Characterization of locally available soil as a liner material for solid waste landfills in Sri Lanka

This study aimed to develop a low-cost and effective clay liner material for solid waste landfills in Sri Lanka. A locally available clayey soil and its admixtures with 5 and 10% bentonite were examined for this purpose. Laboratory experiments to determine soil plasticity and swell index were carried out on the tested samples. Hydraulic conductivity (k) tests were carried out in the laboratory using water and an aqueous solution of CaCl₂ on unconsolidated samples prepared by either dry or slurry packing and pre-consolidated samples with five different consolidation pressures (p) from 10 to 200 kPa. Measured liquid limits for tested admixtures increased with increasing bentonite contents and correlated well with measured values of the swell index. The difference in permeant solutions had little effect on measured k values for both unconsolidated and pre-consolidated samples. The hydraulic conductivities were highly affected by changing p, i.e., the k values decreased on two orders of magnitude as p increased from 10 to 200 kPa. The Kozeny–Carman equation, a theoretical permeability model that expresses the k-porosity relationship, was applied to measured data including reported values. Results showed the Kozeny–Carman equation captured well the porosity-dependent k values for tested soils and their admixtures with bentonite under a wide range of void ratios, suggesting that the Kozeny–Carman equation is a useful tool to estimate the magnitude of k values for differently compacted soil and its bentonite admixtures.     

Fracture evolution and energy mechanism of deep-buried carbonaceous slate

In order to study the influence of confining pressure and water content on the mechanical properties, fracture evolution and energy damage mechanism of deep-buried carbonaceous slate, uniaxial and triaxial compression tests were carried out under natural and saturated states and acoustic emission monitored. The deep-buried carbonaceous slate samples were obtained at a depth of 1020 m from the Lanjiayan tunnel in Sichuan province, China, where the maximum in situ stress has been measured at 44.2 MPa. The results suggest that water has a significant softening effect on the strength and deformation characteristics of carbonaceous slate, but the effect decreases with an increase in the confining pressure. When both the confining pressure and water content are increased, the acoustic emission events and dissipated energy gradually increase at the pre-peak and post-peak stages. Thus, the AE evolution type seen in the natural state under low confining pressure usually presents as a main shock-type event, and it changes to a foreshock–main shock–after shock event when saturated and at high confining pressures. Based on the S-shaped energy evolution law, the damage evolution process of carbonaceous slate was analyzed. The damage stress thresholds σ _ea and σ _eb were obtained, which can be considered as the thresholds of the rock entering the energy-hardening and energy-softening stages. Finally, a new brittleness energy index BDE is proposed to describe the influence of confining pressure and water content on the damage mechanism of deep-buried carbonaceous slate.     

Dewatering Behaviour of a Uranium Ore Slurry Containing Clays

The main objective of this paper was to investigate the dewatering behaviour of a clayey uranium ore slurry. The slurry (containing 28% clay size) exhibited moderate water adsorption (w _l  = 83% and w _p  = 30%). Primarily composed of muscovite (46%) and quartz (30%), the clay minerals included illite (8%), chlorite (5%) and kaolinite (2%) alongside a CEC of 41 (cmol(+)/kg) with Ca²⁺ and Mg²⁺ as the dominant cations. Likewise, the high EC (17,600 μS/cm) and ionic strength (1.15 mol/L) indicated a flocculated microstructure due to the presence of SO₄ ^2? (22,600 mg/L) and Mg²⁺ (1340 mg/L) in the slurry water. Settling included sedimentation and consolidation at low initial solids condition (25–35%) whereas only consolidation was observed at high initial solids contents (40–50%). The average k reduced from 1.2 × 10^?6 m/s (initial s = 25%) to 5.3 × 10^?8 m/s (initial s = 50%) along with a void ratio reduction from 7.4 to 2.6. Due to thixotropic strength, volume compressibility during consolidation showed apparent pre-consolidation at low effective stress (0.3–2 kPa) with a reduction in void ratio from 2.6 to 2.5. The e _s was found to be 2.46 at σ′ = 2 kPa and was followed by a steeper slope with the void ratio reducing to 2.1 at σ′ = 31 kPa. Likewise, the hydraulic conductivity during consolidation decreased from 2.6 × 10^?9 m/s (at e = 2.6) to 2.0 × 10^?10 m/s (at e = 2.1).     

