MEMORANDUM FOR SEE DISTRIBUTION SUBJECT: Aqueous Film Forming(AFFF)Workshop We would like you to attend a one day workshop to discuss the impact ofthe U.S. Environmental Protection Agency' s(U.S.EPA)proposed rule which has the potential to ban future production and import of perfluorooctyl sulfonates(PFOS)chemicals to the Department of Defense. The Mil Spec for AFFF allows the use ofPFOS,perfluorooctanoic acid(PFOA), and telomers as foaming agents. The U.S.EPA released data this past year that indicates PFOS chemicals are persistent, bioaccumulating and toxic. PFOS has been found in the blood ofthe general US population, in wildlife, and in people overseas. The 3M Company,the sole United States producer of ninety PFOS chemicals, has chosen to discontinue their manufacture and sale of all uses globally by December 31, 2002, and substantially reduce their manufacture for the most widespread uses ofthese chemicals by December 31, 2000. The U.S. EPA is evaluating PFOA and telomer chemicals as a substitute for PFOS. PFOA and telomer are also persistence in the environment and more toxic than PFOS. Because of this, they also may be subject to manufacturers' withdrawal from the market place (similar to 3M's action for PFOS)or future EPA rule making. AFFF is used in a number of critical life saving situations in DoD. Currently, there are no known substitutes that are as effective as the materials in the Mil Spec. We've asked the Air Force Research Laboratory, Materials and Manufacturing Directorate to present recommendations and discuss potential substitutes. We plan to discuss "high-risk" uses ofPFOS and what should be done to reduce or eliminate environmental releases ofPFOS. We will also determine if DoD should switched to PFOA or telomer instead ofPFOS. We need a multi-disciplinary team to conduct this review and develop an AFFF replacement strategy. The workshop will be held on March 16, 2001,from 0800hrs - 1630hrs, in the OSD Conference Center, 1E801, Room 4, Pentagon. We also requested the Defense Logistic Agency to brief DoD's uses ofPFOS. Attached is the meeting agenda. My POC for this Workshop is Lt Col Isaac Atkins, Director Occupational Health Policy, ODUSD (ES)/FP. He can be reached at (703)604-1628,if you have any questions. Curtis Bowling Assistant Deputy Under Secretary of Defense Force Protection Attachment: As stated US00003038-D Aqueous Film Forming(AFFF)Workshop Agenda Introduction (Overview) Mr. Curtis Bowling AFFF Environmental Issues Dr. Doug Dierdorf, AFRL Toxicity ofPFOS,PFOA,Telomer TBD, USEPA Impact of AFFF Voluntary Production Ban on Army TBD, DASA(ESOH) Impact of AFFF Voluntary Production Ban on Navy TBD,(E&S) Impact of AFFF Voluntary Production Ban On AF TBD,DASAF(ESOH) Overview of AFFF Uses and Impact to Fire-fighting Operations TBD, National Fire Protection Association Impact AFFF Voluntary Production Ban On FAA TBD,Federal Aviation Administration PFOS Uses TBD,Defense Logistics Agency The Way Ahead Workshop Members US00003039-D Distribution DASAF(ESOH) DASN(E&S) DASA(ESOH) Defense Logistics Agency AFRL/MMD USEPA Federal Aviation Administration National Fire Protection Association US00003040-D From: To: Sent: Subject: Attachments: Toncray Bradley A NNVA Bennett David C NNVA; Chapman Keith D NNVA; Hancock Donald L NNVA; Lowe Donald J NNVA; Geithmann Gary R CONT NNVA; Carty Jeffrey L NNVA; Earehart James NNVA; Korzun Joel A NNVA; Kelly Art G NNVA; Yarashus Thomas R NNVA; Wood Leesa M NNVA 3/9/2001 2:20:08 PM FW: Ban on AFFF Jeff F-1.TIF Original Message----From: Parish Benjamin A NNVA Sent: Friday, March 09, 20018:53 AM To: Toncray Bradley A NNVA; Michael A Turner (CNAP N4342P)(E-mail) Subject: FW: Ban on AFFF Just thought you would like to know. Ben ---Original Message--From: Lewis Edward A NSSC [mailto:LewisEA@NAVSEA.NAVY.MIL] Sent: Friday, March 09,2001 8:41 AM To: Corley Wesley S NSSC Cc: Plunkett R Bryan CONT NSSC: Ngo Tien M NSSC; Parish Benjamin A NNVA: Speca Aaron M NNVA: Wujick Christine A NSSC; Montgomery Mike L CONT NSSC:'Mike Turner Subject: FW: Ban on AFFF Wes, FYI. We will continue to monitor this situation and it's potential impact to the CVN 70 RCOH. V/R, Ed Lewis PEO Aircraft Carriers RCOH Ship Design Manager (703)607-1818 x 331 (Voice) (703)607-2495(Fax) (703)505-6728 (Cell) Lew isea@naysea.navy.mi Original Message----From: Fink Jeff E NSSC Sent: Friday, March 09, 20018:05 AM To: Raber James D NSSC; Snyder CF(Charles) NSSC; Bergner Richard L NSSC; Wujick Chrisbne A NSSC; McAllister Keith R NSSC; Lewis Edward A NSSC; Gimbel Weldon K NSSC; Orski Gary A NSSC; Ngo Tien M NSSC; Waldman Jack S NSSC; Plunkett R Bryan CONT NSSC; Bob Morris (E-mail); Jim Counts (E-mail); Sean Kiely (E-mail) Subject: Ban on AFFF Just wanted to keep everyone up to date on the AFFF issue. For those of you who do not know EPA has proposed a rule which has the potential to ban future production and import of chemicals that are integral to the production of AFFF. Background AFFF was developed by the Navy Labs in the 1960s to provide better fire protection than the older protein foam. AFFF is used in machinery rooms, flight decks and hangar bays on most Navy ships. Mil-Std AFFF is used at most airports throughout the world and is considered by the insurance industry as the premier fire fighting agent. Some of the chemical components of AFFF are categorized as Perfluorocytl Sulfonates(PFOS) which can potentially degrade into PFOSA (acid). PFOSA is highly persistent in the environment and has a strong tendency to bioaccumulate. (which means, like lead, the body absorbs this chemical, but does not get rid of it. Over time the body can accumulate this chemical to toxic levels) Studies indicate that exposure to PFOSA is widespread and recent tests have raised concerns about long term effects in people and wildlife. There are four manufacturers on the QPL for AFFF. 3M won the current contract to supply AFFF to DOD. This contract expires in Dec '02. 3M, worried about the potential future problems, has decided to get out of the market as soon as the contract is over. They have already stopped their production of things like ScotchGuard that have the same PFOS. James Rudroff of N452C wrote a point paper on this issue. (see attachment) I have been told be NAVSEA 051_4 that there is a question as to whether the other manufacturers will stay in the market knowing US00002942 that 3M got out and why they got out. There is an AFFF Workshop being held on March 16th at the Pentagon sponsored by the Assistant Deputy Under Secretary of Defense Force Protection in which NAVSEA 051-4, EPA, DLA will be in attendance. If production of AFFF is discontinued there will certainly be a major impact to Carriers as well as the rest of the Navy. The scope of effort to replace AFFF will be larger than the Freon elimination program. The effort could be on the magnitude of Asbestos elimination. However it is to early to panic and to discuss corrective action. We need to let the tech community and industry experts have a chance to assess the total picture and develop a POA. The Aux and Crew Team here at PEO Carrier will be closely monitoring the situation. Jeff_F-1.TIF Jeff Fink PEO - E DSEM Aux & Crew (703) 607-1701 x343 US00002943 From: To: Sent: Subject: Bowling, Curtis, Mr, OSD-ATL ;;; 3/31/2001 6:24:00 PM FW: Fluorotelorner Chemicals and Related Fluoroorganics We need to talk about the occupational exposure of telomers. > Original Message >From: Dierdorf Doug S Contr AFRL/MLQD >[mailto:Doug.Dierdorf@tyndall.af.mil] >Sent: Friday, March 30, 2001 2:08 PM >To: Curtis Bowling (E-mail) >Cc: Carr Virgil J Contr AFRL/MLQD; Vickers Dick N Civ >AFRL/MLQD; Galindo >Bob Contr AFRL/MLQD >Subject: FW: Fluorotelomer Chemicals and Related Fluoroorganics >Curtis, >I believe that a response to this needs to come from your >office. I will >provide a draft emphasizing the dispersive nature of AFFF and >our concerns >based on the degradation of Telomer surfactants to >perfluorocarboxylic acids >resembling PFOA. > Original Message >From: Stephen H Korzeniowski >[mailto:Stephen.H.Korzeniowski@USA.dupont.comJ >Sent: Friday, March 30, 2001 12:11 PM >To: doug.dierdorf@tyndall.af.mil >Subject: Fluorotelomer Chemicals and Related Fluoroorganics >Doug, I obtained your name from Mary Dominiak of the US EPA. >We met and >spoke again on Tuesday at the public hearing held by the US >EPA on Tuesday >this week in Arlington, VA. >I have a dual role in DuPont. One is as a business manager for a >fluorosurfactants and additives business. And the other is an external >company role in working with the global regulatory agencies and Telomer >consortium (see below). >You were copied on an E-mail note to Mary written by Lt. Col. >Isaac Atkins, >Jr on February 13, 2001referencing a AFFF Workshop held on 16 >March 2001. >This E-mail note refers to a letter (which was attached) >written by Curtis >Dowling of the Office of the Under Secretary of Defense. The subject >letter largely deals with the subject of PFOS chemicals, their >use in fire >fighting, and the proposed ban by the US EPA. >In this letter signed by Mr. Dowling was a comment in the >beginning of the >second paragraph and I quote " PFOA and telomer are also >persistence in the >environment and more toxic than PFOS." We at DuPont do not >understand the >basis on which Mr. Dowling could make such a statement about Telomer >products. Naturally we would like to see the data that led US00003056-D >Mr. Dowling to >the conclusion he cited in this 12 February 2001 letter. We >surely would >welcome the opportunity to talk to you and Mr. Dowling about DuPont >Fluorotelomer products as it relates to descriptive biology/toxicology, >environmental fate and effects, and overall exposure >assessment. I would >like the opportunity to share our data, our testing program, >and relate the >outcome of several meetings we have had with the US EPA over >the past year. >In addition, most of the global telomer manufacturers have >joined together >to form a consortium group called the Telomer Research Program (TRP) to >further study our products. I can also describe this in >detail for you. >Please let me know how you would like to proceed. >I can be reached by E-mail by just responding to this note or using >stephen.h.korzeniowski@usa.dupont.com. This is usually the >easiest way to >reach me due to my travel schedule. I can also be reached by phone on >302-992-3672 and fax - 302-892-1135. >I look forward to discussing these matters with you. >Thank you in advance for your consideration. >Steve US00003057-D From: To: Sent: Subject: Phull, Kotu K COL ASA-I&E ;;; 3/28/2001 10:48:00 AM FW: AFFF Ike: Per conversation this morning. Please call me if you have any questions. Regards, KOTU K (KK) PHULL COL, MS Office of the Deputy Assistant Secretary of the Army for Environment, Safety, and Occupational Health 110 Army Pentagon, Room 2E577 Washington, DC 20310-0110 (703) 697-0440, DSN 227 FAX - (703) 693-8149 Original Message From: Bowling, Curtis, Mr, OSD-ATL (mailto:Curtis.Bowling@osd.mil] Sent: Wednesday, March 28, 2001 6:28 AM To: Phull, Kotu K COL ASA-I&E Subject: RE: AFFF Thanks > Original Message >From: Phull, Kotu K COL ASA-I&E >Sent: Tuesday, March 27, 2001 4:17 PM >To: Bowling, Curtis, Mr, OSD/ATL >Cc: Fatz, Raymond J Mr ASA-I&E >Subject: AFFF >Curtis: >As requested at the 16 March AFFF Workshop, we feel that the >DOD/users would >need to answer the following questions to minimize the impact >of a future >AFFF ban by the EPA. I have also included a list of the potential Army >organizations that should be considered for membership on the DOD AFFF >Steering Group. Our response is based on limited >coordination, due to the >short time available. We will ensure a wider Army-wide >coordination upon >receiving further instructions/tasking from your Office. >Please call me, if >you have any questions. AFFF = All PFOS's, PFOAs, and telomers. >A. QUESTIONS: >1. Quantity of these substances used in the Army >2. Quantity of AFFF that the Army can afford to store as the >Reserves for >continued, critical uses past the phase out >3. Operations where these substances are used. Although the >discussion at U S00003051-D >the Workshop focused primarily on the use of AFFF in >firefighting, we would >need to determine other operations/products related to the use of AFFF, >e.g., aviation hydraulic fluids, semiconductors, etc. > - Need to identify all MILSPECs/STDs, NSNs, and/or commercial >/industry specs that define these materials. >4. Critical uses. We would need to define "critical uses" to ensure >consistency in responses received from the field. >5. Areas where uses can be eliminated, e.g., training >6. Quantity of AFFF that the Army can afford to store >(COST)/must store >(CRITICAL USES) as reserves for continued use past the phase-out >7. Impact of the use of non-Aqueous Film Forming Foams >Operational, e.g., >process modifications for fire-fighting; Cost >8. Environmental Impact of potential releases of AFFF into >the environment >9. Current and projected research, in-house and in partnership with >Industry - ASA(ALT) >Development of AFFF substitutes with AFFF-like performance; >Technology enhancements to improve the performance of non-AFFF products >10. Procurement strategies, i.e., availability and production >capabilities >for alternatives; how to budget and POM for increased >reserves, if the DOD >decides to continue the use of AFFF past the EPA ban, for >increased costs >associated with use of AFFF substitutes, e.g., system >retrofitting, need for >additional equipment, etc.; cost Of disposal Of excess stored >materials that >may have to be disposed of as "hazardous material" >11. Need for occupational assessments and medical monitoring >based on the >review of available data >- Exposure monitoring >- Medical monitoring >- Population to be monitored >- Cost > >12. Environmental, Safety, and health considerations for AFFF >substitutes >B. DOD STEERING GROUP MEMBERSHIP. Some of the following >offices/organizations should be considered for membership: >ACSIM (Assistant >Chief of Staff for Installation Management, ODCSLOG (Deputy >Chief of Staff >for Logistics, APPSO (Army Acquisition Pollution Prevention >Support Office >(to represent AMC (Army Materiel Command and ASA/ALT >(Assistant Secretary of >the Army for Acquisition, Logistics, and Technology), OTSG >(Office of the >Surgeon General), and this Office. ODCSLOG would appear to be >ideal Army >Lead. >Regards, US00003052-D >KOTU K (KK) PHULL >COL, MS >Office of the Deputy Assistant Secretary of the Army > for Environment, Safety, and Occupational Health >110 Army Pentagon, Room 2E577 >Washington, DC 20310-0110 >(703) 697-0440, DSN 227 >FAX - (703) 693-8149 US00003053-D MEMORANDUM FOR SEE DISTRIBUTION SUBJECT: Request Information on Usage ofPerfluorooctly Sulfonates Containing Materials We would like you to provide information on the impact ofthe U.S. Environmental Protection Agency's(U.S.EPA)proposed rule that calls for the phase-out of90 perfluorooctly sulfonate(PFOS)chemicals(See attachment). The Mil Spec for Aqueous Film Forming(AFFF) allows the use ofPFOS, perfluorooctanoic acid(PFOA),and telomers to produce fluorochemical surfactants which are key to helping other AFFF's agents meet low fire-fighting surface tension requirements. AFFF is used in a number of critical life saving situations in DoD and currently, there are no known substitutes that are as effective as the materials in the Mil Spec. The U.S. EPA released data this past year that indicates PFOS chemicals are persistent, bioaccumulating and toxic. PFOS has been found in the blood ofthe general US population, in wildlife, and in people overseas. The U.S.EPA will prevent manufacture or import ofPFOS after the phase-out period, including PFOS-based AFFF,unless a 90-day notice is filed and approved. They are also evaluating PFOA and telomer chemicals. PFOA and telomer are also persistence in the environment and may pose significant health risks. Because of this, PFOA and telomer may also be subject to manufacturers' withdrawal from the market place (similar to 3M's action for PFOS) or future EPA rule making. Request you perform an assessment ofthe impact ofEPA's phase-out ofPFOS to your organization and provide a copy to my office by 08 Jul 01. This assessment should include the quantity (in lbs.) and type of materials that contain PFOS. Include the amount of AFFF or PFOScontaining material in stock, number ofsystems and the amount (in lbs.) used per year. Also list the operations where AFFF or PFOS-containing materials are used and identify all mission critical uses, amounts, usage rate, stockpile, and potential substitutes, if any. Mission critical uses are uses where there are no available substitutes and phase-out ofPFOS will negatively impact operational effectiveness and operational suitability of combat missions or contribute significantly to the degradation of combat capability. In addition, please explain the mission impacts if a fire suppression system is not replaced, of cost replacement options and estimate quantities needed for stockpiling for mission critical uses. Identify any operations that release PFOS-containing materials to the environment and take appropriate steps to prevent or stop these releases. We will use this information to develop a DoD AFFF and PFOS-containing material replacement strategy. My POC is Mr. Gary Hamilton. US00002948 He can be reached at(703) 604-1820, email: gary.hamilton@osd.mil. If you have any questions, please contact him Curtis M. Bowling Assistant Deputy Under Secretary of Defense (Force Protection) Attachment: As stated US00002949 DISTRIBUTION DASA(ESOH) DASN(E&S) DASAF(ESOH) DEFENSE LOGISTICS AGENCY DEFENSE AGENCIES' DESIGNATED AGENCY SAFETY AND HEALTH OFFICIAL US00002950 From: To: Sent: Subject: Bowling, Curtis, Mr, OSD-ATL ;;; 3/31/2001 6:24:00 PM FW: Fluorotelorner Chemicals and Related Fluoroorganics We need to talk about the occupational exposure of telomers. > Original Message >From: Dierdorf Doug S Contr AFRL/MLQD >[mailto:Doug.Dierdorf@tyndall.af.mil] >Sent: Friday, March 30, 2001 2:08 PM >To: Curtis Bowling (E-mail) >Cc: Carr Virgil J Contr AFRL/MLQD; Vickers Dick N Civ >AFRL/MLQD; Galindo >Bob Contr AFRL/MLQD >Subject: FW: Fluorotelomer Chemicals and Related Fluoroorganics >Curtis, >I believe that a response to this needs to come from your >office. I will >provide a draft emphasizing the dispersive nature of AFFF and >our concerns >based on the degradation of Telomer surfactants to >perfluorocarboxylic acids >resembling PFOA. > Original Message >From: Stephen H Korzeniowski >[mailto:Stephen.H.Korzeniowski@USA.dupont.comJ >Sent: Friday, March 30, 2001 12:11 PM >To: doug.dierdorf@tyndall.af.mil >Subject: Fluorotelomer Chemicals and Related Fluoroorganics >Doug, I obtained your name from Mary Dominiak of the US EPA. >We met and >spoke again on Tuesday at the public hearing held by the US >EPA on Tuesday >this week in Arlington, VA. >I have a dual role in DuPont. One is as a business manager for a >fluorosurfactants and additives business. And the other is an external >company role in working with the global regulatory agencies and Telomer >consortium (see below). >You were copied on an E-mail note to Mary written by Lt. Col. >Isaac Atkins, >Jr on February 13, 2001referencing a AFFF Workshop held on 16 >March 2001. >This E-mail note refers to a letter (which was attached) >written by Curtis >Dowling of the Office of the Under Secretary of Defense. The subject >letter largely deals with the subject of PFOS chemicals, their >use in fire >fighting, and the proposed ban by the US EPA. >In this letter signed by Mr. Dowling was a comment in the >beginning of the >second paragraph and I quote " PFOA and telomer are also >persistence in the >environment and more toxic than PFOS." We at DuPont do not >understand the >basis on which Mr. Dowling could make such a statement about Telomer >products. Naturally we would like to see the data that led US00003056-D >Mr. Dowling to >the conclusion he cited in this 12 February 2001 letter. We >surely would >welcome the opportunity to talk to you and Mr. Dowling about DuPont >Fluorotelomer products as it relates to descriptive biology/toxicology, >environmental fate and effects, and overall exposure >assessment. I would >like the opportunity to share our data, our testing program, >and relate the >outcome of several meetings we have had with the US EPA over >the past year. >In addition, most of the global telomer manufacturers have >joined together >to form a consortium group called the Telomer Research Program (TRP) to >further study our products. I can also describe this in >detail for you. >Please let me know how you would like to proceed. >I can be reached by E-mail by just responding to this note or using >stephen.h.korzeniowski@usa.dupont.com. This is usually the >easiest way to >reach me due to my travel schedule. I can also be reached by phone on >302-992-3672 and fax - 302-892-1135. >I look forward to discussing these matters with you. >Thank you in advance for your consideration. >Steve US00003057-D From: To: Sent: Subject: Bowling, Curtis, Mr, OSD-ATL ;;; 3/31/2001 6:24:00 PM FW: Fluorotelorner Chemicals and Related Fluoroorganics We need to talk about the occupational exposure of telomers. > Original Message >From: Dierdorf Doug S Contr AFRL/MLQD >[mailto:Doug.Dierdorf@tyndall.af.mil] >Sent: Friday, March 30, 2001 2:08 PM >To: Curtis Bowling (E-mail) >Cc: Carr Virgil J Contr AFRL/MLQD; Vickers Dick N Civ >AFRL/MLQD; Galindo >Bob Contr AFRL/MLQD >Subject: FW: Fluorotelomer Chemicals and Related Fluoroorganics >Curtis, >I believe that a response to this needs to come from your >office. I will >provide a draft emphasizing the dispersive nature of AFFF and >our concerns >based on the degradation of Telomer surfactants to >perfluorocarboxylic acids >resembling PFOA. > Original Message >From: Stephen H Korzeniowski >[mailto:Stephen.H.Korzeniowski@USA.dupont.comJ >Sent: Friday, March 30, 2001 12:11 PM >To: doug.dierdorf@tyndall.af.mil >Subject: Fluorotelomer Chemicals and Related Fluoroorganics >Doug, I obtained your name from Mary Dominiak of the US EPA. >We met and >spoke again on Tuesday at the public hearing held by the US >EPA on Tuesday >this week in Arlington, VA. >I have a dual role in DuPont. One is as a business manager for a >fluorosurfactants and additives business. And the other is an external >company role in working with the global regulatory agencies and Telomer >consortium (see below). >You were copied on an E-mail note to Mary written by Lt. Col. >Isaac Atkins, >Jr on February 13, 2001referencing a AFFF Workshop held on 16 >March 2001. >This E-mail note refers to a letter (which was attached) >written by Curtis >Dowling of the Office of the Under Secretary of Defense. The subject >letter largely deals with the subject of PFOS chemicals, their >use in fire >fighting, and the proposed ban by the US EPA. >In this letter signed by Mr. Dowling was a comment in the >beginning of the >second paragraph and I quote " PFOA and telomer are also >persistence in the >environment and more toxic than PFOS." We at DuPont do not >understand the >basis on which Mr. Dowling could make such a statement about Telomer >products. Naturally we would like to see the data that led US00003056-D >Mr. Dowling to >the conclusion he cited in this 12 February 2001 letter. We >surely would >welcome the opportunity to talk to you and Mr. Dowling about DuPont >Fluorotelomer products as it relates to descriptive biology/toxicology, >environmental fate and effects, and overall exposure >assessment. I would >like the opportunity to share our data, our testing program, >and relate the >outcome of several meetings we have had with the US EPA over >the past year. >In addition, most of the global telomer manufacturers have >joined together >to form a consortium group called the Telomer Research Program (TRP) to >further study our products. I can also describe this in >detail for you. >Please let me know how you would like to proceed. >I can be reached by E-mail by just responding to this note or using >stephen.h.korzeniowski@usa.dupont.com. This is usually the >easiest way to >reach me due to my travel schedule. I can also be reached by phone on >302-992-3672 and fax - 302-892-1135. >I look forward to discussing these matters with you. >Thank you in advance for your consideration. >Steve US00003057-D Mr. Stephen H. Korzeniowski Business Manager Fluorosurfactants and Additives E. I. Dupont de Nemours & Co.,Inc Dear Mr. Korzeniowski: Thank you for your letter to Dr. Dierdorfexpressing your interest in our Aqueous Film Forming (AFFF)Workshop ofMarch 16,2001. The purpose ofthe workshop was to provide a forum for discussion ofthe Environmental Protection Agency's(EPA)proposed rule that calls for the voluntary phase-out ofperfluorooctly sulfonate(PFOS)chemicals to the Department ofDefense by 2003. DoD is concerned about the availability ofPFOS for use in AFFF and the pending phase-out rule's impact on military fire-fighting capabilities. Dr. Dierdorfasked me to respond to you because I am the author ofthe letter mentioned in your correspondence. The application of AFFF in firefighting is inherently dispersive and results in the distribution of AFFF's chemical components on the surface and in the groundwater. Concern about this distribution prompted Military Service Departments to investigate the biodegradation, possible remediation, toxicity, fate and transport of many ofAFFF's components. These studies date back to 1983 or earlier and are on going. Based on these studies and published literature, the "Lowest Observed Adverse Effect Level"(LOAEL)for perfluorinated carboxylic acids is 0.1 mg/kg/day for mice.' The LOAEL for perfluorooetanyl sulfonates is 0.4 mg/kg/day.' My assertion that PFOA is more toxic than PFOS is based on these data. The association ofthis result with telomer is based on the below unpublished Air Force tests. Several weeks after a large-scale fire-fighting operation using AFFF in Jacksonville Bay, Florida, allegations ofsurfactant related bud kill caused the Air Force to screen AFFF's components to determine if they were non-persistent. The perfluorinated carboxylic and sulfonic acid surfactants were known to be persistent, leaving telomer surfactants as the only potentially non-persistent, commercially available, fluorosurfactant candidates. During 1998, the Air Force Research Laboratory, Fire Technology Group at Tyndall Air Force Base,Florida conducted the screening by monitoring the changes in "Soluble Chemical Oxygen Demand"(COD)and surface tension during biodegradation. Standard procedures for measuring "Biological Oxygen Demand" over a period of28 days were used. Purely by coincidence, the telomer-tested surfactant samples were identified as "Zonyl" branded surfactants, which were supplied by your company. Results indicated that the telomer fluorosurfactant did biodegrade as shown by decreased soluble COD,however,the surface tension remained essentially unchanged. Control samples ofhydrocarbon Developmental toxicity of perfluorodecanoic acid in C57BL/6N mice. Harris MW, Birnbaum LS, Fundam Appl Toxicol, 1989, 442-8 (1989). 