Effect of radial advection on autocatalytic reaction-diffusion fronts.

The reaction-diffusion-advection properties of autocatalytic fronts are studied both theoretically and experimentally in the case where the autocatalytic species is injected radially into the reactant at a constant flow rate. The theoretical part analyzes both polar and spherical cases. At long times or equivalently large radius from the injection point, the well-known properties of one-dimensional reaction-diffusion autocatalytic fronts are logically recovered as the influence of the advection field decreases radially. At earlier times however, the radial advection impacts the dynamics of the front. We characterize numerically the influence in this transient regime of the injection flow rate and of the ratio of initial concentration of reactant and autocatalytic product on the position of the front, the reaction rate and the amount of product generated. We confirm experimentally the theoretical predictions in polar geometries using the autocatalytic chlorite-tetrathionate reaction.

Freezing chicken semen: Influence of base medium osmolality, cryoprotectants, cryoprotectant concentration, and cooling rate on post-thaw sperm survival.

A classical chicken semen diluent (Lake's 7.1 diluent) was modified to have lowered osmolalities (ranging from 290 to 410 mOsm/kg). The modified medium with physiological osmolality of 325 mOsm/kg allowed cold storage of fresh semen for several days with very little loss of membrane integrity and motility, while high osmolalities inhibited motility. This modified medium was then used as base for freezing medium to test effects of the type and concentration of cryoprotective agent (CPA), and the cooling rate (CR). A number of CPAs (methylformamide, methylacetamide, dimethylformamide (DMF), dimethylacetamide (DMA), diethylformamide, and propylene glycol) were first compared by freezing semen with 0.6 mol/l of the respective CPA at a cooling rate of 250 °C/min. Post-thaw motility and membrane integrity were highest with DMA and DMF. Finally, in more detailed factorial experiments, semen from individual cocks or pooled semen was frozen using CRs of 4, 50, 250, and 440 °C/min and DMA concentrations ([DMA]) of 0.4, 0.6, 1.0, and 1.5 mol/l. Straws from each semen sample x treatment combination were divided for semen assessment at three different research groups for sperm motility, membrane integrity, kinked tails, and DNA fragmentation, using microscopy, computer assisted motility analysis, and flow cytometry. There were clear effects of both CR and [DMA] and their interaction. CRs 50 and 250 °C/min gave best post-thaw sperm performance. Higher DMA concentrations gave better post-thaw membrane integrity, but concentrations above 1.0 mol/l can decrease sperm velocity or even inhibit sperm motility. Therefore [DMA] may best be 0.6-1.0 mol/l at a CR of 50-250 °C/min.

Linear stability analysis and nonlinear simulations of convective dissolution in an inclined porous layer between impermeable surfaces.

Convective dissolution can occur in porous media when a given solute dissolves in a host layer from above and increases the density of the host solution. Buoyancy-driven fingering can then develop, which increases the transfer flux of the solute. We investigate here numerically the properties of this convective dissolution when the porous host layer is inclined by an angle θ relative to the horizontal direction. We consider an incompressible flow in porous media governed by Darcy's law, driven by density gradients associated with the concentration of the dissolving solute. The model problem focuses on the case of a very long (infinite) tilted porous layer limited by two parallel impermeable surfaces. A linear stability analysis and nonlinear simulations are performed using the Boussinesq approximation. A vorticity-stream function formulation is adopted to solve the two-dimensional hydrodynamic field through the finite element method. We find that the inclination of the interface decreases the growth rate of the instability and the range of unstable wavenumbers, delaying or even suppressing the onset of the fingering instability. Moreover, it introduces a drift velocity on the perturbations, which is characterized here in both the linear stability analysis and the nonlinear simulations.

Scalings of Rayleigh-Taylor Instability at Large Viscosity Contrasts in Porous Media.

The scalings of the Rayleigh-Taylor instability are studied numerically for porous media flows when the denser fluid lying on top of the less dense one is also much more viscous. We show that, above a critical value of the viscosity ratio M, a symmetry breaking of the buoyancy-driven fingers is observed as they extend much further downward than upward. The asymmetry ratio scales as M^{1/2} while the asymptotic flux across the initial contact line, quantifying the mixing between the two fluids, scales as M^{-1/2}. A new fingering mechanism induced by large viscosity contrasts is identified and shows good agreement with experimentally observed dynamics.

