Polycyclic aromatic hydrocarbons in coal combustion flue gas under electron beam irradiation

The electron beam (EB) technology has been investigated as a one-stage multi-component purification technology. The initial concentrations of SO₂, NO_x, and 16 polycyclic aromatic hydrocarbons (PAH) in flue gas have been reduced simultaneously by over 60%, 50%, and 20%, respectively, in flue gas at the dose of 8 kGy. Determined PAH distribution in the by-product has shown negligible role of adsorption in PAH removal. PAH-based overall toxicity of flue gas decreased remarkably in the range of 30–80% under EB irradiation.     

Ammonia Decomposition Using Electron Beam

This study was carried out to determine the decomposition characteristics of ammonia using an electron beam (EB). Factors influencing these decomposition characteristics such as background gases (air, N₂, O₂, and He), initial ammonia concentration (50–150 ppm), relative humidity (0 or 90 %), and absorbed dose (1–15 kGy) were investigated. In the results of removal characteristics by different background gases, the decomposition efficiency of ammonia was lower (approximately 45 % at 5 kGy) when He was used as a background gas compared to the efficiencies when other background gases were selected. Ammonia removal efficiencies, when initial concentrations were 50 and 150 ppm, were 95 and 75 %, respectively, at 15 kGy. Ozone generation by EB irradiation increased from 2.5 kGy and reached a maximum of 45 ppm when 5 kGy of the absorbed dose was irradiated. However, ozone generation started to decrease when the absorbed dose exceeded 5 kGy and decreased to 0.27 ppm at 15 kGy.     

Decomposition of Trimethylamine by an Electron Beam

To identify the decomposition characteristics of trimethylamine (TMA) by electron beam (EB), we conducted an experiment based on process parameters, including absorbed dose (2.5–10 kGy), background gas (air, O₂, N₂ and He), water content (1,200, 14,300, and 27,500 ppm), initial concentration (50, 100, and 200 ppm) and reactor type (batch or continuous flow system). Air background gas showed a maximum TMA removal efficiency of 86 % at 10 kGy and that was the highest efficiency of all background gases. Energy efficiencies were higher when the absorbed dose was lower (e.g., 2.5 kGy). Decomposition efficiencies of all initial TMA concentrations were approximately >90 % at 10 kGy. Removal efficiencies increased up to 30 % as water vapor increased. As a by-product, it is observed that CH₃ radical formed by EB irradiation was converted into CH₄ by reaction with residual TMA, (CH₃)₂NH, and H. These results suggest that EB technology can be applied for TMA treatment under low concentration and high flow rate conditions.     

Electron beam induced decomposition of chlorinated aromatic compounds in waste incinerator offgas

Gaseous emissions of polychlorinated dibenzo-dioxins and -furanes (PCDD/F) in incinerator flue gas are decomposed to below 0,1 ng m_N⁻³ by the irradiation with accelerated electrons. A mobile off gas cleaning plant (AGATE-M), equipped with a 200 keV electron accelerator (EB), was used to treat a flow of 1000 m_N³ h⁻¹ of flue gas from a waste incinerator. Very high decomposition efficiencies were obtained at a dose of 5 – 10 kGy. A computer model (AGATE-code) was developed to analyze the gas phase chemistry of the process. The experimental and the theoretical results are reported and compared.     

Determination of the Number of OH Radicals in EB-Irradiated Humid Gases Using Oxidation of CO

Electron beam (EB) technology has an advantage for treating dilute environmental pollutants in gases due to high-density population of active species such as radicals and atoms. In general, OH radicals play an important role of initiating the decomposition and removal of such pollutants. It is quite important to understand the behavior of OH radical production for the development of efficient decomposition/removal processes and the comparison with other purification methods. The number of OH radicals produced in humid N₂ at doses of 2.0–10.0 kGy with dose rates of 0.17–2.55 kGy/s under 1-MeV EB irradiation was indirectly determined using an index of oxidation of CO to CO₂, which has been used in atmospheric chemistry. An experiment under conditions where all OH radicals produced react with CO demonstrated that the concentration of CO₂ increased linearly with doses of 0–10 kGy, and the G(OH) was estimated as 4.90.     

