Long-term measurements from satellites and surface stations have demonstrated a decreasing trend of tropospheric carbon monoxide (CO) in the Northern Hemisphere over the past decade. Likely ...explanations for this decrease include changes in anthropogenic, fires, and/or biogenic emissions or changes in the primary chemical sink hydroxyl radical (OH). Using remotely sensed CO measurements from the Measurement of Pollution in the Troposphere (MOPITT) satellite instrument, in situ methyl chloroform (MCF) measurements from the World Data Centre for Greenhouse Gases (WDCGG) and the adjoint of the GEOS-Chem model, we estimate the change in global CO emissions from 2001 to 2015. We show that the loss rate of MCF varied by 0.2 % in the past 15 years, indicating that changes in global OH distributions do not explain the recent decrease in CO. Our two-step inversion approach for estimating CO emissions is intended to mitigate the effect of bias errors in the MOPITT data as well as model errors in transport and chemistry, which are the primary factors contributing to the uncertainties when quantifying CO emissions using these remotely sensed data. Our results confirm that the decreasing trend of tropospheric CO in the Northern Hemisphere is due to decreasing CO emissions from anthropogenic and biomass burning sources. In particular, we find decreasing CO emissions from the United States and China in the past 15 years, and unchanged anthropogenic CO emissions from Europe since 2008. We find decreasing trends of biomass burning CO emissions from boreal North America, boreal Asia and South America, but little change over Africa. In contrast to prior results, we find that a positive trend in CO emissions is likely for India and southeast Asia.
How carbon (C) is allocated to different plant tissues (leaves, stem, and roots) determines how long C remains in plant biomass and thus remains a central challenge for understanding the global C ...cycle. We used a diverse set of observations (AmeriFlux eddy covariance tower observations, biomass estimates from tree-ring data, and leaf area index (LAI) measurements) to compare C fluxes, pools, and LAI data with those predicted by a land surface model (LSM), the Community Land Model (CLM4.5). We ran CLM4.5 for nine temperate (including evergreen and deciduous) forests in North America between 1980 and 2013 using four different C allocation schemes: i. dynamic C allocation scheme (named "D-CLM4.5") with one dynamic allometric parameter, which allocates C to the stem and leaves to vary in time as a function of annual net primary production (NPP); ii. an alternative dynamic C allocation scheme (named "D-Litton"), where, similar to (i), C allocation is a dynamic function of annual NPP, but unlike (i) includes two dynamic allometric parameters involving allocation to leaves, stem, and coarse roots; iii.–iv. a fixed C allocation scheme with two variants, one representative of observations in evergreen (named "F-Evergreen") and the other of observations in deciduous forests (named "F-Deciduous"). D-CLM4.5 generally overestimated gross primary production (GPP) and ecosystem respiration, and underestimated net ecosystem exchange (NEE). In D-CLM4.5, initial aboveground biomass in 1980 was largely overestimated (between 10 527 and 12 897 g C m−2) for deciduous forests, whereas aboveground biomass accumulation through time (between 1980 and 2011) was highly underestimated (between 1222 and 7557 g C m−2) for both evergreen and deciduous sites due to a lower stem turnover rate in the sites than the one used in the model. D-CLM4.5 overestimated LAI in both evergreen and deciduous sites because the leaf C–LAI relationship in the model did not match the observed leaf C–LAI relationship at our sites. Although the four C allocation schemes gave similar results for aggregated C fluxes, they translated to important differences in long-term aboveground biomass accumulation and aboveground NPP. For deciduous forests, D-Litton gave more realistic Cstem ∕ Cleaf ratios and strongly reduced the overestimation of initial aboveground biomass and aboveground NPP for deciduous forests by D-CLM4.5. We identified key structural and parameterization deficits that need refinement to improve the accuracy of LSMs in the near future. These include changing how C is allocated in fixed and dynamic schemes based on data from current forest syntheses and different parameterization of allocation schemes for different forest types. Our results highlight the utility of using measurements of aboveground biomass to evaluate and constrain the C allocation scheme in LSMs, and suggest that stem turnover is overestimated by CLM4.5 for these AmeriFlux sites. Understanding the controls of turnover will be critical to improving long-term C processes in LSMs.
The mechanism of olefin hydrogenation catalyzed by Pd
II and Au
III Schiff base complexes, both with an analog d
8 electronic structure, is analyzed by means of kinetic and computational methods. The ...computational study is able to explain the differences experimentally observed in relation to the influence of the solvent (polarity and proton donor ability) and of the hydrogen pressure on the Au
III- and Pd
II-catalyzed reaction mechanisms. These considerations can guide the proper selection of solid supports for heterogenization of catalysts to significantly increase their activity.
Rhodium and iridium complexes of chiral triaza ligands are described. The fixation of the preformed triethoxysilyl-rhodium and iridium complexes, on mesoporous solids (MCM-41, SBA-15), and their use ...for the hydrogenation reactions are reported. The stable covalent bond between support and complex allows the recovery and recycling of the heterogenised catalysts for a number of cycles.
Rhodium and iridium complexes of the chiral triaza ligands, {
N,
N
′-bis{(2
S)-(1-benzylpyrrolidinyl)methyl}amine (
2),
N,
N
′-bis{(2
S)-(1-benzylpyrrolidinyl)methyl}-N-propylamine (
3),
N,
N
′-bis{(2
S)-(1-benzylpyrrolidinyl)methyl}-N-3-(triethoxysilyl)propylamine (
4)}, are described. All ligands form one to one ML species with the above metal ions. The structures of these complexes were elucidated by analytical and spectroscopic data (elemental analysis, mass spectroscopy, IR,
1H and
13C NMR). The fixation of the preformed triethoxysilyl-rhodium and iridium complexes, on mesoporous solids (MCM-41, SBA-15), and their use, under heterogeneous conditions, for the hydrogenation reactions are reported. The catalytic activity and selectivity of heterogenised complexes are higher to that observed under homogeneous conditions, as a consequence of the complex- and/or reagents-to-support interaction. The stable covalent bond between support and complex allows the recovery and recycling of the heterogenised catalysts for a number of cycles, moreover atomic absorption analysis of the reaction solutions shows that there is not any metal leaching into the solutions.
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