Adsorption of aromatic carboxylate ions to black carbon (biochar) is accompanied by proton exchange with water

We examined the adsorption of the allelopathic aromatic acids (AA), cinnamic and coumaric, to different charcoals (biochars) as part of a study on bioavailability of natural signaling chemicals in soil. Sorption isotherms in pH 7 buffer, where the AAs are >99% dissociated, are highly nonlinear, give distribution ratios as high as 10(4.8) L/kg, and are insensitive to Ca(2+) or Mg(2+). In unbuffered media, sorption becomes progressively suppressed with loading and is accompanied by release of OH(-) with a stoichiometry approaching 1 at low concentrations, declining to about 0.4-0.5 as the pH rises. Sorption of cinnamate on graphite as a model for charcoal was roughly comparable on a surface area basis, but released negligible OH(-). A novel scheme is proposed that explains the pH dependence of adsorption and OH(-) stoichiometry and the graphite results. In a key step, AA(-) undergoes proton exchange with water. To overcome the unfavorable proton exchange free energy, we suggest AA engages in a type of hydrogen bond recognized to be of unusual strength with a surface carboxylate or phenolate group having a comparable pK(a). This bond is depicted as [RCO(2)···H···O-surf](-). The same is possible for AA(-), but results in increased surface charge. The proton exchange pathway appears open to other weak acid adsorbates, including humic substances, on carbonaceous materials.     

Carbon and sulfur cycling by microbial communities in a gypsum-treated oil sands tailings pond

Oil sands tailings ponds receive and store the solid and liquid waste from bitumen extraction and are managed to promote solids densification and water recycling. The ponds are highly stratified due to increasing solids content as a function of depth but can be impacted by tailings addition and removal and by convection due to microbial gas production. We characterized the microbial communities in relation to microbial activities as a function of depth in an active tailings pond routinely treated with gypsum (CaSO(4)·2H(2)O) to accelerate densification. Pyrosequencing of 16S rDNA gene sequences indicated that the aerobic surface layer, where the highest level of sulfate (6 mM) but no sulfide was detected, had a very different community profile than the rest of the pond. Deeper anaerobic layers were dominated by syntrophs (Pelotomaculum, Syntrophus, and Smithella spp.), sulfate- and sulfur-reducing bacteria (SRB, Desulfocapsa and Desulfurivibrio spp.), acetate- and H(2)-using methanogens, and a variety of other anaerobes that have been implicated in hydrocarbon utilization or iron and sulfur cycling. The SRB were most abundant from 10 to 14 mbs, bracketing the zone where the sulfate reduction rate was highest. Similarly, the most abundant methanogens and syntrophs identified as a function of depth closely mirrored the fluctuating methanogenesis rates. Methanogenesis was inhibited in laboratory incubations by nearly 50% when sulfate was supplied at pond-level concentrations suggesting that in situ sulfate reduction can substantially minimize methane emissions. Based on our data, we hypothesize that the emission of sulfide due to SRB activity in the gypsum treated pond is also limited due to its high solubility and oxidation in surface waters.     

Scanning electron microanalysis and analytical challenges of mapping elements in urban atmospheric particles

Elemental mapping with energy-dispersive X-ray spectroscopy (EDX) associated with scanning electron microscopy is highly useful for studying internally mixed atmospheric particles. Presented is a study of individual particles from urban airsheds and the analytical challenges in qualitatively determining the composition and origin of heterogeneous urban-air particles from high-resolution elemental maps. Coarse-mode particles were taken from samples collected in three U.S. cities: Atlanta, Los Angeles, and Seattle. Elemental maps distinguished particles with heterogeneously mixed phases from those with homogeneously mixed phases that also contained inclusions or surface adducts. Elemental mapping at low and high beam energies, along with imaging at an oblique angle helped to classify particles by origin. The impact of particle shape on X-ray microanalysis was demonstrated by having the beam enter the particle at ≥ 52° from normal. Potential misinterpretations of particle composition due to artifacts in the elemental maps were minimized by tilt imaging to reveal particle surface roughness and depth, mapping at low beam energies, noting the position of the EDX detector in the map field, and assessing differences in the mass absorption coefficients of the particle's major elements to anticipate X-ray self-absorption.     

Effect of extrusion on the antioxidant capacity and color attributes of expanded extrudates prepared from purple potato and yellow pea flour mixes

Abstract: Foods with antioxidant capacity provide protection against cardio‐vascular, certain forms of cancers, and Alzheimer's diseases caused by oxidative damages and contribute health benefits. The effect of extrusion cooking on the antioxidant capacity and color attributes of extruded products prepared from 3 selected formulations of purple potato and yellow pea flours using a co‐rotating twin screw extruder were studied. Expansion ratios of the extruded products varied from 3.93 to 4.75. The total antioxidant capacities (TAC) of the extruded products, using DPPH assay, were 3769 to 4116 μg trolox equivalent/g dry weight sample and not significantly different (P > 0.05) from their respective raw formulations. The total phenolic contents (TP) of the extruded products varied from 2088 to 3766 μg of gallic acid equivalent/g dry weight sample and retained 73% to 83% of the TP from the raw formulations after extrusion. The total anthocyanins contents (TA) in the extrudates were 0.116 to 0.228 mg of malvidin‐3‐glucosides/g dry weight sample. Compared with their raw formulations, significant losses (60% to 70%) of the TA in the extruded products occurred due to extrusion cooking. Browning indices and color attributes such as brightness, chroma, and hue angle agreed with degradation of anthocyanins in the extruded products. However, extrusion cooking retained antioxidant capacities of the raw formulations in the extruded products either in their natural forms or degraded products with radical scavenging activity. This study demonstrated the potential for the production of puffed extruded food products with the improved antioxidant content from colored potatoes and pulse formulations.     

