Differences in reactivity of pulverised coal in air (O2/N2) and oxy-fuel (O2/CO2) conditions

The reactivity of four pulverised Australian coals were measured under simulated air (O₂/N₂) and oxy-fuel (O₂/CO₂) environments using a drop tube furnace (DTF) maintained at 1673 K and a thermogravimetric analyser (TGA) run under non-isothermal (heating) conditions at temperatures up to 1473 K. The oxygen concentration, covering a wide and practical range, was varied in mixtures of O₂/N₂ and O₂/CO₂ in the range of 3 to 21 vol.% and 5 to 30 vol.%, respectively. The apparent volatile yield measured in CO₂ in the DTF was greater than in N₂ for all the coals studied. Pyrolysis experiments in the TGA also revealed an additional mass loss in a CO₂ atmosphere, not observed in a N₂ atmosphere, at relatively high temperatures. The coal burnout measured in the DTF at several O₂ concentrations revealed significantly higher burnouts for two coals and similar burnouts for the other two coals in oxy-fuel conditions. TGA experiments with char also revealed higher reactivity at high temperatures and low O₂ concentration. The results are consistent with a char–CO₂ reaction during the volatile yield experiments, but additional experiments are necessary to resolve the mechanisms determining the differences in coal burnout.     

One-step growth of 3-5 nm diameter palladium electrocatalyst in a carbon nanoparticle-chitosan host and characterization for formic acid oxidation

The electrochemical formation of a palladium nanoparticle catalyst composite material has been investigated. A carbon nanoparticle-chitosan host film deposited onto a carbon substrate electrode has been employed to immobilize PdCl₂ as catalyst precursor. A one-step electrochemical reduction process gave Pd nanoparticles within the chitosan matrix with different levels of loading, on different carbon substrates, and with a reproducible catalyst particle diameter of ca. 3-5 nm. High activity for formic acid oxidation has been observed in aqueous phosphate buffer medium. The oxidation of formic acid has been investigated as a function of pH and maximum catalyst activity was observed at pH 6. When varying the formic acid concentration, limiting behaviour consistent with a “resistance effect” has been observed. A flow cell system based on a screen-printed carbon electrode has been employed to establish the effect of hydrodynamic conditions on the formic acid oxidation. Both increasing the convective-diffusion mass transport rate and increasing the concentration of formic acid caused the oxidation peak current to converge towards the same “resistance limit”. A mechanistic model to explain the resistance effect based on CO₂ flux and localized CO₂ gas bubble formation at the Pd nanoparticle modified carbon nanoparticle-chitosan host film has been proposed.     

A Liquid Density Standard Over Wide Ranges of Temperature and Pressure Based on Toluene

The density of liquid toluene has been measured over the temperature range −60 °C to 200 °C with pressures up to 35 MPa. A two-sinker hydrostatic-balance densimeter utilizing a magnetic suspension coupling provided an absolute determination of the density with low uncertainties. These data are the basis of NIST Standard Reference Material® 211d for liquid density over the temperature range −50 °C to 150 °C and pressure range 0.1 MPa to 30 MPa. A thorough uncertainty analysis is presented; this includes effects resulting from the experimental density determination, possible degradation of the sample due to time and exposure to high temperatures, dissolved air, uncertainties in the empirical density model, and the sample-to-sample variations in the SRM vials. Also considered is the effect of uncertainty in the temperature and pressure measurements. This SRM is intended for the calibration of industrial densimeters.     

Extraction of antioxidants from several berries pressing wastes using conventional and supercritical solvents

The solid waste generated in industrial berry juice production was considered as a low cost raw material for the extraction of natural antioxidants. Berries contain phenolic compounds with high antioxidant potential, including anthocyanins, proanthocyanidins, flavonols, catechins, benzoic and cinnamic acids. The solid residues generated from blueberry, cranberry and raspberry after pressing were extracted by conventional solvent extraction or by supercritical CO₂ (SC–CO₂) extraction. The effect of particle size and extraction time on the extraction yield, phenolic yield and phenolic content of the extracts produced by conventional solvents was assessed. Supercritical CO₂ extraction was performed during 2 h operating in the range 80–300 bar at 60 °C using 2.5 L CO₂/h. Maximum solubles yield of 5.20% were extracted from raspberry wastes at 200 bar, 3.89% from cranberry wastes at 250 bar and 1.4% from blueberry wastes at 200 bar. The highest phenolic content of the extracts was observed for blueberry pomace in the trap, with 9 grams of gallic acid equivalents per 100 g of extract. The ABTS (2, 2′-azino-bis-[3-ethylbenzotiazol-6-sulfonic acid]) and DPPH (α,α-diphenyl-β-picrylhydrazyl) radical scavenging capacity of the SC–CO₂ extracts was moderate in comparison with the activity of conventional solvent extracts.     

