Ziwen Du

Adsorption behavior and mechanism of perfluorinated compounds on various adsorbents--a review.

Perfluorinated compounds (PFCs) have drawn great attention recently due to their wide distribution in aquatic environments and potential toxic to animals and human beings. Adsorption not only is an effective technology to remove PFCs from water or wastewater, but also affects PFC distribution at solid-liquid interfaces and their fate in aquatic environments. This article reviews the adsorption behavior of different PFCs (mainly perfluorooctane sulfonate and perfluorooctanoate) on various adsorptive materials. Some effective adsorbents are introduced in detail in terms of their preparation, characteristics, effects of solution chemistry and PFC properties on adsorption. Adsorption mechanisms of PFCs on different adsorbents are summarized, and various interactions including electrostatic interaction, hydrophobic interaction, ligand exchange, and hydrogen bond are fully reviewed. The adsorbents with amine groups generally have high adsorption capacity for PFCs, and formation of micelles/hemi-micelles plays an important role in achieving high adsorption capacity of perfluorinated surfactants on some porous adsorbents. Hydrophobic interaction is mainly responsible for PFC adsorption, but the difference between PFCs and traditional hydrocarbons has not clearly clarified. This review paper would be helpful for the preparation of effective adsorbents for PFC removal and understanding interfacial process of PFCs during their transport and fate in aquatic environments.

Enhanced adsorption of perfluorooctane sulfonate and perfluorooctanoate by bamboo-derived granular activated carbon.

A bamboo-derived granular activated carbon with large pores was successfully prepared by KOH activation, and used to remove perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) from aqueous solution. The granular activated carbon prepared at the KOH/C mass ratio of 4 and activation temperature of 900°C had fast and high adsorption for PFOS and PFOA. Their adsorption equilibrium was achieved within 24h, which was attributed to their fast diffusion in the micron-sized pores of activated carbon. This granular activated carbon exhibited the maximum adsorbed amount of 2.32mmol/g for PFOS and 1.15mmol/g for PFOA at pH 5.0, much higher than other granular and powdered activated carbons reported. The activated carbon prepared under the severe activation condition contained many enlarged pores, favorable for the adsorption of PFOS and PFOA. In addition, the spent activated carbon was hardly regenerated in NaOH/NaCl solution, while the regeneration efficiency was significantly enhanced in hot water and methanol/ethanol solution, indicating that hydrophobic interaction was mainly responsible for the adsorption. The regeneration percent was up to 98% using 50% ethanol solution at 45°C.

Removal of perfluorinated carboxylates from washing wastewater of perfluorooctanesulfonyl fluoride using activated carbons and resins

Perfluorooctanesulfonyl fluoride (PFOSF) washing wastewater contains high concentrations of perfluorinated carboxylates (PFCAs) including perfluorohexanoate (PFHxA, 0.10 mmol/L), perfluoroheptanoate (PFHpA, 0.11 mmol/L), and perfluorooctanoate (PFOA, 0.29 mmol/L). For the first time, we investigated the removal of these PFCAs from actual wastewater using the bamboo-derived activated carbon (BAC) and resin IRA67. Adsorption kinetics, effects of adsorbent dose, solution pH, and inorganic ions, as well as regeneration and reuse experiments were studied. The removal percents of three PFCAs by BAC and IRA67 followed the increasing order of PFHxA < PFHpA < PFOA, but the adsorption equilibrium time conformed to the reverse trend. PFCAs removal on IRA67 decreased with increasing pH, but BAC almost kept stable PFCAs removal at pH above 5.0. Among competitive adsorption of three PFCAs, PFOA was preferentially adsorbed on both BAC and IRA67. PFCAs removal from actual wastewater by BAC was higher than that in simulated solution, due to the presence of high concentration of inorganic ions in the wastewater. However, the co-existing organic compounds in wastewater significantly suppressed the adsorption of PFCAs. Both spent BAC and IRA67 were successfully regenerated by ethanol solution or NaCl/methanol mixture, and IRA67 showed the stable removal of PFCAs in five adsorption cycles.

