PETROLEUM EXPLORATION AND DEVELOPMENT

Volume 37, Issue 5, October 2010

Online English edition of the Chinese language journal

Cite this article as: PETROL. EXPLOR. DEVELOP., 2010, 37(5): 513–522. RESEARCH PAPER

H2S formation and enrichment mechanisms in medium to

large scale natural gas fields (reservoirs) in the Sichuan
Basin
Liu Wenhui1, Tenger1,*, Gao Bo1, Zhang Zhongning2, Zhang Jianyong2, Zhang Dianwei1, Fan Ming1,
Fu Xiaodong1, Zheng Lunju1, Liu Quanyou1
1. Wuxi Research Institute of Petroleum Geology, Sinopec Petroleum Exploration and Production Research Institute, Wuxi 214151, China;
2. Lanzhou Institute of Geology, Chinese Academy of Sciences, Lanzhou 730000, China

Abstract: A comprehensive study on the temporal and spatial distribution of H2S accumulations and the geochemical characteristics of
sour gas fields (reservoirs) in the Sichuan Basin has been conducted. It has been followed by a series of carefully designed simulation
experiments to elucidate an H2S formation mechanism which is able to predict the distribution of H2S. In some reservoirs, for example
P2chT1f, have sufficient magnesic SO42 and abundant hydrocarbons (palaeo pools) present at sufficiently high temperatures to cause
thermochemical sulfate reduction (TSR). This is the major origin of abundant H2S in large to medium scale gas fields. The formation
mechanism of highly sour gas fields (reservoirs) is an in-situ reaction under conditions where sufficient source, enough energy supply,
suitable reservoir volume and severely reducing environments occur. However, in some areas or strata, such as slope belts or on conti-
nental shelf deposits, or formations such as the Jialingjia and Leikoupo Formations, which are dominantly compact carbonatite and have
contemporaneously different facies, it is difficult to form abundant H2S. These formations lack a source of sulphur and energy compared
to the P2chT1f reef flat facies reservoirs. Even though highly sour natural gas migrating from the P2chT1f reservoirs is present, H2S is
often consumed due to long distance migration and results in hydrocarbon-rich sweet natural gas. This study predicts that the Heichiliang
reef flat facies sedimentary zone in northeastern Sichuan to have highly sour natural gas reservoirs.

Key words: northeastern Sichuan; H2S; TSR; enrichment mechanism; highly sour gas field

Introduction tioned gas fields (reservoirs) which adds great difficulty to

There are different H2S concentrations in natural gas re-
sources. Natural gas reserves with H2S concentrations of more
than 1% accounts for 1/4 of China’s natural gas reserves. H2S
is poisonous, polluting and dangerous to mankind and adds
costs to engineering against its corrosive nature in exploration
and development equipment. But it is also an important com-
mercial raw material with high economic value. Therefore,
research on highly sour natural gas is significant for reducing
commercial costs, safeguarding production and promoting the
natural gas industry in China. At the beginning of the 21st
century, the Changxing formationFeixianguan formation
(P2chT1f) medium to large scale natural gas fields (reservoirs)
have been explored at Dukouhe, Luojiazhai and Puguang in
the Northeastern Sichuan Basin. This geographic area is be-
lieved to contain important resources and can be linked to
Sichuan gas transportation network to the east. However, H2S
concentrations generally reach 10%17% in the above men-
production safety. H2S formation and enrichment mechanisms
in the northeastern Sichuan area have therefore become an
important issue in terms of scientific research[1].
The spatial distribution of sour natural gas fields in the Si-
chuan Basin is apparently nonuniform. Highly sour gas fields
(H2S concentrations of more than 5%) are mainly distributed
in the XuanhanDazhou area of Northeastern Sichuan. Verti-
cally, they are concentrated in the Upper Permian and mid-
dle-lower Triassic sediments. H2S concentrations are different
in different wells within the same gas reservoir or in different
horizons (P2ch, T1f) in the same well. For example, the T1f gas
reservoir in Wells Puguang 2 and Puguang 9 in the Puguang
gas field have high sulfur concentrations. However, the T1f
gas reservoir in the neighboring Qingxichang (Well Qingxi 1)
and Maobachang (Well Maoba 1) fields are sulfur-free or have
low sulfur concentrations. In addition, natural gas in gyp-
sum-salt reservoirs and reservoirs close to gypsum-salt rocks

Received date: 11 Apr. 2010; Revised date: 05 Jul. 2010.

