Geological Quarterly, 2004, 48 (3): 267–282 Geochemical and ecological aspects of lower Frasnian pyrite-ammonoid level at Kostom³oty (Holy Cross Mountains, Poland) Grzegorz RACKI, Agnieszka PIECHOTA, David BOND and Paul B. WIGNALL Racki G., Piechota A., Bond D. and Wignall P. B. (2004) — Geochemical and ecological aspects of lower Frasnian pyrite-goniatite level at Kostom³oty (Holy Cross Mountains, Central Poland). Geol. Quart., 48 (3): 267–282. Warszawa. The lower Frasnian (transitans Zone with Ancyrodella priamosica = MN 4 Zone) rhythmic basin succession of marly limestones and shales (upper Szyd³ówek Beds) at Kostom³oty, western Holy Cross Mts., Central Poland, contains a record of the transgressive-hypoxic Timan Event in this drowned part of southern Laurussian shelf. The unique facies consists of organic-rich marly shales and a distinctive pyritic, goniatite level, 1.6 m thick. The faunal assemblage is dominated by pyritized shells of diminutive mollusks with cephalopods (including goniatites Epitornoceras and Acanthoclymenia), buchioline bivalves (Glyptohallicardia) and styliolinids. This interval is marked by moderately low Th/U ratios and pyrite framboid size distributions suggestive of dysoxic rather than permanent euxinic conditions. The scarcity of infauna and bioturbation resulted in finely laminated sedimentary fabrics, as well as the low diversity of the presumed pioneer benthos (mostly brachiopods). In the topmost part of the Szyd³ówek Beds, distinguished by the Styliolina coquina interbedded between limestone-biodetrital layers, the above geochemical proxies and C-isotope positive shift indicate a tendency to somewhat increased bottom oxygen deficiency and higher carbon burial rate linked with a bloom of pelagic biota during high-productivity pulse. The geochemical and community changes are a complex regional record of the initial phase of a major perturbation in the earth-ocean system during a phase of intermittently rising sea level in the early to middle Frasnian, and associated with the highest positive C-isotope ratios of the Devonian. Grzegorz Racki, Agnieszka Piechota, Department of Earth Sciences, Silesian University, Bêdziñska 60, PL-41-200 Sosnowiec, Poland; e-mail: racki@us.edu.pl, apiechot@wnoz.us.edu.pl; David Bond, Paul B. Wignall, School of Earth Sciences, University of Leeds, Leeds LS2 9JT, Great Britain; e-mail: d. bond@earth.leeds.ac.uk, P.Wignall@earth.leeds.ac.uk. Key words: Holy Cross Mountains, Frasnian, pyritic fossils, geochemical proxies, anoxia, Timan Event. INTRODUCTION A number of Devonian biotic events have been identified; these are usually associated with fluctuating anoxia and/or nutrient dynamics in a punctuated greenhouse climatic setting (e.g. House, 1985, 2002; Walliser, 1985, 1996; Becker, 1993; Streel et al., 2000; Copper, 2002; House, 2002; Sageman et al., 2003; Bond et al., 2004). Of these, the environmental change at the Frasnian-Famennian (F-F) boundary, and associated biotic crisis, is the best studied whereas several other Devonian biospheric perturbations remain rather poorly known. House (2002) emphasized an overvalued significance of terminal Frasnian events, however, and urged that study of other events was required to adequately place the F-F mass extinction in its Devonian context. The relatively continuous carbonate sequence in the Holy Cross Mountains, which represents the South Polish part of the Laurussian shelf (Fig. 1), contains well studied F-F boundary sections (e.g. Narkiewicz and Hoffman, 1989; Casier et al., 2000; Joachimski et al., 2001; Dzik, 2002; Racki et al., 2002; Bond and Zatoñ, 2003; Bond et al., 2004). This article presents first results of an interdisciplinary project on the preceding early to middle Frasnian biotic succession and events, inspired by results of previous Belgian-Polish geochemical study presented in Yans et al. (in press). An initial stage of the project focuses on the generally deeper-water, northern Kostom³oty-£ysogóry facies region (Fig. 1B) that remains crudely recognized, mostly due to poorer exposure (Racki, 1993; Szulczewski, 1995). The goal of this study is to provide a documentation of the geochemical and depositional signatures of distinctive lower Frasnian pyritized-fossiliferous level in the Szyd³ówek Beds, well exposed at Kostom³oty, north of Kielce (Szulczewski, 1981; Racki et al., 1985; Racki and Bultynck, 1993). The data are combined with overall palaeontological-ecological characteristics, derived mostly from unpublished master theses (Wiêzik, 1984; Niemczyk, 2003). Tentative interpretation in terms of main pro- 268 Grzegorz Racki, Agnieszka Piechota, David Bond and Paul B. Wignall Fig. 1. A — location of Holy Cross Mountains against the palaeogeographic framework of the Devonian in Poland (modified after Racki, 1993, fig. 1); B — palaeogeographic pattern of the Givetian to Frasnian of Holy Cross Mountains (based on Racki 1993, fig. 2), with a location of the Kostom³oty site Table 1 Diagnostic characteristics of oxygen-controlled facies (modified from Bond et al., 2004, table 1) Conditions (facies) euxinic (euxinic) lower dysoxic (lower dysaerobic) upper dysoxic (upper dysaerobic) oxic (aerobic) Pyrite taphofacies (Brett et al., 1991) no pyritic fossils; finely disseminated framboids only pyritic fossils, nodular, tubular and crustose pyrite 2 cavity lining pyrite druse, sparse nodular pyrite no pyrite concentration Framboidal populations Sedimentary fabric/ Ichnofabric Index (II) (Droser and Bottjer, 1986) Th/U ratio small (< 5 m m), abundant with narrow size range (standard deviation < 2) finely laminated < 1 (carb) < 3 (shales) small (< 5 m m), abundant, but with rare, larger framboids II 1 < 1 (carb) < 3 (shales) moderately common to rare, broad range of sizes, with only a small roportion < 5 m m diameter microburro-wed, bioturbation may partly obscure finely laminated fabric II 2 > 1 (carb) > 3 (shales) no framboids, very rare pyrite crystals burrowed/massive, no fine lamination II 3–5 >> 1 (carb) >> 3 (shales) cesses responsible for the deposition (oxygenation levels vs. productivity and sedimentation