Direct evidence for base-mediated decomposition of alkyl hydroperoxides (ROOH) in the gas phase

Alkyl hydroperoxides (ROOH) are attributed a key role in the biochemical oxidation of lipids during oxidative stress.1 In this chemistry ROOH compounds, where the R groups are unsaturated fatty acids, are viewed as transient ntermediates which are readily degraded, due to the lability of the RO-OH bond, to yield potentially genotoxic aldehydes and ketones.2 Generally, the decomposition of alkyl hydroperoxides is thought to be mediated by radical abstraction or electron transfer processes usually involving enzymes, transition metals, or recently, Vitamin C.3 In this paper we present the first unambiguous experimental and computational evidence for base-mediated heterolytic decomposition of simple alkyl hydroperoxides by the mechanism outlined in Scheme 1.

Base-induced decomposition of alkyl hydroperoxides in the gas phase. Part 3. Kinetics and dynamics in HO-+CH3OOH, C2H5OOH, and tert-C4H9OOH reactions

The E-CO(2) elimination reactions of alkyl hydroperoxides proceed via abstraction of an (x-hydrogen by a base: X- + (RRHCOOH)-R-1-H-2 -> HX + (RRC)-R-1-C-2=O + HO-. Efficiencies and product distributions for the reactions of the hydroxide anion with methyl, ethyl, and tert-butyl hydroperoxides are studied in the gas phase. On the basis of experiments using three isotopic analogues, HO- + CH3OOH, HO- + CD3OOH, and H18O- + CH3OOH. the overall intrinsic reaction efficiency is determined to be 80% or greater. The E(CO)2 decomposition is facile for these methylperoxide reactions, and predominates over competing proton transfer at the hydroperoxide moiety. The CH3CH2OOH reaction displays a similar E(CO)2 reactivity, whereas proton transfer and the formation of HOO- are the exclusive pathways observed for (CH3)(3)COOH, which has no (x-hydrogen. All results are consistent with the E-CO(2) mechanism, transition state structure, and reaction energy diagrams calculated using the hybrid density functional B3LYP approach. Isotope labeling for HO- + CH3OOH also reveals some interaction between H2O and HO- within the E(CO)2 product complex [H2O center dot center dot center dot CH2=O center dot center dot center dot HO-]. There is little evidence, however. for the formation of the most exothermic products H2O + CH2(OH)O-, which would arise from nuclephilic condensation of CH2=O and HO-. The results suggest that the product dynamics are not totally statistical but are rather direct after the E-CO(2) transition state. The larger HO- + CH3CH2OOH system displays more statistical behavior during complex dissociation.

Thermal stability and decomposition kinetics of styrene-butadiene rubber nanocomposites filled with different particle sized kaolinites

A series of styrene-butadiene rubber (SBR) nanocomposites filledwith different particle sized kaolinites are prepared via a latex blending method. The thermal stabilities of these clay polymer nanocomposites (CPN) are characterized by a range of techniques including thermogravimetry (TG), digital photos, scanning electron microscopy (SEM) and Raman spectroscopy. These CPN show some remarkable improvement in thermal stability compared to that of the pure SBR. With the increase of kaolinite particle size, the residual char content and the average activation energy of kaolinite SBR nanocomposites all decrease; the pyrolysis residues become porous; the crystal carbon in the pyrolysis residues decrease significantly from 58.23% to 44.41%. The above results prove that the increase of kaolinite particle size is not beneficial in improving the thermal stability of kaolinite SBR nanocomposites.

The relationship between N2O, NO, and N2 fluxes from fertilized and irrigated dryland soils of the Aral Sea Basin, Uzbekistan

