Physicochemical Properties of 3D-Printed Polylactic Acid/Hydroxyapatite Scaffolds.

The reconstruction or regeneration of damaged bone tissue is one of the challenges of orthopedic surgery and tissue engineering. Among all strategies investigated, additive manufacturing by fused deposition modeling (3D-FDM printing) opens the possibility to obtain patient-specific scaffolds with controlled architectures. The present work evaluates in depth 3D direct printing, avoiding the need for a pre-fabricated filament, to obtain bone-related scaffolds from direct mixtures of polylactic acid (PLA) and hydroxyapatite (HA). For it, a systematic physicochemical characterization (SEM-EDS, FT-Raman, XRD, micro-CT and nanoindentation) was performed, using different PLA/HA ratios and percentages of infill. Results prove the versatility of this methodology with an efficient HA incorporation in the 3D-printed scaffolds up to 13 wt.% of the total mass and a uniform distribution of the HA particles in the scaffold at the macro level, both longitudinal and cross sections. Moreover, an exponential distribution of the HA particles from the surface toward the interior of the biocomposite cord (micro level), within the first 80 µm (10% of the entire cord diameter), is also confirmed, providing the scaffold with surface roughness and higher bioavailability. In relation to the pores, they can range in size from 250 to 850 µm and can represent a percentage, in relation to the total volume of the scaffold, from 24% up to 76%. The mechanical properties indicate an increase in Young's modulus with the HA content of up to ~50%, compared to the scaffolds without HA. Finally, the in vitro evaluation confirms MG63 cell proliferation on the 3D-printed PLA/HA scaffolds after up to 21 days of incubation.

Humic acids modify the pulse size distributions in the characterization of plastic microparticles by Tunable Resistive Pulse Sensing.

Tunable Resistive Pulse Sensing, TRPS, is an emerging technique used in quantification and measuring the size (particle-by-particle) of viruses, exosomes and engineered colloidal spheres in biological fluids. We study the features of TRPS to enhance size characterization and quantification of submicron-sized microplastics, also called plastic microparticles, MP, in freshwater environments. We report alterations on the detection of the resistive pulses in the TRPS caused by humic acids, HA, during the size measurement of polystyrene microspheres used as MP surrogate. We discuss the alteration of the electric field in the measuring channel of the TRPS apparatus induced by the passage of HA. TRPS is a fast and precise technique for counting and size determination of MP but needs the evaluation of the influence of the organic matter on the current blockades. We show that statistical clustering models of the magnitude distribution of the resistive pulses can help to detect and quantify changes in the pulse size distributions induced by flocculation of humic acids. Conclusions of this study indicate that TRPS can be a valuable tool to improve the knowledge of the MP fate in surface waters, in the vadose zone and groundwater.

Modeling the influence of raindrop size on the wash-off losses of copper-based fungicides sprayed on potato (Solanum tuberosum L.) leaves.

Modeling the pesticide wash-off by raindrops is important for predicting pesticide losses and the subsequent transport of pesticides to soil and in soil run-off. Three foliar-applied copper-based fungicide formulations, specifically the Bordeaux mixture (BM), copper oxychloride (CO), and a mixture of copper oxychloride and propylene glycol (CO-PG), were tested on potato (Solanum tuberosum L.) leaves using a laboratory raindrop simulator. The losses in the wash-off were quantified as both copper in-solution loss and copper as particles detached by the raindrops. The efficiency of the raindrop impact on the wash-off was modeled using a stochastic model based on the pesticide release by raindrops. In addition, the influence of the raindrop size, drop falling height, and fungicide dose was analyzed using a full factorial experimental design. The average losses per dose after 14 mm of dripped water for a crop with a leaf area index equal to 1 were 0.08 kg Cu ha(-1) (BM), 0.3 kg Cu ha(-1) (CO) and 0.47 kg Cu ha(-1) (CO-PG). The stochastic model was able to simulate the time course of the wash-off losses and to estimate the losses of both Cu in solution and as particles by the raindrop impacts. For the Cu-oxychloride fungicides, the majority of the Cu was lost as particles that detached from the potato leaves. The percentage of Cu lost increased with the decreasing raindrop size in the three fungicides for the same amount of dripped water. This result suggested that the impact energy is not a limiting factor in the particle detachment rate of high doses. The dosage of the fungicide was the most influential factor in the losses of Cu for the three formulations studied. The results allowed us to quantify the factors that should be considered when estimating the losses by the wash-off of copper-based fungicides and the inputs of copper to the soil by raindrop wash-off.

Effects of past copper contamination and soil structure on copper leaching from soil.

Copper contamination affects biological, chemical, and physical soil properties and associated ecological functions. Changes in soil pore organization as a result of Cu contamination can dramatically affect flow and contaminant transport in polluted soils. This study assessed the influence of soil structure on the movement of water and Cu in a long-term polluted soil. Undisturbed soil cores collected along a Cu gradient (from about 20 to about 3800 mg Cu kg soil) were scanned using X-ray computed tomography (CT). Leaching experiments were performed to analyze tracer transport, colloid leaching, and dissolved organic carbon (DOC) and Cu losses. The 5% arrival time () and apparent dispersivity (λ) for tracer breakthrough were calculated by fitting the experimental data to a nonparametric, double-lognormal probability density function. Soil bulk density, which did not follow the Cu gradient, was the main driver of preferential flow, while macroporosity determined by X-ray CT (for pores >180 µm) proved the best predictor of solute transport. Higher preferential flow due to the presence of well-aligned pores and small cracks controlled water movement in compacted soil. Transport of Cu was rapid during the first flush (≈1 pore volume) in association with the movement of colloid particles, followed by slower transport in association with the movement of DOC in the soil solution. The relative amount of Cu released was strongly correlated with macroporosity as determined by X-ray CT, indicating the promising potential of this visualization technique for predicting contaminant transport through soil.