rate; cf. Brett et al., 1991; Table 1) is presented, in connection with the record of global transgressive-anoxic events (House and Kirchgasser, 1993; Becker and House, 1997; House et al., 2000), as well as a record of profound perturbation of global carbon cycling in the described fragment of Laurussian shelf (Yans et al., in press). GEOLOGICAL SETTING Kostom³oty Hills represent the westernmost outcrops of the Devonian system in the Holy Cross Mountains, approxi- mately 3 km NNE of Kielce (Fig. 2A). This lithologically diverse sequence (Fig. 2B) is exposed in the southern limb of the Miedziana Góra Syncline, which is a subordinate unit of the complex central (Kielce–£agów) synclinorium of the Holy Cross Mountains. The sediments are intensively disharmonically folded due to contrasting lithology; they are also faulted in places (e.g. G¹gol, 1981, fig. 31; Lamarche et al., 1999, fig. 6; Figs. 3 and 5A), and display syn-fold cleavage, related to the intensive polyphase Variscan tectonics sensu lato (Lamarche et al., 1999). Several exposures of Middle to Upper Devonian carbonate rocks, including active quarries, have been studied since the nineteenth century (see review in Szulczewski, 1971 and Racki et al., 1985). Geochemical and ecological aspects of lower Frasnian pyrite-ammonoid level at Kostom³oty 269 Fig. 2. A — generalized composite lithological section of the Givetian to Famennian strata exposed on Kostom³oty Hills (based on Szulczewski, 1981; Wiêzik, 1984; Racki et al., in prep.); B — location of the studied Kostom³oty quarries (MG — Ma³e Górki; M — Mogi³ki) against the geological map of western Holy Cross Mts.; other localities: W — Wietrznia, Œ — Œluchowice, K — Kowala 1985). Higher in the section, within the basal Frasnian part of the Szyd³ówek Beds, a transition to overlying Kostom³oty limestones is marked by the appearance of various, mostly fine-grained, limestone layers (see Fig. 4). The top of the unit is defined by the lowest thick (> 0.5 m) intraclastic bed (Racki et al., 1985; Racki and Bultynck, 1993, fig. 4). Abundant conodonts prove the Ancyrodella pramosica–A. africana level of the transitans Zone (Racki and Bultynck, 1993; Klapper, 1997), whilst the index Palmatolepis punctata was found in the topmost breccia layer of the Szyd³ówek Beds. The first occurrence of this conodont species marks the base of the punctata Zone and the boundary between the lower and middle Frasnian substages (Ziegler and Sandberg, 2001; see http://sds.uta.edu/sds18/page0042.htm). The Givetian to Frasnian boundary interval (Fig. 2B; see details in Racki et al., 1985 and Racki and Bultynck, 1993) consists of dark-coloured marls defined as Szyd³ówek Beds up to 100 m thick (Malec, 2003). They are overlying Middle Devonian dolomites and biostromal-marly Laskowa Góra Beds, and underlying Upper Devonian detrital limestones of the Kostom³oty Beds (Szulczewski, 1981). The lower and uppermost parts the unit comprise micritic and partly bioclastic limestone layers, and this lithological succession is the basis for a three-fold subdivision of the succession (Racki et al., 1985; Racki and Bultynck, 1993), which can be attributed to a shelf-basin system. The lowermost and upper portions of the Szyd³ówek Beds are well exposed in the Kostom³oty quarries, and the highest part was studied in two outcrops (Fig. 2A): 1 — primarily at the Ma³e Górki = Kostom³oty II (Kt-II) active quarry in western hill, where three sections have been logged in different years since 1984, as well as in 2 — the abandoned Mogi³ki = Kostom³oty V (Kt-V) quarry in eastern Kostom³oty Hill, 2 km to E (see Figs. 3–5 and 8). In both exposures, the monotonous middle Szyd³ówek suite is characterized by an interlayering of marly shales (to marls) and marly limestones, with septarian nodule horizons and shelly pavements of the large rhynchonellid Phlogoiderhynchus polonicus (Roemer) (Biernat and Szulczewski, 1975; Sartenaer and Racki, 1992). The position of the Middle-Upper Devonian boundary has been approximated within the upper part of the Fig. 3. A — overall view of folded Upper Devonian strata exposed in the northeastern wall of the Ma³e Górki quarry (lower exploitational level) in July 200, section Kt-IIE; B conodont-poor middle Szyd³ówek Beds (Racki, — close-up of the wall, showing transition from Szyd³ówek to Kostom³oty beds (Fig. 4) 270 Grzegorz Racki, Agnieszka Piechota, David Bond and Paul B. Wignall Fig. 4. A — results of gamma-ray spectrometry analysis across upper Szyd³ówek Beds in the Ma³e Górki section exposed in July 2001 (see Figs. 3 and 4B), and its correlation with the reference section described by Racki (1985) and Racki et al. (1985); interpretation of benthic oxygenation regimes based on multiproxy data. Two main moluscan fossil groups (pyritized goniatite and Buchiolinae bivalve) from the Goniatite Level are shown. Frasnian substages after Ziegler and Sandberg (2001); B — close-up of the logged succession from Figure 4A, with well visible black Styliolina coquina in the topmost Szyd³ówek Beds (Fig. 3B), probably recording the most oxygen-depleted regimes; note the arrowed coin (5 z³.) as a scale; 16, 18 — number of layer MATERIALS AND ANALYTICAL METHODS The upper Szyd³ówek Beds at the Ma³e Górki quarry have been logged in detail and assayed with a field portable gamma-ray spectrometer Envispec GR 320 in 2001 in the eastern wall (section Kt-IIE in Figure 3). This part of the active quarry is now covered, and only the western wall has been accessible since 2002 (Kt-IIW in Figures 5 and 8; Niemczyk, 2003). Seven samples from Kostom³oty were examined under backscatter SEM to determine the size distribution of pyrite framboid populations. To better establish the character of oxygen-depleted regimes in the Szyd³ówek to Kostom³oty Beds passage interval, 35 bulk sediment samples from Ma³e Górki (Kt-IIW section) and Mogi³ki (Kt-V) were investigated for carbon and oxygen isotopes at the Laboratory of Stable Isotopes of Polish Academy of Sciences in Warsaw (Table 2). The analyses were carried out on CO2 Fig. 5. A — transition from Szyd³ówek to Kostom³oty Beds in the western part of the