Complex PFAS Sampling at Two Industrial Sites
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Presented by Jack Sheldon at the National Ground Water Association (NGWA) PFAS Conference.
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Complex PFAS Sampling at Two Industrial Sites
- 1. Complex PFAS Sampling at Two Industrial Sites NGWA – The PFAS Management, Mitigation and Remediation Conference, 19 and 20 June, 2019 The logo and ANTEA are registration trademarks of Antea USA, Inc. © 2018 Google
- 2. Complex PFAS Sampling at Two Industrial Sites Site Comparisons Case 1 - Description, Sampling Techniques, and Quality Assurance Case 2 - Description, Sampling Techniques, and Quality Assurance Summary Agenda
- 3. Similarities • Concern for PFAS in effluent water • Material and infrastructure surface sampling • PFAS use permitted under TSCA • No state requirements at the time of use Differences • AFFF emergency use versus routine manufacturing process • Pre-2002 TSCA PFAS product versus Post-2015 product- (i.e. long-chain versus short-chain) • Concentration scale Site Comparisons
- 4. SITE ONE
- 5. Emergency AFFF Use State regulators required firefighting water to be contained and removed Initial concentrations of PFOS were five orders of magnitude (OM) (160,000 ppt) above state discharge limit of 70 ppt State ordered owner to reduce stormwater to 70 ppt before owner could resume discharge to outfall
- 6. 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 1 10 100 1000 10000 100000 1000000 PRECIPITATIONININCHES (ng/L) EPA Drinking Water Advisory Level PFOA in Stormwater Runoff PFOS in Stormwater Runoff Daily Precipitation October ‘16: Stormwater asphalt cleaning PFOS/ PFOA in Stormwater A decrease after initial high pressure wash Rainfall, stormwater, temperature and concentration relationship – decrease with less precipitation and freezing temperatures – increase with more rain and thaw Ongoing source identification and delineation needed Elevated PFOS - AFFF was likely manufactured prior to 2002
- 7. Regulatory History 2002 2008 2011 2013 2015 2016 2017 2019 US firms discontinue PFOS manufacturing UCMR 3 for PFAS in drinking water supply study EPA publishes PFAS draft procedure for sewage, biosolids UCMR 3 - Results Several drinking water supplies affected TSCA bans PFOA PFOA/PFOS drinking water advisory level 70 ppt TSCA ruling to limit manufacturing, possible health effects TSCA targets PFOS EPA publishes drinking water Method 537 14 PFAS TSCA ruling: Notification before resuming new uses of PFAS containing products EPA Action Plan -MCLs -Hazardous designation
- 8. Infrastructure Sampling Pavement and infrastructure high pressure wash reduced by one order of magnitude (OM) Small decline, with rebound suggested ongoing source Cost to contain, transport and dispose of stormwater $400K per year! Hot spot source and extent assessment needed Not sustainable - duration unpredictable, interferes with operations The Challenge - HOW TO SAMPLE INFRASTRUCTURE?
- 9. Rinse Samples Why? If done consistently, comparable results How? Consistent surface areas and rinse water volume Method blanks and PFAS- free sourced rinse water What? Tanks and pavement surfaces
- 10. Unique Low Cost HDPE sheeting and sand bags to dam up rinse water
