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Cosmic rays entering the Earth's atmosphere produce showers of secondary particles such as protons, neutrons, and muons. The interaction of these particles with oxygen-16 (16O) in minerals such as ice and quartz can produce carbon-14 (14C). In glacial ice, 14C is also incorporated through trapping of 14C-containing atmospheric gases (14CO2, 14CO, and 14CH4). Understanding the production rates of in situ cosmogenic 14C is important to deconvolve the in situ cosmogenic and atmospheric 14C signals in ice, both of which contain valuable paleoenvironmental information. Unfortunately, the in situ 14C production rates by muons (which are the dominant production mechanism at depths of >6 m solid ice equivalent) are uncertain. In this study, we use measurements of in situ 14C in ancient ice (>50 ka) from the Taylor Glacier, an ablation site in Antarctica, in combination with a 2D ice flow model to better constrain the compound-specific rates of 14C production by muons and the partitioning of in situ 14C between CO2, CO, and CH4. Our measurements show that 33.7 % (±11.4 %; 95 % confidence interval) of the produced cosmogenic 14C forms 14CO and 66.1 % (±11.5 %; 95 % confidence interval) of the produced cosmogenic 14C forms 14CO2. 14CH4 represents a very small fraction (%) of the total. Assuming that the majority of in situ muogenic 14C in ice forms 14CO2, 14CO, and 14CH4, we also calculated muogenic 14C production rates that are lower by factors of 5.7 (3.6–13.9; 95 % confidence interval) and 3.7 (2.0–11.9; 95 % confidence interval) for negative muon capture and fast muon interactions, respectively, when compared to values determined in quartz from laboratory studies (Heisinger et al., 2002a, b) and in a natural setting (Lupker et al., 2015). This apparent discrepancy in muogenic 14C production rates in ice and quartz currently lacks a good explanation and requires further investigation.

Electrochemical CO2 conversion is a promising way for sustainable chemical fuel production, yet the conversion efficiency is strongly limited by the sluggish kinetics and complex reaction pathways. Here we report the ultrathin conjugated metalloporphyrin covalent organic framework epitaxially grown on graphene as a two-dimensional van der Waals heterostructure to catalyze CO2 reduction. Operando X-ray absorption and density functional theory calculations reveal the strong interlayer coupling leads to electron-deficient metal centers and speeds up electrocatalysis. The Co(III)-N4 centers exhibit a CO Faradaic efficiency of 97% at a partial current density of 8.2 mA cm-2 in an H-cell, along with a stable running over 30 h. The selectivity of CO approached 99% with a partial current density of 191 mA cm-2 in a liquid flow cell, and the turnover frequency achieved 50 400 h-1 at -1.15 V vs RHE, outperforming most reported organometallic frameworks. This work highlights the key role of strong electronic coupling between van der Waals layers for accelerating the dynamics of CO2 conversion. This work is funded by the Natural Science Foundation of China (Grants 21872039 and 22072030), Science and Technology Commission of Shanghai Municipality (Grants 18JC1411700, 19DZ2270100, and 22520711100), and the Fundamental Research Funds for the Central Universities (20720220008).

Developing new technologies for carbon sequestra-tion and long-term carbon storage is important. Clay minerals are interesting in this context as they are low-cost, naturally abundant, can adsorb considerable amounts of CO2, and are present in storage sites for anthropogenic carbon. Here, to better understand the intercalation mechanisms of CO2 in dehydrated and hydrated synthetic Na-fluorohectorite clay, we have combined powder X-ray diffraction, inelastic and quasi-elastic neutron scattering, and density functional theory calculations. For dehydrated Na-fluorohectorite, we observe no crystalline swelling or spectroscopic changes in response to CO2, whereas for the hydrated case, damping of the librational modes related to the intercalated water was clearly observed. These findings suggest the formation of a more disordered water coordination in the interlayer associated with highly confined water molecules. From the simulations, we conclude that intercalated water molecules decrease the layer-layer cohesion energy and create physical space for CO2 intercalation. Furthermore, we confirm that interlayer confinement reduces the Na+ hydration number when compared to that in bulk aqueous water, which may allow for proton transfer and hydroxide formation followed by CO2 adsorption in the form of carbonates. The experimental results are discussed in the context of previous and present observations on, a similar smectite, Ni-fluorohectorite, for which it is established that CO2 attaches to the edge of nickel hydroxide islands present in the interlayer.

Arctic tundra is facing unprecedented warming, resulting in shifts in the vegetation, thaw regimes, and potentially in the ecosystem-atmosphere exchange of carbon (C). However, the estimates of regional carbon dioxide (CO2) and methane (CH4) budgets are highly uncertain. We measured CO2 and CH4 fluxes, vegetation composition and leaf area index (LAI), thaw depth, and soil wetness in Tiksi (71 degrees N, 128 degrees E), a heterogeneous site located within the prostrate dwarf-shrub tundra zone in northeastern Siberia. Using the closed chamber method, we determined the net ecosystem exchange (NEE) of CO2, ecosystem respiration in the dark (ER), ecosystem gross photosynthesis (Pg), and CH4 flux during the growing season. We applied a previously developed high-spatial-resolution land cover map over an area of 35.8 km(2) for spatial extrapolation. Among the land cover types varying from barren to dwarf-shrub tundra and tundra wetlands, the NEE and Pg at the photosynthetically active photon flux density of 800 mu mol m(-2) h(-1) (NEE800 and Pg(800)) were greatest in the graminoid-dominated habitats, i.e., streamside meadow and fens, with NEE800 and Pg(800) of up to -21 (uptake) and 28 mmol M-2 h(-1), respectively. Vascular LAI was a robust predictor of both NEE800 and Pg(800) and, on a landscape scale, the fens were disproportionately important for the summertime CO2 sequestration. Dry tun- dra, including the dwarf-shrub and lichen tundra, had smaller CO2 exchange rates. The fens were the largest source of CH4, while the dry mineral soil tundra consumed atmospheric CH4, which on a landscape scale amounted to -9 % of the total CH(4 )balance during the growing season. The largest seasonal mean CH4 consumption rate of 0.02 mmol m(-2) h(-1) occurred in sand- and stone-covered barren areas. The high consumption rate agrees with the estimate based on the eddy covariance measurements at the same site. We acknowledge the uncertainty involved in spatial extrapolations due to a small number of replicates per land cover type. This study highlights the need to distinguish different land cover types including the dry tundra habitats to account for their different CO2 and CH4 flux patterns, especially the consumption of atmospheric CH4, when estimating tundra C exchange on a larger spatial scale.

Photoelectrochemical (PEC) CO2 reduction has received considerable attention given the inherent sustainability and simplicity of directly converting solar energy into carbonbased chemical fuels. However, complex photocathode architectures with protecting layers and cocatalysts are typically needed for selective and stable operation. We report herein that bare CuIn0.3Ga0.7S2 photocathodes can drive the PEC CO2 reduction with a benchmarking 1 Sun photocurrent density of over 2 mA/cm(2) (at -2 V vs Fc(+)/Fc) and a product selectivity of up to 87% for CO (CO/all products) production while also displaying long-term stability for syngas production (over 44 h). Importantly, spectroelectrochemical analysis using PEC impedance spectroscopy (PEIS) and intensity-modulated photocurrent spectroscopy (IMPS) complements PEC data to reveal that tailoring the proton donor ability of the electrolyte is crucial for enhancing the performance, selectivity, and durability of the photocathode. When a moderate amount of protons is present, the density of photogenerated charges accumulated at the interface drops significantly, suggesting a faster charge transfer process. However, with a high concentration of proton donors, the H2 evolution reaction is preferred., [GRAPHICS]

Elevated atmospheric CO2 concentrations (e[CO2]) have a significant impact on plant physiology, grain yield and quality and the specific response of plants to e[CO2] is closely linked to cultivars. Here, five Chinese wheat (Triticum aestivum L.) cultivars were grown under ambient CO2 (a[CO2], 400 ppm) and e[CO2] (800 ppm). CO2 enrichment significantly increased net photosynthetic rate and water use efficiency but depressed stomatal conductance. e[CO2] increased the carbon (C) concentration but decreased the nitrogen (N) concentration in all five cultivars, whereas the effect of e[CO2] on grain yield was highly dependent on cultivar. Moreover, e[CO2] caused a significant reduction in grain minerals and protein, although the magnitude of reduction was different among these cultivars. The starch concentrations in the grains and flour viscosity were not significantly affected at e[CO2]. These findings improve our understanding of the interactive effect of CO2 conditions and cultivars on plant performances and provide a research basis to select suitable wheat cultivars to deal with food crisis in future climate.

