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Agenda A FF F Interagency Woridng Group Meeting
0900 - 0915 Opening Remarks 0915 - 0930 Agenda & Air Force AFFF Program 0930 - 1000 Agent Evaluation Program 1000 - 1015 AFFF Phase I/II SBIR 1015 - 1030 BREAK 1030 - 1045 FAA Perspective on AFFF 1045 - 1100 NRL Perspective on AFFF 1100 - 1115 AFFF Mil-Spec 1115 - 1200 Discussion
Mr. Bob Darwin NAVSEA Capt Bob Tetla FIVCF Mr. Doug Nelson FIVCF Dr. Ed Kleiner Dynax Corp.
Mr. Joe Wright FAA Dr. Joe Leonard NRL Mr. Bob Darwin NAVSEA Capt Bob Tetla
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AIR FORCE AFFF PROGRAM
ENVIRONMENTALLY ACCEPTABLE AFFF RESEARCH
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BACKGROUND
CLEANUP - McDill AFB, Whiteman AFB, etc. - Large amount of money
TRAINING - AFFF in ground from old pits - Not enough environmental fire pits
AFFF HANGAR DUMPS
AIR FORCE HAS NEED FOR MORE ENVIRONMENTALLY ACCEPTABLE AFFF
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AFFF TECHNICAL PROBLEMS
SOLVENT PROBLEM - 15 gallons of AFFF spilled is reportable (Glycol Ether)
FOAM PROBLEM - Sewer plants cannot handle
HIGH BIOLOGICAL OXYGEN DEMAND
NEED FILM FORMING FOAM - Knockdown - Burnback
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BIODEGRADATION CONSIDERATIONS
MIL-SPEC AFFF
BOD5/COD:
BOD20/COD:
10% 80%
GOAL
Aerobic Biodegradation - BOD5/COD 40% - BOD20/COD 100% Change Solvent Change Hydrocarbon Surfactant Reduce Fluorocarbon Surfactant Add Bacterial Spores
Anaerobic Biodegradation
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MITIGATION METHODS
- BACTERIAL BREAKDOWN At System Nozzle Added to Tank/Lagoon
- ANTI-FOAMING AGENTS - ULTRA-FILTRATION & ACTIVATED CARBON - ULTRA-SOUND - Sonolysis at 440 KHz to 1MHz
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RESEARCH TARGETS
MAINTAIN CURRENT PERFORMANCE KNOCKDOWN BURNBACK
ELIMINATE GLYCOL ETHERS
DECREASE FOAMING PROBLEMS
INCREASE BIODEGRADABILITY MORE BIODEGRADABLE HYDROCARBON SURFACTANTS REDUCE FLUOROCARBON SURFACTANTS ADDITION OF MICRO-ORGANISMS TO AFFF
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ENVIRONMENTALLY ACCEPTABLE AFFF
COMMERCIAL AGENT EVAL
FORMULATION IMPROVEMENT
SB1R PHASE 1
SBIR PHASE II
MITIGATION ADDITIVES NEXT GENERATION AFFF
ESTABLISH W ORKING GROUP LITERATURE SEARCH COMPUTER MODELING NEW FORMULATIONS LABORATORY ANALYSIS CANDIDATE SELECTION MEDIUM SCALE TESTS LARGE SCALE TESTS
TOP CANDIDATE(S) SELECTION
AfFFSCHO
FY93
FY94 FY95
A
FY96
FY97 FY98
Li
1
$ ft
L ft
f t_ _ ft
ft ft ft
f t __________
ft
ft_ J ft_ J < L ft ftft
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PROJECT GOAL ENVIRONMENTALLY ACCEPTABLE AFFF WITHOUT LOSS OF EFFECTIVENESS
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EVALUATION CRITERIA
SOLVENT HAZARD POTENTIAL BIODEGRADABILITY TOXICITY - FISH / MICOORGANISMS EXTINGUISHMENT EFFECTIVENESS FLAME SPREAD RESISTANCE IMPACT ON DISPERSING EQUIPMENT
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AGENT
MIL-SPEC AFFF CENTRIFOAM 903
PETROSEAL FIREWATER 990
FUEL BUSTER PYROCOOL FEF PETROTECH FE-2 MICRO BLAZEOUT
BCD PHIREX +
BRC II SP 911 FSR-100
SOLVENT
BUTYL CARBITOL HEXYLENE GLYCOL HEXYLENE GLYCOL ETHOXYLATED NONYL PHENOL ISOPROPYL ALCOHOL ISOPROPYL ALCOHOL ISOPROPYL ALCOHOL PROPYLENE GLYCOL PROPYLENE GLYCOL PROPRIETARY PROPRIETARY NONE NONE
