WWRC- 84- 0 3

ORGANIC CONTAMINANT TRANSPORT I N GROUND WATER,

SURFACE WATER, AND SURFACE WATER SEDIMENTS.
YEAR 1 PROGRESS REPORT.

Michael J. C r o s s e y and H a r o l d L. B e r g m a n
September 7, 1984

D e p a r t m e n t of Zoology and Physiology

C o l l e g e of A r t s and Sciences
U n i v e r s i t y of Wyoming

R e s e a r c h Project Technical
Progress R e p o r t (USGS G - 8 7 9 , P r o j e c t No. 03)

Prepared for:
U.S. D e p a r t m e n t of t h e I n t e r i o r
U.S. G e o l o g i c a l Survey

The research o n which this r e p o r t i s based w a s financed

i n p a r t by t h e U n i t e d S t a t e s D e p a r t m e n t of t h e I n t e r i o r
a s authorized by t h e Water R e s e a r c h and D e v e l o p m e n t A c t
of 1978 (P.L. 9 5 - 4 6 7 ) .

C o n t e n t s of t h i s p u b l i c a t i o n do n o t necessarily r e f l e c t
t h e views and p o l i c i e s of t h e U n i t e d S t a t e s D e p a r t m e n t
of t h e I n t e r i o r , nor does mention of t r a d e names o r
commercial products c o n s t i t u t e t h e i r endorsement by t h e
U.S. Government,

Wyoming Water R e s e a r c h C e n t e r
U n i v e r s i t y of Wyoming
Laramie, Wyoming
 ABSTRACT

Q u e s t i o n s concerning t h e t r a n s p o r t and f a t e of contaminants i n

t h e environment have t y p i c a l l y been l i m i t e d t o s i n g l e compounds.

However, t h e g r e a t e s t danger t o w a t e r r e s o u r c e s i s most o f t e n posed

by s i t e s r e l e a s i n g complex m i x t u r e s c o n t a i n i n g many, even hundreds,

o f hazardous chemicals. Hazardous waste d i s p o s a l f a c i l i t i e s , chemical

p l a n t s , o i l r e f i n e r i e s , e t c . , t y p i c a l l y produce complex w a s t e streams

which may c o n t a c t ground w a t e r o r s u r f a c e waters. This progress

r e p o r t p r e s e n t s r e s u l t s of a s t u d y on movement through ground and s u r -

f a c e water o f a complex m i x t u r e of o r g a n i c compounds emanating from

a wood-treatment f a c i l i t y l o c a t e d a d j a c e n t t o t h e L a r a m i e River i n

L a r a m i e , Wyoming. T h i s s t u d y , i n i t i a t e d i n FY 1983, i s c o n t i n u i n g

w i t h USDI f u n d i n g f o r a second y e a r , through summer 1985.

The o b j e c t i v e s o f t h e s t u d y are t o (1) i n i t i a t e a l i t e r a t u r e

review on contaminant t r a n s p o r t models and develop a c o n c e p t u a l model

of contaminant t r a n s p o r t a t t h e Laramie River s i t e ; ( 2 ) conduct

l a b o r a t o r y ( s o i l column) and f i e l d experiments t o i n v e s t i g a t e o i l /

w a t e r emulsion m i g r a t i o n through porous media; and ( 3 ) b e g i n a f i e l d

study a n a l y z i n g contaminant f a t e i n sediments downstream from t h e

wood-treating f a c i l i t y . A f o u r t h o b j e c t i v e , t o supply t h e Wyoming

Department o f Environmental Q u a l i t y (DEQ) w i t h a summarization of

contaminant t r a n s p o r t models, w a s d e f e r r e d t o FY 8 4 b a s e d on r e q u e s t s

from DEQ o f f i c i a l s t o i n c o r p o r a t e t h e Year 2 s t u d y and submit a s i n g l e ,

.Ei n a l r e p o r t .

C u r r e n t l y , mathematical models a r e n o t r e a d i l y a v a i l a b l e t o

ii
simulate the transport and fate of complex mixtures of organic com-

pounds. This is especially true when these contaminants are in high

concentrations producing a multi-phase solution. But a conceptual model

summarizing laboratory and site observations shows: (1) subsurface

transport of contaminants in oil, oil/water emulsions, and ground-

water; and (2) riverine transport of contaminants in water, sorbed

to sediments, and as oil globules.

Experiments with g l a s s columns packed with a uniform material

(1 mm glass beads, sand, or gravel) indicates that in even the most

homogenous, isotropic matrix, oil/water mixtures cannot be expected

to flow in a uniform manner. Creosote sludges and oils break up into

globules and stringers with no uniform front of contamination. Data

from a field study using mini-piezometers in the Laramie River adjacent

to the site confirm this observation.

Chemical analyses of sediments and fish, as well as field obser-

vations indicating oily droplets moving along the river bed, clearly

establish contamination of the Laramie River resulting from offsite

migration of creosote from the wood-treating facility.

iii
 TABLE OF CONTENTS

Page

INTRODUCTION ......................... 1

OBJECTIVES 0 ........ 4

RELATED ACTIVITIES . . . . . . . . . . . . . . . . . . . . . . 5

TASK 1: TRANSPORT MODELS . . . . . . . . . . . . . . . . . . . 7

TASK 2: CONTAMINANT TRANSPORT IN GROUND WATER . . . . . . . . 10

TASK 3: CONTAMINANT TRANSPORT IN SURFACE WATER ....... 16

SUMMARY AND CONCLUSIONS . . . . . . . . . . . . . . . . . . . . 25

REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . 26

iv
 LIST OF FIGURES

Page

Figure 1. Location of Union Pacific Tie Treatment

Plant near Laramie, Wyoming ............ 3

Figure 2. Location of mini-piezometer sampling points

points in the Laramie River adjacent to
the Union Pacific Tie Treatment Plant
near ~aramie,Wyoming ............... 12

