Effect of counterions on properties of micelles formed by alkylpyridinium surfactants .1. Conductometry and H-1-NMR chemical shifts

This paper delineates the influence of counterions on the aggregation behavior of 1-methyl-4-n-dodecylpyridinium surfactants, using conductometry and H-1-NMR spectroscopy. Three types of counterions have been studied: (i) halides, (ii) alkanesulfonates, and (iii) aromatic counterions. The critical. micelle concentration is found to decrease with increasing counterion size and increasing counterion hydrophobicity, whereas the degree of counterion binding increases. The aggregation behavior of 1-methyl-4-n-dodecylpyridinium surfactants with aromatic counterions is shown to be markedly dependent on the substituent (hydrophobicity) and the substitution pattern in the aromatic ring of the counterion. Depending on the molecular architecture of the aromatic counterion, extremely long wormlike micelles can be formed instead of(nearly) spherical micelles. NMR experiments revealed that all aromatic counterions intercalate in between the pyridinium headgroups of the micelles, with more or less the same degree of penetration. All results can be explained on the basis of counterion-surfactant and counterion-water interactions, taking into account the specific microenvironment in the Stern layer

Classification of calorimetric titration plots for alkyltrimethylammonium and alkylpyridinium cationic surfactants in aqueous solutions

Calorimetric titration plots for deaggregation of micelles formed by alkylpyridinium and alkyltrimethylammonium surfactants are classified into three types, A, B and C, depending on the shape of the plot of the enthalpy of dilution as a function of surfactant concentration. For Type A plots the recorded heat of injection q changes sharply between two parts of the titration curve over which the recorded heats are effectively independent of the composition of the solution in the sample cell. For Type B plots, the change is less sharp and both parts of the plot show dependences of heat q on solution composition, a pattern accounted for in terms of solute-solute interactions. Type C plots are complicated, in that no sharp change in q is recorded, the complexity of the plots being accounted for in terms of micelle-monomer equilibria over a range of surfactant concentrations and related enthalpies of deaggregation

The effect of temperature and salinity on the stable hydrogen isotopic composition of long chain alkenones produced by <i>Emiliania huxleyi</i> and <i>Gephyrocapsa oceanica</i>

International audienceTwo haptophyte algae, Emiliania huxleyi and Gephyrocapsa oceanica, were cultured at different temperatures and salinities to investigate the impact of these factors on the hydrogen isotopic composition of long chain alkenones synthesized by these algae. Results showed that alkenones synthesized by G. oceanica were on average depleted in D by 30 per mil compared to those of E. huxleyi when grown under similar conditions. The fractionation factor, ?alkenones-H2O, ranged from 0.760 to 0.815 for E. huxleyi and from 0.741 to 0.788 for G. oceanica. There was no significant correlation of ?alkenones-H2O with temperature but a positive linear correlation was observed between ?alkenones-H2O and salinity with ~3 per mil change in fractionation per salinity unit. This suggests that salinity can have a substantial impact on the stable hydrogen isotopic composition of long chain alkenones in natural environments and, vice versa, that ?D can possibly be used as a proxy to estimate paleosalinity

The coordination and distribution of B in foraminiferal calcite

The isotopic ratio and concentration of B in foraminiferal calcite appear to reflect the pH and bicarbonate concentration of seawater. The use of B as a chemical proxy tracer has the potential to transform our understanding of the global carbon cycle, and ocean acidification processes. However, discrepancies between the theory underpinning the B proxies, and mineralogical observations of B coordination in biomineral carbonates call the basis of these proxies into question. Here, we use synchrotron X-ray spectromicroscopy to show that B is hosted solely as trigonal BO3 in the calcite test of Amphistegina lessonii, and that B concentration exhibits banding at the micron length scale. In contrast to previous results, our observation of trigonal B agrees with the predictions of the theoretical mechanism behind B palaeoproxies. These data strengthen the use of B for producing palaeo-pH records. The observation of systematic B heterogeneity, however, highlights the complexity of foraminiferal biomineralisation, implying that B incorporation is modulated by biological or crystal growth processes.We would like to acknowledge David Nicol, Iris Buisman and Martin Walker for invaluable technical assistance, and James Bryson for his help with synchrotron data collection. Wewould like to thank Jean DeMouthe (California Academy of Sciences) and Mike Rumsey (Natural History Museum, London) for provision of B-containing minerals for use as reference materials. This work was funded by ERC (grant 2010-ADG-267931 to HE), NERC, Jesus College (Cambridge)and the US Department of Energy (via ALS).This is the final published version. It first appeared at http://www.sciencedirect.com/science/article/pii/S0012821X15000849

