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FUNDAMENTAIS
___ OF____
HAZARDOUS
WASTE SITE
REMEDIATION

Kathleen Sellers
CRC Press
Taylor &. Francis Group
Boca Raton London New York

CRC Press is an imprint of the

Taylor & Francis Group, an informa business
Library of Congress Cataloging-in-Publication Data

Sellers, Kathleen.
Fundamentals of hazardous waste site remediation I Kathleen
Sellers.
p. cm.
Includes bibliographical references and index.
ISBN 1-56670-281-X (alk. paper)
I. Hazardous waste site remediation. I. Title.
TD !030.S45 1998
628.5--dc21 98-4419
CIP

This book contains information obtained from authentic and highly regarded sources. Reprinted
material is quoted with permission, and sources are indicated. A wide variety of references are listed.
Reasonable efforts have been made to publish reliable data and information, but the author and the
publisher cannot assume responsibility for the validity of all materials or for the consequences of their use.
Neither this book nor any part may be reproduced or transmitted in any form or by any means,
electronic or mechanical, including photocopying, microfilming, and recording, or by any information
storage and retrieval system, without prior permission in writing from the publisher.
The consent of CRC Press LLC does not extend to copying for general distribution, for promotion,
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Direct all inquiries to CRC Press LLC, 2000 Corporate Blvd., N.W., Boca Raton, Aorida 33431.

Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and
are used only for identification and explanation, without intent to infringe.

© 1999 by CRC Press LLC

Lewis Publishers is an imprint of CRC Press LLC

No claim to original U.S. Government works

International Standard Book Number 1-56670-281-X
Library of Congress Card Number 98-4419

Disclaimer
The publisher has made every effort to trace copyright holders and welcomes correspondence from those
they have been unable to contact.
 The Author

During over twelve years o f experience, Ms. Sellers has focused on developing
and designing solutions to hazardous waste problems. Ms. Sellers received a B.S.
in Chemistry from Indiana University and a M .S. in Environmental Engineering
from the University o f Massachusetts. She began her career with the U.S. Environ­
mental Protection A gency and currently works for Ogden Environmental and Energy
Services in Westford, MA.
Ms. Sellers has worked on a variety o f sites, including former chemical manu­
facturing facilities, coal-gasification waste sites, and landfills. Her work, under both
state and federal regulatory programs, has included development o f site investigation
plans, management o f focused field investigations, feasibility studies, remedial
design, negotiations with regulatory agencies, and public involvement programs.
Ms. Sellers has also helped clients with their industrial wastewater treatment plant
operations. She is a registered professional engineer in Massachusetts and Vermont.
 Acknowledgments
This book is based on the syllabus and handouts that I prepared for a course that
I taught at Tufts University in 1992. Kim M. Henry helped m e to prepare the original
profile o f the hypothetical A ce Solvent Recovery Facility, discussed in Chapter 1,
for that class. It is used herein with her permission. Doug Fannon drafted the figures
in Chapter 1 based on Ms. Henry’s original drawings.
I am grateful to the engineers and scientists who reviewed portions o f this book
in draft and provided helpful comments: Paul Anderson, Ph.D.; Ralph Baker, Ph.D.;
Kristine Carbonneau, P.E.; Jay Clausen, P.G.; Diane Heineman; Kim M. Henry, LSP;
David R. Palmer; Steven M. Pause, P.E., LSP; Kaela Sotnik; Douglas Simmons; and
A llison Nightingale. The editorial team at CRC Press provided m e encouragement
and advice throughout this project. M ost o f all, thanks to m y husband Dave, for his
support.
Finally, I dedicate this book to my mothers and my daughters, and m y other
teachers.
 Contents
Acknowledgments

1 In tro d u ctio n .......................................................................................................................... 1

1.1 A ce Solvent Recovery F acility.............................................................................. 1
1.1.1 Former Operations.......................................................................................1
1.1.2 Scope o f the Site Investigation................................................................2
1.1.3 Results o f the Site Investigation — S o ils ............................................ 3
1.1.4 Results o f the Site Investigation — Groundwater..............................4
1.2 What D o I D o N ow ?................................................................................................. 8
Problem s................................................................................................................................ 11

