Ozonolysis of kerogen in Transvaal stromatolitic limestone

Item Type text; Thesis-Reproduction (electronic)

Authors Zumberge, John Edward, 1948-

Publisher The University of Arizona.

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Link to Item http://hdl.handle.net/10150/554584

OZONOLYSIS O F KEROGEN IN A TRANSVAAL

STRO M A TO LITIC LIM ESTO N E

by

Jo h n E d w ard Z u m b e rg e

A T h e s is S u b m itted to th e F a c u l t y of th e

D E PA R T M E N T O F GEOSCIENCES

In P a r t i a l F u lf il lm e n t of th e R e q u ire m e n ts F o r th e D e g re e of

M A STER O F SC IE N C E

In th e G ra d u a te C o lleg e

TH E UNIVERSITY O F ARIZONA

1 9.7; 3

STA TEM EN T BY AUTHOR

T h is th e s is h as b een su b m itte d in p a r t ia l fu lf illm e n t of r e ­q u ire m e n ts fo r an advanced d e g re e a t The U n iv e rs ity of A r iz o n a and i s d ep o s ite d in th e U n iv e rs ity L ib r a r y to be m ade av a ilab le to b o r ro w e rs u n d e r r u le s of th e L ib ra ry .

B r ie f q u o ta tio n s f ro m th is th e s is a re a llo w ab le w ithout s p e c ia l p e rm is s io n , p ro v id e d th a t a c c u ra te acknow ledgm en t of s o u rc e is m ad e . R e q u e s ts fo r p e rm is s io n fo r ex ten d ed q u o ta tio n f ro m o r re p ro d u c tio n of th is m a n u sc r ip t in w hole o r in p a r t m ay be g ra n te d by th e head of th e m a jo r d e p a r tm e n t o r th e D ean of th e G ra d u a te C o llege w hen in h is ju d g m en t the p ro p o se d u se of th e m a te r ia l is in th e in te r e s t s of s c h o la rs h ip . In a ll o th e r in s ta n c e s , h o w ev er, p e rm is s io n m u s t be o b ta in ed f ro m th e a u th o r .

SIGNED: v

A PPR O V A L BY THESIS D IRECTO R

T h is th e s is h as b een ap p ro v ed on th e da te show n below :

BARTHOLOM EW NAGY P r o f e s s o r of G e o sc ie n c e s

D ate

ACKNOWLEDGMENTS

I am v e ry g ra te fu l to D r . and M rs . B a rth o lo m ew N agy fo r

e n c o u ra g in g and d ire c t in g th is r e s e a r c h . I w ish to th an k D r . K laus

B iem an n of th e M a ss a c h u se tts In s ti tu te of T echno logy fo r th e h igh

r e s o lu tio n m a s s s p e c t ro m e tr ic a n a ly s is . My th a n k s a lso g o es to

E r i c B a n d u rsk i who p ro o fre a d th e m a n u s c r ip t and to D e b o rah D udley

who d id th e a r t w o rk .

T h is r e s e a r c h w as co n d u c ted u s in g funds p ro v id e d by NASA

G ra n t NGR 0 3 -0 0 2 -1 7 1 .

TABLE OF CONTENTS

P a g e

L I S T O F IL L U S T R A T IO N S o o o o o o o o o o o ® o o © o s > o o ® o v

L I S T OF* T A B L E S ©o ©®®©©©®®© © ©@©©@o ©@e o @©®@ vx

KS' I A 1 ̂o o o e o o e e o o o o o o o o o © ® ® © © ® ® ® © ® ® ® ®® "VXX

IN T K O D U C T IO N 0 0 0 0 9 ® 0 0 d 0 0 0 0 0 0 © 0 9 0 0 .0 0 0 9 0 0 © © 1

E X P E R I M E N T A L ® © © © © © © © o © o © © o © © © ® © © ® © © © © © © 5

R E S U L T S o o o o e o e o o o o o o o o o e e e o o o o e o o o oo S o o 11

P y r o l y s i s © © © © © © o o © ® ® © © ® © © © ® © © ® © © © © © ® 11E l e m e n t a l A n a l y s i s © © © © © © © © © © © © © © © © © © © © 13X - r a y D i f f r a c t i o n A n a l y s i s © © © © © © © © © © © © ® © © 13■*■̂ 0 C a r b o n a t e V a lu e . . . . . . . . . . . . . . . . . . . . 16

o n o l y s i s s © ® © © © © © © © © © ® © © © © ® ® © © © © ® ® ® 16

D IS C U S S IO N 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 8 0 0 0 9 0 9 9 © 2 2 "

R JllH^EItliilSf C E S 0 0 0 0 0 0 0 0 0 0 0 0 0 0 © 0 0 0 0 ® 9 0 - © © © ® ® 9 © 30

LIST OF ILLUSTRATIONS

F ig u re P a g e

1 . V a rio u s A ro m a tic F ra g m e n t Io n s f ro m th e T ra n s v a a lS tro m a to lite I^erogeu @ 12

2. C o m p a riso n of a M ass S p e c tru m f ro m th e M ethy l E s t e rF r a c t io n w ith a D im eth y l P h th a la te S ta n d a rd M ass Spectrum . @ » o.® ® * « « ® ® ® ® ® ® ® » ® ® ® • ® ® ® ® ®.». * ® ® 17

' 3. G as C h ro m a to g ra m of th e N e u tra l F r a c t io n f ro m th eT ra n s v a a l S tro m a to lite , (a) A 100 ' X . 02" i . d . OS 138 C olum n w as u se d . T he C olum n w as h e ld I s o th e r - m a lly at 70° C fo r 6 M in. th e n P ro g ra m m e d a t 50 /m in . a t an In it ia l A tten u a tio n of 20. (b) G as C h ro m a to g ra mof th e N e u tra l F r a c t io n f ro m th e B a s a l t B lank.* C ondi­tio n s W ere Id e n tic a l to T h o se in (a) . . . . . . . . . . . . 19

4. M ass S p e c tru m of P e a k s 3 and 4 f ro m th e N e u tr a lF r a c t io n C h ro m a to g ra m . . . . . . . . . . . . . . . . . . . 20

5. S tru c tu r e s of (a) 2 - P ro p y l- 3 - M ethy l T e tra h y d ro fu ra nand(b) 2 - P ro p y l T e tra h y d ro p y ra n . . . . . . . . . . . . . 21

6. M ech an ism of R e a c tio n b e tw een O zone and U n s a tu ra te dH y d ro c a rb o n s . . . o . . . . . . . . . . 22

7. O x id atio n of K eto n es w ith A lk a lin e H ydrogen P e ro x id e . 23 .

8. M eth y la tio n of C arb o x y lic A cid s u s in g D iazo m eth an e . . 23

9. P ro d u c tio n of D iazo m eth an e f ro m E X R -1 0 1 . . . . . . . . . 23

10. P ro d u c tio n of P h th a lic A cid f ro m O zone A ttack of aP o ly m e r -M a tr ix . . . . . . . . . . . . . . . . . . . . . . . . . 24-

11. R eso n an ce S tab iliz a tio n of m /e 85 Ion . . . . . . . . . . . . 26

v

LIST OF TABLES

T ab le . P a g e

I. A c o m p a r iso n of a s ta n d a rd SO? m a s s s p e c tru m w ith th e m a s s s p e c tru m of a p y ro ly s is p ro d u c t f ro m th e T ra n s v a a l s tro m a to l i te . . . . . . . . . . . . . . . . . . . . . 12

II. M /e v a lu e s w ith c o r re sp o n d in g id e n tif ic a tio n f ro m th e p y ro ly s is of th e co ld r in g f ro m th e T ra n s v a a l s tr o m a to l i te . . . e . . . . . . . . . . . . . . . . . . . . . . . . 14

III. C om m on s ily la te d io n s ............. 25

ABSTRACT

T he in so lu b le o rg a n ic m a t te r (k ero g en ) in a c a rb o n a te ro c k

f ro m South A fr ic a (T ra n s v a a l s tro m a to li te ) w as an a ly zed fo r p o s s ib le

b io c h e m ic a l m a r k e r s w hich w ould in d ic a te th e p r e s e n c e of b io lo g ic a l

p r o c e s s e s . T h is ~ 2. 2 b illio n y e a r old s e d im e n ta ry ro c k is know n to

co n ta in m ic ro f o s s i l s w hich a re re m n a n ts of b lu e -g re e n a lg ae (P e t r a -

p h e ra v iv e s c e n tic u la ). T he s tro m a to l i t ic s t r u c tu r e of th e ro c k a lso

im p lie s a s s o c ia tio n w ith a lg a l o r b a c te r ia l c o lo n ie s .

