Age and Origin of the Well-Preserved Organic Matter in Internal Sediments from the Silesian-Cracow Lead-Zinc Deposits, Southern Poland

Maciej Rybicki,1,† Leszek Marynowski,1 Stephen Stukins,2 and Krzysztof Nejbert3 1 University of Silesia, Faculty of Earth Sciences, Be˛dzi´nska Str. 60, 41-200 Sosnowiec, Poland 2 Natural History Museum, Department of Earth Sciences, Cromwell Road, London SW7 5BD, United Kingdom 3 University of Warsaw, Faculty of Geology, Z˙ wirki i Wigury Str. 93, 02-089 Warszawa, Poland

Abstract The molecular and petrographic characteristics of organic matter in internal sediments from the Mississippi Valley-type lead-zinc deposits in southern Poland reveal immature and well-preserved organic matter. Humi- nite reflectance values of organic matter in all internal sediments are low, with a mean value of 0.29%, corresponding to a lignite range of coalification. Most organic compounds in the organic matter (e.g., cadalene, retene, simonellite, perylene, and β-sitosterol and its transformation products stigmastanol and stigmasta- 3,5-dien-one), as well as lignin degradation compound products (e.g., benzoic acid, vanillin, 4-benzaldehyde, benzenedicarboxilic acids, and hydroxybenzoic acids), are of terrestrial origin. Monosaccharides with dominant α- and β-glucose were identified as possible remnants of cellulose degradation products, suggesting an excellent state of organic matter preservation, given that monosaccharides are preserved only under conditions of limited oxygen after sedimentation, resulting from the rapid accumulation of internal sediments in meteoric paleokarst cavities followed by insignificant diagenesis. Petrologic and palynological data on internal sediments clearly indicate a Middle Triassic age for organic matter and for the development of a Triassic meteoric karst system immediately after Anisian carbonate sedimentation.

Introduction Organic matter occurs (1) in the form of so-called dop- Organic matter commonly co-occurs with sediment-hosted ore plerite (Sass-Gustkiewicz and Kwiecińska, 1994, 1999), i.e., deposits and could be involved in the genesis of economically black or brown coal-like fillings of cavities and fissures within valuable mineralization (Püttmann et al., 1988; Disnar and the breccia-type lead-zinc ores, (2) as dispersed organic mat- Sureau, 1990; Greenwood et al., 2013). In many cases, espe- ter within mineralized or unmineralized internal sediments cially in Mississippi Valley-type lead-zinc deposits, hydrocar- (Dz˙ułyński, 1976; Leach et al., 1996; Sass-Gustkiewicz, 1996, bons migrate separately or together with mineralization fluids 2007), a product of internal deposition in hydrothermal and/or within sedimentary basins and deposit in the form of liquid or meteoric paleokarst systems (e.g., Dz˙ułyński, 1976; Dz˙ułyński solid bitumens in the vicinity of sulfides (Spirakis, 1986; Mon- and Sass-Gustkiewicz, 1985; Ford, 1988; Głazek et al., 1989), tacer et al., 1988; Manning and Gize, 1993; Kozłowski, 1995; and (3) in the form of liquid hydrocarbons filling fluid inclu- Spangenberg and Macko, 1998; Spangenberg and Herlec, sions within sphalerite and Ca-Mg carbonates (Kozłowski, 2006; Rieger et al., 2008). Alternatively, organic matter may 1995; Karwowski et al., 2001). be liberated from surrounding sedimentary rocks. Organic Commonly, organic matter associated with Mississippi Val- matter may be also altered due to the impact of thermal fluids ley-type deposits is exposed to several postaccumulation pro- (Püttmann et al., 1988; Williford et al., 2011). In some cases, cesses which may alter its initial composition (Pering, 1973; ore deposits can form within only partially lithified organic Macqueen and Powell, 1983; Gize and Barnes, 1987; Leven- matter-rich marine sediments as a result of deep-ocean hydro- thal, 1990; Henry et al., 1992; Disnar, 1996; Landais and Gize, thermal influences (Simoneit, 1993; Chen et al., 2003). Black 1997; Gize, 1999). These processes include biodegradation shales are commonly enriched in metals and sulfides because (Connan, 1984; Pratt and Warner, 2000), thermal alteration of euxinic conditions during sedimentation that promote the (Simoneit et al., 1981), water washing (Palmer, 1993), and/or formation of ores during hydrothermal alteration (Püttmann oxidation since mining (e.g., Leythaeuser, 1973; Petsch et al., et al., 1989, 1991; Leventhal, 1993). Finally, concentrations of 2000). organic matter in the form of coals or bitumens may co-occur The origin and age of organic matter from the Silesia-Cra- within orebodies without clear inherent connections to the cow zinc and lead deposits, although a subject of study for ore-forming event (e.g., Sass-Gustkiewicz and Kwiecińska, many years (e.g., Kołcon and Wagner, 1983; Sass-Gustkiewicz 1994, 1999). Silesian-Cracow lead-zinc deposits from south- and Kwiecińska, 1994, 1999), have not been determined so ern Poland belong to this last group. These ores are classified far. These issues are important in the field of both organic as Mississippi Valley-type deposits (Sass-Gustkiewicz et al., geochemistry and ore geology; appreciating this perspective 1982, and references therein), with most being economically could lead to a better understanding of the role of organic important resources among the Middle Triassic ore-bearing matter in the formation of Mississippi Valley-type deposits. dolomites of the Silesian-Cracow region. This study aims to clarify the origin, age, and geochemical alteration of organic matter from the Silesian-Cracow lead- zinc deposits using geochemical, palynological, and mineral- † Corresponding author: e-mail, [email protected] ogical analyses.

Submitted: January 6, 2016 0361-0128/17/4489/775-24 775 Accepted: December 16, 2016 776 RYBICKI ET AL.

Geologic Setting The Silesian-Cracow lead-zinc ore deposits are located at The study area is located in the Silesian-Cracow Upland, the contact of the Upper Silesian coal basin, the Cracow- southern Poland, where lead-zinc ore deposits occur in the Myszkow zone, and the Carpathian foredeep (Fig. 1). They are strata-bound, carbonate-hosted sulfide bodies, composed border zone of the Bohemian Massif (Sass-Gustkiewicz predominantly of sphalerite and galena. The deposits occur et al., 1982; Gałkiewicz and Sliwiński,´ 1985; Wodzicki, 1987; mainly in dolostone known as organic matter-poor, ore-bear- Górecka, 1993; Kozłowski, 1995; Sass-Gustkiewicz and ing dolomite (Bogacz et al., 1972, 1975) of Middle Triassic Dz˙ułyński, 1998). The geologic structure of this ore district (Lower Muschelkalk) age, with lesser amounts of ore min- includes the Cracow-Myszkow zone and two tectonic-sedi- erals in rocks of Devonian to Upper Jurassic age (Sliwiński,´ mentary complexes: block-folded Paleozoic rocks, and nearly 1964; Harańczyk, 1979; Viets et al., 1996; Sass-Gustkiewicz horizontal Mesozoic sediments with patches of Tertiary rocks and Kwiecińska, 1999). Most deposits occur in the relatively (Kozłowski, 1995). Considered in greater detail, the Cracow- large area between Bytom in the west, Chrzanów to the south, Myszkow zone is located between two structural units: the Olkusz to the east, and Zawiercie to the north (Górecka, 1993; Upper Silesian Massif to the west, and the Malopolska Massif Fig. 1). to the east. The first massif represents a consolidated Precam- Orebodies, as well as coexisting organic matter, devel- brian microcontinent (Górecka, 1993), whereas the second oped as open-space fillings and mineralized collapse brec- massif constitutes a separate crustal block interpreted as a cias within a complex, possibly meteoric and/or hydrothermal tectonostratigraphic terrane derived from Gondwana (Bełka paleokarst system. The origin of these open spaces, at the et al., 2002). contact of the ore-bearing dolomites and the Lower Gogolin

16°E 18°E 20°E 22°E Erosional edge Kraków-Lubliniec fault zone (KLFZ)

Fault Upper Silesian Coal Basin (USCB) 56°N Gdan´sk Uplifted Devonian sediments Triassic sediments Zones mineralized with Zn-Pb sulfides Warszawa

Lubliniec 54°N

Zawiercie Katowice Myszków Kraków 52°N Carpathian front

Zawiercie

Tarnowskie Góry

Bytom

Katowice Olkusz

Jaworzno

0 10 km Chrzanów

Fig. 1. Map showing the lead-zinc mineralization in Devonian and Triassic deposits of the Silesia-Cracow district (after Cabała, 2002). ORGANIC MATTER IN INTERNAL SEDIMENTS FROM THE SILESIAN-CRACOW LEAD-ZINC DEPOSITS, POLAND 777

Beds, is controversial. According to Sass-Gustkiewicz (1996), the epigenetic hypothesis. Sass-Gustkiewicz et al. (1982), openings were developed at the time of the lead-zinc min- along with Dz˙ułyński and Sass-Gustkiewicz (1985), have dem- eralization, whereas others suggest that they are a meteoric onstrated that the dominant ore-forming processes were meta- paleokarst system used and enlarged by hydrothermal lead- somatic replacements of carbonate rocks and fillings of open zinc solutions during the formation of the Silesian-Cracow spaces generated by hydrothermal karsting. Some authors deposits (Dz˙ułyński, 1976; Leach et al., 1996). Such meteoric proposed that ore formation took place during the Neogene paleokarst systems are recognized in many Mississippi Valley- and was related to intense closing stages of the Alpine orogeny type deposits worldwide (Ohle, 1985; Sangster, 1988; Kesler in the Carpathian orogenic belt (e.g., Gałkiewicz, 1967, 1971; et al., 1988, 2007; Leach et al., 2003, 2005, 2006). The Silesia- Gałkiewicz and Sliwiński,´ 1985; Symons et al., 1995). Others Cracow region saw a major period of meteoric karstification concluded that the ore-forming processes took place dur- during the Middle Triassic, as well as from the Upper Triassic ing early Cimmerian tectonic activity and that the age of the to the Middle Jurassic (Głazek, 1989). The Middle Triassic Silesian-Cracow deposits was Late Triassic or Early Jurassic meteoric paleokarsts occur along the Cracow-Myszkow tec- (e.g., Bogacz et al., 1970, 1972; Sass-Gustkiewicz et al., 1982; tonic zone and are clearly distinguished in the uppermost Wodzicki, 1987; Sass-Gustkiewicz and Dz˙ułyński, 1998). Anisian strata by subaerial exposure fabrics (paleosoils, mete- Górecka (1991, 1993) argued strongly for a post-Jurassic age oric paleokarstic pavements, playa clastics, and the evaporites based on the occurrence of lead-zinc mineralization within of the Tarnowice Beds; Szulc, 1999; Szulc and Becker, 2007), Upper Jurassic limestone. A study based on direct Rb-Sr dat- as well as at the Anisian/Ladinian boundary, marked by a ing of fluid inclusions in sphalerites indicates that the main- paleosol and meteoric paleokarstic horizon (Szulc, 1999). stage mineralizing event occurred in the Lower Cretaceous The origin and age of the sulfide mineralization in the (135 ± 4 Ma), which corresponds to a crustal extension pre- Silesian-Cracow lead-zinc deposits has been the subject of ceding the opening of the northern Atlantic Ocean (Heijlen debate for many years. Hypotheses concerning the origin are et al., 2003). varied. Some argued for a synsedimentary origin, with varying Internal sediment in the Silesia-Cracow district is an degrees of diagenetic modification (e.g., Keil, 1956; Zartman organic matter-rich sedimentary rock that fills caverns mainly et al., 1979). Other authors (e.g., Bogacz et al., 1970, 1975; in the basal portions of orebodies at their contacts with Gogo- Gałkiewicz, 1971; Harańczyk, 1979) favored an epigenetic lin limestone host rocks, open spaces between hydrothermal origin, with hydrothermal metal-bearing fluids originating collapse breccia fragments (Fig. 2), or caverns, cavities, and at depth. Homogenization temperatures of fluid inclusions solution collapse breccias in unmineralized parts of the ore hosted by sphalerite (80°–158°C; Kozłowski, 1995) support deposits (Leach et al., 1996). Internal sediments have been