2 B asic P r in c ip le s.................................................................................................................13
2.1 The Significance o f N um bers.............................................................................. 13
2.2 Chemistry o f Hazardous Materials..................................................................... 14
2.2.1 Term inology................................................................................................ 15
2.2.1.1 U n its............................................................................................15
2.2.1.2 Charge and Polarity................................................................17
2.2.1.3 Solubility....................................................................................18
2.2.1.4 Sorption......................................................................................19
2.2.1.5 Volatility.................................................................................... 20
2.2.1.6 Common Reactions................................................................ 22
2.2.2 Common Contaminants.......................................................................... 23
2.2.2.1 Alkanes.......................................................................................23
2.2.2.2 Aromatic Hydrocarbons........................................................ 23
2.2.2.3 Chlorinated Methanes, Ethanes,and E thenes.................. 24
2.2.2.4 Ketones....................................................................................... 25
2.2.1.5 Polynuclear Aromatic Hydrocarbons (P A H s).................25
2.2.2.6 Polychlorinated Biphenyls (P C B s).....................................25
2.2.2.7 Metals and Other Inorganics.............................................. 27
2.3 Overview o f H ydrogeology................................................................................. 29
2.3.1 Hydrologic C y cle...................................................................................... 29
2.3.2 Geologic Formations................................................................................ 30
2.3.3 Groundwater F lo w ....................................................................................31
2.3.4 Contaminant Transport............................................................................35
2.3.4.1 Nonaqueous Phase Liquids...................................................35
2.3.4.1.1 LN A PL.................................................................. 37
2.3.4.1.2 D N A P L ................................................................. 37
2.3.4.2 D issolved Contamination......................................................39
2.4 How Clean is C lean?............................................................................................. 41
2.4.1 Detection L im its....................................................................................... 43
2.4.2 Background L e v e ls...................................................................................43
2.4.3 Regulatory Standards, Criteria, andScreening L e v e ls ................... 43
 2.4.4Site-Specific Risk A ssessm ent...............................................................45
2.4.4.1 Clean-Up Levels Based on Potential Human
Health R isk s.............................................................................. 45
2.4.4.1.1 Types o f Health R isk s......................................46
2.4.4.1.2 Acceptable R isk ..................................................47
2.4.4.1.3 Exposure A ssu m p tions.....................................48
2.4.4.1.4 Calculation o f Clean-Up L evels.................... 50
2.4.4.2 Clean-Up Goals Based on Potential Risks
to an Ecosystem ....................................................................... 59
2.4.5 Clean-Up Goals Based on Protection o f Groundwater..................61
2.4.6 Clean-Up Levels Based on Mass R em oval....................................... 63
2.5 Reaction Engineering............................................................................................. 64
2.5.1 Types o f R eactors...................................................................................... 64
2.5.2 Mass B alance............................................................................................. 65
2.5.3 Rate o f R eaction........................................................................................68
2.5.4 Treatability T esting...................................................................................69
2.6 Environmental Regulations...................................................................................70
2.6.1 Term inology.................................................................................................70
2.6.2 Waste Site Rem ediation...........................................................................71
2.6.3 Hazardous Waste Treatment, Storage, and D isposal...................... 74
2.6.3.1 Waste C lassification.................................................................74
2.6.3.2 Land Disposal Restrictions................................................... 76
2.6.3.3 Other RCRA R egulations..................................................... 78
2.6.4 Other Pertinent Regulations....................................................................78
2.6.4.1 Clean Water A ct........................................................................78
2.6.4.2 Safe Drinking Water A c t ...................................................... 80
2.6.4.3 Occupational Safety and Health..........................................81
2.6.4.4 Transportation........................................................................... 81
2.7 Cost Estim ation........................................................................................................ 82
2.7.1 Level o f A ccuracy..................................................................................... 82
2.7.2 Basis for E stim ates...................................................................................82
2.7.3 Components o f Cost E stim ates............................................................ 83
2.7.4 Sources o f Information............................................................................86
2.7.5 Shortcuts for Preliminary Estim ates.................................................... 87
2.7.5.1 Updating Capital C osts...........................................................87
2.7.5.2 Scaling Equipment C osts....................................................... 88
2 .1 .5 3 Estimating Costs as a Percentage o f Capital C o sts.....88
2.7.6 Sensitivity A nalysis...................................................................................88
Problems................................................................................................................................90
R eferences............................................................................................................................ 95

3 G roundw ater R em ed iation ......................................................................................... 103

3.1 Physical B arriers....................................................................................................105
3.2 Groundwater Extraction.......................................................................................107
3.2.1 Extraction W ells....................................................................................... 107
 3.2.1.1 Well Construction and Pum ps............................................ 107
3.2.1.2 M odeling the Flow to a Single Extraction W ell......... 110
3.2.1.3 Siting Extraction W ells........................................................114
3.2.1.4 Practical C onsiderations..................................................... 115
3.2.2 Well Point S ystem s................................................................................115
3.2.3 Interceptor T renches............................................................................. 116
3.2.4 Effectiveness o f Pump-and-Treat R em ed ies...................................118
3.2.5 Enhancem ents......................................................................................... 119
3.3 Groundwater D ischarge.......................................................................................120
3.4 Groundwater Treatment....................................................................................... 121
3.4.1 Immobilization Technologies............................................................... 122
3.4.2 Separation T echnologies........................................................................126
3.4.2.1 Sedimentation and Sludge H andling................................ 126
3.4.2.2 Filtration.................................................................................... 128
3.4.2.3 Oil-Water Separators and D issolved Air Flotation.... 129
3.4.2.4 Air Stripping............................................................................131
3.4.2.5 Carbon Adsorption and Related Technologies............. 135
3.4.2.6 Ion E xchan ge...........................................................................140
3.4.2.7 Reverse O sm osis..................................................................... 143
3.4.3 Destruction Technologies...................................................................... 143
3.4.3.1 Biological Treatm ent............................................................ 143
3.4.3.1.1 M odel for B ioreactors.................................... 144
3.4.3.1.2 General D esign Considerations....................145
3.4.3.1.3 Applications to GroundwaterTreatment.. 148
3.4.3.2 Chemical Oxidation............................................................... 149
3.4.3.3 Reduction by Zero-Valent Iron
(Reductive D ehalogenation)...............................................151
3.5 In Situ Treatm ent................................................................................................... 152
3.5.1 Natural A ttenuation................................................................................153
3.5.1.1 Conditions for Microbial Growth;
Electron A cceptors................................................................ 154
3.5.1.2 Degradation o f H ydrocarbons........................................... 155
3.5.1.3 Degradation o f Chlorinated S o lv en ts............................... 155
3.5.2 Air Sparging.............................................................................................. 157
3.5.2.1 Physical Principles..................................................................157
3.5.2.2 Air Sparging Through W ells................................................158
3.5.2.3 E ffectiveness........................................................................... 159
3.5.2.4 In-Well System s.......................................................................160
3.5.3 In Situ Bioremediation........................................................................... 161
3.5.3.1 Aerobic Bioremediation........................................................ 162
3.5.3.2 Anaerobic Biorem ediation................................................... 163
3.5.4 Reductive D ehalogenation.................................................................... 164
3.6 Nonaqueous Phase L iq u id s................................................................................166
3.6.1 Light Nonaqueous Phase Liquids........................................................ 167
3.6.1.1 Extraction.................................................................................. 167
 3.6.1.1.1 Removal o f LNAPL O n ly .............................. 167
3.6.1.1.2 Removal o f LNAPL and
Groundwater......................................................169
3.6.1.1.3 Vacuum Extraction/Multi-Phase
Extraction........................................................... 169
3.6.1.2 D isposal.................................................................................... 174
3.6.2 D ense Nonaqueous Phase L iqu ids......................................................174
3.6.2.1 Water F lo o d in g ...................................................................... 174
3.6.2.2 Surfactants and C osolvents.................................................176
3.6.2.2.1 Surfactants.......................................................... 176
3.6.2.2.2 Cosolvents/Alcohol H o o d in g .......................179
3.6.2.3 Steam Injection......................................................................179
3.6.2.4 Oxidation..................................................................................183
3.7 Control o f Air Emissions from Groundwater Treatment U n its.............. 185
3.7.1 Removal o f Water or Other Liquids.................................................. 186
3.7.2 Vapor-Phase Carbon................................................................................186
3.7.3 Thermal Incineration.............................................................................. 188
3.7.4 Catalytic Incineration............................................................................. 189
3.7.5 Biofilters.....................................................................................................190
Problems..............................................................................................................................190
R eferences.......................................................................................................................... 196