The k e ro g e n w as b ro k e n down u s in g tw o m e th o d s : o zo n o ly s is

and p y ro ly s is . S u lfu r com pounds w e re id e n tif ie d f ro m m a s s s p e c t r a

of .the p y ro ly s is p ro d u c ts . B oth o z o n o ly s is and p y ro ly s is c o n firm e d a

p a r t ia l a ro m a tic s t r u c tu r e fo r th e k e ro g e n . In one of th e o z o n o ly s is

f ra c t io n s , s a tu r a te d a lk y l s u b s titu te d c y c lic e th e r d e r iv a t iv e s w e re

id e n tif ie d u s in g a co m b in a tio n of g as c h ro m a to g ra p h y -m a s s

s p e c tro m e try and c o n firm ed by h igh re s o lu t io n m a s s s p e c tro m e try .

T h ese com pounds com m only o c c u r in r e c e n t hum ic a c id s and they

cou ld be re m n a n ts of c a rb o h y d ra te s , in w h ich c a se i t w ould c o n firm

p a le o n to lo g ic a l ev id en ce of p r im it iv e l ife in th e e a r ly P re c a m b r ia n .

CHAPTER 1

INTRODUCTION

T he T ra n s v a a l s tro m a to l i te i s a c a rb o n a te ro c k f ro m South

A fric a w hich is a p p ro x im a te ly 2. 2 b il l io n y e a r s o ld ( P r e to r iu s , 1971,

1973). S tro m a to li te s a r e s e d im e n ta ry ro c k s t r u c tu r e s w h ich p r e s u m ­

ably fo rm th ro u g h a s so c ia tio n w ith a lg a l m a ts o r p h o to sy n th e tic

b a c te r ia (W alte r, B au ld , and B ro c k , 1972). The T ra n s v a a l s tro m a to ­

l i te s a r e a lso know n to co n ta in m ic ro f o s s i l s , w h ich a p p e a r to be

fo s s i l iz e d b io g e n ic c e l ls of b lu e -g re e n a lg ae ( P e tr a p h e r a v iv e s c e n ti-

cu la) (Nagy, L . A ., 1973). H ow ever, c h e m ic a l ev id en ce of v e ry old

b io lo g ic a l a c tiv ity m u s t be found in o r d e r to c o n f irm s t r u c tu r a l and

p a le o n to lo g ic a l ev id en ce of th e e a r ly e m e rg e n c e of l i fe on th e e a r th .

V ery l i t t l e i s known about k e ro g e n , w hich i s of s e d im e n ta ry

o r ig in , a lthough i t i s th e l a r g e s t accu m u la tio n of o rg a n ic m a te r ia l on .

e a r th . The p r e c u r s o r s of k e ro g e n a p p e a r to have b e e n d ep o s ite d a t

th e s a m e tim e as th e s e d im e n ts . K ero g en , fo r th e m o s t p a r t , i s an

o rg a n ic so lid th a t i s in so lu b le in the u s u a l o rg a n ic s o lv e n ts . In th in

s e c tio n s k e ro g e n a p p e a rs to b e f in e ly d is s e m in a te d in th e m in e ra l

m a tr ix and m ay c o a t in d iv id u a l p a r t ic le s su c h as c la y s . M ost k e ro -

g ens c o n s is t of ra n d o m p o ly m e r- l ik e o rg a n ic m a te r ia l in c o rp o ra tin g

v a r io u s c la s s e s of o rg a n ic com pounds and can b e te n ta tiv e ly c la s s i f ie d

in to d iffe re n t ty p e s , su c h as " c o a ly " m a te r ia l ( a ro m a tic m o ie tie s ) and

"n o n -c o a ly " m a te r ia l (a lip h a tic m o ie tie s and c y c lo a lk a n e s ) (F o re m a n ,

1963),

S o lven t e x t r a c t ab le com pounds f ro m old s e d im e n ts have b e e nA

s tu d ie d e x te n s iv e ly (B u rlin g am e e t a l , , 196.5; S m ith , Schopf, and

K ap lan , 1970). T h e se so lu b le com pounds, h o w ev er, m ay no t be

in d ig en o u s to th e s e d im e n ta ry ro c k . O e h le r , Schopf, and K venvolden

13(1972) m e a s u re d th e C v a lu e s of th e so lu b le and in so lu b le o rg a n ic

f ra c t io n s ( lib e ra te d by ac id d is so lu tio n f ro m th e ro c k ) f ro m th e

T h e e sp ru it fo rm a tio n in th e O n v erw ach t g ro u p ( > 3 , 4 b ill io n y e a r s old)

13and found th a t th e so lu b le o rg a n ic s w e re m u ch l ig h te r in C th an th e

r e s id u e . T h is im p lie s tw o d if fe re n t s o u rc e s fo r th e so lu b le and

in so lu b le o rg a n ic s . E v e n th e m o s t d en se s e d im e n ta ry ro c k s have

so m e p e rm e a b il i ty . In fa c t , i t h a s b e e n r e p o r te d th a t ap p ro x im a te ly

one cub ic m e te r of i n t e r s t i t i a l w a te r cou ld flow th ro u g h one cubic

m e te r of d en se O n v erw ach t c h e r t in 3 x 10^ y e a r s (N agy, B . , 1970).

I t i s p o s s ib le , th e r e fo r e , th a t aqueous so lu tio n s c o n ta in in g sm a ll

am o u n ts of so lu b le o rg a n ic m a te r ia l cou ld have in tro d u c e d th e se co m ­

pounds m u ch l a t e r in geo lo g ic t im e and co n seq u en tly th e s tudy of

k e ro g e n is m o re d e s ir a b le .

The p u rp o se of th is s tudy i s to : 1) d e te rm in e th e n a tu re of

th e k e ro g e n a p p a re n tly a s so c ia te d w ith p a le o n to lo g ic a l and s t r u c tu r a l

ev id en ce of b io lo g ic a l a c tiv ity , and 2} a tte m p t to id e n tify any b io c h e m i­

c a l f o s s i ls p r e s e n t in th e T ra n s v a a l s tr o m a to l i te k e ro g e n . C e r ta in

c h e m ic a ls , su c h as i s o p r eno id h y d ro c a rb o n s , s te r a n e s , p o rp h y rin s ,

am ino a c id s , and fa tty a c id s , can b e c o n s id e re d b io c h e m ic a l f o s s i ls

s in c e th ey p re su m a b ly a r i s e f ro m c h e m ic a ls in tim a te ly a s s o c ia te d w ith

life p r o c e s s e s (E g lin t on and C alv in , 1967). A few of th e above com ­

p ounds, h o w ev er, can b e sy n th e s iz e d ab io lo g ic a lly , u ti l iz in g th e

M il le r -U re y o r F i s c h e r - T r ops ch p r o c e s s e s and th e r e fo r e m ig h t fo rm

f ro m a n o n -b io lo g ic a l p r o c e s s (M ille r and U re y , 1959; S tu d ie r ,

H ay a tsu , and A n d e rs , 1972).

T he m e th o d s em p lo y ed in an a ly z in g th is k e ro g e n p r im a r i ly

e n ta ile d th e u se of 1) ozone and 2) h e a t . O zo n o ly s is can b e u se d to

b re a k down k e ro g e n s in c e ozone s e le c t iv e ly c le a v e s th e co m p lex p o ly ­

m e r ic s t r u c tu r e a t c a rb o n -c a rb o n double bonds (B itz and N agy, 1966).

The o x id a tio n p ro d u c ts r e s u l t in g f ro m o z o n o ly s is can b e an a ly zed , and

i t i s e x p ec ted th a t th e o r ig in a l s t r u c tu r e can be p a r t ia l ly ded u ced .

