S I

15. DATA TRANSMITTED (F) ( G ) Approval Reason

IEl Title or Description of Data for IAI (Cl ID)

NO. NO. Transmitted nator Trans- Item (8) DmumentlDrawing No. Sheet Rev' NO.

mittal

1 HNF-1863 0 Tes t Plan f o r Tank NA 1,3 241-AN-104 D i l u t i o n Stud ies

I 1 . m Page 601921 Of - I

(H) ( 1 ) Origi- Receiv-

Dispo- Dispo- sition sition

er

1

JAN 0 9 i'g98 ENGINEERING DATA TRANSMITTAL

Approva l / re lease o f a t tached Tes t Plan i s requested.

ED-7400-172-2 (05 /96) G E F 0 9 7

ED-7400-1 72-1 (07/91)

S HNF-1863, Rev. 0

Test Plan for Tank 241-AN-IO4 Dilution Studies

D. L. Hert ing Numatec Hanford Company, Richland, WA 99352 U.S. Department o f Energy Contract DE-AC06-96RL13200

EDT/ECN: 601921 UC: 2030 Org Code: 8C510 Charge Code: D2DC4 B&R Code: EW3130010 Total Pages: /g

Key Words: d i l u t i o n , d i s s o l u t i o n , sodium s a l t s , p r i v a t i z a t i o n , v i t r i f i c a t i o n feed, r e t r i e v a l

Abstract : t h e f i r s t tanks t o be r e t r i e v e d f o r low leve l waste pretreatment and immobilization. Retr ieval o f the tank waste w i l l r e q u i r e d i l u t i o n . Laboratory tests a r e needed t o determine t h e amount and type of d i l u t i o n required f o r s a f e r e t r i e v a l and t r a n s f e r of feed and t o re -d isso lve major so luble sodium s a l t s while not p r e c i p i t a t i n g out o t h e r s a l t s . The proposed labora tory t e s t s a r e descr ibed in t h i s document.

Tank 241-AN-104 (104-AN) has been i d e n t i f i e d a s t h e one of

TRADEMARK DISCLAIMER. Reference herein t o any speci f ic comnercial product, process, or service by trade name, trademark, manufacturer, or otherwise, does not necessarily const i tu te or imply i t s endorsement, recomnendation, or favoring by the United States Government or any agency thereof or i t s contractors or subcontractors.

Printed i n the United States of America. TO obtain copies of t h i s document, contact: Document Control Services, P.O. Box 950, Mailstop H6-08, Richland WA 99352, Phone (509) 372-2420; Fax (509) 376-4989.

IT=-===---

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Release Stamp 9 78

R e l e d d p p r o v Dafe

Approved for Public Release

A-6400-073 (01/97) GEF321

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CONTENTS

1.0 INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

2.0 BACKGROUND . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

3.0 DESCRIPTION OF TEST . . . . . . . . . . . . . . . . . . . . . . . . . 5 3.1 Tank Composite Sample Prepara t ion . . . . . . . . . . . . . . . . 5 3.2 D i l u t i o n T e s t i n g Wi th Whole Tank Composite . . . . . . . . . . . 5

3.2.1 D i l u t i o n , s e t t l i n g . and chemical analyses . . . . . . . . 6 3.2.2 V i s c o s i t y . . . . . . . . . . . . . . . . . . . . . . . . 8

3.3 D i l u t i o n T e s t i n g With S e t t l e d S o l i d s . . . . . . . . . . . . . . 8 3.3.1 S e t t l e . decant. and d i l u t e supernatant l i q u i d . . . . . . 8 3.3.2 D i l u t i o n o f s e t t l e d s o l i d s . . . . . . . . . . . . . . . . 9 3.3.3 Temperature e f f e c t . . . . . . . . . . . . . . . . . . . 9 3.3.4 Rheology . . . . . . . . . . . . . . . . . . . . . . . . 9 3.3.5 P a r t i c l e s i z e d i s t r i b u t i o n and microscopy . . . . . . . . 10

4.0 DATA INTERPRETATION . . . . . . . . . . . . . . . . . . . . . . . . . 11 4.1 Phys ica l Data . . . . . . . . . . . . . . . . . . . . . . . . . . 11 4.2 Chemical Data . . . . . . . . . . . . . . . . . . . . . . . . . 13 4.3 Q u a l i t y Assurance . . . . . . . . . . . . . . . . . . . . . . . . 13

