The main objective of this study was to understand the key factors and mechanisms controlling adsorption of sulfonamides to biochars. Batch adsorption experiments were performed for sulfamethoxazole and sulfapyridine to three pine-wood biochars prepared under different thermochemical conditions: pyrolysis at 400 °C (C400) and 500 °C (C500), and pyrolysis at 500 °C followed with hydrogenation (C500-H). For both sulfonamides, the adsorbent surface area-normalized adsorption was stronger to C500 than to C400. This is attributable to the enhanced π–π electron-donor–acceptor interaction with the carbon surface of C500 due to the higher degree of graphitization. Despite the relatively large difference in surface O-functionality content between C500 (12.2%) and C500-H (6.6%), the two biochars exhibited nearly identical adsorbent surface area-normalized adsorption, indicating negligible role of surface O-functionalities in the adsorption to these adsorbents. Effects of solution chemistry conditions (pH, Cu2+, and dissolved soil humic acid) on adsorption were examined.

We observed that the sorption kinetics of nitrobenzene and 2,4-dinitrotoluene (two model polar compounds) was significantly slower than that of 1,4-dichlorobenzene and phenanthrene (two model apolar compounds). The difference was attributable to the strong non-hydrophobic interactions between the polar molecules and soil. Interestingly, sorption kinetics of the polar sorbates to the soil organic matter-free soil, humic/fulvic acid-free soil, and extracted humic acids was very fast, indicating that different soil components played a synergetic role in the observed slow kinetics. We propose that slow sorption kinetics of highly polar sorbates stems mainly from the strong specific interactions (H-bonding, electron donor–acceptor interactions, etc.) with humic/fulvic acids; such specific interactions occur when sorbate molecules diffuse through humic/fulvic acids coiled, in relatively compressed confirmations, within the complex, tortuous, and porous soil matrices formed by mineral grains/particles and soil organic matter.

Binding of polycyclic aromatic hydrocarbons (PAHs) to dissolved organic matter (DOM) can reduce the freely dissolved concentration, increase apparent solubility or enhance diffusive mass transfer. To study the effects of DOM on biodegradation, we used phenanthrene and pyrene as model PAHs, soil humic acids as model DOM and a soil Mycobacterium strain as a representative degrader organism. Humic acids enhanced the biodegradation of pyrene when present as solid crystals but not when initially dissolved or provided by partitioning from a polymer. Synchronous fluorescence spectrophotometry, scintillation counting and a microscale diffusion technique were applied in order to determine the kinetics of dissolution and diffusive mass transfer of pyrene. We suggest that humic acids can enhance or inhibit biodegradation as a result of the balance of two opposite effects, namely, solubilization of the chemicals on the one hand and inhibition of cell adhesion to the pollutant source on the other.

This work investigated the binding behavior of phenanthrene by humic acids (HA-2 and HA-5), proteins (bovine serum albumin (BSA)), lysozyme and pepsin), and their complexes using a passive dosing technique. All sorption isotherms were fitted well with Freundlich model and the binding capability followed an order of HA-5 > HA-2 > BSA > pepsin > lysozyme. In NaCl solution, phenanthrene binding to HA-BSA complexes was much higher than the sum of binding to individual HA and BSA, while there was no enhancement for HA-pepsin. Positively charged lysozyme slightly lowered phenanthrene binding on both HAs due to strong aggregation of HA-lysozyme complexes, leading to reduction in the number of binding sites. The binding enhancement by HA-BSA was observed under all tested ion species and ionic strengths. This enhancement can be explained by unfolding of protein, reduction of aggregate size and formation of HA-BSA complexes with favorable conformations for binding phenanthrene.

Transport of carbon nanotubes (CNTs) in soil/sediment matrixes can regulate their potential eco-effects and has been however rarely studied. Herein, column experiments were conducted to investigate mobility of CNT suspensions stabilized by dodecylbenzenesulfonic acid sodium salt (SDBS), octyl-phenol-ethoxylate (TX-100) and cetylpyridinium chloride (CPC) in four soil samples with certain particle sizes. Humic acid was extracted from a soil sample and was coated on quartz sands to explore the effect of soil organic matter (SOM) on the mobility. Results showed that the positively-charged CPC-CNT was entirely retained in the columns while the negatively-charged SDBS-CNT and TX-100-CNT more or less broke through the columns. Pearson correlation analyses revealed that soil texture rather than SOM controlled the mobility. Electrostatic attraction to and/or precipitation on the grain surfaces together with the straining effect could explain the CNT retention. These novel results will help to understand the eco-effects of CNTs.

Humic acid (HA) is ubiquitous in groundwater, and poses great influence on the biogeochemical controls on, as well as treatment of, contaminants. This study deals with the adsorption of HA on a bimetallic iron system, Cu/Fe, and its influence on the reduction of nitrobenzene in synthetic groundwater. The adsorption kinetics, isotherms, and enthalpy of HA on bimetallic Cu/Fe particles are investigated. Compared with the adsorption of HA on Fe⁰particles, the adsorption on Cu/Fe is faster than that on Fe⁰. The adsorption isotherms of HA at different pH values and temperatures show that the adsorption is always greater on Cu/Fe than on Fe⁰, and increases when the pH decreases and temperature increases. Moreover, the influences of pH and temperature on adsorption by Cu/Fe are less than those observed in adsorption on Fe⁰. The adsorption enthalpy on Cu/Fe is lower than that on Fe⁰, and both adsorptions are spontaneous and endothermic. Characterization of the corrosion products by SEM-EDX, XRD, and XPS reveals the appearance of maghemite (γ-Fe₂O₃) and magnetite (Fe₃O₄) on Cu/Fe with HA adsorption, which were more crystalline than those of Fe⁰, indicating that bimetallic Cu/Fe facilitated the formation of crystalline corrosion products. The adsorption of HA accelerates the release of iron ions but suppresses the reduction of nitrobenzene. Compared with Fe⁰, Cu/Fe accelerates the adsorption of HA and Cu/Fe increases the reduction of nitrobenzene. The suppression on nitrobenzene reduction increased with the increase in HA concentration.

