Oxygen and nitrogen isotopic composition of nitrate in commercial fertilizers,nitric acid,and reagent salts

Nitrate is a key component of synthetic fertilizers that can be beneficial to crop production in agro-ecosystems, but can also cause damage to natural ecosystems if it is exported in large amounts. Stable isotopes, both oxygen and nitrogen, have been used to trace the sources and fate of nitrate in various ecosystems. However, the oxygen isotope composition of synthetic and organic nitrates is poorly constrained. Here, we present a study on the N and O isotope composition of nitrate-based fertilizers. The δ¹⁵N values of synthetic and natural nitrates were 0?±?2?‰ similar to the air N₂ from which they are derived. The δ¹⁸O values of synthetic nitrates were 23?±?3?‰, similar to air O₂, and natural nitrate fertilizer δ¹⁸O values (55?±?5?‰) were similar to those observed in atmospheric nitrate. The Δ¹⁷O values of synthetic fertilizer nitrate were approximately zero following a mass-dependent isotope relationship, while natural nitrate fertilizers had Δ¹⁷O values of 18?±?2?‰ similar to nitrate produced photochemically in the atmosphere. These narrow ranges of values can be used to assess the amount of nitrate arising from fertilizers in mixed systems where more than one nitrate source exists (soil, rivers, and lakes) using simple isotope mixing models.     

15N-Labelled Ammonium and Nitrate Uptake by the Grass Calamagrostis villosa

Abstract

Calamagrostis villosa dominates the understory vegetation in declining spruce forests at higher elevations of the Central European mountain areas which show symptoms of needle yellowing and associated magnesium (Mg) deficiency. It was hypothesized that grasses would preferentially take up nitrate-nitrogen (NO₃-N) over ammonium-nitrogen (NH₄-N) which would support the cation balance in Mg deficient soils. In order to test this hypothesis, growth experiments were carried out in the greenhouse using plants which were cultivated in sand for nine weeks with full nutrient solution containing 0.2 or 2 mmol of N with different NH₄ ⁺ to NO₃ ^? ratios (1:0, 0.5:0.5, 0:1). In a short term experiment with labelled ¹⁵NH₄ ⁺ and ¹⁵NO₃ ^?, uptake of NH₄ ⁺ and NO₃ ^? was measured. When NO₃ ^? was the only N source it was taken up at similar rate per g dry mass as in the experiment in which NH₄ ⁺ was the only N source. However, at high supply pure NO₃ ^? nutrition resulted in higher biomass. In contrast, supply of only NH₄ ⁺ caused accumulation of N in the roots but growth remained restricted. If NH₄ ⁺ and NO₃ ^? were supplied at equal amounts, NH₄ ⁺ was the preferred form for N uptake. Biomass of the plants with mixed supply did not differ from the plants with pure NO₃ ^? nutrition.

The results point to an interesting interaction of carbon and nitrogen relation, but they do not support the initial hypothesis that grasses may prefer NO₃ ^? over NH₄ ⁺.     

聚合反应制备键合型纤维素-三(4-甲基苯基甲酸酯)衍生物类手性固定相

合成了带有甲基丙烯酰基的纤维素-三(4-甲基苯基甲酸酯)衍生物(CTMB),并通过聚合反应将其键合在具有双键的硅胶表面,得到手性固定相(CSP)。用所得到的CSP对9种对映体化合物(丁苯酞、酮基布洛芬、反-2,3-二苯环氧乙烷、安息香、安息香类似物、托葛尔碱、华法令、4,4′-二甲氧基-5,6,5′,6′-二次甲二氧基-2,2′-羰甲基甲酯联苯、4,4′-二甲氧基-5,6,5′,6′-二次甲二氧基-2-羰甲基甲酯-2′-羰甲基乙酯联苯)进行了拆分。考察了CSP制备过程中甲基丙烯酰氯的用量、键合方式以及硅胶     

Microstructure and Thermal and Tensile Properties of Poly(vinyl alcohol) Nanocomposite Films Reinforced by Polyacrylamide Grafted Cellulose Nanocrystals

Abstract

Polyacrylamide grafted cellulose nanocrystals (CNC-g-PAM) were incorporated into poly(vinyl alcohol) (PVA) by a solution casting method to fabricate nanocomposite films with enhanced thermal and tensile properties. The microstructure and the thermal and tensile properties of the PVA/CNC-g-PAM nanocomposite films were investigated as a function of CNC-g-PAM content. Infrared spectroscopy corroborated the presence of hydrogen bonds between PVA and the PAM on the surface of the CNC. Polarized optical microscopy and scanning electron microscopy revealed good dispersion of the CNC-g-PAM in the PVA matrix and good interfacial compatibility. Accordingly, the initial degradation temperature of the nanocomposite films was elevated slightly compared to pristine PVA film. The glass transition temperature, melting temperature, and crystallinity of the PVA also varied slightly after the incorporation of the CNC-g-PAM. At both 0% and 50% RH, the nanocomposite films showed an obvious increase of elastic modulus, no apparent change of breaking strength and a drastic reduction of elongation at break with increasing CNC-g-PAM content.     