5.0 SAFETY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

6.0 WASTE HANDLING . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

7.0 SCHEDULE AND DELIVERABLES . . . . . . . . . . . . . . . . . . . . . . 14

8.0 REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

TABLES

Table 1 . Comparison o f Waste Compositions i n Tanks 104-AN and 105-AN . . . 2

Table 2 . Comparison o f A n a l y t i c a l Resu l ts f o r Supernatant L i q u i d and S e t t l e d S o l i d s Samples . . . . . . . . . . . . . . . . . . . 4

Table 3 . Core Segment Samples A v a i l a b l e f o r Whole-Tank Composite . . . . . 6

Table 4 . Correspondence o f D i l u t i o n s Tests f o r Tanks 104-AN and 105-AN . . 12

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ACRONYMS AND ABBREVIATIONS

Tank 241-AN-104 Tank 241-AN-105 total alpha double shell slurry feed gravity gram gal 1 on gamma energy analysis ion chromatography inductively coupled plasma spectroscopy ki 1 ogram 1 iter liquid sample milliliter polarized light microscopy retained gas sample revolutions per minute scanning electron microscope/energy dispersive x-ray spectroscopy solid sample specific gravity (or density) settled solids supernatant liquid diluted supernatant liquid Tank Characterization Report thermogravimetric analysis total inorganic carbon total organic carbon weight percent whole-tank composite microcurie microgram

104-AN 105-AN AT DSSF G g gal G EA IC ICP

kg Li q mL PLM RGS rPm SEM/EDS Sol SPG SSOl SUP SupD TCR TGA TIC TOC wt% WTC fiC i fig

6

i i i

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1.0 INTRODUCTION

Tank 241-AN-104 (104-AN) has been i d e n t i f i e d as one of t h e f i r s t t anks t o be f o r r e t r i e v e d f o r low leve l waste pretreatment and immobilization. Retr ieval of the tank waste wi l l r e q u i r e d i l u t i o n . Laboratory t e s t s t o determine the amount and type of d i l u t i o n required f o r s a f e and e f f i c i e n t r e t r i e v a l of t h e tank waste a r e descr ibed in this document. tes t requirements es tab l i shed by Process Development (Garf ie ld 1997 and Certa 1998).

The waste in tank 104-AN i s very s i m i l a r i n composition t o t h a t i n tank 241-AN-105 (105-AN). the t e s t i n g of 105-AN waste during f i s c a l year 1997 (Hert ing 1997) should be appl icable t o t h e 104-AN waste. The t e s t s proposed here f o r t h e 104-AN waste a r e designed (1) t o v e r i f y t h e s i m i l a r i t y t o 105-AN waste in chemical and physical behavior , and ( 2 ) t o provide addi t iona l information on d i l u t i o n e f f e c t s .

They a r e based on

See Table 1. Therefore , most of the conclusions from

The 104-AN t e s t s wi l l be done with a whole-tank-composite sample prepared by combining appropr ia te amounts of dra inable l i q u i d and s e t t l e d s o l i d s core segment samples from t h e two core samples t h a t were taken in 1996 (Hu 1997). The t e s t s performed on the composite sample wi l l be aimed pr imar i ly a t t h e a l t e r n a t i v e r e t r i e v a l scenar io i n which t h e tank supernatant l i q u i d i s removed (with some i n - l i n e d i l u t i o n ) before d i l u e n t is added t o the s e t t l e d s o l i d s remaining in t h e tank. Corresponding changes in labora tory procedures r e l a t i v e t o t h e 105-AN t e s t s a r e d e t a i l e d l a t e r i n t h i s t e s t plan.

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a Tables B3-9 and B3-12 in TCR (Jo 1997) Tables 83-4 and 83-7 i n TCR (Hu 1997) Tables 83-14 and 83-17 i n TCR (Jo 1997) Tables 83-9 and B3-12 in TCR (Hu 1997)

e except as noted

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2.0 BACKGROUND

Tank 104-AN c u r r e n t l y conta ins approximately 4.0 mi l l ion l i t e r s (1 .1 mi l l ion g a l ) of waste c l a s s i f i e d as double s h e l l s l u r r y feed (DSSF). samples were taken i n 1996. Based on t h e core sample r e s u l t s , t ank waste l a y e r volumes were est imated (Hu 1997) as 2,100 L (5,500 g a l ) crust, 2.3 mi l l ion L (600,000 g a l ) superna tan t l i q u i d , and 1 .7 mi l l ion L (449,000 g a l ) s e t t l e d s o l i d s . r e f e r r e d t o a s s ludge, s l u r r y , o r wet s a l t c a k e in var ious documents.

