Cadmium (Cd) is one dangerous and widespread heavy metal that of great environmental concern. To cost-efficiently adsorb aqueous Cd under influence of various factors, this study succeeded in fabricating goethite-modified biochar (GBC) derived from distillers’ grains (DGs) for Cd sorption of different concentrations (10–100 mg L⁻¹) at pH of 3, 6 and 8 with and without microcystin-LR (MC-LR). Sorption kinetics and isotherms data revealed that Cd sorption capacity of GBC and unmodified BC increased as pH elevated from 3 to 6 but stabilized when pH further elevated to 8. Pseudo-second-order and Langmuir models more accurately fitted to sorption data for both BCs, implying monolayer chemisorption of Cd onto BCs. GBC exhibited more robust sorption for each Cd concentration than unmodified BC, with the maximum sorption capacity of around 28 mg g⁻¹ at neutral and weak alkaline pH. Notably, goethite-modification obviously increased bulk polarity, specific surface area, porosity and surface oxygenic group abundance of BC, thus strongly enhancing Cd sorption by creating more sorption sites mainly via pore-filling, electrostatic attraction, and also via complexation and cation exchange. Co-existing MC-LR of 100 μg L⁻¹ did not obviously affect Cd sorption by both BCs for most Cd levels at each pH, mostly because sorption mechanisms diverged between MC-LR and Cd to largely avoid their competition for sorption sties. Thus, goethite could modify DG-BC as promising and cost-efficient sorbent for Cd even with co-existing MC-LR, especially at neutral and weak alkaline pH that common in the nature. This study was greatly implicated in modifying and applying DG-BC for Cd immobilization in MC-LR laden waters with various pH circumstances.

The massive generation of medical waste (MW) results in a series of environmental, social, and ecological problems. Pyrolysis is one such approach that has attracted more attention because of the production of value-added products with lesser environmental risk. In this study, the activated biochar (ABC600) was obtained from MW pyrolysis and activated with KOH. The adsorption mechanism of activated biochar on cationic (methylene blue) and anionic (reactive yellow) dyes were studied. The physicochemical characterization of biochar showed that increasing pyrolysis temperature and KOH activation resulted in increased surface area, a rough surface with a clear porous structure, and sufficient functional groups. MB and RYD-145 adsorption on ABC600 was more consistent with Langmuir isotherm (R² ≥ 0.996) and pseudo-second-order kinetics (R² ≥ 0.998), indicating chemisorption with monolayer characteristics. The Langmuir model fitting demonstrated that MB and RYD-145 had maximum uptake capacities of 922.2 and 343.4 mg⋅g⁻¹. The thermodynamics study of both dyes showed a positive change in enthalpy (ΔH°) and entropy (ΔS°), revealing the endothermic adsorption behavior and randomness in dye molecule arrangement on activated-biochar/solution surface. The activated biochar has excellent adsorption potential for cationic and anionic dyes; hence, it can be considered an economical and efficient adsorbent.

Dissolved organic matter (DOM) plays a significant role in the photochemical behavior of nano- and micro-plastic particles (NPs/MPs). We investigated the influence of DOM on the mechanism on the photoaging of NPs/MPs with different molecular structures under UV₃₆₅ irradiation in water. DOM components used in this study are mainly humic acid and fulvic acid. The results showed that DOM promoted the weathering of aliphatic NPs/MPs (polypropylene (PP)), but inhibited or had only a minor effect on the photoaging of aromatic NPs/MPs (polystyrene (PS) NPs/MPs, carboxyl-modified PS NPs, amino-modified PS NPs, and polycarbonate MPs). NPs with a large surface area may adsorb sufficient DOM on the particle surfaces through π-π interactions, which competes with NPs for photon absorption sites, thus, can delay the photoaging of PS NPs. Aromatic MPs may release phenolic compounds that quench •OH, thereby weakening the photoaging process. For aliphatic MPs, the detection of peracid, aldehyde, and ketone groups on the polymer surface indicated that DOM promoted weathering of PP MPs, which was primarily because the generation of •OH due to DOM photolysis may attack the polymer by C–C bond cleavage and hydrogen extraction reactions. This study provides insight into the UV irradiation weathering process of NPs/MPs of various compositions and structures, which are globally distributed in water.