C a rb o x y lic a c id s a re fo rm e d as a r e s u l t of h y d ro g en p e ro x id e ox id a­

tio n of th e a ld eh y d es and k e to n e s (p r im a ry o zo n o ly s is p ro d u c ts ) . S ince

m o s t k e to n e s , a ld eh y d es , and c a rb o x y lic a c id s a r e to o p o la r to p a s s

th ro u g h c a p i l la ry g as c h ro m a to g ra p h ic co lu m n s, v o la ti le d e r iv a tiv e s

of th e s e com pounds m u s t b e m ad e in o r d e r to f a c i l i ta te cou p led gas

c h ro m a to g ra p h ic -m a s s s p e c t ro m e tr ic a n a ly s is . D iazo m eth an e h a s

b e e n u se d ex te n s iv e ly to c o n v e rt c a rb o x y lic ac id s to m e th y l e s te r s

w hich a r e s u ita b le fo r g as c h ro m a to g ra p h ic s e p a ra tio n , bu t th e r a th e r

p o o r v o la ti l i ty of th e r e s u l t in g h igh m o le c u la r w eigh t m e th y l e s t e r s

m a k e s i t d iff ic u lt to s e p a ra te and id en tify a ll of th e se com pounds.

A lte rn a tiv e ly , t r im e th y ls i ly l (TMS) d e r iv a t iv e s of th e ac id s m ay be

p re p a re d (K aufm an, F r ie d m a n , and W en d er, 1967).

P y ro ly s is i s o ften u se d to an a ly ze p o ly m e rs . In th is m ethod

th e s a m p le i s h ea te d in vacuo o r in e r t a tm o sp h e re and th e b reak d o w n

p ro d u c ts a r e d e te rm in e d , u su a lly by m a s s s p e c tro m e try . A lthough

m u ch u s e fu l in fo rm a tio n can be o b ta in ed f ro m p y ro ly s is , i t i s a

r e la t iv e ly h a r s h te c h n iq u e fo r an a ly z in g k e ro g e n . T he r a th e r u n p re ­

d ic ta b le m a n n e r in w hich p y ro ly s is b r e a k s down k e ro g e n m ak es i t

d iff ic u lt to r e c o n s t r u c t th e o r ig in a l s t r u c tu r e . '

T he v e ry fa c t th a t k e ro g e n i s in so lu b le and a ra n d o m p o ly m e r

m a k e s i t s c h a r a c te r iz a t io n so m ew h at d iff ic u lt. H o w ev er, o z o n o ly s is

a p p e a rs to b e a p ro m is in g tech n iq u e f o r e lu c id a tin g th e n a tu re of

k e ro g e n . F u r th e r c h a ra c te r iz a t io n of a l l ty p e s of k e ro g e n by im p ro v e d

o z o n o ly s is and p y ro ly s is te c h n iq u e s m ay no t only p ro v id e c lu es to th e

o r ig in of l i fe on e a r th b u t a lso he lp d e te rm in e th e f e a s ib i l i ty of u s in g

k e ro g e n as fo s s i l fu e ls f ro m w id e s p re a d o il sh a le d e p o s its ( e .g . .

G re e n R iv e r Shale) (D uncan and Sw anson, 1965).

CHAPTER 2

E X PE R IM E N T A L

L a b o ra to ry co n tam in a tio n s m u s t b e avo ided w hen an a ly z in g

s m a ll am o u n ts of o rg a n ic m a te r ia l . A ll g la s s w a re and T eflo n u se d in

th e s e e x p e r im e n ts w as ac id c le a n e d w ith hot ^ S O ^ /H N O g (85:15v/v)o

A ll so lv e n ts u se d w e re r e d is t i l le d f ro m s p e c t r a l o r p e s tic id e g ra d e

r e a g e n ts . The w a te r u se d w as t r ip le d is t i l le d . Two p ro c e d u re b lan k s

ow e re ru n u s in g p o w d ered b a s a l t f i r e d a t 900 C fo r 2 h o u rs in a i r to

in s u re th e a b se n c e of o rg a n ic co n ta m in a tio n in th e s y s te m .

T he ro c k s a m p le s (b a s a lt and T ra n s v a a l s tr o m a to l i te ) w e re

S oxhlet e x tr a c te d w ith a 6:4 (v /v ) b e n z e n e -m e th a n o l m ix tu re to re m o v e

any so lu b le o rg a n ic m a te r ia l and th e n w ash ed th r e e t im e s w ith MeOH

to re m o v e e x c e s s b en zen e and fo u r t im e s w ith H 00 to re m o v e e x c e s s

M eOH. The o u te r s u r fa c e of th e T ra n s v a a l s tr o m a to l i te ro c k s a m p le

w as d r i l le d off and th e r e s t of th e ro c k w as p u lv e r iz e d . Then 95. 3 g

of th e p o w d ered ro c k w e re Soxhlet e x tr a c te d w ith abou t 485 m l of th e

6;4 b e n z e n e -m e th a n o l m ix tu re . A fte r th e e x tra c te d ro c k w as w ash ed

w ith m e th an o l and w a te r , i t w as d ig e s te d in 20% d is t i l le d HC1 to re m o v e

c a rb o n a te s w hich m ig h t s u r ro u n d k e ro g e n and th u s p re v e n t ozone

a tta c k . The r e s id u e w as th e n f i l te r e d and w ash ed w ith d ilu te HC1 arid

5

HgO. Of th e o r ig in a l 9 5 .3 g th e d r ie d r e s id u e w eighed only 6. 3 g.

T h is r e s id u e w as again Soxhlet e x tr a c te d w ith 200 m l of th e b e n z e n e -

m e th an o l m ix tu re . A fte r w ash in g again w ith m e th an o l and H^O, s ix

g ra m s w e re ozo n ized as d e s c r ib e d b e low .

T he o z o n o ly s is a p p a ra tu s c o n s is te d of a W elsh ach T -23 O zona­

to r (T he W elsh ach C o rp o ra tio n , W e s tm o re la n d and S tokeley S tre e ts ,

P h ila d e lp h ia , P a . ) w hich p ro d u c e s a 3% ozone (O^) c o n c e n tra tio n in

Og v ia a s p a rk d is c h a rg e . O xygen f ro m a p r e s s u r iz e d ta n k flow ed

th ro u g h d ry in g tu b e s b e fo re e n te r in g th e o z o n a to r . T he ozone p r o ­

duced w as b u b b led th ro u g h th e s a m p le so lu tio n by m e a n s of a f r i t te d

g la s s tu b e . T he e x c e s s ozone w as th e n b u bb led th ro u g h tw o 5% KI

so lu tio n s of 250 m l eac h to q u a n tita te th e u p tak e of o zo n e . F in a lly , a

w et t e s t flow m e te r m o n ite re d th e v o lu m e of g as flow th ro u g h th e

s y s te m .

The so lv e n t e x tr a c te d ro c k s a m p le s w e re added to 100 m l of

3% KOH so lu tio n in th e r e a c t io n v e s s e l . The s lu r r y w as th e n s t i r r e d

by m e a n s of a m ag n e tic s t i r r e r w h ile th e ozone b u b b led th ro u g h th e

KOH so lu tio n fo r fo u r h o u rs . N ex t, 50 m l of 30% H^Og w as added,

and the m ix tu re w as re f lu x e d fo r tw o h o u rs and a llow ed to s tan d o v e r ­

n ig h t. T he s lu r r y w as f i l te r e d and w ash ed in a m e d iu m p o ro s ity

f r i t te d g la s s f i l t e r w ith tw o 5 m l p o r tio n s of 3% KOH and tw o 5 m l

w ash in g s of H^O. E v a p o ra tio n of th e KOH so lu tio n u n d e r v acu u m to

40 m l w as done in o rd e r to e ffec t a m o re co m p le te e th e r e x tra c tio n of

th e unknow n n e u tr a l com pounds. T he c o n c e n tra te d KOH so lu tio n w as

e x tra c te d th re e t im e s in a s e p a ra to ry fu n n e l w ith eq u a l am o u n ts o f

d ie th y l e th e r to re m o v e th e n e u tr a l com pounds (d e s ig n a te d N EU TR A L

FR A C TIO N ). The KOH so lu tio n w as th e n v acu u m e v a p o ra te d a lm o s t

to d ry n e s s . N aH SO ^’ H^O w as u se d to ac id ify th e o r ig in a l 100 m l of

KOH so lu tio n ( a lm o s t d ry ). F o r ty m l of s a tu ra te d Ba(OH)g so lu tio n

w as th en u se d to c o lle c t th e C 0 0 gas r e le a s e d by th e a c id if ic a tio nCl

p r o c e s s w hich w as c a r r ie d out u n d e r an a rg o n a tm o sp h e re .

