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Atomic emission and atomic fluorescence spectrometry in inductively coupled plasma

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Title:
Atomic emission and atomic fluorescence spectrometry in inductively coupled plasma
Creator:
Nikdel, Seifollah, 1942-
Publication Date:
Language:
English
Physical Description:
ix, 231 leaves : ill. ; 28 cm.

Subjects

Subjects / Keywords:
Atoms ( jstor )
Emission spectra ( jstor )
Flames ( jstor )
Fluorescence ( jstor )
Inductively coupled plasma mass spectrometry ( jstor )
Ions ( jstor )
Lasers ( jstor )
Monochromators ( jstor )
Plasmas ( jstor )
Signals ( jstor )
Emission spectroscopy ( lcsh )
Fluorescence spectroscopy ( lcsh )
Spectrometer ( lcsh )
Genre:
bibliography ( marcgt )
theses ( marcgt )
non-fiction ( marcgt )

Notes

Thesis:
Thesis--University of Florida.
Bibliography:
Includes bibliographical references (leaves 225-230).
General Note:
Typescript.
General Note:
Vita.
Statement of Responsibility:
by Seifollah Nikdel.

Record Information

Source Institution:
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.
Resource Identifier:
023342530 ( ALEPH )
AAL2915 ( NOTIS )
06572087 ( OCLC )

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ATOMIC EMISSION
AND ATOMIC FLUORESCENCE SPECTROMETRY
IN INDUCTIVELY COUPLED PLASMA















BY

SEIFOLLAH NIKDEL


A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL
OF THE UNIVERSITY OF FLORIDA IN
PARTIAL FULFILLMENT OF THE REQUIREMENTS
FOR THE DEGREE OF DOCTOR OF PHILOSOPHY














EDUCATION


FOR INDEPENDENT


THOUGHT


is not enough


to teach


man


a specialty.


Through


it he


come


a kind


of useful


machine


but not a harmoniously


developed


person-


ality.


It is essential


that


the student


acquire


an understanding


of and


a lively


feeling


for values.


He must


acquire


a vivid


sense


of the beau-


tiful


and of the morally


good.


Otherwise


he--with


his specialized


knowledge--more


closely


resembles


a well-trained


than


a harmoniously


developed

beings, t


person.


heir


He must


illusions,


learn


and thei


to understand

r sufferings


the motives


in order


of human

acquire a


proper


relationship


to individual


fellow-men


and to the community.


ALBERT


EINSTEIN


From


York


Times


October


1952














DEDICATION


This dissertation is sincerely dedicated to my wife,


Christine Nik-


del, and my mother,


who have given me their


love and encouraged me to


obtain the endless knowledge within higher education.


In their debt


will always be.














ACKNOWLEDGEMENTS


wish


take


this


opportunity


express


my regard


to the friends


and colleagues


who,


through


their


interest


and discussions,


helped


make


this


time


pass


so easily.


like


to take


particular


pleasure


in express-


special


gratitude


research


director,


Graduate


Research


Profes-


sor Dr.


James


. Winefordner,


for his constant


sincerity


steady


guidance,


and kindly


inspiration


throughout


this


work.


Special


thanks


Drs.


Omenetto


Epstein


and R


Reeves


their


valuable


help


during


course


this


work.


extend


my appreciation


to the University


of Florida


Graduate


School


the financial


support


during


this


time.


And,


the patient


comprehension


and love


wife


Christine


typing


the first


draft


of this


dissertation


has made


this


effort


worth


while.


Her continuous


cheerfulness


and undeniable


sacrifices


offered


inspiration


when


was most


needed.
















TABLE OF CONTENTS



Page


ACKNOWLEDGEMENTS.......................... ... .. .................. iv

ABSTRACT........... ................................................. vii

CHAPTER

ONE INTRODUCTION......................... ..... .. ...... 1


- Atomic Emission..............
A.1 History of the ICP.....


.................
. .... .*..
* C C C C C .


- Theory and Mechanism of Excitation
in ICP.................... ........
- Sensitivity and Growth Curve in ICP


- Atomic Fluorescence..............
B.1 History..................
B.2 Theoretical Considerations.
B.3 Noise and Detection Limit..


*.... 3


C.............
* C .C.C.. ..


MOLECULAR EMISSION SPECTRA AND ATOMIC
EMISSION SPECTROMETRY IN ICP........................


- Molecular Emission Spectra...
A.1 Introduction...........
A.2 Experimental...........
A.3 Results and Discussion.
- Rare Earths Analysis.........
B.1 Introduction...........
B.2 Experimental...........
8.3 Results and Discussion.


THREE


...... .... .a. ..
S.a....... ..... C



a...... ...C.C.C.C..
...... ... C *Ce .*
*.C.....C ..* ..* .....*. *


ATOMIC FLUORESCENCE SPECTROMETRY IN THE FLAME
USING ICP AS A NEW EXCITATION SOURCE "ICP-


EXCITED FASF"


- ICP Diagnostics Using the ICP-Excited FAFS..


A. 1 Introduction...................


S..... ..











- Introduction...........


- Experimental.....................
- Results and Discussion...........


- Applications...........


FOUR


... 109
... 110
... 116


. 128


ATOMIC FLUORESCENCE SPECTROMETRY IN ICP WITH
DYE LASER EXCITATION "LASER-EXCITED AFS IN ICP"


- cw Dye Laser


as an Excitation Source in ICP


- Introduction...........
- Experimental...........
- Results and Discussion.


S.. 135
... 135
... 136
... 141


- Relative Spatial Profiles of Barium Ion
and Atom in the Argon Inductively Coupled


as Obtained by Laser Excited


Fluorescence..........................
B 1 Intr oduction
S1 Introduction... .. .. ......
B.2 Experimental.. ...................
B.3 Results and Discussion..........


- Pulsed Dye Laser
in ICP..........


..... 155
..... 155
....... 158
....... 163


as an Excitation Source


- Introduction...........
- Experimental.........
- Results and Discussion.


FIVE


S..... .. 209


CONCLUSIONS AND FUTURE WORK ON INDUCTIVELY


COUPLED PLASMA EITHER AS ATOM/ION CELL OR AS
AN EXCITATION SOURCE..... ........................... 218


REFERENCES............. ..... ...... ..... ........ ... ...........


BIOGRAPHICAL SKETCH..... .. .4.. .. 231


Plasma


Page














Abstract


Diss


of the Univer


ertation


sity


Pres


Florida


ented


to the Graduate


in Partial


Fulfillment


Council
of the


Requirements


for the Degree


Doctor


Philosophy


ATOMIC


SSION


AND ATOMIC


FLUORESCENCE


SPECTROMETRY


IN INDUCTIVELY


COUPLED


PLASMA


Seifollah

December


Nikdel

1979


Chairman:


James Dudley


Winefordner


Major


Department


Chemi


stry


Molecular


emission


spectra


native


species


and NH)


in the


argon


inductively


coupled


plasma


(ICP)


have


been


studied


as a function


height


in the plasma,


input


power


and adjacent


environment


to the


plasma.


Similar


studi


were


carried


out with


an ICP into


which


is introduced


moderately


concentrated


solutions


elements


forming


stable


monoxides,


such as Sc,


, Gd,


and Lu


Using


a medium


power


.25-1


ICP as an excitation


source


atomic


emission spectrometry


with


a glass


concentric


nebulizer


, aqueous


solutions


rare


earth


elements


pure


solution


and combined


mixture


all the


rare


earth


elements


are measured


except


Analytical


lines


characteristics


for such


measurements


are given.


T aa L 21-2- -


1:-


,-C. -I


-C c, r^ ~ -- i i,


T~,, 1,,,,, L,,:,


L








qualitatively


detected.


In such


means


urements


the flame


is used


as a reso-


nance


detector.


The results


show


that


self-absorption,


while


present


severe


and that


self-reversal


is absent


in the observation


zones


com-


only


used


for analytical


measurements.


Furthermore


use


of the ICP


as excitation


source


in flame


atomic


fluorescence


spectrometry


permitted


low limits


of detection


to be achieved


with


a simple


experimental


set-up.


An inductively-coupled


argon


asma


(ICP)


is used


as a narrow


line


radiation


source


for the excitation


of atomic


fluorescence


in several


analytically


useful


flames


(nitrogen


-separated


air/


acetylene


and nitrous-


oxide/


acetylene).


Detection


limits


14 elements


are compared


to atomic


fluorescence


detection


limits


using


other


radiation


sources


and to those


other


atomic


spectrometric


techniques.


Dominant


noise


sources


which


limit


measurement


precision


and high


concentrations


and the


sig-


nificance


and correction


for the scatter


problem


are di


scussed.


reduction


spectral


interference


observed


in ICP-emission


demonstrated


for the determination


zinc


in unalloyed


copper


SRM-394


and 396)


The technique


is also


applied


to the determination


zinc


SRM-1633


cadmium


and zinc


in simulated


fresh


water


(NBS


SRM-1643


copper


zinc


in orange


juice.


Atomic/ionic


fluorescence


in the ICP


using


a cw dye


laser


as an ex-


citation


source


has been


studied


Detection


limits


elements


such


and V


are given


Also


the results


show


non-Local


Thermo-


dynamic


Equilibrium


excitation


conditions


in our low powered


ICP.


Relative


ionic


and atomic


fluore


science


profiles


for barium


have


been







procedure,


with


a volume


resolution


of approximately


. The profiles


are given


along


the excitation


axis


as well


as along


the observation


axis,


different


heights


above


the coil


and different


input


powers.


At low


heights


ion profile


resembles


a hollow


pencil


with


a typical


double-


peaked,


asymmetric


distribution,


while


the atom


profile


seems


to be


com-


elementary


to the


ion profile.


Some


scatter


from


water


is also


evident


at low heights.


tuning


the laser


at two excitation


transitions


shar-


a common


upper


level


the temperature


the plasma


could


be evalu-


ated.


The atomic


and ionic


fluorescences


iron


barium


and indium


excited


flashlamp-


and nitrogen


laser-pumped


pulsed


lasers


in the


inductively


coupled


plasma


(ICP)


are studied.


Noise


sources


are investi-


gated


and detectability


is compared


to the techniques


of ICP-emission


laser-excited


atomic


fluorescence


spectrometry.















CHAPTER


INTRODUCTION


- Atomi


- History


Emission


the ICP


Earl


developments


ectrodel


ess


charges.


The low-pressure


electrodel


ess


charge


been


known


since


1884.


was discovered


first


Hittorf1


experiments


on the conduction


electricity


through


the noble


cases.


Mavrodineanu


and Hughes


traced


the rf-excitation


of low-pressure


ases


for spectrochemical


Thomson,


1927


analysis


published


to the work


experimental


Tesla


results


in 1891


along


Then


with


theory


the electrodeless


discharge


expressing


the magnetic


and el


field


spatial


distributions


Bessel


functions


, assuming


constant


asma


conductivit


across


the column.


Later


Babat,


in 1942,


discov-


ered


that


a ring


discharge


can be


maintained


while


pressure


creased


modern


up to atmospheric


inductively


evel.


coupled


Thus


asma


Babat


discharge.


the inventor


However


of the


major


terest


developed


only


after


Reed


success


fully


showed


that


one


can pro-


duce


an "Induction


Torch"


where


the plasma


is observabi


above


the torch


useful


as a heat


source.


ec-


* U


. .








engineers,


and second


as a spectrochemical


excitation


source


ana-


lytical


chemists.


main


reason


for the delay


developing


a stable


Inductively


Coupled


Plasma


(ICP


after


Babat's


publication


was the de


sign


a re-


liable


method


cooling


and heat


protection


of the plasma.


Water


cooled


wall


water


jackets


porous


dielectric


walls


were


applied


but Reed


s approach


a gas cooling


system


proven


most


effective


is now


universally


accepted


for spectrochemical


applications.


Reed


s work


showed


three


attractive


properties


for the plasmas


which


were


high


gas temperature


(ii)


capability


of being


sustained


noble


environments


(important


from


free-atom


lifetime


consideration)


iii)


freedom


from


contamination


electrodes


which


were


quired.


After


Reed


groups


Greenfield


and Wendt


and Fassel7


independently


investigated


the potential


use of


induction-heated


plasmas


as an excitation


source


. vaporization


, dissociation,


decomposition


cell


free


atom/


reservoir


for atomic


ssion


spectrometry


Fassel


and co-workers


studied


a great


number


variabi


veloping


group


an analytically


had experienced


useful


problems


ICP system


introducing


Until


sample


1969


into


Fassel


the high


temperature


zone


of the plasmas


. At that


time


Fassel


and Dickinson


were


able


"punch


a hole"


through


the center


of the plasma


intro-


during


high


velocit


carrier


in the sample


injector.


However


same


solution


had been


used


since


1964


Greenfield


in England







results


, (ii)


to be sensitive


give


detection


limits,


(iii)


need


sample


pretreatment


cover


a broad


range


elements


. ideally


measure


all elements


in the periodic


table)


possess


a large


namic


concentration


range


and (vi)


to allow


simultaneous


multi


-element


determination.


Looking


to the field


instrumental


analysis


the optical


tech-


niques


seem


be the most


appropriate


for analytical


purposes.


They


are favored


their


speed


ease


operation


as well


as simple


sample


pretreatment.


The possibilities


handling


many


samples,


giving


high


sensitivity


and of


determining


numerous


elements


simultaneously


are the


other


important


characteristic


relating


this


field.


The inductively


coupled


radio-frequency


argon


plasma


(ICP)


being


an extremely

capability


efficient


atomic/


and the high


chemical


interference


ionic


kinetic

s than


emission


source


temperature


lower


makes


temperature


has multi


less


sources


-element

susceptible


such


flames.


general


chemical


effects


are 1


than


10%.)


pre-


cision


is comparable


flame


atomic


absorption


-5%)


The reported


linear


dynamic


range


approaches


the capabilities


modern


electronic


equipment


which


are indeed


needed


to take


advantage


of this feature


and exceeds


the linear


dynamic


range


flame


atomic


absorpt


cons


erably.


The limits


of detection


reported


most


widely


the literature


ssion


spectrometry


with


the ICP usually


lie i


range


of 0.01-


are one


to three


orders


of magnitude


lower


than


with


high


I-,








phase by the excitation source,


atoms or


i.e.


concentration in condensed phase to


ions per unit volume in the gas phase c-nM;


transition of a


certain number of these atoms/ions


from the ground state to the excited


state


(or metastable state) M-4M


conversion of the excitation energy


into the spectral line radiation M -4M+hhv;


selection of the radiation of


the specific line from the total radiation of the source by the spectral

instrument and its transformation by the recording system into a measur-


able signal


from the line under study


(e.g. photomultiplier photocurrent


in case of photoelectric recording etc.).


A unit volume of the luminous source contains nM atoms or


the analyte.


ions of


The elementary phenomenon leading to the excitation of


ground state atoms/ions and the quenching of the excited atoms/ions


(M+M


are rather varied.


These are collisions of atoms/ions with free


electrons and heavy particles,


the gas in the source,


atoms,


as well as,


ions,


electrons and molecules of


in some cases,


chemical reactions


with the participation of M atoms/ions.


In practical spectral analysis,


resonance


lines of atoms/ions,


corresponding to the transition from the nearest excited level to the


ground state are often measured.


In sources with a high concentration of


electrons, e.g.,


in plasmas,


the basic phenomenon which lead to the


citation of resonance levels and also to atomization/ionization are col-


lisions with electrons.


Collisions with heavy particles are


less effec-


tive.


In the rf-excited


, inductively coupled argon plasma,


the population


ex-







at a given height


(=15 mm) above the induction coil.


Let us assume that


LTE conditions

population of


(T=6000 K)


in AV are disturbed by the creation of


argon metastable atoms


(outside of


an over-


AV) and representing


this by a net inflow of metastables


from the surroundings to AV.


This


inflow has a rate constant k


<(cm
m


-1 and its value depends on exter-
) and its value depends on exter-


nally controllable factors such


as power


input


in the coil region


(energy


addition region),


the plasma gas


flow conditions,


type of ICP (two-flow


argon ICP or a three-flow


ICP with nitrogen as the plasma gas and argon


as the carrier and auxiliary gas)


and the height of


AV from the induc-


tion coil.


Conservation of


energy


charge and mass balance require


16,18


(i) a


net outflow of


argon ions


and electrons


from the coil region having


a rate constant k.(cm
:1


for ambipolar diffusion;


(ii) a net outflow


of argon atoms


(Ar)


in the ground state from the coil region having a


rate constant ka (cm
a


for diffusion;


and (iii)


the following in-


terrelationships to apply


ki=(V
1


k =1-(V
a


where V
m


/V.)k =0.73 k =1-k ,
m/Vi m m l-k



m/V.)k =0.27 k =1-k.,
m i m m i'


is the weighted average excitation potential of the metastable


atoms at 6000 K


V =11.58 eV),
m


the ionization potential of


argon


(V.=15.76 eV), and k
I-


is the rate constant of the inflow of


argon metas-


table atoms


from their surroundings to the volume








as an ionizant,


i.e.


as an early ionizable constituent, eq.


as an


ionizer, eq.


having assigned the "dual role"):


+ 2e,


* +
MP


+, (3a)


+ e + Ar


+ 2e.


These rate constants are interrelated,


for local


thermodynamic con-


editions,


12/k21


-1/cm


34/k43'


where KAr


and KAr


are the Saha equilibrium constants in (cm


defined


=n n /nAr
Ar+ e Ar


=4.83x1015(cm


-3/2)


3/2
T


(Zi/gm)


m)/T)


I' rm/


-/cm


-3/cm


10(-5040(E.i


r\ / v


I kn .^*_^^


/ jkrq







argon and ground state argon


dimensionlesss);


m(eV)
m e


the excitation


energy of the relevant metastable level;


the excitation energy


argon.


For a steady state of the rate equation for Ar+ and electrons from


equations


and 4,


one would obtain the


following:


/dt=0=k +k21nAr+
m 21 Ar+


2n
n -k n
e 12 Ar


dne/dt=O=k1 nAr


n +k n n -k 2nr n
e 34 Ar e 21 Ar+ e


-k4 nA
43 Ar+ e


(10)


Using the quasi-neutrality condition,


ne =nAr+, combining the equations


and 10 would give:


(11)


The general solution of


equation


is an expression for n


in terms of


both KAr


and k /k43.
m 43*


Two special


cases


are of


interest in the


k /k3 >>KA nA n
m 43 Ar Ar e


, this applies to an


ICP; when


T=6000 K, n e1015
e


-1016


, in which the second term in equation


to n


11 is negligible compared


and therefore:


ne=(0.27 km/k43)1/


, (non-LTE),


(12)


for km=0,
m


equation


yields the Saha value of n


(KAr Ar1/2
e Ar Ar


(LTE).


(13)


dnA
Ar+


-k..
1


n-K Arn n -0.27(k /k 3)=0.
e Ar Ar e m 43


LTE).







to be a useful postulate,


as it permits a qualitative understanding of


the high sensitivity of


ionic lines,


the high electron number density,


and the negligible ionization interference observed in ICP's under op-

timum operating conditions.


- Sensitivity and Growth Curve in


Four analytical


figures of merit of


an atomic emission spectrometer


are:


the sensitivity,


the signal-to-noise ratio,


the line to background


ratio,


and the detection limit.


The detection limit is usually expressed


as the concentration which produces a signal equal


standard deviation of the blank.


to three times of the


The standard deviation in the blank


is a difficult quantity to predict


theoretically.


Neglecting the noise


in the detection system,


the following noise sources can be considered


in emission


ICP studies:


source flicker noise,


variation in the aerosol


production,


in the solvent evaporization,


the dry particles,


and instabilities of the plasma


and in the volatilization of


(electrical or fluid


dynamic).


The ICP has the properties of


arc and the flame.


a dynamic source


in common with the


It has a stationary high temperature zone


(coil re-


gion


10000 K)


in a fast


flowing gas stream maintained by forced and/or


free convection.


Sample material injected into the gas stream quickly


passes into the high temperature zone.


Nevertheless,


the ICP


as an ex-


citation source,


has several disadvantages:


(a) concentration of the element in the condensed phase and the

atom/ion population in the excitation zone in the oas chase do not have







and so it has to be supplied at a low constant rate for maintaining a


steady signal;


also material


that has been injected into the source can


not be used for


further


investigation and observation;


incomplete


mixing, unstable


flow and turbulence introduce fluctuations in signal


and background,


which raise


the detection limit;


and (d)


it is almost


impossible to understand the detailed performance of


because of the transient nature and the


a dynamic source


interdependence of the mixing


heating,


dissociation,


excitation,


and ionization processes to which the


analyte is subjected,


combined with the non-uniform velocity and temper-


ature fields of the source.


The sensitivity,


which is generally defined in analytical chem-


istry as the change of the signal per unit change of the analyte concen-


tration is inversely related to the detection limit.


For a linear cali-


bration curve,


it is


the slope of this curve,


which relates,


in its


simplest algebraic expression


14),


the line radiance,


, in (W cm


-1) with the analyze concentration in the gas phase (cm
) with the analyte co ncentration n,. in the gas phase (cm


-3).


It is


clear that to convert solute concentrations to emission of light a great


number of


intermediate physical processes are needed.


B=SnM


14)


In order to inject the sample solution to the plasma,


a means of


transport is needed.


Thus,


the solution is transported up by a nebulizer


and is converted into a fine spray of


droplets.


The larger droplets


fall


into the drain tube and the smaller droplets are carried away to the








Actually


the amount


of liquid


delivered


unit


time


(2.5


mL/min)


diluted


carrier


unit


time


L/min)


a factor


=0.005.


The smaller


droplets


are introduced


into


the high


tempera-


ture


zone


the plasma.


The solvent


which


usually


water


, evaporates


carrier


the free


expansion


model


, expands


with


a factor


where


the kinetic


gas temperature


is room


tempera-


ture.


fraction


the solvent


in the droplets


that


can


be evaporated


depends


on the kinetic


temperature


gradient


which


droplets


must


always


pass


before


reaching


the observation


zone.


Also


the droplet


size


distribution


is important


because


complete


evaporation


of large


droplets


takes


more


time


than


small


ones


This


transit


time


related


linear


velocity


of the


carrier


the temperature


gradient


as well


the droplet


size


and composition


, because


expansion


of the


will


duce


the velocity.


In the literature


, no experimental


results


are avail


able


locate


the height


the plasma


where


all droplets


are


just


evaporated.


However


similar


experiments


flames


suggest


that


sol-


vent


evaporation


will


be completed


rapidly


in the ICP


The next


step


is volatization


in which


a high


kineti


gas temper


ature


is needed


to disintegrate


the particle.


If only


analyte


jected


the dry


particles


will


very


small


However


an excess


another


salt


as a matrix


is present


the dry


particles


will


be larger


The boiling


point


this


salt


can


deviate


greatly


from


that


of the salt


the analyte


Thus


the amount


of analyte


released


in the


presence







As the solid


particles


are transported


deeper


into


plasma


high


temperature


zone)


their


temperature


will


rise


and start


to boil


come


into


gas phase


state.


At this


point


the relationship


between


the solution


concentration


and the total


vapor


concentration


analyte


species


has been


established.


From


here


the most


important


processes


are dissociation


, ionization


and excitation


, which


are all temn-


perature


(and


time)


dependent.


Let us consider


each


process


separately


when


the molecules


original


salt


are in the


gas phase


, they


will


dissociate


into


free


atoms.


Because


the solvent


is water


oxygen


atoms


from


dissociation


of water,


could


react


with


the free


analyte


atoms


to form


substantial


monoxide


spe-


cies


which


been


observed


for stable


monoxides


such


as rare


earths


laboratory


and will


shown


Chapter


The equilibrium


can be


shown


as follows


M+0.


The degree


of atomization


can be calculated


as follows


=nonM/nMO


(nO+Kd


15a)


, (16)


where


according


to Boumans


equilibrium


constant


can be calcu-


lated


from


-5040Ed


=nM/(nO+nMO)


) (


, nT,


=nM/( nM


nT=nM+nMO,


+ nMO


1024







water


is completely


dissociated


, the


value


is the


same


as the


number


density


water


molecule


introduced


nebulizer


into


plasma


x1016


The next


parable


important


to the dissociation


hase


except


process

that t


ionization


he products


which


are ions


com-


and elec-


trons.

here w


The degree


ie are interested


ionization

in atoms


defined


in the


expression


same ma

n for (


inner


-8.)


Because

is used.


. the


fraction


elemental


species


not ionized


+ K.)
I.


(18)


where


Saha


constant


and its numerical


form


.=4.83x1015
1


n )
a e


-5040Ei
i1


(19)


where


the ionization


energy


and Z


temperature


in (K)


are the partition


the ionization


functions


for ion and atom


dimensionlesss


The result


for (


-6.)
1


shown


Table


combining


the relation


these


between


processes


solute


assuming


concentration


complete


and the free


volatili


atom


zation


number


densit


the pi


asma


can be expressed


=apc8,


-si)


and for


ion i


given


nl+=pc8 .


(20b)


where


conversion


factor


in (


atoms


is given Oy


-i1


+ nM+


=nM/(nM








NA=Avogadro's number,


atoms


(molecules) per mole,


6. 0x1023


(dimen-


sionless);


MA=atomic (molecular) weight of


analyte,


(g/mole)


are in (cm


(ug/mL),


respectively.


The next important process in the gas phase is excitation,


which is


the process which transfers the atoms/ions from the ground state to the


excited state.


Upon returning to the ground state


light is emitted,


which the relation of


emitted light and total number density of free


atoms is given by:


J=I1n exp(-E


(21)


ex),


where E


is the excitation potential


in (eV),


is the excitation


temperature


(K),


J the emittance expressed in


(W cm


k is the


Boltzmann constant


(eV K


and 11


is an element dependent


(W sr


(see


Table


which is given by the equation 21a:


(21a)


a)Aul


where


g =the statistical weight of the upper


level,


dimensionlesss)


h =the Planck constant,


uul the
ul


(erg s) or


frequency of the transition u-l,


=the partition function of the atom,


Aul the probability of the transition ul1,


A very important aspect is the quantity,


dimensionless)


the light emitted per sr


nM and


-1),


11=(hul /4)(gu








entire


depth


the plasma.


For a radially


symmetric


plasma


at the


cen-


ter of the plasma,


the radiance,


emitted


a narrow


beam


observa-


tion


given


J(r)dr.


(22)


The complete


expression


is found


substituting


the equations


and 21


into


the equation


B=2IclP


(r)(1-8


(r))exp(-E
1


(23)


/kT
ex


where


the radial


dependence


dissociation,


ionization


and excitation


has been


indicated.


For ionic


lines,


expression


23 changes


to 24:


B=2I c
1


IR 8i(r)exp(-E
0


(24)


It is possible


to calculate


the sensitivity


with


the aid


complete


equations


23 and 24,


but ignoring


the radial


variation


of the


parameters


(see


Table


And the growth


curve


is given


in Figure


the log-log


plot.


high


the slope


1/2,


and for


slope


Under


some


circumstances


, it is logical


use the ionic


line


stead


of the atomic


line


to take


advantage


of the


high


fraction


ionized.


Experimentally


this


has been


recognized


and it


appears


that


applied


a great


number


of elements


(e.g. ,


rare


earths).


I I I I I % \


can


, Mg,


+ r


i I


I 1


|


SI *


* *


I




















C

X

3 Ln
N
**
"1 C11


N
I
CM

3 O
- r-
< X
**
- rn


CO 0
II C


C
cc
*0' Q
^r -r^

o
CO

s3- 0
O -a
COC
II CI)



-D



=3C



x ~ci
D'O
XO
11 -4.

O






**
. II
-X
4 0
-l e


A


































Figure


Growth Curve for Atomic Emission.





17















Js










/





Log nM








plasma,


such


as a change


power,


volume


ratio,


and observation


height,


must


be known;


from


a practical


analytical


point


view,


ignor-


ance


these


relevant


data


is not desirable.


- Atomic


- History


Fluorescence


of Fluorescence


Previous


Investigations.


Although


the fluorescence


atomic/ionic


vapors


was investigated


several


physicists


in the


19th


and 20th


cen-


tries


major


advances


began


1955


when


Boers,


Alkemade,


Smit


used


atomic


fluorescence


for studying


the principle


of physical


and chemical


processes


in flames.


Alkemade


also


suggested


potential


use of atomic


fluorescence


in analytical


spectroscopy.


Although


the principles


of atomic


fluorescence


have


been


known


many


years


its first


use in analytical


chemistry


for spectrochemical


analysis


was b


Winefordne r


and Vickers


1964.


Much


of the credit


for this is attributable

near's group in the U.S.A.


to two research


University


groups i

Florida)


n particular,


and West


s gr


Wineford-

oup in


England


(Imperial


College).


In atomic


fluorescence


, just


as in atomic


absorption


, the sample


atomized


and then


optical


pumping


with


a suitable


external


light


source


radiationally


excited.


Here,


however


the radiation


emitted


deactivation


excited


atoms


is usually


measured


at 90


to the incident


beam.


In atomic


fluorescence


the intensity


linearly


depends


upon


number


of excited


atoms/ions


if there


is nealiaoible


'a .,


1 f-absorotion.


I


_ _








AAS.


It has been


shown


that


the fluorescence


intensity


depends


linearly


on the excitation


source


intensity


and the quantum


efficiency


of the


transition


involved.


It should


be mentioned


that


these


linearities


are valid


only


intensity


sources,


such


as Hollow


Cathode


Lamps


(HCLs)


metal


vapor


dis-


charge


lamps


xenon


arcs,


and Electrodeless


Discharge


Lamps


(EDLs


fact


use of high


intensity


sources,


such


as tunable


lasers,


result


in a near-saturation


upper


energy


level


involved


in the


fluorescence


transition.


Because


of saturation


the fluorescence


radi-


ance


two level


atomic


system


does


not depend


on the


source


inten-


sity

tion


or quantum

is minimize


Tunable


efficiency


the corre


are fairly


lasers


the transition.

ct illumination


expensive


Furthermore,

geometry is u


are


now


useful


sel


ised.


only


f-absorp-
28-31


for slow


sequential


single


element


determination.


Therefore


laser


excited


atomic/


ionic


fluorescence


with


an inductivel


coupled


plasma


is not present


useful


analytical


tool


because


the single


element


limitation


and the


high


cost


both


sources.


However,


use of


lasers


for diagnostic


purposes


in the ICP


promising,


particularly


for profiling


the temper-


ature,


electron


density,


and velocity


of the plasma,


means


of laser-


induced


atomic/ionic


fluorescence


spectrometry.


21,3


The rf-excited


inductively


coupled


argon


plasma


operating


at 36


a maximum


power


output


of 2


was used


for the first


time


Hus-


sein


and Nickless


as an excitation


source


for atomic


fluorescence


spectrometry


in conventional


flames


with


an unsheathed


air/propane


flame








air/acetylene nitrogen-separated flame,


which will be discussed in Chap-


ter 3.


In Chapter 4,


tunable dye laser excitation with an


ICP as


atomizer/ionizer will be considered in more detail.


B.2 Theoretical Considerations


Types of Fluorescence


Transitions.


Fluorescence spectrometry is


based upon the absorption of


radiation of


a specific wavelength by an


atomic/ionic vapor and deactivation of the excited atoms/ions,


called "atomic/ionic fluorescence"'


which are


Both absorption and the measured


atomic/ionic emission processes occur at wavelengths that characterize

the atom/ion species present at the reservoir giving an excellent selec-

tivity to this phenomenon.

Resonance fluorescence occurs when excited species absorb and re-


emit radiation of the same wavelength,


i.e.,


the same two levels are in-


volved in the excitation-fluorescence processes.


is the basis for the


This type of transition


"resonance monochromator" described by Sullivan and


Walsh.


Resonance


fluorescence has been the most useful in analytical


atomic fluorescence spectrometry because resonance line intensities are

significantly greater than the intensities observed with other types of


atomic fluorescence.


A variation of


resonance


fluorescence called ther-


mally assisted resonance


fluorescence occurs when the


lower state


is not


the ground state,


but a metastable,


thermally populated state.


Direct line


fluorescence occurs when an atom or ion radiationally is


excited from the ground state to a state and then undergoes radiational


de-excitation to a lower excited state and emits a photon of


energy


less







predominant source of noise.


All non-resonance processes can be Stokes


or antistokes.

Direct line fluorescence variation called thermally assisted direct

line fluorescence occurs when the excitation process originates from a


state above the ground state;


the fluorescence process occurs to the


ground state and is an antistokes process.


Excited direct line fluorescence


involves all excited states in the


excitation and fluorescence processes;


fluorescence transition can


therefore be either Stokes or antistokes with respect to the excitation

process.


Stepwise


line fluorescence occurs when an atom or


ion is radiation-


ally excited to a state above the ground state, then is collisionally de-

excited to some intermediate state from which it then radiationally de-


activates,


and emitting a photon with lower energy


(Stokes) than that


which is absorbed.


Stepwise


line fluorescence


finds its analytical use-


fulness when excitation source scatter


is the predominant noise source


and there is no possibility for direct line fluorescence or when the


transition probabilities are not


favorable.


A thermally assisted stepwise line fluorescence variation is also


possible.


An atom or


ion is radiationally excited to some upper


level


and while it is in this excited state


(short lifetime),


it is thermally


excited to a more energetic upper state from which it


deactivates to the ground state


then radiationally


(the emission can be either Stokes or


antistokes with respect to the excitation process).








