Energy Sources, Part A, 29:13611370, 2007 Copyright Taylor & Francis Group, LLC ISSN: 1556-7036 print/1556-7230 online

e DOI: 10.1080/15567240701476694

Mossbauer Spectroscopy of Kerogen Isolated from Miocene Petroleum Source Rocks of Three Fields in the Area of Suez Gulf, Egypt
I. KASHIF
Faculty of Science, Physics Department Al Azhar University Cairo, Egypt

M. A. AHMED
Faculty of Science, Physics Department Taif University KSA

E. A. ABDELGAWAD
College of Science, Geology Department UAE University Al Ain UAE
Abstract The method of using room temperature Mossbauer spectroscopy were applied to identify the iron species in kerogen is illustrated for a series of 22 subsurface core samples from three oil elds: July, GS315 and Esh El-Melaha in the Gulf of Suez region, Egypt. The Mossbauer spectra of kerogen showed only two central quadrupole doublets that would be attributed to the presence of iron in pyrite/Fe2C (low spin) and in carbonates possible ankerite/Fe2C (high spin). Possible explanation for the presence of ankerite is discussed and it is suggested that a high level of maturation is the most likely reason. This suggestion is corroborated by data of the total organic carbon and the vitrinite reectance which is available for all the samples studied. Keywords kerogen, Mossbauer spectroscopy, petroleum source rock

Introduction
Oil prospecting in the Gulf of Suez is very difcult, due to many uncertainties. Seismic data are often of limited value, since thick intervals of evaporates tend to hide the underlying structures from seismic investigation. Another problem is that nearly all organic rich horizons in the Gulf of Suez are depleted in Humic macerals, and if vitrinite particles are found, their reectance is lowered in presence of high amounts of liptinite rich algal kerogens (Hutten et al., 1980). In addition, the use of Rock-Eval analysis would
Address correspondence to M. A. Ahmed, Taif University, Faculty of Science, Physics Dept., El Taif 888, Saudi Arabia. E-mail: mamdouh_2000_2000@yahoo.com

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not be reliable in these lithologies, (Tissot et al., 1987). Consequently, application of conventional analysis techniques such as total organic carbon and/or vitrinite reectance requires a combination with other tools in order to be more informative in determination of the digenesis of the organic sediments. Last Century witnessed a high performance for Mossbauer spectroscopy (MS) as a standard research method to study a wide variety of materials containing iron, as well as to identify different iron transformation (Stevens et al., 1988; Garcia et al., 1999). In this article, we report original Mossbauer effect investigation of the iron phases found in kerogen, chemically isolated from 22 sub-surface core samples of three oil elds: July, GS315 and Esh El-Melaha in the Gulf of Suez region, Egypt. As received, samples have been conducted to the analysis of the total organic carbon (TOC) and its corresponding data is presented according to specimens depths in Table 1. Also, given in this table is a summary of maturation levels obtained as exceperssed by oil vitrinite reectance (%Roil vitrinite). The present Mossbauer study was undertaken with the aim to disclose the connection between the maturation levels in kerogen and the presence of ankerite.

Table 1 Data of TOC and vitrinite reectance for the 22 subsurface core samples studied by MS Depth, feet 9,536 9,570 9,670 9,734 9,801 9,811 5,287 5,290 5,299 6,052 7,327 7,527 3,580 3,590 3,599 3,656 3,662 3,664 3,722 3,764 3,811 3,982 TOC, wt% 0.854 2.800 0.521 0.989 0.278 0.593 1.060 0.793 0.713 0.651 0.818 1.820 0.352 0.877 0.977 0.732 0.349 1.120 0.814 0.550 0.740 0.278 Kerogen analysis %Roil vitrinite 0.58 0.72 0.64 0.72 0.69 0.69 0.38 0.37 0.43 0.42 0.42 0.54 0.53 0.69 0.61 0.46 0.46 0.48 0.46 0.57 0.65 0.39

Field July 1 2 3 4 5 6 GS-315 7 8 9 10 11 12 Esh El-Mellaha 13 14 15 16 17 18 19 20 21 22

