WSRC-R P-93-768 ITP Filter Particulate Decontamination Measurement by L. 0. Dworjanyn Westinghouse Savannah River Company Savannah River Site Aiken, South Carolina 29808 DOE Contract No. DE-AC09-89SR18035 This paper was prepared in connection with work done under the above contract number with the U. S. Department of Energy. By acceptance of this paper, the publisher and/or recipient acknowledges the U. S. Government's right to retain a nonexclusive, royalty-free license in and to any copyright covering this paper, along with the right to reproduce and to authorize others to reproduce all or part of the copyrighted paper. ,
by L. 0. Dworjanyn Westinghouse Savannah River Company Savannah River Site Aiken, South Carolina 29808
DOE Contract No. DE-AC09-89SR18035
This paper was prepared in connection with work done under the above contract number with the U. S. Department of Energy. By acceptance of this paper, the publisher and/or recipient acknowledges the U. S. Government's right to retain a nonexclusive, royalty-free license in and to any copyright covering this paper, along with the right to reproduce and to authorize others to reproduce all or part of the copyrighted paper. ,
DISCLAIMER
This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.
This report has been reproduced directly from the best available copy.
Available to DOE and DOE contractors from the Office of Scientific and Technical Information, P. 0. Box 62, Oak Ridge, TN 37831; prices available from (423) 576-8401.
Available to the public from the National Technical Information Service, U. S . Department of Commerce, 5285 Port Royal Road, Springfield, VA 22161.
Portions of this document may be illegible in electronic image products. Images are produced from the best available original document.
DISCLAIMER
Y v.
a O B 0 4 I
WESTINGHOUSE SAVANNAH RIVER COMPANY SAVANNAH RIVER TECHNOLOGY CENTER
TO : W.L. TAMOSAITIS, 773-A
FROM: L.O. DWORJANYN, 779-2A
Keywords: Decon tamina t ion 42~EE-17~ F i l t r a t i o n F t m Crossflow ITP C e s i u m
May 21, 1993
cc: B.G. Crol ley, 241-121H ;,g-CR. Brooke, 241-121H - W.B. V a n P e l t , 241-152H E.W. H o l t z s c h e i t e r , 773-A L . F . Landon, 676-1T S.D. F ink , 773-A W.E. S t e v e n s , 773-A D . D . Walker, 773-A M . J . Barnes , 773-A J . F . McGlynn, 773-A D . B . Burns, 676-1T SRTC Records, 773-A (4)
SUMMARY
A new t e s t method w a s deve loped which showed t h e i n s t a l l e d In-Tank P r e c i p i t a t i o n F i l t e r U n i t #3 p r o v i d e d a t l ea s t 4 0 , 0 0 0 ~ d e c o n t a m i n a t i o n o f t h e p r e c i p i t a t e d p o t a s s i u m t e t r a p h e n y l borate (KTPB) d u r i n g t h e cold chemica l r u n s . T h i s f i l t e r i s expected t o
m e e t t h e needed 4 0 , 0 0 0 ~ hot cesium d e c o n t a m i n a t i o n r e q u i r e m e n t s , assuming t h a t t h e ces ium p r e c i p i t a t e , CsTPB, behaves t h e s a m e as KTPB.
The new method p e r m i t s cold chemica l s f i e l d t e s t i n g of i n s t a l l e d f i l t e r s t o q u a n t i f y p a r t i c u l a t e d e c o n t a m i n a t i o n and v e r i f y f i l t e r i n t e g r i t y b e f o r e going h o t . The method involves a 1OOOx
WSRC-RP-93-768 Page 2 May 21, 1993
c o n c e n t r a t i o n of f i n e p a r t i c u l a t e KTPB i n t h e f i l t r a t e t o a l l o w direct a n a l y s i s by c o u n t i n g f o r n a t u r a l k y radioactive isotope K - 4 0 u s i n g t h e underground SRTC gamma s p e c t r o s c o p y f a c i l i t y . . The p a r t i c u l a t e c o n c e n t r a t i o n w a s accomplished by u l t r a f i l t r a t i o n a t Rhone-Poulenc, N J , u s i n g a small cross-flow bench f a c i l i t y , followed b y c o l l e c t i o n of a l l suspended s o l i d s on a small f i l t e r disc for K a n a l y s i s .
