@article{2-s2.0-85111334635,

title = {Preservation of hemicellulose remnants in sedimentary organic matter},

author = { L. Marynowski and M. Bucha and M. Lempart-Drozd and M. Stępień and M. Kondratowicz and J. Smolarek-Lach and M. Rybicki and M. Goryl and J.J. Brocks and B.R.T. Simoneit},

url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85111334635&doi=10.1016%2fj.gca.2021.07.003&partnerID=40&md5=3db5f77e50b98e7da685875bb2ec57e8},

doi = {10.1016/j.gca.2021.07.003},

issn = {00167037},

year  = {2021},

date = {2021-01-01},

journal = {Geochimica et Cosmochimica Acta},

volume = {310},

pages = {32-46},

publisher = {Elsevier Ltd},

abstract = {Cellulose has been identified in fossil material, but the preservation potential of hemicelluloses, which are less resistant to decomposition than cellulose, is generally considered very low. Here we present the discovery of hemicellulose in Miocene xylites (fossil wood) and Cretaceous xylo-detritic coals from Poland. The main building blocks of hemicelluloses in softwood are mannose, glucose, xylose with lesser amounts of galactose and arabinose. These saccharides were detected in the coals and xylites using independent geochemical methods. Based on chemical analysis, the lignites contained significant holocellulose (22–37%), α-cellulose (8–29%) and hemicellulose (7–13%). In the smoke from a xylite burn test, levoglucosan and mannosan were dominant, the latter a specific hemicellulose alteration product. Glucose and mannose products dominated after methanolysis, with minor galactose and xylose. The main hemicellulosic polysaccharides in lignite appear to be glucomannan and/or galactoglucomannan but with a lower mannose content, possibly connected to wood degradation by fungi. The preservation of hemicelluloses in fossil material may be due to structural interconnection between lignin, cellulose and hemicellulose (i.e. lignocellulose), common in extant wood. This is the first documentation of hemicelluloses in fossil material. Our results show that not only cellulose, but also hemicelluloses can persist for millions of years under favorable conditions with only minor structural changes due to slow microbial and/or diagenetic decay. In fossil wood, types of hemicellulose can help assess whether the ancient plants were related to gymnosperms or angiosperms. © 2021 Elsevier Ltd},

note = {3},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{2-s2.0-85102972550,

title = {Monoterpenylabietenoids, novel biomarkers from extant and fossil Taxodioideae and sedimentary rocks},

author = { B.R.T. Simoneit and M. Rybicki and M. Goryl and M. Bucha and A. Otto and L. Marynowski},

url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85102972550&doi=10.1016%2fj.orggeochem.2020.104172&partnerID=40&md5=f330e429889bbdaac445f551219bde7e},

doi = {10.1016/j.orggeochem.2020.104172},

issn = {01466380},

year  = {2021},

date = {2021-01-01},

journal = {Organic Geochemistry},

volume = {154},

publisher = {Elsevier Ltd},

abstract = {The presence of 7-p-cymenylferruginol and its diagenetic biomarkers occurring in Cenozoic fossil plants and Mesozoic siltstones and coals has been studied using gas chromatography-mass spectrometry. Both 7α- and 7β-p-cymenylferruginol isomers were the dominant natural products, with two novel minor additional isomers, namely 3α- and 3β-p-cymenylferruginol, and two hydrocarbons, 7α- and 7β-p-cymenyldehydroabietane. The other tentatively assigned aromatic hydrocarbons were 9,10-p-cymenylretene and 9-p-cymenylsimonellite, which were present in Upper Cretaceous and Lower Jurassic sedimentary rocks with their further dehydrogenation products. Diterpenoid dimers were also tentatively identified in trace amounts, with 11- and 14-ferruginylferruginol as the dominant compounds. Our results show that the p-cymenylferruginols and p-cymenyldehydroabietanes are not thermally stable and that their occurrence in sedimentary rocks is controlled by the maturity of the organic matter (OM). Also, chamaecydin, identified for the first time in pre-Paleogene strata, was not detectable when the OM maturity based on vitrinite reflectance was higher than ∼0.45–0.5% Rr. © 2020 Elsevier Ltd},

