Adsorption of Supercritical fluids on graphitised thermal carbon black: Molecular layer structure theory versus grand canonical Monte Carlo simulation

This paper presents a detailed analysis of adsorption of supercritical fluids on nonporous graphitized thermal carbon black. Two methods are employed in the analysis. One is the molecular layer structure theory (MLST), proposed recently by our group, and the other is the grand canonical Monte Carlo (GCMC) simulation. They were applied to describe the adsorption of argon, krypton, methane, ethylene, and sulfur hexafluoride on graphitized thermal carbon black. It was found that the MLST describes all the experimental data at various temperatures well. Results from GCMC simulations describe well the data at low pressure but show some deviations at higher pressures for all the adsorbates tested. The question of negative surface excess is also discussed in this paper.

The effect of caudal block on functional residual capacity and ventilation homogeneity in healthy children

Caudal block results in a motor blockade that can reduce abdominal wall tension. This could interact with the balance between chest wall and lung recoil pressure and tension of the diaphragm, which determines the static resting volume of the lung. On this rationale, we hypothesised that caudal block causes an increase in functional residual capacity and ventilation distribution in anaesthetised children. Fifty-two healthy children (15-30 kg, 3-8 years of age) undergoing elective surgery with general anaesthesia and caudal block were studied and randomly allocated to two groups: caudal block or control. Following induction of anaesthesia, the first measurement was obtained in the supine position (baseline). All children were then turned to the left lateral position and patients in the caudal block group received a caudal block with bupivacaine. No intervention took place in the control group. After 15 nun in the supine position, the second assessment was performed. Functional residual capacity and parameters of ventilation distribution were calculated by a blinded reviewer. Functional residual capacity was similar at baseline in both groups. In the caudal block group, the capacity increased significantly (p < 0.0001) following caudal block, while in the control group, it remained unchanged. In both groups, parameters of ventilation distribution were consistent with the changes in functional residual capacity. Caudal block resulted in a significant increase in functional residual capacity and improvement in ventilation homogeneity in comparison with the control group. This indicates that caudal block might have a beneficial effect on gas exchange in anaesthetised, spontaneously breathing preschool-aged children with healthy lungs.

The significance of nitrogen regeneration for new production within a filament of the Mauritanian upwelling system

The Lagrangian progression of a biological community was followed in a filament of the Mauritanian upwelling system, north-west Africa, during offshore advection. The inert dual tracers sulfur hexafluoride and helium-3 labelled a freshly upwelled patch of water that was mapped for 8 days. Changes in biological, physical, and chemical characteristics were measured, including phytoplankton productivity, nitrogen assimilation, and regeneration. Freshly upwelled water contained high nutrient concentrations but was depleted in N compared to Redfield stoichiometry. The highest rate of primary productivity was measured on the continental shelf, associated with high rates of nitrogen assimilation and a phytoplankton community dominated by diatoms and flagellates. Indicators of phytoplankton abundance and activity decreased as the labelled water mass transited the continental shelf slope into deeper water, possibly linked to the mixed layer depth exceeding the light penetration depth. By the end of the study, the primary productivity rate decreased and was associated with lower rates of nitrogen assimilation and lower nutrient concentrations. Nitrogen regeneration and assimilation took place simultaneously. Results highlighted the importance of regenerated NHC 4 in sustaining phytoplankton productivity and indicate that the upwelled NO3 pool contained an increasing fraction of regenerated NO3 as it advected offshore. By calculating this fraction and incorporating it into an f ratio formulation, we estimated that of the 12:38Tg C of annual regional production, 4:73Tg C was exportable.

The significance of nitrogen regeneration for new production within a filament of the Mauritanian upwelling system

The Lagrangian progression of a biological community was followed in a filament of the Mauritanian upwelling system, north-west Africa, during offshore advection. The inert dual tracers sulfur hexafluoride and helium-3 labelled a freshly upwelled patch of water that was mapped for 8 days. Changes in biological, physical, and chemical characteristics were measured, including phytoplankton productivity, nitrogen assimilation, and regeneration. Freshly upwelled water contained high nutrient concentrations but was depleted in N compared to Redfield stoichiometry. The highest rate of primary productivity was measured on the continental shelf, associated with high rates of nitrogen assimilation and a phytoplankton community dominated by diatoms and flagellates. Indicators of phytoplankton abundance and activity decreased as the labelled water mass transited the continental shelf slope into deeper water, possibly linked to the mixed layer depth exceeding the light penetration depth. By the end of the study, the primary productivity rate decreased and was associated with lower rates of nitrogen assimilation and lower nutrient concentrations. Nitrogen regeneration and assimilation took place simultaneously. Results highlighted the importance of regenerated NHC 4 in sustaining phytoplankton productivity and indicate that the upwelled NO3 pool contained an increasing fraction of regenerated NO3 as it advected offshore. By calculating this fraction and incorporating it into an f ratio formulation, we estimated that of the 12:38Tg C of annual regional production, 4:73Tg C was exportable.

