Toxicité de l'ion fluorure envers les organismes d'eau douce et effets de la dureté - revue et nouvelle analyse de données existantes

Les plus importantes sources anthropiques de fluorures dans les systèmes d'eau douce comprennent les eaux usées municipales, les industries productrices de fertilisants et les alumineries. Plusieurs études montrent que la toxicité des fluorures est réduite lorsque le test toxicologique est réalisé en eau dure plutôt qu'en eau douce. Trois mécanismes peuvent être invoqués pour expliquer une telle tendance : (I) influence des ions de dureté (Ca2+ ; Mg2+) sur les organismes tests (soit au niveau de la barrière biologique séparant l'organisme de son milieu, soit au niveau de leur métabolisme interne); (II) complexation entre le fluorure et les ions de dureté dans le milieu d'exposition, menant à une réduction de la concentration en fluorure libre (F-); (III) précipitation de fluorite (CaF2) dans les milieux d'exposition, menant à une réduction de la concentration effective en fluorures. Pour identifier le ou les mécanisme(s) responsables de l'effet protecteur de la dureté, nous avons réalisé une revue de la littérature existante sur les poissons, les invertébrés et les insectes aquatiques d'eau douce. Parmi ces études, les plus complètes ont été sélectionnées et la spéciation des fluorures modélisée pour chaque cas. Les modélisations réalisées indiquent que la spéciation physique du fluorure (distinction entre les espèces dissoutes et particulaires) a beaucoup plus d'importance que sa spéciation chimique en solution dans les systèmes étudiés.Important anthropogenic sources of fluoride to the aquatic environment include municipal waste waters and effluents from fertilizer producing plants and aluminum refineries. Many studies have demonstrated that fluoride toxicity to aquatic organisms is reduced when the toxicological test is performed in hard water rather than soft water. In principle at least three mechanisms could explain this trend: (I) a direct beneficial influence of the hardness cations (Ca2+ ; Mg2+) on the test organism (either externally, at an epithelial membrane, or internally); (II) complexation between fluoride and the hardness cations, leading to a reduction in free the fluoride concentration (F-) in the exposure media; (III) fluorite precipitation (CaF2) in the exposure media, leading to a reduction in the effective fluoride concentration. The present literature review was designed to identify which of these mechanisms might be responsible for the apparent protective effect of hardness on fluoride toxicity.An inventory of the existing literature on the toxicity of fluoride to freshwater fish, invertebrates and aquatic insects was prepared. The most complete studies were selected and the chemical data needed to model cation and anion speciation in the exposure media were extracted from the papers. Speciation at equilibrium was then modelled using as input data the total concentrations of the key constituents (calcium, magnesium, fluoride and chloride), together with the temperature and the pH.The initial speciation calculations revealed a particularity of the chemical systems studied: frequently precipitation of fluorite (CaF2) was predicted by the speciation model (MINEQL+), but the article from which the data had been extracted did not mention the appearance of a precipitate. Fluorite solubility, at a pH of 7 and at an ionic strength of 2.7 mM, is approximately 17 mg CaF2 /L (0.22 mM). When high fluoride concentrations are used in hard water, both fluoride and calcium concentrations are predicted to decrease markedly as a result of fluorite precipitation. This analysis of the published results thus suggests that the reported lower toxicity of fluoride in hard waters is likely due to the chemical precipitation of CaF2 and MgF2, resulting in a decrease in the effective fluoride concentration to which the test organisms are exposed. In other words, changes in the physical speciation of fluoride (i.e., its distribution among dissolved and particulate species) are much more important than changes in its chemical speciation in solution.Given the low solubility of fluoride in hard waters, it would seem difficult if not impossible to carry out fluoride toxicity tests in hard water. However, in a few fluoride toxicity studies the researchers checked for precipitation by monitoring fluoride and calcium concentrations throughout the toxicity test. In some of these cases, even though speciation calculations predicted fluorite formation at the exposure concentrations used, the authors did not detect any precipitation; these systems were thus apparently in a metastable, over-saturated state, where the kinetics of precipitation were slow relative to the duration of the toxicity test. The chemical equilibrium software was used to simulate fluoride speciation in these systems, by allowing the over-saturated solid phases to remain in solution. In particular, we looked for evidence that under such circumstances the hardness cations exerted a beneficial effect. However, no clear picture emerged from this second analysis: two of the studies designed particularly to test the effect of calcium on fluoride toxicity showed a protective effect, whereas one study indicated the opposite effect, i.e. an increase in fluoride toxicity as the calcium concentration was raised. All fish studies for which calcium concentrations were available (N=20 studies; 58 toxicity tests) were pooled and tested for a possible calcium effect on fluoride toxicity. No relationship was observed between fluoride ion toxicity (LC50, expressed as calculated free [F-]) and calculated dissolved calcium concentrations for these pooled data (Fig. 2). Fluorite solubility was the most important factor influencing the data point distribution in the relationship. The same exercise was performed for all the invertebrate studies (N=11 studies; 22 toxicity tests) but again no relationship was found (Fig. 3).Several factors other than hardness affect fluoride toxicity to aquatic organisms. Fluoride toxicity to fish increased with exposure duration up to 200 h, where it reached a threshold LC50 level around 100 mg/L (5.3 mM) expressed as free fluoride (Fig. 4). Fish life stage (Fig. 5), the temperature of the exposure media (Fig. 6) and the chloride concentration also affected fluoride toxicity in fish. For invertebrates, fluoride toxicity increased with exposure duration but to a lesser extent than for fish.In summary, water hardness clearly reduces fluoride toxicity to aquatic organisms by limiting the equilibrium solubility of the fluoride ion. However, in those cases where the precipitation of CaF2 (s) and MgF2 (s) is slow, and where the hardness cations and fluoride co-exist in the dissolved state in the exposure medium, the experimental evidence for a protective effect of hardness on fluoride toxicity is equivocal. To answer the question, new experiments should be performed under conditions that take into account the behaviour of calcium and fluoride in the natural environment. Metastable environments where fluoride concentrations exceed the solubility limit imposed by CaF2 or MgF2 could be reproduced in laboratory toxicity tests by using continuous flow systems. For tests below the solubility limit, toxicity tests with varying levels of Ca or Mg could be designed to stay within the solubility range of CaF2 or MgF2. In both cases, dissolved calcium, magnesium and fluoride concentrations should be monitored throughout the toxicity tests

