Comparing WHAM 6 and MINEQL+ 4.5 for the chemical speciation of Cu2+ in the rhizosphere of forest soils

Metal speciation data calculated by modeling could give useful information regarding the fate of metals in the rhizospheric environment. However, no comparative study has evaluated the relative accuracy of speciation models in this microenvironment. Consequently, the present study evaluates the reliability of free Cu ion (Cu2+) activity modeled by WHAM 6 and MINEQL+ 4.5 for 18 bulk and 18 rhizospheric soil samples collected in two Canadian forested areas located near industrial facilities. The modeling of Cu speciation was performed on water extracts using pH, dissolved organic carbon (DOC), major ions, and total dissolved Al, Ca, Cu, Mg, and Zn concentrations as input data. Four scenarios representing the composition of dissolved organic substances using fulvic, humic, and acetic acids were derived from the literature and used in the modeling exercise. Different scenarios were used to contrast soil components (rhizosphere vs bulk) and soil pH levels (acidic vs neutral to alkaline). Reference Cu2+ activity values measured by an ion-selective electrode varied between 0.39 and 41 nM. The model MINEQL+ 4.5 provided good predictions of Cu2+ activities [root-mean-square residual (RMSR)= 0.37], while predictions from WHAM 6 were poor (RMSR = 1.74) because they overestimated Cu complexation with DOC. Modeling with WHAM 6 could be improved by adjusting the proportion of inert DOC and the composition of DOC (RMSR = 0.94), but it remained weaker than predictions with MINEQL+ 4.5. These results suggested that the discrepancies between speciation models were attributed to differences in the binding capacity of humic substances with Cu, where WHAM 6 appeared to be too aggressive. Therefore, we concluded that chemical interactions occurring between Cu and DOC were key factors for an accurate simulation of Cu speciation, especially in rhizospheric forest soils, where high variation of the DOC concentration and composition are observed.     

Impact of Bifidobacterium animalis subsp. lactis BB-12 and, Lactobacillus acidophilus LA-5-containing yoghurt, on fecal bacterial counts of healthy adults

This randomized, placebo-controlled, double blind, parallel dose-response study investigated the impact of 4-week commercial yoghurt consumption supplemented with Bifidobacterium animalis subsp. lactis (BB-12) and Lactobacillus acidophilus (LA-5) on fecal bacterial counts of healthy adults. Fifty-eight volunteers were randomly assigned to three different groups: 1. placebo (no probiotic, no starter and no green tea extract); 2. Yoptimal (10⁹ cfu/100 g of BB-12 and LA-5 and 40 mg of green tea extract) and 3. Yoptimal-10 (10¹⁰ cfu/100 g of BB-12, 10⁹ cfu/100 g of LA-5 and 40 mg of green tea extract). These yoghurt products also contained Lactobacillus delbrueckii subsp. bulgaricus (10⁷ cfu/100 g) and Streptococcus thermophilus (10¹⁰ cfu/100 g). The quantitative PCR (qPCR) results showed that there were significant increases (P = 0.02) in bifidobacteria counts with the Yoptimal treatment as compared to baseline. The fecal numbers of B. animalis subsp. lactis and LA-5 significantly increased in the two probiotic treatments compared to the placebo treatment. Viable counts of fecal lactobacilli were significantly higher (P = 0.05) and those of enterococci were significantly lower (P = 0.04) after the intervention when compared to placebo. No significant difference was observed between treatments in volunteers' weight, waist girth, blood pressure, fasting plasma triglyceride and HDL-C concentrations, as well as cholesterol/HDL-cholesterol ratio. However, a significant increase in plasma cholesterol levels was observed in the placebo group (P = 0.0018) but the levels remained stable in the two probiotic yoghurt groups. These results show that probiotic strains supplemented in the form of yoghurt remain active during gut transit and are associated with an increase in beneficial bacteria and a reduction in potentially pathogenic bacteria. This trial was registered at clinicaltrials.gov as NCT00730626.     

Implementation of a rational drying process for fish conservation

Fishing is a traditional activity that is widespread in West Africa. One of the greatest problems for fishermen and a cause of lack of food accessibility is the difficulty in conserving fish. Drying is a widely used technique in sub-Saharan Africa for preservation of fish. However, drying is a complex process, making the construction and calibration of efficient drying devices challenging. This paper presents the construction and calibration of five mobile fish dryers in Mali and, for one of them, development of a method for its use. The performances achieved far exceeded those of traditional solar dryers as drying was faster and the fish were not contaminated by being exposed to flies. Furthermore, construction and user manuals were written for the local fishermen which were well understood as the fishermen were able to disassemble and reassemble the dryers when they were required to be moved.     

