anatomical and chemical characteristics of miocene

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Anatomical and chemical characteristics of Miocene Anatomical and chemical characteristics of Miocene Taxodiaceae Taxodiaceae species from species from B B ü ü kk kk á á br br á á ny ny (Hungary) (Hungary) Moln Moln á á r r , S., , S., 1 1 Albert, L., Albert, L., 2 2 Feh Feh é é r r , S., , S., 1 1 B B ö ö rcs rcs ö ö k, Z., k, Z., 1 1 Á Á brah brah á á m m , J., , J., 1 1 Hofmann, T., Hofmann, T., 2 2 Antalfi Antalfi , E. , E. 1 1 1 1 University of West University of West - - Hungary; Faculty of Wood Sciences; Department of Wood Sciences Hungary; Faculty of Wood Sciences; Department of Wood Sciences 2 2 University of West University of West - - Hungary; faculty of Forest Engineering, Department of Chemistry Hungary; faculty of Forest Engineering, Department of Chemistry H H - - 9400 Sopron, 9400 Sopron, Bajcsy Bajcsy - - Zs. Zs. str str . 4. . 4. Introduction Introduction 16 preserved trunks were found in an open cast 16 preserved trunks were found in an open cast coal (lignite) mine near coal (lignite) mine near B B ü ü kk kk á á b b á á rny rny in north in north - - eastern Hungary (Fig. 6). The trunks are 2 eastern Hungary (Fig. 6). The trunks are 2 - - 3 m 3 m in diameter and 5 in diameter and 5 - - 6 m in high. The stumps stood 6 m in high. The stumps stood in the lower level of the mine, at the beginning in the lower level of the mine, at the beginning of the coal deposit. These trees lived in the of the coal deposit. These trees lived in the marshland of the marshland of the Pannon Pannon Lake and the river Lake and the river deltas in the Miocene (Fig. 1), approximately deltas in the Miocene (Fig. 1), approximately 7,5 7,5 - - 8 million year ago. The trunks are especial, 8 million year ago. The trunks are especial, because they are not siliceous, and preserved because they are not siliceous, and preserved their porous structure (Fig. 2 their porous structure (Fig. 2 - - 3). 3). Results Results Anatomy Anatomy Looking the trunks in photos and in the mine, they were seemed t Looking the trunks in photos and in the mine, they were seemed t o have two types. o have two types. Some of them are slim (like Some of them are slim (like Sequioa Sequioa sempervirens sempervirens ), others became broad at the base ), others became broad at the base (like (like Taxodium Taxodium distichum distichum ). ). The main differences between The main differences between Sequoia Sequoia sempervirens sempervirens and and Taxodium Taxodium distichium distichium are the are the visibility of the torus in the visibility of the torus in the tracheids tracheids and the structure of the cell wall between the and the structure of the cell wall between the axial parenchyma cells. These walls in the axial parenchyma cells. These walls in the Sequioa Sequioa parenchyma cells are smooth, and parenchyma cells are smooth, and in in Taxodium Taxodium they are nodular. As Fig. 11 they are nodular. As Fig. 11 - - 12 show, one of them seem to be 12 show, one of them seem to be Sequioa Sequioa sempervirens sempervirens (sample 3), an the sample 5 is (sample 3), an the sample 5 is Taxodium Taxodium distichum distichum , so the two species , so the two species lived there together. lived there together. Chemical tests Chemical tests The Table 1. shows the results of the cellulose, phenol and carb The Table 1. shows the results of the cellulose, phenol and carb ohydrate tests. ohydrate tests. Taxodium Taxodium distichum distichum heartwood was the control. heartwood was the control. Summary Summary The cellulose content of the fossils are between 20 and 30%. The cellulose content of the fossils are between 20 and 30%. Although the strength of the wood was decreased, it could preser Although the strength of the wood was decreased, it