Journal of Petroleum Geology, Vol.

35(1), January 2012, pp 67 - 84

67

EVALUATION OF HYDROCARBON PROSPECTS USING SURFACE GEOCHEMICAL DATA WITH CONSTRAINTS FROM GEOLOGICAL AND GEOPHYSICAL OBSERVATIONS: SAURASHTRA BASIN, INDIA

D. Mani+*, D. J. Patil*, M. S. Kalpana* and A. M. Dayal*

The Saurashtra Basin in western India is considered to have significant hydrocarbon potential. However conventional exploration methods, particularly for Mesozoic prospects, have been hampered by the thick basalt cover. In this study, near-surface geochemical methods are used to investigate the generation of thermogenic gaseous hydrocarbons in the basin. Shallow soil samples were collected from favourable locations identified by integrated geophysical and geochemical studies.The compositional and isotopic signatures of adsorbed gaseous hydrocarbons (methane through pentane) together with soil iodine concentrations were used as surface indicators of petroleum micro-seepages. High concentrations of adsorbed thermogenic methane (C1= 518 ppb) and ethane plus higher hydrocarbons (C2+=977 ppb) along with iodine concentrations up to 68.5 ppm were observed. Total organic and inorganic carbon (TOC and TIC) measurements, fluorescence and X-ray diffraction (XRD) studies showed that the nearsurface hydrocarbon occurrences were seepage related. Elevated hydrocarbon and iodine concentrations were coincident with dykes and lineaments in the study area, which probably served as conduits for the micro-seepage of hydrocarbons.
INTRODUCTION Western India includes prolific oil and gas provinces including the broad shelf area offshore Mumbai and the onshore Cambay graben. Mesozoic and Cenozoic reservoirs in the Jaisalmer, Bikaner-Nagaur and Barmer Basins in Rajasthan (NW India) produce commercial volumes of hydrocarbons, and the Kutch and
* National Geophysical Research Institute (CSIR), Uppal Road, Hyderabad 500007, Andhra Pradesh, India. + Corresponding author, email: devleenatiwari@ngri.res.in

Saurashtra Basins in the north (DGH, 2010) and the Kerala-Konkan Basin in the south also have fair exploration potential. This study focuses on the Saurashtra Basin, which is located north of the commercially proven Mumbai offshore and west of the petroleum-bearing Cambay Basin (Fig. 1a). The basin is considered to have fair hydrocarbon prospects in Mesozoic reservoirs (DGH, 2010; Infraline, 2002). However, the resource potential of the basin is little known owing to the
Key words: Saurashtra Basin, India, hydrocarbon microseepage, near-surface hydrocarbons, surface geochemical prospecting, soil iodine, Deccan Traps, basalt.

2012 The Authors. Journal of Petroleum Geology 2012 Scientific Press Ltd

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Near surface geochemical data, Saurashtra Basin, India

(a)
23.0

69.0

69.5

70.0

70.5

71.0

71.5

72.0 23.0

Kandla Surendranagar

22.5

Jamnagar Dwarka
Study Area

22.5

Rajkot
22.0

22.0

Porbander
21.5

Bhavnagar Junagadh Amreli

21.5

Legend
21.0 Recent / Quaternary Tertiary Deccan Trap 20.5 Cretaceous 69.0 69.5 70.0 70.5 71.0
70.20 70.25

Veraval

21.0

71.5
70.30

72.0
70.35 70.40

20.5

(b)
22.8 Sediment Thickness (m)
Gulf of Kutch

(c)

22.34

22.6
Jamnagar

Matwa

22.34

2500

2000
Matwa

22.29

22.29

22.4

Khandera

Khandera

Ialpur

22.2

Laloi

1500
22.24 22.24

Kalavad

Lodhika

1000

Laloi
500
22.19

Kalavad

22.19

22.0 0 C2+ Conc (ppb) 21.8 69.8 70.0 70.2 70.4 70.6 70.8
0 to 50 50 to 100 100 to 766

22.14

70.20

70.25

Deccan Trap

70.30

70.35

22.14 70.40

Soil Iodine

Adsorbed Hydrocarbons

Fig. 1. (a) Regional location map of the Saurashtra Peninsula in western India (after Mehr, 1995). Box indicates the study area. (b) Location map of the study area in the Saurashtra Peninsula with sediment thicknesses and hydrocarbon concentrations (modified after Satpal et al., 2002; Harinarayana, 2008; Kumar et al., 2004; Kumar et al., 2009). (c) Detailed map showing sample collection points for adsorbed hydrocarbons and soil iodine concentration measurements in the study area.

presence of thick Deccan basalts of Late Cretaceous age, which have hindered studies of the underlying Mesozoic hydrocarbon targets by conventional geophysical methods. Surface geochemical prospecting methods have therefore been applied in the Saurashtra Basin. Geochemical methods seek to demonstrate the presence of adsorbed and/or free hydrocarbons in near-surface soils and sediments (Schumacher and LeShack, 2002). These hydrocarbons have migrated either from source rocks or from breached oil and gas reservoirs, and will have moved along faults and

fractures by a variety of processes to the near-surface environment (e.g. Abrams, 1996a,b; 2005, 2007; Jones and Drozd, 1983; Horvitz, 1985; Kartsev et al., 1959; Klusman, 1993; Mani, 2008; Schumacher, 1996; Sechman, 2011; Whiticar, 2002). Other indirect geochemical indicators for hydrocarbon microseepage include the near-surface soil iodine concentration and the presence of hydrocarbonoxidising microbial populations. Integrated geophysical studies in the Saurashtra Peninsula have indicated that thick Mesozoic sedimentary successions are present in two areas:

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69

W 0 -1

Lodhika Well Deccan Trap

Depth (km.)

