Fine scale variability in methanol uptake and oxidation in the micro-layer and near-surface waters of the Atlantic

The aim of this research was to make the first depth profiles of the microbial assimilation of methanol carbon and its oxidation to carbon dioxide and use as an energy source from the microlayer to 1000 m. Some of the highest reported methanol oxidation rate constants of 0.5–0.6 d−1 were occasionally found in the microlayer and immediately underlying waters (10 cm depth), albeit these samples also showed the greatest heterogeneity compared to other depths down to 1000 m. Methanol uptake into the particulate phase was exceptionally low in microlayer samples, suggesting that any methanol utilised by microbes in this environment is for energy generation. The sea surface microlayer and 10 cm depth also showed a higher proportion of bacteria with a low DNA content, and bacterial leucine uptake rates in surface microlayer samples were either less than or the same as those in the underlying 10 cm layer. The average methanol oxidation and particulate rates were however statistically the same throughout the depths sampled, although the latter were highly variable in the near-surface 0.25–2 m compared to deeper depths. The statistically significant relationship demonstrated between uptake of methanol into particles and bacterial leucine incorporation suggests that many heterotrophic bacteria could be using methanol carbon for cellular growth. On average, methanol bacterial growth efficiency (BGEm) in the top 25 m of the water column is 6% and decreases with depth. Although, for microlayer and 10 cm-depth samples, BGEm is less than the near-surface 25–217 cm, possibly reflecting increased environmental UV stress resulting in increased maintenance costs, i.e. energy required for survival. We conclude that microbial methanol uptake rates, i.e. loss from seawater, are highly variable, particularly close to the seawater surface, which could significantly impact upon seawater concentrations and hence the air–sea flux.

Microbial acetone oxidation in coastal seawater

Acetone is an important oxygenated volatile organic compound (OVOC) in the troposphere where it influences the oxidizing capacity of the atmosphere. However, the air-sea flux is not well quantified, in part due to a lack of knowledge regarding which processes control oceanic concentrations, and, specifically whether microbial oxidation to CO2 represents a significant loss process. We demonstrate that 14C labeled acetone can be used to determine microbial oxidation to 14CO2. Linear microbial rates of acetone oxidation to CO2 were observed for between 0.75-3.5 h at a seasonally eutrophic coastal station located in the western English Channel (L4). A kinetic experiment in summer at station L4 gave a Vmax of 4.1 pmol L-1 h-1, with a Km constant of 54 pM. We then used this technique to obtain microbial acetone loss rates ranging between 1.2 and 42 pmol L-1 h-1.(monthly averages) over an annual cycle at L4, with maximum rates observed during winter months. The biological turnover time of acetone (in situ concentration divided by microbial oxidation rate) in surface waters varied from ~3 days in February 2011, when in situ concentrations were 3 ± 1 nM, to >240 days in June 2011, when concentrations were more than twofold higher at 7.5 ± 0.7 nM. These relatively low marine microbial acetone oxidation rates, when normalized to in situ concentrations, suggest that marine microbes preferentially utilize other OVOCs such as methanol and acetaldehyde.

Maintenance of abyssal benthic foraminifera under high pressure and low temperature: some preliminary results

Abyssal benthic foraminifera have been maintained alive for periods of several weeks under laboratory simulated deep-sea conditions of high pressure and low temperature. In separate experiments, bacterial-sized fluorescent microspheres and three species of microalgae were supplied as food particles. Subsequent light and electron microscopy showed that the algae had been ingested by several foraminiferal species. Furthermore, the fine structure of the foraminiferal cytoplasm was well-preserved which indicates, along with the ingestion of algal food, that they had remained in a viable condition during the incubation. Other observations indicate that abyssal benthic foraminifera ingest naturally occurring photosynthetic cells carried to the deep-sea bed by rapidly sedimenting aggregates. The ability to keep foraminifera originating from depths exceeding 4000 m alive in the laboratory paves the way for the experimental investigation of some important issues in deep-sea biology and palaeoceanography.

