Journal of Earth Science, Vol. 29, No. 4, p. 837–853, August 2018 ISSN 1674-487X Printed in China https://doi.org/10.1007/s12583-018-0792-6
Yuri D Zakharov*1, Micha Horacek2, 3, Alexander M Popov1, Liana G Bondarenko1 1. Far Eastern Geological Institute of Russian Academy of Sciences (Far Eastern Branch), Stoletiya Prospect 159, Vladivostok 690022, Russia 2. BLT Wieselburg, Research Center HBLFA Francisco-Josephinum, Wieselburg 3250, Austria 3. Institute of Lithospheric Research, Vienna University, Vienna 1090, Austria
ABSTRACT: The Kamenushka Formation, exposed in the northern part of South Primorye (Kamenushka-1 and Kamenushka-2 sections), is one of the few localities in the world with richly fos- siliferous Lower–Upper Olenekian sedimentary successions. Lower to Middle Triassic ammonoid-, brachiopod- and conodont-bearing silty-clayey deposits of the Kamenushka-1 and Kamenushka-2 sections have been isotope-geochemically investigated in detail. As a result, these sections, together with the previously investigated Abrek Section, exposed in the southern part of South Primorye, 15 13 provide almost complete Norg- and Corg- records for the Lower Triassic of this region. Nine N- isotope intervals and the five negative C-isotope excursions, reflecting, apparently, unstable climatic and hydrological conditions, have been distinguished in the Lower Triassic of South Primorye. On the basis of the new C-isotope data the Mesohedenstroemia bosphorensis Zone (upper part), Shi- manskyites shimanskyi and Neocolumbites insignis zones of South Primorye are correlated now with the Lower Smithian part of the Yinkeng Formation, the Upper Smithian part of the Helongshan Formation and the Middle Spathian part of the Nanlinghu Formation in South China, respectively, as has been observed in the Abrek, Kamenushka-2, West Pingdingshan and Majiashan sections. KEY WORDS: Triassic, N- and C-isotopes, palaeoclimatology, bio- and chemostratigraphy, Pri- morye, Russia.
0 INTRODUCTION et al., 2018) by demonstrating of N-isotope data, showing cor- 13 13 The results on Corg and Ccarb investigations of the Low- relation with O-isotope data, obtained from Induan and Early er Triassic for many regions are well known (e.g., Wignall et Olenekian conodonts of the Nammal Section in the Salt Range, al., 2015, 1998; Algeo et al., 2014, 2008; Song et al., 2014, Pakistan (Romano et al., 2013). 15 13 2013; Zakharov et al., 2014; Dustira et al., 2013; Takahashi et This paper focuses on detailed Norg and Corg investiga- al., 2013, 2010; Hermann et al., 2011, 2010; Horacek et al., tion of both the Lower and the Upper Olenekian of the Lower 2010a, b, 2009, 2007a, b, c; Luo et al., 2011; Korte and Kozur, Triassic in Kamenushka River Basin, South Primorye (Fig. 1), 2010; Korte et al., 2010; Kaiho et al., 2009, 2001; Grasby and to fill a gap in our knowledge on isotopic change of the upper Beauchamp, 2008; Nakrem et al., 2008; Galfetti et al., 2007; part of the Olenekian in this region in order to assist the corre- Tong et al., 2004; Baud et al., 1989; Holser and Magaritz, lation of Lower Triassic sections of South Primorye with other 15 1987). However, Norg records from the Lower Triassic are isotopic studied sections. restricted mainly to some data from Arctic Canada (Smith Creek Section in the Svedrup Basin; Grasby et al., 2016, 2015) 1 GEOLOGICAL SETTING AND STRATIGRAPHY and South China (e.g., Algeo et al., 2014; Saitoh et al., 2014; The main areas of investigations are the Bureya-Jiamusi- Yin et al., 2012). Khanka superterrane (including Kamenushka River Basin) and Recently, we increased the significance of one of the a cratonic fragment (the Sergeevka terrane) obducted into a Lower Triassic sections in South Primorye (Abrek) (Zakharov Jurassic accretionary wedge (Isozaki et al., 2017; Golozubov, 2006; Kemkin, 2006; Khanchuk et al., 1995). These study areas *Corresponding author: [email protected] are located between the Sino-Korean Craton to the south and © China University of Geosciences and Springer-Verlag GmbH the Sikhote-Alin fold belt to the east (Khanchuk et al., 1995). Germany, Part of Springer Nature 2018 The major part of the Sikhote-Alin orogenic belt is occupied by Jurassic to Cretaceous accretionary complexes and arc-related Manuscript received January 2, 2018. volcano-sedimentary rocks of the Samarka, Taukha, Zhurav- Manuscript accepted June 5, 2018. levka, Kiselevka and Kema belts (Isozaki et al., 2017; Khan-
Zakharov, Y. D., Horacek, M., Popov, A. M., et al., 2018. Nitrogen and Carbon Isotope Data of Olenekian to Anisian Deposits from Kamenushka/South Primorye, Far-Eastern Russia and Their Palaeoenvironmental Significance. Journal of Earth Science, 29(4): 837– 853. https://doi.org/10.1007/s12583-018-0792-6. http://en.earth-science.net 838 Yuri D Zakharov, Micha Horacek, Alexander M Popov and Liana G Bondarenko chuk et al., 2016). The common age spectra of detrital zircons tion Early Triassic conodonts of South Primorye had been in- of the Palaeozoic sandstones in South Primorye and NE-SW vestigated by Buryi (1979) and Bondarenko et al., (2015, 2013). Japan (Isozaki et al., 2017) support the concept of “Greater Based upon comparison of ammonoid assemblages dis- South China” (Isozaki et al., 2014) that is comprised of con- covered from the main Lower Triassic sections in South Pri- terminous South China to extend to Japan/Primorye, which is morye (Fig. 1), eight biozones were defined (e.g., Zakharov et consistent with the mutual similarities recognised in Late Pa- al., 2016; Zakharov and Moussavi Abnavi, 2013). The Induan leozoic, including latest Changhsingian, marine fauna (Isozaki in South Primorye consists of the following two zones: (1) et al., 2014; Zakharov et al., 1997; Zakharov, 1994). Tompophiceras ussuriense and (2) Gyronites subdharmus. The The principle biostratigraphic framework for Middle to Olenekian consists of the following six zones (and beds): (3) Lower Triassic zonal boundary intervals in South Primorye Mesohedenstroemia bosphorensis (Ussuriflemingites abreken- were constrained by ammonoid and conodont fossils. Early and sis and Euflemingites prynadai beds); (4) Anasibirites nevolini; Middle Triassic ammonoids in this region were firstly collected (5) Shimanskyites shimanskyi; (6) Tirolites-Amphistephanites by Margaritov V P and Ivanov D I, who made geologic recon- (Bajarunia dagysi and Tirolites ussuriensis beds); (7) Neoco- naissance work for the construction of the military outpost lumbites insignis; (8) Subfengshanites multiformis; (9) Prohun- Vladivostok and the Trans-Siberian railroad in the 1880s. On garites beds. the initiative of Karpinsky A P, President of the Russian Acad- Two nearby sections (Kamenushka-1 and Kamenushka-2) emy of Sciences, the Induan, Olenekian and Anisian ammono- rich in ammonoid and brachiopod fossils represent an excellent ids, collected in some of the sections (e.g., Schmidt, Zhitkov, record of the Lower–Upper Olenekian deposits which were Ayax and Tri Kamnya), were forwarded to C. Diener (Vienna deposited in a marine deeper water environs. No indications of University), who described them in 1895 (Diener, 1895). Later, sedimentary breaks have been found in these two studied sec- further monographs (e.g., Shigeta et al., 2009; Zakharov, 1978, tions. Observed-ranges of ammonoids across the Olenekian 1968; Kiparisova, 1961) were published on this topic. In addi- interval are summarized in Fig. 2.
