Zachary O. O'Neal Maxwell C. Meadows Andrea K. Tokranov Meagan J. Eagle Jennifer A. O'Keefe Suttles Brian Buczkowski Deborah A. Repert Christopher Greidanus Denis R. LeBlanc 20230620 2.0 tabular data data release DOI:10.5066/P9DM4E66 Reston, VA U.S. Geological Survey O'Neal, Z.O., Meadows, M.C., Tokranov, A.K., Eagle, M.J., O'Keefe Suttles, J.A., Buczkowski, B., Repert, D.A., Greidanus, C., and LeBlanc, D.R., 2023, Concentrations of per- and polyfluoroalkyl substances (PFAS) in lake-bottom sediments of Ashumet Pond on Cape Cod, Massachusetts, 2020 (ver. 2.0, February 2024): U.S. Geological Survey data release, https://doi.org/10.5066/P9DM4E66. https://doi.org/10.5066/P9DM4E66 Lake-bottom sediment and associated quality-control samples were collected in August 2020 from one coring location (U.S. Geological Survey station 413756070321301, ASHUMET POND, MASHPEE MI-ASHPD-0011) in Ashumet Pond downgradient from a former fire-training area on Cape Cod, Massachusetts. The core was collected to determine if per- and polyfluoroalkyl substances (PFAS) were present in the bottom sediments of a lake known to have elevated concentrations of PFAS in surface water and groundwater (Tokranov and others, 2021), and whether the sediments could act as a continuous source of PFAS to the lake. Processing the sediment core entailed collection of discrete samples at intervals ranging from 1-5 centimeters (cm) throughout the length of the 112-cm-long core. Radioisotopic dating analysis was performed along 1-cm intervals for the first 10 cm of sediment. A total of 23 sample intervals were submitted for analysis of 28 PFAS, total organic carbon (TOC) and total nitrogen (TN), and 57 sample intervals were submitted for grain size and dry bulk density analysis. Quality control (QC) samples included an aqueous equipment blank collected from the core barrel that was used for sediment sampling, a set of triplicate sediment samples, and laboratory-provided blanks. All QC samples were analyzed for 28 PFAS. Reference: Tokranov, A.K., LeBlanc, D.R., Pickard, H.M., Ruyle, B.J., Barber, L.B., Hull, R.B., Sunderland, E.M., and Vecitis, C.D., 2021, Surface-water/groundwater boundaries affect seasonal PFAS concentrations and PFAA precursor transformations: Environmental Science—Processes & Impacts, v. 23, no. 12, p. 1893-1905, https://doi.org/10.1039/D1EM00329A. Data were obtained to assess concentrations of per- and polyfluoroalkyl substances (PFAS) in lake-bottom sediment in an area where PFAS concentrations are present in surface water and groundwater. Supplemental Information: Two datasets included within the data release titled: "GS_Ashumet_Pond_2020_ver_2.0.xlsx" and "GS_Metric_Ashumet_Pond_2020_ver_2.0.xlsx" were revised due to a formula error found. See revision history described in Process Step 7 for details. 20200818 sample collection date Complete None planned -70.5369000000000 -70.5368000000000 41.6321000000000 41.6320500000000 ISO 19115 Topic Category environment USGS Thesaurus hydrogeology grain-size analysis chemical analysis PFAS radiometric dating limnology sedimentation vibracoring USGS Metadata Identifier USGS:6427312dd34e370832ff66ec Getty Thesaurus of Geographic Names Cape Cod Falmouth Massachusetts Sandwich Mashpee Eastern United States None. Please see 'Distribution Info' for details. None. Users are advised to read the dataset's metadata thoroughly to understand appropriate use and data limitations. Andrea K Tokranov U.S. Geological Survey, Northeast Region Hydrologist mailing address

331 Commerce Way