Fig. 2. Internal sediment (laminated) composed of dolomite, gypsum, illite, and sulfides (brown laminae are organic matter rich), with so-called dopplerite (black, massive, at upper left). Sample collected from the Pomorzany mine. 778 RYBICKI ET AL. investigated for many years in the Silesian-Cracow Missis- with ore deposition. The most precise age constraints are sippi Valley-type lead-zinc deposits (e.g., Horzemski, 1962; palynological data presented by Zawi´slak (1965), who docu- Zawi´slak, 1965; Bogacz et al., 1970; Lipiarski, 1971; Sass- mented Triassic pollen and spores within internal sediments Gustkiewicz, 1974, 1996, 2007; Zawi´slak and Kruszewska, of the Bytom area. Despite many years of research, attempts 1975; Michalik, 1984, 1997; Dz˙ułyński and Sass-Gustkiewicz, to determine the age and sources of organic matter have been 1985; Sass-Gustkiewicz and Kwiecińska, 1998, 1999). Inter- devoid of convincing and unequivocal evidence. Therefore, nal sediments, also known as vitriol clays in the western part we undertook geochemical, petrographic, and palynological of the Bytom lead-zinc ore district (e.g., Horzemski, 1962; studies to determine the organic matter source and age in the Zawi´slak, 1965; Michalik, 1984, 1997), range from a few cen- Silesian-Cracow lead-zinc deposits. timeters to 2 m in thickness (Zawi´slak, 1965). In the eastern part of the Silesian-Cracow ore district (this study area), inter- Material and Methods nal sediments occurring in caverns at the same stratigraphic position as in the western part may measure a few meters in Samples thickness (Sass-Gustkiewicz, 1996, 2007). Due to availability, two districts, Olkusz and Chrzanów, were Based on their lead, zinc, and iron sulfide contents, two chosen for the current study (Fig. 1). Seventeen samples of types of internal sediments are described here: (1) mineral- internal sediment were collected from underground expo- ized internal sediments within thick lead-zinc deposits and sures. In addition, two organic-poor samples were taken as commonly containing high amounts of detrital lead, zinc, and mine contamination blanks: a marcasite sample from the iron sulfides (Sass-Gustkiewicz, 1985, 1996, 2007; Sass-Gust- Pomorzany mine (MARPM), and a dolostone sample from kiewicz and Kwiecińska, 1999), which have been redeposited the Trzebionka mine (DOLTR). The majority of samples and subsequently altered (mineralogically and chemically) came from two sites in the Olkusz district: from the Pomor- during the formation of the lead-zinc deposits; and (2) non- zany deposit (11 samples; prefix ISPM), and from the Klucze mineralized internal sediments, which do not contain detri- deposit (two samples; prefix ISKL). All samples were collected tal lead, zinc, and iron sulfides (Horzemski, 1962; Michalik, from the hanging-wall parts of the deposits (the Pomorzany 1984), and which are generally found in the distal parts of Graben and the Klucze Graben, respectively). Four samples the ore deposits or within meteoric paleokarst caverns that (prefix ISTR) were collected from the Trzebionka mine in the were apparently isolated during the hydrothermal stage and Chrzanów district before it closed in 2008. not penetrated by lead-zinc–bearing solutions. The main purpose of the sampling was to collect internal The first descriptions of the coaly matter associated with sediments over the greatest possible area in order to acquire lead-zinc deposits of the Silesian-Cracow region were made the most representative samples, including well-mineralized by Althans (1891) and Stappenbeck (1928), describing them locations (mineralized internal sediment samples ISPM1, as humic material called Pechkohle or Humilitkohle. Further ISPM3, ISPM4, ISPM5, ISPM6, ISPM7, ISPM8, ISPM10, descriptions of coal-like organic matter have been recorded ISPM11, and ISTR6), as well as unmineralized, distal parts by Horzemski (1962), Zawi´slak (1965), Lipiarski (1971), Kra- of the deposits (nonmineralized internal sediment samples jewski et al. (1971), Szuwarzyński (1975), Kołcon and Wagner ISPM2, ISPM9, ISKL1, ISKL3, ISTR1, ISTR3, and ISTR4). (1983), and Michalik (1984, 1997), and included morpho- Some samples (ISPM4, ISPM7, ISPM8, ISPM9, ISPM10, logical characteristics of coal accumulations and petrographic ISPM11, ISKL1, and ISKL3) are accompanied by doppler- analyses. ite (Fig. 2), whereas others (ISPM1, ISPM2, ISPM3, ISPM5, Along with descriptions of coal occurrences, there were ISPM6, ISTR1, ISTR3, ISTR4, and ISTR6) occurred as cav- attempts to explain the origins and ages of the coals. Most ern fills. Mines in the Bytom district have not been accessible investigators agree that the organic matter from Silesian- since their closure in 1989, and no samples were available Cracow deposits has an allochthonous origin relative to sur- from the Zawiercie district, which has not yet opened. rounding carbonates (e.g., Krajewski et al., 1971; Lipiarski, 1971; Sass-Gustkiewicz and Kwiecińska, 1994, 1999). Contro- Petrologic methods versies have included potential sources and ages for organic Standard sedimentological and petrographic observations, matter (e.g., Krajewski et al., 1971; Kołcon and Wagner, 1983; including the identification of textures and minerals, were Kwiecińska et al., 1997; Sass-Gustkiewicz and Kwiecińska, performed under reflected light using a NIKON SMZ 1000 1999; Rybicki, 2012; Rybicki et al., 2014), as well as the rela- stereoscopic microscope. Samples of dolomite-rich internal tionship between organic matter and ore deposits. Based on sediments were also examined using JEOL JSM-6380LA and the geotectonic position of the coal from the Bolesław mine, SEM 120 FEI Nova NanoSEM 200 scanning electron micro- Krajewski et al. (1971) favored a Lower Jurassic age for its scopes. The resolution of the Nova NanoSEM 200 micro- organic matter. Kołcon and Wagner (1983) speculated that scope extends down to 1 nm. The chemistry of the minerals the age of the coaly matter from the Pomorzany mine was was determined using a GEN121 ESIS XM4 EDS system, Paleogene based on petrographic studies showing the imma- without standards due to the fine-grained texture of the sam- ture character of its organic matter, whereas Kwiecińska et al. ples. Organic matter was analyzed by epifluorescence micros- (1997), as well as Sass-Gustkiewicz and Kwiecińska (1999), copy using a NIKON ECLIPSE E600 POL equipped with an based on geochemical data for the most likely source of organic EX 380-420 filter. matter, recognized the Keuper shales (or Lower Jurassic Mineralogical compositions were determined using a Phil- brown coals) as a source and assumed that the accumulation ips X-Pert Pro multipurpose diffractometer at the Depart- of organic matter was simultaneous or almost simultaneous ment of Geology at the University of Warsaw. Data were ORGANIC MATTER IN INTERNAL SEDIMENTS FROM THE SILESIAN-CRACOW LEAD-ZINC DEPOSITS, POLAND 779 collected using CoKα radiation over the range from 2.5084 to was first activated at 110°C for 24 h and then put into Pasteur 64.9834° 2Θ, employing a step size of 0.017 2Θ and a count pipettes. The eluents used for collection of the three frac- duration of 1 s per step. tions were: n-pentane (aliphatic), n-pentane, and DCM (7:3, Stable oxygen and carbon isotope data were collected at the aromatic), and DCM and methanol (1:1, polar). All spectro- Isotope Dating and Environment Research Laboratory (ING scopically pure solvents were of superdehydrated grade. The PAN, Warsaw). Stable isotopic ratios of oxygen and carbon in n-hexane aliquot of the polar fraction of selected samples was carbonates were determined using a Thermo KIEL IV Car- converted to trimethylsilyl derivatives by reaction with N,O- bonate Device connected to a Finnigan Delta Plus isotope bis-(trimethylsilyl)trifluoroacetamide (BSTFA) and pyridine ratio mass spectrometer. CO2 gas was extracted from dolomite for 3 h at 70°C. A blank sample (silica gel) was analyzed using using the method described by McCrea (1950). Precision and the same procedure (including extraction and separation on accuracy were checked every 10 samples using the interna- columns). Only trace amounts of phthalates, fatty acids (FAs), tional isotope standard NBS 19. Isotope ratios are expressed and n-alkanols were detected. relative to the Vienna Pee Dee Belemnite (VPDB) standard. The precision of δ13C and δ18O was ±0.03‰ and ±0.07‰, Gas chromatography coupled with mass spectrometry respectively. Gas chromatography (GC), coupled with mass spectrometry (MS) analyses, was carried out with an Agilent Technologies Palynological preparations 7890A gas chromatograph and Agilent 5975C Network mass Nine samples (ISPM6, ISPM7, ISPM8, ISPM9, ISPM10, spectrometer with Triple-Axis detector at the Faculty of Earth ISPM11, ISKL1, ISKL3, and ISTR4) were processed and Sciences, Sosnowiec, Poland. Helium (6.0 grade) was used analyzed for their palynological contents. Each sample was as a carrier gas at a constant flow of 2.6 ml/min. Separation assessed before preparation to create targeted methods which was obtained on either of two fused silica columns: (1) J&W would enhance the chances of palynomorph recovery. Ini- HP5-MS (60 m × 0.32 mm i.d., 0.25-µm film thickness) tially, any sample containing significant amounts of carbonate coated with a chemically bonded phase (5% phenyl, 95% was treated with concentrated hydrochloric acid (37%) before methylsiloxane), for which the GC oven temperature was undergoing hydrofluoric acid (40%) treatment. Due to high programmed from 45°C (1 min) to 100°C at 20°C/min, then organic contents, samples were then treated with an oxidizing to 300°C (held 60 min) at 3°C/min, with a solvent delay agent (Schultz’s solution: a solution of potassium chlorate and = 10 min; and (2) J&W DB35-MS (60 m × 0.25 mm i.d., concentrated nitric acid). Residues were then sieved using a 0.25-µm film thickness) coated with a chemically bonded 15-µm polyester mesh and mounted onto glass slides/cover phase (35% phenyl, 65% methylsiloxane), for which the GC slips using a mounting medium which cures in visible light oven temperature was programmed from 50°C (1 min) to (Rapidslide). 120°C at 20°C/min, then to 300°C at 3°C/min, then held at Slides were examined and imaged using a Leica DMRE 300°C for 60 min, with a solvent delay = 15 min. microscope, and palynomorph identifications were made The GC column outlet was connected directly to the ion based on taxonomic descriptions from original sources and source of the MSD. The GC-MS interface was set at 280°C, references within the John Williams Index of Palaeopalynol- while the ion source and the quadrupole analyzer were set ogy (Riding et al., 2012). at 230° and 150°C, respectively. Spectra were recorded from m/z 45 to 550 (0–40 min) and m/z 50 to 700 (>40 min). The Huminite reflectance measurements mass spectrometer was operated in the electron impact mode, An optical Axio Imager.A2m Carl Zeiss microscope was used with an ionization energy of 70 eV. for random reflectance (Rr) measurements on samples containing organic matter (observations made at ×500 under Quantification and identification oil immersion). Reflectance measurements were taken at 50 An Agilent Technologies MSD ChemStation E.02.01.1177 points (using a sapphire standard with a reflectance of 0.42% and the Wiley Registry of Mass Spectral Data (9th edition) according to ISO 7404-5, 2009), depending on the level of software were used for data collection and spectra process- alteration of the organic matter. ing. Abundances were calculated by comparison of peak areas for the internal standard (9-phenylindene for aromatic frac- Total organic carbon and total sulfur contents tions and 3-methylheneicosane for aliphatic fractions, added Abundances of total carbon, total sulfur, and total inorganic before separation), with peak areas of individual hydrocarbons carbon were determined using an Eltra CS-500 IR-analyzer obtained from the GC-MS ion chromatograms. Component with a total inorganic carbon module. Total organic carbon assignments were made by comparisons with published mass (TOC) was calculated as the difference between total carbon spectra and by interpretations of MS fragmentation patterns. and total inorganic carbon. Calibration was made using Eltra standards. Results Extraction, separation, and derivatization General characteristics of the internal sediment Powdered samples (ca. 15 g) were extracted using a dichlo- Samples of internal sediment studied here typically display romethane (DCM)/methanol mixture (5:1 v:v) with an accel- a layering visible at the macro- and microscales (Fig. 3a, b, erated Dionex ASE 350 solvent extractor. Extracts were d). Their textures are characterized by loosely packed, coarse- separated into aliphatic, aromatic, and polar fractions by mod- grained euhedral dolomite crystals with high intercrystal- ified column chromatography (Bastow et al., 2007). Silica gel line porosities (Fig. 4a, b). Open free spaces within internal 780 RYBICKI ET AL.

A B

2 cm 500 µm D

C D

Fig. 3. Petrography of internal sediment from the Pomorzany mine. A) Internal sediment composed of dolomite, gypsum, and pyrite, with distinctly visible layering. B) Variable grain size between individual layers of internal sediment. C, D) Textures of dolomitic sediments, ranging from coarse (C) to 100 µm 10 µm fine-grained (D) layers. B, C, and D are BSE images, JEOL JSM-6380LA, 15 keV, 5 nA.