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BIODEGRADABILITY
AGENT
SP-911 FUEL BUSTER MHL-SPEC AFFF CENTRIFOAM 903 FIREWATER 990
PHIREX + PETROTECH FE-2
PETROSEAL PYROCOOL FEF
BRC II BCD
MICRO BLAZEOUT
% BOD5/COD
4.8 7.2 8.4 9.1 9.1 10.2 12.4 14.8 17.6 19.3 34.9 43.8
AGENT TYPE
PROTEIN FOAMS FLUOROPROTEIN FOAMS HYDROCARBON SURFACTANT FOAMS
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TOXICITY TO FISH
LESS THAN AFFF
SAME AS AFFF
10X GREATER THAN AFFF
30 -tcoo oo CtoD E F 20Oc) lteo 3 Oc )
s
10 -
0.0
--Jt--
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APPLICATION DENSITY
Application Density (GPM/ft2.) AFFF CENTRIFOAM 903 BRC II - new PTI-FEII PYROCOOL-B MICRO BLAZEOUT
EXTINGUISHMENT TIMES FOR 0.19 GPM/ FT.2APPLICATIO N DENSITY
50 45
T<Couat3n4>
v
AFFF
Centrifoam 903 FEF 42994A
Micro Blazeout
BRC-ll
PTI-FEIi
BCD
FSR-100
DRFS
Firewater 990
Fuel Buster
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FLAME SPREAD RESISTANCE TESTS
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PROBLEMS FOR AIR FORCE EQUIPMENT
FIREWATER 990 PYROCOOL FEF
SP 911 FSR-100
DELIVER AT 0.75% DELIVER AT 1% DELIVER AT 20% OR 40% SOLID, REQUIRES SPECIAL SYSTEM MAY CAUSE CLOGGING
(METERING) (METERING) (TANK) (AGENT TYPE)
OTHER AGENTS NOT A PROBLEM, METERED AT 3% OR 6%
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CONCLUSIONS
SEVERAL AGENTS MORE BIODEGRADABLE THAN MIL-SPEC AFFF
NO COMMERCIAL AGENT TESTED AS EFFECTIVE AS MIL-SPEC AFFF
STAY WITH MIL-SPEC AFFF UNTIL NEW AGENT DEVELOPED
OBTAIN EPA RELIEF ON BUTYL CARBITOL AS INTERIM MEASURE
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FUTURE DIRECTIONS
TEST EMERGING INDUSTRY PRODUCTS STIMULATE INDUSTRY DEVELOPMENT OF
IMPROVED AFFF COORDINATE DOD SPONSORED RESEARCH WITH
INDUSTRY EFFORTS
WRAP-UP
RECOGNIZED PROBLEM MADE ANNOUCEMENT IN CBD FOR PRODUCT TESTED PRODUCTS CONTINUE RESEARCH PROGRAM
SBIR S&T
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DYNAX PHASE II AFFF-EMB R&D
SOLVENT REPLACEMENT STUDY
PHASE I BASE COMPOSITION OPTIMIZATION
1994
1995
A S O N D J F M A M .I J A
**I
'*I
i
i
! Q
iii ii
OPTIMIZE DYNAX FC-SURFACTANT/ SURFACTANT SYSTEM
OPTIMIZE PHASEII BASE COMPOSITION
4 4l
4
SYNTHESIZE EXPLORATORY ADDITIVES
AFFF-EMB AGENT EVALUATION TEST MOST PROMISING AFFF-EMB AGENTS
FIRE TEST SERIES (TYN)
FINAL REPORT
DYHXSCHD
i
ft
A fti
4
$ ! fti
ft
Phase 11 AFFF-EMB Development Scheme
Commercial 1Additives
FC-Cosurfactant HC-Cosurfactants Synergists/ther
AFFF-EMB Development
Evaluate
- 5- Optimize
Formulate
Exploratory Additives
FC/HC Surfactants Synergists Other
Type A 3% AFFF-EMB
Lowest Fluorine Level
Most Environmental Improvement
Least Burnback Improvement
ri
Type B 3% AFFF-EMB
Medium Fluorine Level
Medium Environmental Improvement
Medium Burnback
Improvement
|
ri
% Type C
3 AFFF-EMB
Highest (1%) Fluorine Level Least Environmental Improvement
Most Burnback improvement
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Chemical and Physical parameters for AFFF-EMB Concentrates. Solutions and Foams
Note: P-1 Indicates parameters to be established for Phase II. Values quoted, indtcates same parameters as for AFFFs meeting MIL-F-24385F.