* Corresponding author. E-mail: tenger67@sina.com
Foundation item: Supported by Petrochemical Industry Collaborative Fund Program (40739902; 40839910)
Copyright © 2010, Research Institute of Petroleum Exploration and Development, PetroChina. Published by Elsevier BV. All rights reserved.
 Liu Wenhui et al. / Petroleum Exploration and Development, 2010, 37(5): 513–522
(Wells Maoba 1 and Heba 1) do not contain any H2S. Reser-
voirs with undeveloped gypsum-salt or far from gypsum-salt
rock (P2ch in Wells Puguang 2 and Puguang 9) have natural
gas accumulations with high concentrations of H2S. Therefore,
there is no direct relationship between the presence of H2S in
natural gas accumulations and the presence of a gypsum layer.
The uneven spatial distribution is not only a product of the
H2S formation mechanism, but more affected by the mode of
occurrence. Currently the main theory about the H2S forma-
tion mechanism in this area is that H2S is sourced from gyp-
sum near the T1f gas reservoir by thermochemical sulfate re-
duction (TSR) at high temperature. There is a close relation-
ship between natural gas reservoirs with H2S enrichment and
carbonate rock layers enriched in anhydrite. The existence of
gypsum-salt is therefore necessary for the formation of high
concentrations of H2S[24]. This observation suggests that TSR
is the main H2S formation mechanism of natural gas reser-
voirs in the area; however, it is hard to explain the subsequent
H2S enrichment mechanisms and pattern of distribution in
natural gas reservoirs. Moreover there is disagreement as to
whether gypsum, as TSR reactant, participates in the reaction
or not.
For these problems, based on research results of the spa-
tial-temporal distribution, geochemical characteristics and
Fig. 1 Distribution of sour gas fields in the Sichuan Basin
simulation tests of sour natural gas fields of the Sichuan Basin,
the following point of view is put forward in this paper, i.e.
H2S formation, enrichment and accumulation in the North-
eastern Sichuan P2chT1f reservoir are together controlled by
four factors, namely source, energy, space and preservation.
These processes of source preparation, H2S formation and
accumulation provide an important basis for predicting the
distribution of highly sour gas reservoirs.
1 Geological background of research area
The Sichuan Basin is the largest oil and gas bearing basin
in southern China. More than 20 gas-bearing layers have been
identified and 180 oil and gas fields discovered there. This
includes 30 medium to large scale marine and continental
facies natural gas fields with proven reserves larger than
100×108 m3 [5,6]. This basin also contains the most highly sour
gas distributions and largest scale reserves of methane in
China, where natural gas is mainly concentrated in the
P2chT1f reservoirs of Northeastern Sichuan. There are 9
highly sour gas fields in Northeastern Sichuan with H2S con-
centrations of over 5%, and all distributed along the Guan-
gyuanKaijiang area of continental shelf reef flat facies mar-
gins in the latter part of the late Permian to the earlier part of
the Triassic (Fig. 1).
 Liu Wenhui et al. / Petroleum Exploration and Development, 2010, 37(5): 513–522

Northeastern Sichuan is located at a fault-fold structural
belt in Eastern Sichuan. The western section of the north side
includes the Micangshan uplift and its front, and the eastern
section is the front fault-fold belt of the Dabashan nappe belt.
To the west is the gentle structural belt of the Eastern and
Central Sichuan while to the east and south is the parallel or
arc fault-fold belt in the eastern basin. The main structure is
the NE-ENE fault-fold belt, which includes Huangjinkou
structural belt and Xuanhan structural belt (Fig.1). The
Puguang field is located at the ShuanghuangmiaoPuguang
structural belt of the Huangjinkou structure in Xuanhan region.
As a NE high and steep anticlinal belt, it is a large scale gas
reservoir with a structural - lithological trapping mechanism.
Natural gas is mainly enriched in the porosity of the P2chT1f
reef flat facies. The reservoir has a normal pressure, low tem-
perature and high H2S content and reservoirs oil and gas from
a mainly Upper Permian source and to a lesser extent from the
Lower Silurian. The Heba and Qingxichang gas reservoirs
both contain none to low amounts of H2S in the mainly T1f
fractured reservoir, which has a high pressure regime. The
Qingxichang gas reservoir is located in the Qingxichang NW
structural belt of the Xuanhan structural belt, near to the
ShuangshimiaoPuguang structural belt. The Heba gas reser-
voir is located at the south section of the Tongnanbaciji struc-
tural belt which is a part of the gentle structural belt in Central
Sichuan. The Heba 1 well has been tested for commercial gas
flow in the Jialingjia and Feixianguan formations, which sug-
gests that there are high quality natural gas reservoirs without
H2S in the Hebachang, a low temperature and high pressure
structural gas reservoir[710].
2 Factors controlling the accumulation of highly
sour gas
The special conditions for the formation of H2S and its
chemical activity make its behavior and accumulation differ-
ent to hydrocarbon gases. H2S formation not only needs suffi-
cient source materials, but also the reaction needs a minimum
energy requirement and materials that induce the reduction
reaction. All of these must exist in the same place to make the
reaction possible, and more importantly, the reaction needs
physical and chemical conditions which makes long time
preservation of H2S possible. For the highly sour gas fields of
Northeastern Sichuan, H2S formation and enrichment are con-
trolled by four main factors (1) source: hydrocarbon - en-
riched, high sulfur, Mg containing fluids; (2) thermal source:
deep burial, high temperature; (3) space: source present at the
same time as “ideal” thermal conditions are reached; (4) pres-
ervation: preservation conditions of reduction and trapping.
2.1 Source
The formation of large amounts of H2S needs sufficient
sulfur sources. Based on systematic research on source mate-
rials from different facies in Northeastern Sichuan, it is certain
that there are many types of solid, liquid and gaseous source
materials present such as sulfate (gypsum), sulfide (pyrite and
H2S), organic sulfur and elemental sulfur in marine facies
layers of the area. Each might provide source materials for
H2S formation through different ways (such as decomposition
of unstable source organic matter in kerogen, crude oil and
solid bitumen). But not all of them appear to be contributors
to H2S formation. In this paper, a series of gold tube simula-
tion tests on H2S formation were conducted using different
source materials in the presence of organic matter of different
types and under different testing conditions, summarized be-
low (Table 1, Fig. 2):
Large amounts of H2S are formed under higher tempera-
tures (condensate oil and wet gas stage) and in the presence of
a SO42 solution and hydrocarbons. The generation rate is
much higher than for thermochemical reactions between gyp-
sum and organic matter, and thermal cracking of sulfur-rich
organic matter, which proves that TSR is the main mechanism
for the formation of large amounts of H2S under deep burial