A B

25 µm 25 µm

C D Fig. 4. Morphology of dolomite crystals in layered internal sediment from the Pomorzany mine. A, B) Loosely packed, coarse-grained euhedral dolomite crystals, showing high intercrystalline porosities. The texture of some dolomite crystals indicates dissolution. C) Internal sediment showing the growth texture of dolomite crystals and aggregates of framboidal pyrite. D) Textural relationship between dolomite crystals and sphalerite grains. Detrital sphalerite 10 µm 100 µm grains are indicated by arrows. BSE images, JEOL JSM-6380LA, 15 keV, 5 nA. ORGANIC MATTER IN INTERNAL SEDIMENTS FROM THE SILESIAN-CRACOW LEAD-ZINC DEPOSITS, POLAND 781 sediments (Fig. 5a) and small caverns (Fig. 5b) document the Sulfides were recognized in all samples. Pyrite, the most absence of significant compaction. Some samples are easy to common sulfide, commonly forms framboidal aggregates crumble into powder when rubbed between fingers, unequiv- (Fig. 4c). Sphalerite commonly occurs as small crystals with ocally suggesting poor cementation. The color of the samples a well-developed euhedral habit (Fig. 6a), dispersed within varies from dark brown to yellow due to organic matter and the dolomite matrix, whereas detrital grains are rare (Fig. 4d). minor manganese oxide contents (Table 1). Dispersed organic These observations confirm those of Zawi´slak (1965), who matter does not fluoresce, suggesting thermal immaturity. noted the presence of small euhedral sphalerite grains up to The fine-grained internal sediments consist of dolomite, 0.04 mm in diameter. Other sulfides (e.g., galena) were rarely gypsum, pyrite, quartz, illite, a small amount of calcite, and recognized during our investigations (Fig. 6b), as indicated in organic matter. Analyzed samples are composed mainly of X-ray diffraction (XRD) analyses, which did not detect galena dolomite (28–94%). Samples with lower dolomite contents in most samples (see Table 2). are rich in gypsum and pyrite (constituting up to 35 and Dolomite crystals, constituting a grain-supported frame- 11 wt % of the samples, respectively). Thick gypsum coatings work in internal sediments, occur as euhedral grains ranging and interlayers are observed macroscopically in gypsum- and from about 10 to 100 µm in diameter. SEM photomicro- pyrite-rich samples (Fig. 5c, d). graphs reveal that all grains underwent intense dissolution, as

A B

50 µm 50 µm

C D Fig. 5. Petrography and texture of internal sediments from the Pomorzany mine. A) Contact between two layers of dolomite crystals (see arrow). Note the enhanced porosity close to the contact. B) Open free spaces within internal sediments, docu- menting the lack of compaction. C) Gypsum glazes (see arrow) commonly present within internal sediment. D) Gypsum cement (see arrow) filling primary 50 µm 20 µm open spaces within dolomitic internal sediments. BSE images, JEOL JSM-6380LA, 15 keV, 5 nA.

Table 1. Chemistry of Our Fine-Grained Internal Sediments

Sample no.

Element (wt %) ISKL3 ISPM6 ISPM7 ISPM8 ISPM9 ISPM10 ISPM11

SiO2 3.03 2.81 13.79 0.92 1.94 9.3 9.97 TiO2 b.d.l. b.d.l. 0.07 b.d.l. b.d.l. b.d.l. b.d.l. Al2O3 0.79 1.01 5.43 b.d.l. 0.51 3.67 3.43 MgO 16.74 20.27 10.17 19.67 20.11 15.23 16 MnO b.d.l. b.d.l. 0.48 b.d.l. b.d.l. b.d.l. b.d.l. CaO 43.82 40.13 21.43 52.43 44.34 29.1 26.12 FeO 1.53 7.76 4.39 2.35 2.26 3.77 5.24 ZnO 0.88 2.63 4.15 1.19 1.97 5.13 5.77 PbO b.d.l. b.d.l. b.d.l. b.d.l. b.d.l. 1.11 1.04 Na2O 0.12 0.71 b.d.l. b.d.l. b.d.l. 0.99 b.d.l. K2O 0.26 0.19 1.4 b.d.l. b.d.l. 0.64 0.55 SO3 1.68 2.82 5.45 1.25 2.73 4.75 4.93 CTOT 31.15 21.67 33.23 22.19 26.13 26.31 26.94 Total 100 100 99.99 100 99.99 100 99.99

Abbreviation: b.d.l. = below detection limit 782 RYBICKI ET AL.

A B

Fig. 6. Lead-zinc ore minerals and organic matter C D within internal sediments. A) Automorphic grains of sphalerite within dolomite matrix. Sample ISPM7. B) Galena cements within fine-grained dolomitic internal sediments. Sample ISPM10. C) Thin layer of homogeneous (maceral-free) organic matter from sample ISPM7. D) Detailed internal texture of organic matter from a thick accumulation of organic matter in breccia-type lead-zinc ores from the Pomorzany mine. A, B, and C are BSE images, JEOL JSM-6380LA, 15 keV, 5 nA. D is a BSE image 25 µm recorded using the FEI Nova NanoSEM 200. documented by numerous small etching pits on their surfaces show minor differences (–1.451 and –1.754‰, respectively; (see Fig. 4a, b). The characteristic rhombohedral morphol- Fig. 7). This isotopic signature falls within the field of low- ogy reveals the direction of dolomite crystal growth. Other temperature dolomites of early-diagenetic origin, according features indicating dolomite dissolution comprise the rough to the Allan and Wiggins (1993) diagram. surfaces of all dolomite grains (see Figs. 3c, 4a, b; cf. Kacz- Bulk geochemical parameters, including TOC and total marek and Sibley, 2007) and nearly completely dissolved cen- sulfur contents, as well as extractable amounts of organic tral portions of dolomite crystals, resulting from the preferred matter and huminite reflectances (Rr), are given in Table 3. dissolution of the cores of dolomite crystals having enhanced TOC and total sulfur contents indicate that the sediments calcium concentrations in their cores, in contrast to margins are rich in organic matter, with TOC values between 2.42 rich in magnesium (Randazzo and Cook, 1987). Concentra- and 13.0 wt %. Total sulfur contents are highly variable tions of MgO are high and vary from 10.2 to 20.3 wt % (Table (0–31.9 wt %) and depend on the degree of sulfide (sphal- 1). ZnO, FeO, and SiO2 contents are also enhanced and erite and pyrite) mineralization. The extraction yield was range from 0.88 to 5.77 wt %, 1.53 to 7.76 wt %, and 0.92 to diverse as well, with the content of extractable organic mat- 22.0 wt %, respectively. The whole-rock chemistry of internal ter (EOM) varying from 0.9 to 10.9 mg/g TOC, and averag- sediments (Table 1) corresponds closely to the mineralogy of ing 5.89 mg/g TOC (Table 3). examined samples (Table 2). The polar fraction clearly dominates over aromatic and aliphatic fractions in the samples from Pomorzany and Trzebi- Isotopic and bulk geochemical data onka. In most samples (eight of 11), the polar fraction content Carbon and oxygen stable isotope ratios were determined for was at least 75 wt %. In the other three samples, the polar dolomites of internal sediment samples ISPM1 and ISPM3. fractions ranged from 46 to 62 wt % and predominate in each The δ13C ratios of the two samples are significantly different case. In the majority of samples, the aromatic fraction was the (–0.935 and 1.037‰, respectively), whereas the δ18O ratios least abundant component (Table 3).

Table 2. Mineralogical Compositions of Our Internal Sediments, Determined by XRD Analyses

Sample no.

ISPM7 ISPM8 ISPM9 ISTR1 ISTR3 ISTR6

Rock-forming Dolomite, gypsum, Dolomite, gypsum, Dolomite, Dolomite, Dolomite, quartz, Dolomite, minerals pyrite, Mg-Ca-Fe sulfates, pyrite, marcasite, Mg-Ca-Fe illite, quartz sphalerite pyrite quartz, calcite, illite illite, Mg-Ca-Fe sulfates sulfates

Accessory Calcite, marcasite, Sphalerite Gypsum, pyrite, Gypsum Pyrite, Marcasite, minerals sphalerite sphalerite, quartz, clay minerals sphalerite marcasite, illite ORGANIC MATTER IN INTERNAL SEDIMENTS FROM THE SILESIAN-CRACOW LEAD-ZINC DEPOSITS, POLAND 783

Hydrothermal dolomite Early diagenetic dolomite

Ore-bearing dolomite of I generation

Latest generation of hydrothermal e calcite from Pomorzany mine (diagenetic dolomite) from Pomorzany (after Heijlen et al., 2003) mine (after Heijlen et al., 2003) -PDB)

C(V 5 13

Anisian limestone Allan & Wiggins (1993) δ from Silesian basin 4 after (after Szulc, 2000) Discrimination lin 3 B 2

1 A

δ18O(V-PDB) -10 -8 -6 -4 2 -1

-2 - Isotopic composition of our internal sediment -3 13 18 Ore-bearing dolomite of II generation ISPM1 δ C -0.935 ; δ O -1.451 ISPM3 δ13C 1.037 ; δ18O -1.754 (hydrothermal, simultaneous with lead-zinc ores) -4 from Pomorzany mine (after Heijlen et al., 2003) -5 Middle and upper part of the Olkusz Beds (now homogenous crystalline dolostone) from the BK-287 borehole section (after Narkiewicz, 1993) Fig. 7. Oxygen and carbon isotope signatures of the dolomitic rocks from the Silesian basin and from our internal sediment. Sources of data are indicated on the diagram. Scheme of the diagram taken from Heijlen et al. (2003) and references therein. A) Early diagenetic Triassic dolomites from northern Italy. B) Early diagenetic dolomites from southern Hungary.

The Rr values of all internal sediment samples are low, with with SCh/LCh ratios higher than 2 (Table 3). In some samples, a range from 0.24 to 0.32% and a mean of 0.29% (Table 3). a bimodal distribution is found, with SCh/LCh values near unity (Table 3, Fig. 9a). The carbon preference index, expressed as Palynological data CPI(total) values (defined in Table 3), is approximately 1, with the Among the nine samples processed for their palynological exception of samples ISPM2, ISPM3, and ISPM4, for which content, three (ISPM7, ISPM8, and ISPM10) were either CPI(total) values are well below unity (ranging from 0.64 to 0.77), barren of palynomorphs or yielded indiscernible specimens. and sample ISPM9, which has a CPI(total) value of 1.25. In the The other six samples varied in the preservation of palyno- case of long-chain homologues, a slight odd-to-even carbon morphs, but produced identifiable material (Table 4). number predominance was observed in six samples (ISPM1, Residues of sample ISKL1 yielded the best preserved ISPM4, ISPM5, ISPM7, ISPM9, and ISKL3), with CPI(25–31) assemblage of palynofloras. High numbers of bisaccate pollen, values ranging from 1.25 to 1.75, whereas in five other samples both taeniate and nontaeniate (e.g., Striatoabietites balmei, (ISPM2, ISPM3, ISPM8, ISPM10, and ISTR4), CPI(25–31) val- Stellapollenites thiergartii, Angustisulcites grandis, Protodip- ues were close to unity (Table 3). The values of the maximum loxypinus doubingeri, Ovalipollis spp.), prasinophycean algae carbon number (Cmax, used to denote n-alkanes exhibiting the (Tasmanites spp., Leiosphaeridia spp., and Cymatiosphaera highest concentration in the homologous series) are under spp.), acanthomorph acritarchs (e.g., Micrhystridium spp.), 19 in all cases, and vary from 14 to 18, with n-C18 being the and rare, simple, trilete spores are present (Fig. 8). Organic dominant homologue (in five samples, ISPM1, ISPM2, ISPM3, residues of ISPM6, ISPM9, ISPM10, ISPM11, ISTR4, and ISPM4, and ISPM9). In three samples (ISPM7, ISPM10, and ISKL3 contain palynomorphs occurring in sample ISKL1, but ISTR4), the odd-carbon number homologue (in each case, these samples display less diversity and abundance (Table 4). n-C17) was the most abundant n-alkane (Table 3). In some sam- For example, samples ISPM6 and ISTR4 contain predomi- ples (ISPM1, ISPM5, ISPM7, ISPM8, ISPM10, and ISKL3), nantly prasinophyte algae and acritarchs. an unresolved compound mixture (a so-called hump) is clearly visible (Fig. 9). Molecular composition of extractable organic matter The distribution of two common isoprenoids (pristane [Pr] Aliphatic hydrocarbons: The dominant aliphatic hydrocarbons and phytane [Ph], relative to n-alkanes) is characterized by for all internal sediment samples are n-alkanes and isoprenoids. relatively low values of Pr/n-C17 and Ph/n-C18, which, in most Although the n-alkane distribution differs significantly between cases, does not exceed unity. Pr/Ph ratio values range from samples, all samples contain homologues with carbon chain 0.73 to 1.36. lengths from n-C14 to n-C31. In almost all cases, the short-chain The most abundant hopanoids are 17α(H)21β(H)-hopane n-alkanes (SCh) predominate over long-chain n-alkanes (LCh), (C30αβ), 17α(H)21β(H)-22R homohopane (C31αβ R), and C30 784 RYBICKI ET AL.

