This study examines the structural, chemical, and thermal properties of biochars from slow pyrolysis of hardwood (HW), corn cob (CC), and wheat straw (WS) at 400 °C and 700 °C, evaluating their potential in environmental and industrial applications. A combination of spectroscopic, crystallographic, thermal, and microscopic techniques was employed to monitor the degradation of biomass components and the development of the carbonaceous matrix. The results show that pyrolysis temperature has a significant impact on the properties of biochar. Higher temperatures (700 °C) increased the pH (up to 10.3 for WS700), the carbon content (e.g., 89.8% for HW700), the ash content (up to 24.8% for WS700), and the specific surface area (e.g., 306.87 m2/g for CC700) while decreasing polar functional groups and volatile matter (as confirmed by FTIR). SEM showed enhanced porosity at 700 °C, which was supported by BET analysis. XRD and Raman showed increased graphitization and structural order with temperature, especially for HW and CC biochars, while WS biochars retained mineral components like SiO2 and CaCO3. TGA analysis showed improved thermal stability at 700 °C only for biochar derived from wheat straw, while HW and CC biochars showed similar total mass loss regardless of pyrolysis temperature. These biochars exhibit high potential for soil remediation (high pH), water purification (large surface area), and carbon storage (high aromaticity), with HW700 and CC700 also suitable for high-temperature industrial applications due to their stability.
This study explores biochar-based catalysts made from hardwood (HW) and wheat straw (WS) biomass for activating persulfate (PS) in the removal of lindane and β-endosulfan from water. The effects of pyrolysis temperature, solution pH, and PS concentration were investigated. The results indicated that both feedstock and pyrolysis temperature are key factors influencing biochar composition. Biochars pyrolyzed at 700 °C exhibited higher surface areas compared to those pyrolyzed at 400 °C, suggesting more effective interactions with the target pesticides. Changes in pH had a minimal impact on pesticide removal, while increasing the PS concentration from 0.5 to 3 mM accelerated degradation. However, further increases in PS concentration slowed the degradation of both pesticides. Under optimal conditions (pH of 7.0 ± 0.2 and PS concentration of 3 mM), the HW700/PS and WS700/PS systems achieved > 90% removal of pesticides within 4 h. Quenching experiments confirmed that non-radical species (1O2), generated through persulfate activation by biochar, were the key factor in lindane degradation in both systems, supporting the catalytic role of biochar rather than mere adsorption. In the HW700/PS system, SO4•−, HO•, and 1O2 acted synergistically to enhance the degradation of β-endosulfan, whereas in the WS700/PS system, the degradation was mainly driven by SO4•− and 1O2. Notably, HW700 biochar maintained its activation efficiency during β-endosulfan degradation even after five cycles. This research offers new insights into the potential of biochar-activated PS as a green, cost-effective, and efficient method for water treatment, addressing pesticide-contaminated surface water and promoting agricultural waste recycling.
Emerging microcontaminants benzophenone (BP), benzophenone-3 (BP-3) and caffeine (CF) are widely used anthropogenic markers from a group of pharmaceuticals and personal care products. They have different logD values and charges at neutral pH (2.96 neutral for BP; 3.65 negative and neutral for BP-3; 0.28 and neutral for CF). The goal of this study was to assess the efficacy of coagulation/flocculation/sedimentation (C/F/S), adsorption onto two types of powdered activated carbon (PAC)/sedimentation (PAC/S) and the combination of these two processes in different dosing sequences (PAC/C/F/S) and with/without ultrafiltration (powdered activated carbon/ultrafiltration—PAC/UF, coagulation/UF—CoA/UF) for the removal of selected micropollutants from river water. It was shown that the removal efficiency of benzophenones by coagulation depends on the season, while CF was moderately removed (40–70%). The removal of neutral BP by two PACs unexpectedly differed (near 40% and ˃93%), while the removal of BP-3 was excellent (>95%). PACs were not efficient for the removal of hydrophilic CF. Combined PAC/C/F/S yielded excellent removal for BP and BP-3 regardless of PAC type only when the PAC addition was followed by C/F/S, while C/F/S efficiency for CF diminished. The combination of UF with PAC or coagulant showed also high efficacy for benzophenones, but was negligible for CF removal.
