BG2.4 | Organic matter biogeochemistry - from novel analysis techniques, biomarkers, and DNA to process understanding of organic carbon cycling
EDI
Organic matter biogeochemistry - from novel analysis techniques, biomarkers, and DNA to process understanding of organic carbon cycling
Convener: Simon A. Schroeter | Co-conveners: Carsten Simon, Nicholle Bell, Doreen Huang, Sinikka Lennartz, Chiara Santinelli, Hannelore Waska
Orals
| Thu, 27 Apr, 08:30–12:30 (CEST)
 
Room 2.95
Posters on site
| Attendance Wed, 26 Apr, 16:15–18:00 (CEST)
 
Hall A
Orals |
Thu, 08:30
Wed, 16:15
Natural organic matter (NOM) is ubiquitous and astonishingly complex, and this complexity may be pivotal in sustaining various ecosystem services such as nutrient cycling and carbon storage. For example, microbial uptake, respiration and release of organic matter ultimately control a carbon reservoir larger than all living biomass on earth combined. Organic molecules such as DNA and biomarkers have received increasing attention as tools to reconstruct long-term changes in biodiversity, microbial element cycling, organic matter composition, and environmental constraints.
Our session will thus focus on the following topics:
• NOM biogeochemistry
Modern geochemical tools such as nuclear magnetic resonance spectroscopy, ultrahigh resolution mass spectrometry or liquid chromatography coupled to tandem mass spectrometry show great prospects for revealing the multifaceted nature of NOM, i.e., attributing its variety of functions to the extremely diverse molecular composition of NOM. Key questions include: How can we disentangle the properties, functions, and responses of NOM in terrestrial and marine ecosystems, and which new techniques and experimental setups can help us to achieve this?
• Microbe-DOM interactions
Understanding the main mechanisms regulating the biological availability of DOM is one of the most challenging, but pressing issues in environmental science. In biogeochemical modelling studies, DOM is still over-simplistically parameterized, and linking DOM composition to more easily measured proxies from optical measurements (CDOM/FDOM) remains challenging. Contributions include experimental studies and field observations along environmental gradients, data science approaches focusing on algorithm development, studies linking microbial and biogeochemical data, as well as biogeochemical modelling approaches.
• Biomarkers and environmental DNA
Recent developments in the analysis of biomarkers (lipids, photo-pigments, sterols, etc.) and DNA extracted from environmental samples enable unique insights into the history of terrestrial, freshwater, and marine ecosystems. Molecular techniques offer a differentiated view on the climate-environment-human nexus through investigation of leads/lags in specific proxies resolving cultivated plants, domestic animals, industrial activity, and climate. This section targets advances and challenges when using biomolecules for paleo-environmental reconstructions and covers novel analytical approaches and data analysis.

Orals: Thu, 27 Apr | Room 2.95

Chairpersons: Nicholle Bell, Sinikka Lennartz, Chiara Santinelli
08:30–08:35
Microbial-DOM interactions from molecular to basin-wide scales
08:35–08:45
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EGU23-16877
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On-site presentation
Daniel J. Repeta, Benjamin N. Granzow, Andrew Burger, and Edward F. DeLong

A large fraction of marine primary production is directed towards the synthesis of polysaccharides, most of which are rapidly degraded by heterotrophs, including heterotrophic microbes. However, a novel class of polysaccharides characterized by high N-acetyl aminosugar and 6-deoxysugar content, escapes rapid degradation and accumulates as a constituent of marine dissolved organic matter (DOM). These polysaccharides, which comprise ~25% of total dissolved organic carbon, also represent a large reservoir of the potentially bioavailable organic N and P stored in DOM.   To better understand the accumulation and microbial degradation of DOM polysaccharides we used size-exclusion chromatography and diffusion-ordered NMR spectroscopy to examine the size-distribution and composition of DOM recovered from seawater by ultrafiltration. Our results show that DOM polysaccharides are relatively small, with a molecular weight range of 1.3–7.7 kD and an average molecular weight of ~6 kD in surface waters decreasing to ~3 kD at 900m. Acid hydrolysis of DOM polysaccharides releases a suite of characteristic neutral sugars (glucose, galactose, mannose, rhamnose, fucose and xylose), but most of the polysaccharide (80-90%) resists hydrolysis and undergoes Maillard-like reactions between amino- and reducing sugars. To circumvent this, we modified our hydrolysis conditions to promote sugar-sugar cleavage. With this approach, we were able to generate a suite of oligosaccharides with molecular weights between 0.3-1.8 kD that carry the same spectral characteristics as DOM polysaccharides. We are using transposon insertion sequencing (Tn-seq) of marine bacteria cultured on these oligosaccharides to identify genes and degradation pathways responsible for DOM polysaccharide degradation.

 

How to cite: Repeta, D. J., Granzow, B. N., Burger, A., and DeLong, E. F.: Characterization and microbial degradation of polysaccharides in high molecular weight dissolved organic matter., EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-16877, https://doi.org/10.5194/egusphere-egu23-16877, 2023.

08:45–08:55
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EGU23-16424
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ECS
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On-site presentation
Ömer Kürsat Coskun, William D. Orsi, Steve D'Hondt, and Gonzalo V. Gomez-Saez

Microbial metabolisms are directly responsible for the production, degradation and recycling of dissolved organic matter (DOM) in the ocean. Many compounds within the DOM contain sulfur (dissolved organic sulfur, DOS) and in sum they represent the largest reservoir of organic sulfur in the ocean. Recent studies indicated an abundant and diverse suite of marine bacteria with the genetic capacity for DOS transformation. However, there is currently very little experimental data regarding the marine sediment microbial communities that are actively using DOS substrates as a source of carbon. Here, we use quantitative 13C DNA stable isotope probing (qSIP) to provide the first quantitative measurements of DOS (taurine and methionine) utilization by specific operational taxonomic units in seafloor sediments from continental shelf of Puerto Rico (493 meter below sea surface). Immediately after sampling, seafloor sediments were amended with 500 µg / g 13C-labeled taurine or methionine as well as natural-abundant (12C) substrates as a control and were incubated in gas-tight glass flasks with no headspace in the dark over two different timepoints (30 hours and 10 days) to unravel the active microbial communities. Our preliminary results by gas-chromatography mass spectrometry showed that there was 6 – 10% of 13CO2-remineralization compared to control samples. This indicates that taurine and methionine are important DOS substrates supporting the activity of benthic microbial populations. Notably, the rate of taurine remineralization was five-fold higher than glucose and 50-fold higher than methionine over the first 30-hours of incubation, suggesting that taurine is an underappreciated, yet important DOS substrate for microbial activity at the seafloor. Oxygen was rapidly consumed to anoxic levels over the first 12 hours in all incubations, indicating that the taurine was utilized via anaerobic microbial metabolism. This was reflected by changes in the initial microbial community that was dominated by Thaumarchaeota (29%), Gammaproteobacteria (15%) and Planctomycetes (13%), which changed to being enriched by Firmicutes (8%-43%), Deltaproteobacteria (10%-26%), and Gammaproteobacteria (10%-29%) in the presence of taurine and methionine. Further quantitative DNA isotope probing study (in progress) will reveal the specific anaerobic microbial taxa that are responsible for driving the biogeochemical cycling of these important, yet overlooked DOS substrates at the seafloor.

How to cite: Coskun, Ö. K., Orsi, W. D., D'Hondt, S., and Gomez-Saez, G. V.: Dissolved organic sulfur utilization by marine benthic microbial communities revealed by quantitative DNA stable isotope probing, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-16424, https://doi.org/10.5194/egusphere-egu23-16424, 2023.

08:55–09:05
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EGU23-9999
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ECS
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On-site presentation
Zakhar Kazmiruk and Eric Collins

The Arctic Ocean receives more terrestrial dissolved organic matter (tDOM) on a per volume basis than any other ocean, resulting in Arctic coastal waters harboring the highest concentration of tDOM among the world’s oceans. Due to climate change induced intensification of the hydrological cycle, permafrost thaw, and coastal erosion, tDOM input into Arctic coastal waters has been steadily increasing. Nguyen et al. (2022) have speculated that the increasing presence of tDOM in the Arctic Ocean is causing a shift in the local microbiological communities. This may significantly affect CO2 fluxes and food web dynamics in the ocean. Despite recent incubation experiments reporting substantial biodegradation of tDOM in Arctic coastal waters, very few studies have attempted to examine the genetic capacity of Arctic marine microorganisms to process lignocellulose and other recalcitrant aromatic compounds of terrestrial origin. In this study, we perform comparative metagenomics in order to assess the diversity and distribution of microbial genes responsible for tDOM degradation in the Western Arctic. We searched 361 seawater metagenomes from the Bering Shelf, Bering Strait, and Chukchi Shelf for orthologs responsible for ring-opening reactions associated with degradation of tDOM (Grevesse et al., 2022). Like others, we identified Rhodobacterales as important contributors to microbial communities encoding the ring-opening reactions required for degradation of aromatic compounds such as tDOM and petroleum products, including members of the Roseobacteraceae (Sulfitobacter, Roseomonas) and Rhodobacteraceae (Planktomarina, Ascidiaceihabitans, and uncultured taxa). We found the presence of degradation genes to be widely distributed across temperature-, salinity-, depth-, and latitudinal gradients, with no clear patterns in the richness of genes. Future work will investigate the relative abundance of these functional genes among metagenome assembled genomes derived from these samples. Doing so, we hope to elucidate the environmental factors supporting the presence of tDOM degrading microorganisms. This study will contribute to the accumulating knowledge on adaptability of marine microorganisms to inputs of recalcitrant organic compounds.

How to cite: Kazmiruk, Z. and Collins, E.: Comparative metagenomics of terrestrial organic matter degradation in the Western Arctic, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-9999, https://doi.org/10.5194/egusphere-egu23-9999, 2023.

Opening the black box of NOM: Ecosystems, Processes & Gradients
09:05–09:15
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EGU23-1987
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Highlight
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On-site presentation
Andreas Haas, Craig Nelson, Milou Arts, Benjamin Mueller, Ellen Hopmans, and Linda Kelly

Marine DOM constitutes one of the most complex chemical mixtures on earth containing hundreds of thousands of different compounds. In nearshore systems like coral reefs metabolites exuded by primary producers comprise a significant fraction of this marine DOM pool. To learn more about the chemical composition we performed untargeted molecular analysis of exudates released by coral reef primary producers (corals and algae) using liquid chromatography–tandem mass spectrometry. Of 10,568 distinct ion features recovered from reef waters, 1,667 were primary producer exudates; the majority (86%) of these exudates were organism specific, reflecting a clear divide between coral and algal exometabolomes. The stoichiometric analyses of the exudates revealed a significantly reduced nominal carbon oxidation state of algal- compared to coral exometabolites, illustrating an ecological mechanism by which algal phase shifts engender fundamental changes in the biogeochemistry of reef biomes. Coral exometabolomes were enriched in diverse sources of nitrogen and phosphorus, including tyrosine derivatives, oleoyltaurines, and acyl carnitines. In contrast DOM released by algae was dominated by nonnitrogenous compounds, including diverse prenol lipids and steroids. Additional experiments indicate that exudates, specifically exudates unique to the respective treatment, were the main substrate used by heterotrophic microbes exposed to the respective exometabolome. This data provides molecular-level insights into biogeochemical cycling on coral reefs and illustrates how changing benthic cover on reefs influences reef water chemistry with implications for microbial metabolism.