Ma³e Górki quarry (lower exploitational level) in April 2002; B — close-up of the wall in October 2003, showing the Goniatite Level and basal Kostom³oty Beds (section Kt-IIW see Fig. 8) Geochemical and ecological aspects of lower Frasnian pyrite-ammonoid level at Kostom³oty obtained by dissolution of micrite and/or (sporadically) brachiopod shell material in 100% H3PO4 at 25°C for 24 hours. The measurements were made on a Finnigan MAT Delta plus mass-spectrometer. The results are expressed in ‰ relative to the PDB standard, using a NBS-19 reference sample. The accuracy of measurements approximates ± 0.02 for d13C and ± 0.04‰ for d18O. In addition, the total organic carbon (TOC) content in four samples was determined using a non-automatic Leco CR-12 analyser. GONIATITE LEVEL IN THE UPPER SZYD£ÓWEK BEDS The 4.7 m thick, dark to black upper Szyd³ówek Beds at the Kt-IIE section (Fig. 4) represent a series of thin-bedded, homo- 271 geneous, micritic limestones interbedded, in the middle part, with several shaly-marly partings, up to 0.4 m thick, with common styliolinids and rarer Amphipora branches. This 1.6 m thick clay- and pyrite-rich interval was distinguished as the Goniatite Level by Racki et al. (1985), and is limited in geographical extent to the Ma³e Górki site. In Mogi³ki, neither pyritization nor ammonoid faunas are recognized in coeval, partly clayey interval. A few fossil-poor calcarenites are notable, locally with Phlogoiderhynchus polonicus (small-sized variety of Sartenaer and Racki, 1992) that can also occur in dispersed shelly accumulations which contain many allochthonous, lagoonal microbiotic indicators (calcispheroids and other microproblematics; cf. Racki, 1993) (Fig. 6A–C). In addition to abundant pyritized minute fossils (see Figs. 4A and 6B), other forms of pyrite, including centimeter-sized pyrite crusts flattened parallel to bedding occur over a broader strati- Fig. 6. Photomicrographs of lower Frasnian limestones from western Kostom³oty (A–D) and Mogi³ki (E) sections (Fig. 8) A–C — overall character (A) and details (B–C) of the brachiopod-Amphipora intraclastic grainstone/packstone lenticle (bed 37 in Fig. 8) bounded by shales with Styliolina-rich laminae. Note co-occurrence of numerous Amphipora branches (Ap) and broken brachiopod valves, and pyritized ammonoids (Am), ichthyoliths (Icht) and gastropods (G), as well as presence of cm-sized micritic clasts (In in 6A), and graded styliolinid-intraclastic grainstone (SIG in 6B) capped by Amphipora-Styliolina shale (6C); D — Styliolina grainstone with several brachiopod valves (B; lower half) overlaid by packed Styliolina shale, with a larger pyrite nodule in a central part (P); bed 43 in Figure 8; E — Styliolina packstone with common syntaxial overgrowths on the shells (see Tucker and Kendall, 1973, and Figure 3P in Haj³asz, 1993); bed 41 in Figure 8 272 Grzegorz Racki, Agnieszka Piechota, David Bond and Paul B. Wignall Table 2 Results of carbon and oxygen isotopic analyses for two Kostom³oty sections (Fig. 8) Samples ä13C ä18O Kostom³oty–Ma³e Górki (Kt-IIW) 18 0.018 –4.447 19 0.711 –4.763 20 2.100 –4.517 25 2.509 –4.396 26 3.072 –3.946 32 1.737 –4.463 35 2.044 –4.200 37 0.799 –5.049 39 0.877 –5.559 40 1.058 –5.261 41 1.465 –4.812 42 1.885 –4.428 43 2.197 –3.740 46 3.075 –4,424 47 1.761 –3.692 48 1.363 –4.583 Kostom³oty–Mogi³ki (Kt-V) 7 0.702 –4.229 12 1.854 –4.226 17 0.902 –4.867 20 0.805 –4.863 23 1.896 –3.941 25 2.389 –4.015 29 1.383 –4.104 32 1.188 –4.410 37 1.955 –3.621 40 2.413 –4.159 42 3.338 –3.753 47 3.273 –3.674 53 1.785 –4.663 66* 1.407 –4.247 68 0.012 –4.181 70 0.758 –4.613 71 0.916 –4.553 74 2.145 –4,050 80 2.008 –4.124 * — for breccia the values refer to the matrix Beds becomes clear from the correlation of the nearby sections at Ma³e Górki (Fig. 8). The distinctively black-coloured Styliolina Horizon is 4 to 10 cm thick (Fig. 4B), and is well expressed both at the Kt-IIE section and traced 2 km to E (Mogi³ki site; Fig. 6E). This horizon occurs as a graded styliolinid-brachiopod coquinoid parting within detrital layers of the Kt-IIW section (bed 43 in Figs. 6D and 8) that are characterized by overall higher skeletal content, especially fine crinoid debris. FAUNAL ASSEMBLAGE The collection of fossils (more than 2700 specimens exceeding 0.25 mm in size), studied by Niemczyk (2003), has been obtained from the shaly samples 5 mm mostly by boiling in Glauber salt and washing, or by dissolving in a Fig. 7. Photomicrograph of the basal middle Frasnian breccia (the weak acetic acid. With exception top of the Szyd³ówek Beds), to show large angular clasts of of most brachiopods and Styliolina wackestone in fine lithoclastic-skeletal matrix with criamphiporoids, the macrofossils noid and brachiopod debris, as well as with abundant are preserved as pyritized steincalcispheroids in clasts kerns (see Racki, 1985; Dzik, 2002; Fig. 4A), with sporadic pyrite overgrowth. graphic interval of the As well as styliolinids, molluscs dominate the pyritized diSzyd³ówek Beds (Fig. 6D). minutive fauna of the Goniatite Level. Specimens, below 1 cm in The pyrite content in- size and with an average size of 3–4 mm (Fig. 4A), are mostly creases in places above identifiable only to higher taxonomic levels. Cephalopods 20% (although it is mostly (orthocone nautiloids, ammonoids) and bivalves dominate (ca. between 1 to 2%; G¹gol, 80–90% recovered specimens), together with rare gastropods 1981, table 13). The and brachiopods, as well as amphiporoid and sporadic tabulate fissility of the Goniatite coral branches (Wiêzik, 1984; Niemczyk, 2003). Strongly fragLevel and underlying lay- mented nautiloid shells preclude their taxonomic identification, ers varies according to the as well as a more precise analysis of the faunal composition and carbonate content (mostly dynamics in the lower Frasnian interval. However, in the westabove 25%), whilst the or- ern site Kt-IIW, brachiopods are certainly the most numerous ganic carbon content is component (58% of the collection), followed by ammonoids close to 1% regardless of li- (20%; Niemczyk, 2003). Only the ammonoid fauna was studied thology, with