Figure 1. Location of the examined sections in South Primorye, Russian Far East: 1. Kamenushka; 2. Shmidt; 3. Zhitkov; 4. Ayax; 5. Konechnyj; 6. Tobizin; 7. Atlasov; 8. Tri Kamnya; 9. Golyj; 10. Abrek.
Nitrogen and Carbon Isotope Data of Olenekian to Anisian Deposits from Kamenushka/South Primorye 839
Fossils from the two studied sections (Kamenushka-1 and 1.1 Description of the Kamenushka-1 Section Kamenushka-2; Fig. 3), have been studied in detail (e.g., Popov The Kamenushka-1 Section is situated 6.5 km SSE of the and Zakharov, 2017; Smyshlyaeva and Zakharov, 2017; Zakha- village of Kondratenovka, along a gas pipeline. Its geographic rov and Smyshlyaeva, 2016; Zakharov et al., 2016). Their de- coordinates are: latitude 43o36'11.8"N; longitude 132o10'16.8"E scriptions are not included in this paper. However, the descrip- of Greenwich. The section is exposed of the Lazurnaya, Kame- tion of the Kamenushka-1 and Kamenushka-2 sections is given nushka and Karazin formations. Herein (in both the Kame- for the first time. nushka-1 and the Kamenushka-2 sections), the numbers in the brackets correspond to the samples taken for the C- and N-
Figure 2. Temporal ranges of Olenekian–Earliest Anisian ammonoids from the Kamenushka River Basin. Abbreviations: ?Gyron. subd., ?Gyronites subdhar- mus; Mesoh. b., Mesohedenstroemia bosphorensis; Anas. nevol., Anasibirites nevolini; Shim. shiman., Shimanskyites shimanskyi; Tirolites-Amphisteph., Tirolites- Amphistephanites.
840 Yuri D Zakharov, Micha Horacek, Alexander M Popov and Liana G Bondarenko
Figure 3. The Kamenushka-1 and Kamenushka-2 sections (plan), South Primorye.
Nitrogen and Carbon Isotope Data of Olenekian to Anisian Deposits from Kamenushka/South Primorye 841 isotope measurements. The Kamenushka-1 Section is com- marl (K-333, K-338, K-342 and K-343, K-348, K-351, K-356, posed of the following Lower and Middle Triassic lithological K-361, K-367, respectively). Members 17–18 yield the rare and biostratigraphical combination (in descending order). nautilids and ammonoids Yvesgalleticeras proximus Zakharov et Smyshlyaeva and Koninckitoides popovi (Kummel). 1.1.1 Lower Anisian The thickness of the examined interval of the Neocolum- (1) Leiophyllites pradyumna and Ussuriphyllites amurensis bites insignis is about 47 m. zones Member 27: More than 28.0 m of dark grey striped and (2) Tirolites-Amphistephanites and Shimanskyites shimanskyi spotted sandy siltstone and mudstone intercalated with grey, zones fine-grained sandstone (K-431). The unit is characterised by Members 13–16: These units include an interval of ap- rare ammonoid finds: Hollandites sp. and Leiophyllites sp. proximately 15 m, and consist of dark grey siltstone, sandy These fossils support the Early Anisian Age of Member 27 siltstone and mudstone interbedded with grey fine grained (likely Leiophyllites pradyumna Zone). sandstone and contain rare concretions of calcareous marl and Member 26: 6.0 m of thin intercalation of dark grey silt- lenses of calcareous sandstone in the upper part (K-304 and K- stone and grey, fine grained sandstone (K-420, K-425 and K- 307 from Member 13; K-308, K-313 and K-315 from Member 430). 14; K-316 and K-321 from Member 15; K-324, K-329 and K- Closed interval corresponding to more than 50 m in thick- 33 from Member 16), with poorly preserved fossils. ness. Members 11 (upper part) and 12: About 5 m of dark grey mudstone (K-296, K-300 and K-303 from Member 12). These 1.1.2 Olenekian members yield conodonts (Furnishius triserratus Clark, Ha- (1) Neocolumbites insignis Zone drodontina sp.) and ostracodes. Member 24: About 8 m of dark grey siltstone and mud- Covered interval (10–15 m in thickness). stone with interbeds of grey fine grained sandstone, lenses of Members 10–11 (lower part): About 28 m of dark grey calcareous sandstone-coquina and concretions of calcareous siltstone with interbeds of grey fine grained sandstone in the marl (K-410 and K-415, taken from the upper part of Member lower part and dark grey mudstone with numerous concretions 24). The following fossils were found in this member: abundant of calcareous-marl. The units contain abundant ammonoids brachiopods, preliminarily identified as rhynchonellids (e.g., (Shimanskyites shimanskyi Zakharov et Smyshlyaeva, Arctoce- Piarorhynchella tazawai Popov), terebratulids (Bittnerithyris ras septentrionale (Diener), Prosphingitoides ovalis (Kipariso- margaritovi (Bittner)), spiriferinids (Lepismatina sp.) and athy- va) and ostracodes (Zakharov et al., 2016). ridids (e.g., Hustedtiella planicosta Dagys); rare bivalve mol- Covered interval (15–20 m in thickness). luscs, abundant gastropods; rare nautilids and abundant ammo- noids (Pseudosageceras longilobatum Kiparisova, Cordillerites 1.1.3 Induan sp., Ussurijuvenites sp., Inyoceras singularis Zakharov et ?Gyronites subdharmus Zone Smyshlyaeva, Jeanbesseiceras sp. nov., Yvesgalleticeras prox- Member 5: 5.0 m of conglomerate of small pebbles and a imus Zakharov et Smyshlyaeva, Tirolites opiparus Zakharov et layer of grey fine grained sandstone at the base. Smyshlyaeva, Koninckitoides popovi (Kummel), Nordophice- Member 4: 20.0 m of conglomerate of large pebbles. ratoides praecox Zakharov et Smyshlyaeva, Goricanites sp.) Member 3: 20.0 m of grey fine grained sandstone, with and conodonts Neospathodus sp. A, Neospathodus sp. B (Po- lenses of conglomerate. pov and Zakharov, 2017; Zakharov and Smyshlyaeva, 2016). Member 2: 20.0 m of grey fine