2 3M Submissions in EPA Docket AR-226. US00003058-D surfactants showed decreased soluble COD indicating biodegradation and as expected an increase in surface tension to that ofwater. The research staffinvolved in this work found the results consistent with the degradation oftelomer surfactants to perfluorocarboxylic acids. In the case ofZonyl TBS, the only biodegradable segment is the 1,1,2,2 tetrahydro segment, which can only result in formation ofperfluorononanoic acid. They considered this information insignificant at the time with the required documentation being extensive research notes. I'm sure industry efforts in this area are being revived in light ofthe EPA's pending regulatory action. Dr. Dierdorfhas been collaborating with manufacturers offluorosurfactants to ensure nonpersistent surfactants are developed and commercially available. These chemicals provide the properties essential to effective AFFF fire fighting. Ifyou want a copy ofthe Air Force's unpublished experimental data, please contact Mr. Dick Vickers at(850)283-3707,Dick.Vickers@tyndall.afmil. Curtis M. Bowling Assistant Deputy Under Secretary of Defense (Force Protection US00003059-D AN ABSTRACT OF THE THESIS 0F Cheryl Moody Bartel for the degree of Doctor of Philosophy in Chemistry presented on November 23, 1999. Title: Occurrence and Distribution of Per?uorinated Surfactants in Groundwater Contaminated by Fire-Fighting Activity Redacted for privacy Abstract approved: 1' Jennifer A. Field Aqueous ?lm forming foams are used to extinguish hydrocarbon-fuel ?res and repetitive use, particularly at military sites, has led to wastewater and subsequent groundwater contamination. Per?uorinated surfactants are an important class of specialty chemicals that are used in AF FF agents and have physio-chemical properties that di??erentiate them from hydrocarbon surfactants. In the past, the environmental behavior of per?uorinated surfactants has received little attention, and how the unique properties affect the behavior of per?uorinated smfactants in the environment and their potential impact on eo?contaminant transport and biodegradation are unknown. An analytical method was developed to determine per?uorocarboxylates in groundwater. Solid-phase extraction and derivatization techniques were used to form the methyl esters of per?uoroearboxylates that were then analyzed by gas chromatographyimass spectrometry. Per?uorocarboxylates containing 6 to 8 carbons were detected in groundwater samples collected from Naval Air Station Fallon, NV, Tyndall Air Force Base, FL, and Wurtsmith Air Force Base, MI, with total concentrations ranging from 3 to 7,090 ug/L. The homologous series of per?uorocarboxylates observed in groundwater from the three military sites as well as in commercial AF FF mixtures consisted of even and odd number per?uorinated carboxylates, which is indicative of the electrochemical ?uorination process. At Air Force Base, per?uorocarboxylates detected 500 from the source area were estimated to have a minimum residence time of to 15 years. Additionally, the per?uorocarboxylate concentrations observed in gromdwater are signi?cantly lower than the corresponding methylene blue active substances concentrations, which indicates that there are additional anionic surfactant Species present in the groundwater. Perfiuorinated carboxylates measured at Naval Air Station Fallon, NV, Tyndall Air Force Base, FL, and Wurtsmith Air Force Base, MI, which have not been used since 1988, 1992, and 1986, respectively, provide direct ?eld evidence that this class of per?uorinated surfactants persist under prevailing groundwater conditions and potentially could be used as unique tracers of groundwater impacted by repetitive ?re-training exercises. Occurrence and Distribution of Per?uorinated Surfactants in Groundwater Contaminated by Fire-Fighting Activity by Cheryl Mood),r Bartel A THESIS submitted to Oregon State University in partial ful?llment of the requirements for the degree of Doctor of Philosophy Presented November 23, 1999 Commencement June 2000 Doctor of Philosophy thesis of Cheryl Moody Bartel presented on November 23, 1999. APPROVED: Redacted for privacy MWM, r?arcsenting?Eh?emistry Redacted for privacy Heady Department of Chemistry Redacted for privacy ?an of Graduate Schbol I understand that my thesis will become part of the permanent collection of Oregon State University libraries. My signature below authorizes release of my thesis to any reader upon request. Redacted for privacy K?E??erfl? Moody Wfluthor ACKNOWLEDGEMENTS The author wishes to thank her research adviser, Dr. Jennifer Field, for her advice and guidance throughout this research project. Dr. Doug Barofsky, Dr. Jonathan Istok and Dr. John Westall are gratefully acknowledged for their technical assistance and advice on the final presentation of this manuscript. The author thanks Donald Hagen, Rick Payfer, and Eric Reiner of 3M Co.; Lee Chambers and Martial Pabon of Elf Atochem; Mitch Hubert of Ansul Inc, and Dennis Seisun of IMR International for valuable discussions and technical assistance. I would also like to thank Walter Giger, Chang J'ho, and Erik Kissa for reviewing draft manuscripts. Ron Hoeppel and Art Fisher from Naval Air Station Fallon, Bill Johnson from the University of Utah and Erica Becvar from Tyndall Air Force Base, FL, are gratefully acknowledged for facilitating ?eld sample collection. The author thanks Michael Barcelona and the National Center for Integrated bioremediation research and Development Field Operations Of?ce for valuable discussions, facilitating field sample collection and technical assistance. Sheridan Haack from the United States Geological Survey is acknowledged for technical assistance and for facilitating ?eld sample collection. Steven Strauss, Gretchen Hebert and Matthew Odom from the Department of Chemistry, Colorado State University and Edward Furlong from the United States Geological Survey are acknowledged for additional liquid spectrometry analysis of groundwater samples. This work was ?nancially supported, in part, by the Oregon State Department of Chemistry (N. L. Tartar Research Fellowship) and by a grant from the Environmental Protection Agency (OER R821195). The author acknowledges the NIEHS Environmental Health Science Center Grant No. for its support through the Mass Spectrometry Core Facility. Additionally, the author would like to thank her parents and family for their generous emotional and ?nancial support. The support provided by friends and extended family throughout my education is sincerely appreciated. Specials thanks to Joe Bartel who has been an endless source of strength and inspiration. TABLE OF CONTENTS 1232 CHAPTER 1: INTRODUCTION: PERFLUORINATED SURFACTANTS AND THE WRONMENTAL IMPLICATIONS OF THEIR USE IN FIRE- FIGHTING FOAMS Abstract Introduction - Perfluorinated Surfactant and Properties Per?uorinated Surfactants in Aqueous Film Forming Foams AFF Wastcwater and its Impact on Wastewater Treatment .. Pcr?uorinated Surfactants in Groundwater Bicdegrada?on C0~Contaminant Transport and Degradation .. . . .. Analytical Future Challenges .. .. Literature Cited CHAPTER 2: ANALYTICAL METHOD FOR THE DETERMHNIATION OF PERFLUOROCARBOXYLATES IN GROUNDWATER IMPACTED BY FIRE-FIGHTING ACTIVITY . . Experimental .. ..1 ..2 ..4 .6 ..10 13 19 24 .26 .36 TABLE OF CONTENTS (Continued) Page Results and Discussion 41 Acloiowledgments 52 Literatme Cited nooeJ-DDOIa-t etc-11" CHAPTER 3: OCCURRENCE AND DISTRIBUTION OF PERFLUORINATED SURFACTANT 1N GROUNDWATER ASSOCIATED WITH AIR FORCE BASE FIRE-FIGHTING Introduc?onSB Experimental Section 61 Results and Discussion 66 Acknowledgments78 Literature Cited 79 BIBLIOGRAPHY 85 LIST OF FIGURES Fiwe Page 1.1. 1.2. 1.3. 2.1. 2.2. 2.3. 2.4. 3.1. 3.2. 3.3. Percentage breakdown of United States consumers of AF FF products, where the hydrocarbon processing industry and municipal represent such entities as oil re?neries and ?re departments, respectively. 9 Mixed monolayers at the air-aqueous and aqueous-hydrocarbon phase interfaces. ..11 Breakthrough curves for bromide and per?uorooetane sulfonate obtained from a push-pull ?eld test]?l Map of Naval Air Station Fallon, NV, and Tyndall Air Force Base, FL, ?eld sites indicating location of grotmdwater wells and direction of regional groundwater ?ow. Typical EI GCMS chromatogram of PFCB and PFC12 standards and per?uorinated carboxylates, including PFCT, PFC8 and PFC12 (spiked) in Naval Air Station Fallon, NV, groundwater. 43 EI mass spectrum of methyl PFC8 and an ECNI mass Spectrum of methyl ECNI mass ofmethyl PFC6 and methyl 50 Map of Wurtsmith Air Force Base field site Fire-Training Area Two indicating locations of grotmdwater wells and direction of regional groundwater ?ow. The study site location is highlighted on the map of Michigan (inset) 62 Distribution of per?uorocarboxylate concentrations methylene blue active substances concentrations (pg/L) in shallow FT monitoring wells 71 Distribution of Speci?c conductance measurements (quem) in shallow FT monitoring wells 75 LIST OF TABLES Table . Page 1.1. 1.2. 2.1- 2.2. 3.1. Of ??nal-0091311010 Chemical composition of 3M CF Light WaterTM Aqueous Film Forming Foam Concentrate (St. Paul, MN). 13 Recovery of PFCS and PFC12 Spiked into groundwater samples from Naval Air Station Fa?on,NV46 Concentrations of per?norinated carboxylates in groundwater samples from Naval Air Station Fallon, NV and Tyndall Air Force Base, FL. 48 Summary of groundwater data from PTA-02 sampled wells in November 1998 and June 1999. 69 PREFACE Chapter 1 provides an introduction to aqueous ?lm fonning foams which are used to extinguish hydrocarbon-Eel ?res. Their repetitive use, particularly at military sites, has led to wastewater and subsequent groundwater contamination. Perfluorinated smfactants are an important class of specialty chemicals that are used in AF agents and in the past, the environmental behavior of per?uorinated surfactants has received little attention. The second chapter of this study describes the isolation, identi?cation and quanti?cation of per?uorinated earboxylates in groundwater impacted by ?re?naming activities at Naval Air Station Fallon, NV and Tyndall Air Force Base, FL. Strong anion exchange disks were used to extract per?uorocarboxylates from groundwater collected from ?re-training sites located at the two military facilities. The developed method is the primary tool that was then used to quantitatively determine per?uorocarboxylates in groundwater samples collected for a more extensive groundwater study described in Chapter 3. The work presented in Chapter 3 aids in the understanding of the environmental behavior of one class of per?uorinated surfactants, per?uorocarboxyiates, since virtually no information exists on their occurrence, transport, and biodegradability in the environment. Commercial mixtures containing per?uorinated surfactants were applied at Wurtsmith Air Force Base, Oscoda, MI, including the Fire-Training Area 2 and a site where an airplane crashed. Comparison of the per?uorocarboxylate concentrations to other bulk chemical indicators such as Speci?c conductance, total organic carbon, and methylene blue active substances, add context to the environmental occurrence and distribution of per?uorocarboxylate surfactants. - Occurrence and Distribution of Per?uorinated Surfactants in Groundwater Contaminated by Fire-Fighting Activity Chapter 1 Introduction: Per?uorinated Surfactants and the Environmental Implications of their Use in Fire-Fighting Foams Cheryl A. Moody1 and Jennifer A. Field1 1L'Ieparlmoent of Chemisn'y and of Environmental and Molecular Toxicology, Oregon State University, Corvallis, Oregon 97331 Reprinted with permission ?om Environmental Science and Technolog, submitted for publication. Unpublished work copyright 1999 American Chemical Society. Abstract The recent identi?cation of one class of ?uorinated surfactants in. groundwater impacted by ?re-?ghting activity has created an awareness of the potential environmental issues resulting ?om the use of aqueous ?lm forming foam (AF FF) agents. Aqueous ?lm forming foams are used to extinguish hydrocarbon-fuel ?res and their repeated usage particularly at military sites has led to groundwater. Formulations of agents include ?uorinated surfactants, which are an important class of specialty chemicals that have physio-chemical properties that differentiate them from hydrocarbon surfactants. Little is known about the occurrence, transport, biodegradation and toxicity of ?uorinated surfactants in the environment. The fact that ?uorinated surfactants as well as other AF FF components conoccur with priority pollutants jet fuel components and chlorinated solvents) complicates studies on their fate and effect in the environment. Research is needed to su?iciently characterise the structures and environmental properties of ?uorinated surfactants. Additionally, the environmental behavior of the AF FF mixtures and complex AF F-wastewaters needs to be investigated. Introduction Fluorinated surfactants constitute an important class of ?uorinated compounds that are utilized in ?re-?ghting applications, herbicide and insecticide formulations, cosmetics, greases and lubricants, paints, polishes, and adhesives (1-4). For example, per?uorooctane sulfonate is an important surfactant itself as well as a precursor to other ?uorinated surfactants and pesticides (5). The Organization for Economic Cooperation and Development (OECD) lists per?uorinatcd C5-C18 compounds, which includes most per?uorinated surfactants, as high-production?volume (HPV) chemicals. High- production volume chemicals are those chemicals manufactured or imported in the US. in volumes exceeding 1 million pounds (6). Fluorinated surfactants are different from hydrocarbon surfactants. Although the polar head groups may be similar between hydrocarbon and ?uorocarbon surfactants, the non-polar per?uorocarbon tail is both hydrophobic and oleophobic (oil- repelling), which is in contrast to the tail group of hydrocarbon surfactants, which are only considered hydrophobic in nature. For this reason, ?uorinated surfactants exhibit both hydrophobic and oleophobic characteristics, which accounts for their unique physio- chemical properties as will later be addressed (I). Fluorinated surfactants may be classi?ed as either per?uorinated, in winch all hydrogen atoms are substituted by ?uorine atoms, or as partially-?uorinated where some carbons contain hydrogen atoms. Like other surfactant classes, ?uorinated surfactants generally are classi?ed into one of four categories: nonionic, anionic, cationic, and amphoteric, with anionic ?uorinated surfactants being the most important class (I). Fluorinated surfactants comprise a unique class of Specialty chemicals whose environmental behavior has received little attention. Consequently little information is available to permit a complete life-cycle analysis. The focus of this review is to l) characterize the unique properties of ?uorinated surfactants, 2) describe how the unique properties are utilized for the purpose of ?ghting ?res, and 3) evaluate how the unique properties might affect the behavior of per?uorinated surfactants in the environment and their potential impact on co-contarninant transport and biodegradation. Finally, the need for new analytical methods to measure per?uorinated surfactants is highlighted as a requirement for addressing questions about the occurrence, behavior, and impact of this specialty chemical class in the environment- Per?uon?nated Surfactant and Properties Two principal processes used in the manufacturing of ?uorinated surfactants are electrochemical ?uorination and telomerization (I). With electrochemical ?uorination, the substance to be ?uorinated is dissolved in hydro?uoric acid and an electric current is passed through the media (I, 7). All hydrogen molecules are replaced by ?uorine and per?uorinated molecules result. DeSpite low to moderate yields of per?uorinated compounds and many side products, electrochemical ?uorination is economically attractive because of the relatively low cost of electricity as well as that of the hydrogen ?uoride reagent (7). With the electrochemical ?uorination process, per?uorinated compounds with homologous series of even and odd number per?uorocarbons are generated (I, 8). In contrast, the telomerization process reacts a molecule called a telogen, with two or more unsaturated molecules called taxogens, which creates a telomer that contains only an even number of carbon atoms Because odd and even number per?uorocarbons result from elecn-ochemical ?uorination, the DoomTenoe of odd and even carbon per?uorinated surfactants in the environment can potentially be traced to manufacturers that use the electrochemical ?uorination process (9). When ?uorine is a substituent in organic compounds, unique chemical properties are observed due to the electronegativity of ?uorine as well as the overlap between the 25 and 2p orbitals of ?uorine and the corresponding orbitals of carbon (I, 7). The presence of ?uorine atoms contributes to the rigidity of per?uoroearbon chains relative to hydrocarbon chains. The highly polarized carbon ?uorine bond is the strongest of known covalent bonds With the average C-F bond approximawa 25 kcalfmole stronger than - the corresponding bond in monochloroalkanes (7). Additionally, ?uorination usually strengthens the adjacent C-C bonds (7). The properties of hydrocarbons and, therefore, surfactants, are altered signi?cantly when ?uorine atoms are substituted for hydrogen atoms (1). Per?uorirtated surfactants are more thermally-stable than their corresponding hydrocarbon analogues. In particular, per?uorocarboxylic acids and per?uoroalkanesulfonic acids are considered the most thermally-stable fluorinated surfactants (I). In addition to thermal stability, per?uon'nated surfactants are stable to acids, bases, oxidants and reductants This stability allows ?uorinated surfactants to remain intact in environments where hydrocarbon surfactants are degraded. Per?uorinated anionic surfactants have high-acid strength relative to their hydrocarbon analogs due to the effects of ?uorine substitution, For example, the replacement of hydrogen atoms by ?uorine atoms on octanoic acid to form perfluorooctanoic acid decreases the pKa from 4.89 to 2.80 (Table 1.1) (I, 7). Per?uorinated surfactants are much more surface active than hydrocarbon surfactants (I. 10). The substitution of ?uorine atoms for hydrogen atoms decreases their surface activity for aqueous solutions, which promotes micellization at lower concentrations the critical micelle concentration and lowers the surface tension relative to that of other hydrocarbon analogs (I). For example, the surface tension of perfluorooctanoic acid has been reported as 15.2 dynes?cm (I). The CMC values for C7 and C8 ?uorinated surfactants per?uorocarboxylates and per?uoroalkane sulfonates) are approximately equal to those of C11 and (312 hydrocarbon surfactants (I). The cost of ?uorinated surfactants is higher relative to that of hydrocarbon surfactants. Because of the high prices of ?uorinated surfactants, fluorosurfactant applications are limited to problems that conventional, lower-priced surfactants can not address (4, I 1). Within a speci?c application, ?uorinated surfactants are typically cost effective because their relatively high price is offset by the low concentrations needed to achieve the reduction in interfacial tension or to form micellar solutions (I). In some applications such as AF FF, a mixture of a ?uorinated surfactant and a hydrocarbon-based surfactant are more cost effective andfor perform better than either surfactant separateiy Per?uorinated Surfactants in Aqueous Film Forming Foams Hydrocarbon-fuel ?res pose a serious threat to life and property, and require immediate response. To enable a quick response to hydrocarbon-fuel ?res, effective and Table 1.1. Properties of pcr?uorooctanoic acid. Property Pcr?uorooctanoic acid pKaI 2.80 Critical micellc concentration1 8.7-9.0 Interfacial tern-non3 15.2 1Units for critical micellc concentrations are mMolcst (1). 3Units for surface tension arc (10). ef?cient ?re-extinguishing agents are needed to prevent damage and re-ignition of the ?res. Aqueous ?lm forming foams were developed in the 1960s as important tools for extinguishing ?res involving ?ammable liquid fuels gasoline, kerosene) (12). I Due to the presence of large quantities of ?ammable liquids, municipal ?re departments), hydrocarbon-processing industry oil re?neries), and military sectors utilize (Figure 1.1), with the military comprising 75% of the total market, while the municipal and hydrocarbon-processing industry represents 13% and respectively (13). In 1935, the United States market for products 3% and 6% concentrates) was 6.8 million with a total revenue of 10 million dollars in U. S. sales The military was the single largest consumer of AF FF agents in 1985, with consumption totaling 5.1 million (13). For historical reasons, the U. S. Department of Defense Military Speci?cations Regulations have driven the requirements for AF FF performance by establishing performance criteria. Commercial AF FF formulations are complex proprietary mixtures whose major components include a solvent, which is typically butyl carbitol; fluorocarbon (per?uorinated anionic and partially-?uorinated amphoteric) surfactants; and hydrocarbon-based surfactants (Table 1.2). Fluorinated surfactants in mixtures contribute to the performance of foams as the primary ?re extinguishing chemical and as vapor sealants that prevent re-ignition of fuel and solvents (I, I 4, 15). To evaluate the spreading of and the spontaneous formation of ?lms, a spreading coef?cient can be calculated. The spreading coef?cient (SC) (16) evaluates the reduction in surface and - Military: 75% 4-41 Municipal. 13% - Hydrocarbon Processing Industry: 5% We Other: 7% Figure 1.1. Percentage breakdown of United States consumers of AF FF products, where the hydrocarbon processing industry and municipal represent entities such as oil re?neries and ?re departments, respectively (13). 10 interfacial tension and is de?ned as the difference between the surface tension of a mode] hydrocarbon phase (Ham) (such as cyclohexane at 25 dynes/cm), the surface tension of the aqueous solution (7mm), and the interfacial tension between the aqueous solution and hydrocarbon (I 7). SCtn-iuwufcyulaeum} Tcydahum Yuma: Timeless (1 For military speci?cations the spreading coefficient of the mixture calculated from Equation (1) must be positive (I 8). For example, the ?uorinated surfactant components in lower the surface tension of the aqueous solution to 15-20 dynesfcm while hydrocarbon surfactants lower the interfaciai tension between the aqueous solution and the hydrocarbon phase burning fuel) to 0?2 dynesfcm (19). Thus, the ?lms formed by ?uorocarbon and hydrocarbon solutions consist of two-mixed monolayers of surfactants where the air-aqueous phase monolayer is dominated by the ?uorocarbon surfactant and the aqueous?hydrocarbon phase monolayer is dominated by the hydrocarbon surfactant (Figure 1.2) (19). Wastewater and its Impact on Wastewater Treatment Facilities At installations, such as military bases, ?re?training exercises are part of emergency preparedness plans and therefore are conducted with some freguency. A ?re? training exercise typically consists of ?ooding a ?re pit with ?ammable liquids off- ll Air I Fluorocaroon Surfactant Aqueous Surfactant Solution 0 drooarbon I urlactant Hydrocarbon hose Figure 1.2. Mixed monolayers at the air-aqueous and aqueous-hydrocarbon phase interfaces. Adapted from Reference (1 9). 12 speci?cation jet fuel and waste solvents such as chlorinated solvents (20-22) igniting the ?uids, and subsequently extinguishing the ?re with ?re-?ghting agents (21). For example, training exercises occurred on a weekly to basis (9) at Naval Air Station (N AS) Fallon, NV, and consisted of igniting fuel (average 3000 L/week) (21) and extinguishing the ?re with 1200-3200 of aqueous AF FF solutions. Typically, at this site and others, disposal options for AF FF wastewater included discharge into a wastewater treatment facility andx'or directly onto the ground adjacent to the training facilities. If too much ?re-?ghting foam is. discharged to a wastewater treatment facility at one time, excess foaming may occur, which results in aesthetic and operational problems in sewers and wastewater treatment facilities. Another concern for wastewater treatment facilities is that in-coming 1wastewaters have high biological (BOD) and chemical oxygen demands (COD) (23). For example, for 3M Light WaterTM AF product FC- 203 as a 3% solution, the BOD, (5 day biological oxygen demand), (20 day biological oxygen demand) and COD are 10 ?mg/L, 3.2 10 tug/L, and 3.2 10 mg/L, respectively, and can lead to signi?cantly higher values than those normally,r found at treatment plants (100-400 mg/L BOD5 (23, 24). One of the principle contributors to the high BOD and COD of AF FF is the organic solvent component, butyl carbitol (Table 1.2). In addition to the foaming BOD and COD problems associated with residual fuel is part of AF FF wastewater (I2, 25). Residual fuel in combination with components and potential combustion products complicates the characterization of wastewater and thus its disposal in an economically?and environmentally- 13 Table 1.2. Chemical Composition of 3M FC-203CF Light WaterTM Aqueous Film Forming Foam Concentrate (St. Paul, MN) (73). Chemical Name Percent of Total Composition Water 69.0-71.0 Diethylene glycol butyl ether (butyl carbitol) 20.0 Amphoteric ?uoroalkylamide derivative 1-5 salts 1.0-5.0 Per?uoroalkyl sulfonate salts 0.5-1.5 Triethanolamine 0.5-1.5 (corrosion inhibitor) 0.05 14 acceptable manner Solutions containing free and emulsi?ed oil, ?lel, and components were shown to adversely affect activated sludge processes (12, 25) and the performance of anaerobic sludge digestors (27) in wastewater treatment facilities. Because of the potential problems at wastewater treatment facilities, characterization of wastewater is required in some instances prior to gaining approval to discharge the waste to a wastewater treatment facility. Characterization methods generally are lacking, and thus some ?re-training facilities have had to impound wastewater over extended periods of time- Aqueous ?lm forming foam wastewater and its treatinent have been the focus of investigative studies by the U. S. Department of Defense (26). Several pre-treatments such as precipitation, coagulation, adsorption on activated carbon and ultra?ltration (12, 26) are being evaluated for the treatment of AF FF wastewater before diSpensing it to a wastewater treatment facility (23, 25, 28-30); however, few pretreatment strategies are being implemented. Currently, treatment ef?ciency is judged using only general, non- speci?c parameters such as methylene blue active substances (MBAS) and total organic carbon. Unfortunately, analytical methods are not yet widely available that permit the Specific assessment of the effectiveness of treatment technology ef?ciency on ?uorinated surfactant removal. Per?uurinated Surfactants in Groundwater of contaminated groundwater are associated with past ?re-training sites at several military bases in the United States (20-22, 31' -33) including NAS Fallon, NV, Tyndall Air Force Base, FL, and Wurtsmith Air Force Base, where AF FF wastewater 15 has entered groundwater without prior treatment. Most of these plumes have been characterized with respect to fuel and solvent components unlike the surfactant components, which have received little attention primarily due to the lack of appropriate analytical techniques. A few early reports tentatively identi?ed the presence of ?uorinated surfactants in groundwater impacted by ?re-?ghting activities at Tyndall Air Force Base, FL (31, 3 4). A recent report described the development of an analytical method that permitted the de?nitive identi?cation of per?uorocarboxylates surfactants in groundwater at NAS Fallon, NV, and Tyndall Air Force Base, FL, at concentrations ranging from 125 to 7090 ugfL (9). A current study at Air Force Base, MI, has revealed a plume of per?uorocarboxylates 500 in length with concentrations ranging from 3 to 110 ugfL (3.5, 36). I At each field site both even- and odd-numbered carbon per?uorocarboxylates were identi?ed, which is indicative of- product formulations manufactured by the electrochemical ?uorination process (9). This ?nding is consistent with the fact that the 3M Co., a company that uses electrochemical ?uorination to manufacture per?uorinated surfactants, has held the military contract to supply AF FF for the last 25 years. Laboratory and field data regarding the transport of fluorinated surfactants in groundwater are virtually nonexistent. In an attempt to address this data gap, we performed a single-well push-pull test (3 7) using perfluorcoctane sulfonate in order to obtain transport information. The push-pull test consisted of the injection of a prepared test solution into the saturated zone of an aquifer using an existing monitoring 16 well, followed by the extraction of the test solutionfgroundwater mixture from the same location. For this esperiment, 50 of injeetate containing 97 mg/L bromide (non- reactive tracer) and 26 mg/L potassium per?uorooctane sulfonate, which is one of the major per?uorinated surfactants present in some AF FF mixtures, was injected into a well over a period of 4 hr. Immediately after injection, a total of 98 was extracted from the well over a 9-hr period. Samples were taken during the extraction phase and analyzed for bromide and perfluorooctane sulfonate by ion chromatography and MBAS, respectively. It should be noted that the MBAS test is non-speci?c and does not allow for the deteetion and quantitation of individual anionic surfactant classes. However, for this ?eld study where only a single per?uorinated surfactant was present in the injectate solution and none was present in the backgromd groundwater, the limitations of MBAS did not hinder its application as the analytical method for per?uorooctane sulfonate. Breakthrough curves were constructed for bromide and per?uorooctane sulfonate (Figure 1.3) by plotting the relative concentration for each solute, where is the measured concentration and CD is the injected concentration, versus the cumulative extracted volume divided by the total injected volume of the test solution. Identical breakthrough curves for bromide and per?uorooetane sulfonate were observed indicating that per?uorooctane sulfonate was transported conservatively in this aquifer. In contrast, breakthrough curves for a mixture linear sulfonate (LAS) obtained from a separate single-well push-pull test conducted in the same aquifer (data not shown) indicates the retardation of LAS relative to that of bromide (38). Preliminary data indicates for a given site, per?uorooctane sulfonate (C8) is conservatively transported while its hydrocarbon surfactant analog of 2 to 5 more carbon atoms is cxca 1.50 1.25 - 1.00 0.75 0.50 0.25 0. 