Table
1.
Lithostratigraphic subdivision of Huai Hin Lat Formation (Chonglakmani, 2011; Chonglakmani and Sattayarak, 1978)
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| Citation: | Boonnarong Arsairai, Akkhapun Wannakomol, Qinglai Feng, Chongpan Chonglakmani. Paleoproductivity and paleoredox condition of the Huai Hin Lat Formation in northeastern Thailand. Journal of Earth Science, 2016, 27(3): 350-364. doi: 10.1007/s12583-016-0666-8
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The Huai Hin Lat Formation consists of fluvio-lacustrine sediments of Late Triassic (Norian) age. It is exposed along the margin of the Khorat Plateau and is present in the sub-surface basins beneath the Khorat Group of Rhaetian to Late Cretaceous age. The Kuchinarai Group is the equivalence of the Huai Hin Lat Formation, which occurred in the sub-surface (Booth, 1998). Chonglakmani and Sattayarak (1978) suggested that the Huai Hin Lat Formation was deposited in half-grabens and consisted predominantly of clastic sediments which belong to the alluvial fan, the restricted lacustrine, and the fluviatile facies.
The petroleum exploration has been conducted in the Khorat Plateau since 1962. Two gas fields have been discovered and commercially exploited since 1988. The lacustrine facies of the Huai Hin Lat Formation are believed to be one of the main source rocks of the gas (Booth, 1998). The main research objective is to define the depositional environment and source rock potential of the Huai Hin Lat shale by petrographic and geochemical analyses. The results of the study will provide essential information for petroleum potential evaluation of northeastern Thailand.
Lakes are subjected to interaction of external and internal factors, such as, climate, tectonic and geomorphologic activities, and changes in regional vegetation and aquatic biota (Cohen, 2003). Interaction among these factors is complex as each lake is unique and controlled to some extent by its geographic and geologic setting. The rapid response of lakes to external and internal factors is related to high sedimentation rate. It can lead to the preservation of high-resolution geochemical signals of environmental changes in the deposits that accumulate on the lake bottom (Martín-Puertas et al., 2011; Battarbee, 2000). In addition, lake basins have the potential for providing high resolution paleoclimatic records of various stratigraphic units (Johnson et al., 2007). Significant changes in elemental composition of the sediment geochemistry are likely due to changes in the water mass and the source terrane. Moreover, the palynofacies preserved in the sediments comprises the organic detritus and palynomorphs from intra-basin and terrestrial sources. The petrographical study and the geochemical analysis of shale samples from the studied section were performed to explain the paleoproductivity and the past redox condition (Martín-Puertas et al., 2011; Eusterhues et al., 2005).
Thailand is the result of the collision and fusion of two principal continental terranes, namely the Sibumasu (also called Shan-Thai) (Chonglakmani, 2011) in the west and the Indochina in the east. Both blocks had their origin on the margin of the Gonwana in the Paleozoic. They broke away from their parent continent at different times and had different histories as they drifted north before arriving in tropical latitudes in the Permain–Triassic. The location of the suture and the timing of the collision are still under discussion and opinions differ (Ueno and Charoentitirat, 2011; Ferrari et al., 2008; Sone and Metcalfe, 2008).
This collision was probably responsible for the biggest unconformity in northeastern Thailand. The collision suture is marked by the Nan-Uttaradit ultrabasic belt, which runs along the western side of the Indochina terrane. Contemporaneously with the regional uplifting, the conjugated shear faults brought about a number of narrow and elongated half-graben basins subsequent to the Indosinian I event (Booth and Sattayarak, 2011) in the Permo-Triassic time. The studied area belongs to a part of the Dong Phraya Yen range and represents a portion of the Indosinian fold belt, which is a southward continuation of the Pak Lay zone of Laos. There are many exposed and sub-surface basins distributed in this belt and the Khorat Plateau to the east. Two main exposed basins are the Na Pho Song and the Sap Phlu Basins located at northwest and southwest of the Khorat Plateau respectively. The Huai Hin Lat Formation was deposited in these basins on an eroded surface of the Permian and older rocks (Chonglakmani, 2011) and is overlain unconformably by the Nam Phong Formation of the Khorat Group. It is divided into five units as shown in Table 1 (Chonglakmani, 2011; Chonglakmani and Sattayarak, 1978). The Late Triassic (Norian) age of the Huai Hin Lat Formation is based on the Estheria fauna and spores and pollen (Haile, 1973; Kobayachi, 1973).
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The Sap Phlu Basin is a small basin among the Late Triassic basins of this region. The largest basin is located underneath the Khorat Plateau, 20 km northeast of the Sap Phlu Basin. This large and more prospective basin is being investigated on its potential for petroleum accumulation. The Sap Phlu Basin is orientated in NW-SE direction. The active margin was controlled by a west dipping listric normal fault located in the northeastern part of the basin. To the west, a thick sequence of basal conglomerate was accumulated resting unconformably on the Permian fossiliferous chert and limestone beds. The study of wells drilled by oil companies including seismic interpretation contributes to a better understanding of the subsurface distribution and extension of the Huai Hin Lat Formation. The exposure of the Huai Hin Lat Formation in the Sap Phlu Basin contains well-preserved Estheria fauna and fossil leaf in dark grey shale and marlstone (DMR, 2007).
