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The effect of hydrothermal fluids on Ordovician carbonate rocks, southern

Ordos Basin, China

Bo Jiu, Wenhui Huang, Yuan Li

PII: S0169-1368(19)30945-X
DOI: https://doi.org/10.1016/j.oregeorev.2020.103803
Reference: OREGEO 103803

To appear in: Ore Geology Reviews

Received Date: 29 October 2019

Revised Date: 21 September 2020
Accepted Date: 24 September 2020

Please cite this article as: B. Jiu, W. Huang, Y. Li, The effect of hydrothermal fluids on Ordovician carbonate
rocks, southern Ordos Basin, China, Ore Geology Reviews (2020), doi: https://doi.org/10.1016/j.oregeorev.
2020.103803

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 The effect of hydrothermal fluids on Ordovician carbonate rocks, southern Ordos

Basin, China

Bo Jiu1, Wenhui Huang1, * Yuan Li1

1Key Laboratory for Marine Reservoir Evolution and Hydrocarbon Abundance

Mechanism, School of Energy Resources, China University of Geosciences (Beijing),

Ministry of Education, Xueyuan Road No. 29, Beijing 100083, China

*Corresponding author email: huangwh@cugb.edu.cn

Abstract: Hydrothermal processes have an important influence on the spatial

distribution and formation of carbonate reservoirs, and play a critical role in certain

deep reservoirs where hydrothermal fluid-rock interaction may result in permeability

creation due to carbonate dissolution or permeability destruction due to the deposition

of cementing minerals. This study analyzed certain hydrothermal indicator minerals

(quartz, celestite, multi-stage calcareous fillings) in carbonate rocks from the

Ordovician Majiagou Formation, southern Ordos Basin, China. The petrological and

geochemical characteristics of these indicator minerals imply that the Majiagou

Formation was affected by two metasomatic events related to the Hercynian–Indosinian

and Yanshanian orogenies and linked to magmatic-hydrothermal fluids derived from

basaltic melts. Most of the δCe and δEu values obtained from matrix dolomite samples

were lower than one, but U/Th and V/C ratios showed positive anomalies. The δ13C and

δ18O values of the matrix dolomite were concentrated between -12.8‰ and -6.0‰,

whereas δ13C showed a bipolar distribution at the same depth. Elemental geochemistry

1
results showed that the Ordovician carbonate rocks were subjected to freshwater

leaching followed by evaporation and widespread hydrothermal dissolution

successively. As a result of the multi-episodic hydrothermal activity that affected the

southern Ordos Basin and the path of migration channel, a parental magmatic-

hydrothermal fluid (fluid 1) that had been generated during the underplating of the

southern North China Craton by Mesozoic alkaline basalt melts, separated into two

types of fluids with different chemical properties: an acidic, hydrocarbon-bearing fluid

(fluid 2a) mixed with Cambrian oil and gas and a weakly to moderately alkaline brine

(fluid 2b), not in contact with hydrocarbons. Both fluids 2a and 2b then interacted with

the Ordovician carbonate rocks with fluid 2a having undergone hydrothermal sulfate

reduction with SO42- in the layers in which gypsum was developed, and convection of

fluid 2a having resulted in brine formation. The reaction products of H2S and CO2

together with organic acid co-dissolved carbonate minerals in the Ordovician strata

played a major role in the formation of a high porosity reservoir. Conversely, owing to

the progressive reduction of temperature and solubility during fluid ascent, fluid 2b

precipitated quartz-calcite fillings in the residual pore spaces, resulting in the localized

destruction of the original reservoir permeability. In summary, this study analyzed the

petrological and geochemical characteristics of 60 carbonate rock drill core samples,

established the likely formation mechanism of fluids 2a and 2b, and determined the

effects of these hydrothermal fluids on the Ordovician Majiagou Formation carbonate

reservoir.

2
Keywords: Ordos Basin; hydrothermal fluid; carbonate rock; dissolution; ore deposit;

1. Introduction

The term “hydrothermal fluid” typically refers to a geological fluid derived from the

lower crust that ascends along permeable first- and second-order fault-fracture zones

and has a temperature that is at least >5 °C higher than that of the surrounding wall

rocks. Hydrothermal fluids can be highly reactive and trigger multiple types of chemical

reactions in the rocks they interact with (Cai et al., 2001; Wagner and Jochum, 2002;

Morrow, 2014; Hernandez et al., 2016).

This study focuses on carbonate rocks and their reactions with hydrothermal fluids, as

these can cause dissolution of unstable mineral components, enhanced porosity, fluid

seepage, and ultimately the formation of high-quality hydrocarbon reservoirs. Many

carbonate reservoirs globally have been formed by hydrothermal actions (Qiu et al.,

2012; Biehl et al., 2016; Kunst et al., 2017; Han et al., 2019). In the 1980s, Shukla et

al. (1984) proposed a structural-hydrothermal dolomitization model that triggered a

resurgence of research on hydrothermal activity worldwide whilst in recent years the

research focus has been on the behavior of deep hydrothermal fluids and their influence

on oil and gas reservoirs.

According to Wierzbicki et al. (2006), Biehl et al. (2016) and Su et al. (2016),

hydrothermal fluid transformation, including hydrothermal dissolution and

hydrothermal filling, plays an important role in the development of high-quality

reservoirs globally, particularly of ultra-deep reservoirs. For example, many of the large
3
hydrocarbon reservoirs in major sedimentary basins in the United States and Canada

(such as the Michigan and Anticosti basins) are genetically related to hydrothermal

activity (Smith, 2006; Saller and Dickson, 2011). Typical examples of such activity are

the Devonian–Mississippian oil fields of Eastern Canada, where carbonate reservoirs

were formed due to hydrothermal transformation (Katz et al., 2006; Wierzbicki et al.,

2006; Nurkhanuly and Dix, 2015). With respect to China, geoscientists are currently

focusing their research on better understanding hydrothermal activity in the major

sedimentary basins with clear evidence of such activity emerging from the Cambrian–

Ordovician carbonate reservoirs in the Tarim, Ordos, and Sichuan basins (Hao et al.,

2008; Li et al., 2015; Du et al., 2018).

In recent years, the Ordos Basin has become the focus of oil, gas, and mineral

exploration. This study focuses on the Ordovician of the southern Ordos Basin, which

is mainly composed of marine carbonate rocks. Several previous studies have illustrated

how hydrothermal fluids affected the genesis, the dissolution via thermochemical

sulfate reduction (TSR) reactions, and destruction of hydrothermal precipitations in

Ordovician reservoirs of the Ordos Basin (Zhao et al., 2014; He et al., 2016).

Preliminary research by He et al. (2013) and Wei et al. (2018) addressed the genesis of

hydrothermal dolomite, the characteristics of hydrothermal karst reservoirs, and

hydrothermal diagenesis in the southern Ordos Basin. However, the nature of

hydrothermal fluid migration, the geochemical characteristics of the hydrothermal

fluids, and the effects of these fluids on the Ordovician carbonate rocks has not yet been

4
adequately elucidated.

Here we conducted petrological and geochemical analyses of dolomite samples

collected from 12 wells penetrating the Ordovician Majiagou Formation in the southern

Ordos Basin. In particular, we conducted thin section and cathodoluminescence studies

and oxygen and carbon isotope and fluid inclusion and trace element analyses of the

carbonate matrix defined as the interstitial material between larger grains proposed by

Flügel (2010) (referred to in this paper as matrix rock) and overprinting hydrothermal

minerals contained within the dolomite samples with the aim of better constrain the

nature of the hydrothermal fluids that affected these rocks, particularly their

geochemical characteristics, modes of migration, and overall impact on the Ordovician

Majiagou Formation. The findings presented here have implications for understanding

the genesis and evolution of hydrothermal fluids in sedimentary basins and may assist

in gaining a better understanding of the genesis of spatially associated metalliferous

deposits in the Ordos Basin, such as the many uranium and rare earth element (REE)

deposits.