00 Per?uamoctane sulfonate Bromide Figure 1.3. Breakdlrough curves for bromide and pcr?uomoctane Sl?fonate obtained from a push?pull ?eld test. Extracted Volumellnjected Volume 17 1 3 retarded Because per?uorocarboxylates are weaker acids, their tl'aIISpOI?t may be affected by pH and ionic strength. Therefore, research is required to fully investigate the transport behavior of the per?uorinated surfactants present in However, the conservative transport per?uorooctane sulfonate observed in the ?eld study indicates that per?uorinated surfactants may be good tracers for groundwater. Biodegradation The extent to which AF FF components and priority pollutants in wastewater biodegrade is quite varied. A material safety data sheet for a current AF FF product states that the product contains one or more organic ?uorochemicals that have the potential to resist degradation and persist in the environment (39). The detection of per?uorocarboxylates in groundwater at NAS Fallon, NV, and Tyndall Air Force Base, FL, which have not been used for 7-11 years (9) is consistent with both AF FF product labeling and the widely-held view that per?uorinated surfactants are not biodegradable. Few studies have been conducted to investigate the biodegradability of per?uorinated or partially-?uorinated surfactants Q, 3, 12, 40). Per?uorooctane sulfonic acid was not degraded under aerobic or anaerobic conditions (2 7), while a partially- ?uorinated surfactant, 1H, 1H, 2H, 2H-per?uorooctane sulfonic acid, was partially degraded both aerobically and under sulfur-limiting conditions (2, 3, 5). Biodegradation of partially-?uorinated surfactants appears to be limited to the non-?uorinated portion of the molecule (2, .5, 41). For example, 1H, 1H, 2H, 2H-perfluorodecanol was biotransformed to per?uorooctanoate The recalcitrant nature of per?uorinated 1 9 compounds is attributed, in part, to the strength of the carbon??uorine bond (1, 2, 42) as well as the rigidity of the per?uorocarbon chain (2, 43). In contrast to the recalcitrant nature of the ?uorinated surfactant components present in AF FF mixtures, the alkyl sulfate hydrocarbon surfactants (Table 1.2) (26) present in some AF FF formulations is considered biodegradable under aerobic and anaerobic conditions (44). As mentioned previously, the solvent component of AF FF formulations is also biodegradable as indicated by high BOD values. As a result, the high BOD of butyl carbitol may in?uence the biogeochemical conditions of groundwater by consuming oxygen and thus driving systems anaerobic. Corrosion inhibitors are a component found in AFF formulations that have been shown to persist in the environment (45, 46). While some information is available on individual AF FF components, virtually nothing is [mount about the biodegradation of this complex mixture and any synergistic effects of components upon priority pollutants biodegradation under actual subsurface conditions. Additional research is required to understand the biodegradation components. Ctr?Contaminant Transport and Degradation Because some per?uorinated surfactants appear to persist in groundwater they may affect the environmental fate and transport of other co-contaminants jet fuel and nichloroethylene) that are present in wastewater. Unforttmately, the physical character number of liquid phases) and chemical composition of AF wastewaters have not been widely characterized. However, it is likely that wastewaters resulting from the application of on burning solvents, some of which form dense 20 non-aqueous phase liquids or DNAPLs, are multi-phased systems. Due to the complex nature of wastewater there are a number of potential interactions between components and co-contaminants that can affect co-contaminant transport and biodegradation. For example, some hydrocarbon surfactants above their CMC are known to enhance the apparent solubility andfor the mobility of DNAPL in contaminated aquifers (4 7-49). Because surfactants can cause large reductions in water-DNAPL interfacial tension, surfactants may promote the displacement of residual DNAPL and hence its more rapid migration in the subsurface. The ability of hydrocarbon surfactants to increase the solubility or mobility of DNAPLs is dependent on the physical prOperties of the particular surfactant. Given the oleophobic nature of the per?uorocarbon chain, it is likely that on a per carbon basis, per?uorocarbon surfactants are less effective in increasing the solubility of DNAPL than hydrocarbon surfactants as well as less effective in lowering aqueous-DNAPL interfacial tensions However, to date studies have not been conducted to determine the extent to which ?uorinated surfactants can increase the solubility andfor mobility of DNAPL in the subsurface. By analogy to wastewater treatment systems where AF FF wastewater adversely a?ected the performance, per?uorinated surfactants may have an effect on groundwater microbial populations and their ability to degrade co-contaminants (I2, 25, 27). No information exists on the potential impact of per?uorinated surfactants on microbial populations. Recent studies with hydrocarbon Surfactants have indicated either inhibition (50-52) or promotion {53-55) of organic contaminant degradation The ability of a surfactant to promote or inhibit co-contarninant biodegradation also appears structure speci?c. Unfortunately, structure-activity relations have not been established for 21 ?uorinated surfactants. Therefore, it is not yet possible to predict a prior-i the effect that per?uorinated surfactants will have upon the biodegradation of other contaminants in AFF F-contarninated groundwater. Toxicity The toxicity of formulations to marine and freshwater organisms has been tested in laboratory studies Various diluted AF FF agents were considered mildly toxic to marine life at concentrations near 6.0 g/L (24). Additional components of interest found in concentrate formulations are the corrosion inhibitors such as tolyln'iazole. Recent toxicological studies on toyltriazoles have shown that these compounds have moderate to high toxicity (45. 46). However, realistic toxicity evaluations of mixtures and AF FF wastewater in the environment are dif?cult because AF FF wastewaters are complex mixtures that contain AF FF components, primary pollutants, as well as toxic bum products. In addition, differential degradation during transport of AF FF wastewater components will change the mixtures composition and toxicity over distance and time. Finally, the toxicity of these types of complex mixtures is dif?cult to assess because of the potential synergistic effects between mixture components, making it dif?cult to predict a priori the toxicity of these mixtures in the environment. Release of ?uorinated surfactants to surface waters is not a recommended by manufacturers as a route of disposal for wastewater (56). Fortunately, reports of AF FF wastewater discharge to surface waters are limited. However, AF FF wastewater released to a Florida river in 1993 has been the subject of investigation as a possible cause of sea bird illnesses and deaths in the region (5 58). By analogy to 22 hydrocarbon surfactants, per?uorinated surfactants in wastewater can potentially cause birds to loose their natural oils, thus causing birds to die ?-om hypothermia (59). Analytical Considerations The determination of per?uorinated surfactants is problematic (I2), in part, because the surfactants are nonvolatile and generally do not contain chromophores, which limits their detection using commonly available analytical detectors. The scarcity of analytical methods for ?uorinated surfactants is in sharp contrast to numerous methods available on hydrocarbon surfactant analysis (1 I, 60-62). Creating an analytical method to isolate per?uorinated surfactants from environmental samples is complicated due to the proprietary nature of AF FF formulations and therefore, the lack of knowledge regarding the speci?c structure of per?uorinated surfactants. Furthermore, the isolation of per?uorinated surfactants from water is complicated by their high water solubility. The non-speci?c determination of the total organo?uorine content of a water sample may be obtained using the combustion method (I, 63). A water sample 10 mL) introduced into the torch for combustion is completely mineralized to the ?uoride ion, which is then trapped in an aqueous solution (I, 64, 65). The ?uoride ion is then measured by an ion selective electrode (1, 64, 6 6). As little as 20-40 pg/L ?uorinated surfactant can be detected without the need to concentrate the water sample before combustion (1). Although this method determines the total organo?uorine content of a water sample, it does not provide 23 information. In addition, the mixmres of oxygen and hydrogen present a potentially signi?cant safety hazard. The methylene blue active substances test was used to detect the presence of anionic surfactants in groundwater at a ?re-training area at Tyndall Air Force Base (31). With the MBAS test, anionic surfactants form ion pairs with the methylene blue cation, which then are extracted into chloroform and determined spectrophotometrically (6 7). However, the use of MBAS as a reliable means of detecting ?uorinated surfactants in environmental wastewaters is limited because the MBAS test is non?speci?c and does not allow for the individual identi?cation of anionic surfactants nor for the di??erentiation between anionic hydrocarbon and ?uorocarbon surfactants. When structural infonnation is required to obtain de?nite identi?cation of ?uorinated surfactants in environmental samples, mass spectrometry is the method of choice. Chemical derivatization was combined with gas chromatography/mass spectrometry (GCMS) for the determination of per?uorinated surfactants in groundwater at Tyndall Air Force Base, FL (9, 34). Per?uorocarboxylates were quantitatively determined in groundwater by derivatizing the carboxylates to their methyl esters, which were detected and quanti?ed by electron impact and electron capture negative chemical ionization GCMS. Per?uorooctane sulfonate, which is present in AF FF formulations, was not detected by this method. Although per?uoroalkanesulfonate esters may have been formed during the derivatization step, the esters are tmstable due to excellent leaving group properties of the per?uoroalkanesulfonic group (7, 68). In fact, per?uorooctane sulfonate esters are sold as alkylaring reagents for the derivatization of 24 other analytes. Therefore, derivatization with gas chromatography has limited utility for - determining a broad range of perfluorinated surfactants. Liquid spectrometry is an attractive option for the sensitive and quantitative analysis of non-volatile analytes such as per?uorinated surfactants. Liquid chromatographyz'mass Spectrometry was used to qualitatively identify per?uorooctane sulfonate in groundwater from Tyndall Air Force Base, L, NAS allon, NV, and Air Force Base, (35). To the best of our knowledge, only one other report characterizes the determination of ?uorinated surfactants in water and wastewater by high performance liquid chromatography (HIPLC) together with a thermosmay interface and a tandem mass spectrometer (69). Liquid chromatographyimass spectrometry will most likely prove to be the most useful tool for characterizing the compositions and concentrations of a range of per?uorinated surfactants in environmental samples. Future Challenges Hydrocarbon-fuel ?res pose a serious threat to life and property and therefore the issue of ?re safety must be balanced against the risks that and their per?uorinated surfactants potentially pose to the environment. Fluorinated surfactants are a unique class of chemicals that are directly discharged to natural and engineered aquatic systems. The variety of applications for these types of surfactants is increasing yet little information on the environmental behavior is available. Fluorinated surfactants differ signi?cantly from hydrocarbon surfactants such that direct analogies can not be drawn between the two 25 types of surfactants. Therefore, the environmental behavior of ?uorinated surfactants is worthy of independent investigation. Because commercial formulations of are complex mixtures, the employment of these mixtures in ?re-training situations introduces both priority and non- priority pollutants into the environment. There are signi?cant gaps in the knowledge of how chromatographic separation during transport affeots these complicated mixtures. Because per?uorinated surfactants persist in the environment, they may impact the biogeochemical processes a??ecting the distribution and bioavailability of co- contaminants. The effect that components has upon subsurface microbial ecology and activity is Lmknown. Several different technologies are being evaluated to solve current problems resulting from AFF usage, including the development of products to replace AF FF. The 1998 Presidential Green Chemistry Challenge Award was recently presented to a company for the development of a biodegradable fire?extinguishing agent that does not contain-glycol ethers or ?uorinated surfactants (70, 71). Another approach to addressing the problems associated with ?uorirtated surfactants is to discontinue their use in AF FF agents and to return to prior technology such as protein-based foams. In a related issue, advances in ?re-?ghting product development includes the development and marketing of training foams that are designed to be used during training exercises in lieu of AF FF products that contain ?uorinated surfactants. Training products are attractive for their cost savings due to the absence of eXpensive fluorinated surfactant components. Training products have the added beue?t of being readily treated by conventional wastewater treatment facilities due to the increased biodegradability of the 26 non-per?uo?nated surfactant mixture and its reduced foaming properties. Such training foams eliminate the common environmental concern associated with AF FF and reduce training costs while still allowing for actual practice with ?re-training equipment (72). While training foams are designed to provide expansion characteristics similar to AP FF, they are inadequate ?re extinguishing materials if used in an actual hydrocarbon-Eel ?re. Because the possibility exists that training foams may be mistaken in an emergency for AF FF, some users do not employ training foams. Acknowledgments The authors thank Mitch Hubert and Dennis Seisun for valuable discussions and technical assistance. Additionally, we would like to thank Doug Barofsky, Walter Giger and John Westall for reviewing draft manuscripts. Steven H. Strauss, Gretchen N. Hebert and Matthew A. Odom at the Department of Chemistry, Colorado State University (Fort Collins, C0) are acknowledged for liquid spectrometry analysis of groundwater samples. 27 Literature Cited (1) Kissa, E. inorinaied Surfactants: Synihesis, Properties, and Applications; Marcel Dekker: New York, 1994. (2) Key, B. Howell, R. Criddle, C. S. Environ. Sci. Technoi. 1997, 31 2445- 2454. (3) Key, B. D. Dissertation, Michigan State University, East Lansing, Mi, 1996. (4) Porter, M. R. Handbook of Surfactants, Second ed; Blackie Academic Professional: Londoo, 1994. (5) Key, B. Howell, R. Criddie, C. S. Environ. Sci. Technoi. 1998, 32, 2283- 2237. (6) Rogers, R. S. Chem. Eng. News 1999, April i2, 30-32. (7) Hudlicky, Pavlath, A. 13.; Chemistry of Organic Fluorine Compounds Ii; American Chemical Society: Washington, DC, 1995. (8) Kauck, E. Diesslin, A. R. ind Eng. Chem 1951, 43, 2332-2334. (9) Moody, C. Field, J. A. Environ Sci. Technoi. 1999, 33, 2800-2806. (10) Shinoda, Hate, Hayashi, T- J. Phys. Chem. 1972, 76, 909-914. (11) Cross, .1. Anionic Surfactants: Anoiyiicoi Chemistry; Marcel Dekker: New York, 1998. (12) Darwin, R. Ottman, R. 13.; Norman, E. Gott, J. Hanauska, C. P. Nail. Fire Protect. Assoc. 1995, May fJnne Issue, 67-73. (13) IMR International. "Fire Fighting Foam Concentrates"; San Diego, CA, 1986, pp 2il-2i36. (14) Falk, R. "Aqueous Wetting and Film Forming Compositions"; United States Patent 4090967, 1978. (15) A1111, R. Stern, R. "Aqueous Film-Forming Foamable Solution Useful as Fire Extinguishing Concentrate"; United States Patent 5085286, 1992. (16) Harkins, W. Feldman, A. J. Am. Chem. Soc. 1922, 44, 2665-2685. (17) (13) (19) (20) (21) (22) (23) (24) (25) (26) (27) ?23) (29) (30) (31) (32) 28 Military Speci?cation: Fire Extinguishing Agent, Aqueous Film Forming Foam (AF FF) Liquid Concentrate for Fresh And Sea Water; Report No. U. S. Department of the Navy: Washington DC, 1992. Sche?'ey, J. Wright, J. Anobzsis ofrest criteria for Specyj/ingfoom?re- ?ghting ogentsfor aircro? rescue and ?re?ghting; Report No. 94-04; Hughes Associates, Inc.: Columbia, MD, 1994. Shinoda, Nomura, T. J. hem- 1980, 84, 365-369. Barcelona, M. J. Presented at the Symposium on Natural Attenuation of Chlorinated Organics in Groundwater, Dallas, TX, September 1996. Work Plan for Assessing the Feasibility of Intrinsic Remediation at Installation Restoration Program Sites; Oak Ridge National Laboratory: Oak Ridge, TN, October 1996. Contamination Assessment Report Active Fire Training Area FT-23 Tyndall Air Force Base Panama City, FL, FDER Facility No. United States Army Corps of Engineers: Washington DC, February 1994. O?Brien, A. F. MS. Thesis, University of Maryland, College Park, MD, 1994. Salazar, S. M. Technical Report 825, Naval Ocean Systems Center: San Diego, CA, 1985. Chan, D. Chian, E. S. K. Environ. Progr. 1986, 5, 104-109. Howell, R. Tucker, E. E. Am. Environ Lab. 1996, 12, 10-11. Remde, Debus, R. Chamomile-re 1996, 52, 1563-1574. Bass, C. M. Dissertation, University of Oklahoma, Norman, OK, 1982. Chan, D. Technical Report TM-54-79-19, Civil Engineering Laboratory, Naval Construction Battalion Center: Port Hucneme, CA, 1979. Chan, D. Technical Report Civil Engineering Laboratory, Naval Construction Battalion Center: Port Hueneme, CA, 1978. Levine, A. Libelo, E. Bugna, Shelley, May?eld, Stauffer, T. B. Sci. Total Environ 1997, 208, 179-195. Chapelle, F. 11.; Haack, S. Adriaens, Henry, M. Bradley, P. M. Environ Sci. chhnoi. 1996, 30, 3565-3569. (33) (34) (35) (36) (37) (3 3) (39) (4 0) (41) (42) (43) (44) (45) (45) (47) (43) 29 Bennejo, J. Sauck, W. Atekwana, E. A. GWMR 1997, 131-137- Henley, May?eld, Shelley, T. Abstract of Papers, Pittsburgh Conference, Atlanta, GA, American Chemical Society: Washington DC, 199?; Abstract 519. Moody, C. Furlong, E. Hebert, G. Odom, M. Strauss, S. Field, J. A. Abstract of Papers, Society of Enviromnental Toxicology and Chemisn'y Conference, Philadelphia, PA, 1999; PTA-123. Moody, C. Field, J. A. in preparation. Istok, J. Humphrey, M. Schroth, M. Hyman, M. O'Reilly, K. T. Ground Water 1997, 35, 619-631. Istok, J. Field, J. Schroth, M. Sewer, T. Humphrey, M. D. Ground Water 1999, 37, 590?598. Material Safety Data Sheet for ATC-603 Light Water ATC 3 AR-AF FF 3M Company, St. Paul, MN, 1998. Rosen, M. J. Surfactants and Interfacial Phenomena, Second ed.; John Wiley 3: Sons: New York, 1989. Hagen, D. Belisle, Johnson, J. Venkateswarlu, P. Anal. Biochem. 1981, HS, 336-343. Smart, B. E. In Molecular Structure and Energetics; Liebman, J. F., Greenberg, A., Eda; VCH Publishers: Deer?eld Beach, FL, 1986; Vol. 3, 141-191. Asakawa, Mouri, Miyagishi, Nishida, M. Langmuir 1989, 5, 343-348. Swisher, R. D. Surfactant Biadegradation; Marcel Dekker, Inc.: New York, 1987. Cancilla, D. Martinez, Van Aggelen, G. C. Environ. Sci. Technot. 1998, 32, 3834-3 835. - Lewis, Sr., R. J. Hazardous Chemicals Desk Reference, Third ed.; Van Nostrand Reinhold: Neva.r York, 1993. Gnha, Jaffe, P. Peters, (3. A. Environ Sci. Technol?. 1993, 32, 930-935. West, C. Harwell, J. H. Environ. Sci. Technol. 1992, 26, 2324-2329. (49) (50) (51) (52} (53) (54) (55) (56) (57) (53) (59) (60) (61) (52) (63) (54) (65) (660 30 Abriola, L. Pennell, K. Pope, G. Dekker, T. Luning-Prak, D. J. In Surfactant-EnhancedSubsurface Remediation; Sabatini, D. A, Knox, IL C., Harwell, J. H., Eda; American Chemical Society: Washington, DC, 1995; Vol. 594, pp 10?23. Gaha, Jaffe, P. R. Environ. Sci. Techno-i. 1996, 30, 1332-1391. Cuba, Jaffe, P. R. Environ. Sci. Technoi. 1996., 30, 605-611. Liu, Jacobson, A. Luthy, R. G. Appi. Environ Microbiol. 1995, 61, 145- 151. Laha, R. G. Environ Sci. Technoi. 1991, 25, 1920-1930. Roch, Alexander, M. Environ Toxicoi. Chem. 1995, 14, 1151-1158. Tsonn'des, H. Hughes, J. Thomas, J. Ward, C. H. Environ Toxicoi. Chem. 1995, 14', 953?959. Material Data Safety Sheet for FC-95 Fluorad Brand Fluorochemical Surfactant, 3M Company. St. Paul. MN, 1999. Halton, B. In The Florida Times- Union: Jacksonville, FL, 1993, pp Kinner, D. L. In The iorida Times-Union: Jacksonville, FL, 1998, pp 13?1. A. R. Stickley, Twedt, D. Heisterberg, J. Mott, D. Glahn, J. F. Wild. Soc. Bali. 1986, 14, 412-418. Fendinger, N. Begley, W. McAvoy, D. Eckhoff, W. S. Environ. Sci. Technoi. 1992, 26, 2493-2493. Popenoe, D. Morris, 111, s. Horn, P. Norwood, K. T. Anni. Chem. 1994, 66, 1620?1629. Schmitt, T. M. Analysis of Surfactants; Marcel Dekker: New York, 1992. Sweetser, P. B. Anni. Chem 1965, 28, 1766-1768. Kissa, E.Anai. Chem. 1983, 55, 1445-1443. Kissa, E. Environ. Sci. Technoi. 1986, 20, 1254?1257. Kissa, E. In Anionic Surfactants: Anai?icai Chemistry; Cross, ., Ed.; Marcel Dekker: New York, 1998; Vol. 13. (67) (63) (59) (70) (7 1) (72) (73) 31 Anionic Surfactants as In Standard Methods for the Examination of Water and Wastewoter; Association of American Public Health, Association of American Water Works, Water Environment Federation, Eds; American Public Health Association: Washington DC, 1998, March, J. Advanced Organic Chemistry, Third ed.; John Wiley Sons: New York, 1985. Schr?der, H. F. Vom Wesser 1991, 77, 277-290. Betts, K. s. Environ. Sci. Technol. 1993, 32, 351A. Raber, L. R. Chem. Eng. News 1998, July 6, 25-26. Material Safety Data Sheet for 155 Training Foam, 3M Company, St. Paul, MN, 1999. Material Safety Data Sheet for FC-203CF Light Water Brand Aqueous Film Forming Foam, 3M Company, St. Paul, MN, 1997. 32 Chapter 2 Analy?cal Method for the Determination of Per?uorocarhoxylates in Groundwater Impacted by Fire-Fighting Activity Cheryl A. Moody1 and Jennifer A. ield1 'Department of Chemistry and of Environmental and Molecular Toxicology, Oregon State University, Corvallis, Oregon 97331 Reprinted with permission from Environmental Science and Technology 1999, 33, 2800-2806. Copyright 1999 American Chemical Society. 33 Abstract Per?uorinated surfactants are used in aqueous ?lm forming foam formulations, which are used to extinguish hydrocarbon-fuel ?res. Virtually nothing is known about the occurrence of per?uorinated surfactants in the environment, in particular, at ?re-training areas and emergency response sites where AF FF entered groundwater without prior treatment. Strong anion exchange Empore disks were used to extract per?uorocarboxylates from groundwater collected from ?re-training facilities located on Naval Air Station Fallon, NV, and Tyndall Air Force Base, FL. The carboxylates were simultaneously eluted from the disks and derivatized to their methyl esters for direat analysis by gas Spectrometry. Per?uorocarboxylates containing 6-8 carbons were detected in groundwater collected from the two ?eld sites with total concentrations ranging from 125 to 7,090 ugfL. The detection of per?uorocarboxylates at ?eld sites after 7 to 10 years of inactivity indicates their potential utility as markets for delineating gromldwater impacted by ?re-?ghting activity. 