" • "~ JOURNAL OF

PETROLEUM
SCIENCE &
ENGINEERING
E LS EV l ER Journal of Petroleum Science and Engineering 10 ( 1994 ) 311-319

Types and genetic characterization of spring gases in eastern China

Song Yah, Dai Jinxing, Wang Darui
Scientific Research Institute of Petroleum Exploration and Development, P. 0. Box 910, Belting 100083, China
(Manuscript received May 30, 1993; revised version accepted November 8, 1993 )

Abstract

Based on the analytical data o f gas components, carbon and helium isotopes from more than fifty samples, three
major types of ( h o t ) spring gases in eastern China are identified. Type I is d o m i n a t e d by carbon dioxide with
higher 5 ~3Cco 2 values ( > - 70/ooP D B ) , and originates from volcanic magma or a mixture o f magma and carbonate
metamorphism. Type II is d o m i n a t e d by nitrogen and is related to meteoric waters. Type III is d o m i n a t e d by
methane (CH4) with lower 513 C1 values ( -- 53.1 o/ooto -- 65. l°/oo PDB) and is principally a biogenic gas.

1. Introduction economic possibilities, more than fifty samples

Hot spring gases with complex origins occur
over wide areas in eastern China. These gases are
affected by volcanic activities, block faulting,
biogenic activities and underground water
movement. The spring gases reflect directly the
presence of underground gases. The research on
spring gases has great significance in the explo-
ration of natural gases. Further, there is a close
relation between spring gases and gas from mag-
matic origin. Inorganic primary gases, which were
generated by degassing reactions of the mantle,
migrate along deep faults, zones of subduction,
oceanic ridges, and are transported through
magmatic intrusions or volcanic eruptions into
sediments, the hydrosphere and the atmosphere,
This degassing reaction can be investigated di-
rectly in relative shallow springs. This study will,
therefore, enrich the theory of the inorganic gen-
esis of natural gases,
In order to come to a classification, to gain in-
formation concerning the genesis, and distribu-
tion of gases in hot springs, and to explore its
were investigated for this study from the Yun-
nan, Sichuan, Jilin and Guangdong Provinces
and from Inner-Mongolia (Fig. 1 ). The samples
were analyzed for gas components, carbon iso-
topes of CH4 and CO2 and helium isotope (Ta-
ble 1 ).
2. Assemblage types of spring gases
The analyses revealed three types of gases:
(1) Gases dominated by CO2 (type I). About
60% of the gases belong to this type; the gas con-
tains more than 80% CO2, usually more than 90%
CO2, and in some samples, it has an extremely
low amount of CH4;
(2) Gases dominated by nitrogen (type II) con-
tain more than 90% nitrogen, some CO2 and
some samples have CH4. 30% of the gas samples
belong to type II; and
( 3 ) Gases dominated by CH4 (type III). These
gases are only found samples collected from
Baoshan County, Yunnan Province. This type

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312 S. Yan et al. / Journal of Petroleum Science and Engineering 10 (1994) 311-319

"°l ~ol 13ol -ol

ml 4j

[ ~ o Haerbin

Changchun 0 4o
==2 3

o Xian so

• m 13 Yangtze River
O Chengdu

114
2_5
Fuzhou

¢ z..20

"ol , ~oI 13ol

Fig. 1. Study area and sample location. 1. Wudalianchi in northeastern China, 2. Reshui County, Inner-Mongolia, 3. Changbai
Mountain in northeastern China, 4. Pingjiang, Hunan Province, 5. Pingyuan, Guangdong Province, 6. Fengshun, Guangdong, 7.
Mile, 8. Panxi, Yunnan, 9. Chuxong, Yunnan, 10. Lufeng, Yunnan, 11. Baoshan, Yunnan, 12. Tengchong, Yunnan, 13. Ganzi,
Sichuan Province, 14. Hainan Province.

contains little CO2 and N 2 (Table 1 and Fig. 2 ). either CO2 or N2 is the dominant component; (2)
The results presented in Fig. 2 and Table 1 all samples (except a few gases from the Baoshan
show that the main characteristics of the corn- County and Yunnan Province) have extremely
portents in spring gases in eastern China are: ( 1 ) low CH4 contents (less than 1%); ( 3 ) heavy hy-
 S. Yan et al. / Journal of Petroleum Science and Engineering I 0 (1994) 31 I-3l 9 313

