Stabilization remediation of soils contaminated with per- and polyfluoroalkyl substances (PFASs)

Per- and polyfluoroalkyl substances (PFASs) are a major global concern in pollution of drinking water sources and aquatic environments. Due to the high persistence and mobility of these compounds, remediation methods for PFAS-contaminated soils are urgently needed to protect the surrounding environment and drinking water source areas. This is particularly important at firefighter training sites, due to the historical usage and release of PFAS-containing aqueous foams causing high levels of soil contamination, with high potential for leaching to groundwater and nearby environments. This thesis assessed the efficacy of stabilization remediation methodologies in mitigating PFAS leaching from contaminated soils. Screening of 44 PFAS sorbent materials showed that activated carbons (ACs) (granulated and pulverised, n = 5) were the best sorbent (mean removal efficiency >99.9%) for PFASs in aqueous solution. Based on these results, a commercially available injectable colloidal AC product (PlumeStop®) for soil stabilization was systematically assessed for PFAS retention efficiency. The best treatment efficiency for 10 different soils (fortified with 17 PFASs) treated with colloidal AC was observed for perfluorooctanoic acid (PFOA), 6:2 fluorotelomer sulfonate (6:2 FTSA) and perfluorohexane sulfonate (PFHxS), resulting in sorption increases of >80%. Assessment was also performed of a stabilization-solidification (S/S) technique that uses cementitious material to chemically stabilise PFASs and solidify the soil, decreasing hydraulic conductivity and thereby reducing PFAS leaching potential. The S/S technique was tested on PFAS-spiked soil using a cost-efficient cementitious material with a soil:binder ratio of 9:1 and seven different additives (including ACs) to 0.2% of dry weight (dw). In conservative leaching tests, treatment efficiency was highest for AC additive amended S/S remediation (e.g. >99.9% for longer-chain PFASs such as perfluorooctane sulfonate (PFOS)). To further assess the applicability and long-term stability of S/S treatment, a pilot-scale experiment was set up treating over six tons of field-contaminated soil using 15% cementitious binder and 0.2% dw mass-granulated AC. An artificial irrigation system was used to apply the equivalent of six years of precipitation. The treatment efficiency was >97% for four dominant PFASs homologues (perfluorohexanoic acid (PFHxA), PFOA, PFHxS and PFOS), but low (3%) for shortchain perfluoropentanoic acid (PFPeA). Ultimately, based on laboratory- and pilot-scale experiments, it can be concluded that stabilization remediation of PFAS-contaminated soils can be an efficient technique, in particular for longer-chain PFASs

Thermal desorption as a high removal remediation technique for soils contaminated with per- and polyfluoroalkyl substances (PFASs)

Soils contaminated with per- and polyfluoroalkyl substances (PFASs) are an important source for impacting drinking water delivery systems and surface water bodies world-wide, posing an urgent risk to human health and environmental quality. However, few treatment techniques have been tested for PFAS-contaminated soil hotspots. This study investigated the possibility of thermal desorption as a possible technique to remediate soils contaminated with multiple PFASs. Two fortified soils ( n-ary sumation (9)PFAS approximate to 4 mg kg(-1)) and one field-contaminated soil ( n-ary sumation (9)PFAS approximate to 0.025 mg kg(-1)) were subjected to a 75-min thermal treatment at temperatures ranging from 150 to 550 degrees C. Soil concentrations of PFASs showed a significant decrease at 350 degrees C, with the n-ary sumation (9)PFAS concentration decreasing by, on average, 43% and 79% in the fortified and field contaminated soils, respectively. At 450 degrees C, >99% of PFASs were removed from the fortified soils, while at 550 degrees C the fraction removed ranged between 71 and 99% for the field contaminated soil. In the field contaminated soil, PFAS classes with functional groups of sulfonates (PFSAs) and sulfonamides (FOSAs) showed higher removal than the perfluoroalkyl carboxylates (PFCAs). Thus thermal desorption has the potential to remove a wide variety of PFASs from soil, although more studies are needed to investigate the cost-effectiveness, creation of transformation products, and air-phase vacuum filtration techniques

