Marine and Petroleum Geology 62 (2015) 77e89 Contents lists available at ScienceDirect Marine and Petroleum Geology journal homepage: www.elsevier.com/locate/marpetgeo Research paper Diagenesis and reservoir quality evolution of the Eocene sandstones in the northern Dongying Sag, Bohai Bay Basin, East China Guanghui Yuan a, b, *, Jon Gluyas b, Yingchang Cao a, *, Norman H. Oxtoby c, Zhenzhen Jia a, Yanzhong Wang a, Kelai Xi a, Xiaoyan Li a a b c School of Geoscience, China University of Petroleum, Qingdao, 266580, China Department of Earth Sciences, Durham University, Durham, DH1 3LE, UK 41 Oaken Lane, Claygate, Esher, Surrey, KT10 0RG, UK a r t i c l e i n f o a b s t r a c t Article history: Received 12 October 2014 Accepted 16 January 2015 Available online 27 January 2015 The Eocene sandstones in the northern Dongying Sag, Bohai Bay Basin, China, are reservoirs for large accumulations of hydrocarbons. The sandstones are mainly lithic arkoses and feldspathic litharenites, texturally and compositionally immature. These sandstones have a wide range of porosity (0.4e37%) and permeability (0.004e6969 mD) and show an overall decrease in reservoir quality from 1500 m to 5000 m below sea level. The reduction in reservoir quality is a product of several digenetic processes; these include compaction, precipitation of dolomite and calcite in eodiagenetic stage; compaction, feldspar dissolution, precipitation of quartz cements and clays (kaolin and illite) and precipitation of ferrocalcite and ankerite in mesodiagenetic stage. Mineral distribution pattern and isotopic composition suggest carbonate cements in sandstones originate from sources outside the sandstones. Carbonate cementation, together with compaction reduced the sandstones’ porosity and permeability significantly. In a sandstone bed, marginal sandstones with distance to sandstone/mudstone interface less than one meter always have lower porosity than central sandstones. As burial depth exceeds 4000 m, marginal sandstones have very low porosities (<5%), indicating that thin sandstone beds (<2 m) were totally destroyed by cementation and compaction, and only thick sandstone beds (>2 m) can be potential effective reservoirs. Feldspar dissolution and precipitation of clays and quartz cements have little impact on absolute porosity. Mineral distribution pattern and quantitative data show that leached feldspars are the internal source of authigenic quartz and clays in sandstones, and the volume difference between feldspar secondary porosity and related authigenic cements is generally less than 0.25%. However, although there is little or no net import of matter to the sandstones, the pore architecture changes dramatically. Primary macropores are lost as clays and quartz precipitate while the proportion of microporosity increases, occurring mainly between clay crystals. The overall result is that permeability is significantly degraded. © 2015 Elsevier Ltd. All rights reserved. Keywords: Sandstone diagenesis Reservoir quality Carbonate cements Feldspar dissolution Dongying Sag 0. Introduction Reservoir quality is one of the key controls on prospectivity during petroleum exploration (Taylor et al., 2010). Diagenesis, which consists of physical effects of mechanical compaction and chemical effects of mineral dissolution and precipitation, progressively alters porosity and permeability during burial (Bjørlykke and * Corresponding authors. School of Geoscience, China University of Petroleum, Qingdao, 266580, China. E-mail addresses: [email protected] (G. Yuan), [email protected] (Y. Cao). http://dx.doi.org/10.1016/j.marpetgeo.2015.01.006 0264-8172/© 2015 Elsevier Ltd. All rights reserved. Jahren, 2012; Taylor et al., 2010; Thyne, 2001). Accurate prediction of the porosity in shallow, little cemented sandstones can be made based on the burial history and rock composition (Bjørlykke and Jahren, 2012; Gluyas and Cade, 1997; Taylor et al., 2010; Thyne, 2001). However, prediction of more deeply buried sandstone is much more difficult due to the import and export of materials that related to chemical diagenesis (Bjørlykke and Jahren, 2012; Gluyas, 1997; Gluyas and Witton, 1997; Taylor et al., 2010; Thyne, 2001; Tournier et al., 2010). Thus understanding quantitative diagenetic processes, sources of cements and sinks of dissolved minerals in sandstones are critical for quality prediction of the deeply buried sandstones (Taylor et al., 2010). 78 G. Yuan et al. / Marine and Petroleum Geology 62 (2015) 77e89 The Dongying Sag is a prolific oil-producing province in East China (Guo et al., 2012). Feldspar dissolution pores, carbonate cements, authigenic quartz and clays are common in the Eocene sandstones in the northern Dongying Sag (Zhang et al., 2014). However, diagenetic mass transfer into sediments and the impact on reservoir quality is still the subject for intense debate. Different opinions on diagenesis of the Eocene sandstones have been proposed: (1) CO2, Ca2þ, Mg2þ and SiO2(aq) were moved from mudstones to sandstones (Wang, 2010; Zhang et al., 2014; Zhong et al., 2004); (2) Al3þand SiO2(aq) were removed from sandstones and feldspar dissolution enhanced much porosity during mesodiagenesis stage (Zhu et al., 2007); (3) External carbonates minerals in adjacent mudstones were the only source of the carbonate cements in sandstones (Han et al., 2012). The objectives of this article are to: (1) investigate diagenesis and reconstruct diagenetic history of the Eocene sandstones in the northern Dongying Sag; (2) identify sources of the cements and sinks of the dissolved feldspars in these sandstones; (3) evaluate controls of different diagenesis on reservoir quality. 