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Geochemistry and field spectrometry for detecting hydrocarbon microseepage

H. Yang1*, J. Zhang2, F. van der Meer1, S. B. Kroonenberg3
1

International Institute of Aerospace Survey and Earth Sciences (ITC), P.O. Box 6, 7500 AA Enschede, The Netherlands, 2Institute of Remote Sensing Applications, Chinese Academy of Sciences, P.O. Box 9718, Beijing 100101, PR China, 3Faculty of Applied Earth Sciences, Delft University of Technology, Mijnbouwstraat 120, 2628 RX Delft, The Netherlands inflection point positions of spectra on oil-field wheat were shifted 7 nm to longer wavelengths than off-field wheat samples, and can be positively correlated with the delta carbonate and soil-gas. The absorption of soil spectra at 2.346 mm is at least 0.2% higher over oil-fields than off-fields. This research proves that remote sensing can be used in an monocultural agricultural area to detect hydrocarbon microseepage. Terra Nova, 10, 231235, 1998

ABSTRACT

Remote sensing detection of hydrocarbon reserves would be a valuable addition to conventional methods used currently. Tests were made in a drilled, proven hydrocarbon area predominantly covered by wheat. Field-spectroradiometers measured spectral characteristics of wheat and soil associated with hydrocarbon microseepage. Soil gas and secondary carbonate produced only by hydrocarbon microseepage were at anomalously high levels at the oilwater or gaswater boundaries. Kaolinite and illite in the soil have higher percentages above petroleum reservoirs. The

Introduction
Hydrocarbon seepages are seeping hydrocarbons moving to the surface through their seal rocks, while microseepages are invisible seeping light hydrocarbons that can be detected (chemically) only at the surface (Tedesco, 1995). Satellite-based remote sensing has been used to delineate various hydrocarbon-induced surface manifestations including red-bed bleaching (Donovan, 1974; Malhotra et al., 1989; Segel and Merin, 1989), clay minerals alteration (Segel and Merin, 1989), carbonate anomalies (Patton and Manwaring, 1984; Simpson et al., 1991; Zhu and Zhang, 1991; Thompson et al., 1994) and geobotanical anomalies (Bammel and Birnie, 1994; 1985b; Lang et al., 1985a; Crawford, 1986; Reid et al., 1988; McCoy et al., 1989; Cwick et al., 1995; de Oliveria and Crosta, 1996). Few publications exist on the spectral characteristics of soils and rocks affected by hydrocarbon microseepage. Most research efforts are directed toward mapping geobotanical anomalies in the vegetation canopy where the emphasis is on areas of natural vegetation. The general perception is that vegetation stress due to geological factors can be demonstrated because the red-edge of the vegetation spectrum shifts to shorter wavelength (i.e. the `blue shift'; Collins et al., 1983). Due to the complexity of environmental fac*Correspondence: Tel. + 31/53-4874248; Fax: + 31/53-4874336; E-mail: yang@itc.nl
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tors associated with natural vegetation and the numerous disturbing factors, no statistical confidence can be given to these previous results. We present the results of field spectroscopic analysis for the detection of hydrocarbon microseepages in a monocultural agricultural area planted with Triticum aestivum (spring wheat) and show that spectral characteristics of wheat and soil can be associated with light hydrocarbons at the surface.

The study area

The study area is located 8 km north of the city of Changyi, south of the Yellow River Delta in eastern China. The Wei River dissects the study area and drains to Bohai Bay. Geologically, the area is formed by a marginal basin around the second largest oil field in China. Oil reservoirs are structurally controlled; the main oil reserve structures in the marginal basin are inherited and include fault-noses and fault-related structures. The source rock is a dark mudstone of early Eocene age and the main reservoir rocks containing oil and gas accumulations are sandstones of early and late Eocene age. Reservoirs are located at depths of 5001000 m below the surface. We selected two transects across two structural traps in a drilled proven area with available soil-gas data. At regularly spaced survey points, surface soil samples were collected for analysis of carbonate and clay mineral analysis while wheat and soil spectra were measured in the field using two spectro-