Table 1
Results of the analyses of (hot) spring gases in eastern China

Location Sample Components (%) 613C ( P D B ) 3He/4He

CO2 N2 CH 4 Ar He d 13C 1 d 13Cco2

Lufeng 6 99.05 0.69 0.26 -6.0

Chuxiong 1 97.71 2.29 -6.0
Tengchong 2 96.41 3.59 -6.3
Ganzi 6 94.53 2.20 3.16 0.035 0.008 -26.60 -2.46 4.99+0.14) X 10 -7
Pingyuan 5 97.87 1.55 0.00 0.041 0.014 -4.24 3.09+0.09) X 10 -6
WuDaLianchi 6 93.79 6.0 0.00 0.156 0.049 -3.87 4.43+0.12) X 10 -6
WuDaLianchi 4 98.20 1.80 0.00 -3.93 4 . 1 7 + 0 . 1 2 ) × 1 0 -6
WuDaLianchi 3 83.06 16.79 0.15 -6.84
Changbai 2 99.64 0.29 0.06 0.010 -24.04 -5.81
Hainan 1 0.03 99.82 0.15
Tengchong 2 0.28 99.72
Fengshun 7 3.77 95.64 0.58* -51.16 - 12.28
Mile 1 3.84 94.83 0.35 0.90 0.077 -8.62 3.14+0.19) × 10 -8
Reshui 2 0.19 97.84 0.26 1.05 0.66 -22.74 - 16.05
Baoshan 3 8.84 0.86 90.3 -65.1

*also with C2H 6 (0.01%).