Effect of 2-D Random Field Discretization on Failure Probability and Failure Mechanism in Probabilistic Slope Stability

This paper investigates, using the random field theory and Monte Carlo simulation, the effects of random field discretization on failure probability, p _f, and failure mechanism of cohesive soil slope stability. The spatial sizes of the discretized elements in random field Δx, Δy in horizontal and vertical directions, respectively, are assigned a series of combinational values in order to model the discretization accuracy. The p _f of deterministic critical slip surface (DCSS) and that of the slope system both are analyzed. The numerical simulation results have demonstrated that both the ratios of Δy/λ _y (λ _y  = scale of fluctuation in vertical direction) and Δx/λ _x (λ _x  = scale of fluctuation in horizontal direction) contribute in a similar manner to the accuracy of p _f of DCSS. The effect of random field discretization on the p _f can be negligible if both the ratios of Δx/λ _x and Δy/λ _y are no greater than 0.1. The normalized discrepancy tends to increase at a linear rate with Δy/λ _y when Δx/λ _x is larger than 0.1, and vice versa for p _f of DCSS. The random field discretization tends to have more considerable influence on the p _f of DCSS than on that of the slope system. The variation of p _f versus λ _x and λ _y may exhibit opposite trends for the cases where the limit state functions of slope failure are defined on DCSS and on the slope system as well. Finally, the p _f of slope system converges in a more rapid manner to that of DCSS than the failure mechanism does to DCSS as the spatial variability of soil property grows from significant to negligible.     

Detailed comparison of nine intact rock failure criteria using polyaxial intact coal strength data obtained through PFC<Superscript>3D</Superscript> simulations

Study of intact rock failure criteria is an important topic in rock mechanics. In this study, applicability of nine different intact rock failure criteria is investigated for intact coal strength data. PFC^3D modeling was used to simulate the laboratory polyaxial tests for cubic intact coal blocks of side dimension 110 mm under different confining stress combinations. A modified grid search procedure is proposed and used to find the best-fitting parameter values and to calculate the coefficient of determination (R ²) values for each criterion. Detailed comparisons of the nine criteria are made using the following aspects: R ² values, σ ₁ ? σ ₂ plots for different σ ₃, shapes on the deviatoric plane, linearity or nonlinearity on the meridian planes. Through the comparisons of R ² values, σ ₁ ? σ ₂ plots and meridian lines, the modified Wiebols–Cook and modified Lade criteria were found to fit the intact coal strength data best. The nine failure criteria are categorized into three types based on the appearances on the deviatoric plane.     

DEM simulations of sandstone under true triaxial compressive tests

Numerically simulated true triaxial compression tests (σ ₁ ≥ σ ₂ ≥ σ ₃) are conducted in this study to elucidate the failure mechanism of sandstone using 3D discrete element method (DEM), in particular the effect of the intermediate principal stress (σ ₂). Eight series of tests (σ ₃ = 0, 10, 20, 30, 40, 50, 70, and 100 MPa) are conducted. Within each series, σ ₂ is varied from σ ₂ = σ ₃ to σ ₂ = σ ₁ from test to test. For each test, σ ₁ is raised monotonically to failure while keeping σ ₂ and σ ₃ constant. The DEM simulations reveal the effect of σ ₂ on the variations of peak stress, Young’s modulus, failure plane angles, the brittle–ductile transition, and the evolution of failure modes, the effect beyond the well-understood effect of σ ₃. The simulation is in qualitative agreement with the results obtained experimentally. Detailed analyses performed on the particle-scale responses further the understanding of the microscopic mechanisms. The distribution of contact force becomes more homogeneous with the increase of σ ₃, which leads to the resulting damage being more localized rather than diffused. The interaction between contact force distribution and coalescence of cracks determines the processes and patterns of fracturing in the sample scale. σ ₂ is found to affect the microscopic stress distribution as well as structure evolution, and this effect weakens with the increase of σ ₃.     

