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Ionic surfactants may impact removal efficiency of organic contaminants from aqueous solution, but research regarding the adsorption mechanisms on surfactant-modified carbon nanotubes (CNTs) was limited. In this study, three multi-walled and one single-walled CNTs were used as adsorbents to investigate the adsorption behavior and mechanisms of ciprofloxacin (CIP) on CNTs modified by ionic surfactants (cationic CTAB (Cetyltrimethylamnonium bromide) or anionic SDS (Sodium dodecyl sulfate)). More than 80% (82-88%) of the total removed CIP on CTAB-modified CNTs occurred within the first 6 h, much higher than that on SDS-modified CNTs (57-78%). Modeling adsorption kinetics demonstrated that CIP adsorption on surfactant-modified CNTs was controlled by multiple and faster processes, and both external mass transfer and intraparticle diffusion are limiting factors. Relative to SDS, CTAB was significantly (P < 0.001) concentration-dependent in suppressing CIP removal. Besides, the increase in 1/n values of Freundlich model with increasing CTAB concentration suggested that CTAB could be a stronger competitor for CIP adsorption. Hydrophobic interactions predominated zwitterionic CIP adsorption on all CNTs tested, while electrostatic interactions could help control ionizable CIP adsorption on surfactant-modified CNTs depending upon pH. CIP adsorption on modified SWCNTs significantly declined with increasing ionic strength from 1 mM to 100 mM relative to those multi-walled CNTs because the more favorable aggregation of SWCNTs reduced the CIP adsorption, irrespective of which surfactant was added. Significant desorption hysteresis of adsorbed CIP released by SDS and water was observed, but not by CTAB, by which 32.6-54.4% of adsorbed CIP were removed. For SDS-modified CNTs, the mean release ratio (RR) followed an order of MWCNTs (0.075) > MHCNTs (0.058) > SWCNTs (0.057) > MCCNTs (0.049), significantly (P < 0.001) lower than CTAB-CNTs (0.37-0.56). It can be predicted that the tested surfactants co-existing with CNTs depress removal efficiency of diverse contaminants similar to CIP in aqueous systems., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Metal‐organic frameworks (MOFs) are potential porous adsorbents for benzene, toluene, ethylbenzene and xylene (BTEX). A novel MOF, using low toxic aluminum (Al) as the metal, named as ZJU‐620(Al), with uniform micropore size of 8.37±0.73 Å and specific surface area of 1347 m2 g−1, was synthesized. It is constructed by one‐dimensional rod‐shaped AlO6 clusters, formate ligands and 4,4′,4′′‐(2,4,6‐trimethylbenzene‐1,3,5‐triyl) tribenzoic ligands. ZJU‐620(Al) exhibits excellent chemical‐thermal stability and adsorption for trace BTEX, e.g. benzene adsorption of 3.80 mmol g−1 at P/P0=0.01 and 298 K, which is the largest one reported. Using Grand Canonical Monte Carlo simulations and Single‐crystal X‐ray diffraction analyses, it was observed that the excellent adsorption could be attributed to the high affinity of BTEX molecules in ZJU‐620(Al) micropores because the kinetic diameters of BTEX are close up to the pore size of ZJU‐620(Al). [ABSTRACT FROM AUTHOR]

In this study, a class F fly ash and palygorskite have been acid-modified and then evaluated for the adsorption of phosphate in aqueous solution via bench-scale batch experiments. XRD, XRF, SEM, and FTIR were employed to characterize the acid-modified fly ash (MFA) and palygorskite (MPal). Both MFA and MPal show enhanced phosphate adsorption after the modification treatment. The effects of pH, adsorbent dosage, and co-ions on phosphate adsorption, as well as adsorption thermodynamics and kinetics, and leaching features of spent (used) adsorbents were also investigated. The isotherms data fit well with the Langmuir model rather than the Freundlich model, giving maximum capacities (298 K) of 13.3 mg P g − 1 for MFA and 10.5 mg P g − 1 for MPal, respectively. Surface complexation modeling of P adsorption data with the nonelectrostatic generalized composite (GC) approach indicates that phosphate were directly bound to the metal centers by ligand exchange to form two monodentate complexes, ≡ SHPO 4 − and ≡ SPO 4 2 − . The GC model appears to be an easy and efficient tool to provide an insight into the mechanism of phosphate adsorption on complex adsorbents with limited model parameters. Leaching test results suggest that the spent adsorbents can be safely disposed or further reused. [ABSTRACT FROM AUTHOR]