The s e t t l e d s o l i d s contain approximately 89% by weight i n t e r s t i t i a l l i q u i d and 11% actual s o l i d phase, based on t h e percent water a n a l y t i c a l r e s u l t s . No s p e c i f i c analyses have been done on t h e ac tua l s o l i d phase, but some information can be gleaned by comparing t h e analyses of t h e s e t t l e d s o l i d s l a y e r with analyses of the supernatant l i q u i d l a y e r . This comparison i s made i n Table 2 .

Components t h a t a r e s i g n i f i c a n t l y higher i n t h e s e t t l e d s o l i d s than i n t h e superna tan t l i q u i d include sodium, phosphate, s u l f a t e , t o t a l inorganic carbon (TIC), and t o t a l organic carbon (TOC). The major s o l i d phases, t h e r e f o r e , a r e l i k e l y t o be sodium s a l t s of carbonate , s u l f a t e , phosphate, and oxa la te ; and double s a l t s such as sodium f l u o r i d e s u l f a t e , Na,FSO,, and sodium carbonate s u l f a t e , Na CO (SO,),. so luble than t h e indi6vidual s a l t s , though only a l i t t l e s tudy has been done in this area f o r Hanford waste s o l u t i o n s .

One gram of s e t t l e d s o l i d s conta ins l e s s l i q u i d than one gram of l i q u i d , so components t h a t a r e present only in t h e l i q u i d phase (e .g . Al, K , n i t r i t e , ch lor ide , hydroxide) should have lower concent ra t ions in the s e t t l e d s o l i d s . The f a c t t h a t t h e concentrat ion of n i t r a t e i s near ly t h e same in both t h e l i q u i d and the s e t t l e d s o l i d s implies t h a t t h e r e may be some NaNO, in t h e s o l i d phase.

temperature-dependent. Therefore , temperature i s l i k e l y t o be a key f a c t o r i n t h e d i l u t i o n / d i s s o l u t i o n experiments. The s o l u b i l i t y of sodium o x a l a t e i s very dependent on i o n i c s t r e n g t h , and i s un l ike ly t o d isso lve very much a t t h e d i l u t i o n r a t i o s used f o r these t e s t s .

Two core Each core was composed of 21 segments.

The s e t t l e d s o l i d s a r e a l s o

Typical ly , these double s a l t s a r e l e s s

The s o l u b i l i t i e s of some of t h e sodium s a l t s a r e known t o be very

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Table 2 . Comparison of Analyt ical Resul ts for Supernatant Liquid and S e t t l e d Sol i d s Samples (averages o f segment sample r e s u l t s ) ’

from segment sample averages ( H u 1997) from composite sample averages (Hu 1997) previous column divided by dens i ty t o convert u n i t s

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3.0 DESCRIPTION OF TEST

3.1 Tank Composite Sample Preparat ion

All of the d i l u t i o n / d i s s o l u t i o n tests wi l l begin with a whole-tank composite sample prepared from samples c u r r e n t l y in t h e labora tory . p repara t ion and a l l of t h e t e s t i n g wi l l be done i n h o t c e l l s a t the 222-S Laboratory. s tudy. The weights l i s t e d under t h e heading "Current Inventory" represent t h e t o t a l amount of mater ia l c u r r e n t l y s tored i n t h e l t b o r a t o r y . weights under t h e heading "Avai lable f o r Composite represent t h e amount t h a t TWRS Charac ter iza t ion i s w i l l i n g t o r e l e a s e f o r t h e d i l u t i o n s tudy.

Based on t h e tank waste p r o f i l e and l a y e r d e n s i t i e s reported i n Sect ion 2 , t h e tank conta ins approximately 2.7 mi l l ion kg of s e t t l e d s o l i d s and 3.2 mi l l ion kg of supernatant l i q u i d . wi l l be c rea ted by mixing t h e l a y e r samples in t h e same r a t i o . Thus , approximately 900 g (560 mL) of s e t t l e d s o l i d s samples from Table 3 wi l l be mixed with 1100 g (780 mL) of supernatant l i q u i d samples.

t h e tank t h a t using d i f f e r e n t sample weights from individual segments w i t h i n a l a y e r wi l l not have any adverse e f f e c t on t h e composition of t h e composite sample. In addi t ion , t h e previous t e s t s with waste from tank 105-AN showed t h a t t h e r e i s a l a r g e range of acceptable d i l u t i o n r a t i o s . v i r t u a l l y a l l of t h e "Avai lable f o r Composite" sample can be used. The composite wi l l be mixed and s tored a t t h e ambient ho tce l l temperature . All t e s t s wi l l be done with a l i q u o t s taken from t h e composite sample.

