "pure" El spectrum, the 144+/145+ intensity ratio would be
expected to be 9.0, based on the natural abundance of 13C isotopes of 144+. The
low ratios obtained at low rf levels resulted from solvent ions causing a large
degree of solvent-CI. Ejection of solvent ions decreased the amount of Cl
resulting in increased 144+/145+ ratios; the inability to achieve the expected ratio
for a pure El spectrum indicated that some solvent-CI still occurred in the time
before solvent ions were ejected. Also, lower ratios were observed when the rf
was elevated during ion storage. This is because solvent ions were stored during
the ionization time, which allowed more time for solvent-CI to occur before the
solvent ions were ejected.
Resonant Ejection of Single Ion Species
The other method of solvent ion ejection studied involved resonant ejection
of a single m/z solvent ion species by applying a notch filter (Kelley et al., 1985).
This was accomplished by applying a supplemental 6Vp_p rf signal (resonant
excitation voltage) across the endcap electrodes to kinetically excite a particular
solvent ion m/z species such that it was ejected from the trap. The trajectories
of trapped ions of a particular m/z are generally characterized by their unique
secular frequencies, ujz, which are a complex function of the Mathieu parameters
az and qz, and /?z, which relates to the frequency of the oscillation of the ions.
Application of the resonant excitation voltage at the ioz of a particular solvent ion
m/z results in that ion absorbing power which increases the axial amplitude of its

72
oscillations. The excited ion can then undergo CAD with residual buffer gas
molecules. Alternatively, and of relevance to this discussion, the excited ion
species can also be ejected from the trap if sufficient power is absorbed such that
the amplitude of the oscillations become larger than the trap’s dimensions. The
use of resonant ejection was investigated because it permitted ionization to be
performed at lower values of qz, which may result in better sensitivity for
compounds whose El mass spectra have low m/z base peaks.
As with elevating the rf amplitude, the use of a notch filter was investigated
when applied either during ionization or ion storage. Figure 3-11 illustrates
resonant ejection of the m/z 42 ion of acetonitrile solvent both during ionization
and afterwards, during ion storage. The figure shows that m/z 42 was efficiently
(-100%) ejected when resonant ejection was applied during ion storage. Since
ions of different m/z possess different secular frequencies, no losses in analyte
signal were observed. This process was not nearly as efficient, however, when
applied during the ionization pulse. In this case only about one-third of the
solvent ions were ejected. This is because the ionization and ejection of ions
were acting as competing processes. Ions were constantly being produced
during the ionization event; those created towards the end of the ionization period
were only resonated for a very short period of time, and thus were not efficiently
ejected. Furthermore, ionization times were typically only -1 ms. This
represents the maximum amount of time an ion was resonated during ionization.
However, when applied after ionization, all ions can be resonated for up to 50 ms,
resulting in a much greater ejection efficiency.

Intensity (cts.)
73
a)
1277
(M + H) +
J
Resonant Excitation Voltage
OFF
35
~r~l' n
40
Jl ,
! I I I | I I I1 i p i II I J' I I 1 ! | I I r I I | II
45 50 55 60 65 70
1 1 I 1 ' 1 ' I '
75 80
69 i
'i M | i 'i' i i rr'i 'i 'i
30 40
50
!b*dj L
Resonant Excitation Voltage
ON
'V'ry-^vyv",iY;
60
11 f1 a ^
mass/charge
Figure 3-11: a) Profile mass spectra illustrating resonant ejection of acetonitrile
(M + H)+ solvent ions (m/z 42) during ion storage.

Intensity (cts.)
74
b)
1301 i
866 i
(M + H)-
Resonant Excitation Voltage
OFF
35 40 45 50 55 60 65 70 75 80
i i i i [ i i P i p > ~*i t i | i i i i | i i i i | â–  r i i i | i i i i i
i i
Resonant Excitation Voltage
ON
I I | I TT"T^| ^1-M | 'I I ’I I | I I I r~i> |^l ''I 1 1^1 I I I I | I f I | I I I I | I I i r'i' r
35 40 45 50 55 60 65 70 75 80
mass/charge
Figure 3-11: (continued) b) Profile mass spectra illustrating resonant ejection of
acetonitrile (M+H)+ solvent ions (m/z 42) during ionization.

75
Comparison of Solvent Ion Ejection Methods
The analyte signal obtained for methods which efficiently eject solvent ions
are compared in Figure 3-12. These plots were obtained by varying the ionization
time with a constant amount of diuron (1 ng//yl_ yielding 5 ng/s at 0.3 mL/min.) in
100% methanol flowing through the interface. As illustrated in Figure 2-1, the
base peak of the El spectrum of diuron occurs at m/z 72; its intensity is plotted
in Figure 3-12. Rf levels were elevated such that all ions below m/z 45 were
ejected for methods involving elevated rf levels. For the notch filter mode, the
resonant excitation signal was set to eject the (M+H)+ ion of methanol solvent
(m/z 33) for 10 ms during ion storage. As expected, increasing the ionization time
resulted in linear increases in signal for all methods until space charge develops
due to too many analyte ions being trapped, at which point the plots begin to
level off. The plots also reveal that methods which involved ejection of solvent
ions during ion storage produce about two times greater signal than ejection
during ionization. As discussed previously, we believe this to be because of ion
losses due to quasi-unstable trajectories and smaller ionization volumes at higher
values of qz during ionization (Dawson, 1976). It should be noted that these
effects might not be as significant for compounds whose El mass spectral base
peaks are at higher m/z values. Similar studies monitoring m/z 144 (qz=0.28) of
carbaryl show less than two times difference in signal between these operational
modes. This was not further investigated because the mass spectra of the
compounds being analyzed all had base peaks below m/z 200.

Intensity 72+ (cts.)
76
onization Time (ms)
Figure 3-12: Plots of diuron analyte ion signal (m/z 72) vs. ionization time
comparing methods described in the text which efficiently eject
solvent ions.

77
To obtain maximum sensitivity, all subsequent studies ejected solvent ions
by elevating the rf level after ionization, during ion storage. Although resonant
ejection during ion storage yielded essentially the same sensitivity, elevation of the
rf amplitude ejected all solvent ion species, as well as background ions (air,
water, column bleed, etc.), below the chosen m/z. Also, with standard ITMSâ„¢
software, ejection of more than one m/z solvent ion species by resonant excitation
would require multiple resonant ejection events. Although not all solvent ion
species require 10 ms for efficient ejection, multiple resonant ejection events
would allow more time for undesired ion-molecule reactions to occur. Multiple
resonant ejection events would be necessary for LC/PB/ITMSâ„¢ analyses which
would employ gradient elution or isocratic solvent mixtures.
Application to LC/PB/ITMSâ„¢ Analyses of Simple Pesticide Mixtures
The capabilities of the LC/PB/ITMSâ„¢ system were initially evaluated by
performing isocratic LC/MS analyses of simple pesticide mixtures (i.e. <3
components). The El mass spectral quality, estimated LODs, and instrument
calibration curves were used to evaluate performance under realistic LC
conditions. Ionization was performed at an rf level corresponding to a low mass
cutoff of m/z 20 for 1 ms; solvent ions were ejected during ion storage by
elevating the rf level to eject all ions below m/z 55.
An LC/PB/ITMSâ„¢ analysis of a mixture of three pesticides using LC
conditions described in the experimental section is shown in Figure 3-13. The

Figure 3-13: Total ion chromatogram (TIC), mass chromatograms, and amounts
analyzed from the LC/PB/ITMSâ„¢ analysis of a three-pesticide
mixture using LC conditions described in the text.

Relative Intensity
79
100X
Scan Number
Retention Time (minis)

80
figure displays the total ion chromatogram (TIC), mass chromatograms of the
base peaks of the El mass spectra of each component, and amounts of each
component injected. Structures and El fragmentation of each component were
shown previously in Figure 2-1 and 3-1. These chromatograms illustrate better
than baseline separation of the compounds was achieved in less than 6 min.
The background-subtracted mass spectrum of 80 ng of diuron (m.w.=232
amu) obtained from these analyses is compared with both a reference El
spectrum (Hites, 1985) and the El mass spectrum obtained from solids
probe/ITMSâ„¢ analysis in Figure 3-14. The spectra are quite similar with respect
to both fragmentation patterns and relative fragment ion intensities. The low
abundance of the (M+1)+ ions in the LC/PB/ITMSâ„¢ spectra indicated that only
a small amount of Cl occurred, and did not significantly degrade the overall El
spectral quality. The spectra of the other compounds in the test mixture also
compared favorably with reference and solids probe/ITMSâ„¢ El spectra.
An instrument calibration curve for diuron is shown in Figure 3-15. The
calibration curves were constructed by plotting the integrated ion abundance
(peak area) of the quantitation ion as a function of amount injected. The
quantitation ion for each compound was the base peak of its full-scan El mass
spectrum. It appears from the figure that a linear calibration was obtained from
diuron. The inset of the figure is an expansion of the region from 10-100 ng
which better illustrates the linearity at the low end. The value of the correlation
coefficient (r2 = 0.9984) shows a good linear model exists from 20-500 ng

Figure 3-14: El mass spectra of diuron obtained from (a) library (Hites, 1985), (b)
solids probe/ITMSâ„¢ analysis, and (c) LC/PB/ITMSâ„¢ analysis of 80
ng diuron (background-subtracted).

100 120 140 160 180 200 220 240
mass/charge
-CO
• CO
to
co
to
+
Relative Intensity
S
CD
N>
OOT

Figure 3-15: Diuron instrument calibration curve and results of the linear regression (solid line, r2 = 0.9984)
for linear region (20-500 ng). Inset shows expansion of the low end of the calibration curve.

