Gas Sorption and Luminescence Properties of a Terbium(III)-Phosphine Oxide Coordination Material with Two-Dimensional Pore Topology

The structure, stability, gas sorption properties and luminescence behaviour of a new lanthanide-phosphine oxide coordination material are reported. The polymer PCM-15 is based on Tb(III) and tris(p-carboxylated) triphenylphosphine oxide and has a 5,5-connected net topology. It exhibits an infinite three-dimensional structure that incorporates an open, two-dimensional pore structure. The material is thermally robust and remains crystalline under high vacuum at 150 degrees C. When desolvated, the solid has a CO2 BET surface area of 1187 m(2) g(-1) and shows the highest reported uptake of both O-2 and H-2 at 77 K and 1 bar for a lanthanide-based coordination polymer. Isolated Tb(III) centres in the as-synthesized polymer exhibit moderate photoluminescence. However, upon removal of coordinated OH2 ligands, the luminescence intensity was found to approximately double; this process was reversible. Thus, the Tb(III) centre was used as a probe to detect directly the desolvation and resolvation of the polymer.Welch Foundation F-1738, F-1631National Science Foundation 0741973, CHE-0847763Chemistr

Human-Induced and Climate-Driven Contributions to Water Storage Variations in the Haihe River Basin, China

Terrestrial water storage (TWS) can be influenced by both climate change and anthropogenic activities. While the Gravity Recovery and Climate Experiment (GRACE) satellites have provided a global view on long-term trends in TWS, our ability to disentangle human impacts from natural climate variability remains limited. Here we present a quantitative method to isolate these two contributions with reconstructed climate-driven TWS anomalies (TWSA) based on long-term precipitation data. Using the Haihe River Basin (HRB) as a case study, we find a higher human-induced water depletion rate (−12.87 ± 1.07 mm/yr) compared to the original negative trend observed by GRACE alone for the period of 2003–2013, accounting for a positive climate-driven TWSA trend (+4.31 ± 0.72 mm/yr). We show that previous approaches (e.g., relying on land surface models) provide lower estimates of the climate-driven trend, and thus likely underestimated the human-induced trend. The isolation method presented in this study will help to interpret observed long-term TWS changes and assess regional anthropogenic impacts on water resources

GRUN: an observation-based global gridded runoff dataset from 1902 to 2014

Freshwater resources are of high societal relevance, and understanding their past variability is vital to water management in the context of ongoing climate change. This study introduces a global gridded monthly reconstruction of runoff covering the period from 1902 to 2014. In situ streamflow observations are used to train a machine learning algorithm that predicts monthly runoff rates based on antecedent precipitation and temperature from an atmospheric reanalysis. The accuracy of this reconstruction is assessed with cross-validation and compared with an independent set of discharge observations for large river basins. The presented dataset agrees on average better with the streamflow observations than an ensemble of 13 state-of-the art global hydrological model runoff simulations. We estimate a global long-term mean runoff of 38 452 km³ yr⁻¹ in agreement with previous assessments. The temporal coverage of the reconstruction offers an unprecedented view on large-scale features of runoff variability in regions with limited data coverage, making it an ideal candidate for large-scale hydro-climatic process studies, water resource assessments, and evaluating and refining existing hydrological models. The paper closes with example applications fostering the understanding of global freshwater dynamics, interannual variability, drought propagation and the response of runoff to atmospheric teleconnections. The GRUN dataset is available at https://doi.org/10.6084/m9.figshare.9228176 (Ghiggi et al., 2019)

GRACE-REC: a reconstruction of climate-driven water storage changes over the last century

The amount of water stored on continents is an important constraint for water mass and energy exchanges in the Earth system and exhibits large inter-annual variability at both local and continental scales. From 2002 to 2017, the satellites of the Gravity Recovery and Climate Experiment (GRACE) mission have observed changes in terrestrial water storage (TWS) with an unprecedented level of accuracy. In this paper, we use a statistical model trained with GRACE observations to reconstruct past climate-driven changes in TWS from historical and near-real-time meteorological datasets at daily and monthly scales. Unlike most hydrological models which represent water reservoirs individually (e.g., snow, soil moisture) and usually provide a single model run, the presented approach directly reconstructs total TWS changes and includes hundreds of ensemble members which can be used to quantify predictive uncertainty. We compare these data-driven TWS estimates with other independent evaluation datasets such as the sea level budget, large-scale water balance from atmospheric reanalysis, and in situ streamflow measurements. We find that the presented approach performs overall as well or better than a set of state-of-the-art global hydrological models (Water Resources Reanalysis version 2). We provide reconstructed TWS anomalies at a spatial resolution of 0.5∘, at both daily and monthly scales over the period 1901 to present, based on two different GRACE products and three different meteorological forcing datasets, resulting in six reconstructed TWS datasets of 100 ensemble members each. Possible user groups and applications include hydrological modeling and model benchmarking, sea level budget studies, assessments of long-term changes in the frequency of droughts, the analysis of climate signals in geodetic time series, and the interpretation of the data gap between the GRACE and GRACE Follow-On missions. The presented dataset is published at https://doi.org/10.6084/m9.figshare.7670849 (Humphrey and Gudmundsson, 2019) and updates will be published regularly