The origin of ultra diffuse galaxies: stellar feedback and quenching

We test if the cosmological zoom-in simulations of isolated galaxies from the FIRE project reproduce the properties of ultra diffuse galaxies. We show that stellar feedback-generated outflows that dynamically heat galactic stars, together with a passively aging stellar population after imposed quenching (from e.g. infall into a galaxy cluster), naturally reproduce the observed population of red UDGs, without the need for high spin halos or dynamical influence from their host cluster. We reproduce the range of surface brightness, radius and absolute magnitude of the observed z=0 red UDGs by quenching simulated galaxies at a range of different times. They represent a mostly uniform population of dark matter-dominated galaxies with M_star ~1e8 Msun, low metallicity and a broad range of ages. The most massive simulated UDGs require earliest quenching and are therefore the oldest. Our simulations provide a good match to the central enclosed masses and the velocity dispersions of the observed UDGs (20-50 km/s). The enclosed masses of the simulated UDGs remain largely fixed across a broad range of quenching times because the central regions of their dark matter halos complete their growth early. A typical UDG forms in a dwarf halo mass range of Mh~4e10-1e11 Msun. The most massive red UDG in our sample requires quenching at z~3 when its halo reached Mh ~ 1e11 Msun. If it, instead, continues growing in the field, by z=0 its halo mass reaches > 5e11 Msun, comparable to the halo of an L* galaxy. If our simulated dwarfs are not quenched, they evolve into bluer low-surface brightness galaxies with mass-to-light ratios similar to observed field dwarfs. While our simulation sample covers a limited range of formation histories and halo masses, we predict that UDG is a common, and perhaps even dominant, galaxy type around Ms~1e8 Msun, both in the field and in clusters.Comment: 20 pages, 13 figures; match the MNRAS accepted versio

The Great Observatories Origins Deep Survey: Constraints on the Lyman Continuum Escape Fraction Distribution of Lyman--Break Galaxies at 3.4<z<4.5

