Document 0qvVjQ05n23jm1ar08qDNKJ8x

FINAL REPORT ENVIRONMENTALLY IMPROVED AFFF NOOl 7 3 -7 6 - C -0 2 9 5 BY THE ANSUL COMPANY MARINETTE, W ISCONSIN 5 4 1 4 3 DECEMBER 1 3 , 1977 & 3 1976 Pf US00003106 BY THE ANSUL COMPANY y MARINETTE, WISCONSIN 54143 J yy (Z z J '_ r i US00003107 TABLE OF CONTENTS 1 .0 INTRODUCTION ............................................. 1 .1 CONTRACTOR'S PROPOSAL . . . 1 .1 .1 1.1.2 PROPOSAL OBJECTIVE PROGRAM STEPS . . . 1 . 2 CONTRACT WORK STATEMENT ........................................ .... . 1.2.1 1 .2 .2 INTRODUCTION . . . . . . . . . . . . . . TECHNICAL T A S K S ................ ... 1 . 3 PERFORMANCE FIRE MEASUREMENTS................................ 2 .0 EXPERIMENTAL TECHNIQUES ............................ ... ............................... 2 .1 BIOLOGICAL OXYGEN DEMAND ............................................ 2 .1 .1 2.1 .2 2 .1 .3 2 .1 .4 APPARATUS ................................................................ REAGENTS ....................................................... . . PROCEDURE ............................................ .... . . . BOD CALCULATION ............................................ 2 .2 CHEMICAL OXYGEN DEMAND ........................ ....................... 2 .2 .1 2.2 .2 2 .2 .3 2 .2 .4 APPARATUS................................................................ REAGENTS . . . . . . . . . . ........................ P R O C E D U R E ................................................... . . CALCULATIONS ........................................... . . 2 .3 AQUATIC T O X IC IT Y .................................................................... 2 .4 PHYSIOCHEMIOAL PROPERTIES AND PERFORMANCE . . 3 .0 EXPERIMENTAL RESULTS . . . . . . . . . . . . . . . . . . . . 3.1 ALTERNATE METHODS FOR THE DETERMINATION OF AFFF SOLUTION CONCENTRATION .................................... 3 .2 SUGGESTED S O L U T IO N ........................................ ... . . . . 3 .3 THE WATER SOLUBLE DYE APPROACH . . . . . . . . . 3 .4 RECOMMENDED PRO CED U RE................................................ 3 .5 EXPERIMENTAL . . . . . . . . . . . . . . . . . . . . US00003108 US00003109 LIST OF TABLES PAGE I BOD RESULTS OF EXPERIMENTAL COMPOUNDS EXPRESSED AS MGMS O 2/M G M COMPOUNDS ........................................................ 21 II COD RESULTS OF EXPERIMENTAL C O M P O U N D S .................... .... . 22 III 96-HOUR AQUATIC TOXICITY INVESTIGATION ON FUNDULUS HETEROCLITUS (MUMMICHOGS). ............................ 24 IV 96-HOUR AQUATIC TOXICITY INVESTIGATION ON FUNDULUS HETEROCLITUS {MUMMICHOGS) . . . . . . . . . . . . . . . 25 V 28 S Q .F T . FIRE PERFORMANCE OF EXPERIMENTAL AFFF FO R M U LA TIO N S.................... ........................... ........................................... 26 N 1 ij LIST OF FIGURES PAGE 1 PERCENT TRANSMISSION VS. PROPORTIONING: EXPERIMENTAL LOW SOLVENT AFFF K 76'-312 CONTAINING 120 PPM DYE . . . 31 2 PERCENT TRANSMISSION VS. PROPORTIONING: 3M LIGHT WATER AFFF CONTAINING 120 PPM DYE ................................ .... 32 3 AFFF CONCENTRATE CONTAINING 1 20 PPM DYE AND SELECTED SEA WATER DILUTIONS........................................ ... ................................... 33 4 PERCENT TRANSMISSION VS. PROPORTIONING: EXPERIMENTAL LOW SOLVENT AFFF K76'-31 2-1 0 2 CONTAINING 40 PPM DYE . 34 5 AFFF CONCENTRATE CONTAINING 40 PPM DYE AND SELECTED SEA WATER DILUTIONS . . . . . . . . . . . . . . . . . . . . . 35 US00003110 1.1 1 . 1.1 INTRODUCTION This investigation w as undertaken to try to gain some insights into how the chem ical com position of aqueous film -form ing foam (AFFF) c o n c e n tra te s e f f e c ts th e e n v iro n mental properties of th e se fire extinguishing ag en ts. Since this is a relatively new area of concern and in terest, there w ill be differences of opinion in how to approach the in v e sti gation. The contractor's original proposal and the final work statem ent are presented below for purposes of clarity in ou tlining the work and c rite ria used in th is in v e stig a tio n . . Contractor's Proposal Proposal O bjective (a) The p u rp o se of th is work is to ex p lo re the d ev elo p m en t : o f e x p erim en tal AFFF fo rm u latio n s th a t w ould e x h ib it ; reduced im pact on the environm ent w hile retaining : certain fire suppression c h a ra c te ris tic s . In p articu la r, it is p ro p o sed to ex am in e th e e ffe c t of th e AFFF form ula tion com ponents on the biological oxygen demand of the c o n c e n tra te . In lig h t of re s u lts p rev io u sly obtain ed ^ |j I ; I i US00003111 ! W W P I* W I (b) It is furtherm ore p ro p o sed th a t th e req u ire m en ts of M IL -F-24385, Amendment 8, and the proposed revision th ereto , w ill not apply to the present in v estig atio n . There w ill in a ll probability be a trade-off between biological im pact and physiochem ical c h a ra c te ristic s. Fire perform ance and corrosion ch ara cteristics are of primary im portance, w hereas refractive index, pH, v is c o s ity , foam expansion ra tio , and surface