The success of catalytic schemes for the large-scale valorization of CO2 does not only depend on the development of active, selective and stable catalytic materials but also on the overall process design. Here we present a multidisciplinary study (from catalyst to plant and techno-economic/lifecycle analysis) for the production of green methanol from renewable H2 and CO2. We combine an in-depth kinetic analysis of one of the most promising recently reported methanol-synthesis catalysts (InCo) with a thorough process simulation and techno-economic assessment. We then perform a life cycle assessment of the simulated process to gauge the real environmental impact of green methanol production from CO2. Our results indicate that up to 1.75 ton of CO2 can be abated per ton of produced methanol only if renewable energy is used to run the process, while the sensitivity analysis suggest that either rock-bottom H2 prices (1.5 $ kg−1) or severe CO2 taxation (300 $ per ton) are needed for a profitable methanol plant. Besides, we herein highlight and analyze some critical bottlenecks of the process. Especial attention has been paid to the contribution of H2 to the overall plant costs, CH4 trace formation, and purity and costs of raw gases. In addition to providing important information for policy makers and industrialists, directions for catalyst (and therefore process) improvements are outlined., Journal of Energy Chemistry, 68

Coastal methane (CH4) emissions dominate the global ocean CH4 budget and can offset the "blue carbon" storage capacity of vegetated coastal ecosystems. However, current estimates lack systematic, high-resolution, and long-term data from these intrinsically heterogeneous environments, making coastal budgets sensitive to statistical assumptions and uncertainties. Using continuous CH4 concentrations, delta C-13-CH4 values, and CH4 sea-air fluxes across four seasons in three globally pervasive coastal habitats, we show that the CH4 distribution is spatially patchy over meter-scales and highly variable in time. Areas with mixed vegetation, macroalgae, and their surrounding sediments exhibited a spatiotemporal variability of surface water CH4 concentrations ranging two orders of magnitude (i.e., 6-460 nM CH4) with habitat-specific seasonal and diurnal patterns. We observed (1) delta C-13-CH signatures that revealed habitat-specific CH4 production and consumption pathways, (2) daily peak concentration events that could change >100% within hours across all habitats, and (3) a high thermal sensitivity of the CH4 distribution signified by apparent activation energies of similar to 1 eV that drove seasonal changes. Bootstrapping simulations show that scaling the CH4 distribution from few samples involves large errors, and that similar to 50 concentration samples per day are needed to resolve the scale and drivers of the natural variability and improve the certainty of flux calculations by up to 70%. Finally, we identify northern temperate coastal habitats with mixed vegetation and macroalgae as understudied but seasonally relevant atmospheric CH4 sources (i.e., releasing >= 100 mu mol CH4 m(-2) day(-1) in summer). Due to the large spatial and temporal heterogeneity of coastal environments, high-resolution measurements will improve the reliability of CH4 estimates and confine the habitat-specific contribution to regional and global CH4 budgets.

Hypothesis Imbibition of a fluid into a porous material involves the invasion of a wetting fluid in the pore space through piston-like displacement, film and corner flow, snap-off and pore bypassing. These processes have been studied extensively in two-dimensional (2D) porous systems; however, their relevance to three-dimensional (3D) natural porous media is poorly understood. Here, we investigate these pore-scale processes in a natural rock sample using time-resolved 3D (i.e., four-dimensional or 4D) X-ray imaging. Experiments We performed a capillary-controlled drainage-imbibition experiment on an initially brine-saturated carbonate rock sample. The sample was imaged continuously during imbibition using 4D X-ray imaging to visualize and analyze fluid displacement and snap-off processes at the pore-scale. Findings We discover a new type of snap-off that occurs in pores, resulting in the entrapment of a small portion of the non-wetting phase in pore corners. This contrasts with previously-observed snap-off in throats which traps the non-wetting phase in pore centers. We relate the new type of pore-snap-off to the pinning of fluid-fluid interfaces at rough surfaces, creating contact angles close to 90°. Subsequently, we provide correlations for displacement events as a function of pore-throat geometry. Our findings indicate that having a small throat does not necessarily favor snap-off: the key criterion is the throat radius in relation to the pore radius involved in a displacement event, captured by the aspect ratio.

Excess adsorption of CO2, CH4, N2, and H2 on ZIF-8 was measured gravimetrically in the pressure range ranging from vacuum to 30 MPa at 298.15, 313.15, 333.15, 353.15, and 394.15 K using a magnetic suspension balance. The textural properties of the adsorbent material─i.e., skeletal density, surface area, pore volume, and pore-size distribution─were estimated by helium gravimetry and N2 (77 K) physisorption. The adsorption isotherms were fitted with the Sips isotherm model and the virial equation, and the values of isosteric heat of adsorption and Henry constants for the gases were determined using the latter.

CO2 is the main greenhouse gas in Earth's atmosphere, and has been causing global warming since the industrial revolution. Therefore, technologies to mitigate carbon emissions have attracted extensive research. Shale gas reservoirs could serve as potential sequestration space for CO2. This paper aims to gain insight in the CO2 adsorption behavior and mechanism in Longmaxi shale. The micropore filling theory is the best model for CO2 adsorption in the shale samples with the smallest MSR (Mean Square of Residual). This model fits better than that of the monolayer adsorption and multi-layer adsorption theories. Specifically, micropore filling adsorption mainly occurs in micropores, including the closed end of slit pores, capillary pores, and ink-shaped pores. Molecular layer adsorption mainly occurs in mesopores and macropores, including the open end of slit pores, plate pores, capillary pores, and ink-shaped pores. Moreover, the prediction model of CO2 storage quantity in deep shale gas reservoirs of China is established. This model shows that 91.5-388.89 × 1012 m3 of CO2 could in theory be stored in an adsorbed state. CO2 is mostly stored by an adsorbed state (higher than 95%) and a free state with good security and low leakage risk. The results from this work are of specific interest for global research on CO2 adsorption characteristics and adsorption mechanisms in different pore structures. Furthermore, it provides certain guidance for geological storage of CO2 in shale. ispartof: RSC ADVANCES vol:12 issue:40 pages:25947-25954 ispartof: location:England status: published

Electrolytic formic acid synthesis delivers green formic acid at the right concentration for emerging applications.

Broadband mid-infrared (MIR) spectroscopy is a well-established and valuable diagnostic technique for reactive plasmas. Plasmas are complex systems and consist of numerous (reactive) types of molecules; it is challenging to measure and control reaction specificity with a good sensitivity. Here, we demonstrate the first use of a novel MIR supercontinuum (SC) source for quantitative plasma spectroscopy. The SC source has a wide spectral coverage of 1300–2700 cm−1 (wavelength range 3.7–7.7 μm), thus enabling broadband multispecies detection. The high spatial coherence of the MIR SC source provides long interaction path lengths, thereby increasing the sensitivity for molecular species. The combination of such a SC source with a custom-built FTIR spectrometer (0.1 cm−1 spectral resolution) allows detection of various gases with high spectral resolution. We demonstrate its potential in plasma applications by accurate identification and quantification of a variety of reaction products (e.g. nitrogen oxides and carbon oxides) under low-pressure conditions, including the molecular species with overlapping absorbance features (e.g. acetone, acetaldehyde, formaldehyde, etc.).

