Mechanism for sonochemical reduction of Au(III) in aqueous butanol solution under Ar based on the analysis of gaseous and water-soluble products.

When an aqueous Au(III) solution containing 1-butanol was sonicated under Ar, Au(III) was reduced to Au(0) to form Au particles. This is because various reducing species are formed during sonication, but the reactivity of these species has not yet been evaluated in detail. Therefore, in this study, we analyzed the effects of Au(III) on the rates of the formation of gaseous and water-soluble compounds (CH4, C2H6, C2H4, C2H2, CO, CO2, H2, H2O2, and aldehydes), and the rate of Au(III) reduction as a function of 1-butanol concentration. The following facts were recognized: 1) for Au(III) reduction, the contribution of the radicals formed by the pyrolysis of 1-butanol was higher than that of the secondary radicals formed by the abstraction reactions of 1-butanol with ·OH, 2) ·CH3 and CO acted as reductants, 3) the contribution of ·H to Au(III) reduction was small in the presence of 1-butanol, 4) aldehydes and H2 did not act as reductants, and 5) the types of species that reduced Au(III) changed with 1-butanol concentration.

Sonochemistry of aqueous NaAuCl4 solutions with C3-C6 alcohols under a noble gas atmosphere.

The effect of the type of C3-C6 alcohol, solution temperature, and dissolved gas on the rate of Au(III) reduction was investigated in NaAuCl4 aqueous alcohol solution with a 200-kHz ultrasound irradiation system. It was confirmed in the presence of C3-C6 alcohol that more highly hydrophobic alcohols more effectively accumulated at the argon bubble interface region, and the reducing radicals formed here. To avoid changes in the bubble temperature during collapsing bubble, the effects of the solution temperature on the rate of Au(III) reduction and on the rate of formation of the gaseous compounds (CO, CO2, CH4, C2H2, C2H4, C2H6) were investigated in the presence of low concentration (1.0-mM) of 1-hexanol. Both of the rates showed a good relationship with the gas solubility: the amount of dissolved gas at different solution temperatures affected the number of high-temperature bubbles formed. The changes in the concentrations of the gaseous compounds formed from 1-hexanol degradation suggested that CO and the pyrolysis radicals acted as reductants. Finally, the effect of the type of dissolved gas was investigated in the presence of 1.0-mM Au(III) and 1.0-mM 1-hexanol. The rates of 1-hexanol degradation, Au(III) reduction, and gaseous compound formation increased in the order He

New System for Measuring the Photochemical Ozone Production Rate in the Atmosphere.

We have developed a new system for measuring photochemical ozone production rates in the atmosphere. Specifically, the system measures the net photochemical oxidant (Ox: the sum of ozone (O3) and nitrogen dioxide (NO2)) production rates (P-L(Ox)). Measuring Ox avoids issues from perturbations to the photostationary states between nitrogen oxides (NOx) and O3. This system has "reaction" and "reference" chambers. Ambient air is introduced into both chambers, and Ox is photochemically produced in the reaction chamber and not generated in the reference chamber. Air from the chambers is alternately introduced into an NO-reaction (NO: nitric oxide) tube to convert O3 to NO2, and then the Ox concentration is measured as NO2 using a laser-induced fluorescence technique. P-L(Ox) was obtained by dividing the difference in Ox concentrations between air samples from the two chambers by the mean residence time of the air in the reaction chamber. In this study, the P-L(Ox) measurement system was characterized, and the current detection limit of P-L(Ox) was determined to be 0.54 ppbv h-1 with an integration time of 60 s (S/N = 2), assuming an ambient Ox concentration of 100 ppbv. Field measurements of P-L(Ox) were conducted using the system at a remote forest location.

Thermal dissociation cavity attenuated phase shift spectroscopy for continuous measurement of total peroxy and organic nitrates in the clean atmosphere.

