Pyrite Surface Research Articles

Application of calcium hypochlorite and carboxymethyl chitosan as combined depressants for selective flotation separation of chalcopyrite from pyrite at low alkalinity

Flotation separation of copper-sulfur at low alkalinity has attracted soaring interest in the beneficiation of copper sulfide ore. In this work, application of calcium hypochlorite (Ca(ClO)2) and carboxymethyl chitosan (OCMC) as combined depressants for selective flotation separation of chalcopyrite from pyrite was investigated. A maximum recovery difference of 71.35 % between both minerals is observed under the recommended conditions ([Ca(ClO)2] = 60 mg/L, [OCMC] = 400 mg/L and 40 mg/L SBX at pH=8). Besides, the copper-sulfur flotation separation indexes were assessed by the artificial mixed-mineral tests. Results of contact angle measurement, zeta potential and adsorption amount analysis reveal that the combined depressants severely impede the collector adsorption onto pyrite surfaces, and has a light effect on the chalcopyrite. OCMC exhibits a stronger complexing ability on Ca2+ and Fe2+ ions than Cu2+ ions. XPS results confirm that the combined depressant interact with pyrite surfaces intensively, and prompt a deep conversion of S22- and Sn2-/S0 into S2- and SO42- species, as well as a deep transformation of Fe(II)-S into Fe(III)-O/OH on the pyrite surface. ToF-SIMS and thermodynamic calculation results afford the favorable evidence for the selective suppression of the pyrite with added the combined depressant. Thereby the selective oxidation and intense complexation on the pyrite stemming from the combined depressant synergy are responsible for the selective separation of chalcopyrite from pyrite.

Effect of D-arginine as a novel depressant on the flotation separation of chalcopyrite from pyrite at low alkalinity

Flotation separation of Cu–Fe sulfide minerals typically necessitate the addition of substantial quantities of lime to depress pyrite flotation. Because lime can harm the environment, there is an urgent need to develop novel environmentally friendly depressants that are non-toxic and biodegradable. In this study, we investigated an environmentally friendly pyrite depressant containing amino and carboxyl groups, namely D-arginine (DA). The effect of DA on the surface hydrophobicity of Cu–Fe sulfide minerals and thus collector adsorption was investigated by analyzing zeta potentials, adsorption capacities, and contact angles. Additionally, changes in the surface properties of the minerals induced by DA were examined using X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectroscopy (ToF-SIMS), and atomic force microscopy (AFM). Flotation tests revealed that 2 × 10–4 mol/L DA reduced the flotation recovery of pyrite to 9.96 % at low alkalinity while leaving chalcopyrite recovery unchanged. The results of mineral surface analysis indicated that DA exhibited significantly stronger adsorption on the pyrite surface than on the chalcopyrite surface. Furthermore, DA effectively reduced the adsorption of the collector on the surface of pyrite, thereby weakening pyrite floatability at low alkalinity. Therefore, DA is a promising alternative depressant for the flotation separation of chalcopyrite from pyrite.

The Dissolution Behavior of Pyrite and Chalcopyrite During Low-Temperature Pressure Oxidation: Chalcopyrite Influence on Pyrite Oxidation

The research of this paper was carried out on the low-temperature (100 ± 2 °C) pressure (0.2–0.8 MPa) leaching of pyrite, chalcopyrite and their mixture. According to experiments on chalcopyrite dissolution, increasing the oxygen pressure from 0.2 up to 0.8 MPa had a slight effect on chalcopyrite dissolution. Oxygen pressure and initial sulfuric acid concentration in the range of 10–50 g/L had the greatest positive effect on the pyrite oxidation. The SEM and EDX mappings indicate the chalcopyrite and pyrite surfaces to be passivated by elemental sulfur. The oxidation degree of pyrite in its mixture with chalcopyrite increased significantly from 54.5 up to 80.3% in 0–240 min. The reaction time is relative to the dissolution of the individual mineral, while the dissolution of chalcopyrite remained virtually unchanged. The addition of Cu (II) and Fe (III) ions does not influence pyrite dissolution when chalcopyrite is added in a leaching process, which can be explained by the formation of an electrochemical link between the minerals. The positive effect of chalcopyrite addition is associated with a decreased formation of elemental sulfur on the surface of pyrite. The described method can be used for the hydrometallurgical processing of copper raw materials with increased pyrite content, as well as for the pretreatment of copper concentrates with gold-rich pyrite concentrates to increase the recovery of gold and silver.

