Article pubs.acs.

org/EF

Evaluation of Lower Cambrian Shale in Northern Guizhou Province, South China: Implications for Shale Gas Potential
Shuangbiao Han,*,, Jinchuan Zhang, Yuxi Li, Brian Horseld, Xuan Tang, Wenli Jiang, and Qian Chen

School of Energy Resources, China University of Geosciences, Beijing 100083, Peoples Republic of China German Research Centre for Geosciences (GFZ), Potsdam 14473, Germany Strategic Research Centre of Oil and Gas Resources, Ministry of Land and Resources, Beijing 100034, Peoples Republic of China ABSTRACT: The Lower Cambrian shale is an important source rock for conventional oil and gas in northern Guizhou province (NGP), south China, but has recently been considered as a potential shale gas reservoir. In this study, characterization of this target shale was determined through a systematic series of measurements on core samples. According to total organic carbon (TOC) and Rock-Eval data, the Lower Cambrian shale is overmature but still contains high amounts of organic matter, which is composed mainly of alginite. The TOC content is enriched up to 10.4% at the base of the shale. There are two dierent correlation patterns between trace elements and TOC in the Lower Cambrian shale. A good correlation present in the upper part indicates a non-suldic anoxic sedimentary environment. However, higher enrichments of U, V, and Mo in the basal part exhibit suldic euxinic conditions. Brittle minerals are quite abundant and have a critical eect on articial fracture. Gas sorption volume increases with an increasing TOC, pore volume, and surface area, indicating that pores at the microscale associated with the organic matter fraction are an important control on storage capacity. The contribution of clay minerals to the sorbed gas may be irrelevant because of the presence of moisture. Analysis of data indicates that the basal part of the Lower Cambrian shale demonstrates the greatest potential for gas content and can be explored for production.

1. INTRODUCTION With commercial production in the U.S.A., the shale gas boom is changing the world and has been the exploration focus for energy in many countries and regions (Canada, Europe, South Africa, and Australia) [U.S. Energy Information Administration (EIA); http://www.eia.gov/]. To boost national energy security, the Chinese government is also trying to develop this unconventional resource. Geological surveys and well drilling have increased recently. Strategic investigation by the Ministry of Land and Resources (MLR; http://www.mlr.gov.cn/ mlrenglish/) has revealed that shale gas resources could amount to 10.48 1012 m3 in Guizhou province alone. The Lower Cambrian shale in northern Guizhou province (NGP) of the upper Yangtze block (UYB) is not only rich in organic matter but also shows good gas concentrations and ow characteristics.1 However, few shale gas wells have been drilled in this area, and there is a lack of detailed data characterizing black shale in the literature. Researching the properties of shale gas reservoirs is very important to elucidate potential gas capacities while reducing exploration risk.24 Here, we report an investigation on the Cenye1 well, located in the Cengong area of NGP. This is a national geological investigation shale gas well with a completion depth of 1526 m. Hydrocarbon anomalies were monitored during drilling, and gas was produced after fracturing. The NGP area lies in the southeastern part of the UYB in south China. A disconformity occurred between the Upper Sinian and Lower Cambrian in the Late Proterozoic. During the Early Cambrian, a thick succession was deposited in an open marine platform to marine shelf environment, whose total original thickness could have been up to 1200 m.5,6 The generalized Lower Paleozoic stratigraphy is shown in Figure 1. The Lower
XXXX American Chemical Society

Cambrian succession in this region consists of black shale, carbonate rock, and siltstone and has been studied as a major source rock before.5,6 The organic-rich sedimentary rock sequence is developed widely throughout the NGP area and will be assessed as a potential shale gas reservoir. Because of sea level regression in the Middle to Late Cambrian, a predominantly restricted marine platform environment resulted in a thick carbonate succession. The succession dips gently at 512 in the Cenye1 area (Figure 1).