4000000 n
3000000 -
*
/
00

85
analyzed. The non-linearities at the ends of the calibration curve are presumably
due to particle beam transport problems at the low end (Bellar et al., 1990) and
the onset of space charging caused by too many analyte ions at the high end.
Although diuron here shows linear behavior, nonlinear calibration curves, like that
obtained for linuron in Figure 3-16, are far more prevalent in LC/PB/MS. The
nonlinear behavior of PB has been attributed to transport losses through the
momentum separator region of the interface. This has been observed by several
other laboratories as a limitation of PB/LC/MS for quantitative analyses (Doerge
and Miles, 1991, Brown and Draper, 1991). The use of isotopically labelled
internal standards has been suggested as a possible solution to this problem and
has been the topic of several recent reports (Ho eta!., 1992, Doerge etal., 1992).
Quantitation using PB and the carrier effect will be discussed in greater detail in
Chapter 5.
The instrument detection limits were estimated by selecting a sample
concentration which reliably yielded a 3:1 signal/noise ratio for each compound’s
quantitation ion in the full-scan mass spectrum. Figure 3-17 illustrates the
estimated detection limits routinely obtained on this system for several carbamate
and urea-based pesticides. The LOD’s are typically in the low ng range and are
comparable to LOD’s reported for PB systems which employ quadrupole mass
analyzers (Behymer et al., 1990). The LOD reported here for linuron is 10 times
lower than previously reported (Behymer et al., 1990) because the base peak of
its El spectrum (61+) was below the low mass (m/z 62) employed in the previous

Peak Area 61
86
Figure 3-16: Linuron instrument calibration curve from PB/LC/ITMSâ„¢ analysis.
Dashed line represents region where the onset of space charging
occurred.

Est. Detection Limit (ng)
87
Figure 3-17: Estimated detection limits for several carbamate and urea-based
pesticides routinely obtained on this PB/ITMSâ„¢ for isocratic
analyses described in the experimental section.

88
report to eliminate interferences from using ammonium acetate in the mobile
phase, which necessitated the use of a less intense ion (M+', m/z 248) for
quantitation.
These LODs were obtained from the calibration runs and are not intended
to be presented as the lowest LODs possible for each compound on the
LC/PB/ITMSâ„¢ system. Note that there are a number of options offered by the
LC/PB/ITMS™ system that could further improve these LOD’s, including longer
ionization times, higher multiplier voltages, use of a high voltage conversion
dynode, and addition of mobile phase additives such as ammonium acetate to
improve analyte transport through the interface. Automatic variation of the
ionization time using automatic gain control, AGC (Stafford et al., 1987, Yost et
al., 1987), might lower detection limits and extend the linear dynamic range as
well.
Conclusions
The successful coupling of a PB interface with an ITMSâ„¢ has been
demonstrated in this chapter. When directly coupling a PB interface with an
ITMSâ„¢, it was necessary to eject solvent ions to minimize space charging and
prevent a significant degree of solvent-CI from occurring. The additional third
stage of momentum separation has been demonstrated to reduce the amount of
solvent which reached the trap. Ejection of solvent ions prior to mass analysis
afforded the ability to generate El spectra which compared favorably to library El

89
spectra and El spectra obtained by solids probe/ITMSâ„¢ analyses. Although linear
instrument calibration curves were observed, nonlinear behavior was more
prevalent for LC/PB/ITMSâ„¢ determinations of several pesticides. Typical LODs
for several pesticides have been estimated to be in the low ng range.

CHAPTER 4
APPLICATION OF LC/PB/ITMS TO ANALYSIS OF PESTICIDE MIXTURES
AND COMPARISON TO OTHER LC/PB/MS SYSTEMS
Introduction
The analytical utility of PB relies on the ability to generate classical El
spectra of a wide variety of environmentally and biologically significant
compounds introduced via LC. The vast majority of PB/LC/MS systems currently
in use employ quadrupole mass analyzers due to their widespread availability, low
cost, and tolerance of relatively high operating pressures. Ion traps have seen
limited use in LC/MS systems primarily because of the large amount of solvent
introduced by most LC/MS interfaces. In the previous chapter, several strategies
were investigated which minimized adverse solvent effects and allowed acquisition
of El mass spectra from isocratic LC/PB/ITMSâ„¢ analyses which compared
favorably to reference library spectra.
Although isocratic separations are well suited for individual applications
which require simple separation strategies, they are limited for the analysis of
complex mixtures with components having a wide range of retention times.
Isocratic separations of multicomponent mixtures typically exhibit poor resolution
of early eluting components, bad peak shape of late eluting components, and
unnecessarily long retention times (Snyder and Kirkland, 1979). As a result,
90

91
complex mixtures require the use of gradient elution, which is analogous to
temperature programming for GC. In gradient elution, the composition of the
mobile phase is changed throughout the analysis to increase its eluent strength.
An optimized gradient affords the ability to efficiently analyze a large number of
components in a minimum amount of time.
This chapter will report the application of the LC/PB/ITMSâ„¢ system for the
analysis of a ten-component pesticide mixture. The pesticide mixture required the
use of gradient elution to achieve adequate separation of the components. The
performance of this system for gradient elution analyses will be compared to that
of an LC/PB/MS system which employed a quadrupole mass analyzer with
regards to detection limits, calibration curves, precision, and overall spectral
quality. Finally, the capability of the ion trap to acquire both El and Cl spectra in
alternate scans over the course of an LC peak will be demonstrated.
Experimental
Liquid Chromatography
Chromatographic separations were performed using a Hewlett-Packard
(Palo Alto, CA) 1090L high-performance liquid chromatograph fitted with a
Rheodyne (Cotati, CA) manual injection valve with a 5 jjL sample loop.
Separations were performed on a Waters (Milford, MA) Nova-Pak® 150 mm x 2
mm i.d. C18 reverse phase column, packed with 4 jjm particles. The LC column
was thoroughly conditioned by pumping a 50/50 acetonitrile/reagent water mixture

92
through the column overnight to remove residual impurities and column bleed.
The mobile phase used for these studies was an acetonitrile/0.01 M ammonium
acetate in reagent water mixture at a flow rate of 0.3 mL/min. Post-column
addition was used to increase the percent organic phase through the PB
interface. An ISCO (Lincoln, NE) LC-2600 syringe pump was used for post¬
column addition of 100% acetonitrile at a flow rate of 0.1 mL/min, resulting in a
total mobile phase flow rate of 0.4 mL/min. through the interface.
PB Interface
The LC/MS interface was a prototype Finnigan MAT (San Jose, CA) three-
stage particle beam interface (Figure 1-4). The interface is described in greater
detail in Chapters 1 and 2. Important PB parameters including desolvation
chamber temperature, pressure, and nebulizing He flow rate were optimized by
making several injections of the test mixture under different conditions to provide
maximum sensitivity for a majority of the compounds in the test mixture.
Optimization is more difficult for gradient elution analyses because the
composition of the mobile phase changes throughout the course of the analysis.
Chapter 2 revealed that most PB parameters are largely mobile phase dependant.
Typical pressures in the three stages of the momentum separator were 5-10 torr,
300 mtorr, and 100 mtorr (adjusted by addition of He), respectively. The interface
was inserted into the mass spectrometers via a Vi?" o.d. transfer line probe through

93
a probe lock assembly which allowed insertion and removal without disturbing the
high vacuum of the mass spectrometers.
Ion Trap Mass Spectrometer
The ion trap mass spectrometer used in these experiments was a Finnigan
MAT (San Jose, CA) ITMSâ„¢. Fundamentals of ion trap operation, theory, and ion
motion are discussed in greater detail in Chapter 1. The ITMSâ„¢ vacuum chamber
was maintained at 100°C for all experiments. The filament endcap served as the
particle beam target and was operated 250 °C. Modifications to this endcap were
described in Chapter 2. Electron ionization was employed within the ITMSâ„¢;
detection was accomplished with an electron multiplier setting set to yield 105
gain and with a single conversion dynode at 0V. Helium was added into the
vacuum chamber to produce typical ITMSâ„¢ operating pressures of 1 x 10 4 torr
(uncorrected) as measured with a Bayard-Alpert ionization gauge (Granville-
Phillips, Boulder, CO) mounted on the vacuum chamber. Axial modulation
(Weber-Grabau et al., 1987) was employed at 530 kHz and 6 Vp.p during the rf
analytical scan. The ITMSâ„¢ was repetitively scanned from 62 to 450 u to check
for formation of any adducts and ion/molecule reactions. Data acquisition began
at m/z 62 to minimize background contributions from the ammonium acetate in
the mobile phase. Ten microscans were averaged and returned to the data
system as a single scan.

94
Quadrupole Mass Spectrometer
The quadrupole mass spectrometer used for comparison studies was a
Finnigan MAT (San Jose, CA) TSQâ„¢ 70 triple quadrupole mass spectrometer.
The probe tip of the interface was positioned ~ W away from the ion source
block of the TSQâ„¢. A conventional El ion volume normally used for GC
introduction served as the PB source target. The beam of analyte particles
entered the ion volume through the GC inlet hole and collided with the opposite
wall to produce flash vaporization of the particle beam. The resulting vapor was
then ionized by El using an electron energy of 70 eV and an emission current of
200 ¿/A. The ion source temperature was held at 250°C; the TSQ™ manifold
temperature was set at 100°C. Mass spectra were acquired with Q3 in the full-
scan mode; Q1 and Q2 were operated in the rf-only mode such that all m/z’s
were transmitted. The mass spectrometer was repetitively scanned from 62 to
450 u at 0.5 seconds/scan. Mass calibration was performed using
perfluorotributylamine (FC-43). Detection was accomplished using an electron
multiplier (EM) setting of 1000 V and the conversion dynode at 5 kV. The EM
voltage was chosen such that the detector was not saturated at the highest
standard concentration injected.
Samples and Reagents
Methomyl and mexacarbate were obtained from AccuStandard (New
Haven, CT), rotenone and benzidine from Sigma (St. Louis, MO) and all other

95
pesticide standards were obtained from the U.S. Environmental Protection Agency
(Pesticide Chemical Repository, Research Triangle Park, NC). All standards were
used without further purification. The structures of the standards used in these
studies are shown in Figure 4-1. Also shown are molecular weights and the El
fragmentation which yields the base peak of each compound’s mass spectrum.
Structures, molecular weights and El fragmentation for carbaryl, rotenone, and
diuron were shown previously in Figure 2-1 and for monuron in Figure 3-1. HPLC
grade methanol and acetonitrile were obtained from Fisher Scientific (Pittsburgh,
PA) and reagent water was obtained from a Milli-Q (Millipore Corp., Milford, MA)
water purification system.
Results and Discussion
As stated in the experimental section, the separations described here
utilized reversed phase (RP) LC columns. These columns have a relatively non¬
polar organic stationary phase (e.g. C8 or C18 hydrocarbon) chemically bonded
to silica particles. When using RP columns with gradient elution, the mobile
phase is initially started at its most polar combination and programmed to
become progressively more nonpolar. As such, polar compounds elute before
nonpolar compounds.
The two most commonly used gradient solvent combinations for RP-LC are
methanol-water and acetonitrile-water. Both of these combinations were initially
evaluated for gradient elution with the LC/PB/ITMSâ„¢ system. The affect of