Iron (III) co-precipitation with dissolved organic matter (DOM) is pervasive in many natural environments. However, the effects of DOM on the formation of Fe(III) hydroxysulfate (FHS) and its environmental implications are poorly understood. In this study, fulvic acid (FA) was used as a model DOM compound, and experiments were devised to investigate the effects of FA on the formation of FHS. In addition, the Pb(II) adsorption capabilities of FHSs biosynthesized under various FA dosages, including kinetics and sorption isotherm experiments, were conducted. These experiments showed that co-precipitation of FA promoted the formation of Fe-FA composites, FA-doped schwertmannite, and small particles of jarosite. Co-precipitates are more enriched in carboxyl (–COOH) functional groups due to their preferential binding with FHS. The adsorption kinetics, isotherms and mechanisms of Pb onto the biosynthesized FHSs were then comprehensively characterized and modeled. Though the specific surface area decreased with increasing FA loading, the introduction of FA into FHSs increased Pb(II) adsorption, with the highest concentration of FA addition improving the removal capacity of Pb(II) to 91.54%. Kinetics studies and intra-particle diffusion models indicated that the adsorption of Pb(II) onto the FHSs was correlated with the number of active sites, and two adsorption steps: surface adsorption and the diffusion of Pb(II) in channels inside the biosynthesized FHSs, are suggested. The adsorption mechanism was attributed to cation exchange between Pb(II) and –OH and –COOH functional groups, and the co-precipitated FA provided additional sites for Pb(II) adsorption by FHS.

Although biochar supports were widely adopted to fabricate the biochar (BC) supported layered double hydroxides (LDHs) composites (LDH-BC) for efficient environmental remediation, few studies focus on the important role of biochar support in alleviating the stacking of LDHs and enhancing LDH-BC's performance. Through the analysis of the material structure-performance relationship, the “support effect” of fine biochar prepared by ball milling was carefully explored. Compared with the original LDHs on LDH-BC, the LDHs on ball milled biochar (LDH-BMBC) had smaller particle size (from 1123 nm to 586 nm), crystallite size (from 20.5 nm to 6.56 nm), more abundant O-containing functional groups, and larger surface area (370 m² g⁻¹) and porous structure. The Langmuir model revealed that the maximum theoretical phosphate adsorption capacity of LDH-BMBC (56.2 mg P g⁻¹) was significantly higher than that of LDH-BC (27.6 mg P g⁻¹). The leaching experiment proved that the addition of LDH-BMBC in calcareous soil could significantly reduce the release of soil total phosphate (46.1%) and molybdate reactive phosphate (40.4%), even though pristine BC and BMBC significantly enhanced the soil phosphate leaching. This work fabricated high-performance and eco-friendly LDH-BMBC for phosphate adsorption in solution and phosphate retention in soil and also provide valuable insights into fine biochar support effect on LDHs exfoliation, extending the practical use of the engineered ball milled biochars in environment remediation.

Removal of multi-ionic contaminants from water resources has been a major challenge faced during the treatment of water for drinking and industrial applications. In the present study, varying composition of magnesium doped hydroxyapatite (Mg-HAp) and zeolite nanocomposite embedded porous polymeric beads were synthesized using solvent displacement method and its sorption efficiency towards multi-ion contaminant (such as Ag, Al, As, Ba, Be, Cd, Co, Cr, Cu, Mn, Ni, Pb, Se, Tl, Th, U, V and Zn) was investigated in aqueous solution and spiked groundwater. The prepared beads were characterized using suitable techniques like high-resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), and Brunauer-Emmett-Teller (BET) equation. The surface area and pore radius of the beads varied from 6.996 to 66.469 m²/g and 1.698–3.960 nm respectively according to the composition of the bead. The control bead without nanocomposite showed maximum surface area. Multi-ion adsorptions onto beads were confirmed using an inductively coupled plasma-optical emission spectrophotometer (ICP-OES) and X-ray photoelectron spectrophotometer (XPS). The sorption efficiency was high at pH 5 owing to its anionic surface charge leading to an increase in affinity towards the cations. For validating field application, selected high performance beads were tested in multi-ion spiked groundwater. The results indicated that the Mg-HAp nanocomposite bead dominate all the other bead compositions with more than 90% removal efficiency for most of the multi-ion contaminants. The feasible adsorption mechanism has been discussed. This adsorption study revealed that the Mg-HAp nanocomposite bead is a promising material that is cost-effective, non-toxic, biodegradable, eco-friendly and highly efficient towards the removal of multi-ionic contaminants from groundwater.

