Uptake Of Perfluorooctanoic Acid Research Articles

Unravelling the mechanisms of PFAS toxicity to submerged macrophytes and epiphytic biofilms at metabolic and molecular levels

Per- and poly-fluoroalkyl substances (PFAS) are an emerging class of persistent organic pollutants that are widespread in aquatic ecosystems and pose a serious threat to aquatic organisms. It is thus crucial to explore the toxicity mechanisms of PFAS to submerged macrophytes and biofilms. In this study, Vallisneria natans (V. natans) was exposed to environmentally relevant concentrations of perfluorooctanoic acid (PFOA) and perfluorooctane sulphonate (PFOS). Results showed that PFAS induced the excessive production of reactive oxygen species, triggering antioxidant responses. V. natans exhibited an improved stress tolerance by altering the biosynthesis of several plant secondary metabolites and the histidine, arginine, proline pathways in response to PFAS exposure. Moreover, PIP1–1, PIP2–2, SLAH1 and SLAH2 genes were upregulated, indicating the activation of aquaporins and slow-type anion channels. The uptake of PFOA and PFOS by V. natans was 41.74 % and 52.31 %, respectively. Notably, PFAS bound to functional proteins (GSTF10), promoting the detoxification of plants. Exposure to PFAS also altered the structure of biofilms by inducing the synthesis of large amounts of polysaccharides and proteins. The diversity and richness of the microbial community within periphytic biofilms changed significantly. These results provide a comprehensive description of the responses of aquatic plants and periphytic biofilms to PFAS and the removal mechanism of PFAS, contributing to the environmental risk assessments and removal of PFAS in aquatic ecosystems.

Differential uptake and translocation of perfluoroalkyl substances by vegetable roots and leaves: Insight into critical influencing factors

Crop contamination of perfluoroalkyl substances (PFASs) may threaten human health, with root and leaves representing the primary uptake pathways of PFASs in crops. Therefore, it is imperative to elucidate the uptake characteristics of PFASs by crop roots and leaves as well as the critical influencing factors. In this study, the uptake and translocation of PFASs by roots and leaves of pak choi and radish were systematically explored based on perfluorobutanoic acid (PFBA), perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA), and perfluorooctane sulfonate (PFOS). Additionally, the roles of root Casparian strips, leaf stomata, and PFAS structures in the aforementioned processes were elucidated. Compared with pak choi, PFASs are more easily transferred to leaves after root uptake in radish, resulting from the lack of root Casparian strips. In pak choi root, the bioaccumulation of C4-C8 perfluoroalkyl carboxylic acids (PFCAs) showed a U-shaped trend with the increase of their carbon chain lengths, and the translocation potentials of individual PFASs from root to leaves negatively correlated with their chain lengths. The leaf uptake of PFOA in pak choi and radish mainly depended on cuticle sorption, with the evidence of a slight decrease in the concentrations of PFOA in exposed leaves after stomatal closure induced by abscisic acid. The leaf bioaccumulation of C4-C8 PFCAs in pak choi exhibited an inverted U-shaped trend as their carbon chain lengths increased. PFASs in exposed leaves can be translocated to the root and then re-transferred to unexposed leaves in vegetables. The longer-chain PFASs showed higher translocation potentials from exposed leaves to root. PFOS demonstrated a higher bioaccumulation than PFOA in crop roots and leaves, mainly due to the greater hydrophobicity of PFOS. Planting root vegetables lacking Casparian strips is inadvisable in PFAS-contaminated environments, in view of their higher PFAS bioaccumulation and considerable human intake.