Table 3. Bulk Geochemical Data, Huminite Reflectance Values, Percentage Yields of Fractions, and Basic Molecular Parameters

1 2 3 4 5 7 TOC TS Rr EOM AL Fractions POL 6 8 9 10 11 Sample no. (%) (%) (%) (mg/g TOC) (%) AR (%) (%) CPI(total) CPI(25–31) Cmax Pr/Ph

ISPM1 5.75 20.45 n.a. 10.79 22 3 75 0.97 1.57 18 0.77 ISPM2 11.93 5.73 0.32 5.34 18 6 76 0.77 0.89 18 0.90 ISPM3 6.84 17.83 0.32 5.25 14 3 83 0.64 0.98 18 0.77 ISPM4 11.54 12.71 n.a. 4.72 20 2 78 0.71 1.25 18 0.99 ISPM5 7.87 9.49 n.a. 10.92 7 8 85 1.02 1.31 16 0.96 ISPM7 9.51 13.73 n.a. 0.9 5 9 86 0.95 1.75 17 1.09 ISPM8 12.56 13.06 0.24 2.21 31 23 46 1.04 1.01 14 0.73 ISPM9 11.68 2.44 0.28 3.13 29 9 62 1.25 1.34 18 1.36 ISPM10 2.42 31.89 n.a. 7.75 8 6 86 1.07 1.09 17 1.08 ISKL3 9.02 2.83 0.31 3.36 25 25 50 0.84 1.26 16 1.06 ISTR4 12.97 0 0.28 10.47 10 5 85 0.91 0.96 17 0.94 MARPM <0.2 n.a. n.a. n.a. n.a. n.a. n.a. 1.01 0.78 19 1.54 DOLTR <0.2 n.a. n.a. n.a. n.a. n.a. n.a. 0.96 1.04 22 0.69

C30M/ C31αβS ββ- 12 13 14 15 16 17 18 19 20 21 22 Sample no. Pr/nC17 Ph/nC18 SCh/LCh C30H /(S + R) hopanes MPI1 P/ΣmeP PhNR TrP1 (Ad/Al)v

ISPM1 1.19 1.17 2.78 0.76 0.26 ++ 0.27 2.59 1.95 0.31 0.29 ISPM2 0.83 0.64 33.12 0.54 0.28 - 0.32 2.38 1.93 0.10 0.26 ISPM3 0.49 0.70 52.04 0.60 0.28 - 0.27 2.76 2.20 0.13 0.34 ISPM4 0.63 0.38 7.45 0.86 0.09 + 0.34 2.48 1.24 0.25 0.28 ISPM5 1.13 1.62 0.99 0.72 0.19 ++ 0.22 3.05 2.13 0.00 n.a. ISPM7 0.84 1.24 7.51 0.56 0.27 ++ 0.22 2.78 2.32 0.15 0.47 ISPM8 0.25 0.82 6.41 0.94 0.09 + n.a. n.a. n.a. n.a. n.a. ISPM9 0.91 0.89 3.36 0.82 0.23 + 0.39 1.89 1.99 0.44 0.56 ISPM10 0.90 0.84 1.62 0.17 0.47 - 0.26 2.39 3.37 0.34 n.a. ISKL3 0.77 1.19 3.27 0.18 0.46 - 0.52 1.54 4.89 1.59 n.a. ISTR4 0.80 1.01 21.25 0.61 0.22 ++ 0.20 3.66 1.58 0.00 0.20 MARPM 0.90 0.74 3.43 0.31 0.48 - 0.25 1.96 n.a. n.a. n.a. DOLTR 1.28 1.54 4.46 n.a. n.a. - 0.21 3.65 2.52 0.01 n.a.

Abbreviation: n.a. = not analyzed 1 TOC = total organic carbon (%) 2 TS = total sulfur (%) 3 Rr = huminite reflectance (%) 4 EOM = extractable organic matter 5 AL = aliphatic fraction (%) 6 AR = aromatic fraction (%) 7 POL = polar fraction (%) 8 CPI(total) = carbon preference index; CPI(total) = ((C15 + C17 + … + C27 + C29) + (C17 + C19 + … + C29 + C31))/2(C16 + C18 + … + C28 + C30) 9 CPI(25–31) = carbon preference index; CPI(25–31) = ((C25 + C27 + C29) + (C27 + C29 + C31))/2(C26 + C28 + C30) 10 Cmax = maximum carbon number 11 Pr/Ph = prystane to phytane ratio 12 Pr/nC17 = prystane to n-heptadecane ratio 13 Ph/nC18 = phytane to n-octadecane ratio 14 SCh/LCh = short-chain n-alkanes to long-chain n-alkanes ratio; SCh/LCh = (C17 + C19 + C21)/(C27 + C29 + C31) 15 C30M/C30H = C30-17β-moretane to C30-17α-hopane ratio 16 C31αβS/(S+R) = C31-homohopane 22S/( C31-homohopane 22S + C31-homohopane 22R) 17 ββ-hopanes = 17β,21β(H)-hopane relative content; + low/medium content of 17β,21β(H)-hopanes; ++ high content of 17β,21β(H)-hopanes; – absence of 17β,21β(H)-hopanes 18 MPI1 = methylphenanthrene index; MPI1 = 1.5([2-MP] + [3-MP])/([P] + [1-MP] + [9-MP]) 19 P/ΣMeP = phenanthrene to sum of methylphenanthrenes ratio 20 PhNR = phenylnaphtalene ratio; PhNR = 2-phenylnaphtalene/1-phenylnaphtalene 21 TrP1 = terphenyl ratio; TrP1 = p-TrP/o-TrP 22 (Ad/Al)v = vanillic acid to vanillin ratio

17β(H),21β(H)-hopane (C30ββ) (Fig. 9b). Hop-13(18)-ene ISPM10). The C31αβS/(S + R) homohopane values are small and hop-17(21)-ene, compounds containing double bonds in most samples, ranging from 0.09 to 0.47 (Table 3). in their molecule, are also present in relatively high amounts The C30M/C30H (C30βα -moretane to C30αβ -hopane) values (Fig. 9b). The distribution of extended C31-C35 homohopanes are diverse and vary from 0.17 to 0.94 (Table 3). Moreover, is characterized by a strong predominance of the C31(22S + significant differences are observed between samples in 22R) homologues and a significant excess of the less stable ββ-hopanes and hopenes distributions. Their abundances R epimer. Homohopanes with 34 and 35 C atoms in the in some samples (ISPM1, ISPM5, ISPM7, and ISTR4) are molecule were detected only in two samples (ISPM1 and relatively high, whereas in others (ISPM2, ISPM3, ISPM10, ORGANIC MATTER IN INTERNAL SEDIMENTS FROM THE SILESIAN-CRACOW LEAD-ZINC DEPOSITS, POLAND 785

and ISKL3), ββ-hopanes and hopenes are absent (Table 3). Sterenes, steranes, diasteranes, and diasterenes are present only in trace amounts in all of the samples.

spp. Samples used as contamination blanks (i.e., an organic-

Ovalipollis poor sample from the Pomorzany mine [MARPM] and a dolostone sample from the Trzebionka mine [DOLTR]) are characterized by different n-alkane, isoprenoid, and hopanoid distributions compared to internal sediment samples. In both samples, SCh predominates over LCh, with SCh/LCh values bisaccates of 3.43 and 4.46 for marcasite from the Pomorzany mine and nontaeniate) (taeniate and for dolostone from Trzebionka mine, respectively (Table 3). Other CPI(total) values in both cases are near unity, whereas CPI(25–31) values were distinctly different (0.78 for marcasite and 1.04 for dolostone, Table 3), similar to Cmax values (19 for marcasite and 22 for dolostone, Table 3). Hopanoids are present in only balmei trace amounts in the dolostone sample, whereas in marcasite,

Striatoabietites the most abundant hopanoid is C30αβ-hopane, which clearly predominates over C30βα-moretane, with a C30M/C30H value of 0.31. Among the homohopanes, the compounds with the 22S configuration are almost equal to those with the 22R configuration, with a 31C αβS/(S +R) value at 0.48 (Table 3). oriens ββ-hopanes and hopenes are absent in both contamination

Tsugaepollenites blank samples. Aromatic compounds: The concentrations of aromatic compounds are low (Table 5) and, in some samples, most such compounds fall below the detection limit. However, 38 aro-

grandis matic compounds were identified, based on characteristic mass fragments and retention times (Table 5). Angustisulcites Phenanthrene (P), methylphenanthrene (MP), dimethyl- phenanthrene (DMP), and trimethylphenanthrene (TMP) isomers represent the most abundant aromatic components. Their concentrations vary from 0.073 to 0.713 µg/g TOC for P, and the sum of MP isomers ranges from 0.035 to 0.258 µg/g TOC. DMP and TMP concentrations vary from 0.019 to 0.071 µg/g TOC and from 0.013 to 0.024 µg/g TOC, respectively (Table 5). The methyl phenanthrene index (MPI1) and the ratio of phenenthrene to the sum of methyl phenantherenes P/(ΣMeP) were calculated for most samples (Table 5), giving

doubingeri thiergartii values ranging from 0.20 to 0.52 and from 1.54 to 3.66, respec-

Table 4. Key Palynomorphic Groups in Our Internal Sediments Table tively. Other major polycyclic aromatic hydrocarbons (PAHs) Protodiploxypinus Stellapollenites were fluoranthene (Fl), pyrene (Py), benzo[ghi]fluoranthene (B[ghi]Fl), benzo[ghi]perylene (B[ghi]Pe), indeno[1,2,3-cd] pyrene (I[123-cd]Py), and coronene (Cor). The sums of their concentrations range from 0.036 to 0.201 µg/g TOC (Table 5). (undiff.) Aromatic land-plant biomarkers were also found, including cadalene (Cad), retene (Ret), simonellite (Sim), perylene (Per), and 6-isopropyl-2-methyl-1-(4-methylpentyl) naphtha- lene (iP-iHMN) with their methyl derivatives. The sum of their concentrations ranges from 0.009 to 0.044 µg/g TOC (Table 5). Prasinophyte Acritarchs

algae (undiff.) In addition to methyl derivatives, triaromatic members of phenyl derivatives of PAHs, including phenylnaphtha- lenes (PhNs) and terphenyls (TrPs), were detected in most samples. Their concentrations are low and range from 0.006 to 0.046 µg/g TOC for PhNs, with a slight predomination

Key taxa of 2-phenylnaphthalene, and from 0.001 to 0.011 for TrPs, where the thermodynamically least stable o-terphenyl is the most abundant isomer (Table 5). Oxygen-containing aromatic compounds, such as dibenzofuran (DBF) and methyl (MDBF), dimethyl (DMDBF), and Sample no. ISPM6 ISPM7 Barren ISPM8 Barren ISPM9 ISPM10 Barren ISPM11 ISKL1 ISKL3 ISTR4

786 RYBICKI ET AL.

A B C D

E F G H

Fig. 8. Selection of key taxa (sample reference and England Finder Reference). A) Striatoabietites balmei (ISKL1 U52- 1). B) Protodiploxypinus doubingeri (ISKL1 U51). C) Stellapollenites thiergartii (ISKL1 U44-3). D) Angustisulcites grandis (ISKL1 L61-3). E) Illinites spp. (ISKL1 K36-3). F) Ovalipollis pseudoalatus (ISKL1 M51-2). G) Cymatiosphaera spp. (ISKL1 K56-1). H) Acanthomorph acritarch (ISKL1 P51-2).

