O O  A    Committee on the
                        EPA/6QO/R-93/012b
           4/l\   Challenges of
           / • \   ...  ^            February 1993
        . ^ z—a   Modern Society
     Demonstration of Remedial
       Action Technologies for
Contaminated Land and Groundwater
              Final Report

            Volume 2-Part 1
                Number 190
          North Atlantic Treaty Organization

                 1986-1991

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                                       COMMITTEE ON
                                    THE CHALLENGES OF
N ATO/CCMS                   MOtttjgN SOCIETY
                                        Number 190
                FINAL REPORT
                      Volume 2
                     Appendices
                Part 1: Pages 1 through 662
       Demonstration of Remedial Action Technologies
          for Contaminated Land and Groundwater
                  Pilot Study Directors

             Donald E. Sarmlng, United States - Director
              Vokler Franzius, Germany - Co-Director
             Esther Soczo, The Netherlands - Co-Director


                 Participating Countries

                 Canada        Germany
                 Denmark      The Netherlands
                  France       United States
               Observer and Other Countries

                  Austria         Norway
                   Italy          Turkey
                  Japan       United Kingdom
                     1i86-1991
                                         ^Xฃ> Printed on Recycled Paper

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 Disclaimer

 This publication has been prepared under the auspices of the North Atlantic Treaty Organization's Committee on
 the Challenges of Modern  Society (NATO/CCMS).  it is not a publication  by the United States  Environmental
 Protection Agency or by an agency or department of any other country.

Printing support of this document has been provided by the United States Environmental Protection Agency.
Keywords

Aerobic
Anaerobic
Aqueous extractments
Aroclor(s)
Binder screening
Binders, generic
Binders, Portland cement
Bodegradation
Biological treatment
Bioreaclor
Cement, Portland
Chemical treatment
Chloroform
Composting
Dahalogenatlon
Dtehforobenzene
Dtoxln(s)
Electro-osmosis
Eloctro-phoresis
Electro-reclamation
Emissions, stack gas
Encapsulation
Extracting agents
Extraction
Fixation
Fractured rock
Furan(s)
Ground water, contaminated
Ground water, contaminated, treatment
Hazardous waste
Hazardous waste site
High-pressure jet
Immobilization
In-situ
Incineration
Indirect heating
Infrared incineration
Kiln, rotary
KPEG
Landfarming
Leach testing
Microblal treatment
Microorganisms
Oxidation
PCB
Pesticides
Pozzonanes
Pyroiysis
Remedial investigation/Feasibility study
Remediation
Remedy selection
Separation
Soil, contaminated
Soil, contaminated, treatment
Solidification
Stabilization
Stack gas emissions
Thermal desorptlon
Thermal destruction
Trlchloroethene

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Foreword

The Council of the North Atlantic Treaty Organization (NATO) established the "Committee on the Challenges of
Modem Society (CCMS) in 1969.  The CCMS was charged with developing meaningful environmental and social
programs that complement other international programs with leadership in solving specific problems of the human
environment within the NATO sphere of influence; as well as transferring these solutions to other countries with
similar challenges in environmental protection.

Ground water and soil contamination are among the most complex and challenging environmental problems faced
by most countries today, and there is an ongoing need for more  reliable, cost-effective cleanup technologies to
address these problems.   Many governmental and  private organizations, in many countries,  have committed
resources to the development, test and evaluation and demonstration of technologies to meet this need. The
ongoing challenge to these organizations is how to maximize the value of these technology advancements and
effectively transfer the information to people responsible for making decisions and implementing remedial actions.

Consequently, a NATO Committee on  the Challenges of Modern Society  (NATO/CCMS) Pilot Study on the
Demonstration of Remedial Action Technologies for Contaminated Land and  Ground Water was conducted from
1986 through 1991. It was designed to identify and  evaluate innovative, emerging,  and alternative  remediation
technologies, and transfer technical performance and economic information on them to potential users. The Study
was conducted under the joint leadership of the United States, Germany, and The Netherlands. In addition to these
co-pilot countries, Canada, France, and Denmark actively participated throughout the five year study.  Norway
participated as an "observer" nation, and the United Kingdom, Department of the Environment was represented at
conference and workshop meetings.  Japan was represented at the initial International conference. Organizations
from Hungary and Austria attended the Fifth International Meeting.

This is the detailed report of the findings, conclusions and recommendations produced by that Study. It is intended
to serve as a reference to the state-of-the-technologies examined by the participants.  It is not intended to be a
manual on technology applications but as a guide to the potential application of different technologies to various
types of soil and ground water contamination. The conclusions reached from this Study revealed both the strengths
and weaknesses  of current technologies as well as what efforts are needed to increase the  effectiveness of
remediation tools and their application.

There are several volumes to this report. Volume 1 is the report itself. Volume 2 is the Appendices, and comes in
two parts.  Part 1 contains overviews of national environmental regulations, and papers by NATO/CCMS Guest
Speakers; it consists of pages 1 through 662. Part 2 contains the final reports of the NATO/CCMS Fellows, and
reports of the individual projects; it consists of pages 663 through 1389.

A limited number of copies of this report are available at no charge from two sources:  NATO Committee on
Challenges to Modern Society, Brussels, Belgium; or U.S. Environmental Protection Agency, 26 West Martin Luther
King Drive, Cincinnati, Ohio 45268, United States. When there are no more copies from these sources, additional
copies can be purchased from the National Technical Information Service, Ravensworth Building, Springfield, Vir-
ginia 22161, United States.

                                          Donald E. Sanning
                                         Pilot Study Director
                                 U.S. Environmental Protection Agency
                                            United States
              Volker Franzius                                       Esther Soczo
              Co-Director                                         Co-Director
              Umveltbundesamt                                     Rijksinstituutvoorvolksgezondheid
              Germany                                            en milieuhygiene (RIVM)
                                                                  The Netherlands

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Abstract

This publication reports on the results of the NATO/CCMS Pilot Study "Demonstration of Remedial Action Tech-
nologies for Contaminated Land and Ground Water" which was conducted from 1986 through 1991.  The Pilot
Study was designed to identify and evaluate innovative, emerging and alternative remediation technologies and to
transfer technical performance and economic information on them to potential users.