We use ultra-deep ultraviolet VLT/VIMOS intermediate-band and VLT/FORS1 narrow-band imaging in the GOODS Southern field to derive limits on the distribution of the escape fraction (f_esc) of ionizing radiation for L >~ L*(z=3) Lyman Break Galaxies (LBGs) at redshift 3.4--4.5. Only one LBG, at redshift z=3.795, is detected in its Lyman continuum (LyC; S/N~5.5), the highest redshift galaxy currently known with a direct detection. Its ultraviolet morphology is quite compact (R_eff=0.8, kpc physical). Three out of seven AGN are also detected in their LyC, including one at redshift z=3.951 and z850 = 26.1. From stacked data (LBGs) we set an upper limit to the average f_esc in the range 5%--20%, depending on the how the data are selected (e.g., by magnitude and/or redshift). We undertake extensive Monte Carlo simulations that take into account intergalactic attenuation, stellar population synthesis models, dust extinction and photometric noise in order to explore the moments of the distribution of the escaping radiation. Various distributions (exponential, log-normal and Gaussian) are explored. We find that the median f_esc is lower than ~6% with an 84% percentile limit not larger than 20%. If this result remains valid for fainter LBGs down to current observational limits, then the LBG population might be not sufficient to account for the entire photoionization budget at the redshifts considered here, with the exact details dependent upon the assumed ionizing background and QSO contribution thereto. It is possible that f_esc depends on the UV luminosity of the galaxies, with fainter galaxies having higher f_esc, and estimates of f_esc from a sample of faint LBG from the HUDF (i775<28.5) are in broad quantitative agreement with such a scenario.Comment: 58 pages, 23 figures; submitted to ApJ, revised version in response to referee's comment

Variations in the slope of the resolved star-forming main sequence: A tool for constraining the mass of star-forming regions

The correlation between galaxies' integrated stellar masses and star formation rates (the 'star formation main sequence', SFMS) is a well-established scaling relation. Recently, surveys have found a relationship between the star formation rate (SFR) and stellar mass surface densities on kpc and sub-kpc scales (the 'resolved SFMS', rSFMS). In this work, we demonstrate that the rSFMS emerges naturally in Feedback In Realistic Environments 2 (FIRE-2) zoom-in simulations of Milky Way-mass galaxies. We make SFR and stellar mass maps of the simulated galaxies at a variety of spatial resolutions and star formation averaging time-scales and fit the rSFMS using multiple methods from the literature. While the absolute value of the SFMS slope (αMS) depends on the fitting method, the slope is steeper for longer star formation time-scales and lower spatial resolutions regardless of the fitting method employed. We present a toy model that quantitatively captures the dependence of the simulated galaxies' αMS on spatial resolution and use it to illustrate how this dependence can be used to constrain the characteristic mass of star-forming clumps

A High-Frequency Search for Pulsars Within the Central Parsec of SgrA*

We report results from a deep high-frequency search for pulsars within the central parsec of Sgr A* using the Green Bank Telescope. The observing frequency of 15 GHz was chosen to maximize the likelihood of detecting normal pulsars (i.e. with periods of $\sim 500$\,ms and spectral indices of $\sim -1.7$) close to Sgr A*, that might be used as probes of gravity in the strong-field regime; this is the highest frequency used for such pulsar searches of the Galactic Center to date. No convincing candidate was detected in the survey, with a $10\sigma$ detection threshold of $\sim 10 \mu$Jy achieved in two separate observing sessions. This survey represents a significant improvement over previous searches for pulsars at the Galactic Center and would have detected a significant fraction ($\gtrsim 5%) of the pulsars around Sgr A*, if they had properties similar to those of the known population. Using our best current knowledge of the properties of the Galactic pulsar population and the scattering material toward Sgr A*, we estimate an upper limit of 90 normal pulsars in orbit within the central parsec of Sgr A*.Comment: 10 pages, 7 figures, accepted for publication in the ApJ

Diffusive propagation of cosmic rays from supernova remnants in the Galaxy. I: spectrum and chemical composition

