a quantitative analysis by emission spectroscopy of the

Western Michigan University Western Michigan University

ScholarWorks at WMU ScholarWorks at WMU

Master's Theses Graduate College

12-1972

A Quantitative Analysis by Emission Spectroscopy of the Metallic A Quantitative Analysis by Emission Spectroscopy of the Metallic

Constituents of Biological Samples after Treatment by a Constituents of Biological Samples after Treatment by a

Carcinogenic Agent Carcinogenic Agent

Charles R. Frydrych

Follow this and additional works at: https://scholarworks.wmich.edu/masters_theses

Part of the Biochemical and Biomolecular Engineering Commons, and the Molecular, Cellular, and

Tissue Engineering Commons

Recommended Citation Recommended Citation Frydrych, Charles R., "A Quantitative Analysis by Emission Spectroscopy of the Metallic Constituents of Biological Samples after Treatment by a Carcinogenic Agent" (1972). Master's Theses. 2743. https://scholarworks.wmich.edu/masters_theses/2743

This Masters Thesis-Open Access is brought to you for free and open access by the Graduate College at ScholarWorks at WMU. It has been accepted for inclusion in Master's Theses by an authorized administrator of ScholarWorks at WMU. For more information, please contact [email protected].

http://scholarworks.wmich.edu/


https://scholarworks.wmich.edu/

https://scholarworks.wmich.edu/masters_theses

https://scholarworks.wmich.edu/grad

https://scholarworks.wmich.edu/masters_theses?utm_source=scholarworks.wmich.edu%2Fmasters_theses%2F2743&utm_medium=PDF&utm_campaign=PDFCoverPages

http://network.bepress.com/hgg/discipline/241?utm_source=scholarworks.wmich.edu%2Fmasters_theses%2F2743&utm_medium=PDF&utm_campaign=PDFCoverPages



https://scholarworks.wmich.edu/masters_theses/2743?utm_source=scholarworks.wmich.edu%2Fmasters_theses%2F2743&utm_medium=PDF&utm_campaign=PDFCoverPages

mailto:[email protected]



A QUANTITATIVE ANALYSIS BY EMISSION SPECTROSCOPY OF THE METALLIC CONSTITUENTS OF BIOLOCICAL SAMPLES AFTER

TREATMENT BY A CARCINOGENIC AGENT

by

C h a r l e s R. F r y d r y c h

A T h e s i s S u b m i t t e d t o t h e

F a c u l t y o f The G r a d u a t e C o l l e g e i n p a r t i a l f u l f i l l m e n t

o f t h eD e g r e e o f M a s t e r o f A r t s

W e s t e r n M i c h i g a n U n i v e r s i t y K a l a m a z o o , M i c h i g a n

D e c e m b e r , 1972

R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission.

ACKNOWLEDGEMENTS

I am p l e a s e d a t t h e o p p o r t u n i t y t o a c k n o w l e d g e my

g r a t i t u d e t o Dr . S t a n l e y D e r b y , who d e m o n s t r a t e d an

u n f a i l i n g a i r o f p a t i e n c e , u n d e r s t a n d i n g and e n c o u r a g e

me n t d u r i n g t h e l o n g p r o c e s s o f a s s e m b l i n g t h i s r e p o r t .

My t h a n k s go a l s o t o t h e many i n d i v i d u a l s h e r e a t t h e

u n i v e r s i t y who r e s p o n d e d t o my n u m e r o u s r e q u e s t s w i t h

an a m a z i n g s p i r i t o f c o o p e r a t i o n . F i n a l l y , I w i s h t o

t h a n k my w i f e , M a r y , f o r h e r t o l e r a n c e a nd u n d e r s t a n d i n g

C h a r l e s R. F r y d r y c h


IN F O R M A T IO N T O U S E R S

This dissertation was produced from a m icrofilm copy of the original document. W hile the most advanced technological means to photograph and reproduce this document have been used, the quality is heavily dependent upon the quality of the original submitted.

The follow ing explanation o f techniques is provided to help you understand markings or patterns which may appear on this reproduction.

1. The sign or "target" for pages apparently lacking from the document photographed is "Missing Page(s)". If it was possible to obtain the missing page(s) or section, they are spliced into the film along w ith adjacent pages. This may have necessitated cutting thru an image and duplicating adjacent pages to insure you complete continuity.

2. When an image on the film is obliterated with a large round black mark, it is an indication th a t the photographer suspected that the

copy may have moved during exposure and thus cause a blurred image. You will find a good image of the page in the adjacent frame.

3. When a map, drawing or chart, etc., was part of the material being

p h o to g raph ed the photographer follow ed a defin ite method in "sectioning" the material. I t is customary to begin photoing at the upper le ft hand corner of a large sheet and to continue photoing from left to right in equal sections w ith a small overlap. If necessary, sectioning is continued again — beginning below the first row and continuing on until complete.

4. The m ajority of users indicate that the textual content is of greatest value, however, a som ewhat higher quality reproduction could be made from "photographs" if essential to the understanding o f the dissertation. Silver prints o f "photographs" may be ordered at additional charge by w riting the Order Departm ent, giving the catalog number, title , author and specific pages you wish reproduced.

University Microfilms300 N orth Z e e b R oadAnn A rbor, M ich igan 48106

A Xerox E d u c a tio n C om pany


MASTERS TH ESIS M -4111

FRYDRYCH, Charles R.A QUANTITATIVE ANALYSIS BY EMISSION SPECTROSCOPY OF THE METALLIC CONSTITUENTS OF BIOLOGICAL SAMPLES AFTER TREATMENT BY A CARCINOGENIC AGENT.

Western Michigan U niversity , M.A., 1972 Physics, spectroscopy

University Microfilms, A XEROX Company , Ann Arbor, Michigan


PLEASE NOTE:

Some pages may have

i nd i s t i n e t p r i n t .

F i l m e d as r e c e i v e d .

U n i v e r s i t y M i c r o f i l m s , A X ero x E d u c a t i o n Company


TABLE OF CONTENTS

CHAPTER PAGE

I . THE PROBLEM AND ITS BACKGROUND.......................... 1

I I . ANALYTICAL TECHNIQUE...................................................3

A p p a ra tu s and O p e ra t in g C o n d i t io n s . . . . 6

P r e p a r a t io n o f S ta n d a r d s .................................7

I n t e r n a l S ta n d a r d s ...............................................12

P r e p a r a t io n o f C o n tro l Sam ples andE x p e r im e n ta l S a m p le s ..................................... 14

P ro c e d u re f o r E xposu re o f S a m p le s ..............17

I I I . DATA AND RESULTS............................................................ 20

P ro c e d u re F o r O b ta in in g D e n s i to m e tr ic D a ta ............................................................................20

C a lc u la t in g Scheme f o r D e n s i to m e tr ic D a ta ............................................................................21

IV . CONCLUSIONS........................................................................ 36

APPENDICES

I . D e t a i l s o f Arc C i r c u i t A rra n g e m e n t.................44

I I . Graph o f P l a t e F a c to r v e r s u s W aveleng thf o r H i lg e r S p e c tro g r a p h ..........................................45

REFERENCES.............................................................................................46

BIBLIOGRAPHY........................................................................................4S


LIST OF FIGURES

FIGURE PAGE

F ig u re 1 . C a l i b r a t i o n Curve f o r C a lc ium S ta n d a rd s ............................................................... ................... 23

F ig u re 2 . C a l i b r a t i o n Curve f o r Sodium S ta n d a rd s ..................... 24

F ig u re 3 . C a l i b r a t i o n C urve f o r M agnesiumS ta n d a r d s ........................................................................25

F ig u re 4 . C a l i b r a t i o n Curve f o r C opper S ta n d a rd s ....................................................................................26

F ig u re 5 . C a l i b r a t i o n Curve f o r P o ta s s iu mS ta n d a r d s ........................................................................27

F ig u re 6 . Amount o f C alc ium p r e s e n t i n C o n tro land E x p e r im e n ta l S a m p le s ................................... 39

F ig u re 7 . Amount o f Sodium p r e s e n t i n C o n tro land E x p e r im e n ta l S a m p le s ...................................40

F ig u re S . Amount o f M agnesium p r e s e n t i n C o n tro land E x p e r im e n ta l S a m p le s ................................... 41

F ig u re 9 . Amount o f C opper p r e s e n t i n E x p e r i m e n ta l S a m p le s ........................................................... 42

F ig u re 1 0 . Amount o f P o ta s s iu m p r e s e n t i n C o n tro land E x p e r im e n ta l S a m p le s ................................... 43

F ig u re 1 1 . C urve o f P l a t e F a c to r v s . W av e len g thf o r H i lg e r S p e c t r o g r a p h ..................................... 45

i v


LIST OF TABLES

TABLE PAGE

I . E x p e r im e n ta l A p p a ra tu s and C o n d i t i o n s .................6

I I . The C o m p o sitio n o f th e S y n th e t i c M a t r ix ............9

I I I . Amount o f e le m e n t p r e s e n t i n gram s i ne a c h S ta n d a r d .......................................................................... 12

IV Amount o f e le m e n t p r e s e n t a s p e r c e n ta g e o ft o t a l w e ig h t o f S ta n d a r d ................................................12

V. C o m p o s itio n o f S ta n d a rd m ix tu r e s i n g r a m s . . . 14

VT. C o m p o s itio n o f S a m p le - B u f f e r - I n te r n a l Cont r o l m ix tu re i n g ra m s....................................................... 16

V I I . Mean D e v ia t io n o f D e n s i to m e tr ic D a ta asp e r c e n t a g e ..................................................................................21

V I I I . D a ta T a b le f o r C alc ium C a l i b r a t i o n C u r v e . . . . 2 S

IX . D a ta T a b le f o r Sodium C a l i b r a t i o n C u rv e 2S

X. D a ta T a b le f o r M agnesium C a l i b r a t i o n C u rv e ..2 S

X I. D a ta T a b le f o r C opper C a l i b r a t i o n C u rv e 2S

X I I . D a ta T a b le f o r P o ta s s iu m C a l i b r a t i o nC u rv e .............................................................................................. 29

X I I I . C o m p o s itio n o f C o n t r o l - B u f f e r - I n t e r n a l C o n tro l M ix tu re i n g ra m s ................................................30

XIV. C o m p o s itio n o f E x p e r i m e n t a l - B u f f e r - I n t e r -n a l C o n tro l M ix tu re i n g ra m s ......................................30

XV. Amount o f C a lc ium i n C o n tro l and E x p e r i m e n ta l S am ples as p e r c e n t a g e ......................................31

XVI. Amount o f Sodium i n C o n tro l and E x p e r i m e n ta l S am ples a s p e r c e n t a g e ......................................32

XVTI. Amount o f M agnesium i n C o n t r o l and Exp e r im e n ta l S am ples a s p e r c e n t a g e ............................ 33

v


LIST CF TABLES (c o n t in u e d )

TABLE PAGE

XV TII. Amount o f C opper i n C o n tro l and E x p e r im e n ta l Sam ples a s p e r c e n t a g e .....................................34

XIX. Amount o f P o ta s s iu m i n C o n tr o l and E x p e r i m e n ta l Sam ples a s p e r c e n t a g e .....................................35

v i


CHAPTER I

THE PROBLEM AND ITS BACKGROUND

I n t h e f a l l o f 1 9 6 4 , Dr Leo V a n d e r Beek o f t h e P l a n t

P h y s i o l o g y s e c t i o n o f t h e B i o l o g y D e p a r t m e n t o f W e s t e r n

M i c h i g a n U n i v e r s i t y b r o u g h t t o t h e a t t e n t i o n o f Dr S t a n

l e y De rb y o f t h e P h y s i c s D e p a r t m e n t t h e f a c t t h a t t h e

t r e a t m e n t o f c e r t a i n b i o l o g i c a l s a m p l e s , i n t h i s c a s e t o

ma t o p l a n t s , w i t h a c a r c i n o g e n i c a g e n t - 2 , 4 , 6 d i a b e n z o -

l i c a c i d ( B ^ ( W O 2 )CgH 2 NH2 ) p r o d u c e d a d e f i n i t e t u m o r - l i k e

g r o w t h i n t h e i n t e r s e c t i o n o f t h e p r i m a r y p l a n t s t e m w i t h

t h e s e c o n d a r y l e a f s t e m . A q u e s t i o n o f i n t e r e s t a r o s e a s

t o m h e t h e r t h e m a t e r i a l c o m p r i s i n g t h e t u m o r o u s g r o w t h

d i f f e r e d t o any a s c e r t a i n a b l e d e g r e e f r o m u n - t r e a t e d

p l a n t s a m p l e s o f t h e same s p e c i e s w i t h r e s p e c t t o t h e

m e t a l l i c e l e m e n t s n o r m a l l y p r e s e n t i n g r o w i n g p l a n t s .

