ozonolysis of kerogen in a transvaal...
TRANSCRIPT
Ozonolysis of kerogen in Transvaal stromatolitic limestone
Item Type text; Thesis-Reproduction (electronic)
Authors Zumberge, John Edward, 1948-
Publisher The University of Arizona.
Rights Copyright © is held by the author. Digital access to this materialis made possible by the University Libraries, University of Arizona.Further transmission, reproduction or presentation (such aspublic display or performance) of protected items is prohibitedexcept with permission of the author.
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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 .
