Cyclohexane oxidation and carbon deposition over metal oxide catalysts

Catalytic activity of V, Mn, Ni, Cu, Zn, Mo, Zr and Ce oxides over an -alumina support was evaluated for cyclohexane oxidation under oxygen deficient conditions in order to understand the relation between carbon deposition and catalytic activity/selectivity. Carbon formation over the catalysts during the oxidation reaction was measured by means of Fourier transformed infrared spectroscopy (FTIR). Catalysts Mn/Al₂O₃ and Ce/Al₂O₃, which are selective for deep oxidation of cyclohexane, possessed relatively carbon free surfaces. The catalysts with relatively high carbon deposition (V, Ni, Cu, Zn, Mo and Zr) produced CO in addition to CO₂. Traces of formaldehyde were produced over the catalysts Mo and V.     

Blue carbon in human-dominated estuarine and shallow coastal systems

Estuarine and shallow coastal systems (ESCS) are recognized as not only significant organic carbon reservoirs but also emitters of CO₂ to the atmosphere through air–sea CO₂ gas exchange, thus posing a dilemma on ESCS’s role in climate change mitigation measures. However, some studies have shown that coastal waters take up atmospheric CO₂ (C_atm), although the magnitude and determinants remain unclear. We argue that the phenomenon of net uptake of C_atm by ESCS is not unusual under a given set of terrestrial inputs and geophysical conditions. We assessed the key properties of systems that show the net C_atm uptake and found that they are often characteristic of human-dominated systems: (1) input of high terrestrial nutrients, (2) input of treated wastewater in which labile carbon is highly removed, and (3) presence of hypoxia. We propose that human-dominated ESCS are worthy of investigation as a contributor to climate change mitigation.     

COS,CS2 and SO2 in aluminium smelter exhaust

Measurements of carbonyl sulfide (COS) and carbondisulfide (CS₂) were carried out on samples drawn from a smoke stack of an aluminium smelter. Volume mixing ratios of 6 ppm COS and 0.1 ppm CS₂ were measured for gases from the electrolysis unit that had previously passed an Al₂O₃ fluid bed reactor and electrostatic precipitators. Specific emissions of 1.6 kg COS and 0.03 kg CS₂ per ton of primary aluminium were found. Extrapolating from this particular smelter’s conditions to a world mix specific COS emissions of about 4 kg/t(Al) are calculated resulting in emissions of annually 0.08 Tg COS into the atmosphere due to electrolytic aluminium production in 1995. Besides the photochemical conversion of anthropogenic CS₂ aluminium production is established to be the second major industrial source of COS probably exceeding automotive tire wear’s and coal combustion’s contributions.     

Monitoring trichloroethene remediation at an iron permeable reactive barrier using stable carbon isotopic analysis

Stable carbon isotopic analysis, in combination with compositional analysis, was used to evaluate the performance of an iron permeable reactive barrier (PRB) for the remediation of ground water contaminated with trichloroethene (TCE) at Spill Site 7 (SS7), F.E. Warren Air Force Base, Wyoming. Compositional data indicated that although the PRB appeared to be reducing TCE to concentrations below treatment goals within and immediately downgradient of the PRB, concentrations remained higher than expected at wells further downgradient (i.e. >9 m) of the PRB. At two wells downgradient of the PRB, TCE concentrations were comparable to upgradient values, and delta13C values of TCE at these wells were not significantly different than upgradient values. Since the process of sorption/desorption does not significantly fractionate carbon isotope values, this suggests that the TCE observed at these wells is desorbing from local aquifer materials and was present before the PRB was installed. In contrast, three other downgradient wells show significantly more enriched delta13C values compared to the upgradient mean. In addition, delta13C values for the degradation products of TCE, cis-dichloroethene and vinyl chloride, show fractionation patterns expected for the products of the reductive dechlorination of TCE. Since concentrations of both TCE and degradation products drop to below detection limit in wells within the PRB and directly below it, these downgradient chlorinated hydrocarbon concentrations are attributed to desorption from local aquifer material. The carbon isotope values indicate that this dissolved contaminant is subject to local degradation, likely due to in situ microbial activity.     

Stable isotope signatures reflect competitiveness between trees under changed CO2/O3 regimes

Here we synthesize key findings from a series of experiments to gain new insight on inter-plant competition between juvenile beech (Fagus sylvatica) and spruce (Picea abies) under the influence of increased O₃ and CO₂ concentrations. Competitiveness of plants was quantified and mechanistically interpreted as space-related resource investments and gains. Stable isotopes were addressed as temporal integrators of plant performance, such as photosynthesis and its relation to water use and nitrogen uptake. In the weaker competitor, beech, efficiency in space-related aboveground resource investment was decreased in competition with spruce and positively related to Δ¹³C, as well as stomatal conductance, but negatively related to δ¹⁸O. Likewise, our synthesis revealed that strong belowground competition for water in spruce was paralleled in this species by high N assimilation capacity. We suggest combining the time-integrative potential of stable isotopes with space-related investigations of competitiveness to accomplish mechanistic understanding of plant competition for resources.     

