LA

—11691-M S DE90 00398 8



### Characterization of

Reactive Tracers forC-Wells Field

Experiments I: Electrostatic Sorption Mechanism, Lithium H. R. Fuentes W. L. Polzer E. H. Essington B. D. Newman

DISCLAIMER

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thei r employees , make s an y warranty , expres s o rimplied , o rassume s an y lega l liabilit y o rresponsi bilit y fo rth e accuracy , completeness , o rusefulnes s o f an y information , apparatus , product , o r proces s disclosed , o rrepresent s tha tit s us e woul d no tinfring e privatel y owne d rights . Refer enc e herei n t o an y specifi ccommercia l product , process , o rservic e b y trad e name , trademark , manufacturer , o rotherwis e doe s no tnecessaril y constitut e o rimpl y it s endorsement , recom mendation , o rfavorin g b y th e Unite d State s Governmen to ran y agenc y thereof . Th e view s an d opinion s o f

author s expresse d herei n d o no tnecessaril y stat e o rreflec tthos e o f th e Unite d State s Governmen to ran y agenc y thereof .

Los Alamo s Nationa l Laborator y Los Alamos.Ne

wMexic o 8754 5CONTENT S LIS T O F FIGURE S v i LIS T O F TABLE S vii i ABSTRAC T 1 1. 0 INTRODUCTIO N2 2. 0 TRACE R SELECTIO NCRITERI A5 3. 0 LITHIU M 6 4. 0 MATERIAL S AND METHOD S 1 3 4. 1 Pro wPas s Sample s and J-1 3 Wate r 1 3 4. 2 Procedure s 1 8 4.2. 1 Adsorptio n Kinetic s 1 8 4.2. 2 Desorptio n Kinetic s 2 0 4.2. 3 EquilibriumAdsorptio n 2 1 4.2. 4 EquilibriumDesorptio n 2 1 4.2. 5 Potentiometri c Titratio n 2 1 4.2. 6 Electrophoresi s 2 2 4.2. 7 Abrasio n Effect s 2 4 4. 3 Model s 2 6 4.3. 1 Isotherm s 2 6 4.3. 2 Thermodynamic s 3 0 4. 4 Pre-experimenta l Geochemica l Modelin g 3 4 5. 0 RESULT S AND DISCUSSIO N3 7 5. 1 Kinetic s Experiment s 3 7 5. 2 Equilibrium3 8 5.2. 1 Sorptio n Calculation s 3 8 5.2. 2 Isother mEvaluatio n 4 0 5.2. 3 Thermodynami c Paramete r Estimatio n 5 0 5.2. 4 Deso-ptio n 6 0 5. 3 Potentiometri c Studie s 6 3 6. 0 SUMMAR Y AN

D CONCLUSION S 7 1 ACKNOWLEDGMENT S 7 4 REFERENCE S 7 6 APPENDI X A . ANALYTICA L INSTRUMENTATIO N8 1 APPENDI X B . ESTIMATE S O F LITHIUM ADSORPTIO NAND DESORPTIO NEQUI

LIBRIUM CONCENTRATION S 8 5 APPENDI X C . EQUILIBRIU M CONCENTRATION S AND MODELIN G VARIABLE S ... . 9 5 APPENDI X D . STATISTICA L AND MODE L PARAMETE R ESTIMATE S FO R ISOTHERM S . 11 3LIS T OF FIGURE S Figur e 1 . Observe dan dpredicte dadsorptio no f lithiu m ona Pro w Pas s suspensio ni nJ-1 3 wel l wate r a t 25° C fo r aninitia l concentratio nrang e o f 1 t o 200 0 fig L i m L an da solid-to-liqui d rati o o f 1:20 . Adsorbe dlithiu m i s determine di ntwo ways : (1 ) base do nmeasure dlithiu m i nsolutio n(Li ) an

d(2 ) base dona combinatio no f measure dlithiu m an dothe r cation s i nsolutio n (bes t estimate) . Predicte dlithiu m i s base donth e Modifie d Freundlic hisotherm

4 1 Figur e 2 . Observe dandpredicte dadsorptio no f lithiu m ona Pro w Pas s suspensio ni nJ-1 3 wel l wate r a t 38° C fo r aninitia l concentratio nrang e o f 1 t o 200 0 fig L i mL " anda solid-to-liqui d rati o o f 1:20 . Adsorbe dlithiu m i s determine di ntw

o ways : (1 ) base donmeasure dlithiu m i nsolutio n(Li ) an

d(2 ) base dona combinatio no f measure dlithiu m andothe r cation s i nsolutio n (bes t estimate) . Predicte dlithiu m i s base do nth e Modifie d Freundlic hisotherm

4 2 Figur e 3 . Observe dandpredicte dadsorptio no f lithiu m ona Prow

Pas s suspensio ni nJ-1 3 wel l wate r a t 45° C fo r aninitia l concentratio nrang e o f 1 t o 200 0 fig L i m L anda solid-to-liqui d rati o o f 1:20 . Adsorbe dlithiu m i s determine di ntwo ways : (1 ) base donmeasure dlithiu m i nsolutio n(Li ) an

d(2 ) base dona combinatio no f measure dlithiu m an dothe r cation s i nsolutio n (bes t estimate) . Predicte dlithiu m i s base donth e Modifie d Freundlic hisotherm

4 3 Figur e 4 . Observe dan dpredicte dadsorptio no f lithiu m ona Prow

Pas s suspensio ni nJ-1 3 wel l wate r a t 25° C fo r aninitia l concentratio nrang e o f 1 t o 15 0 fig L i mL " an

da solid-to-liqui d rati o o f 1:10 . Adsorbe dlithiu m i s determine di ntw

o ways : (1 ) base do nmeasure dlithiu m i nsolutio n(Li ) and(2 ) base dona combinatio no f measure dlithiu m andothe r cation s i nsolutio n(bes t estimate) . Predicte dlithiu m i s base donth e Modifie dFreundlic h isotherm 4 4 Figur e 5 . Observe dandpredicte dadsorptio no f lithiu m ona Pro w Pas s suspensio ni nJ-1 3 wel l wate r a t 38° C fo r aninitia l concentratio nrang e o f 1 t o 15 0 fig L i mL " anda solid-to-liqui d rati o o f 1:10 . Adsorbe dlithiu m i s determine dintw

o ways : (1 ) base donmeasure dlithiu m i nsolutio n(Li ) an

d(2 ) base dona combinatio no f measure dlithiu m an dothe r cation s insolutio n (bes t estimate) . Predicte dlithiu m i s base donth e Modifie d Freundlic hisotherm

, 4 5

v iFigur e 6 . Observe dandpredicte dadsorptio no f lithiu m ona Prow

Pas s suspensio ni nJ-1 3 wel l wate r a t 45° C fo r aninitia l concentratio nrang e o f 1 t o 15 0 fig L i mL ~ an

da solid-to-liqui d rati o o f 1:10 . Adsorbe dlithiu m i s determine di ntwo ways : (1 ) base donmeasure dlithiu m i nsolutio n(Li ) and(2 ) base do na combinatio no f measure dlithiu m andothe r cation s i nsolutio n (bes t estimate) . Predicte dlithiu m i s base donth e Modifie d Freundlic hisotherm

4 6 Figur e 7. Observe dandpredicte dadsorptio nanddesorptio no f lithiu m o n a Prow Pas s suspensio ni nJ-1 3 wel l wate r a t 3 8 C fo r an initia l concentratio nrang e o f 1 t o 200 0 fig L i mL " anda solid-to-liqui drati o o f 1:20 . Predicte dlithiu m i s base do nth e Modifie dFreundlic hisotherm 6 4 Figur e 8 . Observe dandpredicte dadsorptio nanddesorptio no f lithiu m on a Prow Pas s suspensio ni nJ-1 3 wel l wate r a t 38° C fo r a n initia l concentratio nrang e o f 1 t o 15 0 fig L i mL " anda solid-to-liqui drati o o f 1:10 . Predicte dlithiu m i s base don th e Modifie dFreundlic bisotherm 6 5 Figur e 9 . Potentiometri c titratio no f Pro w Pas s i nsuspensio nwit h J-1 3 wel l wate r an

dNaClO . electrolyt e a t 38° C withou t th e additio no f lithiu

m 6 7 Figur e 10 . Potentiometri c titratio no f Pro w Pas s i nsuspensio nwit h J-1 3 wel l wate r andNaC10 4 electrolyt e a t 38° C wit hth e additio no f 90 0 fig

L i mL" 1 6 8 Figur e 11 . Electrophoreti c behavio r o f a colloida l suspensio no f Prow

Pas s i nJ-1 3 wel l wate r andNaClO . electrolyt e a t 38° C wit hth e additio no f 90 0 fig L i mL 6 9 Figur e 12 . Electrophoreti c behavio r o f a colloida l suspensio no f Prow

Pas s i nJ-1 3 wel l wate r andNaC10 4 electrolyt e a t 38° C withou t th e additio no f lithiu m 7 0

vi i

### LIS T OF TABLE S I . GENERI C CLASSIFICATIO N OF ADSORPTION

PROCESSE S 3 II . LITHIU

M CHARACTERISTIC S 7 III . LITHIUM

BROMID E CHARACTERISTIC S 8 IV . J-1 3 VATE RBfc?(lR E ANDAFTE REQUILIBRATIO N

VIT HPROV

PAS S MATE RIAL S (ng mL" J 

### ) 1 5 V . PHYSICOCHEMICA L CHARACTERIZATION OF PROV PAS S TUF F SAMPLE S (<50 0 ) USE DI N TH E INVESTIGATION S 1 6 VI . REGRESSIO N

ANDCOMPARISON

BETVEE N SIZ E DISTRIBUTION S BEFOR E AND AFTE RTUMBLING2 5 VII . PREDICTION S FO RLITHIU M DISTRIBUTIO N

I N PROV PAS S ANDJ-1 3 VATE RADSORPTIO N

EXPERIMENT S A T 38° C (L i = 200 0 pg raL" 1 

### A S LiBr ) 3 6 VIII . A

COMPARISO N

OF ESTIMATE DPARAMETER S OF FOURISOTHERM MODEL S FO R TH E ADSORPTIO N

O F LITHIUM

O N A PROV PAS S SUSPENSIO N

I N J-1 3 VEL L VATE RFO RA

N INITIAL CONCENTRATION

RANG E O F 1 T O 200 0 pg

L i mL' 1 

### ANDA SOLID-TO-LIQUI DRATI O OF 1:2 0 4 8 IX . A

COMPARISO N

OF ESTIMATE DPARAMETER S O F FOURISOTHERM MODEL S FOR TH E ADSORPTIO N

O F LITHIU

M O N A PROV PAS S SUSPENSIO N

I N J-1 3 VEL L VATE RFO RA

N INITIAL CONCENTRATION

RANG E OF 1 T O 15 0 fig L i mL" 1 

### ANDA

SOLID-TO-LIQUI DRATI O OF 1:1 0 5 1 X . PARAMETE RVALUE S FO RTH E ESTIMATION OF A THERMODYNAMI C EQUILIBRIUM CONSTAN T FO RTH E LITHIU

M ADSORPTION

O N A PROV PAS S SUSPENSIO N

I N J-1 3 VEL L VATE RA T THRE E TEMPERATURE S FORTH E INITIAL CONCEN TRATION RANG E OF 1 T O 200 0 pg

L i raL' 1 

### ANDA

SOLID-TO-LIQUI D RATI O OF 1:2 0 5 4 XI . THERMODYNAMI C CONSTANT S ESTIMATE DFO RLITHIU M ADSORPTIO N

O N A PROV PAS S SUSPENSIO N

I N J-1 3 VEL L VATE RA T THRE E TEMPERATURE S FORA N INITIAL CONCENTRATIO N

RANG E OF 1 T O 200 0 pg

L i raL" 1 

### AN

DA SOLID TO-LIQUI DRATI O OF 1:2 0 5 5 XII . PARAMETE RVALUE S FORTH E ESTIMATION OF THERMODYNAMI C EQUILIBRIUM CONSTANT S FO RLITHIU

M ADSORPTION

O N A PROV PAS S SUSPENSIO N

I N J-1 3 VEL L VATE RAT 38° C AN D45° C FORTH E INITIAL CONCENTRATIO N RANG E OF 1 T O 15 0 jig

L i mL" 1 

### AN

DA SOLID-TO-LIQUI DRATI O OF 1:10 . 5 7

vii i

### XIII . THERMODYNAMI C CONSTANT S ESTIMATE DFO RLITHIU M ADSORPTION

O N A PROV PAS S SUSPENSIO N

I N J-1 3 VEL L WATE RA T 38° C AN D45° C FOR A N INITIA L CONCENTRATION

RANG E O F 1 T O 15 0 fig

L i raL" 1 

### ANDA SOLID-TO-LIQUI DRATI O OF 1:1 0 5 8 XIV . DATA

USE DI N TH E CALCULATION

OF EQUILIBRIUM

CONSTANT S FO R TH E ADSORPTIO N

OF LITHIU

M O N A PROV PAS S SUSPENSIO N

I N J-1 3 VEL L VATE RA T THRE E TEMPERATURE S FORTH E INITIAL CONCENTRATIO N RANG E OF 1 T O 15 0 ng

L i ml' 1 

### AN

DA SOLID-TO-LIQUI DRATI O OF 1:20 . .. . 6 1 XV . EQUILIBRIUM

CONSTANT S ANDENTHALPIE S FO RTH E ADSORPTIO N O F LITHIU M O N A PROV PAS S SUSPENSION

I N J-1 3 VEL L VATE RA T TEMPERATURE S OF 25°C , 38°C , AN D45° C FO RTH E INITIAL CON CENTRATIO N RANG E OF 1 T O 200 0 fig

L i mL" 1 

### AN

DA SOLID-TO LIQUI DRATI O O F 1:2 0 6 2 B-I . ADSORBE DLITHIU

M CONCENTRATION S A S ESTIMATE DB YTV O METHOD S ANDTHOS E CONSIDERE DBES T ESTIMATE S FO RADSORPTION O N A PROV PAS S SUSPENSIO N

I N J-1 3 VEL L VATE RA T 25° C FORA N INITIAL CONCENTRATIO N

RANG E OF 1 T O 200 0 fig

L i mL' 1 

### ANDA

SOLID-TO-LIQUI D RATI O OF 1:2 0 8 7 B-II . ADSORBE DLITHIU

M CONCENTRATION S A S ESTIMATE DB YTV O METHOD S ANDTHOS E CONSIDERE DBES T ESTIMATE S FORADSORPTIO N O N A PROV PAS S SUSPENSIO N

I N J-1 3 VEL L VATE RA T 38° C FO RA N INITIA L CONCENTRATIO N

RANG E OF 1 T O 200 0 fig

L i mL" 1 

### ANDA

SOLID-TO-LIQUI D RATI O O F 1:2 0 8 8 B-III . ADSORBE DLITHIU

M CONCENTRATION S A S ESTIMATE DB YTVO METHOD S ANDTHOS E CONSIDERE DBES T ESTIMATE S FO RADSORPTIO N O N A PROV PAS S SUSPENSIO N

I N J-1 3 VEL L VATE RA T 45° C FO RA N INITIA L CONCENTRATIO N

RANG E O F 1 T O 200 0 fig

L i mL" 1 

### AN

DA SOLID-TO-LIQUI D RATI O O F 1:2 0 8 9 B-IV . ADSORBE DLITHIU

M CONCENTRATION S A S ESTIMATE DB YTVO METHOD S ANDTHOS E CONSIDERE DBES T ESTIMATE S FO RADSORPTIO N O N A PROV PAS S SUSPENSIO N

I N J-1 3 VEL L VATE RA T 25° C FO RA N INITIAL CONCENTRATIO N

RANG E OF 1 T O 15 0 fig

L i mL' 1 

### AN

DA SOLID-TO-LIQUI D RATI O O F 1:1 0 9 0 B-V . ADSORBE DLITHIU

M CONCENTRATION S A S ESTIMATE DB YTVO METHOD S ANDTHOS E CONSIDERE DBES T ESTIMATE S FORADSORPTION O N A PROV PAS S SUSPENSIO N

I N J-1 3 VEL L VATE RA T 38° C FORA N INITIAL

i

x

### CONCENTRATION RANG E OF 1 T O 15 0 /t

g L i raL" 1 

### AN

DA SOLID-TO-LIQUI D RATI O OF 1:1 0 9 1 B-VI . ADSORBE DLITHIU

M CONCENTRATION S A S ESTIMATE DB YTV O METHOD S AN DTHOS E CONSIDERE DBES T ESTIMATE S FORADSORPTIO N O N A PROV PAS S SUSPENSIO N

I N J-1 3 VEL L VATE RA T 45° C FORA N INITIAL CONCENTRATIO N

RANG E OF 1 T O 15 0 fig

L i ml " * AN

DA SOLID-TO-LIQUI D RATI O OF 1:1 0 9 2 B-VII . TH E BES T ESTIMAT E OF ADSORBE DLITHIU M A S DETERMINE DB YTV

O METHOD S FO RTH E DESORPTIO N OF LITHIU

M FROM A PROV PAS S SUS PENSIO N I N J-1 3 VEL L VATE RA T 38° C FO RA N INITIAL CONCEN TRATIO N RANG E OF 1 T O 200 0 fig

L i ml" 1 

### ANDA

SOLID-TO-LIQUI DRATI O OF 1:2 0 9 3 B-VIII . TH E BES T ESTIMAT E OF ADSORBE DLITHIUM A S DETERMINE DB YTV

O METHOD S FO RTH E DESORPTIO N OF LITHIU

M FROM A PROV PAS S SUS PENSIO N I N J-1 3 VEL L VATE RA T 38° C FO RA N INITIA L CONCEN TRATIO N RANG E OF 1 T O 15 0 fig

L i mL " * AN

DA SOLID - TO - LIQUI DRATI O O F 1:1 0 9 4 C-I . ADSORPTIO N

EQUILIBRIUM

DATA FORTH E 1-200 0 fig

raL' 1 

### RANG E OF INITIA L LITHIUM

CONCENTRATION S I N

SOLUTIO N A T 25°C . CONCEN TRATION S CORRESPON DT O MEASURE DLITHIUM ; SOLID-TO-LIQUI D RATI O = 1:2 0 9 9 C-II . ADSORPTIO N

EQUILIBRIUM

DATA FORTH E 1-200 0 fig

mL" 1 

### RANG E OF INITIA L LITHIUM

CONCENTRATION S I N

SOLUTIO N A T 25°C . CONCEN TRATION S AR E BES T ESTIMATE S FRO M MEASURE DLITHIU

M ANDOTHE R CATIONS ; SOLID-TO-LIQUI DRATI O = 1:2 0 10 0 C-III . ADSORPTIO N

EQUILIBRIUM

DATA FORTH E 1-200 0 /tg

mL ~ ! 

### RANG E OF INITIA L LITHIUM

CONCENTRATION S I N

SOLUTION A T 38°C . CONCEN TRATION S CORRESPON DTO MEASURE DLITHIUM ; SOLID-TO-LIQUI D RATI O = 1:2 0 10 1 C-IV . ADSORPTIO N

EQUILIBRIUM

DATA FORTH E 1-200 0 fig

mL" 1 

### RANG E O F INITIA L LITHIUM

CONCENTRATION S I N

SOLUTION A T 38°C . CONCEN TRATION S AR E BES T ESTIMATE S FROM MEASURE DLITHIU

M ANDOTHE R CATIONS ; SOLID-TO-LIQUI DRATI O = 1:2 0 10 2

### C-V . ADSORPTIO NEQUILIBRIU MDATAFO R TH E 1-200 0 figmL" 1 

### RANG E O F

INITIA L LITHIU MCONCENTRATION S I NSOLUTIO NA T 45°C . CONCEN

TRATION S CORRESPON D T O MEASURE D LITHIUM ; SOLID-TO-LIQUI D RATI O = 1:2 0 10 3 C-VI . ADSORPTIO NEQUILIBRIU MDATAFO R TH E 1-200 0 figmL" 1 

### RANG E O F INITIA L LITHIU MCONCENTRATION S I NSOLUTIO NA T 45°C . CONCEN

TRATION S AR E BES T ESTIMATE S FRO MMEASURE D LITHIU MAND OTHE R CATIONS ; SOLID-TO-LIQUI D RATI O = 1:2 0 10 4 C-VII . ADSORPTIO NEQUILIBRIU MDATAFO R TH E 1-15 0 figmL" l 

### RANG E O F INITIA L LITHIU MCONCENTRATION S I NSOLUTIO NA T 25°C . CONCEN

TRATION S CORRESPON D T O MEASURE D LITHIUM ; SOLID-TO-LIQUI D RATI O = 1:1 0 10 5 C-VIII . ADSORPTIO NEQUILIBRIU MDATAFO R TH E 1-15 0 figmL' 1 

### RANG E O F INITIA L LITHIU MCONCENTRATION S I NSOLUTIO NA T 25°C . CONCEN

TRATION S AR E BES T ESTIMATE S FRO MMEASURE D LITHIU MAN D OTHE R CATIONS ; SOLID-TO-LIQUI D RATI O = 1:1 0 10 6 C-IX . ADSORPTIO NEQUILIBRIU MDATAFO R TH E 1-15 0 figmL" 1 

### RANG E O F INITIA L LITHIU MCONCENTRATION S I NSOLUTIO NA T 38°C . CONCEN

TRATION S CORRESPON D T O MEASURE D LITHIUM ; SOLID-TO-LIQUI D RATI O = 1:1 0 10 7 C-X . ADSORPTIO NEQUILIBRIU MDATAFO R TH E 1-15 0 figmL " J 

### RANG E O F INITIA L LITHIU MCONCENTRATION S I NSOLUTIO NA T 38°C . CONCEN

TRATION S AR E BES T ESTIMATE S FRO MMEASURE D LITHIU MAN D OTHE R CATIONS ; SOLID-TO-LIQUI D RATI O = 1:1 0 10 8 C-XI . ADSORPTIO NEQUILIBRIU MDATAFO R TH E 1-15 0 figmL' 1 

### RANG E O F INITIA L LITHIU MCONCENTRATION S I NSOLUTIO NA T 45°C . CONCEN

TRATION S CORRESPON D T O MEASURE D LITHIUM ; SOLID-TO-LIQUI D RATI O = 1:1 0 10 9 C-XII . ADSORPTIO NEQUILIBRIU MDATAFO R TH E 1-15 0 figmL" 1 

### RANG E O F INITIA L LITHIU MCONCENTRATION S I NSOLUTIO NA T 45°C . CONCEN

TRATION S AR E BES T ESTIMATE S FRO MMEASURE D LITHIU MAN D OTHE R CATIONS ; SOLID-TO-LIQUI D RATI O = 1:1 0 11 0

x i

### C-XIII . DESORPTIO N EQUILIBRIUM

DATA FO RTH E 1-200 0 fig

mL" 1 

### RANG E OF INITIA L LITHIU

M CONCENTRATION S IN

SOLUTION A T 38°C . CONCEN TRATION S AR E BES T ESTIMATE S FROM MEASURE DLITHIU

M ANDOTHE R CATIONS ; SOLID-TO-LIQUI DRATI O = 1:2 0 Il l D-I . STATISTICA L ANDMODE L PARAMETE RESTIMATE S OF TH E LINEAR ISOTHERM FO RTH E ADSORPTIO N

OF LITHIU

M O N A PRO V PAS S SUSPENSIO N IN J-1 3 VEL L VATE RFORA

N INITIAL LITHIU

M CONCENTRATIO N

RANG E OF 1 T O 200 0 fig

L i mL" l 

### AN

DA SOLID-TO LIQUI DRATI O OF 1:20 . 11 4 D-II . STATISTICA L ANDMODE L PARAMETE RESTIMATION S OF TH E LANGMUI R ISOTHERM FO RTH E ADSORPTIO N

OF LITHIU

M O N A PRO V PAS S SUS PENSIO N I N J-1 3 VEL L VATE RFORA

N INITIAL LITHIU

M CONCEN TRATIO N RANG E O F 1 TO 200 0 fig

L i mL" 1 

### AN

DA SOLID-TO-LIQUI D RATION OF 1:2 0 11 5 D-III . STATISTICA L ANDMODE L PARAMETE RESTIMATE S OF TH E FREUNDLIC H ISOTHERM FO RTH E ADSORPTIO N

OF LITHIU

M O N A PRO V PAS S SUSPEN SION I N J-1 3 VEL L VATE RFO RA

N INITIAL CONCENTRATIO N

RANG E OF 1 T O 200 0 fig

L i ml' 1 

### ANDA

SOLID-TO-LIQUI DRATI O OF 1:2 0 . . .11 6 D-IV . STATISTICA L ANDMODE L PARAMETE RESTIMATE S OF TH E MODIFIE D FREUNDLIC HISOTHERM

FO RTH E ADSORPTION

OF LITHIUM

O N A PRO V PAS S SUSPENSIO N

I N J-1 3 VEL L VATE RFORA

N INITIA L CONCEN TRATIO N RANG E OF 1 T O 200 0 fig

L i mL " X

### ANDA

SOLID-TO-LIQUI D RATI O OF 1:2 0 11 7 D-V . STATISTICA L ANDMODE L PARAMETE RESTIMATE S OF TH E LINEARISOTHERM FO RTH E ADSORPTIO N

OF LITHIU

M O N A PRO V PAS S SUSPENSIO N

I N J-1 3 VEL L VATE RFO RA

N INITIAL CONCENTRATIO N

RANG E OF 1 T O 15 0 fig L i mL' 1 

### ANDA

SOLID-TO-LIQUI DRATI O OF 1:1 0 11 8 D-VI . STATISTICA L ANDMODE L PARAMETE RESTIMATE S OF TH E LANGMUI R ISOTHERM FO RTH E ADSORPTIO N

OF LITHIU

M O N A PRO V PAS S SUSPEN SION IN J-1 3 VEL L VATE RFORA

N INITIAL CONCENTRATIO N

RANG E OF 1 T O 15 0 fig

L i mL' 1 

### ANDA

SOLID-TO-LIQUI DRATI O OF 1:1 0 11 9 D-VII . STATISTICA L ANDMODE L PARAMETE RESTIMATE S OF TH E FREUNDLIC H ISOTHERM FO RTH E ADSORPTIO N