note = {2},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{2-s2.0-85085246367,

title = {Variations in δ13C values of levoglucosan from low-temperature burning of lignite and biomass},

author = { M. Rybicki and L. Marynowski and A. Bechtel and B.R.T. Simoneit},

url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85085246367&doi=10.1016%2fj.scitotenv.2020.138991&partnerID=40&md5=5bf73659efcd973eedd0974c9ab2c86c},

doi = {10.1016/j.scitotenv.2020.138991},

issn = {00489697},

year  = {2020},

date = {2020-01-01},

journal = {Science of the Total Environment},

volume = {733},

publisher = {Elsevier B.V.},

abstract = {Levoglucosan, an anhydrosaccharide, is commonly used as an organic tracer for biomass burning, but has also been identified from coal smoke particulate matter (PM) including lignites. Here we showed that stable carbon isotope analysis specifically of levoglucosan may be one possible way to determine the relative contributions from coal combustion versus biomass burning sources. PM samples were collected from low-temperature burning/smoldering of Miocene lignites from Poland and basket willow (Salix viminalis L.) representative of biomass. The calculated levoglucosan δ13C values of xylites varied from −23.6 to −21.6‰, while for detritic coal samples they ranged from −24.2 to −23.1‰, with means of −22.7 and −23.7‰, respectively. The calculated levoglucosan δ13C value of basket willow wood was −27.1‰. Values of willow wood mixtures with xylite varied from −25.8 to −23.4‰ (with an increasing proportion of xylite), while values of mixtures of willow and detritic coal ranged from −26.9 to −24.6‰ (with an increasing proportion of detritic coal). The δ13C values for the mixtures changed proportionally to the contents of individual components with R2 = 0.88 and 0.89 for willow with xylite and detritic coal, respectively. The hopanoid distributions characteristic for low-temperature lignite/peat burning, with a predominance of 22R-α,β-homohopane, ββ-hopanes and hopenes, as well as low or very low values of the homohopane index, were observed in smoke PM from most lignite samples and absent in the basket willow sample. Thus, the relatively high content of hopanes (with the occurrence of 22R-α;β-homohopane; ββ-hopanes and hopenes) in atmospheric PM samples can be treated as additional tracers of lignite combustion. © 2020 The Authors},

note = {9},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{2-s2.0-85079238246,

title = {Composition of organic compounds from low-temperature burning of lignite and their application as tracers in ambient air},

author = { M. Rybicki and L. Marynowski and B.R.T. Simoneit},

url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85079238246&doi=10.1016%2fj.chemosphere.2020.126087&partnerID=40&md5=55288df11ac7f26390e9127aa99067b1},

doi = {10.1016/j.chemosphere.2020.126087},

issn = {00456535},

year  = {2020},

date = {2020-01-01},

journal = {Chemosphere},

volume = {249},

publisher = {Elsevier Ltd},

abstract = {Levoglucosan, a product from thermal decomposition of cellulose, is widely known as an organic tracer of biomass burning, but has also been reported from coal smoke particulate matter (PM) including lignites. This study provides direct evidence that levoglucosan is generated not only during low-temperature burning/smoldering of xylite, but also from other lignite types including detritic and detroxylitic brown coals from Poland. Moreover, only trace amounts of mannosan and galactosan have been detected in PM of lignite smoke. The hopanes in lignite smoke PM comprise the thermodynamically unstable ββ-hopanes and hopenes, with values of the homohopane index 22S/(22S + 22R) ranging from 0.02 to 0.12. This is characteristic for immature organic matter, and combined with the presence of anhydrosaccharides can be used as tracers for lignite combustion in ambient air. Furthermore, almost all Miocene lignite smoke PM samples contain α-, β-, γ-, and δ-tocopherols, and prist-1-ene. This is the first report of the occurrence of all four tocopherol isomers in the geological record (in lignite extracts) and in lignite smoke PM samples. Lower α-tocopherol is observed for the lignite burn-test samples than in the corresponding lignite extracts, probably due to partial chain degradation to prist-1-ene during combustion. © 2020 Elsevier Ltd},

note = {18},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{2-s2.0-85081047423,