1. Geologic background The Dongying Sag is a sub-tectonic unit lying in the southeastern part of the Jiyang Depression of the Bohai Bay Basin, and covers an area of 5700 km2 (Fig. 1) (Cao et al., 2014). It can be further subdivided into five secondary tectonic zones from the north to the south, namely the Northern Steep Slope zone, Northern Sag zone, Central Anticline zone, Southern Sag zone and the Southern Gentle Slope zone (Fig. 1BeC) (Guo et al., 2010). The northern Dongying Sag includes the Northern Steep Slope zone and the Northern Sag zone (Lijin subsag and Minfeng subsag). The tectonic evolution of the Dongying Sag is divided into a synrift stage (65.0 Ma 24.6 Ma) and a post-rift stage (24.6 Ma to the present) (Fig. 2) (Guo et al., 2012). Sediments filled in the Dongying Sag comprise the Paleogene Kongdian (Ek), Shahejie (Es) and Dongying (Ed) formations, the Neogene Guantao (Ng) and Minghuazhen (Nm) formations, and the Quaternary Pingyuan (Qp) Formation (Wang, 2010). The boundary between the Ed and Ng formations is the main regional unconformity in the Dongying Sag (Fig. 2) (Guo et al., 2012). The Eocene Shehejie Formation contains the main source rocks and reservoir rocks, and is divided into four members, Es1, Es2, Es3 and Es4 (from top to base) (Fig. 2). The main objects of this study are the Es4 2 to Es3 2 msub-members where organic-rich source rocks develop. The lower Es4 (Es4 2 ) consists of gray and dark-gray mudstones, gypsum and halite, and interbedded subaqueous fan sandstones deposited in semi-deep and deep lacustrine environment; the upper Es4 (Es4 1 ) comprises brown-gray, gray to black mudstones, shales, dolomites and subaqueous fan sandstone interbeds that were deposited in semi-deep and deep lacustrine environment. The lower Es3 (Es3 3 ) was deposited in semi-deep and deep lacustrine environment and is dominated by lacustrine oil shales, dark-gray mudstones, calcareous mudstones and subaqueous (sublacustrine) fan sandstones; the middle Es3 (Es3 2 ) includes gray to dark-gray mudstones, calcareous mudstones, and Figure 1. (A) Location map of the study area showing the sub-tectonic units of the Bohai Bay Basin, depressions in the Bohai Bay Basin of China are Jizhong Depression (Ⅰ), Huanghua Depression (II), Jiyang Depression (Ⅲ), Bozhong Depression (IV) and Liaohe Depression (V) (Guo et al., 2012). (B) Structural map of the Dongying Sag. The area in the dashed green line is the study area of this article. (C) NeS cross-section (P0 -P) of the Dongying Sag showing the various tectonic-structural zones and key stratigraphic intervals. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.) G. Yuan et al. / Marine and Petroleum Geology 62 (2015) 77e89 79 Figure 2. Generalized CenozoiceQuaternary stratigraphy of the Dongying Sag, showing tectonic and sedimentary evolution stages and the major petroleum system elements (modified from Guo et al., 2012). subaqueous (sublacustrine) fan sandstones deposited in semi-deep and deep lacustrine environment (Guo et al., 2012). Burial history and thermal history of the northern Dongying Sag have been analyzed in detail using data from exploration and production wells and the histories synthesized with the BasinMod software by previous studies (Guo et al., 2012; Song et al., 2009). The maximum burial depth of the Shahejie Formation in the northern Dongying Sag occurs today at approximately 5000 m (Guo et al., 2012; Song et al., 2009). The present-day geothermal gradient is around 34 C/km with an average surface temperature of 14 C, and the present-day maximum temperature is about 180 C at 5000 m (Wang, 2010). According to previous studies, the shales and mudstones in Es4 2 eEs3 2 have total organic carbon (TOC) content of 0.5%e18.6% with an average of about 5%, and organic matter is dominated by type-I and II kerogens (Guo et al., 2010; Zhu et al., 2004). The average vitrinite reflectance (Ro%) varies from 0.35% to 1.5% from 2000 m to 5000 m, indicating source rocks are low mature to mature (Guo et al., 2012). The northern Dongying Sag becomes increasingly overpressured with the increasing depth, and middle-strong fluid overpressure develops commonly in Es4eEs3 2 reservoirs from 2200 m to 5000 m (Cao et al., 2014; Guo et al., 2010; Zhang et al., 2009). 2. Database and methods Rock composition data of 831 thin section samples, 309 bulk rock XRD data and 6335 reservoir porosity and permeability data were collected from Geological Scientific Research Institute of China Sinopec Shengli Oilfield Company. With constraints of the collected data, samples were selected from the Es4eEs3 drill cores of 25 wells in the northern Dongying Sag for this study. 