OF LITHIU

M O N A PROV PAS S SUSPEN SION I N J-1 3 VEL L VATE RFO RA

N INITIAL CONCENTRATIO N

RANG E OF 1 T O 15 0 fig

L i mL" 1 

### ANDA

SOLID-TO-LIQUI DRATI O OF 1:1 0 12 0 D-VIII . STATISTICA L AN

DMODE L PARAMETE RESTIMATE S OF TH E MODIFIE D FREUNDLIC HISOTHERM

FO RTH E ADSORPTION

OF LITHIUM

O N A PROV

xi i

### PAS S SUSPENSIO N I N J-1 3 WEL L VATE RFO RA

N INITIA L CONCEN TRATIO N RANG E O F 1 T O 15 0 fig

L i mL ~ X

### AN DA SOLID-TO-LIQUI D RATI O OF 1:1 0 12 1

xii i

### CHARACTERIZATION O P REACTIVE TRACER S FORC-VEIL S FIEL DEXPERIMENTS I : ELECTROSTATI C SORPTION MECHANISM , LITHIU

M b y H . R . Fuentes , V . L . Polzer , E . H . Essington ,

an dB . D . Newma n ABSTRAC T Lithiu m (Li + ) wa s introduce da s lithiu m bromid e (LiBr) , a s a retarde dtrace r fo r experiment s i nth e C-well s comple xa t Yucc a Mountain , Nevad a Tes t Site , Nevada . Th e objectiv e wa s t o evaluat e th e potentia l o f lithiu m t o sorbpredominatel y

b y physica l forces . Lithiu m wa s selecte da s a candidat e trace r o a th e basi s o f hig hsolubility , goodchemica l andbiologica l stability , an

drelativel y

lo w sorptivity ; lac ko f bioaccumulatio nan

dexclusio na s a priorit y pollutan t i n pertinen t federa l environmenta l regulations ; goo danalytica l detectabilit y

an dlo w natura l backgroundconcentrations ; anda lo w cost . Laborator y

experiment s wer e performe dwit h suspension s o f Prow

Pas s cutting s fro

m dril l hol e CE-25p# l a t depth s betwee n54 9 an

d59 4 m inJ-1 3 wate r a t a pH o f approximatel y

8 andi nth e temperatur e rang e o f 25° C t o 45°C . Batc hequilibriu

m andkinetic s experiment s wer e performed ; estimate dthermodynami c constants , relativ e behavio r betwee n adsorptio nanddesorption , an dpotentiometri c studie s provide d informatio nt o infe r th e physica l natur e o f lithiu m sorption . Modelin g o f th e equilibriu m adsorptio ndat a indicate s tha t lithiu m adsorptio ncanb e effectivel y represente di nth e rang e o f 1 t o 200 0 ng

ml' o f initia l lithiu m concentration s b

y th e followin g isotherms : Linear , Langmuir , Freundlich , andModifie d Freundlich . Th e Modifie dFreundlic hi s a genera l equatio nfrom whic hth e other s ca nb e derived . Th e applicabilit y o f thes e isotherm s t o variou s flow regime s an

dinfluen t condition s mus t b e verifie di nlaborator y colum nan dfiel dexperiments . Thermodynami c estimate s indicat e tha t lithiu m adsorb s t o th e Prow Pas s i ncontac t wit hJ-1 3 wate r b y a physica l (electrostatic ) mechanism . Enthalpie s o f adsorptio nar e i nth e rang e expecte dfo r physica l adsorptio n(<1 2 kca l mole " ) . Thes e result s ar e supporte db y th e reversibilit y

betwee nth e adsorptio nan

ddesorptio no f lithiu

m an db y it s behavio r i n potentiometri c studies . Th e potentiometri c studie s indicat e tha t lithiu

m di dno t caus e a shif t i nth e zer o poin t o f charge , whic hi s indicativ e o f physica l sorption . Th e characteristic s o f lithiu m i ncombinatio nwit hth e analysi s o f th e laborator y batc hequilibriu

m experiment s

### indicat e tha t lithiu m i s a goodcandidat e trace r fo r a fiel d tes t becaus e i t i s expecte dt o b e onl y slightl y retarde d( a retardatio nfacto r o f abou t 2 ) andt o exhibi t reversibility , a characteristi c tha t shoul dpermi t a bette r trace r recover y withi na reasonabl e perio do f time , dependin g onth e desig no f th e fiel dtest . Anadvantag e o f adding Li + 

### a s LiB r i s th e simultaneou s applicatio no f bromide , whic hi s expecte dt o behav e a s a conservativ e trace r fo r flo w characterization .
1. 0 INTRODUCTION Thi s repor t i s par t o f th e laboratory investigation s conducte db y Lo s Alamo s Nationa l Laborator y (Lo s Alamos ) a s par t o f a stud y o f Reactiv e Trace r Experiment s i nth e C-well s andothe r well s i nth e Yucc a Mountai nVicinity , Nevada . Thi s stud

y wil l provid e informatio nrequire db y th e Yucc a Mountai n Projec t (YMP ) t o describ e th e saturated-zon e hydrologi c characteristic s a t Yucc a Mountain . Th e informatio ni s als o require db y th e YM P geochemistr y

tes t program t o evaluat e th e applicabilit y o f laborator y

dat a t o fiel dconditions . Laborator y

investigation s ar e bein g conducte dt o identif y an d characteriz e a grou po f tracer s t o b e use di nth e C-well s fiel dexperiment s a t Yucc a Mountain . Ideally , eac htrace r shoul dadsor bb y on e predominan t sorptio nmechanism , bu t variou s sorptio nmechanism s ca nactuall y occu r simultaneousl y

(fo r example , ionexchang e andmolecula r siev e i nzeolites ) o r sequentiall y

(fo r example , fil m

diffusio nfollowe db

y ionexchange) . Fo r thi s stud

y two broa dclasse s o f sorption--physica l an dchemical--hav e bee ndefine d(1 ) andar e describe di nTabl e I . Physica l adsorptio ni s very rapi d(i f no t limite db

y diffusio nrates) , reversible , non-site-specific , and wit hlo w heat s o f adsorptio n(<1 2 kca l mol e ) (2) . I ncontrast , chemisorptio ni s mor e site-specifi c an dresult s inadsorptio nenergie s simila r t o tha t o f chemica l bondin g (>2 0 kca l mol e ) (2) . Vithi nthes e tw o genera l classe s o f adsorption , tw o majo r overal l mechanism s ar e o f concer ni nthes e 2TABL E I GENERI C CLASSIFICATIO NO F ADSORPTIO NPROCESSE S

Characteristi c Enthalpy , A H (kca l mol e ) Change s i n vibratio n frequenc y Bon d strengt h
Typ e o f bon d

Force s Physica l



### Lo w <1 2 Smal l (~0.l7. )

Veak ; easil y reversibl e Nonspecifi c an d reversibl e To o wea k t o caus e physica l o r chemica l chang e Proces s Chemica l Hig h >2 0 Larg e Strong ; partiall y o r full yirrevers

ibl e Specifi c and reversibl e Stron g enoug ht o caus e physica l an d chemica l chang e Intermediat e



### Lo w (? ) Smal l t o larg e
Veak ; easil y reversibl e Simila r t o physica l an d chemica l Simila r t o physica l and chemica l chang e Sources : Reference s 1 , 2 .investigations : electrostati c and chemical . Electrostati c adsorptio n

represent s a physica l adsorptio n wher e ion s i n solutio n migrat e t o a diffus e laye r (3,4 ) becaus e o f electrostati c attractio n o f ion s t o a surfac e o f opposit e charg e an d becaus e o f th e dispersiv e influenc e o f diffusio n forces . Ion-exchang e behavio r i s include d i n thi s definitio n i f i t i s stoichiometri c an d reversible . Chemisorptio n refer s t o thos e case s wher e force s a s larg e a s thos e o f chemica l bond s hol d th e adsorbat e (solute ) t o a sit e surfac e (3,4) . Th e sorptio n mechanis mo f a trace r ca n b e inferre d b ysevera l kind s o f data : enthalp yan d zer o poin t o f charg e (ZPC) . Th e enthalp yo f sorptio n ca n b e determine d fro misother mdat a obtaine d a t thre e temperatures . Enthalp y value s o f <1 2 kca l mole " ar e indicativ e o f physica l (electrostatic ) sorptio n and thos e o f >2 0 kca l mole " ar e indicativ e o f chemica l sorption . Th e ZP C ca n b e determine d fro mpotentiometri c titration s o f electrolyt e solution s i n contac t wit hth e sorben t materia l an d fro melectrophoreti c measurements . I f th e presenc e o f th e trace r displace s th e ZPC , the n chemica l sorptio n i s indicated ; i f th e ZP C i s no t displaced , the n physica l sorptio n i s indicated . Th e objectiv e o f th e laborator yeffort s i s t o characteriz e lithium(Li) , introduce d a s lithiumbromid e (LiBr) , a s a candidat e trace r o f th e electrostati c sorptio n mechanis mfo r th e fiel d experiments . Laborator ybatc h experiment s wer e conducte d t o evaluat e an d t o mode l th e exten t o f lithium adsorptio n t o prepare d sample s fro mth e Pro wPas s Membe r o f Yucc a Mountai n i n J-1 3 wel l wate r (groundwate r fro mth e Yucc a Mountai n vicinit yuse d a s referenc e wate r i n mos t geochemica l investigations ) b yisotherms . I n a n attemp t t o demonstrat e th e physica l natur e o f th e adsorptio n o f lithium , additiona l tests , includin g desorptio n i n solution s o f differen t ioni c strength s an d potentiometri c studies , wer e conducted .2. 0 TRACE R SELECTIO NCRITERI A

Th e selectio n o f a trace r tha t adsorb s predominantl ybyphysica l adsorptio n wa s base d o n th e followin g criteria :

• physicochemica l properties ,

• environmenta l regulations ,

• detection , and

• cost . Th e mos t importan t physica l propert yi s th e reactio n o f th e trace r wit h th e roc k matrix . Bowever , th e trace r shoul d b e sufficientl ymobil e t o trave l fro mth e injectio n wel l t o th e observatio n well s i n a reasonabl e perio d o f tim e wit hreasonabl e groundwate r flo wrates . Thus , conventiona l tracer s (5 ) tha t migrat e wit hgroundwate r velocitie s ar e no t adequate . O n th e othe r hand , th e trace r mus t b e stabl e s o tha t othe r processe s (fo r example , microbia l uptake , complexation, an d volatilization ) d o no t complicat e th e monitoring , measuring , and modelin g o f th e tracer . On e criterio n fo r th e selectio n o f tracer s i s obtainin g approva l fro menvironmenta l agencie s (federal , state , and local) . Thus , chemical s include d i n majo r regulator yaction s and thei r amendment s hav e no t bee n considered . Organi c compound s wit hsignifican t volatilit yan d potentia l fo r complexatio n and compound s subjec t t o biotransformatio n hav e als o bee n excluded . Thes e constraint s leav e limite d choices . Radioactiv e tracer s tha t offe r advantages , fo r example , simple r analysi s and mor e realisti c simulatio n o f repositor yreleases , hav e bee n exclude d fro mconsideratio n fo r fiel d test s becaus e o f thei r potentia l rejectio n b

yregulator yagencies .3. 0 LITHIU M

Literatur e searche s and consultation s wit hexpert s indicat e tha t lithium a s LiB r ma ysatisf ymos t o f th e requirement s discusse d i n Sectio n 2.G . Table s I I and II I contai n informatio n o n lithiuman d lithiumbromide . Thi s informatio n include s physicochemical , thermodynamic , and toxicologica l characteristics , a s wel l a s reference s t o th e mor e pertinen t federa l environmenta l regulations . Lithiumbromid e dissolve s and speciate s int o L i and B r i n water , thu s producin g tw o tracers , on e reactiv e (nonconservative ) and on e nonreactiv e (conservative) . LiB r i s solubl e i n wate r a t sufficientl y hig hconcentration s fo r eas yus e i n fiel d test s (i.e. , hundred s o f /j g m L ) . Lithiumdoe s no t appea r t o for mcomplexe s tha t ca n complicat e it s chemistr y and analytica l identification . Additionally , it s lo wpotentia l fo r microbia l conversio n increase s it s traceabilit yi n laborator yan d fiel d studies . A s i n th e cas e o f th e res t o f th e alkal i elements , lithiumha s a singl e electro n i n th e outermos t energ yleve l o f it s atom . Thi s electron , whic hi s easil ydetachable , cause s a n extremel yreactiv e chemica l character . Becaus e o f th e smal l siz e o f it s ato mand ion , th e behavio r o f lithiumi s transitiona l betwee n th e behavio r o f th e alkal i metal s an d tha t o f th e alkalin e eart h metals . Thes e group s presen t a hig hioni c potentia l (rati o o f io n radiu s t o io n charge) , whic himplie s tha t lithiumi s expecte d t o b e highl ysolubl e and mor e easil yweatherabl e (leachable ) tha n transitio n metals , aluminu mcations , and oxyanion s (15) . Genera l informatio n o n lithiumi s availabl e fro ma numbe r o f sources . Thermodynami c dat a includ e enthalpy , entropy , and fre e energ yo f formation s fo r lithiumand lithiumspecie s (16 , 17 , 18) . Informatio n o n th e distributio n o f lithiumi n th e lithospher e and i n specifi c geochemica l system s ha s als o bee n documente d (19 , 20) . 6TABL E I I LITHIUM CHARACTERISTIC S
Physicochemica l Atomi c numbe r 3 Atomi c weigh t 6.94 1 Specifi c gravit y0.5 3 a t 20° C (solid ) Hydrate d radiu s 3. 4 A Ioni c radiu s 0.6 8 A Hea t o f solutio n -17,50 0 ca l g Natura l isotope s 6 (7.47 . abundance) , 7 (92.67 . abundance ) Thermodynami c (L i ) . AG° f = -70. 1 kca l mole" 1 a t 298.15 K AH° f = -66. 6 kca l mole' 1 a t 298.15 K S ° = 3. 2 ca l deg" 1 mole" 1 a t 298.15 K Toxicit y

• Th e lithiumio n ma yinjur e kidneys , especiall yi f sodiumintak e i s limited . • Effec t o f lo wconcentration s o n aquati c lif e i s unknown . • Waterfow l toxicit ydata : no t available . • Foo d chai n concentratio n potential : none . • CA S RN : 7 4 39-93-2 , NIOS H No : OJ 554000 0 Environmenta l Regulation s Lithiumi s no t include d i n th e Clea n Wate r Act , th e Resourc e Conservatio n and Recover yAct , th e Superfun d Amendment s Reauthorizatio n Ac t o r th e Saf e Drinkin g Wate r Act . I t i s inventorie d i n th e Toxi c Substance s Contro l Act . Sources : Reference s 6 , 7 , 8 , 9 , 10 , 11 , 1 2TABL E II I LITHIUM BROMID E CHARACTERISTIC S

Phvsicochemica l For m Molecula r weight " Meltin g poin t Boilin g poin t Specifi c gravit y Solubilit yi n 10 0 g wate r Whit e hygroscopi c granula r powde r 86.8 5 550° C 1265° C 3.46 4 a t 25° C 17 7 g a t 20° C 20 2 g a t 40° C 22 4 g a t 60° C Hea t o f solutio n Hydratio n state s Six-fol d coordinatio n 11. 4 ca l mole " (water ) Mono , di , tr i and pent a hydrat e Bon d length : 2.7 5 Angstro m Thermodvnami c 4G° f = -94.9 5 kca l mole" 1 a t 298.15 K 4H° f = -95.6 1 kca l mole" 1 a t 298.15 K S ° = 22. 9 ca l mole" 1 a t 298.15 K Toxicit v 

### L D 5 0 = 1,68 0 mg k g - 1 (test s wit hmice , subcutaneous )

• Larg e dose s ma ycaus e CN S (centra l nervou s system ) depression . Chroni c adsorptio n ma ycaus e ski n eruption s and CN S disturbance s becaus e o f bromide . Ma yals o caus e disturbe d bloo d electrolyt e balance . • CA S RN : 7 5 50-35-8 ; NIOS H No : O J 575500 0 Environmenta l Regulation s Lithiumbromid e i s no t include d i n th e Clea n Vate r Act , th e Resourc e Conservatio n and Recover yAct , th e Superfun d Amendment s and Reauthorizatio n Ac t (lithiumchromate , lithiumhydrid e and bromin e ar e included) , o r th e Saf e Drinkin g Vate r Act . I t i s inventorie d i n th e Toxi c Substance s Contro l Act . Sources : Reference s 6 , 9 , 10 , 11 , 12 , 13 , 1 4Sorptio n informatio n fo r lithiumo n soil s and rock s i s scarce . Asurve y o f th e literatur e indicate s a lac k o f pertinen t investigations . Th e surve y use d compute r searche s t o inventor yjournal s i n th e field s o f environmenta l scienc e o r engineering , soi l chemistry , an d geochemistry . Thi s lac k o f succes s ma yb e becaus e lithiumi s no t a n elemen t o f concer n i n agricultura l productio n an d i s no t considere d a contaminan t accordin g t o environmenta l regulations . Tw o reference s (21 , 22 ) deserv e mentio n becaus e the yconstitut e recen t summarie s o n th e sorptio n o f inorgani c element s b ymaterial s o f th e subsurfac e environment . Th e firs t summar y(21 ) reviewe d literatur e fro m approximatel y50 0 paper s o n catio n exchang e i n soi l systems . Selectivit y coefficient s an d estimate d thermodynami c parameter s wer e compile d fo r soil s an d soi l component s i n well-define d systems . Lithiu mwa s reporte d onl ya s th e residen t catio n o f Li-clay s i n exchange s wit halkal i an d ammoniu mion s NH , i n solutions . Th e estimate s o f th e exces s fre e energ yindicat e tha t th e exchang e favor s th e adsorptio n o f al l th e ion s ove r lithium . Asecon d recen t bibliograph ywa s complete d b yth e Energ yPowe r Researc hInstitut e (EPRI ) (22) . Thi s bibliograph ycontaine d ove r 35 0 references , publishe d befor e Februar y 1983 , dealin g wit hchemica l and biologica l attenuatio n mechanism s fo r 2 1 inorgani c elements ; lithiumwa s no t included . Thi s surve yfoun d tha t adequat e dat a exis t t o mak e quantitativ e estimate s fo r onl ya fe wsolute s and tha t attenuatio n i s expecte d t o var ya s a functio n o f th e chemica l elemen t an d th e compositio n o f th e subsurfac e media . Th e abov e limite d informatio n o n lithium illustrate s it s lac k o f priorit yi n sorptio n research . Mos t availabl e basi c informatio n o n th e adsorptio n o f lithiumb ynatura l adsorbent s refer s t o it s inclusio n i n studie s t o characteriz e difference s o f behavio r amon g ions . Investigation s a s earl ya s 192 2 showe d lo wexchang e o f lithiumfo r bariu mand calciumi n soil s an d hig hexchang e o f lithiumfo r ion s 9wit hatomi c weight s highe r tha n thos e o f bariuman d calcium(23) . Late r investigation s (24 ) examine d th e influenc e o f solutio n concentratio n and th e natur e o f th e interactin g ion s o n lithiumadsorption . Selectivit ysequence s ar e use d t o documen t th e effect s o f io n characteristic s o r behavio r o n adsorptio n preferenc e o f ion s fo r a n adsorbent . Suc hsequence s include d valence , equivalen t volume , polarizability , interaction s wit hresiden t ions , and comple x formation . Adsorptio n o f lithiumdoe s no t see mt o involv e a stron g surfac e interaction . Fo r instance , som e studie s strongl ysugges t tha t lithiumshow s a lowe r preferenc e fo r natura l io n exchanger s tha n d o th e res t o f alkal i cations , namely , sodium(Na T ) , potassiu m( K ), rubidiu m(R b ) , and cesium (Cs + )(25) . Helfferic h(26 ) reporte d tha t exchanger s sho wth e lowes t selectivit yfo r lithiumamon g mos t commo n cations . Othe r finding s fro m investigation s wit hsoil s an d tuf f repor t a lo wadsorptio n o f lithiur c (27 , 28) . Lo wadsorptio n ca n b e a n advantag e fo r a reactiv e trace r becaus e i t wil l resul t i n lowe r retardation , whic hshorten s breakthroug hperiod s i n fiel d tests . Th e genera l orde r o f preferenc e o f monovalen t cation s b ysmectite s (29 ) fo r th e Grou p I Ameta l cation s i s

Cs + > Rb + > K + ft NH 4 + > Na + > Li +
. (3.1 )
Thi s sequenc e indicate s a greate r attractio n o f les s hydrate d cation s t o th e interlaye r o f smectites . Th e les s hydrate d cation s ca n mor e closel yfi t th e cavit yo f th e smectit e six-membere d tetrahedra l rings . Th e sequenc e i s explaine d a t th e molecula r leve l (30 ) b yth e principl e o f har d an d sof t acid s

1 0and bases . Lithiu mi s th e hardes t aci d i n th e selectivit ysequence , s o i t ha s les s abilit yt o exchang e it s solven t wate r molecule s fo r th e oxyge n ion s (sof t base ) i n surfac e functiona l group s tha n d o softe r acid s suc ha s cesium . Ageneral selectivit ysequenc e o f mos t commo n cation s b ygeneral-purpos e catio n exchanger s i s th e followin g (26) :

B a 2 + > Pb 2 + > Sr 2 + > Ca 2 + > Ni 2 + > Cd 2 + > Cu 2 + > Co 2 + > Zn 2 ^ > Mg 2 + , > UD 2 2 + > Tl + > Ag + > Cs + > Rb + > K + > NH 4 + > Na + > Li + , (3.2 )
Thi s selectivit yshow s lithiumwit hth e lowes t preference . I n addition , lithiumi s als o th e leas t strongl yhel d catio n o n syntheti c zeolites , compare d wit hmos t o f th e othe r alkal i element s and wit halkalin e eart helements . Eisenma n (25 ) develope d th e concep t o f "equivalen t anion " t o explai n relativ e bondin g strength s o f cation s i n variou s type s o f exchangers . Fro m th e combinatio n o f catio n size , catio n charge , "equivalen t anion, " an d hydratio n energie s fo r th e cations , prediction s fo r th e bondin g energie s o f th e alkal i element s wer e mad e fo r natura l exchangers . Th e predictions , expresse d a s fre e energies , compare d fairl ywel l wit hexperimenta l measurements . Th e analysi s predict s th e bondin g energie s o f al l alkal i ion s t o clays , zeolites , an d feldspars . I t predict s lithiumt o b e th e leas t adsorbe d io n i n th e presenc e o f sodium , potassium , cesium , o r rubidium . Th e limite d curren t toxicologica l informatio n fo r lithiumbromid e indicate s tha t toxicit yt o aquati c lif e a t lo wlithiumconcentration s ha s no t bee n demonstrate d and tha t bioaccumulatio n i n foo d chain s i s no t expected . Th e absenc e o f regulator yconcer n i n th e majo r environmenta l act s suggest s tha t th e us e o f lithiuma s a trace r shoul d b e feasible . Thi s feasibilit y