Parameters
Refractive Index, minimum
Viscosity, centistoke Maximum at 5C Minimum at 25C
Hydrogen ion concentration (pH)
Spreading coefficient, minimum
Foam ability: Foam expansion, minimum Foam 25% drainage time, minutes, minimum.
Corrosion rate: General
Cold rolled, low carbon steel(UNS G10100), milli ln/yr., maximum
Copper-nickel (9Q10)(UNS C7060), milli tn/yr., maximum uonunuea on Touowma page.
Values Type 3 Type 6
P-1 P-1
P-1 P-1
7.0 to 0.5
3
P-1 P-1
7.0 to 8.5
3
P-1 P-1 P-1 P-1
Application Publication
ASTM D445.74
_
-
NFPA STD 412 NFPA STD 412
Test In MIL-F-24385F
4.7.1 4.7.2
4.7.3
4.7.4
4.7.5 4.7.5
1.5 1.5 1.0 1.0
ASTM E527 ASTM E527
4.7.7.
4.7.7. ............................. ......... .
Chemisgl.anci,Physical Parameters for AFFF-EMB Concentrates, Solutions and Foams
indicates parameters to be established for Phase II. Values quoted, Indicates same parameters as for AFFFs meeting MJL-F-24385F.
Parameters
Corrosion rate (continued): Nickel-copper (70-30) (UNS 04400), mllti in/yr.,
maximum Bronze (UNS C90500),
milligrams maximum Localized, corrosion resistant
CRES) steel, (UNS S30400)
Total halides, p/m, maximum Dry chemical compatibility burnback, resistance time, seconds, minimum
Environmental Impact: Toxicity, LCbo, mg/L, minimum COD, mg/L, maximum BOPw. minimum COD
Type 3
Type 6
1.0
100 No Pits
P-1 P-1
1.0
100 No Pits
P-1 P-1
P-1 P-1 P-1 P-1 P-1 P-1
Application Publication ASTM E527 ASTM E527
ASTM E527
Test In MIL-F-243B5F
4.7.7.
4.7.7. 4.7.7.
4.7.8. 4,7.9.
_
4 7 12 1. 4 7 12 2
- 4.7.12.3.
Physical and Environments! Parameters for AFFF-EMB Agents
,3.%.AFEBEMB parameters ; .v- ""I ' .
TYPE-A -e t y p e ^b : 3% -J:
AFFF-aB AFFF-EMB
TYPEC 3% "
AFFF-EMB
MIL-F .' -24385F 3%AFFF....
