clay and perfluorooctane-sulfonic-acid

Soil is an important sink for perfluorooctane sulfonate (PFOS) that is a typical persistent organic pollutant with high toxicity. Understanding of PFOS sorption to various particle-size fractions of soil provides an insight into the mobility and bioavailability of PFOS in soil. This study evaluated kinetics, isotherms, and mechanisms of PFOS sorption to six soil particle-size fractions of paddy soil at environmentally relevant concentrations (0.01-1 μg/mL). The used soil particle-size fractions included coarse sand (120.4-724.4 mm), fine sand (45.7-316.2 mm), coarse silt (17.3-79.4 mm), fine silt (1.9-39.8 mm), clay (0.5-4.4 mm), and humic acid fractions (8.2-83.7 mm) labeled as F1~F6, respectively. PFOS sorption followed pseudo-second-order kinetics related to film diffusion and intraparticle diffusion, with speed-limiting phase acted by the latter. PFOS sorption isotherm data followed Freundlich model, with generally convex isotherms in larger size fractions (F1~F3) but concave isotherms in smaller size fractions (F4 and F5) and humic acid fraction (F6). Increasing organic matter content, Brunner-Emmet-Teller surface area, and smaller size fractions were conducive to PFOS sorption. Hydrophobic force, divalent metal ion-bridging effect, ligand exchange, hydrogen bonding, and protein-like interaction played roles in PFOS sorption. But hydrophobic force controlled the PFOS sorption, because its relevant organic matter governed the contribution of the soil fractions to the overall PFOS sorption. The larger size fractions dominated the PFOS sorption to the original soil because of their high mass percentages (~80%). This likely caused greater potential risks of PFOS migration into groundwater and bioaccumulation in crops at higher temperatures and c

Topics: Adsorption; Alkanesulfonic Acids; Clay; Fluorocarbons; Humic Substances; Hydrophobic and Hydrophilic Interactions; Kinetics; Particle Size; Soil; Soil Pollutants; Thermodynamics

The widespread use of perfluoroalkylated acids (PFAAs) has led to a global presence in the environment, in which they accumulate and may cause detrimental effects. Although soils are known sinks for many persistent organic pollutants, still little is known on the behaviour of PFAAs in soils. Furthermore, studies that examine the relationships between PFAA concentrations and soil microbial parameters are scarce. The 3 M fluorochemical plant near Antwerp has been characterized as a PFAAs hotspot. In the present study, we examined the vertical distribution of 15 PFAAs and their associations with multiple physicochemical soil properties along a distance gradient from this hotspot. Additionally, we tested the relationships between PFAA concentrations in the top soil with soil respiration, microbial activity and microbial biomass. Our results show that both perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) concentrations were elevated in the subsurface layer (up to 50 cm), after which concentrations decreased again, suggesting a downward migration of both analytes in the soil. This downward movement might pose a potential threat for the contamination of the groundwater and, consequently, organisms that rely on this water for consumption. The soil concentrations were influenced by multiple physicochemical properties of the soil, which suggests differences in bioavailability and sorption/desorption capacities between different soil types. We did not observe any influence of PFAA contamination in the top soil on microbial activity and biomass nor soil respiration.

Topics: Alkanesulfonic Acids; Belgium; Caprylates; Carbon; Chemical Industry; Clay; Fluorocarbons; Hydrogen-Ion Concentration; Soil; Soil Microbiology; Soil Pollutants; Temperature

The sorption of four perfluoroalkyl acids (PFAAs) [perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS), perfluorooctanoic acid (PFOA) and perfluorohexanoic acid (PFHxA)] on three typical minerals [montmorillonite (MM), kaolinite (KL) and hematite (HM)] was studied. The sorption of PFOS and PFHxS was much stronger than PFOA and PFHxA. The sorption of each PFAA on the minerals followed an order of HM>KL>MM, even though MM was positively while KL and HM were negatively charged, implying that the sorption is driven by some other interactions besides electrostatic attraction. The sorption decreased with an increase in pH and a decrease in ionic strength of the solution, and their impacts on PFOS were much stronger than other three PFAAs. Surface complexing and hydrogen-bonding could make great contributions to the sorption of PFOS on the minerals. The results are important for understanding the transport and fate of PFAAs in sediment and ground water.

Topics: Adsorption; Alkanesulfonic Acids; Aluminum Silicates; Bentonite; Caproates; Caprylates; Clay; Ferric Compounds; Fluorocarbons; Hydrogen Bonding; Kaolin; Osmolar Concentration; Static Electricity

The influence of salinity and organic matter on the distribution coefficient (K(d)) for perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) in a brackish water-clay system was studied. The distribution coefficients (K(d)) for PFAs onto inorganic clay surfaces increased with salinity, providing evidence for electrostatic interaction for the sorption of PFAs, whereas the relationship between K(d) and organic carbon content (f(oc)) suggested that hydrophobic interaction is the primary driving force for the sorption of PFAs onto organic matter. The organic carbon normalized adsorption coefficient (K(oc)) of PFAs can be slightly overestimated due to the electrostatic interaction within uncoated inorganic surfaces. In addition, the dissolved organic matter released from coated clay particles seemed to solvate PFA molecules in solution, which contributed to a decrease in K(d). A positive relationship between K(d) and salinity was apparent, but an empirical relationship for the 'salting-out' effect was not evident. The K(d) values of PFAs are relatively small compared with those reported for persistent organic pollutants. Thus, sorption may not be a significant route of mass transfer of PFAs from water columns in estuarine environments. However, enhancement of sorption of PFAs to particulate matter at high salinity values could evoke potential risks to benthic organisms in estuarine areas.

Topics: Alkanesulfonic Acids; Aluminum Silicates; Caprylates; Clay; Fluorocarbons; Geologic Sediments; Kinetics; Salinity; Seawater; Water Pollutants, Chemical