S i n c e a c o n t r o l g r o u p o f p l a n t s a m p l e s had b e e n

s i m u l t a n e o u s l y e x p o s e d t o g r o w t h a n d n u t r i e n t c o n d i t i o n s

w h i c h w e r e s i m i l a r i n a l l r e s p e c t s t o t h o s e t o w h i c h t h e

t r e a t e d p l a n t s h ad b e en s u b j e c t e d a n d s i n c e t h e a n a l y s i s

o f t h e m e t a l l i c e l e m e n t s i n v o l v e d was c o m p a t i b l e w i t h

t h e t e c h n i q u e s o f e m i s s i o n s p e c t r o s c o p y u t i l i z i n g t h e

d . c . a r c , t h e a u t h o r p r o p o s e d t h e f o l l o w i n g i n v e s t i g a t i o n :

a q u a n t i t a t i v e d e t e r m i n a t i o n o f t h e m a j o r m e t a l l i c e l e m

e n t s p r e s e n t i n t h e o o n t r o l s a m p l e s w o u l d b e c o m p a r e d

1


2

w i t h t h e a m o u n t s o f t h e s e e l e m e n t s p r e s e n t i n t h e t r e a t

ed s a m p l e s . A s y n t h e t i c m a t r i x mou l d be u s e d t o c a l i b r a t e

t h e a m o u n t s i n v o l v e d ; t h i s m a t r i x b e i n g d e s i g n e d t o d u p l i c

a t e , i f p o s s i b l e , t h e p r o p o r t i o n o f s u c h e l e m e n t s n o r m a l l y

p r e s e n t i n t h e g r o m i n g p l a n t . . A s u i t a b l e i n t e r n a l s t a n d

a r d m o u l d be c h o s e n t o m o n i t o r u n a v o i d a b l e v a r i a t i o n s i n

t h e e x p o s u r e c o n d i t i o n s b e t m e e n s a m p l e s .


CHAPTER I I

ANALYTICAL TECHNIQUE

The g ro w in g p l a n t , i n th e a b sen c e o f t r a c e contam

i n a n t s a r i s i n g from i t s im m ed ia te e n v iro n m e n ta l c irc u m

s t a n c e s , i s n o rm a lly fo u n d to c o n ta in two g e n e r a l g ro u p s

o f e le m e n ts - th e f i r s t i d e n t i f i e d v a r i o u s ly a s th e

m a jo r e le m e n ts , o r m a c r o - n u t r i e n t s and a se c o n d i d e n t i

f i e d a s t h e m in o r e le m e n ts , t r a c e e le m e n ts , o r m ic ro

n u t r i e n t s . The m a c r o - n u t r i e n t s , g e n e r a l l y p r e s e n t i n

r e l a t i v e l y g r e a t e r a b u n d an c e , c o n s i s t p r i m a r i l y o f n i t

ro g e n (N ), p h o sp h o ru s ( P ) , p o ta s s iu m (K ), s u l f u r ( S ) ,

c a lc iu m (C a ) , m agnesium (Mg) and sodium (N a ) . The m ic ro

n u t r i e n t s , g e n e r a l l y p r e s e n t i n r e l a t i v e l y l e s s e r abund

a n c e , c o n s i s t o f i r o n ( F e ) , c o p p e r (C u ) , m anganese (M n),

z in c (Z n ) , molybdenum (M o), s i l i c o n ( S i ) and b o ro n ( B ) l

Though th e l i s t o f m ic r o - n u t r i e n t s may expand w ith f u r t h

e r i n v e s t i g a t i o n , t h e s e v e n l i s t e d e le m e n ts a r e commonly

th o u g h t t o be e s s e n t i a l f o r th e p r o p e r g ro w th o f th e

h ig h e r p l a n t s ? The p l a n t a ls o c o n ta in s , o f c o u r s e , th e

e le m e n ts c a rb o n (C ) , h y d ro g en (H ), oxygen (0 ) and c h lo

r i n e ( C l ) , b u t t h e s e e le m e n ts - a lo n g w i th th e m acro

n u t r i e n t n i t r o g e n (N) - do n o t le n d th e m s e lv e s t o d e t e r

m in a t io n by th e d . c . a r c te c h n iq u e em ployed h e re b e c a u se

o f t h e i r h i g h e r e x c i t a t i o n e n e r g ie s ? I n t h e c a se o f th e

3


4

e l e m e n t p o t a s s i u m , p r e s e n t a s a m a c r o - n u t r i e n t , F l ame

p h o t o m e t r y i s o f t e n r e co m m en d ed a s a t e c h n i q u e f o r i t s

q u a n t i t a t i v e d e t e r m i n a t i o n . ^ I n p r a c t i c e , h o w e v e r , t h i s

e l e m e n t was f o u n d t o be w e l l - b e h a v e d when d e t e r m i n e d by

t h e g e n e r a l t e c h n i q u e e m p l o y e d f o r a i l o t h e r e l e m e n t s .

The t o m a t o p l a n t s a m p l e s s u b m i t t e d by Dr V a n d e r Beek

h a d a l r e a d y b e e n d r y a s n e d a n d r e d u c e d t o g r a n u l a r f o r m ,

t h u s e f f e c t i v e l y r e m o v i n g t h e o r g a n i c p o r t i o n s o r t h e

o r i g i n a l m a t e r i a l . I n o r d e r t o a c c u r a t e l y d e t e r m i n e t h e

a m o un t o f e a c h m e t a l l i c e l e m e n t p r e s e n t i n t h e s e s a m p l e s ,

i t a p p e a r e d t h a t t h e m o s t s u i t a b l e a p p r o a c h w o u l d be t o

c r e a t e a s e t o f s y n t h e t i c s t a n d a r d s w h i c h w o u l d c o n t a i n

t h e p r o p e r p r o p o r t i o n o f e l e m e n t s p r e s e n t i n a n o r m a l

p l a n t a s h and w h i c h w o u l d a l s o s p a n t h e l i k e l y r a n g e o f

c o n c e n t r a t i o n s . T h e s e s y n t h e t i c s t a n d a r d s w o u l d a l s o be

c o n s t r u c t e d so a s t o p a r a l l e l t h e f o r m o f t h e e l e m e n t a s

p r e s e n t i n t h e a s h e d p o w d e r . T h i s c o n s i d e r a t i o n l e d t o

t h e a d o p t i o n o f a s y n t h e t i c s t a n d a r d mix c o n s t r u c t e d f r o m

o x i d e s o f t h e a p p r o p r i a t e m e t a l s - t h e c h e m i c a l f o r m m o s t

l i k e l y t o be p r e s e n t i n t h e a s h . I n o r d e r t o a l l o w f o r

t h e a n o m a l i e s o f e x p o s u r e a n d d e v e l o p m e n t , a s e a r c h f o r

a s u i t a b l e i n t e r n a l s t a n d a r d a s w e l l a s a j u d i c i o u s c h o i c e

o f a b u f f e r i n g a g e n t was a l s o n e c e s s a r y .

The s u c c e s s o f p o w d e r e d g r a p h i t e a s a b u f f e r i n g

a g e n t h a s b e e n a mpl y d o c u m e n t e d . ^ I t s b e h a v i o u r i n a

d . c . a r c , s e r v i n g t o s t a b i l i z e a r c t e m p e r a t u r e a n d p r o -


5

m ote u n ifo rm e x c i t a t i o n c o n d i t i o n s among sam p le s o f v a ry

in g c o m p o s it io n make i t s a d d i t i o n to b o th th e s y n t h e t i c

m a t r ix a s w e l l a s th e p l a n t sa m p le s d e s ira b le * ? S in c e th e

e le m e n ts w ere s u s p e c te d , i n some c a s e s , t o be p r e s e n t i n

t r a c e am o u n ts , a L i2CC3 c a r r i e r was a l s o added to b o th

th e m a t r ix and th e p l a n t sa m p le s b e f o r e th e y w ere a r c e d .

The p r o p o r t io n o f L i - c a r r i e r t o g r a p h i t e was f i x e d a t 1 :1

and t h i s m ix tu re was u se d t o d i l u t e th e s y n t h e t i c m a t r ix

t o o b t a in t h e c o n c e n t r a t i o n s d e s i r e d o f th e v a r io u s e l e

m en ts p r e s e n t .

V a lle e and P e a t t i e ^ i n an e x te n s iv e a n a l y s i s o f v o l

a t i l i z a t i o n r a t e s o f e le m e n ts i n a d . c . a r c d e m o n s tra te d

th e w ide v a r i a t i o n i n su c h r a t e s w i th th e s u b s e q u e n t i n

f e r e n c e t h a t a c h o ic e o f i n t e r n a l s t a n d a r d - n e c e s s a r y t o

m o n ito r t h e u n a v o id a b le v a r i a t i o n s b e tw een e x p o su re s -

was o f p rim e im p o r ta n c e i n c a r e f u l q u a n t i t a t i v e d e te r m in -£

a t i o n s . The w ork o f Tymchuk, R u s s e l l and Berman, demon

s t r a t i n g th e w id e s p re a d a p p l i c a b i l i t y o f a r a r e e a r t h ,

su c h a s in d iu m , a s an i n t e r n a l s t a n d a r d , was v e r i f i e d

when in d iu m was com pared t o e a r l i e r c h o ic e s f o r an i n

t e r n a l s t a n d a r d s u c h a s s i l v e r and c o b a l t . The a b se n c e

o f in d iu m fro m n o rm al p l a n t sy s te m s i s a n o th e r s t r o n g

reco m m en d a tio n f o r i t s c h o ic e a s an i n t e r n a l c o n t r o l .

The d e t a i l s o f th e p r e p a r a t i o n s in v o lv e d i n con

s t r u c t i n g th e s y n t h e t i c s t a n d a r d s and th e i n t r o d u c t i o n

o f i n t e r n a l s t a n d a r d and b u f f e r t o th e p l a n t sa m p le s

R eproduced with perm ission o f the copyright owner. Further reproduction prohibited without perm ission.

a n a ly z e d a re more f u l l y d e s c r ib e d i n th e s e c t i o n s -which

f o l lo w .

A p p a ra tu s and O p e ra t in g C o n d it io n s

The f o l lo w in g t a b l e sum m arizes th e m a jo r u n i t s o f

e q u ip m en t u se d and th e c o n d i t io n s u n d e r w hich th e s e u n i t s

o p e r a te d :

T a b le I . E x p e r im e n ta l A p p a ra tu s and C o n d i t io n s .

E x c i t a t i o n S y s tem :

S o u rce U n i t ....................................................d . c . a r c .

D is c h a r g e ........................................................ 3 .5 am ps.

Sam ple E le c t r o d e U lt r a -C a r b o n , 3 / 4 ” lo n g x 1/ 4 " d i a . g r a p h i t e , 1 /S " d e e p .U l t r a - C a rb o n , 3 /4 " lo n g x 1/ 4 " d i a . g r a p h i t e , no t a p e r . 30 s e c o n d s .

C o u n te r E le c t r o d e

E x p o su re T im e.

A n a l y t i c a l Gap

P r e b u r n ...............

1 mm.

None.

A tm o sp h e re . .

O p t i c a l S y s tem :

S p e c tro g ra p h

S t a t i c .

W av e len g th C overage

S l i t W id th ....................

Adam H i l g e r , Medium Q u a r tz (2 -1 0 ) K A#, M odel E49S.2500 A° to 4400 A°.

20 m ic ro n s .

E x te r n a l O p t ic s None


7

S te p S e c t o r ................................................... 8 s t e p r o t a t i n gs e c t o r ( s t e p f a c t o r * ^ ) : 5 d a r k e s t s t e p s u s e d .

D e t e c to r .......................................................... E astm an Kodak 4x10in c h SA-3 p l a t e s .

D e v e lo p in g C o n d i t io n s :

D ev e lo p m en t...................................................E astm an Kodak D -19,4 m in u te s .

S to p B a th ........................................................ G a la c ia l a c e t i ca c i d , 2%, 1 m in u te .

F i x i n g ...............................................................E astm an Kodak,K o d a f ix . 5 m in u te s ,

W ash in g .............................................................R unn ing w a te r f o r20 m in u te s . D i s t i l l e d W ater r i n s e .

D ry in g ............................................................... A ir d ry f o r 4 h o u rminimum.

P h o to m e try :

D e n s i to m e te r ................................................ H a rry D ie te r t - A .R .L . D e n s i to m e te r - C o m p ara to r .