2. Geological setting

Located on the North China Craton, the Ordos Basin has been affected by multi-stage

tectonic processes, including the Caledonian, Hercynian, Yanshanian, and Himalayan

orogenies (Dai et al., 2005; Yang et al., 2005). During the sedimentary period of the 5th

member in the Majiagou Formation, the subduction of the Qinling oceanic crust in the

south and the Xingmeng oceanic crust in the north resulted in compression of the

5
Ordovician strata in a north-south direction (Zhao and Zhai, 2013). The entire Ordos

Basin has been experiencing periodic transgression and regression. During the

Caledonian, the entire basin was uplifted and subsequently exposed to weathering and

erosion for hundreds of millions of years. Two major seas with very different

sedimentary system were present in the Ordos area: the North China Sea and the

Qinqihai Sea (Fang et al., 2016). In the eastern basin (the Qinhai Sea) is an epeiric

marine carbonate platform in which the combination of dolomite-gypsum interbeds

frequently occurred. The sedimentary facies of Ordovician strata in western basin (the

North China Sea) is an epicontinental sea carbonate platform composed with thick

limestone-dolomite strata (Li and Li, 2008). Sedimentary facies zones around the

depressions in the eastern part have a circular distribution as shown in Fig.1 with the

flat terrain. The central paleo-uplift occurred during the Ordovician Majiagou period

was exposed to sea level and experienced a hot dry climate in which rock salt occurred

(Ran et al., 2012). The central paleo-uplift in the central basin was an intermittently

exposed uplift during the Majiagou period of the Ordovician. This paleo-uplift played

a major role in controlling the paleogeographic pattern of the Majiagou period in the

central and eastern parts of the basin (Yang et al., 2005). The paleogeographic pattern

of the lithofacies in eastern Basin is affected by the geomorphology of the central

depression and the surrounding uplift. The carbonate rocks in the south of the basin are

composed of various dolomites with dense structures. Several gypsum interbeds

developed in the whole Basin, especially in the south of the basin, with very thin layers.

6
Many studies had shown that the Ordovician strata were affected by hydrothermal

activities in the southern Ordos Basin (Zhao et al., 2014; He et al., 2016). In the south

of Ordos Basin, most of the fillings in pores and fractures were composed of dolomite,

calcite, and clay minerals. Local strata contain hydrothermal minerals, such as

wollastonite, pyrite, authigenic quartz, celestite, and multi-stage authigenic calcite.

3. Samples and methods

To better constrain migration mode of hydrothermal fluids, and to reconstruct the

development of hydrothermal fillings in the Ordovician strata, 60 representative

Majiagou Formation core samples were collected from 12 petroleum wells completed

in the various parts of the Ordos Basin (Fig. 1). The samples were used for a

combination of petrological, geochemical and fluid inclusion analyses.

3.1. Petrological studies

The following instruments were used: to obtain the petrological characteristics of the

matrix minerals and fillings, cathode luminescence (CL) images of 83 thin sections

were observed using a Reliotron (CL) instrument (402d series) equipped on a Zeiss

optical microscope with an acceleration voltage of 10–15 keV, a beam current of 250

μA, and exposure durations of 10 s (magnification 50×), 30 s (magnification 100×), and

60 s (magnification 200×), respectively. An SEM equipped with an energy dispersive

spectrometer (EDS) was used to analyze the micron pore spaces and in situ elemental

composition of minerals in 23 representative samples. Analyses were conducted at the

7
China University of Geoscience (Beijing) using a GeminiSEM 450 with an acceleration

voltage of 15 kV, beam current of 20 nA, and a beam diameter of 1 μm. A micro-drill

(MicroDrill, US) equipped with a Nikon SMZ1500 microscope (drill bit model

OSADAXL-230, minimum drill diameter 20 μm) was used to obtain and determine the

composition of stable oxygen and carbon isotopes. The standard 100% phosphoric acid

method was applied, and samples were reacted with 100% phosphoric acid at a constant

temperature under vacuum conditions. The calcareous portion fully reacted with

phosphoric acid at 25 °C for 24 h, and the dolomitic portion was fully reacted at 50 °C

for 72 h. The collected CO2 gas was sent to MAT253C033 mass spectrometer. PDB

standards were used in both the δ13C and δ18O analyses. The test accuracy of these

standards was <0.01‰.

3.2. Geochemical studies

Constant element analysis was conducted using a JXA08100 electron probe (EMP)

equipped with five crystal spectrometers. An accelerating voltage of 15 kV, working

current of 20 nA, and electron beam diameter of 5 μm were employed throughout the

test. Trace element ICP-MS analysis was conducted using an Agilent 7500a, and

reagents used for the analysis were HNO3 and HF (both were high purity reagents

prepared from a superior grade pure acid via a sub-boiling distillation apparatus) with

18 MΩ • cm deionized water. The standard series used was a multi-element mixed

solution prepared using a Claritas PPT conventional multi-element mixing solution

obtained from the SpeX Company (United States). To conduct fluid inclusion analyses,

8
double-sided polished sheets were examined using a transmission and fluorescence

dual-channel Nikon 80I microscope, with a Linkam 600G cold and hot stage and a 100×

focal working objective. In addition, a Maya 2000 micro-fluorescence spectrometer and

other integrated equipment were used to observe the transmission and fluorescence

petrological characteristics. Major and trace element analyses were conducted at the

Beijing Tian'an Ruida Science and Technology Development Co. Ltd. The remaining

experiments were conducted at the China University of Geosciences, Beijing.

3.3. Fluid inclusion studies

Salinity and temperature (homogeneous temperature) were also observed; the

temperature measurement error was ±0.1 °C, and the detection limit of the inclusion

size was >1 μm. In addition, the effects of hydrothermal fluids occurring on a centimeter,

micron, and nanoscale within the formation were investigated using core, casting thin

section, and scanning electron microscope (SEM) images. Furthermore, the

geochemical characteristics of the stratigraphic matrix rocks and various hydrothermal

fillings were investigated using carbon and oxygen isotope analyses, main and trace

element analyses, and fluid inclusion analysis. Constant and trace element analyses of

31 representative powered samples were conducted to distinguish the origin of matrix

minerals and different pore filling types.

4. Results
4.1. Petrological characteristics

The matrix rock of the Majiagou Formation is mainly composed of fine-grained

dolomite that has no cathodoluminescence color, and gypsum-bearing carbonate

9
interlayers are widely distributed at the bottom of the formation. The dolomite near

cracks or fractures is coarse grained and has an idiomorphic shape and a red

cathodoluminescence color, which suggests that it was precipitated from hydrothermal

fluid. The pore fillings in dolomites in the southern Ordos Basin are composed of

quartz-celestite-pyrite assemblages and multi-stage calcareous cements, and pore

spaces show a bipolar distribution. A part of the sample was in the combination of

crack-mold pore-dissolution pore, and the reservoir was good. Various types of

hydrothermal fillings are developed in other samples and they occupy most of the pore

spaces. The following sections provide greater details of samples and their mineral

specific petrological features.

4.1.1. Quartz-Celestite

Quartz and celestite are the most representative hydrothermal minerals and are widely

accepted as indicators of hydrothermal activity (Orduña et al., 2004; Putnis, 2009; Rusk,

2012). Two occurrence state of quartz are recognized within samples: (i)

microcrystalline or cryptocrystalline quartz with cogenetic calcite in siliceous

limestone (Fig. 2a,b), where energy spectrum analysis suggests the presence of

disseminated grossular and sodalite (Fig. 2c), and (ii) hexagonal, bipyramid quartz

crystals that are typically hosted in dissolution pore-fractures (Fig. 2f) within the

microcrystalline dolomite, which have a calcite–celestite assemblage (Fig. 2e) and are

developed locally along such fractures. Electron microprobe results suggest that the

10
samples are rich in crustal element Ti/K. The mineral assemblages described above

occur in all samples and correspond distinctly with the pore spaces of reservoirs. The

few remaining pores of samples filled with cryptocrystalline quartz-celestite are

occupied by various fillings and only a small number of primary intergranular pores

remain. More importantly, there are no obvious dissolution phenomena occurring in

such places.

Conversely, the samples of gypsum or gypsum limestone mixed with

microcrystalline dolomite show highly developed dissolution pores. The pores,

fractures, and residual intergranular pores together constitute a good pore system, and

quartz with hexagonal bipyramid crystals occurs between the residual pore structure.

For carbonate samples in the study area, different mineral assemblage types and pore

compositions relate to the sedimentary environment of the carbonate samples within

the study area, the burial environment, and the fluid properties in later stages.