Decomposition of Acetaldehyde Using an Electron Beam

This study investigated the decomposition characteristics of acetaldehyde using an electron beam. The removal efficiency (RE) in air, O₂, N₂ and He atmospheres at 10 kGy were 88, 89, 94 and 35 %, respectively. By varying the initial concentration (C₀), G-values at 240 ppm (C₀) were maintained from 6.4 to 7.0 molecules/100 eV, while the G-values at 34 and 60 ppm (C₀) decreased from 4.5 to 1.1 and from 6.6 to 2.0 molecules/100 eV when the absorbed dose increased from 2.5 to 10 kGy. The RE of acetaldehyde at 96 % relative humidity was approximately 10–15 % higher than that at dry air when the absorbed doses were 5–10 kGy. Increasing the water supply did not provide additional improvement of the RE at 2.5 kGy. CO, CO₂, O₃ and trace VOC compounds such as C₂H₄O₂, C₇H₆O, C₆H₆, C₇H₈ and C₈H₁₀ were detected as by-products.     

Degradation and stability of polyaniline on exposure to electron beam irradiation (structure-property relationship)

Polyaniline (PAni) was prepared by electrochemical polymerization and subjected to different doses of electron beam (EB) irradiation. The effect of EB irradiation causes both chain scission and cross-linking process in PAni, which depends on irradiation dose. The degree of chain scission and cross-linking in PAni by EB irradiation is characterized through XRD, TGA, DSC, solubility, EPR and electrical properties measurement. The results reveal that with increase in EB irradiation dose from 0 to 150 kGy DC and AC conductivity and dielectric constant are found to increase mainly due to the chain scission or further doping in PAni. Due to irradiation there is change in the structure of PAni, such as decrease in the d-spacing, inter-chain separation, thermal stability and T_g but increase in the percent crystallinity and solubility. With further increase in the EB irradiation dose from 150 kGy onwards the DC and AC conductivity and dielectric constant are decreased due to the cross-link formation or dedoping in PAni, which causes the decrease in percentage of crystallinity and solubility and increase in d-spacing, inter-chain separation, thermal stability and T_g of PAni.     

Microwave assisted vacuum regeneration for CO2 capture from wet flue gas

Small scale processing of flue gas with the goal of enriching the stream in CO₂ for sequestration or use is an interesting application area for adsorption technology. For example, boiler flue gas which may contain up to 10 % (v/v) CO₂ in air can be readily enriched to a stream containing >70 % CO₂ which may be ideal for use within a process such as acidification, precipitation, stripping, etc. The challenge in these applications is producing high purity CO₂ without excessive energy use and handling high concentrations of water vapor without the added complication of a pre-drying stage. In this study we have examined the use of microwave assisted vacuum as a way of rapidly directing thermal energy to the adsorbent surface to liberate water and CO₂. Preliminary “proof-of-concept” pump down experiments were conducted on a small transparent adsorption column of 13X zeolite pre-saturated with a 12 % CO₂ in N₂ gas mixture. Both wet and dry gas tests were conducted. The addition of microwave radiation improved the rapid desorption of CO₂ and water and improved the integrated CO₂ purity in the blowdown stream from 60 to 80 %. In the case of dry CO₂ mixtures, the enhancement is due to microwave heating of the 13X zeolite facilitated by the high cation density in the faujasite structure. In the case of water and CO₂ desorption, the temperature rise of the adsorbent upon microwave heating was much lower than that predicted by simple heating suggesting that the microwave radiation is absorbed primarily by the adsorbed water. A simplified energy analysis suggests that brief exposure of an adsorbent to microwave radiation will raise the required vacuum level for regeneration of high humidity flue gas streams and may lead to an overall lower energy penalty. The selective ability of microwave radiation to target different species provides scope for optimized, compact, flue gas treatment systems.     

Analysis of Polycyclic Aromatics

Abstract

Polycyclic aromatic hydrocarbons (PAH), among them carcinogenic compounds, have been found to be widely distributed in the human environment. The formation of PAH in processes relevant to environmental pollution will be described (pyrolysis or incomplete combustion of aliphatic and aromatic material, formation in higher plants). The application of the following methods to the analysis of PAH mixtures will be discussed: gas chromatography (capillary columns, use. of liquid crystals and inorganic salts such as LiCl or Cacl₂, as stationary phases in packed columns, selective detectors); luminescence spectroscopy (use of phosphorescence in paper and thin-layer chromatography, Shpol'skii spectra, quenchofluorimetry; mass spectroscopy.     