in te r facial tension are of le sse r im portance. (c) The g e n e ra lly a c c e p te d m ethod for d eterm in in g propor tioned or premixed solution com position is to m easure the refractive index of the so lu tio n . In order to get acceptable accuracy and precision with field type refractometers, solvent lev els of 15-20% are currently used in com mercial products. It is assum ed that th ese le v e ls are d e le te rio u s from a b io lo g ical a s p e c t. Some effort w ill be expended in evaluating altern ate an aly tical te c h n iq u e s for th e m easu rem en t of AFFF so lu tio n c o n c e n tration . : .2 Program Steps (a) Raw M a te ria l BQD20 ~ T w en ty -d a y BOD s tu d ie s w ill be conducted on typical fluorocarbon su rfa c ta n ts, hydro- -2- 1 .2 1 .2 .1 carbon surfactants and so lv e n ts. The purpose w ill be to determ ine the effect of chem ical com position on BOD20 : : (b) BOD20 D esig n E xperim ent - In v e s tig a te th e e ffe c t of com ponent co n cen tratio n and type on BOD2 0 . C a n d i- date form ulations w ill be selected based on this in v e s tig a tio n . (c) Form ulation D esig n E xperim ent - F orm ulations w ill be ' se le c te d b ased on the BOD20 in v estig atio n and screened for fire perform ance and physiochem ical : p roperties. This w ill include corrosion ch ara cteristics and concentrate sta b ility , in addition to fire perform ance. (d) A n aly tical M eth o d s E v alu atio n - An in v e s tig a tio n of altern ate an aly tical methods for determ ining solution concentration w ill be conducted to determire if a sim ple method for u se in the field is fe a s ib le . C ontract Work Statem ent Introduction The present form ulations w ith resp ect to fire suppression are highly effectiv e. H owever, im provem ents are desired in the -3 - '1 : :J I j 1f > U ! j US00003113 1 .2 .2 : 1 .2 .2 .1 environm ental area, i .e . , developm ent of com positions that have a reduced im pact on the environm ent w ithout lo ss of fire suppression effectiv en ess. Technical Tasks (a) The C o n tra c to r s h a ll e x p lo re th e d ev elo p m en t of e x p e ri m ental AFFF fo rm u latio n s th a t w ould e x h ib it a red u ce d impact on the environm ent w hile retaining fire effeetiv eness, (b) The p ro p o sed stu d y w ill exam ine th e e ffe c t of FFF formu la tio n com ponents on th e b io lo g ical oxygen dem and (BOD), chem ical oxygen demand (COD), b io d eg rad ab ility , to x i city toward sew age b a c te ria , fish to x ic ity , effect of com p o n en t c o n c e n tra tio n on s e le c te d e n vironrr.enta 1/b io io g lc a 1 param eters, formulation design experim ents, and analytical methods evaluation. Task I - Raw M aterial BOD20 and COD T w enty-day BOD stu d ie s sh all be conducted on ty p ic a l fluoro carbon su rfactan ts, hydrocarbon surfactants and so lv en ts. The purpose w ill be to determ ine the effect of chem ical com position on BQD2 0 * C hem ical oxygen dem and (COD) m easu rem en ts, -4 V[ --------- Mmmmmmrnm US00003114 to x icity toward sew age b a c te ria , and fish to x icity (kill fish) w ill also be made on the above m aterials. T ask II - Biodeqradability and BOD^r, D esig n E xperim ent Investigate the effect of component concentration on biode gradability and BOD20- C and id ate form ulations w ill be selected based on this investigation. Task III - Form ulation D esign Experiment F o rm u latio n s s h a ll be s e le c te d b a s e d on th e BOD20 b iod e gradability in v estig atio n and screened for fire perform ance and physiochem ical p ro p erties. This w ill include corrosion c h a ra c te ristic s and concentrate sta b ility , in addition to fire perform ance. In th e ev en t th a t a more highly co n cen tre ted m aterial (to be) u s e d in le s s than a 6% so lu tio n ) is d e s ir e d , a ll env iro n m en tal p ro p e rtie s s h a ll be a d ju s te d to a (>% datum b a s e . T ask IV - A n aly tical M eth o d s E v alu atio n An in v e s tig a tio n of a lte r n a te a n a ly tic a l m ethods for d eterm in ing solution concentration sh all be conducted to determ ine if a sim ple method for u se in the field Is fe a s ib le . 1 .3 Performance Fire M easurem ents Compare fire performance of the new formulation with that : of form ulation currently m anufactured and em ployed In the field , by the same te st m ethods. Fire performance te st procedures sh all conform to Paragraph 4 .7 of M IL-F-24385 (NAVY), am endm ent 8 , a s a p p lic a b le . ' I ! ii 1 US00003116 BBflF"'" 2.0. 