The Ban Nong Sai Section is a part of the exposed Sap Phlu Basin (Fig. 1). It is located at 14°38'11.4"N and 101°38'56.2"E between the villages of Nong Sai and Khlong Muang along the Highway No. 2048 (Pak Chong-Wang Nam Khiao), Pak Chong District, Nakhon Ratchasima Province in western margin of the Khorat Plateau close to the Kao Yai National Park. The Huai Hin Lat Formation of the Sap Phlu area has been the subject of earlier lithostratigraphic study and mapping. But it has not previously been investigated geochemically except for a few source rock quality data. The section (Fig. 2) is approximately 14 m thick and consists mainly of calcareous shale, calcareous mudstone, marlstone, and limestone. It can be correlated to a part of the Dat Fa Member of a deep lacustrine facies of the Na Pho Song Basin (Chonglakmani and Sattayarak, 1978). The section can be lithostratigraphically subdivided into 3 parts, i.e., the lower part (beds 1–7), the middle part (beds 8–12), and the upper part (beds 13–20).
The lower part, beds 1–7, is mainly light grey to black calcareous shale. They are massive and highly resistant beds except the bed 3 is thin-bedded which is approximately 6–10 cm thick and can be differentiated into 3A–3D. These beds are orientated in NW-SE direction and are gently dipping approximately 10º–15º. They are conformable to the lower part of Khorat Group. Beds 1, 6, and 7 contain well-preserved Estheria sp. Mud cracks can be observed on the bottom of beds 1, 3, and 4. They indicate a sub-aerial exposure and desiccation in a sunny or an arid condition. The calcareous shale beds are in places characterized by abundant pyrite crystals and spheres. Love (1962) and Vallentyne (1962) concluded that the pyrite spheres in dark color sediments appear to be the product of early diagenesis in an anaerobic environment. The weathered calcareous black shale is generally grey to brownish grey.
The middle part, beds 8–12, consists mainly of light grey to grey marl or muddy limestone and dark grey to grey limestone. They are thick-bedded and extremely resistant especially in the limestone beds. They are gently dipping 15º–18º and are conformable with the lower part. The calcareous shale and mudstone are normally graded into marl. Much of the calcite in these calcareous sediments is extremely fine-grained and there is a few evidence of recrystallization. The limestone is well-bedded and contains high percentage of clay. It is graded to the argillaceous limestone. Graded-bedding and cracks filled with small calcite crystals have been observed in bed 9.
The upper part, beds 13–20, is mainly composed of greenish grey to black calcareous mudstones and light grey to black calcareous shale. The beds are also gently dipping (12º–13º). The calcareous shale beds are higher resistant than the mudstone beds but they are less resistant than the shale beds of the lower part. Beds 15 and 17 contain Estheria sp. The calcareous shales of both lower and upper parts are similar. The calcareous shale is grey to brownish grey and the calcareous mudstone is yellowish brown and greenish grey color.
The section has been measured and described based on its lithologic and sedimentologic characteristics. It is a part of the Huai Hin Lat Formation of the Sap Phlu Basin. Most natural outcrops of the organic rich fine-grained rocks are too weathered for reliable analysis. Unweathered samples were collected from natural outcrops in the studied section and were analyzed in order to assess the petroleum source rock potential. The petrographic study for identification of palynological assemblage and the geochemical analysis for providing the concentration of total organic carbon (TOC) and major, trace, and rare earth elements are performed.
Fresh samples from shale beds of Ban Nong Sai Section were collected and analyzed petrographically in this study. Fifty grams of each sample were processed using standard palynological methods (Albani et al., 2006). The sample was spiked with a known number of lycopodium spores and the mixture was then treated with hydrochloric acid (36.5%) and hydrofluoric acid (40%). The residue was sieved in pure ethanol and then concentrated using zinc bromide solution (S.G. 2.5). The concentrations of amorphous organic matters (AOM), palynomorphs, and phytoclasts were determined from the residue by measuring the frequency ratio of each of these components to lycopodium spores in the concentrated residues using light microscopy.
The total organic carbon (TOC) of fine-grained rocks was measured by using Liqui TOC instrument (±1% error) at the State Key Laboratory of Biogeology and Environmental Geology of the Ministry of Education, China University of Geosciences (Wuhan). Samples were treated with dilute hydrochloric acid and burnt in pure oxygen under static conditions (960–970 ℃). The organic carbon is oxidized to generate carbon dioxide. Helium as carrier gas brings measurement by thermal conductivity detector through the instrument. Then the measured signal value was calculated to organic carbon content.
The samples for geochemical analysis were trimmed to remove the weathered surface and pulverized to 200 meshes in an agate mortar. Major element abundances were measured on fused glass beads using a XRF-1800 instrument (±10% error and < 5% relative standard deviation) based on wavelength-dispersive X-ray fluorescence (XRF) analysis at the State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences (Wuhan). The powdered samples were dried in oven at 105 ℃. The samples and compound flux, weighted 0.700 0±0.000 5 and 5.000 0±0.000 5 g, respectively, were mixed and added 10 drops of 0.15 g/mL LiBr agent. The mixed samples were put with Pt-Al crucible into the high-frequency melting furnace to make a glass disk for XRF analysis. Trace elements and rare earth elements (REEs) were measured by inductively coupled plasma mass spectrometry (ICP-MS) (±5% error) at the Key Laboratory of Biology and Environmental Geology of the Ministry of Education, China University of Geosciences (Wuhan).