-2 -3 -4 -5 0

Mesozoic Sediments

Lochika

Saurashtra

Basement
10 20 30 40 50 Distance (km.) 60 70 80 90

Fig. 2a. An east-west profile across the Saurashtra Peninsula showing the occurrence of a relatively thick sedimentary succession towards the western part of the basin (after Harinarayana, 2008).

around Jamnagar in the NW and near Dwarka to the west (Fig. 1) (Harinarayana, 2008; Rao et al., 2004; Sarma et al., 2004; Satpal et al., 2006). The few wells which have been drilled (e.g. Viramgaom-1, Dhandhuka-1 and Lodhika-1) have indicated varying thickness of basalt (350m-1300m) and underlying Mesozoic sediments (175m-2100m+) (Singh et al., 1997). Mesozoic sediments penetrated in the Lodhika1 well near Rajkot (Fig. 1b) showed fair hydrocarbon potential (Singh et al., 1997). Preliminary surface geochemical studies in the NW of the peninsula showed high light hydrocarbon concentrations (methane through butane) in areas adjoining Jamnagar (Kumar et al., 2004; 2009). Low concentrations of C1-C4 hydrocarbons characterized the soils around Dwarka. In this study, these preliminary geochemical surveys were extended to a detailed grid of closely spaced samples from the Jamnagar area. The objectives of the study were two-fold; firstly, to assess the use of geochemical indicators as a tool for the rapid evaluation of hydrocarbon prospects in this frontier basin; and secondly, to provide an improved understanding of the occurrence of thermogenic hydrocarbons in the Saurashtra Basin by integrating the results of the present study with the available geophysical and geological data. In addition to analysing adsorbed light gaseous hydrocarbons, other data were derived from studies of the stable carbon isotope ratios of the hydrocarbon gases, and soil iodine concentrations which are an indirect indicator of hydrocarbon seepage (Allexan et al., 1986; Goudge, 2007; 2010; Kartsev, 1959; Leaver and Thomasson, 2002; Mani et al., 2011a; 2011b; Moran, 1998; Tedesco et al., 1987; Xie Xuejing and Yang Binzhong, 1989). Analyses of TOC and TIC content and fluorescence and XRD studies were performed on selected samples.

GEOLOGIC SETTING AND STRATIGRAPHY The Saurashtra Basin is a rifted passive margin basin in western India (Fig. 1a), comprising an onshore area of 52,000 km2 and a 20,000 km2 area extending offshore into the Arabian Sea (Biswas, 1982; Merh, 1995). The onland part of the basin, known as the Saurashtra Peninsula, developed by rifting along three intersecting Precambrian orogenic trends: the ENEWSW Narmada Son lineament; the west coast fault with the NNW-SSE Dharwar trend; and the NE-SW Delhi Aravalli trend (Biswas 1980; 1987). In terms of geo-morphological features, the Saurashtra Peninsula is dominated by a central plateau formed of Deccan Trap lavas (Fig. 1a). Post Trappean intrusives of plugs and dykes with faults and lineaments occur in the peninsula (Auden, 1949; Karanth and Sant, 1995; Misra, 1999). Geological and magneto-telluric surveys in the Saurashtra Peninsula have shown the presence of thick Mesozoic sedimentary sequences in the western part (Harinarayana, 2008; Rao and Reddy, 2005), and led to the drilling of the Lodhika-1 well near Rajkot (Fig. 2a) which confirmed the presence of a Mesozoic section beneath the Deccan Traps (Fig. 2b). The Jurassic Lodhika Formation is composed of volcanic rocks with a thickness of more than 535 m. Overlying Cretaceous sedimentary rocks are exposed over an area of approximately 5000 km2 in the NE part of the Saurashtra Peninsula and comprise the Lower Cretaceous Dhrangadhra and Wadhwan Formations. The Dhrangdhra Formation, which crops out in the NE Saurashtra Peninsula, is divisible into Lower and Upper Members. The Lower Dhrangadhra Member has a thickness of 675 m and is dominantly composed of rudaceous sediments with thin claystones and minor siltstone/sandstones. Fossils are absent and the depositional characteristics indicate a non-marine

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Near surface geochemical data, Saurashtra Basin, India

Age

Formation

Depth (m)
0

Litholog

Lithology

Fig. 2b. Generalized lithostratigraphy of the Lodhika-1 well (after Singh et al., 1997). Well location in Fig. 2a.

Upper Cretaceous Paleocene

Deccan Trap

1000

Basalt, weathered basalt with amygdales in places traversed by calcite veins.

1200

Wadhwan

1400

Light grey to brown sandstone with clay alterations.

Upper Jurassic to Lower Cretaceous

1600

1800

Dhrangadhra

2000

Grey, brownish grey sandstone, hard and compact with dark grey to brownish grey claystone, in places carbonaceous.

Upper

2200

2400

Lower

2600

Dominantly polymictic conglomerate with red claystone. Brown sandstone with alterations of siltstone / claystone. Basalt / dolerite.

2800

Jurassic

Lodhika

Upper

3000

Basalt with red claystone.