How to cite: Haas, A., Nelson, C., Arts, M., Mueller, B., Hopmans, E., and Kelly, L.: Molecular characterization of coral reef exometabolites, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-1987, https://doi.org/10.5194/egusphere-egu23-1987, 2023.

09:15–09:25
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EGU23-9168
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ECS
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Highlight
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On-site presentation
Philipp Maurischat, Michael Seidel, Oliver Donnerhack, and Georg Guggenberger

With the Anthropocene, thermogenic organic carbon, also known as black carbon (BC) is increasingly introduced to ecosystems worldwide. BC is formed by incomplete combustion or pyrolysis of fossil fuels, at wildfires or by the intentional burning of biomass, emitted to the atmosphere and hydrosphere or remaining in the bio-/pedosphere. With its high molecular proportion of elemental carbon, BC is regraded to be protected from fast microbial degradation by its inherent molecular properties. In aquatic systems, BC is partly sedimented or buried when reaching endorheic lakes or the ocean, where it is withdrawn from the carbon cycle. The biogeochemical implications of BC or its degradation products in aquatic systems have therefore not received much attention. Especially in sensitive oligotrophic alpine systems, such as the treeless Tibetan Nam Co catchment, part of the biggest connected alpine pasture system in the world, which is exposed to increasing anthropogenic pressure, any nutrient and carbon surplus can threaten the ecological status.

This was studied by an ultra-high resolution mass spectrometry approach that identifies several thousands of molecular formulae in dissolved organic matter (DOM). Including polycondensed aromatics (pcAro) that are considered to include thermogenic DOM.

Incubation experiments of water samples indicated that pcAro DOM was transformed by microbes to a comparable degree such as other natural organic matter (NOM) in the samples, removing pcAro DOM by defunctionalization or metabolization. In the environmental samples we found that pcAro DOM discharged to the endorheic Nam Co Lake was transformed by photodegradation along with other aromatic compounds. For DOM of streams and the lake of the high-alpine Nam Co watershed, most pcAro is likely of local origin, i.e. derived from burning of yak faeces by pastoralist households. This pcAro formed from cellulose-rich and lignin-poor Cyperaceae fodder is chemically distinct from low-land natural biomass, usually including the burning of wood.

Thus pcAro DOM appeared to be a more viable part of the carbon cycle than previously assumed. Our data support the hypothesis that the fate of polycondensed aromatic DOM depends on several environmental factors, such as catchment characteristics, water opacity, solar irradiation and actual light penetration into the water column, as well as on the carbon source, driving the molecular composition of thermogenic NOM.

 

How to cite: Maurischat, P., Seidel, M., Donnerhack, O., and Guggenberger, G.: Assessing the fate of polycondensed aromatic natural organic matter (NOM) in a high-alpine aquatic system, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-9168, https://doi.org/10.5194/egusphere-egu23-9168, 2023.

09:25–09:35
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EGU23-1007
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Highlight
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On-site presentation
Christian Zerfass, Nico Ueberschaar, and Georg Pohnert

Understanding biogeochemical processes in groundwater is paramount for safety management of our water supplies. The AquaDiva project has been investigating a groundwater probing site in central Germany to monitor hydrology, biology and dissolved organic matter (DOM) chemistry in a multiannual project (Küsel et al., 2016). As part of this, we are addressing how deep surface-derived signals can be traced on their passage through the critical zone and into the groundwater.

We acquired a multiannual DOM data set from an untargeted liquid chromatography coupled to mass spectrometry (LC-MS) monitoring and have previously shown that fingerprints from mass-signals associate with water flows (Zerfaß et al., 2022). Using tandem mass spectrometry, we have now identified DEET (N,N-diethyl-m-toluamide) and 7-ODAA (7-oxodehydroabietic acid, putative) in groundwater samples, compounds that are released to aerosols as insect repellent sprays and through conifer wood burning for heating, respectively. We show that these signals are found in groundwater throughout the year, but with elevated intensities in summer (DEET) and winter (7-ODAA), respectively, corresponding to their primary seasons of release.

This demonstrates by the counter-periodic DEET and 7-ODAA patterns how surface-derived (aerosol) organic matter signals arrive in groundwater down to 88 m of sampling depths with intra-annual dynamics.

 

References

Küsel, K., Totsche, K.U., Trumbore, S.E., Lehmann, R., Steinhäuser, C., Herrmann, M., 2016. How Deep Can Surface Signals Be Traced in the Critical Zone? Merging Biodiversity with Biogeochemistry Research in a Central German Muschelkalk Landscape. Front. Earth Sci. 4. https://doi.org/10.3389/feart.2016.00032

Zerfaß, C., Lehmann, R., Ueberschaar, N., Sanchez-Arcos, C., Totsche, K.U., Pohnert, G., 2022. Groundwater metabolome responds to recharge in fractured sedimentary strata. Water Res. 223, 118998. https://doi.org/10.1016/j.watres.2022.118998

How to cite: Zerfass, C., Ueberschaar, N., and Pohnert, G.: Aerosols to groundwater: DEET (N,N-diethyl-m-toluamide) and 7-ODAA (7-oxodehydroabietic acid) as markers for anthropogenic emissions in the Hanich CZO, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-1007, https://doi.org/10.5194/egusphere-egu23-1007, 2023.

09:35–09:45
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EGU23-4329
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ECS
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Highlight
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On-site presentation
Yinghui Wang, Peng Zhang, Chen He, Quan Shi, Randy Dahlgren, Robert Spencer, and Junjian Wang

  Dissolved organic matter (DOM) in soil consists of a diverse mixture of water-soluble soil organic matter (SOM) molecules that are highly mobile and reactive. These molecules play various roles with different capacities in biogeochemical processes. Theoretically, the persistence of DOM molecules in soils is controlled by interactions between i) DOM leaching and desorption that release DOM from plant residues and SOM and ii) sorption and decomposition that remove DOM. However, there is still no consensus on the dominant factor(s) or dimension(s) driving the yield and molecular signatures of DOM in soil environments.

  Molecular variations of soil DOM from distinct geographical regions are primarily attributed to variations in geographical climate conditions and soil clay content. Soil weathering condition is highly related to geographical climate conditions, such as temperature and precipitation, and could be a reflection of the soil mineral characteristics. However, there is a distinct paucity of information concerning how the molecular signatures of soil DOM vary with different degrees of weathering across wide geographic scales.

  Herein, we resolved the DOM molecular signatures from 22 diverse Chinese reference soils and linked them with soil organic matter and weathering-related mineralogical properties. The mixed-effects models revealed that the yields of DOM were determined by soil organic carbon content, whereas the molecular signature of DOM was primarily constrained by the weathering-related dimension. The soil weathering index showed a positive effect on the lability and a negative effect on the aromaticity of DOM. Specifically, DOM in highly weathered acidic soils featured more amino sugars, carbohydrates, and aliphatics, as well as less O-rich polyphenols and condensed aromatics, thereby conferring a higher DOM biolability and lower DOM aromaticity. This study highlights the dominance of the weathering-related dimension in constraining the molecular signatures and potential functions of DOM in soils across a wide geographic scale.

How to cite: Wang, Y., Zhang, P., He, C., Shi, Q., Dahlgren, R., Spencer, R., and Wang, J.: Molecular signatures of soil-derived dissolved organic matter constrained by mineral weathering, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-4329, https://doi.org/10.5194/egusphere-egu23-4329, 2023.

09:45–09:55
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EGU23-11962
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ECS
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On-site presentation
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Dan Frederik Lange, Carsten Simon, Yago Rodrigues Santos, Elaine Pires, Jonismar Souza da Silva, Sávio José Filgueiras Ferreira, Carlos Alberto Quesada, Thorsten Schäfer, and Gerd Gleixner

The variability of the molecular composition of dissolved organic matter (DOM) in soils is predominantly explained by microbial mineralization and assimilation as well as interactions with mineral surfaces and soil organic matter (SOM). From a temperate site with calcareous soil it is established that the molecular composition of DOM shifts from plant-derived towards microorganism-derived signals in soil depth profiles. This variability is largely explained by microbial activity and only to a minor degree by soil-derived parameters like texture and SOM. Here we analyze the molecular composition of DOM in depth profiles of tropical rainforest soils in order to compare its variability to the temperate site as the tropical ecosystems have larger variability in soil texture and mineralogy and lower SOM content. We collected porewater in soil profiles of four ecosystems belonging to two major Amazon rainforest types, terra firme forest on clay soils and white-sand forest on sandy soils. We analyzed the molecular composition of DOM using solid-phase extraction and ultrahigh resolution mass spectrometry.

The concentration and composition of DOM differed strongly between the sandy white-sand and clayey terra firme sites. DOM concentration in white-sand soils was much higher and decreased less with depth compared to the terra firme forests. Topsoil DOM in white-sand forests was characterized by high abundance of aromatic plant-derived compounds, whereas it reflected a stronger microbial imprint in terra firme sites. The molecular composition of DOM changed significantly with depth at all sites. In both terra firme and one white-sand forest the transformation was consistent with the expected shift from plant-derived signals towards increasing microbial reworking. The Bray-Curtis dissimilarity between topsoil and greater depth was considerably higher in terra firme compared to white-sand soils with values of 0.32 +- 0.06 and 0.14 +- 0.04, respectively, suggesting much slower DOM transformation in sandy soils. The dissimilarity was correlated similarly to pH, clay content and mineralogy (Pearson R2 = 0.27, 0.21 and 0.23, respectively). The high dissimilarity in the terra firme sites that vary strongly in clay content and mineralogy was only significantly correlated to pH (R2 = 0.16). This suggests that clay content and mineralogy, likely linked to DOM adsorption, were less important for the observed depth trend, which aligns with results from the temperate site. The significant effect of soil pH on the molecular transformation is in line with the importance of microorganisms for DOM transformation as soil pH is a major control on microbial community structure. Overall, our results suggest that similar processes control DOM transformation in temperate and tropical ecosystems, which are likely linked to microbial processing and formation of DOM.

How to cite: Lange, D. F., Simon, C., Santos, Y. R., Pires, E., da Silva, J. S., Ferreira, S. J. F., Quesada, C. A., Schäfer, T., and Gleixner, G.: Molecular transformation of dissolved organic matter in soils of contrasting tropical rainforest ecosystems is similar to temperate regions suggesting common processes, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-11962, https://doi.org/10.5194/egusphere-egu23-11962, 2023.

