Combination of adsorption/desorption and photocatalytic reduction processes for PFOA removal from water by using an aminated biosorbent and a UV/sulfite system.

Per- and polyfluoroalkyl substances (PFAS) are stable organic chemicals, which have been used globally since the 1940s and have caused PFAS contamination around the world. This study explores perfluorooctanoic acid (PFOA) enrichment and destruction by a combined method of sorption/desorption and photocatalytic reduction. A novel biosorbent (PG-PB) was developed from raw pine bark by grafting amine groups and quaternary ammonium groups onto the surface of bark particles. The results of PFOA adsorption at low concentration suggest that PG-PB has excellent removal efficiency (94.8%-99.1%, PG-PB dosage: 0.4 g/L) to PFOA in the concentration range of 10 µg/L to 2 mg/L. The PG-PB exhibited high adsorption efficiency regarding PFOA, being 456.0 mg/g at pH 3.3 and 258.0 mg/g at pH 7 with an initial concentration of 200 mg/L. The groundwater treatment reduced the total concentration of 28 PFAS from 18 000 ng/L to 9900 ng/L with 0.8 g/L of PG-PB. Desorption experiments examined 18 types of desorption solutions, and the results showed that 0.05% NaOH and a mixture of 0.05% NaOH + 20% methanol were efficient for PFOA desorption from the spent PG-PB. More than 70% (>70 mg/L in 50 mL) and 85% (>85 mg/L in 50 mL) of PFOA were recovered from the first and second desorption processes, respectively. Since high pH promotes PFOA degradation, the desorption eluents with NaOH were directly treated with a UV/sulfite system without further adjustment. The final PFOA degradation and defluorination efficiency in the desorption eluents with 0.05% NaOH + 20% methanol reached 100% and 83.1% after 24 h reaction. This study proved that the combination of adsorption/desorption and a UV/sulfite system for PFAS removal is a feasible solution for environmental remediation.

Sorption of Perfluorooctane sulfonate (PFOS) including its isomers on hydrargillite as a function of pH, humic substances and Na2SO4.

Perfluorooctane sulfonate (PFOS) is a persistent organic pollutant (POP) and emergent contaminant that are widespread in the environment. Understanding the mechanisms controlling the distribution of PFOS and its isomers between hydrargillite and the water phase is important in order to study their redistribution and mobility in the environment. This study investigated the effects of pH, humic acid, fulvic acid and Na2SO4 on sorption of PFOS isomers to hydrargillite. A mixture of PFOS isomers was spiked into water and hydrargillite was added to the system and shaken for one day; the system was tested with different aqueous composition. Concentrations of PFOS isomers in the aqueous phase were quantified using an ultra-performance liquid chromatograph coupled to a triple quadrupole mass spectrometer. Our results showed that the distribution coefficients of PFOS isomers were found to be 0.76, 0.71, 0.93 and 0.90 at pH 6.5, for 3-/4-/5- PFOS, 6-/2-PFOS, L-PFOS and total PFOS respectively. The distribution coefficients increased at lower pH and decreased at alkaline conditions. The presence of humic substances (HS) increased the sorption slightly at the environmental pH of 6.5, although a competition effect was observed during acidic conditions. A tendency of PFOS distribution to hydrargillite in the presence of Na2SO4 was like its behavior in the presence of HS although the mechanisms behind the sorption were interpreted differently. This study revealed that L-PFOS was readily sorbed when no other chemicals were added or in 20 mg/L FA or 100 mg/L Na2SO4. We suggest that an increase in PFOS sorption in the presence of HS may be due to hydrophobic mechanisms while Na2SO4 contributed to increased sorption through ionic strength effects.

Electrochemical degradation of per- and poly-fluoroalkyl substances using boron-doped diamond electrodes.

Electrochemical degradation using boron-doped diamond (BDD) electrodes has been proven to be a promising technique for the treatment of water contaminated with per- and poly-fluoroalkyl substances (PFAS). Various studies have demonstrated that the extent of PFAS degradation is influenced by the composition of samples and electrochemical conditions. This study evaluated the significance of several factors, such as the current density, initial concentration of PFAS, concentration of electrolyte, treatment time, and their interactions on the degradation of PFAS. A 24 factorial design was applied to determine the effects of the investigated factors on the degradation of perfluorooctanoic acid (PFOA) and generation of fluoride in spiked water. The best-performing conditions were then applied to the degradation of PFAS in wastewater samples. The results revealed that current density and time were the most important factors for PFOA degradation. In contrast, a high initial concentration of electrolyte had no significant impact on the degradation of PFOA, whereas it decreased the generation of F-. The experimental design model indicated that the treatment of spiked water under a current density higher than 14 mA cm-2 for 3-4 h could degrade PFOA with an efficiency of up to 100% and generate an F- fraction of approximately 40-50%. The observed high PFOA degradation and a low concentration of PFAS degradation products indicated that the mineralization of PFOA was effective. Under the obtained best conditions, the degradation of PFOA in wastewater samples was 44-70%. The degradation efficiency for other PFAS in these samples was 65-80% for perfluorooctane sulfonic acid (PFOS) and 42-52% for 6-2 fluorotelomer sulfonate (6-2 FTSA). The presence of high total organic carbon (TOC) and chloride contents was found to be an important factor affecting the efficiency of PFAS electrochemical degradation in wastewater samples. The current study indicates that the tested method can effectively degrade PFAS in both water and wastewater and suggests that increasing the treatment time is needed to account for the presence of other oxidizable matrices.

Sorption of PFOS isomers on goethite as a function of pH, dissolved organic matter (humic and fulvic acid) and sulfate.

Understanding the distribution of PFOS isomers between the aqueous phase and goethite is crucial, since it is an abundant sorbent and thus may have a large influence on the mobility of PFOS. This study was conducted to understand the effects of pH, humic acid (HA), fulvic acid (FA) and sulfate on sorption of PFOS isomers. The results will increase the understanding about what parameters may control the fate and transport of PFOS in surface and ground water. The study was conducted by adding PFOS spiked water to a goethite slurry with different aqueous chemistry. Levels of total PFOS and PFOS isomers were quantified using an Ultra-Performance Liquid Chromatograph coupled to a triple quadrupole mass spectrometer. Results showed that sorption of PFOS was mainly dependent on pH; sorption decreased as pH increased. Presence of HA increased log Kd from 1.29 to 2.03, 1.76 to 1.92 and 1.51 to 1.96 at pH 5.50-7.50 for 3-/4-/4-PFOS, 6-/2-PFOS and L-PFOS, respectively. Changes in the aqueous chemistry also affected the behaviour of PFOS as the addition of Na2SO4 enhanced the sorption of PFOS. Results showed that L-PFOS was more readily sorbed to goethite at pH < 4.35 both in the presence and in the absence of humic or fulvic acids. At pH > 4.5 the 3-/4-/5-PFOS isomer group was more associated to goethite. Besides electrostatic interactions, which controlled the sorption of PFOS, this study indicate that the presence of dissolved humic substances in the aqueous phase enhances the sorption via hydrophobic mechanisms.