fluid mixing induced by hydrothermal activity in the ordovician carbonates in tarim basin, china

16
Fluid mixing induced by hydrothermal activity in the ordovician carbonates in Tarim Basin, China L. JIANG 1,2 , W. PAN 3 , C. CAI 1 , L. JIA 1 , L. PAN 4 , T. WANG 1 , H. LI 1 , S. CHEN 1,5 AND Y. CHEN 1 1 Key Lab of Petroleum Resources, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing, China; 2 Department of Geology and Geophysics, School of Environmental Sciences, University of Liverpool, Liverpool, UK; 3 Tarim Oilfield Company, PetroChina, Korla, Xinjiang, China; 4 PetroChina Hangzhou Research Institute of Geology, Hangzhou, China; 5 Energy Resource Department, China University of Geosciences, Beijing, China ABSTRACT Permian hydrothermal activity in the Tarim Basin may have been responsible for the invasion of hot brines into Ordovician carbonate reservoirs. Studies have been undertaken to explain the origin and geochemical characteris- tics of the diagenetic fluid present during this hydrothermal event although there is no consensus on it. We pres- ent a genetic model resulting from the study of d 13 C, d 18 O, d 34 S, and 87 Sr/ 86 Sr isotope values and fluid inclusions (FIs) from fracture- and vug-filling calcite, saddle dolomite, fluorite, barite, quartz, and anhydrite from Ordovician outcrops in northwest (NW) Tarim Basin and subsurface cores in Central Tarim Basin. The presence of hydrothermal fluid was confirmed by minerals with fluid inclusion homogenization temperatures being >10°C higher than the paleo-formation burial temperatures both in the NW Tarim and in the Central Tarim areas. The mixing of hot (>200°C), high-salinity (>24 wt% NaCl), 87 Sr-rich (up to 0.7104) hydrothermal fluid with cool (60100°C), low-salinity (0 to 3.5 wt% NaCl), also 87 Sr-rich (up to 0.7010) meteoric water in the Ordovician unit was supported by the salinity of fluid inclusions, and d 13 C, d 18 O, and 87 Sr/ 86 Sr isotopic values of the diagenetic minerals. Up-migrated hydrothermal fluids from the deeper Cambrian strata may have contributed to the hot brine with high sulfate concentrations which promoted thermochemical sulfate reduction (TSR) in the Ordovician, resulting in the formation of 12 C-rich (d 13 C as low as 13.8&) calcite and 34 S-rich (d 34 S values from 21.4& to 29.7&)H 2 S, pyrite, and elemental sulfur. Hydrothermal fluid mixing with fresh water in Ordovician strata in Ta- rim Basin was facilitated by deep-seated faults and up-reaching faults due to the pervasive Permian magmatic activity. Collectively, fluid mixing, hydrothermal dolomitization, TSR, and faulting may have locally dissolved the host carbonates and increased the reservoir porosity and permeability, which has significant implications for hydrocarbon exploration. Key words: carbonates, dolomitization, hydrothermal fluids, meteoric water, Tarim Basin, thermochemical sulfate reduction Received 30 July 2014; accepted 20 November 2014 Corresponding author: Prof Dr Chunfang Cai, Key Lab of Petroleum Resources, Institute of Geology and Geo- physics, Chinese Academy of Sciences, Beijing 100029, China. Email: [email protected]. Tel: +86 108 299 8127. Fax: +86 106 201 0846 Geofluids (2014) INTRODUCTION In the past few decades, the question of hydrothermal activity due to tectonic movements has gained increasing attention and interest by petroleum geologists in carbonate reservoir exploration (Qing & Mountjoye 1994; Lavoie et al. 2005; Davies & Smith 2006; Saller & Dickson 2011). This is because not only the hydrothermal activity itself can cause faults and fractures that improve the reservoir quality, but also the hydrothermal fluid mixing and hydrothermal dolomitization could either dissolve cal- cite or led to replacement of calcite by dolomite that both created secondary porosity (Corbella et al. 2004; Lavoie et al. 2005; Smith 2005; Davies & Smith 2006; Wendte 2006; Wendte et al. 2009; Lapponi et al. 2014). Lower Ordovician carbonates in the Tarim Basin represent an important hydrocarbon reservoirs associated with karstifica- tion (most commonly in the Yinshan Formation-O 1-2 y), © 2014 John Wiley & Sons Ltd Geofluids (2014) doi: 10.1111/gfl.12125

Upload: independent

Post on 13-Nov-2023

0 views

Category:

Documents


0 download

TRANSCRIPT

Fluid mixing induced by hydrothermal activity in theordovician carbonates in Tarim Basin, China

L. J IANG1 , 2 , W. PAN3 , C. CAI1 , L . J IA1 , L . PAN4 , T . WANG1, H. LI1 , S . CHEN1 , 5 AND Y.

CHEN1

1Key Lab of Petroleum Resources, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing, China;2Department of Geology and Geophysics, School of Environmental Sciences, University of Liverpool, Liverpool, UK; 3Tarim

Oilfield Company, PetroChina, Korla, Xinjiang, China; 4PetroChina Hangzhou Research Institute of Geology, Hangzhou,

China; 5Energy Resource Department, China University of Geosciences, Beijing, China

ABSTRACT

Permian hydrothermal activity in the Tarim Basin may have been responsible for the invasion of hot brines into

Ordovician carbonate reservoirs. Studies have been undertaken to explain the origin and geochemical characteris-

tics of the diagenetic fluid present during this hydrothermal event although there is no consensus on it. We pres-

ent a genetic model resulting from the study of d13C, d18O, d34S, and 87Sr/86Sr isotope values and fluid

inclusions (FIs) from fracture- and vug-filling calcite, saddle dolomite, fluorite, barite, quartz, and anhydrite from

Ordovician outcrops in northwest (NW) Tarim Basin and subsurface cores in Central Tarim Basin. The presence of

hydrothermal fluid was confirmed by minerals with fluid inclusion homogenization temperatures being >10°C

higher than the paleo-formation burial temperatures both in the NW Tarim and in the Central Tarim areas. The

mixing of hot (>200°C), high-salinity (>24 wt% NaCl), 87Sr-rich (up to 0.7104) hydrothermal fluid with cool (60–

100°C), low-salinity (0 to 3.5 wt% NaCl), also 87Sr-rich (up to 0.7010) meteoric water in the Ordovician unit

was supported by the salinity of fluid inclusions, and d13C, d18O, and 87Sr/86Sr isotopic values of the diagenetic

minerals. Up-migrated hydrothermal fluids from the deeper Cambrian strata may have contributed to the hot

brine with high sulfate concentrations which promoted thermochemical sulfate reduction (TSR) in the Ordovician,

resulting in the formation of 12C-rich (d13C as low as �13.8&) calcite and 34S-rich (d34S values from 21.4& to

29.7&) H2S, pyrite, and elemental sulfur. Hydrothermal fluid mixing with fresh water in Ordovician strata in Ta-

rim Basin was facilitated by deep-seated faults and up-reaching faults due to the pervasive Permian magmatic

activity. Collectively, fluid mixing, hydrothermal dolomitization, TSR, and faulting may have locally dissolved the

host carbonates and increased the reservoir porosity and permeability, which has significant implications for

hydrocarbon exploration.

Key words: carbonates, dolomitization, hydrothermal fluids, meteoric water, Tarim Basin, thermochemical sulfate

reduction

Received 30 July 2014; accepted 20 November 2014

Corresponding author: Prof Dr Chunfang Cai, Key Lab of Petroleum Resources, Institute of Geology and Geo-

physics, Chinese Academy of Sciences, Beijing 100029, China.

Email: [email protected]. Tel: +86 108 299 8127. Fax: +86 106 201 0846

Geofluids (2014)

INTRODUCTION

In the past few decades, the question of hydrothermal

activity due to tectonic movements has gained increasing

attention and interest by petroleum geologists in carbonate

reservoir exploration (Qing & Mountjoye 1994; Lavoie

et al. 2005; Davies & Smith 2006; Saller & Dickson

2011). This is because not only the hydrothermal activity

itself can cause faults and fractures that improve the

reservoir quality, but also the hydrothermal fluid mixing

and hydrothermal dolomitization could either dissolve cal-

cite or led to replacement of calcite by dolomite that both

created secondary porosity (Corbella et al. 2004; Lavoie

et al. 2005; Smith 2005; Davies & Smith 2006; Wendte

2006; Wendte et al. 2009; Lapponi et al. 2014). Lower

Ordovician carbonates in the Tarim Basin represent an

important hydrocarbon reservoirs associated with karstifica-

tion (most commonly in the Yinshan Formation-O1-2y),

© 2014 John Wiley & Sons Ltd

Geofluids (2014) doi: 10.1111/gfl.12125

thermochemical sulfate reduction (TSR), and dolomitiza-

tion (most commonly in the Penglaiba Formation-O1p)

(Cai et al. 2001a,b, 2009b; L€u et al. 2008; Yang et al.