Figure 3. Total relative fluorescence for extracts

of mini-piezometer samples ............. 14

Figure 4. Reverse-phase High Performance Liquid

Chromatography (HPLC) gradient
chromatograms for solvent extracts of (a)
cresote saturated glass beads, (b)
contaminated site soil, and (c) sediment
sample taken 3.5 km downstream from the Tie
Treatement Plant (TTP), (d) sediment
sample taken - 5 km upstream from TTP........ 20

V
 LIST OF TABLES

Paqe

T a b l e 1. Summary of f i s h tissue analysis results

f r o m the Laramie River d o w n s t r e a m from
the Union Pacific T i e Treatment P l a n t ,
L a r a m i e , Wyoming.................. 24

vi
 INTRODUCTION

Contaminant t r a n s p o r t modeling i n gromd w&ef, surface w a t e r ,

s o i l s r and s e d i m e n t s h a s been r e s t r i c t e d p r i m a r i l y t o s i n g l e compound

i n t e r a c t i o n s w i t h t h e environment. However, t h e g r e a t e s t danger t o

w a t e r r e s o u r c e s i s more o f t e n posed by s i t e s r e l e a s i n g complex m i x t u r e s

o f chemicals. The problem t h a t arises i s t h a t i n t e r a c t i o n s among

chemicals i n t h e m i x t u r e c a n a f f e c t t h e environmental t r a n s p o r t and

f a t e o f any s i n g l e chemical. T h i s i s e s p e c i a l l y t r u e when o r g a n i c

contaminants are p r e s e n t i n h i g h c o n c e n t r a t i o n s . A s i m p l e example

would b e t h a t t h e s o i l a d s o r p t i o n / d e s o r p t i o n r a t e c o n s t a n t s f o r a

hydrophobic compound d e r i v e d from a n experiment u s i n g water as a s o l v e n t

d o n o t a p p l y t o a system which a l s o c o n t a i n s h i g h c o n c e n t r a t i o n s of

a n o r g a n i c s o l v e n t such a s p h e n o l , t o l u e n e o r benzene.

I n d u s t r i a l p l a n t s , o i l r e f i n e r i e s , d r i l l i n g sites and wood-treat-

i n g p l a n t s produce and may release such complex m i x t u r e s of o r g a n i c

compounds. A t s i t e s such a s t h e s e , a s w e l l as a t hazardous waste

d i s p o s a l s i t e s and chemcial s p i l l s i t e s , hazardous chemicals o f t e n can

w a ~ ; e r / s u r f a c e w a t e r s , and s u r f a c e w a t e r
b e r e l e a s e d i n t o s o i l s , c_--.round

s e d i m e n t s as a n emulsion o r hydrocarbon f l u i d . Once r e l e a s e d i n t h i s

way, contaminants may b e t r a n s p o r t e d through t h e s e systems i n t h r e e

d i f f e r e n t f l u i d p h a s e s : o i l , o i l / w a t e r emulsions, and w a t e r . The a b i l i t y

o f s t a t e and f e d e r a l r e g u l a t o r y a g e n c i e s t o d e t e c t , monitor, and p r e -

d i c t t h e movement and f a t e o f complex contaminant m i x t u r e s , as w e l l

a s t h e i r a b i l i t y t o implement r e m e d i a l a c t i o n , h a s been hampered by

1
a l a c k o f knowledge concerning multi-phase t r a n s p o r t problems such

as these.

T h i s r e p o r t d e t a i l s t h e work t o d a t e and c u r r e n t l y i n p r o g r e s s

a t t h e Union P a c i f i c ' s t i e t r e a t m e n t p l a n t (TTP) fn Laramie, Wyoming

( F i g . 1). T h i s p l a n t had been i n o p e r a t i o n f o r a l m o s t one hundred

y e a r s p r i o r t o i t s c l o s u r e i n t h e s p r i n g of 1983. Severe contamination

from c r e o s o t e w a s t e s i n c l u d i n g p e n t a c h l o r o p h e n o l h a s o c c u r r e d o v e r

approximately 80 acres of t h e s i t e . Groundwater contamination r a n g e s

f r o m t r a c e l e v e l p o l y n u c l e a r a r o m a t i c hydrocarbons t o l e v e l s exceeding

s o l u b i l i t y l i m i t s , i n d i c a t i n g p r e s e n c e of a n o i l / w a t e r emulsion

(CH2M-Hill 1984). I n f a c t , some o n - s i t e r e c o v e r y w e l l s produce creo-

s o t e i n s u f f i c i e n t q u a n t i t y and q u a l i t y t o w a r r a n t a p r o d u c t r e c o v e r y

program ( C H 2 M - H i 1 1 1 9 8 4 ) . I n a d d i t i o n t o o n - s i t e groundwater con-

t a m i n a t i o n , f i e l d i n v e s t i g a t i o n s have shown t h a t t h e L a r a m i e River

a d j a c e n t t o t h e s i t e h a s o i l y s e e p s which are c o n t a m i n a t i n g b o t h t h e

w a t e r and t h e r i v e r sediments downstream from t h e s i t e .

F u r t h e r s t u d i e s have been funded through t h e Wyoming Water

Research C e n t e r (WWRC)/U.S. Department of I n t e r i o r program f o r f i s c a l

y e a r 1984 (FY84). T h i s c o n t i n u a t i o n i n funding w i l l b e used t o con-

t i n u e and expand p o r t i o n s of t h e s t u d y p r e s e n t e d below. Completion of

some of t h e o r i g i n a l FY83 o b j e c t i v e s of t h i s s t u d y have been postponed

t o t h e FY84 p e r i o d b a s e d on recommendations of WWRC p e r s o n n e l and t h e

Wyoming Department of Environmental Q u a l i t y (DEQ).