250 thin sections and 250 red epoxy resin- impregnated thin sections were prepared for analysis of rock mineralogy, diagenesis and visual porosity. Point counts were performed on thin sections for the content of detrital grains and carbonate cements with at least 300 points, which can provide a standard deviation of 5.5% or less (Stroker et al., 2013). For the content of feldspar dissolution pores, quartz cements and authigenic clays, 20 or 40 micrographs of 37 red epoxy resinimpregnated thin sections were taken firstly using the Zeiss microscope. Objectives of 100 for these thin sections were used, and each micrograph has an area of 6.45 mm2. Then the target minerals and pores in each micrograph were identified under the microscope and were drew on computer screen using CorelDRAW, and the total area of each target mineral and pores in every micrograph was obtained using Image-Pro Plus software. Finally, the contents of the target minerals and pores in each thin section were obtained by taking the average of all values in its micrographs. For mediumcoarse grained sandstones, 20 micrographs were used, while 40 micrographs were used for pebbly sandstones in order to ensure that the coarse grain size did not produce any sampling bias. As the authigenic illite is dispersive and it is difficult to do the quantitative work, only two thin sections with mainly illite were analyzed. 25 SEM samples were identified using a Quanta200 SEM combined with EDAX Energy dispersive spectroscopy. Six core samples were prepared as thick doubly polished sections of approximately 100 mm thickness for fluid inclusion petrographic analysis and microthermometric measurement. Microthermometry of aqueous inclusions was conducted using a calibrated Linkam. TH-600 stage. The homogenization temperature (Th) was obtained by cycling. Th measurements were determined using a heating rate of 10 C/min when the temperature was lower than 70 C and a rate of 5 C/min when the temperature exceeded 70 C. The measured temperature precision for Th is ±1 C. 80 G. Yuan et al. / Marine and Petroleum Geology 62 (2015) 77e89 Based on petrological studies, 29 organic matter-free sandstone samples were selected for analysis of the carbon and oxygen stable isotope composition in the carbonate cements. Tightly cemented sandstones were disaggregated directly with a hammer and then crushed in a mortar; porous sandstones were disaggregated using the freezing-heating technique (Wang et al., 2005) to avoid breaking detrital carbonate grains. Then the disaggregated samples were sieved to pass through a 200 mesh sieve (75um) to get the powder. The sample preparation method reduces the possibility of sampling unwanted detrital carbonates. Isotopic data were obtained using Thermo-Finnigan MAT 253 IRMS online with Gas BenchⅡ in Durham University. d13C and d18O values were determined on CO2 liberating from carbonate cements samples and the LAEAC01 standard that were dissolved by 100% H3PO4 at 50 C. Isotopic composition of CO2 is reported in units of ‰ relative to PEE Dee belemnite (V-PDB). Replicate analysis is reproducible to ±0.1‰ for both d13C and d18O. 3.2. Sandstone petrology: detrital mineralogy The studied Eocene sandstones are fine to coarse-grained. The sandstones are generally texture immature. Sorting ranges from poor to moderate sorted and roundness of the detrital grains varies from subangular to sub-rounded. The sandstones are mostly lithic arkoses and feldspathic litharenites (Fig. 4), compositionally immature with an average framework composition of Q32F37L31. The detrital quartz grains are primarily monocrystalline, ranging from 5% to 63% and detrital feldspars ranges from 4% to 74%. Bulk rock XRD analysis data show that, the K-feldspar content is 2%e27% with an average of 12% and the plagioclase content is 2%e40% with an average of 25% (Fig. 4). In general, the K-feldspar content decreases slightly as burial depth increases but the plagioclase content shows no significant trend. The rock fragment content ranges mainly from 3% to 88% (Fig. 4). 3.3. Sandstone petrology: diagenetic mineralogy 3. Results 3.1. Porosity and permeability versus depth The Eocene sandstones have a wide range of porosity from 0.4 % to 37% and the permeability ranges from 0.004mD to 6969mD (measured over the depth interval 1500 me5000 m). In general, the porosity and permeability of the Eocene sandstones decrease as the burial depth increases from 1500 m to 5000 m, though anomalously high porosity and permeability exist in some depth intervals (2800e3300 m, 3300e3700 m and 3900e4400 m respectively) (Fig. 3A, B). Similarly, both the average and peak total visual porosity in thin sections also decreases with the increasing depth (Fig. 3C). Authigenic minerals in sandstones consist mainly of carbonate cements, quartz, kaolin, and illite. The authigenic quartz and clays are usually associated with altered feldspars. Four types of carbonate cements, dolomite (Fig. 5A), calcite (Fig. 5B), ferrocalcite (Fig. 5C) and ankerite (Fig. 5D, E) were identified in sandstones. Dolomite and calcite cements occur as microsparry or sparry interlocking mosaic of crystals with the crystal size varies from 4 mm to 200 mm, these cements fill primary pores and replace some detrital grains. In dolomite or calcite cemented tight sandstones, the cement occupies almost all primary pores and can account for 25%e30% of the sandstone volume. In general, dolomite or calcite cemented sandstones are usually supported by detrital grains with just point contacts or have a floating Figure 3. Core porosity (A) and core permeability (B), total porosity (C) and feldspar secondary porosity (D) in thin sections, the content of kaolin (E) and illite (F) in the Eocene sandstones in the northern Dongying Sag. G. Yuan et al. / Marine and Petroleum Geology 62 (2015) 77e89 81 Figure 4. Rock composition of the Eocene sandstones in the northern Dongying