Microbial degradation of methyl tert-butyl ether and tert-butyl alcohol in the subsurface

The fate of fuel oxygenates such as methyl tert-butyl ether (MTBE) in the subsurface is governed by their degradability under various redox conditions. The key intermediate in degradation of MTBE and ethyl tert-butyl ether (ETBE) is tert-butyl alcohol (TBA) which was often found as accumulating intermediate or dead-end product in lab studies using microcosms or isolated cell suspensions. This review discusses in detail the thermodynamics of the degradation processes utilizing various terminal electron acceptors, and the aerobic degradation pathways of MTBE and TBA. It summarizes the present knowledge on MTBE and TBA degradation gained from either microcosm or pure culture studies and emphasizes the potential of compound-specific isotope analysis (CSIA) for identification and quantification of degradation processes of slowly biodegradable pollutants such as MTBE and TBA. Microcosm studies demonstrated that MTBE and TBA may be biodegradable under oxic and nearly all anoxic conditions, although results of various studies are often contradictory, which suggests that site-specific conditions are important parameters. So far, TBA degradation has not been shown under methanogenic conditions and it is currently widely accepted that TBA is a recalcitrant dead-end product of MTBE under these conditions. Reliable in situ degradation rates for MTBE and TBA under various geochemical conditions are not yet available. Furthermore, degradation pathways under anoxic conditions have not yet been elucidated. All pure cultures capable of MTBE or TBA degradation isolated so far use oxygen as terminal electron acceptor. In general, compared with hydrocarbons present in gasoline, fuel oxygenates biodegrade much slower, if at all. The presence of MTBE and related compounds in groundwater therefore frequently limits the use of in situ biodegradation as remediation option at gasoline-contaminated sites. Though degradation of MTBE and TBA in field studies has been reported under oxic conditions, there is hardly any evidence of substantial degradation in the absence of oxygen. The increasing availability of field data from CSIA will foster our understanding and may even allow the quantification of degradation of these recalcitrant compounds. Such information will help to elucidate the crucial factors of site-specific biogeochemical conditions that govern the capability of intrinsic oxygenate degradation.     

几种湿式烟气脱硫吸收反应的热力学分析

计算了３种湿式烟气脱硫吸收反应达到平衡态时ＳＯ２的分压力。计算结果显示：对于３种湿式脱硫反应，平衡态ＳＯ２的分压力都随温度的升高而增大。所以从化学热力学角度看反应温度高不利于脱硫。综合考虑脱硫效率、运行费用、是否堵塞等因素，推荐采用双碱法进行烟气脱硫。     

Effect of initial temperature on the explosion pressure of various liquid fuels and their blends

In this work, the effect of initial temperature on the explosion pressure, P_ex, of various liquid fuels (isooctane, toluene and methanol) and their blends (isooctane-toluene and methanol-toluene, with three different fuel-fuel ratios) was investigated by performing experiments in a 20-l sphere at different concentrations of vaporized fuel in air. The initial temperature was varied from 333 K to 413 K.Results show that, as the fuel-air equivalence ratio, Φ, is increased, a transition occurs from a “thermodynamics-driven” explosion regime to a “radiant heat losses-driven” explosion regime. The maximum pressure, P_max, is found in the former regime (Φ < 3), which is characterized by a trend of decreasing P_ex with increasing initial temperature. This trend has been explained by thermodynamics. In the latter regime (Φ > 3), P_ex increases with increasing initial temperature. This trend has been addressed to the decrease in emissivity (and, thus, radiant heat losses) with the increase in temperature.     

改性聚乙烯醇吸附镍离子的动力学与热力学研究

研究了自制改性聚乙烯醇对Ni~(2+)的吸附行为,在不同的吸附条件下,探讨相关因素的影响,并对实验数据进行动力学与热力学的拟合。结果表明,室温下,在溶液p H=6.0,NaNO_3的浓度为0.1 mol/L,吸附时间为60 min,液固比为250 m L/g,改性聚乙烯醇对浓度为0.1 mol/L Ni2+的吸附效果好,去除率达到98.05%;当干扰因子设定为0.1 mol/L的Ca(NO_3)_2,对Ni2+的去除率降到59.29%。改性聚乙烯醇对Ni2+的吸附动力学符合准二级动力学方程;Langmuir等温模型的拟合度较高,推测改性聚乙烯醇表面是均一的等质体,计算的最大吸附量为1.35 mmol/g,与实验结果一致;D-R等温模型的拟合度次之,在各温度下,E16 k J/mol,说明改性聚乙烯醇对Ni2+的吸附是以化学吸附为主。通过Van’t Hoff方程的拟合,计算得到的吉布斯自由能以及熵变和焓变表明该吸附过程为吸热化学反应。     

Abatement of SO2-NOx binary gas mixtures using a ferruginous active absorbent: Part I. Synergistic effects and mechanism