1 1coul d b e ensure d b yth e us e o f lo wconcentration s and b yeffectiv e recover yo f injecte d solutions . O f al l th e pertinen t Federa l acts , onl yth e Toxi c Substance s Contro l Ac t (TSCA ) include s lithiuma s par t o f a n inventory . Lithiu mi s no t include d i n th e 12 9 priorit ytoxi c pollutant s (31) . Althoug h regulation s d o no t specificall yaddres s lithium , i t ha s bee n know n t o occu r i n groundwater , a s reporte d b yth e Offic e o f Technolog yAssessmen t (32) . Critica l t o th e constraint s se t b yregulation s i s th e consideratio n o f groundwate r qualit ystandard s define d b ybot hStat e and loca l regulation s i n Nevad a tha t ma yappl yt o th e Yucc a Mountai n area . Th e rol e o f Stat e an d loca l regulation s i s no t discusse d i n thi s study . Lithiu mi n aqueou s solution s ca n b e determine d b ysevera l conventiona l analytica l techniques . O f thes e (33 , 34) , spectroscop y(e.g. , atomi c emissio n spectroscopy ) and chromatography(e.g. , io n chromatography ) offe r competitiv e analytica l cost s an d lo wlimit s o f detection . Limit s o f detectio n ca n b e a t leas t withi n th e part s pe r billio n rang e (ppb ) bu t ca n b e improve d b y concentratio n techniques . Th e backgroun d concentratio n o f lithiumi n J-1 3 wate r i s lo w(abou t 0.0 5 figm L ) compare d wit ha n operationa l rang e a t leas t tw o order s o f magnitud e higher . Th e cos t o f lithiumbromid e i s lo wenoug hno t t o b e o f an yimportanc e i n trace r selection . I n summary , lithiuma s LiB r appear s t o b e a n excellen t candidat e trace r fo r hydrogeochemica l investigation s i n Yucc a Mountai n becaus e o f it s stabilit y and wea k adsorption . I t ma ysho wenoug hadsorptio n t o simulat e th e migratio n o f weakl yreactiv e tracer s i n th e subsurface . Thi s lo wdegre e o f sorptivit y ha s bee n demonstrate d i n intermediate-scal e (caisson ) experiment s conducte d wit hunsaturate d an d saturate d Bandelie r Tuf f (28) . Estimate s fo r lithium retardatio n factor s ar e slightl ygreate r tha n on e (u p t o abou t 1.3 ) whe n experimenta l breakthroug hcurve s (withi n 6 mo f travelin g distanc e fro mth e 1 2source ) ar e fitte d t o a one-dimensiona l advective-dispersiv e equatio n (28) . Simultaneously , lithiumma yb e mor e acceptabl e b yregulator yagencie s fo r us e i n groundwate r studie s tha n othe r tracers , i s detectabl e i n th e figI rang e byconventiona l analytica l equipment , an d i s inexpensive . Currentl yavailabl e equipmen t allow s adaptatio n t o continuous-flo wmonitoring , whic hspeed s u p and improve s th e characterizatio n o f breakthroug hprofile s i n th e field .
4. 0 MATERIAL S AN D METHOD S Thi s sectio n describe s th e Pro wPas s sample s an d th e J-1 3 wel l wate r use d i n al l o f th e investigations . Informatio n abou t experimenta l procedure s and th e applicatio n o f geochemica l modelin g t o experimenta l desig n i s als o presente d i n thi s section .
4. 1 Pro wPas s Sample s an d J-1 3 Vate r Pro wPas s materia l use d i n thes e experiment s consiste d o f cutting s collecte d fro mdril l hol e UE-25p# l abou t 63 0 meas t o f th e C-well s complex . Fiftee n set s o f cutting s fro mdepth s betwee n 180 0 an d 195 0 fee t (54 9 an d 59 4 m ) wer e selecte d becaus e the yrepresen t th e Pro wPas s Member , whic hi s th e firs t geologica l barrie r t o radionuclid e migratio n i n th e saturate d zon e (35) . Th e genera l mineralogica l compositio n o f thes e sample s i s dominate d by feldspars , quartz , and kaolinites , wit hsmal l quantitie s o f smectite , mica , an d hematit e (36) . An analysi s o f a washe d sampl e o f cutting s (se e nex t paragraph ) showe d large r percentage s o f feldspars , quartz , an d cristobalite , wit hsmal l quantitie s o f smectit e and hematit e (37) . Thi s differenc e canno t b e explaine d yet , bu t i t ma yb e relate d t o variabilit yo f sampling . Compare d wit hothe r cutting s fro mth e dril l hole s i n th e C-well s area , thes e sample s appeare d t o hav e th e simples t mineralogi c composition , helpin g t o minimiz e 1 3uncertaint yi n th e laborator ybu t reducin g th e representativenes s o f th e

result s fo r fiel d projections . Th e 1 5 sample s o f cutting s wer e washe d wit hdistille d wate r and composite d t o for msufficien t materia l fo r th e experiments . Durin g drilling , th e cutting s ma yhav e becom e contaminate d wit hoverlyin g roc k material s and drillin g materia l residue s an d additive s tha t woul d interfer e wit hth e experiments . As

s muc ho f th e contaminatin g residu e and additive s a s possibl e wa s remove d bysuspendin g th e cutting s i n distille d wate r an d gentl ysonifyin g and decantin g th e fine s afte r a perio d o f settling . Thirt ysuc htreatment s wer e necessar yt o remov e th e fin e material s believe d t o contai n th e drillin g contaminants . Th e Pro wPas s materia l wa s the n groun d wit ha cerami c pulverize r t o pas s a 500- fi mstainles s stee l sieve . Th e groun d materia l wa s conditione d wit h eigh t successiv e J-1 3 wate r washes ; ke ychemica l constituent s o f th e washe s wer e monitore d fo r completenes s o f conditioning . Table I V summarize s th e ke y constituent s o f th e J-1 3 wate r a s collecte d and afte r th e firs t an d eight h 24- hequilibration s wit htreate d Pro wPas s samples . Base d o n th e limite d chang e ove r th e 8 day s o f treatment , i t wa s conclude d tha t pseudo-equilibriu m ha d bee n reache d withi n th e firs t 2 4 ho f contac t time . Th e dat a fro mth e eight h24- hequilibratio n represen t th e backgroun d compositio n and ar e use d a s a referenc e fo r experiment s wit hJ-1 3 wel l wate r and Pro wPas s materials . Th e <500-// msampl e wa s use d i n al l th e experiments . Characterizatio n o f th e <500-/imfraction s i s give n i n Table V and include s specifi c surfac e area , io n exchang e capacity , mineralog ybyx-ra ydiffraction , an d particl e siz e classification . Specifi c surfac e are a wa s measure d bythre e method s tha t gav e differen t results , a s show n i n Tabl e V . Th e Brunauer-Emmett-Telle r (BET ) metho d 1 4TABL E I V J-1 3 VATE RBEFOR E AN

D AFTE REQUILIBRATIO N VIT H PROV PAS S MATERIAL S {fig

mL " * )

Elemen t A l B B a C a F e X L i N a S i S r C l 

### P O 4 

## so 4 HCO 3 

### p H Origina l

J-1 3 Vate r <0.0 3 0.1 3 <0.00 1 11. 3 0.0 2 5 0.04 0 <0.01 0 0.0 1 4 4 3 0 0.04 0 7 <2. 5 1 9 12 4 

### 7. 2 Firs t

24- h Equilibratio n 0.4 7 0.1 3 0.0 2 13. 5 0.0 5 3 0.0 9 0.7 9 0.00 4 5 0 2 3 0.01 5 8 <2. 5 2 3

~ b

" b Eight h

24- h Equilibratio n 0.2 5 0.1 3 0.00 3 13. 1 0.0 4 3. 0 0.0 5 1. 2 0.00 5 42. 0 27. 0 0.02 0 7 <2. 5 1 9 

### b b C-well a

1 1 2 0.1 1 0.3 8 5 5 2 5 0.04 4 

### 7 2 2 14 2 7. 8

a Source : Referenc e 38 . No t analyzed .

1 5TABL E V PHYSICOCHEMICA L CHARACTERIZATION OF PRO V PAS S TUF F SAMPLE S (<50 0 fim) USE DI N TH E INVESTIGATION S

Propert y Measuremen t 2 - 1 Specifi c Surfac e Are a ( m g " ) : Quantachrome 3 , Brunauer-Emmett-Telle r Microtra c Ethylen e glyco l monoethy l ethe r Catio nexchang e capacit y (me q10 0 g " ) : Na + acetat e (p

H 8.2 ) Exchangeabl e cation s (meq10 0 g " ) : 3.4 6 0.1 9 ± 0.0 6 0.2 6 ± 0.1 2

1 6

C a 2 + M g 2 + 

### Na + 

### K + Li +

X-ra y diffractio n(7i) : feldspa r 60± 7 cristobalit e 15± 1 hematit e 1± 1 Particl e siz e classificatio n|

san d9 6 NH . acetat e (p H 7.0 ) 

### 1 4 0.6 4 4. 2 1. 1 

### ND b



### [7,) C 

### : sil t 4 Na acetat e (p H 8.2 ) 7. 2 0.4 4 1. 8 0.006 8

quart z 22± 2 smectit e 1± 1

clay <0. 3

a Thi s estimat e wa s performe db y Quantachrome Corporatio n(Syosset , NY ) wit ha quantasor bJr . b N D- No t detected . U.S . Departmen t o f Agricultur e classificatio nscheme . 1 6measure s th e amoun t o f nitroge nga s require dt o complet e a monolaye r o f nitroge nmolecule s absorbe db y th e expose dsurfac e o f th e particle . Th e are a wa s estimate dt o b e 3.4 6 m g . Th e ethylen e glyco l monoethy l ethe r (EGME ) method, simila r i nprincipl e t o th e BE T method, gav e result s lowe r tha nthos e from th e BE T metho d(0.2 6 m g ) . Thi s i s understandabl e becaus e th e adsorbin g component , EGME , i s muc hlarge r tha nth e nitroge nga s molecul e and 2 - 1 canno t penetrat e th e smal l pore s accessibl e t o nitrogen . Th e 0.19- m g valu e obtaine dwit hth e Leed s an dNorthru pMicrotra c i s lowe r tha ntha t o f th e EGM E metho dalthoug hno t significantl y different , an

di s obtaine ddurin g measuremen t o f particl e siz e distributio nusin g laser-base dligh t reflectance . Th e mea nparticl e diamete r o f th e groundsample s wa s estimate db y th e Microtra c t o b e abou t 5 0 pm. Assumin g smoot hspherica l particles , th e minimu m specifi c surfac e are a calculate dfo r 50-fiia particle s a t a densit y o f 2. 5 g

- 3 2 1 c m an d0. 5 packin g fractio ni s 0.0 5 ra g " . Th e choic e o f th e valu e o f 2 - 1 surfac e are a t o b e use di ncalculation s wil l b e betwee n0.0 5 an d3.4 6 m g an dwil l depen donth e requirement s o f th e specifi c computations . Catio nexchang e capacit y an dexchangeabl e cation s wer e measure do nth e Prow Pas s material s wit hNH. + (p H 7.0 ) an dNa + (p H 8.2 ) a s exchangin g cation s i nanacetat e buffe r system . Exchangeabl e cation s wer e recovere dupo n treatin g th e NH. + -saturate dPro w Pas s materia l wit hNa + acetat e an dth e Na + -saturate dPro

w Pas s wit hNH 4 + acetate . Particl e siz e classificatio no f th e prepare dProw

Pas s materia l wa s determine db y siev e analysi s fo r fraction s greate r tha n4 4 /t

m an db y a Micromeritic s Sedigraph5000 DParticl e Siz e Analyze r fo r th e smalle r fractions . Vate r from

wel l J-13 , a natura l groundwater , wa s th e primar y solution . Thi s easil y

availabl e wate r ha s bee nuse da s a standar dwate r insorptio n task s fo r th e Yucc a Mountai nProjec t (YMP) . Syntheti c water s ar e th e choic e 1 7fo r developmen t o f fundamenta l informatio nfo r individua l mineral s an d tracers ; however , natura l groundwate r wa s selecte di nanattemp t t o simulat e fiel dcondition s mor e closel y an dt o mee t time an

dresourc e limitations . C-well s water s wer e considere dbu t wer e no t availabl e fo r thes e investigations . Th e compositio no f th e J-1 3 wate r i s no t greatl y differen t fro m tha t o f th e C-well s wate r an dthu s shoul dno t affec t result s fro m thes e laborator y

investigations . Ke y component s o f J-1 3 an dC-well s water s ar e compare di nTabl e IV . Befor e experimenta l use , th e wate r wa s filtere dt o <0.0 5 urni norde r t o remov e potentia l colloida l particulates .

4. 2 Procedure s Detaile dprocedure s (DPs ) hav e bee nformulate daccordin g t o lo s Alamo s Nationa l Laborator y

Qualit y Assuranc e Document s fo r th e Yucc a Mountai n Project , No . 88 , Volume s I , II , an dIII , 1988 . Thes e DP s describ e sorptio n experiments , o r activitie s supportin g thos e experiments , tha t ar e bein g performe di nth e assessmen t o f tracer s fo r th e C-well s project . Thes e procedure s wer e derive do r modifie dfro m peer-reviewe dpublishe dprocedures . Appendi xA

describe s instrumentatio nuse di nth e investigations .

4.2. 1 Adsorptio nKinetic s Two type s o f kinetic s studie s wer e performed : batc htub e studie s t o defin e minimu

m equilibratio ntimes ; an dcontrolle dreacto r studie s t o collec t dat a fo r (a ) evaluatin g th e rol e o f fil m transfe r an

dinterna l diffusio ni n th e laborator y

experiment s an

d(b ) estimatin g activatio nenergies . Th e batch-tub e metho duse d50-m L polyallome r centrifug e tube s wit h2. 0 g o f Prow Pas s material , whic hwa s conditione db y mixin g fo r 2 4 hwit h3 8 m l o f J-1 3 water . Afte r conditioning , 2 m l o f trace r solutio nwa s adde dt o eac h tube , an dmixin g an

dtimin g wer e starte dimmediately . Th e fille dtube s wer e 1 8mixe d continuousl ybytumblin g i n a modifie d Patterson-Kelle yblender . Thre e replicate s fo r eac hsamplin g tim e wer e maintaine d a t a solid-to-liqui d rati o o f 1:2 0 an d a t a controlle d temperatur e o f 38° C (±2°C ) fo r th e duratio n o f th e experiment . Th e samplin g time s o f 1 min , 0. 5 h , 8 h , 2 4 h , 4 8 h , an d 9 6 h wer e expecte d t o cove r th e tim e necessar yfo r th e syste mt o attai n equilibrium . Samplin g involve d centrifugin g th e tube s fo r 1 1 mi n a t a relativ e centrifuga l forc e (RCF ) o f 90 0 an d the n filterin g th e supernatan t throug ha 0.45-/i msyring e filter . Th e sampl e wa s the n spli t int o tw o 20-m l polyethylen e vials . On e via l wa s use d fo r p H measuremen t an d th e othe r wa s acidifie d t o 1% nitri c acid , store d a t 4 C , an d chemicall yanalyzed . Durin g samplin g o f th e firs t batch , bacteri a growt hwa s foun d i n th e tubes , s o al l subsequen t experimenta l material s wer e sterilize d i n a stea mautoclav e befor e bein g use d i n th e sorptio n experiments . Fo r th e controlle d reacto r studies , groun d and sieve d Pro wPas s materia l an d J-1 3 wate r wer e adde d t o a tare d glas s beake r t o mak e th e fina l solid-to-liqui d rati o 1:2 0 o r 1:10 . Th e beake r and it s content s wer e autoclave d an d th e content s wer e transferre d t o th e controlle d reacto r vesse l ( a 500-m l glas s kettl e wit hbaffles , a lid , an d a mixin g syste mwit hspee d control) . Othe r adsorptio n experiment s wit hth e controlle d reactor s wer e conducte d a t 25°C , 38°C , and 45°C , initia l lithiumsolutio n concentration s o f 1 5 and 7 5 /i

g ml " , an d a t mixin g level s o f 700 , 1000 , and 150 0 rpm ; thes e experiment s extende d ove r a perio d o f 1 2 hwit hmor e sample s withdraw n a t th e beginnin g tha n a t th e end . A s wit hth e previou s experiments , equilibriu mwa s reache d withi n th e firs t 2 h , confirmin g th e adequac yo f th e 24- hstandar d equilibratio n time . Th e reacto r and content s wer e allowe d t o conditio n fo r 2 4 ha t constan t mixin g and a temperatur e o f 3 8 ± 2°C . 1 9Durin g mixing , a n appropriat e volum e o f trace r wa s adde d t o th e reactor ; reactio n timin g starte d immediately . Sample s wer e take n bywithdrawin g suspensio n fro mth e reacto r and filterin g throug ha 0.45-/j msyring e filter . Sample s wer e acidifie d t o 17 , nitri c acid , store d a t 4°C , an d chemicall y analyzed . Th e p H wa s measure d o n a sampl e withdraw n fro mth e suspensio n befor e additio n o f th e trace r and agai n afte r th e las t sampl e wa s taken . 4.2. 2 Desorptio n Kinetic s Desorptio n kinetic s wa s evaluate d onl yfo r certai n adsorptio n experimenta l conditions . Th e desorptio n metho d wa s basicall yth e sam e fo r th e batc htub e an d th e controlle d reacto r studies ; exception s ar e note d below . J-1 3 wate r wa s use d a s th e desorbin g solution . Experimenta l conditions , fo r example , temperature , wer e maintaine d th e sam e a s i n th e adsorptio n step . Afte r th e adsorptio n perio d i n th e batc htubes , th e trace r solutio n wa s remove d bycentrifugin g and decanting . Th e tube s wer e weighe d an d th e amoun t o f th e entraine d solutio n wa s determined . Sample s o f solutio n remove d fro m th e tube s wer e collecte d an d analyze d t o determin e th e amoun t o f th e entraine d tracer . Th e solutio n phas e i n th e controlle d reacto r wa s remove d byvacuum filtration . Th e solid s wer e washe d twic e wit hdistille d wate r t o remov e muc h o f th e entraine d nonsorbe d tracer . Asampl e o f th e las t was hwa s retaine d fo r p H an d chemica l analyse s t o determin e th e amoun t o f trace r remainin g i n th e reacto r solution . An amoun t o f J-1 3 wate r wa s adde d t o th e tube s o r t o th e reacto r s o tha t th e solid-to-liqui d rati o wa s maintained . Timin g and mixin g wer e starte d immediatel yafte r additio n o f th e J-1 3 water . Sample s fro mth e batc htube s wer e spli t a s i n th e adsorptio n stag e fo r p H and chemica l analyses . Sample s wer e collecte d fro mth e controlle d reactor s i n 2 0th e sam e manne r a s i n th e adsorptio n stage ; p H wa s measure d o n th e las t sampl e collected . Samplin g time s wer e selecte d t o monito r desorptio n kinetic s fo r period s u p t o 4 8 hfo r th e batc htube s and 96 hfo r th e reactors . 4.2. 3 Equilibriu mAdsorptio n Equilibriu mexperiment s wer e performe d a t 25°C , 38°C , and 45°C , wit hup t o te n initia l trace r concentration s rangin g fro m1 t o 200 0 figml " . Sectio n 4.2. 1 describe s th e basi c setu p and th e genera l procedur e fo r bot hadsorptio n an d desorption . Th e mai n differenc e betwee n th e kinetic s an d equilibriu m experiment s i s tha t samplin g i n equilibriumexperiment s wa s onl ya t th e beginnin g an d en d o f th e equilibratio n period . Th e typica l samplin g tim e fo r equilibriu mstudie s wa s 2 4 hafte r additio n o f th e tracer . 4.2. 4 Equilibriu mDesorptio n Desorptio n equilibriu mwa s evaluate d onl yfo r certai n equilibriu m conditions . J-1 3 wate r wa s use d a s th e desorbin g solution . Sectio n 4.2. 2 describe s th e setup an d procedur e followe d fo r equilibriumdesorption . 4.2. 5 Potentiometri c Titratio n Pro wPas s materia l wa s suspende d i n electrolyt e solution s o f 0.00 5 o r 0. 1 M NaC10 4 i n a rati o o f 2 g solid s t o 4 0 g electrolyte . Asecon d serie s o f sample s wa s prepare d i n th e sam e manner , bu t th e electrolyt e solution s containe d 90 0 figml " lithiuma s LiBr . Eac hsampl e wa s duplicate d an d th e experimen t wa s conducte d a t 38°C . T o eac hsampl e a smal l amoun t o f standardize d 0.2 5 M HC10 4 o r 0.2 5 M NaO H wa s added ; treatment s range d fro m0

2 1t o 300 0 //L . Th e sample s wer e mixe d b ytumblin g fo r 6 h an d wer e the n centrifuged , an d p H wa s measure d directl yo n th e clarifie d supernatant . Concurrently , a separat e se t o f electrolyt e sample s wa s prepare d similarl ybu t withou t Pro wPas s solids . Th e p H measurement s o n thes e sample s wer e use d a s th e referenc e i n th e followin g calculatio n t o estimat e th e ne t adsorbe d charg e (//moles m) :

s Q = k(AH-AOH ) o r (4.1 )

s 0 = k(W a - [OH ] - [H ] + [OH ] ) , (4.2 )

wher e S = ne t adsorbe d charg e (//moles m " ) A H = th e amoun t o f th e adde d H + consumed , //mole s mL " , AO H = th e amoun t o f th e adde d OH " consumed , //mole s m L , [B ] = th e concentratio n o f proton s remainin g afte r reactio n wit hth e solid , //mole s m L , [OH ] = th e concentratio n o f hydroxid e remainin g afte r reactio n wit hth e solid , //mole s mL " , [H] r = th e concentratio n o f proton s remainin g i n th e electrolyt e no t reacte d wit hth e solids , //mole s m L , [0H] r = th e concentratio n o f hydroxid e remainin g i n th e electrolyt e no t reacte d wit hth e solids , //mole s mL " , and

- 2 k = syste mconstant , m L m.
4.2. 6 Electrophoresi s Electrophoresi s refer s t o th e movemen t o f charge d particle s relativ e t o a stationar ysolutio n i n a n applie d potential . Th e p H a t whic ha colloi d i s 2 2electrokineticall yuncharge d i s referre d t o a s th e zer o poin t o f charg e (ZPC) . I f th e ZP C i s displace d b yth e additio n o f a tracer , the n chemica l sorptio n i s indicated ; i f not , the n physica l sorptio n i s indicated . Electrophoreti c mobilit yo f colloida l suspension s i s use d t o determin e th e ZPC . Electrophoreti c mobilit y(EM ) i s a measur e o f th e velocit yo f a colloi d i n respons e t o a n electri c fiel d and i s define d a s th e colloi d velocit yi n micrometer s pe r secon d divide d byth e strengt ho f th e electrica l fiel d i n volt s pe r centimeter . An E M ru n consist s o f timin g th e migratio n o f a numbe r o f particle s ove r a measure d distanc e unde r a n applie d voltage . Measurement s o f E M wer e mad e wit ha Zeta-Mete r 3. 0 System . Th e sample s use d fo r E M wer e th e sam e one s use d i n th e potentiometri c measurements , Sectio n 4.2.5 . Th e solid s wer e resuspende d i n wate r an d the n allowe d a minimu mo f 1 0 ht o settle . Aportio n o f th e sampl e (e.g. , 1 mL ) tha t containe d th e desire d particl e siz e rang e (e.g. , < 2 pm) an d proportio n o f solid s wa s retrieve d fro mth e solutio n afte r 1 0 han d place d i n a separat e container . Th e remainin g sampl e wa s the n centrifuge d a t a n RC F o f 90 0 fo r approximatel y1 0 mi n t o separat e th e majorit yo f th e particle s fro mth e bul k liquid . Th e clarifie d liqui d wa s the n adde d t o th e 1 m l sample . Thi s i s essentiall ythe-metho d o f reconstitutio n describe d byth e manufacture r o f th e Zeta-Mete r 3.0 . Fou r sample s wer e prepare d b yvacuumfiltratio n throug hfilte r pape r wit h a por e diamete r o f 8 fim. Thi s metho d prove d t o b e tim e consuming , however , and reconstitutio n wa s use d fo r th e remainin g samples . E M result s wer e obtaine d o n eithe r reconstitute d o r filtere d duplicat e suspension s i n whic hE M value s compare d favorably : -2.57 8 wit h-2.56 3 an d -2.64 1 wit h-2.74 3 /i mc mpe r vol t second .
2 34.2. 7 Abrasio n Effect s

Tumblin g (o r stirring ) suspension s (tub e o r reactor ) o f soil s and geologica l sample s ma ycaus e abrasio n tha t coul d chang e th e particl e siz e distribution s an d creat e ne wsorptio n surface s o r activ e sites . Th e degre e o f abrasio n o f Pro wPas s wa s evaluate d b ymeasuremen t o f particl e siz e distribution s o n mixe d and nonmixe d materials . Dat a fo r th e averag e mes h size s o f 77 4 throug h3 1 pmwer e applie d t o a mode l fo r particl e siz e distributio n (39 ) tha t wa s use d t o fi t th e equatio n

Y = 1 - ex p (x/x o ) n, (4.3 )

wher e Y = cumulativ e fractio n o f materia l b yweigh t les s tha n siz e x ( x i n Urn), x = characteristi c particl e size , fim, and , n = constan t specifi c t o th e sampl e and breakag e conditions . Linearizatio n o f Equatio n (4.3 ) followe d b ylinea r regressio n provide d a goodnes s o f fi t and a n estimat e o f th e constants . Tabl e V I summarize s thos e estimate s an d regressio n statistics . An F-tes t compariso n o f th e regressio n fo r th e sampl e befor e tumblin g an d tha t afte r tumblin g indicate d tha t th e tw o siz e distribution s wer e significantl ydifferen t a t th e 99.57 . confidenc e level . Thus , reacto r experiment s ma yaffec t distributio n o f sizes , bu t furthe r evaluatio n i s neede d t o estimat e th e variabilit yi n trace r respons e relativ e t o differen t particl e siz e distributions .

2 4

### TABL E V I

REGRESSION

ANDCOMPARISON

BETVEEN SIZ E DISTRIBUTION S BEFOR E ANDAFTE RTUMBLIN

G

Statistics a 

### Sampl e befor e Tumbling Sampl e afte r Tumblin g R 2 

### 0.94 5 0.97 8 C.V . 36.40 0 65.37 0 n2.19 0 1.74 9 x Q

### 194.9 8 186.2 1 F-tes t F-calculate d= 33.5 0 > F-tabulate d(at 99.57 . confidenc e

level ) = 6.27 ; the nth e distribution s ar e significantl y different .
a 

### R= inde xo f determination ; C.V . = coefficien t o f variance ; n , x = constant s i nEquatio n(4.3) .

2 54. 3 Model s

Evaluatio no f th e suitabilit y o f lithiu

m a s a trace r o f physica l sorptio n i nfiel dtest s i nth e C-well s saturate dzon e include dmodelin g wit hisother m andthermodynami c models . Th e isother m model s wer e use dt o determin e th e exten t o f sorptio nan

dt o provid e informatio nfo r th e thermodynami c models . Th e thermodynami c model s wer e ase dt o estimat e energie s associate dwit hth e mechanis m

o f sorption .

