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Sorption of Fluorotelomer Sulfonates, Fluorotelomer Sulfonamido Betaines, and a Fluorotelomer Sulfonamido Amine in National Foam Aqueous Film-Forming Foam to Soil Krista A. Barzen-Hanson, Shannon E. Davis, Markus Kleber, and Jennifer A. Field Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.7b03452 • Publication Date (Web): 02 Oct 2017 Downloaded from http://pubs.acs.org on October 3, 2017
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Environmental Science & Technology
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Sorption of Fluorotelomer Sulfonates, Fluorotelomer Sulfonamido Betaines, and a Fluorotelomer Sulfonamido Amine in National Foam Aqueous Film-Forming Foam to Soil
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Krista A. Barzen-Hanson,a Shannon E. Davis,a,b Markus Kleber,c and Jennifer A. Fieldd*
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a
Department of Chemistry, Oregon State University, 153 Gilbert Hall, Corvallis, Oregon 97331, United States b Currently at School for the Environment, University of Massachusetts, Boston, 100 William T Morrissey Boulevard, Boston, MA 02125, United States c Department of Crop and Soil Science, Oregon State University, 3017 ALS Building, 2750 SW Campus Way, Corvallis, OR 97331, United States d Department of Environmental and Molecular Toxicology, Oregon State University, 1007 ALS Building, 2750 SW Campus Way, Corvallis, Oregon 97331, United States *Corresponding author
13 14 15
Address: Oregon State University, 1007 ALS Building, 2750 SW Campus Way, Corvallis, OR 97331. Phone: (541) 737-2265. Fax: (541) 737-0497. E-mail:
[email protected] 16
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ABSTRACT
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During fire fighter training, equipment testing, and emergency responses with aqueous film-
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forming foams (AFFFs), mg/L concentrations of anionic, zwitterionic, and cationic per- and
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polyfluoroalkyl substances (PFASs) enter the environment. Since the behavior of zwitterionic
21
and cationic PFASs in the subsurface is unknown, batch sorption experiments were conducted
22
using National Foam AFFF, which contains anionic fluorotelomer sulfonates (FtSs), zwitterionic
23
fluorotelomer sulfonamido betaines (FtSaBs), and cationic 6:2 fluorotelomer sulfonamido amine
24
(FtSaAm). Sorption of the FtSs, FtSaBs, and 6:2 FtSaAm to six soils with varying organic
25
carbon, effective cation exchange capacity, and anion exchange capacity was evaluated to
26
determine sorption mechanisms. Due to poor recovery of the FtSaBs and 6:2 FtSaAm with
27
published PFAS soil extraction methods, a new soil extraction method was developed to achieve
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good (90-100 %) recoveries. The 6:2 FtSaAm was depleted from the aqueous phase in all but
29
one soil, which is attributed to electrostatic and hydrophobic interactions. Sorption of the FtSs
30
was driven by hydrophobic interactions, while the FtSaBs behave more like cations that strongly
31
associate with the solid phase relative to groundwater. Thus, the sorption mechanisms of the
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FtSs, FtSaBs, and 6:2 FtSaAm are more complex than expected and cannot be predicted by bulk
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soil properties.
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INTRODUCTION Per- and polyfluoroalkyl substances (PFASs) are ubiquitous contaminants in the
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environment1-3 and in wildlife,4,5 in part due to the release of aqueous film-forming foams
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(AFFFs) during fire-related emergencies, equipment testing, and training. AFFFs are complex
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mixtures that contain solvents, hydrocarbon surfactants, and anionic, zwitterionic, and cationic
40
PFASs.6,7 Because AFFFs are proprietary mixtures, the composition8-11 and concentrations12 of
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PFASs in AFFFs were reverse-engineered to understand their environmental impact. At the time
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of application, AFFFs are diluted to either 3% or 6%,6,7 resulting in high (mg/L) concentrations
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of PFASs12 that subsequently enter the environment.
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Sorption of perfluoroalkyl carboxylates (PFCAs) and perfluoroalkyl sulfonates (PFSAs)
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increases with the organic carbon content in soils and sediments,13-16 as measured by solid-water
46
partition coefficients (Kd) and organic carbon normalized solid-water partition coefficients. The
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contributions to sorption of PFSAs and PFCAs from electrostatic interactions with mineral
48
phases increases when organic carbon is low (0-0.78%).14,17 Within the PFCA or PFSA
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homologous series, longer-chained homologs have higher partition coefficients than short-
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chained homologs.15,16,18-20
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In contrast, the anionic fluorotelomer sulfonates (FtSs) and zwitterionic and cationic
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PFASs present in groundwater,12 soil,21,22 and sediment23-25 have received little attention. Two
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studies report field-derived Kd values for the 6:2 FtS,23,26 while only one study reports field-
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derived Kd values for the zwitterionic 6:2 fluorotelomer sulfonamido betaine (FtSaB) and the
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cationic 6:2 fluorotelomer sulfonamido amine (FtSaAm).23 The ‘n:2’ fluorotelomer-based
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PFASs are characterized by carbon chains with ‘n’ perfluorinated carbons that are bonded to two
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non-fluorinated methylene carbons. For example, 6:2 FtS has six perfluorinated carbons that are
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bonded to two non-fluorinated methylene carbons that are then bonded to a sulfonate group.
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Typically, batch sorption experiments containing a mixture of PFCAs and PFSAs are
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performed under controlled conditions.15,16,20 However, a similar experimental set-up for
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sorption of zwitterionic and cationic PFASs is challenging due to the lack of authentic standards
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and mass-labeled internal standards for the zwitterionic and cationic PFASs, and few reference
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materials are available.12 Furthermore, mass balance of the PFCAs and PFSAs is typically 3 ACS Paragon Plus Environment
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achieved by extracting the soil or sediment.15,16 To date, all studies examining concentrations of
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zwitterionic and cationic PFASs on soil and sediment rely on extracting with methanol and either
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1.5-200 mM acid or base. However, this approach has only been validated by spiking dry soils
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with standards dissolved in methanol and allowing the methanol to evaporate for 2-48 h.22-24,27
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Others demonstrate that higher concentrations of acid (e.g. 0.5-1 M) in methanol are necessary to
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quantitatively recover cations, particularly if the cations have been allowed to equilibrate in
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water with the soil and/or sediment.28-31 If a higher concentration of acid in methanol for the
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extraction of zwitterionic and cationic PFASs from soil, then both concentrations24,25,27 and field-
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derived Kd estimates23 of zwitterionic and cationic PFASs may be significantly underestimated
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due to incomplete extraction of the (presumably) equilibrated soil and sediment.
