Field-scale validation of an automated soil nitrate extraction and measurement system

One of the many gaps that needs to be solved by precision agriculture technologies is the availability of an economic, automated, on-the-go mapping system that can be used to obtain intensive and accurate ‘real-time’ data on the levels of nitrate nitrogen (NO3–N) in the soil. A soil nitrate mapping system (SNMS) has been developed to provide a way to collect such data. This study was done to provide extensive field-scale validation testing of the system’s nitrate extraction and measurement sub-unit (NEMS) in two crop (wheat and carrot) production systems. Field conditions included conventional tillage (CT) versus no tillage (NT), inorganic versus organic fertilizer application, four soil groups and three points in time throughout the season. Detailed data analysis showed that: (i) the level of agreement, as measured by root mean squared error (RMSE), mean absolute error (MAE) and coefficient of efficiency (CE), between NEMS soil NO3–N and standard laboratory soil NO3–N measurements was excellent; (ii) at the field-scale, there was little practical difference when using either integer or real number data processing; (iii) regression equations can be used to enable field measurements of soil NO3–N using the NEMS to be obtained with laboratory accuracy; (iv) future designs of the SNMS’s control system can continue to use cheaper integer chip technology for processing the nitrate ion-selective electrode (NO3 -–ISE) readings; and (v) future designs of the SNMS would not need a soil moisture sensor, ultimately saving on manufacturing costs of a more simple syste

Mechanochemistry of the LiBH4–AlCl3 System: Structural Characterization of the Products by Solid-State NMR

The double-cation metal borohydride, Li4Al3(BH4)(13), mechanochemically produced from a 13:3 mixture of lithium borohydride (LiBH4) and aluminum chloride (AlCl3), has a low hydrogen desorption temperature; however, the material\u27s decomposition is accompanied by a large emission of toxic diborane (B2H6). We found that a decrease of the LiBH4:AICl(3) ratio in the starting mixture yields increased amounts of partially chlorinated products that also dehydrogenate at low temperature, but release negligibly small amounts of diborane. Extensive characterization by solid-state NMR spectroscopy (SSNMR) and powder X-ray diffraction (XRD) found that the 11:3 ratio product maintains the Li(4)A(13)(BH4)(13)-like structure, with additional anions substituting for [BH4](-) compared to the 13:3 mixture. Further decrease of relative LiBH4 concentration in the starting mixture to 9:3 results in a different product composed of tetrahedral [Al(BH4)(4)](-) and [Al(BH4)(2)Cl-2](-) complexes, in which two hydrogen atoms of each borohydride group are bridged to aluminum sites. Additionally, SSNMR revealed the covalent character of the Al-H bonds, which is not observed in Li(4)A(13)(BH4)(13). These findings suggest that the Al-Cl bonding present in the chlorinated complexes prevents the formation of Al(BH4)(3), which is a known intermediate leading to the formation of diborane during thermal dehydrogenation of the nearly chlorine-free Li(4)A(13)(BH4)(13)

A Benign Synthesis of Alane by the Composition-Controlled Mechanochemical Reaction of Sodium Hydride and Aluminum Chloride

Solid-state mechanochemical synthesis of alane (AlH3) starting from sodium hydride (NaH) and aluminum chloride (AlCl3) has been achieved at room temperature. The transformation pathway of this solid-state reaction was controlled by a step-wise addition of AlCl3 to the initial reaction mixture that contained sodium hydride in excess of stoichiometric amount. As in the case of previously investigated LiH-AlCl3 system, complete selectivity was achieved whereby formation of unwanted elemental aluminum was fully suppressed, and AlH3 was obtained in quantitative yield. Reaction progress during each step was investigated by means of solid-state NMR and powder X-ray diffraction, which revealed that the overall reaction proceeds through a series of intermediate alanates that may be partially chlorinated. The NaH-AlCl3 system present some subtle differences compared to LiH-AlCl3 system particularly with respect to optimal concentrations needed during one of the reaction stages. Based on the results we postulate that high local concentrations of NaH may stabilize chlorine-containing derivatives and prevent decomposition into elemental aluminum with hydrogen evolution. Complete conversion with quantitative yield of alane was confirmed both by SSNMR and hydrogen desorption analysis

Mechanochemical reactions and hydrogen storage capacities in MBH4–SiS2 systems (M=Li or Na)