- 11. Soil Samples Soil sampling to assess the vertical extent of PFAS Collected at locations of asphalt cracks
- 12. A-1 27 A-2 50 A-3 13 A-4 212 A-5 226 A-6 160 A-7 50 A-8 144 A-9 55 A-10 34 A-11 51 Asphalt Rinse Results PFAS total (ppt)
- 13. AST and Chip Seal Rinse Results PFAS total (ppt) AST-1 1,742 AST-2 29,800 AST-3 3,891 AST-4 20,470 AST-5 100 CS-1 137 CS-2 9,289 CS-3 432 CS-4 20,290
- 14. eS-1 1,032,000 eS-2 700 eS-3 2,450 eS-4 670 S-1 (0-0.5') 5,680 (0.5-1') 2,770 S-2 (0-0.5') 62,590 (0.5-1') 83,390 S-3 (0-0.5') 360 (0.5-1') 670 S-4 (0-0.5') 1,700 (0.5-1') 550 Soil Boring Results PFAS total (ppt)eS-1 eS-2 eS-3 eS-4
- 15. Crack in pavement Stormwater to excavation was controlled with a berm and diverted away Excavation activity can could also drag PFAS to lower soil horizons Soil Delineation Assessment Analytical Results in ppb Sample ID Depth Date PFBS (ppb) PFHxS (ppb) PFHpA (ppb) PFOA (ppb) PFOS (ppb) PFNA (ppb) S-1 (0-0.5') 3/20/17 < 0.11 0.38 < 0.094 0.14 J 5.3 < 0.089 S-1 (0.5-1') 3/20/17 < 0.13 0.27 < 0.11 < 0.13 2.5 0.20 J S-2 (0-0.5') 3/20/17 1.1 6.3 0.24 0.95 54 < 0.089 S-2 (0.5-1') 3/20/17 0.47 4.9 1.2 0.82 76 < 0.11 S-3 (0-0.5') 3/20/17 < 0.11 < 0.13 < 0.098 < 0.11 0.36 < 0.092 S-3 (0.5-1') 3/20/17 < 0.11 < 0.12 < 0.093 < 0.11 0.67 < 0.088 S-4 (0-0.5') 3/20/17 < 0.11 0.30 0.15 J < 0.11 1.4 < 0.088 S-4 (0.5-1') 3/20/17 < 0.12 0.17 J < 0.099 < 0.12 0.55 < 0.094 DUP01 (0.5-1') 3/20/17 < 0.11 < 0.12 < 0.091 < 0.11 0.35 < 0.086 eS-1 (1.5') 4/11/17 1.1 20 2.9 7.6 1,000 0.66 eS-2 (1.5') 4/11/17 0.17 J 0.40 0.3 <0.14 <0.17 <0.11 eS-3 (1.5') 4/11/17 <0.11 0.45 0.14 J 0.17 J 2.0 <0.091 eS-4 (1.5') 4/11/17 0.14 J 0.67 0.16 J 0.21 J <0.14 <0.090
- 16. Sample ID Date PFBS (ppt) PFHxS (ppt) PFHpA (ppt) PFOA (ppt) PFOS (ppt) PFNA (ppt) A-1 3/21/17 <0.91 2.5 1.3 J 2.1 22 0.78 J A-2 3/21/17 <0.89 9.2 4.9 5.1 31 1.2 J A-3 3/21/17 <0.90 2.0 1.8 J 2.0 8.7 <0.94 A-4 3/21/17 <0.90 26 5.5 60 120 <0.94 A-5 3/21/17 <0.88 26 7.4 11 180 1.9 A-6 3/21/17 <0.92 24 17 15 100 4.2 A-7 3/21/17 <0.93 10 6.6 7.9 23 2.7 A-8 3/21/17 3.5 17 7.4 6.3 110 1.9 J A-9 3/21/17 <0.90 3.7 2.3 3.5 46 0.93 J A-10 3/21/17 <0.93 4.3 3.1 4.5 23 1.1 J A-11 3/21/17 <0.88 8.1 6.1 7.7 27 2.6 AST-1 3/22/17 40 180 75 34 1,400 13 AST-2 3/22/17 210 2,400 1,100 650 25,000 440 AST-3 3/22/17 51 320 92 92 3,300 36 AST-4 3/22/17 400 2,100 400 450 17,000 120 AST-5 3/22/17 < 1.9 6.7 3.4 4.2 86 1.4 J CS-1 3/20/17 <0.81 4.4 1.3 J 3.0 130 0.73 J CS-2 3/20/17 1.9 28 28 170 9,000 62 CS-3 3/20/17 <0.93 9.4 4.0 6.3 410 2.6 CS-4 3/20/17 3.7 79 36 120 20,000 52 DUP02 3/21/17 <0.92 8.9 2.4 3.8 88 0.73 J EB_170320 3/20/17 <0.87 <0.82 <0.76 <0.71 <1.2 <0.62 EB_170321 3/21/17 <0.90 <0.85 <0.78 <0.73 <1.2 <0.64 EB_170322 3/22/17 < 0.86 <0.82 <0.75 <0.70 6.4 <0.61 Rinsate-Structural 4/10/17 1.1 J 1.3 J <0.76 <0.71 8.0 <0.62 All method blanks below MDLs or very low PFAS-free water not a source Cross-contamination during AST sampling at 6.4 ppt where ASTs were up to 25,000 ppt Delineation Assessment Analytical Results