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It is difficult to simulate the complexity of processes that occur at AFFF-impacted field
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sites during sorption experiments. To the best of our knowledge, only two studies report PFCA
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and PFSA sorption in the presence of ionized hydrocarbon surfactants,15,32 which occur at similar
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levels to PFASs in AFFFs along with solvents.6,7 Of the two studies, one reports an increase in
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the sorption of a single compound, perfluorooctane sulfonate (PFOS), in the presence of a single
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cationic hydrocarbon surfactant, and another single anionic hydrocarbon surfactant decreased
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PFOS sorption.32 In the second study, another anionic hydrocarbon surfactant caused either no
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change or a slight decrease in sorption of long-chained (n ≥ 6) perfluoroalkyl acids when present
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in a mixture of PFASs.15 However, neither of the two studies employed conditions that
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simulated the application of AFFF that contain mg/L levels of PFASs and other additives to
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pristine soil at a field site.
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Little is known about the sorption behavior of anionic, zwitterionic, and cationic PFASs
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present in AFFF, especially once concentrated AFFF is applied to soils at field sites. To the best
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of our knowledge, batch sorption experiments have not been conducted using AFFF containing a
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range of PFASs and concentrations in the same range as those found in groundwater (ng/L to
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mg/L) and AFFF applied to fight fires (mg/L to g/L). National Foam AFFF was selected because
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it was approved for use by the U.S. military since 1976,9 contains anionic FtSs, zwitterionic
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FtSaBs, and cationic 6:2 FtSaAm (Fig. 1),9,12 and is still available today on the Qualified Product
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List.33,34 The anionic FtSs are predicted to sorb via hydrophobic interactions as observed for
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PFAAs,14-16,35 while zwitterionic FtSaBs and cationic 6:2 FtSaAm are expected to sorb via 4 ACS Paragon Plus Environment
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electrostatic interactions in a manner analogous to zwitterionic and cationic pharmaceuticals.36-38
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Six uncontaminated soils with ranging levels of organic carbon, effective cation exchange
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capacity (ECEC), and anion exchange capacity (AEC) were used to investigate the sorption
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mechanisms of the FtSs, FtSaBs, and 6:2 FtSaAm contained in National Foam AFFF. While
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sorbate competition is possible, assessing sorbate competition was outside the scope of the study.
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Due to the potential for sorbates (FtSaBs, 6:2 FtSaAm), organic matter, and iron oxides to
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speciate over a range of pHs, the influence of pH on the sorption of the anionic FtSs, zwitterionic
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FtSaBs, and cationic 6:2 FtSaAm sorption was determined with a single soil titrated to pH 4 and
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pH 7 as well as the native pH (pH 5.1). Existing soil extraction methods for zwitterionic and
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cationic PFASs22-24,27 did not provide adequate mass balance; therefore, a new soil extraction
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method was developed to enable complete mass balance.
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EXPERIMENTAL
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Chemicals. A description of all materials, including solvents, chemicals, and analytical
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standards, is provided in the Supporting Information (SI).
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Soil Sample Collection and Characterization. Six uncontaminated soils (Soils 1-6) were
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selected from an archived soil collection at Oregon State University that constrained pH to 5.0-
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5.5 but covered a range of soil characteristics, including organic carbon, ECEC, and AEC (Table
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1, Table S1). Methods for soil characterization are provided in the SI. All soil characterization
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was performed prior to autoclaving, which is known to change organic matter structure and alter
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the clay fraction.39 Soils were sieved to < 2 mm and air dried prior to homogenization with a
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mortar and pestle before use in sorption experiments.
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Batch Sorption Experiments. Analyte Source Selection. Analyte sources and rationale are
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provided in the SI.
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Sorption Isotherm Experiment. All isotherms, with the exception of the preliminary experiment
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involving a commercial Capstone product (see SI), were created using National Foam AFFF.
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Material Safety Data Sheets for National Foam AFFF indicate 4-25 % solvent,7 but after dilution
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in surrogate groundwater, solutions were comprised of < 0.1 % organic solvent. A 21-point
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isotherm was constructed using Soil 1, with initial aqueous phase concentrations (Cwi) of 1.8 –
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240,000 nM for the 6:2 FtSaB. Eleven-point isotherms were constructed using Soils 2-6, and 5 ACS Paragon Plus Environment
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two additional isotherms were constructed with Soil 1 that was titrated to pH 4 and pH 7. For the
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11-point isotherms, Cwi ranged from 1.8 to 440 nM for the 6:2 FtSaB. The upper-end Cwi for the
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21-point and the 11-point isotherms were selected based on the 3% AFFF in water used in
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firefighting and a mid-range concentration for the 6:2 FtS in AFFF-impacted groundwater (21 –
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520 nM),12 respectively. Since all analytes were delivered as a mixture, only the concentration
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range for the most abundant analyte is reported here; the remaining concentration ranges and the
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relative ratios of each analyte are given in Table S2 and Table S3, respectively (see SI).
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Replicates, which consisted of homogenized soil spiked with the same volume of National Foam
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AFFF stock solution, were created for 6:2 FtSaB Cwi of 8.8 nM (n=4), 110 nM (n=3), and
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240,000 nM (n=3). All other data are derived from individual reactors.
