Interaction of Freshly Precipitated Silica Gel with Aqueous Silicic Acid Solutions under Ambient and Near Neutral pH-conditions: A Detailed Analysis of Linear Rate Law

Interaction of freshly precipitated silica gel with aqueous solutions was studied at laboratory batch experiments under ambient and near neutral pH-conditions. The overall process showed excellent reversibility: gel growth could be considered as an opposite process to dissolution and a linear rate law could be applied to experimental data. Depending on the used rate law form, the resulting rate constants were sensitive to errors in parameters/variables such as gel surface area, equilibrium constants, Si-fluxes, and reaction quotients. The application of an Integrated Exponential Model appeared to be the best approach for dissolution data evaluation. It yielded the rate constants k _dissol ∼ (4.50 ± 0.68) × 10⁻¹² and k _growth ∼ (2.58 ± 0.39) × 10⁻⁹ mol m⁻² s⁻¹ for zero ionic strength. In contrast, a Differential Model gave best results for growth data modeling. It yielded the rate constants k _dissol ∼ (1.14 ± 0.44) × 10⁻¹¹ and k _growth ∼ (6.08 ± 2.37) × 10⁻⁹ mol m⁻² s⁻¹ for higher ionic strength (I ∼ 0.04 to 0.11 mol L⁻¹). The found silica gel solubility at zero ionic strength was somewhat lower than the generally accepted value. Based on the and standard Gibbs free energy of silica gel formation was calculated as and −850,318 ± 20 J mol⁻¹, respectively. Activation energies for silica gel dissolution and growth were determined as and respectively. An universal value for growth of any silica polymorph, is not consistent with the value for silica gel growth, which questions the hypothesis about one unique activated complex controlling the silica polymorph growth.     

Abiotic ammonium formation in the presence of Ni-Fe metals and alloys and its implications for the Hadean nitrogen cycle

Experiments with dinitrogen-, nitrite-, nitrate-containing solutions were conducted without headspace in Ti reactors (200°C), borosilicate septum bottles (70°C) and HDPE tubes (22°C) in the presence of Fe and Ni metal, awaruite (Ni₈₀Fe₂₀) and tetrataenite (Ni₅₀Fe₅₀). In general, metals used in this investigation were more reactive than alloys toward all investigated nitrogen species. Nitrite and nitrate were converted to ammonium more rapidly than dinitrogen, and the reduction process had a strong temperature dependence. We concluded from our experimental observations that Hadean submarine hydrothermal systems could have supplied significant quantities of ammonium for reactions that are generally associated with prebiotic synthesis, especially in localized environments. Several natural meteorites (octahedrites) were found to contain up to 22 ppm N_tot. While the oxidation state of N in the octahedrites was not determined, XPS analysis of metals and alloys used in the study shows that N is likely present as nitride (N^3-). This observation may have implications toward the Hadean environment, since, terrestrial (e.g., oceanic) ammonium production may have been supplemented by reduced nitrogen delivered by metal-rich meteorites. This notion is based on the fact that nitrogen dissolves into metallic melts.     

Consumer Diversity Enhances Secondary Production by Complementarity Effects in Experimental Ciliate Assemblages

Diversity within distinct trophic groups is proposed to increase ecosystem functions such as the productivity of this group and the efficiency of resource use. This proposition has mainly been tested with plant communities, consumer assemblages, and multitrophic microbial assemblages. Very few studies tested how this diversity–productivity relationship varies under different environmental regimes such as disturbances. Coastal benthic assemblages are strongly affected by temporal instability of abiotic conditions. Therefore, we manipulated benthic ciliate species richness in three laboratory experiments with three diversity levels each and analyzed biomass production over time in the presence or absence of a single application of a disturbance (ultraviolet-B [UVB] radiation). In two out of three experiments, a clear positive relationship between diversity and productivity was found, and also the remaining experiment showed a small but nonsignificant effect of diversity. Disturbance significantly reduced the total ciliate biomass, but did not alter the relation between species richness and biomass production. Significant overyielding (i.e., higher production at high diversity) was observed, and additive partitioning indicated that this was caused by niche complementarity between ciliate species. Species-specific contribution to the total biomass varied idiosyncratically with species richness, disturbance, and composition of the community. We thus present evidence for a significant effect of consumer diversity on consumer biomass in a coastal ciliate assemblage, which remained consistent at different disturbance regimes.     