Ball milling of pyrite in air to significantly promote the Fenton reaction: A mechanistic study

Natural pyrite (FeS2) has been widely used as heterogenous Fenton catalyst due to the unique iron supplying and ferrous regeneration performance, however, natural pyrite has poor catalytic activity due to the low surface reactivity. Ball milling is commonly used to modify pyrite, but the mechanism has not been thoroughly studied. In our work, by optimizing the ball milling conditions, the catalytic efficiency of modified pyrite is increased by 60 times compared to natural pyrite, and the ball milled pyrite Fenton system was able to degrade dyes and a series of antibiotics within 30 min. Compared to ball milling in nitrogen and vacuum, ball milling in air increased the proportion of S2− and active iron sites on the surface of pyrite, which assisted and accelerated the regeneration of ferrous and enhanced the iron supplying performance. This work explored the mechanisms of ball milling to modify the properties of pyrite, reported a green and efficient ball milled pyrite Fenton system, and provided a new insight in regulating ball milling conditions for mechanochemical modification.

Systematic Exploration of the Interactions between Pyrite and Coal from the View of Density Functional Theory

Coal is often adhered to by pyrite during slime flotation, causing an increase in the sulfur content of clean coal. In order to study the mechanism of pyrite adhesion to coal surfaces, different coal structural units were built and optimized, and the most stable adsorption model of them on pyrite surfaces was determined. The mechanism of pyrite particles adhering to the surface of coal slurries was explored with the method of DFT. The results showed that the interaction mechanism between pyrite surface and Ph-OH and Ph-O-CH3 was the result of a weak interaction between the H atom of Ph-OH and Ph-O-CH3 and the S atom of the pyrite surface. The interaction mechanism between the pyrite surface and Ph-COOH and Ph-CO-CH3 was both as a result of H-S interactions and weak Fe-O interactions. On the whole, there were weak interactions between pyrite particles and the coal slurry, and the pyrite particles can spontaneously adsorb on the surface of the coal slurry.

New Insights on the Understanding of Sulfur-Containing Coal Flotation Desulfurization

The clean and efficient utilization of coal is a promising way to achieve carbon neutrality. Coking coal is a scarce resource and an important raw material in the steel industry. However, the presence of pyrite sulfur affects its clean utilization. Nonetheless, this pyrite could be removed using depressants during flotation. Commonly used organic depressants (sodium lignosulfonate (SL), calcium lignosulfonate (CL), and pyrogallol (PY)) and inorganic depressants (calcium oxide (CaO) and calcium hypochlorite (Ca(ClO)2)) were chosen in this study. Their inhibition mechanism was discussed using FTIR, XPS, and molecular dynamics (MD) methods. The desulfurization ability of organic depressants was shown to be better than inorganic ones. Among the organic depressants, PY proved to be advantageous in terms of low dosage. Physical adsorption was identified as the main interaction form of SL, CL, and PY onto the surface of pyrite, as evidenced from FTIR and XPS analyses. Similarly, MD simulation results showed that hydrogen bonds played a proactive role in the interactions between PY and pyrite. The diffusion coefficient of water molecules on the pyrite surface was also observed to decrease when organic depressants were present, indicating an increase in the hydrophilicity of pyrite. This research is of great significance to utilize sulfur-containing coal and minerals.

Mechanism of pyrite depression by marine Fe(II)-oxidizing bacteria in seawater flotation