title = {Terpenoid biomarkers of ambers from Miocene tropical paleoenvironments in Borneo and of their potential extant plant sources},

author = { B.R.T. Simoneit and D.R. Oros and Ł. Karwowski and Ł. Szendera and J. Smolarek-Lach and M. Goryl and M. Bucha and M. Rybicki and L. Marynowski},

url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85081047423&doi=10.1016%2fj.coal.2020.103430&partnerID=40&md5=bbc4d9da365e778a7079a51113ac8268},

doi = {10.1016/j.coal.2020.103430},

issn = {01665162},

year  = {2020},

date = {2020-01-01},

journal = {International Journal of Coal Geology},

volume = {221},

publisher = {Elsevier B.V.},

abstract = {The chemical composition of ambers is highly diverse, characterized by the occurrence of a variety of terpenoids including: mono-, sesqui-, di-, and triterpenoids. The direct analyses of their chemical constituents in total extracts using polar solvents permits the elucidation of unaltered natural products, which are characteristic of the source plants or paleobiome. At this time, knowledge is limited about the plant origins of fossil resins that formed in tropical climatic conditions. Here, we present the complex chemical characteristics of Miocene fossil resins (resinites; termed here as ambers) from the tropics of Kalimantan (Borneo; Indonesia). Extant plant resins from the same geoclimatic region were also analyzed to identify the potential botanical sources of the ambers. Gas chromatography-mass spectrometry (GC–MS) analyses of total extracts (silylated and methylated) of natural and amber samples were carried out and compared with standard compounds. The main producers of resins forming these Miocene ambers were angiosperms - probably resins of Shorea and less likely Hopea, but not Dipterocarpus species. The key chemotaxonomic marker, present in the ambers and extant Shorea species, was asiatic acid. All samples were composed of sesquiterpenoids and triterpenoids in various proportions, without diterpenoids, characteristic for flowering plants. The sesquiterpenoids in the resins of both ambers and extant plants were primarily natural products with the cadinane skeleton. The triterpenoids of the extant resins of the Dipterocarpaceae and Miocene ambers were characterized by a prevalence of ursane over oleanane types. Polymerization of cadinoids in resins from Shorea species and in the ambers was not extensive. Based on the amber compositions we conclude that the molecular alteration of the Miocene deposits from Kalimantan is rather low, but differs depending on their location. © 2020 Elsevier B.V.},

note = {15},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{2-s2.0-85076608823,

title = {Origin and significance of saccharides during initial pedogenesis in a temperate climate region},

author = { L. Marynowski and O. Rahmonov and J. Smolarek-Lach and M. Rybicki and B.R.T. Simoneit},

url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85076608823&doi=10.1016%2fj.geoderma.2019.114064&partnerID=40&md5=54ee9e53760ab5f89e7e8e87428a1e3f},

doi = {10.1016/j.geoderma.2019.114064},

issn = {00167061},

year  = {2020},

date = {2020-01-01},

journal = {Geoderma},

volume = {361},

publisher = {Elsevier B.V.},

abstract = {Saccharides are common constituents of soils, but their role and origin in the initial phases of pedogenesis remain unclear. Here we show the detailed composition of neutral sugars extracted from arenosols at different development stages, combined with additional lipids of diverse origins using gas chromatography-mass spectrometry (GC–MS). During the first stage (I) of development sucrose is the most abundant saccharide in the soil crust at up to 45,000 µg/g TOC. Sucrose is also the predominant compound in the second and third development stages, but its concentration decreased to the range of 1600 to 16,000 µg/g TOC. Stages II and III of soil development were characterized by a gradual increase in arabitol, mannitol and trehalose, compounds typical for fungi and lichen. Their abundances increased from several percent (compared to the major sucrose) to 10–32% for mannitol and 34–54% for trehalose. Moreover, in stage III there was a considerable increase in the contents of the saccharides: pinitol, myo-inositol, scyllo-inositol, arabinose, together with non-sugar compounds: dehydroabietic acid, p-hydroxybenzoic acid, gallic acid and sitosterol. All these latter compounds are higher plant markers, mainly derived from conifer detritus. The relationships between the ratios of trehalose/sucrose vs. (mannitol + arabitol)/sucrose and TOC vs. (mannitol + arabitol)/sucrose differentiated precisely the top soil layer of arenosols which are covered by different stages of biological soil crust. Our study shows that free sugars, supplemented by lipid biomarkers and total organic carbon contents, are good indicators of soil in the initial phase of pedogenesis. © 2019 The Authors},

