Jahrestagung der Arbeitsgemeinschaft
Stabile Isotope e.V.
26.–29. September 2021 | TU Darmstadt
Eine Übersicht aller Sessions/Sitzungen dieser Veranstaltung.
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|Datum: Sonntag, 26.09.2021|
|14:00 - 17:00||ASI-Juniors|
Virtueller Veranstaltungsort: ASI Juniors - Meeting Link
Impulsvorträge Marshall / Barth / Van Geldern
|Datum: Montag, 27.09.2021|
|10:00 - 12:30||Firmen Geräte & Zubehör|
Virtueller Veranstaltungsort: ASI Firmen - Meeting Link
Online: ThermoFisher Scientific, Elementar, IVA & Envicontrol
Programm IVA Analysetechnik: Imagefilm https://youtu.be/C2Sf1StP-yE
Programm Thermo Fisher: 11 Uhr "Development of an Orbitrap for Isotopes"
10:00 – 11:00 Meet & Greet with the experts from Elementar (technical Q&A session)
11:00 – 12:00 lyticOS software suite - General overview
High temperature GC oven technology for the analysis of δ2H in alkanes
Compound specific δ15N analysis for ecology
iso FLOW GHG - Discover the latest solution for the analysis of greenhouse gases
12:00 – 12:30 Q&A session about the presentations
|12:30 - 13:30||Pause|
|13:30 - 14:00||Eröffnung der Tagung|
Virtueller Veranstaltungsort: Eröffnung - Meeting Link
|14:00 - 15:30||Block 1.1: Analytik, Methoden, Technik und Qualitätssicherung stabiler Isotope|
Virtueller Veranstaltungsort: Block 1.1 - Meeting Link
Chair der Sitzung: Matthias Gehre, UFZ
Chair der Sitzung: Paul Königer, BGR Bundesanstalt für Geowissenschaften und Rohstoffe
14:00 - 14:15
Compound Specific Stable Sulfur Isotope Analysis (δ34S and δ33S) of Organic Compounds Using Gas Chromatography Hyphenated with Multiple Collector Inductively Coupled Plasma Mass Spectrometry (GC-MC-ICPMS)
1Helmholtz-Zentrum für Umweltforschung GmbH - UFZ, Leipzig, Germany; 2Geological Survey of Israel, Jerusalem, Israel; 3Westfälische Wilhelms-Universität Münster, Institut für Geologie und Paläontologie, Münster, Germany
Stable sulfur isotope analysis is applicable in various fields in forensics and environmental analytics to investigate the sources and degradation of organic compounds, many of them being priority pollutants in groundwater and the atmosphere. A broader use of sulfur isotopes of organic compounds in environmental studies is still hampered by the availability of precise and easy-to-use techniques. Here we present a method for the determination of stable sulfur isotope ratios using gas chromatography coupled with multiple-collector inductively coupled plasma mass spectrometry (GC-MC-ICPMS) which can be used for both δ34S and δ33S analysis. The method was evaluated using the reference materials IAEA-S-1, IAEA-S-2 and IAEA-S-3 which were converted offline to SF6 prior to analysis. Standardization was carried out by a two-point calibration approach. The δ34S obtained by our method are in good agreement (within analytical uncertainty) with the results obtained by the conventional dual inlet method. Additionally, the impact of the used mass resolution (low and medium), the influence of auto-protonation of sulfur isotopes and the effect of isobaric interferences of O2+ on the obtained isotopic ratios were investigated. Overall analytical uncertainty including normalization and reproducibility for δ34S and δ33S was usually better than ±0.2 mUr (1σ) for analytes containing at least 100 pmol of S. Thus, the presented compound-specific online method should be sufficiently precise to address a wide variety of research questions involving mass independent isotope effects of sulfur-containing organic compounds to discriminate sources or biological and chemical reactions in the environment.
14:15 - 14:30
New Frontiers in Compound-Specific δ2H Analysis
1University of Bristol, UK; 2University of Plymouth, UK; 3Silicon Austria Labs, Austria; 4International Atomic Energy Agency, Austria; 5Elementar UK Ltd, UK
The hydrogen isotopic composition (δ2H) of lipid “biomarker” compounds (molecules synthesized by and traceable to living organisms) have long been of interest to biogeochemists, with applications ranging from the investigation of food authenticity, to the reconstruction of ancient climate and environment. The preferred method of stable isotope analysis of such lipids employs gas chromatography-isotope ratio mass spectrometry (GC-IRMS), which effectively limits applications to those which measure compounds of relatively low molecular weight and polarity (i.e. compounds which elute from a typical capillary GC column at c. 320-350°C). As such, only very few compounds of molecular weight > c. 500 g/mol have been successfully analyzed intact by GC-IRMS to determine δ2H. However, the hydrogen isotopic composition of larger and/or polar compounds can be of significant interest.
Here we present two pioneering new techniques for the analysis of larger and/or more polar organic molecules of biogeochemical interest which are traditionally considered unsuitable for GC-IRMS analysis. This includes a rapid one-step derivatization procedure for the isotope analysis of the non-exchangeable hydrogen in mono and disaccharides and subsequent conversion to H2 by chromium reduction (Abrahim et al, 2020), and the development of a high-temperature GC-IRMS (HTGC-IRMS) methodology employed for the analysis of a suite of compounds of interest (Lengger et al., 2021). In particular we present the successful HTGC-IRMS analysis of triacylglcerides (TAGs), whose derivative fatty acids are often employed in studies of archaeological diet and modern food authenticity analysis, tetraether lipids including glycerol dialkyl glycerol tetrethers (GDGTs) which have been widely employed as proxies for paleoclimate and environmental analysis based on their relative distributions, and longer chain n-alkanes, the lower molecular weight homologues of which have been widely employed for paleohydrological analysis. We will present initial results demonstrating the performance and validation of the techniques, and their potential application to organic biogeochemistry.
Lengger S.K., Weber Y., Taylor K.W. R, Kopf S. H., Berstan R,, Bull I,D., Mayser J., Leavitt W. D., Blewett J. & Pearson A. (2021). Determination of the δ2H values of high molecular weight lipids by high temperature GC coupled to isotope ratio mass spectrometry. Rapid Communications in Mass Spectrometry 35:e8983.https://doi.org/10.1002/rcm.898310
Abrahim, A., Cannavan, A., & Kelly, S. (2020). Stable isotope analysis of non-exchangeable hydrogen in carbohydrates derivatised with N-methyl-bis-trifluoroacetamide by gas chromatography–Chromium silver reduction/High temperature Conversion-isotope ratio mass spectrometry (GC-CrAg/HTC-IRMS). Food Chemistry 318 (126413) https://doi.org/10.1016/j.foodchem.2020.126413
14:30 - 14:45
A quick one-step sample preparation method with 2,2-Dimethoxypropane (DMP) for isotopic fingerprint analysis of vegetable oil – how does DMP influence the accuracy of the C- and H-CSIA by GC-C/Py-IRMS?”
Stoffstrommanagement und Ressourcenwirtschaft, Institut IWAR, TU Darmstadt
Compound-specific stable isotope analysis (CSIA) of fatty acids (FAs) is an important tool for the investigation of authentication of vegetable oil. Stable isotope ratios of carbon (δ13C) and hydrogen (δ2H) of individual FAs are to be determined from the δ13C and δ2H of fatty acid methyl ester (FAMEs), which are produced by reactions of FAs in oil and methyl group (–CH3) of methanol in the presence of catalysts. This transmethylation process generally involves multiple steps thus often becomes a bottleneck process of the investigation with a large number of samples.
Garcés and Mancha (1993) developed a quick sample preparation method to generate FAMEs directly from seeds in one step in a single reactor. They optimized transmethylation efficiency by adding 2,2-Dimethoxypropane (DMP). The applicability of this one-step method was verified to determine the lipid content and the FA profile of different oilseeds. However, the verification of this method in determining the isotope composition of individual FAs has not yet been reported.
In this study, we evaluated the feasibility of the one-step method for C- and H-CSIA of individual FAMEs in rapeseed samples with the following two concerns: (1) the influence of the aggregate states of samples on the reproducibility of C- and H-CSIA (2) the influence of DMP on the accuracy of δ13C and δ2H values of FAMEs, consequently FAs, by Gas Chromatography-Combustion/Pyrolysis-Isotope Ratio Mass Spectrometry (GC-C/Py-IRMS). DMP in the one-step method will contribute to producing extra methanol as a reaction-intermediate, which can be consumed to generate FAMEs. We investigated the isotope composition of FAMEs produced with and without DMP and evaluated the extent of the involvement of the reaction intermediate methanol in the production of FAMEs in the one-step method.
Our results showed that the reproducibility of the one-step method in C- and H-CSIA for the solid rapeseeds and fluid oil was comparable. Further, we confirmed that no significant differences arose in the carbon and hydrogen isotope compositions of the selected main FAMEs produced with and without DMP, except for the H-CSIA value of C18:3. The reproducibility of the one-step method for rapeseed was in the range of ±0.1 mUr to ± 0.3 mUr for C-CSIA and ±1 mUr to ±3 mUr for H-CSIA of the main FAMEs. The performance of the one-step method for rapeseed samples for the determination of δ13C and δ2H values of FAMEs is satisfying.
14:45 - 15:00
Revisiting SPIN-MIRMS: N-isotopic composition of nitrate and ammonium from aquaeous solutions by isotope ratio mass spectrometry
1Universität Göttingen, Kompetenzzentrum Stabile Isotope, Deutschland; 2Thuenen Institut für Agrarrelevante Klimaforschung, Braunschweig, Deutschland
Analyses of N-isotopic composition of nitrate and ammonium from aqueeous solutions are difficult - especially at natural abundance. The SPIN-MIRMS technique presented previously has the key advantage that no sample pretreatment is necessary and analysis is fast.
Here we present recent insights into the performance and substrate specifity of the approach.
15:00 - 15:15
δ13C Analysis of DOC from Liquid Samples - Proof of Concept
Max-Planck-Institut für Biogeochemie, Deutschland
Both, dissolved organic carbon (DOC) and its corresponding δ13C signature are important parameters for the investigation of the carbon cycle. For example, DOC concentration analyses reveal the organic matter flow in aquatic systems, while δ13C values of DOC can give insights on origin and transformation of organic matter. The combined analysis of DOC and δ13C can require either time-consuming and laborious sample preparation or a wet chemical oxidation method which can underestimate DOC concentrations and lead to isotopic fractionation.
Here we investigate the feasibility of using an elemental analyzer – isotope ratio mass spectrometer (EA-IRMS) system. By attaching a liquid autosampler to the EA and installing a Nafion water trap between the reactor and the GC-column we analyze DOC concentrations and δ13C values of liquids analogous to the way solid samples are measured. With this minor adjustment to the instrument configuration, δ13C measurements with a precision of < 0.1 ‰ can be made on DOC samples with a concentration of 10 mg/ml.
Preliminary tests were designed to test different parameters including linearity, memory effect, and stability. We also investigated whether dissolved carbonates yield a similar measurement precision as dissolved organic compounds, and whether a mix of DOC and DIC affect the overall fidelity of the measurements. For the analytical tests and data evaluation several in-house and international standards including urea, caffeine (IAEA-600), glutamic acid (USGS-40 and 41), carbonates (as inorganic standard) and sugars were dissolved in ultra-pure water. In the future, the method will be optimized for natural samples with smaller DOC concentrations by changing the injection amount or implementing a concentrating step. The preliminary results show that our method is easy to apply in laboratories for quick routine δ13C characterization of high concentration samples.
|15:30 - 16:00||Pause|
|15:30 - 16:00||Sponsorenausstellung|
Virtueller Veranstaltungsort: Sponsorenausstellung - Meeting Link
|16:00 - 17:00||Block 1.2: Analytik, Methoden, Technik und Qualitätssicherung stabiler Isotope|
Virtueller Veranstaltungsort: Block 1.2 - Meeting Link
Chair der Sitzung: Matthias Gehre, UFZ
Chair der Sitzung: Paul Königer, BGR Bundesanstalt für Geowissenschaften und Rohstoffe
16:00 - 16:15
Comprehensive Isotope Ratio MS of Oxyanions with an Electrospray-Orbitrap
1Thermo Fisher Scientific, Deutschland; 2University of Colorado, Boulder, USA
A new, comprehensive approach for IRMS using an electrospray ionization (ESI) Orbitrap gives access to multidimensional isotope signatures of intact polar compounds in liquid samples.
Customized sample introduction and automation, applying IRMS specific rules, were developed by using nitrate as a model compound. In total, 7 isotopologs of nitrate can be quantified simultaneously opening multiple pathways for calculating δ15Ν, δ18O, δ17O and Δ17O values with sub-‰ precision and accuracy. It also offers a unique way to measure nonrandom isotopic distributions (“clumping”) in oxyanions.
The approach can be applied to other oxyanions like nitrite and sulfate. First results will also be shown.
This study bridges the gap between bioanalytical MS and IRMS providing methods to measure new isotopic signatures in intact organic and inorganic compounds.
16:15 - 16:30
The next leap forward in gas IRMS
Thermo Fisher Scientific, Deutschland
Thermo Scientific™ Qtegra™ Intelligent Scientific Data Solution (ISDS) Software is carefully optimized to revolutionize your gas IRMS analyses, delivering simplicity, efficiency and quality in your laboratory. Built to cater to the most diverse applications, Qtegra ISDS Software provides you with the level of control that you require, within a logical, easy-to-use framework, enabling you to dramatically improve your productivity. Join us for a software tour.
To compliment the arrival of Qtegra ISDS Software, we are launching the next generation of Thermo Scientific™ DELTA Series IRMS – the Thermo Scientific™ DELTA Q™ IRMS. DELTA Q IRMS is the world’s first net zero mass spectrometer launched as a part of the IsoFootprint project, a new initiative by the Inorganic Mass Spectrometry team with the aim to set the pathway towards true net zero. All the CO2 emitted to the atmosphere during the manufacture of the instrument (from extraction of the raw materials to transport and assembly) will be removed from the atmosphere through investment in carbon dioxide removal projects. Projects were selected with priority given to those that were permanent, additional, globally sustainable and supporting nascent technology that has the ability to scale
Join us to learn more about sustainable isotope analysis driven by Qtegra ISDS Software. The journey has begun.
16:30 - 16:45
Improved throughput for δ18O and δD measurements of water with Cavity Ring-Down Spectroscopy
1Picarro B.V., Niederlande; 2Picarro Inc., USA
Oxygen (18O/16O) and deuterium (D/H) isotopes are a widespread tool to trace physical and chemical processes in hydrology and biogeosciences. Precision and throughput are key parameters for water isotope analysis. Here, we will present two new methodologies for the Picarro L2130-i Cavity Ring-Down Spectroscopy (CRDS) water isotope analyzer that allow the user to increase the throughput without compromising data quality.
