Search Results (15)

The study investigates the interaction of humic acids (HAs) with road petroleum bitumen to enhance its performance and resistance to technological aging. It addresses a critical gap in understanding the modification mechanisms. The research is motivated by the need for sustainable and effective bitumen modifiers to improve the durability of asphalt pavements. The primary objective was to characterize the interaction between HA and bitumen using advanced analytical techniques, including complex thermal analysis (DTA/DTG), Fourier-transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The results demonstrated that adding two wt.% HA to bitumen BND 70/100 increased its thermal stability, raising the onset temperature of thermo-oxidative processes from 214 to 237 °C and reducing the mass loss rate during heating from 2.5 to 1.9%·min⁻¹. FTIR analysis revealed chemical interactions between polar groups of humic acids (e.g., –COOH, –OH) and bitumen components, forming a denser structure. SEM images confirmed a more homogeneous microstructure with fewer microcracks in the modified bitumen. Practical improvements included a higher softening point (52.6 to 54 °C) and enhanced elastic recovery (17.5 to 28.7%). However, the study noted limitations such as reduced ductility (from 58 to 15 cm) and penetration (from 78 to 72 dmm), indicating increased stiffness. The findings highlight the potential of humic acids as eco-friendly modifiers to improve bitumen’s aging resistance and thermal performance, offering practical value for extending pavement lifespan. The effective use of HA will, in turn, allow the use of Ukrainian lignite, the balance reserves of which are estimated at 2.0–2.9 billion tons, in non-fuel technologies. Full article

Humic acid (HA), a major component of soil organic matter, is a naturally occurring macromolecule formed through the decomposition of plant and microbial residues. Its molecular structure comprises functional groups such as carboxyl, phenolic, hydroxyl, and carbonyl functional groups, which enable HA to interact with soil particles, nutrients, and biological systems. These interactions significantly contribute to soil fertility and overall plant productivity. Functionally, HA enhances soil health by increasing cation exchange capacity, improving water retention, and promoting the formation and stabilization of soil aggregates. In addition to its role in soil conditioning, HA is essential in mitigating plant stress. It achieves this by modulating antioxidant enzyme activity, stabilizing cellular membranes, and alleviating the adverse effects of abiotic stressors such as salinity, drought, and heavy metal toxicity. This review highlights the structural characteristics of HA, its structure-based functions, and the mechanisms involved in plant stress alleviation. Additionally, we explore how HA can be modified through physical, chemical, and biological approaches to enhance its agronomic performance. These modifications are designed to improve HA agronomic efficiency by increasing nutrient bioavailability, reducing environmental losses through minimized leaching and volatilization, and supporting sustainable agricultural practices. Overall, this review underscores the multifaceted roles of HA in promoting plant resilience to environmental stress, highlighting its potential as a key agent in the development of sustainable and eco-friendly crop production systems. Full article

The application of fungicides (such as tebuconazole) can impose harmful impacts on the ecosystem and humans. In this study, a new calcium modified water hyacinth-based biochar (WHCBC) was prepared and its effectiveness for removing tebuconazole (TE) via adsorption from water was tested. The results showed that Ca was loaded chemically (CaC₂O₄) onto the surface of WHCBC. The adsorption capacity of the modified biochar increased by 2.5 times in comparison to that of the unmodified water hyacinth biochar. The enhanced adsorption was attributed to the improved chemical adsorption capacity of the biochar through calcium modification. The adsorption data were better fitted to the pseudo-second-order kinetics and the Langmuir isotherm model, indicating that the adsorption process was dominated by monolayer adsorption. It was found that liquid film diffusion was the main rate-limiting step in the adsorption process. The maximum adsorption capacity of WHCBC was 40.5 mg/g for TE. The results indicate that the absorption mechanisms involved surface complexation, hydrogen bonding, and π–π interactions. The inhibitory rate of Cu²⁺ and Ca²⁺ on the adsorption of TE by WHCBC were at 4.05–22.8%. In contrast, the presence of other coexisting cations (Cr⁶⁺, K⁺, Mg²⁺, Pb²⁺), as well as natural organic matter (humic acid), could promote the adsorption of TE by 4.45–20.9%. In addition, the regeneration rate of WHCBC was able to reach up to 83.3% after five regeneration cycles by desorption stirring with 0.2 mol/L HCl (t = 360 min). The results suggest that WHCBC has a potential in application for removing TE from water. Full article