Synthesis, reactivity, and some photochemistry of ortho-N,N-dimethylaminomethyl substituted aryl and ferrocenyl pentamethylcyclopentadienyl dicarbonyl iron complexes

Supplementary materials: CCDC 928736, 928273, 928738, 928275, 928274 and 928737 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/data_request/cifInternational audienceOrtho-lithiated N,N-dimethylaminomethyl ferrocene and benzyldimethylamine react with Cp*Fe(CO)2I to give the new complexes ((Cp*Fe(CO)2)-2-(CH2NMe2)C5H3)Fe(Cp) and Cp*Fe(CO)2-C6H4(o-CH2NMe2). Access to a wide variety of alkoxy-substituted complexes ((Cp*Fe(CO)2)-2-(CH2OR)C5H3)Fe(Cp) can be easily achieved by tandem quaternization/alcoholysis of ((Cp*Fe(CO)2)-2-(CH2NMe2)C5H3)Fe(Cp). Preliminary results show that chelated complexes can be obtained by displacement of one of the carbonyl ligands by photolysis. Crystal structures of ((Cp*Fe(CO)2)-2-(CH2NMe2)C5H3)Fe(Cp), ((Cp*Fe(CO)2)-2-(CH2OR)C5H3)Fe(Cp) (R = Ph, Bz, CHPh2 and d-menthyl) and [Cp*Fe(CO)2-C6H4(o-CH2NMe2)][I] are reported

Human-Induced and Climate-Driven Contributions to Water Storage Variations in the Haihe River Basin, China

Terrestrial water storage (TWS) can be influenced by both climate change and anthropogenic activities. While the Gravity Recovery and Climate Experiment (GRACE) satellites have provided a global view on long-term trends in TWS, our ability to disentangle human impacts from natural climate variability remains limited. Here we present a quantitative method to isolate these two contributions with reconstructed climate-driven TWS anomalies (TWSA) based on long-term precipitation data. Using the Haihe River Basin (HRB) as a case study, we find a higher human-induced water depletion rate (−12.87 ± 1.07 mm/yr) compared to the original negative trend observed by GRACE alone for the period of 2003–2013, accounting for a positive climate-driven TWSA trend (+4.31 ± 0.72 mm/yr). We show that previous approaches (e.g., relying on land surface models) provide lower estimates of the climate-driven trend, and thus likely underestimated the human-induced trend. The isolation method presented in this study will help to interpret observed long-term TWS changes and assess regional anthropogenic impacts on water resources

CO2 Adsorption Properties of a Ca(II)-Based Organophosphonium Coordination Material

PCM-14 is a dense coordination polymer formed from Ca(II) and an unusual organophosphonium ligand. The dehydrated framework contains 3-coordinate Ca(II) sites within catenated, chiral 3,3-connected nets. PCM-14 exhibits a stark CO2 sorption selectivity over H-2, N-2 and O-2. The maximum CO2 uptake was shown to be highly sensitive to the material pretreatment evacuation temperature.Welch Foundation F-1738Chemistr

Detecting forest response to droughts with global observations of vegetation water content

Droughts in a warming climate have become more common and more extreme, making understanding forest responses to water stress increasingly pressing. Analysis of water stress in trees has long focused on water potential in xylem and leaves, which influences stomatal closure and water flow through the soil-plant-atmosphere continuum. At the same time, changes of vegetation water content (VWC) are linked to a range of tree responses, including fluxes of water and carbon, mortality, flammability, and more. Unlike water potential, which requires demanding in situ measurements, VWC can be retrieved from remote sensing measurements, particularly at microwave frequencies using radar and radiometry. Here, we highlight key frontiers through which VWC has the potential to significantly increase our understanding of forest responses to water stress. To validate remote sensing observations of VWC at landscape scale and to better relate them to data assimilation model parameters, we introduce an ecosystem-scale analog of the pressure–volume curve, the non-linear relationship between average leaf or branch water potential and water content commonly used in plant hydraulics. The sources of variability in these ecosystem-scale pressure-volume curves and their relationship to forest response to water stress are discussed. We further show to what extent diel, seasonal, and decadal dynamics of VWC reflect variations in different processes relating the tree response to water stress. VWC can also be used for inferring belowground conditions—which are difficult to impossible to observe directly. Lastly, we discuss how a dedicated geostationary spaceborne observational system for VWC, when combined with existing datasets, can capture diel and seasonal water dynamics to advance the science and applications of global forest vulnerability to future droughts