Sholkovitz (1995) previously recognized that the same basic biogeochemical process was operated in lake as in ocean. The geochemical proxies depended on organic matter that supplied the substances. The enrichment of all proxies can also indicate high paleoproductivity as in the ocean process.
Sholkovitz (1995) also suggested that the simple patterns of trace element distributions and behavior are rarely seen in lakes unlike the oceans. However, Oliveira et al. (2003) and Martín-Puertas et al. (2011) applied these proxies to successfully evaluate the reducing gradation in lacustrine of their studies. Therefore, the paleoredox proxies that are generally used in marine sediments can be used in lacustrine sediments as well.
The potential of paleoproductivity can be evaluated based on the concentrations of palynological assemblage, TOC, excess SiO2, and normalized Ba/Al and P/Al ratios.
The palynological assemblage of the studied samples comprises abundant AOM, acritarchs, phytoclasts, and a few spores and pollen. The productivity is indicated by the abundance of these palynological components. AOM is structureless products derived from phytoplankton or bacteria, higher plant resins, and reworked microbiological matters. They show no distinct form and are varied in color. AOM often contains palynomorphs and pyrite inclusions, and may exhibit fluorescence (Suárez-Ruiz et al., 2012). Acritarchs are small organic structures of varying origins. The common type is the resting cysts of dinoflagellata or chlorophyta (Shen et al., 2012). Phytoclasts are microscopic plant fragments. The recovered small amount of spores and pollen are true representative of the parent vegetation from the adjacent landmass (Shen et al., 2012) and were transported to accumulate in the lake.
Organic detritus passing from the photic zone through the water column to the sea floor controls nutrient regeneration, fuels benthic life, and affects burial of organic matters in the sediments (Vetö et al., 1997; Suess, 1980). It records only a fraction of the total biological productivity in the surface waters of ocean (Tribovillard et al., 2006) and the lacustrine as well. The concentration of sedimentary organic matter (Gupta and Kawahata, 2006) and the total organic carbon content can be used as a paleoproductivity indicator (Martín-Puertas et al., 2011; Meyers, 1997). Higher productivity is marked by elevated organic matters and organic carbon content (Martín-Puertas et al., 2011).
According to Rona (1988) and Yamamoto (1987), the silica in sediments is derived from hydrothermal, terrigenous, or biogenic sources. The source of silica of the studied samples is not associated with the hydrothermal sources as shown in Fig. 3 and it is partly derived from biogenic SiO2 as represented by the excess silica value following the suggestion of Shen et al. (2014)
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Excess SiO2(%)=SiO2 (measure) −(Almeasure )×(SiO2/Al)PAAS ) |
where SiO2(measure) and Al(measure) are percentage by weight of samples and (SiO2/Al)PAAS is ratio of SiO2/Al of the post-Archean Australian shales (Taylor and McLennan, 1985). The high excess of silica concentrations is common in sediments of high productivity regions of the modern ocean (Shen et al., 2012; Murray and Leinen, 1993) as well as the lacustrine environment. Therefore, the excess silica present in rock is a good geochemical indicator for paleoproductivity (Martín-Puertas et al., 2011; Bertrand et al., 2008; Cohen, 2003). The concentration is proportional to silica-bearing organism and is a reflection of total primary productivity in the lake (Martín-Puertas et al., 2011; Cohen, 2003). Their hard parts are made of hydrated silicon dioxide or frustule and probably preserved in benthic floor of lacustrine and a high concentration may indicate a high productivity.
To compare trace element concentrations in the samples, it usually involves normalized trace element concentrations to aluminum content (Reolid et al., 2012; Calvert and Pedersen, 1993). Van der Weijden (2002) suggested that aluminum normalization of elemental concentrations is useful procedure for examining the degree of enrichment of an element in sediments. Aluminum can be considered as an indicator of the aluminosilicate fraction of the sediments with very little ability to move during diagenesis in most sedimentary deposits (Tribovillard et al., 2006; Piper and Perkins, 2004; Morford and Emerson, 1999; Calvert and Pederson, 1993; Brumsack, 1989).
The normalized Ba/Al is extensively used as a proxy for paleoproductivity (Reolid et al., 2012). Ba is present in the form of barite (BaSO4) and is mainly contained in detrital plagioclase crystals (Tribovillard et al., 2006; Rutch et al., 1995; Bishop, 1988). Many studies have examined the link between surface productivity, export of organic matters from the photic zone, and biogenic Ba abundance in the water column (Jeandel et al., 2000; Monnin et al., 1999; Gingele and Dahmke, 1994; Dymond et al., 1992) as well as in the surface sediments (Tribovillaed et al., 2006; Paytan et al., 2003; Prakash Babu et al., 2002; Paytan et al, 1996; Paytan, 1996).
Trappe (1998) and Mackenzie et al. (1993) suggested that the content of phosphorus in most marine sediments and sedimentary rocks is higher than the average crustal abundance which is about 0.01%. The main source of phosphorus contributed to sediments is the phytoplankton necromass (including fish scales and bones), which reaches the sediment water interface. Van Cappellen and Ingall (1994) confirmed that anoxic bottom water of marine and lacustrine settings enhances the regeneration efficiency of phosphorus from sediments. Phosphorus is a structural element in DNA and RNA, as well as in many enzymes, phospholipids, and biomolecules (Tribovillard et al., 2006). Thus the distributions of phosphorus in sediments or sedimentary rocks are linked to the supply of organic matter possibly resulted from high productivity.