Adsorption of aromatic compounds, including polycyclic aromatic hydrocarbons, nitrobenzenes, phenols, and anilines, on a bamboo biochar produced at 700 °C (Ba700) was investigated with the mechanism discussion by isotherm fitting using the Polanyi-theory based Dubinin–Ashtakhov (DA) model. Correlations of adsorption capacity ( Q 0 ) of organic compounds with their molecular sizes and melting points, as well as correlations of adsorption affinity ( E ) with their solvatochromic parameters (i.e., π * and α m ), on the biochar, were developed and indicating that adsorption is captured by the pore filling mechanism and derived from the hydrophobic effects of organic compounds and the forming of π-π electron donor-acceptor (EDA) interactions and hydrogen bonding interactions of organic molecules with surface sites of the biochar. The effects of organic molecular sizes and melting points on adsorption capacity are ascribed to the molecular sieving effect and the packing efficiency of the organic molecules in the biochar pores, respectively. These correlations can be used to quantitatively estimate the adsorption of organic compounds on biochars from their commonly physicochemical properties including solvatochromic parameters, melting points and molecular cross-sectional area. The prediction using these correlations is important for assessing the unknown adsorption behaviors of new organic compounds and also helpful to guide the surface modification of biochars and make targeted selection in the environmental applications of biochars as adsorbents. [ABSTRACT FROM AUTHOR]

Adsorption of 22 nonpolar and polar aromatic compounds on 10 carbon nanotubes (CNTs) with various diameters, lengths and surface oxygen-containing group contents was investigated to develop predictive correlations for adsorption, using the isotherm fitting of Polanyi theory-based Dubinin-Ashtakhov (DA) model. Adsorption capacity of aromatic compounds on CNTs is negatively correlated with melting points of aromatic compounds, and surface oxygen-containing group contents and surface area ratios of mesopores to total pores of CNTs, but positively correlated with total surface area of CNTs. Adsorption affinity is positively correlated with solvatochromic parameters of aromatic compounds, independent of tube lengths and surface oxygen-containing group contents of CNTs, but negatively correlated with surface area ratios of mesopores to total pores of CNTs. The correlations of adsorption capacity and adsorption affinity with properties of both aromatic compounds and CNTs clearly have physical significance, can be used successfully with DA model to predict adsorption of aromatic compounds on CNTs from the well-known physiochemical properties of aromatic compounds (i.e., solvatochromic parameters, melting points) and CNTs (i.e., surface area and total acidic group contents), and thus can facilitate the environmental application of CNTs as sorbents and environmental risk assessment of both aromatic contaminants and CNTs. [ABSTRACT FROM AUTHOR]

Knowledge of microbial degradation of biochar-adsorbed organic pollutants is essential for recovering adsorption performance of biochars and reducing secondary pollution in soil remediation. In previous study, desorption of organic compounds from biochars was perceived as a prerequisite for the microbial degradation. However, microbial degradation of the nondesorbable organic compounds on biochars has not been studied. Therefore, degradation of nondesorbable naphthalene (NAPH), phenanthrene (PHEN) and pyrene (PYR) on a wood chip-derived biochar (WBC700) by Sphingobium yanoikuyae B1 was investigated. Significant microbial degradations of nondesorbable organic compounds were observed and followed the order of NAPH < PHEN < PYR. It was newly observed in this study that the microbial degradation of nondesorbable organic compounds on WBC700 was mainly attributed to the •OH in extracellular fluid of Sphingobium yanoikuyae B1. The extracellular •OH was produced through a Fenton-like reaction involved siderophore, H 2 O 2 and iron ions, which could be significantly enhanced by WBC700. Microbial degradation was higher for larger organic compound (e.g., PYR), because larger molecules were adsorbed in relatively larger micropores of WBC700 and thus could be accessible to more extracellular •OH for degradation. The obtained results could provide a new insight into the microbial degradation of biochar-adsorbed organic pollutants in soil remediation. [Display omitted] • Significant microbial degradations of nondesorbable PAHs on WBC700 were observed. • Extracellular •OH of S. yanoikuyae B1 was responsible for PAH degradation on WBC700. • Extracellular •OH was produced through a siderophore-catalyzed Fenton-like reaction. • WBC700 can significantly enhance production of extracellular •OH for PAH degradation. • Microbial degradation was higher for larger organic compound adsorbed on WBC700. [ABSTRACT FROM AUTHOR]

