ENVIRONMENTAL EVALUATION GROUP

7007 WYOMING BOULEVARD, N.E.SUITE F-2

ALBUOUEROUE, NEW MEXICO 67109(505) 81003

I AffvLAnsE ACTION EMPLOY

Some Models of ColloidsGeneration and Transport

Y. Hwang Korea Atomic Energy Research Institute

P. L. Chambre, T. H. PigfordUniversity of California

W. W.-L. LeeEnvironmental Evaluation Group

Albuquerque, NM

May 3, 1993K)

Providing an independent technical analysis of the Waste Isoletion Pilot Plant (WIPPI.a lederal transuranic nuclear waste repositoly.

,K>.

Definitions

Radiocolloid. Colloids of radioactive species. Probablyfonned from hydrolysis of actinides.

Natural colloids. Non-radioactive colloidal particlesin natural waters.

V>

Solute. Radioactive species in soluton.

Pseudocolloids. Natural colloids which have sorbedradioactive solute.

K>

.1.1 ... \ .

K)

in porous rock radiocolloid transport

advectiondiffusion

In fractured rockradiocolloid transport

If collolds behave like particles,previously published solutionsapplynew solutions if colloidsInteract with solute

pseudocollold transport >

solutions for

--. pseudocolloid soluteadvection Vdiffusion V Vsorption on

fr. walls V Vfr. solids a

matrix duff. Vdecay - V Vfiltration V

'K>

1. Fluid flowThe continuity equation for steady, incompressible flow aroundan infinite cylinder

V V-(fo)O, (1)where If is the radial coordinate [LI,6 is the angular coordinate [LI, andv(r, 0) is the vector of pore velocity symmetric over 0 = r.

The velocity vector can be decomposed into the radial and an-gular components

V=_U".co ( I- ) e, + O0sin 1 0 a) eA~~A>1

_ aO < 0 < X (2)

2. Colloid concentrationThe steady-state governing equation for colloid concentration inporous media is

v J( 0) + S(r, 9) = O. (3)

whereer + Va0 (4)V =era kife

and J(r, 0) is the colloidal mass flux MIL2-t],a is the waste cylinder radius [LI,Df is the diffusion coefficient of colloid in liquid l2 t],Or is the unit vector in the r' direction,es is the unit vector in the 0 direction, andS(r 0) is the colloid filtration rate per unit volume of liquid perunit time ML 3-tl.

The colloidal mass flux per unit area per unit time is defined as

J(f,8) (Fs)C(r ) -DfAa de

(5)

We need to evaluate the filtration rate term S(r, 0) in cylindricalgeometry.

A ~A ( 2 t S( , ) = AU.,C(r, )/[cos0 1 (-2 + [sin (1+ 2)]

(6)where A is a filtration coefficient for colloids, [1/Li, to be deter-mined.

We solve numerically for the radiocolloid flux from the waste.

I ..

2'10

110

-q

* Experimental dataBi-modal analysist=40 days

.

.0

4.3

Q

U

I'U-

10

.

w-1 0

.. S

I-- .

-2 -I.10 0 5 10 15 20

Figure IDistance from source, cm

. Normalized Neptunium Concentrations from theExperiment and Our Prediction Based on BimodalDistribution of Filtration Coefficient as a Functionof Distance Away from Inlet

K21

10

104

A=20 m1

\10&'103 ml\

0.06 0.1 0.,IB d02 0.25 0.3 0.35 0.4 1Distance from Waste Surface, m

Notmaeizd rocotfold Fluxes as a Function ofDsance for Differmnt PotO VGIocIUGes

T2b

Ir jr

mEMINENNIdlsolul>4

I\ - ' I

We consider one-dimensional advective-diffusive transport within the fracture, and assume that the colloidsare too large to diffuse into the rock matrix. Neglecting the possible colloid filtration within a fracture, thegoverning equation of pseudocolloid migration in'the fracture is

tI + ) +EC6VI ( + SS(, Ot) + -S2 (t)j-lD + elelAcl 0,

,>09,t>0

where is the ratio of liquid volume to total volume in the fracturecI(ac, t) is the amount of species sorbed on the colloid per unit volume of solid colloid MIL?v, Is the colloid pore velocity [tl,DI is the colloid dispersion coefficient [ltj,A Is the decay constant [/ti,el is the porosity within the fracture [-I,

I Is the constant volume fraction of colloids In fracture liquid [-1,cS1 ( as, t) Is the rate of sorption to stationary solid [M/L - tJand E1S(a&, t) is the rate of desorption' from the pseudocollold [M/L 3 - .