radiometers: (i) an IRIS Mark-V fieldspectroradiometer, which measures the 0.42.5 mm wavelength range using sunlight as the energy source and (ii) a PIMA (i.e. Portable Infrared Mineral Analyser) which measures the 1.32.5 mm wavelength range using an internal light source. The IRIS Mark-V in the 0.41.050 mm range has a spectral bandwidth of less than 2 nm and from 1.0502.5 mm the bandwidth is less than 4 nm. Our survey was conducted in early May 1997, while the wheat was green before ear development. At every survey point, we randomly collected wheat stems with leaves in an area with a radius of 10 m, enough to divide them into 3 groups, each with 3 layers of stems. We placed the part with thick leaves under the lens and measured the 3 samples one-by-one for 18 field stations. Measurements in each transect were accomplished within two days with operating times between 11:00 and 15:00 hours in order to minimize diurnal effects and distortions related to observational geometry. Delta carbonate in soil It is widely accepted that light hydrocarbons, while migrating to the surface from a petroleum reservoir, react with oxygen in the near-surface oxidation environment producing carbon dioxide and water. The produced carbon dioxide continues to migrate upwards and reacts with water and salts resulting in secondary carbonate (referred to as `delta carbonate'). Delta carbonate
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Geochemistry and field spectrometry for detecting hydrocarbon microseepage
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prospecting for hydrocarbons exploits this process by measuring the yield of carbon-dioxide released from carbonate by thermal decomposition (DTA) within a given temperature range (Duchscherer, 1986). The amount of carbon dioxide measured using this approach can be used as an indicator for the presence of hydrocarbon resources in the subsurface. In the laboratory, the 18 soil samples were thermally decomposed at temperatures between 500 and 600 8C to release carbon dioxide. The 18 delta carbonate values varied from 0.13 to 0.33 W(CO2)/1072. Duplicate analyses gave identical results. The delta carbonate content of the oil-affected sample was found to be 0.28 W(CO2)/1072, which implies that if delta carbonate content is greater or equal to 028 W(CO2)/1072, the soil is likely to have been affected by hydrocarbon. Ethane concentration (Xu, 1996), delta carbonate and spectral characteristics as well as subsurface geology constrained from seismics (after Xu, 1996) are shown in Fig. 1 and Fig. 2.

Clay minerals Segel et al. (1984) found that the bleached portion of the Wingate sandstone directly overlying an oil field had three to five times more kaolinite than the unbleached rock. The geographical distribution of the kaolinite is inversely related to that of the mixed-layer illite smectite clays, suggesting that the enrichment of kaolinite is related to the depletion of other clay minerals and not only to the alteration of feldspars. Lilburn and Al-Shaieb (1984) discovered that kaolinite and mixed-layer illitesmectite clays of late origin replaced detrital illite in red beds. In this study, we investigated the clay mineralogy of the soils in relation to the subsurface structure and hydrocarbon occurrences over two sections to find additional evidence supporting petroleum prospecting based on spectral characteristics of soil and vegetation. Clay minerals were extracted from soil samples and placed onto a glass plate. X-ray diffraction showed that mixed-layer illitesmectite is the domi-

nant clay mineral; kaolinite, chlorite and vermiculite are smaller fractions of the total weight. Although the overall clay mineral concentration is controlled by the parent materials and weathering processes, the relative clay mineral concentration can be used to evaluate whether clay mineral conversion exists or not. We collected an oilaffected soil sample and found that both kaolinite and illite form a larger constituent compared with a noncontaminated soil sample taken at the same point as shown in Table 1. Soils affected by hydrocarbon microseepages, according to our analysis, typically show low contents of mixed-layer illitesmectite (5 81%) and higher kaolinite + illite content (4 11%). Spectral reflectance of wheat For the reflectance spectra measured along the two transects, we calculated the first derivative spectra in order to determine the wavelength position of the red-edge position (the inflection point) defined as the wavelength of

Fig. 1 Inflection point position, delta carbonate, soil-gas and soil absorption depth at 2346 nm along transect 1.

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Fig. 2 Inflection point position, delta carbonate, soil-gas and soil absorption depth at

2346 nm along transect 2.

Table 1 Clay minerals in soil along two transects.

Description of sample Relative content of clay minerals (%) location in relation to reservoir Illite/smectite illite kaolinite chlorite vermiculite Outside of reservoir Outside of reservoir Oilwater boundary Contaminated at 13 Over oil field Oilgas boundary Over gas field Over gas field Over oil field Outside of reservoir Outside of reservoir Outside of reservoir Over oil field Over oil field Oilwater boundary Outside of reservoir Near a fault by reservoir Over oil field Over oil field 85 82 81 78 72 75 81 79 81 84 83 87 80 78 81 85 75 80 66 7 9 8 13 17 14 9 11 8 9 10 7 10 11 9 7 13 10 19 3 2 3 4 3 3 2 3 5 2 2 2 3 3 3 3 3 3 6 2 2 3 3 3 3 2 2 3 2 2 2 2 2 2 2 3 2 4 3 5 5 2 5 5 6 5 3 3 3 2 5 6 5 3 6 5 5