could preser ve the original ve the original shape. shape. The examinations of the annual rings and the cell types show, th The examinations of the annual rings and the cell types show, th at more species from at more species from the the Taxodiaceae Taxodiaceae were present in the same time ( were present in the same time ( Taxodium Taxodium distichum distichum , Sequoia , Sequoia sempervirens sempervirens ) in that flora. ) in that flora. Further tests are needed (anatomical, macroscopic, some physical Further tests are needed (anatomical, macroscopic, some physical properties). properties). Materials and methods Materials and methods Samples from each trunks were collected (Fig. 4.), but just some Samples from each trunks were collected (Fig. 4.), but just some of the were of the were examined (Fig. 5.), the examination of the others is still runni examined (Fig. 5.), the examination of the others is still runni ng. The degradation of ng. The degradation of the samples were different. For control, samples were collected the samples were different. For control, samples were collected from the from the Taxodium Taxodium distichum distichum and and Sequoia Sequoia sempervirens sempervirens in the Botanical Garden, Sopron. Anatomical in the Botanical Garden, Sopron. Anatomical examination (light and SEM microscopy) were taken for the 3 and examination (light and SEM microscopy) were taken for the 3 and 5 sample, 5 sample, chemical tests were done for the 1 chemical tests were done for the 1 - - 5 samples. In these tests the cellulose, total phenol 5 samples. In these tests the cellulose, total phenol and total carbohydrate contents were measured and and total carbohydrate contents were measured and thermoanalitical thermoanalitical behavior were behavior were examined. The lignin content of the samples wasn examined. The lignin content of the samples wasn t measured, because of the t measured, because of the degradation of the lignin there is no method. All contents indic degradation of the lignin there is no method. All contents indic ted refer to the dry ted refer to the dry weight of the samples. weight of the samples. Fig. 1. The position of the Fig. 1. The position of the Pannon Pannon Lake at the Lake at the Miocene (Magyar et al. 1999) Miocene (Magyar et al. 1999) Fig. 2 Fig. 2 - - 3. Trunks in the open cast mine ( 3. Trunks in the open cast mine ( B B ü ü kk kk á á b b á á rny rny , Hungary) , Hungary) 1 1 2 2 3 3 5 5 4 4 Fig. 4 Fig. 4 - - 6. Collecting samples and some of them, which were 6. Collecting samples and some of them, which were tested tested 5.582 5.582 ± ± 0.264 0.264 0.932 0.932 ± ± 0.024 0.024 33.02 33.02 ± ± 4.84 4.84 5 5 10.83 10.83 ± ± 0.891 0.891 4.071 4.071 ± ± 0.145 0.145 37.42 37.42 controll controll 3.990 3.990 ± ± 0.286 0.286 0.765 0.765 ± ± 0.016 0.016 35.52 35.52 ± ± 4.83 4.83 4 4 3.165 3.165 ± ± 0.082 0.082 0.587 0.587 ± ± 0.063 0.063 30.15 30.15 ± ± 2.98 2.98 3 3 2.875 2.875 ± ± 0.308 0.308 1.280 1.280 ± ± 0.066 0.066 18.17 18.17 ± ± 3.22 3.22 2 2 1.428 1.428 ± ± 0.109 0.109 0.461 0.461 ± ± 0.059 0.059 33.33 33.33 ± ± 2.00 2.00 1 1 c c arbohydrate arbohydrate [mg/g] [mg/g] t. t. p p henol henol [ [ mmol mmol /100g] /100g] c c ellulose ellulose [%] [%] Table. 1. Lignin, cellulose, phenol and carbohydrate contents of Table. 