Formation and Degradability of Per- and Polyfluoroalkyl Substances in River Soils around a Fluoropolymer Manufacturing Plant in Osaka, Japan

doi:10.21203/rs.3.rs-2241593/v1

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Formation and Degradability of Per- and Polyfluoroalkyl Substances in River Soils around a Fluoropolymer Manufacturing Plant in Osaka, Japan

https://doi.org/10.21203/rs.3.rs-2241593/v1

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published 26 Apr, 2023

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Our previous studies reported that perfluorooctanoic acid (PFOA) contamination has decreased in well, tap and surface water around a fluoropolymer plant in Osaka, Japan between 2003 and 2016. In this study, we evaluated the degradability of PFOA and perfluorohexanoic acid in river soils to identify the influence of the degradation on the perfluorocarboxylic acids (PFCAs) in the Yodo River Basin. We also investigated the influence of abiotic oxidation on the formation of PFCAs in soils and measured the fluorotelomer alcohols (FTOHs) as precursors of PFCAs in the soil and air samples collected at Osaka and Kyoto, respectively. No major changes were observed in soils contaminated with PFCA during the 24-week experimental period, while the PFOA levels increased only in the control group. The PFCA levels significantly increased after oxidation in this group. The dominant FTOH in soils was 10:2 FTOH, whereas 6:2 FTOH was dominant in the air samples. These findings suggest that PFOA was rapidly removed from water system but persist in soils. Moreover, the results indicate the need to evaluate not only the PFCAs, but also the FTOHs and other precursors for the accurate prediction of PFCA accumulation and fates in the environment.

Per- and polyfluoroalkyl substances (PFASs) are a large group of chemicals that have been used since the 1950s as ingredients or intermediates of surfactants and surface protectors for assorted industrial and consumer applications. Several PFASs have been recognized as highly persistent, bio-accumulative and toxic(Banzhaf et al., 2017; Boiteux et al., 2017; Daly et al., 2018; Guelfo & Adamson, 2018; Harada et al., 2005; Sunderland et al., 2019) In particular, perfluorooctanoic acid (PFOA) has attracted attention as it is easily bioaccumulated and has a long half-life in humans of 3.8 years(Harada et al., 2005). Several recent studies have found elevated levels of perfluorocarboxylic acids (PFCAs) in house dust, suggesting strongly the presence of indoor sources of these compounds(Banzhaf et al., 2017; Boiteux et al., 2017; Daly et al., 2018; Guelfo & Adamson, 2018; Guo et al., 2009). Previous epidemiological studies have reported the toxicity(Kennedy Jr. et al., 2004; Washino et al., 2009) and carcinogenicity(Barry et al., 2013; Vieira et al., 2013; Wen et al., 2020) of PFOA. In Japan, high levels of PFOA contamination have been reported in environmental samples and residents’ serum samples in the Kansai area(J. Liu et al., 2010b). Investigations of discharged water samples from sewage treatment plants (STPs) and ecological study have strongly suggested that a fluoropolymer (FP) plant (Daikin, in Settsu City, Osaka Prefecture) is the primary source of PFOA contamination(Ye et al., 2014). The company has begun self-regulation to reduce use and emissions of PFOA and has replaced it with shorter-carbon-chain PFCAs such as perfluorohexanoic acid (PFHxA)(Daikin Industries Ltd., n.d.; USEPA, n.d.).