Electrokinetic remediation for removal of per- and polyfluoroalkyl substances (PFASs) from contaminated soil

Uncontrolled use and disposal of per-and polyfluoroalkyl substances (PFASs) in recent decades has resulted in extensive soil and groundwater contamination, necessitating counteraction. Electrokinetic remediation (EKR) offers a promising approach to in-situ soil remediation. Two novel modifications to conventional EKR were tested for the first time in a laboratory-scale study, to explore the capacity of EKR for PFAS removal. The first modi-fication was a two-compartment setup designed for PFAS extraction from soil to an electrolyte-filled chamber. The second was a single-compartment setup designed to transport and confine contaminants in a chamber filled with granular activated carbon (GAC), thus, combining extraction with stabilisation. Electromigration varied for individual compounds, based mainly on perfluorocarbon chain length and functional group. The results indicated up to 89% concentration and extraction of n-ary sumation PFASs for the two-compartment setup, with removal efficiency reaching 99% for individual PFASs with C <= 6. Removed PFASs were concentrated adjacent to the anode at the anion exchange membrane, while short-chain compounds were extracted in the anolyte. The single-compartment setup achieved 75% extraction and accumulation of n-ary sumation PFASs in GAC. This demonstrates, for the first time, good effectiveness of coupling EKR with AC stabilisation for PFAS removal from soil. Perfluorocarbon chain length was a dominant factor affecting treatment efficiency in both setups, with very high removal rates for short-chain PFASs

Spatial distribution and load of per- and polyfluoroalkyl substances (PFAS) in background soils in Sweden

Per- and polyfluoroalkyl substances (PFAS) are known to be persistent, bioaccumulative, and have adverse health effects, but very little is known about PFAS in the terrestrial environment and factors influencing their distribution. This paper presents one of the first comprehensive studies investigating PFAS (n = 28) in background forest soils (n = 27) on national scale across Sweden. The results showed that 16 of 28 target PFAS were present and all sites contained at least three PFAS compounds, with total concentrations ranging between 0.40 ng/g dry weight (dw) and 6.6 ng/g dw. Perfluorooctanesulfonic acid (PFOS) showed the highest detection frequency of 89% and a median concentration of 0.39 ng/g dw. The PFOS loads (ng/m(3)) showed a distinct spatial distribution, with a significant exponential increase from north to south (R-2 = 0.55; p < 0.001) and west to east (R-2 = 0.35; p < 0.01). In some parts of Sweden, the compound 6:2 fluorotelomer sulfonate (6:2 FTSA) had a higher median concentration (1.4 ng/g dw), but was in comparison to PFOS more impacted by local sources. Partial least squares discriminant analysis (PLS-DA) showed regional clustering of PFAS compositional profiles, indicating that PFAS soil background concentrations are functions of spatial variations at local, regional, and countrywide scale. Such spatial trends have not been observed previously and it could not be deduced whether they are indicative of trends on a global scale, or country-specific and better explained by proximity to densely populated urban areas. An interpolation and extrapolation raster map created from the results was used to calculate the average total PFAS load on Swedish soils. Estimated total load in the top 10-cm soil layer was 2.7 +/- 2.4 tons for PFOS and 16 +/- 14 tons for n-ary sumation PFAS, indicating that soil carries a considerable legacy of past PFAS release

Fly ash-based waste for ex-situ landfill stabilization of per- and polyfluoroalkyl substance (PFAS)-contaminated soil

