---W i l s o n L. Orr
MOBlL RESEARCH AND DEVELOPMENT CORPORATION
FIELD RESEARCH LABORATORY
DALLAS, TEXAS, 75221
INTRODUCTION
S u l f u r , a f t e r carbon and hydrogen, i s o f t e n t h e most abundant element
i n f o s s i l o r g a n i c m a t e r i a l s , whereas i n b i o l o g i c a l t i s s u e s and t h e i r d e g r a d a t i o n
p r o d u c t s oxygen and n i t r o g e n u s u a l l y a r e m r e abundant than s u l f u r .
I n rare
cases, the s u l f u r c o n t e n t on a w e i g h t b a s i s even exceeds t h e hydrogen c o n t e n t .
Nevertheless, s u l f u r i n p e t r o l e u m appears t o be n o n - e s s e n t i a l , i . e . , i t i s
n o t a necessary component f o r t h e f o r m a t i o n o f p e t r o l e u m and r e i a r e d bitumens
because some o f these m a t e r i a l s ' c o n t a i n o n l y t r a c e amounts.
The c h e m i s t r y o f s u l f u r i n f o s s i l f u e l s and r e l a t e d m a t e r i a l s i s o f
i n t e r e s t f o r two m a j o r reasons: 1) For i t s b e h a v i o r d u r i n g p r o c e s s i n g and i n
applications:
I t can cause problems i n p r o c e s s i n g and has d e l e t e r i o u s e f f e c t s
on t h e environment i n many a p p l i c a t i o n s , and 2) For i t s geochemical s i g n i f i c a n c e ,
f o r u n d e r s t a n d i n g processes which determine i t s abundance, d i s t r i b u t i o n ,
and chemical c o m b i n a t i o n ( f o r m s ) d u r i n g b o t h t h e f o r m a t i o n and a l t e r a t i o n o f
f o s s i l o r g a n i c m a t e r i a l s i n g e o l o g i c environments.
t h e geochemistry o f
Emphasis i n t h i s paper i s o n t h e second area
s u l f u r i n c r u d e o i l s , o i l sands and r e l a t e d m a t e r i a l s . The f i r s t s e c t i o n o f
t h i s paper b r i e f l y summarizes some o f t h e f a c t u a l knowledge c o n c e r n i n g t h e
abundance and forms o f s u l f u r i n t h e s e m a t e r i a l s , e s p e c i a l l y i n c r u d e o i l s .
F o l l o w i n g t h i s i s a more s p e c u l a t i v e s e c t i o n d i s c u s s i n g o p i n i o n s and o u r unders t a n d i n g o f t h e geochemical processes b e l i e v e d t o c o n t r o l and m o d i f y t h e abundance
and forms o f s u l f u r .
In s p i t e o f much research and a g r e a t body o f f a c t u a l
knowledge, many i m p o r t a n t q u e s t i o n s a r e s t i l l debated and d i v e r s e views w i l l
.
be found i n t h e l i t e r a t u r e .
-i.e.,
--
86
I t i s r e a s o n a b l e t h a t t h e s u l f u r i z a t i o n o f o r g a n i c m a t t e r can o c c u r a t
any s t a g e i n t h e g e o l o g i c a l h i s t o r y o f a g i v e n m a t e r i a l i f p r o p e r c o n d i t i o n s
prevail.
However, ma:dy advocates for a l a t e i n t r o d u c t i o n a p p a r e n t l y d o n o t
a p p r e c i a t e t h e magnitude o f s u l f u r i n c o r p o r a t i o n i n t o i n i t i a l sedimentary o r g a n i c
m a t t e r i n c e r t a i n environments.
For example, humic a c i d s e x t r a c t e d from young
m a r i n e sediments c o n t a i n f r o m 0.8 t o 6 %S, and t h e s e a c i d i c p o l y m e r i c m a t e r i a l s
Humic a c i d s
make up f r o m 20 t o 60% o f t h e o r g a n i c m a t t e r i n many sediments (26).
m y be considered m a j o r p r e c u r s o r s o f kerogen w h i c h i n t u r n can be t h e major
p r e c u r s o r o f p e t r o l e u m (41).