Sample No. 11 12 13 13' 14 15 16 17 18 21 22 23 24 25 26 27 28 29 210

wheat samples on areas without microseepage were found to be located at a wavelength position of 0.73826 mm while an anomalous value of 0.74443 mm was associated with hydrocarbonaffected samples. The inflection point of the survey points above oil-gas intersections was found to be at a wavelength position of 0.74443 mm; a red shift of about 7 nm. To further strengthen our results, linear, logarithmic and quadratic regression analyses were performed between the calculated inflection point positions and the delta carbonate content (Fig. 3) and ethane content (Fig. 4). The number of observations in the first regression analysis is 36; this includes the 18 soil samples and their parallel tests for the delta carbonate analysis vs. the first two sets of red-edge positions inferred from the field spectral analysis. The number of observations in the second regression analysis is 18, including 18 ethane measurements vs. the first set of red-edge positions. The correlation coefficients observed for the first analysis (Fig. 3) are 0.70, 0.719 and 0.724 for the linear, logarithmic and quadratic regression analysis, respectively. The calculated Fs (Freese, 1990) are 33.01, 36.51 and 18.51, respectively. These exceed the tabular F0.05 with 1/ 36 d.f.; thus the regression is deemed significant at the 0.05 level. The correlation coefficients observed from the second analysis (Fig. 4) are 0.709, 0.745 and 0.725 for the linear, logarithmic and quadratic regression analysis, respectively. The calculated Fs in this case are 16.21, 19.78 and 8.3, respectively, again greater than the tabular F0.05 with 1/18 d.f., thus the regression is deemed significant at the 0.05 level. Spectral reflectance of soil Soil samples taken near the drilled wells have low reflectance. They have distinct absorption features at 1.720, 1.760, 2.310 and 2.330 mm, similar to those of crude oil. Hunt (1986) studied reflectance spectra of particulate samples of minerals that commonly occur in soils and found that features in the 2.2 mm region are particularly valuable because they are common to alteration minerals, allowing discrimination from nonalteration minerals which provide features near 2.4 mm. In the alkaline soils in Changyi area, we identified clay minerals and calcite. The previous dis233

maximum dR/d (i.e. change of reflectance over wavelength increment). We found that the inflection points of all measurements fall into the 0.73517 0.74751 mm wavelength region (Fig. 1).
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Comparison of all sets of three spectral measurements at each survey point showed a maximum variability of 2 nm in the estimated position of the inflection point. Inflection points for

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Geochemistry and field spectrometry for detecting hydrocarbon microseepage
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Fig. 3 Inflection point position vs. delta carbonate.

Fig. 4 Inflection point position vs. ethane concentration.

cussion shows that samples that have low concentration of mixed-layer illitesmectite and high concentrations of illite plus kaolinite are likely to be located on oil fields. At the wavelength region of 2.2 mm2.4 mm, kaolinite has spectral absorption bands at 2.209, 2.322, 2.357 and 2.382 mm; illite has spectral absorption bands at 2.211, 2.347, and 2.383 mm; and calcite has spectral absorption bands at 2.305 and 2.337 mm. The depth of the soil absorption features measured in Changyi area was calculated using Hull difference. A Hull is a series of segments that connect various local reflectance maxima within the spectrum. Hull difference is the reflectance difference between the Hull and the spectrum at the band minimum. The absorption band near 2346 nm has been found to be diagnostic. The Hull difference of soil at 2346 nm is 0.2% higher on oilfield than off-field. The Hull difference at 2346 nm of soil is also plotted in Figs 1 and 2.