I t i s widely recognized t h a t one of t h e most d i f f i c u l t problems in a n a l y t i c a l chemistry i s t o obta in a uniform a l i q u o t from a two-phase ( s o l i d / l i q u i d ) sample. To ensure t h e bes t poss ib le uniformity, a l l a l i q u o t s wi l l be taken by syr inge sampling while the composite sample i s being mixed. Duplicate t e s t s performed on s i m i l a r 105-AN samples (Hert ing 1997) showed t h a t t h i s sampling method g ives acceptable r e p r o d u c i b i l i t y .

ease in handling with hotce l l manipulators . be marked with volumetric i n d i c a t o r s . This j a r wi l l be used t o perform an ambient temperature s e t t l i n g r a t e t e s t on a l a r g e r s c a l e than i s poss ib le with t h e 50 m L c e n t r i f u g e cones t h a t wi l l be used f o r most of t h e t e s t s .

3.2

Sample

The core samples shown i n Table 3 a r e a v a i l a b l e f o r use i n t h i s

The smal le r

The whole-tank composite sample

The waste composition i s s u f f i c i e n t l y homogeneous within each l a y e r i n

Therefore ,

The composite sample wi l l be divided i n t o t h r e e 500 mL sample j a r s f o r A t l e a s t one of these j a r s wi l l

Dilut ion Test ing with Whole Tank Composite

The f i r s t t e s t s wi l l represent adding mixer pumps t o t h e tank and mixing t h e waste before any d i l u t i o n o r t r a n s f e r takes place. d u p l i c a t e t e s t s performed on t h e 105-AN samples, but t h e number of t e s t s wi l l be much smaller . Tes ts wi l l be l imi ted t o one temperature (45 "C), which was t h e base l ine temperature f o r t h e 105-AN sample t e s t s .

These t e s t s wi l l

5

Core Segment' Parent2 Current J a r No. Inventory (9)

Segments 2-11 represent supernatant l i q u i d ; 15-21 s e t t l e d s o l i d s RGS = re ta ined gas sample ana lys i s samples

3.2.1 Di lu t ion , s e t t l i n g , and chemical analyses

Two sample a l i q u o t s , 30 m L each, wi l l be t r a n s f e r r e d from t h e whole-tank composite i n t o 50 m L c e n t r i f u g e cones. The cones wi l l be weighed, and t h e n placed i n a cons tan t temperature water bath held a t 45 " C f o r a t l e a s t 16 hours.

Af te r t h e 16 hour e q u i l i b r a t i o n per iod, water wi l l be added t o one of t h e cones t o represent d i l u t i o n t o 50% by volume, i . e . , t h e volume of water added wi l l be one-half of t h e volume of sample in t h e cone before d i l u t i o n . The d i l u t i o n water wi l l be e q u i l i b r a t e d a t t h e same temperature f o r t h e same length o f time as t h e samples. i t wi l l be mixed and s e t t l e d as descr ibed below.

No water wi l l be added t o t h e o t h e r cone, but

Avai lable f o r Composite (9)

6

163

163

164

19 RGS 375 250

21 RGS 225 100

18 RGS 375 250

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As soon as t h e d i l u t i o n water i s added, both cones wi l l be mixed with a vortex mixer. Then t h e cones wi l l be returned t o t h e water bath. A t t h e end of each hour f o r f i v e hours, t h e cones wi l l be mixed again, and returned t o the water bath. The cones wi l l then be allowed t o s e t t l e overnight i n t h e water bath. The fol lowing day, t h e cones wi l l again be mixed and s e t t l e d t h r e e t imes f o r one hour each s e t t l i n g per iod. Af te r t h e t h i r d and f i n a l mixing, readings of volume percent s e t t l e d s o l i d s wi l l be recorded a s a func t ion of time f o r the remainder of t h e work s h i f t . S e t t l i n g w i l l be allowed t o cont inue f o r a minimum of 48 hours a f t e r the f i n a l mixing.