The Picarro Express Method now distinguishes between a memory reduction stage and a sample analysis stage and allows the user to measure up to 50 samples per day while maintaining the excellent precision of CRDS (i.e., 0.01‰ for δ18O and 0.05‰ for δD). This corresponds to doubling the throughput compared to the standard Picarro methodology. The Picarro Survey Method makes use of ultrafast injections and sorts the samples by their measured isotopic values, enabling a powerful new strategy to reduce memory effects.
We present these different measurement strategies that increase the throughput for routine water isotope analysis. The improved methodologies use software based modifications of the injection procedure, and do not require any hardware changes.
16:45 - 17:00
A new infiltration optimized tracer application method for 15N and 18O tracers in field soil experiments
1Institut für Grünland und Futterbauwissenschaften, Agrar- und Umweltwissenschaftliche Fakultät, Universität Rostock, 18059 Rostock; 2Soil and Physical Sciences Department, Faculty of Agriculture and Life Sciences, Lincoln University, PO Box 84, Lincoln, 7647, New Zealand
Nitrous Oxide is a long-lived greenhouse gas with the third most important contribution to radiative forcing the dominant anthropogenic ozone-depleting substance emitted. There are many important pathways from agricultural soils for N2O production besides nitrification and denitrification that are challenging to distinguish. Isotopic tracer methods are applied to aid differentiating between microbial and chemical sources. Commonly used application schemes apply 15N-NH4NO3 (triple labeling method) or additionally 18O-H2O and 18O-NO3 (dual isotope method). Both methods assume a homogenous distribution of the tracers within the examined soil volume. Field experiments can further improve our understanding as they incorporate undisturbed soils with intact soil aggregates and plant effects. Preferential flow represents the biggest obstacle for a homogeneous, fast and large area application of tracer. This effects application methods used for field experiments like by watering can or with sprinklers as they promote ponding. Better infiltration patterns visualized by blue dye solution were achieved by slowing down application speed and promoting infiltration by capillary forces. For a 15N comparative study in grassland, drip irrigation was chosen as it is scalable and a noninvasive method. Application by drip irrigation resulted in a smaller standard deviation of the 15N concentrations and a larger recovery rate compared to application by sprinkler. After successful pretest, application by drip irrigation was implemented for the central experiment in Gießen of the DASIM project (Denitrification in Agricultural Soils: Integrated control and Modelling at various scales) for an area of 13 m² grassland. For this purpose, 3200 cost effective dropper bottles were made and placed onto acrylic sheets closely above ground to set the pattern and spacing of infiltration points. Each dropper bottle provides a reservoir for each infiltration point, resulting in an even distribution of the tracer solution over the soil surface. A reliable dripping speed (100 ml ≙ 55 min +/-5 min) is assured by individual cannulas (0.8 mm x 120 mm) at the tip of each dropper bottle. Dripping can be started fast by removing a rubber stopper at the bottom of the bottle. The areas were split into two sets for application with each finishing within 2 hours with an acceptable failure rate. Tracer application by dropper bottles therefore represents a new, noninvasive and infiltration optimized application method for large field experiments. To solve problems arising from different tracer retention i.e. nitrate (NO3-) and ammonium (NH4+) invasive methods would be needed.
|Datum: Dienstag, 28.09.2021|
|9:30 - 11:00||Block 2.1: Hydrogeologie, Hydrologie und Wasserisotope|
Virtueller Veranstaltungsort: Block 2.1 - Meeting Link
Chair der Sitzung: Christoph Schüth, TU Darmstadt
Chair der Sitzung: Florian Einsiedl, TUM
Chair der Sitzung: Diana Burghardt, TU Dresden
9:30 - 10:00
Oxygen is all around...
1GeoZentrum Nordbayern, Deutschland; 2Friedrich-Alexander-Universität Erlangen-Nürnberg
Oxygen is the most abundant element within the earth system. At the earth´s surface and in its molecular form as O2 it is also one of the most important RedOx agents in both gaseous and dissolved forms. For such reactions, tracing of oxygen can identify fundamental processes including photosynthesis, respiration and exchange between the atmosphere and water. Moreover, as part of the water molecule oxygen can serve as a tracer of origin, mixing and movement of H2O. However, water can also release O2 via its splitting by for instance photosynthesis. Such processes also offer relationships to carbon cycling on various scales. While tracing of water with oxygen stable isotope ratios finds applications in a wide spectrum of fields including hydro(geo)logy, plant sciences and medicine, isotope tracing of gaseous and dissolved O2 is much less common. Future challenges and opportunities lie in combinations of water and molecular oxygen cycles via their stable isotope ratios to outline and constrain sources and sinks of this important element.
10:00 - 10:15
Impact of the 2018-2020 drought in Central Germany on the nitrogen cycling in a meso-scale catchment: Insights from hydrochemical and stable isotope investigations
Helmholtz Centre for Environmental Research UFZ, Deutschland
Recent investigations of the nitrate pollution in groundwater and surface water bodies in Germany confirm the well-known fact that the threshold value for nitrate concentrations (50 mg L-1) is exceeded in 18% of all sampling sites belonging to the nitrate monitoring network (German Federal Environmental Agency). Besides the input of excess nitrogen into the aquatic system by human activities, climate change related hydrological variability (extreme precipitation events or longer summer droughts) may also have an effect on nitrate loads in ground- and surface water.
Especially in the last years (2018-2020), a severe drought was observed in central Germany. In order to find out the potential impact of that drought on the catchment scale nitrogen cycling, we investigated the ground- and surface water compartments of the Holtemme watershed, a meso-scale river catchment in the Harz Mountains, Central Germany. The analysis of nitrate concentrations and corresponding isotopic signatures for groundwater and surface water samples were conducted during the entire dry period and were continued until discharge conditions went back to the long term mean in early 2021. The survey revealed decreasing nitrate concentrations for both compartments during drought conditions and a significant increase in the post-drought phase. Isotopic investigations allowed us to differentiate between distinct nitrate sources and microbial turnover processes. The time series analysis of δ15N-NO3 showed regular oscillations within the year, which illustrates a periodic fertilizer application. Corresponding δ18O-NO3 signatures show higher, seasonal-independent variations that can be explained by the normal isotopic variability of the ambient water that provides two thirds of the oxygen that is incorporated into the nitrate molecule during nitrification. However, flow paths for nitrate mobilization into the surface water seem to be unaffected by the drought because contributions of each nitrate source decreased equally during dry conditions. Nitrate concentrations increased after the dry period independently of recent nitrate supply. This implies that the soil system acts as a storage compartment, from which nitrate is easily released after the drought.
Our study confirms that hydrological variability is a highly important driver for nitrate mobilization at the catchment scale. Therefore, we suggest that the impact of changing hydrological conditions needs to be taken into consideration for management practices and policy actions.
10:15 - 10:30
Spatiotemporal analysis of Central European young water fractions
Universität für Bodenkultur, Wien, Österreich
The travel time of precipitation entering a catchment and leaving it as streamflow varies according to the flow paths precipitation takes. Fast precipitation travel times through catchments are especially interesting as they pose a high risk to river water quality. However, investigating influences on travel times is challenging due to complex water flow through heterogeneous landscapes. In this study, we investigated the fraction of streamflow younger than three months (Fyw) of nine major catchments in Central Europe and compared it to catchment characteristics and a teleconnection pattern that influences European large-scale weather: the North Atlantic Oscillation index (NAO). Adjacent catchments had similar long-term average and time-variable Fyw. These patterns were explained using catchment characteristics in a multiple regression analysis with prior collinearity removal, with grassland and 20-40% tree cover density explaining 84% of Fyw variability. Besides this spatial analysis, the annual changes in Fyw resembled each other in most catchments, leading to the hypothesis that a common, annually changing influence controls it. While total water storage in the catchments had no relationship to the time-variable Fyw, the NAO of the previous year was negatively correlated with this year’s Fyw (R² = 0.68). Three hypotheses are discussed as to how this inter-annual correlation could have happened, but no distinct explanation could be found. We recommend additional studies into this relationship as well as multiple regression with prior collinearity removal for future studies of the complex interplay of spatiotemporal variables on Fyw.
10:30 - 10:45
Stable water isotope analysis and improved lumped-parameter modeling for characterizing unsaturated subsurface flow
Chair of Hydrogeology, Faculty of Civil, Geo and Environmental Engineering, Technical University of Munich, Germany
The characterization of water flow in the unsaturated zone is an important task, e.g., for evaluating water resources and stresses imposed by climate change and for protecting groundwater resources. In a 3-year field study, we have measured stable water isotopes (δ2H and δ18O) in precipitation and the outflow of two vegetated lysimeters situated in Wielenbach, Germany. The lysimeters contained soil cores of different textures, i.e. sandy gravel (Ly1) and clayey sandy silt (Ly2). Maize has been cultivated on top of the lysimeters, and four different herbicides have been applied to the maize plantation.
Lumped-parameter modeling was applied for interpreting stable water isotope observations in lysimeter outflow and for determining the mean transit time of water in the subsurface and the dispersion coefficient. Usually, lumped-parameter model (LPM) approaches consider steady-state flow, which is due to their model structure that implements analytical solutions (with constant coefficients) for simulating stable water isotope transport. In this work, we have extended this approach by subdividing the simulation time into hydrologically relevant sub-periods. Flow and transport parameters vary between these sub-periods, so that temporally varying flow is mimicked (keeping constant coefficients in each sub-period). Furthermore, preferential flow paths were considered and implemented in the model. For validation, numerical modeling of unsaturated flow and stable water isotope transport was carried out using HYDRUS-1D.
Application of the extended LPM approach could significantly improve the simulation of stable water isotopes observed in lysimeter outflow, by considering seasonal changes of flow and transport parameters. In general, LPM results corresponded well to numerical modeling results. Observations were more difficult to describe for Ly2, where the seasonal fluctuation of stable water isotopes seems not fully met by numerical modeling. The consideration of a constant δ18O upshift could improve simulations, i.e. representing, in a simplified assumption, the influence of immobile (isotopically enriched) water as an additional component that contributes to the isotopic signature of lysimeter outflow water. Both the LPM and numerical approach are hence considered to be well suited for decision support. As an advantage of the LPM approach, less input data and fitting parameters (with associated uncertainties) are required, making it a powerful tool for groundwater management methodologies.
10:45 - 11:00
Identifizierung von Oberflächenwasser-Grundwasser-Interaktionen anhand von charakteristischen Isotopensignalen
1Bundesanstalt für Gewässerkunde, Deutschland; 2Freie Universität Bozen-Bolzano, Italien
Die Verwendung stabiler Wasserisotope kann entscheidend zum Prozessverständnis von Oberflächenwasser-Grundwasser-Interaktionen an Flüssen beitragen. Flusswasser weist im Gegensatz zu Grundwasser eine höhere Variabilität in der Isotopenzusammensetzung auf, die durch Abflussereignisse wie Schneeschmelze oder Hochwasser nach Starkregenereignissen gesteuert wird. Die kontrastierende Isotopenzusammensetzung von Flusswasser und Grundwasser kann verwendet werden, um ein Mischungsmodell aus den Eingangsgrößen Flusswasser und Grundwasser vor sowie während des Ereignisses aufzustellen. Hierzu liefert der folgende Beitrag zwei Beispiele mit sehr unterschiedlich großen Einzugsgebieten aus der wissenschaftlichen Praxis.
An der Ahr, einem 53 km langen Gebirgsfluss mit einem Einzugsgebiet von 629 km² (in Südtirol, Italien) wurden monatliche Wasserproben von Flusswasser und Grundwasser von 2016 bis 2018 genommen und auf stabile Wasserisotope (δ18O und δ2H) analysiert. Die durch Schneeschmelzereignisse ausgelöste, isotopisch leichtere Flusswassersignatur (z.B. δ2H: -88,2 bis -101 ‰) konnte als ein charakteristisches Isotopensignal verwendet werden, um ein Mischungsmodell von Flusswasser und Grundwasser aufzustellen. Die Analyse zeigt, dass das Ereigniswasser ca. 41 Tage ± 10 bis zum Brunnen benötigt. Dies entspricht einer Fließgeschwindigkeit von ungefähr 0,2 bis 0,3 m d-1. Der maximale Anteil an Flusswasser im Grundwasser konnte auf ca. 4% ± 1, 15% ± 2, 19% ± 4 and 51% ± 4 für die Ereignisse im Juni 2016, Mai 2017 sowie Mai und Juli 2018 geschätzt werden.
Im deutschen Teil der Mosel, einem 232 km langen Abschnitt des zweitlängsten Nebenflusses des Rheins, werden am Schleusenstandort Lehmen seit Sommer 2020 monatliche Wasserproben von der Mosel im Ober- und Unterpegel der Stauhaltung sowie Grundwasser von 4 Grundwassermessstellen genommen. Die Analyse auf stabile Wasserisotope zeigt, dass hier das Oberflächenwasser isotopisch etwas leichter ist (δ2H: -62,3 ‰) als das Grundwasser (δ2H: -51,3 ‰). Erste Ergebnisse deuten einen monatlichen Versatz der Flusswasser-Isotopensignatur im Grundwasser an. Eine Schleusenwartung im September 2020 führte zu einer Absenkung des Flusswasserspiegels um 1,5 m und damit zu einem veränderten hydraulischen Gradienten zwischen Fluss- und Grundwasser. Es konnten während dieser Zeit nur geringfügige Veränderungen in der Isotopenzusammensetzung des Grundwassers nachgewiesen werden.
Beide Beispiele bestätigen den Nutzen stabiler Wasserisotope bei grundlagenorientierten, wie auch angewandten hydrologischen Fragestellungen, um komplexe Vorgänge bei der Oberflächenwasser-Grundwasser-Interaktion zu verstehen.
|11:00 - 11:15||Poster Kurzvorträge - Themenblock 2: Hydrogeologie, Hydrologie und Wasserisotope|
Virtueller Veranstaltungsort: Poster Kurzvorträge - Meeting Link
11:00 - 11:04
Stable water isotopes as natural tracers in a hydrogeological study of riverbank filtration in N’Djamena, Chad
Federal Institute for Geosciences and Natural Resources (BGR), Groundwater Resources - Quality and Dynamics
To assess the potential of riverbank filtration along the Chari River in the Lake Chad basin, a hydrogeological test site at a large water supply well located in close proximity to the river was established in N’Djamena, Chad. At the site, the aquifer is composed of Quaternary sediments with a total thickness of about 50-55 m and consist of alternating layers of sand and clay or silt. There are two high permeable layers at depths between ̴ 23-27 m and ̴ 45-50 m separated by a fine sand/silt layer. To date, the site consists of five deep and five shallow observation wells located around the supply well, and a shallow and a deep observation well on the opposite riverbank in Cameroon. Since 2019, samples from the Chari River, the supply well, and the observations wells on the Chadian side were collected every two weeks for hydrochemistry and water stable isotopes - with some interruptions - whereas groundwater levels were recorded with automatic data loggers.