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Homogenized soil was weighed (1.00 ± 0.02 g) into each 50 mL polypropylene
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centrifuge tube (VWR, Radnor, PA) and autoclaved for 40 min at 121 °C with a 20-min drying
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time (Consolidated Sterilizer Systems Model SSR-2A-ADVPB, Allston, MA). Vials contained
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the autoclaved soil and 10 mL of a groundwater surrogate (0.5 mM calcium chloride),16,35 to
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which only the diluted National Foam AFFF was spiked (Table S4; see SI). The soil-water ratio
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was optimized for the primary component in the AFFF (6:2 FtSaB). Because the ratios of all
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components were fixed in the AFFF and standards for the individual AFFF components are not
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available commercially, the solution composition could not be optimized for all components.
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Positive controls, consisting of groundwater surrogate and AFFF but no soil, were prepared at
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the Cwi of the replicates. One negative control, consisting of the autoclaved soil and groundwater
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surrogate but no AFFF, was prepared with each isotherm. Vials were allowed to equilibrate for
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24 h on a wrist action shaker at 10° rotation (Burrell Corporation, Model 75, Pittsburg, PA)
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based on previous literature (see SI).13,17,32,35
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Following equilibration, batch reactors were centrifuged at 2808 rcf for 20 min
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(Eppendorf, Model 5810R, Hauppauge, NY), and the supernatant was decanted into a separate
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15 mL centrifuge tube (VWR). The soil was transferred into a separate 50 mL centrifuge tube
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using deionized water. The empty vial from which the aqueous and soil phases had been
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removed (hereafter referred to as ‘vial phase’) and the aqueous phase were stored at -20 °C. The
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soil was freeze dried (VirTis Sentry 2.0, SP Scientific, Warminster, PA) for 48 h and stored in
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the dark at 22 °C until extraction. 6 ACS Paragon Plus Environment
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pH Adjustments to Pre-equilibrated Soil. Methods for pH adjusting the soils are provided
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in the SI. Briefly, soil was pre-equilibrated with groundwater surrogate for 24 h, over-titrated to
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either pH 3.3 or pH 8, and pre-equilibrated for another 24 h before AFFF was spiked.
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Sample Preparation. Aqueous Phase. The aqueous phase sample preparation was based on a
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slight modification of a micro liquid-liquid extraction, as established previously.12 A description
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is provided in the SI.
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Soil phase. Mass balance experiments consisted of quadruplicate vials of Soil 1 with 110 nM 6:2
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FtSaB Cwi. Following equilibration for 24 h, the three phases were separated and extracted
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individually. Initially, mass balance experiments were conducted using the aqueous phase
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extraction and a soil extraction typically used for cationic and zwitterionic PFASs.23,24,27 The
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vial and soil phases were extracted using 1.5 mM ammonium hydroxide in methanol as
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described elsewhere.27 Preliminary experiments indicated poor recovery of the zwitterionic 6:2
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FtSaB and the cationic 6:2 FtSaAm (Table S6) when soil and analytes were equilibrated in an
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aqueous phase (and not methanolic spikes) and extracted using relatively mild conditions (1.5-
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200 mM base in methanol22,24,27).
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Soil extraction methods for cationic, nonfluorinated surfactants typically use either 0.5
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M30 or 1 M HCl28,29,31 in methanol. The 1 M HCl in methanol extraction conditions proved to be
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problematic (unpublished data). Therefore, 0.5 M HCl in methanol was used in all subsequent
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extractions. The soil extraction procedure was modified slightly from Houtz et al.27 and is
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outlined in the SI.
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Mass balance experiments were repeated using the acidic methanol extraction for the vial
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and soil phases. Recoveries improved significantly for the 6:2 FtSaB and the 6:2 FtSaAm (90-
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100 % recovery; Table S6). Having achieved mass balance in separate experiments with an
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experimental set-up analogous to that used to generate isotherms, mass balance was assumed for
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all vials. Mass balances were not determined for each vial used to construct the isotherms due to
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the greater variability associated with subsampling the AFFF concentrate, and therefore, the
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variability in the mass of analyte added to each vial. Mass balance experiments also indicated
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that sorption to the vial walls was minimal for all analytes (unpublished data). Therefore, only
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the aqueous and soil phases were extracted for each vial (not the vial itself).
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LOD and LOQ parameters for soil extractions (Table S7) and descriptions are provided in the SI.
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Analytical Methods. A description of the analytical methods, including chromatography,
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MS/MS, calibration, analyte quality classification, and quality control measures, is based on
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previous literature10,12 and provided in the SI.
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Data Treatment. Measured soil phase concentrations for each analyte were adjusted to account
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for the mass of each analyte remaining in the pore water that was forced onto the soil during
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freeze drying (see SI for details).
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Whole method
Sorption isotherms were fitted using the following Freundlich isotherm model equations:
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= (Eqn 1) or = + (Eqn 2)
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where Kf [(nmol kg-1)(nmol L-1)-n] is the Freundlich sorption coefficient and n (unitless) is a
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measure of nonlinearity and represents the free energy associated with adding more sorbate to
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the sorbent.40 Kf values (Table S8) were converted to the concentration-specific Kd values using
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the following equation:
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= ∗ (Eqn 3)
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where Cw is the equilibrium concentration of the aqueous phase in the 8.8 or 110 nM Cwi vials, to
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enable comparisons between isotherms and across other sorption studies for other PFASs (see SI
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for details). The Kd values at Cwi = 110 nM are used for the FtSs and the 6:2 FtSaAm, while the
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Kd values at Cwi = 8.8 nM are used for the FtSaBs in the discussion below (see SI for rationale).
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Statistical Analysis. Correlation coefficients, 95% confidence intervals (CI), and p-values were
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calculated for all correlations using R (version 3.3.3).41 Correlations were computed using
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Pearson’s moment correlations and did not incorporate the 95% CI of each Kd value. Correlation
203
coefficients and p-values are interpreted with caution due to the non-normal distribution of the
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soil property values.