A f t e r t h e f i n a l readings of volume percent s e t t l e d s o l i d s , t h e cones wi l l be cent r i fuged a t approximately 2000 rpm (300 G force) f o r 20 minutes. Volumes of cent r i fuged s o l i d s wi l l be recorded. Supernatant l i q u i d s wi l l be decanted i n t o sample v i a l s , and the cones wi l l be re-weighed t o determine the weight percent cent r i fuged s o l i d s . wi l l be analyzed f o r % H 0 (gravimetr ic method) and d e n s i t y (SpG). port ion wi l l be analyze: f o r t h e fol lowing:

One por t ion of each supernatant l i q u i d A second

IC ( ion chromatography f o r F - , Cl- , NO,-, NO,., PO:-, SO,'-, and o x a l a t e analyses)

TIC ( t o t a l inorganic carbon) TOC ( t o t a l organic carbon) ICP ( induct ive ly coupled plasma spectroscopy f o r metal ion analyses) OH- ( f r e e hydroxide) GEA (gamma energy ana lys i s ) AT ( t o t a l a lpha) 90Sr and 99Tc.

The remaining f r a c t i o n of each supernatant l i q u i d sample wi l l be s tored i n t h e water bath f o r a t l e a s t one month, and wi l l be observed p e r i o d i c a l l y t o see whether any s o l i d s have formed. I f s o l i d s do form, they wi l l be charac te r ized f o r physical behavior (e .g . ge la t inous o r r a p i d - s e t t l i n g ) . They wi l l be examined by polar ized l i g h t microscopy (PLM) t o a t tempt i d e n t i f i c a t i o n based on c r y s t a l habi t and opt ica l p roper t ies . They may a l s o be analyzed by whatever chemical ana lys i s methods a r e deemed appropr ia te by t h e chemist-in- charge.

The cent r i fuged s o l i d s in each cone wi l l be weighed, and then t r a n s f e r r e d t o a sample v ia l f o r t h e following analyses:

%H,O by thermogravimetric ana lys i s (TGA) d i r e c t s o l i d sample f o r TIC, TOC water d i g e s t f o r IC and OH- acid d i g e s t f o r ICP, GEA, AT, 90Sr and 99Tc.

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3.2.2 Viscos i ty

three samples as a func t ion of temperature over the range ambient t o 65°C. The f i r s t sample wi l l be a fresh a l i q u o t of t h e undi luted whole-tank composite sample. The second sample wi l l be another whole-tank composite sample d i l u t e d t o 50% by volume with water . from an undi luted whole-tank-composite sample.

temperature , then a four th sample wi l l be t e s t e d . the supernatant l i q u i d d i l u t e d 20% by volume with water .

Rotovisco@ RV20 with a CV20 Sensor System. system wi l l be used i n conjunct ion with t h e CV20 f o r the rheological measurements. each with a cone-shaped bottom face . measured a s a func t ion of t h e speed of t h e r o t a t i n g beaker.

Rheology measurements (shear s t r e s s vs. shear r a t e ) wi l l be made on

Jhe t h i r d sample wi l l be t h e superna tan t l i q u i d

I f t h e v i s c o s i t y of t h e supernatant l i q u i d sample i s above 5 C P a t any The four th sample wi l l be

The viscometer used f o r these measurements wi l l c o n s i s t of a Haake

\

A Mooney-Ewart type measuring

The torque on t h e inner cy l inder i s This coaxial cy l inder system c o n s i s t s of a beaker and cy l inder

3 . 3 Dilu t ion Tes t ing with S e t t l e d Sol ids

The next s e r i e s of t e s t s wi l l represent removing t h e superna tan t l i q u i d from t h e tank w i t h i n - l i n e d i l u t i o n , then adding mixer pumps and d i l u t i o n water t o t h e tank t o d i s s o l v e t h e sodium s a l t s in t h e s e t t l e d s o l i d s .

3.3.1 S e t t l e , decant and d i l u t e supernatant l i q u i d

Eight sample a l i q u o t s , 45 m L each, wi l l be t r a n s f e r r e d from the whole-tank composite i n t o 50 m L c e n t r i f u g e cones. The cones wi l l be weighed, and then placed in a cons tan t temperature water bath a t 45 "C f o r a t l e a s t 72 hours.

