The methods and results of determination of the argon and carbon isotope compositions of hydrocarbon gases of Mezozoic complexes of Western Siberia are presented. Based on the Ar-36, Ar-40, C-12, C-13 content of the various deposits and on the presumed mechanisms of entry of these isotopes into the deposits, it is concluded that formation of natural gas in some deposits included vertical migration from a lower complex

Gavrilov, Y. Y.

Teplinskiy, G. I.

Zhurov, Y. A.

English

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j	 N
NASA TECHNICAL MEMORANDUM NASA TM-75134
THE RELATION BETWEEN ISOTOPIC COMPOSITION
OP ARGON AND CARBON IN NATURAL GASES
Ye.Ya. Gavrilov, Yu. A. Zhur ,)v, and G.I. Teplinskiy
(NASA-TN- 7 134) THE RELATION BETWEEN	 N77-30680
ISOTOPIC CGP,ECSITION CF ARGON AND CARBON IN
NATURAL GASES jKanner (leo) Associates)
10 p BC A02/NIF A01	 CSCI. 08G	 Unclas
63/46 42126
t
Translation of "0 sv yaziizotopnogo sostava argona i ugleroda
v prirodnykh gazakh," Doklady Akademii nauk SSSR,
Geokhimiya, Vol. 206, No. 2, 1972, p. 448-451
o	 SEP 1977
RECEIVED
NASA s11 FACiUlt
^l	 INPUT
O
NATIONAL AERONAUTICS AND SPACE ADMINISTRATION
WASHINGTON, D.C. 20546
	 July 1.977
STANDARD TITLE PAGE
f"
1.	 Re o t No.
	
TM -75134_____
___
T.
	 Government Accession No. 3.	 Recipient's Catalog No
4.	 Title and Subtitle
THE RELA`1'iUN	 }BETWEEN	 ISOTO^'-TC	 COMPOSI`I'15,I
S.	 Report Dave July
	
1 !?7'
6.	 Performing Organisation CodeOF ARGON AND CARBON IN NATURAL GASES
7.
	 Author(s)
ie.Ya.
	
Gavrilov,	 Yu.	 A.	 Zhurov,	 and
8.	 Performing Organisa'ion	 !*port No.
10.	 Work Unit No.,.I.	 Teplinski,y
11.	 Contract or Grant No.
9.	 Performing Organisation Name and Address 1J ^'jj.;—c"C L
Type of Report and Period Covered
Trur!s1at, i_uI)
Leo	 KanTli'r	 Ass o,^ 1 atez	 113.
R ­ ii,:nod	 ('it,y,	 ('^1 9 fornia	 94 06 3
12.	 Sponsoring Agency Name and Address
National Aeronautics and Space Admini;-
tration,	 Washington,	 D.C.	 20546
-la.	 Sponsoring Agency cad.
15.	 Supplementary Notes
Translation of "Osv ,yazi izotopr.ot;c sostava argona i uf;leroda
v prirodn ,ykh gazakh," Doklad,y 	 Akaderr,ii	 nauk SSSR,	 Vol.	 206,
No.	 2,	 1972,	 p.	 448-451
16.	 Abstract
The methods and results of deter m ination ')f the ar-on and
carbon isotope compositions of hydrocarbon gases of Mezozoi('
complexes of Western Siberia are presentee. 	 A linear rela-
tionship	 exists between atmospheric arvon an y]	 A 14' of the
various deposits.	 Based on the	 36 Ar,	 40Ar,	 12t.,	 and	 13C
content of the various deposits and on the presumed mechanis ms
of entry of these isotopes into the deposits, 	 it is concluded
that formation of natural gas in some deposits included ver-
tical migration from a lower complex.
17.	 Key Words (Selected by Author(s)) 18.	 Distribution Statement
Unclassified-Unlimit^--d
19.	 Security Closul. (of this report) 20.	 Security Class.(. (of this page) I. No	 of Pages 22	 Price
U11CiU6_2 i flvi_1 i;nCiLi;-,iI1ed
NASA HO
_;
F
j
THE RELATION BETWEEN ISOTOPIC COMPOSITION
OF ARGON AND CARBON IN NATURAL GASES
Ye.Ya. Gavrilov, Yu. A. Zhurov, and G.I. Teplinskiy
In study of the isotope .composition of carbon and argon 	 /448*
in the hydrocarbon gases of the Mesozoic complexes of Western
Siberia, a relation of the isotope composition of the carbon of
methane to the content of -atmospheric argon in the gas was first
found. This relation of the isotope composition of carbon and
argon in natural gases should reflect the general regularities of
formation of the isotope composition of these elements. This is
of indisputable theoretical and practical interest.
Gases of the Pokurskaya series and its analogs (Aptian-
Albian-Senomanian) and Valanginian and.Jurassic locations were
studied. The gases were sampled in metal containers under
pressure, which excluded the intake of atmospheric argon from
the atmosphere. The separation and quantitative measurement of
argon were carried out in a Khlopin-Gering type installation,
with structural changes for determination of the argon content
of the gases. The isotope composition measurements were carried
out in a type MI-1305 mass spectrometer, by the triple beam method,
using a two channel inlet system with electromagnetic valves. At-
mospheric argon was used as the standard. Measurement accuracy was
f
j
i
t
at least+ 1.5%• The excess argon-40 was calculated by the
relation (%):
40Ar ex _	
(36Ar/ "Ar) air - ( 36Ar/ 40Ar)sample
	
