One attraction of using hydrochar (HC) and biochar (BC) in soil is their intrinsic affinity for organic contaminants. Oxidative ageing is likely to induce changes in physicochemical properties and functionality. To explore the long-term potential trajectories for corn stalk HC and BC to adsorb organic pollutants, we employed HC and BC exposure in 5% H2O2 to simulate oxidative ageing and get insights into mechanisms of atrazine adsorption on fresh and artificially aged materials. The physicochemical properties of fresh and aged materials were systematically compared using elemental analysis, SSA, FTIR, XPS and SEM-EDS, alongside K2Cr2O7/H2SO4 treatment to assess chemical oxidation stability. Atrazine is a typical herbicide chemical and hydrophobic organic pollutant. Adsorption isotherms of atrazine were used to reveal differences in mechanisms of sorption to BC and HC, by assessment before and ageing. BC freshly produced at 650 °C displayed higher capacity for atrazine sorption than BC produced at 500 °C, with a dominant role for π-π EDA interactions. The sorption capacity of HC freshly produced at 250 °C was higher than for HC produced at 200 °C HC, owing to higher C content and atrazine partitioning into the organic phase. Ageing increased the surface abundance of oxygenated functional groups for BC and HC and diminished bulk aromaticity. After ageing, atrazine sorption by high temperature BC was lower, but for HC it was increased. Such divergent effects must be considered when developing strategies to co-manage contaminants and carbon through the addition of carbonized materials to land.

In the present study, the competitive adsorption of Cu²⁺, Pb²⁺, and Cd²⁺ by a novel natural adsorbent (i.e., argillaceous limestone) modified with chitosan (C-AL) was investigated. The results demonstrated that both intraparticle diffusion and chemisorption marked significant contributions to the Cu²⁺ adsorption process by both raw argillaceous limestone (R-AL) and C-AL in mono-metal adsorption systems. Antagonism was found to be the predominant competitive effect for Cu²⁺, Pb²⁺ and Cd²⁺ adsorptions by C-AL in the multi-metal adsorption system. The three-dimensional simulation and FTIR analysis revealed that the presence of Cu²⁺ suppressed Pb²⁺ and Cd²⁺ adsorptions, while the effect of Cd²⁺ on Cu²⁺ and Pb²⁺ adsorptions was insignificant. The spectroscopic analyses evidenced that amide groups in C-AL played a crucial role in metal adsorption. The preferential adsorptions of Pb²⁺ > Cu²⁺ > Cd²⁺ were likely due to the different affinities of the metals to the lone pair of electrons on the N atom from the amide groups and/or the O atoms from the –OH and -COO⁻ groups on C-AL. The interactions between C-AL and metal ions and between various metal species influenced their competitive adsorption behaviors. C-AL exhibited a superior metal adsorption capacity in comparison with that the capacities of other natural adsorbents reported during the last decade, suggesting its potential practical applications.

The development of high-efficiency adsorbents and the exploration of their adsorption mechanisms are major challenges in environmental remediation. Herein, MIL-100 was prepared, characterized, and utilized for the adsorptive removal of diclofenac sodium (DCF) from aqueous solutions. A high monolayer adsorption capacity of 773 mg g⁻¹ was recorded. The adsorption mechanism was proposed based on different contributions of two types of pore structure of MIL-100 to the adsorption of DCF from aqueous solutions according to the experimental results and theoretical calculation. During adsorption process, DCF (5.2 × 7.4 × 10.3 Å) diffused through the free area of hexagonal pores (8.6 × 8.6 Å) into the cages of MIL-100, whilst it was adsorbed by the pentagonal pores (4.8 × 5.8 Å) preferentially. Internal mass transfer resistance, which was identified as one of the dominant rate-limiting steps by the mass transfer resistance kinetic models based on the Sips model, will be derived from the diffusion process, which was affected by the size-sieving effect of the pore structure of MIL-100. The successful diffusion of DCF into the interior of MIL-100 and the stable configuration between MIL-100 and DCF accounted for the high adsorption capacity. The capture of DCF into MIL-100 also resulted in the pore size distribution variation of adsorbent, which provided vital experimental evidence for the proposed mechanism. This study may offer deeper insights into other pollutants removal by metal-organic frameworks type adsorbents.