Twenty-nine remediation technology projects were examined which treat, recycle, separate or concentrate con-
taminants In soil, sludges, and ground water. The emphasis was on in situ and pn-s'rte technologies; however, in
some cases, e.g., thermal treatment, fixed facilities off-site were also examined.  Technologies included are;  ther-
mal, stabilization/solidification, soil vapor extraction,  physical/chemical extraction, pump  and treat ground water,
chemical treatment of contaminated soils, and mlcrobial treatment.

This report serves as a reference and guide to the potential application of technologies  to various types of con-
tamination; it is not a design manual. Unique to this study is the examination and reporting of "failures" as well as
successes.

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Acknowledgements

The Pilot and Co-Pilpt Study Directors thank all who made significant contributions to the work of the Pilot Study:

Those representing their countries made a major contribution to the direction of the Study by recommending
projects within their respective countries which would be of particular interest to this Study, and by discussing the
regulatory and general environmental technology situations in their countries.

The various chapters were written by the respective authors after reviewing reports prepared on the Case Studies
for the meetings of the Study Group.

Good use was made of the NATO/CCMS Fellowship Program to further enhance the value of the Study and a
number of Fellows contributed directly to the preparation of this report. Robert QHenbuttel of Battelle also served as
the general editor for the report, supported by Virginia R. Hathaway of JACA Corp., editor.

Expert speakers, often supported by NATO/CCMS travel funds, participated in the workshops and conferences of
the Pilot Study and contributed to the work of the Pilot Study Group.

Until his retirement, the NATO/CCMS International Staff was represented by the former CCMS Director, Mr. Ter-
rance Moran, Dr. Denlz Beten replaced Mr. Moran and attended the Fifth International Meeting.

Ms. Naomi iarkleyof the Office of Research and Development, Risk Reduction Environmental Laboratory, Super-
fund Technology Demonstration Division, U.S. Environmental Protection Agency served as Task Project Manager
for this project.

The names and addresses of all participants in the Study Group are given In Volume Two,

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Contents;  Volume 2
Foreword	i
Abstract	 . . .	ii
Acknowledgements	,	iii

Part I

Appendix 1
1 - A  NATO/CCMS Tour de Table:  National Regulations and Other Overview Topics
      (Given by Countries and Institutions Involved in the NATO/CCMS Pilot Study)

      Participating Countries
         Canada	 3
         Denmark , , , ,	  17
         France		  23
         Germany	  27
         The Netherlands	  37
       ,  United States	  45

      Observer and Other Countries
         Austria	 ,	,	  71
         Norway	  83
         Turkey	  91
         United Kingdom	  99

      United States/German Bilateral Agreement on Abandoned Site Clean-up Projects	113

1 - B  Presentations by NATO/CCMS Guest Speakers	147

      Brett Ibbotson, Canada - AERIS, an Expert Computerized System to Aid in
         the Establishment of Cleanup Guidelines  	149
      Colin Mayfield, Canada - Anaerobic Degradation	 161
      A. Stelzig, Canada - Cleanup Criteria in Canada  	171
      Troels Wenzel, Denmark - Membrane Filtering and Biodegradation	211
      Herve Billard, France - Industrial Waste Management in France	 223
      Christian Bocard, France - New Developments in Remediation of  Oil
         Contaminated Sites and Ground Water  	255
      Jean Marc Rieger, France  - Incineration in Cement Kilns and Sanitary
         Landfilling  	273
      Bruno Verlon,  France - Contaminated Sites -  Situation in France	285
      Fritz Holzwarth, Germany - Cleanup of Allied Military Bases in the
         Federal Republic of Germany		293

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      James Berg, Norway - Cold-Climate Bioremediation:  Composting and
         Groundwater Treatment Near the Arctic Circle at a Coke Works	295
      Gjls Breedveld, Norway - In Situ Bioremediation of Oil Pollution
         in Unsaturated Zone	,	307
      Gunnar Banders, Norway - The History of NATO/CCMS	315
      Robert L. Siegrist, Norway - International Review of Approaches
         for Establishing Cleanup Goals for Hazardous Waste Contaminated
         Land; and Sampling Method Effect on Volatile Organic Compound
         Measurements in Solvent Contaminated Soil  	321
      Guus Annokkee, The Netherlands - Biological Treatment of            ;
         Contaminated Soil and Groundwater	479
      D.B. Janssen, The Netherlands - Degradation of Halogenated Aliphatic       •
         Compounds by Specialized Microbial Cultures and their,Application
         for Waste Treatment		481
      Rene Kleijntjens, The Netherlands - Microbial Treatment	497
      Karel Luyben, The Netherlands - Dutch Research on Microbial Soil
         Decontamination in Bioreactors	 503
      Yalcin B. Acar, United States - Electrokinetic Soil Processing; A
         Review of the State of the Art	 507
      Douglas Amrnon, United States - United States "Clean Sites"	535
      Roy C, Herndon, United States - Environmental Contamination in  Eastern
         and Central Europe	 567
      Gregory Ondich, United States - The Use of Innovative Treatment
         Technologies in Remediating Waste	 .:.	579
      Ronald Probstein, United States - Electroosmotic Purging for In Situ
         Remediation	603
      Hans-Joachim Stietzel, European Economic Community	635

