Effects of Organic Wastes on 

Water Quality from Processing of -^w j . . , ' " o

X~*V " 1 f~^ 1 "I /** 1 Oil Shale from the 

Green River Formation, 

Colorado, Utah, and Wyoming

U.S. GEOLOGICAL SURVEY PROFESSIONAL PA PER 1338

Prepared in cooperation with the 

[f:S, Department of Energy
Effects of Organic Wastes on 

Water Quality from Processing of 

Oil Shale from the 

Green River Formation, 

Colorado, Utah, and Wyoming

By J. A. LEENHEER and T. I. NOYES

U.S. GEOLOGICAL SURVEY PROFESSIONAL PAPER 133

Prepared in cooperation with the 

U.S. Department of Energy

UNITED STATES GOVERNMENT PRINTING OFFICE, WASHINGTON : 1986
DEPARTMENT OF THE INTERIOR 

DONALD PAUL HODEL, Secretary

U.S. GEOLOGICAL SURVEY 

Dallas L. Peck, Director

Library of Congress Cataloging in Publication Data

Leenheer, J. A.

Effects of organic wastes on water quality from processing oil shale from the Green River Formation, Colorado, 

Utah, and Wyoming.

(Geological survey professional paper ; 1338)

Bibliography: p.

Supt. of Docs, no.: L19.16:1338

1. Oil-shale industry Waste disposal Environmental aspects Wyoming. 2. Oil-shale industry Waste disposal Environmental aspects Colorado. 3. Water quality Wyoming. 4. Water quality Colorado. 5. 

Organic water pollutants. 6. Biodegradation. I. Noyes, T. I. II. Title. III. Title: Green River Formation. IV. Series.

TD195.04L44 1985 363.7'394 84-600235

For sale by the

Books and Open-File Reports Section

U.S. Geological Survey

Federal Center

Box 25425 

Denver, CO 80225
CONTENTS

Page

Abstract ..... .... ........ ... ....... ....... 1

Introduction ... ... . . ...... . ............. . 2

Purpose and scope ...... ....................... 4

Acknowledgments ......... ............ ...... 5

Waste-characterization studies .... . . ......... ..... 5

Retort-wastewater characterization . ............. 5

Spent-shale characterization ..... ................ 8

Retort wastewater-spent shale interactions. .... ....... 11

Interactions of individual organic-solute fractions . .... 11

Synergistic interactions of organic-solute fractions

in whole retort wastewater ... . . . ............. 12

Comparison of spent shale as a sorbent with granular

activated carbon ....................... ..... 13

Subsequent studies of retort wastewafeer-spent shale

interactions . . ............. ........ ....... 14

Retort wastewater-soil interactions . . .... ............. 14

Batch-sorption experiments .... ...... ... .... 16

Soil column-sorption experiments . ..... ... .... .16

Physical and inorganic-constituent interactions .... .17

Organic-constituent interactions .... .... . ....... 22

Conclusions about retort wastewater-sorbent

interactions ..... .... .... . . ........ .... 26

Microbiological degradation of organic solutes in retort

wastewater ... ........ ... ................. . . 28

Effects of bacterial growth on dissolved organic-carbon 

concentration in Occidental-6 process and gascondensate retort wastewaters ................... 28

Microbiological degradation of organic solutes 

in retort wastewater Continued

Concurrent independent studies of microbial

degradation of organic solutes in retort wastewaters . 

Conclusions . . ............ ...... .........

Page

.29 

.30

Site studies of effects on water quality from oil-shale

retorting ........ .... ............... ........ 30

Effects of experimental in-situ reporting on ground

water near Rock Springs, Wyoming .......... .... 31

Soil survey of in-situ retorting site near Rock Springs,

Wyoming ... ..... .......... ........... . . 33

Rio Blanco modified in-situ retort site, Piceance Creek

Basin, Colorado ................... . . ... 34

Conclusions ....................... ....... . . 37

Characterization of natural organic solutes in waters

associated with oil shale in the Green River Formation . . 39 

DOC-fractionation surveys of surface and ground

waters...................................... 39

Isolation and fractionation of natural organic solutes

from water .............. .... ............ .40

Organic-solute characterization of ground water at the

Rio Blanco site, Piceance Creek Basin, Colorado .... 41

Organic-solute assessment of the White River ......... 44

Conclusions ................ .................. 53

Summary ....... ........ ....................... 54

References . .... ............. .... . ............ 55

ILLUSTRATIONS

Page

FIGURE 1. Map showing principal oil-shale deposits in the Green River Formation, Upper Colorado River Basin ........ 3

2. Sketch showing organic-carbon classification for organic-solute characterization... ........... .......... 6

3. Sketch showing analytical methods for dissolved organic-carbon (DOC) fractionation .... ........... . . 7

4-13. Graphs showing:

4. Sorption isotherms of dissolved organic-carbon fractions in 150-ton retort wastewater on TOSCO-II

processed shale. Preparative-scale dissolved organic-carbon fractionation preceded sorption ....... 12

5. Sorption isotherms of dissolved organic-carbon fractions in 150-ton retort wastewater on TOSCO-II

processed shale. Analytical-scale dissolved organic-carbon fractionation followed sorption...... . . 13

6. Conceptual model of sorption of organic solutes in retort wastewater during infiltration through a

TOSCO-II spent-shale column . . . ........ ........ ...... ............ ... . . 13

7. Sorption of organic solutes in 150-ton retort wastewater on Calgon F-400 activated carbon and

TOSCO-II spent shale ... . . .... . . ..... . .... ............ ............ ... 14

8. Sorption isotherm data for TOSCO-II spent shale normalized on elemental-carbon content ......... .15

9. Extraction isotherms of dissolved organic-carbon fractions from site-9 soil by Omega-9 retort wastewater 15

10. Sorption isotherms of dissolved organic-carbon fractions in Omega-9 retort wastewater on site-9 soil ... 16

11. Specific-condutance curves of soil-column effluents ........... .... ...... .... ....... .... 17

12. pH curves of soil-column effluents ... ... .............................. ... ......... .18

13. Color curves of soil-column effluents ... ....... .... ... .... .... . . .... ....... ... .19

14. Sketch showing soil-retort wastewater reactions. . ... ....... ... ....... ....... ... ... 20
IV CONTENTS

FIGURES 15-19. Graphs showing: Page

15. Flow-rate curves of soil columns . ... . . . . . ...... ...... ..... ... ........ 21

16. Thiocyanate curves* for soil-column effluents . . . ..... .................... 22

17. Copper curves for soil-column effluents . . . . . . . . . ..................... 23

18. Potassium curves for soil-column effluents ... . ... .... . . . . . ................. 24

19. Sulfate curves for soil-column effluents . . . . . . . . . . ... .... ................... 25

20. Chart of soil analyses for ammonia nitrogen .... . . . . . . . . ....... ... ............... 26

21-25. Graphs showing:

21. Dissolved organic-carbon curves for soil-column effluents . . ........... ... ............... 27

22. Percentage breakthrough curves for dissolved organic-carbon fractionation of Omega-9 retortwastewater leachate . . ... ... . . ... ... ... ..... . . ................... 28

23. Percentage breakthrough curves for aromatic amines in Omega-9 retort-wastewater leachate . . ...... 29

24. Growth curve of microorganisms in inoculated flask I, Occidental-6 process retort wastewater ........ 30

25. Growth curves of microorganisms in inocluated flask II, Occidental-6 process retort wastewater ....... 31

26. Map showing location of experimental in-situ retorting sites near Rock Springs, Wyoming ....... ......... 32

27. Map of wells at the site-9 in-situ retorting experiment near Rock Springs, Wyoming ... . . . ............. 33

28. Soil map of experimental in-situ retorting site near Rock Springs, Wyoming . . . ....................... 35

29. Sketch showing flow of water through mobile laboratory . . . . . . ... ............... 42

30. Sketch showing flow of water through filtration and column-adsorbent system ..... ........ ........... 43

31. Graph showing infrared spectrum of organic acids of ground water in well D-8 . . . . ........ ........ 44

32. Proton nuclear magnetic resonance (NMR) spectrum of organic acids of ground water in well D-8 ............ 45

33-35. Graphs showing:

33. Infrared spectra of humic acids of the White River; river sampled September 1981 . . ............. 49

34. Infrared spectra of strong hydrophobic- and hydrophilic-acid no. 1 fractions of the White River; river

sampled September 1981 . . . . . ....... ... . . . ... . . .... ............ 49

35. Infrared spectra of acid fractions of the White River; river sampled June 1982 ..................... 51

36. Proton nuclear magnetic resonance (NMR) spectra of acid fractions of the White River; river sampled June 1982... 52

TABLES

Page

TABLE 1. Compound groups found in dissolved organic-carbon fractions in oil-shale retort wastewater .................... 8

2. Dissolved organic-carbon fractionations of various oil-shale retort wastewaters ............................... 8

3. Organic-solute analyses of Occidental-6 process and gas-condensate retort wastewaters ........................ 9

4. Inorganic-solute analyses of Omega-9 and 150-ton retort wastewaters.................. ................... 11

5. Concentration of major inorganic sulfur species in four retort wastewaters. .................................. 11

6. Ionic mass balance for ions adsorbed and eluted from soil columns......................................... 20

7. Cation-exchange capacity contributions of Haterton soil constituents ........... .......................... 26

8. Comparison of soil- and liquid-chromatographic-column capacity factors (fe') for aromatic amines ................ 30

9. Dissolved organic-carbon fractionation of sample removed at start of microbial growth in Occidental-6 process

retort wastewater, and at 16 and 32 hours after start of experiment..................................... 31

10. Dissolved organic-carbon fractionations of various waters sampled at and near experimental in-situ retorting site 9

near Rock Springs, Wyoming .................................................................. 34

11. Concentration of thiocyanate, thiosulfate and tetrathionate, and ammonia in water from site-9 wells near Rock

Springs, Wyoming . .................. ................... ................................. 34

12. Chemical analyses of ground waters sampled May 5, 1981, Rio Blanco retort site, Piceance Creek Basin, Colorado. . . 36

13. Inorganic analyses of wastewaters sampled November 19, 1982, from backflooded Rio Blanco retort 1, Piceance

Creek Basin, Colorado ....................................................................... 36

14. Organic analyses of wastewaters sampled November 19, 1982, from backflooded Rio Blanco retort 1, Piceance Creek

Basin, Colorado ............... ............................................................ 38

15. Dissolved organic-carbon fractionations of various surface and ground waters associated with oil shale in the

Green River Formation ... .............................................. .................... 40

16. Variability of dissolved organic-carbon fractionations for 10 surface waters sampled in the White River Basin, Utah,

November 1975 ......... ................................................................... 40

17. Elemental analyses of organic-solute fractions from Rio Blanco well D-8, Piceance Creek Basin, Colorado .......... 42

18. Quantitative organic structural- and functional-group information on well D-8 organic acids .................... 46

19. Organic-carbon recoveries from the White River using filtration and column-adsorbent system ................... 47

20. Subfractionation of strong hydrophobic- and hydrophilic-acid fractions from the White River, sampled September 1981.47

21. Chemical analyses of organic-solute fractions from the White River, sampled September 1981 .................... 47

22. Elemental analyses of organic-solute fractions isolated from the White River, sampled September 1981 ............ 48

23. Chemical and elemental analyses of organic-solute fractions isolated from the White River, sampled June 1982. ..... 50

24. Quantitative organic structural- and functional-group information on organic-acid fractions from the White River,

sampled June 1978 ...... ........... ..... .............................................. 53
CONVERSION FACTORS

Multiply SI unit By To obtain inch-pound unit

Length

micrometer (^m) 

millimeter (mm) 

centimeter (cm) 

meter (m) 

kilometer (km)

0.00003937 

0.03937 

0.3937 

3.281 

0.6214

inch (in.) 

inch (in.) 

inch (in.) 

foot (ft) 

mile (mi)

Volume

milliliter (mL) 

liter (L) 

cubic meter (m3 )

0.03382 

0.2642 

8.3864

ounce, fluid (oz) 

gallon (gal) 

barrel, U.S., liquid

Mass

milligrams (mg) 

gram (g) 

megagram (Mg)

0.00001543 

0.03527 

1.1023

ounce, avoirdupois (oz) 

ounce, avoirdupois (oz) 

ton, short (t)

Flow

liter per minute (L/min) 0.2642 gallon per minute 

(gal/min)

Concentration

milligram per liter (mg/L) 

microgram per liter (^g/L) 

liter per megagram ( L/Mg )

1.000 

0.001 

0.2402

part per million (ppm) 

part per million ( ppm ) 

gallon per ton (gal/t)

Temperature

degree Celsius (°C) F = 9/5°C + 32 degree Fahrenheit (°F)

Specific Conductance

microsiemens per 

centimeter at 25° 

Celsius (^S/cm)

1.000 micromho per centimeter 

at 25° Celsius 

(p-mho/cm at 25°C)

National Geodetic Vertical Datum of 1929 (NGVD of 1929): A geodetic datum derived from a 

general adjustment of the first-order level nets of both the United States and Canada, formerly 

called "mean sea level." NGVD of 1929 is referred to as sea level in this report.

Use of brand and firm names in this report is for identification purposes only and does not 

constitute endorsement by the U.S. Geological Survey.

EFFECTS OF ORGANIC WASTES ON WATER QUALITY FROM PROCESSING OF

OIL SHALE FROM THE GREEN RIVER FORMATION,

COLORADO, UTAH, AND WYOMING

By J. A. LEENHEER and T.I. NOYES

ABSTRACT

A series of investigations was conducted during a 6-year research 

project to determine the nature and effects of organic wastes on 

water quality from processing oil shale from the Green River 

Formation. These investigations included retort-wastewater and 

spent-shale characterization, determination of sorptive characteristics and chemical interactions between soil and spent shale, 

laboratory studies of microbiological degradation of organic constituents in retort wastewater, onsite studies of water-quality 

effects resulting from in-situ oil-shale retorting in Wyoming and 

Colorado, and characterization of natural organic solutes in waters 

associated with oil shale.

An analytical method, dissolved organic-carbon fractionation 

analysis, was developed to classify complex organic-solute mixtures found in natural waters and retort wastewaters, into hydrophobic-acid, -base, and -neutral compound groups. Analytical 

methods were applied to each organic-solute fraction to determine 

quantitatively the organic solutes in a process retort wastewater 

and a gas-condensate retort wastewater produced in a modified 

in-situ oil-shale retort. Fifty percent of the dissolved organic 

carbon was identified as specific compounds in both retort wastewaters. In the process retort wastewater, 42 percent of the dissolved organic carbon consisted of a homologous series of fatty 

acids from C^ to CIQ. Dissolved organic-carbon percentages for 

the other compound classes were as follows: aliphatic dicarboxylic 

acids, 1.4 percent; phenols, 2.2 percent; hydroxypyridines, 1.1 

percent; and aliphatic amides, 1.2 percent. In the gas-condensate 

retort wastewater, aromatic amines were most abundant at 19.3 

percent of the dissolved organic carbon, followed by phenols (17.8 

percent), nitriles (4.3 percent), aliphatic alcohols (3.5 percent), 

aliphatic ketones (2.4 percent), and lactones (1.3 percent). Steamvolatile organic solutes were enriched in the gas-condensate retort 

wastewater, whereas nonvolatile acids and polyfunctional neutral 

compounds were predominant organic constituents of the process 

retort wastewater.

Thiosulfate and thiocyanate were major constituents in four 

retort wastewaters derived from combustion-type processing of 

oil shale. Thiosulfate was the predominant sulfur species with 

concentrations ranging from 420 to 2,200 milligrams per liter. 

Thiocyanate concentrations ranged from 24 to 720 milligrams 

per liter.

The surface chemistry of TOSCO-11 spent shale was assessed 

by determination of its cation- and anion-exchange capacities, 

determination of surface electrical charge, and spectroscopic

studies of its carbonaceous coating after chemical dissolution 

of the mineral matrix. The cation-exchange capacity (3 milliequivalents per 100 grams) was less than that of most soils, but 

the anion-exchange capacity (1 milliequivalent per 100 grams) 

was similar to that of soils. The electrical charge of the spent 

shale is zero at pH 8.5. The carbonaceous coating on the spent 

shale primarily is elemental carbon with few oxygenated functional groups.

Batch-equilibrium sorption studies,using TOSCO-II spent shale 

as the sorbent and combustion-type retort wastewater, determined 

that the spent shale is a very effective sorbent for organic solutes. 

The carbonaceous coating of the spent shale had a sorptive capacity equivalent to that of granular activated carbon. Hydrophobic 

organic solutes had the expected greater sorptive capacities than 

did hydrophilic organic solutes, but acid solutes had much greater 

sorptive capacities than normally found on natural sediment 

sorbents. It is this capacity for acid sorption that makes TOSCOII spent shale an effective sorbent for retort organic wastes 

codisposed with spent shale.

Chemical and physical interactions of an in-situ oil-shale retort 

wastewater with a surface soil were investigated. Major findings 

of this study include an ion exchange-precipitation reaction in 

which exchangeable calcium in the soil is displaced by ammonium 

from retort wastewater and precipitated as carbonate by inorganic 

carbon in retort wastewater. This precipitation process decreases 

soil permeability. Ammonium was strongly adsorbed from retort 

wastewater by the soil and was not removed from the soil by 

subsequent distilled-water leaching and drying. The soil absorbed 

about 40 percent of organic solutes from retort wastewater in 9.4 

pore volumes of leachate; retort wastewater extracted significant 

quantities of natural fulvic and humic acids from the soil. The soil 

adsorbed variable quantities of ammonium, arsenic, barium, boron, 

cadmium, cobalt, copper, fluoride, inorganic carbon, iron, silica, 

and zinc from retort wastewater. Exchangeable calcium, magnesium, 

manganese, lithium, potassium, sodium, and strontium were extracted 

from the soil by ammonium in the retort wastewater. Thiocyanate 

did not interact and was the best tracer, under these conditions, 

for retort wastewater. Thiosulfate in retort wastewater was degraded 

to tetrathionate by passage through the soil columns.

Dissolved organic-carbon fractionation analyses of the soilcolumn effluent determined the following order of increasing affinity of the six organic-compound classes in retort wastewater for 

soil: hydrophilic neutrals nearly equal to hydrophilic acids, followed by hydrophobic acids, hydrophilic bases, hydrophobic bases,

1
EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING

and hydrophobic neutrals. Liquid-chromatographic analysis of 

the aromatic amines in the hydrophobic- and hydrophilic-base fractions showed that the relative order of the rates of migration 

through the soil column as the same as the order of migration on a 

reversed-phase, octadecylsilica liquid-chromatographic column, in 

which the retention of the amine increased with its hydrophobicity.

Microbiological degradation of organic solutes in retort wastewaters was determined to occur preferentially in hydrocarbons and 

fatty-acid groups of compounds. Aromatic amines did not degrade 

and they inhibited bacterial growth where their concentrations were 

significant in a gas-condensate retort wastewater. Thiosulfate was 

converted to polythionates and sulfate during bacterial growth.

Effects of true in-situ retorting on ground-water quality was 

studied near Rock Springs, Wyoming, and modified in-situ retorting was studied at the Rio Blanco site in the Piceance Creek Basin, 

Colorado. True in-situ retorting produced retort wastewater in 

direct contact with native ground water, but no appreciable migration of contaminants occurred as much as 3 years after the burn 

because ground-water flow was toward the previously dewatered 

retort. Ammonia, aromatic amines, and thiocyanate persisted in 

the contamined ground water, but thiosulfate was quantitatively 

degraded 1 year after the burn. A first-order soil survey of the 

retort site at Rock Springs was performed to assess potential 

interactions between soils and retort wastewaters. Shallow permeable soils occur in the upland regions, whereas relatively impermeable sodic soils occur on the alluvium near watercourses.

Retort wastewaters and gases produced in the modified insitu retort at the Rio Blanco site did not contaminate adjacent 

ground waters during the burn because of drawdown due to dewatering of the retort and because of negative gas pressure in 

the retort during the burn. However, ground-water contamination during any future backflooding of the retort after retort 

abandonment poses the main potential for adverse effects on 

ground-water quality.

Natural organic solutes isolated from ground water in contact 

with oil shale in the Green River Formation and from the White 

River, which receives the discharge from the Piceance Creek Basin 

being developed for oil-shale resources, were characterized by 

chemical and physical methods. This characterization included 

elemental analyses, derivatization of carboxyl, carbonyl, and hydroxyl functional groups, infrared spectroscopy, and proton nuclear 

magnetic resonance spectroscopy of both derivatized and underivatized fractions. Organic solutes in ground water were distinguished from organic solutes in surface water by the absence of 

protons associated with hydroxyl, ester, and ether functional groups 

in ground water compared to surface-water organic solutes. In the 

White River, polysaccharides and uronic acids were detected in 

both the humic-acid and hydrophilic-acid fractions, whereas these 

components were nearly absent in the fulvic-acid fraction. Amide 

groups were detected predominately in the humic-acid fraction in 

the White River. Identified biopolymers, as determined by percentages of polysaccharide, uronic acid, and amide moieties, were 

approximately 10 times as abundant in the White River in September at base flow than in June at peak flow. Seasonal changes in 

organic solutes in the White River are believed to be due to 

autochthonous production of organic solutes during base-flow 

periods in the summer and fall, and allocthonous inputs of terrestrial organic solutes during peak flow in the spring.

Concentrations of dissolved organic carbon found in natural 

surface and ground waters (1 to 5 milligrams per liter) in the 

Piceance Creek Basin were 2 to 4 orders of magnitude less than 

those found in retort wastewaters (500 to 500,000 milligrams per 

liter). Organic contaminants of retort origins primarily are small 

molecular-weight monomeric compounds, whereas natural organic 

solutes are complex heterogeneous polymers of biological origin.

INTRODUCTION

Oil shale in the Green River Formation is the most 

promising deposit for synthetic-fuels production in the 

United States. Total oil reserves in known deposits of 

oil shale yielding more than 18.9 L of oil equivalent 

per megagram have been estimated at 636 billion m3 

(Duncan and Swanson, 1965) and economically recoverable reserves have been estimated at 48 billion m3 

(Donnell and Blair, 1970). Currently (1983), no significant production of shale oil has occurred in the United 

States; but several oil-shale conversion technologies have 

been developed and tested, which led to projections by 

the Office of Technology Assessment of shale-oil production goals of as much as 160,000 m3 per day by 1990 

(Sladex and others, 1980). However, given the current 

economic limitations of oil-shale development, perhaps a 

more realistic projection is that significant production of 

shale oil is still 10 to 20 years in the future (Barry, 1981).

The Green River Formation was formed from sediments deposited in interconnected stratified lakes that 

existed during the Eocene Epoch (Bradley, 1930). These 

lake sediments consisted of a mixture of partly degraded 

aquatic organisms that resisted complete decay because 

of reducing conditions at the lake bottom, mineral matter of fluvial and aeolian origin, and precipitate and 

evaporite minerals formed during minimum or dry stages 

of these lakes. These lakes existed for several million 

years and lake sediments accumulated to thicknesses of 

as much as 1,100 m. The location of the principal oilshale deposits in the Green River Formation is shown in 

figure 1.

Oil shale in the Green River Formation ranges from 7 

percent organic matter by weight for low-grade oil shale 

to as much as 35 percent for high-grade oil-shale. The 

organic matter typically is distributed uniformly through 

an inorganic marlstone matrix that principally is composed of dolomite and calcite with lesser quantities of 

plagioclase, illite, quartz, analcite, and orthoclase 

(Hendrickson, 1975). From 5 to 15 percent of the organic 

matter is solvent-extractable bitumens, and the remainder is defined as kerogen (Robinson, 1969). Extensive 

studies of kerogen in the oil shale indicate that it is 

composed principally of aliphatic cyclic structures with 

the majority of oxygen present as ester and ether bridges 

between structural units (Robinson, 1969). When heated 

to 500°C, about 80 percent of the organic carbon in the 

oil shale is converted to shale oil.

