A Murine Oral‐Exposure Model for Nano‐ and Micro‐Particulates: Demonstrating Human Relevance with Food‐Grade Titanium Dioxide

Human exposure to persistent, nonbiological nanoparticles and microparticles via the oral route is continuous and large scale (10¹²–10¹³ particles per day per adult in Europe). Whether this matters or not is unknown but confirmed health risks with airborne particle exposure warns against complacency. Murine models of oral exposure will help to identify risk but, to date, lack validation or relevance to humans. This work addresses that gap. It reports i) on a murine diet, modified with differing concentrations of the common dietary particle, food grade titanium dioxide (fgTiO₂), an additive of polydisperse form that contains micro‐ and nano‐particles, ii) that these diets deliver particles to basal cells of intestinal lymphoid follicles, exactly as is reported as a “normal occurrence” in humans, iii) that confocal reflectance microscopy is the method of analytical choice to determine this, and iv) that food intake, weight gain, and Peyer's patch immune cell profiles, up to 18 weeks of feeding, do not differ between fgTiO₂‐fed groups or controls. These findings afford a human‐relevant and validated oral dosing protocol for fgTiO₂ risk assessment as well as provide a generalized platform for application to oral exposure studies with nano‐ and micro‐particles.     

Analytical Modeling of Quantum Mechanical Tunneling in Germanium Nano-MOSFETS

A simple analytical model has been developed to study quantum mechanical effects (QME)in a germanium substrate MOSFET (metal oxide semiconductor field effect transistor),which includes gate oxide tunneling considering the energy quantization effects in the substrate.Some alternate high dielectric constant materials to reduce the tunneling have also been studied.By comparing with the numerically reported results,the results match well with the existing reported work.     

Microstructure and mechanical properties of mechanically alloyed and spark plasma sintered amorphous–nanocrystalline Al65Cu20Ti15 intermetallic matrix composite reinforced with TiO2 nanoparticles

Multiphase Al₆₅Cu₂₀Ti₁₅ intermetallic alloy matrix composite, dispersed with 10 wt.% of TiO₂ nanoparticles, has been processed by mechanical alloying, followed by spark plasma sintering under pressure in the temperature range of 623–873 K. Differential scanning calorimetry and X-ray diffraction suggest that equilibrium crystalline phases evolve from the amorphous or intermediate crystalline phases. Transmission electron microscopy shows that the composite sintered at 873 K has partially amorphous microstructure, with dispersion of equilibrium, crystalline, intermetallic precipitates of Al₅CuTi₂, Al₃Ti, and Al₂Cu of 25–50 nm size, besides the TiO₂. The composite sintered at 873 K exhibits little porosity, hardness of 5.6 GPa, indentation fracture toughness in the range of 3.1–4.2 MPa√m, and compressive strength of 1.1 GPa. Indentation crack deflection by TiO₂ particle aggregates causes increase in fracture resistance with crack length, and suggests R-curve type behaviour. The study provides guidelines for processing high strength amorphous–nanocrystalline intermetallic composites based on the Al–Cu–Ti ternary system.     

Reactions of coals of different ranks with CO---H2 mixtures with and without sodium aluminate

Well-characterized coals of different H/C atomic ratio and rank were reacted at 365°C with CO, H₂ and CO---H₂ mixtures in water in the presence and absence of sodium aluminate. The optimum H₂/CO ratio for conversion was found to vary with the type of coal. It was <1 : 1 for low-rank and subbituminous coals, whereas the conversion of bituminous coals either did not vary with H₂/CO ratio or reached a maximum at a higher H₂/CO ratio (2 : 1). Even for a bituminous coal there was no advantage in reducing the water/coal ratio below 2 : 1 in NaAlO₂-catalysed reactions. The conversions increased with increasing H/C atomic ratio of the coal and decreasing rank, with or without NaAlO₂. Asphaltene yields increased with increasing coal rank and increasing proportion of CO in the H₂---CO reacting gases. The mechanistic implications of these results are briefly discussed.     

A simplified model of nitric oxide emission from a circulating fluidized bed combustor

A simplified mathematical model leading to a closed form of solution is developed for estimation of nitric oxide emission from a coal fired circulating fluidized bed (CFB) furnace. The furnace is divided into two sections: a lower section below and an upper section above the secondary air injection level. Reactions in the cyclone and the return leg are neglected. Furnace dimensions, coal feed rate, coal composition and furnace temperature are inputs to the model which was validated against several pilot scale and commercial units. Experimental results from two pilot plants and two commercial power plants agree with model predictions. A sensitivity analysis was carried out using the model to examine the effect of different operating parameters and coal properties on the overall NO emission from the furnace. It was found that excess air and furnace temperature are most important factors influencing the NO emission level. The primary to secondary air ratio influences the NO emission level reasonably. Properties of coal are other factors which affect the NO emission to a large extent. The model, though it invovles some simplification, predicts the overall emission of NO with a level of accuracy accepted in commercial operation.     

Effect of alloy grain size and silicon content on the oxidation of austenitic Fe-Cr-Ni-Mn-Si alloys in pure O2

Austenitic Fe-18Cr-20Ni-1.5Mn alloys containing 0, 0.6, and 1.5 wt.% Si were produced both by conventional and rapid solidification processing. The isothermal and cyclic oxidation resistance of the alloys were studied at 900°C in pure O₂ to elucidate the role of alloy microstructure and Si content on oxidation properties. The conventionally-processed, large-grained alloy that contained no silicon formed Fe-rich nodules during oxidation. The nodule formation was effectively eliminated by either reducing the alloy grain size by rapid solidification or by adding Si to the alloy. The lowest weight gains were achieved when a continuous silica layer formed between the alloy and the external chromia scale. The formation of the continuous silica layer required a ombination of fine alloy grain size and high Si content. The presence of S in the alloy was found to be detrimental to oxide scale adherence when the silica layer was continuous.     