Table 1 Simulation test conditions and scheme of H2S thermochemical formation

(Thermochemical Decomposition of sulfur
Thermochemical Sulphate Reduction (TSR)
containing organic matter) TDS
Type of Organic matter Reaction system CaSO4 CaSO4 reaction system MgSO4 MgSO4 reaction system
Crude oil: Tahe T740 well,
Crude oil+H2O Crude oil+CaSO4+H2O Crude oil+MgSO4+H2O
O1, sour 2.25%
Bitumen: Changjianggou of Anhydrite (CaSO4),
Magnesium sulphate
Guangyuan, 1, solid, Ro is Bitumen +H2O Well Maoba 3, T1f, Bitumen+CaSO4+H2O Bitumen + MgSO4+H2O
(MgSO4·7H2O), easily
0.64% 3 872 m, a little
soluble to water
kerogen: Changjianggou of soluble to water
Guangyuan, P2d, II type, Kerogen+H2O Type II+CaSO4+H2O Kerogen+MgSO4+H2O
sulfur content 0.9%
Note: The gold tube TSR simulation test is carried out by Researcher Liu Jinzhong and Dr. Zhang Jianyong at the State Key Laboratory of Or-
ganic Geochemistry (Guangzhou Institute of Geochemistry, Chinese Academy of Sciences), and the gold tube experiments use tubes that have an
ID of 4.2 mm, length of 50 mm, organic matter sample size of 50 mg, 100 mg deionized water, 100 mg sulfate added, a constant temperature of
360°C/450°C, a constant pressure of 35 MPa. Constant temperature is achieved after 10 h, which is then maintained for 10 d (reaction of 240 h).
Gas components can be analyzed online by model 6890N gas chromatograph, and stable carbon isotopic composition can be analyzed by model
ISOCHROM II gas chromatograph / Carbon Isotopic ratio mass spectrometer.
 Liu Wenhui et al. / Petroleum Exploration and Development, 2010, 37(5): 513–522
Fig. 2 Correlation of H2S thermochemical production in differ-
ent reaction systems
and high temperature. These observations further support the
previous opinions on H2S formation mechanisms in the
area[24], and also indicates that sulfate in an ionic state (SO42)
enters into the TSR reaction, such that the TSR reaction only
needs sufficient soluble SO42 in formation waters, instead of
large amounts of gypsum-salt to produce large volumes of
H2S. A more reasonable reaction equation should be:
Mg 2+
Cn H 2n  2  nSO 42  o Cn 1H 2 n  CO 2 n 
(n  1)H 2S n S  H 2O  CO32 (nı2)
Mg2+ is a factor deserving attention, though it is not clear how
it is involved in the reaction mechanism, but a certain amount
of Mg2+ ions in the fluid seem to catalyze TSR and H2S for-
mation. In recent years, the same results have been obtained
by relevant simulation tests conducted by other scholars[1113],
which suggest a mechanism involving MgSO4 ion-pairs[12] and
electric induction effects[13]. In terms of actual geological
conditions, the close correlation between highly sour gas
fields and dolomitization in reservoirs of Northeastern Si-
chuan indicates there is complex cause-effect relationship
between abundant H2S, TSR, Mg2+ and reservoir dolomitiza-
tion, which requires further research. Therefore, the chemical
properties of formation waters, especially the concentration of
MgSO4 might be one of the main factors controlling TSR and
abundant H2S formation in deeper geological formations.
By analyzing the sedimentary structural background, dolo-
mitization properties and hydrocarbon generation history of
the research area, it is clear that sulfate-rich (Mg) fluids are
not lacking in the P2chT1f reservoir, and might come from
multiple sources. A proportion of the fluids might be primary
sedimentary fluids, including connate water of concentrated
sea water deposited synchronous or nearly synchronous with
the P2ch, and T1f, as well as formation water affected by min-
eral solution during deep burial and diagenesis; the upward
migrating deep fluids under the fault controlled structural
conditions of the area might also be a supply of Mg. An un-
derstanding of the chemistry of the connate waters is mainly
based on researching results on the genesis of P2chT1f dolo-
mite reservoirs[1416] in the area. It is believed that deep burial
dolomitized fluids have strong characteristics typical of a sea
water source, mainly coming from synchronous or nearly
synchronous concentrated sea-sourced formation water depo-
sition with high Mg content and high-salinity. Its presence is
mainly related to the structural activities of Northeastern Si-
chuan since the Emei Mountain taphrogenesis, which means,
geologic activities such as volcanic or magmatic mechanisms
can heat deep formation fluids to 510°C higher than that of
adjacent rocks. Earthquakes or other factors may contribute to
the formation of high temperature fluids rich in magnesium
ions from deep crustal locations, or regional structural uplift-
ing can drive deep formation fluids to migrate upwards to
reservoirs such as the P2chT1f along faults, which mix with
existing reservoir fluids to form more complex fluids. In re-
cent years, some scholars have not only proven the existence
of these deep fluids, but revealed that P2chT1f carbonate
sediments affected by these fluids have experienced hydro-
thermal dolomitization and formed current high quality dolo-
mite reservoirs[17,18].
Under geological conditions, besides having enough
MgSO42 solution, abundant reducing agents i.e., hydrocarbon
supply (palaeo pools) is also an important contribution to-
wards large scale TSR reactions and production of H2S. The
range of palaeo pools is determined by solid bitumen contents
in reservoirs through the observation of drilling core slices. A
well containing a bitumen surface porosity > 0.2% is regarded
as an existing palaeo pool. In Fig. 3, there is widely distrib-
uted solid bitumen in the P2chT1f dolomite reservoirs of
Northeastern Sichuan, indicating that this formation experi-
enced a large amount of crude oil migration and accumulation
and marks the hydrocarbon accumulation of palaeo pools.
This crude oil mixed with sulfate-rich (magnesium) formation
waters and formed hydrocarbon-rich, high sulfur and magne-
sic fluids, which provide abundant sources for TSR reactions
in the P2ch and T1f reservoirs.
2.2 Thermal source
Research has demonstrated that TSR occurs at high tem-
peratures with an initial reaction temperature of at least
120 °C[1921]. This is confirmed by the simulation test results
presented here. Also, the relatively high reaction temperatures
result in organic matter types that are mainly at the condensate
and wet gas stages of organic evolution. The presence of light
hydrocarbons is more favorable for TSR, where the gas hy-
drocarbon components become increasingly dry due to the
thermal cracking of heavier hydrocarbon precursors. The test
by Zhang Tongwei and co-authors gives further evidence that
the severe reaction stage of TSR is during the gas condensate
and wet gas generation stage[12]. The hydrocarbon-enriched,
high sulfur and magnesic fluids in the P2chT1f reservoir con-
tinued being buried and heated, thus entering the range for the
energy of activating TSR (temperature ı120 °C) and conse-
quently, a great deal of H2S was formed. For the Puguang gas
field (Well Puguang 2), P2chT1f reservoir fluids were buried
at a depth of 4 000 m and the reservoir temperature reached
120 °C in the Middle Jurassic; by the Late Cretaceous, the
burial depth reached 7 500 m and the temperature reached
 Liu Wenhui et al. / Petroleum Exploration and Development, 2010, 37(5): 513–522