Analysis of perchlorate in human urine using ion chromatography and electrospray tandem mass spectrometry

Because of health concerns surrounding widespread exposure to perchlorate, we developed a sensitive and selective method for quantifying perchlorate in human urine using ion chromatography coupled with electrospray ionization tandem mass spectrometry. Perchlorate was quantified using a stable isotope-labeled internal standard ((18)O(4)-perchlorate) with excellent assay precision (coefficient of variation <5% for repetitively analyzed quality control material). Analytical accuracy was established by blind analysis of certified proficiency testing materials prepared in synthetic urine matrix; calculated amounts deviated minimally from true amounts, with percent differences ranging from 2% to 5%. Selective chromatography and tandem mass spectrometry reduced the need for sample cleanup, resulting in a rugged and rapid method capable of routinely analyzing 75 samples/day. The lowest reportable level (0.025 ng/mL) was sufficiently sensitive to detect perchlorate in all human urine samples evaluated to date, with a linear response range from 0.025 to 100 ng/mL. This selective, sensitive, and rapid method will help elucidate any potential associations between human exposure to low levels of perchlorate and adverse health effects.     

Mapping invasive Phragmites australis in the coastal Great Lakes with ALOS PALSAR satellite imagery for decision support

The invasive variety of Phragmites australis (common reed) forms dense stands that can cause negative impacts on coastal Great Lakes wetlands including habitat degradation and reduced biological diversity. Early treatment is key to controlling Phragmites, therefore a map of the current distribution is needed. ALOS PALSAR imagery was used to produce the first basin-wide distribution map showing the extent of large, dense invasive Phragmites-dominated habitats in wetlands and other coastal ecosystems along the U.S. shore of the Great Lakes. PALSAR is a satellite imaging radar sensor that is sensitive to differences in plant biomass and inundation patterns, allowing for the detection and delineation of these tall (up to 5 m), high density, high biomass invasive Phragmites stands. Classification was based on multi-season ALOS PALSAR L-band (23 cm wavelength) HH and HV polarization data. Seasonal (spring, summer, and fall) datasets were used to improve discrimination of Phragmites by taking advantage of phenological changes in vegetation and inundation patterns over the seasons. Extensive field collections of training and randomly selected validation data were conducted in 2010–2011 to aid in mapping and for accuracy assessments. Overall basin-wide map accuracy was 87%, with 86% producer's accuracy and 43% user's accuracy for invasive Phragmites. The invasive Phragmites maps are being used to identify major environmental drivers of this invader's distribution, to assess areas vulnerable to new invasion, and to provide information to regional stakeholders through a decision support tool.     

Disinfection of Bacillus subtilis spores with chlorine dioxide: a bench-scale and pilot-scale study

Chlorine dioxide (ClO2) inactivation of Bacillus subtilis ATCC 19659 spores was examined at pilot-scale during periods representative of winter and summer temperature extremes at the Britannia Water Treatment Plant in Ottawa, Canada. In addition, bench-scale experiments using the same source water (Ottawa River, Ontario, Canada), as well as buffered and unbuffered laboratory waters were conducted using B. subtilis spores. Bench-scale inactivation of B. subtilis spores by ClO2 was similar to reported values for Cryptosporidium parvum (both organisms being more resistant to ClO2 than Giardia lamblia), suggesting the possibility that these spores may be used as potential indicators for protozoan parasites. Additionally, spore inactivation was observed to be influenced by pH in laboratory (distilled deionised water) water but not in Ottawa River water. At pilot-scale, spore inactivation was influenced by water temperature: a ClO2 dose of 2.5 mg/L resulted in a spore inactivation of approximately 2.0 log10 and 0.5 log10 at water temperatures of 23.2d egrees C and 5.2 degrees C, respectively. Chlorite concentrations remained below both the US EPA maximum contaminant level of 1.0 mg/L and the maximum contaminant level goal of 0.8 mg/L for up to 2.0log10 B. subtilis inactivation.     

Optimization of Supercritical Carbon Dioxide Extraction of Bioactive Flavonoid Compounds from Spearmint (<Emphasis Type="Italic">Mentha spicata</Emphasis> L.) Leaves by Using Response Surface Methodology

The bioactive flavonoid compounds of spearmint (Mentha spicata L.) leaves were obtained by using supercritical carbon dioxide (SC-CO₂) extraction. Extraction was carried out according to face-centred central composite design, and independent variables were pressure (100, 200 and 300 bar), temperature (40, 50 and 60 °C) and co-solvent amount (3, 6 and 9 g/min). The extraction process was optimized by using response surface methodology for the highest crude extraction yield of bioactive flavonoid compounds. The optimal conditions were identified as 209.39 bar pressure, 50.00 °C temperature and 7.39 g/min co-solvent amount. The obtained extract under optimum SC-CO₂ condition was analysed by high-performance liquid chromatography. Seven bioactive flavonoids including catechin, epicatechin, rutin, luteolin, myricetin, apigenin and naringenin were identified as major compounds. The results of quantification showed that spearmint leaves are potential source of antioxidant compounds.