Data workflow to incorporate thermodynamic energies from Calphad databases into grand-potential-based phase-field models

Journal of Materials Science - In order to approximate Gibbs energy functions, a semi-automated framework is introduced for binary and ternary material systems, using Calphad databases. To generate...     

Interregional allocation models of infrastructure investments

This paper deals with the allocation of public investments to some of the prospective key elements in the regional infrastructure. Two optimization models are suggested for allocating investment resources among regions and various infrastructure elements. Applications of the models illustrate solutions based on policy goals of economic efficiency and regional equity. The optimization models draw on the estimation of an aggregate regional production function.     

Elemental analyses of pine bark and wood in an environmental study

Bark and wood samples were taken from the same individuals of Scots pine (Pinus sylvestris L.) from a polluted area close to a Cu-Ni smelter in Harjavalta and from some relatively unpolluted areas in western Finland. The samples were analysed by thick-target particle induced X-ray emission (PIXE) after preconcentration by dry ashing at 550 degrees C. The elemental contents of pine bark and wood were compared to study the impact of heavy metal pollution on pine trees. By comparison of the elemental contents in ashes of bark and wood, a normalisation was obtained. For the relatively clean areas, the ratios of the concentration in bark ash to the concentration in wood ash for different elements were close to 1. This means that the ashes of Scots Pine wood and bark have quite similar elemental composition. For the samples from the polluted area the mean concentration ratios for some heavy metals were elevated (13-28), reflecting the effect of direct atmospheric contamination. The metal contents in the ashes of pine bark and wood were also compared to recommendations for ashes to be recycled back to the forest environment. Bark from areas close to emission sources of heavy metal pollution should be considered with caution if aiming at recycling the ash. Burning of bark fuel of pine grown within 6 km of the Cu-Ni smelter is shown to generate ashes with high levels of Cu, Ni as well as Cd, As and Pb.     

Thioarsenates in geothermal waters of Yellowstone National Park: determination, preservation, and geochemical importance

Mono-, di-, tri-, and tetrathioarsenate, as well as methylated arsenic oxy- and thioanions, were determined besides arsenite and arsenate in geothermal waters of Yellowstone National Park using anion-exchange chromatography inductively coupled plasma mass spectrometry. Retention time match with synthetic standards, measured S:As ratios, and molecular electrospray mass spectra support the identification. Acidification was unsuitable for arsenic species preservation in sulfidic waters, with HCI addition causing loss of total dissolved arsenic, presumably by precipitation of arsenic-sulfides. Flash-freezing is preferred for the preservation of arsenic species for several weeks. After thawing, samples must be analyzed immediately. Thioarsenates occurred over a pH range of 2.1 to 9.3 in the geothermal waters. They clearly predominated under alkaline conditions (up to 83% of total arsenic), but monothioarsenate also was detected in acidic waters (up to 34%). Kinetic studies along a drainage channel showed the importance of thioarsenates for the fate of arsenic discharged from the sulfidic hot spring. The observed arsenic speciation changes suggest three separate reactions: the transformation of trithioarsenate to arsenite (major initial reaction), the stepwise ligand exchange from tri- via di- and monothioarsenate to arsenate (minor reaction), and the oxidation of arsenite to arsenate, which only becomes quantitatively important after thioarsenates have disappeared.     

Influence of nitrogen nutrition and metabolism on ammonia volatilization in plants

Barley (Hordeum vulgare L. cv. Golf) was grown in solution culture with controlled nitrogen availability in order to study the influence of nitrogen nutrition on ammonia emission from the leaves. Ammonia emission measured in cuvettes connected to an automatic NH₃ monitor was close to zero for nitrate grown plants but increased to 0.9–1.3 nmol NH₃ m^-2 leaf area s^-1 after 3–5 days of ammonium nutrition. Increasing concentrations from 0.5 to 10 mM NH₄ ⁺ in the root medium increased NH₃ emission from the shoots, root glutamine synthetase activity and NH₄ ⁺ concentrations in apoplast, xylem sap and bulk tissue, while apoplastic pH values decreased.Inhibition of glutamine synthetase in nitrate grown barley plants by addition of 1 mM methionine sulfoximine (MSO) to the root medium caused ammonia emission to increase 5 to 10-fold after 2–3 hours. At the same time shoot tissue ammonium concentrations started to increase. Addition of an inhibitor of photorespiration, 1 mM pyrid-2-yl hydroxymethane sulfonate (HPMS) reduced this increase in ammonia emission showing a relation between NH₃ emission and photorespiration.Oil seed rape (Brassica napus L. cv. Global) plants grown at 3 different nitogen levels (2N, 4N and 7N) in a sand/soil mixture showed increasing NH₃ compensation points with increasing N level. This increase was highly correlated with increasing NH₄ ⁺ concentrations in the leaf apoplast and total leaf tissue. The NH₃ compensation points could be succesfully predicted on basis of the pH and NH₄ ⁺ concentration in the leaf apoplast.     