Discussion
The delta carbonate content of soil is high at the surface overlying an oil water contact or near a fault. Ethane, not known to be produced by biological processes, also has anomalous values at such locations, which indicates that surface alteration is related to subsurface lithology and structure. Could pollution be considered a source of light hydrocarbons at the surface? The hydrocarbon soil-gas measurements from spills that enter the soil system are typically in parts
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per million to percentage range and are thus very distinctive from the analysis related to natural petroleum accumulations. Another reason that the soil-gas high is not the result of contamination due to pollution is that the soil-gas samples were taken before drilling, which means that there was no pollution source. No signs of stress were observed in the wheat visually; however, the soils above oil and gas traps, were found to have clay mineral associations that are distinctly different. In cases where both kaolinite and illite percentages in the soil are high, the survey point is located above an oil or gas trap; the reason behind this association remains unclear. For wheat spectra, we found that the red-edge inflection point for samples taken on an oil-field shifted 6 to12 nm to longer wavelengths. For soil spectra, the absorption area near 2.346 mm was found to be diagnostic for on/off field identification. If the absorption area is large, the survey point is on-field; if the absorption area is small, the survey point is off-field. Can these measured characteristics of the soil and wheat spectra be diagnostic for hydrocarbon microseepages and as such be used to aid in the detection of surface manifestations of hydrocarbons in the subsurface? As modern silty and subsandy soils in the investigated area developed on alluvial deposits of similar origin, the soil composition can be considered homogenous over the surveyed transects. In a flat area, such as the Changyi area, micromorphology at the sample points can be considered as invariable. The surface conditions at all measured locations are identical, which leads us

to look for reasons underground. Hydrocarbon microseepage is likely to be a suitable argument. We are currently working on the extension of field spectral characteristics to airborne hyperspectral data. An airborne survey with the Chinese Modular Airborne Imaging Spectrometer (MAIS; Van der Meer et al., 1997) has been conducted in the investigated area. With these data we hope to achieve the goal of detecting hydrocarbon microseepage using remote sensing data.

Acknowledgements
The authors wish to thank the Exploration Company of the Shengli oil field for providing soil-gas data. We also owe great debt to Mr Jinxian Sun and Mr Wenyi Zhou of the Agricultural Bureau of Changyi City for their assistance during the fieldwork. We thank Mr Qingjiu Tian of Chinese Academy of Sciences, for his help in measuring the field spectra. Mr Tongjin Cheng of the Geochemistry Center of the Bureau of Petroleum and Marine Geology, performed the delta carbonate analyses and Mr Xiusheng Lin from the China National Petroleum Corporation analysed the clay mineralogy. We wish to specially thank Dr Chris Clayton and for his critical review that have helped to improve the manuscript.

References
Bammel, B.H. and Birnie, R.W., 1994. Spectral response of big sagebrush to hydrocarbon-induced stress in the Bighorn Basin Wyoming. Photogramm. Engng Remote Sens., 60(1), 8796. Collins, W., Chang, S.-H., Raines, G., Canney, F. and Ashley, R., 1983. Airborne biogeophysical mapping of hidden mineral deposits. Econ. Geol., 78, 737749.
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H. Yang et al.

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Crawford, M.F., 1986. Preliminary evaluation of remote sensing data for detection of vegetation stress related to hydrocarbon microseepage: mist gas field, Oregon. In: Proceedings of the Fifth Thematic Conference: Remote Sensing for Exploration Geology, 29 September2 October, Reno, Nevada, USA, pp. 161177. Environmental Research Institute of Michigan, Ann Abor, MI. Cwick, G.J., Bishop, M.P., Howe, R.C., Mausel, P.W., Everitt, J.H. and Escobar, D.E., 1995. Multispectral video data for detecting biogeochemical conditions at an Alabama oil field site. Geocartogr. Int., 10(2), 5966. Donovan, T.J., 1974. Petroleum microseepage at Cement, Oklahoma: evidence and mechanism. Bull. Am. Ass. Petrol. Geol., 58, 429446. Duchscherer, W., 1986. The principle of delta carbonate geochemical hydrocarbon prospecting demonstrated. In: Unconventional Method IV, pp. 1416. Southern Methodist University Press, Dallas, TX. Freese, F., 1990. Statistics for Land Managers, 2nd edn. Paeony Press, Edinburgh. Hunt, G.R., 1986. Near-infrared (1.32.4 mm) spectra of alteration minerals Potential for use in remote sensing. Geophysics, 44(12), 19741986. Lang, H.R., Aldeman, W.H. and Sabins, F.F. Jr, 1985a. Patrick Draw, Wyoming petroleum test case report. In: The Joint NASA/Geosat Test Case Project: Final Report (M.J. Abrams, J.E. Conel, H.R. Lang and H.N. Paley, Eds). Spec. Publ. Am. Ass. Petrol. Geol., 2(2), 11-111-28. Lang, H.R., Curtis, J.B. and Kovacs, J.C., 1985b. Lost river, West Virginia petroleum test site report. In: The Joint NASA/Geosat Test Case Project: Final Report (M.J. Abrams, J.E. Conel, H.R. Lang and H.N. Paley, Eds). Spec. Publ. Am. Ass. Petrol. Geol., 2(2), 12-112-96. Lilburn, R.A. and Al-Shaieb, Z., 1984. Geochemistry and isotopic composition of hydrocarbon-induced diagenetic aureole (HIDA), Cement, Oklahoma. Oklahoma City Geol. Soc. Shale Shaker, 34(5), 5767.