Orthogonal test and regression analysis of the strain on silty soil in Shanghai under metro loading

Cyclic triaxial test by means of the geotechnical digital system is conducted for the soil near the Guoquan Road Station of Metro Line 10 in Shanghai to analyze the strain characteristics and the variation law of saturated silty soil under subway loading. Orthogonal design method is used to arrange the experiment, considering the following factors: frequency ratio f _R, cyclic stress ratio σ _R, vibration time ratio N _R, and the interaction function among them. Results show that the cyclic stress ratio σ _R, the frequency ratio f _R, the vibration time ratio N _R, and the interaction between the cyclic stress ratio σ _R and the vibration time ratio N _R have a significant effect on the axial strain of the subway tunnel. The effect of the interaction between the cyclic stress ratio σ _R and the vibration time ratio N _R is also significant. From the analysis of variance and regression theory, the nonlinear regression equation of the cumulative plastic strain of silty soil under subway loading is established. Residual analysis proves that the equation is ideal and credible. The results have important value for the design of subway tunnels.     

Rogue events in spatiotemporal numerical simulations of unidirectional waves in basins of different depth

The evolution of unidirectional nonlinear sea surface waves is calculated numerically by means of solution of the Euler equations. The wave dynamics corresponds to quasi-equilibrium states characterized by JONSWAP spectra. The spatiotemporal data are collected and processed providing information about the wave height probability and typical appearance of abnormally high waves (rogue waves). The waves are considered at different water depths ranging from deep to relatively shallow cases (k _p h > 0.8, where k _p is the peak wavenumber, and h is the local depth). The asymmetry between front and rear rogue wave slopes is identified; it becomes apparent for sufficiently high waves in rough sea states at all considered depths k _p h ≥ 1.2. The lifetimes of rogue events may reach up to 30–60 wave periods depending on the water depth. The maximum observed wave has a height of about three significant wave heights. A few randomly chosen in situ time series from the Baltic Sea are in agreement with the general picture of the numerical simulations.     

Impact of pore water conductivity and porosity on the electrical conductivity of kaolinite

The purpose of this study is to quantify the magnitudes of surface conduction and pore water conduction from the measured electrical conductivity of kaolinite, with the ultimate goal of estimating the electrical conductivity of kaolinite with a wide range of pore water conductivities (σ _w = 0.013–3.356 S/m) and porosities (n = 0.368–1.0). Therefore, the theoretical background of the electrical conductivity in soils was reviewed, and electrical conductivity measurements on kaolinite were performed using both slurry and consolidation tests in this study. The results of this study demonstrate that the variations of measured electrical conductivity (σ _mix) with n are debatable according to the values of σ _w, because a decrease in n results in both an increase in surface conduction (K _s) and a decrease in pore water conduction (K _w); this causes the relative magnitude of K _s compared to that of K _w to vary with σ _w and n. Consequently, this study develops the relation between the porosity-normalized K _s/K _w and 1/σ _w. Additionally, the surface conductivity of the tested kaolinite is back-calculated and compared with the previous relationship between K _s and zeta potential of kaolinite. The measured and estimated σ _mix values are compared with the varying pore water conductivity and porosity values.     

Modification of fluid inclusions in quartz by deviatoric stress. III: Influence of principal stresses on inclusion density and orientation

Extraction of useful geochemical, petrologic and structural information from deformed fluid inclusions is still a challenge in rocks displaying moderate plastic strain. In order to better understand the inclusion modifications induced by deviatoric stresses, six deformation experiments were performed with a Griggs piston-cylinder apparatus. Natural NaCl–H₂O inclusions in an oriented quartz crystal were subjected to differential stresses of 250–470 MPa at 700–900 °C and at 700–1,000 MPa confining pressure. Independently of the strain rate and of the crystallographic orientation of the quartz, the inclusions became dismembered and flattened within a crystallographic cleavage plane subperpendicular to σ ₁. The neonate (newly formed) inclusions that result from dismemberment have densities that tend towards equilibrium with P _fluid = σ ₁ at T _shearing. These results permit ambiguities in earlier deformation experiments on CO₂–H₂O–NaCl to be resolved. The results of the two studies converge, indicating that density changes in neonate inclusions are promoted by high differential stresses, long periods at high P and high T, and fluid compositions that maximize quartz solubility. Neonates spawned from large precursor inclusions show greater changes in density that those spawned from small precursors. These findings support the proposal that deformed fluid inclusions can serve as monitors of both the orientation and magnitude of deviatoric stresses during low-strain, ductile deformation of quartz-bearing rocks.     