In our previous study, we found that the PFOA concentrations in surface water and groundwater around the FP plant have substantially decreased during 2003 to 2015 in the Yodo River Basin(Shiwaku et al., 2016). Two possible mechanisms for the decline of PFOA in the water environment are decomposition in soils and transfer by the river flows. There are a few studies investigating PFAS degradation in soil(Luo et al., 2018; Zabaleta et al., 2018). Previous studies based on water samples collected from STPs in 2003 showed that wastewater from the FP plant in Settsu was released into surface water (6.6 t year^− 1), air (2.3 t year^− 1) and soil (1.2 t year^− 1)(Niisoe et al., 2010). Therefore, when considering the trend of PFCA contamination in this area, it is necessary to clarify the current levels of PFCAs in the air and soil as well as in the aquatic environment. Moreover, it is necessary to consider the influence of the precursors on clarifying the PFCA contamination since it is known that the PFCA contamination is not only caused by PFCAs themselves, but also affected by the decomposition of precursors such as fluorotelomer alcohols (FTOHs)(C. Liu et al., 2010; Martin et al., 2005). Previous studies have reported that 8:2 FTOH is mainly biotransformed to PFOA and PFHxA, and 6:2 FTOH is decomposed to PFHxA, PFPeA and PFBA by biotransformation (J. Liu et al., 2010a; Remde & Debus, 1996; Wang et al., 2009). Furthermore, it has been reported that C4- to C11-PFCA concentrations increased by 121–220% on average(Ye et al., 2014) through the oxidation process in water samples. In this study, collected soil from impacted sites and aimed to investigate the biotransformation of PFOA and PFHxA in the river soils and to evaluate the influence of precursors such as FTOHs, which can be degraded into PFCAs.

Sampling. Artificially treated surface soils were collected at two points: along the Ai River in Osaka Prefecture at the major FP plant (Daikin)(Saito et al., 2004; Shiwaku et al., 2016) (OS, Fig. 1) (34.759645, 135.533303) and along the Kamo River, Kyoto Prefecture (KS, Fig. 1) (35.023752, 135.771872), on February 23 and March 20, 2016, respectively. Polyethylene bags and metal scoops were used to collect the soil samples. They were used for the degradation experiment. Vegetation, larger soil fauna and stones were removed from the soil prior to passing it through a 2-mm sieve (Test No. 307: Aerobic and Anaerobic Transformation in Soil. OECD Guidelines for the Testing of Chemicals, Section 3 : Environmental Fate and Behaviour, n.d.). The collected soil samples were uniformly mixed and stored at 4°C until analysis. Air samples were collected at the Higashi-Yodogawa area in Osaka (OA, Fig. 1) (34.7532929, 135.5539568) between November 15 and 17, 2016, and the Sakyo area, Kyoto (KA, Fig. 1) (35.023530, 135.776898) between November 30 and December 2, 2016. These air sampling sites were downwind from the FP manufacturing facility. Air sampling and treatment of sampling media were conducted as previously reported(Oono et al., 2008). In brief, quartz fiber filters (QF, 8 inch × 10 inch; QR-100, Sibata, Tokyo, Japan) were used to obtain the particulate matter, and glass columns (90 mm i.d.) with a polyurethane foam (PUF, 50 mm) followed by activated carbon fiber felts (ACF, 10 mm; KF-1700F, Toyobo, Osaka, Japan) were used for the gaseous phase, using high-volume air samplers (HV-700F, Sibata, Tokyo, Japan) at approximate flow rates of 700 L min^− 1 for 48 h. Field blanks (ACF, PUF and QF) were carried to the sampling sites with each set of samples. After the collection, the samples were delivered to the laboratory immediately and kept at 4°C until analysis.

Insert Fig. 1 here

Experimental Methods.

Degradation tests

Degradability tests were conducted following the method of Russell et al.(Russell et al., 2008) A total of 42 glass serum vessels were prepared and were capped with crimp-sealed aluminum foil-lined closures. The vessels were incubated statically at 20 ± 2°C. Approximately 25 g dry weight equivalent of test soil were added to 21 vessels for each of the Kyoto and Osaka samples. Bacteriostatic treatments were performed with 5000 µg of chloramphenicol and cycloheximide, respectively, to further inhibit the microbial growth. Sodium acetate (2 µg/g) was used as positive control of biodegradation.