For many biomedical applications, high-precision CO2 detection with a rapid response is essential. Due to the superior surface-active characteristics, 2D materials are particularly crucial for electrochemical sensors. The liquid phase exfoliation method of 2D Co2Te3 production is used to achieve the electrochemical sensing of CO2. The Co2Te3 electrode performs better than other CO2 detectors in terms of linearity, low detection limit, and high sensitivity. The outstanding physical characteristics of the electrocatalyst, including its large specific surface area, quick electron transport, and presence of a surface charge, can be credited for its extraordinary electrocatalytic activity. More importantly, the suggested electrochemical sensor has great repeatability, strong stability, and outstanding selectivity. Additionally, the electrochemical sensor based on Co2Te3 could be used to monitor respiratory alkalosis.

The coupling of CO-generating molecular catalysts with copper electrodes in tandem schemes is a promising strategy to boost the formation of multi-carbon products in the electrocatalytic reduction of CO2. While the spatial distribution of the two components is important, this aspect remains underexplored for molecular-based tandem systems. Herein, we address this knowledge gap by studying tandem catalysts comprising Co-phthalocyanine (CoPc) and Cu nanocubes (Cu-cub). In particular, we identify the importance of the relative spatial distribution of the two components on the performance of the tandem catalyst by preparing CoPc-Cu-cub/C, wherein the CoPc and Cu-cub share an interface, and CoPc-C/Cu-cub, wherein the CoPc is loaded first on carbon black (C) before mixing with the Cu-cub. The electrocatalytic measurements of these two catalysts show that the faradaic efficiency towards C-2 products almost doubles for the CoPc-Cu-cub/C, whereas it decreases by half for the CoPc-C/Cu-cub, compared to the Cu-cub/C. Our results highlight the importance of a direct contact between the CO-generating molecular catalyst and the Cu to promote C-C coupling, which hints at a surface transport mechanism of the CO intermediate between the two components of the tandem catalyst instead of a transfer via CO diffusion in the electrolyte followed by re-adsorption.

The chemistry of lanthanides is limited to one electron transfer reactions due to the difficulty of accessing multiple oxidation states. Here we report that a redox-active ligand combining three siloxides with an arene ring in a tripodal ligand can stabilize cerium complexes in four different redox states and can promote multielectron redox reactivity in cerium complexes. Ce(iii) and Ce(iv) complexes [(LO3)Ce(THF)] (1) and [(LO3)CeCl] (2) (LO3 = 1,3,5-(2-OSi((OBu)-Bu-t)(2)C6H4)(3)C6H3) were synthesized and fully characterized. Remarkably the one-electron reduction and the unprecedented two-electron reduction of the tripodal Ce(iii) complex are easily achieved to yield reduced complexes [K(2.2.2-cryptand)][(LO3)Ce(THF)] (3) and [K-2{(LO3)Ce(Et2O)(3)}] (5) that are formally "Ce(ii)" and "Ce(i)" analogues. Structural analysis, UV and EPR spectroscopy and computational studies indicate that in 3 the cerium oxidation state is in between +II and +III with a partially reduced arene. In 5 the arene is doubly reduced, but the removal of potassium results in a redistribution of electrons on the metal. The electrons in both 3 and 5 are stored onto d-bonds allowing the reduced complexes to be described as masked "Ce(ii)" and "Ce(i)". Preliminary reactivity studies show that these complexes act as masked Ce(ii) and Ce(i) in redox reactions with oxidizing substrates such as Ag+, CO2, I-2 and S-8 effecting both one- and two-electron transfers that are not accessible in classical cerium chemistry.

A three compartment solar formic acid generator was built using a Sn on Cu foam cathode and NiFe anode. A bipolar combination of a Fumasep FAD-PET-75 and Nafion 117 membrane was mounted between anode and middle compartment, which was filled with Amberlyst 15H ion exchanger beads. A Fumasep FAD-PET-75 membrane separated the middle compartment from the cathode. The generator was powered with a photovoltaic panel and fed with gaseous CO2 and water. Diluted formic acid solution was produced by flowing water through the middle compartment. Common PV-EC devices are operated using aqueous electrolyte and produce aqueous formate. In our PV-EC device, formic acid is produced straight away, avoiding the need for downstream operations to convert formate to formic acid. The electrolyser was matched with solar photovoltaic cells achieving a coupling efficiency as high as 95%. Our device produces formic acid at a faradaic efficiency of ca. 31% and solar-to-formic acid efficiency of ca. 2%. By producing formic acid from CO2 and water without any need of additional chemicals this electrolyser concept is attractive for use at remote locations with abundant solar energy. Formic acid serves as a liquid renewable fuel or chemical building block.

Due to a swift and continuous growth of the insect rearing industry during the last two decades, there is a need for a better understanding of insect diseases (caused by insect pathogens). In the insect production sector, insect diseases are a bottleneck for every type and scale of rearing system with different degrees of technology investment (i.e. semi-open rearing, closed rearing, industrial production, small-scale farming). In this paper, we provide an overview of insect pathogens that are causing disease in the most common insect species reared or collected for use in food and feed. We also include a few examples of diseases of insect species, which are not (yet) reported to be used as food or feed; those examples may increase our understanding of insect diseases in general and for the development of disease prevention and control measures. We pay special attention to the effect of selected biotic and abiotic factors as potential triggers of insect diseases. We discuss the effect of such factors in combination with other production variables on disease development and insect immunocompetence. Additionally, we touch upon prevention and control measures that have been carried out and suggested up to now for insect production systems. Finally, we point towards possible future research directions with possibilities to enhance the resilience of insect production to insect disease outbreaks.

A sustainable future demands a successful transition from a carbon-energy dependent economy towards renewable energy schemes, many of which ultimately rely on the development of efficient electrocatalysis that either converts chemical energy into electricity or uses electrons to produce chemical energy. In general, electrocatalysis studies focus on the interactions (e.g., electron transfer) between the catalyst surface and the reaction intermediates. However, the role of electron spin, as an intrinsic property of electrons, has commonly been overlooked. Recently, controlling the electron spin polarization at the catalyst’s surface demonstrated the great potential of boosting both reaction activity and product selectivity. Molecule-induced electron spin polarization inspired by the chiral-induced spin selectivity (CISS) effect has started to have a remarkable impact in electrocatalysis. In this compact review, we summarize the latest studies that use molecule-induced electron spin polarization to enhance catalytic performance. We focus on the reactions essential to the so-called hydrogen economy, and discuss the feasibility and limitations of this effect. Finally, we share our perspective regarding the more impactful future applications.

While wetlands are the largest natural source of methane (CH4 ) to the atmosphere, they represent a large source of uncertainty in the global CH4 budget due to the complex biogeochemical controls on CH4 dynamics. Here we present, to our knowledge, the first multi-site synthesis of how predictors of CH4 fluxes (FCH4) in freshwater wetlands vary across wetland types at diel, multiday (synoptic), and seasonal time scales. We used several statistical approaches (correlation analysis, generalized additive modeling, mutual information, and random forests) in a wavelet-based multi-resolution framework to assess the importance of environmental predictors, nonlinearities and lags on FCH4 across 23 eddy covariance sites. Seasonally, soil and air temperature were dominant predictors of FCH4 at sites with smaller seasonal variation in water table depth (WTD). In contrast, WTD was the dominant predictor for wetlands with smaller variations in temperature (e.g., seasonal tropical/subtropical wetlands). Changes in seasonal FCH4 lagged fluctuations in WTD by ~17±11days, and lagged air and soil temperature by median values of 8±16 and 5±15days, respectively. Temperature and WTD were also dominant predictors at the multiday scale. Atmospheric pressure (PA) was another important multiday scale predictor for peat-dominated sites, with drops in PA coinciding with synchronous releases of CH4 . At the diel scale, synchronous relationships with latent heat flux and vapor pressure deficit suggest that physical processes controlling evaporation and boundary layer mixing exert similar controls on CH4 volatilization, and suggest the influence of pressurized ventilation in aerenchymatous vegetation. In addition, 1- to 4-h lagged relationships with ecosystem photosynthesis indicate recent carbon substrates, such as root exudates, may also control FCH4. By addressing issues of scale, asynchrony, and nonlinearity, this work improves understanding of the predictors and timing of wetland FCH4 that can inform future studies and models, and help constrain wetland CH4 emissions.

