Electronic Supplementary Material s13

Electronic Supplementary Material

Historical usage of aqueous film forming foam (AFFF): A case study of the widespread distribution from a military airport of perfluoroalkyl acids in groundwater, lakes, soils and fish.

Marko Filipovic1*, Andreas Woldegiorgis2, Karin Norström3 Momina Bibi3, Maria Lindberg2, Ann-Helen Österås2

1Department of Applied Environmental Science (ITM), Stockholm University, SE-10691 Stockholm, Sweden

2WSP Sweden AB, SE-121 88 Stockholm, Sweden

3IVL Swedish Environmental Research Institute, BOX 21060, SE-100 31 Stockholm, Sweden

* corresponding author: [email protected]

Abbreviations: n.a Not analyzed

MDL Method detection limit

PFHxA Perfluorohexanoic acid

PFOA Perfluorooctanoic acid

PFHxS Perfluorohexane sulfonate

PFOS Perfluorooctane sulfonate Contents 1. Interview of participants

The former group. The officers. constituted men in the age of 75- 80 years while the latter (their civilian counterparts) constituted of men in the age of 50-55 years.

Transcripts of all interviews (in Swedish) have been published elsewhere (contact the

Botkyrka municipality for more access. http://www.botkyrka.se/). All interviewees were informed of the purpose of the interview by the interviewer (Dr. Woldegiorgis) and the identity of the customer (Botkyrka Municipality). All interviewees participated unconditionally without any financial or other type of reimbursement to the best of their ability in order to share important information and recollections.

The main information from the interviews of former officers can be summed up as follows; During the air force base époque three different fire-fighting training sites were used (marked 1,2,3 and 4 in Figure 2). Location nr 1 was used during the period

1962-1969. It was not built on any impervious surface, and was deemed most probably not contaminated by the use of PFC-containing AFFF-foams although

AFFF-foams were introduced on the market during the mid-1960s (Place and Field,

2012). Location nr 2 was left unattended since it became clear that the years of service were before 1962 and at that time period firefighting was executed using protein- based foams. Location nr 3 was the main firefighting training facility between 1970 –

1985 (sparsely between 1985-1994). Lastly, at location nr 4 a Napalm training ground was established which was intensively used throughout the 1970s.

Furthermore, and probably different from most civilian airports, the air force base encountered numerous accidents and incidents during the transfer from propeller era to the jet engine era, including planes crashing upon takeoff and landing, fire incidents, accidental dispersion of jet engine starting fuel (isopropyl nitrate, nowadays classified as a low-sensitivity explosive).

At location 5, huge amounts of firefighting foam was dispersed when two J34 Hawker

Hunter crashed on top of each other in a big blast causing pilot casualties. Even though all military interviewees strongly recollects the accident as one of the worst, the exact year still remains unclear, probably during the early 1960s. Furthermore at location nr 6 a plane leaked large quantities of fuel and caught fire resulting in the casualty of an air force base technician along with the dispersion of large quantities of

AFFF-foam in 1975.

A huge cave hangar system (not pin-pointed on any map) hosted all the aircrafts of the air force base. Due to erroneous sprinkler systems, the cave hangar system was accidentally filled with foam at least at one, possibly two occasions during the 1970s and in 1992, whereupon the foam was fanned out on the landing strip..

From the civilian interviewees a huge fire in 2003 (after the military époque) in a hangar of police helicopters stands out as the strongest recollection. No AFFF-foam was used at the occasion since neither the building nor the helicopters were considered possible to rescue in the intensive fire, instead large quantities of water was used to prevent the fire from spreading to nearby buildings. However, none of the interviewees could recollect whether any substantial quantities of AFFF foam were stored in the hangar when it caught fire.

Finally, location 7 was the location of the air force base firefighting squad where large quantities of AFFF were stored, diluted, handled and vehicles and handheld aggregates were re-filled at this location. In addition to the interviews, we observed two potential sites for PFAAs contaminated soil; a soil dumping site and large soil piles on the flight lane, location 8 and 9, respectively.

