Out of the blue: the independent activity of sulfur-oxidizers and diatoms mediate the sudden color shift of a tropical river.

BACKGROUND: Río Celeste ("Sky-Blue River") is a river located in the Tenorio National Park (Costa Rica) that has become an important hotspot for eco-tourism due to its striking sky-blue color. A previous study indicated that this color is not caused by dissolved chemical species, but by formation of light-scattering aluminosilicate particles at the mixing point of two colorless streams, the acidic Quebrada Agria and the neutral Río Buenavista. RESULTS: We now present microbiological information on Río Celeste and its two tributaries, as well as a more detailed characterization of the particles that occur at the mixing point. Our results overturn the previous belief that the light scattering particles are formed by the aggregation of smaller particles coming from Río Buenavista, and rather point to chemical formation of hydroxyaluminosilicate colloids when Quebrada Agria is partially neutralized by Río Buenavista, which also contributes silica to the reaction. The process is mediated by the activities of different microorganisms in both streams. In Quebrada Agria, sulfur-oxidizing bacteria generate an acidic environment, which in turn cause dissolution and mobilization of aluminum and other metals. In Río Buenavista, the growth of diatoms transforms dissolved silicon into colloidal biogenic forms which may facilitate particle precipitation. CONCLUSIONS: We show how the sky-blue color of Río Celeste arises from the tight interaction between chemical and biological processes, in what constitutes a textbook example of emergent behavior in environmental microbiology.

The experimental average refractive index of liquid crystals and its prediction from the anisotropic indices.

Anisotropic optical properties of liquid crystals (LC), combined with their fluidity, are crucial for the development of new liquid crystal devices and applications. The optical anisotropy implies an existence of various refractive indices that depend on the direction of light oscillation relative to the director vector. For some applications, it is, however, necessary to estimate an average refractive index (nav) for the liquid-crystalline material, which is commonly effected through models of combination of the anisotropic refractive indices. The validity of these models lacks proof as the experimental average refractive index for anisotropic fluids has not been published. This article reports an experimental strategy to measure nav of liquid crystals; the method is based on generating multiple orientations of the liquid crystal molecules through their isotropization in mixtures with isotropic liquids. The refractive index of an isotropic mixture is measured; then the apparent refractive index of the liquid crystal is extracted using validated combination models of refractive indices in mixtures. The method was assessed with two nematic liquid crystals (5CB and MBBA) mixed with several isotropic liquids. The results indicate that the average refractive index of a LC is an extrapolation, in the nematic range of temperatures, of the index variation above the nematic-isotropic transition. A new theoretical model to predict the average refractive indices of liquid crystals was developed. Compared with the traditional formulae, the new model represents a significant improvement for the calculation of nav.

Photolysis of the nonsteroidal anti-inflammatory drug sulindac: elucidation of kinetic behaviour and photodegradation pathways in water.

Non-steroidal anti-inflammatory drugs are recognized widely as emerging contaminants. Sulindac has received additional attention as a prodrug in cancer treatment and because of its detection in drinking water and wastewaters. Nevertheless, there is limited knowledge about its kinetic behaviour and fate in the aquatic environment. In this work, the direct photolysis of sulindac, in which photochemical reactions were monitored and phototransformation products identified, was investigated under prolonged periods using UV-A and UV-B radiation and pH conditions (2 and 7) to evaluate the effect of the protonation state and the efficiency of the photolytic process. A novel kinetic mechanism has been proposed in which sulindac exhibits a consecutive reaction pathway, with pseudo-first order kinetics for rapid and reversible Z to E isomerization. Once photoequilibrium was reached, second-order degradation of the isomers in the presence of the new photodegradation products was observed. Photochemical transformation was faster under UV-B irradiation and lower pH, which suggests greater persistence of sulindac at more relevant environmental conditions of UV-A and pH 7. Two novel and major byproducts were identified, corresponding to the oxidative cleavage of the alkene exo to the indene system. The degradation pathway is mainly photoinduced, enhanced by acidic conditions and presumes the double bond as the most reactive site for the parent compound. This research demonstrates an approach for determining kinetics of compounds under challenging conditions, including, absorption from multiple electronic transitions, photoinduced products with unknown extinction coefficients, concentration dependence, photoinduced sensitizing intermediates, and speciation effects. Our work greatly improves our understanding of the degradation process of sulindac and will contribute to exposure assessments and treatment methodologies for this compound in impacted waters.

New method to calculate the anisotropies of polarizability and thermal expansion of uniaxial liquid crystals.