T he ac id ic so lu tio n w as e v a p o ra te d to d ry n e s s and th e d is ­

t i l l a te c o lle c te d in a f la s k co n ta in in g 2. 0 m l of 2. 455 N NaO H . T h is

f ra c t io n co n ta in ed th e unknow n v o la ti le , w a te r - s o lu b le a c id s . T i t r a ­

tio n w ith 0. 305 N HC1 to n o rm a liz e th e b a s ic so lu tio n co n ta in in g th e

v o la ti le ac id f ra c t io n w as c o m p le te d . T he so lu tio n w as le f t in b a s ic

cond ition in o r d e r to k eep th e v o la ti le a c id s as N a s a l t s . The v o la t i le

ac id f r a c t io n ( s a l ts ) w as e v a p o ra te d to co m p le te d ry n e s s u s in g v acu u m

d is t i l la t io n and a v acu u m oven (8 0 -1 0 0 ° C). The s a l t s w e re then

an a ly zed on a P e r k in - E lm e r 137 In f r a re d S p e c tro m e te r by m ean s of

K B r p e l le ts .

T he d ry r e s id u e of th e o r ig in a l ac id if ied so lu tio n w as le f t in

a ce to n e o v e rn ig h t to e x t r a c t th e n o n -w a te r- s o lu b le , n o n -v o la tile a c id s .

T he r e s id u e w as e x tra c te d two m o re t im e s w ith f r e s h ace to n e . The

ace to n e w as e v a p o ra te d to d ry n e s s u n d e r a s t r e a m of e le c tro n ic g ra d e

n itro g e n , and 50 m l of e th e r w as added to th e r e s id u e . S o lv e n t-c le a n e d

MgSO^ (an h y d ro u s) w as added to re m o v e any w a te r . T he e th e r s o lu ­

t io n w as th e n f i l te r e d and c o n c e n tra te d to re m o v e th e M gSO^.

D iazo m e th an e (CH^N^) in e th e r w as added to th e c o n c e n tra te d e th e r

so lu tio n to sy n th e s iz e th e m e th y l e s t e r s of th e n o n -v o la ti le a c id s . T he

d ia zo m e th a n e w as m ade f ro m a m ix tu re of 15 m l 40% NaOH, 2 . 5 m l

a b so lu te e th an o l, 50 m l of e th e r , and 1 .5 g E X R -1 0 1 (N, N '-d in i t r o s o -

N, N ^ -d im eth y l te re p h th a la m id e ) . (E X R -101 w as o b ta in ed f ro m E . I.

Du P o n t De N e m o u rs & C o . , In c .) . T he d ia z o m e th an e w as d is t i l le d

o v e r w ith th e e th e r w hen th e f la s k co n ta in in g th e above m ix tu re w as

im m e rs e d in a w a rm w a te r b a th (4 0 -5 0 ° C). C au tion m u s t be e x e r ­

c is e d th ro u g h o u t th is p ro c e d u re ; no g ro u n d g la s s f it t in g s o r ch ipped

g la s s shou ld be u se d s in c e an ex p lo sio n m ig h t r e s u l t . T he yellow

d ia z o m e th a n e - e th e r so lu tio n w as p ip e tte d in to th e c o n c e n tra te d e th e r

so lu tio n co n ta in in g th e n o n -v o la tile f r a c t io n . T he y e llo w c o lo r

d is a p p e a re d im m e d ia te ly w hen th e r e w e re any a c id s p r e s e n t . T he

d ia zo m e th a n e w as added u n til th e y e llo w c o lo r p e r s i s te d . The r e a c t io n

f la s k w as w a rm e d s lig h tly to c o m p le te th e m e th y la tio n and d r iv e off

e x c e s s d ia z o m e th an e u n til th e so lu tio n w as c le a r ag a in (d e s ig n a te d

M ETH Y L E S T E R 'F R A C T IO N ).

The T ra n s v a a l sa m p le w as r e -o z o n iz e d in a 100 m l of 3% KOH

fo r fo u r h o u rs and 50 m l of w as th en added and re f lu x e d . T he2 z

re s u l t in g ro c k s lu r r y w as f i l te r e d and w ash ed w ith KOH and H „ 0 .2

N allS O ^’ Hg O w as added to th e f i l t r a t e u n til ac id co n d itio n s p e r s i s te d .

and th e f i l t r a te w as c o n c e n tra te d to 150 m l u n d e r a s t r e a m of n itro g e n .

The f i l t r a t e w as th en e x tra c te d th r e e t im e s w ith e th e r to re m o v e c a r -

b o x y lic a c id s . MgSO^ w as added to th e e th e r e x t r a c t . T h is d if fe r s

f ro m th e p re v io u s o z o n o ly s is p ro c e d u re b e c a u s e i t u s e s a l iq u id - l iq u id

e x tra c tio n in s te a d of a l iq u id -s o l id e x tra c t io n . T w en ty -fiv e m l of th e

e th e r e x t r a c t (150 m l to ta l) w as p a s s e d th ro u g h a m il l ip o re f i l t e r to

re m o v e c o llo id a l c la y p a r t ic le s and th en e v a p o ra te d to d ry n e s s . T he

s ily la tio n d e r iv a tiv e s w e re m ad e by add ing 50 yul of N , O -b is ( tr im e th y l-

s i ly l) -a c e ta m id e (BSA) and 50 /jl of t r im e th y lc h lo ro s i la n e (TM CS).

(BSA and TMCS w e re o b ta in ed f ro m P ie r c e C h em ica l C om pany,

R o ck fo rd , I l l in o is .) A fte r th e so lu tio n w as c o m p le te , th e m ix tu re w as

e v a p o ra te d to one h a lf i t s o r ig in a l v o lu m e (d e s ig n a ted SILYLATION

FRA CTIO N ) and in je c te d in to th e g as c h ro m a to g ra p h (GC).

Id e n tif ic a tio n s of th e unknow n com pounds in th e th r e e d if fe re n t

f ra c t io n s (1. N e u tra l F ra c t io n ; 2. M ethy l E s te r F ra c t io n ; 3. S ily la ­

tio n F ra c t io n ) w e re a c co m p lish e d b y in je c tin g p o r tio n s in to a P e rk in

E lm e r M odel 226 g a s c h ro m a to g ra p h coup led to a H ita c h i-P e rk in

E lm e r R M U -6E m a s s s p e c t ro m e te r by m e a n s of a h e a te d t r a n s f e r l in e

and a W a tso n -B ie m a n n m o le c u la r s e p a r a to r . M ost of th e efflu en t

f ro m th e GC co lum n w as s p li t to th e m a s s s p e c t ro m e te r w hile th e

re m a in in g p o r tio n w ent to a h y d ro g en f la m e d e te c to r w h ich r e c o rd e d

th e gas c h ro m a to g ra m s . R ap id m a s s s c a n s w e re m ad e of th e co m ­

pounds s e p a ra te d by th e GC.

10

T he re m a in in g 0 .3 g of th e a c id -d ig e s te d and so lv e n t-

e x tra c te d T ra n s v a a l s tro m a to l i te ro c k sa m p le w as p y ro ly z e d u n d e r

h igh v acu u m at 250° C and 500° C . T he g a s e s g iven off w e re con­

d en sed in a U -tu b e im m e rs e d in liq u id n itro g e n and th e n in tro d u c e d

d ire c t ly in to th e g as in le t s o u rc e of th e m a s s s p e c t ro m e te r . A fte r

th is a n a ly s is a yellow co ld r in g w as o b s e rv e d in th e U -tu b e . T he co ld

r in g w as d is so lv e d in e th e r , e v a p o ra te d , and an a ly zed in th e so lid in le t

o f th e m a s s s p e c t ro m e te r a t te m p e r a tu r e s up to 300° C.

