Document J3DmyGxDpDxQZpB7v964rq7xZ

SUMMARY FOR FOAMING STUDIES DONE ON VARIOUS AFFF PRODUCTS TEST SUBSTANCE Identity:Mixturescontainingperfluorooctanesulfonatweh,ich may also be referredtoas PFOS or FC-95 oras a component ofAFFF products.(I-Octanesulfoniaccid, 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecapfoltuaosrsoi-u,m salt,CAS # 2795-39-3) Remarks field: The testsamples are AFFF productsofvarious compositions. STUDIES The attachedtestingisa compilationofstudiesdone tocharacterizethe capacityof 3M's AFFF productlinetocreatefoam invarioussituations, and, insome cases,the effecbvenessofvariousant-foaming agents.This includesthe effectsoffoaming on wastewater treatmentprocesses. DATA QUALITY ReliabilityN:o rankingofthisdata has been done. These studiesare atypicalh,ave no agency-approved procedure,and were designed to providegeneralguidance to customers and wastewater treatment operatorswho must address the issueoftreatinfgoam afterusingAFFF in a firevent. OTHER Submitter: 3M Company, EnvironmentalLaboratory,P.O. Box 33331, St.Paul,Minnesota,55133 Last changed: 6/28/00 InternaClorrespondence cc: D. R. Ricker - 53--4 C. S. Chow - 21-2W (58) ? -T 13 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/l in primary treatment* 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/l (Photo 1). The jars containing the 10 mg/l 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 bf 10 mg/l, the sludges containing this concentration and 100 mg/l of FC-780 did not settle well after shaking (see Photo 5). Shaking in the presence of 10 mg/l 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/l, 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. 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/l. EAR/cen Attachments PA 10 too 14 mamma T. 100 L-U4e; r- SCOC T.:-.S aim- ril:_-- 'fl" io Co ILI ioo CONT- ioo rialiow "TRO io m lo .000 10 IpLk c=xP. 2,0 m 114 P--M=Nbbg--. i ivo 4T Form 10620-5-PVVO cc: LAO REQUEST BOOK - 42-5W Rp,f:ENVIR.,ASSESS. ING. I- D-1 PRODUCT- PRODUCT REQUEST 4L, ECOLOGICAL ASSESSMENT FOR LABORATORY WORK DIVIISSIIOONN LABREQUESTNO. REQUESTER Name: RequesDtate: @@)ProjectNo... Phone No. a -OQ Prob.No. Code No.: Sample Date: Date Needed: Description: F04 v@" Lc-c-7$j o- Purpose of Tests:ZEn gk,%. Ii-ci-c( 4-4@t- C.,% k, LABORATORY Date Received Sample: - - --/@l Analyst: (4jA@@ DateCompleted: 0-/3-?2 Hours Spent: !C y B-P- PleaseCallRequester IfDelays Are Encountered. PHYSICAL & CHEMICAL PROPERTIES HeatofCombustionCal/G (STU/Lb.) Density Ash 0 -diher WATER POLLUTION pH COD BOD5 SOD, Ultimate TOC Gc Oxygen Uptake DehydrogenaseActivit(yTfC) Other BIOASSAY SpecifyOrganismand Method: dr /600 -ft 7 A ,I, 7Z:/V LEACHATE FROM LEACHING pH COD BOD5 BOD, Ultimate TOC GC Bioarsay Other TEST /40ee r--"7 ('Zl loo- C/ 79() Co v%,W OTHER Sioaccumulation Persistence DegradationProducts e-0 Vol White - Rirturnto Requmto F=- Canory - Environmontel Engrg. Office Fit. j7llAljC,44 AA7Z53ZPOK tED.01 S. Lob - Goldenrod -Romm to Ftoquegter -70 0 12.?oo PROJE,,JL Liu. !,29AA, Subject:)c:4:@OgAiIOAF)C)FC 790 3M TECHNICAL NOTEBOOK L-.o-T- 5-0 1 W 6& Al M IYIFD PAGE NO. Date: 30278 r7 -,7@o 7 -@bject:70 SLI--E; 4-IF-7VEL- Or- *C@c 7;601.407- S-01 7@44--r dhal Se -r#e?5'*TW,a C-J/7-"(47- FlOh7".4AI4 , Refcrence: 6k)1110-OAIAC4)'rAtt L#41a REqttasl- AJO, 5-L)3'9 92 C '/'SO i- or 570 HKAL e--4-.-r Y4& 4@4@ 00 0 00 7%t k"4 x-f FC 780, LO7-S-01 Dl 0 Fd,7e4.1,* 5,0 A,4" I*?e;(,4 -ALA Ilp Si,,n@ittire )ca," Alel4lir4r 'tlwr-c,cA4) ICA 3 #jbf;*" $1 ))O"AM VL Date: PROJECT NO.44@@i Subject: Qi;eip oo;o ject: Reference: e4iit-. '7 d-@ 3M TECHNICAL NOTEBOOK I-RS-7-03PrAGE NO. 502'78 Date: op-6-7@-7p 2 cy-- .L=F)CERIM-jE.Ar e, Ole do o rt /.e /0 -v..t eo@ SiL,nature A5 Date: F@ 0'7 I'P PROJ ECT Subje'ct: jgct: 19 -7001 Z-100 3M TECiTr!NICAL NOTEBOOK PACE NO. 5027S 0 Date: t?-07-'77 Refercnce: IAIS OA)TllD I- Fv4-m 4&14GHi- ?-GAO I mitj. (c#-%) .2.c 11" c P% eM AT#J. cil m;#J No (0K I 0 74@ FC - 5,0 a4L@ 7 @A F-4otM H614 htr *r -rll'4 rio% da, Si,-,nature-4" Datc: CONT. 10 100 T/Af6 0 i3 q-0 7 -79 ex MOM lo -7,7. CONT. Io 100 ioc 0 C) C-ONT. 10 loo 0119700 1 -z17CO PROJ iCT NO. "i Subject: bject: Reference: dont, /* .21 31 ,el 3M TECHMCAL NOTEBOOK NO. Date: PAGE 50278 10 20 L 7%c 'i@A"do, 4 roe1.4t 60,02 Lk Si,-,nLittirc--A" :5-@ Date: L4 - -- - -- coom lqc 10 00 Ro L. loen!l 10 10 MI 0012. ?IDV PR4?J'-CT NO.-J.-I aubject: )@ject: Reference: 64wk IQ FX PoFe IA44FjOU -7- b.) 3OA4.e- 3M TECHNICAL NOTEBOOK !@-03 PAGE NO. 502'7S 11 Date: 4P OJ'-7P 0, i-A4 P, e-I,:>) Date: oop C) z T------------ L./,?A:)C,Yt2-S I . FOAMING STUDY RESULTS I LRN: 6912S 3M ENVIR014MENTAL (AFFF Foaming Protocol Reference: LABORATORY Study) EAR 6/13/81 Sample Description: L-5439, cc8l4-28, 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/l. 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/l and 1,900 mg/l (duplicate analyses). 14th Ed., pp. 89-98. TS Protocol Reference: Standard Methods, 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 Parafilms and mixed by inverting. This prepared a dilution series of 0, 15, 50, 150, and 500 mg/l of AFFF in mixed liquor. The solutions were divided into two 100 ml aliquots. poured into 500-ml gra-duated cylinders and the other left in the 250-ml cylinders. 100 ml was 100 ml was SHAKE TEST The portions which with Parafilm@ and allowed to stand. were left in the 250-ml cyinders vigorously shaken for 30 seconds were covered and then Photographs were taken and the foam volumes were measured following intervals: AFFF Conc. Time-0 t Foam Volume(ml) Min. 5 Min. 20 Min. Hour 0 mg/l 2 0 15 mg/l 2 0 50 mg/l 6 2 150 mg/l 16 8 500 mg/l 36 30 0 0 0 0 0 0 0 0 0 4 2. 