ENERGY EXPLORATION & EXPLOITATION · Volume 32 · Number 4 · 2014 pp.

691–708 691

Geochemistry characteristics of hydrogen

sulphide-bearing gas pools in Sichuan Basin

Zhisheng Li1,2*, Jin Li1,2, Huiying Cui1,2, Dongliang Wang1,2, Se Gong3,

Jian Li1,2, Ying Zhang1,2, Chenghua Ma1,2 and Yifeng Wang1,2
1
Research Institute of Petroleum Exploration and Development, Langfang Branch,
Petrochina, Langfang, Hebei 065007, China
2
The Key Laboratory of Gas Formation and Development, Petrochina, Langfang, Hebei
065007, China
3
CSIRO Earth Science and Resource Engineering, North Ryde, NSW, 2113, Australia
*
Author for corresponding. E-mail: [email protected]

(Received 17 November 2013; accepted 26 February 2014)

Abstract
Sichuan Basin is the oil and gas bearing basin that is discovered in China, with
the most hydrogen sulfide gas pool and the greatest reserve. In this article, gas
pools with high hydrogen sulfide in Sichuan Basin were taken as the object of
study; the geochemistry characteristic of natural gas was systematically studied,
and the origin of natural gas with hydrogen sulfide in Sichuan Basin was
discussed. The hydrogen sulfide content in the hydrogen sulfide gas pools of
Sichuan Basin is 0.6%-14.5%; the sulfur isotope values of hydrogen sulfide gas
have a close relationship with the sulfur isotope values of anhydrite in the same
reservoir, and the sulfur isotope fractionation between the anhydrite and the H2S
is 4‰-14‰, showing that the H2S in natural gas and the anhydrite in reservoir
have the same sulfur source, the H2S in natural gas is the product of TSR
reaction. The relationship among the hydrogen sulfide content in the gas pool, the
hydrogen isotope of methane and the sulphur isotope of hydrogen sulfide is not
obvious; but the high hydrogen sulfide content corresponds to the heavier ethane
carbon isotope composition, and the carbon isotope of carbon dioxide is lower
than -10‰, which belongs to the organic origin and has further verified the fact
of TSR occurrence in the reservoir. There is the phenomenon of carbon isotopic
reversal of methane and ethane in some areas of the Huanglongchang gas field,
Wubaiti gas field and Puguang gas field in the Northeast Sichuan as well as
Weiyuan gas field in South Sichuan, which is mainly caused by the later period
of cracking-based gas-production process of the crude oil. TSR has less influence
on these gas pools.

Keywords: Geochemical characteristics, Sulfur isotope, H2S-bearing gas

reservoirs, Sichuan Basin
692 Geochemistry characteristics of hydrogen sulphide-bearing gas pools
in Sichuan Basin

1. INTRODUCTION
Hydrogen sulfide is widely found in natural gas reservoirs both in China and abroad
(Sokolov et al., 1971; Anderson et al., 1987; Machel et al., 1995; Desrocher et al.,
2004; Zhu et al., 2005), where the contents of hydrogen sulfide are usually less than
5%. The content of hydrogen sulfide at Jurassic limestone reservoir in South Texas of
the US is as high as 98%, ranking the first in the world; that at Zhao Lanzhuang gas
field in Jizhong depression is as high as 92% (Dai, 1985). China’s hydrogen sulfide-
bearing natural gases are mainly distributed in Sichuan Basin, Bohai Gulf Basin, Erdos
Basin and Tarim Basin with the contents of hydrogen sulfide usually less than 0.5%.
The existence of hydrogen sulfide in natural gas brings great danger to the exploration
and safety production of natural gas. Currently, most of the hydrogen sulfide-bearing
gas fields with industrial value found in the world are distributed in carbonate rock
strata. The extensively distributed marine carbonate area in China is an important field
for China’s oil and gas exploration in the future. Therefore, the research on the
genesis, enrichment and distribution characteristics of hydrogen sulfide has great
significance on China’s marine oil and gas exploration.
Foreign scholars began to study hydrogen sulfide early. Many scholars conducted
specific research and experimental analysis on microbial sulfate reduction,
thermochemical sulfate reduction, etc (Anisimov L.A., 1978; Ohmoto and Felder,
1987; Odom, 1990; Machel et al., 1995; Sun and Püttmann, 1996; Worden et al.,
1998; Vester and Ingvorsen, 1998; Saunders et al., 1999). China’s research on
hydrogen sulfide starts relatively late. Shen et al. (1982) and Dai (1984, 1985) are the
first researchers to study geochemical properties, formation conditions and
distribution pattern of China’s hydrogen sulfide-bearing natural gases. With the
discovery of high-content hydrogen sulfide-bearing gas in northeastern Sichuan,
relevant researches attract the attention of some scholars again. Shen et al. (1997),
Wang et al., (2002), Yang et al., (2002), Cai et al. (2003), Jiang et al., (2003), Zhu et
al., (2006), Xie et al., (2008) conducted a series of researches on the distribution,
source and formation of hydrogen sulfide-bearing natural gas in northeastern Sichuan.
It is agreed that the formation of hydrogen sulfide in the middle and lower Triassic and
Sinian gas pools in Sichuan Basin was due to TSR. Hydrogen sulfide levels and sulfur
isotopes are important indices for gas source correlation and formation research.
China’s scholars have made remarkable achievements in this field, but the research on
sulfur isotopes of hydrogen sulfide has obtained little results and is lack of system.
Sichuan Basin is the oil and gas-containing basin with the largest number of hydrogen
sulfide-bearing gas reservoirs and the largest reserves found in China. In this paper we
mainly study high-content hydrogen sulfide-bearing gas reservoirs in Sichuan Basin
using the newly established detection means for sulfur isotopes of hydrogen sulfide. A
comprehensive research was conducted over the formation of hydrogen sulfide by
combining with other geochemical data of the natural gases. We attempted to reveal
the accumulation patterns of these hydrogen sulfide-bearing gases in order to reduce
the exploration risks.
ENERGY EXPLORATION & EXPLOITATION · Volume 32 · Number 4 · 2014 693