drocarbon fractions (e.g., ethane and heavier)
were not found, with the exception of one sam-
pie from Fengchun County, Guangdong Prov-
ince, which had an ethane content of about
0.01%.
3. The genesis of the gas types
3.1. Type I (CO: as the dominant component)
The CO2 content in type I spring gases is high
and contains heavy carbon isotopic ratios be-
tween - 1o/00and - 7%o (PDB).
Although the CO2 genesis is rather complex, it
can have organic origin (including microbiolog-
ical decomposition of organic matter), it can be
formed by thermal degradation ofkerogen, ther-
mal decomposition of oil and combustion gases,
and it can have an inorganic origin caused by
metamorphic processes of carbonates and de-
gassing from magma. Due to the difference in the
isotopic compositions of original carbon
matter for generating CO2, generally the
t~13Corg< __200/00 and ~ 13Cinorg> __ 100/00. The ob-
vious difference in 813C values present in the
carbon dioxides are caused by the organic or in-
organic origin. Moreover, alkane is the domi-
nant phase in the organic gases, but CO2 in the
inorganic gases. Therefore, CO2 abundance is
another measure for identifying the type of gases.
Based on the information from both in and out
of China, the authors made an identification
chart (Fig. 3 ). It is evident that CO2 with 813C
values lower than - 10%0 belongs to organic gas;
CO2 with values higher than - 8%0, belong to in-
organic gas. The gases with values between
- 10%0 and - 8%0 form an overlap of organic and
inorganic CO2. Generally, the CO2 content ofin-
organic gas ranges from low to 100%, for organic
gas, is always below 20%.
Two distribution areas can be clearly recog-
nized in Fig. 4. All the spring gases with high CO2
content fall within area I. Therefore, they are of
inorganic origin.
There are two different mechanisms to gener-
ate inorganic CO2. The first mechanism is high-
temperature decomposition of carbonate, a met-
amorphic process with carbonates:
C a C O 3 ~ C a O + CO2 ( 1)
The metamorphic reaction between carbonates
314 S. Yan et al. /Journal of Petroleum Science and Engineering 10 (1994) 311-319
and silicate minerals is (Patelik, 1968 ):
7MgCa(CO3)2 +2.5 A12Si205 (OH)4
dolomite kaolinite
+ H 2 0 + 3Fe 2+ + 3.502- ~
Mg7 AI2 Fe3 Sis A13020 ( O H ) 16
chlorite
+ 7CACO3 + 7CO2
and:
4CACO3 + K2A14Si6A1202 (OH) 4
calcite potashmica
+ 6SIO2 +Fe 2+ + O 2 - ~
quartz
2Ca2A12 FeSi30 t2 (OH) + 2KAISi30s
epidote K-feldspar
+4CO2 + H 2 0
Temperature is the controling factor in these
subsurface reactions. Weeping rocks/fracture
zones, ferrous-rich brine and the continuous re-
lease of generated carbon dioxide are the basic
conditions for metamorphism of calcite to gen-
crate CO2. The second mechanism originates
from mantle magma. A great volume of CO2 is
separated out because of a decrease in tempera-
ture and pressure during lifting of mantle magma.
This theory has been proven by studies on stim-
ulated conditions of heated igneous samples
(Table 2) (Guan X.R., 1990).
Both types of inorganic CO2 mentioned above
have heavier 613Cco2 values. The CO2 generated
from the metamorphic reaction of carbonate has
a slightly more positive 613Cco~ than the vol-
canic gases. Usually, both values are overlapping
and too close to be identified by carbon isotopes
of CO2. The authors used the following addi-
tional methods to distinguish between them.
(1) Ratio of 3He/4He. Helium in original man-
tie material has a heavier isotope ratio with 3He/
4He ranging from 1.1 to 1.4× 10 -5 (Wang X.B.,
1989 ). Radiogenic helium has a lighter isotopic
ratio of 3He/4He (nX 10 -8) than atmospheric
helium, which is the mixed product of both man-
tie and radiogenic helium, and has an 3He/4He
ratio of 1.4× 10 -6. Because mantle helium is
often mixed with radiogenic helium during lift-
ing, helium with a higher ratio of 3He/4He (up
to 1.4 × 10--6) in gas accumulations are often
thought to have a mantle origin.
Due to the affinity of some coexisting compo-
sitions in gases, it can be inferred that magmatic
C O 2 should be associated with mantle source he-
lium, however, CO2 generated from carbonates
(2) should be associated with crust origin radioac-
tive helium.
(2) Analyses of geologic characters. Volcanic
activity is a prerequisite for the formation of
magmatic gases; therefore, the possibility of the
existence of such gases can be estimated using
historical records of volcanic activities and the
presence of magmatic rocks. For example, vol-
canoes of Wu-Da-Lianchi in northeastern China
(well-known as "Volcano Museum"), produce
(3) springs with CO2 contents up to 83.6-99.95%0,
613Cco2 values ranging from --3.830/o0 to
-6.84%o and 3He/4He ratios ranging between
(4.43_+0.12)X10 -6 and (4.17_+0.12) X10 -6
(i.e., higher than for air, 1.4 × 10-6). Therefore,
CO2 in Wu-Da-Lianchi mainly originated from
an inorganic mantle source.
In Pingyuan County, Guangdong Province,
zones of CO2 gas seepage are distributed along
huge faults and close to magmatic rocks.
613Cco2values range from - 3.39°/0oto - 4.79°/o0,
3He/4He ratio is (3.09 + 0.09 ) × 10-6. This gas
comes mainly from the upper mantle (Dai J.X.
et al., 1990).
The spring gases dominated by carbon dioxide
are basically distributed within areas of high heat
flow caused by the emplacement ofmagmatic and
metamorphic rocks in eastern China. The distri-
bution is principally controlled by tectonic
movements, such as huge faults. For instance, in
the Dianshi area, the strong tectonic movements
and volcanic activities in the Cenozoic caused li-
bration of a vast amount of CO2 from plutonic
intrusions and numerous springs were formed
with high CO2 contents (Dai J.X., 1988; Shang-
guan Z. and Gad S.S., 1990). In some of the car-
bonate sediments, however, the metamorphic
process of carbonate pyrometamorphosis can
similarly librate CO2, caused by magmatic heat.
Therefore, mixed gases of both volcanic-mag-
 S. Yan et al. / Journal of Petroleum Science and Engineering 10 (1994) 311-319 315

