Search

Quantification of land surface–atmosphere fluxes of carbon dioxide (CO 2) and their trends and uncertainties is essential for monitoring progress of the EU27 + UK bloc as it strives to meet ambitious targets determined by both international agreements and internal regulation. This study provides a consolidated synthesis of fossil sources (CO 2 fossil) and natural (including formally managed ecosystems) sources and sinks over land (CO 2 land) using bottom-up (BU) and top-down (TD) approaches for the European Union and United Kingdom (EU27 + UK), updating earlier syntheses (Petrescu et al., 2020, 2021). Given the wide scope of the work and the variety of approaches involved, this study aims to answer essential questions identified in the previous syntheses and understand the differences between datasets, particularly for poorly characterized fluxes from managed and unmanaged ecosystems. The work integrates updated emission inventory data, process-based model results, data-driven categorical model results, and inverse modeling estimates, extending the previous period 1990–2018 to the year 2020 to the extent possible. BU and TD products are compared with the European national greenhouse gas inventory (NGHGI) reported by parties including the year 2019 under the United Nations Framework Convention on Climate Change (UNFCCC). The uncertainties of the EU27 + UK NGHGI were evaluated using the standard deviation reported by the EU member states following the guidelines of the Intergovernmental Panel on Climate Change (IPCC) and harmonized by gap-filling procedures. Variation in estimates produced with other methods, such as atmospheric inversion models (TD) or spatially disaggregated inventory datasets (BU), originate from within-model uncertainty related to parameterization as well as structural differences between models. By comparing the NGHGI with other approaches, key sources of differences between estimates arise primarily in activities. System boundaries and emission categories create differences in CO 2 fossil datasets, while different land use definitions for reporting emissions from land use, land use change, and forestry (LULUCF) activities result in differences for CO 2 land. The latter has important consequences for atmospheric inversions, leading to inversions reporting stronger sinks in vegetation and soils than are reported by the NGHGI. For CO 2 fossil emissions, after harmonizing estimates based on common activities and selecting the most recent year available for all datasets, the UNFCCC NGHGI for the EU27 + UK accounts for 926 ± 13 Tg C yr -1 , while eight other BU sources report a mean value of 948 [ 937,961 ] Tg C yr -1 (25th, 75th percentiles). The sole top-down inversion of fossil emissions currently available accounts for 875 Tg C in this same year, a value outside the uncertainty of both the NGHGI and bottom-up ensemble estimates and for which uncertainty estimates are not currently available. For the net CO 2 land fluxes, during the most recent 5-year period including the NGHGI estimates, the NGHGI accounted for - 91 ± 32 Tg C yr -1 , while six other BU approaches reported a mean sink of - 62 [ -117,-49 ] Tg C yr -1 , and a 15-member ensemble of dynamic global vegetation models (DGVMs) reported - 69 [ -152,-5 ] Tg C yr -1. The 5-year mean of three TD regional ensembles combined with one non-ensemble inversion of - 73 Tg C yr -1 has a slightly smaller spread (0th–100th percentiles of [ -135,+45 ] Tg C yr -1), and it was calculated after removing net land–atmosphere CO 2 fluxes caused by lateral transport of carbon (crop trade, wood trade, river transport, and net uptake from inland water bodies), resulting in increased agreement with the NGHGI and bottom-up approaches. Results at the category level (Forest Land, Cropland, Grassland) generally show good agreement between the NGHGI and category-specific models, but results for DGVMs are mixed. Overall, for both CO 2 fossil and net CO 2 land fluxes, we find that current independent approaches are consistent with the NGHGI at the scale of the EU27 + UK. We conclude that CO 2 emissions from fossil sources have decreased over the past 30 years in the EU27 + UK, while land fluxes are relatively stable: positive or negative trends larger (smaller) than 0.07 (- 0.61) Tg C yr -2 can be ruled out for the NGHGI. In addition, a gap on the order of 1000 Tg C yr -1 between CO 2 fossil emissions and net CO 2 uptake by the land exists regardless of the type of approach (NGHGI, TD, BU), falling well outside all available estimates of uncertainties. However, uncertainties in top-down approaches to estimate CO 2 fossil emissions remain uncharacterized and are likely substantial, in addition to known uncertainties in top-down estimates of the land fluxes. The data used to plot the figures are available at 10.5281/zenodo.8148461 (McGrath et al., 2023). [ABSTRACT FROM AUTHOR]

Reliable quantification of the sources and sinks of atmospheric carbon dioxide (CO 2), including that of their trends and uncertainties, is essential to monitoring the progress in mitigating anthropogenic emissions under the Kyoto Protocol and the Paris Agreement. This study provides a consolidated synthesis of estimates for all anthropogenic and natural sources and sinks of CO 2 for the European Union and UK (EU27 + UK), derived from a combination of state-of-the-art bottom-up (BU) and top-down (TD) data sources and models. Given the wide scope of the work and the variety of datasets involved, this study focuses on identifying essential questions which need to be answered to properly understand the differences between various datasets, in particular with regards to the less-well-characterized fluxes from managed ecosystems. The work integrates recent emission inventory data, process-based ecosystem model results, data-driven sector model results and inverse modeling estimates over the period 1990–2018. BU and TD products are compared with European national greenhouse gas inventories (NGHGIs) reported under the UNFCCC in 2019, aiming to assess and understand the differences between approaches. For the uncertainties in NGHGIs, we used the standard deviation obtained by varying parameters of inventory calculations, reported by the member states following the IPCC Guidelines. Variation in estimates produced with other methods, like atmospheric inversion models (TD) or spatially disaggregated inventory datasets (BU), arises from diverse sources including within-model uncertainty related to parameterization as well as structural differences between models. In comparing NGHGIs with other approaches, a key source of uncertainty is that related to different system boundaries and emission categories (CO 2 fossil) and the use of different land use definitions for reporting emissions from land use, land use change and forestry (LULUCF) activities (CO 2 land). At the EU27 + UK level, the NGHGI (2019) fossil CO 2 emissions (including cement production) account for 2624 Tg CO 2 in 2014 while all the other seven bottom-up sources are consistent with the NGHGIs and report a mean of 2588 (± 463 Tg CO 2). The inversion reports 2700 Tg CO 2 (± 480 Tg CO 2), which is well in line with the national inventories. Over 2011–2015, the CO 2 land sources and sinks from NGHGI estimates report -90 Tg C yr -1 ± 30 Tg C yr -1 while all other BU approaches report a mean sink of -98 Tg C yr -1 (± 362 Tg of C from dynamic global vegetation models only). For the TD model ensemble results, we observe a much larger spread for regional inversions (i.e., mean of 253 Tg C yr -1 ± 400 Tg C yr -1). This concludes that (a) current independent approaches are consistent with NGHGIs and (b) their uncertainty is too large to allow a verification because of model differences and probably also because of the definition of "CO 2 flux" obtained from different approaches. The referenced datasets related to figures are visualized at 10.5281/zenodo.4626578 (Petrescu et al., 2020a). [ABSTRACT FROM AUTHOR]

