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BACK TO MAIN Impinger Studies of Volatility of FC-95 and FC-143 Intoduction and P u p : ?hennospray mass spectrometry was used to quantitate a number of samples for FC-143 and FC-95. The overall purpose of this experiment is to determine whether or not FC-95 andor FC-143 has an appreciable vapor pressure at room temperature. This experiment consists of two parts. The first part of this experiment is to test whether either of these compoundsare removed from a variety of solutions when air is bubbled through them. In the second part of thisexperiment, a solution of ammonium acetate in 1-propano1:water -is used to trap any FC-95 and/or FC-143 that volatilizes at room temperature. Part I The solutions that were tested to see if either or both of Ihe fluomchemicals are removed from them upon passing air through them are described below: Label 1 2 3 4 5 6 7 8 9 lOOA 200A 4OOA 800A 2000A Compound Tetrabutylammonium hydroxide Ammonium acetate Laurylpyridinium chloride n-Alkyldimethylbenzylammonium chloride Cetyltrimethylammonium bromide Tallowtrimethylammonium chloride Dicocodimethylammonium chloride Water/l-pmpanol(5050) Water/l -propanol (5050) Amonium acetate in water/l-propanol(5050) Amonium acetate in water/l-propanol(50:50) AmoNum acetate in waterll-propanol(5050) Amonium acetate in waterll-propanol(5050) Amonium acetate in water/l-propanol(5050) coacurtratim 500 PPm 500 503 500 500 505 500 0 0 500 500 500 500 500 [FC%l 10.0 ppm 10.0 10.0 10.0 10.0 10.0 10.0 10.0 0.00 0.10 0.20 0.40 0.80 2.00 [FC143] 10.0 ppn: 10.0 10.0 10.0 10.0 10.0 10.0 10.0 0.00 0.10 0.20 0.40 0.80 2.00 Part II A 5050 water/l-isopropanol solution containing 500 ppm ammonium acetate was used in the second part of this experiment. In this part of the experiment, FC-95 or FC-143 is placed in an apperatus which air is passed through. Glass wool is placed downwind of the fluorochemicals to trap any particulates. After the air passes over the fluorochemicals and through the glass wool. it is bubbled through a train of impingers - containing the ammonium acetate solution. If the fust part of the experiment shows that there is no loss of fluorochemicals upon passing air through the solutions, it is expected that if there is any fluomchemicals present in the air,they will be transferred to and retained by the ammonium acetate solution. BACK TO MAIN Experimental An Extrel ELQ-400 was used with a Vestec thennospray to quanitate rhese samples. FC-95 is quantified by monitoring the ion current at m/z 499, FC-143 is quantified by monitoring the ion current at m/z 413. A Waters 600-MSHPLC pump with SILK was used with a Waters WISP 712 autoinjector for delivering 10 uL injections of the sample to the thermospray. The mobile phase composition was 39:60:1 acetonitrile:waterl ppm tetrabutylammonium chloride flowed at 1.5 ml/min. The tip temp pot was set to 4.75 while the block pot was set to 5.3. For each sample, three injections were made for both the stock solutions, which were spiked with the fluomchemicals but did not have air blown through them, and the "blow" solutions, which are identical to the stock solutions except that they had 280 liters of air passed through them. Thus, the stock solutions serve as controls for measuring loss of fluorochemicals. The stock and blow solution injections were staggered to minimize the effects of any drift in the mass spec response. The integrated mas of the selected ion currmts for the blow and stock solutions are averaged, adjusted for volume