A thermal dissociation cavity attenuated phase shift spectroscopy (TD-CAPS) instrument was developed for measuring total peroxy nitrates (PNs) and organic nitrates (ONs) concentrations in the clean atmosphere. This instrument is easy to operate and can be applied to continuous measurement of PNs and ONs. A continuously measurable system is convenient to perform observations, especially in remote areas. Three lines (NO2, PNs, and ONs lines) were used for thermal dissociation. The NO2 line contains a quartz tube that is not heated, while the PN and ON lines contain quartz tubes that are heated at 433 K and 633 K, respectively. The concentrations of NO2, NO2 + PNs, and NO2 + PNs + ONs can be obtained from the NO2, PN, and ON lines, respectively. The lower limit values of the detection limit (3σ) for PNs and ONs were estimated to be 21 parts per trillion by volume with an integration time of 2 min. PNs were selectively thermally decomposed in the PNs line and formed NO2 quantitatively. In the ONs line, both PNs and ONs were thermally decomposed to produce NO2 quantitatively, but partial decomposition of HNO3 at 633 K interfered with the ONs measurement. Therefore, a HNO3 scrubber is required before the ONs line. Continuous observations were conducted with the TD-CAPS instrument in a remote area, and the instrument performed well for obtaining PNs and ONs concentrations.

Direct measurement system of nitrogen dioxide in the atmosphere using a blue light-emitting diode induced fluorescence technique.

An instrument for measuring atmospheric nitrogen dioxide has been developed by a light-emitting diode induced fluorescence (LED-IF) technique. Air was introduced into a fluorescence detection cell. A pulsed blue light LED with a peak wavelength of 430 nm was irradiated to excite NO2 molecules in this cell. Fluorescence emitted from excited NO2 molecules was detected by a dynode-gated photomultiplier tube. The current detection limit of the LED-IF instrument was estimated to be 7.0 and 0.91 ppbv (parts per billion by volume) at 1-min and 1-h integration times, respectively, with a signal to noise ratio of 2. This result indicates that this LED-IF instrument can measure sufficiently precise 1-h values of NO2 concentrations in the urban atmosphere. An NO2 test observation and an intercomparison of the LED-IF instrument with an NO2 measurement system based on a photolytic converter/NO-O3 chemiluminescence method were performed in the urban atmosphere. Concentration differences between the two methods were within ±25% for about 90% of the data. It has been demonstrated by these observations that NO2 concentrations can be observed in the urban areas using the LED-IF instrument.

Transboundary secondary organic aerosol in western Japan indicated by the δ13C of water-soluble organic carbon and the m/z 44 signal in organic aerosol mass spectra.

The stable carbon isotope ratio (δ13C) of low-volatile water-soluble organic carbon (LV-WSOC) was measured in filter samples of total suspended particulate matter, collected every 24 h in the winter of 2010 at an urban site and two rural sites in western Japan. Concentrations of the major chemical species in fine aerosol (<1.0 µm) were also measured in real time by aerosol mass spectrometers. The oxidation state of organic aerosol was evaluated using f44; i.e., the proportion of the signal at m/z 44 (CO2+ ions from the carboxyl group) to the sum of all m/z signals in the organic mass spectra. A strong correlation between LV-WSOC and m/z 44 concentrations was observed, which suggested that LV-WSOC was likely to be associated with carboxylic acids in fine aerosol. Plots of δ13C of LV-WSOC versus f44 showed random variation at the urban site and systematic trends at the rural sites. The systematic trends qualitatively agreed with a simple binary mixture model of secondary organic aerosol with background LV-WSOC with an f44 of ∼0.08 and δ13C of -17‰ or higher. Comparison with reference values suggested that the source of background LV-WSOC was likely to be primary emissions associated with C4 plants.

Ultrasound assisted production of fatty acid methyl esters from transesterification of triglycerides with methanol in the presence of KOH catalyst: optimization, mechanism and kinetics.

Ultrasound assisted transesterification of triglycerides (TG) with methanol in the presence of KOH catalyst was investigated, where the changes in the reactants and products (diglycerides (DG), monoglycerides (MG), fatty acid methyl esters (FAME) and glycerin (GL)) concentrations were discussed to understand the reaction mechanism and kinetics under ultrasound irradiation. The optimum reaction condition for the FAME production was the concentration of KOH 1.0 wt.%, molar ratio of TG to methanol of 1:6, and irradiation time of 25 min. The rate constants during the TG transesterification with methanol into GL and FAME were estimated by a curve fitting method with simulated curves to the obtained experimental results. The rate constants of [Formula: see text] were estimated to be 0.21, 0.008, 0.23, 0.005, 0.14 and 0.001 L mol(-1)min(-1), respectively. The rate determining step for the TG transesterification with methanol into GL and FAME was the reaction of MG with methanol into GL and FAME.