INTRODUCTION
The main f u n c t i o n f o r I n Tank P r e c i p i t a t i o n ( I T P ) f i l t e r s i s t h e removal of f i n e precipitated ces ium t e t r a p h e n y l borate. E a r l i e r d e m o n s t r a t i o n i n Tank 48 has shown t h a t t h e f i l t e r e d s a l t s o l u t i o n can be d e c o n t a m i n a t e d from ces ium b y a factor of 40,000 ( R e f . 1 ) . T h i s permits local sa l t disposal as a C l a s s A sal tcrete . The d e c o n t a m i n a t i o n factor (DF) i s a f u n c t i o n of CsTPB s o l u b i l i t y and removal of precipitated CsTPB. The s o l u b i l i t y of ces ium sa l t i n ITP sodium sa l t s o l u t i o n s has been established ( R e f . 2 ) , as shown
CsTPB = ‘ 0 .000032 e x p ( -0 .67 [ N a ] ) m o l / l i t e r a t 2OoC
a n d c o n f i r m e d i n Tank 4 8 p r e c i p i t a t i o n d e m o n s t r a t i o n .
To achieve t h e ces ium D F goal w e must also a s s u r e t h a t the i n s t a l l e d ITP f i l t e r s have n o c r a c k s o r l e a k s a n d provide a p a r t i c u l a t e DF a t least 40,000, assuming negl ig ib le s o l u b l e ces ium. A special C r o s s - f l o w T e s t F a c i l i t y w a s b u i l t a t TNX (Ref. 3) t o test t h e m e c h a n i c a l i n t e g r i t y and p a r t i c u l a t e d e c o n t a m i n a t i o n of new f i l t e r s as t h e y are received a t SRS. However cold chemical I T P f i l t r a t i o n tests s tar ted before t h e T e s t F a c i l i t y w a s complete. T h i s n e c e s s i t a t e d a n a l t e r n a t e approach t o demonstrate p a r t i c u l a t e DF as par t of t h e p l a n t tes ts . This can
‘ be done b y measu r ing the c o n c e n t r a t i o n s of p a r t i c u l a t e p o t a s s i u m t e t r a p h e n y l borate (KTPB) u s e d d u r i n g t h e cold chemicals t es t r u n s s i n c e KTPB behaves s i m i l a r l y t o ces ium fo rming a f i n e 0 .5 micron prec ip i ta te . The r a t i o of s o l i d KTPB i n t h e f e e d s l u r r y over p a r t i c u l a t e KTPB i n the f i l t r a t e d e f i n e s p a r t i c u l a t e D F .
DISCUSSION
Cold Chemical Testina of ITP Fi l t ers
The cold c h e m i c a l tests w e r e conduc ted u s i n g a n “average” h y d r o x i d e / n i t r a t e s a l t c o m p o s i t i o n (Ref 4 ) . The i n i t i a l c o n c e n t r a t i o n w a s a p p r o x i m a t e l y 5 M sodium and t h e s l u r r y c o n t a i n e d 1 . 5 w t % precipi ta ted KTPB. Dur ing t h e t e s t i n g a d d i t i o n a l NaTPB a n d p o t a s s i u m sal ts w e r e added t o i n c r e a s e t h e i n s o l u b l e sol ids t o 4 w t % a n d t h e n t o 10 w t % . Based on a c t u a l a n a l y s e s ( R e f 5 ) t h e f i n a l c o n c e n t r a t i o n w a s 8 . 3 8 w t % s o l i d s c o n s i s t i n g of 6 7 . 7 2 KTPB a n d 32 .3% NaTPB. The observed f i l t e r f l u x ra te i s shown i n
WSRC-RP-93-768 Page 3 May 21, 1 9 9 3
F i g u r e 1, showing a l o g a r i t h m i c c o n c e n t r a t i o n .
Cesium was n o t i n c l u d e d i n t h e s e s l o w p r e c i p i t a t i o n e q u i l i b r i u m ( R e f 6 ) . S i n c e s i m i l a r l y t o c e s i u m and f o r m s a s imilar TPB u s e d fo r a s s e s s i n g f i l t e r p a r t i c u l a t e D F . Po ta s s ium i s n o r m a l l y p r e s e n t i n waste s o l u t i o n s a t a c o n c e n t r a t i o n l O O x ce s ium.