09:55–10:05
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EGU23-6106
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ECS
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On-site presentation
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Rahul Samrat and Wolfgang Wanek

The vital role played by soil microbial communities, including bacteria, fungi, and other microorganisms, in the provision of several essential terrestrial ecosystem services cannot be overstated. To gain a more comprehensive understanding of their multifaceted ecosystem services, it is essential to identify and examine the functional role of these microbial communities and of the pathways by which they facilitate soil organic matter and plant necromass decomposition and nutrient cycling. The determination of microbial community composition in soils, and extending this to the complex decomposer soil food web, has remained a significant challenge. To address this challenge, various techniques such as 16S and 18S rRNA gene sequencing and phospholipid fatty acid (PLFA)-based biomarker analysis have been applied. While PLFA analysis has been used to characterize these communities for over three decades, recent advancements in liquid chromatography (LC) and high-resolution mass spectrometry (HRMS) now enable comprehensive analysis of the soil lipidome based on intact polar lipids, providing greater though unknown opportunities to discover biomarkers of soil microbes and other food web members. In light of this, we developed an untargeted lipidomics workflow using reverse phase liquid chromatography and electrospray ionization tandem mass spectrometry (RPLC ESI MSMS) for the analysis of lipidomes in soil and pure cultures of archaeal, bacterial, and fungal organisms, to be extended to soil fauna and plants. This workflow includes techniques for the rapid and accurate identification and quantification of lipid molecules in complex samples, utilizing internal standards, quality control strategies, Orbitrap based instrument setups, and an advanced data processing pipeline. Key features of the pipeline include compound annotation for unknowns based on SMILES generation, retention time prediction, feature-based molecular networking, as well as the relative quantification of these compounds using ionization efficiency prediction models. The developed method was capable of analyzing and identifying over 2000 unique intact polar lipid molecules from more than 12 classes in a variety of samples, covering Archaea, Gram-positive and Gram-negative bacteria, fungi, arthropods, algae and higher plants. Thus, our method can provide valuable insights into the complex and diverse soil food web by accurately identifying and quantifying a wide range of intact polar lipid molecules and further can be used for biomarker analysis and isotope tracing in soil microbial communities.

How to cite: Samrat, R. and Wanek, W.: Soil Lipidomics: A LC-MS/MS based workflow with advanced data processing for biomarker discovery in soil communities, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-6106, https://doi.org/10.5194/egusphere-egu23-6106, 2023.

10:05–10:15
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EGU23-16956
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Virtual presentation
Christina Hazard, Sungeun Lee, and Graeme W. Nicol

While the complexity of prokaryotic communities in soil is relatively well understood, we are currently ignorant of the role of viruses in influencing their ecology. Viruses infect every living organism and affect rates of biogeochemical processes by killing active cells via cell lysis, or augmenting function through the transfer of auxiliary metabolic genes. The microbially-mediated process of nitrification is central to nitrogen losses and emissions of the greenhouse gas nitrous oxide, contributing to global warming and stratospheric ozone depletion, and viruses may impact this central step of the global N cycle. However, challenges remain in identifying active interactions with specific host or functional groups and virus populations within structurally complex and diverse soil environments. To address this, discrete active interactions between individual hosts and viruses in soil microcosms were examined using the transfer of assimilated carbon from autotrophic prokaryotes to viruses. Microcosms were established with amendments of urea to fuel nitrification and 13C carbon dioxide, followed by DNA stable-isotope probing (SIP) combined with metagenomic analyses. Hybrid analysis of GC mol% fractionation and 13C-DNA-SIP resulted in the identification of active ammonia oxidizing archaea (AOA) hosts and viruses only. To enable characterization of viruses actively infecting all active ammonia- and nitrite oxidizing bacteria (AOB, NOB), a second approach was used where incubations were performed using filtration of virus-like particles to increase the recovery of virus metagenomes. This included differential inhibition of specific nitrifier groups to alleviate competition and potentially increase the abundance of viruses infecting non-inhibited groups. Applications of DMPP or octyne were added to preferentially inhibit AOB and encourage growth of AOA, or acetylene to inhibit all ammonia oxidizing activity as a negative control. This approach dramatically increased the recovery of high-quality virus contigs, with 225 contigs associated with those infecting AOA, AOB or NOB including 69 complete or near-complete genomes. Viruses of ammonia-oxidizers contained auxiliary metabolic genes involved in central metabolic pathways, and analysis of viral hallmark genes revealed that they were distinct from previously cultivated viruses. Results demonstrate that virus infection of nitrifiers and propagation of viruses is a dynamic process during soil nitrification, providing insights into potential impacts of viruses on a specific functional process in soil.

How to cite: Hazard, C., Lee, S., and Nicol, G. W.: Characterization and potential impacts of active nitrifier host–virus interactions in soil, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-16956, https://doi.org/10.5194/egusphere-egu23-16956, 2023.

Coffee break
Chairpersons: Doreen Huang, Marina Morlock, Carsten Simon
10:45–10:48
Opening the black box of NOM: Methods & Data Analysis
10:48–10:58
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EGU23-9304
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ECS
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On-site presentation
Edurne Estévez, Sophia Mützel, Rubén del Campo, Roland Stalder, and Gabriel Singer

Rivers are important contributors to the global carbon cycle as they actively transform terrestrial organic matter (OM) during transport to the oceans. The efficient OM processing results from a diverse assemblage of consumers including heterotrophic microbes (i.e., fungi, bacteria and protists) and macroinvertebrates, which interact with an equally diverse pool of OM. Ecologically, OM can be understood as forming a multidimensional resource space for consumers, whose understanding, however, requires an advanced capability to describe relevant dimensions (i.e., traits of OM) at a level that matches the resolution of consumer diversity, where significant advancement is generated by molecular biological means (i.e., DNA sequencing). This implies moving beyond proxy-based indirect descriptors (e.g., indices derived from absorbance or fluorescence spectroscopic analyses), integrative bulk property measures (e.g., C, N, P, lignin, tannins and fibre content) or bulk amounts of operational size fractions (e.g., dissolved, fine and coarse particulate OM). Recent technological advances such as size-exclusion, liquid or ion chromatography coupled to mass spectrometry have allowed to describe dissolved OM (DOM) on a molecular species level, setting a great step forward in the highly resolved description of DOM properties. However, particulate OM (POM) characterization remains behind significantly. Here, a per-particle basis description with regard to physical features and macromolecular composition is needed. We propose a procedure to asses both physical and chemical molecular properties of individual POM particles by combining (i) photometrical techniques, which are based on image processing and particle analysis (e.g., ImageJ) of pictures obtained with microscopes or cameras, and (ii) attenuated total reflectance infrared spectroscopy (ATR-FTIR) to measure particle-specific chemical composition. We apply this method to POM samples collected along large-scale environmental gradients in river networks.

How to cite: Estévez, E., Mützel, S., del Campo, R., Stalder, R., and Singer, G.: A procedure to characterize physical and chemical molecular properties of individual organic matter particles, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-9304, https://doi.org/10.5194/egusphere-egu23-9304, 2023.

10:58–11:08
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EGU23-16616
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ECS
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On-site presentation
Rebecca Rodrigues Matos, Elaine Jennings, Boris Koch, and Oliver Lechtenfeld

Ultrahigh-resolution mass spectrometry like FT-ICR MS has greatly expanded our view of the complexity and reactivity of complex dissolved organic matter (DOM) in the environment. However, both the structural characterization and (semi)-quantification DOM are methodologically not fully resolved, despite recent advances with coupling liquid chromatography (LC) to FT-ICR-MS that allows isomeric separation. Likewise, matrix effects and the existence of multiple isomers with largely varying – but unknown – ionization efficiencies that are simultaneously ionized and detected in direct infusion (DI)-FT-ICR MS prevents (semi)-quantification of DOM compounds and has limited the comparability of samples. Finally, common normalization strategies applied for non-targeted DOM analysis with DI cannot be easily transferred to LC-type DOM data. Here we present a new method that combines a post-column infusion of internal standard (PCI-IS) with LC-FT-ICR MS in order to reduce and compensate matrix effects as well as to provide a robust and reliable way to normalize MS peak intensities and compare samples measured with LC-FT-ICR MS. To this end, DOM samples were analyzed and the peak intensity data normalized by the internal standard and other frequently used normalization methods (e.g. sum of intensity, base peak), and absolute intensity indicating that PCI-IS normalization provides superior precision and accuracy. The potential of this method to provide semi-quantitative information on polarity fractions of DOM is assessed by testing the precision, accuracy, and linearity of PCI-IS normalization of model compounds spiked into DOM samples. Our results indicate that the use of LC separation reduced matrix effects (as compared to DI) and, in combination with the internal standard, improved to potential to obtain reliable peak intensity information.

How to cite: Rodrigues Matos, R., Jennings, E., Koch, B., and Lechtenfeld, O.: Towards semi-quantification of DOM: isomer separation with LC-FT-ICR-MS combined with a post-column infusion of standard., EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-16616, https://doi.org/10.5194/egusphere-egu23-16616, 2023.

11:08–11:18
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EGU23-2837
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On-site presentation
Oliver Lechtenfeld, Philipp Plamper, Peter Herzsprung, and Anika Groß

Dissolved organic matter (DOM) is a complex mixture of thousands of natural molecules that undergo constant transformation in the environment, such as sunlight induced, photochemical reactions. Despite molecular level resolution obtained by ultra-high resolution mass spectrometry, the mechanistic understanding of DOM transformations is still hampered due to a multitude of simultaneous reactions. Temporal trends of mass peak intensities are currently the only way to follow photochemical induced molecular changes in DOM, but are often limited by low temporal resolution or the necessity to apply monotonic regression models. Here, we present a novel computational approach using a temporal graph (a temporal molecular network) to model the transformation of DOM molecules in a photolysis experiment by employing a predefined set of basic molecular transformation units (like oxidation, decarboxylation, etc.). The new algorithm focuses on the temporal changes of mass peak intensities of molecular formulas by simultaneously considering educt removal and product formation for molecules linked by a transformation unit (e.g. -CO2). The transformations and molecules are further weighted by the extent of intensity change and grouped by unsupervised machine learning algorithms to find clusters of similar reactivity. The temporal graph thus allows to simultaneously identify relevant molecules subject to similar reactions and to study their time course. The graph can be constructed for low and high temporal resolution data without presumptions on reaction kinetics and with different sets of transformation units according to the experimental design. Our approach overcomes previous data evaluation limitations for mechanistic studies of DOM transformation and leverages the potential of temporal graphs to study the reactivity of complex DOM by means of ultra-high resolution mass spectrometry.

How to cite: Lechtenfeld, O., Plamper, P., Herzsprung, P., and Groß, A.: A temporal graph to predict chemical transformations in complex dissolved organic matter, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-2837, https://doi.org/10.5194/egusphere-egu23-2837, 2023.

Novel molecular tools (biomarkers and DNA) in climatic and environmental archives
11:18–11:28
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EGU23-8793
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ECS
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Highlight
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On-site presentation
Ying Liu, Kathleen Stoof-Leichsenring, Bernhard Diekmann, and Ulrike Herzschuh

Grasslands on the northeastern Tibetan Plateau are particularly sensitive to changes in climate and herbivory. As two main compositions, Poaceae and Cyperaceae supply forage and support herbivory survival. However, to taxonomic resolution restriction of traditional plant proxies, the plant composition and richness change of vegetation in particular of Poaceae and Cyperaceae are still largely unknown. Here, we reconstruct the vegetation using Lake Donggi Cona sediment ancient DNA metabarcoding, targeting chloroplast trnL P6 loop (g h primer). To increase Poaceae and Cyperaceae taxonomic resolution we currently also investigate ITS1 of nuclear ribosomal DNA in Poaceae and Cyperaceae. A total of 257 terrestrial higher plant taxa, 14 Pteridophyta taxa and 9 aquatic taxa were detected. Before ca. 12.6 cal ka BP, Asteraceae dominate terrestrial plant communities, which are commonly associated with cold and arid conditions during the late glacial; after 12.6 cal ka BP, Asteraceae abundance decline, Poaceae, Rosaceae, and Salicaceae abundance increase likely related to an increase in precipitation and temperature. At 6.5 cal ka BP, the Asteraceae abundance increase, Poaceae and Salicaceae abundance decrease, which is possibly related to cold and dry environments. The plant richness increase sharply since 6.5 cal ka BP and continually maintain relatively high richness values, which may be related to herbivory. Our analyses combine different plant sedaDNA markers will help to elucidate vegetation shifts in the past with deeper taxonomic resolution and provide reference on grassland protection under future climate change scenarios.