P r e p a r a t io n s o f S ta n d a rd s

The p l a n t sam p le s p r e s e n te d f o r a n a l y s i s c o n s i s t e d

o f 10 d i s c r e t e sam p les w hich had b een t r e a t e d w ith th e

c a rc in o g e n and 9 d i s c r e t e sam p les w hich h ad b e en grown

a s a c o n t r o l g ro u p . A q u a l i t a t i v e a n a l y s i s was p e rfo rm

ed on ran d o m ly s e l e c t e d p o r t io n s o f 5 o f th e 10 e x p e r i

m e n ta l sa m p le s and 4 o f th e 9 c o n t r o l s a m p le s . A pprox i

m a te ly 25 mg o f sam ple was a rc e d f o r e a c h e x p o su re and a

ra n g e o f e x p o su re t im e s o f from 1 0 -120 s e c o n d s was i n

v e s t i g a t e d . A l l n in e l o t s t e s t e d e x h ib i t e d s i m i l a r c h a r

a c t e r i s t i c s . At e x p o su re t im e s o f l e s s th a n 120 s e c o n d s ,


8

e ac h sam ple showed e v id e n c e o f th e p re s e n c e o f Ca, K, Na,

Cu and Mg. At e x p o su re t im e s e x c e e d in g 120 s e c o n d s , th e s e

same e le m e n ts as w e l l a s t r a c e am ounts o f S i ( t h e 2500 A0

g roup and th e 2331 A0 l i n e ) and B ( th e 2496 A° and 2497 A°

l i n e s ) w ere v i s i b l e . When b la n k c a rb o n e l e c t r o d e s w ere

a rc e d a t e x p o su re t im e s r a n g in g from 120-240 s e c o n d s ,

th e y to o r e v e a le d th e same S i and B g ro u p s . At an ex

p o su re tim e o f 240 s e c o n d s , t h e s e b la n k c a rb o n e l e c t r o d e s

a ls o e x h ib i t e d t r a c e am ounts o f A l ( th e 3944 A0 - 396lA °

l i n e p a i r ) . The l i n e d e n s i t i e s o f th e S i , B and Al i n

b o th p l a n t sam ple and b la n k e l e c t r o d e e x p o su re s w ere com

p a r a b l e . On th e b a s i s o f t h i s a n a l y s i s , i t was c o n c lu d e d

t h a t th e S i , B and Al w ere g r a p h i t e c o n ta m in a n ts r a t h e r

th a n c o n s t i t u e n t s o f th e p l a n t sa m p le s a n a ly z e d .

W ith t h i s p r e l im in a r y a n a l y s i s c o n c lu d e d , a s y n th e

t i c m a t r ix was d e s ig n e d c o n ta in in g th e fo l lo w in g r a t i o

o f e le m e n t s :

Ca : Na : Mg : Cu : K

2 .4 3 : 2 .1 0 : 2 .0 9 : 1 .3 9 : 1 . 0 0 .G

The i n v e s t i g a t i o n s o f C onnor and B ass£ Ng, H s ia and

L a i} ^ and B e d ro s ia n , S kogerboe and M o r r i s o n ^ seem r e p r e

s e n t a t i v e o f th e f a c t t h a t s y n t h e t i c m a t r ic e s d e s ig n e d

f o r th e a n a l y s i s o f b i o l o g i c a l sa m p le s v a ry c o n s id e r a b ly

i n th e i n t e r - e l e m e n t r a t i o s u s e d , ev en when th e c la im

( f o o t n o te s 9 and 1 0 ) f o r a p p l i c a b i l i t y to a w ide v a r i e t y

o f b i o l o g i c a l m a t e r i a l s a r e m ade. I t seem ed p ro p e r t o


9

c o n c lu d e , t h e r e f o r e , t h a t th e im p o r ta n t c r i t e r i a i n th e

d e s ig n o f a s y n t h e t i c m a t r ix w ould u l t i m a t e l y be i t s r e -

p ro d u c f b i l i t y when a rc e d and th e s t r u c t u r e o f th e r e s u l t

in g c a l i b r a t i o n c u rv e s p ro d u c e d . The m a t r ix u se d f o r

t h i s a n a l y s i s m et th e s e t e s t s .

The t a b l e be low d e t a i l s th e s y n t h e t i c m a t r ix u s e d .

T ab le I I . The C o m p o sitio n o f th e S y n th e t i c M a t r ix .

Amount, o f s a l t added Amount o f e le m e n t $ o f e le m e n t i n i n gms______________ p r e s e n t i n gms f i n a l m a t r ix

The o x id e s u se d i n c o n s t r u c t in g th e m a t r ix w ere

A .C .S . r e a g e n t g ra d e m a t e r i a l s , o b ta in e d from th e S a r -

g e n t-W e lc h Company w ith th e s i n g l e e x c e p t io n o f th e r a r e

e a r t h o x id e , 1 ^ 0 ^ , w h ich was o b ta in e d from A lfa Chem

i c a l s (B e v e r ly , M a s s .) . The f o l lo w in g se q u e n c e was u se d

i n th e c a se o f e a c h c h e m ic a l com bined i n t o th e m a t r ix :

A bout 1 gram o f th e m a t e r i a l was p la c e d i n an a g a te mor

t a r and g ro u n d to u n i f o r m i ty a f t e r a b o u t 10 m in u te s . The

s a l t was th e n p la c e d i n a w e ig h in g b o t t l e and oven d r i e d

f o r an h o u r a t 100°C . W hile i n th e o v e n , th e b o t t l e ’ s

s to p p e r was l a i d a c r o s s th e m outh o f t h e b o t t l e and th e

1 .0 0 0 7 g CaO

1 .0 2 1 1 g KC104

1 .0 2 7 2 g Na202

1 .0 0 1 2 g MgO

0 .4 9 9 9 g CuG

0 .7 1 5 2 g Ca

0 .2 8 3 2 g K

0 .6 0 5 6 g Na

0 .6 0 3 8 g Mg

0 .3 9 9 4 g Cu

1 5 .7 2 % Ca

6 .3 3 * K

1 3 .3 1 £ Na

1 3 .2 7 Mg

8 .7 8 56 Cu


10

a sse m b ly p la c e d i n s i d e a s m a ll b e a k e r c o v e re d by a w a tch

g l a s s r e s t i n g on t h r e e s p a c e r s -̂2 A f te r d r y in g , th e s a l t

was w e ighed o u t i n t o th e r e q u i r e d p o r t i o n s on an A in s

w o rth R ig h t-A -W eig h B a la n c e , an in s t r u m e n t w hich h a s a

r e a d in g u n c e r t a i n t y o f + 0 .0 0 0 1 g ram . T hese p o r t i o n s

w ere th e n s t o r e d i n a d e s s i c a t o r u n t i l t h e f i n a l m ix

t u r e was a s s e m b le d . When a l l f i v e s a l t s had b e en w eigh

ed o u t i n t o t h e r e q u i r e d a m o u n ts , th e y w ere p la c e d i n a

s m a ll P y re x b o t t l e w i th a p o ly v in y l s t o p p e r . The m ix

t u r e c o n ta in e d i n th e b o t t l e was th e n p la c e d i n a h o ld e r

w h ich p o s i t i o n e d th e c y l i n d r i c a l a x i s o f th e b o t t l e a t

r i g h t a n g le s t o th e bed o f a s m a l l m ach ine l a t h e w hich

sp u n th e m ix tu re f o r 30 m in u te s a t a b o u t 450 rpm . T h is

a g i t a t i o n su c c e e d e d i n ro u g h -m ix in g th e sam ple and th e

p r o c e s s was c o m p le te d w i th a n o th e r 30 m in u te s o f hand

m ix in g i n th e a g a te m o r ta r .

The s y n t h e t i c m a t r ix was d i l u t e d by a g r a p h i t e -

L i2CG3 m ix t h a t was j o in e d i n a r a t i o o f 1 : 1 . The s e l

e c t i o n o f L i2CC3 f o l lo w e d th e e v a l u a t i o n o f s e v e r a l com

p o u n d s , i n c l u d i n g (NH4 ) 2SC4 and CaC0 3 . The r e p r o d u c i b i l

i t y o f l i t h i u m b u f f e r e d sa m p le s was s u p e r i o r t o t h a t o f

th e ammonium b u f f e r e d and c a lc iu m b u f f e r e d g ro u p s by a

f a c t o r o f two when mean d e v i a t i o n s f o r t e s t g ro u p s u s in g

e a c h b u f f e r w ere co m p ared . The i o n i z a t i o n p o t e n t i a l o f

t h e L i a l s o com pared f a v o r a b ly w i th t h e m a jo r i t y o f t h e

e le m e n ts b e in g a n a ly z e d . The d i l u t i o n se q u e n c e f o r o b -


11

t a i n i n g th e ra n g e o f c o n c e n t r a t i o n s o f th e v a r io u s e l e

m en ts i s shown b e lo w . The am ount o f m a t r ix : Li+C b u f f e r

was as f o l l o w s :

S ta n d a rd 1 ................. 1 :0 .2 5S ta n d a rd I I ...............1 :2S ta n d a rd I I I ............ 1 :2 0S ta n d a rd IV ...............1 :1 5 4

T h is d i l u t i o n s e r i e s sp an n ed an a m b i t io u s ly l a r g e

ra n g e o f c o n c e n t r a t i o n s , b u t r e s u l t e d i n a s e t o f c a l i

b r a t i o n c u rv e s f o r th e f i v e e le m e n ts s o u g h t t h a t were

w e l l w i th in th e t o l e r a n c e s d e s i r e d . As a b u f f e r i s add

ed i n i n c r e a s i n g am ounts t h e r e i s th e p o s s i b i l i t y o f a

d e c r e a s e i n s e n s i t i v i t y ^ W ith th e e x c e p t io n o f one

datum D o in t on th e c o n c e n t r a t i o n c u rv e s o f Cu, Na, and

K, no u n to w a rd e f f e c t s w ere o b s e rv e d and th e v a r i a t i o n

o f t h i s s i n g l e datum p o in t was a c c o u n ta b le from a con

s i d e r a t i o n o f m a t r ix e f f e c t s when th e m a t r ix t o b u f f e r

r a t i o s w itc h e d from a m a t r ix c o n c e n t r a t i o n t h a t was l e s s

th a n th e b u f f e r c o n c e n t r a t i o n t o a m a t r ix c o n c e n t r a t i o n

t h a t was g r e a t e r th a n th e b u f f e r c o n c e n t r a t i o n . T h is

e f f e c t i s a l s o c o n s i s t e n t w ith r e s u l t s r e p o r t e d i n th e

l i t e r a t u r e ^

The am ount o f e le m e n t p r e s e n t i n e a c h s t a n d a r d and

th e s u b s e q u e n t p e rc e n ta g e o f t h a t e le m e n t p r e s e n t i s

shown i n th e f o l lo w in g t a b l e s .


12

T ab le I I I . Amount o f e le m e n t p r e s e n t i n gram s i n each S tan d ard .

Ca Na Mg Cu K

S ta n d a rd I 0 .1 3 8 3 0 .1 5 5 3 0 .1593 0 .1 0 5 4 0 .0 7 6 0

S ta n d a rd I I 0 .0 7 5 2 0 .0 6 7 0 0 .0 6 6 3 0 .0 4 4 2 0 .0 3 1 9

S ta n d a rd I I I 0 .0 2 1 1 0 .0 1 7 9 0 .0 1 7 3 0 .0 1 1 3 0 .0 0 3 5

S ta n d a rd IV 0 .0 0 1 2 0 .0 0 1 0 0 .0 0 1 0 0 .0 0 0 7 0 .0 0 0 5

T ab le IV . Amount o f <s le m e n t p r e s e n t a s ■p e rc e n ta g e o f t o t a lw e ig h t o f S ta n d a r d .