P a r t i c u l a t e D F measurements w e r e made on t h e 8 . 3 8 w t % s l u r r y a n d I T P f i l t r a t e from t h a t s l u r r y . T h i s allows h i g h e s t s e n s i t i v i t y fo r d e t e c t i n g so l id s i n t h e f i l t r a t e .
ent Re-
To estimate p a r t i c u l a t e d e c o n t a m i n a t i o n w e must know the i n s o l u b l e KTPB c o n c e n t r a t i o n i n t h e s l u r r y a n d t h e i n s o l u b l e ( p a r t i c u l a t e ) KTPB c o n c e n t r a t i o n i n t h e f i l t r a t e . High sol ids c o n c e n t r a t i o n , greater t h a n 1 w t % c a n be o b t a i n e d by d i f f e r e n c e between t o t a l KTPB a n d f i l t r a t e KTPB ( R e f 7 ) . For t h e t es t s l u r r y t h e p o t a s s i u m c o n c e n t r a t i o n w a s c a l c u l a t e d a t 5 .67 w t % KTPB o r 63 .5 g / l (Appendix E ) . T h e goal f o r 40,000 p a r t i c u l a t e D F is 63500/40,000 = 1 . 6 mg i n s o l u b l e KTPB per l i t e r of f i l t r a t e (0 .17 m g K / l J .
The s o l u b i l i t y o f KTPB i n s a l t s o l u t i o n s i s a f u n c t i o n of sa l t c o n c e n t r a t i o n a n d t e m p e r a t u r e and c a n v a r y be tween 3 and 1 2 m g / l w i t h i n ITP t e s t i n g p r o f i l e , Table 1 ( R e f 8 ) . Dur ing t h e I T P tes ts as t h e so l ids c o n c e n t r a t i o n w a s i n c r e a s e d t h e s o l u t i o n c o n c e n t r a t i o n decreased f r o m 5 M sodium t o a b o u t 3 M sodium due t o d i l u t i o n b y added i n g r e d i e n t s . A measure of t o t a l p o t a s s i u m i n t h e f i l t r a t e o r i n s o l u t i o n would provide l i t t l e g u i d a n c e t o i n s o l u b l e KTPB.
The h i g h s o l u b i l i t y of KTPB makes it a l s o impract ical t o wash any f i l t e r e d precipi ta te . KTPB i s s i g n i f i c a n t l y m o r e s o l u b l e i n p u r e water, a b o u t 60 mg/l, t h a n i n s a l t s o l u t i o n s . S a t u r a t e d w a s h s o l u t i o n c o u l d be u s e d b u t t h i s would r u n t h e r i s k of i n t r o d u c i n g p o t a s s i u m t o t h e prec ip i ta te , p a r t i c u l a r l y s i n c e KTPB c a n r e c r y s t a l l i z e a t l o w e r t e m p e r a t u r e .
I n i t i a l l y three samples w e r e p r e p a r e d by s p i k i n g a n o m i n a l l y c l e a n ITP f i l t r a t e (Sample Ox) w i t h lox KTPB, e q u i v a l e n t t o 4000DF, and lOOx KTPB, e q u i v a l e n t t o 400 DF ( R e f 9 ) . The s p i k e d samples were used f o r e v a l u a t i n g d i f f e r e n t methods f o r KTPB a n a l y s i s , Appendix A .
Scanning Electron Microscopy, showed a w e l l d e f i n e d c r y s t a l l i n e KTPB s t r u c t u r e w i t h a nar row c r y s t a l s i z e d i s t r i b u t i o n , 0 . 2 t o 1 micron, F i g u r e 2 . One d r o p of lOOx sample
WSRC-RP - 9 3- 7 68 Page 4 May 2 1 , 1993
w a s f i l t e r e d a n d washed w i t h two drops of water. A t l ower m a g n i f i c a t i o n s c l u s t e r s of C r y s t a l s W e r e c l e a r l y v i s i b l e , F i g 3A, and t h e y were v i s ib l e i n t h e a c t u a l f i l t r a t e s u s p e n s i o n u s i n g optical microscopy, F i g 3 B . O p t i c a l v i e w i n g u n d e r a cover glass allow t h e o n l y t r u e o b s e r v a t i o n of a f i l t r a t e w i t h o u t f i l t e r i n g , washing o r d r y i n g . However, t he 0 . 5 micron p a r t i c l e s i z e i s a t t h e l i m i t of opt ical r e s o l u t i o n and w e w e r e n o t able t o f i n d any t e c h n i q u e t o a c c e n t u a t e the KTPB c r y s t a l s , e.g. w i t h back l i g h t i n g o r crossed polaroids. KTPB c l u s t e r s w e r e r e a d i l y i d e n t i f i a b l e i n t h e l o x samples, b u t none w e r e found i n t h e u n s p i k e d f i l t r a t e i n d i c a t i n g v i s u a l l y a t least 4000 D F .