Effect of seasons on enteric methane emissions from cattle grazing Urochloa brizantha.

Abstract: The objective of this study was to evaluate the effect of seasons under a tropical climate on forage quality, aswell the effect of an Urochloa brizantha cv. Marandu grazing system on enteric methane (CH4) emissions fromNellore cattle in the Southeast region of Brazil. Sixteen Nellore steers (18 months old and initial weight 318.0 ± 116.59 kg of LW; final weight 469 ± 98.50 kg of LW) were used for a trial period of 10 months, with four collection periods in winter (August), spring (December), summer (February) and autumn (May). Each collection period consisted of 28 days, corresponding to the representative month of each season where the last six days were designed for methane data collection. Animals were randomly distributed within 16 experimental plots, distributed in four random blocks over four trial periods. CH4 emissions were determined using the sulphur hexafluoride (SF6) tracer gas technique measured by gas chromatography and fluxes of CH4 calculated. The forage quality was characterized by higher CP and IVDMD and lower lignin contents in spring, differing specially from winter forage. Average CH4 emissions were between 102.49 and 220.91 g d-1 (37.4 to 80.6 kg ani-1 yr-1); 16.89 and 30.20 g kg-1 DMI; 1.35 and 2.90 Mcal ani-1 d-1; 0.18 and 0.57 g kg-1 ADG-1 and 5.05 and 8.76% of GE. Emissions in terms of CO2 equivalents were between 4.68 and 14.22 g CO2-eq-1 g-1 ADG. Variations in CH4 emissions were related to seasonal effect on the forage quality and variations in dry matter intake.

Chemical functionalities of high and low sulfur Australian coals : a case study using micro attenuated total reflectance–fourier transform infrared (ATR–FTIR) spectrometry

The macerals in bituminous coals with varying organic sulfur content from the Early Permian Greta Coal Measures at three locations (Southland Colliery, Drayton Colliery and the Cranky Corner Basin), in and around the Sydney Basin (Australia), have been studied using light-element electron microprobe (EMP) analysis and micro-ATR–FTIR. Electron microprobe analysis of individual macerals reveals that the vitrinite in both the Cranky Corner Basin and Drayton Colliery (Puxtrees seam) samples have similar carbon contents (ca. 78% C in telocollinite), suggesting that they are of equivalent rank. However, the Cranky Corner coals have anomalously low vitrinite reflectance (down to 0.45%) vs. the Drayton materials (ca. 0.7%). They also have very high organic S content (3–6.5%) and lower O content (ca. 10%) than the equivalent macerals in the Drayton sample (0.7% S and 15.6% O). A study was carried out to investigate the impacts of the high organic S on the functional groups of the macerals in these two otherwise iso-rank, stratigraphically-equivalent seams. An iso-rank low-S coal from the overlying Wittingham Coal Measures near Muswellbrook and coals of slightly higher rank from the Greta Coal Measures at Southland Colliery near Cessnock were also evaluated using the same techniques to extend the data set. Although the telocollinite in the Drayton and Cranky Corner coals have very similar carbon content (ca.78% C), the ATR–FTIR spectra of the vitrinite and inertinite macerals in these respectively low S and high S coals show some distinct differences in IR absorbance from various aliphatic and aromatic functional groups. The differences in absorbance of the aliphatic stretching bands (2800–3000 cm−1) and the aromatic carbon (CC) peak at 1606 cm−1 are very obvious. Compared to that of the Drayton sample (0.7% S and 15% O), the telocollinite of the Cranky Corner coal (6% S and 10% O) clearly shows: (i) less absorbance from OH groups, represented by a broad region around 3553 cm−1, (ii) much stronger aliphatic C–H absorbance (stretching modes around 3000–2800 cm−1 and bending modes around 1442 cm−1) and (iii) less absorbance from aromatic carbon functional groups (peaking at 1606 cm−1). Evaluation of the iso-rank Drayton and Cranky Corner coals shows that: (i) the aliphatic C–H absorbances decrease with increasing oxygen content but increase with increasing organic S content and (ii) the aromatic H to aliphatic H ratio (Har/Hali) for the telocollinite increases with (organic) O%, but decreases progressively with increasing organic S. The high organic S content in the maceral appears to be accompanied by a greater proportion of aliphatic functional groups, possibly as a result of some of the O within maceral ring structures in the high S coal samples being replaced.