note = {7},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{2-s2.0-85019168995,

title = {Age and origin of the well-preserved organic matter in internal sediments from the silesian-cracow lead-zinc deposits, southern Poland},

author = { M. Rybicki and L. Marynowski and S. Stukins and K. Nejbert},

url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85019168995&doi=10.2113%2fecongeo.112.4.775&partnerID=40&md5=06f3f1c99cc24fe8d97ac4067d9a3c7c},

doi = {10.2113/econgeo.112.4.775},

issn = {03610128},

year  = {2017},

date = {2017-01-01},

journal = {Economic Geology},

volume = {112},

number = {4},

pages = {775-798},

publisher = {Society of Economic Geologists, Inc},

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. Huminite 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. © 2017 Society of Economic Geologists, Inc.},

note = {11},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{2-s2.0-85017556257,

title = {Benzohopane Series, Their Novel Di-, Tri-, and Tetraaromatic Derivatives, and Diaromatic 23- and 24-Norbenzohopanes from the Lower Jurassic Blanowice Formation, Southern Poland},

author = { M. Rybicki and L. Marynowski and B.R.T. Simoneit},

url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85017556257&doi=10.1021%2facs.energyfuels.6b03154&partnerID=40&md5=1bd4ead7ece940bd9bf00c35c9bc40c4},

doi = {10.1021/acs.energyfuels.6b03154},

issn = {08870624},

year  = {2017},

date = {2017-01-01},

journal = {Energy and Fuels},

volume = {31},

number = {3},

pages = {2617-2624},

publisher = {American Chemical Society},

abstract = {A total of 17 novel di-, tri-, and tetraaromatic derivatives of the benzohopane series cyclized at C-16 or C-20 as well as 4 diaromatic 23- and 24-norbenzohopanes have been identified in the coal and surrounding sandstone samples from the Lower Jurassic Blanowice Formation of southern Poland using gas chromatography-mass spectrometry. Their possible structures and formation pathway have been proposed on the basis of mass spectra and retention times. Bulk geochemical data and the presence of unsaturated benzohopane derivatives indicate low maturation of the Blanowice coals, characteristic for lignites. The diverse distributions of the benzohopane derivatives in the coals and surrounding sandstones showed differences in the extent of biodegradation. Our observations suggest that the di-, tri-, and tetraaromatic derivatives of benzohopanes cyclized at C-16 may be more resistant to biodegradation than regular benzohopanes. © 2017 American Chemical Society.},

note = {3},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{2-s2.0-84995554168,

title = {Molecular tracers preserved in Lower Jurassic “Blanowice brown coals” from southern Poland at the onset of coalification: Organic geochemical and petrological characteristics},

author = { M. Rybicki and L. Marynowski and M. Misz-Kennan and B.R.T. Simoneit},

url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84995554168&doi=10.1016%2fj.orggeochem.2016.09.012&partnerID=40&md5=ea86b5bdd29f4e9f33514cdc2d375fd7},

