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Abstract A series of the calcium-nickel carbonate solid solutions [(Ca1−xNix)CO3] were synthesized and their dissolution in N2-degassed water (NDW) and CO2-saturated water (CSW) at 25 °C was experimentally investigated. During dissolution of the synthetic solids (Ni-bearing calcite, amorphous Ca-bearing NiCO3 and their mixtures), the Ni-calcite and the Ca-NiCO3 dissolved first followed by the formation of the Ni-bearing aragonite-structure phases. After 240–300 days of dissolution in NDW, the water solutions achieved the stable Ca and Ni concentrations of 0.592–0.665 and 0.073–0.290 mmol/L for the solids with lower Ni/(Ca + Ni) mol ratios (XNi), or 0.608–0.721 and 0.273–0.430 mmol/L for the solids with higher XNi, respectively. After 240–300 days of dissolution in CSW, the water solutions achieved the stable Ca and Ni concentrations of 1.094–3.738 and 0.831–4.300 mmol/L, respectively. For dissolution in NDW and CSW, the mean values of log IAP (Ion activity products) in the final stable state (≈ log K sp, Solubility product constants) were determined to be − 8.65 ± 0.04 and − 8.16 ± 0.11 for calcite [CaCO3], respectively; − 8.50 ± 0.02 and − 7.69 ± 0.03 for the synthetical nickel carbonates [NiCO3], respectively. In respect to the bulk composition of the (Ca1−xNix)CO3 solid solutions, the final log IAP showed the highest value when XNi = 0.10–0.30. Mostly, the mean values of log IAP increased with the increasing XNi in respect to the Ni-calcite, the Ni-aragonite and the amorphous Ca-Ni carbonate. The plotting of the experimental data on the Lippmann diagram for the (Ca1−xNix)CO3 solid solution using the predicted Guggenheim parameters of a 0 = 2.14 and a 1 = − 0.128 from a miscibility gap of XNi = 0.238 to 0.690 indicated that the solids dissolved incongruently and the final Ca and Ni concentrations in the water solutions were simultaneously limited by the minimum stoichiometric saturation curves for the Ni-calcite, Ni-aragonite and the amorphous Ca-Ni carbonate. During dissolution in NDW, the Ni2+ preferred to dissolve into the water solution and Ca2+ preferred to remain in the solid, while during dissolution in CSW for the solids with higher XNi, the Ca2+ preferred to dissolve into the water solution and Ni2+ preferred to remain in the solid. These findings provide valuable insights into understanding the mechanisms governing Ni geochemical cycle in natural environments.

To tackle the prevalent challenges encountered with polyamine-based non-aqueous absorbents (NAAs), particularly the formation of viscous products and inferior regeneration performance, this study proposed an innovative synergistic regulation strategy that integrated 2-amino-2-methyl-1-propanol (AMP) and n-propanol (NPA). Accordingly, a novel tertiary tetraethylenepentamine (TEPA)-AMP-NPA (T-A-N) NAA was devised. The optimized T-A-N maintained complete homogeneity throughout the entire CO2 absorption process and achieved an impressive CO2 loading of 1.15 mol·mol−1 while maintaining a low viscosity of merely 22.47 mPa·s. Remarkably, its absorption capacity showed little decrement after four consecutive absorption-desorption cycles, underscoring its exceptional recyclability. Within the T-A-N system, AMP underwent a reaction with CO2, yielding AMP-carbamate and protonated AMP, while TEPA engaged in CO2 absorption to form zwitterionic carbamates. During the desorption process, NPA served as a regeneration activator, facilitating the conversion of stable TEPA-carbamates into less stable alkyl carbonate intermediates, thereby enhancing the T-A-N's regeneration performance. Moreover, the T-A-N system addressed the issue of TEPA-carbamate self-aggregation into insoluble gelatinous substances by leveraging the synergistic enhancement effects between AMP derivatives and NPA. Specifically, these components effectively bound TEPA-carbamate species via robust electrostatic affinity and intermolecular hydrogen-bond interactions, inhibiting their self-aggregation and preventing the formation of insoluble products. Furthermore, T-A-N exhibited a significant reduction in both sensible and latent heat requirements, by 67 % and 82 % respectively, compared to 30 wt% MEA, highlighting its advantageous energy-saving potential for CO2 capture. Overall, harnessing the synergistic enhancement effects of AMP and NPA was conducive to the development of polyamine-based NAAs that offered superior CO2 capture reversibility, low energy consumption, and resistance to insoluble product formation.