Phosphorus effect on Zn adsorption-desorption kinetics in acid soils.

The adsorption-desorption kinetics of Zn in the absence and presence of P was studied by using the stirred flow chamber technique. The results thus obtained were compared with those previously obtained for Cu. As with copper, the simultaneous addition of P and Zn in a 1:1 mole ratio to soil was found to significantly increased Zn adsorption relative to the absence of P. Unlike Cu, however, Zn was only adsorbed at fast adsorption sites in the absence of P. In any case, the increased adsorption of Zn in the presence of P was largely due to slow adsorption sites, where Zn(2+) ion acted as a bridging element between P and organic matter. Following adsorption in both the presence and absence of P, Zn was desorbed to a much higher extent than was Cu. However, the proportion of Zn desorbed after adsorption in the presence of P was significantly lower than in the absence of P. This indicates that Zn binds more strongly to adsorbing surfaces in the presence of P than in its absence.

Detachment of sprayed colloidal copper oxychloride-metalaxyl fungicides by a shallow water flow.

BACKGROUND: Flow shear stress induced by rainfall promotes the loss of the pesticides sprayed on crops. Some of the factors influencing the losses of colloidal-size particulate fungicides are quantified by using a rotating shear system model. With this device it was possible to analyse the flow shear influencing washoff of a commercial fungicide formulation based on a copper oxychloride-metalaxyl mixture that was sprayed on a polypropylene surface. A factor plan with four variables, i.e. water speed and volume (both variables determining flow boundary stress in the shear device), formulation dosage and drying temperature, was set up to monitor colloid detachment. RESULTS: This experimental design, together with sorption experiments of metalaxyl on copper oxychloride, and the study of the dynamics of metalaxyl and copper oxychloride washoff, made it possible to prove that metalaxyl washoff from a polypropylene surface is controlled by transport in solution, whereas that of copper oxychloride occurs by particle detachment and transport of particles. Average losses for metalaxyl and copper oxychloride were, respectively, 29 and 50% of the quantity applied at the usual recommended dosage for crops. CONCLUSION: The key factors affecting losses were flow shear and the applied dosage. Empirical models using these factors provided good estimates of the percentage of fungicide loss. From the factor analysis, the main mechanism for metalaxyl loss induced by a shallow water flow is solubilisation, whereas copper loss is controlled by erosion of copper oxychloride particles.

Influence of methanol on the dynamics of the retention and release of cyprodinil by an agricultural soil.

The influence of methanol on the adsorption of the fungicide cyprodinil by a crop soil was studied by equilibrium measurements and by determining the retention-release dynamics in a continuous stirred flow tank reactor (CSTR). Equilibrium measurements showed the effective coefficient of partition of cyprodinil between soil and solution, K(dc), decreases linearly as the concentration of methanol in the solution increases until a percentage of 20% is reached. In CSTR experiments, the retention of cyprodinil was found to be almost reversible; up to a 95% of the fungicide was desorbed. The retention-release dynamics showed biphasic behavior and was partially controlled by diffusion. This behavior was reproduced by a model of diffusion into micropores identifying the soil particles as spheres and taking into account both intraparticle nonlinear adsorption and nonlinear adsorption at external surfaces. In all cases, the sorption kinetics was not the limiting step. The main effect of methanol in the retention-release dynamics ended up being based on the changes produced in the adsorption equilibrium. Methanol also increased the effective diffusion coefficient and decreased the mass transfer coefficient. The optimized Freundlich's isotherm coefficients for <5% methanol were lower than those obtained from the batch experiments.

Guía de actuación ante una rinitis alérgica en atención primaria / Allergic rhinitis protocol in primary care

La rinitis alérgica (RA) es una enfermedad muy prevalente en la mayoría de los países desarrollados, afectando a un 10-20 por ciento de la población general. Diversos estudios indican su prevalencia creciente en los países de la CEE en las últimas décadas. En Europa, se estiman unos costes anuales ocasionados por la rinitis alérgica, entre 1.000 y 1.500 millones de euros los costes directos y entre 1.500 y 2.000 millones de euros los indirectos.En todos los casos debe de intentarse la evitación del alérgeno. Si los síntomas son leves u ocasionales, pero el paciente requiere tratamiento, los antihistamínicos son los de elección. Si el paciente presenta síntomas moderados o síntomas de larga duración, o si los síntomas son leves pero no se controlan con antihistamínicos, se recomienda añadir un esteroide tópico nasal. En el caso de que los síntomas oculares concomitantes sean molestos y no se controlen con el esteroide tópico nasal, es recomendable añadir un antihistamínico tópico ocular o una cromona. Si el paciente presenta síntomas graves o si el tratamiento con esteroides tópicos nasales no tiene un efecto adecuado, está indicada la asociación de esteroides tópicos nasales y antihistamínicos (orales o tópicos).Si estas medidas no proporcionan un alivio suficiente de los síntomas, es recomendable añadir ciclos cortos de descongestionantes orales en caso de obstrucción nasal, bromuro de ipratropio en caso de rinorrea acuosa, o una tanda corta de esteroides orales. En los pacientes que presentan síntomas moderados/severos, de estación prolongada, asociados a asma, o de difícil control con medidas ambientales y tratamiento sintomático, está indicada la inmunoterapia específica (AU)