A USANS/SANS study of the accessibility of pores in the barnett shale to methane and water

Shale is an increasingly important source of natural gas in the United States. The gas is held in fine pores that need to be accessed by horizontal drilling and hydrofracturing techniques. Understanding the nature of the pores may provide clues to making gas extraction more efficient. We have investigated two Mississippian Barnett Shale samples, combining small-angle neutron scattering (SANS) and ultrasmall-angle neutron scattering (USANS) to determine the pore size distribution of the shale over the size range 10 nm to 10 μm. By adding deuterated methane (CD4) and, separately, deuterated water (D2O) to the shale, we have identified the fraction of pores that are accessible to these compounds over this size range. The total pore size distribution is essentially identical for the two samples. At pore sizes >250 nm, >85% of the pores in both samples are accessible to both CD4 and D2O. However, differences in accessibility to CD4 are observed in the smaller pore sizes (∼25 nm). In one sample, CD4 penetrated the smallest pores as effectively as it did the larger ones. In the other sample, less than 70% of the smallest pores (<25 nm) were accessible to CD4, but they were still largely penetrable by water, suggesting that small-scale heterogeneities in methane accessibility occur in the shale samples even though the total porosity does not differ. An additional study investigating the dependence of scattered intensity with pressure of CD4 allows for an accurate estimation of the pressure at which the scattered intensity is at a minimum. This study provides information about the composition of the material immediately surrounding the pores. Most of the accessible (open) pores in the 25 nm size range can be associated with either mineral matter or high reflectance organic material. However, a complementary scanning electron microscopy investigation shows that most of the pores in these shale samples are contained in the organic components. The neutron scattering results indicate that the pores are not equally proportioned in the different constituents within the shale. There is some indication from the SANS results that the composition of the pore-containing material varies with pore size; the pore size distribution associated with mineral matter is different from that associated with organic phases.

Efficient articulated trajectory reconstruction using dynamic programming and filters

This paper considers the problem of reconstructing the motion of a 3D articulated tree from 2D point correspondences subject to some temporal prior. Hitherto, smooth motion has been encouraged using a trajectory basis, yielding a hard combinatorial problem with time complexity growing exponentially in the number of frames. Branch and bound strategies have previously attempted to curb this complexity whilst maintaining global optimality. However, they provide no guarantee of being more efficient than exhaustive search. Inspired by recent work which reconstructs general trajectories using compact high-pass filters, we develop a dynamic programming approach which scales linearly in the number of frames, leveraging the intrinsically local nature of filter interactions. Extension to affine projection enables reconstruction without estimating cameras.

Morphometry and abnormalities of the feet of Kaimanawa feral horses in New Zealand

Objective: The present study investigated the foot health of the Kaimanawa feral horse population and tested the hypotheses that horses would have a large range of foot morphology and that the incidence of foot abnormality would be significantly high. Procedures: Abnormality was defined as a variation from what the two veterinarian assessors considered as optimal morphology and which was considered to impact negatively on the structure and/or function of the foot. Fifteen morphometric variables were measured on four calibrated photographic views of all four feet of 20 adult Kaimanawa feral horses. Four morphometric variables were measured from the lateromedial radiographs of the left forefoot of each horse. In addition, the study identified the incidence of gross abnormality observed on the photographs and radiographs of all 80 feet. Results: There was a large variation between horses in the morphometric dimensions, indicating an inconsistent foot type. Mean hoof variables were outside the normal range recommended by veterinarians and hoof care providers; 35% of all feet had a long toe conformation and 15% had a mediolateral imbalance. Abnormalities included lateral (85% of horses) and dorsal (90% of horses) wall flares, presence of laminar rings (80% of horses) and bull-nose tip of the distal phalanx (75% of horses). Both hypotheses were therefore accepted. Conclusions: The Kaimanawa feral horse population demonstrated a broad range of foot abnormalities and we propose that one reason for the questionable foot health and conformation is lack of abrasive wearing by the environment. In comparison with other feral horse populations in Australia and America there may be less pressure on the natural selection of the foot of the Kaimanawa horses by the forgiving environment of the Kaimanawa Ranges. Contrary to popular belief, the feral horse foot type should not be used as an ideal model for the domestic horse foot.

