The 2003/2004 Libby,Montana PM2.5 Source Apportionment Research Study

Except for areas in California, Libby, Montana is the only designated EPA nonattainment area for fine particulate matter (PM _2.5 ) in the mid and western states. During the winter of 2003/2004, PM _2.5 speciated data (mass, elements, ions, organic/elemental carbon) were collected every six days from November 11, 2003 through February 27, 2004. Using a Chemical Mass Balance computer model (Version 8.0), these data were used to apportion the sources of PM _2.5 in the Libby valley. In support of the source apportionment program, a comprehensive evaluation of the particulate matter associated organic compounds (including polar organics, phenolics, polycyclic aromatic hydrocarbons, and ¹⁴ C) present in the airshed was also conducted.

CMB modeling results revealed that emissions from residential wood combustion was the major source of PM _2.5 throughout the winter months in Libby, contributing an average of 82% of the measured PM _2.5 . Levoglucosan, a well-known chemical marker for wood smoke, had the highest measured concentrations of any of the 95 polar organic compounds quantified from the fine fraction, accounting for over 15.5% of the measured organic carbon fraction. Other semi-volatile organic compounds with high measured concentrations during the program were four phenolic compounds commonly found in wood smoke, including phenol, 2-methylphenol ( o -cresol), 4-methylphenol ( p -cresol), and 2,4-dimethylphenol. Results from ¹⁴ C analysis indicate that as much as 82% of the measured ¹⁴ C results from a wood smoke source. These indicators support modeling results that residential wood combustion was the major source of PM _2.5 in Libby, Montana throughout the winter months.     

Analysis of Aerosolized Particulates of Feedyards Located in the Southern High Plains of Texas

The objective of this study was to quantify, size, and examine the composition of particulates found in ambient aerosolized dust of four large feedyards in the Southern High Plains. Ambient air samples (concentration of dust) were collected upwind (background) and downwind of the feedyards. Aerosolized particulate samples were collected using high volume sequential reference ambient air samplers, PM ₁₀ and PM _2.5 , laser strategic aerosol monitors, cyclone air samplers, and biological cascade impactors. Weather parameters were monitored at each feedyard. The overall (main effects and estimable interactions) statistical (P < 0.0001) general linear model statement (GLM) for PM ₁₀ data showed more concentration of dust (μg/m ³ of air) downwind than upwind and more concentration of dust in the summer than in the winter. PM _2.5 concentrations of dust were comparable for 3 of 4 feedyards upwind and downwind, and PM _2.5 concentrations of dust were lower in the winter than in the summer. GLM (P < 0.0001) data for cascade impactor (all aerobic bacteria, Enterococcus spp, and fungi) mean respirable and non-respirable colony forming units (CFU) were 676 ± 74 CFU/m ³ , and 880 ± 119 CFU/m ³ , respectively. The PM ₁₀ geometric mean size (±GSD) of particles were analyzed in aerosols of the feedyards (range 1.782 ± 1.7 μm to 2.02 ± 1.74μm) and PM _2.5 geometric mean size particles were determined (range 0.66 ± 1.76 μm to 0.71 ± 1.71 μm). Three of 4 feedyards were non-compliant for the Environmental Protection Agency (EPA) concentration standard (150 μg/m ³ /24 h) for PM ₁₀ particles. This may be significant because excess dust may have a negative impact on respiratory disease.     

Mass Absorption Cross-Section of Ambient Black Carbon Aerosol in Relation to Chemical Age