For the same species as solute In liquid In the fracture

OC2 (a., U ) Ocz(a0, t) O 2C(AWt q9 O) ______ ___v2 _ - ES 2(z,t)+ cS3(j t)-E 2 cj +EAC1*b+ b -Oa > 0t >

wherec(, U) is the solute concentration in the fracture liquid [M/L3J, V2 Is the solute pore velocity M/t,

S 3(a USI) is the rate of solute sorption on stationary fracture solids [MIL 3 -tib is the fracture half-width IL],

I K-i K).

and q(az, t) is the diffusive solute flux into the rock matrix [MIL2-tj, given by

q(r~ ) cpp B y |9 b S

where p Is the rock porosity 1Dp Is the solute diffusion coefficient In water in porous rock [L/tI,and N(m, y, t) Is the solute concentration in pore water in the rock matrix [ML 3 1.

For solute species sorbed on stationary fracture solids

(l- OC3(a t _ EISj(, t) + (1 - )AC 3 (z, t) = 0, z > 0, t > 0

where c3(ao, t) is the concentration of sorbed solute species [MAL3 1.

For pseudocolloids on the stationary fracture solids

(1 - Oc)g2a, ' t) _ tS&( 9 t) + (I - C 1)42>cC(& ,t) = 0, ar > 0,t > 0

where &2 is the constant volume fraction of the sorbed colloid per unit volume of the stationary fracturesolid [.1.

Inside the rock matrix

4p of -)Dp a (' + 14AN(mg t) = 0 m > 0 t > 0 > 0where Rp is the solute retardation coefficient in the rock matrix [-1

Linear sorption equilibrium between the solute species In the fracture liquid and the same species sorbedon the colloid is assumed. Both the solute species and the colloids In the fracture liquid are assumed to

undergo the linear sorption equilibrium with the fracture solids

ClW t)

CA2W, t)

Adding the above equations, an equation for cl is obtained In terms of an effective retardation factor R,an effective dispersion coefficient D, and the retarded velocity v.

Ract(c t)at

v OCl(, t)oxu :

D 8 2C( ) + RAcl(r, t) +D . e(b = 9 > .t > (*)

where

R= (1+

*v=vl +

D=D (I

Kd)]

KdVI)Kd,u)

D2

.DlKd,)

e ] Kd2 Kd3! '

Then the apparent migration front velocity of solute is

V =-=R Iei (I+ 1 iKd)I + +- -ŽKd2] Kd

wheredV

dKd3

(RIR-2) 3

R.R"A(

I ( ' I )d + (1+ 1 Kd) Id]I

Solving eq.(*) with the following Initial and boundary conditions

N(a, oo, t) =O

.N(mq kg t) = IC~g0Kd 3

N(q, y,0) = 0,

.c 1(0,t) = Kdco,

c 1(oo, t 0,

Cg(A, ) = 0

W > O t >

> t > 0

t > 0

t > 0

W >0

where co Is the Inlet solute concentration, we get the solution for the pseudocollold concentration.

=2Kd3 C , exp IfI erfc [f2] exp [f3] dqir 2 7V-

a > 0,t > 0

where

f =1V 4 RAD -v

2D

K>

f2=A2,p VDAKd3

8Dbeli 2 -

f3 = - 114D)

With FILTRATION, the first equation becomes

8a1(art)+ (IiVI8 + EJS1(aI, t) + -S2 (a, t)c-tlDl awl + C161Aci + eitiliAc, = 0,

> t > where A is a filtration coefficient of radioactive solute sorbed on natural colloids Inside theThe solution for cl remains the same except for

41T

fracture, Il/LI.

=2Kd3 co exp {f } erfc [f2] exp [f3] dq t >

where

fl.V2 + 4R*D - V

2Dand

* = 1 d_ + lA)] + 'Kd]del

A

Kd,

10

U._

-2

_0-100*'K 10*

K m1oS* K" -10'l Pseudo-colloid

DD v0. mrIax 10 2F3

-10'

RDpin10" a/vinlmWev inO.6 rn/a

16-4 WM,00 1 .2 3 4

Distance, m

) )

6 6 7

- I-:. ,., C^110

id1C10°

10

-1

1-2

0 , ,

%

Where do we go from here?

We have developed some analytic means for predicting colloid generationand migration rates.

In so doing we have identified some parameters that need to be measuredin laboratory and field studies:

filtration coefficientssorption coefficientsdiffusion coefficients

T

Do we know what these values are? Can they be measured? Can webound the colloid problem if we have some idea of these values?

Is this an approach to performance assessment?

Is colloids a problem in radioactive waste disposal?

'v

n Isu

Natural Macromolecular Polyelectrolytes(HumicsFulvics)

A. Strong Complexors:e.g., * I ppm; UOgHu : U =5(

B. Colloid Formers:as colloids themselves or as coatiinsurfaces on mineral colloids

C. Strong Reductants:quinone type structures have E ca.PuO2+ = Pu(OH)4

D. Photolyze:produce peroxide in surface watersincreases reduction strength

D0-5000

gs on

0.7v

;,

K)~

MIa

Ali

Go

Br4

Bro

Br4

Br,

letalIA

Irich

Iy . 4

ad. |

ad.

ad.

ad.

assume

basedsolutior

- Humate StipH _1

6.0 6.27-0.04

6.0 .6.68-0.47

6.0 6.1 6-0.38

6.0 6.53-0.30.

