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Clumped isotopes as a novel tracer for the N2O cycle

English title Clumped isotopes as a novel tracer for the N2O cycle
Applicant Emmenegger Lukas
Number 166255
Funding scheme Project funding
Research institution Luftfremdstoffe / Umwelttechnik 500 - Mobility, Energy and Environment EMPA
Institution of higher education Swiss Federal Laboratories for Materials Science and Technology - EMPA
Main discipline Climatology. Atmospherical Chemistry, Aeronomy
Start/End 01.09.2016 - 31.08.2020
Approved amount 298'554.00
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All Disciplines (2)

Discipline
Climatology. Atmospherical Chemistry, Aeronomy
Other disciplines of Environmental Sciences

Keywords (6)

clumped isotopes; nitrous oxide; site-specific; laser spectroscopy; greenhouse gas; global N2O cycle

Lay Summary (German)

Lead
Auf Grund der Vielzahl möglicher Reaktionsmechanismen von Lachgas (N2O) ist es bis heute schwierig, die wesentlichen Bildungswege dieses Treibhausgases und Ozonkillers zu bestimmen und wirksame Minderungsstrategien zu erarbeiten. Die doppelsubstituierten sogenannten „clumped“ Isotope eröffnen eine neuartige Möglichkeit Reaktionsmechanismen zu untersuchen. Im vorliegenden Projekt soll erkundet werden wie die „clumped“ N2O Isotope zu einem verbesserten Verständnis des Lachgaskreislaufs beitragen können.
Lay summary

Lachgas ist ein potentes Treibhausgas und die wichtigste ozonzerstörende Verbindung, welche aktuell emittiert wird. Es gibt eine Vielzahl von Bildungswegen, die räumlich und zeitlich stark variieren können, was eine Quellzuordnung und die Entwicklung von Minderungsmassnahmen schwierig macht. Für verschiedene Atmosphärengase, wie CO2 und CH4, wurde in den letzten Jahren ein neue Methode entwickelt, um deren Stoff-Kreisläufe zu untersuchen, die Analyse der doppeltsubstituierten, sogenannten „clumped“ Isotope.

Im vorliegenden Projekt wird eine Quantenkaskadenlaser basierte Messmethode für die selektive und präzise Bestimmung der häufigsten doppeltsubstituierten N2O Isotopenverbindungen 15N14N18O, 14N15N18O und 15N15N16O entwickelt. Die Analysenmethode umfasst einen Laserspektrometer und eine Aufkonzentriereinheit, mit welcher die N2O Konzentration von Umgebungs- oder Prozesskonzentrationen auf mehrere Prozent erhöht werden kann. Der Vorteil gegenüber existierenden hochauflösenden massenspektrometrischen Messmethoden liegt in der sehr viel einfacheren Anwendbarkeit und der kürzeren Analysendauer, aber vor allem in der Selektivität für die Isotopomere 15N14N18O und 14N15N18O.  Ausserdem kann mit der laserspektroskopischen Methode zusätzlich das 15N15N16O Isotopologue bestimmt werden, welches in der aktuellen massenspektroskopischen Messmethode nicht vorgesehen ist.

Das Potential der neuartigen Messmethode wird anhand einiger Modellanwendungen, wie N2O aus abiotischen Prozessen oder mikrobieller oder Pilzbildung untersucht. Potentielle weitere Anwendungen sind im Bereich der Stratosphärenchemie oder der industriellen Katalyse. Bezüglich des N2O Kreislaufes kann davon ausgegangen werden, dass die doppelsubstituierten N2O Isotope eine neuartige Klasse von Substrat-unabhängigen Tracern auf molekularer Skala darstellen.

