Transport Of Perfluorooctane Sulfonate Research Articles

A systematic investigation of single solute, binary and ternary PFAS transport in water-saturated soil using batch and 1-dimensional column studies: Focus on mixture effects

This study aimed to investigate the transport and release of per- and polyfluoroalkyl substances (PFAS), as single solutes and binary and ternary mixtures, and associated competitive sorption effects in water-saturated soil. Batch sorption isotherm and desorption, and one-dimensional miscible displacement studies were conducted. For the batch study, the mixtures exhibited extensive sorption isotherm nonlinearity at aqueous concentrations exceeding 20 µg/L. At and above this threshold, competitive effects significantly decreased PFAS sorption, mostly affecting perfluorooctanoic acid (PFOA) and perfluorohexane sulfonate (PFHxS). Importantly, mixture effects exacerbated isotherm nonlinearity and may increase the leaching of PFAS in subsurface soil and groundwater. Further, up to 100% desorption occurred for single solutes and mixtures, indicating that the studied PFAS were weakly sorbed. For the column study, at influent concentrations (21 – 27 µg/L, depending on PFAS) near the threshold, PFOA and PFHxS breakthrough curves (BTC) generally exhibited equilibrium (nonlinear) transport, whereas perfluorooctane sulfonate (PFOS) exhibited nonequilibrium transport, with minimal or no mixture effects. Nonequilibrium transport of PFOS was driven by rate-limited sorption, especially as flow interruption tests confirmed the absence of physical nonequilibrium. The sorption distribution coefficients (Kd) from moment and frontal analyses, and 2-site modelling of the BTC, were consistent with the batch-derived Kd, although comparatively smaller. Such discrepancies may limit the applicability of batch-derived Kd values for predictive transport modelling purposes. Overall, understanding mixture impacts may aid effective predictive modelling of PFAS transport and leaching, especially in aqueous film forming foam (AFFF)-source zone areas associated with elevated PFAS concentrations. At low or environmental PFAS concentrations, mixture effects can be expected to be play a minor role in influencing PFAS transport.

Modelling the transport of PFOS from single lined municipal solid waste landfill

The contaminant transport of perfluorooctane sulfonate (PFOS) through the base of a municipal solid waste landfill lined by a single composite liner comprised of a geomembrane over a geosynthetic clay liner (GCL) and a 3.75 m-thick attenuation layer underlain by an aquifer is examined. Both pure diffusive transport and advective transport through holed wrinkles are modelled. The peak concentrations of PFOS predicted for the aquifer beneath the landfill are compared to the maximum allowable PFOS concentration established by Australia, Canada, Europe, and various US states. The results show that (a) in most cases with zero leakage and pure diffusive transport, regulatory limits are met; however, (b) if there are holed wrinkles in the geomembrane, the impact is highly dependent on the length of holed wrinkle per hectare, the geomembrane-GCL interface transmissivity, and the GCL hydraulic conductivity. Factors affecting the length of holed wrinkles are discussed. In many of the cases examined, the peak concentrations of PFOS in the aquifer exceed the limits set by the different jurisdictions, indicating that a single composite liner may not be sufficient to contain PFOS acceptable level and recommends that realistic contaminant impact calculations be performed in each specific case.

Different transport behaviors and mechanisms of perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS) in saturated porous media

Perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS) in soil aroused increasing concern, however there is little information about their transport in porous media, which is urgently needed to better control their environmental risks. In this study, saturated sand columns (considering the coupled effect of solution cation type and pH) and a two-site nonequilibrium transport model (TSM) were used to investigate the transport behaviors and mechanisms of PFOA and PFOS. Breakthrough data and the TSM parameters showed PFOA had higher mobility than PFOS, and divalent cation could inhibit their transport by increasing the nonequilibrium interactions between them and the sand. pH had little influence on PFOA migration when there was only monovalent cation in the solution since PFOA had limited affinity with the sand, however, polyvalent cation could provide additional adsorption sites for it through cation bridging and enhance the effect of pH. Differently, decreasing pH inhibited the transport of PFOS more significantly, and the effect was stronger than that of changing cation type. That proved mechanisms like hydrogen-bonding which were sensitive to solution pH played an important role in PFOS migration. These results provide important scientific basis to the remediation strategy and the migration prediction model development of PFOA and PFOS.

