The oxidative potential (OP) of atmospheric fine particulate matter (PM₂.₅) has been linked to organic content, which includes polycyclic aromatic hydrocarbons (PAHs). The OP of 135 individual PAHs (including six subclasses) was measured using the dithiolthreitol (DTT) consumption assay. The DTT assay results were used to compute the concentration of each PAH needed to consume 50% of the DTT concentration in the assay (DTT₅₀), and the reduction potential of the PAHs (ΔGᵣₓₙ). Computed reduction potential results were found to match literature reduction potential values (r² = 0.97), while DTT₅₀ results had no correlations with the computed ΔGᵣₓₙ values (r² < 0.1). The GINI equality index was used to assess the electron distribution across the surface of unreacted and reacted PAHs. GINI values correlated with ΔGᵣₓₙ in UPAH, HPAH, and OHPAH subclasses, as well as with all 135 PAHs in this study but did not correlate with DTT₅₀, indicating that electron dispersion is linked to thermodynamic reactions and structural differences in PAHs, but not linked to the OP of PAHs. Three ambient PM₂.₅ filters extracts were measured in the DTT assay, alongside mixtures of analytical standards prepared to match PAH concentrations in the filter extracts to test if the OP follows an additive model of toxicity. The additive prediction model did not accurately predict the DTT consumption in the assay for any of the prepared standard mixtures or ambient PM₂.₅ filter extracts, indicating a much more complex model of toxicity for the OP of PAHs in ambient PM₂.₅. This study combined computed molecular properties with toxicologically relevant assay results to probe the OP of anthropogenically driven portions of ambient PM₂.₅, and results in a better understanding of the complexity of ambient PM₂.₅ OP.

In this study, a novel biosorbent is prepared from the pods of Bauhinia variegata is used for defluoridation of the fluoride contaminated water. It is an eco-friendly and economically feasible material. Comparison of adsorption capacity of Physically Treated Bauhinia (PTB) and Chemically Treated Bauhinia (CTB) are carried in this work. Characterization studies like SEM, EDS, FTIR, and XRD are executed to analyze surface morphology and functional groups in PTB and CTB. The experimental procedure was implemented in a batch process where the operating constraints such as dosage, pH, initial fluoride concentration, time, and temperature are varied to attain optimized efficiency. PTB and CTB yield an adsorption capacities of 10.90 mg/g and 15.45 mg/g respectively in the batch process. PTB adheres fluoride in monolayer formation whereas CTB forms multilayer adsorption. The adsorption process was described by the Pseudo first-order model to state the mechanism of physisorption. The negative values of thermodynamic parameters indicate spontaneity and favorable conditions for adsorption process. As CTB has a higher adsorption capacity than PTB, the batch study has been extended to column adsorption. Bed depth, initial fluoride concentration, and flow rate are the experimental variables used to acquire breakthrough curves. Simplified column models like Adam-Bohart, Thomas, and Yoon-Nelson models were analyzed. In column studies, Yoon-Nelson model fitted well in describing the process of adsorption. The maximum adsorption capacity acquired during the column process was found to be 1.176 mg/g with a bed depth of 5 cm and a flow rate of 5 ml/min. Thus, the innocuous and sustainable adsorbent is developed and serves as an excellent defluoridation agent.

In this study, a sustainable NH₂-MIL-101(Al) is synthesized and subjected to characterization for cryogenic CO₂ adsorption, isotherms, and thermodynamic study. The morphology revealed a highly porous surface. The XRD showed that NH₂-MIL-101(Al) was crystalline. The NH₂-MIL-101(Al) decomposes at a temperature (>500 °C) indicating excellent thermal stability. The BET investigation revealed the specific surface area of 2530 m²/g and the pore volume of 1.32 cm³/g. The CO₂ adsorption capacity was found to be 9.55 wt% to 2.31 wt% within the investigated temperature range. The isotherms revealed the availability of adsorption sites with favorable adsorption at lower temperatures indicating the thermodynamically controlled process. The thermodynamics showed that the process is non-spontaneous, endothermic, with fewer disorders, chemisorption. Finally, the breakthrough time of NH₂-MIL-101(Al) is 31.25% more than spherical glass beads. The CO₂ captured by the particles was 2.29 kg m⁻³. The CO₂ capture using glass packing was 121% less than NH₂-MIL-101(Al) under similar conditions of temperature and pressure.