The final


type


atomic


fluorescence


is multiphoton


fluorescence.


more)-photon


absorption


will


observed


only


with


coherent


sources


The last


Figure


excitation


processes


shows


with


have


the variety


extremely


little


intense


analytical


atomic


non-coherent


usefulness


fluorescence


sources)


present.


transitions


which


described.


Several


fluorescence


processes


shown


in Figure


lb have


been


observed


with


laser


excitation


some


transition


elements.


Basic


Fluorescence


Signal


and Analytical


Curve Growth ExDress ions.


The theory


absorption


radiation


atomic


radiation


the excited


fluorescence


can be described


the atomic


atoms


vapor


and the return


in three


parts:


emission


of the sample


(fluorescence)


into


atomic


vapor


within


the volume


observation


These


relationships


well


treated


in the


literature


39-41


21.37


The radiation


absorbed


an atomic


vapor


given


sA[1


-exp


-k z)]


(24a)


where


radiance


absorbed


atomic


vapor


is the


solid


angle


of exciting


radiation


collected


upon


absorption


cell


in(sr


is the


source


spectral


radiance


in (


the atomic


absorption


coefficient


for analyte


atom


at wavelength


the length


of the


absorption


cell


(cm)


see


Figure


Evaluation


integral


after


assuming


source


type


and optical


density


leads


the following


formulas


(see


pages


Continuum


Source


Optical


Destis


When


using


the continuum


Curve


Growth


ExToo n~
L pU o -Lfl


A= A


Densities.


When


I


__


111


I


I

























Figure


atomic


uorescence


transitions
dicative of
their process
okes direct
t line fluo


e-
om).
tate
ce;
i-
okes
s-
e;
te
sted
ng
r
n);


tion
the
(D=d


pt


radiation); h
photon process
are even less


or; nvE=excit
two photon e
es involving
probable than


n wne
velen
m, s
A=acc
hvF=


xcitation
more than
the two


-fluorescence
two identical


photon


process'


, respect
tized
r; A*=
rescence


(multi-
photons
es).











































( -


i


I


(h)


~-

-
I,


1
I






3


--2


1



(1)

I
I


i____









i
(j)







- I _
i


D + hvE


--- a* a


-- A*


A + ,
--vE


3
L 3i I














































*


a


rrr
U

a)



o
0.



S

a,
U
CO


c,
U

CO
-3
U-l
0
D



*rl
0
'4
0
CD

4-i
C


0'


CH

'4j
CO


-C

(Si



-o
r





26




C.l

CD -

/J -,--- ---_^^






// //
/ //








la
1
/















/-
/ / s


^.-,^
< ^ '"'-^








BF=C2Bc


KOnM


YAXD( A/4 ) flu


(25)


where


=continuum source spectral radiance at temperature of


source and at


wavelength x

C2 =(/in2)1/2/2


(W cm


dimensionlesss)


=absorption oscillator strength


=(mc/8r e


dimensionlesss)


(26)


1.51(gu/gl)A ul
uV I ul 0


1=(11'L/A


)=absorption or emission path length (in cm)


A =211'+21L+2Ll'=total surface area of the cell
S
A ,=Einstein coefficient of spontaneous emission


Y=fluorescence quantum efficiency


(see Figure


dimensionlesss)


nM=concentration of species at lower


level


(in cm


AXD=Doppler half-width


(in nm)


QA=excitation source solid angle


K =modified absorption coefficient,
0


impinging in absorption cell


k /nflu
o M lu


(in sr)


(in cm


k =absorption coefficient
0


oM lu


for pure Doppler broadening


2
=XF /cAx C (in cm
so D 2


(in cm


o =peak absorption or emission wavelength


c=speed of light


(in nm)


(in cm


m=mass of


electron


(in g)


=source factor to account


for saturation of


energy


levels


(dimen-


sionless)


2)(gu/g )Aul O=


ire2/mc)=3.0x10-4







Line


Source


Low Optical


Densities.


When


source


half-width


is much


smaller


than


the absorption


line


width


fluorescence


line


radiance


given


BF=B K


onMYllu (A
oM lu A


'4)flu


(27)


where


=radiance


line


source


=factor


to account


finite


line


width


source


compared


absorption


line


(dimension-


ess)


the equations


describing


fluorescence


spectral


radiance


pre-


sented


so far


are involved


absorption


radiation


atoms


ground


state.


Figure


centration


the log


are called


-log


growth


plots

curves.


spectral


To convert


radiance

growth


vs atomic


curves


con-

ana-


lytical


calibration


curves


two other


terms


must


considered.


first


one relates


the second


solution


one relates


concentration


fluorescence


c to number


radiance


to detector


atoms n

output


while

signal


The relationship


c is given


nM=1019(Ra


-8i)


(28)


where


c is the concentration


of analyte


solution


in (ug/mL


solution


uptake


rate


in (


min)


the atomization


efficiency


mensionl


ess)


is the aspiration


efficiency


(dimens


ionl


ess)


flow


rate


gases


into


the flame


plasma)


L/min)


pension


factor


r/"nTT


where


are the number


moles of


ex-



























log


/ ,b


r


Sb


fa








The relation


between


the fluorescence


spectral


radiance


and the


output


signal


given


cP= 4aAA
F


syWHT
s x


BFRT


Where


the signal


in (


is the


area


of the sample


cell


in (cm


the fluorescence


spectral


radiance


in (


W and H


are the


width


height


of the


slit


, cm)


is the transmittance


of the


monochromator


wavelength


dimensionlesss),


is the spectral


band-


pass


of the monochromator


is the photodetector


sensitivity


is the electronic


transfer


function


in (


B.3 Noise


and Detection


Limits.


The signal


measurement


in an optical


spectrometer


is limited


existence


fluctuations


on the signal.


However,


the quantum


nature


the radiation


produces


fluctuations,


which


are called


"photon


noise"


more


general


"shot


noise."


Shot


noise


adds


error


to the desired


that


only


be predicted


statistical


In addition


to the shot


noises


predicted


from


statistics,


additional


fluctuations


occur


"excess


low-frequency"


noise;


such


a noise


a spectral


noise


power


inversely


proportional


to the


frequency


and is called


"flicker


noise.


cause


of these


noise


sources


can be found


in light


sources


absorb-


medium,


detectors,


and electronic


measurement


teams


used


in an op-


tical


spectrometry.


There


are two types


errors:


"systematic


errors"


which


arise


from


procedural


inconsistencies


errors


(sample


nrcnonro nnn


04- n


k ar ,l- T kirnrn ,-1


r%%\ I I I- .-


., a~- L


n 4 T


I I I


~, C,, L,,


I


*


AI-I







analytical


which


figures


reciprocal


of merit,


are "relative


signal-to-noise


ratio


standard


"limit


deviation"


of detection"


which


is the detectable


analyte


concentration


with


a certain


confidence


level;


and "the


sensitivity"


corresponding


to the slope


the analytical


calibration


curve.


The limit


of detection


is definedl9


cL-


-Xbl )
b1


dS/dc)cl
lim


=kabl


/S=(


(30)


which


link


the limit


detection


(concentration,


and the sensitiv-


, S=(dS/dc)
lim


and the


noise


level


(random


errors


in the blank,


is obtained


from


a number


or more


consecutive


readings


mea-


surements


of the blank,


i.e.


are the


average


of the blank


and standard


deviation


the blank,


and k


is a protection


factor


give


a desired


confidence


level


Lim


=k=3


is chosen


which


gives


99.86%


confidence


level).


When


one works


near


the limit


of detection,


one usually


applies


paired


readings,


the background


at t=t


and the signal-plus-back-


ground


is the


s+b'


sampling


time.


The signal


reading


corrected


background


, is given


AX=X


or in another


form


AX=x


o+ )+(dxb (t
a s b


o+r)-dxb(t
o s b


where


dx,(t


is the


statistical


fluctuation


in the meter


deflection


)-xb(t


S/N)lim(abl/S),
1im bl


s+b(t
stb








S/N=x


Ax (32)


with


(dx (t


o+~s)-dxb(t


]1/2


From


equation


variance


can


be expressed


=dx (t
b


+ dxb(t
b


- 2dx (t
b


o+r )dxb
o s b


(34)


For stationary

the time-independent


background

variance


fluctuation

of dxb(t).


, the va

In order


riance


which


to be able


compare


signal-to-noise


ratios


obtained


with


different


types


of noise


with


different


measuring


procedures


and to find


optimum


values


of the


various


characteristic


times,


one


would


take


advantage


of the relation


between


the auto-correlation


function


and the spectral


noise


power.


The auto-correlation


function


a continuously


fluctuating


signal


dx(t)


is defined


=dx(t)dx(t+T),


S=2a
Ax b


-2dxb(t
b


o+r)dxb (t
o s b


0)-iF


36()


where


)=2(


+rs)/0


x(r)),


/


I







To calculate a


, the auto-correlation function is expressed in


terms of the spectral noise power S.
b


(f) of the background current fluc-


tuations and from the Wienner-Khintchine theorem-

a,


(f)cos(2n fT


s)df,


(37)


where


(f)=S.
xib


(f) G(f)j


and G(f

Since,


)


is the frequency response of the


the noise power is a squared quanti


(linear) measuring device.

ty, only the square of the ab-


solute value of the frequency response is needed.


G(f)


Then,


we have


cos(2Trft


(38)


One would obtain the relation between the variance and the spectral


noise power


as follows:


o S.
o b


G(f) 2(1-cos(2wfT


(39)


Because cos(2nfT


sampling time r


for T


is therefore a function of the


T s0O both (ax
S AX


approach zero.


The spectral noise power


(noise power per unit


frequency


interval)


for shot noise in terms of


current


fluctuations


is given by


T )=







electron count rate in (count

as a function of frequency f


-1).


The spectral noise power considered


is called the noise spectrum.


The dimen-


sion of S.
I


is (A2


The bars denote average values.


Noise spectra for


an ICP have been evaluated in this laboratory.


The major sources of flicker noise (or


1/f noise)

and detect


excess


involve random drift of light sources,

on. The spectral noise power for flic


low-frequency noise,

analyte production,


:ker noise in terms of


current fluctuations is given by


Si)fl(f)=


2 -2
K /f)i.
j j


2 -'2
(K ./f)Rte
j J


(41)


where


is the frequency


, K. is a constant with unity dimension which
J


describes the low-frequency stability of the noise source and i. and R.

are as before.

There are peaks occurring in the noise power spectrum which are due


to oscillations


(organ-pipe)


in the plasma torch system.


They may extend


to the audible frequency range and are called "whistle noise"'


(specially


for fluorescence torch configuration).

Another source of noise existing in electrical circuits and compo-

nents but insignificant compared to the other noises when photomulti-


pliers are used,


is the "thermal


(Johnson) noise" which are due to the


random thermal motion of electrical charge carriers in any conductor.


When combining all

noise expression, care


the noises


from different origins into a total


must be taken in the method of addition.


ex-







where C is a correlation coefficient,


and its value is unity,


in the


case of


complete statistical correlations


(both have a common origin),


and its value is zero,


in the case when both noises are completely un-


correlated.


For systems which are shot noise


limited,


modulation of the signal,


regardless of the modulation frequency will not improve the signal-to-


noise ratio.


For systems which are additive


flicker noise


limited,


is necessary to "modulate" only the signal and not the background.


must keep in mind about


the suppression of "excess low-frequency noise"


that the gain in signal-to-noise ratio by modulation is limited to that


modulation frequency at which


frequencies above this limit,


shot noise


(S/N)shot

additive


x (S/N)


flicker.


At modulation


flicker noise still decreases,


is unaffected by modulation and sets a


final limit to the S/N


gain by modulation.


In conclusion, one could say


in practice the absolute magnitude of


both signal and the noise


in the signal have little use.


However,


signal-to-noise ratio can be useful and is directly related to the appli-


ability of any method for an analysis.


The signal-to-noise ratio allows


the limiting detectable concentration to be defined and is used to deter-


mine the values of the experimental parameters at which the limit of


tection as well as the maximum signal-to-noise ratio at higher concen-

trations occur.


Detection limits


(atoms per cm


of hot gases are given for AFS,


AAS and AES21


Table


The conversion factor from atoms/cm













Table


COMPARISON OF CALCULATED DETECTION LIMITS FOR SEVERAL

FLAME/PLASMA SPECTROSCOPIC METHODS21


LIMIT OF DETECTION, atoms cm
C2H2-Air H2-02-Ar ICP


ATOMIC FLUORESCENCE


Laser, Typical operating values
(x =300 nm)


Detector noise limit
Detector noise limit


2 -1
: R =102s-
SD10s1
4 -1
Ds


Background noise


limit


102
10
3x104
3x10


x104


Laser,


Saturation (x


--------- o
Detector noise limit
Detector noise limit


=300nm)


: R =10 s1
D- s
4 -1
: R =10 s
D-


2x10


2x100


Background noise limit


2x10
3x101


2x10


3x101


ATOMIC ABSORPTION (Source noise
limited o =300nm)
0


Xenon Arc Source


Hollow Cathode Discharge


4x108
7x107


8x108
1x108


4x10
7x108


ATOMIC EMISSION (Background noise
limited)


=300 nm
=600 nm


3x103







NA=Avogadro's number, atoms


(or molecules) per mole,


6.0x1023


dimension-


less


MA=atomic (molecular) weight of analyte,


g/mole


F=transport rate of sample solution as determined by nebulizer, cm


e=efficiency of nebulization and desolvation


(fraction of sample solu-


tion transported to chamber and flame which actually gets into flame


or plasma and becomes desolvated particles)

B =efficiency of vaporization of particles in


submicroscopic species,


, dimensionless

flames or plasma to produce


dimensionless


Ba=efficiency of atomization,
a


(atoms, molecules,


i.e.,


fraction of


ions) which end up


submicroscopic species


as atoms, dimensionless


Q=flow rate of unburnt gases


(at room temperature)


into


flame,


cm3/s.














CHAPTER


MOLECULAR


EMISSION


SPECTRA


AND ATOMIC


EMISSION


SPECTROMETRY


IN ICP


- Molecular


Emission


Spectra


- Introduction


rf-excited,


inductively


coupled


argon


plasma


ICP)


is becoming


increasingly


popular


as an excitation


source


for atomic


(and


ionic)


emis-


sion


spectrometry.


standing


advantages


of this


plasma


include


long-term


stability


and the


very


high


temperatures


achieved


throughout


a considerable


volume


of the


plasma.


The temperatures


appear


be suf-


ficiently


high


to bring


about


essentially


complete


decomposition


of almost


all molecules


introduced


into


plasma


in the form


aqueous


aerosols.


a result,


emission


spectroscopy


using


the ICP is relatively


free


those


types


of interference


well


known


in flame


spectroscopy


that


related


to stable


chemical


compound


formation.


various


regions


of the plasma


however,


molecules


exist


and their


emission


spectra


can


be observed.


When


an aqueous


aerosol


containing


organic


salts


is aspirated


through


the center


a toroidal


plasma,


many


processes


(desolvation,


possibly


hydrolysis,


melting,


sublimation


vaporization,


and molecule


decomposition)


take


place


in a manner


analogous








ions


in the


region


where


emission


measurements


are generally


made


25 mm)


above


the coil.


Higher


in the


plasma


oxides


are again


formed


metal


atoms


react


with


entrained


atmospheric


oxygen


with


oxygen


produced


from


water


dissociation).


Other


sources


molecular


emission


from


the plasma


include


OH emi


sion


, arising


from


incomplete


decomposition


of aspirated


water


emis-


sions


arising


from


the entrainment


atmos


pheric


gases


starting


where


the plasma


"tail


flame"


emerges


from


the plasma


torch


ssions


result-


from


atmospheric


gases


and their


reaction


products


include


those


NH and NO.


The conditions


under


which


molecular


emissions


can be


served


from


argon


plasmas


are di


scussed


in thi


chapter


Particular


tention


has been


paid


to the y-band


system


which


extends


from


nm, a wavelength


range


in which


many


elements


have


their


most


use-


emission lines.


Molecular


emissions


are also


observed


when


gases


other


than


argon


used


for plasma


flows


, such as in


nitrogen-cooled


argon


plasmas


when


organic


solvents


are aspirated


or when


various


gases


or vapors


are intro-


duced


as samples.


- Experimental


The instrumentation


used


study


described


n Table


schematic


diagram


the experimental


system


shown


in Figure


present


study


involved


the use of both


the conventional


short)


torch


a long


(for


fluorescence


studi


torch


(see


Figure


. 8


extending


ni lrn- 7


*ha lnnM


rn nil


in fhM lnnn


Fnrr'h


ml


i Y i nn


nF amhi nf


f-mns-


are


fihP


ahnvo


I












a,
I
.4-i


3
O
C u
i; 2


O 0
o n
o Cl


'.
c< '-
C


N
'-C
*H c


10 -
U^ 4 C

Or- V


O r


*- 4. 0
.C4- 0

CC
- -i '

re -


2 0 0
S--


XIr-
2 -z
022
-0 U O
iri o r
LJ W
I X
D uj a


C
CO O
0 0


SW a
050
mac
CO C
03 n
C3

OLE 2
O 0
I-or
Of
0 -
0 0
00 E
1 10
0,110
4JUI. f-^
OCa-
wtEIcf
Ia-Cd


I

-o
r
03
0 i
'r-

W fl
C
CO ^
0 0
O .



D, v
OLs.
4-i *
00 L
cUO )
003
o c
CO
-1


oE
C >E
0 C
-C ON C
03 0

ro Ec
a o


O* N
4 -O -
CO C
0M 00
OO\O


*o
03
c-
0
+J -

C
0 0


x p
>01
0 LL.
.4-
W a

o ~
0 O
C


10
,O
I-a
-CO






02
CO C
O c CD


OW N C
OX: C E "^
c1 Ca s- c
C 2N X


C 0 C

S- ON .j
I I
L Ur


Ya
- c
C
NW I

>
40 0
O3 ^
D0
O
2


I
3


C


c


H)C
O3 0
i- o




SC
-H X


00
4-il
0, -
E C
O O
e c
4J C
C 3
CO
4.)
0
S-p
-c
SC


2:































CO
03
'-I

ID
V



C
0
-4
CO
'(1
CO)
*-
E
W

C
0)
CO
03
'-4
C-



C
-4



a
I

a,


ul


C
0






S
0-I
3
'i-4
03





a
x
LUl
w






cI-
0

E
'V
'-4
03
-4
X



C 0,

OT



CO
.l

-(fl







43









O


O
0
U


CI




ff:
->w



H>
z
-o
C-































Figure


Schematic
thickness


Diagram
of 1 mm


of ICP


Torches


(all


quartz


tubing


has wall


Short
Long


(Conventional)
("Fluorescence")


Torch
Torch

















mm-.


PLASMA


(TANGENTIAL


mm ID


4 mm ID


10
nm
1u


INLET
(TANGENTIAL)


XILIARY


INLET







are of


the short


variety.


Unfortunately


mixing


ambient


occurs


where


the torch


is terminated


- Results


and Di


scussion


Molecular


Emissions


from


Unsalted


Plasmas.


The emission


from


a pure


argon


plasma


consis


ts essentially


Ar atom


lines


superimposed


on a back-


ground


continuum


due to Bremsstrahlung


and ion-electron


recombination


processes.


We have


observed


all recorded


Ar I


lines


range


340-


A weak


Truitt


Ar II line


and Robinson.


at 480.6


Most


nm has


commercial


been


argon


observed


contains


in the plasma


several


core


ug/mL


carbon


as low


molecular


-weight


hydrocarbons


CO and CO


These


traces


lead


to C


lines


193.09


nm and 247.86


but emissions


molecular


species


derived


from


these


trace


impurities


have


been


observed


only


high


-powered


plasmas


such as that


of Greenfield


Emission.


The OH molecule


the most


ubiquitous


molecular


emitter


unsalted


plasmas.


Even


when


water


is not injected


as an aeroso


"after


-flame


above


the plasma


torch


shows


emission


from


the A


band


in the vicinity


of 306.4


nm.


This is apparent


in published


background


emission


spectra


46-49


whether


water


been


injected


or not,


both


for low-powered


and for


high-powered


plasmas.


Where


no water


is aspirated


the emission


arises


from


entrained


atmo


spheric


water


vapor.


OH emission


minimized


when


no water


is aspirated


long


plasma


torch


is used


the plasma


being


observed


through


the torch


wall


made


of Spectrosil


quartz


in our case


. The


band


of the


same


tem i


usually


also


apparent


through


the wavelength


range


from


. CN)


from


I v


__








emission.


most


prominent


emission


band,


which


is at 336.0


been


reported


in the high-powered,


nitrogen-cooled


asmas


Greenfield


et al


and is recorded


as a weak


emission


in the


"after flame"


low-powered


air is introduced


observed


argon-cooled


into


NH emission


plasmas


the coolant


in an argon


NH emission


stream


plasma


also


kW Ar pi


operated


occurs


asma


at low plasma


when


We have


flow


(10-1


L/min)


at 0.55


viewed


18-20 mm


above


the induction


coil


with


ambient air


and with


air being


flushed


through


the pi


asma


pre-


vent overheating


In Figure


, spe


ctra


are given


OH and NH (


306-338


obtained


under


these


conditions


power


L/min


, and


mm ob-


servation


height)


NH has


a very


strong


sharp


branch


at 336.0


influ


ence


ambient


versus


flushed


air on the variation


the NH emission


piration)


signal


as a function


to background a

of observation


t 336 n

height


m (resulting


above


with


the load


water


coil


and for


power


level


is shown


Figure


case


the lower


power


plasma


ambient


air surrounding


the plasma


results


in a rather


sharp


maximum


whereas


flushed


air surrounding


the plasma


spreads


max-


Imum


over


about


mm.


This


is apparent


a result


of considerable


air entrainment


over


a greater


observ


ation


height


in the


latter


case


com-


pared


to the former


case


At higher


input


powers


kW in


our case


the extent


air entrainment


is greater


in both


cases


than


for lower


power


maximum


occurs


at about


same


height


25 mm),


and the


breadth


maximum


are approximat


same


in both


cases


. In













I E
*' E

C CO <
0 (- II
C S

CO



(U CL *r-t
S




6UU


*-1 **
ocrz I
(1 =i~
-IS-
cgr1-


O > **
O E
C 1Q3
O 0
'rf O
0 CI II
(U 5C 11
*rM
f Of
C DJ
cp Uc -


& Cr
O -1 II
l) C)
a,
cn u ^
0-c
1-. 4 ..
C 4C

o ca
Len *.

E *r4 1
L.U .


































Figure


NH Emission


Signal


to Background


Signal


at 336.0


nm Band


Head


vs Observation


Height.


W=25


perimental
F=2 mL/min


Conditions:
(water).


R=15


L/min;


Solid


line


Broken


line


a Air flushed


into
(hou


box (housing)


sing)


containing


containing


torch.


@ Ambient


air in box


torch.

















- -


/
I
I
I
I
I

i/
I

I/

r

i'
/


II

I/I
'\AI


I


































Figure


NH Emission
vs Nebulizer


Signal


Pressure


to Background


Signal


Experimental


at 336.0


Conditions


nm Band


same


Head


as above


training


except
torch.


z=20


mm and


air flushed


into


box (


housing)


con-







53




















10




E 9
C


\.
8-
z








O


C
C










Z

26
o



(11-






1-
h-4









UJ
or 6-


ui


^;i







nitrogen


, which


is then


passed


into


a low-powered


plasma.


Only


very


weak


NH emission


is seen


when


concentrated


ammonium


salt


solutions


are aspirated


directly


into


asma.


emission


emission


which


from


air entrainment


plasma


flame


been


noted


Truitt


and Robinson


and b


cott


Strasheim


major


bandhead


the y-band


system


NO (


at 247


the fine


structure


several


bands


can


be observed


from


-280


nm in


a plasma


operated


kW and viewed


a height


above


the coil.


In Figure


8a, spectra


are shown


in the


-band


tem of


NO (


200-280


and the


band


the A


transition


-300


obtained


under


the above


conditions


slow


scan


expanded)


the 232-248


nm region,


including


the two strongest


NO bands


shown


in Figure


and the (1,0)


band


210-21


shown


detail


in Figure


The 1


of these


bands


been


suggested


as a


possible


cause


of difficulty


in determinations


zinc


using


the Zn I


line


at 213.86


The superimposition


of this


line


on some


of the fine


struc-


ture


of the NO emi


ssion


been


noted


son


et al.


In Figure


continuum


background


spectra


are given


for 3


input


power


level


Ar emission


is observed


through


the quartz


wall


long


torch


eliminate


ambi


air entrainment.


At 0


the back-


ground


signal


is virtually


the photomultiplier


dark


current


level


With


an increase


in input


power


the background


signal


level


increases


as one


would


expect


for a "blackbody"


radiator


In Figure


the variation


NO emission (at


214.9


to background


emiss


ion (also


at 214.9


with





























Figure


Emission


pectra


(y-band)


NO and A2


Band


perimental


Conditions:


P=1 kW


L/min


z=24 mm


W=50


F=2 mL/min


Spectral


Range


of 200-280


nm Showing


y-Band


of NO and A


Band


psi;


































































WAVELENGTH






























en
0]
C

z

CM
N

a -o
0 C



a a1
C 0




ca -I

3 3
o a

<-C

ET E
C C





IrI
N C
N N
o o






0' 0'
E
C C







CO u

Cu CM
I I
CM 0








a a
-r o \




o 0
-D C
cn c
C C







CO Cu
a a


Q3 03


unJ wa



SU L
* *



-a u









58


























U
S-9
N


3









-*4
r'j
















N















MI
am








^i~






















one




M4'































Figure


Argon
Tubing
L/min;


Plasma


Long


Continuum


Torch
H=1


Background


vs X.


N=40


Observed


perimental
si; F=2 mL/


Through


Conditions:
min (Water)


Quartz


z=20


55 kW;


The dark


current


level


this


a P=1.5
studies


x 10


mm.


.0.5


-lOA)






60



















20



4
r&


18-




16-




14-




12





a ~10









6-
ts
-4-





in ,
U 1


20 10-


q
c






6-








0 iri"""- -\






-^nn 11^ IA ii ^-itt-ti*^t-.






























Figure


NO Emission


Signal


Background


Ratio


(1,0)


Band


Head


at 214.9


R=15


nm vs Obse


L/min;


o Argon


W=25


flushed


rvation


urn; H
into b


Height.


mm: N=40


(hou


sing)


Experimental
i; F=2 mL/min


containing


Conditions:


(water).


torch.


W Air flushed


A Ambient


into


air in box


box (hou


(hou


sing)


sing)


containing


containing


torch.


torch.


Key:


Solid


line


P=1 .0


Dashed


line






















1.0




0.9




0.8


0.7 -




0.6



0. -



0.4-.


-aN.


-0 C -r --


// -
S",/

I,' /
/ /


-t n- n -r -. .. -- ---


0 5 10 1S 20 25 30


* ~







reaches


a maximum


at =25


mm for


all "atmospheric


conditions


" the


maximum


having


greatest


amplitude


for ambient


air and to lowest


an Ar


flush.


Other


Molecular


Emissions


Other


emission


spectra


are readily


served


when


various


gases


, vapors


and liquids


are injected


into


the plasma


include


those


and 0


(from


oxygen


),47


and N


(from


nitrogen),


46,47


CN and C


(from


hydrocarbons


CHC1


CC14


and CO)


CO (from


aspira-


tion


of methanol


into


a nitrogen-cooled


asma)


(from


PC13)


and SO


(from


SO 2).


Molecular


Emissions


from


Salted


Plasmas


The existence


metal


oxides


both


in the central


region


a few


millimeters


above


the rf coil


in the outer


part


of the "tailflame"


at heights


of 25-50


can


be demon-


strated


clearly


aspirating


moderate


concentrated


solutions


ments


with


rather


stable


monoxides


, e.g.


1000


of Y


and Zr


In all of these


cases


the molecular


emissions


from


monoxide


appear


a different


part


of the vi


sible


spectrum


from


atom


lines


of the


same


element


is apparent


visual


observation


inductively


coupled


argon


plasma


that


at 1


east


four


rather


distinct


zones


exist


a preheating


=0-10


where


poor


analyte


atomic


or ionic


signal


background


ratios


occur


but with


a very


bright


background;


(ii)


narrow


zone


(=10


-15 mm)


where


fairly


intense


atomic


and ionic


ssion


occurs


but al


where


monoxide


emission


seen


(iii)


analytical


zone


(the


pencil


=20-30


where


ionic


and atomic


emission


measurements


are generally


made


because


the excellent


line-to-background


ratios


I t


ion


Ir *


r I --


*








depends on


a complex


fashion


upon


power


level


, plasma


gas flows,


nebulizer


pressure,


torch


configuration


, and analyte


species


Although


many


workers


use the ICP


as an emission


source


are aware


these phenomena


little


information


has appeared


in the literature


concerning


presence


lecular


mas--see


emission


above


produced


discussion)


salt


into


introduction


the ICP


well


and therefore


as unsalted


the 1


plas-


knowledge-


able


worker


might


attempt


measurement


of radiation


(especially


emission,


but also


absorption


or fluorescence)


under


conditions


where


the signal


-to-


background


ratio


is far from


optimal


In Figure


10a-f


, typical


monoxide


emission


spectra


several


species


observed


in the plume


region


(%45


are given.


It should


be stressed


that


these


spectra


are the result


aspirating


high


concentrations


specific


species


into


the plasma


and of


observations


in the plume


region


Therefore


such emission


will


rarely


affect


analytical


measurements


AEICP


Neverthel


monoxide


emissions do


occur


and workers


should


aware


existence.


In Figure


11a and


the variation


emission


signals


height


several


are shown.


than


which


species


For Y


occurs


(atomic


maximum


ionic


a higher


and molecular)


for Y(II)


height


occurs


than


with


observation


a higher


For Lu,


height


maxi


for Lu(II)


Lu(I)


occurs


was rather


a higher


height


low and constant


over


than


: the


the observation


emission


height


signal


range


10 to


- Rare


Earth


Analys


mo-


mum


mm.


I


I 1~












I
X
SLJ
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S
E
EU
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II
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IE
0\
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e t


0 0
000000 00000


000000 000000
\ O M LA 0 COOui
s~td Ol Mr f^PLFt iAn


C *
*H
EC
-JO10
Er
LIC
rO
*r


-4

0L

Ca



C


1** S
*H [J 0

Zn C
1C kCO

n E ra
15O C Q
Z Il C


*^l co E

0CO C C S M
l- > |0 s 0

*H E CD 3 I
0 ^ -f^ 0 0
(D J SO C7
a u) IC 0
I \0 C C N
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-$ il





L *"O CD
(U ^- -a c O
4 s-i .oC
- -f 0 (C V

II .- CO C
O03 O C 0
S**4 0 *5
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CJ *- 0E 0C
n as cu *
a-I c ao
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c -r C o


VC C
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OC
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x o
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c^ C r- r^^rc (jCoc csfi cD 5r


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CO C0O-
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E
SaE E
C Qa


3
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C
000
000
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Figure


10f.


Background


in 590-650


nm range.







68











10






9-






8






U 7
z
=

'C
>




<~ 6

a

z
2

- 5








33












2J
r(
3 6-







iiCf

rcl-'""""^~---5

























Figure


10b.


1000


Lu (LuO


emission


bands


in 465-475


nm range)


Background


in 465-475


nm range.


Monoxide


Band


Element


Heads


(nm)


Intensity(a)


.175
.416
.800


.231
.546
.500


,310
,270
.100


Same


as fig.


10 a,c,d






70







0!o




9-




(b)
8-






Z



4< 6

4<





z

C,,






3



(Ce)
2





I
0lr5e~~~r





























Figure


Emission Signals of Several Species


Experimental Conditions:


Same


vs Observation Height.


as Figure


500 ppm Y
o YO band head at 614.84 nm
o Y atom line at 619.17 nm.
A Y ion line at 508.74 nm.


(band head intensity=1100)
(atom line intensity=1200)
(ion line intensity=1100)






72











100



90







70-



1 60






30.0






20-
0 10












5 10 15 20 25 30 35 40 45


OBSERVATION HEIGHT (mm)































Figure


11b.


o LuO


band


head


at 466.18


(band


head


intensity=630)


e Lu atom


A Lu


line


ion line


at 500.11
at 499.41


(atom
(ion 1


lin


ine


e intensity=800)
intensity=800)











































































































































































| I. I I







spectroscopic


methods


which


have


been


extensively


used


the quantita-


tive


determination


rare


earth


metals.


Flame


spectra


rare


earth


ele-


ments


were


observed


Rains


et al.


who aspirated


non-aqueous


solutions


these


elements


into


an oxy-hydrogen


flame.


Reducing


flames


aid in


atom


production


were


used


Fassel


et al.


were


successful


in obtain-


analytically


useful


line


spectra


these


elements


in fuel


rich


flames


introducing


ethanol


solution


of the elements.


Further


studies


Mossotti


Fassel


and others


60-62


on these


elements


provided


were


over


successfully


one thousand


used


absorption


quantitative


lines


in the optical


determination


region


rare


earth


which


ele-


ments


atomic


absorption


spectrometry.