Effect of ligand interactions within modified granular activated carbon (GAC) on mixed perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) adsorption

A new adsorbent based on commercial granular activated carbon (GAC) and loaded with Cu(II) (GAC-Cu) was prepared to enhance the adsorption capacity of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). The surface area (SA) and pore volume of GAC-Cu decreased by ∼15% compared to those of pristine GAC. The scanning electron microscopy–energy dispersive spectrometry (SEM-EDS) and leaching test results indicated that, compared with GAC, the Cu atomic ratio and Cu amount in GAC-Cu increased by 2.91 and 2.43 times, respectively. The point of zero charge (PZC) measured using a salt addition method obtained a pH of 6.0 (GAC) and 5.0 (GAC-Cu). According to the isotherm models obtaining highest coefficient of determination (R2), GAC-Cu exhibited a 20.4% and 35.2% increase for PFOA and PFOS in maximum uptake (qm), respectively, compared to those of GAC. In addition, the adsorption affinity (b) for GAC-Cu increased by 1045% and 175% for PFOA and PFOS, respectively. The pH effect on the adsorption capacity of GAC-Cu was investigated. The uptake of PFOA and PFOS decreased with an increase in pH for both GAC and GAC-Cu. GAC-Cu exhibited higher uptake than GAC at pH 6 and 7, but no enhanced uptake was observed at pH 4.0, 5.0, and 8.5. Therefore, ligand interaction was effective at weak acid or neutral pH.

Exceptionally High Perfluorooctanoic Acid Uptake in Water by a Zirconium-Based Metal-Organic Framework through Synergistic Chemical and Physical Adsorption.

Perfluorooctanoic acid (PFOA) is an environmental contaminant ubiquitous in water resources, which as a xenobiotic and carcinogenic agent, severely endangers human health. The development of techniques for its efficient removal is therefore highly sought after. Herein, we demonstrate an unprecedented zirconium-based MOF (PCN-999) possessing Zr6 and biformate-bridged (Zr6)2 clusters simultaneously, which exhibits an exceptional PFOA uptake of 1089 mg/g (2.63 mmol/g), representing a ca. 50% increase over the previous record for MOFs. Single-crystal X-ray diffraction studies and computational analysis revealed that the (Zr6)2 clusters offer additional open coordination sites for hosting PFOA. The coordinated PFOAs further enhance the interaction between coordinated and free PFOAs for physical adsorption, boosting the adsorption capacity to an unparalleled high standard. Our findings represent a major step forward in the fundamental understanding of the MOF-based PFOA removal mechanism, paving the way toward the rational design of next-generation adsorbents for per- and polyfluoroalkyl substance (PFAS) removal.

Analysis of a Passive Sampling Device to Assess the Behavior of Per- and Polyfluoroalkyl Substances in Sediments.

Per- and polyfluoroalkyl substances (PFAS) are an emerging class of compounds that cause health and environmental problems worldwide. In aquatic environments, PFAS may bioaccumulate in sediment organisms, which can affect the health of organisms and ecosystems. As such, it is important to develop tools to understand their bioaccumulation potential. In the present study, the uptake of perfluorooctanoic acid (PFOA) and perfluorobutane sulfonic acid (PFBS) from sediments and water was assessed using a modified polar organic chemical integrative sampler (POCIS) as a passive sampler. While POCIS has previously been used to measure time-weighted concentrations of PFAS and other compounds in water, in our study, the design was adapted for analyzing contaminant uptake and porewater concentrations in sediments. The samplers were deployed into seven different tanks containing PFAS-spiked conditions and monitored over 28 days. One tank contained only water with PFOA and PFBS, three tanks contained soil with 4% organic matter, and three tanks contained soil combusted at 550 °C to minimize the influence of labile organic carbon. The uptake of PFAS from the water was consistent with previous research using a sampling rate model or simple linear uptake. For the samplers placed in the sediment, the uptake process was explained well using a mass transport based on the external resistance from the sediment layer. Uptake of PFOS in the samplers occurred faster than that of PFOA and was more rapid in the tanks containing the combusted soil. A small degree of competition was observed between the two compounds for the resin, although these effects are unlikely to be significant at environmentally relevant concentrations. The external mass transport model provides a mechanism to extend the POCIS design for measuring porewater concentrations and sampling releases from sediments. This approach may be useful for environmental regulators and stakeholders involved in PFAS remediation. Environ Toxicol Chem 2023;00:1-13. © 2023 SETAC.