Three differing techniques were used to measure ambient black carbon (BC) aerosols in downtown Toronto through 20 December 2006 to 23 January 2007. These techniques were thermal analysis, as performed by a Sunset Labs OCEC Analyzer (OCEC); light attenuation, as performed by an Aethalometer (AE); and photoacoustic analysis, as performed by a Photoacoustic Instrument (PA). These measurements of ambient PM _2.5 were used to investigate the effects of coating thickness on BC Mass Absorption Cross-section (MAC). MAC values were determined by comparing 880 nm and 370 nm AE measurements and PA measurements of b _abs (absorption coefficient, Mm^–1) to the OCEC measurements. Based on mass size distributions and supporting criteria, the PM _2.5 was classified as fresh, semi-aged, or aged. The average MAC values in these categories, based on the PA measurements, were 9.3 ± 1.8, 9.9 ± 2.0, and 9.3 ± 2.2 m ² /g (mean ± standard deviation), respectively, suggesting that any difference in coating thickness as a result of aging, on the time scale observed, did not produce a difference in MAC. In a second type of experiment, a thermodenuder was installed upstream of the AE, PA, and OCEC and samples were heated to 340°C in order to evaporate volatile and semi-volatile components within the coating. Based on the PA measurements, the average MAC values of these heated samples, for the fresh, semi-aged, and aged categories were 7.7 ± 2.2, 6.9 ± 2.2, and 9.1 ± 2.0 m ² /g, respectively. Similar differences in MAC were also observed by the AE. The decrease in MAC in the fresh and semi-aged samples was interpreted in terms of the degree of coating of the PM _2.5 . Results agreed well with predictions made by absorption amplification theory and had ramifications for calibration of filter-base attenuation and photoacoustic instruments.     

Development and characterization of an oro-nasal inhalation plethysmography mask exposure system

An oro-nasal inhalation plethysmography mask exposure system (ONIPMES) was developed to challenge nonhuman primates and rabbits with biological agents while determining real-time respiratory parameters. The system included novel challenge plethysmography and sample collection masks that delivered aerosol directly to the breathing zone of the animals and to the sample collection probes. Challenge plethysmography masks were fitted with a differential pressure transducer that interfaced with a signal amplifier and computer software to quantify respiratory tidal volume, frequency, and minute volume. Challenge plethysmography masks were calibrated and verified with certified registered gas-tight syringes. Accuracy was determined from simultaneous comparison tests between the challenge plethysmography mask and head-out plethysmographs using live animals. For cynomolgus macaques, the mean differences in tidal volume, frequency, and minute volume were 4.20 ± 0.872 mL, 3.50 ± 3.15 breaths per minute (bpm), and 99.3 ± 91.7 mL/min. For New Zealand white rabbits, the mean differences in tidal volume, frequency, and minute volume were 1.13 ± 0.551 mL, 1.07 ± 0.404 bpm, and 209.3 ± 97.37 mL/min. Standardized tests were used to characterize the inhalation exposure system. The fractional leak rate was 4.17 × 10^?5 min^?1. The theoretical T₉₉ was 1.694 min and the observed T₉₉ was 0.588 min. Mask to mask spatial variation was 0.9%. The particle size distribution (PSD), mass median aerodynamic diameter (MMAD), and geometric standard deviation (GSD) of a 25 mg/mL saline solution was 1.2 ± 0.01 µm and 1.9 ± 0.20. The ONIPMES minimizes dermal and ocular contamination and multiple species may be used.     

The interaction of hydrogen sulfide with lead- and barium–cadmium–zinc-stabilized poly(vinyl chloride)

Poly(vinyl chloride) polymers stabilized with tribasic lead sulfate discolor upon exposure to hydrogen sulfide gas as a result of lead sulfide formation. The discoloration occurs for samples in both cord and sheet forms and is shown to be a function of total H₂S exposure, reaching a limiting value that is determined by the amount of lead stabilizer used in the polymer formulation. The permeation and diffusion constants for H₂S through PVC stabilized with tribasic lead sulfate and with a liquid Ba–Cd–Zn formulation are found to be P_Pb = (6.0 ± 0.2) × 10^?9, P_BaCdZn = (5.2 ± 0.2) × 10^?9 (both in cm³ gas?cm film/cm² area?sec?cm Hg), D_Pb = (1.3 ± 0.2) × 10^?7 cm²/sec, and D_BaCdZn = (6.4 ± 0.6) × 10^?8 cm²/sec, all measured at 21°C. The stabilizing efficiencies of the formulations were assessed by HCl evolution measurements, which show that exposure to H₂S decreases the initial polymer stability for both Pb-stabilized and Ba–Ca–Zn-stabilized formulations. Protection of stabilized PVC formulations from diffusing hydrogen sulfide is thus advisable for long-term stability as well as for color integrity.     

