Ultraviolet Radiation in the Rhône River Lenses of Low Salinity and in Marine Waters of the Northwestern Mediterranean Sea: Attenuation and Effects on Bacterial Activities and Net Community Production

The high content in nutrients of freshwater outflows induces highly productive and buoyant plumes spreading over marine waters (MW). As a consequence, the growth of organisms developing in these low‐salinity waters (LSW) might be potentially affected by UV‐R (280–400 nm). This study investigated the penetration of UV‐R and its impact on net community production (NCP) and bacterial protein (B_PROTS) and DNA (B_DNAS) synthesis in mesotrophic‐LSW formed from the Rhône River and in oligotrophic MW of the Northwestern Mediterranean Sea (Gulf of Lions) in May 2006. High concentrations of chlorophyll a (up to 8 μg L^?1) measured in the LSW (<37.8 psu, 0–10 m) were the main factor influencing the diffuse attenuation coefficients (K_d) of both UV‐R and photosynthetically active radiation (PAR). The mean ratio of the K_d measured between the LSW and the MW increased with wavelength from 2.4 at 305 nm to 2.9 at 380 nm and 3.1 for PAR indicating more similarity in the UV region. NCP was severely inhibited by UV‐R at the surface of the LSW, whereas no effect was measured in the surrounding MW. In contrast, B_PROTS and B_DNAS were affected deeper by UV‐R in the MW (up to 8 m depth) compared to the LSW where inhibition was only observed at the surface. Differences in response of bacteria in LSW and MW are largely explained by differences in UV‐R transparency; however, transplant experiments indicate that bacterial assemblages from the MW were also more sensitive to UV‐R than those present in the LSW. We also observed that higher activity of bacteria after nutrient additions increased their sensitivity to UV‐R during the day, but favored their recovery during the night incubation period for both LSW and MW. Results suggest that riverine and nutrient inputs may alter the effects of UV‐R on microbial activity by attenuating the UV‐R penetration and by modifying the physiology of bacteria.     

Contrasting effects of solar radiation and nitrates on the bioavailability of dissolved organic matter to marine bacteria

We evaluated the role of nitrate (NO₃^?) as a potential photosensitizer and the bacterial responses to dissolved organic matter (DOM) phototransformation from coastal waters in the northwestern Mediterranean Sea. In spring, without any addition of NO₃^?, the exposure of 0.2 μm filtered seawater (DOM-solution) to natural solar radiation (i.e. Full Sun [FS], including photosynthetically available [PAR: 400–700 nm], ultraviolet-A [UVAR: 315–400 nm] and ultraviolet-B [UVBR: 280–315 nm] radiations) stimulated bacterial production (BP) and abundance (BA) in natural assemblages (0.8 μm filtered seawater) by 80 and 20% as compared to unexposed (Dark) DOM-solutions, respectively. This stimulation resulted primarily from the exposure to PAR. When NO₃^? (30 μM) was added to DOM-solution before irradiation, BP and BA increased by 150 and 65% in FS compared to Dark, respectively, due to both PAR and UVBR. By contrast, in summer, the exposure of DOM-solution caused a decrease in BP by 30% but an increase in BA by 23% in FS compared to Dark, regardless of the NO₃^? addition before irradiation. The inhibition of BP resulted mainly from UVAR, whereas the stimulation of BA resulted from PAR. These results suggest contrasting effects along seasons of solar radiation and NO₃^? on DOM bioavailability, depending on its initial chemical composition.     

Isomer-specific product detection of CN radical reactions with ethene and propene by tunable VUV photoionization mass spectrometry

Product detection studies of CN reactions with ethene and propene are conducted at room temperature (4 Torr, 533.3 Pa) using multiplexed time-resolved mass spectrometry with tunable synchrotron photoionization. Photoionization efficiency curves, i.e., the ion signal as a function of photon energy, are used to determine the products and distinguish isomers. Both reactions proceed predominantly via CN addition to the π orbital of the olefin. For CN + ethene, cyanoethene (C₂H₃CN) is detected as the sole product in agreement with recent studies on this reaction. Multiple products are identified for the CN + propene reaction with 75(±15)% of the detected products in the form of cyanoethene from a CH₃ elimination channel and 25(±15)% forming different isomers of C₄H₅N via H elimination. The C₄H₅N comprises 57(±15)% 1-cyanopropene, 43(±15)% 2-cyanopropene and <15% 3-cyanopropene. No evidence of direct H abstraction or indirect HCN formation is detected for either reaction. The results have relevance to the molecular weight growth chemistry on Saturn's largest moon Titan, where the formation of small unsaturated nitriles are proposed to be key steps in the early chemical stages of haze formation.     

A connection between extreme value theory and long time approximation of SDEs

We consider a sequence _(ξn)n≥1${\left({\xi }_n\right)}_{n\ge 1}$ of i.i.d.   random values residing in the domain of attraction of an extreme value distribution. For such a sequence, there exist (_an)$\left(a_n\right)$ and (_bn)$\left(b_n\right)$, with _an>0$a_n>0$ and _bn∈R$b_n\in \mathbb{R}$ for every n≥1$n\ge 1$, such that the sequence (_Xn)$\left(X_n\right)$ defined by _Xn=(max(_ξ1,…,_ξn)−_bn)/_an$X_n=(max({\xi }_1,\dots ,{\xi }_n)-b_n)/a_n$ converges in distribution to a non-degenerated distribution.     