Part 2

1 - C  Final Reports by NATO/CCMS Fellows	663

      Alain Navarro, France - New French Procedures for the Control of
         Solldificated Waste	665
      Peter Walter Werner, Germany - Biodegradation of Hydrocarbons  .  . .	677
      Alessandro di Domenico, Italy - Sunlight-Induced Inactivation of                <.
         Halogenated Aromaties in Aqueous Media: Photodegradation Study
         of a Benzotrifluoride and an Evaluation of Some Industrial Methods	711
      Sjef Staps, The Netherlands - International Evaluation of In Situ
         Bioremediation of Contaminated Soil and Groundwater	 741
      Resat Apak, Turkey - Heavy Metal and Pesticide Removal from
         Contaminated Ground Water by the Use of Metallurgical
         Solid Waste Solvents	'. ;	767
      Aysen Turkman, Turkey - Cyanide  Behaviour in Soil and Groundwater
         and its Control	815
                                           VI

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      Robert Bell, United Kingdom - Environmental Legislation in Europe	839
      Michael A. Smith, United Kingdom - In Situ Vitrification	-.'.'	843
      James M. Gossett, United States - Biodegradation of Dichloromethane
         Under Methanogenic Conditions	859
      Merten Hinsenveld, United States • Innovative Technologies for Treatment
         of Contaminated Soils and Sediments; and Alternative Physico-Chemical and
         Thermal Cleaning Technologies for Contaminated Soil	<	875
      Robert Olfenbuttel, United States - Summary Report: NATO/CCMS Pilot Study on
         Demonstration of Remedial Action Technologies for Contaminated Land and
         Groundwater	901
      Wayne A. Pettyjohn, United States - Principles of Ground Water:
         Fact and Fiction	903

Appendix 2
Thermal Technology Case Studies

2 - A  Rotary Kiln Incineration, The Netherlands , ,	 911
2 - B  Indirect Heating in a Rotary Kiln, Germany		929
2 - C  Off-site Soil Treatment, Japan	973
2 - D  Electric Infrared Incineration, United States	987

Appendix 3
Stabilization/Solidification Technology  Case Studies

3 T A  In Situ Lime Stabilization (EIF Ecology), and Petrifix Process (TREDI), France   ..,,..., 995
3 - B  Portland Cement (Hazcon, presently IM-Teeh), United States .	  1011

Appendix 4
Soil Vapor Extraction Technology Case Studies

4 - A  In Situ Soil Vacuum Extraction,  The Netherlands	, •. .	1017
4 - B  Vacuum Extraction of Soil Vapor,
      Verona Well Field Superfund Site, United States	1031
4 - C  Venting Methods, Hill Air Force  Base, United States		1053
4 - D  Additional case studies, United States	;..-...  1075

Appendix 5
Physical/Chemical Extraction Technology Case Studies

5 - A  High Pressure Soil Washing (Klockner), Germany	1081
5 - B  Vibration (Harbauer), Germany	>	,	1101
5 - C  Jet Cutting Followed by Oxidation (Keller),  Germany	  1111
5 - D  Electro-reclamation (Geokinetics), The Netherlands	  1113
5 - E  In Situ Acid Extraction {TAUW/Mourikj, The Netherlands	1135
5 - F  Debris Washing,  United States  ..,...,...,	1157
                                            VII

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Appendix 6
Ground Water Pump and Treat Technology Case Studies

6 - A Decontamination of Ville Mercier Aquifer for Toxic Organics,
      Ville Mercier, Quebec, Canada	1167
6 - B Evaluation of Photo-oxidation Technology (Ultrox International),
      Lorentz Barrel and Drum Site, San Jose, California, United States	 1207
6 - C Zinc Smelting Wastes and the liot River, Viviez, Averyon, France	1211
6 - D Separation Pumping, Skrydstrup, Denmark	1231

Appendix 7                                                           ,
Case Studies on Chemical  Treatment of Contaminated Soils; APEG

7 - A Supplementary Information on the APEG Process, Wide Beach, United States	1259
7 - B The AOSTRA-Taciuk Thermal Pyrolysis/Desprption Process, Canada  . .-. ... . ,	1271
7 - C AOSTRA-SoilTech Anaerobic Thermal Processor Wide Beach, United States . .  . . . .  . ,1289
7 - D Site Demonstration  of the SoilTech  "Taciuk" Thermal Desbrber, Waukegan
      Harbor, United States	 ,. , . ... .,,,.,..,.... 1293

Appendix 8
Microblil Treatment Technology Case Studies

8 - A Aerobic/Anaerobic In Situ Degradation of Soil and Ground Water,
      Skrydstrup, Denmark	.,...,	1299
8 - B In Situ Biorestoration of Soil, Asten, The Netherlands	1325
B - C In Situ Enhanced Aerobic Restoration of Soil and Ground Water,
      Eglin Air Force Base (AFB), United States	; . .	1327
8 - D Biological Pre-treatment of Ground Water, Bunschoten, The Netherlands	1349
8 - E Rotary Composting  Reactor for Oily Soils, Soest, The Netherlands	 1363

Appendix 9
List of NATO/CCMS  Pilot Study Participants 	, . . .	1377
                                           VIII

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                                               Appendix 1-A

                                   NATO/CCMS Tour de Table
       National Regulations and Other Overview Topics {Given by
Countries and Institutions Involved in the NATO/CCMS Pilot Study)

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Canada's Tour de Table Presentation

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Contaminated sites - An Update
of Canadian Activities
T.W. Foote, P. Eng.
Environment Canada
Presented at the Fifth Annual NATO, CCMS Conference of the Demonstration of Remedial
Action Technologies for Contaminated Land and Groundwater - November 18lh - 22nJ,  1991
Washington, D.C.

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                       Contaminated Sites - A Canadian Perspective

1.0    Introduction
       This paper provides an over/iew of programs and activities associated with the
       identification, assessment and remediation of contaminated land and groundwater in
       Canada.

2.0    Profile of Canadian Contaminated Site Problems
       Table 1 provides a listing of those municipal and industrial activities that have
       contributed to the creation of contaminated  sites in Canada.