3200

Lower

3400 3500

Tuff.

alluvial fan system. The Upper Member is characterized by sandstones and siltstones with shales containing organic matter, pyrite and siderite. Pollen, spores, plant fossils and gastropod shells have been reported (Bhandari and Kumar, 1970). The presence of deltaic channel, flood plain and levee deposits indicate a fluvial to deltaic depositional environment. The fair to good organic content (Singh et al., 1997) suggests that the Upper Dhrangadhra Member has source rock potential. Deltaic deposition was followed by a marine transgressive phase resulting in deposition of the AptianAlbian Wadhwan Formation (Biswas and Deshpande, 1983), which comprises claystones and sandstones. The formation includes bivalves, echinoids, gastropods, bryozoa and fragments of ammonites and corals, suggesting a shallow marine origin. Regional uplift took place during the Late Cretaceous and was followed by Deccan Trap volcanism (Bose, 1972; Biswas, 1980). The Cenozoic consist dominantly of shallow-marine clays and limestones (Biswas and Deshpande, 1983). Phases of tectonic deformation in the Cenozoic are indicated by extensive unconformities. Post-Trap carbonates and fine-grained clastics are prospective offshore targets.

Petroleum geology The sub-Trappean Mesozoic succession in the Saurashtra Basin is thought to contain about 40 MM tonnes of undiscovered hydrocarbon resources (Singh et al., 1997). Structures include regional and local horsts and grabens along the dominant basement trends (NNW-SSE) (Biswas, 1982; Gombos et al., 1995; Schutter, 2003; Zutshi, 1991). The Lower Cretaceous Dhrangdhra and Wadhwan Formations can be correlated with the Bhuj Formation and Ukra Member, respectively, of the highly prospective Kutch Basin (DGH, 2010). The Deccan Trap volcanics may have protected underlying hydrocarbon accumulations (Zutshi, 1989; 1991). Potential play types in the offshore Saurashtra Basin include carbonate build-ups, transpressional roll-overs, pinch-outs and wedge-outs and the canyon complex in the Indus fan system (DGH, 2010). Possible reservoir rocks are Cretaceous sandstones, Eocene-Miocene shelfal carbonates / reefal build-ups, and Tertiary deep-water sands (Indus Fan). Eocene to Miocene shales and Paleocene to Oligocene shales are possible source

D. Mani et al.

71

and cap rocks, respectively for the offshore area. For the onshore basin, limited information shows that source rocks are present in the Upper Dhrangadhra Member (Singh et al., 1997). The Rajkot depression has been suggested in unpublished reports to be a probable location of hydrocarbon generation, based on data from the Lodhika-1 well. Gravity lows, one around Jamnagar in the north and the other around Dwarka to the west, separated by a basement ridge are considered favourable locales for hydrocarbon entrapment (Satpal et al., 2006). A thicker marine sequence may be present to the west of Lodhika (Srivastava et al., 1995). The burial depth and timing of hydrocarbon generation has been inferred on the basis of thermal maturity and vitrinite reflectance measurements from core/well data (Singh et al., 1997). Initiation of hydrocarbon generation from the Upper Dhrangadhra sediments is inferred to have taken place during the Late Cretaceous, with peak hydrocarbon generation during the Paleocene to Recent. MATERIALS AND METHODS Sampling A total of 150 soil samples, in grid of 1x1 km, were collected for soil gas analyses from the Jamnagar area. They were collected from a depth of 1.5-3.5 m by manual hammering of a hollow metal pipe. For the soil iodine survey, a total of 73 samples from a depth of 2-6 in were collected at an interval of ~ 2 km, at alternate points to the soil gas sampling stations. The samples were packed separately in aluminium foil, sealed in polythene covers and marked with their Global Positioning System (GPS) locations. Precautions were taken to avoid the collection of samples from disturbed or excavated areas; or of soils contaminated with hydrocarbons, chemicals or animal waste; or samples from root zones, swamps and areas under standing water. Fig. 1c shows the sample locations. GPS locations are given in online Appendix S1 (see note on Supporting Information on page 83). Analyses Adsorbed gaseous hydrocarbons Analysis of adsorbed soil gases was based on acidextractable hydrocarbons (Horvitz, 1985). One gram of sieved, <63 soil sample was treated with 50% ortho-phosphoric acid (H3PO4) under partial vacuum conditions to desorb the light hydrocarbons. The gases were collected by water displacement in a degasification apparatus. The carbon dioxide evolved due to the decomposition of carbonates in soil was trapped in 20% potassium hydroxide in a roundbottom flask attached to the apparatus. The volume of the displaced gases was recorded, and 500l was

injected to a Varian CP-3380 gas chromatograph (GC) equipped with Porapak Q column and flame ionization detector (FID). The column oven was programmed at 60o with a hold time of 3 minutes and increased to 120oC at a rate of 20oC/min and held for 18 min with a total time of 24 min. Nitrogen was used as the carrier gas with a flow rate of 30 ml/min. The fuel gases were hydrogen and zero air with a flow of 300 ml/min. The temperature of the injector and detector was maintained at 120oC and 200oC, respectively. A Star workstation was used for data acquisition. Calibration of the gas chromatograph was performed using external standards on a peak areas basis. The adsorbed gases were quantified in ppb per gram weight of the fine-grained fraction of the sediments with corrections for moisture applied. Stable carbon isotope ratios Fifteen samples with high concentrations of adsorbed gases were measured for their stable carbon isotope compositions. The 13 C analyses of desorbed hydrocarbon gases were carried out using a Gas Chromatograph-Combustion-Isotope Ratio Mass Spectrometer (GC-C-IRMS). An Agilent 6890 GC coupled to a Finnigan-Delta PlusXP IRMS via a GC combustion III interface was used for the determination of carbon isotope ratios. One ml of the desorbed gas was injected into the GC which was equipped with a Pora Plot Q capillary column, 25 m in length and with a diameter of 0.32 mm, in splitless mode with helium as the carrier gas at a fixed oven temperature of 28 oC. The chromatographically separated hydrocarbon gases eluted from the GC column entered a pre-oxidized Cu-Ni-Pt combustion reactor maintained at 960 oC, where they were converted into carbon dioxide and water. Water was removed using a Nafion membrane tube prior to entry into the mass spectrometer. The purified CO2 after combustion entered the mass spectrometer for 13C/ 12 C ratio measurement of the individual hydrocarbon components. The GC-C-IRMS was calibrated using Natural Gas Standard (NGS-1) mixture and reported to the Vienna PeeDee Belemnite (VPDB). Replicate analyses of this gas yielded values within 0.5 of the reference value. Soil Iodine For the determination of iodine concentrations, 100 mg of <63 soil sample was treated with 5 ml of 10% tetra-methyl ammonium hydroxide in a Savillex pressure decomposition vessel at 80oC for 6 hrs. After cooling, the solution was diluted with Millipore water and 1 ml of 250 ppb antimony was added to act as an internal standard, and the volume was made up to 25 ml. The final solution containing 2% TMAH and 10 ppb antimony was centrifuged and filtered. The