2. GEOLOGICAL BACKGROUND
Located in middle and western China, Sichuan Basin is one of the largest basins rich
in natural gas, covering an area of approximately 18×104 km2. The basement of
Sichuan Basin is pre-Sinian system, and some areas even include lower Sinian
sediments. Marine strata developed from Sinian Period to mid-Triassic period are
mostly carbonate deposits, with the thickness of 4000 m - 7000 m; the upper Triassic
to quaternary system are continental sediments, which are mainly clastic rocks with
the thickness of 200 m - 5000 m. Seeing from the sedimentary evolution process of
Sichuan Basin, lower Cambrian, lower Silurian, lower Permian, upper Permian, upper
Triassic and lower Jurassic possess the proper geological conditions to form high
quality source rocks. Drilling results and analysis reports show that the first 5 series of
source rocks satisfy the standard of effective gas source rocks. Thus, they are the main
gas source rocks of Sichuan Basin gas reservoirs.
Lower Cambrian source rocks are mainly composted of argillaceous rocks and
carbonate rocks with effective thickness of 200 m-600 m. They are distributed widely
in the whole basin. The organic carbon contents are 0.3%-4.2%, averaging 0.6%; the
kerogen type is Type-I, with high evolution; the average Ro is 3.5%, and the source
rocks are at stage of mainly producing gas. The source rocks of lower Silurian
Longmaxi Formation are composed of black shale and mudstone rich in graptolite,
with the effective thickness of about 300 m. They are distributed mainly in eastern
Sichuan. The organic carbon contents are 0.4%-3.1%, averaging 0.8%; the kerogen
type is Type-I with high evolution; the average Ro is 2.0% or above, and the source
rocks are at stage of mainly producing gas. There are two geological cycles starting
from lower Permian Liangshan Formation to Qixia Formation and Maokou Formation.
The first segment of Qixia Formation formed during marine transgression and the first
and second segments of Maokou Formation are the most favorable sites for the
propagation of organisms and the formation of high quality source rocks. Source
rocks, mainly composed of biological limestone, are rich in foraminifers during the
climax of marine transgression. They are mainly distributed in southern Sichuan, with
the effective thickness of 200 m-400 m. The organic matter contents are 0.4%, and the
kerogen type is Type I and II; the Ro is above 2.0%, and the source rocks are at stage
of mainly producing gas. The sea-land transition facies source rocks of upper Triassic
Longtan Formation are mainly composed of carbonate rocks and coal (including coal
and dark mudstone). With the effective thickness of 130 m-250 m, they are widely
distributed in the whole basin. The organic carbon contents are 0.25% - 12%,
averaging 2.62%; the kerogen type is Type I, Type II and Type III, all in high-over
mature stages (Yang, 2002). The source rocks of upper Triassic Xu Jiahe Formation
are mainly dark gray or gray black mudstone, shale, carbon shale and coal, forming
deep lake-shallow lake-lakeside plain sediments. With large number of source rock
strata, this set of hydrocarbon source rocks are mainly distributed in western and
middle Sichuan. The effective cumulative thickness of source rocks is 150 m-450 m,
and organic carbon contents are between 1.2% and 6.4%. The kerogen type is mainly
Type III, at the mature-high mature stage (Zhu et al., 2006).
According to basement properties, sedimentary cover, gas reservoir (field) features,
natural gas types, etc, Sichuan Basin is divided into four oil and gas accumulation
694 Geochemistry characteristics of hydrogen sulphide-bearing gas pools
in Sichuan Basin

belts: eastern Sichuan gas field, southern Sichuan gas field, middle and western
Sichuan gas field (Fig. 1). Hydrogen sulfide-bearing natural gases are distributed in all
of the four gas reservoirs. Among them, eastern Sichuan gas field has the largest
content of hydrogen sulfide, which is mainly concentrated in middle Permian
Changxing Formation in northeastern Sichuan, lower Triassic Feixianguan Formation,
including Puguang and Luo Jiazhai, Dukou River, Tie Shanpo, Huang Longchang and
Wubaiti gas fields. In addition, high-content hydrogen sulfide is also found in
Jialingjiang Formation of Wolonghe gas field. Southern Sichuan gas field mainly
includes Weiyuan Sinian gas reservoir; middle Sichuan gas field mainly includes
lower Triassic Jialingjiang Formation and middle Triassic Leikoupo Formation gas
reservoir of Moxi gas field; western Sichuan gas field mainly includes middle Triassic
Leikoupo gas reservoir of Zhongba gas field.

Figure 1. Distribution of hydrogen sulfide-bearing gas in Sichuan Basin.

