A complete series of calcite-rhodochrosite solid solutions [(Ca1-xMnx)CO3] are prepared, and their dissolution processes in various water samples are experimentally investigated. The crystal morphologies of the solid solutions vary from blocky spherical crystal aggregates to smaller spheres with an increasing incorporation of Mn in the solids. Regarding dissolution in N2-degassed water, air-saturated water and CO2-saturated water at 25 °C, the aqueous Ca and Mn concentrations reach their highest values after 1240–2400 h, 6–12 h and < 1 h, respectively, and then decrease gradually to a steady state; additionally, the ion activity products (log_IAP) at the final steady state (≈ solubility products in log_Ksp) are estimated to be − 8.46 ± 0.06, − 8.44 ± 0.10 and − 8.59 ± 0.10 for calcite [CaCO3], respectively, and − 10.25 ± 0.08, − 10.26 ± 0.10 and − 10.28 ± 0.03, for rhodochrosite [MnCO3], respectively. As XMn increases, the log_IAP values decrease from − 8.44 ~ − 8.59 for calcite to − 10.25 ~ − 10.28 for rhodochrosite. The aqueous Mn concentrations increase with an increasing Mn/(Ca + Mn) molar ratio (XMn) of the (Ca1-xMnx)CO3 solid solutions, while the aqueous Ca concentrations show the highest values at XMn = 0.53–0.63. In the constructed Lippmann diagram of subregular (Ca1-xMnx)CO3 solid solutions, the solids dissolve incongruently, and the data points of the aqueous solutions move progressively up to the Lippmann solutus curve and then along the solutus curve or saturation curve of pure MnCO3 to the Mn-poor side. The microcrystalline cores of the spherical crystal aggregates are preferentially dissolved to form core hollows while simultaneously precipitating Mn-rich hexagonal prisms.

In this study, coupling electrokinetic (EK) with the permeable reactive barriers (PRB) of Fe/Mn/C-LDH composite was applied for the remediation of arsenic-contaminated soils. By using self-made Fe/Mn/C-LDH materials as PRB filler, the effects of pretreatment and polarization shielding on EK-PRB of Fe/Mn/C-LDH for remediation of arsenic contaminated soils were investigated. For the pretreatment, phosphoric acid, phosphoric acid and water washing, and phosphate were adopted to reduce the influence of iron in soil. The addition of phosphate could effectively reduce the soil leaching toxicity concentration. The removal rate of the soil pretreated with phosphoric acid or phosphoric acid and water washing was better than with phosphate pretreatment. For the polarization shielding, circulating electrolyte, electrolyte type, anion and cation membranes, and the exchange of cathode and anode were investigated. The electrolyte circulates from the cathode chamber to the anode chamber through the peristaltic pump to control the pH value of the electrolyte, and the highest arsenic toxicity removal rate in the soil reaches 97.36%. The variation of total arsenic residue in soil using anion and cation membranes is the most regular. The total arsenic residue gradually decreases from cathode to anode. Electrode exchange can neutralize H+ and OH− produced by electrolyte, reduce the accumulation of soil cathode area, shield the reduction of repair efficiency caused by resistance polarization, enhance current, and improve the removal rate of arsenic in soil.

As an innovative and economical material, hydroxyapatite does little harm to the environment. In this study, a magnesium hydroxyapatite (Mg-HAP) adsorbent was prepared by doping magnesium. Magnesium doping can increase the hydroxyl groups on the surface of Mg-HAP to form more adsorption sites and improve the removal effect of the heavy metal Zn(II) in water. This study was implemented to survey the effect of different sorption elements, including the liquor initial pH, initial concentration, dose of adsorbents, and other factors, on the adsorption effect. The outcomes show that the sorption effect was best at the time that the liquor was weakly acidic (pH = 6); At a pH of 6, the temperature of 25 °C when the optimal dosage of adsorbent is 0.25 g, the maximum adsorption amount is 62.11 mg/g. Through data fitting, the adsorption process can be accurately described as a pseudo-second-order dynamics model and the Langmuir isotherm equation. According to the thermodynamic analysis, the sorption of zinc ions by Mg-HAP belongs to the process of spontaneous endothermic and entropy increase, and the increase of temperature was conducive to adsorption. Material characterization and analysis indicate that surface complexation and dissolution-precipitation was the main mechanism for adsorption of Zn(II).

A complete series of the calcite–otavite solid solutions [(Ca1−xCdx)CO3] were prepared, and their dissolution processes lasting nine months were experimentally investigated. For the dissolution in the N2-degassed water, the Ca concentrations of the aqueous phases increased up to the steady states after 5040 h of dissolution, and the Cd concentrations of the aqueous phases increased up to the highest values and then decreased gradually to the steady states of 0.017–6.476 μmol/L after 5040 h of dissolution. For the dissolution in the CO2-saturated water, the Ca and Cd concentrations of the aqueous phases increased up to the peak values and then decreased gradually to the steady states of 0.94–0.46 mmol/L and 0.046–9.643 μmol/L after 5040 h of dissolution, respectively. For the dissolution in the N2-degassed water at 25 °C, the mean solubility products (log Ksp) and the Gibbs free energies of formation (ΔGfθ) were estimated to be −8.45–−8.42 and −1129.65–−1129.48 kJ/mol for calcite [CaCO3] and −11.62–−11.79 and −671.81–−672.78 kJ/mol for otavite [CdCO3], respectively. Generally, the log Ksp values decreased non-linearly, and the ΔGfθ values increased linearly with the increasing Cd/(Ca+Cd) mole ratio (XCd) of the (Ca1−xCdx)CO3 solid solutions. In the Lippmann diagrams constructed for the sub-regular (Ca1−xCdx)CO3 solid solutions with the estimated Guggenheim coefficients a0 = −0.84 and a1 = −3.80 for the dissolution in the N2-degassed water or a0 = −1.12 and a1 = −3.83 for the dissolution in the CO2-saturated water, the (Ca1−xCdx)CO3 solid solutions dissolved incongruently, moved progressively up to the quasi-equilibrium curves for otavite and then along the quasi-equilibrium curve from right to left, approached the solutus curve and finally reached the minimum stoichiometric saturation curve for calcite. The considerably Cd-poor aqueous phases were finally in equilibrium with the CdCO3-rich solid phases.

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