德意志联邦共和国卢萨提亚褐煤矿区中新世原地化石树桩和树干中的高纤维素含量

IF 5.6 2区 工程技术 Q2 ENERGY & FUELS International Journal of Coal Geology Pub Date : 2024-03-21 DOI:10.1016/j.coal.2024.104494
J. Kus , M. Dolezych , W. Schneider , J.C. Hower , T. Hofmann , E. Visiné Rajczi , A. Bidló , B. Bolodár-Varga , R.F. Sachsenhofer , A. Bechtel , K. Stojanović , D. Životić , I. Kojić , M. Mastalerz , T. Graupner , W.E. Lukens , L. Donaldson
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引用次数: 0

摘要

第二中新世地层群(2nd MFK; germ.: 2. Miozäner Flözkomplex)拥有许多原生的、未经过永久矿化的、纤维素含量较高的树桩和树干化石。本研究采用多种研究方法,对从德意志联邦共和国卢萨提亚褐煤矿区的三个露天矿(Welzow-Süd、Meuro 和 Piskowitz)采集的一组原地树化石(Taxodioxylon cryptomerioides、Sciadopityoxylon wettsteinii 和 Quasisequoioxylon piskowitzense)的保存状况进行了调查。对热不成熟木材化石的保存状态进行了研究,结果表明(1) 保存完好(未变形、未退化、未扁平化)的纹理,(2) 保留了结构的完整性,表现为多层(多分区)细胞,包括主细胞壁、次细胞壁和中间薄片,(3) 微裂纹仅限于次细胞壁、(4) 保留了多酚实质细胞(PP 细胞);(5) 射线气管中的凹坑保存完好;(6) 存在无定形二氧化硅(蛋白石-A)涂层;(7) 晶体二氧化硅(蛋白石-CT)填充小叶片晶体。热重分析结果表明化石样本的凝胶化状态各不相同,支持绿泥石全纤维素检测结果。后者显示出异常高的纤维素值(全纤维素含量为 15.6-37.6%)。获得的显微傅立叶变换红外光谱数据显示,半纤维素(1740 和 1245 厘米-1 处的条带)和纤维素(1110 和 1040 厘米-1 处的条带)均保存完好。显微傅立叶变换红外光谱分析表明,所检测样品中的多糖没有被优先水解去除。结果表明,与皮斯科维兹褐煤相比,Welzow-Süd 的冲天香柏科和浮游大型植物对前体有机物的贡献较低。皮斯科维兹褐煤形成于地下水位稳定的永久性沼泽地,处于还原性中营养条件下。从化石木材中获得的生物标志物组合显示,二萜类化合物和δ13C值(-24.6 ‰至-20.3 ‰)明显占优势,这清楚地证实了裸子植物的来源。二萜和倍半萜以及脂肪酸的分布表明,化石木材中饱和二萜(pimarane、abietane)的含量高于现代木材。这表明还原条件促进了氢化反应。除了低 Eh 值之外,酸性条件、极低的需氧真菌降解程度以及源自濯缨草的树脂对木材的保护也有利于化石木材中纤维素的保存。虽然化石木材的δ13C值与地层趋势和化学分类学分类基本一致,但与已发表的裸子植物化石木材δ13C数据相比,Welzow-Süd和Meuro露天矿中分别记录的T. cryptomerioides和S. wettsteinii的δ13C值略有升高,这也表明纤维素保存良好。中新世化石树桩和树干在原地的保存以及高纤维素含量的保留,都被认为与反复的、由风化控制的干湿循环引起的高振幅时间波动有关:(1) 以凝灰岩和流纹岩为主的酸性火山岩和劳西茨花岗闪长岩的风化,(2) 与此相关的有蚀岩的侵蚀,以及 (3) 泥炭来源的富含腐殖酸和富立酸的水循环。后者导致了中新世高岭石沉积的形成,以及硅酸的释放和随后以蛋白石-A 的形式沉淀。后者影响了化石木材中高纤维素含量的保存。
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High-cellulose content of in-situ Miocene fossil tree stumps and trunks from Lusatia lignite mining district, Federal Republic of Germany

Second Miocene Seam Complex (2nd MFK; germ.: 2. Miozäner Flözkomplex) holds many in-situ, not permineralised fossil tree stumps and trunks with high-cellulose contents. The state of preservation of a set of in-situ fossil trees (Taxodioxylon cryptomerioides, Sciadopityoxylon wettsteinii, and Quasisequoioxylon piskowitzense) collected from three open-cast mines (Welzow-Süd, Meuro, and Piskowitz) in Lusatia lignite mining district, Federal Republic of Germany was investigated using a multi-method research schema.

