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Chapter 11
Contamination Profiles of Perfluorinated Chemicals in the Inland and Coastal Waters of Japan Following the Use of Fire-Fighting Foams S. Taniyasu,1 N. Yamashita,1 E. Yamazaki,1 P. Rostkowski,2 L. W. Y. Yeung,3 S. K. Kurunthachalam,4 K. Kannan,5 and B. G. Loganathan*,6 1National
Institute of Advanced Industrial Science and Technology (AIST), 16-1 Onogawa, Tsukuba, Ibaraki 305-8569, Japan 2University of Sussex, School of Life Sciences, Department of Biology and Environmental Science, BN1 9QG Brighton, United Kingdom 3Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario M5S 3H6, Canada 4Department of Research and Consultancy, Avinashilingam University, Coimbatore 641043, Tamil Nadu, India 5Wadsworth Center, New York State Department of Health and Department of Environmental Toxicology and Health, State University of New York, Empire State Plaza, PO Box 509, Albany, New York 12202-0509, U.S.A. 6Department of Chemistry and Watershed Studies Institute, 1201 Jesse D. Jones Hall, Murray State University, Murray, Kentucky 42071, U.S.A. *E-mail:
[email protected].
This study deals with the effects of natural disasters involving earthquake followed by tsunami and consequent human activities, on the quality of the inland and coastal waters of Japan. Two cases of accidental petrochemical fires in Japan that involved the use of aqueous film-forming foam (AFFF) have been investigated as potential sources of perfluoroalkyl substances (PFASs) in inland and coastal waters of Japan. PFASs were identified and quantified in seawater, lake water, snow, runoff and surface soil samples. Concentrations of individual PFASs were measured in water samples using
© 2015 American Chemical Society In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.
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high-performance liquid chromatography with electrospray tandem mass spectrometry (HPLC-MS/MS). The total concentrations of PFASs in seawater and lake water samples from the city of Tomakomai ranged from 0.43 to 519 ng/L. The greatest concentration of PFOS was found at T19 (311 ng/L) in December 2003. Total fluorine (TF), inorganic fluorine (IF), and extractable organic fluorine (EOF) were also measured in the samples using a newly developed method: combustion ion chromatography for fluorine (CIC-F). Results revealed that IF was the major contributor to TF in water samples. The major portion of EOF still remains unknown, suggesting the occurrence of other fluorinated organic compounds in addition to known individual PFASs such as PFOS, PFOA, and PFNA. In addition, composition and profiles of PFASs in two locations impacted by AFFF were different, suggesting different sources of organic fluorine released from AFFF. In Tomakomai, release of AFFF is believed to be a major source of PFASs, while in Kashima other sources such as byproducts of the fluorochemical industry appear to contribute to contamination.
Introduction In this study, two cases of accidental petrochemical fires in Japan that involved the use of aqueous film-forming foam (AFFF) have been investigated as potential sources of perfluoroalkyl substances (PFASs). The first case of accidental fire occurred near the city of Tomakomai, on the Pacific coast of southern Hokkaido. On 26th September 2003, an earthquake with a magnitude 8.3 (Richter scale) struck off the coast of Hokkaido, Japan. The earthquake and ensuing tsunami injured hundreds of people and resulted in significant damage to port and coastal communities. Following the earthquake, a major fire occurred at an oil storage facility at the Idemitsu Kosan Company in the west part of Tomakomai (Figure 1). Idemitsu Kosan Company is the second largest oil refinery in Japan with a capacity of 140,000 barrels per day. Forty-five of the one hundred-five oil storage tanks at the refinery were damaged, resulting in the release of petroleum naphtha, which ignited accidentally. The first fire was reported immediately after the earthquake and was extinguished after seven hours. The second fire occurred on 28 September 2003 and lasted for forty-four hours. More than three hundred firefighters and about one hundred fire engines were brought from several prefectures to extinguish the fire. More than 130,000 L of fire-fighting foams (FFF) were delivered and at least 40,000 L were used to extinguish these fires (1). Detailed information regarding the types of FFF used was not available. However it is known that AFFF was widely used in the control of these fuel-related fires. Another fire accident occurred on 21 April 2004 at a refinery near the city of Kashima on the eastern Pacific coast of Honshu island (the Kashima oil refinery at that time had the capacity to manufacture 30,000 barrels per day of low sulphur fuel oil) (Figure 1). 222 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.