Extraction

Three preparation groups were established for each soil: 1) PFOA addition (100 ng per 25 g soil in dry weight; 2) PFHxA addition (300 ng per 25 g soil in dry weight); and 3) no treatment (controls). Vessels from Group 1, 2 and 3 were extracted and analyzed at 0, 1, 2, 4, 8, 16, and 24 weeks using the following method: 125 ml of acetonitrile, 10 ml of 200 mM NaOH and 10 µl of a ¹³C-labeled compound (MPFAC-MXA, Wellington Laboratories, Ontario, Canada) for calculating the recovery rate were added to each bottle, and stirred for 3 h on a swing shaker (Powley et al., 2005). After filtration, the filtrate was concentrated with an evaporator. After evaporating the solvent, 5 ml of tetrabutyl ammonium buffer was added and transferred to a 15-ml tube. Next, 10 ml of MTBE was added, and the mixture was treated for 3 min at 1500 rpm, using a centrifugal separator. The organic solvent layer was transferred to a glass test tube. The extract and internal standard solution (11H-Perfluoroundecanoic acid (11H-PFUnDA) were dried at 60°C for 30 min while blowing nitrogen gas. Then, 100 µl of benzyl bromide/toluene was put in the glass test tube and transferred to a vial, heated at 100°C for 60 min, and the concentrations of PFOA and PFHxA in the soil were analyzed using gas chromatography-mass spectrometry (GC-MS) (Agilent 6890 GC/5973 MSD)(Fujii, Yan, et al., 2012). The extraction recoveries of PFCAs were examined for soil samples (n = 7 fortified with PFCAs). Mean recovery rates of PFCAs were 94%, 88%, 95%, 98% and 93% for PFHxA, PFHpA, PFOA, PFNA and PFDA, respectively. Control experiments were conducted using agar powders (n = 5), while no significant contamination was observed.

Total oxidative precursor assay (TOP Assay)

For the oxidation test(Bolan et al., 2021; Houtz & Sedlak, 2012), 12 subsamples were taken from each soil sample. We analyzed five PFCAs (PFHxA, PFHpA, PFOA, PFNA, and PFDA) both before (n = 6) and after (n = 6) oxidation. The oxidation method was as follows: 25 mL of acetonitrile and a 10-mL aliquot of 200 mM NaOH was added to each sample. After the samples were extracted for 3 h using a gyratory shaker table set at 250 rpm, one fifth of eluate was passed through filter paper. The eluate was evaporated to 0.5 mL to avoid the loss of the target compounds during the drying process and 5 ml ultrapure water with 0.5 g of potassium persulfate and 1 mL of 5N KOH was added. The pH of the samples was adjusted between 5 and 9 using NaOH prior to the extraction, and samples were then heated at 85°C for 6 h. Prior to analysis, samples were cooled at room temperature and then analyzed with GC-MS(Fujii, Harada, et al., 2012).

FTOH analysis

Analysis of FTOHs in soil samples was conducted using the same soil samples. Two glass bottles were prepared, and 25 g dry weight of each soil was added. Then, 120 ml of 25% ethyl acetate in hexane and 1 ml of ¹³C-labeled FTOH were added, and the mixture was stirred with a swing shaker for 3 h. After filtration, the filtrate was concentrated using an evaporator. Hexane was added until the total amount reached about 30 ml, leaving about 2 ml of solvent. The extract was then washed with a silica gel column (Presep®-C Silica Gel, Wako Pure Chemicals), eluted in a glass test tube with 3 ml of 25% ethyl acetate/hexane and evaporated to 0.5 ml under high purity nitrogen. The extraction efficiencies of FTOHs were evaluated by spiking the standard solutions of FTOHs on a soil sample (n = 7). Mean recovery rates of analytes were 82%, 89%, 95%, 94% and 92% for 4:2 FTOH, 6:2 FTOH, 8:2 FTOH, 10:2 FTOH, and 8:2 FTOAc, respectively. The GC-MS analysis was based on the previous report(Mahmoud et al., 2009).