2. MATERIALS AND METHODS

2.1. Samples. A total of 31 core samples, including one Precambrian siliceous shale, were selected from the Cenye1 well according to intervals based on stratigraphic data and logging response. Sample distributions are shown in Figure 2 together with detailed core descriptions and well log curves. 2.2. Experimental Approach. In this study, the core samples were geochemically and petrophysically characterized (Table 1). To assess the shale gas signicance of the investigated rocks, total organic carbon (TOC), trace element (TE) content [inductively coupled plasmamass spectrometry (ICPMS)], X-ray uorescence (XRF), mineralogy [Xray diraction (XRD)], Hg porosimetry, pore size distribution, and gas sorption capacity were determined and Rock-Eval pyrolysis was performed. The well logging data were collected from MLR. The TOC content was measured using a Leco SC-632 instrument, and a Rock-Eval 6 instrument was used for pyrolysis analysis, which provides Tmax, S1, S2, and S3. The temperature program was set as 300 C for 3 min and then heating at 25 C/min to 650 C. Tmax is the required Received: January 24, 2013 Revised: May 7, 2013

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Figure 1. Studied locations, geological map of Cenye1 area, and stratigraphic column of the Lower Paleozoic in NGP. temperature for kerogen cracking.S1 is the amount of volatile hydrocarbon. S2 represents the amount of pyrolysis compound. S3 is the amount of CO2 generated.7 Al oxide was analyzed by XRF on dried powdered samples. TE (Sc, Zr, Th, U, V, and Mo) concentrations were determined by ICPMS using sample powders dissolved in HF, HClO4, and HNO3. Bulk mineralogical compositions were measured with XRD using powdered rock samples. According to the International Union of Pure and Applied Chemistry (IUPAC) classication of porous materials, pores are divided into micropores (<2 nm), mesopores (250 nm), and macropores (>50 nm) based on diameter.8 The mesomacropore volume and surface area were detected using nitrogen (N2) gas adsorption. The methods of BrunauerEmmettTeller (BET) and BarrettJoynerHalenda (BJH) were employed for calculation.9,10 Hg porosimetry was conducted on an Autopore IV 9510 series porosimeter. The pressure of Hg was increased up to 414 MPa, and mercury injection data were calculated for porosity (pore diameter > 3 nm).11 Methane sorption isotherms were determined on moistureequilibrated samples under reservoir temperatures. The Langmuir isotherm was used to model gas sorption capacity, V = VLP/(PL + P), where V is the volume of sorbed gas, VL is the Langmuir monolayer volume, P is the equilibrium pressure, and PL is the Langmuir pressure at which the sorption gas equals half of the Langmuir volume.12 The well log response was derived after drilling by the MLR, China.
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3. RESULTS 3.1. TOC and Rock-Eval Pyrolysis. The TOC content and Rock-Eval data for 15 samples from Cenye1 well in NGP are presented in Table 2. TOC values vary from 0.73 to 10.40%, with an average of 4.35%. S1 and S2 values are extremely low in the Lower Cambrian shale (average of 0.06 and 0.11 mg/g, respectively). Anomalously low Tmax values are present in samples G012090 and CUGB22. Corresponding to the high Tmax values, thermal maturities are calculated above 3.0% (Ro = 0.0180Tmax 7.16).13 Meanwhile, hydrogen indices (HI = S2/ TOC 100) range between 1 and 4 mg of hydrocarbon (HC)/g of TOC, and oxygen indices (OI = S3/TOC 100) vary from 3 to 38 mg of CO2/g of TOC. 3.2. TEs. The results for TE abundances and ratios (U/Al, V/ Al, and Mo/Al) in the Lower Cambrian shale of NGP are summarized in Table 3. The concentrations of redox-sensitive TEs (Al, Sc, Zr, Th, U, V, and Mo) show ranges from 1.7 to 13.3%, from 0.779 to 20.5 g/g, from 12.6 to 260 g/g, from 0.481 to 17.8 g/g, from 3.97 to 97.3 g/g, from 98.2 to 1682 g/g, and from 2.55 to 269 g/g, respectively. Meanwhile, U/Al, V/Al, and Mo/Al ratios vary from 0.33 to 13.70% (g/g), from 10 to 236.9% (g/g), and from 0.21 to 128.1% (g/g), respectively (Table 3). The basal shale exhibits relative U, V,
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Figure 2. Lithological column of Cenye1 well, sample locations, and log curves.

and Mo enrichments. Al versus Th, Zr, and Sc show positive correlations in the Lower Cambrian shale (Figure 3; R2 = 0.8548, 0.8921, and 0.9575, respectively). 3.3. Bulk Mineralogy. Mineralogical analysis (XRD) results are shown in Table 4. As the data indicate, the Lower Cambrian shale in NGP mainly contains clay and quartz minerals. Measured ranges of total clays are between 9 and 59% (average 34%), and quartz minerals are between 27 and 86% (average
C