Oscillatory budding dynamics of a chemical garden within a co-flow of reactants.

The oscillatory growth of chemical gardens is studied experimentally in the budding regime using a co-flow of two reactant solutions within a microfluidic reactor. The confined environment of the reactor tames the erratic budding growth and the oscillations leave their imprint with the formation of orderly spaced membranes on the precipitate surface. The average wavelength of the spacing between membranes, the growth velocity of the chemical garden and the oscillations period are measured as a function of the velocity of each reactant. By means of materials characterization techniques, the micro-morphology and the chemical composition of the precipitate are explored. A mathematical model is developed to explain the periodic rupture of droplets delimitated by a shell of precipitate and growing when one reactant is injected into the other. The predictions of this model are in good agreement with the experimental data.

Effects of radial injection and solution thickness on the dynamics of confined A + B → C chemical fronts.

The spatio-temporal dynamics of an A + B → C front subjected to radial advection is investigated experimentally in a thin solution layer confined between two horizontal plates by radially injecting a solution of potassium thiocyanate (A) into a solution of iron(iii) nitrate (B). The total amount and spatial distribution of the product FeSCN2+ (C) are measured for various flow rates Q and solution thicknesses h. The long-time evolution of the total amount of product, nC, is compared to a scaling obtained theoretically from a one-dimensional reaction-diffusion-advection model with passive advection along the radial coordinate r. We show that, in the experiments, nC is significantly affected when varying either Q or h but scales as nC∼Q-1/2V where V is the volume of injected reactant A provided the solution thickness h between the two confining plates is sufficiently small, in agreement with the theoretical prediction. Our experimental results also evidence that the temporal evolution of the width of the product zone, WC, follows a power law, the exponent of which varies with both Q and h, in disagreement with the one-dimensional model that predicts WC∼t1/2. We show that this experimental observation can be rationalized by taking into account the non-uniform profile of the velocity field of the injected reactant within the cell gap.

Influence of rectilinear vs radial advection on the yield of A + B → C reaction fronts: A comparison.

In the presence of advection at a constant flow rate in a rectilinear geometry, the properties of planar A + B → C reaction fronts feature the same temporal scalings as in the pure reaction-diffusion case. In a radial injection geometry where A is injected into B radially at a constant flow rate Q, temporal scalings are conserved, but the related coefficients depend on the injection flow rate Q and on the ratio γ of initial concentrations of the reactants. We show here that this dependence of the front properties on the radial velocity allows us to tune the amount of product obtained in the course of time by varying the flow rate. We compare theoretically the efficiency of the rectilinear and radial geometries by computing the amount of product C generated in the course of time or per volume of reactant injected. We show that a curve γc(Q) can be defined in the parameter space (γ, Q) below which, for similar experimental conditions, the total amount of C is larger in the radial case. In addition, another curve γ*(Q) < γc(Q) can be defined such that for γ < γ*, the total amount of C produced is larger in the radial geometry, even if the production of C per unit area of the contact interface between the two reactants is larger in the rectilinear case. This comes from the fact that the length of the contact zone increases with the radius in the radial case, which allows us to produce in fine more product C for a same injected volume of reactant or in reactors of a same volume than in the rectilinear case. These results pave the way to the geometrical optimization of the properties of chemical fronts.

Confined direct and reverse chemical gardens: Influence of local flow velocity on precipitation patterns.

Various cobalt silicate precipitation patterns can be observed when an aqueous solution of cobalt ions gets into contact with a solution of silicate ions upon injection of one solution into the other in the confined geometry of a Hele-Shaw cell. The properties of these precipitation patterns are studied here as a function of the injection flow rate, densities and viscosities of the solutions, and the choice of which solution is injected into the other one. Our results show that the structure of the precipitation pattern depends on the local velocity as well as on the difference in viscosities between the injected and the displaced solutions. Specifically, decreasing the injection flow rate and/or decreasing the density jump while increasing the difference in viscosities between the reactant solutions results in more circular patterns. Moreover, we show that some structures are robustly observed in given ranges of the local flow velocity in the cell. Locally, precipitation can then transition from one type of pattern to another during injection, according to that preferred structure at the given local velocity. We also show that injection of the cobalt solution into the silicate solution results in the so-called direct patterns that are different from the reverse patterns obtained when the silicate solution is injected in the solution of cobalt ions. Our results help in understanding the production of precipitate structures under nonequilibrium flow conditions.