4.1.2. Pyrite

Pyrite typically implies the existence of a geochemically reducing environment and is

also an indicator of hydrothermal minerals (for example, banded pyrite in carbonate

rocks) (Ledesma et al., 2010; Wei et al., 2015; Zhang et al., 2017). The pyrite recorded

in our samples commonly occurs as strips within vertical cracks and is associated with

abundant residual organic matter (OM) that is typically present in these cracks. Only a

small part of the OM in Fig. 2e (the black color) occurs in an area where hydrothermal

dissolution developed, and OM is well preserved in the primary pores. The occurrence

states of the OM indicate that it was present prior to the arrival of the hydrothermal
11
fluids and pyrite deposition. The presence of both OM and FeS suggests that redox or

TSR reactions may have played an important role in the deposition of pyrite from

hydrothermal fluids (Cai et al., 2003; Marta Sośnicka et al., 2019). The energy spectrum

analysis of the thin section in Fig. 2l shows that in addition to the matrix dolomite,

quartz, orthoclase, and pyrite are present in the fracture, which suggests that these

minerals were deposited by hydrothermal fluids.

4.1.3. Calcite fillings

Hydrothermal calcite associated with quartz is also an indicator of hydrothermal

activity and is useful for determining its relative timing (Perdikouri et al., 2013;

Dubinina et al., 2014; Vaughan et al., 2016). Three different calcite occurrence types

are observed: (i) when part of a pore is filled with calcite, the calcite grains have a

fisheye texture that suggests quasi-syngenetic growth (Fig. 3a); (ii) calcite veins that

occur in many stages (X-type conjugated calcite veins are widely developed within the

strata, and it is considered that fracture-fault calcite veins formed by tectonics could

have been produced during a shallow to deep burial period) (Fig. 3b); and iii) multi-

stage calcite crystals that have a good degree of idiomorphism and occur with

generation cement that was deposited in cracks, fractures, and pores in relation to

hydrothermal activities in the deep burial environment (Fig. 3c).

4.1.4. Hydrothermal dolomite and recrystallized dolomite

Different types of dolomite are found within the study area: (i) quasi-syngenetic

dolomite, (ii) seepage reflux dolomite, (iii) hydrothermal dolomite (Fig. 3e), and (iv)
12
recrystallized dolomite (Fig. 3f). The quasi-syngenetic dolomite mainly developed in

the supratidal zone under an evaporative environment; it has a fine-grained structure

that is close to gypsum lamellae or gypsum dolomite. The seepage reflux dolomite has

a residual oolitic grain structure and the cement is calcite. As previously mentioned,

this study mainly focuses on recrystallized and hydrothermal dolomites. Microscopic

observations show that hydrothermal dolomitization occurred in the fluid flow channel.

The hot fluid provided a constant amount of heat and Ca2+/Mg2+ for dolomitization to

occur, and this resulted in the growth of recrystallized dolomite and hydrothermal

dolomite with a good crystal shape, as shown in Fig. 3f. The recrystallized dolomite is

based on the original matrix rock, and the dolomite recrystallized to form hydrothermal

dolomite, which has a foggy center–bright edge structure and a red

cathodoluminescence on the bright edge. The other type of recrystallized dolomite is

an completely authigenic hydrothermal dolomite precipitated from hydrothermal fluid.

In general, the recrystallized dolomite crystals are slightly larger than those of

authigenic hydrothermal dolomite, but both types of specimens show a high degree of

self-shape and are distributed on both sides of the hydrothermal flow channel.

4.2. Geochemical characteristics

4.2.1. Stable isotopes

The δ13C and δ18O compositions of carbonate rocks closely reflect their sedimentary

environment (Cai et al., 2015; Nejadhadad et al., 2018; Zhang et al., 2019). According

to isotope thermal fractionation theory, the value of δ18O becomes increasingly

13
negative in accordance with an increase in temperature or burial depth. Based on core

and microscopic observations, the authors applied micro-drilling technology to sample

the bedrock dolomite, the hydrothermal dolomite occurring at the same depth (crystal

centers and edges), and calcite fillings. Carbon and oxygen isotope analyses were then

conducted to obtain the paleofluid properties and constrain the evolution of the

diagenetic environment.

Figure 4 shows that δ18O values of the matrix dolomite are concentrated between

−12.8‰ and −6‰. However, δ13C shows a bipolar distribution: one part is associated

with normal marine sediments and values are between −4‰ and 0‰, while the other

part is low in δ13C and ranges from −9‰ to −6‰, which implies the sample was

affected by hydrothermal recrystallization (Fig. 4a). The δ18O and δ13C values of the

hydrothermal dolomite (including crystal center and crystal edge) range from −15‰ to

−13‰ and −7‰ to −4.8‰, respectively; these values are lower than those of the matrix

dolomite at the same depth. Both the δ18O and δ13C values of the fillings and matrix

dolomite are lower than those of normal marine dolomite (δ18O: −8.9‰ to −4.8‰; δ13C:

−1.9‰ to +1.2‰) as measured by Tucker and Wright (1990), and the δ13C values are

considerably lower. This indicates that samples obtained in the southern part of the

basin as Fig.1b shown were affected by both hydrothermal activities and other

geological effects. The most likely explanation is that the carbonate rocks underwent

multiple stages of atmospheric freshwater leaching, the influx of which was controlled

by the multi-stage uplift of the basin. The fresh leaching resulted in a significant bias

14
of δ13C. The corresponding distribution of δ18O and δ13C values in the calcite fillings

are also differentially distributed in both the pores and fractures (Fig. 5b). As shown on

the right side of Fig. 5b, the δ18O and δ13C values are concentrated from −11‰ to −6‰

and −6‰ to −1‰, respectively, which shows they were generated in a shallow burial

environment. The sample isotope values in the lower left part are significantly negative,

and distributed from −22‰ to −13.4‰ and −8‰ to −4‰, respectively, which is even

lower than the hydrothermal dolomite values. This also indicates that the sample on the

left contains calcite with a hydrothermal origin. Compared with the δ18O and δ13C

values of normal marine sediments, all samples have negative anomalies. Although

freshwater fluids can also lead to 18O and 13C depletion, the 18O and 13C values of

freshwater are higher than those of seawater or marine carbonate sediments (Binderman

et al., 2008). In the contemporaneous karsting period, most of the Ordovician sediments

were controlled by freshwater fluid circulating in the phreatic zone; therefore, the 18O

and 13C values are significantly negative due to freshwater interaction. Apart from

registering hydrothermal effects, the values of the calcite fillings are similar to those of

dolomite and are influenced by atmospheric freshwater fluids. In summary, the matrix

rock experienced hydrothermal transformation after normal marine sedimentation, and

different pore filling types formed in the burial environment rather than in the modern

supergene exposure period.

It was thus considered that the fluid properties associated with the burial period

required further analysis, and trace element analysis was conducted to determine the

15
existence of other epigenetic geological processes, such as freshwater leaching or

evaporation.

4.2.2. Trace elements

The REE parameters ∑REE, δCe (Ce/ Ce*), δEu (Eu/Eu*), U/Th, and V/Cr are often

used to determine the existence of hydrothermal action and constrain the diagenetic

environment (Bau and Möller, 1995; Monecke, 2002; Saintilan et al., 2019). REEs and

their distribution relationships are relatively stable in the process of diagenesis and deep

fluid transformation, and they are thus ideal geochemical indicators for use in tracing

the original sedimentary environment. To explore the hydrothermal properties, we first

drew the REE distribution patterns of the matrix rock and calcite fillings in the samples,

and then analyzed the hydrothermal sources in combination with basalt magma

accompanied by Mesozoic tectonism in the upper and lower mantle of the North China

Plate with REE analysis and fluid inclusion data. Figure 6 shows that all the matrix

carbonate samples have right-dip distribution characteristics of light REE relative

enrichment and heavy REE relative loss, particularly those that are cemented by calcite.

Concurrently, the content of Ce is relatively rich, and Eu in the sample shows different

degrees of loss. The calcite filling exhibits weak Eu enrichment that is similar to that

of the basalt upper mantle based on Yang et al (2008) (The average value of Eu: 0.35)

in the southern margin of Ordos Basin, which has the same right-dip partitioning pattern

in the same period. It is thus considered that the hydrothermal fluids were affected by

16
deep basalt magma, and the partitioning mode of trace elements in the formation was

not solely controlled by hydrothermal action.