34 Introduction Aqueous ?lm forming foams (AF FF) are complex mixtures of surfactants and other components used to extinguish hydrocarbon-?lm ?res that occur at fire?training sites as well as in emergency situations. Aqueous ?lm forming foams have been commercially available for ?re-fighting applications since their development by the United States Navy and 3M Co. in the mid-19605 (1). At ?re-training areas that routinely used AF FF mixtures and military emergency response sites, nastewater that entered surface water and groundwater without treatment has led to groundwater and soil contamination. For exanmle, per?uorinated compounds were tentatively identi?ed in groundwater impacted by ?re-training activities at Tyndall Air Force Base (2). Unfortunately, de?nitive identi?cations of the per?uorinated compounds were not reported. Commercial AF FF mixtures- are propreitary in nature and typically contain ?uorinated and non-?uorinated surfactants (1, 3-5). Due to the proprietary nature of AF formulations, the chemical structures of the actual per?uorinated Surfactants used in commercial are not known outside the companies that manufacture them (5). Moreover, the analysis of anionic per?uorinated surfactants that are known to occm in AF FF formulations (6) is problematic because the surfactants are non-volatile and may not contain chromophores. As a result, analytical methods for AF FF formulation components are lacking and therefore it is difficult to assess their occln'rence, fate, and transport in AF F-contarninated groundwater. Because per?uorinated surfactants co- occur with other pollutants g. fuel components, solvents, etc.) in groundwater, it is important to determine if per?uorinated surfactants affect the transport and 35 biodegradation of other contaminants. Free and emulsi?ed oil, fuel, and AF FF components were shown to adversely affect activated sludge processes (6, and the performance of anaerobic sludge digestors (8) in wastewater treatment facilities. For this reason, per?uorinated surfactants may have an adverse a?ect on gromdwater microbial populations and their ability to degrade co-contarninants present in groundwater. In addition to ?uorinated surfactants use in fire-?ghting foams, they are also utilized in herbicides and insecticides, cosmetics, greases and lubricants, and adhesives (3). Fluorinated carboxylic acids of industrial signi?cance- include per?uorooctanoic acid (PFC 8) and per?uorodecanoic acid 0) (9). There is concern regarding the potential toxicity of per?uorinated carboxylic acids. An in vivo study of rat liver response to PF C1 0 indicated the rapid onset of a low-level heptatntoxicity but no detectable damage to the DNA (I 0). Per?uorodecanoic acid and PFCS have been found to inhibit gap - junction intercellular communication in rat liver epithelial cells (I I) and may be involved in tumor promotion (9). In this paper, we describe the isolation, identi?cation and quanti?cation of per?uorinated carboxylates in groundwater impacted by fire-training activities at Naval Air Station (N AS) Fallon, NV, and Tyndall Air Force Base, FL. The development of analytical methods is necessary before investigating the occurrence and distribution of per?uorinated surfactants in groundwater and their effect on co- contaminant transport and biodegradation. 36 Experimental Section Standards and Reagents. Standards of PFCS (9 per?uorododecanoic acid (PFC12) and the internal standard, 2?chlorolepidine were purchased ?'om Aldrich Chemical (Milwaukee, WI). Methyl iodide (neat) was used as purchased from Aldrich Chemical. Field Sites and Sample Collection. From the mid-19505 to 1988, the crash crew training area at NAS Fallon, NV, (Figure 2.1a) was used to conduct fire?training activities, which consisted of ?ooding a ?re pit with ?ammable liquids, igniting the ?uids, and subsequently extinguishing the ?re with ?re-?ghting agents including AF FF (I 2). For a typical training exercise, approximately 75-100 of AF FF concentrate were diluted with 1200-3200 of water according to specifications or 6% solution) and subsequently employed. During the years of activity at the NAS Fallon site, training exercises occurred on a weekly to basis. At the NAS Fallon site, groundwater samples were collected ?'om four monitoring wells located within a 120 radius of the ?re pit where the water table is located between 2 to 3 rn below the land surface. The Tyndall Air Force Base Fire-training Area FT-23 was used from 1980 to 1992 for similar activities (Figure 2.1b) (13). Four groundwater samples were obtained from wells surrounding the ?re-training area; the water table is located between 1 and 2 below the land surface. All samples were collected in high density polyethylene broxvn bottles beoause per-?uorinated carboxylates adsorb to glass (14). Samples were shipped on ice without preservation and stored at 4 prior to analysis. Solid-Phase Extraction and Derivatization. Samples (55-200 mL) were extracted through 25 mm strong anion exchange (SAX) disks in a manner similar to that Grou Norah Flow Direction 1 Scale: 0 50 - Monitoring Well Separator and W1 Field Groundwater Flow Direction Scale: {1 50m - Monitoring Well 37 Figure 2.1. Map of Naval Air Station Fallon, NV, and Tyndall Air Force Base, FL, ?eld sites indicating location of groundwater wells and direction of regional groundwater ?ow. 38 described by Field and Reed (15) 1with the exception that the SAX disks were pre-treated prior to use to remove interfering disk impurities. Pretreatment consisted of soaking the disks in 12 mM HCHacetonitrile for 2 days after which the disks soaked in pure acetonitrile for several hours. Just prior to use the disks were rinsed with a minimum of 350 mL of deionized water in order to sufficiently rinse the 1-101 from the disks and wet them prior to passing groundwater samples through them. Samples (55-200 mL) were passed through the disks under full vacuum and the disks were then allowed to dry. The disks comaining the exchanged analytes were placed in a 2? mL autosampler vial together with 1 mL of acetonitrile, 51.2 pg of internal standard, and 100 pL of methyl iodide. When heated at 80 for 1 h, the acids were sim?taneously eluted from the disk and derivatized to their methyl esters. Spike and Recovery. Spike and recovery experiments were performed to determine the precision and accuracy of the SAX disk extraction and in?vial elution method. A set of errperiments was performed on groundwater samples from NAS Fallon MW SOU and MW 1? that had been previously determined to contain neither PFCS nor PFC 12 above detection. Duplicate grormdwater samples from wells MW 50U and MW 17 were spiked to contain a final concentration of 1,240 rig/L of PFCS and 560 of PFCIZ. Standard addition analyses were performed with NAS Fallon groundwater samples that contained measurable quantities of the samples did not contain PFC12 above detection. Known amounts of PFC8 were added to samples to give a ?nal concentration twice that of the background concentration. For example, groundwater 39 from MW and MW 16, which contained background concentrations of 6,5?0 pig/L and 460 pg/L, respectively, were spiked to give a ?nal concentration of 12,900 pig/L and 1,000 pig/L of PFCS, respectively. Each sample also was spiked with 56.4 pg of PFC12. To determine the detection limit of the method, single samples of groundwater that contained no per?uorinated carboxylates above detection were spiked to give a range of ?nal PFCB concentrations from 18 to 54 pg?L. Gas Chromatography! Mass Spectrometry. Extracts were analyzed using a Hewlett Packard Model 5890 Series II Plus gas chromatograph (GC) equipped with a 30 0.32 mm 4.00 pm SULFUR column (Supelco Inc., Bellefonte, PA). An injection volume of 1 pL was used under splitless conditions with an injector temperature of 200 The GC oven temperature was initially held for 6 min at 60 increased by 6 ?C/min to 190 increased further by 30 ?Cfmin to 270 and then held for 5 min. Quanti?cation of per?uorocarboxylate methyl esters was performed using a Hewlett Packard Model 5972 mass selective detector operated in electron impact (EI) mode (70 eV). The mass selective detector was operated in full scan (50-450 amu) mode and in selected ion monitoring (SIM) mode using a dwell time of 100 ms for each ion. The scanning mode was used for qualitative identi?cation while SIM mode was used for quanti?cation. The ions of In}: 131 ml: 169 and 219 which are characteristic fragments of per?uorocarbons (i 6J8), were used to identify and quantify the methyl esters of per?uorohexanoic acid (PFCG), per?uoroheptanoic acid (PFCY), PFCE and PFC12. The internal standard, Z-chlorolepidine, was quanti?ed with the ions 177 and 115. 40 The identi?cation of per?uorocarboxylate methyl esters was confirmed by electron capture negative ionization (ECNI) which gave unique molecular ions for each of the per?uorinated carboxylate methyl esters 328 for PFCG, mi: 378 for PFC7, 428 for PFCS, and ml: 628 for PFC12). These measurements were performed with a Varian 3400 gas chromatograph interfaced with a Finnigan Model 4023 mass spectrometer. Methane was used as the reagent gas and the mass spectrometer was operated in scan mode (100-650 emu). The gas chromatograph was operated with a column and temperature program identical to that used for the El Initially, samples prepared in deionized water were used as the matrix for constructing calibration curves and stande recoveries were low. However, when samples prepared in tap water, which contains inorganic cations and anions, were used as the matrix for constructing calibration curves quantitative recovery of standards was obtained. It is proposed that the 350 mL of deionzed water does not suf?ciently rinse the disks of residual and tap water is required to completely rinse the disks and obtain quantitative recovery of standards. Therefore, calibration curves for quanti?cation of PFCS were constructed by passing 100 mL tap water samples that had been spiked with 3.6 pg to 1,080 pg PFCS through 25 mm SAX disks and derivatizing the acids to their methyl esters using the in-vial eiution and derivatization technique. The calibration curve for PFC12 was constructed in a similar manner by adding 15 pg to 113 pg standard to 100 mL tap water. For all quantitation standards, a total of 51.2 pg of the 2- chlorolepidine internal standard was added to the autosampler vial just prior to the addition of methyl iodide. Both calibration curves were linear with r2 typically greater 41 than 0.99. Quanti?cation of PF C6 and PF was performed assuming a response factor equal to an equimolar amount of PFCB. Results and Discussion Gas ChromatographyMass Spectrometry. A ?lm thickness of 4 pm (30 0.32 mm Supelco, Bellefonte, PA) was necessary to obtain su?icient retention times for the methyl esters of PFCS and PFC 12 to allow for the separation and quanti?cation (Figure 2.2a). Initial attempts to separate and quantify the per?uorinated carboxylate methyl esters on a thin ?lm (0.25 pm), 30 0.25 mm Scienti?c, Folsom, CA) column were unsuccess?rl regardless of the initial column temperature. Note that the stationary phases in the SULFUR and columns are comparable. A standard of per?uorobutyric acid was not observed under any of the described GC conditions; it is most liker that an initial oven temperature less than 40 would be required. The El mass spectra of methyl PFCS (Figure 2.3a) and PFC12 indicate characteristic per?uorocarbon fragmentation (16, I 7) in which the major ions 69, 119, 169, 219, etc.) differ by 50 earn, which corresponds to the mass of Molecular ions were not observed for any of the per?uorinated carboxylate methyl esters under E1 conditions; however, molecular ions were observed under conditions. For example 428 (in Figure 2.3b) corresponds to the molecular ion of methyl PFCS. Solid-Phase Extraction. Prior to developing a solid-phase extraction method, initial experiments were conducted using diazomethane as the derivatization reagent. 42 When per?uorinated carboxylates were derivatized using ethanol?based diazomethane, multiple peaks corresponding to methyl and ethyl esters were detected (unpublished data). Because EI GCMS did not produce molecular ions, ECNI GCMS was used to 1verify the formation of both methyl and ethyl esters. Consequently, if ethanol-based diazomethane was used for derivatization in conjunction with El GCMS, multiple peaks in a chromatogram could be erroneously interpreted as a greater number of per?uorinated compounds than are actually present. In contrast, only the methyl ester was obtained when butyl carbitol was used to prepare the diazomethane reagent. However, because of the hazards associated with the use of diazomethane and the time-consuming nature of diazomethane derivatization, an alternative method was desired. Derivatiza?on of the per?uorocarboxylates by the solid-phase extraction and the in-vial elution and derivatization technique gave only a single peak that corresponded to the methyl ester of each per?uorinated carboxylate standard; the identi?cation of each methyl ester was con?rmed by GCIMS. In addition, the solid-phase extraction approach combined the steps of isolation and derivatization, which greatly simpli?ed the procedure and eliminated the use of diazomethane. Six replicate analyses of blank 25 mm SAX disks that had not been pre-rinsed with 12 mM HCl/acetonin-ile prior to use, yielded an average of 21 i 1 pg relative stande deviation of PFC8 per disk. No other perfluorinated carboxylates were present in the disks above the detection limit. The PFC8 is associated with the Te?on matrix and not the embedded anion exchange particles (unpublished data). The backgron PFCS was successfully removed 43 1:56 n+5 8 . 2-chioroleold1ne Be+5 :l .0 II :2 4e+5 FFGG asTime (min) 1o+6 PFoa 2-c?orolopidine 3 Eu 'u 694-5 3 .o d: 3 '3 4e+s - o: 29+5 - PFC12 PFoo I 11Time (min) Figure 2.2. Typical EI GCIMS chromatogram of PFC8 and PFC12 standards and por?uorinatod oarboxylatos, including PFCG, PFC7, PFCB and PFC12 (spiked) in Naval Air Station Fallon, NV, groundwater. 1 5&5 59 1.23.0m - 59 0 [Ch1&1 Icqu??. 381 219 231 281 331 359 100 150 2130 250 300 350 ?too 450 sauna 35? - 4mm - 30000 - 403 are 20060 a 312 423 moon - 0' I- 1. .i1- 1n. .IIJ 1 15:: mo 25:: am 350 400 450 mi: Figure 2.3. EI mass spectrum of methyl PFC3 and an ECNI mass spectrum of methyl PFCB. 45 by rinsing the disks prior to use with 12 mM Hleacetonin-ile followed by 350 mL of deionized water. It should be noted that benzoic acid and acid are also present in the disks as artifacts and are removed by the HCUacetonitrile pro-rinse step. Accuracy, Precision and Detectitm Limits. The recoveries of PFCS from blank groundwater samples obtained from NAS Fallon wells MW SOU and 17 were 73 and 74%, respectively, while the recoveries of PFC12 were 77 and 83%, respectively (T able Because detectable levels of PFCE occurred in groundwater from MW 51U and MW 16, standard addition experiments were performed to determine the recoveries of PFC8. The recoveries of the PFC8 spiked into MWSIU and MW 16 groundwater to give a ?nal concentration double that of the background concentration were 83 and 90%, respectively (Table 2.1). The recoveries of from MW 51U and MW 16 groundwater, which did not contain backgound concentrations of PFC12, were 35 and 85%, respectively (Table 1). Although the recovery of PFC8 differs signi?cantly from that of PF C12 (3 in groundwater from MW the recoveries of PFCS and PFC 2_were nearly equivalent for the other groundwater samples. Monitoring well 51U is located closest to the fire pit where AF agents where applied to burning mixtures of fuels and solvents. Due to its proximity to the ?re pit, the groundwater from MW 51U most likely contains the greatest diversity of inorganic and organic constituents, which may adversely a?ect 2 recoveries relative to that of PF C8. Therefore, although the original intent was to use the PFC12 as a surrogate standard because it did not occur in the groundwater samples, PFC12 appears more sensitive to matrix interferences 46 Table . Recovery and PF C1 2 spiked into groundwater samples from Naval Air Station Fallon, PFCS PFC12 Sample - recovery recovery NAS Fallon MW 83? 35 NAS Fallon MW 16 90?1 85 NAS Fallon MW SOU 73 77 NAS Fallon MW 1? 74 88 ?Duplicate samples were analyzed. Sample volume was 100 mL unless o?terwise noted. t?Sample volume was 55 mL. ?Calculated as the ?nal measured concentration divided by backgron concentration plus spike concentration and multiplied by 100. The background concentration was 6,5 70 lug/L- dCalculated as the ?nal measured concentration divided by background concentration plus spike concentration and multiplied by 100. The background concentration was 460 pg/L. 47 compared to PF C8 so that it is an inappropriate choice for a surrogate standard. For this reason, all subsequent quanti?cation was based on the Zachlorolepidine internal standard. The precision, indicated by the RBI), calculated from ?ve replicate analyses each of groundwater from NAS Fallon MW 16 and Tyndall AFB T11-2 ranged from 3.7 to 14% (Table 2.2). The detection and quantitation limit of the method was de?ned as those concentrations of PFC8 needed to produce a signal to noise of 3 :1 and 10: respectively. The detection and quantitation limits for PFCE were 18 rig/L and 36 pg/L, respectively. Application to Groundwater Samples. Four groundwater samples from both NAS Fallon and Tyndall AF were analyzed for per?uorlnated carboxylates. Chromatograms obtained by El GCMS indicated the presence of multiple per?uorinated compounds all having characteristic pcr?uorocarbon ?agmentation (Figure 2.2b). Analysis by ECN I established the identi?cation of PF C6. and PFCS in groundwater obtained from wells MW 5 1U and MW 16 from NAS Fallon. The molecular ions for methyl PFC6 (mfz 328) and methyl (11112 378) were observed for peaks eluting and 2.3 min before that of PFCB (Figure 2.4a and 2.4b). The ECNI mass spectrum for methyl PFCS in MW 51U was similar to that of the PFCS standard (Figure 2.2b). The groundwater samples from NAS Fallon MW 5 1U and MW 16 had total per?uorinated carboxylate concentrations of 7,090 ng/L and 54D pg/L, respectively (Table 2). The PFC6 detected in NAS Fallon groundwater samples from MW 5 1U and MW 16 comprised 5.2% and 11%, respectively, of the total per?uorocarboxylates 48 Table 2.2. Concentrations of per?uorinated carboxylates in groundwater samples from Naval Air Station Fallon, NV, and Tyndall Air Force Base, Sample 11 PFCG PFC3 Total (us/L) (rte/L) (143M (991) NAS Fallon 5,570 150 7,090 1150 NAS FallonMW 16 57: 3 13 :2 4:50:20 540:20 (11%)9 NAS Fallon NAS Fallon Tyndall AFB Pw-lo 2 I 144 33 116 293 Tyndall AFB P311307 2 73 22 9 64 159 73771115113313 711-2 5 64:4 19:1 42:2 124:3 Tyndall AFB TY22FTA 2 nd ad nd nd 'The relative standard deviation is given in parentheses. li'rld, not detected above the detection limit. l"I'he reported value is near the detection limit (SN 5 3 and less than the quantitation limit (SN 5 10). The value has been included in the reported total concentration. 49 detected. The was 2.1% and 3.3% respectively, of the total per?uorinated carboxylates detected in these wells. The dominant perfluorinated carboxylate, PFC8, accounted for 93% and 85%, respectively, of the total per?uorocarboxylate concentration. The highest concentrations of perfluorocarboxylates were observed in groundwater collected from NAS Fallon MW 5 1U, which is the well located closest to i the ?re-training pit (Figure Monitoring well 16, which is located downgradient of MW and the ?re-training pit, had lower but detectable concentrations of per?uorocarboxylates. Groundwater from MW SOU and MW 17, which are located off gradient from the ?re-naming pit, contained no detectable per?uorinated carboxylates. Over the approximate 100 to distance between MW 51U and MW 16, the concentrations of the per?uorinated carboxylates decreased with increasing number of carbons. For example, the concentration of PFC6 decreased 85% over the 100 compared to decreases of 88% and 93% for and PFC8, respectively. The groundwater samples from Tyndall AFB and 1-2 contained total per?uorinated carboxylate concentrations of 298 ug/L, 159 ugfL and 124 pg/L, resPectively (Table 2.2). The compositions of Tyndall AF gmundwater collected from the three wells ranged ?oor 46 to 52% for PFCG40% for PFC8. In contrast to the groundwater samples from NAS Fallon, the dominant per?uorinated carboxylate in Tyndall AF gr0undwater was PFC6. 'l'he highest concentrations of per?uorocarboxylates among the groundwater i sammes from Tyndall AFB were observed in and PW-07, which are the two wells located closest to the ?re-training pit (Figure 2.1b). Monitoring well 1-2, which is I 25000 i 25a 20000 - 150W - .43? 0?1 0) a 100 278 5000 - - 303 323 150 200 250 300 350 400 450 mi: 15000 - 300 150?] 12000 - 262 [Ml cc: 9000 378 5000 259 323 3000 - 200 235 25? . 11,1! Ill 1 I 150 250 300 350 400 450 ml: Figure 2.4. ECNI mass Spam-um of methyl PFC6 and methyl PFC7. 50 1 located downgradient of the ?re-uahring pit, had lower but detectable groundwater concentrations of per?uoroearboxylates. The groundwater collected from a well located north of the ?re-training pit, contained no per?uorinated carboxylates above the detection limit (18 pg/L). It is not surprising to observe a suite of per?uorinated carboxylates since the raw materials used in the of per?uorinated organic compounds are mixtures (3, I9). Different ratios of PFC6, and PFCS may result from the use of different AF FF formulations at the two ?re-training areas. The observed homologous series consisting of even and odd number per?uorinated carboxylates is indicative of the electrochemical fluorination process used by 3M Co. (3). Other ?uorination processes, such as telomerization, produce only even number homologues (3). Because of the proprietary nature of it is not known if perfluorinated carboxylates are present as one of the major surface active agents in formulations or as unreacted starting materials used in the of the principal per?uorinated surfactants used in AF FF formulations. In addition, the carboxvlates may be combustion, biological or non-biological degradation products of the principal per?uorinated components in mixtures. Unfortunately, the exact source and history of AF FF applications at the two ?eld sites are unknown, and, therefore, the relationship behveen the observed per?uorocarboxylate ratios and that of the original AF FF mixtures is unlmown. To the best of our knowledge, very little is known regarding the transport and fate of per?uorocarboxylates in grotmdwater. Adsorption to sludge at wastewater treatment facilities is considered a signi?cant process for the removal of per?uorinated surfactants 52 during treatinent (3). However, detection of per?uorinated carboxylates at the NAS Fallon and Tyndall AF sites, which have not been used since 1988 and 1992, respectively, is consistent with the view that biodegradation of the long chain per?uorocarbon hydrophobe is unliker (6, 9, 19). The recalcitrant nature of perfluorinated compounds is attributed in part to the rigidity of the per?uorocarbon chain (9, 20) as well as the strength of the carbon ?uorine bond (3, 9, To the best of our knowledge this is the ?rst defmitive identi?cation of per?uorinated carbonylates in groundwater impacted by ?re-?ghting activity. Further work is needed to determine if additional per?uorinated components are present, such as per?uorooctane sulfonic acid, which is thought to be one of the principle components in some commercial AFF formulations. In addition, it is of interest to relate the occurrence and distribution of perfluorinated compounds to other site characterization parameters such as dissolved organic carbon, inorganic constituents, and the distribution of co-contaminants and to understand the potential in?uence of per?uorinated compounds on the biotransformation and transport of other co~contan1inants Acknowledgements The authors thank Donald Hagen and Eric Reine! of 3M Co. and Mitch Hubert of Ansul Inc. for valuable discussions and technical assistance. We would also like to thank Chang .Tho and Erik Kissa for reviewing draft manuscripts. Ron Hoeppel and Art Fisher from NAS Fallon, Bill I ohnson from the University of Utah and Erica Becvar from Tyndall AFB are gratefully acknowledged for facilitating sample collection. Supelco, Inc. is gratefully acknowledged for the donation of a GC column and vacuum manifolds. 53 - This work was ?nancially supported by the Oregon State Department of Chemistry (N. L. Tartar Research Fellowship) and by a grant from the Environmental Protection Agency (OER R821195). The authors acknowledge the Oregon State University Environmental Health Science Mass Spectrometry Core Facility for its support through NIEHS grant 13300210. 54 Literature Cited (1) O'Brien, A. F. M.S. Thesis, University of Maryland, College Park, MD, 1994. (2) Henley, May?eld, Shelley; T. Abstracts of Papers, Pittsburgh Conference, Atlanta, GA, American Chemical Society: Washington, DC, 1997; Abstract 519. (3) Kissa, E. Hoorinoted Surfactants: Properties, and Applications; Marcel Dekker: New York, 1994. (4) Bass, C. M. Dissertation, University of Oklahoma, Norman, OK, 1982. (5) Howell, R. Tucker, E. E. Am. Environ. Lab. 1996,12, 10. (6) Darwin, R. Otunan, R. Norman, E. Gott, J. Hanauska, C. P. Natl. Fire Protect. Assoc. 1995, 67. (7) Chan, D. Chian, E. S. K. Environ. Progr. 1986, 5, 104. (8) Remde, Debus, R. Chemosphere 1996, 52, 1563. (9) Key, B. Howell, R. Criddle, C. S. Environ Sci. Technof. 1997, 31, 2445. (10) Godin, C. Myhr, B. Lawlor, T. Young, R. Mnrli, Cifone, M. A. Genotoxicity Assessment of Per?uorodecanoic Acid using a Battery of in vitrc and in vino/in vitro Assays; Harry G. Aerospace Medical Research Laboratory: Kensington, MD, December 1990. (11) Deocampo, N. Upbam, B. Trosko, J. E. Fondant. Appl. Toxicol. (Suppl) 1996, 30, 208. (12) Work Plan for Assessing the Feasibility of Intrinsic Remediation at Installation Restoration Program Sites, Naval Air Station, Fallon, Oak Ridge National Laboratory, October 1996. (13) Contamination Assessment Report Active Fire-training Area FT-23 Tyndall Air Force Base Panama City, FL, FDER Facility No.; United States Anny Corps of Engineers, February 1994. (14) Belisle, Hagen, D. F. Anal. Biochem. 1980, 101, 369. (15) Field, J. Reed, R. L. Environ. Sci. Technol. 1996, 3 0, 3544. (16) McLaffer-ty, F. anecek, F. Interpretation of Mass Spectra, 4 ed.; University Science Books: Sausalito, CA, 1993. (17) (13) (19) (20) (21) 55 Lynn, P. Tamer, K. Gross, M. L. Andi. 1985, 57, 2984. Hudlicky, Pavla?m, A. E. Chemistry of Organic Fiuorine Compounds Ii: A Critical Review; American Chemical Society: Washington, DC, 1995. Key, B. D. PILD. Dissertation, Michigan State University, East Lansing, MI, 1996. Asakawa, Monti, Miyagishi, Nishida, M. Langmuir 1989, 5, 343. Smart, B. E. In Moiecuiar Structure and Energetics; Liebman, J. F., Greenberg, A., Eda; VCH Publishers: Deer?eld Beach, FL, 1986; Vol. 3. 56 Chapter 3 Occurrence and Distribution of Per?uorinated Surfactants in Groundwater at the Wurtsmith Air Force Base Fire-Training Area Two and ICC-135 Crash Site Cheryl A. Moody? and Jennifer A.'Field1 "Department of Chemistry, and of Environmental and Molecular Toxicologyr Oregon State University, Corvallis, Oregon 97331 Environmm?a! Science and Teehnolog, manuscript in preparation. 