Fig. 3 Distribution of palaeo pools and H2S concentration in P2chT1f reservoirs in Northeastern Sichuan

Fig. 4 Micrograph and Laser Raman spectroscopy of gas inclusions in Well Puguang 5 (samples of PG5-6-3, P2ch, 5 166 m)

above 150 °C. Currently, the burial depth of the Feixianguan
Formation, which is the main gas reservoir pay zone, is buried
to 4 5006 000 m and the formation temperature has reached
120130 °C. Laser Raman spectrometry detection results for
gas inclusions from the P2chT1f reservoir indicate that inclu-
sions with uniform trapping temperatures above 150 °C are
rich in CH4 and H2S (Fig. 4). Therefore, prior to the formation
of the gas reservoir by uplift during the Middle Juras-
sic-Himalayan period, the P2chT1f reservoir fluids of the
Puguang gas field were over the activation energy range for
TSR production. This means volumetrically large H2S forma-
tion can be achieved through TSR, if other conditions can also
be met.
2.3 Spatial Distribution
There are worldwide occurrences of large to extra large
highly sour gas fields such as the Puguang gas field in China,
the Kaybob South gas field of the Western Canada basin (re-
coverable reserves of natural gas are 1 070×108 m3 and H2S
concentrations of 17.74%)[22], the Astrakhan gas field of the
Near Caspian Sea (natural gas recoverable reserves of
2.6×1012 m3, oil recoverable reserves of 7.63×108 t and H2S
concentrations of 22.6%)[22]. The common property through-
out these examples is their occurrence in dolomitized reef flat
facies belts of palaeo-uplifts or palaeo-slope settings, accom-
panied by large amounts of solid bitumen. In diagenesis, such
as early dolomitization and organic acid salt erosion, a high
quality reservoir has been formed near or prior to peak hy-
drocarbon generation of the source rocks, which provides
favorable preservation for early accumulation (prior to deep
burial) of large amounts of crude oil. In Northeastern Sichuan,
the Puguang gas field is mainly productive in the P2chT1f
dolomitized reef flat facies complex, and currently the range
of highly sour areas and palaeo pools of hydrocarbons over-
 Liu Wenhui et al. / Petroleum Exploration and Development, 2010, 37(5): 513–522