This study examined the transport behavior of nano zero-valent iron (NZVI) coated with three types of stabilizers (i.e., polyacrylic acid, Tween-20, and starch) in saturated sand- and soil-packed columns under varying geochemical conditions. The cations or ionic strength and humic acid (HA) affected the transport of NZVI in varying degrees for different types of surface-modified NZVI (SM-NZVI). The effects of HA on the transport of SM-NZVI were different in sand- and soil-packed columns. In the sand-packed column, the presence of HA exerted an effect on the particle–particle interaction (i.e., aggregation), resulting in either enhanced or decreased transport of SM-NZVI. However, in the soil-packed column, the HA not only influenced the particle–particle interaction but also exerted an effect on the particle–soil grain interaction (i.e., deposition). Additionally, a significant enhancement in the transport of SM-NZVI in the soil-packed column was observed with increasing particle concentration. Moreover, the adsorption of arsenic on the surface of SM-NZVI exhibited insignificant effect on the transport of SM-NZVI. The release of arsenic from the arsenic-loaded SM-NZVI was detected when subjected to flushing with phosphate-containing groundwater. This fundamental understanding of the subsurface transport of SM-NZVI is of critical importance for the benign use and risk management of SM-NZVI.

Sorption–desorption behavior of the antibiotic tetracycline (TET) and the synthetic estrogen hormone 17α-ethinylestradiol (EE2) with wastewater sludge and sludge-derived humic substances [humic acid (HA) and humin] was investigated. From acidic functional group capacity and elemental analyses, HA had higher polarity, aromaticity, and acidity than humin; humin contained aliphatic chains with high mineral content. The different physicochemical properties of the pharmaceuticals and sludge components yielded different kinds of sorption–desorption interactions. Partitioning coefficients (Kd) of TET to sludge were higher (1,552 ± 41–4,667 ± 41 L/kg) than EE2 (534 ± 52–609 ± 47 L/kg). TET sorption was highly pH-dependent and maximal at pH 9. Ca²⁺ions enhanced sorption, emphasizing the role of polyvalent metal ions in forming TET–sludge complexes. Humin was the dominant component for TET sorption due to its high inorganic matter content. In contrast, EE2 sorption was independent of solution pH, forming mostly hydrophobic interactions with sludge organic matter. EE2 had a high affinity for HA due to its chemical structure. Desorption of the two pharmaceuticals differed as well. The amount of desorbed TET (18.7 ± 1.3–29.8 ± 2 %) was lower than that of EE2 (60.6 ± 3–62.3 ± 2 %), and the hysteresis index was higher for TET than EE2. While TET desorption tended to be delayed in the solid matrix, EE2 desorbed easily and in accordance with the aqueous equilibrium concentration. The conclusions emphasize the need for further research into frequently used pharmaceuticals with different physicochemical properties and the recognition of sludge application as an important source of distribution for these contaminants in the environment.

When released into natural aquatic systems, cerium oxide (CeO₂) nanoparticles (NPs) may have toxic effects to the ecosystems and public health; it is thus important to understand their environmental fate and transport. This work studied the effects of humic acid (HA) concentrations (0–10 mg L⁻¹) and solution chemistry (ionic strength (IS) and pH) on the retention and transport of CeO₂NPs in water-saturated porous media under environmental relevant conditions. HA and IS showed remarkable effect on the retention and transport of CeO₂NPs in the porous media. Even at low concentrations (i.e., 5 and 10 mg L⁻¹), HA stabilized CeO₂NPs in the suspensions by introducing both negative surface charge and steric repulsion and thus enhanced their mobility in the porous media. When solution HA concentration increased or ionic strength decreased, mobility of CeO₂NPs in the porous media enhanced dramatically. Solution pH, however, had little influence on the mobility of the CeO₂NPs under the tested experimental conditions, and increasing solution pH only slightly increased the transport of the NPs. Mathematical models were applied to describe the experimental data. Predictions from the extended Derjaguin–Landau–Verwey–Overbeek (XDLVO) theory and advection–dispersion–reaction (ADR) model matched the experimental data well.

Graphene oxide (GO) nanosheets were used as adsorbent material for the removal of clofibric acid (CA) which was difficult to be removed from wastewater by traditional wastewater treatment technique. Adsorption kinetics, adsorption equilibrium, and effect of pH, ionic strength, and humic acid (HA) of the adsorption of CA onto the GO nanosheets in aqueous solution were investigated in detail. Adsorption isotherm studies indicated that the Langmuir isotherm equation fitted the sorption isotherm data better than Freundlich model and the maximum adsorption capacity of GO nanosheets for CA was 994 mg g⁻¹. In addition, adsorption kinetics data showed that the sorption of CA on GO nanosheets reached equilibration within a few minutes and were well fitted by pseudo second-order model. The results of the effects of environment factors indicated that CA sorption on GO nanosheets was weakly affected by ionic strength and strongly depended on pH and HA because of the structure of CA and the large number of oxygen-containing function groups presented on the surface of GO nanosheets. Besides, the removal efficiency of GO nanosheets for CA was reduced at pH >4 and enhanced at pH <4 in the presence of HA.