Heat capacities of aqueous sodium hydroxide/aluminate mixtures and prediction of the solubility constant of boehmite up to 300 °C

A modified commercial (Setaram C80) calorimeter has been used to measure the isobaric volumetric heat capacities of concentrated alkaline sodium aluminate solutions at ionic strengths from 1 to 6 mol kg-1, with up to 40 mol.% substitution of hydroxide by aluminate, at temperatures from 50 to 300 °C and a pressure of 10 MPa. Apparent molar heat capacities for the mixtures, Cpφ{symbol}, derived from these data were found to depend linearly on the aluminate substitution level, i.e., they followed Young's rule. These quantities were used to estimate the apparent molar heat capacities of pure, hypothetical sodium aluminate solutions, Cpφ{symbol} ('NaAl(OH)4'(aq)). Slopes of the Young's rule plots were invariant with ionic strength at a given temperature but depended linearly on temperature. The heat capacities of ternary aqueous sodium hydroxide/aluminate mixtures could therefore be modelled using only two parameters in addition to those needed for the correlation of Cpφ{symbol} (NaOH(aq)) reported previously from these laboratories. An assessment of the standard thermodynamic quantities for boehmite, gibbsite and the aluminate ion yielded a set of recommended values that, together with the present heat capacity data, accurately predicts the solubility of gibbsite and boehmite at temperatures up to 300 °C

Formation constants of copper(i) complexes with cysteine, penicillamine and glutathione: implications for copper speciation in the human eye

Protonation constants for the biologically-important thioamino acids cysteine (CSH), penicillamine (PSH) and glutathione (GSH), and the formation constants of their complexes with Cu(i), have been measured at 25 °C and an ionic strength of 1.00 mol dm-3 (Na)Cl using glass electrode potentiometry. The first successful characterisation of binary Cu(i)-CSH and Cu(i)-GSH species over the whole pH range was achieved in this study by the addition of a second thioamino acid, which prevented the precipitation that normally occurs. Appropriate combinations of binary and ternary (mixed ligand) titration data were used to optimise the speciation models and formation constants for the binary species. The results obtained differ significantly from literature data with respect to the detection and quantification of protonated and polynuclear complexes. The present results are thought to be more reliable because of the exceptionally wide pH and concentration ranges employed, the excellent reproducibility of the data, the close agreement between the calculated and observed formation functions, and the low standard deviations and absence of numerical correlation in the constants. The present formation constants were incorporated into a large Cu speciation model which was used to predict, for the first time, metal-ligand equilibria in the biofluids of the human eye. This simulation provided an explanation for the precipitation of metallic copper in lens and cornea, which is known to occur as a consequence of Wilson's disease

Investigation of complexation and solubility equilibria in the copper(I)/cyanide system at 25°C

The complexation of copper(I) by cyanide ions (CN−) in aqueous solution has been studied by glass electrode potentiometry at 25 °C and ionic strengths (I) of 1, 3 and 5 M in NaCl media. Overall formation constants, βn, for the equilibria: Cu+(aq) + nCN−(aq) ⇌ Cu(CN)n(n − 1)−(aq) with n = 2, 3 and 4, were quantified, along with the ionization constant (Kw) of water and the acid dissociation constant (Ka) of HCN(aq). The solubility constants *Ksn for the equilibria: CuCN(s) + (n − 1)HCN0(aq) ⇌ Cu(CN)n(n − 1)−(aq) + (n − 1)H+(aq) were also determined from a re-analysis of published solubility data for CuCN(s) in acidic cyanide solutions at I = 1 M(NaCl) and 25 °C. Because of the instability of uncomplexed Cu+(aq) and parameter correlations in the data, neither β1 nor the solubility product Ks0 (CuCN(s) ⇌ Cu+(aq) + CN−(aq)) could be reliably determined from the present data although estimates are presented

Understanding non-ideal paleointensity recording in igneous rocks: Insights from aging experiments on lava samples and the causes and consequences of ‘fragile’ curvature in Arai plots

