Isotopic disequilibrium of Cu in marine ferromanganese crusts: Evidence from ab initio predictions of Cu isotope fractionation on sorption to birnessite

In the oceans, Cu is strongly scavenged by ferromanganese (Fe-Mn) crusts. The isotopic fractionation of Cu between seawater and crusts provides insight into the mechanisms of trace metal cycling in the oceans. Dissolved Cu in seawater is isotopically heavy ( ‰ ) relative to Cu in crusts ( ‰ ). The primary mineral phase sorbing divalent trace metals in Fe-Mn crusts is birnessite. Recent laboratory measurements show that isotopically light Cu is preferentially sorbed on birnessite, with a fractionation factor of ‰ . Here, we use first-principles (quantum mechanical) calculations to predict the isotopic fractionation between aqueous Cu2+ complexes and Cu as a surface complex on birnessite. We find that isotopic fractionation between the Cu(H2O) complex and sorbed Cu should be 0.49‰ (at 25 °C), in close agreement with experiments, confirming that these experimental results reflects equilibrium fractionation. We then predict the isotopic fractionation between dissolved inorganic Cu in seawater and birnessite given the thermodynamic speciation of dissolved Cu at pH 8. We find dissolved inorganic Cu should be 0.94‰ (at 5 °C) heavier than Cu sorbed to birnessite. This value is substantially greater than the observed fractionation between seawater and Fe-Mn crusts (Δsw-fmc ‰ ). Moreover, it is well established that dissolved Cu in seawater is strongly complexed by organic ligands. Based on model Cu complexes and published experimental data, we estimate that fractionation of Cu by organic ligands should increase the equilibrium fractionation between seawater and Fe-Mn crusts by 0.2 to 1.5‰ to yield Δsw-fmc = +1.1 to 2.4‰. We conclude that Cu in marine Fe-Mn crusts in not in isotopic equilibrium with dissolved Cu in seawater, and consider the possible explanations of this surprising finding

Surface complexation of Cu on birnessite (d-MnO2): Controls on Cu in the deep ocean

Hexagonal birnessite (d-MnO2) is a close analogue to the dominant phase in hydrogenetic marine ferromanganese crusts and nodules. These deposits contain 0.25 wt.% Cu which is believed to be scavenged from the overlying water column where Cu concentrations are near 0.1 lg/L. Here, we measured the sorption of Cu on d-MnO2 as a function of pH and surface loading. We characterized the nature of the Cu sorption complex at pH 4 and 8 using EXAFS spectroscopy and find that, at pH 4, Cu sorbs to birnessite by inner-sphere complexation on the {0 0 1} surface at sites above Mn vacancies to give a three to four fold coordinated complex with 6 Mn neighbors at 3.4 A ̊ . At pH 8, however, we find that some Cu has become structurally incorporated into the MnO2 layer by occupying the vacancy sites to give 6 Mn neighbors at 2.91 A ̊ . Density functional calculations on CuMn O ðOHÞ ðH OÞ 4 and CuMn O ðOHÞ ðH OÞ 1 clusters predict a threefold coordinated surface 18 24 30 2 3 18 21 33 2 3 complex and show that the change from surface complexation to structural incorporation is a response to protonation of oxy- gens surrounding the vacancy site. Consequently, we propose that the transformation between sorption via surface complex and vacancy site occupancy should be reversible. By fitting the Cu sorption as a function of surface loading and pH to the formation of the observed and predicted surface complex, we developed a surface complexation model (in the basic Stern approximation) for the sorption of Cu onto birnessite. Using this model, we demonstrate that the concentration of inorganic Cu in the deep ocean should be several orders of magnitude lower than the observed total dissolved Cu. We propose that the observed total dissolved Cu concentration in the oceans reflects solubilization of Cu by microbially generated ligands

