Environmental Toxicology and Chemistry, Vol. 33, No. 8, pp. 1761–1765, 2014 # 2014 SETAC Printed in the USA
Short Communication PARTITIONING OF PERFLUOROOCTANESULFONATE AND PERFLUOROHEXANESULFONATE IN THE AQUATIC ENVIRONMENT AFTER AN ACCIDENTAL RELEASE OF AQUEOUS FILM FORMING FOAM AT SCHIPHOL AMSTERDAM AIRPORT CHRISTIAAN J.A.F. KWADIJK,*y MICHIEL KOTTERMAN,y and ALBERT A. KOELMANSyz
yInstitute for Marine Resources & Ecosystem Studies, Wageningen University, IJmuiden, The Netherlands zAquatic Ecology and Water Quality Management Group, Wageningen University, Wageningen, The Netherlands (Submitted 24 November 2013; Returned for Revision 9 January 2014; Accepted 29 March 2014) Abstract: In summer 2008, an accidental release of aqueous film forming foam (AFFF) took place at Schiphol Amsterdam Airport (The Netherlands). After the release, water, fish, and sediment samples were collected and analyzed for perfluoroalkyl sulfonates (PFSAs). In situ perfluorooctane sulfonate (PFOS) sediment–water distribution factor (KD) values, bioaccumulation factor (BAF) values, and biota– sediment accumulation factor (BSAF) values showed a remarkable agreement among reference and impacted sites, 10 wk after the incident as well as after 3 yr. Environ Toxicol Chem 2014;33:1761–1765. # 2014 SETAC Keywords: Perfluorooctane sulfonate (PFOS) tion factor Environmental partitioning
Perfluorinated compounds (PFCs)
Bioaccumulation
Sediment–water accumula-
end, a sampling strategy was applied in which all compartments were sampled on the same day on various locations along the possibly affected canal, including a reference site. Furthermore, the sampling campaign was repeated 3 yr later. The PFSAs studied included PFOS, perfluorobutane sulfonate (PFBS) and pefluorohexane sulfonate, because the spilled AFFF was based on perfluorinated alkyl sulfonate chemistry.
INTRODUCTION
Perfluoroalkyl sulfonates (PFSAs) are a group of surfactants that have been produced for more than 50 yr. They have been detected in humans, fish, and wildlife all over the world, including in the arctic [1]. Emission pathways into the environment include production, aqueous film forming foam (AFFF), and wastewater treatment plants (WWTP) [2–5]. In June 2008, a fire alarm was accidentally triggered at Schiphol Amsterdam Airport in The Netherlands, causing the release of FC-203CF light water AFFF (3M), known to contain perfluorooctane sulfonate (PFOS). Approximately 143 kg PFOS was released at this event, and a substantial part of this leaked into the environment. The number of studies on the fate of PFSA after such an event is limited [5–9], and it is not clear to what extent resulting environmental distribution patterns and mechanistic inferences apply to other systems. Shortly after release, the environmental distribution of PFSA may not be at equilibrium. Studying the fate of PFSA after release may provide useful information on the time scales by which equilibriums among environmental compartments, including biota, are established. Environmental fate studies also are highly relevant to assess the applicability of parameters and mechanisms deduced from laboratory studies and to find in situ distribution coefficients that can be used in fate and biomagnification models for PFSA after spill incidents. To date, data on field-relevant in situ distribution coefficients and bioaccumulation factors for PFSA are still scarce. The aims of the present study were to characterize concentrations of PFSA in the environment near the spill site, to assess the time trends for PFSA at those locations, to assess in situ sediment water distribution of those PFSA, and to quantify bioaccumulation of PFSA in fish after a major AFFF spill. To this
MATERIALS AND METHODS
Chemicals, analysis, quality assurance, and instrumentation used for the present study were as described previously by Kwadijk et al. [10]. Details are provided in the Supplemental Data. In the present study, primarily the sampling method and study design are described. Samples
Water was sampled from a canal surrounding the airport, named Ringvaart, roughly 2 km from the spill site, at location A, 3 d after the spill in July 2008 (Supplemental Data, Figure S1). Further sampling of fish, water, and sediment from a reference location R, 4 km upstream from the spill site and from locations B (adjacent to the spill site) and C (13 km downstream) took place in October 2008 and June 2011 (Supplemental Data, Figure S1). At each sampling location, sediment was sampled using multiple grabs of the top 10 cm over a 30-m radius. The subsamples were combined, mixed, and sieved. The fractions smaller than 63 mm were subsequently freeze-dried, after which they were stored in glass jars at room temperature. Organic matter content (fOM) was determined gravimetrically as loss on ignition (550 8C for 3 h). Organic carbon (fOC) was estimated as loss on ignition/1.724 [11]. Overlying water was sampled using glass bottles cleaned with acetone. The bottles were thoroughly rinsed 3 times with overlying water before the actual samples were taken. A piece of tin foil was inserted between the cap and the bottle to avoid contamination from the bottle cap. Samples were stored at 4 8C until extraction.