       Given the extent to which our countries' economy  has been based on our vast natural
       resources, it is no surprise that mining, metallurgical  and wood preservation facilities
       account for a large share of the contamination problems being encountered.

       As well, with increasing frequency, urban redevelopment is unearthing contamination
       attributable to abandoned coal gasification plants, some of which have been out of
       operation since  the turn of the century.

       Other problems are a lot more recent, for example  the contaminated sites that resulted
       last year from two enormous  fires at automobile fire  storage areas,  one in Quebec and
       the other in Ontario.

       Scrap yards present an emerging and, because of their numbers, widespread problem
       in Canada.  The fact that many of these facilities have a limited financial base also
       means that when contamination problems are encountered, governments  are often
       likely to inherit them.

       At some of our larger sites such as in downtown Vancouver,  we are encountering
       contamination that covers the spectrum of industrial activities as bhown  in Figure I.

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         Table 1
Profile of Contaminated Site
    Problems in Canada
1. Treatment/Disposal of Wastes
Municipal Sanitary Landfills
(Dumps)
Industrial Waste Landfills
(Dumps)
Mine Tailings
2. Industrial/Commercial
Activities
Chemical and Petrochemical
Facilities
Metallurgical Facilities
Foundries/Steel Mills
Wood Preservation Facilities
Coal Gasification Facilities
Scrap yards/shipyards/rail yards
Pesticide Storage Sites
Waste Storage Sites
Primary Concern
Land settlement
Methane gas
Some toxic organics and
inorganics
Toxic organics and inorganics
Toxic heavy metals,
radionuclides
Acid mine drainage

Toxic organics, inorganics
Heavy metals
Heavy metals, hydrocarbons
Chlorophenolics, toxic metals
Polyaromatic hydrocarbons
Metals, solvents, hydrocarbons,
asbestos
- PCB's
Pesticides
- PCB's, tires

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           A
           N
     FIGURE  I

 PACIFIC  PLACE
VANCOUVER,   B.C
  0      100    2M     300
      Scale Meiers
Legend
       ^ฎ    Aieas of Hazardous Waste

       [  1  |  Parcel Number


Note: The remaining portions ot the site, including ihe
areas represented by the letters F, 1, and L missing from the
list opposite, may include contamination below hazardous
wastes levels. These will be remediated if and as required
In meet provincial sliinriacds
                                            Historical Activities and Land Use
                                            Associated with Major Areas of Contamination

                                            A - Boat building and sawmill (organks)
                                            B - Woodvuaste filllrom sawmill activities
                                            C - Shoreline dumping (lead)
                                            D - Pmisch Coal Gasification Plant (organics, metals)
                                            E  - Shoreline dumping Imelals)
                                            G - Shoreline dumping and fuel lines (metals, organics)
                                            H - Chlorophenol dip tank operation (chlorophenols)
                                            J  - Deep woodwaste fill associated with sawmill activities (organics)
                                            K  - Mixed lumber and industrial activities (orgarucs, metals)
                                            M - Coal-tar dumping associated with BCER Coal Gasification Plant
                                            N - Industrial, lumber and warehouse operations (rnelals.arganics)
                                            Q,P - Coal-tar associated with BCER coal gasification plant

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3.0    Evolution of Legislative Initiatives                                   .    :
       Protection of the environment in Canada is a shared responsibility between the federal
       and provincial levels of government.

       While the federal and ten provincial governments each have comprehensive ,
       environmental legislation, federal regulatory activities have by in large been associated
       with controlling toxic chemicals in the market place (i.e. manufacture or importation)
       and in the development of minimum national effluent and  or emission standards  for
       specific industrial sectors such as petroleum refineries and pulp and paper mills.

       The provinces have and continue to be responsible for issuing operating permits  to
       specific industrial and commercial establishments located within their respective
       borders.  The provinces also have assumed the lead for dealing with contaminated
       sites, except where such sites are located on federal crown land or associated with
       federal government activities (e.g. military bases and airports)

       The evolution of environmental legislation in Canada mirrors that of the majority of
       industrial countries starting in the late 60's and early ?()'*> focusing  on conventional
       pollutants.  In the late 70's and early HO's, a significant shift was  made towards
       controlling toxic substances including more recently those being released to the
       environment from contaminated sites.

       As we are all finding out,  establishing a regulatory framework to deal with sources of
       pollution that were created years ago by companies which either don't exist or haven't
       got the money to carry out the necessary clean-up action presents a significant
       challenge.

       Under the National Contaminated Sites Remediation Program, which will  be dealt with
       in more  detail later in this paper, considerable progress is  being made in putting in
       place the necessary regulations  at the provincial  level to enforce the "polluter pays"
                                             8

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       principle to the maximum extent possible when dealing with contaminated sites.
       Within the past year, Ontario, Quebec, British Columbia and the  Yukon Territories
       have all strengthened their legislation in this regard.

       A new issue has recently come  to the fore in Canada dealing with administration of
       bankruptcy cases.  Specifically,  the question being addressed by both regulators and
       the courts  is whether environmental liability cakes precedence over secured and non-
       secured creditors.

       In a recent case in Alberta, a provincial  court ruled that a bank was  required to bring a
       bankrupt facility into compliance with a provincial clean-up order before any of the
       companies assets could be distributed.  In another case, this time in  British Columbia,
       no trustee  could be found who was willing  to administer the bankruptcy  process
       because of the unknown extent  of environmental liability associated  with the property.

       Government/industry consultations have been initiated in an attempt to identify the full
       scope of this problem and  how  best to resolve it in a way that recognizes both
       financial as well as environmental requirements.

4.0    National Contaminated Sites Program

4.1    Background
       In recognition of the potential magnitude Of the contaminated sites problem in Canada
       and the lack of a consistent national approach to deal with it, this issue was placed on
       the agenda of the Canadian Council'of Ministers of the Environment (CCME) in 1988.

