Ex Situ Treatments of Aqueous Film-Forming Foam Impacted Water

Transcription

1 Ex Situ Treatments of Aqueous Film-Forming Foam Impacted Water Tersus Webinar September 21, 2016

2 Page 2 Acknowledgements David F. Alden, P.E. Tersus Environmental Durham, NC Richard, J. Stewart, PhD Ziltek Pty Ltd Thebarton, South Australia, Australia Jürgen Buhl & Martin Cornelsen Cornelsen Umwelttechnologie GmbH Essen, Germany Ziltek Pty Ltd Thebarton, South Australia, Australia Sensatec GmbH Kiel, Germany Beca Melbourne, Victoria, Australia Cornelsen Umwelttechnologie GmbH Essen, Germany "It's better to hang out with people better than you. Pick out associates whose behavior is better than yours and you ll drift in that direction." Warren Buffet

3 Page 3 Perfluorochemicals Perfluorooctane sulfonate (PFOS) Perfluorooctanoic acid (PFOA) Buck et al. (2011) Integr. Environ. Assess. Manag. 7, Slide from Daniel P. McInnis, Ph.D., University of Minnesota

4 Page 4 Physicochemical Properties Hydrophilic (water soluble) Hydrophobic + Oleophobic Kissa (2001), Fluorinated Surfactants and Repellents, 2 nd ed. Slide from Daniel P. McInnis, Ph.D., University of Minnesota

5 Page 5 Food packaging Personal care products Nonstick cookware PFAS Fire-fighting foams Electronics Stain-resistant carpet NIEHS (2012), Perfluorinated Chemicals Fact Sheet Slide from Daniel P. McInnis, Ph.D., University of Minnesota

6 Page 6 Fire Retardant Foam Aqueous Film-Forming Foam Travis Air Force Base in California, Sept. 24, Photo: U.S. Air Force

7 Page 7 Aqueous Film-Forming Foam after a test of the sprinkler systems Hangar 211 at Mountain Home Air Force Base, Idaho, Dec. 21, Photo: U.S. Air Force Flight deck of the aircraft carrier USS Ronald Reagan, May 19, Photo: U.S. Navy

8 Page 8 Estimates of AFFF Quantities by Sector (Darwin, 2011) Sector PFOS-based AFFF (2004), gallons PFOS-based AFFF (2011), gallons Military & Other Federal 2,100,000 1,094,700 Civil Aviation (Aircraft Rescue and Fire) 130,000 20,000 Oil Refineries 950, ,000 Other Petro-Chem 1,000, ,000 Civil Aviation (Hangars) 190,000 70,300 Fire Departments 120,000 60,000 Miscellaneous 150,000 75,000 TOTALS 4,600,000 1,972,000 Darwin, R. L. (2011). Estimated inventory of PFOS-based Aqueous Film Forming Foam (AFFF), 2011 update to the 2004 report entitled Estimated Quantities of Aqueous Film Forming Foam (AFFF) In The United States. Prepared for the Fire Fighting Foam Coalition, Inc., Arlington, VA.

9 Page 9 Unregulated Contaminant Monitoring Rule 3 (UCMR 3) Assessment Monitoring: List 1 Contaminants Perfluorinated Compounds EPA Method 537 Compound Abbreviation End Group Minimum Reporting Level Perfluoroheptanoic acid PFHpA COOH 0.01 µg/l Perfluorooctanoic acid PFOA COOH 0.02 µg/l Perfluorononanoic acid PFNA COOH 0.02 µg/l Perfluorobutane sulfonate PFBS SO 3 H 0.09 µg/l Perfluorohexane sulfonate PFHxS SO 3 H 0.03 µg/l Perfluorooctane sulfonate PFOS SO 3 H 0.04 µg/l USEPA (2012)

10 Page 10 October 2015 UCMR 3 Data Summary Data visualization: Moiz Syed. Sources: EPA and Department of Defense.

11 Page 11 The Challenge Low solubility Existing treatment processes ineffective / limited GAC & ion exchange limited to longer chain PFASs Poor efficiency Influence of background chemistry Waste disposal costs

12 Page 12 Limited Remediation Options Incineration requires high temp (>1,100 o C) Biological and chemical efficacy not proven Landfill prohibited or require pre-treatment GAC proven for water, but doesn t treat full suite Does RemBind offer a viable and cost-effective alternative for treating PFASs in soil and water?