The thickest and highest grade oil shale occurs in the 

Piceance Creek Basin (fig. 1); consequently, the major 

oil-shale industry probably will develop in Colorado. A 

lesser development probably will occur in the Uinta Basin 

of Utah because of accessibility of thinner zones of highgrade oil shale with little or no overburden in limited
36C

35°

GREEN RIVER FORMATION 

CONTAINING OIL SHALE

SHALE 5 OR MORE METERS 

THICK ANDAVERAGING 56 

OR MORE LITERS OF OIL 

PER TON

SHALE 3 OR MORE METERS 

THICK AND AVERAGING 94 

OR MORE LITERS OF OIL 

PER TON

BOUNDARY OF UPPER 

COLORADO RIVER BASIN

NEW/MEXICO

100 200 KILOMETERS

I 

100 MILES

FIGURE 1. Principal oil-shale deposits in the Green River Formation, Upper Colorado River Basin (modified from

Rickert and others, 1979).
EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING

areas. The Colorado, White, and Green Rivers drain 

these areas and will be affected directly by development 

of the oil-shale resource. Extensive studies have been 

made to determine the effects of oil-shale retorting on the 

hydrology (Weeks and others, 1974) and ground-water 

quality (Robson and Saulnier, 1980; Slawson, 1980) of 

the Piceance Creek Basin.

The nature and quantity of solid, liquid, and gaseous 

wastes produced by retorting of oil shale are very dependent on the type of retorting technology. Summaries of 

various oil-shale retorting technologies, which have been 

tested using oil shale from the Green River Formation, 

are given by Dinneen (1976), Hendrickson (1975), and 

Yen (1976). As retorting temperatures increase, five types 

or zones of spent-shale products have been identified in 

an in-situ retort, each with major chemical and physical 

property differences (Krause and McLean, 1980). These 

zones were described by Krause and McLean (1980) as 

follows:

Zone 1. Black carbonized shale, thin-bedded, fissile; 

Zone 2. Same as zone 1, except light gray to tan

and brown, soft;

Zone 3. Light gray to tan, very soft, "frothy" appearance due to presence of coalescing 

vugs, bedding and fissility substantially 

gone;

Zone4. Variegated greens, black, gray, brown, 

yellow; very porous; fused; clinker-type 

material, hard; not friable; remnant 

bedding present, but not pronounced; 

and 

Zone 5. Buff tan, very soft, similar to zone 3 except

vugs absent.

Water-leaching studies of each zone produced pH 

values as much as 11.5 for zones 3 and 5, and dissolvedsolids concentrations as much as 10,000 mg/L for zone 3. 

The presence of free lime in zones 2-5 produced high 

pH solutions corrosive to silicate minerals.

Because of the somewhat limited and thus expensive 

water resources, the semiarid environment, and wastedischarge restrictions where oil shale occurs, it is most 

likely that the various wastewater streams generated 

by oil-shale industries will be used for spent-shale disposal after some degree of water treatment. Questions 

raised by codisposal of wastewater with spent shale 

include: (1) What is the mobility of wastewater and its 

dissolved constituents within spent shale; (2) what is 

the mobility of wastewater and its dissolved constituents 

within soils and sediments adjacent to spent-shale dumps; 

(3) what are the chemical, physical, and toxilogical 

characteristics of the mix of spent shale and wastewater; 

and (4) how do weathering processes affect spent shalewastewater or soil-wastewater combinations?

In-situ retorting of oil shale poses additional questions regarding water-quality effects: (1) What is the 

fate and water-quality effects of unrecovered retort 

wastewater and shale oil; (2) what is the nature of spent 

shale in an underground retort; (3) what happens to 

spent shale and ground-water quality during and after 

backflooding by ground water of a burned in-situ retort; 

(4) what are the implications of potential physical instability (subsidence) of the retort on ground-water quality; 

and (5) is a burned retort a potential repository for 

wastewaters produced by an associated surface-retorting 

operation?

These questions can only be addressed partly by laboratory and pilot-plant studies; more complete answers to 

these questions are pending development of a full-scale 

shale-oil industry. However, research studies of potential 

water-quality effects related to oil-shale processing should 

aid both the public and private sectors in designing and 

selecting a shale-oil technology that is both efficient and 

environmentally acceptable.

Wastewater from oil-shale processing originates from: 

retorting operations, shale-oil upgrading operations, airemissions-control and gas-cleaning systems, blowdown 

from cooling water and boiler systems, mine dewatering, 

and sanitary-treatment systems. Wastewater from oilshale processing indirectly originates from: leachates 

from raw-shale storage, retorted-shale disposal areas, 

runoff from construction and onsite use, and runoff from 

mining and transport activities (Crawford and others, 

1977). Wastewaters from retorting and gas-cleaning operations contain the largest quantities of organic constituents (Jackson and others, 1975). In-situ retorting operations 

typically generate more wastewater and less surfacedisposed spent shale than do surface retorting operations, 

but more spent shale per unit volume of shale oil is 

produced in the subsurface by in-situ retorting because 

this method is less efficient. Volatile wastewater constituents may be transformed into gaseous wastes by 

wastewater reuse in the retorting and upgrading operations, 

or they may be recovered as valuable byproducts such as 

ammonia and sulfur (Probstein and Gold, 1978).

Approximately 50 percent of the net water consumption of oil-shale technologies using surface retorting has 

been attributed to spent-shale disposal (Probstein and 

Gold, 1978), the other 50 percent of the water is used in 

retorting operations. Water is used in spent-shale disposal for dust control, moisturization to aid in compaction, 

and for re vegetation.

PURPOSE AND SCOPE

Given the magnitude of the oil-shale resource in the 

Green River Formation and the potentially significant 

effects that its development eventually will have on 

water quality and quantity, the U.S. Geological Survey
WASTE-CHARACTERIZATION STUDIES

has been conducting water-resources investigations for 

the past several years on oil-shale development (O. J. 

Taylor, U.S. Geological Survey, written commun., 1983). 

The purpose of this report is to summarize the results 

of a 6-year investigation of the various effects on water 

quality of organic wastes from processing of oil shale 

from the Green River Formation.

This report focuses on liquid and solid organic wastes 

present after oil-shale processing. Organic constituents 

have received less attention and evaluations in other 

water-quality studies related to shale-oil processing. 

These constituents comprise a major part of the wastes 

because of the organic nature of oil-shale and shaleoil products.

This report will address most of the previously posed 

questions regarding water-quality effects with respect to 

organic constituents in wastewater through a discussion 

of a series of onsite and laboratory investigations. Related chemical and hydrologic studies also will be discussed 

to provide a more comprehensive assessment of waterquality effects resulting from oil-shale processing.

ACKNOWLEDGMENTS

The original interest of Lee C. Butcher and the counsel 

of John D. Hem were beneficial in establishing goals and 

providing direction during the initial stages of this study. 

Robert C. Averett and Robert L. Wershaw provided 

direction during the middle and latter stages of this study.

The Laramie Energy Technology Center, U.S Department of Energy, Laramie, Wyoming, provided significant financial support from 1977 to 1980 as administered 

by David S. Farrier and David C. Sheesley. Richard E. 

Poulson and Larry P. Jackson also provided much encouragement and direction. The wastewater samples from 

the Omega-9, Occidental-6, and 150-ton retorts were provided by the Laramie Energy Technology Center.

The Oil Shale Corporation (TOSCO) graciously provided the TOSCO-II spent shale, and Geokinetics Corporation cooperated in the sampling of their in-situ spent 

shale and retort wastewaters. Rio Blanco Oil Shale Corporation was very helpful in the sampling of their modified in-situ mine waters and retort wastewaters.

Professor Patrick McCarthy and Steve Cowling, Colorado School of Mines, and Professor Steven Williams and 

W. Kennedy Gauger, University of Wyoming, provided 

critical elements to this study through research grants. 

Professor Harold Walton, University of Colorado, was 

advisor to Harold A. Stuber's dissertation research supported by this project.

Special thanks is accorded to Glen A. Miller of the 

Area Oil Shale Office, Bureau of Land Management, 

U.S. Department of the Interior, Grand Junction, Colorado, 

who facilitated cooperative studies with government and

industry. Lastly, the major contributions to project research 

of Harold A. Stuber, U.S. Geological Survey, from 1977 

to 1982 need to be acknowledged. His doctoral dissertation on aromatic amine analyses and papers on reduced 

sulfur species in retort wastewater were major original 

contributions to the science.

WASTE-CHARACTERIZATION STUDIES

Most of the water-characterization effort focused on 

wastewaters from various oil-shale retorts because little 

was known about their composition at the beginning of 

this investigation. A more limited investigation was 

conducted on the chemical and physical properties of the 

carbonaceous coating on spent oil shale to determine the 

significance of these coatings with respect to sorptive 

interactions with retort wastewaters.

RETORT-WASTEWATER CHARACTERIZATION

At the beginning of this investigation in 1976, the 

state of knowledge of the properties of retort wastewater 

was summarized by Jackson and others (1975) and 

Hendrickson (1975). It then was recognized that ammonium bicarbonate was the primary dissolved constituent 

accompanied by lesser quantities of sodium, sulf ate, and 

chloride. Significant concentrations of dissolved organic 

constituents were known to be present, as evidenced by 

dissolved organic-carbon concentrations, odor, and color. 

Fatty acids and amines were known to be major organic 

constituents; phenols were of lesser significance. Major 

problems in studies of retort-wastewater characterization were the volatility of several dissolved constituents, 

difficulty in accurate determination of organic-carbon 

content because of volatile organic constituents in addition to large carbonate and bicarbonate concentrations, lack of solvent extractability of many dissolved 

organic constituents, and major discrepancies in anioncation balances after a standard, complete waterchemistry analysis.

A major problem was the inadequacy of organic-solute 

characterization data. A characterization of compound 

classes of organic solutes was needed because comprehensive analyses of specific organic compounds was not 

practicable using available methods. Because of the poor 

solvent extractability of many retort-wastewater organic constituents, a method was developed for compoundclass characterization based on adsorbent-resin fractionations rather than solvent-extraction fractionations.

Accordingly, an organic-compound class f ractionation 

called "dissolved organic-carbon (DOC) f ractionation' 1 

was developed that could be applied to both oil-shale 

retort wastewaters and natural waters (Leenheer and 

Huffman, 1976). The tiered organic-solute classification
6 EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING 

1. Organic-load parameter Dissolved organic carbon

2. Solute - sorption parameters

3. Solute acid-base characteristics based on organic carbon (a) Acids

(a) Hydrophobic organic carbon (b) Hydrophilic organic carbon

4. Solute compound classes

5. Specific solute compounds

6. Solute complexes (both 

organic and inorganic)

Anionic 

detergents

(b) Neutrals

Chlorinated 

hydrocarbon 

insecticides

(c) Bases

Polynuclear 

amines

(d) Acids

Polyuronic 

acids

(e) Neutrals

Polysaccharides

(f) Bases

Amino 

sugars

FIGURE 2. Organic-carbon classification for organic-solute characterization (from Leenheer and Huffman, 1976).

based on DOC fractionation is shown in figure 2 and the 

standard analytical methods (Leenheer and Huffman, 

1979) for DOC fractionation is shown in figure 3.

The organic-compound groups present in oil-shale retort 

wastewater that are separated in the various stages of 

DOC fractionation are shown in table 1, the data are 

based on a recent study of specific organic compounds in 

oil-shale retort wastewater (Leenheer and others, 1982). 

DOC fractionation of seven different oil-shale retort 

waste waters are shown in table 2. Process retort wastewaters typically are found as an emulsion in the raw 

shale-oil product from a retort, and gas-condensate retort 

wastewaters are obtained when hot retort vapors cool 

and condense. Some in-situ retorts do not separate process and gas-condensate retort wastewaters, and some 

surface retorts that recirculate retort gases back into the 

retort do not produce gas-condensate retort wastewaters. 

The volumes and properties of retort wastewaters are 

dependent on the nature of the retort and the mode of 

retort operation. The retort-wastewater samples in table 

2 were obtained from the Laramie Energy Technology 

Center, except for the Geokinetics sample obtained from 

Geokinetics Corporation near Vernal, Utah.

The following conclusions can be drawn from the data 

in table 2: (1) Retort wastewaters of all types generally 

have greater organic-base percentages compared to natural waters whose organic-base content is only 5 to 10 

percent of the DOC concentration (Stuber and Leenheer, 

1978b); (2) in-situ and gas-condensate retort wastewaters 

have smaller organic-solute (DOC) concentrations than

process retort wastewaters; (3) retort wastewaters, containing significant DOC concentrations, such as the Paraho 

and Occidental-6 process retort wastewaters, are greatly 

enriched in hydrophilic acids, probably because of the 

greater solubility of this fraction relative to the other 

fractions; (4) process retort wastewaters in general are 

enriched in acid solutes, and gas-condensate retort wastewaters are enriched in basic and neutral solutes because 

of steam-volatility partitioning (Leenheer and others, 

1982); and (5) DOC fractionation patterns for the two insitu retort wastewaters indicate these waters are a mixture of process and gas-condensate retort wastewaters.

The Occidental-6 process and gas-condensate retort 

wastewaters were fractionated by a preparative DOC 

fractionation procedure (Leenheer, 1981), and the various fractions were analyzed for specific organic compounds (Leenheer and others, 1982). Results of these 

analyses are shown in table 3. Aliphatic-monocarboxylic 

acids from Ci to Cio are by far the most abundant group 

of compounds in the process retort wastewater, but they 

only constitute 0.36 percent of the DOC in the gascondensate retort wastewater, because ionization of carboxyl groups at pH 8.6 of retort wastewater limits the 

volatility of aliphatic-monocarboxylic acids. Other organic components detected in lesser quantities in process 

retort wastewater include aliphatic-dicarboxylic acids, 

aromatic-carboxylic acids, thiocyanate, phenols, aromatic amines, hydroxypyridinines, aliphatic amides, nitriles, 

aliphatic ketones, and lactones.

Organic solutes in the gas-condensate retort wastewater
WASTE-CHARACTERIZATION STUDIES

STEP 1 STEP 2 

200 milliliters Elute with 

filtered sample 0.1 N hydrochloric 

at pH 7 acid 

DOC 1

-Adjust sample pH to 2 with 

hydrocholic acid DOC 2

STEP 3 

Sample at pH 2

STEP 4

Elute with

0.1 N sodium

hydroxide

I

3 milliliters Amberlite XAD 8 resin

DOC 3

DOC 4

3 milliliters

AG-MP-50 BIO RAD H + saturated

Cation exchange resin

DOC 5

6 milliliters

AG-MP-1 BIO RAD OH'saturated

Anion exchange resin

DOC 6 

CALCULATIONS

Hydrophobic DOC (milligrams per liter)

Total =DOC 1 -DOC 4

eluate volume 

Bases = DOC 2 x

sample volume 

eluate volume Acids = DOC 3 x 

sample volume

Neutrals = Total Bases Acids

Hydrophilic DOC (milligrams per liter) 

Total = DOC 4 

Bases = DOC 4-DOC 5

Acids = DOC 5 - DOC 6 

Neutrals = DOC 6

FIGURE 3. Analytical methods for dissolved organic-carbon (DOC) fractionation (from 

Leenheer and Huffman, 1979).

consist mainly of phenols and aromatic amines with 

lesser quantities of nitriles, aliphatic alcohols, aliphatic 

ketones, and lactones. Aromatic amines are mainly responsible for the disagreeable odor of retort wastewaters, and 

the quinolines found in this compound group are some of 

the most toxic organic constituents found in retort 

wastewaters. Generally speaking, monofunctional organic compounds found in retort wastewaters are limited to 

10 carbons or less, because greater molecular-weight 

components, being more insoluble in water, partition 

into shale oil produced with retort wastewaters. Specific 

information on low solubility, solvent-extractable organic compounds in Occidental-6 retort wastewaters is presented in a report by Raphaelian and Harrison (1981).

A second area of research in retort-wastewater characterization is the nature of dissolved sulfur species. Inorganic analyses of major constituents in Omega-9 and

150-ton retort wastewaters are shown in table 4. Comparison of the total sulfur concentration in Omega-9 retort 

wastewater with the sulfate indicated significant quantities of dissolved sulfur species other than sulfate. Acidification of retort wastewaters was found to produce elemental 

sulfur, which is characteristic of certain reduced sulfur 

species. Four retort wastewaters were tested for sulfide, 

polysulfide, sulfite, thiosulfate, polythionate, and thiocyanate anions (Stuber and others, 1978). Most of the 

missing sulfur was accounted for by thiosulfate, tetrathionate, and thiocyanate, as shown by data in table 5. 

Discovery of these reduced sulfur species prompted other investigators, such as Fox and others (1978), to conduct comprehensive inorganic analyses resulting in 

complete anion-cation balances. Recent research (Wallace 

and others, 1981) has shown that most of reduced sulfur 

in retort wastewater is present initially as sulfide that
EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING

TABLE 1. Compound groups found in dissolved organic-carbon 

fractions in oil-shale retort wastewater

Organic-carbon fraction

Hydrophobia organic carbon 

Bases:

Hydrophilic organic carbon 

Bases:

One- and two-ring aromatic amines except 

pyridine.

Aliphatic monocarboxylic carboxylic acids 

of 5 to 11 carbons, 1-ring aromatic 

carboxylic acids, 8 to 11 carbon 

aliphatic dicarboxylic acids and 

phenols.

Aliphatic and aromatic hydrocarbons, 

aliphatic amides and alcohols greater 

than five carbons, aliphatic ketones and 

nitriles greater than four carbons, 

aromatic nitriles and amides, thiophenes, 

thiazoles, furans, pyrroles, lactones.

Hydroxypyridines, pyridine carboxylic

acids, aliphatic amines, pyridine. 

Aliphatic monocarboxylic acids of one to

five carbons, aliphatic dicarboxylic

acids of two to seven carbons,

thiocyanate. 

Aliphatic amides and alcohols of one to

four carbons, aliphatic nitriles, and

aldehydes of two to three carbons,

acetone, urea.

degrades during refrigerated storage at the rate of 20 

percent per day to thiosulfate and polythionates. Thiosulf ate degrades at a more moderate rate to polythionates 

and eventually sulf ate (Stuber and others, 1978; Leenheer 

and others, 1981).

SPENT-SHALE CHARACTERIZATION

The nature of the carbonaceous coating on spent shale, 

resulting when shale is retorted at low temperature, was 

the topic of a Master's thesis by Cowling (1979). This 

research, funded by the U.S. Geological Survey, was 

conducted to evaluate TOSCO-II spent shale as a sorbent for retort wastewaters. Specialized procedures had 

to be developed to determine exchange capacities and 

pH of the zero point of charge because of the calcareous 

and gypsiferous nature of spent shale.

Ion-exchange procedures were developed that omitted 

the wash step between the ionic-saturation steps and 

ionic-replacement steps to minimize dissolution of sparingly soluble minerals in the spent shale. Isopropanol 

was used as a tracer to correct for the volume of solution 

remaining in the moist shale after the saturation step. 

Cation-exchange capacity determinations varied between 

2 and 3 meq/100 g (milliequivalents per 100 grams), and

TABLE 2. Dissolved organic-carbon fractionations of various oil-shale retort wastewaters

[in percent]

Fraction

Total hydrophobic

solutes .

Total hydrophilic

solutes.

Hydrophobic bases.

Hydrophobic acids .

Hydrophobic

neutrals.

Hydrophilic bases.

Hydrophilic acids.

Hydrophilic

neutrals .

Total bases.

Total acids.

Total neutrals.

Dissolved organic

carbon, in

milligrams per

liter.

Omega-9 1

retort

wastewater

(in-situ

retort)

49

51

13

19

17

12

29

10

25

48

27

977

Geokinetics 2

retort

wastewater

(in-situ

retort)

60

40

12

21

27

10

13

17

22

34

44

980

150-ton1

retort

wastewater

(simulated

in-situ

surface

retort)

55

45

9

26

20

15

15

15

24

41

35

5,140

10-ton 1

retort

wastewater

(simulated

in-situ

surface

retort)

36

64

6

16

14

12

40

12

18

56

26

2,940

Occidental-6

process 1

retort

wastewater

(modified

in-situ

retort)

44

56

5

28

11

9

39

8

14

67

19

3,000

Occidental-6

gas-condensate 1

retort

wastewater

(modified

in-situ

retort)

68

32

24

19

25

12

9

11

36

28

36

790

Paraho 1

process

retort

wastewater

(surface

retort)

16

84

2

10

4

5

73

6

7

83

10

54,800

Natural surface

water, White

River Basin,

Utah

(means of

10 samples)

43

57

.3

36

7

7

40

10

7

76

17

7.3

'Obtained from Laramie Energy Technology Center, U.S. Department of Energy, Laramie, Wyoming. 

2 0btained from Geokinetics Corp., Vernal, Utah.
WASTE-CHARACTERIZATION STUDIES 

TABLE 3. Organic-solute analyses of Occidental-6 process and gas-condensate retort wastewaters

[DOC, dissolved organic carbon; mg/L, milligrams per liter;-, no data; HPI-A, hydrophilic acid; HPO-A, hydrophobic acid; HPI-B, hydrophilic base; HPO-B, hydrophobic base,

HPI-N, hydrophilic neutral; HPO-N, hydrophobic neutral; NA, not anlayzed, ND, not detected]

Confound

Aliphatic-taonocarboxylic acids

Formic acid.

Acetic acid.

Propanoic acid.

2-Methylpropanoic acid.

Butanoic acid.

Pentanoic acid.

2- and 3-Methylbutanoic acid.

Hexanoic acid.

Heptanoic acid.

Octanoic acid.

Nonanoic acid.

Decanoic acid.

Aliphatic-dicarboxylic acids

Ethanedioic acid.

Propanedioic acid.

Butanedioic acid.

Pentanedioic acid.

Hexanedioic acid.

Heptanedioic acid.

Octanedioic acid.

Aliphatic-dicarboxylic acids

Nonanedioic acid.

Decanedioic acid.

Aromatic-carboxylic acids

Benzoic acid.

Thiocyanate

Phenols

Phenol.

2-Hydroxytoluene .

3- and 4-Hydroxytoluene.

1 , 2-Dimethyl-4-hydroxybenzene .

Dimethylhydroxybenzene isomers

remaining.

Aromatic amines

Aniline.

2-Aminotoluene.

3- and 4-Aminotoluene.

Pyridine.

2-Methylpyridine .

3-Methylpyridine .

4-Methylpyridine .

2 , 6-Dimethylpyridine .

Dimethylpyridine isomers

remaining.

Aromatic amines

2,4,6-Trimethylpyridine.

Quinoline.

Isoquinoline.

2-Methylquinoline.

DOC 

classification

 

HPI-A

HPI-A

HPI-A

HPI-A

HPI-A

HPO-A

HPO-A

HPO-A

HPO-A

HPO-A

HPO-A

HPO-A

...

HPI-A

HPI-A

HPI-A

HPI-A

HPI-A

HPI-A

HPO-A

HPO-A

HPO-A

...

HPO-A

HPI-A

 

HPO-A

HPO-A

HPO-A

HPO-A

HPO-A

 

HPO-B

HPO-B

HPO-B

HPI-B

HPO-B

HPO-B

HPO-B

HPO-B

HPO-B

HPO-B

HPO-B

HPO-B

HPO-B

Proc

Concentration

(mg/L)

 

ND

1,188

364

119

117

110

151

109

149

131

81

31

...

4.9

8.1

2.0

21.2

4.7

7.2

11.5

12.8

11.7

...

25.4

78.6

...

26.0

7.1

9.6

4.6

36.1

...

1.6

.2

NA

2.3

NA

NA

NA

1.8

NA

4.0

1.9

.5

NA

(DOC = 3,000 mg/L)

DOC

(mg/L) (percent)

1,263.8 42.1

 

475

177

64.9

63.8

64.7

88.8

67.9

96.6

87.6

55.5

22.0

41.6 1.4

1.3

2.8

.8

10.0 

2.3

3.8

6.2

7.4

7.0

16.6 0.5

16.6

16.1 .5

64.5 2.2

20.0

5.5

7.4

3.6

28.3

9.74 .3

1.24

.16

...