How to cite: Liu, Y., Stoof-Leichsenring, K., Diekmann, B., and Herzschuh, U.: Plant sedaDNA reveals grassland change on the Northeastern Tibetan Plateau during the past 17 ka, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-8793, https://doi.org/10.5194/egusphere-egu23-8793, 2023.

11:28–11:38
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EGU23-13403
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ECS
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Highlight
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Virtual presentation
Izabella Baisheva, Boris K. Biskaborn, Kathleen R. Stoof-Leichsenring, Andrei A. Andreev, Stefano Meucci, Lena Ushnitskaya, Luidmila A. Pestryakova, Elisabeth Dietze, and Ulrike Herzschuh

Since many lakes in Yakutia, eastern Siberia, are of thermokarst origin, it can be challenging to reach ages of paleorecords beyond the Holocene, hence limiting the understanding of long-term key interactions between climate change, vegetation dynamics, biodiversity shifts, and lake development. However, with a new paleoenvironmental multiproxy project at an intermontane basin we aim to reconstruct lake-vegetation feedbacks since the Late Glacial Maximum (LGM). For that purpose, a 10.8 m long sediment core has been extracted from the deepest part (22.3 m) of the Lake Khamra (59.99095° N, 112.98345° E) and dated back to 18.4 cal ka BP. Lake Khamra is situated in South-Western Yakutia, the transitional zone of discontinuous to continuous permafrost, it is also in the zone of mixed evergreen-deciduous forest. We applied sedimentological and XRF-derived geochemical parameters in addition to palynological analyses of plant fossils and metabarcoding analyses of diatoms and plants sedimentary ancient DNA (sedaDNA). Our genetic analyses of diatoms revealed 45 unique sequence types. A high distribution of several small fragilarioid types indicates the initial formation of the lake, started in the LGM (15.4 cal ka BP), and high abundance of planktonic taxa since 8 cal ka BP indicates lake deepening in the Mid-Holocene. SedaDNA composition of 38 unique sequence types of aquatic and 155 unique sequence types of terrestrial plants revealed the agreement with pollen and non-pollen palynomorph derived vegetation composition. LGM vegetation was represented as wet tundra and both analyses revealed refugia of Larix. Tundra vegetation only appeared in LGM. The Holocene warming led to the forest establishment and therefore lake vegetation feedback intensification, seen from the turnover of diatoms. Diatoms assemblages of LGM which were represented by only few epiphytic taxa significantly increased the richness, as well as increasing of planktonic and benthic diatom assemblages. The lake expansion resulted in a diversification of emergent aquatic plants. And again, because the lake is not of thermokarst origin it shows more stable insight to environmental variability. This study provides a better understanding of the climate, lake system dynamics, and vegetation in Siberia, and simultaneously fills in the very scarce paleolimnological data in eastern Siberia.

How to cite: Baisheva, I., Biskaborn, B. K., Stoof-Leichsenring, K. R., Andreev, A. A., Meucci, S., Ushnitskaya, L., Pestryakova, L. A., Dietze, E., and Herzschuh, U.: Lake ecology and catchment vegetation changes reconstructed for the last 18,400 years in South-Western Yakutia, Siberia, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-13403, https://doi.org/10.5194/egusphere-egu23-13403, 2023.

11:38–11:48
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EGU23-10354
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Highlight
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On-site presentation
Paula Noble, Sarah Crump, Amelia Muscott, Darren Larsen, Ana Carolina Ruiz Fernandez, Sudeep Chandra, James Simmons, Ayowole Fifo, and Adam Csank

The sediment fill at Summit Lake shows strong potential for reconstructing past changes (Holocene to present) in the paleoecology and regional paleoclimate for the subalpine region of the Black Rock Range, northwestern Nevada, USA. Summit Lake is a high desert terminal lake with a surface elevation of 1780m.a.s.l. and is a eutrophic, alkaline (~8.4), dimictic lake with a maximum depth of ~10 m and a small surface area (2.8 km2). There is abundant growth of macrophytes, including Polygonium (smartweed), Myriophyllum (milfoil), and Ceratophyllum (coon tail), and growth progresses throughout the summer months. The lake falls within the domain of the Summit Lake Paiute Tribe, who has an inextricable cultural connection to the lake via the native Lahontan cutthroat fishery. The tribe’s original name, Agai Panina Ticutta, translates as the Summit Lake Fish Eaters.

In 2021 and 2022 C.E., we collected a series of surface and long sediment cores from multiple sites in the lake. This study focuses on sediments collected from the lake’s central depocenter. Preliminary age control of Summit Lake sediments is determined by 210Pb-dating (corroborated by the stratigraphic profiles of the man-made radionuclides 137Cs, 241Am) for the upper ~40 cm, and the Mount Mazama tephra (~7.6 ka) at 410cm depth. The age model suggests high and increasing sedimentation rates between early 1900 C.E. and 2021 C.E. (from 0.05 to 1.87 cm/yr). In comparison, the mean sedimentation rate between the Mazama tephra and ~1900 C.E. is low (0.05 cm/yr). We present preliminary sedaDNA and diatom data for the last ca. 140 years. Plant sedaDNA shows good preservation, with a stable alpha diversity of ~40 ASVs. The plant record is dominated by the aquatic plants Myriophyllum and Potamogeton (pondweed) in the upper 40cm, and terrestrial plants are also represented, including sagebrush, willow, aspen, and a variety of herbaceous plants, including aster, rose, primrose, buckwheat, borage, lupin, and saxifrage. The diatom flora of the upper 40cm is dominated by the benthic epiphyte Cocconeis placentula, which is consistent with a large macrophyte community seen in the modern system and indicated by the plant sedaDNA. Modern sampling shows the epiphytic relationship between C. placentula and milfoil. Future work will include pairing and harmonizing the diatom record derived from traditional morphotaxonomy and eDNA, contextualizing the plant eDNA with the modern plant community, and refining the age model to better discern Holocene climate events that may be driving the changes in sediment flux and the floral community. These data will be extended down-core to reconstruct the past climate and lake levels, informing the Tribe’s management efforts for a resilient watershed and fishery in the future.

How to cite: Noble, P., Crump, S., Muscott, A., Larsen, D., Ruiz Fernandez, A. C., Chandra, S., Simmons, J., Fifo, A., and Csank, A.: Floral analysis of a ~140 yr sediment record using sedaDNA and diatoms, Summit Lake Nevada, USA, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-10354, https://doi.org/10.5194/egusphere-egu23-10354, 2023.

11:48–11:58
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EGU23-17137
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ECS
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On-site presentation
Jelle A. Dercksen, Laura Maria Stancanelli, and Astrid Blom

Across the globe, freshwater ecosystems have experienced a decline in biodiversity resulting from increasing anthropogenic pressure. Over the past decennia the scientific community has developed new and efficient biomonitoring techniques to register these shifts in biodiversity. A promising technique is the capture and analysis of eDNA and eRNA (environmental DNA and RNA; i.e. eNA). eNA constitutes the genetic material released by a host species into the environment in different forms, such as mucous, skin tissue, scales and saliva. However, in lotic ecosystems, such as streams and rivers, detected eNA concentrations can currently not be translated into the spatial and temporal distribution of the associated species. This is due to the lack of knowledge about the processes (e.g. transport and degradation) that influence eNA presence between the moment of release by its host, and the capture of the eNA by the practitioner.

The authors have conducted a set of laboratory experiments to shed light on these processes (i.e. transport and degradation). The objective was to test the influence of flow velocity on concentrations of both eDNA and eRNA. In an annular flume (depth = 19.7 cm; Ø = 3.7 m), which features counter-rotating bottom and top components, we performed eDNA and eRNA degradation experiments under four different flow rates, each with a duration of seven days. The source of eNA originated from water previously inhabited by wildtype zebrafish (Danio rerio). The tested angular velocities of the top lid (νt top lid) are 0.00, 0.35, 1.05 and 1.80 m/s with corresponding velocities of the bottom component in a constant ratio (νt top lidt bottom) as to reduce secondary circulations in the cross section of the flume. Flow velocity measurements were taken using an acoustic Doppler velocimeter (ADV) across the depth of the flume. During the experiment, abiotic measurements (of pH, temperature and conductivity) as well as water samples were taken. eDNA and eRNA concentrations (in copy numbers per volume) were gathered from these water samples by means of ddPCR, targeting a species-specific 73 base pair fragment in the Cytochrome c Oxidase subunit 1 gene. The abiotic measurements are consistent over the duration of the experiment (average conductivity of 520.1 µS, average temperature of 20.3 °C, average pH of 8.3). Concerning the eNA results, a decrease in both eDNA and eRNA concentrations can be noted over the span of the experiment regardless of the rotation speed. Additionally, eRNA concentrations generally decreased in concentration at a higher rate than eDNA concentrations. These experiments advance the understanding of eNA degradation in lotic ecosystems, and bring forth new directions of research to improve inference in eNA-based biomonitoring.

How to cite: Dercksen, J. A., Stancanelli, L. M., and Blom, A.: The effect of flow velocity on eDNA and eRNA concentration, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-17137, https://doi.org/10.5194/egusphere-egu23-17137, 2023.

11:58–12:08
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EGU23-17512
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Highlight
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On-site presentation
Thorsten Bauersachs, James M. Russell, and Lorenz Schwark

Lacustrine sediment sequences represent highly valuable, continuous records of continental climate and ecosystem change. As such, they provide vital information on both the timing and magnitude of long-term climate trends as well as abrupt climate change events and associated biotic responses. Assessing this information, however, is often not straight forward as many conventional lipid-based temperature proxies are affected not only by temperature but also other environmental parameters. Here, we show that the distribution of heterocyte glycolipids (HGs), which are synthesized by N2-fixing heterocytous cyanobacteria and abundantly present in modern freshwater environments, are strongly correlated to lake surface water temperatures. We used these components, in form of the novel organic temperature proxy HDI26, to reconstruct climate variations in tropical East Africa and simultaneously study the impact of climate change on the frequency and intensity of cyanobacterial blooms using a sediment record from Lake Tanganyika (Tanzania). HDI26-reconstructed surface water temperatures varied from ~22 °C to 26 °C in Lake Tanganyika over the last 40,000 years. Lowest temperatures were observed during the Last Glacial Maximum, which is followed by a 3 to 4 °C deglacial warming to yield highest temperatures in the Late Holocene. This general warming trend is interrupted by up to 1 °C cooling during abrupt climate change events (e.g. Younger Dryas). Lipid-based reconstructions of past cyanobacterial activity indicate that although continuously present in Lake Tanganyika, cyanobacteria only became bloom-forming in the late Holocene and in particular during the last 200 years. Our data thus provides new insights and quantitative estimates on Pleistocene to Holocene climate changes in tropical East Africa and associated ecological responses. Given that heterocyte glycolipids are present ubiquitously in polar to tropical lakes and that they have been identified in lacustrine sediments of Early Cenozoic age, the HDI26 and other HG-based indices provide valuable novel tools to extract the highly sensitive climate and ecosystem information that is stored in sediments of lakes worldwide.