184+'
3.3'-Dimethlvbenzidine
M.W. =212 u
Karbutilate
M.W. = 279 u
M.W. = 222 u
Figure 4-1: Structures of compounds (not previously shown in Figures 2-1 and 3-1) used in pesticide test
mixture. Also shown are molecular weights and the fragmentation which yields the base peak
of each compound’s El mass spectrum.
CO
CT)

97
different compositions of methanol-water and acetonitrile-water had upon the
normalized intensity of the M+‘ ion of caffeine (m/z 194) is shown in Figure 4-2.
The data points represent the averages of triplicate FIA injections of 20 ng
caffeine. Optimization of PB operating parameters was not performed at each
mobile phase composition because it would not be practical to change operating
parameters during the course of a gradient analysis; rather, PB operating
parameters were optimized using 50% water mobile phase for each combination
to better mimic a real gradient elution analysis.
It appeared from these plots that the acetonitrile-water system gave a more
even distribution of ion intensities over a wider range of mobile phase
compositions. Peak areas did not vary by more than 25% over the range of 10
to 80% water for the acetonitrile-water system; however, peak areas varied by
nearly 80% over the same range of mobile phase compositions for the methanol-
water system. Although the data point at 40/60 methanol/water might appear to
be an aberrant data point, these experiments were repeated and the results were
reproducible. The error bars in the figure also indicated the acetonitrile-water
system yielded better precision. For these reasons, the acetonitrile-water gradient
was chosen for development of a gradient elution LC/MS method for the pesticide
mixture.
During these studies it was also observed that using a mobile phase which
contained greater than 80% water resulted in poor reproducibility. When the
mobile phase contained a high water content, the water condensed onto the

Normalized Peak Area 194
98
% H20 in Mobile Phase
Figure 4-2: Plots of normalized intensity of the M+' ion of caffeine (m/z 194) for
different compositions of methanol-water and acetonitrile-water
mobile phases. The data points represent the averages of triplicate
FIA injections of 20 ng caffeine.

99
beam collimator and the skimmers in the interface. This dramatically decreased
sensitivity and caused pressure fluctuations in the interface and ITMSâ„¢ vacuum
chamber which necessitated disassembly and cleaning of the interface.
The gradient for separation of the test mixture was developed off-line using
the filter photometric detector of the LC, whose output was recorded on a
stripchart recorder. The mobile phase composition was held at 30% acetonitrile
for 4 min., linearly ramped to 70% acetonitrile for 20 min, and held at 70%
acetonitrile for 3 minutes. At the conclusion of the gradient, it was necessary to
reequilibrate the column to obtain reproducible retention times and peak shapes.
This was accomplished by linearly ramping the gradient back to 30% acetonitrile
in 2 min. and holding the column at these original starting conditions for 10 min.
The aqueous phase used for this gradient contained 0.01 M ammonium
acetate. The beneficial effects of using mobile phase additives such as
ammonium acetate in the mobile phase for PB analyses have been well
documented (Bellar et al., 1990). The use of volatile buffers has been shown to
yield enhanced signal due to improved transport through the momentum
separator of the interface as a result of a formation of larger particles which have
more momentum. The use of ammonium acetate in the mobile phase also
improved the chromatography of certain compounds in the test mixture.
Benzidine compounds have been shown to elute as broad, weak peaks with no
buffers in an acetonitrile/water mobile phase on the same LC columns (Bellar et
al., 1990). The presence of ammonium acetate resulted in reasonably

100
symmetrical, narrow peaks. Also note that no problems were observed with the
buffer plugging nebulizers or skimmers in the momentum separator.
A chromatogram from a LC/PB/ITMSâ„¢ analysis of the ten-component test
mixture (similar results were obtained on the LC/PB/TSQâ„¢ system) is provided in
Figure 4-3. The figure shows the total ion current (TIC) profile which represents
the sum of the intensities of all ions over the entire scan range. Also shown are
the identities of the chromatographic peaks and the injected amount of each
component. The amount injected for each compound is near the upper end of
the calibration range studied in order to obtain a good profile to better illustrate
the separation of the components. The chromatogram shows that baseline
separation of all the components was achieved in less than 25 min. Retention
times and peak shapes of each component in the test mixture showed good
reproducibility. The split peak of siduron resulted from partial separation of cis
and trans isomers. Baseline separation of the isomers could be obtained by
lowering the slope of the gradient resulting in longer analysis times. Since
quantitation of siduron was performed by summing the peak areas of both
isomers, shorter analysis times were favored over baseline separation of the
isomers.
This test mixture was used to evaluate the capabilities of the ion trap to
perform gradient elution LC/PB/MS analyses. The pesticides were chosen
because they are all of interest to the U.S. Environmental Protection Agency, who
provided the funding for this work. The LC/PB/ITMSâ„¢ system was evaluated with

Figure 4-3:
Total ion current (TIC) profile illustrating LC/PB/ITMSâ„¢ analysis of ten-component
test mixture. Also shown are identities of peaks and amounts injected.

400 800 1200 1600 2000
4:07 8:13 12:20 16:27 20:32
Scan Number
Retention Time (minis)
Relative Intensity
©

103
regards to El mass spectral quality, limits of detection (LOD), precision, and
calibration. These results were also compared with results obtained on an
LC/PB/TSQâ„¢ system to determine if using an ion trap as a mass spectrometric
detector for LC/PB/MS was beneficial.
El Mass Spectra
The mass spectra acquired under real LC conditions in both systems
compared favorably with reference El spectra (Hites, 1985) obtained on other
mass spectrometers and spectra acquired from solids probe/ITMSâ„¢ analysis of
pure standards. No evidence of dimers or adduct ions from solvent or from the
ammonium acetate in the mobile phase were observed throughout these studies.
Figure 4-4 compares the background-subtracted El mass spectra of
mexacarbate obtained on both the ITMSâ„¢ and TSQâ„¢ systems. The
concentration of mexacarbate in the standard analyzed was 105 ng/jjL resulting
in 525 ng injected onto the LC column (5/;L sample loop). Mexacarbate is shown
here because its El mass spectrum exhibited the largest number of different
fragmentations of all the compounds in the test mixture. The figure illustrates that
the same El fragmentation patterns were observed in the spectra from both
systems; however, some subtle differences between the spectra were observed.
The differences are more pronounced in the comparison of El mass
spectra of monuron (275 ng injected) shown in Figure 4-5. This figure illustrates
differences in the relative intensities of some of the fragment ions. In the ion trap
spectrum, the relative intensity of the M+' ion at m/z 198 is about 40% of the

Figure 4-4:
Background subtracted mass spectra of mexacarbate obtained on the (a)
LC/PB/ITMSâ„¢ system and (b) LC/PB/TSQâ„¢ system.

100*
a)
b)
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140 160 180
200
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222
220
165
150
134
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150
\6b
r
mass/charge
r
M+'
222
105

Figure 4-5:
Background subtracted mass spectra of monuron obtained on the (a)
LC/PB/ITMSâ„¢ system and (b) LC/PB/TSQâ„¢ system.

100% 72
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107

108
relative intensity of the base peak of the mass spectrum (m/z 72). The relative
intensity of m/z 198 is only about 20% relative to the base peak in the mass
spectrum obtained on the TSQâ„¢ system. This was believed to be due to
differences between storage efficiencies during the ionization event between low
and high mass ions in the ion trap. Lower mass ions have higher initial kinetic
energies at a given qz value which may cause losses due to quasi-unstable
trajectories (Dawson, 1976), results in lower intensity low mass to high mass ions
(e.g. 72+/198+).
There was also a larger (M+1)+/M+‘ ratio in the mass spectrum obtained
using the ion trap system. This is indicative of a larger degree of self-CI occurring
in the trap. Self-CI is a self-protonation reaction:
M+' + M -* (M + H)+ + (M - H)'
which typically results in a larger intensity of (M+H)+ ions being observed in El
spectra. Typically, M+’ ions are the predominant molecular ion found in El
spectra while (M+H)+ ions are associated with Cl mass spectra. Self-CI occurs
either by proton transfer from a radical molecular ion, M+', to a neutral analyte
molecule, M, or by transfer of an H atom from M to M+' (Harrison, 1992).
The effect of increasing the amount of analyte injected upon the
(M+1)+/M+' ratio (185+/184+) of benzidine in both PB systems is compared in
Figure 4-6. Also shown in the figure is the expected (M+1)+/M+‘ ratio (0.132)
calculated from the natural abundance of 13C isotopes in the molecular ion

Int. 1 85+/184
109
Figure 4-6: Plots of (M+1)+/M+' ratio (185+/184+) vs. amount of benzidine
injected in both PB systems illustrating increased amount of self-CI
which occurred in the PB system. Also shown is the expected ratio
based on relative abundance of 13C isotopes in the molecular ion.