Reliable quantification of the sources and sinks of atmospheric carbon dioxide (CO2), including that of their trends and uncertainties, is essential to monitoring the progress in mitigating anthropogenic emissions under the Kyoto Protocol and the Paris Agreement. This study provides a consolidated synthesis of estimates for all anthropogenic and natural sources and sinks of CO2 for the European Union and UK (EU27 + UK), derived from a combination of state-of-the-art bottom-up (BU) and top-down (TD) data sources and models. Given the wide scope of the work and the variety of datasets involved, this study focuses on identifying essential questions which need to be answered to properly understand the differences between various datasets, in particular with regards to the less-well characterized fluxes from managed ecosystems. The work integrates recent emission inventory data, process-based ecosystem model results, data-driven sector model results, and inverse modelling estimates, over the period 1990-2018. BU and TD products are compared with European national GHG inventories (NGHGI) reported under the UNFCCC in 2019, aiming to assess and understand the differences between approaches. For the uncertainties in NGHGI, we used the standard deviation obtained by varying parameters of inventory calculations, reported by the Member States following the IPCC guidelines. Variation in estimates produced with other methods, like atmospheric inversion models (TD) or spatially disaggregated inventory datasets (BU), arise from diverse sources including within-model uncertainty related to parameterization as well as structural differences between models. In comparing NGHGI with other approaches, a key source of uncertainty is that related to different system boundaries and emission categories (CO2 fossil) and the use of different land use definitions for reporting emissions from Land Use, Land Use Change and Forestry (LULUCF) activities (CO2 land). At the EU27 + UK level, the NGHGI (2019) fossil CO2 emissions (including cement production) account for 2624 Tg CO2 in 2014 while all the other seven bottom-up sources are consistent with the NGHGI and report a mean of 2588 (± 463 Tg CO2). The inversion reports 2700 Tg CO2 (± 480 Tg CO2), well in line with the national inventories. Over 2011-2015, the CO2 land sources/sinks from NGHGI estimates report -90 Tg C yr-1 ± 30 Tg C while all other BU approaches report a mean sink of -98 Tg yr-1 (± 362 Tg C from DGVMs only). For the TD model ensemble results, we observe a much larger spread for regional inversions (i.e., mean of 253 Tg C yr-1 ± 400 T g C yr-1). This concludes that a) current independent approaches are consistent with NGHGI b) their uncertainty is too large to allow a verification because of model differences and probably also because of the definition of CO2 flux obtained from different approaches. The referenced datasets related to figures are visualized at https://doi.org/10.5281/zenodo.4288883 (Petrescu et al., 2020). [ABSTRACT FROM AUTHOR]

The critical cluster is the threshold size above which a cluster will be more likely to grow than to evaporate. In field and laboratory measurements of new particle formation, the number of molecules of a given species in the critical cluster is commonly taken to be the slope of the log-log plot of the formation rate versus the concentration of the species. This analysis is based on an approximate form of the first nucleation theorem, which is derived with the assumption that there are no minima in the free energy surface prior to the maximum at the critical size. However, many atmospherically relevant systems are likely to exhibit such minima, for example, ions surrounded by condensable vapour molecules or certain combinations of acids and bases. We have solved numerically the birth-death equations for both an electrically neutral one-component model system with a local minimum at pre-critical sizes and an ion-induced case. For the ion-induced case, it is verified that the log-log slope of the nucleation rate versus particle concentration plot gives accurately the difference between the cluster sizes at the free energy maximum and minimum, as is expected from the classical form of the ion-induced nucleation rate. However, the results show that applying the nucleation theorem to neutral systems with stable pre-nucleation clusters may lead to erroneous interpretations about the nature of the critical cluster. [ABSTRACT FROM AUTHOR]

The homogeneous vapor-liquid nucleation of argon has been explored at T=70 and 90 K using classical nucleation theory, semiempirical density functional theory, and Monte Carlo simulations using the aggregation-volume-bias algorithm with umbrella sampling and histogram-reweighting. In contrast with previous simulation studies, which employed only the Lennard-Jones intermolecular potential, the current studies were carried out using various pair potentials including the Lennard-Jones potential, a modified Buckingham exponential-six potential, the Barker–Fisher–Watts pair potential, and a recent ab initio potential developed using the method of effective diameters. It was found that the differences in the free energy of formation of the critical nuclei between the potentials cannot be explained solely in terms of the difference in macroscopic properties of the potentials, which gives a possible reason for the failure of classical nucleation theory. [ABSTRACT FROM AUTHOR]

A key goal of the Paris Agreement (PA) is to reach net-zero greenhouse gas (GHG) emissions by 2050 globally, which requires mitigation efforts from all countries. Africa's rapidly growing population and gross domestic product (GDP) make this continent important for GHG emission trends. In this paper, we study the emissions of carbon dioxide (CO 2), methane (CH 4) and nitrous oxide (N 2 O) in Africa over 3 decades (1990–2018). We compare bottom-up (BU) approaches, including United Nations Convention Framework on Climate Change (UNFCCC) national inventories, FAO, PRIMAP-hist, process-based ecosystem models for CO 2 fluxes in the land use, land use change and forestry (LULUCF) sector and global atmospheric inversions. For inversions, we applied different methods to separate anthropogenic CH 4 emissions. The BU inventories show that, over the decade 2010–2018, fewer than 10 countries represented more than 75 % of African fossil CO 2 emissions. With a mean of 1373 Mt CO 2 yr -1 , total African fossil CO 2 emissions over 2010–2018 represent only 4 % of global fossil emissions. However, these emissions grew by +34% from 1990–1999 to 2000–2009 and by +31% from 2000–2009 to 2010–2018, which represents more than a doubling in 30 years. This growth rate is more than 2 times faster than the global growth rate of fossil CO 2 emissions. The anthropogenic emissions of CH 4 grew by 5 % from 1990–1999 to 2000–2009 and by 14.8 % from 2000–2009 to 2010–2018. The N 2 O emissions grew by 19.5 % from 1990–1999 to 2000–2009 and by 20.8 % from 2000–2009 to 2010–2018. When using the mean of the estimates from UNFCCC reports (including the land use sector) with corrections from outliers, Africa was a mean source of greenhouse gases of 262221863239 Mt CO 2 eq. yr -1 from all BU estimates (the subscript and superscript indicate min–max range uncertainties) and of +263717615873 Mt CO 2 eq. yr -1 from top-down (TD) methods during their overlap period from 2001 to 2017. Although the mean values are consistent, the range of TD estimates is larger than the one of the BU estimates, indicating that sparse atmospheric observations and transport model errors do not allow us to use inversions to reduce the uncertainty in BU estimates. The main source of uncertainty comes from CO 2 fluxes in the LULUCF sector, for which the spread across inversions is larger than 50 %, especially in central Africa. Moreover, estimates from national UNFCCC communications differ widely depending on whether the large sinks in a few countries are corrected to more plausible values using more recent national sources following the methodology of Grassi et al. (2022). The medians of CH 4 emissions from inversions based on satellite retrievals and surface station networks are consistent with each other within 2 % at the continental scale. The inversion ensemble also provides consistent estimates of anthropogenic CH 4 emissions with BU inventories such as PRIMAP-hist. For N 2 O, inversions systematically show higher emissions than inventories, on average about 4.5 times more than PRIMAP-hist, either because natural N 2 O sources cannot be separated accurately from anthropogenic ones in inversions or because BU estimates ignore indirect emissions and underestimate emission factors. Future improvements can be expected thanks to a denser network of monitoring atmospheric concentrations. This study helps to introduce methods to enhance the scope of use of various published datasets and allows us to compute budgets thanks to recombinations of those data products. Our results allow us to understand uncertainty and trends in emissions and removals in a region of the world where few observations exist and where most inventories are based on default IPCC guideline values. The results can therefore serve as a support tool for the Global Stocktake (GST) of the Paris Agreement. The referenced datasets related to the figures are available at 10.5281/zenodo.7347077 (Mostefaoui et al., 2022). [ABSTRACT FROM AUTHOR]