In this study, hybrid ultrafiltration which involves adsorption onto activated carbon and/or coagulation was tested for the removal of ibuprofen, caffeine and diclofenac from the municipal wastewater treatment plant effluent (c0 = 2–3 µg/L). Ultrafiltration was tested in combination with powdered activated carbon dose of 5 mg/L separately or with coagulants (FeCl3, dose 4 mg Fe (III)/L and, natural coagulant isolated from bean seeds, dose 33 µL/L). In addition to the removal of organic micropollutants, the removal of As, Cr, Cu and Zn was also tested (c0~100 µg/L). The research was conducted on a laboratory pilot plant (capacity 30 L/h, in-out dead-end filtration, flux of 80 L/m2h). The best results were obtained for caffeine when adsorption on PAC is combined with a FeCl3 (removal efficiency 42–87%). The addition of a natural coagulant did not show benefits for the removal of organic micropollutants compared to the other tested processes, but both coagulants had similar effects on the content of metals and As Hybrid membrane processes proved to be the most efficient for Zn (44–87%) and Cr (33–87%) removal. The lowest efficiency was determined for As (˂19%). Ultrafiltration with PAC and coagulants removed 5–33% of effluent organic matter, depending on the type of coagulant; 57–87% of total nitrogen and PAC/FeCl3/UF was also partially effective for removing total phosphorus (11–39%).
This study investigates the adsorption behavior of 4-methylbenzylidene camphor (4-MBC), a persistent ultraviolet filter, onto microplastic fibers (MPFs) released from domestic textiles, under environmentally relevant conditions. Two types of MPFs were used: MPF A, a heterogeneous blend of synthetic and natural fibers, and MPF B, a uniform polyester source. Adsorption experiments were conducted in municipal wastewater, Danube River surface water, and laundry effluent. Kinetic data best fit the pseudo-second-order model (R2 > 0.95), and the Elovich model indicated chemisorption involving heterogeneous binding sites. MPF A exhibited superior adsorption capacities (qₑ = 85.4–90.1 µg/g) compared to MPF B (58.8–66.8 µg/g). Langmuir isotherms yielded maximum adsorption capacities of 204.9 µg/g for MPF A and 116.7 µg/g for MPF B (R2 = 0.929–0.977), while D–R isotherm energies (12.0–21.7 kJ/mol) confirmed specific interactions, such as π–π stacking and hydrogen bonding. Adsorption efficiency was highest in municipal wastewater (total organic carbon—TOC = 13.12 mg/L, electrical conductivity—EC = 1152 µS/cm), followed by laundry and surface waters. These findings emphasize the critical role of polymer composition and matrix complexity in pollutant transport, suggesting MPFs are effective transporters of hydrophobic micropollutants in aquatic systems.
This study investigates the potential of corn cob-derived biochars produced at 400 °C (BC400) and 700 °C (BC700) as heterogeneous catalysts for the degradation of organochlorine pesticides, lindane and β-endosulfan, through persulfate-based advanced oxidation processes (AOPs). BC700 exhibited enhanced degradation performance compared to BC400, likely due to its greater surface area, higher aromaticity, and lower surface polarity. Under optimized conditions (3.0 mM persulfate, pH 7.02, 0.2 g/L biochar), BC700 enabled the removal of up to 94% of β-endosulfan and 82% of lindane within four hours. Quenching experiments suggested different dominant degradation pathways: singlet oxygen (1O2) appeared to play a key role in lindane degradation, while β-endosulfan degradation likely involved both radical (SO4•−, HO•) and non-radical mechanisms. Reusability tests indicated that BC700 retained catalytic activity for β-endosulfan across multiple cycles, whereas lindane degradation efficiency decreased, possibly due to surface fouling or catalyst deactivation. Experiments conducted in real surface water highlighted the influence of matrix components, with partial inhibition observed for β-endosulfan and an unexpected improvement in lindane removal. These results point to the promise of high-temperature corn cob biochar as a selective and potentially reusable catalyst for AOPs in water treatment, warranting further investigation into regeneration strategies and matrix-specific effects.