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Figure 1. Map showing sampling locations in Japan. The major fire occurred at the Tomakomai location and a smaller fire in Kashima (● indicate sampling locations and indicate fire sites).
The fire in the Kashima plant was caused by damage to the heating tube (No. 4 coil) used in the desulfurization apparatus. The coil was damaged by high temperatures resulting in cracks on the wall of the heating tube. No details regarding the type of FFF used were available. The issue of environmental pollution by poly- and perfluoroalkyl substances including perfluoroalkyl carboxylates (PFACs) and perfluoroalkyl sulfonates (PFASs) has received considerable attention in the last decade (2–4). PFASs possess unique physicochemical properties and exhibit a wide range of volatility/water solubility properties depending on the functional group. Environmental dynamics of PFASs are also complex due to these properties, various compositions, and release from many sources. Fluorinated surfactants are used in a variety of fire-fighting agents. Five kinds of fluorinated fire-fighting foams are commonly used: fluoroprotein foams (FP), widely used to control 223 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.
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fires in hydrocarbon storage tanks and marine applications, aqueous film-forming foams and film-forming fluoroprotein foams (FFFP), used in aviation, marine and shallow spill fires, and alcohol resistant aqueous film-forming foams (AR–AFFF) and alcohol resistant film-forming fluoroprotein foams (AR–FFFP), multi-purpose foams used in hydrocarbon and polar solvent fires (5). PFASs have been used in some AFFF and AR-AFFFs since the 1960s (5, 6). Perfluorooctane sulfonate (PFOS) and related chemicals were the major compornents in AFFF used in military applications, oil and gas production, and petroleum refineries. In periodic training exercises, PFASs were directly released into the environment from ships and oil rigs. PFASs were also released during fire-fighting activities involving the use of AFFF. Previous studies have reported on environmental contamination by PFASs due to accidental release of AFFF (6, 7). The large amount of AFFF released in the Tomakomai oil refinery fire provided an opportunity to study the environmental dynamics of PFASs. A yearly monitoring survey of the environmental levels of PFASs in the Tomakomai region has been conducted since October 2003. This study presents the results of the initial survey conducted between October 2003 and October 2004. Our research objective was to investigate the levels of various PFASs in water samples collected at selected locations in theTomakomai and Kashima areas. Surface water sampled from inland (lake, snow, and runoff) and coastal waters was chosen for analysis. The main criterion for the selection of samples was the distance from the fire sites. Samples from source locations, remote locations, and control locations in and around Tomakomai and Kashima were obtained. In all, 78 samples were analyzed for nine different PFASs, including PFOS and perfluorooctanoate (PFOA) (Table 1). In addition, total fluorine (TF), inorganic fluorine (IF) and extractable organic fluorine (EOF) were also measured in the samples using a newly developed method: combustion ion chromatography for fluorine (CIC-F).
Materials and Methods Chemicals and Standards PFOS, perfluorohexanesulphonate (PFHxS), perfluorobutanesul-phonate (PFBS), perfluorooctanesulfonamide (PFOSA), perfluoro-decanoate (PFDA), perfluorononanoate (PFNA), PFOA, perfluoro-heptanoate (PFHpA), perfluoroundecanoate (PFUnDA), perfluoro-hexanoate (PFHxA) were purchased from different suppliers as described earlier (8). Oasis®HLB (6 cc, 200 mg, 30 μm) and Oasis®Wax (6 cc, 150 mg, 30 μm) solid-phase extraction (SPE) cartridges were purchased from Waters Co. (Milford, MA, USA). Methanol (MeOH), ammonium acetate and acetic acid were purchased from Wako Pure Chemical Industries, Ltd. (Osaka, Japan). Milli-Q water was obtained from Milli-Q Gradient A-10 (Millipore, Billerica, MA, USA). 224 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.