CHAPTER 3

RESU LTS

P y ro ly s is

V a rio u s k in d s of s u lfu r com pounds c o n s titu te m an y of th e

co m p o n en ts id e n tif ie d f ro m m a s s s p e c t r a d u rin g th e p y ro ly s is of th e

T ra n s v a a l s tro m a to l i t ic l im e s to n e . M ass s p e c t r a ta k e n of p y ro ly s is

p ro d u c ts r e le a s e d at 250° C w e re e s s e n t ia l ly id e n tic a l to p ro d u c ts

or e le a s e d at 500 C. H igh re s o lu t io n m a s s s p e c tro m e try re s o lv e d tw o

p eak s at m /e 32, c o n firm in g th e p re s e n c e of su lfu r (m o le c u la r oxygen

b e in g th e o th e r p eak a t m /e 32). S u lfu r d iox ide w as id e n tif ie d as one

of th e p y ro ly s is g a s e s (se e T ab le I). C O g (m /e 44), C g H g (m /e 30),

and C S g fm /e 76) w e re a lso o b se rv e d as p y ro ly s is p ro d u c ts . C arb o n

d isu lf id e (m /e 76) w as c o n firm e d f ro m th e p a re n t (p) + 2 p eak a t m /e

78 w hich w as a p p ro x im a te ly 9% of m /e 76. T h is i s due to th e s ta b le

s u lfu r 34 iso to p e w h ich i s about 4 .4% as abundant a s th e m o re com m on

su lfu r 32 iso to p e . S ince th e r e a r e tw o s u lfu r a to m s in one m o lec u le of

c a rb o n d isu lf id e , th e p + 2 p eak h as tw ice th e in te n s i ty o f th e iso to p e

p eak f ro m a m o le c u le co n ta in in g only one su lfu r a to m .

S m all p e ak s o b s e rv e d at m /e 77, 91, and 105 d e m o n s tra te th e

p re s e n c e of a ro m a tic com pounds in th e p y ro ly s is p ro d u c ts (F ig u re 1 ) .

11

12

TA BLE I. A c o m p a r iso n of a s ta n d a rd SO^ m a s s s p e c tru m w ith the m a s s s p e c tru m of a p y ro ly s is p ro d u c t f ro m th e T ra n s v a a l s tro m a to l i te .

m /e P y ro ly s is p ro d u c t r e l . in t.

s o 2S tan d a rd M. S.

r e l . in t.

64 100% 100%

48 45 49

66 5 5

50 2 2

m /e 91 ( tro p y liu m ion) m / e 105

F ig u re 1. V a rio u s A ro m a tic F ra g m e n t Ions f ro m th e T ra n s v a a l S tro m a to lite K ero g en .

13

T he a n a ly s is of th e y e llo w ish m a te r ia l (co ld r in g ) con d en sed

in th e U -tu b e of th e p y ro ly s is a p p a ra tu s y ie ld e d th e m /e v a lu e s show n

in T ab le II. T he r e la t iv e p eak in te n s i t ie s fo r each f ra g m e n t io n along

w ith a te n ta tiv e id e n tif ic a tio n fo r eac h p eak i s a lso g iv en . S g fm /e 64)

w as th e l a r g e s t com ponen t of th is p y ro ly s is . A lthough 3 0 ^ a lso h a s a

m a s s of 64, i t a p p e a rs th a t su lfu r d iox ide d id no t c o n tr ib u te s ig n if i­

c an tly to th e m /e 64 p eak s in c e th e r e w as no a p p re c ia b le m /e 48 p eak

(a m a jo r p eak in th e m a s s s p e c tru m of 3 0 ^ ) . S g (m /e 96), S ^ (m /e

128), Sc ( m /e 160), S „ (m /e 192), S -C m /e 224), and S0( m /e 256) w e re d o ( o

th e o th e r e le m e n ta l su lfu r p eak s o b s e rv e d . T he m /e 258 io n i s due to

th e su lfu r 34 iso to p e and i s about 33% of th e m /e 256 io n (w hich i s con ­

s is te n t w ith th e e x is tin g e ig h t su lfu r a to m s).

E le m e n ta l A n a ly s is

The T ra n s v a a l s tro m a to l i te p o w d ered ro c k w as su b je c te d to

HC1 and HE to re m o v e c a rb o n a te s and s i l ic a te s . T he r e s u l t in g

m a te r ia l w as se n t to S chw arzkopf M ic ro a n a ly tic a l L a b o ra to ry (W ood-

s id e , N . Y. ) fo r e le m e n ta l a n a ly s is of o rg a n ic c a rb o n , hyd ro g en ,

s u lfu r , n itro g e n , and p h o sp h o ru s . T he sa m p le co n ta in ed 6.93% C,

1.10% H, 1.18% 3, 0% N, and t r a c e am o u n ts of P .

X - ra y D iffra c tio n A n a ly s is

An x - r a y d iff ra c tio n p a t te rn w as o b ta in ed f ro m th e HC1 and H F

t r e a te d T ra n s v a a l s tro m a to l i te ( c o u r te s y of P ro f . J . A nthony,

14

TA B LE II. M / e v a lu e s w ith c o r re sp o n d in g id e n tif ic a tio n f ro m th ep y ro ly s is of th e co ld r in g f ro m th e T ra n s v a a l s t r o m a to l i te .

m /e r e l . in t. (%) p o s s ib le id e n tity

15 8 CH3

16 5 c h 4, o

29 25 C2H5, c h o

30 5 C2H6’ CH2 °

31 37 CH30

34 13 H2S

41 17 C3H5

43 6 C3H 7

44 9 C ^ , C 3H 8

55 7 C4H7

56 10 C4H8

57 18 C4H9

66 832s - 34s

71 14 C5H11

85 8C6H1 3 -C 5H 90

96 15 S3

128 36S4

160 27S5

192 17 , S6

15

TA B LE II, C on tinued .

m /e r e l . in t. (%) p o ss ib le id e n tity

224 5 S7

256 55 s s

258 18 34 32s - s 7

16

U n iv e rs ity of A riz o n a ). A b ro a d p eak a t 29 = 2 5 .4 ° (3. 3759A) w as

o b se rv e d w hich m ig h t be due to a g ra p h i te - l ik e o r c o a l- l ik e m a te r ia l

(S tev en s, 1966).

"^C C a rb o n a te V alue

i s ' " ----------------------------------------------------------------------------------------------T he 8 C r a t io ( re la t iv e to P .D „ B 0) of th e T ra n s v a a l s tr o m a to - •

l i t e c a rb o n a te i s - 0 . 8%0 w h ich i s in th e n a r ro w m a r in e l im e s to n e

ra n g e a c c o rd in g to C ra ig (1957).

O z o n o ly s is

T he M ethy l E s t e r F r a c t io n c h ro m a to g ra m of th e T ra n s v a a l

s tr o m a to l i te gave r a th e r b ro a d p e a k s w h ich w e re d iff ic u lt to id en tify .

In fa c t , d im e th y l p h th a la te w as th e only com ponen t of th is f ra c t io n

w hich w as re c o g n iz a b le f ro m i t s c o r re sp o n d in g m a s s s p e c tru m (se e

F ig u re 2).

T he S ily la tio n F r a c t io n p ro d u c e d a n u m b er of s h a rp peak s on

th e g as c h ro m a to g ra p h and s tro n g m a s s s p e c t r a w e re o b ta in ed . I t i s

u n fo rtu n a te , h o w ev er, th a t l i t t le m a s s s p e c t r a l d a ta i s a v a ila b le in th e

l i t e r a tu r e c o n c e rn in g v a r io u s s i ly la te d ca rb o x y lic a c id s . A n u m b e r of

m a s s s p e c t r a l s ta n d a rd s of c a rb o x y lic a c id s and r e la te d com pounds

w e re o b ta in ed , b u t none of th e se s ta n d a rd m a s s s p e c t r a s e e m e d to

c o r r e la te e x a c tly w ith th e unknow n s p e c t r a . Som e of th e m /e v a lu e s

in th e unknow n s p e c t r a , h o w ev er, d id in d ic a te th a t th e s e s ily la te d

com pounds co n ta in ed T M S -carb o x y l g ro u p s . T h e se s ily la te d com pounds

RELA

TIVE

IN

TENS

ITY

(%)

17

too 1

90- DIMETHYL PHTHALATE STANDARD

80 -

70-MW 194

OCH.