The next s t e p wi l l be t o decant t h e supernatant l i q u i d from each of t h e e i g h t c e n t r i f u g e cones. All of t h e decanted l i q u i d wi l l be c o l l e c t e d i n a s i n g l e j a r o r b o t t l e . Af te r t h e l i q u i d i s mixed (by s t i r r i n g ) , i t wi l l be re-divided i n t o nine 15 mL cen t r i fuge cones, 10 m L per cone. Density of t h e l i q u i d wi l l be measured from t h e volume and weight of l i q u i d i n each cone. The remaining l i q u i d wi l l be used f o r v i s c o s i t y measurement (Sect ion 3.3.4).

and another t h r e e wi l l be d i l u t e d 20% by volume. remain undi lu ted .

Three of t h e l i q u i d samples wi l l be d i l u t e d 10% by volume with water , The o t h e r t h r e e samples wi l l

New d e n s i t i e s wi l l be measured f o r t h e s ix d i l u t e d samples.

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One undi luted sample, one 10%-diluted sample, and one 20%-diluted sample w i l l be held a t ambient temperature (approximately 25 "C) f o r a minimum of one week. Three corresponding samples wi l l be held a t 45 "C, and t h e t h r e e remaining samples a t 65 "C f o r t h e same time per iod. observed f o r poss ib le formation of p r e c i p i t a t e s . the volume and weight of s o l i d s wi l l be measured. The s o l i d s wi l l be examined w i t h a po lar ized l i g h t microscope t o a t tempt i d e n t i f i c a t i o n of t h e s o l i d phase. chemist-in-charge.

All samples wi l l be I f any p r e c i p i t a t e s form,

Additional chemical analyses of t h e s o l i d s may be requested by t h e

3.3.2 Di lu t ion of s e t t l e d s o l i d s

The volume and weight of s e t t l e d s o l i d s remaining a f t e r decant ing t h e superna tan t l i q u i d s w i l l be recorded. Then water wi l l be added t o each cone t o represent d i l u t i o n t o 0 , 40, 80, o r 120% of t h e s e t t l e d s o l i d s volume, each d i l u t i o n made i n d u p l i c a t e . e q u i l i b r a t e d a t t h e same temperature f o r t h e same length of time a s t h e samples .

The remainder of t h e t e s t i n g wi l l fol low the procedure descr ibed f o r t h e whole-tank composite samples descr ibed in Sect ion 3.2. The superna tan t l i q u i d decanted a f t e r cen t r i fuging t h e samples wi l l be d iv ided . One por t ion of each l i q u i d wi l l be s tored in the water bath f o r a t l e a s t one month t o watch f o r p r e c i p i t a t i o n of s o l i d s . The remainder of each l i q u i d and the cent r i fuged s o l i d s wi l l be analyzed a s descr ibed in Sect ion 3.2.1.

3.3.3 Temperature e f f e c t

and 3.3.2) w i l l be repeated a t higher and lower temperatures . c o n s i s t of t h e 80% d i l u t i o n samples a t 65°C and a t 25°C. requirements wi l l be t h e same a s descr ibed i n Sect ion 3.2.1.

3 .3 .4 Rheology

Rheology measurements (shear s t r e s s vs. shear r a t e ) wi l l be made on t h r e e samples a s a func t ion of temperature over t h e range ambient t o 65°C. The f i r s t sample wi l l be t h e undi luted s e t t l e d s o l i d s sample. The second sample wi l l be t h e s e t t l e d s o l i d s sample d i l u t e d t o 80% by volume with water , r e l a t i v e t o t h e volume of s e t t l e d s o l i d s a f t e r decant ing t h e supernatant l i q u i d . The t h i r d sample wi l l be t h e supernatant l i q u i d from t h e 80%-diluted sample.

Before t h e d i l u t i o n s a r e made, the water wi l l be

A subse t of t h e s e t t l e d - s o l i d s d i l u t i o n s e r i e s of t e s t s (Sect ions 3.3.1 The subse t wi l l

Analyt ical

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3.3.5

undiluted solids and one sample of solids remaining after 80% dilution o f the settled solids. Polarized light microscopy (PLM) will be performed on the same two samples to identify changes in morphology caused by dilution. Analysis of the sol ids by scanning electron microscopy with energy dispersive x-ray spectroscoy (SEM/EDS) may be performed in addition to or instead of the PLM, depending on availability and state of repair of the SEM/EDS instrument.