Sag. (Ternary plot refers to sandstone classification standard of Folk et al. (1970)). texture, indicating little compaction when cementation occurred. Ferrocalcite and ankerite are common cements in sandstones with a general content of 0.5e10%. They occur as scattered euhedral rhombs (10e100 mm), sparry crystals (50e200 mm) and clusters with no signs of dissolution. In thin sections, ferrocalcite and ankerite replaces stage-I quartz overgrowths, dolomite (Fig. 5C, D) and calcite, and some ferrocalcites and ankerites were precipitated in feldspar dissolution pores (Fig. 5E), leading to the conclusion that ferrocalcite and ankerite formed after stage-I quartz cementation and feldspar dissolution. Feldspar grains in porous sandstones usually contain significant secondary porosity (Fig. 5E, G, I) that must have developed during burial stage. The feldspar secondary porosity in thin sections can reach up to 4% (Fig. 3D). Significant feldspar secondary pores are Figure 5. Thin section images of sandstones (pore space is shown in red): A, Dolomite filled all intergranular primary pores, feldspar secondary pore with no dolomite; B, Calcite filled all primary pores; C, Dolomite was replaced by ferrocalcite; D, Dolomite was replaced by ankerite; E, Feldspar secondary pores was filled by some ankerite; F, Relationship between ankerite and two stages of quartz cements; G- G-Feldspar secondary pores, kaolin and quartz overgrowths; H, Micropores in authigenic kaolin; I Extensive feldspar dissolution with no dissolution of detrital carbonate grains. Do-Dolomite; Cc-Calcite; Cg-Detrital carbonate grain; Fc-ferrocalcite; An-Ankerite; FD-Feldspar dissolution pore; KKaolin; Qa-Quartz overgrowths. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.) 82 G. Yuan et al. / Marine and Petroleum Geology 62 (2015) 77e89 always accompanied with quartz cements and clays (Figs. 5G and 6B). Authigenic quartz is evident in thin sections and SEM samples (Figs.5F and 6A,B). Quartz cements represent no more than 1% of the whole rock (Fig. 7C) and occur in forms of mainly quartz overgrowths (Figs. 5F and 6A) and some small quartz crystals (Fig. 6B). It is not difficult to discriminate the quartz overgrowths from the detrital grains with the existence of some dust clay rim on the grains in thin sections (Fig. 5F,G). Two stages of quartz overgrowths (Fig. 5F) can be identified, and thickness of the overgrowths ranges mainly from 2um to 50um. The texture relationship between ankerite and two stages of quartz overgrowths indicates that the stage-II quartz cementation occurred after ankerite cementation (Fig. 5F). Kaolin and illite are the two most important types of authigenic clays in the Eocene sandstones. Kaolin mainly occurs as euhedral booklets and vermicular aggregates filling primary pores within the sandstones (Fig. 6C, D). Kaolin aggregates are rich in intercrystalline microporosity (Figs. 5H and 6C, D). SEM observation revealed that kaolin aggregates are composted of closely associated, thin kaolinite platelets (Fig. 6C), and thicker, euhedral blocky crystals of dickite (Fig. 6D). However, the transformation of kaolinite to dickite in these sandstones still needs further research. Illite occurs as fibrous crystal mainly in primary pores (Fig. 6E, F) and sometimes in feldspar secondary pores. XRD data of clay minerals in the <2um fractions of sandstones show that kaolin dominates in reservoirs above 3100 m (T < 125 C) (Fig. 3E), and illite dominates in sandstones with depth deeper than 3100 m (T > 125 C) (Fig. 3F), which can also be verified by the fabric in thin sections and SEM (Fig. 6CeF). In the section above we have considered variations in authigenic mineral content largely in terms of regional trends associated with increased burial depth. There are however variations on smaller scales which correlate with lithological variations in individual wells. For example, from marginal part to central part of sandstone beds, the content of the carbonates cements in sandstones decreases sharply (Fig. 7A). In contrast to the carbonate cements, the marginal sandstones usually contain few feldspar secondary pores (0e1%), quartz cements (0e0.3%) and authigenic clays (0e1.5%), and the central sandstones in thick beds can have more feldspar secondary pores (1e2.5%), quartz cements (0.3e0.5%) and clays (1e3%) (Fig. 7BeD). 3.4. Fluid inclusions Aqueous inclusions can provide valuable information for the precipitation temperature of authigenic minerals (Robinson and Gluyas, 1992). The aqueous inclusions in samples occur primarily along the healed micro-fractures in quartz grains (Fig. 8A) and some aqueous fluid inclusions occur in quartz overgrowths Figure 6. SEM images of sandstones. A, Quartz overgrowths and illite; B, Feldspar secondary pores and quartz crystals; C-Authigenic kaolinite in primary pores; D, Kaolinite and dickite in sandstones; E, Transition of kaolinite to illite; F, Illite is precipitated on ankerite. Q-Quartz grain, FG-Feldspar grain, FD-Feldspar dissolution pores, An-Ankerite, K-Kaolinite, Dick-Dickite, I-Illite; Qa-Quartz overgrowths, Qc-Quartz crystals. G. Yuan et al. / Marine and Petroleum Geology 62 (2015) 77e89 83 Figure 7. The relationship between the content of carbonate cements, feldspar secondary pores, quartz cements, clays in clean medium sandstones-pebbly sandstones and the distance to mudstone/sandstone interface. (Fig. 8B). The aqueous inclusions