Ventilation of the abyss in the Atlantic sector of the Southern Ocean.

The Atlantic sector of the Southern Ocean is the world's main production site of Antarctic Bottom Water, a water-mass that is ventilated at the ocean surface before sinking and entraining older water-masses-ultimately replenishing the abyssal global ocean. In recent decades, numerous attempts at estimating the rates of ventilation and overturning of Antarctic Bottom Water in this region have led to a strikingly broad range of results, with water transport-based calculations (8.4-9.7 Sv) yielding larger rates than tracer-based estimates (3.7-4.9 Sv). Here, we reconcile these conflicting views by integrating transport- and tracer-based estimates within a common analytical framework, in which bottom water formation processes are explicitly quantified. We show that the layer of Antarctic Bottom Water denser than 28.36 kg m[Formula: see text] [Formula: see text] is exported northward at a rate of 8.4 ± 0.7 Sv, composed of 4.5 ± 0.3 Sv of well-ventilated Dense Shelf Water, and 3.9 ± 0.5 Sv of old Circumpolar Deep Water entrained into cascading plumes. The majority, but not all, of the Dense Shelf Water (3.4 ± 0.6 Sv) is generated on the continental shelves of the Weddell Sea. Only 55% of AABW exported from the region is well ventilated and thus draws down heat and carbon into the deep ocean. Our findings unify traditionally contrasting views of Antarctic Bottom Water production in the Atlantic sector, and define a baseline, process-discerning target for its realistic representation in climate models.

Role of the time dependence of Boltzmann open probability in voltage-gated proton channels.

The modeling and simulation of experimental families of current-time (I-t) curves of dimeric voltage-gated proton channels and of proton-conducting voltage sensing domains (VSDs) with a minimum of free parameters requires the movement of protons to be controlled by the rate of increase of the Boltzmann open probability p over time in passing from the holding to the depolarizing potential. Families of I-t curves of protomers and proton-conducting VSDs can be satisfactorily fitted by the use of a single free parameter expressing the rate constant kp for the increase of p over time. Families of I-t curves of dimeric Hv1 channels can be fitted by a model that assumes an initial proton current I1 flowing along the two monomeric units, while they are still operating separately; I1 is gradually replaced by a slower and more potential-dependent current I2 flowing when the two monomers start operating jointly under the control of the coiled-coil domain. Here too, p is assumed to increase over time with a rate constant kp that doubles in passing from I1 to I2, with fit requiring three free parameters. Chord conductance yields erroneously high gating charges when fitted by the Boltzmann function, differently from slope conductance.

Controls on the Isotopic Composition of Nitrite (δ15N and δ18O) during Denitrification in Freshwater Sediments.

The microbial reduction of nitrate, via nitrite into gaseous di-nitrogen (denitrification) plays a major role in nitrogen removal from aquatic ecosystems. Natural abundance stable isotope measurements can reveal insights into the dynamics of production and consumption of nitrite during denitrification. In this study, batch experiments with environmental bacterial communities were used to investigate variations of concentrations and isotope compositions of both nitrite and nitrate under anoxic conditions. To this end, denitrification experiments were carried out with nitrite or nitrate as sole electron acceptors at two substrate levels respectively. For experiments with nitrate as substrate, where the intermediate compound nitrite is both substrate and product of denitrification, calculations of the extent of isotope fractionation were conducted using a non-steady state model capable of tracing chemical and isotope kinetics during denitrification. This study showed that nitrogen isotope fractionation was lower during the use of nitrite as substrate (ε = -4.2 and -4.5‰ for both treatments) as compared to experiments where nitrite was produced as an intermediate during nitrate reduction (ε = -10 and -15‰ for both treatments). This discrepancy might be due to isotopic fractionation within the membrane of denitrifiers. Moreover, our results confirmed previously observed rapid biotic oxygen isotope exchange between nitrite and water.

On the interaction of the highly charged peptides casocidins with biomimetic membranes.

Casocidin I and II (CI and CII) are structurally related antimicrobial peptides made of 39 and 31 amino acids, respectively, which derive from natural proteolytic processing of αs2-casein and adopt an ordered α-helical structure in biomimetic membranes. Their putative membrane-permeabilizing activity was investigated at Hg-supported self-assembled monolayers (SAMs) and at tethered bilayer lipid membranes (tBLMs); the latter consisted of a monolayer of 2,3,di-O-phytanyl-sn-glycerol-1-tetraethylene-glycol-d,l-α lipoic acid ester thiolipid (DPTL), with a dioleoylphosphatidylcholine (DOPC) or dioleoylphosphatidylserine (DOPS) monolayer on top of it. Interaction of CI and CII with these biomimetic membranes was studied by four electrochemical techniques at pH 3, 5.4 and 6.8. Peptide incorporation in tBLMs was attempted via scans of electrochemical impedance spectra. Experiments demonstrated that CI and CII penetrate SAMs as well as the distal DOPC monolayer of DPTL/DOPC tBLMs, but not the proximal phytanyl monolayer, with the only exception of CII at pH 5.4. Conversely, CII permeabilized DPTL/DOPS tBLMs to a moderate extent at all investigated pH values by forming holes across the membrane, but not ion channels. Structural distribution of charged residues seemed to prevent CII from having a hydrophobic side of the α-helix capable of stabilizing a regular ion channel in the lipid matrix.

When and how the melittin ion channel exhibits ohmic behavior.

