Environ. Sci. Technol. 2010, 44, 3746–3751
Distribution of Perfluorinated Compounds in Aquatic Systems in The Netherlands ´ R,† C . J . A . F . K W A D I J K , * ,† P . K O R Y T A A N D A . A . K O E L M A N S †,‡ Institute for Marine Resources and Ecosystem Studies (IMARES), Wageningen UR, P.O. Box 68, 1970 AB IJmuiden, The Netherlands, and Aquatic Ecology and Water Quality Management Group, Wageningen University, P.O. Box 47, 6700 AA Wageningen, The Netherlands
Received February 12, 2010. Revised manuscript received April 14, 2010. Accepted April 15, 2010.
The distribution of 15 perfluorinated compounds (PFCs) among eel (Anguilla anguilla), sediment, and water was investigated for 21 locations in The Netherlands. Furthermore, for perfluorooctanesulfonate (PFOS), a 30 year time series was measured for three locations using historical eel samples. These historical samples revealed concentrations increasing by a factor of 2-4 until the mid-1990s, followed by a return to the initial levels. In the samples described here, PFOS dominated aqueous concentrations, ranging from 4.7 to 32 ng/L in water, from 0.5 to 8.7 ng/g in sediment, and from 7 to 58 ng/g in eel filet. Field-based sediment water distribution coefficients (KD) were calculated and corrected for organic carbon content (KOC), which reduced variability among samples. Log KOC ranges were 2.6-3.7 for the C7-C9 carboxylic acids and 2.2-3.2 for the C4-C8 sulfonates. Bioaccumulation factors (log BAFs) for eel ranged from 1.09-3.26 for the C7-C9 carboxylic acids to 1.4-3.3 for the C4-C8 sulfonates. Perfluoroalkyl chain length correlated well with both sorption and bioaccumulation factors. Magnitudes and trends in KD or BAF appeared to agree well with previously published laboratory data. Results imply that PFCs are mainly present in water, which is important for PFC fate modeling and risk assessment.
Introduction Perfluorinated compounds (PFCs) make up a group of surfactants that have been in production for more than 50 years (1). Pathways of emission into the environment include production, aqueous firefighting foam, and wastewater treatment plants (WWTPs) (2-6). Monitoring in the aquatic environment typically occurs through measurements in fish tissue (7). Analytical techniques have been developed that evolved from Hansen’s ion pair extraction to Powley’s solvent extraction in the past decade (8, 9). To date, most research related to PFCs concerned the occurrence, monitoring, and bioaccumulation and emphasized the analytical chemistry of these compounds. PFCs have been detected in humans, fish, and wildlife all over the globe, including the arctic (10-13). However, data on environmental processes of PFCs, such as the distribution among water, sediment, and biota, * Corresponding author e-mail:
[email protected]; phone: +31 317 487134. † Wageningen UR. ‡ Wageningen University. 3746
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are still limited. There are a few laboratory studies on sorption processes, which provide sorption data under controlled laboratory conditions (14-18). However, the extent to which the resulting distribution parameters and mechanistic inferences apply to conditions in the field is not yet clear. As far as we know, no earlier studies measured PFCs in water, sediment, and biota compartments simultaneously. Still, such studies are highly relevant (a) for the assessment of the applicability of parameters and mechanisms deduced from laboratory studies and (b) for the determination of the distribution coefficients that can be used in fate and biomagnification models for PFCs. The aim of this study was (a) to characterize levels of PFCs in The Netherlands, in relation to their sources, (b) to assess time trends for PFCs, (c) to assess the in situ sediment water distribution of PFCs, and (d) to quantify bioaccumulation of PFCs in eel (Anguilla anguilla). To this end, a sampling strategy was applied in which all compartments were sampled on the same day, at a relatively large number of 21 sampling locations. Furthermore, historical samples were reanalyzed for three locations.
Materials and Methods Chemicals. Acetonitrile, acetone, n-hexane, and methanol were obtained from LGC Standards (Wesel, Germany). Ammonium formate was obtained from Sigma-Aldrich (Zwijndrecht, The Netherlands). Standard solution mixtures for the sulfonates [perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHxS), perfluorooctanesulfonate (PFOS), and perfluorodecanesulfonate (PFDS)] and the carboxylic acids [perfluorobutanoic acid (PFBA), perfluoropentanoic acid (PFPA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDcA), perfluoroundecanoic acid (PFUnA), perfluorododecanoic acid (PFDoA), perfluorotrideconoic acid (PFTriA), and perfluorotetranoic acid (PFTeA)] at concentrations of 2 µg/mL in methanol as well as 13C-labeled PFOS and PFOA were obtained from Wellington Laboratories (Guelph, ON). Sodium sulfate was dried for 20 h at 450 °C before being used. Sampling. Sediment, water, and eel (A. anguilla) samples were collected from 21 major rivers, lakes, and canals in The Netherlands, between May 2007 and August 2007 (Figure 1). For three locations [Rhine at Lobith (17), Hollands Diep (22), and Haringvliet East (23)], stored historical eel tissue samples were available, which were sampled from 1978 onward for monitoring purposes (7). These tissue samples were reanalyzed for PFCs as part of this study, using the analytical techniques that are available now, which are identical to the techniques used for the new samples. Sediments were sampled at 19 locations using a van Veen Grabber. At each location, six grabs were collected over a 30 m radius and subsequently combined into one sample. The mixed samples were collected in polyethylene buckets that had been tested for contamination prior to use. Samples were sieved over a 63 µm sieve, freeze-dried, and stored in glass jars at room temperature prior to extraction. The >63 µm fraction was discarded. The amount of organic carbon in the 99%) at typical suspended solid ranges of 1-10 mg/L. The field data further reflect underlying mechanisms of sorption and accumulation, as indicated by the dependencies of KD and BAF on perfluoroalkyl chain length and functional group. Second, this study showed only limited variation in log BAF for individual chemicals at one point in time. This illustrates the usefulness of eel as a bioindicator for PFCs in retrospective risk assessment and supports the detected downward trend for PFOS over the past decade.
Acknowledgments We thank Evert van Barneveld, Marco Lohman, and Maadjieda Tjon-Atsoi for their efforts during the sampling campaign and contributions to the experimental work.
Supporting Information Available Details about the sampling locations. This material is available free of charge via the Internet at http://pubs.acs.org.
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