2.1 . I .1 EXPERIMENTAL TECHNIQUES Previous work ^ ^ 1 conducted in the area of environ m ental c h a ra c te ris tic s of AITF w as d ire c te d at determ ining th e follow ing w ith reg ard to co m m ercially a v a ila b le AFFF liquid concentrates: BOD (Biological O xygen Demand) * COD (Chemical Oxygen Demand) * Acute Toxicity (C oncentration required to produce a certain level of m ortality in a particular species after - exposure for a certain tim e.) Biological Oxygen Demand The POD determ inations were conducted in accordance with the procedures given in the lite ra tu re W). The d etaile d pro cedure is given as follows; Anpera .us (a) M odel 54 YS1 d is s o lv e d oxygen m onitor w ith M odel 5720 YS1 s e lf - s tir r in g BOD b o ttle probe and M odel 57 35 c a b le a d a p to r. (All of th e s e are a v a ila b le from Fisher S cientific.) (b) In cu b atio n BOD b o ttle s (300 mi) w ith g ro u n d -g la s s stoppers (acid-w ashed before use). -7- : US00003117 (c) In cu b ato r th e rm o s ta tic a lly co n tro lle d a t 20C t 1 C . Ail lig h t m ust be ex clu d ed from th e in c u b a to r to p re v en t form ation of 1X3 by a lg a e in th e sa m p le . R eag e n ts (a) D is tille d w ater of th e h ig h e st q u a lity co n tain in g le s s th a n 0,01 mg/1 copper and free of c h lo rin e , chi oro am ines, caustic alkalinity, organic m aterial, or acid s. (b) P h o sp h ate buffer so lu tio n : D is so lv e 8 .5 g p o tassiu m dihydrogen p h o sp h ate {KH2PO4 ) , 2 1 .7 5 g d ip o ta ssiu m hydrogen phosphate (K2HPO4) , 3 3 ,4 g disodium hydro gen p h o sp h a te h e p tah y d rate (Na2HPC>4 7H2O ), and 1 .7 g ammonium ch lo rid e (NH4CI) in about 500 ml d is tilled H2O and d ilu te to 1 lite r . The pH of th is buffer so lu tio n should be 7 .2 without further adjustm ent. (c) M agnesium s u lfa te so lu tio n : D isso lv e 2 2 .5 g MgSChf 7H2O in d is tille d w ater and d ilu te to 1 lite r. (d) C alciu m c h lo iid e so lu tio n : D issolve; 2 7 .5 g anhydrous C aC l2 in d istille d w ater and d ilu te to 1 lite r. (e) F erric c h lo rid e so lu tio n : D isso lv e 0 .2 5 g F e C lj 6H2O in d is tille d w ater and d ilu te to 1 lite r. (f) Acid and a lk a li s o lu tio n s IN : For n e u tra liz a tio n of sam ples which are either cau stic or a cid ic. (g) Sodium s u lfa te so lu tio n 0 .0 2 5 N ; D is so lv e 1 .5 7 5 g an h y d ro u s N a 2SC>3 in 1000 ml d is tille d w a te r. This solution is not stable and should be prepared when needed. : (h) S eed in g m a te ria l: M ay b e c o lle c te d from re c e iv in g w ater 2-5 m iles below discharge point of industrial w aste w ater. (i) M an g a n e se s u lfa te so lu tio n : D is so lv e 480 g MnSC>4 4H 20 , 400 g M n S 0 4 2H20 , or 364 g MnSChj * H20 in d istille d w ater, filter and dilute to 1 liter. 0) A lkali-iodide-azide reag en t: D issolve 500 g sodium h y d ro x id e, NaOH (or 700 g p o ta ssiu m h y d ro x id e , KOH), and 135 g sodium io d id e , N al (or 150 g p otassium io d id e , KI), in d istille d w ater and d ilu te to 1 lite r. To th is solution add 10 g sodium a z id e , NaN3 , d isso lv ed in 40 ml d is tille d w a te r. P o tassiu m and sodium s a lts may be used interchangeably. -9- : US00003119 Sulfuric Acid, C oncentrate: The strength of this acid Is about 36 N; th e re fo re , 1 ml acid is eq u iv alen t to about 3 ml of the a lk ali-io d id e-az id e reagent. Starch solution: Prepare an em ulsion of 5-6 g potato, arrow root, or soluble starch in a mortar or beaker with a sm all quantity of d istille d water, allow to boll a few m inutes, and let settle overnight. U se the clear, super natant liquid. This solution may be preserved w ith 1.25 g salicy lic acid per liter or by the addition of a few drops of toluene. : Sodium th io s u lfa te sto c k so lu tio n 0.1 ON: D is so lv e 2 4 .8 2 g N a 2S 2 0 3 5H2O in b o ile d an d co o led d is tille d w a te r and dilute to l lite r. Preserve by adding 5 ml chloroform or 1 g NaOH per lite r. Standard sodium th io su lfate titra n t, Q.02SN: Prepare eith er by d ilu tin g 2 5 0 .0 ml sodium th io su lfa te stock solution to 1000 mi or by d is s o lv in g 6 ,2 0 5 g N a2S2 0 j 3H2O in fresh ly b oiled and cooled d is tille d w ater and d ilu tin g to 1 00 ml. S tan d ard sodium th io s u lfa te s o lu tio n may be p re se rv e d by ad d in g 5 ml chloroform or 0 .4 g NaOH per lite r. Standard sodium th io su lfate so lu tio n , e x a c tly 0 . 0 2 50N , is e q u iv a le n t to 0.2Q0 mg DO per 1 .00 m l. - 10- US00003120 S ta n d a rd iz e w ith d ic h ro m a te , d ilu te e x a c tly 1 0 0 .0 ml of 0.2S0N potassium dichrom ate solution used in th e COD determination to 1000 ml. S ta n d a rd iz a tio n of sodium th io s u lf a te s o lu tio n .Q25Q1M: D isso lv e approxim ately 2 g KI, free from io d a te , in an Erlenmeyer fla sk w ith 100 to 150 ml d is tille d w ater; add 10 ml 1 + 9 H2SO4 , follow ed by e x a c tly 2 0 .0 0 ml stan d ard dichrom ate (0 .0 2 SON) so lu tio n . P lac e in dark for 5 m in u tes. D ilu te to 400 ml an d titr a te th e lib e ra te d io d in e w ith th e th io su lfate titra n t, adding starch toward the end of the titration when a pale straw -color is reached. Exactly 2 0 .0 0 ml of 0.0250N th io s u lfa te sh o u ld be req u ired when the solutions under com parison are of equal strength. (o) S p e c ia l re a g e n t - p o ta ssiu m flu o rid e so lu tio n : D isso lv e 40 g KF * 2 U2O in d is tille d w a te r and d ilu te to 1000 m l. 2.1 .3 Procedure The dilution w ater to be used should be d istilled w ater