49%). There is no more than 10% carbonate (calcite and dolomite) minerals (apart from two samples, CUGB11 with 32% and CUGB23 with 15%). Generally, illite is the dominant mineral in clays. There are minor amounts of pyrite and feldspar in the Lower Cambrian shale. Ternary plots of mineral composition are shown, so that a meaningful comparison can be made between the Lower Cambrian shale in NGP (Figure 4b) and hot shales with
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Energy & Fuels Table 1. Experimental Analysis of the Lower Cambrian Shale in NGP
sample analysis TOC and Rock-Eval pyrolysis TE content (XRF and ICPMS) mineralogy (XRD) and mercury (Hg) injection nitrogen (N2) gas adsorption gas sorption capacity well logging data laboratory location Applied Petroleum Technology AS, Norway CNNC Beijing Research Institute of Uranium Geology, China PetroChina, Huabei Oileld Branch, China College of Chemistry and Chemical Engineering, China University of Petroleum, Beijing, China Research Institute of Petroleum Exploration and Development, Langfang Branch, China MLR, China

Article

comparison. The results show that the sorbed gas amount varied from 1.09 to 2.55 m3/ton, with a mean value of 1.79 m3/ton.

successful exploitation in the U.S.A. (Figure 4a). According to the diagram, two distribution regions can be recognized in Figure 4a. For the Bossier shale, the content of clay minerals is below 70%, total quartz, feldspar, and pyrite are lower than 50%, and carbonate varies between 5 and 90%. In the other region, quartz, feldspar, and pyrite minerals range from 25 to 80%, the clay content is between 15 and 65%, and carbonate is lower than 25% in the Ohio and Woodford/Barnett shales (west Texas). For the siliceous Barnett shale, total quartz, feldspar, and pyrite are higher than 40% and clays are no more than 50%. As the comparison indicates (Figure 4b), the mineral composition of the Lower Cambrian shale in NGP is similar to the Ohio and Woodford/Barnett shales (west Texas). 3.4. Porosity. We studied the porosity of the Lower Cambrian shale in NGP through mercury (Hg) injection and nitrogen (N2) gas adsorption determinations. As seen in Table 5, all samples apart from CUGB22 exhibit low values of Hg porosity (<5%) and most porosities are below 2%. The mean value of the BET specic surface area is 7.683 m2/g (range from 0.721 to 30.320 m2/g), while the BJH pore volumes vary from 0.0012 to 0.0170 mL/g, with an average of 0.0058 mL/g. Most of the BET surface area is associated with pores less than 10 nm in diameter (Figure 5). 3.5. Methane Sorption Isotherms. Methane sorption experiments were performed on 11 dierent depth samples from the Lower Cambrian shale (Table 6). Methane sorption capacities were measured at a consistent pressure of 6 MPa for Table 2. TOC and Rock-Eval Results
code CUGB02 CUGB04 CUGB09 G012083 G012084 CUGB15 G012086 G012087 CUGB17 CUGB18 G012090 G012091 G012092 CUGB22 G012094 depth (m) 1224 1290 1366 1421.5 1425 1430 1433 1436 1441 1442 1446 1449.5 1455 1459 1460 TOC (%) 0.73 1.11 2.6 2.59 2.64 4.01 6.27 7.75 10.4 6.79 2.35 4.29 1.77 6.21 5.68 S1 (mg/g) 0.01 0 0.01 0 0.01 0.03 0.02 0.11 0.34 0.05 0.02 0.07 0.04 0.07 0.05 S2 (mg/g) 0.02 0.02 0.04 0.03 0.03 0.07 0.05 0.27 0.42 0.17 0.08 0.09 0.05 0.20 0.10 S3 (mg/g) 0.10 0.08 0.33 0.09 0.24 0.50 0.62 0.87 3.93 0.35 0.20 0.26 0.18 0.66 0.28 Tmax (C) 599 577 590 599 595 601 599 596 599 601 429 600 601 452 600
D