4.5 8.2- 1.0

4.65 7.0-0.3

es Am binds to 3on free Coe gr

in

kbility ConstantsMethod Analysis

LPAS a

UV Spec a

UV Spec a

Ultraf ilt a

Sol Extr b

Spec b

-Co2 a

oups per L. ofa:

b:

K11I

K)

Separation

a) J-13 well water acidified to pH 2 (w. HCI),

b) Passed through columns of XAD-8macroporous resin at 3 - 6 gal/hr.,

c) Humics stripped with 0.1 M NaOH.

d) Eluant adjusted to pHa2 and passedthrough XAD-8, then stripped with 0.1 MNaOH, repeated twice more.

K)

K>1.

Separation (continued)

e) Almost 3000 gal. reduced 2.5 1 after 3columns.

f) Freezed dried, then purified by severalcycles of dissolution In base, precipitationIn acid with ultrafiltration.

g) Overall yield of 60 mg HA, 15 mg FA.

UV-VIS Absorbance

a) Humics characterized by ratio ofabsorbances at 465 and 665 nm(E 4/E 6 ratio.)

V)

b) E 4 /E 6: 4 - 8 for humics.

c) E 4 /E 6 : 4.1 for HA and 4.4 for FA fromJ-13.

0--.

K.)

Infrared Spectra

a) Spectra of HA and FA from J-13 similar tothose of aquatic and lake sediments.

K>b) The spectraspectra from

differ noticeable fromsoil samples.

HA

I.-

Other Properties

a) -13 nmr - typical of low mole. wt. aquaticFA and HA.

b) pH ttration - 2.7 meq/g -CO 2H)/g FA- 4.6 meq/g (-CO2H)/g FA

pKa(a=0.5) = 4.6 FA= 5.6 HA

Properties are all typical of-aquatic humics.

13

12

11

10

9

8

I-

I I I I I I I I I

S.

5

4

a)3.>

U)

2 D)-)

1

'0O

7

6

5

4

3

2

5-.

.

I I I I 1 I I l Ii

0 1 2 3 4 5 6 7 8meq OHm/g HA

Titration and first derivative curves for J-13water humic acid.

C

C ; .

300 200 100 0

Chemical shift in ppm (6)

The CP/MAS C-13 NMR spectrum of the J-13 waterhumic acid.

K>

(I (b)Humic acid from coastalsediment in Bahama

I I _ . I ~ ~ ~~~~~~~~I I

diUCaCa

Cx

200 150 100 50 0(ppm)

K�)

Binding Studies

a) Used solvent extraction method:

0.1 M (NaCIO4) + HDEHP In toluene

b) D vs [-CO21 requires two parameters, p'1and 2.

log P1 = (7.57±1.43)a + (4.47±0.49)log P 2 = (2.68±0.54)a + (10.70±0.18)

K>1

Calculated Speclatlon

No Ca*2

Ra6.98.2

Am9.5e-51.1e-4

AmHu1.01.0

AmCo3le-43e-4

Am(C0312neg6e-5

Am(OH)2e-54e-5

K1,)C e f.Corrected for Ca+

6.98.2

0.030.02

0.93. 0.41

0.04o.43

neg0 D.09

0.0050.05

)

K>

COnlusions

Am(lIl) - HA could affect significantly.

U02+2 - HA probably would not affect unlessTOC > 0.2 ppm.

Pu02 Pu0 2+ 2 - would be reduced to Pu(IV) byHA.

Particulate Material in Well J-13 WaterJ FII ti . Kerrisk and A.., .'I Ogard

Objective* Assess the potential for significant

transport on particulates in flowingradionuclidegroundwater

* Why Well J-13 water?* Establishedljyvell (1963)

* Routinely pumped* Close to Yucca Mountain

* Topopah

* ReferencESpring Member

3: LA-10929-MS

_~~~~~~~~~

Los Alamos

_K

-

F 0

m -m

'46

t

dV8l..- . -*-

GIN

i��z

(a~~~~~~~~~~~

Ia

K ) )

Sample Collection

WellJ-13 -Prefilter' 1ORLm Hollow

FiberFilter5 nm

Membrane 53001 of waterFilter

0.4 urm93001 of water

-� K

Los Alamos

2 .

Sample Analysis

* Membrane Filters (> 0.4 gim)* Water wash, centrifuge, alcohol wash, dry* Weigh

* 0.25 g solid from 9300 1 of water* 2.7 x 1 05 g solid/I water

* Elemental. analysis* Hollow Fiber (0.4 m - 5 nm)

* Backflush* 0.0025 g solid from 5300 1 of water* Elemental analysis

Los Alamos_//-- --- -And K-

Catio>n. Co mpositionParticulate Sample. i .:+ 1. l nbrae fotr Hollow Fiber Filter

0.4 (0.4 jim 5 nm)60% Is

5°_ __1 U

. ' ] ,i, i,\

of

. AIf

4 , I I ~ ~ .j!