A comparative study of different porous amorphous silica minerals supported TiO2 catalysts

Three porous amorphous silica minerals, including diatomite, opal and porous precipitated SiO2wereadopted to prepare supported TiO2catalysts by hydrolysis–deposition method. The prepared compoundmaterials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fouriertransform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and X-ray photo-electron spectroscopy (XPS). Through morphology and physical chemistry properties of the resultingTiO2/amorphous SiO2catalysts, it was proposed that the nature of silica supports could affect the particlesize and the crystal form of TiO2and then further influence the photocatalytic property of TiO2/amorphousSiO2catalysts. The catalytic properties of these porous amorphous silica supported photocatalysts(TiO2/SiO2) were investigated by UV-assisted degradation of Rhodamine B (RhB). Compared with pureTiO2(P25) and the other two TiO2/amorphous SiO2catalysts, TiO2/diatomite photocatalyst exhibits bet-ter catalytic performance at different calcined temperatures, the decoloration rate of which can be upto over 85% even at a relatively low calcined temperature. The TiO2/diatomite photocatalyst possessesmixed-phase TiO2with relatively smaller particles size, which might be responsible for higher photo-catalytic activity. Moreover, the stable and much inerter porous microstructure of diatomite could beanother key factor in improving its activity.

Plasma cytokine changes in relation to exercise intensity and muscle damage

The purpose of this study was to compare the effects of exercise intensity and exercise-induced muscle damage on changes in anti-inflammatory cytokines and other inflammatory mediators. Nine well-trained male runners completed three different exercise trials on separate occasions: (1) level treadmill running at 60% VO2max (moderate-intensity trial) for 60 min; (2) level treadmill running at 85% VO2max (high-intensity trial) for 60 min; (3) downhill treadmill running (-10% gradient) at 60% VO2max (downhill running trial) for 45 min. Blood was sampled before, immediately after and 1 h after exercise. Plasma was analyzed for interleukin-1 receptor antagonist (IL-1ra), IL-4, IL-5, IL-10, IL-12p40, IL-13, monocyte chemotactic protein-1 (MCP-1), prostaglandin E(2), leukotriene B(4) and heat shock protein 70 (HSP70). The plasma concentrations of IL-1ra, IL-12p40, MCP-1 and HSP70 increased significantly (P<0.05) after all three trials. Plasma prostaglandin E(2) concentration increased significantly after the downhill running and high-intensity trials, while plasma IL-10 concentration increased significantly only after the high-intensity trial. IL-4 and leukotriene B(4) did not increase significantly after exercise. Plasma IL-1ra and IL-10 concentrations were significantly higher (P<0.05) after the high-intensity trial than after both the moderate-intensity and downhill running trials. Therefore, following exercise up to 1 h duration, exercise intensity appears to have a greater effect on anti-inflammatory cytokine production than exercise-induced muscle damage

Exercise-induced muscle damage, plasma cytokines and markers of neutrophil activation

Introduction: Unaccustomed eccentric exercise often results in muscle damage and neutrophil activation. We examined changes in plasma cytokines stress hormones, creatine kinase activity and myoglobin concentration, neutrophil surface receptor expression, degranulation, and the capacity of neutrophils to generate reactive oxygen species in response to in vitro stimulation after downhill running. Methods: Ten well-trained male runners ran downhill on a treadmill at a gradient of -10% for 45 min at 60% V̇O2max. Blood was sampled immediately before (PRE) and after (POST), 1 h (1 h POST), and 24 h (24 h POST) after exercise. Results: At POST, there were significant increases (P < 0.01) in neutrophil count (32%), plasma interleukin (IL)-6 concentration (460%), myoglobin (Mb) concentration (1100%), and creatine kinase (CK) activity (40%). At 1 h POST, there were further increases above preexercise values for neutrophil count (85%), plasma Mb levels (1800%), and CK activity (56%), and plasma IL-6 concentration remained above preexercise values (410%) (P < 0.01). At 24 h POST, neutrophil counts and plasma IL-6 levels had returned to baseline, whereas plasma Mb concentration (100%) and CK activity (420%) were elevated above preexercise values (P < 0.01). There were no significant changes in neutrophil receptor expression, degranulation and respiratory burst activity, and plasma IL-8 and granulocyte-colony stimulating factor concentrations at any time after exercise. Neutrophil count correlated with plasma Mb concentration at POST (r = 0.64, P < 0.05), and with plasma CK activity at POST (r = 0.83, P < 0.01) and 1 h POST (r = 0.78, P < 0.01). Conclusion: Neutrophil activation remains unchanged after downhill running in well-trained runners, despite increases in plasma markers of muscle damage.