A novel ferruginous active absorbent, prepared by fly ash, industrial lime and the additive Fe(VI), was introduced for synchronous abatement of binary mixtures of SO2–NOx from simulated coal-fired flue gas. The synergistic action of various factors on the absorption of SO2 and NOx was investigated. The results show that a strong synergistic effect exists between Fe(VI) dose and reaction temperature for the desulfurization. It was observed that in the denitration process, the synergy of Fe(VI) dose and Ca/(S + N) had the most significant impact on the removal of NO, followed by the synergy of Fe(VI) and reaction temperature, and then the synergy of reaction temperature and flue gas humidity. A scanning electron microscope(SEM) and an accessory X-ray energy spectrometer(EDS)were used to observe the surface characteristics of the raw and spent absorbent as well as fly ash. A reaction mechanism was proposed based on chemical analysis of sulfur and nitrogen species concentrations in the spent absorbent. The Gibbs free energy, equilibrium constants and partial pressures of the SO2–NOx binary system were determined by thermodynamics.     

Assessing self-organization of plant communities—A thermodynamic approach

Thermodynamics is a powerful tool for the study of system development and has the potential to be applied to studies of ecological complexity. Here, we develop a set of thermodynamic indicators including energy capture and energy dissipation to quantify plant community self-organization. The study ecosystems included a tropical seasonal rainforest, an artificial tropical rainforest, a rubber plantation, and two Chromolaena odorata (L.) R.M. King & H. Robinson communities aged 13 years and 1 year. The communities represent a complexity transect from primary vegetation, to transitional community, economic plantation, and fallows and are typical for Xishuangbanna, southwestern China. The indicators of ecosystem self-organization are sensitive to plant community type and seasonality, and demonstrate that the tropical seasonal rainforest is highly self-organized and plays an important role in local environmental stability via the land surface thermal regulation. The rubber plantation is at a very low level of self-organization as quantified by the thermodynamic indicators, especially during the dry season. The expansion of the area of rubber plantation and shrinkage of tropical seasonal rainforest would likely induce local surface warming and a larger daily temperature range.     

厌氧条件下硝基苯降解的可行性研究

本文研究了在厌氧条件下硝基苯降解成低级产物甲烷等的可行性,对几种降解途径进行了热力学计算,通过计算和实验,得出硝基苯在厌氧条件下可以降解为甲烷等低级产物。     

Self-organization of tropical seasonal rain forest in southwest China

How to measure development of ecosystems is both a theoretical and practical question in ecology. Species richness and biomass accumulation are familiar figures of merit, but they cannot be instant watched. Self-organization is a tacit character. However, methods to measure the degree of self-organization of ecosystem are problematic. To this end Lin et al. (2009) have devised indicators of energy capture and dissipation so that self-organization defined via maximum energy dissipation can be quantified easily. Here the method is used to analyze long-term data (2004-2006) of a tropical seasonal rain forest included in the ChinaFLUX program. Three years of average self-organization values were clearly separated by seasonal variation. Reflection and long wave radiation are the main two pathways of energy loss. For tropical seasonal rain forest studied, long wave radiation contributed most to energy loss, and was negatively correlated with energy capture ability (Rn/DR). The nocturnal difference between canopy and air temperatures had a strong negative correlation with the long wave radiation loss ratio. However, the long wave radiation loss ratio was slightly lower than the reflection loss ratio in rainy season, when values were very low. Precipitation and wind had significant impact on energy dissipation ability in the hot dry season, but the correlation coefficients between precipitation and wind with thermal response numbers (TRNs) were very low. The results indicated that the self-organization estimation system based on “maximum energy dissipation theory” is applicable for tropical forest.     

Thermal degradation characteristics,kinetics and thermodynamics of micron-sized PMMA in oxygenous atmosphere using thermogravimetry and deconvolution method based on Gauss function

Micron-sized poly (methyl methacrylate) (PMMA) with high flammability is widely applied in industries, constructions and transportations. Study on the thermal degradation behaviors of micron-sized PMMA in oxygenous atmosphere, which receives scarce attention to date, can provide valuable guidance for the prevention and mitigation of injuries and damages arising from the micron-sized PMMA dust explosions and fires. In the present study, the thermal degradation characteristics of micron-sized PMMA in air were investigated by thermogravimetry. Deconvolution method using Gauss function coupled with model-free and model-fitting methods was employed to conduct the kinetic modeling. The values of thermodynamic parameters (ΔH, ΔG and ΔS) were estimated. The results indicated that one peak and one shoulder occurred in the mass loss rate (MLR) variations of the micron-sized PMMA degradation in air. The values of MLR at peak and shoulder both decreased with heating rate. Besides, the average value of the MLR varied little with heating rate. The values of MLR at the peak and the average MLR of micron-sized PMMA degradation in air were both less than those of the traditional-sized PMMA degradation in air. The calculated kinetic parameters can be used to well predict the thermal degradation behaviors of micron-sized PMMA in air. Additionally, the micron-sized PMMA in air was easier to decompose than the traditional-sized PMMA in air. Non-spontaneous reactions were involved in the thermo-oxidative degradation of micron-sized PMMA. Besides, with the progressing of thermo-oxidative degradation, less energy was required and pyrolytic products with well-ordered structures may be generated.