An attempt t o observe KTPB c r y s t a l s by Transmission Electron Microscopy us ing l i q u i d sample membrane w a s n o t s u c c e s s f u l p r o b a b l y b e c a u s e t he membrane allows e v a p o r a t i o n u n d e r vacuum r e s u l t i n g i n s a l t c r y s t a l l i z a t i o n a t t h e s u r f a c e .
Particle Size Analysis offers a p o t e n t i a l tool b u t m e a n i n g f u l r e s u l t s c o u l d no t be o b t a i n e d w i t h the SRTC laser a n a l y z e r . H o w e v e r e x c e l l e n t r e s u l t s were o b t a i n e d u s i n g Lab-Tec a n a l y z e r a t Lockheed Env i ronmen ta l , F i g 4 , showing a u n i f o r m d i s t r i b u t i o n of c l u s t e r s u p t o 60 mic rons a n d a s i g n i f i c a n t c o n c e n t r a t i o n of par t ic les b e l o w 0 . 7 m i c r o n s . S i m i l a r d i s t r i b u t i o n w a s found i n t h e l o x sample. The Ox f i l t r a t e a l so showed a d i s t r i b u t i o n i n d i c a t i n g possible KTPB i n t h e f i l t r a t e . Subsequent SEM e x a m i n a t i o n of t h e Ox f i l t r a t e ref i l tered on 0.2p f i l ter medium showed a v a r i e t y of " junk" s u c h as M g , Al, S i , Ca , C r , Fe, N i , p o s s i b l y e x p l a i n i n g t he s i z e d i s t r i b u t i o n i n t he Ox sample. The Lab-Tech i n s t r u m e n t w a s n o t able t o provide a measure of particle c o n c e n t r a t i o n . T h i s would have a l l o w e d t o d i f f e r e n t i a t e q u a n t i t a t i v e l y between t h e s p i k e d samples.
ICP Mass Spectrometry would have b e e n applicable a n d u s e f u l fo r a n a l y s i s of s m a l l c o n c e n t r a t i o n s i n t he p r e s e n c e of high levels of sodium, however, t h e i n s t r u m e n t is set up w i t h a r g o n carrier gas, MW 4 0 , and t h i s i s too close for effect ive s e p a r a t i o n of po ta s s ium, MW 39 . Ce,sium a t MW 4 5 can be a n a l y z e d r e a d i l y even a t much lower c o n c e n t r a t i o n s t h a n p o t a s s i u m .
Neutron Activation w a s t r i e d a t ORNL b u t t h e sodium a c t i v i t y overshadowed t h e po ta s s ium. ' P a r t i c u l a t e p o t a s s i u m on a f i l t e r p a p e r may be a n a l y z a b l e b u t t h i s w a s n o t t r i ed .
Solid State Track Recording allows t h e o b s e r v a t i o n of b o r o n i n KTPB and NaTPB . C r y s t a l l i n e boron w i l l p roduce c l u s t e r e d t racks w h i l e t h e bo ron i n s o l u t i o n p r o d u c e s random t r a c k s , a l l o w i n g t h e c r y s t a l s t o be c o u n t e d (Appendix B ) . I n i t i a l r e s u l t s f r o m S&T C e n t e r were p r o m i s i n g b u t n o t d e f i n i t i v e . T h i s method c o u l d be developed i f n e c e s s a r y t o s u p p l a n t d i rect K-40 c o u n t i n g .
O t h e r t e c h n i q u e s were c o n s i d e r e d a n d rejected. P r o m p t Gamma a c t i v a t i o n a t S & T C e n t e r r e q u i r e s a large volume of s o l u t i o n and
WSRC-RP-93-768 Page 5 May 21 , 1 9 9 3
s i g n i f i c a n t set up t i m e . I t w a s n o t c lear t h a t p o t a s s i u m c o u l d be i d e n t i f i e d i n h i g h c o n c e n t r a t i o n of sodium. Ion Exchange c o u l d be u s e d t o take up i o n i c po ta s s ium, b u t it was u n l i k e l y t h a t t h e i n s o l u b l e p o t a s s i u m would adsorb on t h e column.