Following stratigraphic deposition, all the subsequent geological processes (such

as exposure during stratigraphic uplift, atmospheric freshwater leaching, and

hydrothermal upwelling) affected the distribution of REEs. Therefore, to determine the

diagenetic environment of a stratum, it is necessary to combine multiple parameters to

conduct a comprehensive analysis. Several studies have proven that the ratios of U/Th

and V/Cr in trace elements are effective indicators of redox conditions in the

depositional environment (Marynowski et al., 2017; Mohammed et al., 2020). The

U/Th and V/Cr ratios in sediment under anoxic conditions are generally greater than

1.25 and 425, respectively, and less than 0.75 and 2, respectively, in an oxidizing

environment. To investigate the influence of hydrothermal fluid on the formation of

carbonate rock in the Majiagou Formation and to determine its sedimentary

environment, well Y1758 was selected for study, as it is known to have been affected

by hydrothermal fluid. The distribution of U/Th and V/Cr values have identical patterns

(as shown in Fig. 6b/c), and those for dolomite and argillaceous dolomite within the

upper part of the Majiagou Formation are representative of a relatively oxidizing

environment. Conversely, the U/Th and V/Cr values are higher for the siliceous

dolomite within the bottom part of the formation, thus representing a weak oxidation–

reduction environment that may have been related to modification of the diagenetic

fluid under burial conditions. Differences in the Th/U ratio are mainly related to

17
changes in the amount of Th, and pure limestone shows greater Th enrichment than

siliceous limestone. Th may have been added during the hydrothermal silicidation (i.e.,

sintering) process, which caused an increase in the Th/U ratio of the siliceous dolomite.

However, as its overall content is still exceedingly low (it has the same order of

magnitude as the veined quartz), the high Th abundance may be related to hot brine

discharged from the source rock.

Ce is often fractionated with other trivalent REEs in normal seawater because of

its sensitive redox properties. Soluble Ce becomes relatively more insoluble and

thermodynamically stable Ce4+ under oxidation conditions, and it preferentially enters

sediment particles. δCe values can thus accurately reflect the redox conditions of the

depositional environment. In general, δCe>1 is a positive anomaly that indicates a

reducing environment, and δCe<0 95 is a negative anomaly that usually suggests a

partial oxidation environment. Most of the Ce within the sample from well Y1758

showed positive anomalies, which reveals that the strata formed in a reducing

diagenetic environment (particularly the section corresponding to siliceous limestone).

It is thus considered that hydrothermal factors within the diagenetic environment were

the main cause of positive δCe anomalies. However, some of the δCe values related to

a negative anomalous oxidizing environment, which was likely associated with the

effect of freshwater leaching.

The δEu value of trace elements is the most sensitive parameter used to determine

hydrothermal deposition. Reductive hydrothermal fluids are often marked by

18
significantly positive δEu anomalies: therefore, larger δEu values imply a close

relationship between δEu and hydrothermal deposition. In well Y1758, the δEu

anomaly was negative overall, but it was weakly positive in the local area. The

parameter reflects the average value of the entire stratum sample; therefore, the low Eu

value of normal marine carbonate rocks decreased the Eu content of hydrothermal

minerals, which then caused negative δEu values in the final test.

The ratio of Sr and Ba can be used to discriminate between marine and continental

sedimentary environments and to estimate salinity within diagenetic fluids. The content

of Sr in seawater is much higher than that of Ba; therefore, the effect of seawater

evaporation on Sr is much greater than that on Ba. In addition, it is easy to precipitate

Ba and form barite when seawater evaporates, and larger Sr/Ba ratios imply higher

seawater salinity. Compared with differences in Sr and Ba in relation to the evaporative

environment, the Sr and Ba contents of hydrothermal fluids affected by mantle magma

are often high. Hydrothermal minerals such as calcite, quartz, and celestite formed by

hydrothermal fluids have high Sr contents. In this respect, an especially large amount

of celestite with a chemical formula of SrSO4 exists in the study area, and it has high

Sr values. Conversely, the ratio of Sr/Ba in fresh water is lower than that of normal

marine carbonate rock, and if a formation has been subjected to fresh water leaching,

the original Sr/Ba decreases. According to its petrological characteristics, the local

gypsum interlayer and the gypsum limestone of the Majiagou Formation in the study

area underwent a certain degree of evaporation. Based on the distribution characteristics,

19
the top of the Majiagou Formation has lower levels of U/Th, V/Cr, δCe, and δEu, which

confirms that they were impacted by freshwater leaching. However, the positive

anomalies of δCe and δEu in the local strata and higher U/Th, V/Cr, and Sr/Ba values

indicate that the study area, was affected by hydrothermal action, and this particularly

affected the bottom of the Majiagou Formation.

4.2.3. Fluid inclusions

Microscopic temperature measurements (Th) of 233 gas-liquid two-phase salt-water

inclusions and hydrocarbon inclusions were conducted on calcite fillings within

dissolved pores, cracks, and fractures (Table 3). Divided into one episode at 15 °C, the

micro-temperature measurement results of salt-water inclusions show that five episodes

of thermal fluid activity occurred in this interval, and the average homogeneous

temperatures of the episodes were as follows: first episode Th1 = 111.2 °C; second

episode Th2 = 126.7 °C; third episode Th3 = 144.9 °C; fourth episode Th4 = 156.0 °C;

and fifth episode Th5 = 220.6 °C. Similarly, the temperature measurements of oil and

gas inclusions show that four episodes of hydrocarbon fluid activity occurred in this

interval, and the average homogeneous temperatures of these episodes were as follows:

Th1 = 110.0 °C; Th2 = 123.7 °C; Th3 = 144.6 °C; and Th4 = 157.2 °C. It can thus be

inferred that the average homogeneous temperature of the four episodes of salt-water

inclusions was close to that of oil and gas inclusions, which suggests that hydrothermal

and hydrocarbon substances entered the formation along migration pathways via a

20
common tectonic process. The homogeneous temperature distribution of the inclusions

shows that Th1/Th2 and Th3/Th4 relate to multi-episodic hydrothermal-hydrocarbon

flow, and that two hydrothermal fluid periods occurred in the study area. The drilling

data (Depth as shown in Table 1) and DST results from well Y1758 show that the

measured formation pressure gradient of the Ordovician Majiagou Formation was 1.42

MPa/100 m. The measured formation temperature at this depth was T = 89 ℃, the

Quaternary temperature was 21 ℃ (60 m), but the measured geothermal gradient was

2.3 ℃/100 m. The burial-hydrocarbon generation history of strata in the southern part

of the basin was plotted based on logging data and the hydrocarbon generation history

of the Ordos Basin (Ye et al., 2000). The restored paleotemperature characteristics

indicate that calcite formation occurred in two stages between 50–70 °C and 100–

120 °C. The theory of carbon and oxygen isotopes proposed by Minoletti et al. (2014)

was also applied to restore the paleotemperature of minerals (Table 1). The results show

that isotopes of the first stage relate to shallow burial calcite and those of the second

relate to precipitation by hydrothermal fluids; these results also corresponds to the

petrological characteristics of the calcite mentioned above.

The inclusion Raman spectra indicate that the first phase of the oil and gas

inclusions relates to residual asphaltene (Fig. 8f), which implies that the source rock

entered the hydrocarbon generation stage. During this period, tectonic activities caused

hydrothermal fluid to rise to Ordovician strata with OM during the Mesozoic

Indosinian–Yanshan orogeny. The Raman spectrum of the second stage oil and gas

21
inclusions show the typical peak associated with methane characteristics (Fig. 8h),

which is associated with the Cambrian source rocks in the lower strata entering the gas

generation phase. Part of the methane dissolved in water was bound by the

hydrothermal calcite, which was formed simultaneously, and a methane-containing

brine inclusion thus developed (Fig. 8i). Late Yanshan tectonic activities caused several

closed faults and fractures to reopen, and the new faults joined to form a channel in

which the hydrothermal fluids rose. Therefore, as with episodic hydrocarbon expulsion,

the opening and closing of fractures in relation to tectonism caused the multi-episodic

migration of hydrothermal fluids, which explains why the analysis of fluid inclusions

shows evidence of multiple episodic occurrences.

5. Discussion
5.1. Carbonate mineral genesis

Y was the first rare earth metal element discovered, and it reacts with hot water and is

easily soluble in dilute acid. Its formation is affected by organic acids, and organic

ligands are enriched by their ability to bind easily with Y, which increases the Y/Ho

ratio. It is acknowledged that the Y/Ho ratio of normal marine carbonate deposits is

normally between 23.4 and 32. Ho is mainly present as monazite in the Earth's crust,

and it belongs to hydrothermal minerals. In sedimentary rocks affected by hydrothermal

fluid, the Ho content is generally high, particularly in relation to acidic magma. Thus,

carbonate minerals dominated by geothermal fluids have lower Y/Ho ratios. The

sample distribution for the study area indicates that most of the sampled Y/Ho ratios
22
(such as 32) are greater than the upper limits of normal marine carbonate deposits,

which indicates that the strata captured the effects of terrigenous debris during the burial

process. Combined with the analysis of the diagenetic environment conducted

previously, it is considered that the terrestrial debris from atmospheric freshwater

leaching acted on the formation through dissolution cracks, as this can be the only

explanation for the high Y/Ho ratio of the sample. For example, even for

hydrothermally controlled siliceous dolomite, the Y/Ho ratio of a sample should be

lower than 23.4.