2012). Significantly, hydrothermal minerals such as calcite,

saddle dolomite, fluorite, barite, anhydrite, and quartz have

been found to occur both in the subsurface cores of Taz-

hong and Tahe areas (Cai et al. 2008; Li et al. 2011; Yang

et al. 2012) and in outcrops of NW Tarim region in the

Ordovician strata (Xing & Li 2012; Dong et al. 2013;

Zhang et al. 2014), as supported by their high homogeni-

zation temperatures in fluid inclusions, positive Eu anoma-

lies as well as characteristic d18O, d13C, and 87Sr/86Sr

isotopic values of the deep burial diagenetic minerals. Pre-

vious studies have argued that hydrothermal fluids during

this period may have been related to Permian magmatic

activity based on the detailed petrological and geochemical

evidence (Cai et al. 2008; L€u et al. 2008; Xing & Li

2012; Dong et al. 2013; Zhang et al. 2014).

However, influx of meteoric water also occurred locally

in the Ordovician strata during hydrothermal fluid move-

ment, leading to a significant decrease in the paleo-water

salinity and Mn abundance (Cai et al. 2008; Li et al.

2011; Zhang et al. 2014), as well as an increase in the

depth of karstification (L€u et al. 2008). Thus, fluid mixing

during the Permian hydrothermal activity in Tarim Basin

was a complicated chemical and physical process, which

not only altered the hydrocarbon properties (Xing & Li

2012) but also significantly affected the reservoir porosity

(L€u et al. 2008; Yang et al. 2012). Although hydrothermal

diagenetic minerals in Ordovician strata in Tarim Basin

have been reported in previous studies, there is no consen-

sus on the origin and geochemical composition of these

hydrothermal fluids, and there is no comprehensive model

to explain all the observations.

In this study, detailed geochemical and petrological

analyses have been performed on the deep burial diagenetic

minerals in Ordovician strata both from subsurface cores in

Tazhong area and from outcrop samples in Taxibei area, in

an attempt to determine the origin of fluids and fluid flow

and mixing during this hydrothermal event. Specifically, we

have addressed the following questions:

(1) What are the petrological and geochemical characteris-

tics of diagenetic minerals during the hydrothermal

event in the Ordovician strata in the Tarim Basin,

China?

(2) What is the model for fluid mixing during the hydro-

thermal event?

(3) What are the implications for the hydrothermal event

on the reservoir quality of carbonate rocks from Ordo-

vician strata?

GEOLOGICAL SETTING

The Tarim Basin is located in the northwest of China

(Fig. 1A). The detailed geology of the Tarim Basin has

been reported in Cai et al. (2009a). Briefly, during the

Cambrian and Ordovician, the study area was located on a

stable shallow marine carbonate platform to deep basin

environment and resulted in the deposition of up to

2000 m carbonates and mudstone, including platform

(A) (B)

Fig. 1. Map of the Tarim Basin showing tectonic units, locations of sampled wells and outcrops (A); lithology of Cambrian to Ordovician strata in the Tarim

Basin (B).

© 2014 John Wiley & Sons Ltd

2 L. JIANG et al.

facies limestone and dolomite, slope facies limestone and

marlstone, and basinal facies mudstone, shale, and marl-

stone (Fig. 1B). During the Silurian to Carboniferous, the

sea level decreased and the Tarim Basin evolved to

undergo deposition of a marine sandstone and mudstone

sequence. The study area had further evolved to result in

the deposition of lacustrine sediment and volcanic rock

during the Permian, and fluvial sandstone and mudstone

during the Mesozoic and Cenozoic.

Several orogenies have led to formation of multiple un-

conformities and resulted in much missing section in the

Tarim Basin. For example, the Middle and Upper Ordovi-

cian in the eastern Central Tarim and Taxibei areas were

completely removed by erosion during the late Caledonian

orogeny at the end of Ordovician. There are no Devonian

or Silurian strata remaining in the majority of the Taxibei

area due to the early Hercynian orogeny at the end of the

Devonian. Moreover, the late Yanshanian orogeny, during

the Neogene, resulted in either no sedimentation or com-

plete removal of the Cretaceous in the Southwest Depres-

sion, eastern Central Tarim. These orogenies, resulting in

fracturing and tilting, have been linked to large-scale fluid

cross-formational flow in the Tarim Basin.

Notably, intense volcanic activities have extensively taken

place in Tarim Basin as a result of convergent subduction

of Middle Tianshan arc to the north in Early Permian

(Chen et al. 1997; Tang et al. 2004). At the end of Perm-

ian, the further amalgamation led to an extensive uplift

and subsequent long-term subaerial exposure and erosion

of the Tarim Basin. The presence of alkaline basalt, dia-

base, and granite intrusions led to invasion of the hydro-

thermal fluids and the growth of hydrothermal minerals

(e.g., fluorite, quartz, barite, saddle dolomite, and calcite)

in the Upper Cambrian to Ordovician strata in study area

(Pan et al. 2009; Yang et al. 2012; Dong et al. 2013).

The burial and geothermal histories of different tectonic

units of the Tarim Basin have been reported previously by Ye

(1994) and Cai et al. (2009a) and references therein. Briefly,

the Ordovician strata in Tazhong area have been buried to

>4000 m, with paleo-temperatures up to about 140°C(Fig. 2A,). In contrast, the burial history of Taxibei outcrops

area shows that the Ordovician strata were buried to about

4000 m during middle Permian before the whole section

was uplifted to the surface in early Triassic (Fig. 2C), and

the maximum paleo-temperature was <140°C (Fig. 2B).

METHODS

A total of 120 carbonate rock samples, with some associ-

ated with anhydrite, barite, fluorite, pyrite, and elemental

sulfur samples from the Ordovician unit, were collected

from Keping, Qingsong, Dawangou, Qieditage, Tuopu-

lang, and Xike’er outcrops in NW Tarim Basin and from

subsurface cores in TZ3, TZ12, TZ161, TZ162, TZ243,

TZ45, TZ62, TZ826, and ZG12,ZG171, ZG 431,

ZG442H, ZG45, ZG51, and ZG9 wells in the Central Ta-

rim Basin (Fig. 3). Selected samples were used for petrol-

ogy and geochemical analyses, including transmitted

microscope and fluid inclusion analyses, carbon, oxygen,

and strontium isotopic analyses. Finely polished and etched

slabs and thin sections were stained with Alizarin Red S

and potassium ferricyanide to distinguish calcite from dolo-

mite and their ferroan equivalents.

Fluid inclusions in double-polished wafers were studied

using a Linkam THMSG 600 heating–cooling stage con-

nected to Zeiss petrographic microscope which was used

(A) (B)

Fig. 2. Burial histories of the Ordovician sediments in different tectonic units: (A) from well TZ29 in Tazhong area and (B) from outcrops in Taxibei area.

© 2014 John Wiley & Sons Ltd

Hydrothermal fluid in ordovician carbonates in Tarim Basin 3

to obtain temperature data. UV fluorescence was per-

formed on these doubly polished wafers to determine

whether they were oil or aqueous inclusions, to identify

inclusion types for further analysis, and to determine their

relationship to the host minerals. Instrumental precision is

�0.1°C. Ice melting temperatures were converted to salin-

ity using standard equations (Oakes et al. 1990; Bodnar

2003).

Fine powder samples of calcite and dolomite were

extracted using a dentist’s drill and subject to carbon and

oxygen isotopes analyses. About 30–50 mg of drilled out

sample was reacted overnight with 100% phosphoric acid

at 25°C under vacuum to release CO2 from the carbonate

minerals. The CO2 was then analyzed for carbon and oxy-

gen isotopes on a Finnigan MAT251 mass spectrometer

standardized with NBS-18. All carbon and oxygen data are

reported in units per mil relative to the Vienna Peedee Bel-

emnite (VPDB) standard, respectively. The precision for

both d13C and d18O measurements is �0.1&.

About 60 mg drilled samples were used for strontium

isotope analyses. Calcite was leached in 0.5 M sub-boiling

distilled acetic acid at room temperature for 4 h, and dolo-

mite was dissolved in 3.4 M acetic acid at 60°C for 24 h,

respectively (Jiang et al. 2013). Anhydrite samples and bar-

ite samples were digested with 2.5 M HCl at 90°C for

24 h and with HF+HNO3+HClO4 at 190°C for 7 days in

Teflon capsules, respectively. Strontium in each component

was further separated by the conventional cation exchange

techniques using ion exchange resin (packed with Bio-Rad

AG50Wx8). Strontium isotope analyses were performed on

a Finnigan MAT-262 multicollector thermal ionization

mass spectrometer (TIMS) at Institute of Geology and

Geophysics, Chinese Academy of Sciences (IGGCAS), Beij-

ing. All 87Sr/86Sr ratios were adjusted to 0.710253 for

NBS987.