Direct link to Lay Summary Last update: 23.09.2016

Responsible applicant and co-applicants

Employees

Project partner

Publications

Publication
Photolytic fractionation of seven singly and doubly substituted nitrous oxide isotopocules measured by quantum cascade laser absorption spectroscopy
Kantnerová Kristýna, Jespersen Malte F., Bernasconi Stefano M., Emmenegger Lukas, Johnson Matthew S., Mohn Joachim (2020), Photolytic fractionation of seven singly and doubly substituted nitrous oxide isotopocules measured by quantum cascade laser absorption spectroscopy, in Atmospheric Environment: X, 8, 100094-100094.
First investigation and absolute calibration of clumped isotopes in N2O by mid‐infrared laser spectroscopy
Kantnerová Kristýna, Yu Longfei, Zindel Daniel, Zahniser Mark S., Nelson David D., Tuzson Béla, Nakagawa Mayuko, Toyoda Sakae, Yoshida Naohiro, Emmenegger Lukas, Bernasconi Stefano M., Mohn Joachim (2020), First investigation and absolute calibration of clumped isotopes in N2O by mid‐infrared laser spectroscopy, in Rapid Communications in Mass Spectrometry, 34(15), e8836.
Quantifying Isotopic Signatures of N2O Using Quantum Cascade Laser Absorption Spectroscopy
Kantnerová Kristýna, Tuzson Béla, Emmenegger Lukas, Bernasconi Stefano M., Mohn Joachim (2019), Quantifying Isotopic Signatures of N2O Using Quantum Cascade Laser Absorption Spectroscopy, in CHIMIA International Journal for Chemistry, 73(4), 232-238.

Collaboration

Group / person Country
Types of collaboration
PD Dr. Reinhard Well and Dr. Dominika Lewicka-Szczebak / Johann Heinrich von Thünen Institute Germany (Europe)
- in-depth/constructive exchanges on approaches, methods or results
Prof. Naohiro Yoshida and Dr. Sakae Toyoda / Tokyo Institute of Technology Japan (Asia)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Exchange of personnel
Prof. John Eiler / Caltech United States of America (North America)
- in-depth/constructive exchanges on approaches, methods or results
Prof. Matthew S. Johnson / University of Copenhagen Denmark (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
EGU General Assembly 2020 Talk given at a conference Clumped isotope analysis in nitrous oxide by mid-IR laser spectroscopy: analytical developments and validation 04.05.2020 Vienna, Austria Mohn Joachim; Kantnerová Kristýna; Emmenegger Lukas; Bernasconi Stefano;
What can we learn from N2O isotope data? Poster Clumped isotopes in N2O: QCLAS method development 23.10.2019 Dübendorf, Switzerland Bernasconi Stefano; Emmenegger Lukas; Kantnerová Kristýna; Mohn Joachim;
Isotopes 2019 Talk given at a conference New reference frame for clumped N2O isotopic analysis 07.07.2019 Raitenhaslach, Germany Kantnerová Kristýna; Mohn Joachim; Emmenegger Lukas; Bernasconi Stefano;
7th International Clumped Isotope Workshop 2019 Talk given at a conference Clumped N2O isotopes analysis by mid-IR laser spectroscopy 25.01.2019 Los Angeles, United States of America Kantnerová Kristýna; Emmenegger Lukas; Bernasconi Stefano; Mohn Joachim;
Empa PhD Symposium 2018 Talk given at a conference Clumped N2O isotopes analysis by mid-IR laser spectroscopy 26.11.2018 Dübendorf, Switzerland Kantnerová Kristýna; Mohn Joachim; Bernasconi Stefano; Emmenegger Lukas;
MASSTWIN Exploratory Workshop Talk given at a conference Singly and doubly substituted isotopocules of nitrous oxide and their application in environmental studies 14.11.2018 Halle, Germany Mohn Joachim; Emmenegger Lukas; Bernasconi Stefano; Kantnerová Kristýna;
ASI 2018 (Arbeitsgemeinschaft Stabile Isotopen e. V.) Talk given at a conference Clumped isotopes of nitrous oxide by mid-IR laser spectroscopy 30.09.2018 Raitenhaslach, Germany Kantnerová Kristýna; Bernasconi Stefano; Mohn Joachim; Emmenegger Lukas;
Swiss Chemical Society (SCS) Fall Meeting 2018 Talk given at a conference Clumped N2O isotopes by mid-IR laser spectroscopy 07.09.2018 Lausanne, Switzerland Mohn Joachim; Emmenegger Lukas; Kantnerová Kristýna; Bernasconi Stefano;
Stable Isotope Summer School 2018 Talk given at a conference Clumped isotopes in nitrous oxide: development of a spectroscopic method. Basic introduction 15.04.2018 Konstanz, Germany Kantnerová Kristýna; Emmenegger Lukas; Bernasconi Stefano; Mohn Joachim;
GGMT 2017 (19th WMO/IAEA Meeting on Carbon Dioxide, Other Greenhouse Gases and Related Measurement Techniques) Poster High precision spectroscopic measurement of N¬2O clumped isotopic species 27.08.2017 Dübendorf, Switzerland Bernasconi Stefano; Kantnerová Kristýna; Mohn Joachim; Emmenegger Lukas;
Swiss Chemical Society (SCS) Fall Meeting 2017 Talk given at a conference High precision spectroscopic measurement of N2O clumped isotopic species 21.08.2017 Bern, Switzerland Emmenegger Lukas; Bernasconi Stefano; Mohn Joachim; Kantnerová Kristýna;
6th International Clumped Isotope Workshop 2017 Talk given at a conference High precision spectroscopic measurement of N2O clumped isotopic species 10.08.2017 Paris, France Mohn Joachim; Bernasconi Stefano; Emmenegger Lukas; Kantnerová Kristýna;
Isotopes 2017 Poster Clumped isotopes in N2O: QCLAS method development 09.07.2017 Ascona, Switzerland Kantnerová Kristýna; Mohn Joachim; Bernasconi Stefano; Emmenegger Lukas;
Empa PhD Symposium 2016 Poster Clumped isotopes as a novel tracer for the N2O cycle 14.11.2016 Dübendorf, Switzerland Bernasconi Stefano; Mohn Joachim; Kantnerová Kristýna; Emmenegger Lukas;