30-

40-

30-

2 0 -

10-

9 0 - COMPONENT FROM METHYL ESTER FRACTION

80-

7 0 -

6 0 -

3 0 -

4 0 -

30-

2 0 -

10-

0 K) 20 30 40 50 60 70 80 90 100 IK) 120 130 140 130 160 170 180 190 200

m/e

F ig u re 2. C o m p a riso n of a M a ss S p ec tru m f ro m th e M ethyl E s t e r F r a c t io n w ith a D im eth y l P h th a la te S tan d ard M ass S p e c tru m .

18

w e re r a th e r v o la ti le s in c e th ey e m e rg e d f ro m th e g as c h ro m a to g ra p h

a s h o r t p e r io d of t im e a f te r in je c tio n and a t low te m p e r a tu r e s (120° C).

T he N e u tra l F r a c t io n gave s u rp r i s in g r e s u l t s . P re v io u s

o z p n o ly se s of o th e r ty p e s of m a te r ia ls fa ile d to y ie ld any co m ponen ts

in th e N e u tra l F r a c t io n (B itz and N agy, 1966). The g as c h ro m a to g ra m

o b ta in ed f ro m th is f ra c t io n along w ith th e c o r re sp o n d in g c h ro m a to ­

g ra m f ro m th e b a s a l t b lan k o z o n o ly s is is show n in F ig u re 3. The two

l a r g e s t co m p o n en ts in th e c h ro m a to g ra m (p eak s 3 and 4) of the; T r a n s ­

v a a l S tro m a to lite N e u tra l F r a c t io n gave e s s e n t ia l ly id e n tic a l m a s s

s p e c t r a (F ig u re 4). T h e se com p o n en ts a r e e i th e r 2 - p r o p y l - 3-m e th y l

te t r a h y d ro fu ra n o r 2 -p ro p y l te t ra h y d ro p y ra n o r bo th (se e F ig u re 5).

19

LU

ATT 10

LU

190" 170" 150" 150" HO® 90® 70® 70"TEMPERATURE (eC) | ISOTHERMAL |

F ig u re 3. G as C h ro m a to g ra m of th e N e u tra l F r a c t io n f ro m th e T ra n s v a a l S tro m a to lite , (a) A 100' X .0 2 " i .d . OS 138 C olum n w as u se d . The C olum n w as held I s o th e rm a lly at 70° C fo r 6 M in . th en P r o ­g ra m m e d at 5 ° /m in . at an In itia l A tten u a tio n of 20. (b) G as C h ro m a to ­g ra m of th e N e u tra l F ra c t io n f ro m th e B a s a lt B lank. C ond itions W ere Id e n tic a l to T h o se in (at).

RELA

TIVE

IN

TENS

ITY

(%)

20

COMPONENT FROM NEUTRAL FRACTION1001

90-

80-

70-

60 -

50-

40-

30-

2 0 -

10-(P) (m/e 128)

20 30 40 50 60 70 80

m/e

F ig u re 4. M ass S p ec tru m of P e a k s 3 and 4 f ro m th e N e u tra l F r a c t io n C h ro m a to g ra m .

21

trans cis

F ig u re 5. S tru c tu re s of (a) 2 - P ro p y l- 3- M ethyl T e tra h y d ro - fu ra n and(b) 2-P ro p y l T e tra h y d ro p y ra n .

CHAPTER 4

DISCUSSION

T he m e c h a n ism by w hich ozone r e a c t s w ith an u n s a tu ra te d

o rg a n ic com pound can be r e g a rd e d as a cus- cy d o ad d itio n a c r o s s th e

c a rb o n -c a rb o n double bond to fo rm an u n s ta b le in te rm e d ia te (I).

(See F ig u re 6). T h is in te rm e d ia te d ec o m p o ses in to an ozon ide (II)

w hich is v io le n tly u n s ta b le lik e m o s t s u b s ta n c e s w ith p e ro x id e lin k a g e s

( i . e . , ex p lo s io n s m ay r e s u l t ) . The o zo n id es a re h y d ro ly z e d , fo rm in g

k e to n e s a n d /o r a ld eh y d es (III). Such r e a c t io n s can a lso ta k e p lace

w ith a ro m a tic com pounds.

0- 0"

c+ o=cc=c.

c=o + o=c

F ig u re 6. M ech an ism of R e a c tio n betw een O zone and U n sa tu ra te d H y d ro c a rb o n s .

22

23

O xidation of th e k e to n e s and a ld eh y d es w ith h y d ro g en p e ro x id e

y ie ld s c a rb o x y lic a c id s . A m e c h a n ism fo r th is r e a c t io n is su g g es ted

in F ig u re 7 (H ouse and W asson , 1957). The re a c t io n of c a rb o x y lic

ac id s w ith d ia zo m e th a n e is show n in F ig u re 8, and the p ro d u c tio n of

d ia zo m e th a n e f ro m E X E -101 a p p e a rs in F ig u re 9.

F ig u re 7. O x idation of K etones w ith A lkaline H ydrogen P e ro x id e .

F ig u re 8. M ethy la tion of C a rb o x y lic A cids u s in g D izao m eth an e .

r

9R-C-OH + C H 2N2

0

> R - C - O C H 3 + N 2t

NO NO

0 E X R - I O I 0e t h e r

NaOH

0 0

F ig u re 9. P ro d u c tio n of D iazo m eth an e f ro m E X R -1 0 1 .

.24

T he p re s e n c e of d im e th y l p h th a la te in th e M ethyl E s te r

F ra c t io n along w ith th e ev id en ce f ro m p y ro ly s is m a k e s p o s s ib le th e

co n c lu s io n th a t the k e ro g e n in th e T ra n s v a a l s tro m a to l i t ic l im e s to n e

h as p a r t ia l a ro m a tic c h a r a c te r . A s c h e m a tic i l lu s t r a t io n of ozone

a ttack in g th e p o ly m e r-m a tr ix of th e k e ro g e n to y ie ld p h th a lic ac id is

show n in F ig u re 10.

P O L Y M E RM A T R I X

H 0 0 C

0 3

r

P H T H A L I C A C I D

F ig u re 10. P ro d u c tio n of P h th a lic A cid f ro m O zone A ttack of a P o ly m e r - M a tr ix .

25

T he re -o z o n o ly s is of th e T ra n s v a a l s tro m a to l i te a lso y ie ld e d

■ v a r io u s c a r boxy l ie ac id s p e c ie s . A fte r th e s e ac id s w e re s ily la te d ,

th ey w e re in je c te d in to a S E -30 150' x „ 02" co lum n, and m a ss s p e c t r a

w e re o b ta in ed of th e in d iv id u a l co m p o n en ts . The f re q u e n t and

abundant a p p e a ra n c e of peak m /e 117 im p lie s th a t m o s t of th e s e

s ily la te d d e r iv a t iv e s a r e c a rb o x y lic ac id an a lo g s . T he id e n tif ic a tio n

of m /e 117 and o th e r com m on s ily la te d io n s found in m a s s s p e c t r a of

th e S ily la tio n F r a c t io n a r e show n in T ab le III ( P ie r c e , 1968).