The paleoredox condition of the water and sediment interface can be evaluated based on the elemental composition of the sediment. The widely used geochemical paleaoredox proxies, i.e., U/Th, V/Cr, Ni/Co, (Cu+Mo)/Zn, Ni/V, and Ce anomalies are considered in this study.
Uranium and thorium are present in detrital fraction associated with heavy minerals or clays (Jones and Manning, 1994). The authigenic uranium enrichment in sediment is controlled by the oxygen penetration depth and the sedimentation rate. The slow sedimentation rate allows more time for diffusion of uranyl ions from the water column into the sediment (Tribovillard et al., 2006; Crusius and Thomson, 2000). As the intensity of sulfate reduction activity is linked to the abundance of reactive organic matters, the uranium abundance usually shows a good correlation with the organic carbon content (Tribovillard et al., 2006; McManus et al., 2005). Th is relatively immobile in the low-temperature surface environment and is concentrated during weathering in resistant minerals. Therefore, the high U/Th may indicate high organic matter accumulation in the water as U also tends to become enriched in marine sediments under reducing condition (Tribovillard et al., 2006; Algeo and Maynard, 2004).
Vanadium is present in a quasi-conservative form of vanadate oxyanions and adsorbed on both Mn- and Fe-oxyhydroxide (Wehrli and Stumm, 1989; Calvert and Piper, 1984) and possibly kaolinite (Tribovillard et al., 2006; Breit and Wanty, 1991). It is associated with a reducing environment. Chromium is usually incorporated within the detrital clastic fraction of sediment and it may substitute Al in clays. It can be adsorbed or occurred as chromite (Jones and Manning, 1994; Patterson et al., 1986; Bjorlykke, 1974). The ratio V/Cr has been employed as an index of paleo-oxygenation in a number of studies (Jones and Manning, 1994; Dill et al., 1988; Dill, 1986; Krecji-Graf, 1975; Bjorlykke, 1974; Ernst, 1970). Krecji-Graf (1975) and Ernst (1970) suggested that the V/Cr values of above 2 represent an anoxic depositional condition with H2S present in the water column overlying the sediment. Values below 2 are indicative of less reducing condition and values around 1 suggest the O2-H2S interface within the sediments (Jones and Manning, 1994).
Nickel is probably incorporated as an insoluble NiS into pyrite, even if the kinematics of the process is slow (Tribovillard et al., 2006; Morse and Luther, 1999; Huerta-Diaz and Morse, 1992, 1990). Grosjean et al. (2004) and Lewen and Maynard (1982) suggested that under reducing of anoxic/ euxinic condition, the nickel may be preserved in sediments by the organic matters. Cobalt in anoxic water forms the insoluble sulfide CoS, which can be taken up in solid solution by authigenic Fe-sulfides (Huerta-Diaz and Morse, 1992). The higher Ni/Co ratio (> 1) is associated with the pyrite diagenesis (Jones and Manning, 1994). The value is lower than 1 probably indicates the less reducing condition. Therefore it is used as a reliable redox proxy because of its higher abundance in clastic material.
Copper behaves partly as a micronutrient (Calvert and Pederson, 1993). It may be released to pore waters and incorporated in solid solution of pyrite (Tribovillard et al., 2006; Morse and Luther, 1999; Huerta-Diaz and Morse, 1992, 1990). Zinc may be released from organometallic complexes to pore waters and also incorporated as solid solution phase in pyrite (Tribovillard et al., 2006; Morse and Luther, 1999; Daskaladis and Helz, 1993; Huerta-Diaz and Morse, 1992). Molybdenum concentrations have been widely used as a proxy for the benthic redox (Meyers et al., 2005) due to their enrichment associated with increasing reducing potential. The (Cu+Mo)/Zn ratios are expected to increase under reducing conditions and decrease while the environment is more oxidizing. Hallberg(1982, 1976) proposed the (Cu+Mo)/Zn relationship as an indicator for the oxygenation condition of bottom waters. Thus the ratios have also been used to interpret the depositional environment and the higher degree of reducing environment is detected by higher Cu contents than Zn.
Ni and V are associated with reducing environment. Lewan (1984) and Lewan and Maynard (1982) suggested that the abundances of Ni and V are controlled by the factors that supply them through diffusion from the overlying water column. In addition, the ratios Ni/V in bitumen and oils decrease in a reducing environment due to the availability of V and removal of nickel as sulphide (Jones and Manning, 1994).
Ce anomalies are useful paleoredox proxies (Shen et al., 2012; Kakuwa and Matsumoto, 2006; German and Elderfield, 1990). They can be calculated by equation of Ce/Ce*=2Ce/(Lan+Prn) (Kato et al., 2006). The higher concentration indicates a more reducing environment and an anoxic condition are achieved if the value exceeds 0.8, which is the cutoff between the oxic-dysoxic and anoxic environments (Shen et al., 2012).
The productivity of the Huai Hin Lat Formation accumulated in the Sap Phlu Basin is evaluated based on the relevance and the abundance of the palynological constituent. Moreover, the association of TOC, excess SiO2, and normalized trace element concentrations (Ba/Al and P/Al) are incorporated in the assessment of the paleoproductivity in this study.
For understanding the paleoenvironment of the Huai Hin Lat Formation, the relevant geochemical indices for paleoredox condition, e.g., the changing relationship of U and Th and the concentration ratios of various trace metals (V/Cr, Ni/Co, (Cu+Mo)/Zn, Ni/V) and REEs (Ce/Ce*) have been evaluated.