       Subsequent problem definition and assessment by the federal, provincial and territorial
       governments culminated in October 1989 with the announcement by CCME to
       establish the  National Contaminated Sites Remediation Program.

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The program has three objectives:

i)      based on the polluter pays principle, to identify, assebs, and remediate, in a
       nationally consistent manner, all contaminated bites that are adversely affecting,
       or have the potential to adversely  affect, human health or the environment,

ii)     to provide the necessary government funds to remediate those high-risk
       contaminated sites (termed "orphan" sites) for which the owner or responsible
       parry cannot be identified or is financially unable to carry out the necessary
       work, and

iii)    to stimulate the development and  demonstration of new and innovative
       remediation technologies.

The NCSRP operates on a cost-shared, five-year, $250 million budget based on
matching funding by the federal government and the provincial/territorial governments.
Of this total, $200 million will  be directed to the remediation of orphan  high-risk
contaminated sites, and the remaining $50 million will be  used to develop and
demonstrate new remediation technologies.

The program is administered  mainly through bilateral  agreements between environment
Canada and the provinces and territories.  These  agreements define administrative
procedures and the role and responsibilities that each party has in cleaning up orphan
sites and in managing individual projects to develop and demonstrate technology.

To date, such agreements have  been signed between the federal government and the
governments of British  Columbia, Alberta, Ontario, Quebec, New Brunswick, Nova
                                                                    i
Scotia and Newfoundland.
                                    10

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4.2    Specific "Orphan" Contaminated Site Activities
       In the first year and a half that the program has been in effect, remediation projects
       have been completed, are  underway, or are  in design-phase at 15 sites.

      : Alberta
       Under the Alberta agreement,  work has begun at three  orphan high-risk sites — Canada
       Creosote in Calgary, Peerless Wood Preservers in Cayley and Purity 99 in Kartell.

       Initial work at the Canada Creosote initially involves on-site containment and free
       product recovery.  Additional  site assessment and the demonstration of a gravel
       washing technology are to be carried out before any further remedial action is planned.

       At the Peerless site, pertachlorophenol contaminated soil will be excavated and sent
       for incineration to the Alberta Special Waste Management Facility in Swan Hills.

       At Hartell, a  former refinery site with widespread hydrocarbon contamination, on-site
       containment accompanied by groundwater recovery and treatment will  be pursued.

       Ontario
       Two sites — one in Hagersville, and the other in Smithville, are the first being
       addressed under the Canada/Ontario agreement.

       Remediation  at the Hagersville site, which  is almost complete, involved the removal of
       contaminated soil, subsurface  oil recovery and the treatment of contaminated  surface
       and groundwater arising from a massive fire at this tire storage facility.

       Remediation  at the Smithville site, a former waste oil transfer site,  is well underway
       using rotary kiln incinerator to destroy PCB liquids and PBC contaminated soils and
       sludges.
                                          11

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Quebec
Sites in Saint-Jean-Sur-Richelieu and Saint Amable are the first to be addressed under
the Canada/Quebec agreement.  Remediation at the Saint-Jean-Sur-Richelieu site,
completed earlier this year, involved the excavation and .secure landfilling of lead
contaminated soil from residential properties located near a battery recycling facility
formerly operated by Balmet Canada Inc.

Remediation at Saint-Amable has initially  focused on the treatment of groundwater
contaminated as a result of the fire at this  tire storage site. Additional remedial action
at the site is being considered.

Nova scotia
The first orphan high-risk contaminated site to undergo clean-up will be a scrap yard
site located  at Five  island Lake near Halifax.  Excavation and secure storage of lead
and PCB contaminated soils is underway.  Additional assessment is  being carried out
to determine whether groundwater contamination at the site is a problem which must
also be addressed.

New Brunswick                                      ,                  ;
Remedial activity has Been initiated at  six sites  under the Canada/New Brunswick
agreement.

Remedial action at  these sites, all of which involve petroleum contaminated soils and
groundwater, employs enhanced bioremediatkm and groundwater recovery/treatment.

Newfoundland                                                       :
Under  rte Canada/Newfoundland agreement, alternative technologies are being
evaluated to remediate a PCB and heavy metal  contaminated soils at a scrap yard site
located in Makinsons.                                            :
                                    12

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4.3    Technology Development and Demonstration Projects
       The principle objective of the DESRT (development and demonstration of site
       remediation technology) component of the program is to accelerate the development of
       new and innovative technologies having the potential to resolve problems which are
       critical to the environmental remediation of contaminated sites.  It covers the areas of
       site characterization, assessment, remediation, and compliance monitoring.

       The first priority is demonstration, over the medium term, of promising new
       technologies that have been developed to the pilot plant stage, but require on-site, field
       evaluation to verify performance and cost information.  The second priority is to
       encourage the advancement of technologies that are in the laboratory stage of
       development, and offer alternative technologies for site remediation over  the medium
       term.

       The basic eligibility criteria for technology projects are as follows:

              The technology must be unique, or used uniquely, and must have  the potential
              for wide application at contaminated sites across Canada, or relate to a serious
              problem identified in an area within Canada.

              The project must involve technological risk, and should be designed to lead,
              ultimately,  to commercialization of the technology.

       -      DESRT funding must bring incremental value to the project; if it  would
              otherwise proceed at the same level of effort without desrt assistance, the
              project  is ineligible.

       As this is a federal-provincial/territorial  program, approval by both levels of
       government is  required.
                                           13

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Technology development/demonstration projects that have to date been approved under
the program are as follows:

British Columbia
The Pacific Place Site in Vancouver is a proposed residential, commercial, and open
space development of 82.5 hectares of land on the north side of False Creek in
Vancouver. The site is  contaminated  with PAHS, other organics, metals, wood waste,
and PCP.  DESRT is participating in treatability studies involving innovative
technologies for stabilization of organics and inorganics, bioremediation, and thermal
extraction. It is expected  that these studies wEI be completed prior to the end of
March, 1991.

