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Characterization of N-Alkanes, Pristane and Phytane in the Cretaceous/ Tertiary Boundary Sediments at Kawaruppu, Hokkaido, Japan

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Characterization of N-Alkanes, Pristane and Phytane in the Cretaceous/ Tertiary Boundary Sediments at Kawaruppu, Hokkaido, Japan Geochemical Journal, Vol. 33, pp. 285 to 294, 1999 Characterization of n-alkanes, pristane and phytane in the Cretaceous/ Tertiary boundary sediments at Kawaruppu, Hokkaido, Japan HAJIME MITA and AKIRA SHIMOYAMA Department of Chemistry, University of Tsukuba, Tsukuba 305-8571, Japan (Received December 24, 1998; Accepted April 22 , 1999) Normal alkanes from C12 to C36, pristane and phytane were identified in the Cretaceous/Tertiary (K/T) boundary sediments at Kawaruppu, Hokkaido, Japan. These compounds were found at the levels of sub to a few nmol g-1. Total concentrations of the n-alkanes within the boundary claystone were generally one third to one half of those in the sediments above and below the claystone. The smaller concentrations within the claystone were mainly due to smaller concentrations of longer chain n-alkanes (C25 to C31) than in the sediments above and below it. The longer chain n-alkanes were likely from terrestrial plants and reflected their small population at the end of Cretaceous. The concentration of longer chain n-alkanes decreased rapidly at the base of the boundary claystone, indicating the sudden cease of terrestrial n-alkane input, continued low to the horizon at the upper two thirds of the claystone and then, started increasing toward the top of the claystone. The n-alkane concentration change indicates the period of the small input of terrestrial n-alkanes to be ca. 7,000 years at most and the recovery period to be ca. 2,000 years. The depth distribution pattern of pristane plus phytane concentrations in the K/T sediments roughly resembles that of the n-alkanes. derived from then-living organisms. However, INTRODUCTION there are few studies of this kind. Those published The massive extinction of organisms, ranging to date report traces of microbial hydrocarbons and from dinosaurs to marine plankton at the end of fatty acids in the K/T boundary claystone and Cretaceous (approximately 65 million years ago) microbial fatty acids and additional terrestrial is one of the most significant biological events in resin acids in the sediments above and below the earth history. A global fallout of debris and dust claystone at Stevns Klint (Simoneit and Bellar, due to the impact of an extraterrestrial body or 1985, 1987; Meyers and Simoneit, 1989). bolide (Alvarez et al., 1980; Smith and Hertogen, The K/T boundary sediments at Kawaruppu, 1980) or to extensive volcanism (Officer and Hokkaido, Japan, provide a good sedimentary se Drake, 1983; McLean, 1985) is thought to be the quence to study the environmental changes at the cause of the extinction. Organic geochemical stud K/T boundary. The boundary claystone is similar ies on the Cretaceous/Tertiary (KIT) boundary in appearance to the well-known "boundary sediments aimed to find evidence for extraterres claystone" of the classical K/T boundary in Eu trial organic compounds (Zhao and Bada, 1989; rope, but is thicker (nearly 14 cm) and can be stud Mita et al., 1996, 1998) and wild fires triggered ied in detail along the depth. Other published stud by the bolide impact (Wolbach et al., 1985, 1988; ies of these sediments dealt with planktonic Venkatesan and Dahl, 1989; Heymann et al., foraminifera (Kaiho and Saito, 1986; Kaiho 1992), 1994a, b, 1996). palynomorphs (Saito et al., 1986), sulfur isotopes Studies of biological organic compounds in the (Kajiwara and Kaiho, 1992), and Ir accumulation K/T boundary sediments provide useful informa and clay minerals (Tasaki et al., 1992). We have tion on the massive extinction, because they are previously studied the organic geochemistry of 285 286 H. Mita and A. Shimoyama amino acids (Mita et al., 1996) and reported aliphatic hydrocarbons. The GC was equipped dicarboxylic acids (Mita et al., 1998) in the with a DB-5ht capillary column (30 m x 0.25 mm sediments. In the present study, we analyzed n i.d.). The oven temperature was programmed to alkanes, pristane and phytane in the sediments hold at 50°C for initial 1 min, and then ramp from above, within, and below the boundary claystone, 50 to 90°C at a rate of 5°C min-1, and from 90 to compared the concentrations, ratios and molecu 300°C at a rate of 4°C min-'. Helium was used as lar distributions of those aliphatic hydrocarbons, the carrier gas with a flow rate of 1.5 ml min 1. and related their characteristics to the environmen The mass spectra were acquired every 0.5 s