Quantifying differences in land use emission estimates implied by definition discrepancies

The quantification of CO2 emissions from anthropogenic land use and land use change (eLUC) is essential to understand the drivers of the atmospheric CO2 increase and to inform climate change mitigation policy. Reported values in synthesis reports are commonly derived from different approaches (observation-driven bookkeeping and process-modelling) but recent work has emphasized that inconsistencies between methods may imply substantial differences in eLUC estimates. However, a consistent quantification is lacking and no concise modelling protocol for the separation of primary and secondary components of eLUC has been established. Here, we review differences of eLUC quantification methods and apply an Earth System Model (ESM) of Intermediate Complexity to quantify them. We find that the magnitude of effects due to merely conceptual differences between ESM and offline vegetation model-based quantifications is ~ 20 % for today. Under a future business-as-usual scenario, differences tend to increase further due to slowing land conversion rates and an increasing impact of altered environmental conditions on land-atmosphere fluxes. We establish how coupled Earth System Models may be applied to separate secondary component fluxes of eLUC arising from the replacement of potential C sinks/sources and the land use feedback and show that secondary fluxes derived from offline vegetation models are conceptually and quantitatively not identical to either, nor their sum. Therefore, we argue that synthesis studies should resort to the "least common denominator" of different methods, following the bookkeeping approach where only primary land use emissions are quantified under the assumption of constant environmental boundary conditions.

Electrochemical CO2 Reduction - A Critical View on Fundamentals, Materials and Applications

The electrochemical reduction of CO2 has been extensively studied over the past decades. Nevertheless, this topic has been tackled so far only by using a very fundamental approach and mostly by trying to improve kinetics and selectivities toward specific products in half-cell configurations and liquid-based electrolytes. The main drawback of this approach is that, due to the low solubility of CO2 in water, the maximum CO2 reduction current which could be drawn falls in the range of 0.01–0.02 A cm–2. This is at least an order of magnitude lower current density than the requirement to make CO2-electrolysis a technically and economically feasible option for transformation of CO2 into chemical feedstock or fuel thereby closing the CO2 cycle. This work attempts to give a short overview on the status of electrochemical CO2 reduction with respect to challenges at the electrolysis cell as well as at the catalyst level. We will critically discuss possible pathways to increase both operating current density and conversion efficiency in order to close the gap with established energy conversion technologies.

Constraining global methane emissions and uptake by ecosystems

Natural methane (CH4) emissions from wet ecosystems are an important part of today's global CH4 budget. Climate affects the exchange of CH4 between ecosystems and the atmosphere by influencing CH4 production, oxidation, and transport in the soil. The net CH4 exchange depends on ecosystem hydrology, soil and vegetation characteristics. Here, the LPJ-WHyMe global dynamical vegetation model is used to simulate global net CH4 emissions for different ecosystems: northern peatlands (45°–90° N), naturally inundated wetlands (60° S–45° N), rice agriculture and wet mineral soils. Mineral soils are a potential CH4 sink, but can also be a source with the direction of the net exchange depending on soil moisture content. The geographical and seasonal distributions are evaluated against multi-dimensional atmospheric inversions for 2003–2005, using two independent four-dimensional variational assimilation systems. The atmospheric inversions are constrained by the atmospheric CH4 observations of the SCIAMACHY satellite instrument and global surface networks. Compared to LPJ-WHyMe the inversions result in a~significant reduction in the emissions from northern peatlands and suggest that LPJ-WHyMe maximum annual emissions peak about one month late. The inversions do not put strong constraints on the division of sources between inundated wetlands and wet mineral soils in the tropics. Based on the inversion results we diagnose model parameters in LPJ-WHyMe and simulate the surface exchange of CH4 over the period 1990–2008. Over the whole period we infer an increase of global ecosystem CH4 emissions of +1.11 Tg CH4 yr−1, not considering potential additional changes in wetland extent. The increase in simulated CH4 emissions is attributed to enhanced soil respiration resulting from the observed rise in land temperature and in atmospheric carbon dioxide that were used as input. The long-term decline of the atmospheric CH4 growth rate from 1990 to 2006 cannot be fully explained with the simulated ecosystem emissions. However, these emissions show an increasing trend of +3.62 Tg CH4 yr−1 over 2005–2008 which can partly explain the renewed increase in atmospheric CH4 concentration during recent years.