1. Lignin, cellulose, phenol and carbohydrate contents of the samples the samples The early wood of the annual rings were The early wood of the annual rings were more degraded (red arrows) than the late more degraded (red arrows) than the late wood (yellow arrows), so wood (yellow arrows), so the the cells in the cells in the early wood collapsed (Fig. 7 early wood collapsed (Fig. 7 - - 10). The rays 10). The rays are are uniseriate uniseriate , homogenous. The cells of the , homogenous. The cells of the axial parenchyma are not grouped, these axial parenchyma are not grouped, these cells are containing some kind of material cells are containing some kind of material (green arrows). There are 2 (green arrows). There are 2 - - 4 4 taxodioid taxodioid or or cupressoid cupressoid pits in the cross fields. pits in the cross fields. Fig. 8 Fig. 8 - - 10. Light microscopic photos of the sample 3. Cross section. Deg 10. Light microscopic photos of the sample 3. Cross section. Deg raded early wood, axial raded early wood, axial parenchymas parenchymas with with some content some content Fig. 7. SEM photo of the sample 3, the early Fig. 7. SEM photo of the sample 3, the early wood is wood is degradated degradated Fig. 6. The location of Fig. 6. The location of B B ü ü kk kk á á br br á á ny ny in Hungary in Hungary Fig. 11 Fig. 11 - - 12. The structure of the cell wall between axial parenchyma cell 12. The structure of the cell wall between axial parenchyma cell s s Sample 3 Sample 3 Sample 5 Sample 5 The cellulose content of the fossils is significantly lower, par The cellulose content of the fossils is significantly lower, par tly disintegrated, so the tly disintegrated, so the lignin content relatively higher lignin content relatively higher ( ( it it wasn wasn t t measured measured ) ) , that , that s why the samples can be s why the samples can be crumbled. Significantly lower concentration of phenols and sugar crumbled. Significantly lower concentration of phenols and sugar s can be measured in s can be measured in the fossils. The degradation process of the fossils. The degradation process of polyoses polyoses can be clearly seen in the case of the can be clearly seen in the case of the samples by DSC (Fig. 13 samples by DSC (Fig. 13 - - 14). According to the DSC analysis too, the amount of 14). According to the DSC analysis too, the amount of cellulose is much lower in the fossils. The fossils show higher cellulose is much lower in the fossils. The fossils show higher thermal stability, which thermal stability, which could be explained by a higher lignin content. could be explained by a higher lignin content. 100 100 ° ° C C 260 260 ° ° C C 390 390 ° ° C C 410 410 ° ° C C Fig. 13 Fig. 13 - - 14. Differential scanning calorimetric (DSC) measurements of the 14. Differential scanning calorimetric (DSC) measurements of the samples. 100 samples. 100 ° ° C C water; water; 260 260 ° ° C C hemicellulose hemicellulose deg.; 390 deg.; 390 ° ° C C cellulose deg.; 410 cellulose deg.; 410 ° ° C C polymerisation polymerisation of the degradation products. of the degradation products. References References Dubois, M., Gilles, K. A., Hamilton, J. K., Dubois, M., Gilles, K. A., Hamilton, J. K., Rebers Rebers , P. A., Smith, F. (1956): Colorimetric method for determination , P. A., Smith, F. (1956): Colorimetric method for determination of sugars and related substances, of sugars and related substances, Anal. Chem. Anal. Chem. 28 28 : 350 : 350 - - 356. 356. Hoadley, R.B. (1990): Identifying wood. The Taunton Press, Newto Hoadley, R.B. (1990): Identifying wood. The Taunton Press, Newto wn, Connecticut, USA. wn, Connecticut, USA. Magyar, I., Geary, D.H., Magyar, I., Geary, D.H., M M ü ü ller ller , P. (1999): , P. (1999): Paleogeographic Paleogeographic evolution of the Late Miocene Lake evolution of the Late Miocene Lake Pannon Pannon in Central in Central Europe. Europe. Palaeogeography Palaeogeography , , Palaeoclimatology Palaeoclimatology , , Palaeoecology Palaeoecology 147: 147: 151 151 - - 167. 167. Singleton, V. L., Rossi, J. A., Jr. (1965): Singleton, V. L., Rossi, J. A., Jr. (1965): Colorimetry Colorimetry of Total of Total Phenolics Phenolics with with Phosphomolybdic Phosphomolybdic - - Phosphotungstic Phosphotungstic Acid Reagents, Acid Reagents, Am. J. Am. J. Enol Enol . . Vitic Vitic . . 16 16 (3): 144 (3): 144 - - 158. 158. Sopron Budapest Bükkábrány