Mechanical Properties and Deformation and Failure Characteristics of Surrounding Rocks of Tunnels Excavated in Soft Rocks

As soft rocks are likely to soften, slime and swell while contacting water, the existence of soft rocks is harmful for stability of surrounding rocks and supporting structures of tunnels. Through uniaxial and triaxial tests under dry condition and triaxial test with different moisture contents, the mechanical properties and failure modes of soft rocks were studied under conditions that the schistosity plane of the rock samples was vertical to, presented an oblique angle with, and paralleled to the loading direction. The results showed that peak strengths in natural and water-bearing states increased with increasing confining pressures, while those in water-bearing state were 40% lower than those in natural state. The samples were mainly subjected to ductile failure in both natural and water-bearing states while the samples in natural state exhibited a certain brittle failure characteristic in post-peak phase. With the increase of confining pressures, the post-peak curve gradually became gentle after certain brittle failure while the post-peak stresses had an insignificant change. In comparison, the samples in water-bearing state showed significant post-peak disparity, that is, exhibited strong ductile failure characteristic. Moreover, the fitting relationship between triaxial compressive strength and moisture of soft rocks can be expresses as σ ₁ = Aω + B (A < 0, B > 0) while that between elasticity modulus and moisture can be expresses as E = Aω + B (A < 0, B > 0).     

Quantification of photosynthetic inorganic carbon utilisation via a bidirectional stable carbon isotope tracer

The amount of bicarbonate utilised by plants is usually ignored because of limited measurement methods. Accordingly, this study quantified the photosynthetic assimilation of inorganic carbon (CO₂ and HCO₃ ^?) by plants. The net photosynthetic CO₂ assimilation (P _N), the photosynthetic assimilation of CO₂ and bicarbonate (P _N’), the proportion of increased leaf area (f _LA) and the stable carbon isotope composition (δ¹³C) of Orychophragmus violaceus (Ov) and Brassica juncea (Bj) under three bicarbonate levels (5, 10 and 15 mm NaHCO₃) were examined to determine the relationship among P _N, P _N’ and f _LA. P _N’, not P _N, changed synchronously with f _LA. Moreover, the proportions of exogenous bicarbonate and total bicarbonate (including exogenous bicarbonate and dissolved CO₂-generated bicarbonate) utilised by Ov were 2.27 % and 5.28 % at 5 mm bicarbonate, 7.06 % and 13.28 % at 10 mm bicarbonate, and 8.55 % and 17.31 % at 15 mm bicarbonate, respectively. Meanwhile, the proportions of exogenous bicarbonate and total bicarbonate utilised by Bj were 1.77 % and 3.28 % at 5 mm bicarbonate, 2.11 % and 3.10 % at 10 mm bicarbonate, and 2.36 % and 3.09 % at 15 mm bicarbonate, respectively. Therefore, the dissolved CO₂-generated bicarbonate and exogenous bicarbonate are important sources of inorganic carbon for plants.     

Synthesis,TEM characterization and thermal behaviour of LiNiSi<Subscript>2</Subscript>O<Subscript>6</Subscript> pyroxene

A pyroxene with composition LiNiSi₂O₆ was synthesized at T = 1,473 K and P = 2.0 GPa; the cell parameters at T = 298 K are a = 9.4169(6) Å, b = 8.4465(7) Å, c = 5.2464(3) Å, β = 110.534(6)°, V = 390.78(3) Å³. TEM examination of the LiNiSi₂O₆ pyroxene showed the presence of h + k odd reflections indicative of a primitive lattice, and of antiphase domains obtained by dark field imaging of the h + k odd reflections. A HT in situ investigation was performed by examining TEM selected area diffraction patterns collected at high temperature and synchrotron radiation powder diffraction. In HTTEM the LiNiSi₂O₆ was examined together with LiCrSi₂O₆ pyroxene. In LiCrSi₂O₆ the h + k odd critical reflections disappear at about 340 K; they are sharp up to the transition temperature and do not change their shape until they disappear. In LiNiSi₂O₆ the h + k odd reflections are present up to sample deterioration at 650 K. A high temperature synchrotron radiation powder diffraction investigation was performed on LiNiSi₂O₆ between 298 and 773 K. The analysis of critical reflections and of changes in cell parameters shows that the space group is P-centred up to the highest temperature. The comparative analysis of the thermal and spontaneous strain contributions in P2₁/c and C2/c pyroxenes indicates that the high temperature strain in P-LiNiSi₂O₆ is very similar to that due to thermal strain only in C2/c spodumene and that a spontaneous strain contribution related to pre-transition features is not apparent in LiNiSi₂O₆. A different high-temperature behaviour in LiNiSi₂O₆ with respect to other pyroxenes is suggested, possibly in relation with the presence of Jahn–Teller distortion of the M1 polyhedron centred by low-spin Ni³⁺.     