S ta n d a rd I 1 2 .3 7 1 0 .4 7 1 0 .4 4 6 .5 1 4 .9 3

S ta n d a rd I I 5 .1 3 4 .3 3 4 .3 7 2 .3 5 2 . OS

S ta n d a rd I I I 1 .3 4 1 .1 4 1 .1 3 0 .75 0 .5 4

S ta n d a rd IV 0 .0 7 9 0 .0 6 6 0 .0 6 6 0 .0 4 6 0 .0 3 3

INTERNAL STANDARDS

A s u rv e y o f th e l i t e r a t u r e o f e m is s io n s p e c t ro s c o p y

r e v e a l s a lo n g l i s t o f p o t e n t i a l c h o ic e s f o r an i n t e r n a l

c o n t r o l f o r q u a n t i t a t i v e a n a l y s i s . A h ig h d e g re e o f

e m p ir ic is m seem s to be in v o lv e d i n th e s e l e c t i o n o f a

p a r t i c u l a r e le m e n t f o r a p a r t i c u l a r s i t u a t i o n . A s e a r c h

f o r a s u i t a b l e i n t e r n a l c o n t r o l w hich w ould com pensate

f o r some o f th e u n c o n t r o l l e d f a c t o r s t h a t i n f lu e n c e l i n e

i n t e n s i t y w h ile r e t a i n i n g th e d e s i r e d r e p r o d u c i b i l i t y

l e d p a s t t h e t r i a l s o f Ag and Co t o t h e r a r e e a r t h o x id e ,

I n 2C3 . U s in g th e c r i t e r i a t h a t th e r e p r o d u c i b i l i t y


13

among 12 r e p l i c a t e s o f a s a m p l e s h o u l d b e , f o r t h e d . c .

a r c m e t h o d u s e d , w i t h i n 2 0%f t h e r a r e e a r t h o x i d e p e r

f o r m e d q u i t e a d e q u a t e l y . A l t h o u g h t h e u s u a l a d m o n i t i o n s

i n s e l e c t i n g an i n t e r n a l c o n t r o l a r e t o p i c k an e l e m e n t

n o t p r e s e n t i n t h e s a m p l e t o be a n a l y z e d ; s e l e c t an

e l e m e n t w i t h e m i s s i o n l i n e s l y i n g w i t h i n 100 A° o f any

l i n e s t o be a n a l y z e d ; s e l e c t a l i n e w i t h a r c c h a r a c t e r

i s t i c s m a t c h i n g t h o s e o f t h e s u b s t a n c e t o be d e t e r m i n e d ,

s a t i s f a c t o r y r e s u l t s w e r e o b t a i n e d when o n l y t h e 3258 A0

1 5l i n e o f I n was u s e d . The f o l l o w i n g l i n e p a i r i n g s w e r e

u s e d i n d e t e r m i n i n g t h e a m o u n t s o f t h e v a r i o u s e l e m e n t s

p r e s e n t i n t h e s a m p l e s :

F o r Ca .............................................. Ca 3 9 6 8 / i n 3258

Fo r N a ......................................................Na 3 3 3 2 / i n 3258

F o r R i g ...................................................... trig 2 8 0 2 / i n 3258

For Cu ...................................................... Cu 3 2 4 7 / I n 3258

Fo r K ........................................................ K 4 0 4 4 / I n 3258

The a v e r a g e mean d e v i a t i o n o f t h e l o g r a t i o o f i n

t e n s i t i e s f o r a l l s a m p l e s a n a l y z e d i n t h e a r c i n g o f t h e

s t a n d a r d s was 1 4 . 1 / o . The a v e r a g e mean d e v i a t i o n o f t h e

l o g r a t i o o f i n t e n s i t i e s f o r a l l s a m p l e s a n a l y z e d i n t h e

a r c i n g o f t h e e x p e r i m e n t a l an d c o n t r o l s a m p l e s was 24.2/o

( s e e T a b l e V I I ) . By e l i m i n a t i n g o n e v a l u e f r om t h i s

t a b l e ( t h e 9 2^ mean d e v i a t i o n o f t h e !Tig 2 8 0 2 / i n 3258 l i n e

i n t h e C o n t r o l g r o u p ) , t h e a v e r a g e mean d e v i a t i o n o f a l l


14

sa m p le s i n th e e x p e r im e n ta l and c o n t r o l g ro u p s w ould be

o n ly 1 5 # .

The p ro c e s s f o r a d d in g th e i n t e r n a l c o n t r o l to th e

m a t r ix a f t e r th e m a t r ix had b e en d i l u t e d w ith th e L i-C

m ix tu re was a s f o l lo w s : th e d i l u t i o n s (show n on page 1 1 )

w ere made i n su c h a m anner t h a t th e t o t a l w e ig h t o f th e

m a t r ix p lu s b u f f e r was a p p ro x im a te ly 1 .5 0 g ra m s . To t h i s

was added 0 .0 2 5 gram s o f In 2 0 3 . The am ounts m ixed a re

shown i n T a b le V, w hich f o l lo w s .

T ab le 7 . C o m p o sitio n o f S ta n d a rd M ix tu re s i n g ra m s.

S ta n d a rd IM a tr ix1 .2 0 0 5

B u f fe r6 .3 0 0 0

I n t e r n a l C o n .T o ta l W eight 0 .0 2 4 9 1 .5 2 5 7

S ta n d a rd I I 0 .5 0 3 7 0 .9 9 3 9 0 .0 2 5 3 1 .5 2 7 9

S ta n d a rd I I I 0 .1 3 4 5 1 .4 1 2 4 0 .0 2 4 6 1 .5 7 1 5

S ta n d a rd IV 0 .0 0 7 7 1 .4 9 2 0 0 .0 2 4 9 1 .5 2 4 6

T h is m ethod a llo w e d th e r a t i o o f I n / t o t a l m ix tu re

t o be m a in ta in e d a s a c o n s t a n t , h a v in g a mean d e v ia t i o n

o f 1 .7 4 # . The a v e ra g e c o n c e n t r a t i o n o f I n i n su c h a

m ix tu re was 0 . 67# .

PREPARATION OF CONTROL SAMPLES AND EXPERIMENTAL SAMPLES

The n in e c o n t r o l sa m p le s and th e t e n e x p e r im e n ta l

sa m p le s w ere h a n d le d i n s i m i l a r f a s h i o n . B o th l o t s con

t a i n e d p l a n t m a t e r i a l o f a r a t h e r l a r g e , g r a n u la r s i z e .


The a v e ra g e w e ig h t o f th e c o n t r o l sa m p le s was 0 .4 5 4 3

grains w ith a mean d e v ia t i o n o f 10 .3& , w h ile t h a t o f th e

e x p e r im e n ta l sa m p le s was 0 .4 2 2 0 g ram s w i th a mean d e v ia

t i o n o f 9 .2 £ . The a s h was com posed o f d i s c r e t e g r a i n s

h a v in g a g r e y , w h i t e , o r y e l lo w c o l o r . The a p p e a ra n c e

o f b o th c o n t r o l and e x p e r im e n ta l sa m p le s was s i m i l a r .

E ach o f th e n in e te e n sa m p le s was g ro u n d in th e a g a te

m o r ta r f o r a p e r io d o f 10 m in u te s and re d u c e d to a f i n e

p o w d er. The pow der was th e n d r i e d f o r 1 h o u r a t 100°C

i n a d r y in g oven and added t o a m ix tu re o f b u f f e r and

i n t e r n a l c o n t r o l t h a t , l i k e w i s e , h ad b e en g ro u n d , d r i e d

and w e ig h e d . T h is new m ix tu re was a g i t a t e d a t 450 rpm

on th e l a t h e - m i x e r and t h i s was fo l lo w e d b y 30 m in u te s

o f h a n d -m ix in g i n th e a g a te m o r ta r . The am ounts o f sam

p l e , b u f f e r and i n t e r n a l c o n t r o l t h a t w ere com bined a re

shown i n T a b le VT w hich a p p e a rs on th e f o l lo w in g p a g e .


T ab le V I. C o m p o sitio n o f S a m p le - B u f f e r - I n te r n a l C o n tro l M ix tu re i n g ram s.

Sam ple B u f fe r I n t . Con. T o ta l W eight

C o n tro l 1 0 .0 7 0 2 1 .3 9 9 8 0 .0 2 4 9 1 .4 9 4 9

C o n tro l 2 0 .0 7 0 0 1 .3 9 9 9 0 .0 2 5 2 1 .4 9 5 1

C o n tro l 3 0 .0 6 9 8 1 .4 0 0 1 0 .0 2 5 3 1 .4 9 5 2

C o n tro l 4 0 .0 7 0 0 1 .3 9 9 9 0 .0 2 5 4 1 .4953

C o n tro l 5 0 .0 7 0 1 1 .4 0 0 0 0 .0 2 4 8 1 .4 9 4 9

C o n tro l 6 0 .0 7 0 8 1 .4 0 0 9 0 .0 2 5 3 1 .4 9 7 0

C o n tro l 7 0 .0 7 0 3 1 .4 0 0 4 0 .0 2 5 0 1 .4 9 5 7

C o n tro l 8 0 .0 7 0 0 1 .3 9 9 7 0 .0 2 5 1 1 .4 9 4 8

C o n tro l 9 0 .0 7 0 5 1 .4 0 0 0 0 .0 2 4 7 1 .4 9 5 2

E x p e r im e n ta l 1 0 .0 6 9 7 1 .4 0 0 3 0 .0 2 5 5 1 .4 9 5 5

E x p e r im e n ta l 2 0 .0 7 0 0 1 .4 0 0 0 0 .0 2 5 1 1 .4 9 5 1

E x p e r im e n ta l 3 0 .0 7 0 3 1 .4 0 0 1 0 .0 2 5 2 1 .4 9 5 6

E x p e r im e n ta l 4 0 .0 6 9 9 1 .4 0 0 5 0 .0 2 4 8 1 .4 9 5 2

E x p e r im e n ta l 5 0 .0 7 0 2 1 .4 0 0 1 0 .0 2 5 1 1 .4 9 5 4

E x p e r im e n ta l 6 0 .0 6 9 7 1 .3 9 9 8 0 .0 2 5 3 1 .4 9 4 8

E x p e r im e n ta l 7 0 .0 6 9 8 1 .4 0 0 4 0 .0 2 5 0 1 .4 9 5 2

E x p e r im e n ta l 8 0 .0 6 9 9 1 .4 0 0 1 0 .0 2 4 5 1 .4 9 4 5

E x p e r im e n ta l 9 0 .0 6 9 9 1 .4 0 0 8 0 .0 2 4 7 1 .4 9 5 4

E x p e r im e n ta l 10 0 .0 7 0 0 1 .3 9 9 7 0 .0 2 4 9 1 .4 9 4 6


P ROCEDURE FOR E X P O S U R E OF S A MP L E S

The f o l l o w i n g p r o c e d u r e was a d o p t e d f o r a l l s o l i d

m a t e r i a l s t h a t w e r e a r c e d d u r i n g t h e c o u r s e o f t h i s i n

v e s t i g a t i o n . The s o l i d s a m p l e s w e r e p a c k e d i n t o t h e

s a m p l e e l e c t r o d e c a v i t y w i t h a c l e a n s p a t u l a so t h a t

t h e s u r f a c e o f t h e m a t e r i a l was l e v e l .

S i n c e t h e s a m p l e c a v i t i e s h a d b e e n u n i f o r m l y e x

c a v a t e d , t h i s p r o c e d u r e i n s u r e d a r e l i a b l e d e g r e e o f

u n i f o r m i t y i n t h e a mo u n t o f m a t e r i a l a r c e d w i t h e a c h

e x p o s u r e •

A f t e r a f u l l r u n o f s a m p l e e l e c t r o d e s - n o r m a l l y

15 - h a d b e e n p o s i t i o n e d i n an a l u mi n u m e l e c t r o d e h o l d e r

t h e u n i t was p l a c e d i n a d r y i n g o v e n s e t a t 100 °C and

d r i e d f o r an h o u r . T h i s s e q u e n c e was i n a u g u r a t e d t o

o v e r c o m e t h e t e n d e n c y o f p o w d e r e d s a m p l e s t o s p l a s h upon

a r c i n g due t o t h e p r e s e n c e o f a b s o r b e d m o i s t u r e .

A f r e s h c o u n t e r e l e c t r o d e - w i t h no t a p e r - was

i n s e r t e d f o r e a c h e x p o s u r e , f o l l o w e d by t h e i n s e r t i o n

o f t h e s a m p l e e l e c t r o d e . The r o t a t i n g s t e p - s e c t o r was

a l l o w e d t o come t o s p e e d b e f o r e t h e f i r s t e x p o s u r e o f

e a c h s e r i e s a nd t h e n p e r m i t t e d t o r e m a i n r u n n i n g t h r o u g h

o u t t h e f u l l r u n o f 15 e x p o s u r e s . The s t e p - s e c t o r s p e e d

was s e t a t 550 +_ 2% rpm. T h i s s p e e d was h i g h e n o u g h t o


18

i n s u r e a g a i n s t t h e i n t e r m i t t e n c y e f f e c t . ^ ° The s a m p l e was

t h e n a r c e d , w i t h no p r e b u r n , f o r a p e r i o d o f 3D s e c o n d s .

The e l a p s e d t i m e u>as m e a s u r e d by s t o p - w a t c h a n d showed

an a v e r a g e v a r i a t i o n o f _+ 0 . 1 s e c o n d . The a r c i n g was

i n a u g u r a t e d by p h y s i c a l l y s h o r t i n g t h e e l e c t r o d e gap w i t h

a s m a l l s e g m e n t o f c a r b o n e l e c t r o d e s e t i n t o an i n s u l a t e d

h a n d l e . The s p e c t r a w e r e r e c o r d e d - s i x t o a p l a t e - t h e

p l a t e r e m o v e d and p r o c e s s e d f o r d e v e l o p m e n t i m m e d i a t e l y .

An o p t i mu m s l i t w i d t h o f 20 m i c r o n s h a d b e e n e s t a b

l i s h e d w i t h some p r e l i m i n a r y e x p e r i m e n t a t i o n and t h e s y s

tem was t e s t e d f o r t h e a b s e n c e o f c o m p o n e n t d e f e c t s u s -1 7i n g t h e m e t h o d r ec ommen d ed by H a r r i s o n . l i i i th t h i s p r o

c e d u r e , s p e c t r a a r e o b t a i n e d u s i n g f u l l s l i t i l l u m i n a t i o n

an d a r e t h e n c o m p a r e d w i t h t h o s e o b t a i n e d w i t h v a r i o u s

p o r t i o n s o f t h e s l i t c o v e r e d by a H a r t m a n n d i a p h r a g m .