0 22 io* io* *The foam appeared less dense then previous observation. at the 'Page I of 3 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 15 50 150 500 mg/l mg/l mg/l mg/l mg/l 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=l 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 wh-ich 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 off the sides. After this, the foam volumes were measured at the following intervals: Page 2 of 3 AFFF FOAMING STUDY - continued LRN: 6912S Date: 6/18/81 Analyst: W.A. Scheil AFFF Conc. Foam Volume(ml) Time 0 1 min. 5 Min. 20 Min. 1 Hour 0 mg/l 0 0 0 0 0 15 mg/l 0 0 0 0 0 50 mg/l 0 0 0 0 0 150 mg/l 5 0 0 0 0 500 mg/l 15 io* io* io* 5* *The foam appeared less dense than the previous observation. The settling of the solids appeared uniform in all concentrations. Page 3 of 3 PIIOTOCOL FOR AFFF FOAMING STUDIES EAR 5/13/81 1. Obtain fresli activated treatment plant. sludge mixed liquor from Metro 2. ll!;ineltli(, 20 teclink(itic,ind the graph of adsorbance at 600 nin versus SS, adjust MLSS to 2000 mg/l by DI water addition or by centrifugation and discarding supernatant. mi)-c @)OO, 150, 50, 15, alicl0 mg/l solutions of this sludge. of AFFF in 200 ml 4. Divide each nolittion int-o '.1,100 ml parts. Placing 1/2 in a jar with at least 200 iiilof head space and the other half in 500 ml volumetric cylinders. S. Cover and shake e-ach jar viqorously for 30 seconds. 6. Take photographs and measure foam height immediately after shaking (time 0) and at 1 minute, 5 minute, 20 minute, and 1 liotir. Also ol)sorve and photograph how well-sludge settles. 7. Aerato the' AFFF sludge mixtures in the volumetric cylinders for 5 ininutes at 500 ml of air per minute using gas (lisp(--t-!-.itotnil)cf;with rritte(i glass ends. $I. Again, observe foam height or volume and sludge settling, again inake photographs. @)HAKT lt@)l VHUIU@) AFFF FOAMING STUDY, LRN: 6812S XF" -RIMC MIAI, --s,3 , 0,% - @; - /SZ H-640. Co&.Z T/me .411V I_Ielv:6afE s or or Page I of.2 SHAKE TEST PHOTOS AFFF FOAMING STUDY, LRN: 6812S SwtiQLF-o AFTCA I HO'A$T 56,-I'LlAj6 P, SM)iRcLrib ZLO -rime Tz ZO it7 Page 2 of 2 AERATION TEST PHOTOS AFFF FOAMING STUDY, LRN: 6812S RIA)G AexA-rioAf - AF7-6R, ---10 zt AIR If 514Ur Page I of AERATION TEST PHOTOS AFFF FOAMING STUDY, LRN: 681 *TIMC 0 am.- go 141M S If. -nMe S')WIAI LRA): 68/Z s P2 U4@.LVSIS FOWA 1036A C-ZNv aot)#-,e0 7T F:oAtAt (V AA FC- lom 0 LOT-Aol---- .Wp- Iwo ,f,-. 's,#4kA-e E* F 0 0: 30 al4p I sm- 12 13 ;:c -"Coe 14 /-01-- !Mz 7r go 20 21 2@- 2 TF- 0 I-RP-ACE 0 Fig V, 4-T a F ILE DATE !Wi;j Uj 3p4 #AALV'S#S.Fdm 103$A' 0 #4 1,JC-% & AA #tE'PC lee),)c 3 F 2. ipjAS F Af-.PA-T io0 -.,7E-s7 ID c Ioo flop E G C) TAACE o 13 0 ovt io 41 o, :4 LAW--, i K 9&&& OA @21 -ff mw_.. 17L rA.4cii5 1/0 t7 C), 0 --510# 22 93 --jUo--rc- o,, -DR!",Eg rIC) n flec)rocz)rRlI-F x 27 FORM 10620 6 PVUO SAMPLE DESCRIPTION 0 ci ENVIRONMENTAL Filp: Pagt, N,@ ENGR. LAS - WORK SHEET Date: Analyst: I_j Hrs.: C-) 1,-ARd-Acp JAIN@ el,4!E.we 2@Cnwqlk \J' 614addilkc yut JAI A :rna__, 67lz4? .2 '7-SJ 3 Reviewed by: -ocot p FoAmiii 1* Otbrteaaitmnenftrepslhanatct.ivat6d'o,@',4dge mix rom 146tio in(i th(@ ec in,-tqtjo-ind the graph 611 adsorb'anc'e @at 600 nin versus- S ad j*ust"'14'yS.Sto 2000 add it ion or by@ gentrt,,uf mg /1 by DI .wate t' %@!E.iLona,nd, didcardin@i supernatant m Of this sludge, utl.Ons..Of AFFF, in 200 nivide each c;oltitionint.9 ino mi parts. jar with at least 200 mi..o.f. Placing- 1/2 in a .500 ml..volumetrip.' cyl,ind head space and the other half in' Cover and shak e, ead.hlj"a.r-,:-v-lqprouslyfor 30 secondr.. ..,.,,,'.@.,sThapakhkeoitn(ogtgriampeh,s0) aanndd 'mae.taIsurmeinuftoea,m height immediately after @-hotir 5 minute, 'Alc;n 'bsntv.e..aln(,Ip 9 toqraph how w' 20 minute, and I e,,I,l sludge settles. .-,Aerate the AFFF for 5 sludge mi x tures in the volumetric cylinders minutes at 500 ml of air per minute 'using gas, -:dispers'iontul)oswith rri,tte(cI7lass ends*" ,.a,g,,aAignainm,aokbeserpvleiotfoo4agmraplhise.l.g.h.'tqrlvolume and.,sludge settling, 10 ki 0-6 -nil -V 4 4w 5H,4KE -FE57 5WI4KE TE ST- 1-,eA)7(o2-S- A-T -TES-r '7(ZoN- L) Alp qc 76 Z.S AIC@9A-rto@j -rIES-T- 762-@- 77TW 4wt -OWL" 7(:,2-F F-- eavll 762-5 0 m 0 loop r(f 5- A4 4-,<A7)62-I- m lAl FormlOM-8-D-Pwo Sample Description 11(9 I L EnvironmentalLab - Work Sheet Lab Request No. Page- of Date: Analyst: yst. oe, C2 tg 4 d(J 0 tin dl' Xt ALA TIech,picalReport Summary Fom 6747 - 11 - N To: Patent & Technical Communications Services - 201-2C.12 Report Summary must be typewritten. Guidelines are on rovers* side. mrspjort Is printed on both sides OIPSP*R, 3M send two copies to P& TC& Document 'Pa"ff-I N-bw Number 0222 To Prowl munlbw .M. T. Pike =--236..mlB-31__ Autho4s) .iT:.;-WJ....M--o..gKan. R. D. Howell - siorvdopannont Environment al -Engine ProiW D*wAption e r,ing-k_-@!Allv 4ti Cqn o:L Papon N~ PWA awtimw In Mmimet O&M Tvpw 8Lk2L@2_ EMPWM Nwnbe" -W-H--29.5--4-6---4 rC LOC omanuation Code 089 1_.Il@&C -EPP-Research- and-D-evelopment. P4pW Title The Effectiveness of Selected Keywords Light Water Brand AFFF Aqueous Film Forming FoamFoam Antifoam Agents Defoaminiz Aj%ents ProjecOtbjectiv&eReportAbstract Antifoam Agents in Suppressing Foam Supression Waste Disposal Wastewater Treatment pa C*vww Foam... 3M recommends tocustomers thatAFFF usage wastes be disposed of by dilutintghewaste and flushingitintoa running sewer thatflows to a wastewater treatment system. R the AFFF inthe sewage isnot sufficientdliylutef,oaming may occur in the aerationbasin of wastewater treatment systems. This may cause cleanup problems and reduced efficiencyinthe treatment works. In thisstudy,the effectivenessand relativecost ofcommercially availableantffoam productswere evaluated.The