The Early-Middle Pleistocene Transition： characterization and proposed guide for the defining boundary

The mid-Pleistocene transition （MPT, c. 1.2 to 0.5 Ma） records fundamental changes in Earth＇s climate state, where low-amplitude 41-kyr obliquity-dominated cycles gave way progressively to the high-amplitude, quasiperiodic （c. 100-kyr） fluctuations that characterize the later Pleistocene and Holocene. We use wavelet analysis on the LR04 δ^l8O benthic foraminiferal stack to confirm low-frequency power as early as 1.25-1.20 Ma, determine the persistence of obliquity-dominated cyclicity through and beyond the MPT, and reveal new levels of complexity in climate evolution.     

Self-diffusion of water and its dependence on temperature and ionic strength in highly compacted montmorillonite, illite and kaolinite

The effect of temperature and ionic strength on the diffusion of HTO parallel to the direction of compaction through 5 highly compacted clay minerals (bulk dry density, ρ_b,d = 1.90 ± 0.05 Mg/m³), namely montmorillonite (Na- and Ca-form), illite (Na- and Ca-form), and kaolinite, was studied. The diffusion experiments were carried out at temperatures between 0 °C and 60 °C and at ionic strengths of 0.01 M and 1 M NaCl for the Na-form clays and kaolinite, and of 0.005 M and 0.5 M CaCl₂ for the Ca-form. The ionic strength had an insignificant influence on the values of the effective diffusion coefficient (variation by less than 10%) for the clays under study at this degree of compaction. The effective diffusion coefficients followed the order Na-montmorillonite < Ca-montmorillonite < Ca-illite < Na-illite  kaolinite. It is thought that the differences between Na- and Ca-montmorillonite originate from the larger size particles, and thus the lower tortuosity of the latter; whereas the differences between Na- and Ca-illite are related to the different degree of solvation of the Na and Ca cations. The activation energies were successfully calculated using the Arrhenius law. Swelling clays (Na- and Ca-montmorillonite) had slightly larger activation energy values (20 kJ/mol) compared to bulk water (17 kJ/mol); Ca-illite (16 kJ/mol), Na-illite (13 kJ/mol) and kaolinite (14.4 kJ/mol) lower values than that of bulk water. The low activation energies of the last three clays may be related to weaker H-bonds between water and the clay surfaces compared to those in bulk water.     

The effect of organics on lead sorption onto Apatite II™

Training activities at firing ranges, both civilian and military, deliver large quantities of Pb bullets into range soils where the physical and geochemical properties of the soil can influence Pb transport. Some best management practices (BMPs) developed for range managers include the addition of phosphate amendments, such as apatite, to immobilize Pb and other metals associated with firing ranges. In this study, the effect of the organic matter content of apatite II™ on its metal sorption properties was investigated. Batch and column experiments were conducted using mechanically, enzymatically, and thermally-treated forms of Apatite II™ to sorb soluble Pb. In batch experiments, mechanically and enzymatically-treated Apatite II™ reduced soluble Pb concentrations from 29% to 96%, depending on the age of the Apatite source. Thermally-treated Apatite II™ consistently reduced soluble Pb concentrations in solution by more than 90%, regardless of aging. The mechanically and enzymatically-treated Apatite II™ produced significantly higher dissolved organic carbon (DOC) and biochemical oxygen demand (BOD) concentrations while undergoing aging. This contrasts with the thermally-treated Apatite II™ that produced very low to non-detectable levels of DOC and BOD while aging. To determine the effects of thermal treatment on performance efficiencies, studies were performed using 500 mg L⁻¹ Pb solutions in columns packed with Apatite II™ that had been preheated at various temperatures for 2 h. The column study showed Pb loading of the Apatite II™ at different thermal treatments that ranged from 10.5% to 16.8% Pb by weight of substrate. The Pb loading capacity (by weight of substrate) increased as the treatment temperature of the Apatite II™ increased.     

Testing the durability of limestone for Cathedral façade restoration

This research aimed to specify an optimum replacement stone for Truro Cathedral. A variety of petrographically and visually similar material to the original Bath stone was initially selected. The stones were subjected to three different durability tests; Sodium sulphate crystallisation and large scale testing with both accelerated and climatic freeze-thaw cyclic loading. The most suitable stone was determined as the one with the best performance characteristics overall.     

