Isolation and identification of organic components of meteorites, and ancient sediment

Kaplan, I. R.

English

NASA Technical Reports Server

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JNIVER~ITY OF CALIFORNIA, LOS ANGELES 
BERKELEY DAVIS IRVINE LOS ANCELES RIVERSIDE SAN DlECO SAN FRANCISCO SANTA BARBARA SANTA CRUZ 
I N S m U T E  OF GEOPHYSICS +ND PLANETARY PHYSICS 
LOS ANGELES, CALIFORNIA 90024 
February 8, 1967 
lA ANALYSIS OF ANCIENT S E D I M E N T S  AND 
NASA Grant No. NGR 05-007-077 
EXTRA-TERRESTRIAL MATERIALS 'o= 
SEMI-ANNUAL REPORT 
June 1 - November 30, 1966 4 
I n t r odu c t i on 
The s t u d i e s  i n i t i a t e d  i n  June 1966 were designed t o  
i s o l a t e  and i d e n t i f y  o rgan ic  ccmponents o f  meteor i  tes,  recen t  
and a n c i e n t  sediments. The b a s i c  i n t e n t i o n ,  i n  a d d i t i o n  t o  
n 
the  g a t h e r i n g  of impor tan t  s c i e n t i f i c  i n fo rma t ion ,  was t o  
g a i n  a d d i t i o n a l  exper ience t h a t  cou ld  be a p p l i c a b l e  t o  the  
lunar  sample recovery  program. 
I t  was dec ided t o  concent ra te  on low mo lecu la r -  
we igh t  o r g a n i c  canpounds t h a t  a re  n o r m a l l y  v o l a t i  le.  I n  t h i s  
manner i t  may be poss ib le ,  f i r s t ,  t o  determine what o rgan ic  
gases were sampled from the  s o l a r  nebula d u r i n g  fo rma t ion  of 
p l a n e t a r y  o b j e c t s  and, second, t o  d i f f e r e n t i a t e  between 
b i o g e n i c  and nonbi  ogen i c components. 
were planned, an e x t r a c t i o n  l i n e  was b u i l t  and c a l i b r a t e d ,  
and a gas chromatography u n i t  was i n s t a l l e d .  Enclosed i s  a 
d e s c r i p t i o n  of the procedure t h a t  has been employed. 
o f  n a t u r a l l y  o c c u r r i n g  s t a b l e  isotopes o f  l i g h t  elements. 
I n  the  f i r s t  h a l f  o f  the budgetary year exper iments 
A second approach i s  the s tudy  o f  the d i s t r i b u t i o n  
I n  c o l l a b o r a t i o n  w i t h  D r .  Me lv in  S i  lverman, an i n v e s t i g a t i o n  
i s  b e i n g  undertaken on the f r a c t i o n a t i o n  of C ' 3 / c 1 *  i n  
methane and carbon d i o x i d e  i n  the produc ts  of metabol ism 
of methane o x i d i z i n g  and methane forming b a c t e r i a .  A dua l -  
c o l  l e c t i n g  h i g h - p r e c i s i o n  mass spec t rane te r  has been 
https://ntrs.nasa.gov/search.jsp?R=19670009791 2020-03-16T18:12:46+00:00Z
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c a l i b r a t e d  a g a i n s t  known standards and i s  now per fo rming  
s a t i s f a c t o r i l y .  I t  i s  capable o f  measuring mic rano le  quan- 
t i t i e s  o f  carbon d i o x i d e .  
I n  connect ion  w i t h  i so tope  measurements,, a vacuum 
l i n e  has been e s t a b l i s h e d  f o r  the q u a n t i t a t i v e  r e d u c t i o n  o f  
s u l f a t e  w i t h  g r a p h i t e  t o  carbon d iox ide .  The 0 /O 
v a r i a t i o n  w i  1 1  be measured i n  t e r r e s t r i a l  and m e t e o r i t e  
s u l f a t e  t o  determine i f  d i f f e r e n c e s  e x i s t .  A d e s c r i p t i o n  
of the technique i s  enclosed. 
18 16 
1. Low- bo i  1 i ng compounds. 
Our e f f o r t s  d u r i n g  the  p e r i o d  from June through 
November 1966 have been d i r e c t e d  toward the s e t t i n g  up o f  
p r e p a r a t i v e  and a n a l y t i c a l  inst ruments f o r  the i s o l a t i o n  and 
i d e n t i f i c a t i o n  o f  the low-boi l i n g  o rgan ic  compounds fran 
s o i  Is, sediments, and me teo r i t es .  A gas c o l l e c t i o n - t r a n s f e r  
m a n i f o l d  has been cons t ruc ted  from g lass  and me ta l  components 
t o  e l i m i n a t e  the contaminat ive  e f f e c t s  of greased stopcocks 
and polymer tub ing.  Sample c rush ing  i s  c a r r i e d  ou t  i n  an 
evacuated h i g h - p u r i  t y ,  impermeable alumina capsule and i s  
connected t o  the m a n i f o l d  v i a  a f l e x i b l e  meta l  tub ing.  Gas 
t r a n s f e r  i s  accomplished by a mercury-powered Toepler pump 
wh ich  compresses the v o l a t i l e  m a t e r i a l  i n t o  a smal l  volume 
c o l l e c t i o n  tube t h a t  can be sea led  i n  g lass  f o r  f u r t h e r  ana lys i s .  
We a r e  c u r r e n t l y  t e s t i n g  the use o f  c ryogen ic  t r a p p i n g  of  the 
o r g a n i c  gases by the use o f  s i l i c a  g e l  a t  l i q u i d  n i t r o g e n  
temperatures.  T h i s  can be done q u a n t i t a t i v e l y  f o r  a l l  hydro- 