4 Soil R em ed ia tio n ............................................................................................................209

4.1 Soil Excavation and Materials Handling........................................................209
4.1.1 P lanning.................................................................................................... 210
4.1.2 Mobilization, Excavation, and Production......................................214
4.1.3 Materials H andling................................................................................ 217
4.1.4 Transportation O ff S ite ......................................................................... 217
4.2 Immobilization Technologies.............................................................................218
4.2.1 Disposal/Landfilling............................................................................... 218
4.2.2 C apping......................................................................................................220
4.2.2.1 Construction o f a Multilayer Cap....................................221
4.2.2.1.1 Bottom or Low-Permeability L ayer..........221
4.2.2.1.2 Middle or Drainage Layer............................. 223
4.2.2.1.3 Top or Erosion-Control Layer......................224
4.2.2.2 Maintenance and M onitoring...........................................224
4.2.3 Asphalt Batching..................................................................................... 224
4.2.3.1 Hot-M ix P rocess...................................................................224
4.2.4 Solidification/Stabilization....................................................................226
4.2.4.1 M echanics o f Treatment.................................................... 227
4.2.4.2 R eagents...................................................................................228
4.2.4.2.1 Pozzolan- or Silicate-Based P rocesses.....228
4.2.4.2.2 Cement-Based P rocesses...............................229
4.2.4.3 Results o f Treatment............................................................230
4.2.5 Vitrification...............................................................................................231
 4.2.5.1 Vitrification o f Excavated S o il.......................................... 232
4.2.5.2 7n 5ifM V itrification...............................................................233
4.3 Separation T echnologies......................................................... 235
4.3.1 Soil Vapor Extraction.............................................................................235
4.3.1.1 Physical Principles............................................................... 235
4.3.1.2 Design o f a Soil Vapor Extraction S y ste m .................. 237
4.3.1.2.1 Soil Vapor Extraction W e lls..........................237
4.3.1.2.2 Optimizing Air Flow Through the S o il....239
4.3.1.2.3 Blowers and Vacuum Pum ps........................ 240
4.3.1.2.4 Vapor Treatment S y ste m ............................... 241
4.3.1.3 E ffectiveness..........................................................................242
4.3.1.4 Related Technologies.......................................................... 244
4.3.2 Thermal D esorption............................................................................... 245
4.3.2.1 Treatment o f Excavated S o il............................................ 245
4.3.2.1.1 Pretreatment and F ee d .................................... 246
4.3.2.1.2 Thermal P rocessor........................................... 246
4.3.2.1.3 Em issions Control............................................ 249
4.3.2.1.4 Operating C onsiderations.............................. 249
4.3.2.2 In Situ Treatment................................................................. 250
4.3.3 Soil Washing, Solvent Extraction, andSoil Flushing................... 251
4.3.3.1 Soil W ashing..........................................................................252
4.3.3.2 Solvent Extraction................................................................ 253
4.3.3.3 Soil Flushing.......................................................................... 253
4.3.4 Electrokinetic Remediation Technologies.........................................255
4.3.4.1 Physical Effects..................................................................... 255
4.3.4.2 Remediation P rocesses....................................................... 259
4.4 Destruction Technologies....................................................................................262
4.4.1 Biological P rocesses.............................................................................. 262
4.4.1.1 Bioremediation.......................................................................262
4.4.1.1.1 O verview ............................................................. 262
4.4.1.1.2 Testing.................................................................. 263
4.4.1.1.3 Process O p tions................................................ 264
4.4.1.1.4 Operating Issues and Variations...................269
4.4.1.2 Phytoremediation..................................................................270
4.4.1.2.1 Treatment M echanism s................................... 270
4.4.1.2.2 Lim itations..........................................................271
4.4.2 Dechlorination..........................................................................................272
4.4.2.1 Glycolite D ehalogenation...................................................272
4.4.2.2 Base-Catalyzed Dechlorination........................................ 273
4.4.3 Incineration...............................................................................................273
4.4.3.1 O verview ................................................................................. 275
4.4.3.2 Process O p tions.....................................................................277
4.4.3.3 Regulatory Requirem ents...................................................279
4.5 Control o f Air Em issions from Soil Treatment U nits................................279
Problems............................................................................................................................. 280
R eferences..........................................................................................................................285
5 Solutions..............................................................................................................297
5.1 Chapter O n e ........................................................................................................... 297
5.2 Chapter T w o........................................................................................................... 297
5.3 Chapter Three..........................................................................................................302
5.4 Chapter F o u r..........................................................................................................311
R eferences..........................................................................................................................317

Index .319
 CHAPTER 1

Introduction

1.1 ACE SOLVENT RECOVERY FACILITY

Consider the A ce Solvent Recovery (ASR) facility.* Between 1974 and 1990 the
facility accepted waste solvents for reclamation. The facility had interim status under
the Resource Conservation and Recovery Act (RCRA), but never received a final
Part B permit. In 1990, the facility lost interim status due to the failure to obtain
required insurance policies or alternative forms o f liability coverage. Shortly there­
after, the owner/operator declared bankruptcy and abandoned the facility. The
owner/operator cannot be located.
In 1990, the state environmental agency removed drums and tanks o f waste solvents
from the site. The removal action also included decontamination o f the building and
removal o f trash and debris from the site. The agency began a site investigation in the
late 1990s. The results o f that investigation are summarized below.