The water level data shows that aquifer discharge conditions prevail throughout the year and that the hydraulic head in the shallow aquifer is always higher than in the deeper one. The largely fluctuating stable isotope compositions from the river can be traced in the shallow aquifer, which allow for an estimation of groundwater flow velocities ( ̴ 0.9 m/d), while the isotopic compositions in the deep observations wells remain constant throughout the year. The isotopic composition of the water supply well lies between that of the shallow and the deep observation wells without any seasonal variations. It is still unclear whether different flow paths and travel times towards the well in the shallow aquifer dampen the isotopic signal, or if a significant groundwater flow component in the fine sand/silt separating the medium sand layers contributes to the water budget of the supply well.
11:04 - 11:08
Isotopen-hydrobiogeochemische Untersuchungen an anoxischen Grundwässern off- und on-shore der norddeutschen Küste
1Leibniz Institute of Baltic Sea Research (IOW), Deutschland; 2University of Greifswald, Deutschland; 3University of Rostock, Deutschland; 4NLWKN Aurich, Deutschland
Die Leybucht liegt im Einzugsgebiet der Osterems und wird durch die vorgelagerten ostfriesischen Inseln vor der offenen Nordsee geschützt. Seit dem Mittelalter steht die Leybucht unter dem Einfluss von Verlandungserscheinungen (NLÖ, 2001). Im Jahre 2017 wurde im Küstenvorfeld in größtenteils fein- und mittelsandigen Sedimenten eine Bohrung (R144) abgeteuft, die für die Grundwasserbeobachtung in 57 bis 61 m unter Geländekante verfiltert wurde. In der vorliegenden Studie wurden das Grundwasser dieser Bohrung sowie zwei on-shore Grundwässer (Leybuchtsiel 1 und 2) in den Jahre 2019 und 2020 beprobt und hydrochemisch auf Haupt- und Spurenelemente analysiert. Diese Messungen wurden ergänzt um die Vermessung der stabilen Wasserisotope (2H, 18O), der C-Isotopenzusammensetzung des DIC sowie der S- und O--Isotopenzusammensetzung des gelösten SO4. Die Daten wurden darüber hinaus einer physikochemischen Analyse mit PHREEQ-C unterzogen.
Die Untersuchungsergebnisse zeigen, dass alle Wässer anoxisch sind und sich durch hohe gelöste Eisengehalte auszeichnen. Die drei Grundwässer unterscheiden sich hinsichtlich ihrer Wasserisotopen-Signatur, liegen aber auf der für Cuxhaven etablierten lokalen meteorischen Wasserlinie und ähneln Süßwasser-beeinflussten Porenwässer, die in tiefen Sanden im Rückseitenwatt der Insel Spiekeroog gefunden wurden (Böttcher et al., 2014). Die Bohrungen R144 und Leybuchtsiel 1 verzeichnen den Einfluss von Nordseewasser. Die Isotopenzusammensetzung des DIC und Sulfats verweist auf die Mineralisierung von gelöstem organischen Kohlenstoff hin unter Verwendung der Elektronenakzeptoren z.B., Sauerstoff, Nitrat, und Sulfat, z.T. hat bereits Methanogenese stattgefunden. Die gelösten Eisengehalte können der dissimilatorisch-mikrobiellen Reduktion von Eisenoxiden und/oder der mikrobiell-katalysierten Zersetzung von Eisensulfiden stammen (z.B., Zhang et al., 2012). Ein Austritt dieser Wässer in der Nordsee hätte eine Erhöhung des Entgasungpotenzials für CO2 zur Folge.
Böttcher M.E., Lipka M., Winde V., Dellwig O., Böttcher E.O., Böttcher T.M.C., Schmiedinger I.(2014) Multi-isotope composition of freshwater sources for the southern North and Baltic Sea. Proc. 23rd SWIM conference, Husum, 46-49.
NLÖ (2001) Beweissicherung Küstenschutz Leybucht. Morphologisch-sedimentologische Untersuchungen. Forschungsstelle Küste. Abschlußbericht.
Zhang Y.-C., Slomp, C.P., Broers H.P., Passier H.F., Böttcher, M.E., Omoregie E.O., Lloyd J.R., Polya D.A. & van Cappellen P. (2012) Isotopic and microbiological signatures of pyrite-driven denitrification linked to pyrite oxidation in a sandy aquifer. Chem. Geol., 300-301, 123-132.
11:08 - 11:12
Measuring high-resolution geochemical depth-profiles in hyporheic stream sediments with focus on aerobic and anaerobic methane oxidation
Technische Universität München, Lehrstuhl Hydrogeologie, Deutschland
A large part of carbon and nutrient cycling in rivers and streams takes place in the hyporheic zone, a hotspot of biogeochemical activity in the river bed where surface- and groundwater meet. Typically, redox zones with different dominant electron acceptors form sequentially, sorted by the energy yield of the respective redox reactions. This zonation is subject to the influence of multiple parameters such as sediment composition, river temperature, surface- and groundwater interaction, water and sediment chemical composition and others. In anaerobic sediments, methane production takes place as last step in this so-called redox ladder making many rivers net carbon emitters. Understanding sources and sinks of methane, the second most important greenhouse gas in the world, is crucial in times of climate change, but due to high spatial and temporal heterogeneity of redox processes in hyporheic sediments the relationship between methanogenesis and microbial methane oxidation is not yet fully understood.
To help filling this knowledge gap, our research group is measuring high-resolution depth-depending geochemical profiles at different locations across a stream bed. A sediment peeper is used to obtain pore water samples with a 1 cm depth-resolution. Concentration gradients of dissolved oxygen, nitrate, nitrite, sulfate, ammonia and methane show depth and width of the different redox zones. To explain the dominant methane production pathway and to interpret concentration gradients, stable carbon isotopes in methane (δ13C-CH4) are measured. The δ13C-CH4 in the methanogenic zone can be used to distinguish between aceticlastic and hydrogenotrophic methanogenesis. An isotopic enrichment in δ13C values of methane towards the sediment surface may indicate microbial degradation while measurements of dissolved oxygen can be used to separate aerobic from anaerobic methane oxidation. In the absence of oxygen, other electron acceptors may become relevant for microbial methane oxidation, for example nitrate, nitrite or sulfate. In addition, the performance of a simple 1D diffusion model will be compared with the results of a 1D diffusion-reaction model in their ability to capture the measured methane concentration gradients. This will be used as a supporting evidence of the findings from concentration and isotope measurements.
In a poster, we want to present geochemical profiles in combination with modeled concentration gradients and carbon stable isotope measurements in methane for different locations across the stream. The different sampling sites are compared in terms of sediment composition and location in the stream bed.
11:12 - 11:15
Karstic springs as strong emitters of CO2
1Friedrich-Alexander Universität Erlangen-Nürnberg (FAU), Deutschland; 2Alberta Environment and Parks, Edmonton, Canada
Inland aquatic systems play an important role in the global carbon cycle. They not only transport terrestrial carbon to the oceans but also emit carbon in the form of carbon dioxide to the atmosphere. Among inland water types rivers are significant sources of CO2 to the atmosphere, and karstic watersheds are particularly important in this respect due to their large availability of inorganic carbon.
In this context, few studies have quantified CO2 fluxes from temperate source springs and headwaters in karstic basins yet. Our study addressed this information gap by investigating CO2 outgassing from streams and groundwater-fed springs in a karstic terrain in central Germany, known as the Franconian Alb. We used DIC concentration and stable isotope (δ13CDIC) data to separate biological and geological factors that might be responsible for temporal and spatial variations and gradients in CO2 losses. This study examined characteristics of dissolved inorganic carbon (DIC) and excess partial pressures of CO2 (epCO2) in the source springs and headwaters of four watersheds in a Central European karstic region, via dissolved inorganic carbon concentration and stable carbon isotope measurements.
Our results showed the most 13C-depleted δ13CDIC values at the source springs, which become rapidly enriched downstream due to CO2 degassing. Concurrently, epCO2 values, while consistently in excess of atmospheric concentrations at the spring sources, show decreases of up to 92% within only 50 m downstream. In conjunction with the large observed flux estimates of up to 88 g C m–2 day–1, these findings suggest that karstic springs can act as focussed major CO2 sources to the atmosphere. Because headwater streams constitute the bulk of the surface area of most watersheds, they may provide a disproportionately large contribution to CO2 effluxes in carbonate-dominated basins, in which source springs play a particularly important role.
Lee, van Geldern and Barth (2021), Extreme gradients in CO2 losses downstream of karstic springs. Science of the Total Environment, 778, 146099, https://doi.org/10.1016/j.scitotenv.2021.146099
|11:15 - 11:30||Pause|
|11:30 - 12:15||Block 2.2: Hydrogeologie, Hydrologie und Wasserisotope|
Virtueller Veranstaltungsort: Block 2.2 - Meeting Link
Chair der Sitzung: Christoph Schüth, TU Darmstadt
Chair der Sitzung: Florian Einsiedl, TUM
Chair der Sitzung: Diana Burghardt, TU Dresden
11:30 - 11:45
Neue Einblicke in die Infiltrationsbedingungen des Oberjura Thermalwassers in der südlichen Bayerischen Molasse mit Hilfe der 14CDOC Methode
Technische Universität München, Deutschland
Der Oberjura Thermalwasser Aquifer im Süddeutschen Molassebecken ist der Hauptexplorationshorizont für die geothermische Energiegewinnung in Bayern. Der karbonatische Oberjura Aquifer zeigt sowohl klein- als auch großräumig starke Heterogenitäten hinsichtlich seines strukturgeologischen Aufbaus auf. So sind im Oberjura Aquifer Karsterscheinungen und tiefreichende Störungssysteme zu finden. Die neusten Literaturarbeiten unterscheiden, anhand von statistischen Clusteranalysen, zwischen drei unterschiedliche Wassertypen hinsichtlich der hydrochemischen und isotopengeochemischen Beschaffenheit im zentralen Teil des Süddeutschen Molassebeckens in Bayern und lassen ein alpennahes Infiltrationsgebiet im Süden des Süddeutschen Molassebeckens vermuten.
Anhand hydrochemischer und isotopengeochemischer Parameter untersuchen wir die Infiltrationsbedingungen des Oberjura Thermalwassers und grenzen den zeitlichen Rahmen der Infiltration mithilfe Piston Flow Grundwasseralter ein.
Prinzipiell ist das Oberjura Thermalwasser in diesem Gebiet vom Na-HCO3-Cl Grundwassertyp, zeigt aber an den südlichen Standorten Ca2+ und Mg2+ Gehalte unter den zu erwartenden Gehalten. Die Werte der stabilen Wasserisotope liegen zwischen -10,6 und -11,7 ‰ für δ18O und -85,0 bis-86,0 ‰ für δ2H und deuten auf eine Infiltration insbesondere während kaltzeitlicher Bedingungen hin.
Die Kombination aus den Ergebnissen der Hydrochemie, stabilen Wasserisotopen und den Piston Flow Grundwasseraltern aus den 14CDOC und 14CDIC Altersbestimmungen in Verbindungen mit 81Kr-Altern aus der Literatur bestätigen die Ergebnisse der stabilen Wasserisotope und geben nun Hinweise darauf, dass sich das Thermalwasser des Oberjura im Süden aus mindestens zwei Grundwasserkomponenten zusammensetzt. Auf Grund der ermittelten Piston Flow Alter der untersuchten Grundwässer ist eine Infiltration nur über „Bypass“-Strukturen, die in der überlagernden Molasse zu finden sind, zu erklären.
11:45 - 12:00
Supporting the interpretation of δ¹⁵N values of dissolved NH₄⁺ and NO₃⁻ in the water column of a seasonal stratified lake using Numerical modeling and PCR gene amplification
1Technical University of Munich; 2TUM School of Life Sciences; 3University of Calgary; 4Helmholtz Centre Munich
Occurring simultaneously with denitrification in anaerobic environments, other pathways like anaerobic oxidation of ammonium (anammox) and dissimilatory nitrate reduction to ammonium (DNRA) may play an important role for the removal of fixed nitrogen (N) to gaseous N₂ from freshwater ecosystems. Recent studies that were conducted in freshwater ecosystems showed that the relevance of anammox, denitrification and DNRA, significantly changes depending on site conditions, and thus significance of anammox in freshwater is still largely unknown.
Here we investigate the pathways and relevance of nitrogen losses at the seasonal stratified lake Fohnsee during the development of the vertical redox stratification. Our approach combines concentration profiles and corresponding stable isotope compositions of NO₃⁻ and NH₄⁺, with qPCR of the hydrazine synthase gene (hzsB), nitrite reductase (nirK and nirS) genes, and numerical modeling of δ¹⁵N-NH₄⁺ values during the stratification period.
Increasing stable isotope values of nitrate (δ¹⁵N and δ¹⁸O) together with the identification of two specific marker genes for denitrification (nirK and nirS) indicate that denitrification is occurring in the anoxic water column of Fohnsee. However, stable isotope values of δ¹⁵N of ammonium and water chemistry results were ambiguous about the occurrence of anaerobic ammonium oxidation within the water column. Modeling results and qPCR analysis using hzsB marker gene for anammox showed that the observed stable isotope shift in δ¹⁵N of ammonium may be the result of mixing processes between ammonium remaining from nitrification in the oxic water column with strongly enriched δ¹⁵N values of 25‰, and ammonium that is formed by degradation of organic carbon during methanogenesis in the lake sediments with δ¹⁵N values of around 11‰.
We concluded that in a highly dynamic ecosystem such as seasonal stratified lakes, anammox bacteria only overcome limiting conditions occasionally, and may be active at most at low rates and on a temporal scale, thus, denitrification is suggested to be the principal path of nitrogen loss at the seasonal stratified lake Fohnsee. Finally, this study highlights the importance of solid understanding of the various transformations and isotope effects within a natural ecosystem for the successful interpretation of isotopic data.
12:00 - 12:15
Investigation of chloroform degradation mechanisms using multi-dimensional isotope fractionation analysis: Hydrodechlorination over Pd and Rh vs reductive dechlorination with Fe0
1Hydrogeology, Institute IAG, TU Darmstadt; 2Material Flow Management and Resource Economics, Institute IWAR, TU Darmstadt
Multi-dimensional isotope fractionation analysis is a useful tool to investigate degradation mechanisms of organic substances. In this study, we investigated the chlorine, carbon and hydrogen isotope fractionation patterns of chloroform during catalytic hydrodechlorination using two commercial catalysts palladium-on-alumina (Pd/Al2O3) and rhodium-on-alumina (Rh/Al2O3). The fractionation patterns of catalytic reaction were further compared to the pattern of reductive dechlorination of chloroform with zero valent iron (Fe0).
100 ml of deionized water in a reactor was saturated with hydrogen, which serves as an electron donor. The initial concentrations of chloroform and catalysts were designed to be 100 mg/l and 0.04 g/l, respectively. At specified time intervals, 1 ml of the water phase was taken from the reactor and placed in a 2 ml vial. Chlorine isotope analysis was implemented by GC-qMS (Agilent Technologies) coupled to a purge and trap sampler (PTA 3000, IMT GmbH) using the water phase from each 2 ml vial. For the carbon and hydrogen isotope analyses, a certain volume of the headspace in the 2 ml vial was injected into GC-C/Py-IRMS (Thermo Fisher Scientific).