Microbial respiratory reduction of nitrous oxide (N2O) to dinitrogen (N2) via denitrification plays a key role within the global N-cycle since it is the most important process for converting reactive nitrogen back into inert molecular N2. However, due to methodological constraints, we still lack a comprehensive, quantitative understanding of denitrification rates and controlling factors across various ecosystems. We investigated N2, N2O and NO emissions from irrigated cotton fields within the Aral Sera Basin using the He/O2 atmosphere gas flow soil core technique and an incubation assay. NH4NO3 fertilizer, equivalent to 75 kg ha−1 and irrigation water, adjusting the water holding capacity to 70, 100 and 130% were applied to the incubation vessels to assess its influence on gaseous N emissions. Under soil conditions as they are naturally found after concomitant irrigation and fertilization, denitrification was the dominant process and N2 the main end product of denitrification. The mean ratios of N2/N2O emissions increased with increasing soil moisture content. N2 emissions exceeded N2O emissions by a factor of 5 ± 2 at 70% soil water holding capacity (WHC) and a factor of 55 ± 27 at 130% WHC. The mean ratios of N2O/NO emissions varied between 1.5 ± 0.4 (70% WHC) and 644 ± 108 (130% WHC). The magnitude of N2 emissions for irrigated cotton was estimated to be in the range of 24 ± 9 to 175 ± 65 kg-N ha−1season−1, while emissions of NO were only of minor importance (between 0.1 to 0.7 kg-N ha−1 season−1). The findings demonstrate that for irrigated dryland soils in the Aral Sera Basin, denitrification is a major pathway of N-loss and that substantial amounts of N-fertilizer are lost as N2 to the atmosphere for irrigated dryland soils.

Decomposition analysis of air pollution abatement in China: empirical study for ten industrial sectors from 1998 to 2009

This study analyzes the management of air pollutant substance in Chinese industrial sectors from 1998 to 2009. Decomposition analysis applying the logarithmic mean divisia index is used to analyze changes in emissions of air pollutants with a focus on the following five factors: coal pollution intensity (CPI), end-of-pipe treatment (EOP), the energy mix (EM), productive efficiency change (EFF), and production scale changes (PSC). Three pollutants are the main focus of this study: sulfur dioxide (SO2), dust, and soot. The novelty of this paper is focusing on the impact of the elimination policy on air pollution management in China by type of industry using the scale merit effect for pollution abatement technology change. First, the increase in SO2 emissions from Chinese industrial sectors because of the increase in the production scale is demonstrated. However, the EOP equipment that induced this change and improvements in energy efficiency has prevented an increase in SO2 emissions that is commensurate with the increase in production. Second, soot emissions were successfully reduced and controlled in all industries except the steel industry between 1998 and 2009, even though the production scale expanded for these industries. This reduction was achieved through improvements in EOP technology and in energy efficiency. Dust emissions decreased by nearly 65% between 1998 and 2009 in the Chinese industrial sectors. This successful reduction in emissions was achieved by implementing EOP technology and pollution prevention activities during the production processes, especially in the cement industry. Finally, pollution prevention in the cement industry is shown to result from production technology development rather than scale merit. © 2013 Elsevier Ltd. All rights reserved.

Decomposition of toxic chemical substance management in three U.S. manufacturing sectors from 1991 to 2008

This study analyzes toxic chemical substance management in three U.S. manufacturing sectors from 1991 to 2008. Decomposition analysis applying the logarithmic mean Divisia index is used to analyze changes in toxic chemical substance emissions by the following five factors: cleaner production, end-of-pipe treatment, transfer for further management, mixing of intermediate materials, and production scale. Based on our results, the chemical manufacturing sector reduced toxic chemical substance emissions mainly via end-of-pipe treatment. In the meantime, transfer for further management contributed to the reduction of toxic chemical substance emissions in the metal fabrication industry. This occurred because the environmental business market expanded in the 1990s, and the infrastructure for the recycling of metal and other wastes became more efficient. Cleaner production is the main contributor to toxic chemical reduction in the electrical product industry. This implies that the electrical product industry is successful in developing a more environmentally friendly product design and production process.

Decomposition of the environmental Kuznets curve : scale, technique, and composition effects

This study decomposed the determinants of environmental quality into scale, technique, and composition effects. We applied a semiparametric method of generalized additive models, which enabled us to use flexible functional forms and include several independent variables in the model. The differences in the technique effect were found to play a crucial role in reducing pollution. We found that the technique effect was sufficient to reduce sulfur dioxide emissions. On the other hand, its effect was not enough to reduce carbon dioxide (CO2) emissions and energy use, except for the case of CO2 emissions in high-income countries.