changes caused by passing the air through the impinger, and then ratioed. This adjusted ratio then reflects the amount of fluorochemical that remained in solution after passing the air through the impinger. A ratio of 1.00 indicates no loss of fluorochemicals, while a ratio of 0.00 would indicate a total loss of the fluorochemicals upon passing air through the solution. Part I The results of Part I of this experiment are summarized below. These results indicate that there is some loss of fluorochemicals upon passing air through most of the solutions, but most of the solutions retained 85% or more of both fluofochemicals. This suggests that both FC95 and FC143 are capable of volatilizing out of most of these solutions. Solution Tetrabutylammonium hydoxide . Ammonim acetate Lautylpyridinium chloride n-Alkyldimethylbenzylammonium chloride Cetylhimethylammonium chloride Tallowtrimethylammonium chloride Dicocodimetbylammonium chloride Water/l-Ropanol(5050) Ammonium acetate in water/l-propano1(5050) 100 ppb Ammonium acetate in water/l-propanol(5050) 200 ppb Ammonium acetate in water/l-propano1(5050) 400 ppb Ammonium acetate in water/l-propanol(5050) 800 ppb Ammonium acetate in water/l-propanol(5050) 2000 ppb % Retained - FC143 83 90 90 101 95 90 89 85 98 108 85 89 92 IRetained - FC96 90 71 90 100 95 93 84 89 96 101 90 95 96 No fluomchemicals were found to be present in either the first or second impinger. This indicates that the amounts of FC95 and FC143 transported from the solids to air and then into the solution is below the sensitivity of the instrument, thus suggesting that both compounds are involatile or have very low vapor pressures as solids. BACK TO MAIN conclusions A solution of 5ooppm ammonium aatatcin a W5Omixmo f ~ l - p r o p a r o wl as used in the secondpart of tbis expaiment. The solutions ofammcmimacetate m w ~ l - p m p a n ohlrd an averagepercentretention of 94% for FC95 and 93%for X143. - Neither FFO nor PFOS was found in any oftbe impingers that were tested in tbe secoodpartof this experiment. Tbe sensitivityoftbe metbod is such that fhe flouaodrermcalsSboaMbedeSectedinthe impingers if tbe vaporpressure of the givencompoundcxcetds approximately 1 . 1 ~ 'tar. since neitber compoundwas obser~edt,be vaporpessure ofboth oftbeseannpmmds is kssthan 1- 107 tom. This experimentdoesoot addressissuesrelakdto kinetics of phase tramfer. whicb may be important. BACK TO MAIN 9-3 X143 9-4 Assuming the air behavesas amixture ofidtalgsstsandtbe air is at standardpssurc, tht numbex of m o b of airmoleculesin 280 limof airat#) +c is: 280 liters (22.414 liters I m2o7l)3 K- 293 K = lL4mol 9-5 since m, fluorocbanicals w a e f d i n any oftbe impingersrhatwaettsted tbe vaportwocompwDdsis less than theminimumvalnes sbown in equadoru d a d 7. of these BACK TO MAIN `. = 3!5m 3w3 -1 a 7 4 444 4254 r1257 l(il go 4184 4361 szsa 3233 40% 3388 3590 3668 Q3 71 2576 2596 2563 2!ja6 2614 a699 2785 aa99 106 go 3890 4120 42s 4187 4243 44% 4595 4421 108 100 2443 2454 2427 2441 2516 2542 2502 2sp 103 Ei 5779 5778 dOB0 5879 6219 4509 66x5 6481 110 93 5436 6031 6175 5881 5778 5#4 5156 5633 % 84 6155 &338 5639 6011 6583 7342 5266 m 105 89 0 0 0 0 0 0 %LLldrrd 134 93 99 109 140 109 106 1 19 % % 175 185 188 163 168 209 210 208 W 101 169 317 316 363 932 306 39 1 382 353 375 90 276 553 568 47 1 ssb 491 615 633 41 1 353 95 468 1303 1286 815 1135 1044 1389 1331 931 1234 % 999 BACK TO MAIN Part I Data PFO Sample 1 -Stock 1 -Blow 2-stock 2-Blow 1st Inject 2963 2989 L 3334 3702 2nd tnject 3157 3407 3247 2533 3rd Inject 3434 3067 2093 262 1 Average 3185 3154 XBlowlStock 99 Adjusted X 83 2891 2952 102 90 3033 3197 3674 3301 3207 347 1 3631 3436 104 90 - 4-StOCk 4751 5466 5877 5365 +Blow 5522 5854 6294 5890 110 101 5-Stock 3884 4612 4444 4313 &Blow 4273 4342 4798 447'1 104 95 &Stock 4052 4107 4207 4122 &Blow 4361 437 1 4540 4424 1 07 90 'I-St~ck 3811 3625 3586 3674 7 - k W 3838 3768 3500 3702 101 89 &Stock 5076 5181 5105 5121 &Blow 5220 5390 5008 5206 102 85 9-Stock 0 9-BloW 0 lOOA 105 lOOB 125 0. 