Sulfur isotopic determinations were carried out on a

Thermo Finnigan Delta S mass spectrometer, calibrated by

a series of IAEA standards. The pyrite and elemental sulfur

was liberated as H2S with chromic chloride solution (Can-

field et al. 1986). 0.1 M AgNO3 was subsequently added

to precipitate Ag2S for stable S isotope composition

(34S/32S) analysis. The d34S values are reported relative to

the Vienna Canyon Diablo troilite (VCDT) standard with

reproducibility better than �0.3&.

RESULTS

Petrology

Fracture- and vug-filling calcite, saddle dolomite, fluorite,

barite, pyrite, sphalerite, galena, and elemental sulfur were

commonly observed in the Ordovician unit both in NW Ta-

rim Basin and in Central Tarim Basin, and many of these

minerals were hydrothermal in origin based on their fluid

inclusion-derived precipitation temperatures being 10–50°Chigher than the highest paleo-temperature inferred from the

burial–thermal history (Fig. 2; Machel & Lonnee 2002; Cai

et al. 2008). This temperature anomaly is too great to be

explained by uncertainty or error in the modeled thermal

history of the area. In this study, we mainly focused on the

Fig. 3. Distribution of hydrothermal minerals

in the Ordovician strata in Central Tarim.

Data from a* (Cai et al. 2008) and b* (Yang

et al. 2012) are incorporated; HTD stands for

hydrothermal dolomite.

© 2014 John Wiley & Sons Ltd

4 L. JIANG et al.

late diagenetic minerals that were more likely to be of hydro-

thermal origin, whereas primary carbonate host rock compo-

nents and early diagenetic minerals were not the main

concern in this contribution. For clarification, we have listed

the paragenetic sequence in Fig. 4, in which the relatively

early diagenetic events were adapted from Cai et al. (2008),

Li et al. (2011), and Dong et al. (2013).

Calcite occurs commonly as cements in enlarged dissolu-

tion vugs and fractures and exhibits a milky white appear-

ance and coarse crystal sizes, commonly associated with

abundant solid bitumen (pyrobitumen) (Fig. 5A,D). Less

commonly, calcite has replaced limestone host rock or bar-

ite and anhydrite (Fig. 5B,G). Barite occurs as tabular,

vug-fillings, and crosscuts giant calcite crystals (Fig. 5B).

Abundant fluorite crystals are present in the caves (Fig 5C)

close to the Ordovician Lianglitage Formation/Yinshan

Formation (O3l/O1-2y) unconformity and are closely asso-

ciated with calcite and anhydrite in some outcrops

(Fig. 5D). Saddle dolomite can also be frequently observed

in the Ordovician unit. The amount of dolomite seems to

increase with increasing age (Fig. 5E), possibly suggesting

that the dolomitizing fluid was likely from the deeper

strata. The saddle dolomites occur close to fractures and

show coarse crystal up to 3 mm (Fig. 5F). The occurrence

of anhydrite dissolution and replacement of anhydrite by

calcite was visible in several thin sections (Fig. 5G). Volu-

metrically minor yellow elemental sulfur was also locally

observed in secondary dissolution pores (Fig. 5H). Euhe-

dral and coarsely crystalline pyrite frequently occurs in

micro-fractures, dissolution vugs, and intergranular cracks

(Fig. 5I), commonly representing less than 1%, but locally

up to 3%, by volume.

Good carbonate reservoirs in the Ordovician strata in

Tarim Basin are commonly associated with faults and

fractures although some of them are filled with the hydro-

thermal minerals mentioned previously (Fig. 5J). Hydro-

thermal dolomitization (HTD) is another common

phenomenon present in both the NW Tarim Basin and

Central Tarim Basin (Fig. 5K); point counting indicates

that these HTDs have relatively high porosity (Fig. 5L)

(locally up to >10%; Fig. 4). Less commonly, in some out-

crops in NW Tarim, large numbers of deep-seated fractures

have been found connecting with giant caves (Fig. 5M),

and these fractures and caves were partially filled by hydro-

thermal minerals (e.g., fluorite, calcite, anhydrite, sulfur).

Therefore, the above findings probably suggest that deep-

seated fractures may have provided pathways for hydrother-

mal fluids to flow and may have been responsible for the

formation or preservation of part of these caves in deep

burial environments.

Fig. 4. Paragenetic sequence of the Ordovician unit in Tarim Basin summarizing major products of seawater, near-surface, shallow-burial, mesogenetic to

deep burial, uplifting diagenesis, and the temperature and porosity in each diagenetic realm. Temperature and porosity data have been revealed by fluid

inclusion analysis and point counting for the thin sections, respectively. Relatively early diagenetic events (seawater diagenesis, near-surface realm, and shal-

low-burial realm) were adapted from Cai et al. (2008), Li et al. (2011), and Dong et al. (2013).

© 2014 John Wiley & Sons Ltd

Hydrothermal fluid in ordovician carbonates in Tarim Basin 5

(A) (B) (C)

(D) (E) (F)

(G) (H) (I)

(J)

(M)

(K) (L)

Colouronline,B&W

inprint

© 2014 John Wiley & Sons Ltd

6 L. JIANG et al.

Fluid inclusion (FI) homogenization temperature and

salinity

Doubly polished detachable wafers (45 in total) of fluorite

and dolomite samples were prepared from subsurface core

samples. Petrography, using transmitted light and UV fluo-

rescence, was performed on doubly polished wafers to

identify inclusion types for further analysis and to deter-

mine their relationship to the host minerals. All minerals

contain primary, two-phase aqueous inclusions. These fluid

inclusions showed no signs of deformation or leakage,

suggesting that the homogenization temperature data are

not an artifact of postformational processes.

Calcite and barite have homogenization temperatures

ranging from 60°C to 180°C (Fig. 6A) and 100°C to

160°C (Fig. 6E), respectively. Note that calcite and barite

with relatively high temperatures have relatively high

salinity values, lying between 14 wt% and 24 wt%

(Fig. 6B) and between 14 wt% and 22 wt% (Fig. 6F),

respectively.

Dolomite samples have a relatively narrow range of

homogenization temperatures, varying from 70°C to

(A) (B)

(C) (D)

(E) (F)

(G) (H)

Fig. 6. Histograms showing homogenization

temperatures and salinities measured from

fluid inclusions of hydrothermal minerals from

the Upper Ordovician strata in Tarim Basin.

Fig. 5. (A) late-stage fracture-filling calcite (yellow arrow) in O3l, from well TZ42, depth 5380 m; (B) late-stage calcite (in red color) and barite (yellow

arrow) replace the limestone host rock in O3p, from well TZ162, depth 5981.4 m; (C) giant cave presented in the Ordovician O3t/O1-2y unconformity, with

fluorite, calcite, and anhydrite locally filling in, from Xike’er outcrop; (D) calcite (write color) and fluorite (purple color; yellow arrow) filling in the fracture in

the Ordovician Yijianfang formation, from Xike’er outcrop; (E) dolomitization along the fractures showed in the yellow framed area, dolomite amount increas-

ing with increased depth, from Qingsong outcrop; (F) saddle dolomite shows undulose extinction under crossed nicols, from Qingsong outcrop; (G) the

photograph shows the dissolution of anhydrite and replacement by calcite; blue dash represents the corrosion interface between anhydrite and calcite, from

well TZ826, Upper Ordovician; (H) the photograph shows yellow elemental sulfur (yellow arrow) filling the isolated pores associated with bitumen, O1 from

well TZ243, depth 5750 m; (I) the photograph shows coarse-crystallized pyrite distributed along the micro-fractures, O1-2y from well TZ3; (J) fracture-related

porosity and late diagenetic infillings (calcite, pyrite, sulfur, etc.) in limestone, from well TZ3, depth 3708.1 m; (K) the photograph shows fracture-related

hydrothermal dolomite (HTD), suggesting fracture provided pathways for hydrothermal fluids for dolomitization, from well TZ12, depth 5237.0 m; (L) thin

section made from (K), showing relatively high porosity (in red color); (M) photograph shows fracture-controlled caves in the Ordovician strata, hydrothermal

minerals (e.g., fluorite, calcite, anhydrite, sulfur) commonly occurred in the caves, outcrop from Xike’er outcrop.

© 2014 John Wiley & Sons Ltd

Hydrothermal fluid in ordovician carbonates in Tarim Basin 7

140°C, with an average value of 97°C (Fig. 6C). Paleo-

water present during dolomite growth has salinities from

16 wt% to 23.3 wt%, with an average value of 21 wt%

(Fig. 6D). Salinities slightly increase with the increasing

temperatures of trapping both for the entire dataset and

for individual samples.

Fluorite samples show a wide range of homogenization

temperatures varying from 142°C to 283°C, with an aver-

age value of 179°C (Fig. 6G). Water salinities at the time

of fluorite growth ranged from 0.5 wt% to 18.3 wt%, with

an average value of 6 wt% (Fig. 6H). The relationship

between salinity and temperature is poor; however, when

the salinities are higher than 10 wt%, the trapping tempera-

ture is lower than 150°C.