All Supplemental Data may be found in the online version of this article. * Address correspondence to [email protected]. Published online 14 April 2014 in Wiley Online Library (wileyonlinelibrary.com). DOI: 10.1002/etc.2602 1761
1762
Environ Toxicol Chem 33, 2014
C.J.A.F. Kwadijk et al.
Fish were sampled by electric fishing. Primary focus was on eel (Anguilla anguilla), but because of initial difficulties while sampling eel at location B, pike (Esox lucius) and perch (Perca fluviatilis) were also sampled at locations B and C. Pike were sampled only in 2008. In 2011, perch were also sampled at the reference location. Further details are provided in the Supplemental Data. Analyses used mixtures of several samples rather than individual samples. For instance, eel fillets from individuals with a length of 30 cm to 60 cm were selected and homogenized using a steel blender. For pike and perch, up to 24 individuals were selected. Because of their small size, the whole fish, instead of fillets, were homogenized using a blender. Samples were stored in glass jars at –20 8C until extraction. RESULTS AND DISCUSSION
Spatial distribution and temporal trends
Although PFBS, PFHxS, and PFOS were monitored, the dominant PFSA found in all samples was PFOS (Supplemental Data, Table S1). In 2008, PFHxS was detected in some of the water and fish samples but only in 2 sediment samples, whereas PFBS was detected only in some water samples and not in fish (
Short Communication PARTITIONING OF PERFLUOROOCTANESULFONATE AND PERFLUOROHEXANESULFONATE IN THE AQUATIC ENVIRONMENT AFTER AN ACCIDENTAL RELEASE OF AQUEOUS FILM FORMING FOAM AT SCHIPHOL AMSTERDAM AIRPORT CHRISTIAAN J.A.F. KWADIJK,*y MICHIEL KOTTERMAN,y and ALBERT A. KOELMANSyz
yInstitute for Marine Resources & Ecosystem Studies, Wageningen University, IJmuiden, The Netherlands zAquatic Ecology and Water Quality Management Group, Wageningen University, Wageningen, The Netherlands (Submitted 24 November 2013; Returned for Revision 9 January 2014; Accepted 29 March 2014) Abstract: In summer 2008, an accidental release of aqueous film forming foam (AFFF) took place at Schiphol Amsterdam Airport (The Netherlands). After the release, water, fish, and sediment samples were collected and analyzed for perfluoroalkyl sulfonates (PFSAs). In situ perfluorooctane sulfonate (PFOS) sediment–water distribution factor (KD) values, bioaccumulation factor (BAF) values, and biota– sediment accumulation factor (BSAF) values showed a remarkable agreement among reference and impacted sites, 10 wk after the incident as well as after 3 yr. Environ Toxicol Chem 2014;33:1761–1765. # 2014 SETAC Keywords: Perfluorooctane sulfonate (PFOS) tion factor Environmental partitioning
Perfluorinated compounds (PFCs)
Bioaccumulation
Sediment–water accumula-
end, a sampling strategy was applied in which all compartments were sampled on the same day on various locations along the possibly affected canal, including a reference site. Furthermore, the sampling campaign was repeated 3 yr later. The PFSAs studied included PFOS, perfluorobutane sulfonate (PFBS) and pefluorohexane sulfonate, because the spilled AFFF was based on perfluorinated alkyl sulfonate chemistry.