The anisotropy of molecular polarizability in liquid crystals is linked to the birefringence in these substances. The classic methods to compute the polarizabilities of liquid crystals assume an average number density of molecules that is equal in all directions. In the present work, a new model is proposed for the anisotropic molar polarization based on a virtual anisotropy of the number density of molecules in the liquid-crystalline material. This new strategy hence allows for the computation of both the anisotropic polarizabilities and the anisotropic thermal-expansion coefficients of liquid crystals. The model is applied to the liquid crystals 4-n-pentyl-4'-cyanobiphenyl and N-(4-methoxybenzylidene)-4-butylaniline, yielding polarizabilities similar to those reported for these materials. For these nematic liquid crystals, the results imply the existence of a positive thermal-expansion coefficient in the direction perpendicular to the director vector throughout the entire nematic temperature range and a negative thermal-expansion coefficient parallel to the director vector near the temperature of the nematic-isotropic transition. At the isotropization temperature, there exists divergent and critical behavior of the anisotropic thermal-expansion coefficients, consistent with the typical discontinuity of volume in first-order transitions.

Increased Nematic-Isotropic Transition Temperature on Doping a Liquid Crystal with Molecularly Rigid Carboxylic Acids.

A thermotropic nematic liquid crystal (LC) becomes an isotropic liquid at the nematic-isotropic transition temperature (TNI), which depends on the molecular order of the mesophase. By means of a polarized optical microscope and a differential scanning calorimeter, it was found that doping the nematic liquid crystal 4-n-pentyl-4'-cyanobiphenyl (5CB) with molecularly rigid carboxylic acids (benzoic, 1-naphthoic, 2-naphthoic, and biphenyl-4-carboxylic acids) increases TNI without modification of the nematic-isotropic transition enthalpy. This increment in TNI is due to the increased order caused by the formation of molecularly rigid and elongated dimers of carboxylic acids in the nematic LC, as confirmed with infrared spectra. Furthermore, TNI increased with the length of the molecularly rigid dimers at the same concentration level. Conversely, doping the LC with molecularly flexible acids caused lowering of TNI. A quantitative correlation was established between the TNI increase of the rigid carboxylic acids and the length of the dimers of these acids; a predictive model for these ΔTNI values as a function of acid molar fraction was developed. It was also demonstrated that the doping of 5CB with rigid carboxylic acids increases the rotational viscosity of the liquid crystal.

Scattering of light by colloidal aluminosilicate particles produces the unusual sky-blue color of Río Celeste (Tenorio volcano complex, Costa Rica).

Río Celeste (Sky-Blue River) in Tenorio National Park (Costa Rica), a river that derives from the confluence and mixing of two colorless streams--Río Buenavista (Buenavista River) and Quebrada Agria (Sour Creek)--is renowned in Costa Rica because it presents an atypical intense sky-blue color. Although various explanations have been proposed for this unusual hue of Río Celeste, no exhaustive tests have been undertaken; the reasons hence remain unclear. To understand this color phenomenon, we examined the physico-chemical properties of Río Celeste and of the two streams from which it is derived. Chemical analysis of those streams with ion-exchange chromatography (IC) and inductively coupled plasma atomic emission spectroscopy (ICP-OES) made us discard the hypothesis that the origin of the hue is due to colored chemical species. Our tests revealed that the origin of this coloration phenomenon is physical, due to suspended aluminosilicate particles (with diameters distributed around 566 nm according to a lognormal distribution) that produce Mie scattering. The color originates after mixing of two colorless streams because of the enlargement (by aggregation) of suspended aluminosilicate particles in the Río Buenavista stream due to a decrease of pH on mixing with the acidic Quebrada Agria. We postulate a chemical mechanism for this process, supported by experimental evidence of dynamic light scattering (DLS), zeta potential measurements, X-ray diffraction and scanning electron microscopy (SEM) with energy-dispersive spectra (EDS). Theoretical modeling of the Mie scattering yielded a strong coincidence between the observed color and the simulated one.

Molecular configuration transitions of a nematic liquid crystal encapsulated in organically modified silicas.

The nematic liquid crystal (LC) 4-n-pentyl-4'-cyanobiphenyl (5CB) was encapsulated as spherical microdroplets dispersed in solid organically modified silica matrices (ORMOSIL), obtained by the sol-gel method. The organic functional groups used to modify the matrix were methyl, ethyl and propyl. The amount of the organic groups in the confining matrix was found to affect the LC surface anchoring properties, and therefore the molecular configurations in the LC droplets. Changes in this molecular configuration by variation of the temperature were identified. The matrix chemical composition-temperature diagrams for the LC configurations were obtained for three sets of ORMOSIL matrices with methyl, ethyl and propyl functionalizations. A radial configuration of the LC droplets is promoted at lower temperatures and higher amounts of modifying groups in the matrix, while a bipolar configuration is obtained at low organic contents and high temperatures. An empirical model was developed to correlate the dependence of the surface anchoring transition phenomena with the chemical composition of the ORMOSIL matrices and the temperature, showing a good correlation with the experimental results.