grained sandstone. Members 21–23: 11.0 m of dark grey siltstone with nu- Member 1: 30.0 m of grey fine grained sandstone, with merous lenses of calcareous sandstone-coquina (K-379, K-384, rare lenses of conglomerate. and K-389 from Member 21; K-390 and K-393 from Member The total thickness of the examined Induan is 95 m. Lower 22; K-394 and K-399 from Member 23). The units contain a Triassic basal conglomerate and sandstone in some other sec- diverse fossil assembage: rare brachiopods, identified as rhyn- tions (e.g., Golyj and Tri Kamnya) are mainly characterised by chonellids (Piarorhynchella tazawai Popov), terebratulids ammonoids Gyronites subdharmus Kiparisova (Zakharov, 1978, (Bittnerithyris margaritovi (Bittner)), spiriferinids (Lepismatina 1968; Kiparisova, 1961). sp.); rare bivalve molluscs, abundant gastropods, rare nautilids and abundant ammonoids (e.g., Inyoceras singularis Zakharov 1.2 Description of the Kamenushka-2 Section et Smyshlyaeva and Yvesgalleticeras proximus Zakharov et The Kamenushka-2 Section is located along a new road, Smyshlyaeva). 100–140 m west of the Kamenushka-1 Section. It exposes the Members 19–20: About 7.0 m of dark grey sandy siltstone Induan Lazurnaya (upper part) and Olenekian Kamenushka with rare lenses of calcareous sandstone-coquina (K-369, K- formations. The Kamenushka-2 Section represents a unique 373, K-375 and K-376, K-378, respectively). Members 19–20 and valuable record of the Lower–Middle Olenekian exposed are characterised by some brachiopods (Bittnerithyris margari- in South Primorye. In descending order, the lithological and tovi (Bittner)), and ammonoids Ussurijuvenites sp. and Ko- biostratigraphical combinations of its Lower Triassic deposits ninckitoides popovi (Kummel). are as following. Members 17–18: 20.5 m of dark grey siltstone with lenses of calcareous sandstone-coquina and concretions of calcareous- (1) Neocolumbites insignis Zone
842 Yuri D Zakharov, Micha Horacek, Alexander M Popov and Liana G Bondarenko
Member 24: About 41 m of dark grey sandy siltstone with Koninckitoides popovi (Kummel), Bajarunia magna Zakharov interbeds of grey fine grained sandstone and concretions of et Smyshlyaeva, Palaeophyllites admirandus Zakharov et calcareous marl (K-295, K-260, K-265, K-270, K-285, K-290). Smyshlyaeva). Member 24 contains brachiopods, identified as rhynchonellids The thickness of the examined interval of the Neocolum- (e.g., Piarorhynchella tazawai Popov), terebratulids (Bittneri- bites insignis Zone (Inyoceras singularis Beds) in the thyris margaritovi (Bittner)) and spiriferinids (Lepismatina sp.); Kamenushka-2 Section is no less than 80.0 m. abundant gastropods; abundant ammonoids (Koninckitoides popovi (Kummel), Inyoceras singularis Zakharov et Smysh- (2) Tirolites-Amphistephanites Zone lyaeva, Nordophiceratoides praecox Zakharov et Smyshlyaeva, Member 16: 4.5 m of intercalation of dark grey siltstone Koninckitoides solus Zakharov et Smyshlyaeva, Albanites vul- and greenish grey fine grained, calcareous sandstone (K-168, garis Zakharov et Smyshlyaeva and fish remains (Popov and K-174, K-176). Member 16 yields the ammonoids Albanites Zakharov, 2017; Zakharov and Smyshlyaeva, 2016). vulgaris Zakharov et Smyshlyaeva and Nordophiceratoides Member 23: 3.5 m of dark grey sandy siltstone lenses of praecox Zakharov et Smyshlyaeva. grey fossil-rich calcareous sandstone-coquina (K-249, K-254). Member 15: 4.0 m of thin intercalations of dark grey mud- Member 23 yields brachiopods, identified as terebratulids (Bit- stone and grey fine grained sandstone, with numerous lenses of nerithyris margaritovi (Bittner) and athyridids (Hustedtiella calcareous sandstone-coquina and concretions of calcareous planicosta Dagys (Bed 961-11), and ammonoid Inyoceras sin- marl (K-161, K-167). gularis Zakharov et Smyshlyaeva. Member 14: 5.0 m of dark grey mudstone with rare, thin Member 22: 2.0 m of dark grey sandy siltstone (K-245, (4 cm) layers of grey sandy siltstone and rare concretions of K-248). calcareous marl with terebratulid brachiopods (e.g., Bittnerithy- Member 21: 5.5 m of dark grey sandy siltstone with inter- ris margaritovi (Bittner)) (K-150, K-155, K-160). calated fossil-rich calcareous sandstone lenses (K-233, K-238, Member 13: About 4.0 m of dark grey siltstone and K-244). Member 21 contains diverse organic remains: abun- mudstone with interbeds of grey fine grained sandstone (K- dant brachiopods, identified as rhynchonellids (Piarorhynchel- 147, K-149). la tazawai Popov), terebratulids (Bittnerithyris margaritovi Member 12: 27.5 m of dark grey mudstone with numerous (Bittner), Heterelasma sp.), spiriferinids (Lepismatina sp.) and concretions of calcareous-marl (K-102, K-107, K-112, K-117, athyridids (Hustedtiella planicosta Dagys), rare bivalve mol- K-122, K-127, K-132, K-137, K-142, K-146). Member 12 con- luscs, abundant gastropods, abundant ammonoids (Pseudosa- tains diverse organic remains: brachiopods, identified as rhyn- geceras longilobatum Kiparisova, Tirolites opiparus Zakharov chonellids (Piarorhynchella tazawai Popov), terebratulids et Smyshlyaeva, Kazakhstanites? sp., Nordophiceratoides (Bittnerithyris margaritovi (Bittner)), spiriferinids (Lepismatina praecox Zakharov et Smyshlyaeva, Khvalynites sp., Eodanu- sp.), rare bivalve and, nautilid molluscs, abundant ammonoids bites sp., Palaeophyllites admirandus Zakharov et Smyshlyae- (Jeanbesseiceras explicatum Zakharov et Smyshlyaeva, Tiro- va) and fish teeth (Popov