1.1.1 Former Operations

A SR accepted waste solvents, primarily tetrachloroethylene (also known as per-

chloroethylene, or PCE) and trichloroethylene (TCE). The facility stored waste
solvents in tanks and drums on concrete pads in an area west o f the office/warehouse
building (see Figure 1.1). These solvents were pumped through above-ground lines
to stills located in the same area. D istilled solvents were collected in tanks and drums
for off-site shipment. Still bottoms were often incinerated; they were occasionally
disposed o f in a shallow lagoon near the western edge o f the property. According
to a former em ployee, the lagoon was backfilled in the early 1980s.
For a short period in the early 1970s, A SR also accepted used transformers.
According to a former em ployee, these transformers were stored on open ground to
the south o f the building (see Figure 1.1). When the transformers were stripped to
recover the metals, the transformer oils were simply drained onto the ground.

* Note: The Ace Solvent Recovery facility is a hypothetical site, created to illustrate many of the common
problems found at hazardous waste sites. It was created with the help of Kim M. Henry, LSP, and is used
with her permission.

1
 THE FUNDAMENTALS OF HAZARDOUS WASTE SITE REMEDIATION

PALMER ROAD

100 200

SCALE IN FEET

Figure 1.1 Site plan, Ace Solvent Recovery facility.

1.1.2 Scope of the Site Investigation

A s shown on Figure 1.2, 35 borings were installed on the site, 7 o f which were
com pleted as monitoring wells. Two additional wells were installed off-site.
Soil samples were collected from the unsaturated zone and analyzed for volatile
organic compounds (VOCs), semivolatile organic compounds (SVOCs), metals, and
polychlorinated biphenyls (PCBs). Soil samples were also tested using the Toxicity
Characteristic Leaching Procedure (TCLP).
Groundwater samples collected from the monitoring w ells were analyzed for
VOCs, SVOCs, metals, and PCBs. Samples were also analyzed for conventional
wastewater parameters used to evaluate and design groundwater treatment systems.
Pumping tests were performed in selected wells.
INTRODUCTION

PALMER ROAD

Figure 1.2 Locations of borings and monitoring wells. Ace Solvent Recovery facility.

1.1.3 Results of the Site Investigation — Soils

Boring logs were used to develop cross sections showing the site stratigraphy, as
shown on Figures 1.3 and 1.4. The surface o f the site is covered with a thin layer
o f fill. A layer o f till, com posed o f fine sand and silt, underlies the fill in the northern
portion o f the site in a layer approximately 20 feet thick; in the southern portion of
the site, the fill is underlain by glacial outwash com posed o f sand and gravel.
Fractured bedrock is present beneath the site and slopes to the south. The bedrock
is highly fractured to a depth approximately 20 feet below the top o f rock. Investi­
gations to a greater depth have not been conducted at this site.
Screening tests o f the soil samples collected from the till indicate that approxi­
mately 15% of the soil volume exceeded 0.5 in. in size. The material used as backfill
in the former lagoon contained som e debris. An estimated 20% o f the fill in the
lagoon exceeded 0.5 in. in size.
 THE FUNDAMENTALS OF HAZARDOUS WASTE SITE REMEDIATION

Figure 1.3 Location of cross-section A-A', Ace Solvent Recovery facility.

The soil near the location o f the former tanks and stills is contaminated with PCE
and TCE, as is the soil in the former disposal lagoon. Concentrations o f total VOCs
ranged up to 730 mg/kg. Tables 1.1 and 1.2 sununarize the pertinent data. As
indicated in Table 1.2, several o f the samples failed the TCLP test for VOCs. The
soil near the former transformer operation is contaminated with PCBs at concentra­
tions o f up to 158 m g/kg. These data are also provided in Table 1.1.

1.1.4 Results of the Site Investigation — Groundwater

Water levels were measured in all monitoring w ells during May and August to
evaluate the seasonal fluctuation. Table 1.3 indicates the water table elevations in
the shallow unconsolidated aquifer during the August monitoring period, and
Figure 1.5 shows the groundwater contours. Groundwater elevations were approxi­
mately 1 foot higher throughout the site during May. Although groundwater eleva­
tions are not provided for the deeper bedrock aquifer, groundwater flow in the
bedrock occurs in the same direction as the unconsolidated aquifer, to the south.
INTRODUCTION

LfGEND

HLL

GLAOAL H IL {FINE SUT AND CLAY)

. , GLAOAL OUTWASH {COARSE SAND AND GRAVEL)

FRACTURED BEDROCK

Figure 1.4 Cross-section A-A', Ace Solvent Recovery facility.

The glacial till layer in the northern portion o f the site has a hydraulic conductivity
o f 1 X 10^ cm /sec and an effective porosity o f 10%. Pumping test data indicate that
a w ell fully screened in this material has a radius o f influence o f approximately 25
feet and can yield a maximum flow o f approximately 0.2 gallons per minute (gpm).
The glacial outwash (sand and gravel layer) in the southern portion o f the site
has a hydraulic conductivity o f 1 x 1(T‘ cm /sec and an effective porosity o f 25%.
Pumping test data indicate that a w ell fully screened in this material has a radius o f
influence o f approximately 500 feet and can yield a maximum flow o f approximately
200 gpm.
THE FUNDAMENTALS OF HAZARDOUS WASTE SITE REMEDIATION