Prediction of rate constants for the gas phase reactions of triphenylene with OH and NO3 radicals using a relative rate method in CCl4 liquid phase-system.

The kinetics of CCl(4) liquid-phase reactions of ten kinds of polycyclic aromatic compounds (PACs) including triphenylene (TP) with NO(3) radicals have been investigated at 273K by a relative rate method using naphthalene (NA) as a reference compound. The obtained relative reaction rates of the tested PACs to NA in CCl(4) were as follows: 2.57±0.24 (acenaphthene), 2.11±0.30 (2,3-dimethylnaphthalene), 1.21±0.13 (fluoranthene), 0.56±0.07 (fluorene), 1.85±0.19 (1-methylnaphthalene), 1.77±0.12 (2-methylnaphthalene), 0.11±0.03 (1-nitronaphthalene), 1.59±0.23 (phenanthrene), 2.40±0.29 (pyrene), 0.22±0.04 (TP). TP is a semi-volatile PAC with four aromatic rings and it is chemically changed into mutagenic 2-nitrotriphenylene (2-NTP) via the gas-phase OH or NO(3) radical-initiated reactions. On the basis of the relative reactivity of the PACs in the CCl(4) liquid phase-system, the rate constants of the gas-phase reactions of TP with OH and NO(3) radicals at 298 K were predicted to be (8.6±1.2)×10(-12) cm(3) molecule(-1) s(-1) and (6.6±1.5)×10(-29)[NO(2)] cm(3) molecule(-1) s(-1), respectively. Based on the ambient concentrations of TP and 2-NTP and the obtained rate constant for the reaction of TP with OH radicals, the atmospheric loss rate of 2-NTP was also evaluated.

Acceleration of ammonium nitrite denitrification by freezing: determination of activation energy from the temperature of maximum reaction rate.

A reaction of ammonium nitrite in ice was investigated. Upon freezing, some nitrite is oxidized by dissolved oxygen and some nitrite reacts with ammonium to produce nitrogen and water in a denitrification reaction. The former reaction was accelerated only during freezing, and the latter one was accelerated even after the whole sample was frozen. The denitrification reaction proceeded at very low concentration in ice, which were conditions under which the reaction would not proceed in solution. The nitrogen production increased linearly with increasing initial concentration of ammonium nitrite. The concentration factor in the unfrozen solution in ice was estimated to be 50.6 when the initial concentration was 0.5 mmol dm(-3), as obtained from comparison of reaction rates in solution and in ice. A new method for determination of the activation energy is proposed that gives a value of 53 to 61 kJ mol(-1) for denitrification. The reaction order of the denitrification process is also determined using our method, and it is concluded to follow third-order kinetics.

Development of a selective light-emitting diode photolytic NO(2) converter for continuously measuring NO(2) in the atmosphere.

A photolytic converter of nitrogen dioxide (NO(2)) to nitric oxide (NO) using light-emitting diodes (LEDs) has been designed to measure NO(2) in the troposphere. The typical electrical power consumption of the photolytic converter (PLC) is only 44 W. The maximum conversion efficiency of NO(2) to NO of the photolytic converter is around 90%, which is higher than that of metal halides or high-pressure Xe arc lamps (up to ∼70%). The conversion efficiency of the PLC was almost constant for at least 2.5 months. The conversion efficiency of peroxyacetyl nitrate by the LED-PLC was measured to be 2.6 ± 0.1% (1σ). The interference of HONO using the PLC was experimentally estimated to be less than 3%, which is within the uncertainty of the instrument. An intercomparison of NO(2) measurements between the PLC-CLD and the laser-induced fluorescence (LIF) technique was conducted, and the NO(2) concentrations measured by the PLC-CLD method were in agreement with those obtained by the LIF technique, within the uncertainties of the instruments. Continuous observations were made on Fukue Island, a remote area. These results demonstrate the performance of the PLC for continuous ambient measurements.