Alberta
The Peerless Wood Preservers site in  Cayley is polluted primarily with PCB.  The
R&D project under DESRT is to  investigate the on-site land treatment of the
contaminated soils,  combined with in  situ enhanced biodegradadon  in fractured till,
and leachate capture in the underlying bedrock aquifer.

Located  on the bank of  the bow river in the centre of Galgary, the Canada Creosote
site is polluted with creosote and  PCP as a result of wood preserving activities.  There
is a dense, non-aqueous phase liquid  (DNAPL) pool within  the gravel overlying
bedrock  under the site; drilling in the riverbed gravels of the bow river showed
DNAPL as well. Creosote can be seen on  the river  bed.  Initial work under DESRT
involves the development of technology for washing the riverbed gravel, allowing  it to
be replaced in the river.

New Brunswick                                                       ;
The Department of Transportation site in Saint John is contaminated with PCBs and
heavy metals—mainly lead. The project under desrt  involves the investigation of soil
                                    14

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      .washing/solvent extraction and bioslurry reactors for use in the treatment train.  The
       study will be completed early in 1992.

4.4    Common Assessment and Remediation Guidelines
       Since the program was announced in 1989, considerable effort has been directed
       towards the development of guidance documents to enhance national consistency in
       assessing and remediating contaminated sites.

       In working towards this goal the CCME has benefited considerably from the
       evaluation of systems and criteria currently in use in various jurisdictions in Canada
       and in other countries.  As well, consultations held between governments, industry and
       public interest groups in  April and November of 1990 have contributed to ensuring
       that site evaluations and criteria proposals are both workable and responsive to the
       needs and expectations of various sectors and interests in Canadian society.

       Due to be published in January 1991, the CCME National Classification System will
       be used to classify contaminated sites into three broad categories of concern, according
       to their level of risk.  A site is designated high-risk when site contamination is such
       that  it represents a real or imminent threat to human health or to the environment.  In
       this case,  immediate action is required  to reduce the threat.

       Another document which was released at the annual GCME meeting on November 7!t
       in Halifax, is the Interim National  Environmental Quality Criteria.  These criteria
       establish numerical standards for the assessment and remediation of soil and water
       based on the safe use of agricultural, residential, commercial, industrial, and park
       lands.  They are based on a review of existing criteria used in some jurisdictions, and
       incorporate the guidelines established by  the CCME in 1987 on Canadian Water
       Quality, as well as Health and  Welfare Guidelines  established in 1989 on Canadian
       Drinking  Water Quality.
                                          15

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Environmental quality criteria for contaminated sites are intended to provide general
technical and scientific guidance to provincial, federal, territorial, and non-
governmental  agencies in the assessment and remediation  of contaminated sites in
Canada.  They serve as benchmarks against which to assess the degree of
contamination at specific sites. More importantly, they constitute a common scientific
basis for the establishment of site specific remediation objectives.  Variations in local
conditions.

In the last decade, environmental concerns have become a major preoccupation.  There
is a recognition  that preventable damage must be avoided  and, where possible,  the
effects of past neglect attenuated.  In the coming year, the National Contaminated
Sites Remediation Program will continue to carry this basic principle forward, and to
focus on consolidating its early gains.
                                    16

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Denmark's Tour de Table Presentation
  17

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         NATO/CCMS Pilot study on
Demonstration of Remedial Action Technologies
   for Contaminated Land and Groundwater
      Contribution to the Tour-de-Table
            Neel Str0bsek, M.Sc.
                Dan!sh-EPA
         5th International Conference
              Washington D.C.
                   USA
                     18

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Contribution to the Tour-de-Table, Neel Str0baek, M.Sc., Danish-EPA

Contents
1. Legislation and financing
2. Status, site investigations and remedial actions
3. Reactions  from society
4. Remedial  action technologies
5. Guidelines
6. Looking at the  Future.
1. Legislation and financing.
The Danish Law on Waste Sites concerns mapping, investigations, remedial actions and
monitoring on former landfills, industrial sites and oil/petrol storages. Regarding orphaned sites
the activities are financed by the authorities, which means that the tax-payer is paying.

The decentralized structure of the Danish Society with 275 Municipalities within 14 Counties
has made it possible to divide the work between the Counties and the State, represented by
the Danish Environmental Protection Agency. In general,  the Counties are responsible for the
actual work,  while the EPA sets up regulations  and guidelines.

The total number of sites are not yet known, and the nessesary funding  are laid down for
periods  of 4  years.  For the 1990-93 period a total amount of 540 mio. Dkr (app. $ 80 mio
U.S.)  is of disposal for investigations, monitoring and remedial actions.
2. Status, site investigations and remedial actions
The inventory of September 1991 counts 2493 waste sites. The total .number must be expected
to be between 6.000 to 10.000.
                                            19

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On the 1st of January 1990, the investigations and risk assessments Were terminated on 306
sites and 102 remedial actions had taken place. Further 21 remedial actions were on the
planning stage.  For the time beeing drafts have been made for 35 remedial actions.The drafts
are evaluated by the EPA.

App. 40 waste site had been totally cleaned up, and no further actions will be needed.

3. Reactions  from society                                                  '
By the 1st of September  1990 a change in regulations stated, that a polluted site must be
registrered  in the Land  Registry, so that potential  buyers, financial  institutes etc.; are able to
get information  of a pollution, if any.  This caused a strong reaction in the real estate  market,
and owners of polluted sites was faced with the fact, that their houses suddenly became of no
value.  By that, the public interest  on the waste site area have changed from an environmental
focus to a  question of private economy. This  is especially the case of owners of orphaned
sites.

The authorities are thereby met with a growing demand  for an even stronger effort, especially
for a larger number of remedial actions.                                     i
4. Remedial action technologies
Up to now remedial action technologies at sites are pump and treat solutions and removal of
contaminated soil. In-situ technologies are very rarely chosen, primaraly because of the very
varied soil conditions in Denmark, and secondly because  of the poor documentation of the
methods. The latter must been seen in connection with  the psycological aspects, which govern
the "no  value"-discussions.

