Transport Of Perfluorooctanoic Acid Research Articles

Insights into the synergistic effects between deposited Fe oxides and dissolved organic matter in influencing perfluorooctanoic acid transport in saturated porous media

Perfluorooctanoic acid (PFOA) transport in the subsurface environment is relevant to drinking water safety, while the compounding effects of soil components on PFOA migration are poorly understood. Laboratory miscible-displacement experiments were conducted using saturated sand columns to explore how metal oxide surfaces and dissolved organic matter (DOM) jointly affect PFOA transport in porous media. Retardation factors indicated that Fe oxide coating inhibited PFOA migration due to electrostatic interaction. However, PFOA recovery rates changed insignificantly, decreasing by less than 4 % when the proportion of Fe oxide-coated sand reached 50 %. DOM (1 mg/L humic acid) in the pore water slightly decreased PFOA recovery rates (by about 10 %) in quartz sand, indicating the effect of hydrophobic interaction on PFOA migration. When the PFOA solution containing 1 mg/L humic acid was injected into the column containing Fe oxide-coated sand, PFOA recovery was significantly decreased by nearly 20 %, and the retardation factor was more than doubled. This could be attributed to the stronger hydrophobic effect provided by the higher DOM deposition on the Fe oxide surface. These results, supported by SEM-EDS, zeta potential, and model fitting data, highlight the microscopic mechanisms by which interactions between metal oxides and DOM influence PFOA transport. However, this inhibitory effect disappeared at higher humic acid concentrations (20 mg/L), indicating the risk of PFOA re-migration when the DOM concentration greatly exceeds the adsorption capacity of the media for it. The findings of this work have implications for predicting or controlling the environmental risks of PFOA in soil and groundwater.

Perfluorooctanoic acid transport and fate difference driven by iron-sulfide minerals transformation interacting with different types of groundwater

Perfluorooctanoic acid (PFOA) is an emerging persistent organic pollutant that threatens human health and ecosystems. However, the intricate mechanism of the change in PFOA transport behavior that interacts with FexSy minerals under groundwater-type differences is not clear. To address this knowledge gap, multi-scale experiments and multi-process reaction models were constructed to investigate the underlying mechanisms. The results showed that different groundwater (NO3-, Cl--Na+, SO42-, and HCO3- types) had significant effects on PFOA transport. NO3-, Cl--Na+, SO42-, and HCO3- decreased the retardation effect of PFOA in the FexSy media. Compared to other groundwater types, the adsorption sites of FexSy were the least occupied in the NO3- groundwater. This observation was supported by the least inhabition of λ in FexSy-NO3- interaction system, which demonstrated that more PFOA was in a high reaction zone and electrostatic repulsion was weakest. The surface tension of different ion types in groundwater provided evidence explaining the lowest inhibition in the FexSy-NO3- system. The 2D spatiotemporal evolution results showed that in FexSy with NO3- system, the pollutant flux (6.00 ×10−5 mg·(m2·s)−1) was minimal. The pollutant flux in the SO42- groundwater system was 9.95-fold that in FexSy with the NO3- groundwater. These findings provide theoretical support for understanding the transport and fate of PFOA in FexSy transformations that interact with different types of groundwater.

Occurrence of a “forever chemical” in the atmosphere above pristine Amazon Forest

Per- and polyfluoroalkyl substances (PFAS), often referred to as “forever chemicals”, are a class of man-made, extremely stable chemicals, which are widely used in industrial and commercial applications. Exposure to some PFAS is now known to be detrimental to human health. By virtue of PFAS long residence times, they are widely detected in the environment, including remote locations such as the Arctics, where the origin of the PFAS is poorly understood. It has been suggested that PFAS may be transported through contaminated waters, leading to accumulation in coastal areas, where they can be aerosolised via sea spray, thereby extending their geographical distribution far beyond their original source regions.The aim of this work is to investigate, for the first time, whether “forever chemicals” could be transported to areas considered to be pristine, far from coastal sites. This study was performed at the Amazonian Tall Tower Observatory (ATTO), a unique remote site situated in the middle of the Amazon rainforest, where a restricted PFAS, perfluorooctanoic acid (PFOA), was observed with concentrations reaching up to 2 pg/m3. A clear trend of increasing concentration with sampling height was observed and air masses from the south over Manaus had the highest concentrations. Atmospheric lifetime estimations, removal mechanisms supported by measurements at two heights (320 and 42 m above the rainforest), and concentration spikes indicated a long-range transport of PFOA to pristine Amazon rainforest. Potential sources, including industrial activities in urban areas, were explored, and historical fire management practices considered.This research presents the first measurements of PFAS in the atmosphere of Amazon rainforest. Remarkably, even in this remote natural environment, appreciable levels of PFAS can be detected. This study provides valuable insights into the long-range transport of the anthropogenic “forever chemical” into a remote natural ecosystem and should raise awareness of potential environmental implications.