Viscous Fingering Induced by a pH-Sensitive Clock Reaction.

A pH-changing clock chemical system, also known to induce changes in viscosity, is shown experimentally to induce a viscous fingering instability during the displacement of reactive solutions in a Hele-Shaw cell. Specifically, a low-viscosity solution of formaldehyde is displaced by a more viscous solution of sulfite and of a pH-sensitive poly(acrylic acid) polymer. The pH change triggered by the formaldehyde-sulfite clock reaction in the reactive contact zone between the two solutions affects the polymer and induces a local increase of the viscosity that destabilizes the displacement via a viscous fingering instability. The influence of changes in the chemical parameters on this fingering instability is analyzed using different techniques and the results are compared with numerical simulations.

Enhanced convective dissolution due to an A + B → C reaction: control of the non-linear dynamics via solutal density contributions.

Chemical reactions can have a significant impact on convective dissolution in partially miscible stratifications in porous media and are able to enhance the asymptotic flux with respect to the non-reactive case. We numerically study such reactive convective dissolution when the dissolving species A increases the density of the host phase upon dissolution and reacts with a reactant B present in the host phase to produce C by an A + B → C reaction. Upon varying the difference ΔRCB = RC-RB between the Rayleigh numbers of the product C and the reactant B, we identify four regimes with distinct dynamics when the diffusion coefficients are the same. When ΔRCB < 0, the density profiles are non-monotonic and the non-linear dynamics are seen to depend on the relative values of the density at the interface and the initial density of the host phase. For ΔRCB > 0, the monotonic density profiles are destabilizing with respect to the non-reactive case above a certain critical value ΔRcr. We analyze quantitatively the influence of varying ΔRCB and the ratio ß = B0/A0 of the initial concentration of B and the solubility of A on the asymptotic steady flux, the wavelength of the fingers and the position of the reaction front. In the context of CO2 geological sequestration, understanding how such reactions can enhance the dissolution flux is crucial for improving the efficiency and safety of the process.

Chemically-driven convective dissolution.

When a solute A dissolves in a host phase with a given solubility, the resulting density stratification is stable towards convection if the density profile increases monotonically along the gravity field. We theoretically and numerically study the convective destabilization by reaction of this dissolution when A reacts with a solute B present in the host phase to produce C via an A + B→C type of reaction. In this reactive case, composition changes can give rise to non-monotonic density profiles with a local maximum. A convective instability can then be triggered locally in the zone where the denser product overlies the less dense bulk solution. First, we perform a linear stability analysis to identify the critical conditions for this reaction-driven convective instability. Second, we perform nonlinear simulations and compare the critical values of the control parameters for the onset of convection in these simulations with those predicted by linear stability analysis. We further show that the asymptotic dissolution flux of A can be increased in the convective regime by increasing the difference ΔRCB = RC-RB between the Rayleigh numbers of the product C and reactant B above a critical value and by increasing the ratio ß = B0/A0 between the initial concentration B0 of reactant B and the solubility A0 of A. Our results indicate that chemical reactions can not only initiate convective mixing but can also give rise to large dissolution fluxes, which is advantageous for various geological applications.

Correction: Influence of mineralization and injection flow rate on flow patterns in three-dimensional porous media.

Correction for 'Influence of mineralization and injection flow rate on flow patterns in three-dimensional porous media' by R. Moosavi et al., Phys. Chem. Chem. Phys., 2019, 21, 14605-14611.

Influence of mineralization and injection flow rate on flow patterns in three-dimensional porous media.

Reactive flows inside porous media play an important role in a number of geophysical and industrial processes. Here, we present three-dimensional experimental measurements on how precipitation and flow patterns change with the flow rate inside a model porous medium consisting of monodisperse glass beads. The sample is initially filled with an aqueous solution of sodium carbonate into which a solution of barium chloride is injected at a constant flow rate. Upon contact and reaction, the two reactants produce water-insoluble barium carbonate which precipitates onto the glass beads. This precipitate then modifies the flow morphology which in turn changes the spatial distribution of the precipitate. We discuss the influence of the flow rate on the morphology of the flow pattern and demonstrate that neither viscous fingering nor the Rayleigh-Taylor instability have any significant influence in our model system.

Implications of crop model ensemble size and composition for estimates of adaptation effects and agreement of recommendations.