doi = {10.1016/j.orggeochem.2016.09.012},

issn = {01466380},

year  = {2016},

date = {2016-01-01},

journal = {Organic Geochemistry},

volume = {102},

pages = {77-92},

publisher = {Elsevier Ltd},

abstract = {The petrographic and molecular characteristics of the Pliensbachian–Toarcian “Blanowice brown coals” and associated sediments are described. These coals are generally dominated by vitrain macerals, although in one sample the inertinite is > 60%. This is interpreted as a result of wildfire or peat fire activity which was confirmed by the co-occurrence of charcoal fragments and elevated relative concentrations of unsubstituted PAHs in the samples. Vitrinite reflectance values are in the range of 0.49–0.56 %Ro and the C content varies from 30.3–61.9%, placing the coals within the sub-bituminous coal group. However, detailed characterization of coal extracts revealed their highly immature character, based on the occurrence of phenolic abietanes such as ferruginol, sugiol and 7-oxototarol, as well as other biomolecules including labdanoic acid, cholesterol and sitosterol. This is one of the first descriptions of natural product compounds in Jurassic sedimentary rocks. Moreover, in addition to typical lignin decomposition products, dicarboxylic acids with a preponderance of succinic acid were identified. To the best of our knowledge free dicarboxylic acids have not been reported previously from coal extracts. These acids are characteristic resin constituents. We speculate that a low (ca. 40–50 °C), but long-term, temperature influence led to an increased vitrinite reflectance values ca. 0.55 %Ro, with only minor changes to the composition of unstable biomarkers and biomolecules. Moreover, the resin matrix could protect unstable compounds against geochemical structural alteration. Vitrinite reflectance values may also be elevated due to oxidation which caused paler in colour reaction rims. The presence of phenolic abietanes and the absence of abietic and dehydroabietic acids suggest that the Cupressaceae and/or Podocarpaceae families were the most likely peat-forming plant species. © 2016 Elsevier Ltd},

note = {15},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{2-s2.0-84896294499,

title = {Determination of multiple organic matter sources in aerosol PM10 from Wrocław, Poland using molecular and stable carbon isotope compositions},

author = { M. Górka and M. Rybicki and B.R.T. Simoneit and L. Marynowski},

url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84896294499&doi=10.1016%2fj.atmosenv.2014.02.064&partnerID=40&md5=9390a1713799db540699f700d4e87110},

doi = {10.1016/j.atmosenv.2014.02.064},

issn = {13522310},

year  = {2014},

date = {2014-01-01},

journal = {Atmospheric Environment},

volume = {89},

pages = {739-748},

publisher = {Elsevier Ltd},

abstract = {The natural and anthropogenic contributions of hydrocarbon groups (aliphatic and aromatic), as well as total organic carbon, in atmospheric PM10 dust (particulate matter <10μm) collected from Wrocław (SW Poland) were assessed using combined molecular (gas chromatography-mass spectrometry - GC-MS) and stable carbon isotopic (isotope-ratio mass spectrometry - IR-MS) analyses. The PM10 samples were taken in the seasonal sampling program in 2007, and represent air pollution from all months of the year. The δ13C values of the total carbon varied seasonally from-27.6 to-25.3- The isotopic mass balance calculations confirmed greater coal burning input, reaching 70.5%, in the heating season and dominant transported sources 47.5% in the vegetative season. The data obtained for the aliphatic fractions: carbon preference index (CPI), carbon number maximum (Cmax), wax n-alkane contents (%WNA), and δ13C values of the aliphatic fractions (-36.6 to-29.4-), indicated a dominant anthropogenic origin (gasoline/diesel/coal combustion) and a lesser biogenic input (biomass burning and natural organic matter). Petroleum and coal combustion emissions were confirmed by the presence of hopanes and moretanes. The molecular analysis of the concentrations and diagnostic ratios of the polycyclic aromatic hydrocarbons (PAHs) and the δ13C values of the aromatic fractions (-35.4 to-26.8-) indicated that the main PAH sources were also collectively from combustion of liquid fuels and coal. Based on PAH discrimination diagrams it is also clear that the main organic carbon source is derived from coal, biomass and petroleum combustion in both seasons. However, taking into account the PAH concentrations during the vegetative and heating seasons, coal and biomass burning seem to be their major source. Additionally, the polar organic compounds (mainly levoglucosan) confirmed a significant contribution from biomass burning to the total anthropogenic input. The general conclusion derived from coupling of organic tracer analysis and carbon isotopic data of PM10 was that the total carbon (including insoluble soot) is likely derived from fossil fuel combustion, while the extractable organic matter is a mixture from different sources with significant inputs of biomass burning. We have also shown that dominant organic tracers do not always represent the major input source in aerosol PM and the unresolved part of the organic matter (soot) is important in the carbon budget. © 2014 Elsevier Ltd.},

note = {59},

keywords = {},

pubstate = {published},

tppubtype = {article}

}