4.3. 1 Isotherm s Isotherm s hav e bee nderive danduse dt o represen t sorptiv e behavio r i na variet y o f discipline s (2 , 3 , 40 , 41) . Thre e o f th e mor e commonl y use d isotherm s ar e th e Linear , Langmuir , an dFreundlich . Thes e thre e model s plu s th e Modifie dFreundlic hisotherm , a genera l isother m fro m whic hth e other s ca n b e derived , wer e fitte dt o th e equilibriu m lithiu m concentrations . Th e simples t an

dmos t widel y

usedo f th e equilibriu m sorptio nisotherm s i s th e linea r relationshi p

S = K d C , (4.4 )

wher e S = concentratio no f solut e sorbe db y th e solid , C = concentratio no f solut e i nsolution , an d K , = distributio ncoefficient .
Thi s expressio ni s widel y use di ntranspor t model s t o describ e th e sorptio no f reactiv e solute s b y solids . On e limitatio ni s tha t th e maximu m quantit y o f adsorptio ni s no t included . Th e distributio ncoefficien t K . i s 2 6th e rati o o f retentio n o f solut e b yth e soli d t o th e solut e i n solutio n and i s assume d t o b e independen t o f concentration . Thi s i s no t alway s th e case , an d conclusion s draw n fro mmodelin g base d o n assumption s o f linea r sorptio n behavio r ma yno t b e valid . Langmui r develope d a quantitativ e mode l tha t ha s als o bee n widel yapplie d t o describ e experimenta l dat a (42) . Th e Langmui r equatio n wa s derive d fo r th e sorptio n o f gase s o n a soli d surface . Nevertheless , i t ha s bee n extende d t o includ e th e sorptio n o f solute s b ysolids . Th e basi c expressio n take s th e for m

c kbC u S = jrp-fl j , (4 . wher e k , b = empirica l constants . Linearizatio n o f Equatio n (4.5 ) provide s th e followin g transformatio n t o b e fitte d t o th e experimenta l data : C/ S = (l/b) C + 1/kb . (4.6 )

I n thi s expression , k i s a measur e o f th e strengt ho f th e sorptio n bon d an d b i s th e maximu mamoun t o f th e solut e tha t ca n b e sorbe d b yth e soli d (40) . Thi s isother mi s base d o n th e theoretica l assumptio n tha t th e sorptio n site s ar e homogeneousl ydistribute d relativ e t o energ ypotentials . Th e Freundlic hisother mha s th e for m

S = KC N, (4.7 )

2 7wher e K, N

= empirica l constants . Estimatio no f th e constant s i s possibl e b y th e logarithmi c transformatio n o f Equatio n(4.7 ) t o
lo g S = N lo g C + lo g K . (4.8 )
Thi s expressio ni s als o very popula r i nth e literatur e becaus e o f th e flexibilit y

o f th e exponentia l functio nt o fi t experimenta l data . Th e equatio ni s a bette r representatio no f heterogeneou s behavior . Th e Linea r andLangmui r isotherm s assume tha t th e energy o f adsorptio ni s th e same fo r al l activ e site s o nth e adsorben t surface . However , th e assumptio nfail s i nmany case s becaus e eithe r pur e minera l o r multiminera l adsorptio nsite s interac t wit hsolute s a t differen t energie s (heterogeneity) . Thes e difference s amon g sit e energie s requir e th e identificatio no f thos e energy distribution s tha t characteriz e th e heterogeneit y o f a particula r adsorbent/solut e interaction . Then , equation s suc ha s th e Freundlic hisother m ar e bette r modelin g alternatives . Sip s (43 ) introduce dan ddiscusse danisother

m tha t suggest s a Gaussian-lik e statistica l functio ntha t coul drepresen t th e distributio no f site/solut e interactions . Thi s isother m i s base do nth e assumptio ntha t localize dadsorptio noccur s withou t interactio namon g site s andwa s presente d a s a nexpansio no f th e conventiona l Freundlic hisotherm . Sposit o (44) , followin g th e derivatio nobtaine db y Sip s (43 ) an

dusin g a Langmui r isother m t o defin e site/solut e interactions , derive da simila r Gaussian-lik e statistica l functio ntha t i s regarde da s a log-norma l distributio no f a variabl e tha t define s th e relativ e affinit y o f a solut e fo r a soli dphase . 2 8Th e isotherm , referre d t o a s Modifie d Freundlich , ca n b e expresse d a s

c — s m a ma x 1 + Kj^ C
wher e S = maximu mavailabl e exchang e capacit yo f soli d phas e an d K D , p = parameter s tha t defin e th e overal l solute/soli d phas e interaction . I f thi s isother mapplies , a mor e comprehensiv e representatio n o f th e heterogeneit yo f th e adsorptio n i s gaine d fro mth e meanin g o f K ^ and p. Thes e tw o parameter s ca n b e foun d b yregressio n analysi s o f a give n se t o f sorptio n dat a o n th e followin g expressio n transforme d fro mEquatio n (4.9) :
lo g g S

_s = Plo g C + lo g (K/) . (4.10 ) ma x Th e paramete r p ha s bee n describe d (44 ) a s a measur e o f ho wsharpl y peaked , abou t a n averag e value , i s th e statistica l functio n fo r th e distributio n o f surface-bindin g energie s a t equilibrium . Thi s paramete r ha s als o bee n describe d byCrickmor e and Vojciechowsk i (45 ) a s th e sprea d o f th e statistica l functio n fo r th e distributio n o f adsorption-desorptio n rat e constants . Th e paramete r K nha s bee n implicitl yrelate d (44 ) t o a n averag e "distributio n coefficient, " o r a n averag e adsorptio n energ yo r affinity . Crickmor e and Vojciechowsk i (45) , o n th e othe r hand , defin e I L a s th e rati o o f th e reactio n rat e constant s tha t represen t simultaneou s /?-orde r adsorption-desorptio n rates . Bot hparameters , Pand K^ , ar e temperatur e and p H dependent . 2 9I t i s importan t t o not e tha t Equatio n(4.9 ) i s th e genera l isotherm fro m whic hcommo nisotherm s ca nb e derive dbase donth e followin g conditions : Linea r isotherm s (/

? = 1 , Kj/H / < < 1) , th e langmui r isotherm (/ ? = 1) , andth e Freundlic hisotherm

( 0 < / ? < 1 , K D V

< < 1) . 4.3. 2 Thermodynamic s Th e thermodynami c parameter s use dt o evaluat e sorptio nmechanism s ar e th e equilibrium

constan t ( K) , th e fre e energ y o f sorptio n(AG°) , th e enthalpy o f sorptio n(AH 0 ) , andth e entropy o f sorptio n(AS 0 ) . Thus , th e equilibriu m constan t fo r io nexchang e i s base do nth e la w o f mas s actio n(26 ) andca nb e writte na s

- Z B Z A

a A • a n

a B * a A fo r th e reactio n

z fi A + z A B = z f i A

+ z A B , (4.12 )

wher e A , B = ionspecie s o f th e binar y system i nsolution , A , B = th e ionspecie s i nth e soli dphase , a. , a. . = th e activitie s o f A andB , respectively , i nth e solutio nphase , *A ' ^ B = t ^ i

e act i v itie s o f A

andB , respectively , i nth e soli dphase , an d z A , z R= th e valence s o f A an dB , respectively .

3 0Equatio

n(4.11 ) ca

nb e expresse

di nterm s o f th e followin

g modifiedrationa l equilibriu

m constant :

2 

### B

= K r \

x Zf i C %k 7 H 

## suc htha t I = \ • - V

• -V- i ( 4 

## - 14 

## ) v A r B -

v B X 

### B C 

### A ^ A wher e 7 , 7 g = th e activit y coefficient s o f A

an dB , respectively , i nth e solutio nphase , 7» , 7 g = th e activit y

coefficient s o f A

andB , respectively , i nth e soli dphase , C^ , C B = th e nola r concentration s o f A andB , respectively , i nth e solutio nphase , an

d *A ' ^ B = ^ e e Q uiva l e n t fraction s o f A andB , respectively , i nth e soli d phase . Therefore , th e thermodynami c equilibriu m constan t ca nb e expresse da s follow s (26) : 

### lnK e 

### = wher e

X R = z.n . + *-n

_( 4 - 16 )
3 1

### an

d n» , n « ar e mole s o f A

an dB , respectively , i nth e soli dphase . Th e integra l i nEquatio n(4.15 ) canals o b e expresse di nterm s o f it s components :

Q

### ( ^ K r 

### ) dx B

### = z f i 

### j l I nC A 

### dx f i 

### - z A 

### j * I n A fi A 

# j + Z

## A 

## f Q l nG

## B di 

## B • Z 

## B 

## f

Q l nC

## A d 

## *0 + Z

## A 

## f

Q l n7 

## B di 

## B " Z 

## B j j l n

## U di 

## B (4.17 ) 

### Th e integra l i nEquatio n(4.17 ) canb e solve db y severa l means , fo r example , graphicall y

o r analytically . Th e parameter s o f th e Modifie dFreundlic hequatio nca nb e substitute d int o Equatio n(4.17 ) andth e thermodynami c equilibriu m constan t ma y

b e evaluated , i f th e component s o f th e lodifie dFreundlic hequatio nar e converte d int o th e same unit s a s thos e o f Equatio n(4.17) . Th e Gibb s fre e energy

o f sorptio nA

Gcanb e determine dfro

m th e thermodynami c equilibriu

m constan t (45 ) throug hth e equatio n
AG ° = -R T l nI , (4.18 )
wher e Ri s th e ga s constan t an dT i s th e absolut e temperature . Th e enthalpy

o f sorptio ncanb e determine dfro m th e van' t Hof f equatio n (18 , p . 348 )

e _A H, , iO 

### ^

3 2Integratio nol Equatio n(4.19) , wit hrespec t t o temperature , give s

AH 0 = I n(K eT2 / K eT1 ) . I/[(T 2 - T^/T^ ] . (4.20 ) Equatio n(4.20 ) indicate s tha t th e equilibriu m constan t mus t be obtaine da t tw o o r mor e temperatures . I f th e equilibriu m constan t i s obtaine da t mor e tha ntwo temperatures , the nAH 0 ca nb e determine dfrom a plo t o f I nK gvs . j . Th e slop e o f th e plo t i s equa l t o -AH°/R . Th e entropy

o f sorptio nAS 0 canb e determine dthroug hth e relatio n

AG ° = AH 0 - TAS ° . (4.21 )

Th e thermodynami c equilibriu m constan t fo r sorptio ni nwhic hionexchang e i s no t considere dca nb e expresse da s 

# K 

# o 

# = I f 

# '

wher e ai , a . ar e th e activitie s o f A i nth e soli dan

dsolutio nphases , respectively . Equatio n(4.22 ) ca nbe expresse da s



### K Q 

### = > A, (4.23 )

3 3wher e 7» , 7 . ar e th e respectiv e activit y coefficient s o f A

i nth e soli dan

d solutio nphases . A t infinit e dilution , 7 1 an d7 . equa l unity . Thu s th e thermodynami c equilibriu

m constan t ca nb e estimate dfro m th e value s o f C . andC . a t infinit e dilution . A

simple r techniqu e i s als o availabl e t o estimat e C . an dCi a t infinit e dilutio nan

dt o calculat e anoveral l equilibriu m constan t betwee nth e concentration s i nth e soli dan di nsolutio no f th e specie s o r compoundo f concer n(46 , 47 , 48) .
4. 4 Pre-experimenta l Geochemica l Modelin g Th e developmen t o f geochemica l code s t o predic t chemica l equilibri a amon g aqueous , solid , andgaseou s component s offer s a ne w desig ntoo l fo r investigator s o f sorptio nphenomen a (49) . Th e purpos e o f geochemica l modelin g wa s fourfold : a . t o evaluat e the ; effec t o f lithiu m bromid e additio no nth e chemica l 2 + 2 - equilibri a o f majo r ions , e.g. , C a an dC( L ; b . t o predic t possibl e precipitatio no r dissolutio no f th e majo r minera l component s o f th e Pro w Pas s sampl e an

dothe r component s tha t coul db e presen t i nth e fiel do r tha t coul dappea r a s precipitate s durin g experiments ; c . t o predic t th e effec t o f p H o nth e precipitatio no r dissolutio no f th e majo r minera l component s o f th e Prow Pas s samples ; and d . t o investigat e th e distributio no f th e lithiu m ionamon g variou s expecte dlithiu

m compounds , e.g. , LiOH , HJCQ*. Thi s stud y ha s use dth e geochemica l cod e PHREEQ E (50 ) a s anai di nth e desig no f laborator y

batc hsorptio nexperiments . Thi s cod e wa s selecte d becaus e i t i s wel l documente dan di s inth e publi c domain . Th e cod e include s 3 4model s fo r precipitation , dissolution , an dadsorption , an

di s supporte db

y a thermodynami c dat a bas e tha t i s easil y expande db

y th e user . Th e simulation s use dth e compositio no f th e J-1 3 wel l water s an dfocuse d onth e mineralogica l component s o f th e Prow Pas s sample s an

dothe r possibl e precipitate s tha t coul dappea r durin g th e experiments . Th e components , in orde r o f compositio nb

y weight , wer e feldspar , quartz , cristobalite , hematite , andmontmorillonite . Other s wer e goethite , barite , calcite , analcime , an d magnetite . Th e result s o f th e simulation s a t 3 8 C predic t tha t th e additio no f LiB r inconcentration s u pt o 200 0 /i g ml " lithiu

m doe s no t significantl y chang e th e equilibri a o f th e majo r cations , C a + , Mg + , Na + , o r th e majo r anions , SO . , CO , , andC l • Th e additio no f LiB r t o J-1 3 wel l wate r i s no t expecte dt o affec t th e potentia l precipitatio nandsolubilit y o f Prow Pas s andothe r minerals . Also , adde dlithiu m i s no t expecte dt o sho w a neffec t whe nth e p H i s varie dfro

m 7 t o 9 . Th e evaluatio no f th e distributio no f lithiu m amon g differen t specie s suggest s tha t >997 . lithiu m wil l b e presen t a s th e fre e io nLi + betwee np H 7 an d9 (Tabl e VII) . Th e specie s studie dwer e liDB , LiSO 4 ~ , Li 2 SD 4 , LiCl , LiML , LinCOo , an

dLiBr . Th e equilibriu m constant s fo r thes e specie s were derive dfro

m reporte dfree energy

value s (18 ) an

dwere include di

nth e thermodynami c dat a base o f PHREEQE . Th e conclusion s fro

m thes e geochemica l simulation s permitte da decreas e i nth e numbe r o f chemica l analyse s o f ion s i nth e experiments . Th e simulation s als o supporte dth e us e o f tota l lithiu m a s a goo dmeasur e o f Li + fo r lithiu

m adsorption .

3 5

### TABL E VI I

PREDICTION S FORLITHIU

M DISTRIBUTION

I N PRO V PAS S AN DJ-1 3 VATE R

Specie s Li + LiO H 

### LiSO 4 

### " Li 2 SO 4 LiC l LiNO g Li 2 CO 3 LiB r 

### ADSORPTION

EXPERIMENT S AT 38° C (L i

p H 1. 4 6. 6 3. 3 7. 0 1. 4 2. 2 

### 4. 4 8. 4 

### 7

X X X X X X X X 10 " 1 10 " 8 10' 5

. 7 10 " 5 10" 6 10" 8

- 4 Concentratio n

pH8 1. 4 x 4. 6 x 3. 3 x 7. 0 x 1. 4 x 1. 1 X 2. 9 x 8. 4 x = 200 0 fig

mL "

(mol e L"l )

io- i 10" 7 10" 5 10" 7

- 5 10 " 5



### _ 7

-4 

### i A 

### s

p H 1. 4 1. 4 3. 3 7. 0 1. 4 1. 2 8. 0 8. 4 LiBr )

9

x10 " 1 xlO" 6 x10 " 5 x10 " 7 x10 " 5 x10 " 5 x10" 7 X10- "

3 6

### 5. 0 RESULT S AND DISCUSSIO N

Thi s sectio n present s th e experimenta l result s an d thei r analysi s an d interpretation . Emphasi s i s o n modelin g o f th e lithiumdat a b yisotherm s and estimatio n o f thermodynami c constants . Thes e constants--th e relativ e behavio r betwee n adsorptio n an d desorption , and potentiometri c studies--ar e use d t o classif yth e controllin g sorptio n mechanis ma s eithe r physica l o r chemical .
5.. t Kinetic s Experiment s Th e kinetic s experiment s ha d tw o mai n objectives : first , t o determin e minimu mequilibratio n times ; second , t o provid e dat a fo r (a ) evaluatin g th e rol e o f fil mtransfe r and interna l diffusio n an d (b ) estimatin g activatio n energies . Batch-tub e kinetic s experiment s conducte d a t 38° C provide d a firs t measur e o f th e minimu mequilibratio n tim e neede d fo r adsorption . Tw o initia l lithiumsolutio n concentrations , 5 an d 25 0 figm l , wer e use d t o estimat e a n equilibratio n period . Althoug hequilibriumwa s reache d rapidl y(abou t 2 hours) , a 24-hou r equilibriu mperio d wa s selecte d a s a standar d fo r al l adsorptio n equilibriu mexperiments . Desorptio n kinetic s wa s evaluate d fo r eac ho f th e abov e adsorptio n experiments . Th e result s indicat e tha t mos t desorptio n ,(-757 0 occur s withi n 6 hours , wit hadditiona l desorptio n occurrin g throug hth e 96-hou r samplin g time . An analysi s o f th e kinetic s dat a fro mth e controlle d reactor s ha s no t bee n performe d fo r thi s report . Th e qualit yand quantit yo f th e kinetic s dat a hav e no t bee n evaluate d fo r usefulnes s i n estimatin g rate s fo r fil mtransfer , particulat e diffusion , o r surfac e reaction . Agenera l inspectio n o f th e dat a suggest s tha t i t ma yb e possibl e t o mode l adsorptio n kinetics . However , th e lac K o f sufficien t observation s durin g th e firs t 1 2 hour s make s th e desorptio n 3 7dat a inadequat e fo r modelin g o f rates . Bot hadsorptio n and desorptio n kinetic s dat a appea r t o b e o f bette r qualit yfo r th e controlle d reactor s tha n fo r th e batc htubes . 5. 2 Equilibriu m Tw o set s o f equilibriu mexperiment s wer e performe d a t thre e temperature s (25°C , 38°C , an d 45°C ; 38° C i s th e averag e temperatur e o f th e Yucc a Mountai n aquife r water) . On e se t wa s performe d ove r a n initia l concentratio n rang e o f 1 t o 200 0 figm L an d a t a solid-to-liqui d rati o o f 1:20 . Th e amoun t adsorbe d i s base d o n th e differenc e betwee n th e initia l concentratio n and th e equilibriu mconcentration . Becaus e adsorptio n wa s low , th e differenc e i n concentratio n wa s minimal relativ e t o th e analytica l erro r o f concentratio n measurements . I n orde r t o minimiz e th e effec t o f th e analytica l error , th e solid-to-liqui d rati o wa s increase d t o 1:1 0 (t o increas e th e numbe r o f potentia l adsorptio n site s pe r volum e o f tracer ) an d th e initia l concentratio n rang e restricte d t o 1-15 0 figm L t o enhanc e th e differenc e i n concentration s compare d wit hth e analytica l erro r o f concentratio n measurement . Th e othe r se t o f experiment s wa s performe d ove r a n initia l concentratio n rang e o f 1 t o 15 0 figml " and a t a solid-to-liqui d rati o o f 1:10 . Thes e experiment s wer e performe d t o determin e th e exten t o f sorptio n and t o selec t suitabl e isotherm s tha t ca n b e applie d t o transpor t modeling . Also , thermodynamii j parameter s wer e calculate d fro mth e sorptio n dat a a t th e thre e temperature s t o hel p i n differentiatin g betwee n physica l and chemica l sorption . 5.2. 1 Sorptio n Calculation s Th e amoun t o f lithiumsorbe d t o th e Pro wPas s soli d fro mJ-1 3 wel l wate r spike d wit hconcentration s o f lithiumwa s determine d fro mth e differenc e i n
3 8concentratio n o f lithiumi n th e solutio n befor e equilibratio n an d tha t i n th e solutio n concentration s afte r equilibration . Preliminar yevaluatio n o f th e sorptio n dat a show s larg e variabilit ya t th e hig hsolutio n concentration s afte r equilibration . Th e variabilit yi s attribute d t o experimenta l condition s and t o th e erro r associate d wit hth e analytica l data . Fo r example , th e differenc e betwee n th e initia l concentratio n o f lithiumand tha t afte r equilibratio n ca n b e show n t o b e withi n th e analytica l erro r o f th e measure d concentration s fo r th e experimenta l condition s 100 0 /igLi mL " initia l concentration , 2 0 m L o f solution , 1 g tuff , 112 0 figL i g " maximu msorptio n (CEC) , an d 37 , analytica l error . Thu s th e variabilit yassociate d wit htha t differenc e i s ver ylarge . Adifferen t procedure , use d t o determin e th e amoun t o f lithiu miorbed , i s base d o n th e assumptio n tha t th e amoun t o f lithiumadsorbe d i s equa l t o th e amoun t o f cation s desorbe d fro mth e solid . Th e dat a obtaine d b yth e tw o procedure s ar e give n i n Appendi x B (Table s B- I throug hB-III) . Th e value s obtaine d b

ycalculatin g difference s i n lithiumconcentratio n ar e highe r a t lo w concentration s o f lithiumtha n thos e obtaine d b ycalculatin g th e difference s i n summe d cations . Smal l difference s existe d betwee n initia l an d equilibrate d concentration s o f som e o f th e individua l cations . Thos e difference s wer e wel l withi n analytica l error ; thu s larg e error s coul d occur . Som e calculate d difference s gav e negativ e values . I n thos e case s a sumo f difference s i n concentration s resulte d i n a lowe r summe d concentratio n o f desorbe d cations . Th e differenc e i n lithiumconcentration s wa s use d i n th e low-concentratio n

3 9rang e an

dth e differenc e i nsumme dcation s wa s use da t th e high-concentratio n rang e fo r th e bes t estimat e o f lithiu m sorbed . 5.2. 2 Isotherm

Evaluatio n Th e fou r isotherms , Linear , Langmuir , Freundlich , an dModifie d Freundlich , wer e use dt o mode l th e tw o set s o f equilibriu

m experiment s discusse dabove . Linear , langmuir , andFreundlic hwer e use dbecaus e o f thei r widesprea dus e i nmodelin g sorptio nandinth e couplin g o f th e sorptio n isotherm s t o transpor t models . Th e fourt hisotherm , th e Modifie dFreundlich , wa s use dbecaus e o f it s theoretica l implications . Appendi xC compile s al l th e dat a from th e adsorptio nanddesorptio nexperiment s use di nth e fittin g o f th e fou r isotherms . Th e statistica l dat a onth e modelin g o f sorptio nb y th e fou r isotherm s indicat e tha t th e sorptio ndat a base donbes t estimate s giv e th e bette r inde x o f determinatio n( R) an dcoefficien t o f variatio n(CV) . Al l fou r isotherm s o gav e Ro f >0.80 . Th e C V wer e 5 5 percen t o r better . Th e Freundlic hand

o 

### Modifie dFreundlic hisotherm s gav e th e bes t RandC V values , wit hth e Freundlic hgivin g slightl y bette r C V values . Detaile dstatistica l and isotherm paramete r dat a ar e give ni nth e Table s i nAppendi xD . Figure s 1 throug h6 sho

w th e result s o f modelin g th e dat a wit hth e Modifie dFreundlic h isotherm . Th e regressio no f th e bes t estimat e dat a show s th e bes t variability . Th e modelin g analyse s indicat e tha t th e sorptio no f lithiu m can be effectivel y

represente db

y al l fou r isotherms . However , th e analysi s o f th e Modifie dFreundlic hisother m provide s additiona l informatio nonth e predictio no f th e exten t andheterogeneit y o f sorption . Thi s exten t and heterogeneit y

o f sorptio nprovide s aninsigh t int o th e transpor t o f lithiu m i n

4 0X
a & 

### 3 0 -
- 1 -
- 2 - - 3 - 

### n

—

. o

— - UObs . U Pred . Bes t Est . Obs . Bes t Es t Pred .



## n

— i 1 

### a

- 1 1

Log Cone . 2

mL~"' ) Figur e 1 . suspensio n t o 200 0 fig determine d base do na estimate) . Observe dand predicte dadsorptio no f lithiu m o na Prow

Pas s i nJ-1 3 wel l wate r a t 25° C fo r a ninitia l concentratio nrang e o f 1 L i ml" 1 an

d a solid-to-liqui drati o o f 1:20 . Adsorbe dlithiu m i s i ntwo ways : (1 ) base donmeasure dlithiu m i nsolutio n(li ) an

d (2 ) combinatio no f measure dlithiu m an d othe r cation s i nsolutio n(bes t Predicte dlithiu

m i s base donth e Modifie dFreundlic hisotherm .

41X

a 

### 3



### _ 2 1 • 0 -

- 1 • • 2 - •

- 3

- 1 D L i Obs .

— - U Pred . O Bea t Eat . Oba .

—Bea t Eat . Pred . 

## o

Log Cone , (jiq

m L 1 ) Figur e 2 . suspensio n t o 200 0 fig determine d base do na estimate) . Observe dand predicte dadsorptio no f lithiu m o na Pro

w Pas s i nJ-1 3 wel l wate r a t 38° C fo r a ninitia l concentratio nrang e o f 1 L i ml " and a solid-to-liqui drati o o f 1:20 . Adsorbe dlithiu m i s i ntwo ways : (1 ) base do nmeasure dlithiu m i nsolutio n(Li ) and (2 ) combinatio no f measure dlithiu m an d othe r cation s i nsolutio n(bes t Predicte dlithiu

m i s base do nth e Modifie dFreundlic hisotherm .

4 2V ) I o

Q 2 1 -
0 • • - 1 - - 2 -

- 3 O U Obs .

L i Pred . O Bes tEst . Oba .

—Bes tEst . Pred ,

- 1 Lo g Cone , {jjq mL~ 1 ) ~ 1 

### Figur e 3 . suspensio n t o 200 0 ng determine d base do na estimate) . Observe dan

dpredicte dadsorptio no f lithiu m ona Prow

Pas s i nJ-1 3 wel l wate r a t 45° C fo r a ninitia l concentratio nrang e o f 1 L i mL anda solid-to-liqui drati o o f 1:20 . Adsorbe dlithiu m i s i ntwo ways : (1 ) base donmeasure dlithiu m i nsolutio n(Li ) an

d(2 ) combinatio no l measure dlithiu m andothe r cation s i nsolutio n(bes t Predicte dlithiu

m i s basedo nth e Modifie dFreundlic hisotherm .

43I

e n I 

## 2 -2+ o o 1 

## •

o

— — L i Obs . L f Pred . Bes t Est . Obs . Bes t Est . Pred .

1 1

_

- 1 0 1

Lo g Cone , (pq

mL " Figur e 4 . Observe dand predicte dadsorptio no f lithiu m o na Pro w Pas s suspensio ni nJ-1 3 wel l wate r a t 25° C fo r a ninitia l concentratio nrang e o f 1 t o 15 0 /t g L i m L and a solid-to-liqui drati o o f 1:10 . Adsorbe dlithiu m i s determine di ntwo ways : (1 ) base do nmeasure dlithiu m i nsolutio n(Li ) and (2 ) base do na combinatio no f measure dlithiu m and othe r cation s i nsolutio n(bes t estimate) . Predicte dlithiu m i s base do nth e Modifie dFreundlic hisotherm .

44I x a 

### XL e n o D Li Obs .

U Pred . O Bes tEat. Obs .

—Bes tEst . Pred .

Lo g Cone , (jiq

m L ' ) 

### Figur e 5 . Observe dandpredicte dadsorptio no f lithiu m o na Prow

Pas s suspensio ni nJ-1 3 wel l wate r a t 38° C fo r aninitia l concentratio nrang e o f 1 t o 15 0 fig

L i mL* 1 

### anda solid-to-liqui drati o o f 1:10 . Adsorbe dlithiu m i s determine di ntwo ways : (1 ) base do nmeasure dlithiu m i nsolutio n(Li ) and(2 ) base do na combinatio no f measure dlithiu m an dothe r cation s i nsolutio n(bes t estimate) . Predicte dlithiu m i s base do nth e Modifie dFreundlic hisotherm .

45I

V) \ X o w e n o - 1 •

—2 -

- 3 D U Obs .

L i Pred . O Bes tEst . Obs .