Influence of oxic/anoxic condition on sorption behavior of PFOS in sediment

Sediment components and redox properties change with oxic/anoxic condition, which affect the environmental transport of perfluorooctane sulfonate (PFOS). Herein, the influence of oxic/anoxic condition on the variation of redox and residual components of sediments, where organic matter, iron and manganese oxides are separated from the original sediment collected from Lake Taihu, China, are investigated. Meanwhile, the distinguishing sorption behaviors of PFOS on various residual sediments under oxic and anoxic condition are studied. Sediment after extracting iron and manganese (S-FeMn), which possessed the highest organic carbon (0.99%), had the highest affinity for PFOS under oxic condition. However, anoxic environment resulted in an increase of the pH, dissolving of organic carbon and de-protonation of S-FeMn, which caused the lower sorption capacity of PFOS on S-FeMn. Sediment after extracting manganese (S-Mn) had the higher sorption ability in anoxic environment because the Fe2+ from S-Mn provided more effective electrostatic sites for anionic PFOS. When the environment changed to oxic condition, the iron existed as trivalent form in S-Mn, which resulted in a block of effective sorption site and reduced the sorption amounts of PFOS. The higher percentage of manganese oxides restrained the sorption of PFOS. Hence, whether or not oxic/anoxic condition promoted the PFOS sorption depended on both the percentage and form of various components in the sediment. The study generated further insight into the environmental transport of PFOS in the sediments with different properties and the wetland system, where oxic/anoxic subsurface flow was constructed.

Exploring the fate, transport and risk of Perfluorooctane Sulfonate (PFOS) in a coastal region of China using a multimedia model

Perfluorooctane Sulfonate (PFOS) and related substances have been widely applied in both industrial processes and domestic products in China. Exploring the environmental fate and transport of PFOS using modeling methods provides an important link between emission and multimedia diffusion which forms a vital part in the human health risk assessment and chemical management for these substances. In this study, the gridded fugacity based BETR model was modified to make it more suitable to model transfer processes of PFOS in a coastal region, including changes to PFOS partition coefficients to reflect the influence of water salinity on its sorption behavior. The fate and transport of PFOS in the Bohai coastal region of China were simulated under steady state with the modified version of the model. Spatially distributed emissions of PFOS and related substances in 2010 were estimated and used in these simulations. Four different emission scenarios were investigated, in which a range of half-lives for PFOS related substances were considered. Concentrations of PFOS in air, vegetation, soil, fresh water, fresh water sediment and coastal water were derived from the model under the steady-state assumption. The median modeled PFOS concentrations in fresh water, fresh water sediment and soil were 7.20ng/L, 0.39ng/g and 0.21ng/g, respectively, under Emission Scenario 2 (which assumed all PFOS related substances immediately degrade to PFOS) for the whole region, while the maximum concentrations were 47.10ng/L, 4.98ng/g and 2.49ng/g, respectively. Measured concentration data for PFOS in the Bohai coastal region around the year of 2010 were collected from the literature. The reliability of the model results was evaluated by comparing the range of modeled concentrations with the measured data, which generally matched well for the main compartments. Fate and transfer fluxes were derived from the model based on the calculated inventory within the compartments, transfer fluxes between compartments and advection fluxes between sub-regions. It showed that soil and costal water were likely to be the most important sinks of PFOS in the Bohai costal region, in which more than 90% of PFOS was stored. Flows of fresh water were the driving force for spatial transport of PFOS in this region. Influences of the seasonal change of fresh water fluxes on the model results were also analyzed. When only seasonal changes of the fresh water flow rates were considered, concentrations of PFOS in winter and spring were predicted to be higher than that under annual average conditions, while the concentrations in summer and autumn were lower. For PFOS fluxes entering the sea, opposite conclusions were drawn compared to the concentrations. Environmental risks from the presence of PFOS in fresh water were assessed for this region through comparison with available water quality criteria values. The predicted concentrations of PFOS in the Bohai coastal region provided by the model were lower than the water quality criteria published by the United States Environmental Protection Agency and Chinese researchers, while the concentrations in more than 80% of the sampling locations exceeded the European Union Water Framework Directive Environmental Quality Standards values. Seasonal variations of flow rate might cause a significant increase in environmental risks.