The dual isotope slopes (ΛC-Cl = Δδ13C/Δδ37Cl) during the catalytic dechlorination of chloroform over Pd and Rh were determined to be 2.3 ± 0.12 and 2.1 ± 0.14, respectively. These values are significantly lower than the reported ΛC-Cl value of 8 ± 2 (Torrentó et al., 2017) and 8 ± 1 (Rodríguez-Fernández et al., 2018) for the reductive dechlorination of chloroform with ZVI. Our results indicate that the degradation mechanism of chloroform over Pd and Rh differs from the mechanisms with ZVI.
We further investigated the apparent kinetic isotope effects (AKIE) of carbon and chlorine isotopes. Whereas no significant difference was observed in AKIEC between degradation with catalysts and ZVI, AKIECl with Pd and Rh (1.037 and 1.032, respectively) are much higher than the theoretical limit for C-Cl bond cleavage (KIECl = 1.013) by Elsner et al., 2005. The large AKIECl with Pd and Rh suggest non-concerted, step-wise reaction, i.e. no intramolecular competition among the three chlorine atoms exists during the degradation process of chloroform, unlike concerted reaction that is known to take place during reductive dechlorination of chloroform with ZVI.
In summary, our study showed that 1) dual isotope slope and AKIE are useful tools to investigate degradation mechanisms and 2) chloroform degradation mechanism over Pd and Rh is assumed to be none-concerted, step-wise reaction based on the AKIE of Cl.
Key words: chloroform hydrodechlorination, Multi-dimensional CSIA, Palladium, Rhodium, Fe0
|12:15 - 13:00||Block 3: Paläoklima, Sedimentologie, Boden|
Virtueller Veranstaltungsort: Block 3 - Meeting Link
Chair der Sitzung: Matthias Hinderer, TU Darmstadt
Chair der Sitzung: Michael Zech, TU Dresden
Chair der Sitzung: Christine Stumpp, BOKU
12:15 - 12:30
Carbon isotope excursions in a Paleocene to early Eocene lignite bearing succession at the southern edge of the proto-North Sea (Schöningen, Germany)
1Senckenberg Forschungsinstitut und Naturmuseum Frankfurt, Deutschland; 2Technische Universität Darmstadt, Institut Für Angewandte Geowissenschaften, Deutschland; 3Senckenberg Biodiversity and Climate Research Centre (SBiK-F), Frankfurt am Main, Deutschland; 4Goethe Universität Frankfurt, Institut für Geowissenschaften, Frankfurt am Main, Deutschland; 5Stanford University, Department of Earth System Science, Department of Geological Sciences, USA
Long-term effects of present global warming on ecosystems on timescales beyond those covered by the human record of the last few centuries are still a matter of speculation. Since long-term greenhouse periods and short-term warming events occurred repeatedly in the history of the earth, they may be the subject for detailed studies on the reaction of ecosystems to global warming on different timescales. The Early Eocene Climatic Optimum (EECO) and its superposed short-term warming events such as the Paleocene-Eocene Thermal Maximum (PETM) represent the last greenhouse period before today which is especially suited for comparisons to the presently developing greenhouse since fauna and flora had reached an evolutionary state already similar to today.
The sedimentary succession of the former Helmstedt Lignite Mining District in northern Germany covers the entire Paleogene greenhouse phase and its gentle demise between the upper Paleocene and the early middle Eocene almost continuously in an estuarine situation at the southern edge of the proto-North Sea. Due to the interaction between changes in sea level, salt withdrawal in the subsurface and climate-related changes in runoff from the hinterland the area was subject to frequent changes between marginal marine and terrestrial conditions, repeatedly leading to peat formation. This offers the rare opportunity to study Paleocene–Eocene near-coastal ecosystems and to trace the effects of long- and short-term climate perturbations on the diversity and composition of the plant communities across 10 million years during the Paleogene greenhouse.
Here, we present high-resolution carbon isotope data of bulk organic matter (δ13CTOC) from a 98 m thick sequence from the lower part of the succession (Schöningen Formation). We observed six negative carbon isotope excursions (CIEs) reflecting massive short-term carbon cycle perturbations, which can be related to the PETM, probably to the Eocene Thermal Maximum 2 and to the EECO. Palynological analysis proved that shifts in δ13CTOC valuesare correlated with changes in the peat forming wetland vegetation. Furthermore, the PETM-related CIE shows a distinct rebound to higher δ13CTOC valuesshortly after the onsetof the CIE, which is here recognized as a common feature of terrestrial and marginal marine PETM-records worldwide and may be related to changes in the vegetation.
12:30 - 12:45
18O analyses of bulk lipids as novel paleoclimate tool in loess research – a pilot study
1Physische Geographie mit SP Paläoumweltforschung, Technische Universität Dresden, Deutschland; 2Institut für Grundwasserwirtschaft, Technische Universität Dresden; 3Bodenbiogeochemie, Martin-Luther-Universität Halle-Wittenberg; 4Universität Novi Sad, Serbien
The analysis of the stable oxygen isotopes 18O and 16O has revolutionized paleoclimate research since the middle of the last century. Particularly, 18O of ice cores from Greenland and Antarctica is used as paleotemperature proxy and 18O of deep-sea sediments is used as proxy for global ice volume. Important terrestrial archives to which 18O as paleoclimate proxy is successfully applied are for instance speleothems, lake sediments or tree rings. By contrast, 18O applications to loess-paleosol sequences (LPSs) are scarce, despite for instance a compound-specific 18O analytical tool for sugar biomarkers was developed and presented already years ago (Zech et al., 2014. Geochimica et Cosmochimica Acta 126, 614-623).
Here we present a first continuous 18O record (n=50) for the LPS Crvenka in Serbia, SE Europe, spanning the last glacial-interglacial cycle. From a methodological point of view, we took advantage of a recently proposed paleoclimate/-hydrological tool/proxy based on bulk 18O analyses of plant-derived lipids. The 18Olipid values range between -10.2 ‰ and +23.0 ‰ and are systematically more positive in the interglacial and interstadial (paleo-)soils compared to the loess layers. In our conference contribution, we compare our 18Olipid record from the LPS Crvenka with the marine oxygen-isotope stages as well as with the Greenland 18Oice core records revealing the famous Dansgaard-Oeschger events (stadials and interstadials). Concerning the interpretation of our LPS 18Olipid record, we will discuss several influencing factors, such as temperature-control on 18O, relative humidity-dependent evaporative leaf water enrichment, post-sedimentary effects and pool-effects.
Zech, M., Mayr, C., Tuthorn, M., Leiber-Sauheitl, K. and Glaser, B., 2014. Oxygen isotope ratios (18O/16O) of hemicellulose-derived sugar biomarkers in plants, soils and sediments as paleoclimate proxy I: Insight from a climate chamber experiment. Geochimica et Cosmochimica Acta 126, 614-623.
12:45 - 13:00
Plant and fungal contributions to soil organic matter fractions assessed by 13C and 15N isotope natural abundances
1Department of Agroecology, Bayreuth Center of Ecology and Environmental Research (BayCEER), University of Bayreuth, Germany; 2Department of Biology, Indiana University Bloomington, IN, USA; 3Department Soil Ecology, Bayreuth Center of Ecology and Environmental Research (BayCEER), University of Bayreuth, Germany; 4Chair of Soil Science, School of Life Sciences, Technical University of Munich, Freising, Germany; 5Soil Science of Temperate Ecosystems, Büsgen-Institute, Georg-August University Göttingen, Germany; 6Department of Geosciences and Natural Resource Management, University of Copenhagen, Denmark
Soil organic matter (SOM) consists of a multitude of organic compounds forming a continuum of decay, from fresh detritus to highly processed organic matter stabilized on mineral surfaces. To date, we still lack crucial knowledge about the contribution of plant and microbial residues to SOM fractions and we know almost nothing about the contribution of distinct fungal functional guilds such as arbuscular (AM), ectomycorrhizal (ECM), and saprotrophic (SAP) fungi to SOM fractions.
Aiming to address this knowledge gap, we investigated sources of particulate and mineral associated organic matter (POM and MAOM) around trees with distinct mycorrhizal types, Liriodendron tulipifera (AM association) and Quercus alba (ECM association), in a temperate deciduous forest in Indiana, USA. In ECM-associated systems, we expect ECM fungi to be the main contributors to SOM, while in AM-associated systems, SAP fungi will mainly contribute to SOM due to the facilitation by AM fungi.
To assess various sources of SOM fractions, we combined stable isotope natural abundance analyses with measurements of microbial residues using amino sugars. Specifically, the 13C and 15N signatures of large-, medium- and small-sized POM and MAOM fractions were analyzed and compared to that of leaves and roots of the two dominant tree species as well as to tissues of mycorrhizal and saprotrophic fungi. The sources of C and N to SOM fractions were calculated by a Bayesian inference isotope mixing model.
Our data revealed a shift from relatively 13C- and 15N-depleted POM, which is close to the isotopic composition of plant material, to 13C- and 15N-enriched MAOM. Mixing model calculations suggests a higher contribution of plant (~ 76 %) than fungal inputs to POM for both tree systems, with a higher contribution of saprotrophic (SAP) fungi than ectomycorrhizal (ECM) fungi (~ 17 % and ~ 5 %, respectively). In contrast, the model for MAOM fractions suggests a dominance of fungal residues relative to plant C, with SAP fungi contributing more than ECM fungi in most SOM fractions, even under the ECM tree. As expected, AM fungal residues contribute only little to SOM fractions. Microbial necromass - measured as amino sugars - confirmed the important role of ECM and SAP fungal residues for SOC storage in both, POM and MAOM fractions.
Overall, our results highlight the importance of distinct fungal functional guilds for soil C storage and call for future studies on the role of mycorrhizal types for soil C storage in a changing world.
|13:00 - 14:00||Mittagspause|
|13:30 - 14:00||Posterausstellung|
Virtueller Veranstaltungsort: Posterausstellung
|14:00 - 14:45||Vortrag Isotopenpreis|
Virtueller Veranstaltungsort: Isotopenpreis - Meeting Link
|14:45 - 15:30||Block 4.1: Ökosysteme|
Virtueller Veranstaltungsort: Block 4.1 - Meeting Link
Chair der Sitzung: Gerhard Gebauer, Universität Bayreuth
14:45 - 15:00
Orchid Cremastra appendiculata on the path to self-supply with changing fungal companion
1BayCEER – Laboratory of Isotope Biogeochemistry, University of Bayreuth, Bayreuth, Germany; 2Biology Department, National Museum of Natural Science, Taichung, Taiwan
Covering one achlorophyllous, leafless and three chlorophyllous, leafy species the orchid genus Cremastra from East Asia allows inference on the evolutionary development from autotrophy to mycoheterotrophy of plant lineages mycorrhizal with saprotrophic fungi (Ogura-Tsujita et al. 2021). Particularly, the chlorophyllous, terrestrial orchid Cremastra appendiculata is unique with respect to its fungal mycorrhiza partners. Rather specialized wood/litter-decaying saprotrophic fungi are known to induce seed germination in the initially mycoheterotrophic protocorm stage (Yagame et al. 2013), while adult individuals either exploit wood-decaying Psathyrellaceae being partially mycoheterotrophic (Suetsugu et al. 2021) or form mycorrhiza with fungi of the ubiquitous saprotrophic rhizoctonia group.
We examined how a change in fungal community and subterranean morphology accompanies a nutrition mode alteration during the life cycle of Cremastra appendiculata.
Trophic strategies were revealed by comparing different development stages of Cremastra appendiculata to surrounding autotrophic reference plants based on multi-element natural abundance stable isotope analyses (δ13C, δ15N, δ2H, δ18O) and total N concentrations. Here we present the first stable isotope patterns of tiny protocorms related to non-rhizoctonia saprotrophic fungal partners and 18O and 2H natural abundance isotopic signatures of fully mycoheterotrophic terrestrial orchid specimens associated with saprotrophic fungi. Mycorrhizal fungi in Cremastra appendiculata protocorms, rhizomes and roots of seedling, and roots of adult were determined using next generation DNA sequencing.
We identified saprotrophic non-rhizoctonia Psathyrellaceae as dominant mycorrhizal fungi in protocorm and seedling rhizomes, while roots of seedlings and mature Cremastra appendiculata were mainly colonizes with rhizoctonia fungi. Mature Cremastra appendiculata did not differ in isotopic signature from autotrophic reference plants suggesting a fully autotrophic nutrition mode. Characteristic of orchid specimens entirely relying on fungal nutrition, Cremastra appendiculata protocorms were enriched in 15N, 13C and 2H compared to reference plants. Seedlings with very early green leaves showed a dispersive, intermediate isotopic signature, underpinning their transitional nutrition mode and the differences in fungal community depending on their subterranean morphology.
In conclusion, chlorophyllous terrestrial orchid Cremastra appendiculata is a key species being able to feature both extremes on the continuous transition from autotrophy to mycoheterotrophy with changing fungal companion during its ontogenetic development. Our results on Cremastra appendiculata together with knowledge from recent literature (e.g. Suetsugu and Matsubayashi (2021)) suggest a high within-species variability in nutrition and fungal association depending on development stage and subterranean morphology of Cremastra appendiculata.
Ogura-Tsujita Y, Yukawa T, Kinoshita A. 2021. Evolutionary histories and mycorrhizal associations of mycoheterotrophic plants dependent on saprotrophic fungi. Journal of Plant Research 134: 19–41.
Suetsugu K, Haraguchi TF, Tayasu I. 2021. Novel mycorrhizal cheating in a green orchid: Cremastra appendiculata depends on carbon from deadwood through fungal associations. New Phytologist.
Suetsugu K, Matsubayashi J. 2021. Subterranean morphology modulates the degree of mycoheterotrophy in a green orchid Calypso bulbosa exploiting wood‐decaying fungi . Functional Ecology: 1–11.
Yagame T, Funabiki E, Nagasawa E, Fukiharu T, Iwase K. 2013. Identification and symbiotic ability of Psathyrellaceae fungi isolated from a photosynthetic orchid, Cremastra appendiculata (Orchidaceae). American Journal of Botany 100: 1823–1830.
15:00 - 15:15
Unravelling shoot:root drought responses in VOC emissions through 13C-pyruvate labelling
Chair of Ecosystem Physiology, Albert-Ludwigs-University of Freiburg, Germany
Plant shoots and roots reveal highly diverse and specialized metabolic adaptations to ensure plant survival above- and belowground while being faced by a multitude of external stressors. Plants hereby produce a plethora of biogenic volatile organic compounds (BVOCs) to communicate with their environment, e.g. to attract pollinators, repel herbivores or directly reduce effects of external stressors such as drought. Root and leaf metabolism are intertwined, with roots delivering minerals, nutrients and water, as well as carbohydrates to the leaves while receiving a multitude of metabolites from the leaves, including precursors for BVOC biosynthesis. Especially under drought stress, balanced resource allocation between leaves and roots is compromised. Even though many studies have focused on the complex dynamics of organ specific metabolome adaptations and changes in resource allocation under drought, little is known about metabolomic adjustments of BVOC biosynthesis of leaves relative to roots.