Abstract Noble metal materials have been identified as high efficiency catalysts for electrocatalytic reduction of nitrate, and the synthesis and manufacture of high catalytic activity and environmentally friendly catalysts of activating hydrogen for water purification applications is extremely attractive. In this work, the Pd–Cu single-atom catalysts (Pd–Cu-N-BC) were first prepared by direct growth of Pd–Cu single-atom on bamboo biochar by regulating the concentration of precursors and doping method, and then enhanced electrocatalytic reduction nitrate performance and N2 generation. The results showed that Pd–Cu-N-BC displayed excellent catalytic activity and reusability in electrocatalytic reduction nitrate with a low potential of 0.47 V vs. RHE (@10 mA cm−2). The maximum nitrate removal efficiency and N2 generation could reach about 100% and 72.32% within 180 min, respectively. The density functional theory (DFT) calculations confirmed that Cu atoms could catalyze the electrochemical reduction of nitrate to nitrite, and Pd atoms anchored in the nitrogen-doped biochar (N-BC) lattice could catalyze electrochemical reduction of nitrite to N2 involving the formation of hydrogen radical (H*). The characterization results of XANES showed that electronic synergistic effect between Pd and Cu single atoms significantly promotes the N2 production through hydrogenation while inhibiting the generation of byproducts, leading to significantly enhanced electrocatalytic reduction of nitrate to N2. Finally, Pd–Cu-N-BC was designed as a 3D particle electrode for enhanced electrocatalytic reduction of nitrate, exhibiting excellent stability and reusability, which could be considered as a suitable candidate for applications in the remediation of nitrate contamination. Graphical Abstract

VOCs can be used instead of ammonia as a reducing agent to remove NO, achieving the effect of removing VOCs and NO simultaneously. Due to the high energy consumption and low photocatalytic efficiency required for conventional thermocatalytic purification, photothermal coupled catalytic purification can integrate the advantages of photocatalysis and thermocatalysis in order to achieve the effect of pollutants being treated efficiently with a low energy consumption. In this study, samples loaded with Co and Mn catalysts were prepared using the hydrothermal method on Fe-MOF with various morphologies. The catalytic performance of each catalyst was analyzed by studying the effects of their physicochemical properties through various characterizations, including XRD, SEM, BET, XPS, H2-TPR, TEM and O2-TPD. The characterization results demonstrated that the specific surface area, pore volume, high valence Co and Mn atoms, surface adsorbed oxygen and the abundance of oxygen lattice defects in the catalysts were the most critical factors affecting the performance of the catalysts. Based on the results of the performance tests, the catalysts prepared with an octahedral-shaped Fe-MOF loaded with Co and Mn showed a better performance than those loaded with Co and Mn on a rod-shaped Fe-MOF. The conversions of acetone and NO reached 50% and 64%, respectively, at 240 °C. The results showed that the catalysts were capable of removing acetone and NO at the same time. Compared with the pure Fe-MOF without Co and Mn, the loaded catalysts showed a significantly higher ability to remove acetone and NO simultaneously under the combination of various factors. The key reaction steps for the catalytic conversion of acetone and NO on the catalyst surface were investigated according to the Mars–van Krevelen (MvK) mechanism, and a possible mechanism was proposed. This study presents a new idea for the simultaneous removal of acetone and NOx by photothermal coupling.

