Document DGdzYDmpX3B40QVm5Reyq5wMM

M Sl9l6 _ 0 9 2 .6 SUMMARY FOR FOAMING STUDIES DONE ON VARIOUS AFFF PRODUCTS TEST SUBSTANCE_______________________________________________ Identity: Mixtures containing perfluorooctanesulfonate, which may also be referred to as PFOS or FC-95 or as a component of AFFF products. (1-Octanesulfonic add, 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluoro-, potassium salt, CAS # 2795-39-3) Rem arks field: compositions. The test samples are AFFF products of various STUDIES__________________________________________ ____________ The attached testing is a compilation of studies done to characterize the capacity of 3M's AFFF product line to create foam in various situations, and, in some cases, the effectiveness of various anti-foaming agents. This includes the effects of foaming on wastewater treatment processes. DATA QUALITY__________________________________________________ Reliability: No ranking of this data has been done. These studies are atypical, have no agency-approved procedure, and were designed to provide general guidance to customers and wastewater treatment operators who must address the issue of treating foam after using AFFF in a fire event. O T H E R __________________________________________ Subm itter: 3M Company, Environmental Laboratory, P.O. Box 33331, St. Paul, Minnesota, 55133 Last changed: 6/28/00 003042 Internal Correspondence r i cc: D. R. Ricker - 53-4 C. S. Chow - 21-2W (58) 2^6. : T o t ^ z : . To: R. R. BURFORD - COMMERCIAL CHEMICALS DIVISION - 236-1 From: E . A. REINER - ENVIRONMENTAL LABORATORY (EE & PC) - 21-2W (58) Subject: FC-780 FOAMING IN ACTIVATED SLUDGE Date: AUGUST 15, 1979 We conducted two sets of tests in the Environmental Laboratory to determine the FC-780 concentration that would cause foaming in activated sludge waste treatment systems. The first set of tests involved shaking 10 and 100_:mg/l of FC-780 in 100 ml of activated sludge. Return sludge was resuspended to 3000 mg/1 in primary treatment* j effluent from the St. Paul Metro Waste Treatment Plant (see Photos 1-5). After 30 seconds of vigorous shaking,, less than one-half inch of foam formed at 100 mg/1 (Photo 1). The jars containing the 10 mg/1 FC-780 solution and the control both had slight foam that only covered the edges of the sludge surface. Though little or no foam was formed at an FC-780 concentration of 10 mg/1, the sludges containing this concentration and 100 mg/1 of FC-780 did not settle well after shaking (see Photo 5). Shaking in the presence of 10 mg/1 of FC-780 entrained air bubbles in. the sludge. A second set of tests was then run in which aeration with an air sparger at 500 ml/min. replaced shaking (see Photos 7-10). No foam formed even at 100 mg/1, and no settling problems developed. These same samples, when shaken, behaved as in the first set of tests (see Photo 11). Primary treatment is the first major step in wastewater treatment in which settleable solids are removed. I > ooidlP- R. R. Burford -2- August 15, 1979 We feel the aeration test more closely simulates the conditions of a waste treatment system than the shaking test. Therefore, we don't anticipate serious foaming or settling problems below 100 mg/1. EAR/cen Attachments 003044 BEST COPY AVAILABLE 003045 C :^ 6 003046 Form 10620-5-PWO cc: L A B REQUEST BOOK - 42-5W U a o *. JU|0 < , 'f b PR O D U C T EC O LO G IC A L ASSESSMENT *cttmraooPi REQUEST FOR LABORATORY WORK Rg$: ENVIR. ASSESS. INQ.. # ^rrvvi4u<u>> PRODUCT-^Pii - 7o & ___________ C " a C a LAB REQUEST NO. 5 ^ Name: Request Date: ^Project No.: Code No.: Sample Date: REQUESTER ___ 2. il g frO /3/700 Phone No. 5 ' 7 ^ /<?**? Prob. N o .. Date Needed: LABORATORY Date Received Sample: Analyst:--------------Date Completed:. Hours Spent: Y ___________B _ --s - t e - r i tAr 7? Description: _ ^ / - d 7ifi T <3^Purpose of Tests: rh~f- e* UiiUA- *a * * * " 0 -Yr<cl^~ Please Call Requester If Delays Are Encountered. PHYSICAL & CHEMICAL PROPERTIES H ea to f C om bustion C al/G (B T U /L b .)___ Density Ash Other WATER POLLUTION pH COD BOD, BOD, U ltim ate TOC >GC 1 VdS^ WOxygen U ptake s' Dehydrogenase A c tiv ity (T T C ) O ther f ^ C ' / i E ! P*- /QO ,/ ^ Z l S-^V0*o y i - H m 02 721 n^C Sz3 -f /Q ^ ^ / f pw, Z 2 & & . ix. `[E M T >A /^L Y- (j>)Aa / kX V l T f 7^ 7^ ac r ^ z 2*__ LL* --- BIOASSAY Specify Organism and Method: & > /' 3 o S ^ c LEACHATE FROM LEACHING TEST pH COD BOD, BOD, U ltim ate TOC GC Bioassau O ther OTHER Bioaccum ulation Persistence Degradation Products fijSC/'fA-o ^ 1. J XttyC-- /gp^A f hj<ri ^U=- i r * je^ck ^ i . *ft^ J*kL J & J S & E 3 M . J / * > / ^ 7 * 0 m. 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J oi! sin * WUH i r2\-^3 (X 00 ill u> ^ ^ <\S i& i u V o cj 5* r (couJ *2> a: nB# ^: O' CO o. o 5 i.5 N r< VA * ^ ` I WS RS o-j. r\j ^tO TS t/5 o* O: U O O CQ W H O .J >--t w c> w H s CO !> S I o<> W* o 5 H . *wu* o K0- o U IS1 to q ottrMt- project NO`ffg33fl<a/ a '7ao Subject: ject: Reference: 04>*C, ^ L r r v - PAGI 3M TECHNICAL NOTEBOOK NO. 50278 Date: ^ - 0 7-7^1 BEST COPY AVAILABLE &se'/i v*rrt M S D otfTflO*- - & lio o ^ /x - 2SA 6 <<(f **0 ^ *H ? t(*\ | M l/J, 2. c **< AT _2 tU i* A yr 2.<kvj y u . * n < s S .VtfM Ta <0 *o 3n KdHt 6 ,3 * m Herrs ! /'/d T & d r y A t Y >4 1 h ZSL i w t &o- +s '^ i- t j 6^- -/C Pc-'J$Q j L o T Sol * AwJl <rxsJrAsts. erf T ^ 4**'f2**p*. <LAa t +Jy fPra^utWXASAK.. ovr^ ^r l t d s u r * --- vrZ-. m r Q&SSSJlXlSS. ____ .... F&tm HI6HT AT -nM ^ - J L J * d i ' 3MIM< la p itL J i& itL -D___ai.fi __ & & M ,/ cm C<K /Ito (J0*4/* ~ -- r , J #r1 :Pd#l . : ^ c>a ~ { J O v *^I. ~.-- w i d M 7 e A . if tm.\ .3 *fe . .Sen* M^tb t, AAtndt, V^- 04- * r < Aas sfirK &4yCZ?L+ j/ FC-78^f c J 7 5*>J /4*SQ**' 0>s Y^Ik v Signature . --- O c A-af /<? -- n.t.- S `"tf7,`^ 9 -- ---- 003050 cmcoo HO O "U -< mIC"D e \ 003051 project No.f2^70017. 7oQl*>nj Subject: 3M TECHNICAL NOTEBOOK NDOat.e: Te3r PAG! 50278 10 bject: Reference: fxPefii/K/J-rtc:) *' Pa. j? &r*-l 04, ^t-T* 3, V ^u( o4rv<. ^ ^ m iu a u .^Uvm^**nW^C.c^ ^ v m I TrWHiJy /.+<*u*ur*2i, C^S*aa4/iJttt* <w D & seM irnm S p f v t f --f -<iiL^> /* 'htf' i V A -dSP J*n*r*s &** 3i '/X<- V m MA^XCerJ .