2
 1 WYOMING

w I I-

TREATMENT
PLANT

F i g u r e 1. Location of Union P a c i f i c T i e Treatment P l a n t n e a r Laramie, Wyoming.

 OBJECTIVES

B r i e f l y t h e f o u r o r i g i n a l o b j e c t i v e s i n t h e F Y 8 3 s t u d y were as

follows .
T r a n s p o r t . model e v a l u a t i o n : L i t e r a t u r e review and evalu-

a t i o n o f contaminant t r a n s p o r t and f a t e models d e a l i n g w i t h

complex o r g a n i c m i x t u r e s .

Contaminant t r a n s p o r t i n ground w a t e r : Laboratory s o i l

column experiments t o i n v e s t i g a t e movement of contaminated

o i l s and o i l / w a t e r emulsions i n ground w a t e r .

Contaminant t r a n s p o r t i n s u r f a c e w a t e r : F i e l d sampling

and a n a l y s i s of Laramie R i v e r sediments downstream from

t h e Union P a c i f i c t i e t r e a t m e n t p l a n t .

Report t o r e g u l a t o r y a g e n c i e s : A summary of e x i s t i n g

knowledge and e x p e r i e n c e p r o v i d i n g p r a c t i c a l guidance t o

r e g u l a t o r y a g e n c i e s and i n d u s t r y f o r a s s e s s i n g t r a n s p o r t o f

complex contaminant m i x t u r e s i n ground w a t e r and s u r f a c e

water.

Through t h e c o u r s e of t h e FY83 s t u d y t h e s e o b j e c t i v e s were modi-

f i e d s l i g h t l y and expanded t o add a d d i t i o n a l i n f o r m a t i o n about contam-

i n a n t t r a n s p o r t and f a t e phenomena a t o u r case-study f i e l d s i t e .

These m o d i f i c a t i o n s were t h e n i n c o r p o r a t e d i n t o t h e FY84 o b j e c t i v e s .

The p r i n c i p a l a d d i t i o n s i n t h e FY84 o b j e c t i v e s a r e , b r i e f l y , t o expand

t h e ground-water contaminant t r a n s p o r t s t u d i e s u s i n g mini-piezometers

and seepage meters on and a d j a c e n t t o t h e f i e l d s i t e , and t o expand

t h e s u r f a c e water contaminant t r a n s p o r t and f a t e s t u d i e s w i t h f i s h and

a d d i t i o n a l sediment c o l l e c t i o n and a n a l y s i s from t h e r i v e r downstream

from t h e s i t e .

4
 RELATED ACTIVITIES

Due to on-going litigation involving the State of Wyoming, the

U.S. Environmental Protection Agency (EPA), and the Union Pacific

Railroad, we have been asked by the State of Wyoming to review data

related to the site as well as report any significant findings from

our own studies to the State, In this capacity we have attended

private and public meetings as well as reviewed technical reports

submitted to the Wyoming DEQ by Union Pacific's consultant CH2M-Hill.

Following the initial site investigations a contaminant assessment

was submitted to the State by the Union Pacific (CH2M-Hil1, 1983).

Evaluation of this draft document led to the conclusions that the tie

treatment plant was severely contaminated, having contaminants in the

groundwater above their solubility in aqueous solutions (Bergman and

Crossey, 1983), and that the evaporation ponds probably leak (Huntoon,

1983). More recent investigations have shown this to be the case

(CH2M-Hill, 1984). A second draft report (CH2M-Hil1, 1984) for which

comments were requested and submitted (Crossey, 1984) has not as yet

been released in final form,

In addition to site investigations the EPA requested comments on

the evaporation pond closure plan (CH2M-Hil1, 1983 and 1984) which is

regulated under the Resource Conservation and Recovery Act (RCRA).

Comments presented at a public hearing in February, 1984 pointed out

the danger of on-site storage of solidified organic wastes due to the

possible infiltration of ground water as well as the questionable

interaction of clay liners and organic fluids such as those found

5
a t the site.

C u r r e n t l y w e a r e reviewing t h e Phase 111, Remedial Action Feas-

i b i l i t y Study, and a r i s k assessment of t h e Union P a c i f i c t i e t r e a t m e n t

p l a n t f o r t h e Wyoming DEQ.

6
 TASK 1: TRANSPORT MODELS

Although the development and use of contaminant transport models

for single chemicals in ground and surface waters has been increasing

markedly in the last 10 to 15 years, there have been few, if any,

attempts to modify these models for complex contaminant mixtures and

contaminated multi-phase fluids. Thus, our aim in this task was to

determine whether recent work by contaminant transport modelers

included such modifications and to evaluate the utility of existing

single-contaminant transport models for complex mixture and multi-

phase fluid transport problems.

Procedures

Hand searches and computerized bibliographic database searches were

conducted to identify recent published literature on the application

of contaminant transport modeling to complex contaminant mixtures and

contaminated multi-phase fluids. Additionally, key researchers and

model users in North America were contacted to determine whether

such models were currently under development in the contaminant

modeling field.

Results and Discussion

Literature searches and contacts with knowledgable researchers in

North America confirmed that no working transport models for complex

contaminant mixtures apparently exist. With regard to this question,

all of the relevant literature discovered dealt only with the concept-

ual framework necessary to approach such a modeling problem (e.g.,

7
Bergman and Meyer, 1982). All of the potentially applicable models

or literature discovered can be classified into three categories:

(1) single-contaminant ground-water transport models, (2) single-

contaminant surface water transport models, and ( 3 ) multi-phase oil/

water transport models that are usually applied to oil reservoir

dynamics problems.