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pKa. pKas for the functional groups on FtSs, FtSaBs, and FtSaAms were estimated by comparing
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the molecules to model compounds in the literature (see SI) and using the estimation software
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Chemicalize42 (Fig. 1). 8 ACS Paragon Plus Environment
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RESULTS AND DISCUSSION
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Commercial Product vs. AFFF. Preliminary experiments were performed to determine if the
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sorption of the 6:2 FtSaB from the Capstone product and National Foam AFFF at low
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concentrations (1.8 – 18 nM) was significantly different at the 95% CI (Fig. S3). This
212
information was used to select the most appropriate product with which to conduct subsequent
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sorption experiments. No significant difference in the sorption of the 6:2 FtSaB between the
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Capstone product and National Foam AFFF was observed. The Capstone product is a simple
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mixture containing only 6:2 FtS, 6:2 FtSaB, and 6:2 FtSaAm with no hydrocarbon surfactants
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but percent levels of solvent,43 while National Foam AFFF contains the analytes plus percent
217
levels of solvents and hydrocarbon surfactants.7 Given the AFFF’s greater complexity and the
218
fact that the AFFF has been used since the 1970s and is still listed on the U.S. Military’s
219
Qualified Products List,33,34 all subsequent sorption experiments were performed with National
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Foam AFFF.
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Sorption Isotherms. Sorption experiments with National Foam AFFF were conducted using six
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soils, with a subset of experiments conducted with a single soil (Soil 1) but at three different pHs
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(pH 4, 5.1, and 7). The objective was to test soils over a range of properties in order to
224
investigate correlations between Kd and organic carbon, ECEC, AEC, and pH. Soil 6 is unique
225
with regard to ECEC, since the clay fraction of Soil 6 is dominated by smectite with low
226
(0.098%) organic carbon (Tables 1, S1). Soil 2, which also has low organic carbon and the
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highest ECEC (double that of Soil 6), contains some smectite as well as pedogenic iron oxides
228
and other clay minerals. Although Soils 2 and 6 have similar organic carbon and ECEC, the
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additional minerals and pedogenic iron oxides present in Soil 2 may interact with the zwitterionic
230
FtSaBs and cationic 6:2 FtSaAm through secondary interactions, such as sorbate-sorbate
231
interactions. Sorption of some organic cations is influenced by the location of mineral and
232
organic matter exchange sites.44 The greater complexity of the mineral phase in Soils 1-5
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indicates the possibility of sorbate-sorbent interactions through a variety of mechanisms not
234
limited solely to electrostatic interactions, although the proportion of each sorption mechanism
235
for a given analyte needs to be determined.
236 237
Sorption was nonlinear for all soils (Table S8) for the 6:2 FtS (n = 0.8-1.2), 8:2 FtS (n = 0.74-1.1), 6:2 FtSaB (n = 0.8-1.5), 8:2 FtSaB (n = 0.41-1.8), and 6:2 FtSaAm (n = 0.17). Ranges 9 ACS Paragon Plus Environment
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for the Kd values (Table S9) are 3.1-12 L/kg (6:2 FtS, Cwi = 110 nM), 17-120 L/kg (8:2 FtS, Cwi =
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110 nM), 23-150 L/kg (6:2 FtSaB, Cwi = 8.8 nM), 34-400 L/kg (8:2 FtSaB, Cwi = 8.8 nM) , and
240
650 L/kg (6:2 FtSaAm, Cwi = 110 nM). The ranges of n for the anionic FtSs are consistent with
241
other batch sorption experiments for the anionic PFCAs and PFSAs.15,16,35 However, the n
242
ranges for the zwitterionic FtSaBs and the 6:2 FtSaAm are wider than the anionic FtSs, which
243
may indicate multiple sorption energies or mechanisms,40 as will be discussed below. Due to
244
the experimental conditions used, complete depletion of several analytes (< 0.18 nM) limits the
245
discussion to the behavior of 6:2 FtS, 8:2 FtS, 6:2 FtSaB, 8:2 FtSaB, and 6:2 FtSaAm (Soil 6
246
isotherm only).
247
Soil 1 Native pH (5.1) Isotherm. Log-transformed Freundlich isotherms (Eqn 2; Fig. 2) of the
248
anionic 6:2 and 8:2 FtS and the zwitterionic 6:2 and 8:2 FtSaB for Soil 1 at pH 5.1 indicates the
249
relative sorption strength of each sorbate. The values of the y-intercepts (i.e. log Kf) indicate that
250
the strongest sorbed analyte is the 8:2 FtSaB, followed by the 8:2 FtS, 6:2 FtSaB, and 6:2 FtS,
251
which is the weakest sorbed analyte. Within each class (FtS and FtSaB), sorption increases as
252
the fluorinated chain length increases. The increase in sorption with fluorinated chain length for
253
other PFASs was observed in previous sorption studies.15,16,19,20,45 The apparent increase of the
254
last 3 points in the 6:2 FtS isotherm and the last 2 points of the 6:2 FtSaB isotherm may suggest
255
an increase in secondary sorbate-sorbate interactions40,46,47 due to n > 1 for the 6:2 FtS and 6:2
256
FtSaB, which may indicate sorbate-sorbate interactions48. The last 2-3 points of the isotherms
257
were included in the analysis since the concentrations used to generate the points are
258
environmentally relevant. Moreover, tentative exclusion of the data points did not significantly
259
alter the observed trend or the quality of the correlation (Table S10). For the purposes of brevity,
260
only the isotherm for Soil 1 at the native pH (5.1) are discussed here. Isotherms for the 6:2 and
261
8:2 FtSs, 6:2 and 8:2 FtSaBs, and 6:2 FtSaAm (Soil 6 isotherm only) for Soils 2-6, Soil 1 pH 4,
262
and Soil 1 pH 7 are provided in the SI (Fig. S4-S10) and are included in the discussion below.
263
The sorption strength of each sorbate in a given soil (Soils 2-6, Soil 1 pH 4, and Soil 1 pH 7)
264
may be different from the order discussed for the Soil 1 native pH isotherm.