Hydrogen sulfide-bearing gas reservoirs in eastern Sichuan are mainly located in

upper Permian Changxing Formation, lower Triassic Feixianguan Formation and
Jialingjiang Formation, with front gentle slope of development platform, biological
reef and biological ford at the edge of platform, open platform and other lithofacies.
The reservoir space types are mainly intragranular dissolution pores, intergranular
dissolution pores, super-large dissolution pores and karst caves; the reservoir rocks are
mainly granular dolostone, reef dolostone and crystalline dolostone, with relatively
poor overall pore structure and generally belonged to crack-porous type low pore and
mid-low permeability reservoirs dominated by secondary porosity.
Weiyuan gas field in southern Sichuan is the oldest gas reservoir in China, which is
mainly distributed in Sinian Dengying Formation and Cambrian Xixiangchi
Formation. Reef flat and algal grain facies belt develop in Sinian Dengying Formation,
ENERGY EXPLORATION & EXPLOITATION · Volume 32 · Number 4 · 2014 695

with the lithology mainly composed of hidden algal dolostone with primary and
secondary pore development. The lithology of Cambrian Xixiangchi Formation is
light gray and beige micrite-powder crystal limestone, thin layer light gray sandstone,
dark gray shale and limestone with ooidal dolostone at bottom. The reservoir is mainly
distributed on top of Xixiangchi Formation. The lithology is dolostone. Dissolution
pores are distributed along the layer, and honeycomb-shaped karst cave layers can be
visible, forming crack-porous type reservoir.
Lower Triassic Jialingjiang Formation and middle Triassic Leikoupo Formation
gas reservoirs of Moxi gas field in middle Sichuan are evaporative carbonate and
gypsum sediments of marine intertidal facies and supralittoral zone. A set of carbonate
tidal flat and evaporative rock sediments forms in middle Triassic Leikoupo
Formation. The reservoir is distributed in upper and middle layers, and the lithology
is dolostone and limestone. The lower layer is gypsum dolostone; the middle and
upper dolostone and limestone are pure in quality. The pinhole dolostone on top of
mesoporous layer is thick in layer and pure in quality, with oolitic and crumble
structure and fully developed dissolution pores. Thus, it is the main industrial
production strata of Moxi gas field.
Located mainly in middle Triassic Leikoupo Formation, the hydrogen sulfide-
bearing gas reservoir of Zhongba gas field in western Sichuan is mainly composed of
a set of dolostone and gypsum rocks rich in blue green algae, particles and grains, the
products of limited shallow water platform environment under good closure
conditions. The reservoirs have relatively high permeability, various types of holes,
pores and cracks, and these are favorable for oil and gas reservoirs.

3. SAMPLING AND EXPERIMENTAL CONDITIONS

The samples of hydrogen sulfide-bearing natural gases sampled from Sichuan Basin
in this paper are from Puguang, Wubaiti, Huanglongchang and Wolonghe gas fields in
eastern Sichuan, Moxi gas field in middle Sichuan, Zhongba gas field in western
Sichuan, Weiyuan gas field in southern Sichuan. The strata involved include Sinian
Dengying Formation (Z2d), Cambrian Xixiangchi Formation (∈2+3x), upper Permian
Changxing Formation (P2ch), Triassic Feixianguan Formation (T1f), Jialingjiang
Formation (T1j) and Leikoupo Formation (T2l). There are a total of 34 natural gas
samples. The natural gas samples are sampled using high-pressure steel cylinders with
valves on both ends and anti-H2S corrosion coating. Before sampling, the cylinder was
flushed with natural gas at the high-pressure wellhead for 10 to 15 minutes. And the
analysis was done within 15 days after sampling.
Gas components were determined on an Agilent 6890 N gas chromatograph (GC)
equipped with a thermal conductivity detector (TCD). Using helium as the carrier gas,
a 30 m×0.32 mm×20 µm PLOT Q or a 30 m×0.53 mm×25 µm PLOT 5A MS column
was used. The inlet temperature was set at 150˚C, and the TCD temperature was 200°.
The initial oven temperature was maintained at 40˚C for 7.5 min and then rose from
40˚C to 90˚C at 15 ˚C/min, finally from 90˚C to 180˚C at 6 ˚C/min.
The carbon isotopic composition of gases was determined on a Delta S isotopic
mass spectrometer (Thermo Fisher Scientific) equipped with an Agilent 6890 N GC.
Individual hydrocarbon gas compounds (C1-C5) were separated using a capillary
696 Geochemistry characteristics of hydrogen sulphide-bearing gas pools
in Sichuan Basin

column (30 m×0.32 mm×20 µm HP-PLOT Q). The inlet temperature was 150°, the
temperature of oxidation oven was 950°, and the gas chromatograph temperature
started at 30˚C for 5 min, and rose from 30° to 80° at 8°/min, then from 80˚C to 170˚C
at 5°/min, and finally from170˚C to 270˚C at 6°/min. The reproducibility and precision
of isotope value are superior to ±0.3‰.
The hydrogen isotopic composition of gases was determined on a MAT253 isotopic
mass spectrometer (Thermo Fisher Scientific) equipped with a Trace GC UltraTM
using the gas chromatography pyrolysis interface and the removing water device.
Helium was used as the carrier gas, and a 30 m×0.32 mm×20 µm HP-PLOT Q column
was used with flow rate 1.4ml/min. The inlet temperature was set at 180˚C. The
methane hydrogen isotope was determined in a split injection mode (split ratio 1:7).
The initial temperature is 40˚C for 5 min. The ethane and propane hydrogen isotopes
were determined in a splitless injection mode (split ratio 1:7). The initial temperature
is 40˚C for 5 min, then from 40˚C to 80˚C at 5 ˚C/min, from 80˚C to 140˚C at 10
˚C/min and from 140˚C to 260˚C at 30 ˚C/min. The temperature of the pyrolysis oven
was 1450°. The gas components were transformed into C and H2. The H2 went into
mass spectrometer to be determined. According to the V-SMOW criterion, the δD was
caculated. The reproducibility and precision of isotope value are superior to ±3‰.
The sulfur isotopes of H2S were measured on a Delta S isotopic mass spectrometer
(Finnigan) equipped with an elemental analyzer. The elemental analyzer operating
conditions were as follows: a 3ft×1/4 in Teflon special analysis column was used with
helium flow rate 110 ml/min; the flow rate of oxygen was 40 ml/min and injection for
15 seconds. The oxidation furnace temperature was 1020˚C. The sulfur isotope in
hydrogen sulfide is expressed as δ34S (‰), calibrating to VCDT standards. The
reproducibility and precision of isotope value are superior to ±0.3‰.