Ground-water modeling was initially developed as a resource

monitoring tool. Models were used to calculate flow, specific yield,

drawdown rates, etc., to enable agencies to manage ground water for

domestic and agricultural uses. Models such as these are now at a

refined state and most situations can be adequately modeled (Freeze

and Cherry, 1979). Ground-water contaminant transport modeling is a

more recent development and has built upon the previously established

resource modeling techniques. There are three types of models available,

advection, advection-dispersion, and geochemical. These types of

models allow one to theoretically incorporate the effects of the

aquifer matrix as well as chemical interactions on the concentrations

of contaminants through distance and/or time. However, in practice

only the simplest, the advection models, are routinely used (Anderson,

1981). These models are limited by the simplifying assumptions of

no dispersion or chemical interaction between the contaminant and

the aquifer matrix. However, these models can be used to estimate

the "worst possible case" scenario for contaminant transport.

Modeling complex organic contaminants in qround-water systems

requires not only incorporation of the aquifer interactions mentioned

8
above but, in addition, the contaminant chemistry itself, since it can

greatly affect migration rates. Heavily contaminated sites in which

hydrocarbon fluids and aqueous fluids are present require multi-phase

flow modeling (Marle, 1981). In general, the theoretical/mathematical

development of contaminant transport models is ahead of the knowledge

about the controlling processes from the field.

Surface water contaminant modeling presents many of the same

short-comings as ground-water modeling. The fate and transport of

complex organic mixtures is not nearly as well researched as dissolved

single compound contaminant models. The complex nature of organic

contaminants does not necessarily preclude modeling but, obviously,

field studies and observations are required to detect and define

the important controlling processes on which the models are to be

based.

9
 TASK 2: CONTAMINANT TRANSPORT I N GROUND WATER

The movement of organic contaminant mixtures i n ground water and

s u r f a c e water i s o f t e n d i f f i c u l t t o p r e d i c t due t o t h e numerous

i n t e r a c t i o n s among compounds w i t h i n t h e mixture. Often physical/

chemical c o n s t a n t s d e r i v e d f o r s i n g l e compounds may n o t r e l i a b l y

p r e d i c t t h e chemical behavior of a compound i n a complex mixture

(Banerjee e t a l . , 1 9 8 4 ) . With t h i s i n mind, t h e s t u d i e s presented

below were designed t o t r e a t a complex mixture ( c r e o s o t e ) a s a whole

and t o d e f i n e p r o p e r t i e s t h a t would d e s c r i b e , i n a g e n e r a l way, t h e

behavior of t h i s mixture i n ground water.

Procedures

G l a s s s o i l columns, 60 cm long x 1 5 cm diameter, with t e f l o n ends

were c o n s t r u c t e d with f o u r g l a s s piezometers extending i n t o t h e

column packing a t v a r i o u s depths t o sample pore f l u i d s . Three column

packings a r e c u r r e n t l y being t e s t e d , 1 m g l a s s beads, s i t e s o i l , and

washed sand. A f t e r column packing, creosote i s introduced through

a n opening i n t h e cap. Water flow, e i t h e r t o p t o bottom o r bottom

t o t o p , i s maintained with t e f l o n tubing f i t t e d i n t o t h e c e n t e r of

each cap. Pore f l u i d s and e l u e n t s from t h e columns a r e analyzed

using t o t a l fluorescence (described below) and HPLC (described i n

Task 3 ) .

I n a d d i t i o n t o t h i s l a b column study, which w i l l be continued

through FY84, a f i e l d study w a s i n i t i a t e d t o i n v e s t i g a t e t h e flow

of c r e o s o t e and water w i t h i n t h e a l l u v i a l a q u i f e r a t t h e TTP. For

10
t h i s purpose mini-piezometers were constructed following the design of

Lee and Cherry (1978). Teflon tubing (3/8" O.D., 1/4" I . D . ) was

perforated (1/16" holes) and screened on one end and i n s e r t e d i n t o

t h e r i v e r sediments, I n t h i s way a water sample could be taken below

t h e bottom of t h e riverbed representing subsurface water. Depending

on the hydraulic gradient, t h i s water would be e i t h e r coming from the

s i t e i n t o t h e r i v e r , moving from t h e r i v e r t o the s i t e o r moving down-

stream with the interflow. Thirty-nine mini-piezometers were placed i n

the Laramie River adjacent t o the west s i d e of the TTP. The depth t o which

t h e piezometers penetrated t h e r i v e r bottom ranged from one t o t h r e e f e e t .

Typically, t h e piezometers were driven through the f i n e sands making up the

r i v e r bottom u n t i l t h e Morrison formation was reached. This formation

underlies t h e Laramie River i n t h i s area and subcrops j u s t e a s t of the

r i v e r on t h e TTP s i t e (Charles Feast, C H 2 M - H i l 1 , Denver, Colorado p e r s .

corn.). The l o c a t i o n of each of t h e mini-piezometer samples is designated

on Figure 2. Samples were c o l l e c t e d on February 23-25, 1984, during a

period when t h e r i v e r was ice-covered.

Samples from t h e subsurface were obtained by applying a vacuum

t o t h e end of t h e piezometer, and t h e samples were drawn i n t o 100 m l

glass jars. J a r s were capped with teflon-lined l i d s and taken t o the

l a b f o r analysis. A t t h e l a b t h e samples were extracted i n t o freon

(30 mls sample t o 5 m l s f r e o n ) . Total fluorescence of t h e e x t r a c t s was

then measured ( e x c i t a t i o n wavelength = 360 nm, emission wavelength = 410 nm).