Experimental and molecular dynamic simulation study of perfluorooctane sulfonate adsorption on soil and sediment components

Soil and sediment play a crucial role in the fate and transport of perfluorooctane sulfonate (PFOS) in the environment. However, the molecular mechanisms of major soil/sediment components on PFOS adsorption remain unclear. This study experimentally isolated three major components in soil/sediment: humin/kerogen, humic/fulvic acid (HA/FA), and inorganic component after removing organics, and explored their contributions to PFOS adsorption using batch adsorption experiments and molecular dynamic simulations. The results suggest that the humin/kerogen component dominated the PFOS adsorption due to its aliphatic features where hydrophobic effect and phase transfer are the primary adsorption mechanism. Compared with the humin/kerogen, the HA/FA component contributed less to the PFOS adsorption because of its hydrophilic and polar characteristics. The electrostatic repulsion between the polar groups of HA/FA and PFOS anions was attributable to the reduced PFOS adsorption. When the soil organic matter was extracted, the inorganic component also plays a non-negligible role because PFOS molecules might form surface complexes on SiO2 surface. The findings obtained in this study illustrate the contribution of organic matters in soils and sediments to PFOS adsorption and provided new perspective to understanding the adsorption process of PFOS on micro-interface in the environment.

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) in soils and groundwater of a U.S. metropolitan area: Migration and implications for human exposure

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) are emerging anthropogenic compounds that have recently become the target of global concern due to their ubiquitous presence in the environment, persistence, and bioaccumulative properties. This study was carried out to investigate the migration of PFOS and PFOA in soils and groundwater in a U.S. metropolitan area.We observed elevated levels in surface soils (median: 12.2 ng PFOS/g dw and 8.0 ng PFOA/g dw), which were much higher than the soil-screening levels for groundwater protection developed in this study. The measured levels in subsurface soils show a general increase with depth, suggesting a downward movement toward the groundwater table and a potential risk of aquifer contamination. Furthermore, concentrations of PFOS and PFOA in monitoring wells in the source zone varied insignificantly over 5 years (2009–2013), suggesting limited or no change in either the source or the magnitude of the source. The analysis also shows that natural processes of dispersion and dilution can significantly attenuate the groundwater contamination; the adsorption on aquifer solids, on the other hand, appears to have limited effects on the transport of PFOS and PFOA in the aquifer. The probabilistic exposure assessment indicates that ingestion of contaminated groundwater constitutes a much more important exposure route than ingestion of contaminated soil. Overall, the results suggest that (i) the transport of PFOS and PFOA is retarded in the vadose zone, but not in the aquifer; (ii) the groundwater contamination of PFOS and PFOA often follows their release to surface soils by years, if not decades; and (iii) the aquifer can be a major source of exposure for communities living near point sources.

Mechanistic study of PFOS adsorption on kaolinite and montmorillonite

Adsorption of perfluorooctane sulfonate (PFOS) on clay minerals is pivotal in the fate and transport of PFOS in the environment. Understanding the PFOS adsorption mechanisms, however, presents challenges, especially in the presence of natural organic substances. In this study, the adsorption mechanism of PFOS on kaolinite and montmorillonite, with and without humic acids (HA), were investigated using batch experiments, ATR-FTIR spectroscopy, zeta potential, NEXAFS, and XRD. The results showed that PFOS had a higher adsorption capacity on kaolinite than on montmorillonite, both with a rapid formation of an outer-sphere complex followed by a slow ligand exchange reaction with the elimination of adsorbed H2O molecules. In addition to nonspecific hydrophobic and electrostatic interactions, specific chemisorption also exists between sulfonate group of PFOS and hydroxyl group on surfaces of clay minerals. The HA coating on clay materials inhibited PFOS adsorption due to its occupation of adsorption sites and increased electrostatic repulsion. The insights gained from this study improve our understanding on the mechanism of multilateral forces on PFOS adsorption at the molecular level.

