Reversibly enhanced aqueous solubilization of volatile organic compounds using a redox-reversible surfactant

Surfactant-enhanced remediation (SER) is an effective method for the removal of volatile organic compounds (VOCs) from contaminated soils and groundwater. To reuse the surfactant the VOCs must be separated from the surfactant solutions. The water solubility of VOCs can be enhanced using reversible surfactants with a redox-acive group, (ferrocenylmethyl)dodecyldimethylammonium bromide (Fcl2) and (ferrocenylmethyl)tetradecanedimethylammonium bromide (Fcl4), above and below their critical micelle concentrations (CMC) under reducing (I⁺) and oxidative (I²⁺) conditions. The CMC values of Fcl2 and Fcl4 in I⁺ are 0.94 and 0.56 mmol/L and the solubilization of toluene by Fcl2 and Fcl4 in I⁺ for toluene is higher than the solubilization achieved with sodium dodecyl sulfate, cetyltrimethylammonium bromide and Trition X-114. The solubilization capacity of the ferrocenyl surfactants for each tested VOCs ranked as follows: ethylbenzene > toluene > benzene. The solubilities of VOCs by reversible surfactant in I⁺ were 30% higher than those in I²⁺ at comparable surfactant concentrations. The effects of Fcl4 concentrations on VOCs removal efficiency were as follows: benzene > toluene > ethylbenzene. However, an improved removal efficiency was achieved at low ferrocenyl surfactant concentrations. Furthermore, the reversible surfactant could be recycled through chemical approaches to remove organic pollutants, which could significantly reduce the operating costs of SER technology.     

低温等离子体-催化协同降解挥发性有机废气

低温等离子体-催化协同技术适合于各类挥发性有机物的治理,特别是大气量低浓度的有机废气的处理.高效催化剂的加入可 以显著提高等离子体反应中有机废气的降解效率,减少有害副产物的生成以及提高反应器的能量利用率.从反应器、催化剂以及背景气体等方面探讨了该技术实现产业化需要解决的问题,结合低温等离子体与催化剂的相互作用、等离子体...     

Effects of metal and acidic sites on the reaction by-products of butyl acetate oxidation over palladium-based catalysts

Catalytic oxidation is widely used in pollution control technology to remove volatile organic compounds. In this study, Pd/ZSM-5 catalysts with different Pd contents and acidic sites were prepared via the impregnation method. All the catalysts were characterized by means of N2 adsorption- desorption, X-ray fluorescence （XRF）, HE temperature programmed reduction （H2-TPR）, and NH3 temperature programmed desorption （NH3-TPD）. Their catalytic performance was investigated in the oxidation of butyl acetate experiments. The by-products of the reaction were collected in thermal desorption tubes and identified by gas chromatography/mass spectrometry. It was found that the increase of Pd content slightly changed the catalytic activity of butyl acetate oxidation according to the yield of CO2 achieved at 90%, but decreased the cracking by-products, whereas the enhancement of strong acidity over Pd-based catalysts enriched the by-product species. The butyl acetate oxidation process involves a series of reaction steps including protolysis, dehydrogenation, dehydration, cracking, and isomerization. Generally, butyl acetate was cracked to acetic acid and 2- methylpropene and the latter was an intermediate of the other by-products, and the oxidation routes of typical by-products were proposed. Trace amounts of 3-methylpentane, hexane, 2-methylpentane, pentane, and 2-methylbutane originated from iso4merization and protolysis reactions.     

Unregulated emissions from diesel engine with particulate filter using Fe-based fuel borne catalyst

The alteration and formation of toxic compounds and potential changes in the toxicity of emissions when using after-treatment technologies have gained wide attention. Volatile organic compound（VOC）, carbonyl compound and particle-phase polycyclic aromatic hydrocarbon（PAH） emissions were tested at European Steady State Cycle（ESC） to study unregulated emissions from a diesel engine with a fuel-borne catalyst and diesel particulate filter（FBC–DPF）. An Fe-based fuel-borne catalyst was used for this study. According to the results, brake specific emissions of total VOCs without and with DPF were 4.7 and4.9 mg/kWh, respectively, showing a 4.3% increase. Benzene and n-undecane emissions increased and toluene emission decreased, while other individual VOC emissions basically had no change. When retrofitted with the FBC–DPF, total carbonyl compound emission decreased 15.7%, from 25.8 to 21.8 mg/kWh. The two highest carbonyls, formaldehyde and acetaldehyde, were reduced from 20.0 and 3.7 to 16.5 and 3.3 mg/kWh respectively. The specific reactivity（SR） with DPF was reduced from 6.68 to 6.64 mg/kWh. Total particle-phase PAH emissions decreased 66.4% with DPF compared to that without DPF. However, the Benzo[a]pyrene equivalent（BaPeq） with DPF had increased from 0.016 to 0.030 mg/kWh.Fluoranthene and Pyrene had the greatest decrease, 91.1% and 88.4% respectively. The increase of two- and three-ring PAHs with DPF indicates that the fuel-borne catalyst caused some gas-phase PAHs to adsorb on particles. The results of this study expand the knowledge of the effects of using a particulate filter and a Fe-based fuel-borne catalyst on diesel engine unregulated emissions.     