The substitution of ethyl acetate for ammonia in NH3-SCR provides a novel strategy for the simultaneous removal of VOCs and NO. In this study, three distinct types of biochar were fabricated through pyrolysis at 700 °C. MnOx and TiO2 were sequentially loaded onto these biochar substrates via a hydrothermal process, yielding a family of biochar-based catalysts with optimized dosages. Upon exposure to xenon lamp irradiation at 240 °C, the biochar catalyst designated as 700-12-3GN, derived from Ginkgo shells, demonstrated the highest catalytic activity when contrasted with its counterparts prepared from moso bamboo and loofah. The conversion efficiencies for NO and ethyl acetate (EA) peaked at 73.66% and 62.09%, respectively, at a catalyst loading of 300 mg. The characterization results indicate that the 700-12-3GN catalyst exhibits superior activity, which can be attributed to the higher concentration of Mn4+ and Ti4+ species, along with its superior redox properties and suitable elemental distribution. Notably, the 700-12-3GN catalyst has the smallest specific surface area but the largest pore volume and average BJH pore size, indicating that the specific surface area is not the predominant factor affecting catalyst performance. Instead, pore volume and average BJH pore diameter appear to be the more influential parameters. This research provides a reference and prospect for the resource utilization of biochar and the development of photothermal co-catalytic ethyl acetate and NO at low cost.

In this study, the degradation system of Shewanella oneidensis MR-1 and goethite was constructed with chlorpyrifos as the target contaminant. The effects of initial pH, contaminant concentration, and temperature on the removal rate of chlorpyrifos during the degradation process were investigated. The experimental conditions were optimized by response surface methodology with a Box–Behnken design (BBD). The results show that the removal rate of chlorpyrifos is 75.71% at pH = 6.86, an initial concentration of 19.18 mg·L−1, and a temperature of 30.71 °C. LC-MS/MS analyses showed that the degradation products were C4H11O3PS, C7H7Cl3NO4P, C9H11Cl2NO3PS, C7H7Cl3NO3PS, C9H11Cl3NO4P, C4H11O2PS, and C5H2Cl3NO. Presumably, the degradation pathways involved are: enzymatic degradation, hydrolysis, dealkylation, desulfur hydrolysis, and dechlorination. The findings of this study demonstrate the efficacy of the goethite/S. oneidensis MR-1 complex system in the removal of chlorpyrifos from water. Consequently, this research contributes to the establishment of a theoretical framework for the microbial remediation of organophosphorus pesticides in aqueous environments.

Abstract 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

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.

In this study, a new generation chromium sorbent, mulberry stem biochar/Mn-Fe binary oxide composite (MBC-MFC), was fabricated by chemical precipitation on carbonized mulberry stem according to response surface methodology (RSM) results. RSM was more convenient to figure out the optimized preparation condition of MBC-MFC theoretically for achieving a maximum removal efficiency of Cr(VI) and total chromium (TCr), compared to labor-intensive orthogonal experiments. The RSM results showed that Fe/Mn concentration (CFe; CMn), MBC activation temperature after soaking in KOH solution (T), and pH during precipitation of Fe-Mn oxide were three main factors to significantly affect the efficiency of MBC-MFC (p < 0.05) in Cr(VI) and TCr removal. With the selected condition (CFe = 0.28 mol/L; CMn = 0.14 mol/L; T = 790°C; pH = 9.0), MBC-MFC was synthesized with a large surface area (318.53 m2/g), and the point of zero charge values of MBC-MFC was 5.64. The fabricated MBC-MFC showed excellent adsorption performance of Cr(VI) and TCr in an aqueous solution. The maximum Cr(VI) and TCr removal capacity of MBC-MFC was 56.18 and 54.97 mg/g (T = 25°C, pH = 3.0, t = 48 h, and dosage = 0.10 g/50 ml), respectively, and the maximum Cr(VI) adsorption of MBC-MFC was 4.16 times that of bare MBC, suggesting the synergistic effects of Fe/Mn oxides and MB on the performance of MBC-MFC in Cr(VI) and TCr removal. The adsorption mechanism of MBC-MFC on chromium was mainly contributed by surface complexation and electrostatic attraction. Our study offers valuable outlooks to develop high-performance biochar-based sorbents for heavy metal removal and sustainable environmental remediation.