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Near surface geochemical data, Saurashtra Basin, India

analyses for samples, blank and soil standards were performed on a PerkinElmer Sciex DRC II Inductively Coupled Plasma Mass Spectrometer (ICP-MS). In the procedure mentioned, SO-1 (I=12 ppm), a matrixmatching international soil standard reference material (Canadian Certified Reference Material; CCRM), was used to calibrate the ICPMS. Online Appendix S2 (see note on page 83) provides details of the soil reference materials, where the measured values are in close agreement with the certified values. The relative standard deviation (RSD) of selected samples was <1% and the limit of detection was 0.027 mg kg-1. Details of the analytical procedure were described by Balaram and Rao (2003) and Mani et al. (2007). Total Organic Carbon (TOC) About 1.5 g of 63 soil sample was treated with 3-4 drops of HCl to remove the inorganic carbon and kept overnight at 50oC in an oven. About 50 mg of the dried, HCl-treated sample was loaded onto a quartz boat and transferred to the furnace of a Soild Module 1000C, a modification of the Liqui TOC analyzer basic unit (Elementar Analysensysteme GmbH) for TOC measurement. Boden Soil Standard (TOC = 4.1%) was used to calibrate the instrument. The CO2 released due to the chemical oxidation of the organic carbon was measured by the Infra Red (IR) detector and expressed in wt %. The relative standard deviation (% RSD) of the procedure was < 1%. The samples were also measured for their total carbon (TC) content with the untreated soil samples. The inorganic carbon (IC) was determined from IC = TC - TOC. Fluorescence Ten near-surface sediment samples with high values for the adsorbed hydrocarbons were selected for fluorescence studies to measure naphthalene, phenanthrene and anthracene concentrations and also subjected to total scanning fluorescence (TSF), using a Perkin Elmer LS-55 spectrophotometer. One gram of finely powdered soil sample was extracted with 15 ml of hexane in an ultrasonic bath (Bandalin Sonorex) for 15 minutes. The sediment extract was centrifuged and the supernatant was used for fluorescence scanning. For the individual aromatic compounds, the instrument was set using following parameters: Wavelength (nm) Split Width (nm) Excitation Emission Excitation Emission Anthracene 254 403 5 4 Phenanthrene 253 368 5 5 Naphthalene 223 360 5 10 For the TSF method, the sample extracts were irradiated with light scanning between 200 to 500 nm at an interval of 5 nm and corresponding emission

wavelengths were recorded. The excitation and emission split width were 5 nm each. X-Ray Diffraction Mineral identification for ten selected samples was carried out on a Bruker AXS D8 Advance X-Ray Powder Diffractometer with Cu K radiation at the Indian Institute of Chemical Technology (IICT-CSIR, Hyderabad). The ground and sieved sample powders were subjected to X-ray diffraction analyses. The instrument parameters were set as: start, 2000o; end, 79.998o (diff. angle); step time, 13.6 s; anode, CuWL1:1.5406. RESULTS Table 1 provides a summary of the results of the geochemical analyses and further details are presented in online Appendix S1 (see note on page 83). The statistical distribution of the data was evaluated to determine whether different groups or populations are present within the data-set and also to distinguish anomalous populations from the background (Belt and Rice, 2002; Koch and Link, 1971; Lepeltier, 1969; Sinclair, 1976). Log histograms, probability diagrams and cross-plots were the statistical techniques used for this purpose. Adsorbed Soil Gas Histograms Log histograms for the adsorbed gases (C1-C5) show the presence of different populations in the data (Fig. 3a-e). In general, the frequency distribution pattern shows more than one modal peak with positive skewness in all the hydrocarbon components. The lowest concentrations shift towards smaller values with an increase in carbon number, i.e. the pentane concentration was found to be the lowest (Fig. 3e). Also, the frequency range becomes narrower with an increase in carbon number from methane to pentane. These characteristics are commonly observed for hydrocarbon gases derived from thermogenic processes (Klusman, 1993; Dai Jinxing et al., 1992). Cross-plots A cross-plot illustrates the correlation between two compositional variables and provides information on a hydrocarbons source and the effects of secondary alteration. Cross-plots between light gaseous hydrocarbons (C1-C5) are plotted in Fig. 4a-c. The plots of C1 versus C2 (Fig. 4a) and C2 versus C3 (Fig. 4b) show linear correlations, suggesting a thermogenic origin for the hydrocarbons. The plot of C1 with C2+ (sum of ethane, propane, i-butane, n -butane, i -pentane and n -pentane) indicates a