Seawater flotation is a promising technique to reduce environmental and economic loads in mineral processing. This study attempted to depress pyrite, a common gangue sulfide mineral, using two marine iron (Fe) oxidizing bacteria (MFeOB), Thalassospira sp. TF-1 and Mariprofundus sp. E-4, in seawater flotation without pH control; the MFeOB could contribute to hydrophilization of the pyrite surface by oxidation and/or adhesion of bacterial cells. Pyrite or chalcopyrite samples were preconditioned in seawater containing MFeOB for different times (15 min or 30 min). As a result of flotation experiments, the recovery of pyrite preconditioned without MFeOB (i.e., control sample) decreased to 64.2 % after 30 min reaction. The same recovery was observed when pyrite was preconditioned with Thalassospira sp. TF-1, whereas the recovery was successfully decreased to 20.2 % after preconditioning with Mariprofundus sp. E-4 for 30 min. X-ray photoelectron spectroscopy analysis of preconditioned pyrite samples showed no significant difference of Fe-oxidizing compounds between with and without MFeOB reaction, suggesting that the formation of hydrophilic substances such as Fe(OH)3 derived from pyrite oxidation by MFeOB is unlikely to be the main reason for the pyrite depression by Mariprofundus sp. E-4. The adhesion experiment revealed that MFeOB cells could cover the pyrite surface but not the chalcopyrite surface, showing that the hydrophilicity of Mariprofundus sp. E-4 cell caused the pyrite depression. This result suggests that the hydrophilic/hydrophobic properties of bacterial cells are a significant determining factor in pyrite recovery in seawater flotation in the case of MFeOB.

Pyrite activation in seawater flotation by copper and lead ions: XPS and in-situ electrochemical investigation

Pyrite, as the main carrier of gold, can be collected via flotation which consumes high volumes of fresh water. Seawater is the promising alternative to fresh water, especially in the fresh water deficient regions. However, pyrite flotation is usually ineffective in seawater, which requires activation prior to recovery. This study mainly focuses on the roles of Cu2+ and Pb2+ on pyrite flotation in seawater. The flotation and contact angle results indicated that Cu2+ and Pb2+ obviously increased pyrite recovery in seawater by enhancing its surface hydrophobicity. Further XPS studies revealed that the formation of Fe-S-Cu(I) and Fe-O-Cu(II) on pyrite surface due to Cu2+ activation while the presence of Fe-O-Pb(II) and Fe-SO-Pb(II) due to Pb2+ activation, thereby improving the active sites and adsorption of xanthate. In addition, the in-situ scanning electrochemical microscopy (SECM) results showed that the formation of Cu2+ and Pb2+ activated products increased the electrochemical reactivity of pyrite surface, which was the main reason for the improved pyrite floatability. Moreover, the current consequence evolution indicated that pyrite activation by Cu2+ was stronger than that by Pb2+. The SECM imaging also showed that the adsorption of xanthate decreased the electrochemical reactivity on pyrite surface, with more significant role observing on the activated surface than that of the un-activated pyrite. It should be noted that the Cu2+/Pb2+ activation and xanthate adsorption were distributed unevenly on pyrite surface. This study therefore provides an in-situ approach to understand the role of inorganic ions and reagents on pyrite flotation in seawater, providing a promising strategy to use seawater for the flotation recovery of gold.

An investigation on pyrite floatability using stable micro-nanobubble-assisted flotation

This study critically examines the impact of micro-nanobubble (MNB)-assisted flotation on pyrite recovery in bulk ore, and clarifies the intricate relationship between pyrite and its associated ore. The physicochemical properties of MNBs and the interaction mechanisms between xanthate collector and pure pyrite mineral were evaluated using advanced analytical techniques, including Dynamic Light Scattering (DLS), Field-Emission Scanning Electron Microscopy coupled with Energy-Dispersive X-ray Spectroscopy (FESEM-EDX), and Ultraviolet-Visible Spectroscopy (UV-Vis), in the absence and the presence of MNBs. MNBs were created through hydrodynamic cavitation, and their characteristics revealed a size increase from 600 nm to 3 µm over 25 days. Notably, the zeta potential measurements indicated an increase from -2.5 to 0 mV at a constant pH of 8, correlating with the geometric mean size of MNBs coarsening from 600 nm to 2-3 µm. The FESEM and EDS analyses disclosed that ultrasonic treatment effectively dispersed ultrafine surface coatings on pyrite particles, increasing iron and sulfur purity by 8% and 6%, respectively, and significantly reducing surface oxygen by 53%. Micro-flotation and batch rougher kinetic flotation experiments were conducted with and without MNBs, leading to a 7% and 8% improvement in recovery for pyrite mono-minerals (-105+53 µm) and its ore (d<sub>80</sub>=150 µm), respectively. The sorption behavior of sodium isopropyl xanthate (SIPX) collector on the particle surface was also investigated at various concentrations (ca. 10-160 µM) in the presence and absence of stable MNBs and demonstrated that the presence of MNBs resulted in a 1.6-fold increase in collector absorption on the pyrite surface, confirming the findings obtained from micro-flotation. Moreover, adsorption behavior is up to 1.3 times compared to the scenario without MNBs. The adsorption process was controlled by a pseudo-second-order model, indicating a chemical sorption mechanism.