the maximum by Dzik (2002), but partly erroneously referred to the adjacent TOC value 1.78% in the Laskowa quarry section. The association is dominated (cf. Kt-IIW/31 sample. Niemczyk, 2003) by Epitornoceras mithracoides (Frech) and A single breccia layer Acanthoclymenia genundewa (Clarke), supplemented by forms the top of the Koenenites lamellosus (Sandberger and Sandberger) and Szyd³ówek Beds at Kt-IIE Linguatornoceras compressum (Clarke). Occurrence of true section (Fig. 7), and to- Manticoceras (Dzik in Racki, 1985) is not confirmed in this ward the west the study. However, according to Becker (e-mail comm., 2004), coarse-grained varieties some of the taxonomy in Dzik (2002) is debatable, and a juvenile are more frequent; in fact, Manticoceras is certainly present in the material: in particular, all the diachronous nature of or a part of the specimens linked with the genus Koenenites the bottom of Kostom³oty probably belongs to the Manticoceras lamed Group. Geochemical and ecological aspects of lower Frasnian pyrite-ammonoid level at Kostom³oty 273 Fig. 8. Stable carbon isotope geochemistry for the lower to middle Frasnian strata in Kostom³oty sections (Fig. 2A), correlated with the reference 1984 section described by Racki (1985) and Racki et al. (1985). Note the time marker styliolinite horizon and a rapid facies transition over a distance of ca. 100 m recorded in the diachronous bottom part of Kostom³oty Beds at Ma³e Górki (Kt-II). The lower-middle Frasnian “background” ä13C value of ca. 1‰ is taken from the regional (Fig. 10) and broadly supra-regional data (Yans et al., in press) Among other fossil groups, provisionally surveyed by Niemczyk (2003), common buchioline bivalves dominantly belong to Glyptohallicardia ferruginea (Holzapfel), with rare Planocardia tennicosta (Sandberger and Sandberger) and unidentified species of Opisthocoelus and Buchiola. Brachiopods are represented by small-sized biernatellids and larger (up to 3 cm) leiorhynchid rhynchonellids, probably mostly P. polonicus, supplemented by sporadic inarticulates (cf. Wiêzik, 1984). Relatively diverse microgastropods, with maximum size 7 mm, include indeterminable subulitids and Palaeozygopleura (Rhenozyga), and Naticopsis kayseri (Holzapfel), but Lahnaspira taeniata (Sandberger) is by far the most numerous of the gastropods (> 80% of the associa- tion). Rock-forming styliolinids include widespread Styliolina ex. gr. nucleata Karpinsky, and S. domanicense Lyashenko (Haj³asz, 1993). GEOCHEMISTRY AND FRAMBOIDAL PYRITE Oxygenation levels were interpreted in the Kostom³oty succession using three independent criteria: sediment fabric (i.e. presence of fine lamination/bioturbation features), authigenic uranium values (cf. Bond et al., 2004) and pyrite taphofacies vs. framboid size populations (Table 1). Interpretation of the oxygen-depleted environments (Byers, 1977; Wignall, 1994) 274 Grzegorz Racki, Agnieszka Piechota, David Bond and Paul B. Wignall Fig. 9. SEM photos of framboidal pyrites from the Goniatite Level at Kt-IIW section (Fig. 8), to present several smaller framboids, accompanied by a few large ones, and also some pyrite macrocrysts, the typical signature of dominantly dysoxic settings; sample Kt-IIW/37 (A–B) and Kt-IIW/43 (C–D) was reinforced by microfacies analysis of limestone layers, as well as carbon isotope secular trends. GAMMA-RAY SPECTROMETRY VS. SEDIMENTARY FABRIC Gamma-ray spectrometry (GRS) of the 3.4 metres thick section of the upper Szyd³ówek Beds at Ma³e Górki was measured, and the laminated shaly interval (the Goniatite Level) revealed Th/U ratios of 2–2.5 (Fig. 4A). Between beds 16 and 18, near the top of Szyd³ówek Beds, the Th/U ratio approaches 1.0. The fabric of the more carbonate-rich layers is less laminated, and essentially nodular to massive (i.e. bioturbated). INTERPRETATION Field portable gamma ray spectrometer can provide a measure of redox conditions because of the enrichment of U under Fig. 10. Stable carbon isotope geochemistry for the lower to middle Frasnian strata at Wietrznia (reference section Ie in Racki and Bultynck, 1993) in Kielce (Piechota and Ma³kowski, in prep.). Note a general similarity of the carbonate C-isotopic trend to the Kostom³oty curves (Fig. 8). The conclusive proof of the distinctive positive ä13C excursion, but initially interrupted by fall in the upper transitans Zone, is provided by organic matter data. A diagenetic bias of the carbonate record is visible in far more varying ä13C values (circles in rows exhibit different values measured in a sample from one bed). In the lower transitans Zone, four ä13C values for brachiopod calcite from Wietrznia cluster around 1‰ (from 0.45 to 1.41‰; Yans et al., in press); for other explanations see Figure 8 anoxic conditions often measured as either authigenic U enrichment or a decline in Th/U ratios (Wignall and Myers, 1988; Allison et al., 1995). Uranium is precipitated in anoxic condi- Geochemical and ecological aspects of lower Frasnian pyrite-ammonoid level at Kostom³oty 275 Fig. 11. Position of the Kostom³oty sections under study (Fig. 1B) against developmental stages of the Middle to Late Devonian bank-to-reef complex of the Holy Cross Mountains; stratigraphic-facies cross-section (after Racki 1993, fig. 3, changed) is shown to emphasise eustatic rhythmic control of the depositional pattern; IIa–IId — transgressive-regressive cycles modified from Johnson et al. (1985) tions thus adding an authigenic component to the detrital sediment component. In contrast sediment Th content is entirely terrigenous in origin. However, the carbonate to clastic ratio of sediments also exerts a fundamental control on Th and U contents: detrital sediments generally have higher Th contents than carbonates with the result that the Th/U ratio of shales is typically greater than 3, but for pure carbonates the ratio is typically lower than 1 (Myers and Wignall, 1987). At Ma³e Górki the fluctuations of the Th/U ratio can be seen to primarily reflect the lithological variations. Thus, the marly layers display higher Th/U values, between 2 and 3, than the purer carbonate