RESUMEN
RATIONALE: Gas chromatography mass spectrometry (GC-MS) with electron ionization (EI) is the most widely used analysis technique of gaseous samples, but it may be time-consuming for online monitoring of mixtures whose concentrations relatively change rapidly. On the contrary, current ionization methods, such as chemical ionization (CI) and proton transfer reaction (PTR), also have some disadvantages such as selectivity. Therefore, appropriate soft ionization sources are searched for rapid online detection. METHODS: Hollow electrode capillary plasma ionization (HECPI) is based on single electrode plasma. A hollow capillary was placed as both the electrode and the inlet of the gaseous samples. The ionization source is coupled with a mass spectrometer for performance evaluation. RESULTS: Several typical compounds have been tested with HECPI-mass spectrometer. In this process, the dominant ion peaks of all compounds can be indexed as molecular ion peaks, and the product ions of HECPI are less than that of dielectric barrier discharge ionization (DBDI). Three gaseous samples (linalool, triethylamine, and styrene) with various concentrations have been used to further confirm the performance of this source, and the detection limit of linalool is as low as 10 ppb. CONCLUSIONS: HECPI is simple in structure and shows good performance. The results also show that HECPI has the potential to be an effective tool for detecting online gaseous samples rapidly.
RESUMEN
On the basis of a well-developed bench-scale pyrolysis model that relates material composition to flammability, this paper applied mathematical simulations to explore the model sensitivity for the prediction of fire behavior of composite materials. A pyrolysis model for poly(lactic acid) blended with melamine and ammonium polyphosphate as the reference material was selected as the case for analysis. The model input parameters for simulations include the heat of reaction, apparent activation energy, and pre-exponential factor of 15 reactions, as well as the thermal conductivity, emissivity coefficient, absorption coefficient, and density of 17 condensed-phase components. Each reaction-related or component-related parameter was adjusted from 80% of the model value to 120% with a 5% or 10% gradient. Finally, 826 simulation cases in total were calculated for analysis. Both the mass loss rate and the heat release rate of each case were calculated to characterize the sensitivity, which showed the same pattern. Finally, seven primary reactions and five key condensed-phase components with high sensitivity were identified. The predicted fire behaviors are highly related to the kinetics of the reactions between virgin components or reactions where virgin components play an important role in, including the pyrolysis of melted poly(lactic acid), the first step in the pyrolysis of melamine, the first step in the pyrolysis of ammonium polyphosphate, the reaction between melted poly(lactic acid) and melamine, the reaction between ammonium polyphosphate and melamine, and further decomposition of the generated new condensed-phase component. Particularly, the activation energy of these reactions is of sensitivity larger than 5% or 15%. The heat of decomposition of pyrolysis of melted poly(lactic acid) also showed a sensitivity of 2%-5%. The pre-exponential factor of all reactions showed a sensitivity of less than 2%, which can be ignored. Inputting the proper density is important for the prediction of fire behavior as the sensitivity is larger than 2%. The sensitivity of the milligram-scale model was also processed and compared. These simulations provided a fundamental understanding of the sensitivity of thermophysical and chemical properties and thus provide advanced insights into fire behavior modeling and new composite material design.
RESUMEN
Sulfamethoxazole (SMX), recognized as emerging pollutant, has been frequently detected in aquatic environment. However, effects induced by SMX and the underneath mechanism on non-target aquatic organisms, marine mussels (Mytilus galloprovincialis), are still largely unknown. In present study, marine mussels were exposed to SMX (nominal concentrations 0.5, 50 and 500 µg/L) for 6 days, followed by 6 days depuration and responses of antioxidant defenses, e.g. superoxide dismutase (SOD), catalase (CAT) and glutathione-S-transferase (GST), etc., at transcriptional, translational and functional levels were evaluated in two vital tissues, gills and digestive glands. Results showed SMX can be accumulated in mussels while the bio-accumulative ability was low under the experimental condition. A systemic but not completely synchronous antioxidant defense at different levels upon SMX exposure. The transcriptional alteration was more sensitive and had the potential to be used as early warning of SMX induced ecotoxicity. Complementary function of antioxidant enzymes with specific alteration of metabolism related gene (gst) suggested that further researches should focused on SMX metabolism and SMX induced effects simultaneously. Significant tissue-specific antioxidant responses were discovered and gills showed earlier and quicker reacting ability than digestive glands, which was closely related to the functional diversity and different thresholds of xenobiotics allowance.