在线气相色谱测定园区中特征污染因子研究

近两年来,随着科学技术的不断发展,在线气相色谱分析仪已逐步在国内监测实际中得到应用,在线气相色谱的应用使挥发性有机物的实时、连续监测成了可能,有效改善了实验室监测数据的滞后性,减少了样品采集、储存、运输过程中产生的误差,结合常州市某化工园区大气特征污染因子预警系统的建设情况,简单介绍了在线气相色谱的工作原理和过程。通过特征污染因子标准曲线的建立和比对试验,说明了在线气相色谱环境监测应用的可行性。     

不同TS浓度互花米草沼渣二次发酵特性研究

中温（35±1）℃条件下,沼渣经6%的NaOH常温下处理48 h后,在TS含量8%、10%、12%的条件下沼气发酵.分析了发酵过程中日产气量、累积产气量、甲烷含量、pH值、挥发性脂肪酸（VFA）的变化,从不同角度考察TS含量负荷对沼渣二次发酵特性的影响.单位TS的日产气高峰分别达10、14、13 mL.g-1,累积产气率为217、227、228 mL.g-1,甲烷含量均在65%以上.发酵过程中最低pH为7.04.乙酸浓度最高分别为3 364、3 286、5 728 mg.L-1,丙酸和丁酸浓度均低于1 100 mg.L-1.结果表明,沼渣为难降解有机物,分解缓慢,不易出现酸化现象,但仍具有较强的产气潜力.     

北京城乡结合地空气中挥发性有机物健康风险评价

采用低温固体吸附采样,热脱附-气相色谱-质谱方法对北京城乡结合地空气中挥发性有机物（VOCs）进行了观测分析,并利用国际公认的健康风险评价四步法评价模型,对北京城乡结合地空气中挥发性有机物的健康风险进行了初步评价.结果表明,芳香族类的非致癌风险值在10-4～10-1数量级,卤代烃的非致癌风险值在10-4～10-5数量级,挥发性有机污染物的非致癌风险系数〈1,不会对暴露人群健康造成明显的非致癌危害.但苯的致癌指数较高（2.21×10-5）,超过了USEPA的建议值（1×10-6）,可能对人体健康造成潜在危害.在一年四季的健康风险中,冬季VOCs的健康风险最高,秋季次之,夏季最低.     

辽宁省典型城市空气中挥发性有机物健康风险评价

美国综合风险评估系统（IRIS）提供了污染物的参考剂量（RFD）和污染物参考浓度（RfC）的相关数据,但某些化合物的RFD和RfC数据不全,造成了风险评价的困难,基于RFD的风险评价很难确定污染物由呼吸系统的准确摄入量。应用SPSS软件剖析了RFD和RfC的相关性,提出了以RfC为基础的风险评价体系,与RFD评价结果对比表明：基于RfC的风险评价更能准确反映VOCs污染的风险。尝试应用RFD和RfC值对沈阳、鞍山、抚顺、葫芦岛四个城市空气中VOCs进行非致癌健康风险评价。     

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.     

Fast increasing of surface ozone concentrations in Pearl River Delta characterized by a regional air quality monitoring network during 2006-2011

Based on the observation by a Regional Air Quality Monitoring Network including 16 monitoring stations, temporal and spatial variations of ozone(O3), NO2and total oxidant(Ox) were analyzed by both linear regression and cluster analysis. A fast increase of regional O3concentrations of 0.86 ppbV/yr was found for the annual averaged values from 2006 to 2011 in Guangdong, China. Such fast O3increase is accompanied by a correspondingly fast NOx reduction as indicated by a fast NO2 reduction rate of 0.61 ppbV/yr. Based on a cluster analysis, the monitoring stations were classified into two major categories – rural stations(non-urban) and suburban/urban stations. The O3concentrations at rural stations were relatively conserved while those at suburban/urban stations showed a fast increase rate of 2.0 ppbV/yr accompanied by a NO2 reduction rate of 1.2 ppbV/yr. Moreover, a rapid increase of the averaged O3 concentrations in springtime(13%/yr referred to 2006 level) was observed, which may result from the increase of solar duration, reduction of precipitation in Guangdong and transport from Eastern Central China. Application of smog production algorithm showed that the photochemical O3production is mainly volatile organic compounds(VOC)-controlled. However, the photochemical O3production is sensitive to both NOx and VOC for O3pollution episode. Accordingly, it is expected that a combined NOx and VOC reduction will be helpful for the reduction of the O3 pollution episodes in Pearl River Delta while stringent VOC emission control is in general required for the regional O3 pollution control.     

Effect of a high strength chemical industry wastewater on microbial community dynamics and mesophilic methane generation

A high strength chemical industry wastewater was assessed for its impact on anaerobic microbial com- munity dynamics and consequently mesophilic methane generation. Cumulative methane production was 251 mL/g total chemical oxygen demand removed at standard temperature and pressure at the end of 30 days experimental period with a highest recorded methane percentage of 80.6% of total biogas volume. Volatile fatty acids （VFAs） analysis revealed that acetic acid was the major intermediate VFAs produced with propionic acid accumulating over the experimental period. Quantitative analysis of microbial communities in the test and control groups with quantitative real time polymerase chain reaction highlighted that in the test group, Eubacteria （96.3%） was dominant in comparison with methanogens （3.7%）. The latter were dominated by Methanomicrobiales and Methanobacteriales while in test groups increased over the experimental period, reaching a maximum on day 30. Denaturing gradient gel electrophoresis profile was performed, targeting the 16S rRNA gene of Eubacteria and Archaea, with the DNA samples extracted at 3 different time points from the test groups. A phylogenetic tree was constructed for the sequences using the neighborhood joining method. The analysis revealed that the presence of organisms resembling Syntrophomonadaceae could have contributed to increased production of acetic and propionic acid intermediates while decrease of organisms resembling Pelotomaculum sp. could have most likely contributed to accumulation of propionic acid. This study suggested that the degradation of organic components within the high strength industrial wastewater is closely linked with the activity of certain niche microbial communities within eubacteria and methanogens.