4. RESULTS AND DISCUSSION

4.1. Characteristics of natural gas components
The geochemical data of hydrogen sulfide-bearing natural gases in Sichuan Basin are
shown in Table 1. Hydrocarbon is the dominant component. The content of
hydrocarbon is up to 80%. The contents of non-hydrocarbon such as CO2, N2 and H2S
are relatively high, varying significantly with geographic locations of gas reservoirs.
The major hydrocarbon gas is methane, whose contents are 70% to 95%. The contents
of heavy hydrocarbon are very low, and their dry coefficients (C1/∑C 1-5) are above
0.96, close to 1 in most cases. Thus, they are typical dry gas.
The hydrogen sulfide-bearing natural gas reservoirs are concentrated in upper
Permian Changxing Formation and Triassic Feixianguan Formation in northeastern
Sichuan. Puguang gas field contains the highest content of nonhydrocarbon in eastern
Sichuan; the contents of methane are only 70%-80%. The H2S contents are between
13.6% and 14.5%, and that of CO2, between 8.2%-11.8%, which is very high. The
content of nitrogen is more or less than 1%. The content of hydrogen sulfide is
relatively low in Wubaiti, Wolonghe and Huanglongchang gas fields, ranging from
1.0% to 7.0%. Except that the content of CO2 in the gas reservoir of Jialingjiang
Formation in Wolonghe gas field is less than 1%, all the other gas fields contain a
larger content of CO2, ranging from 3% to 8%.
ENERGY EXPLORATION & EXPLOITATION · Volume 32 · Number 4 · 2014 697

The contents of methane in natural gases in Sinian and Cambrian gas reservoirs of
Weiyuan gas field in southern Sichuan range from 85% to 87%. The contents of heavy
hydrocarbon are low, being less than 0.1%, and the dry coefficients are close to 1. H2S
content is low, ranging between 0.6% and 1.3%, and the contents of CO2 and N2 are
higher, ranging between 6% and 8% and between 4% and 6% respectively.
The contents of methane in natural gas are between 80% and 85% in Leikoupo
Formation of Zhongba gas field in western Sichuan. The contents of heavy
hydrocarbon are higher than that in hydrogen sulfide-bearing gas fields, being about
3%. The dry coefficient varies from 0.96 to 0.99. The contents of hydrogen sulfide are
relatively high, ranging from 7% to 8%. They also contain high contents of CO2 and
N2, which range from 4% to 6% and from 1.5% to 3.0% respectively.
The contents of methane in natural gas are more than 95% in Leikoupo Formation of
Moxi gas field in middle Sichuan. The dry coefficients are 0.99, and the contents of
hydrogen sulfide range from 2% to 4%; the contents of CO2 and N2 are low, both below 1%.
According to the classification method given by Dai Jinxing (1985) for hydrogen
sulfide-bearing natural gas reservoir, gas reservoir with the content of hydrogen
sulfide less than 0.5% is poor hydrogen sulfide-bearing gas reservoir; gas reservoir
with the content of hydrogen sulfide from 0.5% to 2% is hydrogen sulfide-containing
gas reservoir; gas reservoir with the content of hydrogen sulfide from 2% to 70% is
high-content hydrogen sulfide-bearing gas reservoir; gas reservoir with the content of
hydrogen sulfide over 70% is hydrogen sulfide-bearing natural gas reservoir. Among
the samples collected in this paper, except Huanglongchang gas field in eastern
Sichuan and Weiyuan gas field in southern Sichuan, all the other gas fields contain
high content of hydrogen sulfide.
The content of hydrogen sulfide in natural gas has great impact on natural gas
components. Through the relation graph between the content of methane and the
content of hydrogen sulfide (Fig. 2a), it can be found that with the increase of
hydrogen sulfide content, the content of methane decreases. The content of hydrogen
sulfide is positively correlated with the content of CO2 (Fig. 2b).