Excessive copper (Cu) in contaminated soil and groundwater has attracted continuous attentions due to the bioaccumulation and durability. In this study, the feasibility of remediation of heavy metal pollution in soil and groundwater was investigated using hydroxyapatite/calcium silicate hydrate (HAP/C–S–H) recovered from phosphorus-rich wastewater in farmland. The results show that the pH has a strong effect on copper removal from Cu-contaminated groundwater but the impact of ion strength on the removal is weak. In general, high pH and low ion strength give better results in copper removal. Kinetic and isotherm data from the study fit well with Pseudo-second-order kinetic model and Langmuir isotherm model, respectively. The maximum adsorption capacity of HAP/C–S–H (138 mg/g) was higher than that of C–S–H (90.3 mg/g) when pH value, temperature, and ionic strength were 5, 308 K, and 0.01 M, respectively. Thermodynamics results indicate that Cu removal is a spontaneous and endothermic process. X-ray diffraction (XRD) results show that the mechanism of copper removal involves physical adsorption, chemical precipitation and ion exchange. For the remediation of Cu-contaminated soil, 76.3% of leachable copper was immobilized by HAP/C–S–H after 28 d. Acid soluble Cu, the main contributor to biotoxicity, decreased significantly while reducible and residual Cu increased. After immobilization, the acid neutralization capacity of the soil increased and the dissolution of copper was substantially reduced in near-neutral pH. It can be concluded that HAP/C–S–H is an effective, low-cost and eco-friendly reagent for in-situ remediation of heavy metal polluted soil and groundwater.

In this study, PAHs and their transformed PAH products (TPPs) in road dust were subjected to UV driven photolysis, and then extracted using simultaneous pressurized fluid extraction, and analysed using Shimadzu Triple Quadrupole GC/MS. The results of the analysis were used to investigate the robustness and reliability of 14 existing diagnostic ratios (DRs) and two newly proposed molecular DRs that are relevant for characterizing the sources of PAHs and TPPs. The influence of photolysis on the carcinogenic health risk posed to humans by these hazardous pollutants was then assessed. The findings indicated that the DRs segregated into stable, moderately stable and non-stable classes of source characteristics under the influence of photolysis. Only two of the existing DRs, namely, benzo(a)pyrene/benzo(ghi)perylene (BaP/BghiP) and total index exhibited consistent stability to photolysis, whilst fluoranthene/(fluoranthene + pyrene) (FRT/(FRT+PYR)) showed moderate stability. The two newly proposed DRs, naphthalene/1-nitronaphthalene (NAP/NNAP) and pyrene/(1-nitropyrene + 1-hydroxypyrene) (PYR/(1NPY+HPY)) were found to be highly reliable in post-emission source characterization. The cross-plots of the most stable DRs showed that traffic emissions is the primary source of PAHs, whilst post-emission photolysis is the secondary source of nitro-PAH (NPAH) TPPs. The percent resonance energy thermodynamic stability of the PAH pollutants does not exert any direct influence on the source characteristics of the DRs. Adults are more vulnerable to potential carcinogenic risks as a result of PAH and TPPs photolysis whereas negligible risk exist for children. This study contributes to a more reliable diagnosis of PAH and TPP sources and thus, to the regulatory mitigation of these hazardous pollutants thereby, promoting enhanced protection of human health and the environment.

Polyethylene (PE) and polypropylene (PP) microplastics (MPs), as carriers, can bind with pesticides, which propose harmful impacts to aqueous ecosystems. Meanwhile, carbofuran and carbendazim (CBD), two widely used carbamate pesticides, are toxic to humans because of the inhibition of acetylcholinesterase activity. The interaction between two MPs and two pesticides could start in farmland and be maintained during transportation to the ocean. Herein, the adsorption behavior and mechanism of carbofuran and carbendazim (CBD) by PE and PP MPs were investigated via characterization and density functional theory (DFT) simulation. The adsorption kinetic and thermodynamic data were best described by pseudo-second-order kinetics and the Freundlich models. The adsorption behaviors of individual carbofuran/CBD on both MPs were very similar. The CBD adsorption rate and capacity of PE and PP MPs were higher than those of carbofuran. This phenomenon explained the lower negative effects of DOM (oxalic acid, glycine (Gly)) on CBD adsorption relative to those of carbofuran. The presence of oxalic acid and Gly decreased the PE adsorption by 20.40–48.02% and the PP adsorption by 19.27–42.11%, respectively. It indicated the significance of DOM in carbofuran cycling. The adsorption capacities were negatively correlated with MPs size, indicating the importance of specific surficial area. Fourier transformation infrared spectroscopy before and after adsorption suggested that the adsorption process did not produce any new covalent bond. Instead, intermolecular van der Waals forces were one of the primary adsorption mechanisms of carbofuran and CBD by MPs, as evidenced by DFT calculations. Based on the zeta potential, the electrostatic interaction explained the higher adsorption CBD by MPs than carbofuran.