265
FtS, FtSaB, and 6:2 FtSaAm Sorption. Log Kd. Previous studies based on batch sorption
266
experiments with PFASs report changes in log Kd as the number of CF2 groups increase but only
267
for anionic PFASs. The log Kd increase per CF2 group between the 6:2 and 8:2 homologs for the 10 ACS Paragon Plus Environment
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FtSs and FtSaBs was 0.41 ± 0.059 and 0.20 ± 0.088, respectively (Table S11). The increase in
269
log Kd per CF2 group for the anionic FtSs is consistent with the 0.5-1 log Kd increase for the
270
anionic PFCAs and PFSAs.15,16,18,49 The log Kd increase per CF2 group for the zwitterionic
271
FtSaBs is lower than that for FtSs, and the large 95 % CI may be partially attributed to greater
272
analytical uncertainty about FtSaB concentrations (see Analytical Methods in SI). The increase
273
in log Kd with an increase in the number of CF2 groups indicates that hydrophobic interactions
274
may be an important sorption mechanism15 for the anionic FtSs and to a lesser extent for the
275
zwitterionic FtSaBs. The lower log Kd per CF2 group for the FtSaBs indicates that a different
276
primary sorption mechanism, such as electrostatic interactions, may influence sorption more
277
heavily.
278
For a given fluorinated chain length, the 6:2 FtSaB has a larger Kd (Cwi = 110 nM) than
279
the 6:2 FtS for all soils and conditions, which is likely due to the greater size, molecular weight,
280
and type of charges associated with 6:2 FtSaB. Since the 6:2 FtSaB head group has one positive
281
charge and a terminal negative charge at pH 5.1 (Fig. 1), the positive charge within the head
282
group is contributing to increased interactions, presumably due to electrostatic interactions. The
283
6:2 FtSaAm, which was completely sorbed to all soils except Soil 6, has one terminal positive
284
charge (Fig. 1). The 6:2 FtSaAm has the highest observed Kd value (Cwi = 110 nM, Table S9), so
285
the number of positive charges cannot explain the difference in sorption. Rather, the position of
286
the charges as well as the net charge appear to be relevant. In this case, the terminal positive
287
charge on the 6:2 FtSaAm leads to greater sorption onto soil, whereas the 6:2 FtSaB, while
288
having a net neutral charge, also has a terminal negative charge, which may exert a repulsive
289
effect in close proximity to the soil surface, as was observed in the sorption of oxytetracycline
290
and ciprofloxacin50.
291
The single-point Kd (Cwi = 110 nM) values for the 6:2 FtS (3.1-12 L/kg; Table S9) are in
292
good agreement with the field-Kd values reported (5.8 L/kg23 and 3.2 L/kg26) for sediment-water
293
systems. The Kd (Cwi = 8.8 nM) values for the 6:2 FtSaB range from 23-240 L/kg (Table S9),
294
which are significantly greater than the single field-Kd of 4.5 L/kg23. The single Kd (Cwi = 110
295
nM) value obtained for the cationic 6:2 FtSaAm was 650 L/kg (Table S9), which is also
296
significantly greater than the single reported field-Kd of 34 L/kg23. The lower values reported by
297
Boiteux et al.23 may be due to incomplete extraction of zwitterionic and cationic PFASs from 11 ACS Paragon Plus Environment
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298
sediment using the milder extraction conditions (1% acetic acid in methanol) compared to the 0.5
299
M HCl in methanol in the present study. Alternatively, the organic matter and ECEC properties
300
of the sediment, which were not reported, may have contributed to the lower Kd values.23
301
Correlations. Organic Carbon. The experimental data indicate that anionic 6:2 FtS (0.83, p =
302
0.039) and 8:2 FtS (0.96, p = 0.0019) correlate with organic carbon (Fig. 3, Table S12). The Kd
303
(Cwi = 110 nM) values for the longer-chained 8:2 FtS are consistently greater than those of 6:2
304
FtS except for Soil 4 (Kd = 120 L/kg), in which the 8:2 FtS Kd is disproportionately high for an
305
unknown reason. Removing the Kd values for Soil 4 from the correlation analysis, no correlation
306
exists for the 6:2 FtS (0.21, p = 0.73) or the 8:2 FtS (0.42, p = 0.48), indicating that the Soil 4 Kd
307
(Cwi = 110 nM) values are likely outliers. Log transformations of both Kd and organic carbon did
308
not improve correlations (Table S13). At the lowest levels of organic carbon (0.098 – 0.12%),
309
the Kd (Cwi = 110 nM) values for the 6:2 and 8:2 FtS are similar in magnitude to those for the
310
soils with higher organic carbon (1.0 – 2.3%), which indicates that the mineral phase in the low
311
organic carbon soils (Soils 2, 6) influences sorption.14,17 The nonpolar fluorinated tail of the
312
anionic FtSs may interact with the hydrophobic (nonpolar) nanosites51-54 between the charged
313
sites on the mineral surface55 via weak hydrophobic interactions.14-16,56
314
The lack of a correlation in FtS sorption may be due to variations in the extent of organic
315
matter decomposition of the soils tested. The relationship between C/N in soil organic matter
316
and oxygen-containing functional groups is based on the following two premises: (a) the
317
majority of terrestrial organic matter is decomposed by oxidative depolymerization,57 which adds
318
oxygen-containing functional groups to oxidized compounds,58 and (b) oxidative
319
depolymerization of faunal debris (C/N > 25) is carried out by microbiota (C/N 6-10), in which
320
“fresh” organic debris with a large C/N (i.e. 30) are slowly converted into an amorphous
321
heterogeneous organic phase (humic substances) with a small C/N (i.e. 12).59,60 If the C/N ratio is
322
accepted as a rough proxy for the extent of organic matter decomposition61 with a large C/N
323
(C/N 25) indicating a relative prevalence of aliphatic C and nonpolar functionality (i.e., relatively
324
undecomposed organic matter), the C/N ratio can be treated as a rough proxy for the
325
decomposition stage ( = the "quality" of organic matter).62 Soils 1-3 and 5 have either low
326
organic carbon or a lower C/N ratio (greater number of carboxyl groups; Table 1, Table S1),
327
indicating a minimal influence of organic carbon on sorption (Soil 2) or less hydrophobic organic 12 ACS Paragon Plus Environment
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matter (Soils 1, 3, and 5). Therefore, the lack of correlation of FtS sorption with soil organic
329
carbon may be due to low hydrophobicity of the organic matter of the soils tested, with the
330
exception of Soil 4, which is more hydrophobic (higher C/N ratio; Tables 1 and S1) with fewer
331
carboxyl groups. Alternatively, the 6:2 and 8:2 FtS may require an organic carbon content
332
greater than 2.3% before hydrophobic interactions plays a significant role in their sorption. A
333
trend is difficult to discern without additional soils between 2.3% and 7.7% organic carbon.