The t o t a l fluorescence i s proportional t o the amount of aromatic organic

chemicals i n t h e sample,

11
 10

LARAMIE RIVER

QOXBOW POND
HEAVY CONTAMINATION *
PJEZOMETER
WASTE POND A WELL

Figure 2. L o c a t i o n of mini-piezometer sampling p o i n t s i n t h e Laramie R i v e r a d j a c e n t t o t h e Union

P a c i f i c T i e Treatment P l a n t n e a r L a r a m i e , Wyoming,
Results and Discussion

Only t h e preliminary observation from the column s t u d i e s w i l l be

presented i n t h i s r e p o r t . Delays i n column manufacture and the ex-

tremely slow movement of creosote i n water-saturated columns has

slowed progress i n t h i s phase of the study. I n the f i r s t experiment,

no flow through t h e column was used. Once packed with g l a s s beads,

washed sand, o r s i t e s o i l , the columns were f i l l e d (bottom t o top) with

water. Creosote was then introduced t o t h e top of t h i s s t a t i c column.

I n i t i a l l y no movement could be detected. The creosote appeared t o

" f l o a t " on top of t h e column of water. This creosote sample had a

3
density of 1.01 gm/cm b u t remained i n t h i s unstable equilibrium.

This phenomenon has been described previously i n multi-phase flow

s i t u a t i o n s (Marle, 1981). However, once perturbed by mixing the

top 2 cm of packing, t h e creosote began t o flow i n small s t r i n g e r s

and globules f o r s e v e r a l centimeters. This has a l s o been observed i n

t h e f i e l d a t t h e TTP s i t e ( C H 2 M - H i l 1 , 1984) and i n the mini-piezometer

study presented below. The flow of these s t r i n g e r s and globules v i r t u -

a l l y ceased following t h e i n i t i a l movements (over a two month period no

movement was recorded). Other s t u d i e s t o be completed i n FY84, w i l l provide

a b e t t e r understanding of t h e processes c o n t r o l l i n g t h e flow of creosote

through t h e s e types of matrices.

As can be seen from t h e data f o r t o t a l fluorescence of piezometer

water e x t r a c t s (Fig. 3 ) , t h e r e i s an obvious seep a t sample location

10. This sampling p o i n t l i e s e a s t and s l i g h t l y north of well 23

(Fig. 2 ) . Sample 11 which i s mid-river d i r e c t l y e a s t of sample 1 0

a l s o shows high fluorescence. Sample 1 0 was, i n f a c t , black, o i l y

 Figure 3. Total relative fluorescence for extracts
of mini-piezometer samples, See map
(Figure 2) for corresponding sample
locations.

SO

40

30

20

10

SAMPLE NUMBER
f l u i d which had a strong creosote odor. Other samples had fluorescence

values t h a t i n d i c a t e t h a t they may be near other seeps (samples 3 ,

1 6 , 3 2 , 36, f o r example). Total fluorescence of sample 36 would seem

t o i n d i c a t e t h a t t h e r e may be a seep a t the northern end of the old

r i v e r oxbow near well D-32.

These d a t a confirm t h a t organic contaminants a r e reaching the Laramie

River a s o i l y seeps. The fluorescence data i n d i c a t e t h a t t h e r e may have

been as many as four o r f i v e seeps present during the sampling period i n

February 1984. More seeps may have been present, but they could have been

missed due t o t h e 10-meter spacing of the mini-piezometers. For example,

sample 1 0 was a t h i c k , o i l y f l u i d b u t samples 9 and 1 2 , which were collected

from within 1 0 meters of sample 1 0 , show low t o moderate fluorescence.

For t h i s t o occur, t h e seeps were probably small, on the order of s e v e r a l

inches t o s e v e r a l f e e t , and t h e sampling g r i d of 10 t o 100 meters

may have missed a number of contaminant seeps.

15
 TASK 3 : CONTAMINANT TRANSPORT I N SURFACE WATER

A f u l l u n d e r s t a n d i n g of contaminant t r a n s p o r t i n r i v e r i n e systems

r e q u i r e s knowledge of contaminant t r a n s p o r t i n water, i n suspended

p a r t i c u l a t e s , and i n t h e sediments. Compounds having v e r y low w a t e r

s o l u b i l i t y , such as t h e compounds of p r i n c i p a l concern a t t h e t i e

t r e a t m e n t p l a n t (TTP) s i t e , w i l l b e found mainly sorbed t o t h e r i v e r

bed s e d i m e n t s . F o r t h a t r e a s o n , t h i s s t u d y c o n c e n t r a t e d on c o n t a m i n a t i o n

of r i v e r bed sediments downstream f r o m t h e TTP s i t e as an i n d i c a t o r

of contaminant release from t h e s i t e . Analyses of f i s h t a k e n from t h e

r i v e r a d j a c e n t t o and downstream f r o m t h e s i t e w a s added t o t h e s t u d y

a s a n a d d i t i o n a l i n d i c a t o r of o f f - s i t e movement of contaminants.