S

SI

FeNa

.% I

,. 41�..

i

* i

.1 I

.

; iV

i.

'i.

- ,.

.. I .

.

' . ,...

. I4; ;4 . ,

i ; :

.i . .

* t. ,-

wp 3.

UAl,

.j

1 ) .K .. >.Los Alamos

K )

3i

h cIulates in J-13nuclide Transport;.

, *. O. ,

,, I .

.*ix Is tlc Cis t

the sorptiia i iculaes in J-1 3 water (mlhe 6oncettibn o particulates in J-13 water (g/l)he dissolved radidnufl6dp species concentration irr (moles/)2 ,;R+> s ;$:i;.i fits an,+; ;uateInhv moles Srbebed on"articulates/

1=R 1.00

fg)

i J-13

water

-i

species sorbed on6lid¢; 1Ospecies!I ..* llbI , 1-

II

4

..;i,

I _ _ . _ . . .~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

i

\1

Los Alamos

Kj

mhtcpaq D&%f inetae in .12 Wutaron Radignuclide Transport

. . .. - .} > ~~~~~~~z10=0.01

a?.L; .h*;-*, ........................-...-._

4n7~~~~~~~~~~~~~~~~~~~~~~~~~~~~~:; ' 1 ............... ..E

- - -- ----- |--

r*.

I~~~~IO

d . . 1 ' 1w - x I *t . X . .. , ....,,,, ,

4 ,-6 : jj{1 - ;, -1 - 0

r. O . ... 4 i , I * . . I

- -' ., - t

�vI

K>

c+us 11 WQ uestions

* If particulates in, Well -1 3 water ard representativeof groundwater underthe repository and the

sorption ratipf- part 1,tes is not significantly large-e thai) re6po Qat4i M dlirlonuclide transport byparticulat ignificant problem

;i W J nve of. groundwaterunder h'SerptIn rtPif

What i th otoni ato of the particulate material

)k r

I?54..

. Los Alamos-

I/ ~Kj

g a

U II U U a

U lea

U U U i'u a a

.Intel �446ck 'bZlI l

I i=a9

~~~~~~ e

* a a a

l~~~ V V VU

- ~~~~

f

* e 0- a g -e~~~~~~~~~~~~~~

C - - - C - 9* 0 -

K> K), el

I~~~~~ 1_

~~~~~~~~~- s a

K> K)- I

I _~~~0

*l - - -.6*S

-| S 6 .6 .

-S S S S m S

U . U O~~K -7

-~~~~ A A

**

~~~~~ -- - S-- U -S -

KU K)~~~~~�I-j

0 0

A S

SU -

S. --

m S.

e Se - S 0 S

K)lb

K)j

;-~~~~~~ AA~

l~~ ~~ . -.- *

At

~~- - ee S

-~~ - S

Any, )d

K) vle

K-> K)j

. I

l~~~ *@ S. - 5- 0

-~~ 55 - SS-U-

S.- 5|S S

K>f

Characterization of inorganic colloids from someNTS well waters

t B.E. VianiS.1. Martin

Lawrence Livermore National Laboratory

M. ten BrinkUSGS

* . Ta?

l

K>

Characterization

* Samples collected* t A

f( in pumped wells,. q.

Ov , i -iMasse ind by filrati

* Mass determined by filtration

* Phases d :ifed bk$lEO and XRD

* Individual phase compositions measured by EDXS

K-' K)

NTS groundwater colloids I

* -1 mg/L

* Inorganip

If . nit. f t- 4;

* Fe & Si dxides, layer slicates, exotics, some that go poof

* Mineralogy related to sampling well

I

I>K

Colloid concentrations in some NTS waters

Particles captured b+1.015 tim membrane filters

Well t Particles TDS

4,mg/L mg/L

J-1 3 2a 1.4 281UE-9c. 3.1 151

UE-20n-1 5.1 255

5c 1.1 381

K> K>

Preparation of samples for TEM analysis

I II.

. .I.,I I

. I

.,I

r14

'5.

-.!

I¢''

I

I I

I .

00

sample

filter paper

holey-carbon-coatedcopper grid

K)

Well Jm13 -Mica LU!

I fr.0, , ).

,.s

I , . .I L

.0 ... AV IIf

X .