A novel material named Fe/Mn-C layered double hydroxide composite (Fe/Mn-C-LDH) was synthesized to remove arsenic from an aqueous solution. The removal performance of the composite toward arsenic ions was studied through the batch experiments. The experiment results showed that Fe/Mn-C-LDH exhibited a high adsorption capacity of 46.47 mg/g for As(III) and 37.84 mg/g for As(V) at 318 K, respectively. In addition, the investigation of the release of Fe3+ and Mn2+ in the process of arsenic adsorption revealed that the Fe/Mn-C-LDH exhibited better stability than Fe/Mn-layer double hydroxide (Fe/Mn-LDH) with fewer Mn2+ and Fe3+ releasing under the same condition. The BET results showed that the specific surface area of Fe/Mn-C-LDH decreased after adsorption of As (III) and As (V). Furthermore, the Density Functional Theory (DFT) calculation results proved that the adsorbent combining arsenic by T-site to produce a better adsorption effect for arsenic. Possessing better stability and adsorption capacity, Fe/Mn-C-LDH could potentially serve as a perfect adsorbent for arsenic removal from an aqueous environment. It would provide a promising approach for removing heavy metal from the aquatic environment in the future.

Basic ferric sulfate-arsenates [FeSAsOH, Fe(SO4)x(AsO4)y(OH)z·nH2O] were prepared and characterized to study their potential fixation of arsenic in the oxidizing and acidic environment through a dissolution for 330d. The synthetic solids were well-shaped monoclinic prismatic crystals. For the dissolution of the sample FeSAsOH–1 [Fe(SO4)0.27(AsO4)0.73 (OH)0.27·0.26H2O] at 25–45°C and initial pH 2, all constituents preferred to be dissolved in the order of AsO43− > SO42− > Fe3+ in 1–3 h, in the order of SO42− > AsO43− > Fe3+ from 1–3 h to 12–24 h, and finally in the order of SO42− > Fe3+ > AsO43−. The released iron, sulfate, and arsenate existed dominantly as Fe3+/Fe(OH)2+/FeSO4+, HSO4−/SO42−/FeSO4+, and H3AsO40/H2AsO4−, respectively. The higher initial pHs (6 and 10) could obviously inhibit the release of Fe3+ from solid into solution, and the solid components were released in the order of SO42− > AsO43− > Fe3+. The crystal tops were first dissolved, and the crystal surfaces were gradually smoothed/rounded until all edges and corners disappeared. The dissociations were restricted by the Fe-O(H) breakdown in the FeO6 octahedra and obstructed by the OH− and AsO4 tetrahedra outliers; the lowest concentration of the dissolved arsenic was 0.045 mg/L. Based on the dissolution experiment at 25°C and pH 2, the solubility products (Ksp) for the basic ferric sulfate-arsenate [Fe(SO4)0.27(AsO4)0.73 (OH)0.27·0.26H2O], which are equal to the ion activity products (logˍIAP) at equilibrium, were calculated to be -23.04 ± 0.01 with the resulting Gibbs free energies of formation (ΔGfo) of −914.06 ± 0.03 kJ/mol.