To remove typical herbicide diuron effectively, a novel sludge-derived modified biochar (SDMBC600) was prepared using sludge-derived biochar (SDBC600) as raw material and Fe-Zn as an activator and modifier in this study. The physico-chemical properties of SDMBC600 and the adsorption behavior of diuron on the SDMBC600 were studied systematically. The adsorption mechanisms as well as practical applications of SDMBC600 were also investigated and examined. The results showed that the SDMBC600 was chemically loaded with Fe-Zn and SDMBC600 had a larger specific surface area (204 m²/g) and pore volume (0.0985 cm³/g). The adsorption of diuron on SDMBC600 followed pseudo-second-order kinetics and the Langmuir isotherm model, with a maximum diuron adsorption capacity of 17.7 mg/g. The biochar could maintain a good adsorption performance (8.88–12.9 mg/g) under wide water quality conditions, in the pH of 2–10 and with the presence of humic acid and six typical metallic ions of 0–20 mg/L. The adsorption mechanisms of SDMBC600 for diuron were found to include surface complexation, π–π binding, hydrogen bonding, as well as pore filling. Additionally, the SDMBC600 was tested to be very stable with very low Fe and Zn leaching concentration ≤0.203 mg/L in the wide pH range. In addition, the SDMBC600 could maintain a high adsorption capacity (99.6%) after four times of regeneration and therefore, SDMBC600 could have a promising application for diuron removal in water treatment. Full article

Nickel-cobalt spinel catalyst (NCO) is a promising catalyst for air oxidation of humic acid, which is a typical natural refractory organic matter and a precursor of toxic disinfection by-products. In this study, reductive etchers, NaBH₄ or Na₂SO₃, were used to adjust the NCO surface structure to increase the performance. The modified catalyst (NCO-R) was characterized, and the relationship between its intrinsic properties and catalytic paths was discovered. The results of O₂-temperature programmed desorption, NH₃-temperature programmed desorption, and X-ray photoelectron spectroscopy (XPS) demonstrated that reductant etching introduced oxygen vacancies to the surface of NCO and increased active surface oxygen species and surface acidity. In addition, the modification did not change the raw hollow sphere structure of NCO. The crystallinity and specific surface area of NCO-R increased, and average pore size of NCO-R decreased. XPS results showed that the ratio of Co³⁺/Co²⁺ in NCO-R decreased compared with NCO, while the ratio of Ni³⁺/Ni²⁺ increased. The results of H₂-temperature programmed reduction showed that the H₂ reduction ability of NCO-R was stronger. Due to these changes in chemical and physical properties, NCO-R exhibited much better catalytic performance than NCO. In the catalytic air oxidation of humic acid at 25 °C, the total organic carbon (TOC) removal rate increased significantly from 44.4% using NCO to 77.0% using NCO-R. TOC concentration of humic acid decreased by 90.0% after 12 h in the catalytic air oxidation using NCO-R at 90 °C. Full article

Biochar is a beneficial adsorbent for the treatment of organic pollutants in the environment. The association of oxygen functional groups and adsorption behaviors has not been well investigated. In this paper, the oxidation-modified biochar (O-BC) and the reduction-modified biochar (R-BCX) were prepared by Co²⁺/peroxymonosulfate chemical oxidation and high-temperature reduction, respectively. The modified biochars were used to remove sulfamethoxazole (SMX) from water, and the adsorption amounts of biochar followed the order of R-BC700 (14.66 mg·L⁻¹) > O-BC (4.91 mg·L⁻¹) > BC (0.16 mg·L⁻¹). Additionally, the effects of water chemical conditions (i.e., ionic strength, solution pH and humic acid (HA) concentration) on the adsorption of SMX on biochar, were further investigated. Combining physical adsorption, X-ray electron spectroscopy, and zeta potentiometer characterization techniques, the effect of functional groups on the adsorption mechanism was further explored, revealing the importance of various oxygen functional groups for SMX adsorption. The results showed that C=O and C=C, resulting in π–π interaction, were in favor of the adsorption of SMX, while C-O was not conducive to the adsorption of SMX, due to the steric hindrance and the negative surface charge. Additionally, the hydrophobic effect of the biochar was also one of the adsorption mechanisms. Full article