Amos


and Willis


in their


study


observed


that


when


higher


tempera-


ture


flames


were


employed


as an absorption


cell,


the degree


of ionization


rare


earths


became


significant.


Determination


of traces


rare


earths


atomic


absorption


with


electrothermal


atomization


and by


d.c.


arc emis-


sion


spectroscopy


was discussed


Dittrich


and Borzym.


Dickinson


and Fassel6


with


an ultrasonic


aerosol


generator


and de-


solvation


facility


in their


ICP determined


detection


limits


La and Ce.


Later


Fassel


and Kniseley


reported


detection


limits


rare


earths


which


were


superior


to those


from


flames.


Souilliart


and Robin


used


high


power


(6.6


ICP and ultrasonic


nebulizer


in the study


rare


earth


metals.


In this


study,


we have


used


a conventional


moderate


power


.25-


ICP with


a glass


concentric


pneumatic


nebulizer


for the determina-


tion


detection


limits


(LOD)


and linear


dynamic


ranges


(LDR)


rare







- Experimental


Preparation


Standards.


Individual


stock


solutions


1000


ug/mL


each


rare


earth


element


as well


as mixtures


elements


were


pre-


pared


dissolving


reagent


grade


pure


oxides


(ignited


at 6000C


4 hr)


in hot 3


M HC1.


Successive


dilutions


were


made


before


each


determination


using


distilled-deionized


water


A solution


hydrochloric


acid


ioni


water


was used


as the


blank.


Apparatus


Instrumental


given


Figure


and a 2


ductively


radio


coupled


frequency


plasma


generator


(Plasma T

was used


herm


Kresson


in conjunction


with


with


a glass


a 27 MHz

concentric


neublizer.


The nebulizer


solution


flow


rate


was controlled


with


a syringe


pump


Instruments,


Div.


Orion


Research


Inc.,


Cambridge


list


major


instrumental


components


the ICP


stem


used


in thi


study


given


n Table


Limits


detection


(LOD)


and linear


dynamic


ranges


(LDR)


were


measured


integrating


the electrometer


signal


was taken


that


concentration


equivalent


a signal


three


times


that


the standard


deviation


of 16


consecutive,


integrated


blank


readings.


Experimental


Conditions.


The plasma


was operated


argon


flows


specified


the manufacturer


The ICP


power


was maintained


.25-


throughout


all measurements


the nebuli


zer


solution


flow


rate


maintained


2.2 mL


and the cooling


was controlled


16-20


-1 A
A


spherical


lens (image


placed


in a 3"


metal


tube


, was used


to focus


emission


beam


to the monochromator


entrance


slit.


was














Table


SPECIFIC


COMPONENT


OF EXPERIMENTAL


SYSTEM


Component


Model


Company


Torch


asse


mbly


Plasma


Therm


Kresson


RF Generator


HFP-


500D


Nebulizer


T-220-A2


Meinhard


Associates


Santa


Anna,


Monochromator


1870


SPEX,


Metuchen


Photomultiplier


R-818


Hamamatsu


Corp.


Middl


esex


High


voltage


power


supply


eithly


Instruments,


Clev


eland,


Current


voltage


convertor


Keithly


Instruments


, Cleveland,


Integrator


Lab Constructed







observation


height


could


be adjusted


with


respect


to the


monochromator


optimum


plasma


observation


height


was found


to be


mm above


the load


coil


of the ICP.


- Results


and Discussion


The observed


detection


limits


and linear


dynamic


ranges


rare


earth


elements


with


the lines


used


for measurement


(also


energies


of level


values


are given)


are summarized


in Table


The linear


dynamic


ranges


were


obtained


measuring


the relative


emission


signals


selected


anal


ysis


lines


vs concentration


metal


ions in solution.


analytical


cali-


bration


curves


are linear


over


a concentration


range


s5 orders


mag-


nitude for

calibration


a


11 of

curves


the elements


for La,


being


, Dy


studied.


As representative


and' Lu


are presented


examples,

in Figures


Comparison


of the results


of this


work


with


that


of other


authors


indicates


that


the condition


employed


study


have


resulted


simi


lar or better


limits


of detection


as others


reported


in the literature


13,66


It i


clear


from


the LODs obtained


in the mixture


elements


that


matrix


interference


are negligible


in the ICP


In the present


intense


analytical


studies


, only


ion lines


measurements


rare


were

earth


found

metal


to be


sufficiently


Ion lines


(see


Table


were


selected


on the basi


maximum


of intensity


minimum


spectral


interference


and background


The detection


limits


obtained


study


in pure


or superior


aqueous


to those


3,66


solutions


reported


or rare

in two


earth

previo


mixtures a

us studies


re similar

of ICP exci










O

E
cia

Cu

*H


C (.
Cc
Co

CD
-J
*I


03


O








C~3x
S0 w-

u .
0*






Q -
.. X

I
V


C













.j)
0 c








31C
I<
ClO0
















-J






'It
*P (U











EcD




>) Y



33



r

I E


0 O


N O\


ON\
I
c m

OM
iu i


f^ r\
CM a\



* *


Nor-

0 00 M
r^l F<~
CM CMCMV
NC'.c'
I I I
COC


r\OO

r r


v- 00

cj \o
\ J \O
rr-rfl

4 II
I L\ fM
r^ M r


I r\ lu
ONCN
* *
\a CM Vn











































































O r-






SN*
0r-c


CM CN
SO O


I I
SC







0 O
*\ *































Figure


Analytical


Calibration


Curves


for Lanthanum


and Cerium.


* single


element


x in mixture



































LOb'


" GLOO


10 1' 10 103 104 105 1


ANALYTE


CONCENTRATION


(ng. mi)































Figure


Analytical


Calibration


Curves


Europium


and Dysprosium.


* single


element


x in mixture



































LOD f


/-0LO D


S10 1 104 10 106


ANALYTE


CON CENTRATION


(ng. ml'')































Figure


Analytical Calibration Curves for Holmium and Lutetium.


* single element
x in mixture





86






10







10

S3. Ho
10- x
SyxLU


, I


i 10
LOD Q /

LOODx
1i b5 o1' 1o2 3 ioi io5 160
ANALYTE CONCENTRATION (ng. ml")















CHAPTER THREE

ATOMIC FLUORESCENCE SPECTROMETRY
IN THE FLAME USING ICP AS A NEW EXCITATION
SOURCE "ICP-EXCITED FASF"


- ICP Diagnostics Using the


ICP-Excited Flame AFS


- Introduction


Many physical parameters of the inductively coupled plasma


(ICP)


source


for analytical spectroscopy have been investigated.


review by Barnes


contains an extensive list of


The recent


references covering fun-


damental operating principles and methodologies.


several elements fc

by Human and Scott,


ometer to obtain the p


Emission profiles of


>r several experimental conditions have been reported


who used a pressure-scanning Fabry-Perot interfer-

rofiles. These authors concluded that the spectral


profiles of the lines emitted for the elements investigated


(Ca, Sr, Ar)


depended upon the height of

tion and self-reversal were


observation and that,


observed at certain he


although self-absorp-

ights, these phenomena


did not occur for a range of


at least three orders of magnitude (1-1000


pg/mL)


indicating the excellent characteristics of the


ICP as an emission


source.

This work reports preliminary results showing how several limiting


characteristics of the


ICP emission profiles can be derived if the


ICP is


I __ ___ ___ _1 ~_ ~_


II








suitable


monochromator


mixture


70-73


flame.


This


Therefore


procedure


the flame


is capable


acts


as a resonance


providing


in a very


simple


way qualitative


but unequivocal


information


about


the line


profile


the ICP


emission


without


sophi


sticat


instrumentation


such as high


resolution


monochromators


Fabry-Perot


interferometers.


These


latter


approaches


are the only


ones


giving


complete


quantitative


information


about


the true


line


profiles.


However


, the fluorescence


technique


only


clearly


detects


self-absorption,


is especially


sensitive


cipient


self-reversal


emission


line


profile.


This information


is obtained


from


the experimental


log-log


plot


three


curves


growth


the first


one


is the excitation


curve


growth,


in which


a fixed


concentration


used


the flame


while


increasing


concentrations


are aspirated


into


the flame


acts


as a


resonance


monochromator);


second


fluorescence


curve


growth


, (i.e.,


conventional


curve


growth


obtained


with


a fixed


high)


concentration


a selected


element


in the ICP


while


aspirating


increasing


concentrations


of the


same


element


into


the flame


and the


third


one


is the


common


emission


curve


of growth


which


emiss


from


the ICP is


directly


plotted


vs the concentration


of the analyte


The results


obtained


for the elements


, Mg


and Ca verify


pected


behavior


these


curves.


- Theoretical


Considerations


_








in which


integral


is extended


over


the entire


absorption


line


width


(i.e.,


width


over


which


k (x)
f


differs


markedly


from


zero).


Here


terminology


as follows:


= spectral


irradiance


of the ICP as a function


of wavelength


a given


height


and at


a given


analyte


concentration,


evaluated


at wavelength


a (x)


= fraction


radiation


absorbed


any wavelength


dimension-


less;


kf(x)


= absorption


coefficient


of analyte


atoms


in the flame,


usually


given


product


(peak


absorption


coefficient


purely


tion


Doppler
m-1 for
m : for


broadened


a given


profile)


resonance


and the Voigt


line


and under


profile


given


func-


condi-


tions


and flame


temperature,


is proportional


flame


atomic


concentration


over


all the absorption


line,


all values


= interaction


spectral


length


irradiance


for the absorption


the ICP


process


can


in the flame,


be regarded


as the


exe


product


of the blackbody


spectral


irradiance


at the wavelength


considered


and at the ICP emission


temperature


and the total


absorption


factor


which


a function


of the concentration


in the ICP


and of its emission


depth


in the direction


flame.


When th

fluorescence


e interaction


emission


process i

the flame,


.s studied


then


means


the fluorescence


of the resulting


radiance


cm.








BFa4s
abs


1-exp[-k (x)L}dX


exc


41-exp[-kf(x)f] dx / ~C


k (x)dx] ja


(45)


abs


(X) 1-exp[-k (x)L]dX{[A (n ff)]/[C


Equation 45 is equal to Equation 44 multiplied by a term which takes into

account the self-absorption of the fluorescence radiation leaving the


flame.


Here,


At(n i)


1-exp[-kf(x)z] d),


is the total absorption fac-


tor for the fluorescence radiation in the flame, nf is the flame atomic


concentration,


and t is the


(homogeneous)


fluorescence depth.


Equation


45 simplifies


for the two usual limiting cases of line and continuum ex-


citation sources and for negligible fluorescence self-absorption.


fact,


if nf is low,


then the second factor at


the right hand side of


Equation 45 is unity.


If the


ICP acts as a spectral line source,


ered constant and equal


to its peak value,


maxf


the kf(X) can be consid-

Equation 45 then re-


duces to Equation 46.


BF~~ -exp[-k
F


maxf


L]} E


(x)dx


(46)


exc


Thus the


ICP may act as a line source if


its overall spectral emission


profile is narrower than the absorption profile


in the flame,


even though


its higher temperature would cause the Doppler halfwidth to be larger


than that in the flame by a


factor of


approximately the square root of


Iabs


k (A)dx]










BF,:E


1l-exp[1-kf(x)L]IdX~aE


o)At(nfL)


(47)


in which


is the constant


irradiance


of the


over


the absorp-


tion


line


profile.


Therefore,


when


the interaction


between


the ICP


emission


and the


resonance


absorption


profile


in the flame


is monitored


the fluorescence


emitted


from


a constant


concentration


of flame


atoms,


a slope


of unity


concentrations


in the ICP and a limiting


__


concentrations


in the ICP


should


be obtained.


This


limiting


zero


slope


will


hold,


irrespective


of the amount


of self-absorption,


as long


as self-


reversal


does


not affect


emission


profile.


When


this


happens,


i.e.,


when


the ICP emission


profile


starts


showing


a dip


in the center,


this


will


negative


slope


be reflected


will


immediately


be observed


in the fluorescence


in the experimental


signal


plot.


On the other


tainted


hand


aspirating


the ICP-excited


the flame


fluorescence


increasing


curve


concentrations


of growth


analyte


should


give


the following


information:


if the asymptote


at high


a slope


near


-0.5


then


ICP,


like


at that


a line


particular


source,


height


i.e.,


and atom


spectral


density


profile


behaves


narrower


than


the absorption


profile


in the flame:


(ii)


when


self-absorption


is large


in the


ICP emission,


this


curve

1.. tt^ n s


of growth

S A ,r, t i .


should

4Lt. J- A-


approach


I -


a region
- C_ 1 -


zero


i L I


slope,


.I 1


slooe


r of h i q h


zero


El









These


results


which


are summarized


Table


can


be obtained


from


Equations


45-47


, by


assuming


that


the self-absorption


factor


for the fluo-


rescence


cannot


be considered


negligible


and remembering


that


At(nfL)


At(nrf)

values.


vary


linearly


with


at low


values


and with


at high


- Experimental


Figure


shows


the experimental


arrangement


used.


The ICP


source


(ICP


1500


Plasma


Therm.,


Inc.,


Kresson


was focused


on the


aper


ture


a chopper


and subsequently


onto


the flame


means


spherical


quartz


lenses.


order


to minimi


pre-


and post-filter


effects


a rec-


tangularly


shaped


burner


was used


care


taken


to optimize


properly


illumination

possible inh


and observation


omogeneities


geometries.


in temperature


Furthermore, i

and composition,


n order


the flame


avoid

was


shielded


another


similar


flame


which


could


in turn


be surrounded


an inert


flow.


The fluorescence


was collected


a spherical


quartz


lens and di-


rected


onto


the entrance


slit


a small


monochromator


(Jobin-Yvon


, H-10,


reciprocal


linear


dispersion);


the slit


width


and height


were


unless


otherwise


stated


at 50


mm, respectively.


The out-


signal


a photomultiplier


(Hamamatsu


was fed


a lock-in


plifier


(840


Autolock


, Keithley


Cleve


land


Ohio)


then


a chart


corder.


For the emission


measurements


the ICP


image


was focused


directly


onto


the entrance


slit


on a 0.35-m


monochromator


reciprocal


re-




Full Text
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ATOMIC EMISSION
AND ATOMIC FLUORESCENCE SPECTROMETRY
IN INDUCTIVELY COUPLED PLASMA
BY
SEIFOLLAH NIKDEL
A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL
OE THE UNIVERSITY OF FLORIDA IN
PARTIAL FULFILLMENT OF THE REQUIREMENTS
FOR THE DEGREE OF DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1979

EDUCATION FOR INDEPENDENT THOUGHT
It is not enough to teach man a specialty. Through it he may be¬
come a kind of useful machine but not a harmoniously developed person¬
ality. It is essential that the student acquire an understanding of and
a lively feeling for values. He must acquire a vivid sense of the beau¬
tiful and of the morally good. Otherwise he—with his specialized
knowledge—more closely resembles a well-trained dog than a harmoniously
developed person. He must learn to understand the motives of human
beings, their illusions, and their sufferings in order to acquire a
proper relationship to individual fellow-men and to the community.
ALBERT EINSTEIN
From New York Times
October 5, 1952

DEDICATION
This dissertation is sincerely dedicated to my wife, Christine Nik-
del, and my mother, who have given me their love and encouraged me to
obtain the endless knowledge within higher education. In their debt I
will always be.

ACKNOWLEDGEMENTS
I wish to take this opportunity to express my regard to the friends
and colleagues who, through their interest and discussions, helped make
this time pass so easily. I like to take particular pleasure in express¬
ing special gratitude to my research director, Graduate Research Profes¬
sor Dr. James D. Winefordner, for his constant sincerity, his steady
guidance, and kindly inspiration throughout this work.
Special thanks to Drs. N. Omenetto, M. S. Epstein, and R. D. Reeves
for their valuable help during the course of this work.
I extend my appreciation to the University of Florida Graduate
School for the financial support during this time.
And, the patient comprehension and love of my wife Christine in
typing the first draft of this dissertation has made this effort worth
while. Her continuous cheerfulness and undeniable sacrifices offered
inspiration when it was most needed.
IV

TABLE OF CONTENTS
Page
ACKNOWLEDGEMENTS iv
ABSTRACT vii
CHAPTER
ONE INTRODUCTION 1
A - Atomic Emission 1
A.1 - History of the ICP 1
A.2 - Theory and Mechanism of Excitation
in ICP 3
A.3 - Sensitivity and Growth Curve in ICP 8
B - Atomic Fluorescence 18
B.1 - History 18
B.2 - Theoretical Considerations 20
B.3 - Noise and Detection Limit 31
TWO MOLECULAR EMISSION SPECTRA AND ATOMIC
EMISSION SPECTROMETRY IN ICP 39
A - Molecular Emission Spectra 39
A.1 - Introduction 39
A.2 - Experimental 40
A.3 - Results and Discussion 46
B - Rare Earths Analysis 64
3.1 - Introduction 64
B.2 - Experimental 76
B.3 - Results and Discussion 78
THREE ATOMIC FLUORESCENCE SPECTROMETRY IN THE FLAME
USING ICP AS A NEW EXCITATION SOURCE "ICP-
EXCITED FASF" 87
A - ICP Diagnostics Using the ICP-Excited FAFS.... 87
A.1 - Introduction 87
A. 2 - Theoretical Considerations 88
A.3 - Experimental 92
A.4 - Results and Discussion 96
A. 5 - Detection Limits 108
B - Detection Limits and Real Sample Analysis
Using ICP-Excited Flame AFS 109
v

Page
B.1 - Introduction 109
B.2 - Experimental 110
B.3 - Results and Discussion 116
B.4 - Applications 128
FOUR ATOMIC FLUORESCENCE SPECTROMETRY IN ICP WITH
DYE LASER EXCITATION "LASER-EXCITED AFS IN ICP" 135
A - cw Dye Laser as an Excitation Source in ICP... 135
A.1 - Introduction 135
A.2 - Experimental 136
A.3 - Results and Discussion 141
B - Relative Spatial Profiles of Barium Ion
and Atom in the Argon Inductively Coupled
Plasma as Obtained by Laser Excited
Fluorescence 155
B.1 - Introduction 155
B.2 - Experimental 158
B.3 - Results and Discussion 163
C - Pulsed Dye Laser as an Excitation Source
in ICP 207
C.1 - Introduction 207
C.2 - Experimental 209
C.3 - Results and Discussion 209
FIVE CONCLUSIONS AND FUTURE WORK ON INDUCTIVELY
COUPLED PLASMA EITHER AS AT0M/I0N CELL OR AS
AN EXCITATION SOURCE 218
REFERENCES 225
BIOGRAPHICAL SKETCH 231
vi

Abstract of Dissertation Presented to the Graduate Council
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
ATOMIC EMISSION AND ATOMIC FLUORESCENCE
SPECTROMETRY IN INDUCTIVELY COUPLED PLASMA
By
Seifollah Nikdel
December, 1979
Chairman: James Dudley Winefordner
Major Department: Chemistry
Molecular emission spectra of native species ( OH, NO, and NH) in the
argon inductively coupled plasma (ICP) have been studied as a function of
height in the plasma, input power, and adjacent environment to the plasma.
Similar studies were carried out with an ICP into which is introduced
moderately concentrated solutions of elements forming stable monoxides,
such as Sc, Y, Gd, and Lu.
Using a medium power (1.25-1.5 kW) ICP as an excitation source for
atomic emission spectrometry with a glass concentric nebulizer, aqueous
solutions of rare earth elements in pure solution and combined mixture of
all the rare earth elements are measured except Pm. Analytical lines and
ICP characteristics for such measurements are given.
The characteristics of the emission line profiles of Ca, Zn, and Mg
in the inductively coupled plasma discharge were investigated by means of
atomic fluorescence spectrometry. The combination of the experimentally
obtained excitation and fluorescence curves of growth allowed the self-
absorption and self-reversal effects on the emitted profiles to be
vii

qualitatively detected. In such measurements the flame is used as a reso¬
nance detector. The results show that self-absorption, while present, is
not severe and that self-reversal is absent in the observation zones com¬
monly used for analytical measurements. Furthermore, the use of the ICP
as excitation source in flame atomic fluorescence spectrometry permitted
low limits of detection to be achieved with a simple experimental set-up.
An inductively-coupled argon plasma (ICP) is used as a narrow line
radiation source for the excitation of atomic fluorescence in several
analytically useful flames (nitrogen-separated air/acetylene and nitrous-
oxide/acetylene). Detection limits for 14 elements are compared to atomic
fluorescence detection limits using other radiation sources and to those
of other atomic spectrometric techniques. Dominant noise sources which
limit measurement precision at low and high concentrations and the sig¬
nificance of and correction for the scatter problem are discussed. The
reduction of spectral interference observed in ICP-emission is demonstrated
for the determination of zinc in unalloyed copper (NBS SRM-394 and 396).
The technique is also applied to the determination of zinc in fly ash
(NBS SRM-1633), cadmium and zinc in simulated fresh water (NBS SRM-1643),
and copper and zinc in orange juice.
Atomic/ionic fluorescence in the ICP using a cw dye laser as an ex¬
citation source has been studied. Detection limits for elements such as
Ba, Na, Li, and V are given. Also the results show the non-Local Thermo¬
dynamic Equilibrium excitation conditions in our low powered ICP.
Relative ionic and atomic fluorescence profiles for barium have been
obtained in an argon inductively coupled plasma by exciting different
transitions with a nitrogen-laser pumped tunable dye laser and measuring
the resulting fluorescence pulses with a boxcar averager. Spatially re¬
solved profiles are directly obtained without the need of an Abel inversion
viii

procedure, with a volume resolution of approximately 0.2 mm\ The profiles
are given along the excitation axis as well as along the observation axis,
for different heights above the coil and different input powers. At low
heights, the ion profile resembles a hollow pencil with a typical double-
peaked, asymmetric distribution, while the atom profile seems to be com¬
plementary to the ion profile. Some scatter from water is also evident
at low heights. By tuning the laser at two excitation transitions shar¬
ing a common upper level, the temperature of the plasma could be evalu¬
ated .
The atomic and ionic fluorescences of iron, tin, barium and indium
excited by flashlamp- and nitrogen laser-pumped pulsed dye lasers in the
inductively coupled plasma (ICP) are studied. Noise sources are investi¬
gated and detectability is compared to the techniques of ICP-emission and
laser-excited atomic fluorescence spectrometry.
IX

CHAPTER ONE
INTRODUCTION
A - Atomic Emission
A.1 - History of the ICP
Early developments of electrodeless discharges. The low-pressure
electrodeless discharge has been known since 1884. It was discovered
first by Hittorf in experiments on the conduction of electricity through
the noble gases.
2
Mavrodineanu and Hughes" traced the rf-excitation of low-pressure
gases for spectrochemical analysis to the work of Tesla in 1891. Then,
Thomson,^ in 1927 published his experimental results along with the
theory of the electrodeless discharge expressing the magnetic and elec¬
tric field spatial distributions by Bessel functions, assuming constant
r.
plasma conductivity across the column. Later Babat, in 1942, discov¬
ered that a ring discharge can be maintained while the pressure is in¬
creased up to atmospheric level. Thus, Babat is the inventor of the
modern day inductively coupled plasma discharge. However, the major in¬
terest developed only after Reed^ successfully showed that one can pro¬
duce an "Induction Torch" where the plasma is observable above the torch
and is useful as a heat source.
The discovery of stabilized induction heated plasmas operated at
atmospheric pressure with flowing gases through an open-ended tube by
Reed, has led to two major applications: first as an induction-arc for
i

engineers, and second as a spectrochemical excitation source for ana¬
lytical chemists.
The main reason for the delay in developing a stable Inductively
Coupled Plasma (ICP) after Babat's publication was the design of a re¬
liable method of cooling and heat protection of the plasma. Water-
cooled walls, water jackets, and porous dielectric walls were applied,
but Reed's approach to a gas cooling system has proven most effective
and is now universally accepted for spectrochemical applications.
Reed's work showed three attractive properties for the plasmas which
were (i) high gas temperature, (ii) capability of being sustained in
noble gas environments (important from free-atom lifetime consideration),
and (iii) freedom from contamination by electrodes, which were not re¬
quired .
After Reed, two groups (Greenfield et al.^ and Wendt and Fassel')
independently investigated the potential use of induction-heated plasmas
as an excitation source (i.e. vaporization, dissociation, decomposition
cells, free atom/icn reservoir) for atomic emission spectrometry.
Fassel and co-workers studied a great number of variables for de-
7-10
veloping an analytically useful ICP system. Until 1969, Fassel and
his group had experienced problems introducing samples into the high
10
temperature zone of the plasmas. At that time Fassel and Dickinson
were able to "punch a hole" through the center of the plasma by intro¬
ducing high velocity carrier gas in the sample injector. However, this
11
same solution had been used since 1964 by Greenfield et_ al_. in England.
J Trace analysis. The aim of analytical chemistry has been described
as the chemical characterization of a sample in general and to introduce
1
improved methods for this characterization. It has been stated that the'
requirements for an ideal elemental technique are (i) to give unbiased

3
results, (ii) to be sensitive and give low detection limits, (iii) need no
sample pretreatment, (iv) to cover a broad range of elements (i.e. ideally
measure all elements in the periodic table), (v) to possess a large dy¬
namic concentration range, and (vi) to allow simultaneous multi-element
determination.
Looking to the field of instrumental analysis, the optical tech¬
niques seem to be the most appropriate for analytical purposes. They
are favored for their speed, ease of operation, as well as simple sample
pretreatment. The possibilities of handling many samples, of giving high
sensitivity, and of determining numerous elements simultaneously are the
other important characteristics relating to this field.
The inductively coupled radio-frequency argon plasma (ICP), being
an extremely efficient atomic/ionic emission source, has multi-element
capability and the high gas kinetic temperature makes it less susceptible
to the chemical interferences than lower temperature sources such as
12
flames. (In general, chemical effects are less than 10%.) The pre¬
cision is comparable to flame atomic absorption (1-5%). The reported
13
linear dynamic range approaches the capabilities of modern electronic
equipment, which are indeed needed to take advantage of this feature,
and exceeds the linear dynamic range of flame atomic absorption consid¬
erably.
The limits of detection reported most widely in the literature for
V
emission spectrometry with the ICP usually lie in the range of 0.01-
14
10 ng/mL and are one to three orders of magnitude lower than with high
15
temperature flames in emission spectrometry.
A.2 - Theory and Mechanism of Excitation in the ICP
The principle of spectral analysis is based on the following prin¬
ciples: conversion of the element under study in the sample to the gas

4
phase by the excitation source, i.e. concentration in condensed phase to
atoms or ions per unit volume in the gas phase c+n^; transition of a
certain number of these atoms/ions from the ground state to the excited
■¥r
state (or metastable state) M-*-M ; conversion of the excitation energy
*
into the spectral line radiation M -nM+hv; selection of the radiation of
the specific line from the total radiation of the source by the spectral
instrument and its transformation by the recording system into a measur¬
able signal from the line under study (e.g. photomultiplier photocurrent
in case of photoelectric recording etc.)*
A unit volume of the luminous source contains n.. atoms or ions of
M
the analyte. The elementary phenomenon leading to the excitation of
ground state atoms/ions and the quenching of the excited atoms/ions
*
) are rather varied. These are collisions of atoms/ions with free
electrons and heavy particles, atoms, ions, electrons and molecules of
the gas in the source, as well as, in some cases, chemical reactions
with the participation of M atoms/ions.
In practical spectral analysis, resonance lines of atoms/ions,
corresponding to the transition from the nearest excited level to the
ground state are often measured. In sources with a high concentration of
electrons, e.g., in plasmas, the basic phenomenon which lead to the ex¬
citation of resonance levels and also to atomization/ionization are col¬
lisions with electrons. Collisions with heavy particles are less effec-
16
tive.
In the rf-excited, inductively coupled argon plasma, the population
(concentration) of excited states and degree of ionization exceeds the
values that correspond to the 3oltzmann-Saha expression and this depar¬
ture from LTE is postulated to be due to the influence of argon metas-
1 ó 17
table atoms. ’ Consider a volume element AV in the center of the ICP

5
at a given height (»15 mm) above the induction coil. Let us assume that
LTE conditions (T«6000 K) in AV are disturbed by the creation of an over¬
population of argon metastable atoms (outside of AV) and representing
this by a net inflow of metastables from the surroundings to aV. This
-3 -1
inflow has a rate constant k (cm s ) and its value deoends on exter-
m
nally controllable factors such as power input in the coil region (energy
addition region), the plasma gas flow conditions, type of ICP (two-flow
argon ICP or a three-flow ICP with nitrogen as the plasma gas and argon
as the carrier and auxiliary gas), and the height of aV from the induc¬
tion coil.
16 18
Conservation of energy, charge and mass balance require ’ (i) a
net outflow of argon ions (Ar+) and electrons from the coil region having
-3 -1
a rate constant k^(cm s ) for ambipolar diffusion; (ii) a net outflow
of argon atoms (Ar) in the ground state from the coil region having a
-3 -1
rate constant k (cm s ) for diffusion; and (iii) the following in-
3
terrelationships to apply
and
k.=(V /V.)k =0.73
i m i m
k =1-k
m ó
(1)
k =1-(V /V.)k =0.27 k =1-k.,
a m i m m i
(2)
where is the weighted average excitation potential of the metastable
atoms at 6000 K (V =11.58 eV), the ionization potential of argon
(V^=15.76 eV), and k^ is the rate constant of the inflow of argon metas¬
table atoms from their surroundings to the volume aV.
The ionization of metastable argon atoms and argon atoms by electron
impact and the reverse three-body recombination reactions occur within
the volume AV, are given by equations 3 and 4 (metastable argon atom acts

6
as an ionizant, i.e. as an early ionizable constituent, eq. 3, and as an
ionizer, eq. 3a, having assigned the "dual role"):
k12
Ar^ + e | Ar+ + 2e, (3)
Ar •+• M
m
+ e + Ar ,
(3a)
and
'34
Ar + e
Ar + 2e.
(4)
43
These rate constants are interrelated, for local thermodynamic con¬
ditions, by:
KAr =k12y/|<71 ’ S 1//cm6
m
:5)
and
KAr=k34//k43’ t'CrT’3 s_1)‘
(6)
where K^r and are the Saha equilibrium constants in (cm defined
m
by:
KAr =nAr+ne/nAr ’ (cm~3 cm_3/cm"3)
m m
=4.03x1O15(a»-3 K -3/2) T3/2 (Z./g ) 10(-5040(Ei-Em)/T)
i m
(7)
and
KAr=nAr+ne/nftr' (cr""3 cra"3/cra‘3>
=A.83x1033(cm-3 K-3/2) T3/2 (Z./g ) !0<-5040Ei/T>
1 0
(3)
where is the partition function of Ar+ (dimensionless); T the absolute
temperature (K); g^ and gQ are the statistical weights for metastable

7
argon and ground state argon (dimensionless); E (eV) the excitation
energy of the relevant metastable level; E^(eV) the excitation energy
of argon.
For a steady state of the rate equation for Ar+ and electrons from
equations 3 and 4, one would obtain the following:
dn, /dt=0=k +kOAn. n -k._n. n ,
Ar+ m 21 Ar+ e 12 Ar e’
m
(9:
and
¿7
dn /dt=0=k„on, n +k,.nA n -k„.n. n -k.,n. n -k..
e 12 Ar e 34 Ar e 21 Ar+ e 43 Ar+ e i
(10)
Using the quasi-neutrality condition, ng=n^r+, combining the equations
1, 9, and 10 would give:
n -KA nA n -0.27(k /k/7)=0.
e Ar Ar e m 43
(11)
The general solution of equation 11 is an expression for ng in terms of
both K„ and k /k.,. Two special cases are of interest in the ICP:
Ar m 43 K
,15
(a) k /k,, »K. nA n , this applies to an ICP; when T=600Q K, n «10 -10
m 43 Ar Ar e’ ’ ’ e
cm ^, in which the second term in equation 11 is negligible compared
to n^ and therefore:
e
1 /7
n =(0.27 k /k,,) ' , (non-LTE),
e m 43
(12)
(b) for k =0, equation 11 yields the Saha value of n :
m e
V(KArnAr)1/2> (13)
This model can describe a range of conditions between non-LTE (eq.
12) and complete LTE (eq. 13). The non-LTE model involving a mechanism
in which metastable argon acts as both an ionizer and ionizant appears
16

8
to be a useful postulate, as it permits a qualitative understanding of
the high sensitivity of ionic lines, the high electron number density,
and the negligible ionization interferences observed in ICP's under op¬
timum operating conditions.
A.3 - Sensitivity and Growth Curve in ICP
Four analytical figures of merit of an atomic emission spectrometer
are: the sensitivity, the signal-to-noise ratio, the line to background
ratio, and the detection limit. The detection limit is usually expressed
as the concentration which produces a signal equal to three times of the
19
standard deviation of the blank. The standard deviation in the blank
is a difficult quantity to predict theoretically. Neglecting the noise
in the detection system, the following noise sources can be considered
in emission ICP studies: source flicker noise, variation in the aerosol
production, in the solvent evaporization, and in the volatilization of
the dry particles, and instabilities of the plasma (electrical or fluid
dynamic).
The ICP has the properties of a dynamic source in common with the
arc and the flame. It has a stationary high temperature zone (coil re¬
gion 10000 K) in a fast flowing gas stream maintained by forced and/or
free convection. Sample material injected into the gas stream quickly
passes into the high temperature zone. Nevertheless, the ICP, as an ex¬
citation source, has several disadvantages:
(a) concentration of the element in the condensed phase and the
atom/ion population in the excitation zone in the gas phase do not have
a known unique relationship; they are function of the analyte solution
uptake flow rate and of the carrier gas velocity in the source as well
as the plasma characteristics; (b) analyte injection is not efficient,

9
and so it has to be supplied at a low constant rate for maintaining a
steady signal; also material that has been injected into the source can
not be used for further investigation and observation; (c) incomplete
mixing, unstable flow and turbulence introduce fluctuations in signal
and background, which raise the detection limit; and (d) it is almost
impossible to understand the detailed performance of a dynamic source
because of the transient nature and the interdependence of the mixing,
heating, dissociation, excitation, and ionization processes to which the
analyte is subjected, combined with the non-uniform velocity and temper¬
ature fields of the source.
The sensitivity, S, which is generally defined in analytical chem¬
istry as the change of the signal per unit change of the analyte concen¬
tration is inversely related to the detection limit. For a linear cali¬
bration curve, it is the slope of this curve, which relates, in its
_2
simplest algebraic expression (eq. 14), the line radiance, B, in (W cm
-1 -3
sr ) with the analyte concentration n^ in the gas phase (cm ). It is
clear that to convert solute concentrations to emission of light a great
number of intermediate physical processes are needed.
B=SnM (14)
In order to inject the sample solution to the plasma, a means of
transport is needed. Thus, the solution is transported up by a nebulizer
and is converted into a fine spray of droplets. The larger droplets fall
into the drain tube and the smaller droplets are carried away to the
plasma with carrier gas, which also drives the nebulizer. The ratio of
the volume of droplets which remain in the carrier gas and those origi¬
nally taken up is called the efficiency of the nebulizer (en> in our
case, is «0.10).