The depositional setting of the Huai Hin Lat Formation is reflected in the particulate organic matter (POM) or palynofacies present in the rock, which comprises the mixture of lacustrine palynomorphs and a significant amount of terrestrial organic particles. The studied samples contain a significant amount of amorphous organic matter (AOM), palynomorphs, phytoclasts, and a few spores and pollen but they lack of diversity (Fig. 4). The organic matters were in extremely poor preservation and almost impossible to identify. Nevertheless, a distinctive palynological assemblage was identified. The point-count result and their fraction in a cumulative percentage are given in Table 2 and Figs. 4 and 5a.
| Beds | Palynofacies point count (particles/g) | TOC (%) | |||||||
| AOM | Acritarchs | Phytoclasts | |||||||
| Point count | Fraction | Point count | Fraction | Point count | Fraction | ||||
| 20 | 10 537 | 63.1 | 4 790 | 28.7 | 1 382 | 8.2 | 5.00 | ||
| 19 | 13 347 | 63.3 | 4 975 | 23.6 | 2 764 | 13.1 | 2.00 | ||
| 18 | 10 820 | 75.6 | 2 211 | 15.5 | 1 273 | 8.9 | 5.00 | ||
| 17 | 7 900 | 46.3 | 4 013 | 23.5 | 5 159 | 30.2 | 5.00 | ||
| 16 | 7 047 | 37.7 | 6 048 | 32.4 | 5 592 | 29.9 | 4.00 | ||
| 15 | 2 874 | 20.2 | 5 988 | 42.2 | 5 343 | 37.6 | 5.00 | ||
| 14 | 11 844 | 68.5 | 3 790 | 22.0 | 1 658 | 9.5 | 4.00 | ||
| 13 | 2 916 | 21.3 | 6 520 | 47.6 | 4 252 | 31.1 | 2.00 | ||
| 12 | 62 | 2.8 | 1 184 | 54.0 | 948 | 43.2 | 3.48 | ||
| 11 | 289 | 4.4 | 3 178 | 47.8 | 3 178 | 47.8 | 3.61 | ||
| 10 | 10 060 | 64.2 | 395 | 2.5 | 5 212 | 33.3 | 5.00 | ||
| 9 | 2 112 | 12.6 | 7 998 | 47.6 | 6 702 | 39.8 | 5.00 | ||
| 8 | 1 187 | 57.8 | 603 | 29.4 | 264 | 12.8 | 5.00 | ||
| 7 | 12 606 | 69.3 | 1 437 | 7.9 | 4 146 | 22.8 | 6.00 | ||
| 6 | 1 132 | 52.3 | 479 | 22.1 | 553 | 25.6 | 5.00 | ||
| 5 | 4 235 | 55.9 | 1 800 | 23.8 | 1 543 | 20.3 | 5.00 | ||
| 4 | 3 979 | 75.5 | 676 | 12.8 | 614 | 11.7 | 5.00 | ||
| 3D | 5 428 | 57.5 | 2 556 | 27.1 | 1 451 | 15.4 | 6.00 | ||
| 3C | 4 436 | 77.0 | 369 | 6.4 | 958 | 16.6 | 6.00 | ||
| 3B | 6 735 | 85.5 | 762 | 9.7 | 381 | 4.8 | 7.00 | ||
| 3A | 2 317 | 73.7 | 553 | 17.5 | 276 | 8.8 | 7.00 | ||
| 2 | 2 257 | 49.9 | 1 726 | 38.2 | 539 | 11.9 | 6.00 | ||
| 1 | 8 869 | 55.8 | 4 896 | 30.8 | 2 132 | 13.4 | 5.00 | ||
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AOM concentration (Figs. 4m and 5b) of the lower part is moderate with an average value of 5 478 particles/g. It shows two high peaks of 8 869 and 12 606 particles/g in beds 1 and 7, respectively. The middle part is low with an average value 3 404 particles/g but exhibits one peak of 10 060 particles/g in bed 10. The upper part shows the high value with an average of 8 350 particles/g. It shows an increasing trend with two peaks of 11 844 and 13 347 particles/g in beds 14 and 19, respectively.
Acritarch shows occasional blooms of a few acritarch species (Figs. 4a–4d) and its concentration is low in the lower part with the upward decreasing trend and is approximately 1 700 particles/g on the average (Fig. 5c). However, it shows the high peak of 4 896 particles/g in the basal part (bed 1). The middle part is high ranging from 395 to 7 997 with an average of 3 107 particles/g. It shows two peaks of 7 997 and 3 178 particles/g in beds 9 and 11, respectively. The upper part is high, ranging from 2 211 to 6 520 with an average of 5 100 particles/g. It shows three peaks of 6 520, 6 048, and 4 975 particles/g in beds 13, 15–16, and 19, respectively.
Phytoclast concentration (Figs. 3h–3m and 5d) is generally lower than the other two. The trend closely conform to that of acritarchs. The trend is higher in the lowest and the top of the lower part with an average value of 1 418 particles/g. The trend shows the peak in bed 9 of the middle part as those of acritarchs. The concentration of the upper part is moderate except the two high peaks at the middle of bed 13 and beds 15–17 similar to the acritarchs trend.