13 Page 13 Applications Soil remediation Groundwater hot spots and plumes Complex groundwater chemistries Recovered fire fighting water Drinking water POE systems

14 Page 14 RemBind

15 Page 15 What is RemBind? Powdered reagent that binds to organic contaminants in soil/water to prevent leaching Chemical fixation or immobilization Binds to range of contaminants including TPH, PAH, and perfluorinated compounds US Patent 8,940,958

16 Page 16 How Does RemBind Work? Main ingredients: o Activated carbon o Aluminium hydroxide (amorphous) o Organic matter and additives Large surface area with mixed charges Chemical and physical interactions

17 Page 17 Absorption and Adsorption

18 Page 18 Binding PFASs Perfluoroalkyl Sulfonates (n = 2-10) Anions Perfluoroalkyl Sulfonamide Amino Carboxylates (n = 3-8) Perfluoroalkyl Carboxylates (n = 2-13) Perfluoroalkyl Sulfonamido Amines (n = 3-8) Cations Fluorotelomer Betaines (n = 5,7,9) Zwitterions After: Per and Polyfluoroalkyl Substances (PFAS) in AFFF Formulations and Groundwater, Jennifer A. Field, Ph.D., April

19 Point of zero charge > ph 7.7 Page 19 Proposed mechanisms of action Electrostatic interactions Organic Matter - Hydrophobic Interactions Aluminium Hydroxide (Amorphous) Physical Binding Van der Waals Activated Carbon

20 Page 20 How is RemBind Applied Add RemBind to soil at 1-10% by weight Adjust to ~30% moisture Binding occurs within 48 hours Mixing equipment pug mill or loader

21 Page 21

22 Page 22 Treatability Study: PFOS in Soil Two commercial airport sites in Australia All lab work independently audited Site soils mixed with RemBind or RemBind Plus at various addition rates

23 Page 23 PFOS and PFOA Soil Results

24 Page 24 PFOS and PFOA Soil Results

25 Page 25 PFOS and PFOA Soil Results * Soil leachates prepared using the Toxicity Characteristic Leaching Procedure (TCLP)

26 Page 26 How Stable is Binding? Multiple Extraction Procedure (US EPA 1320) Simulates 1,000 years acid rain in an improperly designed sanitary landfill 1 x 24 hour leach at ph 5, 9 leaches ph 3 Site 1-5% RemBind Plus Treatment Leach EP PFOS ug/l <0.02 < <0.02 <0.02 <0.02 <0.02 <0.02 Risk assessment independent plant studies have commenced with an Australian University

27 Page 27 RemBind used to Immobilize PFAS in Water Independent evaluation carried out by a testing company in Germany - Sensatec Passed PFAS contaminated water (1.8 mg/l) through a column, up to 100 pore volumes Compared RemBind Plus with activated carbon

28 Page 28 Evaluated RemBind to remove short- and long-chain PFAS from water Test Compound C-F Chain Length Terminal Group PFOS n=8 Sulfonic acid PFOA n=7 Carboxylic acid PFBS n=4 Sulfonic acid PFBA n=3 Carboxylic acid

29 residual concentration in % of starting concentration residual concentration in % of starting concentration Page 29 Using RemBind to remove short- and longchain PFAS from water 2% RemBind Plus Residual PFAS Concentration After Specific Contact Time with 2% RemBind Plus Total Conc. PFAS [%] PFOS [%] PFBS [%] PFOA [%] PFBA [%] Residual PFAS Concentration After 60 Minute Contact Time With RemBind Plus Total Conc. PFAS [%] PFOS [%] PFBS [%] PFOA [%] PFBA [%] Contact Time [min] 0 M1 start 6,5 mg l-1 M1 M2 start 650 µg l-1 M2 M3 start 65 µg l-1 M3 M4 start 6,5 µg l-1 M4