—Bes tEst . Pred

- 1 1

Lo g Cone , (/ig

ml_ ~ ' ) Figur e 6 . Observe dand predicte dadsorptio no f lithiu m o na Prow

Pas s suspensio ni nJ-1 3 well wate r a t 45° C fo r a ninitia l concentratio nrang e o f 1 t o 15 0 fig

L i m l an

d a solid-to-liqui drati o o f 1:10 . Adsorbe dlithiu m i s determine di ntwo ways : (1 ) base donmeasure dlithiu m i nsolutio n(Li ) and (2 ) base do na combinatio no f measure dlithiu m and othe r cation s i nsolutio n(bes t estimate) . Predicte dlithiu m i s base do nth e Modifie dFreundlic hisotherm .

4 6laborator ycolumn an d fiel d tests . Ahighe r degre e o f heterogeneit y{fl- value

i n th e Modifie d Freundlic hisother mapproache s zero ) implie s tha t a wide r spectrumo f retardatio n factor s wil l occu r i n transport . Thi s spectrumwil l hav e a n averag e exten t o f retardatio n a s define d byth e K n -valu e o f th e sam e isotherm . Consequently , th e followin g analysi s use s th e Modifie d Freundlic h isother ma s a referenc e i n predictin g th e behavio r o f lithiumi n transport . Th e exten t o f sorptio n i s relate d t o anyo f th e K parameter s o f th e fou r models , fo r example , K i n th e Freundlic hisother mand k i n th e Langmui r isotherm . For a bette r understandin g o f th e relativ e retardatio n o f lithium predicte d byth e fou r isotherms , th e retardatio n parameter s wer e normalize d o r transforme d t o thos e o f th e linea r isotherm , K. , and th e Modifie d Freundlic h isotherm , I L an d /? . Th e isother mparameter s K, , Kg , an d 0 ar e give n i n Tabl e VIII , alon g wit h th e transformations . Th e result s indicat e tha t al l value s o f K . ar e 2 m L g " o r less ; th e Langmui r isother mgive s th e highes t value s an d th e Freundlic h give s th e lowes t values . Retardatio n ca n b e expresse d byth e followin g equatio n



### R f 

### = 1 + - p 

### , (5.1 )
wher e R ^ i s th e retardatio n facto r an d i s define d a s th e mea n velocit yo f th e movin g liqui d relativ e t o th e mea n velocit ya t whic hth e trace r moves ; /> , i s th e dr ybul k densit yo f th e medium ; and 9 i s th e volumetri c moistur e content . I n general , a K , o f 2 o r les s indicate s littl e sorption-cause d retardatio n o f th e tracer . Thu s lithiumappear s t o b e a suitabl e trace r fo r th e C-well s fiel d tes t becaus e o f lo wsorptivity . 4 7TABI E VII I ACOMPARISO NO F ESTIMATE D PARAMETER S O F FOU R ISOTHER M MODEL S FO R TH E ADSORPTIO NO F LITHIU M O NAPRO W PAS S SUSPENSIO NI NJ-1 3 WEL L WATE R FO R A NINITIA L C^CENTRATIO N

RANG E O F 1 T O 200 0 ja g L i inL" 1 AN D ASOLID-TO-LIQUI D RATI O O F 1:2 0

25° C 38° C 45° C

Linea r Iangnui r Freundlic h Modifie d Freundlic h 0.4 3

2. 0 3.3x1 0 0.9 8 - 2 3.9X1 0

2.8X1 0 - 3 3.0x1 0 8.9x10 " 1 .

1 . 0 . 0 . 0 0 7 2 8 2 0 . 1 . 2 . 0 . 4 3 6 

### oxio" 2 7 3 3 .

2 . 1 . 6 . 9x1 0 ' 3xlO~ 3 8xlO~ 5 6xlO~ 4 1

1 0 0 . 0

. 0 .6 8 .7 7 0 . 1 . 1 . 0 . 2 7 2 0x1 0 3 3 - 2 2.4X1 0

2.4X1 0 - 4

- 3 9.5x1 0 2.8x1 0 .- 4 1. 0 1. 0 0.6 5 0.7 0

Transformations : Linear : K d = Kd Freundlich : K K 1/N

' d S. max K ma x ma

x 1/N

Langmuir : K . • Id

s Modified Freundlich : K d-Base d o n theoretica l considerations , th e K « paramete r i s a measur e o f th e mea n energ ysorptio n o f lithium , an d th e / ? p?ramete r i 6 a measur e o f th e distributio n o r sprea d o f individua l energie s abou t th e mean . Thu s unde r flo w conditions , I L i s a measur e o f th e sorption-cause d retardatio n o f th e trace r an d 0 i s a measur e o f th e sorptiv e dispersio n cause d b yth e heterogeneit yo f sorption ; thi s dispersio n i s i n additio n t o an yhydrodynami c dispersio n tha t ma yoccur . Thu s th e compariso n o f 1 L and 0 paramete r value s i n Tabl e VII I fo r th e linear , Langmuir , an d Freundlic hisotherm s ( 1 t o 200 0 figL i m L ) ca n b e interprete d a s follows . 1 . Th e Freundlic hisother munderestimate s retardatio n and overestimate s sorptiv e dispersion . 2 . Th e Langmui r isother moverestimate s retardatio n an d underestimate s sorptiv e dispersion . 3 . Th e Linea r isother munderestimate s bot hretardatio n an d sorptiv e dispersion . Th e effect s o f overestimatio n an d underestimatio n ca n onl yb e inferre d fro m these analyses . Prope r statistica l discriminatio n analysi s i n combinatio n wit hcolumn experiment s i s neede d t o identif yth e bes t isother munde r flo w conditions . Th e statistica l and modelin g result s fo r th e concentratio n rang e 1 t o 15 0 figL i mL " an d a solid-to-liqui d rati o o f 1:1 0 ar e give n i n Appendi x D , Table s D- V throug hD-IX , fo r th e Linear , Langmuir , Freundlich , an d Modifie d Freundlic hisotherms , respectively . Th e dat a ar e base d o n lithiumanalysi s an d bes t estimates , a s wa s th e cas e i n th e rang e 1 t o 200 0 figL i m L . Th e result s indicat e tha t th e statistic s ( R and CV ) i n genera l d o no t diffe r greatl yfro mth e result s fo r th e l-to-2000-/jg-L i m L dat a set . Overall , th e best-estimat e data , a s determine d fro ma combinatio n o f lithiumdat a an d th e 4 9summe d catio n data , ca n als o b e represente d b yth e fou r isother mexpressions . Tabl e I X summarize s th e estimate d parameter s fo r th e fou r isotherm s withi n thi s concentratio n range . Th e parameter s ar e als o expresse d i n term s o f K, , Kp , an d /? , i n orde r t o compar e th e expecte d outcome s o f usin g specifi c isotherm s i n transpor t modeling . A s i n th e cas e o f th e l-to-2000-/zg-L i m L dat a set , th e interpretatio n give n t o thes e dat a i s a s follows . 1 . Th e Freundlic hisother munderestimate s retardatio n an d overestimate s sorptiv e dispersion . 2 . Th e langmui r isother moverestimate s retardatio n and underestimate s sorptiv e dispersion . 3 . Th e Linea r isother moverestimate s retardatio n and underestimate s sorptiv e dispersion . Acompariso n o f thes e result s wit hthos e o f th e l-to-2000-/rg-L i mL " rang e indicate s tha t i n bot hcase s th e Freundlic hisother munderestimate s retardatio n an d overestimate s sorptiv e dispersion . Th e Langmui r isother m mode l overestimate s retardatio n and underestimate s sorptiv e dispersio n fo r bot hcases . However , th e overestimatio n o f retardatio n appear s significantl y greate r fo r th e 1

- to-150

- /ig- L i m L experimen t tha n fo r th e l-to-2000-^g-L i m L experiment . Th e Linea r isother moverestimate s retardatio n i n th e forme r bu t underestimate s retardatio n fo r th e latter , eve n thoug hth e amoun t o f overestimatio n an d underestimatio n appear s t o b e small . Consequently , car e shoul d b e exercise d whe n selectin g a n isother mamon g severa l possibl e alternatives , regardles s o f thei r relativel ygoo d correlatio n statistics . 5.2. 3 Thermodynami c Paramete r Estimatio n Thermodynami c parameter s wer e estimate d fo r th e lithiumsorptio n o f th e Pro wPas s mediu mfro mJ-1 3 wel l wate r fo r th e concentratio n rang e o f 1 t o 5 0TABL E I X ACOMPARISO NO F ESTIMATE D PARAMETER S O F FOU R ISOTHER M MODEL S FO R TH E ADSORPTIO NO F

LITHIU M O NAPRO W PAS S SUSPENSIO NI NJ-1 3 WEL L WATE R FO R A NINITIA L OMIC3ENTRATIO

NRANG E O F 1 T O 15 0 M g L i iriL*" 1 AN D ASOLID-TO-LIQUI D RATI O O F 1:1 0

25° C 38° C 45° C K ,

Linea r Langmui r Freundlic h Modifie d Freundlic h 0

2 3 0
Transformations : Linear :

Langmuir : 0

K d 0 =

=

= .8 7 .1 7 .7X1 0 .49 7

K d 

# V s 

# ! , 1 k b k 1 - 2 7.9x1 0 1. 0 0.9 6 8.7x1 0

1.3X1O" 2 1. 0 2.0 6 1.2x1 0 3.6xlO~ 5 0.75 9 7.3xlO~ 2 6.6x1 0 4.5X10 4 0.77 7 0.80 6 7.3x10 "



# r 2

- 5 1. 0 1. 0 0.83 1 0.85 2 1.2 4

2.7 7 3.7X1 0 0.66 2 - 2 1.1X1 0

1.3x10 " 3.3X10 " 6.0X10 " - 3 1. 0 1. 0 0.72 2 0.74 8

ma x Freundlich : K , d 1/

N S ma x ma

x 1/ N S ma x N= & Modifie d Freundlich :

L n200 0 /i

g l i m L an d a solid-to-liqui d rati o o f 1:20 . Th e assumptio n i n thes e calculation s i s tha t lithiumsorptio n ca n b e modele d a s pseudo-binar y ion-exchang e sorption . Durin g sorption , lithiumreplace d primaril ycalciu m an d sodiumions . Typically , lithiumwa s exchange d wit hcalciuman d sodiumi n a n equivalen t rati o o f 1.6: 1 (Ca:Na ) i n th e highe r concentratio n regio n o f lithiuman d nearl yth e revers e i n th e lowe r concentratio n region . Therefore , calciu man d sodiumar e considere d a s a composit e io n [io n B i n Equatio n (4.12) ] i n thes e calculations . Th e valenc e o f th e composit e io n B wa s estimate d a s follows .

A t hig hconcentrations ,

1 f\ i Z D = i—Ti~f i zn~ + T77~7t % » = 1.61 . Dl.+i. o u a l+i. o wa A t lo wconcentrations ,

1 R 1 Z 

### B = 

### 17+17 6 z 

### N a + 

### I+T7 8 z 

### C a = 1>38 < 

### Therefor e averag e Z g i s approximatel y1.5 . Th e integrate d for mo f Equatio n (4.18 ) wa s use d t o calculat e th e thermodynami c equilibriumconstant .

e vD
+ z A( 1 + vp -»-° ) [I n (- B ; ° + C B o ) - 1 ] - z Arp - B

- ° [I n C B o - 1 ] C B o Tf> C B o + z AI n 7 B - Z g I n 7 A+ z g I n M A+ z g I n K ^ , (5.2 )

52wher e Z g = valenc e o f th e composit e io n B ;

z. - valenc e o f lithium ; /? = isother mparameter ; C n = th e initia l concentratio n o f composit e io n B adsorbe d expresse d a s /jraole s B mL " solid ; C g - th e initia l concentratio n o f composit e io n B i n th e solutio n phas e expresse d a s /anole s B mL " HgO ; r = solution-to-soli d rati o expresse d a s m L H^ O g solid ; p - soli d densit yexpresse d a s g soli d mL " solid ; 7 B = (?C a ^Na ^ = activit ycoefficien t o f composit e io n B ; 7 i = activit ycoefficien t o f lithiumi n solutio n phase ; 1 ^ = molecula r weigh t o f lithiumexpresse d a s ftgL i /imole' Li ; an d K p = isother mparamete r expresse d a s m L jigLi ;

Th e paramete r value s use d t o calculat e th e thermodynami c equilibriu mconstant s fro mEquation s (4.19 ) throug h(4.22 ) ar e give n i n Tabl e X . Th e estimate d value s fo r th e equilibriu mconstant s ( K ) , Gibb' s fre e energie s o f sorptio n (AG°) , an d enthalp y(AH 0 ) ar e give n i n Tabl e II . Th e result s indicat e tha t th e thermodynami c equilibriu mconstan t decrease s wit ha n increas e i n temperature , a s doe s Gibb' s fre e energ yo f sorption . Th e enthalp yo f sorptio n betwee n 25° C an d 38° C wa s estimate d t o b e - 5 kca l mol e . However , th e AH 0 betwee n 38° C an d 45° C wa s estimate d t o b e abou t -3 6 kca l mol e . Th e - 5 kca l mol e i s mor e consisten t wit htha t expecte d wit hlithium , tha t is , electrostati c o r physica l sorption . Th e 7° C differenc e betwee n 38° C an d 45° C i s small . Therefore , difference s i n equilibriumconstant s wil l b e smalle r tha n whe n th e temperatur e differenc e i s great . I n case s wher e smal l 5 3TABL E X

PARAMETE RVALUE S FO RTH E ESTIMATIO N O F A THERMODYNAMI C EQUILIBRIUM CONSTAN T FO RTH E LITHIUM ADSORPTIO N

O N A PROV PAS S SUSPENSIO N

I N J-1 3 VEL L WATE RA T THRE E TEMPERATURE S FO RTH E INITIA L CONCENTRATIO N RANG E O F 1 T O 200 0 fig

L i mL" 1 AN DA

SOLID-TO-LIQUI DRATI O O F 1:2 0



### 25° C 38° C 45° C 0

0 0 

## 0 .82 3 .77 5 .70 3 9 6 2 K 

### D .17x10" 4 .90x10" 4 .97x10" 4 1

0 . 0 . 0 . 

### L i 978 94 1 

### 94 0 7 0 . 0 . 0 . 

### C a 78 7 78 3 78 1 0 0 0 7 

### N a .97 4 .93 9 .93 8 0 0 0 .87 6 .85 7 .85 6

z A = 1 ~p= 2.5 4 g soli dmL" 1 soli dC fi o= 270.9 3 /zraol e B mL soli d z f l = 1. 5 r = 2 0 m L H 2 0 g " * soli dC fi o= 1.79 8 fimoles B mL" 1 Hg O M A = 6.9 4 jig

L i mole" 1 M f i = 3 3 (tg

B fimole' 1

5 4TABL E X I

THERMODYNAMI C CONSTANT S ESTIMATEDFORLITHIU M ADSORPTIO

N O N A PRO V PAS S SUSPENSIO

N I N J-1 3 VELL VATERAT THRE E TEMPERATURE S FORA N INITIA L CONCENTRATIO

N RANGE O F 1 T O 200 0 p g L i ml" 1 AN DA SOLID-TO-LIQUI DRATI O O F 1:2 0

K e 

## AG ° (kca l 

### AH0 (kca l mole " ) mole " ) 25° C

0.00195 4 3. 7 -5. 4 3 8

0 . 4 . 

## ° C 001 3 1 -35. 5 45° C

0.0003 7 5. 0

5 5difference s i n equilibriu mconstant s occur , th e relativ e erro r i s expecte d t o increase . Thus , estimate d enthalpie s (equatio n 4.20 ) ar e subjec t t o mor e erro r whe n temperatur e difference s ar e smal l tha n whe n the yar e large . T o evaluat e th e -3 6 kca l mol e estimate , th e enthalp yfro mth e l-to-150-/jg-L i ml T experimen t fo r 38° C and 45° C wa s calculated . Th e experimenta l desig n differe d i n tha t th e solid-to-liqui d rati o wa s 1:1 0 instea d o f 1:20 . Th e effectiv e valenc e o f th e pseudo-solut e B wa s abou t 1.2 , compare d wit h1. 5 fo r th e firs t dat a set . Th e parameter s use d i n calculatin g thermodynami c constant s ar e give n i n Tabl e XI I fo r th e 38° C and 45° C dat a sets . Th e thermodynami c constant s ar e give n i n Tabl e XIII . Th e equilibriu mconstan t valu e fo r 38° C i s slightl yhighe r tha n fo r th e firs t dat a se t (0,030 3 compare d wit h0.0239) . Thi s differenc e ca n b e attribute d t o difference s i n th e effectiv e valenc e o f th e pseudo-io n B . However , th e AH 0 estimate d fo r th e 38° C an d 45° C dat a i s - 5 kca l mole " , whic hi s th e sam e a s tha t fo r th e 25° C t o 38° C dat a o f th e l-to-2000-/jg-L i mL" 1 dat a set . I t shoul d b e state d tha t th e metho d o f calculatin g th e enthalp yo f sorptio n i s sensitiv e t o th e erro r associate d wit hth e estimat e o f th e thermodynami c equilibriu mconstant . Smal l error s i n th e equilibriu mconstant s ma yresul t i n larg e difference s i n enthalp yestimates . Fo r instance , i n th e cas e o f equatio n 4.20 , error s associate d wit hth e natura l logarithmo f th e rati o o f th e equilibriu m constant s i s multiplie d b yth e larg e produc t o f tw o absolut e temperatures . Thus , th e abov e conclusion s shoul d b e kep t withi n th e contex t o f th e trend s fro ma numbe r o f dat a sets ; th e averag e value s o f enthalp yshoul d no t b e take n a s absolute . Asecon d approac hi n estimatin g th e enthalp yo f sorptio n wa s use d t o tes t th e abov e conclusions . Th e best-estimat e dat a o f th e l-to-2000-/*m-L i m l

5 6

### TABL E XI I

PARAMETE R VALUE S FO R TH E ESTIMATIO NO F THERMODYNAMI C EQUILIBRIU M CONSTANT S FO R LITHIU M ADSORPTIO NO

NAPRO V PAS S SUSPENSIO NI NJ-1 3 VEI L WATE R A T 38° C AN D 45° C FO R TH E INITIA L CONCENTRATIO NRANG E O F 1 T O 15 0 figL i mL" 1



### AND ASOLID-TO-LIQUI D RATI O O F 1:1 0

38° C 45° C

Z 

### A= Z 

### B = 1 1. 2 0 . 0 . 85 2 74 8 7 . 6 . i
3x10" 4 0x10" 4 7

0 0

P r L i

.97 8 .94 0

= 2 .

= 1 0 5 4 m L ?C a
0.78 3 0.78 1

g soli d ^Og" 1 0 .

0 . ml" 1 Y a
.93 9 .93 8 soli d soli d 7

0 0 

### B
.85 7 .85 6

M A= 6.9 4 figL i fimole' 1 C fi o = 270.9 3 fimoles B raL" 1 soli d M g = 2 7 figB fimole' 1 C^ Q = 1.79 8 pinole s B mL" 1 H 2 0

5 7TABL E XII I THERMODYNAMI C CONSTANT S ESTIMATE DFORLITHIU M ADSORPTION

O N A PRO V PAS S SUSPENSION

I N J-1 3 VEL L VATE RA T 38° C AN

D45° C FOR . A

N INITIA L CONCEN TRATION RANG E O F 1 T O 15 0 ng

L i mL" 1 AN

DA SOLID-TO-LiqUI DRATI O O

F 1:1 0

Constan t 38° C 45° C

K e 

### AG ° (kca l 

### AH 0 (kca l mole"* ) mole" 1 ) 0 .

2 . 009 3 9 -5. 2 0 .

3 . 007 7 1

5 8concentratio n rang e experiment s wer e use d i n thi s approach . Th e Freundlic h equatio n wa s use d t o sho wth e relationshi p betwee n th e concentratio n o f lithiumsorbe d and th e concentratio n i n solutio n a t equilibrium . Th e paramete r value s fo r tha t equatio n ar e give n i n Appendi x D , Tabl e D-III . I n thi s approac hth e concentratio n o f lithiumadsorbe d (C o ) i s expresse d a s /j g L i s ml " o f solutio n i n contac t wit hth e surfac e o f th e solid . Thi s valu e ca n b e calculate d fro mth e equatio n (47 , 48 )

wher e p i s th e densit yo f wate r ( g m L ) , H i s th e molecula r weigh t o f wate r (g) , 2 - 1 Ai s th e cross-sectiona l are a o f wate r (cmmolecule " ) , Ni s Avogadro' s number , 2 - 1 S o i s th e surfac e are a o f th e soli d (cmg " ) , and S i s th e specifi c adsorptio n (in g kg " ) . Th e cross-sectiona l are a o f wate r wa s calculate d fro mth e followin g equatio n (46) :

A= 1.09 1 x 10" i 6 [( I x lO 2 4 )^/?)" 1 ] 2 / 3

. (5.4 )

Fo r th e condition s o f th e lithiumexperiment , p = 1 g m l , M = 1 8 g , A= 10 5 x 10" 1 5 cm 2 molecule" 1 , S , = 3 4 60 0 cm 2 g" 1 , and N= 6.0 2 x 10 2 3 ; therefor e C c l S = 101 5 x S . Equatio n 5. 3 wa s use d t o calculat e C fo r a serie s o f S values . Also , C s e wa s calculate d fo r th e sam e S value s b yinvertin g th e Freundlic hisother m 5 9data . Thos e result s ar e give n i n Tabl e XIV
- Fro mthos e data , I n ( C / C ) wa s plotte d agains t C and th e curv e wa s extrapolate d t o C - • 0 ; a s C -^ 3 0 , S fa o ( C / C ) = a / a = K , wher e K i s a n equilibriumconstan t fo r th e sorptio n process . Th e K value s obtaine d fro mth e sorptio n o f lithiuma t th e thre e temperature s (25°C , 38°C , and 45°C ) ar e give n i n Tabl e XV , a s ar e averag e enthalpie s calculate d wit hEquatio n (4.19) . Th e estimate d averag e enthalpie s (base d o n trends ) indicat e tha t th e mechanis mo f lithiumsorptio n i s physica l (electrostatic) . Th e result s ar e consisten t wit hthos e yielde d byth e assumptio n o f io n exchang e method . 5.2. 4 Desorptio n Th e objectiv e o f th e desorptio n experimen t wa s t o evaluat e th e reversibilit yo f lithiumsorption . Knowledg e o f th e reversibilit yo f lithium sorptio n wil l hel p i n determinin g model s fo r th e transpor t o f lithiumi n th e fiel d and i n supportin g a controllin g sorptio n mechanis mo f lithium ; th e electrostati c sorptio n mechanis mi s expecte d t o sho wreversibility . Afte r th e adsorptio n experiment , th e solutio n wa s decante d and replace d wit hJ-1 3 wate r withou t lithium . Som e lithiumremaine d i n solutio n afte r decanting . Th e concentratio n o f lithiumi n th e remainin g solutio n wa s determine d fro manalysi s o f a n aliquo t o f th e decante d was hsolution . J-1 3 wate r wa s equilibrate d wit hth e soli d containin g adsorbe d lithium . Th e solutio n wa s the n analyze d fo r lithiumand othe r cations . Vit hth e concentratio n o f ion s i n th e adsorbe d and solutio n phase s known , th e amoun t o f lithiumgaine d i n solutio n wa s compare d wit hth e amoun t o f cation s (excludin g lithium ) los t fro msolution , and a bes t estimat e wa s obtaine d fo r th e amoun t o f lithiumsorbe d afte r desorptio n equilibration . Thes e results , give n i n 6 0TABL E XI V

DAT AUSE D I NTH E CALCULATIO NO F EQUILIBRIU M CONSTANT S FO R TH E ADSORPTIO NO F LITHIU M ONAPRO V PAS S SUSPENSIO NI NJ-1 3 VEL L WATE R A T THRE E TEMPERATURE S FO R TH E INITIA L CONCENTRATIO NRANG E O F 1 T O 15 0

figL i mL' 1 AN D ASOLID

- TO

- LiqUI D RATI O O F 1:2 0



## s faglig" 1 

## )

4 2 5 10 0 25 0 37 5 50 0 (figL i mL" 1 )

4.06xl0 3 2.54xlO 4 1.02xl0 5 2.54xlO 5 3.81xlO 5 5.08xl0 5 25° C

0.9 6 12. 2 83. 6 29 8 52 2 78 0 

# C

(figL i mL' 1 ) 38° C 0.8 1 12. 1 92. 7 35 6 64 7 98 6 45° C

1.0 0 17. 0 145 59 8 112 0 175 0 C i s calculate d b

yusin g Equatio n (5.3) . C i s calculate d usin g it s relationshi p t o S a s modele d b yth e Freundlic hisotherm(se e Sectio n 5.2. 3 fo r th e relationship) .