The removal of antibiotics in subsurface flow constructed wetlands is performed through various removal mechanisms, such as adsorption, hydrolysis, microbial degradation and plant uptake. However, the contribution rates of the removal mechanisms in constructed wetlands are still not well studied. This study conducted a series of experiments and used multivariate statistical analysis to determine contribution rates for substrate adsorption, hydrolysis, and microbial degradation. Multiple stepwise regression analysis indicated that specific surface area and salt content were the main factors influencing sulfonamide adsorption, while temperature and pH were the main factors influencing sulfonamide hydrolysis. Variance partitioning analysis showed that the influence of physical-chemical factors was greater than that of nutrients on the microbial community. Partial least squares path analysis showed that the path coefficients of microbial degradation, adsorption and hydrolysis for sulfonamides removal in vertical subsurface flow constructed wetlands were 0.6339, 0.3608 and 0.0351, respectively, while the corresponding path coefficient were 0.5658, 0.4707 and 0.1079 in horizontal subsurface flow constructed wetlands, respectively. This means that microbial degradation contributes the most to the removal of sulfonamides in subsurface flow constructed wetlands. Enhanced microbial degradation may be a powerful measure to improve the removal of sulfonamides. These results will be helpful for understanding the removal mechanism of antibiotics and will provide a definite direction for pertinently improving sulfonamide removal efficiency in constructed wetlands.

Zero valent iron-loaded biochar (Fe⁰-BC) has shown promise for the removal of various organic pollutants, but is restricted by reduced specific surface area, low utilization efficiency and limited production of reactive oxygen species (ROS). In this study, iron carbide-loaded activated biochar (Fe₃C-AB) with a high surface area was synthesized through the pyrolysis of H₃PO₄ activated biochar with Fe(NO₃)₃, tested for removing bisphenol A (BPA) and elucidated the adsorption and degradation mechanisms. As a result, H₃PO₄ activated biochar was beneficial for the transformation of Fe⁰ to Fe₃C. Fe₃C-AB exhibited a significantly higher removal rate and removal capacity for BPA than that of Fe⁰-BC within a wide pH range of 5.0–11.0, and its performance was maintained even under extremely high salinity and different water sources. Moreover, X-ray photoelectron spectra and density functional theory calculations confirmed that hydrogen bonds were formed between the COOH groups and BPA. ¹O₂ was the major reactive species, constituting 37.0% of the removal efficiency in the degradation of BPA by Fe₃C-AB. Density functional reactivity theory showed that degradation pathway 2 of BPA was preferentially attacked by ROS. Thus, Fe₃C-AB with low cost and excellent recycling performance could be an alternative candidate for the efficient removal of contaminants.

In recent years, biochar has become of considerable interest for environmental applications, it can be used as a catalyst for sulfides reduction of perchloroethylene, but the crucial role of biochar properties played in catalyzing dechlorination remained ambiguous investigation. To pinpoint the critical functional groups, the modified biochars were respectively produced by HNO₃, KOH and H₂O₂ with similar dimensional structures but different functional groups. Combined with the adsorption and catalytic results of different biochars, the acid-modified biochar had the best catalytic performance (99.9% removal) due to the outstanding specific surface area and ample functional groups. According to characterization and DFT results, carboxyl and pyridine nitrogen exhibited a positive correlation with the catalytic rate, indicating that their contribution to catalytic performance. Customizing biochar with specific functional groups removed depth demonstrated that the carboxyl was essential component. Further, alkaline condition was conducive to catalytic reduction, while tetrachloroethylene cannot be reduced under acidic conditions, because HS⁻ and S²⁻ mainly existed in alkaline environment and the sulfur-containing nucleophilic structure formed with biochar was more stable under this condition. Overall, this study opens new perspectives for in situ remediation by biochar in chlorinated olefin polluted anoxic environment and promotes our insight of modifying for biochar catalyst design.