In this paper we investigate the effect of stochasticity in the spatial and temporal distribution of supernova remnants on the spectrum and chemical composition of cosmic rays observed at Earth. The calculations are carried out for different choices of the diffusion coefficient D(E) experienced by cosmic rays during propagation in the Galaxy. In particular, at high energies we assume that D(E)\sim E^{\delta}, with $\delta=1/3$ and $\delta=0.6$ being the reference scenarios. The large scale distribution of supernova remnants in the Galaxy is modeled following the distribution of pulsars, with and without accounting for the spiral structure of the Galaxy. We find that the stochastic fluctuations induced by the spatial and temporal distribution of supernovae, together with the effect of spallation of nuclei, lead to mild but sensible violations of the simple, leaky-box-inspired rule that the spectrum observed at Earth is $N(E)\propto E^{-\alpha}$ with $\alpha=\gamma+\delta$, where $\gamma$ is the slope of the cosmic ray injection spectrum at the sources. Spallation of nuclei, even with the small rates appropriate for He, may account for slight differences in spectral slopes between different nuclei, providing a possible explanation for the recent CREAM observations. For $\delta=1/3$ we find that the slope of the proton and helium spectra are $\sim 2.67$ and $\sim 2.6$ respectively at energies above 1 TeV (to be compared with the measured values of $2.66\pm 0.02$ and $2.58\pm 0.02$). For $\delta=0.6$ the hardening of the He spectra is not observed. We also comment on the effect of time dependence of the escape of cosmic rays from supernova remnants, and of a possible clustering of the sources in superbubbles. In a second paper we will discuss the implications of these different scenarios for the anisotropy of cosmic rays.Comment: 28 pages, To appear in JCA

G-protein Signaling Modulator-3 Regulates Heterotrimeric G-protein Dynamics through Dual Association with Gβ and Gα i Protein Subunits

Regulation of the assembly and function of G-protein heterotrimers (Gα·GDP/Gβγ) is a complex process involving the participation of many accessory proteins. One of these regulators, GPSM3, is a member of a family of proteins containing one or more copies of a small regulatory motif known as the GoLoco (or GPR) motif. Although GPSM3 is known to bind Gαi·GDP subunits via its GoLoco motifs, here we report that GPSM3 also interacts with the Gβ subunits Gβ1 to Gβ4, independent of Gγ or Gα·GDP subunit interactions. Bimolecular fluorescence complementation studies suggest that the Gβ-GPSM3 complex is formed at, and transits through, the Golgi apparatus and also exists as a soluble complex in the cytoplasm. GPSM3 and Gβ co-localize endogenously in THP-1 cells at the plasma membrane and in a juxtanuclear compartment. We provide evidence that GPSM3 increases Gβ stability until formation of the Gβγ dimer, including association of the Gβ-GPSM3 complex with phosducin-like protein PhLP and T-complex protein 1 subunit eta (CCT7), two known chaperones of neosynthesized Gβ subunits. The Gβ interaction site within GPSM3 was mapped to a leucine-rich region proximal to the N-terminal side of its first GoLoco motif. Both Gβ and Gαi·GDP binding events are required for GPSM3 activity in inhibiting phospholipase-Cβ activation. GPSM3 is also shown in THP-1 cells to be important for Akt activation, a known Gβγ-dependent pathway. Discovery of a Gβ/GPSM3 interaction, independent of Gα·GDP and Gγ involvement, adds to the combinatorial complexity of the role of GPSM3 in heterotrimeric G-protein regulation

Diffusive propagation of cosmic rays from supernova remnants in the Galaxy. II: anisotropy

We investigate the effects of stochasticity in the spatial and temporal distribution of supernova remnants on the anisotropy of cosmic rays observed at Earth. The calculations are carried out for different choices of the diffusion coefficient D(E) for propagation in the Galaxy. The propagation and spallation of nuclei are taken into account. At high energies we assume that $D(E)\sim(E/Z)^{\delta}$, with $\delta=1/3$ and $\delta=0.6$ being the reference scenarios. The large scale distribution of supernova remnants in the Galaxy is modeled following the distribution of pulsars with and without accounting for the spiral structure of the Galaxy. Our calculations allow us to determine the contribution to anisotropy resulting from both the large scale distribution of SNRs in the Galaxy and the random distribution of the nearest remnants. The naive expectation that the anisotropy amplitude scales as D(E) is shown to be an oversimplification which does not reflect in the predicted anisotropy for any realistic distribution of the sources. The fluctuations in the anisotropy pattern are dominated by nearby sources, so that predicting or explaining the observed anisotropy amplitude and phase becomes close to impossible. We find however that the very weak energy dependence of the anisotropy amplitude below $10^{5}$ GeV and the rise at higher energies, can best be explained if the diffusion coefficient is $D(E)\sim E^{1/3}$. Faster diffusion, for instance with $\delta=0.6$, leads in general to an exceedingly large anisotropy amplitude. The spiral structure introduces interesting trends in the energy dependence of the anisotropy pattern, which qualitatively reflect the trend seen in the data. For large values of the halo size we find that the anisotropy becomes dominated by the large scale regular structure of the source distribution, leading indeed to a monotonic increase of $\delta_A$ with energy.Comment: 21 Pages, to appear in JCA