Superb green cycling strategies for microbe-Fe0 neural network-type interaction: Harnessing eight key genes encoding enzymes and mineral transformations to efficiently treat PFOA

To address time-consuming and efficiency-limited challenges in conventional zero-valent iron (ZVI, Fe0) reduction or biotransformation for perfluorooctanoic acid (PFOA) treatment, two calcium alginate-embedded amendments (biochar-immobilized PFOA-degrading bacteria (CB) and ZVI (CZ)) were developed to construct microbe-Fe0 high-rate interaction systems. Interaction mechanisms and key metabolic pathways were systematically explored using metagenomics and a multi-process coupling model for PFOA under microbe-Fe0 interaction. Compared to Fe0 (0.0076 day−1) or microbe (0.0172 day−1) systems, the PFOA removal rate (0.0426 day−1) increased by 1.5 to 4.6 folds in the batch microbe-Fe0 interaction system. Moreover, Pseudomonas accelerated the transformation of Fe0 into Fe3+, which profoundly impacted PFOA transport and fate. Model results demonstrated microbe-Fe0 interaction improved retardation effect for PFOA in columns, with decreased dispersivity a (0.48 to 0.20 cm), increased reaction rate λ (0.15 to 0.22 h−1), distribution coefficient Kd (0.22 to 0.46 cm3∙g−1), and fraction f´(52 % to 60 %) of first-order kinetic sorption of PFOA in microbe-Fe0 interaction column system. Moreover, intermediates analysis showed that microbe-Fe0 interaction diversified PFOA reaction pathways. Three key metabolic pathways (ko00362, ko00626, ko00361), eight functional genes, and corresponding enzymes for PFOA degradation were identified. These findings provide insights into microbe-Fe0 “neural network-type” interaction by unveiling biotransformation and mineral transformation mechanisms for efficient PFOA treatment.

Pore size distribution and Al oxide content significantly regulated the effects of humic acid on perfluorooctanoic acid transport in natural soils

The ubiquity of dissolved organic matter (DOM) makes it encounter the released perfluorooctanoic acid (PFOA) in subsurface environment. However, the effect of DOM (e.g., humic acid, HA) on PFOA transport in soils and the critical influencing factors and mechanisms remain obscure. Column experiments were conducted to explore PFOA transport with the presence of different concentrations of HA in three types of soils and two types of Al oxide coated sand. Results revealed soil properties significantly regulate the effects of HA on PFOA transport, for which pore size distribution, minerals content (e.g., Al oxide) and pH were critical influencing soil–properties. For soil with large mesopore volume, pore blockage caused by HA controlled the effect of HA on PFOA transport. Large mesopore volume significantly alleviated pore blockage of HA, and led to insignificant effects of HA on PFOA transport. For soil exhibited minimum mesopore volume, Al oxide content and pH dominated the effect of HA on PFOA transport. Results from Al oxide coated sand (low mesopore volume) columns further proved that higher Al oxide content and lower pH caused more significant facilitating effect of HA on PFOA transport via site competition. Results highlighted the importance of considering pore size distribution and Al oxide content when assessing PFOA mobility capacity with co–transport with DOM in soils.

Mechanisms of heating-electrokinetic co-driven perfluorooctanoic acid (PFOA) adsorption on zeolite

Slow release of emerging contaminants limits their accessibility from soil to pore water, constraining the treatment efficiency of physio-chemical treatment sites. DC fields mobilize organic contaminants and influence their interactions with geo-matrices such as zeolites. Poor knowledge, however, exists on the joint application of heating and electrokinetic approaches on perfluorooctanoic acid (PFOA) transport in porous media. Here, we investigated electrokinetic PFOA transport in zeolite-filled percolation columns at varying temperatures. Variations of pseudo-second-order kinetic constants (kPSO) were correlated to the liquid viscosity variations (η) and elctroosmotic flow velocities (vEOF). Applying DC fields and elevated temperature significantly (>37%) decreased PFOA sorption to zeolite. A good correlation between η, vEOF, and kPSO was found and used to develop an approach interlinking the three parameters to predict the joint effects of DC fields and temperature on PFOA sorption kinetics. These findings may give rise to future applications for better tailoring PFOA transport in environmental biotechnology.

