Pedological trends and implications for forest productivity in a Holocene soil chronosequence, Calvert Island, British Columbia, Canada.

Chronosequence studies of soil formation and ecosystem development provide important insights into the pathways and rates of change occurring on centennial and millennial time scales. In cool or temperate humid environments, Podzols are the predominant soil type formed under coniferous forests in coarse-textured parent material and have been a major focus of chronosequence studies. This study examined the rate and mechanisms of Podzol development and related forest productivity in a sand dune chronosequence in a hypermaritime climate in coastal British Columbia (BC). The sequence spans 10,760 ± 864 years over eight sites and is the first documented chronosequence in coastal BC to span most of the Holocene Epoch. Soil samples from each genetic horizon were analyzed for bulk density, pH and concentrations of total carbon (C), pyrophosphate- and oxalate-extractable aluminum (Al) and iron (Fe), and total elements. Within ~3,500 years a mature Podzol had formed, with cemented horizons (ortstein and placic) present. Organo-metallic complexation appeared to be the dominant mechanism involved in podzolization . Despite a mild, moist climate conducive to chemical weathering, all soils had similarly low values for the Chemical Index of Alteration, suggesting that congruent dissolution of primary minerals may be occurring. Ecosystem retrogression is apparent in the latter stages of the chronosequence – a phenomenon not previously documented in coastal BC. Further research is needed to examine the interactions of nutrient limitation, soil physical barriers, and other possible drivers of ecosystem retrogression.

Numerical Phase-Field Model Validation for Dissolution of Minerals

Modelling of a mineral dissolution front propagation is of interest in a wide range of scientific and engineering fields. The dissolution of minerals often involves complex physico-chemical processes at the solid–liquid interface (at nano-scale), which at the micro-to-meso-scale can be simplified to the problem of continuously moving boundaries. In this work, we studied the diffusion-controlled congruent dissolution of minerals from a meso-scale phase transition perspective. The dynamic evolution of the solid–liquid interface, during the dissolution process, is numerically simulated by employing the Finite Element Method (FEM) and using the phase–field (PF) approach, the latter implemented in the open-source Multiphysics Object Oriented Simulation Environment (MOOSE). The parameterization of the PF numerical approach is discussed in detail and validated against the experimental results for a congruent dissolution case of NaCl (taken from literature) as well as on analytical models for simple geometries. In addition, the effect of the shape of a dissolving mineral particle was analysed, thus demonstrating that the PF approach is suitable for simulating the mesoscopic morphological evolution of arbitrary geometries. Finally, the comparison of the PF method with experimental results demonstrated the importance of the dissolution rate mechanisms, which can be controlled by the interface reaction rate or by the diffusive transport mechanism.

Discontinuous Geochemical Monitoring of the Galleria Italia Circumneutral Waters (Former Hg-Mining Area of Abbadia San Salvatore, Tuscany, Central Italy) Feeding the Fosso Della Chiusa Creek

The Galleria Italia waters drain the complex tunnel system of the former Hg-mining area of Abbadia San Salvatore (Tuscany, central Italia) and feed the 2.5 km-long Fosso della Chiusa creek. The mining exploitation was active for more than one century and more than 100,000 tons of liquid mercury were produced by roasting processes of cinnabar (HgS). In this work, a discontinuous geochemical monitoring of the Galleria Italia circumneutral waters was carried out from February 2009 to October 2020, during which the main physicochemical parameters, main and minor dissolved species and trace elements (including Hg) were determined. In the observation period, significant variations in the water chemistry were recorded, particularly when flooding waves, due to intense precipitations, occurred, with the two main events being recorded in February 2009 and January 2010. The chemical composition of the Galleria Italia waters was Ca(Mg)-SO4 and related to congruent dissolution of gypsum/anhydrite at which a contribution from carbonatic and silicatic minerals and partial solubilization of CO2 and and H2S oxidation is to be added. Regarding the trace elements, Al, Mn and Fe were up to 1500, 768 and 39520 μg L−1, with these elements also showing high contents in the sediment precipitating by the Galleria Italia waters. In most cases, dissolved mercury was below the instrumental detection limit (<0.1 μg L−1), although occasionally it reached >1 μg L−1. Considering a mean flow rate of 40 L s−1 of the discharged water, the amount of dissolved mercury released from Galleria Italia was computed, although most mercury was occurring in the sediment (1.2 mg kg−1). A more realistic computation of mercury released from Galleria Italia should involve a sampling network along the Fosso della Chiusa before entering the riverine system of the Tiber basin, into which dissolved and suspended mercury are to be determined along with that occurring in the sediments.

Investigation of the solid–liquid ternary phase diagrams of 2HNIW·HMX cocrystal

The ternary phase diagrams of 2HNIW·HMX cocrystal system in ethyl acetate at 15 °C. In the HMX–HNIW–ethyl acetate system, HMX and HNIW showed congruent dissolution behavior, and the cocrystal exhibits a wider thermodynamically stable region.

