Leaf scale quantification of the effect of photosynthetic gas exchange on Δ47 of CO2

The clumped isotope composition (Δ47, the anomaly of the mass 47 isotopologue relative to the abundance expected from a random isotope distribution) of CO2 has been suggested as an additional tracer for gross CO2 fluxes. However, the effect of photosynthetic gas exchange on Δ47 has not been directly determined and two indirect/conceptual studies reported contradicting results. In this study, we quantify the effect of photosynthetic gas exchange on Δ47 of CO2 using leaf cuvette experiments with one C4 and two C3 plants. The experimental results are supported by calculations with a leaf cuvette model. Our results demonstrate the important roles of the Δ47 value of CO2 entering the leaf, kinetic fractionation as CO2 diffuses into, and out of the leaf and CO2–H2O isotope exchange with leaf water. We experimentally confirm the previously suggested dependence of Δ47 of CO2 in the air surrounding a leaf on the stomatal conductance and back-diffusion flux. Gas exchange can enrich or deplete the Δ47 of CO2 depending on the Δ47 of CO2 entering the leaf and the fraction of CO2 exchanged with leaf water and diffused back to the atmosphere, but under typical ambient conditions, it will lead to a decrease in Δ47

Fractionation of clumped isotopes of CO2 during photosynthesis

Stable isotope (δ13C and δ18O) and mole fraction measurements of CO2 are used to constrain the carbon cycle. However, the gross fluxes of the carbon cycle, especially photosynthesis and respiration, remain uncertain due to the challenging task of distinguishing individual flux terms from each other. The clumped isotope composition (Δ47) of CO2 has been suggested as an additional tracer for gross CO2 fluxes since it depends mainly on temperature but not on the bulk isotopic composition of leaf, soil and surface water, unlike δ18O of CO2. In this study, we quantify the effect of photosynthetic gas exchange on Δ47 of CO2 using leaf cuvette experiments with two C3 and one C4 plants and discuss challenges and possible applications of clumped isotope measurements. The experimental results are supported by calculations with a leaf cuvette model. Our results demonstrate how the effect of gas exchange on Δ47 is controlled by CO2-H2O isotope exchange (using plants with different carbonic anhydrase activity), and kinetic fractionation as CO2 diffuses into and out of the leaf (using plants with different stomatal and mesophyll conductance). We experimentally confirm the previously suggested dependence of Δ47­­ on the stomatal conductance and back-diffusion flux

Methane emissions from the Munich Oktoberfest

This study presents the first investigation of the methane (CH4) emissions of a large festival. Munich Oktoberfest, the world's largest folk festival, is a potential source of CH4 as a large amount of natural gas for cooking and heating is used. In 2018 we measured the CH4 emissions of Oktoberfest using in situ measurements combined with a Gaussian plume dispersion model. Measurements were taken while walking and biking around the perimeter of the Oktoberfest premises (Theresienwiese) at different times of the day, during the week and at the weekend. The measurements showed enhancements of up to 100 ppb compared to background values and measurements after Oktoberfest. The average emission flux of Oktoberfest is determined as (6:7 ± 0:6) μ g.m2 s/-1. Additional analyses, including the daily emission cycle and comparisons between emissions and the number of visitors, suggest that CH4 emissions of Oktoberfest are not due solely to the human biogenic emissions. Instead, fossil fuel CH4 emissions, such as incomplete combustion or loss in the gas appliances, appear to be the major contributors to Oktoberfest emissions. Our results can help to develop CH4 reduction policies and measures to reduce emissions at festivals and other major events in cities. Furthermore, events with a limited duration have not yet been included in the state-of-the-art emission inventories, such as TNO-MACC, EDGAR or IER. Our investigations show that these emissions are not negligible. Therefore, these events should be included in future emission inventories

Methane emissions from the Munich Oktoberfest

This study presents the first investigation of the methane (CH4) emissions of a large festival. Munich Oktoberfest, the world's largest folk festival, is a potential source of CH4 as a large amount of natural gas for cooking and heating is used. In 2018 we measured the CH4 emissions of Oktoberfest using in situ measurements combined with a Gaussian plume dispersion model. Measurements were taken while walking and biking around the perimeter of the Oktoberfest premises (Theresienwiese) at different times of the day, during the week and at the weekend. The measurements showed enhancements of up to 100 ppb compared to background values and measurements after Oktoberfest. The average emission flux of Oktoberfest is determined as (6:7 ± 0:6) μ g.m2 s/-1. Additional analyses, including the daily emission cycle and comparisons between emissions and the number of visitors, suggest that CH4 emissions of Oktoberfest are not due solely to the human biogenic emissions. Instead, fossil fuel CH4 emissions, such as incomplete combustion or loss in the gas appliances, appear to be the major contributors to Oktoberfest emissions. Our results can help to develop CH4 reduction policies and measures to reduce emissions at festivals and other major events in cities. Furthermore, events with a limited duration have not yet been included in the state-of-the-art emission inventories, such as TNO-MACC, EDGAR or IER. Our investigations show that these emissions are not negligible. Therefore, these events should be included in future emission inventories