Table 2 H2S concentrations in T1f reservoired natural gases from some wells in Northeastern Sichuan
Well No. Depth/m H2S/% Well No. Depth/m H2S/% Well No. Depth/m H2S/%
3 8583 970 14.20 Puguang 10 6 0806 190 13.96 Guan 6* 0.010
Maoba 6 * *
4 7454 841 14.96 Po 1 3 4003 460 14.19 Guan 9 0.010
* *
Maoba 4 4 0504 102 12.73 Po 2 4 0224 162 14.51 Guan 22 0.010
Dawan 2 4 8044 900 14.06 Po 4* 3 3653 395 16.05 Cao 14* 2 173 0.001
* *
5 0295 130 15.73 Du 1 4 3064 354 16.21 Cao 8 0.001
Dawan 1 * *
5 1535 279 13.18 Du 2 4 3624 385 16.24 Cao 10 0.001
Puguang 1 5 638 12.31 Du 3* 4 2724 342 17.06 Chuanfu 82 4 2014 211 0.400
*
4 7774 828 14.80 Du 5 15.86 Chuanyue 83 0.001
Puguang 2 4 9344 985 16.89 Qilibei 1 16.25 Tieshan 5* 0.020
5 0285 102 15.82 Luojia 1* 10.49 Tieshan 11* 2 8242 970 0.740
* *
Puguang 4 5 775 17.10 Luojia 2 3 2113 286 8.77 Tieshan 13 0.590
Puguang 6 5 075 14.05 Luojia 4* 7.13 Tieshan 21* 0.630
* *
5 4855 547 12.79 Luojia 5 2 9322 997 13.74 Cheng 16 0.210
Puguang 7 * *
5 5725 590 13.85 Luojia 6 8.21 Cheng 16 2 5632 669 0.130
5 7395 852 14.03 Luojia 7* 3 8563 956 10.41 Cheng 22* 3 0243 040 0.190
Puguang 9 *
5 9165 993 13.65 Luojia 9 11.68 Qingxi 1 4 285 0.010
Puguang 101 5 7765 786 14.43 Zi 2* 9.23 Shuangmiao 102 4 0504 309 0
*
Note: data from references [14]