Gransch and Posthuma (16) conclude t h a t m s t o f t h e s u l f u r i n c r u d e o i l s
o r i g i n a t e s from o r g a n i c a l l y combined s u l f u r i n t h e kerogen o f s o u r c e r o c k s , and
t h e r e f o r e t h e m a j o r s u l f u r compounds and hydrocarbons a r e formed t o g e t h e r .
They g i v e a number o f examples i l l u s t r a t i n g t h a t h i g h - s u l f u r kerogens produce
h i g h - s u l f u r o i l s and v i c e versa. They a l s o concluded f r o m l a b o r a t o r y experiments
t h a t more s u l f u r compounds a r e formed d u r i n g t h e e a r l y stages o f o i l g e n e r a t i o n
from a g i v e n kerogen than d u r i n g t h e l a t e r stages o f i t s decomposition.
Thus
t h e s u l f u r c o n t e n t o f an o i l i s a f u n c t i o n o f b o t h t h e i n i t i a l s u l f u r c o n t e n t
o f i t s source kerogen and i t s s t a t e o f m a t u r a t i o n o r e v o l u t i o n .
I b e l i e v e these
c o n c l u s i o n s a r e e s s e n t i a l l y c o r r e c t and a r e accepted by a l a r g e number o f geochemists.
N e v e r t h e l e s s , t h e r e a r e subsequent changes and a l t e r a t i o n s i n o i l s
a f t e r they a r e formed, p o s s i b l y d u r i n g t h e i r m i g r a t i o n , and a f t e r t h e i r accumul a t i o n i n reservoirs.
Many q u e s t i o n s remain about t h e n a t u r e and importance o f
these e f f e c t s .
Evidence o f l a t e s u l f u r i z a t i o n and competing d e s u l f u r i z a t i o n o f
o i l s d u r i n g thermal m a t u r a t i o n i n some h i g h temperature r e s e r v o i r s has been
demonstrated (27, 291, b u t s i n c e t h i s does n o t r e l a t e d i r e c t l y t o heavy o i l s
i t w i l l n o t be discussed.
S t u d i e s o f s u l f u r i s o t o p e r a t i o s (34S/32S)q have c o n t r i b u t e d t o o u r unders'tanding o f t h e o r i g i n o f s u l f u r i n p e t r o l e u m and s u p p o r t t h e v i e w f o r i t s e a r l y
'i'ncorporation i n t o o i l p r e c u r s o r m a t e r i a l s . These s t u d i e s i n d i c a t e t h a t a l a r g e
p o r t i o n o f t h e s u l f u r has been d e r i v e d f r o m reduced s u l f u r !H2S and/or S o ) showing
t y p i c a l isotopic f r a c t i o n a t i o n a t t r i b u t e d t o microbial reduction o f s u l f a t e
%der c o n d i t i o n s where t h e s u p p l y o f s u l f a t e i s n o t l a r g e l y reduced (i.5,i n
an open system)(27, 36, 37, 38).
I t has been e s t a b l i s h e d t h a t t h e 6%
v a l u e s o f sea w a t e r have f l u c t u a t e d
c o n s i d e r a b l y w i t h g e o l o g i c p e r i o d s (17, 37, 38) and t h a t 6%
values of s u l f u r
c r u d e o i l s show p a r a l l e l f l u c t u a t i o n s w i t h g e o l o g i c age b u t a r e commonly
/oo l i g h t e r i s o t o p i c a l l y than sea w a t e r s u l f a t e o f t h e same age. These
s e r v a t i o n s a r e m s t r e a s o n a b l y e x p l a i n e d by i s o t o p i c f r a c t i o n a t i o n d u r i n g
c r o b i a l r e d u c t i o n o f sea w a t e r s u l f a t e a t t h e t i m e o f sediment d e p o s i t i o n .
e H2S and/or So thus formed became i n c o r p o r a t e d i n t o sedimentary o r g a n i c
matter w i t h r e t e n t i o n of i t s i s o t o p i c r a t i o .