Potential use of tannic acid (TA) as an additive for fabrication of polyvinylidene difluoride (PVDF) membrane was investigated. The TA was introduced by blending into the dope solution with varying concentrations of 0, 1, 1.5, and 2 wt%. The prepared membranes were characterized and evaluated for filtration of humic acid (HA) solution. The stability of the membrane under harsh treatment was also evaluated by one-week exposure to acid and alkaline conditions. The results show that TA loadings enhanced the resulting membrane properties. It increased the bulk porosity, water uptake, and hydrophilicity, which translated into improved clean water flux from 15.4 L/m².h for the pristine PVDF membrane up to 3.3× for the TA-modified membranes with the 2 wt% TA loading. The flux recovery ratio (FRR) of the TA-modified membranes (FRRs = 78–83%) was higher than the pristine one (FRR = 58.54%), with suitable chemical stability too. The improved antifouling property for the TA-modified membranes was attributed to their enhanced hydrophilicity thanks to improved morphology and residual TA in the membrane matric. Full article

In this work, a facile preparation method was proposed to reduce natural organics fouling of hydrophobic membrane via UV grafting polymerization with methacrylic acid (MAAc) and methyl acrylamide (MAAm) as hydrophilic monomers, followed by multihydrogen bond self-assembly. The resulting poly(vinylidene fluoride)-membranes were characterized with respect to monomer ratio, chemical structure and morphology, surface potential, and water contact angle, as well as water flux and organic foulants ultrafiltration property. The results indicated that the optimal membrane modified with a poly(MAAc-co-MAAm) polymer gel layer derived from a 1:1 monomer ratio exhibited superior hydrophilicity and excellent gel layer stability, even after ultrasonic treatment or soaking in acid or alkaline aqueous solution. The initial water contact angle of modified membranes was only 36.6° ± 2.9, and dropped to 0° within 13 s. Moreover, flux recovery rates (FRR) of modified membranes tested by bovine serum albumin (BSA), humic acid (HA), and sodium alginate (SA) solution, respectively, were all above 90% after one-cycle filtration (2 h), significantly higher than that of the pure membrane (70–76%). The total fouling rates (R_t) of the pure membrane for three foulants were as high as 47.8–56.2%, while the R_t values for modified membranes were less than 30.8%. Where R_t of BSA dynamic filtration was merely 10.7%. The membrane designed through grafting a thin-layer hydrophilic hydrogel possessed a robust antifouling property and stability, which offers new insights for applications in pure water treatment or protein purification. Full article

Polycyclic aromatic hydrocarbons (PAHs) are hazardous compounds originating from anthropogenic activity. Due to their carcinogenic properties for humans, several technologies have been developed for PAH removal. Sorption with natural and organic materials is currently one of the most studied due to its low cost and its environmentally friendly nature. In this work, a hybrid sorbent involving functionalized humic acids (HAs) and nano-zeolite is proposed to entrap PAHs. The use of functionalized HAs immobilized in a porous support is designed to address the instability of HAs in solution, which has been already reported. HA functionalization was carried out to increase the non-polarity of HAs and aliphatic group formation. The HAs were functionalized by esterification/etherification with alkyl halides, and their chemical changes were verified by FTIR and NMR. The sorption isotherms of the functionalized HAs in micro- and nano-zeolites were used to assess the performance of the nano-zeolites in adsorbing these HAs. The hybrid support allowed the removal of anthracene and pyrene at percentages higher than 90%; fluoranthene, of angular molecular structure, was adsorbed at 85%. PAHs are ubiquitous in the environment, and a stable sorption of them in solid matrices will allow their removal from the environment through effective and environmentally friendly methods. Full article