C/O/S/Sr isotope data

Carbon and oxygen isotopic composition of the Ordovi-

cian carbonates are presented in Fig. 7 and Table 1. Frac-

ture- and vug-filling calcites show broadly similar d13Cvalues falling within a range between �7.11& and 2.49&,

with d18O values between �17.39& and �5.41&(Fig. 7). Saddle dolomite has a narrow range of both d13Cvalues (between �1.37& and �0.76&) and d18O values

(between �8.33& and �7.98&; Fig. 7).

Sulfur isotopic composition of pyrite from four subsur-

face core samples and of one elemental sulfur core sample

are presented in Table 1. The pyrites show a narrow range

from 22.3& to 29.7&, and the elemental sulfur sample

has d34S ratio of 21.4&.

Strontium isotopic compositions of the dolomite, calcite,

anhydrite, fluorite, and barite are presented in Fig. 8 and

Table 1. Calcite and saddle dolomite samples in the Ordovi-

cian show 87Sr/86Sr ratios from 0.708823 to 0.710445 and

from 0.708824 to 0.709840, respectively. Anhydrite samples

have 87Sr/86Sr ratios from 0.709110 to 0.710136. One bar-

ite sample has a high 87Sr/86Sr ratio of 0.710009 (Table 1).

DISCUSSION

Hydrothermal origin of deep burial diagenetic minerals

Hydrothermal minerals (e.g., saddle dolomite, fluorite,

barite, calcite, pyrite, galena, sphalerite) in the Ordovician

strata in Tarim Basin occur as fracture- and vug-fillings or

cements in fault zones, or as cements or infillings in caves

either close to or far away from the unconformity, which

connected with deep-seated fractures (Figs 5 and 10; Cai

et al. 2008; Pan et al. 2009; Yang et al. 2012). Thus, the

hydrothermal minerals may have been controlled by local

structures, and fracture networks may have provided favor-

able conduits and pathways for the deep basinal hydrother-

mal fluids (Cai et al. 2001a; L€u et al. 2008; Li et al. 2011;

Yang et al. 2012; Dong et al. 2013). Apart from the

hydrothermal mineral assemblage, it has been commonly

reported that granite intrusions and diabase dikes, as well

as the metamorphic limestone, outcrop in the NW Tarim

Basin (Pan et al. 2009; Zhang et al. 2014). Hence, it is

possible that the late-stage diagenetic minerals in this study

are hydrothermal in origin or are closely related to the

hydrothermal activity.

Two-phase aqueous inclusions with relatively high

homogenization temperatures were trapped within saddle

dolomite, fluorite, calcite, and barite. The two-phase aque-

ous inclusions in saddle dolomite in the Keping, Penglaiba,

and Qingsong outcrops show that dolomite growth

occurred during burial diagenesis when the temperatures

were between 70°C and 138°C (Fig. 6C), being similar to

the reported Upper Cambrian hydrothermal dolomite

(HTD) temperature in the Keping outcrop (Dong et al.

2013), and within the HTD precipitation temperature

ranges worldwide as summarized by Davies & Smith

(2006). The two-phase aqueous inclusions in fluorite in

the Sanjianfang, Xikeer, and Tumuxiuke outcrops show

that fluorite growth occurred during hydrothermally influ-

Fig. 7. Cross-plot of d18O and d13C values in

the fracture-, vein-, and vug-filling calcite and

saddle dolomite in the Ordovician unit in

Tarim Basin.

© 2014 John Wiley & Sons Ltd

8 L. JIANG et al.

enced burial diagenesis when the temperature was between

142°C and 283°C (Fig. 6G), which is significantly higher

than the reported fluorite temperatures in the Tazhong

area (Cai et al. 2008; Li et al. 2011). Burial diagenetic

vug- or fracture-filling calcite, both in this study and in

previous studies, has a relatively wide precipitation temper-

ature range, from 80°C to 160°C (Fig. 6A; Li et al.

2011). Barite has also precipitated at temperatures up to

160°C, which is significantly higher than the highest burial

temperature (140°C; Fig. 2) in the Ordovician strata

(Fig. 6G), whereas Upper Cambrian to Ordovician vug-

filling quartz cement has been reported to have fluid inclu-

sion homogenization temperatures even up to 300°C(Xing & Li 2012). The formation temperatures of all

above-mentioned minerals (dolomite, calcite, fluorite, bar-

ite, quartz) have their highest homogenization tempera-

tures significantly higher (>10°C; Fig. 6) than the hottest

burial temperatures (Fig. 2), suggesting there was an inva-

sion of hydrothermal fluid into the Ordovician strata in the

Tarim Basin (Smith 2005; Davies & Smith 2006; Cai et al.

2008; Wendte et al. 2009; Lapponi et al. 2014).

Two-phase aqueous inclusions in saddle dolomites, vug-

and fracture-filling calcites, and barites all show relatively

high salinities (up to 24 wt% NaCl; Fig. 6D), and their

salinities systematically increase with increasing fluid

inclusion homogenization temperatures. There are only a

few ways for formation waters to achieve salinities >24 wt%

NaCl: (i) extreme evaporation of seawater or connate water

Table 1 d13C, d18O, and 87Sr/86Sr values of the dolomites in the Ordovician Strata.

sample formation description d13C& VPDB d18O& VPDB d34S& VCDT 87Sr/86Sr

KP10-1 O1p Fracture-filling calcite �0.84 �14.86 – 0.709286QD-1 O Fracture-filling calcite �1.61 �7.49 – 0.708823QD-2 O Fracture-filling calcite �1.49 �7.65 – 0.708935TZ12-1 O3l Vug-filling calcite – – 0.709774

TZ12-2 O3l Vug-filling calcite – – 0.709211TZ45-1 O3l Vug-filling calcite – – 0.707970TZ45-2 O3l Vug-filling calcite – – 0.709408QS-9-1 O1-2y Vug-filling calcite 2.49 �16.57 – 0.709249QS-9-2 O1-2y Vug-filling calcite 0.82 �13.79 – 0.709462QS-11 O1-2y Vug-filling calcite �1.86 �10.50 – 0.708985

DWG-1 O Vug-filling calcite �7.11 �14.14 – 0.709226QS-16 O1-2y Vug-filling calcite �1.75 �10.32 – 0.709260KP10-2 O1p Vug-filling calcite �0.80 �8.28 – 0.709171KP-14 O1p Vug-filling calcite �2.29 �11.37 – 0.709083TPL-1 O Vug-filling calcite �1.66 �16.13 – 0.710313TPL -2 O Vug-filling calcite �2.32 �17.39 – 0.710445TPL -3 O Vug-filling calcite �2.72 �14.99 – 0.709537

TPL -4 O Vug-filling calcite �2.66 �15.50 – 0.709625TPL -5 O Vug-filling calcite �4.98 �13.30 – 0.709905XKE-1 O Vug-filling calcite 0.63 �5.41 – –XKE-2 O Vug-filling calcite 0.66 �7.65 – –KP-13 O1p Saddle dolomite �0.76 �7.98 – 0.708824QS-13-1 O1-2y Saddle dolomite �1.37 �8.33 – 0.709231

QS-13-2 O1-2y Saddle dolomite �0.88 �8.30 – 0.709840TZ161 O3l Pyrite – – 24.6 –Z12 O1-2y Pyrite – – 29.0 –TZ12-1 O3l Pyrite – – 29.7 –TZ12-2 O3l Pyrite – – 22.3 –TZ826 O Elemental sulfur – – 21.4 –TPL -6 O Anhydrite vein – – – 0.710015TPL -7 O Anhydrite vein – – – 0.710136TPL -8 O Anhydrite vein – – – 0.709910XKE-3 O Anhydrite vein – – – 0.709124TZ12-16-a a* O3 Anhydrite vein – – 24.5 –XKE-2 O Barite vein – – – 0.710009TZ12-17-c a* O3 Barite vein – – 46.6 0.708969

TZ12-9 a* O3 Barite vein – – 45.3 0.709023TZ12-16-d a* O3 Barite vein – – 42.1 0.709568TZ12-17-e a* O3 Barite vein – – – 0.709577TZ45-7-b a* O3 Fluorite vein – – – 0.710364TZ45-12 a* O3 Fluorite vein – – – 0.709514TZ45-6094.6 a* O3 Fluorite vein – – – 0.709124

TZ45-6100.2 a* O3 Fluorite vein – – – –TZ45-6100.9 a* O3 Fluorite vein – – – 0.709305TZ45-6061.8 a* O3 Fluorite vein – – – 0.708891

–: data not measured or unavailable; a* data from Cai et al. (2008).

© 2014 John Wiley & Sons Ltd

Hydrothermal fluid in ordovician carbonates in Tarim Basin 9

(Cai et al. 2001a; Davies & Smith, 2006) which then pen-

etrates underlying porous formation and (ii) dissolution of

buried halite-bearing evaporites (Worden 1996; Stueber

et al. 1998; Jiang et al. 2014a,b). In the Ordovician strata

(and the water had a salinity of >24 wt% NaCl) in Tarim

Basin, dissolution of evaporites seems to be the best sce-

nario to explain the elevated salinity in formation salinity,

which was supported by the geographic and stratigraphic

trends of water chemistry in the Ordovician strata (Cai

et al. 2001a), as well as supported by the presence of evap-

orites in Middle Cambrian strata (Fig. 1). These Cambrian

evaporites may have dissolved and migrated into the Ordo-

vician strata conducted by faults during the Permian

hydrothermal activity mentioned previously (Cai et al.