How to cite: Bauersachs, T., Russell, J. M., and Schwark, L.: Heterocyte glycolipids: novel tools to obtain high-resolution climate and ecosystem data from lacustrine archives, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-17512, https://doi.org/10.5194/egusphere-egu23-17512, 2023.

12:08–12:18
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EGU23-14571
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On-site presentation
Francesco Pilade, Iuliana Vasiliev, Daniel Birgel, Marcello Natalicchio, Francesco Dela Pierre, Alan Mancini, Francesca Lozar, and Rocco Gennari

Alkenones are unsaturated long-chained ketones produced by haptophyte algae living in the photic zone of the water column. In cultures of Emiliania huxleyi, the alkenones’ degree of unsaturation between C37 alkenone isomers (UK37’) is proportional to thetemperature of the water in which this haptophyte lives. Besides the UK37’ providing a paleotemperature proxy in the marine realm, the identification of long-chain alkenones in modern lacustrine waters and sediments allowed the recognition of non-marinehaptophyte algae able to produce alkenones. At different salinities, the haptophytes produce a different measure of alkenones molecules in particular: the abundance of C37:4 against the other C37 isomers; the different C38Et/C38Me ratio, and the differentratio between ∑C37/∑C38 isomers.

One of the best laboratories to explore and extend the usage of alkenones as a tool for reconstructing changes in sea surface temperature (SST) and salinity (SSS) is the Mediterranean domain during the Miocene - Pliocene, a boundary marked by the abrupt transition from uppermost Messinian brackish and shallow waters of the Lago-Mare event (5.55-5.33 Ma) to lower Pliocene open marine (Zanclean; 5.33 Ma). Here, we will further address the challenge of using alkenones coupled with a novel combination of commonly used proxies to reconstruct the highly varying water surface condition affecting the Mediterranean Sea during the Miocene to Pliocene transition. Therefore, we studied three time-equivalent sections from the northern part of the basin.

The integration of micropaleontological data with inorganic and organic geochemical ones allowed to evaluate of the changes of the alkenones producers across the Miocene to Pliocene transition and to test the reliability of the C37/C38 ratio, the C37:4% andC38Et/C38Me ratio as paleoenvironmental proxies.

Our results indicate that alkenone-based proxies can be confidently used for tracing SSS changes at the Miocene-Pliocene transition. Their reliability is supported by comparison with the micropaleontological assemblages (body fossils). In particular, the Pliocene sediments are dominated by alkenone marine producers, which records limited SSSs variations, confirmed by the abundant anddiversified calcareous plankton assemblage. For the marine Pliocene, our calculated SSTs (average 20 °C) and SSSs (35-38 PSU) are in the range of the values for that time.

In contrast, for the Lago Mare phase, the scarcity or absence of in situ body fossils of marine calcareous plankton and the mixing of freshwater and marine alkenones producers suggest more significant salinity fluctuations, with a general increase in salinity approaching the Miocene-Pliocene boundary. For the Lago Mare event, our reconstructed SSTs are in the range of those in Pliocene, and the reconstructed salinities for the latestMiocene samples (33 to 36 PSU) are not so different from the ones in Pliocene. Although the presence of marine primary producers inthe Lago Mare sediments is not conclusive concerning establishing a marine-typical salinity environment before the Pliocene in the Mediterranean, the calculated SSSs reflect the reconstruction proposed by alkenones. The high SSSs values and the presence of marine primary producers in the latest Lago Mare may suggest sporadic influxes of oceanic waters.

How to cite: Pilade, F., Vasiliev, I., Birgel, D., Natalicchio, M., Dela Pierre, F., Mancini, A., Lozar, F., and Gennari, R.: Alkenones, as tool for reconstructing surface water temperature and salinity changesduring the Miocene-Pliocene transition in the northern Mediterranean basin, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-14571, https://doi.org/10.5194/egusphere-egu23-14571, 2023.

12:18–12:28
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EGU23-4100
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Virtual presentation
Maoguo Hou, Ming Zha, and Hua Liu

The organic-rich mudstones and dolostones of the Permian Fengcheng Formation (Fm.) are typically alkaline lacustrine source rocks, which are typified by impressively abundant β-carotane. Abundant β-carotane has been well acknowledged as an effective indicator of biological sources or depositional environments. However, the coupling control of biological precursors and environmental factors on the enrichment of β-carotane in the Fengcheng Fm. remains obscure. Based on a comprehensive investigation of the bulk and molecular geochemistry of sedimentary rocks and the biochemistry of phytoplankton in modern alkaline lakes, we proposed a new understanding of the biological precursors of β-carotane and elucidated the coupling control of biological precursors and environmental factors on the enrichment of β-carotane in the Fengcheng Fm. The results show that the biological precursors crucially control the enrichment of β-carotane in the Fengcheng Fm. The haloalkaliphilic cyanobacteria are the primary biological sources of β-carotane, which is suggested by a good positive correlation between 7-+8- methyl heptadecanes/Cmax and β-carotane/Cmax in sedimentry rcoks and the predominance of cyanobacteria with abundant β-carotene in modern alkaline lakes. Land plants and algae do not significantly contribute to the enrichment of β-carotane, which is indicated by negative or weak correlations between terrigenous/aquatic ratio, C19 tricyclic terpene/C23 tricyclic terpene ratio, the concentration of C27 sterane, and β-carotane/Cmax. The environmental facors such as paleoclimate, paleoredox, paleosalinity, and thermal maturity are the indirect factors that control the enrichment of β-carotane by affecting the precursor supply from cyanobacteria and the preservation conditions in the Fengcheng Fm.

How to cite: Hou, M., Zha, M., and Liu, H.: The coupling control of biological precursors and environmental factors on β-carotane enrichment in alkaline lacustrine source rocks: a case study from the Fengcheng Formation in the western Junggar Basin, NW China, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-4100, https://doi.org/10.5194/egusphere-egu23-4100, 2023.

12:28–12:30

Posters on site: Wed, 26 Apr, 16:15–18:00 | Hall A

Chairpersons: Simon A. Schroeter, Hannelore Waska, Tobias Schneider
Microbial-DOM interactions from molecular to basin-wide scales
A.228
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EGU23-14893
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ECS
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Highlight
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Giancarlo Bachi, Marta Furia, Cecilia Balestra, Raffaella Casotti, Giuseppe Civitarese, Gianpiero Cossarini, Mirco Guerrazzi, Daniel Repeta, Maurizio Ribera d'Alcalà, and Chiara Santinelli

Dissolved Organic Matter (DOM), the largest pools of reduced carbon on Earth, represents the major source of energy for micro-heterotrophs, starting the microbial loop. In the open ocean, most of the autochthonous DOM is labile and is therefore respired within days, but a small fraction, called recalcitrant, persists for years to millennia. There are large oligotrophic areas in the oceans, such as the North Atlantic subtropical gyre and the Mediterranean Sea, where the decoupling between production and consumption of DOM leads to its accumulation with implications for the microbial loop.

The main goal of this study is to investigate the putative functioning of the microbial loop all across the Mediterranean Sea following the main path of the Atlantic water entering through the Gibraltar Strait. Dissolved Organic Carbon (DOC) concentration and fluorescence of chromophoric DOM were measured together with heterotrophic prokaryotes, nanoflagellates and virus abundance by flow cytometry. Samples were collected during the MSM72 oceanographic cruise carried out in March-April 2018. Results show that in the western Mediterranean Sea the heterotrophic prokaryotes are relatively abundant and DOM is efficiently removed, suggesting an active transfer of carbon to the higher trophic levels. In contrast, in the eastern Mediterranean Sea DOM accumulates, prokaryote abundance is low and low nucleic acid prokaryotes dominates, suggesting a malfunctioning of the microbial loop leading to a less efficient carbon transfer to the food web. Following the core of the Atlantic Water flowing eastward, as the nutricline deepens, an ecological succession in the phytoplankton communities (from picoeukaryotes to cyanobacteria) is observed, together with a depletion of the fluorescent components in the DOM pool, reflecting changes in the DOM quality.

Different hypotheses can be formulated to explain these observations: the microbial communities could be limited by nutrient availability, by an enhanced top-down pressure by grazers or viruses or by the quality of DOM that could be recalcitrant due to abiotic processes such as photobleaching or to the progressive use of its labile fraction by micro-heterotrophs.

With the upcoming increase in water column stratification, a change in the quality of DOM due to the combined effect of abiotic (e.g., photobleaching) and biotic (e.g., change in the phytoplankton community) is expected with consequences for the functioning of the microbial loop. The questions about the malfunctioning of the microbial loop and its implications in a global change scenario have puzzled the scientists for years and the Mediterranean Sea is a well-suited natural laboratory to answer them.

How to cite: Bachi, G., Furia, M., Balestra, C., Casotti, R., Civitarese, G., Cossarini, G., Guerrazzi, M., Repeta, D., Ribera d'Alcalà, M., and Santinelli, C.: DOM accumulation in oligotrophic surface waters: new insights from the Mediterranean Sea, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-14893, https://doi.org/10.5194/egusphere-egu23-14893, 2023.

A.229
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EGU23-12378
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ECS
Alexandra Loginova, Kinga Hoszek, and Piotr Kowalczuk

Recent studies suggested that sediment pore waters may serve as a source of bioavailable DOM to the overlying water column, which may stimulate microbial activity in the nearbottom waters. However, a combination of DOM measurements with proxies of heterotrophic activity was not a priority of those studies. In this study, we aim to assess the bioavailability of DOM, released by sediments, and whether it may stimulate an increase in heterotrophic cell number. For this, we conduct the measurements of dissolved organic carbon (DOC) and DOM optical properties, such as chromophoric (CDOM) and fluorescent (FDOM) DOM, from the sediment pore waters of the Baltic Sea Deeps and in the water column in order to evaluate the initial supply flux (return flux) to the bottom waters and provide essential insights on the starting composition of DOM. We combine those measurements with the temporal changes of DOC, CDOM and FDOM during ex-situ incubations of the sediment cores with overlying water to infer quantitative and qualitative transformations of DOM during the incubation time. We discuss those data in combination with microbial abundance, oxygen and nutrient consumption as a proxy for sediment released DOM to serve as a substrate for heterotrophic communities to grow and function.

How to cite: Loginova, A., Hoszek, K., and Kowalczuk, P.: Microbial Dissolved Organic Matter utilisation at the nearsediment waters in the Baltic Sea Deeps, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-12378, https://doi.org/10.5194/egusphere-egu23-12378, 2023.