layers. However, these values are typical of dysoxic clastic deposits (Myers and Wignall, 1987; Fig. 4A) suggesting oxygen-restriction during deposition of the pyritic level. PYRITE TAPHOFACIES VS. FRAMBOID SIZE POPULATIONS Framboidal pyrite is common in the western Kostom³oty samples from the upper Szyd³ówek Beds, including the finely laminated Goniatite Level. Four shaly samples are all dominated by syngenetic populations with most framboids being 5–10 m m, but with rarer larger forms supplemented by some pyrite macrocrysts (Fig. 9A–B). Sparse, and on average smaller and less variably sized, pyrite framboids are found locally in the styliolinite sample (Fig. 9C–D). In contrast, sample Kt-IIW/47 from the overlying fine-grained variety of Kostom³oty Beds does not contain framboids but merely blebs of pyrite. INTERPRETATION Studies of recent and ancient sediments reveal that, where secondary pyrite growth is limited, framboid size distribution may be reliably used to indicate redox conditions. If bottom waters become euxinic, then framboids develop in the sulfidic water column but are unable to achieve diameters much larger than 5 m m before they sink below the Fe-reduction zone and cease growth (Wilkin et al., 1996). Thus, euxinicity produces populations of tiny framboids with a narrow size range. In contrast, in dysoxic settings, where anoxic conditions are restricted to the surficial sediments, size is largely governed by the local availability of reactants; thus, the framboids are larger and more variable in dimension (Wilkin et al., 1996), especially when a long-term euxinicity is punctuated by brief sea-floor oxygenation (see Bond et al., 2004). Framboidal pyrite from the upper Szyd³ówek Beds has a size distribution indicative of dysoxic conditions. The presence of pyritic fossils paired with nodular and crustose pyrite aggregates is characteristic of upper dysoxic facies (Brett et al., 1991; see Table 1). In the Styliolina Horizon, episodes of anoxic conditions are suggested, whilst limited pyrite data from Kostom³oty Beds are indicative of far better oxygenation. CARBON ISOTOPES The C isotope record, based on the Kt-IIW section (Fig. 8; Table 2), shows two positive ä13C excursions in the transitans Zone (Szyd³ówek Beds) and the transitional transitanspunctata zonal interval (Kostom³oty Beds). The first shift is observed mostly below the Goniatite Level, where values of ä13C increase from 0 to 3‰. The gradual decrease in ä13C is registered near the top of the Szyd³ówek Beds with a 0.8‰ minimum within the upper Goniatite Level. The upper less distinctive positive excursion in ä13C is affirmed higher in this succession. The increase in ä13C culminates up to ca. 3.1‰ above the Styliolina Horizon. This latter isotopic trend is reproduced by preliminary data from the more extended Mogi³ki succession. Like in the 276 Grzegorz Racki, Agnieszka Piechota, David Bond and Paul B. Wignall Fig. 12. Early to middle Frasnian event stratigraphy scheme to show relationships between eustatic/biotic events (based mostly on fig. 1 in House, 2002; Racki, 1993), presumed global carbon-isotopic cyclicity (inorganic record only from Ardennes; modified from fig. 3 in Yans et al., in press), and their manifestation the western Holy Cross Mountains (based on Kostom³oty, Œcignia, Wietrznia, Œluchowice and Kowala sections, Racki, 1993 and references cited; see Figs. 2A and 11). Long-lasting Rhinestreet “Event” encompasses several deepening pulses from the punctata to at least jamieae Zones (= MN6 to MN11 Zones; Klapper and Becker, 1999) Kt-IIW section, the uppermost Szyd³ówek Beds are marked by the significant ä13C shift from 1.4‰ to above 3.3‰, with a peak located also just above the guide styliolinite intercalation (Fig. 8). However, the lower positive excursion is obscured by highly fluctuating values, with a 2.4‰ maximum in a level approximately corresponding to the Goniatite Level. In addition, a gradual increase in ä13C values (from 0 to 2.1‰) is recorded in the basal Kostom³oty Beds in the punctata Zone. INTERPRETATION Diagenetic alteration of carbonates frequently obscures the primary carbon and oxygen isotope pattern, but brachiopod shells and micritic matrix may retain its general features through time (e.g. Azmy et al., 1998; Stanton et al., 2002; Brand et al., 2004). Values of ä13C and ä18O from the mostly organic-rich micrites of upper Szyd³ówek Beds at Ma³e Górki (Table 2) show a moderate level of covariance (r = 0.57 for 16 samples) suggestive of some post-sedimentary modification but, as discussed by Marshall (1992), not definitely; therefore, only more reliable carbon isotopic data (as summarized in Brand, 2004; see also Joachimski et al., 2004) are interpreted below. Positive ä13C excursions, established at the Kostom³oty sections, are of the similar range in absolute values, and up to 2.3‰ above the assumed lower-middle Frasnian “background” ä13C value of ca. 1‰ (Fig. 10). These signals could be most simply explained as a global pulse of elevated organic carbon production (e.g. Azmy et al., 1998; Caplan and Bustin, 1999), although other factors are possibly involved as well (Kump and Arthur, 1999; Saltzman, 2002; Sageman et al., 2003; see below). An increase in ä13C may serve as indicator of enhanced burial of organic matter that is expected to reduce the concen- tration of oceanic dissolved carbon dioxide (Brasier, 1995; Caplan and Bustin, 1999; Joachimski et al., 2002). On the contrary, the noticeable drop in ä13C characterizes black-shale facies (especially the upper Goniatite Level). A diagenetic signal, with proportionally more 12C-enriched carbonate coming from the sulphate-reduction zone during deposition of the clay-rich goniatite interval, is very likely but remains undetermined. Organic carbon isotopic data from the reference fore-reef Wietrznia succession at Kielce, located in the same sedimentary basin (see Figs. 2A and 10–11), reveal the ä13C “low” in the uppermost transitans Zone (Piechota and Ma³kowski, in prep.). Thus, regionally primary character of the lower Frasnian negative ä13C excursion is unquestioned and may record a