Well J10-70
00 00 00 00 00 00

Age/Fm L. Rudes
00 00 00 00 00

GS-315-1
00 00 00 00 00

Belayim
00 00

GS-315-B2 EM-4
00 00 00 00 00 00 00 00 00 00

Kareem U. Rudes Kareem Kar/Rudes

00 00 00 00 00 00 00 00

S. Gharib

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Experimental
Sample Preparation Proper grinding of the samples is necessary. About 9 g of a sample (handpicked and washed with distilled water) are treated for 10 sec in a tempered chrome steel mortar of a vibratory cup mill. After 10 sec, the mortar is opened and the sample powder is brushed carefully from the side wall cover and the grinding set of the mortar. The grinding is then repeated again for 10 sec. Analysis of the grain size distribution have showed that the sample is then equivalent to 250 mesh (<63 m). After brushing and homogenizing, the sample is manually split and 7 g are taken away for Kerogen isolation. The remaining 2 g are ground again for 3 10 sec in the manner described above. After the 5th treatment, the sample size was smaller than 10 m and it is now ready for TOC analysis. Total Organic Carbon Total organic carbon (TOC) in the samples as received was measured by LECOS 244 analyzer. The instrument is a simultaneous carbon-sulfur automatic analyzer based on combustion in a high frequency induction furnace followed by infrared detectors to quantify the evolved gases. TOC analyses were run on sample pretreated with HCl (10%) for carbonate removal. Kerogen Isolation The procedure used for kerogen isolation was that described by Ganz (1986) and Ganz et al. (1987, 1990). Before isolation, a few drops of Methanol are added into the samples in order to enhance their wettability. A careful HCl (10%) treatment is then used for the destruction of carbonates. The solution is decanted after centrifuging and the sample is treated with conc. HF (about 15 ml). In order to obtain a good suspension, the mixture is stirred carefully. Up to 24 beakers are placed in water bath at 70 C for about 48 hrs (Dinkelberg Laktotherm). Each day the beakers are lled up with additional HF and distilled water. The solution is decanted after centrifuging and treated with hot HCl (20%) to remove uorides that might have formed during the dissolution of the minerals. The amount of newly formed uorides depends mainly on the content of clay minerals and would be prevented if centrifuging and washing of the samples is practiced every 12 hrs. After HCl treatment, the samples are washed twice with hot distilled water and dried after decantation at 60 C in an ordinary laboratory oven. Since up to 24 samples (or 48 samples if using 2 water baths) are isolated at one time, total working time for the kerogen isolation procedure is less than 15 min/sample. Comparison with cold acid techniques used in earlier studies (Ganz 1986) indicates that the hot acid treatment and the drying at elevated temperatures for a limited time do not inuence the composition of kerogen. After drying, the kerogen is ground by hand in an agate mortar for 2 min. Measurement of the grain size distribution has revealed that the diameter of the particles is smaller than 10 m. Kerogen samples are then ready for Mossbauer analysis at room temperature (RT). Mossbauer Measurements Kerogen samples were not exposed to any pre-chemical treatment before analysis by Mossbauer spectroscopy (MS). Mossbauer absorbers were prepared from the powdered

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kerogen, which was gently pressed in Plexiglas absorber holders. The sample thickness was 200250 mg per cm2 . Mossbauer spectra were obtained by a conventional time-mode spectrometer and 50 mci 57 Co/Rh source. Fe absorber at RT was used for calibration and for isomer shift (Fe ) calculation. Spectra were computer tted based on lorentzian line proles, using least-square minimization techniques. To obtain the goodness of t criteria the following aspects were considered: (1) Equal intensities (1:1) were assumed for the doublets, since no grain texture is expected; (2) standard errors of parameters (Chi squared); and (3) residuals (differences between original and tted spectra). Finally, each phase assigned in this paper is characterized by an isomer shift (Fe ), quadrupole splitting () and a relative spectral area in (%). In determining the relative areas it is assumed that the f-factors are equal for all the individual components and the relative areas then reect the relative amounts of iron in each phase.

Results and Discussion

TOC The TOC content of the Miocene possible source rocks in the areas under study is generally varies between 0.52.8 wt% (Table 1) except 4 samples <0.5 wt%. The maximum content occur in the lower Rudes rocks (Shale and limestone) and the Kareem formation (Shale). Vitrinite Reectance The maturation levels in the horizons studied here was found to be increased regularly with increasing depth as indicated by the increase of %Roil vitrinite from 0.39 (South Gharib formation) to 0.72 (lower Miocene, L. Rudied unite) (see again Table 1). The data of vitrinite reectance allowed the deduction that: (1) L. Rudes unite in the section of July oil eld is marginally mature (0.580.72 %Roil vitrinite); (2) U. Rudes unite in the section of GS-315 oil eld is immature; (3) Kareem/Rudes in the section of Esh Mellaha eld id immature (6 samples) to marginally mature (4 samples); and (4) Kareem/Belayim formations are immature (0.380.54 %Roil vitrinite). It is important to mention that although some of the above samples seem to be immature due to low vitrinite reectance (<0.6) but at the same time, these samples are considered as good potential for oil and gas, since it contain high amounts of TOC. Mossbauer Analysis Each iron bearing phase exhibits a characteristic Mossbauer absorption in an absorber and the resulting spectrum is thus, the superposition of a number of Mossbauer absorption due to different iron minerals present. Typical Mossbauer spectra of kerogen samples, recorded at room temperature are shown in Figures 1, 2, and 3a, 3b. The Spectra of all consisted out of two doublets, (labeled as P and A). Values of the calculated , and the relative area of each are given in Table 2 and are to some extent in agreement with those published in literature (Ahmed et al., 2003; Fajardo et al., 1999; Morup et al., 1984; Waanders et al. 2003). From the Mossbauer tted spectra, the respective components P and A were assigned as ferrous in pyrite and in carbonate possible ankerite. The analysis of the relative areas (%) for both allowed the deduction that the major phase is pyrite and the minor is ankerite. As pyrite is quite common in most of the