A.230
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EGU23-2572
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ECS
Qiang Zhang, Yinghui Wang, Xiaolang Zhang, Hailong Li, Jiu Jimmy Jiao, Qinglong Fu, and Junjian Wang

Elucidating the characteristics and molecular composition of dissolved organic matter (DOM) is critical to understanding carbon cycling in increasingly saline lakes in arid and hyper-arid areas; however, the ages and molecular signatures of DOM in these widely distributed saline lakes remain poorly understood. Here, variations in DOM ages and other characteristics with salinity were investigated across 10 small saline lakes within the Badain Jaran Desert based on 14C-isotopic analysis, absorption and fluorescence spectroscopy, in addition to Fourier transform ion cyclotron resonance mass spectrometry. The results showed that brine lakes had dissolved organic carbon (DOC) levels 3-fold higher than brackish lakes, and the 14C age of DOC in brine lakes was twice as old. Compared to brackish lake DOM, brine lake DOM had more significant signatures of microbial contributions, as indicated by the higher fluorescence index values and greater relative abundances of microbial humic-like fluorescent components, in addition to sulfur-containing compounds. Moreover, brine lakes showed lower relative abundances of aromatic lignin-like components, as well as higher relative abundances of lipid- and condensed-aromatics-like components. Regarding halogen-containing DOM, the brine lakes showed higher abundances of halogen-containing lignin- and lipid-like components, supporting the preferential transformation of aromatic compounds into halogenated lignin- and lipid-like components. This study demonstrates the strong impacts of salinization on DOM aging, accumulation, and halogenation in inland saline lakes and highlights the critical role of brine lakes as a persistent carbon pool.

How to cite: Zhang, Q., Wang, Y., Zhang, X., Li, H., Jiao, J. J., Fu, Q., and Wang, J.: Dissolved organic matter characteristics and composition of small saline lakes in the Badain Jaran Desert, China, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-2572, https://doi.org/10.5194/egusphere-egu23-2572, 2023.

A.231
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EGU23-15884
Gonzalo V Gomez-Saez, Ömer K Coskun, Yanik Oertel, Jutta Niggemann, Thorsten Dittmar, Timothy G Ferdelman, and William D Orsi

Marine dissolved organic matter (DOM) is one of the largest active carbon pools on Earth, storing one thousand times more carbon than all living organisms in the ocean combined, and similar amounts of carbon than all CO2 in the atmospheric reservoir. Coastal upwelling systems are extremely productive marine regions where surface waters mix with nutrient-rich waters from below, generating hotspots for carbon cycling with highly active microbial communities in the surface and low dissolved oxygen concentration in the deep waters. However, there is a lack of mechanistic understanding with respect to DOM accumulation in upwelling systems, and the sources and processing of DOM within these productive systems are an understudied topic. Here, we performed a novel spatial analysis of the DOM dynamics in the Benguela upwelling system off Namibia both regionally (from shelf to open ocean) and vertically (from surface ocean to subseafloor). To do so, we applied state-of-the-art molecular characterization of DOM using Fourier transform ion-cyclotron resonance mass spectrometry (FT-ICR-MS). By FT-ICR-MS, we identified 29,769 DOM molecular formulas from 75 water column and 8 pore water samples. Molecular DOM analyses were complemented by organic and inorganic quantitative geochemical data and microbial 16S rRNA gene-based diversity coupled with shotgun metagenomic analyses. Furthermore, we performed a set of incubation experiments onboard to test the biodegradability of DOM, with special focus on the dissolved organic sulfur compounds and potential genes involved in sulfur cycling. Preliminary results showed highest differences in the molecular analyses between the sediment pore water DOM and the water column DOM. Most of the variability in the DOM dataset could be explained by the high proportion of compounds containing heteroatoms different than oxygen in the sediments (N, S and P), while oxygen concentrations did not show a clear effect on the DOM molecular composition in the water column. In addition, metagenomic sequencing revealed that marker genes involved in sulfur oxidation and reduction such as periplasmic sulfur-oxidizing proteins (sox), dissimilatory sulfite reductase (dsr), reverse dissimilatory sulfite reductase (rDsr), and adenylyl-sulfate reductase (apr) present throughout the water column and subseafloor. Remarkably, the highest abundance of sulfur-reducing genes was observed in sulfidic sediments whereas sulfur-oxidation genes showed minimal differences in abundance along the water column profile. Further statistical analyses (in progress) will allow us to identify connections between the microbial biosphere and the chemical diversity of DOM, which will help to better understand the mechanisms of biodegradation and accumulation of DOM in coastal upwelling systems and deoxygenated regions.

How to cite: Gomez-Saez, G. V., Coskun, Ö. K., Oertel, Y., Niggemann, J., Dittmar, T., Ferdelman, T. G., and Orsi, W. D.: Spatial dynamics of marine dissolved organic matter in the Benguela upwelling system, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-15884, https://doi.org/10.5194/egusphere-egu23-15884, 2023.

Opening the black box of NOM: Novel analytical techniques reveal the multifaceted nature of Natural Organic Matter in terrestrial and aquatic ecosystems
A.232
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EGU23-13174
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ECS
Livia Vieira Carlini Charamba, Tobias Houska, Klaus-Holger Knorr, and Karsten Kalbitz

In forested catchments, soil organic matter leaching leads to the transport of dissolved organic matter (DOM) into deeper soil horizons and surface waters, directly affecting the composition and functions of surface water DOM undergoing microbial decomposition and photochemical reactions. The knowledge of the amounts and composition of DOM in the soil is, thus, fundamental for characterizing its role in aquatic ecosystems. Differences in DOM composition might be used to identify major DOM sources in streams, e.g. to distinguish the influence of peatland and upland mineral soils, considering that each source has its own typical DOM fingerprint. Furthermore, a deeper understanding of the complex interactions at the terrestrial-aquatic interface could shed a light on the role of DOM composition in nutrient cycling in surface water, which is so far not well described in the literature. Thus, the aim of this study is to present a preliminary analysis of DOM composition along the terrestrial-aquatic continuum as the basis for source identification in streams characterized by long-term increasing dissolved organic carbon concentrations.

Soil water samples from different depths and stream water samples were taken biweekly for roughly a year in the catchment area of the Sosa drinking water reservoir located in the Ore Mountains (Saxony, Germany). Four different sub-catchments were analyzed. Two of them consisted mainly of peatland and degraded peatland soils (P1 and P2, respectively) and the remaining two of mineral soils such as Podzols and Cambisols (M1 and M2). The aqueous samples (soil and surface water) and soil solid phase samples (forest floor and topsoil peat horizons) from the four sub-catchments were analyzed by pyrolysis gas chromatography mass spectrometry (Py-GC-MS) and the results were further processed in Rstudio to facilitate and standardize the chemical identification of the pyrolysates. A principal component analysis (PCA) was applied to the Rstudio results.

With the PCA results we can clearly differentiate soil samples from soil water and stream water samples in principal component 1, i.e. PC1 (25.6%). Even different layers within the soil can be separated, with the deepest layer being most similar to the stream water. Lignin-derived compounds were mainly responsible to distinguish the different sample types (i.e. soil, soil water and stream water), e.g. vanillin lactoside, guaiacol, creosol, apocynin, trans-m-propenylguaiacol, and 4-ethylguaiacol. From those, only guaiacol was found to be present in stream water of P1 and P2 and in soil water of P1, with decreasing concentration along the terrestrial-aquatic continuum (i.e. from soil to stream water). PC2 (7.2%) accounted for differences i) in soil type, i.e., peatland vs. mineral soil and ii) between soil and stream water, including the different sampling sites.

In conclusion, our research indicates that DOM composition clearly changes along the terrestrial-aquatic continuum. These differences can be used to separate two important potential DOM sources, i.e. DOM from peatlands and DOM from the forest floor horizon of mineral soils. Py-GC-MS coupled with a semiautomatic data processing routine and PCA is a very promising tool for identifying DOM from different sources in stream water samples.

How to cite: Vieira Carlini Charamba, L., Houska, T., Knorr, K.-H., and Kalbitz, K.: Characterization of dissolved organic matter composition along the terrestrial-aquatic continuum in the Oren Mountains, Germany, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-13174, https://doi.org/10.5194/egusphere-egu23-13174, 2023.

A.233
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EGU23-8125
Peter Herzsprung, Wolf von Tümpling, Norbert Kamjunke, and Oliver J. Lechtenfeld

Natural organic matter (NOM) is often still a black box considering its isomeric composition. From the analytical point of view the highest resolution of NOM can be achieved by Fourier-transform ion cyclotron resonance mass spectroscopy (FT-ICR-MS). This analytical tool generates elemental compositions of thousands of NOM components (molecular formulas, MFs) which can be extracted from aqueous samples (e.g., via solid phase extraction) and which are ionizable (e.g. via electrospray ionization). The comparison of NOM quality in waters of different ecosystems has generated useful insights about ecosystem-specific molecular differences. However, NOM is not an inert mixture of compounds and can undergo chemical changes by photochemical or microbial reactions or adsorptive fractionation. By following the relative intensity changes of single MFs during simple experiments close to nature or monitoring, elucidation of the reactivity of the underlying NOM compounds is possible.

We have combined a photochemical degradation experiment close to nature with monitoring results from two German drinking water reservoirs with the perspective to disentangle photochemical and microbial reactions in the reservoirs. Bacterial induced transformations were widely excluded in the photo degradation experiment by filtration of the sample water before irradiation. During the reservoir monitoring, both microbial and photochemical reactions can be suggested from relative intensity differences of single MFs during lake stratification (between epi- and hypolimnion). MFs show intensity changes both in the photo experiment and in the lake monitoring are regarded as photo labile or photo products. Those MFs with intensity differences only in the lake monitoring can be regarded as microbial reactive.

A great number of highly reactive MFs were found to be present in all samples of both the photo degradation experiment and the lake monitoring. MFs like C9H12O6, C10H14O6, C10H14O7, C11H16O5 were photo products, MFs like C20H16O14, C19H14O13, C18H12O12 were photo degraded. MFs like C10H10O7 and C9H10O7 could be suggested to be microbial products because they showed elevated intensity in epilimnetic waters but minor reactivity in the photo experiment.

Our studies (1, 2, 3) provide the attempt to follow NOM reactivity by visualization of single MFs relative intensities versus time and / or space.

1) Wilske, C.et al.,Water MDPI (2020) 12 (2).

2) Herzsprung P. et al., Environ. Sci. Technol. (2020), 54, 13556-13565

3) Wilske C. et al., Water MDPI (2021), 13, 1703.

How to cite: Herzsprung, P., von Tümpling, W., Kamjunke, N., and Lechtenfeld, O. J.: Insights into NOM quality changes by combination of easy designed experiments close to nature and monitoring using FT-ICR-MS, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-8125, https://doi.org/10.5194/egusphere-egu23-8125, 2023.