In our controlled climate chamber experiment, we aimed to unravel these dynamics by measuring compound-specific 13C-incorporation in BVOCs after position-specific ([1-13C]/[2-13C]-pyruvate) labelling of leaves and roots of potted, two-year old Fagus sylvatica and Picea abies saplings before and during drought stress, using flow-through chambers. BVOC emissions were measured online by PTR-TOF-MS in combination with GC-C-IRMS for further compound validation and 13C incorporation into specific monoterpenes. To quantify [1-13C]- and [2-13C]-pyruvate allocation into decarboxylation processes during primary and secondary metabolism, we used 13CO2 laser spectroscopy. Drought stress was determined by controlling soil moisture and measuring of plant physiological traits, such as leaf transpiration, assimilation rate and leaf water potential.
With this approach, we aim to identify active metabolic pathways responsible for BVOC biosynthesis in leaves and roots and how regulatory patterns changed due to drought. Considering our preliminary results, net CO2 assimilation, transpiration and respiration declined under drought. Overall BVOC composition and drought response, however, varied between organs in both species. Leaf emissions showed higher BVOC diversity even under drought. Monoterpene composition in leaves and roots of Fagus sylvatica differed and overall emissions were higher in roots. Contribution of de-novo synthesis of BVOCs in leaves was elevated due to storage depletion under drought in both species. Our results indicate major changes in BVOC emission pattern in leaves and roots under drought stress, providing first insights to elucidate drought-induced trade-offs in resource allocation into BVOCs above- and belowground.
15:15 - 15:30
Field 15N pool dilution approach to determine gross nitrification rate
Nitrification is the microbial oxidation of ammonium (NH4+) to nitrate (NO3–) and is one of the most important processes of the terrestrial nitrogen cycle. Nitrification is known to promote nitrogen leaching from soils as the less mobile cation ammonium (NH4+) is oxidized by nitrifiers to the mobile anion nitrate (NO3–). Additionally, nitrification promotes NO and N2O formation, directly as a by-product of nitrate formation and indirectly as a source of substrate for denitrification.
In numerous studies gross nitrification rates are determined using 15N pool dilution technique in laboratories, but only few field experiments with undisturbed soil structure were done. An appropriate in situ sprinkler method with a low irrigation rate and very even 15N-nitrate application was developed 2018 for sandy soils. The first test with a tracer solution confirmed that high amounts of the soil water can replaced from the top soil by applying a low irrigation rate by a special sprinkling device, and therefore all assumptions of the 15N-pool dilution technique can be fulfilled in the field by this method. Subsequently, the method was used to measure the small scale field heterogeneity (dm to m) and variability between field of gross nitrification at eight 3m*3m plots at sites with sandy soils (Fuhrberger Feld, northern Germany) in spring 2021. The results of the first application of the new method and der measurements in the Fuhrberger Feld will be shown. Different approaches to calculate the nitrification rates between two sampling dates t0 and t1 will be presented, and the heterogeneity of the nitrification rate will be discussed.
|15:30 - 15:45||Poster Kurzvorträge - Themenblock 3: Paläoklima, Sedimentologie, Boden|
Virtueller Veranstaltungsort: Poster Kurzvorträge - Meeting Link
15:30 - 15:33
Ein ~15 ka δ2Hn-alkane-Record vom Bichlersee, Oberbayern
1Physical Geography, Institute of Geography, Friedrich Schiller University Jena, Jena, Germany; 2Heisenberg Chair of Physical Geography, Institute of Geography, Technische Universität Dresden, Dresden, Germany
Die Alpen sind eine Schlüsselregion, um vergangene Veränderungen des Klimas und der atmosphärischen Zirkulation in Europa zu rekonstruieren. Biomarker- und komponentenspezifische Stabilisotopenanalysen in Seesedimenten bieten dabei großes Potenzial, sind aber bisher im Alpenraum kaum angewendet worden. Wir präsentieren neueste Ergebnisse vom Bichlersee, Oberbayern, die vor allem das Spätglazial hochaufgelöst (50 Proben) abdecken. Die Blattwachsmuster (n-Alkane) zeigen durchweg einen dominanten Eintrag langkettiger Homologe (C27 bis C33), also ein terrestrisches Signal (im Vergleich zu kürzerkettigen, aquatischen Homologen von Algen und Makrophyten). Die markante Abnahme der mittleren Kettenlänge von >30 auf <30 am Ende der Jüngeren Dryas hängt vermutlich mit der Wiederbewaldung zu Beginn des Holozäns zusammen. Die 2H-Isotopie der dominanten C29- und C31-Kettenlängen ändert sich sehr konsistent und nahezu stetig im Verlauf des Spätglazials von –180 auf –210‰, um dann im Holozän wieder auf positivere Werte anzusteigen. Auch wenn wir dies im Moment insbesondere auf eine Änderung der Niederschlagsisotopie zurückführen, können wir den Einfluss sich verändernder Vegetation – z. B. durch mehr Gräser während des Spätglazials – und evapotranspirativer Anreicherung nicht quantifizieren. Dazu sind für die folgenden Arbeiten komponentenspezifische 18O-Analysen an Zuckern geplant.
15:33 - 15:36
Last millennium hydroclimate variability from Lake Höglwörth, Bavaria, Germany
1Physical Geography, Institute of Geography, Friedrich Schiller University, Jena, Germany; 2Heisenberg Chair of Physical Geography, Institute of Geography, Technische Universität Dresden, Dresden, Germany
During the past decades, unusual rapid warming and significant changes in the precipitation seasonality and pattern have been recorded in almost the entire European Alps. To put these recent changes and climate projections into an adequate context, reconstructions of paleoenvironmental and –climate dynamics on a regional and local scale are prerequisite. Moreover, paleoenvironmental studies help to identify drivers and forcings of past (hydro)climate variability. In this study we present a high resolution continuous environmental and hydroclimatic record from a small forealpine lake “Lake Höglwörth” (Bavaria, Germany), covering the past millennium based on n-alkanes and their compound-specific isotopic composition (δ2H). The relatively high abundance of C27 to C33 indicates input from higher terrestrial plants, but also abundance of C23 and C25 document the presence of aquatic plants, particularly from AD 1100 to 1300, between AD 1550 and 1750, as well as since 1850. C29 and C31 reveal very similar isotopic (δ2H) signal and down-core trends. They are relatively enriched (~ -202.1 ‰ for C31) between AD 1100 and 1450 with maximum enrichment (~ -180 ‰ for C31) between AD 1200 and 1300. Rather depleted values (~ -210 ‰ for C31) are found from AD 1450 to 1650, however, an enrichment is obvious after 1650. Due to the primarily origin of the C29 and C31 in terrestrial vegetation, we assume that δ2H of these n-alkanesmainly reflects past changes in the isotopic composition of precipitation. However, effects related to changing vegetation and evapotranspirative enrichment cannot be ruled out. However, C23 is variably enriched compared to C29 and C31, and we suggest that this reflects the evaporative enrichment of the lake water and might thus enable to calculate relative humidity. We are now aiming to (i) increase the temporal resolution (continuous ~ decadal), (ii) compare our results to other regional records, and (iii) establish high-resolution d18O records from sugar biomarkers in order to more robustly disentangle the various factors influencing the isotopic composition of the leaf waxes.
15:36 - 15:39
Ca isotope partitioning upon experimental precipitation of carbonated hydroxy-apatite (CHAP)
1Institut für Mineralogie, Westfälische Wilhelms Universität Münster; 2Leibniz Institute of Baltic Sea Research and University of Greifswald, Deutschland; 3Institute of Geosciences, Goethe-University of Frankfurt, Germany, and Senckenberg Biodiversity and Climate Research Center, Frankfurt (Main), Germany; 4Economic Geology, University of Greifswald, Germany; 5Department of Experimental and Applied Mineralogy, Georg-August-University of Göttingen, Germany
Carbonated hydroxy-apatite (CHAP) was experimentally synthesized in batch-type set-ups by mixing of calcium (Ca)- and phosphate-bearing aqueous solutions and the transformation of calcite powder in aqueous solution between 11° and 65°C (Gussone et al., 2020). Compositional changes of the experimental solution and solid phase products were followed by elemental analysis, Raman spectroscopy, scanning-electron microscopy, and powder XRD. In the mixing experiments, crystallization of CHAP took place following the precipitation of metastable brushite as precursor that was then transformed into CHAP. In the transformation experiments using synthetic calcite as a precursor phase it was found that the reaction at pH values between 7.5 and 7.9 occurs via the direct replacement of calcium carbonate by CHAP.
Calcium isotope fractionation led to an enrichment of the light isotope in the solid CHAP compared to the aqueous solution by about -0.5 to -1.1 ‰, independent from the experimental approach, and the magnitude was essentially independent of temperature. The metastable brushite formed prior to transformation to CHAP showed a reduced fractionation compared to the CHAP. The observed Ca isotope fractionation into the CHAP lattice resembles that of natural phosphorites and lies within the range of the view existing theoretical and experimental studies.
Reference: Gussone N., Böttcher M.E., Conrad A.C., Fiebig J., Pelz M., Grathoff G., Schmidt B.C. (2020) Calcium isotope fractionation upon experimental apatite formation. Chem. Geol., 551, 119737
The study was supported by German Science Foundation (DFG) to M.E.B and J.F. within the EXCALIBOR project (BO1548/8 and FI 948/7), and to N.G. (GU1035/10), and by Leibniz IOW.
15:39 - 15:42
Stable isotopic and trace elemental fingerprints in carbonate precipitated by modern hard-water creeks of the temperate climate zone
1Leibniz Institute of Baltic Sea Research, FRG; 2Marine Geochemistry, University of Greifswald, FRG; 3Present address: Hydroisotop, Schweitenkirchen, FRG; 4Naturhistorisches Museum, Berlin, FRG; 5Applied Geology, University of Greifswald, FRG; 6Ecoandmore, Freiburg, FRG
Processes in the dissolved carbonate system of surface waters may contribute and are sensitive to variations of boundary conditions associated with climate change. Carbon dioxide super- and calcium carbonate -saturated ground waters that emerge from springs lose dissolved carbon dioxide to the atmosphere; this process leads to the development of CaCO3 supersaturation of the aqueous solution. When exceeding a critical value, solid carbonates precipitate, thereby linking the past marine with the present terrestrial carbon cycles. The associated distribution of trace elements and stable isotopes leads to proxy formations. The magnitude of trace element and isotope fractionations is linked to non-equilibrium processes, impacted by the initial solution composition, hydrodynamics, and possible biological activity in the stream beds.
Two examples of recent sinter formation from streams in the temperate climate zone were investigated: Site R is positioned in a cliff zone of Rügen Island, southern Baltic Sea and Site W near Westerhof in the south-western Harz foreland. Two phases of surface water development can be differentiated: An induction period starting at the spring, where only degassing of carbon dioxide takes place, and a second stage where calcite formation from the highly supersaturated solution is continuously driven by further degassing. The liberation of CO2 is associated with an enrichment of the heavy carbon isotope in the remaining dissolved inorganic carbon. By following the isotope and trace element composition of aqueous solutions and recent calcite precipitates along the flow path, distribution coefficient (Li, Na, Mg, Sr, Ba, SO4, 13C, 18O) are derived. The empirical quantitative observations at Site W can be compared with observations dating back to the late 60s of the last century. Those at Site R are compared to results from laboratory experiments using the natural water as starting solution. Furthermore, the distribution coefficients are compared to calibrated experimental studies to estimate calcite precipitation rates. Trace-element based rate estimates for Site W are higher than published direct measurements, which is likely due to hydrodynamic boundary conditions impacting the in-situ growth experiments. Idiomorphic BaSO4 was observed in recent carbonate sinter at Site W for the first time, which is in agreement with slight supersaturations modeled for the stream water.
At the bottom of the cliff (Site R), the carbonate stream water is finally entering the Baltic Sea where mixing with brackish surface waters occur. The excess in dissolved CO2 compared to the atmosphere is enhancing the degassing capacity in the mixed coastal waters.
15:42 - 15:45
Identification of paleosols of a Namibian sediment core (WW203303) using pedogenic features, trace fossils and stable isotope compositions
1TU Darmstadt, Deutschland; 2Federal Institute for Geosciences and Natural Resources, Geozentrum Hannover
Stable carbon and oxygen isotopes of carbonates from paleosols can be used as proxies to reconstruct paleoclimate and paleoenvironment conditions (Cerling & Quade, 1993). Paleosols are identified from the Namibian sediment core WW203302 (Houben et al., 2020) using stable isotopes, pedogenic features and a conceptual model generated by Hasiotis et al. (2012). Pedogenic features such as nodules, mottling and peds are clear indexes for paleosol in sediment. However, these features appear only sporadically in this 400 m long sediment core, trace fossils are used as index to distinguish paleosols from sediment.
Bioturbation patterns generally created by trace fossils occur nearly in the entire sediment core. Density, abundance, and depth of bioturbation follow the degree of soil development (Hasiotis et al. 2012). Pedogenesis, bioturbation and sedimentology are criteria to classify paleosols in sediment sections, from which nodules were selected, into compound, composite, and cumulative fractions (Kraus, 1999). Stable carbon and oxygen isotopes of bulk samples from different types of paleosols are compared to that of nodules to examine whether bulk samples from this sediment core can be used for paleoclimate interpretations.
The δ13C values of all types of bulk samples show basically the same trend as nodule samples (r2=0.88), bulk samples from well-developed paleosols, compound and composite paleosols show a better correlation to corresponding nodule samples than cumulative paleosols and phreatic layers for δ18O values (r2=0.64). Covering sands of nodule samples are more negative than corresponding nodules for δ18O, but either more negative or positive than nodules for δ13C, regardless of soil types. Furthermore, dolomites as a component of nodule samples, are generally more enriched in δ18O and mostly depleted in δ13C, regardless of soil type.
Cerling, T. E., & Quade, J. (1993). Stable Carbon and Oxygen Isotopes in Soil Carbonates. 217–231.