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Table 2 Values for the isomer shift , the quadrupole splitting , and the relative area RA of each kerogen sample
Field July 1 2 3 4 5 6 GS-315 7 8 9 10 11 12 Esh El-Mellaha 13 14 15 16 17 18 19 20 21 22 Depth, feet Phase 1 , mm/s C0.01 2 , mm/s C0.03 RA, % 3 , mm/s C0.03 Assignments Fe2C in pyrite Fe2C in ankerite Fe2C in pyrite Fe2C in ankerite Fe2C in pyrite Fe2C in ankerite Fe2C in pyrite Fe2C in ankerite Fe2C in pyrite Ferrous sulfates Fe2C in pyrite Ferrous sulfates Fe2C Fe2C Fe2C Fe2C Fe2C Fe2C Fe2C Fe2C Fe2C Fe2C Fe2C Fe2C in in in in in in in in in in in in pyrite ankerite pyrite ankerite pyrite ankerite pyrite ankerite pyrite ankerite pyrite ankerite

9,536 9,570 9,670 9,734 9,801 9,811

P A P A P A P A P S P S P A P A P A P A P A P A P S P S P S P A P S P S P S P A P A P S

0.28 1.23 0.25 1.23 0.27 1.25 0.26 1.25 0.28 1.38 0.30 1.42 0.26 1.28 0.26 1.26 0.24 1.28 0.23 1.25 0.24 1.34 0.28 1.48 0.27 1.34 0.22 1.33 0.29 1.40 0.29 1.29 0.26 1.36 0.26 1.36 0.22 1.32 0.30 1.22 0.24 1.18 0.25 1.31

0.57 2.27 0.61 2.29 0.64 2.34 0.64 2.40 0.66 2.56 0.63 2.33 0.59 2.31 0.64 2.34 0.67 2.48 0.68 2.54 0.69 2.57 0.61 2.07 0.66 2.36 0.76 2.69 0.71 2.60 0.66 2.40 0.61 2.14 0.65 2.32 0.73 2.69 0.59 2.71 0.53 1.92 0.61 2.20

91.90 8.00 77.50 22.50 53.30 46.60 59.20 50.70 83.50 16.50 67.50 32.40 82.50 17.40 70.30 29.60 59.40 40.50 56.90 43.00 69.70 30.20 92.90 7.00 60.70 39.20 43.40 56.50 57.10 42.80 56.70 43.20 89.50 10.40 87.90 12.00 43.40 56.50 65.90 34.00 65.00 34.90 83.50 16.40

0.33 0.22 0.34 0.38 0.33 0.41 0.32 0.56 0.37 0.35 0.32 0.65 0.30 0.31 0.35 0.45 0.32 0.40 0.36 0.41 0.33 0.33 0.33 0.15 0.27 0.44 0.32 0.39 0.32 0.39 0.29 0.40 0.34 0.32 0.37 0.38 0.32 0.39 0.40 0.55 0.23 0.46 0.32 0.44

5,287 5,290 5,299 6,052 7,327 7,527

3,580 3,590 3,599 3,656 3,662 3,664 3,722 3,764 3,811 3,982

Fe2C in pyrite Ferrous sulfates Fe2C in pyrite Ferrous sulfates Fe2C in pyrite Ferrous sulfates Fe2C in pyrite Fe2C in ankerite Fe2C in pyrite Ferrous sulfates Fe2C in pyrite Ferrous sulfates Fe2C in pyrite Ferrous sulfates Fe2C in pyrite Fe2C in ankerite Fe2C in pyrite Fe2C in ankerite Fe2C in pyrite Ferrous sulfates

a is the isomer shift and corresponding to the center of gravity of the two absorption maxima, measured relative to the center of gravity of an iron metal at RT. b is the quadrupole splitting and is the magnitude of the separation between the two absorption maxima. c is the line width which is the full width of the absorption line measured at half of the maximum intensity.

