Simplified structure of the condensed phase of fire retarded PA6 nanocomposites in TGA as related flammability

This paper concerns with the analysis of the nature of the mass residue of PA6 and its nanocomposites in nitrogen. To assess the structure of the condensed phase during pyrolysis, this study presents thermal (by TGA in nitrogen) and condensed phase analysis of the residue (by FTIR-ATR) of PA6 nanocomposites consisting of phosphorous based flame retardants (FR) and/or nanoparticles (based on modified Montmorillonite clay). The thermal analysis reveals that the nanoparticles do not change the pyrolysis kinetics of PA6 whereas the FR does. The FR and NC used in the polymer nanocomposites (PNC) are capable of changing the structure of the char compared with pure PA6, where the char structure consists of polycyclic aromatic hydrocarbons (PAH) whereas the PA6 does not leave any considerable amount of mass residue. This residue analysis for decomposition samples in TGA in Nitrogen of the PA6/FR/NC composites complements previously published work for gas phase analysis ( FTIR-gas) as well as cone calorimeter characterization for their flammability. The overall aim, addressed here also, is to find out to what extent microscale measurements (e.g. TGA/FTIR/DSC/ATR) can be used a priori to delineate the flammability of polymer fire retarded composites. It is shown that FTIR-gas and FTIR (ATR) residue can be used to determine the fire retardant action (solid and/or gaseous) only qualitatively.     

Summer fluxes of atmospheric greenhouse gases N2O, CH4 and CO2 from mangrove soil in South China

The atmospheric fluxes of N₂O, CH₄ and CO₂ from the soil in four mangrove swamps in Shenzhen and Hong Kong, South China were investigated in the summer of 2008. The fluxes ranged from 0.14 to 23.83 μmol m⁻² h⁻¹, 11.9 to 5168.6 μmol m⁻² h⁻¹ and 0.69 to 20.56 mmol m⁻² h⁻¹ for N₂O, CH₄ and CO₂, respectively. Futian mangrove swamp in Shenzhen had the highest greenhouse gas fluxes, followed by Mai Po mangrove in Hong Kong. Sha Kong Tsuen and Yung Shue O mangroves in Hong Kong had similar, low fluxes. The differences in both N₂O and CH₄ fluxes among different tidal positions, the landward, seaward and bare mudflat, in each swamp were insignificant. The N₂O and CO₂ fluxes were positively correlated with the soil organic carbon, total nitrogen, total phosphate, total iron and NH₄⁺-N contents, as well as the soil porosity. However, only soil NH₄⁺-N concentration had significant effects on CH₄ fluxes.     

Emission of N2O and CH4 from a constructed wetland in southeastern Norway

The Skjønhaug constructed wetland (CW) is a free surface water (FSW) wetland polishing chemically treated municipal wastewater in southeastern Norway and consists of three ponds as well as trickling, unsaturated filters with light weight aggregates (LWA). Fluxes of nitrous oxide (N₂O) and methane (CH₄) have been measured during the autumn, winter and summer from all three ponds as well as from the unsaturated filters. Physicochemical parameters of the water have been measured at the same localities. The large temporal and spatial variation of N₂O fluxes was found to cover a range of − 0.49 to 110 mg N₂O–N m^− 2 day⁻¹, while the fluxes of CH₄ was found to cover a range of − 1.2 to 1900 mg m^− 2 day^− 1. Thus, both emission and consumption occurred. Regarding fluxes of N₂O there was a significant difference between the summer, winter and autumn, with the highest emissions occurring during the autumn. The fluxes of CH₄ were, on the other hand, not significantly different with regard to seasons. Both the emissions of N₂O and CH₄ were positively influenced by the amount of total organic carbon (TOC). The measured fluxes of N₂O and CH₄ are in the same range as those reported from other CWs treating wastewater. There was an approximately equal contribution to the global warming potential from N₂O and CH₄.     