0 0 0 81 a8 89 90 X 0/A %/100A 91 101 98 98 200A 136 164 129 143 157 2008 181 163 181 175 108 169 400A 295 274 31 1 293 32 1 4008 316 326 292 31 1 85 273 BOOA 515 532 365 47 1 515 8008 530 537 301 456 89 459 1201 11% 590 996 1090 1226 1182 712 1040 92 1002 Part II Data PFO sample Tl I1 T1 I2 T2 I1 T2I2 T2 I1 T2 I2 1st Inject 0 0- 2nd Inject 0 0 3rd Inject 0 0 Average 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0- 0 0 0 PFOS sample T1 I1 nI2 T2 11 T2 I2 T3 I1 T3 I2 1st Inject 0 0 2nd Inject 0 0 3rd Inject 0 0 Average 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 BACK TO MAIN BACK TO MAIN Nu(BER COUDOUY)WME 1 Tetrabutyl ammonium hydroid8 2 Ammoniumacetate 3 Laurylpyridinium chloride 4 n-Alkyldimethylbenzy&mmonium c h W 5 Cetyttrimethylammonlumchloride 6 Tallow trimethylammonium chloride 7 Dicocodimethyl ammoniumchloride 8 H N 1 -propand(5050) FCWl43 9 W1pro(;and 10 . 2 5 d 11 .5ml 12 1 mi 13 2ml 14 5mi 15 16 C C Y Y C P J T R 4 T # N C I I T U L W F I W m STAClTTlWE (m*9 9nlq) aOW 5ooppm 25 5ooppm 25 Wppm 25 500 ppm 25 mppm 25 Wppm 25 5ooppm 25 10 ppm 25 ??? 25 looppb 25 mppb 25 4ooppb 25 mppb 25 2ppm 25 21 11:s 1616 22 11:s 1616 21.5 11:s 1616 23 11:s 1616 23 11:s 1616 21 9:s Auto 22 9:s AUO 21 9:s AUO 22 9:s Auto 22 852 AlAO 22 852 AUO 20 8:52 AlAO 23 8:52 Allto 22 852 Aut0 W p 6 w a D ROWAIlE TVDIALAR- 280 1 280 280 1 280 280 1 280 280 1 280 280 1 280 280 1 280 280 1 280 280 1 280 280 1 280 280 1 280 280 1 280 280 1 280 280 1 280 280 1 280 BACK TO MAIN 25 1045 ++-t-- I t - 25 I I 1045 1045 lo:# 1o:# lo:# ) - Aut0 280 Aut0 280 Aut0 280 Aut0 280 Ado socommwd Auto I so-1 COMMENTS: Pump on Train 3 huedat 181 minutes. There was a 25 minute span of tlme when no sample was being pumped. The total sampletime was 255 minutes. 7VTMAU KKUT 0 1 280 1 280 1 280 1 1 1 BACK TO MAIN D U 0 ~ [ 3 0 1 , 1 ) D 4 7 2 1 , , 07-OCT-93, 05:06:51 Sl Sns: 1-8409, Max: 2032, C Max: 203: RT: 0.0, 171.0 MsS. LS n s : 1 - 8 4 0 ~ 412.6-413.5, lax : 8 8 0 , 31 se C Max: 88( L 0.0, c=: 5: .dib =r i= 1000 1 2 00 ? 3000 4000 I, 5000 .. 7000 8000 BACK TO MAIN fl Ms 07-OCT-93, 08:41:19 4 9 8 . 6 - 4 9 9 . 5 , Sns: 1-10032, Max: 2528, C Max: 2528, RT: 0 . 0 , 204.0 L~2000 1000 3000 4000 5000 4 I I I DUO:[301 ,1]04722 , 07-OCT-93, 08:41:19 S1 M s s : 4 1 2 . 6 - 4 1 3 . 5 , Sns: 1.10032, Max: 9 7 9 , r T 1 IO0 I 00 b 2 3000 -: , 1 I 1. ' I I. .I 4000 5000 6000 C Max: , I I 1 8000 7000 I- 8000 979, RT: 0 . 0 , 1 .* 1 ' 1 ' . ' . ' I ', I 7000 8000 1ib1 -I--~ 9000 204.0 I ,1 11r1 0000 .'. . BACK TO MAIN DUO:[301D1]D4723, , 07-OCT-93, 12:07:58 1S1 M s s : 498.6-499.5, S n s : 1 - 1 0 0 3 3 , M a x : 722, C Max: 722, RT: 0.0, 204.0 JI4 P 1000 2000 3000 4000 6 DUO:[301,1]D4723, , 07-OCT-93, 12:07:58 S1 M s s : 4 1 2 . 6 - 4 1 3 . 5 , S n s : 1 - 1 0 0 3 3 , M a x : 00 378, 6000 C Max: 7000 378, RT: 8000 0.0, 9000 204.0 1000 2000 3000 11 -, 5 -;. , F-1- , , , -., ~ 4000 100 6000 7000 8000 ,.; , , , , rl 9000 .. BACK TO MAIN DUO:[301,1]04724, , 07-OCT-93, 15~33121 S1 M s s : 4 9 8 . 6 - 4 9 9 . 5 , Sns: 1 - 1 0 0 3 3 , Max: 1 0 , C Max: 1 0 , RT: 0 . 