Determining the fate of CO2 respired in woody tissues is necessary to understand plant respiratory physiology and to evaluate CO2 recycling mechanisms. An aqueous 13 C-enriched CO2 solution was infused into the stem of 3-4 m tall trees to estimate efflux and assimilation of xylem-transported CO2 via cavity ring down laser spectroscopy and isotope ratio mass spectrometry, respectively. Different tree locations (lower stem, upper stem and leafy shoots) and tissues (xylem, bark and leaves) were monitored in species with tracheid, diffuse- and ring- porous wood anatomy (cedar, maple and oak, respectively). Radial xylem CO2 diffusivity and xylem [CO2 ] were lower in cedar relative to maple and oak trees, thereby limiting label diffusion. Part of the labeled 13 CO2 was assimilated in cedar (8.7 %) and oak (20.6 %) trees, mostly in xylem and bark tissues of the stem, while limited solution uptake in maple trees hindered detection of label assimilation. Little label reached foliar tissues, suggesting substantial label loss along the stem-branch transition following reductions in the radial diffusive pathway. Differences in respiration rates and radial xylem CO2 diffusivity (lower in conifer relative to angiosperm species) might reconcile discrepancies in efflux and assimilation of xylem-transported CO2 so far observed between taxonomic clades. This article is protected by copyright. All rights reserved.

Despite being desirable high-value products of the electrochemical CO2 reduction reaction (CO2RR), alcohols are still obtained with lower selectivity compared to hydrocarbons and the reaction pathways leading to their formation are still under debate. In this joint experimental-computational work, we exploit structural sensitivity effects to elucidate the ethanol-producing active sites on Cu-Ag CO2RR tandem catalysts. Specifically, methane-selective Cu nano-octahedra (Cuoh), enclosed by (111) facets, and ethylene-selective Cu nano-cubes (Cucub), enclosed by (100) facets, are mixed with CO-selective Ag nanospheres (Agsph) to form Cuoh-Ag and Cucub-Ag bimetallic catalysts. Ethanol is selectively enhanced via the *CHx-*CO coupling pathway at the terraces of Cuoh-Ag in the CO-enriched environment generated by the Agsph . Conversely, on Cucub-Ag ethanol is selectively produced via the same pathway at the edges and corners of Cucub while ethylene continues to be produced at the terraces. Such facet dependence explains the higher ethanol-to-ethylene ratio on the Cuoh-Ag. These findings illustrate how tandem catalysis and structure-sensitive effects can be combined to obtain notable changes in the selectivity of electrochemical reactions. This work was financially supported by Gaznat S.A. J.R.P. acknowledges the H2020 Marie Curie Individual Fellowship grant SURFCAT with agreement number 837378. This publication was created as part of NCCR Catalysis, a National Centre of Competence in Research funded by the Swiss National Science Foundation. The theoretical effort was supported by Spanish MICIUN’s RTI2018-095460-B-I00, Ramón y Cajal RYC-2015-18996, and María de Maeztu MDM-2017-0767 grants and partly by Generalitat de Catalunya via 2017SGR13, XRQTC grants. M.J.K. and F.C.-V. are thankful to Red Española de Supercomputación (RES) for supercomputing time at SCAYLE (projects QS-2019-3-0018, QS-2019-2-0023, and QCM-2019-1-0034). The use of supercomputing facilities at SURFsara was sponsored by NWO Physical Sciences.

Personal cloud, termed as the difference in air pollutant concentrations between breathing zone and room sites, represents the bias in approximating personal inhalation exposure that is linked to accuracy of health risk assessment. This study performed a two-week field experiment in a naturally ventilated office during the COVID19 pandemic to assess occupants' exposure to common air pollutants and to determine factors contributing to the personal cloud effect. During occupied periods, indoor average concentrations of endotoxin (0.09 EU/m3), TVOC (231 mu g/m3), CO2 (630 ppm), and PM10 (14 mu g/m3) were below the recommended limits, except for formaldehyde (58 mu g/m3). Personal exposure concentrations, however, were significantly different from, and mostly higher than, concentrations measured at room stationary sampling sites. Although three participants shared the same office, their personal air pollution clouds were mutually distinct. The mean personal cloud magnitude ranged within 0-0.05 EU/m3, 35-192 mu g/m3, 32-120 ppm, and 4-9 mu g/m3 for endotoxin, TVOC, CO2, and PM10, respectively, and was independent from room concentrations. The use of hand sanitizer was strongly associated with an elevated personal cloud of endotoxin and alcohol-based VOCs. Reduced occupancy density in the office resulted in more pronounced personal CO2 clouds. The representativeness of room stationary sampling for capturing dynamic personal exposures was as low as 28% and 5% for CO2 and PM10, respectively. The findings of our study highlight the necessity of considering the personal cloud effect when assessing personal exposure in offices.

Activation of CO2 is the first step towards its reduction to more useful chemicals. Here we systematically investigate the CO2 activation mechanism on Cu3X (X is a first-row transition metal atom) using density functional theory computations. The CO2 adsorption energies and the activation mechanisms depend strongly on the selected dopant. The dopant electronegativity, the HOMO-LUMO gap and the overlap of the frontier molecular orbitals control the CO2 dissociation efficiency. Our calculations reveal that early transition metal-doped (Sc, Ti, V) clusters exhibit a high CO2 adsorption energy, a low activation barrier for its dissociation, and a facile regeneration of the clusters. Thus, early transition metal-doped copper clusters, particularly Cu3Sc, may be efficient catalysts for the carbon capture and utilization process. ispartof: PHYSICAL CHEMISTRY CHEMICAL PHYSICS vol:23 issue:38 pages:21738-21747 ispartof: location:England status: published

The photochemical reduction of carbon dioxide (CO2) into methanol is very appealing since it requires sunlight as the only energy input. However, the development of highly selective and efficient photocatalysts is still very challenging. It has been reported that CO2 can be spontaneously activated on gallium nitride (GaN). Moreover, the photocatalytic activity for CO2 conversion into methanol can be drastically enhanced by incorporating a small amount of Mg dopant. In this work, density functional theory (DFT) based on a cluster model approach has been applied to further explore the photocatalytic activity of bare GaN towards CO2 adsorption and conversion. We extended the investigation of Mg-doping replacing one Ga atom with Mg on three different sites and evaluated the consequent effects on the band gaps and CO2 adsorption energies. Finally, we explore different routes leading to the production of methanol and evaluate the catalytic activity of bare GaN by applying the energetic span model (ESM) in order to identify the rate-determining states which are fundamental for suggesting modifications that can improve the photocatalytic activity of this promising material.

Among all CO2 electroreduction products, methane (CH4) and ethylene (C2H4) are two typical and valuable hydrocarbon products which are formed in two different pathways: hydrogenation and dimerization reactions of the same CO intermediate. Theoretical studies show that the adsorption configurations of CO intermediate determine the reaction pathways towards CH4/C2H4. However, it is challenging to experimentally control the CO adsorption configurations at the catalyst surface, and thus the hydrocarbon selectivity is still limited. Herein, we seek to synthesize two well-defined copper nanocatalysts with controllable surface structures. The two model catalysts exhibit a high hydrocarbon selectivity toward either CH4 (83%) or C2H4 (93%) under identical reduction conditions. Scanning transmission electron microscopy and X-ray absorption spectroscopy characterizations reveal the low-coordination Cu-0 sites and local Cu-0/Cu+ sites of the two catalysts, respectively. CO-temperature programed desorption, in-situ attenuated total reflection Fourier transform infrared spectroscopy and density functional theory studies unveil that the bridge-adsorbed CO (COB) on the low-coordination Cu-0 sites is apt to be hydrogenated to CH4, whereas the bridge-adsorbed CO plus linear-adsorbed CO (COB + COL) on the local Cu-0/Cu+ sites are apt to be coupled to C2H4. Our findings pave a new way to design catalysts with controllable CO adsorption configurations for high hydrocarbon product selectivity. (C) 2020 Science China Press. Published by Elsevier B.V. and Science China Press. All rights reserved.