The effect of temperature, salinity and growth rate on the stable hydrogen isotopic composition of long chain alkenones produced by <I>Emiliania huxleyi</I> and <I>Gephyrocapsa oceanica</I>

International audienceTwo haptophyte algae, Emiliania huxleyi and Gephyrocapsa oceanica, were cultured at different temperatures and salinities to investigate the impact of these factors on the hydrogen isotopic composition of long chain alkenones synthesized by these algae. Results showed that alkenones synthesized by G. oceanica were on average depleted in D by 30 compared to those of E. huxleyi when grown under similar temperature and salinity conditions. The fractionation factor, ?alkenones-H2O, ranged from 0.760 to 0.815 for E. huxleyi and from 0.741 to 0.788 for G. oceanica. There was no significant correlation of ?alkenones-H2O with temperature but a positive linear correlation was observed between ?alkenones-H2O and salinity with ~3 change in fractionation per salinity unit and a negative correlation between ?alkenones-H2O and growth rate. This suggests that both salinity and growth rate can have a substantial impact on the stable hydrogen isotopic composition of long chain alkenones in natural environments

The ‘algebra of evolution’: the Robertson–Price identity and viability selection for body mass in a wild bird population

By the Robertson–Price identity, the change in a quantitative trait owing to selection, is equal to the trait’s covariance with relative fitness. In this study, we applied the identity to long-term data on superb fairy-wrens Malurus cyaneus, to estimate phenotypic and genetic change owing to juvenile viability selection. Mortality in the four-week period between fledging and independence was 40%, and heavier nestlings were more likely to survive, but why? There was additive genetic variance for both nestling mass and survival, and a positive phenotypic covariance between the traits, but no evidence of additive genetic covariance. Comparing standardized gradients, the phenotypic selection gradient was positive, βP = 0.108 (0.036, 0.187 95% CI), whereas the genetic gradient was not different from zero, βA = −0.025 (−0.19, 0.107 95% CI). This suggests that factors other than nestling mass were the cause of variation in survival. In particular, there were temporal correlations between mass and survival both within and between years. We suggest that use of the Price equation to describe cross-generational change in the wild may be challenging, but a more modest aim of estimating its first term, the Robertson–Price identity, to assess within-generation change can provide valuable insights into the processes shaping phenotypic diversity in natural populations. This article is part of the theme issue ‘Fifty years of the Price equation’G.K.H. was supported by the U.K. Natural Environment Research Council (grant no. NE/L002558/1) through the University of Edinburgh’s E3 Doctoral Training Partnership, and L.E.B.K. was funded by an ARC Future Fellowship FT110100453. The long-term superb fairy-wren study research has been facilitated by a series of Discovery Project grants from the Australian Research Council to A.C. and L.E.B.K., most recently DP150100298

Effects of ocean acidification on invertebrate settlement at volcanic CO<inf>2</inf> vents

We present the first study of the effects of ocean acidification on settlement of benthic invertebrates and microfauna. Artificial collectors were placed for 1 month along pH gradients at CO2 vents off Ischia (Tyrrhenian Sea, Italy). Seventy-nine taxa were identified from six main taxonomic groups (foraminiferans, nematodes, polychaetes, molluscs, crustaceans and chaetognaths). Calcareous foraminiferans, serpulid polychaetes, gastropods and bivalves showed highly significant reductions in recruitment to the collectors as pCO2 rose from normal (336-341 ppm, pH 8.09-8.15) to high levels (886-5,148 ppm) causing acidified conditions near the vents (pH 7.08-7.79). Only the syllid polychaete Syllis prolifera had higher abundances at the most acidified station, although a wide range of polychaetes and small crustaceans was able to settle and survive under these conditions. A few taxa (Amphiglena mediterranea, Leptochelia dubia, Caprella acanthifera) were particularly abundant at stations acidified by intermediate amounts of CO2 (pH 7. 41-7.99). These results show that increased levels of CO2 can profoundly affect the settlement of a wide range of benthic organisms. © 2010 Springer-Verlag