^o *-*-> 7 . * rf-vi^ VV*A^tUAA4-^ T - i 7^ -- r ^ J> 7T o * ' fc` ' Of~*A. Signature A 4 j>, - $ U u ^ // AT* - --V- 003052 tv# (.y 'Tibi ^ a j T t ------------- su*' '7^ 3 a c itijdy ' BEST COPY AVAILABLE I 003053 npotZTOO ___ PRQJ3CT NO,: 2 rZ`? Subject: \ )bject: Reference: x p e & i / * e ( >) ~ fU s<sv-es^ 3 ^ , M. ro3gr PAG 3M TECHNICAL NOTEBOOK NDOat.e: P5- O0 2S -778^ 1 BEST COPY AVAILABLE -> ( c ) ^ u j > w? A ~*ArtLAk0,/ <- ">K^feAie^ Al' 'S^A-C- r 01My/tm4 *t,dP ^0 'yy'^i^UA.ii^ ^ v ^ V c ^XP. o>) >*v>v 1 c ^ ^***1 K. > Sianaturc 1 ^ A *{j $. # Ro:>il -in`i I'jvI.t t<'iv| P-c: 8 - f i t - 19 ____ ov 003054 sua L.RV'. G Y r z $ 00305ft b e s t copy available CO h- C0 111 I cc >- Q D H CO zo < o u. LRN: 6912S 3M ENVIRONMENTAL LABORATORY (AFFF Foaming Study) Protocol Reference: EAR 6/13/81 Sample Description: L-5439, cc814-28, F-6661, Lot 501 Date: 6/18/81 Analyst; W.A. Scheil The activated sludge mixed liquor was obtained from the Metro Treatment Plant (Pig's Eye) on 6/18/81. The estimated MLSS , concentration using the Spec. 20 technique was 2,100 mg/1. The concentration was not adjusted prior to running the foaming study. The MLSS of the mixed liquor was analyzed using the standard protocol for TS and found to be 2,100 mg/1 and 1,900 mg/1 (duplicate analyses). TS Protocol Reference,: Standard Methods, 14th Ed., pp. 89-98. A stock solution of 1.0 g AFFF/100 ml was prepared by dilution with deionized water. Five 250-ml graduated cylinders were filled to the 200-ml mark with the fresh mixed liquor. When the solids had settled far enough, aliquots of clear supernate were drawn off as follows: Cylinder # 1 - 0 ml; Cylinder #2 - 0.30 ml; Cylinder #3 - 1.0 ml; Cylinder #4 - 3.0 ml; Cylinder #5 - 10 ml. Then the same volume of AFFF stock solution was added to the cylinders as the volumes of clear supernate drawn off. The cylinders were then covered with Parafilm and mixed by inverting. This prepared a dilution series of 0, 15, 50, 150, and 500 mg/1 of AFFF in mixed liquor. The solutions were divided into two 100 ml aliquots. 100 ml was poured into 500-ml graduated cylinders and the other 100 ml was left in the 250-ml cylinders. SHAKE TEST The portions which were left in the 250-ml cyinders were covered with Parafilm and vigorously shaken for 30 seconds and then allowed to stand. Photographs were taken and the foam volumes were measured at the following intervals: -O l * Foam Volume(ml) AFFF Cone. Time 0 (I Min. 5 Min. 20 Min. | Hour 0 mg/1 15 mg/1 50 mg/1 150 mg/1 500 mg/1 2 2 6 16 36 0 0 2 8 30 00 00 00 42 22 10* 0 0 0 0 10* *The foam appeared less dense then previous observation. Page 1 of 3 003057 LRN: 6912S Date: 6/18/81 Analyst: W.A. Scheil AFFF FOAMING STUDY - continued The foam volume (ml) was measured in lieu of foam height by reading the graduates on the cylinders. The settling of the solids was observed after 1 hour. AFFF Concentration Volume of Settled Solids Volume of Floating Solids 0 mg/1 15 mg/1 50 mg/1 150 mg/1 500 mg/1 20 ml 16 ml 10 ml 9 ml 6 ml 10 ml 11 ml 12 ml 13 ml 12 ml After 1 hour of settling, the cylinders were swirled and a photograph was taken after 1 minute of settling. See photo titled 'Swirled After 1 Hour Settling, T=1 Min.' The cylinders were then swirled a second time and a photograph was taken after 20 min. See photo titled 'Swirled a 2nd Time, T=20 Min.' At this point, the settling of the solids appeared uniform in all concentrations. AERATION TEST The 100-ml portions which were poured into the 500-ml cylinders were each aerated for 5 minutes at approx. 500 ml of air per minute using gas dispersion tubes with fritted glass ends. Foam in the 500-mg/l solution had to be controlled from coming over the top of the cylinder by swirling the air supply tubing. The foaming in the 150 and 500-mg/l solutions carried considerable amounts of the mixed liquor solids up the sides of the cylinder and in the body of the foam. Almost all of the solids in the 500-mg/l solution were removed from solution during the aeration period. See photos titled 'During Aeration' and 'After 5 Min. Aeration.' At the end of the aeration period, the cylinders were covered with Parafilm and inverted several times to wash the solids o f f the sides. After this, the foam volumes wete measured at the following intervals: Page 2 of 3 003058 - AFFF FOAMING STUDY - continued LRN: 6912S Date: 6/18/81 Analyst: W.A. Scheil Foam Volume(ml) AFFF Cone. Time 0 1 Min. 5 Min. 20 Min. 1 Hour 0 mg/1 0 0 00 15 mg/1 0 0 00 50 mg/1 0 0 00 150 mg/1 5 0 00 500 mg/1 15 10* 10* 10* 0 0 0 0 5* *The foam appeared less dense than the previous observation. The settling of the solids appeared uniform in all concentrations. Page 3 of 3 003059 PROTOCOL FOR AFFF FOAMING STUDIES EAR 5 /1 3 /8 1 Obtain fresh activated sludge mixed liquor from Metro treatment plant. using tho spec 20 techn iguo and the graph of adsorbance at 600 nm versus SS, adjust MLSS to 2000 mg/1 by DI water addition or by centrifugation and discarding supernatant. Moke 500, L50, 50, 15, and 0 mg/1 solutions of AFFP in 200 ml of this sludge. Divide each solution into 2, 100 ml parts. Placing 1/2 in a jar with at least 200 ml of head space and the other half in 500 ml volumetric cylinders. Cover and shake each jar vigorously for 30 seconds. Take photographs and measure foam height immediately after shaking (time 0) and at 1 minute, 5 minute, 20 minute, and 1 hour. Also observe and photograph how well sludge settles. Aerate the AFFF sludge mixtures in the volumetric cylinders for 5 minutes at 500 ml of air per minute using gas dispersion tubes with fritted glass ends. Again, observe foam height or volume and sludge settling, again make photographs. BEST COPY AVAILABLE \ 003 v* V* SHAKE TEST PHOTOS AFFF FOAMING STUDY, LRN : 6812S LU 3 >- CL O O aiF-- CD CD It* - TST- rK.*y, veo: . \ M f t W M ; wiJ*. ?icrmx>t Afc r e * etfc /ij8t <sa i Pt-XZCj LOTSO/ 2 3 h iq /A . 4 9 "0 V j f * J&&* 7 S SO &S& w gK. 9 " ` : 10 M 12 13 P C ~ U > G C j L O T -< O Z 14 (5 > J r Mq/JL 19 j & 17 A X?- ^ <9 /S o y<o ./ 1 COO ^ 9 0 w 20 2 22 23 H 2S 2 fp o T E i 27 28 1 . - 29 .*" .;' ' -. .-' , -r . - O o 2 - - o /o o ; o / r 3.. TtocG XM6 3o - ` - i r * 13* 75* t :i v-: / f ..-l'y.' a m it r 0U*A KjLAjuy J /jL.*C/\f ;j /y y 4eeui'htl. cuettt, j *r3*nV 7^* STP; ,<out /w ^/ ^-4.A-;.m.-., k l - *T\/ Pd/ fr\ iJJiK &AJ.*r r/y A/-V r /kr.4 r Ppeyi*WJ Jktiw j _ - ;1 ":vy."'" 1 'T*> ' c? : O 0o . 'V o O' o > LO rHAC 0 Vo I f . s <p o 7_.`\'*.;u.' yr y Ar*t~ *, /W /rf JAJ-tSW<*fVfirfA~ wl. l, 21um / r tT rt* ,r^ 4lia >1^.0, LZ f o f o r / y ^7\ i ^ y&< - t S0 ? '^JL^fT .rfS a.tA: i am X f M tr t-- *. TJ-<a c/ ' -T C t ..; TTt m ; /) u r t O, T// -y f j a r At/ pe , y V-3ur P uyvtA e fi# - 5y77.Vy r / / Z u rh C<ry/; Tfl: y* ''.;V'v: W /c X.A,''SMfcLfy- 'ga-f-a-3 ' .,*S.