D. Mani et al.

73

Table 1. Summary of geochemical results from soil samples from the Jamnagar area.
Adsorbed hydrocarbons (ppb) C1 Min. 3 C2 0 C3 0 331 i-C4 0 297 n-C4 i-C5- n-C5 0 116 0 31 0 23 Carbon isotopes (0/00) Iodine
13 C1 13C2 13C3

TOC1

TIC

(ppm) 1.5

(ppm) (ppm) 1116 363

-45.5 -27.6 -32.6 -27 -20.9 -20.4

Max. 518 430 TOC 2 (ppm) Min. Max. 2315 10670

68.5 49410 52470 XRD

Fluorescence (ppb) Naphthalene Phenanthrene Anthracene 34.40 97.66 25.23 96.45 9.08 1.29

Quartz, Feldspar, Carbonate, and Smectites

TOC1 = 1.2- 3.5 m depth; TOC2 = 2-6 inches depth

No. of Samples

No. of Samples

Fig. 3. Histogram showing the presence of different populations in the data set for: (a) methane; (b) ethane; (c) propane; (d) i- + n-butane (e) i- + n-pentane.

40

40

a
30 20 10 0 0 40 0.8 1.6 2.4 Conc. of C1(log ppb)

b
30 20 10 0 3.2 40 30 20 10 0 0 0.8 1.6 2.4 Conc. of C2(log ppb) 3.2

c
No. of Samples No. of Samples
30 20 10 0 40 30 20 10 0 0 0.8 1.6 2.4 Conc. of C5(log ppb) 0 0.8 1.6 2.4 Conc. of C3(log ppb)

3.2

e
No. of Samples

0.8 1.6 2.4 Conc. of C4(log ppb)

3.2

3.2

bimodality (Fig. 4c), possibly indicating two different sources for the hydrocarbons (Belt and Rice, 2002; Jones and Drozd, 1983). Probability diagrams Threshold and anomaly estimates using probability plots or cumulative frequency diagrams are widely used in the interpretation of surface geochemical data (Abrams, 2005; Sinclair; 1976; 1991). A probability plot between the cumulative frequency (%) and the concentration of desorbed light gaseous hydrocarbons C1 and C2+ is

shown in Figs. 5a and b, respectively. The change in slope at about 1.75 log ppb of methane was defined as the threshold value, which indicates that ~27% of the samples with concentration above 56 ppb are likely to be anomalous (Fig. 5a). The lower portion of the plot represents the background concentration range of the methane. The threshold for C2+ is defined at a concentration of 2.25 log ppb, and the anomalous samples above 142 ppb are represented by ~ 10% of the data set in the probability diagram (Fig. 5b).

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Near surface geochemical data, Saurashtra Basin, India

Conc. o of C2 (ppb)

400 300 200 100 0 0 100 200 300 400 500 600 Conc. of C1 (ppb)
1200 1000

Conc. o of C3 (ppb)

500

R = 0.9

400 300 200 100 0 0

R = 0.9

100

200

300

400

500

Conc. of C2 (ppb)

c
R2 = 0.9

Conc. of C C2+ ( ppb)

800 600

R2 = 0.9
400 200 0

200

400

600

Conc. of C1 (ppb)

Fig. 4. Soil gas hydrocarbons cross-plot of (a) methane (C1) versus ethane (C2); (b) ethane (C2) versus propane (C3); and methane versus ethane plus higher hydrocarbons (C2+).

Bernard plots Stable carbon isotopes yield information on the origin of hydrocarbons from varied locations or sources (Fuex, 1977; Faber and Stahl, 1983; 1984; Schoell, 1983; Stahl, 1977; Stahl et al., 1981; Whiticar, 1996; 1999). A Bernard plot can be used to differentiate light hydrocarbon gases derived from thermogenic or bacterial sources (Bernard et al., 1976). C1/C2+C3 ratios <100 and 13 C 1 heavier than -60 are characteristic of thermogenic hydrocarbons; whereas C1/C2+C3 ratios > 1000 and 13C1 lighter than -60 indicate an origin from biogenic sources (Bernard et al., 1976). A Bernard plot showing the relationship between methane 13C1 and C1/C2+C3 from the soil samples from the Saurashtra Peninsula is shown in Fig. 6. The plot indicates the likelihood of a thermogenic source for the light hydrocarbons. Soil iodine concentrations A probability plot between the cumulative frequency and the concentration of iodine in ppm is shown in Fig. 7. The presence of multiple populations is indicated by the change in slope of the curve. The population with lower values is assumed to represent background; the middle set of values are transitional; and the highest values are considered to be anomalous. The inflection point at about 1.5 log ppm of iodine has been defined as the threshold value (Fig. 7). About 15% of the samples with concentrations above 28 ppm of soil iodine are therefore likely to be associated with a seepage-related anomaly.