0 , 2 0 4 . 0 1 1 S 1 M s s : 4 1 2 . 6 - 4 1 3 . 5 , S n s : 1 - 1 0 0 3 3 , M a x : 7 , C M a x : 7 , R T : 0 . 0 , 2 0 4 . 0 1 Ill II Ill I IIlII L 1""1""1""1""1""1""l""l""l""l 1000 2000 3000 4000 5000 6000 7000 8000 9000 ... . BACK TO MAIN 1D U 0 : [ 3 0 1 , 1 ] 0 4 7 2 5 , , 0 7 - O C T - 9 3 , 2 0 : 5 5 : 5 0 Q1 M s s : 4 9 8 . 6 - 4 9 9 . 5 , Sns: 1 - 6 6 5 6 , Max: 3 0 2 , C M a x : 3 0 2 , RT: 0 . 0 , 0 . 0 - - 1 - I I I"'"""I""""'1""""'1""""'l""""'l""" 1000 2000 3000 DUO:[301,1]D4725, , 07-OCT-93,2 0 : 5 5 : 5 0 4000 5000 - - 6000 1000 2000 3000 4000 5000 6000 .. ,* DUO:[301,1]D4726, , 08-OCT-93, 11:31:13 BACK TO MAIN 1000 2000 3000 DUO:[301,1]D4726, , OB-OCT-93, 11:31:13 4000 5000 1000 2000 3000 4000 5000 I I BACK TO MAIN DlJ0:(301,1]04727, , 08-OCT-93, 1 3 ~ 3 1 ~ 3 1 S1 M s s : 4 9 8 . 6 - 4 9 9 . 5 , Sns: 1 - 6 0 0 8 , Max: 5 9 4 , C Max: 5 9 4 , RT: 0 . 0 , 122.2 II S1 M s s : 4 1 2 . 6 - 4 1 3 . 5 , S n s : 1 - 6 0 0 8 , Max: 2 4 1 , C Max: 2 4 1 , RT: 0 . 0 . 1 2 2 . 2 HI BACK TO MAIN Vapor Pressure Measurements of FC95 and FC143 Experiment #3 Introduction This is a continuation of a series of experiments designed to obtain measurements of the vapor pressures of FC95 and FC143. This is the third experiment in this series. A second experiment was run prior to this experiment, but a solution was accidently used in the impingers that had been spiked with 10ppm FC95 and 10 ppm FC143. The intent of this experiment is to measure the vapor pressure of these two compounds at 90 C. The apperatus use in this experiment was described in a report entitled Imninner Studiese f u of FC143. which is filed in the LIRN system under L3306. Results and Discussion During this experiment, a l-pmpanokwater (5050) solution containing 500 ppm ammonium acetate was used in the impingers to catch any volatilized fluorochemicals. This solution was used to be consistant with the f i t experimentfor measuring the vapor pressures of FC95 and FC143 at room temperature. FC143 was found in all three impingers of both trains, indicating that FC143 has a measureable vapor pressure at 90 C. It also indicates that the solution used in the impinger trains is not efficientat catching fluorochemicalsin the air that passes through them at the flow rates that were used in this experiment, The vapor pressure of FC95 at 90 C measured much lower than the vapor pressure of FC143 in this experiment, but it does appear that FC95 has a measureable vapor pressure at this temperature. The amount of FC95 measured in the fEst impinger of both trains was higher than any of the reagant or impinger blanks. The values measured for the amounts of FC95 in the blank impingers were subtracted from the values measured for the amounts of FC95 in the impingers after the warm air had been bubbled through them before the vapor pressure calculations were performed. The raw data and integrated data are shown in the following pages. The results of this experimentare given below. These results are minimum vapor pressures for the two compounds at 90 C, since it appears that the impinger trains did not catch all of the fluorochemicals that had been volatilized. FC95 FC143 1.2-10-~ton 1.140" torr BACK TO MAIN Vapor Pressure Calculations Total amount of fluorochemicals found in the impinger trains : FC95 Impinger train #1 (0.05 15+0.02* 18+0.01* 7)=1.2 Ug C, 7 s 6'j 0.3'&) O . O I A A S + Impinger train #2 (0.02* 9+0.02* 16 0.00 8)=0.5 Ug d,ltA> O * i < . q FC143 Average = 0.8 ug - Impinger train #1 (1.43 15+0.92* 18 + 2.34-7)= 54.4 U g Eq. 1A Eq. 1B Eq. 2A Impinger train #2 (0.95-9+2.00-16+1.91*8)= 55.8 Ug Eq. 2B Average = 55.1 ug Using the average values measured for the number of grams of Fc95 and FC143 The number of moles of FC95 and FC143 : FC95 0.840" g = 1.5-10-'mol Eq. 3 538 g I mol FC143 55.1*104 g 431 g l mol = 1.3.10" Eq. 4 Assuming the air behaves as a mixture of ideal gases and the air is at standard pressure, the number of moles of air molecules in 280 liters of air at 20 *C is: 280 liters 273 K (22.414liters I mol) . 