Table 1.1 Summary of Soil Data

ASR Site
Location Depth (ft) PCE TCE PCB
B-1 1 to 2 ND ND 2
B-2 0 to 2 ND ND ND
4 to 6 2 1 NA
B-3 0 to 2 ND ND NA
4 to 6 4 ND NA
B-4 0 to 2 1 ND NA
2 to 4 10 5 NA
B-5 2 to 4 3 2 NA
B-6 0 to 2 31 32 NA
4 to 6 112 87 NA
B-7 0 to 2 50 29 NA
2 to 4 171 150 NA
4 to 6 208 170 NA
B-8 0 to 2 39 17 NA
4 to 6 128 83 NA
B-9 0 to 2 2 4 NA
4 to 6 15 23 NA
B-10 0 to 2 7 6 NA
2 to 4 49 23 NA
4 to 6 107 87 NA
B-11 0 to 2 43 22 NA
2 to 4 199 104 NA
4 to 6 218 143 NA
B-12 0 to 2 12 16 NA
2 to 4 72 87 NA
B-13 0 to 2 ND ND NA
4 to 6 2 1 NA
B-14 0 to 2 2 3 NA
4 to 6 67 76 NA
B-15 0 to 2 19 9 ND
2 to 4 270 324 3
4 to 6 295 367 NA
B-16 0 to 2 3 4 NA
4 to 6 176 198 NA
B-17 0 to 2 11 13 NA
2 to 4 263 427 NA
B-18 2 to 4 198 429 8
4 to 6 227 503 14
B-19 0 to 2 4 2 NA
4 to 6 23 16 NA
B-20 0 to 2 14 8 ND
4 to 6 57 63 ND
B-21 0 to 2 5 4 2
4 to 6 38 32 ND
B-22 0 to 2 1 ND 10
2 to 4 3 1 2
B-23 0 to 2 NA NA 158
2 to 4 NA NA 43
4 to 6 NA NA 1
B-24 0 to 2 NA NA 67
4 to 6 NA NA 12
INTRODUCTION

Table 1.1 Summary of Soil Data

ASR Site (continued)
Location Depth (ft) PCE TCE PCB
B-25 0 to 2 NA NA 5
2 to 4 NA NA 1
B-26 0 to 2 NA NA 23
2 to 4 NA NA 7
B-27 0 to 2 NA NA 12
4 to 6 NA NA 3
B-28 0 to 2 NA NA 4
MW-1 0 to 2 ND ND 1
2 to 4 ND ND ND
MW-3 0 to 2 ND ND 3
2 to 4 ND ND ND
MW-4 2 to 4 2 2 NA
4 to 6 12 17 NA
Notes: All data In mg/kg. ND, not detected; NA,
not analyzed.

Table 1.2 Summary of TCLP Data

ASR Site
Sample depth
Location (ft) PCE TCE
B-11 2 to 4 4.1 2.3
B-15 2 to 4 4.3 5.6
B-18 2 to 4 3.5 7.4
B-20 2 to 4 ND ND
Regulatory standard 0.7 0.5
Notes: All data in mg/L. ND, not detected.

Table 1.3 Groundwater Elevation

Data — Overburden Wells
August 28, 1997
ASR Site
Water level
Well (ft MSL)
MW-1S 145.4
MW-2S 144.4
MW-3S 141.5
MW-4S 142.2
MW-5S 142.5
MW-6S 139.9
MW-7S 138.7
MW-8S 138.8
MW-9S 135.5
MW-1 OS 144.6
 THE FUNDAMENTALS OF HAZARDOUS WASTE SITE REMEDIATION

PAU4ER ROAD

L£GCNO
Q U0NITCR1NG WELL

SCALE IN FEET

Figure 1.5 Groundwater contour map, Ace Solvent Recovery facility.

Analytical data from shallow monitoring w ells screened at the bottom o f the
unconsolidated aquifer (indicated with an “S” in the w ell identification number) and
from w ells screened approximately 20 feet below the top o f the bedrock aquifer
(indicated with an “R” in the w ell identification number) are provided in Tables 1.4
and 1.5. Based on these data, chlorinated organic compounds have migrated off-site
in the bedrock aquifer, but are still confined to the site property in the shallow aquifer.
D oes the A SR site need to be cleaned up? How?

1.2 WHAT DO I DO NOW?

Every site presents a unique challenge. Nonetheless, every site can be analyzed
in terms o f a limited set o f fundamental features, and a cost-effective solution based
INTRODUCTION

Table 1.4 Groundwater Quality Data

Organic Compounds
ASR Site
Well TCE PCE 1,2-DCE VC PCB
MW-IS ND ND ND ND ND
MW-1R ND ND ND ND ND
MW-2S 0.002 0.002 ND ND NA
MW-2R 0.003 0.001 ND ND NA
MW-3S ND ND ND ND NA
MW-3R 0.001 ND ND ND NA
MW-4S 97.080 82.140 37.450 4.730 NA
MW-4R 120.000 98.000 42.691 3.781 NA
MW-5S 52.430 41.870 29.800 1.370 0.001
MW-5R 61.587 37.894 12.798 0.119 0.001
MW-6S 0.015 0.008 ND 0.003 ND
MW-6R 12.489 7.623 1.847 0.241 ND
MW-7S 0.005 0.001 ND ND NA
MW-7R 3.417 1.245 1.007 0.125 NA
MW-8S ND ND ND ND ND
MW-8R ND 0.001 ND ND ND
MW-9S ND ND ND ND ND
MW-9R 0.090 0.025 0.045 ND NA
MW-10S 0.950 0.035 0.009 ND ND
MW-10R 1.145 1.497 ND ND NA
Notes: All data In mg/L. Abbreviations; DOE, dichloroethylene;
VC, vinyl chloride; ND, not detected; NA, not analyzed.

Table 1.5 Groundwater Quality Data

Inorganic Parameters
ASR Site
Well Iron Manganese Calcium Magnesium TDS TSS pH
MW-2S 10 4 23 10 250 32 7
MW-2R 5 1 15 6 187 1 6.8
MW-4S 24 10 61 26 230 152 6.7
MW-4R 7 ND 12 5 163 ND 6.9
MW-5S 19 7 17 9 212 56 7.1
MW-10S 15 4 26 15 243 41 6.6
Notes: All data except pH in mg/L. Abbreviations: TDS, total dissolved solids; TSS,
total suspended solids.

on those features. Remedial solutions for hazardous waste sites depend on four broad
considerations:

The types of contaminants and their chemical characteristics determine whether

and how a site requires remediation. The physical properties of a contaminant
determine how it moves through or persists in the environment. These properties
also determine how a contaminant may be treated. The chemical stmcture of a
contaminant determines its toxicity to people and to the ecosystem, and thus the
extent to which a site must be cleaned up.
10 THE FUNDAMENTALS OF HAZARDOUS WASTE SITE REMEDIATION