110
(C12H12N2+'). The figure shows that with the LC/PB/TSQâ„¢ system, the ratio
remained relatively constant and close to the expected ratio over the range of
amounts injected. Changes in the 184+/185+ ratio were not expected in the
LC/PB/TSQâ„¢ system because the brief ion residence time in the El ion source
(~ 10 /js) does not allow enough time for ion/molecule reactions, such as self-CI,
to occur to any great extent. Because of the short residence time in the source,
much higher pressures (typically 1 torr), and usually a more enclosed ion source,
are required to promote ion-molecule reactions such as those employed in Cl.
In the LC/PB/ITMSâ„¢ system, the 185+/184+ ratio remained relatively
constant and near the expected value for amounts below 125 ng (Figure 4-6).
With increasing amounts above 125 ng, there was a dramatic increase in the
185+/184+ ratio, indicating an increase in the amount of self-CI. At larger amounts
of analyte injected, a larger number of analyte neutrals were present within the
trap which increases the probability of self-CI occurring. This was not surprising
because ion/molecule reactions are more prevalent in ion traps than beam
instruments because ions are stored within the ion trap cavity for hundreds of ms
(105 x longer than residence time in conventional source) prior to mass analysis.
Instrument Detection Limits
The instrumental limits of detection (LOD) were estimated by selecting a
sample concentration which reliably yielded a 3:1 signal/noise ratio for the
extracted ion profile from each compound’s quantitation ion in the full-scan mass

111
spectrum. For most of the compounds in the test mixture, detection limits ranged
from 5 to 50 ng; methomyl and monuron yielded LODs of 80 and 150 ng,
respectively. These LODs were obtained from the gradient elution analyses to
simulate real analysis conditions. They are not intended to be presented as the
lowest detection limits possible for each compound on the LC/PB/ITMSâ„¢ system.
Individual detection limits could be lowered by optimizing the chromatography
and interface parameters for a specific compound and mobile phase, albeit not
dramatically. For these gradient elution studies, optimization was performed to
provide the best overall performance for all compounds in the test mixture. Lower
LODs could also be obtained by using longer ionization times and higher
multiplier voltages; however, this would result in saturation of the data system at
high analyte concentrations.
Figure 4-7 compares the estimated detection limits routinely obtained on
both LC/PB/MS systems for the compounds in the test mixture. Although the
LODs for methomyl are about three times lower on the ion trap system, the
remainder of the compounds yielded comparable LODs. These results were
unexpected since the ion trap is known as a more sensitive mass spectrometer
particularly when compared in the full-scan mode. This is believed to be because
the LODs obtained for LC/PB/MS analyses are limited by the interface rather than
the mass spectrometric detector used. The ion trap might provide lower LODs
if the interface were able to provide more efficient analyte transport to the mass
spectrometer.

112
Figure 4-7: Comparison of estimated LODs for each compound in the test
mixture obtained on both the LC/PB/ITMSâ„¢ and LC/PB/TSQâ„¢
systems.

113
Instrument Calibration Curves
Instrument calibration curves were constructed by plotting the integrated
ion abundance (peak area) of the quantitation ion as a function of amount
injected for each compound in the test mixture. The quantitation ion for each
compound was the base peak of its full-scan El mass spectrum. Five to twelve
data points were used to construct the analytical curves. Although linear
calibrations were reported for diuron in Chapter 3, nonlinear calibrations were far
more prevalent for the compounds in the test mixture, including diuron, using
both LC/PB/MS systems. Figure 4-8 reveals typical instrument calibration curves
for diuron obtained on both systems. The peak areas of both plots are
normalized with respect to the largest data point in each data set. Comparison
of the actual intensity data between the two mass spectrometers was of little
analytical use since the peak areas were calculated using two different data
systems. Figure 4-8 illustrates that both curves clearly exhibited nonlinear
behavior. Although linear calibrations (r2 = 0.998) were observed for karbutilate
on the ion trap system, the linearity was not reproducible and nonlinear
calibrations were far more prevalent. The nonlinear behavior of PB has been
attributed to transport losses through the momentum separator region of the
interface (Bellar ef a/., 1990). This has been observed by several other
laboratories as a limitation of PB/LC/MS for quantitative analyses (Doerge and
Miles, 1991, Brown and Draper, 1991). The use of coeluting isotopically labeled
internal standards has been suggested as a possible solution to this problem and

Figure 4-8:
Typical instrument calibration curves for diuron obtained on both the
(a) LC/PB/ITMSâ„¢ and (b) LC/PB/TSQâ„¢ systems.

cr
Normalized Area 72+
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115

116
has been the topic of several recent reports (Ho etal., 1992, Doerge etal., 1992).
Quantitation using PB and the carrier effect will be discussed in greater detail in
Chapter 5.
Precision of Peak Areas
The precision of both systems was evaluated by calculating the relative
standard deviation (RSD) of the LC peak area of each compound’s quantitation
ion in the full scan mass spectrum for eight to ten replicate injections of the test
mixture. The precisions obtained for a midrange calibration standard on both PB
systems are compared in Figure 4-9. Although the amounts of each component
were different in the standard used, the amounts between the two PB systems
were equal to provide a good comparison. The RSDs ranged from 3.6% to 6.3%
on the LC/PB/ITMSâ„¢ system and 2.3% to 6.9% on the LC/PB/TSQâ„¢ system. The
precisions of both systems were comparable for each component in the test
mixture and differed by less than 2% for all compounds in the test mixture. The
figure also shows that better precision was obtained for compounds which eluted
later in the analysis when the percentage of water in the mobile phase was less.
As expected, the precision near the instrumental LODs were slightly worse. These
RSDs ranged from 3.9% to 9.3% on the LC/PB/ITMSâ„¢ system and 4.1 % to 10.4%
on the LC/PB/TSQâ„¢ system and were again comparable between the two
systems for each component in the test mixture.

% RSD
117
Ion Trap
Quadrupole
Figure 4-9: Comparison of precision of peak areas obtained for a midrange
calibration standard on both LC/PB/MS systems.
Rotenone

118
Alternating El/Cl Acquisitions
Although the primary advantage of LC/PB/MS systems is their ability to
generate library searchable El spectra, the ability to generate Cl spectra can also
be advantageous. Molecular weight determinations are often more appropriately
performed with Cl because this "soft" ionization process can produce
predominantly protonated molecules, (M+H)+, with the choice of a suitable Cl
reagent ion. Furthermore, some compounds produce little or no M+' ion upon
El. Molecular weight information from Cl spectra would be an attractive
complement to the structural information from El spectra which could provide
better confirmation of unknowns encountered during LC/PB/MS analyses.
One advantage the ITMSâ„¢ possesses over other mass spectrometers is the
ability to acquire both El and Cl spectra with no hardware modifications. The
TSQâ„¢ used in these studies requires a more enclosed ion volume in the ion
source to perform Cl. In addition, the Cl reagent gas is introduced into the ion
source at typically torr. The more enclosed ion source and higher Cl reagent gas
pressures are necessary because the residence time of ions in the ion source of
the TSQâ„¢ is extremely short, about 10 jjs (Harrison, 1992). The high pressure of
reagent gas and more enclosed source ensure that a sufficient number of
ion/molecule reactions occur to provide adequate sensitivity.
The ITMSâ„¢ represents a low-pressure Cl alternative to the high-pressure
Cl source of quadrupole instruments. The ability of the ITMSâ„¢ to store ions for
long periods of time provides a means for Cl to be performed at much lower Cl

119
reagent gas pressures (typically 10'5 torr). In the ITMSâ„¢, acquisition of Cl spectra
is accomplished simply by altering the El scan function to include reaction times
to accumulate Cl reagent ions and subsequently analyte ions. It is also desirable
to mass-select a particular Cl reagent ion to prevent mass spectral contributions
from other ionization processes such as El and hydride abstraction or proton
transfer from other Cl reagent ions (Berberich et al., 1989). These contributions
can cause different degrees of fragmentation which may lead to ambiguity and
difficult spectral interpretation.
Since no hardware modifications were necessary, it was possible to acquire
El and Cl spectra in alternating scans when PB was coupled directly with the
ITMSâ„¢. This was accomplished using the FORTH programming option of the
ITMSâ„¢. A FORTH program was written which alternately downloaded an El and
a Cl scan function into the ITMSâ„¢ firmware and acquired the El and Cl data to
two separate datafiles. The timing sequence of the alternating El/Cl acquisition
is illustrated in Figure 4-10. Shown are the rf timing traces (not to scale) which
represent the individual El and Cl scan functions and an illustration of the type of
mass spectrum which can be expected from each segment. The break in the rf
timing trace represents the point where the software writes the data collected to
its respective datafile and subsequently downloads the other scan function to the
firmware. Using this method, the time required to acquire one El and one Cl scan
was approximately one second.

El Acquisition
Cl Acqusition
Figure 4-10: Rf timing traces (not to scale) illustrating alternating El/Cl acquisition on the LC/PB/ITMSâ„¢
system. Also shown are illustrations of the type of mass spectrum expected from each
segment.

121
An interesting feature of performing alternating El/Cl acquisitions with the
LC/PB/ITMSâ„¢ system was that the residual solvent introduced into the trap by the
interface could be utilized to produce the Cl reagent ions. The utility of
performing solvent-CI was investigated previously in our labs (Eades eta!., 1991)
because the residual solvent totally consumed any reagent ions produced from
methane which was introduced as the Cl reagent gas. Mass-selection of the
protonated acetonitrile solvent (m/z 42) as the Cl reagent ion provided a means
of generating Cl spectra.
The acquisition of El and Cl spectra over the elution of LC peaks was
demonstrated using a simple pesticide mixture of monuron and diuron. These
two compounds were chosen because diuron is a dichloro analogue of monuron
(Figures 2-1 and 3-1, respectively); as a result, their El spectra display some
similarities. Most notably, both compounds exhibit m/z 72 as the El mass spectral
base peak. The separation of the two compounds utilized the same LC and RP
column described in the experimental section; however, since this was a simple
mixture, an isocratic separation using 60/40 acetonitrile/0.01 M aqueous
ammonium acetate as the mobile phase provided adequate separation of the two
components. Note that alternating El/Cl acquisitions might be complicated by
using gradient elution separations due to changing mobile phase conditions
which might affect the solvent-CI process.
Figure 4-11 illustrates the alternating El/Cl acquisition of 250 ng of monuron
and 100 ng diuron. Shown are the mass chromatograms of the most abundant

122
a) El Data
b) OI Data
(M + H)+
Scan Number
Retention Time (minis)
Figure 4-11: Mass chromatograms of (a) the most abundant fragment ion (m/z
72, both compounds) from the El acquisition and (b) the protonated
molecular ion of monuron (m/z 199) and diuron (m/z 233) from the
Cl acquisition.