Revealing the vital role of sulfur site on the surface of pyrite in 1O2 formation for promoting ciprofloxacin degradation via peracetic acid activation

Pyrite has been widely utilized to activate oxidants for water treatment, yet the regulation of reactive oxygen species (ROS) by sulfur sites on its surface has been overlooked. In this study, the surface sulfur sites were regulated by thermal modification of natural pyrite in the N2 atmosphere (denoted as P-X, where X represented pyrolysis temperatures ranging from 400 to 700 °C), and these modified pyrites were employed to activate peracetic acid (PAA) for ciprofloxacin (CIP) degradation. The results revealed that the degradation rate of CIP increased as the reduced sulfur content increased, with the P600/PAA system achieving the highest apparent degradation rate (kobs = 0.0999 min−1). Quenching experiments and electron paramagnetic resonance (EPR) analysis identified various ROS involved in the P-X/PAA system, with hydroxyl radical (·OH) and singlet oxygen (1O2) identified as dominant reactive species responsible for CIP degradation. The reduced sulfur sites served as the primary active sites facilitating the conversion of organic radicals (·CH3C(O)OO) into superoxide radicals (·O2−) and 1O2. Furthermore, the P600/PAA system demonstrated robust adaptability under both acidic and neutral pH conditions, efficiently degrading CIP even in the presence of complex matrices such as Cl−, NO3−, SO42−, NH4+, or humic acid (HA) in water bodies, although HCO3− was found to inhibit CIP degradation. This study significantly enhances our understanding of the interaction between reduced sulfur sites and ROS in PAA-based advanced oxidation processes (AOPs), offering a promising technology for efficient antibiotic treatment in water purification.

Acid mine drainage activation mechanism on lime-depressed pyrite flotation from copper sulfide ore

The lime-depressed pyrite from Cu differential flotation tailings with acid mine drainage (AMD) as a natural activator was recovered. The effect of AMD on lime-depressed pyrite flotation was investigated by a series of laboratory flotation tests and surface analytical techniques. Flotation test results indicated that AMD could effectively activate the pyrite flotation with a sodium butyl xanthate (SBX) collector, and a high-quality sulfur concentrate was obtained. Pulp ion concentration analysis results indicated that AMD facilitated desorption of Ca2+ and adsorption of Cu2+ on the depressed-pyrite surface. Adsorption measurements and contact angle analysis results confirmed that adding AMD improved the adsorption amount of SBX collector on the pyrite surface and increased the contact angle by 31°. Results of Raman spectroscopy and X-ray photoelectron spectroscopy analysis indicated that AMD treatment promoted the formation of hydrophobic species (S0 hydrophobic entity and copper sulfides) and the removal of hydrophilic calcium and iron species on the pyrite surface, which reinforced the adsorption of collector. The findings of the present research provide important theoretical basis and technical support for a cleaner production of copper sulfide ores.

Overlooked pyrite-mediated heterogeneous Fenton processes: Mechanisms of surface hydroxyl radical generation and associated decontamination performance