experimental work consisted of adding the antffoam and 3M AFFF products to an aerated solutionofwater or activated sludge mixed liquorT.he effectivenessof the antffoams was determined by theirabilittyo prevent foaming in the aerated solutions. Inthe initiaslcreening tests,the 31 antffoams supplied by nine manufacturers were evaluatedfortheirabilittyo control foaming by a 500 mgtl solutionof AFFF in a delonized water solution.Twelve antgoams passed thistest.A second set of testsconsisted of successively adding an AFFF solutionto an aerated antffoam solution.Additionsof the AFFF stock solutioncaused the concentrationof AFFF to increase inthe solutionwhile the anfdoam concentrationdecreased. Nine antffoams were found to be effectivein these experiments: GE SiliconesAntffoam ErriulsibAnF-72, Antffoam Emulsion AF-93, and Antffoam Emulsion AF-9020; Henkel Defoamer WB-209 and Foanunaster Tm DS-.Union Carbide SAG 2001 Organosiricone Emulsion; Wacker SiliconesAnrdoam Agerd SE-36, Ardloam Agent SWS-214, and Antffoam Emulsion SRE. Of these,the most cost effectiveare Henkel WB-209, GE SHIcQnes AF-9020, Henkel Foammaster Tm DS, and Wacker SiliconesSRE. ReportType Security NCIODCX*Rolwemg E R & D Researchand Development 0 PiLotPlant 0 MANufacturing 0 Management SUMmary B Open Reportand Summary 0 Informal,- ususan initiais 0 TRP TriporFieldReport 0 FACtoryExperiment 0 ENGinearing 0 ROI RecordofInvention 0 TECH. Service 0 GOVT. Project 0 OTHER ClosedReport-Open Summary 3M Chemical 0 Now Chemicals Reported Registry usetwmow2 toantw intcohwww poostry Far P A TCS Use Only Fwn Clod* Do.-- - P & TCS EdilorIrJlials of POO" ----------- THE EFFECNVENESS OF SELECTED ANTIFOAM AGENTS INSUPPRESSING FOAM CAUSED BY LIGHT WATER BRAND AFFF SOLUTIONS INTRODUCTION Aqueousfilmforminfgoams(AFFF)arewaterbased,surfactacnotntaininpgroductussed primariltyocontrolcombustion hazards and extinguishfiresinvolvinghydrocarbon liquids. Intheiruse, AFFF agents are dilutedinwater and sprayed througha foam formingnozzle so thatthe foam spreads over the hydrocarbon liquidA.pplicatioonfAFFF preventsand extinguishesClass B firesby spreadinga vapor-sealingfilmover the liquidfuel.This vapor sealinhibitrseflasheven when the foam blanketisrupturedand alsoenables the producttobe used to preventignitioonfnon-ignitedspillsI.nadditionA,FFF provides excellentpenetratingand weftingqualitiewshen used on Class A firesA.ftertheiruse, waste AFFF solutionsfrom actualor simulatedfirefightinagctivitieasre partially biodegradableand have low toxicittyo aquaticorganisms includingthe microorganisms in wastewatertreatmentsystems.Therefore,wastes from AFFF usage can be discharged at controlledratesintoa wastewater treatmentsystem fordisposal. A disposalproblem inherenttoimproperlyhandled AFFF wastes isfoaming inwastewater treatmentaerationbasins.Excessivefoaming inan aerationbasincan cause a dual problem.Firstt,he suspended activatedsludge solidscan attachto the foam and be lifted from the aerationbasin.This causes clean-upproblems atthe wastewater treatment plant.Second, the remainingactivatedsludge mixed liquorisdepletedof much of its suspended microbialsolidsand thereforeisnot as effectivientreatingwastewater. Commonly, excessivefoaming iscaused by disposalrecommendations not being followed.3M recommends thatLightWaterTm AFFF waste should firsbte treatedinan oil-watesreparatorfollowedby metered dischargeofthe aqueous fractionto a running sewer. Ifpropedy metered, LightWaterTmAFFF concentrationsreachingthe aeration basinofa wastewater treatmentsystem willnotcause excessivefoaming.3M's AFFF productsare designed tobe used at either6% or 3% concentrationsinwater.For its6% AFFF concentrates,3M recommends a dischargeratesuch thatthe AFFF concentration inthe receivingaerationbasinwillnot exceed 100 mg AFFF concentrateper liteorf sewage. Due to itshighersurfactanctoncentrationf,orits3% AFFF concentrates3M recommends a dischargeratesuch thatthe AFFF concentrationinthe receivingaeration basinwillnotexceed 50 mg AFFF concentrateper liteorfsewage. The values forthe acceptableconcentrationsofLightWater' AFFF have been determinedexperimentally and aresomewhat conservativet;hereforeiftheAFFF wastes aredischargedto a sewer atapprop(iatleevelst,heywillnotcause excessivefoaming inthe receivingaeration basin. Some wastewatertreatmentsystems areofan insufficiesnitzeto make metered dischargeofthecollecteAdFFF wastes practicableF.or such sites3,M recommends one oftwo disposalalternative1s):transportincgollectewdaste materialsby tank trucksfor metereddischargeintoa largerwaste treatmentfacilitoyr;2) dischargingthe waste at a higherrate(upto800 mg/L vs.50 or100 mg/L)withappropriateconcentrationosfan antifoamagentadded tothewaste system to suppress foaming. Consequently,thereisa need to identifyjhmeost effectivaentifoamagents to be used in cases ofimproperdisposalofAFFF waste or when the AFFF waste must be discharged athigherratesT.o achievethisgoal,a two phased studywas completed to evaluatethe effectivenesosfseveralcommerciallyavailablaentifoamagentson currentLightWater TM AFFF products.Similarstudiesconductedinthe 3M EnvironmentalLaboratorybetween 1982 and 1987(')f,oundSWS-214 suppliedby SWS SiliconeCsorporationand WB-209 suppliedby Diamond Shamrock to be the most effectiveT.herefore,care was taken to includetheseproductsinthisstudy.SWS-214 isnow produced by Wacker Silicones Corporatioannd WB-209 isnow produced by Henkel Corporation. Phase one ofthisstudywas a surveyofantifoammanufacturers.Eleven companies were contactedand asked torunindependentteststoevaluatetheeffectivenesosftheir antifoamson LightWaterTm AFFF solutionsO.f the elevenmanufacturerscontacted,nine suppliedsamples and