Smoke gas analysis by Fourier transform infrared spectroscopy – summary of the SAFIR project results

The determination of toxic components from fire gases is difficult because the environment is hot, reactions are often temperature dependent, and a lot of soot may be produced. Due to the different properties of the gas components, a different time‐consuming procedure for each species has traditionally been used. The use of FTIR (Fourier transform infrared) spectrometers as a continuous monitoring technique overcomes many of the problems in smoke gas analyses. FTIR offers an opportunity to set up a calibration and prediction method for each gas showing a characteristic spectral band in the infrared region of the spectrum. The objective of the SAFIR project was to further develop the FTIR gas analysis of smoke gases to be an applicable and reliable method for the determination of toxic components in combustion gases related to fire test conditions. The optimum probe design, filter parameters and the most suitable sampling lines in terms of flow rate, diameter, construction material and operating temperature have been specified. In the large scale, special concern was given to the probe design and the effects of the probe location as well as practical considerations of the sampling line length. Quantitative calibration and prediction methods have been constructed for different components present in smoke gases. Recommendations on how to deal with interferents, non‐linearities and outliers have been provided and a verification method for the spectrometer for unexpected variations and for the different models have been described. FTIR measurement procedures in different fire test scenarios have been studied using the recommendations of this project for measurement techniques and analysis and an interlaboratory trial of the FTIR technique in smoke gas analysis was carried out to define the repeatability and reproducibility of the method in connection with a small scale fire test method, the cone calorimeter. Copyright © 2000 John Wiley & Sons Ltd.     

Electrical conductivity modeling of carbon black/polycarbonate,carbon nanotube/polycarbonate,and exfoliated graphite nanoplatelet/polycarbonate composites

Adding conductive carbon fillers to electrically insulating thermoplastic polymers increases the resulting composite's electrical conductivity, which would enable them to be used in electrostatic dissipative and semiconductive applications. In this study, varying amounts of carbon black (CB: 2 to 10 wt %), multiwalled carbon nanotubes (CNT: 0.5 to 8 wt %), or exfoliated graphite nanoplatelets (GNP: 2 to 15 wt %) were added to polycarbonate (PC) and the resulting composites were tested for electrical conductivity (EC = 1/electrical resistivity). The percolation threshold was ～ 1.2 vol % CNT, ～ 2.4 vol % CB, and ～ 4.6 vol % GNP. In addition, three EC models (Mamunya, additive, and general effective media) were developed for the CB/PC, CNT/PC, and GNP/PC composites. The general effective media (GEM) model showed the best agreement with the experimental results over the entire range of filler concentrations (above and below the percolation threshold) for all three composite systems. In addition, the GEM model can be easily adapted for composites containing combinations of different conductive fillers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Chirality of synergistic sex pheromone components of the western hemlock looperLambdina fiscellaria lugubrosa (HULST) (Lepidoptera: Geometridae)

Bakers' yeast reduction of (2E)-3-(2-furanyl)-2-methyl-2-propenal yielded the synthetic intermediate, (2S)-3-(2-furanyl)-2-methylpropanol, of high chiral purity (>97% ee) for the synthesis of the enantiomers of 2,5-dimethylheptadecane and 7-methylheptadecane, two synergistic sex pheromone components of the western hemlock looper (WHL),Lambdina fiscellaria lugubrosa Hulst. In electrophysiological bioassays, (7S)- but not (7R)-7-methylheptadecane elicited strong antennal responses by male WHL antennae. In field trapping experiments, addition of (7S)- but not (7R)-7-methylheptadecane to (5R,11S)-5,11-dimethylheptadecane, the major sex pheromone component of WHL, increased attraction. Attraction to (5R,11S)-5,11-dimethylheptadecane in combination with (7S)-7-methyiheptadecane was further enhanced by the addition of (5S)- but not (5R)-2,5-dimethylheptadecane. Similarly, attraction to (5R,11S)-5,11-dimethylheptadecane combined with (5S)-2,5-dimethylheptadecane increased when 7S- but not (7R)-7-methylheptadecane was added as a third component. We conclude that (7S)-7-methylheptadecane and (5S)-2,5-dimethylheptadecane are the synergistic sex pheromone components of WHL. The synthetic methodology described is applicable to the synthesis of chiral methyl-branched pheromones in other orders of the Insecta, particularly Coleoptera, Diptera and Orthoptera.     

Circumpolar study of perfluoroalkyl contaminants in polar bears (Ursus maritimus)

Perfluoroalkyl substances were determined in liver tissues and blood of polar bears (Ursus maritimus) from five locations in the North American Arctic and two locations in the European Arctic. Concentrations of perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate, heptadecafluorooctane sulfonamide, and perfluoroalkyl carboxylates with C(8)-C(15) perfluorinated carbon chains were determined using liquid chromatography tandem mass spectrometry. PFOS concentrations were significantly correlated with age at four of seven sampling locations, while gender was not correlated to concentration for any compound measured. Populations in South Hudson Bay (2000-2730 ng/g wet wt), East Greenland (911-2140 ng/g wet wt), and Svalbard (756-1290 ng/g wet wt) had significantly (P < 0.05) higher PFOS concentrations than western populations such as the Chukchi Sea (435-729 ng/g wet wt). Concentrations of perfluorocarboxylic acids (PFCAs) with adjacent chain lengths (i.e., C9:C10 and C10:C11) were significantly correlated (P < 0.05), suggesting PFCAs have a common source within a location, but there were differences in proportions of PFCAs between eastern and western location sources. Concentrations of PFOS in liver tissue at five locations were correlated with concentrations of four polychlorinated biphenyl congeners (180, 153, 138, and 99) in adipose tissue of bears in the same populations, suggesting similar transport pathways and source regions of PFOS or precursors.     