Radium ion: A possible candidate for measuring atomic parity violation

Single trapped and laser cooled Radium ion as a possible candidate for measuring the parity violation induced frequency shift has been discussed here. Even though the technique to be used is similar to that proposed by Fortson [1], Radium has its own advantages and disadvantages. The most attractive part of Radium ion as compared to that of Barium ion is its mass which comes along with added complexity of instability as well as other issues which are discussed hereComment: Conference proceedin

An inhomogeneous toy-model of the quantum gravity with explicitly evolvable observables

An inhomogeneous (1+1)-dimensional model of the quantum gravity is considered. It is found, that this model corresponds to a string propagating against some curved background space. The quantization scheme including the Wheeler-DeWitt equation and the "particle on a sphere" type of the gauge condition is suggested. In the quantization scheme considered, the "problem of time" is solved by building of the quasi-Heisenberg operators acting in a space of solutions of the Wheeler-DeWitt equation and the normalization of the wave function corresponds to the Klein-Gordon type. To analyze the physical consequences of the scheme, a (1+1)-dimensional background space is considered for which a classical solution is found and quantized. The obtained estimations show the way to solution of the cosmological constant problem, which consists in compensation of the zero-point oscillations of the matter fields by the quantum oscillations of the scale factor. Along with such a compensation, a slow global evolution of a background corresponding to an universe expansion exists.Comment: 18 page

CAM therapies among primary care patients using opioid therapy for chronic pain

<p>Abstract</p> <p>Background</p> <p>Complementary and alternative medicine (CAM) is an increasingly common therapy used to treat chronic pain syndromes. However; there is limited information on the utilization and efficacy of CAM therapy in primary care patients receiving long-term opioid therapy.</p> <p>Method</p> <p>A survey of CAM therapy was conducted with a systematic sample of 908 primary care patients receiving opioids as a primary treatment method for chronic pain. Subjects completed a questionnaire designed to assess utilization, efficacy and costs of CAM therapies in this population.</p> <p>Results</p> <p>Patients were treated for a variety of pain problems including low back pain (38.4%), headaches (9.9%), and knee pain (6.5%); the average duration of pain was 16 years. The median morphine equivalent opioid dose was 41 mg/day, and the mean dose was 92 mg/day. Forty-four percent of the sample reported CAM therapy use in the past 12 months. Therapies utilized included massage therapy (27.3%, n = 248), chiropractic treatment (17.8%, n = 162), acupuncture (7.6%, n = 69), yoga (6.1%, n = 55), herbs and supplements (6.8%, n = 62), and prolotherapy (5.9%, n = 54). CAM utilization was significantly related to age female gender, pain severity income pain diagnosis of neck and upper back pain, and illicit drug use. Medical insurance covered chiropractic treatment (81.8%) and prolotherapy (87.7%), whereas patients primarily paid for other CAM therapies. Over half the sample reported that one or more of the CAM therapies were helpful.</p> <p>Conclusion</p> <p>This study suggests CAM therapy is widely used by patients receiving opioids for chronic pain. Whether opioids can be reduced by introducing such therapies remains to be studied.</p

Proteomics as a quality control tool of pharmaceutical probiotic bacterial lysate products

Probiotic bacteria have a wide range of applications in veterinary and human therapeutics. Inactivated probiotics are complex samples and quality control (QC) should measure as many molecular features as possible. Capillary electrophoresis coupled to mass spectrometry (CE/MS) has been used as a multidimensional and high throughput method for the identification and validation of biomarkers of disease in complex biological samples such as biofluids. In this study we evaluate the suitability of CE/MS to measure the consistency of different lots of the probiotic formulation Pro-Symbioflor which is a bacterial lysate of heat-inactivated Escherichia coli and Enterococcus faecalis. Over 5000 peptides were detected by CE/MS in 5 different lots of the bacterial lysate and in a sample of culture medium. 71 to 75% of the total peptide content was identical in all lots. This percentage increased to 87–89% when allowing the absence of a peptide in one of the 5 samples. These results, based on over 2000 peptides, suggest high similarity of the 5 different lots. Sequence analysis identified peptides of both E. coli and E. faecalis and peptides originating from the culture medium, thus confirming the presence of the strains in the formulation. Ontology analysis suggested that the majority of the peptides identified for E. coli originated from the cell membrane or the fimbrium, while peptides identified for E. faecalis were enriched for peptides originating from the cytoplasm. The bacterial lysate peptides as a whole are recognised as highly conserved molecular patterns by the innate immune system as microbe associated molecular pattern (MAMP). Sequence analysis also identified the presence of soybean, yeast and casein protein fragments that are part of the formulation of the culture medium. In conclusion CE/MS seems an appropriate QC tool to analyze complex biological products such as inactivated probiotic formulations and allows determining the similarity between lots