Advanced oxidation of aromatic VOCs using a pilot system with electron beam–catalyst coupling

The decomposition of volatile organic compounds (VOCs) using a pilot system of electron beam (EB)–catalyst coupling was investigated. Two aromatic VOCs, toluene (1800 ppmC) and o-xylene (1500 ppmC), were irradiated with a dose range of 0–10 kGy at room temperature. The removal efficiencies for toluene and o-xylene were 92.4% and 94.5%, respectively, under a 10 kGy absorbed dose condition, which were higher than the results of 45.7% and 52.3% when EB-only was used, respectively. The CO₂ selectivity approached 100% for both toluene and o-xylene using the EB-catalyst coupling system, while the concentrations of O₃ formed were 0.02 ppm (toluene) and 0.003 ppm (o-xylene) at 10 kGy. The aerosol concentration was also measured as 43.2 μg/m³ (toluene) and 53.4 μg/m³ (o-xylene) at 10 kGy absorbed dose.     

Oxidation of Dimethyl Sulfide in Air Using Electron-Beam Irradiation,and Enhancement of its Oxidation Via an MnO<Subscript>2</Subscript> Catalyst

The decomposition of dimethyl sulfide (DMS) at initial concentrations of 4.5–18.0 ppmv in air was studied under electron-beam (EB) irradiation. Doses to decompose 90% of input DMS were 2.5 kGy for 4.5 ppmv, 3.4 kGy for 10.6 ppmv, and 3.9 kGy for 18.0 ppmv. HCOOH, (CH₃)₂SO, and trace CH₃OH and (CH₃)₂SO₂ were produced as irradiation products in addition to CO₂ and CO. Application of an O₃ decomposition catalyst to an irradiated sample gas led to an enhancement in the oxidation of DMS and its products into CO₂ and the decomposition of O₃. For 10.6 ppmv DMS/air, the mineralization ratio increased from 41% via only EB irradiation to 100% via the combination treatment at 6.3 kGy. The yield of CO₂ to CO_x increased from 5.3 to 87.6% by combination with catalytic oxidation. This combination treatment enables the irradiation energy used to deodorize gas streams containing DMS to be reduced.     

Evaluation of needle trap micro-extraction and automatic alveolar sampling for point-of-care breath analysis

Needle trap devices (NTDs) have shown many advantages such as improved detection limits, reduced sampling time and volume, improved stability, and reproducibility if compared with other techniques used in breath analysis such as solid-phase extraction and solid-phase micro-extraction. Effects of sampling flow (2–30 ml/min) and volume (10–100 ml) were investigated in dry gas standards containing hydrocarbons, aldehydes, and aromatic compounds and in humid breath samples. NTDs contained (single-bed) polymer packing and (triple-bed) combinations of divinylbenzene/Carbopack X/Carboxen 1000. Substances were desorbed from the NTDs by means of thermal expansion and analyzed by gas chromatography-mass spectrometry. An automated CO₂-controlled sampling device for direct alveolar sampling at the point-of-care was developed and tested in pilot experiments. Adsorption efficiency for small volatile organic compounds decreased and breakthrough increased when sampling was done with polymer needles from a water-saturated matrix (breath) instead from dry gas. Humidity did not affect analysis with triple-bed NTDs. These NTDs showed only small dependencies on sampling flow and low breakthrough from 1–5 %. The new sampling device was able to control crucial parameters such as sampling flow and volume. With triple-bed NTDs, substance amounts increased linearly with increasing sample volume when alveolar breath was pre-concentrated automatically. When compared with manual sampling, automatic sampling showed comparable or better results. Thorough control of sampling and adequate choice of adsorption material is mandatory for application of needle trap micro-extraction in vivo. The new CO₂-controlled sampling device allows direct alveolar sampling at the point-of-care without the need of any additional sampling, storage, or pre-concentration steps.     

1-Chloronaphthalene decomposition in different gas mixtures under electron beam irradiation

The decomposition by electron beam (EB) irradiation of 1-chloronaphthalene in different gas matrices (air, N₂) was studied. Over 80% 1-chloronaphthalene was decomposed in air at 58 kGy dose when the initial concentration of 1-chloronaphthalene was 12–30 mg/Nm³. Over 50% 1-chloronaphthalene was decomposed in nitrogen when the initial concentration of 1-chloronaphthalene was 15–42 mg/Nm³.     