Pressure dependencies of copper oxidation for low- and high-temperature parabolic laws

Studies of the oxidation kinetics of copper have been conducted in the thin-film range at temperatures of 383–398 K and in the oxygen pressure range of 0.278–21.27 kPa; whereas in the thick-film regime at 1123 K, studies have been conducted in the oxygen pressure range of 2.53–21.27 kPa. Furthermore, the effect of continuously impressed direct current with oxygen pressure variation in Wagner's parabolic range has been studied also in order to have a better understanding of the effective charge on the migrating species. In the low-temperature range, the rate constant, k_P ∝ \(P_{O_2 }^{1/4} \) , suggesting that the migration of neutral vacancies in the growing film predominates. At high temperature, 1123 K, in the Wagnerian regime, the observed approximate pressure dependencies of the parabolic rate constants are the following: $$\begin{gathered} {\text{k}}_{\text{p}} (normal oxidation) \propto \sim {\text{P}}_{{\text{O}}_{\text{2}} }^{{\text{1/7}}} \hfill \\ {\text{k}}_{\text{p}} (sample cathodic) \propto \sim {\text{P}}_{{\text{O}}_{\text{2}} }^{{\text{1/5}}} \hfill \\ \end{gathered} $$ and $${\text{k}}_{\text{p}} (sample anodic) \propto \sim {\text{P}}_{{\text{O}}_{\text{2}} }^{{\text{1/10}}} $$ .     

Oxidation behavior of copper at high temperatures under two different modes of direct-current applications

Oxidation kinetics of copper in the temperature range of 973–1173 K atP _{O 2}=21.27 kPa exhibit enhancement and deceleration in the rates with changing polarity compared to normal oxidation under interrupted mode of directcurrent application. These conditions are achieved by connecting the oxidizing copper covered with an initially formed thin oxide film to the positive and negative terminal of a dc source, respectively. However, the influence of direction of the current is found to be opposite under uninterrupted mode of impressed current flow in the same temperature range. The effect of short-circuiting the metal to the outer oxide/air interface on the reaction kinetics is also reported. The rate of oxide-scale growth under normal condition, and two different modes of current applications as well as with shorting circuitry attachment conform to the parabolic growth law. The results pertaining to the two different modes of impressed current have been discussed considering both the phenomena of electrolysis of the oxide electrolyte and the polarization at the two phase boundaries. The enhancement and the reduction in rates under uninterrupted impressed current conditions are explained on the basis of increased and decreased average defect concentrations, respectively, within the oxide layer. The acceleration and deceleration in the rates under interrupted mode of current flow have been explained in the light of sustenance of a steeper and flatter electrochemical-potential gradient of defects, respectively, across the growing-oxide layer. The possible different responses of the metal/oxide and oxide/air interfaces to the impressed current brought into play by two different modes of current application, have enabled to display a better insight on the mechanistic aspects of scale growth under the influence of an externally applied current.     

Phosphorous limitation in an arctic river biofilm—A whole ecosystem experiment

A fourth-order arctic river was experimentally enriched with phosphate (7.7 ± 7.0 μ g 1⁻¹) to determine the effect of such a loading (equivalent to a community of 10,000 people) upon the trophically important biofilm. The effect upon a light-grown biofilm (an autotrophic/heterotrophic assemblage) and a dark-grown biofilm (predominantly heterotrophic assemblage) was determined after 28 days of colonization. Seven attributes of the biofilms were monitored, 2 autotrophic indices, chlorophyll , [¹⁴C]HCO₃ incorporation into lipids and 5 heterotrophic indices; [¹⁴C]acetate incorporation into lipids, metabolic heat output, turn-over times of microbially labile glucose and glutamate and mineralization of microbially recalcitrant ring-labelled [¹⁴C]hydroxybenzoic acid. The findings showed that the addition of phosphorus resulted in a substantial stimulation of both autotrophic and heterotrophic processes suggesting that arctic rivers of this type would be liable to cultural eutrophication.     

Hydrochemistry and mercury cycling in a High Arctic watershed

Mass budgets for total mercury, major ions and nutrients were calculated for Amituk Lake, located on Cornwallis Island, Nunavut, Canada. Total mercury in two distinct snowpacks averaged 1.25 and 4.21 ng L(-1); the discharge-weighted concentration of influent streams averaged 0.76 ng L(-1). The recent and pre-industrial Hg(T) fluxes in atmospheric deposition to the catchment were estimated to be 0.57 and 0.23 microg m(-2) but through retention within the catchment and/or re-volatilization from the melting snowpack, these decreased by 69% in the lake inflow. The spring freshet was the prime conduit for transporting Hg(T) into Amituk Lake. Because of limited mixing of surface runoff with the lake water column during snowmelt, 59% of the Hg(T) input was directly discharged through the outflow, 16% entered the lake water column where concentrations increased from 0.23 to 0.33 ng L(-1) from June to August and 25% was deposited to the bottom sediments producing a sediment Hg(T) flux of 3.1 microg m(-2).