and Zakharov, 2017; Zakharov and lites? sp., Koninckitoides popovi (Kummel), Koninckitoides Smyshlyaeva, 2016). solus Zakharov et Smyshlyaeva, Bajarunia magna Zakharov et Member 20: 3.0 m of dark grey siltstone with lenses of Smyshlyaeva, Albanites vulgaris Zakharov et Smyshlyaeva, calcareous sandstone-coquina (K-228, K-232). Nordophiceratoides praecox Zakharov et Smyshlyaeva), ostra- Member 19: 4.0 m of dark grey sandy siltstone (K-219, K- codes and conodonts (Popov and Zakharov, 2017; Zakharov 224, K-227). Member 19 yields ammonoids Koninckitoides and Smyshlyaeva, 2016). popovi (Kummel) and Nordophiceratoides praecox Zakharov et The thickness of the examined interval of the Tirolites- Smyshlyaeva and brachiopod Piarorhynchella tazawai Popov. Amphistephanites (Bajarunia magna Beds) in the Kamenushka-2 Member 18: 13.0 m of dark grey siltstone with lenses of Section is 45.0 m. calcareous sandstone-coquina (K-193, K-198, K-203, K-208, K-213, K-218). Member 18 contains diverse organic remains: (3) Shimanskyites shimanskyi Zone brachiopods, identified as rhynchonellids (Piarorhynchella Member 11: 9.0 m of dark grey mudstone and siltstone tazawai Popov), terebratulids (Bittnerithyris margaritovi (Bitt- with numerous concretions of calcareous-marl (K-83, K-88, K- ner)), ammonoids Inyoceras singularis Zakharov et Smysh- 93, K-98, K101 from the southern block and K-58, K-63, K-68 lyaeva, Tirolites opiparus Zakharov et Smyshlyaeva, Tirolites? from the northern block). Member 11 yields brachiopods (Pia- sp., Koninckitoides popovi (Kummel), Albanites vulgaris Zak- rorhynchella tazawai Popov, Bittnerithyris margaritovi (Bitt- harov et Smyshlyaeva, Kamenushkaites acutus Zakharov et ner), Lepismatina sp.), ammonoids (Ussuriidae gen. et sp. in- Smyshlyaeva (Popov and Zakharov, 2017; Zakharov and det., Parussuria sp., Pseudosageceras longilobatum Kiparisova, Smyshlyaeva, 2016). Ussuriaspenites sp., Kamenushkaites sp., Xenoceltites? subva- Member 17: 8.0 m of greenish grey mudstone with thin (3 riocostatus Zakharov et Smyshlyaeva, Shimanskyites shimans- mm) layers of sandy siltstone, lenses of calcareous sandstone- kyi Zakharov et Smyshlyaeva, Arctoceras subhydaspis (Kipari- coquina and concretions of calcareous marl (K-177, K-182, K- sova), Churkites syaskoi Zakharov et Shigeta, Anasibirites 187, K-192). Member 17 yields rhynchonellid brachiopods simanenkoi Zakharov et Smyshlyaeva, Monneticeras kalinkini (Piarorhynchella tazawai Popov), abundant gastropods, abun- Zakharov et Smyshlyaeva, Mianwaliites ziminu Zakharov et dant ammonoids (Inyoceras singularis Zakharov et Smysh- Smyshlyaeva, Hemiprionites klugi Brayard et Bucher, Nyala- lyaeva, Yvesgalleticeras proximus Zakharov et Smyshlyaeva, mites? sp., Ussurijuvenites sp., Owenites carpenteri Smith,
Nitrogen and Carbon Isotope Data of Olenekian to Anisian Deposits from Kamenushka/South Primorye 843
Prionites markevichi Zakharov et Smyshlyaeva, Prionites sub- (Thermo, Bremen/Germany), connected via a CONFLO IV tuberculatus Zakharov et Smyshlyaeva, Radioprionites abre- (Thermo, Bremen/Germany) to a Delta advantage mass- kensis Shigeta et Zakharov, Juvenites sp.), nautiloids (Tremato- spectrometer (Thermo, Bremen/ Germany) in Wieselburg/ ceras sp.), ostracodes and conodonts (Furnishius triserratus Austria (HBLFA Francisco-Josephinum). Bulk sediment ma- Clark, Hadrodontina sp. and Neospathodus sp.) (Zakharov et terial was decarbonated by placing the samples in glasses on a al., 2016). heated surface (58–60 °C) and addition and frequent replace- ment of HCl (10% v/v), until decarbonation was completed. (4) Anasibirites nevolini Zone Completion of decarbonation was checked by occurrence of Member 10: 11.5 m of dark grey mudstone and bandy silt- bubbles after addition of HCl. Maximum decarbonation time stone with interbeds of fine-grained sandstone and numerous was several weeks. concretions of calcareous-marl (K-73, K-78, K-82 from the The results are reported in the conventional-notation in southern block and K-34, K-39, K-44, K-49, K-54, K-57 from permil (‰) relative to the international V-PDB (Vienna Pee- the northern block). Dee) and N-air standards for carbon and nitrogen, respectively. The unit contains diversed organic remains: abundant Reproducibility of replicate standards are better than ±0.2‰ for ammonoids (Pseudosageceras sp., Prosphingitoides ovalis carbon and ±1‰ for nitrogen (because of low content of the (Kiparisova), Owenites koekeni Hyatt et Smith, Arctoceras latter in the samples). subhydaspis (Kiparisova), Arctoceras septentrionale (Diener), Churkites cf. syaskoi Zakharov et Shigeta, Anasibirites cf. ne- 3 RESULTS AND DISCUSSION volini Burij et Zharnikova., Prionites markevichi Zakharov et The detailed N- and C-isotope investigation of the Kame- Smyshlyaeva, Xenoceltites? subvariocostatus Zakharov et nushka-1 and Kamenushka-2 sections and data from the earlier Smyshlyaeva, Mianwaliites zimini Zakharov et Smyshlyaeva), investigated the Abrek Section (Zakharov et al., 2018), have ostacodes and conodonts (Furnishius triserratus Clark, Hadro- revealed that nine N-isotope intervals, indicated as I–IX, and dontina sp.) (Zakharov et al., 2016). some C-isotope excursions can be recognised in the Lower Position of a tectonic fault (the upper part of the Mesohe- Triassic of this region (Figs. 4–6). denstroemia bosphorensis Zone in this section is absent). Interval I corresponds to the lower part of Induan layers of Tompophiceras