The La/Ho ratio is an indicator of the source and migration of hot fluid. Bau et al.

(1994) established a La/Ho–Y/Ho intersection map to determine the genesis of

carbonate rock. A larger La/Ho ratio implies a greater degree of influence of

hydrothermal fluid, and this is confirmed by the lower La/Ho ratios of siliceous

dolomite compared to those of normal marine sedimentary dolomite. These results also

show that the La/Ho ratio decreased sharply and the Y/Ho ratio decreased slightly as

the degree of silicidation increased.

In addition to using the REE index, analyzing the enrichment of major elements

such as Fe and Mn in sedimentary rocks is also important for revealing the origin of the

hydrothermal fluid. According to the alkaline hydrothermal mineral spectra of

labradorite, calcium aluminum garnet, and sodalite from the fluid inclusion data and

trace element partition pattern analyses, it is considered that the hydrothermal fluid in

the study area was controlled by the Mesozoic alkaline basalt magma. The chemical

23
composition of alkaline basalt is plagioclase (mid-feldspar-elongate), olivine, calcium-

rich pyroxene, titanopyroxene (and others), and it has a low Al content; therefore, the

Al in the Majiagou Formation is mainly related to a terrigenous clastic material.

Similarly, the REEs were controlled by terrigenous debris. According to these results,

an intersection diagram of Al/(Al+Fe+Mn)–ΣREE/Fe was established (Fig. 10). Higher

Al and ΣREE contents show that the sample was highly influenced by terrigenous

debris. In addition, a high Fe+Mn content suggests that the effect of the hydrothermal

solution on the sample is greater. Based on the distribution of the matrix dolomite,

siliceous dolomite, and calcite fillings, the hydrothermal effects on these three fillings

increased in turn. Some calcite samples exhibit high Al/(Al+Fe+Mn) and low ΣREE/Fe

values, which is evidence of a hydrothermal genesis.Moller et al. (1980) noted that the

Yb/La ratio exhibits a certain regularity in carbonate minerals that have a magmatic or

normal marine origin, owing to the chemical composition and temperature of the mantle,

and they proposed a Yb/La–Yb/Ca intersection map that has subsequently been used to

explore the origin of carbonate minerals. The higher the Yb/Ca ratio, the more likely it

is that the minerals originated from hydrothermal fluids. The distribution of sample

points in this study indicates that some of the siliceous dolomite and calcite veins were

affected by hydrothermal fluids, whereas the corresponding bedrock dolomite

originated from normal marine deposits (Fig. 11).

5.2. Hydrothermal migration mode

Studies have shown that hydrothermal fluids mainly flow along faults and large-scale

fractures (Ameen et al., 2012). Influenced by their orogenies, the carbonate rocks of the
24
Majiagou Formation developed four fault-fracture system stages between the

sedimentary period and the deep burial period, including an epigenetic-near surface

shallow burial period, a Caledonian weathering and karsting period, a mid-Yanshanian

structural inversion period, and a late Yanshanian–early Himalayan basal uplift

formation period. The preserved karst structures relating to the early shallow burial

period include diagenetic shrinkage fractures, hydration expansion fractures of

anhydrite, and micro-fractures, all of which are mostly filled with mud. The Caledonian

orogeny caused weathering of the fractures and collapse of the karst structures, which

created a vertical, oblique, and horizontal irregular network that provided a high-quality

intra-layer migration channel for the upward movement of hydrothermal fluid.

According to the fluid inclusion and petrological analyses, the Yanshanian–Himalayan

orogeny enabled heat flow through the large faults and fractures of the Ordovician

carbonate formation, which were the principal hydrothermal fluid pathways.

The entire hydrothermal-tectonic system was affected by upwelling of the

asthenosphere below the North China plate and the associated mafic underplating of

the thinned crust. Some of the basalt magma ascended along deep-seated fractures,

forming various types of intermediate-basic intrusive rocks. Dominated by the

temperature gradient and solubility of the Ordovician, molecules rich in K+, Ca2+, Mg2+,

and Fe2+/Fe3+, continuously precipitated throughout the magma emplacement process,

together with other substances such as SiO2. The hydrothermal activity corresponds

with the hydrocarbon generation period of the Cambrian source rock, and hydrothermal

25
fluid carried these molecules into the Cambrian stratum at a high temperature. However,

it is important to determine whether the hydrothermal fluid flowed through the source

rock, and in this respect, two scenarios are considered.

In the first scenario, when the fluid flowed through the source rock via the fractures

and microcracks, the local stratum exchanged ions with the hot fluid. During the entire

process, several SiO2/Ca2+/Mg2+ molecules and other substances precipitated, and the

fluid carried large quantities of OM into the Ordovician Majiagou Formation. A TSR

reaction occurred when the hydrothermal fluid carrying the OM encountered the

gypsum-bearing carbonate interlayer, which provided the SO42- for the TSR reaction

during migration and flow. The acidity and alkalinity of the hydrothermal fluids

inherited from the intermediate-basic basalt magmatic components were altered by the

TSR reaction products, H2S and CO2, and organic acids in the original fluids. The acidic

hot fluid with large amounts of H+ then transformed the pores and fractures of original

carbonate rock, and many of the calcite and dolomite fillings dissolved in this process.

Finally, reservoirs with high porosity and permeability formed in the localized

Ordovician formation.

In the second (alternative) scenario, no reaction occurred between the

hydrothermal fluid carrying various basalt magma ions and the Cambrian source rocks.

As the fluid movement along the faults occurred due to strong fluid suction, it migrated

directly along large faults and cracks to the Majiagou Formation prior to oil and gas

formation; ultimately, oil and gas developed in the Ordovician reservoir. At this time,

26
thermal convection occurred between the extremely high temperature fluid and the

formation fluid at a lower temperature, and the temperature of the hydrothermal fluid

thus continuously reduced. SiO2 with low solubility and highly abundant Ca2+/Mg2+

precipitated quartz and calcite in turn (Lambrecht et al., 2008; Bénézeth et al., 2013;

Radha and Navrotsky, 2013), and thus, multi-stage hydrothermal precipitation occurred.

Primary pores and fractures in the carbonate formations were cemented by

hydrothermal minerals, and the reservoir properties of the formation were drastically

reduced. When the oil and gas subsequently surged along the residual cracks, most of

the pore-cracks were filled with calcite or siliceous material, which prohibited the

formation of high-quality hydrocarbon reservoirs in the Cambrian rocks.

From the fluid inclusion data, the authors also speculate that the hydrothermal

migration mode was similar to that of the episodic charging of hydrocarbons, which

was controlled by the opening or closing of cracks in relation to tectonic activities.

When hydrothermal fluids migrated into the Cambrian strata, the formation pressure

continued to rise with the formation of hydrocarbons, and most of the cracks and faults

closed. Upon recurring tectonic movement, the original cracks and fault reopened along

with the newly formed cracks and hydrothermal migration channels formed. During a

single period of hydtrothermal activity, hydrothermal fluids mixed with hydrocarbons

inside the fractures and faults in Cambrian strata. These multi-stage hydrothermal

activity eventually formed the multi-stage calcite–quartz filling.

27
5.3. Fluid modification model for carbonate reservoir

5.3.1. Model based on acidic hydrocarbon and hydrothermal fluids

There are two different types of hydrothermal fluids in the study area as mentioned

before: fluid 2a and fluid 2b. After entering the gypsum dolomite or phenolic dolomite

formation, the OM-carrying hydrothermal fluid (fluid 1) underwent a TSR reaction with

SO42-,

nCaSO4 + CnH2n+2 = nCaCO3 (CO2) + H2S + (n-1)S + nH2O; (1)

and carbonate dissolution occurred with the reaction product H2S,

CaCO3 / MgCO3 + H2S = Ca2+/Mg2+ HCO3- + HS-. (2)

The hydrocarbons were then consumed to form H2S, CO2, and other reaction products

(Worden et al., 1995; Lu et al., 2011; Hao et al., 2015).