Hasiotis, S. T., & Platt, B. F. (2012). Exploring the sedimentary, pedogenic, and hydrologic factors that control the occurrence and role of bioturbation in soil formation and horizonation in continental deposits: An integrative approach. The Sedimentary Record, 10(3), 4–9
Houben, G. J., Kaufhold, S., Miller, R. M. G., Lohe, C., Hinderer, M., Noll, M., Hornung, J., Joseph, R., Gerdes, A., Sitnikova, M., & Quinger, M. (2020). Stacked megafans of the kalahari basin as archives of paleogeography, river capture, and cenozoic paleoclimate of Southwestern Africa. In Journal of Sedimentary Research (Vol. 90, Issue 9)
Kraus, M. J. (1999). Paleosols in clastic sedimentary rocks: Their geologic applications. Earth Science Reviews, 47(1–2), 41–70.
|15:45 - 16:00||Pause|
|16:00 - 17:30||Block 4.2: Ökosysteme|
Virtueller Veranstaltungsort: Block 4.2 - Meeting Link
Chair der Sitzung: Gerhard Gebauer, Universität Bayreuth
16:00 - 16:30
Carbon isotope ratio as a measure of photosynthetic water-use efficiency: reconciling a biophysical discrepancy
SLU, Swedish University of Agricultural Sciences
In most plants, d13C of their tissues provides an estimate of the carbon:water exchange, or water-use efficiency, of photosynthesis. This is important because photosynthesis and transpiration represent an important evolutionary trade-off for plants, but also because they link two major parts of the ecosystem carbon and water cycles. The discovery that this trade-off could be quantified with d13C led to a burst of research in fields as diverse as plant breeding, ecosystem ecology, and global climate change. However, there was always some concern that the predicted isotopic composition did not exactly match biophysical theory, which was essentially a Rayleigh distillation model with a strong enzymatic fractionation. The discrepancy favoured overestimates and was approximately as large as the isotope effects under study, leading to some scepticism about the isotopic technique. I will review proposed explanations for the discrepancy, ending with the recent convergence on mesophyll conductance. Mesophyll conductance can now be measured with high precision in the field, offering a mechanistic adjustment leading to water-use efficiency estimates with high precision and accuracy. Eliminating this discrepancy returns d13C to a position of credibility as a measure of the linkage between carbon and water fluxes of plant leaves and canopies.
16:30 - 16:45
Impact of nutrient and water availability on grassland functioning - achieving a process based understanding across scales
1Zalf, Deutschland; 2Uni Freiburg, Deutschland; 3FZ Jülich, Deutschland
Two important threats to the sustainable functioning of seminatural grasslands in temperate zones are (1) nutrient loading due to agricultural fertilization and pollution, and (2) the increase of extreme drought events due to climate change. These threats may cause substantial shifts in species diversity and abundance and considerably affect the carbon and water balance of ecosystems. The synergistic effects between those two threats, however, can be complex and are poorly understood. Here, we experimentally investigated the effects of nitrogen addition and extreme drought (separately and in combination) on a seminatural temperate grassland, located in Freiburg (South Germany). To study the grassland response, we combined eddy-covariance techniques, open gas exchange systems from the leaf to the plot scale with biomass and beiodiversity assessments. Open gas exchange chambers were connected to an infrared gas analyzer and water isotope spectrometer, which allowed the partitioning of net ecosystem exchange and evapotranspiration. Vegetation parameters were described by species richness, species abundance, and leaf area index. Our results suggest that grassland communities, strongly weakened in their stress response by nitrogen loading, can substantially lose their carbon sink function during drought. While nitrogen addition caused a significant loss in forb species (−25%), precipitation reduction promoted a strong dominance of grass species at season start. Consequently, the grass-dominated and species-poor community suffered from a strong above-ground dieback during the dry summer months, likely caused by lower water use efficiency and weaker drought adaptations of the species community. Over the growing season (April-September), the carbon sequestration of the studied grassland was reduced by more than 60% as a consequence of nitrogen addition. Nitrogen addition in combination with precipitation reduction decreased carbon sequestration by 73%. Eutrophication can severely threaten the resilient functioning of grasslands, in particular when drought periods will increase as predicted by future climate scenarios. Our findings emphasize the importance of preserving high diversity of grasslands to strengthen their resistance against extreme events such as droughts.
16:45 - 17:00
Application of 2-dimensional stable isotope measurements of methane to constrain sources and sinks in a seasonally stratified freshwater lake
1Institute of Earth Sciences, Heidelberg University, Heidelberg, Germany; 2MARUM – Center for Marine Environmental Sciences and Department of Geosciences, University of Bremen, Bremen, Germany; 3Institute for Plant Nutrition, Justus Liebig University, Giessen, Germany; 4Heidelberg Center for the Environment (HCE), Heidelberg University, Heidelberg, Germany
Supersaturation of methane (CH4) in the oxic surface water layer of lakes has been suggested to play an important role in releasing CH4 to the atmosphere and emissions are predicted to increase with future climate change. Microbial CH4 oxidation in limnic systems as a counteracting sink has the potential to efficiently diminish CH4 effluxes. In this study, sources and sinks of CH4 were investigated in a seasonally stratified, eutrophic lake in southwestern Germany during summer using carbon and hydrogen stable isotope measurements.
In the lake water body, aerobic CH4 oxidation at the oxic-anoxic interface increased in intensity with rising CH4 concentrations over summer. This was accompanied by a strong increase in stable carbon and hydrogen isotope values of the CH4 pool. Incubation experiments with 13C-labeled CH4 revealed CH4 oxidation rates varying between 49-106 nM/d. In the lake sediment, anaerobically produced CH4 was reduced in its concentration through microbial anaerobic CH4 oxidation in sulfate-methane transition zones possible due to high sulfate concentrations in the lake (~2 mmol/l). The decrease in upward migrating sedimentary CH4 was partly accompanied by increasing stable carbon and hydrogen isotope values.
Sources of CH4 were characterized using a novel isotope indicator Δ(2,13) recently introduced by Tsunogai et al. (2020), which is based on dual isotope characterization of CH4 and corrects for isotopic fractionation effects caused by CH4 oxidation. Surface water CH4 showed different Δ(2,13) values if compared with CH4 from the hypolimnion and sediment and was furthermore distinguishable from littoral Δ(2,13) values. In order to investigate the occurrence of oxic CH4 production in the surface water layer, an incubation experiment was performed with 13C-labeled methylphosphonate, a known precursor substrate for aerobic CH4 formation, which showed a strong increase in the stable carbon isotopic composition of CH4 over time. In conclusion, our results strongly indicate internal oxic CH4 production by aerobic organisms as a possible source of excess CH4 in the surface water layer of the lake.
Tsunogai, U. et al. 2020. Dual stable isotope characterization of excess methane in oxic waters of a mesotrophic lake. Limnol. Oceanogr. 65: 2937–2952.
17:00 - 17:15
Belowground C allocation of tropical rainforests in response to drought: an ecosystem 13CO2 labeling approach
1Biogeochemistry of Agroecosystems, Department of Crop Science, Faculty of Agriculture, Georg August University of Göttingen; 2Ecosystem Physiology, University of Freiburg, Freiburg, Germany; 3School of Natural Resources and the Environment, University of Arizona, Tucson, United States of America; 4Biosphere 2, University of Arizona, Tucson, United States of America
Drought affects carbon (C) sources and sinks in forest ecosystems, with potential consequences for belowground C allocation, a vital process of the terrestrial C cycle. However, the extreme drought impacts on the ecosystem are poorly understood, particularly in the tropical rainforests. Within the framework of our large-scale ecosystem manipulation experiment on "Rain Forest Water, Atmosphere, and Life Dynamics" (WALD) at the Biosphere 2 in Arizona, we conducted a whole ecosystem stable isotope labeling with atmospheric 13CO2 to gain in-depth insights into tree belowground C allocations and the C partitioning at the soil–microbe-root interface under ambient conditions and drought stress. In particular, we hypothesized that key drought-adaptation strategies would include i) increased C allocation into subsoil layers that drought down slower than topsoil and ii) increased C investment into rhizodeposits and mycorrhizal fungi. Our data on tree C allocation highlight that drought stress increased the proportion of recently assimilated C translocated into the roots in both the top- and sub-soil with no correlation of C allocation with soil water content or root biomass. In response to drought, the rhizodeposition, and thus allocation of assimilated C into rhizospheres soil, was reduced in topsoil but increased in subsoil. However, we found pronounced plot-specific differences in belowground C allocation, especially between plots with only understory plants vs those with tall trees, suggesting species-specific drought response strategies. However, generally our observations underline that trees attempt to invest assimilated C into the deeper soil layers’ roots and rhizosphere to access subsoil resources. The C investment into deeper soil layers and the absence of any correlation with root biomass suggest that drought adaptation strategies are based on rhizomicrobial mechanisms rather than on C investment into root growth. The upcoming results of 13C incorporation into phospholipid fatty acids will provide further insights into microbial C utilization in the rhizosphere and complete our picture of belowground drought adaptation strategies. In summary, quantification of tree C belowground allocation patterns at the plant-microbe-soil interface will enable us to disentangle belowground drought response strategies of tropical rainforests.
|17:30 - 19:00||ASI Mitgliederversammlung|
Der Link zur Mitgliederversammlung wurde allen Mitgliedern per Mail zugesandt. Bitte schauen Sie in Ihrem Postfach nach.
|17:30 - 19:00||Posterausstellung|
Virtueller Veranstaltungsort: Posterausstellung
|Datum: Mittwoch, 29.09.2021|
|9:00 - 9:30||Posterfrühstück|
Virtueller Veranstaltungsort: Posterausstellung - Meeting Link
|9:30 - 10:30||Block 6: Physiologie, Metabolismus, Medizin, Doping, Forensik, Lebensmittel|
Virtueller Veranstaltungsort: Block 6 - Meeting Link
Chair der Sitzung: Frank Keppler, Universität Heidelberg
9:30 - 9:45
Stable isotopes for planetary health: Synthetic methionine
University of Colorado Boulder, USA
Methionine is an amino acid that humans and farm animals must derive from food. This metabolite, a tightly regulated resource in ecosystems, has become a mass commodity in the global economy, with well over 1 million tons being produced annually from petroleum to fortify livestock feed. Methionine synthesis is an excellent exemplar of a planetary scale anthropogenic activity that manifests at the molecular scale of cellular metabolism, with potential systemic effects on human health and environments. Taking a planetary health perspective, I will explore in this talk the scale and historical trajectory of the methionine industry and provide a preliminary model for tracing this amino acid through the food supply into the human body. We now want to test this model empirically using isotope analytics to quantify the synthetic proportion of methionine in foods and humans. The proposed approach is to use a mass spectrometry method developed in the last five years that is based on ESI-Orbitrap. It can reveal intramolecular stable isotope compositions of organic molecules at the natural abundance level. I will also briefly discuss alternative isotope approaches for this project, as well as highlight topics where the new stable isotope technology might contribute insights in a biomedical context.
1. Neubauer C, Landecker H (2021) A planetary health perspective on synthetic methionine: Implications of opening the tap on a historically limiting nutrient. Lancet Planet Health
2. Neubauer C, Sweredoski MJ, Moradian A, Newman DK, Robins RJ, Eiler JM (2018). Scanning the isotopic structure of molecules by tandem mass spectrometry. Int J Mass Spec
9:45 - 10:00
Carbon isotope ratios of endogenous steroids found in human serum – method development, validation, and reference population-derived thresholds
Deutsche Sporthochschule Köln, Deutschland
In order to detect the misuse of testosterone (T) and testosterone prohormones, urinary steroids and steroid ratios are quantified and monitored in a longitudinal manner to enable the identification of atypical samples. These suspicious samples are then forwarded to isotope ratio mass spectrometry (IRMS)-based methods for confirmation. Especially concentration ratios like T over epitestosterone (E) or 5α-androstanediol (5αAdiol) over E proved to be valuable markers. Unfortunately, depending on the UGT2B17 genotype and/or the gender of the athlete, these markers may fail to provide evidence for T administrations when focusing exclusively urine samples.
In recent years, the potential of plasma steroids has been carefully investigated, which were found to be suitable to detect T administrations especially in female volunteers.[1-5] A current drawback of this approach is the missing possibility to confirm that elevated steroid concentrations found in plasma are solely derived from an administration of T or T-prohormones and cannot be attributed to possible confounding factors. Therefore, and in parallel to the procedure applied to urine samples, an IRMS method for plasma steroids has been developed and validated taking into account the limited sample volume for serum samples (usually not more than 1 mL). As endogenous reference compounds, unconjugated cholesterol and dehydroepiandrosterone-sulfate were found suitable while androsterone and epiandrosterone (both sulfoconjugated) were chosen as target analytes.
The method was based on multi-dimensional gas chromatography coupled to IRMS in order to increase recovery compared to liquid chromatography-based sample clean-up. The method was validated employing linear mixing models, and finally a reference population encompassing n = 65 males and females was investigated to enable the calculation of population-based thresholds. As proof-of-concept, several serum samples from volunteers participating in T-replacement therapies were analyzed and found to be significantly depleted in their serum steroid target analytes.
1) Ponzetto F, Mehl F, Boccard J, et al. Anal Bioanal Chem 2016; 408: 705-719
2) Handelsman DJ, Bermon S. Drug Test Anal 2019; 11: 1566-1571
3) Elmongy H, Masquelier M, Ericsson M. J Chrom A 2020; 1613: 460686
4) Salamin O, Ponzetto F, Cauderay M, et al. Bioanalysis, 2020, DOI: 10.4155/bio-2020-0046
5) Knutsson JE, Andersson A, Baekken LV, et al. J Clin Endocrin & Metab 2020, DOI: 10.1210/clinem/dgaa904
6) Putz M, Piper T, Casilli A, et al. Analytica Chimica Acta 2018; 1030: 105-114.
10:00 - 10:15
Making plant methane formation visible – the effect of light exposure and light intensity on plant methane formation by application of 13C-labelled dimethyl sulfoxide
1Heidelberg University, Heidelberg, Germany; 2Bingen University of Applied Sciences, Bingen, Germany; 3Center for Organismal Studies, Heidelberg, Germany; 4Heidelberg Center for the Environment, Heidelberg University, Germany
In recent years methane (CH4) formation by vegetation in the presence of oxygen has been studied intensively, but its underlying formation process(es) are still poorly understood. Currently, reported CH4 emission rates vary by orders of magnitude and thus make global estimates of CH4 emissions by vegetation difficult. In addition, the process(es) of plant CH4 formation are mostly unknown. In this presentation, we introduce a new approach for a making CH4 formation by plants visible. By application of 13C-labelled dimethyl sulfoxide (DMSO) onto the leaves of tobacco plants (Nicotiana tabacum) and Chinese silver grass (Miscanthus sinensis), DMSO was identified as a precursor of CH4 in plants and the effect of light on CH4 formation was examined by measuring δ13C-CH4 values during incubations via Cavity Ring-Down Spectroscopy.
Both plant species clearly showed an increase in δ13C-CH4 values, and therefore CH4 formation, during the incubations while exposed to light. Higher light intensities lead to higher CH4 formation rates in N. tabacum and to lower CH4 formation rates in M. sinensis. When examined in the dark no formation of CH4 could be detected for N. tabacum, whilst M. sinensis still produced around 50 % of CH4 in the dark when compared to light exposure. Our findings unambiguously confirm DMSO as a precursor of plant CH4 and suggest that CH4 formation in plants is highly dependent on light exposure, light intensity, and plant species. Furthermore, our work presents a new isotopic approach for investigating mechanisms of CH4 formation in plants which has the potential to identify the underlying physiological processes, that without the use of stable isotopes could not be solely determined by CH4 concentration measurements.