-V' '* -*'K 99000 FORM t 0620 PWO S A M PLE D E S C R IPTIO N F r : Page N o ENVIRONMENTAL ENGR. LAB - WORK SHEET BEST COPY AVAILABLE o., Lfikr~TC Zi>' 3-12-SZ Analvt: Mrs.: L-J < , S ' S~fu.dcj -- M ^ T c S L d L* cm S/ t iJ t l a .. -- J/Ul^ilCQ--LjP iaj& X ia~. { [ L * ^ b __ Sfx<;~lYr<>__ H tH oD ci ajo d Av ^ a A A t \ S 7s - a (t ' L ts rJ T U s t cLgtt ' nfisfoz . P/C?ic0*f tce * tA'. 'fr . __________ (&<- L^* y . 7 k i ^ U u ^ P h uss rs s ) o ^V **. irvf^-- ~Ao Jb*. 2/ _LdiC_L<l- ^zr^c-^tr-P Jh-^ ~TS5 . A __________________ _____ ,, K) : d . s c & & 3 - / 7 -^ 2 - Reviewed by: " -- Ot>37 ;Hf5in<j the , 600 nm versus S S ; adjust jrtbss to 2000 mg/X by ^.addition or by centrifir^^n; ^ H g L ' `.Mni'O 500 , 150, : of this sludge, S* 1 v^' ai^ f ;A^lFP?^n^:200' - ;S7':7 I ', , .'Pivide each ;so lotion intp 2, 100 ml Pimping*; l / 2 */ it''/,.-.',^.'::.'V'.' ~--"- - ' C'y'7' V : ..Take photographs and measure foam heightimmediately after .hSohuark.ingA:-l(i:stL'oiU!m'eo;bse)rva'ned'-a'nadh.- p1homitnou7gt,,re_a,_p.lh 5homiwnuwtel,l-.s20l;udmgi>en7u7ts7e1;t:t*"Vla-venlsd-. l7'.':;j;7--7v':.:-" Y ?'77 Aerate the AFFF sludge mixtures in the volumetric cylinders for 5 minutes at 500 ml of air per minutehsing gas dispersion tubes l^ith7frttte<l glass ends'/'.' 'V;:: -:: . .HV'fv . "'- -'?v,.:.' " '.. -: Again, observe foam height or volume and kludge settling, ;again make photographs;. 'Of- :-7'7 t > :-i Lfi- &#AC D '' r-!:.;ac' H-V l*. - <,- -, - -%:; 7. / pd "v ^ 7 ; * . hf\\Ti' i . :v7 ^ %, M.wvW'f*y iA.;>*7 p .cOvV" sm ;/'.'-N m BEST CQPYAVAILABLE t'y fY'-,`v$i~ vV::V:; ... iiS'ffivv'i:c;'''' " ..............^ ...... . 003068 > h /i k e r e s ? F C - Z o J C' 7"^ 0 MifJ, BEST COPY AVAILABLE f lvo%&' M/. 5 > W C IFsr l w lur c7,o . 3-/7^/2- stfAxe res, l a a J 76 2J 003070 Form 10620-8-O-PWO Sam ple Description -b h b 5 ^ /0 .u. *nU<**cL ~ A, A>*'-*- Environm ental Lab -- W ork Sheet Lab Request No. Page ________ o f _______ Pate:<^ s 3 //f r / / ? 0 A n a lv s tT r^ ^ f/ ^ ^ tX S J U V m g /JL , /0 _ /a o o y iz x / * /o d o y as _ _______ /O ________ __________.,--------------------- .--.(y d lS __________________ . v5 > _________________________/ Q-.O___________________________ j ________________ __ JQ-O._________________U 2J2_____________________ Y S A & B ___''f g g jf ijr s //d s e / '(* r 7 7 T )________________________ . _________ _________ Cu>ol leH a v u c o k d -d iK jn d ___J S U O ^ ^ M - ^ ^ r f o a j 4 4 g j f j __YC AOQO'A^aJ.Li___a A r i __ M illlp O r - e - ( K H l i - 1 003073 Technical R eport Sum m ary fotm S 747-11-H JTo: Patent & Technical Communications Services -- 201-2C-12 ReportSummarymustbetypewritten. Guidelinesareonreverseside. ItreportIsprintedonbothsidesofpaper,sendtwocopiestoPi TCS. DNoucmubmere.nt 00*p2*2rtm2*_m_N_um_b_*' Profact Numbar Raport Numbor (Placa additional O ita in Abolracl tm ) M.To T. Pike .r-J236.-1Bt33___________________ OoloTypod 3.L1.131. T._J.Author) Morgan. R. D. Hovell________________ OMEalonn/vDaipraoflmnamnt ental-Engineering &Pollution Contro l .EPP_Research..Profact Oaserlptlon andJD.ev.elopment.______________ i J_QL 089LOC Employa* Numbor) JBEI=29J5SM. EE&PCOrganization Copo TheRaportT Eltla ffectiveness of Selected Antifoam Agents in Suppressing Foam.PartedCovarad KLAADFeoyiqenwaguftmoohierfadotomsuaWsminaFgtAielArmgegBneFrtnasotnsrmd iAngFFFFoam WWFoaaamsstteeSwDuapitserpreosTssiraoelnatment Project Objective & Report Abstract 3M recommends to customers that AFFF usage wastes be disposed of by diluting the waste and flushing it into a running sewer that flows to a wastewater treatment system. If the AFFF in the sewage is not sufficiently dilute, foaming may occur in the aeration basin of wastewater treatment systems. This may cause cleanup problems and reduced efficiency in the treatment works. In this study, the effectiveness and relative cost of commercially available antifoamproductswere evaluated. The experimental work consisted of adding the antifoam and 3M AFFF products to an aerated solution ofwater or activated sludge mixed liquor. The effectiveness of the antifoams was determined by their ability to prevent foaming in the aerated solutions. In the initial screening tests, the 31 antifoams supplied by nine manufacturers were evaluated fortheir ability to control foaming by a 500 mg/L solution of AFFF in a deionized water solution. Twelve antifoams passed this test. A second set of tests consisted of successively adding an AFFF solution to an aerated antifoamsolution. Additions of the AFFF stock solution caused the concentration of AFFF to increase in the solutionwhile the antifoamconcentration decreased. Nine antifoams were found to be effective in these experiments: GE Silicones Antifoam Emulsibn AF-72, Antifoam Emulsion AF-93, and Antifoam Emulsion AF-9020; Henkel Defoamer WB-209 and FoammasterTM DS; Union Carbide SAG 2001 Organosilicone Emulsion; Wacker Silicones AntifoamAgent SE-36, AntifoamAgent SWS-214, and Antifoam Emulsion SRE. Of these, the most cost effective are Henkel WB-209, GE SilipQnes AF-9020, Henkel Foammaster TM DS, and Wacker Silicones SRE. Report Typo B R A D Research and Development TRP Trip or Field Report TECh. Service PILot Plant FACtory Experiment GOVt. Project MANufacturtng ENGlneerlng OTHER Management SUMmary ROI Record of Invention Security E Open Report and Summary Closed Report *Open Summary 3M Chemical New Chemicals Reported Registry Um term B082 to f l i t Inlo Ch*micaj Raglatry Notabook h l w n For P A TCS Use Only PMmCoda N im bar or Pag* Inlorm ailon U n io n In itia l* P& TCS Editor Initia l* 003074 THE EFFECTIVENESS O F SELECTED ANTIFOAM AG ENTS IN SUPPRESSING FOAM C AUSED BY LIGHT W ATER BRAND AFFF SO LUTIO NS IN T R O D U C T IO N Aqueous film forming foams (AFFF) are water based, surfactant containing products used primarily to control combustion hazards and extinguish fires involving hydrocarbon liquids. In their use, AFFF agents are diluted in w ater and sprayed through a foam forming nozzle so that the foam spreads over the hydrocarbon liquid. Application of A FFF prevents and extinguishes Class B fires by spreading a vapor-sealing film over the liquid fuel. This vapor seal inhibits reflash even when the foam blanket is ruptured and also enables the product to be used to prevent ignition of non-ignited spills. In addition, A FFF provides excellent penetrating and wetting qualities when used on Class A fires. After their use, waste AFFF solutions from actual or simulated fire fighting activities are partially biodegradable and have low toxicity to aquatic organisms including the microorganisms in wastewater treatment systems. Therefore, wastes from AFFF usage can be discharged at controlled rates into a wastewater treatment system for disposal. A disposal problem inherent to improperly handled AFFF wastes is foaming in wastewater treatment aeration basins. Excessive foaming in an aeration basin can cause a dual problem. First, the suspended activated sludge solids can attach to the foam and be lifted from the aeration basin. This causes clean-up problems at the wastewater treatment plant. Second, the remaining activated sludge mixed liquor is depleted of much of its suspended microbial solids and therefore is not as effective in treating wastewater. Commonly, excessive foaming is caused by disposal recommendations not being followed. 