A.234
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EGU23-1634
Guo-Xiang Li and Stefan B. Haderlein

Natural Organic Matter (NOM) shows both oxidizing and reducing capabilities through its quinone/hydroquinone functional groups and takes part in various geochemically redox reactions. Here four natural and synthetic quinone model compounds (anthraquinone-2,6-disulfonate, AQDS; anthraquinone-2-sulfonate, AQS; 2-hydroxyl-1,4-naphthoquinone, Lawsone; and anthraquinone-2,3-dicarboxylic acid, AQDC) were used to study the effect of adsorption of redox active organic matter on mediating ferrihydrite reduction. The studied quinone compounds varied regarding reduction potential and their tendency to adsorb at ferrihydrite. An electrochemical setup rather than iron reducing bacteria was used to circumvent potential inhibitory effects of the model quinones on microbial activity. Iron speciation, dissolved and adsorbed quinone concentrations and their redox state were monitored to elucidate controlling factors in mediated ferrihydrite reduction. Results show that all model quinones present at 100 µM total concentration enhanced the initial iron reduction rate of ferrihydrite, however, to very different extents. At -0.45 V (vs. Ag/AgCl) redox potential applied, the initial reduction rates increased compared to quinone free systems by factors of 62.53, 43.11, 32.26 and 2.91 for AQDS, AQS, Lawsone and AQDC, respectively. In contrast to AQDC and Lawsone, AQDS and AQS did not show significant adsorption at ferrihydrite under the conditions of our study. Due to the high sorption, the initial dissolved AQDC concentration was only 3.60 μM. The initial dissolved concentration of Lawsone was 85.70 µM and decreased further during ferrihydrite reduction. Adsorbed Fe(II) promoted the adsorption of Lawsone on ferrihydrite thereby decreasing the rate of iron reduction. Our findings demonstrate that the rate of ferrihydrite reduction correlated with dissolved quinone concentrations. As a result, AQDS and AQS showed the highest acceleration of ferrihydrite reduction. At the redox conditions applied (-0.45 V vs. Ag/AgCl) the fraction of reduced quinone species was higher for AQDS than for AQS, consistent with the higher efficiency of AQDS in mediating ferrihydrite reduction.

The possibility of conducting experiments at defined redox potentials and precisely controllable experimental conditions reveals the perspectives of an electrochemical setup for the investigation of biogeochemical redox reactions.

How to cite: Li, G.-X. and Haderlein, S. B.: Quinone-Mediated Electrochemical Reduction of Ferrihydrite: Effect of Sorption and Redox Potential, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-1634, https://doi.org/10.5194/egusphere-egu23-1634, 2023.

A.235
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EGU23-17392
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ECS
Akanksha Rai, Markus Lange, Oliver Lechtenfeld, and Gerd Gleixner

A plethora of experimental studies manipulating plant diversity have shown a positive effect of biodiversity on ecosystem functions (aboveground biomass, microbial biomass etc.), which strengthens over time. Tightening of the interactions between plant and soil microorganisms over time is considered to be one of the mechanisms responsible for the observed strengthening of the biodiversity-ecosystem functioning (BEF) relationship. Belowground plant-microorganism interactions occur via the exchange of molecules present in the dissolved organic matter (DOM). Hence, an untargeted ultrahigh resolution mass spectrometric analysis of DOM provides an opportunity to understand the mechanisms of interaction between plants and microorganisms in soil. To investigate if and how plants-soil interactions changed over time, we took advantage of the highly replicated DBEF experiment of the Jena Experiment (JE) (Roscher et al., 2004, Vogel et al., 2019). In this experiment, the duration of plant-soil interactions (“history”) and the respective effects of plant diversity on ecosystem functioning were manipulated. Here, we analyzed the water extractable organic matter fraction of topsoil (WEOM; analogous to DOM in this study) using online nano solid phase extraction FTICR-mass spectrometry. While the molecular composition of the WEOM was not impacted by soil history, plant diversity effect differs among the soil history treatments. Specifically, plant diversity had a significant impact on the molecular composition of WEOM in treatments with plant and soils history. In addition, the molecular composition of WEOM in this treatment held a large number of molecular formulae that significantly correlated with plant diversity. This suggests that the strengthening of the biodiversity-ecosystem functioning over time is reflected in the WEOM molecular composition. Thus, the molecular composition of WEOM potentially provides insight into the mechanism underlying the strengthening of biodiversity-ecosystem functioning.

 

 

Roscher, C., Schumacher, J., Baade, J., Wilcke, W., Gleixner, G., Weisser, W. W., ... & Schulze, E. D. (2004). The role of biodiversity for element cycling and trophic interactions: an experimental approach in a grassland community. Basic and Applied Ecology, 5(2), 107-121.

Vogel, A., Ebeling, A., Gleixner, G., Roscher, C., Scheu, S., Ciobanu, M., ... & Eisenhauer, N. (2019). A new experimental approach to test why biodiversity effects strengthen as ecosystems age. In Advances in ecological research (Vol. 61, pp. 221-264). Academic Press.

How to cite: Rai, A., Lange, M., Lechtenfeld, O., and Gleixner, G.: FTICR-mass spectrometry reveals shifts in plant-microorganism interactions over time, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-17392, https://doi.org/10.5194/egusphere-egu23-17392, 2023.

A.236
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EGU23-13604
Hannelore Waska, Jessika Füssel, Katharina Paetz, Marit Renken, and Thorsten Dittmar

In current dissolved organic matter (DOM) research, solid-phase extraction (SPE) with Bond Elut PPL resins is the gold standard for desalination and concentration. This method routinely recovers 50-65% of marine and terrestrial DOM. However, in unusual samples, for example from hydrothermal vents, early-stage microalgal cultures, the sea-surface microlayer, or sediment leachates, DOM recovery drops to 20% or less, presumably because the prevalent organic compounds are outside the polarity or molecular size window of the PPL sorbent. Here, we adjusted individual steps of the standard protocol, such as acid type, acid strength, and solvent polarity to increase DOM yields in notoriously low-recovery samples. We compared acidification of a coastal marine sample with either HNO3 or HCl at pH 1 and pH 2. From samples of the sea-surface microlayer, the underlying seawater, and macroalgal and intertidal sediment leachates, we performed two subsequent extractions at environmental pH and at pH 2. Following DOM extraction, we compared several eluents, including methanol, acidic methanol, tetrahydrofuran, and dichloromethane. We evaluated the different approaches by determining dissolved organic carbon (DOC) and dissolved black carbon (DBC) yields as well as changes in molecular DOM composition using ultra-high resolution mass spectrometry.

Lowering the pH from 2 to 1 increased the DBC yield but resulted in slightly lower DOC recoveries, indicating a shift in molecular composition of the retained compounds rather than expansion of the SPE window. HNO3 may furthermore cause nitration, nitrosation and oxidation of DOM. However, combining sequential extraction at neutral and acidic pH with a series of eluents increased DOC recoveries substantially in comparison to the standard protocol. The inter-sample differences in the molecular composition (as detected via ultrahigh-resolution mass spectrometry on a molecular formula level) of the extracted DOM exceeded those caused by variations in the protocol and followed similar trends compared to the standard procedure. The co-variance of molecular degradation indicators with PPL performance emerged as a general trend: Recoveries with the standard protocol increased with the DOM degradation state. We conclude that PPL is much more versatile than its regular use indicates and encourage exploring a larger bandwidth of experimental setups for a better representation of natural DOM from a wide variety of sources.

How to cite: Waska, H., Füssel, J., Paetz, K., Renken, M., and Dittmar, T.: Improving solid-phase extraction of dissolved organic matter (DOM), EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-13604, https://doi.org/10.5194/egusphere-egu23-13604, 2023.

A.237
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EGU23-17175
Gerd Gleixner, Vanessa-Nina Roth, Markus Lange, and Carsten Simon

Although representing only a small portion of all the organic matter being present in soils, dissolved organic matter (DOM) is its most mobile and reactive fraction. Along its transport down the soil profile, DOM interacts with minerals via sorption and aggregation phenomena, and with organisms via uptake, exudation or internal recycling. During this downward passage DOM composition changes too, shifting from a dominant plant/ plant decomposition product character to a more decomposer-driven signature. Such trends have been documented well by ultrahigh resolution mass spectrometry (FT-MS) which reveals thousands of molecular compositions (formulas) in one DOM sample (Roth et al. 2019). However, complementary properties of the molecules that constitute these signatures are largely missing. To test if the downward trend in molecular composition would also affect DOM’s fragmentation sensitivity, and if these effects could obscure the final ecological interpretation, we obtained direct injection FT-MS data with and without source-induced fragmentation (SID) at 45 eV. As a test dataset, we used samples from suction plates installed in three soil profiles (at 5, 10, 20, 30 and 60 cm depth) developed on aeolian sand deposits (podzols, cambisols) in Linde, Brandenburg (Germany). These three sites vary mainly in vegetation cover (grassland, oak, pine). All sites showed a clear depth trend as reported earlier, especially without SID turned on. SID clearly decreased the ion abundance of signals in the molecular weight range 300-500 Da (center ~350), while signals in the range 150-400 Da (center ~ 225) increased; more formulas were detected with SID on. With depth, the population of molecules decreasing/ increasing changed significantly, especially between 30 and 60 cm depth, across all sites. At 60 cm depth, decreasing formulas were more aliphatic while increasing formulas were more confined to a narrow area in the center of the van Krevelen space (“island of stability”). Interestingly, the formulas decreasing significantly across all sites were largely CHO (no other heteroatoms, at all depths), S-containing (at 5, 10, 20 and 30 cm) or P-containing (30 and 60 cm), while formulas increasing were CHO (at all depths) and N-containing ones (at all depths, but mainly at 20 and 30 cm), thereby indicating depth-dependent differences and ionization of new N-containing molecules. In ordination space, sites were clearly differentiated according to SID status, depth and site (in this order), but SID did not affect the separation in terms of depth or site, i.e., the ecological interpretation of DOM fingerprints remained similar independent of the SID status. This means that trends in soil DOM studies are likely not obscured by differences in fragmentation during the electrospray ionization process.

Reference: Roth, V.-N., Lange, M., Simon, C., Hertkorn, N., Bucher, S., Goodall, T., Griffiths, R. I., Mellado-Vázquez, P. G., Mommer, L., Oram, N. J., Weigelt, A., Dittmar, T., Gleixner, G. (2019): Persistence of dissolved organic matter explained by molecular changes during its passage through soil. Nat. Geosci. 12: 755–761.

How to cite: Gleixner, G., Roth, V.-N., Lange, M., and Simon, C.: Depth trends revisited: Source-induced fragmentation of soil dissolved organic matter, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-17175, https://doi.org/10.5194/egusphere-egu23-17175, 2023.

Novel molecular tools (biomarkers and DNA) in climatic and environmental archives – challenges, advances, and prospects
A.238
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EGU23-15566
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ECS
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Highlight
Doreen Yu-Tuan Huang, Nick Cutler, Saúl Rodriguez, Marina Morlock, and Jonatan Klaminder

Environmental DNA (eDNA) in sediments (soils, lake and marine sediments) can – in principle - be used to reconstruct past environments, provided the DNA is readily preserved and is relatively immobile within the sedimentary sequence (to allow accurate dating). Concerns over the mobility of DNA in soils have meant that these sediments have not been considered a reliable source of eDNA for palaeo-reconstruction. However, eDNA in soils could be preserved and immobilized through adsorption to secondary minerals (predominantly clays) in sediments. The potential of clay minerals to immobilize DNA is poorly understood; to address this knowledge gap, we conducted an experiment to evaluate the vertical mobility of eDNA between soil layers.

Our experiment involved the application of spiked (non-indigenous) DNA to an experimental plot in eastern Greenland over a period of two years. During this period, we took soil samples at different depths below the plot and sequenced the samples to detect the spiked DNA. In addition to our experiment, we analyzed plant DNA from sequences of paleosols at a site in west Greenland and a site in south Iceland, to attempt to reconstruct long-term changes in vegetation cover.