Magnesium Leachability of Mg-Silicate Peridotites: The Effect on Magnesite Yield of a Mineral Carbonation Process

The aim of this study was to increase feedstock availability for mineral carbonation. Acid dissolution and carbonic acid dissolution approaches were used to achieve higher Mg extractions from peridotites. Acid dissolution studies of raw dunite, heat-activated dunite, heat-transformed dunite, and twin sister dunite have not been reported in the literature. Heat-activated dunite is more reactive as compared to heat-transformed dunite, raw dunite, and twin sister dunite. The fraction of magnesium extracted from heat-activated dunite was 57% as compared to 18% from heat-transformed dunite, 14% from raw dunite, and 11% from twin sister dunite. Similarly, silicon and iron extractions were higher for heat-activated dunite compared to that of heat-transformed dunite, raw dunite, and twin sister dunite. Materials rich in forsterite (twin sister dunite and heat-transformed dunite) showed preferential Mg release and exhibited incongruent dissolution similar to that of forsterite. Heat-activated dunite (amorphous magnesium silicate rich) on the other hand behaved differently and showed congruent dissolution. Olivine did not dissolve under carbonic acid dissolution (with concurrent grinding) and acidic conditions. Under carbonic acid dissolution with concurrent grinding conditions, olivine was partially converted into nanometer sized particles (d10 = 0.08 µm) but still provided 16% Mg extraction during 4 h of dissolution.

Reactivity of Metakaolin in Alkaline Environment: Correlation of Results from Dissolution Experiments with XRD Quantifications

Systematic investigation of filtrates and filter residues resulting from a 24 h treatment of metakaolin in different alkaline solutions were performed. On filtered metakaolin particles, inductively coupled plasma-optical emission spectrometry (ICP-OES) measurements reveal an enrichment of iron and titanium, which suggests an inhomogeneous distribution of these cations. Since the SiO2/Al2O3 ratio remains constant in all filter residues examined, the dissolution of the Si and Al monomers is congruent. Structural differences, identified by attenuated total reflection–Fourier transform infrared spectroscopy (ATR-FTIR) as a consequence of alkali uptake, influence the X-ray scattering contribution of metakaolin, and thus quantifications with the partial or no known crystal structure (PONKCS) method. This leads to deviations between the degree of reaction calculated from Si and Al solubility from filtrate and that quantified by quantitative powder X-ray diffraction (QPXRD) using the filter residue. Nevertheless, the described changes do not cause a shift in the X-ray amorphous hump in case of congruent dissolution, and thus allow the quantification of the metakaolin before and after dissolution with the same hkl-phase model.

Diffusive processes in aqueous glass dissolution

High level nuclear waste is often immobilised in a borosilicate glass for disposal. However, this glass corrodes in contact with aqueous solutions. To predict radionuclide releases from wasteforms, their dissolution mechanisms must be understood. Understanding glass dissolution mechanisms presents a challenge across numerous other disciplines and many glass dissolution models still remain conflicted. Here we show that diffusion was a significant process during the later stages of dissolution of a simplified waste glass but was not evidenced during the initial stages of dissolution. The absence of measurable isotopic fractionation in solution initially supports models of congruent dissolution. However, the solution becoming isotopically lighter at later times evidences diffusive isotopic fractionation and opposes models that exclude diffusive transport as a significant mechanism. The periodically sampled isotopic methodologies outlined here provide an additional dimension with which to understand glass dissolution mechanisms beyond the usual measurement of solution concentrations and, post-process, nano-scale analysis of the altered glass.

Calcium silicate hydrate (C-S-H) gel dissolution and pH buffering in a cementitious near field

A cementitious backfill has been proposed in many geological disposal concepts for intermediate-level waste and low-level waste in the UK and elsewhere. In this paper, the main features of the chemical evolution of backfill and the associated changes in the near-field pH are illustrated with results from recent work. For example, interaction of the groundwater with calcium silicate hydrate (C-S-H) phases in a backfill is expected to play an important role in the long-term pH-buffering behaviour. Existing experimental data for the dissolution of C-S-H gels are compared with recent experimental results from leach tests on gels of a lower calcium to silicon ratio (C/S) to provide a consistent set of data across the full C/S range. The results confirm that a congruent dissolution point around C/S = 0.8 is approached by leaching from below (i.e. for gels with 0.29 < C/S < 0.8), as well as from above, as reported elsewhere. In addition, a spreadsheet model has been developed to calculate the volume of backfill required at the vault scale to meet specified pH performance criteria. This model includes the major reactions of the backfill with the groundwater, waste encapsulants and waste components. It can also consider the effects of specific waste packages on local pH performance to allow comparison with the vault-scale calculations.