Ammonium Nitrate as an Eco–Friendly Oxidizer for Composite Solid Propellants: Promises and Challenges

Ammonium nitrate (AN) has received attraction globally not only as a nitrogenous fertilizer but also as an oxidizer in gas generators and propellants. Nowadays, great attention is being focused on the development of composite solid propellants with green oxidizers in realizing eco–friendly combustion products. The ammonium perchlorate (AP), which is the work horse oxidizer in composite propellant, needs replacement due to its environmental and human health issues. In this context, AN is regarded as an alternative to AP because of its easy availability and environmentally friendly chlorine free combustion products. However, AN has its own inherent drawbacks such as hygroscopicity, room temperature phase transition, and low burning rate. Recently, several studies have been focused on its phase stabilization and burning rate modification so as to develop solid propellants with improved properties. The knowledge of thermal characteristics of AN is a crucial factor for its applications in propellants and gas generators. This article details the different aspects of polymorphism, phase stabilization, thermal decomposition, hygroscopicity, specific impulse, and burn rate modification of AN and also addresses ways to overcome the inherent weakness of AN as a propellant oxidizer in formulating an effective propellant composition.     

A Computational Study of CIONO2H+: Structure and Vibrations

Two protonated forms of chlorine nitrate, HClONO⁺ ₂ and ClONO₂H⁺, are treated ab initio by the Hartree-Fock and the second order Møller-Plesset perturbation approach with the standard 6–31G* basis set. Both minimum energy structures are planar (C ₃ symmetry) and their structural, energy, and vibrational parameters are reported. The computations conclude that the proton attacks the chlorine nitrate at its central, not end, oxygen atom. The protonation causes a considerable elongation of the central ON bond which becomes most probable place of cleavage. The dissociation should yield the neutral HOCl and NO⁺ ₂. These quantum-chemical findings well agree with the previous experimental indications.

     

FTIR-ATR与显微成像法结合观察NaNO3气溶胶结晶过程

阶梯状改变环境湿度, 利用FTIR-ATR(Attenuated Total Reflection)技术以及显微成像技术观察NaNO3气溶胶微粒的结晶动力学。多次实验证实NaNO3液滴在饱和点74.5%RH之后开始陆续风化, 至风化点53%RH之后结晶速率明显增快, 但并不是相对湿度越低, 结晶速率越快, 而是相对湿度的变化率越大, 结晶速率越快。对数据进行非线性拟合发现在湿度下降处结晶速率呈指数关系, 在湿度稳定時结晶速率呈线性关系。并且通过显微镜观察到尽管样品NaNO3液滴的直径在同一个数量级上, 仍能看出结晶速率与液滴半径关系紧密, 半径越大越易结晶, 结晶的相对湿度越高。     

硝酸溴与三重态氧原子反应机理的密度泛函研究

用密度泛函理论方法 (B3LYP) ,在 6 311+G(d ,p)水平上对硝酸溴与三重态氧原子的反应进行了研究 ,计算了反应中各驻点物种的平衡构型、振动频率、总能量和零点能 (ZPE) .对计算得到各可能反应途径的过渡态经内禀反应坐标分析加以了证实 ,对反应途径中的键长和能量的变化作了IRC解析 .在B3LYP优化的基础上利用了耦合簇理论方法 (CCSD(T) )在 6 311+G(d ,p)水平上对各驻点物种的单点能进行了修正 .研究表明 ,存在三种可能的反应途径 ,其产物分别为 :cis BrONO和 3 O2 、trans BrONO和 3 O2 以及BrOO和NO2 .其中第三个通道由于活化能垒较低 ,是主要反应 .     

Electronic Spectra and the Mechanism of Complexing of Uranyl Nitrate in Water–Acetone Solutions

Based on the analysis of electronic absorption and luminescence spectra, the processes of complexing in an aqueous solution of uranyl nitrate hexahydrate (UO₂(NO₃)₂·6H₂O) on gradual addition of small amounts of acetone have been investigated. In a pure aqueous solution, uranyl exists as the UO₂·5H₂O complex. It is shown that addition of acetone to the solution leads to displacement of some water molecules from the first coordination sphere of uranyl and formation of uranyl nitrate dihydrate complexes, UO₂(NO₃)₂·2H₂O. It has been established that the stability of these complexes is determined by the decrease in both the water activity and the degree of hydration of uranyl and nitrate. This is the result of the local increase in the concentration of the molecules of acetone (due to its hydrophobicity) in those regions of the solution in which there are uranyl and nitrate ions. The experimental facts supporting the proposed mechanism are given.     

The millimeter-wave spectrum of chlorine nitrate (ClONO2): The ν6 vibrational state

The pure rotational spectrum of chlorine nitrate in its v₆ = 1 excited vibrational state has been studied. A total of 2901 lines, with K_a extending to 33 in the ³⁵Cl isotopologue and 30 in the ³⁷Cl isotopologue, respectively, have been recorded and assigned. This analysis, along with our recently reported study of the ν₅/ν₆ν₉ dyad and the improved energy levels of ν₉ reported in this paper, should make possible accurate simulation of the corresponding ν₆ band and its complex hot band structure near 435 cm⁻¹.