The hydrogen storage properties, and phase compositions of mechanochemically prepared mixtures of xMBH4-SiS2 (x = 2–8), where M = Li or Na, were investigated using gas sorption analysis, powder X-ray diffraction, and infrared and solid-state NMR spectroscopic methods. The 2LiBH4:1SiS2 system forms an amorphous product that releases ca. 4.3 wt % of H2 below 385 °C with a Tonset of 88 °C without detectable diborane emission. The dehydrogenated sample reversibly absorbs 1.5 wt % of H2 at 385 °C under 160 bar pressure. The H2 release from materials with varying LiBH4:SiS2 ratios peaks at 8.2 wt % for the 6LiBH4:1SiS2 composition, with a reversible hydrogen storage capacity of 2.4 wt %. The H2 desorption capacities of the Li-containing systems surpass those of Na-containing systems. Solid-state NMR studies indicate that products of mechanochemical reactions in the LiBH4SiS2 system consist of one-dimensional chains of edge-sharing SiS4/2 tetrahedra in which the non-bridging S-ends are terminated with Li+, which are further coordinated to the [BH4]− anions. A variety of possible polymorphs in the LiSiS-(BH4) composition space have been identified using first principles and thermodynamic modeling that supports the likelihood of formation of such novel complexes

Desenvolvimento e avaliação de dispositivos de controle de vazão derivada em canais de irrigação.

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Mesoporous Silica Nanoparticles Loaded with Surfactant: Low Temperature Magic Angle Spinning 13C and 29Si NMR Enhanced by Dynamic Nuclear Polarization

We show that dynamic nuclear polarization (DNP) can be used to enhance NMR signals of13C and 29Si nuclei located in mesoporous organic/inorganic hybrid materials, at several hundreds of nanometers from stable radicals (TOTAPOL) trapped in the surrounding frozen disordered water. The approach is demonstrated using mesoporous silica nanoparticles (MSN), functionalized with 3-(N-phenylureido)propyl (PUP) groups, filled with the surfactant cetyltrimethylammonium bromide (CTAB). The DNP-enhanced proton magnetization is transported into the mesopores via 1H–1H spin diffusion and transferred to rare spins by cross-polarization, yielding signal enhancements εon/off of around 8. When the CTAB molecules are extracted, so that the radicals can enter the mesopores, the enhancements increase to εon/off ≈ 30 for both nuclei. A quantitative analysis of the signal enhancements in MSN with and without surfactant is based on a one-dimensional proton spin diffusion model. The effect of solvent deuteration is also investigated

Changes in preterm birth and stillbirth during COVID-19 lockdowns in 26 countries

Preterm birth (PTB) is the leading cause of infant mortality worldwide. Changes in PTB rates, ranging from −90% to +30%, were reported in many countries following early COVID-19 pandemic response measures (‘lockdowns’). It is unclear whether this variation reflects real differences in lockdown impacts, or perhaps differences in stillbirth rates and/or study designs. Here we present interrupted time series and meta-analyses using harmonized data from 52 million births in 26 countries, 18 of which had representative population-based data, with overall PTB rates ranging from 6% to 12% and stillbirth ranging from 2.5 to 10.5 per 1,000 births. We show small reductions in PTB in the first (odds ratio 0.96, 95% confidence interval 0.95–0.98, P value <0.0001), second (0.96, 0.92–0.99, 0.03) and third (0.97, 0.94–1.00, 0.09) months of lockdown, but not in the fourth month of lockdown (0.99, 0.96–1.01, 0.34), although there were some between-country differences after the first month. For high-income countries in this study, we did not observe an association between lockdown and stillbirths in the second (1.00, 0.88–1.14, 0.98), third (0.99, 0.88–1.12, 0.89) and fourth (1.01, 0.87–1.18, 0.86) months of lockdown, although we have imprecise estimates due to stillbirths being a relatively rare event. We did, however, find evidence of increased risk of stillbirth in the first month of lockdown in high-income countries (1.14, 1.02–1.29, 0.02) and, in Brazil, we found evidence for an association between lockdown and stillbirth in the second (1.09, 1.03–1.15, 0.002), third (1.10, 1.03–1.17, 0.003) and fourth (1.12, 1.05–1.19, <0.001) months of lockdown. With an estimated 14.8 million PTB annually worldwide, the modest reductions observed during early pandemic lockdowns translate into large numbers of PTB averted globally and warrant further research into causal pathways