Transverse approach between real world concentrations of SO2, NO2, BTEX, aldehyde emissions and corrosion in the Grand Mare tunnel

With regard to automotive traffic, a tunnel-type semi enclosed atmosphere is characterized by a higher concentration of gaseous pollutants than on urban traffic roads and highlights the gaseous effluent species having an impact on material degradation. Therefore, a transverse approach between air quality and its consequences upon the longevity of materials is necessary, implying better knowledge of tunnel atmosphere and a better understanding of material degradation inside a tunnel for operating administration. Gaseous pollutant measurements carried out in a road tunnel in Rouen (Normandy) give the real world traffic concentrations of experimental exposure conditions. The sampling campaigns, achieved in summer and winter include SO₂, NO₂, BTEX and aldehyde analyses. Effluent profiles in the upward and downward tubes have been established. The current work shows that SO₂, NO₂, formaldehyde, acetaldehyde, propanal and butanal must be considered in the degradation process of materials in a stuffy environment. As regards NO₂, its concentration depends on the modification of the automotive fleet. The total aldehyde concentrations indicate no particular trend between the two bores. Formaldehyde, acetaldehyde, propanal, butanal and acrolein species are the most abundant species emitted by vehicles and represent 90% to 95% of the total aldehyde emissions.     

Effect of CeO2 and Al2O3 on the activity of Pd/Co_3O_4/cordierite catalyst in the three-way catalysis reactions (CO/NO/CnHm)

The present article studies the effect of CeO₂ and Al₂O₃ on the activity of Pd/Co₃O₄/cordierite catalyst in conversion of NO, CO, C_nH_m. The catalysts were characterized by temperature programmed reduction with hydrogen, X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. It is shown that the effect of CeO₂ on the properties of Pd/Co₃O₄/cordierite catalyst depends on preparation method. The catalyst obtained by co-deposition of cerium and cobalt oxides has higher activity in CO oxidation (CO + O₂ and CO + NO) and total hexane oxidation (C₆H₁₄ + O₂). Such phenomenon is probably caused by more than stoichiometric amount of formed oxygen vacancies, an increase in both mobility of surface oxygen and dispersity of components in the catalytic composition. It is demonstrated that CeO₂ addition promotes the SO₂ resistance of Pd/Co₃O₄/cordierite. The second support decreases the activity of Pd/Co₃O₄/cordierite catalyst in the reactions of CO and C₆H₁₄ with oxygen because of CoAl₂O₄ formation.     

pH-dependent leaching behaviour and other performance properties of cement-treated mixed contaminated soil

Portland cement has been widely used for stabilisation/solidification (S/S) treatment of contaminated soils. However, there is a dearth of literature on pH-dependent leaching of contaminants from cement-treated soils. This study investigates the leachability of Cu, Pb, Ni, Zn and total petroleum hydrocarbons (TPH) from a mixed contaminated soil. A sandy soil was spiked with 3000 mg/kg each of Cd, Cu, Pb, Ni and Zn, and 10,000 mg/kg of diesel, and treated with ordinary Portland cement (CEM I). Four different binder dosages, 5%, 10%, 15% and 20% (m/m) and different water contents ranging from 13%-19% dry weight were used in order to find a safe operating envelope for the treatment process. The pH-dependent leaching behaviour of the treated soil was monitored over an 84-day period using a 3-point acid neutralisation capacity (ANC) test. The monolithic leaching test was also conducted. Geotechnical properties such as unconfined compressive strength (UCS), hydraulic conductivity and porosity were assessed over time. The treated soils recorded lower leachate concentrations of Ni and Zn compared to the untreated soil at the same pH depending on binder dosage. The binder had problems with Pb stabilisation and TPH leachability was independent of pH and binder dosage. The hydraulic conductivity of the mixes was generally of the order, 10^-8 m/sec, while the porosity ranged from 26%-44%. The results of selected performance properties are compared with regulatory limits and the range of operating variables that lead to acceptable performance described.     

