Evaluating Interactions of Fracturing F

and Degradation Products with Radionuand Degradation Products with Radionu

Contained in Organic-rich Solid-phase 

Materials

Zoltan Szabo

U.S. Geological Survey
NORM in Produced Waters:

Analogue studies characterization of bedroAnalogue studies, characterization of bedro

radionuclide occurrence, geochemistry, & w

•

Characterize h

a

racteriz

e U, Ra, other isotope ratios

and mixtures 

produced waters. What isotopes account for the radio

• Determine U and Ra-226 occurrence in the solid matr

black shale to 

gg 

ain understandin

g of the source and th

for mobilization

• Define or design benchtop experiments and/or models 

likel

ygp chan

ges in 

produced water concentrations of ra

(U, Th ,or Ra) on the basis of leaching experiments 

• Is increase in rate of entry of radionuclide wastes into 

matrixes indicated? Can it be modeled? Does it providund di f lid i l d d i derstanding o

f solid mater

i

a

l

degra

dat

ion processes

• Weathering processes from black shales from near su

exposures as analogues for deeper “gas” shales?
NORM in produced waters:

Analo

g , ue Studies, Characterization of Bedr

Radionuclide occurrence, Geochemical factor

wastes

• Isotopic forensics for wastes – to study 

preci t d d f i ti 

ise measuremen

ts nee

d

e

d o

f var

i

ati

concentrations and isotope ratios

• Characterize and monitor chan

ges in the 

produced wastes: brines, pipe scale, slud

salts. 

• Desi

g gg p n leachin

g/de

gradation ex

perimen

on information percieved from waste mand analogue studies
Tools for Analysis for Monitoring Radionucli

Tools for Analysis for Monitoring Radionucli

the Solid Matrix 

• Auto-Radiography • Fission-Track Radiography• Scanning electron microscopy energy dispersive x-ray 

(SEM/EDX) 

•

X-ray ab ti d t bsorption near e

dge spec

troscopy - monit i 

itor

ing 

speciation/atom coordination

• -microfocused X-ra

y () Fluorescence 

(uSXRF

) microfoc

ray absorption near edge spectroscopy (uXANES) from synchrotron beam (Brookhaven National Lab; StanforSynchrotron Radiation Lightsource) Synchrotron Radiation Lightsource)

• -Organic Molecular analysis of U-organo matrix
Leaching/degradation experiments

• Di ib i i lid b f d f l 

Distribut

ion 

in solids 

b

e

fore an

d a

fter 

le

• Ongoing Isotopic monitoring of evolvin

with precise measurements

• Possible on

gg 

oin

g solids characterization 

leaching experiments? (using synchrotroli

g ) htsource

)

• Characterize organo-U complexes
Fission Track Autoradioagraphy (U fission stimulated 

Des

pg g g 

ite hi

gh U in zircon 

grain, most U is in 

grain 
Shallow black shale. In places, U distributed evenly in 

surprising local reconcentration found in carbonate-rezones. I li i f i l & ? (SEM

Implicat

ions 

for m

inera

logy 

& transport

? (SEM

+ autoradiograph images
Autoradiograph: Radionuclides redistributed in oxides 
Additional findings from analouge studies Additional findings from analouge studies

-Radionuclides concentrated alon

g pressure solu

These zones may be enhanced zones of fluids m-Radionuclides associate with secondary mineralsi l di it If t d illi il di l i including pyrite. If

true, 

d

rilling spoils disposal is a

(acid drainage and radionuclide mobilization issue

Design of any process study (leaching?) experimeneeds pre-existing information of distribution in sounlikely that the process behavior will be the samrespect to various modes of occurrence in the sol