Awards

Title Year
ETH Silver Medal for an outstanding doctoral thesis 2021
METAS Award 2021 for an outstanding contribution to the field of metrology in chemistry and/or biology 2021
Stable Isotope Summer School 2018, University of Konstanz, Germany, oral presentation “Clumped isotopes in nitrous oxide: development of a spectroscopic method. Basic introduction”, award for the best oral presentation 2018
Swiss Chemical Society (SCS) Fall Meeting 2018, Lausanne, Switzerland, oral presentation, “Clumped N2O isotopes by mid-IR laser spectroscopy”, SCS-Metrohm Award for best oral presentation in Analytical Sciences 2018
D-ERDW and D-USYS Graduate Research Symposium 2017, ETH Zürich, Switzerland, poster presentation “Clumped isotopes in nitrous oxide: development of a spectroscopic method“, poster prize 2017
Swiss Chemical Society (SCS) Fall Meeting 2017, Bern, Switzerland, oral presentation “High precision spectroscopic measurement of N2O clumped isotopic species”, SCS-Metrohm Award for 2nd best oral presentation in Analytical Sciences 2017

Associated projects

Number Title Start Funding scheme
172585 N2O from the Swiss midlands - regional sources and hot spots - 18 month extension 01.06.2017 Project funding
176584 High-resolution QCL frequency comb spectrometer for the detection of trace gases and their isotopes 01.05.2018 Bridge - Discovery
198227 ICOS-CH Phase 3 01.07.2021 Research Infrastructure
150237 N2O from the Swiss midlands - regional sources and hot spots 01.06.2014 Project funding
183294 QCL4CLUMPS: Simultaneous QC laser spectroscopic analysis of clumped 13C-D and D-D (2 x 2) isotopes in CH4 01.03.2020 R'EQUIP

Abstract

Nitrous oxide is a major greenhouse gas and the most important ozone destructing species emitted today. Its sources are disperse and highly variable which, combined with the long lifetime of N2O, makes source studies and thus mitigation challenging. Measuring the doubly substituted “clumped” isotopes of N2O will add new and unique dimensions to our ability to fingerprint and constrain the N2O biogeochemical cycle, as has been shown in recent years for other atmospheric constituents such as CO2, CH4, and O2. We propose to develop a quantum cascade laser based analytical technique for the selective and precise analysis of the most abundant doubly substituted N2O isotopic species: 15N14N18O, 14N15N18O, and 15N15N16O. The measurement setup will consist of a laser spectrometer coupled to a field deployable preconcentration device, capable of enhancing N2O mixing ratios from ambient or process levels to the percentage range. The novel analytical technique will surpass alternative, currently emerging high-resolution mass spectrometric approaches in terms of ease-of-use, sample throughput, precision, and most importantly, its inherent selectivity for the clumped isotopomers 15N14N18O and 14N15N18O. In addition, laser spectroscopy offers the capability for 15N15N16O analysis, which is not included in the current mass spectrometric procedure and presents a significant additional effort. The analytical accuracy will be obtained by referencing the measurements to N2O thermally equilibrated at distinct temperatures. Being a completely new and exciting field of research, analysis of clumped N2O isotopes offers a broad range of prospective applications. This will be demonstrated by testing three exemplary research hypotheses on N2O produced by microbial, fungal and abiotic sources processes. In a larger perspective, this new technique may also be applied to other research areas such as stratospheric chemistry or industrial catalytic processes. With respect to biogeochemical N2O cycles, clumped N2O is expected to significantly advance our understanding by providing a new class of reservoir-insensitive approaches and molecular-scale insights.
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