Influence of pH and temperature on alunite dissolution: Rates, products and insights on mechanisms from atomistic simulation

This is the author accepted manuscript. The final version is available from Elsevier via the DOI in this recordThe processes, rates, controlling factors and products of alunite (KAl3(SO4)2(OH)6) dissolution were assessed using batch dissolution experiments at pHs of c. 3, 4, 4.6, 7 and 8, and temperatures of c. 280, 293 and 313K. Alunite dissolution is roughly congruent at pH3, while at pH≥3.9 the process is incongruent, giving a lower Al/K ratio in solution than in the pristine alunite sample. The decrease in the Al/K ratio appears to be caused by precipitation of secondary aluminium sulfate/hydroxysulfate minerals coating the surface of the dissolving alunite, as inferred from SEM images and XPS determinations, but these minerals do not passivate the alunite surface for the time frame of the experiments (up to 400h). The lowest dissolution rates are obtained for pH4.6 and 280K. Both the temperature increase and any pH variation from that point lead to faster dissolution rates. Based on the potassium release to solution, the influence of pH and temperature on the alunite dissolution rate for pH of 4.8 and below can be expressed as;. rateK= 104.4 ± 0.5aH+0.10 ± 0.02e32±3/RTwhere rateKis the alunite dissolution rate (in mol·m-2·s-1); aH+is the activity of hydrogen ions in solution; R is the Universal gas constant (in kJ·mol-1·K-1) and T is temperature (in K).For pH of 4.6 and above, the alunite dissolution rate can instead be expressed as;. rateK= 102.5±0.8aOH0.14±0.02e-39±4/RTwhere aOH-is the activity of hydroxyl ions in solution. In light of the calculated values for the activation energy under the two sets of pH conditions (32 ± 3 and 39 ± 4 kJ·mol-1), alunite dissolution appears to be surface-controlled. Examination of the most stable solvated alunite surfaces obtained by atomistic computer simulations suggests that the least energetically favourable steps during alunite dissolution are the detachment of either Al atoms or SO4tetrahedra from exposed surfaces. Thus, these processes are most probably the rate-determining steps in alunite dissolution.This work has been funded by the EC Marie Curie Intra-European Fellowship program (Project entitled ‘Reactivity of Aluminium Sulfate Minerals in Mine Wastes’; RASMIM) through a fellowship to P.A. The authors acknowledge also the NERC (National Environmental Research Council, United Kingdom) for partially funding the characterisation of mineral samples through the project ‘Characterisation of nanometre-sized aluminium sulphates: implications for mobility of aluminium from mine wastes’ (FENAC/2013/11/001)

Thermal-Error Regime in High-Accuracy Gigahertz Single-Electron Pumping

Single-electron pumps based on semiconductor quantum dots are promising candidates for the emerging quantum standard of electrical current. They can transfer discrete charges with part-per-million (ppm) precision in nanosecond time scales. Here, we employ a metal-oxide-semiconductor silicon quantum dot to experimentally demonstrate high-accuracy gigahertz single-electron pumping in the regime where the number of electrons trapped in the dot is determined by the thermal distribution in the reservoir leads. In a measurement with traceability to primary voltage and resistance standards, the averaged pump current over the quantized plateau, driven by a 1-GHz sinusoidal wave in the absence of a magnetic field, is equal to the ideal value of ef within a measurement uncertainty as low as 0.27 ppm

Detecting recent selective sweeps while controlling for mutation rate and background selection

A composite likelihood ratio test implemented in the program sweepfinder is a commonly used method for scanning a genome for recent selective sweeps. sweepfinder uses information on the spatial pattern (along the chromosome) of the site frequency spectrum around the selected locus. To avoid confounding effects of background selection and variation in the mutation process along the genome, the method is typically applied only to sites that are variable within species. However, the power to detect and localize selective sweeps can be greatly improved if invariable sites are also included in the analysis. In the spirit of a Hudson–Kreitman–Aguadé test, we suggest adding fixed differences relative to an out‐group to account for variation in mutation rate, thereby facilitating more robust and powerful analyses. We also develop a method for including background selection, modelled as a local reduction in the effective population size. Using simulations, we show that these advances lead to a gain in power while maintaining robustness to mutation rate variation. Furthermore, the new method also provides more precise localization of the causative mutation than methods using the spatial pattern of segregating sites alone.Christian D. Huber, Michael DeGiorgio, Ines Hellmann, Rasmus Nielse

Significance of herpesvirus immediate early gene expression in cellular immunity to cytomegalovirus infection

Interstitial pneumonia linked with reactivation of latent human cytomegalovirus due to iatrogenic immunosuppression can be a serious complication of bone marrow transplantation therapy of aplastic anaemia and acute leukaemia1. Cellular immunity plays a critical role in the immune surveillance of inapparent cytomegalovirus infections in man and the mouse1−7. The molecular basis of latency, however, and the interaction between latently or recurrently infected cells and the immune system of the host are poorfy understood. We have detected a so far unknown antigen in the mouse model. This antigen is found in infected cells in association with the expression of the herpesvirus 'immediate early' genes and is recognized by cytolytic T lymphocytes (CTL)8. We now demonstrate that an unexpectedly high proportion of the CTL precursors generated in vivo during acute murine cytomegalovirus infection are specific for cells that selectively synthesize immediate early proteins, indicating an immunodominant role of viral non-structural proteins