Synthesis of Extraction Resin Containing N,N,N′,N′-Tetraisobutyl Diglycolamide and its Application for Separation of Sr(II) from Rb(I)

Abstract

A novel Levextrel resin containing N,N,N′,N′-tetraisobutyl diglycolamide (TiBDGA) was synthesized by suspension polymerization of styrene and divinylbenzene and its performance for separation of Sr(II) from Rb(I) was investigated. The effects of crosslink degree, stirring speed, and the ratio of porogenic-agents on the resin synthesized were examined. The optimum TiBDGA resin with 40 wt.% divinylbenzene as cross linking agent and 20 wt.% of n-octanol as porogenic-agents provided excellent adsorption capacity of 22.5 mg/g. The distribution coefficient (K _d) of Sr(II) in HNO₃ media onto the resin depended heavily on the acidity in the aqueous solution. The maximum K _d for Sr(II) (7300 mL/g) was observed when the HNO₃ concentration in aqueous phase reached 2 mol/L. The difference in the Sr(II) and Rb(I) distribution coefficients of several orders of magnitude implied that ⁸⁹Sr may be separated from ⁸⁶Rb with a radionuclide purity greater than 99%. And the maximum static adsorption capacity of Sr(II) on the resin was 22.5 mg/g.     

Influence of Sr2+ on Calcium‐Deficient Hydroxyapatite Formation Kinetics and Morphology in Partially Amorphized α‐TCP

Hydration of partially amorphized α‐TCP powders with Sr²⁺ concentrations ranging from 0 to 10 mol% substitution for Ca²⁺ was analyzed by isothermal calorimetry and quantitative in‐situ XRD. Hydration of both crystalline α‐TCP and amorphous TCP (ATCP) forming CDHA was retarded to an increasing extent with increasing Sr²⁺ content. Sr²⁺ slightly reduced the crystallite size (XRD coherent scattering domains) of the CDHA formed during hydration, while the size of crystals visible under SEM was not noticeably affected. Reaction enthalpies of ΔH_{R(Sr‐α‐TCP→Sr‐CDHA)} = 122 ± 8 J/g_TCP and ΔH_{R(Sr‐ATCP→Sr‐CDHA)} = 257 ± 8 J/g_TCP were determined for the hydration of crystalline α‐TCP and ATCP containing 5 mol% Sr²⁺ substitution for Ca²⁺. This is comparable with the corresponding reaction enthalpies previously obtained for undoped samples, which are 106 ± 7 J/g_TCP for α‐TCP and 250 ± 7 J/g_TCP for ATCP.     

Size-Resolved Anhydrosugar Composition in Smoke Aerosol from Controlled Field Burning of Rice Straw

A field study was conducted to determine the effects of ambient conditions and burning practices of rice fields in Taiwan on the chemical and physical characteristics of the smoke aerosol. Rice straw was burned on an actual rice field under typical conditions and smoke particles were collected immediately downwind of the field over the full particle size spectrum. Here we present size distributions of levoglucosan, a common molecular tracer for biomass burning, as well as detailed concentration patterns of three anhydrosugars, including mannosan, and galactosan, in addition to smoke aerosol concentrations of inorganic ions and carbonaceous species. The generated smoke aerosol was characterized by a high OC/EC ratio (10) and a large fraction of potassium (K⁺) and chloride (Cl^?) ions at a Cl^?/K⁺ ratio of 2. Levoglucosan showed a distinct bimodal distribution in the smoke particles with a large fraction (up to 56%) of the total levoglucosan mass observed in very large particles (PM _{> 10} ). The prevailing ambient conditions (such as relatively high humidity), atmospheric processes (e.g., particle coagulation, hygroscopic growth, and deposition), the specific burning practices of rice fields in Taiwan (slow burning of straw spread in thin layers on the ground), as well as the inherent properties of rice straw likely influenced the particle size characteristics of the smoke tracer. Moreover, the relative abundance of the three biomass burning tracers showed a unique pattern (in good agreement with previous chamber burn measurements): levoglucosan-to-mannosan ratios were distinctly higher (with an average value of 27) than those observed for other types of biomass, such as softwood, hard wood, peat, or leaves, in previous studies. Such chemical fingerprint may be used in source apportionment studies for the assessment of contributions from the combustion of specific types of biomass.     