A m/z 71 ISPM5

n-C17 n-C Pr Ph 27 n-C29

o squalane

p n-C25

e n-C15

R n-C

i t n-C23

e n-C19

R n-C21

n-C33

n-C35

Retention Time

B m/z 191 31αβ ISTR4 R

30αβ 30ββ

o Tm

s Ts

e 29αβ

a 30βα

R 29ene 30ene S 32αβ 31ββ 29ββ R 27ene 31ene 33αβ 33ene 32ene 32ββ S S R

Retention Time Fig. 9. Distribution of (A) n-alkanes and isoprenoids and (B) hopanoids in analyzed samples. ORGANIC MATTER IN INTERNAL SEDIMENTS FROM THE SILESIAN-CRACOW LEAD-ZINC DEPOSITS, POLAND 787

Table 5. Concentrations of Aromatic Compounds (µg/g TOC) in Selected Internal Sediments

Occurrence and concentrations in the selected samples1 m/z Identified compounds ISPM1 ISPM2 ISPM3 ISPM7 ISPM9 Identification

Polycyclic aromatic hydrocarbons (PAHs) 178 Phenanthrene 0.128 0.519 0.713 0.096 0.073 MS 192 3-Methylphenanthrene 0.014 0.081 0.077 0.009 0.013 Radke et al. (1986) 192 2-Methylphenanthrene 0.012 0.050 0.071 0.008 0.010 Radke et al. (1986) 192 9-Methylphenanthrene 0.014 0.051 0.062 0.010 0.009 Radke et al. (1986) 192 1-Methylphenanthrene 0.009 0.036 0.048 0.008 0.006 Radke et al. (1986) 206 Dimethylphenanthrenes2 0.026 0.060 0.071 0.019 0.021 MS 220 Trimethylphenanthrenes2 0.018 0.024 0.022 0.014 0.013 MS 202 Fluoranthene 0.026 0.099 0.148 0.013 0.013 MS 202 Pyrene 0.017 0.039 0.045 0.008 0.008 MS 226 Benzo[ghi]fluoranthene 0.001 0.002 0.002 0.001 0.001 MS 276 Benzo[ghi]perylene 0.005 0.002 0.002 0.001 0.002 MS 276 Indeno[1,2,3-cd]perylene 0.002 n.d. n.d. 0.001 0.001 MS 300 Coronene 0.005 0.004 0.006 0.012 0.014 MS Phenyl derivatives of polycyclic aromatic compounds 204 1-Phenylnaphtalene 0.003 0.012 0.014 0.002 0.002 Marynowski et al. (2001) 230 o-Terphenyl 0.001 0.006 0.007 0.001 0.001 Marynowski et al. (2001) 204 2-Phenylnaphtalene 0.006 0.023 0.032 0.004 0.004 Marynowski et al. (2001) 230 m-Terphenyl 0.001 0.003 0.003 n.d. 0.001 Marynowski et al. (2001) 230 p-Terphenyl n.d. 0.001 0.001 n.d. n.d. Marynowski et al. (2001) Oxygen-containing aromatic compounds 168 Dibenzofuran 0.013 0.027 0.007 0.002 0.003 Radke et al. (2000) 182 4-Methyldibenzofuran 0.006 0.022 0.017 0.003 0.004 Radke et al. (2000) 182 2-Methyldibenzofuran 0.001 0.003 0.004 0.001 0.001 Radke et al. (2000) 182 3-Methyldibenzofuran 0.009 0.037 0.031 0.005 0.005 Radke et al. (2000) 182 1-Methyldibenzofuran 0.009 0.017 0.021 0.006 0.005 Radke et al. (2000) 196 Dimethyldibenzofurans2 0.020 0.086 0.102 0.014 0.012 Marynowski and Simoneit (2009) 210 Trimethyldibenzofurans2 0.011 0.045 0.067 0.012 0.010 Marynowski and Simoneit (2009) Sulfur-containing aromatic compounds 184 Dibenzotiophene 0.006 0.019 0.022 0.003 0.002 Marynowski et al. (2002) 198 4-Methyldibenzotiophene 0.004 0.010 0.009 0.001 0.002 Marynowski et al. (2002) 198 2+3-Methyldibenzotiophene 0.002 0.004 0.003 0.001 0.001 Marynowski et al. (2002) 198 1-Methyldibenzotiophene 0.001 0.002 0.002 0.001 0.001 Marynowski et al. (2002) 212 Dimethyldibenzotiophenes2 0.011 0.013 0.012 0.003 0.004 Marynowski et al. (2002) Aromatic land-plant biomarkers 198 Cadalene 0.002 0.007 0.008 0.006 0.002 Simoneit and Mazurek (1982) 252 Simonellite n.d. 0.007 0.002 0.004 0.001 Simoneit and Mazurek (1982) 197 iP-iHMN n.d. 0.008 0.002 0.008 0.001 Bastow et al. (1999) 211 4-Me-iP-iHMN n.d. 0.002 0.001 0.003 0.001 Bastow et al. (1999) 234 Retene 0.002 0.013 0.008 0.008 0.003 Bastow et al. (1999) 248 9-Methylretene 0.001 0.004 0.003 n.d. n.d. Bastow et al. (1999) 248 2-Methylretene 0.001 0.002 0.002 n.d. n.d. Bastow et al. (2001) 252 Perylene 0.003 0.001 0.001 0.001 0.001 Marynowski et al. (2013)

Abbreviations: n.d. = not detected 1Concentrations in mg/g TOC 2Calculated as sum of all isomers trimethyl (TMDBF) derivatives, were identified in relatively Aromatic compound distributions are similar in both con- high concentrations, ranging from 0.002 to 0.027 µg/g TOC tamination blank samples containing P and its methylation for DBF, and from 0.015 to 0.079 µg/g TOC for the sum of products (MP, DMP, and TMP), Py, Fl, PhNs, and TrPs, as MDBFs. Concentrations of DMDBFs and TMDBFs vary well as DBT and its methyl and dimethyl derivatives. from 0.012 to 0.102 µg/g TOC and from 0.010 to 0.067 µg/g Polar compounds: The principal compounds in the polar TOC, respectively (Table 5). fraction are 1,3-benzenedicarboxilic acid (in samples ISPM7 Sulfur-containing aromatic compounds, including diben- and ISTR4) and n-hexadecanoic acid (in samples ISPM1 zothiophene (DBT) and its methyl (MDBT) and dimethyl and ISPM9). In sample ISPM6, 2-ethoxyphenol dominates (DMDBT) derivatives, occur in low amounts (0.002–0.022 (Table 6, Fig. 10), and it is also one of the major components for DBT, 0.003–0.016 µg/g TOC for the sum of MDBTs, and of all other samples (Table 6). Important compounds in the 0.003–0.013 µg/g TOC for DMDBTs; see Table 5). fraction are n-fatty acids and n-alkanols, sterols, and stanols 788 RYBICKI ET AL. 0.0 0.0 6.3 3.6 7.7 0.0 2.0 6.6 1.2 5.0 1.9 4.0 3.8 7.0 8.5 0.2 0.0 0.0 2.0 0.0 4.3 0.0 4.2 5.5 100 10.9 32.3 38.7 76.5 41.9 11.6 10.2 12.6 78.8 13.3 12.3 11.9 21.2 64.9 ISTR4 0.3 0.0 1.2 1.5 1.1 4.5 0.7 4.1 5.1 0.2 2.9 1.3 1.3 0.4 2.1 0.7 0.7 3.7 1.4 6.6 1.2 0.7 4.5 7.7 1.1 1.6 0.8 0.9 9.3 1.6 3.6 1.7 7.5 8.1 100 32.4 35.6 26.4 0.3 0.0 0.5 2.7 2.1 2.0 1.4 8.3 0.5 5.6 1.8 1.7 0.6 6.1 2.6 1.0 7.8 0.9 2.8 2.3 0.9 3.8 7.3 1.1 0.7 0.4 0.6 5.8 9.5 1.1 2.2 2.7 3.9 7.5 100 15.0 37.5 54.2 0.4 0.0 1.9 2.7 2.5 4.7 2.4 6.5 0.3 2.5 0.4 1.5 0.4 1.1 0.8 0.4 3.4 1.8 4.4 1.4 2.9 4.7 1.2 1.1 0.8 3.8 4.4 7.8 1.0 1.7 1.7 4.1 6.2 100 34.0 0.03 34.2 39.8 1.8 1.1 9.7 7.7 0.7 2.0 0.1 4.9 5.4 1.8 0.9 1.1 1.4 0.3 5.2 3.8 4.0 0.0 0.4 2.0 4.5 4.6 3.5 2.1 2.3 1.8 0.7 2.3 0.2 0.3 0.1 0.0 5.7 9.8 3.5 9.0 3.3 1.3 0.9 0.0 0.0 9.0 0.9 3.4 1.5 5.1 5.6 100 13.0 28.5 35.9 14.3 18.7 22.2 54.7 81.7 40.6 17.1 10.3 19.9 ISPM1 ISPM6 ISPM7 ISPM9

Lignin Lignin Lignin Lignin Lignin Lignin Lignin Lignin Lignin Lignin Lignin Lignin Lignin Source Bacteria? Bacteria? Bacteria? Bacteria? Bacteria? Bacteria? Bacteria? Bacteria? Bacteria? Bacteria? Bacteria? Bacteria? Cellulose? Cellulose? Cellulose? Cellulose? Cellulose? Cellulose? Cellulose? Bacteria or Bacteria or Bacteria or Bacteria or Bacteria or higher plants higher plants higher plants higher plants higher plants 75(100), 73(95), 173(65), 187(45), 159(40) 145(10), 75(95), 112(60), 73(60), 117(50), 187(40), 129(40) 73(100), 117(65), 116(30), 147(20), 103(20) 73(55) 105(100), 179(90), 77(80), 135(50), 194(8) 75(75), 75(100), 73(98), 201(85), 117(60), 129(30), 132(28), 131(26), 145(15) 73(40) 201(100), 73(100), 147(55), 205(45), 103(30), 117(30), 133(20), 2018(15) 194(60), 131(100), 73(60), 147(20), 132(10), 133(8) 75(100), 73(98), 215(80), 117(65), 129(35), 132(25), 131(22), 145(15) 151(80), 162(20) 151(100), 73(80), 210(20), 195(20), 167(15) 179(100), 91(40), 73(100), 224(30), 165(25), 135(22), 91(20) 147(100), 73(55) 75(100), 229(98), 73(95), 117(80), 129(45), 132(30), 131(20), 145(20) 250(10) 194(100), 209(50), 224(30), 73(30) 75(75), 73(100), 243(95), 75(95), 117(80), 129(50), 132(35), 145(30), 131(28) 161(28), 243(100), 267(100), 73(60),193(50), 223(40), 282(40) 191(30), 235(100), 75(50), 73(48), 219(20) 235(100), 73(100), 267(85), 193(50), 223(50), 282(20) 237(100), 163(50), 193(30), 221(20), 252(8) 257(100), 73(98), 75(95), 117(90), 237(50), 129(48), 163(25), 193(20) 147(100), 73(60), 295(20), 310(5) 73(100), 75(95), 147(55), 303(50), 213(25), 287(20) 73(100), 117(95), 271(90), 75(90), 129(50), 132(45), 145(25) 295(100), 73(25), 279(20), 221(20), 310(15) 73(100), 297(98), 267(70), 312(65), 223(60), 253(50), 282(50) 295(100), 221(30), 103(23), 73(20), 251(20), 310(10) 75(100), 223(95), 149(50), 221(45), 73(40), 163(25), 119(15), 279(15), 294(5) 73(100), 285(95), 117(90), 75(80), 129(50), 132(45), 145(30), 300(5) 217(100), 73(90), 191(25), 147(25), 319(15) 204(100), 73(65), 191(35), 147(30), 217(30), 435(5) 204(100), 73(55), 191(30), 147(25), 217(25) 125(100), 77(55), 51(50), 218(40), 97(20) 73(100), 299(95), 117(90), 75(80), 129(60), 132(45), 145(40), 314(5) 299(100), 75(45), 103(20) 204(100), 73(85), 191(40), 147(30), 217(25), 435(5) 117(10), 73(90), 75(80), 129(60), 311(45), 326(5) 73(100), 75(98), 129(65), 311(65), 117(50), 145(25), 326(5) 73(100), 117(100), 313(95), 75(80), 129(60), 132(50), 145(35), 328(10) 221(100), 339(35), 103(25), 295(10) 75(100), 82(40), 96(40), 129(25), 325(25), 340(5) (%) Characteristic fragments m/z

162 218 92(308) 130(202) 130(202) 106(250) 122(194) 144(216) 144(216) 179(467) 158(230) 138(210) 122(194) 152(224) 172(244) 152(224) 186(258) 186(258) 138(282) 138(282) 180(252) 200(272) 166(310) 214(286) 166(310) 168(312) 166(310) 228(300) 180(540) 180(540) 180(540) 242(314) 242(314) 180(540) 254(326) 254(326) 256(328) 268(340) Mol. mass Table 6. Main Polar Compounds (by elution order on DB-5MS column) and Proportions (%) in Selected Internal Sediments Table