Investigation into Cationic Surfactants and Polyelectrolyte-Coated β-Zeolites for Rapid and High-Capacity Adsorption of Short- and Long-Chain PFAS

Per- and polyfluoroalkyl substances (PFASs) are aqueous contaminants associated with serious health consequences. Conventional PFAS adsorbents are limited by slow kinetics and low short-chain PFAS uptake, driving interest in high-performing alternatives. Here, β-zeolites were investigated for short- (<C8) and long-chain (≥C8) PFAS removal. β-zeolites with high (CP811C) and low (CP814E) silica/alumina ratios were coated with cetyltrimethylammonium bromide (CTAB) or poly(diallyldimethylammonium chloride) (PDADMAC) to enhance short- and long-chain PFAS retention, represented by heptafluorobutyric acid (PFBA) and perfluorooctanoic acid (PFOA). PFAS rapidly adsorbed onto β-zeolites, reaching equilibrium within 1–2 h. Greater PFOA uptake (91.87 vs 57.77 mg/g) was reported onto the silica-rich β-zeolite, CP811C. While the CTAB coatings reduced PFOA adsorption capacity by 58.7%, the PDADMAC coatings increased PFBA adsorption capacity by 51.3%. On unmodified CP811C, PFOA and PFBA exhibited maximum adsorption capacities of 181.87 and 27.89 mg/g, respectively. Fast and high-capacity adsorption make β-zeolites highly promising PFAS adsorption technology.

Investigating the Electrochemically Driven Capture and Release of Long-Chain PFAS by Redox Metallopolymer Sorbents.

The remediation of perfluoroalkyl substances (PFAS) is an urgent challenge due to their prevalence and persistence in the environment. Electrosorption is a promising approach for wastewater treatment and water purification, especially through the use of redox polymers to control the binding and release of target contaminants without additional external chemical inputs. However, the design of efficient redox electrosorbents for PFAS faces the significant challenge of balancing a high adsorption capacity while maintaining significant electrochemical regeneration. To overcome this challenge, we investigate redox-active metallopolymers as a versatile synthetic platform to enhance both electrochemical reversibility and electrosorption uptake capacity for PFAS removal. We selected and synthesized a series of metallopolymers bearing ferrocene and cobaltocenium units spanning a range of redox potentials to evaluate their performance for the capture and release of perfluorooctanoic acid (PFOA). Our results demonstrate that PFOA uptake and regeneration efficiency increased with more negative formal potential of the redox polymers, indicating possible structural correlations with the electron density of the metallocenes. Poly(2-(methacryloyloxy)ethyl cobaltoceniumcarboxylate hexafluorophosphate) (PMAECoPF6) showed the highest affinity toward PFOA, with an uptake capacity of more than 90 mg PFOA/g adsorbent at 0.0 V vs Ag/AgCl and a regeneration efficiency of more than 85% at -0.4 V vs Ag/AgCl. Kinetics of PFOA release showed that electrochemical bias greatly enhanced the regeneration efficiency when compared to open-circuit desorption. In addition, electrosorption of PFAS from different wastewater matrices and a range of salt concentrations demonstrated the capability of PFAS remediation in complex water sources, even at ppb levels of contaminants. Our work showcases the synthetic tunability of redox metallopolymers for enhanced electrosorption capacity and regeneration of PFAS.

Health Risk Exposure Assessment of Migration of Perfluorooctane Sulfonate and Perfluorooctanoic Acid from Paper and Cardboard in Contact with Food under Temperature Variations.

Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) are extensively used in food-contact paper and cardboard. However, they may migrate from food-contact materials to food, and the migration rate may be increased at elevated temperatures. In addition, there is a positive association of PFOS/PFOA levels with total cholesterol. Therefore, this study aims to assess the human health risk of increased total cholesterol associated with long-term exposure to PFOS and PFOA migration from food-contact paper and cardboard under temperature variation scenarios in adults. An exposure assessment was performed using an uptake dose model to estimate the uptake doses of PFOS and PFOA for the high-, intermediate-, and low-exposure scenarios. Benchmark dose (BMD) modeling was conducted to describe the dose-response relationships between PFOS/PFOA and total cholesterol levels. Finally, a margin of exposure (MOE) approach was used to characterize the risk. The results of the exposure assessment showed that PFOS and PFOA uptake doses in the high-exposure scenarios were around one and two orders of magnitude greater than those in the intermediate- and low-exposure scenarios, respectively. Under high-exposure scenarios, the uptake levels of hundredth-percentile PFOS and PFOA at high temperatures may raise health concerns (MOE < 1). This study provides a methodology to assess the health risks associated with exposure to migration of food contaminants from various types of paper and cardboard that come into contact with food.