Pyrite-based Fenton-like processes have been extensively studied for wastewater decontamination; however, most relevant studies placed excessive emphasis on the homogeneous Fenton reaction mediated by aqueous Fe2+, resulting in the proposed technologies facing issues such as additional acid requirements for pH adjustment and excessive iron sludge production. Herein, through in situ shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS), custom dual-chamber reactor experiments, and a series of control experiments, significant hydroxyl radical generation was identified during the pyrite/H2O2 process, while the dominant reactive iron species was verified to the structural Fe sites on the pyrite surface, rather than structural Fe(II) in secondary iron minerals and surface adsorbed Fe2+. Consequently, even with significant suppression of the homogeneous Fenton pathway, the pyrite/H2O2 process exhibited significant degradation efficiency for sulfamethoxazole (SMX) at pH 4. Moreover, the pyrite/H2O2 process was found to selectively remove 50 μM of pollutants with high affinity for pyrite (bisphenol A, carbamazepine, nitrobenzene, and SMX), even in the presence of 50–100 mM methanol. Compared to the typical iron-based reductive catalyst (zero-valent iron, ZVI), pyrite mediated a Fenton process with greater potential for practical applications at pH 4, achieving a 43.75-fold reduction in iron sludge production and almost doubling the H2O2 utilization efficiency. Additionally, in contrast to ZVI, minimal iron oxide formed on the pyrite surface during the oxidation process. Thus, after seven cycles of degradation experiments, the decontamination efficiency of the pyrite/H2O2 process remained stable. These findings are crucial for understanding the complex environmental behavior of pyrite in both natural and engineering processes and provide a new perspective for the efficient utilization of pyrite resources as well.

Separation of galena and pyrite via green organic macromolecules at low alkalinity: Flotation response and surface adsorption mechanisms

Pyrite must be separated from galena during the beneficiation stage because it releases toxic gases during pyrometallurgy. However, the separation of the two minerals presents a huge obstacle as they have comparable hydrophobicity. This work offers an environmentally friendly pyrite depressant, pullulan polysaccharide (PP), for concentrating galena. Single mineral flotation showed that the ability of PP to deteriorate floatability was significantly stronger for pyrite than for galena within the pH range of 6.00 − 12.00. PP preadsorption assisted in separating galena from pyrite in a low-alkalinity pulp. The recovery of galena was 71.20 % higher than that of pyrite in the binary mineral flotation system. Characterization results confirmed that the Fe sites of pyrite were more susceptible to forming a stable coordination with the O atoms of PP’s C−O−H group compared to the Pb sites of galena. PP can impede the sodium butyl xanthate (BX) sorption on the pyrite surface, thus effectively depressing the pyrite. By contrast, the sorption of BX onto the galena surface was unaffected by PP, and the galena remained floatable. Thus, PP could be considered as an alternative to conventional inorganic depressants in the galena–pyrite flotation system. This work provides a scientific reference for the green and sustainable exploitation of non-ferrous metal resources.

Dynamics of Cu isotope fractionation during the reactions of pyrite with Cu(I)-bearing hydrothermal fluids

Experimental investigation of the fractionation behavior of Cu isotopes during the replacement of pyrite by Cu-bearing sulfides (chalcopyrite, bornite, and chalcocite) was conducted under hydrothermal conditions. At the initial stages of the replacement reaction, small mounds of product formed on the pyrite surface; these mounds then grew and coalesced, progressively covering the pyrite grains as the reaction proceeded. Chalcopyrite, bornite, and chalcocite formed sequential monomineralic zones from the pyrite reaction front towards the solution. During the early stage of the reaction, Cu isotope fractionation between the solids and the aqueous solution (Δ65Cusolid-aqueous, Δ65Cusolid-aqueous = δ65Cusolid – δ65Cuaqueous) was approximately –0.6 ‰, similar to the calculated equilibrium Cu isotope fractionation factors between Cu-bearing sulfides (chalcopyrite, bornite, and chalcocite) and CuCl2–. However, the Δ65Cusolid-aqueous moved progressively further from equilibrium with prolonged reaction time, with fractionation factors ranging from approximately –0.6 ‰ to –1.2 ‰. We found that significant fractionation of Cu isotopes between the solid products and aqueous solution was mainly controlled by the amount of chalcopyrite that formed in the product layers. We interpret that the Δ65Cusolid-aqueous was controlled by the diffusion of aqueous Cu(I) species among the product layers and the changes in Cu redox state during the precipitation of chalcopyrite. These results imply that the δ65Cu values measured in sulfides from low-temperature hydrothermal deposits may be controlled by the local chemistry of the fluids in product layers that precipitate sulfides. This study highlights the importance of local fluid characteristics, such as redox conditions, metal speciation, and diffusion, in controlling isotope fractionation pathways during non-equilibrium mineral replacement.