The long-term use of animal manure in agriculture has resulted in estrogen pollution, which poses risks to facility vegetable soils. Owing to the complex soil composition, estrogen may exhibit a variety of behaviors at the water/soil interface. This study demonstrated the role of humic acid (HA) on the 17β-estradiol (E2) adsorption by clay minerals (montmorillonite, kaolinite, and hematite). The interfacial behaviors were investigated using adsorption kinetics and isotherms data. Then, the effects of temperature, pH, and bisphenol A (BPA) on the interactions between humic-mineral complexes and E2 were explored. The adsorption of E2 is an exothermic and spontaneous process, and the addition of HA to minerals significantly promoted their E2 adsorption capacities. Higher pH levels (>10) and the presence of BPA decreased the adsorption capacities of minerals and mineral complexes for E2. Moreover, intercalation, hydrophobic partitioning, π-π interactions and hydrogen bonding could dominate the E2 adsorption onto complexes. These results provided insight into the interfacial behaviors of E2 on the surfaces of humic-mineral complexes and promoted the understanding of the migration and transport of estrogens in soils.

Proper management of waste crop residues has been an environmental concern for years. Yellow mealworms (larvae of Tenebrio molitor Linnaeus, 1758) are major insect protein source. In comparison with normal feed wheat bran (WB), we tested five common lignocellulose-rich crop residues as feedstock to rear mealworms, including wheat straw (WS), rice straw (RS), rice bran (RB), rice husk (RH), and corn straw (CS). We then used egested frass for the production of biochar in order to achieve clean production. Except for WS and RH, the crop residues supported mealworms’ life activity and growth with consumption of the residues by 90% or higher and degraded lignin, hemicellulose and cellulose over 32 day period. The sequence of degradability of the feedstocks is RS > RB > CS > WS > RH. Egested frass was converted to biochar which was tested for metal removal including Pb(II), Cd(II), Cu(II), Zn(II), and Cr(VI). Biochar via pyrolysis at 600 °C from RS fed frass (FRSBC) showed the best adsorption performance. The adsorption isotherm fits the Langmuir model, and kinetic analysis fits the Pseudo-Second Order Reaction. The heavy metal adsorption process was well-described using the Intra-Particle Diffusion model. Complexation, cation exchange, precipitation, reduction, deposition, and chelation dominated the adsorption of the metals onto FRSBC. The results indicated that crop residues (WS, RS, RB, and CS) can be utilized as supplementary feedstock along with biochar generated from egested frass to rear mealworms and achieve clean production while generating high-quality bioadsorbent for environment remediation and soil conditioning.

Antibiotics in water and soil are persistent, bioaccumulative and toxic to aquatic organisms and human health. To address it, as one of the new technologies, green synthesized magnetic Fe₃O₄ nanoparticles by Excoecaria cochinchinensis extract used to remove rifampicin (RIF) was investigated in this study. Results showed the adsorption efficiency of RIF reached 98.4% and the maximum adsorption capacity is 84.8 mg/g when 20 mL of RIF at a concentration of 20 M was adsorbed by 10 mg Fe₃O₄ at a temperature of 303 K. The morphology of the green Fe₃O₄ characterized by SEM demonstrated the dimensions ranging from 20 to 30 nm. The N₂ adsorption/desorption isotherms revealed that the surface area of Fe₃O₄ was 111.8 m²/g. In addition, adsorption studies indicated that the kinetics fitted the pseudo second-order and isothermal adsorption conformed to the Langmuir isotherm. Furthermore, due to their magnetic properties, the Fe₃O₄ nanoparticles were easily separated and reused and the mechanism for removing RIF occurred through adsorption rather than chemical redox reaction. Finally, the reusability of Fe₃O₄ for adsorption of RIF showed that the removal efficiency decreased to 61.5% after five cycles.

Norfloxacin (NOR) is a persistent organic pollutant and can be effectively removed from effluent by adsorption of biochar. However, the presence of other emerging contaminants, such as surfactants, will potentially alter adsorption performance of norfloxacin by biochar and the molecular-scale mechanisms of the interaction between surfactants and biochar remain poorly understood. In this study, adsorption of norfloxacin on magnetic biochar prepared with iron-containing furfural residue (FRMB) in the presence or absence of anionic surfactants was investigated. The adsorption of NOR was significantly affected by the initial pH and anionic surfactants-sodium dodecyl sulfate (SDS) and sodium dodecyl benzene sulfonate (SDBS). In the presence of SDS and SDBS, the maximum sorption capacities of NOR were 2.33 and 1.97 times higher than that in the absence of surfactants, reached to 698.6 mg g⁻¹ and 589.9 mg g⁻¹, respectively. The optimal pH condition which was 4 indicated that electrostatic adsorption played a decisive role in the adsorption process after introduction of SDS/SDBS. The adsorption data were fitted well by the Elovich model and Freundlich model at the optimal conditions in which both SDS and SDBS were hemimicelle (0.8 mM SDS or 0.4 mM SDBS), indicating surface heterogeneity of FRMB and the adsorption mechanism was related to the assembly of surfactants on biochar. FTIR results showed that FRMB and SDS/SDBS interacted through hydrophobic action, and more complex or aggregates were formed between the NOR and biochar/SDS/SDBS. This work highlights the synergistic enhancement effects of tested surfactants on the removal of NOR by magnetic biochar from aqueous systems.