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Anatomical and chemical characteristics of Miocene Anatomical and chemical characteristics of Miocene TaxodiaceaeTaxodiaceae species from species from BBüükkkk áábrbr áányny (Hungary)(Hungary)

MolnMoln áárr , S.,, S.,11 Albert, L.,Albert, L., 22 FehFehéérr , S.,, S.,11 BBöörcsrcsöök, Z.,k, Z.,11 ÁÁbrahbraháámm, J.,, J.,11 Hofmann, T.,Hofmann, T.,22 AntalfiAntalfi , E., E.11

11 University of WestUniversity of West--Hungary; Faculty of Wood Sciences; Department of Wood SciencesHungary; Faculty of Wood Sciences; Department of Wood Sciences22 University of WestUniversity of West--Hungary; faculty of Forest Engineering, Department of ChemistryHungary; faculty of Forest Engineering, Department of Chemistry

HH--9400 Sopron, 9400 Sopron, BajcsyBajcsy--Zs. Zs. strstr . 4.. 4.

IntroductionIntroduction

16 preserved trunks were found in an open cast 16 preserved trunks were found in an open cast coal (lignite) mine near coal (lignite) mine near BBüükkkkáábbáárnyrny in northin north--eastern Hungary (Fig. 6). The trunks are 2eastern Hungary (Fig. 6). The trunks are 2--3 m 3 m in diameter and 5in diameter and 5--6 m in high. The stumps stood 6 m in high. The stumps stood in the lower level of the mine, at the beginning in the lower level of the mine, at the beginning of the coal deposit. These trees lived in the of the coal deposit. These trees lived in the marshland of the marshland of the PannonPannon Lake and the river Lake and the river deltas in the Miocene (Fig. 1), approximately deltas in the Miocene (Fig. 1), approximately 7,57,5--8 million year ago. The trunks are especial, 8 million year ago. The trunks are especial, because they are not siliceous, and preserved because they are not siliceous, and preserved their porous structure (Fig. 2their porous structure (Fig. 2--3).3).

ResultsResultsAnatomyAnatomy

Looking the trunks in photos and in the mine, they were seemed tLooking the trunks in photos and in the mine, they were seemed to have two types. o have two types. Some of them are slim (like Some of them are slim (like SequioaSequioa sempervirenssempervirens), others became broad at the base ), others became broad at the base (like (like TaxodiumTaxodium distichumdistichum). ).

The main differences between The main differences between Sequoia Sequoia sempervirenssempervirens and and TaxodiumTaxodium distichiumdistichium are the are the visibility of the torus in the visibility of the torus in the tracheidstracheidsand the structure of the cell wall between the and the structure of the cell wall between the axial parenchyma cells. These walls in the axial parenchyma cells. These walls in the SequioaSequioa parenchyma cells are smooth, and parenchyma cells are smooth, and in in TaxodiumTaxodium they are nodular. As Fig. 11they are nodular. As Fig. 11--12 show, one of them seem to be 12 show, one of them seem to be SequioaSequioasempervirenssempervirens (sample 3), an the sample 5 is (sample 3), an the sample 5 is TaxodiumTaxodium distichumdistichum, so the two species , so the two species lived there together.lived there together.

Chemical testsChemical tests

The Table 1. shows the results of the cellulose, phenol and carbThe Table 1. shows the results of the cellulose, phenol and carbohydrate tests. ohydrate tests. TaxodiumTaxodium distichumdistichum heartwood was the control. heartwood was the control.