of the highest purity and as near 20C as p o ssib le. The w ater should a ls o be sa tu ra te d w ith DO*. P lace th e d esired am ount of d is tille d w ater in a su ita b le b o ttle and add 1 ml eac h of phosphate buffer, magnesium su lfate, calcium chloride, and ferric chloride *D is solved Oxygen L. - 11- A US00003121 r solutions for each liter of dilution w ater, For th is te s t p ro ced u re, 25 ml of se e d w ater (1/3 m unicipal sew age treatm ent plant w ater and 2/3 river water) w as added for each lite r of dilution w ater. : The sam p les should be n e u tra liz e d to pH 7 .0 w ith eith er the IN H2SO4 or NaOH. For th is t e s t , 5 , 1 0 and 20 ml o f th e p re -d ilu te d sam p les were p ip e tte d in to th e 300 ml BOD b o ttle s w hich w ere th e n to p p ed off w ith the seeded dilution w ater and placed in the incubator. Also placed in th e incubator w as a b o ttle of the se e d e d , aerated dilution w ater. C are must be taken when filling the b o ttles with the seeded dilution w ater to ensure that no air bubbles are en train ed . The b o ttles w ill be stored in the incubator for 20 d a y s a t 20C t 1 C . The DO o f th e sam p les and th e s e e d e d : dilution w ater w ill be checked a t 5, 1 0 , 15 and 20 d ay s. : Before c h e c k in g th e DO w ith th e YS1 DO m e ter, th e m eter w ill be c a lib ra te d u sin g the DO value obtained by azid e m odification of the iodornetric m ethod for d eterm in in g DO. Two ['OD b o ttles w ill be filled w ith a eia tod di itili oo w ater. One w ill be titra te d while the other will be used as a calibration standard. - 12- j 1 : | 1 j 1 i US00003122 - ... V....... The dissolved oxygen content of the sam ples and the seeded dilution w ater control were checked ju st prior to being placed in the Incubator, They were found to be: 5 ml sam p les - 9 .3 0 mg/1 10 ml sam ples - 9 .2 0 mg/1 20 ml sam ples - 9 .1 0 mg/1 Seed dilution w ater control - 9 .3 0 mg/1 The procedure for the azide m odification of the iodometric method for determination of DO follow s: (a) To th e sam p le a s c o lle c te d in th e 300 ml bottle: add 2 ml m anganese s u lfa te so lu tio n follow ed by 2 ml a l k a liio d id e-azid e reagent w ell below the surface of the liq u id ; stopper w ith care to exclude a ir bubbles and mix by inverting the bottle several tim es. When the precipi tate se ttle s, leaving a clear supernatant above the manga nese hydroxide floe, shake again. When the settling has produced a t le a s t 100 ml c le a r su p em a te, c a re fu lly rem ove th e sto p p e r and Im m ediately add 2 ml concentrated h 2s o 4 by allow ing the acid to run down the neck of the b o ttle. R estopper and mix by gentle inversion until d isso lu tio n is com plete. The iodine should be uniformly distributed US00003123 2 .1 .4 throughout the bottle before decanting the amount needed for titra tio n . This amount should be 203 ml. (b) T itra te w ith 0 .0 2 5 N sodium th io s u lfa te so lu tio n to a ! p a le s tra w -c o lo r. Add 1 -2 ml (15d rops recom m ended) :: fre sh ly p rep ared s ta rc h s o: lu tio n andco n tin u e th e t i t r a tion u n til th e firs t a p p ea ran ce of blue co lo r. Each ml of sodium th io su lfa te required is equal to 1 mg/1 DO. The DO m eter is then calibrated using th is figure a s a c o n s ta n t. During the p ro c e ss of taking the DO re a d in g s, th e IX) probe must be rinsed and recalibrated before each m easurem ent. The rinsing is necessary to prevent any carry-over betw een sa m p le s. After each m e asu re m en t, the bottle is returned to the incubator as soon as p o ssib le. BOD C a lc u la tio n The eq u atio n by w hich th e BOD w as c a lc u la te d is a s fo llo w s: mg/1 BOD = (D\ - P i ) - Bj - B2) f P: D] = O riginal DO D2 = DO after incubation Bi = DO of d ilu tio n w a te r b efo re in c u b a tio n B2 = DO of d ilu tio n w a te r a fte r in c u b atio n f = Ratio o f se e d in sam ple to seed in control P = Decimal fraction of sim ple used : 1 I :m.| < i .! > ^ : . I : ; ; ! | ! US00003124 2.2 2 .2 .1 2 .2 .2 for 5 ml sam p le = .983 f for 10 ml sam p le = .9 6 7 f for 20 ml sam p le = .933 P- 5 ml sam ple at 1/5000 = 3.333 x 10-6 1/ 1 2500 = 1 .3 3 3 x 10~ 1/8333 = 2.000 x 10-6 10 ml sam ple 20 ml sam ple at 1/5000 = 6.667 x 10" 1/12500 = 2.667 x 10-6 1/8333 = 4.000 x 10-6 ; at 1/5000 = 1 .333 x 10~6 1/12500 = 5.333 x 10-6 1/8333 = 8.000 x 10-6 Chem ical Oxygen Demand The COD determ inations were conducted in accordance w ith the procedure given in the l i t e r a t u r e ^ . The d etailed pro cedure is given as follows; A pparatus Reflux a p p a ra tu s (250 ml E rlenm eyer or Florence fla s k w ith ground g la s s 2 4 /4 0 n eck and 300 mm Jack et L ie b ig , W e s t, or equivalent condensers with 24/40 ground g la ss jo in t, heating mantle or hot plate.) R eag e n ts (a) S tan d ard p o ta ssiu m d ich ro m ate s o lu tio n 0 .2 5 0 N (12.259 g dried primary standard grade, 103C for j j j j S j || . ! : I 1II 1I 1 I1 US00003125 two h o u rs in d istille d w ater and dilute