Compressibility of strontium orthophosphate Sr<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript> at high pressure

High pressure in situ synchrotron X-ray diffraction experiment of strontium orthophosphate Sr₃(PO₄)₂ has been carried out to 20.0 GPa at room temperature using multianvil apparatus. Fitting a third-order Birch–Murnaghan equation of state to the P–V data yields a volume of V ₀ = 498.0 ± 0.1 Å³, an isothermal bulk modulus of K _T  = 89.5 ± 1.7 GPa, and first pressure derivative of K _T ′ = 6.57 ± 0.34. If K _T ′ is fixed at 4, K _T is obtained as 104.4 ± 1.2 GPa. Analysis of axial compressible modulus shows that the a-axis (K _a  = 79.6 ± 3.2 GPa) is more compressible than the c-axis (K _c  = 116.4 ± 4.3 GPa). Based on the high pressure Raman spectroscopic results, the mode Grüneisen parameters are determined and the average mode Grüneisen parameter of PO₄ vibrations of Sr₃(PO₄)₂ is calculated to be 0.30(2).     

High-pressure displacive phase transition of a natural Mg-rich pigeonite

A high-pressure single-crystal X-ray diffraction study has been carried out on a P2₁/c natural Mg-rich pigeonite sample with composition ca. Wo₆En₇₆Fs₁₈ using a diamond anvil-cell. The unit-cell parameters were determined at 14 different pressures to 7.14 GPa. The sudden disappearance of the b-type reflections (h + k = odd) and a strong discontinuity (about 2.8%) in the unit-cell volume indicated a first-order P2₁/c–C2/c phase transition between 4.66 and 4.88 GPa. The P(V) data of the P2₁/c phase were fitted to 4.66 GPa by a third-order Birch–Murnaghan equation of state (BM3 EoS), whereas the limited number of experimental data collected within the C2/c phase between 4.88 and 7.14 GPa were fitted using the same equation of state but with K′ constrained to the value obtained for the P2₁/c fitting. The equation of state coefficients are V ₀ = 424.66(6) ų, K _T0 = 104(2) GPa and K′ = 8(1) for the P2₁/c phase, and V ₀ = 423.6(1) ų, K _T0 = 112.4(8) GPa, and K′ fixed to 8(1) for the C2/c phase. The axial moduli for a, b, and c for the P2₁/c phase were obtained using also a BM3-EoS, while for the C2/c phase only a linear calculation could be performed, and therefore the same approach was applied for comparison also to the P2₁/c phase. In general the C2/c phase exhibits axial compressibilities (β _c > β _a >> β _b) lower than those of the P2₁/c phase (β _b > β _c ≈ β _a; similar to those found in previous studies in clinopyroxenes and orthopyroxenes). The lower compressibility of the C2/c phase compared with that of the P2₁/c could be ascribed to the greater stiffness along the b direction. A previously published relationship between P _c and M2 average cation radius (i.r.) has been updated using all the literature data on P2₁/c clinopyroxene containing large cations at M2 site and our new data. The following weighted regression was obtained: P _c (GPa) = 26(4) ? 28(5) ×  i.r (Å), R ² = 0.97. This improved equation can be used to predict the critical pressure of natural P2₁/c clinopyroxene samples just knowing the composition at M2 site.     