A two-step continuous ultrasound assisted production of biodiesel fuel from waste cooking oils: a practical and economical approach to produce high quality biodiesel fuel.

A transesterification reaction of waste cooking oils (WCO) with methanol in the presence of a potassium hydroxide catalyst was performed in a continuous ultrasonic reactor of low-frequency 20 kHz with input capacity of 1 kW, in a two-step process. For the first step, the transesterification was carried out with the molar ratio of methanol to WCO of 2.5:1, and the amount of catalyst 0.7 wt.%. The yield of fatty acid methyl esters (FAME) was about 81%. A yield of FAME of around 99% was attained in the second step with the molar ratio of methanol to initial WCO of 1.5:1, and the amount of catalyst 0.3 wt.%. The FAME yield was extremely high even at the short residence time of the reactants in the ultrasonic reactor (less than 1 min for the two steps) at ambient temperature, and the total amount of time required to produce biodiesel was 15h. The quality of the final biodiesel product meets the standards JIS K2390 and EN 14214 for biodiesel fuel.

Effect of extraction temperature on pressurized liquid extraction of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and dioxin-like polychlorinated biphenyls from a sediment sample using polar and non-polar solvents.

This study is the first to investigate the effect of extraction temperature (150, 175, and 200 degrees C) on the simultaneous pressurized liquid extraction (PLE) of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (DL-PCBs) from a sediment sample (certified reference material: JSAC 0431). To provide basic data that will help to determine the optimum conditions for PLE, six single solvents (toluene, dichloromethane [DCM], benzene, acetonitrile, acetone, and methanol) were used as an extraction solvent. The results obtained by PLE with each solvent were compared with those obtained by Soxhlet extraction using toluene. The efficiency of PLE for 2,3,7,8-substituted PCDDs, 2,3,7,8-substituted PCDFs, and DL-PCBs, as obtained by PLE using the solvents toluene, DCM, benzene, and acetonitrile, showed an increase with increasing extraction temperature. The recoveries of PCDDs, PCDFs, and DL-PCBs obtained by PLE using toluene were similar to or inferior to those obtained using the Soxhlet method. In contrast, their recoveries obtained by PLE using DCM, benzene, and acetonitrile were similar to or higher than those obtained using the Soxhlet method. Notably, the recoveries of PCDDs, PCDFs, and DL-PCBs using benzene at 200 degrees C were 117+/-15, 123+/-13, and 115+/-12%, respectively. When using acetone and toluene, the recoveries of tetra-hexaCDDs and tetra-hexaCDFs also increased with extraction temperature. In particular, the recoveries of 2,3,7,8-tetraCDD and 2,3,7,8-tetraCDF obtained with acetone at 200 degrees C were 181+/-21 and 167+/-14%, respectively. However, the efficiency of PLE for heptaCDDs and/or heptaCDFs was insufficient at all the tested temperatures. Furthermore, the efficiency of PLE for octaCDD and/or octaCDF showed a pronounced decrease with increasing extraction temperature, yielding recoveries of approximately 40% at 200 degrees C. We found that heptaCDF isomers were produced from authentic octaCDF during the PLE procedure with acetone at 200 degrees C, indicating that the lower recoveries of highly chlorinated DDs and/or DFs are attributable to their degradation.

Ultrasound-assisted production of biodiesel fuel from vegetable oils in a small scale circulation process.

Biodiesel production from canola oil with methanol was performed in the presence of a base-catalyst by a circulation process at room temperature. In this process, the transesterification was accelerated by ultrasonic irradiation of low frequency (20 kHz) with an input capacity of 1 kW. The influences of various parameters on the transesterification reaction, including the amount of catalyst, the molar ratio of methanol to oil and the reaction time, were investigated. The objective of this work was to produce biodiesel satisfying the biodiesel-fuel standards of low energy consumption and material savings. The optimal conditions were: methanol/oil molar ratio of 5:1 and 0.7 wt.% catalyst in oil. Under these conditions, the conversion of triglycerides to fatty acid methyl esters was greater than 99% within the reaction time of 50 min. Crude biodiesel was purified by washing with tap water and drying at 70 degrees C under reduced pressure.