Pembroke New Hampshire 03275 United States 508-490-5017 508-490-5068 atokranov@usgs.gov A data quality evaluation was provided by SGS AXYS Analytical Services Ltd (Sidney, BC, Canada) to support the accuracy of the analytical PFAS and PFAS quality-assurance/quality-control results. The SGS AXYS analytical review assessed in detail if Laboratory Method Blanks, Spiked Samples, Recoveries, and Calibrations all met acceptance criteria. All criteria were acceptable, and additional comments provided in the report explained that no biases could be drawn from the dataset. The SGS AXYS analytical review is available upon request from the dataset point of contact. Data quality grades were assigned to each sample analyzed for grain size, indicating the accuracy of the grain size distribution of the sample's coarse fraction. Standards are regularly run for quality control, ensuring accuracy of grain-size measurements of the fine fractions. Radionuclide detection limits are specific to an individual sample and are a function of: 1) the detector efficiency at the energy level of the peak being measured; 2) the branching ratio (expected fraction of decay events at the energy level), 3) the background activity within the sample. Detector efficiency was determined from U.S. Environmental Protection Agency standard pitchblende ore in the same geometry as the samples. Activities of 7Be, 137Cs, and excess 210Pb (i.e. unsupported) were decay-corrected to time of collection. Suppression of low-energy peaks by self-absorption was corrected for according to methods published by Cutshall and others, (1983). Peak detection, with respect to background activity, is calculated for each radionuclide in the GENIE peak integration spectroscopy software during sample analysis. The minimum detected radionuclide activity for this sample set was greater than or equal to 0.3126 decays per minute per gram (dpm/g) for 210Pb, and 1.008 dpm/g for 226Ra; 7Be and 137Cs radioactivity was not detectable in this sample set. Reference: Cutshall, N.H., Larsen, I.L., and Olsen, C.R., 1983, Direct analysis of 210 Pb in sediment samples—Self-absorption corrections: Nuclear Instruments and Methods in Physics Research, v. 206, issues 1–2, p. 309–312, https://doi.org/10.1016/0167-5087(83)91273-5. No formal logical accuracy tests were conducted. The analytical data accurately matches the details provided and falls within expected ranges. There were no outliers encountered and no data points were omitted. Sample IDs consistent across each dataset so comparisons can be made. Dataset is considered complete for the information presented, as described in the abstract. Users are advised to read the rest of the metadata record and Data Dictionary carefully for additional details about numerical, non-numerical, and blank cell definitions, as well as value reporting units. No formal horizontal positional accuracy tests were conducted. No formal horizontal positional accuracy tests were conducted. Core Collection and Sectioning: A lake-bottom sediment core was collected for the analysis of per- and polyfluoroalkyl substances (PFAS). Vibration direct push coring techniques were used to obtain the core from the lake bottom. Before sample collection, the core liner underwent thorough decontamination procedures to ensure the core would not be impacted. An aqueous field blank taken with PFAS-free water confirmed there were zero detections of PFAS in the core liner. The sediment core that was collected in the field was returned to shore in a vertical orientation to ensure the sediments at the top of the core were not mixed. Residual water at the top core was drained by drilling a hole above the sediment surface in the barrel. Excess core liner was cut away, and the core was capped. The core was brought to the U.S. Geological Survey (USGS) laboratory in Woods Hole, Massachusetts where it was laid horizontally, cut into sub-sections, then the sub-sections were capped. Core sub-sections were first kept on dry ice before storage at -20 degrees Celsius (°C). The sub-sections were kept at -20°C until they were sampled for further analysis. 20200818 PFAS Analysis: Core subsections were sampled at targeted intervals ranging from 1-5 centimeters (cm) throughout the length of the 112-cm-core. The sampled intervals were submitted to SGS AXYS Analytical Services Ltd (Sidney, BC, Canada) for the analysis of 28 PFAS through application of SGS AXYS method MLA-110. MLA-110 is an isotope dilution liquid chromatography tandem mass spectrometry (LC-MS/MS) method for PFAS, which is the predecessor to the US Environmental Protection Agency (EPA) Draft Method 1633, published in August 2021. Batch-specific data files were compiled into individual spreadsheets for publication (PFAS_Ashumet_Pond_2020.xlsx; PFAS_QA_QC_Ashumet_Pond_2020.xlsx). 