Multimodality Treatment with Conventional Transcatheter Arterial Chemoembolization and Radiofrequency Ablation for Unresectable Hepatocellular Carcinoma

Background/Aims: To evaluate the efficacy of multimodality treatment consisting of conventional transcatheter arterial chemoembolization (TACE) and radiofrequency ablation (RFA) in patients with non-resectable and non-ablatable hepatocellular carcinoma (HCC). Methods: In this retrospective study, 85 consecutive patients with HCC (59 solitary, 29 multifocal HCC) received TACE followed by RFA between 2001 and 2010. The mean number of tumors per patient was 1.6 +/- 0.7 with a mean size of 3.0 +/- 0.9 cm. Both local efficacy and patient survival were evaluated. Results: Of 120 treated HCCs, 99 (82.5%) showed a complete response (CR), while in 21 HCCs (17.5%) a partial response was depicted. Patients with solitary HCC revealed CR in 91% (51/56); in patients with multifocal HCC (n = 29) CR was achieved in 75% (48 of 64 HCCs). The median survival for all patients was 25.5 months. The 1-, 2-, 3- and 5-year survival rates were 84.6, 58.7, 37.6 and 14.6%, respectively. Statistical analysis revealed a significant difference in survival between Barcelona Clinic Liver Cancer (BCLC) A (73.4 months) and B (50.3 months) patients, while analyses failed to show a difference for Child-Pugh score, Cancer of Liver Italian Program (CLIP) score and tumor distribution pattern. Conclusion: TACE combined with RFA provides an effective treatment approach with high local tumor control rates and promising survival data, especially for BCLC A patients. Randomized trials are needed to compare this multimodality approach with a single modality approach for early-stage HCC. Copyright (C) 2011 S. Karger AG, Base

Subtle changes in the flavour and texture of a drink enhance expectations of satiety

Background: The consumption of liquid calories has been implicated in the development of obesity and weight gain. Energy-containing drinks are often reported to have a weak satiety value: one explanation for this is that because of their fluid texture they are not expected to have much nutritional value. It is important to consider what features of these drinks can be manipulated to enhance their expected satiety value. Two studies investigated the perception of subtle changes in a drink’s viscosity, and the extent to which thick texture and creamy flavour contribute to the generation of satiety expectations. Participants in the first study rated the sensory characteristics of 16 fruit yogurt drinks of increasing viscosity. In study two, a new set of participants evaluated eight versions of the fruit yogurt drink, which varied in thick texture, creamy flavour and energy content, for sensory and hedonic characteristics and satiety expectations. Results: In study one, participants were able to perceive small changes in drink viscosity that were strongly related to the actual viscosity of the drinks. In study two, the thick versions of the drink were expected to be more filling and have a greater expected satiety value, independent of the drink’s actual energy content. A creamy flavour enhanced the extent to which the drink was expected to be filling, but did not affect its expected satiety. Conclusions: These results indicate that subtle manipulations of texture and creamy flavour can increase expectations that a fruit yogurt drink will be filling and suppress hunger, irrespective of the drink’s energy content. A thicker texture enhanced expectations of satiety to a greater extent than a creamier flavour, and may be one way to improve the anticipated satiating value of energy-containing beverages