Role of Air Bubbles Overlooked in the Adsorption of Perfluorooctanesulfonate on Hydrophobic Carbonaceous Adsorbents

Hydrophobic interaction has been considered to be responsible for adsorption of perfluorooctanesulfonate (PFOS) on the surface of hydrophobic adsorbents, but the long C-F chain in PFOS is not only hydrophobic but also oleophobic. In this study, for the first time we propose that air bubbles on the surface of hydrophobic carbonaceous adsorbents play an important role in the adsorption of PFOS. The level of adsorption of PFOS on carbon nanotubes (CNTs), graphite (GI), graphene (GE), and powdered activated carbon (PAC) decreases after vacuum degassing. Vacuum degassing time and pressure significantly affect the removal of PFOS by these adsorbents. After vacuum degassing at 0.01 atm for 36 h, the extent of removal of PFOS by the pristine CNTs and GI decreases 79% and 74%, respectively, indicating the main contribution of air bubbles to PFOS adsorption. When the degassed solution is recontacted with air during the adsorption process, the removal of PFOS recovers to the value obtained without vacuum degassing, further verifying the key role of air bubbles in PFOS adsorption. By theoretical calculation, the distribution of PFOS in air bubbles on the adsorbent surfaces is discussed, and a new schematic sorption model of PFOS on carbonaceous adsorbents in the presence of air bubbles is proposed. The accumulation of PFOS at the interface of air bubbles on the adsorbents is primarily responsible for its adsorption, providing a new mechanistic insight into the transport, fate, and removal of PFOS.

Effect of co-existing organic compounds on adsorption of perfluorinated compounds onto carbon nanotubes

Co-existing organic compounds may affect the adsorption of perfluorinated compounds (PFCs) and carbon nanotubes in aquatic environments. Adsorption of perfluorooctane sulfonate (PFOS), perfluorooctane acid (PFOA), perfluorobutane sulfonate (PFBS), and perfluorohexane sulfonate (PFHxS) on the pristine multi-walled carbon nanotubes (MWCNTs-Pri), carboxyl functionalized MWCNTs (MWCTNs-COOH), and hydroxyl functionalized MWCNTs (MWCNTs-OH) in the presence of humic acid, 1-naphthol, phenol, and benzoic acid was studied. Adsorption kinetics of PFOS was described well by the pseudo-second-order model and the sorption equilibrium was almost reached within 24 h. The effect of co-existing organic compounds on PFOS adsorption followed the decreasing order of humic acid>1-naphthol>benzoic acid>phenol. Adsorbed amounts of PFOS decreased significantly in the presence of co-existing or preloaded humic acid, and both adsorption energy and effective adsorption sites on the three MWCNTs decreased, resulting in the decrease of PFOS adsorption. With increasing pH, PFOS removal by three MWCNTs decreased in the presence of humic acid and phenol. The adsorbed amounts of different PFCs on the MWCNTs increased in the order of PFBS<PFHxS<PFOA<PFOS. The increase of both initial concentrations and the number of aromatic rings of co-existing organic compounds suppressed PFOS adsorption on the MWCNTs.

Selective and Fast Adsorption of Perfluorooctanesulfonate from Wastewater by Magnetic Fluorinated Vermiculite

A novel magnetic fluorinated adsorbent with selective and fast adsorption of perfluorooctanesulfonate (PFOS) was synthesized via a simple ball milling of Fe3O4 and vermiculite loaded with a cationic fluorinated surfactant. The loaded Fe3O4 nanoparticles increased the dispersibility of fluorinated vermiculite (F-VT) in water and allowed the magnetic separability. The nanosized Fe3O4 was homogeneously embedded into the adsorbent surfaces, improving the hydrophilicity of F-VT external surface, and this hybrid adsorbent still kept the hydrophobic fluorinated interlayer structure. With this unique property, Fe3O4-loaded F-VT has very fast and selective adsorption for PFOS in the presence of other compounds, due to the fluorophilicity of C-F chains intercalated in the adsorbent interlayers. This novel adsorbent has a high sorption capacity for PFOS, exhibiting PFOS removal from fire-fighting foam wastewater that is much higher than that of powdered activated carbon and resin due to its high selectivity for PFOS. The used Fe3O4-loaded F-VT was successfully regenerated by methanol and reused five times without reduction in PFOS removal and magnetic performance. The Fe3O4-loaded F-VT demonstrates promising application for PFOS removal from real wastewater.