Determination of absolute gas adsorption isotherms: simple method based on the potential theory for buoyancy effect correction of pure gas and gas mixtures adsorption

The absolute adsorption isotherms are necessary to correctly evaluate the selectivity of the adsorbent material or to design adsorption processes at high pressure (e.g., H₂ purification from syngas processes, removal of acid gas from natural gas,…). The aim of this work is thus to propose an easy method to correct the buoyancy effect of the bulk phase on the adsorbed phase volume during both pure gas and gas mixtures adsorption for pressures up to 10 MPa. The potential theory of adsorption and the Dubinin–Radushkevich relation are adapted by introducing mixing parameters based on simple Berthelot rules. The concept of internal pressure used to characterize the adsorbed phase is also adapted for mixtures. The method is then improved on a commercial activated carbon (AC), when adsorbing pure H₂S and CH₄, and their mixtures up to 5 MPa. The study points out the importance to carefully consider the buoyancy effect of the bulk phase on the adsorbed phase volume. Its impact on the adsorbent material selectivity at high pressures could affect the design and the performances of PSA or TSA processes. For example, only considering the excess adsorption data leads to an apparent selectivity 13 % greater than the absolute one for a concentration of 6 ppm of H₂S in a CH₄ matrix at 5 MPa (298 K) on the AC.     

Identification of gamma-irradiated Chinese herbs by thermoluminescence analysis

The feasibility of thermoluminescence (TL) to differentiate irradiated Chinese medicinal herbs from non-irradiated was investigated. Thirty different dried Chinese herbs were tested, including root, flower, ramulus, rhizome, cortex, and whole plant samples. Irradiation of Chinese herbs was associated with strong TL peaks at ~150–250 °C, while TL curves of non-irradiated herbs had very low intensities above 250 °C, which was also confirmed by the TL ratio (non-irradiated, TL₁/TL₂ < 0.1). The ability to determine the irradiation dose by the TL method was influenced by the amount and types of minerals in the samples. All levels of irradiation doses could be detected when between 0.1 and 1.0 kGy, except for three herbs at 0.1 kGy dose. Different blends with small quantities (0.1–10 %) of irradiated herbs were also tested in this study. Samples with powder mixtures containing 1 % irradiated components could be differentiated (TL₁/TL₂ > 0.1) except for sterculia lychnophora, semen cassia, flos inulae, and anemone root. TL ratios of some herbs indicated irradiation (TL₁/TL₂ > 0.1) even if the irradiated components were as low as 0.1 %. Thus we demonstrated that TL analysis had excellent sensitivity and reliability for the identification of irradiated Chinese herbs.     

Selective Separation of Oxy-PAH from n-Alkanes and PAH in Complex Organic Mixtures Extracted from Airborne PM2.5

A fast and simple fractionation method was optimized to selectively separate oxy-PAH from polycyclic aromatic hydrocarbons (PAH) and n-alkanes contained in solvent extracted organic matter (SEOM) from atmospheric particles with an aerodynamic diameter ≤2.5 μm (PM_2.5). Samples were collected in Mexico City. Multivariate parameters were adjusted on a standard mixture, and on SEOM spiked with pure standard mixture solutions: type and amount of phase; packing densities; type, proportion and amount of solvents, and elution flow rates were tested under several elution schemes. Cyanopropylsilyl-bonded phase material was the selected stationary phase. The separation method was applied to real samples of SEOM (2.6, 5.6 and 8.5 mg) spiked with n-alkanes, PAH and oxy-PAH. n-Alkanes overlapped with PAH due to an excess of n-alkanes in real samples overloading the capacity of the stationary phase. Oxy-PAH was separated totally from n-alkanes and PAH. Mean recoveries ± confidence intervals (95%) for n-alkanes ranged from 53 ± 17% (n-tetracontane) to 101 ± 11% (n-hexacosane); for PAH from 58 ± 5% (phenanthrene) to 85 ± 9% (benzo[k]fluoranthene); and for oxy-PAH from 68 ± 12% (9,10-dihydrobenzo[a]pyren-7(8H)one) to 108 ± 9% (1,2-benzopyrone). This method is an efficient fractionation procedure to be applied to oxy-PAH, PAH and n-alkanes in complex organic mixtures extracted from PM_2.5.     