Characteristics of the abundance of polychlorinated dibenzo-p-dioxin and dibenzofurans, and dioxin-like polychlorinated biphenyls in sediment samples from selected Asian regions in Can Gio, Southern Vietnam and Osaka, Japan.

The levels of polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/PCDFs), and dioxin-like polychlorinated biphenyls (DL-PCBs) were determined in sediment samples from Can Gio, South Vietnam, and Osaka, Japan. Can Gio is known for the defoliation of its mangrove forests by aerial spraying with Agent Orange during the Vietnam War, whereas Osaka is renowned for a PCDD/PCDF pollution accident at a municipal solid-waste incinerator. For comparison, we also analyzed PCDD/PCDFs and DL-PCBs in sediment samples from Hue and Hanoi, Vietnam. The toxic equivalent quantity (TEQ) values in Can Gio were as high as those in Hue, Hanoi, and suburban areas of Osaka, but much lower than those in urban areas of Osaka. The proportion of the World Health Organization (WHO)-TEQ value contributed by 2,3,7,8-tetrachlorinated dibenzo-p-dioxin (TCDD) in Can Gio was approximately 30%, higher than the values in the other sample areas. These data suggest that residual sedimentary TCDD that originated from aerial spraying of Agent Orange occur in only low concentrations in Can Gio. The main contributors to WHO-TEQ values in Can Gio are natural sources, as in Hue. In contrast, commercial PCBs are the dominant contributors to WHO-TEQ values in Hanoi. In Osaka, agrochemicals used in rice cultivation, the incineration of solid waste, and commercial PCBs equally contributed to WHO-TEQ values at suburban locations. The dumping of incinerator-related materials and/or the inadequate management of commercial PCBs have resulted in significantly elevated WHO-TEQ values of 240-370 ng kg(-1)dw at urban locations in Osaka.

The chemistry of drying an aqueous solution of salts.

The fate of salts in drying aqueous solution was investigated. In the drying of acidic solutions, weak acid ions and chloride ions combine with protons and evaporate, depending on the proton concentration. In the drying of alkaline solutions, weak acid ions evaporate or remain as salts depending on the ratio of the concentrations of excess nonvolatile cations (the difference between concentrations of nonvolatile cation and nonvolatile anion) to volatile anions defined as DeltaCA. Under neutral and alkaline conditions, the fate of nitrite depends not only on DeltaCA but also on the drying speed. Nitrite is converted to N2, which is formed by reacting nitrite with ammonium (denitrification), NO and NO2, HONO and salts. In urban areas, nitrite and ammonium can appear in high concentrations in dew. HONO in the atmosphere affects the ozone concentration, but dew formation decreases the concentration of HONO. If chemical denitrification occurs, nitrogen species will decrease in the environment, and as a result, the ozone concentration could decrease. Ozone levels show an ozone depression when dew formed, and a Box model simulation showed an ozone depression by decreasing HONO levels.

Seasonal change in the atmospheric concentration of particulate polycyclic aromatic hydrocarbons in Ho Chi Minh City, Vietnam.

We analyzed atmospheric particulate polycyclic aromatic hydrocarbons (PAHs) in Ho Chi Minh City, Vietnam, for 19 months. The average concentrations of total PAHs at dry and rainy seasons were 4.28 +/- 2.83 and 15.71 +/- 8.21 ng m(-3), respectively. The use of motorcycles without catalytic converters, estimated to be main emission sources of PAHs, would be higher during the dry season. PAH concentrations show a negative correlation with sunshine duration (r = -0.51). Furthermore, the ratio of average PAH concentration in the dry season to that in the rainy season shows a positive correlation with photolytic half-life (r = 0.94). Thus, seasonal changes in PAH concentrations are attributable to their photolytic degradation.

Sonochemical decomposition of organic acids in aqueous solution: understanding of molecular behavior during cavitation by the analysis of a heterogeneous reaction kinetics model.

