Abatement of sulfur hexafluoride emissions from the semiconductor manufacturing process by atmospheric-pressure plasmas

Sulfur hexafluoride (SF6) is an important gas for plasma etching processes in the semiconductor industry. SF6 intensely absorbs infrared radiation and, consequently, aggravates global warming. This study investigates SF6 abatement by nonthermal plasma technologies under atmospheric pressure. Two kinds of nonthermal plasma processes--dielectric barrier discharge (DBD) and combined plasma catalysis (CPC)--were employed and evaluated. Experimental results indicated that as much as 91% of SF6 was removed with DBDs at 20 kV of applied voltage and 150 Hz of discharge frequency for the gas stream containing 300 ppm SF6, 12% oxygen (O2), and 40% argon (Ar), with nitrogen (N2) as the carrier gas. Four additives, including Ar, O2, ethylene (C2H4), and H2O(g), are effective in enhancing SF6 abatement in the range of conditions studied. DBD achieves a higher SF6 removal efficiency than does CPC at the same operation condition. But CPC achieves a higher electrical energy utilization compared with DBD. However, poisoning of catalysts by sulfur (S)-containing species needs further investigation. SF6 is mainly converted to SOF2, SO2F4, sulfur dioxide (SO2), oxygen difluoride (OF2), and fluoride (F2). They do not cause global warming and can be captured by either wet scrubbing or adsorption. This study indicates that DBD and CPC are feasible control technologies for reducing SF6 emissions.     

Pattern recognition of the movement tracks of medaka (Oryzias latipes) in response to sub-lethal treatments of an insecticide by using artificial neural networks

Specimens of medaka (Oryzias latipes) were observed continuously through an automatic image recognition system before and after treatments of an anti-cholinesterase insecticide, diazinon (0.1 mg/l), for 4 days in semi-natural conditions (2 days before treatment and 2 days after treatment). The "smooth" pattern was typically shown as a normal movement behavior, while the "shaking" pattern was frequently observed after treatments of diazinon. These smooth and shaking patterns were selected for training with an artificial neural network. Parameters characterizing the movement tracks, such as speed, degree of backward movements, stop duration, turning rate, meander, and maximum distance movements in the y-axis of 1-min duration, were given as input (six nodes) to a multi-layer perceptron with the back propagation algorithm. Binary information for the smooth and shaking patterns was separately given as the matching output (one node), while eight nodes were assigned to a single hidden layer. As new input data were given to the trained network, it was possible to recognize the smooth and shaking patterns of the new input data. Average recognition rates of the smooth pattern decreased significantly while those for the shaking pattern increased to a higher degree after treatments of diazinon. The trained network was able to reveal the difference in the shaking pattern in different light phases before treatments of diazinon. This study demonstrated that artificial neural networks could be useful for detecting the presence of toxic chemicals in the environment by serving as in-situ behavioral monitoring tools.     

Colloid migration in symmetrical non-uniform fractures: particle tracking in three dimensions

A three-dimensional model for the migration of colloids in a saturated fracture is presented, which considers the motion of colloids as a result of advection and diffusion, as well as colloid-surface interactions at the fracture walls. This model is successfully incorporated into a three-dimensional particle tracking algorithm that tracks particles within a continuum and allows consideration of the migration of colloids in symmetrical, three-dimensional, non-uniform fractures. The framework is general enough to incorporate non-local interactions that provide colloid motion relative to the fluid. The algorithm is verified against classical Taylor dispersion, and its generalization to a sorbing phase, in a uniform fracture and shows excellent agreement with theory. A simple, non-uniform fracture that has an analytically tractable velocity field is also considered, and both quantitative and qualitative comparisons are made with the uniform fracture case. The modelling of more complex fracture geometries is also discussed and a particular case is implemented within the particle tracking framework.     

Hygroscopic organic aerosols during BRAVO?

The hygroscopic properties of the organic fraction of aerosols are poorly understood. The ability of organic aerosols to absorb water as a function of relative humidity (RH) was examined using data collected during the 1999 Big Bend Regional Aerosol and Visibility Observational Study (BRAVO). (On average, organics accounted for 22% of fine particulate matter with an aerodynamic diameter less than 2.5 microm (PM2.5) mass). Hourly RH exceeded 80% only 3.5% of the time and averaged 44%. BRAVO aerosol chemical composition and dry particle size distributions were used to estimate PM2.5 light scattering (Bsp) at low and high ambient RH. Liquid water growth associated with inorganic species was sufficient to account for measured Bsp for RH between 70 and 95%.     

Analysis of nitrated polynuclear aromatic hydrocarbons

A derivatization-gas chromatography/electron capture detector (GC/ECD) method has been developed for the measurement of trace nitrated polynuclear aromatic hydrocarbons (NPAHs) in air. The method involves first the derivatization of parent nitro-PAHs to their corresponding fluorinated derivatives, followed by GC/ECD analysis. The sensitivity of the method is an order of magnitude higher than those of direct GC/ECD analysis of NPAHs themselves. The method is simple and robust and thus ideally suited for the routine monitoring of NPAHs in air samples. The sensitivity and reproducibility of GC/negative ion chemical ionization MS (NICIMS) for the measurement of NPAHs after derivatization has been evaluated. The method has sensitivity comparable to GC/ECD, but is less reproducible in quantification. The method is therefore suitable for method validation and NPAHs peak confirmation rather than routine operations.     