have a diameter about 2e10 mm, and most of them are two phase inclusions and have gas bubbles at room temperature. The measured homogenization temperatures (Th) of the aqueous fluid inclusions from this study and previous studies (Han et al., 2012; Guo et al., 2012) are shown in Table 1. Figure 9 presents the distribution of the homogenization temperature of the aqueous inclusions in healed microfractures in quartz grains, quartz overgrowths and carbonate cements. The aqueous inclusions in healed microfractures yield Th rangs mainly from 95 C to 125 C and 150 Ce180 C. Th of the aqueous inclusions in quartz overgrowths ranging mainly from 100 C to 120 C and from 160 C to 180 C, suggests two stages of quartz cementation in mesodiagentic stage, which is in consistent with thin section observation (Fig. 5F). Th of the aqueous inclusions in carbonate cements by previous studies ranges from 115 C to 140 C (Han et al., 2012; Guo et al., Figure 8. Photomicrographs of aqueous inclusions under transmitted light observed at room temperature in sandstones from the northern Dongying Sag. (A) Aqueous inclusions along healed microfractures in quartz grains. (B) Aqueous inclusions in quartz overgrowths. AI-Aqueous fluid inclusions, Q-Quartz grains, Qa-Quartz overgrowths. Table 1 Microthermometric data of the aqueous fluid inclusions in the Eocene sandstones in the northern Dongying Sag. Th: homogenization temperature; e: no available data. Well Strata Depth, m Aqueous inclusions in healed microfractures in quartz grains Aqueous inclusions in quartz overgrowths Data source Size, um Th, C (Number) Size, um Th, C (Number) Tuo762 Tuo762 FS1 F8 F8 Tuo719 Es4 1 Es4 1 Es4 2 Es4 2 Es4 2 Es4 1 3438.0 3451.0 3684.9 4201 4055.35 3562.1 4e10 4e8 4e12 3e9 2e8 4e13 98e125 (12), 166e179 (7) 110e130 (8), 165e170 (1) 90e125 (10),180e185 (2) 110e125 (6), 155e170 (25) 130e180 (13) 100e110 (10) e 7 4e10 6 3e8 5e8 e 113e117 110e125 164 (1) 140e170 100e125 Yan22-22 FS3 Es4 1 Es4 2 3403 4867 e e e e e e 110e115 (2) 155 (2) Wang, 2010. Tuo731 Tuo711 FS10 FS1 Es3 2 Es3 3 Es4 2 Es4 2 2944.0 3195.6 4263.5 4323 e e e e 103e118 114e130 141e169 156e179 e e e e e e e 160e165 (1) Guo et al., 2012. (14) (16) (29) (14) This study (2),165e170 (1) (6) (5) (3), 175e180 (1) 84 G. Yuan et al. / Marine and Petroleum Geology 62 (2015) 77e89 Figure 9. Histograms of homogenization temperature (Th) for aqueous inclusions in healed microfractures of quartz grains, quartz overgrowths and carbonate cements from the Eocene sandstones in the northern Dongying Sag. AI: Aqueous inclusions. 2012), also reveals that the ferrocaltcite and ankerite formed after the stage-I quartz cements and before stage-II quartz cements, concluding similarly with the petrography texture relationship (Fig. 5F). 3.5. Isotopic composition of carbonate cements Isotopic composition of carbonate cements was measured in 29 sandstone samples, and the types and contents of carbonate cements in samples were counted with thin sections (Table 2). Most dolomite and calcite have a relative wide range of d18O values from 7‰ to 13‰ and d13C from þ2‰ to þ7‰. Ferrocalcite and ankerite have a range of d18O values from 15‰ to 19‰ and d13C from 7‰ to þ2‰. Samples contain a mixture of these cements show intermediate values. 4. Discussion 4.1. Diagenetic sequences The relative timing of the major diagenetic sequence of the Eocene sandstones in the northern Dongying Sag, which has been determined from thin sections and SEM examination, is based on texture relationship (Figs. 5, 6, 10). In summary, the dominant eogenetic features in the Eocene sandstones are the compaction and the precipitation of dolomite and calcite. Subsequent mesogenetic processes experienced by these sandstones include (1) compaction, (2) feldspar dissolution/precipitation of quartz cements and kaolin, (3) precipitation of ferrocalcite and ankerite, (4) illitization of kaolin/feldspar dissolution/precipitation of quartz cements and illite. With constraints of the isotopic composition, the homogenization temperature (Th) of the aqueous fluid inclusions in cements, and burial-thermal history of well Fengshen-1 in the northern Dongying Sag (Song et al., 2009), the diagenetic history of the Eocene sandstones can be summarized in Figure 10. 4.2. Sources of carbonate cements in sandstones Detrital carbonate grains in the studied sandstones show no signs of dissolution (Fig. 5I) (Cao et al., 2014), and the distribution pattern of carbonate cements (Fig. 7A) suggests external sources for these cements (Thyne, 2001). The average d18OPDB value (0.85‰) of lacustrine sedimentary dolomite in the Es4 Formation in the Dongying Sag (Liu, 1998) suggests d18OSMOW value of lake water to be 4.8‰ with a water temperature of 10 C (Matthews and Katz, 1977). With the d18OSMOW value of 4.8‰ of pore water at eodiagenetic stage, and different oxygen isotope fractionation factor for dolomite-water (Matthews and Katz, 1977) and calcite-water (Friedman and O'Neil, 1977), calculated precipitation temperatures for the dolomite and calcite cements in sandstones range mainly from 30 C to 70 C (Table 2). These dolomite and calcite have relative positive d13C values between þ2‰ and þ7‰ (Table 2), as interbedded mudstones contain much organic matter (TOC up to 18.6%) (Guo et al., 2010), fermentative degradation of the organic matter must be an important carbon source of these cements (Curtis, 1978). Bulk rock XRD data