Abstract: The pH-dependent behavior, including the transformation of 1-naphthol by oxidative polymerization to form precipitates in solution and the adsorption of 1-naphthol onto carbon nanotubes (CNTs), was examined. Neglecting the precipitate loss of 1-naphthol and possibly of similar chemicals may result in the overestimation of their adsorption and inadequate interpretation of the underlying adsorption mechanisms. Surface oxygen-containing groups on CNTs and the dissociated species of these groups can interact with the dissociated and neutral species of 1-naphthol in a way similar to polymerization, thus promoting the adsorption of 1-naphthol onto CNTs. Adsorption onto CNTs may reduce the polymeric precipitates of 1-naphthol in solution by possibly decreasing aqueous 1-naphthol concentrations. These observations and the underlying mechanisms are important for predicting the fate and risks of naphthalene and carbaryl in the environment because 1-naphthol is a primary metabolite of naphthalene and carbaryl. In addition, it is possible to enhance the removal of 1-naphthol and similar chemicals by controlling the pH and designing specific surface functional groups for CNTs. [Copyright &y& Elsevier]

• Adsorption of 21 aromatics on 11 commercial ACs were well fitted by DA model. • DA-fitted adsorption parameters were correlated with properties of aromatics and ACs. • Surface area, micropore structure and H/C of ACs were incorporated into correlations. • Solvatochromic parameters and melting points of aromatics were included. • Adsorption of aromatics on ACs can be successfully predicted by the correlations. Correlations capable of predicting organic compound adsorption by activated carbons (ACs) are essential to the applications of ACs as environmental adsorbents in water treatment. Adsorption isotherms of 21 aromatic compounds on 11 ACs both with various physicochemical properties were conducted and fitted by Dubinin-Ashtakhov model to develop the predictive correlations in this study. In addition to the correlations of adsorption capacity with total surface area of ACs, micropore surface area ratios (R micro) of ACs and chemical molar volume reported in previous studies, the negative correlation of adsorption capacity with chemical melting point was newly observed in this study. This negative correlation could be attributed to expansion of chemicals adsorbed on the mesopore or external surface of ACs. Meanwhile, in addition to the positive correlations of adsorption affinity with R micro of ACs, chemical polarity/polarizability and hydrogen bonding donor ability reported also in previous studies, the negative correlation of adsorption affinity with H/C of ACs was newly observed in this study, which should be attributed to that ACs with higher aromaticity could have stronger π - π interaction potential, hydrogen bonding interaction potential and hydrophobic effects for aromatic compounds. These observed correlations can be used to predict aromatic compound adsorption by ACs with readily available properties of both ACs (i.e., surface area, R micro and H/C) and aromatic compounds (i.e., molar volume, melting point and solvatochromic parameters). Moreover, these predictive correlations, incorporating various adsorptive forces, steric hindrance effect and packing efficiency in adsorption and having clearly physicochemical significance, are important for exploring the adsorption mechanisms, and guiding the synthesis of ACs with desired physicochemical properties, and selecting ACs as adsorbents in water treatment applications. [ABSTRACT FROM AUTHOR]

KOH-activated carbon (KAC) with high surface area and abundant micropores are widely used in adsorbing volatile organic compounds (VOCs). Kinetic diameters (σ) of VOCs are an important factor controlling diffusion of VOCs into pores of adsorbent. Yet the influence of kinetic diameters of VOCs on their adsorption by KAC remains unclear. Here, we investigated the dynamic adsorption of VOCs with various kinetic diameters on a prepared KAC with high surface area of 3100 m2/g, pore volume of 2.08 cm3/g and average pore width (D) of 2.68 nm. Adsorption affinity was negatively correlated with size difference (D- σ), indicating that pore width of adsorbent should close to σ to obtain a strong interaction between VOCs and adsorbents. Amounts adsorbed were positively correlated with σ at low relative pressures (p / p 0 < 0.01), and negatively correlated with σ at high relative pressures (p / p 0 > 0.044). The above results suggest that larger molecules with higher affinities are preferentially adsorbed at low relative pressures, amounts adsorbed of smaller molecules are larger than that of bigger molecules at high relative pressures. This study provided new insights into adsorption mechanisms mediated by σ and the development of next generation adsorbents for efficient removal of VOCs. [Display omitted] • High surface area and large pore volume KOH-activated carbon (KAC) was fabricated. • Remarkable adsorption performance for acetone and BTEXs was observed on KAC. • Adsorption mechanism triggered by kinetic diameter (σ) was quantitatively studied. • Average pore width of KAC and its proximity to σ of VOCs facilitate large affinity. • Relationships among amounts adsorbed and σ were dependent on relative pressure. [ABSTRACT FROM AUTHOR]