threecompletedevaluationsoftheirproducts.The three manufacturersthatcompletedevaluationwsere Henkel,Dow Cornin and Wacker SiliconesT.hese evaluationwsere completedusingtwo LightWater ?Im-AFFF products.The productsused were FC-203CF and FC-600. Henkel rantestsoftheirproductsand senttheirthreetop performers:Defoamer WB-209, Foammastet:TmDS, and FoammasterTm SZU. Of the three,Defoamer WB-209 receivedthe highestrecommendationfrom Henkel notonlybecause ofitseffectivenessb,utalso because ofitslow price.Thisagreed withthe resuftsofthe previous3M Environmental studiesand thepresentwork. Dow Corningsenttwo productsamples aftercompletingtheirtestingT.heirtwo products were 151O-US Food Grade AntifoamEmulsion and FG1 0 AntifoamEmulsion.Theirfirst recommendation was the151O-US Food Gr@de AntifoamEmulsion.Inthe testsdone for thisstudy,neitheroftheDow Corningproductswere found to be effective. Wacker Siliconeaslsoconductedindependentteststo determinetheirmost effective antifoams.AlthoughSWS-214 has been recommended by 3M to our customers inthe past,Wacker found threeoftheirotherproductsto be more effectivtehan SWS-214. The threeWacker productswere AntifoamAgent SE-36, AntifoamEmulsion SE-39, and 2 Antifoam Emulsion SRE. This study concurred withWackers resultsand found SE-36 and SRE to be effectiveW.hen consideringcost-effectivenesWsa,cker Silicones SWS-214 isalso acceptable. - The objectivesofthe second phase ofthe study were threefoldT.he firswtas to evaluate the relativeeffectivenessofthe 31 anfifoamproductsthatthe ninecompanies submitted and to identiftyhe top performers.The second was tofindthe antifoamconcentrationsof the top performer-tshatcould suppress foaming caused by AFFF concentrationsgreater than the recommended disposalconcentrations.The finalobjectivewas a costanalysisof the top performersto determine the most cost-effectivaentifoams. MATERIALS AND METHODS PRODUCTSTESTED LightWater Brand AFFF productsused inthe evaluationwere FC-203CF, FC-206CF, FC-600, and FC-600F. Thirty-onesamples were receivedfrom the antifoammanufacturers.The productswere: AirProducts SURFYNOLTM SU RFYNOLTM SURFYNOLTM SURFYNOLTM 104A Surfactant DF1 1OL Defoamer DF-75 Defoamer 420 Surfactant BASF PLURONIC'M L61 PLURONIC'"mLlOl PLURONIC@mLl2l PLURONIC@m3lRl Dow Coming 1510-US Food Grade AntifoamerEmulsion FG10 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 Defoamer WB-209 FoammasterTm DS FoammasterTm SZU 3 6 Nalco 7 Union Carbide 8 Wacker Silicones 7455 Antifoam7460 Antifoam 7470 Antifoam 7471 Antifoam 7472 Antifoam SAG 2001 OrganosiliconeEmulsion AntifoamAgent SE-36 AntifoamAgent SWS-214 Antifoam Emulsion SE-39 Antifoam Emulsion SRE 9 Witco Bubble Breaker" 776P Bubble BreakerTm 3056A Bubble BreakeiTm 913 PROCEDURE Tests were done using a modifiedJ.J.Bikerman foam controltest(2) Equipment used: Ministatic'pmump, Manostat Inc. flowmeter, GilmontInstruments 1000 mL graduated cylinderF,isherbrand gas dispersiontube,Ace Glass Inc.ASTM 70-100 g The pump was used toproduce an adjustableairflowthatwas bubbled throughthe test solutioninthe graduated cylinderT.his airflowas measured by the flow meter and deliveredintothe testsolutiotnhroughthe gas disr rsiontube.To bettersimulatean aerationbasinand forconsistencyt,he Ministatic pump was adjustedto maintaina constantairflow rateof2000 mumin. This ratesimulatedthe agitationand turbulent conditionsinan activatedsludge aerationbasin.Resultswere dedved from the presence and amount offoam thatbuiltup inthe graduated cylinderT.he measurement ofthe amount offoam was somewhat subjectiveand'@vasdetermined by a combination ofthe heightand densityofthe foam. For improved objectivitbyetween experimentalruns, resultswere recorded by takingphotographs ofthe testsatpredeterminedtimes forside by sidecomparisons ata latertime. 4 RESULTS Firsot4jectivTeo: evaluatteherelatievfefectiveneosftshe31 antifoapmroductst,hereby identifyintghe top performers. For the initisaclreen,the 31 antifoamagents were testedusing a 100 ppm antifoam concentrationtocontrola 500 mg/L concentrationofAFFF ina deionizedwater solution. The AFFF solutionwas prepared by dilutinwgeighed amounts ofAFFF, and the antifoamerwas dispensed intothe AFFF solutionby micropipetteand then mixed. The Ught WaterT"AFFF productsused forthistestwere FC-203CF, FC-600, and FC-600F. Resultswere recordedatthreeand ten minutes.Antifoamproductswere ratedfortheir effectivenesson a scaleof"A7 to"F",wit@"A" being the best and "F"forfailingT.hisinitial screen reduced the fielodf31 to 12 effectivaentifoams. Duringthisscreen,itwas alsodetermined thatthe antifoamswere essentialleyqually effectivoen each ofthe threeLightWater"4 AFFF products.Therefore,allremainingtests were preformed usingonly FC-203CF. The twelve antifoamsthatpassed the firsstetoftestsare: AirProducts SURFYNOLTM DF-75 Defoamer GE Silicones Antifoam Emulsion AF-60 AntifoamEmulsion AF-72 AntifoamEmulsion AF-93 Antifoam Emulsion AF-9020 Henkel Defoamer WB-209 Foammaste@m DS Union Carbide SAG 2001 OrganosiliconeEmulsion Wacker Silicones Antifoam Agent SE-36 AntifoamAgent SWS-214 AntifoamEmulsion SE-39 Antiloam Emulsion SRE The nextsetoftestswas completed using a revisedprocedure.Insteadof each expedment having a setconcentrationofAFFP and antifoamerfrom beginningtoend, the amount ofantifoamerinthe testsolutionremained constantwhileadditionsof Light WaterTm AFFF stocksolutionwere added at 10 minute intervalsT.he totalvolume ofthe testsolutionbegan at 100 mL withthe antifoamconcentrationat 100 mg/L. The AFFF stocksolutionconta7ined2 grams of FC-203CF per liteorfsolutionW.hile aeratingthe test 5 solution1,0 mL ofAFFF stocksolutionwas added at 10 minute intervalsT.he aeration rateused was 1100 mumin insteadofthe 2000 