The theory for recording of thermally blocked remanences predicts a quasilinear relationship between low fields like the Earth's in which rocks cool and acquire a magnetization. This serves as the foundation for estimating ancient magnetic field strengths. Addressing long-standing questions concerning Earth's magnetic field requires a global paleointensity data set, but recovering the ancient field strength is complicated because the theory only pertains to uniformly magnetized particles. A key requirement of a paleointensity experiment is that a magnetization blocked at a given temperature should be unblocked by zero-field reheating to the same temperature. However, failure of this requirement occurs frequently and the causes and consequences of failure are understood incompletely. Recent experiments demonstrate that the remanence in many samples typical of those used in paleointensity experiments is unstable, exhibiting an “aging” effect in which the (un)blocking temperature spectra can change over only a few years resulting in nonideal experimental behavior. While a fresh remanence may conform to the requirement of equality of blocking and unblocking temperatures, aged remanences may not. Blocking temperature spectra can be unstable (fragile), which precludes reproduction of the conditions under which the original magnetization was acquired. This limits our ability to acquire accurate and precise ancient magnetic field strength estimates because differences between known and estimated fields can be significant for individual specimens, with a low field bias. Fragility of unblocking temperature spectra may be related to grain sizes with lower energy barriers and may be detected by features observed in first-order reversal curves

Biologically induced mineralization of dypingite by cyanobacteria from an alkaline wetland near Atlin, British Columbia, Canada

Background: This study provides experimental evidence for biologically induced precipitation of magnesium carbonates, specifically dypingite (Mg(CO)(OH) ·5HO), by cyanobacteria from an alkaline wetland near Atlin, British Columbia. This wetland is part of a larger hydromagnesite (Mg(CO)(OH) ·4HO) playa. Abiotic and biotic processes for magnesium carbonate precipitation in this environment are compared. Results: Field observations show that evaporation of wetland water produces carbonate films of nesquehonite (MgCO ·3HO) on the water surface and crusts on exposed surfaces. In contrast, benthic microbial mats possessing filamentous cyanobacteria (Lyngbya sp.) contain platy dypingite (Mg (CO)4(OH)·5HO) and aragonite. Bulk carbonates in the benthic mats (δC avg. = 6.7%, δO avg. = 17.2%) were isotopically distinguishable from abiotically formed nesquehonite (δC avg. = 9.3%, δO avg. = 24.9%). Field and laboratory experiments, which emulated natural conditions, were conducted to provide insight into the processes for magnesium carbonate precipitation in this environment. Field microcosm experiments included an abiotic control and two microbial systems, one containing ambient wetland water and one amended with nutrients to simulate eutrophic conditions. The abiotic control developed an extensive crust of nesquehonite on its bottom surface during which [Mg] decreased by 16.7% relative to the starting concentration. In the microbial systems, precipitation occurred within the mats and was not simply due to the capturing of mineral grains settling out of the water column. Magnesium concentrations decreased by 22.2% and 38.7% in the microbial systems, respectively. Laboratory experiments using natural waters from the Atlin site produced rosettes and flakey globular aggregates of dypingite precipitated in association with filamentous cyanobacteria dominated biofilms cultured from the site, whereas the abiotic control again precipitated nesquehonite. Conclusion: Microbial mats in the Atlin wetland create ideal conditions for biologically induced precipitation of dypingite and have presumably played a significant role in the development of this natural Mg-carbonate playa. This biogeochemical process represents an important link between the biosphere and the inorganic carbon pool

HPK1 Associates with SKAP-HOM to Negatively Regulate Rap1-Mediated B-Lymphocyte Adhesion

BACKGROUND: Hematopoietic progenitor kinase 1 (HPK1) is a Ste20-related serine/threonine kinase activated by a range of environmental stimuli including genotoxic stress, growth factors, inflammatory cytokines and antigen receptor triggering. Being inducibly recruited to membrane-proximal signalling scaffolds to regulate NFAT, AP-1 and NFkappaB-mediated gene transcription in T-cells, the function of HPK1 in B-cells to date remains rather ill-defined. METHODOLOGY/PRINCIPAL FINDINGS: By using two loss of function models, we show that HPK1 displays a novel function in regulating B-cell integrin activity. Wehi 231 lymphoma cells lacking HPK1 after shRNA mediated knockdown exhibit increased basic activation levels of Ras-related protein 1 (Rap1), accompanied by a severe lymphocyte function-associated antigen-1 (LFA-1) dependent homotypic aggregation and increased adhesion to intercellular adhesion molecule 1 (ICAM-1). The observed phenotype of enhanced integrin activity is caused downstream of Src, by a signalling module independent of PI3K and PLC, involving HPK1, SKAP55 homologue (SKAP-HOM) and Rap1-GTP-interacting adaptor molecule (RIAM). This alters actin dynamics and renders focal adhesion kinase (FAK) constitutively phosphorylated. Bone marrow and splenic B-cell development of HPK1(-/-) mice are largely unaffected, except age-related tendencies for increased splenic cellularity and BCR downregulation. In addition, naïve splenic knockout B-cells appear hyperresponsive to a range of stimuli applied ex vivo as recently demonstrated by others for T-cells. CONCLUSIONS/SIGNIFICANCE: We therefore conclude that HPK1 exhibits a dual function in B-cells by negatively regulating integrin activity and controlling cellular activation, which makes it an interesting candidate to study in pathological settings like autoimmunity and cancer