laps. In Fig. 3, the H2S abundance contour map is mainly
based on natural gas composition data from every well re-
ported in Table 2.
Due to the unique property of H2S and complexity of its
generation, enrichment and preservation, highly sour gas res-
ervoir distributions show strong non-uniformity. The Ti-
eshanpo, Puguang, Dukouhe and Luojiazhai gas fields in
Northeastern Sichuan generally contain abundant H2S in the
Feixianguan Formation, which is their common pay layer.
This is demonstrated by the relative uniformity of H2S con-
centrations of 12.31%17.10% in the Tieshanpo, Puguang and
Dukouhe fields, with an average of 14.80% (26 samples).
46% of samples have H2S concentrations in the range of
14%16%, while samples with H 2 S concentrations of
12%14% and 16%18% each account for 27% of samples.
In the Luojiazhai region H2S concentrations are relatively low,
ranging from about 7.13% to 13.74%, with an average of
9.96% (8 samples). For adjacent areas, H2S concentrations
drop to below 1% (Fig. 3, Table 2), which demonstrates that
conditions for H2S formation and enrichment in the Tieshanpo,
Puguang and Dukouhe fields are similar, and that these gas
fields belonged to a larger well communicated and uncom-
partmentalized oil and gas fields (reservoirs) when large vol-
umes of H2S formed. Another powerful source of evidence for
common TSR generating mechanisms in this region is that the
presence of these H2S rich areas overlap with current high
reservoir bitumen concentrations (Fig. 3). The fields only
become isolated and independent natural gas fields (reservoirs)
after the adjustment of late tectonic movement. The
neighboring Qingxichang gas reservoir is also located in the
T1f zone, but at present, the gas mainly occurs in later frac-
tures, no solid bitumen is seen, nor development of early reef
flat or other good quality reservoir features favorable for the
formation of palaeo pools. The Heba gas reservoir lacks large
volumes of organic matter for H2S formation due to lack of
space to accomodate early oil and gas migration and accumu-
lation. Therefore, it is necessary that early and effective ac-
cumulation space is available and matches hydrocarbon peak
generation time. For example good quality reservoirs of
dolomitized reef flat facies or palaeo karsts have provided
timely and effective accomodation space for the early accu-
mulation (prior to deep burial) of hydrocarbon-enriched, high
sulfur and magnesic fluids to provide optimal conditions for
TSR reaction of H2S formation and its subsequent enrichment
and accumulation.
2.4 Preservation
H2S, a strong reductant with high levels of chemical activ-
ity is easily consumed quickly under many conditions during
its formation, migration and accumulation. So in order to mi-
grate, accumulate and reside with other gases, additional spe-
cific accumulation and preservation principles must be ful-
filled beside the normal principles in migration, accumulation
and preservation of natural gas. Lean and heavy metal ion
fluids, timely development of accumulation space (specifi-
cally in carbonate rocks), in-situ or near accumulation are all
important factors for H2S enrichment and preservation. As a
result, many highly sour gas fields discovered in the world are
found distributed in carbonate rock or evaporitic sequences
rather than in clastic rocks. Many minerals or rocks containing
heavy metals (Fe, Cu, Pb etc.), especially Fe-group elements
react with H2S to form metal sulfides, which consume H2S.
Previously, the author carried out TSR simulation tests[23] with
the same reactants and under the same testing conditions as
 Liu Wenhui et al. / Petroleum Exploration and Development, 2010, 37(5): 513–522
gold tube simulation tests, in which he chose four test vessels
or autoclaves made of normal stainless steel, special corrosion
resistance (KA4145) alloy steel, glass and quartz tubes, only
to find no H2S was produced, and even the injected H2S was
lost. The reasons lie in: (1) H2S reacts with metal vessels, and
after the test, there was the presence of black precipitates in
the vessel and copper sulfide formed on the copper seal ring;
(2) H2S reacts with glass and quartz tubing and after the test
there was erosion features in the glass tube. Furthermore,
there was the presence of some white material which was
insoluble in water found outside the tube when removing
products from the vessel. Energy spectrum analysis confirmed
the material as SiO2, thus implying a series of reactions be-
tween test tubes and H2S; (3) the formed H2S might be soluble
in water. These preliminary tests clearly demonstrate that rigid
conditions for the selection of TSR simulation test materials
are important for the determination of the environment of
formation and preservation of H2S. Therefore, in actual geo-
logical conditions, the type of reservoir of H2S accumulation,
the chemistry of the formation water in which the H2S might
be dissolved, or the mineral layers passed through during mi-
gration, may all consume H2S so long as they contain heavy
metal ions. Pyrite is commonly seen in the P2chT1f reservoir
of the Puguang gas field, whose sulfur isotopic compositions
have high values (2 samples of the T1f in Well Maoba 3,
Mb3-5-2/3 882 m, Mb3-5-4/3 886 m; and a P2ch rock sample
Pg8-2-4/5 512 m in Well Puguang 8 have į34S of 20.7‰,
15.9‰ and 6.8‰ respectively), indicating abiogenic sulfur,
and being converted from thermochemically produced H2S in
the reservoir.
Generally speaking, clastic rocks and marls are enriched in
heavy metals and easily reactive with H2S to form sulfides,
such as pyrite and galena. When there are large scale activities
of fluids that are H2S-rich, it might contribute to the formation
of sedimentary metal sulfide deposits, such as the Laisvall
sediment-hosted lead and zinc deposits of Sweden[24]. Car-
bonate rocks tend to be poor in heavy metals so that pure car-
bonate rocks are far more favorable for H2S accumulation and
preservation. When formation waters containing heavy metal
ions pass through carbonate rocks, it increases reactions with
H2S in carbonate rocks to form large amounts of sulfides.
Small scale fluid flow can form sulfides like pyrite, or large
scale activities can form Mississippi Valley Type (MVT) sul-
fide mineral resources, such as at Pine Point and the Upper
Mississippi lead and zinc deposits in America and Canada, as
well as the MVT lead and zinc deposits in Sichuan, Yunnan
and Guizhou in China[24].
Table 3 Rock mineralogical composition of the Liangshan Formation in eastern Sichuan[27]
Clay mineral
Well Depth /m Lithology Relative content Relative content
/%
of Quartz
Chi 53 3 0263 029 7.4 16.5
Clay rock
Mingyue 2 3 6193 625 14.2 22.6
Moreover, H2S is easily oxidized to sulfide and deposited
when in contact with formation waters containing free oxygen
or other oxidants, especially with surface fresh water. There-
fore, much H2S is consumed with large amounts of under-
ground water in the basin providing a source of oxygen. This
also indicates that H2S formation and enrichment has been
