Thermodynamic parameters including acid dissociation constants for bromochlorophenols (BCPs)

This contribution reports standard gas-phase enthalpies of formation (ΔfH°298), entropies (S°298), and heat capacities (Cp°(T)) for all plausible 64 bromochlorophenols (BCPs) at the M062X meta hybrid level using a polarized basis set of 6-311+G(d,p). Isodesmic work reactions served to calculate the standard enthalpies of formation for all bromochlorophenol molecules and several bromochlorophenoxy radicals. Standard entropies and heat capacities comprise correction terms due to the treatment of O-H bonds as hindered rotors. Values of the bond dissociation enthalpies (BDHs) of O-H bonds, calculated for a selected series of bromochlorophenols, vary slightly with the change in the pattern and degree of halogenation of the phenyl ring. A thermodynamic cycle facilitated the estimation of pKa values, based on the calculated solvation and gas-phase deprotonation energies. We estimated the solvation energies of 19 out of 64 BCPs and their respective anions based on the integral equation formalism polarizable continuum model using optimized structures in the aqueous phase. Values of pKa decrease significantly from around 9 for monohalogenated to around 3 for pentahalogenated phenols

IUPAC-NIST solubility data series. 81. Hydrocarbons with water and seawater - Revised and updated. Part 8. C9 hydrocarbons with water

The mutual solubility and related liquid-liquid equilibria of C9 hydrocarbons with water are exhaustively and critically reviewed. Reports of the experimental determination of solubility in 18 chemically distinct binary systems that appeared in the primary literature prior to the end of 2002 are compiled. For 8 systems, sufficient data are available to allow critical evaluation. All data are expressed as mass percent and mole fraction, as well as the originally reported units. In addition to the standard evaluation criteria used throughout the Solubility Date Series, a new method based on the evaluation of the all experimental data for a given homologous series of aliphatic and aromatic hydrocarbons was used

IUPAC-NIST solubility data series. 81. Hydrocarbons with water and seawater-revised and updated. Part 5. C7 hydrocarbons with water and heavy water

The mutual solubility and related liquid-liquid equilibria of C7 hydrocarbons with water and heavy water are exhaustively and critically reviewed. Reports of experimental determination of solubility in 23 chemically distinct binary systems that appeared in the primary literature prior to end of 2002 are compiled. For 9 systems sufficient data are available to allow critical evaluation. All data are expressed as mass percent and mole fraction as well as the originally reported units. In addition to the standard evaluation criteria used throughout the Solubility Data Series, a new method based on the evaluation of the all experimental data for a given homologous series of aliphatic and aromatic hydrocarbons was used

Glasslike Behavior in Aqueous Electrolyte Solutions

When salts are added to water, the viscosity generally increases suggesting the ions increase the strength of the water's hydrogen-bond network. However, infrared pump-probe measurements on electrolyte solutions have found that ions have no influence on the rotational dynamics of water molecules implying no enhance-ment or breakdown of the hydrogen-bond network. Here we report optical Kerr-effect and dielectric relaxa-tion spectroscopic measurements, which have enabled us to separate the effects of rotational and transitional motions of the water molecules. These data show that electrolyte solutions behave like a supercooled liquid approaching a glass transition in which rotational and translational molecular motions are decoupled. It is now possible to understand previously conflicting viscosity data, nuclear magnetic resonance relaxation, and ultrafast infrared spectroscopy in a single unified picture

Tracing the source of ancient reworked organic matter delivered to the North Atlantic Ocean during Heinrich Events

A major effort of the geochemical and paleoclimate community has been to identify the specific sources of the ice-rafted debris (IRD) in Heinrich Layers (HLs). Although the general consensus is that the majority of the IRD originated from the Hudson area of northern Canada, the specific sources are not well constrained. Here we compare the diagnostic organic geochemical signature of HLs to that of a number of Paleozoic outcrops across the former margin of the Laurentide ice sheet. We show that the biomarker signature of Upper Ordovician strata from Southampton and Baffin Island is compatible with that found in HLs in the Labrador Sea and North Atlantic, while the biomarker signature of other Paleozoic formations from the former margin of the Laurentide ice sheet is not. In addition to the biomarker signature, key-inorganic characteristics (δ18O, εNd, and 87Sr/86Sr ratios) of these formations from Southampton and Baffin Island are consistent with those reported from HLs. The location of these formations in and around the Hudson Strait is compatible with palaeo-ice flow regimes through the Hudson Strait, allowing for easy entrainment and rapid transport to the ocean. Based on these results we propose that these specific Upper Ordovician formations form a main source of IRD in HLs and hence infer an active role of the Hudson Strait paleo-ice flow in these events