3M recommends that Light W aterTM AFFF waste should first be treated in an oil-water separator followed by metered discharge of the aqueous fraction to a running sewer. If properly metered, Light W aterTM AFFF concentrations reaching the aeration basin of a wastewater treatment system will not cause excessive foaming. 3M 's A FFF products are designed to be used at either 6% or 3% concentrations in water. For its 6% AFFF concentrates, 3M recommends a discharge rate such that the AFFF concentration in the receiving aeration basin will not exceed 100 mg AFFF concentrate per liter of sewage. Due to its higher surfactant concentration, for its 3% AFFF concentrates 3M recommends a discharge rate such that the AFFF concentration in the receiving aeration basin will not exceed 50 mg AFFF concentrate per liter of sewage. The values for the acceptable concentrations of Light W aterTM AFFF have been determined experimentally 1 003075 and are somewhat conservative; therefore if the AFFF wastes are discharged to a sewer at appropriate levels, they will not cause excessive foaming in the receiving aeration basin. Some wastewater treatment systems are of an insufficient size to make metered discharge of the collected AFFF wastes practicable. For such sites, 3M recommends one of two disposal alternatives: 1) transporting collected waste materials by tank trucks for metered discharge into a larger waste treatment facility; or 2) discharging the waste at a higher rate (up to 800 mg/L vs. 50 or 100 mg/L) with appropriate concentrations of an antifoam agent added to the waste system to suppress foaming. Consequently, there is a need to identify the most effective antifoam agents to be used in cases of improper disposal of AFFF waste or when the AFFF waste must be discharged at higher rates. To achieve this goal, a two phased study was completed to evaluate the effectiveness of several commercially available antifoam agents on current Light W aterTM AFFF products. Similar studies conducted in the 3M Environmental Laboratory between 1982 and 1987(1), found SW S-214 supplied by SW S Silicones Corporation and W B-209 supplied by Diamond Shamrock to be the most effective. Therefore, care was taken to include these products in this study. SW S-214 is now produced by W acker Silicones Corporation and W B-209 is now produced by Henkel Corporation. Phase one of this study was a survey of antifoam manufacturers. Eleven companies were contacted and asked to run independent tests to evaluate the effectiveness of their antifoams on Light WaterTM AFFF solutions. Of the eleven manufacturers contacted, nine supplied samples and three completed evaluations of their products. The three manufacturers that completed evaluations were Henkel, Dow Corning, and W acker Silicones. These evaluations were completed using two Light W aterTM A FF F products. The products used were FC-203CF and FC-600. Henkel ran tests of their products and sent their three top performers: Defoam er W B-209, FoammasterTM DS, and FoammasterTM SZU. Of the three, Defoam er W B -209 received the highest recommendation from Henkel not only because of its effectiveness, but also because of its low price. This agreed with the results of the previous 3M Environmental studies and the present work. Dow Corning sent two product samples after completing their testing. Their two productswere 1510-US Food Grade Antifoam Emulsion and FG 10 Antifoam Emulsion. Their first recommendation was the 1510-US Food Grade Antifoam Emulsion. In the tests done for this study, neither of the Dow Corning products were found to be effective. W acker Silicones also conducted independent tests to determine their most effective antifoams. Although SW S-214 has been recommended by 3M to our customers in the past, Wacker found three of their other products to be more effective than S W S -214. The three Wacker products were Antifoam Agent S E-36, Antifoam Emulsion SE-39, and - - 2 003076 Antifoam Emulsion SRE. This study concurred with W acker's results and found SE-36 and SRE to be effective. W hen considering cost-effectiveness, W acker Silicones SW S-214 is also acceptable. The objectives of the second phase of the study were threefold. The first was to evaluate the relative effectiveness of the 31 antifoam products that the nine companies submitted and to identify the top performers. The second was to find the antifoam concentrations of the top performers that could suppress foaming caused by AFFF concentrations greater than the recommended disposal concentrations. The final objective was a cost analysis of the top performers to determine the most cost-effective antifoams. M ATERIALS AND M ETH O D S PRODUCTS TESTED Light W ater Brand AFFF products used in the evaluation were FC -203C F, FC-206CF, FG-600, and FC -600F. Thirty-one samples were received from the antifoam manufacturers. The products were: Air Products SURFYNOLTM 104A Surfactant SURFYNOLTM DF110L Defoamer SURFYNOLTM DF-75 Defoam er SURFYNOLTM 420 Surfactant BASF PLURONICTM L61 PLURONICTM L101 PLURONICTM L121 PLURONICTM 3 1 R1 Dow Corning 1510-U S Food Grade Antifoamer Emulsion FG 10 Antifoam Emulsion GE Silicones Antifoam Emulsion AF-60 Antifoam Emulsion AF-72 Antifoam Emulsion AF-75 Antifoam Emulsion AF-93 Antifoam Emulsion AF-9020 Henkel Defoam er W B-209 FoammasterTM DS Foam msterTM SZU 3 003077 6 Nalco 7 Union Carbide 8 W acker Silicones 7455 Antifoam 7460 Antifoam 7470 Antifoam 7471 Antifoam 7472 Antifoam SAG 2001 Organosilicone Emulsion Antifoam Agent SE-36 Antifoam Agent SW S-214 Antifoam Emulsion SE-39 Antifoam Emulsion SRE 9 Witco Bubble BreakerTM 776P Bubble BreakerTM 3056A Bubble BreakerTM 913 PROCEDURE Tests were done using a modified J. J. Bikerman foam control te s t<2). Equipment used: MinistaticTM pump, Manostat Inc. flow m eter, Gilmont Instruments 1000 mL graduated cylinder, Fisherbrand gas dispersion tube, Ace Glass Inc. ASTM 70-100 p The pump was used to produce an adjustable airflow