- 17. 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 1 10 100 1000 10000 100000 1000000 PRECIPITATIONININCHES (ng/L) EPA Drinking Water Advisory Level PFOA in Stormwater Runoff PFOS in Stormwater Runoff Daily Precipitation October ‘16: Stormwater asphalt cleaning March ‘17: AST removal April ‘17: Chip seal removal May ‘17 Stormwater after AST and chip seal removal Success and Value Achieved closure within one year Saved client several million dollars in long- term on-site treatment and OM&M PFOS/ PFOA in Stormwater
- 18. 1 10 100 1,000 10,000 100,000 1,000,000 PFOA (ng/L) PFOS (ng/L) PFBS (ng/L) PFHxS (ng/L) Stormwater Runoff Sampling Data 10/21/16 11/2/16 12/1/16 1/5/17 1/13/17 1/23/17 2/23/17 3/20/17 4/3/17 4/24/17 5/9/17 6/1/17 0.1 1 10 100 1000 10000 100000 PFOA (ppt) PFOS (ppt) PFBS (ppt) PFHxS (ppt) Rinse Data A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 0.01 0.1 1 10 100 PFOA (ppb) PFOS (ppb) PFBS (ppb) PFHxS (ppb) Soil Boring Samples S-1 (0-0.5') S-1 (0.5-1') S-2 (0-0.5') S-2 (0.5-1') S-3 (0-0.5') S-3 (0.5-1') S-4 (0-0.5') S-4 (0.5-1') Media Pattern Comparisons
- 19. Site One Takeaways • PFAS of concern are resilient and persist after high intensity washing. Residuals can remain in infrastructure for decades above regulated levels • Small cracks in pavement resulted in migration to underlying soils • Rinse samples are effective to define hot spots and extent • PFAS readily mobilizes into soil. Excavation into paved areas could introduce PFAS to deeper soil horizons • Elevated PFOS in all media samples suggests the AFFF was likely made before 2002
- 20. SITE TWO
- 21. C A T H O D E A N O D E Chromic Acid Mist Gas Bubbles due to Hydrolysis Facility formulates fume suppressants for chrome plating baths Changing regulatory climate prompted facility to think about product safety and messaging to its customers Historically, used exempted long-chain raw materials (fluoro surfactants) to formulate their products Chemical Manufacturing Facility
- 22. PFAS Management Plan • Conduct site walk • Review raw material Safety Data Sheets (seven total) and CAS numbers versus analytical CAS numbers • Develop plan to sample raw materials, wastewater, and production infrastructure • Discuss analytical method with lab, especially dilution • Review results and complete data validation • Determine path forward with client
- 23. Facility Map Stormwater flow Tank Floor drain Sump & pump Wastewater treatment line Overhead wastewater treatment line
- 24. Sampling Procedures Standard PFAS SOP No cosmetics or deodorant No waterproof clothing Nitrile gloves Face shield
- 25. Production Area Considerations • Identify raw material use in each area of the plant • Determine method to sample infrastructure • Determine impact of steam cleaning
- 26. Raw Material/Sump Sampling • Sample only new drums or containers • Avoid retainage samples stored in glass • Use polypropylene pump or pour into polypropylene beaker for transfer to sample containers Sump area Raw materials
- 27. Dip Sampler Used for Weir and Sumps
- 28. Wastewater Sampling • Six tanks that can individually discharge to municipal sewer, blend with roof water • Treatment only for cyanide, metals, and phosphorus • Receives water from stormwater sump plus facility
- 29. Sampling Results - Raw Materials • PFAS concentrations ranged from 0.27 ng/L to 2.6% in raw materials! • 6:2 FTS precursor major constituent of raw materials • PFOA and PFHxS detected!