10
Actually the amount of liquid delivered per unit time (2.5 mL/min)
is diluted by the carrier gas per unit time (0.5 L/min) by a factor of
V/V =0.005. The smaller droplets are introduced into the high tempera¬
ture zone of the plasma. The solvent, which is usually water, evaporates
and carrier gas, by the free jet expansion model, expands with a factor
Tg/y where T^ is the kinetic gas temperature and Tr is room tempera¬
ture.
The fraction of the solvent in the droplets that can be evaporated
depends on the kinetic gas temperature gradient, which the droplets must
always pass before reaching the observation zone. Also the droplet size
distribution is important, because complete evaporation of large droplets
takes more time than small ones. This transit time is related to the
linear velocity of the carrier gas, the temperature gradient as well as
the droplet size and composition, because expansion of the gas will re¬
duce the velocity. In the literature, no experimental results are avail¬
able to locate the height in the plasma, where all droplets are just
20
evaporated. However, similar experiments in flames suggest that sol¬
vent evaporation will be completed rapidly in the ICP.
The next step is volatization, in which a high kinetic gas temper¬
ature is needed to disintegrate the particle. If only analyte is in¬
jected, the dry particles will be very small. However, if an excess of
another salt as a matrix is present, the dry particles will be larger.
The boiling point of this salt can deviate greatly from that of the salt
of the analyte. Thus, the amount of analyte released in the presence of
a matrix is different from that without the matrix. This could produce
a different signal level, which is generally called a chemical/physical
interference effect.

11
As the solid particles are transported deeper into the plasma (the
high temperature zone), their temperature will rise and start to boil and
come into the gas phase state. At this point the relationship between
the solution concentration, c, and the total vapor concentration, n^., of
analyte species has been established. From here on, the most important
processes are dissociation, ionization and excitation, which are all tem¬
perature (and time) dependent.
Let us consider each process separately, when the molecules of the
original salt are in the gas phase, they will dissociate into free atoms.
Because the solvent is water, the oxygen atoms from dissociation of water,
could react with the free analyte atoms to form substantial monoxide spe¬
cies which has been observed for stable monoxides such as rare earths in
this laboratory and will be shown in Chapter 2. The equilibrium can be
shown as follows:
MO
M+0.
(15)
The degree of atomization Sa can be calculated as follows:
nT=n,,+n.K .—nnn,./n..ri
T M MO’ d 0 M MO
(15a)
sa=nM/(nM + "mO^/'VV’
(16)
20
where according to Boumans, , the equilibrium constant, can be calcu¬
lated from eq. 17:
uk \ c ,n24 ,n(-5040E ,/T ,)
Kd=nM/(n0+nM0)ai5x10 10 d d ’
:17)
where n's are denoted to the particle densities, T^ is the dissociation tem¬
perature (K) and E^ the dissociation energy in (eV) (see Table 1). Because

12
water is completely dissociated, the value for is the same as the
number density of water molecules introduced by the nebulizer into the
, , -n16 -3
plasma, i.e. 5x10 cm
The next important gas phase process is ionization, which is com¬
parable to the dissociation except that the products are ions and elec¬
trons. The degree of ionization is defined in the same manner. Because
here we are interested in atoms only, the expression for (1-6^) is used,
i.e. the fraction of elemental species not ionized
1-6.=n /(n
l M M
nM+)=n,y + K. ),
M e e i
(18)
where K. is the Saha constant, and its numerical form is
i ’
K.=4.83x1015
i
T.3/2(Z./Z n )
1 18 6
10v
-5040E./T.)
1 1 >
(19)
where T^ is the ionization temperature in (K), is the ionization
energy in (eV), Z^ and Zg are the partition functions for ion and atom
(dimensionless). The result for (1-s^) is shown in Table 1.
By combining these processes and assuming complete volatilization,
the relation between the solute concentration and the free atom number
21
density in the plasma can be expressed as
nM=cpC8a(1_Bi)’
(20a)
and for ion is given by
nM+=cpcSi,
(20b)
-3 -1
where 9 is the conversion factor in (atoms cm /yg ml ), and is given by
-6 -
,=(VV(Vvq)(Tr/T„)(10 >v
(20c)
with

13
23
N^=Avogadro's number, atoms (molecules) per mole, 6.0x10 (dimen¬
sionless); M^ratcmic (molecular) weight of analyte, (g/mole), n^ and c
are in (cm and (yg/mL), respectively.
The next important process in the gas phase is excitation, which is
the process which transfers the atoms/ions from the ground state to the
excited state. Upon returning to the ground state light is emitted,
which the relation of emitted light and total number density of free
atoms is given by:
J=IlnMexp(-Eex/kTex), (21)
where Egx is the excitation potential in (eV), Tgx is the excitation
-3 -1
temperature (K), J the emittance expressed in (W cm Sr ), k is the
-1 -1
Boltzmann constant (eV K ), and 1^ is an element dependent (W sr ),
(see Table 1), which is given by the equation 21a:
I,=ChUul/4„)(gu/Za)Aul, (21a)
where
g^rthe statistical weight of the upper level, (dimensionless)
2
h =the Planck constant, (erg s) or (W s )
*
uui=the frequency of the transition u+1, (s ')
Z -the partition function of the atom, (dimensionless)
A =the probability of the transition u->-l, (s ).
A very important aspect is the quantity, B, the light emitted per sr
per area element in the plasma source. However, when the intensity is
measured, the detector receives its light from many different volume ele¬
ments as far as they fall within the observation zone of the optics. In
fact, the light emitted along the line of sight is collected over the

14
entire depth of the plasma. For a radially symmetric plasma at the cen¬
ter of the plasma, the radiance, B, emitted by a narrow beam of observa¬
tion given by:
,R
B=2 J J(r)dr. (22)
o
The complete expression is found by substituting the equations 20
and 21 into the equation 22:
B=2I1c

J 3 1 6X SX
0
where the radial dependence of dissociation, ionization and excitation
has been indicated. For ionic lines, expression 23 changes to 24:
8=21.0 fR 6. (r)exp(-E /kT )dr. (24)
I J 1 SX S X
o
It is possible to calculate the sensitivity, S, with the aid of the
complete equations 23 and 24, but ignoring the radial variation of the
parameters (see Table 1). And the growth curve is given in Figure 1 in
the log-log plot. For high n^, the slope is 1/2, and for low n^, the
slope is 1.
Under some circumstances, it is logical to use the ionic line in¬
stead of the atomic line to take advantage of the high fraction ionized.
Experimentally this has been recognized and it appears that it can be
applied to a great number of elements (e.g., Ba, Mg, Fe, Mo, Nb, Pd, Ti,
V, W, Ca, and rare earths).
In conclusion, it can be mentioned that (i) the fundamental param¬
eters which determine the sensitivity in the ICP should be known, in
order to optimize the analysis to obtain the best results; and (ii) the
dependence of these parameters upon a change of operating conditions in

Table 1
CALCULATED VALUE OE SENSITIVITY IN ICP
Data
Element
Na
Ca
Zn
X
(nm)
508.99
422.67
213.06
*1
(W si' )
5.92x10-1<4
3.75x10~13
2.52x10-1
E
ex
(eV)
2.1Ü
2.93
5.80
Ed
(eV)
3.90 (Na Gil)
4.7(CaO)
4.0 (ZnO)
E.
i
(eV)
5.14
6.11
9.09
expi-E^/kT^)
T = 5000l<
ex
7.6x10~3
1.1x10~3
1.4x10-6
0a
T ,=4000K
d
1.00
0.99
1.00
T ,=5000K
d
1.00
1.00
1.00
(1-e.)
T.=5000K
i
0.65
0.82
1.00
1
T.=8000K
i
0.01
0.01
0.44
S=R/nM
M
(W cm sr ^
LTE: T =
ex
non-LTE: T =
ex
) LTE 6.1x10-21
non-LTE 1.1x10-22
T ,=T. =5000 K
d i
5000 K; T .=4000 K; T.=8000 K
d ’ i
-21
7.2x10
-22
1.1x10
-23
7.1x10
-23
3.9x10 z
ex=excitation, d=dissociation and i=ionization

Figure 1. Growth Curve for Atomic Emission.

Log B

18
the plasma, such as a change in power, gas volume ratio, and observation
height, must be known; from a practical analytical point of view, ignor¬
ance of these relevant data is not desirable.
B - Atomic Fluorescence
B.1 - History of Fluorescence
Previous Investigations. Although the fluorescence of atomic/ionic
vapors was investigated by several physicists in the 19th and 20th cen-
22
turies;- the major advances began in 1955, when Boers, Alkemade, and
23
Smit“ used atomic fluorescence for studying the principle of physical
and chemical processes in flames. Alkemade also suggested the potential
use of atomic fluorescence in analytical spectroscopy.
Although the principles of atomic fluorescence have been known for
many years, its first use in analytical chemistry for spectrochemical
24
analysis was by Winefordner and Vickers in 1964. Much of the credit
for this is attributable to two research groups in particular, Wineford-
ner's group in the U.S.A. (University of Florida) and West's group in
England (Imperial College).
In atomic fluorescence, just as in atomic absorption, the sample is
atomized and then by optical pumping with a suitable external light source
25-27
radiationally excited. Here, however the radiation emitted by the
deactivation of excited atoms is usually measured at 90° to the incident
beam. In atomic fluorescence the intensity linearly depends upon the
number of excited atoms/ions if there is negligible self-absorption.
Since the fluorescence intensity from the excited species is controlled
by the intensity of the exciting source, the intensity of this source
(within the absorption profile) is much more important in AFS than in

19
AAS. It has been shown that the fluorescence intensity depends linearly
on the excitation source intensity and the quantum efficiency of the
transition involved.
It should be mentioned that these linearities are valid only for low
intensity sources, such as Hollow Cathode Lamps (HCLs) metal vapor dis¬
charge lamps, xenon arcs, and Electrodeless Discharge Lamps (EDLs). In
fact the use of high intensity sources, such as tunable dye lasers, may
result in a near-saturation of the upper energy level involved in the
fluorescence transition. Because of saturation, the fluorescence radi¬
ance (for two level atomic system) does not depend on the source inten¬
sity or quantum efficiency of the transition. Furthermore, self-absorp-
28—31
tion is minimized if the correct illumination geometry is used.
Tunable dye lasers are fairly expensive and are now useful only for slow
sequential single element determination. Therefore, laser excited atomic/
ionic fluorescence with an inductively coupled plasma is not presently a
useful analytical tool because of the single element limitation and the
high cost of both sources. However, the use of lasers for diagnostic
purposes in the ICP is promising, particularly for profiling the temper¬
ature, electron density, and velocity of the plasma, by means of laser-
21 32 33
induced atomic/ionic fluorescence spectrometry. ’ ’
The rf-excited inductively coupled argon plasma operating at 36 MHz
and a maximum power output of 2.5 kW was used for the first time by Hus¬
sein and Nickless^ as an excitation source for atomic fluorescence
spectrometry in conventional flames with an unsheathed air/propane flame
as atomizer, and introducing 1000-4000 ug/mL metal solutions as source
material into the plasma.^ Since then, no other research has been done
on the use of ICP-excited flame atomic fluorescence spectrometry until
we investigated this excellent source for use as an excitation source in

20
air/acetylene nitrogen-separated flame, which will be discussed in Chap¬
ter 3. In Chapter 4, tunable dye laser excitation with an ICP as
atomizer/ionizer will be considered in more detail.
B.2 - Theoretical Considerations
Types of Fluorescence Transitions. Fluorescence spectrometry is
based upon the absorption of radiation of a specific wavelength by an
atomic/ionic vapor and deactivation of the excited atoms/ions, which are
called "atomic/ionic fluorescence". Both absorption and the measured
atomic/ionic emission processes occur at wavelengths that characterize
the atom/ion species present at the reservoir giving an excellent selec¬
tivity to this phenomenon.
Resonance fluorescence occurs when excited species absorb and re¬
emit radiation of the same wavelength, i.e., the same two levels are in¬
volved in the excitation-fluorescence processes. This type of transition
is the basis for the "resonance monochromator" described by Sullivan and
Walsh.Resonance fluorescence has been the most useful in analytical
atomic fluorescence spectrometry because resonance line intensities are
significantly greater than the intensities observed with other types of
atomic fluorescence. A variation of resonance fluorescence called ther¬
mally assisted resonance fluorescence occurs when the lower state is not
the ground state, but a metastable, thermally populated state.
Direct line fluorescence occurs when an atom or ion radiationally is
excited from the ground state to a state and then undergoes radiational
de-excitation to a lower excited state and emits a photon of energy less
than that which it absorbed (Stokes process).
Direct line fluorescence is most useful analytically when the scat¬
ter of source radiation, by particles within the atomizer, is the

21
predominant source of noise. All non-resonance processes can be Stokes
or antistokes.
Direct line fluorescence variation called thermally assisted direct
line fluorescence occurs when the excitation process originates from a
state above the ground state; the fluorescence process occurs to the
ground state and is an antistokes process.
Excited direct line fluorescence involves all excited states in the
excitation and fluorescence processes; the fluorescence transition can
therefore be either Stokes or antistokes with respect to the excitation
process.
Stepwise line fluorescence occurs when an atom or ion is radiation-
ally excited to a state above the ground state, then is collisionally de-
excited to some intermediate state from which it then radiationally de¬
activates, and emitting a photon with lower energy (Stokes) than that
which is absorbed. Stepwise line fluorescence finds its analytical use¬
fulness when excitation source scatter is the predominant noise source
and there is no possibility for direct line fluorescence or when the
transition probabilities are not favorable.
A thermally assisted stepwise line fluorescence variation is also
possible. An atom or ion is radiationally excited to some upper level
and while it is in this excited state (short lifetime), it is thermally
excited to a more energetic upper state from which it then radiationally
deactivates to the ground state (the emission can be either Stokes or
antistokes with respect to the excitation process).
Sensitized fluorescence occurs when one species, called the donor,
is excited and transfers excitation energy to an atom of the same or an¬
other species, called the acceptor, either of which de-excites radiation¬
ally.

22
The final type of atomic fluorescence is multiphoton fluorescence.
Two (or more)-photon absorption will be observed only with coherent
sources of excitation (or with extremely intense non-coherent sources).
The last two processes have little analytical usefulness at present.
Figure 2a shows the variety of atomic fluorescence transitions which are
described. Several fluorescence processes shown in Figure 1b have been
37-39
observed with laser excitation of some transition elements.
Basic Fluorescence Signal and Analytical Curve of Growth Expressions.
The theory of atomic fluorescence can be described in three parts: the
absorption of radiation by the atomic vapor, the emission (fluorescence)
of radiation by the excited atoms and the return of the sample into the
atomic vapor within the volume of observation. These relationships are
39-41 21 37
well treated in the literature. ’ ’
The radiation absorbed by an atomic vapor is given by
GO
Ba=(«a/47T) / BsA^1-exp('-kXil^ dA (24a)
o
-2 -1
where is radiance absorbed by atomic vapor in (W cm sr ), is the
solid angle of exciting radiation collected upon the absorption cell
_2 -1 -1
in(sr), B is the source spectral radiance in (W cm sr nm ), k is
S A A
the atomic absorption coefficient for analyte atom at wavelength X, and
I is the length of the absorption cell in (cm) (see Figure 2b).
Evaluation of the integral after assuming the source type and optical
density leads to the following formulas (see pages 27 and 28).
Continuum Source at Low Optical Densities. When using the continuum
source (or broad line source), the source half-width is assumed to be
wider than the absorption line width (source intensity over the absorp¬
tion line width is constant). The fluorescence line radiance is given
by

Figure 2a. Types of atomic fluorescence transitions (the spacings be¬
tween atomic levels is not indicative of any specific atom),
a, resonance fluorescence (either process); b, excited state
resonance fluorescence; c, Stokes direct line fluorescence;
d, excited state Stokes direct line fluorescence; e, anti¬
stokes direct line fluorescence; f, excited state antistokes
direct line fluorescence; g, Stokes stepwise line fluores¬
cence; h, excited state Stokes stepwise line fluorescence;
i, antistokes stepwise line fluorescence; j, excited state
antistokes stepwise line fluorescence; k, thermally assisted
Stokes or antistokes stepwise line fluorescence (depending
upon whether the absorbed radiation has shorter or longer
wavelengths, respectively, than the fluorescent radiation);
1, excited state thermally assisted Stokes or antistokes
stepwise line fluorescence (depending upon whether the ab¬
sorbed radiation has shorter or longer wavelengths, respec¬
tively, than the fluorescence radiation); m, sensitized
fluorescence (D=donor; D*=excited donor; A=acceptor; A*=
excited acceptor; hvr=exciting radiation; hvr=fluorescence
t r
radiation); h, two photon excitation-fluorescence (multi¬
photon processes involving more than two identical photons
are even less probable than the two photon processes).

24
(b)
2
O
(c
(d)
2
J
(9)
P )
i )
(?)
(h)
(i)
3
2
â–  1
0
( j)
5
2
0
k
3
2
1
0
(1)
—
—
.
' 1
4.
3
2
0
(m)
D + byâ„¢ -D*
Hi
D * + A —- A * D
A * __ 4 + V»
A — A „.vE
(n)
HYPOTHETICAL
0

Figure 2b. Schematic Diagram of Atomic Fluorescence Sample Cell.

EXCITATION
i
1
n
EMISSION
B
B
F
SLIT
hO
ON

27
BF=C2BcA KOnM YlAXD(V4^)flu (25)
o
where
B ^continuum source spectral radiance at temperature of source and at
0 -2 -1 -1
wavelength A (W cm sr nm )
o
C7 = ( ’r/ln2)-'//2/2 (dimensionless)
fx absorption oscillator strength (dimensionless)
= (mc/8Tr2e2)(gu/gl)AulA2 = 1.51(gu/gl)AulA2 (26)
1=(11'L/A )=absorption or emission path length (in cm)
A =211'+21L+2L1'=total surface area of the cell (see Figure 2)
A ^=Einstein coefficient of spontaneous emission (in s )
Y=fluorescence guantum efficiency (dimensionless)
n^rconcentration of species at lower level (in cm ^)
AAp=Doppler half-width (in nm)
P^=excitation source solid angle impinging in absorption cell (in sr)
2
K =modified absorption coefficient, k /n..f, (in cm^)
o r ’ o M lu
kQ=absorption coefficient for pure Doppler broadening
=K nMf, =XF A2/caa C,(in cm ^)
o M lu so D 2
X=( ire^/mc)=3• 0x10 4 (in cm2 s ^)
AQ=peak absorption or emission wavelength (in nm)
_1
c=speed of light (in cm s )
m=mass of electron (in g)
Fs=source factor to account for saturation of energy levels (dimen¬
sionless )
The guantum efficiency of a transition is defined by Y=A ^/(A ^+K), where
A is the emission transition probability, and K is the probability of
radiationless transitions.

28
Line Source at Low Optical Densities. When the source half-width
is much smaller than the absorption line width, the fluorescence line
radiance is given by
Br=B. K nMYl<5, (i2A/4ir)f.
F L o M lu A lu
(27)
where
B^=radiance of line source, (W cm “ sr nm ); á^rfactor to account for
finite line width of source compared to absorption line (dimension¬
less) .
All the equations describing fluorescence spectral radiance pre¬
sented so far are involved in absorption of radiation by atoms in the
ground state.
In Figure 3, the log-log plots of spectral radiance vs atomic con¬
centration are called growth curves. To convert growth curves to ana¬
lytical calibration curves, two other terms must be considered. The
first one relates solution concentration c to number of atoms n., while
the second one relates fluorescence radiance to detector output signal.
The relationship of n^ and c is given by
n =1019(RB c e/Q f )(1-8.) g /Z (28)
M a n e i o
where c is the concentration of analyte solution in (yg/mL), R is the
solution uptake rate in (mL/min), 8 is the atomization efficiency (di-
3
mensionless), en is the aspiration efficiency (dimensionless), Q is the
flow rate of gases into the flame (plasma) in (L/min), f is the gas ex¬
pansion factor (n T /riTT , where n and nT are the number of moles of
r r I g r r
flame gases at room temperature T^ and gas temperature, T ), gQ is the
statistical weight of the ground state, and Z is the electronic parti¬
tion function Z=g +g exp (-E /kJ)...).
o m m

v*l
o

31
The relation between the fluorescence spectral radiance and the
output signal is given by
$¡-=4itAA yWHT A 6,-RT (29)
i S A S r I
2
Where $p is the signal in (V), Ag is the area of the sample cell in (cm ),
-2 -1
Bp is the fluorescence spectral radiance in (W cm sr ), W and H are the
width and height of the slit (cm, cm), T is the transmittance of the
A
monochromator at wavelength \ (dimensionless), is the spectral band¬
pass of the monochromator (nm), y is the photodetector sensitivity in
-1 -1
(AW ), and is the electronic transfer function in (V A ).
B.3 - Noise and Detection Limits.
The signal measurement in an optical spectrometer is limited by the
existence of fluctuations on the signal. However, the quantum nature of
the radiation produces fluctuations, which are called "photon noise", or
more generally "shot noise." Shot noise adds error to the desired sig¬
nal, that may only be predicted statistically. In addition to the shot
noises predicted from statistics, additional fluctuations occur due to
"excess low-frequency" noise; such a noise has a spectral noise power
inversely proportional to the frequency and is called "flicker noise."
The cause of these noise sources can be found in light sources, absorb¬
ing medium, detectors, and electronic measurement systems used in an op¬
tical spectrometry. There are two types of errors: (i) "systematic
errors" which arise from procedural inconsistencies and errors (sample
preparation, etc.), background, stray light, detector offset, etc. and
could be corrected by blank subtraction, modulation, calibration, etc.
and (ii) "random errors" which result from reading and digitizing errors
which can be minimized by improved experimental technique.

32
The analytical figures of merit, are "relative standard deviation"
which is the reciprocal of signal-to-noise ratio; "limit of detection"
which is the detectable analyte concentration with a certain confidence
level; and "the sensitivity" corresponding to the slope of the analytical
calibration curve.
19
The limit of detection is defined by
c. = (x. -7. )/(dS/dc) =ka. ,/S=(S/N), . (a, ,/S), (30
L L bi c. . bl lim bl
lim
which link the limit of detection (concentration, c^) and the sensitiv¬
ity, S=(dS/dc) , and the noise level (random errors) in the blank,
Clim
is obtained from a number (16 or more consecutive readings) of mea¬
surements of the blank, i.e. x^ and are the average of the blank
and standard deviation of the blank, and k is a protection factor to give
a desired confidence level ((S/N). . =k=3 is chosen which qives 99.86?á
Lim
confidence level).
When one works near the limit of detection, one usually applies
paired readings, the background, x^, at t=t and the signal-plus-back¬
ground, xg+k> t=tQ+Ts; ts is the sampling time. The signal reading
corrected for background, ax, is given by^
or in another form
Ax=x , (t +T )-x. (t )
s+b os bo
(31)
AX = X (t +T ) + (dx, (t +T )-dx, (t ))
sos bos bo
where dx, (t) is the statistical fluctuation in the meter deflection or
b
integrator output due to the background alone. The signal-to-noise is

33
(32)
with
(33)
From equation 33 the variance can be expressed as
(34)
For stationary background fluctuation, the variance is o^, which is
the time-independent variance of dx^(t). In order to be able to compare
the signal-to-noise ratios obtained with different types of noise and
with different measuring procedures, and to find optimum values of the
various characteristic times, one would take advantage of the relation
between the auto-correlation function and the spectral noise power.
The auto-correlation function of a continuously fluctuating signal
, v 42
dx(t) is defined by
Â¥ (-r)=dx(t)dx(t+T),
(35)
and so
(360
where
2 2
b’
and

34
2
To calculate cr'^, the auto-correlation function is expressed in
terms of the spectral noise power S. (f) of the background current fluc-
tuations and from the Wienner-Khintchine theorem-
*x(x ) = / Sx(f)cos(2irft )df, (37)
o
where
S(f)=S. (f) | G(f)| ,
X Xb
and G(f) is the frequency response of the (linear) measuring device.
Since, the noise power is a squared quantity, only the square of the ab¬
solute value of the frequency response is needed. Then, we have
(x )= f S. (f)IG(f)|2cos(2xfx )df.
: s J i, 1 1 s
o b
(33)
One would obtain the relation between the variance and the spectral
noise power as follows:
o2 =2 fS. (f) G(f)|2(1-cos(2xfx ) )df.
AX j 1, 1 S
(39)
o b
Because cos(2iTfx ) = 1, for x =0, a is therefore a function of the
s s ax
sampling time x ; and as x -*-0 both a and x approach zero.
S S AX s
The spectral noise power (noise power per unit frequency interval)
for shot noise in terms of current fluctuations is given by
n _ n _ ?
(S.),(f).=S =2e z i-=2 £ R.eZ
1 sh 10 j=i j j=i j
(40)
where e is the elementary charge in (C), i. is the j-th component in the
0
current, emitted e.g. by a photocathode in (A), and R. is the corresponding

35
electron count rate in (counts s ). The spectral noise power considered
as a function of frequency f is called the noise spectrum. The dimen-
sion of is (A“s). The bars denote average values. Noise spectra for
an ICP have been evaluated in this laboratory.
The major sources of flicker noise (or excess low-frequency noise,
1/f noise) involve random drift of light sources, analyte production,
and detection. The spectral noise power for flicker noise in terms of
current fluctuations is given by
(S ) (f)= 2 (K2/f)I2= z (K2/f)R2e2 (41)
j=1 J J j=1 J J
2
where f is the frequency, K . is a constant with unity dimension which
J
describes the low-frequency stability of the noise source and i . and R .
I 1
are as before.
There are peaks occurring in the noise power spectrum which are due
to oscillations (organ-pipe) in the plasma torch system. They may extend
to the audible frequency range and are called "whistle noise" (specially
for fluorescence torch configuration).
Another source of noise existing in electrical circuits and compo¬
nents but insignificant compared to the other noises when photomulti¬
pliers are used, is the "thermal (Johnson) noise" which are due to the
random thermal motion of electrical charge carriers in any conductor.
When combining all the noises from different origins into a total
noise expression, care must be taken in the method of addition. For ex¬
ample, if two noises with r.m.s. values ag and exist together, the
r.m.s.-value of the total noise a-p is given by
1/2
2 2
aT=(a +a, +2Ca a, )
T a b a b
(42)

36
where C is a correlation coefficient, and its value is unity, in the
case of complete statistical correlations (both have a common origin),
and its value is zero, in the case when both noises are completely un¬
correlated .
For systems which are shot noise limited, modulation of the signal,
regardless of the modulation frequency will not improve the signal-to-
noise ratio. For systems which are additive flicker noise limited, it
is necessary to "modulate" only the signal and not the background. One
must keep in mind about the suppression of "excess low-frequency noise"
that the gain in signal-to-noise ratio by modulation is limited to that
modulation frequency at which (S/N) ^ ^ » (S/N) flicker. At modulation
frequencies above this limit, additive flicker noise still decreases, but
shot noise is unaffected by modulation and sets a final limit to the S/N
gain by modulation.
In conclusion, one could say, in practice the absolute magnitude of
both signal and the noise in the signal have little use. However, the
signal-to-noise ratio can be useful and is directly related to the appli¬
cability of any method for an analysis. The signal-to-noise ratio allows
the limiting detectable concentration to be defined and is used to deter¬
mine the values of the experimental parameters at which the limit of de¬
tection as well as the maximum signal-to-noise ratio at higher concen¬
trations occur.
Detection limits (atoms per cm^) of hot gases are given for AFS,
21 3
AAS and AES in Table 2. The conversion factor from atoms/cm to
ug/ml_ is given by
I n D V 3 I M
where

37
Table 2
COMPARISON OF CALCULATED DETECTION LIMITS FOR SEVERAL
FLAME/PLASMA SPECTROSCOPIC METHODS21
LIMIT OF DETECTION, atoms cm
C2H2-Air H2-02-Ar ICP
ATOMIC FLUORESCENCE
Laser, Typical operating values
(\ =300 nm)
o
— 2-1
Detector noise limit : Rn=10_s
— 4 -1
Detector noise limit : Rp=10 s
Background noise limit
Laser, Saturation (x =300nm)
0 — 2-1
Detector noise limit : Rn=10 s
— 4 -1
Detector noise limit : R^=10 s
Background noise limit
ATOMIC ABSORPTION (Source noise
limited - X =300nm)
o
Xenon Arc Source
Hollow Cathode Discharge
ATOMIC EMISSION (Background noise
limited)
X =300 nm
o
X =600 nm
o
?
10¿
102
2
10z
„3
3
3
10
10
10
105
3x104
3x10
2x10“1
2x10-1
2x10
2x10°
2x10°
2x10
102
X
o
3x10
4x108
8x108
4x10
7x107
X>
o
X
T—
7x10
10
10
10
105
104
3x10
4
-1
0
1
9
8
3

38
?3
N^rAvogadro's number, atoms (or molecules) per mole, 6.0x10“ , dimension¬
less
M^=atomic (molecular) weight of analyte, g/mole
F=transport rate of sample solution as determined by nebulizer, cm'Vs
e=efficiency of nebulization and desolvation (fraction of sample solu¬
tion transported to chamber and flame which actually gets into flame
or plasma and becomes desolvated particles), dimensionless
8v=efficiency of vaporization of particles in flames or plasma to produce
submicroscopic species, dimensionless
S =efficiency of atomization, i.e., fraction of submicroscopic species
(atoms, molecules, ions) which end up as atoms, dimensionless
Q=flow rate of unburnt gases (at room temperature) into flame, cm /s.