Iron (hydr)oxide dynamic transformation-induced perfluorooctanoic acid transport and attenuation effect: Impacts of initial goethite and associated minerals content and groundwater type

Perfluorooctanoic acid (PFOA) has been widely utilized, leading to serious contamination. Iron (hydr)oxide transformation was varied in media. Whereas, dynamic transformation effect was extensively unclear. Here, iron (hydr)oxide dynamic transformation-induced PFOA transport and attenuation was investigated by emphasizing initial goethite (α-FeOOH) and associated minerals content and groundwater type based on the multi-process attenuation model. Results revealed that groundwater type did not affect the PFOA attenuation pathway. However, it controlled the iron (hydr)oxide dynamic transformation differences. PFOA transport behavior (retardation factor R from 2.61 to 1.91) was significantly affected by iron (hydr)oxide dynamic transformation. Iron (hydr)oxide transformation induced the greatest PFOA transport risk (R = 1.91, attenuation rate λ = 0.0001 min−1) in SO42− environment, where complex α-FeOOH, Fe3O4, and β-Fe2O3·H2O transformed to simplex β-FeOOH, leading to instantaneous (Kd) and kinetic (α) two-site sorption fraction change. Furthermore, the associated mineral Fe3O4 of goethite was crucial in PFOA attenuation (λ from 0.0001 to 0.0002 min−1). Fe3O4 released Fe2+ and the oxidation of Fe2+ to Fe3+ provided electrons, facilitating the formation of F–(CF2)7–COO· radicals, which played a key role in the following cycle attenuation process. This study provides a theoretical basis for understanding the interaction mechanism of PFOA and iron (hydr)oxide dynamic transformation under groundwater differences.

Retention and transport of PFOA and its fluorinated substitute, GenX, through water-saturated soil columns

Perfluoro-2-propoxypropanoic acid (GenX) has emerged as a substitute for perfluorooctanoic acid (PFOA) especially since PFOA was listed among the persistent organic pollutants (POPs) by the Stockholm Convention in 2019. However, limited knowledge exists regarding the behavior and mobility of GenX in natural soils hindering the prediction of its environmental fate. This study investigated the mobility and retention of GenX and PFOA in soils under batch and water-saturated flow-through conditions. Batch experiments revealed that GenX has a lower binding affinity to soil than longer-chained PFOA, potentially threatening groundwater resources. Unlike metal-oxides/minerals (ferrihydrite, gibbsite and manganese dioxide), biochar (BC) and activated carbon (AC) amendments significantly enhanced the sorption of both GenX and PFOA in soil. Sorption data on minerals and carbonaceous materials implied that for shorter-chained GenX, the predominant mode of sorption was through electrostatic (ionic) interactions, while for longer-chained PFOA, hydrophobic interactions became progressively more important with increasing chain length. The dynamic flow experiments demonstrated that these soil amendments enhanced the retention of both compounds, thereby decreasing their mobility. Simultaneous injection of both compounds into columns pre-loaded with either PFOA or GenX increased their retardation. GenX sorption was more affected by pre-sorbed PFOA compared to the minimal impact of pre-loaded GenX on PFOA sorption. A newly developed reactive transport model, which incorporates a two-site sorption model and accounts for kinetic-limited processes, accurately predicted the sorption and transport of both compounds in single and binary contamination systems. These findings have important implications for predicting and assessing the fate and mobility of per- and polyfluoroalkyl substances (PFAS) in soils and groundwaters.