SummarySummary

•• The cellulose content of the fossils are between 20 and 30%. The cellulose content of the fossils are between 20 and 30%. •• Although the strength of the wood was decreased, it could preserAlthough the strength of the wood was decreased, it could preserve the original ve the original

shape. shape. •• The examinations of the annual rings and the cell types show, thThe examinations of the annual rings and the cell types show, that more species from at more species from

the the TaxodiaceaeTaxodiaceae were present in the same time (were present in the same time (TaxodiumTaxodium distichumdistichum, Sequoia , Sequoia sempervirenssempervirens) in that flora. ) in that flora.

•• Further tests are needed (anatomical, macroscopic, some physicalFurther tests are needed (anatomical, macroscopic, some physicalproperties).properties).

Materials and methodsMaterials and methods

Samples from each trunks were collected (Fig. 4.), but just someSamples from each trunks were collected (Fig. 4.), but just someof the were of the were examined (Fig. 5.), the examination of the others is still runniexamined (Fig. 5.), the examination of the others is still running. The degradation of ng. The degradation of the samples were different. For control, samples were collected the samples were different. For control, samples were collected from the from the TaxodiumTaxodiumdistichumdistichum andand Sequoia Sequoia sempervirenssempervirens in the Botanical Garden, Sopron. Anatomical in the Botanical Garden, Sopron. Anatomical examination (light and SEM microscopy) were taken for the 3 and examination (light and SEM microscopy) were taken for the 3 and 5 sample, 5 sample, chemical tests were done for the 1chemical tests were done for the 1--5 samples. In these tests the cellulose, total phenol 5 samples. In these tests the cellulose, total phenol and total carbohydrate contents were measured and and total carbohydrate contents were measured and thermoanaliticalthermoanaliticalbehavior were behavior were examined. The lignin content of the samples wasnexamined. The lignin content of the samples wasn’’ t measured, because of the t measured, because of the degradation of the lignin there is no method. All contents indicdegradation of the lignin there is no method. All contents indicted refer to the dry ted refer to the dry weight of the samples.weight of the samples.

Fig. 1. The position of the Fig. 1. The position of the PannonPannonLake at the Lake at the Miocene (Magyar et al. 1999)Miocene (Magyar et al. 1999)

Fig. 2Fig. 2--3. Trunks in the open cast mine (3. Trunks in the open cast mine (BBüükkkkáábbáárnyrny, Hungary), Hungary)

1122

33

5544

Fig. 4Fig. 4--6. Collecting samples and some of them, which were 6. Collecting samples and some of them, which were testedtested

5.582 5.582 ±± 0.2640.2640.932 0.932 ±± 0.0240.02433.02 33.02 ±± 4.844.845 5

10.8310.83±±0.8910.8914.0714.071±±0.1450.14537.4237.42controllcontroll

3.990 3.990 ±± 0.2860.2860.765 0.765 ±± 0.0160.01635.52 35.52 ±± 4.834.834 4

3.165 3.165 ±± 0.0820.0820.587 0.587 ±± 0.0630.06330.15 30.15 ±± 2.98 2.98 3 3

2.875 2.875 ±± 0.3080.3081.280 1.280 ±± 0.0660.06618.17 18.17 ±± 3.223.222 2

1.428 1.428 ±± 0.109 0.109 0.461 0.461 ±± 0.0590.05933.33 33.33 ±± 2.002.0011

ccarbohydratearbohydrate[mg/g][mg/g]

t. t. pphenolhenol[[mmolmmol/100g]/100g]

ccelluloseellulose[%][%]

Table. 1. Lignin, cellulose, phenol and carbohydrate contents ofTable. 1. Lignin, cellulose, phenol and carbohydrate contents ofthe samplesthe samples

The early wood of the annual rings were The early wood of the annual rings were more degraded (red arrows) than the late more degraded (red arrows) than the late wood (yellow arrows), so wood (yellow arrows), so thethe cells in the cells in the early wood collapsed (Fig. 7early wood collapsed (Fig. 7--10). The rays 10). The rays are are uniseriateuniseriate, homogenous. The cells of the , homogenous. The cells of the axial parenchyma are not grouped, these axial parenchyma are not grouped, these cells are containing some kind of material cells are containing some kind of material (green arrows). There are 2(green arrows). There are 2--4 4 taxodioidtaxodioid or or cupressoidcupressoidpits in the cross fields. pits in the cross fields.