Effects of physicochemical properties and co-existing zinc agrochemicals on the uptake and phytotoxicity of PFOA and GenX in lettuce.

Even though the potential toxicity and treatment methods for per- and polyfluoroalkyl substances (PFAS) have attracted extensive attention, the plant uptake and accumulation of PFAS in edible plant tissues as a potential pathway for human exposure received little attention. Our study in a hydroponic system demonstrated that perfluorooctanoic acid (PFOA) and its replacing compound, 2,3,3,3-tetrafluoro-2-(heptafluoropropoxy) propanoic acid (GenX) displayed markedly different patterns of plant uptake and accumulation. For example, the root concentration factor (RCF) of PFOA in lettuce is almost five times of that of GenX while the translocation factor (TF) of GenX is about 66.7% higher than that for PFOA. The co-presence of zinc amendments affected the phyto-effect of these two compounds and their accumulation in plant tissues, and the net effect on their plant accumulation depended on both the properties of Zn amendments and PFAS. Zinc oxide nanoparticles (ZnONPs) at 100mg/L did not affect the uptake of PFOA in either lettuce roots or shoots; however, Zn2+ at the same concentration significantly increased PFOA accumulation in both tissues. In contrast, both Zn amendments significantly lowered the accumulation of GenX in lettuce roots, but only ZnONPs significantly hindered the GenX accumulation in lettuce shoots. The co-exposure to ZnONPs and PFOA/GenX resulted in lower oxidative stress than the plants exposed to PFOA or GenX alone. However, both zinc agrochemicals with or without PFAS led to lower root dry biomass. The results shed light on the property-dependent plant uptake of PFAS and the potential impact of co-existing nanoagrochemicals and their dissolved ions on plant uptake of PFOA and GenX.

Perstraction: A Membrane-Assisted Liquid–Liquid Extraction of PFOA from Water

This study represents a first time that perstraction was assessed as a process to remove perfluorooctanoic acid (PFOA) from water. In the perstraction process, PFOA permeates through a membrane from water to a solvent. The membrane used in this study was polydimethylsiloxane (PDMS). The experimental approach included the following: (1) measurement of partition coefficients for PFOA between water and selected solvents; (2) determination of solubility and diffusivity of the solvents in PDMS; (3) determination of the uptake of PFOA in PDMS; (4) determination of the effects of selected particles imbedded in the PDMS on PFOA uptake and solvent absorption; and (5) demonstration of the perstraction process to remove PFOA from water. PFOA preferentially partitioned to alcohols over water. In addition, ZnO and CuO particles in PDMS significantly enhanced the rate at which PFOA was absorbed in PDMS from deionized water due to ionic interactions. The perstraction of PFOA from deionized water into hexanol was demonstrated. However, perstraction was not successful at removing PFOA from tap water. While the application of perstraction to removing PFOA from water is limited, the idea was demonstrated and information contained within this manuscript is new.

Tissue-specific accumulation, depuration, and effects of perfluorooctanoic acid on fish: Influences of aqueous pH and sex

Perfluorooctanoic acid (PFOA) is widely distributed in nature, particularly in aquatic environments. Its bioaccumulation and toxicity in aquatic organisms can be affected by both the chemical status of PFOA in water and the physiology of the organism. However, research on the patterns of these effects is scarce. In this study, we investigated the influence of aqueous pH (pH 6, acidic; pH 7.5, neutral; pH 9, basic) and fish sex on PFOA uptake, clearance, and biochemical effects in crucian carp (C. auratus) using flow-through exposure. In the 17-d kinetic experiment, PFOA bioaccumulation adhered to a uniform first-order model in which PFOA uptake rates from water to blood and liver in acidic conditions were faster than those in other conditions, indicating possible acidic pH influence on PFOA uptake. PFOA clearance rates in these compartments of males were slower than in females, which was attributed to the notably stronger expression of Oat2 (organic anion transporter 2, responsible for reabsorption) in the kidneys of males. Similar responses were observed for peroxisome proliferation-related biomarkers at different pH levels and in different sexes. These biochemical responses were driven by the internal concentrations of PFOA. The inhibition acetylcholinesterase activity in the fish brain was closely linked to changes in P-glycoprotein content, demonstrating a protective relationship. Collectively, an aqueous pH lower than 7.5 might affect the uptake of PFOA by fish. The clearance discrepancies between the sexes highlight the importance of anion carriers for ionizable organic compounds in aquatic organisms.