Examination of preservation state of thermally immature fossil woods revealed: (1) well-preserved (non-deformed, non-degraded, and non-flattened) textinite, (2) a retained structural integrity represented by multilayered (multi-zoned) cells with primary, secondary cell wall, and middle lamella, (3) microfracturing restricted to secondary walls only, (4) preservation of polyphenolic parenchyma cells (PP cells), (5) excellent preservation of pits in ray tracheids, (6) presence of amorphous silica (opal-A) coating, and (7) crystalline silica (opal-CT) fillings of small-bladed crystals.

Thermogravimetric analysis results showed dissimilar gelification status of fossil samples, supporting chlorite holocellulose assay results. The latter indicated anomalously high-cellulose values (15.6–37.6% holocellulose). The micro-FTIR data obtained revealed an excellent preservation of both hemicellulose (bands at 1740 and 1245 cm−1) and cellulose (bands at 1110 and 1040 cm−1). Micro-FTIR spectrometry indicated lack of preferential hydrolytic removal of polysaccharides in examined samples.

Biomarker patterns in lignite revealed forested and prevailing reed-mire vegetation. The results indicated lower contribution of Cupressaceae and emergent macrophyta to precursor organic matter of Welzow-Süd in comparison to Piskowitz lignite. Piskowitz lignite formed in permanent mire with stable water table under reducing, mesotrophic conditions. In contrast, more pronounced water level fluctuations (reducing to slightly oxic settings) and/or post-depositional events are postulated for Welzow-Süd samples.

Biomarker assemblages obtained from fossil wood show a distinct dominance of diterpenoids and δ13C values (−24.6 ‰ to −20.3 ‰) that clearly confirm gymnosperm sources. Distributions of diteprenoids and sesquiterpenoids, as well as fatty acids indicate the higher amount of saturated diterpenoids (pimarane, abietane) in fossil than in modern wood. This indicates reducing conditions promoting hydrogenation reactions. In addition to low Eh, preservation of cellulose in fossil wood was also favored by acidic conditions, very low degrees of aerobic fungal degradation, and protection of wood by Cupressaceae-derived resins.

While δ13C values of fossil wood are generally consistent with stratigraphic trends and chemotaxonomical classification, slightly elevated δ13C values recorded in T. cryptomerioides and S. wettsteinii in Welzow-Süd and Meuro open-cast mines, respectively, compared to published δ13C data of fossil gymnosperm wood are also indicative for good cellulose preservation.

Both preservation of in-situ Miocene fossil stumps and trunks and retention of high-cellulose contents are suggested to be related to high-amplitude temporal fluctuations associated with repeated eustatically-controlled wet-dry cycling inducing: (1) weathering of tuff- and rhyolite-dominated acidic volcanics and Lausitz granodiorite, (2) associated erosion of saprolites, and (3) peat-sourced circulation of humic acid- and fulvic acid-rich waters. The latter led to the formation of Middle Miocene kaolinite deposits, as well as to the release of silicic acid and its subsequent precipitation in form of opal-A. The latter influenced preservation of high-cellulose contents in fossil wood.

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来源期刊
International Journal of Coal Geology
International Journal of Coal Geology 工程技术-地球科学综合
CiteScore
11.00
自引率
14.30%
发文量
145
审稿时长
38 days
期刊介绍: The International Journal of Coal Geology deals with fundamental and applied aspects of the geology and petrology of coal, oil/gas source rocks and shale gas resources. The journal aims to advance the exploration, exploitation and utilization of these resources, and to stimulate environmental awareness as well as advancement of engineering for effective resource management.
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