Technical note: Novel estimates of the leaf relative uptake rate of carbonyl sulfide from optimality theory

In order to estimate the gross primary productivity (GPP) of terrestrial ecosystems from the canopy uptake of carbonyl sulfide (COS), the leaf relative uptake rate (LRU) of COS with respect to carbon dioxide needs to be known a priori. Currently, the variability of the LRU between plant species in different biomes of the world is poorly understood, making the choice of an appropriate LRU uncertain and hampering further progress towards developing COS as an alternative tracer of GPP. Here we propose a novel approach for estimating LRU based on plant optimality principles, validate it against in situ leaf gas exchange measurements and provide global monthly climatological estimates. The global vegetation season average simulated LRUs fall into the range of 0.5&ndash;1.4 and are thus lower than any other published global estimates. We advocate these LRU estimates to be adopted by global modellers in order to test to what degree these are compatible with our current understanding of the sources and sinks in the global COS budget.</p

Soil carbonyl sulfide exchange in relation to microbial community composition: Insights from a managed grassland soil amendment experiment

The viability of carbonyl sulfide (COS) measurements for partitioning ecosystem-scale net carbon dioxide (CO2) fluxes into photosynthesis and respiration critically depends on our knowledge of non-leaf sinks and sources of COS in ecosystems. We combined soil gas exchange measurements of COS and CO2 with next-generation sequencing technology (NGS) to investigate the role of soil microbiota for soil COS exchange. We applied different treatments (litter and glucose addition, enzyme inhibition and gamma sterilization) to soil samples from a temperate grassland to manipulate microbial composition and activity. While untreated soil was characterized by consistent COS uptake, other treatments reduced COS uptake and even turned the soil into a net COS source. Removing biotic processes through sterilization led to positive or zero fluxes. We used NGS to link changes in the COS response to alterations in the microbial community composition, with bacterial data having a higher explanatory power for the measured COS fluxes than fungal data. We found that the genera Arthrobacter and Streptomyces were particularly abundant in samples exhibiting high COS emissions. Our results indicate cooccurring abiotic production and biotic consumption of COS in untreated soil, the latter linked to carbonic anhydrase activity, and a strong dependency of the COS flux on the activity, identity, abundance of and substrate available to microorganisms.Austrian National Science Fund (FWF) | Ref. P27176-B16Tyrolean Science Fund (TWF) | Ref. UNI-0404/1801Ministerio de Economía y Competitividad | Ref. RYC-2016-2123

Technical Note: Novel Estimates of the Leaf Relative Uptake Rate of Carbonyl Sulfide from Optimality Theory

In order to estimate the gross primary productivity (GPP) of terrestrial ecosystems from the canopy uptake of carbonyl sulfide (COS), the leaf relative uptake rate (LRU) of COS with respect to carbon dioxide needs to be known a priori. Currently, the variability of the LRU between plant species in different biomes of the world is poorly understood, making the choice of an appropriate LRU uncertain and hampering further progress towards developing COS as an alternative tracer of GPP. Here we propose a novel approach for estimating LRU based on plant optimality principles, validate it against in situ leaf gas exchange measurements and provide global monthly climatological estimates. The global vegetation season average simulated LRUs fall into the range of 0.5-1.4 and are thus lower than any other published global estimates. We advocate these LRU estimates to be adopted by global modellers in order to test to what degree these are compatible with our current understanding of the sources and sinks in the global COS budget

Exploring the oxidation behavior of undiluted and diluted iron particles for energy storage: Mössbauer spectroscopic analysis and kinetic modeling