Sisyphus Cooling of Electrically Trapped Polyatomic Molecules

The rich internal structure and long-range dipole-dipole interactions establish polar molecules as unique instruments for quantum-controlled applications and fundamental investigations. Their potential fully unfolds at ultracold temperatures, where a plethora of effects is predicted in many-body physics, quantum information science, ultracold chemistry, and physics beyond the standard model. These objectives have inspired the development of a wide range of methods to produce cold molecular ensembles. However, cooling polyatomic molecules to ultracold temperatures has until now seemed intractable. Here we report on the experimental realization of opto-electrical cooling, a paradigm-changing cooling and accumulation method for polar molecules. Its key attribute is the removal of a large fraction of a molecule's kinetic energy in each step of the cooling cycle via a Sisyphus effect, allowing cooling with only few dissipative decay processes. We demonstrate its potential by reducing the temperature of about 10^6 trapped CH_3F molecules by a factor of 13.5, with the phase-space density increased by a factor of 29 or a factor of 70 discounting trap losses. In contrast to other cooling mechanisms, our scheme proceeds in a trap, cools in all three dimensions, and works for a large variety of polar molecules. With no fundamental temperature limit anticipated down to the photon-recoil temperature in the nanokelvin range, our method eliminates the primary hurdle in producing ultracold polyatomic molecules. The low temperatures, large molecule numbers and long trapping times up to 27 s will allow an interaction-dominated regime to be attained, enabling collision studies and investigation of evaporative cooling toward a BEC of polyatomic molecules

Fission yeast Pcp1 links polo kinase-mediated mitotic entry to γ-tubulin-dependent spindle formation

The centrosomal pericentrin-related proteins play pivotal roles in various aspects of cell division; however their underlying mechanisms remain largely elusive. Here we show that fission-yeast pericentrin-like Pcp1 regulates multiple functions of the spindle pole body (SPB) through recruiting two critical factors, the γ-tubulin complex (γ-TuC) and polo kinase (Plo1). We isolated two pcp1 mutants (pcp1-15 and pcp1-18) that display similar abnormal spindles, but with remarkably different molecular defects. Both mutants exhibit defective monopolar spindle microtubules that emanate from the mother SPB. However, while pcp1-15 fails to localise the γ-TuC to the mitotic SPB, pcp1-18 is specifically defective in recruiting Plo1. Consistently Pcp1 forms a complex with both γ-TuC and Plo1 in the cell. pcp1-18 is further defective in the mitotic-specific reorganisation of the nuclear envelope (NE), leading to impairment of SPB insertion into the NE. Moreover pcp1-18, but not pcp1-15, is rescued by overproducing nuclear pore components or advancing mitotic onset. The central role for Pcp1 in orchestrating these processes provides mechanistic insight into how the centrosome regulates multiple cellular pathways

Disfluency in dialogue:an intentional signal from the speaker?

Disfluency is a characteristic feature of spontaneous human speech, commonly seen as a consequence of problems with production. However, the question remains open as to why speakers are disfluent: Is it a mechanical by-product of planning difficulty, or do speakers use disfluency in dialogue to manage listeners' expectations? To address this question, we present two experiments investigating the production of disfluency in monologue and dialogue situations. Dialogue affected the linguistic choices made by participants, who aligned on referring expressions by choosing less frequent names for ambiguous images where those names had previously been mentioned. However, participants were no more disfluent in dialogue than in monologue situations, and the distribution of types of disfluency used remained constant. Our evidence rules out at least a straightforward interpretation of the view that disfluencies are an intentional signal in dialogue. © 2012 Psychonomic Society, Inc

Ultracold dense gas of deeply bound heteronuclear molecules

Recently, the quest for an ultracold and dense ensemble of polar molecules has attracted strong interest. Polar molecules have bright prospects for novel quantum gases with long-range and anisotropic interactions, for quantum information science, and for precision measurements. However, high-density clouds of ultracold polar molecules have so far not been produced. Here, we report a key step towards this goal. Starting from an ultracold dense gas of heteronuclear 40K-87Rb Feshbach molecules with typical binding energies of a few hundred kHz and a negligible dipole moment, we coherently transfer these molecules into a vibrational level of the ground-state molecular potential bound by >10 GHz. We thereby increase the binding energy and the expected dipole moment of the 40K-87Rb molecules by more than four orders of magnitude in a single transfer step. Starting with a single initial state prepared with Feshbach association, we achieve a transfer efficiency of 84%. While dipolar effects are not yet observable, the presented technique can be extended to access much more deeply bound vibrational levels and ultimately those exhibiting a significant dipole moment. The preparation of an ultracold quantum gas of polar molecules might therefore come within experimental reach.Comment: 5 pages, 5 figure