Low temperature surface nitridation processes for dielectric-Ge interfaces

Germanium MOS capacitors have been fabricated with a high-? HfO dielectric using ALD. An in-situ low temperature (250°C) nitrogen plasma treatment on the germanium surface prior to the deposition of HfO was found to be beneficial to the electrical properties of the devices. Germanium MOS capacitors have also been fabricated with a SiO dielectric deposited by an atmospheric pressure CVD 'silox' process. The same low temperature plasma nitridation was found to degrade the electrical properties of the silox devices. The effect of a post-metal anneal in H and N on both types of capacitor structure was also found to degrade device electrical properties. copyright The Electrochemical Society.

Behavior of the heterogeneous electron-transfer rate constants of arenes and substituted anthracenes in room-temperature ionic liquids

We report the anodic oxidation of several arenes and anthracenes within room-temperature ionic liquids (RTILs). In particular, the heterogeneous electron-transfer rates (k(0)) for substituted anthracenes and arenes are also investigated in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C(2)mim][NTf2]) and found not to obey the outer-sphere Marcus-type behavior of these compounds in contrast to the behavior in traditional organic solvents,in particular the predictions for k(0) with molecular size and solvent static dielectric constant. To obtain the electron-transfer rate for 9-phenylanthracene, the dimerization and heterogeneous electron-transfer kinetics of its electrogenerated radical cations is studied in [C(2)mim][NTf2] and eight other RTILs and are both found to be largely independent of the solution viscosity.

Relaxation processes in room temperature ionic liquids: The case of 1-butyl-3-methyl imidazolium hexafluorophosphate

A detailed investigation on the nature of the relaxation processes occurring in a typical room temperature ionic liquid (RTIL), namely, 1-butyl-3-methyl imidazolium hexafluorophosphate ([bmim][PF6]), is reported. The study was conducted using both elastic and inelastic neutron scattering over a wide temperature range from 10 to 400 K, accessing the dynamic features of both the liquid and glassy amorphous states. In this study, the inelastic fixed energy scan technique has been applied for the first time to this class of materials. Using this technique, the existence of two relaxation processes below the glass transition and a further diffusive process occurring above the glass-liquid transition are observed. The low temperature processes are associated with methyl group rotation and butyl chain relaxation in the glassy state and have been modeled in terms of two Debye-like, Arrhenius activated processes. The high temperature process has been modeled in terms of a Kohlraush-Williams-Watts relaxation, with a distinct Vogel-Fulcher-Tamman temperature dependence. These results provide novel information that will be useful in rationalizing the observed structural and dynamical behavior of RTILs in the amorphous state.

A comparative electrochemical study of diffusion in room temperature ionic liquid solvents versus acetonitrile

Measurements on the diffusion coefficient of the neutral molecule N,N,N',N'-tetramethyl-para-phenylenediamine and the radical cation and dication generated by its one- and two-electron oxidation, respectively, are reported over the range 298-348 K in both acetonitrile and four room temperature ionic liquids (RTILs). Data were collected using single and double potential step chronamperometry at a gold disk electrode of micrometer dimension, and analysed via fitting to the appropriate analytical expression or, where necessary, to simulation. The variation of diffusion coefficient with temperature was found to occur in an Arrhenius-type manner for all combinations of solute and solvent. For a given ionic liquid, the diffusional activation energies of each species were not only closely equivalent to each other, but also to the RTIL's activation energy of viscous flow. In acetonitrile supported with 0.1 M tetrabutylammonium perchlorate, the ratio in diffusion coefficients of the radial cation and dication tot he neutral molecule were calculated as 0.89 +/- 0.05 and 0.51 +/- 0.03, respectively. In contrast, amongst the ionic liquids the same ratios were determined to be on average 0.53 +/- 0.04 and 0.33 +/- 0.03. The consequences of this dissimilarity are considered in terms of the modelling of voltammetric data gathered within ionic liquid solvents.

Low-temperature catalytic decomposition of N2O on platinum and bismuth-modified platinum: identification of active sites

Classification of the active surface sites of platinum catalysts responsible for low temperature N2O decomposition, in terms of steps, kinks and terraces, has been achieved by controlled addition of bismuth to as-received platinum/graphite catalysts.