A Protein-Adsorbent Hydrogel with Tunable Stiffness for Tissue Culture Demonstrates Matrix-Dependent Stiffness Responses

Although tissue culture plastic has been widely employed for cell culture, the rigidity of plastic is not physiologic. Softer hydrogels used to culture cells have not been widely adopted in part because coupling chemistries are required to covalently capture extracellular matrix (ECM) proteins and support cell adhesion. To create an in vitro system with tunable stiffnesses that readily adsorbs ECM proteins for cell culture, a novel hydrophobic hydrogel system is presented via chemically converting hydroxyl residues on the dextran backbone to methacrylate groups, thereby transforming non-protein adhesive, hydrophilic dextran to highly protein adsorbent substrates. Increasing methacrylate functionality increases the hydrophobicity in the resulting hydrogels and enhances ECM protein adsorption without additional chemical reactions. These hydrophobic hydrogels permit facile and tunable modulation of substrate stiffness independent of hydrophobicity or ECM coatings. Using this approach, it is shown that substrate stiffness and ECM adsorption work together to affect cell morphology and proliferation, but the strengths of these effects vary in different cell types. Furthermore, it is revealed that stiffness-mediated differentiation of dermal fibroblasts into myofibroblasts is modulated by the substrate ECM. The material system demonstrates remarkable simplicity and flexibility to tune ECM coatings and substrate stiffness and study their effects on cell function.     

金属标准物质中杂质的辉光放电质谱法溯源分析

标准物质定值分析的溯源性要求比常规分析高很多。在常规分析中,有证标准物质（CRM）可用于校准以及建立可溯源性。尽管与标准物质生产和认定相关的ISO导则并没有十分明确地提到校准,但众多标准物质生产者在定值分析时却不接受基准标准物质用于校准。这些要求制约了标准物质定值方法的使用,因为这些方法可以采用已知高纯度的标准物质、化学计量法及已知高纯度标准物质的混合物进行校准。有效的固体取样技术,例如通常使用的块状标准物质进行校准的辉光放电质谱法（GD MS）或火花源发射光谱法（spark OES）,似乎不太适合定值分析。尤其是固体样品中痕量元素分析测定的有力工具辉光放电质谱法,除金属杂质外,使用特定气体混合物,这种方法也可以分析相关的非金属杂质如硫和磷。我们开发了一种可以使用已知高纯度的标准物质混合物和化学计量法的校准方法,这种校准方法同样可用于辉光放电质谱法。与溶液中基体匹配技术类似,此校准方法基于掺杂的粉末压片。本文还结合铜和钢标准物质的定值分析结果进行了陈述。     

Volatile metals and metalloids in hydrothermal gases

Volatile metals and metalloids were sampled from hot springs, fumaroles, and a hydrothermally influenced wetland in Yellowstone National Park. The sampling was based on diffusion through gas sampling chambers. Collected gases were stabilized by dissolution and oxidation in 1:100 diluted NaOCl. Special procedures were developed to analyze the oxidized samples by GF-AAS and HG-AAS. For ICP-MS, samples had to be blank-corrected for polyatomic isotope interferences, especially by 23Na35Cl+ and 23Na37Cl+ on 58Ni and 60Ni and by 40Ar23Na+ on 63Cu. From the concentrations trapped in solution, net diffusion rates were calculated by Fick's first law. The highest concentrations reached a maximum of 8 g/m3 for volatile silicon. Volatile nickel, tungsten, zinc, copper, and molybdenum, previously only known from anthropogenic sources, occurred naturally in the hydrothermal gases in ranges of tens to hundreds of microg/m3. Replicate measurements indicated significant temporal variations in concentrations, probably the result of complex changes in the hydrothermal regime as well as varying microbial activity. Global correlations between gaseous and superficial aqueous phases were missing.