to 1000 m l. Add .1 2 g sulfam ic a c id .) (b) C o n c e n tra te d H2SC>4 c o n ta in in g 22 g Ag2S0 4 p er 9 - lb . b o ttle (1 -2 d a y s req u ire d fo r d is s o lu tio n ) (c) 0.1 ON s ta n d a rd Fe (IMH4)2 (8 0 4 )2 : D is so lv e 39 g a n a ly ti c a l g rad e Fe (NH4)2 (S04) 2 * 6H20 in d is tille d H20 . Add 20 ml concentrated H2SO4 , co o l and dilute to 1000 ml. (d) F erroin In d ic a to r so lu tio n ; D is so lv e 1 .4 8 5 g 1 ,1 0 phenanthroline monohydrate together with 0.695 g FeSC>4 * 7H 2 0 in w ater (d istille d ) an d d ilu te to 100 m l. (e) S ilv er s u lf a te , re a g e n t pow der (see b) (f) M ercu ric s u lf a te , a n a ly tic a l g rad e c r y s ta ls (g) S u lfam ic a c id , a n a ly tic a l g rad e (see a) Procedure (a) P lace 0 .4 g HgSC>4 the reflu x in g f la s k , add 20 ml o f p re-d iluted s a m p le , sw irl to m ix. Add 1 0 .0 ml 0 . 2 SON K2Cr 20 ? . C a re fu lly add 3 0 .0 ml c o n c e n tra te d H2SO4 US00003126 c o n ta in in g Ag2SC>4 w ith m ix in g . Add 3 or 4 b o ilin g ch ip s (previously ig n ited a t 6Q0C for 1 hour) or g la ss beads to prevent bumping. ftj) Reflux for tw o h o u rs , co o l a n d w ash down c o n d e n so r neck with d istille d w ater. (c) D ilu te th e m ixture w ith d is tille d w a te r to ab o u t 140 ml, cool to room tem perature and titra te the e x c e ss dichrotnate w ith standard ferrous ammonium su lfa te , using ferroin indicator. G enerally 2-3 drops of indicator are used and the amount should not vary among sam ples. The color change is sh a rp , going from b lu e -g re en to reddish-brow n. (d) A b lan k c o n s is tin g of 20 ml d is tille d w ater in s te a d of th e sam ple, together with the re a g e n ts, is refluxed and titrated in the same m anner. (e) Each d ay th e ferro u s ammonium s u lfa te <fo (NH4) 2 (8 0 4 )2) m ust be s ta n d a rd iz e d . T his is done by d ilu tin g 1 0 .0 ml standard potassium dichrom ate solution to about 100 ml. Add 30 ml c o n c e n tra te d H2SQ 4 and allo w to c o o l. T itra te w ith the ferrous ammonium su lfate titrant u sin g 2-3 drops of ferroin indicator. -1 7 - 1 i 1. 1 i ; i I ; ....................................... ............................................................................................................ US00003127 N orm ality Fe(NH4)2 $ 04)2 ~ ^ C ^ O ? x 0.25 ml Fe ( m i 4) 2 ($0A) 2 C alculations The equation used to calcu late the COD follows: M gA g sam ple COD = (a-b)c x 8000 - dilution ratio (straight compound) ml sam ple W here: a = ml Fe ( N H ^ $ 0 4 ) 2 6H 2O u s e d for b lan k b = ml Fe (NH4)204)2 * 6H2O u se d for sam ple c = n o rm ality of Fe (NH4)2 0 0 4 ) 2 * 6H2O sam p le s iz e = 20 m' To g et COD of d ilu ted sam p le, do not divide by d ilution ra tio . Aq u a tic T o x icity The aq u atic toxicity in v estig atio n was conducted on the s p e c ie s funduius h e te ro c litu s (kill! fis h , mummichog) in acc o rd an ce w ith NSRDC p r o c e d u r e s ^ . Phvsiochcmical Properties and Performance The determ ination of the physiochem ical properties of the -18- experim ental form ulations and their fire performance c h a ra c te ristic s were conducted in accordance with the pro cedures given in M IL-F-24385 , Amendment 8 . - 19ik US00003129 EXPERIMENTAL RESULTS The experim ental asp ects of this investigation were based upon th e r e s u lts o b ta in e d u sin g 2 0 -d a y BOD sc re e n in g of various raw m aterials. Aqueous film -form ing foams can be broken down into three general com ponents: Fiuorochemical. Surfactants Hydrocarbon Surfactants Solvents Throe compounds wore selec ted as being typical for each one of these com ponents. These compounds were selected and s u b je c te d to 2 0 -d a y BOD s tu d ie s . B ased on th e s e m aterials, the most likely com binations were formulated in to AFFF c o n c e n tra te s an d s u b je c te d to fu rth er s c re e n in g . * Fiuorochem ical Surfactants Lodyne S - l 05 - an io n ic Lodyne S -l 10 - am photeric Lodyne S -l 16 - catio n ic * Hydrocarbon Surfactants D eriphat D-l 60C - partial sodium sa lt of n -lauryi B im inodipropionic acid - 20- US00003130 Tergitol 15-S -12 - nonionic su rfactant based on lin e a r alcohol fu n ctio n ality {isomer d istrib u tio n C 11 ~ C 1 8 Conco EL-30 - a sulfonic acid derivative of cocoa butter - anionic Solvents (50/50 M ixtures) Butoxy ethoxy p ro p an o l-2 /h ex y len e glycol Proposal B/ethylene glycol Butyl c arb ito l/p ro p y lcn e glycol The r e s u lts of th e BOD in v e s tig a tio n are g iv en in T able I. Table I BOD R esu lts of Experim ental Compounds E xpressed a s mgms 0 2 /mgm Compounds M aterial bodyno S - l 05 Lodyne S - l 10 Lodyne S -l 16 D erip h at D -l BOG Conco EL-30 Tergitol 15-S -l 2 BEP/HEG Propasol B/EG BC/PG BODn .443 .245 .118 .336 .458 .150 .444 1.070 1.109 BOD} 5 .409 .272 .059 .378 .423 .111 .440 .716 .701 ROD20 .430 .286 .103 .431 .407 .121 .51 7 . 