I f c o m p a r a b l e l i n e s h a r p n e s s i s o b t a i n e d , one c a n c o n

c l u d e t h a t t h e s p e c t r o g r a p h i s c o r r e c t l y f o c u s e d a nd t h e

s y s t e m i s f r e e f r om c o m p o n e n t d e f e c t .

D u r i n g a c t u a l e x p o s u r e s , t h e H a r t m a n n d i a p h r a g m

was s e t t o i t s f i s h t a i l p o s i t i o n t o i n t e r c e p t t h e c e n

t r a l beam w i t h an e x p o s e d h e i g h t o f 10 mm.

The e l e c t r o d e s w e r e o b s e r v e d t h r o u g h o u t t h e d u r

a t i o n o f t h e b u r n w i t h t h o s e s a m p l e s e x h i b i t i n g s i g n i f i

c a n t s p u t t e r i n g , o r n o n - u n i f o r m a r c i n g b e i n g d i s c a r d e d .

I n t h e s e c a s e s a new s a m p l e e l e c t r o d e was p r e p a r e d i n

o r d e r t o k e e p t h e n u m b e r o f r e p l i c a t e s e x p o s e d , a c o n


19

s t a n t , a t 1 5 . The two m ost p r e v a l e n t ex am p les o f n o n -

u n ifo rm a r c i n g w ere i n s t a n c e s when th e a rc was l o c a l i z e d

on th e e l e c t r o d e r im w ith no e v id e n c e o f a rc w ander

th ro u g h th e sam ple r e g io n an d , s e c o n d ly , th o s e o c c a s io n s

when th e a rc s p o n ta n e o u s ly e x t in g u i s h e d i t s e l f b e fo r e th e

r e q u i s i t e t im e had e la p s e d . The p h o to g ra p h ic p l a t e s on

w h ich th e e x p o s u re s w ere r e c o rd e d w ere rem oved t o th e

dark room and p ro c e s s e d im m e d ia te ly . D u rin g th e tim e o f

d e v e lo p m e n t, th e t r a y s c o n ta in in g th e d e v e lo p e r w ere/ T d

a g i t a t e d a c c o rd in g to th e m a n u f a c tu r e r s re c o m m e n d a tio n . 0

T h is te c h n iq u e s e r v e s t o re d u c e th e E b e rh a rd E f fe c t^ S

w h ich r e s u l t s when f r e s h d e v e lo p e r i s n o t c o n t in u o u s ly

s u p p l ie d t o th e ex p o sed e m u ls io n s u r f a c e . A f te r d e v e lo p

m ent th e p l a t e s w ere a i r d r i e d f o r a p e r io d o f a t l e a s t

f o u r h o u rs and th e n a n a ly z e d a s d e s c r ib e d i n th e fo l lo w

in g s e c t i o n .


CHAPTER I I I

DATA AND RESULTS

P ro c e d u re F o r O b ta in in g D e n s i to m e tr ic D a ta

A D i e t e r t - A .R .L . D e n s ito m e te r -C o m p a ra to r was u se d

t o o b t a in a d e n s i to m e t r i c r e a d in g o f t h e a n a l y s i s l i n e s

from e a c h e x p o sed p l a t e . The u n i t u t i l i z e d was b a la n c e d

t o r e a d a 0 t o 100 t r a n s m is s io n s c a le w i th a c l e a r p l a t e

r e a d in g s e t a t 1 0 0 . The u n i t was r e b a la n c e d w henever a

new p l a t e was i n s e r t e d . A warm -up tim e o f 30 m in u te s

was u se d to a v o id t r a n s i e n t h e a t in g e f f e c t s . A maximum

o f se v e n s t e p s was a v a i l a b l e f o r d e n s i to m e t r i c r e a d in g s

w ith th e a v e ra g e l i n e e x h i b i t i n g f i v e r e a d a b le s t e p s .

The m odal num ber o f l i n e s r e a d f o r e ac h a n a l y t i c a l p o in t

i n e ac h c o n c e n t r a t i o n ra n g e was f i f t e e n f o r t h e s t a n

d a rd s . The m odal num ber o f l i n e s r e a d f o r e a c h a n a l y t

i c a l p o i n t i n th e c o n t r o l and e x p e r im e n ta l g ro u p s was

s i x .

The mean d e v i a t i o n f o r th e r e a d in g s o f t h e lo g r a t i o

o f i n t e n s i t i e s o b ta in e d f o r e a c h s t a n d a r d , c o n t r o l and

e x p e r im e n ta l g ro u p i s shown i n th e t a b l e on t h e fo l lo w in g

p a g e :

20


21

T a b le V I I . Mean D e v i a t io n o r D e n s i t o m e t r i c D a ta a s P e r c e n ta g e .

Log R a t io o f I n t e n s i t i e s

Ca396Sln 3 2 4 8

Na3302T 5J258

Mg2S02ln 3 2 5 8

Cu3247ln 3 2 $ 8

K 4044 In3 2$8

S ta n d a r d I 1 4 .0 0 4 .3 8 3 7 .0 0 2 0 .3 0 5 .0 0

S ta n d a r d I I 1 1 .2 0 1 .1 4 3 4 .0 0 1 4 .6 0 1 2 .9 0

S ta n d a r d I I I 1 0 .0 0 0 .0 7 1 3 .0 0 3 1 .0 0 1 4 .9 0

S ta n d a r d IV 1 0 .0 0 1 0 .4 7 2 2 .0 0 6 .9 0 9 .5 0

C o n t r o l 3 4 .0 0 5 .2 7 9 2 .0 0 1 4 .7 0

Exp e r im e n t a l 9 .0 0 7 .2 0 3 1 .8 0 9 .3 0 1 5 .0 0

C a l c u l a t i n g Scheme F o r D e n s i to m e t r i c D ata

The t e c h n i q u e u se d t o c o n v e r t l i n e d e n s i t y r e a d i n g s

t o t h e i r a s s o c i a t e d c o n c e n t r a t i o n s o f s p e c i f i c e le m e n ts

i n v o l v e s t h e f o l l o w i n g a s s u m p t io n s :

a . ) T h a t t h e r e l a t i o n s h i p b e tw ee n l i g h t i n t e n s i t y

and l i n e d e n s i t y can be a c c u r a t e l y e s t a b l i s h e d

by a p l o t o f d e n s i t y v s . t h e l o g o f r e l a t i v eon

i n t e n s i t y .

b . ) T h a t t h e l i n e d e n s i t y i s p r o p o r t i o n a l t o t h e

amount o f t h e p a r t i c u l a r e le m e n t b e in g s t u d i e d ? ^

c . ) T h a t t h e f a c t o r s t h a t c o n t r o l t h e v a r i a b i l i t y

o f t h e s p e c t r a l l i n e s b e in g s t u d i e d c an be b a l

a n ce d by t h e u s e o f an i n t e r n a l c o n t r o l whose


p r o p e r t i e s a re co m parab le t o t h e e le m e n ts b e

in g s t u d i e d .

The l o g a r i t h m i c r e s p o n s e o f t h e e m u ls io n t o t h e i n

c i d e n t l i g h t can be s i m p l i f i e d by t h e u se o f a m athe

m a t i c a l f u n c t i o n known a s t h e S e i d e l f u n c t i o n . T h is

t r a n s f o r m a t i o n a d j u s t s t h e l o g a r i t h m i c r e s p o n s e o f t h e

e m u ls io n t o a more e a s i l y a n a ly z e d l i n e a r p l o t by t r a n s

fo rm in g t h e d e n s i t y , d e f i n e d as t h e - Log T r a n s m i t t a n c e ,

t o t h e S e i d e l f u n c t i o n A t d e f i n e d a s t h e Log( 1 / T r a n s

m i t t a n c e - 1 ) . I f t h e T r a n s m i t t a n c e i s e x p r e s s e d a s a

p e r c e n t a g e , t h e c o r r e s p o n d in g fo r m u la i s g iv e n a s A =22Log( 1 0 0 / ^T - 1 ) . I n p r a c t i c e , a t a b l e i n w hich t h e

S e i d e l v a lu e s c o r r e s p o n d in g to t h e t r a n s m i t t a n c e r e a d

in g s o b t a i n e d from t h e d e n s i t o m e t e r can be u se d ?^ (Sev

e r a l e r r o r s i n t h e t a b l e c i t e d have been n o te d i n a l e t

t e r t o be p u b l i s h e d i n t h e J a n u a ry 1S73 i s s u e o f A p p l ie d

S p e c t r o s c o p y , s u b m i t t e d by t h i s au th o r) .

The c a l i b r a t i o n c u rv e s p r e p a r e d from t h e s t a n d a r d s

c o n t a i n i n g Ca, Na, Mg, Cu, and K i n v a r y i n g am ou n ts , a s

w e l l a s t h e a v e ra g e am ounts o f t h e s e e le m e n ts fo u n d i n

b o th t h e c o n t r o l and e x p e r im e n ta l p l a n t sa m p le s a r e

.shown g r a p h i c a l l y on t h e f o l lo w in g p a g e s .

R eproduced with perm ission o f the copyright owner. Further reproduction prohibited without perm ission.

■o

" C D

CM

CO

“ CMO

•H CM

•Hr-HO

M ..C \J

CMCO* CM


Log

(%C

a)

..CO

. .C MCM

" O

cn. .C M

CM•H

cn

o"CO

•H

o

..o

•H

CM CM CO^ r .CM

o


U)

"00

CM'CM

•H

O

•H

O'00

C M00

Reproduced with perm ission o f the copyright owner. Further reproduction prohibited without perm ission.

4 g

| Fi

gure

4.

C

alib

rati

on

Curv

e fo

r C

oppe

r S

tan

dar

ds

c o _’0 0 =5

• u oCD

‘C O O'O

. \ r

C \JCM

26

- o

c\ jC\J

. ^ r

i

CDCO

CDCD

i*

O

i

1 1 1—

§• 3 8L ^ r r y O O l

—I—CMCM*

CD O


"CO

__^rc\ j

CM

- Oa.

CM

o

. / s rCM

•H

•H

O

•H

- + -

CO-4 -CM

H--------------1---------CM v -

8S*rN I( J f t O O O I


LOG(

% K

)

2 8

T a b le V I II : Data T ab le f o r C alcium C a l ib r a t io n C u rv e.

?SCa Log(^Ca)

S ta n d a r d I 0 .0 7 9 - 0 .1 0 2 0 .2 2

S ta n d a rd I I 1 .3 4 0 .1 2 7 2 .6 8

S t a n d a r d l l l 5 .1 8 0 .7 1 4 3 .6 2

S ta n d a rd IV 1 2 .3 7 1 .0 9 2 5 .0 4

T a b le IX : D a ta T ab le f o r Sodium C a l i b r a t i o n C u rv e .

5&Na Log(£Na) T ,Na3302 v L°s(T n 7 S 5 8 )

S ta n d a r d I 0 .0 6 6 - 1 .1 8 - 3 .6 7

S ta n d a r d I I 1 .1 4 0 .0 5 7 - 0 .8 5

S t a n d a r d l l l 4 .3 8 0 .6 4 1 1 .2 5

S ta n d a r d IV 1 0 .4 7 1 .0 2 5 .13

T a b le X: D a ta T ab le .f o r Magnesium C a l i b r a t i o n C u rv e .

Log($Mg)

S ta n d a rd I 0 .0 6 6 - 1 .1 8 - 2 .3 5

S ta n d a r d I I 1 .1 3 0 .053 0 .7 1

S t a n d a r d l l l 4 .3 7 0 .6 4 0 1 .9 9

S ta n d a rd IV 1 0 .4 4 1 .0 2 3 .1 6

T a b le X I: D a ta T ab le f o r Copper C a l i b r a t i o n C u rv e .

^Cu Log(^Cu) T ,Cu3247> L° s ( r r i5 5 'J5 )

S ta n d a r d I 0 .0 4 6 - 1 .3 4 1 .0 8

S ta n d a r d I I 0 .7 5 - 0 .1 2 5 1 .5 7

S t a n d a r d l l l 2 .8 9 0 .4 6 1 1 .7 2

S ta n d a r d IV 6 .9 1 0 .8 3 9 4 .8 0


29

T ab le X II : D ata T a b le f o r P o ta ss iu m C a l ib r a t io n C u rve.

5&K Log(^K) L° s ^ § 2 5 '6^

S ta n d a r d I 0 .3 3 -0 .4 S 2 - 2 . S i

S ta n d a r d I I 0 .5 4 -0 .2 6 S - 2 .0 2

S ta n d a rd I I I 2 .0 9 0 .3 2 0 - 0 . 4 0

S ta n d a r d IV 4 .9 S 0 .6 9 7 3 .5 7

The c o m p o s i t io n o f t h e c o n t r o l sa m p le s w hich were

m ixed w i th t h e b u f f e r and t h e i n t e r n a l c o n t r o l i s shown

i n T a b le X I I I . The c o m p o s i t io n o f t h e e x p e r im e n ta l sam

p l e s w hich w ere m ixed w i th t h e b u f f e r and t h e i n t e r n a l

c o n t r o l i s shown i n T ab le XIV. B o th t a b l e s a p p e a r on

t h e f o l lo w in g p a g e .