mumin used forthe initiaslcreen.This lowerrateproduced sufficienaterationand reduced the strainon the airpumps. The additionsof AFFF solutionincreasedthe concentrationofAFFF whilereducingthe concentrationofantifoamer.The additionsofAFFF were continueduntilthe antifoams couldno longercontrolexcessivefoaming..Resultswere photographed ateach interval. The photographs were used to identiftyhe maximum additionsofAFFF atwhich the antifoamercouldsuppress foaming to acceptablelevels.The number of additionsof AFFF, the starfinvgolume, and the initicaolncentrationofantifoamerwere used to calculatethe antifoamand AFFF concentrationsB.ased on the resultsofthistestthe field oftwelveantifoamswas reduced tothe finalfieldofthe top nine. The top nine antifoamsare: GE Silicones Antifoam Emulsion AF-72 Antifoam Emulsion AF-93 Antifoam Emulsion AF-9020 Henkel Defoamer WB-209 Foammaste@' DS Union Carbide SAG 2001 OrganosiliconeEmulsion Wacker Silicones AntifoamAgent SE-36 AntifoamAgent SWS-214 Antifoam Emulsion SRE Second objective:To determinethe concentrationsofthe top antifoamsthatcan suppress foaming caused by AFFF concentrationsgreaterthan the recommended disposalconcentrations. The procedure used was the same procedure used to findthetop nine antifoamswithone exception.To more accuratelysimulatea wastewater treatmentaerationbasin,fresh sludgewas used forallofthe remainingtests.The sludge was obtainedfrom Metropolitan Wastewater Treatment PlantinSaintPaul,Minnesota.Duringthe weeks oftestingt,he MLSS ofsludge ranged from 2.4to 3.5 g/L,a@d the pH ranged from 6.1to 7.9.Using this sludge,data were collectedforeach ofthe nine remainingantifoamsatfourinitial antifoamconcentrationsT.o geta range ofdata,fourinitialntifoamconcentrationsinthe sludgewere evaluated:300, 600, 1000 and 5000 mg/L. The studyfound the maximum 6 concentratioofnFC,203CFatwhicheachconcentratioofnthetopnineantifoamcsould suppressexcessivfeoamingR.esultasrepresentegdraphicalilnyFigure1 and tabulated attheendofthereport. IftheAFFF concentratiionntheaeratiobnasinisknown,theappropriataemountof antifoamecran be determinefdromFigure1.Thisinformatiiosnusefulforminimizintghe amountofantifoamT.hisisan importanctonsideratifoonrreducintgreatmenctostand avoidinfgoamingcausedby theadditionfexcessivaentifoamT.he possibiloiftfyoaming due toexcessivaentifoacman bestbe seenintheabnormalshapeofthegraphofHenkel WB-209 inFigure1.The graphshowsthataboveabout300 mg/L ofWB-209 the antfoambecomes increasingilnyeffecfaitvsouppressinAgFFF foam and may actually causefoaming. ThirdobiectiveT:o performa costanalysiosfthetopnineantfoams. The costanalysiwsas basedon thepriceandtheamountofantifoanmeededto suppressexcessivfeoamingcausedbyAFFF concentratiognrseatetrhan50 mg/L.The antifoaumnitcostusedinthisanalysiwsas thecostperpoundwhen purchasinogneto sevenbarrelAsn.tifoampriceasretabulateadttheend ofthisreportA.lthougthheprices aresubjecttochangeand varybasedon locatioand purchasevolume,thegraphsfrom thisanalysicsan be usefuwlhen comparingrelaticvoestofdifferepnrtoductsF.igure2 illustrattheesrelationsbheitpweenAFFF concentratiaonnd thecosttosuppressfoaming in1000gallonosfsewage.Figure3 isan expandedscaleofthesame datagivenin Figure2. 7 3000 2500 2000 0 '1Z. -5 c 1500 0 0 E C13 0 1000 < GE SiliconeAsF-72 GE SiliconeAsF-93 o-o GE SiliconeAsF-9020 0-0 HenkelFoammaster DS A-& HenkelDefoamerWB-209 w-m Union CarbideSAG-2001 *-* Wacker SiliconeSsE-36 Wacker SiliconeSsRE +-+ Wacker SiliconeSsWS-214 500 0 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 FC-203CF Concentration(mVL) Figure1. Antifoamconcentrationrequiredtocontrolfoamingfrom FC-203CF. 8 $70 $60 cn c $50 0 7@ cr) C:) C:) CD $40 CL 0 (CY.) )$30 c E co 0 c: $20 mi--mGE SiliconesAF-72 o-o GE SiliconeAsF-93 o-o GE SiliconeAsF-9020 o-o HenkelFoammaster DS ,&-& HenW Defoamer WB-209 iK-m Union CarbideSAG-2001 Wacker SiliconesSE-36 v-v Wacker SiliconeSsRE +-+ Wacker SiliconeSsWS-214 $10 $0 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 FC-203CF Concentration (mg/L) Figure 2. Cost comparison forantifoaming 1000 gallonsof solutionconta@ining variousconcentratons of FC-203CF. 9 $20 $15 ccn 0 co C)) C) C:) C:) CL -cb.n- $10 0 C) cm c E cri 0 a < $5 o-o GE SilicoreAsF-72 o-o GE SiliconeAsF-93 o,-@oGE SiliconeAsF-9020 0--o HenkelFoammasterDS HenkelDefoamer WB-209 UnionCarbideSAG-2001 Wacker SiliconeSsE-36 v-v WackerSilioDmSRE +-+ Wacker SiliconeSsWS-214 $0 0 100 200 300 400 500 600 700 800 900 1000 FC-203CF Concentration(mg/W Figure3. Costcomparisonforantifoamin1g000 gallonsofsolutiocnontaining variousconcentratonosfFC-203CF. (Expandedscale.) 10 CONCLUSIONS IncaseofimpropedrisposaolfLighWtaterTmAFFF wastesorwhenthewastesmustbe dischargedata higherratethan optimallyrecommended, themost cost-effectiavnetifoam agentsare Henkel WB-209, GE SiliconesAF-9020, Henkel FoammasterTm DS, and Wacker SiliconesSRE. Ifthe AFFF concentrationis600 mg/L or less,WB-209 isthe most cost-effectiavnetifoam.Note thatwhen usingWB-209 careshouldbe taken notto use toomuch, because concentrationosfWB-209 greaterthen about 300 mg/L have a greatlyreducedefficacaynd may actuallcyause foaming. IftheAFFF concentratioinsgreaterthan 600 mg/L, or WB-209 isnot readilayvailable, GE SiliconeAsF-9020 isrecommended. AF-9020 iseffectivoevera much largerrange thanWB-209 and isthesecond most costefficienatntifoam.The second choicefora largerange antifoamisHenkel FoammasterTm DS. Foammaste@' DS gave results comparabletothe GE AF-9020 butwas slightlmyore expensive.Anotherantifoamthat preformedverywellover a largerange and was onlymoderatelymore expensiveto use, was Wacker SRE. Althoughallfourofthe recommended antifoamsare availablfeor export,a consideratiofnorSRE isthatitisproduced inEurope and thereforemay be more readilayvailablfeorthe European market.The recommended concentrationtso controlconcentrationosfAFFF can be found foreach ofthe recommended productsby usingFigure1 orthe datatabulatedatthe end ofthe reportA.lso,to findtheapproximate costofsuppressingfoam atvariousAFFF concentrationcsan be found usingFigure2 or Figure3 foran expanded scale. REFERENCES 1.EnvironmentalLaboratoryLab Request No. Dl 629. 