T y p i c a l l y a q u a t i c sediments have been t h o u g h t of as a s i n k r a t h e r

t h a n s o u r c e of c o n t a m i n a t i o n , Recently r e s e a r c h h a s been d i r e c t e d

toward i d e n t i f y i n g t h e p r o c e s s e s t h a t c o n t r o l t h e t r a n s p o r t , f a t e ,

and b i o a v a i l a b i l i t y of contaminants bound t o t h e sediments (Baker,

1980). The importance o f sediment as a t r a n s p o r t mechanism f o r

o r g a n i c compounds h a s been e x p r e s s e d w i t h r e g a r d t o environmental

f a t e modeling (Urchin and Weber, 1980; Burns, 1 9 8 2 ) . Field studies

a s w e l l have s t r e s s e d t h e importance of sediment b i n d i n g and t r a n s p o r t

of o r g a n i c compounds r e s u l t i n g i n e x t e n s i v e low-level contamination of

a q u a t i c systems (Black, 1982; P i e r c e e t a l . , 1 9 8 0 ) . D a t a presented

below d e s c r i b e s t h e methods developed t o sample, e x t r a c t , and a n a l y z e

s e d i m e n t s downstream from t h e TTP t o e v a l u a t e o f f - s i t e contaminant

migration.

16
 Hydrophobic compounds such a s those found i n creosote can be

bioaccumulated. T o a s s e s s the contaminant concentrations i n f i s h

l i v i n g near t h e TTP we sampled a four kilometer s t r e t c h immediately

downstream from t h e s i t e .

Procedures

In t h e f a l l of 1983, 16 sediment samples were c o l l e c t e d i n slow

backwater a r e a s over a distance of 16 k m downstream from the TTP.

Surface sediment was scraped and collected i n t o a two l i t e r g l a s s

beaker. This sediment and r i v e r water were s t i r r e d vigorously t o

suspend t h e organic f i n e s , clays, and p a r t i c u l a t e organic matter.

This s o l u t i o n was then decanted i n t o another two l i t e r beaker, leaving

behind t h e coarse sands and gravel which were discarded. The second

beaker containing f i n e sediments was allowed t o s e t t l e f o r f i v e t o

t e n minutes, and t h e water was then decanted and discarded. Following

t h i s procedure s e v e r a l times a t a given s i t e allowed us t o c o l l e c t

approximately 500 m l s of "organic r i c h " sediments. S t i c k s , leaves,

and coarse p a r t i c u l a t e organic matter were removed and discarded.

Samples were then frozen u n t i l analyses were performed. This sampling

scheme was developed because s e v e r a l authors have s t r e s s e d the importance

of t h e organic f r a c t i o n i n t h e t r a n s p o r t of contaminants (Black, 1982;

Lopez-Avila and Hites, 1980; Pierce e t a l . , 1980).

A batch e x t r a c t i o n method was developed t o rapidly process

samples f o r High Performance Liquid Chromatography (HPLC). The

e x t r a c t i o n solvent consisted of a c e t o n i t r i l e , freon, and a c e t i c acid

(1000, 1 0 , 2 m l s , r e s p e c t i v e l y ) . One gram of air-dried sediment was

17
p l a c e d i n a 250 m l Erlynmeyer f l a s k t o which 25 m l s e x t r a c t i o n s o l v e n t

w a s added. The f l a s k s were capped with t e f l o n - l i n e d screwcaps and

p l a c e d on a shaker t a b l e (150 rpm) f o r 24 h r s . Following e x t r a c t i o n ,

samples were allowed t o s e t t l e and a 2 m l a l i q u o t of t h e e x t r a c t i o n

s o l v e n t w a s removed, f i l t e r e d through a 0.2 pm t e f l o n f i l t e r , and

i n j e c t e d d i r e c t l y i n t o t h e HPLC without f u r t h e r processing.

Chromatographic a n a l y s e s were performed on a Waters l i q u i d

chromatograph using a one hour l i n e a r g r a d i e n t , 100% HPLC grade water

c o n t a i n i n g 0 . 3 m l s / l a c e t i c a c i d t o 100% a c e t o n i t r i l e , a t a flow of

2 mls/min. Absorbance a t 254 nm and 280 nm was used f o r d e t e c t i o n .

I n a d d i t i o n t o r e t e n t i o n time, t h e r a t i o of absorbance a t 254 nm t o

280 nm (254 nm/280 nm) w a s used f o r compound i d e n t i f i c a t i o n . Retention

t i m e s and absorbance r a t i o s were compared t o a mixture of p u r i f i e d

s t a n d a r d s as w e l l a s an e x t r a c t of o n - s i t e contaminated s o i l .

F i s h were sampled from a b o a t using electroshocking equipment.

Four composite samples were analyzed. A f t e r sampling, f i s h were e v i s -

cerated, d e c a p i t a t e d , and i n d i v i d u a l l y wrapped i n aluminum f o i l and

frozen. Analyses were performed a t t h e U.S. F i s h and W i l d l i f e S e r v i c e ,

Columbia National F i s h e r i e s Research Laboratory. For determinations of

polynuclear aromatic hydrocarbons (PNAs) and phenols, each sample was

s u b j e c t e d t o column e x t r a c t i o n with methylene c h l o r i d e of a d r i e d

powder mixture of t h e f i s h t i s s u e and sodium s u l f a t e , followed by two

f r a c t i o n a t i o n s t e p s using g e l permeation chromatography. Each sample was

spiked p r i o r t o t h e e x t r a c t i o n a t 100 ng/g with n se*:ies of i n t e r n a l

r e f e r e n c e compounds, s i x d e u t e r a t e d PNAs and 4-iodophenol. Additionally

18
one sample was processed in triplicate, with two of the triplicate samples

spiked with the internal standards and the third spiked with both the

internal standards and a mixture of eleven representative PNAs and eleven

representative phenols (the EPA Priority Pollutant phenols). Four control

samples (no fish tissue) were also included in this set of samples for

purposes of providing recovery and procedural background data. The analyses

of the latter four samples were not completed at the time of this report.

Determinations of the target compounds were by high resolution

gas chromatography/low resolution mass spectrometry using a 30 meter

DB-5 capillary column and a Finnigan 4023 mass spectrometer. Individual

confirmations of component identity were made for each compound in

each sample.