Background Progressive CO2-induced ocean acidification (OA) impacts marine life in ways that are difficult to predict but are likely to become exacerbated over generations. Although marine fishes can balance acid–base homeostasis efficiently, indirect ionic regulation that alter neurosensory systems can result in behavioural abnormalities. In marine invertebrates, OA can also affect immune system function, but whether this is the case in marine fishes is not fully understood. Farmed fish are highly susceptible to disease outbreak, yet strategies for overcoming such threats in the wake of OA are wanting. Here, we exposed two generations of the European sea bass (Dicentrarchus labrax) to end-of-century predicted pH levels (IPCC RCP8.5), with parents (F1) being exposed for four years and their offspring (F2) for 18 months. Our design included a transcriptomic analysis of the olfactory rosette (collected from the F2) and a viral challenge (exposing F2 to betanodavirus) where we assessed survival rates. Results We discovered transcriptomic trade-offs in both sensory and immune systems after long-term transgenerational exposure to OA. Specifically, RNA-Seq analysis of the olfactory rosette, the peripheral olfactory organ, from 18-months-old F2 revealed extensive regulation in genes involved in ion transport and neuronal signalling, including GABAergic signalling. We also detected OA-induced up-regulation of genes associated with odour transduction, synaptic plasticity, neuron excitability and wiring and down-regulation of genes involved in energy metabolism. Furthermore, OA-exposure induced up-regulation of genes involved in innate antiviral immunity (pathogen recognition receptors and interferon-stimulated genes) in combination with down-regulation of the protein biosynthetic machinery. Consistently, OA-exposed F2 challenged with betanodavirus, which causes damage to the nervous system of marine fish, had acquired improved resistance. Conclusion F2 exposed to long-term transgenerational OA acclimation showed superior viral resistance, though as their metabolic and odour transduction programs were altered, odour-mediated behaviours might be consequently impacted. Although it is difficult to unveil how long-term OA impacts propagated between generations, our results reveal that, across generations, trade-offs in plastic responses is a core feature of the olfactory epithelium transcriptome in OA-exposed F2 offspring, and will have important consequences for how cultured and wild fish interacts with its environment.

Peatlands are globally significant carbon stocks and may become major sources of the greenhouse gases (GHGs) carbon dioxide and methane in a changing climate and under anthropogenic management pressure. Diffusion is the dominant gas transport mechanism in peat; therefore, a proper knowledge of the soil gas diffusion coefficient is important for the estimation of GHG emissions from peatlands. Pore network modeling (PNM) is a potential tool for the determination of gas diffusivity in peat, as it explicitly connects the peat microstructure and the characteristics of the peat pore network to macroscopic gas transport properties. In the present work, we extracted macropore networks from three-dimensional X-ray micro-computed tomography (µCT) images of peat samples and simulated gas diffusion in these networks using PNM. These results were compared to the soil gas diffusion coefficients determined from the same samples in the laboratory using the diffusion chamber method. The measurements and simulations were conducted for peat samples from three depths. The soil gas diffusion coefficients were determined under varying water contents adjusted in a pressure plate apparatus. We also assessed the applicability of commonly used gas diffusivity models to peat. The laboratory measurements showed a decrease in gas diffusivity with depth due to a decrease in air-filled porosity and pore space connectivity. However, gas diffusivity was not extremely low close to saturation, which may indicate that the structure of the macropore network is such that it enables the presence of connected diffusion pathways through the peat matrix, even in wet conditions. The traditional gas diffusivity models were not very successful in predicting the soil gas diffusion coefficient. This may indicate that the microstructure of peat differs considerably from the structure of mineral soils and other kinds of porous materials for which these models have been constructed and calibrated. By contrast, the pore network simulations reproduced the laboratory-determined soil gas diffusion coefficients rather well. Thus, the combination of the µCT and PNM methods may offer a promising alternative to the traditional estimation of soil gas diffusivity through laboratory measurements.

In his editorial, Kevin Staley criticizes our recent work demonstrating the lack of effect of bumetanide in a novel model of neonatal seizures. The main points in our response are that (1) our work is on an asphyxia model, not one on "hypercarbia only"; (2) clinically relevant parenteral doses of bumetanide applied in vivo lead to concentrations in the brain parenchyma that are at least an order of magnitude lower than what would be sufficient to exert any direct effect-even a transient one-on neuronal functions, including neonatal seizures; and (3) moreover, bumetanide's molecular target in the brain is the Na-K-2Cl cotransporter NKCC1, which has vital functions in neurons, astrocytes, and oligodendrocytes as well as microglia. This would make it impossible even for highly brain-permeant NKCC1 blockers to specifically target depolarizing and excitatory actions of gamma-aminobutyric acid in principal neurons of the brain, which is postulated as the rationale of clinical trials on neonatal seizures.

Herein, we report a series of easily accessible bidentate N-heterocyclic carbene (NHC) cobalt catalysts, which enable the hydrogenation of hindered alkenes under mild conditions. The four-coordinated bidentate NHC-Co(II) complexes were characterized by X-ray diffraction, elemental analysis, ESI-HRMS, and magnetic moment measurements, revealing a distorted-tetrahedral geometry and a high-spin configuration of the metal center. The activity of the in situ formed catalytic system, which was obtained from easily available NHC precursors, CoCl2, and NaHBEt3, was identical with those of well-defined NHC-cobalt catalysts. This highlights the potential utility of this reaction system.

The synthesis of fuels from CO2 has made tremendous progress in recent years, although practical applications remain limited. Herein, we describe a cyclic process that produces MeOH from CO2via formamide intermediates, which are initially reduced using NaBH4 to form methanol and concomitantly release the corresponding amine, from which the formamide is subsequently regenerated in the presence of CO2/NaBH4. By tuning the substituents on the formamide/amine, the selectivity of both steps can be controlled, allowing the process to proceed in high yields, either in two separate steps or in a single step process. The observed trends in reactivity were rationalized with a resonance model of the formamide, which supports the observed trends in reactivity, and further consolidated by spectroscopy and calculations. Fil: Uranga, Jorge Gustavo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina. École Polytechnique Fédérale de Lausanne; Suiza Fil: Gopakumar, Aswin. École Polytechnique Fédérale de Lausanne; Suiza Fil: Pfister, Tim. École Polytechnique Fédérale de Lausanne; Suiza Fil: Imanzade, Gunay. École Polytechnique Fédérale de Lausanne; Suiza Fil: Lombardo, Loris. École Polytechnique Fédérale de Lausanne; Suiza Fil: Gastelu, Gabriela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Züttel, Andreas. École Polytechnique Fédérale de Lausanne; Suiza Fil: Dyson, Paul. École Polytechnique Fédérale de Lausanne; Suiza

BACKGROUND: Modern health concerns related to air pollutant exposure in buildings have been exacerbated owing to several factors. Methods for assessing inhalation exposures indoors have been restricted to stationary air pollution measurements, typically assuming steady-state conditions. Objective We aimed to examine the feasibility of several proxy methods for estimating inhalation exposure to CO2, PM2.5, and PM10 in simulated office environments., METHODS: In a controlled climate chamber mimicking four different office setups, human participants performed a set of scripted sitting and standing office activities. Three proxy sensing techniques were examined: stationary indoor air quality (IAQ) monitoring, individual monitoring of physiological status by wearable wristband, human presence detection by Passive Infrared (PIR) sensors. A ground-truth of occupancy was obtained from video recordings of network cameras. The results were compared with the concurrent IAQ measurements in the breathing zone of a reference participant by means of multiple linear regression (MLR) analysis with a combination of different input parameters., RESULTS: Segregating data onto sitting and standing activities could lead to improved accuracy of exposure estimation model for CO2 and PM by 9-60% during sitting activities, relative to combined activities. Stationary PM2.5 and PM10 monitors positioned at the ceiling-mounted ventilation exhaust in vicinity of the seated reference participant accurately estimated inhalation exposure (adjusted R-2 = 0.91 and R-2 = 0.87). Measurement at the front edge of the desk near abdomen showed a moderate accuracy (adjusted R-2 = 0.58) in estimating exposure to CO2. Combining different sensing techniques improved the CO2 exposure detection by twofold, whereas the improvement for PM exposure detection was small (similar to 10%)., SIGNIFICANCE: This study contributes to broadening the knowledge of proxy methods for personal exposure estimation under dynamic occupancy profiles. The study recommendations on optimal monitor combination and placement could help stakeholders better understand spatial air pollutant gradients indoors which can ultimately improve control of IAQ.