2. Estimation of PFOS in soil

In order to assess the amount of PFCs in the soil layer at the most contaminated spots at the F18 airfield site representative average concentrations of PFOS, was calculated using the Upper Confidence Limit of Mean, UCLM95. The UCLM95-value is interpreted as a “5 % risk of having PFOS-concentrations in the soil are exceeding the average value”. All calculations of the UCLM95-averages were made by the software

ProUCL v4.0 (U S EPA, www.epa.gov/esd/tsc/software.htm). Different methods were then applied in the calculations of UCLM95for the different areas of the airforce base; depending on the number of soil samples analysed and the number of non-detects. As for the main fire-fighting training facility and the napalm training ground, the high detection frequency of PFOS in the soil generated data which fits a lognormal distribution and therefore, methodology of the UCLM95 were chosen.

Based on the UCLM95-average concentrations, the depth profile of PFOS at the particular sites, and an assumption of a soil density of 1.8 kg*dm-3, the amount of

PFOS in the top soil (down to 3.5 meters) could be calculated. For the area of main fire-fighting training facility and the napalm training ground (a volume of estimated

21 000 m3) the amount of PFOS dispersed was modeled as approximately 21 kg. The corresponding amount at the site of the old fire stations was modeled 0.2 kg of PFOS. 3. Background information on the chemicals

Table S1. Acronyms and chemical structures of the chemicals studied. Name Acronym Structure

F F F F O

F Perfluorohexanoic acid PFHxA OH F F F F F F

F F F F F F O

F Perfluorooctanoic acid PFOA OH F F F F F F F F

Perfluorohexane sulfonate PFHxS

F F F F F F F F O F Perfluorooctane sulfonate PFOS S F OH F F F F F F F O

4. Analysis

The water samples were filtered using glass fiber filters (GF/C, diameter 47 mm,

Whatman) prior to extraction by using Oasis WAX cartridges (Waters, 150 mg, 6 mL,

30 μm) according to ISO/DIS 25101:2008. In short, the dissolved phase was spiked

with 25 ng of och of the internal standards. The GF/C filters were extracted using 5

mL methanol which were combined with the water sample The cartridges were

preconditioned with 4 mL of 0.1% ammonium hydroxide in methanol, 4 mL of

methanol, and finally 4 mL of Millipore water and the cartridges were loaded with the samples at approximately one drop per second. The cartridges were then washed with

4 mL of 25 mM ammonium acetate buffer (pH 4) in Millipore water and the analytes eluted with 4 mL of methanol and 4 mL of 0.1% ammonium hydroxide in methanol.

Fresh fish muscle samples (1 g) were homogenized and extracted based on the solid- liquid extraction method described by Powley et al. (2005) with a few modifications(Verreault et al., 2005). In short, aliquots of 1–2 g homogenates were spiked with 25 ng of each of the internal standards and then extracted twice with 5 mL of acetonitrile for 15 min in an ultrasonic bath. After centrifugation, the combined extract was gentle concentrated by nitrogen blow down to 1 mL and cleaned using a dispersive clean up with ENVI-Carb (100 mg, 1 mL, 100–400 mesh, Supelco, USA) and glacial acetic acid (Powley et al., 2005). A volume of 0.5 mL of the supernatant was transferred to a vial and 0.5 mL of 4 mM ammonium acetate in Millipore water was added, The extract was stored in a freezer until instrumental analysis.

The soil samples were freezed dried overnight and aliquotes of 1 g soil was extracted by solid-liquid extraction method described by (Powley et al., 2005). The soil sample were spiked with 25 ng of each of the internal standards 5 mL 0.2 M sodiumhydroxide was added. The samples were then extracted twice with 5 mL methanol in an ultrasonic bath for 30 min. After centrifugation, the extracts were combined and 50 μL hydrochloric was added for neutralization. The extract was concentrated to 1 mL before analysis and then cleaned using ENVI-Carb as described for the fish tissue samples.