The sonochemical decomposition of a low concentration of butyric acid was performed in an aqueous solution by use of 200 kHz ultrasound to discuss the reaction kinetics and molecular behavior during cavitation. Taking into account a Langmuir-type adsorption model, we propose a heterogeneous reaction kinetics model, which is based on the local reaction zone at the interface region of the cavitation bubbles, where the adsorption and desorption of butyric acid molecules from the bulk solution occur during bubble oscillation and then the existing molecules inside the local reaction zone are finally decomposed. To confirm our proposed kinetics model, the rates of decomposition were investigated as a function of the initial concentration of butyric acids in the different pH solutions. It was confirmed that our model could be reasonably applied to explain the obtained results and the pseudo rate constant (k) and the equilibrium constant (K) were able to be calculated: k is 8.0 microM min(-1) (pH 2) and 3.5 microM min(-1) (pH 10), and K is 5.7 x 10(-3) microM(-1) (pH 2) and 8.0 x 10(-3) microM(-1) (pH 10), respectively. By the analysis of the obtained K values, it was clear that the ionized organic acid molecules are relatively difficult to accumulate at the reaction zone, because of their lower hydrophobicity compared with that of the neutral ones. The results obtained in the sonochemical decomposition of benzoic acid were also able to be analyzed with the proposed kinetics model. In addition, we proposed an opinion toward the interpretation of a Langmuir-type adsorption model which has often been applied to explain heterogeneous reaction systems.

Influence of adding salt on ultrasonic atomization in an ethanol-water solution.

Ethanol was enriched by ultrasonic atomization. Enrichment ratios were increased by adding salt to the ethanol solution. Different enrichment ratios were observed for different types of salts in a range of low ethanol concentrations. The enrichment ratio was significantly improved by adding K(2)CO(3) or (NH(4))(2)SO(4). It is concluded that this is due to enhanced interfacial adsorption of the ethanol. Addition of Na(2)CO(3) to the ethanol solution also enhanced the interfacial adsorption of the ethanol, but the effect was relatively small. Addition of NaCl to the ethanol solution did not enhance the interfacial adsorption of the ethanol.

Effect of reaction vessel diameter on sonochemical efficiency and cavitation dynamics.

The influence of reaction vessel diameter on the sonochemical yield was investigated by using reaction vessels with five different diameters. It was revealed that the formation of H(2)O(2) and chloride ion, from the sonolysis of pure water and 1,2,4-trichlorobenzene aqueous solution, was affected by the reaction vessel diameter. That is, these yields increased as the reaction vessel diameter increased up to ø 90 mm and then decreased over ø 90 mm. From the analyses of the measurement of sonochemiluminescence and the calorimetry, it was suggested that active cavitation bubbles were formed at certain zones. In the case of a larger diameter reaction vessel, it was suggested that bubble nuclei that have not grown up to the resonance size, escaped from the sonication zone to the non-sonication zone and dissolved away. As a result, the number of active cavitation bubbles and the yields of H(2)O(2) and chloride ion would decrease in the case of a larger diameter reaction vessel.

A gaseous nitric acid analyzer for the remote atmosphere based on the scrubber difference/NO-ozone chemiluminescence method.

An in situ nitric acid analyzer has been designed for sensing in the remote atmosphere. Its operation is based on measuring the concentration difference between the total odd nitrogen species (NO(y)) and HNO(3)-scrubbed NO(y). NO(y) was measured by an NO-ozone chemiluminescent detector equipped with a molybdenum converter. A temperature-controlled annular denuder coated with NaCl was used as a scrubber of gaseous HNO(3). The current detection limit of the HNO(3) analyzer was estimated to be 158 and 71 pptv (parts per trillion by volume) with an integration time of 2 and 10 min (2sigma), respectively. The analyzer was calibrated using standard gaseous HNO(3) to verify its performance. The HNO(3) concentrations measured by the scrubber difference and the NO-ozone chemiluminescence methods (SDCL method) were in agreement with those obtained by the denuder method within the experimental uncertainties (more than +/-4%). We conducted limited field observations of NO(y) and HNO(3) in the remote atmosphere using the newly designed SDCL method at Cape Hedo, Okinawa, Japan.