10:15 - 10:30
Geographical provenance determination of wood through combination of isotope ratios
1Thünen-Institut für Forstgenetik, Deutschland; 2Thünen-Institut für Agrarklimaschutz, Deutschland
As illegal logging develops more and more into a global problem, analytical methods to proof timber origin are necessary. In two pilot studies wood samples were collected to examine the possibilities of provenance determination of wood with stable isotope analyses as an addition of the “Large Scale Project” to develop genetic reference data to identify timber origin. The project was led by the Thuenen-Institute of Forest Genetics. In the first pilot study, wood samples of the tree species Carapa guianensis and Hymenaea courbaril were collected on a country scale at five locations for both species and an additional location for Hymenaea courbaril in Brazil with multiple 100 km distances up to 3,000 km between the geographical groups (locations) (Large Scale). The second pilot study addressed the regional scale in three different countries (Small Scale). In a range of 100 km wood samples were gathered for Hymenaea courbaril and H. jutai in two forest concessions in Brazil and for Dipteryx ferrea in Peru and Lophira alata in Cameroon in three concessions each. Forest concession are areas where logging companies received the permission for timber harvest from the state.
In the Large Scale study most isotope ratios showed differences between the geographical groups with most differences being statistical significant. Furthermore, weak significant correlations with latitude and longitude for d18O were observed, for d13C and d2H only with longitude and d15N correlated weakly with latitude. In a statistical self-assignment, the success rate in total was 59% for Carapa guianensis and 54% for Hymenaea sp.. Nevertheless the locations in Brazil were not distinguishable from each other in a principal component analysis.
In the Small Scale study, the isotope ratios of C and N, measured so far, did not allow for a significant separation of forest concession nor did they show significant correlation with latitude or longitude.
In conclusion there seems to be a geographical signal in the isotope results of the different location for the four isotope ratios of C, N, O and H but it was not strong enough for a secure geographic assignment. As next steps we want to check the performance of a combined application of gene markers and stale isotopes for geographic assignment of timber. Sampling design and lab methods also offer space for optimisation.
|10:30 - 10:50||Poster Kurzvorträge - zu Themenblock 4; 1; 5|
Virtueller Veranstaltungsort: Poster Kurzvorträge 4;1;5 - Meeting Link
Block 4: Ökosysteme
Block 1: Analytik, Methoden, Technik und Qualitätssicherung stabiler Isotope
Block 5: Klima und Atmosphäre
10:30 - 10:33
Using in-situ and destructive measurements of stable water isotopes to quantify ecohydrological feedback processes of different forest stands
Albert-Ludwigs-Universität Freiburg, Professur für Hydrologie, Deutschland
Stable water isotopes are a promising tracer for studying water movement through ecosystems. Traditionally, destructive sampling techniques are applied to measure the isotopic signature in soils and plant xylem but these methods are limited in their temporal resolution and have proven to be fraught with uncertainty. Recent development of in-situ membrane-based probes for direct measurements of soil and tree xylem water isotopes (SWIP) allow continuous observations along soil profiles or within trees at different heights. Such new in-situ measurements provide an unprecedented combination of high temporal and spatial resolution data. Also, by using the same probes for the soil as well as the plant compartment, all measurements can be compared directly.
Here, we present preliminary results of our in-situ isotope measuring platform from different forest stands in the Black Forest (Germany). The measurement setup encompasses three experimental treatments: i) pure beech, ii) pure spruce and iii) mixed beech and spruce stands. By measuring soil water in different depths as well as xylem water at different heights, we will not only identify species-specific differences in their water uptake patterns but also the impact of interspecific competition for water. Additional destructive measurements of stable water isotopes from throughfall, stemflow, soil and tree xylem water will be used to gain further information but also to compare in-situ with destructive isotope measurement techniques.
10:33 - 10:36
Antibiotics increase methane production rates in freshwater sediments: Evidence from an anaerobic incubation
1iES Landau, Institute for Environmental Sciences, University of Koblenz-Landau; 2Eusserthal Ecosystem Research Station, University of Koblenz-Landau; 3Department of Molecular Ecology, University of Technology Kaiserslautern; 4Department of Aquatic Sciences and Assessment, Swedish University of Agricultural Sciences
Methane (CH4) is after carbon dioxide (CO2) the second most important greenhouse gas and is inter alia produced in natural freshwater ecosystems. In the face of increasing CH4 emissions from natural sources, researchers have investigated environmental factors and climate change feedbacks to explain this increment. Despite being omnipresent in freshwaters, knowledge on the influence of chemical stressors of anthropogenic origin (e.g. antibiotics) on methanogenesis is not present to date. To address this knowledge gap, we incubated freshwater sediment for 42 days under anaerobic conditions in presence of a five-component antibiotic mixture at four levels (from 0 to 5000 µg/L). Weekly measurements of CH4 and CO2 in the headspace showed that the CH4 production rate can be increased by up to 94% at 5000 µg/L and up to 29% at field-relevant concentrations (i.e., 50 µg/L). The compound-specific δ13C values of CH4 and CO2 indicate that the processing dynamics are changed while the successional stages are not. Despite the complications of transferring experimental CH4 production rates to realistic field relevant CH4 emissions, the study suggests that chemical stressors contribute to the emissions of greenhouse gases by affecting the methanogenesis in freshwaters.
10:36 - 10:39
Exploring fundamentals of quantitative 13CO2/12CO2 tracer studies of CO2 exchange and biomass in plants: assessment of system performance and determination of isotopic end-members for mixing model
Technical University of Munich, Deutschland
Labelling with carbon isotopes is the technique of choice to study carbon dynamics in plants, including CO2 exchange, biomass and carbohydrates. Labelling experiments consist of two phases: An establishment phase, where plants are grown in the presence of CO2 with constant isotopic composition, and a labeling phase, where the establishment CO2 is replaced by a CO2 with differing isotopic composition. However, labelling systems can be prone to technical artifacts like contamination with extraneous CO2, fluctuations of the isotopic composition of the establishment and labelling CO2 etc. Also, the accurate determination of carbon tracer kinetics requires an accurate determination of the two end-members for isotopic mixing models. So far, systematic testing of labelling systems has been rare and incomplete. Here, we present details of a chamber labelling system for plant mesocosms and the analysis of its performance with respect to possible technical artifacts. This also includes the analysis of different approaches for the end-member determination. We performed labelling experiments with perennial ryegrass (Lolium perenne L.) combined with 13CO2/12CO2 gas exchange and carbohydrate measurements, in growth chambers under three CO2 concentrations: 200, 400, and 800 mmol mol-1. Each treatment was run in two growth chambers, with identical growth conditions but with two different CO2 sources (13C-depleted: δ13C -43.5 ‰ or 13C-rich: δ13C -5.6 ‰). After the establishment phase, the CO2 supplied to each chamber was switched from depleted to enriched or vice versa for a 7 days-long labelling phase. When gas exchange rates were approximately steady on a day-by-day basis, CO2 concentrations and δ13C in the chambers were also virtually constant over time. The spread in δ13C of the CO2 sources during the establishment phase matched the spread in δ13C of the two CO2-sources at the chamber outlets at all CO2 concentrations, showing that chamber CO2 was not contaminated with extraneous CO2. This was also confirmed by the close correspondence of C-isotope discrimination (Δ) during gas exchange in the light at every CO2 concentration. However, due to inevitable opening of the chambers during maintenance and plant sampling operations, Δ determined on respiratory CO2, shoot and root biomass as well as shoot carbohydrates was slightly (1.1 ‰), but consistently (P < 0.01) smaller in the 13C-depleted relative to the 13C-rich CO2 chambers during the establishment phase. Thus, for precise analyses of tracer kinetics in respiratory CO2, biomass or carbohydrates, the determination of the end-members of the mixing model had to be based on sample type-specific Δ measurements.
10:39 - 10:42
Unravelling the diet of extinct cave bears in Romania using δ15N isotopic analysis of amino acids
1Senckenberg Gesellschaft für Naturforschung, Deutschland; 2Universität Tübingen, Deutschland; 3Nagoya University Museum, Japan
Compound specific isotopic analysis of individual amino acids (CSIA-AA) was performed to unravel dietary information on Late Pleistocene cave bears (Ursus spelaeus). In contrast to other regions of Europe, U. spelaeus from Romaniashowed variable and exceptionally high δ15N values (5.2 to 9.8‰) that leads to speculation of meat consumption. The CSIA-AA approach used is unique in that it offsets the natural baseline δ15N variation (e.g. environmental, behavioural or physiological traits). It can thereby provide a more accurate estimate of trophic position (TP).
Amino acids from ancient bone collagen of U. spelaeus were derivatized, separated via gas chromatography, combusted/reduced, then measured for δ15N using stable isotope mass spectrometry (GC-C-IRMS). This method is based on the differential fractionation of two amino acid groups: trophic AAs (i.e., glutamic acid) that fractionate 15N greatly (~8.0‰) compared to source AAs (i.e., phenylalanine) that fractionate 15N very little (~0.4‰) per trophic step. The latter (δ15Nphe) thus reflects the nitrogen source baseline (i.e. the primary producers) of the ecosystem.
Results rule out (i) significant dietary aquatic resources; (ii) carnivory as the main feeding behaviour. Rather, TPs of 1.8–2.2 (N = 6) are indicative of a plant-dependent diet, including for those cave bears with high bulk δ15N values. Using CSIA-AA, TPs of 1.9-2.1 were determined for U. spelaeus confirming a pure herbivorous diet (see Figure 1). Bulk collagen δ15N values of can be explained by (i) a δ15N shift of the baseline in the local ecosystem, and/or (ii) the consumption of some specific plants with high δ15N values. Our findings have interesting implications regarding the evolution of herbivory among carnivorans. Furthermore, understanding feeding behaviour of U. spelaeus may provide key insights into their extinction.
We used an Agilent 7890B GC coupled to an Elementar GC5 Interface module in line with a reduction furnace, cryogenic trap (LN2) and an IsoPrime 100 IRMS.
Naito, Y.I., Meleg, I.N., Robu, M. et al. Heavy reliance on plants for Romanian cave bears evidenced by amino acid nitrogen isotope analysis. Sci Rep 10, 6612 (2020). https://doi.org/10.1038/s41598-020-62990-0
10:42 - 10:45
Development of an open-split-based dual-inlet system for mass spectrometers
1Universität Bern, Schweiz; 2Oeschger Centre for Climate Change Research
The inlet system integrated into the Elementar isoprime precisION is a changeover-valve-based dual-inlet system which is not ideally suitable for high-precision measurements of elemental and stable isotope ratios. In order to attain higher precisions an open-split-based dual-inlet system was designed and built by the Climate and Environmental Physics Division of the University of Bern featuring almost no metallic surfaces and altering the pressure of the measured gases in the ionization chamber as little as possible. By means of these two measures the occurrence of fractionation processes during the transfer of gases from the gas containers to the mass spectrometer as well as in the ionization chamber is noticeably reduced by the in-house built dual-inlet system when compared to the dual-inlet system built by Elementar.
10:45 - 10:48
Tracing nitrogen transformations induced by 15N labelled cattle slurry applied with different techniques in winter wheat
Thünen-Institut für Agrarklimaschutz, Deutschland
The effects of slurry application techniques on ammonia (NH3) volatilisation and nitrous oxide (N2O) fluxes are well documented. However, application techniques may also impact dinitrogen (N2) fluxes, as they can influence denitrification activity by changing slurry and soil aeration (e.g. by injection techniques), nitrate formation (e.g. by adding nitrification inhibitors) and the pH value (e.g. by slurry acidification). Up to now, measuring N2 fluxes and following pathways of slurry nitrogen (N) transformation under field conditions is still challenging.
Thus, we applied a combined 15N labelling approach including slurry NH4+-N and soil NO3--N in undisturbed soil cores, set up as lysimeters and with growing winter wheat for a study period of 60 days. Slurry treatments include the following application techniques: trailing hose with and without acidification (H2SO4), slot injection with and without nitrification inhibitor (DMPP). Soil cores without slurry application were used as control. In a first step, soil nitrate was 15N labelled by homogeneous injection of a K15NO3- solution at a low N application rate (4 kg N ha-1), while one week later, 68 kg N ha-115N-labelled cattle slurry was applied. The 15N labelled cattle slurry consisted of fresh dairy cattle faeces (natural abundance), water and 15N labelled synthetic urine. N2O and N2 emission were measured using the modified 15N gas flux method with N2-depleted atmosphere. To close the N balance and follow the different N transformation pathways, 15N losses by leaching, 15N uptake by plant and residual 15N in belowground biomass, microbial biomass and soil were analysed by IRMS.
The major gaseous loss pathway was NH3 with up to 8 kg N ha-1 in the trailing hose treatment, while slot injection significantly reduced NH3-N losses. Regardless the application technique, N2O fluxes were very low (up to 0.1 kg N2O-N ha-1), while N2 reached up to 3 kg N ha-1. The N2O/(N2O+N2) ratio of dentification was always <0.1. The main pathways of the total N budget were gaseous N losses (NH3, N2O, N2) with 11-44%, soil N pool with 32-48% and plant uptake with 18-26% of 15N applied. N leaching and changes in the residual mineral nitrogen pool played only a minor role in the total N balance. Although there were no differences in the application techniques, it should be highlighted that the 15N recovery was almost complete, indicating that the experiment was able to capture the relevant 15N fates with the comprehensive setup that was applied.