A pilot-scale experiment is carried out for treating mixed wastewater containing pharmaceutical wastewater (PW) and domestic wastewater (DW), by a process that is a combination of hydrolysis acidification-ozone-modified anaerobic–anoxic–aerobic-ozone (A²/O) (pre-ozone) or hydrolysis acidification-modified A²/O-ozone (post-ozone). The effects of different mixing ratios of PW and DW and pre-ozone treatment or post-ozone treatment on the removal of nitrogen and phosphorus and chemical oxygen demand (COD) are compared and studied. The optimal ratio of PW in mixing wastewater is 30%, which has the optimal COD removal efficiency and minimum biotoxicity to biological treatment. The pre-ozone treatment shows more advantages in removing nitrogen and phosphate but the post-ozone treatment shows more advantages in COD removal. Analysis of dissolved organic matter (DOM) demonstrates that post-ozone treatment has a more significant effect on the removal of fulvic acid and humic acid than the effect from the pre-ozone treatment, so the COD removal is better. Overall DOM degradation efficiency by post-ozone treatment is 55%, which is much higher than the pre-ozone treatment efficiency of 38%. Microbial community analysis reveals that the genus Thauera and the genus Parasegetibacter take great responsibility for the degradation of phenolics in this process. All the results show that the post-ozone treatment is more efficient for the mixed wastewater treatment in refractory organics removal. Full article

Carbon nanotubes (CNTs) are a robust material and proven as a promising candidate for a wide range of electronic, optoelectronic and environmental applications. In this work, two different methods were utilized for the preparation of CNTs exhibiting different aspect ratios via chemical vapor deposition (CVD). The as-prepared CNTs were analyzed using scanning electron microscopy (SEM), transmission electron microscopy (TEM), N₂adsorption isotherms, thermogravimetric analysis and Raman spectroscopy in order to investigate their morphological and structural properties. Free-standing CNTs “buckypaper” membranes were fabricated, characterized and tailored to meet the requirements of two applications, i.e., (1) the removal of humic acid (HA) from water and (2) separation of oil-in-water emulsions. It was revealed that the hydrophobic buckypapers showed high separation performance for Shell oil-in-water emulsions filtration, with up to 98% through the accumulation of oil droplets onto the membrane surface. The absorption capacity of buckypaper membranes for various organic liquids (oil, chloroform and toluene) was evaluated over 10 absorption cycles to investigate their recyclability and robustness. Moreover, surface modification was introduced to the pristine CNTs to increase their surface hydrophilicity and improve the pure water permeability of buckypapers. These modified buckypapers showed high flux for HA solutions and excellent HA rejection efficiency up to 95%via size exclusion and electrostatic repulsion mechanisms. Full article

In this study, a facile and effective method is adopted to prepare mechanochemically robust super antifouling membrane surfaces. During the process, vinyl trimethoxy silane (VTMS) was used as the reactive intermediate for coupling the hydrophilic inorganic SiO₂ nanoparticle layer on to the organic ultra-high-molecular-weight polyethylene (UHMWPE) membrane surface, which created hierarchical nanostructures and lower surface energy simultaneously. The physical and chemical properties of the modified UHMWPE composite membrane surface were investigated. FTIR and XPS showed the successful chemical grafting of VTMS and SiO₂ immobilization, and this modification could effectively enhance the membrane’s surface hydrophilicity and filtration property with obviously decreased surface contact angle, the pure water flux and bovine serum albumin (BSA) rejection were 805 L·m⁻²·h⁻¹ and 93%, respectively. The construction of the hydrophilic nano-SiO₂ layer on the composite membrane surface for the improvement of membrane antifouling performance was universal, water flux recovery ratio values of BSA, humic acid (HA), and sodium alginate (SA) were all up to 90%. The aim of this paper is to provide an effective approach for the enhancement of membrane antifouling performance by the construction of a hydrophilic inorganic layer on an organic membrane surface. Full article