In response to world-wide soil and groundwater contamination per- and polyfluoroalkyl substances (PFAS), stakeholders require immediate mitigation. Soil deposition in landfill is a common mitigation scheme, but PFAS losses occur via landfill leachate. These leaching losses can be reduced by strategically utilizing other deposited waste materials for ex-situ contaminant stabilization. This screening study tested activated carbon (AC) and eight types of wastes (compost, rubber granulate, bentonite clay, industrial sludge, incineration slag, incineration bottom ash (n=4), incineration fly ash-based air pollution control residue (FA-APC) (n=16)) in amending (adding 4%, 5%, 10% or 25% sorbent) field-contaminated (n=19) and PFAS-fortified (n=11) soils. A subset of FA-based residue types, all originating from grate-fire incineration (G-F-I) plants, achieved extraordinarily high removal of PFAS. The removal was up to 98% (25% addition) of the sum of six dominant PFAS for field-contaminated soil and >99% of the sum of 11 PFAS for fortified soil (10/25% addition) (>99.9% for PFOS). Calculated partitioning coefficient revealed significant trends between sorption strength and perfluorocarbon chain length (0.21-0.47 log units per CF2-moiety), indicating high importance of hydrophobic sorption (R2>0.98). However, with incremental G-F-I FA-APC addition this relationship disappeared, indicating an alternative sorption mechanism. The exceptional PFAS sorption by G-F-I FA-APC was not explained by G-F-I surface area, surface charge, soil mineral- and metal composition, or solution DOC, metal, or ion composition (H+, Ca2+, Mg2+, Al3+ and Ba2+). Although the mechanism remains unknown, this study showed that landfill sites can utilize G-F-I FA-APC for ex-situ stabilization at negative cost, thus preventing PFAS-containing leachate

Long-distance transport of per- and polyfluoroalkyl 2 substances (PFAS) in a Swedish drinking water aquifer

Use of per-and polyfluoroalkyl substance (PFAS)-containing aqueous film-forming foams (AFFF) at firefighting training sites (FFTS) has been linked to PFAS contamination of drinking water. This study investigated PFAS transport and distribution in an urban groundwater aquifer used for drinking water production that has been affected by PFAS-containing AFFF. Soil, sediment, surface water and drinking water were sampled. In soil (n = 12) at a FFTS with high perfluorooctane sulfonate (PFOS) content (87% of sigma PFAS), the sigma PFAS concentration (n = 26) ranged from below detection limit to 560 ng g(-1)dry weight. In groundwater (n = 28), the sigma PFAS concentration near a military airbase FFTS reached 1000 ng L-1. Principal component analysis (PCA) identified the military FFTS as the main source of PFAS contamination in drinking water wellfields > 10 km down-gradient. Groundwater samples taken close to the military FFTS site showed no sigma PFAS concentration change between 2013 and 2021, while a location further down-gradient showed a transitory 99.6% decrease. Correlation analysis on PFAS composition profile indicated that this decrease was likely caused by dilution from an adjacent conflating aquifer. sigma PFAS concentration reached 15 ng L-1 (PFOS 47% and PFHxS 41% of sigma PFAS) in surface river water (n = 6) and ranged between 1 ng L-1 and 8 ng L-1(PFHxS 73% and PFBS 17% of sigma PFAS) in drinking water (n = 4). Drinking water had lower PFAS concentrations than the wellfields due to PFAS removal at the water treatment plant. This demonstrates the importance of monitoring PFAS concentrations throughout a groundwater aquifer, to better understand variations in transport from contamination sources and resulting impacts on PFAS concentrations in drinking water extraction areas

Laboratory-scale and pilot-scale stabilization and solidification (S/S) remediation of soil contaminated with per- and polyfluoroalkyl substances (PFASs)

Remediation of soil contaminated with per-and polyfluoroalkyl substances (PFAS) is critical due to the high per-sistence and mobility of these compounds. In this study, stabilization and solidification (S/S) treatment was evaluated at pilot-scale using 6 tons of soil contaminated with PFAS-containing aqueous film-forming foam. At pilot scale, long-term PFAS removal over 6 years of precipitation (simulated using irrigation) in leachate from non-treated contaminated reference soil and S/S-treated soil with 15 % binder and 0.2 % GAC was compared. PFAS removal rate from leachate, corresponding to reduction in leaching potential after 6 years, was 97 % for four dominant PFASs (perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA), perfluorohexanesulfonic acid (PFHxS) and per-fluorooctanesulfonic acid (PFOS)), but low (3%) for short-chain perfluoropentanoic acid (PFPeA). During the pilot scale experiment, PFAS sorption strength (i.e., soil-water partitioning coefficient (Kd)) increased 2to 40-fold for both reference and S/S-treated soil, to much higher levels than in laboratory-scale tests. However, PFAS behavior in pilot scale and laboratory-scale tests was generally well-correlated (p &lt; 0.001), which will help in future S/S recipe optimization. In addition, seven PFASs were tentatively identified using an automated suspect screening approach. Among these, perfluorohexanesulfonamide and 3:2 fluorotelomer alcohol were tentatively identified and the latter had low removal rates from leachate (&lt; 12 %) in S/S treatment