Environmental regulations specify the procedures to be used to study a waste site

and select a remedy; requirements for handling and disposing of certain types of
waste and wastewater (groundwater); and many other features of waste site reme­
diation.
The location, use, and physical features of a site fundamentally affect the clean­
up goal and the methods used to reach that goal. Consider the following examples.
Far more stringent clean-up requirements are typically imposed on a site in a
residential area than in an industrial area. A community group may oppose on-site
incineration. Contamination in a wetland cannot be managed simply by contain­
ment beneath an impermeable cap. Man-made features such as process piping or
underground utilities can hinder excavation and increase remediation costs if they
must be relocated. These examples show how fundamentally the location, use,
and physical features of a site can affect the extent and type of remediation required.
The natural characteristics of soil and groundwater often determine the systems
needed to treat soil or groundwater. While the chemical characteristics of a waste
indicate how it may be treated, the physical characteristics of a waste determine
how it can be treated. For soils or sludges, materials handling — that is, converting
the waste into a form that can be treated, and conveying it from the source through
the treatment process — is the critical step in most treatment processes. Charac­
teristics such as viscosity, for sludges, and particle size, for soil or other solid
waste, can complicate or preclude treatment by certain methods. Certain natural
components of groundwater can also complicate site remediation. Many ground-
waters contain naturally high levels of hardness, iron, or manganese. These metals
can precipitate, forming solid particles that can clog or foul common types of
treatment equipment. Pretreatment to modify a natural characteristic of soil, sludge,
or groundwater can be a large, expensive component of remediation.
The capabilities of remedial technologies under site-specific conditions can vary
widely. Remediation technologies act to contain contamination, separate it from
the soil or groundwater, or destroy the contaminants. A limited set of physical
mechanisms forms the basis for most of the hundreds of technologies that have
been proposed or used to clean up hazardous waste sites. Understanding these
mechanisms and the properties of contaminants enables an engineer to analyze and
ultimately to apply an unfamiliar technology. The use of a particular technology
depends, in addition to the site-specific factors described above, on its availability,
proven or projected reliability, status (bench-scale, pilot-scale, or full-scale), and cost.

Chapter 2 o f this book provides a framework for the reader to begin this funda­
mental analysis. C hapters describes groundwater remediation technologies, and
Chapter 4, soil remediation technologies. The objective o f this book is to help the
reader to develop a multidisciplinary approach to solving hazardous waste problems.
Rules o f thumb are presented throughout this book. Rules o f thumb should always
be applied with a strong dose o f common sense; they are guidelines, based on
practical experience, and not absolute rules.
INTRODUCTION 11

Problems

1.1 Reread the description of the ASR site. Write down all of the technical terms that
you do not understand.

1.2 This exercise is intended to help you to explore and define your personal views on
environmental protection, as personal opinions almost invariably affect the selection
and design of remediation options for hazardous waste sites. Consider a hypothetical
site contaminated with tetrachlorogoop (TCG), a potential human carcinogen which
has caused cancer in laboratory animals at relatively low doses. TCG is leaching
from the soil into the groundwater, which is migrating toward a wetland. Four
remediation options are under consideration for the soil:
• Option 1: Cap the contaminated soil, to prevent people from contacting the soil
and to minimize the leaching of TCG to groundwater. Fence the site. Maintain the
cap and fence indefinitely. Estimated cost: $120,000.
• Option 2: Excavate contaminated soil, including some soil beneath the groundwa­
ter table, so that residual contamination is at a level which should not pose a human
health threat or leach to groundwater above trace levels. Dispose of the soil in a
hazardous waste landfill in another state. Backfill the excavation. Estimated cost:
$800,000.
• Option 3: This option is similar to option 2, but the contaminated soil would be
incinerated at an off-site facility to destroy the TCG. Estimated cost: $3.5 million.
• Option 4: This option is similar to option 3, except that the site would be restored
to background conditions rather than to risk-based clean-up levels. (Since TCG is
not a naturally occurring compound, “background conditions” means that no TCG
could be detected in soil that would remain at the site.) Estimated cost: $25 million.
What should be done to clean up the site? Consider two alternative site settings;
determine what should be done in each case, and present your rationale.
[a] The site is on the grounds of a large chemical-manufacturing facility. TCG was
accidentally spilled from a storage tank. The multinational corporation which
owns the facility made marginal profits in the last year.
[b] The site is located behind an elementary school. Contamination resulted from
activities in the maintenance shed. Because of a large influx of new students,
the school department is low on funds and may need to lay off art and music
teachers, close the computer lab, and limit after-school sports. Funding for the
school comes from property taxes in this affluent town; the townspeople have
voted down property tax increases for ten years in a row.
[c] Did your answers for (a) and (b) differ? If so, why?
 CHAPTER 2

Basic Principles

Developing and designing solutions to hazardous waste problems requires knowl­

edge o f many disciplines: chemistry, toxicology, chemical engineering, civil engi­
neering, hydrogeology, and environmental regulations. Most problems are solved by
teams o f people in different disciplines. However, each team member needs to have
a basic understanding o f the fundamental principles o f each discipline to work
effectively. This chapter summarizes those principles. For more detailed information,
see the references cited in this chapter.

2.1 THE SIGNIFICANCE OF NUMBERS

The concepts o f significant figures and accuracy are central to understanding

analytical data, risk-assessment conclusions, groundwater-transport m odels, or cost
estimates. Their importance is best explained by example:

• A risk-assessment specialist has calculated that the average concentration of con­

tamination in the soil on a site should not exceed 6.2389 mg/kg tetrachlorogoop
(TCG). He has also calculated that the average of TCG concentrations measured
on the site is 6.24 mg/kg. Does the site need to be cleaned up?
• For another project, an engineer has prepared two preliminary cost estimates for
site remediation. She estimated that option 1 would cost $1,326,279.86 and option
2 would cost $1,343,623.67. Based on these estimates, which option would be the
most cost-effective choice?

The TCG-contaminated site may not need to be cleaned up, and neither option 1 nor
option 2 may be more cost effective based on the estimates presented. The answers
depend upon the accuracy o f the estimates and the number o f significant figures.
Accuracy is a sim ple concept: the more accurate an estimate, the closer it is to
the true value. Increasing accuracy generally requires increasing cost, whether for
collecting more data, running more sophisticated chemical analyses, or spending
more labor hours working on the project.