Efficiency and degradation products elucidation of the photodegradation of mefenpyrdiethyl in water interface using TiO2 P-25 and Hombikat UV100

The photodegradation of mefenpyrdiethyl (MFD), an herbicide safener, was investigated in aqueous suspensions by using Degussa P-25 and Hombikat UV100 titanium oxide under simulated sunlight irradiation. The effects of initial concentration of the herbicide, pH, catalysts and hydrogen peroxide doses as well as their combinations were studied and optimized. Accordingly, the kinetic parameters were determined and the effectiveness of the processes was assessed by calculating the rate constants. A pseudo first-order kinetics was observed. Under experimental conditions, the degradation rate constants were strongly influenced using P-25 and no noticeable effect was observed for Hombikat UV100. DFT calculations with B3LYP/6-311+G(2d,p)//B3LYP/6-31+G(d,p) level of theory were performed to check whether significant conformational changes occur when the charge state of the MFD substrate changes and whether these changes could play a role in the dependency of photodegradation rate constant on the studied pH. High resolution mass spectrometry (FT-ICR/MS) was implemented to identify the main degradation products.     

Seasonal trend of ambient PCDD/Fs in Tianjin City, northern China using active sampling strategy

The spatial concentrations, seasonal trends, profiles and congener pairs of ambient polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were investigated within a seasonally active sampling scheme during Jun 2008 and Jan 2009 in Tianjin City, northern China. The PCDD/F concentrations ranged 14.2-172 fg I-TEQ/m³ (average 69.3 fg I-TEQ/m³) in summer and (89.8-1.01) × 10³ fg I-TEQ/m³ (average 509 fg I-TEQ/m³) in winter, respectively, except for the E-waste dismantling site where much higher values were observed (1.04 × 10³ fg I-TEQ/m³ in summer and 7.123 × 10³ fg I-TEQ/m³ in winter). The results indicated a significantly seasonal trend with higher TEQ values in winter as compared with summer, which could be related to increased emission sources and seasonal variations of the atmospheric boundary layer height. 2,3,4,7,8-PeCDF was the dominant contributor to the total PCDD/F toxic equivalents, and 2,3,7,8-TCDD was detected at almost all the sampling sites in winter. Most of the similarly substituted PCDD/F congener pairs exhibited high correlations, suggesting that they might have similar environmental fate or sources. But different seasonal and spatial distributions of PCDD/F concentrations indicated that the emission sources might be intermittent.     

Soil warming effect on net ecosystem exchange of carbon dioxide during the transition from winter carbon source to spring carbon sink in a temperate urban lawn

The significant warming in urban environment caused by the combined effects of global warming and heat island has stimulated widely development of urban vegetations. However, it is less known of the climate feedback of urban lawn in warmed environment. Soil warming effect on net ecosystem exchange (NEE) of carbon dioxide during the transition period from winter to spring was investigated in a temperate urban lawn in Beijing, China. The NEE (negative for uptake) under soil warming treatment (temperature was about 5℃ higher than the ambient treatment as a control) was -0.71 μmol/(m².sec), the ecosytem was a CO₂ sink under soil warming treatment, the lawn ecosystem under the control was a CO₂ source (0.13 μmol/(m².sec)), indicating that the lawn ecosystem would provide a negative feedback to global warming. There was no significant effect of soil warming on nocturnal NEE (i.e., ecosystem respiration), although the soil temperature sensitivity (Q₁₀) of ecosystem respiration under soil warming treatment was 3.86, much lower than that in the control (7.03). The CO₂ uptake was significantly increased by soil warming treatment that was attributed to about 100% increase of α (apparent quantum yield) and A_max (maximum rate of photosynthesis). Our results indicated that the response of photosynthesis in urban lawn is much more sensitive to global warming than respiration in the transition period.     