15
(a) Huanglongchang
(b)
Puguang
Wolonghe
12
Wubaiti
Weiyuan
Zhongba
9
CH4 (%)

M oxi
CO2(%)

0
H2 S(%) 0 4 8 12 16 20
H2S(%)

Figure 2. Relational diagram between the content of hydrogen sulfide and that of
methane in natural gas (a), Relational diagram between the content of hydrogen
sulfide and that of carbon dioxide (b).
 Table 1. Geochemical data on natural gas from gas fields in Sichuan Basin.
698

34
D S
13
Content (%)
Gas Filed Well Strata Depth (m)

CO2 H2S C1 C2 C3 C4+ CO2 C1 C2 C3 C1 C2 H2S

HL1 P2ch 4004.0 2.81 1.30 95.09 0.39 0.01 0.00 -31.0 -32.1 -124 16.6
Huanglongchang
HL10 P2ch 4102.0 2.84 1.36 95.04 0.38 0.01 0.00 -0.6 -30.8 -31.9 -131 17.7

PG5 T1f 5141-5243.8 8.26 13.46 77.58 0.05 0.00 0.00 4.4 -30.1 -28.8 -139 -84 15.8

PG6-1 P2ch 5295-5385.2 8.86 14.16 76.17 0.05 0.00 0.00 0.3 -28.1 -29.0 -145 -102 14.3

PG6-2 T1f 5030-5158 8.87 14.53 76.34 0.05 0.00 0.00 -0.4 -29.5 -28.4 -147 -101 14.0

Puguang PG7 T1f 5484.7-5546.7 8.93 13.83 76.57 0.06 0.00 0.00 -29.8 -29.7 -27.9 -134 -148 13.4

PG7 T1f 5571.7-5590 8.91 13.83 76.25 0.06 0.00 0.00 -29.5 -29.1 -133 12.4

PG8 P2ch-T1f 5502-5592 7.23 14.57 71.96 0.19 0.08 0.09 -1.1 -29.6 -30.6 -138 -112 15.9

PG9 P2ch 6110-6130 11.80 13.68 72.71 0.50 0.25 0.18 -1.3 -30.0 -31.5 -138 -99 13.5

W3 T1j 0.33 4.89 92.92 1.33 0.00 0.00 -17.0 -34.8 -27.5 -24.0 29.9

Wolonghe W57 T1j3 0.00 2.63 95.69 0.86 0.13 0.09 -10.5 -31.9 -32.0 -24.0 -136 -131 31.0

W6 T1j 0.35 4.62 92.94 1.45 0.00 0.00 -32.6 -28.9 30.4

TD002-11 P2ch 4232.0 3.93 2.16 93.10 0.52 0.01 0.00 -31.8 -33.6 -127 16.3

TD021-3 P2ch 5045.0 7.05 6.69 85.76 0.25 0.00 0.00 -0.2 -31.8 -31.0 -127 17.3

Wubaiti TD10 P2ch 4962.0 3.35 2.03 93.69 0.61 0.02 0.00 -0.9 -31.7 -32.9 -128 16.8

TD53 P2ch 4450.0 7.56 7.05 84.91 0.24 0.01 0.00 -1.6 -31.8 -31.1 -131 -110 18.4

TD72 P2ch 4368.0 6.64 6.02 86.78 0.32 0.01 0.00 -0.2 -31.6 -31.9 -130 18.0
Geochemistry characteristics of hydrogen sulphide-bearing gas pools
in Sichuan Basin
 Table 1. Geochemical data on natural gas from gas fields in Sichuan Basin (continued).

34
D S
13

Gas Filed Well Strata Depth (m) (VSMOW, (VCDT,

CO2 H 2S C1 C2 C3 C 4+ CO2 C1 C2 C3 C1 C2 H 2S

WY39 Z 2d 2986 4.54 1.22 87.01 0.12 0.00 0.00 -5.5 -32.9 -33.8 -146 -137 16.9

WY42 Œ2+3x 2178 4.95 1.15 87.60 0.05 0.00 0.00 -1.4 -32.3 -32.9 -144 -133 14.4

WY5 Œ2+3x 1911-2037 4.51 0.71 87.62 0.06 0.00 0.00 -3.7 -32.0 -35.7 -145 15.7

Weiyuan WY65 Œ2+3x 2206 5.82 1.07 86.70 0.05 0.00 0.00 -5.4 -32.4 17.9

WY70 Z 2d 3064 4.05 1.00 86.30 0.09 0.00 0.00 -2.5 -32.4 -147 -137 14.9

WY93 Π1+2 1196-2052 5.02 0.63 87.19 0.07 0.00 0.00 -8.3 -32.3 -36.2 -143 16.0

WS2 Œ2+3x 2109 6.06 0.87 86.73 0.06 0.00 0.00 -3.0 -32.6 -34.0 -144 -135 17.2

Z21 T 2l 3 3303 4.85 7.78 81.78 1.59 0.49 1.05 -35.4 -31.1 -30.3 -156 -135 16.5

Z23 T 2l 3 3100 4.48 7.28 82.94 1.62 0.49 0.90 -35.1 -28.0 -157 -136 17.1

Z40 T 2l 3 3121.7 5.22 7.57 82.35 1.51 0.47 0.85 -35.9 -29.3 -27.1 -156 -137 16.5
ENERGY EXPLORATION & EXPLOITATION · Volume 32 · Number 4 · 2014

Zhongba
Z42 T 2l 3 3358.75 5.35 7.65 82.10 1.63 0.59 1.05 -33.5 -28.2 -154 -138 16.7

Z46 T 2l 3 3134.51 5.10 7.15 82.96 1.62 0.50 0.95 -34.2 -29.3 -158 -141 16.6

Z81 T 2l 3 3231.7 4.88 6.94 84.03 1.42 0.44 0.82 -34.2 -28.6 -157 -135 16.9

M128 T 2l 2694.4 0.14 2.96 95.42 0.51 0.01 0.00 -1.4 -33.4 -32.8 -134 11.3

Moxi M14 T 2l 2679.5 0.18 3.49 94.69 0.50 0.01 0.01 -1.8 -33.2 -31.4 -25.9 -134 9.3