6 1TABL E X V EQUILIBRIU

M CONSTANT S AN

DENTHALPIE S FORTH E ADSORPTION OF LITHIU M O N A PRO V PAS S SUSPENSION

I N J-1 3 VEL L VATER AT TEMPERATURE S O

F 25°C , 38°C , an

d45° C FORTH E INITIA

L CONCENTRATION

RANG E OF 1 TO 200 0 fig L i mL1 AN

DA SOLID-TO-LIQUI DRATI O O F 1:2 0

K o 

### AH 0 Constan t

(Kca l mol e ) 

### 25° C

7.8 1

0.0 9 (25°C-38°C ) 38° C

7.8 5

-0.3 2 (25°C-45°C ) 45° C

7.5 5

-1.1 2 (38°C-45°C )

6 2Figur e 7 , indicat e tha t desorptio n dat a follo wth e adsorptio n dat a i n th e lo w concentratio n range , bu t i n th e hig hconcentratio n rang e th e amoun t o f sorbe d lithiumi s highe r fo r th e desorptio n experimen t tha n fo r th e adsorptio n experiment . Thi s differenc e i s attribute d t o th e probabilit ytha t equilibriu m wa s no t reache d i n th e desorptio n experimen t becaus e o f th e hig hconcentratio n o f lithiu mi n solution ; tha t concentratio n i n solutio n ma yreduc e th e rat e o f outwar d diffusion . T o furthe r substantiat e thes e conclusions , th e desorptio n dat a fo r th e l-to-150-/*g-L i m l experimen t a t 38° C wer e evaluate d similarly . Th e results , give n i n Figur e 8 , indicat e tha t lithiumconcentration s i n th e desorptio n experimen t essentiall yfollo wthos e o f th e adsorptio n experimen t ove r th e rang e o f desorptio n concentrations . Astatistica l compariso n o f th e Modifie d Freundlic hisotherm s indicate s a significan t differenc e i n th e tw o regression s a t th e 957 i confidenc e level , bu t tha t differenc e i s attribute d t o th e adsorptio n data a t concentration s highe r tha n thos e o f th e desorptio n data . Th e abov e result s indicat e tha t th e sorptio n o f lithiu mi s reversibl e and hysteresi s i s no t evident . Th e conclusio n tha t lithiumsorptio n i s reversibl e als o support s th e conclusio n draw n fro mth e enthalp ydata : physica l sorptio n i s th e predominan t mechanis mfo r th e sorptio n o f lithiumo n th e Pro wPas s matrix . 5. 3 Potentiometri c Studie s Potentiometri c analysi s o f minera l surface s ca n provid e informatio n t o permi t understandin g th e mechanism s o f sorptio n exhibite d bya solut e ion . Data generate d bytitratin g th e soli d materia l wit hpotential-determinin g ion s (e.g. , H + an d OH" ) ma yals o b e use d wit hmodel s t o investigat e furthe r th e natur e o f solut e interaction s wit hth e medi a (30) . 6 3I— I 

# r w i 

# s C OLog 1 0

- 1

- 2

- 3

- 4 D

' " O Adsorp . Obs .

Adsorp . Pred . Desorp . Obs . n Oesorp . Pred . ©/ ^ 

# *y 

# o

—i—— i 1 — 1

- 1 1

Lo g Cone , (pjq Figur e 7 . Observe dand predicte dadsorptio nand desorptio no f lithiu m o na Prow Pas s suspensio ni nJ-1 3 wel l wate r a t 38° C fo r a ninitia l concentratio n rang e o f 1 t o 200 0 fig

l i ml" 1 and a solid-to-liqui drati o o f 1:20 . Predicte d lithiu m i s base donth e Modifie dFreundlic hisotherm .

6 4X 

# I 1 . 2

3 -
4 - D

. O Adsorp . Obs . Adsorp . Pred . Desorp . Obs . Desorp . Pred .

1 — i 1



### - 1 1

Log Cone , (jig

mL" 1 ) 

### Figur e 8 . Observe dandpredicte dadsorptio nanddesorptiono f lithiu m o na Pro w Pas s suspensio ni nJ-1 3 wel l wate r a t 38° C fo r a ninitia l concentratio n rang e o f 1 t o 15 0 p g L i ml" 1 

### anda solid-to-liqui drati o o f 1:10 . Predicte d lithiu m i s base do nth e Modifie dFreundlic hisotherm .

6 5Result s o f th e potentiometri c titration s ar e summarize di nFigur e 9 fo r n o lithiu m adde dan dFigur e 1 0 fo r lithiu

m added . Al l fou r curve s o f s k plotte dagains t resultan t p H sho w th e sam e pattern . N o clea r intersection s ar e observe dfo r th e two electrolyt e concentrations , an dth e lo w electrolyt e curve s ar e almos t alway s below th e hig helectrolyt e curves . Th e p H a t whic h th e two electrolyt e concentration s intersec t i s indicativ e o f th e ZPC . Th e graph s d o exhibi t a characte r simila r t o thos e reporte db y othe r investigator s (51 ) i ntha t th e two electrolyt e concentration s tendt o converg e an dremai n almos t indistinguishabl e belo w p H 9 . Result s o f th e electrophoresi s experimen t ar e summarize di nFigure s 1 1 an d1 2 fo r th e same sample s generate di nth e titratio nexperiment . Vherea s th e titratio nmeasurement s wer e mad e o nth e whol e sampl e (<500-/jm particl e diameter) , electrophoresi s wa s measure donl y onth e colloida l fractio n(<10-/j m diameter) . Th e colloida l fractio nmay represen t th e mor e reactiv e portio no f th e sample . EM

approached , bu t di dno t attain , a zer o value . Thes e result s suppor t thos e o f th e potentiometri c t.i.tratio nstudy . I nal l cases , bot hmethod s indicate dnegativel y charge dparticles . Th e decreas e i np H t o 2 wit hth e additio no f aci dwa s insufficien t t o neutraliz e th e negativ e surfac e charge s o nth e particles . Th e curve s do , however , sugges t tha t a ZP C may

occu r below

p H 2 . Thi s findin g agree s wit hpublishe d ZP C dat a (41 ) fo r silicate s (SilL) , feldspar , an dmontmorillonit e clay , al l o f whic hhav e ZPC s nea r o r below p H 2 . Thes e material s hav e bee nidentifie da s th e majo r minera l constituent s o f th e Pro w Pas s Membe r (36) . Smal l amount s o f material s wit hhighe r ZP C may b e presen t i nth e sample , bu t thei r effec t i s obscure db y th e dominanc e o f charge s contribute db y th e

6 62 0 

# L 1 0

0 •

o -10 "

-2 0 O—O0.005MNaCI0 4 D—O0.1 M NQC10 4



### P H 1 4



### Figur e 9 . Potentiometri c titratio no f Pro w Pas s i nsuspensio nwit hJ-1 3 wel l wate r andNaC10 4 

### electrolyt e a t 38° C withou t th e additio no f lithium .

6 72 0

o -10 - - 2 0 0- - - O—O0.005 M NaCI04 D—D0.1 M NaCI04

p H 8 1 0 12 14

Figur e 10 . Potentiometri c titratio no f Pro w Pas s i nsuspensio nwit hJ-1 3 wel l wate r and NaC10 4 electrolyt e a t 3 8 C wit hth e additio no f 90 0 fig L i ml " .

6 8E u

o o n 

# a - 2

- 3

- 5 O— O 0.005MNaCI04 • — D 0.1MNaCI0 4

6 P H 8 1 0 1 2

Figur e 11 . Electrophoreti c behavio r o f a colloida l suspensio n o f Pro wPas s i n J-1 3 wel l wate r an d NaC10 4 electrolyt e a t 38° C wit hth e additio n o f 90 0 /i g L i m l - 1

6 9E

o

o 

### 8

U i 0

- 1

- 2

- 3

- 4

- 5 O — O 0.005MNaCI0 4 D — •0.1MNaCI0 4

Cb- Q 

# N A -D— •

—f

6 p H 8 1 0 12

Figur e 12 . Electrophoreti c behavio r o f a colloida l suspensio no f Prow Pas s in J-1 3 wel l wate r an dNaCll helectrolyt e a t 38° C withou t th e additio no f lithium .

7 0bul k sample . Fo r example , i n natura l setting s coating s o n transmissiv e fracture s o r o n th e bul k material s ma yb e importan t i n definin g th e sorptio n mechanism s unde r hydrologi c conditions . Th e electrophoresi s and th e titratio n method s o f determinin g ZP C bot hindicat e th e lac k o f a ZP C betwee n p H 2 and 1 2 fo r th e Pro wPas s materia l i n th e presenc e o r absenc e o f adde d lithium .
6. 0 SUMMAR Y AN D CONCLUSION S Thi s repor t include s th e result s fro mbatc hexperiment s tha t wer e conducte d t o evaluat e th e potentia l o f lithium , whe n adde d a s lithiumbromide , a s a reactiv e (nonconservative ) trace r fo r test s i n th e saturate d zon e o f th e C-well s subsurfac e i n Yucc a Mountain. Th e mai n objective s wer e t o mode l th e exten t o f lithiu msorptio n o n Pro wPas s suspension s i n J-1 3 wel l water s an d t o estimat e thermodynami c constant s tha t i n combinatio n wit hpotentiometri c studie s suppor t th e classificatio n o f lithiumsorptio n eithe r a s physica l o r a s chemical . Lithiu m(a s lithiu mbromide ) wa s considere d a suitabl e candidat e o n th e basi s o f th e followin g characteristics : hig hsolubility , goo d chemica l an d biologica l stability , an d relativel ylo wsorptivity ; n o suspicio n o f bioaccumulatio n an d exclusio n a s a priorit ypollutan t i n pertinen t environmenta l regulations ; goo d analytica l detectabilit yan d lo wnatura l backgroun d concentrations ; an d lo wcost . Additionally , th e literatur e indicate d tha t retardatio n byadsorptio n o r b yexchang e wit hadsorber s i s lowe r tha n th e retardatio n o f mos t cation s and tha t it s recover yshoul d b e reasonabl yfas t (i.e. , withi n th e contex t o f th e C-well s pump-trace r tests) . Geochemica l simulation s performe d befor e th e experiment s wit hth e cod e PHREEQ E sugges t tha t mos t o f th e lithiumwil l remai n i n th e for mo f fre e lithiumwit honl * trace s i n th e for mo f othe r species . Th e simulation s als o indicat e tha t i n a p H rang e o f 7 t o 9 neithe r th e stabilit yo f th e minera l 7 1component s o f th e Pro wPas s sample s no r th e potentia l fo r th e formatio n o f ne w precipitate s i s significantl yaffected . Althoug hresourc e constraint s prevente d validatio n o f th e geochemica l cod e predictions , thes e simulation s suppor t th e assumptio n tha t lithium analysi s i s a measur e o f th e lithiumcatio n (Li + ) concentratio n an d thu s ca n b e use d fo r estimatin g concentration s fo r th e isother mparameter s and thermodynami c constants . Thes e simulation s als o show , withi n th e limitation s o f th e dat a bas e and compute r cod e calculations , tha t precipitatio n o r dissolutio n di d no t significantl yaffec t th e concentratio n o f lithiumi n solution . Thi s predictio n support s th e assumptio n tha t th e remova l o f lithium fro msolutio n wa s primaril ydu e t o sorptio n processes . Biologica l activit yi n initia l experiment s wa s confirme d byth e detectio n o f bacteri a an d substrates . Thi s occurrenc e wa s minimize d durin g subsequen t experiment s b

yautoclavin g container s an d material s befor e eac hexperiment . Autoclavin g wa s a compromis e betwee n havin g les s contro l o f th e sorptio n processe s i n thes e experiment s an d potentiall ychangin g th e characteristic s o f th e experimenta l materials . Abrasio n o f samples , cause d bytumblin g o r stirrin g o f suspensions , i s a concer n becaus e o f th e generatio n o f mor e sorptio n are a o r activ e sites . Th e ge , jratio n o f mor e sorptio n are a o r activ e site s ma yaffec t sorptio n durin g th e performanc e o f batc hexperiments . Abrasio n effect s coul d b e importan t i n thi s studybecaus e o f th e significant , bu t small , differenc e betwee n siz e distribution s befor e an d afte r th e contac t period . Abrasio n ha s no t bee n shown definitivel yt o b e a seriou s effec t becaus e significan t difference s amon g replicate d representativ e Pro wPas s sample s hav e no t bee n estimated . Nevertheless , thi s effec t i s difficul t t o exclud e becaus e o f th e natur e o f th e batc hexperiments , s o it s exten t shoul d b e characterized . 7 2Th e equilibriumsorptio n experimenta l dat a indicat e tha t lithiumsorptio n ca n b e modele d b

yth e fou r isotherms : Linear , Langmuir , Freundlich , and Modifie d Freundlich . However , theoretica l consideration s sugges t tha t unde r flo wcondition s th e fou r isotherm s wil l predic t varie d pattern s o f lithium migration . Th e Modifie d Freundlic hisother mi s a genera l isotherm , base d o n theoretica l considerations , an d th e other s ar e specia l case s o f thi s genera l case . Therefore , th e Modifie d Freundlic happear s t o b e th e bes t isother mfo r modelin g migratio n o f lithiumunde r flo wconditions . Thi s conclusio n need s t o b e verified , however , bylaborator ycolumn experiments . Lithiu mapparentl yadsorb s t o th e Pro wPas s matri x fro mJ-1 3 wel l wate r bya n electrostati c o r physica l mechanism . Sorptio n o f lithiumi s easil y reversible , a conditio n consisten t wit hth e theor yo f electrostati c sorption . Also , th e enthalp yo f sorptio n appear s t o b e i n th e rang e consisten t wit hth e enthalpie s o f physica l sorptio n (<1 2 kca l mole " ) . Potentiometri c and electrophoreti c studie s wer e inconclusiv e becaus e th e ZP C coul d no t b e determine d withi n th e desig n o f th e experiments . Th e electrophoreti c result s sugges t tha t th e ZP C wa s a t a p H les s tha n 2 , th e lowes t p H considere d i n thes e experiments . Som e recommendation s fo r futur e laborator ywor k ar e a s follows . 1 . Expan d th e temperatur e an d p H rang e o f th e experiment s fo r th e evaluatio n o f th e enthalp yo f sorption . 2 . Continu e t o analyz e sample s fro msorptio n experiment s fo r th e trace r o f interes t and fo r othe r constituent s tha t wil l provid e supportin g informatio n o n th e sorptio n o f th e tracer . 3 . Perfor msorptio n experiment s i n binar ysystem s a s wel l a s i n a syste mo f J-1 3 wel l water . Fo r example , determin e th e sorptio n behavio r o f lithiumi n a calciumsyste man d i n a sodiumsystem . Th e 7 3thermodynamic s o f thes e system s shoul d permi t a n extrapolatio n o f

result s t o a syste mi n whic hbot hcalciuman d sodiumca n contro l th e sorptio n behavio r o f lithium(e.g. , J-1 3 wel l wate r system) . 4 . Ds e additiona l roc k sample s a s wel l a s representativ e individua l mineral s t o increas e th e representativenes s o f th e result s fo r th e fiel d tests . 5 . Expan d th e effor t t o characteriz e kinetic s t o improv e th e understandin g o f th e relativ e contro l b yphysica l o r chemica l sorptio n processes . 6 . Tes t th e abilit yo f th e develope d isotherm s t o predic t th e breakthroug hpattern s obtaine d fro mcolumn studie s unde r variou s velocitie s ar. d influen t conditions . Th e overal l conclusio n fro mth e laborator yeffort s i s tha t lithium bromid e i s a goo d candidat e trace r fo r a fiel d tes t i n a n environmen t wher e th e chemistr yclosel yresemble s th e chemistr yo f th e Pro wPas s materia l i n contac t wit hJ-1 3 wate r an d i n th e presenc e o f dissolve d oxyge n withi n a temperatur e rang e o f 25-45° C an d a p H rang e o f abou t 8 . Lithiumi s expecte d t o b e slightl yretarde d (retardatio n facto r o f abou t 2 ) wit hgoo d reversibility . It s adsorption , a s suggeste d b yth e thermodynami c constants , fall s i n th e categor yo f physica l adsorption . 

### ACKNOWLEDGMENT S Th e author s wis ht o than k Dr . H . Gopal a Rao , collaborato r fro mHowar d University , fo r th e calculatio n and interpretatio n o f thermodynami c data . Also , w e wis ht o than k Dr . F . A . Tome i fo r characterizin g th e microbia l growt h

7 4tha t wa s observe d i n ou r initia l experiments . Ke ycontribution s hav e bee n th e analytica l chemistr yservice s performe d b yD . J . Hoar d and G . E . Bentley , CLS-1 , an d th e particl e siz e distributio n analyse s performe d byJ . Hunter , MST-6 . Finally , w e than k Sylvi a M . Gonzale s fo r he r effort s i n maintainin g th e qualit yassuranc e documentatio n an d i n wor d processin g th e manuscript .

7 5

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Press , Ne wYork , NY . 31 . Sittig , M . (ed. ) 1980 . Priorit ytoxi c pollutants . Noye s Dat a Corporation , Par k Ridge , NJ . 32 . OTA-0-233 . 1984 . Protectin g th e nation' s groundwate r fro m contamination . Offic e o f Technolog yAssessment , Washington , DC . 33 . APHA , AVVA , VPCF . 1985 . 16t h'Ed . Standar d method s fo r th e examinatio n o f wate r an d wast e water . America n Publi c Healt hAssociation , Vashington , DC . 34 . ASA , SSSA . 1982 . 2n d Ed . Method s o f analysis , Par t 2 . America n Societ yo f Agronomy , Inc. , Madison , VI . 35 . Bish , D . L. , D . T . Vaniman , F . M . Byers , Jr. , and D . E . Broxton . 1982 . Summar yo f th e mineralogy-petrolog yo f tuff s o f Yucc a Mountai n an d th e secondary-phas e therma l stabilit yi n tuffs . Lo s Alamo s Nationa l Laborator yrepor t LA-9321-MS , Lo s Alamos , NM . 36 . Chipera , S . J . and D . L . Bish . 1988 . Mineralog yo f dril l hol e UE-25p# l a t Yucc a Mountain , Nevada . Lo s Alamo s Nationa l Laborator yrepor t LA-11292-MS , Lo s Alamos , NM . 37 . Memorandum . Jun e 17 , 1988 . S . J . Chiper a an d D . L . Bis ht o G . Lopez . Sample s fo r x-ra yanalysis . TV S #ESS-1-6/88-15 , Lo s Alamo s Nationa l Laboratory , Lo s Alamos , NM . 38 . Benson , L . V . an d P . V . McKinley . 1985 . Chemica l compositio n o f groun d wate r i n th e Yucc a Mountai n Area , Nevada , 1971-84 . U . S . Geologica l Surve yrepor t USGS-OFR-85-484 , Denver , CO . 39 . Rosin , P . and E . Rammler . 1933 . Law s coverin g th e finenes s o f Powdere d Coal . J . Inst . Fuel . 7:29-36 . 40 . Greenland , D . J . an d Hayes , M . H . B . Eds . 1981 . Th e chemistr yo f soi l processes . Joh n Vile yand Sons , Ne wYork , NY . 41 . Krauskopf , K . B . 1979 . Introductio n t o geochemistry . McGraw-Hil l Boo k Co. , Ne wYork , NY . 42 . Langmuir , I . 1918 . Th e adsorptio n o f gase s o n plan e surface s o f glass , mic a an d platinium . J . Am . Chem . Soc . 40:1361 . 43 . Sips , R . 1948 . On th e structur e o f a catalys t surface . J . Chem . Phys . 16:490 . 44 . Sposito , G . 1980 . Derivatio n o f th e Freundlic hequatio n fo r io n exchang e reaction s i n soils . Soi l Sci . Soc . Am . J . 44:652-654 .

7 845 . Crickmore , P . J . and B . V . Vojciechowski . 1977 . Kinetic s o f adsorptio n

o f energeticall yheterogeneou s surfaces . J . Chem . Soc . Farada yTrans . 173:121 6 46 . Sparks , D . L . 1986 . Soi l physica l chemistry . CR C Press , Boc a Raton , PI . 47 . Biggar , J . V . and M . V . Cheung . 1973 . Adsorptio n o f Piclora n (4-amino-3,5,6-trichoropicolini c acid ) o n Panoche , Ephrata , and Palous e soils : a thermodynarai c approac ht o th e adsorptio n mechanism . Soi l Sci.Soc . Am . J . 37 : 863-868 . 48 . IcCloskey , V . B . and D . E . Bayer . 1987 . Thermodynamic s o f fluridon e adsorptio n an d desorptio n o n thre e Californi a soils . Soi l Sci . Soc . Am . J . 51 : 605-612 . 49 . EA-3417 . 1984 . Geohydrochemica l model s fo r solut e migration , Volum e 1 : Proces s descriptio n and compute r cod e selection . Energ yPowe r Researc h Institute , Pal o Alto , CA . 50 . Parkhurst , D . L. , D . C . Thorstenson , and L . N . Plummer . 1980 . PHREEQ E - a compute r progra mfo r geochemica l calculations . U . S . Geologica l Surve y Water , Resource s Investigation s 80-96 . 51 . Parker , J . C , L . V . Zelazny , S . Sampath , and V . G . Harris . 1979 . A critica l evaluatio n o f th e extensio n o f zer o poin t o f charg e (ZPC ) theor y t o soi l systems . Soi l Sci . Soc . Amer . J . 43:668-674 . 52 . SA S 0-917382-66-8 . 1985 . SA S user' s guide , statistics , versio n 5 edition . SA S Institute , Inc. , Cary , NC .

7 9

### Appendi xA ANALYTICAL INSTRUMENTATION

8 1A

variet y o f analytica l instrument s hav e bee nuse di nmeasurement s an d characterizatio no f eithe r liqui do r soli dsamples . liqui dsample s wer e analyze do na routin e basi s b y inductivel y

couple dplasma-atomi c emissio n spectroscopy

(ICP-AES ) fo r cation s wit hatomi c weight s les s tha n80 , b y inductivel y

couple dplasma-mas s spectroscopy (ICP-MS ) fo r cation s wit hatomi c weight s greate r tha n80 , an db y ionchromatograph

y (IC ) fo r anions . Th e pH o f solution s wa s measure dwit ha Cornin g pH-Mete r Mode l 13 0 (expande dpH-range ) wit ha nOrio nCombinatio nElectrod e (precisio no f *0.0 2 p H units) . Characterizatio no f geologica l sample s (Pro w Pas s cuttings ) wa s accomplishe d wit ha Siemen s D-50 0 X-Ra y Diffractio nSystem

(XRD) . Unsuccessfu l attempt s t o determin e th e presenc e o r absenc e o f surfac e lithiu m o nProw Pas s materia l wer e mad e wit ha x-ra y

photoelectro nspectroscop e (XPS) . A nalternativ e approac ht o determin e surfac e lithiu m wa s explore dwit hcylindrica l interna l reflection-Fourie r transform infrare dspectroscopy

(CIR-FTIR) . Thi s effor t wa s discontinue dafte r preliminar y result s di dno t prov e immediatel y successful . Surfac e are a analysi s o f th e /ro w Pas s sample s wa s performe dwit ha Quantasor bJr . instrument . Th e particl e siz e distribution s fo r th e sam e sample s wer e obtaine dwit hvariou s instruments : U.S.A . standar dtestin g sieve s o f stainles s stee l (V . S . Tyler , Inc. ) upt o 4 4 /* m (mes h325) , an

da Micrometritic s Sedigraph5000 DParticl e Siz e Analyze r fo r les s tha n4 4 /xr a bu t equa l t o o r greate r tha n2 5 /im. Durin g th e developmen t o f experimenta l procedure s th e appearanc e o f microbia l growt hmotivate da simpl e characterizatio no f th e growt handorgani c substrate . Growt hwa s observe db y a nOlympu s microscop e (phas e contras t an d

8 2fluorescenc e photomicrographs) . Bacteria l densit ywa s estimate d b y adenosine-triphosphat e (ATP ) measurement s wit ha Lo s Alamo s Diagnostic s Mode l 535 Y Luminometer . Colloida l siz e distribution s wer e determine d wit ha flo w cytometer . Tota l organi c carbo n (TOC ) analyse s wer e performe d o n a Photoche m tota l organi c analyze r fo r th e determinatio n o f organi c substrate . Potentiometri c studie s comprise d titrametri c an d electrophoreti c measurements . Titrametri c measurement s wer e mad e wit ha combinatio n o f a Fishe r Burett e Mode l 394 , a Fishe r Titrat e Stirre r Mode l 385 , an d a Fishe r Electromete r Mode l 380 . Electrophoreti c mobilit ymeasurement s employe d a Zet a Mete r 3. 0 System . Batc hstudie s use d bot ha modificatio n o f a Patterson-Kelle yTwi n Shel l Dr ya s a rotato r (2 0 rpm ) an d 500-m L glas s resi n kettles . Mixin g i n th e kettle s wa s accomplishe d wit hpaddle s turne d b y6 . K . Heller , G T 21-1 8 Stirrers . Routin e wor k als o employe d tw o Sartoriou s balance s (Mode l 370 4 wit ha precisio n o f 0.00 5 g , an d Mode l 371 3 wit ha precisio n o f 0.005/0.0 5 g) , riffl e splitter s an d pulverizer s fo r geologica l samples , an d centrifuge s fo r liquid/soli d separation . Al l experiments , tests , an d measurement s wer e conducte d i n a n environmenta l roo mwit hcontrolle d temperatur e whe n a constan t temperatur e wa s required . Th e roo mtemperatur e ca n b e maintaine d t o withi n 

### *1°C .

### Appendi xB ESTIMATE S OF LITHIU I ADSOiPTION ANDDESOtPTION

EQUILIBilU l CONCENT1ATION S

8 5Appendix B i s a compilatio n o f dat a fo r th e adsorptio n and desorptio n o f lithiumo n a Pro wPas s suspensio n i n J-1 3 wel l wate r a t 25°C , 38°C , an d 4 5 C . Give n dat a ar e base d o n tw o method s o f evaluatin g adsorbe d and desorbe d lithium . Bes t estimat e value s ar e als o give n an d wer e use d i n th e evaluatio n o f th e selectio n o f lithiuma s a trace r exhibitin g physica l sorptiv e propertie s fo r th e C-well s fiel d tests . Table s B- I throug hB-II I contai n adsorptio n dat a fo r experiment s performe d a t a n initia l concentratio n rang e o f 1 t o 200 0 figL i m L an d a solid-to-liqui d rati o o f 1:20 . Table s B-I V throug h B-V I sho wadsorptio n dat a fo r experiment s performe d a t a n initia l concentratio n rang e o f 1 t o 15 0 figl i ml " and a solid-to-liqui d rati o o f 1:10 . Tabl e B-VI I show s desorptio n dat a fo r thos e experiment s performe d a t 38° C a t a n initia l concentratio n rang e o f 1 t o 200 0 figL i ml " an d a solid-to-liqui d rati o o f 1:20 . Tabl e B-VII I show s desorptio n dat a fo r thos e experiment s als o performe d a t 38° C bu t a t a n initia l concentratio n rang e o f 1 t o 15 0 figL i mL " an d a solid-to-liqui d rati o o f 1:10 .