Generation and Characterization of Hardwood Smoke Inhalation Exposure Atmospheres

An inhalation exposure system and operating protocol were developed that resulted in consistent achievement of targeted exposure concentrations of hardwood smoke without compromising the desire to include multiple phases of a burn cycle. A conventional, noncatalyzed stove was operated in a temperature-controlled room with a three-phase (kindling, high burn, and low burn) cycle. Equally sized wood of similar moisture content was loaded in a consistent fashion each day of the study. A stable and controllable dilution system was employed that involved simultaneous withdrawal of smoke from a primary dilution tunnel. Exposure operators utilized real-time measurements of particulate matter (PM), CO, and stove temperature, along with operational experience, to gauge when adjustments to dilution air or the firebox were necessary. Dilutions of smoke were controlled in four separate inhalation atmospheres with daily average particle mass concentrations of 30, 100, 300, and 1000 μg/m³. Each of these atmospheres was characterized in detail, including gas, semivolatile, and particle phases. Gas phase hydrocarbons were composed mostly of carbonyls (especially furans) and acids (especially low molecular weight aliphatic acids). Several classes of gas-phase semivolatile organics were measured, with the highest proportions of material in classes of polycyclic aromatic hydrocarbons and methoxy phenols. The particle phase was primarily organic carbon (> 90%) with small amounts of ions, elements, and black carbon. Approximately 15% of the organic carbon was identified and quantified, with the largest contribution of material from sugars and sugar derivatives.     

The external mass transfer of basic and acidic dyes on wood

The parameters affecting the initial adsorption rates of Astrazone Blue dye (Basic Blue 69) on to wood have been studied. A simple model has been proposed to determine the external mass transfer coefficients and these have been compared with values obtained using a more complex procedure. The external mass transfer coefficient, β, has been shown to vary linearly with agitation and initial dye concentration using log-log coordinates; furthermore β is independent of particle size. The effect of temperature has been studied and the activation energy for the process is 44 ± 2 kJ mol^?1. Similar correlations were obtained for the adsorption of Telon Blue dye (Acid Blue 25) on wood. Using log-log correlations, the external mass transfer coefficient was found to vary with (rev min^?1)^0.14, C₀^?0.27; and a small dependence on particle size was also observed. The activation energy for the external mass transfer process was 25 ± 2 kJ mol^?1.     

An In Situ Method for Sizing Insoluble Residues in Precipitation and Other Aqueous Samples

Particles are frequently incorporated into clouds or precipitation, influencing climate by acting as cloud condensation or ice nuclei, taking up coatings during cloud processing, and removing species through wet deposition. Many of these particles, particularly ice nuclei, can remain suspended within cloud droplets/crystals as insoluble residues. While previous studies have measured the soluble or bulk mass of species within clouds and precipitation, no studies to date have determined the number concentration and size distribution of insoluble residues in precipitation or cloud water using in situ methods. Herein, for the first time we demonstrate that nanoparticle tracking analysis (NTA) is a powerful in situ method for determining the total number concentration, number size distribution, and surface area distribution of insoluble residues in precipitation, both of rain and melted snow. The method uses 500 μL or less of liquid sample and does not require sample modification. Number concentrations for the insoluble residues in aqueous precipitation samples ranged from 2.0–3.0 (±0.3)?×?10⁸ particles cm^?3, while surface area ranged from 1.8 (±0.7)–3.2 (±1.0) × 10⁷ μm² cm^?3. Number size distributions peaked between 133 and 150 nm, with both single and multi-modal character, while surface area distributions peaked between 173 and 270 nm. Comparison with electron microscopy of particles up to 10 μm show that, by number, >97% residues are <1 μm in diameter, the upper limit of the NTA. The range of concentration and distribution properties indicates that insoluble residue properties vary with ambient aerosol concentrations, cloud microphysics, and meteorological dynamics. NTA has great potential for studying the role that insoluble residues play in critical atmospheric processes.