2001a; Dong et al. 2013).

Meteoric water origin of diagenetic minerals associated

with hydrothermal minerals

Both deep-seated faults and up-reaching faults have been

formed during the hydrothermal event (L€u et al. 2008),

which may have brought deeper high saline water and

meteoric water into the Ordovician strata in the Tarim

Basin, resulted in fluid mixing and hydrothermal mineral

precipitation. Fluorite and calcite samples, associated with

the hydrothermal calcite, dolomite, anhydrite, and barite,

show relatively lower homogenization temperatures

(<120°C) with salinities much lower than the coexisting

hydrothermal minerals in the NW Tarim area (Fig. 6).

Late-stage diagenetic fracture-filling calcite, barite, and

fluorite with low temperatures and salinities have also been

reported in the Ordovician strata in Central Tarim area

(Cai et al. 2008; Li et al. 2011). Importantly, low-temper-

ature (as low as 60°C) calcite and fluorite have similar REE

patterns with significant high Eu anomalies to their high-

temperature (up to 180°C) counterparts, also indicating

the invasion of hydrothermal fluid (Cai et al. 2008). In

addition, the salinity of hydrothermal dolomite broadly

decreased with the decreasing temperature, which probably

suggests that there is an episode of influx of fluid with low

temperature and low salinity (most likely meteoric water)

during the formation of the saddle dolomite. Therefore,

the above findings all suggest that there must have been an

invasion of fresh water during the hydrothermal period,

and the mixing of fresh water with saline hydrothermal flu-

ids resulted in the diagenetic minerals having a wide range

of homogenization temperatures (from 60°C to 240°C)and salinities (from 0.5 to 24 wt% NaCl), with salinities

decreasing with decreasing temperatures (Fig. 6). Referring

to the burial histories in NW Tarim and Central Tarim

areas, meteoric water most likely charged the Ordovician

strata in the NW Tarim area during the significant uplift

stage from the late Permian to the early Triassic (Fig. 2B).

Meteoric water then flowed westward to the Central Tarim

and mixed with hydrothermal fluid and connate water

along its pathways (Cai et al. 2001a; Cai et al. 2008).

The petrological appearance (Fig. 5) and geochemical

characteristics (Fig. 6) indicate that hydrothermal minerals

(e.g., dolomite, calcite, fluorite, and barite) were closely

related to regional igneous rocks (Yang et al. 2012; Pan

et al. 2009). The dating of U-Pb zircon from the diabase

in the Ordovician strata suggests the regional igneous

rocks intrusion occurred in Early Permian

(390.5 � 2.9 Ma) (Dong et al. 2013). The above findings

led to the conclusion that hydrothermal event in the

Upper Cambrian to Lower Ordovician strata in Tarim

Basin most likely postdates the extensive magmatic

emplacement and volcanic eruption event during early

Permian and the regional magmatic event most likely has

provided heat source, fluid pathway, fluids flow tensional

stress fields, and even a small part of hydrothermal fluids

for the consequent hydrothermal event (Davies & Smith

2006; Dong et al. 2013). Therefore, the influx of freshwa-

ter and hydrothermal fluid in the Ordovician strata and

resulting fluid mixing were most likely nearly simultaneous

(probably during late Permian to early Triassic).

From the homogenization temperature and salinity data

in late-stage diagenetic minerals, we therefore conclude

that there are two end-member fluids named hydrothermal

fluid (hot and high saline brine) and meteoric water (cool

and low-salinity water), which have been added to the

paleo-water in the Ordovician strata in Tarim Basin during

the period.

TSR origin of 12C-rich Calcite, 34S-rich Sulfide and

elemental Sulfur

In the Central Tarim Basin, carbon isotope values of the

carbonate samples both in this study and in previous stud-

ies (Cai et al. 2001b, 2008; Li et al. 2011) suggest that

Fig. 8. 87Sr/86Sr isotopic ratios of hydrothermal calcite, fluorite, dolomite,

anhydrite, and barite in the Ordovician unit in Tarim Basin.

© 2014 John Wiley & Sons Ltd

10 L. JIANG et al.

calcite cement, saddle dolomite, CO2, and formation water

contain carbon sourced from isotopically light carbon

sources. Isotopically light carbon (down to �2&) could be

achieved from mantle-originated hydrothermal fluids (Xing

& Li 2012; Dong et al. 2013) or from involving meteoric

water (Allan & Mathews 1982). However, the rather nega-

tive carbon isotope values of the calcite (down to

�7.11&) and formation water (down to �13.8&) suggest

that there are other isotopically light carbon inputs (Li

et al. 2011). An exotic source of carbon or atmospheric

CO2 (e.g., in meteoric-influenced systems) is potentially

supported by the low salinity water recorded in inclusions

within calcite and fluorite (Fig. 5); however, it could not

explain the isotopically lighter carbon with d13C values

< �2& VPDB. Bacterial sulfate reduction (BSR) can be

excluded by the high precipitation temperatures (>80°C)of most of these burial diagenetic minerals (Machel 2001).

Therefore, the only other possible explanation for the low

carbon isotope values of the later diagenetic calcites is ther-

mochemical sulfate reduction (TSR) (Cai et al. 2001b,

2008; Li et al. 2011). This assertion is further supported

by the high sulfur isotopic values ranging from 21.4& to

29.7& (VCDT), being close to the sulfur isotopic values

of coeval or slightly older seawater (Strauss 1997) and

anhydrite vein in this formation (Cai et al. 2008).

Thermochemical sulfate reduction has not been previ-

ously reported in NW Tarim. Thus, it is of great impor-

tance to know whether TSR happened in the Ordovician

strata in NW Tarim, as different styles of diagenesis may

lead the different patterns of reservoir quality and thus dif-

ferent exploration strategies between NW Tarim and Cen-

tral Tarim areas. In this study, evidence to support the

interpretation of TSR in Ordovician strata in NW Tarim is

(i) the relatively lighter carbon isotopic values of the late

diagenetic calcites (down to �7.11& VPDB, and carbon

isotope values decreasing with decreasing oxygen isotopes

in calcite cements; Fig. 7); (ii) late diagenetic, coarse crys-

talline pyrite, and elemental sulfur being closely grown

with the isotopically light carbon calcite; (iii) the higher

temperatures recorded by calcite fluid inclusions (Fig. 6;

Xing & Li 2012), which exceed the reported global lowest

temperature for TSR (>100°C; Worden et al. 2000; Ma-

chel 2001); and (iv) very high salinity of the FIs in the late

diagenetic minerals (Fig. 6), suggesting abundant SO2�4

was most likely transported from underlying Cambrian

anhydrite bearing strata into the Ordovician strata by

deep-seated faults (Cai et al. 2001a; L€u et al. 2008).

Collectively, both in the Central Tarim and in the NW

Tarim, the petrological and isotopical evidence from diage-

netic calcite, sulfide, and elemental sulfur in the Ordovician

strata suggest that they were most likely derived from ther-

mochemical sulfate reduction (TSR) (Worden et al. 1995,

2000; Cai et al. 2001b, 2003, 2004, 2008, 2009b; Jiang

et al. 2014a). Hot brine from the deeper Cambrian strata

during the hydrothermal event may have contributed both

heat and sulfate as required by TSR.

Isotopic evidence for fluids mixing

The d18O values of calcite cements from the Upper Cam-

brian to Ordovician strata (Table 1) are between �17.39

and �7.49& V-PDB, with most of the value ranging from

�7.5 to �15& V-PDB (Fig. 7; Li et al. 2011; Dong et al.

2013). Early diagenetic calcite with high oxygen isotope

values lies between �7 and �5& V-PDB (average at about

�6&; Li et al. 2011; Table 1), within the reported late

Cambrian to early Ordovician carbonate oxygen isotope

value range (from �10 to �5& V-PDB) (Veizer et al.

1999). These calcites contain numerous single phase inclu-

sions, which probably formed below 50°C (Goldstein &

Reynolds 1994), during early diagenesis. Using the O’Neil

et al. (1969), calcite-water oxygen isotope fractionation

equation, the d18O value of the water present during the

growth of isotopically heavy early diagenetic calcite was

between 0& and 2& V-SMOW. However, the isotopically

lighter deep burial diagenetic calcites were precipitated

between the temperature of 60°C and 180°C (Fig. 5).