Perfluorooctane sulfonate (PFOS) distribution and effect factors in the water and sediment of the Yellow River Estuary, China

The distribution of perfluorooctane sulfonate (PFOS) was investigated in a total of 15 water and sediment samples from the Yellow River Estuary, China in April 2011. The results indicated that the concentrations of PFOS in the water and sediment samples averaged 157.5ng/L and 198.8ng/g and ranged from 82.30 to 261.8ng/L and 75.48 to 457.0ng/g, respectively. The concentrations of PFOS in the sediment column increased from 45.32 to 379.98ng/g with the decrease of the sampling depth, which showed that the increased PFOS pollution in the sediment appeared in this region in over recent years. The distribution coefficient (K d) of PFOS between water and sediment linearly increased from 0.37 to 4.80L/g as the salinity (S‰) increased from 0.18 to 4.47. Correlation analysis revealed that K d was significantly and positively correlated to the contents of total organic carbon and clay of the sediment, and salinity. Therefore, salinity was an important parameter in controlling the sediment-water interactions and the fate or transport of PFOS in the aquatic environment. The results of this study showed that the estuary was an important sink for PFOS and suggested that PFOS might be carried with the river water and transported for long distances before it reached to the sea and largely scavenged to the sediment in the estuaries due to the change in salinity.

Adsorption Behavior of Perfluorochemicals (PFCs) on Boehmite: Influence of Solution Chemistry

Abstract With global distribution, persistence nature, and strong bioaccumulation, the fate and transport of perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) in natural environment have recently attracted strong attentions. As boehmite is a common form of hydrated aluminum oxide existing in soils and sediments, this study successfully revealed the adsorption behavior of PFOS and PFOA on boehmite and the influence from solution chemistry. The results of kinetic experiments show that the adsorption equilibrium can be achieved within 48 hours and the boehmite surface is generally receptive to PFOS and PFOA adsorption. The adsorption isotherms estimated the maximum adsorption capacities of PFOS and PFOA on boehmite to be 0.877 μg/m 2 and 0.633 μg/m2, respectively. The increase of pH can lead to a moderate decrease of PFOS and PFOA adsorption, owing to the increase of ligand exchange reaction and the decrease of electrostatic interaction. With the compression of electrical double layers, the competitive adsorption from the other ions and the Ca2+ bridging effect between perfluorochemicals have demonstrated their negative influence for PFOS and PFOA adsorption on boehmite surface. Finally, humic acid (HA) also showed significant retardant effects on the sorption of perfluorooctanesulfonate (PFOS) and perfluorobutanesulfonate (PFBuS) on boehmite.

Sediment–water distribution of perfluorooctane sulfonate (PFOS) in Yangtze River Estuary

Analysis of Perfluorooctane sulfonate (PFOS) distribution in water and sediment in Yangtze River Estuary showed that the estuary was a sink for PFOS. Salinity was an important parameter in controlling the sediment–water interactions and the fate or transport of PFOS in the aquatic environment. As the salinity (S‰) increased from 0.18 to 3.31, the distribution coefficient (K d) between sediment and water linearly increased from 0.76 to 4.70 L g −1. The study suggests that PFOS may be carried with the river water and transported for long distances before it reaches to the sea and largely scavenged to the sediment in the estuaries due to the dramatic change in salinity.