However, as the hydrothermal fluid provided a high temperature, the entire reaction

accelerated within the thermal environment (Hao et al., 2000). In this respect, as with

all TSR reactions, the acidic product dissolved the carbonate minerals, and cracks and

microcracks expanded in relation to dissolution. In addition, the CO32- formed by the

reaction moved along the direction of fluid migration and temperature decline, and

ultimately combined with the Ca2+ in the formation water. When the saturated solubility

of CaCO3 was reached, new calcite precipitates formed. The H2S produced by the TSR

reaction combined with Fe2+ in the hydrothermal fluid to form FeS, which is similar to

calcite, and this eventually formed banded pyrite fillings along the pore fractures. In

addition to the above reactions, a certain amount of SiO2 remained in the hydrothermal

fluid. When convection occurred with the deep formation water, the fluid temperature
28
decreased, and the mixed fluid carried the SiO2 through high permeability channels,

such as the large micro-fractures and dissolution pores. As the deep fluid migration was

relatively smooth and slow, SiO2 precipitated out of the fluid with the decrease in

temperature and formed hexagonal bipyramid quartz fillings between the pore spaces.

Ultimately, the reaction greatly improved the reservoir and permeability of the

formation, and resulted in the local carbonate formation, which is thus a prospective

hydrocarbon reservoir.

5.3.2. Model based on weakly to moderately alkaline hydrothermal and formation

brine

The hydrothermal fluid that inherited the basalt magma ions and molecules (K+, Ca2+,

Mg2+, Fe2+/Fe3+, SiO2) did not pass directly through the source rocks along the large

fractures and faults into the carbonate formation, and the fluid continued to rise in the

direction of high permeability (the micro-fractures and dolomite intercrystalline pores).

During the period of fluid migration, many CO32- molecules were thus produced during

hydrothermal dissolution,

H2S + CaCO3= Ca2+ CO32- + S2-. (3)

Under ion equilibrium, the CO32- rich hydrothermal fluid changed from acidic to

alkaline following the TSR reaction. The S2- thus occurred between the hydrothermal

flow channels in the form of FeS or other sulfides. The reversible ion equilibrium

reaction between CO32- and HCO3- is

CO32- + H2O = HCO3- + OH-, (4)

29
and with the continuous formation of CO32-, the reversible reaction moved in the

direction of OH-. The formation water rich in Ca2+ underwent thermal convection with

the hydrothermal fluid, and the two fluids rich in Ca2+ and CO32- precipitated a large

number of calcite crystals in the medium-weak alkaline environment. Similar to the

formation of hexagonal bipyramid quartz, calcite with the second lowest solubility

(SiO2<CaCO3<MgCO3 under a weak alkaline environment) slowly precipitated from

the fluid when in contact with the mixed fluid, and finally the multi-stage calcite filling

precipitated in cracks and pores that had a high seepage ability (Shock et al., 2013;

Stefánsson et al., 2013). Influenced by the fluid temperature and pH value, the

precipitation sequence of SiO2 was either preceded by calcite precipitation, or followed

by it, and this formed the unique siliceous dolomite or wollastonite. However, the

mixed fluid could easily have had a destructive impact on the reservoirs of carbonate

rocks, as many of the flow channels and reservoir spaces were occupied by various

types of fillings or minerals with few remaining pores, which would have made it

difficult to form an effective reservoir. However, regardless of if hydrocarbon-rich

acidic hydrothermal fluid or medium-weak alkaline hydrothermal-formation water was

present, activation energy at higher temperatures and abundant Mg2+ for dolomitization

would have been provided when the fluid rose along cracks or faults. In addition, the

two kinds of hydrothermal fluids would have coexisted in the Majiagou Formation and

interacted with each other.

30
5.4. Ore deposits associated with hydrothermal fluids

The Ordos Basin is rich in energy resources (such as coal, coal seam gas, and oil shale)

and metalliferous resources (such as sandstone-hosted uranium and coal-type REE

deposits). The latter are products of hydrothermal activity, evidence of which has also

been recorded in the Ordovician carbonate rocks that are the focus of this article.

5.4.1. Sandstone-hosted uranium deposit

The Triassic sandstone-hosted uranium deposits are the main ore deposits in the Ordos

Basin, and they were formed by uranium-bearing, low- to moderate-temperature

hydrothermal activity. The uranium deposits in the Ordos Basin (Fig. 13) are located

along the entire basin margin, which was a hydrothermally active zone (Zhang et al.,

2017; Chen et al., 2019). The southern orogenic belts, as shown in Fig. 12, developed

low-temperature hydrothermal fluids (fluid 2b) that migrated into the basin along

permeable reservoirs and fractures and were driven by gravity. Hydrocarbons played

an important role in the formation (i.e., TSR reactions) and preservation (i.e., fixation)

of the uranium deposits. As demonstrated in previous studies, the δ18O isotopic

composition of hydrothermal calcite associated with the uranium mineralization ranges

from −14.0‰ to −4.7‰, whilst the 13O values range from −9.1‰ to −4.8‰, which is

consistent with the results shown in Figure 4 (Liu et al., 2018; Zhu et al., 2019). The

research of He et al. (2013) showed that alkaline hydrothermal fluids generated in

deeper parts of the basin rose along faults and entered the sandstone formations.

Microbial metabolism then stopped at a relatively high temperature of 140–160 °C.

31
Meanwhile, the hydrothermal fluid extracted the dispersed and adsorbed uranium from

the sandstone and formed a uranium-rich mineral solution. Following the alkaline

hydrothermal activity, microorganisms again become active because of the decreasing

temperature of the formation water, and the uranium in the fluid was mineralized by

microorganisms, such as sulfate-reducing bacteria. Meanwhile, the ore-bearing

sandstones were enriched in hydrothermal calcite and biogenic pyrite.

The distribution of uranium is related to the hydrothermal activities and Ordovician

oil and gas. In this respect, the mixed hydrothermal fluid and oil and gas caused the

same filling types to be developed, such as siliceous cements and multi-stages calcite,

in both the Ordovician reservoir and Triassic strata, and all of these fillings have similar

δ18O and δ13C values. The TSR reaction potentially provided the SO42- for the sulfate-

reducing bacteria during uranium mineralization. This multi-stage hydrothermal

process resulted in the superimposition of oil–gas reservoirs and sandstone-hosted

uranium within different layers in the southern Ordos Basin.

5.4.2. Coal-type REE deposits

Numerous coal deposits, coal-seam gas, and oil shale plays are distributed across the

entire Ordos Basin, whereas the sandstone-hosted uranium and coal-type REE deposits

are typically restricted to previously hydrothermally active zones along the basin

margin (Rao et al., 2011; Zhao et al., 2019; Li et al., 2020). Stratigraphically, the coal-

type REE deposits are mainly contained in the Carboniferous–Permian coal measures.

Owing to the organic affinity of REEs, Zhao et al. (2019) pointed out that an REE-

32
enriched hydrothermal fluid would have been concentrated within OM when flowing

through a coal seam. The migration and accumulation of coal-based metal elements

represents an open dynamic change process (Dai et al., 2020) in which hydrothermal

fluid acts as a carrier of REEs (Xiang et al., 2017; Horn et al., 2020), and the migration

and aggregation of coal-based metal elements vary with the metamorphism of coal and

its OM content (Dai et al., 2016). Therefore, the characteristics of the metal elements

occurring in coal measures are the result of the superposition of both multi-phase

tectonic movements and hydrothermal activity, and developed fracture systems are

useful spaces for the formation of coal-based metal elements as well as the migration

of REE-rich hydrothermal fluid.

Hydrothermal activity along the margin of the southern Ordos Basin resulted in the

formation of coal measures that include an interbedded coal bed methane sequence. The

same recurring low-temperature hydrothermal activity in the southern Ordos Basin also

controlled the formation of Ordovician carbonate reservoirs and Triassic sandstone-

hosted uranium deposits.

6. Conclusions

The results of the petrological and geochemical analyses undertaken as part of this study

are consistent with a model whereby the southern Ordos Basin was affected by two

stages of hydrothermal activity that occurred between Carboniferous and Jurassic times.