1.75

...

 

 

1.41

...

3.17

1.59

.42

 

Concentratic

(mg/L)

...

1.0

3.4

1.2

.5

.4

.3

NA

NA

NA

NA

NA

NA

 

NA

NA

NA

NA

NA

NA

NA

NA

NA

- f

ND

8.1

...

54.3

23.2

42.6

5.6

54.5

 

21.3

3.4

5.2

14.7

9.2

6.5

6.3

9.5

37.6

70.1

5.8

2.4

1.6

idensate retort wastew

(DOC = 790 mg/L)

DOC 

>n

(mg/L)

2.87

.26

1.36

.58

.27

.22

.18

 

...

...

...

 

...

NA

 

 

 

 

 

...

 

 

...

 

 

1.68

140.2

41.8

18.1

33.1

4.4

42.8

152.1

16.5

2.7

4.1

11.2

7.1

5.0

4.9

7.5

29.5

55.5

4.8

2.0

1.3

(percent)

0.36

 

...

 

 

 

 

...

 

...

...

 

...

...

 

...

 

...

 

 

 

...

...

...

...

0.2

17.8

...

 

 

...

 

19.3

 

 

 

 

 

 

 

 

 

 

 

 

 
10 EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING

TABLE 3. Organic-solute analyses of Occidental-6 process and gas-condensate retort wastewaters Continued

Compound

Aliphatic amines 1

Methylamine .

Ethyl amine.

Hgdroxypyridines

2-Hydroxypyridine .

3-Hydroxypyridine .

4-Hydroxypyridine .

2-Hydroxy-6-methylpyridine .

Pyridinecarboxylic acids

2-Pyridinecarboxylic acid.

3-Pyridinecarboxylic acid.

4-Pyridinecarboxylic acid.

Aliphatic amides

Formamide.

Acetamide.

Propionamide.

Butyramide.

Urea.

Nitriles

Acetonitrile.

Propionitrile.

Isobutyronitrile.

Butyronitrile .

Valeronitrile.

Benzonitrile.

Aliphatic alcohols

Methanol .

Ethanol .

Propanol .

Isopropanol.

sec-Butylalcohol .

Aliphatic ketones

Acetone .

2-Butanone.

2-Pentanone.

Aliphatic aldehydes

Acetaldehyde.

Lactones

y-Butyrolactone .

y-Valerolactone.

Pyrrols

Identified DOC

DOC 

classification

 

HPI-B

HPI-B

...

HPI-B

HPI-B

HPI-B

HPI-B

...

HPI-B

HPI-B

HPI-B

...

HPI-N

HPI-N

HPI-N

HPI-N

HPI-N

 

HPI-N

HPI-N

HPO-N

HPO-N

HPO-N

HPO-N

...

HPI-N

HPI-N

HPI-N

HPI-N

HPI-N

...

HPI-N

HPO-N

HPO-N

...

HPI-N

...

HPO-N

HPO-N

HPO-N

...

Prc

(mg/L)

...

1.8

2.4

...

13.6

5.6

4.0

25.6

 

.3

.5

.4

...

ND

52.7

23.2

2.0

22.8

 

5.8

ND

ND

ND

ND

ND

 

ND

ND

ND

2.5

ND

...

3.9

 

...

 

2.4

13.7

15.2

ND

 

(DOC = 3,000 mg/L)

DOC

(mg/L)

 

 

 

31.5

8.6

3.5

2.5

16.9

.70

.18

.29

.23

38.5

21.4

11.4

1.1

4.6

3.4

3.4

 

...

...

...

 

1.5

 

...

1.5

2.42

2.42

...

 

1.31

1.31

16.7

7.6

9.1

1,508.4

(percent)

 

...

 

1.1

...

 

...

 

Trace

 

 

...

1.2

...

...

 

 

 

0.1

...

...

 

...

 

 

Trace

 

 

 

 

...

.1

 

...

 

Trace

...

.6

...

...

...

50.3

Concentration

(mg/L)

 

1.8

3.0

ND

ND

ND

ND

ND

NA

NA

NA

NA

 

2.0

4.0

.6

ND

NA

 

38.9

8.5

2.3

2.5

.6

2.7

...

3.4

2.8

.2

26.6

13.0

 

19.5

10.2

.9

 

ND

 

9.6

11.3

4.9

 

(DOC = 790 mg/L)

(mg/L)

 

...

 

...

 

 

...

...

...

 

 

 

2.46

.53

1.63

.30

 

 

34.3

22.8

5.6

1.6

1.7

.4

2.2

27.26

1.28

1.46

.12

16.0

8.4

20.7

12.1

7.9

.7

 

...

12.2

5.4

6.8

3.56

397.3

DOC

(percent)

 

 

...

...

 

 

...

...

...

...

 

...

0.3

 

 

 

...

 

4.3

 

...

 

...

...

...

3.5

 

...

 

2.6

 

...

...

...

 

1.3

...

...

.4

50.3

'Tentative data not included in carbon balance.

anion-exchange capacities were less than 1 meq/100 g at 

ambient pH of 8.5 to 9.0 for TOSCO-II spent shale. 

The cation-exchange capacity of a soil developed on oil 

shale in the Green River Formation ranged from 7 to 10 

meq/100 at ambient pH. Anion-exchange capacities 

were undetectable.

Adsorption of anionic and cationic dyes of fixed charge

as a function of pH was a new procedure developed to 

measure pH of the zero point of charge. The pH of the 

zero point of charge of TOSCO-II spent shale was found 

to be 8.5. Changes in cation-exchange capacity on destruction of the carbonaceous coating by oxygen-plasma ashing and destruction of the inorganic matrix by hydrochloric-hydrofluoric acids indicated that approximately
RETORT WASTEWATER-SPENT SHALE INTERACTIONS 11

TABLE 4. Inorganic-solute analyses of Omega-9 and 150-ton 

retort wastewaters

[Data in milligrams per liter except as indicated]

Property or Omega-9 retort wastewater 

constituent (in-situ retort)

pH

Specific conductance

(microsiemens per centimeter

at 25° Celsius)

Calcium

Magnesium

Sodium

Potassium

Bicarbonate

Carbonate

Chloride

Fluoride

Sulfate

Total sulfur

Ammonium as nitrogen

Total kjeldahl nitrogen

8.5

25,800

8

12

4,100

43

15,100

2,100

3,900

56

1,400

2,300

3,800

4,000

150-ton retort wastewater, 

barrel 66, run 13 

(simulated in-situ 

surface retort)

8.6

48,000

4

16

188

24

33,400

14,900

2,800

12

1,340

...

 

18,000

50 to 70 percent of the cation-exchange capacity was associated with the carbonaceous coating on the spent shale.

The carbonaceous coating (4.5 percent by weight) of 

TOSCO-II spent shale was examined by X-ray diffraction, 

X-ray fluorescence, electron microscopy, and infrared 

spectroscopy as the inorganic shale matrix was degraded successively through a series of acid treatments. The 

carbonaceous coating was found to be virtually elemental carbon with a trace of carbonyl functional groups.

The minimal exchange-capacity values, the pH of the 

zero point of charge near environmental pH levels, and 

the general lack of oxygen-containing functional groups 

in the carbonaceous coating all indicate that TOSCO-II 

spent shale is a neutral adsorbent that should have only 

slight degrees of ionic and polar interactions with dissolved constituents in water. The predominant sorptive

1 interaction should be hydrophobic interactions on the 

elemental carbon coating. Because of the relatively large 

surface area of the silt-sized TOSCO-II spent shale, coupled with an appreciable elemental-carbon content, this 

spent shale should be a good sorbent for hydrophobic 

solutes in wastewaters codisposed with the spent shale.

RETORT WASTEWATER-SPENT SHALE 

INTERACTIONS

The topic of retort wastewater-spent shale interactions is an issue of considerable importance because 

several technologies have proposed codisposal of retort 

wastewater and spent shale. Currently, the U.S. Environmental Protection agency does not allow codisposal 

because: (1) There is concern that two separate disposal 

problems may be combined into a potentially more serious disposal problem; and (2) there is a lack of data 

pertaining to the environmental acceptability of codisposal 

(Stanwood and others, 1980). To obtain information relevant to the above concerns about codisposal, a series of 

batch-type adsorption experiments were conducted with 

the TOSCO-II spent shale (characterized by Cowling, 

1979) as the sorbent and organic solutes in retort 

wastewater (obtained from the 150-ton retort, barrel 66, 

run 13, Laramie Energy Technology Center) as sorbates.

INTERACTIONS OF INDIVIDUAL 

ORGANIC-SOLUTE FRACTIONS

The complex organic-solute mixture in retort wastewater 

was simplified for sorption studies by generating more 

homogeneous compound groups by the DOC fractionation procedure. Because the DOC fractionation procedure is based on sorptive interactions, it also served as 

an interpretive tool for assignment of sorption mechanisms of the individual fractions on spent shale. The 

experimental design of the first set of experiments was

TABLE 5. Concentration of major inorganic sulfur species in four retort wastewaters

[Data in milligrams per liter]

Sample

150-ton retort wastewater

Geokinetics gas-condensate

Total

sulfur

1,290

Sulfate as

sulfur

446

390

Thiosulfate

as sulfur

690

525

Tetrathionate

as sulfur

<5

<5

Thiocyanate

as sulfur

405

13

retort wastewater 

Geokinetics process retort 

wastewater
12 EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING

to test whether the adsorption of the various individual 

solute fractions on spent shale would sum to the sorption 

of all organic components in the unfractionated retort 

wastewater. Lack of summation would indicate synergistic solute interactions that affect sorption.

A preparative-scale DOC fractionation was conducted 

on 150-ton retort wastewater to generate gram quantities of the various fractions; the fractions were redissolved in a synthetic inorganic retort-wastewater matrix 

at concentrations equivalent to retort-wastewater concentrations, and varying quantities of spent shale were 

added and equilibrated in stirred systems contained in a 

25°C water bath (Stuber and Leenheer, 1978a; Leenheer, 

1980). The quantity of sorbent was varied rather than 

the sorbate concentration to better observe the chromatographic effect resulting from differential affinities of 

organic-solute fractions for spent shale. Results of this 

first set of sorption experiments are graphed in the sorptionisotherm data in figure 4.

The unfractionated sorption isotherm did not coincide 

with the sum of the organic-solute-fraction sorption 

isotherms, indicating that both positive and negative 

synergistic interactions occurred. Secondly, the exponential increase of the unf ractioned sorption isotherm beginning near 70 percent of initial concentration probably is 

related to preferential sorption of the hydrophobic-neutral 

fraction that could not be tested as an individual fraction 

because of its solubility in water in the absence of the 

other fractions. As expected, the hydrophobic fractions 

had greater sorptive capacities than the hydrophilic fractions because of hydrophobic sorption on the elemental 

carbon of the spent shale; however, the greater sorptive 

capacities of the acid fractions than the base fractions 

were unexpected, because cation-exchange capacities, 

although small, previously were found to exceed anionexchange capacities for this spent-shale sorbent by factors of 2 to 3.

SYNERGISTIC INTERACTIONS OF ORGANIC-SOLUTE 

FRACTIONS IN WHOLE RETORT WASTEWATER

To obtain better insight into the nature of synergistic 

sorptive interactions on spent shale, a second set of 

sorption-isotherm experiments was performed under the 

same conditions as the first experiment except that 

analytical-scale DOC fractionations (Leenheer and 

Huffman, 1979) were performed on the non-sorbed solutes 

in whole retort wastewater after equilibration. Thus, 

relative sorption of the various fractions could be determined by comparison of DOC fractionations before and 

after sorption. Results of this experiment are shown in 

figure 5 (Leenheer, 1980).

This experiment confirmed the expected great sorptive capacity for the hydrophobic-neutral fraction predicted

(INCREASING QUANTITY OF SORBENT)

o

0 10 20 30 40 50 60 70 80 90 100

EQUILIBRIUM CONCENTRATION AS A PERCENTAGE OF 

INITIAL CONCENTRATION OF 500 MILLIGRAMS PER 

LITER OF DISSOLVED ORGANIC CARBON

FIGURE 4. Sorption isotherms (25°C) of dissolved organic-carbon 

fractions in 150-ton retort wastewater on TOSCO-II processed 

shale (from Leenheer, 1980). Preparative-scale dissolved organiccarbon fractionation preceded sorption. (HPO-A is hydrophobic 

acids; HPI-A is hydrophilic acids; HPO-B is hydrophobic 

bases; HPI-B is hydrophilic bases; and HPI-N is hydrophilic 

neutrals.)

by the previous experiment and showed some synergistic relationships between the hydrophobic-neutral fraction and hydrophobic- and hydrophilic-acid fractions. It 

appears that sorption of the hydrophobic-neutral fraction deactivates the spent-shale sorbent for sorption of 

the acid fractions at about 70 percent of initial concentration (fig. 5). At less than 70 percent of initial concentration, 

the hydrophobic-neutral fraction is mostly removed from 

solution and the acid fractions have greater sorptive 

capacities, which is partly reflective of the sorption isotherms shown in figure 4. At more than 70 percent of 

initial concentration the acid fractions also show increased 

sorption, which may be an absorption phenomenon in 

the hydrophobic-neutral films coating the shale particles 

in this range of the sorption isotherm. All the other 

fractions also show the absorptive interaction with the 

hydrophobic-neutral fraction at more than 70 percent of 

initial concentration. Adsorption of the acid fractions is 

minimal at about 70 percent of initial concentration, 

probably because of charge exclusion due to the negative 

charge that shale particles obtain from coabsorbed acids 

in the hydrophobic-neutral coating.
RETORT WASTEWATER-SPENT SHALE INTERACTIONS 13

3.75

(INCREASING QUANTITY OF SORBENT)

80 90 100

EQUILIBRIUM CONCENTRATION AS A PERCENTAGE OF 

INITIAL CONCENTRATION OF 500 MILLIGRAMS PER 

LITER OF DISSOLVED ORGANIC CARBON

FIGURE 5. Sorption isotherms (25°C) of dissolved organiccarbon fractions in 150-ton retort wastewater on TOSCO-II 

processed shale (from Leenheer, 1980). Analytical-scale dissolved organic-carbon fractionation followed sorption. (HPO-A 

is hydrophobic acids; HPI-A is hydrophilic acids; HPO-B is 

hydrophobic bases; HPI-B is hydrophilic bases: and HPI-N 

is hydrophilic neutrals.)

The mechanism of organic-acid adsorption at less than 

70 percent of initial concentration is less clear. It may be 

because retorting at 500°C produces alumina (Huggins 

and Green, 1973), which may adsorb organic anions 

during its rehydration with water. Retorting appears to 

activate oil shale with respect to sorption of organic-acid 

anions as a soil incorporating an oil-shale matrix from 

the Green River Formation showed no preferential sorption of organic-acid anions (Leenheer, 1980).

A conceptual model relating adsorption-isotherm data 

in figure 5 to retort-wastewater infiltration through a 

TOSCO-II spent-shale column is presented in figure 6. 

Zone 2 is about five times the length of zone 1 based on 

sorptive-capacity data assuming equilibrium sorption.

Retort water

100

90 -

^ n 80

70

60

50

40

30

20

10

0

Unfractionated 

sorption isotherm

ZONE1

Sorbed

hydrophobic

neutrals plus

coabsorbed

fractions

ZONE 2 

Sorbed 

acids, hydrophobic bases, 

and hydrophobic 

neutrals

ZONE 3 

Sorbed 

acids, hydrophilic bases, 

and hydrophilic 

neutrals

0 1.0 2.0 3.0 4.0 5.0 

SORPTIVE CAPACITY, IN MILLIGRAMS 

OF ORGANIC CARBON PER GRAM 

OF SHALE

N on sorbed

hydrophilic

solutes

FIGURE 6. Conceptual model of sorption of organic solutes in 

retort wastewater during infiltration through a TOSCO-II spentshale column.

No limits can be established for the relative length of 

zone 3, because 100 percent sorption of DOC was not 

attained in the experiments. Some hydrophilic organic 

solutes may never be preferentially sorbed relative to 

water and will elute from the column at the point of water 

breakthrough. The lower limit of zone 2, at which point 

75 percent of the DOC was removed, corresponded to a 

1:1 weight ratio of spent shale and retort wastewater. 

Because most proposals for codisposal involve a much 

greater ratio of TOSCO-II spent shale to retort wastewater, 

very large percent of adsorption of DOC on spent shale 

should be expected.

COMPARISON OF SPENT SHALE AS A SORBENT WITH 

GRANULAR ACTIVATED CARBON

The sorption-isotherm experiments presented previously indicated that the 4.5-percent elemental-carbon content of the TOSCO-II spent shale may be important in
14 EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING

imparting a hydrophobic character to the sorbent surface, 

which facilitates sorption of hydrophobic solutes. To test 

this hypothesis, a sorption isotherm using Calgon 

Filtrasorb 400 granular activated carbon as the sorbent 

and 150-ton retort wastewater was determined under the 

same experimental conditions as described previously 

for the TOSCO-II spent shale. A direct comparison of 

the sorption isotherms for the TOSCO-II spent shale and 

the activated carbon (fig. 7) indicates relatively minimal 

sorptive capacities for the TOSCO-II spent shale. However, 

when the data are normalized for the elemental-carbon 

content of 4.5 percent, the spent-shale sorption isotherm 

compares with the activated carbon-sorption isotherm 

within a factor of 2 (fig. 8).

The TOSCO-II spent-shale sorption isotherm exceeds 

the activated carbon-sorption isotherm in figure 8 at 

both small and large equilibrium concentrations indicating that other factors besides elemental carbon control 

the sorption surface. At small equilibrium concentrations, 

spent shale shows a moderate affinity for acid anions, 

which may be related to basic oxide surfaces (CaO, MgO) 

created by retorting. At large equilibrium concentrations, 

coabsorption of all organic-solute fractions within a 

hydrophobic-neutral film is an important factor. Therefore, 

three factors appear to promote the sorption of organic 

solutes on TOSCO-II spent shale: (1) The elementalcarbon coating; (2) uptake of acid anions by a mineral 

surface activated by retorting; and (3) coabsorption of 

all organic-solute fractions within a sorbed hydrophobicneutral film. These various sorption mechanisms probably do not act independently on organic solutes, but 

rather reinforce each other (in most instances) resulting 

in increased sorption of solutes by multiple mechanisms.

SUBSEQUENT STUDIES OF RETORT WASTEWATERSPENT SHALE INTERACTIONS

After the completion of this study of retort wastewaterspent shale interactions, two subsequent studies of this 

topic were made by Fox and others (1980) and Jackson 

and Jackson (1982). Fox and others (1980) conducted 

batch- and column-type studies using six separate spent 

shales and five different process retort wastewaters. Both 

studies found that the type of spent shale was a much 

more significant variable for sorption of organic solutes 

than was the type of retort wastewater. Organic-solute 

sorption increased as the elemental-carbon content of 

the spent shale increased, and sorption decreased as the 

retorting temperature increased, because increases in 

retorting temperature typically result in less carbonaceous coatings. Calcined and fused-clinker spent shales 

produced by high temperature retorting were poor adsorbents for organic constituents, but they removed most 

(97 to 99 percent) of the carbonate from retort wastewater.

240

(INCREASING QUANTITY OF SORBENT)

Calgon F 400 activated carbon

50 100 150 200 250 300 350 400 450 500 

EQUILIBRIUM CONCENTRATION, IN MILLIGRAMS 

PER LITER OF DISSOLVED ORGANIC CARBON

FIGURE 7. Sorption of organic solutes in 150-ton retort wastewater on Calgon F-400 activated carbon and TOSCO-II spent 

shale (from Stuber and Leenheer, 1978a).

The most effective spent-shale sorbent for organic solutes 

was the TOSCO-II spent shale, which removed 48 to 73 

percent of the DOC at a 1:1 weight mixture of spent shale 

and retort wastewater.

The study by Jackson and Jackson (1982) used standard leach tests (American Society for Testing and 

Materials, 1982; U.S. Environmental Protection Agency, 

1980) to determine if organic and inorganic constituents 

in four retort wastewaters codisposed with their four 

respective spent shales could be removed by leaching. 

They found efficient adsorption of total organic carbon 

from all tested retort wastewaters on spent shales, and 

the sorbed organic solutes were not leached significantly 

under the conditions of the test. These results are in 

accord with the results of this study and the study by 

Fox and others (1980), as all of the tested spent-shale 

sorbents were not calcined and had elemental-carbon 

coatings that made them efficient sorbents for organic 

constituents.

RETORT WASTEWATER-SOIL INTERACTIONS

The retort wastewater-soil interactions phase of this 

study was extensively researched because of the financial support by the Laramie Energy Technology Center, 

U.S. Department of Energy. Their support was to study 

the effect of a spill of retort wastewater on soils at their 

Rock Springs, Wyoming, experimental in-situ retorting 

site. A retort wastewater, designated Omega-9, produced 

at their site-9 retort, was collected in large quantities and 

preserved under refrigeration by Farrier and others (1977) 

and characterized by Fox and others (1978).
RETORT WASTEWATER-SOIL INTERACTIONS 15

(INCREASING QUANTITY OF SORBENT)

Calgon F 400 activated carbon

Tosco II spent shale 

(Data normalized on 

elemental carbon 

content)

50 100 150 200 250 300 350 400 450 500

EQUILIBRIUM CONCENTRATION, IN MILLIGRAMS 

PER LITER OF DISSOLVED ORGANIC CARBON

FIGURE 8. Sorption isotherm (25° Celsius) data for TOSCO-II 

spent shale normalized on elemental-carbon content (4.5 percent by weight).

140

After characterizing the physical and chemical properties of the soils at the site by a first-order soil survey 

(Woodward-Clyde Consultants, 1978), the deepest soil at 

the site from the Haterton soil series was selected for 

intensive study. The deepest soil was selected to maximize interactions with retort wastewater passed through 

the soil. This soil was sampled approximately 193 km 

east of site 9 where the Omega-9 retort wastewater was 

produced. The soil was classified as a fine-loamy, mixed 

(calcareous) frigid, shallow family of Typic Torriorthents, 

whose surface (A) horizon is a light gray, alkaline loam, 

approximately 50 mm thick, with various subsoil (C) 

horizons consisting of alkaline clay loams. During 

sampling, the soil was divided into the following horizons: 

A (0-50 mm depth); Ci (50-360 mm depth); C2 (360-660 

mm depth); and Ca (660-1,000 mm depth). Directly 

below the Ca horizon is weathered oil shale of the Green 

River Formation.

Results of the retort wastewater-soil interactions study 

have been extensively presented and interpreted in prior 

publications (Leenheer, 1980; Leenheer and others, 1981;

10 15 20 25 30 35 40 45 50

SOIL TO WATER RATIO

FIGURE 9. Extraction isotherms (25°C) of dissolved organic-carbon fractions from site-9 soil by Omego-9 retort wastewater (from 

Leenheer, 1980). (HPO-A is hydrophobic acids; HPI-A is hydrophilic acids; HPI-B is hydrophilic bases; and HPI-N is 

hydrophilic neutrals.)
16 EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING

Leenheer and Stuber, 1981). Therefore, only a minimal 

description of the experimental procedures and data will 

be presented in this report, and the results and interpretations will be emphasized.

BATCH-SORPTION EXPERIMENTS

The first set of sorption experiments with soil used the 

same batch-equilibrium methods as was used previously 

with spent shale. However, more organic carbon was 

extracted from the soil by retort wastewater under certain conditions than was sorbed from retort wastewater 

by soil. To quantify and ascertain the nature of these 

organic constituents, a synthetic inorganic retort wastewater was prepared based on the analysis of Omega-9 

retort wastewater by Fox and others (1978). Organiccarbon extraction isotherms were generated using the 

same methods for sorption isotherms presented previously (Stuber and Leenheer, 1978a), except that synthetic 

retort wastewater and the A horizon of the Haterton soil 

were used, and DOC fractionation was performed on the 

extracted organic solutes after equilibration. The extraction-isotherm data are shown in figure 9 (Leenheer, 1980).