Influence of dietary bioactive compounds on the bioavailability and excretion of PFOA and its alternative HFPO-TA: Mechanism exploration

Oral ingestion is considered an important route of human exposure to perfluorooctanoic acid (PFOA) and its alternative hexafluoropropylene oxide trimer acid (HFPO-TA). Bioactive compounds are widely used as dietary supplements and food additives. However, little is known about the influence of dietary bioactive compounds on the bioavailability of PFOA and HFPO-TA. Here, three dietary bioactive compounds, β-carotene, quercetin and curcumin, were selected to study their influence on the relative bioavailability (RBA) of PFOA and HFPO-TA in soil using a mouse model. Compared to the control group (68.7 ± 6.27 %), quercetin and curcumin at medium and high doses (20 and 100 mg/kg/d) significantly (p < 0.05) decreased PFOA RBA to 55.2 ± 4.85–56.4 ± 4.57 % and 48.3 ± 5.49–48.6 ± 5.44 %, respectively. Mechanism study showed that medium- and high-dose quercetin as well as high-dose curcumin increased urinary excretion of PFOA by 33.6–35.6 % and 32.2 % through upregulating renal expression of multidrug resistance protein 2 (Mrp2) (1.52–1.63 folds) and Mrp4 (1.26–1.53 folds), thereby reducing PFOA accumulation. In PFOA-treated groups, quercetin at medium and high doses dramatically downregulated the hepatic expression of organic anion transport polypeptides (Oatp1a6, Oatp1b2), organic anion transport proteins (Oat1, Oat2), and fatty acid binding proteins (FABP4, FABP12), while curcumin at medium and high doses inhibited the hepatic expression of Oatp1a6, Oat1 and Oat2. These downregulated genes may reduce the transport of PFOA from blood to liver, and in turn decrease the PFOA RBA. However, β-carotene, quercetin and curcumin exhibited no significant effect on RBA and excretion of HFPO-TA (p > 0.05). This indicated the different absorption mechanisms between PFOA and HFPO-TA, and further research is warranted. This study provided a novel perspective for establishing environmentally friendly ways to reduce health hazards from per- and polyfluoroalkyl substances (PFASs).

Effect of dietary antioxidants on excretion of perfluorooctanoic acid (PFOA) via regulating uptake transporters expression and intestinal permeability in mice

Dietary antioxidants, including 2,6-di-tert-butyl-hydroxytoluene (BHT), α-tocopherol (αT) and tea polyphenol (TP), have been widely used in food. However, no data about the effect of food antioxidants on PFOA excretion were available. In this study, excretion of PFOA toward mice (four mice in each group) under the influence of co-ingested food antioxidants (i.e., BHT, αT, and TP) were investigated, and mechanism involved in excretion of PFOA, including RNA expression of uptake and efflux transporters in kidneys and liver involved in PFOA transport and intestinal permeability were also investigated. Chronic exposure to BHT (1.56 mg/kg) increased urinary PFOA excretion from 1795 ± 340 ng/mL (control) to 3340 ± 29.9 ng/mL (BHT treatment). TP treatment (12.5 mg/kg) decreased urinary excretion of PFOA, i.e., with a decrease percentage of 70% compared to the control. Organic anion transporting polypeptides (Oatps) act as uptake transporter mediate renal elimination or reabsorption of PFOA in the kidney. The decrease in urinary excretion of PFOA under TP treatment was associated with significantly (p < 0.05) enhanced expression of Oatp1a1 in the kidney (1.78 ± 0.58 vs 1.00 ± 0.18 in control), which facilitated renal reabsorption of PFOA and in turn decreased urinary excretion of PFOA. αT treatment (12.5 mg/kg) increased fecal PFOA excretion with a value of 228 ± 95.8 ng/g vs control (96.8 ± 22.7 ng/g). Mechanistic investigation revealed that αT treatment reduced intestinal permeability, resulting in increased fecal PFOA excretion.

Effects of biofilms on the retention and transport of PFOA in saturated porous media.

Understanding the fate and transport of perfluorooctanoic acid (PFOA) in soil and groundwater is essential to reliable assessments of its risks. This study investigated the impacts of Gram-positive Bacillus subtilis (BS), Gram-negative Pseudomonas aeruginosa (PA) and wild microbiota (WM) biofilm on the transport of PFOA in saturated sand columns at two ionic strengths (i.e., 1.0 and 20.0mM NaCl). The retention of PFOA in biofilm-coated sand columns was higher than that in uncoated sand columns, due to biofilm-induced reinforced hydrophobic interactions and surface roughness, and decreased zeta potential. However, the retention effects varied among biofilm bacterial species with PFOA retardation factors in PA, WM and BS columns of 1.29-1.38, 1.21-1.29 and 1.11-1.15, respectively. Notably, PA biofilm had the most pronounced effect on PFOA retention. While increasing ionic strength promoted the retention of PFOA in BS biofilm-coated sand, it had no significant impact on PFOA transport in PA and WM biofilm-coated sand. This could be attributed to the differences in biofilm composition, deviating the ionic strengths effects on electrostatic double layer compression. The advection dispersion equation coupled with two-site kinetic retention model well described the transport of PFOA in all saturated columns. Our findings reveal that biofilm plays important roles in PFOA transport in porous media, instructive for risk assessment and remediation of PFOA contamination.