4. DISCUSSION 4.1. Source Rock Characteristics. The Lower Cambrian shale evolved into the dry gas and thermogenic gas window, with organic matter being overmature (Ro 2%) in NGP. Although overmaturity was attained by shale rocks, the total organic carbon content is still relatively high. Sedimentation and organic carbon productivity rates are the controlling factors inuencing the TOC concentration. With a changing depth of burial, both maturity and hydrocarbon generation levels were aected by geothermal heating. During the Late Jurassic, the geothermal temperature of the Lower Cambrian shale was close to 220 C, which is signicantly higher than present day temperatures, which range from 140 to 160 C,14,15 and therefore, a complex thermal history can be inferred. It is noteworthy that there is no correlation between TOC and maturity of the Lower Cambrian shale in NGP, unlike the inverse relationship present in the Lower Cretaceous shale in northeastern British Columbia.16 Because of the high maturation levels, no distinct S2 peaks were present in Rock-Eval pyrolysis (Table 2); hence, erroneous Tmax values occurred with unreliable S2 values (less than 0.2 mg/g).17 The original kerogen type cannot be identied directly using a pseudo-Van Krevelen plot because of the extremely low hydrogen and oxygen indices. Previous studies demonstrated a sapropelic (type I) organic material composed mainly of alginite.6,18 This kind of organic matter has good to excellent generation capability before reaching overmaturity. Hunt19 suggested that the thermally mature elds may still potentially generate gas from the secondary cracking of hydrocarbon in situ. Jarvie et al.20 considered cracking gas to be the primary source for the Barnett shale in Newark East Field. Despite the fact that the Lower Cambrian black shale holds very low remaining hydrocarbon generation potential, large amounts of oil and gas must have been generated during its geological history. This case may show an insight for shale gas in NGP. 4.2. Redox Conditions. The redox classication of sedimentary settings is characterized by oxic, suboxic, and anoxic (including suldic and non-suldic) conditions. In response to the changing redox conditions, TE concentrations can be used as indicators of the paleoenvironment.21 Normalizing TE concen-

PI (wt ratio) 0.33 0 0.20 0 0.25 0.30 0.29 0.29 0.45 0.23 0.20 0.44 0.44 0.26 0.33

HI (mg of HC/g of TOC) 3 2 2 1 1 2 1 3 4 3 3 2 3 3 2

OI (mg of CO2/g of TOC) 14 7 13 3 9 12 10 11 38 5 9 6 10 11 5

Ro (%) calculated 3.62 3.23 3.46 3.62 3.55 3.66 3.62 3.57 3.62 3.66 0.56 3.64 3.66 0.98 3.64

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Energy & Fuels Table 3. TE Concentrations and Ratios for the Lower Cambrian Shale
code CUGB01 CUGB02 CUGB03 CUGB04 CUGB05 CUGB06 CUGB07 CUGB09 CUGB11 CUGB13 CUGB15 CUGB17 CUGB19 CUGB21 CUGB22 CUGB23 depth (m) 1210 1224 1274 1290 1317 1350 1355 1366 1414.5 1424 1430 1441 1445 1450 1459 1469 Al (%) 10.5 7.6 12 10.5 8 10.1 13.3 11.6 9.9 9.9 8.7 7.6 9.1 7.1 2.1 1.7 Sc (g/g) 16.6 11.7 16.8 16.4 13.3 15.5 20.5 15.9 13.8 15.9 13.5 9.14 12.5 11 0.779 1.01 Zr (g/g) 192 159 260 209 155 175 222 228 156 186 153 115 207 167 12.8 12.6 Th (g/g) 16.8 12.3 17.8 16.1 11.6 13.2 15.5 15.1 9.62 10.5 9.65 8.62 11.8 9.77 0.481 0.637 U (g/g) V (g/g) 8.03 4.64 4 7.54 7.2 10.4 5.02 4.86 4.07 12.5 30.3 89.8 63.3 97.3 3.97 14.1 151 98.2 147 195 280 199 133 191 151 389 923 1406 561 1682 166 347 Mo (g/g) U/Al (%, g/g) 22.3 10.6 2.55 32.8 23.2 27.6 5.2 3.89 4.32 35.2 97.5 256 104 227 269 24.5 0.76 0.61 0.33 0.72 0.90 1.03 0.38 0.42 0.41 1.26 3.48 11.82 6.96 13.70 1.89 8.29 V/Al (%, g/g) 14.38 12.92 12.25 18.57 35.00 19.70 10.00 16.47 15.25 39.29 106.09 185.00 61.65 236.90 79.05 204.12