57 Abstract Per?uorinated surfactants are a major component in aqueous ?lm forming foam (AF FF) formulations, which are used to extinguish hydrocarbon-?re] ?res. As a result of past ?re-training exercises, as well as response to emergency situations, wastewater containing ?rels, solvents, and other materials directly entered groundwater without prior treatment. Historically, AFF mixtures containing perfluon'nated surfactants were applied at Wurtsmith Air Force Base, M, including at Fire?Training Area Two and a location where a airplane crashed. Perfluorocarboxylate (containing 6 to 8 carbons) concentrations ranging from the detection limit (3 pgfL) to 110 ug/L were measured in groundwater sampled over an extensive well array at Fire- Training Area Two where as none were detected atthe airplane crash site. Per?uorocarboxylates detected over 500 from the source area have an approximate minimum residence time of 5 to 15 years, and provide direct ?eld evidence that this class of pcr?uorinated surfactants persists under prevailing groundwater conditions. Signi?cantly higher concentrations 400-3600 rig/L) of methylene blue active substances which is an indirect measurement of anionic surfactants, indicates that the per?uorocarhoxylates are only a small fraction of the anionic surfactant species present in the groundwater. The transport of per?uorocarboxylates in groundwater was not fully characterized such that additional research is needed to characterize the transport of per?uorocarhoxylates in groundwater. 53 Introduction - In ?uorinated surfactants, the hydrophobic portion of the surfactant molecule contains ?uorine. To classify a surfactant as per?uorinated, all hydrogen atoms in the hydrophobic segment are replaced by ?uorine atoms. The substitution of ?uorine for hydrogen in ?uorinated surfactants differentiates these surfactants from hydrocarbon surfactants. For examme, ?uorinated smfactants have unique wetting and spreading characteristics that make them better suited than hydrocartbon surfactants in coating, paint, ink, and polish applications (I. 2). Because of the ?uorocarbon hydrophobe, fluorinated surfactants are usually more physically, chemically, and biologically stable than hydrocarbon surfactants (2). Hydrocarbon-fuel ?res pose serious threats to life and property, and aqueous ?lm forming foams are employed to extinguish these types of ?res. Fluorinated surfactants are a major component in AFF formulations (3). Physical characteristics, such as the ability to lower surface tension, aid in the formation of a water ?lm that forms over the surface of a hydrocarbon fuel), which makes ?uorinated surfactants well- suited for applications. While the stability of per?uorinated surfactants make them . suitable for applications that involve extreme environments, it also leads to their apparent persistence in the environment Due to the presence of large quantities of ?ammable liquids, municipal (i ?re departments), hydrocarbon-processing industry oil re?neries), and military sectors utilize with the military comprising 75% of the total market, while the municipal and hydrocarbon-processing industry represents 13% and respectively (5). In 1985, the United States market for AF FF products 3% and 6% concentrates) was 6.8 59 million with a total revenue of 10 million dollars in U. S. sales (5). The military was the single largest consumer of AF FF agents in 1985, with consumption totaling 5.1 million (5). Currently, the Organization for Economic Cooperation and Development (OECD) classi?es per?uorinated C5 to C18 compounds as high-production-volinne (HPV) chemicals, where HPV chemicals are those chemicals manufactured or imported in the U.S. in quanti?es exceeding 1 million pounds (6). This class of chemicals encompasses the per?uorinated and partially??uorinated surfactants used in AF FF. Data is needed for an environmental and toxicological database that will be developed for HPV chemicals under a voluntary program led by the U.S. Environmental Protection Agency and the Chemical Manufacturer?s Association. Planned database entries for the HPV chemical testing program include physical and chemical properties, environmental fate and pathways, fate and environmental distribution assessment, and mammalian toxicity currently much of this information for per?uorinated surfactants is either unlmown or unavailable. In preparation for hydrocarbon-Eel ?res, training exercises at military bases often are conducted. As a result, at military emergency response sites and ?re-training areas, the repetitive use of AF and release of wasteivater to the environment has led to groundwater contamination. Positive identi?cation of one class of per?uorinated surfactants, per?uorocarboxylates, was reported for a limited number of groimdwater samples obtained from Naval Air Station (N AS) Fallon, NV, and Tyndall Air Force Base, FL (4). Although not listed as a component in material safety data sheets from manufacturers, the per?uorocarboxylates were found in some 60 AF FF products (unpublished data). An additional report tentatively identi?es perfluorinated compounds in groundwater impacted by ?re-training activities at Tyndall Air Force Base (8). Few publications report the occurrence of perfluorinated surfactants in the environment, primarily due to the lack of sensitive and speci?c analytical methods. The methylene blue active substances (MBAS) test has been used as an indicator of hydrocarbon anionic surfactants in soils (9) and groundwater (I 0-H). A study at Tyndall Air Force Base used MBAS to qualitatively identify the presence of anionic surfactants in groundwater (I5). With the MBAS test, anionic surfactants form ion pairs with the methylene blue cation, which then are extracted into chloroform and determined spectrophotometrically. Reasons for employing the MBAS test include that it is inexpensive, relatively simple, and ?eld-ready. However, the MBAS method is non- speci?c and does not allow for the detection and quantitietion of the individual surfactants present. In the case of groundwater, a number of anonic surfactants could be present including per?uorinated and non-?uorinated surfactants (16- 18). For these reasons, the use of MBAS should be limited to that of a screening tool for enviromnental samples (13). This ?eld study addresses the gap in information consenting the occurrence, distribution, and transport of per?uorinated surfactants in the environment, speci?cally in groundwater at Wintsmith Air Force Base (WAFB) in Oscoda, MI. The concentrations of per?uorinated carboxyiates detected in grotmdwater impacted by ?re-training activities at WAF provide infonnation regarding the movement and persistence of per?uorinated surfactants in groundwater at Fire-Training Area Two. 61 Additionally, general chemical indicators, such as speci?c conductance, total organic carbon (TOC) and MBAS were measured for the Study to ?n'ther delineate the distribution of perfluorinated surfactants in groundwater contaminated by ?re-training activities at this site. Experimental Section Field Site Descriptions. Wurtsmith Air Force Base is located in northeast Michigan and was decommissioned in June of 1993. Historically, Fire-Training Area Two (PTA-02) (Figure 3.1) at WAFB was used for U. S. military personnel training in ?re-?ghting procedures. The site was used from 1952-1986 for training exercises that consisted of ?ooding a ?re pad with ?ammable liquids, igniting the ?uids, and subsequently extinguishing the ?re with ?re-?ghting agents including AF FF (1 9, 20). Before the concrete pad was installed in 1982, as well as an oila?water separator, ?lel was dumped directly onto a gravel area and ignited for each ?re?training exercise (19). The aquifer at WAF is comprised of alternating eolian sands and glacial out wash material that is highly permeable and exhibits hydraulic conductivities on the order of 30 mfday (21-23). The water table is located between 5 and 8 below land surface. Aquifer solids are comprised of greater than 85% quartz minerals, with organic carbon and inorganic carbon contents below 0.1% and approximately respectively {21, 22). Flow in the sand and gravel upper aquifer is generally eastward towards Lake Van Etten and south-southeast to the Au Sable River discharge areas at average rates of 0.1 to 0.3 mfday (22-24). Direction of groundwater ?ow at WAFB does not change signi?cantly from season to season (23). Fire Training Pad sepaiaoorSM Drain Field Cr-- c-va _ Flow Uirecticn N Scale: o to n, • Monitoring Well FIGURE 1. Map of (a) Naval Air Station Fallon and (b) Tyndall Air Force Base field sites indicating location of groundwater wells and direction of regional groundwater flow. peefluorinated carboxylatesadsorb bo glass(14).Samples were shipped on ice without preservation and stored at4°C prior to analysis. 5otid-PhaseF.xtractionand Derivatiration.Samples(55— .200 mL) were extracted through 25 mm strong anion exchange(SAX} disks in a manner similar to that described by Field and Reed (IS)with the exception that the SAX disks disk were pretreated prior to use to remove in impurities.Pretreatmentconsisted ofsoaking the disksin 12 nrM HCllacetoxiitrile for 2 days after which the disks were soaked in'pure acetonitrTle for several hours. Just -prior to use, the .disks were rinsed with a minimum of 350 mL of deioitized:water in order to sufficiently rinse the HCl from the disks and wetthem prior to passing groundwatersamples through them. Samples.(55-2Q0 mL)were passed through the.disks strider full vacuum,and the disks were then allowed to dry. The disks containing the exchanged atralytes were placed.in a 2 mL autosampler vial together with 1 mL of acetorritrile,51.2feg ofinternalstandard,and 10014ofmethyl iodide: When Treated at 80 °C for 1 h, the acids were simultaneously eluted from the disk and derivatized to their methyl esters. Spike and Recovery.Spike and recovery experiments were performed to determine the. precision and accuracy of the SAX - disk,extraction and in-vial elution method. A set of experiment's was performed on groundwater sarnples from NAS Fallon.MW 50U and MW 17 that had been previously Quantification of perfluorocarboxylate methylesters was performed usingaHewlett-Packard Model5972 mass selective detector operated In electmn.impact (E17 mode(70 eV). The mass selective detector wa's operated in full scan(50450 amu)mode and in selected ion monitoring (SIM) mode using a dwell time of.100 ms for each ion. The scanning mode was used farquali#ativeidentification while S1M mode was used fior quantification.The ions ofm/z131[GsFs]+,m/z 169 [C3Fr[+, and m/z 219 [C4F9]+, which are characteristic fragments ofpertluoracarbons(16=18),were used toidentify and quantify the methyl esters of perftuorohexanoic acid (PFC6), perlluoroheptanoic acid (PFC7), PFC8, and PFC12. The internalstandard;2-chlorolepidine,was quantified with the ions at m/z 17'7 and m/z 115. The identification of perfluorocarboxylate methyl esters was confirmed byelectron captluenegativeionizat3on(fiCN)7 GC/MS, which gave unique molecular ions-for each of the pertluorinated cartrozylate methyl esters (e.g. m!z 328 for PFCfi, m/z378forl?F67, m/z428 for PFC8,and m/z628 for PT?C12).These measurements were performed with a Varian 3400 gas chromatograpltinterfaced with a Finnigan Model 4023 mass spectrometer. Methane was used as the reagent gas, and the rnass:spectrometer `vas operated in full scan mode(100-650amu).The gas cliromatograph was operated with a column and temperature program identical to that used for the II GYMS. Initially,samples prepared in deionized water were used asthe matrixforconstructing calibration curves,and standard recoveries were:low. However, when samples prepared in tap water,whichcdnfains•inbrganlc cations and anions,were used as the mattax for: constructing calibration curves, quantitative recovery: of standards was obtained. It is proposed that the 350 mL of. deionzed water does .not sufficiently rinse the disks of residual HCI and tap water is required to completely jrinsethe disksand-obtain quantitative recovery, of standards. Therefore, calibration curves for quant4H6aEton ofPFCSwere constructed by passing IOD mL oftap water samples thathad been spiked with 3.6-1080,ug ofPFC8through 25 nvn SAX disks and derlvatizing the acids to their methyl esters using the in-vial elution and deriva- tization technique, The calibration curve for PFC12 was constructed in a simil2lr manner by adding 7.5-113 kg of PFG12standard to 100:rnL oftap water.For all quantization B m ENVIRON. SG.& TECHNOL./ VOL xx, NO.xx, xxxx US00002579 1e+6 (a) Relative Abundance 8e+5 - 2-chlomiepidine 6e+5 - 4e+5 2e+5 0 5 10 i5 20 35 30 25 Time (min) le+6 {b} 2-chlorolepkiine Relative Abundance 8e+5 - 6e+5 4e+5 2e+5 0 5 10 15 20 25 30 35 Time(min) FIGURE Z. (a) Typical El GCIMS chromatogram of PFC8 and PFC12 standards and (b) perfluorinated carboxylates, including PFC6, PFC1, PFC8, and PFCI2(spiked) in Naval Air Station Fallon groundwater. standards. a toial of 5 i.2 ug of the 2-chlorolepidine internal standard was added to the autosamplerviafjust prior to the addition of methyliodide_ Both calibration curves were linear with rz typically greater than 0.99. Quantification of PFC6 and PFC7 was performed assuming a response factor equal to an equimolar amount of PFC8. Results and Discussion Gas Chromatography/Mass Spectrometry.A film thickness of um(30 m x 0.32 mm SPB-1 SULFUR:Supelco. Bellefonte, PA) was necessary to obtain sufficient retention times for the methyf esters ofPFC8 and PFC12 to allow for the separation and quantification (Figure Za). Initial attempts to separate and quantify the perfluorinated carboxylate methyl esters on athin fihn(0.25Itm),30 m x 0.25 mm D13-1(J&W Scientific; Folsom, CA) column were unsuccessful regardless of the initial column temperature. Note that the stationary phases in the SPB-1 SULFUR and DB-1 columns are comparable. A standard of periluorobutyric acid was not observed under any of the described GC conditions; it Is most likely that an Initial oven temperature less than 40 °C would be required. The £I massspectra of methylPFC8(Figure 3a)and PFC12 indicate characteristic perfluorocarbon fragmentation (16, 17) in which the major ions(e.g.,69, I 19, 169,219,etc.) differ by 50 amu,which corresponds to the mass of CFZ.,Molecular ions were not observed for any of the perfluorinated carboxyiate methyl esters under EI conditions: however. molecular ions(Ml- were observed under ECM conditions. For example m/z 428 (in Figure 3b) corresponds to the molecular ion of methyl PFC8. VOL. xx. NO. xx. xx" / ENVIRON. SCI. R TTCHNOL..0 US00002580 1.6e+5 59 (a) Relative Abundance 1.2e+5 8.0e+4 69 [CzFj' 131 4.0e+4 [CsFr]' 119 169 [GsFl.j' ' [C6Fit1 [CTF,~* 381 281 219 231 369 331 1C4Fs]+ 181 0.0 100 50 150 200 I 1 , 250 300 350 t 450 400 [n/L 60000 ~[?} 350 50000 40000 Z. S C 408 30000 378 (M] 428 312 20000 - 10000 - 0 150 t [ el 200 250 300 .., 350 ]t, 400 450 mlz FIGURE 3. (a) El mass spectrum of methyl PFC8.(b) ECNI mass spectrum of methyl PFC8_ Solid-Phase Extraction.Prior to developing asolid-phase extraction method,initial experiments were conducted using diazomethane as the derivatization reagent_ When perfluorinated carboxylates were derivatized using ethanol-based diazomethane, multiple peaks corresponding to methyl and ethyl esters were detected (unpublished data). Because EI GC/MS did not produce molecular ions, ECNI GC/MS was used to verify the formation ofboth methyl and ethyl esters. Consequently, if ethanol-based diazomethane was used for derivauzation in conjunction with El GC/MS,multiple peaks in a chromatogram could be erroneously interpreted as a greater number of perfluorinated compounds than are actually present. In contrast, only the methyl ester was obtained when butyl carbitol (2-(2-butoxyethoxy)ethanol) was used to .prepare the diazomethane reagent. However, because of the hazards associated with the use of diazo- methane and the time-consuming nature of diazomethane derivatization, an alternative method was desired. Derivatizatlon ofthe perfluorocarboxylates by solid-phase extraction and thein-vial elution and derivadzation technique gave only a single peak that corresponded to the methyl ester ofeach perfluorinated carboxylate standard:the identification of each methyl ester was confirmed by ECNI GC/MS. In addition,thesolid-phase extraction approach combined the steps of isolatiop and derivatization,which greatly simplified the procedure and eliminated the use of diazomethane. Six replicate analyses of blank 25 mm SAX disks that had not been prerinsed with 12 mM HCl/acetonitrile prior to use, yielded an average of 21 t 1 ug (4.8`Yo relative standard deviation (RSD)) of PFC8 per disk. No other perfluorinated carboxylates were present in the disks above the detection limit. The PFC8 is associated with the Teflon matrix and not D ■ ENVIRON. SCI. & TECHNOL.!VOL. xx. NO. xx, xxxx US00002581 TABLE 1. Recovery of PFC8 and PFC12 Spiked into Groundwater Samples from Naval Air Station Fallen' % recovery sampie PFC8 PFC12 NAS Fallon MW 51U5 NAS Fallon MW 16 NAS Fallon MW 50U NAS Fallon MW 17 83° 90d 73 74 35 85 77 88 •Duplicate samples were analyzed. Sample volume was 100 mL unless otherwise noted, a Sample volume was 55 mL ' Calculated as the final measured concentration divided by background concentration plus spike concentration and multiplied by 100. The background concentration was 6,570 ug/L dCalcutated as the final measured concentration divided by background concentration plus spike concentration and multiplied by 100. The background concentration was 460 pgtL the embedded anion exchange particles(unpublished data). The background PFC8 was successfully removed by rinsing the disks prior to use with 12 mM HCVacetonitrile followed by 350 rnL ofdeionized water.Itshould be noted that benzoic acid and ethyllrexyfphthalic acid are also present in the disks as artifacts and are removed by the HCl/acetonitrile prerinse step. Accuracy,Precision,and Detection Limits.The recoveries ofPFC8from blank groundwatersamples obtained from NAS Fallon wells MW 50U and MW 17 were 73 and 74%, respectively, while the recoveries ofPFC12were 77and 88%, respectively (Table 1). Because detectable levels of PFC8 occurred in groundwater from MW 5iU and MW 16,standard addition experiments were performed to determine the recoveries of PFC8. The recoveries of the PFC8 spiked into MW 51 U and MW 16 groundwater to give a final concentration double that of the background concentration were 83 and 90%, respectively (Table 1). The recoveries of PFC12 from MW 5IU and MW 16 groundwater, which did not contain background concentrations of PFC12, were 35 and 85%, respectively (Table 1). Although the recovery of PFC8 (83%) differs significantly from that of PFC12 (35%) in groundwaterfrom MW 51 U.the recoveriesofPFC8 and PFC12 were nearly equivalent for the other groundwater samples. Monitoring well 51U is located closest to the fire pit where AFFF agents where applied to burning mixtures offuels and solvents- Due to its proximity to the fire pit,the groundwater from MW 51 U most likely contains the greatest diversity of Inorganic and organic constituents, which may adversely affect PFC12 recoveries relative to that of PFC8,Therefore, although the original intent was to use the PFCIZ as a surrogate standard because it did not occur in the groundwater samples, PFC12 appears more sensitive to matrix interferencescompared to PFC8so that it is an inappropriate choice for a surrogate standard. For this reason, all subsequent quantification was based on the 2-cWorolepidine Internal standard. The precision,indicated bythe RSD,calculated from five replicate analyses eachofgroundwaterfrom NAS Fallon MW 16 and Tyndall AFB T11-2 ranged from 3.7 to 14% (Table 2). The detection and quantitatlon limit of the method was defined as those concentrations ofPFC8 needed to produce a signal-to-noise (RAO-of 3.1 and 10.1, respectively. The detection and quantitation limits for PFC8 were 18 and 36 µg/L, respectively. Application toGrotmdwater5amp1es.Four groundwater samplesfrom both NASFallonandTyndal[AFB were analyzed for perfluorinated carboxylates- Chmmatograms obtained by fin GUMS indicated the presence of multiple perfluorinated compounds all having characteristic perfluorocarbon fragmentation (Figure 2b). Analysis by ECNI GC/MS established the identification of PFC6,PFC7 and PFC8 in groundwater obtained from wells MW 51 U and MW 16 from NAS Fallon. The molecular ions[Ml- for methyl PFC6(m/z 328) and methyl PFC7(m/z378) were observed for peaks eluting 4.7 and 2.3 min before that ofPFC8 (Figure 4a,b).The ECNI mass spectrum for methyl PFC8 in MW 51U was similar to that of the PFC8 standard (Figure 2b). The groundwater samples from NAS Fallon 14iW 51 U and MW 16 had total perfluorinated carboxylate concentrations of 7090 and 540 #g/L, respectively (Table 2). The PFC6 detected in NAS Fallon groundwatersamplesfrom MW 51 U and MW 16 comprised 5.295 and 11%, respectively, of the total perfluorocarboxylates detected.The PFC7 was 2.1% and 3.3% respectively, of the total perfluorinated carboxylates detected in these wells. The dominant perfluorinated carboxylate,PFC8,accounted for 93% and 85%,respectively,of the total perfluorocarboxylate concentration. The highest concentrations ofperfluorocarboxylates were observed in groundwater collectedfrom NAS Fallon MW 51 L', which is the well located closestto the fire-training pit(Figure la). Monitoring well 16, which is Iocated downgradient of MW 51 U and the fire-training pit had lower but detectable concentrations ofperfluorocarboxylates.Groundwaterfrom MW 5OU and MW 17,which are located off gradientfrom the fire-training pit, contained no detectable perfluorinated carboxylates. Over the approximate 100 in distance between MW 51 U and MW I6,the concentrations ofthe perfluorinated carboxyfates decreased with increasing number of carbons. For example,the concentration ofPFC6 decreased 85% over the 100 m compared to decreases of88% and 931/o for PFC7 and PFC8, respectively. The groundwater samplesfrom Tyndall AFB PW-10,PW07, and TI 1-2 contained total perfluorinated carboxylate concentrations of298,159,and 124 µg/L,respectively(Table 2). The compositions of Tyndall AFB groundwater collected from the three wells ranged from 46 to 52% for PFC6, from 13 to 15% for PFC7 and from 34 to 40% for PFC8.In contrast to the groundwater samples from NAS Fallon,the dominant perfluorinated carboxylate in'Tyndall AFB groundwater was PFC6. TABLE 2. Concentrations of Perfluorinated Carbollylates in Groundwater Samples from Naval Air Station Fallon and Tyndall Air Force Base"" , sample n PFC6(ug/i) PFC7(pgQ PFC8(Og/L) total(IJA 3 NAS Fallon MW 51 U 372:!: 4(1,1%) 7090 ± 160(2.3%) 149:L 5(3.4%) 6570 _;l: 150(2-3%) NAS Fallon MW 16 5 57 t 8(14%) 540 t 20(3,7%) 18 t 2(11 %)° 460 ~-_ 20(4.3%) NAS Fallon MW SOU 3 nd nd rid nd 3 rid NAS Fallon MW 17 nd nd nd Tyndall AFB PW-10 2 144 298 38 116 Tyndall AFB PW-07 2 73 159 64 22c 124:1:8(6.6%) Tyndall AFB T11-2 5 64 ~E 4(6.3%) 42 -!- 2(4.13%) 19f 1 (5.3%)c nd nd Tyndall AFB TY22FTA 2 nd nd deviation is given in parentheses. Ind: not detected above the detection limit. `The reported value is near the detection The relative standard limit (SI.N s 3) and less than the quantitatlon limit (STN ~S 10).-The value has been included In the reported total concentration. VOL. xx, NO. xx, xxxx I ENVIRON. SCI. a TECHNOL. x E US00002582 25000 250 (a) 20000 - ~ 15000 N C Q1 C 10000 - 278 5000 - 308 [M]. 328 r lit 150 200 250 450 400 350 300 fil/Z 18000 300 (b) 15000 12000 252 IM] C: 378 8000 C 6000 3000 - 328 259 285 200 250 JI 0 150 200 250 300 Ali I 350 400 450 mIZ FIGURE 4. ECIVI [Hass spectra of (a) methyl PFC5 and (b) methyl PFC7. It is not surprising to observe a suite of perfluorinated carboxviates since the raw materials used in the synthesis of the electrochemical fluorination process used by 3M Co.(3j. Otherfluorination processes,such astelomerization, produce only even number homologues(3).Because ofthe proprietary nature of AFFFs,itis not known if perfluorinated carboxylates are present as one ofthe major surface active agents in AFFF formulations or as unreacted starting materials used in the synthesis of the principal perfluorinated surfactants used in AFFF formulations. In addition, the carboxylates may be combustion, biological, or nonbiological degradation products of the principal perfluorinated components in AFFF mixtures. Unfortunately,the exactsource and history ofAFFF applications at the two field sites are unknown,and therefore, perfluorinated organic compounds are mixtures (3, 19)_ Different ratios of PFC6, PFC7, and PFC8 may result from the use ofdifferent AFFF formulations at the two fire-training areas_ The observed homologous series consisting of even and odd number perfluorinated carboxylates is indicative of the relationship between the observed perfluorocarboxyiate ratios and that of the original AFFF mixtures is unknown. To the bestofour knowledge,very little is known regarding the transport and fate of perfiuorocarboxylates in groundwater. Adsorption to sludge at wastewater treatmentfacilities The highest concentrations of periluorocarboxviates among the groundwater samples from Tyndall AFB were observed in PW-10and PW-07,which are the two wells located closest to the fire-training pit (Figure 1b). Monitoring well T11-2,which islocated downgradient ofthe fire-training pit. had lower but detectable groundwater concentrations of perfluorocarboxyiates- The groundwater collected from awell located north of the fire-training pit, TY22FTA. contained no perfluorinated carboxylates above the detection limit (18 ug/L). F ■ ENVIRON. SCI. a TECHNOL. I VOL. xx. NO. xx, xxxx .\ U S00002583 is considered a significant process for the removal of perfluorinated surfactants during treatment (3). However, detection of perfluorinated carboxylates at the NAS Fallon and Tvndall AFB sites, which have not been used since 1988 and 1992, respectively, is consistent with the view that biodegradation of the long chain perfluorocarbun hydrophobe is unlikely (6, 9, 19). The recalcitrant nature of perfluorinated compounds is attributed in partto the rigidity of the perfluorocarbon chain (9, 20) as well as the strength of the carbon—fluorine bond (3. 9, 21). To the best of our knowledge this is the first definitive identification of perfluorinated carboxylates in groundwater Impacted by fire-fighting activity. Further work is needed to determine if additional perfluorinated components are present, such as perfluorooctane sulfonic acid, which is thought to be one of the principle components in some commercial AFFF formulations. In addition, it is ofinterest to relate the occurrence and distribution of perfluorinated compounds to other site characterization parameters such as dissolved organic carbon,inorganic constituents,and the distribution of co-contaminants and to understand the potential influence of perfluorinated compounds on the biotransformation and transport of other co-contaminants. Acknowledgments The authors thank Donald Hagen and Eric Reiner of3M Co. and Mitch Hubert ofAnsel Inc.for valuable discussions and technical assistance. We would also like to thank Chang Jho and Erik Kissa for reviewing draft manuscripts. Ran HoeppeI and Art Fisher. from NAS Fallon, Full Johnson from the University of Utah, and Erica Becvar from Tyndall AFB are gratefully acknowledged for facilitating sample collection, Supelco. Inc- is gratefully acknowledged for the donation of a GC column and vacuum manifolds. This work was financially supported by the Oregon State Department of Chernistry(N.L. Tartar Research Fellowship)and by a grant from the Environmental Protection ^gency(OER R8211 5. The authors acknowledge the Oregon State University Environmental Health Scienca Mass Spectrometry Core Facility for its support through NIEIIS Grant ES00210. Literature Cited (1) O'Brien,A.F. M.S.Thesis,UniversityofMaiyland,College ParK Marvland. 