1.0 pm . T

K> K)

Well J=13-Hematite

1.0 pm

i T

IlCountsto

C

IC

IC

SC

Sc

3C

2(

'I

O

ho

mo

0o

00

0

I a

I

I

lu

101

oeCu he Ca

1 6

lb S2 14 Is is 20k*V

Well J-13 -Illite|

41~~~~~~~~~~~~~~~~~~~~~~~~~~~~~o

Counts

90

so

?0

to

so

Fe

So .K~~~~~~~~~~~~~~~~s~e

K> v)

Well 19c-Cdstobaite

1.0 Pm

4 .

t '. ,

Counts

t0

120

0

60

I Cu

kaw44-a S a

KU1-

Well 19c-Amorphous silica

1.0 pim

too ~~~~~Cu

1 *120

. 0 6

soCu Cu

sokCr

K-> K)

Well 5c -Hematite

iI

0.5 Plm. ?

480

420

360

300

240

ISO

120

50

0*

a4,

t. .

0

Fs

F a

4

Cu__L -at" 12 14 1 1 d

K>.,; a a t2 t4 1 a A

A cMW~UwIe 20 A WA .1 "i 3)0. tIe Kt. 12_ A___ _

Topopah Springs tuff fracture flow experiment -0.05 rn/day -Hematite

lohm

I

1.0PMCount

:8o

.120

360

300

240

120

4 .

:3 ¶~~~~~~~~~~~~~~

a

Fe

K> Go0JICr.F*Cu tISM ~ WL~C

-- - -- - -- - - - k*lV

Topopah Springs tuff fracture flow experiment -0.05 m/day -Quartz

.W

I

1.0 amCounti T

10

ISO

120

60

so

a St

I

Cu

U

I

6%b-%ft#ov4LAK> k*V K)I I i 4 \-A 6 i a i 10

Conclusions

* Most of the Inorganic phases identified are consistent withminerals in formation.

* Contamination inferred from presence of exotic phases orcompositions.

* Different wells display differences in mineralogy.- Well J-13: Iron oxides, layer silicates, and Ca-phase

. .

- Well 5c: Iron oxides and layer silicates- Well 19c: Silicon oxides

* Particles that are damaged by the electron beam, and those thatare not captured by the holey-carbon-flim are not sampled.

* Inorganic colloids in "clean" groundwaters and those generatedin core-flow experiments are readily detected and identifiedusing this method.

Direct Quantification of Organic Material

in NTS Well Waters

a .

Cynthia E. A. PalmerRobert J. SilvaHoward L. Hall

Gregory L. KlunderRichard E. RussoDavid A. Wruck

L -�� ........ K. K�11� .

Total organic carbon in NTS well water

NTS Well

4

8

16D

20W

Cane Springs

A

0.229

0.247

0.227

0.254

0.551

Sample Preservation Method

B C D

0.113 0.00951 -0.0626

0.507 -0.0587

0.135 0.00914 -0.0386

0.153 -0.0213 -0.0776

0.416 0.254 0.233

E

0.0203

-0.0154

0.0157

0.0262

0.268

. .

I .,

Methods A:

B:c:

D:

E.

H 3 P04 , light, ambient temperature, plastic bottle

H 2SO4 , dark, cold room, plastic bottle

H 2SO4 , dark, cold room, glass bottle (EPA protocol)

H 2SO4 , light, ambient temperature, glass bottle

Na03 , H2SO4 , dark, cold room, glass bottle (Whitbeckprotocol)

N-es: Aldrich Humic Acid (Na salt) 44 78% C by weightw~~~~~~~~~~~~~~~~_ - - K)j

Technical Issues

* Appropriate "zero'

* High concentration of Inorganic carbon measured beforelow organic carbon concentration

- adjust pH to 3- bubble Ar through sample - 30 minutes- three determinations of [TOC]

, T

*Standard Additions I .

K)

Analyses of H 2 0 Background ILUDetector Response

(mV)

MiIII-Q H 20 B. 281

Milli-Q H 20 B. 222

MiIIIQ H 20 B. 151

HPLC H 2 0 ,

lowest NTS groundwater

32.391

52.054

51.398

20.484

13.389

K> K)

Charge Transfer Fluorescence Determination

Groundwater< 0.20 ppm TOC

100 ppm Eu+3

Complex _1o Eu-organicFormation

Laser Excitation

of organic ligandwith 354 nm light

Eu-organic*

Eu-organic Charge WTransfer

Eu-organic*Fluorescence

Eu-organic

T

K)

Effects of varying concentration of Humic Acid

[Eu+3 ] = 100 ppm pH = 5.24

450

400

3504-

' 300

0u 250C

0(nL 2000

150

100

500 100 200 300 400 500 600 700 800 900 1000

HA Concentration (ppb)

K>-- KJ

Effect of varying pH

[Eu*3] = 100 ppm [HA] = 300 ppb

200 1.8

180

160

E 140E_ 1200

4T 100-y

80a-

cC

'4

E

(a

a)

to0

aly

a0

60

40

20

pH

--- 49 2 nm -- 613 nm & 492nm/613nm

< -I

Technical Issues

* Precipitation formed in well water samples

* Photodegradation of material In well water samples

* * Eu fluorescence observed

* Tunable excitation

* Less powerful excitation source

K> KYV

Swedish EffortAbsorb

DEAE - cellulose

Desorb0.3 It-- mNaOH

IAcidify

II

SolubleAsorbXA-

Desorb0.1 we agoNaOH

ion exchange

Lyophilize

Fulvic Acid

.1

I .