334
To the best of our knowledge, studies examining PFAS sorption do not consider metrics
335
for the extent to which decaying organic matter is decorated with ionizable, oxygen containing
336
functional groups, which needs to be examined further. Many sorption studies of PFCAs and
337
PFSAs observe an increase in Kd with increasing organic carbon without any organic carbon
338
threshold,13-16 while a single study found little change in Kd with increasing organic carbon.63
339
No statistical evidence exists for correlations between the zwitterionic 6:2 FtSaB (-0.37, p
340
= 0.47) and the 8:2 FtSaB (-0.60, p = 0.40) and organic carbon (Fig. S11, Table S12), which is
341
consistent with reports that Kd values for zwitterionic pharmaceuticals do not correlate with
342
organic carbon content.36,37,64 The Kd (Cwi = 8.8 nM) values for the 8:2 FtSaB are consistently
343
and proportionally higher than the 6:2 FtSaB, due to the increased hydrophobicity of the
344
additional two CF2 groups. Relative to the anionic FtSs, the magnitude of the Kd values for the
345
zwitterionic FtSaBs are higher, which is likely due to the positive charge associated with the
346
polar head group, as will be discussed below. Cation exchange and electrostatic interactions
347
dominate,38 since electrostatic interactions are more thermodynamically favorable than
348
hydrophobic interactions65,66 or anionic ligand exchange,38 although hydrophobicity may help
349
exclude the sorbate from solution and aid in a higher extent of sorption.40 However, assessing
350
the thermodynamic favorability of the FtSaBs was outside the scope of the present study.
351
ECEC. No statistical evidence exists for correlations between the 6:2 FtS (-0.56, p = 0.25) and
352
the 8:2 FtS (-0.41, p = 0.42) and ECEC (Fig. 4a, Table S12), likely due to repulsion between
353
negatively charged organic matter and mineral surfaces and the negatively charged sulfonate
354
group. The high Kd (Cwi = 110 nM) of 120 L/kg for the 8:2 FtS in Soil 4 with an ECEC of 5.7 ±
355
0.80 meq/100 g is attributed to the more hydrophobic nature of the organic matter as discussed
356
above rather than cation exchange processes. The extent of cation bridging between Ca2+ and the
357
anionic FtSs was not assessed and is the focus of on-going research. 13 ACS Paragon Plus Environment
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Strong statistical evidence for positive correlations exist for the zwitterionic 6:2 FtSaB
359
(0.94, p = 0.0052) and 8:2 FtSaB (0.99, p = 0.0051) and ECEC (Fig. 4b, Table S12). The
360
proportionate increase in Kd (Cwi = 8.8 nM) from the 6:2 FtSaB to the 8:2 FtSaB may arise from
361
the greater affinity of the 8:2 FtSaB to the hydrophobic nanosites in between the localized
362
negative charges on the smectite surface.55 Alternatively, the hydrophobic perfluoroalkyl moiety
363
may allow easier exclusion from aqueous solution due to solvation effects.67 The cationic 6:2
364
FtSaAm was completely depleted from the aqueous phase in all but one soil (Soil 6; Fig. 4b),
365
which has the second highest ECEC (10 ± 3.4 meq/100 g). The terminal positive charge in the
366
cationic 6:2 FtSaAm may interact more readily with the cation exchange sites than the FtSaBs, in
367
which the terminal carboxyl group of the FtSaBs may repel the negatively charged CEC sites68.
368
Similarly, sorption studies with zwitterionic and cationic veterinary pharmaceuticals,36-38,64,69
369
organic cations,44,65 and cationic hydrocarbon surfactants70 indicate that electrostatic interactions
370
dominate, and contributions from hydrophobic partitioning are almost non-existent.38,44,65,70
371
Although the strong correlations between the zwitterionic FtSaBs and ECEC and the
372
single Kd (Cwi = 110 nM) value for the cationic 6:2 FtSaAm for Soil 6 indicate that electrostatic
373
interactions heavily influence sorption of zwitterionic and cationic PFASs, other mechanisms,
374
such as hydrophobic interactions, clearly have some impact since the 8:2 FtSaB has higher Kd
375
values than the 6:2 FtSaB. Similar to pharmaceuticals and other organic cations, traditional soil
376
properties may not be adequate to predict PFAS sorption, and new Kd models, such as those
377
developed by MacKay and Vasudevan,71 Droge et. al,44 and Jolin et. al,72 need to be incorporated
378
to assess the influence of electrostatic interactions, hydrophobic interactions, surface
379
complexation, and sorbate molecular volume.
380
AEC. No statistical evidence exists for a correlation between the anionic 6:2 FtS (0.58, p = 0.23)
381
and AEC, whereas some evidence exists for a correlation between the 8:2 FtS (0.83, p = 0.031)
382
and AEC (Fig. 5). However, the 8:2 FtS Kd value for Soil 4 is believed to be an outlier as
383
discussed in the Organic Carbon section; therefore, excluding Soil 4 from the correlation, no
384
evidence exists for a correlation between the 8:2 FtS (-0.50, p = 0.39) and AEC. Analysis of the
385
Kd values using AEC/ECEC73 and log-log transformations did not improve correlations (Table
386
S12, Table S13). The sorption of the 8:2 FtS is proportionally greater than the 6:2 FtS, except in
387
Soil 4. Since Soil 4 has both the highest organic carbon and the highest AEC, the influence of 14 ACS Paragon Plus Environment
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388
electrostatic interactions due to Soil 4’s positive charge and hydrophobic interactions cannot be
389
determined.