T
(	 36Ar/40Ar)air j
The isotope composition of the carbon was determined by methods {
=j described earlier [1,2].	 The results are presented in the values
of 5 11C, relative to the internation_PDB standard.: The accuracy of {
^^
Numbers
I
in the marginindicate pagination in the foreign text.
l
p.l
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i s
.. r— ..— _.,^
.,,
i	 :; {. t:.i_, wd.%	 nveAoll . k	 .•	 i...	 :.	
-'
U'	 \5	 ClLrccnaait	 dno3pacr	 Ar	 do	 Ar 9	 \rnow	 a9bfzcro DO;a omle	 cea	 nep^pona4,u1.	 ¢ogacRro-	 113G'	 CFI:X	 pi,	 `La. x.	 %	 9.11.31.	 9.11.x.
oGUn 9r	 patx	 a 3m	 5 C
S^ornnscsoe	 3	 794-796	 Crism	 916,.7	 6,2	 7,2	 109 5	 -6 03
ioxcoxoahmoo	 7	 971-977	 :To me
	 89,3
	 10,3	 9,2	 80,1	 -5'47
lunurccf;oe	 6	 1148-1176	 »	 u	 68,1
	 8,4	 5,7	 62,4	 -5,29.
Ypeurolim<oe	 '13
	
1280-1230
	
a	 v	 63,2	 9:1	 5,8	 574	 -5.02
It"Inemme	 12	 1132-113$	 u	 r)	 58,8	 14,3	 8,4	 50.4	 4:93Ie^mm^l,e	 11	 1139-1165	 a	 n	 56,4	 13,5	 7,6 . 	48,8	 -4,91.
llecconxe-mo	 P-9	 $33-839	 n	 u	 26,5
	 31,8	 8,4	 18,1	 -4,11
^lonouonronct<oe	 79	 1796-1802	 Crivlg ..
	12,.1	 53, 41	 6,5 . 	5,5	 -
Ionotlopromnoe	 70	 1828-1835	 ^To am
	
7,2
	 53,9	 3,9	 3,3	 -3,00
, peuroiicroc	 17	 3000-3020	 J	 8,2	 59,7
	
4,9	 3,3	 I	 -3,84
I
b•
7•
determination of 6 136 was t 0.05%. The methane was extracted by
fractionation of the hydrocarbons.
i
	
The measurement results are presented in Table 1. A curve
of the isotope composition of the carbon of methane vs. atmospheric
argon content was plotted from these data. To explain the linear
relation, some questions of the geochemistry of the carbon and
argon isotopes, as well as the specific conditions of formation of
the gas deposits of Western Siberia, must be examined.
Table l
ISOTOPE COMPCSITION OF
METHANE CARBON AND ARGON OF NATURAL GASES
Deposit
Well #
Drilling :interval m
Reservoir age
Artotal^ PPM
40 Arex
Arrad ; PPM
Arair: PPm
Same
Vengayakhskoye
Komsomollskoye
Nydinskoye
Urengoyskoye
iiedve zh 1 ye
Messoyakhskoye
Novoportovsko,ye
Urengoyskoye
-2
'	 %*F.s.-- _ ., -..--, 	 _..^.__,.. arxe+mr-afF--=rrx^a:cnc-r	 --.
	