An investigation of catalysts for the on board synthesis of NH3. A possible route to low temperature NOx reduction for lean-burn engines

Platinum group metal catalysts have been investigated for the formation of NH3 from NO + H-2 at low temperatures in the absence and presence of CO. Although CO inhibits the formation of NH3, substantial amounts are still observed with a Pt catalyst. By combining Pt with a support (ceria-zirconia) that has low temperature NOx storage characteristics it has been shown in transient experiments that NH3 can be formed and stored in situ under rich conditions, and may then be used to reduce NOx under lean burn conditions.

The effects of the specific adsorption of anion on the reactivity of the Ru(0001) surface towards CO adsorption and oxidation: in situ FTIRS studies

The dynamics of adsorption and oxidation of CO on Ru(0001) electrode in sulfuric acid solution have been studied using in situ FTIR spectroscopy under potential control and at open circuit, the latter at 20 and 55 degrees C. The in situ IR data show clearly that the bisulfate anion adsorbs on the Ru(0001) surface over the potential range from -200 mV to 350 mV (vs. Ag/AgCl) at 20 degrees C in the absence and presence of adsorbed CO; however, increasing the temperature to 55 degrees C and/ or increasing the concentration of dissolved O-2 reduces the bisulfate adsorption. The formation of surface (hydro-) oxide at higher potentials replaces the bisulfate adsorbates. Both linear (COL) and three-fold hollow bonded CO (COH) adsorbates were produced following CO adsorption at Ru(0001) in H2SO4, as was observed in our previous studies in HClO4. However, the amount of adsorbed CO observed in H2SO4 was ca. 10% less than that in HClO4; in addition, the COL and COH frequencies were higher in H2SO4, and the onset potential for COads oxidation 25 mV lower. These new results are interpreted in terms of a model in which the adsorbed bisulfate weakens the CO adlayer, allowing the active Ru oxide layer to form at lower potentials. Significantly different results were observed at open circuit in H2SO4 compared both to the data under potential control and to our earlier data in HClO4, and these observations were rationalized in terms of the adsorbed HSO4- anions (pre-adsorbed at -200 mV) inhibiting the oxidation of the surface at open circuit (after stepping from the initial potential of -200 mV), as the latter was no longer driven by the imposed electrochemical potential but via chemical oxidation by trace dissolved O-2. Results from experiments at open circuit at 55 degrees C and using oxygen-saturated H2SO4 supported this model. The difference in Ru surface chemistry between imposed electrochemical control and chemical control has potential implications with respect to fuel cell electrocatalysis.

Investigating the Mechanism and Electrode Kinetics of the Oxygen vertical bar Superoxide (O-2 vertical bar O-2(center dot-)) Couple in Various Room-Temperature Ionic Liquids at Gold and Platinum Electrodes in the Temperature Range 298-318 K

The reduction of oxygen was studied over a range of temperatures (298-318 K) in n-hexyltriethylammonium bis(trifluoromethanesulfonyl)imide, [N-6,N-2,N-2,N-2][NTf2], and 1-butyl-2,3-methylimidazolium bis(trifluoromethanesulfonyl)imide, [C(4)dmim][NTf2] on both gold and platinum microdisk electrodes, and the mechanism and electrode kinetics of the reaction investigated. Three different models were used to simulate the CVs, based on a simple electron transfer ('E'), an electron transfer coupled with a reversible homogeneous chemical step ('ECrev') and an electron transfer followed by adsorption of the reduction product ('EC(ads)'), and where appropriate, best fit parameters deduced, including the heterogeneous rate constant, formal electrode potential, transfer coefficient, and homogeneous rate constants for the ECrev mechanism, and adsorption/desorption rate constants for the EC(ads) mechanism. It was concluded from the good simulation fits on gold that a simple E process operates for the reduction of oxygen in [N-6,N-2,N-2,N-2][NTf2], and an ECrev process for [C(4)dmim][NTf2], with the chemical step involving the reversible formation of the O-2(center dot-)center dot center dot center dot [C(4)dmim](+) ion-pair. The E mechanism was found to loosely describe the reduction of oxygen in [N-6,N-2,N-2,N-2][NTf2] on platinum as the simulation fits were reasonable although not perfect, especially for the reverse wave. The electrochemical kinetics are slower on Pt, and observed broadening of the oxidation peak is likely due to the adsorption of superoxide on the electrode surface in a process more complex than simple Langmuirian. In [C(4)dmim][NTf2] the O-2(center dot-) predominantly ion-pairs with the solvent rather than adsorbs on the surface, and an ECrev quantitatively describes the reduction of oxygen on Pt also.