Atmospheric inverse modeling describes the process of estimating greenhouse gas fluxes or air pollution emissions at the Earth's surface using observations of these gases collected in the atmosphere. The launch of new satellites, the expansion of surface observation networks, and a desire for more detailed maps of surface fluxes have yielded numerous computational and statistical challenges for standard inverse modeling frameworks that were often originally designed with much smaller data sets in mind. In this article, we discuss computationally efficient methods for large-scale atmospheric inverse modeling and focus on addressing some of the main computational and practical challenges. We develop generalized hybrid projection methods, which are iterative methods for solving large-scale inverse problems, and specifically we focus on the case of estimating surface fluxes. These algorithms confer several advantages. They are efficient, in part because they converge quickly, they exploit efficient matrix-vector multiplications, and they do not require inversion of any matrices. These methods are also robust because they can accurately reconstruct surface fluxes, they are automatic since regularization or covariance matrix parameters and stopping criteria can be determined as part of the iterative algorithm, and they are flexible because they can be paired with many different types of atmospheric models. We demonstrate the benefits of generalized hybrid methods with a case study from NASA's Orbiting Carbon Observatory 2 (OCO-2) satellite. We then address the more challenging problem of solving the inverse model when the mean of the surface fluxes is not known a priori; we do so by reformulating the problem, thereby extending the applicability of hybrid projection methods to include hierarchical priors. We further show that by exploiting mathematical relations provided by the generalized hybrid method, we can efficiently calculate an approximate posterior variance, thereby providing uncertainty information. National Science Foundation ATD program [DMS-2026841, DMS-2026830, DMS-2026835]; National Aeronautics and Space Administration [80NSSC18K0976]; National Science Foundation [DMS-1638521]; NASA Carbon Monitoring System project Andrews (CMS 2014) Regional Inverse Modeling in North and South America Published version This work was partially supported by the National Science Foundation ATD program under grant nos. DMS-2026841, DMS-2026830, and DMS-2026835 and by the National Aeronautics and Space Administration under grant no. 80NSSC18K0976. This material was also based upon work partially supported by the National Science Foundation under grant no. DMS-1638521 to the Statistical and Applied Mathematical Sciences Institute. The OCO-2 CarbonTracker-Lagrange footprint library was produced by NOAA/GML and AER Inc with support from NASA Carbon Monitoring System project Andrews (CMS 2014) Regional Inverse Modeling in North and South America for the NASA Carbon Monitoring System. We especially thank Arlyn Andrews, Michael Trudeau, and Marikate Mountain for generating and assisting with the footprint library. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation.

In this study, we report the effects of co-catalysts of Pt nanoparticles and Fe3O4 clusters on photocatalytic behaviors of g-C3N4 (CN) and the use of the resulting photocatalyst for CO2 photoreduction to solar fuels in a flow reactor operated at room-temperature. In presence of H2O vapors, the selectivity of photogenerated electrons was emphasized, and found that the yield rate and selectivity of CH4 were improved by deposition of Pt on CN. With further inclusion of Fe3O4 over Pt/g-C3N4 (PtCN), the CH4 yield rate was significantly enhanced and H2 formation inhibited simultaneously, resulting in improved CH4 selectivity. Results show that the optimized Fe3O4/ Pt co-decorated CN (0.50 %FPtCN) heterostructure possesses significantly enhanced CO and CH4 yield rates of 1.83 mu molg- 1h- 1 and 0.532 mu molg- 1h- 1, respectively, which were 9 and 38 times superior to pure CN, attributed predominantly synergistic effects of Pt, Fe3O4, and CN. Owing to exceptional conductivity and electron-sink function, Pt NPs are an excellent electron transporter, which facilitates interfacial charges transfer and prohibits their recombination, while, the Fe3O4 clusters can synergistically promote the CO2 photoreduction by effectively using electrons as the oxidation - reduction center. Finally, insight obtained from results is used to propose a possible underlying mechanism for superior photocatalytic performance.

The science of the total environment 826, (2022). doi:10.1016/j.scitotenv.2022.154089, Published by Elsevier Science, Amsterdam [u.a.]

In the last decade, growing awareness about CO2 emissions is supporting the authorities in a more sustainable society. The proposed solutions embrace different topics, such as renewable energy implementation, lower waste production, and carbon capture and storage technologies (CCS). The latter is based upon the best available knowledge about the thermophysical properties of CO2, which are not always satisfactory for its complete characterization. In this work, it is investigated the interaction of the CO2 in solid phase (dry-ice) with sandy soil, a phenomenon that can potentially occur following pipeline ruptures. An experimental setup and a numerical model have been developed to measure and validate the temperature profiles beneath the dry-ice bank at steady-state conditions. The model has been validated with the experimental data by defining a suitable range of the thermal conductivity at the solid phase (0.25–0.30 W m−1 K−1) that led to the best match (deviation of 7.81%). Finally, the overall heat transfer coefficient (85.56–86.35 W m−2 K−1) has been numerically calculated.

Aquatic ecosystems are globally significant sources of greenhouse gases (GHG) to the atmosphere, offsetting the terrestrial sinks. A one-year field study was carried out in a shallow eutrophic Lake Wuliangsuhai, Inner Mongolia (draining waters from one of the largest irrigation areas in China), to estimate diffusive GHG fluxes and their relative importance in global warming potential (GWP). Our results showed high spatiotemporal variation in dissolved CO2, CH4 and N2O concentrations, while they did not differ significantly between the bottom and surface layers of the shallow waterbody. In general, GHG concentrations and diffusive fluxes were higher in the north part of the lake than in the south. GHG concentrations in the water under the ice were significantly higher than those during the open-water period. Spatial variability of GHG concentrations varied with the bathymetry of the lake. The location of study sites relative to the main inflow and abundance of submerged macrophytes were the main controlling factors of GHG concentrations, as indicated by the consistency of GHG concentrations at the sampling sites, particularly for N2O. The total diffusive GHG emission from Lake Wuliangsuhai was 76.9 ± 5.4 Gg CO2 equivalents yr−1, with CO2, CH4 and N2O contributing 16 %, 83 %, and 1 %, respectively. Overall, the results suggest that shallow lakes in mid-latitude arid areas with cold winters can be potentially important GHG sources. However, those lakes are insufficiently represented in the scientific literature, and therefore they deserve more research attention. Highlights • Greenhouse gases emissions from a shallow lake in semi-arid area were estimated. • Considerable spatiotemporal variation in dissolved CO2, CH4, and N2O concentrations. • Spatial variability of GHG was associated with lake bathymetry and abundance of macrophytes. • CH4 contributed 83% to the total emissions as CO2-equivalents. • Lakes are an important source of carbon to the atmosphere.