Micrometric pyrite catalyzes abiotic sulfidogenesis from elemental sulfur and hydrogen

Hydrogen sulfide (H2S) in environments with temperatures below 100 °C is generally assumed to be of microbial origin, while abiotic H2S production is typically restricted to higher temperatures (T). In this study, we report an abiotic process for sulfidogenesis through the reduction of elemental sulfur (S0) by hydrogen (H2), mediated by pyrite (FeS2). The process was investigated in detail at pH 4 and 80 °C, but experimental conditions ranged between 40 and 80 °C and pH 4–6. The experiments were conducted with H2 as reducing molecule, and µm-sized spherical (but not framboidal) pyrite particles that formed in situ from the H2S, S0 and Fe2+ present in the experiments. Fe monosulfides, likely mackinawite, were identified as potential pyrite precursors. The absence of H2 production in controls, combined with geochemical modelling, suggests that pyrite formation occurred through the polysulfide pathway, which is unexpected under acidic conditions. Most spherical aggregates of authigenic pyrite were composed of nanometric, acicular crystals oriented in diverse directions, displaying varying degrees of organization. Although it was initially hypothesized that the catalytic properties were related to the surface structure, commercially sourced, milled pyrite particles (< 50 μm) mediated H2S production at comparable rates. This suggests that the catalytic properties of pyrite depend on particle size rather than surface structure, requiring pyrite surfaces to act as electron shuttles between S0 and H2.

Synergistic adsorption of ethyl xanthate and butyl xanthate on pyrite surfaces: A DFT study

AbstractPyrite is the most widely distributed sulfide mineral with a wide range of uses, and pyrite is mainly recovered by means of flotation in practical production, and the commonly used flotation collectors are mainly xanthates with good flotation performance. The adsorption behavior of commonly used collectors ethyl xanthate and butyl xanthate on the surface of pyrite is investigated by using the density functional tight bounding theory (DFTB). The results show that when a single reagent acts on the pyrite surface, butyl xanthate has a stronger effect than ethyl xanthate, and the adsorbed mineral surface shows obvious hydrophobicity. The interaction between ethyl xanthate and butyl xanthate had a stronger effect than that of a single reagent, and the simulation of the flotation environment at ordinary temperature using molecular dynamics revealed that the synergistic adsorption of the two different reagents on the surface of pyrite was more hydrophobic, that is, the synergistic adsorption of the combined collector of ethyl xanthate and butyl xanthate on the surface of pyrite was stronger. The results of the study are of great significance for the synergistic effect between the combined collector and the mineral.

An evaluation of pyrite as a component of respirable coal dust

Over the past two decades, the rise in coal worker’s pneumoconiosis has prompted research into the effects of respirable coal dust components. This study explores how coal-pyrites produce hydroxyl radicals (•OH), a reactive oxygen species closely associated with particle toxicity, and assesses the ability of safe chemical additives to reduce •OH production at various pH levels. Promising candidates were evaluated in various solutions, including tap and process waters and simulated lung fluid. We employed electrokinetic measurements, infrared and X-ray photoelectron spectroscopies, and ab initio atomistic simulations to analyze particle surfaces. The study also looked at how surface aging affects •OH production. Our results show that •OH generation of the pyrite varies and is catalyzed by elements like silicon, aluminum, and iron in pyrite. Carboxymethyl cellulose was effective in reducing •OH production by targeting surface sulfide and silicon sites and affecting surface hydration and charge. Atmospheric aging was found to increase •OH production, especially in the pyrite with high iron and silicon and low calcium contents, relative to other samples. This highlights the role of the pyrite surface properties and chemical composition, and the solution pH and composition in •OH generation by coal-pyrites.

Treatment of eutrophic water in pyrite-filled constructed wetland integrated with microelectrolysis driven by iron/sulfur cycle: Performance and mechanism

This study developed a microelectrolysis-integrated constructed wetland with pyrite filler around the cathode (e-PCW) to treat eutrophic water. Results indicated that e-PCW effectively enhanced pyrite dissolution, converting solid-phase electron donors into bioavailable forms, thereby facilitating the enrichment of various denitrifying bacteria on pyrite surfaces. Importantly, iron-reducing and sulfur-reducing bacteria attached to the pyrite surfaces enhanced the conversion of ferric iron and sulfate, thereby driving iron and sulfur cycles and promoting electron transfer. Therefore, synergistic effects of pyrite and microelectrolysis made e-PCW achieve higher total nitrogen (TN) and total phosphorus (TP) removal efficiencies. With a hydraulic retention time of 24 h, the highest removal efficiencies of TN and TP achieved 78% and 75%, respectively. Furthermore, when eutrophic water containing high concentration of algae was fed into e-PCW, it consistently demonstrated superior TN and TP removal capabilities. This work provides a valuable approach to optimizing constructed wetland technology for treating eutrophic water.