20201224 Carbon and Nitrogen Analysis: Samples were submitted to the USGS Water Mission Area Laboratory in Boulder, Colorado for the analysis of total organic carbon (TOC) and total nitrogen (TN). The samples were dried at 50°C then sieved through a 4 millimeter (mm) sieve. The <4 mm fraction was then ground and analyzed on an Exeter Analytical CE440 CHN Elemental Analyzer. Thermal conductivity detection was used for measuring carbon (as the sum of TOC and total inorganic carbon), hydrogen, and nitrogen, after combustion at 980°C and reduction at 700°C (Smith and others, 2013). It is assumed that very little inorganic carbon existed in the samples, therefore the reported carbon values reflect mostly, or entirely organic carbon. Reported results were collected as the average of 3 replicate analyses of each sample that was submitted. Batch-specific data files were compiled into an individual spreadsheet for publication (C_N_Ashumet_Pond_2020.xlsx). Reference: Smith, R.L., Repert, D.A., Barber, L.B., and LeBlanc, D.R., 2013, Long-term groundwater contamination after source removal—The role of sorbed carbon and nitrogen on the rate of reoxygenation of a treated-wastewater plume on Cape Cod, Massachusetts, USA: Chemical Geology, v. 337-338, p. 38-47, https://doi.org/10.1016/j.chemgeo.2012.11.007. 20210209 Sediment Dry Bulk Density Analysis: Samples were submitted to the USGS Sediment Laboratory in Woods Hole, Massachusetts for dry bulk density analysis using a HumiPyc II gas pycnometer. The samples were assigned unique analysis identifiers (Analysis_ID) in preparation for analysis. Samples were thawed and collected from bags of previously collected sediment using a spatula, then placed into pre-weighed glass beakers. Samples were then dried at 100°C for at least 24 hours, and then reweighed. Sample dry bulk densities were calculated using a HumiPyc II gas pycnometer (helium gas). Net weights and volumes, run twice for each sample, along with calculated densities were recorded-on the spreadsheet AT02_sample_DBD.xlsx. The volume of the empty chamber (Vc) was recorded each day during the analytical run. Sample dry bulk density analytical results were copied and pasted into a final Microsoft Excel spreadsheet (AT02_DBD_results.xlsx, where AT02 is the batch number assigned to the sample submission). The processed data were quality control checked. Processed data were released to the submitter and incorporated into the laboratory's database. All raw analytical data generated by the samples were archived in the Sediment Laboratory. Batch-specific data files were compiled into individual spreadsheets for publication (DBD_Ashumet_Pond_2020.xlsx; Sed_Wt_Ashumet_Pond_2020.xlsx). 20210525 Radioisotope Analysis: Ten (10) to 80 grams (g) of dried sediment sample were blended and homogenized prior to sealing in a jar radioisotope analysis. Jars were placed on a planar-type gamma counter for 24 to 48 hours to measure 7Be, 137Cs, 210Pb, and 226Ra at 477, 662, 46.5 and 352 kiloelectron volts (KeV) energies, respectively (Canberra Inc., USA). Detector efficiency was determined from EPA standard pitchblende ore in the same geometry as the samples. Excess 210Pb was calculated as the decay-corrected difference between total 210Pb and supported 210Pb (considered to be equal to 226Ra). Activities of 7Be, 137Cs, and excess 210Pb were decay-corrected to time of collection, using their respective half-lives. Suppression of low-energy peaks by self-absorption was corrected for according to methods published by Cutshall and others (1983). Gamma spectroscopy detection limits were determined in GENIE software for each sample; refer to the attribute accuracy section of this metadata for further details. Values reported are above this limit, while values below are reported as 0. Core sections not analyzed are reported as blank cells. All gamma analyses were done in 2021. Sediment age and linear sedimentation rate were determined with the constant initial 210Pb concentration model (also referred to