13
14 THE FUNDAMENTALS OF HAZARDOUS WASTE SITE REMEDIATION

The concept o f significant figures is less intuitive. Calculated values are often
reported simply as they appear on a calculator or spreadsheet which has been set to
show an arbitrary number o f figures after the decimal point. Those figures may not
all be m eaningful (i.e., significant figures). Depending on the assumptions used in
the calculation, the clean-up level described above could be 6 mg/kg, 6.2 mg/kg, or
6.2389 mg/kg. Thus, the number o f significant figures in that calculation and in the
estimate o f the average concentration on site may determine whether or not the site
must be remediated.
How are significant figures determined? The number o f significant figures is at
least the number o f nonzero digits. Zeros may be significant figures, unless they are
used only to locate the decimal point.' For example, the follow ing numbers all have
three significant figures: 6.24, 0.000233, 1.00 x 10^, and 12,700.
The number o f significant figures in a calculated value — such as the clean-up
level or cost estimates in the examples above — depends on the uncertainty in the
numbers used to calculate that value. Two types o f uncertainty are considered:
absolute uncertainty and relative uncertainty. The absolute uncertainty in a number
is a single unit o f measurement. The relative uncertainty is the ratio o f the absolute
uncertainty to the total quantity.' For example, a pump priced at $1499 may be a
line item in a cost estimate. The absolute uncertainty in that cost is $1, and the
relative uncertainty is 1/1499.
When numbers are added or subtracted, the absolute uncertainty in the result
equals the largest absolute uncertainty among the components.' In less exact terms,
the answer should contain digits only as far as the first column containing significant
figures.^’^ For example, consider the sum o f 1200 + 1399.4 + 0.43. Without consid­
ering significant figures, the answer is 2599.83. However, only two figures are
significant and thus the answer is 2600.
When numbers are multiplied or divided, the relative uncertainty in the result
equals the largest relative uncertainty among the components.' Less precisely, the
number o f significant figures in the answer should be the same as the number of
significant figures in the least exact factor.^-^ U sing this guideline, the product of
0.4375, 1.0, and 6 is 3, not 2.625.
When a series o f calculations are performed, the final result should he rounded
o ff to the proper number o f significant figures, and not the intermediate results.
Exact numbers, such as the number o f tanks in a groundwater treatment system or
the number o f soil samples used to calculate an average concentration, are not
considered in determining the number o f significant figures.^-^
Exam ples 2.1 and 2.2 later in this chapter illustrate the use o f significant figures.

2.2 CHEMISTRY OF HAZARDOUS MATERIALS

Remediation technologies attempt to

separate contaminants from soil, water, or other media;

isolate or immobilize contaminants; or
destroy contaminants.
BASIC PRINCIPLES 15

The behavior o f chemical compounds determines how they may be remediated.

Common contaminants fall into one o f a relatively small number o f categories. The
information that follow s describes the general behavior o f common contaminants.
The discussion begins with a review o f basic terminology.

2.2.1 Terminology

Chemical compounds are classified as organic or inorganic. Organic compounds

are based on carbon atoms (with the exception o f cyanide, which is inorganic). They
can be anthropogenic (man-made) or naturally occurring compounds. Inorganic
compounds are non-carbon based, and com m only include metals. Whether organic
or inorganic, the chemical structure o f a compound determines its polarity or charge,
solubility, volatility, and ability to react with other substances.

2.2.1.1 Units

Concentration is com m only reported in a variety o f units. A mole is the mass o f

a chem ical compound which contains 6.022 x 10* m olecules. This unit is com m only
used to balance chemical equations and to characterize concentrations in air and
water. Chemists work with units o f gram moles, which are calculated by dividing
the mass in grams by the gram molecular weight. Chemical engineers often use
pound moles, calculated by dividing the mass o f a compound in pounds by the
m olecular weight. Gram m oles are used in this book rather than pound m oles. The
molecular weight, sometimes called the formula weight, is determined by summing
the atomic weights o f the constituent atoms. Atom ic weights are summarized in the
Periodic Table or tabulated in chemistry texts and references.
Contaminant concentrations in water are com m only reported in units o f milli­
grams p er liter (mg/L) or parts p er million (ppm), and micrograms p er liter (¡ig/L)
or parts p er billion (ppb). Data for highly contaminated water samples are som etim es
reported as a percentage. The concentration may be converted to molarity, or m oles
per liter (abbreviated M), for certain calculations. Units o f mole fraction (x j, which
is the ratio o f the m oles o f substance I to the total m oles o f all components, are also
used in som e calculations.

Example 2.1: An analytical laboratory has reported that a groundwater sample con­
tains 273 pg/L benzene (chemical formula C^Hj). Convert the units to mg/L, ppm, ppb,
%, M, and x,.
Convert to mg/L:
1000 pg = 1 mg
(273 pg/L) • (1 mg/1000 pg) = 0.273 mg/L

Convert to ppm:

, /, . , V 1 mg contaminant „
1 ppm (by weight) = -----^ ------------------= 0.0001 percent by weight (2.1)
10 mg water
16 THE FUNDAMENTALS OF HAZARDOUS WASTE SITE REMEDIATION

Density of water (STP) = 998 g/L = 998,000 mg/L

In general, 1 mg contaminant/l L water = 1 mg/998,000 mg = 1.002004008 ppm;
(0.273 mg/L) ■(1 L/998,000 mg) = 0.2735470942 ppm
Since the original concentration had only three significant figures, the concentration
in ppm should only have three significant figures: 273 |xg/L = 0.274 ppm

Convert to ppb:
1 |xg/L = 1 ppb, analogous to the derivation above for ppm
so 273 pg/L = 274 ppb

Conversion to percentage:
From Equation 2.1, 1 ppm = 0.0001%
(0.274 ppm) ■(0.0001%/! ppm) = 0.0000274%

Conversion to M:
The chemical formula of benzene is .
The atomic weight of carbon is 12.011; the atomic weight of hydrogen is 1.0079.
The molecular weight of benzene is 6 • (12.011 + 1.0079) = 78.1134 g/mole.
(0.273 mg/L) • (1 g/1000 mg)/(78.1134 g/mole) = 3.494913926 x 10-® M.
Since the least number of significant figures in the numbers used in this calculation is
3, the molarity should be rounded off to 3.49 x 10-® M.