Using the same equation from O’Neil et al. (1969), the

isotopically lighter calcite grew from water with d18O rang-

ing from �6.7 to 12.5& V-SMOW, while the connate sea-

water should has d18O lies between 2.6 to 14.1& V-

SMOW, in the temperature range from 60°C to 180°C.Hydrothermal dolomites (HTD) in the Upper Cambrian

to Ordovician strata show d18O values lie between �5.88

and �10.24& V-PDB (Table 1; Dong et al. 2013), these

dolomites formed in a temperature range from 70°C to

140°C, by employing the dolomite-water oxygen isotope

fractionation equation from Land (1983), the water

responsible for the growth of saddle dolomite has d18Ovalues ranging from 1.0 to 9.4& V-SMOW. Invasion of

meteoric water is precluded by the high salinity data from

fluid inclusions in saddle dolomite. Therefore, the high-

salinity hydrothermal dolomitizing fluid indicated the con-

tribution of halite and evaporites from the Cambrian

strata.

As calculated above, the fluids responsible for the forma-

tion of deep burial diagenetic calcite in the Ordovician

strata show a relatively wider range of d18O values (from

�6.7 to 12.5) than the calculated fluids from hydrothermal

dolomite (1.0 to 9.7& V-SMOW). Moreover, the calcu-

lated connate seawater has d18O values between 2.6 and

14.1& V-SMOW, and the coeval brine has d18O value of

about 15& SMOW during Cambrian and Ordovician

(Claypool et al. 1980). Hence, the isotopic lighter values

of the late diagenetic calcites (as low as �6.7& V-SMOW)

suggest that meteoric water was most likely involved in this

diagenetic period (Cai et al. 2001a), and this conclusion is

supported by the very low salinity data (down to 0.5 wt%

© 2014 John Wiley & Sons Ltd

Hydrothermal fluid in ordovician carbonates in Tarim Basin 11

NaCl) obtained from the calcite and fluorite fluid inclu-

sions (Fig. 6B,H).

The Sr isotope ratios of the calcite cements, anhydrites,

barites, dolomites, and fluorites lie in a range from

0.708823 to 0.710445 (Fig. 8, Table 1). Except for some

early diagenetic calcite cements within the Sr isotope ratios

range of early Ordovician seawater (Veizer et al. 1999;

McArthur & Howarth 2004), all the other deep burial dia-

genetic minerals show significantly higher Sr isotopic values

(up to 0.7010), possibly suggesting that the influxed mete-

oric water or invaded hydrothermal fluid may have leached

other rocks on their pathways (Cai et al. 2008; Li et al.

2011). The Sr isotope values of calcite cements increase

with decreasing oxygen isotopes (Fig. 9) suggesting an

increasing influence of meteoric water or the increasing

temperature sourced from the hydrothermal activity. Salin-

ity data obtained from fluid inclusions in some fluorite and

calcite cements show very low values (down to 0.5 wt%

NaCl), but high Sr isotope values up to 0.7010 (Table 1;

Fig. 8), suggesting that these calcite and fluorite must have

precipitated from meteoric water that obtained 87Sr from

clastic sediments during fluid flow. In contrast, calcite

cement, fluorite, saddle dolomite, and barite samples have

relatively high salinity in fluid inclusions (from 15 to 25 wt

% NaCl) and high 87Sr/86Sr ratios (up to 0.7010),

suggesting that hydrothermal fluid derived from the Cam-

brian also leached Sr from potassium-bearing rocks (likely

clastic sediments or K-rich igneous rocks). Although no

salinity data have been obtained from anhydrite cement,

the relatively high Sr isotopes and REE distribution similar

to the Cambrian anhydrite may suggest that the anhydrite

may have been related to the halite- and evaporate-bearing

Cambrian strata (Cai et al. 2008).

In summary, the key attributes of meteoric water and

hydrothermal fluid are summarized in Table 2. There are

differences in the two end members of fluid in terms of

diagenetic minerals, their fluid inclusion temperatures,

Fig. 9. Cross-plot of d18O and 87Sr/86Sr ratio in the fracture- and vug-fill-

ing calcites in the Ordovician unit in Tarim Basin.

Tab

le2Inferred

salinities,

temperatures,

d18O,an

d87Sr/8

6Sr

ratiosofen

d-m

ember

fluids.

end

mem

bers

occurren

cein

rock

crystal

form

diagen

etic

minerals

d18O

fluid

V-SMOW

d13Ccarbonate

V-PDB

87Sr/8

6Sr

temperature

salinity

Meteo

ricwater

vugfillormicro-fracture

fill

(subcm

tom-scale

fractures)

blocky

fabric

calcite,

fluorite

�6.7

to0&

downto

�2&

upto

0.7010

60°C

to100°C

0to

<3.5

wt%

NaC

l

Hyd

rothermal

fluids

vugfillormicro-fracture

fill

(subcm

tom-scale

fractures)

blocky

fabric

calcite,

saddle

dolomite,

barite,

anhyd

rite,

fluorite,an

dquartz

1to

12.5&

downto

�13.8&

upto

0.7104

140to

>200°C

upto

>24wt%

NaC

l

© 2014 John Wiley & Sons Ltd

12 L. JIANG et al.

salinities, d13C, and 87Sr/86Sr isotope values, as well as the

calculated d18O values of the fluids.

Hydrothermal model and its implication to exploration

Previous studies have shown that the hydrothermal fluid

was related to regional Permian magmatic activity (Chen

et al. 1997; Tang et al. 2004; Yang et al. 2007, 2012;

Tian et al. 2010; Zhang et al. 2010; Xing & Li 2012;

Dong et al. 2013). The regional Permian magmatic activity

could have led to rock fracturing and thermal diffusion,

driving hydrothermal fluid to migrate into the overlying

Ordovician strata (Fig. 10). On the other hand, induced

fractures, right up to the surface, may also have been

related to the Permian igneous activity (Fig. 10; L€u et al.

2008), allowing meteoric water to penetrate into the

Ordovician strata and mix with hydrothermal fluid and

connate formation water (Cai et al. 2008; Xing & Li

2012). This scenario is supported by fluid inclusion salini-

ties and homogenization temperatures, as well as the d13C,d18O, and 87Sr/86Sr values of the hydrothermal minerals

(Figs 7–9; Table 2).

In the Tarim Basin, hot hydrothermal fluid with high

d18O value (up to 12.5& V-SMOW), high temperature

(>200°C), high salinity (up to 24 wt% NaCl), and high87Sr/86Sr ratio (up to 0.7010) was most likely expelled from

Pre-Cambrian and Lower Cambrian strata into the Ordovi-

cian strata (Cai et al. 2008; Jia et al. in press) by means of

tectonic movement and thermal convection (Davies &

Smith 2006). Hydrothermal fluid was likely to flow either

westward or eastward along the Ordovician strata. However,

cooler meteoric water with low d18O value, low tempera-

tures (<60°C), very low salinity (0.5–3.5 wt% NaCl), but

also high 87Sr/86Sr ratios (up to 0.7010) was most likely

introduced into the Ordovician strata by gravity in NW Ta-

rim area. Both hydrothermal fluid and meteoric water flowed

and then mixed with the formation water in the Ordovician

strata along regional conduits (e.g., fault, fracture, uncon-

formity). The mixed fluid probably resulted in decrease in

homogenization temperatures, salinities, and 87Sr/86Sr

ratios of hydrothermal minerals, but increase in d18O values

of saddle dolomites and calcites along its pathway (Figs 9

and 10). The Ordovician strata likely acted as a deeply bur-

ied regional porous and permeable conduit system for focus-

ing and channeling basinal fluid flow in the Tarim Basin.

Hence, the fluid flow and mixing scenario in the Ordovician

in the Tarim Basin is similar to the case in the Middle Devo-

nian in West Canada Sedimentary Basin (WCSB), where the

hot, radiogenic hydrothermal fluids moved eastward up-dip

along the Presqu’ile barrier and mixed with cooler ambient

formation waters during tectonic movements (Qing &

Mountjoye 1992). The basinal hydrothermal fluid flow and

mixing in the WCSB also precipitated hydrothermal minerals

and led to dolomitization of the host carbonate in the Mid-

dle Devonian, which locally improved reservoir quality

(Qing & Mountjoye 1992, 1994).

Both in this study and in previous studies, it has been

shown that contact metamorphic limestones, close to gran-

ite intrusions and diabase dikes, commonly have very low

porosity in outcrops in the NW Tarim Basin (Pan et al.

2009; Zhang et al. 2014). In contrast, carbonate reservoirs

away from granite intrusions and diabase dikes have rela-

tively high porosity (locally >10%). Significantly, good

quality carbonate reservoirs contain abundant fractures

filled by hydrothermal minerals (Figs 5 and 7–9). Collec-tively, these findings suggest that cross-formational hydro-

thermal fluid flow induced by the Permian magmatic

activity, rather than the volcanic hydrothermal fluid, may

have improved the reservoir quality (Pan et al. 2009).

Mixtures of hydrothermal fluid and meteoric water with

the connate formation water can lead to either precipitation

of hydrothermal minerals decreasing reservoir porosity or

Fig. 10. The hydrothermal model for fluids

mixing induced by Early Permian magmatic

activity in the Ordovician unit in Tarim Basin.