The separation and detection of PFASs were performed by high-performance liquid chromatography (HPLC, UFLC Shimadzu, model CBN-20A, Japan) coupled to a mass spectrometer interfaced with an electrospray ionization source in a negative-ion mode (ESI-MS/MS, API 4000, AB Sciex, Foster City, CA, USA). The temperature of the LC column was held constant at 40 °C. Aliquots of 10 μL were injected on a C8 column (50 mm x 3 mm, 5 μm particle size, Thermo Scientific, Dalco Chromtech)

–1 using a gradient of 400 μL min methanol and water (both with 2 mM NH4OAc). The initial gradient was set at 40/60 (v/v) methanol/water (hold for 0.5 min), then increased to 95/5 methanol/water (hold for 5 min) and then decrease to 40/60 methanol/water (hold for 8 min). The MS/MS was operated at the most sensitive transition from precursor ion to product ions in the multiple-reaction monitoring

(MRM) mode. The isotope dilution method was used for quantification. 5. Instrumental analysis and quantification

Table S2. Blanks corresponding to average batch MDLs.

Sample type Scale MDL MDL MDL MDL PFHxA PFOA PFHxS PFOS A < 2 < 0.3 < 0.1 < 1 Soil ng g-1 d.w. B < 1.5 < 0.1 < 0.02 < 0.5 Water C ng L-1 < 0.5 < 1 < 0.5 < 1 samples D <1 <0.05 <0.5 <1 Fish E ng g-1 f.w. <0.1 <0.05 <0.5 <1 muscle F <1 <0.1 <0.02 <1 G <1 <0.1 <0.5 <1 A) Old fire station B) J34 Hawker Hunter impact site C) Surface water, Ground water and Tap water wells D) Blank samples for fish collected at Lake Bysjön. E) Blank samples for fish collected at Lake Getaren. F) Blank samples for fish collected at Lake Axaren G) Blank samples for fish collected at Lake Hacksjön

Table S3. Mean recoveries of internal standards standard deviation.

Sample type 13C4-PFOA 13C4-PFOS

A 84% ±19% 86% ± 14% B 111% ± 17% 80% ±24% C 111% ± 17% 80% ±24% D 85% ±15% 70% ± 9% A) Mean recoveries for PFAAs in soil B) Mean recoveries for PFAAs in Surface water. C) Mean recoveries for PFAAs in Ground water and Tap water wells. D) Mean recoveries for PFAAS in fish. 6. Detection frequencies in soil, fish, ground water and surface water

Table S4. Detection frequency in (%) of PFAAs in the soils

n PFHxA PFOA PFHxS PFOS

A 5 0 80 100 100 B 5 0 20 0 0 C 15 27 87 100 100 D 10 0 30 80 40 E 10 0 10 40 20 A) Old fire station. B) J34 Hawker Hunter impact site C) Napalm-/ Main firefighting training facility D) Intermediate soil depot E) Soil Depot Table S5. Detection frequency in (%) of PFAAs in the soil cores

A 8 n.a 100 n.a 100 B 8 n.a 87.5 n.a 100 C 6 n.a 100 n.a 100 A) Napalm training ground B) Old fire station. C) Main firefighting training facility (n.a) denotes not analyzed.

Table S6. Detection frequency in (%) of PFAAs in the groundwater. surface waters

A 14 36 64 64 79 B 16 56 75 69 94 C 10 0 10 10 10 A) Surface water B) Ground water C) Tap water wells Table S7. Detection frequency in (%) of PFAAs in the fish muscle tissue

Species n PFHxA PFOA PFHxS PFOS

Roach 4 0 0 50 100 Carp Bream 4 0 0 50 100 Ruffe 3 0 0 0 100 Northern Pike 2 0 0 0 100 European Perch 8 0 0 62.5 100

7. PFAAs in soil samples

Table S8. PFAAs in the soil samples from Old fire station. Sampling location Concentrations of PFSAs [ng g-1 d.w.] (Old fire station)