M18 T 2l 2656.7 0.12 2.51 96.11 0.48 0.01 0.01 -0.8 -33.6 -33.5 -134 12.2
699
 700 Geochemistry characteristics of hydrogen sulphide-bearing gas pools
in Sichuan Basin

4.2. Characteristics of isotopes of natural gas

Carbon isotopes in methane of hydrogen sulfide-bearing natural gases in eastern
Sichuan range from -33‰ to -30‰ and carbon isotopes in ethane, from -33‰ to -
28‰. Carbon isotope reversal for methane and ethane exists in some samples. Carbon
isotopes in methane of Sinian and Cambrian gas reservoirs of Weiyuan gas field in
southern Sichuan range from -33‰ to -32‰, and carbon isotopes in ethane, from -
36‰ to -33‰ (less than -30‰). Thus, they are typical oil-type gas. The same reversal
for methane and ethane also exists. Carbon isotopes in methane of natural gases in
Leikoupo Formation of Zhongba gas field in western Sichuan range from -36‰ to -
34‰, and carbon isotopes in ethane, from -31‰ to -28‰. Carbon isotopes in methane
of natural gases of Leikoupo Formation of Moxi gas field in middle Sichuan are about
-33‰, and carbon isotopes in ethane, between -33‰ and -31‰.
Carbon isotopes in methane of hydrogen sulfide-bearing natural gas reservoirs in
Sichuan Basin range between -35.9‰ and -28.1‰, and carbon isotopes in ethane,
between -36.2‰ and -27.5‰ (Fig. 3). Carbon isotopes are generally heavier. It is
noteworthy that natural gas in hydrogen sulfide-bearing natural gas reservoirs in
Sichuan Basin is originated from marine source rocks, so it should be composed of
lighter carbon isotopes in ethane; however, in the Wolonghe gas field, Zhongba gas
field and Puguang gas field, the natural gas has lighter ethane carbon isotope
composition, which shows that the hydrogen sulfide content has big influence on the
ethane carbon isotope, and there is no obvious relationship between the hydrogen
sulfide content and the methane carbon isotope (Fig. 3a).
Hydrogen isotopes in methane of hydrogen sulfide-bearing natural gas reservoirs in
Sichuan Basin are widely distributed, ranging from -160‰ to -125‰ (Fig. 4).
Hydrogen isotopes in methane are the heaviest in Huanglongchang gas field and
Wubaiti gas field in northeastern Sichuan, ranging from -135‰ to -125‰, while the
hydrogen isotopes in methane are the lightest in Zhongba gas field, ranging from -
160‰ to -155‰. Generally, hydrogen isotopes in methane of hydrogen sulfide-

(a) (b)
CC2H6 (VPDB, )
)
CCH4 (VPDB,
13

13

H2 S(%) H2 S(%)

Figure 3. A. Relational diagram between the content of hydrogen sulfide in natural

gas and carbon isotopes in methane; b. Relational diagram between the content of
hydrogen sulfide and ethane carbon isotopes.
ENERGY EXPLORATION & EXPLOITATION · Volume 32 · Number 4 · 2014 701

DCH4 (VSMOW

13
CCH4 (VPDB

Figure 4. Relational diagram between carbon and hydrogen isotopes in methane of

natural gas.

bearing natural gas reservoirs in Sichuan Basin have the trend that they become
heavier as carbon isotopes in methane become heavier, which indicates that hydrogen
isotopes of hydrogen sulfide-bearing natural gas are greatly influenced by the degree
of maturity. However, hydrogen isotopes in methane have no obvious relationship
with the content of hydrogen sulfide (Fig. 5), which suggests that TSR reaction has
little influence on hydrogen isotope in methane.
DCH4 (VSMOW

H2 S(%)

Figure 5. Relational diagram between hydrogen isotopes in methane and content of

hydrogen sulfide of natural gas.
702 Geochemistry characteristics of hydrogen sulphide-bearing gas pools
in Sichuan Basin

SH2S (VCDT,
34

H2S(%)

Figure 6. Relational diagram between the content of hydrogen sulfide in natural gas
in Sichuan Basin and sulfur isotope.

It seems that sulfur isotope in hydrogen sulfide of hydrogen sulfide-bearing natural

gas in Sichuan Basin has little association with the content of hydrogen sulfide. The
heaviest sulfur isotopes of hydrogen sulfide occur in Wolonghe gas field, being up to
30‰; the lightest occur in Moxi gas field in middle Sichuan, ranging from 9‰ to
12‰; the distribution of sulfur isotopes in hydrogen sulfide in other areas is
comparatively concentrated, varying from 13‰ to 18‰ (Fig. 6). The heaviest sulfur
isotopes of hydrogen sulfide occur in Jialingjiang Formation on the section, above or
below which the sulfur isotopes become lighter (Fig. 7).
SH2S(VCDT,
34

T1l3 T2l1 T1j T1f P2ch 2+3x Z2d

Figure 7. Distribution diagram of sulfur isotopes of hydrogen sulfide in natural gas in

each series of Sichuan Basin.
ENERGY EXPLORATION & EXPLOITATION · Volume 32 · Number 4 · 2014 703

Ssulfate(VCDT,
34

T1l3 T2 l1 T1 j T1f P2 ch 2+3x Z2 d

Figure 8. Distribution diagram of sulfur isotopes of sulfate in each series of Sichuan

Basin.