Particle size distribution and microscopy

Particle size distribution analysis will be performed on one sample of

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4.0 DATA INTERPRETATION

4.1 Physical Data

Volumes and weights of s e t t l e d and cent r i fuged s o l i d s wi l l be the primary measurements used t o eva lua te d i l u t i o n parameters. All of t h e d i l u t i o n parameters match those used f o r t e s t s performed l a s t f i s c a l year on waste from tank 105-AN. Therefore , d i r e c t comparison of the r e s u l t s f o r t h e two tank wastes wi l l be poss ib le . Table 4 shows t h e correspondence.

Di lu t ion with NaOH solu t ion wi l l not be performed on t h e 104-AN waste samples because t h e NaOH concentrat ion i s higher in 104-AN waste than in 105-AN waste. f o r d i l u t i o n of the 104-AN waste.

Therefore , i t i s very unl ike ly t h a t NaOH s o l u t i o n would be used

Temperature may have a complex e f f e c t on t h e volume of s o l i d s . Increasing temperature i s expected t o cause increas ing s o l u b i l i t y of sodium s u l f a t e , phosphate, and n i t r a t e , but cause decreasing s o l u b i l i t y of sodium carbonate .

Rheology measurements a r e needed t o a s s e s s pump c h a r a c t e r i s t i c s t h a t wi l l be requi red f o r mixing and t r a n s f e r r i n g t h e waste. wi l l be provided as a func t ion of temperature f o r t h e fol lowing samples:

These measurements

undi luted whole-tank composite sample whole-tank composite sample d i l u t e d 50% by volume with water undi luted s e t t l e d s o l i d s sample with t h e supernatant l i q u i d decanted s e t t l e d s o l i d s sample d i l u t e d 80% by volume undi luted tank waste supernatant l i q u i d superna tan t l i q u i d from 80%-diluted s e t t l e d s o l i d s sample.

In a l l of t h e d i l u t i o n t e s t s , decanted cent r i fuged l i q u i d samples wi l l be s tored f o r a t l e a s t one month t o determine whether s o l i d s form a f t e r d i l u t i o n . Any s o l i d s t h a t form wi l l be evaluated f o r physical p r o p e r t i e s (e .g . gel formation) , and analyzed by PLM and chemical analyses i f deemed appropr ia te .

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WTC = whole-tank composite sample; SSol = s e t t l e d s o l i d s sample a Sol/Liq = chemical and physical ana lys i s of s o l i d / l i q u i d phases

t e s t s performed i n dupl ica te Sup = superna tan t l i q u i d from undi luted sample SupD = supernatant l i q u i d from 80%-diluted sample

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4.2 Chemical Data

Chemical analyses of cent r i fuged l i q u i d and s o l i d phases wi l l be used t o develop an understanding of t h e physical da ta . With analyses of both phases, i t wi l l be poss ib le t o c a l c u l a t e t h e cont r ibu t ion of t h e i n t e r s t i t i a l l i q u i d t o t h e cent r i fuged s o l i d s t o provide a composition of t h e t r u e s o l i d phase. Knowledge of which s o l i d phases a r e present as a func t ion of d i l u t i o n r a t i o should provide t h e information needed t o explain t h e physical da ta .

As a f i r s t approximation, t h e assumption wi l l be made t h a t a l l of t h e water in t h e cent r i fuged s o l i d s can be a t t r i b u t e d t o i n t e r s t i t i a l l i q u i d . I f t h e c a l c u l a t i o n s and/or PLM r e s u l t s suggest t h a t t h e t r u e s o l i d phase conta ins some s a l t s t h a t a r e highly hydrated [e .g . Na,F(P04),.19H,0], then an i t e r a t i v e c a l c u l a t i o n may be required t o d i s t r i b u t e t h e water i n t h e cent r i fuged s o l i d s between t h e t r u e s o l i d phase and the i n t e r s t i t i a l l i q u i d phase.

Analyt ical determinat ions wi l l be t h e same as those f o r the 105-AN samples done e a r l i e r , except t h a t :

(1) Water d i g e s t wi l l added t o t h e ana lys i s of t h e cent r i fuged s o l i d s so t h a t t h e s o l i d s can be analyzed by IC and OH- f o r water-soluble anions. This wi l l g ive a more d i r e c t ind ica t ion than in t h e 105-AN study of whether n i t r a t e and o ther IC spec ies a r e present in t h e s o l i d phase.

and include t h e " less - than" elements t h a t were not reported f o r t h e 105-AN samples. This wi l l allow more of t h e P r i v a t i z a t i o n envelope s p e c i f i c a t i o n s (ana ly te t o sodium mole r a t i o s ) t o be evaluated.