The majority of extracted material was found to be 

organic acids that are derived from soil humic and fulvic 

acids. Insignificant quantities of hydrophobic-base and 

hydrophilic-neutral fractions were extracted; therefore, 

these data were not plotted in figure 9. The hydrophobicneutral fraction does not parallel extraction trends of the 

other DOC fractions, but decreases after reaching a maximum near the 25-percent soil to water ratio. This decrease 

may be related to a salting-out effect caused by coextracted 

organic acids and bases.

The extraction isotherms in figure 9 were used to 

correct the batch-sorption isotherms for extracted organic matter, and the resulting retort wastewater-soil sorption isotherms are presented in figure 10. The sorption 

isotherms in figure 10 when compared to the sorption 

isotherms in figure 5 indicate that soil is not as efficient a 

sorbent as TOSCO-II spent shale because sorptive capacities of the unfractionated isotherm for soil are only about 

two-thirds the sorptive capacity for spent shale. The 

sorptive capacities for the base and neutral fractions are 

similar for both soil and spent shale, but most of the 

reduced sorptive capacity for soil can be attributed to 

the lower sorptive capacities for the acid fraction. The 

cation-exchange capacity data for soil and spent shale 

(Cowling, 1979) indicate that soil is much more negatively charged than spent shale, thus minimizing sorption of 

acids through charge (ion) exclusion. The formation of 

enhanced negative charge through coabsorbed acids in 

the hydrophobic-neutral film is not apparent in soil as it 

was for spent shale as evidenced by the minima in sorptive capacities for the acid fractions at Ceq (carbon

(INCREASING QUANTITY OF SORBENT)

5.5

CJ

70 80 90 100

EQUIVALENT CONCENTRATION AS A PERCENTAGE 

OF INITIAL CONCENTRATION OF 1000 MILLIGRAMS 

PER LITER OF DISSOLVED ORGANIC CARBON

FIGURE 10. Sorption isotherms (25° Celsius) of dissolved organiccarbon fractions in Omega-9 retort wastewater on site-9 soil 

(modified from Leenheer, 1980). Analytical-scale dissolved 

organic-carbon fractionation followed sorption. (HPO-A is 

hydrophobic acids; HPO-B is hydrophobic bases; HPO-N is 

hydrophobic neutrals; HPI-A is hydrophilic acids; HPI-B is 

hydrophilic bases; and HPI-N is hydrophilic neutrals.)

equivalent) = 70 percent in figure 5. The negative-charge 

density of soil is most likely already significant enough 

to prevent additional negative charges from forming 

through the sorption of organic acids. The soil data 

again show the importance of organic-acid sorption on 

spent shale.

SOIL COLUMN-SORPTION EXPERIMENTS

A number of soil-column experiments were done to 

obtain information about the various interactions of retortwastewater solutes with soil. Omega-9 retort wastewater 

was passed through a large soil column composed of 

reconstituted horizons from the Haterton soil. Three 

experiments were conducted to differentiate among soil 

constituents that are leachable with distilled water, constituents that are extracted from or adsorbed by soil 

using synthetic inorganic retort wastewater, and constituents that are extracted from or adsorbed by soil using 

Omega-9 retort wastewater. In the soil-column experiments that used synthetic and Omega-9 retort wastewaters, 

distilled water was passed through the column after the
RETORT WASTEWATER-SOIL INTERACTIONS 17

 i r 

DISTILLED WATER

_Influent specific 

conductance level

UJ ^u

U

tr. m 30

w

§20

i

=! 10

z 

 n

t SYNTHETIC RETORT? WASTE WATER ( Distilled water

1

1 9 Influent specific " A-*-- 1 __ * T~~~ "\ v_ conductance level

** 

OMEGA 9 RETORT? WASTE WATER Distilled water

Influent specific 

conductance level

12 16 20 24 28

SOIL- COLUMN EFFLUENT VOLUME, IN LITERS

_______ I _______ I ______ I ______ I _______ I

32 36 40 44

567 

SOIL-COLUMN VOID VOLUMES

8 10 11 12

FIGURE 11. Specific-conductance curves of soil-column effluents (modified from Leenheer and others, 1981).

retort wastewater to determine which sorbed constituents would be released in a situation analogous to precipitation leaching of soil after a retort-waste water spill. 

Leenheer and others (1981) describe the physical and 

inorganic-constituent interactions; Leenheer and Stuber 

(1981) describe organic-constituent interactions.

PHYSICAL AND INORGANIC-CONSTITUENT 

INTERACTIONS

All the soil-column-effluent data were graphed in the 

same manner with influent concentrations marked on 

the ordinate and with identical concentration-volume 

and void-volume scales for all three soil-column experiments. About twice the volume of Omega-9 retort 

wastewater was passed through the soil column compared to the effluent volumes of the previous two experiments to obtain more complete information about the 

retention of organic solutes in retort wastewater. Specific conductance is plotted in figure 11, pH in figure 12, 

and color in figure 13.

Significant values for specific conductance in the first 

liter of eluate (fig. 11) for all three experiments indicate 

soluble salts leaching from the column. The decrease in 

specific conductance to values less than those of the 

influent from until about 0.5 to 7 L of effluent and passed 

through the columns during the retort-wastewater experiments indicates reactive processes, which are removing 

ionic solutes. Examination of the elution curves of major 

constituents (Leenheer and others, 1981) in the region 

where the decrease in specific conductance occurred 

revealed that as ammonium and bicarbonate were being 

sorbed by the soil column, magnesium, calcium, and 

potassium were being eluted. An ionic mass balance for 

major ions adsorbed and eluted from the soil columns in 

shown in table 6. Precipitates analyzed to be calcium 

carbonate were observed eluting from the soil column 

during the decrease in the specific conductance, and the 

deficit in cations eluted (table 6) is evidence that most of 

the displaced calcium exchanged by ammonium ion 

remained in the column as precipitated calcium carbonate. 

Thus, the decrease in the specific conductance is due to
18 EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING

10.0 

9.4 

8.8 

8.2 

7.6

7.0 

10.0

DISTILLED WATER

Influent pH

9.4 

8.8 

8.2 

7.6 h

. SYNTHETIC RETORT? WASTE WATER

7.0

 Influent pH

Distilled water

OMEGA- 9 RETORT? WASTE WATER

Distilled water

7.0

12 16 20 24 28 32 

SOIL-COLUMN EFFLUENT VOLUME, IN LITERS

_____I______I______I______I______I______L

36 40 44

45678 

SOIL-COLUMN VOID VOLUMES

10 11 12

FIGURE 12. pH curves of soil-column effluents (modified from Leenheer and others, 1981).

removal of ammonium ion by ion exchange and removal 

of bicarbonate by precipitation with calcium. Magnesium is the major ion eluted by this exchange process 

because of its abundance on soil-exchange sites and lack 

of controls on its solubility.

The pH data graphed in figure 12 show three plateaus 

for the retort-wastewater experiments. The pH of the 

first plateau of 7.2 results from sodium and magnesium 

bicarbonate buffering of the effluent, after removal of 

ammonium by cation exchange and carbonate by precipitation. The pH of the second plateau of 8.6 corresponds 

to the influent pH, and the pH of the third plateau of 

nearly 9.5 results from a decrease of the common-ion 

effect during the distilled-water rinse on ammonium 

humates formed during retort-wastewater saturation of 

the soil.

The color curves in figure 13 give an indication of the 

points in the elution curves where soil organic matter is 

extracted by retort wastewater. A small color peak occurs 

where ion-exchange and precipitation processes discussed 

affect effluent chemistry; however, the major extraction 

of soil organic matter occurs during the distilled-water 

rinse. A conceptual model of major soil-retort wastewater 

interactions is presented by the two reactions in figure 

14. When ammonium breaks through the soil column in 

the first reaction (fig. 14), a minor quantity of mimic 

substances is solubilized as ammonium salts, which causes the first color peak of the elution curve; however, the 

relative large ammonium concentration of retort wastewater compresses the electrical double layer around humate 

macromolecules, which limits the dissolution of sparingly 

soluble ammonium humate salts through the common-
RETORT WASTEWATER-SOIL INTERACTIONS 19

1.5

1.0

0.5

n n

DISTILLED WATER

-

^^

 I .. ~ ....... .,, - Influent rolor '

T- ' U

W

cc

LU 1.5 IUJ

o 1-0

2

<

2 0.5

O

CO* 

. 0.0

Distilled water

^

SYNTHETIC RETORT? WASTE WATER N

1 \

I \

/ \

7 \

/ ^L

1 \.

1

 ~»^_ 7

s ^ _ * J *J- / 

 

^^ , x Influent color '

2.5 

2.0 

1.5 

1.0 

0.5 

0.0

OMEGA- 9 RETORT? WASTE WATER

.Influent color

Distilled water

12 16 20 24 28

SOIL-COLUMN EFFLUENT VOLUME, IN LITERS

_____I______I______I_____I______I 

32 36 40 44

567 

SOIL-COLUMN VOID VOLUMES

8 10 11 12

FIGURE 13. Color curves of soil-column effluents (modified from Leenheer and others, 1981).

ion effect. When ammonium concentrations are decreased 

during the subsequent distilled-water rinse, a flush 

peak of humate anions occurs due to the decrease of the 

common-ion effect on solubility, as shown by the second 

reaction (fig. 14).

These chemical reactions also affect soil permeability 

and porosity. Flow rate of the soil-column effluent gave 

an estimate of the physical changes occurring within the 

soil column because the hydrostatic pressure on the top 

of the soil column was kept approximately constant 

throughout the experiments. Flow-rate curves are presented in figure 15. The flow-rate curve for the distilledwater leaching experiment showed nearly a linear decrease 

with volume, as the soil dispersed and compacted. However, 

flow-rate curves of the retort-wastewater experiments 

showed major variations that coincided with the effluent 

volumes of the various reactions discussed previously. 

Flow rate initially decreased from 0.5 to as much as 1 

void volume. This decrease was most likely related to

calcium carbonate precipitation and displacement of air 

within the columns. Flow rate then increased to a peak at 

approximately 2 void volumes. This peak probably was 

related to soil colloid shrinkage because of electrical 

double-layer compression due to the great ionic strength 

of retort waste water. The subsequent flow-rate decrease 

similar to that of the distilled-water rinse probably represented gradual disaggregation of soil aggregates; a final 

small decrease in flow rate during the distilled-water 

rinse may have represented soil-colloid expansion with 

the decrease of the common-ion effect on the electrical 

double layer.

Most of the minor inorganic constituents in the retort 

wastewaters interacted analogously with soil similarly 

to the major elements just discussed with the exception 

of thiocyanate, chloride, and molybdenum. These three 

constituents are anions with few or no solubility controls. 

The elution curve for thiocyanate (fig. 16) demonstrates 

that thiocyanate may be an excellent tracer for retort-
20 EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING

TABLE 6. Ionic mass balance for ions adsorbed and eluted from 

soil columns

Synthetic Omega-9

Constituent experiment 

(milliequivalents)

experiment 

illiequivalents)

Total nitrogen adsorbed

(estimate for ammonia). 

Bicarbonate adsorbed. 

Calcium eluted. 

Magnesium eluted. 

Potassium eluted.

Total bicarbonate adsorbed 

(includes calcium, 

magnesium, and potassium 

eluted).

496

73

351

62

303

51

347

94

wastewater migration in soils and sediment because of 

its lack of sorptive interactions, its uniqueness to retort 

wastewater, and its moderately large concentration in

retort wastewater. Thiocyanate does not biodegrade in 

anaerobic ground-water systems and can be detected by 

colorimetric methods at concentrations as low as 10 yUg/L.

Inorganic solutes sorbed from retort wastewater by 

soil include the cations: barium, cadmium, cobalt, copper, 

iron, and zinc, and the anions: arsenic, boron, and fluoride. 

The cations were sorbed through ion-exchange and complexation processes, and the anions were retained through 

solubility controls causing precipitation such as calcium 

fluoride precipitation. When the distilled-water rinse followed retort-wastewater leaching, decrease of solubility 

controls and release of humic acids and non-ionic ammonia caused the desorption of arsenic, barium, boron, 

cobalt, copper, fluoride, iron, and zinc. A typical sorptiondesorption elution curve is shown for copper in figure 17.

Lithium, sodium, potassium, strontium, and manganese were extracted by retort wastewater from the soil 

by the exchange process discussed previously for ammonium, magnesium, and calcium. A typical ion-exchange 

elution curve for potassium is shown in figure 18. Most 

of the soluble salts were leached from the soil columns 

within the first liter (0.26 void volume) of leachate. The 

salts consisted mainly of sodium, calcium, and magnesium chlorides, sulfates, and nitrates. Most of the nitrate 

was found to reside in the Cs soil horizon. Boron, silica,

Soil + Retort waste water *- Ammonium (NH4) - saturated soil + Soil effluent + Calcium carbonate (CaCO3) precipitate

Salt coating (MA)

Organic 

coating

Mg

NH4 (HCO3 

NaHCO,

Organic 

coating

NHt

NH

CaCO,

HC0

Ammonium (NH4) - saturated soil + Distilled water > Ammonium(NH4) - saturated soil + Extracted organic matter

Organic v|^f 

coating

NH

NH'

+ HJD

Organic 

coating

NH

Soil colloid y + NH t HumateNH; If H2°lt

NH3 Humic Acid

+ +

H + OH'

FlGURE 14. Soil-retort wastewater reactions (modified from Leenheer and others, 1981).
RETORT WASTEWATER-SOIL INTERACTIONS 21

1000

750

500

250

DISTILLED WATER

SYNTHETIC RETORT WASTE WATER

LL 1000

750

500

250

0

Distilled water

OMEGA-9 RETORT WASTE WATER

12 16 20 24 28

SOIL-COLUMN EFFLUENT VOLUME, IN LITERS 

______I______|______|______I_______I

32 36 40 44 

I

567 

SOIL-COLUMN VOID VOLUMES

8 10 11 12

FIGURE 15. Flow-rate curves of soil columns (modified from Leenheer and others, 1981).

and vanadium leached at a slower rate from the soil. 

Anomalously large concentrations of vanadium were found 

in the soil leachates. A typical salt leachate curve is 

shown by the curve for sulfate in figure 19.

The reduced sulfur species, thiosulfate and tetrathionate, 

were found to be partly oxidized to sulfate during their 

passage through the soil column. In addition, 84 percent 

of the thiosulfate in Omega-9 retort wastewater oxidized 

to polythionates and sulfate during 3 years of refrigerated storage.

After the soil-column leaching experiments were 

completed, the soil was unpacked from the columns and 

dried for 2 weeks. Subsequent soil analyses for ammonia 

nitrogen (fig. 20) showed that much of the ammonium 

still was retained by the soil after drying. Data comparison of the total quantity of ammonium found by soil 

analysis of the columns leached with synthetic and Omega-9 

retort wastewaters with the soil-exchange capacity of 

these columns found that about 65 percent of the exchange 

sites still were occupied by ammonium ion. This finding

is somewhat surprising, because removal of a large percentage of ammonium was predicted during the distilledwater rinse that followed retort-waste water leaching, by 

biological nitrification of ammonium to nitrate, and by 

volatilization from the alkaline soil during the 2-week 

drying period. At pH 9.5, which occurred during the 

distilled-water rinse, 76 percent of the ammonium plus 

ammonia species are present as free ammonia, which 

should leach or be volatilized from the soil. Significant 

losses of ammonium appeared to have occurred only in 

the shallow A horizon of the soil profile (fig. 20). Loss of 

ammonium in the A horizon may due to both leaching of 

ammonium humates and biological nitrification.

Soil minerology of the Haterton soil was determined 

to provide insight into the mechanism of anomalous 

ammonium ion retention. Little variation was found in 

minerology among the various horizons. An average 

minerological soil composition and the contribution of 

each mineral to the cation-exchange capacity of the soil 

is given in table 7.
22 EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING

SYNTHETIC RETORT? WASTE WATER .Distilled water

Influent concentration 

^u

100 

8D

60 

40 

20

0 

C

OMEGA- 9 RETORT? WASTE WATER Distilled water

-A ^ ,. f -, Influent

______________ | _______________ | ______________ | ______________ , _______________ | ______________ , | 1 1 ^*»-»t* ,

4 8 12 16 20 24 28 32 36 40 4 

SOIL- COLUMN EFFLUENT VOLUME, IN LITERS 

I I I I I I I I I I J I

567 

SOIL-COLUMN VOID VOLUMES

10 11 12

FIGURE 16. Thiocyanate curves for soil-column effluents (modified from Leenheer and others, 1981).

One-half of the cation-exchange capacity in the Haterton soil was due to analcime, which is a zeolite; this is a 

significant finding, because analcime has small lattice 

pores, which permit moderately rapid cation exchange of 

sodium and potassium. Ammonium exchange is permitted, 

but the kinetics are slow. After drying, a slightly decrease 

in pore size fixes ammonium within the crystal lattice of 

analcime (El-Nahel and Wittig, 1973). This explains why 

ammonium was not lost by volatilization from soil during drying, and the slow kinetics of ammonium exchange 

may explain why it was not removed by the distilledwater rinse after retort-water leaching. Analcime occurs 

in most soils and sediments derived from the Green 

River Formation, thus ammonium sorption may be a 

major interaction between retort wastewater and soil.

Saponite and sepiolite clays account for most of the 

remaining exchange capacity. Both of these clays are 

magnesium enriched; this helps explain why magnesium 

was the most abundant cation exchanged for ammonium 

shown in the data in table 6. The total cation-exchange

capacity of 31 meq/100 g based on estimates of data 

shown in table 7 is somewhat similar to the exchangecapacity determination (20 meq/100 g) of WoodwardClyde Consultants (1978), because it is not an unreasonable 

estimate that some of the soil-exchange sites may be 

chemically and physically blocked resulting in a smaller 

experimentally determined value.

ORGANIC-CONSTITUENT INTERACTIONS

Dissolved organic-carbon curves for the soil-column 

effluents are shown in figure 21. The DOC in each of 

these three Curves was subdivided by the DOC-fractionation procedure. Results for the distilled-water and 

synthetic retort-waste water effluents, which extracted 

soil organic matter, were similar to the results of the 

batch-sorption procedure shown in figure 9. To determine the sorption on soil of organic solutes from Omega-9 

retort wastewater, DOC-fractionation data from synthetic retort-wastewater column effluent was subtracted from
RETORT WASTEWATER-SOIL INTERACTIONS 23

240

180

120

60

DISTILLED WATER

Influent concentration _

300

£240

§120 

DC

o

5 60

£E 0

LJJ

Q.

O_

O 300

O

240

180

120

60

SYNTHETIC RETORT WASTE WATER 

Precipitate

Distilled water

Influent concentration 

OMEGA- 9 RETORT WASTE WATER,

Distilled water

Influent 

concentration

12 16 20 24 28

SOIL- COLUMN EFFLUENT VOLUME, IN LITERS 

______I______I______I______I______I

32 36 40 44

5678 

SOIL- COLUMN VOID VOLUMES

10 11 12

FIGURE 17. Copper curves for soil-column effluents (modified from Leenheer and others, 1981).

DOC-fractionation data of Omega-9 retort-wastewater 

effluent. The results of this data subtraction was plotted 

on the ordinate as the percent of influent concentration 

(fig. 22).

For the effluent-volume range from 10 to 36 L (2.6 to 

9.4 void volumes), DOC fractions increased in affinity 

for the soil in the following order: hydrophilic neutrals ^ 

hydrophilic acids < hydrophobic acids < hydrophilic 

bases < hydrophobic neutrals ^ hydrophobic bases. The 

previous batch-sorption isotherm study using the same 

retort wastewater and soil found that the hydrophobicneutral fraction had a much greater affinity than the 

other five fractions (fig. 10). However, the greater affinity for the hydrophobic-neutral fraction (fig. 10) only 

occurred at soil to water ratios corresponding to the 11 to 

140 void-volume range, which was greater than the effluentvolume range of the present study. Examination of the

data in figure 22 shows that the hydrophobic-neutral 

fraction becomes the fraction of greatest affinity for soil 

after 26 L (6.8 void volumes); the data in figure 10 

indicate that the hydrophobic-neutral breakthrough curve 

continues to diverge from the other five fractions at 

larger effluent volumes.

In figure 22, the flush peaks, which occur with the 

distilled-water rinse, elute later, become broader, and tail 

more as the affinities of the DOC fractions for soil increase. 

The flush peaks for the acid fractions can be ascribed to 

the decrease of the common-ion effect on solubility of 

ammonium salts of the acids, as ammonium concentration is decreased during the distilled-water rinse. However, 

flush peaks that also occur in the hydrophobic-base, 

hydrophilic-base, and hydrophobic-neutral fractions indicate some type of association between these fractions 

and organic acids of either soil or retort-wastewater origin,
24 EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING

600

450

300

150

0

DISTILLED WATER

 Influent concentrationSYNTHETIC RETORT WASTE WATER

750

600

450

300

150

0

OMEGA- 9 RETORT WASTE WATER

Distilled water

Influent 

concentration

0 12 16 20 24 28

SOIL-COLUMN EFFLUENT VOLUME, IN LITERS

32 36 40 44

45678 

SOIL-COLUMN VOID VOLUMES

10 11 12

FIGURE 18. Potassium curves for soil-column effluents (modified from Leenheer and others, 1981).

which are released during the distilled-water rinse. The 

hydrophilic-neutral fraction, which is least likely to associate with any sorbent or other solutes, does not show a 

flush peak.

The observed order of affinity of the DOC fractions for 

soil follows expectations based on soil properties as a 

sorbent. The hydrophilic-neutral fraction should have 

the least affinity for soil, because it did not sorb on the 

synthetic resins used in the DOC fractionation. This 

fraction does not have acid or base properties that can 

cause sorption by anion or cation exchange, and its 

hydrophilic properties limit physical sorption. Soil usually has a relatively large cation-exchange capacity compared to its anion-exchange capacity, which means that 

it is a negatively charged sorbent at most soil pH levels. 

Anions and organic acids should have less affinity for 

soil because of ionic exclusion between negatively charged

solutes and negatively charged sorbents. The hydrophilicacid fraction has little affinity for soil. The hydrophobicacid fraction has greater affinity because of physicaladsorption interactions that can occur between the nonpolar hydrocarbon parts of hydrophobic-acid solutes and 

the nonpolar sorption sites on the soil column. The 

hydrophobic-neutral fraction has the greatest affinity 

for soil because it is the most water-insoluble, nonpolar 

fraction that is sorbed by the physical-sorption process. 

The DOC-fractionation data shown in figure 22 offer 

qualitative mechanistic insights into the migration of 

various organic-compound groups through the soil column, 

but quantitative mechanistic interpretations of these 

data are complicated by the large number of compounds 

with different sorptive-capacity factors within each DOC 

fraction. The hydrophobic-base fraction was selected for 

the quantitative mechanistic study because of the ease
RETORT WASTE WATER-SOIL INTERACTIONS 25

1 5,000

DISTILLED WATER

Influent concentration J

SYNTHETIC RETORT WASTE WATER .Distilled water

0 

1 2,000 

9000 

6000 

3000 

n

 ***>w Influent concentration 

^^- - -| A

L

EGA - 9 RETORT WASTE WATER 

I Distilled water

Influent 

^ A. concentration 

r V^.-

12 16 20 24 28

SOIL-COLUMN EFFLUENT VOLUME, IN LITERS

I 1 _____I______I______I

32 36 40 44

4567

SOIL-COLUMN VOID VOLUMES

8 10 11 12

FIGURE 19. Sulfate curves for soil-column effluents (modified from Leenheer and others, 1981).

of specific compound analysis by liquid chromatography 

and the importance of aromatic amines in this fraction as 

environmental contaminants.