show that about half of the mudstones in the Es3eEs4 formations contain more than 30% carbonate minerals (Qian et al., 2009). When some of these carbonates in adjacent mudstones were dissolved by the CO2 generated by bacterial fermentation (Dutton, 2008), the dissolved masses could be transported into sandstones and provide carbon for the carbonate G. Yuan et al. / Marine and Petroleum Geology 62 (2015) 77e89 85 Table 2 Mineralogical and isotopic composition of carbonate cements, and calculated formation temperature of cements in the Eocene sandstones in the northern Dongying Sag. Cacalcite, Do-dolomite, Fc-ferrocalcite, An-ankerite. Well Yong925 Yanxie21 Yan22_22 Tuo73 Yong924 Tuo717 Tuo76 Yan222 Yong928 Yan23 Tuo762 Tuo121 Tuo125 Yong92 Fengshen3 Yong920 Feng8 Yan22_22 Yan22_22 Tuo718 Yong925 Tuo767 Tuo720 Yong924 Tuo168 Tuo75 Tuo764 Tuo714 Fengshen4 Depth (m) 2545.30 3045.40 3490.60 3371.45 2866.80 2995.04 2938.12 4074.48 3756.30 3672.85 3439.13 2111.30 2462.64 2972.72 4867.00 3370.90 4197.91 3350.25 3375.30 3270.20 2496.05 3824.80 3535.00 2892.01 3110.10 2422.23 4166.10 2843.06 4476.15 Strata Es3 3 Es4 1 Es4 1 Es4 1 Es4 1 Es3 2 Es3 2 Es4 1 Es4 1 Es4 1 Es4 1 Es3 3 Es4 1 Es4 1 Es4 2 Es4 1 Es4 2 Es4 1 Es4 1 Es3 3 Es3 3 Es4 1 Es3 3 Es4 1 Es4 1 Es4 1 Es4 1 Es3 2 Es4 2 Carbonate minerals 100%An 30%Ca þ 30%Fc þ 40%An 100%Ca 80%Ca þ 20%Do 40%Ca þ 40%Do þ 20%An 90%Ca þ 10%Do 100%Do 80% An þ 20Fc 70%An þ 30%Do 100%Do 100%Do 100%Ca 100%Do 80%Ca þ 20%An 100%An 90%An þ 10%Ca 80%Do þ 20%An 20%An þ 60%Fc þ 20%Ca 40%An þ 30%Fc þ 30%Do 100%Do 80%An þ 20%Do 95%Do þ 5%Ca 90%Do þ 10%An 20%Fc þ 80%An 70%Ca þ 30%Do 100%Do 80%Ca þ 20Do 100%Do 100%Do Carbonate cement content, % d18O-PDB (‰) d13C-PDB ( ‰) d18OSMOW ¼ 4.8‰ Temp ( C) Temp.( C) d18OSMOW ¼ 3‰ Temp. ( C) d18OSMOW ¼ 0‰ 7 6 30 10 8 5 25 6 7 26 25 20 15 10 6 10 15 15 14 20 14 15 15 8 15 25 20 5 15 16.8 14.6 12.8 10.0 12.9 9.8 8.2 16.5 13.5 10.7 9.6 11.1 9.1 13.3 18.3 18.4 13.5 16.7 14.9 9.8 15.9 10.8 7.9 18.3 9.8 5.6 11.3 12.0 10.3 0.4 1.4 1.3 3.7 2.1 2.7 7.1 2.8 0.7 5.7 3.7 3.3 2.1 2.3 6.5 2.1 4.3 3.8 2.8 3.6 1.4 5.3 7.1 1.9 2.0 6.3 5.4 5.7 7.2 103 e 57 40 e 39 43 100 e 58. 51 46 49 61 116 118 75 e e 52 95 59 42 117 e 30 48 66 56 120 e 70 51 e 49 54 117 e 69 62 58 59 74 136 137 89 e e 63 111 70 52 136 e 39 60 79 67 154 e 94 71 e 69 72 150 e 91 82 80 79 99 174 175 114 e e 84 142 92 70 175 e 55 81 102 87 Note: Only isotopic data of samples with the content of one specific type of carbonate up to 80% were used to calculate the temperature. The equations used for fractionation between carbonates and water are: 1000lnacalcite/ferrocalcite-water ¼ 2.78*106/T2 e 2.89 (Friedman and O'Neil, 1977) and 1000lnadolomite/ankerite-water ¼ 3.06*106/T2 e 3.24 (Matthews and Katz, 1977). cements in sandstones, and the d13C values (þ3‰ to þ10‰) (Liu, 1998) of these carbonates in mudstones also suggest that they can be another carbon source. Previous studies show that pore-water becomes isotopically heavier with increasing burial as isotopic composition of the porewater was modified by reactions of feldspars alternation (Fayek et al., 2001; Savin, 1980). Th of the aqueous inclusions in ferrocalcite and ankerite shows that these latter carbonate cements were precipitated from 115 to 140 C (Fig. 9). With the oxygen isotope fractionation factor for dolomite-water of Matthews and Katz (1977) and calcite-water of Friedman and O'Neil (1977), precipitation temperatures of ankerite and ferrocalcite were calculated with assuming d18OSMOW values of 4.8‰, 3‰ and 0‰. The results show that, when d18OSMOW value of the pore water is 3‰, the precipitation temperature ranges mainly from 115 C to 137 C (Table 2), which is consistent with the homogenization temperature of aqueous fluid inclusions in carbonate cements. As feldspars in the studied sandstones were dissolved extensively, evolution of the d18OSMOW value of the pore water from 4.8‰ to 3‰ is acceptable. Ankerite and ferrocalcite have relative negative d13C values from 7‰ to þ2‰ (Table 2), which indicate that decarboxylation of the organic matter in mudstones must be one important carbon source (Curtis, 1978). Experienced relative high temperature, large amounts of organic acids and CO2 from thermal evolution of organic matter can dissolved some carbonates in source rocks (Dutton, 2008), which may be another source when the carbon was imported into the sandstones. Thus, the d13C values (7‰ e þ2‰) probably represent a mixture of carbon from decarboxylation of organic matter and dissolution of carbonates in source rocks. After deposition, porosities of the Eocene mudstones in the northern Dongying Sag generally evolved from nearly 60% to less than 10%e15% at present (Zhang et al., 2009). During such a period, large amounts of advective compaction fluids were expelled from mudstones to sandstones (Bjørlykke, 1993; Bjørlykke and Jahren, 2012). In Es4 2 -Es3 2 sub-members, the concentration of Ca2þ and Mg2þ in pore water is up to 26,000 ppm (Cao et al., 2014), the high concentration of Ca2þ and Mg2þ in pore water promised the massive transfer of these masses from mudstones to adjacent sandstones. Dissolution of some anorthite in sandstones may provide some Ca2þ, but the amount is not important as only less than 4% feldspars were dissolved in the sandstones (Milliken et al., 1994). 