390
Anion exchange sites are fully protonated (pH ≤ 6; Fig. S13), singly coordinated
391
hydroxyl groups that arise from poorly crystalline forms of iron oxides (ferrihydrite) and
392
aluminosilicates.74 Soil 3 is a particularly oxide rich Ultisol, and Soil 4 has a poorly crystalline
393
mineral phase (“andic” soil properties) that contains singly coordinated hydroxyl groups (Table
394
1, Table S1). In the case of Soil 4 with the anionic 8:2 FtS, inner sphere complex formation via
395
anionic ligand exchange with the singly coordinated hydroxyl groups74 may contribute to the
396
observed increase in sorption. However, if contributions from inner sphere complex formation
397
strongly influenced the 8:2 FtS sorption in Soil 4, a proportional increase in the sorption of the
398
6:2 FtS would be expected. The lack of correlation between FtS sorption and AEC indicates that
399
the sulfonate group may not be as effective at surface complexation as carboxyl groups74,75 or
400
carboxyl groups with neighboring hydroxyl groups76.
401
No statistical evidence exists for correlations between the zwitterionic 6:2 FtSaB (-0.21, p
402
= 0.69) and 8:2 FtSaB (-0.58, p = 0.42) and AEC (Fig. S12). AEC trends with zwitterion
403
sorption are less frequently studied, but zwitterionic pesticide sorption experiments found either
404
an increase75 or no change77 in sorption with increasing AEC. The lack of correlation with the
405
zwitterionic FtSaBs and AEC is not unexpected because, in the case of zwitterionic
406
pharmaceutical sorption, the contribution of surface complexation and electrostatic interactions
407
with anion exchange sites has less influence than electrostatic interactions with cation exchange
408
sites.38,65,66
409
pH. As pH increases from 4 to 7 in Soil 1, Kd (Cwi = 110 nM) values remain unchanged for the
410
anionic 6:2 FtS (-0.55, p = 0.63) but decrease for the anionic 8:2 FtS (-0.99, p = 0.019; Fig. 6).
411
For the zwitterionic FtSaBs, however, Kd (Cwi = 8.8 nM) values decrease then remain constant as
412
pH increases (6:2 FtSaB: -0.81, p = 0.39; 8:2 FtSaB: -0.69, p = 0.51; Fig. 6). Due to the limited
413
statistical power with three data points, the correlations discussed should be interpreted
414
cautiously.
415 416
The decrease in Kd (Cwi = 110 nM) with increasing pH for the anionic 8:2 FtS is consistent with observed decreases in sorption for organic acids78 and other anionic PFASs16 15 ACS Paragon Plus Environment
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417
with an increase in pH. The decrease is approximately 0.17 log units per unit increase in pH,
418
assuming a linear fit, which is less steep relative to other anionic PFASs.16 Since the 6:2 and 8:2
419
FtS remain anions in the pH range studied (Fig. S13), the decrease in sorption is likely due to
420
deprotonation of the negatively charged organic matter (pKa ~ 4.5; Fig. S13)79,80 and thus anion
421
repulsion. Given that the zero-point-of-charge of iron and aluminum oxides is approximately
422
8.5, the oxide surfaces are increasingly protonated with decreasing pH and become increasingly
423
available to undergo anionic ligand exchange81 and, thus, result in a higher Kd at lower pH. The initial decrease in Kd (Cwi = 8.8 nM) that was then followed by no change in Kd (Cwi
424 425
= 8.8 nM) as pH increased for the zwitterionic FtSaBs is likely not due to the speciation of the
426
FtSaBs (Fig. S13) but rather the protonation of organic matter. Between pH 4 and pH 7, the
427
FtSaBs are zwitterionic with ~99 % deprotonated carboxyl group (negative charge) and a
428
positively charged quaternary amine, indicating that speciation does not significantly change in
429
the pH range studied. Soil 1 has an ECEC of 6.8 meq/100g at pH 5.1, and a batch reactor
430
containing Soil 1 and 440 nM 6:2 FtSaB Cwi has 6.8*10-2 mmol charge and 6.7*10-6 mmol
431
positively charged PFASs, indicating that the ECEC, even with changes in pH, would not be
432
exceeded in the current system.37 Instead, the speciation of the organic matter changes. At pH 4,
433
more than 50 % of carboxylic functional groups in soil organic matter will be protonated,
434
resulting in a joint contribution of hydrophobic interactions and electrostatic interactions through
435
cation exchange sites to FtSaB sorption. As pH increases and the carboxyl groups in the organic
436
matter become deprotonated, electrostatic interactions still influence sorption, but the negatively
437
charged organic matter likely repels the terminal carboxyl group of the FtSaB, causing sorption
438
to decrease. The finding contrasts those from sorption studies of veterinary pharmaceuticals in
439
which speciation changed as a function of pH and significantly influenced zwitterion sorption.36-
440
38,77
441
IMPLICATIONS
442
The low Kd values for the anionic 6:2 FtS suggest that the 6:2 FtS is highly mobile in
443
groundwater. Analysis of AFFF-impacted groundwater12,82 indicates that the 6:2 FtS is present
444
in high concentrations (up to mg/L). The higher Kd values indicate that the anionic 8:2 FtS,
445
zwitterionic FtSaBs, and cationic 6:2 FtSaAm are more likely to be associated with soil and
446
sediment. The anionic 8:2 FtS has been found in higher concentrations on AFFF-impacted soils 16 ACS Paragon Plus Environment
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447
and sediments,22,27,83 while the first reports of zwitterionic FtSaBs and cationic FtSaAms on
448
soil21 and sediment are currently being presented.22-25
449
By analogy, the anionic 8:2 FtS, zwitterionic FtSaBs, and cationic 6:2 FtSaAm are likely
450
to be found in PFAS source zones, especially where AFFFs were repeatedly applied at a field
451
site. However, current estimates of the mass of PFASs in the source zone are likely to be
452
significantly underestimated. Although the high Kd analytes may be immobilized in the source
453
zone, the complex interactions between anionic, zwitterionic, and cationic PFASs and soil may
454
impact their mobility in the subsurface. Furthermore, the high Kd values of the anionic 8:2 FtS,
455
zwitterionic FtSaBs, and the cationic 6:2 FtSaAm may not accurately predict the mobility of
456
these polyfluoroalkyl substances at all AFFF-impacted sites, as cationic PFASs have been found
457
in high abundance in AFFF-impacted groundwater.11 Mobile cationic PFASs have the potential
458
to impact drinking water sources, and non-fluorinated cations have been found to be more toxic
459
to aquatic species.84,85 Therefore, cationic PFASs might be more toxic by analogy. Removal of
460
mobile zwitterionic and cationic PFASs from drinking water sources is unknown, in part due to
461
the current analytical methods employed by the private sector, which only focus on well-studied
462
anionic PFASs (i.e. PFCAs and PFSAs).