Breakthrough curves for pyridine, 2-methylpyridine, 

3- and 4-methylpyridine, a dimethylpyridine, and three 

quinoline compounds from the soil column are shown in 

figure 23. An important finding is that the relative order 

of the rates of migration through the soil column is 

exactly the same as the order of migration through the 

octadecylsilica, high-performance liquid-chromatography 

column used in the analysis of the aromatic amines.

To determine whether order of migration of aromatic 

amines through the soil column is quantitatively similar 

to the reversed-phase, high-performance, liquid-chromatography column, column capacity factors (k 1') for both 

the soil and the analytical-chromatography column were 

computed, and their ratios for each aromatic amine were 

compared in table 8. The capacity-factor ratio rapidly 

decreases between 2-methylpyridine and dimethylpyridine, 

which corresponds to an elution-volume range where the

retort-wastewater mobile-phase chemistry changed because 

of salt (fig. 11) and DOC leaching of the column (fig. 21), 

ammonium sorption (table 6), and calcium carbonate 

precipitation (fig. 14). A physical consequence of the 

ion-exchange and precipitation reaction front was the 

displacement of air that would increase the wetted surface area of the column. Therefore, the likely cause of the 

sudden increase in soil-column capacity factors probably 

is related to the increase in wetted surface area and the 

change in retort-wastewater mobile-phase chemistry. These 

reaction-front changes affecting solute-column capacity 

factors also are probably instrumental in causing the 

unusual variations in DOC-fractionation data (fig. 22) 

for the 0.25 to 2.5 void-volume range. The column capacityfactor ratio (table 8) nearly is constant for dimethylpyridine, 

quinoline, and methylquinoline, which indicates that the 

hydrophobic effects that control the rate of migration 

through the analytical-chromatography column also are 

the primary sorptive mechanism in the soil column after 

the passage of the reaction front.
26 EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING

UNTREATED SOIL

VJ

10

20

W 30

DC

LLJ

hH 40

P 

Z

u 50

z

£ 60

(-

Q.

LU

Q 70

80

90

inn

A ' ' '

C-1

.

-

C-2

_

-

C-3

-

I I I

SOIL LEACHED WITH 

DISTILLED WATER

SOIL LEACHED WITH

SYNTHETIC 

RETORT WASTE WATER

SOIL LEACHED WITH

OMEGA-9 

RETORT WASTE WATER

i I

C 1

C-2

C-3

0 300 600 900 1200 0 300 600 900 1200 0 300 600 900 1200

AMMONIA NITROGEN, IN MILLIGRAMS PER KILOGRAM

300 600 900 1200

FIGURE 20. Soil analyses for ammonia nitrogen (modified from Leenheer and others, 1981).

The aromatic amines all show significant flush peaks 

when distilled water is applied to the column (fig. 23). 

The size of this peak apparently is affected both by the 

quantity of the amine sorbed by the soil column and by 

its desorption rate in distilled water. Note that the deTABLE 7. Cation-exchange capacity contributions of Haterton 

soil constituents

[NS, not significant]

Constituent

Calcite

Dolomite

Quartz

Plagioclase

feldspar

Potash feldspar

Ana Ic ime

llllte mica

Saponite

Sepiolite

Kaolinite

Amphibole

Organic matter

Exchange

capacity

(milliequivalents

per 100 gramsj

NS

NS

NS

NS

NS

400

12

76

32

6

NS

200

Soil-exchange

Percentage capacity

(milliequivalents

composition ^ ^ ^ (

18 NS

11 NS

20 NS

7 NS

4 NS

4 16

9 1

12 9

11 3

1 NS

2 NS

1 2

Exchange

capacity

(percent)

NS

NS

NS

NS

NS

51

3

29

9

NS

NS

6

creasing slope of the flush peaks is steepest for the most 

soluble amines (pyridine, methylpyridine) and flattest 

for the most hydrophobic amines (quinolines). As discussed in the previous section, these flush peaks are a 

result of stripping the natural organic-matter coating 

from the soil by distilled water.

CONCLUSIONS ABOUT RETORT 

WASTEWATER-SORBENT INTERACTIONS

The TOSCO-II spent shale of this study is an effective 

sorbent for many organic constituents in retort wastewater 

and would be worthy of future research for a candidate 

sorbent matrix in which retort wastewaters could be 

codisposed. Sorption of organic acids is an unusual property of TOSCO-II spent shale, which makes it more 

effective as a sorbent compared to other spent shales and 

soils. Subsequent studies by other investigators have 

confirmed these findings about the TOSCO-II spent shale 

and also have indicated that calcined spent shales produced by higher temperature retorting processes are 

very poor sorbents for organic solutes in retort wastewaters. 

In an in-situ retort where a variety of spent-shale types 

are produced, ground-water flow paths during backflooding 

or retort wastewater reinjection should be an important
RETORT WASTEWATER-SOIL INTERACTIONS 27

1250

1000

750

500

cc 25°

LU

= 0

DC

LU

Q.

CO 1250

g 1000

Hi

1 750

Z

-£ 500

O

m

% 250

DISTILLED WATER

 Influent concentration

SYNTHETIC RETORT WASTE WATER

Distilled water

 Influent concentration

g 1500 

a

> 1250

_i 

O

CO 1000

750

500

250

Distilled water

OMEGA- 9 RETORT WASTE WATER

12 16 20 24 28 

SOIL- COLUMN EFFLUENT VOLUME, IN LITERS

32 36 40 44

5678 

SOIL- COLUMN VOID VOLUMES

10 11 12

FIGURE 21. Dissolved organic-carbon for soil-column effluents (modified from Leenheer and others, 1981).

factor in determining which types of spent shale are 

contacted and are the potential sorbents for various 

organic and inorganic constituents in retort wastewaters. 

Soils developed where oil shale in the Green River 

Formation occurs have significantly different properties 

as a sorbent compared to spent shale. The Haterton soil 

of this study had good sorbent properties for ammonium 

because of the presence of analcime, which occurs in 

most soils and sediments of this region. Soils developed 

on the Uinta Formation, which overlies the Green River 

Formation, also typically contain significant quantities 

of analcime. The capacity for ammonium adsorption and 

fixation is a desirable property because ammonia generally is thought to be the source of most of the toxicity of

retort wastewater. However, ammonium saturation of 

soil also resulted in extraction of large quantities of soil 

organic matter and concommitant release of previously 

sorbed organic and inorganic constituents when leaching by distilled water (or rainwater) followed retortwastewater application. This organic-matter extraction 

phenomenon should only occur after a relatively large 

retort-wastewater application (1 to 3 void volumes), which 

saturates the soil with ammonium. Smaller volume retortwastewater applications should result in partial to complete retention of most retort-wastewater organic solutes 

in the soil profile where they can be degraded by additional chemical and biological processes after retortwastewater evaporation.
28 EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING

130

Total dissolved organic carbon

12 16 20 24 28 32 

SOIL-COLUMN EFFLUENT VOLUME, IN LITERS

_______I_______I_______I________I________I_______L

36

567 

SOIL-COLUMN VOID VOLUMES

8 10 11 12

FIGURE 22. Percentage breakthrough curves for dissolved organic-carbon fractionation of Omega-9 retort-wastewater leachate

(modified from Leenheer and others, 1981).

MICROBIOLOGICAL DEGRADATION OF 

ORGANIC SOLUTES IN RETORT WASTEWATER

The question of the biodegradability of retort-wastewater 

constituents is important because of the environmental 

effects of retort-wastewater constituents after discharge 

and the treatability of retort wastewaters through biological processes. Omega-9 retort wastewater developed considerable turbidity after several days of storage at room 

temperature. This turbidity was caused by growth of 

rod-shaped bacterial cells (Farrier and others, 1977). Fox 

(1978) found that these cells removed significant quantities of potassium, calcium, iron, nickel, copper, zinc, and 

mercury from retort wastewater. Felix and others (1977) 

noted significant changes in high-performance, liquidchromatographic fractionation patterns of organic solutes 

when bacterial growth occurred in retort wastewater. In 

retort wastewater, it was noted that almost all the thiosulfate was converted to tetrathionate when bacterial 

growth occurred. Gauger (1981) applied DOC-fractionation analysis to Omega-9 retort wastewater during 

incubation and found that primarily hydrophobic constituents were disappearing from retort wastewater 

during bacterial growth. The largest decrease occurred 

in the hydrophobic-neutral fraction.

EFFECTS OF BACTERIAL GROWTH ON

DISSOLVED ORGANIC-CARBON CONCENTRATION

IN OCCIDENTAL-6 PROCESS AND GAS-CONDENSATE

RETORT WASTEWATERS

The subject study was conducted under a research 

grant awarded to Dr. Stephen Williams of the University 

of Wyoming. The two retort wastewaters initially were 

sterilized by passage through three sterile filter membranes (1.2-, 0.45-, and 0.22-yum pore size) stacked in 

series. These sterilized waters were stored in glass containers at 1°C for about 6 months before the growth 

experiments could be made. The results of the growth 

experiments indicated that significant degradation 

occurred in some.of the samples during storage.

The growth experiments were made in Erlenmeyer 

flasks in which Occidental-6 retort wastewaters were
MICROBIOLOGICAL DEGRADATION OF ORGANIC SOLUTES IN RETORT WASTEWATER 29

160

120

80

40

0

160

120

80

40

0

160

120

80

40

3 and 4- methylpyricfine

4 8 12 16 20 24 28 32 36 40 

SOIL-COLUMN EFFLUENT VOLUME, IN LITERS

3456 789 

SOIL-COLUMN VOID VOLUMES

10 11 12

FIGURE 23. Percentage breakthrough curves for aromatic amines 

in Omega-9 retort-wastewater leachate (modified from Leenheer 

and others, 1981).

inoculated with organisms taken from Omega-9 retort 

wastewater. The samples were incubated at 20°C on a 

rotary shaker, and periodic samples were removed for 

DOC fractionations and microbial-population determinations. Microbial populations were determined using 

spread-plate technique on a solid synthetic retortwastewater agar formulation supplemented with ammonium nitrate, dipotassium phosphate, magnesium sulfate,

and sodium acetate. Once the plates were spread with a 

diluted sample aliquot, they were incubated at 25°C and 

counted after 3 days. Three flasks were used in each 

growth experiment, with two being inoculated and the 

third used as a control.

Bacterial growth occurred readily in the Occidental-6 

process retort wastewater but could not be established in 

the Occidental-6 gas-condensate retort wastewater even 

after dilution by two, four, and eight times. Bacterial 

growth curves for flasks I and II of the Occidental-6 

process retort wastewater experiment are shown in figures 24 and 25. The growth curves were typical in that 

the organisms exhibited a brief lag phase, followed by a 

logarithmic growth phase, and finally a stationary or 

death phase.

Dissolved organic-carbon fractionation of Occidental-6 

process retort wastewaters in flasks II and III at 0, 16, 

and 32 hours into the growth experiment show that loss 

of carbon occurred as hydrophobic-acid DOC (table 9). 

However, the control flask showed the same degree of 

carbon loss as the inoculated flask, and growth was not 

observed in the control flask. The Occidental-6 process 

retort wastewaters in the inoculated or control flasks 

probably had degraded at the start of the growth 

experiments, because the DOC content decreased from 

3,000 mg/L (table 3) to 834 to 964 mg/L (table 9). In 

flask I where DOC fractionation was not made, the DOC 

concentration was 2,300 mg/L at the start of the 

experiment. This variance in DOC must have occurred 

during the 6-month sample storage after filter sterilization 

because the three flasks were stored separately. Apparently, 

some organic solutes in the Occidental-6 process retort 

wastewater are so readily degraded that the major share 

of DOC loss occurred during refrigerated storage.

CONCURRENT INDEPENDENT STUDIES OF

MICROBIAL DEGRADATION OF ORGANIC SOLUTES

IN RETORT WASTEWATERS

Torpy and others (1982) and Jones and others (1982) 

recently completed studies of physical- and biologicaltreatment processes designed to remove organic constituents from Occidental-6 process retort wastewater. 

Torpy and others (1982) found that use of activated 

sludge with powdered activated carbon to treat ammoniastripped retort wastewater alleviated many problems 

related to toxicity and limited biological growth. The 

powdered activated carbon adsorbed organic constituents 

such as aromatic amines, which are inhibitory to biological treatment, and was essential to the formation of 

a settleable floe. Certain organic solutes in Occidental-6 

process retort wastewater that neither adsorb on powdered 

activated carbon nor were biologically degraded were
30 EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING

TABLE 8. Comparison of soil- and liquid-chromatographiccolumn capacity factory (k 1) for aromatic amines

[ODS, octadecylsilica]

Soil-column 

Compound . ,

Pyridine

2-methylpyridine

3- and 4-methylpyridine

Dimethylpyridine

Quinoline

Methylquinoline

0.33

.43

1.46

4.05

5.39

7.03

ODS-column 

k 1

1.04

1.58

1.81

2.38

2.95

3.42

ODS-column k' / 

soil-column k'

3.15

3.69

1.24

.59

.55

.49

oxygenated, unsaturated nitrogen heterocyclic compounds. The most biodegradable constituents were fatty 

acids, which were removed almost completely by the 

activated-sludge treatment.

The study by Jones and others (1982) came to the 

same conclusions as the previous study regarding biodegradable and refractory organic constituents in retort 

waste water. The study found that TOSCO-11 spent shale 

could be used as well as powdered activated carbon to 

remove biologically refractory constituents. Ultraviolet 

irradiation, ozonation, and chemical oxidants had few 

beneficial effects in promoting subsequent biological degradation of refractory retort-wastewater constituents. 

Steam stripping of ammonia and hydrogen sulfide had 

beneficial effects on biodegradation of organic constituents. 

The major limiting nutrient for microbial growth in retort 

wastewater initially was phosphate and then carbon, 

because much of the DOC is refractory and cannot be 

used.

CONCLUSIONS

The results of the microbial-growth studies presented 

in this section are quite definitive and agree with each 

other. Much of the dissolved organic carbon in retort 

wastewaters is refractory or toxic or both, which limits 

microbial growth. Aromatic amines seem to be the most 

refractory class of compounds and they need to be removed 

by adsorption or steam stripping before growth can 

occur using compounds such as fatty acids as carbon 

sources. Thus, it is not surprising that bacterial growth 

occurs in Occidental-6 process retort wastewater that 

contains abundant fatty acids and that is deficient in 

aromatic amines. In contract, growth does not occur in 

Occidental-6 condensate retort wastewater that contains 

large concentrations of aromatic amines (table 3). Aromatic amines released by oil-shale retorting have been 

found to persist for several years in soils adjacent to a

HOURS AFTER EXPERIMENT STARTED

FIGURE 24. Growth curve of microorganisms in inoculated flask 

I, Occidental-6 process retort wastewater.

retort (Riley and others, 1981). Therefore, biological treatment of retort wastewaters alone is not sufficient to 

remove refractory toxic organic constituents from 

wastewaters, but needs to be combined with physical 

treatment processes such as adsorption and steam 

stripping. Aromatic amines may present the greatest 

problem in retort wastes because of their toxicity, noxious odors, and persistence in the environment.

SITE STUDIES OF EFFECTS ON WATER 

QUALITY FROM OIL-SHALE RETORTING

Most of the site studies involving water-quality effects 

of oil-shale retorting were performed at the in-situ retorting site of the Laramie Energy Technology Center, U.S. 

Department of Energy. This site was located approximately midway between Green River and Rock Springs, 

Wyoming. Two major studies were made at this site: (1) 

Changes in chemical constituents with time in monitoring wells surrounding the site-9 retort after this retort 

was burned; and (2) a first-order soil survey of the entire 

in-situ retorting site to determine the chemical and physi-
SITE STUDIES OF EFFECTS ON WATER QUALITY FROM OIL-SHALE RETORTING 31

10 15 20 25 30 35 40 45 

HOURS AFTER EXPERIMENT STARTED

50 55

FIGURE 25. Growth curves of microorganisms in inoculated flask 

II, Occidental-6 process retort wastewater.

cal characteristics of the soils that might be affected 

after a retort-waste water spill.

After the Rock Springs site studies, modified in-situ 

retorting and its effects on ground water were studied at

the Rio Blanco Oil Shale Corporation retorts located in 

Piceance Basin, Colorado, on leased tract C-a. The goals 

of this latter study were to determine vapor-phase transport processes of volatile retort-wastewater constituents 

into ground water during retorting and to study the 

natural organic-solute composition of ground waters found 

in oil shale.

EFFECTS OF EXPERIMENTAL IN-SITU

RETORTING ON GROUND WATER NEAR

ROCK SPRINGS, WYOMING

A map of the in-situ retorting site near Rock Springs, 

Wyoming, is shown in figure 26, and the wells at site 9 

are shown in figure 27. Details of well construction and 

water chemistry are given in a report by Jackson and 

others (1975). The pattern wells at site 9 used for insitu retorting operations are all about 80 m deep whereas 

the observation wells range from 73 to 93 m in depth 

with the exception of well 0-1, the project water-supply 

well, which is 382 m deep. Major constituents in the 

ground water are sodium, bicarbonate, sulfate, and 

chloride. The dissolved-solids concentrations are extremely variable, ranging from 1,100 to 44,900 mg/L. 

Organic-constituent concentrations also are extremely 

variable, with total organic-carbon concentrations 

ranging from undetectable to 1,890 mg/L.

The site-9 retort was burned from April to October 

1976 (Long and others, 1977) and 47,933 L of retort 

wastewater (designated Omega-9) were collected, filtered, 

and stored under refrigeration (Farrier and others, 1977). 

Various pattern and observation wells that remained 

operational after retorting were sampled during May

TABLE 9. Dissolved organic-carbon fractionation of sample removed at start of microbial 

growth in Occidental-6 process retort wastewater, and at 16 and 32 hours after start

of experiment 

[Data are for an inoculated flask (flask II) and an uninoculated flask (flask III), reported in milligrams of carbon per liter]

Hours since inoculation

Organic-carbon fraction

Inoculated Control Inoculated Control Inoculated Control

Total disso

Hydrophohic

Hydrophobic

Hydrophobic

Hyd rophobic

Hydrophilic

Hydrophilic

Hydrophilic

Hydrophilic

Ived-organic carbon

total

acids

bases

neutrals

total

acids

bases

neutrals

9b4

236

113

75

48

728

582

54

92

834

388

232

53

103

445

90

157

198

755

333

3

69

261

422

198

167

57

726

270

5

81

184

456

160

182

114

720

265

0

72

193

455

380

54

21

806

290

1

84

205

515

336

125

54
32 EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING

R. 106 W.

T. 18 N.

0 600 1200 FEET 

FIGURE 26. Location of experimental in-situ retorting sites near Rock Springs, Wyoming (modified from Jackson and others, 1975).

1977, October 1977, and September 1977. Changes in 

organic-solute composition of ground water were monitored by DOC f ractionation, and the results are shown in 

table 10.

The following conclusions can be made from the data 

in table 10:

1. Organic contaminants in ground water from the 

pattern wells were detected by changes in DOC-fractionation patterns, especially by increases in the hydrophobic- and hydrophilic-base fractions that are almost 

absent from native ground water. Retort-wastewater contamination of ground water was not always evidenced by 

increases in DOC concentration because of the highly 

variable DOC concentrations in native ground water 

shown by the observation-well analyses.

2. Water from pattern wells on the eastern side of the 

retort-9 well pattern have smaller concentrations of organicbase contaminants than does water from the remaining 

wells of the pattern.

3. Organic-base contaminants generally decrease with 

time in water from the pattern wells and hydrophobicacid concentrations generally increase because of the 

incursion of native ground water containing significant 

quantities (50 percent) of hydrophobic acids.

4. Evidence of organic contamination in water from 

observation wells was not detected 1 year after the retort 

was burned.

5. The average DOC-fractionation pattern of water 

from the observation wells is similar to the DOCfractionation pattern of a black "trona water" reported 

previously (Leenheer and Huffman, 1976). This fractionation pattern can be regarded as typical for kerogen from 

the Green River Formation extracted by alkaline carbonatetype ground waters.

6. The DOC concentration of Bitter Creek, flowing 

near the southern boundary of the site, is much less than 

DOC concentrations in ground waters in contact with oil 

shale, and its DOC-fractionation pattern is typical of 

surface waters of this region (Stuber and Leenheer, 1978b).

Because of the tendency of retort-wastewater constituents to sorb on some aquifer solids and to degrade 

chemically and biologically, a few major constituents 

largely unique to retort wastewater were determined 

quantitatively to determine the persistence of these 

constituents. The results are shown in table 11 (Stuber 

and others, 1978).

During the 1-year post-retorting period, thiosulfate 

and tetrathionate were removed quantitatively from retort 

wastewater, probably by chemical and biological redox 

processes. Sorption was not significant as shown by the 

previous soil-column studies. The mean concentrations 

of thiocyanate and ammonium are approximately one 

order of magnitude less than in Omega-9 water as shown 

in table 11. Dilution of these wastes by inflow of ground
SITE STUDIES OF EFFECTS ON WATER QUALITY FROM OIL-SHALE RETORTING 33

EXPLANATION

5 PATTERN WELL 

AND NUMBER

°C OBSERVATION WELL 

AND LETTER

00-1 WATER-SUPPLY

WELL AND NUMBER

NOT TO SCALE

00-1

'Direction of retort waste water 

migration (K. C. Glover, U.S. 

Geological Survey, written commun., 1983)

FIGURE 27. Wells at the site-9 in-situ retorting experiment near 

Rock Springs, Wyoming (modified from Jackson and others, 

1975).

water, by diffusion, and by pumping are factors contributing to a general decrease in waste-solute concentrations. 

The ratio of the mean concentration of thiocyanate to the 

mean concentration of ammonium in the wells sampled 

during October 1977 is very close to the ratio of these 

constituents in Omega-9 retort wastewater, indicating 

that these two constituents, which are unique to retort 

wastewater, probably are not being degraded by biological, 

oxidative, or sorptive processes, which would likely change 

the ratio. Ammonium tends to be rapidly sorbed by 

cation exchange; therefore, the spent shale in the in-situ 

retort must have a small cation-exchange capacity for 

ammonium to persist. Thiocyanate probably is the best 

indicator for retort-wastewater contamination because 

of its conservative nature and stability.

A current study (K.C. Glover, U.S. Geological Survey, 

written commun., 1984) has found that retort wastewater 

has migrated about 0.8 km south of site 9 in the Wilkens 

Peak Member of the Green River Formation, a sandstone 

that overlies the Tipton Shale Member of the Green River 

Formation, in which retorting occurred. Thiocyanate 

was used in this study to monitor waste migration.

SOIL SURVEY OF IN-SITU RETORTING SITE NEAR 

ROCK SPRINGS, WYOMING

A soil survey of the in-situ oil-shale retorting site near 

Rock Springs, Wyoming, was made by Woodward-Clyde 

Consultants (1978). Results of the soil survey are shown 

on the soils map (fig. 28). Soil series found on the undulating uplands were Horsley clay loam, Haterton loam, 

Terada loamy fine sand, and Monte fine sandy loam. 

These soil series have moderate to high permeabilities so 

that a wastewater spill most likely would infiltrate these 

soils before running off into Bitter Creek. The Horsely 

and Haterton soil series are shallow (15 to 51 cm) and are 

underlain with weathered and factured oil shale in the 

Green River Formation that readily receives ground water 

that infiltrates through the soil profiles. The Terada and 

Monte soil series are deeper (76 to 152 cm), and alkaline 

carbonates tend to accumulate in the underlying subsoils. 

The dissolved-solids concentration of the ground water 

underlying these soils probably results from variable 

leaching of these alkaline carbonates from soils into 

isolated vertical fractures so that there is limited mixing 

of adjacent ground waters depending on the fracture 

pattern. The Terada and Monte series have topsoils that 

are suitable for salvage to reclaim mining-operation sites.