Effects of clay minerals on the transport of perfluorooctanoic acid in saturated porous media

We examined the effects of representative clay minerals, montmorillonite (M) and kaolin (K), on perfluorooctanoic acid (PFOA) transport under saturated conditions. Results showed that low amounts of M or K addition increased and high addition amounts reduced PFOA retardation in quartz sand during the transport. With increasing addition of clay minerals (0-50%, weight ratio), the retardation factor of the M-added system increased from 1.03±0.00 to 1.31±0.03 and then decreased to 0.72±0.06, while that of the K-added system increased to 1.30±0.02 and then decreased to 0.49±0.11. Results of the tracer experiment showed that low amount of M or K addition did not produce preferential flow, while high amount addition induced obvious preferential flow, which resulted in the decrease in PFOA retardation. In addition, due to limitations of the highly negative-charged surface of the M or K modified sand and the solid-liquid ratio of column experiment, the modified M or K sand had low adsorption capacity of PFOA and thus almost did not affect PFOA retention. However, the adsorption and desorption of PFOA by clay minerals might still be responsible for the increases in PFOA retardation with low amount of M or K addition. The results are of great significance for accurately assessing the transport process and eco-environmental risks of PFOA in soil-groundwater systems.

Investigation of the effect of surfactant on the electrokinetic treatment of PFOA contaminated soil

Perfluorooctanoic acid (PFOA) is a persistent, nonbiodegradable environmental pollutant progressively becoming more problematic. Due to its ubiquitous use, PFOA is one of the PFAS chemicals frequently detected in the environment. This study assessed electrokinetic (EK) technology as an in-situ remediation procedure to remove PFOA from kaolinite as a model soil. In this study, a 100 mg/kg of PFOA/kaolinite mixture was used, and the effectiveness of the unenhanced EK was compared with the surfactant-enhanced EK experiments with SDS, NaC, and Tween80. 5% (w/w) surfactants were added to the cathode in the EK experiments of one and two weeks long. The study evaluated the impacts of processing time and electric current on the EK performance. Electroosmosis and electromigration mechanisms affected PFOA transport in soil, causing PFOA to accumulate in the middle of the soil. However, the minimal accumulation of PFOA in the cathode region suggests that electromigration was the main transport mechanism. In a one-week EK experiment, the PFOA removal efficiency in the unenhanced EK process was 14.49% at 10 mA and 19.00% at 20 mA, while in surfactant enhanced EK, it was 17.67% at 10 mA and reached 32.66% at 20 mA. The PFOA removal in surfactant enhanced EK reached 75.58% in the two weeks EK experiments carried out at 20 mA. The NaC-EK experiment exhibited the highest PFOA removal, followed by the SDS-EK experiment and TW80-EK experiment. The outcomes show the feasibility of removing PFAS from contaminated soil using the surfactant-enhanced EK technique. • Enhanced EK for the removal of PFOA from kaolinite soil using three types of surfactants. • PFOA removal from kaolinite doubled by increasing the EK duration from 1 to 2 weeks. • PFOA removal is in the following order EK-NaC > EK-SDS > EK > EK-TW80. • NaC-EK tests achieved 75% PFOA removal, the highest among all surfactant-EK tests.