Vertebral deformities can impair health, welfare, and product quality in farmed Atlantic salmon. Deformities detected early in the production cycle raise questions about their further development: which types of deformities will progress and which types of deformities will worsen over time? To study this, Atlantic salmon parr (start experimental feeding weight 13.5 g) were fed diets with low (6.8 g/kg), regular (10.0 g/kg), or high (13.0 g/kg) total dietary P for 11 weeks to provoke deformities. This was followed by long-term monitoring of deformity development up to harvest size (4.5 kg) through repeated radiology of individually tagged animals. Further insights were obtained by histological analyses, mineral analyses, and testing for mechanical properties of vertebral centra. Four categories of deformity development were defined: (1) recovery, (2) containment, (3) progression, and (4) late-onset. Deformities detected early, in freshwater, which affected the vertebral centra but not the intervertebral joints, could fully recover in seawater. These involved low-mineralised vertebrae, single vertically shifted vertebrae, hyper-dense vertebrae (HDV), and two or three adjacent vertebrae with compression-related deformities. HDV were provoked by low dietary P but disappeared in seawater. Fusions were either contained (two to three vertebrae) (stable vertebral fusions) or progressed (more than three vertebrae) (progressive vertebral fusions). Vertical shifts, fusions, and compressions could also have a late-onset in seawater but did not develop into severe deformities in harvest size animals. In conclusion, low-mineralised vertebrae and HDV are abundant in animals with LP diet history but can recover in seawater. The frequency of all other types of deformities was not significantly different among animals of different diet history groups. Under the current experimental conditions, a period of high or low dietary P in freshwater had no significant effect on the prevalence of early- or late-onset deformities at harvest.

The role of precipitation (P) variability with respect to evapotranspiration (ET) and its two components, transpiration (T) and evaporation (E), from savannas continues to draw significant research interest given its relevance to a number of ecohydrological applications. Our study reports on 6 years of measured ET and estimated T and E from a grazed savanna grassland at Welgegund, South Africa. Annual P varied significantly with respect to amount (508 to 672 mm yr−1), with dry years characterized by infrequent early-season rainfall. T was determined using annual water-use efficiency and gross primary production estimates derived from eddy-covariance measurements of latent heat flux and net ecosystem CO2 exchange rates. The computed annual T for the 4 wet years with frequent early wet-season rainfall was nearly constant, 326±19 mm yr−1 (T/ET=0.51), but was lower and more variable between the 2 dry years (255 and 154 mm yr−1, respectively). Annual T and T/ET were linearly related to the early wet-season storm frequency. The constancy of annual T during wet years is explained by the moderate water stress of C4 grasses as well as trees' ability to use water from deeper layers. During extreme drought, grasses respond to water availability with a dieback–regrowth pattern, reducing leaf area and transpiration and, thus, increasing the proportion of transpiration contributed by trees. The works suggest that the early-season P distribution explains the interannual variability in T, which should be considered when managing grazing and fodder production in these grasslands.

River inflow affects the spatiotemporal variability of carbon dioxide (CO2) in the water column of lakes and may locally influence CO2 gas exchange with the atmosphere. However, spatiotemporal CO2 variability at river inflow sites is often unknown leaving estimates of lake-wide CO2 emission uncertain. Here, we investigated the CO2 concentration and flux variability along a river-impacted bay and remote sampling locations of Lake Onego. During 3 years, we resolved spatial CO2 gradients between river inflow and central lake and recorded the temporal course of CO2 in the bay from the ice-covered period to early summer. We found that the river had a major influence on the spatial CO2 variability during ice-covered periods and contributed similar to 35% to the total amount of CO2 in the bay. The bay was a source of CO2 to the atmosphere at ice-melt each year emitting 2-15 times the amount as an equally sized area in the central lake. However, there was large interannual variability in the spring CO2 emission from the bay related to differences in discharge and climate that affected the hydrodynamic development of the lake during spring. In early summer, the spatial CO2 variability was unrelated to the river signal but correlated negatively with dissolved oxygen concentrations instead indicating a stronger biological control on CO2. Our study reveals a large variability of CO2 and its drivers at river inflow sites at the seasonal and at the interannual time scale. Understanding these dynamics is essential for predicting lake-wide CO2 fluxes more accurately under a warming climate.

Different types of heterogeneous catalysts designed for a cyclocarbonation reaction between an epoxidized source and CO2 under supercritical conditions have been synthesized. The process implied a quaternization step where a (haloalkyl)trimethoxysilane reacted with tributylamine leading to a tributyl(trimethoxysilylalkyl)ammonium halide, with iodine and bromine as halogens. Then, a grafting step onto commercial fumed silica through condensation reaction between the silane part and Si OH surficial groups provided the immobilized catalyst. The efficiency of grafting has been validated by liquid 1H NMR, solid 29Si NMR and TG-DSC-MS analyzes. The benchmark cyclocarbonation reaction of polyethylene glycol diglycidylether at 80 °C and 100 bar during 4 h showed that the best immobilized catalyst was tributylpropylammonium iodide (IC3Q-EH5). It has also been shown that immobilization provided -surprisingly!- better conversions than the corresponding homogeneous catalyst’s: this phenomenon has been explained through an epoxide-ring-opening activating effect thanks to Si−OH surficial groups. Furthermore, kinetic studies performed by in situ Raman spectroscopy on IC3Q-EH5 showed that temperature had a strong influence on the yield of the reaction while CO2 pressure had only a small effect. Recycling of the catalyst has also been considered, but no precise conclusions could be conducted because of the high catalyst dispersion. Finally, the addition of a fluorinated alcohol co-catalyst allowed obtaining a similar yield but at 80 °C and 55 bar during only 2,5 h with the best candidate.

We report investigations performed at some hydrocarbon gas seeps located in the French Subalpine Chains in zones of outcropping Jurassic black shales, increasing the reported number of such occurrences in this part of the Alps. We present the characteristics of each of the seeps, based on soil flux measurements and soil gas measurements. Gases emitted are CH4-rich (87–94%) with the exception of one site (78.5% CH4 + 8.2% CO2) where an active landslide may induce dilution by atmospheric air. CO2 is generally measured at low levels (2H6 are more variable, from less than 1% to more than 2.3%. Gas is emitted over areas of various sizes. The smallest gas emission area measures only 60×20 cm, characterized by a strong hydrocarbon flux (release of about 100 kg of CH4 per year). At a second site, hydrocarbon emissions are measured over a surface of 12 m2. For this site, methane emission is evaluated at 235 kg per year and CO2 emission is 600 kg per year, 210 kg being related to gas seepage. At the third site, hydrocarbons are released over a 60 m2 area but strong gas venting is restricted to localized seeps. Methane emission is evaluated at 5.1 tons per year and CO2 emission at 1.58 tons per year, out of which 0.53 tons are attributed to gas seepage. Several historical locations remain uninvestigated at present, and numerous others may still be unknown. We outline strategies to search for such unrecorded sites. Considering the topography of the potential alpine and perialpine emission areas, the possibilities to detect gas emissions appear of the size recorded so far seem to be restricted to ground-based methods or to methods offering the possibility to point orthogonally to the soil towards the seep maximum. If such sites are to be investigated in the future in the frame of Environmental Baseline Assessment (EBA), even establishing appropriate monitoring protocols will be challenging.

Corrigendum: Agricultural and Forest Meteorology 297, 15 February 2021, 108284. https://doi.org/10.1016/j.agrformet.2020.108284 We studied the inter- and intra-annual dynamics of the photosynthesis of forest floor vegetation and tree canopy in a subarctic Scots pine stand at the northern timberline in Finland. We tackled the issue using three different approaches: 1) measuring carbon dioxide exchange above and below canopy with the eddy covariance technique, 2) modelling the photosynthesis of the tree canopy based on shoot chamber measurements, and 3) upscaling the forest floor photosynthesis using biomass estimates and available information on the annual cycle of photosynthetic capacity of those species. The studied ecosystem was generally a weak sink of carbon but the sink strength showed notable year-to-year variation. Total ecosystem respiration and photosynthesis indicated a clear temperature limitation for the carbon exchange. However, the increase in photosynthetic production was steeper than the increase in respiration with temperature, indicating that warm temperatures increase the sink strength and do not stimulate the total ecosystem respiration as much in the 4-year window studied. The interannual variation in the photosynthetic production of the forest stand mainly resulted from the forest floor vegetation, whereas the photosynthesis of the tree canopy seemed to be more stable from year to year. Tree canopy photosynthesis increased earlier in the spring, whereas that of the forest floor increased after snowmelt, highlighting that models for photosynthesis in the northern area should also include snow cover in order to accurately estimate the seasonal dynamics of photosynthesis in these forests.