The FTOH analysis in air was conducted as previously reported(Oono et al., 2008). For extraction of samples, the three-sampling media were soaked for 10 min in 50 mL of ethyl acetate three times (150 mL total). The aliquots were combined and dried with sodium sulfate. Isotope-labeled 8:2 FTOH was added to all extracts to determine recoveries. The extracts were evaporated and reconstituted into hexane. The concentrates were cleaned on a silica gel column (Presep®-C Silica Gel, Wako Pure Chemicals). The eluates were combined with 5 mL of 25% ethyl acetate in hexane. Finally, 1H,1H-heptadecafluoro-1-nonanol was added as an internal standard just prior to the GC-MS analysis to correct for volume differences. The eluates were evaporated to 0.5 mL under high purity nitrogen and were then analyzed using GC-MS as described previously. In this study, the LOD was shown in Table 1.

Table 1

Detection limit of fluorotelomer alcohols in air and soil samples.
	Limit of detection
	Air (pg m^− 3)	Soil (ng g^− 1)
4:2 FTOH	8	0.1
6:2 FTOH	4	0.07
8:2 FTOH	2	0.05
10:2 FTOH	3	0.1
8:2 FTOAc	0.2	0.002

Insert Table 1 here

There is no decrease in concentration is not sufficient if there is nothing to show that the soil is microbially active.

Degradability of PFCAs in Soil Samples

Sodium acetate as positive control showed 86.2 ± 8.9% degradation after 24 weeks of observation. In the PFOA and PFHxA addition groups, no remarkable changes were observed in PFOA and PFHxA concentrations within 24 weeks (Fig. 2 (a)). Even after 24 weeks of measurement, the concentrations of PFOA and PFHxA were almost the same as those of Week 0 (PFOA: 1.0 time in the Ai River soil, 0.8 times in the Kamo River soil; PFHxA: 0.9 times in the Ai River soil, 1.0 time in the Kamo River soil). These results showed that PFOA and PFHxA are not easily decomposed in soil within a short period. Thus, this study supports the hypothesis that the short-term decline of PFCAs in the Yodo River Basin can be explained by transferring of the river flow and diffusion into groundwater rather than by decomposition in river soil. Our previous study suggested that PFOA was distributed within the groundwater in the Yodo River Basin(Shiwaku et al., 2016). In addition, another study reported PFCA contamination downstream of the Ai River and estuary of Osaka Bay(Takemine et al., 2014). Therefore, this study suggests that PFCAs released into Ai River stream through STPs eventually flow out into Osaka Bay.

In contrast, unlike the PFCA addition groups, increasing trends of PFOA concentrations were observed in the control group. The PFOA concentrations increased 1.8 times in Ai River soil samples and 1.7 times in the Kamo River soils over 24 weeks (Fig. 2 (b)). These results suggest that the precursors contained in the soil may have been decomposed into PFCAs over the 24-week study period.

Insert Fig. 2 here

Oxidation in Soil Samples

The concentrations of PFCAs in soil increased significantly after oxidation in both Ai River and Kamo River soil samples (Fig. 3 (a) and (b)). In the Ai River soil samples, the concentrations of PFHpA and PFOA increased significantly after oxidation. Similarly, PFHxA, PFHpA, PFOA, PFNA and PFDA were significantly increased in the soils of Kamo River (Fig. 3 (a), (b)). The presence of precursors in the soil samples could indicate that PFCAs increased as a result of the decomposition of the precursors.

Insert Fig. 3 here

FTOHs in Soil and Air Samples

In the Ai River soil samples, 10:2 FTOH (8.76 ng g^− 1) was the dominant substance among the FTOHs followed by 8:2 FTOH (2.16 ng g^− 1), 4:2 FTOH, and 6:2 FTOH, respectively, while 8:2 FTOAcryl was not detected. In the Kamo River soil samples, 10:2 FTOH (11.83 ng g^− 1) was the predominated, followed by 8:2 FTOH (2.63 ng g^− 1), 6:2 FTOH (0.10 ng g^− 1) and 8:2 FTOAcryl (0.005 ng g^− 1), but 4:2 FTOH was below the LOD (Table 2).