CHAPTER TWO
MOLECULAR EMISSION SPECTRA
AND ATOMIC EMISSION SPECTROMETRY IN ICP
A - Molecular Emission Spectra
A.1 - Introduction
The rf-excited, inductively coupled argon plasma (ICP) is becoming
increasingly popular as an excitation source for atomic (and ionic) emis¬
sion spectrometry. Outstanding advantages of this plasma include its
long-term stability, and the very high temperatures achieved throughout
a considerable volume of the plasma. The temperatures appear to be suf¬
ficiently high to bring about essentially complete decomposition of almost
all molecules introduced into the plasma in the form of aqueous aerosols.
As a result, emission spectroscopy using the ICP is relatively free of
those types of interferences well known in flame spectroscopy, that are
43
related to stable chemical compound formation.
In various regions of the plasma, however, molecules exist and their
emission spectra can be observed. When an aqueous aerosol containing in¬
organic salts is aspirated through the center of a toroidal plasma, many
processes (desolvation, possibly hydrolysis, melting, sublimation and
vaporization, and molecule decomposition) take place in a manner analogous
to that occurring in flames, except that argon plasmas contain a much
lower concentration of oxygenated species than do most analytical flames.
Metal monoxides appear to exist briefly in the center of the plasma for
some distance above the rf coil before decomposing into metal atoms and
39

40
ions in the region where emission measurements are generally made (» 15 to
25 mm) above the coil. Higher in the plasma, oxides are again formed as
metal atoms react with entrained atmospheric oxygen (or with the oxygen
produced from water dissociation).
Other sources of molecular emission from the plasma include OH emis¬
sion, arising from incomplete decomposition of aspirated water, and emis¬
sions arising from the entrainment of atmospheric gases, starting where
the plasma "tail flame" emerges from the plasma torch. Emissions result¬
ing from atmospheric gases and their reaction products include those of
N£, N+, NH and NO. The conditions under which molecular emissions can be
observed from argon plasmas are discussed in this chapter. Particular at¬
tention has been paid to the y-band system of NO, which extends from 200
to 280 nm, a wavelength range in which many elements have their most use¬
ful emission lines.
Molecular emissions are also observed when gases other than argon are
used for plasma gas flows, such as in nitrogen-cooled argon plasmas, when
organic solvents are aspirated, or when various gases or vapors are intro¬
duced as samples.
A. 2 - Experimental
The instrumentation used in this study is described in Table 3. A
schematic diagram of the experimental system is shown in Figure 4. The
present study involved the use of both the conventional (short) torch and
a long (for fluorescence studies) torch (see Figure 5). By extending the
quartz tube above the load coil in the long torch, mixing of ambient atmos¬
phere with the plasma is eliminated and cooling of the plasma due to the
mixing is also reduced. The upper end of the long torch becomes cloudy
with use and causes transmission losses where observations of emission are
made below the end of the quartz tube. Therefore, conventional torches

Table 3
INSTRUMENTATION AND EXPERIMENTAL PARAMETERS
USED IN THE PRESENT STUDIES
Component
Model, Manufacturer
Parameters
ICP Torch Assembly
Generator
Pt-1500 Torch Assembly and
HFP-1500D RE Generator
Plasma Therm, Inc., Kresson,
NJ 08053
0.55-1.5 kW
10-16 L/min Ar Plasma (coolant)
gas flow
<0.5 L/min Ar auxiliary gas flow rate
ICP Short Torch
Laboratory Constructed -
(see Figure 5)
ICP Long Torch
Laboratory Constructed -
(see Figure 5)
ICP Nebulizer
Concentric
Ring Glass - T 220 - A2
J. E. Meinhard Assoc., Santa Anna,
CA 92705
40 psi (20 mL/min Solution Uptake Rate)
<1 L/min Ar gas flow rate
Monochromator
E-700 Monochromator, Heath Co.,
Benton Harbor, MI 49022
(0.35 m, f/6.8, 1100 grooves
1mm, Glazes at 250 nm, 2nm/mm)
1 mm slit height
25 mm slit width
(0.05 nm spectral handpass)
Photomultiplier
R-920, Hamamatsu TV Corp.,
Ltd., Middlesex, NJ 08046
-1000 V
Current-to-VoItage
Converter
Model 427, Keithley Instrument Co.,
Cleveland, OH 44139
Recorder
Model Potentiometric, Texas Instru¬
ment, Houston, TX 77006

Figure 4. Schematic Diagram of Experimental Set-up Used in present Emission Studies.

LENS

Figure 5. Schematic Diagram of ICP Torches (all quartz tubing has wall
thickness of 1 mm).
A. Short (Conventional) Torch
B. Long ("Fluorescence") Torch

oo
45
A
B

46
are of the short variety. Unfortunately, mixing of ambient air occurs
44
where the torch is terminated.
A,3 - Results and Discussion
Molecular Emissions from Unsalted Plasmas. The emission from a pure
argon plasma consists essentially of Ar atom lines superimposed on a back¬
ground continuum due to Bremsstrahlung and ion-electron recombination
43
processes. We have observed all recorded Ar I lines in the range 340-
600 nm. A weak Ar II line at 480.6 nm has been observed in the plasma core
by Truitt and Robinson.4^ Most commercial argon contains several yg/ml of
carbon as low molecular-weight hydrocarbons, CO and CO2. These traces lead
to C I lines at 193.09 nm and 247.86 nm, but emissions of molecular species
(e.g. CN) derived from these trace impurities have been observed only in
high-powered plasmas, such as that of Greenfield et al.^
OH Emission. The OH molecule is the most ubiquitous molecular emitter
in unsalted plasmas. Even when water is not injected as an aerosol, the
"after-flame" above the plasma torch shows emission from the A^E+ - X^n
(0,0) band in the vicinity of 306.4 nm. This is apparent in published
background emission spectra,^ ^ whether water has been injected or not,
both for low-powered (0.3 - 2 kW) and for high-powered (2-7 kW) plasmas.
Where no water is aspirated, the emission arises from entrained atmospheric
water vapor. OH emission is minimized when no water is aspirated and a
long plasma torch is used, the plasma being observed through the torch
wall (made of Spectrosil quartz in our case). The (1,0) band of the same
system is usually also apparent through the wavelength range from 281 to
300 nm. Parts of the (1,1), (2,2) and (0,1) bands can also be seen between
310-350 nm. The relative intensities of lines of the (0,0) band between
307 and 309 nm have been used^ to obtain OH-rotational temperatures in
the plasma.

47
NH emission. The most prominent NH emission band, which is at 336.0
nm, has been reported in the high-powered, nitrogen-cooled plasmas of
47
Greenfield et_ al_. and is recorded as a weak emission in the "afterflame"
46 51
of low-powered argon-cooled plasmas. NH emission also occurs when
46
air is introduced into the coolant stream of a 4 kW Ar plasma. We have
observed NH emission in an argon plasma operated at low plasma gas flow
(10-15 L/min), at 0.55 - 1.5 kW, viewed 18-20 mm above the induction coil,
with ambient air and with air being flushed through the plasma box to pre¬
vent overheating. In Figure 6, spectra are given of OH and NH (306-338 nm)
obtained under these conditions (1.5 kW power, 12 L/min Ar, and 18 mm ob¬
servation height); NH has a very strong, sharp Q branch (0,0) at 336.0 nm
(A3n - xY).
The influence of ambient air versus flushed air on the variation of
the NH emission signal to background at 336 nm (resulting with water as¬
piration) as a function of observation height above the load coil and for
two power levels is shown in Figure 7a. For the case of the lower power
(1.0 kW) plasma, ambient air surrounding the plasma results in a rather
sharp maximum, whereas flushed air surrounding the plasma spreads the max¬
imum out over about 10 mm. This is apparently a result of considerable
air entrainment over a greater observation height in the latter case com¬
pared to the former case. At higher input powers (1.5 kW in our case),
the extent of air entrainment is greater in both cases than for lower
power, the maximum occurs at about the same height (« 25 mm), and the
breadth of the maximum are approximately the same in both cases. In
Figure 7b, the linearity of NH emission to background signals at 336 nm
with variation in nebulizer pressure (or solution aspiration rate) is
shown. NH emission has been used as the basis of a method of determin-
+ C1 +
ing NH^ in solution. The NH^ is oxidized by hypobromite to give

Tigure 6. Emission Spectra of OH and NH in the wavelength Region of 306-338 nm. Experimental Condi¬
tions: ICP input power, P=1 kW; Observation height above load coil, z=24 mm; Plasma Ras
Flow Rate, R=15 L/min; Monochromator Slit Width W=50 pm; Monochromator Slit height, H=1 mm
Nebulizer Gas Pressure, N=40 psi; Solution Nebulization Flow Rate, E=2 mL/min.

WAVELENGTH (am)
to
to
cc
EMISSION SIGNAL (RELATIVE UNITS)
to
to
CO
CO
c
Co
ho
cr¬
eo
ho
ho
to
c—
CK
to
â–º-*
•O.
to
c
CO
O'
t'O CO .£»
O'
-L
617
(IT

Figure 7a. NH Emission Signal to Background Signal at 336.0 nm Band Head
vs Observation Height. Experimental Conditions: R=15 L/min;
W-25 pm; H=1 mm; N=40 psi; F=2 mL/min (water).
Key: Solid line P=1.0 kW; Broken line P=1.5 kW; © Air flushed
into box (housing) containing torch. © Ambient air in box
(housing) containing torch.

Nil EMISSION (336 nm)/BACKGROUND EMISSION (336 nin)
51
OBSERVATION HEIGHT (mm)

Figure 7b. NH Emission Signal to Background Signal at 336.0 nm Band Head
vs Nebulizer Pressure. Experimental Conditions: same as above
for 5a except z=20 mm and air flushed into box (housing) con¬
taining torch.

53
I
10-
0
10
20
30
40
NEBULIZER PRESSURE (psi)
o.s
1.0
1.5
2.0
SOLUTION FLOW RATE mL/min

54
nitrogen, which is then passed into a low-powered (1 kW) plasma. Only
very weak NH emission is seen when concentrated ammonium salt solutions
are aspirated directly into the plasma.
NO emission. NO emission which arises from air entrainment in the
46
plasma flame has been noted by Truitt and Robinson and by Scott and
Strasheim. The major bandhead of the y-band system of NO (A - Xu)
is at 247.1 nm; the fine structure of several bands can be observed from
200-280 nm in a plasma operated at 1.1 kW and viewed at a height of 24 mm
above the coil. In Figure 8a, spectra are shown in the y-band system of
NO (200-280 nm) and the (1,0) band of the A^z+ - X^n transition of OH
(281.1-300 nm) obtained under the above conditions. A slow scan (expanded)
of the 232-248 nm region, including the two strongest NO bands, (0,1) and
(0,2), is shown in Figure 8b, and the (1,0) band (210-215 nm) is shown in
52
detail in Figure 8c. The last of these bands has been suggested as a
possible cause of difficulty in determinations of zinc using the Zn I line
at 213.86 nm. The superimposition of this line on some of the fine struc¬
ture of the NO emission has also been noted by Larson et al.^
In Figure 9a, continuum background spectra are given for 3 input
power levels; the Ar emission is observed through the quartz wall of the
long torch to eliminate ambient air entrainment. At 0.55 kW, the back¬
ground signal is virtually at the photomultiplier dark current level. With
an increase in input power, the background signal level increases as one
would expect for a "blackbody" radiator. In Figure 9b, the variation of
NO emission (at 214.9 nm) to background emission (also at 214.9 nm) with
observation height is shown for several different experimental conditions.
It is apparent that at the lower input power (1.0 kW), the ratio increases
from an undetectable level at around 10-15 mm, depending upon the atmo¬
sphere surrounding the plasma. At higher input power (1.5 kW), the ratio

Figure 8. Emission Spectra (y-band) of NO and A- X^H Band of OH.
Experimental Conditions: P=1 kW; R=15 L/min; z=24 mm; W=50 urn;
H=1 mm; N=40 psi; F=2 mL/min.
a. Spectral Range of 200-280 nm Showing y-Band of NO and A^s+ -
X2n Band of OH.

WAVELENGTH (nm)
EMISSION SIGNAL (RELATIVE UNITS)
Ul
On

Figure 8:
b. Expanded Spectral Range of 232-240 nm showing (0,1) and (0,2) NO bands.
c. Expanded Spectral Range of 210-216 nm showing (1,0) NO band.

WAVELENGTH (nm)
EMISSION SIGNAL [RELATIVE UNITS)
85

Figure 9a. Argon Plasma Continuum Background Observed Through Quartz
Tubing of Long Torch vs X. Experimental Conditions: R=15
L/min; W=25 um; H=1 mm; N=40 psi; F=2 mL/min (Water); z=20 mm.
Key: © P=0.55 kW; © P=1.0 kW; A P=1.5 kW
The dark current level in this studies is «0.5 nA(5 x 10” UA)

ARGON PLASMA BACKGROUND (nA)
60
i ! I 1 ! —
200 220 240 260 230 300 320 340
WAVELENGTH (nm)

Figure 9b. NO Emission Signal to Background Ratio at (1,0) Band Head
at 214.9 nm vs Observation Height. Experimental Conditions
R=15 L/min; W-25 um; H=1 rnm; N=40 psi; F=2 mL/min (water),
o Argon flushed into box (housing) containing torch.
0 Air flushed into box (housing) containing torch.
A Ambient air in box (housing) containing torch.
Key: Solid line P=1.0 kW; Dashed line P=1.5 kW

nm)/BACKGROUND EMISSION (214.
1.0
0.9 -
0.3 -
O
2
O
r~n
’S'.
o
2:
0.7 -
0. ó
0.5 -
OBSERVATION HEIGHT (mm)

63
reaches a maximum at «25 mm for all "atmospheric conditions," the maximum
having the greatest amplitude for ambient air and to lowest for an Ar
flush.
Other Molecular Emissions. Other emission spectra are readily ob¬
served when various gases, vapors and liquids are injected into the plasma
include those of 0^ and 0?+ (from oxygen),^ and (from nitrogen)
CN and C^ (from hydrocarbons, CHCl^, CCl^, and C0),^ CO (from the aspira¬
tion of methanol into a nitrogen-cooled plasma),^ P0 (from PCl^) and SO
(from SO^)."^
Molecular Emissions from Salted Plasmas. The existence of metal
oxides, both in the central region a few millimeters above the rf coil and
in the outer part of the "tailflame" at heights of 25-50 mm, can be demon¬
strated clearly by aspirating moderately concentrated solutions of ele¬
ments with rather stable monoxides, e.g., 1000 ug/mL of Y, Sc, Gd, Sm, Lu
and Zr.^ In all of these cases, the molecular emissions from the monoxide
appear in a different part of the visible spectrum from the atom and ion
lines of the same element. It is apparent, by visual observation of an
inductively coupled argon plasma that at least four rather distinct zones
exist: (i) a preheating («0-10 mm) where poor analyte atomic or ionic
signal to background ratios occur but with a very bright background; (ii) a
narrow zone («10-15 mm) where fairly intense atomic and ionic emission
occurs but also where monoxide emission is seen; (iii) the analytical zone
(the pencil system, «20-30 mm) where ionic and atomic emission measurements
are generally made because of the excellent line-to-background radios;
(iv) the plume region (>35 mm) where the plasma gases have expanded and
cooled and where considerable ambient air is entrained; in this region
monoxide emission can again occur, but where atomic and ionic emission sig¬
nals to background ratios are quite poor. The location of these zones

depends on a complex fashion upon power levels, plasma gas flows, nebulizer
pressure, torch configuration, and analyte species. Although many workers
who use the ICP as an emission source are aware of these phenomena, little
information has appeared in the literature concerning the presence of mo¬
lecular emission produced by salt introduction (as well as unsalted plas¬
mas—see above discussion) into the ICP and therefore the less knowledge¬
able worker might attempt measurement of radiation (especially emission,
but also absorption or fluorescence) under conditions where the signal-to-
background ratio is far from optimal.
In Figure 10a-f, typical monoxide emission spectra of several species
observed in the plume region («¡45 mm) are given. It should be stressed
that these spectra are the result of aspirating high concentrations of the
specific species into the plasma and of observations in the plume region.
Therefore, such emission will rarely affect analytical measurements by
AEICP. Nevertheless, monoxide emissions do occur and workers should be
aware of its existence. In Figure 11a and 11b, the variation of emission
signals of several species (atomic, ionic, and molecular) with observation
height are shown. For Y, the maximum for Y(II) occurs at a higher height
than for Y(I) which occurs at a higher height than YO. For Lu, the maxi¬
mum for Lu(II) occurs at a higher height than for LuO; the emission signal
for Lu(I) was rather low and constant over the observation height range of
10 to 45 mm.
B - Rare Earth Analysis
B.1 - Introduction
The analysis of rare earths in materials by chemical methods is plagued
with separation and detection difficulties, and so most workers have re¬
sorted to spectroscopic measurement techniques. Fassel^ has reviewed

Figure 10. Monoxide Emission Spectra of Several Species in Spectral Range of 465-475 nm and 590-630 nm. Ex¬
perimental Conditions: P=1.1 kW; R=16 L/min; N=30 psi; F=1.5 mL/min; W=25 pm; ||=1 mm; z=45 mm.
Backgrounds e and f are at dark current level «0.5 nA (5 x 10-^ A).
a. 1000 ppm Gd (GdO emission bands in 61B-620 nm range)
c. 500 ppm Sc (ScO emission bands in 590-620 nm range)
d. 500 ppm Y (Y0 emission bands in 590-630 nm range)
Monoxide Band
Intensity^
Element
Heads (nm)
GdO
618.268,620.006
110,110
621.171,622.093
110,110
ScO
601.707,603.617
160,620
606.431,607.265
490,440
607.930,610.107
620,320
610.993,611.597
370,370
614.870,613.393
180,150
610.009,619.290
150,150
Y0
597.204,590.764
1300,1000
600.360,601.907
740,620
603.660,613.206
500,1400
614.036,616.500
1100,820
610.223,619.982
560,590
621.796
450
(a) W. T. Meggers, C. H. Corliss, and B. F. Scribner, NBS Monograph 145, Part I (1975).
(They are relative intensities for DC arc)

WAV1U.ENGTII (mu)
EMISSION SIGNAL (RELATIVE UNITS)
CC
99

Figure 10f. H?0 Background in 590-650 nm range.

9
8
7-
6-
5
■t •
3
2
1-
ó
68
Cf)
630
610
390
WAVELENGTH (run)

Figure 10b. 1000 ppm Lu (LuO emission bands in 465-475 nm range)
e. H?0 Background in 465-475 nm range.
Element
Monoxide Band , .
Heads X(nm) Intensity 3
LuO
466.175,467.231 630,310
468.416,469.546 420,270
470.800,473.500 190,100
(a) Same as fig. 10 a,c,d

WAVELENGTH (nm)
EMISSION SIGNAL (RELATIVE UNITS)
H
I—‘ ro oí i— tn CT- "i Go i.q o
-I 1 1 I I I I I|i
o

Figure 11. Emission Signals of Several Species vs Observation Height.
Experimental Conditions: Same as Figure 10.
a. 500 ppm Y
o Y0 band head at 614.84 nm. (band head intensity=1100)
3 Y atom line at 619.17 nm. (atom line intensity=1200)
^ Y ion line at 508.74 nm. (ion line intensity=1100)

EMISSION SIGNAL (nA)
72
OBSERVATION HEIGHT (mm)

Figure 11b. 500 ppm Lu
o LuO band head at 466.18 nm. (band head intensity=630)
Q Lu atom line at 500.11 nm. (atom line intensity=800)
a Lu ion line at 499.41 nm. (ion line intensity=800)

EMISSION SIGNA), (nA)
74
200
OBSERVATION HEIGHT (ram)

75
spectroscopic methods which have been extensively used for the quantita¬
tive determination of rare earth metals. Flame spectra of rare earth ele-
58
ments were observed by Rains et al_. who aspirated non-aqueous solutions
of these elements into an oxy-hydrogen flame. Reducing flames to aid in
59
atom production were used by Fassel et al_. who were successful in obtain¬
ing analytically useful line spectra of these elements in fuel rich flames
by introducing ethanol solution of the elements.
Further studies by Mossotti, Fassel and others^ ^ on these elements
provided over one thousand absorption lines in the optical region which
were successfully used for quantitative determination of rare earth ele¬
ments by atomic absorption spectrometry.
Amos and Willis^ in their study observed that when higher tempera¬
ture flames were employed as an absorption cell, the degree of ionization
of rare earths became significant. Determination of traces of rare earths
by atomic absorption with electrothermal atomization and by d.c. arc emis-
64
sion spectroscopy was discussed by Dittrich and Borzym.
Dickinson and Fassel^ with an ultrasonic aerosol generator and de-
solvation facility in their ICP determined detection limits for La and Ce.
13
Later Fassel and Kniseley reported ICP detection limits of rare earths
which were superior to those from flames. Souilliart and Robin'^ used a
high power (6.6 kW) ICP and ultrasonic nebulizer in the study of rare earth
metals. In this study, we have used a conventional moderate power (1.25-
1.5 kW) ICP with a glass concentric pneumatic nebulizer for the determina¬
tion of detection limits (LOD) and linear dynamic ranges (LDR) of rare
earth elements in pure solution and in a mixture of all the rare earth
elements.

76
B.2 - Experimental
Preparation of Standards. Individual stock solutions of 1000 pg/mL
of each rare earth element as well as mixtures of the elements were pre¬
pared by dissolving reagent grade pure oxides (ignited at 600°C for 4 hr)
in hot 3 M. HC1. Successive dilutions were made before each determination
using distilled-deionized water. A solution of hydrochloric acid in de¬
ionized water was used as the blank.
Apparatus. Instrumental set up is given in Figure 4, and a 2 kW in¬
ductively coupled plasma (Plasma Therm Inc., Kresson, NJ) with a 27 MHz
radio frequency generator was used in conjunction with a glass concentric
neublizer. The nebulizer solution flow rate was controlled with a syringe
pump (Sage Instruments, Div. of Orion Research Inc., Cambridge, MA). A
list of major instrumental components of the ICP system used in this study
is given in Table 4.
Limits of detection (LOD) and linear dynamic ranges (LDR) were measured
by integrating the electrometer signal for 10 s. The LOD was taken to be
that concentration equivalent to a signal three times that of the standard
deviation of 16 consecutive, integrated blank readings.
Experimental Conditions. The plasma system was operated at argon
flows specified by the manufacturer. The ICP power was maintained at 1.25-
1.5 kW throughout all measurements; the nebulizer solution flow rate was
maintained at 2.2 mL min and the cooling gas was controlled to 16-20 L
min . A spherical lens (image 1:1), placed in a 3" metal tube, was used
to focus the emission beam to the monochromator entrance slit. The en¬
trance slit of the monochromator was set at 30 pm in width because it was
the lowest value, which could be used and 2 cm in height; the exit slit was
adjusted to a width of 16 pm to reduce the signal from the background emis¬
sion. The ICP was mounted on an adjustable (x-y-z) table so that the

77
Table 4
SPECIFIC COMPONENTS OF EXPERIMENTAL SYSTEM
Component
Model #
Company
ICP
Torch assembly
RF Generator
PT 1500
HFP-1500D
Plasma Therm Inc., Kresson,
NJ
Nebulizer
T-220-A2
JE Meinhard Associates,
Santa Anna, CA
Monochromator
1870
SPEX, Metuchen, NJ
Photomultiplier
R-818
Hamamatsu Corp., Middlesex, NJ
High voltage power supply
224
Keithly Instruments, Cleveland,
OH
Current/voltage convertor
601
Keithly Instruments, Cleveland,
OH
Integrator
Lab Constructed

78
observation height could be adjusted with respect to the monochromator.
The optimum plasma observation height was found to be 12 mm above the load
coil of the ICP.
B.3 - Results and Discussion
The observed detection limits and linear dynamic ranges of rare earth
elements with the lines used for measurement (also energies of levels and
gA values are given) are summarized in Table 3. The linear dynamic ranges
were obtained by measuring the relative emission signals of selected anal¬
ysis lines vs concentration of metal ions in solution. The analytical cali¬
bration curves are linear over a concentration range of «5 orders of mag¬
nitude for all of the elements being studied. As representative examples,
calibration curves for La, Ce, Eu, Dy, Ho, and Lu are presented in Figures
12, 13 and 14.
13 66
Comparison of the results of this work with that of other authors ’
indicates that the condition employed in this study have resulted in simi-
13 66
lar or better limits of detection as others reported in the literature. ’
It is also clear from the LODs obtained in the mixture of elements that
matrix interferences are negligible in the ICP.
In the present studies, only ion lines were found to be sufficiently
intense for analytical measurements of rare earth metals. Ion lines (see
Table 4) were selected on the basis of maximum of intensity and minimum
spectral interference and background. The detection limits obtained in
this study in pure aqueous solutions or rare earth mixtures are similar
13 66
to or superior to those ’ reported in two previous studies of ICP exci¬
tation of rare earths. The excellent linear dynamic ranges in this study
should be stressed; unfortunately, LDRs were not obtained in any of the
previous studies.

Table 5
LIMITS OF DETECTION AND LINEAR DYNAMIC RANGES OF RARE EARTH METALS
Linear Dynamic
Energy.
gA
x108(s 1)
Limits of Detection nq/mL
Range
Wavelength
Levels3
This
Work—ICP
Previous
Works—ICP
(dimensionless)
ElemenL
(nm)
(K)
Pure Soln. Mixture
Ref. (13)
Ref. (66)
This Work
L&U
394.91
3250-20565
5.0
5
5
>2x105
379.40
1971-28315
2.3
3
6
CoH
394.27
0-25360
2.0
20
10
7
30
>105
Pril
391.89
2998-28509
2.0
20
20
A
>5x10
390.8
4437-30018
1.9
60
30
Nd 11
401.22
5086-30002
5.2
10
10
50
10
>105
Smn
360.95
2238-29935
3.9
20
20
>5x104
442.43
3910-26540
1.3
20
30
EuII
420.50
0-23774
3.2
3
4
>3x105
412.97
0-24208
1.9
1
3
381.97
0-26173
4.8
3
“i!
376.84
633-27162
8.3
10
7
>105
342.25
1935-31146
19.0
7
10
336.22
633-30367
12.0
20
Tbn
350.92
0-20488
NRb
9
10
200
20
>105
vl
vO

iuD±e ^--continued
DyII
353.17
0-28307
19.0
8
H° 11
345.6
NRb
NR
8
ErII
349.91
440-29011
9.9
10
337.28
0-29641
13.0
Tm 11
384.80
0-25980
1.1
6
YbII
369.42
0-27062
0.74
2
328.94
0-30392
1.4
Lun
350.74
0-28503
0.20
10
a. See Reference (67).
b. NR = not recorded.
7
4
9
>105
7
10
10
>105
10
1
10
>103
7
7
10
>105
4
0.9
5
>5x10
10
8
10
>105
OQ
c

Figure 12. Analytical Calibration Curves for Lanthanum and Cerium.
• single element
x in mixture

RELATIVE INTENSITY (Arbitrary unit)

Figure 13. Analytical Calibration Curves for Europium and Dysprosium.
• single element
x in mixture

Q*
O-
Ol
o-
(X>
ANALYTE CONCENTRATION (ng.ml
^001
^RELATIVE INTENSITY
O o O
j t o*
(Arbitrary unit)
O

Figure 14. Analytical Calibration Curves for Holmium and Lutetium.
• single element
x in mixture

86

CHAPTER THREE
ATOMIC FLUORESCENCE SPECTROMETRY
IN THE FLAME USING ICP AS A NEW EXCITATION
SOURCE "ICP-EXCITED FASF"
A - ICP Diagnostics Using the ICP-Excited Flame AF5
A.1 - Introduction
Many physical parameters of the inductively coupled plasma (ICP)
source for analytical spectroscopy have been investigated. The recent
68
review by Barnes contains an extensive list of references covering fun¬
damental operating principles and methodologies. Emission profiles of
several elements for several experimental conditions have been reported
69
by Human and Scott, ' who used a pressure-scanning Fabry-Perot interfer¬
ometer to obtain the profiles. These authors concluded that the spectral
profiles of the lines emitted for the elements investigated (Ca,Sr,Ar)
depended upon the height of observation and that, although self-absorp¬
tion and self-reversal were observed at certain heights, these phenomena
did not occur for a range of at least three orders of magnitude (1-1000
pg/mL) indicating the excellent characteristics of the ICP as an emission
source.
This work reports preliminary results showing how several limiting
characteristics of the ICP emission profiles can be derived if the ICP is
used as an excitation source for atomic fluorescence spectrometry. The
emission of selected atomic species introduced into the plasma is moni¬
tored via the fluorescence signal observed when a given (low) concentra¬
tion of the same element is aspirated into an air-acetylene or another
87

88
suitable gas mixture flame. Therefore, the flame acts as a resonance
70-73
monochromator.
This procedure is capable of providing in a very
simple way qualitative but unequivocal information about the line profile
of the ICP emission without sophisticated instrumentation such as high
resolution monochromators of Fabry-Perot interferometers. These latter
approaches are the only ones giving complete quantitative information
about the true line profiles. However, the fluorescence technique, not
only clearly detects self-absorption, but is especially sensitive to in¬
cipient self-reversal of the emission line profile.
This information is obtained from the experimental log-log plot of
three curves of growth: the first one, is the excitation curve of growth,
in which a fixed low concentration is used in the flame while increasing
concentrations are aspirated into the ICP, (i.e., the flame acts as a
resonance monochromator);^ the second one, is the fluorescence curve of
growth, (i.e., the conventional curve of growth obtained with a fixed
(high) concentration of a selected element in the ICP while aspirating
increasing concentrations of the same element into the flame); and the
third one, is the common emission curve of growth, in which the emission
from the ICP is directly plotted vs. the concentration of the analyte in
it.
The results obtained for the elements Zn, Mg and Ca verify the ex¬
pected behavior of these curves.
A. 2 - Theoretical Considerations
The interaction between the radiation emitted by the ICP and the
absorbing atoms in the flame is described by the following "excitation
function"
74-76,21,37
E
X
exc
(44)

89
in which the integral is extended over the entire absorption line width
(i.e., the width over which k^(X) differs markedly from zero). Here the
terminology is as follows:
E (x) = spectral irradiance of the ICP as a function of wavelength at
exc
a given height and at a given analyte concentration, evaluated
-1 -2 -1
at wavelength X, 3 s cm “ nm ;
oif(x) = fraction of radiation absorbed at any wavelength X, dimension¬
less ;
k^(x) = absorption coefficient of analyte atoms in the flame, usually
given by the product of kQ (peak absorption coefficient for a
purely Doppler broadened profile) and the Voigt profile func-
-1
tion, cm ; for a given resonance line and under given condi¬
tions and flame temperature, k(X) is proportional to n^, the
flame atomic concentration, over all the absorption line, for
all values of n^.
L = interaction length for the absorption process in the flame, cm.
The spectral irradiance of the ICP, E (x), can be regarded as the
exc
product of the blackbody spectral irradiance at the wavelength considered
and at the ICP emission temperature and the total absorption factor which
is a function of the concentration in the ICP and of its emission depth
in the direction of the flame.
When the interaction process is studied by means of the resulting
fluorescence emission in the flame, then the fluorescence radiance is
given by the following proportionality:

90
BpCcrj J* Ex (X) { 1-exp[-kf(X)L]}dX }
abs exc
\L
Ex (x)
ábs exc
\ J jl-exp[-kp(x)a]}dx /[i /kf(x)dx]L
'abs abs )
11-exp[-kf(\)L]dx| j[At(nfO ]/[«. J kf(x)dx]j
(45)
Equation 45 is equal to Equation 44 multiplied by a term which takes into
account the self-absorption of the fluorescence radiation leaving the
flame. Here, A^. (n^i.)-exp[-kp(X) &] | dx , is the total absorption fac¬
tor for the fluorescence radiation in the flame, n^ is the flame atomic
concentration, and l is the (homogeneous) fluorescence depth. Equation
45 simplifies for the two usual limiting cases of line and continuum ex¬
citation sources and for negligible fluorescence self-absorption. In
fact, if n^ is low, then the second factor at the right hand side of
Equation 45 is unity.
If the ICP acts as a spectral line source, the kp(x) can be consid¬
ered constant and equal to its peak value, k . Equation 45 then re-
fT)3X p
duces to Equation 46.
E (X)dx
exc
(46)
Thus the ICP may act as a line source if its overall spectral emission
profile is narrower than the absorption profile in the flame, even though
its higher temperature would cause the Doppler halfwidth to be larger
than that in the flame by a factor of approximately the square root of
two (assuming a Maxwellian velocity distribution exists).
If the ICP acts as a spectral continuum because, at high concentra¬
tions, self-absorption has broadened the emission profile to such an ex¬
tent that it becomes larger than the absorption profile in the flame,
then Equation 45 reduces to Equation 47.

91
BpocEx (Xo) / jl-exp[1-kf(x)L](dXc£x (XQ)At(nfL) (47)
exc abs exc
in which E^ (x ) is the constant irradiance of the ICP over the absorp-
exc
tion line profile.
Therefore, when the interaction between the ICP emission and the
resonance absorption profile in the flame is monitored by the fluorescence
emitted from a constant concentration of flame atoms, a slope of unity
for low concentrations in the ICP and a limiting slope of zero for high
concentrations in the ICP should be obtained. This limiting zero slope
will hold, irrespective of the amount of self-absorption, as long as self-
reversal does not affect the ICP emission profile. When this happens,
i.e., when the ICP emission profile starts showing a dip in the center,
this dip will be reflected immediately in the fluorescence signal, and a
negative slope will be observed in the experimental plot.
On the other hand, the ICP-excited fluorescence curve of growth ob¬
tained by aspirating in the flame increasing concentrations of analyte
should give the following information:
(i) if the asymptote at high np has a slope near -0.5, then the
ICP, at that particular height and atom density n^, behaves
like a line source, i.e., its spectral profile is narrower
than the absorption profile in the flame;
(ii) when self-absorption is large in the ICP emission, this
curve of growth should approach a region of zero slope,
which indicates that the emission profile is broader than
the absorption profile; and
(iii) the absence of self-reversal in the emission profile can be
inferred unequivocally by the combined observations of this
curve of growth with the previously described excitation
curve of growth obtained at the same experimental settings.

92
These results, which are summarized in Table 6, can be obtained from
Equations 45-47, by assuming that the self-absorption factor for the fluo¬
rescence cannot be considered negligible and remembering that A^(n^-L) and
A^(n^i) vary linearly with n^. at low n^ values and with n^2 at high n^
values.
A.3 - Experimental
Figure 15 shows the experimental arrangement used. The ICP source
(ICP 1500 Plasma Therm., Inc., Kresson, N.J.) was focused on the aper¬
ture of a chopper and subsequently onto the flame by means of spherical
quartz lenses. In order to minimize pre- and post-filter effects, a rec¬
tangularly shaped burner was used and care taken to optimize properly
illumination and observation geometries. Furthermore, in order to avoid
possible inhomogeneities in temperature and composition, the flame was
shielded by another similar flame, which could in turn be surrounded by
an inert gas flow.
The fluorescence was collected by a spherical quartz lens and di¬
rected onto the entrance slit of a small monochromator (Jobin-Yvon, H-10,
8 nm/mm reciprocal linear dispersion); the slit width and height were
set, unless otherwise stated, at 50 urn and 10 mm, respectively. The out¬
put signal of a photomultiplier (Hamamatsu 1P28) was fed to a lock-in am¬
plifier (840 Autolock, Keithley, Cleveland, Ohio) and then to a chart re¬
corder. For the emission measurements, the ICP image was focused directly
onto the entrance slit on a 0.35-m monochromator (2 nm/mm reciprocal
linear dispersion, 25 ym slit width, 15 mm slit height Model No. EV-700,
Heath, N.Y.). Neutral density filters (Corion, Massachusetts) allowed
the verification of the linearity of the response of both emission and
fluorescence photomultiplier and associated detection electronics.