over tal changes of the K/T boundary sediments at m/z 40 to 510 in the electron impact ionization Kawaruppu. mode and mass fragmentograms every 0.2 s. Iden tification and quantification of n-alkanes, pristane and phytane were generally made by comparison EXPERIMENTS of peak retention times and areas, respectively, on Samples mass fragmentograms for selected ions with those The K/T boundary sediments occur near of standard compounds. These compounds used Kawaruppu Town, Tokachi District, Hokkaido were even carbon numered n-alkanes in the range (Saito et al., 1986; Kaiho and Saito, 1986). The of C 12to C24, and C28, C32 and C36 besides pristane location of Kawaruppu, the lithology and sample and phytane. horizons of the sediments were reported in our Analytical grade hexane (Wako pure chemi previous studies (Mita et al., 1996, 1998). Briefly, cals), and twice distilled methanol and benzene the sedimentary sequence at Kawaruppu consists were used. All glassware was heated at 500°C for predominantly of a marine, dark gray siltstone, at least 3 h prior to use in order to eliminate or bearing occasional calcareous concretions. The ganic contaminants. A procedural blank was car boundary claystone is grayish black and nearly 14 ried out with 0.5 g pre-ignited sand powder and it cm thick. Thirteen sediment samples from differ was found that there was no significant contami ent horizons within the boundary claystone (0 to nation during the analysis. 13.7 cm), 5 samples above (40 to 495 cm) and 6 samples below (-395 to 0 cm) the boundary RESULTS AND DISCUSSION claystone were analyzed for aliphatic hydrocar bons. Concentrations Normal alkanes ranging from C,2 to C36, Analyses pristane and phytane were identified. For exam For each analysis, 1 g of powdered sediment ple, the mass fragmentogram (m/z 57) of these was extracted three times with 5 ml of a mixture aliphatic hydrocarbons in the sediment at the mid of benzene and methanol (4:1 by vol.) by sonica dle horizon (5.5 to 6.3 cm) of the boundary tion for 30 min. The extracted solutions were com claystone is shown in Fig. 1. Concentrations of bined, concentrated under reduced pressure, and these aliphatic hydrocarbons are listed in Table 1. applied to a silica gel column (130 mm x 10 mm The total concentrations of n-alkanes within the i.d.; Keiselgel-60, Merck). Aliphatic hydrocarbons boundary claystone (0 to 13.7 cm) were in the were obtained by eluting with hexane (10 ml). This ranges of 4.7 to 18.2 nmol g-1 with the mean value hexane solution was concentrated to 50 ul under of 8.7 nmol g-1, in the ranges of 14.0 to 17.6 (mean nitrogen flow for the analysis of individual value 16.5) nmol gl in the sediments above (40 aliphatic hydrocarbons. to 495 cm) and 16.4 to 26.5 (mean value 21.7) A gas chromatograph (GC) combined with a nmol g-1 in those below (-395 to 0 cm) the bound mass spectrometer (MS) (Shimadzu GC-MS QP ary claystone. The concentrations of pristane plus 5000) was used for separation and detection of the phytane within the boundary claystone were in the K/T boundary sediments at Kawaruppu, Hokkaido 287 18 17 32 pristane 33 I/ phyphytane 10, 34 L 35 36 m/z = 57 18 19 20 21 22 23 16 17 24 25 T 15 C N 14 G I (21h28 29 12 13 3031 32 10 20 30 40 50 60 Retention time (min) Fig. 1. Mass fragmentogram (m/z 57) of n-alkanes, pristane and phytane in the KIT boundary claystone (5.5 to 6.3 cm). Peak numbers correspond to those of the carbon number of the n-alkanes. 400 a b c 200 J 20 E U .r R. D 10 U a 0 -200 V YQ~ -400 U 0 20 40 0 5 10 0.0 0.4 0.8 1.2 Total n-alkanes Pristane plus phytane Total organic carbon (nmol g-t -rock) (nmolg-I -rock) (%) Fig. 2. Depth distributions of a: total concentrations of n-alkanes (C12 to C36),b: concentrations of pristane plus phytane, and c: total organic carbon content (Mita et al., 1996) in the KIT boundary sediments at Kawaruppu. ranges of 0.24 to 1.6 (mean value 0.59) nmol g 1, claystone from those in the sediments below the in the ranges of 1.8 to 3.1 (mean value 2.6) nmol boundary claystone. The decreased concentration g-1 in the sediments above and 2.1 to 3.1 (mean of n-alkanes continued over the lower two thirds value 2.7) nmol g-1 below the boundary claystone. portion (0 to 10.6 cm) of the boundary claystone Concentrations of the total n-alkanes and pristane and then sharply increased in the upper one third plus phytane at each sample horizon are shown in (10.6-13.7 cm) of the claystone. The concentra Fig. 2, together with the total organic carbon con tion increase ceased at the top of the boundary tents (Mita et al., 1996). claystone, and remained rather constant in the Total concentration of n-alkanes decreased sig sediments above the claystone.
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