Guest editorial for the theme section on modeling language engineering

Software and Systems Modeling -     

From P-type to N-type: Peripheral fluorination of axially substituted silicon phthalocyanines enables fine tuning of charge transport

Silicon phthalocyanines (R₂-SiPcs) are a family of promising tunable materials for organic electronic applications. We report the chemistry of the synthesis of axially substituted fluorinated SiPcs (tb-Ph)₂-F_xSiPc (where X = 0, 4, 8, or 16) and explore how the degree of fluorination effects optical and electronic properties. A new treatment with boron trichloride was included to obtain Cl₂-F_XSiPcs from F₂-F_XSiPcs, activating the axial position for further functionalization. We observed that as the degree of fluorination increased, so did the electron affinity of the compounds, leading to a drop in frontier orbital levels, as measured by electrochemistry and ultraviolet photoelectron spectroscopy (UPS). The deeper energy levels enabled successful (tb-Ph)₂-F₄SiPc and poly [[6,7-difluoro[(2-hexyldecyl)oxy]-[5,8-quinoxalinediyl]-2,5-thiophenediyl]] (PTQ10) blends for organic photovoltaics and photodetectors. All four compounds were incorporated in organic thin-film transistors (OTFTs), where the degree of fluorination influenced device operation, changing it from p-type conduction for (tb-Ph)₂-F₀SiPc, to ambipolar for (tb-Ph)₂-F₄SiPc, and n-type for (tb-Ph)₂-F₈SiPc and (tb-Ph)₂-F₁₆SiPc. The OTFT devices made with (tb-Ph)₂-F₁₆SiPc achieved a low average threshold voltage of 7.0 V in N₂ and retained its n-type mobility when exposed to air.     

Gas permeation and thermomechanical properties for macroporous alumina focused on necking size at grain boundaries

The gas permeation and thermomechanical properties of macroporous alumina used as a support substrate for microporous ceramic permselective membranes were investigated. The porosity, pore size, and apparent necking size between grains of macroporous alumina were systematically varied, and the relationships between the porous microstructure and material properties were examined. The grain necking size at alumina grain boundaries was evaluated by microstructural observations. The nitrogen gas permeance of the porous alumina increased with increasing pore size. All the measured thermal and mechanical properties decreased with increasing porosity. The properties of porous alumina samples with extensive grain necking showed higher values even in samples with the largest pore size. The high thermal conductivity of porous alumina with extensive grain necking was due to the low interfacial thermal resistance at grain boundaries. Porous alumina with extensive grain necking had high thermal shock strength due to the higher thermal conductivity. It was demonstrated that a porous structure combining high gas permeability and excellent fracture resistance could be successfully achieved.     

Strong Magnetic Field Annealing for Improved Phthalocyanine Organic Thin-Film Transistors

Thin-film microstructure, morphology, and polymorphism can be controlled and optimized to improve the performance of carbon-based electronics. Thermal or solvent vapor annealing are common post-deposition processing techniques; however, it can be difficult to control or destructive to the active layer or substrates. Here, the use of a static, strong magnetic field (SMF) as a non-destructive process for the improvement of phthalocyanine (Pc) thin-film microstructure, increasing organic thin-film transistor (OTFTs) mobility by twofold, is demonstrated. Grazing incident wide-angle X-ray scattering (GIWAXS), X-ray diffraction (XRD), and atomic force microscopy (AFM) elucidate the effect of SMF on both para- and diamagnetic Pc thin-films when subjected to a magnetic field. A SMF is found to increase the concentration of oxygen-induced radical species within the Pc thin-film, lending a paramagnetic character to ordinarily diamagnetic metal-free Pc and resulting in magnetic field induced changes to its thin-film microstructures. In a nitrogen environment, without competing degradation effects of molecular oxygen, SMF processing is found to favorably improve charge transport characteristics and increase OTFT mobility. Thus, post-deposition thin-film annealing with a magnetic field is presented as an alternative and promising technique for future thin-film engineering applications.