On the crystal chemistry and elastic behavior of a phlogopite 3<Emphasis Type="Italic">T</Emphasis>

The crystal chemistry and the elastic behavior under isothermal conditions up to 9 GPa of a natural, and extremely rare, 3T-phlogopite from Traversella (Valchiusella, Turin, Western Alps) [(K_0.99Na_0.05Ba_0.01)(Mg_2.60Al_0.20Fe _0.21 ²⁺ )[Si_2.71Al_1.29O₁₀](OH)₂, space group P3₁12, with a = 5.3167(4), c = 30.440(2) Å, and V = 745.16(9) ų] have been investigated by electron microprobe analysis in wavelength dispersion mode, single-crystal X-ray diffraction at 100 K, and in situ high-pressure synchrotron radiation powder diffraction (at room temperature) with a diamond anvil cell. The single-crystal refinement confirms the general structure features expected for trioctahedral micas, with the inter-layer site partially occupied by potassium and sodium, iron almost homogeneously distributed over the three independent octahedral sites, and the average bond distances of the two unique tetrahedra suggesting a disordered Si/Al-distribution (i.e., 〈T1-O〉 ~ 1.658 and 〈T2-O〉 ~ 1.656 Å). The location of the H-site confirms the orientation of the O–H vector nearly perpendicular to (0001). The refinement converged with R ₁(F) = 0.0382, 846 unique reflections with F _O > 4σ(F _O) and 61 refined parameters, and not significant residuals in the final difference-Fourier map of the electron density (+0.77/?0.37 e ^?/ų). The high-pressure experiments showed no phase transition within the pressure range investigated. The P–V data were fitted with a Murnaghan (M-EoS) and a third-order Birch-Murnaghan equation of state (BM-EoS), yielding: (1) M-EoS, V ₀ = 747.0(3) ų, K _T0 = 44.5(24) GPa, and K′ = 8.0(9); (2) BM-EoS, V ₀ = 747.0(3) ų, K _T0 = 42.8(29) GPa, and K′ = 9.9(17). A comparison between the elastic behavior in response to pressure observed in 1M- and 3T-phlogopite is made.     

Hydraulic Conductivity of Fly Ash-Amended Mine Tailings

The objective of this study was to evaluate the effect of fly ash addition on hydraulic conductivity (k) of mine tailings. Mine tailings used in this study were categorized as synthetic tailings and natural tailings; two synthetic tailings were developed via blending commercially-available soils and natural tailings were collected from a garnet mine located in the U.S. Two fly ashes were used that had sufficient calcium oxide (CaO) content (17 and 18.9 %) to generate pozzolanic activity. Hydraulic conductivity was measured on pure tailings and fly ash-amended tailings in flexible-wall permeameters. Fly ash was added to mine tailings to constitute 10 % dry mass of the mixture, and specimens were cured for 7 and 28 days. The influence of fly ash-amendment on k of mine tailings was attributed to (1) molding water content and (2) plasticity of the mine tailings. Tailings that classified as low-plasticity silts with clay contents less than 15 % exhibited a decrease in k when amended with fly ash and prepared wet of optimum water content (w _opt ). Tailings that classified as low-plasticity clay exhibited a one-order magnitude increase in k with addition of fly ash for materials prepared dry or near w _opt . The decrease in k for silty tailings was attributed to formation of cementitious bonds that obstructed flow paths, whereas the increase in k for clayey tailings was attributed to agglomeration of clay particles and an overall increase in average pore size. The results also indicated that the effect of curing time on k is more pronounced during the early stages of curing (≤7 days), as there was negligible difference between k for 7 and 28-days cured specimens.     

Influence of oxygen fugacity and temperature on the redox state of iron in natural silicic aluminosilicate melts

The influence of oxygen fugacity (fO₂) and temperature on the valence and structural state of iron was experimentally studied in glasses quenched from natural aluminosilicate melts of granite and pantellerite compositions exposed to various T-fO₂ conditions (1100–1420°C and 10^?12–10^?0.68 bar) at a total pressure of 1 atm. The quenched glasses were investigated by Mössbauer spectroscopy. It was shown that the effect of oxygen fugacity on the redox state of iron at 1320–1420°C can be described by the equation log(Fe³⁺/Fe²⁺) = k log(fO₂) + q, where k and q are constants depending on melt composition and temperature. The Fe³⁺/Fe²⁺ ratio decreases with decreasing fO₂ (T = const) and increasing temperature (fO₂ = const). The structural state of Fe³⁺ depends on the degree of iron oxidation. With increasing Fe³⁺/Fe²⁺ ≥ 1, the dominant coordination of Fe³⁺ changes from octahedral to tetrahedral. Ferrous iron ions occur in octahedral (and/or five-coordinated) sites independent of Fe³⁺/Fe²⁺.