INTRODUCTION
Perfluoroalkyl sulfonates (PFSAs) are a group of surfactants that have been produced for more than 50 yr. They have been detected in humans, fish, and wildlife all over the world, including in the arctic [1]. Emission pathways into the environment include production, aqueous film forming foam (AFFF), and wastewater treatment plants (WWTP) [2–5]. In June 2008, a fire alarm was accidentally triggered at Schiphol Amsterdam Airport in The Netherlands, causing the release of FC-203CF light water AFFF (3M), known to contain perfluorooctane sulfonate (PFOS). Approximately 143 kg PFOS was released at this event, and a substantial part of this leaked into the environment. The number of studies on the fate of PFSA after such an event is limited [5–9], and it is not clear to what extent resulting environmental distribution patterns and mechanistic inferences apply to other systems. Shortly after release, the environmental distribution of PFSA may not be at equilibrium. Studying the fate of PFSA after release may provide useful information on the time scales by which equilibriums among environmental compartments, including biota, are established. Environmental fate studies also are highly relevant to assess the applicability of parameters and mechanisms deduced from laboratory studies and to find in situ distribution coefficients that can be used in fate and biomagnification models for PFSA after spill incidents. To date, data on field-relevant in situ distribution coefficients and bioaccumulation factors for PFSA are still scarce. The aims of the present study were to characterize concentrations of PFSA in the environment near the spill site, to assess the time trends for PFSA at those locations, to assess in situ sediment water distribution of those PFSA, and to quantify bioaccumulation of PFSA in fish after a major AFFF spill. To this
MATERIALS AND METHODS
Chemicals, analysis, quality assurance, and instrumentation used for the present study were as described previously by Kwadijk et al. [10]. Details are provided in the Supplemental Data. In the present study, primarily the sampling method and study design are described. Samples
Water was sampled from a canal surrounding the airport, named Ringvaart, roughly 2 km from the spill site, at location A, 3 d after the spill in July 2008 (Supplemental Data, Figure S1). Further sampling of fish, water, and sediment from a reference location R, 4 km upstream from the spill site and from locations B (adjacent to the spill site) and C (13 km downstream) took place in October 2008 and June 2011 (Supplemental Data, Figure S1). At each sampling location, sediment was sampled using multiple grabs of the top 10 cm over a 30-m radius. The subsamples were combined, mixed, and sieved. The fractions smaller than 63 mm were subsequently freeze-dried, after which they were stored in glass jars at room temperature. Organic matter content (fOM) was determined gravimetrically as loss on ignition (550 8C for 3 h). Organic carbon (fOC) was estimated as loss on ignition/1.724 [11]. Overlying water was sampled using glass bottles cleaned with acetone. The bottles were thoroughly rinsed 3 times with overlying water before the actual samples were taken. A piece of tin foil was inserted between the cap and the bottle to avoid contamination from the bottle cap. Samples were stored at 4 8C until extraction.
All Supplemental Data may be found in the online version of this article. * Address correspondence to [email protected]. Published online 14 April 2014 in Wiley Online Library (wileyonlinelibrary.com). DOI: 10.1002/etc.2602 1761
1762
Environ Toxicol Chem 33, 2014
C.J.A.F. Kwadijk et al.
Fish were sampled by electric fishing. Primary focus was on eel (Anguilla anguilla), but because of initial difficulties while sampling eel at location B, pike (Esox lucius) and perch (Perca fluviatilis) were also sampled at locations B and C. Pike were sampled only in 2008. In 2011, perch were also sampled at the reference location. Further details are provided in the Supplemental Data. Analyses used mixtures of several samples rather than individual samples. For instance, eel fillets from individuals with a length of 30 cm to 60 cm were selected and homogenized using a steel blender. For pike and perch, up to 24 individuals were selected. Because of their small size, the whole fish, instead of fillets, were homogenized using a blender. Samples were stored in glass jars at –20 8C until extraction. RESULTS AND DISCUSSION
Spatial distribution and temporal trends
Although PFBS, PFHxS, and PFOS were monitored, the dominant PFSA found in all samples was PFOS (Supplemental Data, Table S1). In 2008, PFHxS was detected in some of the water and fish samples but only in 2 sediment samples, whereas PFBS was detected only in some water samples and not in fish (