957 .899 The re su lts oi the COD determ ination are given in Table II and show little co n cen tratio n d ep en d en ce. -21- T able II COD R esults of Experimental Compounds M aterial D ilu tio n COD (mqms/1) Lodyne S - l 05 Lodyne S - l 05 Lodyne S - l 10 Lodyne S - l 10 Lodyne S - l 16 Lodyne S -l 16 Deriphat D-160C D eriphat D -l 60C Conco EL-30 Coneo EL-30 Tergitol 15-S-12 BEP/HG Propasol B/EG BC./PG 1:12,500 1:5,000 1 :1 2 ,5 0 0 1:5,000 1:12,500 1:5,000 1:12,500 1:5,000 1:12,500 1:5,000 1:12,500 1:8,333 1:8,333 1:8,333 776,875 780.850 498,000 539.950 368,500 509.950 597,625 669,300 507,750 533.850 2 ,1 0 1 ,5 0 0 2 ,0 6 4 ,9 1 7 1 ,789,428 1 ,9 2 2 ,2 0 3 Based on th ese re s u lts , the most lik ely fiuorochem ical surfactant w as Lodyne S -l 05. The hydrocarbon surfactants could eith er be D eriphat D -160C or Conco EL-30. Any of the solvent system s selected would be ac c e p ta b le , assum ing th a t a minimum BOD20 to COD ra tio of .15 can be u sed to define biodegradability. Prelim inary 28 s q .f t , fire te s tin y elim in a te d Lodyne S - l 10 from further co n sid eratio n due to poor extinguishm ent and burn back c h a ra c te ristic s . The use of the solvent system Propasol B/Ethylene Glycol also resu lted in poor expansion ra tio s (c 2-3} and poor burnback r e s is ta n c e . -22- It w as therefore decided to screen for fish toxicity based upon the following: Lodyne S - l 05 Conco EL-30 Butyl C arb ito l/P ro p y len e G lycol Butoxy Ethoxy Propanol-2 /H ex y ln e G lycol P revious work ^ involving form ulations u sin g D eriphat D -160C a s th e hydrocarbon s u rfa c ta n t in e x p erim en tal AFFF form ulations had resulted in reasonably good fish toxicity values. The u su its of the 90-hour aquatic toxicity studies on the lu o ro ch em ical { S -l05) and th e h ydrocarbon s u rfa c ta n t (EL-30), as w ell a s the two solvent sy ste m s, are given in Table III. -23- , a , .............--- Mm US00003133 Table III 96-Hour Aquatic Toxicity Investigation on Fundulus H etero clitu s (Mutrimichogs) Compound Houi LCso PPm Confidence Limits No Effect 95% Level (ppm) EL-30 48 4 6 .0 34.6 - 61.2 72 4 2 .0 2 9 .8 - 5 9 .2 96 3 4 .5 2 3 .8 - 5 0 .0 -- 15 S-105 48 3000 72 2500 96 2150 2521 - 3570 2136.8 - 2925.0 1869.6 - 2472.5 ... ~~ 1300 5 0 /5 0 Butyl C arbitol & Propylene Glycol 48 72 96 4800 4350 4125 4485.9 - 5136.0 4103.8 - 4611.0 4004.8 - 4248.8 -- 3000 50/50 Hexylene G lycol & BEP 48 2150 72 1875 96 1690 1837.6 - 2515.5 1644.7 - 2137.5 1469.6 - 1943.5 -- 1100 As a r e s u lt of th e 2 0 -d ay BOD s tu d ie s , th e follow ing form ula tions were prepared and tested . M aterial F-117 Formulation Number r-i 18 F-121 F-I22 S-105 EL-30 D -l 60C BC/PG* 3 .07 4.07 --5.07 3.07 6 . 0% -7 . 0% 3 .0% -- 4.07 5 . 0% 3 .0% -- 6, 0% 7 .0% *507o/50% m ixture by w eight of butyl carb ito l and hexylene -24- j- -I k . - ............... - ...^ -------------- ....................... - ........................i i US00003134 The aquatic toxicity studies for these form ulations is given in T able IV. Compound F-l 17 F-118 F -l 21 F - l 22 T able IV 96-Hour Aquatic T oxicity Investigation on Fundulus H eteroclitus (Mummichogs) Hour LCsO C onfidence Lim its No Effect .PPm 95% Level (ppm) 48 595 4 5 0 .8 - 785.4 72 455 3 8 8 .9 - 5 3 2 .4 96 365 3 0 1 .7 - 4 4 1 .7 105 48 475 413.0 - 546.3 72 435 3 8 1 .6 - 4 9 5 .9 -- 96 395 3 5 5 .9 - 4 3 8 .5 180 48 1855 1650.4 - 2070.2 72 1385 1 1 1 2 .8 - 1 S 6 5 .6 -- 96 1 31 5 1 0 9 0 .7 - 1 4 9 7 .9 1300 48 1850 1659.8 - 2090.2 72 1365 1100.2 - 1580.4 -- 96 1330 1 0 6 0 .7 - 1 5 0 8 .8 1330 The 28 s q .f t, fire testin g of th e se form ulations is given in T able V. No a p p re c ia b le c h a n g e s in perform ance or foam quality w ere noted after aging at 1 S0F for 10 d a y s. -2 b- . ...................................... ... ...................................................................................... US00003135 T ---! Table V 2 8 S q .F t. Fire Perform ance of E x p erim en tal AFFF F orm ulations 90% E xt. 25% 25% Form. Solution C ontrol Time Time Bumba ck Exp. Drain Time No. Cone. (Sec.) (see) (sec.) Ratio (sec.) F-117 r-i 17 6F 6S 18 24 480 6 . 6 204 19 33 480 4 .7 174 F-118 F-118 6F es 18 24 480 7 .6 260 1 8 24 480 6 . 2 222 F-121 F-121 6F 6S 19 23 480 6 .8 230 19 26 480 5 .4 198 F-122 F-122 6F 6S 18 24 480 6 .7 207 19 26 480 4 .9 247 B ased on the aq u a tic to x icity data co n tain ed in Table IV, the u se of EL-30 a s a hydrocarbon su rfacta n t is d e le te rio u s from an environm ental asp ect oven though the fire performance c h a r a c te r i s t ic s , a s show n in T able V, a re a c c e p ta b le . It is also clear that higher solvent lev els and higher hydrocarbon su rfactan t le v els tend to give b etter foam q u ality . It should a ls o be noted th at thus*- two com ponents have little or no e ffe c t on the fire perform ance c h a r a c te r is tic s . It a ls o su b s ta n tia te s i!k.' fact that tlii; p re s e n t u s e le v e ls of 15--20>3 s o l vent have little or no effect on fin- perform ance a s well as foim q u a lity , assu m in g a 5:1 ex p a n sio n ra tio is a c c e p ta b le . US00003136 A lte rn a te M eth