Sampling Sampling Date PFHxA PFOA PFHxS PFOS depth (m) 2012-05-22/24 0.5-1.0 < 2 0.91 6 35.7 2012-05-22/24 0.5-1.0 < 2 0.77 5.2 287 2012-05-22/24 0.5-1.0 < 2 0.53 3.6 39 2012-05-22/24 0.5-1.0 < 2 < 0.3 1.6 166 2012-05-22/24 0.5-1.0 < 2 1.2 2.3 278 Table S9. PFAAs in the soil samples from J34 Hawker Hunter impact site Sampling location -1 (J34 Hawker Concentrations of PFSAs [ng g d.w.] Hunter impact site) Sampling Sampling Date PFHxA PFOA PFHxS PFOS depth (m) 2012-05-22/24 0.5-1.0 < 2 < 0.3 < 0.1 < 1 2012-05-22/24 0.5-1.0 < 2 < 0.3 < 0.1 < 1 2012-05-22/24 0.5-1.0 < 2 0.50 < 0.1 < 1 2012-05-22/24 0.5-1.0 < 2 < 0.3 < 0.1 < 1 2012-05-22/24 0.5-1.0 < 2 < 0.3 < 0.1 < 1 Table S10. PFAAs in the soil samples from Napalm-/ Main firefighting training facility Sampling location (Napalm-/ Main Concentrations of PFSAs [ng g-1 d.w.] firefighting training facility) Sampling Sampling Date PFHxA PFOA PFHxS PFOS depth (m) 2012-05-22/24 0.5-1.0 < 2 < 0.3 0.55 18.97 2012-05-22/24 0.5-1.0 < 2 1.4 1.3 53.12 2012-05-22/24 0.5-1.0 < 2 1.6 2.2 65.94 2012-05-22/24 0.5-1.0 < 2 1.4 0.43 16.9 2012-05-22/24 0.5-1.0 12 37.4 14.4 379 2012-05-22/24 0.5-1.0 4.1 65.8 8.3 204 2012-05-22/24 0.5-1.0 3.8 14.4 3.2 61.2 2012-05-22/24 0.5-1.0 < 2 15.2 2.1 46.6 2012-05-22/24 0.5-1.0 13.3 19.9 21.3 555 2012-05-22/24 0.5-1.0 < 2 18.5 0.80 26.1 2012-05-22/24 0.5-1.0 < 2 0.5 0.49 2.12 2012-05-22/24 0.5-1.0 < 2 2.5 2.2 195 2012-05-22/24 0.5-1.0 < 1.5 1.4 0.10 20.6 2012-05-22/24 0.5-1.0 < 1.5 0.35 0.12 4.38 2012-05-22/24 0.5-1.0 < 1.5 < 0.1 0.30 24.4

Table S11. PFAAs in the soil samples from Intermediate soil depot Sampling location Concentrations of PFSAs [ng g-1 d.w.] (Intermediate soil depot) Sampling Sampling Date PFHxA PFOA PFHxS PFOS depth (m) 2012-05-22/24 0-2 < 1.5 < 0.1 0.11 < 0.5 2012-05-22/24 1.5-3 < 1.5 < 0.1 0.10 < 0.5 2012-05-22/24 0-2.5 < 1.5 < 0.1 0.06 < 0.5 2012-05-22/24 1.5-3 < 1.5 0.49 0.22 2.2 2012-05-22/24 0-2 < 1.5 0.37 1.4 6.1 2012-05-22/24 1.5-2.5 < 1.5 < 0.1 < 0.02 < 0.5 2012-05-22/24 0-1.5 < 1.5 < 0.1 1.3 3.8 2012-05-22/24 1.5-3 < 1.5 < 0.1 < 0.02 < 0.5 2012-05-22/24 0-1.5 < 1.5 0.11 3.1 2 2012-05-22/24 0-2 < 1.5 < 0.1 0.11 < 0.5 Table S12. PFAAs in the soil samples from Soil depot. Sampling location Concentrations of PFSAs [ng g-1 d.w.] (Soil depot)