463
Overall, the lack of correlations between the anionic FtSs, zwitterionic FtSaBs, and
464
cationic 6:2 FtSaAm and bulk soil parameters, such as organic carbon content, ECEC, and AEC,
465
indicates that the bulk parameters do not adequately predict sorption, at least for the compounds
466
studied. The influence of electrostatic interactions, hydrophobic interactions, cation bridging,
467
surface complexation, and structures of PFASs need to be understood in source zones before
468
robust remediation strategies can be proposed. For example, the multilayer sorption observed for
469
the anionic 6:2 FtS and the zwitterionic 6:2 FtSaB indicates that soil surfaces may become
470
coated in PFASs. Sorption of additional PFASs in AFFF to a soil already saturated with PFASs
471
may increase the sorption of the added PFASs, due to fluorophilic interactions between PFASs
472
sorbed to the surface and additional PFASs in solution.86 Furthermore, the impact of PFCAs and
473
PFSAs in the subsurface from AFFFs9,12 and biodegradation87-89 on the sorption of zwitterionic
474
and cationic PFASs remains unknown. Additionally, desorption and therefore the reversibility of
475
sorbed zwitterionic and cationic PFASs need to be determined, as the reversibly bound PFASs
476
may become mobile in the subsurface.20 17 ACS Paragon Plus Environment
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477
Notes
478
The authors declare no competing financial interest.
Page 18 of 32
479 480
ACKNOWLEDGEMENTS
481
K. Barzen-Hanson was supported by the National Science Foundation’s Graduate Research
482
Fellowship Program Fellowship 1314109-DGE. The study was supported by the Strategic
483
Environmental Research and Defense Program Grant ER-2128 (J. Field). The authors would like
484
to thank Nicole Riddell and Alan McAlees of Wellington Laboratories, Inc. for providing the
485
pKa estimates and rationale, Steven Droge for suggesting Chemicalize for pKa values, and
486
Christopher Higgins of Colorado School of Mines for the insightful comments in the preparation
487
of this manuscript.
488 489
SUPPORTING INFORMATION AVAILABLE
490
Chemicals, details on isotherm set-up, absolute extraction efficiencies, soil extraction method
491
validation, analytical methods, pKa rationale, Tables S1-S13, Figures S1-S13. This information
492
is available free of charge via the Internet at http://pubs.acs.org.
493 494 495 496 497 498 499 500
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Page 20 of 32
Table 1. Soil properties. a
b
%N
C/N Ratio
CECc (meq/100g)
ECECd (meq/100g)
AECe (meq/100g)
% Clay
% Sand
% Silt
b
Soil #
pH
% OC
1
5.1
1.5
0.13
13
14 ± 0.59f
6.8 ± 0.68
0.20
22
6.3
71
2
5.5
0.12
0.02
6.8
22 ± 4.2
17 ± 2.2
0.58
26
10
64
3
5.1
2.3
0.20
13
17 ± 3.1
5.1 ± 0.56
1.2
48
14
39
4
5.0
7.7
0.43
21
36 ± 3.6
5.7 ± 0.80
2.2
18
37
45
5
5.0
1.0 ± 0.19
0.084 ± 0.0087
12 ± 1.1
16 ± 1.6
7.5 ± 0.44
0.28g
23 ± 3.2
4.8 ± 0.29
72 ± 3.0
6
5.2
0.098
0.004
30
16 ± 1.5
10 ± 3.4
0.33
24
3.6
73
504 505 506 507 508 509
a
pH at which the isotherm was conducted. bPercent organic carbon (% OC) and percent nitrogen, as determined by the method of Goni et al.90 cCation Exchange Capacity, measured by summation method, pH 7. dEffective cation exchange capacity measured at the native soil pH, as determined by the method of Gillman and Sumpter.91,92 eAnion exchange capacity at native soil pH (using water). fError computed as the 95% CI determined from a blind triplicate analysis. gOnly two values were valid, which has limited statistical power. No 95% CI was calculated.
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510 511
Figure 1. Structures of the dominant species of (A) the FtSs, (B) the FtSaBs, and (C) the 6:2
512
FtSaAm in National Foam AFFF at all native soil pHs.
513
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514 515
Figure 2. Log-transformed Freundlich isotherms for the anionic 6:2 and 8:2 FtSs and the
516
zwitterionic 6:2 and 8:2 FtSaBs for the Soil 1 native pH isotherm. The ovals highlight the sharp
517
increase in sorption.
518
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519 520
Figure 3. A lack of correlation for the anionic FtSs as a function of soil organic carbon. Error
521
bars indicate the 95% CI.
522
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523 524
Figure 4. A lack of correlation for (A) the anionic FtSs and (B) strong, positive correlations for
525
the zwitterionic 6:2 and 8:2 FtSaBs and the cationic 6:2 FtSaAm with increasing ECEC. Error
526
bars represent the 95% CI. The aqueous phase concentration was