3D

T a b le X I I I : C o m p o sitio n o f C o n t r o l - B u f f e r - I n t e r n a l Con-

Sample B u f f e r I n t . Con. T o t a l W eight

C o n t r o l 1 0 .0 7 0 2 1 .3 9 9 # 0 .0 2 4 9 1 .4 9 4 9

C o n t r o l 2 0 .0 7 0 0 1 .3 9 9 9 0 .0 2 5 2 1 .4 9 5 1

C o n t r o l 3 0 .0 6 9 # 1 .4 0 0 1 0 .0 253 1 .4 9 5 2

C o n t r o l 4 0 .0 7 0 0 1 .3 9 9 9 0 .0 2 5 4 1 .4953

C o n t r o l 5 0 .0 7 0 1 1 .4 0 0 0 0 .0 2 4 # 1 .4 9 4 9

C o n t r o l 6 0 .0 7 0 # 1 .4 0 0 9 0 .0 253 1 .4 9 7 0

C o n t r o l 7 0 .0 7 0 3 1 .4 0 0 4 0 .0 2 5 0 1 .4 9 5 7

C o n t r o l # 0 .0 7 0 0 1 .3 9 9 7 0 .0 7 0 0 1 .4 9 4 #

C o n t r o l 9 0 .0 7 0 5 1 .4 0 0 0 0 .0 2 4 7 1 .4 9 5 2

T a b le XIV: C o m p o s i t io n o f E x p e r i m e n t a l - B u f f e r - I n t e r n a lC o n t r o l M ix tu re i n g ra m s ..Sample B u f f e r I n t . Con. T o ta l W eight

E x p e r . 1 0 .0 6 9 7 1 .4 003 0 .0 2 5 5 1 .4 9 5 5

E x p e r . 2 0 .0 7 0 0 1 .4 0 0 0 0 .0 2 5 1 1 .4 9 5 1

E x p e r . 3 0 .0 7 0 3 1 .4 0 0 1 0 .0 2 5 2 1 .4 9 5 6

E x p e r . 4 0 .0 6 9 9 1 .4 0 0 5 0 .0 2 4 # 1 .4 9 5 2

E x p e r . 5 0 .0 7 0 2 1 .4 0 0 1 0 .0 2 5 1 1 .4 9 5 4

E x p e r . 6 0 .0 6 9 7 1 .3 9 9 # 0 .025 3 1 .4 9 4 #

E x p e r . 7 0 .0 6 9 # 1 .4 0 0 4 0 .0 2 5 0 1 .4 9 5 2

E x p e r . # 0 .0 6 9 9 1 .4 0 0 1 0 .0 2 4 5 1 .4 9 4 5

E x p e r . 9 0 .0 6 9 9 1 .4 0 0 # 0 .0 2 4 7 1 .4 9 5 4

E x p e r . 10 0 .0 7 0 0 1 .3 9 9 7 0 .0 2 4 9 1 .4 9 4 6


31

The a m o u n t s o f t h e e l e m e n t s a s p r e s e n t i n t h e c o n t r o l a n d e x p e r i m e n t a l s a m p l e s , a s d e t e r m i n e d f r o m t h e s e c a l i b r a t i o n c u r v e s , i s a s f o l l o w s :

T a b l e XV: Amount o f C a l c i u m i n C o n t r o l and E x p e r i m e n t a lS a m p l e s a s p e r c e n t a q e .

L o o ( C a 3 9 6 8 ) Log (/oCa) %CaI n 3258

C o n t r o l 1 2 . 4 7 0 . 4 5 2 . 8 1

C o n t r o l 2 2 . 2 7 0 . 4 0 2 . 5 1

C o n t r o l 3 2 . 6 2 0 . 4 9 3 . 0 9

C o n t r o l 4 2 . 4 5 0 . 4 4 2 . 7 5

C o n t r o l 5 2 . 0 9 0 . 3 5 2 . 2 3

C o n t r o l 6 2 . 2 1 0 . 3 4 2 . 1 8

C o n t r o l 7 2 . 1 0 0 . 3 4 2 . 1 8

C o n t r o l 8 2 . 5 0 0 . 4 5 2 . 8 8

C o n t r o l 9 1 . 9 2 0 . 3 1 2 . 0 4

The a v e r a g e Ca p r e s e n t i s ( 2 . 5 2 + 0 . 3 2 ) * .

E x p e r . 1 2 . 2 9 0 . 4 0 2 . 5 1

E x p e r . 2 1 . 9 2 0 . 3 1 2 . 0 4

E x p e r . 3 2 . 2 2 0 . 34 2 . 1 8

E x p e r . 4 1 . 7 3 0 . 2 5 1 . 8 2

E x p e r . 5 2 . 1 9 0 . 38 2 . 3 9

E x p e r . 6 1 . 7 8 0 . 2 8 1 . 9 0

E x p e r . 7 2 . 1 0 0 . 3 4 2 . 1 8

E x p e r . 8 1 . 8 7 0 . 3 0 1 . 9 9

E x p e r . 9 1 . 8 9 0 . 3 1 2 . 0 4

E x p e r . 10 1 . 7 8 0 . 2 8 1 . 9 0

The a v e r a g e % Ca p r e s e n t i s ( 2 . 0 9 + 0 . 1 8 )/3.


32

T a b l e XUI: Amount o f Sod i um i n C o n t r o l and E x p e r i m e n t a lS a m p l e s a s p e r c e n t a g e .

Log ( Na 3302 ̂I n 3258

Log (°oNa) ^Na

C o n t r o l 1 - 4 . 7 5 - 1 . 5 6 0 . 0 2 75

C o n t r o l 2 - 5 . 1 5 - 1 . 6 9 0 . 0 2 0 4

C o n t r o l 3 - 4 . 4 0 - 1 . 4 3 0 . 0 3 7 2

C o n t r o l 4 - 5 . 3 5 -1 . 7 9 0 . 0 1 6 2

C o n t r o l 5 — 4 . 3 5 -1 . 61 0 . 0 3 0 9

C o n t r o l 6 - 5 . 2 0 -1 . 7 4 0 . 0 1 8 2

C o n t r o l 7 -4 . 9 0 -1 . 64 0 . 0 2 2 9

C o n t r o l 8 - 5 . 1 0 - 1 . 7 0 U. 0200

C o n t r o l 9 - 4 . 8 0 - 1 . 5 3 0 . 0 2 6 3

The a v e r a g e ,'b Na p r e s e n t i s ( 0 . 0 2 4 4 + 0 . 0 0 5 4 ) ^ .

E x p e r . 1 - 4 . 7 8 - 1 . 5 7 0 . 0 2 6 9

E x p e r . 2 - 5 . 4 0 - 1 . 8 0 0 . 0 1 5 8

E x p e r . 3 - 4 . 6 0 - 1 . 4 9 0 . 0 3 2 4

E x p e r . 4 - 5 . 1 7 - 1 . 7 3 0 . 0 1 8 6

E x p e r . 5 - 5 . 0 7 - 1 . 5 5 0 . U 2 1 9

E x p e r . 6 - 5 . 1 5 - 1 . 6 9 0 . 0 2 0 4

E x p e r . 7 - 4 . 6 7 -1 . 5 4 0 . 0 2 8 8

E x p e r . 8 - 5 . 4 5 - 1 . 8 4 0 . 0 1 4 4

E x p e r . 9 - 5 . 5 0 -1 . 8 6 0 . 0 1 3 8

E x p e r . 10 - 4 . 8 2 -1 . 5 9 0 . 0 2 5 7

The a v e r a g e % Na p r e s e n t i s ( 0 . 0 2 1 9 + 0 . 0040 )/a.


f a b l e XV II ; Amount o f i f l aqnesium i n C o n t r o l and E x p e r i -m e n t a l S a m p l e s a s p e r c e n t a g e .

L a g ( mg 2 8 ° 2 ) In 3258

Log (/olTlg) }S!Tlg

C o n t r o l 1 - U . 2 0 - 0 . 3 0 0 . 5 0 1

C o n t r o l 2 - 0 . 1 2 - 0 . 2 5 0 . 5 6 2

C o n t r o l 3 - 0 . 4 8 - 0 . 4 1 0 . 3 8 9

C o n t r o l 4 - 0 . 4 0 - 0 . 3 7 0 . 4 2 6

C o n t r o l 5 - 0 . 5 5 - 0 . b2 0 . 2 3 9

C o n t r o l 6 - 0 . 5 2 - 0 . 4 3 0 . 3 7 1

C o n t r o l 7 -1 . 0 7 - 0 . 6 5 0 . 2 2 3

C o n t r o l 8 - 1 . 8 6 - 0 . 9 8 0 . 1 0 2

C o n t r o l 9 -1 . 0 9 - 0 . 6 5 0 . 2 2 3

The a v e r a g e (Tig p r e s e n t i s ( 0 . 3 3 7 + U . 1 1 2 )%.

E x p e r . 1 - 0 . 7 9 - 0 . 5 4 0 . 2 8 8

E x p e r . 2 - U . 85 - 0 . 5 5 U. 275

E x p e r . 3 - Q . 4 4 - 0 . 3 8 0 . 4 1 6

E x p e r . 4 - 0 . 7 4 - 0 . 5 2 0 . 3 0 9

E x p e r . 5 - 0 . 7 8 - 0 . 5 3 0 . 2 9 5

E x p e r . 6 - 1 . 0 8 - 0 . d5 0 . 2 2 3

E x p e r . 7 - 0 . 2 7 - U . 3 2 0 . 4 7 8

E x p e r . 8 - 1 . 1 3 - 0 . 7 5 0 . 1 7 7

E x p e r . 9 - 1 . 7 6 - 0 . 9 4 0 . 1 1 4

E x p e r . 10 - 0 . S U - 0 . 5 4 0 . 2 8 8

The a v e r a g e % (Tig p r e s e n t i s ( 0 . 2 8 6 + 0 . 0 7 1 ) £ .


34

T a b l e X U I I I : Amount o f C o p p e r i n C o n t r o l and E x p e r i m e n t a l S a m p l e s a s p e r c e n t a g e .

The a mo u n t o f C o p p e r p r e s e n t i n t h e c o n t r o l s a m p l e s

mas b e l ow t h e l e v e l o f d e t e c t a b i l i t y . The a mo un t a p p e a r

i n g i n t h e e x p e r i m e n t a l s a m p l e s , e x t r a p o l a t e d f r om t h e

c a l i b r a t i o n c u r v e , i s shown b e l o w .

L° 9 ( j n 32 58 ̂ L° 9 ^ CU

E x p e r . 1 - 5 . 4 0 - 8 . 9 0 1 . 2 6 X 1 0 ~ 9

E x p e r . 2 - 6 . 2 0 - 1 1 . 0 0 1 . 0 0 X 1 0 -11

E x p e r . 3 - 5 . 62 - 9 . 5 0 3 . 1 5 X 1 0 - 1 0

E x p e r . 4 - 4 . 7 4 - 7 . 1 0 7 . 9 4 X 1 0 “ 8

E x p e r . 5 - 3 . 8 5 - 4 . 7 0 2 . 0 0 X 1 0 - 5

E x p e r . 6 -6 . 2 7 - 1 1 . 2 0 6 . 31 X 1 0 “ 12

E x p e r . 7 - 5 . 3 7

a00.CO• 1 . 5 8 X 1 0 ~ 9

E x p e r . a - 5 . 5 0 - 9 . 2 0 5 . 3 1 X 1 0 - 1 0

E x p e r . 9 -5 . 7 2 - 9 . 7 0 2 . 0 0 X 1 0 - 1 0

E x p e r . 10 - 5 . 4 1 - 9 . 9 0 1 . 2 6 X 1 0 ~ 10

The a v e r a g e % Cu p r e s e n t i s 2 . 0 1 x 1tJ~D/o.


35

T a b l e XIX; Amount o f P o t a s s i u m i n C o n t r o l a nd E x p e r i m e n t a l S a m p l e s a s p e r c e n t a g e .

L o g ( K 4 0 4 4 ) In 3250

L o g ( ^ K ) cf 1/ /oK

C o n t r o l 1 - 1 . 7 2 - 0 . 1 3 2 0 . 7 3 7

C o n t r o l 2 - 1 . 4 6 - 0 . 0 4 2 0 . 9 0 8

C o n t r o l 3 - 1 . 3 1 0 . 0 1 0 1 . 0 2 0

C o n t r o l 4 - 1 . 5 9 - 0 . 0 2 4 0 . 9 4 6

C o n t r o l 5 -1 . 5 4 - 0 . 1 0 8 0 . 7 8 0

C o n t r o l 6 -1 . 73 - 0 . 1 5 6 0 . 6 9 8

C o n t r o l 7 - 1 . 5 1 - 0 . 0 7 2 0 . 8 4 7

C o n t r o l 8 - 2 . 4 8 - 0 . 3 9 6 0 . 3 9 8

C o n t r o l 9 - 1 . 1 9 0 . 0 6 0 1 . 1 5 0

The a v e r a g e ^ K p r e s e n t i s ( 0 . 8 3 1 + 0 . ' 1 47 )/a.