1 (ethylene glycol-TMS) 1-Methyl, 4-TMS 4-oxohexanoic acid-TMS 5-oxohexanoic acid-TMS 3,6,9-Trioxa-2,10-disilaundecane Benzoic acid-TMS Octanoic acid-TMS 1-Nonanol-TMS Glycerol-TMS D-Glucosamine-TMS? Nonanoic acid-TMS 2-Ethoxyphenol-TMS 4-Benzaldehyde-TMS Phenoxyacetic acid-TMS 1,4-Diacetylbenzene Decanoic acid-TMS Vanillin-TMS Undecanoic acid-TMS 1-Dodecanol-TMS m -Hydroxybenzoic acid-TMS Unknown Unknown p -Hydroxybenzoic acid-TMS 1,4-Benzenedicarboxilic acid Dodecanoic acid-TMS 1,2-Benzenedicarboxilic acid-TMS Unknown acid-TMS Tridecenoic 1,3-Benzenedicarboxilic acid-TMS acid-TMS Vanillic 1,4-Benzenedicarboxilic acid-TMS Unknown acid-TMS Tetradecanoic β -D-galactofuranose? α -Glucopyranose (glucose)-TMS β -Galactose-TMS? 1,1’-Sulfonyldibenzene Pentadecanoic acid-TMS 1-Hexadecanol-TMS β -Glucopyranose (glucose)-TMS cis -9-Hexadecenoic acid-TMS trans -9-Hexadecenoic acid-TMS Hexadecanoic acid-TMS Unknown Octadec-9z-enol-TMS Compound 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 No. ORGANIC MATTER IN INTERNAL SEDIMENTS FROM THE SILESIAN-CRACOW LEAD-ZINC DEPOSITS, POLAND 789 1.8 5.7 1.3 1.3 3.0 2.7 5.4 3.4 5.6 7.2 5.7 9.2 2.2 4.2 0.0 4.1 6.9 6.3 6.6 9.5 3.8 2.2 7.0 2.3 1.2 8.6 17.0 26.1 14.5 10.2 21.5 12.5 ISTR4 1.4 5.5 1.1 1.3 2.1 3.8 4.2 2.2 5.0 9.8 3.1 3.7 1.8 1.8 2.9 1.8 2.2 1.7 3.4 5.4 4.6 0.0 3.7 6.2 6.2 3.8 30.8 30.5 88.1 20.9 10.9 10.3 8.2 0.7 4.9 1.9 0.5 1.2 2.6 2.5 1.4 5.2 2.1 3.3 1.7 6.1 0.9 2.6 0.9 1.7 4.6 3.3 4.3 7.4 2.1 3.0 3.3 1.6 4.6 16.3 21.2 18.1 12.8 25.5 8.4 0.8 3.6 1.9 0.8 1.1 1.7 2.1 1.0 8.3 4.7 2.1 2.3 1.9 5.7 0.9 1.7 0.9 1.5 2.8 3.2 2.2 7.9 7.0 0.0 1.5 3.4 1.6 0.9 4.8 13.0 18.7 1.1 6.2 2.4 2.2 1.5 1.2 1.3 2.1 2.0 3.7 3.3 2.0 3.5 8.4 2.7 4.7 2.4 1.4 0.8 1.6 1.5 1.9 1.5 3.1 0.9 0.5 0.8 1.5 2.2 1.0 0.8 2.1 0.0 2.1 5.5 5.4 5.3 0.0 3.3 6.4 2.7 2.2 1.8 2.9 3.8 2.0 2.4 2.9 4.2 4.1 4.4 1.6 4.1 1.7 2.9 6.2 3.0 6.8 18.6 42.7 11.3 16.3 10.6 11.4 22.1 18.5 19.7 10.5 12.5 ISPM1 ISPM6 ISPM7 ISPM9

Source Bacteria? Bacteria? Bacteria or Bacteria or Bacteria or Bacteria or higher plants higher plants higher plants higher plants Higher plants Higher plants Higher plants Higher plants Higher plants Higher plants plants Higher plants Higher plants Higher plants Higher plants Higher plants Higher Higher plants Higher plants Higher plants Higher plants Higher plants plants Higher plants Higher Marine organisms? Marine organisms? Table 6. (Cont.) Table (%) Characteristic fragments m/z 159(100), 73(95), 117(90), 75(60), 143(50), 132(50), 369(50), 384(5) 73(100), 75(85), 117(65), 129(55), 339(55), 145(30) 73(100), 339(60), 75(55), 117(50), 129(50), 145(30) 73(100), 117(95), 341(85), 75(80), 129(60), 132(50), 145(45), 356(10) 103(15) 265(100), 73(60), 147(40), 103(35), 383(35), 221(20), 283(10) 75(45), 117(100), 355(100), 73(95), 75(80), 129(60), 132(60), 145(45), 370(10) 355(100), 265(100), 73(30), 149(30), 104(28), 383(25), 339(10) 73(100), 117(95), 369(85), 75(75), 129(50), 132(50), 145(45), 384(10) 117(100), 383(95), 73(90), 132(60), 75(55), 129(50), 145(50), 398(20) 383(100), 75(45), 103(15) 117(100), 73(90), 397(90), 132(60), 75(55), 129(50), 145(50), 412(20) 103(15) 117(100), 73(95), 411(85), 75(70), 132(60), 129(50), 145(50), 426(20) 117(100), 73(95), 425(90), 75(60), 132(60), 145(60), 129(55), 440(25) 75(45), 117(100), 73(98), 439(80), 75(75), 132(60), 145(60), 129(55), 454(25) 439(100), 103(15) 57(50) 73(100), 75(95), 485(75), 204(45), 469(40), 217(30), 395(30) 296(100), 104(70), 341(68), 76(50), 324(45), 240(20), 384(10) 75(45), 143(70), 73(100), 117(95), 453(90), 75(75), 129(50), 132(50), 145(45), 368(10) 453(100), 135(70), 341(100), 104(70), 76(60), 208(60), 324(45), 236(40), 296(30), 397(8) 103(15) 394(100), 75(45), 73(100), 117(90), 467(75), 75(70), 129(50), 132(50), 145(45), 482(20) 467(100), 129(100), 329(85), 368(55), 353(40), 458(30) 117(100), 73(98), 481(80), 75(65), 145(60), 132(55), 129(50), 496(40) 341(100), 208(50), 76(40), 104(35), 236(40), 324(45), 296(30), 397(8) 219(100), 103(50), 73(48), 147(45), 453(45), 480(10) 495(100), 75(45), 103(15) 129(100), 357(85), 396(65), 486(40), 381(30), 471(10) 149(25) 75(100), 215(60), 473(30), 488(25), 383(20), 305(15), 398(15), 431(15) 161(50) 73(100), 367(55), 395(50), 410(40), 341(35) 208(35), 73(100), 117(92), 509(60), 75(65), 145(60), 132(55), 129(50), 524(35) 410(75), 385(100), 104(40), 296(30), 149(25), 509(10) 104(40), 103(15) 174(100), 385(100), 75(45), 385(100), 208(45), 104(35), 149(25), 472(105) 523(100), 73(100), 327(100), 117(90), 75(80), 129(55), 132(50), 145(40), 342(8) 327(100), 75(40), 103(15)

410 312(384) 282(354) 282(354) 284(356) 298(370) 298(370) 312(384) 326(398) 326(398) 340(412) 354(426) 368(440) 382(454) 382(454) 396(468) 396(468) 410(482) 410(482) 386(458) 424(496) 438(510) 414(486) 416(488) 452(524) 466(538) 270(342) 270(342) Mol. mass

1 decanoic acid (phytanic acid) Compound 3,7,11,15-tetramethylhexa- trans -9-Octadecenoic acid-TMS cis -9-Octadecenoic acid-TMS? Octadecanoic acid-TMS Unknown Nonadecanoic acid-TMS 1-Eicosanol-TMS Unknown Eicosanoic acid-TMS Heneicosanoic acid-TMS 1-Docosanol-TMS Docosanoic acid-TMS acid-TMS Tricosanoic acid-TMS Tetracosanoic Pentacosanoic acid-TMS 1-Hexacosanol-TMS Unknown Unknown Hexacosanoic acid-TMS 1-Heptacosanol-TMS Unknown Unknown Heptacosanoic acid-TMS 1-Octacosanol-TMS Cholesterol-TMS Octacosanoic acid-TMS Unknown Unknown 1-Triacontanol-TMS β -Sitosterol-TMS Stigmastanol-TMS Unknown acid-TMS Triacontanoic Unknown Stigmasta-3,5-dien-7-one Unknown Unknown 1-Dotriacontanol-TMS Heptadecanoic acid-TMS 1-Octadecanol-TMS Identification based on literature data (Kuroda, 2000; Fabbri et al., 2002, 2009; Medeiros and Simoneit, 2007; Dickens et al., 2007) mass spectra interpretation Identification based on literature data (Kuroda, 2000; Fabbri et al., 2002, 2009; Molecular mass (as trimethylsilyl derivative in parentheses) No. 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 44 45 1 2 790 RYBICKI ET AL.

10 O-TMS O O-TMS TIC O CH 3 Silylated polar compounds

TMS-O O O O-TMS O S O TMS-O O 29 41 27 TMS-O

69 72 49 45 56 57 62 71 74 59 75 7 23 37 42 25 35 ISPM6

O-TMS = n-alkanols O = n-alkanoic acids TMS-O O 41 e 29 O-TMS O 56 49 69 72 76 10 O 75 15 23 37 57 59 62 9 14 43 ISPM7 19 28 30 41 Relative Respons

29 27 45 49 37 69 44 56 74 57 31 36 40 59 75 10 23 42 58 ISPM9 7 14 25 32 47 53 54

20.0030.00 40.0050.00 60.0070.00 80.00 [min] Retention Time Fig. 10. GC-MS total ion current (TIC) traces for silylated polar fractions of our internal sediments. Explanations for peak numbers are given in Table 6.

(with β-sitosterol predominating), as well as lignin degrada- that the sediment may be allochthonous, a more precise age tion products, including benzoic acid, vanillin, 4-benzalde- cannot be suggested. A more refined age, to a distinct biozone hyde, benzenedicarboxilic acids, hydroxybenzoic acids, and (such as the P. doubingeri subzone of Kürschner and Walde- many other less distinctive compounds (see Fig. 10, Table 6). maar Herngreen, 2010), would necessarily be based on pollen Notably, moderate amounts of sugars were detected using abundances and the origins/extinctions of species, but these the Aldrich internal standard. Two glucose isomers are domi- taxa are not present in our samples. Furthermore, an assump- nant: α- and β-glucopyranose, and putatively identifiedα - and tion would have to be made that the sediment (and its palyno- β-glucofuranose (Fig. 11, Table 6). Significant portions of morph content) were both from a finite age source (within the the polar fraction contain unidentified organic compounds. Anisian) and that no mixing/sorting had occurred. No palyno- Characteristic fragments for all samples are listed in Table 6, morphs were encountered that would contradict the assigned together with their molecular masses and possible sources. Anisian age.

Discussion Sources of organic matter The molecular composition of organic matter in the sediments Age of internal sediments studied suggests a multisource origin and/or that secondary, The presence of Striatoabietites balmei, Protodiploxypinus in situ processes were involved (e.g., oxidation, biodegrada- doubingeri, Angustisulcites grandis, Ovalipollis spp., Illinites tion). According to current literature, the occurrence and pre- chitonoides, and Stellapollenites thiergartii in our samples ponderance of short-chain over long-chain n-alkanes in most (see above) is diagnostic of an Anisian age (early Middle Tri- samples suggests a primary marine source of organic matter assic; Kürschner and Waldemaar Herngreen, 2010). Given (Gelpi et al., 1970; Grimalt and Albaigés, 1987). The short ORGANIC MATTER IN INTERNAL SEDIMENTS FROM THE SILESIAN-CRACOW LEAD-ZINC DEPOSITS, POLAND 791