1994. (2) Henley, M.: Mayfield. H.; Shelley, T. Abstracts of Papas, Pittsburgh Conference,Atlanta,GA,American Chemical Society Washington, DC. 1997; Abstract 519. (3) Kissa, E Fluorinated Surfactants: Synthesls, Properties, and Appifeationx Marcei(Dekker. New York. 1994. (4) Bass,C.M.Ph.D.Dissertation,Uni►visityofOklahoma,Norman, OK. 1982. (5) Howell, R. D.; Tucker,E E. Am. Errvirvn. Lab. 1996, 12, 10. (6) Darwin,Lt L;Ottman.R.E.:Nomran,E.C.:Gott,J.E.;Hanauska, C. P. NatL Fire Pfotect Assoc 1995,67. (7) Chan. D. B.; Chian, E- S.K Envirvn. Pro& 1986. 5,104. (8) Remde, A.: Debus. R. Cbenxsphe a 1996, 52, 1563. (9) Key, B: D.; Howell, R- D.; Criddle. C.S. Environ. Sd. Tmhnoi. 1997. 31, 2445. (10) Godin,C.S.; Nlyhr, B. C.; Lawlor,T. E.; Young,R. R.; Mudi,H.; Clfone, M- A. Genotoxicity Assessment of Perfluorodecanoic Acid usingaBatteryofinvitroand in vivo/in vitro Assays:Harry G. Armstrong Aerospace Medical Research Laboratory. Kensington, MD,December 1990. (I1) Deocampo, N. D; Upham. B. L;Troska,J. E Fundam. Appl. Toxicol. (Suppl.) 1996, 30.2D& (12) Work Plan for Assessing the Feasibility ofIntrinsicRemedlation at Installation Restoration Program Sites: Oak Ridge National Laboratory: Oak Ridge, TN, October 1996. (13) Contamination Assessment Report Active Fire-Training Area FT-23 Tyndall Air Force Base Panama City, FL, FDER Facility No. United Star-; Army Corps of Engineers: Washington, DC, February 1994. (14) Belisle. J.: Hagen, D. F. AnaL Biochem. I980, 101, 369. (15) Field, J. A-: Reed, R_ L. Envirnn. Sci. Technol. 1996, 30, 3544. (16) McLafferty, F. W.; Turecelt, F. rnterprrtatian of Mass Spectra, 4th ed.: University Science Books: Sausalito, CA. 1993. (17) Lyon, P. A; Tomer, K B.: Gross, M. L AnaL Chem. 1985, 57, 2984. (18) Hudllckv, Iv ; Pavlath, A. E. Chemistry of Organic Fluorine Compounds 11• A Critical Review. Amercan Chemical Society. Washington, DC, I995, (19) Key, B. D. Ph.D. Dissertation, Michigan State University, Fast Lansing, MI, 1996. (20) Asakawa, T.; Mouri, M.; Miyagishi, S.: NlshidA M_ Langmuir 1989, 5,343. (21) Smart, B. E. In MolecularStructure and Energettcs: Liebman. J. F., Greenberg, A,Eds.: VCH Publishers: Deerfield Beach, FL, 1986 Vol. 3. Received for review December 29, 1998. Revised manuscript received May 12, 1999. Accepted May 21, 1999. ES981355+ PAGE EST: 6.6 VOL_ xx, NO; xx, xxxx!ENVIRON. SCI. & TECHNOL. ■ G US00002584 DEPARTMENT OF THE NAVY NAVAL RESEARCH LABORATORY 4555 OVERLOOK AVE SW WASHINGTON DC 20375-5320 ,m RcrL, RSr'ER to 7555 Ser 6180/0394 SEP 19 1000 From: Commanding Officer, Naval Research Laboratory To: Distribution Subj: DOD AFNk ENVIRONMENTAL MEETING Encl: (1)Minutes ofsubject meeting 1. The Navy Technology Center for Safety and Survivability ofthe Naval Research Laboratory hosted the DOD AFFF Environmental Meeting on 2-3 August 2000. The meeting was held to exchange information on environmental issues surrounding AFFF. The meeting was sponsored jointly by The Naval Facilities Engineering Command and the Naval Air Systems Command. 2. Enclosure(1)is a copy ofthe minutes of the meeting. 3. The NRL point ofcontact for this program is Dr. Frederick W. Williams, Code 6180,(202) 767-2476, email: fwilliam@ccs.nrl.navy,mil. Distribution Authorized to US Government Agencies and their Contractors Only: Al other requests shall be forwarded to: Commanding Officer Naval Research Laboratory, Wash. DC. THIS INFORMATION HAS NOT BEEN APPROVED FOR PUBLIC RELEASE. US00000605 Distribution: CNO(Code N-451H Barbeau) (Code N457C Ellis) NAVSEASYCOM (Code 05L4 McCrory, Williams) NAWC/WD (Code 4T3 OD Bowman) (Code 4T43 I OD Hoover, Wilson) (Code 4T42EOD Roper) MSC((DCE Parks) HQ/USMC(ASL-38 Bungcayao, Jr) (CSLE-ESE Romero) (LFL-6 Doherty) USACE(CECEW-ETE DiAngelo) USA/SFIM(AEC-EQC Scott) USA/FP (Kochhar) EPA (Dominick) (Code 6205J Rubenstein) FAA/TC(AAR-411 Bagot) NAVFACENGCOM (Donnally) (Code SF Gott) (Code ESC421 Lee) (CFPE Ruffini) (CFPE Simone) (F&MS Killen) HQ/AFCESA/CESM(Hansen, Walker) HQ/USAF/CEVQ (Shah) USAF(ARA Dierdort) MSC (Code N72PC1) NAVAIRSYSCOM (Code 4.3.5.1 Leach) (Code 8.1 Wolfe) NADEP(Code 4.3.4.7 Whitfield) DSC(Code IDA Klein) 2 US00000606 6380/0394A:F'WW September 12, 2000 Minutes Of the DOD AFFF Environmental Meeting Held at the Naval Research Laboratory Navy Technology Center for Safety and Survivability Washington, D.C. On 2-3 August 2000 End (1)to NRL Ltr 9555 6180/0394:FWW Distribution Authorized to US Government Agencies and their Contractors Only; All other requests shall be forwarded to: Commanding Officer Naval Research Laboratory, Wash. DC. THIS INFORMATION HAS NOT BEEN APPROVED FOR PUBLIC RELEASE. US00000607 Minutes of DOD AFFF Environmental Meeting Naval Research Laboratory 2-3 August 2000 Summary A meeting to discuss AFFF environmental issues within the Department of Defense(DoD)was held at the Naval Research Laboratory(NRL), Washington, D.C., on 2-3 August 2000. The meeting was hosted by Dr. Fred Williams, NRL, Director, Navy Technology Center for Safety and Survivability. The meeting was jointly sponsored by the Naval Facilities Engineering Command(NAVFAC)and the Naval Air Systems Command (NAVAIR). The agenda for the meeting is shown in Appendix (1). A list of attendees is provided in Appendix (2), along with a photo of attendees present at the opening general session on 2 August 2000. To facilitate future exchanges of information on this subject, Appendix(2)includes mailing addresses, phone numbers and E-Mail addresses for each attendee. Objective The overall objective ofthe meeting was to provide a forum for open discussion on AFFF environmental issues within DoD. Additionally, the meeting was called to address three specific objectives: (1) Assist NAVFAC in the development ofa DoD design policy for AFFF systems in aircraft hangars and other shore facilities to minimize adverse environmental impact. (2) Obtain information to assist NAVAIR in finalizing their AFFF Environmental Safety and Health Need Assessment Summary(ESH NAS)and in preparing the follow-on Development Plan. (3) Provide information for attendees on the relevant issues surrounding the decision by the 3M Company to phase-out production of AFFF and other products containing perfluorooctyl sulfonate(PFOS). Background There has been growing concern in the past few years about the potential adverse environmental impact of AFFF. This concern has been spawned by a number offactors: The establishment by EPA in 1994 ofthreshold quantities for reporting spills of AFFF due to the butyl carbitol commonly used as a solvent in AFFF Inadvertent activations of AFFF systems in hangars and the resultant clean-up and disposal Reports of problems created by the discharge of AFFF to waste water treatment facilities I US00000608 - Limitations on overboard discharges of AFFF by ships under the Uniform National Discharge Standards(UNDS)ofthe Clean Water Act Anecdotal reports of damage to aquatic life by discharge of AFFF to streams and waterways Various designations of AFFF waste, necessitating expensive disposal by specialty contractors Recognition ofthe persistence and limited biodegradability ofthe fluorocarbon surfactants in AFFF Publicity surrounding 3M's decision to phase-out production of AFFF and other chemicals containing perfluorooctyl sulfonate(PFOS) Claims by vendors of so-called "environmentally-friendly" AFFF alternatives As a result ofthese concerns, the affected Navy Systems Commands have undertaken various actions: - - NAVFAC,under the auspices ofthe DoD Fire Protection Coordinating Committee, has started the development of design policy for shore facility Ai~PT systems to minimize discharges and to address environmental issues. NAVAIR has funded Concurrent Technologies Corporation to draft an ESH Need Assessment Study on AFFF, to be followed by a Development Plan that will recommend future action to alleviate identified problems. NAVSEA has reduced the frequency oftesting ofshipboard AFFF systems to minimize overboard AFFF discharge in compliance with the UNDS regulations. The meeting was called to share recent information and discuss issues relevant to the above concerns and on-going actions. Meeting Scope/Presentations The meeting consisted of general session discussions and presentations as well as two specifically focused breakout sessions. Copies ofthe general session presentations are provided as Appendices(3)— (10). Presentations given at the Hangar Facility breakout session are contained in Appendices(11) and (12). Overall summaries of each breakout session are provided in Appendices(13)and (14). Significant Discussion and Presentation Points There were many important points raised during discussion sessions or contained in formal presentations. Those considered to be the most significant are summarized below (additional details are contained in the appendices): - AFFF is a vital fire fighting agent for controlling and extinguishing flammable liquid fires. Within DoD, it is especially critical for fire scenarios where life safety is paramount, where ordnance is exposed or high value assets are threatened. 2 US00000609 The AFFF military specification (Mil Spec)is considerably more demanding than the applicable UL standard relative to speed ofextinguishment of a flammable liquid pool fire. The AFFF Mil Spec is widely cited in procurement specifications in the civil sector, especially at municipal airports. There are currently 5 manufacturers that have AFFFs on the Mil Spec Qualified Products List. There are many fire fighting foams that are commercially available. However, no non-AFFFs have been able to match the rapid fire extinguishment performance of AFFF. - At present there is no regulation or directive to modify the AFFF Mil Spec. - There is no recognized or universally accepted definition of"environmentally friendly" fire fighting foam. - NAVSEA is the designated DoD technical custodian ofthe existing AFFF Mil Spec. Only NAVSEA can formally change the Mil Spec, though it may be possible to develop a separate specification just for shore-based applications. Inconsistent policy and guidance have led to expensive and questionable secondary containment designs in recent shore facility projects. 3M is voluntarily phasing-out production of AFFF because the fluorocarbon surfactant in their AFFF biodegrades to perfluorooctyl sulfonate(PFOS). PFOS has been identified by EPA as environmentally persistent, bioaccumulative in blood, and toxic to aquatic life and laboratory animals(the degree varies by species). Levels ofPFOS measured in humans and found in blood banks is not considered to present a heath hazard at present levels. Concern is the potential for build-up over time. Other AFFF manufacturers do not produce AFFF that is currently believed to biodegrade to PFOS. It is not known if other AFFFs have a similar problem. EPA is currently in a fact-finding mode relative to other AFFFs. At present the EPA does not prohibit or limit specifically the manufacturing of AFFF. A comprehensive review offederal and local environmental regulations applicable to AFFF (and other foam agents) has just been completed (see Appendix (8)). All fire fighting foams have environmental properties and/or constituents that are regulated. Adverse impact on waste water treatment facilities is a major concern, primarily due to foaming. A "risk based" approach, using the Frequency Vs Severity concepts in Military Standard 882C, has been shown to be feasible for managing AFFF environmental issues in shore facilities. Such an approach may be applicable to other AFFF applications as well. The NAVFAC Facility AFFF Management Working Group will continue development of policy, with a completion goal of approximately 6 months. 3 US00000610 The next meeting ofthe NAVFAC Working Group is scheduled for October 12, 2000. NAVAIR will complete the AFFF Need Assessment Study and prepare the Development Plan to recommend a future course of action. There was a general consensus that a second follow-on DoD meeting should be held (host, location, dates — TBD). Depending on developments between now and the next meeting, a decision could be made to establish a governing charter for a DoD AFFF Environmental Steering Group and perhaps to designate a formal DoD "advocate" for the effort. 4 US00000611 List of Appendices (1) Meeting Agenda (2) List of attendees and photo (3) Presentation: "AFFF Performance Perspective," R.Darwin, Hughes Associates (4) Presentation: "NAVSEA Comments on the AFFF Mil Spec", R. Williams, NAVSEA (5) Presentation: "Hangar Facility AFFF Management Breakout Session Introduction", J. Gott, NAVFAC (b) Presentation: "AFFF Environmental Impact Breakout Session Introduction", J. Hoover, NAWCWD China Lake (7) Presentation: "Issues With 3M's Withdrawal from the Market", C. Hanauska, Hughes Associates (S) Presentation: "AFFF Environmental Impact Review", W. Ruppert, Hughes Associates (9) Presentation: "AFFF Management — Risk Based Approach", D. Verdonik, Hughes Associates (10) Presentation: "Phasing out a Problem: Perfluorooctyl Sul£onate", M.Dominiak, EPA (11) Presentation: Facilities Background and AFFF Issues", J. Simone, NAVFAC (12) Presentation: "AFFF Risk Assessment", A. Wakelin, Hughes Associates (13) Presentation: "Summary of Shore Facility AFFF Management Breakout Session", D. Verdonik, Hughes Associates (14) Presentation: "Summary of AFFF Environmental Breakout Session", J. Hoover NAWCWD China Lake and R. Darwin, Hughes Associates US00000612 APPENDIX (1) Meeting Agenda DOD AFFF Environmental Meeting Location: Building 207(Chemistry Building) Naval Research Laboratory, 4555 Overlook Ave, Washington DC,20735 Agenda: Wednesday August 2nd 0830 —0845 Welcome and Introduction -- Dr Fredrick Williams, NRL,Director, Navy Technology Center for Safety and Survivability. 0845-0915 AFFF Performance Perspective — Robert Darwin, Senior Engineer, Hughes Associates,Inc. 0915-0925 NAUSEA Comments on the AFFF Military Specification - Robert Williams, NAVSEA Fire Protection and Damage Control Division 0925— 0935 Hangar Facility AFFF Management Breakout Session Introduction Joseph Gott, NAVFAC,Director, Navy Facilities Safety and Health Office 0935 —0945 AFFF Environmental Impact Breakout Session Introduction —Dr.Jim Hoover, NAWCWD,Head, Combustion Research Branch 0945— 1000 Break 1000-1015 Issues Surrounding 3M Withdrawal from the Market — Chris Hanauska, Senior Engineer, Hughes Associates, Inc. 1015-1100 Presentation of AFFF Environmental Regulatory Aspects — Bill Ruppert, Senior Environmental Engineer, Hughes Associates,Inc. 1100-1130 Summary Presentation on Risk Assessment for Hangar Facilities — Dr. Dan Verdonik, Hughes Associates, Inc. 1130 —1230 Lunch 1230-1600 Breakout sessions Thursday August 3nd 0830 —0930 3M Withdrawal from Market — Mary Dominiak,EPA,Chemical Control Division, Office ofPrevention, Pesticides & Toxic Substances. 0930 —1230 Presentation of Breakout Session Conclusions. Discussion ofany further requirements to complete breakout session action items. US00000614 Hangar Facility AFFF Management Breakout Session Session Objectives and Details: The objectives of the Naval Facility Engineering Command(NAVFAC)hangar facility AFFF Management breakout session are: • To begin efforts toward developing a policy that details requirements for hangar facilities that will provide "adequate measures" to: (a) prevent an accidental AFFF discharge, (b)limit any adverse environmental impacts from a release. • To achieve an agreement on the definition of"adequate measures" and to begin to establish design criteria to meet them. Initial draft design criteria and costs ofspecific engineering solutions will be presented and discussed as a starting point. Agenda 1230 1315 1315- 1430 1430-1600 Facility Background and Issues — Joe Simone, Head Fire Protection Engineer, Naval Facilities Engineering Command Risk Assessment for Hangar Facilities — Alison Wakelin; Fire Protection Engineer, Hughes Associates, Inc. Design Criteria Discussion and Development List of Breakout Session Attendees: D. Verdonik (Chair) J. Gott W.Ruppert A. Wakelin J. Simone V. Donnally T. Ruffini D. Roderique G. Sadler L. Wolf K. Ellis M. Doherty K. Kochar B. Scott R. Talbot R. Hansen J. Shah F Williams US00000615 AFFF Environmental Impact Breakout Session Session Objectives and Details: The objective of this meeting is to share the technical data related to the environmental impact, status and the planned future use of AFFF. NAVAIR will use output from this session to ensure their Environmental Safety and Health(ESH)Need Assessment Summary (the where we are today)is accurate and complete, and to ensure their Development Plan (the where we go from here) is consistent with the need to provide sound fire protection in an environmentally responsible manner. The AFFF Environmental Impact working group will address the following questions: • What current and future environmental regulations impact AFFF use and why (data and politics)? • What data do we have(or lack) on the environmental impact of AFFF? • What technology or products exist that could help reduce AFFF releases into our environment or mitigate the impact ofthose releases? • What technology or products could be applied to recycle or reuse AFFF? • What alternatives to AFFF currently exist and how do they compare in effectiveness, cost, environmental impact, availability, etc? List of Breakout Session Attendees: J. Hoover(Chair) R.Darwin J. Scheffey C. Hanauska W.Leach D. McCrory R. Williams S. Wade M. Wade K.Bagot R. Morris B. Parks S. Johnson P. Bungcayo R. Lee R. DiAngelo D. Dierdorf J. LaPoint 1. Young US00000616 APPENDIX (2) List of? Attendees and Photo [B -L] Keith Sagot FAA FAA Technical Center AAR-411, Bldg. 296 Atlantic City International Ai Atlantic City, NJ 08405 Phone: 609-485-6383 Kathy Ellis Air & Wastewater Program Manager OPNAV(N45) Chief of Naval Operations, N4570 2211 Soulh Clark Place Rm 644 Arlington, VA 22206 Phone: 703-602-2568 bagot: kehh.bagot@tc.faa.gov ellis: Ellis.Kathy@HQ.NAVY.MIL Les Bowman NAWCWD China Lake Weapons Division Code 4T310D China Lake, CA 93555-6100 Paul G Sungcayao Jr USMC HOMC-ASL-38 2 Navy Annex Washington DC, DC 20380 United States Phone: 760-939-8813 Phone: 703-614-183v Fax: 703-697-7343 Phone: 410-737-8677 Phone Ext.: 228 Fax: 410-737-8688 darwin: bdarwin@haifire.com Robert M. DlAngelo CECEW-ETE Army Headquarters U.S. Army Corps of Engineers 20 Massachusetts Avenue, NW Washington DC, MD 2031 4-1000 Phone: 202-761-4803 Phone: 850-283-3734 Fax: 850-283-9797 Phone: 703-695-8541 Fax: 703-695-8550 doherty: dohertymc@hgmc.usmc.mil Mary F. Dominiak EPA U.S. Environmental Protection Agency 1200 Pennsylvania Avenue, NW Washington DC, MD 20460 dominiak: Dominiak.Mary@epamail.epa.gov Vincent R. Donnally Design Criteria Manager NAVFAC 1510 Gilt>ert Street Norfolk, VA 23511-2699 Phone: 410-737-8677 Phone Ext.: 242 Fax: 410-737-8688 hanauska: hanauska@haifire.com Raymond Hansen Fire Protection Engineer USAF HQ AFCESAlCESM 139 Barnes Drive Suite 1 Tyndall AFB, FL 32403-5319 United States Phone: 850-283.6317 James M. Hoover Commander NAWCWD China Lake Naval Air Warfare Center Weapons Division 1 Administration Circle AItn:Code 4T431 OD, J.M. Hoover China Lake, CA 93555-6100 Phone: 760-939-1645 Phone Ext.: 473 Fax: 760-939-2597 hoover: HoeverJM@navair.navy.mil dierdorf: Doug.Dierdorf@tyndall.af.mil Michael C. Doherty Water Program Manager USMC Headquarters, U.S. Marine Corps (LFL-6) 2 Navy Annex Washington DC, MD 20380-1775 Christopher P. Hanauska Senior Engineer Hughes Associates, Inc. 3610 Commerce Drive Suite 817 Baltimore, MD 21227-1652 Hansen, Ray: Ray.Hansen@AFCESA.AF.MIL diangelo: Robert.M.DiAngelo@HQ02.USACE.ARMY.MIL Douglas S. Dierdorf Principle Scientist USAF (ARA) 139 Barnes Drive Applied Research Associates Suite 2 Tyndall AFB, FL 32403 Phone: 202-685.9323 gott: GottJE@navfac.navy.mil bungcayao: bungcayaoJRPG@hgmc.usmc.mil Robert L. Darwin Senior Engineer Hughes Associates, Inc. 3610 Commerce Drive Suite 817 Baltimore, MD 21227-1652 Joseph E. Gott Director, Safety & Occupational Health NAVFAC Naval Facilities Engineering Command Code SF 1322 Patterson Avenue,SE Suite 1000 Washington Navy Yard, DC 20374-5065 Phone: 202-260-7768 Fax: 202-260-10% Samuel R. Johnson Enviromental Engineer MSC MSC code N72PC1 Washington Navy Yard Bldg 914 Charles Morris Ct, S.E. Washington DC, MD 20375 Kiran C.Kochhar Fire Protection Engineer Army P. O. Box 2250 201 Prince Frederick Drive Winchester, VA 22604-1450 Phone: 202-685-5765 Phone:540-665-3907 kochhar: Kiran.C.Kochhar@tacOl.usace.army.mil John LaPoint Manager Enviromental Processes Concurrent Technologies Corp. 9570 Regency Square Blvd. Suite 400 Jacksonville, FL 32225 Phone: 904-722-2505 lapoint: lapointj@ctc.com donnally: DonallyVR@efdlant.navfac.mil anrw. -Ct. w.w.m., US00000618 L-V William B. Leach Fire Protection Team Leader NAVAIR Naval Air Warfare Center Aircraft Division Attn: Bill Leach, Code 4.3.5.1 Bldg 562-3 Highway 547 Lakehurst, NJ 08777-5049 Phone: 732-323-1184 William H. Ruppert Senior Engineer Hughes Associates, Inc. 3610 Commerce Drive Suite 817 Baltimore, MD 21227-1652 Phone: 410-737-6677 Phone Ext.: 283 Fax: 410-737-8688 ruppert: wruppert@haifire.com leach: LeachWB@navair.navy.mil Dr. Richard Lee Project Manager NFESC Code ESC421 Naval Facilities Engineering 1100 23rd Avenue Port Hueneme, CA 93043 Phone: 805-982-1670 Fax:805-982-4832 Joseph L. Scheffey Director Hughes Associates, Inc. 3610 Commerce Drive Suite 817 Baltimore, MD 21227-1652 Dennis McCrory NAVSEA Naval Sea Systems Command Attn: Code 051-4 2531 Jefferson Davis Ffwy. Arfington, VA 22242-5160 Phone: 703-412-7687 Billy Ray Scott CWA Wastewater Program Manager Army SF I M-AEC-EQC BLDG E-4435 Aberdeen Proving Ground, MD 21010 Phone: 410-436-7073 Scott: Billy.Scott@aec.apgea.army.mii morris: morris_renee@bah.com Phone: 202-685-5764 Jay Shah USAF HQ USAF/CEVQ 1260 Air Force Pentagon Pentagon Washington DC, MO 20330-1260 Phone: 703-607-0120 shah: jayant.shah@pentagon.AF.mil Parks: Brad.Parks@msc.navy.mil Dawn Roderique TAMS Consultants, Inc. 2101 Wilson Blvd Suite 300 Arlington, VA 22201 Phone: 410-737-8677 Phone Ext.: 220 Fax: 410-737-8688 scheffey: joe@haifire.com mccrory: McCrMDM@NAVSEA.NAW.MIL Braddock L. Parks Damage Control Engineer MSC Military Sealift Command 914 Charles Morris Court Washington Navy Yard Washington DC, MD 2039&5540 Phone: 757-627-1112 sadler. gosadier@transystems.com lee: leed@nfesc,navy,mil Renee Morris Associate Booz, Allen & Hamilton, Inc. 1725 Jefferson Davis Highway Suite 1203 Arlington, VA 22202 George 4.Sadler Principal Glenn & Sadler 150 Boush Street Suite 1000 Norfolk, VA 23510 Phone: 703-312-1275 Joseph A. Simone Chief Fire Protection Engineer NAVFAC Naval Facilities Engineering Command 1322 Patterson Avenue SE Suite 1000 Washington DC, MD 20374-5065 Phone: 202-685-9177 simone: SimoneJA@navfac.navy.mil roderique: Droderique@TAMSCONSULTANTS.COM R Rubenstein EPA Code 6205 J U.S. EPA 1200 Pennsylvania Ave, NW Washington DC, MD 20460 Phone: 202-564-9155 Robert Talbot SVERDRUP 234 South Fraley Blvd. Suite 100 Dumfries, VA 22026 ta l bot: 9talborp@sverdrup.com rubenstein: rubenstein.reve@epa.gov T Ruffini NAVFAC c/o Chief Fire Protection Engineer 1322 Patterson Ave, SE Suite 1000 Washington DC, MD 20374-5065 P--61I Daniel P. Verdonik Director, Enviromental & Pollution Prevention Prog Hughes Associates, Inc. 3610 Commerce Drive Suite 817 Baltimore, MD 21 227-1652 Phone: 202-685.9177 Phone: 410-737-8677 Phone Ext.: 236 Fax: 410-737-8688 verdornik: danv@haifire.com •]- P--KT'b N US00000619 [W -Y] S. Michael Wade Contractor ASN (S & S) OAS (I& E) Safety & SuvWbility Office Washington Navy Yard Bldg 36 720 Kennon Street, SE Rm 110 Washington DC, MD 20374-5028 Phone: 202-685-6858 Fax: 202.685-6862 wade: wade.stanleyghq.navy.mil Stanley R Wade Jr Senior Engineering Technician M. Rosenblatt & Sons 2341 Jefferson Davis Hwy Suite 500 Arlington, VA 22202-3885 Phone:703-415-7800 Phone Ext.: 640 Fax: 703-415-7828 Wade, S: swadeomrosenblati.amsec.com Alison Wakelin Fire Protection Engineer Hughes Associates, Inc. 3610 Commerce Drive Suite 817 Baltimore, MD 212274 United States Phone: 410-737-48677 Phone Ext.: 282 Fax: 410.737-8677 wakelin: awakelin@haifire.com Fred Williams Director NRL NRL Code 6180 4555 Overlook Avenue SE Washington DC, MD 20375 Phone: 202-767-2476 Fax: 202-767-1716 Wiliams: WI iam(Dccs.nrl.navy.ntil Robert B. Williams NAVSEA Naval Sea Systems Command,051_4 2351 Jefferson Davis Hwy. Arlington, VA 22242-5160 Phone: 703-602-5552 Phone Ext.: 301 williams: WilliamsRB@NAVSEA.NAVY.MIL Eric Wilson Materials Manager NAWCWD China Lake Commander 1 Administrative Circle Code 4T4310D (E. Wilson) Ridgecrest, CA 93555 Phone: 760-939-8064 Wilson: wilsone@navair.navy.mil Larry Wolfe NAVAIR Code 8.1 NAVAIRSYSCOM Bldg 404 22145 Arnold Circle Patuxant River, MD 20670-1541 Phone: 301-757-2132 wolfe: wotfelg@navair.navy.mil Iris Young Chemist-Analytical & Environmental Studies Canada National Defense Dept. of National Defense Quality Engineering Test Est. Ottawa, ON, Canada K1 OK2 Phone: 819-9941681 Fax: 619-997-4096 young: i.young@debbs.ndhq.dnd.ca RtvQm YIVIOW RYAN rN~MTI b 1MnlCM US00000620 Top Row: C. Hanauska, D. McCrory, J. Simone, L. Wolf, K. Bagot, M. Doherty, B. Parks, J. LaPoint, S. Johnson, R. Hansen, R. DiAngelo Middle Row: W. Ruppert, B. Williams, D. Roderique, J. Hoover, J. Gott, J. Scheffey, D.Verdonik, J. Shah, W.Leach, P. Bungcayo, R. Darwin, K. Kochar, R. Talbot, S. Wade Bottom Row: F. Williams, R. Morris, T. Ruffini, A. Wakelin, D. Dierdorf, B.R. Scott, I. Young, K. Ellis, G. Sandler, R. Lee, M. Wade US00000621 APPENDIX(3) Presentation: "AFFF Performance Perspective" R. Darwin, Hughes Associates, Inc. Baltimore MD US00000622 AFFF Performance Perspective Robert L. Darwin,PE Senior Engineer 2 August 2000 Hughes Associates, Inc. US00000623 History of Foam 1920-40 Chemical Foam 1940-70 Protein Foam (Air Foam) 1970-2000 AFFF AFFF Key Events: 1961 First experiments with fluorocarbon surfactants at NRL 1962 First Mil-Spec(Mil-F-23905, 1 Nov 63) 25 % concentration (fresh water only) Emphasis on twin agent application 1963 Large scale tests at NAS pensacola Led to procurement of 100 twin agent units 1964 Helo air borne TAU tests at NAS Miramar US00000624 1965 6% concentration developed by 3M (FC-194) 1966 Testing ofFC-194 in airfield crash trucks Selective conversion ofsome crash trucks 1967 Flight deck conflagration on USS Forrestal TAUS to aircraft carriers Push to develop seawater-compatible AFFF 1967 Seawater —compatible AFFF developed by 3M/NRL 1968 Additional crash truck tests at NAS Miramar 1968 Shipboard equipment tests w/ seawater at NAS Jacksonville First edition ofseawater/AFFF mil spec(Mill-F-24385) 1969 Flight deck conflagration on USS Enterprise Push to convert ships to AFFF 1970 Navy starts comprehensive conversion ofship systems and crash trucks 1973 USAF starts converting all USAF crash trucks US00000625 UL Listed Foams (Per UL 162-"Foam Equipment & Liquid Concentrates") AFFF — Aqueous Film Forming Foam FFFP — Film Forming Fluoroprotein FP — Fluoroprotein PF — Protein Foam Manufacturers Concentrates AFFF 24 110 FFFP 5 16 FP 12 26 PF 5 6 US00000626 Mil Spec Qualified Product List(QPL) Ansul Ansulite 3(AFC-5A)* Ansulite 6(AFC-5) * Type 3 Type 6 3M FC-203C FC-203CE FC-203CF Type 3 FC-206C FC-206CE FC-206CF Type 6 Chemguard C-301MS Type 3 National Foam Aer-O-Water 3-EM Aer-O-Water 6-EM Type 3 Type 6 Angus Tridol M Type 3 * Also UL Listed US00000627 "Application Density"(Defined as the Gallons of Agent Per Unit Area ofPool Fire Size) is the best measure of effectiveness for a flammable liquid pool fire Application Rate = GPM/Sq Ft of fire area Application Rate x Ext Time = Application Density GPM/Sq Ft x Minutes = Gals/Sq Ft Example Fire Area = 1000 Sq Ft Appl Rate of Agent — 200 GPM Ext Time = 0.5 minutes Appl Rate — 200 GPMJ1000 Sq Ft = 0.2 GPM/Sq Ft Appl Density = Appl Rate x Time = 0.2 GPM/SgFt x 0.5 minutes = 0.1 Gals/SgFt AFFF Performance Requirements Mil Spec(Mil-F-24385): Max Appl Density 2 gpm/28 sq ft x 30/60 minutes = .036 gal/sq ft 2 gpm/50 sq ft x 50/60 minutes = .033 gal/sq ft Underwriters Laboratory: 2 gpm/50 sq ft x 3 minutes = .12 gal/sq ft (Maximum extinguishment time is 5 minutes for fluoroprotein and protein foam) US00000629 Rapid Extinguishment ofPool Fires is Critical When: •Pool fire threatens high value assets(such as an aircraft hangar) •Pool fire under an occupied aircraft(must maintain fuselage integrity and rescue occupants) •Pool fire exposes weapons to potential "cook off' US00000630 Relative Performance ofFoam Agents on Pool Fires (Best) AFFF(Mil-Spec) AFFF(UL listed, non Mil-Spec) AFFF (non UL,non Mil-Spec) FFFP FP PF (Worse) Wetting Agents USOD000631 UL Listed Wetting Agents (Based on NFPA 18) "A liquid concentrate for addition to water to produce a solution having a greater fire extinguishing, efficiency than plain water" Manufacturers: 11 Agents: 13 US00000632 If Use Non-Film Formers: • Extinguishment time will be slower, unless application rate is increased • Higher application rate causes Greater system cost Greater quantity of agent emitted • Must consider possible need for "air aspiration" Replace nozzles Less reach than "non air aspirated" US00000633 AFFF Environmental Issue - 1994 Glycol Ethers(Butyl Carbitol), solvent in most AFFFs, placed on EPA list of hazardous air pollutants. Since no reporting threshold had been established, a default quantity of one pound per day was established for required reporting under CERCLA. Because Diethylene Glycol Butyl Ether(DGBE)typically comprises about 20 % of AFFF,spills ofjust a few gallons of AFFF had to be reported to the National Response Center and to State and local officials. One pound per day reporting requirement dropped in 1996. Some manufacturers substituted Propylene Glycol for Ethylene Glycol and declared their foam to be "environmentally friendly". US00000634 DOD Uses of AFFF • Shipboard Foam Systems • CFR Vehicles at Airfields • Aircraft Hangar Foam Systems • Misc Shore Facilities Hush Houses Jet Engine Test Facilities Hardened Aircraft Shelters Aircraft Fueling Stations Fuel Farms • Foam Sytems on Structural Pumpers US00000635 DOD AFFF Discharges • Fires • Training Evolutions • System Tests and Maintenance • Accidental/Malicious Discharges • Research and Development US00000636 There is a Need to Quantify and Characterize: • All DOD AFFF applications(What precisely do we use it for ?) • Precise quantities in service and in reserve stocks(How much do we have ?) • Annual emmisions(type and quantity)(How much do we discharge ?) US00000637 APPENDIX (4) Presentation: `NAUSEA Comments on the AFFF Mil Spec" R. Williams, Naval Sea Systems Command US00000638 NAVSEA Comments On the AFFF Military Specification Mil-F-24385F (Amendment 1 of 8/94) (Talking Points) Presentation to DOD AFFF Environmental Meeting 2 August 2000 Robert B. Williams Fire Protection & Damage Control Division Naval Sea Systems Command (Technical Custodian of the AFFF Mil-Spec) US00000639 1. I would like to express appreciation to NAVFAC and NAVAIR for sponsorship of this Conference. Also, I appreciate the opportunity to establish the NAVSEA perspective up front. 