This paper reports the application of silica derived from natural biomasses of rice husk and bagasse ashes as membrane modifying agents. The modification was conducted on poly(ether sulfone) (PES) membrane by blending the silica into the dope solution. The modification was aimed to improve the structure and hydraulic performance of the resulting PES membrane. The effects of silica addition to the membrane system were evaluated through the analysis of change in chemical structure using ATR-FTIR, surface morphological change using AFM, and surface hydrophilicity using water contact angle measurement. SEM and AFM images show the silica loading significantly affects the membranes morphologies. Silica loading also promotes hydrophilic property as shown by the decrease in water contact angles from 82° to 52–60° due to the presence of polar groups in some residual silica in the membrane matrix. Silica blending also leads to the formation of membranes with higher permeability of up to three folds but lower humic acid rejection (78–62%). The findings indicate the role of silica to enhance the membrane pore size. The ability of membrane to reject humic acid (of 0.8 nm minimum diameter) indicating that the resulting membranes were in between tight ultrafiltration and nanofiltration type. Nonetheless, applying too-high silica concentration decreased the humic acid rejection most likely due to over enlargement of the membrane pore size. Full article

The removal of impurities from water or wastewater by the membrane filtration process has become more reliable due to good hydraulic performance and high permeate quality. The filterability of the membrane can be improved by having a material with a specific pore structure and good hydrophilic properties. This work aims at preparing a polyvinylidene fluoride (PVDF) membrane incorporated with phospholipid in the form of a 2-methacryloyloxyethyl phosphorylcholine, polymeric additive in the form of polyvinylpyrrolidone, and its combination with inorganic nanosilica from a renewable source derived from bagasse. The resulting membrane morphologies were analyzed by using scanning electron microscopy. Furthermore, atomic force microscopy was performed to analyze the membrane surface roughness. The chemical compositions of the resulting membranes were identified using Fourier transform infrared. A lab-scale cross-flow filtration system module was used to evaluate the membrane’s hydraulic and separation performance by the filtration of humic acid (HA) solution as the model contaminant. Results showed that the additives improved the membrane surface hydrophilicity. All modified membranes also showed up to five times higher water permeability than the pristine PVDF, thanks to the improved structure. Additionally, all membrane samples showed HA rejections of 75–90%. Full article

Over the years, various technologies have been utilized for Natural Organic Matter (NOM) removal with varying degrees of success. Conventional treatment methods comprising of coagulation, flocculation, sedimentation, or filtration are widely used to remove NOM. An alternative to these conventional methods is to use spiral wound membranes. These membranes tend to remove too much hardness whilst being ineffective in disinfection. They also have a low tolerance to chlorine and thus, have limited chemical cleaning options. In this study, we investigated how an alternative and new innovative filtration concept, based on capillary NF membranes from modified polyethersulfone (PES), may be used to treat soft but humus-rich surface waters. Comprehensive performance tests, with a fully automated membrane pilot equipped with a full-scale sized test module (40 m² membrane surface), were conducted at WTP Görvälnverket, which is operated by the water utility Norrvatten, providing drinking water from Mälaren (SUVA = 2.7–3.3, TOC = 7.0–10.0 mg·L⁻¹) for about 500,000 people in the northern part of the Swedish capital of Stockholm. The removal of both UV and DOC was modeled using a solution diffusion approach. The optimized parameters allow deducing optimal operation conditions with respect to energy, water consumption, and permeate water quality. Optimal cross flow velocity was determined to be 0.75 m·s⁻¹ at 80% recovery and a flux of 12–18 L·m⁻²·h⁻¹. Under these conditions, 80% of the UV, 75% of the Humic Substances (MW = 600) and 70% of TOC were removed (from 8 to below 2 mg·L⁻¹). A higher cross flow velocity led to marginal improvement (+2%) while both higher and lower membrane fluxes degraded permeate water quality. Apparent optimized diffusion coefficients for UV and TOC were around 1.2–2.4 × 10⁻¹⁰·m²·s⁻¹ and were similar to values found in the literature. Due to their higher diffusion coefficients and higher permeability coefficient, only 40% of the low molecular weight acids (MW = 300–400) were retained. Approximately 30%–40% of the low molecular weight acids in the permeate can be further removed using GAC post NF. The resulting energy consumption of a hypothetical four-stage design, at average operating temperature of 5.73 °C, was calculated to be around 0.6 kWh·m⁻³ produced water. Full article