Ultrasonic acoustic emissions in drought-stressed trees - more than signals from cavitation?

Ultrasonic acoustic emission (UAE) in trees is often related to collapsing water columns in the flow path as a result of tensions that are too strong (cavitation). However, in a decibel (dB) range below that associated with cavitation, a close relationship was found between UAE intensities and stem radius changes. • UAE was continuously recorded on the stems of mature field-grown trees of Scots pine (Pinus sylvestris) and pubescent oak (Quercus pubescens) at a dry inner-Alpine site in Switzerland over two seasons. The averaged 20-Hz records were related to microclimatic conditions in air and soil, sap-flow rates and stem-radius fluctuations de-trended for growth (ΔW). • Within a low-dB range (27 ± 1 dB), UAE regularly increased and decreased in a diurnal rhythm in parallel with ΔW on cloudy days and at night. These low-dB emissions were interrupted by UAE abruptly switching between the low-dB range and a high-dB range (36 ± 1 dB) on clear, sunny days, corresponding to the widely supported interpretation of UAE as sound from cavitations. • It is hypothesized that the low-dB signals in drought-stressed trees are caused by respiration and/or cambial growth as these physiological activities are tissue water-content dependent and have been shown to produce courses of CO2 efflux similar to our courses of ΔW and low-dB UAE.

Fabric-mechanical property relationships of trabecular bone allografts are altered by supercritical CO2 treatment and gamma sterilization

Tissue grafts are implanted in orthopedic surgery every day. In order to minimize infection risk, bone allografts are often delipidated with supercritical CO2 and sterilized prior to implantation. This treatment may, however, impair the mechanical behavior of the bone graft tissue. The goal of this study was to determine clinically relevant mechanical properties of treated/sterilized human trabecular bone grafts, e.g. the apparent modulus, strength, and the ability to absorb energy during compaction. They were compared with results of identical experiments performed previously on untreated/fresh frozen human trabecular bone from the same anatomical site (Charlebois, 2008). We tested the hypothesis that the morphology–mechanical property relationships of treated cancellous allografts are similar to those of fresh untreated bone. The morphology of the allografts was determined by μCT. Subsequently, cylindrical samples were tested in unconfined and confined compression. To account for various morphologies, the experimental data was fitted to phenomenological mechanical models for elasticity, strength, and dissipated energy density based on bone volume fraction (BV/TV) and the fabric tensor determined by MIL. The treatment/sterilization process does not appear to influence bone graft stiffness. However, strength and energy dissipation of the bone grafts were found to be significantly reduced by 36% to 47% and 66% to 81%, respectively, for a broad range of volume fraction (0.14 < BV/TV < 0.39) and degree of anisotropy (1.24 < DA < 2.18). Since the latter properties are strongly dominated by BV/TV, the clinical consequences of this reduction can be compensated by using grafts with lower porosity. The data of this study suggests that an increase of 5–10% in BV/TV is sufficient to compensate for the reduced post-yield mechanical properties of treated/sterilized bone in monotonic compression. In applications where graft stiffness needs to be matched and strength is not a concern, treated allograft with the same BV/TV as an appropriate fresh bone graft may be used.

Impact of an abrupt cooling event on interglacial methane emissions in northern peatlands