ussuriense-Pseudoproptychites hiemalis in (5) Mesohedenstroemia bosphorensis Zone (lower part) the Abrek Section, which is characterised by frequent alterna- Member 9: 12.5 m of thin intercalations of dark grey silt- tion of negative (up to -4‰) and positive (up to +2.2‰) δ15N stone and grey fine grained sandstone, with rare concretions of values. calcareous-marl (K-10, K-15, K-20, K-25, K-33 from the north- Interval II, corresponding mainly to the upper Induan Gy- ern block, which has been subjected to folding and faulting). ronites subdharmus Zone and the lower part of the Lower Olene- Member 9 yields bivalves (Bakevellia exporecta Gordon), kian Mesohedenstroemia bosphorensis Zone in the Abrek Sec- ammonoids (Pseudosageceras sp., Arctoceras septentrionale tion, is mainly characterised by positive δ15N values (up to +8‰). (Diener), Balchaeceras subevolvens (Zakharov), Ussurijuvenites Interval III, covering the middle part of the Lower Ole- artyomensis Smyshlyaeva et Zakharov) (Zakharov et al., 2016). nekian Mesohedenstroemia bosphorensis Zone in the Abrek Member 8: 2.5 m of dark grey mudstone with numerous Section, is characterised by predominantly negative δ15N values concretions of calcareous-marl (K-6, K-9), containing poor (up to -5.8‰). preserved ammonoids (e.g., Arctoceras? sp.). Intervals IV and V, corresponding to the upper part of Member 7: 1.0 m of thin intercalations of dark grey silt- the Mesohedenstroemia bosphorensis Zone in the Abrek Sec- stone and grey fine grained sandstone (K-3, K-4). tion, are characterised by frequent alternation of negative (up to Member 6: 0.5 m of dark grey mudstone with rare concre- -2.1‰) and positive (up to +1.8‰) δ15N values and predomi- tions of calcareous-marl, yielding small bivalve molluscs (K-1, nantly positive δ15N values (up to +1.0‰), respectively. K-2). The total thickness of the examined interval of the Ole- However, there is, apparently, only the lowermost part of nekian in the section is about 167 m. N-isotope interval V in the Abrek Section (Fig. 6). In the Kamenushka-2 Section, the possible continuation of this inter- 1.3 Induan val, also characterised by predominantly positive δ15N values, ?Gyronites subdharmus Zone seems to be extending into the lower part of the Upper Members 4 and 5: About 25 m of conglomerate with in- Olenekian Tirolites-Amphistephanites Zone. Therefore, the terbeds of grey fine grained sandstone. The total thickness of Kamenushka-2 Section provides more complete record on in- the examined interval of the Induan–Olenekian deposits in the terval V. Kamenushka-2 Section is about 192 m. In contrast with the Abrek Section (Zakharov et al., 2018), the Induan strata of the Kamenushka-2 Section is represented 2 MATERIAL AND METHODS by conglomerate and sandstone, which rock types are usually Material was collected with care taken to avoid mudstone unsuitable for isotopic investigation. The Lower Olenekian intervals with visible diagenetic features. From 425 samples of sequences, known in the northern block of the Kamenushka-2 Olenekian and Anisian mudstone from the Kamenushka-1 and Section (Arctoceras septentrionale-Balchaeceras subevolvens Kamenushka-2 sections, 116 samples, taken in sampling inter- beds) are mainly characterised by positive δ15N values (up to val of approximately 1–3 m, were analyzed using a Flash EA +1.51‰; samples K-1, K-2, K-3, K-4, K-6, K-9, K-10, K-15,
844 Yuri D Zakharov, Micha Horacek, Alexander M Popov and Liana G Bondarenko
K-20, K-25, K-30, K-33). ered at the base of Member 21 (Sample K-233). 13 This interval V, corresponds to members 10–12 (Anasibi- This interval is also characterised by quite stable δ Corg rites nevolini, Shimanskyites shimanskyi and Tirolites- values, ranging from -25.3‰ to -24.0‰. Amphistephanites (lower part) zones), which is characterised Interval IX, corresponding to the main part of members mainly by positive δ15N values. δ15N data ranges from -0.81‰ 24 of the Neocolumbites insignis Zone, is characterised by to +1.49‰, with a mean of +0.33‰ (the samples K-73, K-78, predominantly positive δ15N values, ranging from -0.62‰ to K-82, K-83, K-88, K-93, K-98, K-101, K-102, K-107, K-112, +1.69‰, with a mean +0.73‰ (the samples K-260, K-265, K- K-117, K-122, K-127, K-132, K-137, K-142, K-146 from the 270, K-275, K-280, K-285, K-290 from the southern block of southern block, and K-34, K-39, K-44, K-49, K-54, K-57, K-58, the Kamenushka-2 Section, the Sample K-415 from the south- K-63, K-68 from the northern block of the Kamenushka-2 Sec- ern block of the Kamenushka-1 Section). The maximal value tion and the samples K-295, K-300, K-303 from the southern (+1.69‰) was discovered at the middle part of Member 24 block of the Kamenushka-1 Section). The maximal δ15N value (Sample K-275). was measured from the Anasibirites nevolini-Shimanskyites The Late Olenekian interval IX exhibits a significant de- 13 shimanskyi boundary beds (Sample K-58). This interval is cha- crease in the δ Corg values (down to -27.4‰ in the middle part 13 racterised by comparatively variable δ Corg values, ranging of Member 24 (Sample K-270), closed to -26.7‰, obtained from -26.9‰ to -23.3‰, with the three carbon isotope mini- from the Sample K-430, which was taken from Member 27 of mum. The first of them (-26.1‰) is located near the boundary Early Anisian Age (Fig. 4). between the Anasibirites nevolini and Shimanskyites shimans- kyi zones (Sample K-83), two others (-26.9‰ and -25.8‰) are 3.1 N-Isotope Records located in the middle part of Member 12 (samples K-117 and Nitrogen is one of the most common elements of the solar K-127, respectively) of the Tirolites-Amphistephanites Zone. system, the main component of air on Earth (in the form of