Later w i t h t h e formation o f petroleum
by thermal processes r e s u l t i n g f r o m deeper b u r i a l , t h e s u l f u r compounds formed
$ i t h t h e hydrocarbons r e t a i n t h e i s o t o p i c r a t i o r e f l e c t i n g t h e o r i g i n a l i s o t o p i c
fractionation.
The amount o f s u l f u r i n i t i a l l y i n c o r p o r a t e d i n t o sedimentary o r g a n i c
m a t t e r may be expected t o be determined by I ) t h e abundance o f s u l f a t e i n t h e
w a t e r , 2) t h e Eh o f t h e environment near t h e sediment-water i n t e r f a c e which i s
one o f t h e c o n t r o l s on t h e i n t e n s i t y o f m i c r o b i a l s u l f a t e r e d u c t i o n , 3) t h e
ip
i"'
*Sulfur
\
?. '
i s o t o p e r a t i o s a r e r e p o r t e d as d e v i a t i o n s (6
(O/oo) from a s t a n d a r d a c c o r d i n g t o t h e r e l a t i o n s h i p :
89
B.
E f f e c t s o f B i o d e g r a d a t i o n and Water-Washing on S u l f u r i n F o s s i l F u e l s
These crude o i l a l t e r a t i o n processes have been a d e q u a t e l y d i s c u s s e d i n
t h e l i t e r a t u r e ( I , 2, 8, 1 3 , 32, 42) and o n l y s e l e c t e d a s p e c t s can be reviewed
here. These processes a r e d i s c u s s e d t o g e t h e r because t h e y commonly o c c u r t o g e t h e r
i n o i l r e s e r v o i r s . An a c t i v e a q u i f e r f a c i l i t a t e s b o t h processes.
Water-washing r e f e r s t o t h e e x t r a c t i v e removal o f crude o i l components
which, o f course, depends o n t h e i r s o l u b i l i t y i n t h e aqueous phase.
Biodegradat i o n r e f e r s t o t h e o x i d a t i o n of c r u d e o i l components by b a c t e r i a and t h e r e f o r e
has b i o c h e m i c a l l y c o n t r o l l e d s e l e c t i v i t y w h i c h may be d i f f e r e n t f o r v a r i o u s
m i c r o b i a l communities.
M i c r o b i a l a c t i v i t y has an upper temperature l i m i t whereas water-washing
does n o t .
Nevertheless, a c t i v e a q u i f e r s a s s o c i a t e d w i t h p e t r o l e u m r e s e r v o i r s a r e
commonly s h a l l o w and temperatures a r e t h e r e f o r e s u f f i c i e n t l y low f o r m i c r o b i a l
a c t i v i t y . The a q u i f e r may s u p p l y oxygen f o r a e r o b i c b a c t e r i a and/or s u l f a t e f o r
anaerobic s u l f a t e reducing bacteria.
M i c r o b i a l u t i l i z a t i o n o f hydrocarbons by a e r o b i c microorganisms has been
known f o r many y e a r s by m i c r o b i o l o g i s t s ( 3 , 8, 4 0 ) , b u t , t h e u t i l i z a t i o n o f hydrocarbons by a n a e r o b i c microorganisms i s debated and i s d i f f i c u l t t o demonstrate
i n t h e laboratory (8).
N e v e r t h e l e s s , f i e l d s t u d i e s and n a t u r a l o b s e r v a t i o n s
p r o v i d e s t o n g evidence o f m i c r o b i a l r e d u c t i o n o f s u l f a t e (an a n a e r o b i c process)
i n many s i t u a t i o n s where p e t r o l e u m hydrocarbons a r e t h e most l i k e l y o r g a n i c
s u b s t r a t e a v a i l a b l e (8, 14, 19, 32).
Furthermore, t h e r e i s ample evidence t h a t
i n many such cases secondary c a l c i t e has been formed w h i c h has carbon i s o t o p e
r a t i o s i n d i c a t i n g t h a t i t s carbon must have been d e r i v e d f r o m t h e o x i d a t i o n Of
90
hydrocarbons (14).
I t must be concluded t h a t m i c r o b i a l o x i d a t i o n o f c r u d e o i l s
i n t h e subsurface does o c c u r and may i n v o l v e b o t h a e r o b i c and a n a e r o b i c m i c r o organisms.