Effect of thermal treatment on adsorption-desorption of ammonia and sulfur dioxide on palygorskite : change of surface acid-alkali properties

Thermally activated Palygorskite (Pg) has been found to be a good adsorbent material for ammonia (NH3) and sulfur dioxide (SO2). This research investigated the effect of thermal treatment on pore structure and surface acid-alkali properties of Pg through the adsorption-desorption of NH3 and SO2. The results showed that, up to 200 °C, the adsorption of NH3 on Pg was significantly higher than SO2. This was due to NH3 being adsorbed in the internal surface of Pg and forming hydrogen bonds (H-bonds) with coordinated water. The increase in thermal treatment temp. from 150 to 550 °C, showed a gradual decrease in the no. of surface acid sites, while the no. of surface alk. sites increased from 200 to 400 °C. The change of surface acidity-alk. sites is due to the collapse of internal channels of Pg and desorption of different types of hydroxyls assocd. with the Pg structure.

Surface sulfur measurements on stratospheric particles

The surface chemistries of three particulate samples collected from the lower stratosphere have been determined using a Scanning Auger Microprobe (SAM). These samples are typical of the most abundant natural and anthropogenic particles observed within the stratosphere in the >2µm diameter size fraction. Successive sputtering and analysis below the first few adsorbed monolayers of all particles shows the presence of a thin <150A) sulphur layer. These sulphur regions probably formed by surface reaction of sulphur-rich aerosols with each particle within the stratosphere. Settling rate calculations show that a typical sphere (10µm diameter) may reside within the aerosol layer for ~20 days and thus, provide a qualitative guide to surface sulphur reaction rates.

Sulfur resistant emissions catalyst

A catalyst comprising one or more complex oxides having a nominal compn. as set out in formula (1): AxB1-y-zMyPzOn (1) wherein A is selected from one or more group III elements including the lanthanide elements or one or more divalent or monovalent cations; B is selected from one or more elements with at. no. 22 to 24, 40 to 42 and 72 to 75; M is selected from one or more elements with at. no. 25 to 30; P is selected from one or more elements with at. no. 44 to 50 and 76 to 83; x is defined as a no. where 0

Ion-molecule reactions of O,S-Dimethyl methylphosphonothioate : Evidence for intramolecular sulfur oxidation during VX perhydrolysis

The alkaline perhydrolysis of the nerve agent O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX) was investigated by studying the ion-molecule reactions of HOO(-) with O,S-dimethyl methylphosphonothioate in a modified linear ion-trap mass spectrometer. In addition to simple proton transfer, two other abundant product ions are observed at m/z 125 and 109 corresponding to the S-methyl methylphosphonothioate and methyl methylphosphonate anions, respectively. The structure of these product ions is demonstrated by a combination of collision-induced dissociation and isotope-labeling experiments that also provide evidence for their formation by nucleophilic reaction pathways, namely, (i) S(N)2 at carbon to yield the S-methyl methylphosphonothioate anion and (ii) nucleophilic addition at phosphorus affording a reactive pentavalent intermediate that readily undergoes internal sulfur oxidation and concomitant elimination of CH(3)SOH to yield the methyl methylphosphonate anion. Consistent with previous Solution phase observations of VX perhydrolysis, the toxic P-O cleavage product is not observed in this VX model system and theoretical calculations identify P-O cleavage to be energetically uncompetitive. Conversely, intramolecular sulfur oxidation is calculated to be extremely exothermic and kinetically accessible explaining its competitiveness with the facile gas phase proton transfer process. Elimination of a sulfur moiety deactivates the nerve agent VX and thus the intramolecular sulfur oxidation process reported here is also able to explain the selective perhydrolysis of the nerve agent to relatively nontoxic products.

Sulfur-containing amide-based [2]rotaxanes and molecular shuttles

We report the synthesis, structure and properties of [2]rotaxanes prepared by the assembly of benzylic amide macrocycles around a series of amide and sulfide-/sulfoxide-/sulfone-containing threads. The efficacy of rotaxane formation is related to the hydrogen bond accepting properties of the various sulfur-containing functional groups in the thread, with the highest yields (up to 63% with a rigid vinyl spacer in the template site) obtained for sulfoxide rotaxanes. X-Ray crystallography of a sulfoxide rotaxane, 5, shows that the macrocycle adopts a highly symmetrical chair-like conformation in the solid state, with short hydrogen bonds between the macrocycle isophthalamide NH-protons and the amide carbonyl and sulfoxide S-O of the thread. In contrast, in the X-ray crystal structures of the analogous sulfide (4) and sulfone (6) rotaxanes the macrocycle adopts boat-like conformations with long intercomponent NH…O=SO and NH…S hydrogen bonds (in addition to several intercomponent amide-amide hydrogen bonds). Taking advantage of the different hydrogen bonding modes of the sulfur-based functional groups, a switchable molecular shuttle was prepared in which the oxidation level of sulfur determines the position of the macrocycle on the thread.