as the constant activity model and similar to the constant flux-constant sedimentation rate [CF:CS] model). A constant sedimentation rate results in constant initial 210Pbexcess concentrations in the top layer of sediment, leaving radioactive decay as the only process controlling the down-core activity of 210Pb (Goldberg, 1963). Therefore, the following equations were used to calculate age of the sample: 1) C_x = C_0 e^(-λt) where Cx is the activity at depth x, C0 is the initial activity at time 0, -λ is the decay constant of 210Pb (0.03118 y^-1) and t is the age. All activities are reported as 210Pbexcess: 2) 210Pbexcess = 210Pbtotal – 226Ra In this model, a plot of the log normalized210Pbexcess activity versus depth will result in a linear relationship, with the ratio of sediment depth to the linear sedimentation rate (LSR, i.e. mm y^-1) substituting for time, t, such that the slope (m) is related to the linear sedimentation rate: 3) LSR = λm The sediment age (in years) was then calculated as: 4) Age = x/LSR Where x is the midpoint depth of the interval. Finally, the year represented by the midpoint depth was determined as: 5) Year = Time collection – Age Where Time collection is the date of collection. Batch-specific data files were compiled into an individual spreadsheet for publication (Age_Data_Ashumet_Pond_2020.xlsx). References: Cutshall, N.H., Larsen, I.L., and Olsen, C.R., 1983, Direct analysis of 210 Pb in sediment samples—Self-absorption corrections: Nuclear Instruments and Methods in Physics Research, v. 206, issues 1–2, p. 309–312, https://doi.org/10.1016/0167-5087(83)91273-5. Goldberg, E.D., 1963, Geochronology with 210 Pb, in Miller, J.A., convener, Radioactive dating: International Atomic Energy Agency Symposium on Radioactive Dating, Athens, Greece, November 19-23, 1962, [Proceedings], p. 121-131. 20200603 Sediment Grain Size Analysis: Samples were submitted to the USGS Sediment Laboratory in Woods Hole, Massachusetts for grain size analysis using a Horiba laser diffraction unit (LA-960) and sieving of the ≥ -2 phi fraction. The samples were assigned unique analysis identifiers (Analysis_ID), and divided into batches of no more than 30 samples. Each batch was entered into a Microsoft Excel data entry spreadsheet (AT02_LD Worksheet Template.xlsx, where AT02 is the identifier assigned to the sample submission) to record the initial and dried sample weights, as well as the sieved coarse fraction weights. Each batch was also entered into macro-enabled Microsoft Excel data entry spreadsheets (GrainSizeWorksheet_LD1-30_AT02(batch_yy).xlsm or GrainSizeWorksheet_LD31-60_AT02(batch_yy).xlsm, where AT02 was the identifier assigned to the sample submission, “LD1-30” and “LD31-60” refer to the pre-labeled and weighed glass laser diffraction vials the samples were analyzed in, and “batch_yy” refers to the sample batch: AT02_GrainSizeWorksheet_LD1-30.xlsm, AT02_GrainSizeWorksheet_LD31-60.xlsm, and AT02_GrainSizeWorksheet_LD1-30(replicates).xlsm) to record the measurement data coming from the laser diffraction unit and incorporate the initial, dried, and sieved weights. About 10-15 grams (g) of wet sediment were placed in a pre-weighed beaker and the gross weight was recorded. The sample was wet sieved through a 4 millimeter (mm) (No. 5) sieve. If there was any coarse fraction remaining in the sieve, the coarse material was oven dried at 100 degrees Celsius (°C) in a pre-weighed beaker and weighed again when dry. This coarse fraction was dry sieved to determine the individual weights of the -2 to -5 phi fractions, and the weights were recorded in the data entry spreadsheet AT02_LD Worksheet Template.xlsx. The fine fraction in water was collected in a pre-labeled and weighed glass laser diffraction vial. If there was any coarse fraction remaining in the sieve from wet sieving, the vial was also oven dried at 100°C and weighed when dry. If there was no coarse fraction remaining from wet sieving, the sample proceeded directly to processing for analyses by the Horiba laser diffraction unit (LA-960). Fine fractions ready for analysis by the Horiba laser diffraction unit