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Mo/Al (%, g/g) 2.12 1.39 0.21 3.12 2.90 2.73 0.39 0.34 0.44 3.56 11.21 33.68 11.43 31.97 128.10 14.41

Figure 3. Correlation plots for Al, Th, Zr, and Sc in the Lower Cambrian shale.

trations to aluminum (Al) is a general method to correct for the dilution eects by organic matter and authigenic minerals.21 This convention is only valid when Al originates from siliciclastic ux and is immobile within diagenetic processes. To conrm this prerequisite, checking the correlations of Al versus Th, Zr, and Sc
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is a suitable method. If a positive linear relationship exists, the siliciclastic origin of Al can be inferred. This appears to be true for the Lower Cambrian shale in NGP (Figure 3). According to previous research, redox-sensitive TEs U, V, and Mo show potential discrimination in sedimentary systems.2224
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Energy & Fuels Table 4. Mineralogical Analysis Results for the Lower Cambrian Shale in NGP
code CUGB01 CUGB02 CUGB03 CUGB04 CUGB05 CUGB06 CUGB07 CUGB09 CUGB10 CUGB11 CUGB12 CUGB13 CUGB15 CUGB17 CUGB19 CUGB21 CUGB22 CUGB23 depth (m) 1210 1224 1274 1290 1317 1350 1355 1366 1369 1414.5 1418 1424 1430 1441 1445 1450 1459 1469 total clay (%) 45 25 41 44 35 46 59 42 41 35 46 34 32 25 25 19 11 9 chlorite (%) 9 6 10 7 6 10 9 8 9 1 <1 1 <1 <1 <1 <1 <1 <1 illite (%) 25 14 23 26 19 24 34 21 19 24 25 21 22 21 16 12 8 7 illite/smectite (%) 12 6 7 11 10 12 17 13 14 10 20 12 10 4 9 7 3 2 quartz (%) 44 65 52 45 52 46 32 45 40 27 31 44 49 46 37 61 86 76 carbonate (%) (calcite + dolomite) 4 calcite (%) 2 dolomite (%) 2 feldspar (%) 11 4 6 7 9 5 5 10 9 4 8 10 8 11 23 11

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pyrite (%) 2 1 4 3 3 4 3 6 2 5 9 5 9 12 7

4 32 10 3 6 9 3 2 3 15

1 5 2 0 0 2

2 13

3 27 8 3 6 7 3 2 1 2

Figure 4. Ternary diagrams of black shale mineralogy: (a) U.S.A. hot shales, modied from Halliburton, and (b) Lower Cambrian shale.

Table 5. Porosity, BET Surface Area, and BJH Pore Volume of the Lower Cambrian Shale in NGP
code CUGB01 CUGB02 CUGB03 CUGB04 CUGB05 CUGB07 CUGB10 CUGB11 CUGB12 CUGB13 CUGB15 CUGB17 CUGB19 CUGB21 CUGB22 CUGB23 depth (m) 1210 1224 1274 1290 1317 1355 1369 1414.5 1418 1424 1430 1441 1445 1450 1459 1469 Hg porosity (%) 2.20 0.90 4.10 0.70 0.80 0.20 1.50 1.70 1.30 1.10 0.80 2.10 0.80 2.70 6.20 1.40 BET surface area (m2/g) 4.997 1.644 0.811 5.762 5.710 1.915 5.159 3.500 5.985 6.331 12.270 30.320 21.410 15.520 0.870 0.721 BJH pore volume (mL/g) 0.0029 0.0024 0.0015 0.0088 0.0066 0.0014 0.0047 0.0038 0.0085 0.0077 0.0050 0.0132 0.0170 0.0062 0.0015 0.0012

Figure 5. BET surface area and pore size diameter distributions in the Lower Cambrian shale in NGP.