Results and Discussion

The methods developed during the course of this study have proven

to be satisfactory and only minor modifications are planned for

FY84 sampling, extraction and analysis.

The complexity of the organic contaminants at the TTP precludes

identification of all the compounds adsorbed to the sediments. How-

ever, based on identical retention times and 254 nm/280 nm absorbance

ratios, phenanthrene, anthracene, and chrycene were tentatively iden-

tified on the HPLC chromatograms for a creosote extract and extracts

of TTP site soil and Laramie River sediments 3.5 km downstream from

the site (Fig. 4). The chromatograms also can be used to describe

the general distribution of compounds ("fingerprint") in the mixture.

Illustrations of this "fingerprint" are the chromatograms of on-site

19
F i g u r e 4. Reverse-phase High Performance L i q u i d Chromatography

(HPLC) g r a d i e n t chromatograms f o r s o l v e n t e x t r a c t s of

( a ) c r e o s o t e s a t u r a t e d g l a s s b e a d s , ( b ) contaminated

s i t e s o i l , and ( c ) sediment sample t a k e n 3 . 5 km down-

s t r e a m from t h e T i e Treatment P l a n t (TTP), (d) sediment

sample t a k e n .5 km upstream from TTP. W absorbance

i n t e n s i t y a t 254 nm i s shown f o r each sample, and a n

absorbance s c a l e (AU = absorbance u n i t s ) i s i n d i c a t e d

b e s i d e each chromatogram. R e t e n t i o n t i m e s of f i v e

major compounds a r e i n d i c a t e d above each chromatogram,

as f o l l o w s : 1 = p e n t a c h l o r o p h e n o l ( C H C 1 O H ) , 2 = naph-
6 5 5
thalene (C H ) , 3 = phenanthrene ( C H ) , 4 = anthra-
10 8 1 4 10
cene ( C H ) I and 5 = c h r y s e n e (C18H12). Peaks A, R ,
1 4 10
and C i n t h e chromatograms a r e t e n t a t i v e l y i d e n t i f i e d

on t h e b a s i s of r e t e n t i o n t i m e and 254nm/280nm alosorb-

ance r a t i o s as phenanthrene, a n t h r a c e n e , and cwycene

respectively. See t e x t f o r d e t a i l s of e x t r a c t i o n

p r o c e d u r e s and chromatographic c o n d i t i o n s .

20
 2 4 5
I I I

a. 0.02 AU
I

I I I I 1 I 1
t 2 34 5
I I II I
A

b. 0.02 AU
I

I
I I I I I ~ -1

I
C. I 0.02 AU
I 2
I
34
II
A
5
I

d. 0.02 AU
I
I I I I I I
0 20 40 do
RETENTION TIME (min)
21
contaminated s o i l and L a r a m i e R i v e r sediment ( F i g . 4 b , c ) . This p a t t e r n

i s n o t s e e n i n upstream sediment samples ( F i g . 4 d ) . A second i n t e r e s t -

i n g comparison i s t h e chromatogram f r o m a n e x t r a c t o f 1 m m g l a s s beads

which had been contaminated w i t h c r e o s o t e from t h e TTP ( F i g . 4 a ) . These

g l a s s b e a d s were used i n t h e column experiments d e s c r i b e d above. Free o i l

w a s allowed t o d r a i n f r o m t h e beads p r i o r t o e x t r a c t i o n . The e x t r a c t i o n

r a t i o w a s similar t o t h e sediments and soils (1 gm/20 m l s ) . Clearly

t h e p a t t e r n shown i n F i g u r e 4 a , b , c i s v e r y s i m i l a r , t h e d i f f e r e n c e s b e i n g

o n l y q u a n t i t a t i v e and n o t q u a l i t a t i v e .

Not a l l of t h e downstream samples show t h i s contaminant f i n g e r p r i n t .

T h i s i n d i c a t e s t h a t t h e downstream areas are n o t uniformly contaminated

n o r do t h e y show d e c r e a s i n g c o n t a m i n a t i o n w i t h d i s t a n c e from t h e TTP

as s e e n by Black (1982). T h i s heterogeneous contaminant d i s t r i b u t i o n

may b e a f u n c t i o n o f t h e h y d r o l o g i c regime a t t h e s i t e which c a u s e s

s p o r a d i c s e e p s t o appear and a p u l s e of contaminated sediments may

move down t h e r i v e r and s e t t l e i n one area. A d d i t i o n a l l y , as d i s c u s s e d

i n t h e p r e c e d i n g s e c t i o n , t h e p r e s e n c e of o i l y d r o p l e t s o r g l o b u l e s

may c a u s e t h i s t y p e of contaminant d i s t r i b u t i o n . S e a s o n a l o r day t o day

changes i n t h e flow o f t h e r i v e r may govern where t h e s e o i l d r o p l e t s s e t t l e

and how f a r t h e y t r a v e l . If t h e c o n t a m i n a t i o n downstream i s a secondary

e f f e c t due t o c l e a n sediments c o n t a c t i n g t h e s e o i l y d r o p l e t s t h i s may

i n c r e a s e t h e v a r i a b i l i t y i n contaminant c o n c e n t r a t i o n s i n downstream

sediments. T h i s phenomenon h a s been n o t e d i n an e s t u a r y system

(Lopez-Avila and H i t e s , 1 9 8 0 ) .