reduction in primary productivity as well as a decreased oceanic mixing and/or a sea level fall during their deposition (e.g. Caplan and Bustin, 1999; Immenhauser et al., 2003). Nonetheless, a pronounced inter-locality variation within the ä13C shifts in the transitans Zone, registered only in the certainly diagenetically-biased carbonate samples (initial event I in Fig. 10), remains a puzzle for further chemostratigraphical research. It is notable as well that coeval ä13C values for a brachiopod calcite from Ardennes indicate a distinctly higher increase to values around 4.4‰ (Fig. 12; Yans et al., in press). DISCUSSION Above appraisal of different proxies for oxygen-deficient environments, studied in the Szyd³ówek Beds to Kostom³oty Beds transition, provides a starting point for the elucidation of the evolving habitats and biofacies from regional and global viewpoints. Geochemical and ecological aspects of lower Frasnian pyrite-ammonoid level at Kostom³oty DEPOSITIONAL ENVIRONMENT AND BIOTA The Kostom³oty-£ysogóry basin represents a submerged, small (“tongue”-like) part of the Laurussian shelf (Fig. 1), formed during the latest Eifelian deepening pulse (Fig. 11; Racki, 1993). The Szyd³ówek Beds are an example of the rhythmic Givetian to Frasnian hemipelagic deposition in the oxygen-depleted basin of the Kostom³oty transitional zone, occasionally affected by bioclastic-debris supplied from adjacent shoals, especially from vast lagoonal areas of the evolving Kielce carbonate platform (Racki and Bultynck, 1993). Northward, in the £ysogóry area, a comparable deeper-water facies is thicker (ca. 300–400 m, Nieczulice Beds; Czarnocki, 1950; Turnau and Racki, 1999; Malec, 2003). A similar ammonoid fauna with Epitornoceras mithracoides and Acanthoclymenia genundewa, but probably somewhat more advanced phylogenetically, was described by Dzik (2002) from lower Frasnian (priamosica-africana fauna; Racki, unpub.) black marly shales and limestones at Œcignia near Bodzentyn in this region (Fig. 2A). Laminated sedimentary fabric and the dominantly pelagic biota of the Goniatite Level (styliolinids, cephalopods) suggest benthic anoxia (Oxygen Restricted Biofacies, ORB 2 of Wignall, 1994; Allison et al., 1995). However, Th/U ratios and pyrite framboid sizes imply only dysoxic conditions. Very intensive early skeletal pyritization is evident from non-compacted shelly fossils, which additionally supports the dysaerobic facies assignment (Table 2; Brett et al., 1991). Among shelly benthos (see below), numerous leiorhynchid brachiopods occur in places in the bottom part of shaly layers with the pyritized fossils (Krawczyñski, pers. comm., 2004), suggesting perhaps transient colonization of atypical lower dysaerobic–type habitat (ORB 4). Nonetheless, the preservation of fine lamination indicates that a soft-bodied bioturbating community was mostly excluded, and presence of bacterial mats, restricting seawater recharge, could be an explanation for a sharp gradient in redox potential at the sediment-water interface (Powell et al., 2003). Moreover, a key role of microbial biofilm in fossil pyritization processes has recently been emphasized by Borkow and Babcock (2003). These unusual low-oxygen environments are part of hemipelagic settings that developed during early Frasnian deepening pulse (Fig. 11) under conditions of decreased carbonate productivity (an important factor in fossil pyritization; Brett et al., 1991). This sea level rise is manifested also in the fore-reef environment over the northern slope of the Dyminy Reef by the onset of the storm-affected hemipelagic deposition found in the middle Wietrznia Beds (Szulczewski, 1971; Racki 1993; Racki and Bultynck, 1993). Basinal oxygen-deficiency probably increased near the close of the early Frasnian and was associated with a Styliolina acme producing a coquina resembling recent pteropod ooze (Tucker and Kendall, 1973). This marker horizon (Fig. 8) certainly records an interval of increased biotic productivity, reflected in the positive ä13C excursion. The spectacular bloom of a suspension-feeding macroplankton (Thayer, 1974) was probably an immediate biotic response to enhanced nutrient supply. On the other hand, Kostom³oty basin was somewhat susceptible to transient oxygenation episodes and variable redox regimes (see examples in 277 Raiswell et al., 2001 and Racki et al., 2002), and progressive bioturbation of bottom muds in the early to middle Frasnian transition timespan is revealed by sedimentary fabric data (Fig. 4A). This changing level of bottom-water oxygenation permitted colonization by a pioneer soft-bodied infaunal biota, perhaps similar to high-density, symbiont-bearing annelid faunas encountered in modern dysoxic settings (Levin et al., 2003). The stagnant depositional phase in the Kostom³oty basin was followed by high-energy events recorded in the basal Kostom³oty Beds. As discussed by Racki and Narkiewicz (2000), synsedimentary tectonic pulses probably caused large-scale resedimentation phenomena and coarse-detrital deposition (see Fig. 6) during the basal middle Frasnian sea level rise (IIc cycle of Johnson et al., 1985; Racki, 1993). In ecological terms, the typical goniatite/“Buchiola” dark shales carry a pyritized diminutive fauna, suggestive of a hypothetical site of ammonoid breeding (House, 1975, p. 482). It is somewhat uncertain whether the minute individuals are mostly juveniles or dwarfed adults (e.g. opportunistic species; see a comparable Cretaceous community in Lukeneder, 2003). Nonetheless, an increased juvenile mortality was a prominent biotic character of many hypoxic habitats, exemplified by low-diversity gastropod association described from a Carboniferous black shale by Nützel and Mapes (2001). Episodic pioneer colonization by specialized shelly faunas occurred as benthic oxygenation, and probably gradual shallowing, occurred westward in the Kostom³oty area (see Fig. 8). In fact, leiorhynchid and lingulid brachiopods are well-known dwellers of muddy low-oxygen habitats (Wignall, 1994; Allison et al., 1995), exemplified in the early to middle Frasnian Phlogoiderhynchus