Sol-Gel Particulate Float Process to Make Vitreous Silica Bodies

Particulate sol-gel technology uses larger particles than that of alkoxide-derived gels and provides larger pore sizes in the gelled object. This allows relatively rapid drying and fabrication of large rods or tubular shapes. However, the formation of more complex or flat shapes, which require extensive surface contact with a mold, is more difficult. The shrinkage during drying, with the significantly greater stress of surface friction due to adhesion, frequently leads to cracking.We have demonstrated a solution to this problem by floating the gel on the surface of a dense liquid. Dry silica panels up to 28 × 40 × 0.7 cm³ were prepared in this way. The use of patterning molds allowed the fabrication of more sophisticated shapes. These bodies were sintered to transparent vitreous silica articles of near net dimensions.     

工业污染排放中气──固两相流的光学测量

烟尘及各种工业性粉尘排放是典型的气-固两相系．迄今为止，国内外尚缺少有效的监测其排放的手段．本文基于光的散时原理，提出了一种非接触的光学方法，能对上述固体颗粒物的污染排放浓度及粒径大小进行实时、在线的监测。计算机模拟和实验研究表明，该方法具有广阔的工业应用前景。     

Hydride generation atomic fluorescence spectrometric determination of As, Bi, Sb, Se(IV) and Te(IV) in aqua regia extracts from atmospheric particulate matter using multivariate optimization

A highly sensitive and simple method, based on hydride generation and atomic fluorescence detection, has been developed for the determination of As, Bi, Sb, Se(IV) and Te(IV) in aqua regia extracts from atmospheric particulate matter samples. Atmospheric particulates matter was collected on glass fiber filters using a medium volume sampler (PM1 particulate matter). Two-level factorial designs have been used to optimise the hydride generation atomic fluorescence spectrometry (HG-AFS) procedure. The effects of several parameters affecting the hydride generation efficiency (hydrochloric acid, sodium tetrahydroborate and potassium iodide concentrations and flow rates) have been evaluated using a Plackett-Burman experimental design. In addition, parameters affecting the hydride measurement (delay, analysis and memory times) have been also investigated. The significant parameters obtained (sodium tetrahydroborate concentration, sodium tetrahydroborate flow rate and analysis time for As; hydrochloric acid concentration and sodium tetrahydroborate flow rate for Se(IV); and sodium tetrahydroborate concentration and sodium tetrahydroborate flow rate for Te(IV)) have been optimized by using 2ⁿ + star central composite design. Hydrochloric acid concentration and sodium tetrahydroborate flow rate were the significant parameters obtained for Sb and Bi determination, respectively. Using a univariate approach these parameters were optimized. The accuracy of methods have been verified by using several certified reference materials: SRM 1648 (urban particulate matter) and SRM 1649a (urban dust). Detection limits in the range of 6 × 10⁻³ to 0.2 ng m⁻³ have been achieved. The developed methods were applied to several atmospheric particulate matter samples corresponding to A Coruña city (NW Spain).     

Analysis of nitro-PAHs in diesel exhaust particulate extracts with multicolumn HPLC

Summary A method is described for the determination of nitrated polynuclear aromatic hydrocarbons (nitro-PAHs), in particular 1-nitropyrene, in diesel particulate extracts. The method employs a multidimensional HPLC (column switching) technique with final on-line peak identification by UV-VIS spectral comparison with standards. To achieve exceptional chromatographic selectivity for nitro-PAHs, a new pyrene butyric acid amide phase has been prepared which is capable of forming donor-acceptor complexes with them. With this technique it is possible to confirm the presence of 1-nitropyrene in the range 3–100 ng/mg on filter-collected diesel soot. Its utility was demonstrated with diesel exhaust extracts spiked with varying levels of 1-nitropyrene and proved to be highly selective.Parts of this work have been presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984.Dedicated to Prof. J. F. K. Huber at the occasion of his 60th birthday.     

SOOT combustion. co and k catalysts supported on different supports

The catalytic combustion of particulate material was studied on cobalt catalysts promoted with potassium using different supports for its preparation. Silica, aluminium oxides and hydroxides, zirconium oxide and hydroxide were used as supports. The catalytic activity for combustion depends on the type of support used, the higher activity corresponding to the supported catalyst on zirconium oxide. TPR studies indicate that the interaction metal/support allows to explain the higher activity of the CoK/SiO₂ catalyst with respect to the CoK/Al₂O₃ but the high activity found in CoK/ZrO₂is not explained by this interaction. In all cases the Co and K improved the performance of the catalysts.     

Identification of oxygenated polycyclic aromatic hydrocarbons in diesel particulate matter by capillary gas chromatography and capillary gas chromatography/mass spectrometry

Summary Using a two-step liquid chromatographic separation on normalphase cartridges, crude extracts of diesel particulate matter can be separated without time-consuming sample handling into special fractions which mainly contain slightly-polar oxygenated polycyclic aromatic hydrocarbons (oxy-PAH) and nitrated polycyclic aromatic hydrocarbons (nitro-PAH). Subsequent analysis was by fused-silica capillary gas chromatography on a SE54 column along with flame-ionisation (GC/FID) and positive-ion electron-impact mass spectrometric detection (GC/MS) respectively. A number of individual oxy-PAH belonging to four different chemical classes (ketones, quinones, anhydrides and aldehydes) and several individual nitro-PAH were characterized by their retention times and mass spectra. Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984     

Capillary electrophoresis determinative and GC-MS confirmatory method for water-soluble organic acids in airborne particulate matter and vehicle emission

Urban fine airborne particulate matter (PM2.5) and vehicle emission samples were studied for water-soluble low-molecular-weight carboxylic acids using CE with indirect UV detection. Further identification of these acids was achieved using GC-MS as their butyl esters (after derivatization with BF3/butanol). Several dicarboxylic acids in the range C2-C10 including straight-chain, branched-chain, cis- and trans-unsaturated, and aromatic acids were confirmed by GC-MS. In addition, aromatic acids such as benzoate, phthalate, terephthalate, isophthalate, and 4-methylphtalate were present in such samples, but some of these were not well resolved by the used CE method. Oxocarboxylic acids (Cn(w) with n > 4) were also identified by GC-MS but not determined by CE due to lack of standards. The rapidity and simplicity of the CE method were clearly demonstrated, and the method was observed to be advantageous for routine monitoring of water-soluble organic acids in airborne PM2.5 and vehicle emission at low microg/L levels.     