Thermodynamic modeling of crystal deposition in humans

The prevention and treatment of crystal deposition in the human body are based on the understanding of the physicochemical properties underlying the precipitation of the substances involved. Among these properties, the solubilities of the crystals are very important. Recently, experimentally determined solubility data of substances related to urolithiasis, such as calcium oxalate hydrates, uric acid and urates, cystine, and xanthine, were critically assessed. Unfortunately, reported solubilities of these substances were found to be either scarce or in large disagreement. Consequently, detailed studies were carried out in our laboratory, and the results will be discussed in this communication with emphasis on the thermodynamic consistency of the experimentally determined data. Since proper modeling of the solubilities of these substances in artificial urine solutions serves as a prerequisite for solubility predictions in real urine, the Joint Expert Speciation System (JESS) software package was employed to create a comprehensive computer model including the relevant, low-molecular inorganic and organic components of urine. The results of the simulations lead to some useful suggestions regarding the prevention and treatment of stone disease

The boehmite ‘solubility gap’

Boehmite, rather than gibbsite, precipitation has been proposed in the literature as a potential energy-saving modification of the Bayer process for the production of alumina. Previous experimental studies have reported that true equilibrium solubilities were not attained during boehmite precipitation. Instead, a pseudo-equilibrium or an apparent 'steady-state' aluminate concentration of about twice the boehmite solubility was reached. In this work, the dissolution and precipitation reactions in synthetic and plant liquors using seeds of (i) pure boehmite and (ii) various boehmite/gibbsite ratios were investigated at 95 °C. Only boehmite precipitation was observed on pure boehmite seed at relatively low supersaturation (alumina (A)/total caustic (TC) 0.56). The aluminate concentrations measured as a function of time decreased continuously and did not exhibit an apparent 'steady state'. Stable equilibrium, as established by boehmite solubility measurements, was approached very slowly but not attained even after ten weeks. At higher supersaturation (A/TC 0.67), after an initial desupersaturation, 'steady-state' aluminate concentrations of about twice the boehmite solubility were observed. There is convincing evidence that these 'steady states' correspond to metastable solubility equilibria with gibbsite, which is precipitated initially and gradually transforms into the stable phase, boehmite. Gibbsite also nucleated in the case of pure boehmite seeds. 'Steady states' were attained in one up to several days and remained constant for one to ten days. The length of these periods correlated with the gibbsite content of the seeds. After sufficient recrystallisation of gibbsite to boehmite, the aluminate concentrations decreased significantly and eventually approached boehmite solubility, thereby following a much slower precipitation kinetics typical for boehmite. Due to short observation times, previous workers did not detect the end of the 'steady-state' periods and therefore failed to identify the observed 'steady-state' aluminate concentrations as arising from metastable solubility equilibria with gibbsite

Solubility equilibria. From data optimization to process simulation

Models that accurately predict solid–solute phase equilibria in aqueous electrolyte solutions are of mounting importance for numerous industrial processes, especially those operating at high temperatures, pressures, and concentrations. The incorporation of such electrolyte models into process simulators is in great demand. This communication will focus on thermodynamically consistent models that can simultaneously predict densities, heat capacities, and apparent molar enthalpies of multicomponent electrolyte mixtures together with activities of their constituents. Data optimization issues to be discussed include the CALPHAD (CALculation of PHAse Diagrams) method applied to electrolyte systems and the generation of robust models that extrapolate well outside the parameterization space. Recent development of software suitable for the simulation of industrial processes involving concentrated electrolyte solutions will be outlined