2. Bikerman,J.J.Foams Springer-VeriagN:ew York 1973. Antifoamconcentrationrequiredto suppressAFFF atvaryingconcentratiofnorthetop nineantifoamproducts.Allconcentrationasre inmg/L. GE Silicones FC-203CF AFF1-72 i5-i'07c5 0 57500 214 57550 F 1S68690 400 890 526 1150 2083 GE SiliconesFC-203CF AF-93 50 0 575 214 667 400 906 526 1180 2000 GE Silicones FC-203C AF-9020 50 0 575 214 665 400 870 556 1160 2273 Henkel FoammasterTm DS 50 550 667 875 1190 FC-203CF 0 214 400 556 2000 Henkel WB-209 50 580 630 571 300 FC-203CF 0 214 400 714 4167 Union Carbide SAG 2001 50 333 450 550 800 FC-203CF 0 250 461 714 2941 Wacker WackESeE-r36 46510 461 582655 755605 750 825 FC-203CF 0 231 429 625 2778 Wacker SRE 50 571 675 880 889 FC-203CF 0 214 375 556 2778 Wacker SWS-214 50 400 500 590 580 FC-203CF 0 231 429 667 3333 12 Antifoampricesused inthecostanalysisT.he priceswere obtainedby telephonefrom the manufacturersduringthemonth ofJuly,1992. GE Silicones 1-800-332-3390 AntifoamEmulsion AF-72 AntifoamEmulsion AF-93 AntifoamEmulsion AF-9020 Henkel 1-800-922-0605 Defoamer WB-209 FoammasterTm DS Union Carbide', 1-800-523-5862 SAG 2001 OrganosiliconeEmulsion Wacker Silicones1-800-248-0063 AntifoamAgent SE-36 AntifoamAgent SWS-214 AntifoamEmulsion SRE $3.93Ab 3.74 1.93 0.45 2.315 1.61 2.50 1.34 2.63 13 AiFiFr-armn-@tri, I w a4ev- LtlAya-,V@de-oit-tieid -3H %kfp-IkU-7Cklwo -a5CSCC3) -@Lo.Oe4n-51L c-iC-ASCQ@) Z-5,5rr5/L Cl-%@ A,o amt@&r' ZC)5 PC-- Z05CF@ Lci--1501 loyyllj@ 10 ,50- 100. CFVI cc .505 LA -ec@ tA Cetii'S- VAM Cil8%tei ft pev5i6it4ke ? W.;M*q Cf roa,,VK-- -toi@ta.l5f;-aea W%VLA. 15 " K ;@\1 at 15 -Ara-Suctvt*vivwi-avcLuld -iAAbe-) 30ne ai a4 IvW@& --),-r@ooild QXOU.VO4 +L,-b s+ I-PAIK sotltd -3 42@wmi",,f aabec I vict '501 CA Vk. IZMAWA v,_iZo@=uAd4ub at T8@'q@Zcb@@d--d 5VVIK kuv- '&Lite T,62".O Cor"Aed , er Y)o cr Falm4747-11 -K To: Patent& TechnicaClommunicationSservice-s201-2C-12 R"MdSUMM&Y mustbe "w,iffes.Guido&wsaivontvvomo*Vs. Document a p-,l Nwrbw Number 10222 To D. L.BACON A~oi R. D. HOWELL fto" Nwnbw 1 ENVIRONMENTAL ps D-W"- TECHNOLOGY & SERVICES AFFF WASTE TREATMENT PAP"Mft PRECIPITATION AND ULTRAFILITRATION EXPERIMENTS Keywo"k -70 UG 089 WITH 3M FC-203CF 3M Nwftw P'Wm addmo" 01" In Ab*ad ate* Do@ rfpw 03/20/95 NUM*-(S) 295864 OMwftadon Co" Perw covww 11/94-12/94 AFFF; WASTEWATER TREATMENT; LIGH7WATER BRAND; FLOCCULANT, SURFACTANT, FLUOROCHEMICAL; AQLJEOUS FILM FORMING FOAM; COAGULANT; PRECIPITATION ProjectObjective& Rqmd Mntwt AFFF usage waste disposalisoftena problem for3M customers afteractualfirest,estingextinguishmentsystems or* aftertraininegxercises.3M reconwneridsmetered dischargeofAFFF usage wimes toa municipalor industrial wastewatertreatmentsystem so thatbiodegradablecomponents willbe mineralizedO.ften,thisisnotpracticablecause ofthe smallcapacityofthe waste treatmentsystem,regulatorlyimitso,r because of excessivefoaming.We have been investigatinegw methods forwaste treatmenti,ncludintgurfactanptrecipfttiownithpotycat;oniscurfactantasnd inorganiscafts(seeTechnicalReportby lgffberlByekes,7/30/93)and uhmfiftmtioTnh.is reportincludesresultosf precipitatiaond precipitatioon4pledwithuftrafiftratBiootnh.methods show promiseas AFFF usage waste treatment processes,but theultmfiftratmieotnhod ismuch more costlybothinterms of capitaalnd operatingexpense.We are continuintgodevelopa solutiontoft AFFF disposalproblem and we are seeldnga thirdpartywastewatertreatment firmtoperforma full-scadlemonstration. Report Type Security NWebmk 0- R & D Research and Development 0 PiLotPlant 0 MANufseWring 0 Mwiagament SUMniary B Open Report and SLmnmary 0 0 TRP Tripor Reid Report 0 FAC%ory Exparknent 0 ENGin"dng 0 ROI Recordof lnvandw 0 TECH. Servir.9 0 GOVL Project 0 OTHER ClomW Report-Open Summary 3M Chmical 0 Now ChaniicWs Reported PA48try U. lom OM j.. toinoowd,.o S@Owy For P A TCS Use Only: ffreporitsprintoendbothsideosfpapers,endtwocop@etsoP TCS. Precipitatioannd Ultrariltration Experknents with 3M FC 203-CF Edwin E. Tucker 1805 Aladdin St. Norman, OK 73072 December 8, 1994 Table of Contents PrecipitatioMneasurements ................................. UltrafiltratiMoenasurements ................................3... Summary and Conclusions ..................................6..... Experiments with 3M AFFF Two types of experiments were performed with aqueous solutionsof AFFF. The firsttype was precipitatioonf the fluorinatedsurfactantsFC-95 and L4640 with an added cationicpolyelectrolyteT.he second type was ultrafiltratitorneatment with an excess concentration of the cationicpolyelectrolytteo produce a treated water (permeate) stream with reduced fluorinatedsurfactantcontent and a concentrated waste stream containingfluorinatedsurfactants. PrecipitatioMneasurements The hypothesis in the precipitationmeasurements was that, by adding a stoichiometricamount of a positivelycharged polymer to an aqueous solutionof AFFF, negativelycharged surfactantions (includingFC-95 and perhaps the amphoteric FC-1 240) could be precipitatedas an electricallyneutral complex. Calculation suggested that the anionic charge equivalence in the originalAFFF solutionwas ca. 0.003 M (when dilutedto working concentration). Solutions were made up so that the polymer concentrationwould range from 0.001 M to 0.005M insolution(initially) at