N a t u r a l p o t a s s i u m c o n t a i n s 0.00118% radioactive K-40 which releases 11% of i t s gamma i n t e n s i t y a t 1460 K e V . T h i s can be c o u n t e d d i r e c t l y by Low-Level Gamma Spectrometry. The ETS Underground Coun t ing F a c i l i t y c a n detect K-40 levels down t o 1 p C i , o r a b o u t 1 m g n a t u r a l p o t a s s i u m . S c o u t i n g tests u s i n g 100 m l of 1 O O x s p i k e d l i q u i d sample showed a m e a s u r a b l e K-40 c o n c e n t r a t i o n , i n d i c a t i n g t h a t 10 l i t e rs of lx (40,000 DF) l i q u i d sample would have a m e a s u r a b l e amount of p o t a s s i u m , provided tha t t h e volume c o u l d be r e d u c e d one hundred f o l d t o 100 m l or less w i t h o u t d e s t r o y i n g t h e p a r t i c u l a t e KTPB. w a s calibrated w i t h known KTPB s l u r r y a n d weighed KC1 (Appendix C) .
The c o u n t i n g geometry
Earl ier c o n t a c t s w i t h Rhone Pou lenc t o f i n d a l t e r n a t e f i l t r a t i o n s y s t e m s f o r l a te washing have i d e n t i f i e d a compact bench scale cross-flow f i l t r a t i o n u n i t , Appendix D . The u n i t s are d e s i g n e d t o c i r c u l a t e as l i t t l e as 100 m l of s o l u t i o n . The f i l t e r medium i s a t h i n l a y e r of Z r 0 2 / T i O 2 on p o r o u s c a r b o n a n d poros i ty i s avai lable f r o m 0 . 4 5 micron down t o 0 . 0 8 micron a n d lower fo r biological f i l t r a t i o n .
For D F measurement f o u r g a l l o n s of ITP f i l t r a t e sample (SIM-386) w a s d e c a n t e d b y s i p h o n i n g of f 15 l i ters fo r c o n c e n t r a t i o n a t Rhone-Poulenc. The bottom 780 m l c o n t a i n e d a l i g h t white precipitate a n d w a s k e p t s e p a r a t e l y f o r a n a l y s i s . The 15 l i t e r sample w a s t h e n " c o n c e n t r a t e d " t o a b o u t 100 m l a t Rhone Pou lenc b y r e f i l t e r i n g w i t h 0 . 1 4 micron C a r b o s e p o membranes. The f i l t e r w a s t h e n r i n s e d w i t h water for separate p o t a s s i u m a n a l y s i s . P a r t i c u l a t e solids f r o m a l l t h r e e samples (sample bottoms, c o n c e n t r a t e , a n d r i n s e w a t e r ) w e r e collected on separate 0 . 2 micron Mil l ipore f l u o r o c a r b o n f i l t e r s a n d c o u n t e d together f o r K-40. The t o t a l p o t a s s i u m w a s less t h a n 2 mg, i n d i c a t i n g a p a r t i c u l a t e DF >40,000.
\
E a r l i e r o b s e r v a t i o n s have shown t h a t a f i n e precipi ta te o f t e n appears i n r e t a i n e d f i l t r a t e samples . T h i s w a s a n a l y z e d e a r l i e r t o be a n aluminum s i l i ca t e . A s m a l l amount of f i n e precipi ta te w a s p r e s e n t i n most ITP r e t a i n e d samples i n c l u d i n g t h e 4 gal sample u s e d for D F measurement . I n t h i s case a n y precipi ta ted KTPB w a s less t h a n 2 m g K . However as the sample t e m p e r a t u r e d r o p s KTPB c a n be precipi ta ted. About 40 m l w a s s i p h o n e d o u t f r o m t h e bottom of 1 g a l l o n S I M 379 r e t a i n e d f i l t r a t e . 20 m l w a s
WSRC-RP- 9 3 - 7 68 Page 6 May 2 1 , 1993
f i l t e r e d a n d r e s u l t e d i n 25 m g unwashed s o l i d s . Another 20 m l w a s f i l t e r ed a n d washed three t i m e s w i t h 20iml water e a c h t i m e . The r e s i d u a l d r y solids w a s r educed t o 3.5 m g and examined unde r SEM showing a mass o f potassium c r y s t a l s , F i g 7 . Some o f t h e KTPB c r y s t a l s w e r e e x c e p t i o n a l l y large, greater t h a n 10 microns , i n d i c a t i o n a s l o w c r y s t a l l i z a t i o n d u r i n g sample a g i n g a t r e d u c e d t e m p e r a t u r e . However aluminum and s i l i c o n were also observed c o n f i r m i n g ear l ier a n a l y s e s . .