o d s for the Determi nation of AFFF S o lu tio n C o n cen tratio n In order to determ ine if an aly tical methods other than refrac tiv e in d ex could be u s e d to d eterm in e AFFF s o lu tio n com po sitio n , the following study was undertaken. The ab ility to reduce the solvent lev els would resu lt in a product having a low er environm ental im pact and a lower cost to the en d -u ser. To th is end, the follow ing in v e stig atio n w as undertaken. Aboard N avy s h i p s , aq u e o u s film -fo rm in g foam (AFFF) is usually stored as a concentrate. When used to extinguish a fire, the concentrate is pumped through a proportioning device where it is mixed with sea w ater and th is mixture is sp ray ed from a n o z z le . Optimum AFFF perform ance re q u ire s th a t th e p ro p o rtio n in g be a s c lo s e to 94 volum es of se a w ater to 6 v olum es of AFFF c o n c e n tra te a s p o s s ib le . Because of po ssib le m echanical shortcom ings, the propor tioning system may not achieve the optimum volume ratio and would require adjustm ent. Therefore, a means of deter mining th e d ilu tio n of an AFFF c o n c e n tra te is re q u ire d . At p resen t, refractive index is used to monitor the accuracy of a proportioning system and to achieve a sufficiently large change in refractive index w ith dilution requires that a q u a lifie d 'AFFF c o n c e n tra te c o n ta in 15 to 20% o rg an ic s o l v en ts. Since the surfactant activ e ingredient content of q u a lifie d AFFF c o n c e n tra te is o n ly in th e ran g e of 4 -6 % , th e ad d ed so lv e n t re p re s e n ts a 4 -fo ld in c re a s e In th e BOD loading of the system . If an altern ativ e method for m onitoring the performance of a proportioning system can be developed, a significant d e c r e a s e in th e en v iro n m en tal im pact of an AFFF sy stem would be re a liz e d . This report d escrib e s the developm ent of a sim ple field te st method of meamating the dilution of AFFF c o n c e n tr a te s . Suggested Solution Based on the resu lts of investigation described below , the dilu tio n of an AFIT c o n ce n trate can be a c c u ra te ly determ ined by the addition of a w ater soluble dye to the concentrate and m easuring the absorbance of the proportioned solution with an inexpensive field colorim eter. The dilution is determined from a d ilu tio n v s . a b so rb an ce w orking cu rv e. The accu racy of the method is b etter than t 0.5% proportioning, ab so lu te. U sin g l e s s d y e , an a c c u ra c y of t 1% is a c h ie v e d . T his m ethod is a p p lic a b le to a n y AFFF c o n c e n tra te . 3.3 The W ater Soluble Dve Approach . A w ater soluble dye, diphenyl brilliant blue, was obtained ' : i |> from the D yestuffs and C h em icals D ivision of C iba-G elgy j i C orporation, G reensboro, North C arolina. The Color Index ; ! i co d e for th is dye is D irect Blue I. A 120-1 30 ppm so lu tio n ; I: o f th e dye w as p rep ared in an e x p e rim e n ta l, low so lv e n t AFFF : c o n c e n tra te and th is s o lu tio n w as d ilu te d from 2% to 10% by volum e w ith natural sea w ater. The w avelength of minimum percent tran sm issio n , i . e . , g reatest absorbance for the d y e, was determ ined by m easuring the percent transm ission of a dilu tion a s a function of w av ele n g th . The minimum w as found to be a t 635 nm. The percent tran sm issio n of the prepared d ilu tio n s was m easured on both a Metrohm Spectrocol arim eter and on the Bausch and Lomb Spectronic M ini 20. The re s u lts of th o se : m easurem ents are plotted on the graph in Figure 1. A smooth curve is obtained on eith er instrum ent, and the change In per- US00003139 cent transm ission is sufficient that a difference of 0 . 5% ab so lu te in pro p o rtio n in g can be d e te rm in e d . S im ila rly , u sin g 3M LIGHT WATLFi FG -206 AFFF, c u rv e s o f % T v s . pro p o rtio n in g w ere co n stru cted and are shown in Figure 2. The d ifferences in the two curves in Figures 1 and 2 re fle c t the differen ces that are typically observed between two instrum ents. This points up th e n eed to c o n s tru c t a w orking cu rv e for e a c h AFFF an d e a c h in s tru m e n t. A p h o tograph o f AFFF c o n c e n tra te an d s e le c te d d ilutions in sea w ater are shown in Figure 3. In o rd er to re d u c e th e co lo r of th e AFFF c o n c e n tra te and d ilu tio n s , the precision of the method with one-third the amount of dye w as determ ined. The curve relating proportioning and percent transm ission is shown in Figure 4. A smooth curve is obtained but h as lo s s slope than th o se shown in Figures 1 and 2. The p re c isio n of th is m ethod is 1 1% pro p o rtio n in g a b s o lu te . Figure 5 is a photograph of th e AFFF c o n c e n tra te and s e le c te d s e a w ater dilutions containing the reduced amount of dye. Recommended Procedure : (a) A djust th e w av ele n g th of th e co lo rim eter to 635 nm . (b) C o lle c t a sam p le o f th e s e a w a te r d ilu e n t. I j > 1 US00003140 rcent Tr^ts-iss i