Level in Holy Cross Mts. (Sartenaer and Racki, 1992; Racki, 1993). Moreover, biernatellid athyroids successfully settled the Kostom³oty basin during deposition of middle Szyd³ówek Beds (Baliñski, 1995). For the Buchiolinae, in contrast to traditional view of these minute, ribbed, cardiolid bivalves as an epiplankton (Thayer, 1974; House, 1975), Grimm (1998) suggested exclusively benthic mode of life (as did Allison et al., 1995). On the other hand, allochtonous amphiporoids (also calcispheroids and enclosing intraclasts; see Figs. 6A–C and 7), as well as crinoid detritus and some reef-dwelling gastropods (palaeozygopleurids; Krawczyñski, 2002), are distal signatures of basinward transport of skeletal-muddy material from the Dyminy Reef during severe storm episodes (Racki and Bultynck, 1993). RECORD OF THE GLOBAL DEEPENING-ANOXIC EVENT The peculiar hypoxic regimes of the Goniatite Level are a typical example of the starved deeper-water regimes of the £ysogóry Basin (sensu lato) developed throughout early Frasnian eustatic rise of the IIb/c Subcycle (Figs. 11–12), as discussed by Racki (1993, p. 156–157) and Narkiewicz (1988). The diminutive ammonoid fauna from Kostom³oty is interpreted by Dzik (2002) as related to the Genundewa-Frasne deepening interval, a global bio-event. The reference Genundewa Limestone of New York is considered as a transgressive anoxic facies marked by pelagic styliolinites with a meagre benthos (House and Kirchgasser, 1993; Thayer, 1974). In general terms, the early Frasnian biotic turnover 278 Grzegorz Racki, Agnieszka Piechota, David Bond and Paul B. Wignall (called also Manticoceras Event; Walliser, 1985, Racki, 1993), is regarded as a stepwise evolutionary change promoted by intermittent pulsatory transgression (House, 2002). Dzik (2002) recorded Acanthoclymenia genundewa that suggested correlation between the Goniatite Level and the Genundewa Limestone together with the overlying West River Shale of New York State (see House and Kirchgasser, 1993). However, the Genundewa Event has been dated as the upper part of the MN 2 Zone of Klapper (1997; see House and Kirchgasser, 1993; Becker and House, 1997; House et al., 2000). Thus, this event predates the Kostom³oty hypoxic and eutrophic episode, and the conodont data (cf. Over et al., 2003) point to time-equivalency of the Goniatite Level and the West River Shale. This implies delayed migration of the goniatite community toward this part of Laurussian shelf, as noted also for coeval conodonts by Racki and Bultynck (1993). On the other hand, the timing of the Goniatite Level (i.e. transitans Zone with Ancyrodella priamosica = MN 4 Zone; Klapper and Becker, 1999; Over et al., 2003) points to its link with the Timan Event of Becker and House (1997) (Fig. 12), even if the guide genus Timanites has not yet been found; the absence of this genus in Poland is typical for the western Palaeotethys (Becker, 2000, p. 391, fig. 2). The main styliolinite depositional phase of North Africa lies in the transitans Zone (Wendt and Belka, 1991: “Lower Kellwasser Beds”; Becker and House, 2000), and has been used jointly with Australian (Becker and House, 1997) and Timan evidence (House et al., 2002) to define the global Timan Event. Notably, according to Becker and House (1997), this deepening pulse was characterized by a diversity of oxygenation regimes. In general terms, however, organic-enriched deposition, with common styliolinid coquinas, is a remarkable supra-regional feature during early Frasnian spreading of oxygen-depleted waters onto the shelves, interpreted as evidence for an ongoing rise of the oxygen minimum zone (OMZ) triggered by transgressive pulses (Lüning et al., 2003, 2004). Remarkably, this characteristic facies is described also from the basal middle Frasnian in the submerged Silesia-Cracow part of the southern Polish Devonian shelf (see Fig. 1A; Narkiewicz, 1978; Sobstel, 2003), and is also typical of the celebrated middle Frasnian Domanik suite of Eastern Laurussia (Maksimova, 1970; Kuzmin et al., 1997). This depositional phase is especially well recorded in black organic-rich strata (TOC up to 14%) of the North Gondwanan shelf (Walliser, 1985, p. 404; Wendt and Belka, 1991; Becker and House, 1997, p. 135; Lüning et al., 2003, 2004), where maximum anoxia is developed distinctly earlier, in MN 1-2 corresponding to the earliest Frasnian (Lüning et al., 2004). The oxygen-poor denitrified waters could indeed be attractive for biota due to increased chemical availability of nutrients occurring as reduced nitrogen compounds (anoxitropic biotope of Berry et al., 1989). This still poorly-known niche (Levin et al., 2003) was occupied by Palaeozoic plankton and nekton, such as styliolinids, thin-shelled bivalves and brachiopods, small orthocone nautiloids, and early ammonoids (e.g. Thayer, 1974), and was widespread across the oxygen-deficient shelves during sea level highstand in greenhouse climates (Berry et al., 1989). Blooming of the specially adapted biota during some anoxic events, exemplified by the Late Famennian annulata Event, is well known (Becker, 1992; Walliser, 1996). REGIONAL RESPONSE TO THE MAJOR BIOGEOCHEMICAL PERTURBATION The recent high-resolution carbon isotopic data of Yans et al. (in press) from lower to middle Frasnian brachiopod calcites of Belgium (Ardennes) reveal the most significant Devonian positive d13C shift to 5.85‰, followed by the abrupt negative excursion in the punctata Zone to –1.20‰ (cycle 6 in Fig. 12). This carbonate “heavy carbon” interval, that commenced during deepening pulse in the late transitans Zone and lasted ca. 0.5 m.y., is generally supported by isotopic data from Holy Cross Mts., including one brachiopod measurement (d13C = 4.32‰) from the punctata Zone at Kostom³oty–Ma³e Górki. Although a global extent of this isotope anomaly still awaits detailed study it is nevertheless strongly suggested by similar biogeochemical signals reported from the lower to middle Frasnian passage strata of Moravia and South China (Yans et al., in press; see also van Geldern and Joachimski, 2001; Geršl and Hladil, 2004). The advanced study