Table 2

Concentrations of soil FTOHs in the Keihan area (pmol g− 1).
Place	Latitude	Longitude	Date	4:2 FTOH	6:2 FTOH	8:2 FTOH	10:2 FTOH	8:2 FTOAcryl	ΣFTOH
OS	34.760047	135.53644	23 Feb. 2016	N.D.	N.D.	4.65	15.53	N.D.	20.19
KS	35.023171	135.771854	7 Mar. 2016	N.D.	0.27	5.67	20.97	0.01	26.92
N.D. = not determined.

Insert Table 2 here

The highest concentrations of airborne FTOHs in Osaka near the Yodo River Basin were the 6:2 FTOH (122.3 pg m^− 3), followed by 8:2 FTOH (75.3 pg m^− 3), 4:2 FTOH (16.3 pg m^− 3), 10:2 FTOH (14.5 pg m^− 3), and 8:2 FTOAcryl (2.03 fmol m^− 3). In Kyoto near the Kamo river Basin, the 6:2 FTOH (77.2 pg m^− 3) was the most abundant compound among the FTOHs, followed by 8:2 FTOH (29.8 pg m^− 3), 10: 2 FTOH (4.9 pg m^− 3), and 8:2 FTOAcryl (0.23 pg m^− 3), while 4:2 FTOH was below the detection limit (Table 3).

Table 3

Concentrations of airborne FTOHs in the Keihan area (fmol m− 3).
Place	Latitude	Longitude	Date	4:2 FTOH	6:2 FTOH	8:2 FTOH	10:2 FTOH	8:2 FTOAcryl	ΣFTOH
OA	34.75329	135.553957	15 Nov.–17 Nov. 2016	61.91	335.79	162.26	25.66	3.93	589.56
KA	35.022858	135.776804	30 Nov.–2 Dec. 2016	N.D.	212.11	64.29	8.56	0.46	285.42
N.D. = not determined.

Insert Table 3 here

In this study, FTOHs were detected in both air and soil samples, but there were differences in ratios between the air and the soil. The most dominant FTOHs in soil samples were 10:2 FTOH, followed by 8:2 FTOH and 6:2 FTOH, whereas 6:2 FTOH was the most prevalent in the air samples, followed by 8:2 FTOH and 10:2 FTOH. We presume that the precursors with large molecular weights tend to be adsorbed to soils(J. Liu & Lee, 2007). Moreover, a previous study of the FTOHs in the air samples conducted at the Yodo River Basin in 2005 showed that the most prevalent FTOHs were 8:2 FTOH, followed by 10:2 FTOH, and 6:2 FTOH(Oono et al., 2008). In contrast, 6:2 FTOH was dominant in the air samples in the current study, demonstrating differences in the mixture profiles between air and soil. The air samples reflect the recent situation in which the manufacturer has reduced the use of long-chain PFCs and switched to PFAS. However, the soil samples show the previous situation in which long-chain PFCs were frequently used, since it takes a long time for FTOHs in air to deposit to the soil. There have been studies investigating the fate of FTOHs in the soil.

Formation of PFCAs in the Soil Samples

Various organic fluorine compounds have been reported to be sources of PFCAs, and recent surveys have shown that PFCAs concentrations were increased through the biological treatment of wastewater containing FTOHs in the STP(Takemine, n.d.). Many studies also indicate that the metabolic oxidation of 8:2 FTOH leads to formation of PFOA(Butt et al., 2014). However, there is not a mass balance between the sum of the FTOHs before oxidation and the sum of the increase in PFCAs post-oxidation. This suggests that FTOHs could be changed into different carbon chain or shorter carbon chain PFCAs such as PFBA and PFHpA, which we did not measure in this study(Janda et al., 2019; Xu et al., 2021).

We compared the total molar FTOH concentration (pre-oxidation) in non-oxidized soils with the total molar increase in PFCA concentration after oxidation (Fig. 4). In the Ai River soil, the concentrations of PFHxA (C6) after oxidation were higher than the sum of PFHxA and 6:2 FTOH in non-oxidized soils, but the sum of the PFCAs and FTOH of C8 and C10 in non-oxidized soils was substantially higher than after oxidation in both the Ai River and Kamo River soil samples.