Coupled chemical processes at clay/electrolyte interface: a batch titration study of Na-montmorillonites

The present work addresses the protolytic charge of montmorillonite, which occurs on the broken-bond sites at the particle edges. The purpose is to overcome the general difficulty arising in potentiometric titration due to coupled side reactions, which severely impede the titrant budget (partial dissolution of the clay and of secondary phases, hydrolysis and readsorption of dissolved species, cation exchange). Batch potentiometric titrations were carried out on the montmorillonite fractions extracted from two bentonites (MX80 and SWy2) to quantify their protolytic charge. The effects of equilibration time (24 h and 7 days), pH from 4 to 10, and ionic strength (0.1 and 0.01 mol L(-1)) were extensively studied for the MX80 sample. Quantification of dissolution was achieved by analysis of the equilibrium solutions for dissolved species and by La(3+) exchange of the readsorbed species. The results clearly show that secondary phases such as iron- or silica-rich minerals contribute to the dissolved species, according to the nature of the raw bentonite. Furthermore, readsorption affects significant amounts of dissolved species. The overconsumption of proton/hydroxide due to dissolution, readsorption, and hydrolysis of dissolved species was evaluated using a self-consistent thermodynamic calculation. The ability of such calculation to correct the raw titration curves in order to extract the titrable surface charge of montmorillonite was evaluated by comparison with the continuous titration procedure. Especially in the alkaline domain, correcting the raw batch titration curves for the measured side reactions failed to reproduce the continuous titration curves. These observations demonstrate the limitations of the batch titration method and the superiority of fast, continuous methods for quantifying the dissociable surface charge of clays.     

Theoretical study of the acid-base properties of the montmorillonite/electrolyte interface: influence of the surface heterogeneity and ionic strength on the potentiometric titration curves

The parallel shape of the potentiometric titration curves for montmorillonite suspension is explained using the surface complexation model and taking into account the surface heterogeneity. The homogeneous models give accurate predictions only if they assume unphysically large values of the equilibrium constants for the exchange process occurring on the basal plane. However, the assumption that the basal plane is energetically heterogeneous allows to fit the experimental data (reported by Avena and De Pauli [M. Avena, C.P. De Pauli, J. Colloid Interface Sci. 202 (1998) 195-204]) for reasonable values of exchange equilibrium constant equal to 1.26 (suggested by Fletcher and Sposito [P. Fletcher, G. Sposito, Clay Miner. 24 (1989) 375-391]). Moreover, we observed the typical behavior of point of zero net proton charge (pznpc) as a function of logarithm of the electrolyte concentration (log[C]). We showed that the slope of the linear dependence, pznpc=f(log[C]), is proportional to the number of isomorphic substitutions in the crystal phase, which was also observed in the experimental studies.     

How phonons govern the behavior of short, strong hydrogen bonds in urea-phosphoric acid

Recent neutron diffraction data have shown that the hydrogen atom involved in the short, strong hydrogen bond in urea-phosphoric acid migrates toward the midpoint of the hydrogen bond as the temperature increases. With the help of solid state ab initio calculations and inelastic neutron scattering, we have investigated the temperature dependence of the structural and vibrational properties of the system. The potential energy surface of the proton in the short, strong hydrogen bond and the thermal population of the energy levels therein cannot account for the observed proton migration. Ab initio molecular dynamics simulations clearly reveal the migration of the proton. This molecular dynamics result was reported recently by other authors, but they only offered a tentative explanation in terms of a resonance between high-frequency vibrations, which is not supported by the calculations presented here. We explain the proton migration in terms of phonon-driven structural fluctuations and their impact on the temperature-dependent evolution of the potential energy surface of the short hydrogen-bond proton.     

Broad-bandwidth shot-noise-limited class-A operation of a monomode semiconductor fiber-based ring laser

We demonstrate the operation of a monomode semiconductor laser with a relative intensity noise limited by the shot-noise floor, -156 dB/Hz for a typical detected photocurrent of 1 mA, over a large frequency range from 50 MHz to 18 GHz. We achieve direct control of photon lifetime to turn an initially class-B laser into a relaxation-oscillation-free class-A one while preserving strict single-mode operation. Finally, we confirm experimentally that the laser operation in the desired class-A regime allows a dramatic filtering out of the relative intensity noise.     

Control of an external-cavity laser diode operating in the regular pulse package regime with a frequency shift of the optical feedback

I demonstrate numerically that the regular pulse package regime observed in an external-cavity laser diode can be controlled by means of an adequate shift of the optical feedback frequency. This control leads to a stable pulsed behavior.     

Predicting ductile fracture of low carbon steel sheets: Stress-based versus mixed stress/strain-based Mohr–Coulomb model

Two distinct implementations of the Mohr–Coulomb failure model are used in conjunction with a non-associated quadratic plasticity model to describe the onset of fracture in low carbon steel sheets. The stress-based version corresponds to the original Mohr–Coulomb model in stress space. For the mixed stress/strain-based version, the Mohr–Coulomb failure criterion is first transformed into the space of stress triaxiality, Lode angle parameter and equivalent plastic strain and then used as stress-state dependent weighting function in a damage indicator model. Basic fracture experiments including tensile specimens of different notch radii and a punch test are performed to calibrate the material parameters of the respective models. Subsequently, the models are used to predict the crack initiation in a Hasek test and during the stamping of an anticlastic structure. Unlike for the calibration experiments, the loading history during stamping is highly non-linear. Both models can be calibrated with similar accuracy, but the strain-based model predicts the instant of onset of fracture with greater accuracy in the stamping experiment which is an advantage of the empirical damage accumulation rule.