+wr,..-.	 __ _ ......._.-...m-. ..,...-vn..>*e.a•-....--...
Key: a.
b.
C.
d.
e.
f.
g•
h.
i.
1.
2.
3.
4.
5•
6.
7•
8.
It is seen from Table 1 and
t
Fig. 1 that the atmospheric argon
_.	
--ay	
!	 content of the Jurassic and Valan-.
too
9	 ginian deposit gases, which are 	 t
^b	 marine fascies, is significantly less
^so	 ^o4s
	
(3.5-5.5 ppm '), than that in the
,r	 Senomanian cor_,;inentalformations
•d	 6
F (18.1-109.5 ppm).	 According to the
^s°^,	 model of V.P.	 Savchenko [3], atmo-
spheric argon enters the gas form-
Fig. 1.	 1. Vengayakhskoye, 	 ations from connate waters, which
2. Komsomol'skoye,
3• Nydinskoye, 4. Uren-	 previously were in equilibrium with
goyskoye, 5. Medvezh'ye,	 the air.	 Under these conditions,
6. Messoyakhskoye,
7. Novoportovskoye,	 the maximum possible vapor pressure
8. Urengoyskoye deposits; 	 of atmospheric argon in the formations,
I. Senoman ian de osits; 
II. Jurassic and	 in readhing phase equilibrium, is
Valanginian deposits.	 determined by the temperature and
Key: a. ppm	 mineralization of the water in theb. Arair
sedimentation basin,on the one hand,
and by change in these parameters
during burial of the deposits, on the other hand.
	 However, the
t
difference in concentration of atmospheric argon in the gases of
the upper and lower complexes cannot be explained by a change in
solubility of the atmospheric argon with different mineralization
of the initial sedimentation basins or by change i.i temperature of
the connate waters
	 alone, since the difference in argon concen-
tration in this case is not over 1.5-2 fold.
The change in argon vapor pressure in the gas formations is
not changed by the phase equilibrium mechanism alone.
	 Argon from
the 1^-siding system car, be removed together with the hydrocarbons,
1 ppm	 parts per million.
3 P
.J
4,	 r
,^	 ^ . A
r
I-	 3
by migration of the latter in the gas phase. In this case, the
connate waters., which are the supplier of argon to the gas form
ation, are depleted of argon [4], which determines a reduction in
the maximum possible vapor pressure in the newly formed gas form-
ation. With the migration of hydrocarbons from the bedding system,
both atmospheric and radiogenic argon nre lost. The fact that
radiogenic argon is continually generated and enters the bedding
system and the atmospheric, in the absence of active infiltration
water exchange, is not replenished, leads to the situation that the
percentage of radiogenic argon in total argon increases with the
passage of time.
The low Arair and Arrad concentrations, as well as the in_
crease in Arex concentration in the gases of the Jurassic and
l
	