Our Greenland experiment indicated that faint traces of alien DNA can be transported to deep (thus old) soil horizons by percolating rainwater and can remain intact for at least two years. We suspect this occurred in Greenland because a) rainfall is high and b) the soils are skeletal and exceptionally porous. Despite this result, we observed changes in plant DNA with depth at our other two sites; these changes seemed to track century-scale environmental changes. We could not date the changes in the Greenlandic record due to the scarcity of macrofossils for radiocarbon dating. However, macroscopic tephra layers at the site in Iceland provided isochrons (time parallel marker beds) that allowed us to assign approximate dates using tephrochronology.

Our results indicate that most of the spiked eDNA was either retained at the surface or degraded in the soil profile: only very tiny quantities leached to deep soil horizons. Therefore, we propose that eDNA in paleosols, especially those on tephra beds, possesses great potential in palaeo-reconstruction, especially when other archives (fossils, lake sediments) are not available. However, we recommend that more studies are required to examine how mineralogy and soil types govern eDNA mobility and longevity in soils.

How to cite: Huang, D. Y.-T., Cutler, N., Rodriguez, S., Morlock, M., and Klaminder, J.: Does vertical mobility of eDNA in old soils affect the reconstruction of past environments?, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-15566, https://doi.org/10.5194/egusphere-egu23-15566, 2023.

A.239
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EGU23-2631
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ECS
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Highlight
Marina A. Morlock, Saúl Rodriguez-Martinez, Doreen Yu-Tuan Huang, and Jonatan Klaminder

Environmental DNA (eDNA) analysis from lake sediments shows promise to become a great paleoecological technique. Nevertheless, our knowledge regarding catchment processes that influence the eDNA signal preserved in sediments creates uncertainties when interpreting temporal changes in reconstructed biodiversity. Are changes in species composition the result of ‘real’ changes in species abundances or simply the result of altered DNA transport processes in the catchment?

In this presentation, we investigate the role of erosion for sediment eDNA-based reconstructions. We utilize sediment records from the Central Alps and compare the plant and mammal DNA pools in lake sediments of similar age but deposited under different erosion regimes: detrital event layers formed during heavy precipitation events vs. hemi-pelagic background sedimentation.

We find strong differences in the reconstructed plant and mammal communities both across space and time. Temporal changes across the Holocene were the main drivers of change for reconstructed plant communities, but sediment type -and thus erosion regime- was the second most important factor of variance. Around 30% of all plant and mammal taxa were uniquely detected in event layers. Our results highlight that the two sediment types preserved their unique assembly of plant and animal DNA, suggesting that post-depositional mobility of terrestrial DNA is insignificant on Holocene timescales. However, our results also highlight the challenge when attributing changes in erosion regimes to the appearance of new species in an eDNA-based paleo-record because increased erosion will also increase the representation of taxa already present in the lake’s catchment. In our case, this mechanism was an important factor for DNA-inferred species composition and taxonomic richness recorded in the sediments.

How to cite: Morlock, M. A., Rodriguez-Martinez, S., Huang, D. Y.-T., and Klaminder, J.: Erosion regime controls sediment eDNA-based community reconstruction, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-2631, https://doi.org/10.5194/egusphere-egu23-2631, 2023.

A.240
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EGU23-8474
Kathleen Stoof-Leichsenring, Stella Buchwald, Dirk Nürnberg, Lars Harms, and Ulrike Herzschuh

Understanding past ecosystems in the Arctic and subarctic oceans is important to project ecosystem development under enhanced warming. Sedimentary ancient DNA (sedaDNA) is a fantastic proxy providing information with sufficient taxonomic width and depth to comprehensively reconstruct past ecosystems. This study uses shotgun metagenomics of 42 sediment samples to decipher phyto- and zooplankton community changes over the last glacial-interglacial cycle back to the Eemian in the subarctic western Bering Sea. We aim to understand the sensitivity of plankton community composition to climate changes and its consequences on food web dynamics and carbon export. Our results indicate that micro- phytoplankton, like sea-ice associated diatoms, and cold-adapted chlorophytes, along with crustaceous zooplankton (copepods) dominated during the last glacial period. Contrarily, pico/nano-sized phytoplankton and the diatom family Chaetocerotaceae accompanied by heterotrophic protists and reduced abundance of copepods characterized the interglacial plankton communities. Further, we identified profound differences between the Holocene and Eemian. Particularly, the Holocene records a pronounced increase of pico-sized cyanobacteria, whereas in the Eemian, cold-water related taxa like Bathycoccaceae and Triparmaceae sub-dominate the community, supporting unique communities in both interglacials, challenging an analogy to future warming scenarios. In summary, our study shows evidence for a shift from micro-sized towards pico-sized phytoplankton with climate warming in the Holocene, accompanied by a more diverse zooplanktonic community dominated by bacterial grazing heterotrophic protists. Under future warming, decreased phytoplankton cell size and shifts in the grazing communities could affect food web linkages and result in reduced potential carbon sequestration and export in the subarctic Bering Sea, weakening its function as an effective carbon sink.

How to cite: Stoof-Leichsenring, K., Buchwald, S., Nürnberg, D., Harms, L., and Herzschuh, U.: Sedimentary ancient DNA reveals plankton community shifts in subarctic western Bering Sea back to the Eemian interglacial, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-8474, https://doi.org/10.5194/egusphere-egu23-8474, 2023.

A.241
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EGU23-7912
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ECS
Saúl Rodriguez-Martinez, Marina Morlock, Doreen Y-T. Huang, and Jonatan Klaminder

Abstract

Analysis of DNA fragments preserved in natural archives, such as lake sediments and buried soil layers, has increased our understanding of past environments and their organism communities.  High throughput sequencing of genetic material from these matrixes and the linkage of DNA barcode databases (e.g. metabarcoding) has played, and still play, an important role for palaeoecological reconstructions. Yet, scrutinization of results derived using metabarcoding approaches – methods that fairly recently have become common within environmental science – is critical. Tag jumping is a process where sample-specific labels (tags), added to DNA sequences to allow identification of individual samples in a pooled DNA library, are unintentionally changed during sampling handling (during the end repair step). If occurring, tag jumping can result in DNA sequences being associated with the wrong sample. Nevertheless, tag jumping is rarely discussed within the paleoecological community, and the importance of the process remains largely unquantified.

Using example datasets from lake sediments and soils, we assessed the impact of tag jumping on metabarcoding data and how it affects paleo-reconstructions. We find that tag jumping can lead to substantial false positive detection of taxa in sedimentary samples. That tag jumping generated a very characteristic topological sample cross-contamination pattern allowed us to estimate that up to 80% of data in some data sets was distorted by this process(Rodriguez‐Martinez et al., 2023). We further compared a set of sedimentary DNA samples processed according to commonly applied, tag-jumping sensitive protocols with the same set of samples processed following a tag jumping free protocol. Our results suggest that tag jumping can affect paleoecological interpretations by: i) masking significant environmental change at a Holocene time-scale by making samples more similar; and; ii) adding species to sediment samples where they were not originally present (false positive detections). Our data clearly shows that tag jumping can represent a major source of bias for paleoecological reconstructions based on metabarcoding techniques. Importantly, the problem is easily circumvented if the right protocols are used.

 

References

Rodriguez‐Martinez, S., Klaminder, J., Morlock, M.A., Dalén, L., Huang, D.Y., 2023. The topological nature of tag jumping in environmental DNA metabarcoding studies. Mol. Ecol. Resour. 1755–0998.13745. https://doi.org/10.1111/1755-0998.13745

How to cite: Rodriguez-Martinez, S., Morlock, M., Huang, D. Y.-T., and Klaminder, J.: Tag jumping may produce major distortion of paleoecological reconstructions derived using metabarcoding approaches, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-7912, https://doi.org/10.5194/egusphere-egu23-7912, 2023.

A.242
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EGU23-6233
Leszek Marynowski, Dorota Staneczek, and Dariusz Więcław

Central Carpathian Palaeogene Basin (CCPB) is a wedge-top basin that opened in the Central Western Carpathians in Lower Palaeogene. Orava sub-basin (OSB), located in N-Slovakia, comprises the NW remnants of CCPB. Based on previous studies (Środoń et al., 2006), OSB is the least mature part of CCPB. Yet, the estimated palaeotemperatures are relatively high and reach 95-100oC. Obtained results based on biomarkers study show differences in thermal maturity depending on the location of sampling sites and lithostratigraphy. Generally, maturation increases from N to S and Biely Potok (Upper Oligocene) to Huty Fm (Lower Oligocene). The occurrence of ββ-hopanes, hopenes, oleanenes, and low values of 22S/(22S+22R) homohopane ratio (~0.4), as well as 20S/(20S+20R) sterane ratio (~ 0.1 - 0.2), suggests low thermal maturity of organic matter in N and NE part of OSB. On the contrary, the S part is characterized by relatively high values of 22S/(22S+22R) ratio (>0.5), the 20S/(20S+20R) ratio (>0.4) and lack of unsaturated compounds, indicating that these units have reached the oil window stage. Rock-Eval analysis reveals the dominance of III-type kerogen in both Lower and Upper Oligocene due to terrestrial organic matter input. Biomarkers of terrestrial origin were detected in all samples including both angiosperm and gymnosperm affinity. Moreover, in less mature samples perylene is present as one of the major compound. This compound is interpreted as derived from soil and/or wood degrading fungi (Marynowski et al., 2013). In the Lower Oligocene, dysoxic to euxinic depositional environments are prevalent, which is manifested by the occurrence of isorenieratane and its derivatives, as well as small (<5µm) pyrite framboid diameters in many samples. However, a change of sedimentary conditions to oxic/dysoxic was found in Upper Oligocene samples. The results show larger framboid diameters (>5µm), a lack of isorenieratane and homohopanes with more than 33 carbon atoms in the molecule. In summary, sedimentary conditions in the Oligocene of CCPB changed from predominantly anaerobic to aerobic, with increased input of terrestrial organic matter.

 

This work was supported by the National Science Centre, Poland (grant 2018/31/B/ST10/00284 to LM).

 

Środoń, J., Kotarba, M., Biroń, A., Such, P., Clauer, N., Wojtowicz, A., 2006. Diagenetic history opf the Podhale-Orava Basin and the underlying Tatra sedimentary structural units (Western Carpathians): evidence from XRD and K-Ar of illite-smectite. Clay Miner. 41, 751–774.

Marynowski, L., Smolarek, J., Bechtel, A., Philippe, M., Kurkiewicz, S., Simoneit, B.R.T. 2013. Perylene as an indicator of conifer fossil wood degradation by wood-degrading fungi. Org. Geochem. 59, 143–151.

How to cite: Marynowski, L., Staneczek, D., and Więcław, D.: Thermal maturity and depositional conditions in the Orava part of Central Carpathian Palaeogene Basin, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-6233, https://doi.org/10.5194/egusphere-egu23-6233, 2023.

A.243
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EGU23-3696
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ECS
New microbial sources of 2- and 3-methylhopanoids from anoxic, acidic, sulfidic hydrothermal springs
(withdrawn)
Marisa Mayer, M. Niki Parenteau, Thomas Evans, Linda Jahnke, Roger Summons, Michael Madigan, Gordon Love, and Paula Welander