Carbohydrate supplementation and alterations in neutrophils, and plasma cortisol and myoglobin concentration after intense exercise

The present study examined the effect of carbohydrate supplementation on changes in neutrophil counts, and the plasma concentrations of cortisol and myoglobin after intense exercise. Eight well-trained male runners ran on a treadmill for 1 h at 85% maximal oxygen uptake on two separate occasions. In a double-blind cross-over design, subjects consumed either 750 ml of a 10% carbohydrate (CHO) drink or a placebo drink on each occasion. The order of the trials was counter-balanced. Blood was drawn immediately before and after exercise, and 1 h after exercise. Immediately after exercise, neutrophil counts (CHO, 49%; placebo, 65%; P<0.05), plasma concentrations of glucose (CHO, 43%; P<0.05), lactate (CHO, 130%; placebo, 130%; P<0.01), cortisol (CHO, 100%; placebo, 161%; P<0.01), myoglobin (CHO, 194%; placebo, 342%; P<0.01) all increased significantly. One hour post-exercise, plasma myoglobin concentration (CHO, 331%; placebo, 482%; P<0.01) and neutrophil count (CHO, 151%; placebo, 230% P<0.01) both increased further above baseline. CHO significantly attenuated plasma myoglobin concentration and the neutrophil count after exercise (P<0.01), but did not affect plasma cortisol concentration. The effects of CHO on plasma myoglobin concentration may be due to alterations in cytokine synthesis, insulin responses or myoglobin clearance rates from the bloodstream during exercise. Plasma cortisol responses to CHO during exercise may depend on the intensity of exercise, or the amount of CHO consumed. Lastly, cortisol appears to play a minor role in the mobilisation of neutrophils after intense exercise.

Changes in neutrophil surface receptor expression, degranulation, and respiratory burst activity after moderate- and high-intensity exercise

Intense exercise stimulates the systemic release of a variety of factors that alter neutrophil surface receptor expression and functional activity. These alterations may influence resistance to infection after intense exercise. The aim of this study was to examine the influence of exercise intensity on neutrophil receptor expression, degranulation (measured by plasma and intracellular myeloperoxidase concentrations), and respiratory burst activity. Ten well-trained male runners ran on a treadmill for 60 min at 60% [moderate-intensity exercise (MI)] and 85% maximal oxygen consumption [high-intensity exercise (HI)]. Blood was drawn immediately before and after exercise and at 1 h postexercise. Immediately after HI, the expression of the neutrophil receptor CD16 was significantly below preexercise values (P < 0.01), whereas MI significantly reduced CD35 expression below preexercise values (P < 0.05). One hour after exercise at both intensities, there was a significant decline in CD11b expression (P < 0.05) and a further decrease in CD16 expression compared with preexercise values (P < 0.01). CD16 expression was lower 1 h after HI than 1 h after MI (P < 0.01). Immediately after HI, intracellular myeloperoxidase concentration was less than preexercise values (P < 0.01), whereas plasma myeloperoxidase concentration was greater (P < 0.01), indicating that HI stimulated neutrophil degranulation. Plasma myeloperoxidase concentration was higher immediately after HI than after MI (P < 0.01). Neutrophil respiratory burst activity increased after HI (P < 0.01). In summary, both MI and HI reduced neutrophil surface receptor expression. Although CD16 expression was reduced to a greater extent after HI, this reduction did not impair neutrophil degranulation and respiratory burst activity.