IInsoluble

sorXAD-8

Desorb0.1 eI

NaOHt

Ion exchanget

Lyophilize

Humic AcidK-I

Technical Issues U:* No acidification of well water required

* Unsuccessful at rinsing DEAE free of organic materialbefore loading well water

* Laser light scattering

* Flow cytometryT

.

RADIONUCLIDE MIGRATION AT THE NEVADA TEST SITE

JAMES R. HUNT

DEPARTMENT OF CIVIL ENGINEERINGUNIVERSITY OF CALIFORNIA AT BERKELEY

SUPPORT:HYDROLOGY AND RADIONUCUDE MIGRATION PROGRAM

LAWRENCE LIVERMORE NATIONAL LABORATORY

. s

K)

NEVADA TEST SITE

J3cn (P52 P55)

*CambAcus.(RNM-1, WUM23)

\'s IWeOs r + c

0 5 1OiA0 5 . , IO 5 10 15 m

9LtL

CAMBRIC SITE CROSS SECTION

Depth(n)

CambricUse RNM-A Surface 3132 ft

(6/15/85) (620/74) 0-II1IIII 1O0-

I AlluviumI EstimatedI chimney

I'

CAMBRIC8000-

J 6000 DITCH

O DEEPCL ~~~~~~~~~LYSIMETER

4000X

2000- ow

0'75 80 85 90

YEAR

,L. . N

PWV41.6" 0.4 2 -a r"tQ

jqT3CJ qr�� *+WT )

Y�'. V . Tn &. A -�, - ) Qgt. IC14 a. )LiCL-377¶-w % iLPLNL

0

200

400

E 600

Ca800

1000

1200

1400

Figure 2.L Vertical section of the Cheshire study area, showing schematically the relationship be-twen the UEZkn-1 satlite wel and the cavity and formation samplin points in the U2anPS hole.The hypothesized direction of groundwater movement is upward from the cavity through the chimneyto the upper permeable zone, and thn lateraly to the formation and saellte sampling points

6

PARTICLE CONCENTRATIONS BY SEQUENTIAL ULTRAFILTRATION

LOCATION

CAVITY

SIZE RANGE

200-6 nm50-3

CONCENTRATION

55 mg/L10

FORMATION 50-3 4

. Y

I ,.WL4 Lt"t)

KJ

TRANSPORT OF RADIONUCLIDES FROM THE CAVITY

HALF LIFE FORMATION FRACTION SATELLITERADIONUCLIDE IY TO CAVITY DISSOLVED TO CAVITY

RATIO IN CAVITY RATIO

3H 12.26 0.86 1.0 1.1522Na 2.6 0.126 0.93

oCo 6.27 0.034 0.021

'°Ru 1.02 0.25 0.1412Sb 2.76 0.54 0.97 0.22

_"Cs_ . 2.065 0.072 0.684 I-

' 87Cs 30.17 . 0.17 0.65 0.001Ual.". US6Eu 4.7-13.4 0.026

CHESHIRE RADIONUCUDES

WA6C '..

o 0.1 0.2 0.3 OA 05 0 0.7 0.8 0X 1.0Fraction dissolved, cavity

\K)

Prokllhs oS Ck.ask\e Do-to. Set

1, mrpd la"Ies

z. Stor'cl4 bowles4. (Jr at lcrd w 5cnrel

14. UTviam 4ior ve

-S, 4I\ CASIH19

9.-.

PARTIALLY CLOGGED FRACTURE

4

zaiD -- - ~ ~ ~ ~ ~ IPo +x

-

IX-0

tDat >)'I4

)Ž

K>f

PARTICLES MOVE FASTER THAN WATERIF EXCLUDED FROM POROUS REGION

APERTURE - 0.1 cm

POROSITY = 0.95

CONSTANT PRESSURE GRADIENT

PERMEABILITY, k cm2)

0-

-J

so

tll

:

X

10

la

10

2.5-

10

1.5~

10

0.5

k-10 1

k-I 8

I

0.2 0. 4 0.6 0.8 10NORMALIZED POROUS REGION THICKNESS

4 .4, " Nkj. (CA- , 4u JiA4)

TAYLOR DISPERSION IN FRACTURE

OVERALL LONGITUDINAL DISPERSION

+ 2 b 2DL = Db 210

Db = BROWNIAN OR MOLECULAR DIFFUSIVITY

= 1 0-5 cm2/s FOR SOLUTE

= 4x1 O9 cm2Is FOis 1 pum PARTICLE

!~ ~ 'K)