The labile pool of manganese in soil: Comparison of E and L value measurements with extraction methods

The size of the manganese labile pools of three sandy soils from south east Scotland with a history of Mn deficiency was investigated by four methods: extraction with CaCl₂; extraction with DTPA; E-value determination by exchange with ⁵⁴Mn; and L-value determination using barley as the test crop. There was little agreement between the methods. The L-values varied with the period of plant growth and with soil bulk density but greatly exceeded the E-values, which in turn were about twice the quantities obtained by prolonged extraction with CaCl₂ and an order of magnitude greater than the quantities extracted after 1 h with CaCl₂-DTPA extraction gave values three to six times those obtained with CaCl₂. Extractable Mn increased dramatically after prolonged air drying, indicating the need for standardisation of both pre-extraction conditions and extraction times when comparing the Mn availability of different soils.     

Chemical and structural characterisation of almond oil bodies and bovine milk fat globules

Lipids in almonds are present as oil bodies in the nut. These oil bodies are surrounded by a membrane of proteins and phospholipids and are a delivery vehicle of energy in the form of triglycerides, similarly to the more studied bovine milk fat globule membrane. Chemical, physical and microscopic analyses revealed major differences in the composition and structure of almond oil bodies and bovine milk fat globules. The lipids of both natural emulsions differed in degree of unsaturation, chain length, and class. The almond oil body membrane does not contain any cholesterol or sphingomyelin unlike the bovine milk fat globule membrane. Therefore, the phospholipid distribution at the surface of the oil bodies did not present any liquid-ordered domains. The membranes, a monolayer around almond oil bodies and a trilayer around bovine fat globules, may affect the stability of the lipid droplets in a food matrix and the way the lipids are digested.     

(Z,Z)-4,7-tridecadien-(S)-2-yl acetate: sex pheromone of Douglas-fir cone gall midge,Contarinia oregonensis

Our objectives were to identify and field test the sex pheromone of female Douglas-fir cone gall midge, Contarinia oregonensis (Diptera: Cecidomyiidae). Coupled gas chromatographic–electroantennographic detection (GC-EAD) analyses of pheromone extract revealed a single compound (A) that elicited responses from male antennae. Hydrogenation of pheromone extract, followed by renewed GC-EAD analysis, revealed a new EAD-active compound with chromatographic characteristics identical to those of tridecan-2-yl acetate on five fused silica columns (DB-5, DB-210, DB-23, SP-1000, and Cyclodex-B). Syntheses, chromatography, and retention index calculations of all possible tridecen-2-yl acetates suggested that the candidate pheromone A was a tridecadien-2-yl acetate with nonconjugated double bonds. Synthetic candidate pheromone component (Z,Z)-4,7-tridecadien-2-yl acetate (Z4Z7) cochromatographed with A on all analytical columns and elicited comparable antennal activity. In GC-EAD analyses that separated the enantiomers (Z,Z)-4,7-tridecadien-(S)-2-yl acetate (2S-Z4Z7) and (Z,Z)-4,7-tridecadien-(R)-2-yl acetate (2R-Z4Z7) with baseline resolution, only 2S-Z4Z7 as a component in a racemic standard or in pheromone extract elicited antennal responses. In Douglas-fir seed orchards, sticky traps baited with 2S-Z4Z7 captured male C. oregonensis, whereas 2R-Z4Z7 was behaviorally benign. Comparable catches of males in traps baited with racemic Z4Z7 (50 g) or virgin female C. oregonensis suggested that synthetic pheromone baits could be developed for monitoring C. oregonensis populations in commercial Douglas-fir seed orchards.     

Grain Boundary Responses to Heterogeneous Deformation in Tantalum Polycrystals

The evolution of heterogeneous deformation in a tantalum polycrystal was examined during a three-point bending experiment using electron backscatter pattern mapping. Slip bands formed at strains as low as 1%, and they became more intense with strain. Heterogeneous deformation was evident as intragranular orientation gradients as large as 30° were observed after a strain of about 8%. Nonmonotonic changes in the local average misorientation distribution were observed, implying that dislocation substructure developed in a complex manner. Slip bands were analyzed using plane traces computed from local orientation information. With the assumption of uniaxial stress, Schmid factors for favorable slip systems were identified for each grain and compared with observations, showing evidence for macroscopic activity on both {110} and {112} slip systems. Reconstructed boundary data were used to estimate the geometric potential for slip transfer at grain boundaries. The correlations indicated that when active slip systems were favorably oriented for slip transfer across the boundary, it was often observed in the form of continuous slip bands aligned across the boundary. In boundaries where geometrical alignment and Schmid factors were not favorable for slip transfer, there was a higher likelihood to form ledges (topographic discontinuities) along the grain boundaries. Dislocation pileups at grain boundaries were also correlated with a low potential for slip transfer.