Electrical and thermal properties of PTFE-Sr<Subscript>2</Subscript>ZnSi<Subscript>2</Subscript>O<Subscript>7</Subscript> composites

A new polymer-ceramic composite was prepared using PTFE and low loss Sr₂ZnSi₂O₇. The dielectric properties of the composite were studied in the microwave and radiofrequency ranges. The relative permittivity (ε_r) and dielectric loss (tan δ) increased with the filler loading from 0.10 to 0.50 volume fractions (v_f). The observed values of ε_r, thermal conductivity and coefficient of thermal expansion (CTE) were compared with the corresponding theoretical predictions. The ability of the composite towards moisture absorption resistance was studied as a function of filler loading. It was also found that the variation of ε_r was less than 2% in the temperature range 25–90 °C, at 1 MHz. For a filler content of 0.50 v_f, the PTFE/Sr₂ZnSi₂O₇ composite exhibited ε_r = 4.4_, tan δ = 0.003 (at 4–6 GHz), CTE = 38.3 ppm/°C, thermal conductivity = 2.1 W/mK and moisture absorption = 0.09 wt%.     

Synthesis,structural analysis and microwave dielectric properties of LnTiSb<Subscript>x</Subscript>Nb<Subscript>1−x</Subscript>O<Subscript>6</Subscript> (Ln = Ce,Pr) ceramics

LnTiSb_xNb_1−xO₆ (Ln = Ce, Pr) ceramics were prepared by the conventional solid state ceramic route for x = 0, 0.05, 0.1, 0.15, 0.2 and 0.25. The structure of the materials was analyzed using X-ray diffraction techniques. The cell parameters and the theoretical densities of the samples were calculated using least square methods. The samples are sintered to more than 90% of the theoretical density at 1,325–1,350 °C. The microwave dielectric properties were measured using the cavity resonator method. The surface morphology of the sintered sample was analyzed using Scanning Electron Microscopy. All the materials have good microwave dielectric properties and are suitable for dielectric resonator applications.     

Development of a new solar thermal engine system for circulating water for aeration

This paper presents a numerical study about the performance of a Beta Stirling solar thermal engine system. This system is composed of a solar collector box connected to a regenerator hydraulic system and a transmitting power system. The objective of the system is to offer a new alternative to help solving stagnant water pollution in hot countries like Thailand by circulating water in canals, lakes, ponds etc. for aeration using solar energy.The purpose of this study is to determine the power output and actual heat transfer on the performance of the solar thermal engine. The solar thermal engine is analyzed using a mathematical model based on the first law of thermodynamics for processes with finite speed, with particular attention to the energy balance at the receiver. The result of calculations showed that the regenerator volume and phase angle must be chosen carefully to fulfill the requirement that total fluid mass in the system is constant and to obtain maximum power output throughout the day.     

Solar radiation estimation using artificial neural networks

Artificial Neural Network Methods are discussed for estimating solar radiation by first estimating the clearness index. Radial Basis Functions, RBF, and Multilayer Perceptron, MLP, models have been investigated using long-term data from eight stations in Oman. It is shown that both the RBF and MLP models performed well based on the root-mean-square error between the observed and estimated solar radiations. However, the RBF models are preferred since they require less computing power. The RBF model, obtained by training with data from the meteorological stations at Masirah, Salalah, Seeb, Sur, Fahud and Sohar, and testing with those from Buraimi and Marmul, was the best. This model can be used to estimate the solar radiation at any location in Oman.     

DNA-encoding to improve performance and allow parallel evaluation of the binding characteristics of multiple antibodies in a surface-bound immunoassay format

High affinity capture agents against protein targets are essential components for immunoassays, regardless of specific analysis format. Here, we describe the use of DNA-encoded antibodies for rapidly screening the kinetic and equilibrium binding properties of twelve commercial antibodies in a parallel analysis format using a multiplexed array of microring optical resonators. We show that DNA-encoding offers advantages in terms of antigen binding capacity, compared to covalently tethered antibodies; we also demonstrate that this linkage modality facilitates the rapid self-assembly of multiplexed arrays on account of complementarity between the DNA sequences on the antibodies and sensor array, respectively. Furthermore, DNA-encoded antibodies also allow for sensor array regeneration and reprogramming, as chaotropic agents can be used to disrupt the DNA-DNA duplexes that link the capture agents to the sensor without harming the underlying DNA on the surface, which can subsequently be reloaded with antibodies either targeting the same or different antigens.