Insert Fig. 4 here

The sum of the C8 and C10 concentrations of the PFCAs and FTOHs in non-oxidized soils was much higher than PFCAs concentrations after oxidation. In the case of 8:2 FTOH, the concentrations of PFOA after oxidation tended to be higher in the Ai River soil than the Kamo River soil, even though the concentrations of 8:2 FTOH in the soil samples collected in the Ai River and Kamo River were almost the same. This showed that 0.70 pmol g^− 1 (15.1% of 8:2 FTOH in the soil) were formed by oxidation in the Ai River soil, while and 0.28 pmol g^− 1 (4.9% of 8:2 FTOH in the soil) were formed by oxidation in the Kamo River soil. These results indicate that substances other than 8:2 FTOH in Ai River soil may have been degraded to PFOA by the oxidation process. Based on these results, we suggest that the transformation degradation of 8:2 FTOH to PFOA is about 5% in soil samples. Recently, a modified TOP assay that works without prior extraction has been conducted(Göckener et al., 2021; Meng et al., 2021).

In general, degradation and formation kinetics of substances in soil largely depend on the properties of soils and surrounding environmental conditions. Therefore, the dynamics of PFCAs in studied soils may not be generalized to other regions. Moreover, unmeasured substances, such as PFBA, PFPeA and other PFCAs or precursors, may affect the results in the oxidation process, which was not considered in this study. We conducted extraction of soil samples by acetonitrile for oxidation experiments while the extraction is not necessarily effective to extract acrylate-linked fluorotelomer polymer (AFTP)(Washington et al., 2009). Then, potential PFCAs from AFTP may be underestimated.

Taken together, this study suggests that it is necessary to consider the influence of precursors when examining environmental pollution by PFCAs. Moreover, the results suggest that is possible to predict the potential environmental pollution of PFCAs by oxidizing the soil samples.

Conflicts of Interest

The authors have no financial conflicts of interest regarding the publication of this paper.

Author Contributions

Phayong Thepaksorn-reviewing, writing, editing. Pureum Lee- reviewing, writing, formal analysis, data management, Yoko Shiwaku- reviewing, writing, formal analysis, data management, Bo Zheng- reviewing, writing, formal analysis, data management, Akio Koizumi- conceptualization, data curation, funding acquisition, investigation, methodology, project administration, resources. Kouji H. Harada- conceptualization, supervision, data curation, formal analysis, funding acquisition, investigation, methodology, project administration, resources.

Acknowledgments

This study was supported by management expense grants from the Department of Health and Environmental Sciences, Kyoto University Graduate School of Medicine and Fujiwara Memorial Foundation. The funding sources were not involved in conducting this research.

Total Oxidizable Precursor (TOP) Assay

The Total Oxidizable Precursor (TOP) Assay is an oxidative sample pretreatment method aimed at converting the PFAS (Perfuoroalkyl Substances) within a sample into the stable perfluoroalkyl acids that can be quantified by conventional LC/MS/MS analytical techniques, thereby providing a greater understanding of the extent of PFAS within a sample. The oxidation is achieved by hydroxyl radicals, formed under heated alkaline conditions from prescribed amounts of potassium persulfate (KPS) and sodium hydroxide(NaOH) added to the sample prior to incubation.

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Formation and Degradability of Per- and Polyfluoroalkyl Substances in River Soils around a Fluoropolymer Manufacturing Plant in Osaka, Japan

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Abstract

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Introduction

Materials And Methods

Degradation tests

Extraction

Total oxidative precursor assay (TOP Assay)

FTOH analysis

Results And Discussion

Degradability of PFCAs in Soil Samples

Oxidation in Soil Samples

FTOHs in Soil and Air Samples

Formation of PFCAs in the Soil Samples

Declarations

References

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