Adsorptive removal of emerging polyfluoroalky substances F-53B and PFOS by anion-exchange resin: A comparative study

Chrome plating is an important emission source of perfluorinated compounds (PFCs) industrial uses in China, where two commercial products potassium 2-(6-chloro-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyloxy) (F-53B) and perfluorooctane sulfonate (PFOS) are applied as mist suppressant, causing non-negligible environmental risk. In this paper, anion-exchange resin IRA67 was evaluated for F-53B and PFOS removal from simulated and actual wastewater. Adsorption kinetics exhibited higher adsorption velocity and capacity of IRA67 for PFOS than F-53B due to their difference in molecular structures. Adsorption isotherms demonstrated the adsorption capacity of F-53B and PFOS on IRA67 was 4.2mmol/g and 5.5mmol/g, respectively. Because of the deprotonating of amine groups, solution pH had significant effect on IRA67 at pH>10. The results indicated that besides anion exchange other interactions including hydrophobic interaction and the formation of micelles or hemi-micelles were all involved in adsorption process. Coexisting sulfate and chromate in wastewater decreased adsorption capacities of F-53B and PFOS. The spent resin could be regenerated by the NaCl/NaOH and methanol mixed solution. In the mixed system and actual wastewater IRA67 can simultaneously remove F-53B and PFOS without obvious preference but the removal percent can be affected by competitive effect.

Adsorption of perfluorooctane sulfonate on carbon nanotubes: influence of pH and competitive ions

Perfluorooctane sulfonate (PFOS) is one of the persistent organic pollutants that has aroused global concern. Carbon nanotubes (CNTs) have drawn much research attention due to their unique properties. This study was aimed to investigate the adsorption behaviour of PFOS with relation to CNTs and clarify their interactions. Electrostatic repulsion suppressed the sorption of PFOS to multi-walled carbon nanotubes (MWCNTs), resulting in low sorption at high pH. With the increase of anion concentration, the removal of PFOS decreased by 20 to 30% because ionic strength changed the aggregation of the MWCNTs. Unlike inorganic anions, cationic metals including Cu(II) and Pb(II) had a significant impact on the sorption of PFOS onto the MWCNTs. At low concentrations of Cu(II) and Pb(II), PFOS removal decreased due to the suppressive effect of ionic strength, while the removal of PFOS increased rapidly with increasing metal concentrations, especially for functionalized MWCNTs. The enhanced adsorption of PFOS at high Cu(II) and Pb(II) concentrations was attributed to the adsorbed cationic metals which might further adsorb PFOS.

Effect of hydro-oleophobic perfluorocarbon chain on interfacial behavior and mechanism of perfluorooctane sulfonate in oil-water mixture

Perfluorocarbon chain of perfluorooctane sulfonate (PFOS) is not only hydrophobic but also oleophobic, and its effect on PFOS distribution in oil-water mixture and underlying mechanism are unclear. For the first time, we propose that PFOS can emulsify oil-water mixture only in the presence of air, completely different from hydrocarbon surfactants. The perfluorocarbon chain repels hydrophobic compounds and its oleophobicity increases with decreasing polarity of organic solvents. The formed emulsion in oil phase contains high concentrations of PFOS, resulting in PFOS decrease in water. The increase of shaking speed and time as well as oil and air volume all increase the emulsification and decrease PFOS concentrations in water. During the settling process, the emulsion gradually disappears and the concentrated PFOS is released into water. The emulsification mechanism of PFOS based on air bubbles is proposed, and PFOS partitions to the interfaces of air bubbles with the hydro-oleophobic perfluorocarbon chain stretching into air bubbles and the polar head in water. This study clarifies the ambiguous understanding of the oleophobicity of perfluorocarbon chain in PFOS, and it is helpful for the understanding of the transport and fate of PFOS at oil-water interfaces in aquatic environments as well as the enhanced removal of PFOS from wastewater.