Sampling Sampling Date PFHxA PFOA PFHxS PFOS depth (m) 2012-05-22/24 0-1.5 < 1.5 < 0.1 < 0.02 < 0.5 2012-05-22/24 0-1.5 < 1.5 < 0.1 < 0.02 < 0.5 2012-05-22/24 1.5-3 < 1.5 < 0.1 < 0.02 < 0.5 2012-05-22/24 0-1.5 < 1.5 < 0.1 0.052 < 0.5 2012-05-22/24 0-1.5 < 1.5 < 0.1 < 0.02 < 0.5 2012-05-22/24 1-2 < 1.5 0.16 0.33 1.6 2012-05-22/24 0-0.3 < 1.5 < 0.1 0.047 < 0.5 2012-05-22/24 1.5-2.5 < 1.5 < 0.1 0.16 0.64 2012-05-22/24 0-1 < 1.5 < 0.1 < 0.02 < 0.5 2012-05-22/24 0-1.5 < 1.5 < 0.1 < 0.02 < 0.5 8. PFAAs in soil core.

Table S13. PFAAs in the soil samples from Main firefighting training facility Sampling location -1 (Main firefighting Concentrations of PFAAs [ng g d.w.] training facility) Sampling Sampling Date PFOS PFOA depth (m) 2011-12-02 0-0.5m 8520 219 2011-12-02 0.5-1m 5220 234 2011-12-02 1-1.5m 3960 287 2011-12-02 1.5-2m 2720 212 2011-12-02 2-2.5m 118 5.89 2011-12-02 2.5-3m 138 6.98 Table S14. PFAAs in the soil samples from Napalm-training ground. Sampling location -1 (Napalm-training Concentrations of PFAAs [ng g d.w.] ground) Sampling Sampling Date PFOS PFOA depth (m) 2011-12-02 0-0.5m 20.2 1.11 2011-12-02 0.5-1m 41.4 0.86 2011-12-02 1-1.5m 64.96 1.13 2011-12-02 1.5-2m 91.3 1.51 2011-12-02 2-2.5m 140 1.12 2011-12-02 2.5-3m 126 1.25 2011-12-02 3-3.5m 71.6 1.35 2011-12-02 3.5-4m 6.6 0.51 Table S15. PFAAs in the soil samples from Old fire station. Sampling location Concentrations of PFAAs [ng g-1 d.w.] (Old fire station)

Sampling Sampling Date PFOS PFOA depth (m) 2011-12-02 0-0.5m 7.12 0.16 2011-12-02 0.5-1m 63.2 0.98 2011-12-02 1-1.5m 69.9 0.33 2011-12-02 1.5-2m 85.7 1.37 2011-12-02 2-2.5m 7.2 0.22 2011-12-02 2.5-3m 2.6 0.22 2011-12-02 3-3.5m 2.2 < 0.12 2011-12-02 3.5-4m 9.96 2.95 9. PFAAs in fish muscle

Table S16. PFAAs in the fish muscle tissue. Concentrations of PFAAs [ng g-1 w.w.]

Sampling Species PFOA PFHxA PFOS PFHxS location

Bysjön Roach < 0.05 < 1 34.8 0.85 Carp Bream < 0.05 < 1 27.2 0.84 Ruffe < 0.05 < 1 22.1 <0.5 European Perch 1 < 0.05 < 1 76.5 < 0.5 European Perch 2 < 0.05 < 1 106 0.53 European Perch 3 < 0.05 < 1 370 0.80 Getaren Roach <0.05 <1 21.4 <0.5 Carp Bream <0.05 <1 25.3 <0.5 Ruffe <0.05 <1 12.4 <0.5 Northern Pike <0.05 <1 12.7 <0.5 European Perch 1 <0.05 <0.1 18.4 0.1 European Perch 2 <0.05 <0.07 51.4 <0.05 European Perch 3 <0.05 <0.07 34.6 0.32 Axaren Roach < 0.1 < 1 0.81 0.075 Carp Bream < 0.1 < 1 1.5 <0.02 Ruffe < 0.1 < 1 0.70 <0.02 Northern Pike < 0.1 < 1 4.1 < 0.02 European Perch 1 <0.1 < 1 3.6 <0.02 European Perch 2 < 0.1 < 1 34.2 0.23 Hacksjön Roach <0.1 <1 2.3 0.11 Carp Bream <0.1 <1 8.5 0.12 References:

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