In order to better simulate heat fluxes over multilayer ecosystems, in particular tropical forests and savannahs, the next generation of Earth system models will likely include vertically-resolved vegetation structure and multi-level energy budgets. We present here a multi-level radiation transfer scheme which is capable of being used in conjunction with such methods. It is based on a previously established scheme which encapsulates the three dimensional nature of canopies, through the use of a domain-averaged structure factor, referred to here as the effective leaf area index. The fluxes are tracked throughout the canopy in an iterative fashion until they escape into the atmosphere or are absorbed by the canopy or soil; this approach explicitly includes multiple scattering between the canopy layers. A series of tests show that the results from the two-layer case are in acceptable agreement with those from the single layer, although the computational cost is necessarily increased due to the iterations. The ten-layer case is less precise, but still provides results to within an acceptable range. This new approach allows for the calculation of radiation transfer in vertically resolved vegetation canopies simulated in global circulation models. [ABSTRACT FROM AUTHOR]

A key goal of the Paris Agreement (PA) is to reach net-zero Greenhouse Gasses (GHG) emissions by 2050 globally, which requires mitigation efforts from all countries. Africa's rapidly growing population and GDP makes this continent important for GHG emission trends. In this paper, we study the emissions of carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O) in Africa over three decades (1990-2018). We compare bottom-up approaches including UNFCCC national inventories, FAO, PRIMAP-hist, process-based ecosystem models for CO2 fluxes in the Land Use, Land Use Change and Forestry (LULUCF) sector, and global atmospheric inversions. Our database is available from Zenodo at: https://doi.org/10.5281/zenodo.7347077 (Mostefaoui et al., 2022). For inversions, we applied different methods to separate anthropogenic CH4 emissions. The bottom-up (BU) inventories show that over the decade 2010-2018, less than ten countries represented more than 75% of African fossil CO2 emissions. With a mean of 1373 MtCO2 yr-1, total African fossil CO2 emissions over 2010-2018 represent only 4% of global fossil emissions. Yet, these emissions grew by +34% from 1990-1999 to 2000-2009 and by +31% over 2000-2009 to 2010-2018, more than doubling in 30 years. This growth rate is more than twice faster than the global growth rate of fossil CO2 emissions. The anthropogenic emissions of CH4 grew by 5% from 1990-1999 to 2000-2009 and by 14.8% from 2000-2009 to 2010-2018. The N2O emissions grew by 19.5% from 1990-1999 to 2000-2009; and by 20.8% from 2000-2009 to 2010-2018. When using the mean of estimates from UNFCCC reports (including the land use sector), with corrections from outliers, Africa was a mean source of greenhouse gasses of +2622 $%&' ($() MtCO2e yr-1 from all bottom-up estimates (sub- and superscript indicating min-max range uncertainties), and of +2637%,'% -&,(MtCO2e yr-1 from top-down methods, during their overlap period from 2001 to 2017. Although the mean values are consistent, the range of top-down estimates is larger than the one of bottom up, indicating that sparse atmospheric observations and transport model errors do not allow us to use inversions to reduce the uncertainty of bottom-up estimates. A main source of uncertainty comes from CO2 fluxes in the land-use sector (LULUCF) for which the spread across inversions is larger than 50%, especially in Central Africa. Moreover, estimates from national UNFCCC communications differ widely depending on whether the large sinks in a few countries are corrected to more plausible values using more recent national sources following the methodology of Grassi et al. (2022) The median of CH4 emissions from inversions based on satellite retrievals and in situ surface networks are consistent with each other within 2% at continental scale. The inversion ensemble also provides consistent estimates of anthropogenic CH4 emissions with bottom-up inventories such as PRIMAP-hist. For N2O, inversions systematically show higher emissions than inventories, on average about 4.5 times more than PRIMAP-hist, either because natural N2O sources cannot be separated accurately from anthropogenic ones in inversions, or because bottom-up estimates ignore indirect emissions and under-estimate emission factors. Future improvements can be expected thanks to a denser network for monitoring atmospheric concentrations. This study helps to introduce methods to enhance the scope of use of various published datasets and allows to compute budgets thanks to recombinations those data products. Our results allow to understand uncertainty and trends of emissions and removals in a region of the world where few observations exist and most inventories are based on default IPCC guidelines values. The results can therefore serve as a support tool for the Global Stocktake (GST) of the Paris Agreement. The referenced datasets related to figures are available at: https://doi.org/10.5281/zenodo.7347077 (Mostefaoui et al., 2022). [ABSTRACT FROM AUTHOR]

Knowledge of the spatial distribution of the fluxes of greenhouse gases (GHGs) and their temporal variability as well as flux attribution to natural and anthropogenic processes is essential to monitoring the progress in mitigating anthropogenic emissions under the Paris Agreement and to inform its global stocktake. This study provides a consolidated synthesis of CH 4 and N 2 O emissions using bottom-up (BU) and top-down (TD) approaches for the European Union and UK (EU27 + UK) and updates earlier syntheses (Petrescu et al., 2020, 2021). The work integrates updated emission inventory data, process-based model results, data-driven sector model results and inverse modeling estimates, and it extends the previous period of 1990–2017 to 2019. BU and TD products are compared with European national greenhouse gas inventories (NGHGIs) reported by parties under the United Nations Framework Convention on Climate Change (UNFCCC) in 2021. Uncertainties in NGHGIs, as reported to the UNFCCC by the EU and its member states, are also included in the synthesis. Variations in estimates produced with other methods, such as atmospheric inversion models (TD) or spatially disaggregated inventory datasets (BU), arise from diverse sources including within-model uncertainty related to parameterization as well as structural differences between models. By comparing NGHGIs with other approaches, the activities included are a key source of bias between estimates, e.g., anthropogenic and natural fluxes, which in atmospheric inversions are sensitive to the prior geospatial distribution of emissions. For CH 4 emissions, over the updated 2015–2019 period, which covers a sufficiently robust number of overlapping estimates, and most importantly the NGHGIs, the anthropogenic BU approaches are directly comparable, accounting for mean emissions of 20.5 Tg CH 4 yr -1 (EDGARv6.0, last year 2018) and 18.4 Tg CH 4 yr -1 (GAINS, last year 2015), close to the NGHGI estimates of 17.5±2.1 Tg CH 4 yr -1. TD inversion estimates give higher emission estimates, as they also detect natural emissions. Over the same period, high-resolution regional TD inversions report a mean emission of 34 Tg CH 4 yr -1. Coarser-resolution global-scale TD inversions result in emission estimates of 23 and 24 Tg CH 4 yr -1 inferred from GOSAT and surface (SURF) network atmospheric measurements, respectively. The magnitude of natural peatland and mineral soil emissions from the JSBACH–HIMMELI model, natural rivers, lake and reservoir emissions, geological sources, and biomass burning together could account for the gap between NGHGI and inversions and account for 8 Tg CH 4 yr -1. For N 2 O emissions, over the 2015–2019 period, both BU products (EDGARv6.0 and GAINS) report a mean value of anthropogenic emissions of 0.9 Tg N 2 O yr -1 , close to the NGHGI data (0.8±55 % Tg N 2 O yr -1). Over the same period, the mean of TD global and regional inversions was 1.4 Tg N 2 O yr -1 (excluding TOMCAT, which reported no data). The TD and BU comparison method defined in this study can be operationalized for future annual updates for the calculation of CH 4 and N 2 O budgets at the national and EU27 + UK scales. Future comparability will be enhanced with further steps involving analysis at finer temporal resolutions and estimation of emissions over intra-annual timescales, which is of great importance for CH 4 and N 2 O, and may help identify sector contributions to divergence between prior and posterior estimates at the annual and/or inter-annual scale. Even if currently comparison between CH 4 and N 2 O inversion estimates and NGHGIs is highly uncertain because of the large spread in the inversion results, TD inversions inferred from atmospheric observations represent the most independent data against which inventory totals can be compared. With anticipated improvements in atmospheric modeling and observations, as well as modeling of natural fluxes, TD inversions may arguably emerge as the most powerful tool for verifying emission inventories for CH 4 , N 2 O and other GHGs. The referenced datasets related to figures are visualized at 10.5281/zenodo.7553800 (Petrescu et al., 2023). [ABSTRACT FROM AUTHOR]