Non-target and suspect screening strategies for electrodialytic soil remediation evaluation: Assessing changes in the molecular fingerprints and per- and polyfluoroalkyl substances (PFASs)

Contamination of soils with organic pollutants is an increasing global problem, so novel soil remediation techniques are urgently needed. One such technique is electrokinetic remediation, in which an electric field is applied over the soil to extract contaminants. Previous evaluations of the technique have been limited to a few specific compounds. In this study, we integrated the latest advances in high-resolution mass spectrometry (HRMS) to identify molecular fingerprints, and used the results to improve the mechanistic understanding necessary for successful remediation. A laboratory-scale 0.38 mA cm(-2) electrodialytic treatment was applied for 21 days to a contaminated soil from a firefighter training facility in Sweden. Non-target analysis allowed generic evaluation of changes in the soil organic fraction by tentatively determining the elemental composition of compounds present. The results showed that smaller oxygen-rich molecules were significantly transported to the anode by electromigration, while larger hydrogen-saturated molecules were transported to the cathode by electroosmotic flow. Wide suspect screening with >3000 per- and polyfluoroalkyl substances (PFASs) tentatively identified seven new PFASs in the test soil, including perfluoroheptanesulfonic acid (PFHpS), and PFASs with butoxy, ethoxy, ethanol, and ethylcyclohexanesulfonate functional groups

Occurrence and removal of chemicals of emerging concern in wastewater treatment plants and their impact on receiving water systems

Wastewater treatment plants (WWTPs) are considered the main sources of chemicals of emerging concern (CECs) in aquatic environments, and can negatively impact aquatic ecosystems. In this study, WWTP influent, effluent, and sludge, and upstream and downstream waters from the WWTP recipient were investigated at 15 locations for a total of 164 CECs, including pharmaceuticals, personal care products, industrial chemicals, per- and polyfluoroalkyl substances (PFASs), and pesticides. In addition, zebrafish (Dania rerio) embryo toxicity tests (ZFET) were applied to WWTP influent and effluent, and upstream and downstream waters from WWTP recipients. A total of 119 CECs were detected in at least one sample, mean concentrations ranging from 0.11 ng/L (propylparaben) to 64,000 ng/L (caffeine), in wastewater samples and from 0.44 ng/L (ciprofloxacin) to 19,000 ng/L (metformin) in surface water samples. Large variations of CEC concentrations were found between the selected WWTPs, which can be explained by differences in CEC composition in influent water and WWTP treatment process. The sludge-water partitioning coefficient (K-d) of CECs showed a significant linear con-elation to octanol/warer partition coefficient (K-ow) (p &lt; 0.001), and thus could be used for predicting their fare in the aqueous and solid phase. The Sigma CEC concentrations in WWTPs declined by on average 60%, based on comparisons of WWTP influent and effluent concentrations. The high concentrations of CECs in WWTP effluent resulted in, on average, 50% higher concentrations of CECs in water downstream of WWTPs compared with upstream. Some WWTP samples showed toxicity in ZFET compared with the respective control group, but no individual CECs or groups of CECs could explain this toxicity. These results could provide a theoretical basis for optimization of existing treatment systems of different designs, and could significantly contribute to protecting recipient waters. (C) 2020 The Authors. Published by Elsevier B.V

Noggrannhet i svenska segmenterade och osegmenterade i avbördningskurvor : Med hänsyn till mätosäkerhet och heteroskedacitet