B'ternative Membrane IntecrritY T P W
Commercial t e c h n i q u e s are a v a i l a b l e for t e s t i n g t h e i n t e g r i t y of f i l t e r e l e m e n t s , seals and c o n n e c t i o n s , Ref 10 . These methods r e q u i r e no precipitate and r e l y on "bubb le p o i n t " f o r m a t i o n or d i f f u s i o n t e s t i n g . These tes ts can be specified for a c c e p t a n c e of new f i l t e rs . - Solids concentration offers a s i m p l e a n d u s e f u l t e c h n i q u e fo r a n a l y s i s of i n s o l u b l e r e s i d u e s . Direct we igh ing of t h e collected solids c a n provide a g u i d e t o the c o n c e n t r a t i o n of i n s o l u b l e so l ids . C o n v e n t i o n a l chemica l a n a l y s e s c a n t h e n be u s e d much m o r e e f f e c t i v e l y s i n c e m o s t of t h e s o l u b l e m a t r i x s o l u t i o n h a s been removed. It may a l so be p o s s i b l e t o develop q u i c k cold r i n s i n g t o wash o f f t he s o l u b l e sa l ts a n d p r o v i d e a more q u a n t i t a t i v e measure of r e t a i n e d solids.
REFERENCES
1. Memorandum, E . B . S n e l l a n d C . J . Heng t o O.M. Morriss, "Sal t Decon tamina t ion Demons t r a t ion Resul t s" , DPSP 83-17-8, 6/20/83.
2. L.M. L e e and L . L . K i l p a t r i c k , "A P r e c i p i t a t i o n Process f o r S u p e r n a t e Decontaminat ion" , DP-1636, 11/1982.
3 . L . L . K i l p a t r i c k , Job P l a n 678-T-91-8-1, 9/09/92.
4 . D . D . Walker a n d G . K . Georgeton " V i s c o s i t y a n d D e n s i t y of S i m u l a t e d Sa l t S o l u t i o n s " WSRC-RP-89-1088, 10/19/89.
5 . E - M a i l , D . B . McCabe t o L.O. Dworjanyn, 3/3/93.
6. E - M a i l , L . L . K i l p a t r i c k t o D . F . Brown e t a l . , 4/9/92.
7 . E.W. Banwann t o W.A. Spence r , " D e t e r m i n a t i o n of T e t r a p h e n y l Borate by P o t e n t h o u r e t r i c T i t r a t i o n w i t h S i l v e r N i t r a t e " , DPST- 86-845, 12/3/86.
WSRC-RP-93-768 Page 7 May 2 1 , 1993
8 . L.O. Dworjanyn, "Review of T e t r a p h e n y l Borate S o l u b i l i t i e s i 1 , WSRC-RP-93-1001 t o be issued.
9. M . J . Barnes , Resea rch Notebook - WSRC-NP-90-161, pages 113 t o 115, 11/11/92.
10. Millipore D i r e c t Catalog, 1991-1992, pages 1 0 t o 11.
=,i- r f i Jr i I r-ci; Fl F i-.TF ,: .,-, i -S,z*r- ; 3 , fi&7J;:.,e:; = 0
I 1 v..
! \ I ii I ! ........... i i
. i i
4 I j : i i
: i i
. I : i
....................... i ................... :.... i : i I ! . I
....................... : ...................... : ... i : i ; !
: 1
I!.. .. ................................................................................................ I
i . . i !
I 1
I . i
.... : I
1 - 1 8-
i . . . . . . . .......................................................................
I ; .!
. . : I !i 1 1 : i
. . . . . .
Microprobe Analysis
Techniques for Potassium Measurement
Analytical Method Capability Comments Direct K40 Activity Direct Potassium measurement Detect lOOX sample
Bill Winn, ET 725-2057 Need 1 OOX concentration Neutron Activation of filter paper w/ppt K, Cs Direct K measurement in Na matrix not
Paul Cloessner/Marti Finney, A D S 725-2 198/9656 possible. Unwashed K particulates on filter Larry Robinson, ORNL (615) 574-4912 paper: Na still too high.
Identify Boron Crystals Direct B crystal count not effective. Frank Ruddy, S&TC (412) 256-1064 Need ppte on filter paper.