Spores and pollen concentration (Figs. 4e–4g) is generally low throughout the section. The spore coloration index (SCI) is 7.5–8.5. The dark brown color and almost opaque palynomorphs indicate a value of 6–7 on the thermal alteration scale (TAS), which corresponds to the temperature exposure between 170–200 ℃ in the late catagenesis stage (Schneebeli-Hermann et al., 2012; Batten, 1996).
The organic matters of the studied samples consist mainly of AOM and acritarchs, which suggest that they belong to type I and type II kerogen respectively. They also contain some mixture of type III kerogen by the presence of phytoclasts in the assemblage (Suárez-Ruiz et al., 2012). The organic matters of the Huai Hin Lat Formation, based on the kerogen type and the thermal history, have already generated oil and some gas.
The TOC proxy of the studied section showing the values ranging from 1.9% to 7.1% with an average of 4.9% indicates a high productivity especially in the lower section. It shows the peak in bed 3, which does not correspond with the relatively low values of AOM, acritarchs, and phytclasts. The trend shows consistently declining from base of the middle part to middle of bed 13 of the upper part (Fig. 5e). This lowest TOC does not correspond with the high peaks of acritarchs and phytoclasts. The trend then increases upward to a high value of about 4.34% on the average.
The excess silica of the studied samples was mainly derived from hard parts of diatom. The values range from 1%–13.4% with an average of 5.5% as shown in Fig. 5f. The values slightly decline upward in the lower part (averaging 5.86%). They show two high peaks of 7.8% and 8.4% in beds 1 and 6, respectively. The middle part shows high value averaging 6.89% with the two high peaks in the carbonate rocks of beds 10 and 12, respectively. The lower peak corresponds with the high peaks of phytoclasts, acritarchs, and AOM. The values of the upper part are relatively low with an average value of 5.6%.
The ratio of Ba/Al in rocks of the measured section varies between 11.9 (10-4) to 49.6 (10-4) with an average of 25.1 (10-4) (Fig. 5g). The lower part highly fluctuates with the high peaks in beds 1 and 6, which corresponds with the high peaks of excess SiO2, phytoclasts, and AOM. The middle part shows an average value of 28.1 (10-4) and the high peak of 33.1 (10-4) in beds 9–10. The pattern corresponds with the high peaks of AOM, acritarchs, phytoclasts, and excess silica. The upper part is in general declining with the low average value of 18.1 (10-4).
The normalized P/Al trend is similar to the trend of excess SiO2 and normalized Ba/Al throughout the section. The values range from 0.01 (10-4) to 0.02 (10-4) with an average of 0.014 (10-4) as shown in Fig. 5h. The lower part shows two high peaks, which corresponds with Ba/Al, excess SiO2, phytoclasts, and AOM. The trend declines through the carbonate of the middle part to the upper part with an average of 0.016 (10-4) and 0.011 (10-4), respectively.
The TOC concentration is moderate to high, which suggests a relatively high productivity of the surface water. A covariation between acritarch concentration and TOC shows the coefficient R=0.266 (Fig. 6b), which indicates moderate relation. However, the positive covariation of coefficient R=0.523 between acritarch and phytoclast concentration exhibits close relation (Fig. 6c). The Ba/Al and P/Al show similar trends, which are depleted in the middle beds of the lower part and most of the upper part. The positive covariation between the normalized Ba/Al and P/Al exhibits the coefficient R=0.522 (Fig. 6a), which suggests the close association between them.
The U/Th ratio trend illustrated in Fig. 7a shows relatively high fluctuation throughout the section. The ratios maintain a high value averaging 0.17 and ranging from 0.12 to 0.20. The lower part shows a high value of > 0.15 with two peaks in beds 3 and 6 with the value of about 0.18. The middle part declines to approximately 0.12–0.16 in marlstone and argillaceous limestone. The upper part constantly increases and shows a relatively high value (0.19) with a low interval in bed 19.
The V/Cr ratio ranges of 1.5–3.3 and is 2.6 on the average as illustrated in Fig. 7b. The lower part shows substantial variation of high values (1.9–3.3, averaging 2.8) with a high peak as that of U/Th in bed 3 with the value of 3.3. The values abruptly decline (averaging 2.1) in the middle part of carbonate rocks. They show two peaks in beds 9 and 11 with about the same value of 2.1. The upper part increases (averaging 2.6) and shows three high peaks in middle of bed 13, bed 15 and bed 17 with the value of 2.9, 3.0, and 3.3, respectively.
The ratios of Ni/Co vary between 0.4 and 1.3 and are 0.65 on the average. The lower and the middle parts rarely fluctuate. They maintain a normal level ranging from 0.5 to 0.8 and stabilize at an average value of 0.6 with a slight high peak in bed 3 (Fig. 7c). In the upper section, the trend rises but is highly fluctuates. It shows high peaks in beds 13, 15, and 19 with an average value of 0.75.
The (Cu+Mo)/Zn relationship ranges from 0.52 to 1.04 with an average of 0.73 (Fig. 7d). The lower part shows moderate value with substantial variation, ranging of 0.61–0.81 with an average of 0.71. It exhibits three high peaks in bed 3, beds 4–5, and bed 7. The peak in bed 3 well corresponds with the peaks shown in U/Th, V/Cr, and Ni/Co. The trend declines to around 0.69–0.52 with an average of 0.59 in the middle part of carbonate rocks. Then the trend rises in the upper part, ranging from 0.65 to 1.03 with an average of 0.86. It shows three high peaks in beds 14, 15, and 19.