Controlled uptake of PFOA in adult specimens of Paracentrotus lividus and evaluation of gene expression in their gonads and embryos

Perfluorooctanoic acid (PFOA) has been largely used in the manufacturing industry but a few years ago it turned out to be a dangerous pollutant which is now of concern for terrestrial and aquatic environments. Here, we investigated the bioaccumulation of PFOA in the sea urchin Paracentrotus lividus after exposure to different concentrations of the pollutant for 28 days. We observed rapid uptake of PFOA in the coelomic fluid collected weekly during the exposure period and high bioaccumulation in gonads at the end of the experiment. Interestingly, animals were also able to fast depurate when relocated to a clean environment. In addition, to assess the effect of PFOA on sea urchins’ physiological pathways, we analysed the expression profile of some marker genes both in the gonads and in the embryos obtained from parents exposed to PFOA. Our results suggest that PFOA is a persistent, bioaccumulative compound that adversely affects the health of the exposed organisms and their offspring by causing significant changes in the expression of some key target genes and the occurrence of developmental anomalies in the embryos.

Installation of synergistic binding sites onto porous organic polymers for efficient removal of perfluorooctanoic acid

Herein, we report a strategy to construct highly efficient perfluorooctanoic acid (PFOA) adsorbents by installing synergistic electrostatic/hydrophobic sites onto porous organic polymers (POPs). The constructed model material of PAF-1-NDMB (NDMB = N,N-dimethyl-butylamine) demonstrates an exceptionally high PFOA uptake capacity over 2000 mg g−1, which is 14.8 times enhancement compared with its parent material of PAF-1. And it is 32.0 and 24.1 times higher than benchmark materials of DFB-CDP (β-cyclodextrin (β-CD)-based polymer network) and activated carbon under the same conditions. Furthermore, PAF-1-NDMB exhibits the highest k2 value of 24,000 g mg−1 h−1 among all reported PFOA sorbents. And it can remove 99.99% PFOA from 1000 ppb to <70 ppt within 2 min, which is lower than the advisory level of Environmental Protection Agency of United States. This work thus not only provides a generic approach for constructing PFOA adsorbents, but also develops POPs as a platform for PFOA capture.

Foliar uptake overweighs root uptake for 8:2 fluorotelomer alcohol in ryegrass (Lolium perenne L.): A closed exposure chamber study

Fluorotelomer alcohols (FTOHs) are a kind of volatile monomers that can be released from FTOH-based products and their ubiquitous occurrence raises concerns for their plant uptake. To study plant uptake pathway, translocation, and transformation characteristics of 8:2 FTOH, ryegrass (Lolium perenne L.) was selected as a model plant for 8:2 FTOH exposure via air and/or soil uptake for 4 weeks in custom-built closed exposure chambers. The bio-degradation of spiked 8:2 FTOH in the soil led to the production of C6-C8 perfluoroalkyl carboxylic acids (PFCAs) and other intermediates, and perfluorooctanoic acid (PFOA) was the main product (54.9%–88.9%). In the ryegrass, foliar uptake of 8:2 FTOH contributed 78.1% ± 3.4% to the total shoot accumulation while PFOA in shoot was mainly from root uptake of PFOA and the further biotransformation of other unmonitored intermediates biodegraded from 8:2 FTOH in the soil (83.7% ± 7.3%). The results in this study provides the first laboratory evidences that foliar uptake of airborne 8:2 FTOH can be a major pathway over root uptake and its subsequent biotransformation contribute to the burden of PFCA accumulation in plants.