The strata containing high content of hydrogen sulfide in Sichuan Basin are mainly
Triassic Feixianguan Formation, Jialingjiang Formation and Leikoupo Formation.
These reservoirs are located in carbonate rocks rich in gypsum and anhydrite. Lin
Yaoting (2003) pointed out that the sulfur isotopes in sulfate (gypsum, anhydrite)
collected from Triassic Feixianguan Formation and Leikoupo Formation in Sichuan
Basin showed a decreasing distribution from bottom to top on the section, with little
changes on the plane. The sulfur isotopes in sulfate in the gas reservoir of the same
strata show stable distribution. Sulfur isotopes in sulfate in the strata of Feixianguan
Formation in eastern Sichuan range from 18.1‰ to 30.7‰ (Wang et al., 2002; Zhu et
al., 2006); that in sulfate in Jialingjiang Formation in eastern Sichuan range from
26.0‰ to 35.4‰. Sulfur isotopes in the first segment of Leikoupo Formation in
middle Sichuan range from 25.0‰ to 30.6‰. Sulfur isotopes in the fourth segment of
Leikoupo Formation are the lightest, ranging from 14.7‰ to 18.9‰ (Lin, 2003). In
addition, sulfur isotopes in sulfate in Sinian Dengying Formation of Weiyuan gas field
in southern Sichuan range from 22‰ to 25‰ (Fig. 8) (Zhu et al., 2006).

4.3. Genesis of hydrogen sulfide in gas reservoirs

The studies on the genesis of hydrogen sulfide in gas reservoir enable us to understand
the formation process of natural gas reservoir and the pattern of gas reservoir
accumulation, which would be helpful to discovery more gas reservoirs. The
geological genesis of hydrogen sulfide in natural gas includes cracking of sulfur-
bearing organic matters, bacterial sulfate reduction and thermochemical sulfate
reduction.
The cracking of sulfur-bearing organic matters refers to the release of sulfur in
some sulfur-bearing organic matters during thermal evolution of organic matters to
form hydrogen sulfide; the generation is influenced by the type of organic matters and
the degree of thermal evolution of organic matters; the concentration of hydrogen
sulfide is generally not higher than 3%. The fractionation degree of sulfur isotopes is
usually high and the sulfur isotopes are always about 15‰. The bacterial sulfate
reduction (BSR) refers to the reaction that hydrocarbons (mainly liquid hydrocarbons)
704 Geochemistry characteristics of hydrogen sulphide-bearing gas pools
in Sichuan Basin

are degraded by means of bacterial sulfate reduction to reduce S+6 in gypsum and
anhydrite to S2-, giving H2S (or FeS2) and CO2. This process requires low temperature,
as the temperature above 80˚C will restrict bacterial activities and terminate the
reaction. In modern sedimentary environment, this reaction can be observed in the
sedimentary formation rich in organic matter under algal mat near the sea level.
Currently most scholars agree that the degradation of hydrocarbons via such reaction
occurs mainly in shallow-buried environment with the temperature below 60˚C-80˚C,
where oil and gas is immature and sulfur isotopes of hydrogen sulfide generated
through bacterial sulfate reduction are generally lighter than 8‰. In addition, the
reaction process requires the mechanism in which the reaction product H2S is
removed, for in a closed system the excessive H2S will restrict the activities of sulfate
reducing bacteria. The stable sulfur isotopes of the products (H2S, S0, FeS2, etc)
generated by bacterial sulfate reduction are relatively lighter. But the fractionation of
sulfur isotopes in bacterial sulfate reduction can reach -15‰--30‰, or even -65‰
(Ohmoto and Rye, 1979). Under high temperature, sulfate is reduced to hydrogen
sulfide with the hydrocarbon as the reducing agent. This reaction is called
thermochemical sulfate reduction, or abiogenic, inorganic and thermogenic sulfate
reduction (Ohmoto and Rye, 1979). Most of recent research results indicate that this
process takes place at 100˚C or 150˚C-200˚C, and Ro is equal to 1%-4% deep buried
high temperature environment. And at the same time, the presence of sulfate is
required. For example, hydrocarbons often have secondary reactions in strata
containing gypsum or developed gypsum-bearing rocks. In either BSR or TSR,
hydrocarbons are degraded as the reducing agent in the reaction (Sun and Püttmann,
2000). Under high temperature, if there is enough sulfate, gas or liquid hydrocarbons
may be completely destroyed, eventually form hydrogen sulfide-bearing gas
reservoirs. The reactants produced in TSR include FeS2, CaCO3, MgCa(CO3)2 and S0
in addition to H2S, asphalt and CO2. The stable sulfur isotopes of these
sulfocompounds are obviously heavier than those in BSR. Stable carbon isotopes of
carbonate generated in the reaction are lighter than stable carbon isotopes of
sedimentogenic carbonate minerals, because the former is due to biological causes, i.e.
from hydrocarbons. The dynamic fractionation of sulfur isotopes in TSR is less than
that in BSR, being generally less than 20‰. The fractionation decreases with the
increase of temperature. At the temperature of 100˚C, fractionation is about 20‰;
when the temperature reaches 150˚C, fractionation is about 15‰; at 200˚C,
fractionation is only 10‰ (Harrison and Thode, 1957; Husain and Krouse, 1978;
Kiyosu and Krouse, 1990).
After knowing the three basic formation routes of hydrogen sulfide, the positive
correlation between H2S and CO2 contents in Figure 3b can be explained to be caused
by thermochemical sulfate reduction (TSR). In TSR, hydrogen sulfate is generated in
the reaction of hydrocarbons and sulfate; carbon dioxide is also generated, with light
carbon isotopes. For instance, carbon isotopes of CO2 in the reservoir of Jialingjiang
Formation of Wolonghe gas field are very light, generally below -10‰.
Figure 4 shows that higher content of hydrogen sulfide corresponds to heavier
carbon isotope in ethane, which confirms the occurrence of TSR in the reservoir.
During TSR, sulfate ions will first oxidize 12C-12C bond in hydrocarbons, resulting in
ENERGY EXPLORATION & EXPLOITATION · Volume 32 · Number 4 · 2014 705