The Ni/V ratios ranges of 0.10–0.16 with an average of 0.13 at the lower part. The low peak in bed 3 corresponds with the high peaks of U/Th, V/Cr, Ni/Co, and (Cu+Mo)/Zn. The values rise in the middle part and maintain a level ranging from 0.16 to 0.20. They stabilize at an average value of 0.19. The values of the upper part are relatively moderate and frequently fluctuate. They range from 0.09 to 0.19 with an average of 0.14 as shown in Fig. 7e. They show high peaks in middle beds 13 and 15, which correspond with the low peaks of (Cu+Mo)/Zn.
The section contains high ratio of Ce anomalies with the value ranging of 0.84–1.19 and an average of 0.97 (Fig. 7f).
The lower part increases from 0.84 to 1.01 with an average of 0.92. It exhibits two high peaks in beds 3 and 6, which correspond with the high peaks of U/Th. The values rise to 0.88–1.19, averaging 1.03 in the middle part. The upper part is about 1.00 on the average and shows a slight declining trend with a sudden increasing shift interval in bed 19.
Integration of the obtained petrographical and geochemical results leads us to a more precise characterization of the paleoenvironmental conditions of the Huai Hin Lat Formation, which could be related to the paleoproductivity and development of the reducing events of the basin.
In the studied section, the high paleoproductivity can be distinguished by the high peaks or high values of the paleoproductivity proxies.
The lower part shows two prominent high peaks of AOM, acritarchs, phytoclasts, excess SiO2, Ba/Al, and P/Al in the lower and upper beds (beds 1 and 7). These beds indicate a high paleoproductivity, which is supported by the high TOC. Although the middle bed (bed 3) shows relatively lower productivity based on the paleoproductivity proxies but the TOC exhibits the highest peak, which can be explained by the high rate of preservation of organic matters.
The middle part shows a high peak in beds 9 and 10, which is exhibited in high AOM, acritarchs, phytoclasts, excess SiO2, and Ba/Al. Although the high peak in P/Al is not shown, however, the values are relatively high. It indicates the relatively high productivity in the beds of the middle part, which is supported by the high TOC.
The upper part shows three high peaks in beds 13, 15–16, and 19. The lower peak is shown only in acritarchs and phytoclasts but the concentrations of AOM, excess SiO2, Ba/Al, P/Al, and TOC are relatively low. It indicates lower productivity compared to the other two. The middle peak is similar to the lower one but the concentration of SiO2 and TOC are higher, so it indicates a higher productivity than the lower peak. The upper peak shows high concentration of AOM, acritarchs, and phytoclasts but TOC is in the low peak. It suggests that the productivity is high but the rate of preservation is low.
The high peaks of palynological and the geochemical proxies of the studied section reflect a variation of high productivity. Two relatively lower productivity intervals are present in the middle of the lower part (bed 3) and the lower bed 13 of the upper part. The bed 3 of the lower part shows the highest peak TOC, which can be explained by the excellent preservation condition. The lower bed 13 shows relatively lower TOC, which indicates a poorer preservation condition than bed 3.
The geochemical paleoredox indices, i.e., U/Th, V/Cr, Ni/Co, (Cu+Mo)/Zn, Ni/V, and Ce anomalies, have been calculated from the analysis results of the studied samples. The degree of the paleoredox condition may be evaluated based on the values and high peaks of the relevant indices.
The lower part shows two prominent high peaks of U/Th, V/Cr, Ni/Co, (Cu+Mo)/Zn, and Ce/Ce* in beds 3 and 6. They indicate the relatively high reducing condition. The bed 3 is substantiated by the high peaks of V/Cr, Ni/Co, and Ce/Ce* and the low peak of Ni/V.
The trends of U/Th, V/Cr, and (Cu+Mo)/Zn are fluctuated and declining upward in the middle part suggests a less reducing condition. The upward increasing trend of Ni/V also supports this interpretation.
The upper part shows three high peaks in beds 13, 15, and 17. The lower peak of bed 13 is shown in V/Cr and Ni/Co and is corresponded with a high value of U/Th. The beds 15 and 17 exhibit high peaks or high values of V/Cr and Ni/Co, which are supported by the high values of U/Th and Ce/Ce*. All the high peaks of the upper part are, therefore, indicating the high reducing condition.
The study section shows many high peaks or high values of paleoredox proxies except the middle part and the lower bed (lower bed 13) of the upper part. It indicates that the section was mainly under reducing condition, which is supported by Ce/Ce* and V/Cr values. The studied samples yield the Ce/Ce* ranging 0.84–1.19, which is above the cutoff value of 0.8 for the anoxic condition. The V/Cr values are 2.6 on the average, which is also above the cutoff value of 2.0 for the anoxic condition. The middle of the lower part (bed 3) shows the lower productivity but it contains the highest peak TOC, which conforms to the excellent preservation in the reducing condition. The middle part, which shows high productivity, exhibits a less reducing condition. So it contains relatively lower TOC compared to the more reducing intervals. The lower bed 13 of the upper part shows less reducing condition and low TOC, which conforms to the lower productivity.
High resolution of geochemical and palynological analyses provide new insights into elucidation of the depositional environment, the characterization of the organic matter content, and the assessment of source rock potential.
