Statement of Work.pdf

Per- and Polyfluoroalkyl Substances (PFASs) Uptake and Bioaccumulation in Fish in the Columbia Slough, Portland, OR

Objective We propose to evaluate PFASs in fish tissues and blood from Columbia Slough, which receives stormwater effluent from aqueous film forming foams (AFFF)-impacted sites at Portland International Airport (PDX) and the Portland Air National Guard (PANG) base, Oregon. The objective is to analyze over 240 individual PFASs in tissues and blood of multiple fish species collected from Columbia Slough. Target PFASs, most discovered only recently, include zwitterionic, cationic, and anionic classes with homologs ranging in fluorinated chain length from C2 to C14 (Barzen-Hanson et al., 2017).

Background Per- and polyfluoroalkyl substances have been produced for over 50 years and have found a wide range of consumer and industrial applications such as protective coatings for paper and textile fabrics, lubricants, and as a component of AFFF used for firefighting (Buck et al., 2011). Soil and groundwater contamination by PFASs has been detected at PDX and the PANG base (APEX, 2017). Stormwater from those facilities drains directly to Columbia Slough and PFASs have been detected in sediments from Columbia Slough (APEX, 2016). In addition, it has been very recently reported that surface water and groundwater samples collected from the PANG base had extremely high levels of PFASs (Schick, 2019). We propose to collect aquatic organisms from Columbia Slough and analyze tissues and blood for PFASs to evaluate their uptake and bioaccumulation.

Site Description The Columbia Slough is located south and parallel to the Columbia River and consists of approximately 19 miles of predominantly urbanized waterway. The Slough drains approximately 32,700 acres of land with industrial, commercial, residential, and agricultural uses. Much of the City of Portland’s industrial and commercial land is contained within the watershed’s boundaries. Management of the Slough system for flood control and water withdrawal supply has resulted in long residence times, causing increased algal growth, increased temperatures, and other water quality problems (Bureau of Environmental Services, 2007). Drainage from PDX is discharged to the Middle Slough through approximately nine Port-owned stormwater outfalls.

The Middle Slough comprises approximately 1.8 miles, and is separated from the Lower Slough by a large levee. The watershed is at the junction of the Columbia and Willamette rivers, and is a key area along migratory routes for birds and fish. Our fish sampling would be centered on the Middle Slough reach and a reference reach in the Upper Slough that has no known upstream sources of PFASs.

Laboratory Analytical Methods Frozen tissues will be cut into pieces and approximately 1 gm will be weighed out. Stable isotope (extraction) internal standards will be added and the sample will be vortexed and then allowed to equilibrate for 1.5 h. Basic methanol (2.5 mL of 0.01 MKOH in methanol) is added and sonicated for 30 min. The sample is then centrifuged for 5 min at 250 rpms. The supernatant is removed and the extraction is repeated one more time. The collected supernatant is evaporated to 3 mL under nitrogen at 35oC. The extract is cleaned up by passing the extract through an ENVI-Carb column, which is then eluted with methanol. The final extract is spiked with injection internal standards of PFOS and PFOA and evaporated to 1 mL prior to LC-MS/MS analysis (Reiner et al., 2012).

One gram of blood is weighed and combined with stable isotope (extraction) internal standards.

The mixture is allowed to equilibrate for 1.5 h before adding 4 mL acetonitrile. Samples are sonicated for 30 min and then centrifuged for 5 min at 2500 rpms. The supernatant is removed and solvent exchanged into methanol before cleanup on ENVI-Carb columns. The sample is then treated as described above for tissue analysis prior to analysis by LC-MS/MS (Reiner et al., 2012).

PFASs are isolated from organic extracts onto ion-exchange guard columns that are then eluted onto a C18 analytical column for separation. The chromatography methodology described in Backe et al. (2013) and Barzen-Hanson et al. (2015) captures approximately 240 individual PFASs, most of which were recently discovered using non-target high resolution mass spectrometry (Barzen-Hanson et al., 2017). The expanded panel of PFASs includes zwitterionic, cationic, and anionic classes with homologs ranging in fluorinated chain length from C2 to C14.

The expanded chromatography separates branched and linear isomers, so information is obtained on branching of PFCAs and PFSAs.