10:48 - 10:50
Applying the 15N gas flux method in a lab incubation as an alternative to laborious field studies
1Thünen Institut für Agrarklimaschutz, Deutschland; 2Universität Trier, Raum- und Umweltwissenschaften, Bodenkunde, Deutschland
Applying the 15N gas flux method (15NGF) in the field can be very challenging. The establishment of a reliable setup is time consuming, expensive, and requires a decent infrastructure at the field sites. Additionally, the atmospheric N2 background reduces measurement precision for detecting low tracer-derived N2 emissions. We incubated undisturbed soil cores (14.4 cm diameter and 35 cm height) from two remote field sites: an annual cropping system (Zea mays) and a perennial cropping system (Silphium perfoliatum). The incubation took place in a fully-automated facility, which provided us with an N2-reduced atmosphere, options to control temperature, irrigation and drainage, and allowed better control over the homogeneity of 15N-nitrate pool labelling, as compared to what is possible in the field. Using the 15NGF method with undisturbed soil cores allowed us to quantify differences in source-specific N2 and N2O emissions while including the effect of soil structure under dynamic waterlogged conditions. Additional information about nitrogen transformation processes between the cropping systems were obtained in bulk soil by analysing soil mineral 15N (NO3- and NH4+) via membrane-inlet mass spectrometry. The incubation experiment consisted of three different phases with increasing soil water content: (1) entire core just below field capacity; (2) lower 10 cm waterlogged; and (3) lower 25 cm waterlogged. The soil from the S. perfoliatum field had a significantly lower product ratio of denitrification (N2O/N2+N2O) with increasing waterlogging than the Z. mays soil. However, pool-derived N2O emissions from the S. perfoliatum soil were not significantly lower than from Z. mays soil. Hence, we could show that the soil structure from the perennial cropping field resulted in higher N2 emissions rather than lower N2O emissions. Although perennial systems are generally expected to provide a greenhouse gas mitigation potential, we were able to replicate conditions that could not have been easily addressed in the field, and show that, in comparing soil from these fields, that was not the case.
|10:50 - 11:00||Pause|
|11:00 - 12:30||Block 7: Deutsches Isotopennetz GIN|
Virtueller Veranstaltungsort: Block 7 - Meeting Link
Chair der Sitzung: Robert van Geldern, Universität Erlangen-Nürnberg
Chair der Sitzung: Nils Michelsen, TU Darmstadt
11:00 - 11:15
Die Tritiumverteilung in Niederschlag und Oberflächenwasser in Deutschland – ein Beitrag zum deutschen Isotopennetzwerk
Bundesanstalt für Gewässerkunde, Deutschland
An der Bundesanstalt für Gewässerkunde (BfG) werden seit den 1970iger Jahren Oberflächenwasser- und Niederschlagsproben auf Tritium untersucht. Hierzu betreibt die BfG - mit Unterstützung der Wasserstraßen- und Schifffahrtsverwaltung (WSV), des Deutschen Wetterdienstes (DWD) und einiger Landesämter - ein bundesweites Netz aus insgesamt 69 Probenahmestationen mit dem Ziel, die Umweltradioaktivität großräumig zu überwachen. Dazu werden die Wasserproben aller Stationen als Monatsmischproben in den Laboren der BfG elektrolytisch angereichert und radiochemisch analysiert. Mittlerweile liegen alleine für Tritium mehr als 8000 Einzeldatensätze für Niederschlag und 23000 Einzeldatensätze für Oberflächenwasser frei zugänglich vor und können z.B. im Rahmen der Initiative „German Isotope Network - GIN“ verwendet werden.
Tritium (H-3) wird natürlicherweise durch Spallationsreaktionen in der Atmosphäre gebildet, anschließend zu überschwerem Wasser oxidiert und durch Niederschlag in die Oberflächengewässer eingetragen, wodurch es Bestandteil des hydrologischen Kreislaufes ist.
Die Tritiumkonzentrationen im Niederschlag sind im langjährigen Mittel (Untersuchungszeitraum 2010-2020) an der Station Cuxhaven (Nordsee) mit 10 TU am höchsten; landeinwärts verringern sich die Gehalte generell und liegen beispielsweise bei 8,9 TU an der Station Garmisch (Alpen). Das „Spring Leak“ – Phänomen führt im Frühsommer, im Vergleich zum restlichen Jahr, zu erhöhten Werten. Ebenso lagen die Tritiumkonzentrationen aufgrund geringer Niederschläge im Jahr 2018 an allen Stationen zwischen 15 % und 25 % über dem langjährigen Mittel.
Die Tritiumgehalte der Oberflächenwasserproben sind ebenfalls an der Nordseeküste mit etwa 33 TU (Station Helgoland) am höchsten; im Bereich der Ostsee liegen sie bei 7 TU (Station Travemünde) und sind damit mit den Konzentrationen im Landesinneren vergleichbar (z.B. 6,3 TU - Station Ulm). Überlagert werden diese natürlichen Werte durch z.T. stark erhöhte Tritiumkonzentrationen im Bereich von Kernkraftwerken, da diese im Rahmen ihres Routinebetriebes Tritium-haltiges Wasser diskontinuierlich über die Vorfluter in die Flüsse abgeben. So wird beispielsweise durch das französische Kernkraftwerk Cattenom regelmäßig Tritium in die Mosel eingeleitet, welches dann mit dem Fluss transportiert und durch Dispersionsprozesse verdünnt wird. So werden beispielsweise bis zu 500 TU im Oberflächenwasser an der Station Wincheringen (Fluss-km 222) und bis zu 200 TU an der Station Koblenz (Fluss-km 1,2) gemessen.
Diese Tritiumvariationen im Oberflächen- und Niederschlagswasser lassen sich für eine Vielzahl von wissenschaftlichen Fragestellungen verwenden. Im Rahmen dieser Präsentation sollen einige Anwendungen vorgestellt und anhand dessen die Möglichkeiten der Nutzung von Tritium als aquatischer Tracer auch heutzutage skizziert werden.
11:15 - 11:30
Tritium in der südlichen Nordsee: ein Tracer für lokal gebildeten Wasserdampf
Universität Bremen, Deutschland
Weltweit wurden ab Beginn der Wasserstoffbombentests Tritium-Konzentrationen im Niederschlag aufgezeichnet.
Das Global Network of Isotopes in Precipitation (GNIP) wurde 1958 von der IAEA und der WMO gegründet und ging 1961 in Betrieb. Seit dieser Zeit nahm die Anzahl der durchgeführten Analysen kontinuierlich ab. In der südlichen Hemisphäre und auch in tropischen und subtropischen Regionen der Nordhemisphäre verringerten sich Tritiumkonzentrationen bis heute auf Werte, die der Grenze der technisch möglichen Auslösung mit Szintillationszählern entsprechen. Die Bedeutung der Messwerte aus diesen Regionen nahm daher stark ab und Messprogramme wurden eingestellt.
Das Bundesamt für Gewässerkunde (BfG) misst Tritium im Niederschlag als Monatsmittel aus fast zwei Dutzend Orten in Deutschland. Diese Datenreihen und deren Besonderheiten werden mit Tritium im Niederschlag in der deutschen Küstenregion der Nordsee vergleichen.
Es werden Tritiumkonzentrationen im Niederschlag der Stationen des BfG mit Tritiumkonzentrationen im Grundwasser nahe der Deutschen Bucht verglichen.
Messungen von Tritium im Oberflächenwasser der Nordsee zeigen einen starken Anstieg der Werte seit Mitte der 1990iger Jahre. Zu dieser Zeit stiegen die Tritiumemissionen der Wiederaufbereitungsanlage in LaHague massiv.
Die Regensammler Station in Cuxhaven zeigt bis 1990 Tritiumwerte unterhalb anderer Stationen in Deutschland. Nach 2000 liegen die Werte aus Cuxhaven aber immer oberhalb der Werte anderer Stationen. Auch Grundwasserproben von den Ostfriesischen Inseln und nahe der Nordseeküste in Schleswig-Holsteins datiert auf Neubildungszeiten nach 2000 weisen deutlich höhere Tritiumkonzentrationen als der deutschlandweite Mittelwert der Niederschläge auf.
In der Nordsee zeigt sich die Ausbreitung von Tritium aus LaHague im östlich strömenden Küstenrandstrom und beschränkt damit räumlich die Region in der tritiumreicher Wasserdampf gebildet werden kann.
11:30 - 11:45
Distribution of young groundwater in the North German Basin
The Federal Institute for Geosciences and Natural Resources (BGR) is currently collecting all available groundwater age data on the territory of the Federal Republic of Germany. The background to this is that the German Site Selection Act for radioactive waste disposal sites defines groundwater age as an exclusion criterion. If young groundwater is detected in the vicinity of potential host formations, these sites must be excluded as a repository for high-level radioactive waste. In the by-laws, detectable concentrations of tritium (3H) and carbon-14 (14C) are specifically mentioned as indicators for young groundwater.
Groundwater ages also can be used for many other scientific questions, e.g. for studies on the transport of pollutants, such as nitrate and pesticides, for groundwater recharge estimations and for the calibration of regional groundwater models.
In addition to the collection of data, which will be archived in a publicly accessible database, the project will investigate the influence of various parameters on the determination of groundwater age, e.g. the screen length and the recharge rate and the distribution of young groundwater in the various hydrogeological units.
In the presentation, a short introduction to the database will be given and the first results on the spatial distribution will be shown. In addition, the first statistical evaluations on the depth-specific distribution of young groundwater in the North German Basin will be presented.
11:45 - 12:00
Stable isotope patterns of German rivers with aspects of scales and continuity
1Groundwater Resources Quality and Dynamics, Federal Institute for Geosciences and Natural Resources (BGR), Hannover, Germany; 2Institute for Soil Physics and Rural Water Management, University of Natural Resources and Life Sciences (BOKU), Vienna, Austria; 3Institute of Groundwater Ecology, Helmholtz Zentrum München, Neuherberg (HMGU), Germany; 4Environmental Radioactivity and Monitoring, Federal Institute of Hydrology (BfG), Koblenz, Germany
The stable isotope composition of river water (2H, 18O) in large basins mainly reflect precipitation, snow-melt or ice-melt inputs and modifications due to surface storage, mixing and contributions of time delayed groundwater components. Continuous observations of river water stable isotope patterns in high-resolution of time and space serve as characteristic fingerprints for specific locations or whole river basins. In Germany, river monitoring for radioactive isotopes started in the mid 1970s organized by the Federal Institute of Hydrology (BfG). Today a monitoring network for stable isotopes at 50 stations in monthly resolution is available [1, 2, 3] as part of the monitoring program of the BfG. The time series for stable isotopes are longer than three years and for some stations of up to 30 years. Additionally, daily river water samples were collected during the extraordinary dry autumn in October 2018 until January 2019 at six selected stations in the Rhine and five stations in the Elbe basin.
Most dominating stable isotope effects in river water are those of seasonality and altitudes, but also a continental effect is visible from δ18O vs. δ2H plots. Snow and ice-melt contribution in the Rhine and Danube during the summer months and a consecutive dilution of these signals by tributary rivers is visible. Close to the coasts in northern Germany, stable isotope patterns reflect influence of seawater and tides. Daily patterns during the dry season 2018/2019 do surprisingly not exhibit extreme changes but rather trends on enhanced groundwater contribution. Comparing German river basins of different sizes and mean catchment altitude reveal influences of scales. Long time series allows a discussion of the challenge to collect continuous data, but also uncertainties of measurements and the need for laboratory inter-comparisons.
 Reckerth A., Stichler W., Schmidt A., Stumpp C. (2017): Long-term data set analysis of stable isotopic composition in German rivers. J Hydrol. 552: 718-731.
 Stumpp C., Klaus J., Stichler W. (2014): Analysis of long-term stable isotopic composition in German precipitation. J Hydrol. 517: 351-361.
 Koeniger P., Leibundgut Ch., Stichler W. (2009): Spatial and temporal characterization of stable isotopes in river water as indicators of groundwater contribution and confirmation of modelling results; a study of the Weser River, Germany. IEHS 45 (4): 289-302.
12:00 - 12:15
Very high resolution Automated Rain Water Sampler for stable water isotope monitoring
GFZ Potsdam, Deutschland
With changing climate, increasing world population, the linked shortage of resources and pollution of the environment necessitates adequate tools and technics to monitor the Earth’s system. Measuring isotope ratios and trace elements dissolved in rainwater are useful utensils to understand the system and trace sources and pathways as well as to examine the timescales of transport of rainwater. Yet, it is very difficult to track, trace and measure rainwater pathways over landscapes and oceans. In particular, sampling and sample preservation is notoriously difficult and, in many cases, very laborious in manpower and technical demanding. Comprehensive and automated monitoring of precipitation waters in space and time can improve our process understanding to better predict the nature and magnitude of future hydrometeorological changes. Today, no commercial, and only a few research level, automated sampling devices for rainwater exist. However, no existing sampling technology fulfills the quality criteria for sophisticated hydro-chemical rainwater analysis in particular in remote areas over long time periods.
Facing this lack of high-quality technical solutions, we present a newly developed automatic and autonomous precipitation water sampler for stable water isotope analysis of rainwater. Our autosampler can take 165 discrete rainwater samples with a minimum time resolution of 5min or volume wise 2mm of rainfall. The device is designed to be highly autonomous and robust for long-term deployment in harsh and remote areas and fulfills the high demands on sampling and storage for isotope analysis (i.e. sealing of samples from atmospheric influences, no contamination and preservation of the sample material). The sampling device is portable, has low power consumption, is remotely accessible and thus has a real-time adaptable sampling protocol strategy, and can be maintained at distance without any need to visit the location.
The device was tested in several evaluation and benchmarking cycles. First lab tests with dyed waters and waters with strongly differing isotopic signature demonstrate that the device can obtain, store and conserve samples without cross contamination over long periods of time. The device has been tested so far under several conditions, e.g. heavy summer thunderstorms with more than 50mm/24h of rainfall, sustained winter rainfall and in cold conditions involving melting of snow. Furthermore, we run a benchmark test with several devices in parallel. Finally, in October 2020, we had installed six devices, in collaboration with Germany's National Meteorological Service (Deutscher Wetterdienst DWD), in a South-West to North-East transect across the Harz mountains in Germany.
This automated rainwater sampler provides a sophisticated technological solution for monitoring moisture pathways and water transfer processes with the analytical quality of laboratory standard measurements on a new level of temporal and spatial resolution.
12:15 - 12:30
GIN and beyond: Cumulative rain collectors for isotope studies in challenging climates
1Institute of Applied Geosciences, Technical University of Darmstadt, Germany; 2BGR Bundesanstalt für Geowissenschaften und Rohstoffe, Hannover, Germany
Data on the isotopic composition of precipitation often represent a key component in isotope studies of the water cycle. For gathering the corresponding samples, various types of cumulative precipitation collectors are available. Among these samplers, the tube-dip-in-water collector with pressure equilibration tube (Gröning et al., 2012) is particularly popular, largely due to its simplicity and rather effective evaporation reduction (Michelsen et al., 2018).
In cool climates however, the use of this sampler can be challenging, because water may freeze inside the collection bottle and block the inlet tube (Gröning et al., 2012). Extended exposure to warm conditions can be problematic as well, particularly if the collected water volume is small compared to the size of the collection vessel (Michelsen et al., 2018).
Here, we outline a few simple designs, which can help to overcome the above-mentioned difficulties and may hence be useful in the German Isotope Network (GIN) and beyond.
Gröning, M., Lutz, H.O., Roller-Lutz, Z., Kralik, M., Gourcy, L., Pöltenstein, L., 2012. A simple rain collector preventing water re-evaporation dedicated for δ18O and δ2H analysis of cumulative precipitation samples, Journal of Hydrology 448–449, 195–200.
Michelsen, N., van Geldern, R., Roßmann, Y., Bauer, I., Schulz, S., Barth, J. A. C., Schüth, C., 2018. Comparison of cumulative precipitation collectors used in isotope hydrology, Chemical Geology, 488, 171–179.
|12:30 - 13:30||Poster/Vortragspreis: ASI-Preise und Abschluss|
Virtueller Veranstaltungsort: Vortragspreis/Closing - Meeting Link
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