The lowland alluvial soils adjacent to Bitter Creek 

southeast and southwest of the site have poor to moderate permeabilities because of extensive clay and sodium 

content, which expands clay minerals and restricts 

permeability. These are deep deposits and bedrock was 

not detected at the maximum depth (152 cm) of the 

model-pedon sampling pit. Wastewaters discharged on 

these alluvial deposits would have a good probability of 

discharging into Bitter Creek because of its proximity 

and the restricted permeability of these soils.

The various soil series were sampled by horizon at the 

model-pedon location and laboratory analyses were made 

for calcium, magnesium, sodium, potassium, cationexchange capacity, organic carbon, total kjeldahn nitrogen, 

ammonia nitrogen, phosphate, electrical conductivity, 

equivalent calcium carbonate, selenium, boron, molybdenum, lead, arsenic, and particle-size distribution. Most 

soils were alkaline (pH 7.4 to 8.6), contained 0.5 to 2.0 

percent organic carbon, and had small nitrogen and phosphorous contents, which would make these soils relatively infertile. The lowland 13 series soils also had significant 

salinities (electrical conductivities of 8 to 27 mS/cm) 

which limited plant growth. Boron in certain horizons of 

the Haterton soils series almost equaled or exceeded the 

toxicity limit of 10 ppm for most plants. All other constituents were within normal expected ranges.

According to Woodward-Clyde Consultants (1978), the 

soil survey indicated soils of little agricultural value 

except for grazing. Several of the soils were so shallow or
34 EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING

TABLE 10. Dissolved organic-carbon fractionations of various waters sampled at and near 

experimental in-situ retorting site 9 near Rock springs, WyomingSample source

Percent 

Dissolved organic

Hydrophobic Hydrophobic Hydrophobic Hydrophilic Hydrophilic Hydrophilic 

(milligrams per liter) baseg acidg neutrals bases acids neutrals

Omega-9 retort 977 13 19 17 12 29 10 

wastewater. 

Ground-water composite 122 1 37 32 8 17 5 

collected from pattern 

wells before 

retorting.

Pattern wells

Well 3; sampled 5-77 

Well 3; sampled 10-77 

Well 4; sampled 5-77 

Well 4; sampled 10-77 

Well 4; sampled 9-79 

Well 5; sampled 10-77 

Well 6; sampled 10-77 

Well 8; sampled 5-77 

Well 8; sampled 10-77 

Well 9; sampled 5-77 

Well 9; sampled 10-77

Observation wells

Well B; sampled 10-77 

Well C; sampled 10-77 

Well E; sampled 10-77 

Well F; sampled 10-77 

Well G; sampled 10-77 

Well I; sampled 10-77

Average (wells B to I) 

sampled 10-77. 

Bitter Creek; 

sampled 10-77.

TABLE 11. Concentration 

thionate, and ammonia 

Springs, Wyoming

Thiocyanate 

Sample as sulfur 

(10-18-77) (milligrams 

per literj

Omega-9 75 

Well 3 8.8 

Well 4 2.2 

Well 5 8.4 

Well 6 8.8 

Well 8 4.4 

Well 9 0

500 14 29 19 12 19 7 

395 7 39 24 7 13 10 

80 13 34 19 11 17 6 

344 6 34 28 6 18 8 

134 5 40 24 5 18 8 

479 5 49 23 2 14 7 

386 8 39 26 7 6 12 

140 10 32 21 9 18 10 

338 7 43 20 7 11 12 

120 4 39 22 8 22 5 

88 6 28 49 0 7 10

284 4 53 17 6 19 1 

20.8 3 34 24 0 31 8 

112 6 52 19 4 10 , 9 

176 3 52 32 1 11 1 

304 3 36 33 0 26 2 

1,340 0 71 17 0 12 1

373 3 50 24 2 18 3 

12.5 3 32 2 5 43 15

of thiocyanate, thiosulfate and tetrain water from site-9 wells near Rock

Thiosulfate 

and

. . Ammonium tetrathionate

as sulfur (milligrams 

(milligrams P er llterj 

per liter)

1,350 4,880 

0 421 

0 283 

0 221 

0 3J5 

0 446 

0 30

so alkaline that they could not be used for mine reclamation, 

and this may indicate a potential problem for oil-shale 

development and restoration in certain areas. Retort 

wastewaters discharged in soils located on undulating 

upland areas most likely will rapidly infiltrate these 

permeable soils and enter the vertical fractures of underlying oil shale, whereas retort wastewaters discharged 

on the sodic lowland alluvial soils will either pool and 

evaporate or will run off into Bitter Creek, which discharges into the Green River.

RIO BLANCO MODIFIED IN-SITU RETORT SITE, 

PICEANCE CREEK BASIN, COLORADO

From April 1981 through November 1982, native ground 

water and ground water that leaked into retort 1 of the 

Rio Blanco Oil Shale Corporation were sampled to characterize their composition before, during, and after the 

burning of the retort. The purposes of this study were to 

characterize the organic-solute composition of native
SITE STUDIES OF EFFECTS ON WATER QUALITY FROM OIL-SHALE RETORTING 35

Base from U.S. Geological Survey 

Kanda 1:24,000, 1978

R. 106 W.

600 METERS

EXPLANATION

MAPPING-UNIT 

NAME

HORSELY CLAY LOAM, 3 to 

9 percent slopes

HATERTON LOAM, 3 to 6-percent slopes

TERADA LOAM FINE SAND, 3 

to 9 percent slopes

MONTE FINE SANDY LOAM, 

STRONGLY ALKALINE 

PHASE 3 to 8 -percent 

slopes

ROCK OUTCROP

"13" CLAY LOAM, 0 to 3- 

percent slopes

"13" LOAM, COARSE-LOAMY 

PHASE, 0 to 3 percent slopes

"13" CLAY LOAM, FINE PAHSE 

0 to 3 percent slopes

RECLAIMED GRAVEL PIT

HORSELY-HATERTON COMPLEX , 0 to 6 - percent slopes

HORSELY-ROCK OUTCROP 

COMPLEX, 6 to 40- percent 

slopes

MODAL- PEDON LOCATION 

AND NUMBER

0 2000 FEET 

CONTOUR INTERVAL 7.6 METERS (25 FEET) 

DATUM IS SEA LEVEL

FIGURE 28. Soil map of experimental in-situ retorting site near Rock Springs, Wyoming (modified from Woodward-Clyde Consultants,

1978).

ground waters (discussed in the next section of this 

report) and to determine the transport processes that 

move wastes from the retorting process into ground 

water during retorting.

Most of the ground water initially present in the retort 

area was removed by wells and pumps in mine workings 

surrounding the retort. Residual waters that infiltrated 

the various mine workings and shafts surrounding the 

retort were pumped from a sump in the main shaft to a 

lined holding pond. This ground water that infiltrated 

the retort area was sampled from the SUB-E mine sump 

before the retort burn. During the burn, personnel from 

the Rio Blanco Oil Shale Corporation periodically monitored the sump water for constituents such as ammonium,

which would indicate retort contamination of ground 

water adjacent to the retort. No contamination was 

detected, so there was no intensive sampling for retort 

constituents during the burn. The retort was designed to 

burn under negative air pressure relative to the mine 

workings and shafts in order to contain combustion 

products within the retort. Apparently, this design was 

successful in minimizing contact of retort wastes with 

mine water during the burning of retort 1.

Chemical analyses of ground-water samples collected 

from discharges at fractures in the SUB-E development 

level and from two of the dewatering wells are presented 

in table 12. Only minor variations were detected between 

samples.
36 EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING

TABLE 12. Chemical analyses of ground waters sampled May 5, 1981, Rio Blanco retort site, Piceance Creek

Basin, Colorado

I Data in milligrams per liter except as indicated; juS at 25°C, microsiemens per centimeter at 25° Celsius]

Determination

Specific conductance

((JS at 25°C).

Dissolved organic carbon

pH (units)

Calcium

Magnesium

Sodium

Potassium

Bicarbonate

Sulfate

Chloride

Ammonium as nitrogen

SUB-E1

935

4.6

7.8

48

99

180

.5

573

425

8.3

0

SUB-E2

820

3.5

8.0

33

87

190

.3

542

399

9.4

.28

SUB-E3

791

3.5

7.7

34

84

190

.3

617

318

7.3

.10

SUB-E4

746

4.5

8.0

31

65

190

.3

544

294

8.8

0

SUB-E5

731

2.5

7.9

15

50

210

.3

461

311

21.2

.24

SUB-E6

820

4.1

8.3

35

80

190

.3

576

356

7.4

0

SUB-E7

835

...

7.9

36

78

200

.4

550

384

8.6

0

Well D-6 Well D1,370

1.8 2.

7.

45 55

58 89

200 180

.3

524 649

363 375

7.2 8.

.01

8

8

9

3

4

15

During October 1982, breakdown of pumps that dewater the mine enabled native ground water to partly 

backflood the retort. On November 19, water samples 

from the retort-sump discharge to a lined evaporation 

pond, and from the pond to which the retort-sump 

wastewater was being discharged, were collected by D. J. 

Hayes of the U.S. Geological Survey office in Meeker, 

Colorado, and by G. A. Miller from the U.S. Bureau of 

Land Management Oil Shale office in Grand Junction, 

Colorado, and were sent to the author's laboratory for 

analyses. The samples were completely analyzed within 

2 weeks of receipt because biological degradation and 

chemical oxidation would cause changes with time of 

important constituents even under refrigerated storage. 

Inorganic analyses were made by the U.S. Geological 

Survey's water-quality laboratory in Denver, Colorado, 

by methods adapted to oil-shale retort wastewater 

(Leenheer and others, 1981) and organic analyses were 

made in the author's laboratory by methods developed 

specifically for retort waste water s (Leenheer and others, 

1982). Organic constituents also were identified and confirmed by gas chromatography-mass spectrometry performed in the water-quality laboratory.

Inorganic analyses of the water sampled November 19, 

1982, from the evaporation pond containing retort-sump 

wastewater and freshly discharged water from the sump 

of retort 1 are shown in table 13. Pond water had a lower 

specific conductance (and dissolved-solids concentration) 

than the retort-sump wastewater because retort-sump 

wastewater discharged into the pond was diluted by a 

large volume of native ground water that infiltrated the 

retort and was previously discharged into the pond; 

chemistry of native ground water is shown in table 12.

TABLE 13. Inorganic analyses of wastewaters sampled November 

19, 1982, from backflooded Rio Blanco retort 1, Piceance Creek 

Basin, Colorado

[yug/L, micrograms per liter; mg/L, milligrams per liter; /jS, microsiemens per 

centimeter at 25° Celsius"

Constituent

Barium

Beryllium

Cadmium

Calcium

Cobalt

Copper

Hardness

Iron

Lead

Lithium

Magnesium

Manganese

Molybdenum

Nitrogen (NH4 as N)

Nitrogen (NH4 as NH4 )

pH

Silica

Sodium

Specific conductance

Strontium

Vanadium

Zinc

Sulfur species

Total sulfur

Thiocyanate

Thiosulfate

Tetrathionate

Sulfate

Units

Mg/L

Mg/L

Mg/L

mg/L

Mg/L

Mg/L

mg/L

Mg/L

Mg/L

Mg/L

mg/L

Mg/L

Mg/L

mg/L

mg/L

mg/L

mg/L

MS

Mg/L

Mg/L

Mg/L

mg/L

mg/L

mg/L

mg/L

mg/L

Discharged retortsump wastewater

68

2.7

<3

160

<9

<30

820

320

<30

1,900

100

47

600

14

18

8.2

25

400

3,650

7,500

<18

47

530

.9

<1

<2

530

Water from

evaporation pond 

containing retortsump water

68

1.8

<3

110

<9

<30

650

370

<30

750

90

54

260

12

15

8.2

25

290

2,590

7,300

<18

38

310

1.2

<1

<2

310
SITE STUDIES OF EFFECTS ON WATER QUALITY FROM OIL-SHALE RETORTING 37

Inorganic constituents and physical properties that had 

significant increases in the retort-sump wastewater compared to background values in native ground water were 

calcium, ammonium, sodium, specific conductance, and 

thiocyanate, which is not found in natural waters.

Ammonium concentrations are affected by biological 

uptake and cation-exchange effects, and calcium, lithium, 

and sodium are affected by cation-exchange interactions. 

Calcium and hardness concentrations are dependent on 

calcining of carbonate minerals and surface chemistry 

changes of spent shale during retorting. The absence of 

thiosulfate and tetrathionate in both the retort-sump 

and pond wastewaters probably indicate their oxidation 

to sulfate by sulfur-oxidizing bacteria that are known 

to be present in the access levels and shafts adjacent 

to the retort.

Organic analyses of the Rio Blanco retort-sump and 

pond wastewaters are shown in table 14. The organicwaste constituents in these wastewaters are similar to 

constituents in the retort wastewaters from the Occidental-6 retort at Logan Wash, Colorado, except that 

the more soluble and volatile constituents are depleted in 

the Rio Blanco wastewaters. Most likely these soluble 

and volatile constituents were removed in retort wastewaters produced during the burn, and the remaining 

organic constituents with lesser solubility and volatility 

are now being leached from the spent shale and unrecovered shale oil.

Biological degradation of organic acids and phenols 

occurred in the pond water prior to the sampling on 

November 19. Phenols and dicarboxylic acids degraded 

at a faster rate than aliphatic and aromatic monocarboxylic acids, as shown by concentration differences between 

retort-sump and pond wastewaters in table 14. Phenols 

degrade by both aromatic-ring cleavage and enzymatic 

oxidative-coupling mechanisms, with the degradation 

rate being directly related to phenol solubility. Residual 

concentrations of phenols found in the pond water reflect 

the microbial degradation rates published for these phenols (Fitter, 1975).

Aliphatic acids degrade through coenzyme-A conjugates with the carboxyl group in Kreb's-cycle oxidation. 

Dicarboxylic acids have twice as many carboxyl-group 

sites of attack for biological oxidation as monocarboxylic acids, thus they degrade at a faster rate (table 14). 

Aliphatic-monocarboxylic acids are degraded successively into two-carbon fragments that are converted into 

acetyl coenzyme A until a three-carbon chain is obtained; 

this chain is converted into propionyl coenzyme A, which 

degrades through a slower metabolic pathway. The nearly equivalent concentrations of propanoic and 2-methylpropanoic acid concentrations in the retort-sump and 

pond wastewaters show the effect of the slower degradation rate of the propionyl coenzyme-A pathway compared to the acetyl coenzyme-A pathway, which is operative 

with the other aliphatic-rnonocarboxylic acids.

Aromatic amines are not significantly affected by biological degradation, and therefore, their relative concentration is much greater than the organic acids in the 

pond wastewater. The more soluble, lower molecularweight aromatic amines are more enriched in the pond 

wastewater than the retort-sump wastewater, which may 

indicate that concentrations of conservative constituents were much greater in wastewaters pumped from the 

backflooded retort prior to the November 19th sampling 

of the retort-sump wastewater.

The DOC-fractionation data clearly have a retortwastewater signature with large percentages of organic 

bases, but it does not show the effects of biological 

degradation of acids and phenols in the pond wastewater. 

Apparently, degradation products such as humic and 

fulvic acid are a part of the same compound classes as the 

acid precursors, and a significant shift in the data does 

not occur.

CONCLUSIONS

No migration of retort wastes to adjacent ground 

waters during the retort burn was detected at either the 

Rock Springs or the Rio Blanco sites; no migration for as 

much as 2 years after the burn was detected at the Rock 

Springs site. However, a recent study (K. C. Glover, U.S. 

Geological Survey, written commun., 1984) found significant waste migration at the Rock Springs site after 

backflooding of the retort by native ground water was 

completed. Backflooding of water toward the dewatered 

retort at the Rock Springs site, mine dewatering, and 

burning the retort under a negative pressure differential 

at the Rio Blanco site were factors that prevented subsurface migration of retort wastes. No vapor-phase transport of organic contaminants to native ground water was 

detected during burning of Rio Blanco retort 1, and 

water contaminated during partial backflooding of retort 

1 after the burn was removed from the retort and contained in a lined evaporation pond. Analyses of wastewaters 

pumped from Rio Blanco retort 1 indicate that significant 

quantities of retort contaminants are released into water 

from spent shale and unrecovered shale oil when a modified 

in-situ oil-shale retort is backflooded after retorting.

Subsurface retorting can have a major impact on groundwater hydrology because of creation of a dewatered zone 

surrounding the retort, creation of a burned retort with 

different aquifer characteristics, and creation of liquid 

and gaseous products and wastes within the retort. Determination of retort-waste migration and ground-water 

quality changes will be a long-term monitoring effort far 

beyond the time-scale of this project, because of the long
38 EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING

TABLE 14. Organic analyses of wastewaters sampled November

5, 1982, from backflooded Rio Blanco retort

Basin, Colorado

[fjg/L,, micrograms per liter;

1, Piceance Creek

ND, not detected; NA, not analyzed; mg/L,

milligrams per liter]

Compound

Aiiphatic-monocarboxyJic acids

Acetic acid 1

Propanoic acid 1

2-Methylpropanoic acid 1

Butanoic acid 1

2-Methylbutanoic acid2

3-Methylbutanoic acid2

Pentanoic acid 1

C-6 acid isomers 2

Hexanoic acid 1

C-7 acid isomers 2

Hepanoic acid 1

C-8 acid isomers 2

Octanoic acid 1

C-9 acid isomers 2

Nonanoic acid 1

C-10 acid isomers 2

Decanoic acid 1

C-ll acid isomers 2

AJiphatic-monocarboxyJic acids

Tridecanoic acid2

Tetradecanoic acid 2

Pentadecanoic acid2

9-Hexadecenoic acid2

Hexadecanoic acid2

Hepatadecanoic acid2

9-Octadenoic acid2

Octadecanoic acid2

Aiiphatic-dicarfcoxyJic acids

Ethananedioic acid 2

Propanedioic acid2

Pentanedioic acid 2

C-6 acid isomers 2

C-7 acid isomers 2

C-8 acid isomers 2

C-9 acid isomers 2

C-10 acid isomers 2

Aromatic acids

Benzoic acid2

2-Methylbenzoic acid 2

Aromatic acids

3-Methylbenzoic acid2

4-Methylbenzoic acid2

Dimethylbenzoic acid isomers 2

Trimethylbenzoic acid isomers 2

Pheno.Zs

Phenol 1

2-Hydroxytoluene 1

3- and 4-Hydroxytoluene 1

l,2-Dimethyl-4-Hydroxybenzene 1

Dimethylhydroxybenzene isomers 2

Discharged retortsump wastewater

(Mg/L)

680

101

291

497

176

232

438

573

520

271

612

150

295

126

48

98

29

38

ND

9

ND

8

36

ND

4

12

681

179

327

231

104

19

22

10

123

18

40

12

40

10

196

92

238

27

236

Water from

evaporation pom

containing retort

sump wastewatei

(Mg/L)

250

92

260

254

104

120

344

198

330

101

262

73

79

50

16

20

15

3

14

12

19

46

4

10

20

185

12

40

60

14

2

3

40

5

14

4

15

9

ND

10

36

9

167

TABLE 14. Organic analyses of wastewaters sampled November

19, 1982, from backflooded Rio Blanco retort 1,

Basin, Colorado Continued

Compound

Aromatic amines

Aniline 2

Aminotoluene isomers 2

Pyridine 1

2-Methylpyridine 1

3- and 4-Methylpyridines 1

2,6-Dimethylpyridine 1

Dimethylpyridine isomers 2

C-3 alkylpyridine isomers 2

C-4 alkylpyridine isomers 2

Aromatic amines

C-5 alkylpyridine isomers 2

C-6 alkylpyridine isomers 2

C-7 alkylpyridine isomers 2

C-8 alkylpyridine isomers 2

Quinoline 1

Isoquinoline 1

Methylquinoline and methyl isoquinoli

isomers^

C-2 alkylquinoline and C-2 alkylisoqu

isomers^

C-3 alkylquinoline and C-3 alkylisoqu

isomers 2

N-phenylbenzeneamine 2

N-phenyltolueneamine isomers 2

Carbazole2

Acridine 2

Benzo-f-quinoline 2

Methylbenzo-f-quinoline isomer 2

Hydroxypridines

2-Hydroxypyridine 1

4-Hydroxypyridine 1

Hydr oxypy ri dines

2-Hydroxy-6-methylpyridine 1

Dissolved organic-ca

_ . Discharg Fraction

sump w

DOC (mg/L)

Total DOC 26.0

Hydrophobic bases 2.0

Hydrophobic acids 4.8

Hydrophobic neutrals 5.0

Hydrophilic bases 3.0

Hydrophilic acids 8.0

Hydrophilic neutrals 3.2

1 Identif ications confirmed and q

2 Tentative identifications and q

chromatography-mass spectrometry .

Discharged retortsump wastewater

(M8/L)

00 0 J

63

68

35

36

29

56

159

151

90

38

6

4

7

4

ne 37

incline 65

incline 20

5

15

1

.8

ND

.7

57

3

94

rbon (DOC) fractionati

Wate

ed retort- , pond

astewater

Piceance Creek

Water from

evaporation pond

containing retortsump wastewater

(Mg/L)

268

214

241

57

96

54

122

194

178

85

53

7

3

11

4

55

96

29

4

20

ND

1.0

1.0

ND

NA

NA

NA

on

r from evaporation

containing retortump wastewater

Percent DOC DOC (mg/L) Percent DOC

100 30

8 2

20 6

21 8

13 3

25 7

13 3

.6 100

.4 8

.2 20

.6 28

.0 10

.2 24

.2 10

uantified with standards.

uantif ication only by gas
CHARACTERIZATION OF NATURAL ORGANIC SOLUTES 39

period required for original ground-water flow patterns to 

be re-established after retort abandonment. An additional 

complicating factor will be the very directional nature of 

waste migration due to fracture flow of ground water.

Monitoring of retort-wastewater constituents within 

the site-9 retort at Rock Springs and Rio Blanco retort 1 

detected rapid degradation of certain reduced sulfur species (thiosulfate and tetrathionate), but thiocyanate persisted and was a tracer to determine retort-wastewater 

dilution by backflooding ground water. Aromatic amines 

in the hydrophobic- and hydrophilic-base fractions of 

DOC fractionation also persisted and can be unique indicators of retort-wastewater contamination.

A soil survey at the Rock Springs site indicated that a 

wastewater spill on an upland soil would infiltrate fairly 

rapidly through the soil and underlying fractured shale 

to the ground water. However, if wastewater spill runoff 

reached an alluvial soil with significant clay and alkali 

content, commonly found near watercourses in this region, 

the spill would either run off or evaporate and the potential for surface-water contamination is much greater.

CHARACTERIZATION OF NATURAL

ORGANIC SOLUTES IN WATERS

ASSOCIATED WITH OIL SHALE IN

THE GREEN RIVER FORMATION

To determine changes in water quality that occur 

during development of oil-shale resources, it is necessary 

to determine the quantity and type of natural organic 

constituents of ground water because at the mine site, 

much of the impacting oil-shale wastes also are organic 

in nature. Distinguishing characteristics of natural and 

contaminant organic constituents related to oil-shale 

retorting will be examined in this section of the report. 

Many of the procedures for both the isolation and characterization were developed specifically for this study because the state of the science for determination of natural 

organic constituents is not as advanced as for organiccontaminant determinations.

DOC-FRACTIONATION SURVEYS OF SURFACE 

AND GROUND WATERS

DOC fractionation was used as a relatively inexpensive reconnaissance tool to define compound-class compositions of natural waters associated with oil shale in 

the Green River Formation. DOC fractionations of ground 

waters at the Rock Springs site are shown in table 10; 

DOC fractionations of surface waters sampled in the 

White River Basin area of Utah are presented in a report 

by Stuber and Leenheer (1978b). Summary averages of

these and other data sets are shown in table 15. The 

variability of the DOC fractionations within a data set is 

represented by standard deviations and coefficients of 

variation shown in table 16 (Stuber and Leenheer, 1978b).