Conversion to X/t
Assume that the groundwater contains primarily water, which has a chemical formula
of HjO and a molecular weight of (2 • 1.0079) + 15.9994 = 18.0152 g/mole. Using the
density o f water and the molarity of the solution (see above), (3.494913926 x 10-®
moles benzene/L water) • (1 L/998 g water) • (18.0152 g/mole water) = 6.3087748 x
l(h*, or, considering the number of significant figures, 6.31 x l(h*. (Note that the mole
fraction is unitless.)

Contaminant concentrations in solids such as soil, sediment, and sludge are

presented in units o f milligrams p er kilogram (mg/kg), micrograms p er kilogram
(Hg/kg), and percent. Concentrations may be expressed as wet weight, which includes
the w eight o f the water in the sample as it was collected from the environment, or
as dry weight. Common analytical methods for environmental analysis often report
the data on a dry-weight basis, but may report it on a wet-weight basis (e.g..
Reference 4).
Contaminant concentrations in air are com m only expressed in parts p er million
by volume (ppmv), parts p e r billion by volume (ppbv), mole fraction (y,), and partial
pressure (p,). Highly concentrated contaminants may be reported as percentages.

Example 2.2: An air sample at 25°C and 1 atm contains 210 milligrams of benzene
per cubic meter (mg/m^). Convert this concentration to ppmv, y,-, and p,.
From Example 2.1, the molecular weight of benzene is 78.1134 g/mole. Air is approx­
imately 78.1% nitrogen (N2, molecular weight 28.0134 g/mole) by volume and 20.9%
BASIC PRINCIPLES 17

oxygen (O2, molecular weight 31.9988 g/mole). Therefore, the molecular weight of air
is approximately (0.781 • 28.0134) + (0.209 ■31.9988) = 28.566215 g/mole.

Convert to ppmv:
At 25°C and 1 atm, 1 gram mole of an ideal gas has a volume of 22.41 liters. In general.

1 volume o f contaminant
1 ppm v =
10“ volumes air, including contaminant (2 .2)

= 0.0001 percent by volume

Then,

( 2\Q mg benzene'V\Q ^ g^^ 1 mol benzene Y 22.41

\ 1 m^ air mg j 78.1134 g jL mol )1 10“ J

volumes benzene
= 60.24702549
volumes air

or, considering significant figures, 60.2 ppmv.

Convert to y¡:

^ 210 mg benzene^ ^10 ^ g ''^ l mol b e n z e n e ^ 22.41 L V 10 ^

1 air } mg 78.1134 g mol

mol benzene
= 0.0000602
mol air

Convert to p-,:
In general.

P i ~ Pioial y i (2.3)

Since p„, = 1 atm, p-, = 0.0000602 atm.

2.2.1.2 Charge and Polarity

Charge and polarity are similar properties which help to determine the solubility
o f a compound and its ability to adsorb to solids.
An ion is a charged atom or fragment o f a molecule. M ost inorganic chem icals
dissolved in groundwater are ions. Certain organic compounds can also be ions under
certain conditions. A cation is positively charged because it lacks one or more
electrons from its structure. Examples include Ca^^, Cr+^, and Cri“. An anion is
negatively charged because it carries excess electrons. Examples include Cl” and
18 THE FUNDAMENTALS OF HAZARDOUS WASTE SITE REMEDIATION

Cr203^. The valence state o f an ion describes the degree o f charge (e.g., +2, +3). It
changes in redox reactions. (See the discussion o f redox reactions in Section 2.2.1.6.)
N onionic species can be characterized as polar or nonpolar. In a polar m olecule,
electrons are not shared equally between atoms. A s a result, different parts o f the
m olecule have slight positive and slight negative electronic charges. Certain atoms
are more electronegative than other atoms; such atoms tend to attract electrons and
thus carry a slight negative charge. Electronegativity increases as follows:^

F>0>C1, N>Br>C, H

Polar compounds are more soluble in water than similar nonpolar compounds.

2.2.1.3 Solubility

Solubility, in com m on environmental applications, is the amount o f a compound

that can dissolve in water. In general, solubility decreases with increasing size for
similar organic m olecules, and polar compounds are more soluble than similar
nonpolar compounds.
For ionic compounds, solubility is characterized by the solubility product constant
(Kjp). For the equilibrium reaction

(where A and B are ions and x and y are integers)

(2.4)

The solubility o f a particular compound depends on temperature and pressure. It

also depends on the types and concentrations o f other compounds in the water. The
presence o f a relatively high concentration (i.e., percentage level) o f one organic
compound can increase the solubility o f a second compound by cosolvation.^ ’' The
pH o f the water affects the solubility o f ionic compounds. Complexation can increase
the solubility o f ionic compounds; for example, mercury can form soluble com plexes
with chloride in solution such as HgCl^^. Complexation can increase the solubility
o f a compound above the concentration predicted by the solubility product constant
for the hydroxide, for example.
Certain types o f compounds with relatively low solubility may exist as a separate
phase in an aquifer. Light nonaqueous phase liquids (LNAPL), also known as floaters,
are separate-phase liquids which are less dense than water. These substances have
a speciflc gravity (i.e., density relative to that o f water) o f less than one. Dense
nonaqueous phase liquids (DNAPL), or sinkers, are more dense than water. They
have a specific gravity greater than one. LNAPL and DNAPL are discussed further
in Section 2.3.4.1.
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 XIXe Situation : Tuer un des siens inconnu 92
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XXIIe Situation : Tout sacrifier à la Passion 104
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(Conséquences) 173
 ACHEVÉ D’IMPRIMER
Le 10 Novembre 1894
POUR LE
MER CVRE D E F RANC E
PAR
C. RENAUDIE
56, RUE DE SEINE, 56
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