Preparation, characterization and application of CuCrO2/ZnO photocatalysts for the reduction of Cr(VI)

The delafossite CuCrO₂ elaborated by sol-gel from 40 nm diameter colloid is optically active in the visible region. It is characterized physically and photoelectrochemically. The microstructure is fairly homogenous with a mean crystallite size of ca. 2 μm. The optical gap (1.30 eV), determined from the diffuse reflectance, is well suited to the sunlight spectrum. The Mott Schottky plot is characteristic of P-type conductivity with a flat band potential of -0.26 V_SCE. As application, the photoreduction of chromate is successfully achieved in air-equilibrated suspension CuCrO₂/ZnO (1/1). CuCrO₂ is photoactivated by visible light and the electrons in the conduction band (-1.34 V_SCE) are injected to ZnO. In the presence of salicylic acid, a conversion of Cr(VI) to Cr(III) of 57% is obtained under optimal conditions (pH 3 at 25℃, 5×10^-4 mol/L) because of the HCrO₄^- dark adsorption onto ZnO (4HCrO₄^- + 3C₇H₆O₃ + 18O₂ + 16H⁺ → 4Cr³⁺ + 21CO₂ + 19H₂O, ΔG⁰ = -557 kcal/mol). Prolonged illumination is accompanied by a deceleration in the photoactivity owing to the competitive water reduction, an issue of energetic concern. The hetero-system exhibits self sensitization for hydrogen production with an evolution rate of 149 μmol/(hr·g).     

耐汞好氧反硝化菌的鉴定及适应汞离子的特性研究

从实验室保存的高效好氧反硝化菌种中筛选得到一株抗汞细菌并命名为X1,经生理生化特性和16SrRNA基因序列分析,初步鉴定该菌为恶臭假单胞菌(Pseudomonasputida).对菌株X1进行Hg2适应特性研究,结果表明,对于Hg2浓度为2、67++4、、mg·L-1的实验组,菌体分别需要被延滞12、284018、、h后进入对数期,而8mg·L-1实验组则不能进入对数期;在好氧反硝化过程中,Hg2浓度在7mg·L+-1范围内各实验组的好氧反硝化过程中NO3-N浓度变化速率、NO2-N累积峰值、pH特征点出现时刻随着Hg2浓度的增大而增大(延迟),而Hg2浓度呈现出同硝氮一致的下降趋势,并且在对数期内除汞率能达到100%.研究表明,菌株X1对Hg2最大适宜耐受浓度为7mg·L+-1,相应适应时间约为40h.在最大耐受浓度范围内,菌株X1的生长和好氧反硝化过程呈现出"被抑制-适应-受刺激"的变化规律,其中,被抑制的时间和受刺激的程度都随着Hg2浓度的增大而增大,主要表现为延滞期的延长和对数期的缩短.此外,在对数期,菌株X1的生长速率、达到稳定期的浓度和好+氧反硝化速率也都随着Hg2浓度的增大而增大,且大于无Hg2菌组.++     

利用皂土吸附和介电泳方法间接去除水中的Mn2+

水中重金属去除一直是水处理的技术难点.锰虽然是动物必需的微量元素之一,但是人和动物摄入过量的锰会对神经系统等产生毒害.利用皂土吸附水中的重金属Mn2+,在装有微电极阵列芯片的介电泳池研究装置中,通过调节外加交流电压,捕获悬浮液中的皂土从而间接去除Mn2+.吸附了微量重金属离子的皂土被捕获到电场强度较大的区域,发生了正介电泳.该研究为建立一种从废水中间接去除重金属离子的实际可行方法奠定了实验基础,不存在二次污染.     

活性焦负载MnO2对气态Hg0的吸附脱除研究

研究了活性焦(AC)及负载MnO2的活性焦(MnO2/AC)对气态Hg0的吸附脱除,发现负载MnO2到AC明显提高了其对Hg0的吸附脱除能力.考察了MnO2负载量、温度、Hg0浓度和烟气成分等对MnO2/AC吸附脱除Hg0的影响.结果表明,MnO2/AC对Hg0的吸附脱除能力随MnO2负载量的增加而增强;在120～200℃的温度范围内,随着温度升高,MnO2/AC对Hg0的吸附脱除能力增强;O2和HCl对MnO2/AC吸附脱除Hg0具有促进作用,而SO2和H2O具有抑制作用.SEM-EDX和逐级化学提取结果证实,MnO2将Hg0催化氧化为HgO并吸附在AC上,这是MnO2/AC具有较高的吸附脱除Hg0能力的原因.