a working concentrationof AFFF (3 partsconcen'trateto 97 parts water). The cationicpolymer used for these experiments was Merquat 100 which is a high molecular weight (ca. 200K Daltons) quaternary amine polymer (polydiallyldimethylammoniumchloride). The polymer was a product of Calgon (Merck) and was suppliedas a 40% by weight aqueous solution.The concentrations referredto above are interms of monomolarity. For example, ifthe repeat unitofthe polymer has a molecular fragment weight of 163, then a 1 M solutionwould consist of 163 grams of polymer inone liteorf water. Table 1 below reportsanalyticalresults by Jim Wolter of 3M for the precipitatseamples sent to 3M on 9-6-94 Table1: Resultsof AFFF PrecipitatiwointhCatioaicPolyelectrolyte Sample 02 [FC-95] PPM 28.39 [L4640] PPM 720.5 [Cat]' m 0 1 22.86 295.1 0.001 2 1.63 115.9 0.002 3 0.36 102.3 0.003 4 0.08 73.5 0.004 5 5.27 163.54 0.005 I Total(mono)molar concentrationof cationipcolymer inthesolutio.n 2Sample 0 representsthe composition(in ppm offluorinatecdomponents) of a blanksample containingonlyAFFF and deionizedwater. The totalorformal concentrationsof FC-95 and L4640 should be thesame as thisfor saipiple1s-5. The analyticalresultsforAFFF fluorinatedcomponents inthe supernatant solutions generallyconform to expectations. There isa continuous decrease in FC-95 and L4640 concentrationsin solutionas the cationicPolymer concentration in solution increases up to a point estimated as near charge equivalence. This decrease is presumed to occur through precipitatioonf a fractionof the polymer and anionic solutionconstituentsas a neutralsolid- At the highestconcentrationof Merquat 100 (sample #5), the solutionconcentrationsof FC-95 and L4640 appear to increase. This increaseisexpected because an excess of cationicpolymer willtend to keep the anionicconstituentsin solution. Inprevious work (with the samples sent to 3M on 3-20-94) utilizinag range of polymer concentrations from 0.003 to 0.03 M to investigateprecipitatioinn AFFF solutions,itwas found that no visibleprecipitate appeared in solutionswith polymer concentrations above 0.006 M. This indicates thata charge excess of more than 100%, i.e.,a polymer to AFFF anionicconstituents ratioof 2:1 or higher,is sufficiento keep the AFFF fluorinatedcomponents in solution.On thisbasis,a concentrationof 0.01 M polymer was chosen foruse inthe ultrafiltratieoxnperiments (see below). Conditionsforthe precipitatioenxperiments were as follows: A stock solutionof AFFF was made by delivering3 mL of AFFF conceritrateinto a 50 mL volumetric flask. The flaskwas then filletdo the mark with deionizedwater. This solution containsAFFF attwice the normal working concentration of 3 partsAFFF concentrate to-97 partswater. 5 ml of the AFFF stock solutionwas placed ineach of six20 mL screw cap vials.5 mL of deionizedwater was added to vial#0 as a controlsample. A stock solutionof 0.01 M cationicpolymer in water was prepared by dilutinga weighed amount of polymer concentrate(40% by weight inwater). Volumes of stock polymer of 1, 2, 3, 4, and 5 mL, respectively,were added to vialsnumbered 1 through 5 containing5 mL of AFFF stock. Deionized water involumes of 4, 3, 3, 1, and 0 mL, respectively,was added to vials1 through 5, respectively.@klivialsthen contained 10 mL of AFFF at a working concentration ratioof 3 parts AFFF*io 97 parts water. Vials 1 through 5 also contained 0.001 to 0.005 M polymer in numerical. sequence. Allvialswere shaken brieflyby hand to mix the contents. Allsamples showed visibleprecipitatioonf tan colored-particleswithin at leasta few minutes. Some qualitativoebservations are that the samples below and above the charge equivalence pointappeared to produce more finelydivided precipitates. Samples near the equivalence point (#3 and #4) produced some largerparticulate matter on the order of 1-2 mm in diameter. These largerparticlesdid not settle rapidlyand appeared to adhere to the glass walls of the vial. 2 UltrafiltrMaetaisounrements The figurbeelowgivesa schematiocfa simpleultrafiltr(aUtFi)osnetup.The columndepicteidnthisfiguriesa hollofwibecrolumn.Thistypeofcolumnwas used inthepreviouUsF experimenotn AFFF (3-20-94)F.orthecurrenetxperimental resultass,o-callsepdirawlound UF columnwas employed.The hollowfibecrolumn is constructeodf a number of membrane tubulespottedwith adhesivein a configuratqiuointseimiltaoranordinarlyaboratocroyndenserT.he FeedUF solution flowsintoneendofthefibelrumenandPermeatleiquiedxittshefibeartrighatngles througthhemembranepores.The remaininsgolutiointhefibe(rRetentateex)itast thetopend ofthefibelrumen.The spirawlound columnconsistosf a dual-face membraneenvelopceoncentricawloluynd withflowspacersseparatienagchwinding. Feedsolutioinspumped intoone end of thecolumn. Liqui(dPermeatew)hich penetrattehsemembranecirculatienasspiraflashiotnoa centetrubeforwithdrawal. The remaininsgolutiownhichdoesnotpenetratehemembraneexitass Retentataet thecolumnendoppositteotheFeedentrance. Figure1. HollowFibeUrltrafiltrAaptpiaornatus vi R T2 let,v ?I p dfpn t Feed P2 Reservoir 6T4i@@ p 7hfeeerdeserivsao5giarlplolnyetlhaynl7keh.nteeanckotuaertieunsterrneaclilrycautal3a0t0ed galLhra.tbeypumPp2.FeesdoluitfsioornciendthoheolfliobwbeyrpsumPpIw,hihcahasnaccurately contrpowlnlperidanutgpeto2Llmi7n7.tefairrbeeprrsebsyetnhttehevidenrtliicnaRelest.enetxaiattteshe toopfthceoluamnpndermeeaxtitethsefihboerriszofnltoawoliulnttygh,rotuhgtehumbaerkPe.d7hecolwnn iasHar1p8incpho,lysmuetmfbornhaeonlelowcfairbterwri2dtfghte2anradeIaOmKoLwtc.ut(-MoWfCfO). TIand72arperestsruarnesdmuecaesruisrnipnaugntodut(pbuatpcrkm)urreess,pecutptiov5e0plsyfi,ogr thceoluamndndisplraeyaidnoigntnhgdesigpiatnamelelt(edrpmV)a.rivaobllusempeliotftfieinengrdteotentate anpdermefartaectiisaocncsompblyiospheendoirncglosvianlVgviewhimcohdyc7o&lubmancpkressure. RestroifrcettieonntbayptaerftlciolawolsvliaynlVgvIiencrtehaesfersoafcfteiexodinhtoirnigzo(nttharloluygh thefwiabletlrotsh)ceoluamspner7n7ehaaetpep.ariaostpuesrianstteedsatdamytoedweitbhotrheteanntdate perynbeeairtnegcytcotlhefedeerdeserSvaomiprlp.ionifgnotfrseerde,tenatnapdteer,mefaltoaewrneot showWni.thdorfaswaamlpleasnfaollryesaitdsoasslidgehctrienafseceodncenotvreatrthcieoounorfsaen e-rperIinamdednitto.tihocenomposoiftthieofsneoelduthiteownio,nierdepenodfefnpetuefmdapcritanotgres andretentfaltoewrestricmiaiyobnemodifiteodchangseeparaticon ditions. 