Evaluating the potential of KOH-modified composite biochar amendment to alleviate the ecotoxicity of perfluorooctanoic acid-contaminated sediment on Bellamya aeruginosa

Modified composite biochar offers a cost-effective solution for the remediation of contaminated sediments; however, few studies have evaluated the effects of modified composite biochar amendment on the ecotoxicity of contaminated sediment based on benthic macroinvertebrates. A 21-day sediment toxicity test was conducted using the freshwater snail Bellamya aeruginosa to examine the intrinsic ecotoxicity of a novel KOH-modified composite biochar (KOH-CBC) and its efficacy for reducing the bioavailability, uptake, and ecotoxicity of perfluorooctanoic acid (PFOA). It was found that KOH-CBC is toxic to B. aeruginosa, which may be attributed to its high polycyclic aromatic hydrocarbons (PAHs) content and alkalinity. The addition of KOH-CBC to PFOA-contaminated sediments can markedly reduce the bioavailability and uptake of PFOA by more than 90% and 50%, respectively, and subsequently alleviate the toxicity of PFOA to B. aeruginosa by at least 30%. Increasing the KOH-CBC dosage is not beneficial for further mitigating the toxicity of PFOA-contaminated sediments. Our findings imply that KOH-CBC is a promising sorbent for the in-situ remediation of PFOA-contaminated sediments. Application of acidified KOH-CBC at a dosage of approximately 1–3% will be sufficient to control the ecotoxicity of PFOA; however, its long-term environmental effects should be further validated.

Effect of soil organic matter on the plant uptake of perfluorooctanoic acid (PFOA) and perfluorooctanesulphonic acid (PFOS) in lettuce on granular activated carbon-applied soil.

The presence of perfluorooctanoic acid (PFOA) and perfluorooctanesulphonic acid (PFOS) in crops is an important consideration for food safety. The soil organic matter (SOM) content may affect the adsorption potential of PFOA and PFOS in water and soil and their subsequent uptake in crops. To better understand these dynamics, the adsorption and uptake of PFOA and PFOS in lettuce were investigated using granular activated carbon (GAC)-treated soils with varying SOM content. The adsorption potential of GAC was investigated, with maximum adsorption capacities for PFOA and PFOS calculated to be 9.091mgg-1 and 27.778mgg-1, respectively. These values decreased to 5.208mgg-1 and 17.241mgg-1, respectively, after the addition of 0.04 wt% humic acid. The average plant uptake factor (PUF) in low and high perfluoroalkyl and polyfluoroalkyl acid (PFAA)-contaminated soils with 4.0 wt% SOM was restricted to 0.353 for PFOA and 0.108 for PFOS. The PUFs were approximately two times lower than those for soil with 2.6 wt% SOM. Addition of 1 wt% GAC to the soil successfully reduced the PUF by up to 99.4%, with values of 0.006 (PFOA) and 0.005 (PFOS) in 2.6 wt% SOM-treated soil and 0.079 (PFOA) and 0.023 (PFOS) in 4.0 wt% SOM-treated soil. Although the PUF in the GAC-treated soil was drastically decreased, the PUF of the soil with 4.0 wt% SOM was at least four times higher than that with 2.6 wt% SOM. Therefore, SOM content is an important consideration in the remediation of PFOA- and PFOS-contaminated farmland soil using carbonaceous adsorbent.

Rapid and Efficient Removal of Perfluorooctanoic Acid from Water with Fluorine-Rich Calixarene-Based Porous Polymers.

On account of its nonbiodegradable nature and persistence in the environment, perfluorooctanoic acid (PFOA) accumulates in water resources and poses serious environmental issues in many parts of the world. Here, we present the development of two fluorine-rich calix[4]arene-based porous polymers, FCX4-P and FCX4-BP, and demonstrate their utility for the efficient removal of PFOA from water. These materials featured Brunauer-Emmett-Teller (BET) surface areas of up to 450 m2 g-1, which is slightly lower than their nonfluorinated counterparts (up to 596 m2 g-1). FCX4-P removes PFOA at environmentally relevant concentrations with a high rate constant of 3.80 g mg-1 h-1 and reached an exceptional maximum PFOA uptake capacity of 188.7 mg g-1. In addition, it could be regenerated by simple methanol wash and reused without a significant decrease in performance.