I n t e r e s t i n b i o d e g r a d a t i o n o f c r u d e o i l s i n r e s e r v o i r s r e c e i v e d a new
s t i m u l u s by t h e r a t h e r d e f i n i t i v e s t u d y o f t h e B e l l Creek F i e l d r e p o r t e d by
I n t h i s case t h e b i o d e g r a d a t i o n was a t t r i b u t e d
W i n t e r s and W i l l i a m s i n 1969 ( 4 2 ) .
l a r g e l y t o a e r o b i c microorganisms because o f r e l a t i o n s h i p s between changes i n o i l
c o m p o s i t i o n and l o c a t i o n s o f w e l l s i n t h e f i e l d .
Shallower o i l s c l o s e r t o t h e
a q u i f e r o u t c r o p were more degraded than deeper o i l s f u r t h e r from t h e o u t c r o p .
V a r i a t i o n s o f oxygen w i t h d i s t a n c e from t h e o u t c r o p were c o n s i d e r e d t o be a cont r o l l i n g factor.
Most r e c e n t l y , P h i l i p p i (32) has taken a s t r o n g p o s i t i o n s u g g e s t i n g t h a t
a l l "primary" crude o i l s a r e p a r a f f i n i c , and t h a t a l l "naphthenic" crude o i l s
a r e t h e r e s u l t o f m i c r o b i a l a t t a c k on t h e p r i m a r y o i l s . He a l s o b e l i e v e s t h a t
anaerobes a r e e f f e c t i v e i n t h e s e t r a n s f o r m a t i o n s .
B a i l e y et&. ( I ) a l s o assume
t h a t b a c t e r i a can m e t a b o l i z e most t y p e s o f hydrocarbons i n c l u d i n g a r o m a t i c s and
naphthenes a l t h o u g h n-alkanes a r e most r e a d i l y a t t a c k e d . Thus, i t has become
common f o r geochemists t o accept c e r t a i n c r i t e r i a ' a s evidence o f m i c r o b i a l
degradation.
Major gross c r i t e r i a a r e a r e l a t i v e decrease i n n-alkanes, an i n c r e a s e
i n d e n s i t y (decrease i n API g r a v i t y ) , and an i n c r e a s e i n c y c l o a l k a n e s , a r o m a t i c s
and h e t e r o a t o m i c compounds ( N , S, and 0 compounds).
Isoprenoids, 59, p r i s t a n e
and phytane, i n i t i a l l y show an apparent i n c r e a s e r e l a t i v e t o n-alkanes because
o f t h e i r slower u t i l i z a t i o n b u t s u b s e q u e n t l y t h e y decrease r e l a t i v e t o c y c l o alkanes and o t h e r compounds.
P h i l i p p i and o t h e r s have discussed a d d i t i o n a l
c r i t e r i a based on t h e r e l a t i v e amounts o f v a r i o u s compound types and/or isomer
ratios.
U n f o r t u n a t e l y , no a b s o l u t e l y s t a b l e marker i s known which would a l l o w
assessment o f a b s o l u t e changes r a t h e r than r e l a t i v e changes.
Our i n t e r e s t i n t h i s paper c e n t e r s m a i n l v on t h e i n c r e a s e i n s u l f u r
content of o i l s during biodegradation.
We subsckibe t o t h e t h e s i s t h a t t h e
i n c r e a s e i n s u l f u r c o n t e n t occasioned by b i o d e g r a d a t i o n i s l a r g e l y due t o losses
o f n o n - s u l f u r compounds r a t h e r than t o an i n t r o d u c t i o n o f a d d i t i o n a l s u l f u r .
Some consequences o f t h i s t h e s i s and evidence f o r i t s s u m o r t a r e a i v e n below.
However, i t should be c l e a r t h a t d e f i n i t i v e d a t a a r e s t i i l l a c k i n g - a n d t h e p r o b l e m
needs f u r t h e r study.