Valanginian deposits can be explained by the export of argon by
the hydrocarbdn gases to 	 the atmosphere,before deposition of
a clay covering during the Valanginian. There was less migration
of gases to the atmoshpere from the Senomanian deposits, in
connection with the fact that the regional Turonian--Paleogene
clay cover developed before submergence of the parent gas form -
ation into the catagenesis zone, i.e., before the beginning of
active gas formation in the Pokurskaya series. The assumption
made, of large scale loss of gas from the lower complex, is con -
firmed by the distribution of _radiogenic argon, the content of
which in the Senouanian deposit gases averages 1.5 times that of the
Jurassic and Valanginian deposit gases. In this case, the pos-
sibility of post-Valanginian vertical migration of the hydrocarbons
through lithofascial windows of the Valanginian covering is not
excluded since the latter was not maintained lithologically. This
process leads to the entry of gases into the upper complex, which
are depleted of Arair. This should cause a reduction in its con.
centration in the Senomanian formation gases. The mixing of
Ll
,I
r
Ii
s n exieic ases.of.the.Pokurs ka a	 ry g	 g	 Y series with gases of the lowe..
comple-k ih various proportions was the cause of wide variations
in the atmospheric argon content of the upper complex gases. In /450
this case, migration of the gas ff'om the lower complex to the
upper was accompanied by its enrichment in methane, compared with 	 } .
the heavier hydrocarbons [5].
I
The role of vertical migration in the formation of the
Senomanian formations was noted earlie- [6,7]; together with this, 	 II
a number of authors [8,9] deny the possibility of the development
-^of vertical migration in this region. Recently, works [10,11]
have been published, in which an attempt is made, on the basis of
differences in isotope composition of the carbon of i,he gases of
the two complexes, to confirm the latter point of view, without
td
considering the variations in isotope composition of carbon within
the complexes, in this case.
A combined examination of the isotope composition of carbon'
and argon and determination of the relations between the isotopes
of these elements has permitted a new interpretation of the ex-
perimental data.
a
On consideration that the methane formed at various stages
`^
of 'conversion of organic matter was more enriched in the light
r
isotope 12 C than the methane of the latter stages of gas	 gener-
9
ation [12], it can be assumed that the losses of the hydrocarbons
of early stages of gas generation of the gas parent deposits in ?
vertical migration leads, in the general case, to an increase in
the contrast of the isotope composition of carbon of the methane '	 a
of the gas formations locat6d at different depths. 	 Consequently,
the same process, the process of the loss of gas by the parent gas i	 1
"deposits, leads to a unidirectional change in the isotope compo- j
sitiort of both the methane 'carbon and argon. f
i
5
If it is assumed that the gas of the Senomanian formation
of the Vengayakhskoye deposit is syngeneic, to decide from the
maximum atmospheric argon concentration (109.5 p pm) and from the
minimum It isotope content of the methane (OC = -6.03%), the
variations in isotope composition of carbon can be explained by
mixing of the syngeneic gases and those migrating from the lower
complex, in which the fraction of the migrating gases differs in
different formations. It is at a maximum in the gas of the
Messoyakhskoye deposit, exceeding 75%. The correctness of this
assumption is confirmed by the linear relation between !hair and
d 11C.
Thus, the conditions of formation of gas deposits affects
the distribution of the argon and carbon isotopes in the formations
to a considerable degree, and joint study of them can be a sup-
plementary demonstration of the conditions of the migration and
accumulation of natural gases. Such a combined study of the
isotope composition of the elements has already yielded positive
results. Thus, a study of the carbon and sulfur isotopes [13,14]
has enabled the basic features of native sulfur deposits to be
determined and a number of questions of the genesis of sulfur de-
posits to be answered.
Thecombined study of the isotope composition of carbon and
argon in natural gases we have performed pi ,ovides a qualitatively
new possibility of interpretation of the conditions of formation
of gas deposits.
It should be noted in conclusion that atmospheric argon is
found, not only in the free and dissolved gases of sedimentary
strata, but in the gases of all. minerals studied, of both sedi-
mentary and magmatic rock. This permits the use of data on the
6
VI'
a^
atmospheric argon content in both gas geology, and in the
answering of questions relating to determination of the conditions
i
of lithogenesis and metamorphism of sedimentary rock. 	 j
The authors thahk V.P. Savchenko, A_e. Kozlov, and Yu. A.
Borshchevskiy for discussion of the manuscript and for valuable
comments.
4
rya
{	 y
1
5
^- I r L'
5
1
I
j.
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na primere Zapadno-Sibersk-oy i drugikh epigertsinskikh plit
SSSR Conditions of Formation and Regularities of Deposition
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issue 3, 1967.
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A
9. Nemchenko, N.N. and A.3. Rovenskaya, Geol. i ra7.v. mazovykh
ag zokondensatnykh mestorozhdenLL [Geology and Developmerrt
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nefti i gaza 6,(1968).
11. Vasil'yev, V.G,, V.I. Yermakov et a1, Ibid. 4, (1970).
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10, (1961).
14. Dessau, G., M.L. Jensen and N. Nakai, Econ. Geol. 57, (1962)
8


The relation between isotopic composition of argon and carbon in natural gases

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