Effect of confining pressure on diffusion coefficients in clay-rich, low-permeability sedimentary rocks.

The effect of confining pressure (CP) on the diffusion of tritiated-water (HTO) and iodide (I-) tracers through Ordovician rocks from the Michigan Basin, southwestern Ontario, Canada, and Opalinus Clay from Schlattingen, Switzerland was investigated in laboratory experiments. Four samples representing different formations and lithologies in the Michigan Basin were studied: Queenston Formation shale, Georgian Bay Formation shale, Cobourg Formation limestone and Cobourg Formation argillaceous limestone. Estimated in situ vertical stresses at the depths from which the samples were retrieved range from 12.0 to 17.4MPa (Michigan Basin) and from 21 to 23MPa (Opalinus Clay). Effective diffusion coefficients (De) were determined in through-diffusion experiments. With HTO tracer, applying CP resulted in decreases in De of 12.5% for the Queenston Formation shale (CPmax=12MPa), 30% for the Georgian Bay Formation shale (15MPa), 34% for the Cobourg Formation limestone (17.4MPa), 31% for the Cobourg Formation argillaceous limestone (17.4MPa) and 43-46% for the Opalinus Clay (15MPa). Decreases in De were larger for the I- tracer: 13.8% for the Queenston shale, 42% for the Georgian Bay shale, 50% for the Cobourg Formation limestone, 55% for the Cobourg Formation argillaceous limestone and 63-68% for the Opalinus Clay. The tracer-specific nature of the response is attributed to an increasing influence of anion exclusion as the pore size decreases at higher CP. Results from the shales (including Opalinus Clay) indicate that the pressure effect on De can be represented by a linear relationship between De and ln(CP), which provides valuable predictive capability. The nonlinearity results in a relatively small change in De at high CP, suggesting that it is not necessary to apply the exact in situ pressure conditions in order to obtain a good estimate of the in situ diffusion coefficient. Most importantly, the CP effect on shale is reversible (±12%) suggesting that, for argillaceous rocks, it is possible to obtain De values that are representative of the in-situ condition by conducting measurements on re-pressurized samples that were obtained with standard drilling practices. This may not be the case for brittle rock samples as the results from limestone suggest that irreversible damage occurred during the pressure cycling.

Diffusive anisotropy in low-permeability Ordovician sedimentary rocks from the Michigan Basin in southwest Ontario.

Diffusive anisotropy was investigated using samples from Upper Ordovician shale and argillaceous limestone from the Michigan Basin of southwest Ontario, Canada. Effective diffusion coefficients (De) were determined for iodide (I(-)) and tritiated water (HTO) tracers on paired cm-scale subsamples oriented normal (NB) and parallel to bedding (PB) prepared from preserved drill cores within one year from the date of drilling. For samples with porosity >3%, an X-ray radiography method was used with I(-) tracer for determination of De and porosity accessible to I(-) ions. A through-diffusion method with I(-) and HTO tracers was used for most siltstone and limestone samples with low-porosity (<3%). The De values range from 7.0×10(-13) to 7.7×10(-12) m(2)·s(-1) for shale, 2.1×10(-13) to 1.3×10(-12) m(2)·s(-1) for limestone, and 5.3×10(-14) to 5.6×10(-13) m(2)·s(-1) for siltstone and limestone interbeds within the Georgian Bay Formation shale. The sample-scale anisotropy ratios (De-PB:De-NB) for De values obtained using the I(-) tracer are 0.9 to 4.9, and the anisotropy ratios for the HTO tracer are in the range of 1.1 to 7.0. The influence of porosity distribution on diffusive anisotropy has been investigated using one-dimensional spatially-resolved profiles of I(-)-accessible porosity (shale only) and the use of AgNO3 for fixation of I(-) tracer in the pores, allowing for SEM visualization of I(-)-accessible pore networks. The porosity profiles at the sample scale display greatest variability in the direction normal to bedding which likely reflects sedimentary depositional processes. The SEM imaging suggests that diffusion pathways are preferentially oriented parallel to bedding in the shale and that diffusion occurs dominantly within the argillaceous component of the limestone. However, the fine clay-filled intergranular voids in the dolomitic domains of the limestone are also accessible for diffusive transport.

Neuromuscular control and ankle instability.

Lateral ankle sprains (LAS) are common injuries in athletics and daily activity. Although most are resolved with conservative treatment, others develop chronic ankle instability (AI)-a condition associated with persistent pain, weakness, and instability-both mechanical (such as ligamentous laxity) and functional (neuromuscular impairment with or without mechanical laxity). The predominant theory in AI is one of articular deafferentation from the injury, affecting closed-loop (feedback/reflexive) neuromuscular control, but recent research has called that theory into question. A considerable amount of attention has been directed toward understanding the underlying causes of this pathology; however, little is known concerning the neuromuscular mechanisms behind the development of AI. The purpose of this review is to summarize the available literature on neuromuscular control in uninjured individuals and individuals with AI. Based on available research and reasonable speculation, it seems that open-loop (feedforward/anticipatory) neuromuscular control may be more important for the maintenance of dynamic joint stability than closed-loop control systems that rely primarily on proprioception. Therefore, incorporating perturbation activities into patient rehabilitation schemes may be of some benefit in enhancing these open-loop control mechanisms. Despite the amount of research conducted in this area, analysis of individuals with AI during dynamic conditions is limited. Future work should aim to evaluate dynamic perturbations in individuals with AI, as well as subjects who have a history of at least one LAS and never experienced recurrent symptoms. These potential findings may help elucidate some compensatory mechanisms, or more appropriate neuromuscular control strategies after an LAS event, thus laying the groundwork for future intervention studies that can attempt to reduce the incidence and severity of acute and chronic lateral ankle injury.