I n r e p o r t e d s u i t e s o f o i l s b e l i e v e d t o r e p r e s e n t undegraded and biodegraded
o i l s from a common source, t h e s u l f u r c o n t e n t o f t e n i n c r e a s e s by a f a c t o r o f 2
o r 3 ( I , 2, 13, 16)"; t h e f a c t o r may be g r e a t e r i n v e r y heavy a s p h a l t s and t a r
sands b u t d e f i n i t i v e d a t a a r e n o t a v a i l a b l e t o my knowledge.
I f t h i s increase
i s m e r e l y a c o n c e n t r a t i o n o f s u l f u r compounds from t h e r e l a t i v e loss o f n o n - s u l f u r
compounds, i t r e q u i r e s t h a t 50 t o 70% o f t h e i n i t i a l o i l must be destroyed.
I n most cases t h i s i s g r e a t e r than t h a t p o s s i b l e from s e l e c t i v e removal o f n-alkanes
a l o n e and t h e r e f o r e a p p r e c i a b l e l o s s e s o f i s o - and c y c l o - a l k a n e s and a r o m a t i c s
are required.
I f some o f t h e s u l f u r compounds a r e a l s o u t i l i z e d , then, o f course,
losses must be even g r e a t e r I n t h e absence o f an a b s o l u t e marker o r complete
m a t e r i a l balance i n f o r m a t i o n , we cannot draw a f i n a l c o n c l u s i o n . N e v e r t h e l e s s ,
such l a r g e losses may be p o s s i b l e .
The l i m i t e d d a t a on s u l f u r i s o t o p e r a t i o s f o r Midway-Sunset o i l s shown
i n F i g . 8 a r e c o n s i s t e n t w i t h t h e above s u g g e s t i o n t h a t t h e s u l f u r i n c r e a s e
d u r i n g b i o d e g r a d a t i o n does n o t n e c e s s a r i l y i n v o l v e t h e i n t r o d u c t i o n o f new s u l f u r
formed by m i c r o b i a l r e d u c t i o n o f s u l f a t e .
These t h r e e o i l s , which v a r y i n s u l f u r
c o n t e n t from 0.51 t o 1.08% and i n A P I g r a v i t y from 26.1 t o 15.1", have e s s e n t i a l l y
i d e n t i c a l s u l f u r i s o t o p e r a t i o s . T h i s suggests t h a t e i t h e r l i t t l e or no new
s u l f u r was i n t r o d u c e d o r t h e r a t h e r u n l i k e l y c o i n c i d e n c e t h a t t h e s u l f u r i n t r o d u c e d
91
had t h e same s u l f u r i s o t o p e r a t i o as t h a t i n t h e o r i g i n a l o i l .
Further isotopic
s t u d i e s o f t h i s t y p e i n c l u d i n g measurements on a s s o c i a t e d hydrogen s u l f i d e and
s u l f a t e s s h o u l d h e l p a e l i n e a t e s i t u a t i o n s where s u l f u r i z a t i o n does o r does n o t
occur d u r i n g b i o d e g r a d a t i o n o f c r u d e o i l s .
Another b i t o f evidence s u p p o r t i n g t h e above p o s i t i o n may be found i n
t h e homogeneity o f s u l f u r i s o t o p e s i n crude o i l s . Monster (23) demonstrated
t h a t s u l f u r i s o t o p e r a t i o s were a l m o s t i d e n t i c a l i n t h e a s p h a l t e n e s and v a r i o u s
I f t h e c o n c l u s i o n s o f Bestougeff
chromatographic f r a c t i o n s f r o m a few c r u d e o i l s .
and Combaz ( 5 ) a r e v a l i d , one would e x p e c t t h e newly i n t r o d u c e d s u l f u r t o be
m o s t l y i n t h e more p o l a r and h i g h e r m o l e c u l a r w e i g h t f r a c t i o n s . T h e r e f o r e ,
a homogeneous d i s t r i b u t i o n o f s u l f u r i s o t o p e r a t i o s would n o t be expected
u n l e s s t h e r e a c t i n g hydrogen s u l f i d e and/or elemental s u l f u r had t h e same i s o t o p e
r a t i o s as t h a t o f t h e s u l f u r i n i t i a l l y i n t h e o i l s . The o i l s examined by Monster
a r e regarded as biodegraded o i l s . They i n c l u d e d two o f t h e M i s s i o n Canyon (MC-5)
oils s t u d i e d by B a i l e y sal. ( 2 ) and t h e Athabasca o i l sand. Only a few o i l s
have been examined f o r homogeneity o f s u l f u r i s o t o p e s . Another case i s t h e
Fourbear o i l f r o m t h e B i g Horn Basin.