Climate change is expected to severely affect cropping systems and food production in many parts of the world unless local adaptation can ameliorate these impacts. Ensembles of crop simulation models can be useful tools for assessing if proposed adaptation options are capable of achieving target yields, whilst also quantifying the share of uncertainty in the simulated crop impact resulting from the crop models themselves. Although some studies have analysed the influence of ensemble size on model outcomes, the effect of ensemble composition has not yet been properly appraised. Moreover, results and derived recommendations typically rely on averaged ensemble simulation results without accounting sufficiently for the spread of model outcomes. Therefore, we developed an Ensemble Outcome Agreement (EOA) index, which analyses the effect of changes in composition and size of a multi-model ensemble (MME) to evaluate the level of agreement between MME outcomes with respect to a given hypothesis (e.g. that adaptation measures result in positive crop responses). We analysed the recommendations of a previous study performed with an ensemble of 17 crop models and testing 54 adaptation options for rainfed winter wheat (Triticum aestivum L.) at Lleida (NE Spain) under perturbed conditions of temperature, precipitation and atmospheric CO2 concentration. Our results confirmed that most adaptations recommended in the previous study have a positive effect. However, we also showed that some options did not remain recommendable in specific conditions if different ensembles were considered. Using EOA, we were able to identify the adaptation options for which there is high confidence in their effectiveness at enhancing yields, even under severe climate perturbations. These include substituting spring wheat for winter wheat combined with earlier sowing dates and standard or longer duration cultivars, or introducing supplementary irrigation, the latter increasing EOA values in all cases. There is low confidence in recovering yields to baseline levels, although this target could be attained for some adaptation options under moderate climate perturbations. Recommendations derived from such robust results may provide crucial information for stakeholders seeking to implement adaptation measures.

Reaction-driven oscillating viscous fingering.

Localized oscillations can develop thanks to the interplay of reaction and diffusion processes when two reactants A and B of an oscillating reaction are placed in contact, meet by diffusion, and react. We study numerically the properties of such an A+B→ oscillator configuration using the Brusselator model. The influence of a hydrodynamic viscous fingering instability on localized concentration oscillations is next analyzed when the oscillating chemical reaction changes the viscosity of the solutions involved. Nonlinear simulations of the related reaction-diffusion-convection equations with the fluid viscosity varying with the concentration of an intermediate oscillatory species show an active coupling between the oscillatory kinetics and the viscously driven instability. The periodic oscillations in the concentration of the intermediate species induce localized changes in the viscosity, which in turn can affect the fingering instability. We show that the oscillating kinetics can also trigger viscous fingering in an initially viscously stable displacement, while localized changes in the viscosity profile can induce oscillations in an initially nonoscillating reactive system.

Randomised controlled trial of transanal endoscopic microsurgery versus endoscopic mucosal resection for large rectal adenomas (TREND Study).

OBJECTIVE: Non-randomised studies suggest that endoscopic mucosal resection (EMR) is equally effective in removing large rectal adenomas as transanal endoscopic microsurgery (TEM), but EMR might be more cost-effective and safer. This trial compares the clinical outcome and cost-effectiveness of TEM and EMR for large rectal adenomas. DESIGN: Patients with rectal adenomas ≥3 cm, without malignant features, were randomised (1:1) to EMR or TEM, allowing endoscopic removal of residual adenoma at 3 months. Unexpected malignancies were excluded postrandomisation. Primary outcomes were recurrence within 24 months (aiming to demonstrate non-inferiority of EMR, upper limit 10%) and the number of recurrence-free days alive and out of hospital. RESULTS: Two hundred and four patients were treated in 18 university and community hospitals. Twenty-seven (13%) had unexpected cancer and were excluded from further analysis. Overall recurrence rates were 15% after EMR and 11% after TEM; statistical non-inferiority was not reached. The numbers of recurrence-free days alive and out of hospital were similar (EMR 609±209, TEM 652±188, p=0.16). Complications occurred in 18% (EMR) versus 26% (TEM) (p=0.23), with major complications occurring in 1% (EMR) versus 8% (TEM) (p=0.064). Quality-adjusted life years were equal in both groups. EMR was approximately €3000 cheaper and therefore more cost-effective. CONCLUSION: Under the statistical assumptions of this study, non-inferiority of EMR could not be demonstrated. However, EMR may have potential as the primary method of choice due to a tendency of lower complication rates and a better cost-effectiveness ratio. The high rate of unexpected cancers should be dealt with in further studies.