Arsenic is very harmful to most living organisms. The solubility data of As-containing compounds are significant in geoscience and environmental science. The arsenic-incorporated natroalunite precipitation has been proposed to eliminate arsenic from water, both for industrial practice and remediation of polluted areas. Unfortunately, only few works have been made on partial arsenic incorporation in natroalunite and the thermodynamic data for natroalunite and arsenic-incorporated natroalunite now are still lacking. Moreover, the dissolution mechanisms of arsenic-incorporated natroalunites have never been studied. In the present work, the dissolution of the synthetic natroalunite [Na0.93(H3O)0.61Al2.82(SO4)2(OH)6] and the synthetic arsenic-incorporated natroalunite [Na0.88(H3O)2.44Al2.35(AsO4)0.38(SO4)1.62(OH)6] at 25°C, 35°C, and 45°C was experimentally examined in HNO3 solution (pH of 2.00 and 4.00) and pure water. The characterizations confirmed that the solids showed no recognizable change after dissolution. All dissolutions underwent a pH variation, which was caused by a great depleting of H3O+/OH− ions, typically at the reaction beginning. The dissolution in H3O+ medium proved to be near-stoichiometric within the short beginning period, and the dissolved Na+, Al3+, SO42−, and AsO43− concentrations were stoichiometric according to the initial solids and then appeared to be nonstoichiometric with the Na/SO4 mole ratios higher and the Al/SO4 and AsO4/SO4 mole ratios lower than the stoichiometry until the experimental end, indicating that the components were released from solid to solution preferentially after the following order: Na+ (H3O+) > SO42− > AsO43− > Al3+. From the experimental results under the condition of initial pH 2.00 and 25°C, the solubility products [Ksp] and the Gibbs free energies of formation [ΔGf°] were calculated to be 10−81.02±0.33∼10−81.04±0.27 and −4713 ± 2 to −4714 ± 1 kJ/mol for the natroalunite and 10−92.30±0.30∼10−92.41±0.37 and −5078 ± 2 to −5079 ± 2 kJ/mol for the arsenic-incorporated natroalunite, respectively. The thermodynamic quantities, ΔG°, ΔH°, ΔS°, and ΔCp°, were determined to be 462303.43 J/K·mol, 122466.83 J/mol, −1140.39 J/K·mol, and 4280.13 J/K·mol for the natroalunite dissolution reaction at initial pH 2.00 and 25°C and to be 526925.48 J/K·mol, 159674.76 J/mol, −1232.38 J/K·mol, and 1061.12 J/K·mol for the dissolution of the arsenic-incorporated natroalunite at initial pH 2.00 and 25°C, respectively.

The fixed-bed column adsorption-desorption of As(V) by the porous composite of iron oxides and carbon with eucalyptus wood hierarchical microstructure (PC-Fe/C) was experimentally studied. The increase in the influent As(V) concentration and the inflow rate resulted in an earlier exhaustion of the column. The breakthrough curves indicated that a larger adsorbent mass, a smaller adsorbent grain size and a lower influent pH prolonged the column life span. The operating temperature had negligible effect. All breakthrough curves could be well fitted with the Thomas and Yoon–Nelson models. Under the condition of the influent flow rate of 5.136 mL/min, the influent As(V) concentration of 20 mg/L, the influent pH of 3, the adsorbent mass of 2 g, the adsorbent grain size of

Dissolution of the synthetic cadmium fluorapatite [Cd5(PO4)3F] at 25°C, 35°C, and 45°C was experimentally examined in HNO3 solution, pure water, and NaOH solution. The characterization results confirmed that the cadmium fluorapatite nanorods used in the experiments showed no obvious variation after dissolution. During the dissolution of Cd5(PO4)3F in HNO3 solution (pH = 2) at 25°C, the fluoride, phosphate, and cadmium ions were rapidly released from solid to solution, and their aqueous concentrations had reached the highest values after dissolution for