4.3. Sources of authigenic clays and quartz in sandstones Precipitation of authigenic quartz, kaolin and illite occurred in the mesodiagenetic stage (Fig. 10). Unlike the Ca2þ and Mg2þ, the concentration of SiO2(aq) (<100 ppm) and Al3þ (<10 ppm) is extremely low in deep buried sediments (Bjørlykke and Jahren, 2012; Ronald and Edward, 1990), with constraints of water volume and considerable heterogeneity in porosity and permeability, none of the advective flow, thermal convection or diffusion can take responsible for long distance and massive transfer of external SiO2(aq) and Al3þ into sandstones (Bjørlykke et al., 1988; Bjørlykke and Jahren, 2012), particularly in geochemical systems where overpressure develops. Also, the distribution patterns of such cements (Fig. 7C, D) in sandstones do not support that they originate from external sources out of sandstones. With no external source, the most possible source for authigenic clays should be the dissolution of feldspars within the sandstones 86 G. Yuan et al. / Marine and Petroleum Geology 62 (2015) 77e89 Figure 10. Burial, thermal and diagenetic history of the Eocene sandstones in the northern Dongying Sag (Burial and thermal history of well Fengshen-1 were modified from Song et al., 2009). (Giles and De Boer, 1990; Higgs et al., 2007). On the thin section scale, we can identified that a positive relationship exists between feldspar secondary pores and byproducts, that is little feldspar secondary pores are commonly accompanied with little byproducts nearby and massive feldspar secondary pores with massive byproducts in nearby primary pores (Figs. 5G and 6B). The amount of clay in thin sections increases linearly with the increase of feldspar secondary porosity (Fig. 11A). The perfect positive linear relationship between the amount of feldspar secondary pores and clays suggest that the dissolution of feldspars is the source of the authigenic clays in sandstones. In sandstones with quartz grains as dominant clastic component and with much quartz cements (1e30%), quartz dissolution at grain contacts, quartz dissolution along stylolites, feldspar dissolution were suggested to be internal silica sources (Tournier et al., 2010; Walderhaug, 2000). As the studied sandstones experienced minimal pressure dissolution, the most likely source for quartz cements should be the internal dissolution of feldspars. Indeed, there is a positive correlation between the quantity of quartz cement and the number of partially dissolved feldspars (Fig. 11B). At the same time, the quartz cement content increases slightly as burial depth increases (Fig. 13), which suggests high temperature and deep burial probably promote its development (Walderhaug, 2000). All in all, the petrography texture relationship, the distribution pattern and the quantitative data all suggest that feldspar dissolution is the internal source for authigenic clays and quartz in sandstones. And the distribution pattern of authigenic minerals in the northern Dongying Sag suggests that during the diagenetic processes, when the temperature was below 125 C (depth < 3100 m), feldspar dissolution was accompanied by precipitation of kaolin and quartz. When the temperature exceeded 125 C, illite became more stable than kaolin, products of feldspar dissolution was precipitated as illite and quartz, and kaolin formed at lower temperature was also transformed to illite (Chuhan et al., 2001; Franks and Zwingmann, 2010; Lander and Bonnell, 2010). 4.4. Diagenetic control on reservoir quality The porosity versus permeability diagrams of different lithology show that with similar burial depth and cement contents, medium G. Yuan et al. / Marine and Petroleum Geology 62 (2015) 77e89 Figure 11. Relationship between the content of feldspar secondary pores, authigenic clays and quartz cements in the Eocene sandstones of the northern Dongying Sag. sandstones, coarse sandstones and pebbly sandstones have the best properties and permeability (Fig. 12C), followed by siltstones and fine sandstones (Fig. 12B), and shaley sandstones and fine-grained conglomerates own the worst properties and permeability (Fig. 12A, D). When it comes to single lithology, the reservoir properties (porosity and permeability) of each lithology still show 87 considerable heterogeneity (Fig. 12). This heterogeneity must be induced by the sandstone's complex diagenetic history, which resulted in various types of diagenetic alterations that controlled the sandstone's porosity and permeability (Salem et al., 2005). Figure 12 show that for each lithology, the porosity and permeability of sandstones with similar cement content generally decrease as the burial depth increases, indicating compaction can damage the reservoir quality. Also, the porosity and permeability of sandstones with similar depth generally decrease as the content of carbonate cements increases, indicating cementation processes with external mass sources can reduce porosity and permeability significantly through occupation of pore space in sandstones (Fig. 12). The difference between feldspar secondary porosity and the sum of authigenic quartz and clays in the sandstones is usually less than 0.25% (Fig. 13), which means with the sandstones themselves as sources and sinks of chemical diagenetic processes, these processes have little impact on absolute reservoir porosity. However, although there is little or no net import of matter to the sandstones, the pore architecture changes dramatically. Primary macropores are lost as clays and quartz