93
Table 6
THEORETICAL LIMITING SLOPES FOR THE THREE CASES
CONSIDERED IN ABSENCE OF SELF-REVERSAL(a}
Technique
Atom Density in the Source
Very Low Very High
Emission
0.5
Excitation
0
Atom Density in the Flame
Very Low Very High
Fluorescence
(line source excitation) 1 -0.5
Fluorescence
(continuum source excitation) 1 0
(a) When self-reversal in the source is effective at high concentrations,
the slope of the emission technique decreases and that of the exci¬
tation technique becomes negative. When self-reversal occurs in the
flame, the high density slopes will display similar trends. Self-
reversal in the flame here means that a temperature gradient exists ^
in the flame and should not be confused with the post-filter effect.

Figure 15. Layout of the experimental set-up used.

95
ICP
LENS
CHOPPER LENS
SHIELDED
LIGHT
TRAP
PMT
H.V.

96
Standard solutions were made from reagent grade chemicals, dissolved
in the minimum amount of HC1, and brought to the desired concentration
level with deionized water.
A.4 - Results and Discussion
Figures 16, 17 and 18 show the excitation curves of growth obtained
for the elements Mg, Zn, and Ca when a constant low concentration of each
element (1,1, and 10 yg/mL, respectively) was aspirated into the air-
acetylene flame and the ICP concentration was varied from 10 to 20,000
yg/mL. This last concentration caused no problem in the operation of the
ICP, although a deposit was observed after prolonged operation on the
aerosol injection orifice. A similar effect was also reported by Larson
and Fassel7"7 when aspirating high sodium concentrations.
As one can deduce from these figures, the general limiting trends
predicted by the theory are qualitatively well verified experimentally.
In the case of magnesium, Figure 16 shows that self-reversal in the ICP
is totally absent at the heights which are commonly used for analysis
(curves b and c). Indeed, to observe self-reversal (curves d and e) it
was necessary to increase the observation height to 37 mm above the coil,
in a region practically never utilized for analysis. One can also note
the utility of detecting incipient self-reversal in the ICP by means of
the flame fluorescence signal, since the ICP emission is still increasing,
although with a smaller slope (curve f). Figure 16 shows also clearly
(see insert c) that at an observation height of 13 mm above the coil, the
emission is still increasing almost linearly (slope of 0.9) and the fluo¬
rescence is also increasing (slope of 0.6); this indicates that self¬
absorption in the ICP is not very pronounced even at concentrations as
high as 20,000 uq/mL. This unique feature of the ICP as an excitation
source indicates that it behaves as an optically thin discharge. When

Figure 16. Emission and Excitation curves of growth for Mg at 285.2 nm.
(a) ICP emission, height of observation above coil, z=18 mm;
(b) ICP excitation curve, z=18 mm; 1 ug/mL of Mg aspirated
into the air-acetylene flame; (c) same as (b) but at z=25 mm;
(d) same as (b) but at z=30 mm; (e) same as (b) but at z=37
mm; (f) emission from ICP at z=37 mm; (g) ICP emission (upper
line) and excitation (lower line) curves for the three con¬
centrations reported in the abscissa at z=13 mm. All curves
were obtained at an operating power of 1.5 kW.

HüO(«ic*nc« Signal* (Afbllrary Unit* )
98
102 'O3 10*
Us ! I L
Mg m ICP. nq/rnt

Figure 17. Emission and Excitation curves of growth for Zn at 213.9 nm.
(a) ICP emission, z=18 mm; (b) ICP excitation curve, z=18 mm,
1 ug/mL of Zn aspirated into the air-acetylene flame; (c) ICP
emission (upper line) and excitation (lower line) curves for
the three concentrations reported in the abscissa at z=37 mm.
All the curves were obtained at an operating power of 1.5 kW.

fluoi«i(fn(« Signal» Uibiliaiy Unit»)
100
In .« ICP M9/ml

Figure 18. Emission and Excitation curves of growth for Ca at 422.7 nm.
(a) ICP emission at z=37 mm; (b) same as (a) but at z=13 mm;
(c) Excitation curve, z=37 mm, 10 ug/mL of Ca aspirated into
air-acetylene flame; (d) same as (c) but at z=13 mm; (e) same
as (c) but at an operating power of 1 kW. All other curves
were obtained at 1.5 kW.

102
Caiciwm in ICP, ^g/mi

1Ü3
self-absorption broadens the line and the emission curve reaches a slope
of «0.5 (curve a), the excitation curve approaches a slope of zero (curves
b and c).
Even more striking are the results for zinc presented in Figure 17.
In fact, no sign of self-reversal is observed even at 37 mm above the
coil, while self-absorption seems to be complete at this height (see in¬
sert c). The results obtained with calcium (Figure 18) are similar to
those for magnesium and zinc. As with Mg, Ca emission shows self-reversal
at 37 mm above the coil (curve c), and this increases at a power of 1 kW
(curve e).
Figures 19 and 20 show the fluorescence curves of growth for Mg and
Zn in the air-C2H2 flame obtained at several fixed concentrations in the
ICP. By recalling the conventional behavior of the fluorescence curves
of growth (see Table 6), one can conclude from both figures that the ICP
should be considered essentially a "line" excitation source compared to
the absorption profile in the flame. Indeed, all the fluorescence curves
(a to d in both figures) have a slope close to -0.5 for high analyte con¬
centrations in the flame. Moreover, the intersection points of the
asymptotes for the curves are not significantly displaced from each
other when the concentration in the ICP increases from 1,000 to 20,000
ug/mL. This indicates that the ^-parameter (which is indicative of the
ratio between collisional and Doppler broadening) is not changing much,
which is in qualitative agreement with the behavior shown by the excita¬
tion curves of growth, obtained at the same heights, of Figures 16 and
17. This is as expected, since the major source of collisional broaden¬
ing would be interaction with the argon plasma gas.
Since at 37 mm above the coil, zinc self-absorption was essentially
complete (see Figure 17, insert c), flattening of the fluorescence growth

Figure 19. Fluorescence curves of growth for Mg at 285.2 nm and at z=18 mm.
The different curves correspond to different concentrations in
the ICP: (a) 1,000 ug/mL; (b) 4,000 ug/mL; (c) 8,000 ug/mL;
(d) 20,000 ug/mL.

fkwf«K*n<« Sifftoli (Aikiliaiy Unlit)
105

Figure 20. Fluorescence curves of growth for Zn at 213.9 nm and at z=18 mm.
The different curves correspond to different concentrations in
the ICP: (a) 1,000 yg/mL; (b) 4,000 yg/mL; (c) 8,000 yg/ml;
(d) 20,000 yg/mL. The insert (e) in the figure shows the dif¬
ference in the results obtained at z=37 mm, when the ICP con¬
centration is fixed at 1,000 yg/mL (lower curve) and at 20,000
yg/mL (upper curve).

¿01
Fiuoiatcanca Signal» (Atbllitry Until)

108
curve should be observed at this height when 20,000 yg/ml of Zn is as¬
pirated in the ICP. Results, shown in the insert (e) of Figure 20,
verify that a flattening is indeed observed at the highest ICP concen¬
tration. However, for analyte concentrations in the flame above 2,000
ug/mL, a negative slope in the fluorescence growth curve still occurs,
which could probably be explained by the additional broadening of the ab¬
sorption profile in the flame.
A.5 - Detection Limits
Although considered beyond the scope of the present work, the limits
of detection were measured with the present non-optimized system for the
three elements investigated. Sixteen consecutive integrated blank meas¬
urements were performed by aspirating water into the air-acetylene flame
and the highest concentration of the element into the plasma. When water
was aspirated into the plasma, the noise level remained essentially the
same. The slit width of the fluorescence monochromator was set at 1 mm
for Ca and Zn and at 50 urn for Mg. The actual concentrations aspirated
into the flame were 0.01 ug/mL for Mg, 0.1 ug/mL for Zn and 0.1 yg/mL for
Ca. The calculated detection limits (at 3 times the standard deviation
of the blank) were found to be 13, 4, and 23 ng/mL for Zn, Mg, and Ca,
respectively.
Although the experiment arrangement was not optimized for illumina¬
tion and collection efficiencies, the detection limits are equivalent or
within an order of magnitude of those obtained with conventional atomic
fluorescence excited by an electrodeless discharge lamp (Ca) or an Eimac-
21
Xe continuum source (Mg, Zn). These detection limits are similar or
better than those reported by Hussein and Nickless"^ for a 36 MHz (2.5 kW)
induction-coupled plasma and an air propane flame.

B - Detection Limits and Real Sample Analysis
Using "ICP-Excited Flame AFS"
109
B.1 - Introduction
13
The inductively-coupled argon plasma (ICAP) has been demonstrated
to be an excellent source for emission spectrometry. However, the spec¬
tral characteristics of the emission from this source, such as high in¬
tensity, excellent short and long term stability, narrow linewidth and
freedom from self-reversal, make it an ideal radiation source for the
excitation of atomic fluorescence in flames.
The first reported use of a radiofrequency, induction-coupled plasma
(36 MHz, 2 kW, Model SC15, Radyne Ltd., U.K.) as an excitation source for
flame atomic fluorescence spectrometry (AFS) by Hussein and Nickless^
resulted in relatively poor detection limits'^ (see Table 8) which prob¬
ably contributed to the absence of further development of the ICAP as a
source for AFS. However, the tremendous growth in the use of the ICAP
for emission in the last decade has resulted in significant improvement
78
in sample introduction and plasma stability, which now makes the ICAP
an excellent source for AFS as seen in part A.
The advantage of the ICAP compared to other AFS sources is its flex¬
ibility with respect to the availability of intense atomic and ionic line
radiation for many elements. Changing from one element to another is
simply a matter of aspirating a different solution into the plasma,
taking less than one minute. The availability of many intense non-
resonance and ionic lines allows scatter correction to be easily per-
79
formed using the two-line technique.
ICAP-excited AFS can also offer an alternative to ICAP-emission
when spectral interferences which are observed with monochromators of
medium resolution (>0.01 nm spectral bandpass) significantly limit

110
emission analysis. Interferences in emission due to changes in the
plasma background radiation (which require a background correction pro¬
cedure) are not observed using AFS and line spectral interferences which
cannot be resolved may be reduced or eliminated because of the spectral
selectivity of flame AFS, based on differences in atomization, excita¬
tion, and ionization properties of the flame and plasma; on differences
in quantum efficiencies between analyte and interferent lines; and on the
property of the flame as a resonance detector with an effective spectral
bandwidth equivalent to the width of the absorption transition.
We have investigated the application of the ICAP as an excitation
source for atomic fluorescence using a simple optical setup, low resolu¬
tion monochromator, and nitrogen-separated air/acetylene and nitrous-oxide/
acetylene flames. Detection limits obtained for 14 elements are compared
to AFS detection limits using other excitation sources and to detection
limits of other atomic spectrometric techniques, such as flame atomic
absorption and ICAP-emission. The noise sources limiting precision at
low and high concentrations are delineated and the effect of various in¬
strumental parameters such as spectral bandpass and ICAP nebulizer pres¬
sure on signal-to-noise ratios is described. The scatter problem is
evaluated and the two-line method is applied for scatter correction.
ICAP-emission and ICAP-excited AFS are applied to the analysis of zinc
in unalloyed copper (NBS SRM-394 and 396) and the AFS technique is em¬
ployed to correct for a zinc-copper spectral interference at the 213.9 nm
line in ICAP-emission. ICAP-excited AFS is also employed for the analy¬
sis of copper and zinc in orange juice, zinc in fly ash (NBS SRM-1633)
and cadmium and zinc in simulated fresh water (NBS SRM-1643).
B.2 - Experimental
Instrumentation. The instrumentation used in this study is described
in Table 7 and a diagram of the arranqement of eXDerimpnfP1 rnmnrinonfo

Table 7
Component
ICAP
Nebulizer
Emission
monochromator
Fluorescence
monochromator
Emission
photomultiplier
INSTRUMENTATION AND OPERATING PARAMETERS
Description
PT-1500 torch assembly and
HFP-1500D RE generator (Plasma
Therm Inc., Kresson, N.J.)
Concentric-ring glass nebulizer
T-220-A2 (J. E. Meinhard Assoc.,
Santa Anna, CA)
EU-700 monochromator (Heath
Company, MI), 0.35-m focal
length, f/6.8 aperture, 1180
groves/mm, grating blazed for
250 nm, adjustable slits,
2 nm/mm reciprocal linear
dispersion
H-10 monochromator (UV-V) (JY
Instruments, Metuchen, N.J.)
0.1-m focal length, f/3.5 aper¬
ture, 8 nm/mm reciprocal linear
dispersion, holographic grating
with 1200 groves/mm, with 0.05,
0.5, 1, 2 mm slits providing
spectral bandpasses of 0.4, 4,
8, and 16 nm, respectively.
R-928, (Hamamatsu TV Corp. Ltd.,
Middlesex, N.J.)
Operating Parameters
1.5 kW power, 15 L/min argon coolant flow
rate
Nebulizer pressure optimized for individual
elements - from 15 to 35 psi (Solution Uptake
Rate=1.75 mL/min)
1 mm slit height
25 n m slit width
(effective 0.05 nm spectral bandpass)
2 mm slit width except where noted in text;
1 cm slit height
1000 V

Table 7—continued.
Fluorescence
photomultiplier
1P28, (RCA Corp.,
Harrison, N.J.)
Current-to-
Voltage
Converter
Keithley 427 (Keithley Instrument
Company, Cleveland, Ohio)
Lock-in
Amplifier
Keithley 840 Autoloc amplifier,
wideband
Recorder
Texas Instruments, Houston, TX
Chopper
Model 125, (Princeton Applied
Research Corp., Princeton, N.J.)
Nebulizer
and mixing
chamber for
flame
Perkin-Elmer adjustable nebulizer
and mixing chamber with flow
spoiler (Perkin-Elmer Corp.,
Norwalk, Conn.)
Burner heads
Circular stainless steel capillary
burner head with auxiliary sheath
Lenses
Spectrosil, 5 cm diameter, 9 cm
focal length)
Mirror
5 cm aluminum-coated spherical
with 5 cm focal length (Klinger
Scientific Corp., Jamaica, N.Y.)
600 to 900 V, depending on background emission
from flame
1 or 3 second time constant
600 Hz
5-8 mL/min aspiration rate

113
is shown in Figure 21. Radiation from aqueous solutions of the analyte
element aspirated into the ICAP is modulated at 600 Hz and focused by
spherical quartz lenses on the separated flame. A reflector is placed
behind the flame to provide a double-pass system. The fluorescence mono¬
chromator is placed 4 cm from the flame center and the viewing area is
centered 2 cm above the burner head. A light trap is placed opposite
the flame from the monochromator to reduce stray light and scatter ef¬
fects. Once optical alignment is attained, the only ICAP parameters that
must be optimized for different elements are the argon pressure to the
nebulizer and the concentration of the solution nebulized. Torch posi¬
tion is not critical, since the entire emission area above the coils is
focused on the area of the flame viewed by the fluorescence monochroma¬
tor .
Emission measurements from the ICAP were performed as described pre¬
viously in Chapter 2.
Excitation Source (ICAP) Solutions. The solutions used for excita¬
tion of analyte emission from the ICAP contained 10 to 20 mg/mL of the
analyte. Whenever possible, these "excitation" solutions were prepared
by acid dissolution of the high purity metal or metal oxide, although
other compounds (nitrates, chlorides, etc.) were employed when the former
were not available. The selectivity of the fluorescence technique using
line source excitation (i.e., its ability to discriminate against spec¬
tral interferences) depends on the spectral purity of the line source,
and if significant interferent contamination exists in the excitation
solution, interferent emission will be excited in the ICAP which may de¬
grade the selectivity. The effect of such contamination is discussed
more fully for the analysis of zinc in unalloyed (high-purity) copper.
The use of solutions of such high concentrations does not signifi¬
cantly degrade the ICAP performance by clogging the sample orifice of

Figure 21. Diagram of Experimental Layout of Components for Measurement
of ICAP-excited AFS and ICAP-emission.

115

116
the torch or the nebulizer during an 8-hour working day. However, to
prevent such degradation on prolonged use, which would result in source
intensity drift, the torch is cleaned after a days' use in a solution of
1:3 V:V HNO-j/HCl.
Fluorescence Standards. Standards for AFS measurements were pre¬
pared from the same solutions used for excitation in the ICAP using
serial dilution with deionized water and sub-boiling distilled acids
prepared in this laboratory.^
Sample Preparation. The samples analyzed by ICAP-excited AFS and
ICAP-emission were prepared as follows:
1)Orange juice - dry ashing procedure is described by McHard et
2) Fly ash (NBS SRM-1633) - wet ashing procedure is described by
Epstein et_ al
3) Unalloyed copper (NBS SRM-394 and 396) - dissolution of 1 g of
copper is carried out in 10 mL of sub-boiling distilled HC1 with dropwise
addition of sub-boiling distilled HNO^ until complete, reduction in vol¬
ume after dissolution by evaporation to 2 mL, and finally the solution
is diluted to a volume of 100 mL.
4) Simulated Fresh Water (NBS SRM-1643) - direct analysis is per¬
formed .
B.3 - Results and Discussion
Limits of Detection. As shown in Table 8, limits of detection for
many of the elements examined using ICAP-excited AFS approach, equal, or
even exceed in one case (Mo) the best atomic fluorescence detection
limits ever obtained in similar flames (i.e., nitrogen-separated air/
acetylene or nitrogen-separated nitrous-oxide/acetylene) using a rela¬
tively conservative time constant (3 s) or integration time (1 s) and a

Table 8
LIMITS OF DETECTION (ng/mL)
ICAP-excited
AESC,d
ICAP-emission
Element
X(nm)3
ri b
El ame
this work
ref 34
i • e
same line
•
commercial
best^
AES lineh
AAS
A1
308.2
309.3
S-NOA
1000
-
23
15
1
120
30
As
233.0
S-AA
5000
-
142
25
25
70
100
Ca
422.6
S-AA
4
100
10
4J
0.0005
0.3
1
Cd
228.8
S-AA
0.8
80
2.7
1
0.3
0.2
1
Co
240.7
241.1
241.4
242.5
S-AA
11
>23
2
0.4
1.5
10
Cr
357.8
359.3
360.5
S-AA
2
23
4
1
0.3
3
Cu
324.7
327.4
S-AA
2
50
5.4
2
0.3
0.3
2
Ee
248.3
248.8
249.0
S-AA
6
>20
2
0.2
0.6
10
Mg
285.2
S-AA(fr)
0.09
5
1.6
20j
0.01
0.09
0.1
Mn
279.5
279.8
280.1
S-AA
2
100
12
0.5
0.06
0.5
2
Mo
313.3
315.8
S-NOA
400
-
>37
5
0.5
750
30

Table 8—continued.
Pb
203.3
S-AA
800
-
142
20
10
V
310.5
310.4
310.3
S-NOA
400
>17
2
0.2
Zn
213.9
S-AA
0.5
00
1.0
2
0.3
g
Wavelengths of major fluorescence line(s) contributing to the fluorescence spectral intensity. Since the
spectral bandpass of the monochromator is 16 nm, other lines may contribute some intensity.^5
flame type: S-AA = nitrogen-separated air/acetylene; (fr) = fuel-rich; S-NOA = nitrogen-separated nitrous-
ox ide/acety lene,
c
Detection limits from this work correspond to an analyte fluorescence signal equal to 3 times the standard
deviation of the baseline (SNR=3) calculated from either 16 one-second integrations or from 3/3 the peak-to-
peak noise on the baseline using a three second time constant.
^From references 34, 33 (SNR=2).
e 03
Predicted ICAP-emission limits of detection for the same line(s) used to excite AFS.
f 04
Commercial multi-element limits of detection based on SNR = 2 for ICAP-emission.
^State-of-the-art limits of detection for ICAP-emission using pneumatic nebulization (SNR=2).^
^Line source atomic fluorescence detection limits in a similar flame (SNR=2).^
1Atomic absorption detection limits (SNR=2).^
JLimit of detection based on the normal analytical line, not the most sensitive line.

119
rigorous (SNR = 3) definition of detection limit. While the fluorescence
detection system for ICAP-excited AFS is well optimized for a background
shot-noise limited, dispersive system, using double-pass optics, light
traps and a very low resolution (spectral bandpass = 16 nm) monochroma¬
tor, the optical transfer of the ICAP emission to the flame can be im¬
proved by at least an order of magnitude by the use of an ellipsoidal
87 88
reflector ’ placed off-axis or behind the plasma to collect a much
larger solid angle of emission. This should improve detection limits by
the increase in the light gathering power, assuming scatter does not be¬
come a significant noise source. We are presently collecting only about
2 percent of the source radiation using 5 cm spherical lenses with a
focal length of 9 cm.
The ICAP-excited AFS detection limits are a function of the atomic
emission intensity from the ICAP and the flame background emission inten¬
sity. Shot-noise induced by the flame background emission is the limit¬
ing noise source at the detection limit using the 16 nm spectral bandpass
with both separated air- and nitrous-oxide/acetylene flames. The effect of
spectral bandpass (slit width) on the signal-to-noise ratio (SNR), and thus
on the detection limit, is shown in Figure 22 for cadmium in an air/acetylene
and vanadium in a nitrous-oxide/acetylene flame. In the former flame, the
SNR shows a slight decrease upon changing from a 16 nm spectral bandpass
(2 mm slits) to a A nm spectral bandpass (0.5 mm slits), which is consist¬
ent with the changes in solid angle observed using the H-10 monochromator
without focusing optics. Geometrical considerations show that over 2 cm
of flame height are observed by the collimator although the vignetted
region is considerably extended, due to the small collimator effective
aperture (2.86 cm). In all cases, the slit width is such that the over¬
all width of the flame is viewed by the collimator. The considerable

Figure 22. The Effect of Slit Width on the ICAP-excited AFS signal-to-
noise ratio from ( â–  ) cadmium in a nitrogen-separated air/
acetylene flame and (â– &) vanadium in a nitrogen-separated
nitrous-oxide/acetylene flame. (20 ng/mL Cd; 100 yg/mL V)

SNR. CADMIUM
O .t* oo ro o>
SNR. VANADIUM

122
decrease in SNR upon a further 10-fold decrease in spectral bandpass is
due to a change of the dominant noise from flame background-induced shot-
noise to photomultiplier dark-current shot-noise and/or electronic noise.
In the case of vanadium in the nitrous-oxide/acetylene flame, the more
significant decrease in SNR for the decrease in spectral bandpass from
16 to 4 nm is likely due to the exclusion of fluorescing lines from the
bandpass which decreases the signal more than the case of cadmium, which
involves one fluorescing line. The less significant decrease in SNR ob¬
served in the change from 4 nm to 0.4 nm is also due to the exclusion of
fluorescing lines and geometrical considerations, since the flame back-
ground-induced shot-noise is still limiting at the smaller bandpass.
For some elements, the ICAP-excited AFS detection limits are within
an order of magnitude of the best reported ICAP-emission detection limits
(Zn, Cr, Cd, Mg, Cu) listed in Table 8. Furthermore, the ICAP-excited
AFS detection limits are better or equal to the detection limits obtain¬
able on a commercial ICAP spectrometer for these same elements. These
detection limits are representative of what we can obtain using our me¬
dium resolution monochromator (0.04 nm spectral bandpass) for ICAP-emis¬
sion .
Of further interest is a comparison of detection limits for ICAP-
excited AFS and ICAP-emission using the same line. A recent publication
83
by Winge et_ al_. estimated detection limit capabilities for the promi¬
nent lines of 70 elements emitted in an ICAP excitation source. Their
estimated detection limits using the lines with the best signal-to-back-
ground ratio are very close to the experimentally determined detection
limits for a commercial ICAP instrument which were presented in Table 8.
The predicted ICAP-emission detection limits for the atomic resonance
8 3
lines which we used to excite fluorescence are also presented in Table

123
8. It is interesting to note that for every element (except Pb) deter¬
mined in a nitrogen-separated air/acetylene flame, the ICAP-excited AFS
detection limits are from two to twenty times better than the predicted
ICAP-emission detection limits for the same lines.
When detection limits are determined at the same line, the factors
which must be considered are the solid angle of the ICAP-emission focused
on the flame versus the solid angle viewed by the emission monochromator,
the emission intensity of the excitation solution (10 mg/mL) in the ICAP
versus the emission intensity of the solution used to determine the ICAP-
emission detection limit, the noise sources limiting detection for each
technique, and the efficiency of emission and fluorescence excitation,
collection and detection. Although the signal in ICAP-excited AFS will
lose with respect to factors such as the fluorescence quantum efficiency
(typically 0.01 - 0.03 in an air/acetylene flame) and monochromator
collection efficiency (since only a small percentage of fluorescence
radiation is collected), ICAP-excited AFS will gain based on the solid
angle of collection of ICAP-emission and relative background emission
intensities of the ICAP and the nitrogen-separated air/acetylene flame.
The qualitative significance of these factors are illustrated by the im¬
provement of the "same line" ICAP-emission detection limits using ICAP-
excited AFS as a detection system, as shown in Table 8.
Precision and Linearity. In Figure 23(A), a typical ICAP-excited
AFS analytical growth curve is shown, in this case for zinc, which is
linear over slightly less than L orders of magnitude. In Figure 23(B),
a precision plot is shown for this same element, based on sixteen 1 sec¬
ond integrations at each data point and repeated twice. The analytical
precision at high concentrations is on the order of one to 2 percent
and is primarily limited by the source (ICAP) stability. This is in

Figure 23. ICAP-excited AFS analytical growth curve (A) and precision
curve (B) For zinc in a nitrogen-separated air/acetylene
flame at 213.9 nm.

RELATIVE FLUORESCENCE
125

126
71 17
agreement with other researchers ’ who have reported the ICAP preci¬
sion to be limited primarily by fluctuations in the nebulization and
sample transport system to about one percent.
17
The long term stability of the ICAP emission is excellent, on the
order of a few percent over long time periods, and thus its use to excite
fluorescence represents a considerable advantage over many previous
sources used for AFS such as electrodeless discharge lamps, which must
90
be carefully thermostatted under certain conditions, and the Eimac
91
short-arc xenon lamp, which has a much lower intensity in the ultra¬
violet.
Scatter. The problem of scattered radiation is perhaps the most
significant interference in AFS when resonance transitions are employed.
Scatter can occur from environmental sources, such as reflections off
mirrors and burner heads, but this type of scatter is only significant
when it becomes a dominant noise source due to either source-induced
shot-noise or flicker. The latter is a problem with some pulsed dye
92
lasers, where pulse to pulse variations may be ten percent at a mini¬
mum. In ICAP-excited AFS, we observed environmental scatter to be sig¬
nificant only for those elements with detection limits less than about
5 ng/mL, and even in the case of magnesium, with a detection limit of
0.09 ng/mL, the scatter signal was not a significant noise source.
The other type of scattered radiation is that due to undissociated
matrix particulates in the analytical flame. This scatter has been cate¬
gorized as primarily being of the Mie variety (i.e., due to particulates
73 93
much larger than the wavelength of scattered radiation) ’ and does not
have an easily defined relationship to wavelength as Rayleigh scatter
does (I a X ^). An error in accuracy will result from this type of scat¬
ter, since it may be mistaken for atomic fluorescence. The scatter

127
interference is much more severe using continuum excitation sources than
line sources, because of the greater spectral width of the former.
The primary method for correction using line excitation sources, the
73 94
two line technique, ’ is based on the narrow linewidth of the atomic
fluorescence and the assumption that the scatter signal does not change
appreciably in the wavelength vicinity of the atomic fluorescence line.
Another line from the source, which does not excite significant analyte
or matrix fluorescence, is found near to the analyte line and the scatter
signal is measured at that line, corrected for the relative intensities
of the two lines, and subtracted from the signal excited by the analyte
source line.
The ICAP is the ideal source for scatter correction using the two-
line technique because of the great number of intense ion lines excited
by the plasma. The ionic population of air/acetylene and electron-buffered
(1 mg/mL K as KC1) nitrous-oxide/acetylene flames is insignificant for
most elements and thus these ion lines are available for scatter correc¬
tion along with many other non-resonance transitions. These lines are
equally as useful for the correction for broad band molecular fluorescence
interferences although such interferences would be expected to be more
severe with a continuum source than a line source.
The magnitude of the matrix-scatter interference in ICAP-excited
AFS was investigated for the zinc 213.9 nm line using a 5 percent high-
purity lanthanum solution. The scatter signal was equivalent to a con¬
centration of 6G ng/mL Zn and could be corrected for completely using the
Cd II line at 214.4 nm generated by 10 mg/mL Cd in the ICAP. It should
be noted that any solutions used for production of "scatter-correction"
radiation in the ICAP must be significantly free of analyte or an over-
correction may result. Comparison of analyte emission line intensity and

128
scatter correction emission line intensity from the ICAP is made experi-
73 95
mentally using a 5 percent high-purity lanthanum solution. ’ The
presence of analyte contamination in the scatter correction solution
aspirated into the ICAP can be evaluated by observing if any signal is
generated by an analyte standard in the flame. In general, care must be
taken that the "scatter correction" solution does not emit spectral com¬
ponents capable of exciting fluorescence within the spectral bandpass of
the monochromator.
Another possible method for scatter correction using the ICAP is
72
based on the shape of the "excitation" curve of growth. The technique
96
is similar to the method described by Haarsma et al., which takes ad¬
vantage of the self-absorption of the source at high concentrations. In
the concentration range on the plateau region of the excitation curve of
growth the fluorescence intensity will not appreciably increase while
the emission intensity and thus the scatter will increase. Aspirating
two different high concentrations of the element being determined into
the plasma and knowing the effect of the two different concentrations
on the fluorescence and the emission signals, one can calculate the
scatter signal and subtract it out.
B.4 - Applications
Zinc in Unalloyed Copper (NBS SRM-394 and 396). The determination
of trace zinc in high purity copper is a difficult analytical problem
using either atomic absorption or ICAP-emission. The major zinc reso¬
nance line at 213.856 nm is subject to a direct spectral interference by
the copper 213.853 nm non-resonance transition (11203 - 57949 cm ).
This interference has been reported^ for flame atomic absorption analy-
97
sis and requires an electrodeposition of the copper from solution or a
high-resolution atomic absorption technique employing wavelength modulation

129
and line-nulling before accurate analysis can be performed. The prob¬
lem using ICAP-emission is illustrated in Figure 24 by a scan of the
wavelength region of the zinc 213.856 nm line for the unalloyed copper
SRM 396. While the majority of the copper lines are easily resolved, the
213.853 nm line cannot be with the resolution available in spectrometers
typically used for ICAP-emission. Even with an echelle spectrometer,
98
this line pair has been shown to exhibit an overlap. The emission from
this line at a concentration of 10 mg/mL copper is equivalent to the
emission from approximately 20 yg/mL of zinc, making analysis impossible
without the use of zinc-free copper for matrix-matching. The Zn II line
at 206.2 nm can be used for the determination of zinc by ICAP-emission
without line spectral interference from copper, although background cor¬
rection by scanning over the wavelength region of the line is still re¬
quired to correct for a change in the background level caused by either
stray light due to copper emission or changes in the plasma background.
The zinc detection limit for this line was found to be approximately 4x
worse than at the 213.9 nm line, in agreement with the results of Winge
83
et al. While SRM 394 was analyzed (375 yg/g certified value), SRM 396
(4.7 yg/g certified value) could not be analyzed because of its low zinc
concentration, the poorer detection limit and the continuous background
in the vicinity of the 206.5 nm Zn II line generated by the copper matrix.
The background was equivalent to approximately 1 yg/mL zinc at this wave¬
length. The analysis values for SRM 394 were approximately 10 percent
less than the certified value, indicating a slight interference by ICAP-
emission .
The determination of zinc in both SRM 394 and 396 by ICAP-excited
AFS is summarized in Table 9 along with the ICAP-emission results. The
AFS results agree well with the certified values. There is no significant

Figure 24. Wavelength scans of (A) 20 ug/m!_ zinc and (B) 10,000 yg/mL
copper as SRM 396 (unalloyed copper) illustrating the spec¬
tral interferences observed in ICAP-emission for zinc analy¬
sis in copper.

cun
Cu i
Cull
Cu n
Cun
Cun
Cun
214 8 97
213.853
213 598
213 4 35
213 123
212 603
212 297
00
3
WAVELENGTH (nm
>
Znl 213 856

Table 9
SAMPLE ANALYSIS USING ICAP-EXCITED AFS AND ICAP-EMISSION
Sample
Element
Certified Value (pq/g)a
Analyzed Values
ICAP-excited AES
(pg/q)
ICAP-emission
Unalloyed copper (SRM-394)
Zn
375 ± 38
376 ± 3
325 ± 25
Unalloyed copper (5RM-396)
Zn
4.7 ± 0.3
4.8 ± 0.1
c
fresh water (SRM-1643)
Zn
0.065 ± 0.003
0.0656 ± 0.0008
d
Cd
0.008 ± 0.001
0.0079
d
Ely ash (SRM-1633)
Zn
210 ± 20
219 ± 4
d
Orange juice
Cu
e
0.57
0.60
Zn
e
0.45
0.46
Office of Standard Reference Materials, National Bureau of Standards, Washington, D.C. 20234.
k± one standard deviation of analytical results where multiple samples were analyzed.
Q
cannot be analyzed by ICAP-emission with our experimental setup.
^analysis capability of ICAP-emission for this element in this matrix already established.
0
not a standard reference material.