The effects of cold air (-110°C) and water (8°C) cryotherapy on knee skin temperature

Exposure to cold air, whole body cryotherapy (WBC), is a novel treatment employed by athletes. In WBC individuals dressed in minimal clothing are exposed to a temperature below -100°C for 2-4 min. The use of WBC has been advocated as a treatment for various knee injuries. PURPOSE: To compare the effects of two modalities of cryotherapy, -110°C WBC and 8°C cold water immersion (CWI) on knee skin temperature (Tsk). METHODS: With ethical approval and written informed consent 10 healthy active male participants (26.5±4.9 yr, 183.5±6.0 cm, 90.7±19.9 kg, 26.8±5.0 kg/m2, 23.0±9.3% body fat (measured by DXA), 7.6 ± 2.0 mm patellar skin fold; mean±SD) were exposed to 4 min of CWI and WBC. The treatment order was randomised in a controlled crossover design, with a minimum of 7 days between treatments. During WBC participants stood in a chamber (-60±3°C) for 20 s before entering the main chamber (-110°C±3°C) where they remained for 3 min and 40 s. For CWI participants were seated in a tank filled with cold water (8±0.3°C) and immersed to the level of the sternum for 4 min. Right knee Tsk was assessed via non-contact, infrared thermal imaging. A quadrilateral region of interest was created using inert markers placed 5 cm above and below the most superior and inferior aspect of the patella. Tsk within this quadrilateral was recorded pre, immediately post and every 10 min thereafter for 60 min. Tsk changes were examined using a two-way (treatment x time) repeated measures analyses of variance. In addition, a paired sample t-test was used to compare baseline Tsk before both treatments. RESULTS: Knee Tsk was similar before treatment (WBC: 29.9±0.7°C, CWI: 29.6±0.9°C, p>0.05). There was a significant main effect for treatment (p<0.05) and time (p<0.001). Compared to baseline, Tsk was significantly reduced (p<0.05) immediately post and at 10, 20, 30, 40, 50 and 60 min after both cooling modalities. Knee Tsk was lower (p<0.05) immediately after WBC (19.0±0.9°C) compared to CWI (20.5±0.6°C). However, from 10 to 60 min post, knee Tsk was lower (p<0.05) following the CWI treatment. CONCLUSION: WBC elicited a greater decrease in knee Tsk compared to CWI immediately after treatment. However, both modalities display different recovery patterns and Tsk after CWI was significantly lower than WBC at 10, 20, 30, 40, 50 and 60 min after treatment.

Measurement error of rearfoot kinematics during running between a 100Hz and 30Hz camera

Background: Measurement accuracy is critical for biomechanical gait assessment. Very few studies have determined the accuracy of common clinical rearfoot variables between cameras with different collection frequencies. Research question: What is the measurement error for common rearfoot gait parameters when using a standard 30Hz digital camera compared to 100Hz camera? Type of study: Descriptive. Methods: 100 footfalls were recorded from 10 subjects ( 10 footfalls per subject) running on a treadmill at 2.68m/s. A high-speed digital timer, accurate within 1ms served as an external reference. Markers were placed along the vertical axis of the heel counter and the long axis of the shank. 2D coordinates for the four markers were determined from heel strike to heel lift. Variables of interest included time of heel strike (THS), time of heel lift (THL), time to maximum eversion (TMax), and maximum rearfoot eversion angle (EvMax). Results: THS difference was 29.77ms (+/- 8.77), THL difference was 35.64ms (+/- 6.85), and TMax difference was 16.50ms (+/- 2.54). These temporal values represent a difference equal to 11.9%, 14.3%, and 6.6% of the stance phase of running gait, respectively. EvMax difference was 1.02 degrees (+/- 0.46). Conclusions: A 30Hz camera is accurate, compared to a high-frequency camera, in determining TMax and EvMax during a clinical gait analysis. However, relatively large differences, in excess of 12% of the stance phase of gait, for THS and THL variables were measured.