precipitate while the proportion of microporosity increases, occurring between clay crystals (Nadeau and Hurst, 1991) and within the partially dissolved remains of feldspars. The overall result is that permeability is significantly degraded (Yuan et al., 2013). Compaction and carbonate cementation mainly control the porosity evolution of the sandstones in the northern Dongying Sag. The introduction of masses from external sources (adjacent mudstones) to sandstones resulted in extensive carbonate cementation in marginal sandstones, and this thickness of these marginal cemented sandstones (with cements more that 10e15%) can reach up to one meter (Figs. 7 and 14), leading thin sandstone beds to be tightly cemented totally. Figure 12. Core porosity verse permeability diagrams of the Eocene sandstones with different carbonate cements, different lithology and at different depth in the northern Dongying Sag. 88 G. Yuan et al. / Marine and Petroleum Geology 62 (2015) 77e89 Figure 13. The vertical distribution of the content of feldspar secondary pores, clays and quartz and the difference between secondary porosity and the byproducts in the Eocene sandstones in the northern Dongying Sag. 62.5% was used in the calculation as kaolin generally own 25%e50% microporosity (Nadeau and Hurst, 1991). From 2000 m to 5000 m, for central sandstones in thick sandstone beds (>2 m), the porosity reduced by cementation is usually less than 10%, and compaction usually reduce more porosity than carbonate cementation. Porosities of such central sandstones can still be maintained to be more than 10% when the burial depth is deeper than 4000 m (Fig. 14), which are higher than the porosity cutoff (5%e6%) of effective hydrocarbon reservoirs in the study area (Wang, 2010). While for marginal sandstones, their porosities are usually much lower than that of central sandstones in thick beds. With extensive carbonate cementation (>15% carbonate cements) and increasing compaction, when burial depth exceeds 4000 m, porosities of most marginal sandstones with distance to sandstone/ mudstone interface less than one meter are lower than 5% (Fig. 14), which indicates that thin sandstone beds (<2 m) have been totally destroyed by extensive cementation and compaction, and only the thick beds can be potential effective hydrocarbon reservoirs. 5. Conclusion Figure 14. Ternary plot of core porosity, volume of carbonate cements and the porosity reduced by mechanical compaction in medium sandstones e pebbly sandstones with initial porosity of 40%. ‘D’ represents the distance from sandstone samples to the sandstone/mudstone interface. Note that destruction of original porosity by mechanical compaction and cementation are different for sandstones with different position in the sandstone beds. (1) The porosity and permeability of the Eocene sandstones in the northern Dongying Sag are of considerable heterogeneity, with a wide range of porosity from 0.4 % to 37% and permeability from 0.004mD to 6969mD. (2) The Eocene sandstones in the northern Dongying Sag experienced compaction and precipitation of calcite and dolomite in eodiagecetic stage, and in mesodiagenetic stage, main chemical processes are feldspar dissolution, precipitation of quartz, kaolin, illite, ferrocalcite and ankerite, and illitization of kaolin. (3) Different chemical diagenetic processes have different impact on reservoir quality. With external mass sources, carbonate cementation reduced considerable porosity and permeability of the sandstones, particularly for sandstones at the margin of sandstone beds. While as dissolution of feldspars provided just the internal source for precipitation of authigenic quartz and clays in sandstones, these chemical diagenetic processes have little impact on porosity. But because grains are replaced by platy or fibrous clays, permeability can be significantly reduced. (4) Compaction and carbonate cementation mainly control the quality evolution of the sandstones together, and their impact is different for sandstone with different position in a sandstone bed. Porosities of marginal sandstones are always G. Yuan et al. / Marine and Petroleum Geology 62 (2015) 77e89 much lower than that of central sandstones in sandstone beds. In deeply buried layers (>4000 m), thin sandstone beds are of poor quality due to extensive cementation and compaction, and only the thick sandstone beds (>2 m) can be potential effective hydrocarbon reservoirs. Acknowledgments This study was financially supported by the Natural Science Foundation of China Project (No. U1262203), the National Science and Technology Special Grant (No. 2011ZX05006-003), the National Basic Research Program of China (973 Program) (No.E1401004B), and Foundation for the Author of National Excellent Doctoral Dissertation of PR China. Thanks are also given to the following individuals and institutions: Wen L. of China University of Petroleum; Dr. Macpherson C.G. and Peterkin J. of Durham University; Shengli Oilfield Company of Sinopec provided all the related core samples and some geological data of Dongying Sag. References Bjørlykke, K., 1993. Fluid flow in sedimentary basins. Sediment. Geol. 86, 137e158. Bjørlykke, K., Mo, A., Palm, E., 1988. Modelling of thermal convection in sedimentary basins and its relevance to diagenetic reactions. Mar. Pet. Geol. 5, 338e351. Bjørlykke, K., Jahren, J., 2012. 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