m/z 204 + 217

O-TMS ? TMS-O O O-TMS

O -Glucos e TMS-O O-TMS TMS-O β TMS-O O-TMS O-TMS O-TMS e -D-Glucofuranose β

? O-TMS -Glucos e O

α TMS-O -Mannose β TMS-O O-TMS Relative Respons O-TMS -Mannose α

ISPM9 40.00 41.00 42.00 43.00 44.00 45.00 [min] Retention Time Fig. 11. Summed mass chromatogram for m/z 204 + 217 of the silylated polar fraction, showing the distribution of monosaccharides. chain n-alkanes, with carbon numbers lower than C22, are (dibenzothiophene and its methylation products) compounds, commonly considered to have originated from marine algal may indicate that combustion processes in the mine, includ- and/or bacterial derivatives (Gelpi et al., 1970; Grimalt and ing mine vehicle exhausts, may have mildly contaminated our Albaigés, 1987). Marine phytoplankton produce mostly short- samples. Diesel and lubricating oil emissions are well known chain n-alkanes with C15, C17, and C19 as the most abundant in underground mining and are treated as a routine source of homologues and a strong odd-to-even carbon preference petrochemical contamination (van Niekerk et al., 2002; Miller (Gelpi et al., 1970; Meyers, 1997). On the other hand, the et al., 2007; Noll et al., 2007). Wildfires or peat fires may also predominance of short-chain and even carbon-numbered have been a source of the pyrolytic organic matter (see, for n-alkanes in the range of C12 to C22 is distinctive for micro- example, Marynowski and Simoneit, 2009). Anisian wildfires organisms, including phytoplankton, and petroleum (Grimalt are well documented in Germany (Uhl et al., 2010), in Jordan and Albaigés, 1987). (Abu Hamad et al., 2013), and in Italy (Uhl et al., 2014). Our However, in some internal sediment extracts, a bimodal mine contamination blank samples do contain considerable distribution has been found, due to the explicit contribution amounts of pyrolitic compounds such as PAHs, PhNs, and of the terrestrial higher plants. As a major wax component, TrPs, as well as DBT and its methyl and dimethyl derivatives, terrestrial higher plants produce long-chain n-alkanes with indicating that combustion processes in the mine are a likely carbon numbers from C25 to C35 and a strong odd-to-even car- source of the compounds mentioned above. bon preference, with C27, C29, and C31 as the most abundant The terrestrial input is confirmed by the presence of land- homologues (Eglinton and Hamilton, 1967). The low CPI(total) plant aromatic biomarkers, such as cadalene, retene, simonel- and even Cmax values for most of our samples indicate no odd- lite, perylene, and iP-iHMN, with more or less intense methyl to-even carbon numbered n-alkane preference (see Table derivatives (see Table 5). These compounds clearly indicate 3). Nevertheless, in samples ISPM1, ISPM5, and ISPM7, that conifer-derived hydrocarbons have contributed to the CPI(25–31) values suggest inputs from terrestrial organic matter organic matter (e.g., Bastow et al., 1999; Otto and Simoneit, (Table 3). The distribution of n-alkanols and n-alkanoic acids 2001; Hautevelle et al., 2006; Marynowski et al., 2007), as differs from that of n-alkanes and, in both cases, long-chain well as the perylene degradation of woody material by wood- homologues occur in amounts comparable to their short- degrading fungi (Grice et al., 2009; Marynowski et al., 2013). chain homologues. The exceptions are n-hexadecanoic and However, a minor marine input into the organic matter of our n-octadecanoic acids, which clearly dominate in all samples internal sediments cannot be excluded because, as allochtho- (Table 6). However, these compounds can be generated by nous and heterogeneous material, this organic matter may both bacteria (e.g., Summons et al., 2013) and higher plants have had multiple sources. (e.g., Hedges et al., 1997). The occurrence of unresolved com- As for the polar fraction, most of the organic compounds are pound mixtures in some samples (Fig. 9a) suggests biodegra- degradation products of lignin and, possibly, cellulose (Table 6). dation of organic matter (Macqueen and Powell, 1983; Gize, Although the abundant 1,2-, 1,3-, and 1,4-benzenedicarboxilic 1999). However, n-alkanes (including short-chain n-alkanes) acids are found in urban particulate matter (Li et al., 2006; Ma are consistently present in all of our samples, implying that et al., 2010) and as combustion products of plastics (Simoneit biodegradation was rather mild (Peters et al., 2005). et al., 2005), their sources can be diverse. Benzenedicarboxilic Small amounts of compounds typical of pyrolytic processes, acids are commonly reported as important decomposition con- such as PAHs and aromatic oxygen-containing (dibenzo- stituents of terrestrial organic matter (Almendros et al., 1998, furan and its methylation products) and sulfur-containing 1999; Tinoco et al., 2006; Dickens et al., 2007), including lignite 792 RYBICKI ET AL. deposits (Allard and Derenne, 2007).These authors conclude C31αβ S/(S + R) homohopane ratio, confirming the low degree that concentrations of benzene polycarboxylic acids increase of thermal maturity (Peters et al., 2005); however, in these with lignite humification. Therefore, the comparatively high cases, the scatter of results is wide, ranging from 0.1 to 0.5 relative concentrations of benzenedicarboxilic acids in our (Table 3). internal sediments suggest an advanced stage of lignin decom- Distributions of polycyclic aromatic compounds indicate a position and extensive humification of organic matter. Pheno- low degree of thermal maturity, as well. Values of MPI1, a com- lic compounds are represented by many structures (Table 6), monly used maturity parameter, are diverse (Table 3). How- among which benzoic acid, vanillin, hydroxybenzoic acids, and ever, the use of this index is not recommended in the case of vanillic acid are recognized as typical decomposition products vitrinite reflectance values lower than ca. 0.5% (Radke, 1987). of gymnosperm lignin (Thevenot et al., 2010; Bertrand et al., Nevertheless, the distribution of triaromatic members of phe- 2013). Interestingly, the vanillic acid to vanillin ratio (Ad/Al)v nyl derivatives of PAHs, PhNR (the relative abundance of the values are relatively low (in the range of 0.2–0.56; see Table 3), more stable 2-PhN to the less stable 1-PhN), and TrP1 (the suggesting minor lignin degradation, in contrast to values for p-terphenyl to o-terphenyl ratio) does confirm the low matu- benzene polycarboxylic acids (Hedges et al., 1985, 1988; Tareq rity of organic matter in our internal sediments (Marynowski et al., 2004). et al., 2001). According to that study, the low maturity is The occurrence of monosaccharides, most probably expressed by low values of PhNR (not exceeding 2.5 in nine of derived from polysaccharide degradation, also supports a ter- 11 samples) and by the definite preponderance of ortho- over restrial origin for the organic matter. Furthermore, relatively metha- and para-isomers in terphenyls, as reflected by TrP1 high concentrations of dibenzofuran and its alkyl derivatives ratios below 0.5 in 10 of 11 samples (Table 3). suggest land-derived diagenetic products of polysaccharides Experimental (Faure et al., 1999) and field (Marynowski (Sephton et al., 1999, 2005). The next polar biomarkers com- and Wyszomirski, 2008) studies show that oxidation processes ing from higher plants are sterols, represented by sitosterol may have resulted in the alteration of long-chain n-alkanes and and its transformation products, including stigmastanol and in the obliteration of differences between even and odd long- stigmasta-3, 5-dien-7-one. All of these biomarkers indicate a chain n-alkanes. Oxidation of organic matter can also alter the terrestrial origin. distribution of such biomarkers as hopanes and steranes, lead- Thus, palynological analyses have not only provided strong ing to the conversion of thermodynamically less stable com- evidence for the age of the source, but also for the origin of pounds to more stable ones (Elie et al., 2000). In the case of the organic matter. The majority of the palynomorphs are our internal sediments, we suggest hydrothermal fluids pro- terrestrially derived sporomorphs. Assemblages from marine duced a mild oxidation of organic matter, which altered the or higher-salinity environments are also recognized. Without compositions of organic constituents. According to fluid inclu- dinoflagellate cysts in the Middle Triassic of this region or the sion data, the approximate temperatures of fluids were 80° to presence of foraminiferal test linings, the only palynologi- 158°C, with the higher temperatures of this range occurring cal indicators for potentially higher salinities and, therefore, to the south and lower temperatures to the north (Kozłowski, potential marine sources of organic matter are acritarchs and 1995). It has been shown experimentally that low-tempera- possibly prasinophytes. Samples with reliable indicator taxa ture hydrothermal alteration of wood biomass may produce occur in both the Pomorzany and Klucze region, as well as in mainly phenolic compounds (Karagöz et al., 2005), similar to the Trzebionka mine, implying that the various processes dis- those noted here. Moreover, low temperatures would explain cussed above and the sources of organic matter in the internal differences between the molecular compositions of organic sediment are of regional and not only local importance. constituents in our internal sediments and the indicators of In summary, taking into account the compositions of inter- organic maturation (Table 3). nal sediment extracts and palynomorph assemblages, it is Unsubstituted polycyclic aromatic hydrocarbons predomi- clear that terrestrial organic matter is dominant in all samples, nate over their methyl derivatives, which is characteristic of while marine input is also possible but not clearly proven. oxidized organic matter. The phenanthrene to methylphen- Despite conflicting results concerning the preservation of anthrenes ratio, described by Püttmann et al. (1989), Speczik lignin, we conclude that the general degradation of geopoly- et al. (1995), Bechtel et al. (2001), and Oszczepalski et al. (2002) mers is advanced and can be related to mild oxidation of kero- for Permian Kupferschiefer samples and by Marynowski and gens by hydrothermal fluids. Low to moderate vanillic acid Wyszomirski (2008) for Triassic samples from the Holy Cross to vanillin-(Ad/Al)v ratios, typical of nondegraded lignin, are Mountains and the Upper Silesia basin, is considered to be a not considered reliable because our data are based on natural good indicator of the level of oxidation. In the current study, oxidation, not on laboratory CuO lignin degradation (sensu the P/(ΣMP) values are higher than unity in all samples (Table Hedges et al., 1988). 3), and are indicative of intense oxidation of organic matter. However, elevated concentrations of phenanthrene in internal Maturity and preservation of organic matter sediment samples can originate from pyrolytic processes and The organic matter content of our samples is immature and would explain the higher P/(ΣMeP) values in our internal well preserved, which is unusual for an Anisian sediment. sediments. Moreover, significant differences between samples Huminite reflectance values do not exceed 0.32% (Table 3), in the C30M/C30H values and in the absence of hopanes with characteristic of the lignite range of maturity (Hayes, 1991; a ββ configuration in some samples (see Table 3) could be Hunt, 1995). The polar fractions, clearly dominant in all sam- attributed to the advanced oxidation of organic matter. Based ples (Table 3), are characteristic of immature organic matter on experimental data, a similar effect was attributed by Elie (Tissot and Welte, 1984). Low values were also found for the et al. (2000, 2004) to descending oxygen-rich meteoric water ORGANIC MATTER IN INTERNAL SEDIMENTS FROM THE SILESIAN-CRACOW LEAD-ZINC DEPOSITS, POLAND 793