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Sample Collection Surface water samples were collected from the coastal and inland area of Tomakomai, from Lake Utonai (T24) as a remote site, and from Oshamanbe (H1) and Hakodate (H2) as control sites on Hokkaido (Figure 1). Sources of contamination in the remote and control sites are not known. Snow, runoff and surface soil samples were also collected from Tomakomai. Seawater and pond water were collected near the area affected by the fire in Kashima, Ibaraki (Figure 1). All water samples were collected using a stainless steel bucket which was pre-cleaned by rinsing with methanol, Milli-Q water, and then rinsed with the water to be sampled. The samples were then stored in 1 L narrow-mouth polypropylene bottles with screw caps. Snow samples were collected in clean, blank-checked polypropylene bags and, after melting at room temperature, stored in 1 L polypropylene bottles. Whenever possible, samples were extracted within 24 hours after collection. Otherwise, the samples were stored at 4 °C until extraction.
Extraction and Purification The analytical procedures for individual PFASs in water samples using solid phase extraction by Oasis® WAX cartridges and Oasis® HLB cartridges were similar to that described earlier (8). Prior to extraction, Oasis® WAX cartridges were preconditioned by eluting with 4 mL of 0.01 % NH4OH/H2O followed by 4 mL of MeOH and 4 mL of Milli-Q water, respectively. Water samples were then passed through preconditioned cartridges at a rate of 1 drop/sec. The cartridges were then washed with 4 mL of 25mM sodium acetate buffer and then the target analytes were eluted with 4 mL of MeOH and 4 mL of 0.1% NH4OH/MeOH. We also analyzed TF in the samples. Removal of IF from organic fractions was achieved by additional washing of the cartridge with a mixture of NH4OH/H2O before elution of target analytes. The analytical procedure for the determination of TF, EOF, and IF total fluorine is described in detail elsewhere (2).
Instrumental Analysis Concentrations of PFASs were determined by use of an Agilent HP1100 liquid chromatograph interfaced with a Micromass Quattro Ultima Pt mass spectrometer (HPLC-MS/MS) operated in an electrospray negative ionization mode using parameters that are described in detail elsewhere (8). Analyses of TF, IF, and EOF were performed by CIC-F, by a combination of an automated combustion unit (AQF–100 type AIST; DIA Instruments Co., Ltd.) and an IC system (ICS–3000 type AIST; Dionex Corp., Sunnyvale, CA), that enabled determination of fluoride at sub ppb (µg-F/L) levels (2). 225 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.
date
PFBS
PFHxS
PFOS
PFOSA
PFHpA
PFOA
PFNA
PFDA
PFUnDA
Total PFASs
Oct-03
0.05
3.39
17.1
0.61
< LOQ
1.09
4.02
< LOQ
0.22
26.5
Dec-03
< LOQ
0.42
1.07
0.24
0.06
0.32
0.50
0.02
0.01
2.64
Apr-04
0.01
1.07
1.54
0.11
0.07
0.69
0.91
0.12
0.07
4.60
Jun-04
0.02
0.42
1.64
0.04
0.11
0.37
0.51
0.06
0.08
3.23
Oct-04
0.02
0.15
0.69
< LOQ
0.07
0.18
0.11
0.01
0.02
1.26
Dec-03
0.03
0.27
0.42
0.18
0.05
0.19
0.28
0.01
0.02
1.44
Apr-04
0.09
0.43
0.43
0.02
0.05
0.12
0.18
0.02
0.02
1.35
Jun-04
0.11
0.71
0.81
0.04
0.12
0.38
0.33
0.04
0.03
2.56
Oct-04
0.05
0.22
0.26
0.02
0.34
2.11
0.13
0.03
0.03
3.19
Dec-03
0.01
0.99
1.09
0.38
0.01
0.29
0.57
0.01
0.03
3.37
Apr-04
0.02
1.34
1.14
0.14
0.07
0.30
0.44
0.02
0.03
3.50
Jun-04
0.19
1.58
1.00
0.04
0.12
0.39
0.37
0.04
0.04
3.76
Oct-04
0.06
0.59
0.42
0.02
0.15
0.37
0.13
0.02
0.02
1.78
Oct-03
< LOQ
2.44
11.57
2.73
0.11
0.88
2.95
< LOQ
0.42
21.1
Dec-03
0.05
2.56
14.2
5.29
0.24
2.56
10.8
0.30
0.75
36.8
Apr-04
0.01
0.94
0.75
0.07
0.05
0.26
0.37
0.01
0.03
2.49
site Tomakomai, Hokkaido Seawater (ng/L)
T1
T4
226
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Table 1. Individual PFAS Concentrations in Seawater, Lake Water, Snow, Runoff, Pond Water (ng/L), and Surface Soil (ng/g-dry wt.)