X射线荧光光谱法测定电解铝灰中SiO2、Fe2O3、MgO、CaO、K2O、Na2O、MnO、TiO2、P2O5的含量

电解铝灰、铝渣是铝在电解过程中产生的一种浮渣,电解过程中漂浮在电解槽铝液的上方,主要成分为电解过程中未反应的冰晶石、氧化铝、金属铝等混合物,回收价值较高。对电解铝灰的成分分析,相对于化学滴定等分析方法,X射线荧光光谱法样品前处理更加简单方便,且可以同时对多组分进行分析。用粉末压片-X射线荧光光谱法测定电解铝灰中SiO₂、Fe₂O₃、MgO、CaO、K₂O、Na₂O、MnO、TiO₂、P₂O₅的含量。以成分含量相近的铝土矿国家标准物质样品绘制具有一定浓度梯度的标准曲线,通过理论α系数校正方法和经验校正法校正。所得结果表明:各元素含量在标准工作曲线中标准样品的含量范围内时,测定结果和常规分析方法测定结果相符。在方法的精密度实验中,含量较高的SiO₂的极差为0.2%,其他元素值也较为稳定,满足质量要求。     

CO2 加氢合成甲醇催化剂的研究进展

CO_2加氢合成甲醇的运用是在现代社会中对CO_2循环利用的重要方式之一。也同样是对环境保护的重要要求。无论是在CO_2的合成反映之中,还是在新型的催化剂的研制过程之中。在环境保护的过程之中,全球变暖的问题的存在,是急需面对的一个重要问题。所以,对CO_2加氢合成甲醇催化剂的研究非常重要。     

Degradation of the antibiotic oxolinic acid by photocatalysis with TiO2 in suspension

In the work presented here, a photocatalytic system using titanium Degussa P-25 in suspension was used to evaluate the degradation of 20 mg L⁻¹ of antibiotic oxolinic acid (OA). The effects of catalyst load (0.2-1.5 g L⁻¹) and pH (7.5-11) were evaluated and optimized using the surface response methodology and the Pareto diagram. In the range of variables studied, low pH values and 1.0 g L⁻¹ of TiO₂ favoured the efficiency of the process. Under optimal conditions the evolution of the substrate, chemical oxygen demand, dissolved organic carbon, toxicity and antimicrobial activity on Escherichia coli cultures were evaluated. The results indicate that, under optimal conditions, after 30 min, the TiO₂ photocatalytic system is able to eliminate both the substrate and the antimicrobial activity, and to reduce the toxicity of the solution by 60%. However, at the same time, ∼53% of both initial DOC and COD remain in solution. Thus, the photocatalytical system is able to transform the target compound into more oxidized by-products without antimicrobial activity and with a low toxicity. The study of OA by-products using liquid chromatography coupled with mass spectrometry, as well as the evaluation of OA degradation in acetonitrile media as solvent or in the presence of isopropanol and iodide suggest that the reaction is initiated by the photo-Kolbe reaction. Adsorption isotherm experiments in the dark indicated that under pH 7.5, adsorption corresponded to the Langmuir adsorption model, indicating the dependence of the reaction on an initial adsorption step.     

Degradation of bromoxynil and trifluralin in natural water by direct photolysis and UV plus H2O2 advanced oxidation process

The degradation of two pesticides, bromoxynil and trifluralin, was investigated in ultrapure and natural water solutions under ultraviolet (UV) light and a combination of UV and hydrogen peroxide (H₂O₂). The effect of pH on the photooxidation of the pesticides was also studied. The results indicated that under direct photolysis with monochromatic light at 253.7 nm and different conditions, the photochemical rates followed first-order kinetics, with fluence-based rate constants ranging from 9.15 × 10⁻⁴ to 6.37 × 10⁻³ cm² mJ⁻¹ and 7.63 × 10⁻³ to 1.47 × 10⁻² cm² mJ⁻¹ for bromoxynil and trifluralin, respectively. Quantum yields, in the range of 0.08-0.25 for bromoxynil and 0.12-0.72 for trifluralin, were observed in experiments using ultrapure water. The study also found that the UV/H₂O₂ process enhanced the oxidation rate in comparison to direct photolysis. A 90% degradation with UV dose of 333 and 188 mJ cm⁻² was achieved for bromoxynil and trifluralin, respectively, in natural water, in presence of 8.8 × 10⁻⁴ M H₂O₂. To assess the aquatic toxicity, the Microtox^® 81.9% screening test protocol was used before and after treatment. The test results indicated a decrease in the acute toxicity of the samples after treatment for both pesticides.     