Copyright 2015 American Association for Aerosol Research     

COMPARISON OF ION EXCHANGE AND DONNAN EQUILIBRIUM MODELS FOR THE PH-DEPENDENT ADSORPTION OF SODIUM AND CALCIUM IONS ONTO KRAFT WOOD PULP FIBERS

ABSTRACT

Management of nonprocess element (NPE) accumulation in pulp washing operations requires equilibrium models that predict the distribution of metals between the wash liquor and the pulp fibers. The overall goal of this study was to assess models for predicting the multi-component adsorption of hydrogen ions (H⁺), sodium ions (Na⁺), and calcium ions (Ca⁺²) onto bleached and unbleached kraft pulp fibers over a pH range of 2.7–11. As part of this study, binary equilibrium constants for hydrogen and metal ion exchange on carboxylate sites in bleached pulp (0.041 meq/g dry pulp) were measured at 25°C, with log K ^Na/Ca = ?1.604 ± 0.119, log K ^H/Ca = 0.633 ± 0.087, and intrinsic dissociation constant pK _io of 3.64 ± 0.46. Ion exchange and Donnan equilibrium models adequately predicted the multi-component equilibrium data for competitive adsorption of H⁺, Na⁺, and Ca⁺² onto bleached kraft wood pulp fibers. The ion exchange model was fully predictive, whereas the Donnan model required that the solution pH be known. At pH 2.7–6, the Donnan model predicted the adsorption of Na⁺ and Ca⁺² onto both bleached and unbleached wood pulp fibers better than the ion exchange model. The ion exchange model assumed that residual carboxylate in the pulp served as the only site for the competitive binding of hydrogen and metal ions. In contrast, the Donnan model assumed a non site-specific distribution of metal ions between charged fiber and external solution phases and a carboxylate site specific adsorption of hydrogen ions. Above pH 6, both models failed to predict that the calcium adsorption on unbleached brownstock pulp increased beyond the carboxylate site capacity, suggesting that other functional groups within the brownstock pulp with intrinsic dissociation constant values higher than carboxylate were providing additional binding sites for calcium.     

A case study of the effect of Ni substitution on the sintering behaviours of Ba0.5Sr0.5Co0.8Fe0.2O3−δ oxygen transport membranes

ABSTRACT

The sintering behaviours of undoped and 8 mol% B-site Ni-doped Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ (BSCF) under various conditions are systematically investigated. Ni doping increases the lattice parameter of BSCF. The grain size of the undoped BSCF increases from 1.52 to 64.8 μm with increasing sintering temperature from 900 at 1150 °C, while the grain size of the Ni-doped counterpart increases from 3.06 to 34.1 μm as the sintering temperature increases from 1000 to 1200 °C. The grain growth kinetics is analysed using the expression Dⁿ = tK ₀exp(-Q/RT). The grain growth exponent n is found to be 3 for the undoped BSCF and 4.7 for the Ni-doped BSCF. The grain growth activation energy (Q) is 650.7±30 kJ/mol for the undoped BSCF and 803.4±37 kJ/mol for the Ni-doped BSCF. This indicates that the Ni dopant has a negative influence on the densification and grain growth of BSCF.     

Quantification of Bacillus subtilis and Bacillus sp. Adhesion on Fez Medina Cedar Wood

The adhesion of Bacillus subtilis and Bacillus sp. isolated from Fez cedar wood decay has been investigated. Furthermore, the physicochemical proprieties including hydrophobicity and electron donor/electron acceptor (Lewis acid–base) of both bacteria and substrata were evaluated using contact angle measurements. The results show that Bacillus subtilis has a hydrophobic character (ΔG _iwi = –20 mJ/m²). In contrast, Bacillus sp. exhibits a hydrophilic (ΔG _iwi = –20 mJ/m²), electron donating (γ^–) and weakly electron accepting (γ⁺) character. With respect to the substrata surface, we found that the cedar wood used in this work, was hydrophobic in character, having relatively more electron-donor that electron-acceptor properties (γ^– = 6 ± 4 mJ/m²; γ⁺ = 0 ± 3 mJ/m²). The phenomena of adhesion were observed by environmental scanning electron microscopy (ESEM) and cell adhesion was quantified using a Matlab program. The analysis of images obtained by ESEM show that the both cells was able to adhere to the wood substrata and the quantitative adhesion results showed that the surface coverage by Bacillus sp. (90%) was higher than that by the Bacillus subtilis strain (40%).     