T5
T8
In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.
T9
T10
227
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site
T11
date
PFBS
PFHxS
PFOS
PFOSA
PFHpA
PFOA
PFNA
PFDA
PFUnDA
Total PFASs
Jun-04
0.20
1.31
0.84
0.03
0.13
0.41
0.34
0.03
0.04
3.31
Oct-04
0.05
0.61
0.90
0.03
0.29
0.33
0.18
0.01
0.09
2.48
Oct-03
0.29
2.83
9.73
1.19
< LOQ
0.58
2.73
< LOQ
0.25
17.6
Dec-03
0.03
1.38
1.46
0.22
0.15
0.51
0.70
0.03
0.04
4.50
Apr-04
0.20
1.09
0.80
0.07
0.17
0.27
0.40
0.02
0.03
3.05
Jun-04
0.06
1.36
1.36
0.07
0.13
0.40
0.46
0.03
0.05
3.92
Oct-04
0.59
0.44
0.28
0.10
0.11
0.21
0.08
0.02
< LOQ
1.82
Oct-03
0.23
3.03
122
6.52
0.26
1.64
16.9
0.43
2.16
153
Dec-03
0.16
1.24
2.68
0.26
0.83
1.25
1.48
< LOQ
< LOQ
7.89
Apr-04
0.01
0.88
0.59
0.06
0.09
0.27
0.31
0.01
0.03
2.24
Jun-04
0.19
1.27
0.98
0.05
0.23
0.60
0.43
0.02
0.04
3.81
Oct-04
0.03
0.36
0.17
< LOQ
0.20
0.31
0.04
< LOQ
< LOQ
1.10
Oct-03
0.33
3.61
17.7
1.51
0.18
0.86
3.28
< LOQ
0.43
27.9
Dec-03
0.06
1.38
2.50
0.22
0.25
0.73
1.14
0.04
0.08
6.40
Apr-04
0.21
1.21
1.01
0.08
0.15
0.42
0.43
0.02
0.04
3.54
Jun-04
0.01
1.34
0.90
0.04
0.02
0.35
0.35
0.03
0.04
3.07
Oct-04
0.08
0.36
0.35
0.01
0.11
0.22
0.07
0.01
0.03
1.23
Continued on next page.
In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.
site
date
PFBS
PFHxS
PFOS
PFOSA
PFHpA
PFOA
PFNA
PFDA
PFUnDA
Total PFASs
T16
Oct-03
0.19
26. 0
75.5
2.40
0.18
2.06
17.7
< LOQ
0.46
124
Dec-03
0.12
5.08
29.2
5.36
0.80
3.36
19.5
< LOQ
0.56
63.9
Apr-04
0.39
3.54
8.28
0.66
1.47
1.40
3.05
< LOQ
< LOQ
18.8
Jun-04
< LOQ
5.19
14.2
3.34
2.00
1.37
6.01
< LOQ
0.17
32.3
Oct-04
0.05
0.73
2.07
0.25
0.11
0.21
0.40
< LOQ
0.05
3.88
Dec-03
7.27
107
311
10.5
3.03
9.75
68.3
0.28
2.17
519
Apr-04
0.12
3.35
9.98
1.02
0.33
1.05
1.59
0.02
0.07
17.5
Jun-04
0.31
8.79
26.5
4.97
3.08
4.10
10.5
0.07
0.46
58.8
Oct-04
0.75
20.8
77.4
28.8
3.06
9.76
15.1
0.04
0.23
156
Dec-03
0.35
5.55
7.78
0.31
0.93
1.65
2.93
0.04
< LOQ
19.5
Apr-04
0.12
0.17
0.77
< LOQ
0.12
0.28
0.22
0.03
0.01
1.71
Jun-04
0.07
1.74
7.33
0.26
0.27
1.24
1.97
0.05
0.10
13.0
Oct-04
0.17
2.70
1.67
0.10
0.28
0.92
1.22
0.02
0.21
7.29
Dec-03
< LOQ
0.63
2.14
0.28
< LOQ
0.22
0.67