Fluorine'Content Limiteri to:
Environmental Impact improvement
Low level 1Med. Level
.'T': Very Much 1 Much
Max. 1% -'
Limited
Not Limited --
Bumback Resistance Improvement
: limited 1 Much : Very Much
Refractive Index, Minimum
Viscosity, centistokes Maximum at 5 C Minimum at 25 C
Spreading coefficient. Minimum
Foamability: Foam Expansion, Minimum Foam '/ Drairi Time, Minutes, Minimum
Total Halides, p/m, Maximum
Environmental Impact: Toxicity,LCa ,mg/L,Minirriurn COD, ma/L1r Maximum BODTM, Minimum COD
NS"
MIL-F MiL-F
3
MIL-F
MIL-F MIL-F or
15002
150031 5004' 0.80^ I
MIL-F
MIL-F MIL-F
5
MIL-F
3.0 MIL-F or
1500*
1003' 75041 0.8G4)
MIL-F
40 4
6
MIL-F 3.5
MIL-F or 1500*
1000! 75C41 0.804)
1.3630
20
2
3I
2.5 500
500 1000 0.65
^ Not to be specified; refractive index will be lower than MIL-F. 21 To be negotiated for Phase 11; higher halide ievel (chloride) will leave more
formulation possibilities open and corrosion specs can still be met. 3) No fish toxicies run in Phase 1; improvements could be higher. 4) No COD and BOD determinations done in Phase I. Better values potentially
achievable.
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Fire Performance Parameters for A F rr-E M B Agents.
.. 3%
-, T * X .
- p --
'Parameters ' TYPE A ' 3% ; . . v
AFFF-EMB
'T Y P E S T TYPE C : - MiL-F3% : : 24385F
AFFF-EMB. AFFF-EMB. 3% AFFF
Fluorine Content Limited tor
Environmental impact improvement: .-y* .
! Low Level Med. Level I
Max. 1%
1
Very Much Much : Limited
Not Limiied
--
Bumback Resistance Improvement .
Limited
Much
Very Much
28 Sa. R_ Ftre Foam application time to extinauish, seconds, maximum
Half Strength Full Strength 5 x Strength
45 (3/4) M fl-F MIL-F
Bumback Tme of resulting
foam cover, seconds, minimum
Half Strength Full Strength 5 x Strength
300 (3/4)' 360 240
50 So. Ft Fine Foam application time to extinguish, seconds, maximum
MIL-F
MIL-F MIL-F MIL-F
MIL-F 420 300
MIL-F
MIL-F MIL-F ML-F
360 480 360
MIL-F
45 30 55
300 360 200
50
Bumback Time of resulting
foam cover, seconds, minimum
40 second summation
360 420 4S0 360 320 340 360 320 J,
Note: Solvents in AFFF-EMB agents not on Hazardous Air Pollutant list of the 1990 Clean Air Act nor subject to SARA Title III, Section 313 regulations.
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Abstract o f Analysis o f the Toxic Effects, COD and BOD o f Fire Fighting Foams by the German Office for Defense Technology and Procurements (BWB), May 23, 1989.
Toxicity Teste, COD and BOD of W orst and Best Foam Candidates
Multi Purpose Foams
(5)
AFFF Agents
(6)
FFFP Foam
(D
F-Protein Foam (3)
EC10 (jjfl water) for Photobacterium P hosp ho reum 15
EC,a(pfl water) Scenedesmus subspicatus21
0.6
30
7,500
2,000
to to 6.0 2,000
88
to
1 107,500
35
to to
to
35 36
| 509
LC,0(jt//1 water) for Daphnis
12
20 3,700
200
Magna35
to to
to
75 85
3,700
LCS0Ct>/l water) for Brachydanio rerio45
65
144 10,000
1,369
to to
to
173 3,075
10,000
COD of 3% solution (mg 0 2/I water)
30,000 to
52,000
21,000
19,600
to
41,200 j
14,100 to
17,000
BOD5 of 3% soiution (mg O j/I of water
15,200 I 8,700 to to
30,500 | 23,200
12,300
8,700 to
14,500
b o d 5/c o d
0.29 I 0.35 to to
0.86 0.75
0.63
0.62 to
0.89
I
`} Concentration (of foam substance) which reduces the light power of the phoiobacteria by 10%.
25 Concentration which produces 10% growth inhibition o f fresh water algae after 72 hours.
3) Concentration in which 10% of test Crustacea lost their buoyancy over 24 hours. 4) Highest concentration tested in which 50% of the 2ebra fish died within 48 hours.
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FAA PERSPECTIVE
MR. JOE WRIGHT
FEDERTAELCAHVNIOALTOIOGNYACDEMNITNEISRTRATION
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NRL PERSPECTIVE
DR. JOE LEONARD
NAVAL RESEARCH LABORATORY
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