Flux variability of phyto- and zooplankton communities in the Mauritanian coastal upwelling between 2003 and 2008

Continuous multiyear records of sediment-trap-gained microorganism fluxes are scarce. Such studies are important to identify and to understand the main forcings behind seasonal and multiannual evolution of microorganism flux dynamics. Here, we assess the long-term flux variations and population dynamics of diatoms, coccolithophores, calcareous and organic dinoflagellate cysts, foraminifera and pteropods in the eastern boundary upwelling ecosystem of the Canary Current. A multiannual, continuous sediment trap experiment was conducted at the mooring site CBeu (Cap Blanc eutrophic; ∼20∘ N, 18∘ W; trap depth is ca. 1300 m) off Mauritania (northwest Africa), between June 2003 and March 2008. Throughout the study, the reasonably consistent good match of fluxes of microorganisms and bulk mass reflects the seasonal occurrence of the main upwelling season and relaxation and the contribution of microorganisms to mass flux off Mauritania. A clear successional pattern of microorganisms, i.e., primary producers followed by secondary producers, is not observed. High fluxes of diatoms, coccolithophores, organic dinoflagellate cysts, and planktonic foraminifera occur simultaneously. Peaks of calcareous dinoflagellate cysts and pteropods mostly occurred during intervals of upwelling relaxation. A striking feature of the temporal variability of population occurrences is the persistent pattern of seasonal groups contributions. Species of planktonic foraminifera, diatoms, and organic dinoflagellate cysts typical of coastal upwelling, as well as cooler-water planktonic foraminifera and the coccolithophore Gephyrocapsa oceanica, are abundant at times of intense upwelling (late winter through early summer). Planktonic foraminifera and calcareous dinoflagellate cysts are dominant in warm pelagic surface waters, and all pteropod taxa are more abundant in fall and winter when the water column stratifies. Similarly, coccolithophores of the upper and lower photic zones, together with Emiliania huxleyi, and organic dinoflagellate cysts dominate the assemblage during phases of upwelling relaxation and deeper layer mixing. A significant shift in the “regular” seasonal pattern of taxa relative contribution is observed between 2004 and 2006. Benthic diatoms strongly increased after fall 2005 and dominated the diatom assemblage during the main upwelling season. Additional evidence for a change in population dynamics is the short dominance of the coccolithophore Umbilicosphaera annulus, the occurrence of the pteropod Limacina bulimoides and the strong increase in the flux of calcareous dinoflagellate cysts, abundant in warm tropical oligotrophic waters south of the study area after fall 2005. Altogether, this suggests that pulses of southern waters were transported to the sampling site via the northward Mauritania Current. Our multiannual trap experiment provides a unique opportunity to characterize temporal patterns of variability that can be extrapolated to other eastern boundary upwelling ecosystems (EBUEs), which are experiencing or might experience similar future changes in their plankton community

A Case of Relapsing-Remitting Neuroborreliosis? Challenges in the Differential Diagnosis of Recurrent Myelitis

We report the case of a 31-year-old woman with 4 episodes of myelitis with pleocytosis, a positive Borrelia burgdorferi serology with positive antibody indices, and full recovery each time after antibiotic and steroid treatment, suggesting neuroborreliosis. We nevertheless believe that recurrent neuroborreliosis is improbable based on the levels of the chemokine CXCL13 in cerebrospinal fluid and favor the diagnosis of post-infectious autoimmune-mediated transverse myelitis possibly triggered by an initial neuroborreliosis as the cause of the relapses observed in our patient. We demonstrate the diagnostic steps and procedures which were important in the differential diagnosis of this unusual and challenging case