8 6

### TABL E B- I

ADSORBE D LITHIU MCONCENTRATION S A S ESTIMATE D B Y TVO METHOD S AN D THOS E CONSIDERE D BES T ESTIMATE S FO R ADSORPTIO NO NAPRO V PAS S SUSPENSIO NI NJ-1 3 VEI L WATE R A T 25° C FO R ANINITIA L CONCENTRATIO N RANG E O F 1 T O 200 0 /j

g L i mL" 1 

### AND ASOLID-TO-LIQUI D RATI O O F 1:2 0

Targete d Initia l Concentratio n 

### (ngL i mL" 1 

### ) 1 5 1 0 5 0 10 0 25 0 50 0 75 0 100 0 200 0 Adsorbe d Lithium(figg

LithiumLos s fro mSolutio n 3.4 7 13. 9 19 8 83. 3 16 3 101 0 0. 0 17 4 59 0 55 5 Cation s Gaine d

i n Solutio n 0. 0 83. 3 10. 4 65. 9 11 5 28 1 31 9 39 2 88 8 60 4 1 Solid )

Bes t Estimat e 3.4 7 13. 9 10. 4 83. 3 16 3 39 2 31 9 39 2 59 0 60 4

8 7TABL E B-I I

ADSORBE D LITHIU M CONCENTRATION S A S ESTIMATE D B Y TW O METHOD S AN D THOS E CONSIDERE D BES T ESTIMATE S FO R ADSORPTIO NO NAPRO V PAS S SUSPENSIO NI NJ-1 3 VEL L VATE R A T 38° C FO R A NINITIA L CONCENTRATIO N RANG E O F 1 T O 200 0 figL i mL" 1 AND ASOLID-TO-LiqUI D RATI O O F 1:2 0

Targete d Initia l Concentratio n (/i g L i mL " ) 1 5 1 0 5 0 10 0 25 0 50 0 75 0 100 0 200 0 Adsorbe d Lithium(figg ~ Lithiu mLos s fro mSolutio n

2.7 8 18. 7 21. 9 10 1 22 1 72. 9 10. 4 20 1 37 8 239 0 Cation s Gaine d

i n Solutio n

-29. 5 -20. 1 -30. 5 50. 0 12 6 15 3 36 7 42 3 49 4 60 5 1 Solid )

Bes t Estimat e

2.7 8 18. 7 21. 9 50. 0 12 6 15 3 36 7 42 3 49 4 60 5

8 8

### TABL E B-II I

ADSORBE DLITHIU

M CONCENTRATION S A S ESTIMATE DB YTV O METHOD S ANDTHOS E CONSIDERE DBES T ESTIMATE S FO RADSORPTION O N A PROV PAS S SUSPENSIO N I N J-1 3 VEL L VATE RA T 45° C FO RA N INITIAL CONCENTRATIO N RANG E O F 1 T O 200 0 /t

g L i mL" l 

### ANDA

SOLID-TO-LIQUI DRATI O O F 1:2 0

Targete d Initia l Concentratio n (figL i mL" 1 ) 1 5 1 0 5 0 10 0 25 0 50 0 75 0 100 0 200 0 Adsorbe dLithiu m (fig g Lithiu m Los s 

### fro m Solutio n

3.4 7 13. 9 31. 2 90. 2 25 0 51 0 31 2 72 9 59 0 104 0 Cation s Gaine d



### inSolutio n

45. 1 6.9 4 13. 9 11 1 13 2 90. 2 20 8 21 9 24 3 50 0 1 Solid )

Bes t Estimat e

3.4 7 6.9 4 13. 9 11 1 13 2 90. 2 20 8 21 9 24 3 50 0

8 9

### TABL E B-I V

ADSORBE D LITHIU MCONCENTRATION S A S ESTIMATE D B Y TVO METHOD S AN D THOS E CONSIDERE D BES T ESTIMATE S FO R ADSORPTIO NONAPRO V PAS S SUSPENSIO NI NJ-1 3 VEL L VATE R A T 25° C FO R A NINITIA L CONCENTRATIO NRANG E O F 1 T O 15 0 figL i mL' 1 

### AND ASOLID-TO-LIQUI D RATI O O F 1:1 0

Targete d Initia l Concentratio n {tigL i mL" 1 ) 1 5 1 0 2 0 5 0 10 0 15 0 Adsorbe d Lithium(/z g g LithiumLos s fro mSolutio n

1.8 0 4.5 1 11. 1 18. 0 -22. 0 64. 0 5.0 0 Cation s Gaine d

i n Solutio n

-5.5 8 5.6 0 15. 5 29. 0 74. 9 67. 0 11 1 1 Solid )
Bes t Estimat e

1.8 0 5.6 0 15. 5 29. 0 75. 0 67. 0 11 1

9 0TABL E B- V

ADSORBE D LITHIU M CONCENTRATION S A S ESTIMATE D B Y TV O METHOD S AN D THOS E CONSIDERE D BES T ESTIMATE S FO R ADSORPTIO NONAPRO V PAS S SUSPENSIO NI NJ-1 3 VPI L VATE R A T 38° C FO R ANINITIA L CONCENTRATIO N RANG E O F 1 T O 15 0 /i

g L i raL" * AN D ASOLID-TO-LttJUI D RATI O O F 1:1 0

Targeted Initia l Concentration (figL i raL" 1 ) 1 5 1 0 2 0 5 0 10 0 15 0 Adsorbe d Lithiu m(/igg Lithiu mLos s fro mSolutio n

1.9 0 12. 5 21. 0 50. 0 11 0 12 7 19 5 Cation s Gaine d i n Solution

-4.5 8 4.0 5 21. 2 33. 7 83. 1 92. 9 94. 7 1 Solid )

Bes t Estimat e

1.9 0 4.0 5 21. 2 33. 7 83. 0 93. 0 95. 0

9 1TABL E B-V I

ADSORBE D LITHIU M CONCENTRATION S A S ESTIMATE D B Y TVO METHOD S AND THOS E CONSIDERE D BES T ESTIMATE S FO R ADSORPTIO NONAPRO V PAS S SUSPENSIO NI NJ-1 3 VEL L VATE R A T 45° C FO R ANINITIA L CONCENTRATIO NRANG E O F 1 T O 15 0 # g L i mL' 1 AN D ASOLID-TO-LIQUI D RATI O O F 1:1 0

Targete d Initia l Concentratio n {figL i mL' 1 ) 1 5 1 0 2 0 5 0 10 0 15 0 Adsorbe d Lithiu m[figg " Lithiu mLos s fro mSolutio n
2.5 9 10. 6 19. 7 56. 0 14. 5 17 5 19 0 Cation s Gaine d

i n Solutio n
-15. 5 -5.0 0 5.1 1 21. 6 10 3 99. 6 12 9 1 Solid )

Bes t Estimat e
2.6 0 10. 6 19. 7 38.8 1 58.5 1 137 1 160 1 Value s represen t th e mea n o f lithiu mlos t and cation s gained .

9 2TABL E B-VI I TH E BES T ESTIMAT E O F ADSORBE DLITHIUM A S DETERMINE DB Y TVO METHOD S FO RTH E DESORPTIO N O F LITHIUM

FRO M A PRO V PAS S SUSPENSIO N

I N J-1 3 VEL L VATE RA T 38° C FO RA N INITIA L CONCENTRATIO N RANG E O F 1 T O 200 0 fig

L i mL" 1 AN D A

SOLID-TO- LiqUI DRATI O O F 1:2 0

Targete d Initia l Solutio n Concentratio n (/* g L i mL' 1 ) 1 5 1 0 5 0 100 250 50 0 

### 75 0 100 0 200 0 Lithium

Soli dPhas e Befor e Desorptio n 

## teg" 1 

## ) 2.7 8 18. 7 21. 9 50. 0 12 6 15 3 36 7 423 49 4 605 Lithium

Gaine di n Solutio n (/*eq )

0.72 5 4.8 2 4.0 2 16. 1 22. 6 -10. 2 -45. 9 0.8 0 -7.5 3 -8.5 8 Cation s

Los s Fro m Solutio n (/«eq )

5.4 7 4.5 9 10. 5 13. 9 20. 1 38. 5 45. 0 54. 3 -11. 2 54. 6 Bes t

Estimat e (/*eq )

0.72 5 4.8 2 4.0 2 16. 1 21. 3 38. 5 45. 0 54. 3

— 54. 6 Lithium

i nSoli dPhas e afte r Desorptio n (Z^gg" 1 )

0.26 4 2.0 0 7.9 5 2.0 0 52. 0 19. 0 21 1 235

— 415 Excludin g lithium .

9 3TABL E B-VII I TH E BES T ESTIMAT E O F ADSORBE DLITHIUM A S DETERMINE DB Y TVO METHOD S FO RTH E DESORPTIO N O F LITHIUM

FROM A PRO V PAS S SUSPENSIO N

I N J-1 3 VEL L VATE RA T 38° C FO RA N INITIA L CONCENTRATIO N RANG E O F 1 T O 15 0 fig

L i ml" 1 ANDA

SOLID-TO-LiqUI DRATI O O F 1:1 0

Targete d Initia l Solutio n Concentratio n (fig Li mL' 1 ) 1 5 1 0 20 50 100 15 0 Lithium

i n Soli dPhas e Befor e Desorptio n

1.9 0 4.4 1 21. 2 33. 7 83. 1 92. 9 94. 7 Lithium

Gaine di n Solutio n (/teq )

0.62 5 2.7 8 5.0 2 11. 0 20. 4 24. 9 27. 7 Cation s

Los s From Solutio n (/<eq )

-2.4 2 1.2 6 2.7 4 7.5 4 20. 3 24. 8 27. 9 Bes t

Estimat e 

## Ueq )

0.62 5 2.7 8 5.0 2 11. 0 20. 3 24. 9 27. 8 Lithium

i n Soli dPhas e Afte r Desorptio n (/* g g' 1 )

0.4 5 1.5 0 9.5 9 12. 3 36. 1 35. 3 30. 5 Excludin g lithium .

### Appendi xC

EqUILIBlIU l CONCENTRATION S ANDMODELINGVARIABLE S

9 5Appendi x C compile s al l th e dat a set s fro mth e adsorptio n and desorptio n equilibriu mbatc hexperiment s tha t ar e referre d t o i n thi s report . Th e table s correspon d t o experiment s conducte d a t 25°C , 38°C , and 45° C fo r tw o range s o f initia l concentration s o f lithiumi n solution , tha t is , 1 t o 200 0 and 1 t o 15 0 figmil . Column s labele d S « throug hS , an d C Q throug hC . ar e transformation s o f equilibriu mconcentration s C and S use d t o calculat e th e linea r regressiona l parameter s o f th e Langmuir , Freundlich , an d Modifie d Freundlic h isotherms . Th e regressio n o f th e Linea r isother muse s th e C an d S value s directly . Al l thes e variable s ar e input s t o a cod e base d o n SA S routine s (52 ) tha t generate s th e parameter s an d th e regressiona l statistic s fo r eac h isotherm . Th e variou s column s ar e define d a s follows :

C = initia l concentratio n CE C = catio n exchang e capacit yo f Pro wPas s material , figL i g soli d S = equilibriu mconcentratio n o n th e solid , figL i g " soli d C = equilibriu mconcentratio n i n solution , figL i mL " 1L 0 S g = C S , dependen t variabl e use d i n th e regressio n fo r th e Langmui r isother m C g = C , independen t variabl e use d i n th e regressio n fo r th e Langmui r isother m S , = lo g S , dependen t variabl e use d i n th e regressio n fo r th e Freundlic hisother m C g = lo g C , independen t variabl e use d i n th e regressio n fo r th e Freundlic hisother m S 4 = lo g [S(CEC-S) " ] , dependen t variabl e use d i n th e regressio n fo r th e Modifie d Freundlic hisotherm .
9 6C , = lo g C , independen t variabl e use d i n th e regressio n fo r th e

Modifie d Freundlic hisother m Dat a set s ar e organize d i n accordanc e wit hth e followin g sequence : 1 . Adsorptio n equilibriumdat a fo r th e 1

- to
- 2000

- figml " rang e o f initia l concentration s a t a solid-to-liqui d rati o o f 1:20 . 1. 1 Temperatur e = 25° C Dat a se t base d o n measure d lithium . Dat a se t base d o n measure d lithiuman d othe r cation s (bes t estimate) . 1. 2 Temperatur e = 38° C Dat a se t base d o n measure d lithium . Dat a se t base d o n measure d lithiuman d othe r cation s (bes t estimate) . 1. 3 Temperatur e = 45° C Dat a se t base d o n measure d lithium . Dat a se t base d o n measure d lithiuman d othe r cation s (bes t estimate) . 2 . Adsorptio n equilibriumdat a fo r th e l-to-150-/i g ml " rang e o f initia l concentration s a t a solid-to-liqui d rati o o f 1:10 . 2. 1 Temperatur e = 25° C Dat a se t base d o n measure d lithium . Dat a se t base d o n measure d lithiuman d othe r cation s (bes t estimate) . 2. 2 Temperatur e = 38° C Dat a se t base d o n measure d lithium .

9 7Dat a se t base d o n measure d lithiumand othe r cation s (bes t

estimate) . 2. 3 Temperatur e = 45° C Dat a se t base d o n measure d lithium . Dat a se t base d o n measure d lithiumand othe r cation s (bes t estimate) . 3 . Desorptio n equilibriu mdat a a t 3 8 C an d a solid-to-liqui d rati o o f 1:10 . 3. 1 Dat a se t base d o n measure d lithiumand othe r cation s fo r 1 t o 200 0 figrnL' 1

. 3. 2 Dat a se t base d o n measure d lithiumand othe r cation s fo r 1 t o 15 0 ftgml' 1

.

9 8TABL E C- I ADSORPTIO

N EQUILIBRIU

M DATA FO RTH E 1-200 0 fig

nt' 1 RANG

E OF INITIA

L LITHIU M CONCENTRATION S I

N SOLUTIO N AT 25°C . CONCENTRATION S CORRESPON D T O MEASURE D LITHIUM ; SOLID-TO-L1QUI D RATI O = 1:20 .

CE C 1.0 0 1.0 0 4.8 6 4.8 6 10.2 0 10.2 0 53.S 0 53.5 0 112.0 0 112.0 0 200.0 0 200.0 0 446.0 0 '446.0 0 682.0 0 682.0 0 895.0 0 895.0 0 1844.0 0 1844.0 0 0.8 7

0.8 7 4.0 8 4.2 7 9.0 3 9.0 7 47.7 0 50.7 0 103.0 0 105.0 0 162.0 0 153.0 0 444.0 0 461.0 0 676.0 0 666.0 0 861.0 0 870.0 0 1751.0 0 1882.0 0 110 4

110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 2.S 2

2.5 8 15.6 0 11.8 0 23.4 0 22.6 0 116.0 0 56.0 0 180.0 0 140.0 0 760.0 0 940.0 0 40.0 0 -300.0 0 120.0 0 320.0 0 680.0 0 500.0 0 1860.0 0 -760.0 0 0.8 7

0.8 7 4.0 8 4.2 7 9.0 3 9.0 7 47.7 0 50.7 0 103.0 0 105.0 0 162.0 0 153.0 0 444.0 0 461.0 0 676.0 0 666.0 0 861.0 0 870.0 0 1751.0 0 1882.0 0 0.346 8

0.337 6 0.261 5 0.361 9 0.385 9 0.401 3 0.411 2 0.905 4 0.572 2 0.750 0 0.213 2 0.162 8 11.100 0 -1.536 7 5.633 3 2.081 3 1.266 2 1.740 0 0.941 4 -2.476 3 -0.0584 9

-0.0599 8 0.6106 6 0.6304 3 0.9556 9 0.9576 1 1.6785 2 1.7050 1 2.0128 4 2.0211 9 2.2095 2 2.1846 9 2.6473 8 2.6637 0 2.8299 5 2.8234 7 2.9350 0 2.9395 2 3.2432 9 3.2746 2 0.4014 0

0.4116 2 1.1931 2 1.0718 8 1.3692 2 1.3541 1 2.0644 6 1.7481 9 2.2552 7 2.1461 3 2.8808 1 2.9731 3 1.6020 6 • 2.0791 8 2.5051 5 2.B3Z5 1 2.6989 7 3.2695 1 • -0.0584 9

-0.0599 8 0.6106 6 0.6304 3 0.9556 9 0.9576 1 1.6785 2 1.7050 1 2.0128 4 2.0211 9 2.2095 2 2.1846 9 2.6473 8 2.6637 0 2.8299 5 2.8234 7 2.9350 0 2.9395 2 3.2432 9 3.2746 2 -2.640 6

-2.630 3 -1.843 7 -1.966 4 -1.664 4 -1.679 9 -0.930 3 -1.272 2 •0.710 4 -0.837 9 0.344 3 0.758 3 -1.424 9 • -0.913 8 -0.389 2 0.205 1 -0.082 1

•

9 9TABLE C-I I

ADSORPTIO N EQUILIBRIU M DAT A FO R TH E 1-200 0 fig

mL" 1 RANG

E OF INITIA L LITHIU M CONCENTRATIONS I N SOLUTIO N A

T25°C . CONCENTRATION S ARE BES TESTIMATE S FRO

M MEASURE

D LITHIU M AN

D OTHE R CATIONS ; SOLID-TO-LIQUI D RATI O = 1:20 .

CE C 0.8 7 4.1 8 9.0 5 49.2 0 104.0 0 158.0 0 452.0 0 671.0 0 895.0 0 1844.0 0 3.4 7

13.8 8 10.4 1 83.3 0 163.1 0 281.0 0 319.0 0 392.0 0 590.0 0 604.0 0 110 4

110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 0.8 7

4.1 8 9.0 5 49.2 0 104.0 0 158.0 0 452.0 0 671.0 0 895.0 0 1844.0 0 0.2507 2

0.3011 5 0.8693 6 0.5906 4 0.6376 5 0.5622 8 1.4169 3 1.7117 3 1.5169 5 3.0529 8 •0.0604 8

0.6211 8 0.9566 5 1.6919 7 2.0170 3 2.1986 6 2.6551 4 2.8267 2 2.9518 2 3.2657 6 0.5403 3

1.1423 9 1.0174 5 1.9206 5 2.2124 5 2.4487 1 2.5037 9 2.5932 9 2.7708 5 2.7810 4 -0.0604 8

0.6211 8 0.9566 5 1.6919 7 2.0170 3 2.1986 6 2.6551 4 2.8267 2 2.9518 2 3.2657 6 -2.501 3

-1.895 1 •2.021 4 -1.088 3 -0.761 1 •0.466 7 -0.391 1 -0.259 2 0.059 9 0.082 1

10 0TABL E C-M I ADSORPTION

EQUILIBRIU

M DAT A FO RTHE 1-200 0 /i

g ml" 1 RANGE O

F INITIA L LITHIU M CONCENTRATION S I

N SOLUTIO N AT 38°C . CONCENTRATION S CORRESPON DT O MEASURE DLITHIUM ; SOLID-TO-LIQUI DRATI O = 1:20 .

CE C 0.9 8 0.9 8 4.9 1 4.9 1 10.1 0 10.1 0 53.9 0 53.9 0 111.0 0 111.0 0 230.0 0 230.0 0 470.0 0 470.0 0 690.0 0 690.0 0 959.0 0 959.0 0 1915.0 0 1915.0 0 0.8 1

0.8 3 3.8 0 4.1 4 8.6 3 9.3 9 48.5 0 49.2 0 98.9 0 101.0 0 224.0! ) 229.0 0 460.0 0 479.0 0 704.0 0 656.0 0 973.0 0 907.0 0 1910.0 0 1680.0 0 110 4

110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 3.4 0

3.0 0 22.2 0 15.4 0 29.4 0 14.2 0 108.0 0 94.0 0 242.0 0 200.0 0 120.0 0 20.0 0 200.0 0 -180.0 0 -280.0 0 680.0 0 -280.0 0 1040.0 0 100.0 0 4700.0 0 0.8 1

0.3 3 3.8 0 4.1 4 8.6 3 9.3 9 48.5 0 49.2 0 98.9 0 101.0 0 224.0 0 229.0 0 460.0 0 479.0 0 704.0 0 656.0 0 973.0 0 907.0 0 1910.0 0 1680.0 0 0.238 2

0.276 7 0.171 2 0.268 8 0.293 5 0.661 3 0.449 1 0.523 4 0.408 7 0.505 0 1.866 7 11.450 0 2.300 0 -2.661 1 -2.514 3 0.964 7 -3.475 0 0.872 1 19.100 0 0.357 4 -0.0915 1

-0.0809 2 0.5797 8 0.6170 0 0.9360 1 0.9726 7 1.6857 4 1.6919 7 1.9952 0 2.0043 2 2.3502 5 2.3598 4 2.6627 6 2.6803 4 2.8475 7 2.8169 0 2.9881 1 2.9576 1 3.2810 3 3.2253 1 0.5314 8

0.4771 2 1.3463 5 1.1875 2 1.4683 5 1.1522 9 2.0334 2 1.9731 3 2.3838 2 2.3010 3 2.0791 8 1.3010 3 2.3010 3

2.8325 1 3.0170 3 2.0000 0 3.6721 0 -0.0915 1

-0.0809 2 0.5797 8 0.6170 0 0.9360 1 0.9726 7 1.6857 4 1.6919 7 1.9952 0 2.0043 2 2.3502 5 2.3598 4 2.6627 6 2.6803 4 2.8475 7 2.8169 0 2.9881 1 2.9576 1 3.2810 3 3.2253 1 -2.510 2

-2.564 7 -1.687 8 -1.849 3 -1.562 9 -1.885 1 -0.964 8 -1.031 2 -0.551 7 -0.655 1 -0.913 8 -1.734 0 -0.655 1 • « 0.205 1 • 1.210 9 -1.001 7

10 1TABL E C-I V

ADSORPTION

EQUILIBRIU

M DATA FO RTHE 1-200 0 fig

mL~ 1 RANGE OF INITIA

L LITHIU M CONCENTRATION S I N SOLUTIO N AT 38°C . CONCENTRATION S AR E BES T ESTIMATE S FRO M MEASURE DLITHIU

M AN DOTHER CATIONS ; SOLID-TO-LIQUI DRATI O = 1:20 .

CE C 0.8 2 3.9 7 9.0 0 48.9 0 100.0 0 226.0 0 470.0 0 680.0 0 940.0 0 1795.0 0 2.7 8

18.7 0 21.9 0 50.0 0 126.0 0 153.0 0 367.0 0 423.0 0 494.0 0 605.0 0 110 4

110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 0.8 2

3.9 7 9.0 0 48.9 0 100.0 0 226.0 0 470.0 0 680.0 0 940.0 0 1795.0 0 0.2949 6

0.2123 0 0.4109 6 0.9780 0 0.7936 5 1.4771 2 1.2806 5 1.6075 7 1.9028 3 2.9669 4 -0.0861 9

0.5987 9 0.9342 4 1.6893 1 2.0000 0 2.3541 1 2.6721 0 2.8325 1 2.9731 3 3.2540 6 0.4440 4

1.2718 4 1.3404 4 1.6989 7 2.1003 7 2.1846 9 2.5646 7 2.6263 4 2.6937 3 2.7817 6 -0.0861 9

0.5987 9 0.9542 4 1.6893 1 2.0000 0 2.3541 1 2.6721 0 2.8325 1 2.9731 3 3.2540 6 -2.597 8

-1.763 7 -1.693 8 -1.323 9 -0.890 0 -0.793 5 -0.302 8 -0.206 8 -0.091 6 0.083 7

10 2TABL E C- V

- 1 ADSORPTIO

N EQUILIBRIU

M DAT A FO RTHE 1-200 0 /J

g m L RANGE O F fHITtA

L LITHIU M CONCENTRATION S I

N SOLUTIO N AT 45°C . CONCENTRATION S CORRESPON DT O MEASURE DLITHIUM ; SOLID-TO-LIQUI DRATI O = 1:20 .

. C CE C 1.0 3 1.0 3 4.8 9 4.8 9 10.8 0 10.8 0 53.4 0 53.4 0 115.0 0 115.0 0 162.0 0 162.0 0 468.6 0 468.6 0 655.9 0 655.9 0 941.4 0 941.4 0 2044.0 0 2044.0 0 0.8 8

0.8 8 4.2 1 4.1 9 9.2 1 9.1 8 49.0 0 48.8 0 101.0 0 104.0 0 126.0 0 147.0 0 445.7 0 460.1 0 699.0 0 685.0 0 908.3 0 916.2 0 1974.0 0 2004.0 0 110 4

110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 2.9 6

3.0 0 13.6 0 14.0 0 31.8 0 32.4 0 88.0 0 92.0 0 280.0 0 220.0 0 720.0 0 300.0 0 458.0 0 170.0 0 -862.0 0 -582.0 0 662.0 0 504.0 0 1430.0 0 800.0 0 0.8 8

0.8 8 4.2 1 4.1 9 9.2 1 9.1 8 49.0 0 48.8 0 101.0 0 104.0 0 126.0 0 147.0 0 445.7 0 460.1 0 699.0 0 685.0 0 908.3 0 916.2 0 1974.0 0 2004.0 0 0.297 7

0.293 1 0.309 6 0.299 3 0.289 6 0.283 3 0.556 8 0.530 4 0.360 7 0.472 7 0.175 0 0.490 0 0.973 1 2.706 5 -0.810 9 -1.177 0 1.372 1 1.817 9 1.410 0 2.505 0 •0.0545 8

-0.0555 7 0.6242 8 0.6222 1 0.9642 6 0.9628 4 1.6902 0 1.6884 2 2.0043 2 2.0170 3 2.1003 7 2.1673 2 2.6490 4 2.6628 5 2.8444 8 2.8356 9 2.9582 3 2.9619 9 3.2953 5 3.3019 0 0.4715 9

0.4774 1 1.1335 4 1.1461 3 1.5024 3 1.5105 5 1.9444 8 1.9637 9 2.4471 6 2.3424 2 2.8573 3 2.4771 2 2.6608 7 2.2304 5

2.8208 6 2.7024 3 3.1461 3 2.9030 9 -0.0545 8

-0.0555 7 0.6242 8 0.6222 1 0.9642 6 0.9628 4 1.6902 0 1.6884 2 2.0043 2 2.0170 3 2.1003 7 2.1673 2 2.6490 4 2.6628 5 2.8444 8 2.8356 9 2.9582 3 2.9619 9 3.2953 5 3.3019 0 -2.570 2

-2.564 4 -1.904 0 -1.891 3 -1.527 8 -1.519 5 -1.062 4 -1.041 4 -0.468 8 -0.604 0 0.273 0 -0.428 1 -0.149 4 -0.739 9

0.175 4 -0.075 7

. 0.420 2

10 3TABL E C-V I

ADSORPTIO N

EQUILIBRIU

M DAT A FO RTH E 1-200 0 M 9 ml-" 1 RANG E O F INITIA L LITHIU M CONCENTRATION S IN SOLUTIO N

A T 4S°C . CONCENTRATION S AR E BES T ESTIMATE S FRO M MEASURE DLITHIU

M AN DOTHE R CATIONS ; SOLID-TO-LIQUI DRATI O = 1:20 .