The DOC fractionations of sets of samples from the 

White River Basin, Utah, are virtually identical for the 

two different sampling periods (table 15). However, the 

variability data for one of these sample sets indicate 

considerable variability among samples within a set. 

The published deviations for the standard DOC-fractionation method (Leenheer and Huffman, 1979) exceed 

the concentrations of hydrophobic and hydrophilic bases 

and equal the concentration of hydrophobic neutrals 

found for the data in table 16; thus, variability of these 

fractions mostly is due to analytical variability. Most of 

the real variability in table 14 is in the hydrophilic-acid 

and -neutral fractions. These two fractions contain more 

biodegradable organic constituents than the hydrophobicacid fraction that contains biologically refractory fulvic 

acid. The rapid biological conversion processes within 

the hydrophilic-acid and -neutral fractions, are postulated to be the reason for the variability between samples 

for this and other surface-water data sets shown in table 25.

Surface-water samples from the Piceance Creek Basin 

differ from samples from the White River Basin primarily in the greater hydrophilic-neutral concentration in the 

Piceance Creek Basin samples. This difference probably 

is related to sampling date (June) and location, because 

much of the Piceance Creek Basin water is used for flood 

irrigation of hay in June, whereas the White River Basin 

waters sampled for this study largely are unused for 

irrigation. Plant leachates (such as hay) contain significant percentages (40 percent) of polysaccharides that 

fall into the hydrophilic-neutral fraction (Caine, 1982).

A second interesting trend is the decrease in hydrophilicneutral concentration in the headwater streams of the 

Piceance Creek Basin (26.6 percent) to Piceance Creek 

(15.8 percent) to the White River (5.4 percent). This 

decrease again can be related to decay of biodegradable 

plant polysaccharides leached by irrigation in headwater 

regions of the Piceance Creek Basin. The lower DOC in 

the White River may be partly related to decay of biodegradable organic constituents; the other factor is related 

to dilution by minimal DOC water from its headwaters in 

the Flattops region. A White River sample collected in 

June 1982, 4 km below Trappers Lake, contained 0.3 

mg/L DOC.

The ground-water samples shown in table 15 have 

their own unique fractionation patterns. The DOC fractionations from site-9 near Rock Springs, Wyoming, 

discussed previously appear to be similar to trona blackwater acids. The ground water sampled from leased tracts 

in Colorado differs from the Rock Springs samples in 

that they are from much deeper sources, are much more
40 EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING

TABLE 15. Dissolved organic-carbon fractionations of various surface and ground waters associated with oil shale in the Green

River Formation 

[Data in percent dissolved-organic carbon (DOC); mg/L, milligrams per liter]

Source of samples

DOC 

(mg/L)

Hydrophobic 

bases

Hydrophobic Hydrophobic Hydrophilic Hydrophilic Hydrophilic 

acids neutrals bases acids neutrals

White River Basin, Utah, surface water sampled

November 1975 (average of 10 samples). 

White River Basin, Utah, surface water sampled

April 1976 (average of 9 samples). 

Piceance Creek Basin, Colorado, surface water

sampled June 1975 (average of 12 samples) 1 . 

Piceance Creek, Colorado, sampled

June 1975 (average of 4 samples) 1 . 

White River sampled November 1975 near

Bonanza, Utah, and October 1981 near

Rangely, Colorado, (average of 2 samples). 

Ground water from site-9 near Rock Springs,

Wyoming, sampled October 1977 (average of

6 samples). 

Well D-8, tract C-a, Piceance Creek Basin,

Colorado, sampled October 1981. 

Wells SG-6-1, SG-6-2, SG-6-3, SG-8R, SG-10R,

SG-20, tract C-b, Piceance Creek Basin,

Colorado (data from Slawson, 1980).

7.3 

6.7

36.0

36.5

17.3

19.3

29.8

15

18.8

3.3 

5.4

20.0

31.3

34.1

14.0

14.2

26.6

15.8

5.4

24 9

____Total_____ 

29.2

Preliminary nonstandard methodology (Leenheer and Huffman, 1976) was used, which resulted in shifts of dissolved-organic carbon from the 

hydrophobic-acid and hydrophilic-acid fractions into the hydrophobic-neutral fraction.

TABLE 16. Variability of dissolved organic-carbon fractionations 

for 10 surface waters sampled in the White River Basin, Utah, 

November 1975

[DOC, dissolved-organic carbon]

Mean 

(percent of DOC)

Standard Coefficient of 

variation

Hydrophobic bases 

Hydrophobic acids 

Hydrophobic neutrals 

Hydrophilic bases 

Hydrophilic acids 

Hydrophilir neutrals

reducing as evidenced by hydrogen sulfide, are more 

homogeneous in solute chemistry, and their DOC concentration is much less (table 15). The wells listed in table 15 

for the leased tracts in Colorado withdraw ground water 

that resides in the richest kerogen zones of Green River 

oil shale, and details of their construction are given in the 

report edited by Slawson (1980). Approximately onefifth of the DOC of the Colorado ground waters resides in 

the base fractions, which is an unusual aspect of these 

samples. The significant organic-nitrogen concentration 

of kerogen in the Green River Formation may be reflected in the large organic-base solute concentration in these 

ground waters. The larger DOC and organic-acid concentrations in the Rock Springs ground waters most likely 

are related to oxidative weathering of kerogen of shallow 

oil shale, which cannot occur in the deeper oil-shale strata being developed at the leased tracts in Colorado.

ISOLATION AND FRACTIONATION OF 

NATURAL ORGANIC SOLUTES FROM WATER

To obtain more specific structural information than 

analytical DOC-fractionation data about natural organic 

solutes in water, the preparative DOC-f ractionation procedure (Leenheer, 1981) was scaled up and modified to 

produce gram quantities of natural organic-solute fractions from processing a few hundred liters of water 

(Leenheer and Noyes, 1985). These large organic-solute 

fractions then were characterized by elemental analysis, 

functional-group analysis, infrared spectroscopy, and proton nuclear magnetic resonance spectroscopy to obtain 

organic structural information.

A modular filtration and column-adsorbent system 

was constructed for onsite concentration and fractionation of organic solutes from large volumes of water. 

This system was housed in a mobile laboratory, and flow 

of water to and from the mobile laboratory is shown in 

figure 29. Flow of water through the filtration and columnadsorbent system within the mobile laboratory is shown 

in figure 30. An average of 1 to 2 L/min of water was 

processed through this system, and a fortyfold to fiftyfold
CHARACTERIZATION OF NATURAL ORGANIC SOLUTES 41

concentration factor of organic solutes in water was 

attained at the field sampling site. Additional concentration by vacuum rotary evaporation, desalting, and freezedrying was done in the laboratory after sampling. Specific 

details on the operation of the filtration and column adsorbent system and on the final processing of the organicsolute fractions is given by Leenheer and Noyes (1985).

ORGANIC-SOLUTE CHARACTERIZATION OF

GROUND WATER AT THE RIO BLANCO SITE,

PICEANCE CREEK BASIN, COLORADO

A preliminary run of well D-8 ground water through 

the preparative DOC-fractionation procedure revealed 

that large quantities of sulfur were being isolated with 

the hydrophobic-acid fraction as evidenced by sulfur 

fouling of the XAD-8 resin. Subsequent tests on this 

sulfur revealed that most of this sulfur was speciated as 

polysulfide anion. Polysulfide imparted a yellowish-green 

color to well D-8 ground water, and it slowly decomposed 

to elemental sulfur and hydrogen sulfide when the water 

samples, columns, and fraction concentrations were 

acidified. Because the elemental sulfur that was produced fouled the adsorbent resin columns, a method was 

sought to eliminate polysulfide and hydrogen sulfide 

from the water before it was processed. The addition of 

40 mg/L of zinc as zinc sulf ate was found to quantitatively remove polysulfide and sulfide from solution after 1 

hour of precipitate formation. Gravimetric determination of the precipitate found 24.5 mg/L sulfur as sulfide. 

About 10 percent of the dissolved organic carbon 

coprecipitated with the zinc sulfide, and no satisfactory 

method was found to recover this carbon from the 

precipitate.

On December 2, 1981, 304 L of well D-8 water was 

processed through the filtration and column-adsorbent 

system after zinc-sulfide precipitation. A total of 786 mg 

of organic carbon was recovered (89-percent recovery of 

DOC), which was fractionated as follows: 13 mg C (carbon) 

as hydrophobic bases, 12 mg C as weak hydrophobic 

acids, 19 mg C as hydrophilic bases, and 742 mg C as 

strong hydrophobic and hydrophilic acids. The strong 

hydrophobic- and hydrophilic-acid fractions were not 

separated because the column capacity-factor (k') cutoff 

was kept as low as 2 during the laboratory desalting of 

this fraction on a column of XAD-8 resin.

The hydrophobic- and hydrophilic-base fractions were 

assayed for pyridines, quinolines, and hydroxypyridines 

by liquid-chromatographic procedures used for the analyses of oil-shale retort wastewaters (Leenheer and others, 

1982). No aromatic amines were found. Only broad, undefined peaks characteristic of natural organic polymeric 

material were obtained.

Elemental analyses of certain organic-solute fractions 

from well D-8 ground water are shown in table 17. A 

complete elemental analysis was possible only on the 

strong hydrophobic- and hydrophilic-acids fraction, because 

insufficient material was obtained in the other fractions 

isolated. The hydrophilic-base fraction had a significant 

nitrogen concentration, and its minimal carbon concentration indicated that much of the material isolated in 

this fraction was inorganic in nature. The combined 

acids fraction also contained a relatively large nitrogen 

concentration (2.6 percent) compared to most aquatic 

organic acids whose nitrogen concentration is near 1 

percent (E. M. Thurman and R. L. Malcolm, U.S. Geological Survey, written commun., 1982). The large nitrogen concentration in these fractions is reflective of kerogen 

in the Green River Formation. The nitrogen concentration of kerogen averages 2.2 percent (Saxby, 1959).

The acids fraction had a much greater oxygen concentration (33 percent versus 6.0 percent) and smaller hydrogen (5.4 percent versus 10.3 percent) and carbon (49.7 

percent versus 80.5 percent) concentrations than kerogen in the Green River Formation. The large oxygen and 

nitrogen concentrations and smaller carbon and hydrogen concentrations in organic solutes in ground water in 

the Green River Formation compared to kerogen in the 

Green River Formation, probably represent water-solubility 

partitioning of polar oxygen- and nitrogen-containing 

constituents of kerogen into ground water. Apparently, a 

very small percentage of kerogen is soluble in ground 

water at well D-8 because the DOC concentration is only 

2.3 mg/L.

Carbon and sulfur analysis of the zinc-sulfide precipitate indicated that the precipitate was not pure zinc 

sulfide. Dissolution of the precipitate in nitric acid followed by plasma atomic-emission spectroscopic analysis 

found certain heavy metals (Cr, Co, and Mo) that are 

characteristic of, and may be derived from, stainless 

steel corrosion products in the well-pump system at well 

D-8. The carbon concentration in the precipitate is indicative of coprecipitated organic solutes discussed previously.

The fraction characterized in greatest detail was the 

strong hydrophobic- and hydrophilic-acids fraction that 

comprised 94 percent of the isolated material. These 

acids were almost pure white in color after freeze-drying. 

An aqueous titration of this acid fraction with sodium 

hydroxide found 5.5 meq/g of acid that was taken as a 

measure of free carboxyl groups. The remaining characterizations were made by combining chemical derivatizations with infrared and nuclear magnetic resonance 

spectroscopic characterizations.

The infrared spectrum of the underivatized acid fraction of well D-8 is shown in figure 31. This spectrum is 

distinguished by two features: (1) The strong carboxyland carbonyl-group absorbance at 1,720 cm-1 (reciprocal 

centimeters), which is indicative of its acid concentration;
42 EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING

MOBILE LABORATORY

-Liter 

measure 

carboy

Pump 

FIGURE 29. Flow of water through mobile laboratory (from Leenheer and Noyes, 1985).

and (2) the silica bands at 1,080, 950, and 800 cm-1 . This 

silica most likely is silicic acid esterified to organic acids 

and alcohols and probably is the major component of the 

5.86-percent ash concentration shown by data in table 

17. There was no indication of any aromatic character of 

these organic acids.

Proton nuclear magnetic resonance (NMR) spectra of 

the well D-8 acids were run in deuterium oxide and 

deuterated dimethylsulfoxide solvents. A trace amount 

of trifluoroacetic acid was added to the dimethylsulf oxide 

to shift the adsorbed water peak from the spectral region 

of interest. The two NMR spectra were combined, the 

solvent peaks were subtracted, and the composite NMR 

spectrum is shown in figure 32. Integration of the proton 

NMR spectrum results in the quantitative assignment 

of hydrogen to the following structures: aliphatic-methyl 

and methylene hydrogen (0 to 1.75 ppm)=61.5 percent 

of total integral; aliphatic hydrogen on carbons alpha 

to carboxyl and carbonyl groups (1.75 to 3.0 ppm)=29.7 

percent; aliphatic hydrogens on carbons attached to 

ester, ether, and hydroxyl oxygens (3.0 to 5.0 ppm)= 

7.1 percent; and aromatic hydrogens (7.0 to 8.5 ppm)= 

1.7 percent.

TABLE 17. Elemental analyses of organic-solute fractions from 

Rio Blanco well D-8, tract C-a, Piceance Creek Basin, Colorado

Elements

Carbon

Hydrogen

Oxygen

Nitrogen

Sulfur

Ash

Hydrophilic Strong hydrophobic

bases and hydrophilic acids

(percent) (percent)

18.22 49.67

5.21 5.4

33.0

13.44 2.43

1.97

5.86

Zinc sulfide

and polysulfide

precipitate

(percent)

0.89

...

 

...

23.88

 

Quantitative information on carbonyl concentration 

in well D-8 organic acids was obtained by synthesizing 

the methoxime and measuring the increase in hydrogen 

concentration by proton NMR as determined by the 

methoxy peak at 3.5 to 3.8 ppm. The methoxime was 

synthesized by heating the sample in 0.1 N (normal) 

methoxime acetate at 85°C for 1 hour, passing the sam-
CHARACTERIZATION OF NATURAL ORGANIC SOLUTES 43

Stain less-steel filters 

25 micrometers

Specificconductance

Desorption pump meter and cell 

(to inlets)

Overflow 

to source

Sodium 

hydroxic 

infusion

pump

B

Exit 

tubing

Desorpt ionpump intake

EXPLANATION 

= ADSORPTION TUBING 

» DESORPTION TUBING 

 AIR BLEED TUBING

1-WAY VALVE

2-WAY VALVE

3-WAY VALVE

FIGURE 30. Flow of water through filtration and column-adsorbent system (from Leenheer and Noyes, 1985).

pie through a hydrogen-saturated cation-exchange resin 

to remove unreacted methoxime cations and freeze-drying 

the sample to remove water and acetic acid.

Lastly, aliphatic-hydroxyl groups were determined by 

forming the trifluoroethyl ethers by reacting the sample 

suspended in methylene chloride with trifluorodiazoethane
44 EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING

16 1820 25 3035

4000 3500 3000 2500 2000 1800 1600 1400 1200 1000 800 600 400 200

WAVENUMBERS (CM' 1 )

FIGURE 31. Infrared spectrum of organic acids of ground water in well D-£

(Roller and Dorn, 1982). Aliphatic-alcohol ether derivatives can be resolved from carboxylic-acid ester derivatives by F-19 (fluorine-19) NMR. When the F-19 NMR 

spectrum was run on the derivatized well D-8 organic 

acids, only trifluoroethyl ester derivatives were detected, 

and therefore, aliphatic-hydroxyl concentration, if present, 

must be minimal.

A summary of all qualitative organic structural and 

functional-group information is given in table 18. The 

following conclusions can be reached about well D-8 

organic acids, which closely conform to the Yen-YoungShih structure model of kerogen in the Green River 

Formation (Yen, 1976):

1. Aromatic-carbon systems are present only in minute quantities; however, this does not rule out the presence of isolated double bonds such as those present in 

substituted hydroaromatic or heterocyclic systems.

2. The bulk of the carbon skeleton consists of aliphatic-naphthenic rings. Five- and six-membered rings 

predominate.

3. Free-end and flexible long-chain linear polymethylene 

structures are absent, as evidenced by the absence of 

terminal methyl groups in the proton NMR spectrum.

4. Aliphatic-naphthenic ring clusters most likely are 

predominately linked with ether bridges and to a lesser 

extent, linked with ester bridges. Significant quantities 

of oxyen are not associated with hydrocarbon structures; 

therefore, these bridges are at Tertiary or Quaternary 

carbon sites.

The major difference between the well D-8 organic 

acids and the Yen-Young-Shih model of kerogen is the

significant carboxyl concentration in well D-8 acids. The 

water solubility of these acids undoubtedly is due to its 

polar carboxylate concentration. There is slightly more 

than one carboxyl group on each naphthenic ring.

The close correspondence of well D-8 organic acids to 

the structure of kerogen in the Green River Formation 

provides a valuable indicator to distinguish these solutes 

from organic contaminants and organic solutes of natural origin in surface waters. The proton NMR spectrum, 

in particular, is the best tool for assaying the unique 

characteristics of organic solutes derived from oil shale 

of the Green River Formation.

ORGANIC-SOLUTE ASSESSMENT 

OF THE WHITE RIVER

In addition to the analytical DOC-fractionation data 

discussed previously in connection with table 13, two 

large-volume samples from the White River were processed through the preparative DOC-fractionation procedure to obtain sufficient material for extensive chemical 

characterization (Leenheer and Noyes, 1985). The sampling site was 25.4 km east of Rangely, Colorado, on 

State Highway 64 at a Rio Blanco County road bridge 

that crosses the White River. The first sampling was 

during a low-flow period from September 21 to 25, 1981. 

The second sampling was during the peak of the spring 

runoff from June 7 to 11, 1982. The sampling site was 

downstream from all surface-water inputs to the White 

River from the Piceance Creek Basin and upstream from 

the city of Rangely. The volume of water processed and
CHARACTERIZATION OF NATURAL ORGANIC SOLUTES 45

987654321

CHEMICAL SHIFT, IN PARTS PER MILLION

FIGURE 32. Proton nuclear magnetic resonance (NMR) spectrum of organic acids of ground water in well D-8.

quantity of organic solutes recovered in the various fractions are summarized in table 19.

Organic-carbon recoveries are underestimated in table 

19 because hydrophobic- and hydrophilic-neutral fractions (estimated to be about 30 percent of the carbon 

from the White River, based on data from table 15) were 

not recovered in the preparative fractionation. Therefore, 

the September 1981 sample gave about the correct recovery (64 percent) for the remaining four fractions, but the 

June 1972 sample gave an overestimated recovery (154 

percent). Variations in DOC concentration with time are 

the most probable reasons for the significant carbon 

recovery of the June sample, because only one sample for 

DOC determination was taken during the 4-day sampling period.

The September 1981 sample was subjected to one of 

the first organic structural studies ever undertaken of 

both humic and non-humic substances of natural origin 

in a surface water. Therefore, much of this sampling was 

devoted to developing and applying characterization methods for these organic-solute fractions.

About 94 percent of the recovered carbon resided in

the strong hydrophobic- and hydrophilic-acid fractions 

in the September 1981 sample. To obtain more specific 

information on the various acid groups within this mixture, 

this acid fraction was subdivided further by the following procedures. The entire solute fraction was concentrated about tenfold by vacuum rotary evaporation. A 

precipitate formed that was designated humic-acid no. 1. 

After separating this percipitate by centrifugation, the 

concentrate was acidified to pH 2, and a second precipitate formed that was designated humic-acid no. 2. The 

acidified concentrate was passed through a XAD-8 column so that all acids with capacity factors (&') greater 

than ten were retained. After desorption, this acid fraction was designated strong hydrophobic acids. The column effluent containing hydrophilic acids was passed 

through two successive XAD-8 columns to isolate a 

hydrophilic-acid no. 1 fraction whose fe'for XAD-8 ranged 

from 2 to 10 and a hydrophilic-acid no.2 fraction whose k' 

for XAD-8 ranged from 0.3 to 2.0. Acids whose k' for 

XAD-8 was less than 0.3 were called ultrahydrophilic 

acids, and they were isolated from inorganic salts by a 

series of recrystallation, precipitation, and evaporation
46 EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING

TABLE 18. Quantitative organic structural- and functional-group information on well

D-8 organic acids

[NMR, nuclear magnetic resonance]

Structural- or 

functioridlgroup unit

Empirical formula.

Hydrogen (H) distribution 

Acidic-carboxy1 hydrogen.

Isolated aliphatic-hydrocarbon 

hydrogen.

Aliphatic hydrogen on carbons

alpha to carbonyl, carboxyl,

and ester groups. 

Aliphatic hydrogen on carbons

attached to hydroxyl ester and

ether oxygens. 

Aromatic hydrogen.

Oxygen (O) distribution 

Carboxyl oxygen.

Oxygen (O) distribution 

Carbonyl oxygen.

Quantitative

C 67 H S8034 N 3 S

Silica oxygen. 

Aliphatic-hydroxyl oxygen. 

Ether oxygen.

Sulfur concentration. 

Number of rings or double bonds

Carboxyl oxygen double bonds. 

Carbonyl oxygen double bonds.

Ester oxygen double bonds. 

Aromatic rings and double bonds 

associated with aromatic H.

Unaccounted rings and double bonds

Ratio of unaccounted rings and 

double bonds with structural

Elemental analysis.

Titration data. 

Proton NMR.

Proton NMR. 

Proton NMR.

Proton NMR. 

Titration data.

Methoxime derivative,

proton NMR. 

Proton NMR.

Infrared spectrum, 

ash concentration.

fluorine NMR. 

Difference from total

oxygen. 

Elemental analysis.

1-S Elemental analysis.

24 Calculated from C:H 

ratio of empirical 

formula. 

8 Titration data.

3 Methoxime derivative, 

proton, NMR.

2 Proton NMR.

3 Proton NMR.

7 Difference from total 

rings and double 

bonds.

1 ring or All of above, 

double bond

Assumptions

All acidic H are

carboxyl H. 

No other hydrogen

types in assigned

NMR peak. 

Do.

All acidic H are 

carboxyl H.

Quantitative

derivatization. 

One-half of 6-H

associated with

esters and ethers

are esters, and

hydrogens are

methylene-H. 

Ash is 100 percent

silica. 

Quantitative

derivatization. 

All residual oxygens

are ether oxygen. 

Basic nitrogen would

not be present in

acids. 

None.

None.

All acidic hydrogen 

are carboxyl H.

Quantitative 

derivative 

forma tion.

Same as ester oxygen.

33 percent of rings 

are substituted with 

aromatic hydrogen.

All of above.

srbon (excluding carboxyl carbon). per 9.7 carbons.
CHARACTERIZATION OF NATURAL ORGANIC SOLUTES 47

TABLE 19. Organic-carbon recoveries from the White River using 

filtration and column-adsorbent system

(mg/L, milligrams per liter; L, liters; mg C, milligrams of carbon]

Sample

September 21-25, 1<381 June 7-11, 1982

Dissolved organic carbon (mg/L) 

Water volume processed (LJ 

Hydrophobic bases (nig C) 

Hydrophilic bases (mg C) 

Weak hydrophobic acids (mg C) 

Strong hydrophobic and hydrophilic

acids (mg C) 

Estimated organic-carbon recovery

(percent)

2.3

1,091

1.5

46

51

1,498

steps (Leenheer and Noyes, 1985). The material balance 

for these subfractionation steps of the acid fractions is 

shown in table 20.

The two humic-acid fractions were treated with a mixture of hydrochloric and hydrofluoric acids (HCL-HF) 

to remove silica (Leenheer and Moe, 1969), which was a 

major component of these fractions. Fifty-eight percent 

of humic-acid no. 1 and 50 percent of humic-acid no.2 

were converted into fulvic acid by the HCL-HF treatment indicating that silica is instrumental in converting 

fulvic acid to humic acid.