The r e s u l t s p r e s e n t e d i n Table 1 i n d i c a t e contamination of

22
f i s h l i v i n g downstream from t h e TTP. Pentachlorophenol has been

shown t o be depurated w i t h i n a few days i f a f i s h i s returned t o c l e a n

water (EPA, 1980; Lech e t a l . , 1978; Akitake and Kobayashi, 1975)-

Therefore, t h e pentachlorophenol p r e s e n t i n t h e f i s h i n d i c a t e s e i t h e r

a n exposure event w i t h i n one t o two days p r i o r t o sampling o r a chronic

low-level exposure l e a d i n g t o t h e observed body burden of pentachloro-

phenol i n t h e f i s h , The l a t t e r case would seem t h e most p l a u s i b l e .

23
Table 1. Summary of f i s h t i s s u e a n a l y s i s r e s u l t s from t h e L a r a m i e River
downstream from t h e Union P a c i f i c T i e Treatment P l a n t , L a r a m i e ,
Wyoming .
Distance
a a
Sample Description downstream Compound Concentra ion
(km) (PPb)
&

Composite of 0 Acenaphthalene 142

3 white suckers; Dibenzofuran 65
e d i b l e portion; Fl u o r ene 56
608, 794 and Naphthalene 117
907 gm Pentachlorophenol 147

2 Composite of 0,254 5 . Methylnaphthalene 114

2 white suckers; Naphthalene 58
whole f i s h ; C-2 Naphthalene 51
200 gm each

3 Composite of 2 Pentachlorophenol 79
3 brown t r o u t ;
e d i b l e portion;
597, 793 and
1,134 - g M

4 Composite of 3.5 Naphthalene 73

2 brown t r o u t ; Pentachlorophenol 119
e d i b l e portion;
294 and 1,250 gm

a
Only t h o s e compounds found a t c o n c e n t r a t i o n s g r e a t e r t h a n 50 ppb a r e
reported.
b
ppb = p a r t s per b i l l i o n = ng/gm.

24
 SUMMARY AND CONCLUSIONS

1) To date it appears that no models exist that adequately describe

the transport and fate of complex organic mixtures in surface

water and/or groundwater systems.

2) Lab and field studies indicate that, for multi-phase contaminant

transport in ground water, there is rarely a uniform front or

plume but rather small. stringers and isolated globules.

3) Organic contaminants can be traced several kilometers downstream

from the Union Pacific Tie Treatment Plant, and there appears

to be heterogeneous distribution of contaminants in downstream

backwater areas.

4) Droplets of free oil (creosote) are probably an important compon-

4

ent of the mass flux of contaminants from the site to the river

system.

5) The soil columns, mini-piezometers, sediment sampling methods,

and analytical methods (fluorescence and HPLC) developed in FY83

have proven to be satisfactory and will be continued in the FY84

study .
6) The FY84 studies will require increased sampling of sediments

and mini-piezometers and the use of seepage meters to better quantify

the rate of contaminant movement to the Laramie River from the Tie

Treatment Plant.

25
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chlorophenols in fish - 111. Isolation and identification of
conjugated PCP excreted by gold fish. Bull. Jap. SOC. Sci. Fish.
41:322.

Anderson, M. P. 1981, Groundwater quality models - state of the art.

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Baker, R, A. 1980. Ed. Contaminants and Sediments, Vols. 1 and 2.

Ann Arbor Science. Ann Arbor, MI.

Banerjee, S. 1984. Solubility of organic mixtures in water. Environ.

Sci. Technol., Vol. 18, No. 8, 587-591.

Bergman, H. L., and M. Crossey. 1983. Comments on the CH2M/Hill

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Black, J. J. 1982. Movement and Identification of a creosote-derived

PAH Complex Below a River Pollution Point Source. Arch. Environ.
Contam. Toxicol. 11:16.

Burns, L. A. 1982. Identification and Evaluation of Fundamental

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Arbor, MI.

CH2M/Hill. 1983. Phase I Report. Investigative Research and Remedial

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CH2M/Hill. 1984. Phase I11 Report. Remedial Action Feasibility

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Crossey, M. C. 1984. Comments on t h e C H 2 M / H i l l Phase I1 D r a f t R e p o r t , .
a t t h e r e q u e s t o f Marion Yoder, A s s t . Attorney G e n e r a l , S t a t e of
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Lech, J. J . , e t a l . 1978. S t u d i e s on t h e u p t a k e , d i s p o s i t i o n and

metabolism o f p e n t a c h l o r o p h e n o l and p e n t a c h l o r o a n i s o l e i n rainbow
t r o u t (Salmo g a i r d n e r i ) . I n : K. R. Rao ( e d . ) . , Pentachlorophenol:
Chemistry, Pharmacology and Environmental Toxicology. Plenum
P r e s s , New York. p . 107.

Lopez-Avila, V . , and R. A. H i t e s . (1983). Organic compounds i n a n

i n d u s t r i a l wastewater. Their t r a n s p o r t i n t o sediments. Environ.
S c i . Technol., Vol. 1 4 , N o . 11, 1382-1390.

Marle, C. M. 1981. Multi-phase Flow i n Porous Media. Gulf P u b l i s h i n g

Co. Houston, TX. 254 pp.

P i e r c e , R. H . , S. A. Gower, and D. M. V i c t o r . 1980. P e n t a c h l o r o -

p h e n o l and d e g r a d a t i o n p r o d u c t s i n l a k e sediment. i n : Contaminants
and Sediments. Vol. 2. R. A. Baker (ed.) . Ann Arbor S c i e n c e .
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U.S. EPA. 1980. Ambient Water Q u a l i t y C r i t e r i a f o r Pentachlorophenol.

EPA 440/5-80-065.

Uchrin, C. G . , and W. J. Weber, Jr. 1980. Modeling of T r a n s p o r t

P r o c e s s e s f o r Suspended S o l i d s and A s s o c i a t e d P o l l u t a n t s i n
River-Harbor-Lake Systems, i n : Contaminants and Sediments, V o l .
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27