carbon gases i n c l u d i n g  methane, b u t  the problem o f  recovery  
o f  the  a r a n a t i c  gases from the s i l i c a  g e l  may prec lude the use 
of t h i s  technique. 
v e r s a t i  l e  gas-chromatographic ins t rument  f o r  the s e p a r a t i o n  
and i d e n t i f i c a t i o n  of the v o l a t i  l e  compounds. Since gas-chroma- 
tography  may be the  s o l e  means o f  i d e n t i f i c a t i o n  due t o  the l o w  
C o i n c i d e n t i a l l y ,  we have purchased and s e t  up a 
-3  - 
amount o f  ma te r ia l ’  p resent  i n  the  samples, we have decided 
on a h i g h - r e s o l u t i o n  c a p i l l a r y  system s o  t h a t  t he re  w i l l  be no 
amb igu i t i es  i n  e s t a b l i s h i n g  i d e n t i t y  of the canpounds. As 
a f u r t h e r  a i d  i n  i d e n t i f y i n g ,  we are s imu l taneous ly  u s i n g  a 
second means o f  d e t e c t i o n  - an e l e c t r o n - c a p t u r e  d e t e c t o r  which 
i s  s e n s i t i v e  t o  the e l e c t r o p h i  l i c  cha rac te r  of v o l a t i  l e  
compounds. The e f f l u e n t  gases f rom the capi  l l a r y  column i s  
s p l i t  i n  two s o  t h a t  h a l f  goes t o  each de tec to r .  The r e l a t i v e  
response o f  each canpound can then be used as a means o f  
iden t i f i ca t i on .  
We are c u r r e n t l y  invo lved i n  work ing 
duc i  b l e  method o f  temperature-programming from 
temperatures and i n  ca 1 i b r a t  i ng the apparatus. 
ou t  a repro-  
s u b- amb i en t 
2. 0 ~ 8 / 0 ’ 6  r a t i o s  i n  s u l f a t e s .  
A method has been developed t o  q u a n t i t a t i v e l y  reduce 
barium s u l f a t e  t o  barium s u l f i d e  and carbon d i o x i d e  by 
r e a c t i o n  w i t h  g raph i te .  Since one of the products  o f  the 
r e a c t i o n  i s  carbon monoxide, i t  i s  conver ted t o  carbon 
d i o x i d e  by d i s p r o p o r t i o n a t i o n  i n  a corona d ischarge.  The 
f o l l o w i n g  technique has been adopted. Approximately 20 mg o f  
bar ium su ’ l f a te  and 20 mg spec t rograph ic  grade g r a p h i t e  are 
weighed on a p iece  o f  g lazed paper. The m i x t u r e  i s  then 
ground i n  a smal l  s t e e l  mor tar  and p e s t l e  and t r a n s f e r r e d  
c a n p l e t e l y  t o  a p l a t i n u m  combustion c r u c i b l e .  The c r u c i b l e  
f i t s  i n s i d e  a molybdimum c y l i n d e r  t o  p revent  t i p p i n g  over and 
i s  then p laced i n s i d e  the furnace. The system i s  degassed a t  
6OO0C f o r  10 minutes by vacuum pumping. 
be less  than one mic ron  a f t e r  10 minutes.  
The pressure should 
Before r e a c t i n g  the sample, the U t r a p  i s  immersed 
i n  l i q u i d  n i t r o g e n  t o  c o l l e c t  carbon d i o x i d e  f r o m  the r e a c t i o n  
and a spot  o f  l i q u i d  n i t r o g e n  i s  p laced on the t i p  o f  the 
corona vessel  t o  c o l l e c t  C02 f rom the d i s p r o p o r t i o n  r e a c t i o n .  
I . 
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Valve 1 i s  shu t  and v a l v e  2 and va l ve  3 are  open. The pumps 
a re  shu t  o f f  and the furnace i s  heated f rom 95O0-10OO0C. 
the pressure  begins t o  r i s e ,  va l ve  2 i s  ad jus ted  s o  t h a t  the 
pressure of C O  i n  the corona i s  kep t  under 100 microns and 
the corona i s  turned on. The pressure i n  the corona chamber 
remains h i g h  as long as the r e a c t i o n  i s  con t i nu ing ,  b u t  as 
the C O  i s  conver ted t o  C02 and f rozen  i n  the bottom o f  the 
t rap ,  the pressure begins t o  f a l l  a f t e r  about 10 minutes when 
the r e a c t i o n  i s  over.  The furnace and h i g h  v o l t a g e  are  then 
shu t  o f f .  The l i q u i d  n i t r o g e n  on the U t r a p  i s  exchanged 
f o r  d r y  i c e  - acetone .to ca tch  any water and t o  a l l o w  the C02 
c o l l e c t e d  from the r e a c t i o n  t o  d i s t i l l  over i n t o  the corona 
vessel .  I f  there  i s  any C O  present  the corona i s  a c t i v a t e d  
t o  b r i n g  the pressure down. Valve 2 i s  shut,  n i t r o g e n  i s  
p laced on the c o l d  f i n g e r  and the C02 i s  a l lowed t o  f reeze 
over and be measured and c o l l e c t e d .  
When 
I. R .  Kaplan 
P r  i n c i  pa 1 I n v e s t  i ga to r  


Analysis of ancient sediments and extra-terrestrial materials Semiannual report, 1 Jun. - 30 Nov. 1966

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