River discharge estimation is the basic hydrological information for most hydrological applications in various socioeconomic planning. Increasing the accuracy of the traditional rating curve in relation to river discharge estimation would be very valuable to hydrological applications. Suggestions have been made that the traditional power function rating curve should be divided into several segments because this is often motivated by the physical characteristics of the river. Each curve is commonly constructed by regression and each requires 3 estimated parameters. However stage-discharge data is often scarce, and this scarcity could lead to overparametrization and deterioration of accuracy. By constructing many unsegmented and segmented rating curves accounting for measurement uncertainty, the models can be validated, it can be determined if segmented rating curves suffers from overparametrization. The results showed that two-segmented rating curves did not yield better fits to data, and nor did it generate larger errors than unsegmented rating curves in extrapolation. Segmentation only reduced errors in low flow interpolation, when there is a clear segmentation.  It could also be concluded that unsegmented rating curves were slightly more robust when extrapolating. The biggest impact on rating curve errors was shown not to be determined by segmentation, but rather much more dependent on the amount of discharge measurement uncertainty or choice of regression method. With a mean discharge uncertainty of ±5 %, the errors from in high flow was 60 % in interpolation and 35 % in extrapolation. For low flows, the interpolation errors were around 95 % end extrapolation error estimation was 250 %. Conclusions could also be made that the relative errors from rating curves increased with lower discharges. Other important regression factors, such as heteroscedasticity, sometimes showed to have substantial impact on rating curve regressions, generally reduced from 59 % occurrence in unsegmented rating curves to 14-15 % in segmented rating curves. Uppskattning av vattenflöden i vattendrag är den grundläggande informationen för de flesta hydrologiska applikationer vid olika typer av socioekonomisk planering. Att förbättra noggrannheten i avbördningskurvor då vattenflödet uppskattas vid en mätstation skulle vara värdefullt för de flesta tillämpningar där vattenflöden används. Tidigare studier har föreslagit att avbördningskurvor borde delas upp i flera segment, eftersom vattendrag inte sällan har olika segment med olika fysikaliska karaktärer. Varje segment kräver dock att 2-3 regressionsparametrar bestäms, men flödesmätningar vid olika vattennivåer är ofta få, och knappheten kan göra att en utökad modell blir överparametriserad och än mer osäker.   Genom att konstruera många avbördningskurvor, segmenterade och osegmenterade, kan dessa valideras mot valideringsdata och var det möjligt se om segmenterade avbördningskurvor blev överparametriserade. Studien visade att segmenterade avbördningskurvor vid kalibrering, interpolation och extrapolation generellt inte gav bättre prediktion än osegmenterade avbördningskurvor. Vid låga flöden och tydligt motiverade segmenteringar gav segmenterade avbördningskurvor en bättre interpolation, men dock inte vid extrapolation, vilket är en indikation att segmenterade avbördningskurvor var något överparametriserade. Den största inverkan på att minska felen i avbördningskurvor var var att minska mätosäkerheten i flödesmätningarna. Med en genomsnittlig mätosäkerhet i flödesmätningarna på ±5 % kunde osäkerheten kvantifieras till kring 60 % för interpolerade osegmenterade avbördningskurvor vid höga flöden och kring 95 % vid låga flöden. Variansen var dock stor. Osäkerheten från modellvalideringen av extrapolation för osegmenterade avbördningskurvor vid höga flöden kvantifierades till kring 35 % vid höga flöden och kring 250 % vid låga flöden. Resultaten visade att de relativa felen från avbördningskurvor blev större för ju lägre flödet blir.   Heteroskedastitet, som kan generera osäkerheter i avbördningskurvor, visade sig vara vanligare (59 %) i osegmenterade avbördningskurvor jämfört med segmenterade (14-15 %). Även antalet flödesmätningar hade en betydelse för felen i avbördningskurvor.Avbördningskurva, icke-linjär regression, flöde, flödesmätning, osäkerhet, validering, hydrologi, överparametrisering, vattenstån