Modeling the Global Fate and Transport of Perfluorooctane Sulfonate (PFOS) and Precursor Compounds in Relation to Temporal Trends in Wildlife Exposure

A global-scale fate and transport model was applied to investigate the historic and future trends in ambient concentrations of perfluorooctane sulfonate (PFOS) and volatile perfluorooctane sulfonyl fluoride (POSF)-based precursor compounds in the environment. First, a global emission inventory for PFOS and its precursor compounds was estimated for the period 1957-2010. We used this inventory as input to a global-scale contaminant fate model and compared modeled concentrations with field data. The main focus of the simulations was to examine how modeled concentrations of PFOS and volatile precursor compounds respond to the major production phase-out that occurred in 2000-2002. Modeled concentrations of PFOS in surface ocean waters are generally within a factor of 5 of field data and are dominated by direct emissions of this substance. In contrast, modeled concentrations of the precursor compounds considered in this study are lower than measured concentrations both before and after the production phase-out. Modeled surface ocean water concentrations of PFOS in source regions decline slowly in response to the production phase-out while concentrations in remote regions continue to increase until 2030. In contrast, modeled concentrations of precursor compounds in both the atmosphere and surface ocean water compartment in all regions respond rapidly to the production phase-out (i.e., decline quickly to much lower levels). With respect to wildlife biomonitoring data, since precursor compounds are bioavailable and degrade to PFOS in vivo, it is at least plausible that declining trends in PFOS body burdens observed in some marine organisms are attributable to this exposure pathway. The continued increases in PFOS body burdens observed in marine organisms inhabiting other regions may reflect exposure primarily to PFOS itself, present in the environment due to production and use of this compound as well as degradation of precursor compounds.

Method development for the determination of perfluorinated organic compounds (PFCs) in surface water

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) are emerging anthropogenic compounds that have recently become the target of global concern due to their ubiquitous presence in the environment, persistence, and bioaccumulative properties. This study was carried out to investigate the migration of PFOS and PFOA in soils and groundwater in a U.S. metropolitan area.We observed elevated levels in surface soils (median: 12.2 ng PFOS/g dw and 8.0 ng PFOA/g dw), which were much higher than the soil-screening levels for groundwater protection developed in this study. The measured levels in subsurface soils show a general increase with depth, suggesting a downward movement toward the groundwater table and a potential risk of aquifer contamination. Furthermore, concentrations of PFOS and PFOA in monitoring wells in the source zone varied insignificantly over 5 years (2009–2013), suggesting limited or no change in either the source or the magnitude of the source. The analysis also shows that natural processes of dispersion and dilution can significantly attenuate the groundwater contamination; the adsorption on aquifer solids, on the other hand, appears to have limited effects on the transport of PFOS and PFOA in the aquifer. The probabilistic exposure assessment indicates that ingestion of contaminated groundwater constitutes a much more important exposure route than ingestion of contaminated soil. Overall, the results suggest that (i) the transport of PFOS and PFOA is retarded in the vadose zone, but not in the aquifer; (ii) the groundwater contamination of PFOS and PFOA often follows their release to surface soils by years, if not decades; and (iii) the aquifer can be a major source of exposure for communities living near point sources.

Effect of cationic and anionic surfactants on the sorption and desorption of perfluorooctane sulfonate (PFOS) on natural sediments

Sorption and desorption of PFOS at water-sediment interfaces were investigated in the presence of a cationic surfactant, cetyltrimethylammonium bromide (CTAB), and an anionic surfactant, sodium dodecylbenzene sulfonate (SDBS). CTAB remarkably enhanced the sorption of PFOS on the sediment. In contrast, the influence of SDBS to the sorption of PFOS was concentration dependent. Two contrasting factors were responsible for the phenomenon. One was the sorption of the surfactant itself to the sediment, which enhanced the sorption of PFOS. The other was the increase in solubility of PFOS caused by the adding of surfactants, which decreased the sorption of PFOS. SDBS had a much lower sorption capacity, but rather strong ability to increase the solubility of PFOS. High levels of SDBS remarkably reduced the sorption of PFOS on the sediment. These results imply that cationic and anionic surfactants may have contrast impacts on the distribution and transport of PFOS in the environment.