BREAKTHROUGH CURVES FOR U = 1 m/dAND 1 m DOWNSTREAM

1.0

0.8

0

a

J:

US

S

c

0

0,.I:

0.6

0.4

0.2

0.0 L.0.7 0.8 0.9 1.0 1.1 1.2

Time [day]

1.3

V 0,,,A ��

9

SCHEMATIC OF PARALLEL PLATE FLOW SYSTEM

from daystock tank

direction

of fow

o constant flow6tcnt~kreturn u toIstock takstock tank

pressure A " ")transducer

PARALLEL PLATES - Top View

K> K)�11�

EXPERIMENTAL PARAMETERS

* Parallel plate dimensions:- aperture, b = 0.026 cm- width, WTOT = 10.2 cm

- length, L = 25.4 cm

* Approach velocity of 184 m/day (flow rate = 3.38 mUmIn)* Montmorillonite, Initial concentration = 500 mgIL* O.IM NaCI, 0.IM CaCI2, lg/L NaN3* Experiment duration of approximately 820 hours

RUN 7 NORMALIZED HEAD VERSUS TIME DATA

12

10

8e

I eX

- - / -

.S -

S ~ S~

I I f * - _

6

4

)

2

n- - - - - - - - - - - - - - - --

0 100 200 300 400 500 600 700 800

Time [r]

900

3?

10

a

E . | RUN 7 DATA

6- 6 |estimated

circles: measured(average of three)

0C 40 ~~VJAJ~

2

0 100 200 300 400 500 600 700 800

Time [hr]

FOR A PARTIALLY CLOGGED FRACTURE

PARTICLE VELOCITY > SOLUTE VELOCITY

PARTICLE DISPERSION > SOLUTE DISPERSION

V. PARTICLES ARRIVE SOONER THAN SOLUTES

EXPERIMENTALLY, WHEN SOLIDS OCCUPY 1 % OF FRACTUREVOLUME, HEAD LOSS INCREASES BY A FACTOR OF 10

EXPECT COMPLETE CLOGGING IF HEAD LOSS IS CONSTANT4?,

1

Ue )

Bu444JAA + 4U-. Too i AdA _AAJ : t 4 ' go

Tf"+ sews. %ce.% 9 3, £s-s .8.

ramp Dow -S,

Tha"t

clI Z)ja"4

Alu" 4.1i

F'l'o%±'t " ThIWA4- 6* C i¶9) -4 t 4uwu~c&iJAL4%5 XJap "4a Co o .~Ž.4 4Ao~*

" -read , I

ag Wfiur .

- . i Aj.AAJ4.f

i f-Axj

tw""tN

CA.,� Xi - PhD A, U. C.

ot v& 'ru* STh , j>op/3v- , tC- 70S.

1)

Lu~ II "ICrlo s cwut-2

FULSCO

7)IF Flow Is 044) T

(be_ l~ ts ftjo noU.

jr4 roA 5k~

t o

c..o1Igi4 UW II c6eo;t 0-ta-t~ cJ.3 4fciluAe&.

3

Utasum. 7pg

*'

T*mWseoar

4 T s

I"j'

I

I

f

I

rgI

?

I

!I

0

e

0

f

*9991

"I*% %O.

Ad "satT LoaSE.

1)m

Cqotuwrn Sr'SaILTAtu"Se-sm-.

a.

b

.

I',

Co

co

el

I . .

pi

P.

)

r~

Iola A.t vs

v.A, cde

-. ..

1.0?ar 'ells�

9-

_~. _o

Characteristics and Mobilityof Actinides in an

Aquifer in a Semi-arid Region

by

W. L. PolzerE. H. Essington

Environmental Science GroupLos Alamos National Laboratory

Based on'Cooperative Studywith

Argonne National Laboratory

W. R. Penrose, D. M. Nelson,and K. A. Orlandini

Liquid Waste Treatment Processat LANL

. Addition of iron sulfate and lime

* Precipitation of iron hydroxide and calciumcarbonate

)'

9

Treated Waste EffluentDischarge Area

• Shallow alluvium aquifer in Mortandad Canyon

• Storage capacity of aquifer(20-30) x 103 m 3

• Annual storm runoff(25-125) x 103 m 3

* Annual effluent discharge-40 x 103 m 3

* Water movement-90% subsurface

10o 1

z 10°

C t^ 24 Am (MBq)

101l * Total Pu (MBq)

0 Volume (k.m3)

102~

1980 1981 1982 1983 1984

Year

Monitoring Access WellsMortandad Canyon Shallow Aquifer

Lm,. Water Table

I

MCO-5.Alluvium

MCO-75SCAM.