123
fragment ion (m/z 72, both compounds) from the El acquisition and the
protonated molecular ion of monuron (m/z 199) and diuron (m/z 233) from the Cl
acquisition. The chromatograms show better than baseline separation was
achieved in approximately four minutes. The background-subtracted mass
spectra from both acquisitions are shown in Figure 4-12. The spectra illustrate
the complementary nature of the two types of spectra. While the El spectra
exhibit more fragmentation and structural information, the (M+H)+ ions in the Cl
spectra provide for better molecular weight determinations. The ability to provide
both structural and molecular weight information could provide more positive
confirmation of unknowns, especially for those compounds whose El spectra
exhibit little or no molecular ion mass peak.
Conclusions
The utility of the LC/PB/ITMSâ„¢ system has been demonstrated for
performing gradient elution analyses of complex pesticide mixtures. Although the
fragmentation of El spectra obtained the LC/PB/ITMSâ„¢ showed good
comparisons with El spectra obtained on the LC/PB/TSQâ„¢ system, some
differences in the relative intensities of fragment ions were observed. At high
analyte concentrations, the LB/PB/ITMSâ„¢ system also exhibited a larger amount
of self-CI, as indicated by a larger (M+1)+/M+* ratio. Estimated LODs were in the
low ng range and are comparable to LODs obtained on the quadrupole system.
The LODs obtained are believed to be limited by the interface rather than the type

Figure 4-12: Background subtracted mass spectra from mass chromatograms of
Figure 4-11 for monuron and diuron obtained from alternating (a) El
and (b) Cl acquisitions.

125
a) El Spectra
ieey ya
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100
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124
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b) Cl Spectra
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126
of mass spectrometric detector. This would explain why lower LODs were not
observed using the more sensitive ITMSâ„¢. Precisions of replicate injections were
between 2 and 7% RSD and again were comparable between the two systems.
Although linear calibrations have been observed, nonlinear calibrations are far
more prevalent. Although comparable LODs and precision were obtained on both
systems, only the LC/PB/ITMSâ„¢ system has the ability to acquire alternating El
and Cl spectra over the elution of an LC peak. The structural information
obtained from El spectra and the molecular weight information from Cl spectra
may provide better confirmation of unknown compounds.

CHAPTER 5
IMPROVED QUANTITATION USING COELUTING ISOTOPICALLY
LABELED INTERNAL STANDARDS
Introduction
Although LC/PB/MS has gained popularity because of its ability to generate
classical El spectra, the use of PB as a quantitative tool has not been widely
accepted. Chapters 3 and 4 revealed that PB/LC/MS analyses typically yield non¬
linear calibration curves. This non-linearity has been recognized as the primary
limitation to employing LC/PB/MS as a quantitative tool (Brown and Draper, 1991).
The non-linearity has been generally attributed to a "carrier effect" (Bellar et al.,
1990) through the momentum separator region of the interface. With increasing
analyte concentrations, larger particles are formed within the interface which have
more momentum and are more efficiently transported through the momentum
separator; the smaller particles formed at low analyte concentrations may have
insufficient momentum to be transported through the momentum separator
efficiently, if at all. The use of mobile phase additives such as volatile salts (e.g.
ammonium acetate, ammonium formate, maleic acid, etc.) has been shown to
increase sensitivity and improve linearity at low analyte concentrations (Bellar et
al., 1990; Kim et al., 1990); however, mobile phase additives do not completely
alleviate the non-linear behavior (Apffel and Perry, 1991).
127

128
Recently, the use of isotopically labeled internal standards (IS) has been
suggested as a means to improve quantitation with LC/PB/MS. Isotope dilution
(ID) with isotopically labeled IS is known to provide extremely accurate
quantitation because ID can compensate for analytical error introduced by
improper sample preparation, sampling, and changes in mass spectrometer
detector response (Brown and Draper, 1991). Since isotopically labeled
analogues exhibit virtually identical chemical behavior as the native compound,
they typically coelute from a chromatographic separation. Because of this, a
coeluting IS could improve transport and linearity in the same manner as mobile
phase additives, while eliminating other sources of analytical error. Indeed, the
use of coeluting IS has been demonstrated to improve quantitation using
LC/PB/MS (Brown and Draper, 1991, Ho et al., 1992, Doerge et al., 1992).
A major disadvantage of the ion trap is its susceptibility to space charge
effects which cause loss of mass resolution and degradation of spectral quality.
This has resulted in limited applications of this sensitive mass spectrometer to
quantitative analyses employing isotopically labeled internal standards (IS). An
analyte and its isotopically labeled IS typically coelute, potentially producing
space charge conditions which limit the dynamic range of the instrument.
Although feedback control of the ionization time via automatic gain control (AGC)
has been shown to dramatically reduce the effects of space charge (Stafford et
al., 1987) and increase the dynamic range (Yost et al., 1987) as individual
compounds are introduced into the trap, problems occur when differing

129
concentrations of two compounds coelute. The AGC software selects optimum
ionization times for the more abundant component, which may result in
insufficient sensitivity and non-linear response for the minor component.
In these studies, quantitation using isotopically labeled IS was first
investigated using gas chromatography/mass spectrometry (GC/MS). The
sensitivity and versatility of the ITMSâ„¢ would appear to make GC/ITMSâ„¢ the
method of choice for GC/MS trace analysis. Indeed, good quality, full-scan
spectra of <10 pg of analytes introduced via GC are commonly obtained (Yost
et al., 1987). However, the trap’s susceptibility to space charge which can limit
the dynamic range of GC/MS analyses has limited applications of this sensitive
mass spectrometer for quantitative analyses employing isotopically labeled IS.
This chapter presents results from investigations of several ion trap
operational modes aimed at improving quantitation based on coeluting
isotopically labeled IS. The use of axial modulation (Weber-Grabau et al., 1987)
and mass-selective storage, i.e. rf/dc isolation of a single m/z (Strife et al., 1988),
were both investigated to reduce space charge and extend the linear dynamic
range. The results of initial GC/MS studies were used to determine the best
method of ion trap operation for quantitative studies using isotopically labeled IS.
This method was then applied to LC/MS to investigate whether the use of
coeluting standards improved the quantitative utility of LC/PB/ITMSâ„¢.

130
Experimental
Gas Chromatography
A Varían Associates (Walnut Creek, CA) 3300 gas chromatograph was used
for all GC/MS investigations. Gas chromatography was performed using an 11
m X 0.25 mm i.d. DB-5 column (J & W Scientific, Folsom, CA) with a 0.25 /vm film
thickness. Helium was used as a carrier gas at flow rates of approximately 1
mLVmin. One-microliter injections were performed manually in the split mode
using a measured split ratio of 40:1. The temperature of the GC was held at
110°C for 30 s and ramped to 180°C at a rate of 50°C/min. A homemade,
resistively heated transfer line probe operated at 220 °C was employed to
interface the GC to the mass spectrometer. The design of the probe allowed
insertion and removal without disturbing the high vacuum of the ITMSâ„¢.
Liquid Chromatography
A Hewlett-Packard (Palo Alto, CA) 1090L high-performance liquid
chromatograph fitted with a Rheodyne (Cotati, CA) manual injection valve with a
5 /yL sample loop was used for all LC/MS investigations. Separations were
performed isocratically with a mobile-phase composition of 50/50
acetonitrile/reagent water using a Waters (Milford, MA) Nova-Pak® 150 mm x 2
mm i.d. C18 reversed phase column, packed with 4 //m particles at a flow rate of
0.3 mL/min. The analytical column was thoroughly conditioned by pumping a
50/50 acetonitrile/reagent water mixture through the column overnight to remove

131
residual impurities and column bleed. Post-column addition was used to increase
the percent organic phase through the PB interface. An ISCO (Lincoln, NE) LC-
2600 syringe pump was used for post-column addition of 100% acetonitrile at a
flow rate of 0.1 mL/min., resulting in a flow rate of 0.4 mL/min. through the
interface. The LC was interfaced to the mass spectrometer via a prototype
Finnigan MAT (San Jose, CA) particle beam interface (Figure 1-4). The operating
principles of the interface are described in more detail in Chapter 2.
Mass Spectrometer
All experiments were performed on a Finnigan MAT (San Jose, CA) ITMSâ„¢.
The vacuum manifold was maintained at 100°C for all GC/MS and LC/MS studies.
The ITMSâ„¢ was operated at a multiplier setting which yielded 105 gain and the
conversion dynode at 0V. The helium carrier gas of the GC also served as the
buffer gas inside the ion trap; typical manifold pressures were approximately 2.5
X 10'5 torr for GC/MS studies as measured by a Bayard-Alpert ionization gauge
(Granville-Phillips, Boulder, CO) mounted on the vacuum chamber. For LC/MS
studies, helium buffer gas was introduced into the vacuum manifold to yield a
pressure of 1.5 X 10'5 torr. These pressures were read directly from the meter
with no correction factor for type of gas used.
One modification to the standard spectrometer software was necessary for
these studies. Standard ITMSâ„¢ software stops data acquisition 4 u below the
end (high) mass specified by the user in the data acquisition table of a scan

132
function due to a bug in the software. Modification of the ITMSâ„¢ software
allowed acquisition over the entire mass range specified in the data acquisition
table of the scan function. Note this modification would not be necessary for
analyses employing an analyte and IS that are separated by more than 4 u. Mr.
Nathan Yates is gratefully acknowledged for his help with modifying the ITMSâ„¢
software for these studies.
Samples and Reagents
The analyte and deuterated IS for GC/MS studies were provided by the
Sandoz Research Institute (East Hanover, NJ). Isotopic labelling involved
replacement of the CH2 groups on a five-membered ring with CD2 groups (see
Figure 5-1). Samples were dissolved in methanol or o-xylene and serial dilutions
performed.
For LC/PB/MS, benzidine (Figure 4-1) was used as the analyte and
deuterated IS. Native benzidine was purchased from Sigma (St. Louis, MO) and
the deuterated IS was purchased from Cambridge Isotope Labs (Cambridge, MA).
Isotopic labelling of the IS standard involved replacement of all eight hydrogen
atoms on the aromatic rings with deuterium atoms. Samples were dissolved in
acetonitrile (Fisher Scientific, Pittsburgh, PA) and serial dilutions performed.