Degradation of emergent contaminants by UV,UV/H2O2 and neutral photo-Fenton at pilot scale in a domestic wastewater treatment plant

This study focuses on the removal of 22 selected micropollutants in an effluent from a municipal wastewater treatment plant (MWTP) at pilot scale. A reactor of 37 L with five low pressure mercury lamps emitting at 254 nm (UV₂₅₄) was used. The 22 micropollutants include 15 pharmaceuticals, 2 X-Ray contrast medias, 1 corrosion inhibitor and 4 biocides/pesticides. Five of these 22 compounds were used as indicative substances as proposed by the Swiss Federal Office for the Environment (FOEN) (carbamazepine, diclofenac, sulfamethoxazole, benzotriazole and mecoprop).     

纳米TiO2光催化性能研究进展及其影响因素探讨

阐述了TiO2的光催化机理及影响TiO2光催化活性的因素,并综述了近年来TiO2光催化的改性研究方法,最后指出了纳米TiO2光催化剂的不足和研究发展的重点,以期推动纳米TiO2光催化技术的工业化进程。     

Enhance the photocatalytic activity for the degradation of organic contaminants in water by incorporating TiO2 with zero-valent iron

Titanium dioxide (TiO₂) has become the most popular photocatalyst in treating persistent organic pollutants. The main disadvantage of TiO₂ is the diminishing photocatalytic activity over time due to the electron-hole pair recombination. Many studies have aimed to prolong the photocatalytic life of TiO₂. Among them, incorporation of zero-valent iron (ZVI) is one of the approaches. In this study, a novel nano TiO₂/Fe⁰ composite (NTFC) was synthesized from a nano neutral TiO₂ sol and a nano zero-valent iron (nZVI), both prepared in our laboratory. The structure, composition and physical property of the NTFC are characterized. The photocatalytic activity of the NTFC was evaluated by the reductive decolourization of an azo dye, Acid Black-24 (AB-24), and was found superior to those of nZVI and nano neutral TiO₂ sol. Evidence suggests that the enhanced activity of NTFC is highly correlated to the ratio of ferrous to ferric ion in the system. The quantities of ferrous and ferric ions in the nZVI and NTFC systems were monitored separately. In the nZVI system, the concentration of ferric ions decreased significantly with time while a high level of ferrous ions was maintained in the NTFC suspension. The ferrous/ferric ratio of the NTFC suspension was substantially increased after irradiation by UV. Evidence from EPR analysis suggests that the excited electrons in the conduction band of the TiO₂ can be trapped by the half reaction of Fe³⁺/Fe²⁺, reducing the probability of electron-electron hole pair recombination and sustaining the catalytic life of TiO₂. Corrosion tests further proved that by incorporating TiO₂ with zero-valent iron the surface oxidation of nZVI can be effectively prevented.     

Nitrate removal by a paired electrolysis on copper and Ti/IrO2 coupled electrodes - Influence of the anode/cathode surface area ratio

In this study, nitrate removal in alkaline media by a paired electrolysis with copper cathode and Ti/IrO₂ anode enabled the conversion of nitrate to nitrogen. Optimum conditions for carrying out reduction of nitrate to ammonia and subsequent oxidation of the produced ammonia to nitrogen were found. At the copper cathode, electroreduction of nitrate to ammonia was optimal near −1.4 V vs Hg/HgO. At the Ti/IrO₂ anode, a pH value of 12, the presence of chloride and a potential fixed around 2.3 V vs Hg/HgO permitted the production of hypochlorite, leading to the oxidation of ammonia to nitrogen with a N₂ selectivity of 100%. Controlling the cathode/anode surface area ratio, and thus the current density, appeared to be a very efficient way of shifting electrode potentials to optimal values, consequently favoring the conversion of nitrate to nitrogen during a paired galvanostatic electrolysis. A cathode/anode surface area ratio of 2.25 was shown to be the most efficient to convert nitrate to nitrogen.     