K> K>V

Actinide Characteristics

* Concentration

* Distribution ratio

. Oxidation state (Pu)

* Ion-exchange properties

* Size fractionation

* Chemical reactivity

Rate of movement

9

Surface Sampling Station and Monitoring Wellsin Mortandad Canyon (March 1983)*

Parameter Surface MCO-4 MCO-5 MCO-6 MCO-7.5

Distance 1900 1807 2235 2660 3390fromoutfall, m

Depth of 5.2 7.3 12.5 18.6well, m

Depth to *' 1.2 -4.3 9.1 13.1water, m

Pump 4.4 6.6 11.9 18.0depth, m

Sampling 4.1 2.8 3.8 1.9rate,Umin

*Distances are measured along the stream bed.

K> K>

10°

Cr

0-W

-I

C:

00

l-1

102

*............ l.... .. .. * . ..... ***** ..******. -.

24 1Am

. i

103- 2 3 9 , 24 0 pU

rvlay 198241A4I

1800 2200 2600 3000 3400

Distance from Outfall (m)

Characteristics of Aquifer Water

pHEh02Oxidation stateDOC

6.4 10.1>200 mV>0.3 gg/mL>90% Pu[lIlIV]

106

i52 3 9, 24 0 PU

-J

-

C:

041o

id .

10

id

Lee..c *I ........ e.....

24 1 AmMay 19811�-

1800 2200 2600 3000 3400

Distance from Outfall (m)

K -\ , K�Ij-

Low Molecular Weight OrganicsMortandad Canyon Aquifer

Concentration (ppb)

WaterPyridenes(pyridene)

Natr'I prod(quaiacol)

Phenols(phenol)

Organ acids(isobutyric)

Alkyl benz(o-xylene)

MCO-4 2.4 24 23 140 13

Surface

MCO-5

MCO-6

MCO-7.5

* 1.3T! ,

3.7

2.3

3.1

14

20

19

16

8.4

28

32

38

90

160

110

94

9.4

17

140

12

K> K)

10

i1

104

z

00 0 0

0 00

0U

U0

0 U0 0

0 a 0 . 0

.

t. , a 0.

r

o MCO-5* MCO-75o mcO-6

1i. . . . . . . . I , . . . ..... a I a I . a a a I. a

-1 IdCOLLOIDAL

icdDOC (ppm)

i1'I

V)

Distribution of Charged SpeciesMortandad Canyon Aquifer

Percent23 99 4 0pu 2 4 1 Am

Water Anionic Neutral Anionic Neutral

Wasteoutfall

MCO-4

Surface

MCO-5

MCO-6

MCO-7.5

7

T2

3

3

4

94

99

93

96

91

11 78

3 98

3 97

17

46

31

84

s63

8 94 93

Distribution of Anionic PuMortandad Canyon Aquifer

Percent

Water 239Pu (ambient) 23Pu (tracer)

Background -- 20Waste outfall .7 13

MCO-4 2 29Surface 3 --MCO-5 3 24MCO-6 4 -, -

MCO-7.5 8 56

Distribution of Anionic 2'AmMortandad Canyon Aquifer

Percent

Water Ambient- Tracer

Background - 26Waste outfall 11 6

MCO-4 3 17Surface 3 20MCO-5 17 18MCO-6 46 18

MCO-7.5 31 37

Actinides in Colloidal - Size FactionsMortandad Canyon MCO-5 Water

Percent

*Size Pu Amfraction Ambient Tacer Ambient Tracer

0.025,um-0.45,am

lOOK MW-0.025,m

1OK MW-lOOK MW

Actinides in

Actinides in >10K MWSize FactionsMortandad Canyon MCO-5 Water

Percent

Sizefraction

Pu AmAmbient Thacer Ambient Thacer

0.025,um-.0.45gm

lOOK MW-0.025,Am

1OK MW-lOOK MW

.94... I

34

0.5 2

70

2

28

56

6

385.5 64

K> K>

238pu to 239240Pu Ratios inMortandad Canyon Samples, - 1982 and 1983

Distance from Outfall (m)l l l l l l l

1807 1900 2235 2400 2660 3180 3390

Aquifer water 0.21 0.30 0.59 5.01982

Suspended sediment * 0.04 - 0.59 0.35 0.081982

Aquifer water 0.19 0.77 1.6 6.81983

Suspended sediment 0.18 0.38 0.60 0.231983

Surface sediment 0.15 0.16 0.251983

. n (Th

10

0c _o

cr:

M

co

co

0

0

'*1Gi0)

1

0.11976 1978 1980 1982 1984 1986

Year

Characteristics of Actinidesin Mortandad Canyon Shallow Aquifer

Pu > 90% Pu(lll,IV)

Charge distributionPredominantly neutralSome negative charge

Size distribution 3Pu -Colloidal (0.025-0.45 gm)Am -Colloidal (0.025-0.45 jm)

-Soluble (

Characteristics of Actinidesin Mortandad Canyon Shallow Aquifer

(cont'd)

* Reactivity (isotopic equilibrium)Irreversible-very slow to react(laboratory and field)

• Rate of movement (relative)Pu < water (tritium)(e.g., Pu -1 0 times slower than tritium)