- 30. 6:2 Fluorotelomer Sulfonic acid (6:2 FTS) (C6) 8:2 Fluorotelomer Sulfonic acid (8:2 FTS) (C8) Perfluorobutanoic acid (PFBA) (C4) Perfluoropentanoic acid (PFPeA) (C5) Perfluorohexanoic acid (PFHXA) (C6) Perfluorobutanesulfonic acid (PFBS) (C4) Perfluorohexanesulfonic acid (PFHxS) (C6) Perfluoroheptanoic acid (PFHpA) (C7) Perfluorooctanoic acid (PFOA) (C8) 22 ng/L of 6:2 FTS in field blank Sampling Results - Raw Materials
- 31. • 2 rounds of sampling • PFAS concentrations ranged from 3.1 ng/L to 290,000 ng/L! • 4:2, 6:2 and 8:2 FTS precursors detected • PFOA, PFOS and PFHxS detected! • More PFAS analytes in wastewater than raw materials analysis showed Sampling Results - Wastewater
- 32. 17 PFAS Analytes Detected in Wastewater per Event PFAS Analyte WW 1 WW 2 6:2 FTS (C6) Yes Yes 8:2 FTS (C8) Yes Yes PFPeA (C5) Yes Yes PFHxA (C6) Yes Yes PFBS (C4) Yes Yes PFHxS (C6) Yes Yes PFNA (C9) Yes Yes PFDA (C10) Yes Yes PFUnA (C11) Yes Yes PFDoA (C12) Yes Yes PFTriA (C13) Yes Yes PFTeA (C14) Yes Yes PFHpS (C7) Yes Yes PFOS (C8) Yes Yes PFHpA (C7) Yes Yes PFOA (C8) Yes Yes PFOSA or FOSA (C8) Yes No Field Blank = No detections
- 33. Site Two Takeaways • PFAS of concern are resilient and persist after high intensity washing. Residuals can remain in infrastructure for decades above regulated levels • Raw materials may contain impurities • Precursors can be present at significant concentrations • Many wastewater treatment system are not able to remove PFAS • Sampling in complex scenarios requires careful planning and consultation with the lab
- 34. We do more than effectively solve client challenges; we deliver sustainable results for a better future. Thank you If you have more questions… Jack Sheldon, Senior Remediation Specialist Caron Koll, LSP, PG Katie Angel, EIT Gordon Hinshalwood, PhD, PG
Hinweis der Redaktion
- Photo by Jack Sharp on Unsplash
- Photo by Jack Sharp on Unsplash
- A graph of the PFOA and PFOS concentrations in stormwater over the first 4 months after a single AFFF application on a petroleum fire shows the persistence and rebound. This client was required to contain stormwater until 70 ppt was achieved. As you can see, the concentrations are quite high compared to the clean up standards. In this graph, the ratio between PFOA and PFOS stayed roughly the same showing how stable and resistant to degradation. High pressure wash had some effect but was not effective alone, nor did the rainfall events simply wash it a way from the equipment. Rinse samples of the AST sidewall sprayed with foam showed up to 30,000 ng/L after 5 months. Note: Temperatures of a petroleum fire are a little under 500 degrees F; around 2000 degrees F is needed to destruct PFAS.
- Nearly 20 years ago, in 2000 Most US manufacturers volunteered to remove long chained PFAS from production or switch to short chain PFAS due to concerns of the persistent properties of long chain and possible health effects associated with long chain PFAS. Shortly after that in 2002 EPA established rules under Toxic Substance Control Act (TSCA) significant new use rules to phase out of long-chain PFAS. PFOS was banned in 2002 and PFOA in 2015 Stop In 2008, the EPA developed a method for drinking water (Method 537) due to escalating concerns surrounding PFAS. In 2013 testing for six PFAS compounds was required at drinking water suppliers under the UCMR 3 rule. In 2015, TSCA rules stiffened on PFAS reporting and use. In 2016, the data became available shortly after which EPA established a 70 ppt lifetime drinking water advisory level at 70 ppt. In 2018, following an EPA summit, EPA pledges to determine whether a Maximum Contaminate Level (MCL) is needed, evaluate the need for cleanup levels and evaluate the need for hazardous waste designation. On Valentines Day this 2019, The EPA PFAS Action Plan was published with a time frame of 2020 for MCL, and designation of certain PFAS compounds a HW. These were only two of the initiatives. STOP As of October 2, 2018, the EPA is in the selection process of a group to develop an analytical methods for other media (solid waste, landfills, landfill leachate, and surrounding environmental media such as landfill gas, surface soil, surface water, sediment, subsurface soil, and groundwater. ) STOP EPA EPA-G2018-STAR-B1, Practical Methods to Analyze and Treat Emerging Contaminants (PFAS) in Solid Waste, Landfills, Wastewater/Leachates, Soils, and Groundwater to Protect Human Health and the Environment. https://www.epa.gov/sites/production/files/2018-04/documents/pfas_methods_tech_brief_02apr18_revison.pdf Although, long-chain PFAS were manufactured in other parts of the world, most have now switched to short chain PFAS. Some studies suggest short-chain PFAS replacements are as toxic as the long-chain. Some undergo transformations to PFOA.
- Developed an SOP - for consistent process Developed FSP and QAPP like the old days Wipe samples were not appropriate or comparable to stormwater. We wanted to mimic the stormwater plus the solubility values supports rinse sampling is representative Low cost simple.
- Same volume of water Same size area from location to location Low cost – Methylene blue test kit for screening was used but inconclusive, detection limits were too low.