Iron is an abundant and non-toxic element that holds great potential as energy carrier for large-scale and long-term energy storage. While from a general viewpoint iron oxidation is well-known, the detailed kinetics of oxidation for micrometer sized particles are missing, but required to enable large-scale utilization for energy production. In this work, iron particles are subjected to temperature-programmed oxidation. By dilution with boron nitride a sintering of the particles is prevented enabling to follow single particle effects. The mass fractions of iron and its oxides are determined for different oxidation times using Mössbauer spectroscopy. On the basis of the extracted phase compositions obtained at different times and temperatures (600–700 °C), it can be concluded that also for particles the oxidation follows a parabolic rate law. The parabolic rate constants are determined in this transition region. Knowledge of the particle size distribution and its consideration in modeling the oxidation kinetics of iron powder has proven to be crucial

Evaluation of carbonyl sulfide biosphere exchange in the Simple Biosphere Model (SiB4)

The uptake of carbonyl sulfide (COS) by terrestrial plants is linked to photosynthetic uptake of CO2 as these gases partly share the same uptake pathway. Applying COS as a photosynthesis tracer in models requires an accurate representation of biosphere COS fluxes, but these models have not been extensively evaluated against field observations of COS fluxes. In this paper, the COS flux as simulated by the Simple Biosphere Model, version 4 (SiB4), is updated with the latest mechanistic insights and evaluated with site obser- vations from different biomes: one evergreen needleleaf forest, two deciduous broadleaf forests, three grasslands, and two crop fields spread over Europe and North America. We improved SiB4 in several ways to improve its representation of COS. To account for the effect of atmospheric COS mole fractions on COS biosphere uptake, we replaced the fixed atmospheric COS mole fraction boundary condition originally used in SiB4 with spatially and temporally varying COS mole fraction fields. Seasonal amplitudes of COS mole fractions are similar to 50-200 ppt at the investigated sites with a minimum mole fraction in the late growing season. Incorporating seasonal variability into the model reduces COS uptake rates in the late growing season, allowing better agreement with observations. We also replaced the empirical soil COS uptake model in SiB4 with a mechanistic model that represents both uptake and production of COS in soils, which improves the match with observations over agricultural fields and fertilized grassland soils. The improved version of SiB4 was capable of simulating the diurnal and seasonal variation in COS fluxes in the boreal, temperate, and Mediterranean region. Nonetheless, the daytime vegetation COS flux is underestimated on average by 8 +/- 27 %, albeit with large variability across sites. On a global scale, our model modifications decreased the modeled COS terrestrial biosphere sink from 922 Gg S yr(-1) in the original SiB4 to 753 Gg S yr(-1) in the updated version. The largest decrease in fluxes was driven by lower atmospheric COS mole fractions over regions with high productivity, which highlights the importance of accounting for variations in atmospheric COS mole fractions. The change to a different soil model, on the other hand, had a relatively small effect on the global biosphere COS sink. The secondary role of the modeled soil component in the global COS budget supports the use of COS as a global photosynthesis tracer. A more accurate representation of COS uptake in SiB4 should allow for improved application of atmospheric COS as a tracer of local- to global-scale terrestrial photosynthesis.Peer reviewe

Exploring the oxidation behavior of undiluted and diluted iron particles for energy storage: Mössbauer spectroscopic analysis and kinetic modeling

Iron is an abundant and non-toxic element that holds great potential as energy carrier for large-scale and long-term energy storage. While from a general viewpoint iron oxidation is well-known, the detailed kinetics of oxidation for micrometer sized particles are missing, but required to enable large-scale utilization for energy production. In this work, iron particles are subjected to temperature-programmed oxidation. By dilution with boron nitride a sintering of the particles is prevented enabling to follow single particle effects. The mass fractions of iron and its oxides are determined for different oxidation times using Mossbauer spectroscopy. On the basis of the extracted phase compositions obtained at different times and temperatures (600-700 degrees C), it can be concluded that also for particles the oxidation follows a parabolic rate law. The parabolic rate constants are determined in this transition region. Knowledge of the particle size distribution and its consideration in modeling the oxidation kinetics of iron powder has proven to be crucial. Measuring the composition at different stages of oxidation enables extracting the kinetics and highlighting differences and similarities of iron particles to bulk material