A series of Zn-substituted hydroxylapatites [(ZnxCa1−x)5(PO4)3OH, Zn-Ca-HA] with the Zn/(Zn + Ca) molar ratio (XZn) of 0~0.16 was prepared and characterized, and then the dissolution of the synthesized solids in aqueous solution was investigated by batch experiment. The results indicated that the aqueous zinc, calcium, and phosphate concentrations greatly depended on the Zn/(Zn + Ca) molar ratio of the Zn-Ca-HA solids (XZn). For the Zn-Ca-HA dissolution at 25°C with an initial pH of 2.00, the final solution pH increased, while the final solution calcium and phosphate concentrations decreased with the increasing XZn. The final solution zinc concentrations increased with the increasing XZn when XZn≤0.08 and decreased with the increasing XZn when XZn = 0.08~0.16. The mean Ksp values for (ZnxCa1−x)5(PO4)3OH at 25°C decreased from 10−57.75 to 10−58.59 with the increasing XZn from 0.00 to 0.08 and then increased from 10–58.59 to 10–56.63 with the increasing XZn from 0.08 to 0.16. This tendency was consistent with the dependency of the lattice parameter a on XZn. The corresponding free energies of formation (ΔGfo) increased lineally from −6310.45 kJ/mol to −5979.39 kJ/mol with the increasing XZn from 0.00 to 0.16.

Dissolution of the hydroxypyromorphite [lead hydroxyapatite, Pb5(PO4)3OH] in HNO3 solution (pH = 2.00), ultrapure water (pH = 5.60), and NaOH solution (pH = 9.00) was experimentally studied at 25°C, 35°C, and 45°C. The XRD, FT-IR, and FE-SEM analyses indicated that the hydroxypyromorphite solids were observed to have indistinguishable change during dissolution. For the hydroxypyromorphite dissolution in aqueous acidic media at initial pH 2.00 and 25°C, the aqueous phosphate concentrations rose quickly and reached the peak values after 1 h dissolution, while the aqueous lead concentrations rose slowly and reached the peak values after 1440 h. The solution Pb/P molar ratio increased constantly from 1.10 to 1.65 near the stoichiometric ratio of 1.67 to 209.85~597.72 and then decreased to 74.76~237.26 for the dissolution at initial pH 2.00 and 25°C~45°C. The average Ksp values for Pb5(PO4)3OH were determined to be 10−80.77 (10−80.57−10−80.96) at 25°C, 10−80.65 (10−80.38−10−80.99) at 35°C, and 10−79.96 (10−79.38−10−80.71) at 45°C. From the obtained solubility data for the dissolution at initial pH 2.00 and 25°C, the Gibbs free energy of formation [ΔGfo] for Pb5(PO4)3OH was calculated to be −3796.71 kJ/mol (−3795.55~−3797.78 kJ/mol).

The solubility products for calcite-group minerals are very important to interpretate their behavior in natural water, which have a great influence on the migration and transformation of heavy metals in the environment. But discrepant solubility values for these minerals were reported previously. In the present work, calcite, rhodochrosite, smithsonite and otavite were prepared, and their dissolution processes lasting nine months were then experimentally investigated. After the 5040h dissolution in the airsaturated water, the aqueous concentrations of Ca, Mn, Zn and Cd attained the steady state of 0.511 ~ 0.562 mmol/L for calcite, 0.211 ~ 0.234 mmol/L for rhodochrosite, 0.277 ~ 0.314 mmol/L for smithsonite and 0.00346 ~ 0.00648 mmol/L for otavite, respectively. For the dissolution in the N2-degassed water, the air-saturated water and the CO2-saturated water Ksp) and the Gibbs free energies of formation mated to be -8.38±0.07 ~ -8.43±0.04 and -1129.27 ±0.40 ~3), -10.18±0.04 ~ -10.29±0.12 and -814.00±0.22 ~ - 3), -10.70±0.04 ~ -10.50±0.09 and -735.97±0.25 ~ -3), -11.55±0.08 ~ -11.71±0.11 and -671.40±0.46 ~ -672.30±0.64 kJ/mol for otavite CdCO3), respectively. [ABSTRACT FROM AUTHOR]