Observation of particulates OM filter paper K particles observed in 1OX and lOOX Dan Steedly, ADS 725-2324 spiked samples. None in ITP filtrate.
Liquid sample observation and count. K agglomerates observed in 1OX and Cliff Carlson, ET 725-54 16 lOOX spiked samples.
Argon carrier gas interferes with No Cs in cold feed Justin Halverson, ET potassium measurement. 5-9625 Needs development
Liquid sample observation Potassium masked by sodium salt Mike Tosten, MT 725-6230 crystallization.
Accurate Cs and K determination SRTC instrument not available for at least six months
Not effective on particulate,
High setup and development
Works directly on 1OX to lOOX filtrate. Cannot distinguish from filtrate "trash". Unable to interpret optical data.
Requires filter relocation to TNX, or equipment setup in ITP Area.
Solid State Track Recording of paper
Scanning Electron Microscopy
Optical Microscopy
ICP Mass Spectrometry
Transmission Electron Microscopy
Fourier Mass Spectrometery Bob Weller, ET 725-95 57 Michelle Buchannan, ORNL (61 5) 574-4868
Analytical after IX on column Chuck Coleman, ADS needs development.
Prompt Gamma Neutron Activation Frank Ruddy, S&TC
Particle size analysis John Domenech, Lockheed Env.
Laser Particle Size Analysis Jane Bibler
TNX Leak Test Lester Kilpatrick
Selective adsorption and analysis
Used for soil analysis. Need large volume eg. 2 m3 soil Size analysis without dilution (702) 36 1-0740 Particle size distribution > 1 pm
Particulate K in filtrate
Dwojanyn E:WWTPVTP-DF.DOC
APPENDIX B
RESULTS OF KTBP ANALYSIS USING SOLID STATE TRACK RECORDERS
F. H. Ruddy (W) STC (412) 256-1064
In December of 1992, i n i t i a l measurements were conducted t o develop The method a new method f o r analysis of potassium precipi ta ted as KTBP.
is based on assay of boron i n KTBP using the following reast ion:
4 'OB + n + 'Li + He
The energe t ic 4He nucleus (alpha pa r t i c l e ) produced can be detected by means of a Sol id S t a t e Track Recorder (SSTR). CR-39 polymer SSTRs are sens i t i ve t o alpha p a r t i c l e s such as those produced i n t h e above react ion, and can therefore be used t o de tec t boron ( B) or t o de tec t KTBP v i a its boron content.
10
Three so lu t ions were supplied, labeled as follows:
(1) OOX f i l t r a t e 0.4 ppm KTBP 1.17 g/cc NaN03, NaOH
(2) 1OX f i l t r a t e 4 ppm KTBP 1.17 g/cc NaN03, NaOH
(3) lOOX F i l t r a t e 40 ppm KTBP 1.17 g/cc NaN03, NaOH
CR-39 polymer SSTR s t r i p s with approximate dimensions 1 c m x 1 c m x O . l c m were imersed i n each of the three solut ions and a Rblankn solut ion made a t STC, which contained a solut ion made by mixing two p a r t s water with one p a r t 6N NaOH solut ion. After t h e SSTRs were placed i n the v i a l s , t he solut ipns were ag i ta ted , and then allowed t o s e t t l e i n a posi t ion t h a t would allow p a r t i c l e s t o come t o r e s t on t he SSTR top surface. polyethylene-walled thermalization cavity and bombarded with neutrons or ig ina t ing from a 14 MeV D-T neutron generator. i r r ad ia t ed for a t o t a l of 2500 seconds a t the f u l l neutron generator
A l l four s o l u t i o n bo t t l e s were positioned ins ide of a
The samples were
8 power of 1 x 10 f h e n c e within the thermalizing cavity was measured using 235U SSTRs.
neutrons per second. The resu l t ing thermal neutron
After the neutron i r r ad ia t ion , the CR-39 polymer SSTRs were etched with 6N NaOH f o r 2 hours a t 70' C t o develop the alpha t racks produced by neutron react ions i n boron. with an op t i ca l microscope t o determine the number of alpha p a r t i c l e s present. correlated c lus t e r s of two or more t racks were counted. The c lus t e r s . correspond t o concentrated boron i n precipi ta ted form.