© 2014 John Wiley & Sons Ltd

Hydrothermal fluid in ordovician carbonates in Tarim Basin 13

dissolution of the host carbonate rocks increasing the reser-

voir porosity; the dissolution and precipitation process was

mainly controlled by water chemistry (e.g., Ca, carbonate,

and other chemical composition concentrations), pH, and

fluid flux (Corbella et al. 2004). The formation of faults

during the hydrothermal activity could increase the reservoir

quality and result in fractured hydrocarbon reservoirs (Smith

2005; L€u et al. 2008). Hydrothermal dolomitization has

been reported to significantly enhance carbonate reservoir

quality either by replacing or dissolving calcite, or by brecci-

ation (Qing & Mountjoye 1994; Machel & Lonnee 2002;

Lavoie et al. 2005; Smith 2005; Davies & Smith 2006;

Wendte et al. 2009; Saller & Dickson 2011). Some authors

have presented evidence that shows a decrease in porosity

due to excess dolomitization and sulfate cementation (e.g.,

Lucia 2004; Jones and Xiao, 2005). However, in this study,

point counting indicates that the hydrothermal dolomitiza-

tion is more likely to be a mole-for-mole replacement pro-

cess and the replaced highly crystalline dolomite can resist

compaction and retain much of the original porosity than

limestone (Lucia 2004). Hence, hydrothermal dolomitiza-

tion in this study seems to have enhanced reservoir quality

(Fig. 4; Qing & Mountjoye 1994; Saller & Dickson 2011).

Thermochemical sulfate reduction (TSR) in the deep

burial carbonate reservoirs may have potential in enhancing

porosity by dissolving either sulfates or carbonates during

and after this physical and chemical process (Cai et al.

2014). Moreover, the best carbonate reservoirs were clo-

sely related to the invasion of hydrothermal fluids and the

associated TSR as well as the influx of meteoric water

(Yang et al. 2012). Therefore, fluid mixing, dolomitiza-

tion, TSR, and faulting caused by the hydrothermal event

have significantly improved the Ordovician reservoirs in

Tarim Basin (Fig. 5; Qing & Mountjoye 1992, 1994; Cor-

bella et al. 2004; Lavoie et al. 2005; Smith 2005; Davies

& Smith 2006; L€u et al. 2008; Pan et al. 2009; Yang

et al. 2012).

CONCLUSIONS

(1) Calcite, saddle dolomite, fluorite, barite, quartz, and

anhydrite, both from a number of outcrops in NW Ta-

rim Basin and from a number of subsurface cores in

Central Tarim Basin in the Ordovician in Tarim Basin,

show FIs homogenization temperatures 10°C higher

than the formation temperatures and thus are of

hydrothermal origin.

(2) In Tarim Basin, mixing of hot and high-salinity hydro-

thermal fluids with cool and low-salinity meteoric

water was likely occurred in the Ordovician strata,

which is supported by the homogenization tempera-

tures and salinities of fluid inclusions as well as d13C,d18O, and 87Sr/86Sr isotope values of the deep burial

diagenetic minerals.

(3) TSR most likely occurred both in NW Tarim Basin

and in Central Tarim Basin, when sulfate-rich hydro-

thermal fluid migrated into the Ordovician during the

Permian, leading to the formation of 12C-rich calcites,

and pyrite and elemental sulfur with d34S values close

to the Cambrian to Ordovician seawater.

(4) The structurally controlled hydrothermal activity

induced by Permian magmatism in Tarim Basin

resulted in the formation of deep-seated fracture, and

less commonly of up-reaching fractures, leading to

the migration of hydrothermal fluids into the Ordo-

vician, and locally mixed with meteoric water in Ta-

rim Basin.

(5) Hydrothermal fluid mixing, faulting, dolomitization,

and TSR in the Ordovician strata in Tarim Basin can

locally dissolve and/or replace the host carbonate min-

erals to increase the reservoir porosity, which has sig-

nificant implications for hydrocarbon exploration.

ACKNOWLEDGEMENTS

This work is financially supported by Special Major Project

on Petroleum Study (Grant No. 2011ZX05008-003),

China National Funds for Distinguished Young Scientists

(Grant No. 41125009), Natural Science Foundation of

China (Grant No. 41402132), and China Postdoctoral Sci-

ence Foundation (Grant No. 2014M550835). Construc-

tive comments on the previous version of this paper by

Chief Editor Professor Richard H. Worden and two anon-

ymous reviewers were very helpful.

REFERENCES

Allan JR, Mathews RK (1982) Isotope signatures associated with

early meteoric diagenesis. Sedimentology, 29, 797–817.Bodnar RJ (2003) Reequilibration of fluid inclusions. In: FluidInclusions-Analysis and Interpretation (eds Sampson I, Anderson

A, Marshall D), pp. 213–31. Special Publication. MineralogicalAssociation of Canada.

Cai CF, Franks S, Aagaard P (2001a) Origin and migration ofbrines from Paleozoic strata in Central Tarim, China: constraints

from 87Sr/86Sr, dD, d18O and water chemistry. AppliedGeochemistry, 16, 1269–84.

Cai CF, Hu WS, Worden RH (2001b) Thermochemical sulphatereduction in Cambro-Ordovician carbonates in Central Tarim.

Marine and Petroleum Geology, 18, 729–41.Cai CF, Worden RH, Bottrell SH, Wang LS, Yang CC (2003)Thermochemical sulphate reduction and the generation of

hydrogen sulphide and thiols (mercaptans) in Triassic carbonate

reservoirs from the Sichuan Basin, China. Chemical Geology,202, 39–57.

Cai CF, Xie ZY, Worden RH, Hu GY, Wang LS, He H (2004)

Methane-dominated thermochemical sulphate reduction in the

Triassic Feixianguan formation East Sichuan Basin, China:

towards prediction of fatal H2S concentrations. Marine andPetroleum Geology, 21, 1265–79.

Cai CF, Li KK, Li HT, Zhang BS (2008) Evidence for cross

formational hot brine flow from integrated 87Sr/86Sr, REE and

© 2014 John Wiley & Sons Ltd

14 L. JIANG et al.

fluid inclusions of the Ordovician veins in Central Tarim, China.

Applied Geochemistry, 23, 2226–35.Cai CF, Li KK, Ma AL, Zhang CM, Xu ZM, Worden RH, WuGH, Zhang BS, Chen LX (2009a) Distinguishing Cambrian

from Upper Ordovician source rocks: evidence from sulfur

isotopes and biomarkers in the Tarim Basin. OrganicGeochemistry, 40, 755–68.

Cai CF, Zhang CM, Cai LL, Wu GH, Jiang L, Xu ZM, Li KK,

Ma AL, Chen LX (2009b) Origins of Palaeozoic oils in the

Tarim Basin: evidence from sulfur isotopes and biomarkers.

Chemical Geology, 268, 197–210.Cai CF, He W, Jiang L, Li KK, Xiang L, Jia LQ (2014) Petrological

and geochemical constraints on porosity difference between

Lower Triassic sour-and sweet-gas carbonate reservoirs in the

Sichuan Basin. Marine and Petroleum Geology, 56, 34–50.Canfield DE, Raiswell R, Westrich JT, Reaves CM, Berner RA

(1986) The use of chromium reduction in the analysis of

reduced inorganic sulfur in sediments and shales. ChemicalGeology, 54, 149–55.

Chen HL, Yang SF, Dong CW, Jia CZ, Wei GQ (1997)

Confirmation of Permian basite zone in Tarim Basin and its

tectonic significance. Geochimica (Beijing), 126, 77–87 (inChinese).

Claypool GE, Holser WT, Kaplan IR, Sakai K, Zak I (1980)

The age curves of sulfur and oxygen isotopes in marine

sulfate and their mutual interpretation. Chemical Geology, 28,199–260.

Corbella M, Ayora C, Cardellach E (2004) Hydrothermal mixing,

carbonate dissolution and sulfide precipitation in MississippiValley-type deposits. Mineralium Deposita, 39, 344–57.

Davies G, Smith L (2006) Structurally controlled hydrothermal

dolomite reservoir facies: an overview. American Association ofPetroleum Geologists Bulletin, 90, 1641–90.

Dong SF, Chen DZ, Qing HR, Zhou XQ, Wang D, Guo ZH,

Jiang MS, Qian YX (2013) Hydrothermal alteration of

dolostones in the Lower Ordovician, Tarim Basin, NW China:

multiple constraints from petrology, isotope geochemistry andfluid inclusion microthermometry. Marine and PetroleumGeology, 46, 270–86.

Goldstein RH, Reynolds TJ (1994) Systematics of fluid inclusionsin diagenetic minerals: Short course 31, SEPM (Society for

Sedimentary Geology), p. 199.

Jia LQ, Cai CF, Yang HJ, Li HX, Wang TK, Zhang BS, Jiang L,

Tao XW (in press). Thermochemical and bacterial sulfatereduction in the Cambrian and Lower Ordovician carbonates in

the Tazhong Area, Tarim Basin, NW China: evidence from fluid

inclusions, C, S and Sr isotopic data. Geofluids. doi: 10.1111/gfl.12105.