TA B LE H I. C om m on s ily la te d io n s .

m /e Id e n tif ic a tio n

73 (CH3)3 Si+

- 75 H & S i (CH 3 )2

45 CH3S1+H2

103 CH2 =<5si(CH3)3 .

117 + C ^ °-0-S i(C H 3)3

147 (CHg) 2Si=<5-Si(CH3)3

The p re s e n c e of s a tu r a te d a lk y l su b s titu te d c y c lic e th e r s in th e

T ra n s v a a l s tro m a to l i t ic k e ro g e n could p ro v e to b e s ig n if ic a n t. The

id e n tif ic a tio n of th is com pound w as b a s e d la rg e ly on th e m a s s s p e c tru m

of th is com ponen t f ro m th e N e u tra l F r a c t io n . (See F ig u re 4 . ) T he

m /e 85' b a s e peak i s v e ry c h a r a c te r i s t i c of a m e th y l te tra h y d ro fu ra n

26

ion su b s titu te d in th e 3 o r 4 p o s itio n o r a te tra h y d ro p y ra n ion . T h e se

two io n s canno t be d is tin g u ish e d u s in g m a s s s p e c tro m e try (B iem ann ,

1973) (se e F ig u re 11). T h is ion is re a d ily fo rm e d w hen an alky l g roup

su b s titu te d in th e 2 -p o s itio n is p re s e n t , s in c e lo s s of th e alky l g roup

g iv es r i s e to th is v e ry s ta b le ion (B iem an n , 1962). The m o le c u la r

w eigh t of th is com pound (M . W. 128) su g g e s ts th a t th e lo s t a lky l g roup

w as a p ro p y l g ro u p (-C ^H ^) w hich h as an m /e v a lu e of 43. The

seco n d l a r g e s t p eak in th e m a s s s p e c tru m is m /e 43.

F ig u re 11. R eso n an ce S ta b iliz a tio n of m /e 85 Ion.

F u r th e r c o n f irm a tio n of th e s e s t r u c tu r e s is su g g e s te d by the

r e s u l t s of h igh re so lu tio n m a s s s p e c t ro m e try (B iem ann , 1973). The

m a jo r peak at m /e 85 h as a fo rm u la c o n s is te n t w ith th e s p e c ie s in

F ig u re 11 ( i . e . , C^H ^O ). The p a re n t p eak (m /e 128) h a s a m o le c u la r

fo rm u la of C g H ^ O , th e sa m e fo rm u la as the a lk y l-s u b s ti tu te d t e t r a -

h y d ro fu ra n o r te tra h y d ro p y ra n .

■ 27

I t i s no t p o s s ib le th a t th e m /e 85 p eak could r e p r e s e n t an acy l

ion : = O. T h is io n w ould be d e r iv e d f ro m th e f ra g m e n ta tio n of

an a lip h a tic ac id , e s te r o r k e to n e w ith a su b s titu e n t. The m a s s

s p e c tru m of th is com ponen t (F ig u re 4), a long w ith a m o le c u la r fo rm u la

of CgH^gO ( m /e 128), p re c lu d e s th e p o s s ib i l i ty of th is com pound b e in g

an ac id o r e s te r ; b o th c o n ta in tw o oxygen a to m s . A lso , th e N e u tra l

F r a c t io n f ro m w hich th is com ponen t o r ig in a te s w as e x tr a c te d f ro m a

b a s ic -a q u e o u s m ed iu m in w h ich c a rb o x y lic a c id s w ould e x is t as ion?

iz a b le s a l t s and, th e r e fo r e , w ould no t be e x tr a c te d by e th e r . I t i s

a lso doubtfu l if any k e to n e s w ould s t i l l r e m a in a f te r th e ad d itio n of an

e x c e s s of h y d ro g en p e ro x id e p r io r to th e e x tra c t io n of th e N e u tra l

F r a c t io n . Any k e to n e s w ould be o x id ized to a c id s by "this p ro c e d u re

(se e F ig u re 7). A gain , th e m a s s s p e c tru m of th is com ponen t is q u ite

d is s im i la r to m a s s s p e c t r a of k e to n e s co n ta in in g a s u b s titu e n t.

I t is a lso u n lik e ly th a t th e te t ra h y d ro fu ra n o r te tra h y d ro p y ra n

found in th e T ra n s v a a l s tro m a to l i te i s a sy n th e tic o z o n o ly s is p ro d u c t.

The o zo n o ly s is l i t e r a tu r e , to th e a u th o r 's know ledge, d o es not s i te

any of th e s e d e r iv a t iv e s as re a c t io n p ro d u c ts b e tw een ozone and

v a r io u s c la s s e s of o rg a n ic com pounds. C y c lic h y d ro c a rb o n s (e. g . »

cy c lo h ex an e), fo r e x a m p le , r e a c t w ith ozone to fo rm c y c lic k e to n es

and a lco h o ls ( e . g . , cyc lo h ex an o n e and cy c lohexano l) (H am ilto n ,

R ib n e r , and H e ilm an , 1968). H am ilto n (1973) doub ts th a t

28

te t ra h y d ro fu ra n s cou ld fo rm f ro m a lk an es u n d e r th e co n d itio n s u se d

in th e a u th o r 's o zo n o ly s is p ro c e d u re .

I t is p o s s ib le th a t th e c y c lic e th e r s could b e r e m n a n ts of

c a rb o h y d ra te s ; S im m onds, S hulm an, and S tem b rid g e (1969) show ed

th a t c a rb o h y d ra te s d e g ra d e to fu r an d e r iv a t iv e s upon h e a tin g . F e a th e r

(1970) d o cu m en ts th e c o n v e rs io n of p e n to se s to 2- fu ra ld e h y d e and

h e x o se s to 5 -h y d ro x y m e th y l-2 -fu ra ld e h y d e u n d e r a c id ic co n d itio n s .

C ond itions su ch as a c id ity and h e a t a r e p o s s ib le in th e g eo lo g ic e n v i­

ro n m e n t to w hich th e T ra n s v a a l s tr o m a to l i t ic k e ro g e n w as su b je c te d

d u rin g i t s 2. 2 b ill io n y e a r sp an . T he re d u c tio n of th e f u r an d e r iv a ­

t iv e s to te t ra h y d ro fu ra n d e r iv a t iv e s i s a lso p o s s ib le s in c e th e r e a r e

m e ta l c a ta ly s ts and m o le c u la r h y d ro g en in s e d im e n ta ry s y s te m s . T he

s a tu r a te d h y d ro c a rb o n , p h y tan e , a p p e a rs to be fo rm e d by re d u c tio n of

th e phy to l s id e ch a in of c h lo ro p h y ll in th e geo log ic e n v iro n m e n t.

S im ila r ly , o le f in ic fa tiy a c id s , w h ich a re a b sen t in s e d im e n ts bu t

abundant in p la n t and a n im a l t i s s u e , s e e m to have b e e n re d u c e d d u r in g

geo lo g ic t im e (Jo h n so n and C a ld e r , 1973).

F iv e -m e m b e re d r in g s co n ta in in g oxygen a re r e p o r te d as c o m ­

p o n en ts of th e s t r u c tu r e s of co a l and h u m ic a c id s . A llo b e tu lin , a

t r i te r p e n o id w ith a t e t r ahy d r o fu r an r in g in i t s s t r u c tu r e , w as found in

a b ro w n co a l (S tr e ib l and H er out, 1969). A lkyl fu r an s w e re found as

p y ro ly s is p ro d u c ts of h u m ic ac id s by W ersh aw and B o h n e r (1969).

D ih y d ro fu r an r in g s a lso e x is t in so m e c a ro te n o id s w hich a r e in vo lved

29

in p h o to s y n th e s is . B e s id e s b e in g found in a ll g re e n p la n ts , c a r o t r ..

en o id s e x is t in so m e n o n p h o to sy n th e tic b a c te r ia (S chw end inger, 1969).

By r a n d e r iv a t iv e s a re r e p o r te d to be co n ta in ed in so m e su g g es ted

s t r u c tu r e s of h u m ic ac id (S tev en so n and B u tle r , 1969). The p r e s e n c e

of c y c lic e th e r d e r iv a t iv e s in m a te r ia ls su c h as co a l and h u m ic a c id s ,

w hich a r e know n to be of b io lo g ic a l o r ig in , s tr e n g th e n s th e p o s s ib il i ty

th a t th e c y c lic e th e r d e r iv a t iv e s p r e s e n t in th e T ra n s v a a l s tr o m a to l i te

m ay b e b io lo g ic a l m a r k e r s , th u s c o n firm in g th e m ic ro p a le o n to lo g ic a l

ev id en ce of p r im it iv e life d u rin g th is t im e . If th e s e s a tu r a te d alky l

s u b s titu te d c y c lic e th e r s d e r iv e d f ro m in d ig en o u s o rg a n ic m a t te r , a r e

in d e e d 're m n a n ts of s u g a r s , th e n b io lo g ic a l s y s te m s can b e shown to be

fu n c tio n in g 2 .2 b ill io n y e a r s ago.