133
fluorescence excited at the 213.853 nm copper line in the flame, due to
a combination of the relatively low thermal population in the air/acetylene
flame of the 11203 cm energy level and the quantum efficiency of the
fluorescence process. This combination effectively minimizes copper
4
spectral interference in ICAP-excited AF5 by more than a factor of 10
compared to the ICAP-emission case. The effect of the flame as a reso¬
nance monochromator is not significant in this example, since even 10 mg/
mL Cu in the ICAP did not excite any fluorescence from the Cu 213.853 nm
line.
When the 16 nm spectral bandpass is used on the fluorescence mono¬
chromator, several resonance copper lines at 216.5 nm, 217.8 nm, and
218.2 nm are included. Although no spectral interference is observed
when a pure zinc solution (20 mg/mL) is used for excitation in the ICAP,
we found that our supposedly 99.99+ zinc standard contained about 5 yg/mL
copper, indicating a purity of less than 99.98. This was enough copper
to excite fluorescence at the resonance copper lines, and although no
interference was observed for the analysis of SRM 394 in the part-per-
million concentration range, a slightly higher value (approximately 20
percent greater) than the certified value for SRM 396 was obtained using
the 16 nm spectral bandpass. The enhancement due to the copper fluores¬
cence from the resonance lines, equivalent to approximately 10 ng/mL
zinc, was completely eliminated by using the 0.4 nm spectral bandpass.
A scatter signal of approximately 4 percent for SRM 396, equivalent to
2 ng/mL zinc, was observed and corrected for using the Cd II 214.4 nm
line.
Fly Ash (NBS SRM-1633) and Trace Elements in Water (NBS SRM-1643).
Zinc was determined in fly ash and cadmium and zinc in simulated fresh
water by ICAP-excited AFS. No chemical interferences were observed in

134
either case, and the results are presented in Table 9. Excellent agree¬
ment with the certified values was obtained.
Orange Juice. The determination of copper and zinc in Florida orange
juice was performed using both ICAP-excited AFS and ICAP-emission. The
optical arrangement for the former was as described in reference 81.
Agreement of results between the two techniques was good, as illustrated
in Table 9. Matched-matrix standards were employed so that background
correction by wavelength scanning was not required.
In the analysis of orange juice for zinc by ICAP-emission, a series
of wavelength scans through the vicinity of the 213.9 nm zinc line showed
not only the gradually increasing continuum background from the argon
plasma but also superimposed on this background were bands of the y -
2 + 2
system of NO (A z * X n) degraded to shorter wavelengths, resulting from
44
the entrainment of the ambient air, with bandheads at 214.91 nm and
215.49 nm. Furthermore, the phosphate present in the matrix blanks and
in the orange juice produced a strong emission at 213.620 nm. However,
the monochromator resolution was sufficient to eliminate the effect of
these spectral interferences.
For the copper analysis by ICAP-emission, the wavelength scans from
323 nm to 326 nm showed several lines of argon (323.45, 323.681, 324.369,
and 325.76 nm) and strong OH bands (323.5 and 325.7 nm) with some less
intense OH peaks at other wavelengths (323.7, 324.4, and 324.7 nm).
Under our experimental conditions, the argon lines and OH bands caused
no problems in the copper analysis at the 324.7 nm line.

CHAPTER FOUR
ATOMIC FLUORESCENCE SPECTROMETRY IN ICP WITH DYE LASER
EXCITATION "LASER-EXCITED AFS IN ICP"
A - cw Dye Laser As An Excitation Source in ICP
A.1 - Introduction
The radio frequency inductively coupled plasma has become a widely-
99 100
used tool for multi-element atomic emission analysis. ’ Investiga¬
tion of excitation processes in spectroscopic systems is very important
for the full realization of any new tool's analytical utility. This is
particularly true in the case of plasma sources, where the excitation
101 17
mechanisms have been shown to be different from those in flames. ’
102
Mermet and Trassy designed a special rf plasma torch atomic absorp-
g
tion measurement, and Wendt and Fassel determined elements which are
strong monoxide formers by atomic absorption measurements in an rf plasma.
Using electrodeless discharge lamps as the primary excitation source,
103
Montaser and Fassel reported atomic fluorescence in the ICP tail plume
(3-5 cm above coil). Higher signals for fluorescence than emission were
obtained for cadmium, zinc, and mercury, but a special torch configura¬
tion was required.
In this work, the analytical utility of a continuous-wave (cw) argon
ion pumped dye laser excitation source and a conventional ICP torch
atomizer/ionizer was investigated. A cw dye laser was chosen for this
study because: (i) large fluorescence signal levels resulted for those
elements capable of undergoing excitation, by the dye laser used; (ii)
1 is

136
amplitude modulation of the laser allowed use of synchronous detection
techniques; and (iii) the instrumental system was relatively simple.
The major drawback in using a cw laser is the limited wavelength
range (from 573 to 620 nm with a 5 W pump). Smith et used a simi¬
lar cw dye laser with a nitrous oxide/acetylene flame and determined the
possibility of overcoming the limited wavelength range by using excited
lower states and a variety of nonresonance fluorescence processes in
order to increase the number of elements which could be measured. The
higher excitation temperatures in the ICP will increase the populations
of the excited lower levels and should give greater excitation flexibil¬
ity with the cw-laser-ICP than was available in the previous cw laser-
flame studies. This work is a continuation of the Smith et al
study. Although the ICP has much higher excitation temperatures, the
lack of complete thermodynamic equilibrium in the ICP was not necessarily
105
expected to give predictable results as in combustion flames.
A.2 - Experimental
A block diagram of the experimental system is shown in Figure 25.
The Rhodamine 6G cw dye laser, pumped by all lines of the 5 W argon ion
laser, produced «1 W peak output power over the tuning range from 575 to
620 nm. Output power dropped off quickly near the wavelength limits.
Typically the spectral bandwidth of the dye laser was =0.05 nm. The
laser beam was chopped (260 Hz) and focused into the ICP plasma. The
ICP was mounted on an adjustable (x-y-z) table so that any part of the
plasma could be illuminated by the laser without disturbing the alignment
of the laser with respect to the monochromator (0.35 m; f/6.8; 2 nm/mm).
Because two different areas of the plasma were investigated (the
intense analyte pencil region above the coil (0.5-2.5 cm above the coil),

Figure 25. Block Diagram of ICP-CW Laser Fluorescence Spectrometer.

138
I CP - CW LASER FLUORESCENCE SPECTROMETER

139
where atomic emission measurements are performed, and the cooler tail
plasma (3-3 cm above the coil) where mixing of ambient air with the
44
plasma occurs), two slightly different optical arrangements were needed.
In studies of tail plume fluorescence, the monochromator slit was placed
parallel to the laser beam at right angles to the plasma axis. A spher¬
ical lens was used to focus the laser beam to «1 mm while passing through
the plasma. For atomic fluorescence measurements in the analyte pencil
area, the monochromator slit was placed in a vertical position similar
to that used in flame emission measurements. It was found that atomic
fluorescence signals could be increased by a factor of 2-3x through
matching the fluorescing volume of the plasma to the monochromator ob¬
servation area by using a cylindrical lens that focused the laser beam
(normally 1 cm in diameter) to a 1 cm x 1 mm column at the analyte pencil
in the plasma. For spatial fluorescence profiles, the monochromator slit
was placed perpendicular to the focused horizontal laser beam so that
«1 mm x 0.3 mm spatial resolution was possible. The monochromator slit
width was adjusted to 70 urn (spectral bandpass of 0.14 nm) for all emis¬
sion studies and 300 ym (spectral bandpass of 0.6 nm) for all fluores¬
cence studies; the slit widths were determined by maximizing the signal-
to-noise ratio.
Major components of the system are listed in Table 10. The plasma
system was operated at combined Ar flows of 17 L/min. (Cooling flow
rate = 15 L/min; plasma flow rate = 1 L/min; nebulizer flow rate = 0.5
L/min.) The right angle nebulizer supplied with the plasma system was
replaced with the concentric nebulizer listed in Table 10; the nebulizer
flow rate was controlled with a syringe pump (a 1.5 mL/min flow rate was
simple to maintain and operate). Reflected power was kept to a minimum
by the automatic matching network. Limits of detection for the ICP in

Table 10
SPECIFIC COMPONENTS OE EXPERIMENTAL SYSTEM
Component
Model //
Company
Argon Ion Laser
550
Control Laser Corp.
Orlando, EL
Oye Laser
491
Coherent Radiation
Palo Alto, CA
Chopper
125
Princeton Applied Research
Princeton, NJ
ICP Torch Assembly
PT 1500
Plasma Therm INC
RE Generator
HEP 15000
Kresson, NJ
Nebulizer
T-220-A2
JE MEINHARO ASSOCIATES
Santa Anna, CA
Monochromator
EU-700
GCA McPherson
Chicago, IL
Photomultiplier
1P28A
RCA
Somerville, NJ
Current/Voltage Converter
427
Keithly Instruments
Cleveland, OH
Lock in Amplifier
040
Keithly Instruments
Cleveland, OH
Integrator
Lab Constructed

141
the atomic emission mode were found to be similar to those previously
. . 100
reported.
Atomic fluorescence signals were measured with a synchronous detec¬
tion system. For measuring limits of detection (LOD), the lock-in output
was integrated for 10 s. The LOD was taken to be that concentration
equivalent to a signal 3 times that of the standard deviation of 16 con¬
secutive, integrated blank readings. Aqueous standards of analytical
grade reagents were made using deionized water.
Noise sources were characterized in two ways. Background and ana¬
lyte noises were studied by placing neutral density filters between the
plasma and the monochromator and by varying the analyte concentration,
respectively. Peak to peak noise for a 1 s lock-in time constant was
measured as a function of the average signal output.
A 3G0 W EIMAC xenon arc continuum source was substituted for the
laser for comparison purposes. Two spherical lenses were used to focus
radiation from the lamp through the chopper and into the rf plasma.
A.3 - Results and Discussion
For atomic emission measurements, optimal measurements in the ICP
were made in or just above the analyte pencil region. For normal opera¬
tion (powers of 1.2-1.5 kW), the background and analyte emission was so
intense that the fluorescence could not be separated from the background
and/or analyte emission noise coming through the lock-in amplifier. In
Figure 26, the relative intensity profiles for fluorescence, emission,
and background are shown for sodium at 589.0 nm. The emission LOD for
sodium (RF power of 1.2-1.5 kW and measured at 3 cm above the plasma load
13
coil in the tail plume) was 0.2 ppm; instability of the tail plume
suited in this poor LOD.
re-

Figure 26. Relative Intensity Profile for Sodium (589.0 nm, 1 pg mL
Na, 2.5 cm above coil, 1.2 kW).
Na fluorescence
Na emission
background

143

144
By decreasing the power of the plasma in order to decrease the back¬
ground, and by measuring the fluorescence in the analyte pencil region,
the fluorescence signal-to-noise ratio (SNR) increased dramatically. In
Figure 27, the relative sodium spatial intensity profile for this case is
shown. Both background and analyte emission signals were greatly re¬
duced, the fluorescence signal now being »20x the emission signal at the
optimum power for sodium fluorescence which was 700 W. In fact, the
bright fluorescence signal of a 2 pg/mL Na solution was readily observ¬
able by eye.
In Table 11, LODs are given for the elements with excitation tran¬
sitions in the wavelength range of the laser system. Included for com-
104
parison are the values obtained by Smith et_ al_. for excited-state
flame fluorescence with the same cw dye laser. Also listed in Table 11
are atomic emission (with ICP) LODs. The analytical calibration curves
for Ba and Na, shown in Figure 28, have a linear dynamic range of at
least 5 orders of magnitude. Elements studied which gave no measurable
fluorescence for 1000 pg/mL aqueous solutions included Mo, Rh, Sc, Sr,
Cd, and U.
Contrary to our expectations, it is important to note that elements
having fluorescence lines involving excited lower states resulted in
104
poorer LODs with the ICP than with a flame. In fact, for many other
elements having potentially useful atomic transitions, no fluorescence
signals were observed even though observable atomic emission signals for
these levels involved were present. For example, in the case of Ba, the
Ba atomic ground state resonance transition at 553.5 nm which was used By
104
Smith et_ al_. was outside of the wavelength range of the dye used in the
present studies and so could not be investigated. No fluorescence sig¬
nals for Ba could be found for any of the excited state atomic transitions

Figure 27. Relative Intensity Profile for Sodium (589.0 nm, 1 yg mL
Na, 1.5 cm above coil, 0.7 kW). Key to lines same as in
Figure 26.

146
2

147
Table 11
LIMITS OF DETECTION (ug/mL)
CW - LASER FLUORESCENCE
Fluorescence
SPECIES
- Wavelength
X (nm)
FLAME
ICP
EMISSION
ICP
Na (I)
589.0
.0003
.0001
.0002
Ba (I)
553.7
.04
ND
Ba (II)
455.4
. 006a
.0001
Li (I)
610.3
.5
.4
. 003b
V (I)
609.0
.3
5.
a. excited at 585.4 nm
b. excited at 670.7 nm

Figure 28. Analytical Calibration Curves for Na and Ba with ICP-cw Dye
Laser Spectrometric System.

5
H
m
8
o
m
2
5
O
-3
OO-
o «
go.
*-
o 5
* -X
C 3
U3 u3
V. \
3 3
0.01
FLUORESCENCE INTENSITY (ARBITRARY UNITS)
- 6 o 5 o q o
N U .it c»
J I I I I 1 I I
149

150
within the wavelength range of our dye laser and listed by Smith et al.^^
in their flame study. In contrast, however, large signals for barium ion
fluorescence were observed. Suitable barium ion transitions exist in the
wavelength range of the dye laser and are shown in Figure 29 along with
detection limits for various excitation-fluorescence possibilities. These
results for Ba show that analytical line selection is best made on the
basis of highest laser power for the excitation wavelength and high spon¬
taneous emission transition probability for the observed fluorescence
transition. In addition, many elements are best observed as ions in the
ICP; unfortunately, many ion lines exist in the higher energy end of the
spectrum which negated studies with the present cw dye laser.
Although the operation of the plasma at lower power is undesirable
for emission spectrometry (presumably due to lower effective excitation
temperatures), this does not necessarily follow for fluorescence measure¬
ments in the ICP. No visible change in the torodial nature of the plasma
was apparent at the lower powers used and relative stability (as judged
by relative recorder fluctuations) was the same for all powers. The ex¬
citation process for our low power rf plasma was evaluated according to
17
the procedure described by Boumans and DeBoer. They found in a 1 kW
plasma that the ratio of Ba(II) emission intensity at 455.4 nm to that of
the Ba(I) line at 553.5 nm was 3Q0x that expected for an excitation source
at 5858 K in local thermodynamic equilibrium (LTE). The system in this
study gave comparable results at 1 kW power; even at the lowest power
used (0.6 kW), the emission intensity ratio 8a(II)/Ba(I) was 90x the LTE
expected value for a temperature of 5850 K (see Figure 30). Therefore,
non-LTE excitation is most likely taking place at the lower powers used
17
in this study just as at the 1 kW power used by Boumans and DeBoer.

Figure 29. Barium Ion
Transition
Transition
Transition
Transition
Limits of Detection
(uq/mL)
60
>1000
200
100
Energy Level Diagram.
(1):
X
= 493.4
nm;
gA
(2):
X
= 455.4
nm;
gA
(3):
X
= 585.3
nm;
gA
(4):
X
= 614.2
nm;
gA
0.19x108 s"1
0.90x108 s'1
0.19x108 s~1
0.38x108 s'1
Excitation X
(nm)
585.3
585.3
614.2
614.2
Fluorescence X
(nm)
585.3
614.2
585.3
614.2

152
1 Bad)

Figure 30. Barium ion emission at 453.4 nm to Barium atom emission at
553.5 nm for non-LTE study.

154
I 3aü45í
I Bat-5^4
100-
10-
1 -
BARIUM lOty/ATOM INTENSITY RATIOS
1.3 KW
1X1 KW *
Q.9KW
LTE T
THEORY
+ 80 U MANS l 0 E BOER

155
All noise measurements of analyte fluorescence, analyte emission,
and ICP background at two powers 1 kW and 0.6 kW were found to be limited
by "shot noise" except for the case of high concentration fluorescence
which is analyte "flicker noise" limited. Thus, the ICP is "shot noise"
42
limited.
Results with the 300 W EIMAC xenon arc lamp for Cd, Ba, Na, Zn, Mn,
Ca, U, Eu, Mg I, and Mg II were all negative except for magnesium (I) at
285.2 nm. Magnesium, which traditionally gives the best results of any
element with EIMAC excitation, produced a detection limit of 0.3 ug/mL
at 500 W plasma power. On this basis, it was concluded that sources with
excitation temperatures similar to that of the EIMAC xenon arc lamp are
unsuitable for use as a primary excitation source in the present ICP-AFS
system.
3 - Relative Spatial Profiles of Barium Ion and Atom
in the Argon Inductively Coupled Plasma
As Obtained by Laser Excited Fluorescence
B.1 - Introduction
The electron, atom, ion concentration and the temperature are among
the most relevant physical figures of merit of the inductively coupled
argon plasma discharge (rf-ICP) and are certainly the critical parameters
characterizing the usefulness of this device as an atomizer, ionizer and
68
exciter in analytical spectroscopy. Such parameters are known to vary
as a function of input power, plasma and nebulizer gas (argon) flow rates,
analyte species and matrix types, nebulizer and torch design and rf gen¬
erator type and coupling mechanism.
Any modeling of the plasma processes and therefore any prediction
of the optimal analytical conditions to be used rely on the value of the
above mentioned parameters. However, as clearly stated by Kornblum and

156
106“108
DeGalan, these quantities must be obtained as a function of the
spatial coordinates (x,y,z) in the plasma and not merely as an integrated,
average line of sight measurements. Thus, when the data are obtained via
106—115
the emission or absorption techniques, an Abel inversion procedure
is usually applied to convert the values into radially resolved informa¬
tion. Among the limitations of the Abel inversion technique, we may in¬
clude (i) a precise measurement of the lateral intensity distribution
at a number of discrete steps (or continuous scan) over the entire width
of the plasma is needed, (ii) the step width must be smaller than the dis¬
tance over which the intensity changes appreciably, and so at least 20
steps are needed, (iii) the exact location of the central point of the
intensity distribution is needed or else large errors in the radial sig¬
nals lead to anonuleus (even negative) signals at r=0, (iv) the plasma
must be exactly symmetrical and (v) the solution of the Abel integral
equation must be solved via a computer, which is not a serious limitation
but does place an additional burden on the processing of even a relatively
simple set of measurements.
So far, all spatial studies in the ICP have been carried out via
Abel inverted emission and/or absorption measurements to obtain relative
107 108
concentration and temperature profiles. Kornblum and DeGalan ’
have measured axial and radial distribution of temperature, electron
concentration and element concentration in a rf-ICP at atmospheric pres¬
sure operated at 2 kW and 50 MHz and at 0.5 kW and 50 MHz. They also
studied the interference of cesium and phosphate on calcium and magnesium
106 109—113
in the above mentioned low power plasma. Mermet et_ al_. have
also measured radial intensity profiles in an argon plasma operated at
1.3 kW and at 40 MHz in order to determine spatial excitation tempera-
114 115
tures and electron concentrations. Kalnicky et al. ’ have measured

157
spatially resolved excitation temperatures and electron concentrations
in the observation zone of a 27 MHz, Ar rf-ICP operated at 1 kW, this
being the plasma and experimental conditions commonly used in commercial
rf-ICP systems.
It is well known that diagnostic techniques based upon elastic light
scatter (Rayleigh or Mie scatter) and inelastic light scatter (fluores¬
cence or Raman scatter) are capable of direct spatial resolution with no
need for an Abel inversion procedure to be performed. The fluorescence
technique, both atomic and molecular, is well suited to obtain spatially
resolved information on concentration of species and temperature, as it
21
has been shown theoretically and in some cases experimentally. How¬
ever, the high temperature and excitation capabilities of the ICP makes
the fluorescence measurements with conventional excitation sources ex¬
ceedingly difficult, because of the low signal-to-noise ratio, if one at¬
tempts to obtain a reasonably good («1 mm^) resolution. The use of a
pulsed, tunable dye laser and gated detector will combine the advantages
of spatial resolution (because of the high collination of the excitation
beam) and good signal-to-noise ratio (because of the gated operation of
the detection system, if the photomultiplier tube does not saturate be¬
cause of the strong d.c. emission background).
For the first time, to the author's knowledge, experimental spatially
resolved fluorescence intensity profiles of barium ions and atoms in an
ICP plasma, were obtained by measuring the signal from a small plasma
volume (a.0.2 mm^) excited by a nitrogen laser pumped, tunable dye laser.
The aim of this work is to show the great information capability of such
technique, rather than to give an extensive discussion of the results ob¬
tained in terms of the physical processes occurring in the discharge.
We will discuss the feasibility of the laser excited fluorescence method

158
in obtaining absolute concentration profiles of species as well as tem¬
perature profiles.
B.2 - Experimental
A block diagram of the experimental set-up is shown in Figure 31.
116
Individual components as well as model numbers and manufacturers are
collected in Table 12. The actual experimental operating conditions are
given in the figure's captions. The barium concentration used through¬
out all measurements was 100 yg/mL. The choice of this concentration
resulted in a good signal to noise ratio also for the far-edge signals
in both excitation and observation directions. Moreover, all measurements
taken with 100 yg/mL were free from self-absorption and/or self-reversal
(post filter) effects. This was demonstrated experimentally by varying
10 times the barium concentration (down to 10 yg/mL) and obtaining the
same profile as that given by 100 yg/mL, the only difference being the
tenfold decrease of the fluorescence intensity.
As seen from Figure 31, the laser beam was directed into the ICP by
means of two plane mirrors. A small aperture (1 mm) was placed in the
excitation direction, approximately 50 cm away from the ICP. Because of
the slight divergence of the laser beam its diameter throughout the ICP
was measured to be approximately 3 mm. The ICP discharge is imaged at
1:1 magnification outs the entrance slit of the monochromator whose height
is fixed at 1.0 mm and whose slit width was typically set at 0.07 mm.
Thus, the discharge volume over which the measurements are averaged was
approximately 0.2 mm^. It must be noted, however, that the linear resolu¬
tion in the excitation axis (x_ in Figure 31b), dictated by the slit width,
and that in the observation axis (y_ in Figure 31b), dictated by the laser
beam diameter, are different. As far as the height of observation is con¬
cerned (_z in Figure 31b), this will of course be determined by the slit

Figure 31. a) Schematic diagram of the experimental set-up; b) geometrical arrangement referred to
in the other Figure Captions.

a b
LAS EH
160

Table 12
INSTRUMENTAL COMPONENTS AND OPERATING PARAMETERS
Component
Description
Operating
Parameters
rf'-ICP
PT-1500 Torch Assembly
UPE-1500D rf Generator,
Plasma Therm Inc.,
Kresson, N.H.
0.7-1.5 kW
Argon Plasma Gas
flow rate: 13 L/min
Nebulizer
Concentric ring glass
nebulizer, T 230-A3,
J. E. Meinhard Assoc.,
Santa Anna, CA
Nebulizer gas pressure
set at AO psi, except
where noted in text.
Torch //I
Plasma Therm torch,
modified as described by
Genna et al.^' with 1 mm
side arm for Ar plasma
(coolant) gas
Torch //2
Plasma Therm Torch,
unmodified
Monochromator
EU-700, 0.35-m focal
length; 1180 grooves/mm
grating, blazed at 230
nm; f-6.8; 2 nm/mrn
reciprocal linear dis¬
persion. Heath Co.,
Benton Harbor, MI
Slit height: 1 mm, slit
width: 0.070-0.075 mm,
unless otherwise noted in
the text.

Table 12—continued.
Photomultiplier
R-92Ü (Hamamatsu Co.,
Middlesex, N.J.)
-1000 V
H.V. Power
Supply
Current to
Voltage Converter
Keithley 244
Keithley 247
(Keithley Co., Cleveland,
OH)
N^-Laser
UV-14
See Weeks
Dye Laser
DL-
Trigger generator
E-H Research Laboratories
Inc., Oakland, CA
Boxcar
Integrator
160-162
Princeton Applied Research,
Princeton, N.J.
Recorder
Servagor, Gelman Instru¬
ments Co., Ann Arbor, MI
116
162

163
height or by the laser diameter, whichever is smaller. It is worth
stressing that the slit height was set at 1.0 mm mainly to decrease the
ICP d.c. background emission seen by the photomultiplier, rather than
merely to improve the spatial resolution. A low power, He-Ne laser was
used to assure proper alignment of the two apertures. Finally, the line¬
arity of operation of the photomultiplier was always checked with the
insertion of neutral density filters during the measurement procedure.
This simply consisted in tuning the dye laser at the appropriate excita¬
tion wavelengths (either 453.A nm or 614.2 nm), adjusting the ICP housing
by an x-y-z adjustment constructed from a milling table (see Figure 31b)
to allow excitation of the desired spatial element and measuring the re¬
sulting fluorescence pulse with a monochromator-photomultiplier-boxcar
averager system. Several x-y-z values were monitored. Conventional line
of sight integrated emission measurements were also taken to provide a
direct comparison with the fluorescence data. However, no attempt was
made to transform such averaged values into radial values.
B.3 - Results and Discussion
The Ba resonance ionic fluorescence and emission intensities at
455.4 nm obtained at 12 mm above the coil are shown in Figures 32-34 as
a function of the input power to the plasma. In these Figures, the pro¬
files are taken along the excitation axis. The characteristic features
which can be derived from these figures are (i) both fluorescence and
emission profiles show an asymmetric hollow pencil configuration, indi¬
cating a remarkably inhomogeneous distribution of barium ions, (ii) the
asymmetry and the depth of the trough change as the power increases, the
hollow pencil becoming deeper and the asymmetry being rotated over 180°
with respect to the plasma axis, (iii) the emission profile is wider than

Figure 32. Resonance ionic fluorescence and emission profiles for barium
at 453.4 nm. Experimental conditions: ICP power P = 0.7 kW;
monochromator slit: width w= 75 urn, height H= 1 mm. Solu¬
tion nebulization flow rate F = 2.0 mL/min; nebulizer pres¬
sure: 40 psi; barium concentration: 100 ug/mL; z = 12 mm;
y = -1.50 mm. Fluorescence profile taken along the excitation
axis.
a) fluorescence profile
b) emission profile

Intensity (Arbitrary Unit)
165

Figure 33. Resonance ionic fluorescence and emission profiles for barium
at 455.4 nm. ICP power: P = 1.1 kW; monochromator slit width
70 um. All other conditions as in Figure 32. Fluorescence
profile taken along the excitation axis.
a) fluorescence profile; y = -1.50 mm
b) emission profile; y = -1.50 mm
c) water scatter; y = 0.0 mm
d) corrected fluorescence; y = 0.0 mm

(mm)
Intensity (Arbitrary Unit)
167

Figure 34. Resonance ionic fluorescence, emission and scatter profiles
for barium at 455.4 nm. ICP power: P = 1.5 kW; monochromator
slit width = 70 pm; y = 0.00. All other conditions as in
Figure 32. Fluorescence profile taken along the excitation
axis.
a) uncorrected fluorescence profile
b) emission profile
c) scatter profile
d) corrected fluorescence profile

intensity (Arbitrary Unit)
r09

170
the fluorescence profile, especially at lower powers, (iv) the trough is
less pronounced in the emission profile as compared to the fluorescence
profile (both items iii and iv are understandable in terms of the inte¬
grated emission measurements as compared to the spatially resolved fluor¬
escence measurements, and (v) perhaps the most curious observation is
that at the center of the plasma, at this observation height, a scatter
signal is clearly evident when water was aspirated (see Figures 33 and
34). The position of the maximum scatter signal was displaced about 1 mm
along each axis (x_ and y) from the central geometric axis of the plasma.
This asymmetry might be determined by the alignment of the nebulizer tube
and the precision of manufacture of the orifice. Extensive checks were
made to insure that this signal was not due to other sources. Wavelength
scanning of both laser and monochromator showed that the signal was not
due to the carry-over of barium contamination in the spray chamber.
Moreover, careful cleaning of the whole nebulizer/torch assembly gave
no reduction in the signal, showing that it was not due to scattering
from solid impurity particles carried from nebulizer or aerosol tube when
water was aspirated into the plasma. As shown in the subsequent figures,
the scatter signal decreases in importance with height of observation.
It seems therefore justified to conclude that this scatter indicates the
presence of minute water droplets. Further measurements have confirmed
the presence of these droplets at heights up to 13-18 mm above the coil
when nebulizer gas pressures of 30-40 psi are used and at least up to
12 mm even when the pressure is reduced to 25 psi.
A similar trend is also observed when the fluorescence profile is
taken along the observation axis (Figures 35 and 36). Here, however,
the trough tends to be filled when the input power increases.

Figure 35.
Resonance ionic fluorescence profile for barium at 455.4 nm. ICP power: P = 1.5 kW. All
other conditions as in Figure 32. Fluorescence profile taken along the observation axis.
a) x = -1.0 mm
b) x = 0.0 mm
c) x = 1.5 mm

Intensity (Arbitrary Unit)
Y (mm)
-4
hO

Figure 36(i). Resonance ionic fluorescence profile for barium at 455.5 nm. x = 1.5 mm. All other
conditions as in Figure 32. Fluorescence profile taken along the observation axis.
a)
ICP
power:
P = 0.7
kW
b)
I CP
power:
P = 1.1
kW
c)
ICP
power:
P = 1.5
kW

Intensity (Arbitrary Unit)
7o -
a
b
c
60
50
'to
30
Ü0
10
o

Figure 36(ii). Same as in Figure 36(i) except for x =
a)
ICP
power:
P = 0.7
kW
b)
ICP
power:
P = 1.1
kW
c)
ICP
power:
P = 1.5
kW
-1.0 mm.

Intensity (Arbitrary Unit)
o
fO
o o
-c- V
© o
i ;
V\ “
S'
a
t
O'
I
9LI

177
Figures 37-39 represent the fluorescence profiles obtained at an
observation height of 18 mm above the coil, again along both the excita¬
tion and observation axis. These figures clearly show that (i) the asym¬
metry in the profile is still observed and it is more pronounced along
the laser axis as compared to the monochromator axis, (ii) the profile
starts flattening out, even at low powers, when the measurements are taken
for both x_ and v_, displaced from the plasma center, (iii) there is no sig¬
nificant increase in the width of the profiles as compared to that at
12 mm, (iv) the H^O scatter is now insignificant, and (v) the trough in
the profile decreases with increasing input power, indicating an approach
to a more uniform distribution of species.
When the observation height is increased to 24 mm above the coil,
the hollow pencil configuration turns into a rather broad, fairly uniform
distribution, at least along the laser axis (see Figures 40-42). It seems
logical to conclude that the plasma expands radially with height while its
optical depth increases. This fact is indeed confirmed by the presence
of self-absorption effects at high concentrations at these and greater
heights from the results seen in chapter 3 and the work of Human and
69
Scott. By increasing the input power, the distribution becomes nar¬
rower .
Figures 43-45 show similar measurements at 12 mm above the coil ob¬
tained at tuning the laser at 614.2 nm while still observing the fluores¬
cence at 455.4 nm. The laser transition originates from an excited metas¬
table barium ion level and reaches the same level from which the fluor¬
escence at 455.4 nm is emitted, i.e., we are now observing the antistokes
105
direct line ionic fluorescence. The overall profile distribution does
not seem to change from one already observed in the previous figures, and
similar results are also obtained when the observation height is increased

Figure 37(i). Resonance ionic Fluorescence profile for barium at 455.4 nm. z = 18 mm. All other con¬
ditions as in Figure 32. Fluorescence profile taken along the excitation axis.
a) y : -1.0 mm
b) y = 1.0 mm
(ii). Same as (i). Fluorescence profile taken along the observation axis.
a) x = 0.0 mm
b) x = 2.0 mm

Intensity (Arbitrary Unit)
K
3*
3
T
I
Q
á
P'
¿Li
un

Figure 38(i). Resonance ionic fluorescence profile for barium at 455.A nm. z = 18 mm; monochromator
slit width: W = 70 pm; ICP power P = 1.1 kW. All other conditions as in Figure 32.
Fluorescence profile taken along the excitation axis.
a) y = -1.0 mm
b) y = 1.Ü mm
Same as (i). Fluorescence profile taken along the observation axis.
a) x = 0.G mm
b) x : 1.5 mm
(ii).