E x p e r . 1 - 1 . 5 1 - 0 . 0 7 2 0 . 8 4 7

E x p e r . 2 - 1 . 6 9 - 0 . 0 1 2 0 . 9 7 3

E x p e r . 3 - 1 . 7 3 - 0 . 1 3 3 0 . 7 3 6

E x p e r . 4 - 1 . 5 0 - 0 . 0 6 0 0 . 8 7 1

E x p e r . 5 - 1 . 2 4 0 . 0 3 6 1 . 0 9 0

E x p e r . 6 - 1 . 9 0 - 0 . 0 2 4 0 . 9 4 5

E x p e r . 7 -1 . 6 5 - 0 . 1 0 9 0 . 7 7 8

E x p e r . 8 - 2 . 1 5 - 0 . 2 3 8 0 . 5 1 5

E x p e r . 9 - 2 . 3 6 - 0 . 3 6 0 0 . 4 3 6

E x p e r . 10 - 2 . 0 4 - 0 . 2 5 2 0 . 5 5 9

The a v e r a g e % K p r e s e n t i s ( 0 . 7 7 5 + 0 . 1 6 0 ) g .


CHAPTER IV

CONCLUSIONS

The p r o c e s s o f u s i n g a s y n t h e t i c m a t r i x f o r th e

a n a l y s i s o f b i o l o g i c a l m a t e r i a l s i s , i n p r i n c i p l e ,

s t r a i g h t f o r w a r d . The g e n e r a l p r o p o r t i o n s o f t h e e l e

m ents p r e s e n t and t h e i r c h e m ic a l fo rm c a n , i n p r i n c i p l e ,

be d u p l i c a t e d . The c o n d i t i o n s o f e x p o s u re and t h e i n

t e r e l e m e n t e f f e c t s c an a l s o , i n p r i n c i p l e , be n o rm a l

i z e d by t h e u s e o f an i n t e r n a l s t a n d a r d .

I n p r a c t i c e , h o w ev er , t h e c o n t r o l o f t h e s e i te m s

i s d i f f i c u l t t o a c h i e v e . The p r o c e d u r e a d o p te d f o r t h i s

a n a l y s i s h a s d e m o n s t r a t e d , i t se em s , t h a t a s y n t h e t i c

m a t r ix can be c o n s t r u c t e d w hich w i l l p ro d u c e a c a l i b r a

t e d r e s p o n s e o v e r a w ide c o n c e n t r a t i o n ra n g e and th e

u se o f a r a r e e a r t h o x id e d o e s l e n d i t s e l f t o a h ig h

d e g re e o f n o r m a l i z a t i o n o f t h e b a s e l i n e c o n d i t i o n s a f

f e c t i n g b o th t h e s t a n d a r d and t h e a n a l y t i c a l sam p les

i n v e s t i g a t e d . The p o s s i b i l i t y o f e l i m i n a t i n g i n t e r e l e

ment e f f e c t s w i l l , h o w ev er , be d i f f i c u l t t o a c h ie v e

w henever m i x t u r e s w hich m u s t , o f n e c e s s i t y , v a r y w id e ly

t o o b t a i n t h e r e q u i s i t e c o n c e n t r a t i o n s a r e u t i l i z e d .

I n t h e c a s e o f t h e a n a l y s i s o f tu m o ro u s and n o rm al

p l a n t s a m p le s p e r fo rm e d h e r e , t h e s y n t h e t i c m a t r i x u s e d

i n t h e c o n s t r u c t i o n o f t h e s t a n d a r d c o n c e n t r a t i o n c u rv e s

a l lo w s one t o make t h e f o l l o w i n g o b s e r v a t i o n s a b o u t t h e

36


37

a mo un t of Ca, Na , Mg, Cu and K f o u n d t o be p r e s e n t .

C a l c i u m :

The c o n t r o l s a m p l e s c o n t a i n e d an a v e r a g e o f

( 2 . 5 2 _+ 0 , 3 2 ) % o f Ca w h i l e t h e e x p e r i m e n t a l s a m p l e s c o n

t a i n e d an a v e r a g e o f ( 2 . 0 9 +_ 0 . 1 8 ) ^ , f r o m w h i c h o ne c a n

c o n c l u d e t h a t t h e r e i s a d e c r e a s e i n t h e a m o u n t o f

C a l c i u m p r e s e n t i n e a c h g r o u p o f p l a n t m a t e r i a l .

S o d i u m :


( 0 . 0 2 4 4 _+ 0 . 0 0 5 4 ) ^ of Na w h i l e t h e e x p e r i m e n t a l s a m p l e s

c o n t a i n e d an a v e r a g e o f ( 0 . 0 2 1 9 _+ Q . 00 4 0 ) / a Na , f r om w h i c h

o n e c a n c o n c l u d e t h a t t h e r e i s a v e r y s l i g h t d e c r e a s e i n

t h e a mo u n t o f Sod ium p r e s e n t i n e a c h g r o u p o f p l a n t m a t

e r i a l .

M a g n e s i u m :


( 0 . 3 3 7 +_ 0 . 1 1 2 ) ^ o f Mg w h i l e t h e e x p e r i m e n t a l s a m p l e s c o n

t a i n e d an a v e r a g e of ( 0 . 2 8 6 _+ 0 . 0 7 1 )% Mg, f r o m w h i c h o n e

c a n c o n c l u d e t h a t t h e r e i s a v e r y s l i g h t d e c r e a s e i n t h e

amo un t o f Mag n es iu m p r e s e n t i n e a c h g r o u p o f p l a n t m a t e r

i a l .

C o p p e r :

The a mo u n t o f Cu p r e s e n t i n t h e c o n t r o l s a m p l e s

was s o i n s i g n i f i c a n t t h a t i t was u n d e t e c t a b l e u n d e r t h e

s t a n d a r d c o n d i t i o n s a d o p t e d f o r t h i s a n a l y s i s . I n t h e

e x p e r i m e n t a l s a m p l e s , h o w e v e r , t h e r e was an o b s e r v a b l e


38

a m o u n t o f t h e m a t e r i a l p r e s e n t . The c a l i b r a t i o n c u r v e s

c o n s t r u c t e d f o r t h i s e l e m e n t c o u l d be e x t r a p o l a t e d t o t h e

r e g i o n o f l e s s e r i n t e n s i t y a n d , f r o m t h i s p r o c e d u r e , an

o r d e r o f m a j n i t u d e f i g u r e o f 2 . 0 1 x 1 0 " ^ c o u l d be e s t

i m a t e d . T h i s p r o c e d u r e l e a d s one t o b e l i e v e t h a t t h e r e

i s , i n f a c t , an i n c r e a s e i n t h e C o p p e r l e v e l s due t o t h e

a c t i o n o f t h e c a r c i n o g e n on t h e p l a n t s y s t e m .

P o t a s s i u m :


( 0 . 8 3 1 _+ 0 .147)>o K w h i l e t h e e x p e r i m e n t a l s a m p l e s e x h i b i t

e d ai a v e r a g e c o n c e n t r a t i o n o f ( 0 . 7 7 5 +_ 0 . 1 6 0 ) / o K, f r om

w h i c h o ne c a n c o n c l u d e t h a t t h e r e i s a v e r y s l i g h t d e c r e a s e

i n t h e a m o un t o f P o t a s s i u m p r e s e n t i n e a c h g r o u p o f p l a n t

m a t e r i a l . The d i f f i c u l t y o f c o n t r o l l i n g t h e b e h a v i o u r o f

P o t a s s i u m i n t h e d . c . a r c i s e v i d e n t . T h e s e r e s u l t s a r e

d i s p l a y e d g r a p h i c a l l y i n F i g u r e s 6 - 1 0 on t h e f o l l o w i n g

p a g e s .

I n s u m ma r y , t h e s y n t h e t i c m a t r i x d o e s seem t o be a

u s e f u l d e v i c e i n a l l o w i n g o ne t o d e t e r m i n e t h e c o n c e n t r a t

i o n o f e l e m e n t s when i n c o m b i n e d f o r m , b u t t h e d i f f i c u l t i e s

i n t r o d u c e d i n o b t a i n i n g t h e v a l u e s o f w i d e l y v a r y i n g

c o n c e n t r a t i o n s by t h e m e t h o d o f d i l u t i o n s i s l i m i t e d by

t h e i n t e r e l e m e n t e f f e c t s . T h e s e , u l t i m a t e l y , l i m i t t h e

p r e c i s i o n t o t h e g e n e r a l a r e a o f 2 0 - 2 5 ^ .


3.25"o

u oo 3.05"

2 .85" - r 2 .84

<? 2.522.45"

1 - 2.272.25"2.20

d> 2.092.05-

1.85-

1.65 EX.

F ig u r e 6 . Amount o f C a lc ium p r e s e n t i n C o n t r o l and E x p e r im e n ta l Sam ples


AO

.0310id t .0298

.0270'.0259

0230-

.0190-

A .0244

©.0219

.0190-*-.0179

0150^C. EX.

F i g u r e 7 . Amount o f Sodium p r e s e n t i n C o n t r o l a n d E x p e r i m e n t a l S a m p l e s .


/oM

g41

o 490-

370-

330"

286

216

F i g u r e 8 . Amount o f m a g n e s i u m p r e s e n t i n C o n t r o l a n d E x p e r i m e n t a l S a m p l e s


icn- ©2.oixio'fc

1 0 7

1 0

10

-1010

1 0

- 12-

10

notdetectable

C. EX.

F i g u r e 9 . Amount o f C o p p e r p r e s e n t i n E x p e r i m e n t a l S a m p l e s .


43

-r.978

t .935

6 6 -

EX.C.F i g u r e 1 0 . Amount o f P o t a s s i u m p r e s e n t i n C o n t r o l

a n d E x p e r i m e n t a l S a m p l e s .


A P P E N D I X I

CL

M— U.

o >/ O o

/ o ^ >c \ j

U)

u> Cl +->os > t j - oQ Q.

C \JO o^ ID

D e t a i l s o f Arc C i r c u i t A r r a n g e m e n t

44


Reproduced

with perm

ission of the

copyright ow

ner. Further

reproduction prohibited

without

permission.

5 0 " F ig u re 1 1 . Curve o f P l a t e F a c to r v s . W aveleng thf o r H i lg e r S p e c t ro g r a p h

40"

2700 3100 3500 3900 4300 X

APPENDIX II

REFERENCES

1 . Underwood, E . J . , T rac e E le m e n ts i n Human and Anim al N u t r i t i o n , Academic P r e s s I n c . , New Y ork , 1956 , p . 2 .

2 . i b i d .

3 . Saw yer, R a lp h , A E x p e r im e n ta l S p e c t r o s co p y , 2nd e d . , P r e n t i c e - H a l l , New Y ork , 1951 , p . 32 1 .

4 . K o l t h o f f , I . M . , E lv i n g , P h i l l i p J . and S a n d e l l , E rn e s t B . , T r e a t i s e on A n a l y t i c a l C h e m is t r y , P a r t 1 , V o l . 6 , I n t e r s c i e n c e P u b l i s h e r s , New Y ork, 1965 ,p . 34 66 .

5 . S l a v i n , M o r r i s , E m iss io n S p e c t r o c h e m ic a l A n a l y s i s , V o l . 3 6 , W i l e y - I n t e r s c i e n c e , New Y ork , 1971 , p . 207 .

6 . o p . c i t . , p . 3 4 3 4 .

7 . V a l l e e , B e r t L . and P e a t t i e , R u th W., " V o l a t i l i z a t i o n R a te s o f E le m e n ts i n t h e H elium D i r e c t C u r r e n t A r c . ” A n a l y t i c a l C h e m is t r y , V o l . 24 , No. 3 , March 195 2 , p p . 4 3 4 -4 4 4 .

S. Tymchuk, P . , R u s s e l l , D .S . and Berman, S . S . , ’’TheUse o f a C o m b in a t io n o f Atom and I o n L in e s a s I n t e r n a l S t a n d a r d s i n G e n e ra l S p e c t r o c h e m ic a l A na ly s i s . ” A p p l ie d S p e c t r o s c o p y , V o l . 17 , No. 6 , 1963 ,p p . I 63 - 1 6 5 .

9 . C onnor, J a n e and B a s s , S . T . , "Use o f a H ig h -V o l ta g e Arc S o u rc e f o r t h e S p e c t r o c h e m ic a l A n a ly s i s o f P l a n t T i s s u e . ” A p p l ie d S p e c t r o s c o p y , V o l. 1 6 , No.5, 1962 , p . 1 52 .

1 0 . Ng, S .K . , H s ia , R .C .H . and L a i , P . T . , " S p e c t r o g r a - p h ic D e t e r m in a t io n o f C a lc iu m i n L a te x o f N a t u r a l R ubber ( H e v e a b r a s i l i e n s i a ) . ” A p p l ie d S p e c t r o s c o p y , V o l . 24 , No. 6 , 19 70 , p . 53 4 .