A practical comparison of manual and autonomous methods for acoustic monitoring

1. Autonomous acoustic recorders are widely available and can provide a highly efficient method of species monitoring, especially when coupled with software to automate data processing. However, the adoption of these techniques is restricted by a lack of direct comparisons with existing manual field surveys. 2. We assessed the performance of autonomous methods by comparing manual and automated examination of acoustic recordings with a field-listening survey, using commercially available autonomous recorders and custom call detection and classification software. We compared the detection capability, time requirements, areal coverage and weather condition bias of these three methods using an established call monitoring programme for a nocturnal bird, the little spotted kiwi(Apteryx owenii). 3. The autonomous recorder methods had very high precision (>98%) and required <3% of the time needed for the field survey. They were less sensitive, with visual spectrogram inspection recovering 80% of the total calls detected and automated call detection 40%, although this recall increased with signal strength. The areal coverage of the spectrogram inspection and automatic detection methods were 85% and 42% of the field survey. The methods using autonomous recorders were more adversely affected by wind and did not show a positive association between ground moisture and call rates that was apparent from the field counts. However, all methods produced the same results for the most important conservation information from the survey: the annual change in calling activity. 4. Autonomous monitoring techniques incur different biases to manual surveys and so can yield different ecological conclusions if sampling is not adjusted accordingly. Nevertheless, the sensitivity, robustness and high accuracy of automated acoustic methods demonstrate that they offer a suitable and extremely efficient alternative to field observer point counts for species monitoring.

Characterization of the sulphate mineral amarantite Fe3 2 3+ (SO4)O 7H2O using infrared, Raman spectroscopy and thermogravimetry

The mineral amarantite Fe23+(SO4)O∙7H2O has been studied using a combination of techniques including thermogravimetry, electron probe analyses and vibrational spectroscopy. Thermal analysis shows decomposition steps at 77.63, 192.2, 550 and 641.4°C. The Raman spectrum of amarantite is dominated by an intense band at 1017 cm-1 assigned to the SO42- ν1 symmetric stretching mode. Raman bands at 1039, 1054, 1098, 1131, 1195 and 1233 cm-1 are attributed to the SO42- ν3 antisymmetric stretching modes. Very intense Raman band is observed at 409 cm-1 with shoulder bands at 399, 451 and 491 cm-1 are assigned to the v2 bending modes. A series of low intensity Raman bands are found at 543, 602, 622 and 650 cm-1 are assigned to the v4 bending modes. A very sharp Raman band at 3529 cm-1 is assigned to the stretching vibration of OH units. A series of Raman bands observed at 3025, 3089, 3227, 3340, 3401 and 3480 cm-1 are assigned to water bands. Vibrational spectroscopy enables aspects of the molecular structure of the mineral amarantite to be ascertained.

The Tashi project 2004-2010 : developing methods for creating theatre works that fully engage children aged between 3 and 10

Over a seven-year period, Mark Radvan directed a suite of children’s theatre productions adapted from the original Tashi stories by Australian writers Anna and Barbara Fienberg. The Tashi Project’s repertoire of plays performed to over 40,000 children aged between 3 and 10 years old, and their carers, in seasons at the Out of the Box Festival, at Brisbane Powerhouse and in venues across Australia in two interstate tours in 2009 and 2010. The project investigated how best to combine an exploration of theatrical forms and conventions, with a performance style evolved in a specially developed training program and a deliberate positioning of young children as audiences capable of sophisticated readings of action, symbol, theme and character. The results of this project show that when brought into appropriate relationship with the theatre artists, young children aged 3-5 can engage with sophisticated narrative forms, and with the right contextual framing they enjoy heightened dramatic and emotional tension, bringing to the event sustained and highly engaged concentration. Older children aged 6-10 also bring sustained and heightened engagement to the same stories, providing that other more sophisticated dramatic elements are woven into the construction of the performances, such as character, theme and style.

The catalytic role of an isolated-Ti atom in the hydrogenation of Ti-doped Al(001) surface : An ab initio density functional theory calculation

Recent work [S. Chaudhuri, J.T. Muckerman, J. Phys. Chem. B 109 (2005) 6952] reported that two Ti-substituted atoms on an Al(0 0 1) surface can form a catalytically active site for the dissociation of H2, but the diffusion barrier of atomic H away from Ti site is as high as 1.57 eV. By using ab initio density functional calculations, we found that two hydrogen molecules can dissociate on isolated-Ti atom doped Al(0 0 1) surface with small activation barriers (0.21 and 0.235 eV for first and second H2, respectively). Additionally, the diffusion barrier of atomic H away from Ti site is also moderate (0.47 eV). These results contribute further towards understanding the improved kinetics observed in recycling of hydrogen with Ti-doped NaAlH4.