In this model, the initial hydrothermal fluid (fluid 1) of the first hydrothermal stage was

generated as a result of a tectonothermal event linked to the underplating of the southern

33
North China Craton by Mesozoic alkaline basalt melts with fluid 1 having inherited the

geochemical signature of these melts. After having passed through the Cambrian rocks

of the Ordos Basin, a stratigraphic sequence that includes hydrocarbon source rocks,

fluid 1 separated into an acidic hydrocarbon-bearing fluid (fluid 2a) and an alkaline

hydrothermal-formational brine (fluid 2b). The former contributed to the hydrothermal

dissolution of the Ordovician carbonate sequence, whereas the latter precipitated

various types of pore- and fracture-filling mineral cements preserved in the Ordovician

carbonate rocks.

The authors speculate that, as with the hydrocarbon expulsion process recorded by

the Cambrian hydrocarbon source rocks, hydrothermal fluid migration occurred

episodically and was triggered during and driven by episodes of recurring tectonic

activity that enabled fluid flow along permeable structures.

In addition to the above, the results of this study suggest that the search for new

hydrocarbon reservoirs in the southern Ordos Basin is most likely to result in discovery

success if focusing on areas where carbonate formations display evidence for

simultaneous hydrothermal dolomitization and hydrothermal dissolution.

In the context of the Ordos Basin as a whole, alkaline hydrothermal activity (fluid

2b) has been identified by others as a key ingredient in the formation of and control on

the spatial distribution of the many Triassic sandstone-hosted uranium deposits

discovered in the Ordos Basin. Concurrently, hydrothermal fluids enriched in REE are

known to have infiltrated coal-bearing strata and been instrumental in the formation of

34
unique, hydrothermal, “coal-type” REE deposits.

Acknowledgments

This work received financial supported from the ‘National Natural Science Foundation

of China’ (Grant No. 41972172 and No.). Special thanks are extended to Dr. Oliver

Kreuzer (OGR Editor) who reviewed four versions of this manuscript and whose

suggestions significantly improved the clarity and quality of this article.

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Figure captions

Fig. 1 (a) Stratigraphy of the Ordovician Majiagou Formation in the Ordos Basin

46
(modified based on Guo et al., 2014); (b) distribution map of sedimentary facies in the

Majiagou Formation.

Fig. 2. (a) Y1758, locally distributed wollastonite in strata and (b) unipolarized image

of subfigure (a). Pores are filled with quartz and calcite. (c) Grossular and sodalite are

hydrothermal indicator minerals developed in the wollastonite interlayers. (d)

Hexagonal bipyramidal quartz precipitated in the fractures and pores, Y1758. (e)

Hydrothermal dissolution pores developed between crystal powder dolomite with

hexagonal bipyramidal quartz. (f) Chromatographic mass spectrometry of minerals in

(c). (g) Single celestite. (h) Results of energy spectrum analysis of the entire rock in

(g). (i) Pore spaces are completely cemented by celestite and calcite. (j) High-angle

fractures in dolomite cores are filled with pyrite. (k) Pyrite stringers. (l) Results of

energy spectrum analysis of entire rock in Fig. 3c.

Fig. 3. Representative calcite and dolomite occurrences in the Majiagou Formation,

southern Ordos Basin. (a) Calcite cemented in the top and bottom structure relating to

syngenetic filling. Part of the pore was retained in this process. (b) Crosscutting calcite-

filled fractures that formed during shallow to deep burial. (c) Multi-stage calcite that

appeared with multi-periods cement. (d) Hydrothermal recrystallization dolomite with

foggy center and a bright edge structure. (e) Authigenic hydrothermal dolomite

showing a red, luminous color. (f) Hydrothermal dolomite and matrix dolomite

captured by SEM imagery.

Fig. 4. (a) Distribution characteristics of δ18O and δ13C in matrix dolomite and

47
hydrothermal dolomite of the Majiagou Formation in the southern Ordos Basin. (b)

Characteristic δ18O and δ13C isotopes of calcite fillings in pores and fractures.

Fig. 5. (a) Simplified lithologic column of the Majiagou Formation. From top to bottom,

fracture-residual primary intergranular pores (filled with calcite), stylolite-fractures,

and developed intergranular pores-hydrothermal dissolved pores. Distribution

characteristics of (b) U/Th; (c) V/Cr; (d) δCe; (e) δEu; and (f) Sr/Ba.

Fig. 6. Rare Earth Element (REE) partition patterns of matrix rock and filings of sample

Y1758.

Fig. 7. Burial-hydrocarbon evolution history of the Ordovician Majiagou Formation in

the southern Ordos Basin (modified based on Guo et al., 2014).

Fig. 8. Petrological characteristics and Raman analysis of fluid inclusions in carbonate

rock samples from the study area. (a) Fluid inclusions in fracture-hosted calcite crystals

(transmitted light), sample Y1757. (b) Liquid phase and hydrocarbon inclusions inside

the calcite fillings in the crack, sample Y431. (c) Fluid inclusions (transmitted light)

inside the calcite filling in the pore, sample Y431. (d) Fluid inclusions in a vein-hosted

calcite crystal, sample T34. (e) Asphalt inclusions in hydrothermal calcite, sample

Y1758. (f) Raman analysis spectrum of inclusions in Fig. 8e illustrating typical asphalt

characteristics and peaks. (g) Methane inclusions in hydrothermal calcite, sample

Y1758. (h) Raman analysis spectrum of inclusions in Fig. 8g illustrating typical

methane characteristics and peak. (i) Single brine inclusions in hydrothermal calcite,

without any characteristic peaks of hydrocarbons, sample Y1758. (g) Raman analysis

48
spectrum of inclusions in Fig. 8i. (k) Methane-bearing brine inclusions in hydrothermal

calcite, sample Y1758. (l) Raman analysis spectrum of inclusions in Fig. 8k, illustrating

a typical methane peak.

Fig. 9. Graph illustrating the relationship between La/Ho and Y/Ho.

Fig. 10. Intersection diagram of Al/(Al+Fe+Mn)-REE/Fe between dolomite and calcite

fillings in carbonate rocks of the Majiagou Formation, southern Ordos Basin.

Fig. 11. Graph illustrating the relationship between Yb/La and Yb/Ca, which indicates

that calcite and dolomite have a marine sedimentary to hydrothermal origin.

Fig. 12. (a)–(b) Before and after the Permian crustal movement, magma-tectonic

evolution model of southern margin of the North China Craton. (c) Hydrothermal

migration model for the southern Ordos Basin. (d) Hydrothermal modification model

of Ordovician carbonate reservoir along a single fault.

Fig. 13. Sandstone-hosted uranium deposit in Ordos Basin modified from Zhu et al.

(2019).