(Brown, 2005) or to weathering (Marynowski and Wyszomir- 1993). Meteoric paleokarsts also developed in the Upper Tri- ski, 2008; Marynowski et al., 2011a, b). assic and the Lower Jurassic (Głazek, 1989, and references Differences in oxidation levels between samples could also therein). Narrow voids, filled by siliciclastic sediments and be attributed to the development of complex meteoric and locally by black organic matter-rich clays, developed at that hydrothermal paleokarst systems within ore-hosting dolo- time (Gilewska, 1965). mites (see Bogacz et al., 1970; Sass-Gustkiewicz, 1974, 1996; Meteoric paleokarst channels and small cavities, filled or Dz˙ułyński and Sass-Gustkiewicz, 1985). Samples ISPM10 and not by fine-grained internal sediments and devoid of lead-zinc ISKL3 show the highest oxidation levels, with significantly mineralization, are common in Olkusz and Pomorzany ores. lower C30M/C30H values (0.17 and 0.18, respectively) com- Spectacular meteoric paleokarst caves were discovered dur- pared to other samples, as well as relatively lower TOC values ing the exploitation of unweathered parts of the sulfide ores in (especially for sample ISPM10, with 2.42%) and an absence the Pomorzany and Trzebionka mines (Motyka et al., 1996). of ββ-hopanes. However, oxidation processes, if they had an These meteoric paleokarsts are only partially filled by organic impact on other samples, could not have been intense, given matter (previously interpreted mistakenly as Lower Jurassic the high TOC values of most of these internal sediments and in age due to the lack of palynological data), whereas lead-zinc the excellent preservation of unstable organic compounds. mineralization is absent in these caves. Moreover, pre-ore This contention applies in particular for polar compounds, paleokarst breccias without sulfide mineralization have been among which saccharides, sterols, and polyphenols (lignin described by Leach et al. (1996), suggesting that the develop- degradation products) were identified (Figs. 10, 11). ment of many paleokarst features was independent of sulfide Saccharides are especially unstable compounds and are deposition. During the Lower Cretaceous mineralizing event, rarely reported in sedimentary rocks older than Pleistocene this part of the meteoric paleokarst system was probably iso- age (Moers et al., 1994; Fabbri et al., 2009). The only reli- lated from the lead-zinc–bearing hydrothermal fluids. These ably reported identification of monosaccharides in Mesozoic observations indicate that the Triassic meteoric paleokarst sys- sediments is that of Moers et al. (1994), who identified low tem was not destroyed during Jurassic and Cretaceous time. concentrations of monosugars with significant glucose in the The origins of three components of the internal sediments Toarcian shales of the Paris basin (France) and in the Posido- (grain-supported dolomite, iron-zinc sulfides, and organic nia shale (Germany). To the best of our knowledge, we have matter) are crucial for genetic explanations of the internal sed- identified the oldest saccharides in the geologic record. Their iments and the lead-zinc ores of the Silesia-Cracow area. Pet- preservation is attributed to the rapid accumulation of internal rographically, our samples of internal sediments are classified sediments in their meteoric paleokarst cavities. The mineral- as dolosparites. The complex genesis of these internal sedi- ogical composition of the internal sediments confirms that the ments involved three initial meteoric stages: (1) dolomitiza- organic matter had no contact with clay minerals, which would tion of lime ooze, resulting in the growth of dolomite crystals; have increased the rate of alteration of organic matter (Heller- (2) alteration of the host dolostone in a meteoric paleokarst Kallai et al., 1996). Moreover, the burial temperature of the environment, which led to the dissolution of remnant calcite host rocks has never exceeded ca. 50°C (based on low vitrinite and partial disintegration of dolomite to form dolomite sand; reflectance values). However, we do not exclude a mild oxi- and (3) resedimentation of dolomite sand within meteoric dation of some internal sediments, which would have led to paleokarst channels and caves, followed by lithification and partial decomposition of lignin and cellulose geopolymers and the deposition of late constituents (e.g., sphalerite, framboidal to the occurrence of monomers in the polar fraction (Table 6). pyrite, and gypsum), which is clearly documented by sedimentary structures characteristic of all internal sediments exam- Affiliation of internal sediments, meteoric and hydrothermal ined here (see Figs. 2, 3a, b). The textures and mineralogy of paleokarsts, and lead-zinc mineralization the grain-supported dolostone indicate their detrital origin. Meteoric paleokarsts are common in the Silesia-Cracow The well-developed layering (see Fig. 3A), the uniform grain region. Middle Triassic meteoric paleokarsts are best rep- size of the dolomite crystals within separate layers, and the resented at the Stare Gliny quarry, where meteoric karstic high porosities and subordinate clay mineral contents suggest processes developed a fossil mogote of Devonian dolostones deposition in a dynamic environment within large caverns and surrounded by Triassic carbonate sediments (Lis and Wójcik, meteoric paleokarst-like channels, accompanied by extensive 1960). A meteoric paleokarst cave at Stare Gliny was filled by grain segregation. The final stage (4) concerns hydrothermal fine-grained carbonate sediment and bone breccia composed sulfide replacement of internal sediments. This stage is not of reptile bones and fish teeth and scales of Middle Triassic recorded in all internal sediments, but only in those which age (Głazek, 1989, and references therein). A well-developed were altered during the formation of lead-zinc deposits (see meteoric paleokarst has also been documented in logging the Leach et al., 1996). Klucze-1 drill core (Górecka, 1991). In the hanging wall of Occurrences of unusually well preserved organic matter, the Upper Devonian carbonates, numerous meteoric paleo- together with palynomorphs, are useful to constrain the envi- karst cavities are filled by clayey marl and reddish carbonate ronments of deposition and the ages of the internal sediments sediments. According to Górecka (1991) and Kurek (1993), filling the caverns. The palynomorphs recognized during this lead-zinc–bearing hydrothermal fluids exploited open spaces study are Anisian (early Middle Triassic) in age, and are domi- created during Permian-Triassic time in Devonian rocks. nated by terrestrial assemblages with subordinate amounts of Interestingly, the economically important lead-zinc resources marine material. Our palynological data are consistent with in the Zawiercie region occur as stratoidal orebodies in Devo- the results of Zawi´slak (1965), who also suggested a Middle nian dolostones and Middle Triassic limestones (Górecka, Triassic age for poorly preserved palynomorphs observed in 794 RYBICKI ET AL. her study. The consistent Anisian age of organic remnants and karst-hosted internal sediments. These sulfide components the lack of Lower Jurassic and/or younger palynomorphs in were redistributed or resedimented only during the Lower our samples of internal sediment probably resulted from the Cretaceous lead-zinc mineralization (Sass-Gustkiewicz, 1996, limitation of karsting to Anisian time only. The unusual pres- 2007). This type of internal sediment was redeposited as detri- ervation of the organic matter within our internal sediments tal grains during the intensely focused flow of hydrothermal is likely due to their contemporaneous sedimentation in the solutions through meteoric paleokarst channels during the well-developed open spaces of the meteoric paleokarst system simultaneous chemical deposition of the main stage of lead- under conditions of limited oxygen availability immediately zinc mineralization. Such processes destroyed primary sedi- after sedimentation, with the absence of significant diagen- mentary structures and led to the mixing of dolomitic sand esis (e.g., the lack of compaction, long-term thermal effects), with detrital sulfides and organic matter previously deposited and with the deposition of late diagenetic cements. The most in the meteoric paleokarst system. probable source area for generally terrestrial organic matter The regularity of the mode of ore formation provides addi- would have been an archipelago of small islands located along tional indirect evidence that widespread Triassic meteoric the Cracow-Myszkow tectonic zone (Szulc and Becker, 2007; paleokarsts in the Silesia-Cracow region have been used by Matysik, 2014). Tectonic activity on this zone during Triassic lead-zinc–bearing hydrothermal fluids (Szuwarzyński, 1996). time is manifested by shallow-water carbonates sedimenta- Near the Cracow-Myszkow tectonic zone, nest-like orebodies tion, associated with the development of numerous hiatiuses with breccia texture predominate in the eastern part of the ore during sedimentation and episodes of early-diagenetic dolo- districts (Pomorzany, Olkusz, Zawiercie, Kalety). Here, the mitization (Myszkowska, 1992; Szulc, 1999, 2000; Matysik, orebodies are irregular (generally concentrated in the hanging 2014). Moreover, tectonic movement on this zone would walls of ore-bearing dolomite), and their size is diverse. The have also been crucial to the rapid elevation of Triassic car- biggest orebodies are over the 30 m in thickness. These lead- bonates deposited on the Upper Silesia block (immediately zinc ores probably formed using the well-developed meteoric after carbonate sedimentation), as well as the rapid develop- paleokarst system, consisting of several caves of consider- ment of meteoric paleokarsts, which explains the narrow time able size. Regularly distributed lead-zinc-iron mineralization span between Triassic carbonate sedimentation and the age predominates over several ore horizons in the western and of organic matter in the internal sediments. Note that the southern parts of the ore districts (Bytom, Tarnowskie Góry, Cracow-Myszkow tectonic zone had been active from Car- Chrzanów). It is inferred from these observations that these boniferous to present time (Buła et al., 1997; Z˙ aba, 1999; ores represent the distal parts of the meteoric paleokarst sys- Buła, 2000; Matyszkiewicz et al., 2006; Jurewicz et al., 2007; tem developed in narrow leached horizons concordant with Olszewska-Nejbert and Swierczewska-Gładysz,´ 2009), and it carbonate platforms or with the water table during Triassic controlled the sedimentary environment as well as tectonic meteoric karst-forming processes. and magmatic processes along the contact zone between the The observations in the Pomorzany and Olkusz mines indicate Upper Silesian and Małopolska blocks. that ore mineral incrustations occur rarely below mineralized Dolomite grains (Fig. 4) show traces of intense dissolution internal sediments at the contact with the basal limestone (Sass that may have developed during meteoric or hydrothermal Gustkiewicz, 1985, and references therein). The largest concen- paleokarsting (e.g., Sass-Gustkiewicz, 1985; Leach et al., 1996). trations of ore minerals occur above the mineralized internal The oxygen and carbon isotope signatures of dolomitic grains sediment, continuing upward into cracked dolostone zones or suggest that the internal sediments were derived from dissolved breccia zones above. This distribution indicates that mineral- Triassic dolomites and show early-diagenetic isotopic signatures ized internal sediments currently filling open spaces at the base (Fig. 7). The Middle Triassic carbonate sequence consists of of orebodies were present before the main-stage ore-forming three different early-diagenetic dolomites (Szulc, 1999, 2000), event. During hydrothermal karsting, unlithified meteoric karst- which can be considered to have been the source of dolomite hosted internal sediments were redeposited by hydrothermal grains for our internal sediments. These dolomite grains are fluids and mixed with the lead-zinc-iron sulfides and residues of represented by early-diagenetic Röt dolomite, by Diplopora carbonate dissolution, according to the model proposed by Sass- Dolomite that occurs in the lower- and uppermost parts of the Gustkiewicz (1985). In lead-zinc–rich parts of the ore depos- Middle Triassic carbonate sequence, and by the first-genera- its, redeposited mineralized internal sediments predominate, tion (i.e., early diagenetic; see Narkiewicz, 1993; Matysik, 2014) whereas in isolated parts of the meteoric paleokarst systems, ore-bearing dolomite that hosts economic lead-zinc mineraliza- through which hydrothermal fluids did not flow, the origi- tion. The early-diagenetic dolomite also forms the Tarnowickie nal meteoric paleokarstic nonmineralized internal sediments and Boruszowickie beds that constitute the uppermost Middle remain and include well-preserved Anisian palynomorphs. Triassic carbonates of the Silesia-Cracow area (Szulc, 1999, 2000). Sphalerite, pyrite, and rare galena form sulfide cements Conclusions or small euhedral grains (Fig. 6a, b), strongly suggesting that The organic matter of internal sediment in the Silesian- the nonmineralized internal sediments were deposited during Cracow lead-zinc deposits is immature and corresponds to meteoric paleokarst of the Middle Triassic dolostones and lime- the vitrinite reflectance values characteristic for lignites. The stones. Small amounts of sphalerite and galena indicate only main source of organic matter was terrestrial higher plants, a limited infiltration by ore-forming solutions invading these with a minor marine input, as well. The dominant compo- meteoric karst-hosted internal sediments. nent of the organic matter is partially degraded lignin and On the other hand, detrital remnants of lead-zinc-iron sul- products of polysaccharide degradation. The occurrence of fides constitute a significant component of the hydrothermal monosaccharides between polar compounds is unusual and ORGANIC MATTER IN INTERNAL SEDIMENTS FROM THE SILESIAN-CRACOW LEAD-ZINC DEPOSITS, POLAND 795 provides evidence of a good state of preservation for Trias- Bertrand, O., Mansuy-Huault, L., Montargès-Pelletier, E., Faure, P., Losson, sic organic matter. Petrological and paleontological data of B., Argant, J., Ruffaldi, P., and Michels, R., 2013, Recent vegetation history from a swampy environment to a pond based on macromolecular organic the internal sediments of the Silesian-Cracaw lead-zinc dis- matter (lignin and fatty acids) and pollen sedimentary records: Organic trict clearly indicate the development of a Triassic meteoric Geochemistry, v. 64, p. 47–57. paleokarst system immediately after Anisian carbonate sedi- Bogacz, K., Dz˙ułyński, S., and Harańczyk, C., 1970, Ore-filled hydrothermal mentation. This meteoric paleokarst system was used during karst features in the Triassic of the Upper Silesian region: Acta Geologica the Lower Cretaceous by hydrothermal solutions responsible Polonica, v. 20, p. 247–267. Bogacz, K., Dz˙ułyński, S., Harańczyk, C., and Sobczyński, P., 1972, Contact for the formation of lead-zinc mineralization in the Silesia- relations of the ore-bearing dolomite in the Triassic of the Cracow-Silesia Cracow area. The excellent preservation of organic matter region: Annales Societatis Geologorum Poloniae, v. 42, p. 347–380. in the Silesian-Cracow meteoric paleokarst systems is due Bogacz, K., Dz˙ułyński, S., and Harańczyk, C., 1975, Origin of the ore-bearing to sedimentation under conditions of limited oxygen avail- dolomite in the Triassic of the Cracow-Silesian Pb-Zn district: Annales Soci- etatis Geologorum Poloniae, v. 45, p. 139–155. ability immediately after sedimentation, and to the absence Brown, A.C., 2005, Refinements for footwall red-bed diagenesis in the sedi- of significant diagenesis, e.g., the lack of compaction and ment-hosted stratiform copper deposits model: Economic Geology, v. 100, long-lasting thermal effects, and the lack of late-diagenetic p. 765–771. cements. Lower Cretaceous lead-zinc mineralization did not Buła, Z., 2000, The lower Palaeozoic of Upper Silesia and West Małopolska: contribute significantly to the degradation of organic matter Prace Państwowego Instytutu Geologicznego, v. 171, p. 1–63. (in Polish with English abstract) in the internal sediments. Buła, Z., Jachowicz, M., and Z˙ aba, J., 1997, Principal characteristics of the Upper Silesian block and Małopolska block border zone (southern Poland): Acknowledgments Geological Magazine, v. 134, p. 669–677. This work was supported by NCN grants DEC-2012/05/N/ Cabała, J., 2002, Geological structure and physical features of rock mass of ST10/00486 to MR and 2015/19/B/ST10/00925 to LM. Dr. Zawiercie Zn-Pb region: Publications of the Institute of Geophysics, Polish Academy of Sciences Monographic Volume M-24, v. 340, p. 195–203. Magdalena Misz-Kennan (Faculty of Earth Sciences, Sosnow- Chen, J., Walter, M.R., Logan, G.A., Hinman, M.C., and Summons, R.E., iec) is thanked for help with huminite reflectance measure- 2003, The Paleoproterozoic McArthur River (HYC) Pb/Zn/Ag deposit of ments. The technical assistance of Dr. Sławomir Kurkiewicz northern Australia: Organic geochemistry and ore genesis: Earth and Plan- and Mariusz Gardocki is also gratefully acknowledged. This etary Science Letters, v. 301, p. 382–392. paper was greatly improved by the careful and critical remarks Connan, J., 1984, Biodegradation of crude oils in reservoirs, in Brooks, J., and Welte, D.H., eds., Advances in petroleum geochemistry, v. 1: London, and suggestions by reviewers Andrew P. Gize and Donald F. Academic Press, p. 299–335. Sangster, as well as associate editor Alex C. Brown. 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