carried out in both closed and reducing systems, which can
verify dolomitization of deep carbonate rocks reservoirs and a
closed system of burial dissolution[14]. The dissolution and
degassing of H2S in formation water is a complex dynamic
process closely dependent on the formation temperature and
pressure. After the H2S is formed, there is always some H2S
soluble in the formation water but not involved in natural gas
accumulation, even under high temperature high pressure
(HTHP) conditions or as a consequence of uplift and de-
gassing. H2S of uplifted reservoirs and degassing might be
consumed strongly due to long distance migration or other
reasons. The test proves air adsorption capacity of the rock is
improving with the increasing boiling point. Compared with
other gases such as CO2, CH4, and N2, the boiling point of
H2S is higher, so its adsorption capacity on rocks is stronger.
Some H2S is adsorbed to rock layers during long distance
migration and accumulation and removed by migration, even
reacting with some metal elements to form sulfide and be
deposited. This is clearly seen in Carboniferous natural gas
reservoirs of Eastern Sichuan. There are large amounts of
solid bitumen in Carboniferous Systems of Eastern Sichuan,
indicating the existence of palaeo pools, but currently H2S
concentrations in natural gas there is quite low. Amounts av-
erage between 0.000.93% (with the exception of 5% in Well
Tiandong 21) and variations may be related to H2S preserva-
tion conditions. The roof and floor of the Carboniferous res-
ervoir in Eastern Sichuan are both clastic rock layers. The
base of the roof is a mudstone layer of lower Permian age
with a thickness of more than 10 m, and part of the coal
measures of the Liangshan formation[25,26], in which H2S is
consumed easily and difficult to accumulate and maintain H2S
due to the presence of enriched metal elements. X-ray fluo-
rescence analysis of rocks in the Liangshan formation in
Eastern Sichuan shows that pyrite is the main mineral com-
ponent, with a concentration of over 50% (Table 3). This is
clearly a product of Redox reactions between H2S and iron
group elements in this formation and direct evidence of H2S
consumption in this Carboniferous gas field. Therefore, long
distance migration and accumulation increases the chance of
H2S consumption, while reduction reactions and closed sys-
tems are the most important guarantee for H2S enrichment and
Non clay mineral /%
Relative content Relative content Absolute
of feldspar of pyrite of calcite content
09.3 71.9 2.3 92.6
18.5 58.9 85.8
 Liu Wenhui et al. / Petroleum Exploration and Development, 2010, 37(5): 513–522
preservation.
The gypsum-salt layer of the 4th member of the Feixianguan,
Jialingjia and Leikoupo Formations in Northeastern Sichuan,
with thicknesses of tens or hundreds of meters, provide the
best closed systems for medium to large scale natural gas
fields in the area. The presence of gypsum is also one of the
important factors for H2S formation and enrichment in this
area.
3 Highly sour gas accumulation mechanisms in
Northeastern Sichuan
The formation of highly sour gas reservoirs is complex.
Compared with normal hydrocarbon gas reservoirs, conditions
for successful its accumulation are stricter and timing critical.
Based on TSR formation H2S mechanisms, taking the
Puguang gas field as a model and referring to its geological
background, we put forward a highly sour gas accumulation
mechanism consisting of the following steps of “good source
and reservoir for early accumulation; sulphur formation
within the reservoir, cracking to form gas, uplift and migration,
adjustment and hydrocarbon accumulation”.
3.1 Good source and reservoir for early accumulation
Based on analysis of sedimentary structures in the area[7,8],
after the formation of the P2chT1f organic reef flat facies
complex, the infiltration of high salinity Mg-enriched (sulfuric
acid) fluids of nearby lagoons and from the evaporation of
marine waters have led to dolomitization of a reef flat facies
complex. As good quality source rock entered into the early
stages of maturity in the Indosinian (T2 end) and Upper Per-
mian (P2), the P2 source rock provided organic acid and CO2 –
enriched acid fluids while the deep fractured area of NE
Huayingshan began to activate, and the Kaijiang Pa-
laeo-Uplifts and accompanying fault conduit systems began to
form. This caused acid-rich fluids to flow from highs to lower
positions and migrated along the channels like faults, passing
reef flat facies complexes, which altered the alkaline dolo-
mitization fluids to acidic. Subsequent burial corrosion
formed good reservoir space with good porosity and perme-
ability, as well as providing magnesium enriched sulphate
fluids. Meanwhile, immature to low-mature crude oil gener-
ated by the good P2 source rocks first filled in the nearby P2ch
dolomitization reef reservoir. In the Yanshan period (J1J2), P2
source rocks got mature and crude oil and light oil began to
fill the P2ch to T1f reservoirs; the crude oil from the good
source rocks of the Silurian can also fill the P2chT1f reservoir
through a fault system, which forms early crude oil pools be-
fore deep burial. At that point, sulphur-rich and magnesic flu-
ids from many sources accumulated in the reservoir, and
mixed with crude oil to form hydrocarbon-enriched, highly sour
and magnesic fluids, which generate ideal conditions for TSR.
3.2 Sulphur formation within the reservoir & cracking to
form gas
With the burial and heating of P2chT1f reservoir fluids, the
organic matter entered the maturehighly mature stage where
kerogen and sulphur-containing heterocycles or groups of
unstable sulphur-containing organic compounds cracked un-
der thermal stress and formed H2S. Sulphur concentrations of
kerogen is about 0.2%5.0%, with the combination of sulfur
functional groups and C and O dominating. Sulphur concen-
trations of the oils is 0.05%8.00%, mainly existing in the
form of thiols, thioethers, disulfide and thiophene. When these
sulphur-containing organic compounds were buried at a cer-
tain depth, with higher thermal evolution, it is possible to
form H2S due to the breaking of CS or SS bonds, for ex-
ample, mercaptan can be the source of H2S by thermal crack-
ing (RCH2CH2SHėRCH = CH2 + H2S), by which H2S con-
centrations in natural gas is generally below 2%[28]. The simu-
lation test carried out also proves the limitation of its forma-
tion (Fig. 2), which is not enough for highly sour gas fields
with H2S concentrations of over 10%. But this part of H2S
generation produces a strongly reducing environment for fur-
ther H2S formation and preservation in reservoir fluid sys-
tems, stimulating TSR reactions. The presence of these hy-
drocarbon-enriched, highly sour and magnesic fluids activate
TSR reactions, whose function stimulates the TSR reaction
making it easier to occur[12] when a little H2S is added in the
reaction system prior to the test. When organic matter enters
into the wet gas-condensate stage of maturity, and reservoir