5. Guidelines
Several  guidelines within the field of site investigations and risk assessment are made or are
in preparation. First of all a guideline on how to make an order of priority among drafts for'1
                                            20

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remedial actions on a National basis have been discussed. In Denmark, where app. 99 % of
the drinking water comes from groundwater, the groundwater protection aspects are of very
high priority. This explains the high number of "pump and treat" remedial actions. Another
aspect of great concern is of course the risks of health concerning living  on polluted soil.

The "how clean is clean" discussion in Denmark is now followed up by guidelines on soil
quality criteria, and guidelines on the demands of the quality of microbiogical treated soil,
when the soil is reused.

6. Looking at the Future.
The Danish Government has  stated, that there must be found a solution to the  "no-value"
problems. The  innocent owners of polluted sites must in one way or the other  be compen-
sated. It can be foreseen, that the compensation  will be in the form of cleanup activities and
the regulations and nessary additional funding will be laid down  around 1992/1993.

Investigation planning, sampling and analysis have been implemented. Uniform risk assessment
methods are in function  and in general it  can be said, that the work done by the counties and
their consultants are of very high quality.

There is, though, a lack  of knowledge in  understanding the behavior of chemicals in soil and
groundwater. The on-going research, national and  international, must be seen as a major input
to the risk assessment.
       1                        '     -.-.-•;        ,          ,    '"..  .'''.'
Looking in "the light of the rear-view mirror" it can be underlined,  that concerning remedial
action technologies, there is a strong need for cost effective and  documented technologies.
In Denmark the needs are primaraly focused on soil treatment technologies, on and off site.

International cooperation and discussion is highly  needed, and the participation in the
NATO/CCMS Pilot Study has broadened the view of the possibilities and limitations. The
Danish  EPA will recommend a continuation  of the Study for the benefit of the environment in
                                           21

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the participating countries.

The Danish EPA would like to express its gratitude to all the participating scientist in this
study, and wishes especially to thank the Pilot  Study Director Mr. Donald E. Sanning  and
Mr.  Robert F. Olfenbuttel for the very fine work done on the final report of this Pilot Study.
                                            22

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France's Tour de f ablfe Presentation
 23

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            NATO - CCMS INTERNATIONAL CONFERENCE
                WASHINGTON DC  (NOV  18 -  22,  1991)
              TOUR DE TABLE - FRENCH PRESENTATION
   Considering the question of contaminated sites in France at the present time, we can mention
two main aspects : legal and administrative on one side, technical and industrial on the other side.


ป. -LEGAL AND ADMINISTRATIVE  ASPECT

   I. 1. - On January 9, 1989, the Ministry of Environnement issued  of a directive for the local
Authorities facing  situations of impossibility  to  find  responsible parties able to pay  for
investigations and/or rehabilitation of contaminated sites.

   The main steps of the resulting procedure are as follows :

     1. The local Authorities must carry out all the  existing legal possibilities to find the polluter
      and make him realize and pay the rehabilitation project.

     2. In the  case  of impossibility  to find a reliable responsible  party  the local Authorities
     inform the central level and ask its agreement  for the following step which is a follows : the
     prefect  of the Department, acting as representative of the government, will'designate  the
     National Agency for Waste  Recovery and Disposal (ANRED) to carry out the rehabilitation of
     the considered site.

     3.  In this situation, Anred will  carry out the  rehabilitation project financed by  the
     government and after completion will engage  lawsuits to find the responsible party of the
     contamination and try to get the repaying of the expenses.

   At the present time 15 cases have occured and the total amount of public money spent is about
22 millions francs However is  has to be mentioned that:

   _ These cases are very different  in importance  : from some drums of PCB waste or some
hundred of kilograms of laboraty waste abandonned in the country to industrial derelict sites or
dumps invoilng some millions francs for rehabilitation. Among the 15 considered sites,  two cases
are requiring additional works to  treat contaminated soil and water.                          :

   - Up to now, the budget given to ANRED is about 10 millions francs/year wich is  not enough to
take In charge important cases with much higher costs for rehabilitation (the main example is a
very severely contamined site  located south of  Paris  Region, the cost  of  a first step of
                                          24

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rehabilitation being 20 millions, and much more  for completion). A project of a tax  on landfilling
of waste has been proposed by the Minister of Environnement in the Frame of a Plan National pour
I'Environnement (P. N. E.), the  product of such tax should be partly  reserved to finance such
cases. Howewer, up to now this project has bean posponed because of the opposition of the mn'ister
of Finances.

   On the  other hand, in application of the  directive, ANRED has carried out lawsuits against
potentially responsible parties in  every case of intervention.  Up to now,  five judgments  have been
issued by the courts (in the first stage of the procedure), ail of them are favorable for ANRED.

   1.  2. - The ministry of Environnement is preparing :

   - a project  of  regulation  obliging vendors of industrial sites for redevelopment to carry out
assement studies of the state of contamination  of the land before selling.

   -  a project  of  directive   to  the  local  authorities, giving  technical guidelines  to deal with
problems of contamined land :

      - nature and characteritics of the investigations to be carried out to  assess the state of
contamination of industrial sites or waste disposal sites.

      - nature and features of the techniques to be utilized for the rehabilitation of contamined
sites.

   ANRED is deeply  involved in these projects which  would take in  account the  national and
international experiences in connection with new research and development actions in two main
directions :

   -  soil quality, assessment of contamination levels/decontamination goals, decision making
procedures                                 .......           .........

   - developpment of new treatment processes (or improvment of existing).

   1.  3.  -  In connection with  these efforts  to  improve the  mastery  of contamined sites, the
particular case of  ancient gaswork sites has to  be mentioned because the main  industrial party
concerned, Gaz de France, (National Gas Board) owner of most of the sites (about 600) where town
gas plants were located has decided to develop an important action to face its responsabilities both
on technical and economical point of view.