The distribution of acids as k' for XAD-8 increased 

was bimodal in nature, with the majority of material 

found at fc'>10 and fc'<0.3. This may indicate two sources

TABLE 20. Subfractionation of strong hydrophobic- and hydrophilic-acid fractions from the White River, sampled September 

1981

Fraction

Strong hydrophobic and hydrophilic acids

llumi c-aci d no . 1

Hum ic-.it id no. 2

Strong hydrophobic acids (k' > 10)

Hvdrophilic-acids no. 1 (k' =2-10)

Hydroplnlic-aiids no. 2 (k' = 0.3 - 2)

UHr.ihydrophilic acids (k' - 0.3)

Milligrams

of carbon

1,498

122

115

621

240

78

272

Percent

of total

100

8

7

41

16

5

18

.1

.7

.5

.0

.2

.2

and (or) processes that lead to this bimodal distribution 

of material.

Various wet-chemical tests were performed on the 

fractions to better elucidate components in these mixtures. The acids were titrated with standard sodium 

hydroxide. The titer of the acids up to pH8 was strong 

acids and the titer from (pH8-10x2) was defined as 

weak acids (E. M. Thurman and R. L. Malcolm, U.S. 

Geological Survey, written commun., 1982). Total 

polysaccharides were determined by the colorimetric 

phenol-sulfuric acid test (Kedeti and Lederer, 1974) and 

uronic acids were determined by the colorimetric carbazole test (Kedeti and Lederer, 1974). Results for 

these analysis are shown in table 21.

Two end-member types of organic solutes are indicated by the data in table 19. The first type represents a 

humified solute probably resulting from a decay sequence

TABLE 21. Chemical analyses of organic-solute fractions from the White River, sampled

September 1981

Strong acids Weak acids Polysaccharides Uronic acids

Fraction (milliequivalents (milliequivalents (percent of (percent of

per gram carbon) per gram carbon) fraction carbon) fraction carbon)

Humic-acid no. I 1

Humic-acid no. 2 1

Strong hydrophobic acids (k'>10)

Hydrophilic-acids no. 1 (k'=2-10)

Hydrophilic-acids no. 2 (k'=0.3-2)

Ultrahydrophilic acids (Ar'<0.3)

Hydrophilic bases

9.48 2.72

5.55 2.22

12.70 1.38

15.63 1.78

6.24 1.10

 

---

2.9

18.1

1.9

4.5

7. 1

26.9

16.0

1.0

3.6

.3

.5

.3

2.4

.9

removed by HC1-HF.
48 EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING

TABLE 22. Elemental analyses of organic-solute fractions isolated from the White River, sampled September 1981

 , . Humic-acid no. I 1 Humic-acid no. 2 2 Element

(percent) (percent)

Carbon 45.09 40.68

Hydrogen 4.26 5.15

Oxygen 26.7 22.44

Nitrogen 4.06 5.31

Sulfur

Ash 9.95 16.71

Empirical formula C 13 H 150 6N C 9H 140 4N

Strong hydrophobic acids

(percent)

50.35

5.08

41.36

1.73

1.08

1.37

Cl25HlSl°77N4Sl

Hydrophilic acids Hydrophilic 

k' = 2-10 bases

(percent) (percent)

42.85 29.65

4.41 4.85

40.2 26.0

2.78 7.85

1.54 2.83

6.52 28.53

£74892^52^481 £28855018^68

Index of hydrogen deficiency/ 0.50 

number carbons.

Index of hydrogen deficiency per .39 

number of carbons after subtracting carboxyl-group (strong 

acidity) double bonds.

Silica removed by HC1-KF. 

2 Isolated as ammonium salts.

that is high in strong-acid acidity and low in carbohydrate and uronic-acid concentrations. These humified 

materials are represented by the strong hydrophobicacid and hydrophilic-acid no. 1 fractions. The second 

type of material probably represents undecomposed or 

partly decomposed material of biological origin, which is 

low in acidity and high in polysaccharide and uronic-acid 

concentration. This material is represented by hydrophilicacid no. 2, ultrahydrophilic acids, hydrophilic bases, and 

humic-acid no. 2. The ultra hydrophilic-acid fraction has 

the largest polysaccharide concentration (26.9 percent of 

fraction carbon), which undoubtedly results in the very 

hydrophilic character of this fraction. The humic-acid 

no. 2 fraction has the greatest uronic-acid concentration, 

because plant hemicelluloses high in uronic acids partition into this fraction (Robinson, 1980).

Elemental analyses of organic-solute fractions isolated from the White River in the September 1981 sample 

are shown in table 22. The most significant information 

derived from data in table 22 is the ratio of the index of 

hydrogen deficiency (number of rings and double bonds) 

to the number of carbons in the empirical formula. This 

ratio gives an estimate of the degree of unsaturation of 

the mixture of molecules in each fraction. The hydrophilicbase fraction is saturated almost completely with hydrogen. 

The strong hydrophobic- and hydrophilic-acid fractions 

are moderately unsaturated, but approximately one-half

of this unsaturation can be accounted for by carboxylate 

concentration as estimated by the strong-acid acidity 

shown in the data in table 22. The humic-acid no. 2 

fraction gives about the same degree of unsaturation as 

the strong hydrophobic- and hydrophilic-acid fractions 

after factoring in the carboxylate concentration, but the 

humic-acid no. 2 fraction has a much greater degree of 

unsaturation than the remaining fractions. Part of this 

unsaturation is due to conjugated rings and double bonds 

that produce color, and this solute fraction has a much 

darker color than the remaining fractions. The elemental 

data in table 22 also show that nitrogen, sulfur, and ash 

concentrations tend to increase as the fractions become 

more hydrophilic. The nitrogen and sulfur heteroatoms 

and the ash representing inorganic constituents all may 

be integral organic structural components of these 

fractions. The isolation procedures were developed and 

tested to discriminate against inorganic solutes (Leenheer 

andNoyes, 1985).

Qualitative information that substantiated the chemical analytical data was provided by infrared spectroscopy. 

Infrared spectra of the two humic-acid fractions are shown 

in figure 33, and the spectra of the strong hydrophobicand hydrophilic-acid fractions are shown in figure 34. 

The aromatic character of humic-acid no. 1 is shown by 

bands at 1,630 and 1,500 cm"1 , whereas the hydroxylic 

character resulting from polysaccharide components of
CHARACTERIZATION OF NATURAL ORGANIC SOLUTES 49

2.5 3.0 4.0 5.0

MICROMETERS 

6.0 7.0 8.0 9.0 10 12 14 16 18 20 25 3035

3500 3000 2500 2000 1800 1600 

WAVENUMBER (CM

1400 1200 1000 800 600 400

FIGURE 33. Infrared spectra of humic acids of the White River; river sampled September 1981.

MICROMETERS

in o in o o

Stong Hydrophobic 

Acids k' > 10

0

4000 3500 3000 2500 2000 1800 1600 1400

WAVENUMBER (CM ' 1

1200 1000 800 600 400 200

FIGURE 34. Infrared spectra of strong hydrophobic- and hydrophilic-acid no. 1 fractions of the White River; river sampled September

1981.

humic-acid no. 2 is evidenced by the C-O alcohol band at 

1,040 cm"1 . The amide I and II bands in humic-acid no. 2 

are indicative of the proteinaceous character of this fraction,

which is substantiated by the large nitrogen concentration (5.31 percent) in this fraction. In figure 34, the 

hydrophilic-acid fraction differs from the hydrophobic-
50 EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING

acid fraction in the greater intensity of the broad OH 

band from 3,700 to 2,300 cm and greater band broadening due to hydrogen bonding. Both of these differences 

result from the greater hydrophilic or hydroxylic character of the hydrophilic-acid fraction.

Comparison of the infrared spectrum of the strong 

hydrophobic-acid fraction from the White River (fig. 34) 

with the infrared spectrum of the well D-8 organic acids 

(fig. 31) shows no differences between these two samples 

except for the silica bands in the well D-8 sample. However, 

the other chemical and proton NMR data indicate major 

differences, which demonstrate that infrared spectroscopy can be nondefinitive in certain instances. Much of the 

September 1981 sample was used to develop more definitive methods based on functional-group derivatization 

and proton NMR spectroscopy. This newly developed 

method then was applied to the well D-8 sample discussed 

previously, and the June 1982 sample from the White 

River to be discussed in the following paragraphs.

The strong hydrophobic- and hydrophilic-acid fractions 

of the June 1982 sample were concentrated and acidified 

to generate two humic-acid samples similar to the September 1981 sample. However, no humic acid formed 

during the concentration step and a humic-acid precipitate comprising only 55 mg of carbon formed during the 

acidification step. Only 1.8 percent of the total isolated 

carbon in the June 1982 sample was humic acid, whereas 

humic acid in the September 1981 sample comprised 14.8 

percent of the isolated carbon.

In the September 1981 sample, the acids fractionated 

according to their column capacity-factor (&') affinities 

for XAD-8 resin showed a bimodal distribution with k' 

with the valley between the two distributions occurring 

near k'=2. Each distribution has distinctive chemical 

properties. Therefore, to sample these two distributions 

for the June 1982 sample, the combined strong hydrophobic- and hydrophilic-acid fraction was subdivided by 

column chromatography on XAD-8 resin so that the 

strong hydrophobic acids were defined for fc'>2.6 and the 

hydrophilic acids were defined as fe'<2.6. Chemical data 

characterizing the various fractions of the June 1982 

sample are shown in table 23. The humic-acid fraction 

was not characterized chemically because of lack of sufficient material, and the hydrophilic-base fraction was 

found to be almost identical to the weak hydrophobicacid fraction by chromatography on ion-exchange cellulose; therefore, it was not chemically characterized as 

a unique fraction.

Most of the material isolated in the June 1982 sample 

resides in the hydrophobic-acid fraction (table 23), which 

is in contrast to the September 1981 sample that had a 

much greater percentage of hydrophilic acids (table 22). 

The hydrophilic-acid fraction of the June 1982 sample is 

characterized by its very large acid concentration. AssumTABLE 23. Chemical and elemental analyses of organic-solute 

fractions isolated from the White River, sampled June 1982

(Data in percent except as indicated; mg C, milligrams of carbon; 

meq/g C, milliequivalents per gram carbon]

Element

Quantity (mg C)

Strong acids (meq/g C)

Weak acids (meq/g C)

Carbon

Hydrogen

Oxygen

Nitrogen

Sulfur

Chlorine

Phosphorous

Ash

Weak 

hydrophobic 

acids

188

75.4

2.2

49.19

5.65

28.21

 

 

...

 

12.72

Strong 

hydrophobic 

acids

2,410

11

3

48

4

39

1

2

1

.7

.8

.66

.82

.26

.64

.39

.66

.55

.04

Hydrophilic 

acids 1

95

33.

7.

20.

2.

40.

6.

1.

--

--

30.

5

8

02

01

53

48

67

-

-

4

Empirical formula

Index of hydrogen deficiency 0.34

per number carbons. 

Index of hydrogen deficiency .28

per number of carbons after

subtracting carboxyl-group

(strong acidity) double

bonds.

1 Isolated as sodium salts.

ing that carboxyl-group concentration is equivalent to 

the strong-acid titration data for the hydrophilic-acid 

fractions, 40.2 percent of the carbons are carboxyl carbons and 52.6 percent of the oxygens are carboxyl oxygens. 

The strong hydrophobic-acid and weak hydrophobicacid fractions have progressively less acid and oxygen 

concentrations and greater hydrogen concentrations. The 

index of hydrogen deficiency per carbon after correction 

for carboxyl-acid concentration shows a tendency for increasing unsaturation when going from hydrophilic acids 

to strong hydrophobic acids to weak hydrophobic acids. 

The infrared spectra of the four acid fractions from the 

June 1982 sample are shown in figure 35; the proton 

NMR spectra are shown in figure 36. Structural- and 

functional-group assignments are noted on the spectra 

in figures 35 and 36. The proton NMR spectra in figure 

36 give more definitive quantitative information than 

the infrared spectra in figure 35, but the infrared spectra 

give qualitative information on silica and certain functional groups that is not obtainable by proton NMR. By 

using the proton NMR spectral data in figure 36 and the 

chemical and elemental analyses in table 23, quantitative structural- and functional-group information for three 

of the organic-acid fractions from the June 1982 sampling of the White River is shown in table 24. Methods of 

data acquisition and interpretation were the same as
CHARACTERIZATION OF NATURAL ORGANIC SOLUTES 51

2.5 4.0 5.0

MICROMETERS

6.0 7.0 8.0 9.0 10

0

4000

12

T

14 16 18 20 25 30

100

3500 3000 2500 2000 1800 1600 1400 1200 1000 800 600 400

WAVENUMBER (CIVM) 

FIGURE 35. Infrared spectra of acid fractions of the White River; river sampled June 1982.

described previously for the well D-8 organic acids shown 

in table 17.

Each of the organic-solute fractions isolated from the 

White River during the June 1982 sample have unique 

chemical and physical characteristics. The model for the 

strong hydrophobic-acid fraction, which constitutes the 

largest solute fraction (85 percent of carbon isolated), 

only can be described generally as an aquatic fulvic acid. 

Specific structures for any soil or aquatic fulvic acids 

have not been clarified yet. The White River fulvic acid is 

characterized by having a typical carboxyl-group concentration, typical aliphatic- to aromatic-hydrocarbon 

ratio, significant ester and ether concentration, and a 

minimal hydroxyl-group concentration. Most of the original free hydroxyl groups of precursors of this fulvic acid 

must have been converted to ester and ether groups 

through humification processes.

The weak hydrophobic-acid fraction can be regarded 

as the natural detergent fraction in the White River. Its

significant isolated aliphatic-hydrocarbon concentration, 

as shown in the proton NMR, produces surface activity 

that causes foaming in the water. This fraction also has a 

minimal carboxylic-acid concentration, a moderate aromatic concentration, and a large silica concentration. 

The silica conjugated to this fraction is responsible for 

its weak-acid characteristics, which enable its separation 

from the strong hydrophobic acids.

The hydrophilic acids have very significant carboxylgroup acidity and a moderate hydroxyl-group concentration as evidenced by bands at 1,350 and 1,050 cm"1 in the 

infrared spectra. This fraction is almost entirely aliphatic in nature, and almost every carbon is attached to an 

oxygen substituent. The significant nitrogen concentration in this fraction is unusual, and the infrared spectra 

do not show evidence of amide bands indicative of proteins. 

Nitrogen in this fraction may reside as Shiff base linkages resulting from sugar-amine condensation reactions. 

The sugar-amine condensation, also called the browning
52 EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING

10 76543 

CHEMICAL SHIFT, IN PARTS PER MILLION

FIGURE 36. Proton nuclear magnetic resonance (NMR) spectra of acid fractions of the White River; river

sampled June 1982.
CHARACTERIZATION OF NATURAL ORGANIC SOLUTES 53

TABLE 24. Quantitative organic structural- and functionalgroup information on organic-acid fractions from the White 

River, sampled June 1978

[H, hydrogen: O. oxygen]

Hydrogen distribution 

Strong-acid (carboxyl)

hydrogen. 

Weak-a id (phenolic,

enol c, silicic acid)

hydr gen. 

Isolat d aliphatichydr carbon hydrogen. 

Alipha ic hydrogen on carbons

alph to carbonyl, carboxyl,

and ster groups. 

Alipha .ic hydrogen on carbons

att

Aromat

4.7

bed to hydroxyl, 

ther oxygen, 

hydrogen.

5.5 

1.1

Oxygen distribution

Carboxyl oxygen. 64-0 

Carbonyl oxygen. 15-0 

Hydroxyl oxygen. 1-0 

Ester oxygen. 21-0 

Ether oxygen. 35-0

Number of rings or double bonds 92

Carboxyl oxygen double bonds. 32

Carbonyl oxygen double bonds. 15

Ester oxygen double bonds. 11

Aromatic rings and double bonds 24 3. 

associated with aromatic 

hydrogen.

Unaccounted rings and double 2 

bonds.

Ratio of unaccounted rings and 1 ring or double 32 

double bonds with structural bond per 113 carbons, 

carbon (excluding carboxyl 

carbon).

reaction, is one of the major theories of humic-substance 

formation as summarized by Stevenson (1982). Thus, 

these hydrophilic acids can be described as a mixture of 

hydroxycarboxylic acids of significant non-basic, nonamide nitrogen concentration.

The humic-acid fraction, which only constituted a trace 

of the June 1982 sample, was characterized by its significant aromatic-hydrogen concentration as shown by the 

proton NMR (fig. 36). It also contained many hydrogenbonding groups as evidenced by the major peak at 3.8 

ppm in the proton NMR spectra. Molecular interactions 

between these hydrogen-bonding groups probably are

responsible for the precipitation of this fraction on 

acidification.

CONCLUSIONS

Natural organic solutes characterized by this study 

were very different from organic contaminants produced 

by the oil-shale retorting process. Organic contaminants 

from oil-shale processing listed in table 3 are all low 

molecular-weight monomeric compounds, whereas natural organic solutes are complex heterogeneous polymers 

of biological origin. Assays for aromatic amines of natural origin in surface and ground waters by the identical 

method used for oil-shale retort wastewaters failed to 

find any simple aromatic amines at concentrations near 

1 yug/L. Concentrations of DOC in natural waters are two 

to four orders of magnitude less than DOC in retort 

wastewaters. It is unlikely that many of the monomeric 

organic solutes in retort wastewaters will persist for a 

decade if discharged into the White River; they will be 

degraded through biological, chemical, and photolytic 

processes, and the residual fragments will be incorporated into humic-type substances. The aromatic-amine 

fraction, which is the most resistant to biological 

degradation, will predominantly partition onto and be 

transported by sediment.

Natural organic solutes in ground water of the Rio 

Blanco well D-8 can be distinguished from natural organic solutes in the White River by the absence of the peak 

at 3.8 ppm in the proton NMR spectrum of well D-8 

organic acids. This peak is indicative of alcohols, esters, 

and ethers, which for unknown reasons are not present in 

the ground-water sample. The ground-water organic acids 

also have a smaller aromatic concentration than the 

surface-water organic acids.

Seasonal and flow variations in composition of White 

River organic solutes were distinguished mainly by the 

greater humic-acid and hydrophilic-acid concentrations 

during the fall sample at low flow. These two fractions 

had the greatest hydroxyl and carbohydrate concentrations, and their abundance in the fall is believed to be 

related to the primary productivity from phytoplankton 

in the river at low flow when suspended sediment concentrations are minimal and allothonous inputs of organic constitutents are minimized. In the spring during 

high flow, organic inputs to the river are of allocthonous origin, and these organic constituents are already 

partly decayed, which decreases their hydroxyl and resulting humic-acid and hydrophilic-acid percentages. 

The hydrophilic-acid fraction probably is degraded rapidly in the river, and its percentage may be more related to competing rates of input and decay than to 

total mass of material input in this fraction.
54 EFFECTS OF ORGANIC WASTES ON WATER QUALITY, COLORADO, UTAH, AND WYOMING

SUMMARY

Onsite processing of oil shale in the Green River Formation generates liquid, solid, and gaseous wastes, which 

may impact the quantity and quality of local water 

resources. Liquid and gaseous wastes from oil-shale 

retorting are similar to coal-conversion and petroleumrefining wastes, but are different in the significantly 

greater levels of nitrogenous waste constituents produced. Solid spend-shale wastes also are different compared to coal-conversion processes and petroleum-refining 

operations in the vast quantities produced and their 

chemical and physical properties that are dependent both 

on the properties of the parent oil shale and the nature 

of the retorting process. The characteristics of water 

and sediment derived from the Green River Formation 

are different compared to most other hydrologies and 

geologies associated with fossil-fuel productions because of the unique assemblage of minerals in the alkaline lacustrine deposit of the Green River Formation.

Hydrophobic organic-waste constituents (table 3) have 

a much greater tendency to be sorbed on aquifer solids 

or sediments in surface waters than hydrophilic constituents that are likely to be transported as solutes. 

Soils developed from sediments of the Green River and 

overlying Uinta Formations have a relatively large 

capacity to immobilize hydrophobic organic-waste constitutents by sorptive processes, and the majority of the 

hydrophilic-waste constituents are fatty acids that are 

readily biodegradable. Application of concentrated retort 

wastewater on soil adversely affects soil structure and 

extracts soil organic matter into solution. Immobilization 

of wastewaters by codisposal with low-temperature retorted spent shale is especially attractive because of its 

excellent sorbent tendencies for organic constituents. 

Organic-waste compounds that are not readily sorbed 

or biodegraded include thiocyanate, acetonitrile, and 

oxygenated nitrogen heterocycles; however, these compounds are not known to be especially toxic or mutagenic. 

Thiocyanate was found to be useful as a conservative 

organic-solute tracer for retort-wastewater presence in 

ground waters.

Organic constituents in wastewaters, consisting mostly of small molecular-weight monomeric solutes, are 

readily distinguished by chemical analyses from large 

molecular-weight polymeric organic constituents found 

in native surface and ground waters. Natural organicsolute concentrations in surface and ground waters (in 

this study), with the exception of very alkaline trona 

waters, generally are less than the concentrations of 

organic constituents found in sediments of the Green 

River Formation.

Retorting wastes can be treated and disposed of in 

surface-retorting processes much more readily than with

in-situ retorting processes because of the lack of accessibility for waste treatment with in-situ processes. True 

in-situ retorting processes have the greatest potential 

for ground-water contamination, but these processes are 

unlikely to become viable technologies in the near future 

because of fundamental limitations in the fracturing 

process prior to retorting. Modified in-situ retorting 

processes have succeeded in managing waste emissions 

and preventing ground-water contamination during retorting, but there is a significant potential for groundwater contamination after retort abandonment.

Waste-treatment technologies, previously developed 

by petroleum-refining and coal-conversion technologies, 

should be adaptable to treatment of liquid and gaseous 

oil-shale retorting wastes. Two of the most hazardous 

waste constituents, ammonia and sulfides, have the 

potential to be recovered by treatment processes and 

sold as ammonium salts and elemental sulfur. Disposal, 

compaction, and revegetation of spent shale is the largest 

waste problem facing the shale-oil industry, but spent 

shale also has been proposed and tested as a source of 

alumina, as cement, and as a sorbent for acid-retort 

gases and wastewaters.

Aromatic amines are the organic-compound group most 

likely to cause problems in retorting wastes. Aesthetic 

problems resulting from their noxious odors probably 

will outweigh their toxicological and mildly mutagenic 

properties. It is unlikely that aromatic amines will persist as solutes in water because of their tendency for 

sorption, but their volatilization from sediments and 

spent shale may cause long-term odor problems. Thiocyanate and phenols in retort wastes will need to be 

considered when designing treatment processes. Chlorination should not be used when these compounds are 

present because toxic cyanogen chloride and chlorinated 

phenols will be produced with chlorine treatment.

The research in this report concerned wastes produced 

by experimental and pilot plant oil-shale retorting processes and the results may be limited in their predictive 

capabilities by the experimental nature, long-term storage of samples before analysis, and small scale of the 

retorting process. Ground-water hydraulic studies need 

to go hand in hand with water-quality studies. As the 

oil-shale industry scales up its operations to commercial 

level production of shale oil, there needs to be continued 

studies of water-quality effects associated with shale-oil 

production to refine predictive capabilities for better 

water-resource planning. The retention and degradation 

of waste organic constituents on surface sediments needs 

the most attention at this point in time. However, enough 

presently is known about retorting processes, and the 

nature, behavior, and environmental effects of retort 

wastes and waste-treatment processes to select those 

technologies that result in a self-sustaining shale-oil 

industry with minimal long-term environmental effects.
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& U.S. GOVERNMENT PRINTING OFFICE: 1986 773-047/46,010 REGION NO. 8