3 The ultrafiltratieoxnperiment was initiatebdy mixing 240 mL of AFFF concentrate with 8L of aqueous cationicpolymer solutionat a concentrationof 0.01 M. One sample from thismixture was taken to providea referencepoint. Conditions were then adjusted inthe UF system to produce ca. 30% of the flow through the column as permeate liquidwith the remaining 70% existingas retentate. Samples of retentateand permeate liquidswere taken at thispoint. Two furthersets of samples of permeate and retentatewere taken at conditionsnear 40 and 80% flow as permeate liquidr,espectively.Totalliquidflow through the column ranged from a high of ca. 600 mL/min at 30% permeate (Recovery)to a low of ca. 120 mL/min at 80% recovery. Table 2 gives analyticalresultsfor these severalsamples as well as the Recovery percentages and the appliedpressure at the column entrance. Table 2: Results of UF Experiment on AFFF with Cationic Polyelectrolyte Sample 0' [FC--951 P,ppm -- [FC-951 R,ppm 39.7 [L46401 P,ppm -- [L46401 R,ppm 1261.9 Recov. .% -- Pres. psi -- 1 0.04 47.6 106.9 1497.5 31.7 26.4 2 1.12 48.6 125.8 1497.1 40.3 33.5 3 1 5.29 ill .0 199.2 1419.4 82.7 41.8 I Sample 0 represents the composition tinppm of fluorinatedcomponents) of the originalFeed solutionprior to commencing the UF. experiment. This sample was marked as Fl in the analyticalresultsprovided by Jim Wolter of 3M. Results are arbitrarilpylaced in the retentate (R) column for Sample 0 even though the composition of the feed solutionismeasured here. ' To examine the effectiveness of the UF process in removing fluorinatedAFFF components we can look at the Recovery (percentage of liquidflow passing through the membrane as permeate) and the levelof the components inthisliquid.For sample #2, 40.3% of the feed liquidappears as permeate water. Relativeto the composition of Sample #0 (Feed),the fractionof FC-95 remaining inthe permeate is1.12/39.7 or 0.028. This means that 97.2% of FC-95 has been removed from this liquid. Likewise,the fractionof L4640 remaining in the permeate for Sample #2 is 125.8/1261.9 or 0.0996. This means that 90% of L4640 has been removed from the permeate liquid,relativeto the Feed under the conditionsforSample #2. As the pressure isincreased on the system and more liquidisforced through the membrane as permeate for Sample #3, the qualityof the separation becomes somewhat worse. At thispoint,82.7% of the feed liquidis being produced as 4 permeate. The removal of FC-95 from the permeate is 5.29/39.7 or 0.133 for fractionremaining (86.7% of FC-95 has been removed from the permeate). The removalof L4640 from the permeate is199.2/1261.9 orO.158 forfractionremaining (84.2% of L4640 has been removed from the permeate liquid).The removal percentages for FC-95 and L4640 are comparable at this point. However, the retentateconcentrationof L4640 (1419.4 ppm) in the retentatedoes not appear reasonable. Just as the retentateconcentrationof FC-95 increased forSample #2 to Sample #3 (i.e.4,8.6 to 111.0) the retentateconcentration of L4640 should have increased by a substantialamount, instead of the slightdecrease shown. In summary, the removal of FC-95 and L4640 from aqueous solution by ultrafiltratiwointh an excess of cationicpolyelectrolyteappears to be reasonably successful. There are three specificpoints,however, which deserve comment: 1). Itisdisturbingthatthe analyticalresultsshow thatthe initiacloncentration in the Feed sample (Marked 0 in the Table above) for ultrafiltratiosnsome 50% higher than the concentrationof the AFFF stock solutionwhich was used for the precipitatiosntudies. The initiailntentwas to use the same concentrationof AFFF in both studies;i.e.,3 parts by volume of AFFF contained in 100 volumes of solution. The only known differencein the two solutionsig that the zeroth solutionfor precipitatiocnontained only distillewdater and AFFF while the zeroth (Fl)solutionfor UF experimentation contained distillewdater, cationicpolyelectrolytea,nd AFFF. If one assumes thatthe analyticalresultsare correct,then itislikelythat a repeatofthe UF experiment (at the lower AFFF concentrations apparent in the precipitation experiment) would show improved results.That is,the removal of AFFF fluorinated components should be betterthan the resultsshown inTable 2 above. 2). With referenceto Table 2 above, itisinprinciplepossibleto check the mass balance of a particularcomponent in the system. Because the totalflow in the UF system isrecycled (both permeate and retentatefluidsare returnedto the'feedtank), the following relationshipshould apply: [Feed] = Recovery [Permeate] + (1-Recovery) [Retentatel {1) where (Feed],(Permeate],and [Retentate]are analyticalconcentrationsof a particular component inthe feed,permeate, and retentatesolutions,respectively,and Recovery is the fractionof the totalliquidFeed in the system which appears as permeate. Taking data from Sample #0 (Feed concentration)and forSample #1 above forFC-95, the followingrelationshipshould be an identity: (39.71 = 0.317 [0.041 + 0.683 [47-61 however, [39.71 ;d [32.51 5