Uranium (U) is present mainly in the soluble form UVI in uranyl carbonate complexes [UO2(CO3)34] in oxic to suboxic
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settings. UVI can be reduced to UIV with crystalline uraninite (UO2) or metastable precursors precipitated in the sediments under certain anoxic conditions.21 This reduction procedure requires sulfate bacteria catalysis and is related to organic matter content.21,24 In non-suldic anoxic facies, U exhibits a good correlation with TOC.23,24
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Energy & Fuels Table 6. Methane Sorption Capacities of the Lower Cambrian Shale in NGP
code CUGB01 CUGB03 CUGB05 CUGB07 CUGB10 CUGB12 CUGB15 CUGB17 CUGB19 CUGB21 CUGB23 depth (m) 1210 1274 1317 1355 1369 1418 1430 1441 1445 1450 1469 VL (m3/ton) 1.39 1.25 3.07 1.13 1.83 1.48 2.60 3.72 3.97 3.41 2.51 PL (MPa) 0.35 0.39 2.79 0.20 1.26 1.53 2.04 2.84 3.33 2.38 1.90 sorption capacity at 6 MPa (m3/ton) 1.31 1.17 2.10 1.09 1.51 1.18 1.94 2.52 2.55 2.44 1.91

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Vanadium (V) is concentrated in reducing environments in sediments and sedimentary rocks.24,25 There is a two-step conversion process for V removal from water. From oxic to reducing conditions, the reaction of VV to VIV is facilitated by humic and fulvic acids. In suldic (euxinic) facies, further reduction of VIV to VIII occurs in the presence of free H2S. V exhibits a weak correlation with TOC under euxinic conditions.26 Molybdenum (Mo) is present mainly as MoVI in the form of molybdate (MoO42) in the seawater column. Its concentration in sediments is promoted through the reaction of stable MoO42 with particle-reactive elements.27 This conversion may be rapid with the formation of free H2S in a suldic (euxinic) sedimentary environment. Mo accumulation is related to the eect of sulfate-

reducing bacteria on organic matter, and a good correlation exists between Mo and TOC concentrations in non-suldic facies.23,24 It is possible to distinguish redox conditions by evaluating TOC/TE relationships. Algeo et al.23 inferred controls on TE behavior in the Upper Pennsylvanian black shale and characterized two patterns of TE enrichment and TOC, i.e., strong and weak euxinic anities. Pi et al.28 researched the redox environment of the Niutitang Formation in the Lower Cambrian black shale in Guizhou Province and inferred an upward changing trend of suldic (euxinic) to non-suldic conditions. In the present study, relationships between TOC and TE enrichment factors (U/Al, V/Al, and Mo/Al) were used to reconstruct paleoredox conditions in NGP (Figure 6). In comparison to the Black Sea suldic (euxinic) sediments [U/ Al, 3.3% (g/g); V/Al, 28.8% (g/g); and Mo/Al, 4.3% (g/ g)],21 the basal part of the Lower Cambrian shale in NGP displays U, V, and Mo enrichment (Figure 6) and with variable decreases in the upper part. Obvious correlations (U/Al-TOC, V/Al-TOC, and Mo/Al-TOC) were observed in the upper part of the shale, which point to a non-suldic anoxic depositional environment. However, TE ratios in the basal shale show a weak anity with TOC. This case indicates that generally suldic (euxinic) conditions occurred. 4.3. Gas Sorption Capacity. Estimation of the potential gas content in the shale reservoir is a challenging task, but it is critical to determine an exploration strategy for shale gas, especially in a frontier area. The gas can be stored in three dierent states, namely, (1) adsorbed gas associated with the organic and inorganic components in black shales, (2) free gas principally

Figure 6. Correlation plots between TOC and U/Al, V/Al, and Mo/Al in the Lower Cambrian shale.
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Figure 7. Three-dimensional plots relating sorption gas capacity with TOC content, BET surface area, BJH pore volume, and clay mineral content.

controlled by rock porosity, and (3) solute gas dissolved in water or hydrocarbon uids.29 Some previous studies have quantied the free gas proportion of total gas-in-place (GIP) volume by assuming that open pores are saturated with gas (water saturation = 0).16,30,31 Under laboratory measurements, the sorption gas capacity may include adsorbed gas and solute gas, which cannot be dierentiated in experiments. Controls on the amount of sorbed gas in the Lower Cambrian shale are poorly constrained in NGP; hence, there is a need for experimental analysis on the gas sorption content of black shale in the present studied area. The methane sorption capacity of the Lower Cambrian shale in NGP increases with the TOC content (Figure 7), which can be used as a parameter to select the vertical interval and target area with a high gas content in shale gas exploration. The organic matter in the studied shale is microporous with an internal surface area and pore volume. In addition, nitrogen BET surface area or BJH pore volume exhibit a positive correlation with TOC (Figure 7). Despite the limited pore size distribution and small pore volume, a potential amount of gas, including solution gas, could be stored within the bituminite matrix of black shales.32 Meanwhile, clay minerals are also thought to inuence the sorption properties. Some authors have postulated that aluminosilicates, such as illite, contribute to the gas sorption capacity.31,3335 However, a moderate negative correlation (R2 =
H