that was bubbled through the test solution in the graduated cylinder. This airflow was measured by the flow meter and delivered into the test solution through the gas dispersion tube. To better simulate an aeration basin and for consistency, the MinistaticTM pump was adjusted to maintain a constant airflo w rate of 2000 mL/min. This rate simulated the agitation and turbulent conditions in an activated sludge aeration basin. Results were derived from the presence and amount of foam that built up in the graduated cylinder. The measurement of the amount of foam was somewhat subjective ancfwas determined by a combination of the height and density of the foam. For improved objectivity between experimental runs, results were recorded by taking photographs of the tests at predetermined times for side by side comparisons at a later time. - 4 003078 RESULTS First objective: To evaluate the relative effectiveness of the 31 antifoam products, thereby identifying the top performers. For the initial screen, the 31 antifoam agents were tested using a 100 ppm antifoam concentration to control a 500 mg/L concentration of AFFF in a deionized water solution. The AFFF solution was prepared by diluting weighed amounts of AFFF, and the antifoamer was dispensed into the AFFF solution by micropipette and then mixed. The Light WaterTM AFFF products used for this test were FC-203CF, FC-600, and FC -600F. Results were recorded at three and ten minutes. Antifoam products were rated for their effectiveness on a scale of "A" to "F", with "A" being the best and " P for failing. This initial screen reduced the field of 31 to 12 effective antifoams. During this screen, it was also determined that the antifoams were essentially equally effective on each of the three Light W aterTM AFFF products.-Therefore, all remaining tests were preformed using only FC-203CF. The twelve antifoams that passed the first set of tests are: Air Products SURFYNOLTM DF-75 Defoamer GE Silicones Antifoam Emulsion AF-60 Antifoam Emulsion AF-72 Antifoam Emulsion AF-93 Antifoam Emulsion AF-9020 Henkel Defoamer W B-209 Foam masterTM DS Union Carbide SAG 2001 Organosilicone Emulsion W acker Silicones Antifoam Agent SE-36 Antifoam Agent SW S-214 Antifoam Emulsion SE-39 Antifoam Emulsion SRE The next set of tests was completed using a revised procedure. Instead of each experiment having a set concentration of A FFf1and antifoamer from beginning to end, the amount of antifoamer in the test solution remained constant while additions of Light WaterTM AFFF stock solution were added at 10 minute intervals. The total volume of the test solution began at 100 mL with the antifoam concentration at 100 mg/L. The AFFF stock solution contained 2 grams of FC -203CF per liter of solution. W hile aerating the test 5 003079 solution, 10 mL of AFFF stock solution was added at 10 minute Intervals. The aeration rate used was 1100 mL/min instead of the 2000 mL/min used for the initial screen. This lower rate produced sufficient aeration and reduced the strain on the air pumps. The additions of AFFF solution increased the concentration of AFFF while reducing the concentration of antifoamer. The additions of AFFF were continued until the antifoams could no longer control excessive foaming. Results were photographed at each interval. The photographs were used to identify the maximum additions of AFFF at which the antifoamer could suppress foaming to acceptable levels. The number of additions of AFFF, the starting volume, and the initial concentration of antifoamer were used to calculate the antifoam and AFFF concentrations. Based on the results of this test the field of twelve antifoams was reduced to the final field of the top nine. The top nine antifoams are: GE Silicones Antifoam Emulsion AF-72 Antifoam Emulsion AF-93 Antifoam Emulsion AF-9020 Henkel Defoam er W B-209 FoammasterTM DS Union Carbide SAG 2001 Organosilicone Emulsion W acker Silicones Antifoam Agent SE-36 Antifoam Agent SW S-214 Antifoam Emulsion SRE Second objective: To determine the concentrations of the top antifoams that can suppress foaming caused by AFFF concentrations greater than the recommended disposal concentrations. The procedure used was the same procedure used to find the top nine antifoams with one exception. To more accurately simulate a wastewater treatment aeration basin, fresh sludge was used for all of the remaining tests. The sludge was obtained from Metropolitan W astewater Treatment Plant in Saint Paul, Minnesota. During the weeks of testing, the MLSS of sludge ranged from 2.4 to 3.5 g/L, and the pH ranged from 6.1 to 7.9. Using this sludge, data were collected for each of the nine remaining antifoams at four initial antifoam concentrations. To get a range of data, four initial antifoam concentrations in the sludge were evaluated: 3 0 0 ,6 0 0 ,1 0 0 0 and 5000 mg/L. The study found the maximum 6 003080 concentration of FC-203CF at which each concentration of the top nine antifoams could suppress excessive foaming. Results are presented graphically in Figure 1 and tabulated at the end of the report. If the AFFF concentration in the aeration basin is known, the appropriate amount of antifoamer can be determined from Figure 1. This information is useful for minimizing the amount of antifoam. This is an important consideration for reducing treatm ent cost and avoiding foaming caused by the addition of excessive antifoam. The possibility of foaming due to excessive antifoam can best be seen in the abnormal shape of the graph of Henkel W B-209 in Figure 1. The graph shows that above about 300 mg/L of W B -209 the antifoam becomes increasingly ineffective at suppressing A FFF foam and may actually cause foaming. Third objective: To perform a cost analysis of the top nine-antifoams. The cost analysis was based on the price and the amount of antifoam needed to suppress excessive foaming caused by AFFF concentrations greater than 50 mg/L. The antifoam unit cost used in this analysis was the cost per pound when purchasing one to seven barrels. Antifoam prices are tabulated at the end of this report. Although the prices are subject to change and vary based on location and purchase volume, the graphs from this analysis can be useful when comparing relative cost of different products. Figure 2 illustrates the relationship between A FFF concentration and the cost to suppress foaming in 1000 gallons of sewage. Figure 3 is an expanded scale of the sam e data given in Figure 2. 