Mafic and Felsic Magma Interaction in Granites: the Hercynian Karkonosze Pluton (Sudetes, Bohemian Massif)

The Hercynian, post-collisional Karkonosze pluton contains severallithologies: equigranular and porphyritic granites, hybrid quartzdiorites and granodiorites, microgranular magmatic enclaves,and composite and lamprophyre dykes. Field relationships, mineralogyand major- and trace-element geochemistry show that: (1) theequigranular granite is differentiated and evolved by smalldegrees of fractional crystallization and that it is free ofcontamination by mafic magma; (2) all other components are affectedby mixing. The end-members of the mixing process were a porphyriticgranite and a mafic lamprophyre. The degree of mixing variedwidely depending on both place and time. All of the processesinvolved are assessed quantitatively with the following conclusions.Most of the pluton was affected by mixing, implying that hugevolumes (>75 km³) of mafic magma were available. This maficmagma probably supplied the additional heat necessary to initiatecrustal melting; part of this heat could have also been releasedas latent heat of crystallization. Only a very small part ofthe Karkonosze granite escaped interaction with mafic magma,specifically the equigranular granite and a subordinate partof the porphyritic granite. Minerals from these facies are compositionallyhomogeneous and/or normally zoned, which, together with geochemicalmodelling, indicates that they evolved by small degrees of fractionalcrystallization (<20%). Accessory minerals played an importantrole during magmatic differentiation and, thus, the fractionalcrystallization history is better recorded by trace rather thanby major elements. The interactions between mafic and felsicmagmas reflect their viscosity contrast. With increasing viscositycontrast, the magmatic relationships change from homogeneous,hybrid quartz diorites–granodiorites, to rounded magmaticenclaves, to composite dykes and finally to dykes with chilledmargins. These relationships indicate that injection of maficmagma into the granite took place over the whole crystallizationhistory. Consequently, a long-lived mafic source coexisted togetherwith the granite magma. Mafic magmas were derived either directlyfrom the mantle or via one or more crustal storage reservoirs.Compatible element abundances (e.g. Ni) show that the maficmagmas that interacted with the granite were progressively poorerin Ni in the order hybrid quartz diorites—granodiorites—enclaves—compositedykes. This indicates that the felsic and mafic magmas evolvedindependently, which, in the case of the Karkonosze granite,favours a deep-seated magma chamber rather than a continuousflux from mantle. Two magma sources (mantle and crust) coexisted,and melted almost contemporaneously; the two reservoirs evolvedindependently by fractional crystallization. However, maficmagma was continuously being intruded into the crystallizinggranite, with more or less complete mixing. Several lines ofevidence (e.g. magmatic flux structures, incorporation of granitefeldspars into mafic magma, feldspar zoning with fluctuatingtrace element patterns reflecting rapid changes in magma composition)indicate that, during its emplacement and crystallization, thegranite body was affected by strong internal movements. Thesewould favour more complete and efficient mixing. The systematicspatial–temporal association of lamprophyres with crustalmagmas is interpreted as indicating that their mantle sourceis a fertile peridotite, possibly enriched (metasomatized) byearlier subduction processes. KEY WORDS: Bohemian Massif; fractional crystallization; geochemical modelling; hybridization; Karkonosze     

The structure of the lower crust at the Argentine continental margin, South Atlantic at 44°S

It is well established that the Argentine passive margin is of the rifted volcanic margin type. This classification is based primarily on the presence of a buried volcanic wedge beneath the continental slope, manifested by seismic data as a seaward dipping reflector sequence (SDRS). Here, we investigate the deep structure of the Argentine volcanic margin at 44°S over 200 km from the shelf to the deep oceanic Argentine Basin. We use wide-angle reflection/refraction seismic data to perform a joint travel time inversion for refracted and reflected travel times. The resulting P-wave velocity-depth model confirms the typical volcanic margin structure. An underplated body is resolved as distinctive high seismic velocity (v_p up to 7.5 km/s) feature in the lower crust in the prolongation of a seaward dipping reflector sequence. A remarkable result is that a second, isolated body of high seismic velocity (v_p up to 7.3 km/s) exists landward of the first high-velocity feature. The centres of both bodies are 60 km apart. The high-velocity lower-crustal bodies likely were emplaced during transient magmatic–volcanic events accompanying the late rifting and initial drifting stages. The lateral variability of the lower crust may be an expression of a multiple rifting process in the sense that the South Atlantic rift evolved by instantaneous breakup of longer continental margin segments. These segments are confined by transfer zones that acted as rift propagation barriers. A lower-crustal reflector was detected at 3 to 5 km above the modern Moho and probably represents the lower boundary of stretched continental crust. With this finding we suggest that the continent–ocean boundary is situated 70 km more seaward than in previous interpretations.