Interaction of Pure Marangoni Convection with a Propagating Reactive Interface under Microgravity.

A reactive interface in the form of an autocatalytic reaction front propagating in a bulk phase can generate a dynamic contact line upon reaching the free surface when a surface tension gradient builds up due to the change in chemical composition. Experiments in microgravity evidence the existence of a self-organized autonomous and localized coupling of a pure Marangoni flow along the surface with the reaction in the bulk. This dynamics results from the advancement of the contact line at the surface that acts as a moving source of the reaction, leading to the reorientation of the front propagation. Microgravity conditions allow one to isolate the transition regime during which the surface propagation is enhanced, whereas diffusion remains the main mode of transport in the bulk with negligible convective mixing, a regime typically concealed on Earth because of buoyancy-driven convection.

Testosterone in human studies: Modest associations between plasma and salivary measurements.

Testosterone is involved in many processes like aggression and mood disorders. As it may easily diffuse from blood into saliva, salivary testosterone is thought to reflect plasma free testosterone level. If so, it would provide a welcome noninvasive and less stressful alternative to blood sampling. Past research did not reveal consensus regarding the strength of the association, but sample sizes were small. This study aimed to analyse the association in a large cohort. In total, 2,048 participants (age range 18-65 years; 696 males and 1,352 females) were included and saliva (using cotton Salivettes) and plasma were collected for testosterone measurements. Levels were determined by enzyme-linked immunosorbent assay and radioimmunoassay respectively. Free testosterone was calculated by the Vermeulen algorithm. Associations were determined using linear regression analyses. Plasma total and free testosterone showed a significant association with salivary testosterone in men (adjusted ß = .09, p = .01; and ß = .15, p < .001, respectively) and in women (adjusted ß = .08, p = .004; and crude ß = .09, p = .002 respectively). The modest associations indicate that there are many influencing factors of both technical and biological origin.

Flow Control of A+B→C Fronts by Radial Injection.

The dynamics of A+B→C fronts is analyzed theoretically in the presence of passive advection when A is injected radially into B at a constant inlet flow rate Q. We compute the long-time evolution of the front position, r_{f}, of its width, w, and of the local production rate R of the product C at r_{f}. We show that, while advection does not change the well-known scaling exponents of the evolution of corresponding reaction-diffusion fronts, their dynamics is however significantly influenced by the injection. In particular, the total amount of product varies as Q^{-1/2} for a given volume of injected reactant and the front position as Q^{1/2} for a given time, paving the way to a flow control of the amount and spatial distribution of the reaction front product. This control strategy compares well with calcium carbonate precipitation experiments for which the amount of solid product generated in flow conditions at fixed concentrations of reactants and the front position can be tuned by varying the flow rate.

Chemical control of dissolution-driven convection in partially miscible systems: nonlinear simulations and experiments.

Chemical reactions can impact mixing in partially miscible stratifications by affecting buoyancy-driven convection developing when one phase dissolves into the other one in the gravity field. By means of combined nonlinear simulations and experiments, we explore the power of an A + B → C type of reaction to either enhance or refrain convective dissolution with respect to the nonreactive system depending on the relative contribution to density of the dissolving species A, of the reactant B initially dissolved in the host phase and of the product C. Nonlinear simulations are performed by solving reaction-diffusion-convection equations describing the dissolution and reactive dynamics when a less dense phase of A is layered on top of a reactive denser solution of B, in which A is partially miscible with a given solubility. The spatio-temporal dynamics and convective patterns observed in the numerical study compare favorably with experiments carried out with (i) a liquid alkyl-formate stratified on top of an aqueous solution in which the ester dissolves and undergoes a hydrolysis reaction and (ii) gaseous CO2 dissolving into an aqueous solution of NaOH. We show that the same reaction type can induce a different effect on the convective dynamics depending on the reactant in the host phase. The efficiency of convective dissolution in partially miscible systems can hence be controlled by the chemicals present in the host fluid and their concentration. The direct comparison between the convective dynamics observed during CO2 dissolution in an aqueous phase and in the ester/water stratification validates the latter as a convenient liquid-liquid model system for the interpretation of the impact of chemical reactivity in geological CO2 sequestration.