49
50
51
 1000
Sample/Chondrite

100

10

1
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

0.1
Siliceous dolomite Dolomite

Argillaceous dolomite Calcite filling

Dolomitic limestone Magmatic Rocks of Mesozoic North China

Upper mantle Lower mantle

52
53
54
55
56
Table 1. Characteristics of δ18O and δ13 in matrix and calcite fillings and corresponding
paleotemperature.
Geographi Well - Depth Lithology Sampling δ18O δ13C T
c location Sample (m) position (˚C)
ID
Yulin F67-1 2483. Micrite limestone Matrix dolomite −8.79 −1.4 62.44
9 7
Yulin F38-1 2260. Micrite dolomite Matrix dolomite −8.99 −2.3 63.73
8 6
Yulin F38-2 2261. Micrite dolomite Matrix dolomite −10.5 −1.9 74.08
9 4 9
Yulin F38-3 2265. Micrite dolomite Matrix dolomite −9.18 −1.1 64.96
0 2
Yulin F38-4 2269. Micrite dolomite Matrix dolomite −9.18 −2.3 64.96
0 1
Yulin F38-5 2270. Dolomitic limestone Matrix calcite −8.35 −1.6 59.63
6 7
Hejin L17-1 2807. Argillaceous limestone Matrix calcite −7.76 −0.8 55.95
57
 5 6
Hejin L17-2 2808. Argillaceous limestone Matrix calcite −8.59 −1.5 61.16
5 4
Dongling Y257-1 2938. Dolomitic limestone Matrix calcite −6.99 −0.7 51.29
2 5
Mount Qi L187-1 2357. Micrite dolomite Calcite in −9.63 −1.7 67.93
9 fractures 3
Hejin L61-1 3029. Micrite dolomitic Calcite in −6.91 −3.9 50.81
4 limestone fractures 2
Hejin L61-2 3032. Micrite dolomitic Calcite in pores −8.42 −3.2 60.08
1 limestone 4
Hejin L61-3 3033. Micrite dolomitic Calcite in pores −10.5 −3.6 74.29
4 limestone 7 1
Yulin F17-1 3034. Micrite dolomitic Calcite in pores −10.2 −4.2 72.03
7 limestone 4 8
Fuxian Y1757-1 3271. Dolomitic limestone Calcite in pores −9.19 −3.4 65.03
8 9
Fuxian Y1757-2 3275. Dolomitic limestone Calcite in pores −9.32 −5.6 65.88
1 4
Fuxian Y1757-3 3316. Dolomitic limestone Calcite in pores −8.38 −2.6 59.82
6 6
Fuxian Y1757-4 3317. Dolomitic limestone Crystal edge of −13.8 −5.0 98.60
6 HD 9 6
Fuxian Y1757-5 3320. Dolomite Matrix dolomite −11.7 −2.9 82.82
3 8 1
Mount Qi S14-1 2773. Dolomite Matrix dolomite −8.48 −6.6 60.46
6 8
Mount Qi S8-1 2408. Dolomite Matrix dolomite −11.8 −8.2 83.54
5 8 8
Fuxian Y431-1 2863. Dolomite Calcite in −12.3 −8.1 87.26
2 fractures 9 6
Fuxian Y431-2 2864. Dolomite Matrix dolomite −9.02 −3.9 63.92
8 5
Fuxian Y1758-1 3064. Siliceous dolomite HD −10.9 −7.8 76.79
7 3 1
Fuxian Y1758-2 3068. Siliceous dolomite HD −13.3 −6.4 94.68
3 8 9
Fuxian Y1758-3 3108. Siliceous dolomite Calcite in −14.4 −6.8 102.7
3 fractures 2 6 5
Fuxian Y1758-4 3110. Siliceous dolomite The center of −15.9 −8.0 114.9
0 HD 3 9 6
Fuxian Y1758-5 3117. Siliceous dolomite Calcite in pores −14.3 −4.8 102.2
58
 4 6 8 8
Yulin S39-1 2802. Siliceous dolomite Calcite in −21.3 −7.9 163.5
2 fractures 4 7 9
Yulin L39-2 2804. Dolomite Calcite in −15.8 −5.8 114.2
5 fractures 4 2 2
Hejin L3-1 2732. Dolomite Calcite in −14.0 −4.8 99.85
2 fractures 5 6
HD = hydrothermal dolomite; T = calculated paleotemperature

Table 2. Rare earth element (REE) concentrations in matrix rock and calcite fillings.
Sample- Litholo L C P N S E Gd Tb D H Er T Y L
ID gy a e r d m u y o m b u
F67-1 Dolomit 1 1 6. 4. 3. 1. 2.1 1.7 1. 1. 1. 1. 1. 1.
e 6. 1 7 2 1 6 7 4 2 1 4 1 2 0
8 . 0 7 8 1 9 1 5 6 2
4 4
8
F38-2 Dolomit 1 9 6. 4. 2. 1. 2.0 1.3 1. 0. 0. 0. 0. 0.
e 1. . 2 3 8 7 5 2 0 9 9 7 8 6
9 4 7 4 0 4 8 5 1 7 1 7
2 1
F38-3 Dolomit 3 2 1 7. 4. 3. 3.1 2.8 2. 2. 3. 3. 3. 3.
e 5. 0 0. 3 3 5 2 6 7 9 2 8 6 4
4 . 7 7 1 0 4 5 0 4 2 1
9 6 6
8
L17-1 Argillac 1 9 6 4 1 8. 11. 10. 9. 8. 9. 9. 1 1
eous 3 1 4. 1. 7. 4 30 52 2 9 5 1 0. 0.
dolomit 5. . 1 7 0 4 2 7 1 8 2 2
e 4 1 7 6 5 9 9
2 2
Y1757- Dolomit 1 8 5. 3. 1. 1. 1.1 1.1 0. 0. 0. 0. 0. 0.
5 e 1. . 0 6 8 1 1 2 8 7 7 7 8 6
9 5 9 2 6 2 4 3 8 5 4 0
7 0
Y431-1 Dolomit 5. 5 3. 3. 1. 0. 0.9 0.7 0. 0. 0. 0. 0. 0.
e 6 . 6 0 7 8 5 1 5 4 3 3 2 3
8 0 7 9 0 7 1 3 7 0 9 0
5
L61-1 Micrite 4. 4 3. 2. 1. 0. 0.8 0.5 0. 0. 0. 0. 0. 0.
limesto 5 . 2 6 4 7 1 6 3 3 2 2 2 1
59
 ne 0 2 6 5 7 4 6 2 8 3 0 9
8
L17-2 Argillac 1 8 6 4 2 9. 15. 13. 1 1 1 1 1 1
eous 2 7 2. 2. 2. 9 04 53 1. 1. 2. 1. 1. 2.
dolomit 1. . 9 5 5 1 5 4 0 6 9 3
e 6 7 3 6 1 3 9 4 9 3 0
0 9
Y1757- Siliceou 3 2 1 7. 4. 3. 3.1 2.8 2. 2. 3. 3. 3. 3.
1 s 5. 0 0. 3 3 5 2 6 7 9 2 8 6 4
dolomit 4 . 7 7 1 0 4 5 0 4 2 1
e 9 6 6
8
S8-1 Dolomit 1 1 9. 6. 5. 2. 3.4 2.8 2. 1. 1. 1. 1. 1.
e 3. 4 2 9 0 5 3 5 0 5 5 2 2 3
4 . 3 5 1 7 8 6 2 8 5 4
3 3
3
Y1757- Calcite 1 7 5. 4. 2. 1. 1.6 1.9 1. 1. 1. 1. 1. 1.
5 filling 0 . 4 3 6 9 6 1 4 3 3 2 2 2
1 0 3 6 9 2 9 8 3 4 4
7
Y1757- Dolomit 3 2 1 8. 4. 1. 4.9 6.2 7. 8. 8. 9. 1 9.
1 ic 3. 3 4. 9 6 8 4 0 1 2 6 8 0. 4
limesto 3 . 2 0 6 7 0 0 2 4 1 6
ne 2 2 1 3 2 7
6
North Magmat 1 9 5 3 3 22. 1 1 1 1
China ic rocks 2 4 9. 4. 1. 16 7. 4. 4. 3.
Plate of 9. . 8 6 3 0 8 3 6
Mesozo 6 1 3 6 6 4 0 0 6
ic* 1 8
North Upper 2. 1 8.
8. 1 8 27. 55 1 1 1 1 1 2
China mantle* 2 . 13 5 7 41 3.1 3. 2. 8. 9. 6. 4.
Plate 5 3 93 3. 0. 1 9 2 0 7 7 8
6 8 7 7 5 9 5 4 4
6 5
*REE concentrations of Magmatic rocks of Mesozoic and Upper mantle from Zeng et
al. (2010).

Table 3. Fluid inclusion data for calcite grains from carbonate rocks in the southern
Ordos Basin.
60
Well Sample Salt-water inclusion Hydrocarbon
Sample Th1 Th2 Th3 Th4 Th5 Th1 T
ID
Y431-1 Calcite in 121.0 146.8 152.2 110.8 1
fractures
Y431-1 Calcite in 156.5 161.9 1
fractures
Y431-1 Calcite in 143.3 155.2
fractures
Y431-2 Calcite in 140.9 156 1
fractures
Y1757-1 Calcite in 126.9
fractures
Y1757-2 Calcite in 107.6 142.7
fractures
Y1757-3 Calcite in 129.2 156.7 1
fractures
Y1757-4 Calcite in 154.4
fractures
Y1758-5 Calcite in pore 220.6
Y1758-3 Calcite in 144.6
fractures
S39-1 Calcite in 114.9 128.9 137.3 112.3
fractures
S39-2 Calcite in 127.8 106.9 1
fractures

 Two stages of hydrothermal fluids inherited from basalt magma

composition and thermal energy developed in the Ordovician in the southern Ordos

61
 Basin.

 The primary hydrothermal fluid is divided into acidic hydrocarbon-hydrothermal

fluid and alkaline basalt hydrothermal-formation fluid.

 The hydrothermal fluid in the study area migrates in a multi-episodic manner just

like the hydrocarbon expulsion of organic matter.

 Searching for hydrothermal dolomitization and carbonate karst

dissolution between hydrothermal mineral and matrix dolomite in carbonate

formation is the key to the exploration of hydrocarbon reservoirs.

62