Fig. 8Fig. 8--10. Light microscopic photos of the sample 3. Cross section. Deg10. Light microscopic photos of the sample 3. Cross section. Degraded early wood, axial raded early wood, axial parenchymasparenchymaswith with some contentsome content

Fig. 7. SEM photo of the sample 3, the early Fig. 7. SEM photo of the sample 3, the early wood is wood is degradateddegradated

Fig. 6. The location of Fig. 6. The location of BBüükkkkáábrbráányny in Hungaryin Hungary

Fig. 11Fig. 11--12. The structure of the cell wall between axial parenchyma cell12. The structure of the cell wall between axial parenchyma cellss

Sample 3Sample 3 Sample 5Sample 5

The cellulose content of the fossils is significantly lower, parThe cellulose content of the fossils is significantly lower, partly disintegrated, so the tly disintegrated, so the lignin content relatively higherlignin content relatively higher((itit wasnwasn’’ tt measuredmeasured)), that, that’’ s why the samples can be s why the samples can be crumbled. Significantly lower concentration of phenols and sugarcrumbled. Significantly lower concentration of phenols and sugars can be measured in s can be measured in the fossils. The degradation process of the fossils. The degradation process of polyosespolyosescan be clearly seen in the case of the can be clearly seen in the case of the samples by DSC (Fig. 13samples by DSC (Fig. 13--14). According to the DSC analysis too, the amount of 14). According to the DSC analysis too, the amount of cellulose is much lower in the fossils. The fossils show higher cellulose is much lower in the fossils. The fossils show higher thermal stability, which thermal stability, which could be explained by a higher lignin content. could be explained by a higher lignin content.

100100°°CC 260260°°CC 390390°°CC 410410°°CC

Fig. 13Fig. 13--14. Differential scanning calorimetric (DSC) measurements of the14. Differential scanning calorimetric (DSC) measurements of thesamples. 100samples. 100°°C C –– water;water;260260°°C C –– hemicellulosehemicellulosedeg.; 390deg.; 390°°C C –– cellulose deg.; 410cellulose deg.; 410°°C C –– polymerisationpolymerisationof the degradation products. of the degradation products.

ReferencesReferences

Dubois, M., Gilles, K. A., Hamilton, J. K., Dubois, M., Gilles, K. A., Hamilton, J. K., RebersRebers, P. A., Smith, F. (1956): Colorimetric method for determination, P. A., Smith, F. (1956): Colorimetric method for determinationof sugars and related substances, of sugars and related substances, Anal. Chem.Anal. Chem. 2828: 350: 350--356.356.

Hoadley, R.B. (1990): Identifying wood. The Taunton Press, NewtoHoadley, R.B. (1990): Identifying wood. The Taunton Press, Newtown, Connecticut, USA.wn, Connecticut, USA.

Magyar, I., Geary, D.H., Magyar, I., Geary, D.H., MMüüllerller, P. (1999): , P. (1999): PaleogeographicPaleogeographicevolution of the Late Miocene Lake evolution of the Late Miocene Lake PannonPannonin Central in Central Europe. Europe. PalaeogeographyPalaeogeography, , PalaeoclimatologyPalaeoclimatology, , PalaeoecologyPalaeoecology147:147: 151151--167.167.

Singleton, V. L., Rossi, J. A., Jr. (1965): Singleton, V. L., Rossi, J. A., Jr. (1965): ColorimetryColorimetry of Total of Total PhenolicsPhenolicswith with PhosphomolybdicPhosphomolybdic--PhosphotungsticPhosphotungsticAcid Reagents, Acid Reagents, Am. J. Am. J. EnolEnol. . ViticVitic.. 1616 (3): 144(3): 144--158.158.

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