Relative Intensity
a)
100%
-] r*\
: / \
Analyte / \
J m/z 163 /
i i i i I i i i i | i i ' i I i rr FT i i i i | i i i i | i i rv| m i i | i i11 i | i i t i i i i n i" i i | ¡
16%
Retention Time (minis)
Figure 5-1: Mass chromatograms showing coelution of (a) the analyte (100 pg) and (b) the isotopically
labeled IS (10 pg) during GC/ITMSâ„¢ analysis. Also shown are partial structures of both
components as well as cleavage of R, to form the fragment ions monitored. Asterisks indicate
sites for isotopic labelling of IS.
133

134
Gas Chromatoqraphv/Mass Spectrometry
As stated previously, these studies were initiated using GC/MS. A
GC/ITMSâ„¢ analysis of the compound studied is illustrated in Figure 5-1. Shown
are the mass chromatograms of the ions monitored for the analyte and internal
standard, 163+ and 167+, respectively. Also shown are partial structures of both
components as well as cleavage of R1 upon El to form the fragment ion
monitored. Asterisks indicate sites for isotopic labelling of the IS. The mass
chromatograms show coelution of the analyte (100 pg) and IS (10 pg) occurred
in just over 1 min. with a baseline peakwidth of ~ 1 s.
Benefits of Axial Modulation
Typically during mass analysis, an additional axial modulation signal is
applied across the endcap electrodes (Chapter 1). This supplemental signal is
applied at 530 kHz (slightly less than half the rf drive frequency of 1.1 MHz) at
approximately 6 Vp.p. Just prior to ejection, the ions come into resonance with the
axial modulation signal, which increases the amplitude of the ion’s trajectory in
the z direction. This results in the ions being more tightly bunched upon ejection,
yielding increased mass resolution and detection efficiency (Weber-Grabau etal.,
1988).
The improvements observed with the use of axial modulation can be seen
in the instrument calibration curves in Figure 5-2. The curves are plotted in log-
log format and are shown spanning three orders of magnitude. Although larger

Figure 5-2:
Instrument calibration curves from GC/ITMSâ„¢ analyses both (a) with
and (b) without axial modulation employed during mass analysis.

136

137
amounts of analyte were analyzed, space charging began to occur at higher
concentrations at which point the plots began to level off. To construct the
curves, samples were dissolved in o-xylene and serial dilutions performed to
produce standards with analyte concentrations ranging from 200 pg///L to 2000
ng///L. The concentration of the IS was 50 ng//vl_ in all cases. This resulted in 5
pg to 50 ng of analyte and 1.25 ng of IS being injected onto the chromatographic
column. The curves show that better linear models resulted when axial
modulation was employed. The results of linear regression analysis of the data
is shown in Table 5-1. The correlation coefficients (r2) and precision of triplicate
injections (expressed as %RSD), also show that axial modulation improved
quantitation and provided excellent linearity and precision over three orders of
magnitude.
Figure 5-3 depicts mass chromatograms of the analyte and IS from GC/MS
analyses of 10 ng of analyte, both with and without axial modulation being
employed during mass analysis. These chromatograms illustrate improved peak
shape with the use of axial modulation during the analytical scan. The mass
spectra taken from the apex of each GC peak also illustrate that incorrect mass
assignments caused by space charging were eliminated. The incorrect mass
assignments resulted in poor chromatographic peak shape, as illustrated in the
mass chromatograms of the analyte and IS of the analysis without axial
modulation. The improved peak shape provided much better quantitation and
precision to be obtained for GC/ITMSâ„¢ analyses when axial modulation was

Figure 5-3: Chromatograms from GC/ITMSâ„¢ analysis of 100 pg analyte and 10
pg IS illustrating peak shape and resulting mass spectra both (a)
with and (b) without axial modulation employed during mass
analysis.

Scan Number
cr
Relative Intensity
CS
CD
N
CD
CD
CO
CD
09
100X
Z9I.Z/UJ ^¿9T
Relative Intensity

140
Table 5-1: Summary of linear regression results revealing improvements with
use of axial modulation.
Without Axial Modulation
rf slope RSD
0.9756 1.086 <16%
0.9754 1.082 <21%
With Axial Modulation
2 0.9991 0.993 <3%
3 0.9994 0.983 <6%
Orders of
Magnitude
2
3
employed. Because of these improvements, axial modulation was used in
subsequent studies involving mass-selective storage (rf/dc isolation).
Alternating Mass-Selective Storage Scans
The use of mass-selective storage to reduce the effects of space charge
has been applied to quantitative analyses employing isotopically labeled internal
standards both in this lab and elsewhere (Strife et al., 1990). Space charge was
reduced by isolating a single m/z corresponding to an ion characteristic of the
analyte or the isotopically labeled IS in alternate scans during their
coelution.These studies utilized an additional FORTH program to permit the
ITMSâ„¢to alternate between two different scan functions, each optimized for either
the analyte or the IS, and collect the data to two separate datafiles.

141
An instrument calibration curve (log-log) resulting from this type of analysis
is shown in Figure 5-4. The analytical curve showed poor linearity and precision
of triplicate injections. Problems resulted from not being able to acquire enough
data points over the elution of a GC peak. The FORTH program repeatedly
loaded the scan functions from the PC hard drive into the ITMSâ„¢ firmware, which
is a relatively slow process. The ability to obtain only about one to two scans per
second resulted in poor averaging and GC peak shape definition. Although
space charging was reduced, faster software routines were needed to realize the
benefits of using alternating mass-selective scans to improve quantitation of
coeluting compounds.
Table 5-2 shows a condensed listing of a scan function developed which
also uses alternating mass-selective storage scans to quantitate an analyte and
coeluting IS. The method combines two separate mass-selective storage scan
functions which contain separate ionization, isolation, and mass analysis (data
acquisition) sequences optimized for either the analyte or the IS. Since both
acquisitions are contained within one scan function, the ITMSâ„¢ software sums the
acquired ion signal from both "sub"-scans to create a single scan. Because of
this, it was important that the mass analysis ranges of each subscan did not
overlap. This also prevented problems which may have resulted from incomplete
isolation of one component from the other because data are acquired with unit
mass resolution for only one component in each subscan.

Area 163+/Area 167
142
Figure 5-4: Instrument calibration curve (log-log) from GC/ITMSâ„¢ analysis using
alternating mass-selective storage scans. A supplemental FORTH
program was used to permit the ITMSâ„¢ to alternate between two
different scan functions.

143
Table 5-2: Condensed listing of a new ITMSâ„¢ scan function for combined rf/dc
isolations, including the component analyzed during each segment
and the time required for each table, as well as total time for the
entire scan function.
Component
Analyzed
Scan Table(s)
Time(ms)
Trigger
0.10
1st Ionization Pulse
0.50
Analyte
1st rf/dc Isolation
2.70
(m/z 163)
1st Data Acquisition Ramp*
(m/z 161 -* m/z 165)
0.72
rf Shut Down
0.10
Trigger
0.10
2nd Ionization Pulse
1.00
Internal Std.
2nd rf/dc Isolation
2.70
(m/z 167)
2nd Data Acquisition Ramp*
(m/z 165 m/z 169)
0.72
rf Shut Down
0.10
8.74
includes application of axial modulation

144
This new method provided a more rapid means of alternating between rf/dc
isolating/analyzing an analyte and its isotopically labeled IS. The entire scan
function was loaded from the PC hard drive into the ITMSâ„¢ firmware only once,
at the beginning of the GC/MS analysis. This eliminated the time-consuming step
of repeatedly accessing and loading the scan function into the firmware between
every scan, and resulted in performing the same task more rapidly than when
using a FORTH program. Times measured on an oscilloscope (Model 5440,
Tektronix, Inc., Beaverton, OR) showed that to acquire and average three
microscans for both components required ~ 105 ms. Timing traces for the new
scan function and the scan functions which utilized a FORTH program are shown
in Figure 5-5. These traces are shown for one microscan/scan (no averaging) for
clarity. Also shown is the time required to analyze and acquire data for both
components using each method. The traces show that although the actual
ionization/isolation/mass analysis steps require similar times, the necessary disk
read/write/load steps require much longer times with the FORTH controlled
method. These traces show that the new scan function was more than eight
times faster than the previously used method.
The benefits of the faster acquisition rate of the new scan function are
illustrated in Figure 5-6. Shown are mass chromatograms obtained for triplicate
injections of 50 pg of analyte (10 pg IS) using both the new scan function and the
previously used method. The peaks in the chromatograms obtained by using the
new scan method show excellent reproducibility, whereas those from the latter are

a) New scan method
b) FORTH controlled method
Figure 5-5: Scan function timing diagrams showing rf amplitude versus time (not to scale) indicating the
time required to analyze the analyte and IS with the (a) new combined rf/dc scan function and
(b) FORTH controlled alternating rf/dc isolations. Trace (a) corresponds to the scan function
listed in Table 5-2.

Rel. Intensity Reí. Intensity
Retention Time
Figure 5-6: Mass chromatograms (m/z 163) of analyte (50 pg) obtained from triplicate injections using the
(a) new combined rf/dc scan function and (b) FORTH controlled alternating rf/dc isolations.
Oí

147
irreproducibly skewed or shaved off. These improvements were attributed to the
ability to acquire more data points (eight to nine) over a GC peak with the new
scan function, yielding more reproducible GC peak shapes.
Figure 5-7 shows a typical instrument calibration curve in log-log format
obtained using this new scan function. The curve shows excellent linearity
spanning four orders of magnitude (0.5 pg to 5 ng analyte with 10 pg IS on
column). The summary of linear regression results in Table 5-3 shows the new
method provides much improved linear correlations (r2 > 0.999) and precision of
triplicate injections (RSD <6%) than the previous method, which utilized a
supplementary FORTH program. Slopes <1 (typically 0.6-0.7) are believed to
result from differences in the isolation efficiencies of the analyte and IS.
Table 5-3: Summary of linear regression results comparing methods of
alternating mass-selective storage (rf/dc isolation) scans.
FORTH Controlled
if slope RSD
0.9492 0.679 <15%
0.9255 0.152 <19%
0.9779 0.106 <19%
Combined Scan Function
2
0.9994
0.734
<5%
3
0.9992
0.629
<6%
4
0.9991
0.632
<6%
Orders of
Magnitude
2
3
4

Area 163+/Area 167
148
100
+
10
1
0.1
Figure 5-7:
Instrument calibration curve (log-log) for triplicate injections
spanning four orders of magnitude for compound studied using new
combined rf/dc scan function.