of the Frasnian localities of Holy Cross Mts. (Piechota and Ma³kowski, in prep.) has confirmed and refined this overall positive-to-negative pattern. The somewhat fluctuating positive carbonate d13C excursion up to 4.5‰ is especially well-proved in bulk micrite samples from Kowala in the southern Kielce region (for a location see Fig. 2A), as well as in organic matter from Wietrznia (Fig. 10). Comparison with the d13C curves from the Kostom³oty sections (Fig. 8) shows that the Goniatite Level and Styliolina Horizon likely correspond to the variously recorded initial phase of this d13Ccarb rise (event I), better developed in the Kostom³oty successions. Thus, the above discussed high-productivity styliolinid acme in progressively more hypoxic conditions was a conspicuous regional feature closely preceding the major worldwide perturbation in a carbon cycling (Fig. 12). The highly positive C-isotope ratios are a signature of exceedingly enhanced bioproductivity and organic matter burial during the early to middle Frasnian rising sea level stands (Yans et al., in press). An extraordinary acceleration of plant-mediated chemical weathering, promoted by a land-derived nutrient input, is usually assumed to be a crucial control on the generally elevated Frasnian marine bioproductivity (Algeo et al., 1995; Joachimski et al., 2001, 2002). Furthermore, influx of heavy carbon 13C due to augmented carbonate weathering may have also enhanced a positive d13C signal (Kump and Arthur, 1999; Saltzman, 2002). The weathering biogeochemical impact would be especially significant only when linked to an accelerated water cycle during intensified greenhouse conditions (Ormiston and Oglesby, 1995; Saltzman, 2003); nevertheless, a prominent increase in surface water temperature is observed later in the middle Frasnian, with calculated ocean-surface water temperatures rising to 32°C during the late Frasnian (Joachimski et al., 2004). Potentially important in the climatic-weathering context, Frasnian volcanism in the nearby Pripyat Trough (Belarus) associated with a development of a large-scale intraplate rifting, was Geochemical and ecological aspects of lower Frasnian pyrite-ammonoid level at Kostom³oty also essentially younger (see Aizberg et al., 2001) than the worldwide biogeochemical perturbation under discussion. More importantly, if nutrients were supplied exclusively from weathering of continental rocks, the nearshore domains (and not the distal pelagic areas) should show extensive evidence of eutrophication. However, the reverse is mostly true, what supports a marine nutrient recycling and/or upwelling as a main fertilization source for open carbonate shelves (Becker, e-mail comm., 2004; cf. also Racki et al., 2002; Hiatt and Budd, 2003; Sageman et al., 2003). In fact, the Frasnian sea level rises are seen as a key stimulus for organic matter burial (e.g. Lüning et al., 2003, 2004; Sageman et al., 2003), and the model of transgression-promoted migrating OMZ may be generally applied for the Kostom³oty intrashelf basin because the positive d13C shift is observed in intermittent, two-step eustatic sea level rise across the early to middle Frasnian transition (Racki, 1993; Fig. 12). In addition, the geochemical impact of meteoric fluids is diminished during sea level rise, and thus 13C-depleted water masses effectively mixed with isotopically dissimilar 13C-enriched oceanic waters (Immenhauser et al., 2003). This positive d13C trend was temporarily reversed in its initial phase at least in the described part of the Laurussian shelf (Fig. 10). Nevertheless, an origin and maybe supra-regional extent of this signal (Fig. 12) requires additional investigation. An intricate intra-regional record of the major biogeochemical perturbation in the Devonian earth-ocean system (appearing conspicuous even when compared with the F-F boundary event; Yans et al., in press) is especially noteworthy. CONCLUSIONS In the lower Frasnian (transitans Zone) rhythmic basin succession of upper Szyd³ówek Beds at Kostom³oty (western Holy Cross Mts.) includes a distinctive horizon named the 279 Goniatite Level. It is 1.6 m thick, highly fossiliferous, and pyrite- and organic-rich (Racki et al., 1985). The mostly pelagic assemblage is dominated by diminutive (?mostly juvenile) molluscs including goniatites (Dzik, 2002), bivalves and styliolinids. This shaly-dominated interval is marked by a Th/U ratio and pyrite-framboid size-signature suggestive of dysoxic environments. The scarcity of infauna and bioturbation, resulting in laminated fabrics, as well as a low diversity of the presumed benthos (mostly brachiopods), suggest a stressful benthic habitat under conditions of reduced carbonate productivity and overall sediment starvation. In the topmost part of the Szyd³ówek Beds, distinguished by the Styliolina coquina intertwined between limestone-biodetrital layers, the above geochemical proxies indicate a tendency to somewhat increased (?fluctuating) bottom oxygen deficiency and higher carbon burial rate linked with a bloom of pelagic biota during high-productivity episode. The specialized biota and distinctive environments were paired with invasion of oxygen-depleted waters during the transgressive Timan Event (cf. Becker and House, 1997) in the drowned part of southern Laurussian shelf that was free, however, of a sulfidic lower water column in the Kostom³oty basin. Acknowledgments. This work has been supported by the State Committee for Scientific Research (KBN grant 3 P04D 040 22 for G. Racki). The British Council funded the Polish fieldwork for English co-authors as an element of the Academic Research Collaboration (ARC) scheme. Anonymous journal reviewer and T. Becker are kindly acknowledged for thoughtful examination of a draft and many constructive suggestions for improving the manuscript. Several workers and students of the Silesian University, particularly Dr. W. Krawczyñski, Dr. M. Racka, M. Lewandowski, M. Rakociñski, I. Jab³eka and A. Witek, assisted in the field and laboratory works. Drs. M. Sobstel, K. Ma³kowski and L. 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