Interval VI, corresponding to members 13–17 (the upper diatomic molecules N2). Nitrogen is a chemical element abso- part of the Tirolites-Amphistephanites Zone and lowest part of lutely necessary for the existence of living organisms. It is a the Neocolumbites insignis Zone), is characterised by signifi- major component of biomass and is required for photosyntesis cantly fluctuating δ15N values, from -1.83‰ to +1.31‰, with a (Robinson et al., 2012). The main part of the molecular nitro- mean of +0.05‰ (the samples K-147, K-149, K-150, K-155, K- gen of air is fixed precisely biotically (Bauersachs et al., 2009), 160, K-168, K-174, K-176, K-177, K-182, K-187, K-192 from by certain types of cyanobacteria (diazotrophic cyanobacteria– the southern block of the Kamenushka-2 Section and the sam- other phytoplankton representatives do not possess such abili- + ples K-304, K-307, K-308, K-313, K-315, K-316, K-321, K-323, ties). As a result, ammonium compounds (NH4 ) and ammonia K-324, K-329, K-332, K-333, K-338, K-342 from the southern (NH3), products that are well assimilated by plants, are formed. block of the Kamenushka-1 Section). The minimal δ15N value (- The combined nitrogen is transmitted along the food chain to
1.83‰) was discovered at Tirolites-Amphistephanites- herbivores and carnivores, and, being oxidized to nitrate (NO3-) Neocolumbites insignis boundary beds (Sample K-176). and nitrite (NO2-), it enters the sea and fresh water bodies in a 13 The δ Corg values of interval VI are somewhat higher and dissolved form. The tissues of the dead organisms undergo the less variable, ranging from -24.3‰ to -23.9‰, with lack of any three main processes: ammonification (decomposition with the distinct excursions. release of ammonium), anammox (anaerobic ammonium oxida- Interval VII, corresponding to Member 18 of the Neoco- tion) and denitrification (reduction of nitrate to nitrite and fur- lumbites insignis Zone, is characterised by mainly positive, ther to nitrogen gaseous oxides and molecules) (Glud et al., weakly fluctuating δ15N values ranging from -0.52‰ to +1.60‰, 2009), which largely compensate for the loss of nitrogen in the with a mean +0.41‰ (the samples K-193, K-198, K-203, K-208, atmosphere. However, the fundamental aspects of the nitrogen K-213, K-218 from the southern block of the Kamenushka-2 cycle in the atmosphere, investigated with the N-isotopic me- Section and the samples K-343, K-348, K-351, K-356, K-361, thod, still require further in-depth study (Sigman et al., 2009). K-367 from the southern block of the Kamenushka-1 Section). Studies of the isotope composition of nitrates in the mod- The interval VII is also characterised by less variable ern subtropics of the northern Pacific showed that relatively 13 15 δ Corg values, ranging from -25.0‰ to -23.9‰, with a small low values of δ NO3- (1‰–3‰) are typical for depths from 13 positive excursion (δ Corg = -23.9‰) in the lower part of 100 to 500 m, and steadily high values (4.5‰–5.5‰) for Member 18 (Sample K-198). depths exceeding 1 000 m (Altabet et al., 2005). A similar de- Interval VIII, corresponding to members 19–23 and the pendence of the N-isotopic composition of matter on the depths lower part of Member 24 of Neocolumbites insignis Zone, is of the ocean is also shown on the example of modern corals characterised by predominantly positive, significantly fluctuat- from low, middle and high latitudes (Wang et al., 2015). ing δ15N values, ranging from -0.45‰ to +2.60‰, with a mean In connection with the selective absorption of substances +0.88‰, with the two positive excursions (the samples K-219, with a light isotope 14N by phytoplankton this organic isotope K-224, K-226, K-227, K-228, K-232, K-233, K-238, K-244, K- is often enriched with organic substances deposited in modern 248, K-249, K-254, K-255 from the southern block of the Ka- seas in seasons of biological activity of phytoplankton. In the menushka-2 Section and the samples K-368, K-373, K-375, K- Sea of Japan, for example, such an isotopic effect demonstrat- 376, K-378, K-379, K-384, K-389, K-390, K-393, K-304, K- ing the relationship between the seasonal variability of phytop- 399, K-410, K-415 from the southern block of the Kamenush- lankton productivity and the N-isotopic composition of precipi- ka-1 Section). The maximal δ15N value (+ 2.60‰) was discov- tating organic particles is associated with phytoplankton, which
Nitrogen and Carbon Isotope Data of Olenekian to Anisian Deposits from Kamenushka/South Primorye 845 develops at the end of autumn-early winter, and especially in In Junium and Arthur’s (2007) opinion, the δ15N data sup- spring, when the temperature of surface waters fluctuates from port the hypothesis of expanded nitrogen fixation driven by about 10 to 17 ºC (Nakanishi and Minagawa, 2003). upwelling of nutrient-nitrogen poor, phosphorous replete
Figure 4. The Kamenushka-1 Section: Upper Olenekian–Lowest Anisian C- and N-isotope data. Abbreviations: Tirolites-Amphist, Tirolites-Amphistephanites; Us. Amurensis-Lei. pr., Ussuriphyllites amurensis-Leiophyllites pradyumna; Hollandites-Leioph., Hollandites-Leiophyllites; Kam.-1. Kamenushka-1; Kam-2 (s. bl.). Kamenushka-2 (southern block).