Melittin exhibits an ohmic behavior in a lipid bilayer having a DOPC distal leaflet and interposed between a 2.25nm tetraethyleneoxy chain tethered to a mercury drop and an aqueous solution. This behavior is induced in a pH6.8 buffer solution of 0.8µg/mL melittin by a pretreatment consisting of series of electrochemical impedance spectroscopy measurements at bias potentials varied by 50mV steps over a transmembrane potential range from about +250 to -250mV. This metastable ohmic behavior remains unchanged for hours, even after acidifying the solution to pH3. The midpoint potential E1/2 between the positive and negative peaks of the resulting cyclic voltammogram is almost coincident with that of the ohmic channels gramicidin and syringopeptin 25A and shifts by the same amount toward more positive potentials with a pH decrease from 6.8 to 3. This common cyclic voltammetry behavior is explained by a tilt of the DOPC polar heads around the channel mouth of these three peptides and is simulated by a modelistic approach. The ohmic behavior of melittin is explained by the persistence of the peptide orientation initially assumed at trans-negative potentials even after application of trans-positive ones, at sufficiently high peptide-to-lipid molar ratios.

Stable isotopes in the atmospheric marine boundary layer water vapour over the Atlantic Ocean, 2012-2015.

The water vapour isotopic composition (1H216O, H218O and 1H2H16O) of the Atlantic marine boundary layer has been measured from 5 research vessels between 2012 and 2015. Using laser spectroscopy analysers, measurements have been carried out continuously on samples collected 10-20 meter above sea level. All the datasets have been carefully calibrated against the international VSMOW-SLAP scale following the same protocol to build a homogeneous dataset covering the Atlantic Ocean between 4°S to 63°N. In addition, standard meteorological variables have been measured continuously, including sea surface temperatures using calibrated Thermo-Salinograph for most cruises. All calibrated observations are provided with 15-minute resolution. We also provide 6-hourly data to allow easier comparisons with simulations from the isotope-enabled Global Circulation Models. In addition, backwards trajectories from the HYSPLIT model are supplied every 6-hours for the position of our measurements.

A capacitive probe for Electron Spin Resonance detection.

The use of the magnetic field associated with Maxwell displacement current in a capacitor is proposed for the detection of Electron Spin Resonance. A probe based on this concept is realized and successfully tested with CW radio-frequency in the band going from 200MHz to 1GHz with a DPPH sample. A significant increase of Signal to Noise Ratio is observed while increasing the frequency.

Photoelectric response of purple membrane fragments adsorbed on a lipid monolayer supported by mercury and characterization of the resulting interphase.

Purple membrane (PM) fragments were adsorbed on a dioleoylphosphatidylcholine (DOPC) monolayer supported by mercury to investigate the kinetics of light-driven proton transport by bacteriorhodopsin (bR). PM fragments were also adsorbed on a mercury-supported triethyleneoxythiol (TET) monolayer. On both monolayers, the light-on current exhibits a finite, potential dependent stationary component that decreases linearly with a positive shift in the applied potential. The light-on and light-off capacitive photocurrents were interpreted on the basis of a simple equivalent circuit, which accounts for the potential dependence of the stationary light-on current. The potential of zero stationary current is about equal to +0.010 V vs. saturated calomel electrode (SCE) on DOPC-coated mercury. The absolute potential difference across the PM fragments adsorbed at this applied potential was estimated on the basis of extrathermodynamic considerations and amounts to about +260 mV; it compares favorably with the value, +250 mV, of the transmembrane potential of zero stationary current across an oocyte plasma membrane incorporating bR [Biophys. J. 74 (1998) 403.]. The effect of the proton pumping activity of photoexcited PM fragments on the electroreduction kinetics of ubiquinone-10 incorporated in the DOPC monolayer underlying the PM fragments was investigated.

Electron-paramagnetic resonance detection with software time locking.

A setup for electron paramagnetic resonance with narrow band digital detection is described. A low frequency reference tone is added to the radio frequency signal. This reference signal, after digital detection, is used to lock the resonance signal, even in the absence of hardware time locking among the radio frequency generator, the conversion local oscillators, and the sampling stage. Results obtained with 2,2-Diphenyl-1-Pycryl-Hydrazil are presented and discussed.

Use of scanning probe microscopy to study the evolution of nanometer sized liquid structures.

The evolution of the profile of nanometer sized water drops on a mica surface has been studied through hydration scanning probe microscopy. A time range from a few seconds down to a fraction of millisecond after the formation of the drop has been explored. This high time resolution has been obtained by sampling a series of statistically equivalent drops. This approach also avoids any probe interference during the drop evolution process.

Photoinduced electroreduction of chlorophyllide on alkanethiol-coated mercury.

Monolayers of n-alkanethiols of chain length from C12 to C18 were self-assembled on a hanging mercury drop electrode, and a film of chlorophyllide (Chlide) was adsorbed on top of them. The reduction photocurrents following illumination of the Chlide film were measured over the potential range in which the Chlide is electroinactive in the dark, and their action spectra were determined. Plotting the derivative of the photocurrents with respect to the applied potential against potential yields bell-shaped curves that can be fitted to a Gaussian. The potential of the Gaussian maximum was used to determine the reorganization energy lambda for the Chlide electroreduction process. An increase in the thiol chain length causes lambda to decrease regularly and the photocurrent to decay exponentially with the monolayer thickness, with a decay constant beta of about 0.17 A(-1).