temperatures reach 120150 °C, hydrocarbon-enriched and
highly sour fluids in the reservoir become involved in the TSR
reaction, and sulfate from hydrocarbon reduction is used to
form more H2S. This is the main mechanism of H2S formation
in the Northeastern Sichuan P2chT1f reef flat facies reser-
voirs. Also this reaction is within the reservoir, which is
proved by the coexistence of abundant H2S and large amounts
of reservoir bitumen (Fig. 3). The sulphur content of these
reservoir bitumens (T1f, 15 samples, sulfur content
10.9%26.4%, average of 17.46%) is apparently higher than
in such palaeo pools as the Majiang palaeo pools (O1h, 3 sam-
ples, sulfur content 2.52%6.57%, average of 4.66%), mainly
occurring in the form of thiophene. The sulfur isotope compo-
sitions of organic sulfur and its coexisting pyrite have high
positive values indicating abiogenesis (Well Puguang 8,
Pg8-2-4 rock sample, P2ch, 5 512 m, fill in solid bitumen and
pyrite in dolomite fracture, į34S is 11.3‰ and 6.8‰ respec-
tively), indicating it is formed by extensive aromatization
through reservoir crude oil pyrolysis and TSR, processes
which have been preserved until today.
3.3 Uplift, migration and adjustment for hydrocarbon
accumulation
From the Late Cretaceous to Paleogene period, the research
area was uplifted by the Himalayan orogeny, which decreased
the formation temperature and pressure and formed new traps
(including lithologic–tectonic composite traps) and fracture
systems. Large amount of H2S from highly sour gas fields
(reservoirs) such as the Puguang gas field was re-accumulated
in the original place or nearby reservoirs (as mentioned above,
 Liu Wenhui et al. / Petroleum Exploration and Development, 2010, 37(5): 513–522
the coexistence of H2S and reservoir bitumen proves its mi-
gration and accumulation system has been in the reduction
and closed state, which is the necessary environment for H2S
continued existence). The H2S was also mixed with hydro-
carbons and other non-hydrocarbon gases during accumula-
tion, and finally formed the current highly sour gas fields
(reservoirs) observed today.
4 H2S distribution and prediction of marine facies
natural gas reservoirs in Northeastern Sichuan and
its periphery
The prediction of highly sour gas distribution is based on
the main controlling factors and pooling mechanisms of
highly sour gas, as well the matching of the four main con-
trolling factors of source, energy, space and preservation.
In the period of P2chT1f deposition, there was a sedimen-
tary reef flat facies formed in the HuanguagnwangKai-
jiangLiangping continental shelf margin, which evolved to
produce a good quality reservoir through diagenesis (dolo-
mitization and erosion) before deep burial, and formed palaeo
pools with good spatial-temporal matching of evaporation
facies (salt-water systems) and deep water facies (hydrocar-
bon source), creating a basis for H2S formation by TSR in
deeply buried areas. One example is the P2chT1f palaeo
pools of Northeastern Sichuan (Fig. 3); until the period of
T1T2, there was a sedimentary gypsum-salt rock layer in the
Sichuan Basin, which accounts for 100-600m in Northeastern
Sichuan, as the seal for the preservation of P2chT1f sour
natural gas. It also provides sulphur –rich and magnesic ma-
rine source fluids for the P2chT1f reservoir. In the Heichili-
ang region is the block being explored by Sinopec, which is
located at the northern end of the NE Tongnanba anticlinal
structural belt in middle of Sichuan. To the south is the Lower
Triassic gas reservoir of Heba, whose sedimentary facies belt
is located in a reef flat facies on the northern margin of the
Huanguangwang-Kaijiang-Liangping continental shelf as is
the Puguang gas field. Seismic data and research have proved
this region has a large P2chT1f reef flat facies abnormality,
indicating large reserve potential[29,30]. Therefore, it is pre-
dicted that the Heichiliang P2chT1f reef flat facies is a fa-
vorable region where early stage oil and gas accumulation
went through TSR to form large quantities of H2S due to late
stage deep burial, identified during exploration. While in other
regions, including the inside of the slope belt and continental
shelf, their composition is of compact carbonate rocks which
are mainly fractured and formed at a later stage, they also and
lack the accumulation conditions for the formation of early
stage palaeo pools. This means a lack of conditions for large
scale H2S formation, such as at the Heba and Qingxichang gas
reservoirs. Therefore, other marine facies carbonate rock lay-
ers of the region such as the Jialingjia and Leikoupo Forma-
tions also lack the conditions more typical of H2S preservation,
that is an absence of palaeo pools, even though there are
highly sour gases migrating from the P2chT1f reservoir. But
due to the long distance migration, sulphur was largely con-
sumed and the highly sour gas becomes a sweet natural gas.
Marine and continental facies, clastic rock layers such as the
Silurian, Xujiahe Formation cannot form highly sour gas field,
even with H2S concentrations due presence of heavy
metal-enrichment, which has been proved by continental fa-
cies oil and gas exploration and the drilling results of Well
Jianshen 1 in Southwestern Sichuan.
5 Conclusions
In Northeastern Sichuan, there are two H2S formation
mechanisms for the P2chT1f reservoir under geological con-
ditions of burial and heating: pyrolysis of sulphur-rich organic
matter, and Thermochemical Sulfate Reduction (TSR) of hy-
drocarbon-enriched, high sulphur and magnesic fluids. Among
which, the latter needs enough magnesic SO42 solution and
hydrocarbon supply, which is the main materials for H2S for-
mation. The formation of highly sour gas reservoirs is not
only about H2S formation mechanisms, it also concerns H2S
enrichment, which is controlled by source supply, energy
range, formation environment and preservation conditions. In
other words, sufficient materials, enough energy supply,
proper accumulation space and a rigid reduction environment
are the main controlling factors for H2S formation and the
enrichment of medium to large scale natural gas fields in
Northeastern Sichuan. The series of factors and timing de-
pendence between them is the main mechanism for the forma-
tion of highly sour gas fields. Based on this mechanism, it is
predicted that there is the possibility of developing highly
sour gas reservoirs in the Heichiliang reef flat facies sedimen-
tary area in Northeastern Sichuan. While in regions dominated
by compact carbonatite of a syndepositional relationship in
the P2chT1f reef flat facies reservoirs, including slope belt,
inner continental shelf and the Jialingjia and Leikoupo For-
mations, the lack of materials, namely palaeo pools, or short-
age of energy, makes it difficult to form highly sour gas res-
ervoirs. Even though there are highly sour gases migrating
from the P2chT1f reservoir, sulphur was greatly consumed
during long distance migration, producing a sweet natural gas.
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