Comparison of a novel spray congealing procedure with emulsion-based methods for the micro-encapsulation of water-soluble drugs in low melting point triglycerides

The particle size characteristics and encapsulation efficiency of microparticles prepared using triglyceride materials and loaded with two model water-soluble drugs were evaluated. Two emulsification procedures based on o/w and w/o/w methodologies were compared to a novel spray congealing procedure. After extensive modification of both emulsification methods, encapsulation efficiencies of 13.04% tetracycline HCl and 11.27% lidocaine HCl were achievable in a Witepsol (R)-based microparticle. This compares to much improved encapsulation efficiencies close to 100% for the spray congealing method, which was shown to produce spherical particles of similar to 58 mu m. Drug release studies from a Witepsol (R) formulation loaded with lidocaine HCl showed a temperature-dependent release mechanism, which displayed diffusion-controlled kinetics at temperatures similar to 25 degrees C, but exhibited almost immediate release when triggered using temperatures close to that of skin. Therefore, such a system may find application in topical semi-solid formulations, where a temperature-induced burst release is preferred.

Non-invasive VHF monitoring of low-temperature atmospheric pressure plasma

A real-time VHF swept frequency (20–300 MHz) reflectometry measurement for radio-frequency capacitive-coupled atmospheric pressure plasmas is described. The measurement is scalar, non-invasive and deployed on the main power line of the plasma chamber. The purpose of this VHF signal injection is to remotely interrogate in real-time the frequency reflection properties of plasma. The information obtained is used for remote monitoring of high-value atmospheric plasma processing. Measurements are performed under varying gas feed (helium mixed with 0–2% oxygen) and power conditions (0–40 W) on two contrasting reactors. The first is a classical parallel-plate chamber driven at 16 MHz with well-defined electrical grounding but limited optical access and the second is a cross-field plasma jet driven at 13.56 MHz with open optical access but with poor electrical shielding of the driven electrode. The electrical measurements are modelled using a lumped element electrical circuit to provide an estimate of power dissipated in the plasma as a function of gas and applied power. The performances of both reactors are evaluated against each other. The scalar measurements reveal that 0.1% oxygen admixture in helium plasma can be detected. The equivalent electrical model indicates that the current density between the parallel-plate reactor is of the order of 8–20 mA cm-2 . This value is in accord with 0.03 A cm-2 values reported by Park et al (2001 J. Appl. Phys. 89 20–8). The current density of the cross-field plasma jet electrodes is found to be 20 times higher. When the cross-field plasma jet unshielded electrode area is factored into the current density estimation, the resultant current density agrees with the parallel-plate reactor. This indicates that the unshielded reactor radiates electromagnetic energy into free space and so acts as a plasma antenna.

Development of the kinetic model of platinum catalyzed ammonia oxidation in a microreactor

The ammonia oxidation reaction on supported polycrystalline platinum catalyst was investigated in an aluminum-based microreactor. An extensive set of reactions was included in the chemical reactor modeling to facilitate the construction of a kinetic model capable of satisfactory predictions for a wide range of conditions (NH3 partial pressure, 0.01-0.12 atm; O-2 partial pressure, 0.10-0.88 atm; temperature, 523-673 K; contact time, 0.3-0.7 ms). The elementary surface reactions used in developing the mechanism were chosen based on the literature data concerning ammonia oxidation on a Pt catalyst. Parameter estimates for the kinetic model were obtained using multi-response least squares regression analysis using the isothermal plug-flow reactor approximation. To evaluate the model, the behavior of a microstructured reactor was simulated by means of a complete Navier-Stokes model accounting for the reactions on the catalyst surface and the effect of temperature on the physico-chemical properties of the reacting mixture. In this way, the effect of the catalytic wall temperature non-uniformity and the effect of a boundary layer on the ammonia conversion and selectivity were examined. After further optimization of appropriate kinetic parameters, the calculated selectivities and product yields agree very well with the values actually measured in the microreactor. (C) 2002 Elsevier Science B.V. All rights reserved.