Dimethyl phthalate (DMP) degradation in aqueous solution by gamma-irradiation/H<Subscript>2</Subscript>O<Subscript>2</Subscript>

This work includes the applications of radiation processing to decompose dimethyl phthalate (DMP) with gamma and gamma/H₂O₂ processes. Changes in amounts of DMP, dissolved oxygen, total acidity and formaldehyde with irradiation dose were followed. The qualitative analysis of the DMP and the intermediates were determined by using a gas chromatography combined to mass spectrometry and ion chromatography. The results indicated that degradation rate of DMP was affected by H₂O₂ concentration, irradiation dose and removal efficiency of 25 mg L^?1 DMP can reach 100% for 1.42 kGy irradiation dose in the concentration of 4.8 mM H₂O₂, respectively.     

Effect of dose rate on inactivation of microorganisms in spices by electron-beams and gamma-rays irradiation

Total aerobic bacteria in spices used in this study were determined to be 1 × 10⁶ to 6 × 10⁷ per gram. A study on the inactivation of microorganisms in spices showed that doses of 6–9kGy of EB (electron-beams) or γ-irradiation were required to reduce the total aerobic bacteria in many However, a little increase of resistance was observed on the inactivation of total aerobic bacteria in many spices in case of EB irradiation. These difference of radiation sensitivities between EB and γ-rays was explained by dose rate effect on oxidation damage to microorganisms from the results of radiation sensitivities of Bacillus pumilus and B. megaterium spores at dry conditions. On the other hand, these high dose rate of EB irradiation suppressed the increase of peroxide values in spices at high dose irradiation up to 80 kGy. However, components of essential oils in spices were not changed even irradiated up to 50 kGy with EB and γ-rays.     

Simultaneous Enhancement of Mechanical and Dynamic Mechanical Properties of Natural Rubber/Recycled Ethylene-Propylene-Diene Rubber Blends by Electron Beam Irradiation

Mechanical and dynamic mechanical properties of natural rubber/recycled ethylene-propylene-diene rubber (NR/R-EPDM) blends were simultanoeusly enhanced by electron beam (EB) irradiation. The cross-linking promoter, trimethylolpropane triacrylate (TMPTA), was also introduced into the blends to induce the cross-linking. By applying EB irradiation, the tensile modulus, hardness, swelling, cross-link density, and storage modulus increased with increase in the irradiation dose; an irradiation dose of 50 kGy was efficient to gain optimum tensile strength. The formation of irradiation-induced cross-links after EB irradiation is a major concern for the enhancement of mechanical, swelling resistance, and dynamic mechanical properties of the blends.     

Radiodegradation of nadolol in the solid state and identification of its radiolysis products by UHPLC–MS method

Nadolol ((2R*,3S*)-5-{[(2R*)-3-(tert-butylamino)-2-hydroxypropyl]oxy}-1,2,3,4 tetrahydronaphthalene-2,3-diol) in substantia was exposed to ionizing radiation generated by a beam of high-energy electrons in an accelerator, in the standard sterilisation dose of 25 kGy and in higher doses of 50 ? 400 kGy. The irradiated and non-irradiated (control) samples were analysed by the infrared spectrophotometry, electron paramagnetic resonance, differential scanning calorimetry (DSC) and ultra-high performance liquid chromatography coupled with mass spectrometry (UHPLC–MS). The irradiated samples were found to contain free radicals in concentrations much higher than that observed for the other irradiated β-blockers. On the basis of UHPLC–MS results, it was possible to establish structures of 11 compounds of the impurities and/or products of nadolol decomposition. The main product of radiodegradation was concluded to be formed as a result of abstraction of the hydroxyl group and aromatization of the tetrahydronaphthalene ring. The results of DSC measurements confirmed the presence of radiolysis products in the irradiated samples of nadolol. A shift of the endothermic peak corresponding to melting towards lower temperatures (by 4.4 °C at the dose of 400 kGy) was directly proportional to the doses of radiation used, which permits concluding that this method is sensitive and suitable for evaluation of radiodegradation of nadolol in solid phase.