7 003081 i Figure 1. Antifoam concentration required to control foaming from FC-203CF. 8 003082 i 100 200 300 400 500 600 700 800 900 1000 1100 1200 FC-203CF Concentration (mg/L) Figure 2. Cost comparison tor antifoaming 1000 gallons of solution containing various concentrations of FC-203CF. 9 f 003083 i CO co 0C5D OO O 8. oCD C E coa c < 300 400 500 600 700 FC-203CF Concentration (mg/L) 1000 Figure 3. Cost comparison for antifoaming 1000 gallons of solution containing various concentrations of FC '203C F. (Expanded scale.) 10 003084 C O N C L U S IO N S In case of Improper disposal of Light W aterTM AFFF wastes or when the wastes must be discharged at a higher rate than optimally recommended, the most cost-effective antifoam agents are Henkel W B-209, G E Silicones A F-9020, Henkel FoammasterTM DS, and W acker Silicones SRE. If the AFFF concentration is 600 mg/L or less, W B -209 is the most cost-effective antifoam. Note that when using W B-209 care should be taken not to use too much, because concentrations of W B -209 greater then about 300 mg/L have a greatly reduced efficacy and may actually cause foaming. If the AFFF concentration is greater than 600 mg/L, or W B-209 is not readily available, GE Silicones AF-9020 is recommended. A F-9020 is effective over a much larger range than W B-209 and is the second most cost efficient antifoam. The second choice for a large range antifoam is Henkel FoammasterTM DS. FoammasterTM D S gave results comparable to the G E A F-9020 but w as slightly more expensive. Another antifoam that preformed very well over a large range and was only moderately more expensive to use, was W acker SRE. Although all four of the recommended antifoams are available for export, a consideration for SRE is that it is produced in Europe and therefore may be more readily available for the European market. The recommended concentrations to control concentrations of AFFF can be found for each of the recommended products by using Figure 1 or the data tabulated at the end of the report. Also, to find the approximate cost of suppressing foam at various AFFF concentrations can be found using Figure 2 or Figure 3 for an expanded scale. REFERENCES 1. Environmental Laboratory Lab Request No. D1629. 2. Bikerman, J. J. Foams Springer-Verlag: New York 1973. 11 003 Antifoam concentration required to suppress AFFF at varying concentration for the top nine antifoam products. All concentrations are in m g/L GE Silicones A F -7 2 50 575 660 890 1150 FC -203C F GE Silicones A F -9 3 0 214 400 526 2083 50 575 667 90 1180 F C -2 0 3 C F 0 214 400 526 2000 GE Silicones A F -9 0 2 0 50 575 665 870 1160 """I 0 214 400 556 2273 Henkel Foam m asterTM DS F C -203 C F 50 550 667 875 I____ 1190 0 214 400 556 2000 Henkel W B-209 50 580 630 571 300 F C -203 C F 0 214 400 714 4167 Union C a rb id e SAG 2001 50 333 450 550 800 F C -2 0 3 C F 0 250 461 714 2941 W acker S E -3 6 50 461 565 750 825 F C -2 0 3 C F 0 231 429 625 2778 W acker SRE 50 571 675 880 889 F C -2 0 3 C F 0 214 375 556 2778 Wacker . SW S-214 IF C -2 0 3 C F 50 0 400 231 500 429 590 667 580 3333 12 003086 Antifoam prices used in the cost analysis. The prices were obtained by telephone from the manufacturers during the month of July, 1992. GE Silicones Henkel Union Carbide 1-800-332-3390 Antifoam Emulsion AF-72 Antifoam Emulsion AF-93 Antifoam Emulsion A F-9020 1-800-922-0605 Defoam erW B-209 FoammasterTM DS 1-800-523-5862 SAG 2001 Organosilicone Emulsion W acker Silicones 1-800-248-0063 Antifoam Agent SE-36 Antifoam Agent SW S-214 Antifoam Emulsion SRE $3.93/lb 3 .7 4 1.93 0 .4 5 2 .3 1 5 1.61 2.50 1.34 2 .6 3 13 003087 iS ^ 55 t v S UJ Ia .ST Cj H B EST COPY VAILAL i - 003088 lo flc $ rW a + \o n 5 10 ts 50is .. 10O. F&ZOS U rt-5 0 3 P o a n Fonm a^vovi _____________ C b i ^ e * ^ (S^iisyit) M illi-Q BEST COPY AVAILABLE C -V<^V4q ^ N o n -e Po^vu^d K ovtc. -foV-VM-d fc io tn e , VOrUKd M qva -K V w td N one. vowvted MOtnc fb rw c i K o v ie , -Pcy'wtg^ ..p-odr'vOnteScfife\ vf.mim,i*s;itZe_-O.CO.. 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HOWELL CIM onlPp*>W n t ENVIRONMENTAL TECHNOLOGY & SERVICES fn*.r.aiyivo^( u^sten|MPn_ AFFF WASTE TREATMENT cc Loe 01 0 8 9 n *port TIB* PRECIPITATION AND ULTRAFILITRATION EXPERIMENTS WITH 3M FC-203CF Keyword Raport N w nter te a ts *** OaMTpad 0 3 /2 0 /9 5 Employ** Numb*r(*) 295864 OtganlnUon Cod* P*rtod C ov*f*d 1 /94 -1 2 /9 4 AFFF; WASTEWATER TREATMENT; LIGHTWATER BRAND; FLOCCULANT; SURFACTANT, FLUOROCHEMICAL; AQUEOUS FILM FORMING FOAM; COAGULANT; PRECIPITATION Project O bjective t R aport A bstract AFFF usage waste disposal is often a problemfor 3M customers after actual fires, testing extinguishment systems or aftertraining exercises. 3M recommends metered discharge of AFFF usage wastes to a municipal or industrial wastewater treatment system so that biodegradable components will be mineralized. Often, this is not practical because of the small capacity of the waste treatment system, regulatory fimits, or because of excessive foaming. We have been investigating new methods for waste treatment, including surfactant precipitation with polycationic surfactants and inorganic salts (see Technical Report by Kimberly Bekes, 7/30/93) and ultrafiltration. This report includes results of precipitation and precipitation coupled with ultrafiltration. Both methods showpromise as AFFF usage waste treatment processes, but the ultrafiltration method is much more costly both in terms of capital and operating expense. We are continuing to develop a solution tothe AFFF disposal problemand we are seeking a third party wastewatertreatment firmtoperform a full-scale demonstration. Report Type Security Nof book ftfl f ocA E3 R 4 D Research and Davalopmant P lU t Plant MANufacturing Managamant SUMmary TRP Trip or Raid Raport FACtory Experiment ENGinaaring ROI Record of Invention TECh. Service GOVt Project OTHER S3 Opan Raport and Summary Cloaad Raport - Open Summary 3M Chem ical Naw Chamicala Raportad R agiatry U , form 8 2 to * r t* f into Ch*niE(fl*9i*try information Uatoon InltMa Ifreportisprintedonbothsidesofpaper, sendtwocopiestoP& TCS. 003091 Precipitation and Ultrafiltration Experiments with 3M FC 203-CF E18d0w5inAEla.dTdiunckSetr. Norman, OK 73072 December 8, 1994 Table o f Contents * Precipitation M e a s u re m e n ts .....................................................................................................I U ltrafiltration M easurem ents ............................................................ 