846 Yuri D Zakharov, Micha Horacek, Alexander M Popov and Liana G Bondarenko
Figure 5. The Kamenushka-2 Section: Lower–Upper Olenekian C- and N-isotope data. Abbreviations: M. bos. (l.p.), Mesohedenstroemia bosphorensis (lower part); Anas. n., Anasibirites nevolini; Shim. s., Shimanskyites shimanskyi; Ar. s.-Bal. s., Arctoceras septentrionale–Balhaeceras subevolvens; Kam-2 (n.bl.). Kamenushka-2 (northern block); Kam-2 (s.bl.). Kamenushka-2 (southern block); Kam-1. Kamenushka-1. Other designations as in Fig. 4.
Nitrogen and Carbon Isotope Data of Olenekian to Anisian Deposits from Kamenushka/South Primorye 847
Figure 6. Correlation of Lower Triassic layers in South Primorye (Abrek and Kamenushka) and Salt Range, Pakistan (Nammal) based on N- and O-isotope and palaeotemperature data. Abbreviations: Tompoph.u., Tompophiceras ussuriensis; Gyr.s., Gyronites subdharmus; P.k, Pseudoaspidites aff. kvansia- nus. ?A., ?Anasibirites nevolini; An.n., Anasibirites nevolini; S.s., Shimanskyites shimanskyi; Tirolites-Amphisteph., Tirolites-Amphistephanites; Ch., Changhsingian; Lo. Lower; Temp. .in (and N.i.i.). palaeotemperature interval (and N-isotope interval).
848 Yuri D Zakharov, Micha Horacek, Alexander M Popov and Liana G Bondarenko waters during Late Mesozoic oceanic anoxic events (OAEs), warm conditions prevailed in South Primorye in the Middle when “black shale” facies were common. However, they con- Induan followed by mainly cooler conditions during Late sider that upwellings are not required for nitrogen fixation but Induan–Olenekian and after that (the second part of the Meso- they are necessary maintain the phosphate flux that is needed hedenstroemia bosphorensis chron) again mainly warmer con- for long-term productivity and the consequent phosphate re- ditions. The first part of the Anasibirites nevolini chron is cha- lease. Cretaceous “black shales” are significantly depleted in racterised by rather cooler conditions, followed by warmer ones 15N compared to modern “black shales” forming basins such as during its second part. Subsequent cooler conditions during the the Black Sea despite the important role of biological nitrogen Shimanskyites shimanskyi and Tirolites-Amphistephanites fixation in both environments (Junium and Arthur, 2007). (lower part) chrons were followed, apparently, by warmer once. Of particular interest to our research is the data on the N- More or less stable cooler conditions during the Early Triassic isotopic composition of marine sediments deposited under took place, possibly, only during the Late Olenekian Neoco- greenhouse and glacial conditions (e.g., Algeo et al., 2014, lumbites insignis chron, which is in agreement with O-isotope 2008; Jenkyns et al., 2001; Altabet et al., 1995). They show the palaeotemperature calculations, based on data from conodonts important role of the marine cycle of nitrogen in long-term from the Nammal Section, Salt Range (Fig. 6). climate change and give a general trend of higher 15N-values Some workers mark a causal link between cooler condi- during times of cool climate (cool-house) and low 15N-values tions and increase in taxonomic diversity of marine fossils dur- during warm period (hot-house). The high nitrogen isotope ing the Early Triassic, because it was a time of mainly extreme values are explained by increased denitrification in the water warmth (e.g., Grigoryan et al., 2015; Schobben et al., 2014; column, whereas low 15N-values are related to increase nitro- Goudemand et al., 2013; Romano et al., 2013; Joachimski et al., gen fixation by cyanobacteria (e.g., Algeo et al., 2014; Luo et 2012; Sun et al., 2012). If the hypothesis concerning interpreta- al., 2011). tion of N-isotope data, recorded for South Primorye, is correct, Marine sedimentary organic matter can be diagenetically it seems to be plausible to assume that the greatest increase in altered. However, Algeo et al. (2014) argued that organic mat- abundance and partly in taxonomic diversity of both ammono- ter diagenetic alteration usually only has a minor effect on the ids and brachiopods from the Upper Olenekian Neocolumbites N-isotope ratio. Thus, marine sediments usually are regarded as insignis Zone of the Kamenushka-2 and Kamenushka-1 sec- quite robust, as published compound specific N-isotope offsets tions is also connected with cooler conditions of some N- from the bulk ratio can dominantly be accounted to photosyn- isotope intervals (e.g., VII–IX; Fig. 6; see also description of thetic effects. Furthermore, deeper burial does not seem to sig- members 17–24 in the “Geological setting and stratigraphy” nificantly affect N-isotopes of marine sediments, as metamor- section). Still, it needs to be noted and kept in mind that the low phosed sediments show similar values as sediments that did not amounts of N in the samples also will account for some fea- undergo deep burial. Therefore, it is concluded that marine tures identified in the sections, and the patterns thus need to be sediments are a quite robust archive of seawater-fixed nitrogen confirmed in other sections. (Algeo et al., 2014; Robinson et al., 2012; Higgins et al., 2010) and we follow this reasoning. 3.2 C-Isotope Records For the Kamenushka-1 and Kamenushka-2 sections, a ra- Reasons according for the worldwide negative δ13C excur- ther distal shelf-slope is assumed and thus only a very minor sions, including that at the Permian-Triassic boundary, is still a influence of terrigenous organic matter on the sediment organic topic at debate (e.g., Korte et al., 2010; Renne et al., 1995; matter. Therefore, as terrigenous organic matter has a higher C : Erwin, 1994; Baud et al., 1989; Gruszczyński et al., 1989; N ratio than marine organic matter, no significant influence on Holser and Magaritz, 1987). According to a well recognized the N-isotope ratio is assumed. version (e.g., Schobben et al., 2014; Sobolev et al., 2011; Korte 15 According to Algeo et al. (2014), the Phanerozoic δ Nsed et al., 2010; Horacek et al., 2007a, b, c; Chumakov, 2004; Iso- curve has a strong relationship with first-order climate cycles, zaki, 1997; Renne et al., 1995), the global end-Permian nega- with low values occurring during the greenhouse climate mod- tive C-isotope excursion has been provoked mainly by large es (mid-Permian, mid-Jurassic and Cretaceous) and high values imput of mantle-derived CO2 from the eruption of the Siberian occurring during the icehouse climate modes (mid-Palaeozoic traps. The most depleted δ13C values for the Permian-Triassic and Cenozoic). Cretaceous strata are strongly 15N-depleted boundary have been documented in New Zealand by Krull et al. (-4‰ to 0), whereas Carboniferous units are highly 15N- (2000), who hypothesized that methane release could have been enriched (+6‰ to +14‰). in part responsible for the larger isotopic shift in southern high On the basis of data on the Induan and Lower Olenekian palaeolatitudes. 