DISCUSSION Light hydrocarbons Gases of thermogenic origin generally show a trend of decrease in concentration from methane to pentane i.e. C1>C2>C3>C4>C5 (Klusman, 1993; Tedesco, 1995; Sanez, 1984). The light hydrocarbon gases from the Jamnagar soil samples are highly correlated and follow a similar pattern as shown by the frequency distribution charts (Fig. 3 a-e) and cross-plots (Fig. 4a-c). The isotopic signatures of a few samples, J-79, J-98, and J-100, also show a progressive depletion in 13C from propane to ethane to methane (see online Appendix S1). However, an enrichment of 13C 2 compared to 13C3 is observed in a few samples which may be due to mixing between thermal gases of different maturities (Berner and Faber, 1988; Chung et al., 1988; James, 1990; Mani et al., 2011b). These gases appear to have been derived from mixed sources as indicated by the bi-modality of the cross-plot in Fig. 3c. Detailed isotopic studies of the adsorbed gases from the Jamnagar area indicate that they are an admixture of thermally-generated hydrocarbon gases from humic and sapropelic kerogens (Mani et al., 2011 b). Soil iodine The concentration of soil iodine in samples from the Jamnagar area shows relatively higher values compared to the average distribution of iodine in sedimentary rocks. Shales, sandstones and carbonates

D. Mani et al.

75

3.5 1000 3
Conc of C2+ (ppb)
1000

3.5

Conc. of C C1 ( ppb)

2.5 2

Conc. of C C1 (log ppb)

Anomalous values
100

2.5 100

Anomaly Threshold Background Values

2 1.5 1 0.5

10

Background Values

Anomaly Threshold

1.5 1 0.5

10

1 0% 20% 40% 60% Cumulative Frequency 80%

0 100%

1
0% 20% 40% 60% 80%

0
100%

Cumulative Frequency

Fig. 5.Cumulative frequency diagrams showing the background and anomalous populations of (a) methane and (b) ethane plus higher hydrocarbons in soil samples from the Saurashtra Peninsula.The anomaly threshold is defined where the change of slope occurs. In Fig. 5a, the slope change occurs at 1.75 log ppb and matches with the mean (56 ppb). In Fig. 5b, the change of slope occurs at 2.25 log ppb and matches with the mean plus half of the standard deviation (60 + 150/2).

Fig. 6. Log C1/(C2+C3) versus 13C1 (Bernard plot) for adsorbed light hydrocarbon gases from the Jamnagar area, Saurashtra Peninsula (modified after Mani et al., 2011).

100000 10000
C1/C2+C3

Biogenic Thermogenic

1000 100 10 1 -30 -70 -50 0 13 CH4 /00

100

-90

2.50

ne (log ppm) Conc. of Iodin

1.50 1.00 Background Values 0.50 0.00 0% 20%

Anomalous Values

Anomaly Threshold

10

Cumulative Frequency

40%

60%

80%

1 100%

Fig. 7. Cumulative frequency diagram for soil iodine concentrations in soil samples from the Saurashtra Basin.

dine (ppm) Conc. of Iod

2.00

Conc of C2+ (log ppb)

Anomalous Values

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Near surface geochemical data, Saurashtra Basin, India

Fig. 8. Composite map of iodine with desorbed hydrocarbon gases ( C2+). Symbols show the range of iodine concentration and the contours are the concentration of adsorbed hydrocarbon gases.

contain an average of 2.3, 0.8 and 2.7 ppm of iodine, respectively (Kebata-Pendias and Pendias, 1992; Fuge and Johnson, 1986), whereas iodine concentrations in soil samples from the Jamnagar area are up to 68.4 ppm. Organic matter is believed to be a major concentrator of iodine in petroliferous sedimentary basins (Birkle, 2006; Collins and Egleson, 1969; Fabryka-Martin et al., 1985; Kartsev, 1959; Mani et al., 2011a; Moran et al., 1995; Moran, 1996; Fehn et al., 2007; Muramastu and Wedepohl, 1998; Sheppard et al., 1995; Vinogradov, 1959; Whitehead, 1978). Soil iodine geochemistry has been related to subsequent drilling results, and iodine anomalies have been observed to exhibit a strong correlation with hydrocarbon accumulations (Leaver and Thomasson, 2002). Fixing of iodine in soil particles due to the interaction of seeping hydrocarbons with iodine in the form of iodo-organic compounds (Allexan et al., 1986; Tedesco, 1995), or transport through vertical migration of subsurface brines, have been suggested as probable causes for elevated concentrations of soil iodine (Moran, 1996; Fehn et al., 2007; Land, 1991). The source of iodine in brines in basins with large accumulations of hydrocarbons may be the organic matter which is the precursor of the crude oil. Elevated levels of iodine in the soil samples from the study area may result from the fixing of iodine by the organic compounds derived from the micro-seepage of hydrocarbons in the near-surface environment. The possibility of recent organic matter binding with soil iodine cannot be ignored; hence, soil samples were analyzed for their TOC content to investigate the correlation of surficial TOC with the iodine concentration. The TOC content of the soil samples varies between 2315 ppm and 1.067 %, and shows a poor correlation with soil iodine (r<<1). This suggests the possibility of a different organic component as a source of the interaction with iodine. This component could be the seeping hydrocarbons.

The lack of binding of iodine with surficial organic matter is supported by the soil types occurring in the study area. Soils generally contain 0.01-6 mg/kg of iodine (Kebata-Pendias and Pendias, 1984). The average content of iodine in continental shales and limestone is 1.8 ppm and 2.5 ppm, respectively, whereas greywackes and sandstones on average contain 150 ppb and 120 ppb, respectively (Muramastu and Wedephol, 1998). Most of the Saurashtra Peninsula is covered with red soils which are weathering products of the basalts, together with alluvium and some black soil (Merh and Chamyal, 1993). These soils are highly argillaceous and contain high proportions of calcium and magnesium carbonates; however they are poor in organic matter. These soil lithologies have a low potential to fix iodine (Fuge, 1987). In the sampled area, the geometric mean value (g/ g) of bound iodine in soil fractions is <2.2 (Fuge and Johnson, 1986). However, iodine values reported here are significantly high, indicating the possibility of a different organic component source which may be seepage related. An increase in soil iodine is also observed to occur with an increase of hydrocarbon gas concentration at most locations in the study area (Fig. 8). A good correlation between the two variables can be seen, and the pattern of iodine anomalies matches with the soil gas anomalies, especially around Laloi and Khandera. Microseepage-related anomalies The near-surface expression of hydrocarbon microseepage may vary greatly but the mechanisms causing these variations are poorly understood. Diverse physico-chemical variations can cause non seepagerelated anomalies. To ascertain the occurrence of subsurface seepage, total scanning fluorescence (TSF), TOC/TIC and XRD studies were carried out on selected samples.