Kinesin is a molecular motor that hydrolyzes adenosine triphosphate (ATP) and moves along microtubules against load. While motility and atomic structures have been well-characterized for various members of the kinesin family, not much is known about ATP hydrolysis inside the active site. Here, we study ATP hydrolysis mechanisms in the kinesin-5 protein Eg5 by using combined quantum mechanics/molecular mechanics metadynamics simulations. Approximately 200 atoms at the catalytic site are treated by a dispersion-corrected density functional and, in total, 13 metadynamics simulations are performed with their cumulative time reaching ~0.7 ns. Using the converged runs, we compute free energy surfaces and obtain a few hydrolysis pathways. The pathway with the lowest free energy barrier involves a two-water chain and is initiated by the Pγ—Oβ dissociation concerted with approach of the lytic water to PγO3–. This immediately induces a proton transfer from the lytic water to another water, which then gives a proton to the conserved Glu270. Later, the proton is transferred back from Glu270 to HPO42– via another hydrogen-bonded chain. We find that the reaction is favorable when the salt bridge between Glu270 in switch II and Arg234 in switch I is transiently broken, which facilitates the ability of Glu270 to accept a proton. When ATP is placed in the ADP-bound conformation of Eg5, the ATP-Mg moiety is surrounded by many water molecules and Thr107 blocks the water chain, which together make the hydrolysis reaction less favorable. The observed two-water chain mechanisms are rather similar to those suggested in two other motors, myosin and F1-ATPase, raising the possibility of a common mechanism. [ABSTRACT FROM AUTHOR]

Enantiomerically enriched forms of a sulfoximine-based myristic acid analogue are prepared using either an asymmetric desymmetrization with a chiral base, or an enantioselective oxidation procedure as key steps. Additionally, a variety of 2-oxa-2-alkyl 3,4-dihydro 2,1-benzothiazines are synthesized via intramolecular metal-catalyzed N-arylation of appropriately functionalized sulfoximines with tethered 2-bromoaryl substituents. In turn, the sulfoximines are prepared by lithiation--alkylation sequences including enantioselective deprotonation steps or the use of an optically active sulfoxide. Using this methodology, the range of accessible 3,4-dihydro 2,1-benzothiazine derivatives is expanded. [ABSTRACT FROM AUTHOR]

First principles Monte Carlo simulations in the Gibbs and isobaric–isothermal ensembles were performed to map the vapor–liquid coexistence curves of methanol and methane described by Kohn–Sham density functional theory using the Becke–Lee–Yang–Parr (BLYP) exchange and correlation functionals with the Grimme correction term for dispersive (D2) interactions. The simulations indicate that the BLYP-D2 description with the TZV2P basis set underpredicts the saturated vapor densities and overpredicts the saturated liquid densities and critical and boiling temperatures for both compounds. Although the deviations are quite large, these results present a significant improvement over the BLYP functional without the correction term, which misses the experimental results by a larger extent in the opposite direction. Simulations at one temperature indicate that use of the larger QZV3P basis set may lead to improved saturated vapor densities, but not to significant changes in the liquid density. [ABSTRACT FROM AUTHOR]

Abstract: Gibbs ensemble Monte Carlo simulations were carried out to investigate the properties of a frozen-electron-density (or Kim–Gordon, KG) model of water along the vapor–liquid coexistence curve. Because of its theoretical basis, such a KG model provides for seamless coupling to Kohn–Sham density functional theory in mixed quantum mechanics/molecular mechanics implementations. The Gibbs ensemble simulations indicate limited transferability of a KG model to other state points. Specifically, a KG model that was parameterized by Barker and Sprik to the properties of liquid water at 300K, yields saturated vapor pressures and a critical temperature that are significantly under- and overestimated, respectively. [Copyright &y& Elsevier]

Three new (+)-sparteine-like diamines were prepared from (-)cytosine and evaluated as sparteine surrogates in the α-lithiation rearrangement of cyclooctene oxide and the palladium(II)/diamine catalyzed oxidative kinetic resolution of 1-indanol. The new diamines exhibited opposite enantioselectivity to that observed with (-)-sparteine but increasing the steric hindrance of the N-alkyl group beyond N-Et had a detrimental effect on enantioselectivity. The optimal N-Me diamine was evaluated with much success in five other (-)-sparteine-mediated processes involving different metals (lithium, magnesium, and copper) and different types of reaction mechanisms. [ABSTRACT FROM AUTHOR]

Density functional calculations of a series of metaphosphates, acyclic and cyclic phosphates and phosphoranes relevant to RNA catalysis are presented. Solvent effects calculated with three well-established solvation models are analyzed and compared. The structure and stability of the compounds are characterized in terms of thermodynamic quantities for isomerization and ligand substitution reactions, gas-phase proton affinities, and microscopic solution pKa values. The large dataset of compounds allows the estimation of bond energies to determine the relative strengths of axial and equatorial P-O phosphorane single bonds and P---O single and double bonds in metaphosphates and phosphates. The relative apicophilicty of hydroxyl and methoxy ligands in phosphoranes are characterized. The results presented here provide quantitative insight into RNA catalysis and serve as a first step toward the construction of a high-level quantum database for development of new semiempirical Hamiltonian models for biological reactions. [ABSTRACT FROM AUTHOR]

A suite of allenic hydrocarbons, previously unknown as a molecular class from insects, has been characterized from several Australian melolonthine scarab beetles. The allenes are represented by the formula CH[sub 3](CH[sub 2])[sub n]CH=·=CH(CH[sub 2])[sub 7]CH[sub 3] with n being 11-15, 17 and 19, and thus, all have Δ[sup 9,10]-unsaturation. These structures have been confirmed by syntheses and comparisons of spectral and chromatographic properties with those of the natural components. The enantiomers of (±)Δ[sup 9,10]-tricosadiene and Δ[sup 9,10]-pentacosadiene were separable on a modified β-cyclodextrin column (gas chromatography), and the natural Δ[sup 9,10]-tricosadiene (n = 11) and Δ[sup 9,10]-pentacosadiene (n = 13) were shown to be of >85% ee. Syntheses of nonracemic allenes of known predominating chirality were acquired using both organotin chemistry and sulfonylhydrazine intermediates, and comparisons then demonstrated that the natural allenes were predominantly (R)-configured. [ABSTRACT FROM AUTHOR]