149
Liquid Chromatoqraphv/Mass Spectrometry
The results from the initial GC/MS studies were then applied to LC/MS to
investigate whether the use of coeluting standards improved the quantitative utility
of LC/PB/ITMSâ„¢. Since benzidine provided a baseline LC peak width of ~45 s
(as compared to 1-2 s for GC), the FORTH controlled mass-selective storage
method may have provided enough data points across the LC peak to produce
adequate quantitation. The faster acquisition rate of the new scan function,
however, allowed a greater number of microscans to be averaged by the data
system. In addition, data analysis was also simplified because all data were
acquired to one datafile using the new scan method.
Figure 5-8 shows an instrument calibration curve for benzidine obtained
from the LC/PB/ITMSâ„¢ calibration runs discussed in Chapter 4. The curve
illustrates the nonlinear behavior typically associated with LC/PB/MS analyses.
An ID calibration curve from the LC/PB/ITMSâ„¢ analysis of benzidine using the
combined mass-selective storage scan is illustrated in Figure 5-9. The amount
of d8-IS injected was 100 ng for all standards. Plotted in the figure is the ratio of
the peak area of the analyte (184+) and IS (192+) vs. the amount of amount of d0
injected. The inset is a blowup of the region below 100 ng to better illustrate the
linearity at the low end of the curve. The analytical curve exhibited good linearity,
even at the low end. The same linear dynamic range achieved in the GC/ITMSâ„¢
studies (3-4 decades) could not be obtained with LC/MS because of the much

Normalized Area 184
150
Figure 5-8: Benzidine instrument calibration curve with no IS illustrating
nonlinearity typically associated with LC/PB/MS analyses.

Figure 5-9: Isotope dilution calibration curve from the LC/PB/ITMSâ„¢ analysis of benzidine using the
combined mass-selective storage scan. The amount of d8-IS injected was 100 ng for all
standards. The inset is a blowup of the region of the curve below 100 ng of d0 injected.

Area 184+/Area 192+
O —‘ K) OJ > en CT)
b b b b b b b
Z9l

153
higher LODs (low nanogram) associated with LC/PB/ITMSâ„¢ compared to the
LODs achieved with GC/ITMSâ„¢ (low picogram).
The increased linearity shown in Figure 5-9 was largely attributed to
improved transport through the interface caused by coelution of the internal
standard. Individual calibration curves (log-log) for both the analyte (184+) and
IS (192+) from ID analyses with three different concentrations of IS are shown in
Figure 5-10. The analyte curves (Figure 5-10a) show that an enhancement in the
analyte ion signal was observed for increasing quantities of coeluting IS. As a
result, LODs were lowered as the amount of IS injected was increased. While
LODs were determined to be 5 ng when 50 ng IS was injected, LODs were ~ 1.2
ng when 100 and 250 ng of IS were injected. In contrast, LODs were observed
to be only ~10 ng during these studies when no coeluting IS was used. The
enhancement in signal and lower LODs were a result of the coeluting IS acting
as a "carrier," which improved analyte transport through the interface, much as the
use of ammonium acetate in the mobile phase (Bellar et al., 1990).
Although the amount of IS injected was constant throughout the course of
the calibration runs, all the IS calibration curves in Figure 5-10b exhibit a decrease
in signal at larger amounts of analyte. This drop in signal was probably due to
space charging prior to rf/dc isolation which could cause losses of the ion of
interest during mass-selective storage. The decrease in IS response could also
result from a larger degree of self-CI occurring via ion/molecule reactions with
either species at larger amounts injected due to the large amount of neutrals
present in the ion trap. Since isotopically labeled compounds exhibit virtually

Figure 5-10: Calibration curves for both the (a) analyte (184+) and (b) IS (192+)
from isotope dilution LC/PB/ITMSâ„¢ analyses with different amounts
of IS injected.

Peak Area 192 Peak Area 184
100000-
10000
i i i i i i 111 i r
1 10 100
Amt. d0 Injected (ng)
T 1 1 1 I I I I |
1
10
T 1 1 I I I ! I |
.100
T
1

156
identical chemical behavior, it is feasible that the IS ion (m/z 192) could have a
proton abstracted by either a native or deuterated benzidine neutral molecule
yielding (M+H)+ ions at m/z 185 or 193, which would either be ejected during
mass isolation of the IS ion or not included in the peak area determinations,
depending upon when formed during the scan function. As expected, the
decrease in signal occurred earlier in the calibration run when larger amounts of
IS were used. Prior to the loss of signal, however, the response for each amount
of IS was relatively constant, although some enhancement of signal at low
amounts of analyte can also be seen in the curve with 50 ng IS which was likely
due to transport losses.
The variations in IS signal caused nonlinearities at the ends of the ID
calibration curves. The ID calibration curves from LC/PB/ITMSâ„¢ analyses with
both 250 ng and 50 ng of IS injected with the native benzidine are shown in
Figure 5-11. The nonlinear behavior is evident in both the ID curve in Figure 5-
11a (250 ng IS) and the ID curve shown previously in Figure 5-9. Nonlinearity is
also evident at the low end of the calibration curve in Figure 5-11b (50 ng IS) and
is attributed to transport losses of small, low momentum particles.
As mentioned previously, the linearity observed in the ID calibration curves
was believed to be largely the result of improved transport through the interface.
It has been suggested that there is some "critical level" where the transport of
particles becomes reasonably constant until the interface or mass spectrometer
becomes saturated with analyte (Ho ef a/., 1992). To test this hypothesis, aseries

Figure 5-11: Isotope dilution calibration curves from LC/PB/ITMSâ„¢ analyses
using (a) 250 ng IS and (b) 50 ng IS.


159
of standards were prepared with varying concentration of analyte and IS. The
concentrations of each component were chosen such that the total amount (i.e.
sum) of analyte and IS injected was constant throughout the calibration runs.
Figure 5-12 shows the results of these experiments where the sum of native and
deuterated benzidine injected was kept at a constant amount -250 ng. The
calibration of both components are independently linear due to the elimination of
transport efficiency deviations. Also, the effects of space charging and self-CI
which caused variable response in Figure 5-11b would be constant throughout
these calibration runs. The differences in intensities of the two components
probably resulted from different rf/dc isolation efficiencies of the two ions.
Figure 5-13 reveals the ID calibration curve (log-log) which resulted from
the data shown in Figure 5-12. Since the amount of IS injected was not constant,
the ratio of the peak areas is plotted against the ratio of the amounts of analyte
and IS injected. The curve shows good linearity and precision of duplicate
injections. The cun/e also exhibits a wider linear dynamic range (- 2.5 decades)
than the ID calibration curves previously shown which used a constant amount
of IS (Figure 5-9); however, this method would not be as practical for quantitation
of unknowns in real-world samples. The use of a variable amount of IS would
necessitate an initial screening of the unknown to determine the appropriate
amount of IS to be used.
The results of these LC/MS studies suggest that the use of coeluting
isotopically labeled IS may be the best method for quantitation using LC/PB/MS.
The use of a coeluting IS could compensate for difference in analyte transport

Figure 5-12: Calibrations for both analyte and IS from LC/PB/ITMSâ„¢ analysis where the sum of native and
deuterated benzidine injected was kept at a constant amount of 250 ng.

Amt. d0 Injected (ng)
Peak Area 184+ (cts.)
Peak Area 192+ (cts.)
191
Amt. d8 Injected (ng)

Area 184+/Area 192
162
Figure 5-13: Isotope dilution calibration curve from constant sums experiment
described in text.

163
through the interface caused by unknown coeluting substances in real-world
samples and lower detection limits as well. Indeed, it has been suggested that
the use of coeluting IS may the only reliable approach for quantitative analyses
of real-world samples (Ho et a/., 1992).
Conclusions
A new method of rapidly performing alternating rf/dc isolation scans on the
ITMSâ„¢ has been demonstrated. When applied to GC/ITMSâ„¢ analyses employing
isotopically labeled IS, this method shows excellent linearity over four orders of
magnitude. The sensitivity, linearity, and reproducibility are largely due to the
ability to alternate between analyzing analyte and IS ions rapidly enough to obtain
an adequate number of data points (eight to nine) over a GC peak approximately
1 s wide. The use of axial modulation during mass analysis has also been shown
to provide improved chromatographic peak shapes as well as excellent linearity
and precision over three orders of magnitude.
Although not reported here, the use of resonant ejection (notch filter) to
reduce space charging and extend the dynamic range was also investigated.
These studies were similar to the initial mass-selective storage experiments in that
a supplemental FORTH program was used to alternate between scan functions
which ejected either the analyte or IS in alternating scans. The ability to acquire
only 1-2 data points across a chromatographic peak resulted in poor quantitative
results. Better results might be obtained by combining the two resonant ejection

164
scan functions in the same manner as the combined mass-selective storage scan
function reported in this chapter to allow more data points to be obtained across
a chromatographic peak; however, the use of mass-selective storage was more
attractive because of its potential to reduce space charging to a greater extent by
eliminating all but a single ion of interest, rather than a single ion species.
The use of isotopically labeled IS also provided more reliable quantitation
for PB/LC/ITMSâ„¢. The improvements were largely due to the coeluting IS acting
as a "carrier" which improved analyte transport through the interface. Linear
calibrations (r2 = 0.998) have been demonstrated using the combined scan
function developed for GC/ITMSâ„¢. The LC/PB/ITMSâ„¢ calibration curves,
however, did not exhibit as wide a linear dynamic range as was achieved with
GC/ITMSâ„¢. This was due to poor transport through the PB interface at low levels
of analyte. As a result, LODs for LC/MS were about 1000 times higher than those
observed for GC/MS. It should be noted that the use of isotopically labeled IS is
limited, however, by their limited availability and high cost.