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Fig. 9. (a, above left). Three-dimensional (TSF) fluorogram of sample J-79. (b, above right). Three-dimensional (TSF) fluorogram of sample J-142. Table 2. Intensity (nm) and concentration (ppb) determined by fluorescence analyses of soil samples from the Jamnagar area.
Phenanthrene Intensity Conc. nm (ppb) 181.5 159.18 133.98 128.2 159.09 221.10 100.61 182.94 111.71 383.64 45.52 39.91 33.59 32.14 39.89 55.44 25.23 45.87 28.01 96.45 Anthracene Intensity Conc nm (ppb) 26.37 24.03 17.81 15.58 21.73 39.79 11.71 29.95 17.52 81.60 2.91 2.65 1.96 1.72 2.39 4.39 1.29 3.31 1.94 9.08 Naphthalene Intensity Conc nm (ppb) 172.04 200.98 268.44 255.44 241.29 489.46 197.01 265.97 214.88 408.75 25.91 34.64 55.75 51.69 47.26 124.90 33.41 54.98 38.99 99.66

Sample ID

J/10 J/20 J/26 J/39 J/51 J/55 J/79 J/122 J/141 J/142

Fluorescence spetrometry Ultraviolet fluorescence spectrometry can be used to detect and measure aromatic hydrocarbons in nearsurface soils and sediments which may have migrated from underlying reservoirs (Abrams, 2005; Barwise and Hay, 1996). Recent organic matter, oil spills and non petroleum-related compounds also fluoresce, but the maximum fluorescence of these compounds is obtained at different wavelengths and intensities, allowing them to be discriminated from migrated hydrocarbons. In total scanning fluorescence (TSF), the maximum fluorescence intensity (MFI) is recorded

along with the emission wavelength (Max_Em) and excitation wavelength (Max_Ex) (Brooks et al., 1983; Abrams, 2005). The results of fluorescence studies are summarized in Table 1 and the details with MFI data are given in Table 2. It is notable that naphthalene, phenanthrene and anthracene occur in all the samples analysed by fluorescence spectrometry. Three-dimensional fluorograms of two samples (J-79 and J-142) are shown in Figs. 9a and 9b. The MFI for these samples is 480 and 705 nm, respectively. The overall pattern of fluorescence intensities and concentrations are

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Near surface geochemical data, Saurashtra Basin, India

60

TOC
50
TOC/TIC (p ppmx1000)

TIC

Fig. 10. Variation of TOC and TIC with C2+ hydrocarbons.

40 30 20 10 0 0 200 400

R (TIC) = 0.05

R (TOC) = 0.2

600 800 C2+ (ppb)

1000

1200

Table 3. Data of light hydrocarbon gases with minerals and clays identified using XRD in soil samples from the Jamnagar area.

Sample C1
J/10 J/51 J/79 J/122 J/142 J/20 J/26 J/39 J/55 J/141 121 223 321 202 103 39 35 34 33 28

Light Gaseous concentration (ppb) C2

48 137 222 131 30 8 17 5 8 11

Mineralogy n-C5
0 6 13 0 0 0 0 0 0 0 Carbonate Quartz Feldspar Smectite Smectite Quartz Feldspar Carbonate Quartz Smectite Feldspar Carbonate Quartz Feldspar Smectite Carbonate Smectite Carbonate Quartz Feldspar Carbonate Quartz Feldspar Smectite Quartz Carbonate Feldspar Smectite Carboanate Quartz Feldspar Smectite Carbonate Quartz Feldspar Smectite Carbonate Quartz Feldspar Smectite

C3
27 66 149 99 20 4 10 3 5 6

i-C4
3 6 22 17 0 0 0 0 0 1

n-C4
3 14 58 40 0 0 0 0 0 3

i-C5
0 0 0 4 0 0 0 0 0 0

consistent with other geochemical parameters measured, and indicate the possibility of seepagerelated compounds in the near-surface soils. TOC/ TIC contents A check on false anomalies can be achieved from the TOC/TIC content (Abrams, 2010; Brekke, 1997). Traces of light hydrocarbons such as ethane, propane, butane and pentane, as well as methane, are produced by microbial activity on surficial organic matter and have previously been reported (Hunt, 1980; 1981; 1984; 1995; Klusman; 1996). If the light hydrocarbon gases are assumed to be derived from deep-lying, organic-rich source rocks associated with oil and gas accumulations, then the TOC of near-surface organic matter should show a poor correlation with the concentration of light hydrocarbon gases. Mineralogical differences in soil samples can also cause false anomalies (Brekke, 1997). The TOC

andTIC content of fifty-three soil samples from the Saurashtra Peninsula showed a very poor correlation (r2 << 1) with the acid-extracted ethane and higher hydrocarbon yield (C2+) (Fig 10). This suggests that the adsorbed gases in the soil samples do not have any correlation with the organic matter of the surficial sediments, supporting the likeliness of a seepageinduced anomaly. To further discriminate carbonate-induced anomalies in the near-surface sediments, ten samples with varying gaseous hydrocarbon concentrations were subjected to X-ray diffraction studies. The XRD analyses showed that clays, carbonates, quartz and feldspar were the main mineral phases. Table 3 shows the mineralogy and light gaseous hydrocarbon concentrations of the selected soil samples, and the XRD spectra typical of high and low gas concentration are represented in Figs. 11a and 11b, respectively. A trend that is evident from the XRD observations is

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Fig. 11a. XRD spectrum of soil sample J-79 showing that this sample with a high gas yield has a mineral assemblage dominated by clays and quartz.