Knowledge of the spatial distribution of the fluxes of greenhouse gases and their temporal variability as well as flux attribution to natural and anthropogenic processes is essential to monitoring the progress in mitigating anthropogenic emissions under the Paris Agreement and to inform its Global Stocktake. This study provides a consolidated synthesis of CH4 and N2O emissions using bottom-up (BU) and top-down (TD) approaches for the European Union and UK (EU27+UK) and updates earlier syntheses (Petrescu et al., 2020, 2021). The work integrates updated emission inventory data, process-based model results, data-driven sector model results, inverse modelling estimates, and extends the previous period 1990-2017 to 2020. BU and TD products are compared with European National GHG Inventories (NGHGI) reported by Parties under the United Nations Framework Convention on Climate Change (UNFCCC) in 2021. The uncertainties of NGHGIs were evaluated using the standard deviation obtained by varying parameters of inventory calculations, reported by the EU Member States following the guidelines of the Intergovernmental Panel on Climate Change (IPCC) and harmonized by gap-filling procedures. Variation in estimates produced with other methods, such as atmospheric inversion models (TD) or spatially disaggregated inventory datasets (BU), arise from diverse sources including within-model uncertainty related to parameterization as well as structural differences between models. By comparing NGHGIs with other approaches, the activities included are a key source of bias between estimates e.g. anthropogenic and natural fluxes, which, in atmospheric inversions are sensitive to the prior geospatial distribution of emissions. For CH4 emissions, over the updated 2015-2019 period, which covers a sufficiently robust number of overlapping estimates, and most importantly the NGHGIs, the anthropogenic BU approaches are directly comparable, accounting for mean emissions of 20.5 Tg CH4 yr-1 (EDGAR v6.0, last year 2018) and 18.4 Tg CH4 yr-1 (GAINS, 2015), close to the NGHGI estimates of 17.5 ± 2.1 Tg CH4 yr-1. TD inversions estimates give higher emission estimates, as they also detect natural emissions. Over the same period, high resolution regional TD inversions report a mean emission of 34 Tg CH4 yr-1. Coarser-resolution global-scale TD inversions result in emission estimates of 23 Tg CH4 yr-1 and 24 Tg CH4 yr-1 inferred from GOSAT and surface (SURF) network atmospheric measurements, respectively. The magnitude of natural peatland and mineral soils emissions from the JSBACH-HIMMELI model, natural rivers, lakes and reservoirs emissions, geological sources and biomass burning together could account for the gap between NGHGI and inversions and account for 8 Tg CH4 yr-1. For N2O emissions, over the 2015-2019 period, both BU products (EDGAR v6.0 and GAINS) report a mean value of anthropogenic emissions of 0.9 Tg N2O yr-1, close to the NGHGI data (0.8 ± 55 % Tg N2O yr-1). Over the same period, the mean of TD global and regional inversions was 1.4 Tg N2O yr-1 (excluding TOMCAT which reported no data). The TD and BU comparison method defined in this study can be 'operationalized' for future annual updates for the calculation of CH4 and N2O budgets at the national and EU27+UK scales. Future comparability will be enhanced with further steps involving analysis at finer temporal resolutions and estimation of emissions over intra-annual timescales, of great importance for CH4 and N2O, which may help identify sector contributions to divergence between prior and posterior estimates at the annual/inter-annual scale. Even if currently comparison between CH4 and N2O inversions estimates and NGHGIs is highly uncertain because of the large spread in the inversion results, TD inversions inferred from atmospheric observations represent the most independent data against which inventory totals can be compared. With anticipated improvements in atmospheric modelling and observations, as well as modelling of natural fluxes, TD inversions may arguably emerge as the most powerful tool for verifying emissions inventories for CH4, N2O and other GHGs. The referenced datasets related to figures are visualized at https://doi.org/10.5281/zenodo.6992472 (Petrescu et al., 2022). [ABSTRACT FROM AUTHOR]

First-principles molecular dynamics simulations, in which the forces are computed from electronic structure calculations, have great potential to provide unique insight into structure, dynamics, electronic properties, and chemistry of interfacial systems that is not available from empirical force fields. The majority of current first-principles simulations are driven by forces derived from density functional theory with generalized gradient approximations to the exchange-correlation energy, which do not capture dispersion interactions. We have carried out first-principles molecular dynamics simulations of air-water interfaces employing a particular generalized gradient approximation to the exchange-correlation functional (BLYP), with and without empirical dispersion corrections. We assess the utility of the dispersion corrections by comparison of a variety of structural, dynamic, and thermodynamic properties of bulk and interfacial water with experimental data, as well as other first-principles and force field-based simulations. [ABSTRACT FROM AUTHOR]

The article reports on a novel ligand exchange approach to catalytic asymmetric deprotonation--electrophilic trapping. It suggests that use of (-)-sparteine and (+)-sparteine in this methodology allows access to either enantiomer of useful products in good yields using substoichiometric amounts of chiral diamines. It also illustrates the catalytic asymmetric deprotonation methodology, by applying it to the synthesis of bis-phosphine boranes which are precursors of useful chiral bis-phosphines for asymmetric hydrogenation. It also reports the experimental procedures and characterization of the compounds.

New (a)biotic conditions, resulting from climate change, are expected to change disturbance dynamics, e.g., wind throw, forest fires and insect outbreaks, and their interactions. Unprecedented natural disturbance 30 dynamics might alter the capability of forest ecosystems to buffer atmospheric CO2 increases in the atmosphere, even leading to the risk that forests transform from sinks into sources of CO2. This study aims to enhance the capability of the ORCHIDEE land surface model to study the impacts of climate change on bark beetle dynamics and subsequent effects on forest functioning. The bark beetle outbreak model is based on previous work by Temperli et al. 2013 for the LandClim landscape model. The new implementation of this model in ORCHIDEE r7791 35 accounts for the following differences between ORCHIDEE and LandClim: (1) the coarser spatial resolution of ORCHIDEE, (2) the higher temporal resolution of ORCHIDEE, and (3) the pre-existing process representation of wind throw, drought, and forest structure in ORCHIDEE. Qualitative evaluation demonstrated the model's ability to simulate a wide range of observed post-disturbance forest dynamics: (1) resistance to bark beetle infestation even in the presence of windthrow events; (2) slow transition (3-7 years) from an endemic into an epidemic bark beetle population following medium intensity window events at cold locations; and (3) fast transition (1-3 years) from endemic to epidemic triggered by strong windthrow events. Although all simulated sites eventually recovered from disturbances, the time needed to recover varied from 5 to 10 years depending on the disturbance dynamics. In addition to enhancing the functionality of the ORCHIDEE model, the new bark beetle model represents a fundamental change in the way mortality is simulated as it replaces a framework in which mortality is conceived as a continuous process by one in which mortality is represented by abrupt events. Changing the mortality framework provided new insights into carbon balance estimates, showing the risk of overestimating the short-term sequestration potential under the commonly used continuous mortality framework. [ABSTRACT FROM AUTHOR]