3 Summary and C on clu sion s.......................................................................... 6 003092 Experiments with 3M A FFF Tw o types of experiments were performed with aqueous solutions of AFFF. The first type w as precipitation of the fluorinated surfactants F C -9 5 and L4640 with an added cationic polyelectrolyte. The second type w as ultrafiltration treatment with an excess concentration of the cationic polyelectrolyte to produce a treated water (permeate) stream with reduced fluorinated surfactant content and a concentrated waste stream containing fluorinated surfactants. Precipitation Measurements The hypothesis in the precipitation measurements w as that, by adding a stoichiometric amount of a positively charged polymer to an aqueous solution of AFFF, negatively charged surfactant ions (including F C -9 5 and perhaps the amphoteric F C -12 4 0 ) could be precipitated as an electrically neutral complex. Calculation suggested that the anionic charge equivalence in the original A FFF solution was ca. 0 .0 0 3 M (when diluted to working concentration). Solutions were made up so that the polymer concentration would range from 0 .0 0 1 M to 0 .005M in solution (initially) at a working concentration of A FFF (3 parts concentrate to 9 7 parts water). The cationic polymer used for these experiments w as Merquat 1 0 0 which is a high m olecular w eight (ca. 20 0 K Daltons) quaternary amine polymer (polydiallyldimethylammonium chloride). The polymer was a product of Calgon (Merck) and w as supplied as a 4 0 % by weight aqueous solution. The concentrations referred to above are in terms of monomolarity. For example, if the repeat unit of the polymer has a molecular fragment weight of 16 3 , then a 1 M solution would consist of 1 6 3 grams of polymer in one liter of water. Table 1 below reports analytical results by Jim Wolter of 3M for the precipitate samples sent to 3M on 9 -6 -9 4 Table 1: Results of AFFF Precipitation with Cationic Polyelectrolyte Sample # [FC-95] ppm [L4640] ppm CP 28.39 720.5 1 22.86 295.1 . 2 1.63 115.9 3 0.36 102.3 4 0.08 73.5 5 5.27 163.54 [Cat]' M 0 0.001 0.002 0.003 0.004 0.005 pc'poTmnocteoanlftf(rlmautooiornnions)amoteofdlFacCroc-m9o5npcoaennnedtnrtaLst)4io6on4f0aosfbhcloaauntilkodnsabicmepptohleleymcsaoemnrteainianstinhtgehsiosonfllouytriAosFna.FmFp2laeSnsadm1d-p5el.ieo0nirzeepdrwesaetnerts. thTehecotomtaploosirtifoonrm(inat 1 003033 The analytical results for A FFF fluorinated components in the supernatant solutions generally conform to expectations. There is a continuous decrease in F C -9 5 and L4640 concentrations in solution as the cationic polymer concentration in solution increases up to a point estimated as near charge equivalence. This decrease is presumed to occur through precipitation of a fraction of the polymer and anionic solution constituents as a neutral solid. At the highest concentration of Merquat 10 0 {sample #5), the solution concentrations of F C -9 5 and L4640 appear to increase. This increase is expected because an excess of cationic polymer will tend to keep the anionic constituents in solution. In previous work (with the samples sent to 3M on 3 -2 0 -9 4 } utilizing a range of polymer concentrations from 0 .0 0 3 to 0 .0 3 M to investigate precipitation in A FFF solutions, it w as found that no visible precipitate appeared in solutions with polymer concentrations above 0 .0 0 6 M. This indicates that a charge excess of more than 1 0 0 % , i.e ., a polymer to A FFF anionic constituents ratio of 2 :1 or higher, is sufficient to keep the A FFF fluorinated components in solution. On this basis, a concentration of 0 .0 1 M polymer was chosen for use in the ultrafiltration experiments (see below). Conditions for the precipitation experiments were as follows: A stock solution of AFFF was made by delivering 3 mL of A F F F concentrate into a 5 0 mL volumetric flask. The flask w as then filled to the mark with deionized water. This solution contains A FFF at twice the normal working concentration of 3 parts AFFF concentrate to 9 7 parts water. 5 ml of the A FFF stock solution w as placed in each of six 20 mL screw cap vials. 5 mL of deionized water w as added to vial #0 as a control sample. A stock solution of 0 .0 1 M cationic polymer in water was prepared by diluting a weighed amount of polymer concentrate ( 4 0 % by weight in water). Volum es of stock polymer of 1 , 2, 3 , 4, and 5 mL, respectively, were added to vials numbered 1 through 5 containing 5 mL of A FFF stock. Deionized water in volumes of 4, 3 , 3, 1 , and 0 mL, respectively, was added to vials 1 through 5, respectively. All vials then contained 1 0 mL of AFFF at a working concentration ratio of 3 parts A FFF to 9 7 parts water. Vials 1 through 5 also contained 0 .0 0 1 to 0 .0 0 5 M polymer in numerical sequence. All vials were shaken briefly by hand to mix the contents. v All samples showed visible precipitation of tan colored'particles within at least a few minutes. Some qualitative observations are that the samples below and abovethe charge equivalence point appeared to produce more finely divided precipitates. Samples near the equivalence point (#3 and #4) produced some larger particulate matter on the order of 1 - 2 mm in diameter. These larger particles did not settle rapidly and appeared to adhere to the glass walls of the vial. 2 003094 Ultrafiltration Measurements The figure below gives a schematic of a simple ultrafiltration (UF) setup. The column depicted in this figure is a hollow fiber column. This type of column was used in the previous UF experiment on A FFF (3-20 -9 4). For the current experimental results, a so-called spiral wound UF column w as employed. The hollow fiber column is constructed of a number of membrane tubules potted with adhesive in a configuration quite similar to an ordinary laboratory condenser. The Feed UF solution flows into one end of the fiber lumen and Permeate liquid exits the fiber at right angles through the membrane pores. The remaining solution in the fiber (Retentate) exits at the top end of the fiber lumen. The spiral wound column consists of a dual-face membrane envelope concentrically wound with flow spacers separating each winding. Feed solution is pumped into one end of the column. Liquid (Permeate) which penetrates the membrane circulates in a spiral fashion to a center tube for withdrawal. The remaining solution which does not penetrate the membrane exits as Retentate at the column end opposite to the Feed entrance. Figure 1 . Hollow Fiber Ultrafiltration Apparatus Thefeed reservoir is a 5 gallon polyethylene tank. The tank contents are internally recirculated at a 300 