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Figure 1. RT Mossbauer Spectra of Kerogen samples isolated from July Field, Suez Gulf, Egypt. Depths in feet at which samples were collected are indicated.

ore substances, its presence in our kerogen samples is not unexpected. The range of values identied for pyrite, FeS2 is 0.69 mm/s to 0.57 mm/s for and 0.29 mm/s to 0.22 mm/s for Fe which is characterizing the ferrous ion in low spin conguration state and localized in slightly distorted octahedral symmetry. As the six d-electrons are occupying the T2g ground state, pure pyrite, (cubic) is not magnetic, (Ahmed et al., 1999). The other form of FeS2 , marcasite (orthorhombic) has nearly the same values of isomer shift and slightly smaller quadrupole splitting, but is not easily distinguished from pyrite lines in a Mossbauer spectrum when both are present. Moreover, Fe2C in clay minerals or in super paramagnetic oxides and hydroxides may have similar Mossbauer parameters and therefore contributions from such species to components P can not be excluded. Furthermore, the abnormal increase in the electric quadrupole splitting of pyrite in a few samples (c.f. samples 14 and 15) presumably reects the existence of signicant amounts

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Figure 2. RT Mossbauer Spectra of Kerogen samples isolated from GS-315 Field, Suez Gulf, Egypt. Depths in feet at which samples were collected are indicated.

of arsenic. In the absence of these impurities, the range of values for the Mossbauer parameters of pyrite is considerably reduced. The increase in the electric quadrupole splitting associated with the relatively high arsenic contents is far of potential importance as it suggests that 57 Fe Mossbauer spectroscopy of pyrite would be used to monitor the extent of arsenic solution in the pyrite lattice (Evans et al., 1982). It is reasonably certain that the second phase A represents iron in carbonate minerals. Siderite has been of general interest in theoretical Mossbauer studies and its Mosssbauer parameters are known (Sirvastava, 1983; Price, 1978). Pure siderite, FeCO3 has a quadrupole splitting of 1.89 mm/s and an isomer shift of 1.23 mm/s at RT. In our kerogen samples, the isomer shifts were nearly in the order of 1.23 mm/s; however the quadrupole splitting were slightly smaller than those of siderites. In siderite each iron is coordinates with

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(a) Figure 3. RT Mossbauer Spectra of Kerogen samples isolated from Esh-El-Mellaha Field, Suez Gulf, Egypt. Depths in feet at which samples were collected are indicated.

six oxygen neighbors belonging to six different CO3 ions, and each of these oxygen neighbors is bound to one atom of carbon and to two iron ions. The substitution of calcium and magnesium atoms in the structure, such as in dolomite and ankerite, would disturb the original octahedral structure. This deviation is expected to slightly decrease the quadrupole splitting. The slight reduction in quadrupole splitting of our samples suggests that the iron in the carbonates may in the form of Fe-dolomite and/or ankerite (Cole et al., 1978). Iron atoms substituted in calcium (CaCO3 ) give a quadrupole splitting of 1.50 mm/s at RT, i.e., similar to those of Fe2C in ferroan dolomite and ankerite. However, the isomer shift is a little bit higher (Fe D 1:29 mm/s). Therefore Fe2C in calcite may be distinguished from Fe2C in ferroan dolomite and ankerite in spectra in which the

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(b) Figure 3. RT Mossbauer Spectra of Kerogen samples isolated from Esh-El-Mellaha Field, Suez Gulf, Egypt. Depths in feet at which samples were collected are indicated.

component A is well resolved. Overall, complete investigation of the dependence of the Mossbauer parameters on the composition of pure carbonate minerals has not yet been made and therefore it is not possible to give a detailed interpretation of the component A in the spectra. In conclusion, we feel that this work has provided extra evidence on the correlation between the formation of ankerite and the source rock maturity which have previously been reported by several authors. For instance, Morup et al. (1984) and the references therein found an apparent correlation between the relative amounts of iron in ankerite and the content of oil and/or gas in shales from Colorado, Illinois/Kentauky as well as Danish land area. This result suggests that the correlation between the maturation levels in kerogen and the presence of ankerite found in the present study may exist in

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sediments from other oil and gas elds. The mechanism of formation of ankerite during diagenesis of organic rich sediments is not known in detail. The release of the CO2 C H2 O and metal ions during the diagenesis of organic matter may be of great importance and these species may precipitate as carbonates. The Egyptian Miocene sediments in the area of Suez Gulf contain a large amount of algal material which is characterized by a high Mg2C/Ca2C ratio (Essam) and this may favor precipitation of ankerite rather than calcite during diagenesis. Hence, the apparent correlation between the maturity in the possible Miocene source rocks in the area of Suez Gulf (Table 1) and the presence of ankerite (identied by MS) may be explained by precipitation of ankerite from species which are released from the organic sediments.

References
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