C02
xoo%

o Bao6han, Yunnan a//# " '~~ A Ganzi, Sichuan

• Tengehong and Chuxiong,
Yunnan • ~ Pingjiang, Hunan
<>Panxi and Mile, Yunn . Wudalianchi,
-e Northeastern China
<! Pingyuan, • ÷ ~ Changbai Mountain,
Fengshun, o~ Northeastern China
®Guangdong •X ~ Reshui, Inner-Mongolia
x
land

CH4 N2
20% 20%
COz COz
40% ~o~

CH4 N2 CH4 N2
100~ 40~ 10% 100%
Fig. 2. Plots showing the distribution of the components of hot spring gases in China.

matic and carbonate-metamorphic origin can be
found in these regions.
3.2. Type H (N2 as the dominant component)
Type II spring gases are usually found in areas
favorable for precipitation cycles. 02, constantly
carried into the subsurface by precipitation is
easily consumed during oxidization, N2 is stored
in groundwater and interstices and then can re-
turn to the surface in springs (Fig. 5 ).
Apart from the high N2 content, the spring
gases also are characterized by the following. ( 1 )
The gases have a very low CO2 content because
the carbon dioxide generated at the surface or in
shallow strata is carried away by surface water
into the subsurface; these springs not only have
a low content of CO2 but also a low t~13Cco2,
< - 8%o, these samples appear in areas of or-
ganic-origin CO2 (Fig. 4). (2) The underground
 316 S. Yan et al. / Journal of Petroleum Science and Engineering 10 (1994) 311-319

--40

[~ OrganicC02 in China
Organic CO, out of Ch/na
[~ InorganicC02 in China
-- 30 ' [~ InorganicCO, out of China
o I

[--~ OrganicCO, area

• ' ~ InorganicC02 area
, o [ ~ Mixed area with both inorganic
• and organic C02
--20

t~
o°
f-~
!,,a • •

t~
i~..o.
'i"
~.. •
• 0

, Oo
--10
--8 •,, •A • • ~.,[ I t~ 4 4~x
4 4
• ~
]1
•

• 4 ( ~ •42 4 • , 4 , • ••
AZX ~4
• , . ~ 4 •
4

• 4

0 " • 4 4 II •

-I-8 ~ , , •
i

0 i0 20 30 40 50 60 70 80 90 I00

C02 Content ( ~ )

Fig. 3. Identificationchart for organic and inorganicCO2 (ReferencesincludingAustralia, Tailand, New Zealand, The Philip-
pines, Canada, Japan and Russia).

water associated with the spring gases have high the springs are filled by atmospheric precipita-
H C O ; content in carbonate sediments. This is tion (Ying W.H. and Hung L.H., 1989). The
caused by reactions between atmospheric pre- fi~3r,
'--,CO 2 values range from 12.64%o to
cipitation and the carbonate sediments. The six- -18.83% o, i.e., the CO2 has an organic origin.
teen springs on Sangzhi-Shimen synclinorium in The groundwater is of H C O ; -type.
northwestern Hunan Province have N2 content Where magma is present, the spring gas in in-
up to more than 90%. The D H 2 o value shows that filtrated by gases from magmatic origin. For ex-
 S. Yan et al. / Journal of Petroleum Science and Engineering I0 (1994) 311-319 317

' z&ir'q I
°- ++i ° [
+
I
+ ,;÷J

g
5O

0 -10 -20
51SCco, (PDB, ~00)

Fig. 4. Distribution of CO2 content and J~3CO2 values of spring gases in eastern China. I: inorganic CO2,//: organic CO2 (for
legend see Fig. 1).

Table 2 T h e spring w a t e r has certain rare elements asso-

Gas compositions in different types of igneous rocks ciated with m a g m a t i c rocks a n d radioactive
Rock Gas composition (%) elements.