psaRegtttaciThohshexonane1epeorpandlsdmf.wetactioH/rrrprbohneniioefecalmerad.tultrt.relrthimemeepoTnerWnwdntn2ae1btacpa.ati8eaotoeatulethilnelriInfmsudfnbnedr)lfgmrcyeroppdtaahatoiwnrpeirwdn,cseenudtgppatcashtrmiiolyanlsoteeraicultodpsanoyyelcrttefnpsisfreoePnldusieloctgai2uutrlostrfwmtm.mpioraooteanpnhentnbacFoteasleyhdecdaetmms2oceiepsuenfomafdeacpLogeemymerepx/ssremrtrpibolbiosdtmiaaoseslrinnulnhmaserltm.ittenayahetiheidoeslteoocaeyeeTnflhndss.brdoihuioibvyisisofersoglieTiflienlffioinoirherdottbgpsgwhaa.ereetedlvhcfaorinpfiasneopSsebialpncdrptaeveanoihgueamdzrreiatoraenlVpocnsaantmoalrgrtosIntiuelranleeduiipcsttglgtnrhstlleriooiyicheeerdopsr,suptsgnofe(iohetadlndepa,iopnornegpsutewatwlchtemeltrstrovseidiiae)t(fnoawh.tbottabnlhgewavsf2rydeVieecoocfbffkatitroeuhenii)V2rannnetreipacsadtIdfstertertthbie,ihreetwebroliadaiseoordynnhdseenuaviupyptccovsgoenreuh.oeshelnfdnumtrnfstadmettmaa,cihpteeceteoeerne1adnePd,mts0lttsfipreuKaIlpfaoaixil,bcneneidtmiteitctsewdetooiitsonmninhcr.wpvlggsoi.aeecoilhRtrrwloohuhvymkoemfet,fehf.rbtfreeedienuaocaznetepstouhPtthdbedanet.ata-prftotnioelcaceunoTkoftl5mteafelwhouy0(xpncepMrirrct(pstiaeeatscuneWhststrorgeiearseogalCnouutratffutOnrmteaaonaheglot)tynnd.reehe.t ~ 3 003095 The ultrafiltration experiment was initiated by mixing 24 0 mL of A FFF concentrate with 8L of aqueous cationic polymer solution at a concentration of 0 .0 1 M. One sample from this mixture was taken to provide a reference point. Conditions were then adjusted in the UF system to produce ca. 3 0 % of the flow through the column as permeate liquid with the remaining 7 0 % existing as retentate. Samples of retentate and permeate liquids were taken at this point. Two further sets of samples of permeate and retentate were taken at conditions near 40 and 8 0 % flow as permeate liquid, respectively. Total liquid flow through the column ranged from a high of ca. 6 00 mL/min at 3 0 % permeate (Recovery) to a low of ca. 1 2 0 mL/min at 8 0 % recovery. Table 2 gives analytical results for these several samples as well as the Recovery percentages and the applied pressure at the column entrance. Table 2: Results of UF Experiment on AFFF with Cationic Polyelectrolyte Sample # 0* 1 2 3 [FC-95] P,ppm -- 0.04 1.12 5.29 [FC-95] R,ppm 3 9 .7 47.6 48.6 111.0 [L4640] P,ppm -- 10 6 .9 12 5 .8 19 9 .2 [L4640] R,ppm 126 1.9 14 9 7 .5 14 9 7 .1 14 19 .4 Recov. % -- 3 1.7 40.3 8 2 .7 Pres. > psi -- 26.4 33.5 4 1.8 ' S am p le 0 re p res en ts the com position (in p p m o f flu o rin a ted com ponents) o f the original F e e d solution p rio r to com m encing the U F . experim ent. This sam ple w as m ark e d as F1 in the analytical results provided b y Jim W olter o f 3 M . Results are arb itrarily p la c e d in the rete n ta te (R) colum n fo r Sam ple 0 even though the com position o f the fe ed solution is m easured here. '.T To examine the effectiveness of the UF process in removing fluorinated A FFF components we can look at the Recovery (percentage of liquid flow passing through the membrane as permeate) and the level of the components in this liquid. For sample # 2 , 4 0 . 3 % of the feed liquid appears as permeate water. Relative to the composition of Sample # 0 (Feed), the fraction of F C -9 5 remaining in the permeate is 1 . 1 2 / 3 9 .7 o r 0 .0 2 8 . This means that 9 7 . 2 % of F C -9 5 has been removed from this liquid. Likewise, the fraction of L4640 remaining in the permeate for Sample #2 is 1 2 5 . 8 / 1 2 6 1 . 9 or 0 .0 9 9 6 . This means that 9 0 % of L4640 has been removed from the permeate liquid, relative to the Feed under the conditions for Sample #2. A s the pressure is increased on the system and more liquid is forced through the membrane as permeate for Sample #3, the quality of the separation becomes, somewhat worse. At this point, 8 2 . 7 % of the feed liquid is being produced as 4 003096 permeate. The removal of F C -9 5 from the permeate is 5 .2 9 /3 9 .7 or 0 . 1 3 3 for fraction remaining ( 8 6 .7 % of F C -9 5 has been removed from the permeate). The removal of L4640 from the permeate is 1 9 9 .2 / 1 2 6 1 .9 or 0 .1 5 8 for fraction remaining ( 8 4 .2 % of L4640 has been removed from the permeate liquid). The removal percentages for F C -9 5 and L4640 are comparable at this point. However, the retenate concentration of L4640 ( 1 4 1 9 .4 ppm) in the retntate does not appear reasonable. Ju st as the retntate concentration of F C -9 5 increased for Sample # 2 to Sample # 3 (i.e., 4 8 .6 to 1 1 1 . 0 ) the retenate concentration of L4 6 4 0 should have increased by a substantial amount, instead of the slight decrease shown. In summary, the removal of F C -9 5 and L4640 from aqueous solution by ultrafiltration with an excess of cationic polyelectrolyte appears to be reasonably successful. There are three specific points, however, which deserve comment: 1 ) . It is disturbing that the analytical results show that the initial concentration in the Feed sample (Marked 0 in the Table above) for ultrafiltration is some 5 0 % higher than the concentration of the A FFF stock solution which w as used for the precipitation studies. The initial intent was to use the same concentration of A FFF in both studies; i.e., 3 parts by volume of A F F F contained in 10 0 volumes of solution. The only known difference in the two solutions i that the zeroth solution for precipitation contained only distilled water and A FFF while the zeroth ( F 1 ) solution for UF experimentation contained distilled water, cationic polyelectrolyte, and AFFF. If one assum es that the analytical results are correct, then it is likely that a repeat of the UF experiment (at the lower A FFF concentrations apparent in the precipitation experiment) would show improved results. That is, the removal of A FFF fluorinated components should be better than the results shown in Table 2 above. 2 ) . With reference to Table 2 above, it is in principle possible to check the mass balance of a particular component in the system . Because the total flow in the UF v system is recycled (both permeate and retntate fluids are returned to the'feed tank), the following relationship should apply: [Feed] = Recovery [Permeate] + ( 1 -Recovery) [Retntate] {1} where [Feed], [Permeate], and [Retenate] are analytical concentrations of a particular component in the feed, permeate, and retntate solutions, respectively, and Recovery is the fraction of the total liquid Feed in the system which appears as permeate. Taking data from Sample #0 (Feed concentration) and for Sample # 1 above for F C -9 5 , the following relationship should be an identity: [39.7] = 0 .3 1 7 [0.04] + 0.683 [47.6] however, [39.7] & [32.5]