Afforestation and forest management are considered to be key instruments in mitigating climate change. Here we show that since 1750, in spite of considerable afforestation, wood extraction has led to Europe's forests accumulating a carbon debt of 3.1 petagrams of carbon.We found that afforestation is responsible for an increase of 0.12 watts per square meter in the radiative imbalance at the top of the atmosphere, whereas an increase of 0.12 kelvin in summertime atmospheric boundary layer temperature was mainly caused by species conversion. Thus, two and a half centuries of forest management in Europe have not cooled the climate. The political imperative to mitigate climate change through afforestation and forest management therefore risks failure, unless it is recognized that not all forestry contributes to climate change mitigation. [ABSTRACT FROM AUTHOR]

Canopy structure is one of the most important vegetation characteristics for land-atmosphere interactions, as it determines the energy and scalar exchanges between the land surface and the overlying air mass. In this study we evaluated the performance of a newly developed multi-layer energy budget in the land surface model ORCHIDEE-CAN (Organising Carbon and Hydrology In Dynamic Ecosystems - CANopy), which simulates canopy structure and can be coupled to an atmospheric model using an implicit coupling procedure. We aim to provide a set of acceptable parameter values for a range of forest types. Top-canopy and sub-canopy flux observations from eight sites were collected in order to conduct this evaluation. The sites crossed climate zones from temperate to boreal and the vegetation types included deciduous, evergreen broad leaved and evergreen needle leaved forest with a maximum LAI (all-sided) ranging from 3.5 to 7.0. The parametrization approach proposed in this study was based on three selected physical processes - namely the diffusion, advection and turbulent mixing within the canopy. Short-term sub-canopy observations and long-term surface fluxes were used to calibrate the parameters in the sub-canopy radiation, turbulence and resistances modules with an automatic tuning process. The multi-layer model was found to capture the dynamics of sub-canopy turbulence, temperature and energy fluxes. The performance of the new multi-layer model was further compared against the existing single-layer model. Although, the multi-layer model simulation results showed little or no improvements to both the nighttime energy balance and energy partitioning during winter compared with a single-layer model simulation, the increased model complexity does provide a more detailed description of the canopy micrometeorology of various forest types. The multi-layer model links to potential future environmental and ecological studies such as the assessment of in-canopy species vulnerability to climate change, the climate effects of disturbance intensities and frequencies, and the consequences of biogenic volatile organic compounds (BVOC) emissions from the terrestrial ecosystem. [ABSTRACT FROM AUTHOR]

Cuticular hydrocarbon components in beetles of six Australian melolonthines whose larvae damage sugarcane, Antitrogus parvulus (Britton), A. consanguineus (Blackburn), Lepidiota negatoria (Blackburn), L. picticollis (Lea), L. noxia (Britton) and Dermolepida alborhirtum (Arrow), are identified and compared. These species demonstrate species-specific cuticular hydrocarbon profiles with a number of unprecedented structures. Major components have been identified as polymethylated hydrocarbons, 3-methyl substituted n-alkanes, 9,10-allenes and the corresponding C9 alkenes. The similarity of these compounds shows some correlation with the phylogeny of the beetles, but two polymethylated C22 hydrocarbons are unique to A. parvulus. One C25 allene is shown to have a potential role in mate recognition in A. consanguineus. [ABSTRACT FROM AUTHOR]

Reliable quantification of the sources and sinks of greenhouse gases, together with trends and uncertainties, is essential to monitoring the progress in mitigating anthropogenic emissions under the Paris Agreement. This study provides a consolidated synthesis of CH4 and N2O emissions with consistently derived state-of-the-art bottom-up (BU) and top-down (TD) data sources for the European Union and UK (EU27 + UK). We integrate recent emission inventory data, ecosystem process-based model results and inverse modeling estimates over the period 1990–2017. BU and TD products are compared with European national greenhouse gas inventories (NGHGIs) reported to the UN climate convention UNFCCC secretariat in 2019. For uncertainties, we used for NGHGIs the standard deviation obtained by varying parameters of inventory calculations, reported by the member states (MSs) following the recommendations of the IPCC Guidelines. For atmospheric inversion models (TD) or other inventory datasets (BU), we defined uncertainties from the spread between different model estimates or model-specific uncertainties when reported. In comparing NGHGIs with other approaches, a key source of bias is the activities included, e.g., anthropogenic versus anthropogenic plus natural fluxes. In inversions, the separation between anthropogenic and natural emissions is sensitive to the geospatial prior distribution of emissions. Over the 2011–2015 period, which is the common denominator of data availability between all sources, the anthropogenic BU approaches are directly comparable, reporting mean emissions of 20.8 TgCH4yr-1 (EDGAR v5.0) and 19.0 TgCH4yr-1 (GAINS), consistent with the NGHGI estimates of 18.9 ± 1.7 TgCH4yr-1. The estimates of TD total inversions give higher emission estimates, as they also include natural emissions. Over the same period regional TD inversions with higher-resolution atmospheric transport models give a mean emission of 28.8 TgCH4yr-1. Coarser-resolution global TD inversions are consistent with regional TD inversions, for global inversions with GOSAT satellite data (23.3 TgCH4yr-1) and surface network (24.4 TgCH4yr-1). The magnitude of natural peatland emissions from the JSBACH–HIMMELI model, natural rivers and lakes emissions, and geological sources together account for the gap between NGHGIs and inversions and account for 5.2 TgCH4yr-1. For N2O emissions, over the 2011–2015 period, both BU approaches (EDGAR v5.0 and GAINS) give a mean value of anthropogenic emissions of 0.8 and 0.9 TgN2Oyr-1 , respectively, agreeing with the NGHGI data (0.9 ± 0.6 TgN2Oyr-1). Over the same period, the average of the three total TD global and regional inversions was 1.3 ± 0.4 and 1.3 ± 0.1 TgN2Oyr-1 , respectively. The TD and BU comparison method defined in this study can be operationalized for future yearly updates for the calculation of CH4 and N2O budgets both at the EU + UK scale and at the national scale. The referenced datasets related to figures are visualized at 10.5281/zenodo.4590875 (Petrescu et al., 2020b). [ABSTRACT FROM AUTHOR]

Intermediates involved in the conversion of 3-alkyl-3,4-dihydro-2H-1,3-benz[e]oxazines into 2-N,N-dialkylaminomethylphenol derivatives, using morpholine and other high boiling secondary amines, have been identified and characterised. Additional experiments have established the involvement of o-quinone methide intermediates in the retro-Mannich reactions. Axially chiral resorcinarenes have been prepared by utilising the exchange reactions. [Copyright &y& Elsevier]