Malhotra, R.V., Birnie, R.W. and Johnson, G.D., 1989. Detection of surfacial changes associated with hydrocarbon seepage sheep mountain anticline, bighorn basin, Wyoming. In: Proceedings of the Seventh Thematic Conference on Remote Sensing for Exploration Geology, 26 October, Calgary, Alberta, Canada, pp. 10971110. Environmental Research Institute of Michigan, Ann Abor, MI. McCoy, R.M., Scott, L.F. and Hardin, P., 1989. The spectral response of sagebrush in areas of hydrocarbon production. In: Proceedings of Seventh Thematic Conference on Remote Sensing for Exploration Geology, Environment Research Institute of Michigan, Ann Arbor, MI, USA, pp. 751756. de Oliveria, W.J. and Crosta, A.P., 1996. Detection of hydrocarbon seepage in the Sao Francisco basin, brazil, through Landsat TM, soil geochemistry and airborne/field spectrometry data integration. In: Proceedings of the Eleventh Thematic Conference and Workshops on Applied Geologic Remote Sensing, 2729 February, Las Vegas, Nevada,USA, pp. I-155I-165. Environmental Research Institute of Michigan, Ann Abor, MI. Patton, K.H. and Manwaring, M.S., 1984. Evaluation of a Landsat derived tonal anomaly for hydrocarbon microseepage, Southwest Kansas. In: Proceedings of the International Symposium on Remote Sensing of Environment, Third Thematic Conference, Remote Sensing for Exploration Geology, 1619 April, Colorado Springs, Colorado, USA, pp. 441450. Environmental Research Institute of Michigan, Ann Abor, MI. Reid, N., Iwashita, A., Yamashita, Y. and Thompson, K., 1988. High resolution imaging of geobotanical anomalies associated with subsurface hydrocarbons. In: Proceedings of the Sixth Thematic Conference on Remote Sensing for Exploration Geology, Huston, Texas, USA, Vol. 1, pp. 213223. Environmental Research Institute of Michigan, Ann Abor, MI. Segel, D.B. and Merin, I.S., 1989. Successful use of Landsat Thematic Mapper data for

mapping hydrocarbon microseepageinduced mineralogic alteration, Lisbon Valley, Utah. Photogramm. Engng Remote Sens., 55(8), 11371145. Segel, D.B., Ruth, M.D., Merin, I.S., Watanabe, H., Soda, K., Takano, O. and Sano, M., 1984. Correlation of remotely detected mineralogy with hydrocarbon production, Lisbon valley, Utah. In: ERIM Proceedings of International Symposium On Remote Sensing For Exploration Geology, pp. 273292. Environmental Research Institute of Michigan, Ann Abor, MI. Simpson, C.J., Wilford, J.R., Macias, L.F. and Korsch, R.J., 1991. Remote sensing of petroleum gas seepage alteration palm valley gas field, Amadeus basin, central Australia. In: Proceedings of the Eighth Thematic Conference on Geologic Remote Sensing, 29 April2 May, Denver, Colorado, USA, pp. 14631472. Environmental Research Institute of Michigan, Ann Abor, MI. Tedesco, S.A., 1995. Surface Geochemistry in Petroleum Exploration. Chapman & Hall, New York. Thompson, C.K., Saunders, D.F. and Burson, K.R., 1994. Model advanced for hydrocarbon microseepage, related alterations. Oil and Gas J., 14, 9599. Van der Meer, F., Fan, L. and Bodechtel, J., 1997. MAIS Imaging spectrometer data analysis for Ni-Cu prospecting in ultramafic rocks of the Jinchuan group, China. Int J. Remote Sens., 18(13), 2743 2761. Xu, W., 1996. Rapid geochemical prospecting for oil and gas. In: Recognition and Prospecting of Natural Gas (Y. Yang and W. Han, Eds), pp. 86 100. Petroleum University Press, Shangdong, China Zhu, Z. and Zhang, J., 1991. Detecting oil and gas resources in the east of Junggar Basin, Xinjiang. In: Proceedings of the 12th Asian Conference on Remote Sensing, Singapore, October, Vol. II, P.I-4-1.

Received 8 July 1998; revised version accepted 21 December 1998

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