CCH4(VPDB, )
13
CC2H6-
13

H2S(%)

Figure 9. Relational diagram between the content of H2S and δ13C C2H6-δ13C CH4
value in natural gas in Sichuan Basin.

enriched 13C in the residual hydrocarbons. At 140˚C, chemical thermodynamics

calculation results of the reactions of CH4,, C2H6, C3H8, C4H10 and anhydrite show that
the larger the number of carbons in hydrocarbon, the lower the activation energy will
be, the more active the gas, the more easily TSR will occur. Thus, C2H6, C3H8 and
C4H10 are easier to undergo TSR than CH4, with heavier carbon isotopes, which gives
rise to the phenomenon that higher content of hydrogen sulfide usually corresponds to
heavier carbon isotope in ethane.
Figure 7 and 8 indicate that the differences between sulfur isotopes of sulfate
correspond well to those in hydrogen sulfide. The difference between sulfur isotopes
of sulfate and that in hydrogen sulfide in lower Triassic Jialingjiang Formation in
Wolonghe gas field is the minimum (4‰-5‰). Sulfur isotopes of hydrogen sulfide in
other strata are lighter, being between 6‰ and 14‰ and being 9‰-11‰ in most cases.
Thus, they are the products of thermochemical sulfate reduction. According to the
above analysis, there is carbon isotope reversal for methane and ethane in some of the
reservoirs of Jialingjiang Formation in Wolonghe gas field, with a high content of oil
cracked gas in the later period. Sulfur isotopes of hydrogen sulfide are closely to those
in sulfate. The fractionation degree of sulfur isotopes is small, and the difference is
only 4‰-5‰. This indicates that the temperature is high during TSR in the reservoir,
higher than 200˚C. This condition is consistent with geothermal conditions for
cracking of oil to gas. Carbon isotopes of CO2 are below -10‰. The CO2 is generated
through oxidization of hydrocarbons by sulfate in TSR.
The natural gas with carbon isotopic reversal of methane and ethane in Sichuan
Basin is mainly located in some areas of the Huanglongchang gas field, Wubaiti gas
field and Puguang gas field in the Northeast Sichuan area as well as Weiyuan gas field
in South Sichuan. Except that there is specially high hydrogen sulfide content in
Puguang gas field, the hydrogen sulfide content in the natural gas with carbon isotopic
706 Geochemistry characteristics of hydrogen sulphide-bearing gas pools
in Sichuan Basin

reversal is generally less than 5% (Fig. 9). In the foregoing document, it has already
been pointed out that, if the TSR reaction has big influence on the natural gas
component, it will create the phenomenon of heavier ethane carbon isotope. As for the
phenomenon that ethane carbon isotope is lighter than the methane carbon isotope in
the gas fields, it is thought that this is mainly caused in the gas production process by
cracking the crude oil and TSR has small influence on these gas pools. Pitch in the
Triassic Feixianguan Formation reservoir in Northeast Sichuan area is well developed;
asphalt silting is also generally observed in Sinian and Cambrian reservoir in Weiyuan
gas field; part asphalt is distributed in layer, which indicates that there had been
ancient oil deposit in the early time, and in later period the crude oil cracked in the
thermal evolution process. In addition, the oil cracking gas mainly occurred in the
stage of dry gas production in the later period, and massive methane with heavier
carbon isotope was mixed with the original oil gas in the reservoir, thus the present
phenomenon with heavier methane carbon isotope was created.

5. CONCLUSIONS
The contents of hydrocarbons in hydrogen sulfide-bearing natural gases in Sichuan
Basin are generally above 80%. The contents of non-hydrocarbons such as CO2, N2
and H2S are relatively high. The dry coefficients are above 0.96, and close to 1 in most
cases. Thus, it is typical dry gas.
The hydrogen sulfide content in the hydrogen sulfide gas pools of Sichuan Basin is
0.6%-14.5%; the sulfur isotope values of hydrogen sulfide gas have a close
relationship with the sulfur isotope values of anhydrite in the same reservoir, showing
that the H2S in natural gas and the anhydrite in reservoir have the same sulfur source,
the H2S in natural gas is the product of TSR reaction. The relationship among the
hydrogen sulfide content in the gas pool, the hydrogen isotope of methane and the
sulphur isotope of hydrogen sulfide is not obvious; but the high hydrogen sulfide
content corresponds to the heavier ethane carbon isotope composition, and the carbon
isotope of carbon dioxide is lower than -10‰, which belongs to the organic origin and
has further verified the fact of TSR occurrence in the reservoir.
There is the phenomenon of carbon isotopic reversal of methane and ethane in
some areas of the Huanglongchang gas field, Wubaiti gas field and Puguang gas field
in the Northeast Sichuan as well as Weiyuan gas field in South Sichuan, which is
mainly caused by the later period of cracking-based gas-production process of the
crude oil. Thermochemical sulfate reduction has less influence on these gas pools.

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