Jiang L, Cai CF, Worden RH, Li KK, Xiang L (2013) Reflux

dolomitization of the Upper Permian Changxing Formation and

the Lower Triassic Feixianguan Formation, NE Sichuan Basin,

China. Geofluids, 13, 232–45.Jiang L, Worden RH, Cai CF (2014a) Thermochemical sulfate

reduction and fluid evolution of the Lower Triassic Feixianguan

Formation sour gas reservoirs, Northeast Sichuan Basin, China.American Association of Petroleum Geologists Bulletin, 98, 947–73.

Jiang L, Worden RH, Cai CF, Li KK, Xiang L, Cai LL, He XY

(2014b) Dolomitization of gas reservoirs: the Upper PermianChangxing Formation and Lower Triassic Feixianguan

Formation, Northeast Sichuan Basin, China. Journal ofSedimentary Research, 84, 792–815.

Jones GD, Xiao Y (2005) Dolomitization, anhydrite cementationand porosity evolution in a reflux system: insights from reactive

transport models. American Association of Petroleum GeologistsBulletin, 89, 577–601.

Land LS (1983) The application of stable isotopes to studies ofthe origin of dolomite and to problems of diagenesis of clastic

sediments. In: Stable Isotopes in Sedimentary Geology (eds ArthurMA, Anderson TF, Kaplan IR, Veizer J, Land LS), SEPM ShortCourse Notes 10, 4-1-4-22.

Lapponi F, Bechstadt T, Boni M, Banks D (2014) Hydrothermal

dolomitization in a complex geodynamic setting (Lower

Palaeozoic, northern Spain). Sedimentology, 61, 411–43.Lavoie D, Chi G, Brennan-Alpert P, Desrochers A, Bertrand R(2005) Hydrothermal dolomitization in the Lower Ordovician

Romaine Formation of the Anticosti Basin: significance for

hydrocarbon exploration. Bulletin of Canadian PetroleumGeology, 53, 454–72.

Li KK, Cai CF, He H, Jiang L, Cai LL, Xiang L, Huang SJ,

Zhang CM (2011) Origin of palaeo-waters in the Ordovician

carbonates in Tahe oilfield, Tarim Basin: constraints fromfluid inclusions and Sr, C and O isotopes. Geofluids, 11, 71–86.

L€u XX, Yang N, Zhou XY, Yang HJ, Li JJ (2008) Influence of

Ordovician carbonate reservoir beds in Tarim Basin by faulting.Science in China Series D: Earth Sciences, 51, 53–60.

Lucia FJ (2004) Origin and petrophysics of dolostone pore space.

Geological Society, London, Special Publications, 235, 141–55.Machel H (2001) Bacterial and thermochemical sulfate reductionin diagenetic settings–old and new insights. SedimentaryGeology, 140, 143–75.

Machel HG, Lonnee J (2002) Hydrothermal dolomite – aproduct of poor definition and imagination. SedimentaryGeology, 152, 163–71.

McArthur J, Howarth R (2004) Strontium isotope stratigraphy.

In: A Geologic Time Scale 2004 (eds Gradstein FM, Ogg JG,Smith AG), pp. 96–105. Cambridge University Press,

Cambridge.

Oakes CS, Bodnar RJ, Simonson JM (1990) The system NaCl-

CaCl2-H2O: I. the ice liquidus at 1 atm total pressure.Geochimica et Cosmochimica Acta, 54, 603–11.

O’Neil JR, Clayton RN, Mayeda TK (1969) Oxygen isotope

fractionation in divalent metal carbonates. Journal of ChemicalPhysics, 51, 5547–58.

Pan WQ, Liu YF, Dickson JAD, Shen AJ, Han J, Ye Y, Gao HL,

Guan P, Zhang LJ, Zheng XP (2009) The geological model of

hydrothermal activity in outcrop and the characteristics ofcarbonate hydrothermal karst of Lower Paleozoic in Tarim

Basin. Acta Sedmentologica Sinica, 27, 983–94 (in Chinese).

Qing H, Mountjoye W (1992) Large-scale fluid flow in the

Middle Devonian Presqu’ile barrier, Western CanadaSedimentary Basin. Geology, 20, 903–6.

Qing H, Mountjoye W (1994) Formation of coarsely crystalline,

hydrothermal dolomite reservoirs in the Presqu’ile barrier,

Western Canada Sedimentary Basin. American Association ofPetroleum Geologists Bulletin, 78, 55–77.

Saller AH, Dickson JA (2011) Partial dolomitization of a

Pennsylvanian limestone buildup by hydrothermal fluids and itseffect on reservoir quality and performance. AmericanAssociation of Petroleum Geologists Bulletin, 95, 1745–62.

Smith LB (2005) Origin and reservoir characteristics of Upper

Ordovician Trenton-Black River hydrothermal dolomitereservoirs in New York. American Association of PetroleumGeologists Bulletin, 90, 1691–718.

Strauss H (1997) The isotopic composition of sedimentary sulfur

through time. Palaeogeography Palaeoclimatology Palaeoecology,132, 97–118.

© 2014 John Wiley & Sons Ltd

Hydrothermal fluid in ordovician carbonates in Tarim Basin 15

Stueber AM, Saller AH, Ishida H (1998) Origin, migration and

mixing of brines in the Permian Basin: geochemical evidence

from the eastern Central Basin platform, Texas. AmericanAssociation of Petroleum Geologists Bulletin, 82, 1652–72.

Tang LJ, Zhang YW, Jin ZJ, Jia CZ (2004) Opening-closing

cycles of the Tarim and Qaidam Basins, northwestern China.

Geological Bulletin of China, 23, 254–60 (in Chinese).Tian W, Campbell IH, Allen CM, Guan P, Pan WQ, Chen

MM, Yu HJ, Zhu WP (2010) The Tarim picrite-basalt-

rhyolite suite, a Permian flood basalt from northwest China

with contrasting rhyolites produced by fractional crystallizationand anatexis. Contributions to Mineralogy and Petrology, 160,407–25.

Veizer J, Ala D, Azmy K, Bruckschen P, Bruhn F, Buhl D,

Carden G, Diener A, Ebneth S, Goddris Y, Jasper T, Korte C,Pawellek F, Podlaha O, Strauss H (1999) 87Sr/86Sr, d18O and

d13C evolution of Phanerozoic seawater. Chemical Geology, 161,59–88.

Wendte J (2006) Origin of molds in dolostones formed by the

dissolution of calcitic grains: evidence from the Swan Hills

Formation in west-Central Alberta and other Devonian

formations in Alberta and northeastern British Columbia.Bulletin of Canadian Petroleum Geology, 54, 91–109.

Wendte J, Byrnes A, Sargent D (2009) The control of

hydrothermal dolomitization and associated fracturing on

porosity and permeability of reservoir facies of the UpperDevonian Jean Marie Member (Redknife Formation) in the July

Lake area of northeastern British Columbia. Bulletin ofCanadian Petroleum Geology, 57, 387–408.

Worden RH (1996) Controls on the halogen content of

sedimentary formation waters. Mineral Magazine, 60, 259–74.

Worden RH, Smalley PC, Oxtoby NH (1995) Gas souring by

thermochemical sulfate reduction at 140°C. AmericanAssociation of Petroleum Geologists Bulletin, 79, 854–63.

Worden RH, Smalley PC, Cross MM (2000) The influence of

rock fabric and mineralogy on thermochemical sulfate reduction:

Khuff Formation, Abu Dhabi. Journal of Sedimentary Research,70, 1210–21.

Xing FC, Li ST (2012) Genesis and Environment Characteristics

of Dolomite-Hosted Quartz and Its Significance for

Hydrocarbon Exploration, in Keping Area, Tarim Basin, China.

Journal of Earth Science, 23(4), 476–89.Yang SF, Li ZL, Chen HL, Santosh M, Dong CW, Yu X (2007)

Permian bimodal dyke of Tarim Basin, NW China: geochemical

characteristics and tectonic implications. Gondwana Research,12, 113–20.

Yang HJ, Li KK, Pan WQ, Xiao ZY, Cai CF (2012) Burial

hydrothermal dissolution fluid activity and its transforming

effect on the reservoirs in Ordovician in Central Tarim. ActaPetrologica Sinica, 28, 73–792. (in Chinese).

Ye DS (1994) Deep dissolution of Cambrian-Ordovician

carbonates in the Northern Tarim Basin. Acta SedimentologicalSinica, 12, 66–70 (in Chinese).

Zhang CL, Xu YG, Li ZX, Wang HY, Ye HM (2010) Diverse

Permian magmatism in the Tarim Block, NW China: genetically

linked to the Permian Tarim mantle plume. Lithos, 119, 537–52.

Zhang W, Guan P, Jian X, Feng F, Zou CN (2014) In situ

geochemistry of Lower Paleozoic dolomites in the northwestern

Tarim Basin: implications for the nature, origin, and evolutionof diagenetic fluids. Geochemistry, Geophysics, Geosystems, 15,2744–64.

© 2014 John Wiley & Sons Ltd

16 L. JIANG et al.