The SSTRs were then manually scanned
Because boron is expected t o be present i n solut ion, only
For so lu t ion (3), a t o t a l of 41 c l u s t e r s were observed i n an SSTR 2 area of 0.55 cm , and for solut ion (l), 5 c lus t e r s were found i n an area
of 0.52 cm . Although the t rack dens i t ies , 74.5+11.6 - and 9.6+4.3, - respect ively, a r e not inconsis tent with the expected KPTB amounts present, the method lacks su f f i c i en t s e n s i t i v i t y as presently applied.
2
The s e n s i t i v i t y of the method would improve by many orders of magnitude i f t he solut ion were f i l t e r e d , and the analysis were car r ied o u t on the f i l t e r paper. In the preliminary measurements, only those p rec ip i t a t e p a r t i c l e s which were s e t t l e d out on or were within about 20 microns of t he SSTR surface could be detected, because of t he l imited range of t he alpha p a r t i c l e i n the solut ion.
The conclusions of these preliminary measurements are:
(1) The SSTR boron analysis method is capable of detect ing KTBP pa r t i c l e s , but lacks the required s e n s i t i v i t y when solut ions are viewed d i r ec t ly .
(2) The method would undoubtedly y ie ld sa t i s f ac to ry r e su l t s i f the par t ic les were f i l t e r e d before analysis .
APPENDIX C
WESTINGHOUSE SAVANNAH RIVER COMPANY SAVANNAH RIVER TECHNOLOGY CENTER
Low-Level Gamma Spectrometry of K-40 for Appraisal of DWPF/ITP Filters
A number of samples have been counted for IWT to appraise the performance of filters to be used for removing cesium/potassium tetraphenyl-borate precipitates after In Tank Precipitation for DWPF. Particulate potassium salt in the filtrate serves as a measure of the filter efficiency and the expected decontamination factor. Naturally occurring K-40 can be counted to measure the amount of particulate potassium collected.
The low-level gamma spectrometric capabilities of the ETS Underground Counting Facility allow quantifying K-40 at levels as low as 1 pCi. Coupling this sensitivity with techniques for evaporative concentration of a liquid sample on a small area (-10 cm') has resulted in demonstrating DF's in excess of 40,000 for the filters studied. A chronological summary of the measurements on IWT test samples is given in Table 1, where brief comments identify the samples according to IWT sample labels,
The sample analyses in the Underground Counting Facility utilized a passive/active-shielded HPGe detector with 90% standard efficiency relative to a 31tx381 NaI(T1) detector, The counting chamber is 50 ft below ground, and is shielded by low- background materials ( 4 " thick pre-WWII steel walls surrounded by 4-7 ft of specular hematite). The facility is constructed as a Class 10,000 Clean Room, and the detector sample cavities are purged of radon backgrounds with nitrogen that evaporates from the detector dewars. The detector used in this work is constructed with low-background materials.
The above facility/detector design features reduce the backgrounds from cosmic-rays, natural radioactivity, and local
1
sources by orders of magnitude. Because the facility is well isolated from backgrounds from surface effects, the resulting. low background is quite constant and thus suitable for long sample counting. In the present work, sample coilnting of 1-3 days was used. Because of a small K-40 contribution in the background, special background counts were conducted to affirm its value.
The counting geometries for these samples approximated those for which calibrations had been measured; in particular, a 3.2 cm diameter vial, calibrated as a function of sample filling, was assumed suitable for both liquid and filter samples. As a check, a filter sample standard of 21.7 mg K was counted, yielding a value of 16.3 & 1.0 pCi for K-40, which is in reasonable agreement with 18.2 pCi calculated from the natural K-40 component of K. Based on this calibration check, a multiplicative correction factor of 1.12 2 0.07 might be applied to the K-40 values of Table 1; however, such a correction is not very significant relative to the present study, and the correction factor is within 20 of 1.00 which corresponds to no correction, Accordingly, no renormalization of the data has been applied.
MICRO-CARBOSEP@ 20, 40 and 60 are tubular ultrafiltration and microfiltration modules, specially designed for processing small quantities. They are multi-purpose. easily adaptable and compact. and are an ideal 1001 for research laboratories. They are particularly suitable for feasibility studies.
The system can be sterilized in an autoclave and can process a wide variety of fluids. With a liquid channel 0.5 or 6 mrn thick. it can operate at low pressure (c l .5 bar) or high pressure (>1.5 bar), at a low (30 Vh) or high (500 Vh) recirculation rate, depending on the product to be processed. It can stand on any laboratory bench and can be fed with a peristaltic pump found in all laboratories (see Appenaix 11).