US00003141 Percent Irc.sr.issio US00003142 1 AFFF Concentrate i0 l Proportioning ,,6 Z Proportioning 2 7. Proportioning Figure 3. AFFF Concentrate Containing 120 ppm Dye and Selected Sea Water Dilutions -3 3- Jmmmmm US00003143 90 80 70 60 50 40 30 20 10 0 US0000314 AFFF Concentrate 9l Proportioning 11 Proportioning 5 7. Proportioning 3 7. Propor Honing Figure 5. AFFF Concentrate Containing 40 ppm Dye and S e le c te d Sea Water D ilu tio n s 11 US00003145 r (c) P lac e th e s e a w ater d ilu e n t in th e 1 cm sam p le c e ll supplied with the instrum ent, place the cell in the instrum ent, and adjust the scale rending to 100% tran s m ission , (d) U sing th e M TF c o n c e n tra te in q u e s tio n , co n tain in g the dye, construct a working curve of % transm ission v s. proportioning using solutions of known dilution and measuring their percent transm ission, (e) C o llect the proportioned so lu tio n in question in the usual manner. (f) R inse the c e ll with the proportioned solution and fill it w ith the proportioned so lu tio n . (g) Read th e p erce n t tra n sm issio n and d eterm in e th e pro portioning from the working curve co n stru cted for th e AFFF s y ste m . E xperim ental Al' d ilu tio n s w ere prepared using standard volum etric g la s s w a re . The sam p les u se d in th is stu d y w ere: (1) A C ib a-G eigy ex p erim en tal AFFF c o n c e n tra te c o n ta in in g no ad d ed so lv e n t coded K '7b-312 , and (2) 3M Company F C -206, Lot 1 1 . "36- US00003146 Percent transm issions of solutions were m easured on a Metrohm M odel E 1009 Spectrocolorim eter a n d /o r a Bauseh and Lomb S p e c tro n ic M ini 20 s p e c tro p h o to m e te r. One c e n ti meter path length curvettes were used throughout. S y n th e tic s e a w a te r w as p rep ared a c c o rd in g to ASTM D -1141 52. N atural sea w ater w as obtained from Long Island Sound. The w ater soluble dye u sed w as C iba-G eigy Diphenyl Bril liant Blue FF Supra 1 . flH -37- US00003147 4 .0 CONCLUSIONS A series of nine com ponents, consisting of fluorochetnica 1 su rfactan ts, hydrocarbon surfactants and so lv en ts, were s u b je c te d to 2 0 -d a y BOD s tu d ie s a s w ell a s COD s tu d ie s . These nine com ponents were further reduced to one fluorochem ical su rfactan t, two hydrocarbon su rfa c ta n ts, and two solvent system s based on fire perform ance using the MIL-F24385 28 s q .f t, fire te s t. A concentration design experim ent using the two different hydrocarbon su rfactan ts a t two different concentrations and the two so lvent sy stem s a t two d ifferent co n centrations w as conducted. Aquatic toxicity stu d ies elim inated one of the surfactants and one of the solvent system s. The concentration experiment showed that the fish toxicity w as independent of the com position and the 28 s q .f t, fire perform ance w as equally accep tab le at both le v e ls . The major effect of solvent level and hydrocarbon surfactant lev el is to give a b etter quality foam with no difference In e ith e r e x tin g u ish m e n t or 25% burn back r e s is ta n c e . The aquatic toxicity appears to depend on the fluorochem tcal US00003148 Surfactant and the hydrocarbon su rfactan t more than so lv e n t type or concentration. An a lte r n a te m ethod for d eterm in in g AFFF s o lu tio n c o n c e n tra tion was developed which allow s an accuracy of t .5%. This method is based upon the m easurem ent of the absorbance of a dye doped solution of AFFF. The method requires the preparation of a calibration curve and is capable of being conducted in the field using an instrum ent of com parable cost but greater accuracy than the present refractive index m ethod. : It is possible using the lev els of com ponents described in th is rep o rt to form ulate AFFF c o n c e n tra te s h av in g a c c e p ta b le b io d e g ra d a b ility (BOD20/C O D >15) and a q u a tic to x ic ity (LC50 96-h o u r - 1500 ppm ). F u rth er com ponents in a q u a tic toxicity will require the synthesis of le ss surface active fluoiochem icai su iiactan ts which w ill require some trade-off in fire fighting perform ance. -39- ... ......^ ......... ........................ .........: ----- -------- -------------- US00003149 BIBLIOGRAPHY (1) T e c h n ic a l Report EHL (K) 7 4 - 3 , B io d eg rad ab ility and T oxicity of F C -2 0 0 , Aqueous Film Forming Foam, February 1974. (2) T ec h n ical Report EHL (K) 7S-3 Biodegradability and Toxicity of Ansul K'74-100 Aqueous Film Form ing Foam, January 1975. (3) Com m ander NAVFAC M em o, 13 M ay 19 7 5 , A queous Film Forming Foam (AFFF), R evised D isp o sa l G uidance. (4) S tan d ard M ethod for th e E xam ination of W a ste an d W a s te w a te r, APHA, AWWA, WPCF, 12th E d itio n . (5) S tan d ard M arin e B io a sse y P ro ced u res for S hipboard C hem icals, David W . Taylor, Naval Ship Research and D evelopm ent C en ter (DTNSRDC). (6) F our-D ay S ta tic A quatic T o x icity on Mummichogs of K '7j 268-144, Industrial B io-Test L aboratories, In c ., January 1 976. US00003150