化学合成类制药行业工艺废气VOCs排放特征与危害评估分析

以浙江台州6家典型化学合成类制药企业为代表,对其排放工艺废气中的18项挥发性有机物(VOCs)特征污染物(如甲苯、甲醛、二氯甲烷等)进行监测和分析,并采用臭氧产生潜力(OFP)和健康风险评价指标对VOCs所产生的环境与健康危害进行初步的评价.结果表明,化学合成类制药企业排放的总VOCs浓度为14.9~308.6 mg·m-3,其产生环境危害的OFP值为3.1~315.1 mg·m-3,主要贡献物质为甲苯、四氢呋喃、乙酸乙酯等6种物质,存在较大的潜在环境危害.另外,健康危害中的非致癌风险指数和总致癌风险指数介于9.48×10-7~4.98×10-4a-1和3.17×10-5~6.33×10-3之间,主要是苯、甲醛和二氯甲烷这3种致癌物.     

大连星海地区环境空气中挥发性有机物的臭氧生成潜势研究

以该实验的观测资料为基础,通过数据分析表明,对大连星海地区OH自由基消耗的主要环境VOCs组分是烯烃类物质,对O3生成潜势贡献最高的环境VOCs组分是芳香烃类物质;综合LiOH及OFP值评价,识别影响大连星海地区O3生成的关键环境VOCs反应活性物种为丙烯、甲苯、间对二甲苯等物质。     

Field monitoring of volatile organic compounds using passive air samplers in an industrial city in Japan

Highly portable, sensitive, and selective passive air samplers were used to investigate ambient volatile organic compound (VOC) levels at multiple sampling sites in an industrial city, Fuji, Japan. We determined the spatial distributions of 27 species of VOCs in three campaigns: Mar (cold season), May (warm season), and Nov (mild season) of 2004. In all campaigns, toluene (geometric mean concentration, 14.0microg/m3) was the most abundant VOC, followed by acetaldehyde (4.76microg/m3), and formaldehyde (2.58microg/m3). The spatial distributions for certain VOCs showed characteristic patterns: high concentrations of benzene and formaldehyde were typically found along major roads, whereas high concentrations of toluene and tetrachloroethylene (PCE) were usually found near factories. The spatial distribution of PCE observed was extremely consistent with the diffusion pattern calculated from Pollutant Release and Transfer Register data and meteorological data, indicated that passive air samplers are useful for determining the sources and distributions of ambient VOCs.     

Co3O4/介孔分子筛催化剂对苯催化完全氧化的研究

分别以介孔分子筛MCM-41、MCM-48、SBA-15为载体,采用等体积浸渍法制备了氧化钴/介孔分子筛催化剂,利用N₂吸附、X射线衍射、程序升温还原等技术对催化剂进行了表征,考察了Co₃O₄的负载量及载体的孔结构对催化剂完全催化氧化苯的性能的影响。结果表明,Co₃O₄的负载量为20%时,催化剂的催化活性最好;载体的孔径和催化剂的可还原性能是影响催化活性的主要因素,催化剂活性顺序为Co₃O₄ /SBA-15> Co₃O₄ /MCM41> Co₃O₄ /MCM-48。     

Interactions of forests with secondary air pollutants: some challenges for future research

The effects of ozone and other photochemical oxidants on individual trees have been studied for several decades, but there has been much less research on the potential effects on entire forest ecosystems. Given that ozone and other oxidants affect the production and subsequent fate of biogenic volatile organic compounds that act as signalling molecules, there is a need for more detailed study of the role of oxidants in modifying trophic interactions in forests. Deposition of fine particulates to forests may act as a source of nutrients, but also changes leaf surface properties, increasing the duration of surface wetness and modifying the habitat for epiphytic organisms, leading to increased risks from pathogens. Even where this pathway contributes a relatively small input of nutrients to forests, the indirect effects on canopy processes and subsequent deposition to the forest floor in throughfall and litter may play a more important role that has yet to be fully investigated.     

Influence of Relative Humidity and Ozone on the Sampling of Volatile Organic Compounds on Carbotrap/Carbosieve Adsorbents

By using a dynamic dilution system, the atmospheric measurement of 11 selected toxics VOCs (ethylene, acetylene, propene, 1-butene, 1,3-butadiene, 1-pentene, 1-hexene, benzene, toluene, ethylbenzene, m+p-xylene) from the list WHO of 1996 and TO-14 method of US EPA by preconcentration by thermal desorption (TD), analysis by gas chromatography (GC), identification and quantification with a flame ionisation detector (FID) was developed and validated in term of metrology, especially the techniques of sampling of these VOCs with adsorbents cartridges "Air Toxics" when used with an "UMEG sampler" equipped in the inlet with a nafion membrane. In particular the influence of climatic conditions (temperature and relative humidity) and the influence of chemical factors like ozone, on the representativity of sampling were studied. Experiments made with various humidities showed that the addition of a nafion membrane in the inlet of the sampling system was required. Without this membrane, losses of compounds were observed for RH >50%. With this membrane, storage for 2 weeks in a refrigerator, as for canisters, did not induce a loss of compounds. No significative decrease of concentrations of the studied VOCs after 14 days storage, which are known to react with ozone, were observed with an ozone concentrations of 55 ppb. One explanation is that nafion membrane, placed in the inlet of the sampler, will neutralize ozone before entering the sampling tubes. This observation is in accordance with literature which states that the sampling of VOCs on Carbotrap cartridges without ozone scrubber induce a loss of compounds.