J-79

Fig. 11b. XRD spectrum of soil sample J-39 showing that this sample with a low gas yield has a mineral assemblage dominated by carbonates.

J-39

that higher gas yields are represented by a mineral assemblage in which quartz and clays are dominant. The increased presence of carbonates is typical of samples with a comparatively lower light gaseous hydrocarbon concentration. Hence, it is unlikely that the occurrence of light hydrocarbon gases in the nearsurface soils of the Jamnagar area is carbonate induced. INTEGRATION OF GEOCHEMICAL DATA WITH GEOLOGICAL AND GEOPHYSICAL DATA A model integrating the geochemical observations with geological and geophysical data is shown in Fig. 12. Focussed fluid migration along faults, discontinuities or unconformities is more effective than non-focussed seepage through a sedimentary column (Abrams, 1992; Brown, 2000). Intrusions, such as sills and dykes, represent preferential pathway for fluid migration and may be associated with active hydrocarbon seepage (Gay et al., 2006; Rollet et al., 2006). A series of dolerite dykes mainly trending NESW and NW-SE occur in the Saurashtra Peninsula. The Jamnagar area is almost entirely covered by the Deccan Trap volcanics and numerous dykes are present. Two NNW-trending faults are identified 40 km west and 30 km east of Jamnagar, respectively

(Reddy, 2005), and a major NNW trending dyke occurs close to Khankotda (Chopra et al., 2008). Light hydrocarbons and soil iodine concentrations were plotted on the map of dykes and lineaments (Fig. 12). High values of light hydrocarbons were seen around the dykes and lineaments, particularly in the south. In the NE where dykes and lineaments are absent, soil hydrocarbon concentrations appear to be low. Thus elevated hydrocarbon and iodine concentrations are coincident with dykes and lineaments, which probably serve as preferential conduits for micro-seepage of hydrocarbons. Geophysical studies (Satpal et al., 2006) show that thick Mesozoic sediments (about 2 km) occur in the NW of the Saurashtra Peninsula around Jamnagar. The Deccan Traps are in general 1.53 km thick in the south, but are thinner in the NW, possibly allowing the migration of hydrocarbons towards the surface here. A map of light gaseous hydrocarbons C2+ contoured over the Mesozoic sediment thickness (Satpal et al ., 2006) is shown in Fig.12. The concentrations of adsorbed light hydrocarbons correlate well with sediment thickness, and high concentrations occur over areas with higher sediment thicknesses, especially near Laloi. When the concentrations of hydrocarbons are related to Trap thickness, it appears that the adsorbed gas anomalies are located in areas where Trap thickness is less

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Near surface geochemical data, Saurashtra Basin, India

Dyke Fault & Lineament Depth (m) C2+(ppb) Iodine (ppm)

Fig. 12. An integrated model of the geochemical (adsorbed hydrocarbons C2+ and iodine), geological (dykes, faults and lineaments), and geophysical (sediment,Trap and basement thickness) details of the Jamnagar area, Saurashtra Peninsula.

compared to other regions. Thus the surface prospecting methods complement the geological and geophysical results available for the area. CONCLUSIONS Using an integrated approach involving near-surface geochemical indicators, light gaseous hydrocarbons and their isotopic compositions and soil iodine concentrations, this study suggests that thermogenic hydrocarbons occur in the subsurface of the basaltcovered onshore Saurashtra Basin. Elevated concentrations of adsorbed hydrocarbon gases were observed around Laloi and around Khandera. A few point anomalies are scattered south of Kalavad and Matwa. Fluorescence studies showed the presence of high molecular weight hydrocarbon, not indigenous to near-surface soils, and indicate that the occurrence of near-surface PAHs (napthalene, anthracene and phenanthrene) is seepage related. The concentrations of light hydrocarbon gases correlate well with soil iodine concentrations. Near-surface lithology and mineralogy as indicated by the XRD, TOC, and TIC studies rule out the possibility of false near-surface anomalies, indicating the sources of theses gases to be deep-seated. The geochemical

results are in accordance with the occurrence of dykes, faults and lineaments which may be migration conduits. ACKNOWLEDGEMENTS D.M. is grateful to the Council for Scientific and Industrial Research (CSIR) for a Research Associateship. B. Kumar is thanked for the encouragement to pursue the study. C. Vishnu Vardhan and M. A. Rasheed are acknowledged for their contributions towards the fieldwork. K. Ravi Kumar (CSIR-IICT, Hyderabad) is acknowledged for XRD analyses. The authors thank the Director, CSIRNGRI, for permitting the publication of this work. The Oil Industry Development Board, New Delhi, is acknowledged for providing financial assistance for setting up of geochemical facility. Journal reviews by P. K. Saraswasti and S. Dutta are acknowledged with thanks. REFERENCES
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Supporting information Additional supporting information may be found in the online version of this article: Appendix S1. Geochemical results of soil sample analyses and coordinates of sample locations. Appendix S2. Certified and measured concentrations of iodine with standard deviations (%) using ICPMS in soil reference materials. Please note: Wiley-Blackwell are not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing material) should be directed to the corresponding author for the article.