Insight into the thermal decomposition of kaolinite intercalated with potassium acetate : an evolved gas analysis

The thermal decomposition process of kaolinite–potassium acetate intercalation complex has been studied using simultaneous thermogravimetry coupled with Fourier-transform infrared spectroscopy and mass spectrometry (TG-FTIR-MS). The results showed that the thermal decomposition of the complex took place in four temperature ranges, namely 50–100, 260–320, 320–550, and 650–780 °C. The maximal mass losses rate for the thermal decomposition of the kaolinite–potassium acetate intercalation complex was observed at 81, 296, 378, 411, 486, and 733 °C, which was attributed to (a) loss of the adsorbed water, (b) thermal decomposition of surface-adsorbed potassium acetate (KAc), (c) the loss of the water coordinated to potassium acetate in the intercalated kaolinite, (d) the thermal decomposition of intercalated KAc in the interlayer of kaolinite and the removal of inner surface hydroxyls, (e) the loss of the inner hydroxyls, and (f) the thermal decomposition of carbonate derived from the decomposition of KAc. The thermal decomposition of intercalated potassium acetate started in the range 320–550 °C accompanied by the release of water, acetone, carbon dioxide, and acetic acid. The identification of pyrolysis fragment ions provided insight into the thermal decomposition mechanism. The results showed that the main decomposition fragment ions of the kaolinite–KAc intercalation complex were water, acetone, carbon dioxide, and acetic acid. TG-FTIR-MS was demonstrated to be a powerful tool for the investigation of kaolinite intercalation complexes. It delivers a detailed insight into the thermal decomposition processes of the kaolinite intercalation complexes characterized by mass loss and the evolved gases.

Turbulence measurements in a shallow tidal estuary : analysis based on triple decomposition

In an estuary, mixing and dispersion are the result of the combination of large scale advection and small scale turbulence which are both complex to estimate. A field study was conducted in a small sub-tropical estuary in which high frequency (50 Hz) turbulent data were recorded continuously for about 48 hours. A triple decomposition technique was introduced to isolate the contributions of tides, resonance and turbulence in the flow field. A striking feature of the data set was the slow fluctuations which exhibited large amplitudes up to 50% the tidal amplitude under neap tide conditions. The triple decomposition technique allowed a characterisation of broader temporal scales of high frequency fluctuation data sampled during a number of full tidal cycles.

Analysing the similarity of proteins based on a new approach to empirical mode decomposition

The function of a protein can be partially determined by the information contained in its amino acid sequence. It can be assumed that proteins with similar amino acid sequences normally have closer functions. Hence analysing the similarity of proteins has become one of the most important areas of protein study. In this work, a layered comparison method is used to analyze the similarity of proteins. It is based on the empirical mode decomposition (EMD) method, and protein sequences are characterized by the intrinsic mode functions (IMFs). The similarity of proteins is studied with a new cross-correlation formula. It seems that the EMD method can be used to detect the functional relationship of two proteins. This kind of similarity method is a complement of traditional sequence similarity approaches which focus on the alignment of amino acids

Rainfall variability drives interannual variation in N2O emissions from a humid, subtropical pasture

Variations in interannual rainfall totals can lead to large uncertainties in annual N2O emission budget estimates from short term field studies. The interannual variation in nitrous oxide (N2O) emissions from a subtropical pasture in Queensland, Australia, was examined using continuous measurements of automated chambers over 2 consecutive years. Nitrous oxide emissions were highest during the summer months and were highly episodic, related more to the size and distribution of rain events than soil water content. Over 48% of the total N2O emitted was lost in just 16% of measurement days. Interannual variation in annual N2O estimates was high, with cumulative emissions increasing with decreasing rainfall. Cumulative emissions averaged 1826.7 ± 199.9 g N2O-N ha−1 yr−1 over the two year period, though emissions from 2008 (2148 ± 273 g N2O-N ha−1 yr−1) were 42% higher than 2007 (1504 ± 126 g N2O-N ha−1 yr−1). This increase in annual emissions coincided with almost half of the summer precipitation from 2007 to 2008. Emissions dynamics were chiefly driven by the distribution and size of rain events which varied on a seasonal and annual basis. Sampling frequency effects on cumulative N2O flux estimation were assessed using a jackknife technique to inform future manual sampling campaigns. Test subsets of the daily measured data were generated for the pasture and two adjacent land-uses (rainforest and lychee orchard) by selecting measured flux values at regular time intervals ranging from 1 to 30 days. Errors associated with weekly sampling were up to 34% of the sub-daily mean and were highly biased towards overestimation if strategically sampled following rain events. Sampling time of day also played a critical role. Morning sampling best represented the 24 hour mean in the pasture, whereas sampling at noon proved the most accurate in the shaded rainforest and lychee orchard.