A qualitative UV spectroscopic method as an initial guide to source origins of polycyclic aromatic hydrocarbons

A qualitative method is described, using ultraviolet spectroscopy, to determine the source origins of polycyclic aromatic hydrocarbons present in the environment. The technique takes advantage of the fact that aromatic compounds exhibit strong absorption in the ultraviolet region. It offers a fast and convenient alternative to other methods, which normally require extensive sample clean-up to avoid or limit interference from other materials during analysis. In contrast, this method requires only basic column chromatography to isolate the compounds of interest. Examples of the application of the technique are presented; the results are corroborated by those previously obtained by other methods.     

Microbial removal of uranium in uranium-bearing black shale

The effects of several conditional factors on efficiency of U bioleaching using an iron-oxidizer, Acidithiobacillus ferrooxidans, from U-bearing black shale (349 mg kg-1 of U) were investigated. When batch-type reactors containing black shale were initially inoculated with the cells, lower pH, higher redox potential and higher amount of aqueous Fe3+ than those of non-inoculated reactor were observed until 200 h. Such development of condition, which was facilitated by microbial activity, can enhance the rate and extent of U leaching from the solid substrate. However, under the condition of enough nutrients and energy source (Fe2+) supplied, indigenous Fe-oxidizers in the non-inoculated black shale were activated over time. They exerted almost same influence on the leaching efficiency with the inoculated samples after 250 h. Low initial Fe2+ supply (5 g l-1) and no addition of inorganic nutrients resulted in nearly identical extent of U leaching with that of 9 g l-1 of initial Fe2+ and nutrients supply. The results indicate that, in a practical process of bioleaching, the expenses for Fe2+ and nutrients addition can be reduced.     

Removal of ammonia by biofilters: a study with flow-modified system and kinetics

The characteristics of ammonia removal by two types of biofilter (a standard biofilter with vertical gas flow and a modified biofilter with horizontal gas flow) were investigated. A mixture of organic materials such as compost, bark, and peat was used as the biofilter media based on the small-scale column test for media selection. Complete removal capacity, defined as the maximum inlet load of ammonia that was completely removed, was obtained. The modified biofilter showed complete removal up to 1.0 g N/kg dry material/day. However, the removal capacity of the standard biofilter started to deviate from complete removal around 0.4 g N/kg dry material/day, indicating that the modified biofilter system has higher removal efficiency than the standard upflow one. In kinetic analysis of the biological removal of ammonia in each biofilter system, the maximum removal rate, Vm, was 0.93 g N/kg dry material/day and the saturation constant, Ks, was 32.55 ppm in the standard biofilter. On the other hand, the values of Vm and Ks were 1.66 g N/kg dry material/day and 74.25 ppm, respectively, in the modified biofilter system.     

Effect of photosensitizer diethylamine on the photodegradation of polychlorinated biphenyls

The objective of this study was to investigate the effect of diethylamine and xenon simulated sunlight on the photodegradation of two forms of PCBs including PCBs in transformer oil and PCB congener 138. The result of GC chromatograms illustrated the shifting pattern of higher chlorinated biphenyls in transformer oil degraded to lower chlorinated biphenyls with the extension of exposure time. The effect of diethylamine and xenon simulated sunlight was significant on the photodegradation of both PCBs in transformer oil and congener 138. The initial degradation rates of congener 138 (1.14 x 10(-9) to 4.47 x 10(-9) mol l(-1) h(-1)) were in direct proportion to the initial concentrations of congener 138 which confirmed the pseudo-first-order reaction of PCB photodegradation. The apparent quantum yields (phi) of congener 138 using diethylamine in xenon photoreactor were ranged between 2.08 x 10(-2) and 9.8 x 10(-4). PCB congeners 123, 97, 70, 67, 33, 29, 17, 12, and 9 were detected as the descendants of the photodegradation of congener 138 through dechlorination. The major pathway of congener 138 photodegradation in this study was via para-dechlorination.     

Factors affecting EDTA extraction of lead from lead-contaminated soils

The effects of solution:soil ratio, major cations present in soils, and the ethylenediaminetetraacetic acid (EDTA):lead stoichiometric ratio on the extraction of lead using EDTA were studied for three different Superfund site soils, one rifle range soil, and one artificially lead-contaminated soil. Extraction of lead from the lead-contaminated soils was not affected by a solution:soil ratio as low as 3:1 but instead was dependent on the quantity of EDTA present. Results of the experiments showed that the extraction efficiencies were different for each soil. If sufficiently large amount of EDTA was applied (EDTA-Pb stoichiometric ratio greater than 10), most of the lead were extracted for all soils tested except for a Superfund site soil from a lead mining area. The differences in extraction efficiencies may be due to the major cations present in soils which may compete with lead for active sites on EDTA. For example, iron ions most probably competed strongly with lead for EDTA ligand sites for pH less than 6. In addition, copper and zinc may potentially compete with lead for EDTA ligand sites. Experimental results showed that addition of EDTA to the soil resulted in a very large increase in metals solubility. The total molar concentrations of major cations extracted were as much as 20 times the added molar concentration of EDTA. For some of the soils tested, lead may have been occluded in the iron oxides present in the soil which may affect lead extraction. While major cations present in the soil may be one of the factors affecting lead extraction efficiency, the type of lead species present also play a role.