Rapid changes in atmospheric methane (CH4), temperature and precipitation are documented by Greenland ice core data both for glacial times (the so called Dansgaard-Oeschger (D-O) events) as well as for a cooling event in the early Holocene (the 8.2 kyr event). The onsets of D-O warm events are paralleled by abrupt increases in CH4 by up to 250 ppb in a few decades. Vice versa, the 8.2 kyr event is accompanied by an intermittent decrease in CH4 of about 80 ppb over 150 yr. The abrupt CH4 changes are thought to mainly originate from source emission variations in tropical and boreal wet ecosystems, but complex process oriented bottom-up model estimates of the changes in these ecosystems during rapid climate changes are still missing. Here we present simulations of CH4 emissions from northern peatlands with the LPJ-Bern dynamic global vegetation model. The model represents CH4 production and oxidation in soils and transport by ebullition, through plant aerenchyma, and by diffusion. Parameters are tuned to represent site emission data as well as inversion-based estimates of northern wetland emissions. The model is forced with climate input data from freshwater hosing experiments using the NCAR CSM1.4 climate model to simulate an abrupt cooling event. A concentration reduction of ~10 ppb is simulated per degree K change of mean northern hemispheric surface temperature in peatlands. Peatland emissions are equally sensitive to both changes in temperature and in precipitation. If simulated changes are taken as an analogy to the 8.2 kyr event, boreal peatland emissions alone could only explain 23 of the 80 ppb decline in atmospheric methane concentration. This points to a significant contribution to source changes from low latitude and tropical wetlands to this event.

Independent variations of CH₄ emissions and isotopic composition over the past 160,000 years

During the last glacial cycle, greenhouse gas concentrations fluctuated on decadal and longer timescales. Concentrations of methane, as measured in polar ice cores, show a close connection with Northern Hemisphere temperature variability, but the contribution of the various methane sources and sinks to changes in concentration is still a matter of debate. Here we assess changes in methane cycling over the past 160,000 years by measurements of the carbon isotopic composition delta C-13 of methane in Antarctic ice cores from Dronning Maud Land and Vostok. We find that variations in the delta C-13 of methane are not generally correlated with changes in atmospheric methane concentration, but instead more closely correlated to atmospheric CO2 concentrations. We interpret this to reflect a climatic and CO2-related control on the isotopic signature of methane source material, such as ecosystem shifts in the seasonally inundated tropical wetlands that produce methane. In contrast, relatively stable delta C-13 values occurred during intervals of large changes in the atmospheric loading of methane. We suggest that most methane sources-most notably tropical wetlands-must have responded simultaneously to climate changes across these periods.

Ice-Core Based Assessment of Historical Anthropogenic Heavy Metal (Cd, Cu, Sb, Zn) Emissions in the Soviet Union

The development of strategies and policies aiming at the reduction of environmental exposure to air pollution requires the assessment of historical emissions. Although anthropogenic emissions from the extended territory of the Soviet Union (SU) considerably influenced concentrations of heavy metals in the Northern Hemisphere, Pb is the only metal with long-term historical emission estimates for this region available, whereas for selected other metals only single values exist. Here we present the first study assessing long-term Cd, Cu, Sb, and Zn emissions in the SU during the period 1935–1991 based on ice-core concentration records from Belukha glacier in the Siberian Altai and emission data from 12 regions in the SU for the year 1980. We show that Zn primarily emitted from the Zn production in Ust-Kamenogorsk (East Kazakhstan) dominated the SU heavy metal emission. Cd, Sb, Zn (Cu) emissions increased between 1935 and the 1970s (1980s) due to expanded non-ferrous metal production. Emissions of the four metals in the beginning of the 1990s were as low as in the 1950s, which we attribute to the economic downturn in industry, changes in technology for an increasing metal recovery from ores, the replacement of coal and oil by gas, and air pollution control.

Inhibition of photosynthesis by high temperature in oak (Quercus pubescens L.) leaves grown under natural conditions closely correlates with a reversible heat-dependent reduction of the activation state of ribulose-1,5-bisphosphate carboxylase/oxygenase