Enhanced adsorption of perfluorooctanoic acid (PFOA) from water by granular activated carbon supported magnetite nanoparticles

A new composite material (Fe3O4@GAC, Fe3O4 nanoparticles loaded on a commercial granular activated carbon (GAC)) was prepared through a facile hydrothermal process at controlled Fe2+:Fe3+ molar ratios in air. Fe3O4@GAC was thoroughly characterized and tested for adsorption of perfluorooctanoic acid (PFOA) in water. Fe3O4@GAC(2:1), prepared at an Fe2+:Fe3+ molar ratio of 2:1, showed the best PFOA removal and offered 28.8% higher adsorption capacity than the parent GAC at final pH 4.0. The enhanced adsorption of PFOA was attributed to concurrent hydrophobic, electrostatic and complexation interactions between PFOA, GAC and Fe3O4. GAC in the composite played an important role for PFOA adsorption. The presence of Ca2+ ions (10 mM) at final pH 5.0–10.0 more than doubled the PFOA equilibrium uptake of PFOA by Fe3O4@GAC(2:1) due to the calcium bridging effect between PFOA and the Si-OH or Fe-OH groups in Fe3O4@GAC(2:1), and because of the Ca2+-modification induced formation of PFOA hemi-micelles on the surface or in the relatively large pores (2.27 nm) of Fe3O4@GAC(2:1). Fe3O4@GAC(2:1) was amenable to efficient regeneration using a mixture of NaOH solution and methanol. Fe3O4@GAC holds the potential to be used as a simple and low-cost adsorbent for enhanced adsorption of PFOA, especially in waters of high hardness and alkalinity.

Removal of perfluorooctanoic acid from water using calcined hydrotalcite – A mechanistic study

Calcined hydrotalcite (CHT) was evaluated for its potential removal of perfluorooctanoic acid (PFOA) from water in this study. The uptake of PFOA by CHT could be as high as 1587 mg/g (ca. 3.8 mmol/g), slightly larger than the anion exchange capacity (AEC) of the hydrotalcite (HT). Such a high removal was fast and pH independent, suggesting the versatile use of CHT. Due to the structural memory effect of HT, the removal involved adsorption of PFOA during HT recovery and intercalation of PFOA into the interlayer of restructured HT at low and high initial concentrations, respectively. Limited by the specific surface area and AEC, the intercalated PFOA would form a vertical bilayer or admicelle conformation. As such, the HT intercalated with PFOA became one-layer stacking with a basal spacing of 2.04 nm in contrast to the 3R polytype of recovered HT having a layer thickness of 0.78 nm, as confirmed by X-ray diffraction, thermogravimetric, and infra-red analyses. Due to its high PFOA removal capacity and large partitioning coefficient, the amount of CHT used, thus, the disposal of PFOA-laden solid could be minimized.

Genotypic variation and mechanism in uptake and translocation of perfluorooctanoic acid (PFOA) in lettuce (Lactuca sativa L.) cultivars grown in PFOA-polluted soils

The cultivation of crop cultivars with low pollutant accumulation is an important strategy to reduce the potential health risks of food produced from polluted soils. In this study, we identified three loose-leaf lettuce cultivars with low accumulation of perfluorooctanoic acid (PFOA), a highly toxic and persistent organic pollutant. PFOA concentrations in the shoots of low-PFOA cultivars were 3.7–5.5-fold lower than those of high-PFOA cultivars. The identification of low-PFOA cultivars could contribute to ensuring food safety despite cultivation in highly polluted soils (1 mg/kg) based on the tolerable daily PFOA intake (1.5 μg/kg/d). We detected lower desorbing fractions of PFOA in rhizosphere soil, lower bioconcentration factors, and higher distribution in the cell walls and organelles of roots in low-PFOA cultivars, all of which are key factors in limiting PFOA uptake and translocation from soil to shoots, than in high-PFOA cultivars. This study reveals the mechanism of PFOA uptake from soil to crop and lays a foundation for establishing a cost-effective strategy to plant crops in polluted soil and reduce exposure risk due to persistent organic pollutants in crops.