Transport of perfluorooctanoic acid in unsaturated porous media mediated by SDBS

Per– and polyfluoroalkyl substances (PFAS) contamination is ubiquitous and likely co–exist with hydrocarbon surfactants in the subsurface environment. The transport of PFAS in unsaturated porous media (quartz sand–packed columns) with an anionic hydrocarbon surfactant was investigated using perfluorooctanoic acid (PFOA) and sodium dodecyl benzene sulfonate (SDBS) as representative PFAS and hydrocarbon surfactant at 1.5 and 30 mM NaCl, respectively. Our results show that SDBS inhibited the retardation of PFOA during transport. The degree of the inhibited retardation was more significant at higher concentration of SDBS (CSDBS) for a given concentration of PFOA (CPFOA) and higher ionic strength. In contrast, PFOA only marginally affected the transport of SDBS under all tested conditions. This is mainly due to the greater surface activity of SDBS with respect to PFOA, favoring the competitive preferential adsorption of SDBS at the air–water interface and then the transport of PFOA in the unsaturated sand. This assumption is further supported by the greater air–water adsorption coefficient (Kai) and surface excess (Γ) for SDBS than those for PFOA, as well as the surface tension isotherms that fairly weighted toward to SDBS in the binary PFOA–SDBS system. Our findings indicate the critical role of anionic hydrocarbon surfactant in retarding PFOA transport in unsaturated zone. This should be considered when assessing the transport potential and environmental risk, and developing remedial strategies of PFAS in the subsurface environment.

Perfluorooctanoic Acid Transport in Soil and Absorption and Distribution in Alfalfa (Medicago sativa)

Perfluorooctanoic acid (PFOA) is used as a surfactant in consumer and industrial products and is frequently found in biosolids from wastewater treatment plants. When present in biosolids applied to croplands, PFOA can contaminate feed and fodder used by livestock, but the extent of PFOA transfer from soil to plants is not well characterized. A single dose of radiocarbon (14C)-tagged PFOA was applied to unplanted soil or soil containing growing alfalfa. PFOA transport through unplanted soil and uptake by alfalfa was monitored over a 10-week study period. Radiocarbon was initially measured in roots, stems, and leaves 7 days after [14C]-PFOA application to soil. PFOA accumulation was greatest in leaves during the 10-week sampling. By week 10, PFOA migration through unplanted soil had reached a depth of 22.8 ± 2.5 cm. In contrast, PFOA migrated to 7.5 ± 2.5 cm in soil containing alfalfa plants. The greatest predictor of PFOA concentration in alfalfa leaves was PFOA concentration in the top 5 cm of soil; PFOA concentrations at lower depths were not correlated with alfalfa PFOA concentrations. PFOA transport through soil may be slowed by the presence of forage; however, PFOA accumulation in edible portions of forage plants may increase food animal exposure to PFOA residues.

Effects of anionic hydrocarbon surfactant on the transport of perfluorooctanoic acid (PFOA) in natural soils.

The widespread usage of per- and polyfluoroalkyl substances (PFASs) has led to their ubiquitous co-existence with hydrocarbon surfactants in the subsurface environment. In this study, column experiments were conducted to investigate the effect of an anionic hydrocarbon surfactant (sodium dodecylbenzene sulfonate, SDBS, 1 and 10mg/L) on the transport of perfluorooctanoic acid (PFOA) in two saturated natural soils under different cation type (Na+ and Ca2+) conditions. Results showed that SDBS (10mg/L) significantly enhanced the transport of PFOA in two soils. This was likely because SDBS had a stronger adsorption affinity to the soils than PFOA, and can outcompete PFOA for the finite adsorption sites on the soil surface. The effect of SDBS on PFOA transport varied greatly in the two soils. More negatively charged soil surface and greater soil particle size likely contributed to the more noticeable transport-enhancement of PFOA resulting from the presence of SDBS. Also, the enhancement effect of SDBS (10mg/L) with Ca2+ on PFOA transport was more significantly than that with Na+. This was possibly due to the blocking effect of SDBS to the more positively charged soil surface induced by Ca2+. Findings of this study point out the importance of anionic hydrocarbon surfactants on PFOA transport when assessing its environmental risks and implementing remediation efforts.

Research progress on the pollution, adsorption, and transport of perfluorooctanoic acid (PFOA ) at the sediment-water interface.

Perfluorooctanoic acid (PFOA) is an important perfluorinated surfactant, which has received great attention as an emerging pollutant, due to its persistence, high toxicity, and bioaccumulation. Sediment is an important environmental reservoir for PFOA, while polluted sediment can serve as a long-term contamination source causing pollution to overlying surface water and surrounding groundwater. Here, the source, pollution level, adsorption and transport of PFOA at the sediment-water interface were systematically reviewed. Industrial discharge was the major release for PFOA entering surface water and sediment. PFOA was generally at ng·L-1 and ng·g-1 levels in global surface water and sediment. More serious pollution was found in some parts of China. Sediment composition, hadrochemical condition, natural organic matter, and surfactants could strongly affect PFOA adsorption in sediment, though the controlling mechanisms were controversial. Research on PFOA transport in sediment had just been started with limited progress. There is a great gap in understanding the mechanisms underlying PFOA transport in sediment, which should be strengthened in the future.