This study investigated the competitive adsorption mechanisms of pharmaceuticals (i.e., naproxen, diclofenac, and ibuprofen) toward the pristine and NaOH-activated biochars from spent coffee wastes (SCW) in lake water and wastewater effluent. The kinetic and isotherm studies revealed that the improved physicochemical characteristics and physically homogenized surfaces of the pristine SCW biochar through the chemical activation with NaOH were beneficial to the adsorption of pharmaceuticals (competitive equilibrium adsorption capacity (Qₑ, ₑₓₚ): NaOH-activated SCW biochar (61.25–192.07 μmol/g) > pristine SCW biochar (14.81–20.65 μmol/g)). The adsorptive removal of naproxen (Qₑ, ₑₓₚ = 14.81–18.81 μmol/g), diclofenac (Qₑ, ₑₓₚ = 15.73–20.00 μmol/g), and ibuprofen (Qₑ, ₑₓₚ = 16.20–20.65 μmol/g) for the pristine SCW biochar showed linear correlations with their hydrophobicity (log D at pH 7.0: ibuprofen (1.71) > diclofenac (1.37) > naproxen (0.25)). However, their Qₑ, ₑₓₚ values for the NaOH-activated SCW biochar (naproxen (176.39–192.07 μmol/g) > diclofenac (78.44–98.74 μmol/g) > ibuprofen (61.25–80.02 μmol/g)) were inversely correlated to the order of their log D values. These results suggest that the reinforced aromatic structure of the NaOH-activated SCW biochar facilitated the π-π interaction. The calculated thermodynamic parameters demonstrated that the competitive adsorption of pharmaceuticals on the NaOH-activated SCW biochar compared to pristine SCW biochar occurred more spontaneously over the entire pH (5.0–11.0) and ionic strength (NaCl: 0–0.125 M) ranges. These observations imply that the NaOH-activated SCW biochar might be potentially applicable for the removal of pharmaceuticals in lake water and wastewater effluent.

For effective removal of cadmium (II) (Cd(II)) from polluted water, a magnetic adsorbent of Fe₃O₄@SiO₂ core-shell microspheres modified with methyl-protected thiol groups (Fe₃O₄@SiO₂-SH-Protected) was synthesized and characterized by scanning electron, transmission electron, energy dispersive X-ray spectroscopy, Fourier transform infrared spectroscopies, as well as X-ray diffraction, Raman spectroscopy, and magnetic measurements. Characterization results showed that thiol groups on the surface of Fe₃O₄@SiO₂ material were protected to avoid disulfide formation. Batch adsorption experiments were conducted by varying the contact time, initial pH, solid-liquid ratio, temperature, Cd(II) concentrations, and interfering cations. Fe₃O₄@SiO₂-SH-Protected material exhibited much higher adsorption capacity than Unprotected forms and other adsorbents due to methyl group protection. The maximum adsorption capacity calculated from the Langmuir fitting was 27.5 mg·g⁻¹ (pH 7, 25 °C), and the adsorption kinetics followed a pseudo-second-order model, and adsorption mainly dominated by film diffusion processes. Thermodynamic parameters indicated that the adsorption process was a spontaneous, endothermic, and positive entropic process. Cd(II)-loaded on the adsorbent was easily desorbed with 0.1 M HCl and the adsorbent stable in 0.1 M HCl for long times, showing good reusability and stability.

The shell surrounding fruits of the jatobá-do-cerrado tree, in its natural state, was modified by the addition of HNO₃ and NaOH and used as an adsorbent in the removal of Cu(II) and Ni(II) from aqueous solutions. The untreated (JIN) and chemically modified (JCT) fruit shell samples were characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and X-ray diffraction. Their efficiency as adsorbents in the removal of Cu(II) and Ni(II) ions from aqueous solutions was studied under different conditions of pH (2-9) and it was observed that the optimal pH for Cu (II) adsorption was 5.5 and for Ni (II) it was 6.0. The adsorption isotherms were obtained at different temperatures (298, 308, 318 K) and the qₘₐₓ values ranged from 33.96 to 41.00 mg g⁻¹. The adsorbents presented higher selectivity toward Cu ions (II). The thermodynamic analysis results suggest that the adsorption process studied is of a physical nature. Supported by quantum mechanical calculations, the interaction sites of the ion-cellulose and ion-lignin complexes were identified, evidencing the central role of water molecules in stabilization of the complexes. The experimental and theorical results indicate that JIN and JCT have good potential for the adsorption of Cu(II) and Ni(II) ions and are thus promising materials for the removal of other metal ions in aqueous systems.

Condensates of vapor-gas streams were collected during field and laboratory experiments for the determination of the volatility of chemical elements in sulfide tailings under ambient conditions. The object of research was the Ursk waste heaps (Kemerovo region, Russia). Field experiments were performed on the top of the heap and in neighboring territories; the elements’ concentrations in condensates from the top exceed the background values in 2–3 orders of magnitude. To obtain condensates in the laboratory, the waste material was heated to 60 °С. Laboratory condensate–contended high concentrations Ca, Mg, but Fe, Cd, Mo, Sn, Zr, and W were lower by more than 2 orders of magnitude. Also, chemical elements such as Au, Zr, Cs, U, and Tl were determined in the laboratory condensates at elevated temperatures. Also, solid samples were leached with water at the laboratory. A high positive correlation of condensate compositions with compositions of water extracts obtained from parallel samples was established. The most mobile elements transferred in the steam-gas phase are alkaline (Li, Cs, Na, K), alkaline earth (Ca, Sr), chalcophile metals (Hg, Zn, Cu), and metalloids (As, Sb, Se). The numerical experiment of metal transfer forms using thermodynamic modeling methods has been performed, including those with organic ligands.