0.6039) is observed between the clay content and sorbed gas capacity of the Lower Cambrian shale in NGP (Figure 7), which we attribute to the moisture content and temperature conditions in the laboratory measurements. In the present study, methane sorption analysis was performed on moisture-equilibrated shale powders under reservoir temperatures. The sorptive capacities of clay minerals could be restricted and irrelevant as a result of the presence of moisture, which constrains gas adsorption on clay surfaces and sorptive sites. In recent studies, a signicant decrease in the gas sorption content was measured and researched on dry and moisture-equilibrated samples, including pure illite.30,35 The physical adsorption of gas molecules in shale is assumed to be exothermic;31 therefore, relatively high temperatures may lead to a reduction in gas adsorption ability. A similar reduction occurs in Besa River and Mattson shale formations of the western Canada sedimentary basin, with temperatures ranging from 30 to 100 C.31 According to the depth of the Cenye1 well and the geothermal gradient in NGP, we conducted the methane sorption experiments at subsurface reservoir conditions (5664 C), which is considered to be an inuencing factor. Other factors, such as organic matter type and thermal maturity, have been reported.2,16,31,34,35 Some qualitative characteristics and suggestions were explained and discussed, but no clear relationship was found.
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5. CONCLUSION (1) A thick succession of overmature black shale was deposited in NGP during the Early Cambrian. The organic matter type is sapropelic (type I), which has strong hydrocarbon generation potential throughout the geological history of the succession. TOC values increase up to 10.4% toward the base of the Lower Cambrian shale, and there is a 40 m thick interval (14201460 m) with high organic carbon content (average 5%). A comprehensive assessment indicates that the Lower Cambrian shale holds the exploration potential for shale gas. (2) The basal part of the Lower Cambrian shale shows U, V, and Mo enrichment relative to Black Sea sediments, and good TETOC correlations are observed in the upper shale. Redox conditions in the Lower Cambrian shale are non-suldic anoxic in the upper part and change to suldic euxinic toward the base. The reducing sedimentary environment favors the accumulation of organic matter. (3) The mineral composition of the Lower Cambrian shale exhibits a quartz content of 49% on average, which is an empirical prerequisite for good fracability. The overall minerals are similar to those present in the Ohio and Woodford/Barnett shales (west Texas), which have successfully produced commercial shale gas. Meanwhile, the porosity is characterized by rather low values. Pores less than 10 nm in diameter contribute to most of the BET surface area. (4) Organic matter is an important control on gas sorption capacity. The microporous shale could provide surface and volume at the microscale onto which the gas is adsorbed, shown by the positive correlations between sorbed gas and BET surface area and BJH pore volume. The capability of clay minerals to sorb gas may be blocked by the presence of moisture. The sorbed gas volumes range from 1.09 to 2.55 m3/ton, with an increasing trend toward the base. The Lower Cambrian shale, especially the basal part, is an ideal target for shale gas exploration and development in NGP.

AUTHOR INFORMATION

Corresponding Author Notes

*Telephone: +86-010-82322756. E-mail: bjcuphan@163.com. The authors declare no competing nancial interest.

ACKNOWLEDGMENTS Our study is supported by the National Oil and Gas Strategic Investigation Program (Grant 2009GYXQ-15), the National Natural Science Foundation Research (Grants 41102088 and 41272167), and the Open Research Programs of the Tectonics and Petroleum Resources Key Laboratory, Ministry of Education (Grants TPR-2011-25 and TPR-2012-11). Special thanks go to the China Scholarship Council (CSC). Associate editor Richard G. Mallinson and all anonymous reviewers are gratefully acknowledged.
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dx.doi.org/10.1021/ef400141m | Energy Fuels XXXX, XXX, XXXXXX