2. This conference is important and timely: Recently there has been a proliferation of Navy groups active in AFFF; usually with no focus, some scattered and uncoordinated EPA contacts. Recently there has been aggressive commercial marketing of so-called "environmentally friendly foams"; yet there is no established definition of "environmentally friendly foam". AFFF is subject of considerable hype: effect on sewage plants, danger to aquatic life, exposure results in mutant first born, etc. AFFF spills are media friendly- very visible, makes for good "films at 1111 , photos provide permanent record, helps stir up environmental activists Real issues from my perspective: 3M withdrawal and fall out relative to other QPL AFFFs Restrictions by AHJs; technical basis or not Unknown forthcoming EPA activity All are on agenda to be addressed 3. The product I personally desire of this conference is to specifically identify what the problems are regarding MILSPEC AFFF, and problems that are inherent to any foam alternative (visible, wastewater treatment plants). Appears money is & will be directed at AFFF. My concern is that funding needs to be attached to a focus on specifics that are documented as requiring resolution. US00000640 Navy labs and contractors see a golden egg out there on this topic; I personally don't want to see them going off into the sunset with a generic task to find an environmentally friendly firefighting agent. (whatever friendly means). The specific problems to be resolved require documentation before charging onto a search for solutions; doesn't always happen in correct order. The agenda appears to support what I hope is the conference objective. 4. A few quick comments about the MILSPEC and shipboard applications: NAVSEA is custodian; only NAVSEA can revise. appointed cannot. Self However, an alternate extinguishing agent specification under someone else's cognizance could be created. For example, it might be feasible to develop a separate specification just for shore facility use (fresh water only, one percent, universal foam, no refractive index requirement, etc). NAVSEA goal regarding the spec: Satisfy environmental requirements without degradation of firefighting effectiveness. If maintaining performance requirements is not possible, then where do we draw the trade-off line in the sand? (fish vs. sailors; national defense vs. environment) MILSPEC contents - shipboard oriented, even though it is essentially the national standard ashore and afloat: AFFF is for two dimensional shallow spill fires, rapid control and extinguishment are essential. No "foam-of -themonth" has matched the performance of mil-spec AFFF. Environmental provisions in spec; fish kill, BOD/COD limits, chemical restrictions. Compatibility: seawater effectiveness, intermixing of products from different manufacturers on QPL. It is an integrated match with our capital investment in hardware: viscosity, corrosion, pipe & tank materials, effect on seals/gaskets, a refractive index, container size & strength. US00000641 5. Our primary environmental involvement has been with the Uniform National Discharge Standards (UNDS) program which is relative to overboard discharge of liquids; basically a Clean Water Act action item. Our imput to EPA, which has been accepted thus far, is discharge management: New construction/alterations - no repeat testing, at sea Preventative Maintenance - reliable hardware, reduced testing periodicity Fewer ships Geographic restrictions: no discharges within 3 miles of coast, must be making at least 10 knots for discharges within 3-12 miles, preference for only discharging when greater than 12 miles out 6. In closing, I pass along that as custodian of the MILSPEC, I have no direction, pressure, or formal or informal tasking to conduct an environmental review of MILSPEC AFFF aside from the UNS. At NFPA aviation committee meetings I have queried major airport fire chiefs, all of whom stated no direction to pursue an alternative to MILSPEC AFFF. However, we at NAVSEA know whether politically, technically, or regulatory driven, environmental restrictions on AFFF may be coming. We fully support this conference, identification of problems & potential problems, and initiation of remedial research/actions. US00000642 APPENDIX(S) Presentation: "Hangar Facility AFFF Management Breakout Session Introduction" J. Gott, Naval Facilities Engineering Command US00000643 Hangar Facility AFFF Management Breakout Session Introduction (Talking Points) Presentation to AFFF Environmental Meeting 2 August 2000 Joseph Gott Director, Navy Facilities Safety and Health Office Naval Facilities Engineering Command US00000644 AFFF DOD Meeting 'Talking Points • Need a consistent DOD position on AFFF management • If we are not proactive, AFFF will become our next halon 1301 • AFFF is only product on market right now that meets our needs • Time for the design engineers, and environmental engineers to come together • The services have already done this with the Unified Design Guidance Group • As past chair ofDOD HE committee, we wrote the first tri-service design criteria • Fixed containment systems are affecting our mission because they have already caused the omission of AFFF from some hangars resulting in the air wings inability to perform their mission • This is the beginning ofa working group to address this important issue • Need to get all the right players • Need to address AFFF management from a risk assessment approach • Need to dismiss all the myths and fears and address the facts • Need to give the local regulators something to reference as adequate protection • Need to determine if additional research is needed to produce a different AFFF • Discuss changes to NFPA 409 - mandatory drains, reduced AFFF, various protection options • NAVFAC has long history in fixed AFFF systems, their behavior, problems, and design characteristics US00000645 APPENDIX(6) Presentation: "AFFF Environmental Impact Breakout Session Introduction" J. Hoover, Naval Air Warfare Center China Lake CA US00000646 AFFF Environmental Impact Breakout Session Introduction ('Talking Points) Presentation to DOD AFFF Environmental Meeting 2 August 2000 Dr. Jim Hoover Head,Combustion Research Branch NAWCWD China Lake US00000647 The purpose of the AFFF Environmental Impact Breakout Session will be to share technical information within the DoD on AFFF use and environmental impact. This information will be used to assist the completion of two environmental planning documents used by the Naval Air Systems Command (NAVAIR)- an Environmental Safety and Health Needs Assessment Summary(NAS)and a Development Plan. The NAS will provide a "snap-shot" of technical issues surrounding AFFF use and environmental impact, and the Development Plan will recommend a strategy for future efforts within NAVAIR. Background: The importance of AFFF in protecting Navy personnel and assets must not be understated. Likewise, public safety and commercial assets are highly dependent on AFFF for fire protection. Its firefighting performance remains unmatched and much remains unknown about its human health and environmental effects. Other services and agencies have data and experiences with AFFF that could assist the Navy in future decision making,so a forum for technical information exchange is needed. In planning for the future, all aspects of technical knowledge about AFFF (and all of its formulated components) should be considered. These should include costs, performance/function, human health and environmental effects, availability, inventory, alternatives, etc. Break-out Session Format: The following questions will be asked of the participants to promote discussion and information exchange. Participants will be invited to provide other questions. 1. What current and future environmental regulations impact AFFF use and why (data and politics)? 2. What data do we have (or Iack) on the environmental impact of AFFF? US00000648 3. What technology or products exist that could help reduce AFFF releases into our environment or mitigate the impact of those releases? 4. What technology or products could be applied to recycle or reuse AFFF? 5. What alternatives to AFFF currently exist and how do they compare in effectiveness, cost, environmental impact, availability, etc? b. What related planning documents exist with other services or agencies? 7. Whatfollow--on strategies should be considered? US00000649 APPENDIX (7) "Issues With 3M's Withdrawal From the Market" C. Hanauska Hughes Associates, Inc_ Baltimore MD US00000650 Issues with 3M's Withdrawal from the Market AFFF DoD Meeting Christopher Hanauska HUGHES ASSOCIATES, INC. FIRE SCIENCE & ENGINEERING August 2, 2000 US00000651 Purpose of this Presentation ■ Mary Dominiak of EPA will provide more detailed information tomorrow ■ Provide some background for her presentation ■ Frame the issue relative to the subjects of this meeting ■ This presentation is only an executive summary US00000652 Fluorochemical Surfactants (FC's) ■ FC's are a component of AFFF - One of several components in AFFF - FC's are difficult and expensive to make - Formulators have minimized (and attempted to eliminate) the FC content for 30 years - Necessary for performance (especially for CFR) • rapid fire knockdown • relatively low application rates US00000653 What is an F ? ■ CU17-functional group ■ Length of carbon chain varies ■ Fluoronated carbon chain is very stable ■ Functional group gives different properties j USOODO0654 FC's for AFFF Do Not Fully Biodegrade ■ 3M's FC's => PFOS (Perfluorooctyl Sulfonate) ■ Other FC's => ? ■ Functional group may biodegrade, but something is always left ■ Ultimate fate unknown ■ "Persistent" ~a USOODO0655 3M Performed Testing (Last 2 Years) ■ Found PFQS - in blood banks around the US - in fish and birds ■ Discovered toxicity issues - reproductive sub-chronic studies ■ `Bioaccumulative" and "Toxic" Vj US00000656 3M Voluntarily Phasing Out PFOS Related Chemicals ■ Scotchguard, Scotchban, industrial uses, AFFF ■ About 2 years for complete halt of production ■ Decision made at highest level of3M - were in discussion with EPA at the time ■ An unexpected and extreme action Vj US00000657 If Only 3M PFOS FC's are a Problem ■ Other non-PFOS FC based AFFF's are on the QPL ■ Possibly a short term supply issue ■ Should not be a major fire protection/environmental concern US00000658 Do Non=PFOS FC's Have a Problem-? ■ EPA has asked manufacturers to examine and test ■ What constitutes a "problem" uncertain - "Bioaccumulative""Toxic" ■ EPA will do risk/benefit and risk/risk analysis - Understanding of importance of AFFF to fire protection US00000659 Conclusions ■ No FC specific regulations exist ■ No apparent short teliii(1 year) problems ■ Mid-teint(2-3 years) problems related to supply only - as 3M withdraws from market ■ Potentially no long term problems(3+ years) ■ Unless other FC's have significant problems US00000660 APPENDIX(8) Presentation: "AFFF Environmental Impact Review" W. Ruppert Hughes Associates, Inc. Baltimore MD US00000661 Aqueous Film Forming Foam (AFFF) ENVIRONMENTAL IMPACT REVIEW Bill Ruppert HUGHES ASSOCIATES, INC. FIRE SCIENCE & ENGINEERING u.cnnnnnaao Background: AFFF Constituents ■ MILSPEC based on Performance, not Constituents ■ Must be on Qualified Products List - QPL ■ Main Ingredients in Firefighting Strength Foam: - WATER = 98%-99% - Butyl Carbitol (Glycol Ether)= 0.5%-1.1% - Fluorosurfactants & Hydrocarbon Surfactants = 0.03%-0.45% - Ethylene Glycol(Not in all formulations)= 0.34%-0.60% - Urea(Not in all formulations)= 0.2-0.4% V~ US00000663 Background: AFFF `Environmental' Properties ■ MIL-F-24385F Requirements - Chemical Oxygen Demand 3% Concentrate - 1,000,000 mg/L Max 6% Concentrate - 500,000 mg/L Max • Calculated Firefighting Strength - 30,000 mg/L Max Biochemical Oxygen Demand (20 Day) • =(0.65 X COD)or greater - Aquatic Toxicity (LC50, Killiefish) • 3% Concentrate - 500 mg/L Min • 6% Concentrate -1000 mg/L Min • Calculated Firefighting Strength - 16,667 mg/L Min ■ Persistence and Bioaccumulation Only Fluorosurfactants - Not in other constituents -- example: Butyl Carbitol log BCF = 0.46 ■ Foams j US00000664 Background: AFFF Properties MILSPEC vs. Typical QPL Product Property MIL-F-24385F Requirements 3% Chemical Oxygen Demand (mg/L) Biochemical Oxygen Demand 6% Typical QPL Product FF 1,000,000 5009000 30,000 7509000 Max Max Max BOD20 > 0.65 x COD 720,000 6% FF 341,000 22400 2745000 21,600 (0.%*COD) (0.80*COD) (mom) Aquatic Toxicity (Killiefish) (mg/L) 3% 500 Min 1000 Min 16,667 >1000 >1000 >16,777 or >33,333 E US00000665 Codes and Standarus Survey Approach ■ Electronic Review ■ Federal Environmental Regulations - "AFFF" - MILSPEC AFPF Constituents(19) • Surfactants • Fluorosurfactants • Glycol Ethers • Urea, etc. - AFF'N "Environmental" Properties • Biochemical And Chemical Oxygen Demands • Aquatic Toxicity • Foaming ■ DOD,State And Local Regulations 46 MILSPEC AYFF Constituents j US00000666 Codes and Standards Survey Federal Environmental Regulations ■ Clean Air Act(CAA) - Air Emissions Air Discharge Permits ■ Emergency Planning and Community Right-to-Know Act(EPCRA) Toxics Release Inventory(TRI) Chemical Storage and Use ■ Comprehensive Environmental Response, Compensation,& Liability Act(CERCLA) Superfund Amendments and Re-authorization Act(SARA) Spills and Clean-up Of Spills ■ Resource Conservation and Recovery Act(RCRA) - Hazardous Waste ■ Safe Drinking Water Act(SDWA) - Regulates Contaminants in Treated Drinking Water ■ Clean Water Act(CWA) - Water Discharges Water Discharge Permits j US00000667 Federal Environmental Regulations Results ■ Clean Air Act(CAA) - Glycol Ethers In AFFF Are Hazardous Air Pollutants(HAPs) - HAP Releases Are Regulated by the Installation Air Permit • Major Sources for HAPs Might Have Potential Permit Issue ■ EPCRA and TRI - Glycol Ethers are Covered Because CAA Defines them as HAPs. - Chemicals Released Above a Reportable Quantity(RQ)Must Be Reported • Default RQ was One(1)Pound • EPA Established a No RQ - At-4F 'Discharges Do Not Currently Need to Be Reported Under EPCRA and TRI - Ethylene Glycol Specifically Listed - No Other Constituent is Currently Regulated by EPCRA and TRI VUS00000668 Federal Environmental Regulations Results ■ CERCLA and SARA - Glycol Ethers are Covered Because CAA Defines them as HAPs Glycol Ethers May Need to Be "Cleaned Up" After a Spill • Air Pollutants So Expected to be Volatile — Are not volatile when mixed with water • Biodegradable So Might Be "Cleaned Up" Naturally ■ Resource Conservation And Recovery Act(RCRA) - AFFP and Its Constituents are Not Classified as Hazardous Waste - RCRA Does Not Apply ■ Safe Drinking Water Act: - Primary Drinking Water Regulations (Health Properties) • Does not regulate AFFF or its constituents - Secondary Drinking Water Regulations (Aesthetic Properties): • Foaming Agents <0.5 mg1L in drinking water • Do not regulate foaming agents in source water • Guideline for State Regulations Only(Not Federally Enforceable) j US00000669 Federal Environmental Regulations Results(Continued) ■ Clean Water Act(CWA) - Installations Require Discharge Permits • Storm Water • Treated Sewage from Installation Wastewater Treatment Plant • Raw Sewage to Public Wastewater Treatment Plant(Locale Specific) - Regulates Wastewater that: • Foam • Remove Oxygen From Water • Disrupt Wastewater Treatment Plants, etc. - AFFF • Persistent Foam • Removes High Amounts of Oxygen From Water(High BOD and/or COD) • Untreated, Undiluted AFFF Will Disrupt Wastewater Treatment Plant • (Even Diluted AFFF Can Disrupt Wastewater Treatment Plant) SDWA Vj US00000670 Codes and Standards Survey State/Local Environmental Regulations ■ State Regulations Can be More Strict Than Federal - No Specific Instances Found for AFF'F - Storm Sewer Regulations Emphasized ■ Nothing Additional in County and City Regulations ■ Representative Jurisdictions - Telephone Surveys - Focused on Jurisdictions In: • Virginia • Hawaii • Florida • California ■ Local Anecdotal AFFF `Problems' - Sewage Treatment Plants Becoming `Bubble Baths' - Pump Stations Burned-up' - Storm Sewer Overflowing With Foam j US00000671 State/Local Environmental kegulations (Continued) ■ Foaming the Greatest Concern ■ Perception: - Foam Is Highly Toxic to Everything - No Concentration is Okay for a WWTP ■ Results - Local Jurisdictions CAN and DO Regulate AFFF by Name - Have Water Discharge Permit Authority - Local Waste Water Treatment Plants Often Ban AFFF • Based on Direct Experience with a Disruption • High Oxygen Demand • Foaming ~a US00000672 Environmental Consequences ■ Media Considered - Air - Groundwater - Soil - Surface Water • Via storm water • Via wastewater treatment plant ■ Both Constituent Characteristics and AFFF Solution Properties V,~ US00000673 Environmental Consequences Media: Air ■ HAPS: Butyl Carbitol, Ethylene Glycol ■ Low Migration Potential(All Constituents) - Highly Soluble in Water • Tends to stay with liquid water • Not very volatile - If Volatilized, Half-lives in Air 4 Hr - 3.5 Days US00000674 Environmental Consequences Media: Groundwater ■ Consequence Varies Depending on Subsurface Conditions ■ Fluorosurfactants: Not Mobile ■ All Other Constituents: - Highly Soluble, Highly Mobile - Degrades Rapidly in Soil • 30% Degradation Over 24 Hour Period ■ Drinking Water Wells `Under the Influence of Surface Water' Could Receive Undegraded AFFF Constituents ~j US00000675 Environmental Consequences Media: Soil ■ Consequence varies depending on soil type ■ Fluorosurfactants and break-down products - Persistent in soil - No quantified environmental impact - EPA will discuss further tomorrow ■ Other constituents highly mobile in water, will not adsorb to soil ~j US00000676 Environmental Consequences Media: Surface Water Via Storm Water ■ Foaming: - Aesthetic Concern ■ Oxygen Demand - Robs Oxygen from Water - Usually near water's surface ■ Aquatic Toxicity Considered `Practically Nontoxic' by the US Fish and Wildlife Service. - Lowest toxicity value in 40 CFR 300 ■ Surface Water May influence Groundwater ■ `Environmental' Threat - Depends on Sensitivity of Receiving Water: Worst Cases • Kaneohe Bay, HI Risk Analysis "Potential for significant ecological damage ... relatively small" • Wetlands — Waterfowl-Fluorosurfactant Interaction being studied in St. Johns River Basin in Florida. • LC50 > 1000 mg/L in concentrate • --160 mg/L in most sensitive species • Much Lower Toxicity in Firefighting Strength - Anecdotal Reports of Higher Toxicity j US00000677 Environmental Consequences Media: Surface Water Via Direct Discharge to WWTP ■ Disrupts plant through: - Foaming • Disrupts mechanical devices • Causes `sludge bulking' • Causes Froth - High Oxygen Demand ■ Disrupted plant: - Contaminates receiving water - Could cause fish kill - Makes water unfit for: • Drinking • Recreation, etc. • Removes all oxygen - killing microorganisms used to treat sewage • Causes `sludge bulking'. - Aquatic Toxicity • Of lower concern than Foaming and Oxygen Demand • May cause `sloughing' of organisms from certain processes ~a US00000678 Representative Dilution Factors for Treatment of MAX M ILSPEC AFFF at a WWTP 700 600 600 IN Foam Solution (Firefighting Strength) T- 500 X ® 400 v ca ® 300 200 100 60 60 Foaming Aquatic Microbe Oyster Larvae w/anti-foaming agent ToxicityKiiliefish Toxicity (EC50) Toxicity t BO D20 COD Foaming US00000679 Representative Dilution Factors for COD of Foam Solution (Firefighting Strength) 70 y. 60 ❑ MILSPEC MAX(6%) ® MILSPEC MAX (3%) ■ QPL (MILSPEC)AFFF(3%) 60, 60' - ,--~ 50 X 46 •Fluoro-Protein Foam (3%) •Non-MILSPEC AFFF(3%) ■ Baby Shampoo(3%) ® Protein Foam (3%) ❑ Class A Foam (1 %) El HI-EX (1 %) 46 0 40 U ❑ Baby Shampoo (1%) tC LL C 30 0 22 0 20 16 12 vo US00000680 Summary ■ Under Context of Current Laws/Regulations, AFFF and all other Foams Regulated Based On: - Properties • BOD,COD,Foaming and Aquatic Toxicity - "Listed" Chemical Constituents • Butyl Carbitol, Surfactants, Ethylene Glycol, Urea, etc. - Water Issues are Most Prevalent - Foaming is Major Issue for WWTP ■ Potential Environmental Impacts Generally Low - Impacts Consequence of • Foaming • 02 Demand • Aquatic Toxicity - Upset of WWTP Creates Greatest Impact J US00000681 APPENDIX(9) Presentation; AFFF Management — Risk Based Approach" D. Verdonik Hughes Associates, Inc. Baltimore MD US00000682 AFFF Management Risk Based • pproach Dr. Dan Verdonik HUGHES ASSOCIATES, INC. viFIRE SCIENCE & ENGINEERING 1 US00000683 Why a isk. Based . Coach- ■ From Environmental Review - AFFF / Foams have Similar Environmental Impacts • Based on the Properties of Foams in General • Worst Impact for WWTP - Hazard Exists - Cannot Alter What Would Happen IF Released ■ Can Reduce the If or Likelihood of Release - Example - Double Hulled Oil Tankers • Hazard Exists from Potential Oil Spill • Double Hull Reduces Probabili~v of Having the Oil Spill • Double Hull Does Not Reduce Environmental Impact IF Have Oil Spill • Reducing Probability Reduces the Risk to the Environment ■ Need to Evaluate Probability ofFoam Release s Probability + Severity = Risk 6~j US00000684 Risk and ji,sk Assessments: ■ Military Standard 8820: System Safety Program Requirements - Define Terms • Risk - Combination of hazard severity AND hazard probability • Hazard Probability: Aggregate probability ofthe individual events • Hazard Severity: Consequences of worst credible mishap • Control: Action to Eliminate Hazard or Reduce Risk Applicable to All DOD Systems and Facilities Identify the Hazards and Impose Design Requirements and Management. Controls to Prevent Mishaps Tailor to Application • AFFF/Foam Discharge from Facility Fixed Fire Suppression System • Accidental Discharge • Pre-planned testing ■ Have Hazard Severity, Need Hazard Probability - Determine Risk - Risk Decision ~a US00000685 M1L =STD=882D 4.5,2 Hazard Probability ■ Potential occurrences per unit of time, events, population, items, or activity - Quantitative probability for potential design generally not possible - Qualitative probability • Derived from research, analysis, and evaluation of historical data ■ Given for Specific Individual Item or Fleet / Inventory ■ Assign Probability of Having Environmental Consequence USOD000686 Quafitative ® r ty LevelS Specific Individual Item obabl"f FREQUENT (A) Likely to occur frequently PROBABLE (B) Will occur several times in the life of an item OCCASIONAL (C) Likely to occur some time in the life of an item REMOTE (D) Unlikely but possible to occur in the life of an item IMPROBABLE (E) So unlikely, it can be assumed occurrence may not be experienced 5 Vj US00000687 4.5.' eat ■ Hazard Severity Category Definition - Provide Qualitative Measure of Worst Credible Mishap - Result of: • Personnel Error • Environmental Conditions • Design Inadequacies • Procedural Deficiencies • System, Subsystem or Component Failure or Malfunction US00000688 Q itatiVre Hazard Severity Categories CATASTROPHIC (1) Death, System Loss, or Severe Environmental Damage CRITICAL (2) Severe Injury, Severe Occupational Illness Major System or Environmental Damage MARGINAL (3) Minor Injury, Minor Occupational Illness, Minor System or Environmental Damage NEGLIGIBLE (4) Less Than Minor Injury, Occupational Illness, Less Than Minor System or Environmental Damage V-J US00000689 Risk. ji ssessment and Acceptance L CATEGORY I I CATASTROPHIC 2 CRITICAL 3 MARGINAL 4 NEGLIGIBLE FREQUENCY A - FREQUENT B - PROBABLE t C - OCCASIONAL D - REMOTE E - IMPROBABLE m Risk Index - Suggested Acceptance Criteria in MIL-STD-8820 Unacce 9 table: Undesirable: Acceptable w/ Review b DanalinI Activi Acce stable w/out Review: IA,IB,1C.2A.2D4 3A ID 2C 2D 3B 3C 4Cs_4D,,4E10 im I US00000690 eSJ.a] wit Cn, ena M,n ■ Design for minimum risk Review design criteria for inadequate or overly restrictive requirements Design to eliminate hazards If hazard cannot be eliminated • Reduce risk to an acceptable level through design selection • Interlocks, redundancy, fail safe design, system protection, fire suppression, and protective clothing, equipment, devices, and procedures ■ Recommend new design criteria supported by study, analyses, or test data. s VO US00000691 System Description Hazard Identification Probabilities Estimation Consequences Estimation Risk Determination Risk Acceptance Modify System Operate System US00000692 Probability Estimation 3 Parts to Probability Estimation Probability of foam release Reliability of system controlling foam movement Likelihood of environmental consequence 11 VLI USOD000693 , fit Estwimati ba ' PROBABILITY OF FOAM RELEASE -- RELIABILITY OF FOAM CONTROL MEASURES FIRE NO FOAM SYSTEM ACTIVATION it NO FIRE I LIKELIHOOD OF ENVIRONMENTAL CONSEQUENCE Normal Operating Condition SYSTEM SUCCESSFUL ► CONSEQUENCE NO CONSEQUENCE' FOAM SYSTEM ACTIVATION CONSEQUENCE SYSTEM FAILURE NO CONSEQUENCE US00000694 Accident Probability Est U011 ental, Conse nee Of Environ AIR 1. Sanitary sewer, WWTP 2. Segregated Storm Sewer 3. Plugged, Storm Sewer 4. Pavement, Plugged Storm Sewer/drains 5. Pavement, Plugged Combined Sewer/drains 6. Pavement, Combined Sewer WWTP 7. Pavement, Storm Sewer 8. Unlined Pond, Percolates 9. Lined Pond, Pump Off-Site 10 Lined Pond, evaporate 11. Lined Pond, Meter WWTP 12. Lined Pond, Meter Storm Sewer 13. Lined Pond, Degrade WWTP 14. Lined Pond, Degrade Storm Sewer 15. Tank, Pump Off-Site 16. Tank, Meter WWTP 17. Tank Meter Storm Sewer 18. Tank, Degrade WWTP 19. Tank, Degrade Storm Sewer E E E E Sensitive Body of Water _ C C D D Soil Ground Water E E E E Wastewater Treatment Plant C E D E E D E D E C E C E E E E E E E E C E E E D C D D E E E E E E E E E E E E D D D D E E E E E E D C D D E E E E E E D D D D ,3~ai US00000695 Consequence Estimation Severity of Environmental Impact Negligible/Marginal* Sensitive Body of Water Marginal Soil Ground Water Marginal Critical *Air becomes marginal if foam in WWTP US00000696 1. Sanita sewer, WWTP 2. Se re ated Storm Sewer 3. Plu ed, Storm Sewer 4. Pavement, Plugged Storm Sewer/drains 5. Pavement, Plugged Combined Sewer/drains 6. Pavement, Combined Sewer WWTP 7. Pavement, Storm Sewer 8. Unlined Pond, Percolates 9. Lined Pond, Pume Off-Site 10 Lined Pond, evas orate 11. Lined Pond, Meter WWTP 12. Lined Pond, Meter Storm Sewer 13. Lined Pond Des rade WWTP 14. Lined Pond, Degrade Storm Sewer 15.