were rehydrated with distilled water if they had been dried. Fifteen (15) milliliters (ml) of pre-mixed 40 grams per liter (g/l) sodium hexametaphosphate [(NaPO3)6] were added to each sample. If the height of the fluid in the laser diffraction vial is less than 5 cm, more distilled water was added to raise the level to no more than 8 cm in the vial. The samples were gently stirred, covered, and allowed to soak for at least 1 hour (for samples that were not dried), up to 24 hours (for samples that were dried). Soaked vials were placed into an ultrasonic bath and run for 10 minutes at a frequency of 37 Hz with a power level of 100. If the samples appeared to be fully disaggregated, they were placed into pre-determined autosampler locations, and were run using Windows Horiba LA-960 software to obtain the fine fraction grain size distributions. The fine fraction distribution data were added to the appropriate data entry spreadsheets (AT02_GrainSizeWorksheet_LD1-30.xlsm, AT02_GrainSizeWorksheet_LD31-60.xlsm, and AT02_GrainSizeWorksheet_LD1-30(replicates).xlsm). These spreadsheets were used to calculate a continuous phi class distribution from the original fractions. Continuous phi class distribution from the original fractions were transposed to the "results" tab in the macro-enabled Microsoft Excel data entry workbooks (AT02_GrainSizeWorksheet_LD1-30.xlsm, AT02_GrainSizeWorksheet_LD31-60.xlsm, and AT02_GrainSizeWorksheet_LD1-30(replicates).xlsm). Macros in the workbook (“GS_MoM_Arithmatic,” "GS_statistics," and "sedimentname") were run to calculate grain-size classification and statistical analyses to finish processing the data. Sample, navigation, and field identifiers, along with continuous phi class distribution data, grain-size classification, and statistical analysis results were copied and pasted into a final Microsoft Excel spreadsheet (AT02_GS-LD_results.xlsx, where AT02 is the batch number assigned to the sample submission: AT02_GS-LD_results.xlsx). The processed data were quality-control checked and assigned a quality grade based on the examination of the analytical data. When considering replicate run values, if there is over a 10% difference between relative fraction percentages in this sample and the replicate, a quality grade of B will be assigned, over 15% would be assigned a C, and over 20% would be assigned a D. Quality grades for sample data that do not have any additional comments are assigned based on the calculated percent difference between the weights of the coarse fraction remaining after wet sieving and the sum of all of the weighed fractions after dry sieving the coarse fraction, indicating an estimated differing amount of material which could skew the calculated grain size results: A = percent differences between 0% and ±1.5%, B = percent differences between ±1.5% and ±3%, C = percent differences between ±3% and ±4.5%, and D = percent differences greater than ±4.5%. The quality grade is followed by a hyphen and the initials of the person who assigned the grade: BJB is Brian J Buczkowski; JDC is Jason D Chaytor; SJW is Sarah J Widlansky. Processed data were released to the submitter and incorporated into the laboratory's database. All raw analytical data generated by the samples were archived in the Sediment Laboratory. Batch-specific data files were compiled into individual spreadsheets for publication (GS_Ashumet_Pond_2020.xlsx; GS_Metric_Ashumet_Pond_2020.xlsx). 20200603 Version 2.0: Grain size data were reprocessed in September 2023 as part of a corrective action taken after an issue was identified in the Microsoft Excel data processing workbook (version 1.0) used to calculate grain size statistics and phi class distributions from raw data obtained from the Sediment Lab's Horiba LA-960 laser diffraction unit. Data coming from the instrument and weights recorded from sieving were not faulty. An error was found in a formula embedded in the workbook that translates data originally formatted in columns into rows. There are 96 bins of particle size distribution information recorded for each sample run on the instrument. The error resulted in a