( «JUJ) x < ( muí)
o
o
O
Intensity (Arbitrary Unit)
~c
o
o
^r\
O
O
C
v
i
-Ei
L8l

Figure 39(i). Resonance ionic fluorescence profile for barium at 455.4 nm.
z = 13 mm; monochromator slit width W = 70 pm; ICP power
P = 1.5 kW. All other conditions as in Figure 32. Fluor¬
escence profile taken along the excitation axis.
a) y : -1.0 mm
b) y = 1.0 mm
(ii). Same as (i). Fluorescence profile taken along the obser¬
vation axis.
a) x : 0.0 mm
b) x ; 1.5 mm

(aun) i (¡mn)
Intensity (Arbitrary Unit)
CD
100

Figure 40(i). Resonance ionic fluorescence and emission profiles for
barium at 455.4 nm. z = 24 mm. All other conditions as
in Figure 32. Fluorescence profile taken along the exci¬
tation axis.
a) emission; y = -1.0 mm
b) fluorescence; y = -1.0 mm
c) fluorescence; y = 1.0 mm
(ii). Resonance ionic fluorescence profile for barium at 455.4 nm.
z = 24 mm. All other conditions as in Figure 32. Fluores¬
cence profile taken along the observation axis.
a) x r 0.0 mm
b) x = 2.0 mm

(mm)
hoi

Figure 41(i). Resonance ionic fluorescence and emission profiles for
barium at 455.4 nm. z = 24 mm; ICP power P = 1.1 kW;
monochromator slit width W = 70 ym. All other conditions
as in Figure 32. Fluorescence profile taken along the
excitation axis.
a) emission; y = -1.0 mm
b) fluorescence; y = -1.0 mm
c) fluorescence; y = 1.0 mm
(ii). Resonance ionic fluorescence profile for barium at 455.4 nm.
Conditions as in (i). Fluorescence profile taken along
the observation axis,
x = 0.5 mm

Intensity (Arbitrary Unit)
Vj*
(U)

Figure 42(i). Resonance ionic fluorescence and emission profiles for barium at 455.4 nm. z = 24 mm;
ICP power P = 1.5 kW; monochromator slit width W = 70 yin for fluorescence, 50 ym for
emission. All other conditions as in Figure 32. Fluorescence profile taken along the
excitation axis.
a) emission; y = -0.5 mm
b) fluorescence; y = -0.5 mm
(ii). Resonance ionic fluorescence profile for barium at 455.4 nm. Conditions are the same
as in (i). x = 0.5 mm. Fluorescence profile taken along the observation axis.

X (mra)
(ID
Y (nun ) *-
189

Figure 43(i). Antistokes direct line ionic fluorescence profile for
barium at 453.4 nm (excitation wavelength 614.2 nm). All
other conditions as in Figure 32. Fluorescence profile
taken along the observation axis.
a) x : -1.0 mm
b) x : 0.0 nim
c) x = 1.5 mm

(san)
intensity (Arbitrary Unit)
\o
100

Figure 43(ii). Same as Figure 43(i). Fluorescence profile taken along
the excitation axis.
a) y : -1.5 mm
b) y = 2.0 mm

(aun)
Intensity (Arbitrary Unit)
o
o
i
ro
o
1
o
—L
p- a\
o o o
J I l-
vO
O
1
J L
100

Figure 44(i). Antistokes direct line ionic fluorescence profile for
barium at 455.4 nm (excitation wavelength 614.2 nm). ICP
power P = 1.1 kW; monochromator slit width W = 70 ym. All
other conditions as in Figure 32. Fluorescence profile
taken along the observation axis.
a) x = 0.0 mm
b) x : 1.5 mm

íntenaity (Arbitrary Unit)
v^>
o
vO
v_n
1017:

Figure 44(ii). Same as Figure 44(i).
the excitation axis.
a) y = -2.0 mm
b) y : 0.0 mm
c) y = 2.0 mm
Fluorescence profile taken along

Intensity (Arbitrary Unit)
rv>
o
1
O
1
o
o
J I L
v£>
110

Figure 45(i). Antistokes direct line ionic fluorescence profile for barium
at 455.4 nm (excitation wavelength 614.2 nm). ICP power
P = 1.5 kW; monochromator slit width = 70 pm. All other
conditions as in Figure 32. Fluorescence profile taken
along the observation axis.
a) x = 0.0 mm
b) x = 1.5 mm
Same as (i). Fluorescence profile taken along the excitatioi
axis.
a) y = -2.0 mm
b) y = 0.0 mm
(ii).

110
100
90
80
70
60
50
4-0
30
20
10
0
199
(i)
(ii)
a
i i
i i
v (na)
X (am)

200
However, some points are worth being stressed here (i) the fluorescence
technique is versatile, since many combinations of excitation/fluores-
cence wavelengths can be found, (ii) obviously, even if present, scatter¬
ing would not affect the results here, (iii) the concentration of a me¬
tastable level rather than that of the ground state is sensed here. This
21
has interesting possibilities for measuring the plasma temperature. In¬
deed, the ratio of the antistokes to resonance fluorescence gives an im¬
mediate qualitative indication of the excitation (ion) temperature profile
for the transitions considered, under those particular experimental con¬
ditions. Figure 46 shows both the resonance fluorescence profile and the
antistokes fluorescence profile on the same scale; the ratioing of these
profiles should reproduce the temperature profile.
In an attempt to follow the atom distribution as well as the ion
distribution, the resonance atomic fluorescence of barium was observed
by tuning the laser at 553.5 nm. The resulting profile along the exci¬
tation axis is shown in Figure 47 for three different powers. It is in¬
teresting to note the ion and atom profile are complementary to each
other. In fact, the atom distribution is narrower than the ion distri¬
bution and peaked almost at the position where the ion profile show a
minimum. Presumably, the barium atom distribution would be much less
sensitive to the temperature variation than the barium ion distribution.
Finally, a spatial profile of the ionic resonance fluorescence was
obtained in the same conditions as those reported in Figure 32 and at
three different powers. This was done in order to ascertain if major
differences in the profiles could be found with the two torches, indicat¬
ing some artifact with the torch used for obtaining the reported profiles.
As Figure 48 indicates, the commercial torch shows the same double-peaked,

Figure 46. Resonance and antistokes ionic fluorescence of barium at
455.4 nm. Profiles taken along the observation axis. ICP
power P = 0.7 kW; x = -1 mm; z = 12 mm. Other conditions as
in Figure 32.
a) resonance ionic fluorescence
b) antistokes ionic fluorescence

(mm)
Intensity (Arbitrary Unit)
I'J
o
bo
200

Figure 47. Resonance atomic fluorescence profiles for barium at 553.5 nm.
Nebulizer pressure: 25 psi; monochromator slit width W = 150
urn. All other conditions as in Figure 32. Fluorescence pro¬
file taken along the excitation axis.
a)
corrected fluorescence, P =
0.7
kW
b)
corrected fluorescence, P =
1.1
kW
c)
corrected fluorescence, P =
1.5
kW
d)
scatter profile, P = 0.7 kW
e)
scatter profile, P = 1.1 kW
f)
scatter profile, P = 1.5 kW

Intensity (Arbitrary Unit)
o
ho
o
100

Figure 48. Resonance ionic fluorescence profile for barium at 455.4 nm
as obtained with Torch #2 (see Table 12). Conditions are the
same as in Figure 2 except for y = 1.0 mm.
a) ICP power P = 0.7 kW
b) ICP power P = 1.1 kW
c) ICP power P = 1.5 kW

(nun)
Intensity (Arbitrary Unit)
o
o
IV> ^
o o
i L
o
J
Vjl
o
L
ON
o o
J I
I
V^-> -
>
is)
o
ON
+
VjJ
1-08

207
asymmetric distribution along the excitation axis. We therefore believe
that the obtained profiles are representative of the relative distribu¬
tions of the barium species in the plasma.
C - Pulsed Dye Laser as an Excitation Source in ICP
C.1 - Introduction
The advantages of the inductively-coupled plasma (ICP) as an atomic/
13
ionic vapor cell for emission spectrometry have been well documented.
The high temperature (-6000 K) as well as long residence time experi¬
enced by the analyte makes the ICP extremely effective for vaporization,
atomization, and/or ionization processes and also produces an extremely
complex and intense spectrum with many analytically useful atomic and
ionic emission lines. There are, however, inherent disadvantages to the
ICP when used for emission spectrometry (ICPAES). A high resolution
monochromator is required to isolate the analyte emission from the plasma
background and matrix element emission. Background correction procedures
are mandatory for accurate analytical determinations using the ICP for
emission. Most significant, however, is that the detectability of the
present ICPAES method is fundamentally limited by the characteristics of
the technique itself. Although some improvement may be expected from
refinements in nebulization design and increases in rf power applied to
the plasma, only a major development similar to the development of elec¬
trothermal atomization for atomic absorption spectrometry will result in
"orders of magnitude" improvement in ICPAES detection limits.
One major advantage that the technique of atomic fluorescence spec¬
trometry (AFS) exhibits over other atomic spectrometric techniques is
the direct dependence of sensitivity on the intensity of the excitation

208
source (short of saturation of the spectral transition). Application
of the ICP to AFS measurements should thus provide an extremely effective
combination. The inert gas atmosphere provides a high quantum efficiency
and the high temperature will not only reduce chemical interferences, but
will also increase the number of analytically useful fluorescence tran¬
sitions. Background correction using ICPAFS is not as critical as in
ICPAE5 since matrix-induced changes in the plasma background are not ob¬
served or are easily corrected for by blocking the laser, and spectrom¬
eters of moderate resolution are satisfactory. Most important, however,
is the simplicity of improving detection limits by increasing source in¬
tensity.
Several investigators have used the ICP as an atomic/ionic vapor
cell for AFS. Using electrodeless discharge lamps as the excitation
103
source, Montaser and Fassel reported atomic fluorescence in the ICP
tail plume (3 to 5 cm above the coil). Better detection limits for fluor¬
escence than emission were obtained for cadmium, zinc and mercury using
a special torch configuration. In section A of this chapter we have in¬
vestigated the application of a continuous-wave dye laser to AFS in the
ICP for barium, sodium, lithium, and vanadium. We were restricted, how¬
ever, by the limited wavelength range of our laser and found that a power
level of 0.7 kW provided the best signal-to-noise ratio (SNR).
At the present state-of-the-art, the pulsed tunable dye laser is
the most useful laser for the excitation of fluorescence in atomic vapor
cells because of the wide wavelength range that can be covered. In this
investigation, we have studied the application of two such lasers, a
flashlamp-pumped dye laser and a nitrogen laser-pumped dye laser, to the
excitation of atomic and ionic fluorescence in the ICP.

209
C.2 - Experimental
The nitrogen laser-pumped dye laser (UV-14, Molectron Corp., Sunny-
116
vale, CA) and the flashlamp-pumped dye laser (CMX-4, Chromatix Inc.,
118 119
Sunnyvale, CA) ’ were used as the excitation sources for AFS in the
ICP. The experimental system was similar to that described in section
A of this chapter with the following modifications. Experimental meas¬
urements with the flashlamp-pumped dye laser were made using rhodamine
6G laser dye, frequency doubling, and narrowing of the spectral bandwidth
of the laser to approximately 0.003 nm using a high finesse etalon. The
laser radiation was focused by a lens (Spectrosil, 2.3 cm diameter,
f.1 -=30 cm) to a spot 0.1 to 0.2 cm in diameter 1.5 to 2.5 cm above the
coil in the pencil region of the plasma. The resulting fluorescence was
focused 1:1 on the 0.35-m monochromator which employed a 3 mm slit height
and 0.5 mm slit width (spectral bandpass =1 nm). The photomultiplier
116
was modified for pulsed, high current operation and synchronous gated
(boxcar) detection was employed. A stripchart recorder and integrator
were used for readout. Experimental measurements with the nitrogen laser-
116
pumped dye laser were as described by Weeks et_ al_. and Omenetto et_
120
al. “ as well as the detection and signal processing systems for both
lasers. The forward power to the ICP was 0.65 kW for the atomic lines
and 1.1 kW for the ionic lines studied.
C.3 - Results and Discussion
Flashlamp-pumped dye laser. Detection limits for laser-excited ICP-
atomic fluorescence spectrometry (LICPAFS), ICP atomic emission spectrom¬
etry (ICPAES), and laser-excited flame AFS (LFAFS) are given in Table 13.
For the two elements investigated, the detection limits for LICPAFS were
approximately two orders of magnitude worse than the best ICPAES detec¬
tion limits which are reported in the literature using pneumatic

Table 13
DETECTION LIMITS (ng/mL)
ELEMENT
FLUORESCENCE WAVELENGTI l(rtm)
^ Xexcitatior/*fluorescence^
LICPAES
PulsedC cw^
LEAES
Pulsed
ICPAES
Iron3
Eel
296.7/373.5
50
-
0.06e
26(4.3)h, 0.21
Tin
SnI
300.9/317.5
500
-
3f
200(111)h, 61
q . b
Barium
Ball
455.4/455.4
2
-
-
1(1.3)h, 0.061
Ball
614.2/455.4
30
6
-
-
Indium^
Ini
410.2/410.2
300
-
0.8CJ
400(187)h, 301
aElash.lamp-pumped dye laser.
^Nitrogen laser-pumped dye laser.
c
This work, with detection limit defined as 3 x std. deviation of the noise using an observed time constant
of 1 s.
Continuous wave dye laser detection limit (Section A of this chapter).
0
LEAES detection limit using the same transition as LICPAES with a 10 s time constant and multipass cell
(Ref. 110).
f
LEAES detection limit using the same transitions as LICPAES with a 1 s time constant and single pass cell
(Ref. 119).
l^LEAES detection limit using the same transitions as LICPAES with a time constant from 0.5 to 5 s and a single
pass cell (Ref. 116).
a

Table 13—continued.
best ICPAtS detection limits using our monochromator/detection system
ICPAES detection limits (Ref. 83) for same lines in parenthesis.
1State-of-the-art ICPAES detection limits using pneumatic nebulization
with a 0.3 s time constant;
(Ref. 83).
estimated

212
nebulization, although they are almost identical to the best detection
limits that we can obtain with our instrumentation by ICPAES. Further¬
more, they are within an order of magnitude of the estimated detection
83
limits for ICPAES published by Winge et_ al_. for the same lines.
Of more significance, however, since they were performed with the
same laser system, is a comparison of LEAFS with LICPAFS. The LFAFS de¬
tection limits using a nitrogen-separated air-acetylene flame are two to
three orders of magnitude better than the LICPAFS detection limits.
While a factor of 3 difference in laser power resulting from losses in
reflective optics used to direct the laser beam into the ICP (3 mirrors
and 1 lens compared to only 1 mirror for the LFAFS system) can ac¬
count in a small part for the poorer LICPAFS detection limits, the
greatest effect is undoubtedly due to the greater background emission
(and noise) of the plasma. The LICPAFS and LFAFS detection limits were
obtained under shot-noise limited conditions. In Figure 49, the effect
of rf power on the SNR of the fluorescence signal from 10 ug/mL Fe at
power levels of 0.65 kW and 1.25 kW is shown. 'While the background sig¬
nal increases by a factor of approximately 18 with increasing power, the
SNR decreases by approximately 4 fold, characteristic of a shot-noise
limited system.
Factors influencing the signal and SNR for the LFAFS and LICPAFS
methods include: efficiency and rate of atom production; quantum effi¬
ciency of the atomic transition; luminosity of the entrance optical-
monochromator-detection system; and background emission of the atomiza¬
tion system. The efficiency and rate of atom production in the flame
and ICP depends on the rate and efficiency of sample introduction;
although no measurements were made of this parameter, it is assumed that
the ICP is a much more efficient atomizer. Similarly, it is also assumed

213
that the ICP is a much less efficient quencher of excited atoms as com¬
pared to combustion flames. The luminosity (throughput) of the LFAFS
system (16 nm spectral bandpass and an f/3.5 aperture) was much greater
(^64x) than that of the LICPAFS system (1 nm spectral bandpass and an
f/6.8 aperture). Finally, the background emission of the ICP is several
orders of magnitude greater than that of the nitrogen-separated air/
acetylene flame.
As shown in Figure 49, detector/electronic noise (the noise con¬
tributed by the detector and electronics in the absence of photons strik¬
ing the detector) is a major noise source at low ICP power levels (0.65
kW), although the dominant noise is ICP background emission shot-noise.
At the higher ICP power level used (1.25 kW), the ICP background emission
shot-noise is the only major noise source. The noise sources in an ICP
analysis will therefore vary from detector/electronic noise at very low
background emission intensities, through a region of moderate background
emission intensity where background emission shot-noise is dominant, to
finally, at high background emission intensities, background emission
flicker is the major noise source. The best region to perform an analy¬
sis, based on signal-to-noise ratio considerations, is the background
emission shot-noise limited region (when the background emission is es¬
sentially a continuum over the spectral bandpass of the wavelength dis¬
persive device). In the detector/electronic noise region, the noise is
not a function of optical throughput, so the SNR (i.e., the signal com¬
ponent) may be increased by increasing the throughput. In the background
emission flicker noise region (again, under conditions of a continuum
background, which we observed for the elements we investigated), the
noise may be decreased at a rate faster than the signal by decreasing
the spectral bandpass, thus again improving the SNR. Thus, methods of

Figure 49. Recorder tracings of laser-excited atomic fluorescence signals from 10 pg/mL iron in the
ICP.
(A) Detector/electronic noise with photomultiplier shutter closed.
(B) Baseline and fluorescence signal at 0.65 kW forward power to the ICP.
(C) Baseline and fluorescence signal at 1.25 kW forward power to the ICP.

(A)
— ZERO
INTENSITY
215

216
improving the SNR for the aforementioned noise regions place one in the
background emission shot-noise limited region. Here, an increase or de¬
crease in spectral bandpass does not change the SNR as long as the upper
or lower noise regions, where new noise sources are added, are not too
closely approached. The SNR can be improved in the background emission
shot-noise limited region by increasing the optical throughput by means
other than increasing the spectral bandpass, such as increasing the f-
number of the optical system to match that of the spectrometer. This
method will be effective until the background emission flicker noise re¬
gion is reached, where further increases in throughput will not improve
the SNR.
As mentioned previously, the throughput of the LFAFS system is much
greater (»64x) than the throughput of the LICPAFS system. Figure 49 il¬
lustrated the LICPAFS analysis to lie in the background emission shot-
noise limited region (0.65 kW) close to the detector/electronic noise
limited region. The significantly lower background level of the separated
flame would thus place the LFAFS analysis far into the detector/electronic
noise region using the optical throughput of the LICPAFS system. There¬
fore, the increased throughput of the LFAFS system significantly improves
detection limits using flames compared to the ICP for laser-excited AFS,
as was illustrated in Table 13.
Nitrogen Laser-pumped Dye Laser. Detection limits shown in Table
13 are similar to those observed for the flashlamp-pumped dye laser, rela¬
tive to the other techniques listed. The limiting noise sources for
LICPAFS (with the nitrogen laser-pumped dye laser) were a combination of
radiofrequency interference noise from both the ICP and the nitrogen laser
(using the 15 ns gate) and the background emission snot-noise from the
plasma.

217
The expected improvements in LICPAFS detection limits due to an im¬
provement (compared to flames) in the quantum efficiency and in the re¬
stricted volume of the analyte in the plasma (which is optimal for laser
excitation) are more than offset by the increase in the background in¬
tensity of the ICP compared to separated flames. The detection limit
differences between LICPAFS and ICPAES are largely due to the duty cycle
differences in the measurement systems (cw compared to 1 ps or 5 ns
pulsed times the repetition rate) under shot-noise limited conditions
(flashlamp-pumped) or radio-frequency interference/shot-noise limited
conditions (nitrogen laser-pumped). Barium fluorescence, for example,
is saturated using the nitrogen laser-pumped dye laser, so the fluores¬
cence intensity is significantly greater than the emission intensity when
measured over the gatewidth of the boxcar averager used for signal
processing. Nevertheless, the ICPAES detection limit under continuous
d.c. processing conditions is about the same as the LICPAFS detection
limit. In such cases, improvement in AFS detection limits can only be
obtained by using lasers of greater duty cycle, assuming complete, uni¬
form illumination of the atomic vapor by the intense central (spatial)
portion of the laser beam.
The major noise source at high concentrations in LICPAFS is flicker
noise due to pulse-to-pulse variations (intensity and spatial) of the
118 119
laser; a similar noise component was observed in flame cells. ’
Analytical growth curves for the elements studied were linear up to ap¬
proximately 1000 ug/mL.

CHAPTER 5
CONCLUSIONS AND FUTURE WORK ON INDUCTIVELY
COUPLED PLASMA EITHER AS ATOM/ION CELL OR
AS AN EXCITATION SOURCE
As stated in the literature the ICP is an excellent source of exci¬
tation for atomic/ionic emission spectroscopy. Based on the results pre¬
sented in Chapter 2, one can minimize molecular interferences by mini¬
mizing ambient air mixing with plasma gas; a more common way is to use a
longer torch. In practice, as time passes, the torch becomes cloudy and
spectral analysis proves difficult. The second way would be to design £
new induction torch configuration allowing use of an argon (or nitrogen)-
separated plasma or simply by making a smaller housing for the torch
and flushing it with argon or nitrogen. Doing this and using a 1 m JY
monochromator would result in a lower detection limit for atomic/ionic
emission spectrometry. Also, the use of liquid argon because of lower
impurity than the commercial argon would be beneficial.
Since the behavior of heating and decomposition of dry particles
injected into an argon and a nitrogen ICP discharge have been investi-
121
gated with a computer simulation technique by Barnes and Nikdel and
it was shown that the nitrogen ICP discharge overall is more effective
than the argon ICP discharge, it would be interesting to verify their
results experimentally by using a high power rf-generator with nitrogen
as a plasma gas in atomic/ionic emission spectrometry. Also, from the
diagnostic point of view "laser induced fluorescence" with a N^-pulsed
218

219
dye laser or excimer-laser in this type of ICP would provide valuable
information to spectroscopists, in the field.
The effectiveness of the nitrogen ICP is probably due to a large
population (concentration) of metastable nitrogen molecules which are
then mixed with a thermally vaporized metallic species in the induction
torch. The large excess and long life-time of the metastable nitrogen
permits multiple excitation-emission cycles to occur during the resident
time of the analyte in the torch which is based upon the energy transfer
from metastable nitrogen molecules to the metal atoms/ions.
From the results presented in Chapter 3, we can conclude: (i) that
the ICP is undoubtedly an excellent excitation source as far as its spec¬
tral emission characteristics are concerned. In agreement with the re-
69
suits of Human and Scott the very long linear concentration ranges ob¬
tained are due to the remarkably low self-absorption and to the absence
of self-reversal at the heights used for analytical measurements. Re¬
sults are preliminary and must be considered on a qualitative basis only.
For example, the spatial (height) resolution was low; the results are an
average over the stated height ±5 mm; (ii) similar information concern¬
ing ionic emission can be obtained provided that a sufficient density of
ions is created in the flame atomizer; here one can use two ICP's to
study the ion characteristic in plasmas.
Several other conclusions can be derived from the experimental eval¬
uation of characterization of the ICP as an excitation source in atomic/
ionic fluorescence spectrometry in Chapter 3: (1) as stated originally,
the ICP has been confirmed to be an extremely versatile and intense ex¬
citation source for the atomic fluorescence determination of all the ele¬
ments investigated; (2) the ICP combines the versatility of a continuum
source with the high spectral irradiance and selectivity of a line source;

220
(3) the excellent multi-element excitation capability of the ICP simpli¬
fies the application of the 2-line method of correcting for scattering
problems using resonance transitions because of the many neutral as well
as ionic lines are available; (4) the spectral selectivity of the atomic
fluorescence technique is shown to be advantageous in certain analytical
applications where the emission technique is plagued with spectral in¬
terferences. The ICP proved to be an excellent excitation source for
atomic fluorescence, allowing low detection limits to be obtained. Be¬
cause of its extreme versatility (due to the excitation capability of a
great number of elements), this source could prove to be useful for se¬
lected, specific applications in which the fluorescence technique presents
fewer problems than the emission technique. Therefore, even though the
ICP has been shown to be of marginal use as an atomizer in atomic fluores-
103 122
cence, ’ its potential as an excitation source is worthy of more in¬
vestigation, particularly when the experimental facilities are already
available in the laboratory and where spectral interferences cause prob¬
lems with the emission technique using the available spectrometer resolu¬
tion .
In addition to this, several promising future areas of application
for this source can be devised and are discussed below.
(1) Because of the high excitation power and freedom from inter-
element interferences, the ICP emission of several elements aspirated
simultaneously will result in little, if any, degradation of the detec¬
tion limits obtained in atomic fluorescence, provided that no spectral
interferences will result. Therefore, the use of a programmable slew-
scan monochromator would permit the sequential determination of several
elements in one sample.

221
72
(2) The shape of the "excitation" curve of growth should allow
the possibility of scatter correction by taking advantage of the differ¬
ences in the source emission intensity and excited-fluorescence intensity
dependence on concentration due to self-absorption in the source.
(3) Relatively high concentrations of the element investigated in
a given matrix can be analyzed directly by aspirating the sample into
the ICP rather than in the flame, while monitoring the fluorescence
signal from a standard aspirated into the flame. This avoids the neces¬
sary dilution of the sample solution, should the analysis be performed
in the conventional manner by AFS.
(4) The system may also prove useful for electrothermal atomiza¬
tion techniques or hydride generation techniques, where the very low
emission levels of these atomization cells may further improve detection
limits.
(5) To increase the spectral irradiance of the ICP, it is possible
to use a double coil system constructed one to two inches in distance
apart and then by focusing the volume between them into the flame or any
other atom/ion cell for atomic/ionic fluorescence spectrometry. This
type of design should produce a higher spectral irradiance than the
normal one coil system, and highly stable source of excitation for in¬
troduction of very high concentration solutions into the ICP.
(6) Although, in principle, the ICAP could also be advantageously
used as a primary source in atomic absorption analysis, especially for
elements which exhibit low hollow cathode lamp intensity, this applica¬
tion does not seem to offer any advantage as compared to the emission
technique, not even for specific applications as in the case of atomic
fluorescence.

222
In conclusion, it is my opinion that the ICAP-excited AFS technique
is an ideal adjunct to an ICAP-emission spectrometer, capable of solving
many specific analytical problems. An increase in the collection effi¬
ciency of the ICAP-emission focused on the flame should considerably im¬
prove the already impressive detection limits.
The results in Chapter A, show that the atomic fluorescence in the
ICP using a cw dye laser source is possible and can be done. However,
the system as described is not analytically useful because of the limited
wavelength range of the present cw dye laser, the rather high cost of
the additional components needed to convert an ICP-AE system into a cw
laser excited ICP-AF system, and the rather poor (or not substantially
improved) detection limits compared to the ICP-AE system. The use of
lower powers (0.5-1 kW) in the ICP is possibly undesirable due to the
unknown effects of lower power upon desolvation and vaporization proc¬
esses for samples more complex than those employed in this study. It was
predicted that both the limited wavelength range and the necessity that
power be reduced to decrease background radiation could be overcome
through the use of a pulsed laser with gated detection. All results from
17
this study support the non-LTE excitation conditions. The use of
fluorescence in the ICP using a laser source should certainly be a prac¬
tical tool in diagnostic studies (spatial temperatures and densities) of
plasmas.
The results presented in this investigation (Chapter A) have clearly
demonstrated the remarkable attractiveness of the laser excited fluores¬
cence technique in modeling directly the relative distribution of species
in the ICP discharge with high spatial resolution. As stated in the
previous literature, such measurements are compulsory if any at¬
tempt is made to understand the complex processes occurring in the plasma.

223
It is also worth pointing out that the fluorescence intensity de¬
pends upon linearity of the quantum efficiency of the transition as long
as the fluorescence intensity varies linearly with the excitation inten¬
sity. The quantum efficiency may vary locally in the plasma and there¬
fore the measured profiles might be affected by such variations. The
measurement of absolute concentration profiles is possible if the laser
21
is able to saturate the observed transition. Preliminary measurements
carried out in our laboratory have shown that this can be achieved with
our pulsed laser. But the use of an excimer laser would clearly intro¬
duce saturation and then the laser-induced fluorescence in ICP would be
interesting to take another look from the analytical point of view as a
new tool.
While the initial evaluation of laser-excited AFS in the ICP has not
indicated the technique to be superior to ICPAE5 or to LFAFS, the appli¬
cation of multipass optical cells to reflect the laser beam several times
118
through the ICP, as well as the use of more powerful, higher repetition
rate laser sources, should improve detection limits enough so that the
advantages inherent in the combination of a high-temperature atomic vapor
cell with the atomic fluorescence method will be fully realized. Fur¬
thermore, laser-excited AFS is still a very powerful tool for diagnostic
studies of the ICP."'“^
Metal complexation may be used for the following purposes in gas
chromatography with inductively coupled plasma as a detector: (i) to
help the separation of certain compounds present in the sample. (In this
case complexation is performed by using a stationary phase containing a
metal); (ii) to utilize GC-ICP for the calculation of stability constants
or other physical/chemical data; (iii) to increase sensitivity for inor¬
ganic and organic compounds by forming metal complexes.

224
The effect of the formation of electron-donor-acceptor complexes
(EDA) of transition metal cations with organic molecules containing ir-
bond(s) or free electron pairs (N, 0, S, halogens) may be used for the
gas chromatographic separation of these molecules with the ICP as a de¬
tector of the metal complexes because of the considerable differences
in the retention time of the metal complexes.
In the case of a 1:1 complex formation, GC-ICP is convenient for
the determination of the stability constants of the newly formed adducts.
The formation of u-complexes with cations of the transition metals are
particularly useful in GC-ICP. The thermal stability of these complexes
changes in a very broad temperature range depending on the metal and the
ligand. The ICP atomic emission spectrometry has been known to be a
sensitive technique for metal analysis, thus it will provide a sensitive
method for the ligand forming complexes with the metals.
The gas generation technique is known to be effective for the con¬
densation of analyte in solution and minimizing the matrix effect. One
could apply this technique to atomic and molecular emission/fluorescence
spectrochemical analysis of non-metallic elements, which are difficult
to be measured by usual spectrochemical methods. Boron trifluoride can
be generated from a specially designed high temperature cuvette, in which
boron containing samples are heated with calcium fluoride and sulfuric
acid. The gas is carried into a plasma and then atomic emission or fluor¬
escence of boron, emission of boron dioxide, and molecular emission of
boron monofluoride can be monitored. Ammonium-N also can be generated
as ammonia gas by heating from a strongly alkali solution and then car¬
ried into the plasma. This method can also be applicable to the analysis
of nitrate-N and nitrite-N by reducing them to ammonia gas with appro¬
priate reducing reagent.

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BIOGRAPHICAL SKETCH
In 1942, Seifollah Nikdel was born in Bojnourd, Iran. After gradu¬
ating from Amirkabir High School, he went on to Tehran to earn a Bache¬
lor of Science degree in chemistry at the University of Tehran, com¬
pleting it in 1966. After serving for two years in the Iranian Army,
he was employed as an instrumental laboratory instructor at Pars College
in Tehran. In 1971, he took an industrial job with the Damavand White
Cement Plant as a supervisor in the physical/chemical laboratory.
Later, in 1972, he decided to further his education in the USA.
After completing an intensive program of study in an English School in
Washington, D.C., he entered the graduate school at the University of
Massachusetts. There, he received the Master of Science degree in ana¬
lytical chemistry in 1975. In September 1976, he then began study on
his doctoral degree at the University of florida in Gainesville, Florida.
He is a member of the American Chemical Society and the Society for
Applied Spectroscopy.
231

I certify that I have read this study and that in my opinion it con¬
forms to acceptable standards of scholarly presentation and is fully ade¬
quate, in scope and quality, as a dissertation for the degree of Doctor
of Philosophy.
/ames D. Winefordney, Chairman
Graduate Research Professor of Chemistry
I certify that I have read this study and that in my opinion it con¬
forms to acceptable standards of scholarly presentation and is fully ade¬
quate, in scope and quality, as a dissertation for the degree of Doctor
of Philosophy.
Roger G/ Bates
Professor of Chemistry
I certify that I have read this study and that in my opinion it con¬
forms to acceptable standards of scholarly presentation and is fully ade¬
quate, in scope and quality, as a dissertation for the degree of Doctor
of Philosophy.
Martin T. Vala
Professor of Chemistry

I certify that I have read this study and that in my opinion it con¬
forms to acceptable standards of scholarly presentation and is fully ade¬
quate, in scope and quality, as a dissertation for the degree of Doctor
of Philosophy.
and Human Nutrition
I certify that I have read this study and that in my opinion it con¬
forms to acceptable standards of scholarly presentation and is fully ade¬
quate, in scope and quality, as a dissertation for the degree of Doctor
of Philosophy.
írhard M. Schmid
Associate Professor of Chemistry
This dissertation was submitted to the Graduate Faculty of the De¬
partment of Chemistry in the College of Liberal Arts and Sciences and to
the Graduate Council, and was accepted as partial fulfillment of the re¬
quirements for the degree of Doctor of Philosophy.
December 1979
Dean, Graduate School

UNIVERSITY OF FLORIDA
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