Performance characteristics of suspended particulate reagent-iminodiacetate as a binding agent for diffusive gradients in thin films

The performance characteristics of an alternative binding agent, suspended particulate reagent-iminodiacetate (SPR-IDA), for use with DGT methodology were investigated. The parameters investigated during this study included gel hydration, blank levels, elution factor (f_e), capacity, the effects of pH on the binding of trace metals by DGT. The novel application of this resin for use as a quantitative standard for laser ablation ICP-MS was also evaluated. To further constrain the results for the SPR-IDA binding agent, parallel experiments were performed using resin gel containing Chelex 100, which has been widely reported in the literature. Hydration results showed that the SPR-IDA resin gel reached a stable dimension and weight within ∼30 min and was dimensionally stable for ≤6 months. The measured DGT blanks for the SPR-IDA resin were 0.0023, 0.15, 0.21, 0.0033 and 0.011 ng disc⁻¹ for Co, Ni, Cu, Cd and Pb, respectively. The elution factor differed for the two resin types with the Chelex 100 recoveries slightly lower than previous reports and the SPR-IDA resin showing on average ∼5-9% better recoveries than DGT containing Chelex 100. The measured capacity of DGT discs containing the SPR-IDA binding agent was 0.26 mg Cd, similar to the calculated value of 0.29 mg Cd, indicating the entire resin layer was available for metal uptake.Both resin types performed equally well when deployed in 1 mM NaNO₃ solutions with DGT measurements of ∼100% of direct solution measurements for Co, Ni and Cd. However, DGT measurements of Cu and Pb systematically decreased with increasing solution pH down to ∼50% of solution values at pH 8.0, due to artifacts resulting from colloid formation during the addition of the metals. This was remedied by adding the metals as dilute salt standards and addition of Mg(NO₃)₂ to eliminate adsorption to the container walls. In the latter experiments, DGT measured concentrations of Co, Ni, Cu, Cd and Pb were in agreement with solution concentrations. Deployment of DGT in solutions with increasing concentrations of trace metals yielded linear results, suggesting that quantitative analysis using simplified laser ablation techniques should be possible using this newly characterized SPR-IDA resin gel.     

Methodology for Bioassay-Directed Fractionation Studies of Air Particulate Material and Other Complex Environmental Matrices

Abstract

A normal phase HPLC methodology using a semi-preparative polyaminocyano column in conjunction with a selection of short-term genotoxicity assays has been developed for bioassay-directed fractionation studies of complex environmental mixtures. To illustrate the effectiveness of this methodology, an organic extract prepared from respirable air particulate samples collected in Hamilton, Canada was separated into a non-polar aromatic fraction and a polar aromatic fraction using a combination of alumina and Sephadex LH20 chromatography. These fractions were evaluated for their genotoxic potential using the Salmonella/microsome (Ames) assay with six different strains of Salmonella.

The non-polar aromatic fraction was analyzed by normal phase HPLC and the eluent was collected in one-minute subfractions; these subtractions were bioassayed in three different Salmonella strains (YG1021 -S9, YG1024 -S9 and YG1029 +S9) to afford three different mutation profiles of this sample. Some subfractions which exhibited high mutagenic responses were subjected to further chemical analyses using GC/MS in order to identify those compounds responsible for the genotoxic responses. The nitroarene compounds 2-nitrofluoranthene, 1-nitropyrene and 2-nitropyrene and higher molecular weight polycyclic aromatic hydrocarbons such as benzo[a]pyrene and indeno[l,2,3-cd]pyrene were identified and quantified in some of the biologically active subfractions. The normal phase gradient conditions afforded very reproducible retention times for a series of polycyclic aromatic standards with a broad range of compound polarities. In addition, polycyclic aromatic hydrocarbons (PAH) were observed to elute from the normal phase HPLC column in a series of peaks; successive peaks contained PAH of increasing molecular weight while any individual peak was shown to contain PAH of the same molecular weight.     

Real‐Time Measurement of the Size Distribution of Diesel Exhaust Particles using a Portable 4‐stage Electrical Low Pressure Impactor

For this study, a 4 stage electrical low pressure impactor was designed to measure the real‐time size distribution of diesel particulate matter (DPM). For the performance evaluation, sodium chloride (NaCl) particles and dioctyl sebacate (DOS) particles were used. After evaluating the collection efficiency of each stage of the impactor, the size distributions of test particles were estimated using electrical current data and their inversion algorithm, and this was found to agree with the results obtained by a scanning mobility particle sizer (SMPS). For measurement of DPM, a common‐rail direct injection (CRDI) diesel engine, for engine speeds of 1,200 rpm and 1,500 rpm at 2.7 kgf·m, was used. Therefore, it was found that the size distribution of the DPM could be easily obtained, with the currents measured by the impactor and the data inversion algorithm, in less than 5 seconds. Furthermore, the effective density of the DPM could be obtained using the calculated results and the SMPS data.