While some recent research has examined the prevalence and severity of posttraumatic stress disorder (PTSD)-like symptoms following cancer treatment, no research has examined temporal change or stability in these symptoms in cancer survivors. Female breast cancer survivors (n =46) participated in an initial telephone interview and a follow-up interview 12 months later. PTSD symptoms associated with breast cancer were assessed using the PTSD Checklist—Civilian version (PCLC). In general, PTSD symptoms in this population did not diminish over time. While group analyses indicated that PCLC-total and subscale scores were stable across the two assessments, analyses of PCLC scores indicated that many patients exhibited fairly large (>0.5 S.D.) increases and/or decreases in PCLC-total or subscale scores. Some evidence suggested that decreases in PCLC scores between the two study assessments were associated with greater social support and experience of fewer traumatic stressors prior to breast cancer diagnosis. Most significantly, the research suggested that women with greater PTSD symptoms at the initial interview were less likely to participate in the follow-up interview. Implications of this for research and clinical management of PTSD in this population are discussed. Copyright © 2000 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Reliable quantification of the sources and sinks of greenhouse gases, together with trends and uncertainties, is essential to monitoring the progress in mitigating anthropogenic emissions under the Paris Agreement. This study provides a consolidated synthesis of CH4 and N2O emissions with consistently derived state-of-the-art bottom-up (BU) and top-down (TD) data sources for the European Union and UK (EU27+UK). We integrate recent emission inventory data, ecosystem process-based model results, and inverse modelling estimates over the period 1990-2018. BU and TD products are compared with European National GHG Inventories (NGHGI) reported to the UN climate convention secretariat UNFCCC in 2019. For uncertainties, we used for NGHGI the standard deviation obtained by varying parameters of inventory calculations, reported by the Member States following the IPCC guidelines recommendations. For atmospheric inversion models (TD) or other inventory datasets (BU), we defined uncertainties from the spread between different model estimates or model specific uncertainties when reported. In comparing NGHGI with other approaches, a key source of bias is the activities included, e.g. anthropogenic versus anthropogenic plus natural fluxes. In inversions, the separation between anthropogenic and natural emissions is sensitive to the geospatial prior distribution of emissions. Over the 2011-2015 period, which is the common denominator of data availability between all sources, the anthropogenic BU approaches are directly comparable, reporting mean emissions of 20.8 Tg CH4 yr-1 (EDGAR v5.0) and 19.0 Tg CH4 yr-1 (GAINS), consistent with the NGHGI estimates of 18.9 ± 1.7 Tg CH4 yr-1. TD total inversions estimates give higher emission estimates, as they also include natural emissions. Over the same period regional TD inversions with higher resolution atmospheric transport models give a mean emission of 28.8 Tg CH4 yr-1. Coarser resolution global TD inversions are consistent with regional TD inversions, for global inversions with GOSAT satellite data (23.3 Tg CH4yr-1) and surface network (24.4 Tg CH4 yr-1). The magnitude of natural peatland emissions from the JSBACH-HIMMELI model, natural rivers and lakes emissions and geological sources together account for the gap between NGHGI and inversions and account for 5.2 Tg CH4 yr-1. For N2O emissions, over the 2011-2015 period, both BU approaches (EDGAR v5.0 and GAINS) give a mean value of anthropogenic emissions of 0.8 and 0.9 Tg N2O yr-1 respectively, agreeing with the NGHGI data (0.9 ± 0.6 Tg N2O yr-1). Over the same period, the average of the three total TD global and regional inversions was 1.3 ± 0.4 and 1.3 ± 0.1 Tg N2O yr-1 respectively, compared to 0.9 Tg N2O yr-1 from the BU data. The TU and BU comparison method defined in this study can be operationalized for future yearly updates for the calculation of CH4 and N2O budgets both at EU+UK scale and at national scale. The referenced datasets related to figures are visualized at https://doi.org/10.5281/zenodo.4288969 (Petrescu et al., 2020). [ABSTRACT FROM AUTHOR]

The search for a long-term benchmark for land-surface models (LSM) has brought tree-ring data to the attention of the land-surface community as they record growth well before human-induced environmental changes became important. The most comprehensive archive of publicly shared tree-ring data is the International Tree-ring Data Bank (ITRDB). Many records in the ITRDB have, however, been collected almost exclusively with a view on maximizing an environmental target signal (e.g. climate), which has resulted in a biased representation of forested sites and landscapes and thus limits its use as a data source for benchmarking. The aim of this study is to propose advances in land-surface modelling and data processing to enable the land-surface community to re-use the ITRDB data as a much-needed century-long benchmark. Given that tree-ring width is largely explained by phenology, tree size, and climate sensitivity, LSMs that intend to use it as a benchmark should at least simulate tree phenology, size-dependent growth, differently-sized trees within a stand, and responses to changes in temperature, precipitation and atmospheric CO2 con¬cen¬tra¬tions. Yet, even if LSMs were capable of accurately simulating tree-ring width, sampling biases in the ITRDB need to be accounted for. This study proposes two solutions: exploiting the observation that the variation due to size-related growth by far exceeds the variation due to environmental changes; and simulating a size-structured population of trees. Combining the proposed advances in modelling and data processing resulted in four complementary benchmarks - reflecting different usage of the information contained in the ITRDB - each described by two metrics rooted in statistics that quantify the performance of the benchmark. Although the proposed benchmarks are unlikely to be precise, they advance the field by providing a much-needed large-scale constraint on changes in the simulated maximum tree diameter and annual growth increment for the transition from pre-industrial to present-day environmental conditions over the past century. Hence, the proposed benchmarks open up new ways of exploring the ITRDB archive, stimulate the dendrochronological community to refine its sampling protocols to produce new and spatially unbiased tree-ring networks, and help the modelling community to move beyond the short-term benchmarking of LSM. [ABSTRACT FROM AUTHOR]

Earth system models (ESMs) are currently the most advanced tools with which to study the interactions among humans, ecosystem productivity, and the climate. The inclusion of storm damage in ESMs has long been hampered by their big-leaf approach, which ignores the canopy structure information that is required for process-based windthrow modelling. Recently the big-leaf assumptions in the large-scale land surface model ORCHIDEE-CAN were replaced by a three-dimensional description of the canopy structure. This opened the way to the integration of the processes from the small-scale wind damage risk model Forest-GALES into ORCHIDEE-CAN. The integration of Forest-GALES into ORCHIDEE-CAN required, however, developing numerically efficient solutions to deal with (1) landscape heterogeneity, i.e. account for newly established forest edges for the parameterization of gusts; (2) downscaling spatially and temporally aggregated wind fields to obtain more realistic wind speeds that would represents gusts; and (3) downscaling storm damage within the 2500 km2 pixels of ORCHIDEE-CAN. This new version of ORCHIDEECAN was parameterized over Sweden. Subsequently, the performance of the model was tested against data for historical storms in southern Sweden between 1951 and 2010 and south-western France in 2009. In years without big storms, here defined as a storm damaging less than 15×106 m3 of wood in Sweden, the model error is 1.62×106 m3, which is about 100% of the observed damage. For years with big storms, such as Gudrun in 2005, the model error increased to 5.05×106 m3, which is between 10 and 50% of the observed damage. When the same model parameters were used over France, the model reproduced a decrease in leaf area index and an increase in albedo, in accordance with SPOTVGT and MODIS records following the passing of Cyclone Klaus in 2009. The current version of ORCHIDEE-CAN (revision 4262) is therefore expected to have the capability to capture the dynamics of forest structure due to storm disturbance on both regional and global scales, although the empirical parameters calculating gustiness from the gridded wind fields and storm damage from critical wind speeds may benefit from regional fitting. [ABSTRACT FROM AUTHOR]