* Tank, Pum....Off-Site 16. Tank, Meter WWTP 17. Tank Meter Storm Sewer 18. Tank Des rade WWTP 19. Tank Des rade Storm Sewer Wastewater Sensitive Body of Soil Treatment Plant Water Ground Water.......... 3C r.:3E 2C 3E,. ... .. . . . . 3D 3E, .... . . .. ......213 3D 2E ` 3E-' 4E 4E 4E L; 4E 3E 4E 4E 4E 4E 3D . .. .......... .. .. . .... . . .. ....................... !.%. ,. -44 .. . . . . . 2C 21) 2D 2D 3E 21) 3E. 3E 3E 3D3E 313 3E 2D 2D 21) 20 3E gg " ~hl' z-I IM4i 3r3D 3D 4E 4E 3E 4E 2D 3E E . 3E 3E 3E 3E 3E 4E 4E .3E A .... .. ..i L 3E 2E' E A 00fE Q 3E US00000697 Summary, ■ Control and. Management of AFFF Solutions - Based on Risk of Environmental Consequence • Risk Decision • Probability AND Severity - No "Unacceptable" Risks from Accidental Discharge - "Undesirable" Risks Avoidable through Design - Remaining Options All have Equivocal Residual Risk ■ Basis for Design Criteria - Ensure Risk is "Acceptable w/ Review by Managing Activity" Category - Minimizes Risk to the Environment - Does Not Increase Risk to Life-Safety/ Fire Loss 16 ~L US00000698 APPENDIX (1 o) Presentation: "Phasing Out a Problem: Perfluorooctyl Sulfonate" M. Dominiak Environmental Protection Agency US00000699 .iawnwi a. a we. . . wwym?k? .2: ?g 52. L. :PFOS is a very,stable chemical that does not''' .,:break down or degrade in the environment;.. =once it's thee, it stays,;. - PFOS can build up over time; its ha~flli "human blood is about 4 yeas: — Higher-ups in the food chain are exposed to the . Mull dose of what has. built up in their food US00000704 nfo .. . .: .. .xrqun xx?. . ?a my. . ?1123:, $35 ?may . .H . . . .xwmy 2 Em, W, 9.: i. y. yw 3M will stop manufac PFOS for S`urf'ace ,-; treatment products by 12/31/2000; includes~~~~~~~ fabricicarpetlleather soil and stain resista~ Oe man paper coating products, bil cludingfood contact n .APB'• ~ ^'~ • Caveat: May request permission for extended production for specific performance uses for; which adequate substitutes do not exist or can' s tracleo s, national, qualified in time; risk/risk security, technical performance issues US00000711 • All documents on PFOS in public EPA Administrative Record, File AR-226 — Includes all health studies submitted on PFOS — Available in hard copy or on CD ROM. 401 ;VI St, SW,Room NE B-607, Wash., DC,noon to 4 PM Eastern, Monday-Friday; telephone 202 260-7099. • Workin:g on website; not up yet, stay tuned • Interim:EPA "Voice of PFOS:" Mary Dominiak, phone 202-260-7768; doiiiiiiialc.iiiaryi~epa.crov US00000716 APPENDIX(11) Presentation: "Facilities Background and AFFF Issues" J. Simone Naval Facilities Engineering Command US00000717 Facilities Background And AFFF Issues Presentation to Hangar Facilities Breakout Session DOD AFFF Environmental Meeting 2 August 2000 Joe Simone Naval Facilities Engineering Command US00000718 FACILITIES BACKRCUND • Facilities that use AFFF - Aircraft Hangars, HAZIFLAM Buildings, Fire Fighters Test Facilities, Hush Houses, and others • Variety of Fire Protection Criteria in dw Last 10 Years • Variety of Containment Requirements • No Risk Analysis with respect to Environmental • Budget Proposals Guess or Don't Address Funding NAVAIR/NAVFAC HANGAR PROJECTS • Evaluated Detector & Sprinkler Response Time in Hangars • Evaluated Removing AFFF from Overhead Sprinkler Systems — Evaluated Using Lower AFFF Application Rate • Evaluated New Low Level AFFF Distibution Systems • Evaluated Variety of Optical Flame Detectors • Developed New Fire Protection Criteria s 3 US00000719 DESIGN PREVIOUS DESIGNS • Deluge AFFF Sprinklers • High Volume AFFF System (20,000 sq.ft. _> 5,000 gpm AFFF). • AFFF is used in the Ceiling and Low Level Systems • Full Discharge Testing • May or May not have Drainage System CURRENT DESIGNS • Closed Head, Water only Sprinklers • Low Volume AFFF System (20,000 sq.ft. _> 2,000 gpm AFFF & 3,000 gpm water) • AFFF is used in the Low Level System only • Test Ports for Discharge Testing • Drainage • Detection Technology • Can Include Abort Switches 3 AFFF MANAGEMENT ISSUES • Environmental Hazard is Not Quantified -- Toxicity?, Air?, Water? • No Uniform Criteria for AFFF Management(site specific) • Current Containment Requirements are Based on Worst Case • Cost of Containment Exceeds Project Funding • Exceeding Project Funding Results in Removal of Fire Protection Systems from Hangars - Impaired Mission 4 2 US00000720 CONTAINMENT ISSUES If Containment is Required: • Manual Intervention or Fixed Containment? • How Do You Size Containment(10 minutes of AFFF supply)? • Disposal - Is it necessary? 5 3 US00000721 APPENDIX(12) Presentation: "AFFF Risk Assessment" A. Wakelin Hughes Associates, Inc. Baltimore MD US00000722 Aqueous Film, Forming Foam (AFFF)Risk Assessment For discharges of AFFF from fixed fire protection systems in shore facilities Alison Wakelin HUGHES ASSOCIATES, INC. FIRE SCIENCE & ENGINEERING August 2, 2000 US00000723 Overview ■ Develop physical control options - Performance Criteria ■ Probability Estimation ■ Consequence Estimation ■ Risk Assessment ~j US00000724 System Description Hazard Identification Consequences Estimation Probabilities Estimation Risk Determination Risk Acceptance Operate System M od ify System V-j US00000725 Develop Physical Options c ®ntrol ■ Hangar drainage requirements(NFPA 449) ■ Foam to the WWTP? ■ Other options for maintaining positive control of foam E US00000726 Hangar Floor Drainage I Sanitary Drains, Oil Water Separator, etc I To WWTP AFFF Discharge No Hangar Floor Drainage V-j US00000727 Diverted from WWTP to? . ___j Hangar Floor Drainage AFFF Discharge No Hangar Floor Drainage Apron/Pavement Vj US00000728 Storm System Diverted from W WTP to? Ditch/Pond Containment Tank Apron/Pavement with drainage E US00000729 Percolate Evaporate Ditch/Pond r Degrade into WWTP or Storm System Containment Tank Storm System Dilute Into WWTP or Storm System Pump & treat off-site Hold in Storm System r Apron/Pavement with drainage Environment V11 US00000730 Physical Control Options ■ 19 different control options ■ Sufficient number to show range of risks ■ Three options will be presented - data from all available on request Vj US00000731 ■ ;le Physical C 1. Sanitary sewer with direct access to WWTP Hangar Floor Drains Sanitary System WWTP 2. Plugged, totally segregated storm sewer Hangar Floor Drains Diversion AFFF Release Normal Operation Sanitary Sewer Plugged Storm Sewer Pump & treat off-site Do- 3. Pond, Percolate (drains into soil) Hangar Floor Drains Diversion Normal Operation Unlined AFFF Release—► Ditch/Pond Sanitary Sewer Percolation Evaporation US00000732 Performance Criteria ■ Detailed investigation of control options ■ What are performance goals of control options? - How much of a discharge needs to be controlled? ■ Accidental discharge shut-off in 3 mins? ■ Accidental discharge of all foam? V-] US00000733 Proposed Foam Control Criteria ■ Conservative approach all foam has drained to beyond diversion point ■ No emergency shut-off ■ 6 min drainage time ■ Single "module hangar 100 ft by 200 ft ■ Total flow - 16 min @ 2000 gpm = 32,000 gal Vj US00000734 Proposed Foam Control Criteria Drainage Diversion Point Underground Drainage Pipes T Hangar Bay Floor Drainage Trenches Trenches x-50 it on center—~ I Single Module l~ Hangar Bay 200 it by 100 it 01 US00000735 Probability Estimation 3 Parts to Probability Estimation Probability of foam release Reliability of system controlling foam movement Likelihood of environmental consequence -,/I 11~,- E US00000736 ProbalbalI!t , Estimation RELIABILITY OF FOAM CONTROL MEASURES PROBABILITY OF FOAM RELEASE ► FIRE NO FOAM SYSTEM ACTIVATION ► LIKELIHOOD OF ENVIRONMENTAL CONSEQUENCE Normal Operating Condition NO FIRE SYSTEM SUCCESSFUL ► CONSEQUENCE 1~ NO CONSEQUENCE I. CONSEQUENCE FOAM SYSTEM ACTIVATION SYSTEM FAILURE NO CONSEQUENCE a. 00 US00000737 Probability Estimation ~ation A FREQUENT Likely to occur frequently B PROBABLE Will occur several times in the life of an item C OCCASIONAL Likely to occur some time in the life of an item D REMOTE Unlikely but possible to occur in the life of an item E IMPROBABLE So unlikely, it can be assumed occurrence may not be experienced V-0 US00000738 P .011ty Estulmati asii Foam System Activation PROBABILITY OF FOAM RELEASE LIKELIHOOD OF ENVIRONMENTAL CONSEQUENCE RELIABILITY OF FOAM CONTROL MEASURES FIRE, NO FOAM SYSTEM ACTIVATION i~0 FiR Normal Operating Condition CONSEQUENCE SYSTEM SUCCESSFUL I b. NO CONSEQUENCE FOAM SYSTEM. ACTIVATION CONSEQUENCE ► SYSTEM FAILURE NO CONSEQUENCE 0a US00000739 Probability Estimation Foam System Activation ■ Accidental activation of a low level foam system ■ Likely to occur some time in the life of an item Occasional C Vj US00000740 Pre iabilityr AstiMatia, Foam Control Measures PROBABILITY OF FOAM RELEASE LIKELIHOOD OF ENVIRONMENTAL CONSEQUENCE RELIABILITY OF FOAM CONTROL MEASURES ffRF • -I. NO FOAM SYSTEM ACTIVATION Normal Operating Condition/,, ' NO FIRE CONSEQUENCE i SYSTEM SUCCESSFUL I 1* NO CONSEQUENCE FOAM SYSTEM ACTIVATION CONSEQUENCE SYSTEM FAILURE NO CONSEQUENCE E US00000741 Probability Estimation Foam Control Measures ■ An engineered design of each control measure is evaluated for: - Reliability • Likelihood of Control System Failure is Established • Failure based on complexity of system V~ US00000742 W • ML t110a t a_~MiltY r . .ac_..tioa gelihood of system talilure 1. Sanitary sewer with direct access to WWTP Hangar Floor Drains Sanitary System Improbable E WWTP 2. Plugged, totally segregated storm sewer Hangar Floor Drains Diversion Normal Operation Plugged Storm Sewer AFFF Release Sanitary Sewer Pump & 0 treat off-site 3. Pond, Percolate (drains into soil) Hangar Floor Drains Diversion Normal Operation Sanitary Sewer Occasional C AFFF Release 10 Unlined Ditch/Pond Percolation Evaporation ~a US00000743 ability Esti'matuion Environmental Consequence PROBABILITY OF FOAM RELEASE RELIABILITY OF FOAM CONTROL MEASURES LIKELIHOOD OF ENVIRONMENTAL CONSEQUENCE FIRE NO FOAM SYSTEM ACTIVATION ► /ormal\~ Operating \ondition; i ► NO FIRE SYSTEM SUCCESSFUL ► CONSEQUENCE NO CONSEQUENCE FOAM SYSTEM ACTIVATION CONSEQUENCE P. SYSTEM FAILURE NO CONSEQUENCE VI-1 US00000744 Pr aba f Estmli at, l f ~ ental Consequence EViron:m n Successful Foam Control (Risk By Media) AIR Sensitive Body ~ of Water 1. Sanitary sewer, WWTP 2. Plugged, Storm Sewer Remote Remote Frequent Improbable 3. Unlined Pond, Percolates Remote Remote Soli Ground Water Wastewater Treatment Plant Improbable Frequent Improbable Remote Improbable Improbable Unsuccessful Foam Control (Risk By Media) 1. Sanitary sewer, WWTP 2. Plugged, Storm Sewer 3. Unlined Pond, Percolates _ AIR Sensitive Body of Water Soil Ground Water Wastewater Treatment Plant Remote Remote Remote Frequent Occasional Occasional Remote Remote Occasional Frequent Occasional Occasional _ VI-1 US00000745 abolillix y Esti mattl, Environmental Consequence PROBABILITY OF FOAM RELEASE F---io- RELIABILITY OF FOAM CONTROL MEASURES LIKELIHOOD OF ENVIRONMENTAL CONSEOUIENCE FIRE i NO FOAM SYSTEM ACTIVATION NO FIRE /rural\\\ Operating I> condition/ %, \, CONSEQUENCE SYSTEM SUCCESSFUL NO CONSEQUENCE FOAM SYSTEM ACTIVATION CONSEQUENCE -I. SYSTEM FAILURE ! 1~ NO CONSEQUENCE va US00000746 rosabillity Estimation Environmental Consequences Option 2: Plugged storm sewer Sensitive body of water PROBABILITY OF FOAM RELEASE 1 0 RELIABILITY OF FOAM CONTROL MEASURES LIKELIHOOD OF ENVIRONMENTAL CONSEQUENCE FIRE NO FOAM SYSTEM ACTIVATION IMPROBABLE SYSTEM SUCCESSFUL NO FIRE FOAM SYSTEM ACTIVATION CONSEQUENCE NO CONSEQUENCE OCCASIONAL OCCASIONAL CONSEQUENCE SYSTEM FAILURE NO CONSEQUENCE PROBABLE Vj US00000747 Probability Estimation Frequency Estimation A FREQUENT Suggested Range -1 X > 10 B PROBABLE 10-1 > X > 10-2 C OCCASIONAL .3 10 > X > 10 D REMOTE 10"3 > X > 10-6 E IMPROBABLE -2 10-6 > X E US00000748 rosab"Efi y Estimation Environrw,ien al Consequence 1. Sanitary sewer, WWTP 2. Plugged, Storm Sewer 3. Unlined Pond, Percolates AIR Sensitive Body of Water Soil Ground Water Wastewater Treatment Plant E E E C D E E E E C D E V~ US00000749 Consequence Estimation Severity of Environmental Impact Negligible/Marginal* Sensitive Body of Water Marginal Soil Ground Water Marginal Critical *Air becomes marginal if foam in WWTP Vj US00000750 Risk Assessment, & Acce.ptanice 1 CATEGORY CATASTROPHIC 2 CRITICAL 3 MARGINAL 4 NEGLIGIBLE FREQUENCY A - FREOUENT B -PROBABLE C - OCCASIONAL D - REMOTE 1D 2D E - IMPROBABLE UNACCEPTABLE: UNDESIRABLE: '.1 A, 1 B,1 C,2A,2B,3XI7 1D,2C9 2D,3B9 3C ACCEPTABLE WITH REVIEW: ACCEPTABLE WITHOUT REVIEW: 4C,4D,4E US00000751 Risk Assessment Environmental Consequence AIR 1. Sanitary sewer, WWTP 2. Pluqqed, Storm Sewer 3. Unlined Pond, Percolates 4E 4E Sensitive Body of Water 3C Soil Ground Water Wastewater Treatment Plant 2C 2D ~j 0600000752 ■ Estimallt! O)nl Pr Foam System Activation PROBABILITY OF FOAM RELEASE RELIABILITY OF LIKELIHOOD OF FOAM CONTROL MEASURES ENVIRONMENTAL CONSEQUENCE FIRE NO FOAM SYSTEM ACTIVATION Normal Operating Condition ► NO FIRE SYSTEM SUCCESSFUL —~= CONSEQUENCE NO CONSEQUENCE FOAM SYSTEM ACTIVATION i • CONSEQUENCE i NO CONSEQUENCE SYSTEM FAILURE 6 d j US00000753 Probability Estimation Foam System Testing ■ Should foam control systems be used for testing? ■ Foam system activation becomes probable ■ Reliability improved as testing supervised ~j US00000754 sk Assessment Environmental: Consequence For Foam Testing AIR 1. Sanita sewer, WWTP 2. Plugged, Storm Sewer 3. Unlined Pond, Percolates Sensitive Body of Water Wastewater Treatment Plant Soil Ground Water 28 2D 313 4D 4D For Accidental Release AIR 1. Sanitary sewer, WWTP 2. Plugged, Storm Sewer 3. Unlined Pond, Percolates Sensitive Body of Water 3C 4E 4E Wastewater Treatment Plant Soil Ground Water _ 2C 2D V-US00000755 Risk Assessment Enviranmental. Consequence AIR 1. Sanitary sewer, WWTP 2. Segregated Storm Sewer 3. Plugged, Storm Sewer 4. Pavement, Plugged Storm Sewer/drains 5. Pavement, Plugged Combined Sewer/drains 6. Pavement, Combined Sewer WWTP 7. Pavement, Storm Sewer 8. Unlined Pond, Percolates 9, Lined Pond, Pump Off-She 10 Lined Pond, evaporate 11. Lined Pond, Meter WWTP 12. Lined Pond, Meter Storm Sewer 13. Lined Pond, Degrade WWTP 14. Lined Pond, Degrade Storm Sewer 15. Tank, Pump Off-Site 16. Tank, Meter WWTP 17. Tank Meter Storm Sewer 18. Tank, Degrade WWTP 19. Tank, Degrade Storm Sewer 4E 4E 4E Sensitive Body of Water 3C 3C 2D 3C 4E 4E 2C 3C 3C 2D 2D 21) 21) 3C 2D 21) 2D 2D 4E 4E Wastewater Treatment Plant 2C 2D 4E 4E 4E 4E 4E Soil Ground Water US00000756 Costs ■ Single module, 16 minutes offoam discharge ■ Costs options we have identified are in the $0-200K range ■ More stringent control criteria can lead to much greater costs ■ However risk of an environmental consequence is not reduced ~j X300000757 APPENDIX(13) Presentation: "Summary of Shore Facility AFFF Management Breakout Session" D. Verdonik Hughes Associates, Inc. Baltimore MD US00000758 Summary of Shore Facility AFFF Management Break-Out Session Dan Verdonik 3 August 2000 US00000759 Facility AFFF Management Working Group • Decision to `formalize' a Working Group — Develop Facility Policy for AFFF Management • Changed name from "Hangar" to "Facility" to reflect broader scope • Target for Completion: Approximately 6 months — Develop a draft DoDI • Staff Through Environmental Side of Services • Present to OSD -- Next Meeting Scheduled for October 12 • Accepted-in-Principle the Risk Based Approach — Use as the Basis for the Policy -- Need to Review Details and Back-up Information — Report will be Provided Prior to Next Meeting US00000760 Facility AFFF Management Working Group -Membership Service Navy Navy Navy Navy Navy Navy Army Army Army Army USAF USAF USMC USMC Office HQ NAVFAC HQ NAVFAC NAVFAC CNO N457C NAVAIR HQ NAVFAC (Contractor Representative) USACE USAGE ACSIM F&H USAGE/ACE AFCESA HQ USAF ILEV HQUSMC DCS/I&LFL HQUSMC DCS/I&LFF Name Joe Gott Joe Simone Vincent Donnally Ms. Kathy Ellis Larry Wolf Kim DePaul Dawn Roderique Bob DiAngelo K.C. Kochhar Bruce Park Billy Ray Scott Fred Walker Jayant Shah Michael Doherty Kevin King _ • Additional Members To Be Identified Prior to Next Meeting US00000761 APPENDIX(14) Presentation_ Summary of AFFF Environmental Breakout Session" J. Hoover Naval Air Warfare Center China Lake CA R. Darwin Hughes Associates, Inc. Baltimore MD US00000762 Summary Of AFFF Environmental Impact Breakout Session Naval Research Laboratory 3 August 2000 Dr. Jim Hoover Head, Combustion Research Branch NAWCWD China Lake Robert Darwin Senior Engineer Hughes Associates, Inc. US00000763 Purpose ofBreakout Session Share Information on AFFF History, performance, chemical composition Environmental and human health impacts Regulations — current and future Replacement activity and status Future management strategy US00000764 (1) What current and future environmental regulations impact AFFF and why (data and policies)? Current: Different regulations affect different components of AFFF Presentation by Bill Ruppert yesterday provided good summary Except for UNDS,there are no definitive restrictions at present and no identified directives for change Future: Depends on future EPA assessment of AFFF as data is reviewed US00000765 (2) What data do we have(or lack) on the environmental impact of AFFF? Lacking: Component toxicityBOD/Persistence (Fate)/Bio-accumulation Accurate and appropriate dilution factors when AFFF discharged in open bodies of water Predictive capability/data regarding releases for estimating potential environmental damage. Must consider where the release occurs (shore hangars, runways, unpaved ground, ship bilges, at sea, etc) US00000766 (3) What technology or products exist that could help reduce AFFF releases into our environment or mitigate the impact ofthose releases? Depends on the type and location ofthe release Reducing releases: Reduction in system tests, efficiency improvements Spill response/advance planning/preparedness Mitigation: ASH (Air•sparged hydrocyclone) RO (Reverse osmosis) Biological/microbial systems Education and Planning: DOD guidance/standards on prevention, clean-up and disposal, training, intentional discharges US00000767 (4) What technology or products could be applied to recycle or reuse AFFF? Not considered to be feasible or cost effective (reformulation, losses, contamination) US00000768 (5) What alternatives to AFFF currently exist and how do they compare in effectiveness, cost, environmental impact, availability, etc ? None meet performance specification(mil spec) Development of an AFFF alternative was proposed as project under ONR Future Naval Capability Platform Protection Program Potential SERDP statement of need Some UK effort on environmentally friendly foam US00000769 (6) What related planning documents exist with other services or agencies? UK is reportedly working on a standard definition of"biodegradability" EPA presentation mentioned international dialog on AFFF PFOS issue USAF needs included in draft NAVAIR ESH-Needs Assessment US00000770 (7) What follow-on strategies should be considered ? Need accurate quantitative definition ofthe problem DOD inventory status How much AFFF in DOD/where used/in-service and reserve stocks/concentrate types DOD AFFF discharges How much released/consumed annually (training, system testing and maintenance, accidental discharges, research, fires) Review current DOD regs and policy Need a definition of"environmentally friendly"(need "green" definition—what are acceptable thresholds from an environmental standpoint) Persistence Biodegradability Bio-accumulation BOD/COD Toxicity US00000771 Follow-On Strategies(con't) Need for future research SBIR Goals for Universities ONR Need to develop small scale screening tests Develop"SNAP-equivalent" guidance Need for "worst case" transition plan (short/mid/long term) Information distribution to all levels(users, requirers, trainers, regulators, etc) Develop AFFF detection capability (learn method used by 3M) Define hazard protocols and appropriateness of AFFF(use and response) US00000772 Follow-On strategies (con't) Assess commercial state-of-the-art CBD announcement "Turkey shoot" of all available AFFF alternatives Quantify performance, chemical and physical properties Obtain EPA endorsement of screening tests Consider fixture mods to AFFF mil spec Prioritze requirements Consider trade-offs Establish formal AFFF working group Info sharing Formal charter DOD primary advocate? Future meetings/host/agenda topics US00000773 Summary Of AFFF Environmental Impact Breakout Session Naval Research Laboratory 3 August 2000 Dr. Jim Hoover Head, Combustion Research Branch NAWCWD China Lake Robert Darwin Senior Engineer Hughes Associates,Inc. US00000774 Purpose ofBreakout Session Share Information on AFFF History, performance, chemical composition Environmental and human health impacts Regulations — current and future Replacement activity and status Future management strategy US00000775 {1) What current and future environmental regulations impact AFFF and why (data and policies)? Current: Different regulations affect different components of AFFF Presentation by Bill Ruppert yesterday provided good summary Except for UNDS,there are no definitive restrictions at present and no identified directives for change Future: Depends on future EPA assessment of AFFF as data is reviewed US00000776 (2) What data do we have(or lack) on the environmental impact of AFFF? Lacking: Component toxicity/BOD/Persistence (Fate)/Bio-accumulation Accurate and appropriate dilution factors when AFFF discharged in open bodies of water Predictive capability/data regarding releases for estimating potential environmental damage. Must consider where the release occurs(shore hangars, runways, unpaved ground,ship bilges, at sea, etc) US00000777 (3) What technology or products exist that could help reduce AFFF releases into our environment or mitigate the impact ofthose releases? Depends on the type and location ofthe release Reducing releases: Reduction in system tests, efficiency improvements Spill response/advance planning/preparedness Mitigation: ASH (Air-sparged hydrocyclone) RO (Reverse osmosis) Biological/microbial systems Education and Planning: DOD guidance/standards on prevention, clean-up and disposal, training, intentional discharges US00000778 (4) What technology or products could be applied to recycle or reuse AFFF? Not considered to be feasible or cost effective (reformulation, losses, contamination) US00000779 (5) What alternatives to AFFF currently exist and how do they compare in effectiveness, cost, environmental impact, availability, etc ? None meet performance specification (mil spec) Development of an AFFF alternative was proposed as project under ONR Future Naval Capability Platform Protection Program Potential SERDP statement of need Some UK effort on environmentally friendly foam US00000780 (6) What related planning documents exist with other services or agencies? UK is reportedly working on a standard definition of"biodegradability" EPA presentation mentioned international dialog on AFFF PFOS issue USAF needs included in draft NAVAIR ESH-Needs Assessment US00000781 (7) What follow-on strategies should be considered ? Need accurate quantitative definition ofthe problem DOD inventory status How much AFFF in DOD/where used/in-service and reserve stocks/concentrate types DOD AFFF discharges How much released/consumed annually (training, system testing and maintenance, accidental discharges, research, fires) Review current DOD regs and policy Need a definition of"environmentally friendly"(need "green" definition--what are acceptable thresholds from an environmental standpoint) Persistence Biodegradability Bio-accumulation BOD/COD Toxicity US00000782 Follow-On Strategies(con't) Need for future research SBIR Goals for Universities ONR Need to develop small scale screening tests Develop "SNAP-equivalent" guidance Need for "worst case" transition plan (short/mid/long term) Information distribution to all levels(users, requirers, trainers, regulators, etc) Develop AFFF detection capability(learn method used by 3M) Define hazard protocols and appropriateness of AFFF(use and response) US00000783 Follow-On strategies(con't) Assess commercial state-of-the-art CBD announcement "Turkey shoot" of all available AFFF alternatives Quantify performance, chemical and physical properties Obtain EPA endorsement ofscreening tests Consider future mods to AFFF mil spec Prioritze requirements Consider trade-offs Establish formal AFFF working group Info sharing Formal charter DOD primary advocate? Future meetings/host/agenda topics US00000784