CHAPTER 6
CONCLUSIONS AND FUTURE WORK
Conclusions
These studies have demonstrated the successful coupling of a prototype
three-stage particle beam LC/MS interface with a quadrupole ion trap mass
spectrometer. The analysis of several pesticide mixtures has been demonstrated
using both isocratic and gradient elution LC separations. Results obtained on the
LC/PB/ITMSâ„¢ system have also been compared to results obtained on an
LC/PB/TSQâ„¢ system which utilized the same PB interface.
Due to variations between commercially available PB interfaces,
characterization of important PB operating parameters is necessary to intelligently
develop effective LC/MS methods. Parameters including the nebulizing gas flow
rate, desolvation chamber temperature, desolvation chamber pressure, and
source target temperature have all been demonstrated to affect the sensitivity of
the LC/PB/ITMSâ„¢ system. Most of these parameters were found to be largely
mobile phase dependent; however, some compound dependence was observed,
most notably for the PB target temperature. Modifications to the ion trap endcap
electrode (target) were made which allowed optimum target temperatures (250°
165

166
to 300°C) to be utilized while maintaining other mass spectrometer components
(e.g. electron multiplier) at normal operating temperatures.
Although the additional third stage of momentum separation has been
demonstrated to reduce the amount of solvent which reached the trap, it was
necessary to eject solvent ions prior to mass analysis to minimize space charging
and prevent a significant degree of solvent-CI from occurring. Two different
modes of ion trap operation using standard ITMSâ„¢ software were shown to
effectively eject solvent ions prior to mass analysis. This afforded the ability to
generate El spectra which compare favorably to both library El spectra and El
spectra obtained from solids probe/ITMSâ„¢ analyses.
The utility of the LC/PB/ITMSâ„¢ system was demonstrated for performing
both isocratic and gradient elution LC/MS analyses of pesticide mixtures. The
results obtained from the gradient elution LC/PB/ITMSâ„¢ analyses were also
compared to results obtained on an LC/PB/TSQ system. Although the fragment
ion abundances of the El spectra obtained the LC/PB/ITMSâ„¢ showed good
agreement with El spectra obtained on the LC/PB/TSQ system, some differences
in the relative intensities of fragment ions were observed. At high analyte
concentrations, the LB/PB/ITMSâ„¢ system also exhibited a larger amount of self-
Cl, as indicated by a larger (M+1)+/M+' ratio. Estimated LODs were in the low
ng range and were comparable between the two systems. The LODs obtained
appear to be limited by the interface rather than the type of mass spectrometric
detector. This would explain why lower LODs were not observed using the more

167
sensitive ITMSâ„¢. Relative standard deviations of replicate injections were less
than 10% for midrange calibration standards and near the estimated LODs.
Although linear calibrations have been observed, nonlinear calibrations were more
prevalent. The ability to acquire both El and Cl spectra in alternating scans
during the elution of a chromatographic peak on the LC/PB/ITMSâ„¢ system has
also been demonstrated.
Quantitation using isotopically labeled internal standards for GC/MS and
LC/MS analyses on the ion trap has also been investigated. Despite their high
cost and limited availability, isotopically labeled IS are attractive for their abiility
to provide extremely accurate quantitation. A new method of rapidly performing
alternating mass-selective storage scans on the ITMSâ„¢ has been demonstrated
to extend the linear dynamic range to four orders of magnitude for GC/ITMSâ„¢
analyses. The use of axial modulation during mass analysis has also been shown
to improve quantitation by reducing space charging and thereby providing
improved chromatographic peak profiles for quantitation.
When applied to LC/PB/ITMSâ„¢, the use of isotopically labeled IS also
provided more reliable quantitation. The improvements were largely due to the
coeluting IS acting as a "carrier" which improved analyte transport through the
interface. Linear calibrations (r2 = 0.998) have been demonstrated using the
alternating mass-selective storage scan function developed for GC/MS. The
LC/MS calibration curves, however, did not exhibit the wide linear dynamic range

168
which was achieved with GC/ITMS. This was because the LODs for LC/PB/ITMSâ„¢
were about 1000 times higher than those observed for GC/ITMSâ„¢.
Suggestions for Future Work
Future directions suggested for the this project include the development
of improved ion trap instrumentation including the use of an external ion source
and ion injection system. Ion injection would reduce problems with ion/molecule
reactions such as self-CI, because the number of neutrals which reach the trap
would be dramatically reduced. Problems with space charging could also be
minimized by controlling the number of mass range of injected ions (Yost and
Pedder, 1989). Ion injection into traps has previously been demonstrated using
both on-axis (Louris et al., 1989) and off-axis (Pedder et al., 1989) ion sources.
Development of ion injection sources is currently in progress in our labs here at
UF. To facilitate this, a new cradle vacuum manifold capable of differential
pumping has been constructed and interfaced to Finnigan MAT (San Jose, CA)
ITS-40 electronics during the course of this project.
The use of ion injection would also allow a wider variety of LC interfaces
and ionization methods to be utilized. Although PB is recognized for its ability to
generate classical El spectra, the use of other vaporization/ionization techniques
might be advantageous. Many thermally labile and involatile compounds are not
amenable to PB because they decompose under flash vaporization or El. Since
PB is truly a transport interface in that the analyte is merely desolvated and

169
transported to the mass spectrometer as solid crystals, other vaporization and
ionization techniques could be implemented to widen the scope of compounds
that could be analyzed by LC/PB/MS. Experiments are currently being performed
to examine the feasibility of using laser desorption (both matrix-assisted and non-
matrix-assisted) of the particle beam to obtain mass spectra of thermally labile
and involatile compounds (Richardson and Browner, 1992). The development of
an ion injection system would allow these studies to be performed using an ion
trap. Although these experiment might broaden the range of compounds which
could be analyzed by LC/PB/MS, the carrier effect through the momentum
separator would likely not be improved. As a result, non-linear calibrations would
probably still be obtained.
One of the major advantages of the ion trap is the ability to perform
multiple stages of mass spectrometry (MS/MS, MS") with no hardware changes.
Some compounds exhibit little fragmentation upon El which complicates
identification of some unknown compounds. Tandem mass spectrometry could
be employed to attempt to produce structural information using collisionally
activated dissociation (CAD); however, not all compounds CAD extensively. The
use of MS" would also be of value for analysis of samples with complex matrices
which would be difficult to separate with the limited chromatographic efficiency
of LC, as compared to capillary GC. The use of MS" could relieve some
requirements for extensive sample preparation of crude extracts. Since matrix-
assisted laser desorption typically produces predominantly molecular ions, the

170
use of MS/MS could also be used to produce structural information from
molecular ions [e.g. M+', (M+H)+] produced from the PB/laser desorption
experiments suggested previously.
The methods of solvent ion ejection presented in this dissertation were
implemented with standard ITMSâ„¢ software. Other solvent ion ejection methods
could be implemented with modifications to the ITMSâ„¢ source code or additional
instrumentation. These include the use of waveforms comprised of multiple
frequencies based upon broadband and frequency sweeps (Eades et al., 1991,
McLuckey et al., 1991) and stored waveform inverse Fourier transform, SWIFT
(Julian et al., 1992).
The use of a membrane separator could also be investigated to reduce the
amount of solvent which reaches the ion trap. Preliminary studies with coupling
a commercially available membrance separator (Vestec, Houston, TX) with the
three-stage momentum separator were largely unsuccessful. This membrane
required a large flow of He to be swept along the membrane which caused high
operating pressures inside the ion trap. The use of the differentially pumped ion
injection system could allow these studies to be performed by preventing large
pressures in the analyzer.
In Chapter 2, it was demonstrated that an increase in sensitivity was
observed at lower mobile phase flow rates. However, use of lower flow rates
results in increased analysis times. The use of micro-LC (capillary) columns offer
the advantages of higher column efficiencies and drastically reduced flow rates.

171
State-of-the-art microcolumns are open tubular capillary columns (i.d. 40-200 /jrr\)
packed with 3-20 //m particles which typically have total numbers of theoretical
plates well over 20,000 (Novotny, 1988). This would permit better separations
with lower flow rates without extending analysis times.
The sensitivity and dynamic range of the ion trap for quantitative GC/MS
analyses employing isotopically labeled IS could be improved by development of
an automatic gain control (AGC) routine which could be implemented with the
alternating mass-selective storage scan function described in this dissertation.
Currently, AGC cannot be implemented with custom scan functions. Because
AGC and selects an ionization time based upon an estimation of the total number
of ions in the trap determined from a short "prescan", the AGC software selects
optimum ionization times for the more abundant component when compounds
of different concentrations coelute; this may result in poor sensitivity and nonlinear
response for the minor component. It would be advantageous if the AGC
software could automatically select an ionization time which is dependent only
upon the intensity of the ion of interest. In this manner, discrimination against the
less abundant coeluting component (or a component present with a large
background) could be minimized.

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BIOGRAPHICAL SKETCH
Brent LaMar Kleintop was born in Palmerton, PA, on August 14, 1966, the
younger of two sons of Sherwood and Jean Kleintop. His secondary education
was obtained in the Palmerton Area School District, where he graduated in the
top ten percent of his class in June, 1984. After high school, he enrolled at
Wittenberg University in Springfield, OH. During the summer prior to his senior
year, he participated in a summer research program sponsored by the University
of Florida in Gainesville. He received the Bachelor of Arts degree in June, 1988,
with a chemistry major. He eagerly returned to the University of Florida in August,
1988. He has remained at Florida, under the direction of Dr. Richard A. Yost,
while completing work on his Ph.D. in analytical chemistry, specializing in mass
spectrometry. Upon graduation, he will begin work in the northeast district offices
of the Finnigan Corp. located in Livingston, NJ, as an applications chemist.
181

I certify that I have read this study and that in my opinion it conforms to
acceptable standards of scholarly presentation and is fully adequate, in scope
and quality, as a dissertation for the degree of Doctor of Philosophy.
Richard A. Yost,(£hair
Professor of Chemistry
I certify that I have read this study and that in my opinion it conforms to
acceptable standards of scholarly presentation and is fully adequate, in scope
and quality, as a dissertation for the degree of Doctor of Philosophy.
¡-K
James D. Winefordner
Graduate Research Professor of Chemistry
I certify that I have read this study and that in my opinion it conforms to
acceptable standards of scholarly presentation and is fully adequate, in scope
and quality, as a dissertation for the degree of Doctor of Philosophy.
V
- \A
Veneica Y. Young I
Associate Professor of Ghemistr
I certify that I have read this study and that in my opinion it conforms to
acceptable standards of scholarly presentation and is fully adequate, in scope
and quality, as a dissertation for the degree of Doctor of Philosophy.
• James M. Boncella
Associate Professor of Chemistry
I certify that I have read this study and that in my opinion it conforms to
acceptable standards of scholarly presentation and is fully adequate, in scope
and quality, as a dissertation for the degree of Doctor of Philosophy.
Jogfefch J. Déífino
Professor of Environ
Sciences
ental Engineering

This dissertation was submitted to the Graduate Faculty of the Department
of Chemistry in the College of Liberal Arts and Sciences and to the Graduate
School and was accepted as partial fulfillment of the requirements for the degree
of Doctor of Philosophy.
May, 1993
Dean, Graduate School

UNIVERSITY OF FLORIDA
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