Leaf scale quantification of the effect of photosynthetic gas exchange on Δ47 of CO2

The clumped isotope composition (Δ47, the anomaly of the mass 47 isotopologue relative to the abundance expected from a random isotope distribution) of CO2 has been suggested as an additional tracer for gross CO2 fluxes. However, the effect of photosynthetic gas exchange on Δ47 has not been directly determined and two indirect/conceptual studies reported contradicting results. In this study, we quantify the effect of photosynthetic gas exchange on Δ47 of CO2 using leaf cuvette experiments with one C4 and two C3 plants. The experimental results are supported by calculations with a leaf cuvette model. Our results demonstrate the important roles of the Δ47 value of CO2 entering the leaf, kinetic fractionation as CO2 diffuses into, and out of the leaf and CO2–H2O isotope exchange with leaf water. We experimentally confirm the previously suggested dependence of Δ47 of CO2 in the air surrounding a leaf on the stomatal conductance and back-diffusion flux. Gas exchange can enrich or deplete the Δ47 of CO2 depending on the Δ47 of CO2 entering the leaf and the fraction of CO2 exchanged with leaf water and diffused back to the atmosphere, but under typical ambient conditions, it will lead to a decrease in Δ47

Global 3‐D Simulations of the Triple Oxygen Isotope Signature Δ17O in Atmospheric CO2

The triple oxygen isotope signature Δ17O in atmospheric CO2, also known as its “17O excess,” has been proposed as a tracer for gross primary production (the gross uptake of CO2 by vegetation through photosynthesis). We present the first global 3‐D model simulations for Δ17O in atmospheric CO2 together with a detailed model description and sensitivity analyses. In our 3‐D model framework we include the stratospheric source of Δ17O in CO2 and the surface sinks from vegetation, soils, ocean, biomass burning, and fossil fuel combustion. The effect of oxidation of atmospheric CO on Δ17O in CO2 is also included in our model. We estimate that the global mean Δ17O (defined as urn:x-wiley:jgrd:media:jgrd55562:jgrd55562-math-0001 with λRL = 0.5229) of CO2 in the lowest 500 m of the atmosphere is 39.6 per meg, which is ∼20 per meg lower than estimates from existing box models. We compare our model results with a measured stratospheric Δ17O in CO2 profile from Sodankylä (Finland), which shows good agreement. In addition, we compare our model results with tropospheric measurements of Δ17O in CO2 from Göttingen (Germany) and Taipei (Taiwan), which shows some agreement but we also find substantial discrepancies that are subsequently discussed. Finally, we show model results for Zotino (Russia), Mauna Loa (United States), Manaus (Brazil), and South Pole, which we propose as possible locations for future measurements of Δ17O in tropospheric CO2 that can help to further increase our understanding of the global budget of Δ17O in atmospheric CO2.JRC.C.5-Air and Climat

Fractionation of clumped isotopes of CO2 during photosynthesis

Stable isotope (δ13C and δ18O) and mole fraction measurements of CO2 are used to constrain the carbon cycle. However, the gross fluxes of the carbon cycle, especially photosynthesis and respiration, remain uncertain due to the challenging task of distinguishing individual flux terms from each other. The clumped isotope composition (Δ47) of CO2 has been suggested as an additional tracer for gross CO2 fluxes since it depends mainly on temperature but not on the bulk isotopic composition of leaf, soil and surface water, unlike δ18O of CO2. In this study, we quantify the effect of photosynthetic gas exchange on Δ47 of CO2 using leaf cuvette experiments with two C3 and one C4 plants and discuss challenges and possible applications of clumped isotope measurements. The experimental results are supported by calculations with a leaf cuvette model. Our results demonstrate how the effect of gas exchange on Δ47 is controlled by CO2-H2O isotope exchange (using plants with different carbonic anhydrase activity), and kinetic fractionation as CO2 diffuses into and out of the leaf (using plants with different stomatal and mesophyll conductance). We experimentally confirm the previously suggested dependence of Δ47­­ on the stomatal conductance and back-diffusion flux