Impact of a Hydrocarbon Surfactant on the Retention and Transport of Perfluorooctanoic Acid in Saturated and Unsaturated Porous Media.

The transport and retention behavior of perfluorooctanoic acid (PFOA) in the presence of a hydrocarbon surfactant under saturated and unsaturated conditions was investigated. Miscible-displacement transport experiments were conducted at different PFOA and sodium dodecyl sulfate (SDS) input ratios to determine the impact of SDS on PFOA adsorption at solid-water and air-water interfaces. A numerical flow and transport model was employed to simulate the experiments. The PFOA breakthrough curves for unsaturated conditions exhibited greater retardation compared to those for saturated conditions in all cases, owing to air-water interfacial adsorption. The retardation factor for PFOA with a low concentration of SDS (PFOA-SDS ratio of 10:1) was similar to that for PFOA without SDS under unsaturated conditions. Conversely, retardation was greater in the presence of higher levels of SDS (1:1 and 1:10) with retardation factors increasing from 2.4 to 2.9 and 3.6 under unsaturated conditions due to enhanced adsorption at the solid-water and air-water interfaces. The low concentration of SDS had no measurable impact on PFOA air-water interfacial adsorption coefficients (Kia) determined from the transport experiments. The presence of SDS at the higher PFOA-SDS concentration ratios increased the surface activity of PFOA, with transport-determined Kia values increased by 27 and 139%, respectively. The model provided very good independently predicted simulations of the measured breakthrough curves and showed that PFOA and SDS experienced various degrees of differential transport during the experiments. These results have implications for the characterization and modeling of poly-fluoroalkyl substances (PFAS) migration potential at sites wherein PFAS and hydrocarbon surfactants co-occur.

Effects of ionic strength and cation type on the transport of perfluorooctanoic acid (PFOA) in unsaturated sand porous media

Current understanding of perfluorooctanoic acid (PFOA) transport in unsaturated porous media is still limited with significant variability in solution chemistry. Column experiments were conducted to systematically evaluate the impacts of ionic strength (1.5−30 mM) and cation type (Na+ and Ca2+) on PFOA transport in unsaturated quartz sand. The results showed that an increase in ionic strength (1.5−30 mM) led to greater PFOA retardation in unsaturated columns. Meanwhile, Ca2+ caused more PFOA retardation than Na+ at the same unsaturated conditions. These findings were supported by bubble column experiments, which indicated greater PFOA adsorption at the air-water interface with increasing ionic strength or in the presence of Ca2+ in comparison to Na+. Furthermore, the air-water interfacial (AWI) adsorption coefficients calculated from surface tension isotherms also increased with increasing ionic strength or in the presence of Ca2+ in comparison to Na+. These results clearly confirm that higher ionic strength or cation valence significantly promoted PFOA adsorption at the air-water interface, and thus caused greater PFOA retardation during transport in unsaturated porous media. This work points out the importance of considering solution ionic strength and cation type in assessing the transport behavior of PFOA in unsaturated porous media.

Importance of surface roughness on perfluorooctanoic acid (PFOA) transport in unsaturated porous media

Understanding the subsurface transport of perfluorooctanoic acid (PFOA) is of considerable interest for evaluating its potential risks to humans and ecosystems. In this study, packed-column experiments were conducted to examine the influence of surface roughness on PFOA transport in unsaturated glass beads, quartz sand and limestone porous media. Results showed decreasing moisture content significantly increased the air-water interfacial adsorption of PFOA and led to greater retardation in all three types of porous media. Particularly, rougher surface (limestone > quartz sand > glass beads) and smaller grain size (i.e. a larger solid specific surface area, SSSA) significantly enhanced PFOA retardation under unsaturated conditions. These results were further supported by bubble column experiments and SSSA analysis of porous media, which demonstrate that except for the factors affecting PFOA transport in solid-water interface (e.g. surface charge and chemical heterogeneity), the greater retardation of PFOA during transport is attributed to the larger air-water interfacial areas associated with rougher surface and smaller grain size and hence greater interfacial adsorption of PFOA. Our results indicated the importance of surface roughness on the retention and transport of PFOA in the unsaturated zone.