Task 1. Field work Collection of fish tissue samples from Columbia Slough, OR. USGS will carry out this task using all appropriate field methods and equipment during the summer of 2020.

Milestones/Deliverables Frozen tissue samples shipped to the contractor’s laboratory which are the deliverable for this task.

Task 2. Lab analyses Samples will be analyzed in contractor’s laboratory as described above.

Base Year 60 samples Option Year 1 – 60 samples Option Year 2 – 60 samples Option Year 3 – 60 samples

Milestones/Deliverables Monthly phone calls and data spreadsheets will be the deliverable for this task. The contractor and Dr. Nilsen will have monthly calls to discuss the status of the laboratory analyses.

Spreadsheet will be provided from the contractor to USGS as the data are completed.

Task 3. Data release We will publish a USSGS data release including all of the data generated for the project following USGS Fundamental Science Practices.

Milestones/Deliverables The USGS Data Release will be the deliverable for this task.

Period of Performance: Base year - September 1, 2020 to August 31, 2021

Option Year 1: September 1, 2021 to August 31, 2022 Option Year 2: September 1, 2022 to August 31, 2023 Option Year 3: September 1, 2023 to August 31, 2024

Literature Cited APEX, 2016. Sediment Sampling Investigation Report Colwood – Middle Columbia Slough Portland, Oregon, Task Order No. 20-13-52.

http://www.deq.state.or.us/Webdocs/Controls/Output/PdfHandler.ashx?p=eb698b84-4162-47d7- 94bf-e5f38b74d5eepdf&s=Sediment_Sampling_Investigation_Report_12-1-16.pdf

APEX, 2017. Original and Former Fire Training Facilities Investigation Results Report, Portland International Airport, Portland, Oregon ECSI No. 3324.

http://www.deq.state.or.us/Webdocs/Controls/Output/PdfHandler.ashx?p=5defcbb4-6644-4ad7-90ec-b90414ae30e9.pdf&s=Phase%20II%20Fire%20Training%20Investigation%20Report.pdf

Backe, W. J.; Day, T. C.; Field, J. A., Zwitterionic, cationic, and anionic fluorinated chemicals in aqueous film forming foam formulations and groundwater from us military bases by nonaqueous large-volume injection HPLC-MS/MS. Environ. Sci. Technol. 2013, 47, (10), 5226-5234.

Barzen-Hanson, K. A.; Roberts, S. C.; Choyke, S.; Oetjen, K.; McAlees, A.; Riddell, N.; McCrindle, R.;

Ferguson, P. L.; Higgins, C. P.; Field, J. A., Discovery of 40 Classes of Per- and Polyfluoroalkyl Substances in Historical Aqueous Film-Forming Foams (AFFFs) and AFFF-Impacted Groundwater.

Environ. Sci. Technol. 2017, 51, (4), 2047-2057.

Barzen-Hanson, K.; Field, J., Discovery and implications of C2 and C3 perfluoroalkyl sulfonates in aqueous film forming foams (AFFF) and groundwater. Environ. Sci. Technol. 2015, 2, 95-99.

Bureau of Environmental Services, 2007. Columbia Slough Watershed Long-Term Monitoring Plan, August 2007, City of Portland, https://www.portlandoregon.gov/bes/article/175915

Reiner, J. L.; O'Connell, S. G.; Butt, C. M.; Mabury, S. A.; Small, J. M.; De Silva, A. O.; Muir, D. C. G.;

Delinsky, A. D.; Strynar, M. J.; Lindstrom, A. B.; Reagen, W. K.; Malinsky, M.; Schaefer, S.;

Kwadijk, C. J. A. F.; Schantz, M. M.; Keller, J. M., Determination of perfluorinated alkyl acid concentrations in biological standard reference materials. Anal. Bioanal. Chem. 2012, 404, (9), 2683- 2692.

Schick, Tony. “Firefighting Foam Contaminated Northeast Portland Groundwater” Oregon Public Broadcasting, 2/27/19. Retrieved from: https://www.opb.org/news/article/groundwater-contaminated-near-portland-wells-used-for-drinking-water/ https://www.portlandoregon.gov/bes/article/175915