13 of the Abrek Section, reported by us earlier (Zakharov et al., However, the δ Corg values of the most part of the Upper 2018), intervals of the Lower Triassic, characterised by the Olenekian interval in the Kamenushka-2 and Kamenushka-1 lower (often negative) δ15N values, were found to be associated sections are not so depleted as in New Zealand (Fig. 7). The 13 with warmer conditions (in comparison with intervals with the most prominent negative δ Corg excursions in the Lower Trias- higher (positive) values). sic of South Primorye are found in the following levels: (1) the The authors demonstrate this correlation between N- uppermost part of the Lower Olenekian Mesohedenstroemia isotopes and seawater temperature for the entire Lower Triassic bosphorensis Zone (up to -29‰ in the Abrek Section); (2) the (Abrek and Kamenushka-2 sections). According to this correla- uppermost part of the Lower Olenekian Anasibirites nevolini tion, the N-isotope record can be interpreted as showing fairly Zone (up to -26.1‰) of the Kamenushka-2 Section; (3) the
Nitrogen and Carbon Isotope Data of Olenekian to Anisian Deposits from Kamenushka/South Primorye 849
Figure 7. Correlation of Lower Triassic layers in South Primorye (Abrek and Kamenushka) and Chaohu, South China (Western Pingdingshan and South Majia- shan), based on C-isotope and palaeontological data. Abbreviations: Tomp.u., Tompophiceras ussuriensis; Gyr.s., Gyronites subdharmus; An.n., Anasibirites nevolini; Sh., Shimanskyites shimanskyi; Tirolites–Amphisteph., Tirolites–Amphistephanites; Helongsh., Helongshan; P.k, Pseudoaspidites aff. kvansianus.
850 Yuri D Zakharov, Micha Horacek, Alexander M Popov and Liana G Bondarenko lower part of the Upper Olenekian Tirolites-Amphistephanites birites nevolini chron, (4) the Early Olenekian (Late Smithian) Zone (up to -26.9‰) of both the Kamenushka-2 and the Kame- Shimanskyites shimanskyi chron and the beginning of the Late nushka-1 sections and (4) the upper part of the Middle Olene- Olenekian (Early Spathian) Tirolites-Amphistephanites chron, kian Neocolumbites insignis Zone (up to about -28‰) of both (5) the beginning of the Late Olenekian (Middle Spathian) the Kamenushka-2 and the Kamenushka-1 sections. C-isotope Neocolumbites insignis chron, (6) the middle part of the Late records documented from the Lower Triassic in South Pri- Olenekian Neocolumbites insignis chron, (7) the end of the morye, might reflect possibly some cycles of sea level fluctua- Late Olenekian Neocolumbites insignis chron. By and large this tions during the Middle–Late Induan, Olenekian and Earliest pattern is mainly in agreement with O-isotope palaeotempera- Anisian times (Zakharov et al., 2018). ture data from the Salt Range (Romano et al., 2013). 13 Our isotopic data enable a regional and global geochemical 4. The most prominent Lower Triassic negative δ Corg correlation between Lower Triassic sections of South Primorye excursions of South Primorye, allowing correlation with cor- (Zakharov et al., 2018) and Lower Triassic sections from Chao- responding Induan and Olenekian units of many Tethyan re- hu, South China (Tong et al., 2004, see also Fig. 7). gions, including South China (Tong et al., 2004), fall on the 13 There is no doubt that the negative δ Corg excursion 2, following intervals, (1) the uppermost part of the Early Olene- presented in the uppermost part of the Mesohedenstroemia kian Mesohedenstroemia bosphorensis Zone), (2) the upper- bosphorensis Zone in the Abrek Section (Fig. 7), corresponds most part of the Early Olenekian Anasibirites nevolini Zone, (3) 13 to the negative δ Ccarb excursion of the upper part of the Yin- the lower part of the Late Olenekian Tirolites-Amphistephanites keng Formation in the West Pingdingshan Section. This level Zone and (4) the upper part of the Upper Olenekian Neocolum- in South China rather corresponds to the uppermost part of the bites insignis Zone. Flemingites-Euflemingites Zone, than the lowermost part of the Anasibirites Zone in Tong et al.’s (2004) interpretation. ACKNOWLEDGMENTS Upper Olenekian interval, located between excursions 4 This research was funded by the grant RFBR 18-05- and 5 in both the Kamenushka-1 and the Kamenushka-2 sec- 00023A. We gratefully acknowledge Prof. Jinnan Tong (China tions, as well as in the South Majiashan Section, are characte- University of Geosdiences) for his unpublished information on 13 13 rised by higher δ C values. Taken into account these data, as Corg data from the Chaohu area, Doctor G. I. Guravskaya well as position of the excursion 5 in the uppermost part of the (FEGI, Vladivostok, Russia) for her consultation on Early Tri- Neocolumbites insignis Zone in South Primorye, the latter ap- assic conodonts and Doctor O. P. Smyshlyaeva (FEGI, Vladi- pears to be correlative in general with middle member of the vostok, Russia) for her help in collection of fossils and ano-
Nanlinghu Formation (Fig. 7). However, as the Corg present in nymous reviewers for helpful comments that improved this the samples can be of marine or terrigenous origin (with the manuscript. Processing of the samples by C. Panzenböck and latter possessing slightly higher carbon isotope values) the isotope measurements by E. Riegler are thankfully acknowl- variations in δ13C can be to some extent explained by various edged. The final publication is available at Springer via amounts of terrigenous organic matter. https://doi.org/10.1007/s12583-018-0792-6.
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