Selective redox degradation of chlorinated aliphatic compounds by Fenton reaction in pyrite suspension

Selective redox degradation of chlorinated aliphatics by Fenton reaction in pyrite suspension was investigated in a closed system. Carbon tetrachloride (CT) was used as a representative target of perchlorinated alkanes and trichloroethylene (TCE) was used as one of highly chlorinated alkenes. Degradation of CT in Fenton reaction was significantly enhanced by pyrite used as an iron source instead of soluble Fe. Pyrite Fenton showed 93% of CT removal in 140 min, while Fenton reaction with soluble Fe(II) showed 52% and that with Fe(III) 15%. Addition of 2-propanol to the pyrite Fenton system significantly inhibited degradation of TCE (99% to 44% of TCE removal), while degradation of CT was slightly improved by the 2-propanol addition (80-91% of CT removal). The result suggests that, unlike oxidative degradation of TCE by hydroxyl radical in pyrite Fenton system, an oxidation by the hydroxyl radical is not a main degradation mechanism for the degradation of CT in pyrite Fenton system but a reductive dechlorination by superoxide can rather be the one for the CT degradation. The degradation kinetics of CT in the pyrite Fenton system was decelerated (0.13-0.03 min⁻¹), as initial suspension pH decreased from 3 to 2. The formation of superoxide during the CT degradation in the pyrite Fenton system was observed by electron spin resonance spectroscopy. The formation at initial pH 3 was greater than that at initial pH 2, which supported that superoxide was a main reductant for degradation of CT in the pyrite Fenton system.     

Adsorption of fulvic acid by carbon nanotubes from water

This study investigated adsorption of fulvic acid (FA) by single-walled (SWCNT) and multi-walled carbon nanotubes (MWCNT) and activated carbon. Adsorption of FA depends greatly on the adsorbent surface area and solution pH. SWCNT has higher adsorption than MWCNT and activated carbon. Lower E4/E6 (absorbance at 465 nm to that at 665 nm) and higher E2/E3 (absorbance at 250 nm to that at 365 nm) ratios of the residual FA in solution after adsorption than that of original FA in low pH ranges suggest that aromatic rich FA fractions with polar moieties readily adsorb on the adsorbents. The apparent interaction mechanisms between FA and CNT surfaces include electrostatic, hydrophobic, π-π and hydrogen-bond interactions. FA adsorption was reduced greatly with increasing pH because of the increase of electrostatic repulsion and the decrease of hydrophobic and hydrogen-bond interactions.     

微环境新风量的检测原理及方法研究

新风量是评价室内微环境空气卫生质量的主要卫生指标之一,也是计算室内某种气体单位时间排放量的重要参数。以CO2作为示踪气体,利用于冰升华和人体呼吸产生CO2示踪气体两种测量方法对室内和车内微环境进行了检测,并考虑室内人呼出CO2量的影响,运用箱子模式的各种推导公式（稳态法、解析解法和差分法）对新风量进行了计算,并对结果进行了讨论。结果表明,没有人存在下,用箱子模式的解析解法和差分法计算的新风量值没有明显的统计差异;微环境内有人时必须考虑人释放的影响,这样箱子模式的各种推导公式都可以计算新风量值,且结果准确,准确度高。利用人体呼吸产生CO2示踪气体法,用差分法计算结果不理想,偏差很大;用稳态法计算重现性高,结果可靠。     

Response of stable carbon isotope in epilithic mosses to atmospheric nitrogen deposition

Epilithic mosses are characterized by insulation from substratum N and hence meet their N demand only by deposited N. This study investigated tissue C, total Chl and δ¹³C of epilithic mosses along 2 transects across Guiyang urban (SW China), aiming at testing their responses to N deposition. Tissue C and total Chl decreased from the urban to rural, but δ¹³C_moss became less negative. With measurements of atmospheric CO₂ and δ¹³CO₂, elevated N deposition was inferred as a primary factor for changes in moss C and isotopic signatures. Correlations between total Chl, tissue C and N signals indicated a nutritional effect on C fixation of epilithic mosses, but the response of δ¹³C_moss to N deposition could not be clearly differentiated from effects of other factors. Collective evidences suggest that C signals of epilithic mosses are useful proxies for N deposition but further works on physiological mechanisms are still needed.     

火化过程中二噁英类污染物减排技术研究

为减少火化过程中二噁英类污染物的排放,研究了"热交换器 布袋除尘器 活性炭纤维毡"三级组合对火化遗体烟气中二噁英类污染物的去除效果.利用急冷技术将二次燃烧室排出的火化烟气温度降到90～130℃.实验表明,布袋除尘器去除火化烟气中二噁英类污染物的效率为57.4%;布袋除尘器分别与厚度为5、15 mm的活性炭纤维毡组合去除火化烟气中二噁英类污染物的效率分别为64.0%和89.2%.