Inhibition of the net photosynthetic CO2 assimilation rate (Pn) by high temperature was examined in oak (Quercus pubescens L.) leaves grown under natural conditions. Combined measurements of gas exchange and chlorophyll (Chl) a fluorescence were employed to differentiate between inhibition originating from heat effects on components of the thylakoid membranes and that resulting from effects on photosynthetic carbon metabolism. Regardless of whether temperature was increased rapidly or gradually, Pn decreased with increasing leaf temperature and was more than 90% reduced at 45 °C as compared to 25 °C. Inhibition of Pn by heat stress did not result from reduced stomatal conductance (gs), as heat-induced reduction of gs was accompanied by an increase of the intercellular CO2 concentration (Ci). Chl a fluorescence measurements revealed that between 25 and 45 °C heat-dependent alterations of thylakoid-associated processes contributed only marginally, if at all, to the inhibition of Pn by heat stress, with photosystem II being remarkably well protected against thermal inactivation. The activation state of ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) decreased from about 90% at 25 °C to less than 30% at 45 °C. Heat stress did not affect Rubisco per se, since full activity could be restored by incubation with CO2 and Mg2+. Western-blot analysis of leaf extracts disclosed the presence of two Rubisco activase polypeptides, but heat stress did not alter the profile of the activase bands. Inhibition of Pn at high leaf temperature could be markedly reduced by artificially increasing Ci. A high Ci also stimulated photosynthetic electron transport and resulted in reduced non-photochemical fluorescence quenching. Recovery experiments showed that heat-dependent inhibition of Pn was largely, if not fully, reversible. The present results demonstrate that in Q. pubescens leaves the thylakoid membranes in general and photosynthetic electron transport in particular were well protected against heat-induced perturbations and that inhibition of Pn by high temperature closely correlated with a reversible heat-dependent reduction of the Rubisco activation state.

The promoting effect of water on the electroreduction of CO2 in acetonitrile

The promoting effect of water on the electrochemical reduction of carbon dioxide (CO2) from non-aqueous solvents has been studied by means of cyclic voltammetry and in-situ surface-enhanced infrared absorption spectroscopy (SEIRAS). CO2 electroreduction on gold is known to be highly selective towards CO formation in aqueous and in non-aqueous media. The use of non-aqueous solvents is advantageous due to the significantly increased solubility of CO2 compared to aqueous systems. However, in the absence of any proton source, extremely high overpotentials are required for the CO2 electroreduction. In this work, we demonstrate for the first time a tremendous accelerating effect of water additives on the electroreduction of CO2 taking place at gold/acetonitrile interfaces. Already moderate amounts of water, in the concentration range of 0.5 to 0.7 M, are sufficient to decrease significantly the overpotential of CO2 reduction while keeping the CO2 concentration as high as in the pure acetonitrile. The effect of water additives on the mechanism of CO2 electroreduction on gold is discussed on the basis of electrochemical and IR spectroscopic data. The results obtained from gold are compared to analogue experiments carried out on platinum.

Continuous CO2/CH4/CO measurements (2012–2014) at Beromünster tall tower station in Switzerland

The understanding of the continental carbon budget is essential to predict future climate change. In order to quantify CO₂ and CH₄ fluxes at the regional scale, a measurement system was installed at the former radio tower in Beromünster as part of the Swiss greenhouse gas monitoring network (CarboCount CH). We have been measuring the mixing ratios of CO₂, CH₄ and CO on this tower with sample inlets at 12.5, 44.6, 71.5, 131.6 and 212.5 m above ground level using a cavity ring down spectroscopy (CRDS) analyzer. The first 2-year (December 2012–December 2014) continuous atmospheric record was analyzed for seasonal and diurnal variations and interspecies correlations. In addition, storage fluxes were calculated from the hourly profiles along the tower. The atmospheric growth rates from 2013 to 2014 determined from this 2-year data set were 1.78 ppm yr⁻¹, 9.66 ppb yr⁻¹ and and -1.27 ppb yr⁻¹ for CO₂, CH₄ and CO, respectively. After detrending, clear seasonal cycles were detected for CO₂ and CO, whereas CH₄ showed a stable baseline suggesting a net balance between sources and sinks over the course of the year. CO and CO₂ were strongly correlated (r² > 0.75) in winter (DJF), but almost uncorrelated in summer. In winter, anthropogenic emissions dominate the biospheric CO₂ fluxes and the variations in mixing ratios are large due to reduced vertical mixing. The diurnal variations of all species showed distinct cycles in spring and summer, with the lowest sampling level showing the most pronounced diurnal amplitudes. The storage flux estimates exhibited reasonable diurnal shapes for CO₂, but underestimated the strength of the surface sinks during daytime. This seems plausible, keeping in mind that we were only able to calculate the storage fluxes along the profile of the tower but not the flux into or out of this profile, since no Eddy covariance flux measurements were taken at the top of the tower.