I n t h i s case v e r y l i t t l e d i f f e r e n c e i n
s u l f u r i s o t o p e r a t i o s was found i n d i s t i l l a t i o n s c u t s and t h e d i s t i l l a t i o n r e s i d u e
(see F i g . 1 1 i n r e f e r e n c e 27). T h i s i s one of t h e h e a v i e s t and p r o b a b l y mast
biodegraded o i l s i n t h e B i g Horn Basin.
A t h i r d argument f o r o u r t h e s i s may be t h e f a c t t h a t biodegraded heavy
o i l s and t a r sands do n o t n e c e s s a r i l y have a h i g h s u l f u r c o n t e n t .
T h i s was
(7) i n r e p o r t i n g on t h e heavy o i l s o f t h e Emeraude
emphasized by C l a i r e t
F i e l d and some nearby b u t deeper l i g h t oils. The l i g h t o i l s w i t h o n l y about
0.12%5 were concluded t o be t h e t y p e o f o i l which d u r i n g b i o d e g r a d a t i o n i n t h e
These a u t h o r s make t h e f o l Emeraude F i e l d produced heavy o i l s w i t h about 0.8%.
l o w i n g statement ( T r a n s l a t e d from French t e x t ) : We a r e l e d t o suppose t h a t t h e
s u l f u r enrichment i n t h e c o u r s e o f b i o l o g i c a l d e g ~ d a t i o n s ~ a ~ n ~ a n e f f e c t o f c o n c e n t r a t i o n o f t h e p r o d u c t s not consumed by microorganisms, and does
n o t i m p l y any a p p r e c i a b l e i n t r o d u c t i o n o f s u l f u r f r o m o u t s i d e .
zt.
--
92
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*
p
w
14.
95
ALKANETHIOL
METHANETHIOL
ALKYLDISULFIDE
2,2-DITHIAHEPTANE
ALKANETHIOL
1 PENTANETHIOL
CYCLOALKYLTHIOL
CYCLOHEXANETHIOL
ALKYLSULFIDE
2- THIAPENTANE
THIACYCLOALKANE
THIACYCLOHEXANE
THIACYCLOALKANE
2.2-DIMETHY LTHIACYCLOPENTANE
THIABICYCLOALKANE
8-THIABICYCLO [3,2,1] OCTANE
THIATRICYCLOALKANE
THIAADAMANTANE
AKYLTHIOPHENE
2-ETHYL- 3,4,5-lRIMETHYL
THIOPHENE
ARYLTHIAALKANE
(2-METHYLTHIABUTYL 1
BENZENE
BENZOTHIOPHENE
BMETHY-BENZO [b] THIOPHENE
9-THIA-l,2-BENZOFLUORENE
2-METHY LTHIENOTHOPHENE
[ 3. 2, b]
2.2-DIMETHYL-I -THIAINDAN
3-ETHYL-6.18-DIMETHYLNAPHTHO[l. 2, b ] THIOPHENE
<
A l I A V U 9 IdV ONISV3M3NI
97
--*-FOURBEAR
-SLICK
CREEK
-----X----MANDERSON
3.14%S
2.32%S
1.82XS
13.8 API.
30.0 API'
33.2 API'
100
200
300
400
BOILING POINT OF DISTILLATION FRACTIONS ( 'C)
% SULFUR
Figure 7
MIDWAY
MIDWAY
VALLEY
98
Ax798
CX799
MIDNORTH X20
WOEIL
SON GRAIL X 10
SEA LEVEL
P
-1
9v,
W
-1
LOCATION
S
834S
-APlO
-K+3.2%0
A+798
Br001
C1799
15.1
26.1
19.4
1 .00
0.51 +3,2OAo
0.96 + 4 . 0 %
8'3-.ww
-22.8Xo
-22.7%0
-22.9Xo
99
z
W
G
z