Effects of high volume upper extremity plyometric training on throwing velocity and functional strength ratios of the shoulder rotators in collegiate baseball players.

To achieve maximal force output, clinicians and coaches have been experimenting with upper extremity plyometric exercises for years, without sufficient scientific validation of this training method. The goal of this study was to examine the effects of an 8-week course of high volume upper extremity plyometric training on the isokinetic strength and throwing velocity of a group of intercollegiate baseball players. Twenty-four Division I collegiate baseball players (age: 19.7 +/- 1.3 years; height: 183.9 +/- 5.9 cm; mass: 90.7 +/- 10.5 kg) were recruited to participate in this study. Throwing velocity, isokinetic peak torque, isokinetic functional strength ratios, and time to peak torque were measured pre- and posttraining. Subjects were rank-ordered according to concentric internal rotation (IR) strength and were assigned randomly to either the plyometric training group (PLY) or the control group (CON). Training consisted of 6 upper extremity plyometric exercises ("Ballistic Six") performed twice per week for 8 weeks. Subjects assigned to CON performed regular off-season strength and conditioning activities, but did not perform plyometric activities. PLY demonstrated significant increases (p < 0.05) in throwing velocity following 8 weeks of training when compared with CON (83.15 mph [pre] vs. 85.15 mph [post]). There were no statistically significant differences in any of the isokinetic strength measurements between PLY and CON groups pre- to posttraining. Statistically significant differences were seen within PLY for concentric IR and eccentric external rotation (ER) isokinetic strength at 180 degrees x s(-1) and 300 degrees x s(-1); and within CON for eccentric ER isokinetic strength at 300 degrees x s(-1) and concentric IR isokinetic strength at 180 degrees x s(-1). The Ballistic Six training protocol can be a beneficial supplement to a baseball athlete's off-season conditioning by improving functional performance and strengthening the rotator cuff musculature.

Spatially resolved measurement of rock core porosity.

Density weighted, centric scan, Conical SPRITE MRI techniques are applied in the current work for local porosity measurements in fluid saturated porous media. The methodology is tested on a series of sandstone core samples. These samples vary in both porosity and degree of local heterogeneity due to bedding plane structure. The MRI porosity measurement is in good agreement with traditional gravimetric measurements of porosity. Spatially resolved porosity measurements reveal significant porosity variation in some samples. This novel MRI technique should have applications to the characterization of local porosity in a wide variety of porous media.

Geochemical reactions resulting from in situ oxidation of PCE-DNAPL by KMnO4 in a sandy aquifer.

Although the potential for KMnO4 to destroy chlorinated ethenes in situ was first recognized more than a decade ago, the geochemical processes that accompany the oxidation have not previously been examined. In this study, aqueous KMnO4 solutions (10-30 g/L) were injected into an unconfined sand aquifer contaminated by the dense non-aqueous-phase liquid (DNAPL) tetrachloroethylene (PCE). The effects of the injections were monitored using depth-specific, multilevel groundwater samplers, and continuous cores. Two distinct geochemical zones evolved within several days after injection. In one zone where DNAPL is present, reactions between KMnO4 and dissolved PCE resulted in the release of abundant chloride and hydrogen ions to the water. Calcite and dolomite dissolved, buffering the pH in the range of 5.8-6.5, releasing Ca, Mg, and CO2 to the pore water. In this zone, the aqueous Ca/Cl concentration ratio is close to 5:12, consistent with the following reaction for the oxidation of PCE in a carbonate-rich aquifer: 3C2Cl4 + 5CaCO3(s) + 4KMnO4 + 2H+ --> 11CO2 + 4MnO2(s) + H2O + 12Cl- + 5Ca2+ + 4K+. In addition to Mg from dolomite dissolution, increases in the concentration of Mg as well as Na may result from exchange with K at cation-exchange sites. In the second zone, where lesser amounts of PCE were present, KMnO4 persisted in the aquifer for more than 14 months, and the porewater pH increased graduallyto between 9 and 10 as a resultof reaction between KMnO4 and H2O. A small increase in SO4 concentrations in the zones invaded by KMnO4 suggests that KMnO4 injections caused oxidation of sulfide minerals. There are important benefits of carbonate mineral buffering during DNAPL remediation by in situ oxidation. In a carbonate-buffered system, Mn(VII) is reduced to Mn(IV) and is immobilized in the groundwater by precipitating as insoluble manganese oxide. Energy-dispersive X-ray spectroscopy analyses of the manganese oxide coatings on aquifer mineral grains have detected the impurities Al, Ca, Cl, Cu, Pb, P, K, Si, S, Ti, U, and Zn indicating that, similar to natural systems, precipitation of manganese oxide is accompanied by coprecipitation of other elements. In addition, the consumption of excess KMnO4 by reaction with reduced minerals such as magnetite will be minimized because the rates of these reactions increase with decreasing pH. Aquifer cores collected after the KMnO4 injections exhibit dark brown to black bands of manganese oxide reaction products in sand layers where DNAPL was originally present. Mineralogical investigations indicate that the manganese oxide coatings are uniformly distributed over the mineral grains. Observations of the coatings using transmission electron microscopy indicate that they are on the order of 1 microm thick, and consequently, the decrease in porosity through the formation of the coatings is negligible.