R E F E R E N C E S

B iem an n , K„ (1962) M ass S p e c tro m e try . New Y o rk : M cG raw -H ill, pp . 3 3 -3 9 . .

B iem an n , K . (1973) M a ss a c h u se tts In s ti tu te of T echno logy , D e p a r t­m e n t of C h e m is try , C am b rid g e , M assach u se tts -, p e r s o n a l co m m u n ic a tio n .

B itz , M . C. and N agy, B . (1966) O z o n o ly s is of " P o ly m e r -T y p e 11M a te r ia l in C oal, K ero g en , and in th e O rg u e il M e te o r ite : A P r e l im in a r y R e p o r t . P r o c . N a t. A cad . S c i . , 56, 1383.

B u rlin g a m e , A. , H aug, P . , B e lsk y , T . , and C alv in , M. (1965)O c c u r re n c e of B io g en ic S te ra n e s and P e n t a c y c lic T r i te rp a n e s in an E o cen e S hale (52 m illio n y e a r s ) and in an E a r ly P re C a m ­b r ia n Shale (2 . 7 b il l io n y e a r s ) : A P r e l im in a r y R e p o r t. P r o c . N at. A cad . S c i . , 54, 1406-1412 .

C ra ig , H. (1957) Iso to p ic S ta n d a rd s fo r C a rb o n and O xygen andC o rre c t io n F a c to r s fo r M a ss S p e c tro m e tr ic A n a ly s is of C a rb o n D iox ide . G eo ch im . C o sm o ch im . A cta , 12, 133.

D uncan, D. C. and Sw anson, V. E . (1965) O rg a n ic -R ic h S hale of th e U n ited S ta te s and W orld L and . A re a s . G eo lo g ica l S urvey C ir c u la r 523 .

E g lin to n , G . and C a lv in , M . (1967) C h e m ic a l F o s s i l s . S c ien tific A m e ric a n , 216, 32.

F e a th e r , M . S. (1970) T he C o n v e rs io n of D -X y lo se and D -G lu c u ro n ic A cid to 2-F u ra ld e h y d e . T e tra h e d ro n L e t t e r s , 4 8 , 4 1 4 3-4145 .

F o rs m a n , J . R . (1963) G e o c h e m is try of K ero g en . In : O rg an ic G e o c h e m is try (ed . I. A. B r e g e r ) . New Y o rk ; P e rg a m o n P r e s s , p . 177.

H am ilto n , G . A . (1973) U n iv e rs ity of C a lifo rn ia , D e p a r tm e n t ofB io c h e m is try , B e rk e le y , C a lifo rn ia , p e r s o n a l co m m u n ica tio n .

30

31

H am ilto n , G„ A „ , R ib n e r , B„ S . , and H eilm an , T„ M„ (1968) M echa­n is m of A lkane O x idation by O zo n e . A dvan. C hem . S erv , 77, 1 5 -2 5 .

H ouse , H . O . and W asso n , R„ L , (1957) The R e a c tio n of K eto n es w ith P e ro x id e s in A lk a lin e S o lu tion . J . O rg . C h e m ., 22, 1157.

Jo h n so n , R . W. and C a ld e r , J . A. (1973) E a r ly D ia g e n e s is of F a t ty A cids and H y d ro c a rb o n s in a S alt M a rs h E n v iro n m e n t.G eo ch im . C o sm o ch im . A cta , 37, 1943-1955 .

K aufm an , M . , F r ie d m a n , S . , and W en d er, I . (1967) G as C h ro m a to ­g ra p h ic S e p a ra tio n s of B en zen e c a r boxy l ie A cids D e riv e d f ro m C oal. A nal. C h e m ., 39, 1011.

M ille r , S. L . and U re y , H . C. (1959) O rg an ic C om pound S y n th esis on th e P r im i t iv e E a r th . S c ie n c e , 130, 2 45-251 .

N agy, B . (1970) P o ro s i ty and P e r m e a b i l i ty of th e E a r ly P r e c a m b r ia n O n v erw ach t C h e r t: O rig in of th e H y d ro c a rb o n C on ten t.G eo ch im . C o sm o ch im . A c ta , 34, 525.

. N agy, L . A. (1973) T ra n s v a a l S tro m a to l i te : F i r s t E v id e n c e fo r th e D iv e rs if ic a t io n of C e lls - 2 .2 X 10^ Y e a rs Ago. S c ie n c e , in p r e s s .

O e h le r , D . F . , Schopf, J . W . , and K venvolden , K . A. (1972) C arb o n Iso to p ic S tu d ies of O rg a n ic M a tte r in P r e c a m b r ia n R o ck s . S c ie n c e , 175, 1246.

P ie r c e , A. E . (1968) S ily la tio n of O rg a n ic C o m pounds. R o ck fo rd , I l l in o is : P ie r c e C h em ica l C o ., pp . 33 -3 9 .

P r e to r iu s , D. A. (1971, 1973) T he U n iv e rs ity of th e W itw a te rs ra n d , J o h a n n e sb u rg , South A fric a , p e r s o n a l c o m m u n ica tio n .

S ch w en d in g er, R . B . (1969) C a ro te n o id s . In: O rg an ic G e o c h e m is try (e d s . G. E g lin to n and M. T. J . M urphy). New Y o rk : S p r in g e r - V e r la g , p . 425.

S im m o n d s, P . G . , S hulm an, G. P . , and S tem b rid g e , C . H. (1969) O rg a n ic A n a ly s is by P y r o ly s is - G a s C h ro m a to g ra p h y -M a ss S p e c tro m e try . A C an d id ate E x p e r im e n t f o r th e B io lo g ica l E x p lo ra tio n of M a rs . J o u rn a l of C h ro m a to g ra p h ic S c ien ce ,7, 3 6 -4 1 . ~

32

S m ith , J . W ., Schopf, J . W . , and K ap lan , I. R . (1970) E x tra c ta b leO rg a n ic M a tte r in P re c a m b r ia n C h e r ts . G eo ch im . C o sm o ch im . A c ta , 34, 659-675 .

S tev en s , G. R . (1966) A n a ly s is and P a ra g e n e t ic H is to ry ofA n th ra x o lite in O rd o v ic ia n S la te , E a s te r n P e n n sy lv a n ia . In: C oal S c ien ce (ed . R . F . G ould). W ash ing ton , D. C. :A m e ric a n C h em ica l S ocie ty P u b lic a tio n s , p . 98.

S tev en so n , F . J . and B u tle r , J . H. A. (1969) C h e m is try of H um ic A cids and R e la te d P ig m e n ts . In : O rg an ic G e o c h e m is try (e d s .G. E g lin to n and M. T. J . M urphy). New Y o rk : S p r in g e r - V e rla g , p. 534.

S tre ib l , M. and H e r out, V . (1969) T e rp e n o id s . In: O rg a n ic G eo­c h e m is try (ed s . G. E g lin to n and M. T. J . M urphy). New Y o rk : S p r in g e r -V e r la g , p . 401 .

S tu d ie r, M. H . , H ay a tsu , R . , and A n d e rs , E . (1972) O rig in ofO rg a n ic M a tte r in E a r ly S o la r S y s te m -V . F u r th e r S tud ies of M e te o r itic H y d ro ca rb o n s and a D isc u ss io n of T h e ir O rig in . G eo ch im . C o sm o ch im . A cta , 36, 189-215 .

W a lte r , M. R . , B auld , J . , and B ro c k , T . D. (1972) S ilic e o u s A lgal and B a c te r ia l S tro m a to li te s in Hot S p rin g and G e y s e r E fflu en ts of Y e llo w sto n e N a tio n a l P a r k . S c ien ce , 178, 4 0 2 -4 0 5 .

W ersh aw , R . L . and B o h n er, G. E . (1969) P y ro ly s is of H um ic and F u lv ic A cid s . G eoch im . C o sm o ch im . A cta , 33, 757-762 .