Land use change (LUC) is among the main anthropogenic disturbances in the global carbon cycle. Here we present the model developments in a global dynamic vegetation model ORCHIDEE-MICT v8.4.2 for a more realistic representation of LUC processes. First, we included gross land use change (primarily shifting cultivation) and forest wood harvest in addition to net land use change. Second, we included sub-grid evenly aged land cohorts to represent secondary forests and to keep track of the transient stage of agricultural lands since LUC. Combination of these two features allows the simulation of shifting cultivation with a rotation length involving mainly secondary forests instead of primary ones. Furthermore, a set of decision rules regarding the land cohorts to be targeted in different LUC processes have been implemented. Idealized site-scale simulation has been performed for miombo woodlands in southern Africa assuming an annual land turnover rate of 5% grid cell area between forest and cropland. The result shows that the model can correctly represent forest recovery and cohort aging arising from agricultural abandonment. Such a land turnover process, even though without a net change in land cover, yields carbon emissions largely due to the imbalance between the fast release from forest clearing and the slow uptake from agricultural abandonment. The simulation with sub-grid land cohorts gives lower emissions than without, mainly because the cleared secondary forests have a lower biomass carbon stock than the mature forests that are otherwise cleared when sub-grid land cohorts are not considered. Over the region of southern Africa, the model is able to account for changes in different forest cohort areas along with the historical changes in different LUC activities, including regrowth of old forests when LUC area decreases. Our developments provide possibilities to account for continental or global forest demographic change resulting from past anthropogenic and natural disturbances. [ABSTRACT FROM AUTHOR]

Land use change (LUC) is a fundamental anthropogenic disturbance in the global carbon cycle. Here we present model developments in a global dynamic vegetation model ORCHIDEE-MICT for more realistic representation of LUC processes. First, we included gross land use change (primarily shifting cultivation) and forest wood harvest in addition to net land use change. Second, we included sub-grid even-aged land cohorts to represent secondary forests, and to keep track of the age of agricultural lands since LUC, which are associated with variable soil carbon stocks. Combination of these two features allows simulating shifting cultivation with a short rotation length involving mainly secondary forests instead of primary ones. This is in contrast with the traditional approach where a single patch is used for a given land cover type in a model grid cell and forests are thus close to primary ones. We have tested the model over Southern Africa for the period 1501-2005 forced by a historical land use change data set. Including gross land use change and wood harvest has increased LUC emissions in both simulations with (Sage) and without (Sageless) sub-grid secondary forests, but larger increase is found in Sageless (by a factor of 2) than Sage (by a factor of 1.5). Emissions from bi-directional land turnover alone are 35 % lower in Sage than Sageless, mainly because the secondary forests cleared for agricultural land have a lower aboveground biomass than primary ones. We argue that, without representing sub-grid land cohort demography, the additional emissions from land turnover/gross land use change are overestimated. In addition, our developments provide possibilities to account for continental or global forest demographic change resulting from past anthropogenic and natural disturbances. [ABSTRACT FROM AUTHOR]

Canopy structure is one of the most important vegetation characteristics for land-atmosphere interactions, as it determines the energy and scalar exchanges between the land surface and the overlying air mass. In this study we evaluated the performance of a newly developed multilayer energy budget in the ORCHIDEE-CAN v1.0 land surface model (Organising Carbon and Hydrology In Dynamic Ecosystems - CANopy), which simulates canopy structure and can be coupled to an atmospheric model using an implicit coupling procedure. We aim to provide a set of acceptable parameter values for a range of forest types. Top-canopy and sub-canopy flux observations from eight sites were collected in order to conduct this evaluation. The sites crossed climate zones from temperate to boreal and the vegetation types included deciduous, evergreen broad-leaved and evergreen needle-leaved forest with a maximum leaf area index (LAI; all-sided) ranging from 3.5 to 7.0. The parametrization approach proposed in this study was based on three selected physical processes - namely the diffusion, advection, and turbulent mixing within the canopy. Short-term sub-canopy observations and long-term surface fluxes were used to calibrate the parameters in the sub-canopy radiation, turbulence, and resistance modules with an automatic tuning process. The multi-layer model was found to capture the dynamics of sub-canopy turbulence, temperature, and energy fluxes. The performance of the new multi-layer model was further compared against the existing single-layer model. Although the multi-layer model simulation results showed few or no improvements to both the nighttime energy balance and energy partitioning during winter compared with a single-layer model simulation, the increased model complexity does provide a more detailed description of the canopy micrometeorology of various forest types. The multi-layer model links to potential future environmental and ecological studies such as the assessment of in-canopy species vulnerability to climate change, the climate effects of disturbance intensities and frequencies, and the consequences of biogenic volatile organic compound (BVOC) emissions from the terrestrial ecosystem. [ABSTRACT FROM AUTHOR]

Molecular cluster ions H+(H2O)n, H+(pyridine)(H2O)n, H+(pyridine)2(H2O)n, and H+(NH3)(pyridine)(H2O)n(n= 16–27) and their reactions with ammonia havebeen studied experimentally using a quadrupole-time-of-flight massspectrometer. Abundance spectra, evaporation spectra, and reactionbranching ratios display magic numbers for H+(NH3)(pyridine)(H2O)nand H+(NH3)(pyridine)2(H2O)nat n= 18, 20, and 27.The reactions between H+(pyridine)m(H2O)nand ammonia allseem to involve intracluster proton transfer to ammonia, thus givingclusters of high stability as evident from the loss of several watermolecules from the reacting cluster. The pattern of the observed magicnumbers suggest that H+(NH3)(pyridine)(H2O)nhave structures consistingof a NH4+(H2O)ncore with the pyridine molecule hydrogen-bonded to the surfaceof the core. This is consistent with the results of high-level abinitio calculations of small protonated pyridine/ammonia/water clusters. [ABSTRACT FROM AUTHOR]

The enantioselective lithiation of N-Boc-pyrrolidine using sec-butyllithium and isopropyllithium in the presence of sparteine-like diamines has been studied experimentally and computationally at various theoretical levels through to B3P86/6-31G*. Of the (-)-cytisine-derived diamines (N-Me, N-Et, N-nBu, N-CH2†- Bu, N-iPr) studied experimentally, the highest enantioselectivity (er 95:5) was observed with the least sterically hindered N-Me-substituted diamine, leading to preferential removal of the pro-R proton i.e., opposite enantioselectivity to (-)-sparteine. The experimental result with the N-Me-substituted diamine correlated well with the computational results: at the B3P86/6-31G* level, the sense of induction was correctly predicted; the lowest energy complex of isopropyllithium/diamine/N-Boc-pyrrolidine also had the lowest activation energy (ΔH‡ = 11.1 kcal/mol, ΔG‡ = 11.5 kcal/mol) for proton transfer. The computational results with the N-iPr-substituted diamine identified a transition state for proton transfer with activation energies of ΔH‡ = 11.7 kcal/mol and ΔG‡ = 11.8 kcal/mol (at the B3P86/6-31G* level). Although comparable to (-)-sparteine and the N-Me-substituted diamine, these Δ‡ and Δ‡ values are at odds with the experimental observation that use of the N-iPr-substituted diamine gave no product. lt is suggested that steric crowding inhibits formation of the prelithiation complex rather than increasing the activation enthalpy for proton transfer in the transition state. Three other ligands (N-H and O-substituted as well as a five-membered ring analogue) were studied solely using computational methods, and the results predict that the observed enantioselectivity would be modest at best. [ABSTRACT FROM AUTHOR]