Effect of smoke,charred wood,and nitrogenous compounds on seed germination of ten species from woodland in central-western Spain

The effect of smoke, charred wood, and nitrogenous compounds on germination was tested on 10 species of the Cistaceae, Poaceae, Fabaceae, and Asteraceae, from fire-prone, shrubby woodlands in central-western Spain. Dry seeds were exposed to smoke, by watering with distilled water–charred wood suspensions, or NaNO₂, KNO₃, NH₄Cl, and NH₄NO₃. Smoke enhanced germination in 9 of 10 of the species. In species of Poaceae, germination was stimulated by 20 min of smoke exposure. In Asteraceae and Fabaceae species, 10 min of smoke exposure was the most effective treatment for enhancing germination. Three species—Cistus ladanifer, Cistus crispus, and Cistus monspeliensis—had a positive response to 20 min of smoke exposure; germination of Cistus salviifolius L. was also enhanced after 10 min. The effect of charred wood was variable, with no consistent germination pattern within the families. Trifolium angustifolium and Retama sphaerocarpa showed no stimulation of germination under most of the charred wood concentrations. Similarly, germination of Senecio jacobea under the charred wood treatment did not surpass that of the control. NaNO₂ promoted seed germination in Dactylis glomerata (10 mM), Cistus ladanifer (1, 10, and 25 mM), and Cistus crispus (1 and 10 mM). KNO₃ enhanced germination in Dactylis glomerata (1 and 25 mM), Dittrichia viscosa (10 and 25 mM), C. ladanifer (1, 10, and 25 mM), Cistus crispus (1 and 25 mM), and C. salviifolius aud C. monspeliensis (25 mM). NH₄Cl induced germination of Dactylis glomerata and Dittrichia viscosa (1 mM), and Cistus species germinated best in 25 mM of this salt. NH4NO3 induced germination only in Cistus species. Holcus lanatus had the highest level of germination regardless of treatment.     

Contribution of Selected Dicarboxylic and ω-Oxocarboxylic Acids in Ambient Aerosol to the m/z 44 Signal of an Aerodyne Aerosol Mass Spectrometer

The Aerodyne aerosol mass spectrometer (AMS) employs flash vaporization (600°C) followed by 70-eV electron impact ionization (EI) to detect organic and inorganic aerosols. The signal at mass-to-charge ratio (m/z) 44 (mainly CO ₂ ⁺ ) is considered the most reliable marker of oxygenated organic aerosol. This study is the first to evaluate the contribution of selected low molecular weight dicarboxylic acids (diacids) and ω-oxocarboxylic acids (ω-oxoacids) to the particle-phase m/z 44 signal of the AMS mass spectrum. Ambient measurements were conducted at a surface site in Tokyo (35°39 ′ N, 139°40 ′ E) during August 3–8, 2003. Diacids and ω-oxoacids were measured using a filter sampling followed by extraction, derivation, and gas chromatograph-flame ionization detector (GC-FID) analysis. The mass concentrations of diacids and ω-oxoacids show tight correlation with the m/z 44 signal (r ² = 0.85–0.94) during the measurement period. Laboratory experiments were also performed to determine the fragment patterns of selected diacids (C₂–C₆ diacids and phthalic acids) and ω-oxoacid (glyoxylic acid) in ambient aerosols. Here, we report for the first time that the selected organic acids could account for 14 ± 5% of the observed m/z 44 signal on average during the measurement period. Oxalic acid (C₂) is the largest contributor, accounting for 10 ± 4% of the observed m/z 44 signal. These results would be useful for interpreting the m/z 44 signals obtained from ambient measurements in various locations.     

Sintering Rates for Pristine and Doped Titanium Dioxide Determined Using a Tandem Differential Mobility Analyzer System

Sintering rates of pristine and V-doped TiO ₂ were obtained using a tandem DMA system. A range of experiments were conducted to first map out the variation of mobility size of a monodisperse (by mobility) agglomerate with time at three fixed temperatures. Using relationships of the surface area to the mobility size, the sintering equation was solved to determine the activation energy and pre-exponential factor. The value of the activation energy was 236 (± 46) kJ/mol for pristine TiO ₂ and 363 (± 1) kJ/mol for V-doped TiO ₂ . The corresponding pre-exponential factors were 7.22 × 10 ¹⁹ and 2.22 × 10 ¹² s/m ⁴ K, respectively. These values were then used to predict changes in mobility diameter at different temperatures, and good agreement was obtained with measurements. Possible reasons for faster sintering rates of V-TiO ₂ relative to pristine TiO ₂ were conjectured.     