CE C 

### h 0.8 8 4.2 0 9.2 0 48.9 0 102.5 0 136.5 0 453.0 0 692.0 0 912.0 0 1989.0 0 3.4 7

6.9 4 13.9 0 111.0 0 132.0 0 90.2 0 208.0 0 219.0 0 243.0 0 500.0 0 110 4

110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 0.8 8

4.2 0 9.2 0 48.9 0 102.5 0 136.5 0 453.0 0 692.0 0 912.0 0 1989.0 0 0.2536 0

0.6051 9 0.6618 7 0.4405 4 0.7765 2 1.5133 0 2.1778 8 3.1598 2 3.7530 9 3.9780 0 -0.0555 2

0.6232 5 0.9637 9 1.6893 1 2.0107 2 2.1351 3 2.6561 0 2.8401 1 2.9599 9 3.2986 3 0.5403 3

0.8413 6 1.1430 1 2.0453 2 2.1205 7 1.9552 1 2.3180 6 2.3404 4 2.3856 1 2.6989 7 -0.0555 2

0.6232 5 0.9637 9 1.6893 1 2.0107 2 2.1351 3 2.6561 0 2.8401 1 2.9599 9 3.2986 3 -2.501 3

-2.198 9 -1.894 5 -0.951 6 -0.867 1 -1.050 7 •0.634 2 •0.606 5 -0.549 4 -0.082 1

10 4TABL E C-VI I 1 ADSORPTION

EOUILIBRIU

H DATA FO RTHE 1-15 0 fig

m L RANGE O F INITIA

L LITHIU M CONCENTRATION S I

N SOLUTIO N A T 25°C . CONCENTRATION S CORRESPON D T O MEASURE D LITHIUM ; SOLID-TO-LIQUI D RATI O = 1:10 .

CE C 0.74 4 0.74 4 3.97 0 3.97 0 8.37 0 8.37 0 21.20 0 21.20 0 60.70 0 60.70 0 89.60 0 89.60 0 138.00 0 138.00 0 0.54 9

0.57 5 3.56 0 3.47 0 7.21 0 7.31 0 19.40 0 19.40 0 62.90 0 62.90 0 81.00 0 85.30 0 135.00 0 140.00 0 110 4

•110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 1.9 5

1.6 9 4.1 0 5.0 0 11.6 0 10.6 0 18.0 0 18.0 0 -22.0 0 -22.0 0 86.0 0 43.0 0 30.0 0 -20.0 0 0.54 9

0.57 5 3.56 0 3.47 0 7.21 0 7.31 0 19.40 0 19.40 0 62.90 0 62.90 0 81.00 0 65.30 0 135.00 0 143.00 0 0.281 5

0.340 2 0.868 3 0.694 0 0.621 6 0.689 6 1.077 8 1.077 8 •2.859 1 -2.859 1 0.941 9 1.983 7 4.500 0 -7.000 0 -0.2604 3

-0.2403 3 0.5514 5 0.5403 3 0.8579 4 0.8639 2 1.2878 0 1.2878 0 1.7986 5 1.7986 5 1.9084 9 1.9309 5 2.1303 3 2.1461 3 0.2900 3

0.2278 9 0.6127 8 0.6989 7 1.0644 6 1.0253 1 1.2552 7 1.2552 7 • • 1.9345 0 1.6334 7 1.4771 2 # -0.2604 3

-0.2403 3 0.5514 5 0.5403 3 0.8579 4 0.8639 2 1.2878 0 1.2878 0 1.7986 5 1.7986 5 1.9084 9 1.9309 5 2.1303 3 2.1461 3 -2.752 2

-2.814 4 -2.428 6 •2.342 0 -1.973 9 -2.013 5 -1.780 6 -1.780 6

• -1.073 2 -1.392 2 -1.553 9

10 5TABL E C-VI1 I

ADSORPTIO N

EQUILIBRIU

M DATA FO RTH E 1-15 0 fig

nrt."1 RANG E O F INITIA

L LITHIU M CONCENTRATION S I N SOLUTION

AT 25°C . CONCENTRATION S AR E BES T ESTIMATE S FRO M MEASURE DLITHIU

M AN D OTHER CATIONS ; SOLID-TO-LIQUI DRATI O = 1:10 .

CE C 0.56 2 3.52 0 7.26 0 19.40 0 62.90 0 83.20 0 138.00 0 1.8 2

5.6 0 15.5 0 29,1 0 74.9 0 66.9 0 .110 4 110 4 110 4 110 4 110 4 110 4 0.56 2

3.52 0 7.26 0 19.40 0 62.90 0 83.20 0 0.3087 9

0.6285 7 0.4683 9 0.6666 7 0.8397 9 1.2436 5 -0.2502 6

0.5465 4 0.8609 4 1.2878 0 1.7986 5 1.9201 2 0.2600 7

0.7481 9 1.1903 3 1.4638 9 1.8744 8 1.8254 3 -0.2502 6

0.5465 4 0.8609 4 1.2878 0 1.7'586 5 1.9201 2 -2.782 2

-2.292 6 -1.846 5 -1.567 5 -1.138 0 -1.190 4 111.0 0 110

4 138.00 0 1.2432 4 2.1398 8 2.0453 2 2.1398 8 -0.951 6

10 6TABLE C-I X ADSORPTIO N EQUILIBRIU M DAT A FO R TH E 1-15 0 fig

mL* 1 RANG

E O F INITIA L LITHIU M CONCENTRATIONS I N SOLUTIO N A

T38°C . CONCENTRATION S CORRESPOND T O MEASURE

D LITHIUM ; SOLID-TO-LIQUI D RATI O = 1:1(1 .

CE C 1.0 0 1.0 0 4.9 0 4.9 0 9.8 0 9.8 0 24.0 0 ?4.0 0 75.0 0 75.0 0 93.2 0 93.2 0 143.0 0 143.0 0 0.8 3

0.7 9 3.6 0 3.7 0 7.7 0 7.7 0 19.0 0 19.0 0 64.0 0 64.0 0 80.6 0 80.4 0 130.0 0 117.0 0 110 4

110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 1. 7

2. 1 13. 0 12. 0 21. 0 21. 0 50. 0 50. 0 110. 0 110. 0 126. 0 128. 0 130. 0 260. 0 0.8 3

0.7 9 3.6 0 3.7 0 7.7 0 7.7 0 19.0 0 19.0 0 64.0 0 64.0 0 80.6 0 80.4 0 130.0 0 117.0 0 0.4882 4

0.3761 9 0.2769 2 0.3083 3 0.3666 7 0.3666 7 0.3800 0 0.3800 0 0.5818 2 0.5818 2 0.6396 8 0.6281 2 1.0000 0 0.4500 0 -0.0809 2

-0.1023 7 0.5563 0 0.5682 0 0.8864 9 0.8864 9 1.2787 5 1.2787 5 1.8061 8 1.8061 8 1.9063 4 1.9052 6 2.1139 4 2.0681 9 0.2304 5

0.3222 2 1.1139 4 1.0791 8 1.3222 2 1.3222 2 1.6989 7 1.6989 7 2.0413 9 2.0413 9 2.1003 7 2.1072 1 2.1139 4 2.4149 7 -0.0809 2

-0.1023 7 0.5563 0 0.5682 0 0.8864 9 0.8864 9 1.27S7 5 1.2787 5 1.6061 8 1.8061 8 1.9063 4 1.9052 6 2.1139 4 2.0681 9 -2.811 9

-2.719 9 -1.923 9 -1.959 0 -1.712 4 -1.712 4 -1.323 9 -1.323 9 -0.956 0 -0.956 0 -0.890 0 -0.882 2 -0.874 6 -0.511 4

10 7TABL E C- X

ADSORPTION

EQUILIBRIU

M DAT A FO RTHE 1-15 0 fig

trl' 1 RANGE OF INITIA

L LITHIU M CONCENTRATION S I N SOLUTION

A T 38°C . CONCENTRATION S ARE BES T ESTIMATE S FRO M MEASURE DLITHIU

M AN DOTHER CATIONS ; SOLID-TO-LIQUI DRATI O = 1:10 .

CE C 0.8 1 3.6 5 7.7 0 19.0 0 64.0 0 80.5 0 124.0 0 1.9 0

4.4 0 21.2 0 33.7 0 83.1 0 92.9 0 94.6 0 110 4 110 4 110 4 110 4 110 4 110 4 110 4 0.81 0

3.65 0 7.70 0 19.00 0 64.00 0 80.50 0 124.00 0 0.4263 2

0.8295 5 0.3632 1 0.5638 0 0.7701 6 0.8665 2 1.3107 8 -0.0915 1

0.5622 9 0.8864 9 1.2787 5 1.8061 3 1.9058 0 2.0934 2 0.2787 5

0.6434 5 1.3263 4 1.5276 3 1.9196 0 1.9680 2 1.9758 9 -0.0915 1

0.5622 9 0.8864 9 1.2787 5 1.8061 8 1.9058 0 2.0934 2 -2.763 5

-2.397 8 -1.703 2 -1.501 9 -1.089 4 -1.036 8 •1.028 2

10 8TABL E C-X I ADSORPTION

EQUILIBRIU

M DATA FO RTH E 1-15 0 fig

ml* 1 RANGE OF INITIA

L LITHIU M CONCENTRATION S I

N SOLUTIO N A T 45°C . CONCENTRATION S CORRESPON DT O MEASUREDLITHIUH ; SOLID-TO-LIQUI DRATI O = 1:10 .

CE C 0.7 7 0.7 7 4.4 0 4.4 0 9.1 0 9.1 0 23.5 0 23.5 0 101.0 0 101.0 0 159.0 0 159.0 0 0.5 2

0.5 0 3.4 0 3.4 0 7.3 0 7.1 0 17.5 0 18.3 0 80.0 0 86.0 0 140.0 0 140.0 0 110 4

110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 2. 5

2. 7 10. 0 10. 0 18. 0 20. 0 60. 0 52. 0 210. 0 150. 0 190. 0 190. 0 0.5 2

0.5 0 3.4 0 3.4 0 7.3 0 7.1 0 17.5 0 18.3 0 80.0 0 86.0 0 140.0 0 140.0 0 0.2080 0

0.1851 9 0.3400 0 0.3400 0 0.4055 6 O.3S50 0 0.2916 7 0.3519 2 0.3809 5 0.5733 3 0.7368 4 0.7368 4 -0.2840 0

-0.3010 3 0.5314 8 0.5314 8 0.8633 2 0.8512 6 1.2430 4 1.2624 5 1.9030 9 1.9345 0 2.1461 3 2.1461 3 0.3979 4

0.4313 6 1.0000 0 1.0000 0 1.2552 7 1.3010 3 1.7781 5 1.7160 0 2.3222 2 2.1760 9 2.2787 5 2.2787 5 •0.2840 0

-0.3010 3 0.5314 3 0.5314 8 0.8633 2 0.8512 6 1.2430 4 1.2624 5 1.9030 9 1.9345 0 2.1461 3 2.1461 3 -2.644 0

-2.610 5 •2.039 0 -2.039 0 -1.780 6 -1.734 0 -1.240 5 -1.306 0 -0.629 1 -0.803 5 -0.682 2 T0.682 2

10 9TABL E C-XI I ADSORPTION EQUILIBRIU M DAT A FO R THE 1-15 0 fig

mL* 1 RANG

E O F INITIA L LITHIU M CONCENTRATION S I N SOLUTIO N A

T45°C . CONCENTRATION S AR E BES TESTIMATE

S FRO M MEASURE

D LITHIU M AN

O OTHE R CATIONS ; SOLID-TO-LIQUI D RATI O = 1:10 .
CE C 0.51 1 3.40 0 7.16 0 17.90 0 63.55 0 83.55 0 140.00 0 2. 6 110 4 0.51 1 0.1965 4 -0.2915 8 0.4149 7 -0.2915 8 -2.627 0

10. 6 110 4 3.40 0 0.3207 5 O.5314 S 1.0253 1 0.53K 8 -2.013 5 19. 7 110 4 7.16 0 0.3634 5 0.8549 1 1.2944 7 0.8549 1 -1.740 7 21. 6 110 4 17.90 0 0.8287 0 1.2528 5 1.3344 5 1.2528 5 -1.699 9 103. 0 110 4 63.55 0 0.6169 9 1.8031 2 2.0128 4 1.8031 2 -0.987 6 100. 0 110 4 83.55 0 0.8355 0 1.9219 5 2.0000 0 1.9219 5 -1.001 7 129. 0 110 4 140.00 0 1.0852 7 2.1461 3 2.1105 9 2.1461 3 -0.878 4

11 0TABL E C-XII I OESORPTIO N EQUILIBRIU M DAT A FO RTH E 1-200 0 /l gnt" 1 RANG E O F INITIA L LITHIU M CONCENTRATIONS I N SOLUTIO N AT 38°C . CONCENTRATION S AR E BES T ESTIMATE S FRO M MEASURE

D LITHIUM AN

D OTHE R CATIONS ; SOLID-TO-LIOUI D RATI O = 1:20 .

CE C 0.2 3 1.1 0 1.3 9 5.4 8 8.6 6 14.5 0 35.80 34.7 0 104.0 0 0.26 4

2.00 0 7.95 0 2.00 0 52.10 0 19.30 0 210.80 0 234.72 0 415.00 0 .110 4

110 4 110 4 110 4 110 4 110 4 110 4 110 4 110 4 0.2 3

1.1 0 1.3 9 5.4 8 8.6 6 14.5 0 35.8 0 34.7 0 104.0 0 0.8712 1

0.5500 0 0.1748 4 2.7400 0 0.1662 2 0.7513 0 0.1698 3 0.147E 4 0.2506 0 -0.6382 7

0.0413 9 0.1430 1 0.7387 8 0.9375 2 1.1613 7 1.5538 8 1.5403 3 2.0170 3 -0.5784 0

0.3010 3 0.9003 7 0.3010 3 1.7168 4 1.2855 6 2.3238 7 2.3705 5 2.6180 5 -0.6382 7

0.0413 9 0.1430 1 0.7387 8 0.9375 2 1.1613 7 1.5538 8 1.5403 3 2.0170 3 -3.621 3

-2.741 2 -2.139 5 -2.741 2 -1.305 1 -1.749 8 -0.627 1 -0.568 6 -0.220 2

### Appendi xD

STATISTICAL AN

DIODE L PAIAKTE I ESTIMATE S FO l ISOTIEII S

11 3TABL E D- I

STATISTICAL AN D MODE L PARAMETE R ESTIMATE S O F TH E LINEA R ISOTHERM FO R TH E ADSORPTIONO F LITHIUM O NAPRO W PAS S SUSPENSIO NI NJ-1 3 WEL L WATE R FO R A NINITIA L CONCENTRATION RANG E O F 1 T O 200 0 jx

g I d Mi" 1 AN D ASOLIEHFO-LIQUI D RATI O O F 1:2 0

R 2 CV Slop e (K d ) L i Dat a

0.1 8 22 4 0.35±0 . 25° C

1 7 Bes t Esti

mat e Dat a

0.84 5 5 5 0.43±O.0 6 L i

Dat a

0.35 4 26 4 0.94+O.2 9 38° C Bes t Esti

mat e Dat a

0.90 5 4 5 0.425±0.04 6 L i

Dat a

0.40 7 18 8 0.45-t0.1 2 45° C

Bes t Esti

mat e Dat a

0.92 4 4 0 0.27+0.0 3
Equation : S = K. C Regression : Svs C Units : S = figL i g ~ soli d C - ngL i ml" 1 H 2 O K d= m L H 2 O g"* 1 soli dTABL E D-I I

STATISTICA L AN D MODE L PARAMETE R ESTIMATE S O F TH E IANQflJI R ISOTHER M FO R TH E ADSORPTIO N O F LITHIUM O NAPRO W PAS S SUSPENSIO NI NJ-1 3 WEL L WATE R FO R A NINITIA L LITHIUM CONCENTRATIO NRANG E O F 1 T O 200 0 ju g L i mL* 1 AN D ASOLID-TO-LIQUI D RATI O O F 1:2 0

R2 C V Slop e (1/b ) Intercep t (1/kb ) b k Equation : Regression : 25C

L i Dat a 0.000 4 24 0 -0.0000 9 ±0.00 1 1.23+0.8 0 l.lxio" 4 7.3X10*" 5
S -^ g C/ S V S C 

### > c Bes t Esti

mate Data 0.92 ? 2 2 0.00 1 ±0.000 1 0.50410.09 6 71 4 2.8X10" 3 38° C

L i Data 0.17 5 29 9 0.00 4 ±0.00 2 O.O13±1.3 3 2.5X10 2 3.1X10"* 1 Units : S = ng Bes t

Esti

mat e Data 0.88 8 2 5 0.001 4 ±0.000 2 0.60±0.1 2 71 4 2.3X10" 3 L i g" 1 soli d L i mL" 1 H

2 O L i Data 0.25 2 12 7 0.000 8 ±0.000 3 0.32*0.2 3 1.3X10 3 2.5X10" 3
b = k= 45° C Bes t

Esti

mat e Data 0.79 2 4 0 0.002 0 ±0.000 4 0.85±0.2 7 50 0 2.4X10" 3

pg JA g~ soli d

•• m L H 2 O jig*" 1 L iTABL E D-II I STATISTICA L AN D MODE L PARAMETE R ESTIMATE S O F TH E FREUNDLIC H ISOTHERM FO R TH E ADSORPTIO NO F LITHIUM O NAPRO W PAS S SUSPENSIO NI NJ-1 3 WEL L WATE R FO R A NINITIA L OONCENTRATIONRANG E O F 1 T O 200 0 pq L i mL" 1 AN D ASOLID-TO-LIQUI D RATI O O F 1:2 0

R 2 C V Slop e (N ) Intercep t (logK ) L i

Dat a
0.79 4 2 1 0.72± 0 0.651 0 25° C
Bes t

Estimat e
0.96 3 8. 3 .0 9 0.72±0.0 9 .1 9 0.61+0.1 1 L i

Dat a
0.73 6 2 4 0.67±0 . 0.71±0 . 38° C

1 0 2 1 Bes t Estimat e
0.97 9 5. 9 0.68±0.0 3 0.66±0.0 8 L i

Dat a
0.92 6 1 1 0.73± 0 0.71+ 0 45° C

.0 5 .1 1 Bes t Estimat e
0 . 9 . 0 . 0 ,95 2

. 3 ,65±0.0 5 .60±0.1 1 Equation : S = KC r Regression : lo g S v s lo g C Units : S - nq L i g" 1 soli d
N= dimensionles s K - (mL fig"" 1 Li) N(pg L i g" 1 solid )TABL E D-I V STATISTICA L AN D MODE L PARAMETE R ESTIMATE S O F TH E MODIFIE D FREUNDLIC H ISOTHER M FO R TH E ADSORPTIO NO F LITHIU M O NAPRO W PAS S SUSPENSIO NI NJ-1 3 WEL L WATE R FO R A N INITIA L CONCENTRATIO NRANG E O F 1 T O 200 0 fi g L i mL* 1 AN D ASOUD-TO-LIQUI D RATI O O F 1:2 0

R 2 C V Slop e (0 ) Intercep t (01o g K J

« D 25° .

L i Dat a

0.67 5 5 6 0.80t0.14 . -2.410.2 8 

### l.oxio" 3 r%

Bes t

Estimat e

0.97 3 1 7 0.8210.0 5 -2.50ttO.1 0 8.9xlO~ 4 38° C

L i Dat a

0.64 2 5 3 0.72+.0.1 5 -2.3+0.2 8 6.7X10" 4 Bes t

Estimat e

0.98 1 1 3 0.77+.0.0 4 -2.45±0.0 8 6.6xlO~ 4 45° C

L i Dat a

0.90 9 3 2 0.86±(L0 7 -2.4tO.1 4 1.2X10" 3 Bes t

Estimat e

0.95 8 1 5 0.70+0.0 5 -2.49+0.1 1 2.8X10" 4

Equation : S^,^ - S ) Regression : lo g - 1 " Units : S = jt

g I i g soli d

- S)~ x ] v s lo g C S ma x = u g soli d L i mL* 1 H 2 O C = 0 = dimensionles s

» m L H 2 O LiTABL E D- V

STATISTICAL AN

DMODE L PARAMETERESTIMATE S OF TH E LINEA R ISOTHER M FO RTH E ADSORPTION

OF LITHIU

M O N A PRO V PAS S SUSPENSION

I N J - 1 3 WEL L VATE RFORA

N INITIAL CONCENTRATION

RANG E O F 1 TO 15 0 /i

g raL" 1 AN DA SOLID-TO-LIQUI DRATI O OF 1:1 0

R 2 C V L i Dat a 0.66 4 9 2 25° C Bes t

Estimat e 0.96 8 2 6 L i

Dat a 0.97 0 2 6 38° C Bes t

Estimat e 0.93 3 3 6 L i

Dat a 0.92 5 4 1 45° C Bes t

Estimat e 0.95 7 3 1 Slop e 0.47±0.1 1 0.87±0.0 6 1.87*0.0 9 0.96±0.1 0 1.58*0.1 4 1.24*0.1 1

Equation : S = K. C Units : S = figL i g soli d Regression : S v s C C = /* g L i ml " H 2 0 K d= m L H 2 0 g' 1 soli d

11 8TABL E D-V I STATISTICA L AN D MODE L PARAMETE R ESTIMATE S O F TH E IANOKJI R ISOTHERM FO R TH E ADSORPTIO NO F LITHIUM O NAPRO W PAS S SUSPENSIO NI NJ-1 3 WEL L WATE R FO R A NINITIA L CONCENTRATION

RANG E O F 1 t o 15 0 ji g L i mL* 1 AN D ASOLID-TO-LIQUI D RATI O O F 1:1 0

R 2 C V Slop e L i

Dat a

0.77 3 5 0 0.0231 0 25° C

.00 4 Bes t Estimat e

0.84 3 2 0 0.00610.00 1 38° C

U Dat a

0.51 5 2 1 0.002010.000 7 Bes t

Estimat e

0.73 7 2 5 0.005810.001 6 45° C

L i Dat a

0.83 9 1 9 0.003010.000 4 Bes t

Estimat e

0.58 7 4 0 0.0047+0.001 7

Intercep t 0.44±0.2 3 0.4810.0 8 0.3710.0 4 (1/kb ) b k 43. 5 16 7

5.2x1 0 - 2 1.3x1 0 - 2 50 0 0.48+0.1 0

17 2 5.4X1 0 - 3 1.2X1 0 - 2 0.280+0.02 8 0.3510.1 2 33 3 21 3 1.1x1 0 - 2 1.3x1 0 - 2

kb C Equation : S - j^j g Regression : C/ S v s C Units : S • t>q L i g" 1 soli d b = ji g L i g soli d C - ju g L i mL" 1 H 2 O k = m L H 2 O pq~ l Li

-t o O TABLE D-VI I

STATISTICA L AN

D MODE L PARAMETE

RESTIMATE S O F THE FREUNDLIC H ISOTHER M FO RTH E ADSORPTIO N O F LITHIU M ON A PRO W PAS S SUSPENSIO N I N J-1 3 WEL L WATE RFO RA N INITIA L CONCENTRATIO

N RANG E O F 1 t o 15 0 pq L i UlL" 1 AN D A SOLID-TO-LIQCJI D RATI O O F 1:1 0

R 2 CV Slop e (N ) 25° C

L i Dat a

0.92 4 1 5 0.638±0.06 1 Bes t

Estimat e

0.98 7 6. 1 0.759±0.03 9 38° C

L i Dat a

0.98 1 6. 6 0.90010.03 8 Bes t

Estimat e

0.95 8 1 1 0.833+0.07 7 L i

Dat a

0.98 6 5. 9 0.807+ 0 45° C

.03 1 Bes t Estimat e

0.98 1 6. 5 0.722±0.04 5 Intercep t0.413±0.077 0.444+0.05 5 0.477±0.05 1 0.37±0.1 1 0.632±0.042 0.643±0.06 4 (K ) Equation : S = KC

r Regression : lo g S v s lo g C Units : S = /i g L i g ~ soli d C - fi g L i mL" 1 H 2 0 N = dimensionles s K- (m L /tg" 1 Li) NQig L i g" 1 solid )

# I i TABL E D-VII I

STATISTICA L AN D MODE L PARAMETE R ESTIMATE S O F TH E MODIFIE D FREUNDLIC H ISOTHER M FO R TH E ADSORPTIO NO F LITHIUM O NAPRO W PAS S SUSPENSIO NI NJ-1 3 WEL L WATE R FO R A N INITIA L OONCENTRATTO NRANG E O F 1 t o 15 0 (iq L i JtiL" 1 AN D ASOLID-TO-LIQUI D RATI O O F 1:1 0

L i Dat a 25° C
Bes t

Estimat e L i

Dat a 38° C
Bes t

Estimat e L i

Dat a 45° C
Bes t

Estimat e
R0.92 1 0.98 8 0.98 2 0.96 1 0.98 5 0.97 9 C V 8. 2 4. 8 6. 6 9. 2 6. 1 6. 9 Slop e 0.647±0.06 3 0.777+0.03 9 0.936±0.03 8 0.852*0.07 7 0.844*0.03 3 0.7481:0.04 9 Intercep t -2.63±0.07 9 2.60±0.0 6 -2.58±0.05 1 -2.67±0.1 1 -2.42±0.0 4 -2.41t0.0 7

8.6X1 0 .- 5 4.5x1 0 1.75x1 0 7.3X1 0 - 4 1.35xl O ~ 3 6.0X1 0 " 4 Equation : Regression : lo g = ) v s lo g C ~ Units : S = nq L i g

~ soli d

S ma x i g^soli d

H 2 O C = nq L i 0 = dimensionles s K p = m L F fig" 1 L iTh e followin g numbe ri s fo rOffic e o f Civilia n Radioactiv e Wast e Managemen t(OCRWM ) record s managemen tpurpose s onl y an d shoul d no tb e use d whe n orderin g thi s publication . Accessio n Numbe rNNA.890919.007 7

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