CO2 H20 CO CH 4
3.3. Type III ( C H 4 as the d o m i n a t e d component)
extrusive rock 66.0 19.4 12.3 2.3
basalt 64.6 19.9 13.8 2.5
andesite 74.6 13.6 10.6 2.2
rhyolite 57.1 30.6 12.3 This gas, with ~ I 3 C c H 4 values ranging f r o m
intrusive rock 25.5 67.6 4.5 2.5 --53.1%o to --65.1%o, was f o u n d in only one
gabbro 16.6 77.4 3.7 2.3 spring in B a o s h a n County, Y u n n a n Province.
diorite 12.0 80.6 3.2 4.3
granite 33.4 59.5 5.2 2.3 Based on the collected data, the authors esti-
diabase 44.7 50.7 3.2 1.9 m a t e d the distribution of~13CcH4values for dif-
whole rock 47.5 42.0 8.0 2.5 ferent genetic C H 4 types (Fig. 6 ). It is clear that
the $'3CcH , values fall within the area o f bio-
genic gas. Therefore, CH4 in this spring gas is
ample, spring gases in a high terrestrial heat flow generated b y bacterial f e r m e n t a t i o n on the sur-
area caused b y m a g m a in K e s h i k e t e n g C o u n t y , face, or within shallow sediments, a n d then
I n n e r - M o n g o l i a , are e n r i c h e d in inorganic CH4. t r a n s p o r t e d with g r o u n d w a t e r to the surface.
318 S. Yan et al. / Journal of Petroleum Science and Engineering 10 (1994) 311-319

Nz-'~Oz

o I l+co, 1 I N, +.,o
CO2

_0_o .,<

Fig. 5, Schematic drawing of the geochemicalcycle of atmospheric N2.

i i I I I I i

I ! Inorganic C H (

I CH( of coal-type gas

4 CH( of oil=type thermal cracking gas

) q CH( of oil-type thermolysis gas

•--I CH( of biogenic gas

• & CH( in hot spring of Baoshan county, Yunnan

! r ! I r 1 I i

--80 --70 --60 --50 --40 --30 --20 --10 0

5J3C (PDB, %0)

Fig. 6. Distribution of ~ ~3CcH, values for different genetic origins of CH4,

4. Conclusions the vicinity o f faults, using pathways for lifting

and m o v e m e n t o f u n d e r g r o u n d water and spring
The results o f this investigation suggest that gases. The fractured zones provide an ideal place
spring gases in eastern C h i n a usually appear in for the a c c u m u l a t i o n o f water and gas. Spring
 S. Yan et al. / Journal of Petroleum Science and Engineering 10 (1994) 311-319
g a s e s h a v e c o m p l e x o r i g i n s : ( 1 ) T y p e I is m o s t l y
of a volcanic-magmatic origin, but can show a
mixture of both volcanic and carbonate-meta-
m o r p h i c gases, ( 2 ) T y p e I I h a s a n a t m o s p h e r i c
origin, and (3) Type III has a biogenic origin.
All three types, however, may have other
origins and show mixing of gases.
References
Dai Jinxing, 1988. Characteristics of stable isotopic compo-
sition and origin of the natural gas in Sulfur-mud Pool in
Tongchong County, Yunnan Province, China. Chinese Sci.
Bull., 33 ( 15 ): 1168-1170 (in Chinese).
Dai Jinxing, Zeng Guanyun and Chen Xueliang, 1989. Car-
bon dioxide show in Zeh-gulong, Pingyuan County,
319
Guangdong Province, China. Oil Gas Geol., 11 (2): 205-
207 (in Chinese).
Guan Xiaoru, 1990. Genesis of carbon dioxide with high pu-
rity in east China. Exp. Petrol. Geol., 12 ( 3 ): 248-257 (in
Chinese).
Patelik, L.J., 1968. The origin of carbon dioxide in Silto geo-
thermal system, southeastern California, U.S.A. 8th Int.
Geol. Conf., 17:185-194 (Chinese translation).
Shangguan Zhiguan and Gao Songsheng, 1990. Earthquake
and liberation of carbon dioxide in western Yunnan
Province, China. Seismol. Acta, 12(2): 186-192 (in
Chinese).
Wang Xianbin, 1989. Isotopic geochemistry and cosmo-
chemistry of rare gas. Science Press, Beijing (in Chinese ).
Ying Weihua and Huang Lianghan, 1989. The retention con-
ditions of natural gas in Lower Palaeozoic on the Sangzhi-
shimen composite syncline, northwest Hunan Province,
China. Oil Gas Geol., 10 ( 2 ): 170-180 (in Chinese).