- Note Stormwater retention pond. Red oval fire location and AFFF application area Drainage direction arrow . High pressure wash was more effective than rainfall on asphalt Tried Methylene Blue test kit field screening on asphalt without success 50 ppt detection limit plus too low and stopped. Likely stopped to soon.
- Rinse samples of the AST sidewall showed nearly 30,000 ng/L after 5 months of precipitation, whereas the adjacent AST was less than 100 ng/L of total PFAS, suggesting that there was little evidence that the mist from the AFFF traveled far from the site of application in this case. Rainfall did not removed the PFAS from AST surfaces. Equipment surface and pavement sampling SOP provided effective tool to define the extent of the PFAS sources to storm water and hot spots Based on the elevated and predominate PFOS and PFOA concentrations in the samples, the AFFF was a pre- 2000 formulation before TSCA regulation to eliminate one of the long chain PFAS, PFOS from AFFF.
- Soil beneath asphalt was collected where cracks were observed. A crack in asphalt resulted in PFAS transport to underlying soil. PFAS in soil was detected an OM greater than stormwater at one location. Not many cracks but at eS-1 asphalt was damaged during fire. Red oval location of tank fire. Blue AFFF drainage and stormwater pathway. Although a stormwater barrier was installed around the excavation and the hotspot was over excavated, concentrations in surface soils were high after excavation. Conclusion - PFAS readily mobilized into soil. Solution - In areas where PFAS might be used, such as under petroleum based ASTs, maintain pavement. Prior to excavation pressure wash paved surface. During excavation, use rigorous equipment decontamination procedures. Excavated cleaner areas first and then heavily contaminated areas lastly. Try more surgical removal process. Install berms to prevent stormwater from entering excavation. We used a berm around the excavation.
- PFAS has no indicator properties – no color, no odor. Equipment blanks below detection except day of AST rinse testing 6.4 ppt.
- A graph of the PFOA and PFOS concentrations in stormwater over 8 months we monitored after AFFF application on a petroleum fire shows the persistence.. In this graph, the ratio between PFOA and PFOS stayed roughly the same showing how stable and resistant to degradation. Source removal was selected and approved by the state agency in this case. Closure with the state was achieved. The residual sticks around for a long time. Note: Temperatures of a petroleum fire are a little under 500 degrees F; around 2000 degrees F is needed to destruct PFAS.
- Because of the apparent consistent ratio between PFOA and PFOS, we looked at two other long chain compounds in a radar diagram to see if there were consistent patterns between media of the same AFFF.
- Neither rain nor high-pressure steam cleaning wash, removed the PFAS from surfaces. High pressure wash was more effective than rinsing or rainfall. Crack in asphalt resulted in PFAS transport to underlying soil. Equipment surface and pavement sampling SOP provided effective tool to define the extent of the PFAS sources to storm water and hot spots Although a stormwater barrier was installed around the excavation and the hotspot was over excavated, concentrations in surface soils were higher after excavation, than before excavation. Solution more rigorous decontamination procedures, more surgical removal process and better berms to prevent stormwater from entering excavation. Based on the elevated and predominate PFOS and PFOA concentrations in the samples, the AFFF was a pre- 2000 formulation before TSCA regulation to eliminate one of the long chain PFAS, PFOS from AFFF. In summary, PFAS have been manufactured for over 70 years, fulfilling a vital role in consumer products but there has been a consequence resulting in some of the largest environmental clean up settlements in history. AFFF and other products are needed for public safety. However, because of PFAS innate properties, when released, they persist in the environment, migrate great distances, bioaccumulate and biomagnifying up the food chain. PFAS is found drinking water supplies, distributed globally and in 95% of the human population. There are reported health affects on 20 of the PFAS and 70 more slated for toxicological profiles. Still many unknowns. PFAS hotspots are found near industrial areas, military areas, WWTPs and airports. States have begun to regulate, in advance of EPA. There are hundred of PFAS sites and number of lawsuits filed against both manufacturers and industrial users of raw materials containing PFAS even those shorter-chained. An internal audit can help you to understand and manage your risk. https://www.epa.gov/sites/production/files/17-02/documents/ucmr3-data-summary-january-17.pdf
- Key features include: Floor sumps Stormwater flow Wastewater treatment area Tanks, hoses, pumps, and mixers. RESULT Antea Group provided its client with an analysis of its wastewater stream, as well its raw products. A deep technical analysis of the results was provided, as well as analysis of the regulatory setting, albeit rapidly evolving as it was. Antea Group’s client was able to then evaluate its strategic business plans and also maintain its obligations to regulators.