Oxidation of iodide and iodine on birnessite (δ-MnO2) in the pH range 4-8

The oxidation of iodide by synthetic birnessite (δ-MnO₂) was studied in perchlorate media in the pH range 4-8. Iodine (I₂) was detected as an oxidation product that was subsequently further oxidized to iodate (IO₃⁻). The third order rate constants, second order on iodide and first order on manganese oxide, determined by extraction of iodine in benzene decreased with increasing pH (6.3-7.5) from 1790 to 3.1 M⁻² s⁻¹. Both iodine and iodate were found to adsorb significantly on birnessite with an adsorption capacity of 12.7 μM/g for iodate at pH 5.7. The rate of iodine oxidation by birnessite decreased with increasing ionic strength, which resulted in a lower rate of iodate formation. The production of iodine in iodide-containing waters in contact with manganese oxides may result in the formation of undesired iodinated organic compounds (taste and odor, toxicity) in natural and technical systems. The probability of the formation of such compounds is highest in the pH range 5-7.5. For pH <5 iodine is quickly oxidized to iodate, a non-toxic and stable sink for iodine. At pH >7.5, iodide is not oxidized to a significant extent.     

Energy use, CO2 emissions and waste throughout the life cycle of a sample of hotels in the Balearic Islands

Tourism is the most developed economic sector in the Balearic Islands. The great rise in construction activities within the last 50 years, the increase in energy use, in CO₂ emissions and in waste production due to tourism, as well as an electrical energy production system mainly based on coal and fossil fuels is not an environmentally sustainable scenario. The aim of this study is to identify the processes that have had the greatest impact on the life cycle of a tourist building. In order to do this, the energy uses, CO₂ emissions and waste materials generated have been estimated, assuming a life cycle of 50 years, within a sample of hotels from the Balearic Islands. The results show that the operating phase, which represents between 70% and 80% of the total energy use, is the one with the greatest impact; that the energy use due to the manufacture of materials represents a fifth of the total and that electric consumption is the main cause of CO₂ emissions because of the regional energy system.     

Variation in indoor particle number and PM2.5 concentrations in a radio station surrounded by busy roads before and after an upgrade of the HVAC system

Indoor particle number and PM_2.5 concentrations were investigated in a radio station surrounded by busy roads. Two extensive field measurement campaigns were conducted to determine the critical parameters affecting indoor air quality. The results indicated that indoor particle number and PM_2.5 concentrations were governed by outdoor air, and were significantly affected by the location of air intake and design of HVAC system. Prior to the upgrade of the HVAC system and relocation of the air intake, the indoor median particle number concentration was 7.4×10³ particles/cm³ and the median PM_2.5 concentration was 7 μg/m³. After the relocation of air intake and the redesign of the HVAC system, the indoor particle number concentration was between 2.3×10³ and 3.4×10³ particles/cm³, with a median value of 2.7×10³ particles/cm³, and the indoor PM_2.5 concentration was in the range of 3–5 μg/m³, with a median value of 4 μg/m³. By relocating the air intake of the HVAC, the outdoor particle number and PM_2.5 concentrations near the air intake were reduced by 35% and 55%, respectively. In addition, with the relocation of air intake and the redesign of the HVAC system, the particle number penetration rate was reduced from 42% to 14%, and the overall filtration efficiency of the HVAC system (relocation of air intake, pre-filter, AHU and particle losses in the air duct) increased from 58% to 86%. For PM_2.5, the penetration rate after the upgrade was approximately 18% and the overall filtration efficiency was 82%. This study demonstrates that by using a comprehensive approach, including the assessment of outdoor conditions and characterisation of ventilation and filtration parameters, satisfactory indoor air quality can be achieved, even for those indoor environments facing challenging outdoor air conditions.     

Coupled reservoir–geomechanical analysis of the potential for tensile and shear failure associated with CO2 injection in multilayered reservoir–caprock systems

Coupled reservoir–geomechanical simulations were conducted to study the potential for tensile and shear failure—e.g., tensile fracturing and shear slip along pre-existing fractures—associated with underground CO₂-injection in a multilayered geological system. This failure analysis aimed to study factors affecting the potential for breaching a geological CO₂-storage system and to study methods for estimating the maximum CO₂-injection pressure that could be sustained without causing such a breach. We pay special attention to geomechanical stress changes resulting from upward migration of the CO₂ and how the initial stress regime affects the potential for inducing failure. We conclude that it is essential to have an accurate estimate of the three-dimensional in situ stress field to support the design and performance assessment of a geological CO₂-injection operation. Moreover, we also conclude that it is important to consider mechanical stress changes that might occur outside the region of increased reservoir fluid pressure (e.g., in the overburden rock) between the CO₂-injection reservoir and the ground surface.