Degrading aquatic organic pollutants efficiently is very important but strongly relied on the design of photocatalysts. Porous graphene could increase photocatalytic performance of ZnO nanoparticles by promoting the effective charge separation of electron-hole pairs if they can be composited. Herein, porous graphene, ZnO nanoparticles and porous graphene/ZnO nanocomposite were prepared by fine tuning of partial combustion, which graphene oxide imperfectly covered by the layered Zn salt was combusted under muffle furnace within few minutes. Resulting ZnO nanoparticles (32–72 nm) are dispersed uniformly on the surface of graphene sheets, the pore sizes of porous graphene are in the range from ∼3 to ∼52 nm. The synthesized porous graphene/ZnO nanocomposite was confirmed to show enhanced efficiency under natural sunlight irradiation compared with pure ZnO nanoparticles. Using porous graphene/ZnO nanocomposite, 100% degradation of methyl orange can be achieved within 150 min. The synergetic effect of photocatalysis and adsorption is main reason for excellent MO degradation of PG/ZnO nanocomposite. This work may offer a new route to accurately prepare porous graphene-based nanocomposite and open a door of their applications.

Fly ash (FA), a solid waste generated in thermal power plants, is considered an environmental pollutant. Therefore, measures must be taken to dispose of FA in an environmentally friendly manner. In this paper, an electrospinning technique was employed to incorporate FA particles onto zinc oxide nanofibers (ZnO NFs), and the product (FA/ZnO composite) was used for the removal of methylene blue (MB) from the water. Herein, ZnO NFs may serve as effective semiconductor photocatalysts and provide sufficient surface area for FA, while the FA particles serve as an effective adsorbent. The adsorption capacity and photocatalytic efficiency of the as-synthesized nanocomposite fibers were enhanced compared to those of the pristine ZnO NFs, and this result is attributed to the uniform distribution of FA on the surface of the ZnO NFs. The as-synthesized nanocomposite could have great significance in wastewater treatment.

To investigate the removal characteristics of ammonium-nitrogen (NH₄⁺-N), nitrite-nitrogen (NO₂⁻-N), nitrate-nitrogen (NO₃⁻-N), and total nitrogen from groundwater by a degradable composite active medium, kinetics, thermodynamics, and equilibrium adsorption, experiments were performed using scoria and degrading bacteria immobilized on scoria. Removal of NH₄⁺-N, NO₂⁻-N, and NO₃⁻-N was conducted in adsorption experiments using different times, initial concentrations, pH values, and groundwater chemical compositions (Ca²⁺, Mg²⁺, HCO₃⁻, CO₃²⁻, Fe²⁺, Mn²⁺, and SO₄²⁻). The results showed that the removal of nitrogen by the composite active medium was obviously better than that of scoria alone. The removal rates of NH₄⁺-N (C₀ = 5 mg/L), NO₂⁻-N (C₀ = 5 mg/L), and NO₃⁻-N (C₀ = 100 mg/L) by the composite active medium within 1 h were 96.05%, 82.40%, and 83.16%, respectively. The adsorption kinetics were well fitted to a pseudo-second order model, whereas the equilibrium adsorption agreed with the Freundlich model. With changes in the pH, variation in the removal could be attributed to the combined effect of hydrolysis and competitive ion adsorption, and the optimum pH was 7. Different concentration conditions, hardness, alkalinity, anions, and cations showed different promoting and inhibiting effects on the removal of nitrogen. A careful examination of ionic concentrations in adsorption batch experiments suggested that the sorption behavior of nitrogen onto the immobilized medium was mainly controlled by ion exchange. The degrading bacteria on the scoria surface were eluted and analyzed by metagenomic sequencing. There were significant differences in the number of operational taxons, relative abundances, and community diversity among degrading bacteria after adsorption of the three forms of nitrogen. The relative abundance of degrading bacteria was highest after NO₃⁻-N removal, and the diversity was highest after NO₂⁻-N removal. Pseudomonas and Serratia were the dominant genera that could efficiently remove NH₄⁺-N and NO₂⁻-N.