Vegetation emissions of volatile organic compounds (VOCs) are intensively studied world-wide, because oxidation products of VOCs contribute to atmospheric processes. The overall aim of this study was to identify and quantify the VOCs that originate from boreal podzolized forest soil at different depths, in addition to studying the association of VOC concentrations with VOC and CO2 fluxes from the boreal forest floor. This is the first published study that measures belowground VOC concentrations at different depths in a podzol soil combined with simultaneous flux measurements from the boreal forest floor. The VOC concentrations were determined by sampling VOCs from air inside soil layers using the gas collectors and adsorbent tubes. Forest floor VOC fluxes were determined using a dynamic enclosure technique. All the VOC samples were analysed using a thermal desorption-gas chromatograph-mass spectrometer. More than 50 VOCs, dominated by monoterpenes and sesquiterpenes, were detected in the air space in the soil during two measurement campaigns. The O-horizon was a significant monoterpene source, because it contained fresh isoprenoid-rich litter. Belowground monoterpene concentrations were largely decoupled from forest floor monoterpene fluxes; thus, it seems that production processes and storages of VOCs partly differ from those VOCs that are simultaneously released from the forest floor. Both fluxes and concentrations of the monoterpenes and sesquiterpenes correlated with the CO2 fluxes in autumn, indicating that VOC release was driven by microbial activity. This is the first study where below-ground VOC concentrations were quantified in situ, and for this reason, this study provides valuable insights to the VOC sources present in soils.

Northern peatlands form a major soil carbon (C) stock. With climate change, peatland C mineralization is expected to increase, which in turn would accelerate climate change. A particularity of peatlands is the importance of soil aeration, which regulates peatland functioning and likely modulates the responses to warming climate. Our aim is to assess the impacts of warming on a southern boreal and a sub-arctic sedge fen carbon dioxide (CO2) exchange under two plausible water table regimes: wet and moderately dry. We focused this study on minerotrophic treeless sedge fens, as they are common peatland types at boreal and (sub)arctic areas, which are expected to face the highest rates of climate warming. In addition, fens are expected to respond to environmental changes faster than the nutrient poor bogs. Our study confirmed that CO2 exchange is more strongly affected by drying than warming. Experimental water level draw-down (WLD) significantly increased gross photosynthesis and ecosystem respiration. Warming alone had insignificant impacts on the CO2 exchange components, but when combined with WLD it further increased ecosystem respiration. In the southern fen, CO2 uptake decreased due to WLD, which was amplified by warming, while at northern fen it remained stable. As a conclusion, our results suggest that a very small difference in the WLD may be decisive, whether the C sink of a fen decreases, or whether the system is able to adapt within its regime and maintain its functions. Moreover, the water table has a role in determining how much the increased temperature impacts the CO2 exchange. This article is protected by copyright. All rights reserved.

Over the past few years, nickel catalysis "encountered" allenes in organic transformations, opening direct access to a plethora of chemical scaffolds in straightforward manner. The activation of allenes or their reaction partners by means of [Ni(0)] as well as [Ni(II)] species enabled chemical diversity and complexity to be achieved simultaneously through desirable concepts like selectivity, functional group tolerance and mildness. An overview of the most recent findings in the area is presented herein.

Poly(lactic acid) or PLA is currently considered as one of the most promising substitutes of conventional plastics, with low environmental impact, especially for food packaging applications. Nevertheless, some drawbacks, such as high permeability to oxygen, are still limiting its industrial applications. The objective of this study was to highly increase the oxygen barrier performance of PLA without compromising its sustainable nature and following the principles of circular economy perspective. Coproducts coming from mill industries, such as wheat gluten proteins (WG), were used to produce PLA-WG-PLA multilayer complexes with improved barrier performance. Different technologies of industrial interest were considered: high-pressure homogenization of WG film forming dispersions, corona treatment of industrial PLA films, wet casting and spin coating for tailoring the WG coating thickness, and hot-pressing for shaping the multilayers. The impact of all these strategies on the properties (surface and bulk) and performances (barrier and adhesion) were investigated on the single constituent layers as well as on the final laminate. The most efficient complex increased more than 20 times (or 2000%) the barrier properties to oxygen and ∼20% the barrier properties to water vapor, considering application conditions (50% relative humidity and 25 °C). The low thickness (∼60 μm) of this complex also matched the requirement for flexible packaging applications. High-pressure homogenization, WG coating thickness, and hot-pressing positively and highly impacted the final properties of the multilayer, while the contribution of corona treatment was limited. This study unambiguously evidenced the potential of PLA-WG-PLA complexes as a valid sustainable substitute for high performing conventional plastics, and it could open an unexplored PLA market opportunity. In addition, it could motivate further investigations on PLA-based laminates for industrial interest, using other biopolymers from agro-industrial waste or byproducts.

CO2 storage capacity in saline aquifers can dramatically be reduced by pressure build up due to the CO2 injection process. In this paper, a novel optimisation strategy that maximises the CO2 storage capacity utilisation and net profits before tax is presented in a scenario of simultaneous CO2 injection and brine production to help control pressure build up and increase the effective storage capacity. The strategy is tested at the region surrounding the Forties and Nelson fields, assuming both as pure saline aquifer traps. The optimisation was performed considering constraints such that the CO2 plume distribution does not migrate outside the license boundaries, the fracture pressure is not reached within the reservoir, and the CO2 injection and brine production rates occur within feasible limits. The problem was first formulated analytically with the aid of surrogate models, and then optimised using the SIMPLEX and Generalized Reduced Gradient methods. Results for the Forties and Nelson fields show that by allowing five brine production wells producing up to 2.2 MMtonnes/year, the CO2 storage capacity increased between 112-145% compared to the case where no brine production is practiced.

When using undiluted H2 + CO2 feeds in stoichiometric ratios, it is necessary to use a reactor outlet temperature below about 320 °C in CO2 methanation in order to achieve equilibrium conditions which allow the specifications of natural gas to be met. Under these conditions, a deactivation mechanism different from that reported for higher temperature studies is observed in Ni/AlOx catalysts. The water which is formed in situ in the CO2 methanation reaction induces the formation of Ni-hydroxide, which at these low temperatures is not completely reduced to metallic nickel with a consequent decrease of the active phase (metallic Ni), easier sintering and formation of inactive side species. By using a catalyst with a nanosheet structure, prepared from hydrotalcite precursors containing low amounts of Fe, it is possible not only to obtain higher activity and selectivity, but also to enhance the reducibility of Ni-hydroxide during the catalytic reaction, obtaining stable catalysts under extended reaction tests. Under these reaction conditions, no deactivation by coke formation is observed.

The main purposes of this research work were to realize the potential of sludge valorization by converting the sludge into adsorbents and to investigate the performance of sludge-based adsorbents for rare earth elements (REEs) recovery from dilute aqueous solutions. Hydrochloric acid and Fenton reagents were employed as pretreatment procedures to enhance the surface area and adsorption yield. Following this, sludge-based alginate beads were prepared by using HCl treated (HT) and Fenton treated (FT) sludge materials. The chemical composition and surface chemistry of sludge-based adsorbent beads were thoroughly analyzed by state-of-the-art analytical techniques, such as Scanning Electron Microscope (SEM), Fourier Transform Infrared Spectroscopy (FTIR) and Brunauer-Emmett-Teller (BET) analysis. The prepared beads were then investigated for the recovery of REEs. The batch adsorption studies revealed that the FT sludge beads performed better in comparison to the HT sludge beads. Among REEs, the HT- and FT-sludge beads demonstrated higher affinity towards Sm3+ ions, displaying the maximum adsorption capacities of 2.83 mg/g and 4.16 mg/g, respectively, in a multi-component system (C o = 25 ppm of each REE; pH = 5, t = 24 h and dosage = 5 g/L). In conclusion, the results from this work showed that the prepared sludge-based alginate beads can be used for REEs recovery from diluted waste streams and the tested sludge treatment options were also found effective in converting the waste to resource i.e., sludge to adsorbent for REEs recovery.