(1) The paleoproductivity is assessed by the concentration of the AOM, acritarchs, phytoclasts, TOC, excess SiO2, Ba/Al, and P/Al proxies. The strata of high productivity can be distinguished by high peaks or high values of its proxies. The geochemical indices of U/Th, V/Cr, Ni/Co, Ni/V, (Cu+Mo)/Zn, and Ce anomalies have been used for assessment of the benthic redox condition. The strata of high reducing condition can be distinguished by high peaks or high values of its proxies but they show the opposite on Ni/V.
The middle of the lower part (bed 3) shows the lower productivity but it contains the highest TOC, which conforms to the excellent preservation of organic matters in the reducing condition. The middle part, which shows high productivity, exhibits a less reducing condition. Thus it contains a relatively lower TOC compared to the stronger reducing intervals (bed 3). The lower bed 13 of the upper part shows lower productivity and less reducing condition, which conforms to the lower TOC.
(2) The Huai Hin Lat shale contains high TOC (1.9% to 7.1%) which is classified as good to excellent source rock. It consists mainly of AOM and acritarchs, which suggests that they belong to type I and type II kerogens respectively. It has already generated significant amount of oil and some gas to the Sap Phlu Basin based on its high thermal maturity level (Ro).
ACKNOWLEDGMENTS: This study was supported by the Commission on Higher Education, Ministry of Education of Thailand and the Royal Golden Jubilee Program of the Thailand Research Fund (RGJ-TRF), the NSFC (No. 41172202), the China Geological Survey Program (No. 1212011121256), and the Special Funding from the State Key Laboratory of Geological Processes and Mineral Resources. Many thanks are conveyed to the officials at the State Key Laboratory of Geological Processes and Mineral Resources and State Key Laboratory of Biology and Environmental Geology, China University of Geosciences, Wuhan. The final publication is available at Springer via http://dx.doi.org/10.1007/s12583-016-0666-8.| Adachi, M., Yamamoto, K., Sugisaki, R., 1986. Hydrothermal Chert and Associated Siliceous Rocks from the Northern Pacific Their Geological Significance as Indication OD Ocean Ridge Activity. Sedimentary Geology, 47(1/2): 125-148. doi: 10.1016/0037-0738(86)90075-8 |
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Boonnarong Arsairai, Akkhapun Wannakomol, Qinglai Feng, Chongpan Chonglakmani. Paleoproductivity and paleoredox condition of the Huai Hin Lat Formation in northeastern Thailand. Journal of Earth Science, 2016, 27(3): 350-364. doi: 10.1007/s12583-016-0666-8
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| Beds | Palynofacies point count (particles/g) | TOC (%) | |||||||
| AOM | Acritarchs | Phytoclasts | |||||||
| Point count | Fraction | Point count | Fraction | Point count | Fraction | ||||
| 20 | 10 537 | 63.1 | 4 790 | 28.7 | 1 382 | 8.2 | 5.00 | ||
| 19 | 13 347 | 63.3 | 4 975 | 23.6 | 2 764 | 13.1 | 2.00 | ||
| 18 | 10 820 | 75.6 | 2 211 | 15.5 | 1 273 | 8.9 | 5.00 | ||
| 17 | 7 900 | 46.3 | 4 013 | 23.5 | 5 159 | 30.2 | 5.00 | ||
| 16 | 7 047 | 37.7 | 6 048 | 32.4 | 5 592 | 29.9 | 4.00 | ||
| 15 | 2 874 | 20.2 | 5 988 | 42.2 | 5 343 | 37.6 | 5.00 | ||
| 14 | 11 844 | 68.5 | 3 790 | 22.0 | 1 658 | 9.5 | 4.00 | ||
| 13 | 2 916 | 21.3 | 6 520 | 47.6 | 4 252 | 31.1 | 2.00 | ||
| 12 | 62 | 2.8 | 1 184 | 54.0 | 948 | 43.2 | 3.48 | ||
| 11 | 289 | 4.4 | 3 178 | 47.8 | 3 178 | 47.8 | 3.61 | ||
| 10 | 10 060 | 64.2 | 395 | 2.5 | 5 212 | 33.3 | 5.00 | ||
| 9 | 2 112 | 12.6 | 7 998 | 47.6 | 6 702 | 39.8 | 5.00 | ||
| 8 | 1 187 | 57.8 | 603 | 29.4 | 264 | 12.8 | 5.00 | ||
| 7 | 12 606 | 69.3 | 1 437 | 7.9 | 4 146 | 22.8 | 6.00 | ||
| 6 | 1 132 | 52.3 | 479 | 22.1 | 553 | 25.6 | 5.00 | ||
| 5 | 4 235 | 55.9 | 1 800 | 23.8 | 1 543 | 20.3 | 5.00 | ||
| 4 | 3 979 | 75.5 | 676 | 12.8 | 614 | 11.7 | 5.00 | ||
| 3D | 5 428 | 57.5 | 2 556 | 27.1 | 1 451 | 15.4 | 6.00 | ||
| 3C | 4 436 | 77.0 | 369 | 6.4 | 958 | 16.6 | 6.00 | ||
| 3B | 6 735 | 85.5 | 762 | 9.7 | 381 | 4.8 | 7.00 | ||
| 3A | 2 317 | 73.7 | 553 | 17.5 | 276 | 8.8 | 7.00 | ||
| 2 | 2 257 | 49.9 | 1 726 | 38.2 | 539 | 11.9 | 6.00 | ||
| 1 | 8 869 | 55.8 | 4 896 | 30.8 | 2 132 | 13.4 | 5.00 | ||
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