30 residual concentration in % of starting concentration residual concentration in % of starting concentration Page 30 RemBind Outperforms Activated Carbon RemBind 100 Residual PFAS Concentration After 100 Passes Through RemBind Plus Column Activated Carbon 100 Residual PFAS Concentration After 100 Passes Through Activated Carbon Column Total Conc. PFAS [%] From Start Concentration PFOS [%] PFBS [%] PFOA [%] PFBA [%] Total Conc. PFAS [%] From Start Concentration PFOS [%] PFBS [%] PFOA [%] PFBA [%] Column Passages Column Passages

31 Page 31 RemBind Outperforms Activated Carbon

32 Page 32 Using RemBind to remove short- and longchain PFAS from water Summary of data: RemBind Plus removed shorter chain PFASs more effectively than activated carbon 60 minute contact time is optimal Estimated PFOS adsorption capacities: o ~2,000 µg/g for RemBind Plus o ~1,000 µg/g for activated carbon

33 Page 33 Removal of PFAS from fire training wastewater using RemBind Independent trials carried out by BECA using raw wastewater from fire training ground Results summary: o PFOS reduced from 50 µg/l to: <0.02 µg/l at 0.1% (w/v) addition rate o PFOS adsorption capacity = 2,560 µg/g o 60 minute contact time is optimal

34 Page 34 Removal of PFAS from fire training wastewater using RemBind

35 Page 35 Conclusions RemBind Outperformed activated carbon in binding shorter chain compounds PFBS/PFBA Showed double the adsorption capacity of the activated carbon Strongly bound to PFOS and PFOA in soil/water Bound 18 PFAS additional compounds to varying degrees

36 Page 36 Treatment Train

37 Relative Concentration Page 37 Why Treatment Train? Breakthrough Behavior of Adsorbers Sum of PFC without PerfluorAd Sum of PFC with PerfluorAd Throughput

38 Page 38 PerflourAd Surface active liquid ingredient Developed by Cornelsen Added to contaminated water Dosing rate adjustable (PFAS conc. or target) Micro-flocs are generated Removable by precipitation/filtration

39 Page 39 PerfluorAd System Mobile Treatment System PerfluorAd Stirring Reactors

40 Page 40 Test Sites Nuremberg & Düsseldorf Airport

41 Page 41 Groundwater Chemistry BTEX: Ethylbenzene & Xylene VOC: cdce, TCE, VC Hydrocarbons (C5-C10, > C 10) & PAH (traces)

42 Page 42 PFAS Chemistry Sum PFASs Average 423,60 µg/l Maximum 522,24 µg/l Minimum 243,44 µg/l

43 Page 43 Project Summary Treatability Study Pilot Test 2014 (Sep-Nov) Data evaluation o PerflorAd found as most economical technique o PerflorAd selected for full scale Installation Sep 2015

44 Page 44 PerfluorAd Plant ph, Iron Removal, Flocculent Dosing, Stripping, PerfluorAd Dosing, Reactor, Filtration, Backwashing, and Adsorption

45 Page 45 PerfluorAd System Flow rate ~ 2 m³/hr (8.8 gpm) Remediation target 0.3 µg/l o For PFOS, PFOA & PFHxS (sum) Plus max 0.23 µg/l PFOS Remote control 1 or 2 site visits per week

46 Page 46 Results Sum of PFASs

47 Page 47 Results PFAS Treatment Nuremberg Airport More Than 90% Reduction with PerfluorAd

48 Page 48 Benefits for Contaminated Sites Independently validated as a rapid, low-cost remediation option PerfluorAd: water RemBind : soil & water Minimize disposal costs Readily available from Tersus Hangar 211 at Mountain Home Air Force Base, Idaho, Dec. 21, Photo: U.S. Air Force

49 Page 49 Applications Groundwater hot spots and plumes Complex groundwater Recovered fire fighting water Drinking water (subject to local regulation)

50 Page 50 Thank You! Gary M. Birk, P.E. Managing Partner Tersus Environmental x (cell)