363 K =9.39mol Eq. 5 'Ihe following quation then gives the minimum vapor pressure the fluorochemical salts must have to be measured by this experiment : FC95 FC143 Eq. 7 BACK TO MAIN Di.mri W o k 3MEnvironmcntal Dear Dr. WaItcr: Par&I: Volatilization of fluorochemicals from some aqueous solutions With the vapor pressureswhich FC95 and FC143are W y tohave, it is difficult to believe . that thcse salts would be removed by air passing through solutions except by two mechiflllsms The first is entrainment where microdropletsofwater could carry ma!uial out of solution. A second mechanism would be appropriate in cases whaethe fluomchemical is dissolved in an aqueous solution containingmfktant. At mrfktant concentrations near or even below the CMC (critical micelle concentration) the passage of ah through the solution should lead to an appreciable production of foam bubbles. A number of pmceses involve foam fractionation to remove dissolved materials from solution and I believe that it is certainly possible in the present case with sufacMat solutions (e.g., 500 ppm of =AB, cetyltrimethyl- ammonium bromide) to extract FC95 andor FC143 under the conditions of these experiments. Part II: Gas satwation attempt to measure vapor pressures of solid FC95 and FC143 Based on a minimum detection level, the Mpor pressure calculations seem appropriate (except for a trivial question about molecular weights: FC143 seems to have an ammonium counterion and FC95 seems to have a potassium counterion?). The calculated vapor pressures are semi-plausible but I don't thinkthat the experimentalconditionsprovide firm evidence that the numbers are reasonable. A crucial point in the gas Saturation method is the a!!ainmmt of vapor equilibrium with the flowing gas. With no detectable signal, one does not have a handle on thisquestion. In the general sense,it would be highly desirable tohave a reference substance with known vapor pressure done in a similar experiment. From the brief literatwe reading which I have done, it appears that the gas Saturation method is not recommended far demxhtion of vapor prtssurts below a few millitom. Knudsen effusionmight be employed in the case of very low vapor presmu. Since these fluomchemicals are very stable, a possible alternative procedure would be to repeat the gas Saanation eXperiment at substantially higher tmpmtum such as 100 to 150deg. C,for example. Finding measllrable signals in such a range should enable extrapolation to a mom temperature vapor pnssute. sin-Iy yours, E d h E. Tuck, Ph. D. Chemistry Departmeat-University of Olclahoma Norman,OK 73019 Td. (405) 325-2054; F ~ x(405) 325-6111 0 6 1 Is/zootr t N V m N l A L LA6(3RAIUHY ARCHIVED FINAL REPORT 1BACK TO MAIN LAB REQUEST NO. L3306 REQUESTOR NAME: JW DEPARTMENT: 0222 PROJECT NO: 0 6 DATE RECEIVED: 12/13/1993 DESC: VOLATILITY OF FC95 AND FC143 CONTRACT M ( S ) : EXP COMP DATE: 12/17/1993 DATE COMPLETED: 12/15/1993 PRWECT LEAD: PHONE NO: 3M FAX NO: 651-778-6176 Iapinger study I . JTW-SPEC SPECIAL STUDY - JTW COMPLETE