1 1 . B e d r o s i a n , A . J . , S k o g e rb o e , R .K . and M o r r i s o n , G .H ., " D i r e c t E m is s io n S p e c t r o g r a p h i c Method f o r T ra c e E le m e n ts i n B i o l o g i c a l M a t e r i a l s . " A n a l y t i c a l C h e m is t r y , V o l . 4 0 , No. 6 , May 1963 , p . £54 .

1 2 . K o l t h o f f , I . M . , S a n d e l l , E . B . , Meehan, E . J . and B r u c k e n s t e i n , S t a n l e y , Q u a n t i t a t i v e C hem ica l

4 6


47

A n a l y s i s , 4 t h e d . , The M a c m i l l a n C o . , T o r o n t o , Ont a r i o , 1 9 6 9 , p . 5 1 9 .

1 3 . H o l d t , G . , "A S t u d y o f t h e I n f l u e n c e o f B u f f e r s on t h e A c c u r a c y a nd S e n s i t i v i t y o f S p e c t r o c h e m i c a l R e s u l t s . " A p p l i e d S p e c t r o s c o p y , V o l . 1 6 , No. 3 , 1 9 6 2 , p p . 9 6 - 9 7 .

1 4 . l o c . c i t . , p . 99 .

1 5 . B r o d e , W a l l a c e R . , C h e m i c a l S p e c t r o s c o p y , 2nd e d . , Bohn UJi ley and S o n s , Neu/ Y or k , 1 9 6 5 , p p . 3 1 2 - 3 1 3 .

1 6 . P i e r c e , l i l .C. and N a c t r i e b , N . H . , " P h o t o m e t r y i n S p e c t r o c h e m i c a l A n a l y s i s . " I n d u s t r i a l a n d E n q i n s e r - i n q C h e m i s t r y , V o l . 1 3 , No. 1 1 , Nov. 1 5 , 1 9 4 1 , p .775 . --------

1 7 . H a r r i s o n , G e o rg e R. , L o r d , R i c h a r d C. and L o o f b o u r o i u , Bohn R . , P r a c t i c a l S p e c t r o s c o p y , Neu B e r s e y , P r e n - t i c e * H a l l , I n c . , 1 9 4 8 , p . 1 0 1 .

1 3 . KODAK M a t e r i a l s Fo r E m i s s i o n S p e c t r o s c o p y , 2nd e d . , P a m p h l e t No. P - 1 0 , R o c h e s t e r , Neu Y o r k , Ea s t m a n Kodak C o . , 1 9 6 3 , p . 1 4 .

1 9 . ( llee s , C . E . K . , Barnes , T . H . , The T h e o r y o f t h e P h o t o g r a p h i c P r o c e s s , 3 r d e d . , Neu Y o r k , The M a c m i l l a n C o . , 1 9 5 6 , p p . 5 2 1 - 5 2 2 .

2 0 . P i e r c e a n d N a c t r i e b , o p . c i t . , p . 7 7 4 .

2 1 . i b i d .

2 2 . M e t h o d s F o r E m i s s i o n S p e c t r o c h e m i c a l A n a l y s i s , A m e r i c a n S o c i e t y F o r T e s t i n g a n d M a t e r i a l s , 4 t h e d . , P h i l i d e l p h i a , P a . , 1 9 6 4 , p . 7 3 , S e c t i o n E116 .

2 3 . C o r d i n g l y , D . C . , L a c e y , L . B . a n d S a n d i f o r d , P . B . , " E x t e n d e d T a b l e s o f S e i d e l F u n c t i o n F o r S p e c t r o - g r a p h e r s . " A p p l i e d S p e c t r o s c o p y , V o l . 8 , 1 9 5 4 , p p . 9 2 - 9 3 .


BIBLIOGRAPHY

BOOKS:

B ro d e , W allace R . , C hem ica l S p e c t r o s c o p y , 2nd e d . , New Y ork: John W iley & S o n s , i n c . , 1 9 6 $ . Pp . x i + 6 7 7 .

H a r r i s o n , George R . , L o rd , R ic h a rd C. and Loofbourow ,John R . , P r a c t i c a l S p e c t r o s c op y , New J e r s e y : P r e n t i c e - H a l l , I n c . , 1 9 4 8 . P p . x i v + 6 6 5 .

K o l t o f f , I .M . and E l v i n g , E r n e s t B . , ( E d s . ) , T r e a t i s e on A n a l y t i c a l C h e m is t ry * V o l . 6 , P a r t 1 , New Y o rk : I n t e r s c i e n c e P u b l i s h e r s , 1 9 6 $ . P p . x x i i i + 3 3 4 7 -4 2 4 6 .

K o l t o f f , I .M . , S a n d e l l , E . B . , MeehoJi, E . J . , B ru c k en - s t e i n , S t a n l e y , Q u a n t i t a t i v e C hem ica l A n a l y s i s . 4 t h e d . , New Y ork : The M acm illan C o . , 1 5 6 5 . Pp. x i i + 1 199 .

L a t im e r , W endell M. and H i ld e b r a n d , J o e l H . , R e fe re n c e Book Of I n o r g a n i c C h e m is t r y , 3 rd e d . , New Y ork: The M a cm illa n C o . , 1 9 5 1 . P p . x i i + 6 2 $ .

M ees, C. K enneth and Ja m es , T .H . , The T heory o f t h e P h o to g r a p h ic P r o c e s s . 3 r d e d . , New Y ork: The M acm illan C o . , 1 9 6 6 . Pp . x i + 591 .

N e b l e t t e , C.B. (E d ) , P h o to g ra p h y : I t s M a t e r i a l s and P ro c e s s e s . 6 t h e d . , New Y ork : Van N o s t r a n d -R e in h o ld Comp a n y , 1 9 6 2 . Pp . v i + 5 06 .

Saw yer, R a lph A ., E x p e r im e n ta l S p e c t r o s c o p y . 2nd e d . ,New Y ork: P r e n t i c e - H a l l , 1 951 . P p . x + 3 5 # .

S l a v i n , M o r r i s , E m is s io n S p e c t r o c h e m ic a l A n a l y s i s . V o l. 3 6 , New Y ork: W i l e y - I n t e r s c i e n c e P u b l i s h e r s , 1 971 . Pp . v i + 25 4 .

Underwood, E . J . , T ra c e E le m e n ts I n Human and Animal N u t r i t i o n . New Y ork : Academic P r e s s I n c . , 1956 . P p . x + 4 3 0 .

W a l l i s , W. A l l e n and R o b e r t s , H a r ry V ., S t a t i s t i c s : A New A pproach . New Y ork: The F re e P r e s s , 195 6 . P p . x x x v i i i + 6 4 6 .

W east, R o b e r t C. ( E d ) , Handbook o f P h y s ic s and C h e m is t r y .

4 S


5 0 t h e d . , C l e v e l a n d : The C h e m i c a l R u b be r C o . , 1 9 7 0 , P p . x x i v + 2 3 5 6 .

____________ , m e t h o d s F o r E m i s s i o n S p e c t r o c h e m i c a lA n a l y s i s , 4 t h e d . , P h i l i d e l p h i a : A m e r i c a n S o c i e t y F o r T e s t i n g and m a t e r i a l s , 1 9 6 4 . Pp . x v i + 8 6 2 0


50

PERIODICALS:

B a r n e s , Ramon ffl., " E m i s s i o n S p e c t r o s c o p y . " ( b i b l i o g r a p h i c r e v i e w ) , A n a l y t i c a l C h e m i s t r y , XLIV, No. 5 ( A p r i l , 1 9 7 2 ) , 1 2 2 R - 1 50 R.

B e d r o s i a n , A . 3 . , S k o g e r b o e , R.K. a nd M o r r i s o n , G . H . , " D i r e c t E m i s s i o n S p e c t r o g r a p h i c Met hod f o r T r a c e E l e m e n t s i n B i o l o g i c a l M a t e r i a l s . " A n a l y t i c a l C h e m i s t r y ,XL, No. 6 (May, 1 9 6 8 ) , 8 5 4 - 8 6 U .

C o n n o r , Dane a nd B a s s , S . T . , " Us e o f a H i g h - V o l t a g e AC Arc S o u r c e f o r t h e S p e c t r o c h e m i c a l A n a l y s i s o f P l a n t T i s s u e . " A p p l i e d S p e c t r o s c o p y . XVI, No. 5 , 1 9 6 2 , 1 5 0 - 1 5 4 .

C o r d i n g l y , D . C . , L a c e y , L . 3 . , S a n d i f o r d , P . O . , " E x t e n d e d T a b l e s o f S e i d e l F u n c t i o n f o r S p e c t r o g r a p h e r s . " A p p l i e d S p e c t r o s c o p y , V I I I , 1 9 5 4 , 9 2 - 9 4 .

H a r r i s o n , G e o r g e R . , " C o m p i l a t i o n s o f S p e c t r o s c o p i c D a t a . " O o u r n a l o f A p p l i e d P h y s i c s , ( b i b l i o q r a p h y ) . X. (November", ' 1 3 5 9 )',' T & O -T e? '.

H o l d t , G . , "A S t u d y o f t h e I n f l u e n c e o f B u f f e r s on t h e A c c u r a c y a n d S e n s i t i v i t y o f S p e c t r o c h e m i c a l R e s u l t s . " A p p l i e d S p e c t r o s c o p y , XVI, No. 3 , l y 6 2 , 9 6 - 1 0 0 .

R l a r g o s h e s , M a r v i n , " E x c i t a t i o n a n d I o n i z a t i o n i n Arc a nd Spa rK S p e c t r o s c o p i c S o u r c e s . " A p p l i e d S p e c t r o s c o p y , XXI, No. 2 , 1 9 6 7 , 9 2 - 9 9 .

M e g g e r s , UJ .F. , K i e s s , C . C . a n d S t i m s o n , F . O . , " P r a c t i c a l S p e c t r o g r a p h i c A n a l y s i s . " B u r e a u o f S t a n d a r d s S c i e n t i f i c P a p e r s , X V I I I , ( A p r i l , 1 9 2 2 ) , 2 3 5 - 2 5 5 .

Ng, S . K . , H s i a , R . C . H . , L a i , F . T . , " S p e c t r o g r a p n i c D e t e r m i n a t i o n o f C a l c i u m i n L a t e x o f N a t u r a l R u b b e r ( H e v e a b r a s i l i e n s i a ) . " A p p l i e d S p e c t r o s c o p y , XXIV, No. 6 , 1 9 7 0 , 5 8 3 - 5 8 7 .

P i e r c e , iiJ.C. a n d N a c h t r i e b , N. H. , " P h o t o m e t r y i n S p e c t r o c h e m i c a l A n a l y s i s . " I n d u s t r i a l a n d E n g i n e e r i n g Chemi s t r y ( A n a l y t i c a l E d i t i o n ) , X I I I , No. 1 1 (November 1 9 4 1 ) , 7 7 4 - 7 8 1 .

Tho mp so n , G e o f f r e y a n d B a n d s t o n , D o n a l d C . , " S a m p l e Cont a m i n a t i o n f r o m G r i n d i n g and S i e v i n g D e t e r m i n e d by E m i s s i o n S p e c t r o s c o p y . " A p p l i e d S p e c t r o s c o p y , XXIV, No. 2 ,


51

1 9 7 0 , 2 1 0 - 2 1 9 .

Tymchuk , P . , R u s s e l l , D . S . a n d B e r m a n , S . S . , "The Use o f a C o m b i n a t i o n o f Atom a n d I on L i n e s a s I n t e r n a l S t a n d a r d s i n G e n e r a l S p e c t r o c h e m i c a l A n a l y s i s . " A p p l i e d S p e c t r o s c o p y , XVI I , No. 6 , 1 9 6 3 , 1 6 3 - 1 6 5 .

V a l l e e , B e r t L. and P e a t t i e , Ru t h Ui. , " V o l a t i l i z a t i o n R a t e s o f E l e m e n t s i n t h e H e l i u m D i r e c t C u r r e n t A r c . " A n a l y t i c a l C h e m i s t r y , XXIV, No. 3 ( f i l a r ch , 1 9 5 2 ) , 4 3 4 - 4 4 4 .

PAMPHLETS:

_____________ , Kodak m a t e r i a l s F o r E m i s s i o n S p e c t r o s c o p y ,2 nd e d . , Kodak P a m p h l e t No. P - 1 0 , R o c h e s t e r : E a s t m a n Kodak C o . , 1 9 5 8 , P p . 1 5 .

_____________ , Kodak P l a t e s a n d F i l m s F o r S c i e n c e and I n d u s t r y , Xodak P a m p h l e t No. P - 9 , R o c h e s t e r : E a s t m a n Kodak C o . , 1 9 6 7 r P p . 3 2 .


a quantitative analysis by emission spectroscopy of the

Documents