shifting of data by one bin (the values in bin number one in the column of data coming from the machine were translated into the position for bin number 2 in the corresponding row, and so on). Overall, the resulting data coming from version 1.0 of the processing workbook are affected by a slight shift in grainsize distribution. This error in the formula was corrected in September 2023 and a new version of the workbook (version 2.1) was generated and approved for use in the Sediment Lab. In addition, labeling for the logarithmic d10, d25, d75 and d90 headings was updated. Note the differing order of these values between Logarithmic and Arithmetic Method of Moments statistics. All affected grain size datasets using data from the laser diffraction unit have been reprocessed, reviewed, and prepared for release. Batch-specific data files were compiled into individual spreadsheets for publication, and revised to the following titles: "GS_Ashumet_Pond_2020_ver_2.0.xlsx" and "GS_Metric_Ashumet_Pond_2020_ver_2.0.xlsx". 2023 U.S. Geological Survey Brian Buczkowski Physical Scientist, Sediment Laboratory mailing and physical

384 Woods Hole Rd

Woods Hole MA 02543-1598 United States 508-548-8700 x2361 508-457-2310 gs-wh_sedlab@usgs.gov 0.00001 0.00001 Decimal degrees North American Datum of 1927 (NAD 27) Clarke 1866 6378206.4 294.978698214 Ten files are provided with this data release: 1. A data dictionary specific to this dataset (file "Data_Dictionary_Ashumet_Pond_2020.xlsx"). The data dictionary contains two tabs: Dictionary and Abbreviations. In the Dictionary tab, the definitions for each column in each data file are provided. In the Abbreviations tab, definitions, Chemical Abstract Service Numbers, and detailed descriptions are provided for abbreviations found in the data files. 2. Environmental sample PFAS data (file: "PFAS_Ashumet_Pond_2020.xlsx"). 3. QA/QC PFAS data (file: "PFAS_QA_QC_Ashumet_Pond_2020.xlsx"). 4. Total organic carbon and Total Nitrogen data (file: "C_N_Ashumet_Pond_2020.xlsx"). 5. Sieved sediment weight data (file: "Sed_Wt_Ashumet_Pond_2020.xlsx"). 6. Radioisotopic age dating data (file: "Age_Data_Ashumet_Pond_2020.xlsx"). 7. Dry bulk density data (file: "DBD_Ashumet_Pond_2020.xlsx"). 8. Grain size data (file: "GS_Ashumet_Pond_2020_ver_2.0.xlsx"). 9. Metric grain size data (file: "GS_Metric_Ashumet_Pond_2020_ver_2.0.xlsx"). 10. Data release version history summary (file: "USGS_data_release_version_history_P9DM4E66_(ver 2.0).txt"). A data dictionary specific to this dataset is provided on the landing page (file "Data_Dictionary_Ashumet_Pond_2020.xlsx"), https://doi.org/10.5066/P9DM4E66 and describes the contents of the other 8 files in this data release: "PFAS_Ashumet_Pond_2020.xlsx", "PFAS_QA_QC_Ashumet_Pond_2020.xlsx", "C_N_Ashumet_Pond_2020.xlsx", "Sed_Wt_Ashumet_Pond_2020.xlsx", "Age_Data_Ashumet_Pond_2020.xlsx", "DBD_Ashumet_Pond_2020.xlsx", "GS_Ashumet_Pond_2020_ver_2.0.xlsx", "GS_Metric_Ashumet_Pond_2020_ver_2.0.xlsx". U.S. Geological Survey GS ScienceBase mailing address

Denver Federal Center, Building 810, Mail Stop 302

Denver CO 80225 United States 1-888-275-8747 sciencebase@usgs.gov Unless otherwise stated, all data, metadata and related materials are considered to satisfy the quality standards relative to the purpose for which the data were collected. Although these data and associated metadata have been reviewed for accuracy and completeness and approved for release by the U.S. Geological Survey (USGS), no warranty expressed or implied is made regarding the display or utility of the data for other purposes, nor on all computer systems, nor shall the act of distribution constitute any such warranty. Any use of trade, firm, or product names is for descriptive purposes only and does not imply endorsement by the U.S. Government. XLSX https://doi.org/10.5066/P9DM4E66 None 20240228 Andrea K Tokranov U.S. Geological Survey, Northeast Region Hydrologist mailing address

331 Commerce Way

Pembroke New Hampshire 03275 United States 508-490-5017 508-490-5068 atokranov@usgs.gov FGDC Content Standard for Digital Geospatial Metadata FGDC-STD-001-1998