Kinetics study on the temperature-dependent reduction of aqueous U(VI) by natural pyrite

Previous studies have indicated that acid-washed pyrite is inert toward aqueous U(VI) under most pH conditions at ambient temperature, even though insoluble UO2 is the thermodynamically predicted product for the reduction of U(VI) by pyrite. Considering the exothermic nature of nuclear waste, the interaction between uranyl nitrate/acetate and natural pyrite was studied at temperatures ranging from 25 °C to 85 °C and at pH values between ∼4.0 and ∼9.5, to simulate the scenarios encountered in a high-level radioactive waste repository. The results revealed that the reactivity of pyrite toward aqueous U(VI) significantly increased with rising temperature, and the reaction could be described by a pseudo-first-order kinetic equation. Activation energies were calculated to be 79.4 ± 10.6 and 45.7 ± 3.8 kJ⋅mol−1 for the reduction of uranyl nitrate, and 78.2 ± 5.2 and 42.2 ± 5.8 kJ⋅mol−1 for the reduction of uranyl acetate, at pH values of ∼4.5 and ∼5.0, respectively. These values indicate that the reaction is controlled by the surface chemical processes. In addition, the complete reduction of aqueous U(VI) to UO2 product was first observed for the reactions at pH ∼4.0 to ∼5.5 when the temperature was ≥75 °C. Conversely, non-stoichiometric UO2+x(s) (0 < x ≤ 0.67) was found at lower temperatures within the same pH range, and also at 85 °C with a reaction pH of ∼9.5. Moreover, the ratio of reduced U(IV/V) on pyrite surfaces increased gradually over time, indicating that reaction time played a significant role in the reduction products. The findings are essential not only for the safety assessment of the high-level radioactive waste repository, but also for understanding the metallogenic mechanism of U(IV)-bearing ore deposits under the relevant anaerobic and hydrothermal conditions.

Maximizing pollutant removal and greenhouse gas emission reduction in vertical flow constructed wetlands: an orthogonal experimental approach.

Owing to the impact of the effluent C/N from the secondary structures of urban domestic wastewater treatment plants, the denitrification efficiency in constructed wetlands (CWs) is not satisfactory, limiting their widespread application in the deep treatment of urban domestic wastewater. To address this issue, we constructed enhanced CWs and conducted orthogonal experiments to investigate the effects of different factors (C/N, fillers, and plants) on the removal of conventional pollutants and the reduction of greenhouse gas (GHG) emission. The experimental results indicated that a C/N of 8, manganese sand, and calamus achieved the best denitrification efficiencies with removal efficiencies of 85.7%, 95.9%, and 88.6% for TN, NH4+-N, and COD, respectively. In terms of GHG emission reduction, this combination resulted in the lowest global warming potential (176.8mg/m2·day), with N2O and CH4 emissions of 0.53 and 1.25mg/m2·day, respectively. Characterization of the fillers revealed the formation of small spherical clusters of phosphates on the surfaces of manganese sand and pyrite and iron oxide crystals on the surface of pyrite. Additionally, the surface Mn (II) content of the manganese sand increased by 8.8%, and the Fe (III)/Fe (II) and SO42-/S2- on pyrite increased by 2.05 and 0.26, respectively, compared to pre-experiment levels. High-throughput sequencing indicated the presence of abundant autotrophic denitrifying bacteria (Sulfuriferula, Sulfuritalea, and Thiobacillus) in the CWs, which explains denitrification performance of the enhanced CWs. This study aimed to explore the mechanism of efficient denitrification and GHG emission reduction in the enhanced CWs, providing theoretical guidance for the deep treatment of urban domestic wastewater.