Correlation of 13C‐NMR analysis with fungal decay tests of polymeric structural wood constituents. I. Basidiomycetes

Heat treatment at relatively high temperatures (from 150 to 260°C) is an effective method to improve the durability of wood. This study investigates the reasons for the decay resistance of heat‐treated and nontreated wood with respect to the polymeric structural constituents by solid‐state cross‐polarization/magic‐angle spinning (CP–MAS) ¹³C‐NMR analysis before and after exposure to brown rot and white rot fungi. An industrial two‐stage heat‐treatment method under relatively mild conditions (<200°C) has been used to treat the samples. Brown rot fungi attack polymeric carbohydrates of nontreated Scots pine sapwood at C4, resulting in cleavage and eventually depolymerization of cellulose and hemicelluloses. The attack at the carbohydrate C6, which has never been observed before, is remarkable because the C6 ? CH₂OH group has no covalent structural function but acts in fixing the three‐dimensional carbohydrate configuration just by secondary forces. The ? CH₂OH group carries ? OH, which forms some of the strongest hydrogen bonds in the structure of the crystalline native cellulose. It is suggested that the fungus tries to cleave this group to open the cellulose crystalline structure into an amorphous structure to decrease its water repellency to facilitate enzymatic cellulose degradation. Considerable degradation of the hemicelluloses occurs during brown rot fungal exposure, whereas in general the attack on lignin is rather limited, being mainly demethoxylation. However, Gloeophyllum trabeum is an active brown rot fungus in the (partial) degradation of lignin because there is some indication of ring opening of the aromatic ring of lignin during fungal exposure. Aromatic ring opening has also been observed after exposure to Coriolus versicolor, a white rot fungus. The demethoxylation of lignin and some attack on wood carbohydrates are also characteristic of the attack of this white rot fungus. The CP–MAS ¹³C‐NMR spectra of heat‐treated Norway spruce reveal similarities but also clear differences after fungal exposure in comparison with nontreated Scots pine sapwood. Brown rot fungi seem to have a preference to attack the carbohydrates of heat‐treated wood at C4 and especially C1, cleaving the skeleton of cellulose and glucomannans. In untreated Scots pine sapwood, this attack mainly occurs at C4, the nonreducing end of the glucose unit. An attack on the out‐of‐the‐ring alcoholic group ? CH₂OH of the carbohydrates of heat‐treated Norway spruce is less obvious than that in untreated Scots pine. The attack on C3/C5 of the carbohydrates is remarkable, indicating ring opening of the glucose units, which has not been observed in nontreated Scots pine sapwood. Lignin degradation is limited to demethoxylation, and low or no aromatic ring opening is observed, even after C. versicolor exposure. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2639–2649, 2006     

Inkjet Aerosol Generator as Monodisperse Particle Number Standard

The AIST-inkjet aerosol generator (IAG) can generate highly monodisperse solid or liquid aerosol particles in the particle diameter range from 0.3 to 20 μm at precisely known particle generation rates. The device has been developed for evaluating the counting efficiencies of optical and condensation particle counters. Particle generation efficiency of the IAG is defined as the number of aerosol particles generated by one voltage pulse sent to an inkjet head. The 95% confidence interval of the efficiency were 0.998 ± 0.006 within the 0.4 to 10 μm particle diameter range. The efficiencies remained close to unity when the droplet generation rates were within 20–500 s^?1 and 100–900 s^?1 using ultrapure-water and isopropyl alcohol (IPA) as the solvent of the inkjet solution, respectively. The operating aerosol flowrate range of the IAG is currently 0.5 and 1.0 L/min. The coefficients of variations (C.V.) of the size distributions were 2 to 3% indicating the generated particles were highly monodisperse. The generated particle sizes were defined as the volume equivalent diameter, D_ve. The uncertainty analysis on the factors affecting D_ve indicated that 95% confidence interval of the D_ve is expected to be ±5%. The uncertainty of D_ve was entirely caused by the uncertainty of the average mass of a droplet. The reproducibility of particle sizes within 0.5 to 10 μm was evaluated using an aerodynamic particle sizer. The C.V. of the measured particle sizes were less than 6% and 4% when NaCl particles and ionic liquid droplets were generated, respectively.

Copyright 2014 American Association for Aerosol Research