(2) The l i s t of ana ly tes from t h e ICP t h a t wi l l be reported wi l l be longer ,

4 .3 Q u a l i t y Assurance

HNF-PRO-233, th is t e s t plan i s assigned Approval Designator N/A. Approval s i g n a t u r e s a r e required from t h e author , immediate manager, and customer.

All t e s t i n g wi l l fol low t h e "Process Chemistry & S t a t i s t i c s Q u a l i t y Assurance Plan", WHC-SD-CP-QAPP-018, Rev. 0 (Meznarich 1996). S p e c i f i c labora tory i n s t r u c t i o n s wi l l be reviewed and approved by Process Chemistry management, 2 2 2 4 Radiological Control , 222-S Environmental, and 222-S Indus t ia l Safe ty p r i o r t o i n i t i a t i o n of t e s t i n g . The i n s t r u c t i o n s w i l l be recorded i n a cont ro l led labora tory notebook before work begins; observat ions and d a t a w i l l be recorded as t h e work i s done.

Based on t h e requirements i n "Review and Approval of Documents",

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5.0 SAFETY

All of t h e s a f e t y requirements t h a t apply t o t h i s t e s t plan a r e descr ibed in "Development of Instrumentat ion, Methods and Performance of Process Tes t ing" , Hanford Analyt ical Serv ices Laboratory Operating Procedure LO-140-100, Rev. B-0, re leased J u l y 8, 1997.

6.0 WASTE HANDLING

Three waste streams a r e expected t o be generated from this tes t program. Stream #1 i s t h e waste r e s u l t i n g from analys is of samples. generated from these r o u t i n e analyses wi l l be handled in accordance with t h e i n s t r u c t i o n s i n t h e procedures f o r t h e respec t ive analyses .

expected t o be l e s s than 1 kg, wi l l be discardec! t o t h e 219-S Building tanks v i a a ho tce l l d r a i n , per,,procedure LO-100-107, Disposal , and Management .

Stream #3 i s t h e s o l i d hotce l l waste cons is t ing of used c e n t r i f u g e cones, used sample v i a l s , and used p l a s t i c syr inges. This waste wi l l be r insed w i t h water , loaded i n t o waste cans, removed from the h o t c e l l , and disposed of according t o LO-100-151,

Other than t h e waste streams just descr ibed, t h e r e wi l l be no accumulating of hazardous waste. Waste Compatibi l i ty Assessment documentation wi l l be requi red .

Each waste

Stream #2 i s t h e used and le f t -over tank waste m a t e r i a l . This mater ia l ,

Cubicle Housekeeping, Waste

Therefore , no Waste Stream Fact Sheet o r

7.0 SCHEDULE AND DELIVERABLES

This t e s t plan i s scheduled t o be issued by December 31, 1997. Management approval f o r t h e s p e c i f i c labora tory i n s t r u c t i o n s wi l l be obtained by January 15, 1998. Laboratory work wi l l commence by January 20, 1998.

A complete r e p o r t of t h e t e s t r e s u l t s wi l l be issued in t h e form of a d r a f t support ing document by May 20, 1998. Informal in te r im s t a t u s r e p o r t s wi l l be issued t o the customer v i a cc:Mail on a weekly bas is .

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8.0 REFERENCES

%a, P. J . (1998), Data Quality Objectives for TWRS Privatization Phase I : Confirm lank T i s an Appropriate Feed Source for Low-Activity Waste Feed Batch X , PSDQO-01, HNF-1796, Rev. 0 (DRAFT).

Cer

Garfield, J . S. (1997), Tank 241-AN-105 DilutionlDissolution Test Requirements, Numatec Hanford Corporation Internal Memo 8C451-97-004, March 27.

Herting, D. L. (1997), Results of Dilution Studies with Waste from Tank 241-AN-105, HNF-SD-WM-DTR-046, Rev. 0, Numatec Hanford Corporation, Richland, Washington.

Hu, T. A. (1997), L. W . Shelton and T. L. Welsh, Tank Characterization Report for Double-Shell Tank 241-AN-104, HNF-SD-WM-ER-690, Rev. 0, Lockheed Martin Hanford Corporation, Richland, Washington.

Jo , J . (1997), L. W. Shelton, T. L. Welsh and J. Stroup, Tank Characterization Report for Double-Shell Tank 241-AN-105, HNF-SD-WM-ER-678, Rev. 0, Lockheed Martin Hanford Corporation, Richland, Washington.

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