   II-TECHNICAL AND INDUSTRIAL ASPECT

   The main fact to be mentioned is the creation or the development of technical capacities to deal
with the problems of investigations and rehabilitation of contamined sites.

   -  For sites  caracterisation and evaluation this occurs generaly by  the  way of developing
specific departments  in  consulting firms dealing with geologlcal/hydrogeological  expertises. On
national level at least 6 to 7 of such firms  take  part  and for some of them with international
pastnership (Germany, U.S.A, Canada)

   -  For rehabilisation of sites the increase is  even  more  important since  the begining  of this
year. At the present  time it  can be estimate that at least 14 firms intend to be present on a
significant  basis at the national  level. Some  of them  are trying to develop their own capability  (
biore'rnediation  and in situ soil venting are the more frequently proposed techniques ) and more
have  engaged international partnership in-order to  import and adapt existing proven  technologies.
Among the 14 mentioned entreprises 8 are developing  such  cooperation (3 American, 3 German, 1
Dutch, 1 Canadian).
                                             25

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   Most  of  these trench firms  entering the  market are subsidiaries of important companies
specialized mainly in water and waste managment or in public works (construction, road building,
dams...)

   Ill - CONCLUSION

   As a conclusion, it can be mentionned that there is a new significant progress in France to deal
with the  problem  of contaminated sites. Not only because the Authorities  are  improving their
capability to master these problems (limitation of action remains because of too  limited financial
resources)  but  mostly  because  of the fast growing technical capability  for expertise and
rehabilitation.  Consequently, it can be estimated that the previously existing limitation resulting
of the lack of  rehabilitation techniques has deseapeared. In addition an other  reason of technical
progress with  result of the  application of new regulation  on landfilling (now in preparation) that
will imply very strong limitation of occeptance of untreated waste and contaminated soils.
                                             26

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Germany's Tour de Table Presentation
  27

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                      NATO/CCMS Pilot Study
        Demonstration of Remedial Action Technologies for
                Contaminated Land and Groundwater

                  Fifth  International  Conference
                         Washington, D.C.
                      18-22 November 1991
                                                       ;
Recent  Developments in  National Programs:  Federal Republic  of
Germany

1. introduction

As a  result of  the unification  of  the two  German states  on 3
October 1990, the Federal Government's responsibility for environ-
mental  protection  now   also  extends  to  the five new  federal
states. The  expressed aim  is  to cancel  out the  differences  in
environmental  conditions  between  the  two  parts  of  Germany,
brought on by 40  years  of  a planned economy,  within the next ten
years.  In  accordance with  Article 34-of the  Unification Treaty,
ecological remediation and development programmes are to be drawn
up, with priority to be given to measures aimed at the prevention
of hazards to the health of the population.

The "Eckwerte der okologischen  Sanierung und Entwicklung" (basic
data  on ecological  remediation and  development), submitted  in
November 1990 by the Federal Minister for the Environment, Nature
Conservation and  Nuclear Safety,  form the  overall conceptional
framework for a set  of  measures in the new federal states,  which
are  described  in the  following  as   they relate tq  abandoned
contaminated sites.                                    :
                               28

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2.  Identification of abandoned contaminated sites      ,

Deficits in the enforcement of environmentally acceptable manage-
ment  of  household,  commercial  and industrial  waste as  well as
negligence in handling substances posing a hazard to the environ-
ment have led to a large  number of soil and groundwater contami-
nations due to abandoned waste disposal and industrial sites. The
problem is aggravated  by  the fact, that a  large number of former
lignite  opencast  mines  and  other pits  hardly  suitable geolo-
gically  for  the  depositing  of wastes  were  used  as  landfills
without any containment measures.  Furthermore,  the improper and,
in  some  cases,  negligent handling  of toxic  substances  at the
sites of numerous industrial plants and commercial businesses has
resulted in dramatic hazards to human beings and the environment.

In  the preliminary  survey  of  potential  contaminated sites,  a
total  of  27,877  sites were  identified by  November ,199O.  This
figure comprises  approx.  11,000 abandoned waste disposal sites,
approx.  15,000  former  industrial  sites,  approx.  700  abandoned
munitions and  explosives  production  sites,  as well  as  approx.
1,000 widespread  contaminations.  This is estimated  to. cover not
more than 60%  of all potential: contaminated sites.  Of the total
number of  potential contaminated  sites identified,  2,457 sites
were  classified as  being contaminated,  the cleanup  ;of  196 of
which is accorded high priority.,

As of:1 October  1991,  the number of  potential  contaminated sites
identified in the  new  federal states  rose, to 47,023. When adding
the sites identified as potentially  contaminated in the original
federal states,  the status  of  identification  stands  at  approx.
105,000 potential  contaminated  sites.  When taking the results of
a very detailed pilot  survey conducted in  Baden-Wiirttemberg as a
basis  (one  potential  contaminated  site  per   300  inhabitants),
projections of-more than 200,000 potential contaminated sites are
arrived at for the Federal Republic of Germany.

                                29

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To  supplement  the  afore-mentioned  "basic  data  on  ^ecological
remediation  and  development",  investigations  over large  areas
have  been   performed   for  high-pollution  areas.  These  areas
comprise:

- Leipzig, Bitterfeld, Halle, Merseburg (chemical industry)
- Mansfelder Land  (copper/ore mining and smelting)
- Lower Lusatia (mining and energy generation)
- Dresden and upper Elbe valley
- Wismut  (uranium ore mining)                           :
- coastal region of Mecklenburg (shipbuilding industry).

Parallel  to  these regional investigations,  studies  for  environ-
mental media related remediation are being performed. Altogether,
the financing needed is gigantic.  The cleanup of lignite opencast
mines  alone  is  estimated at  DM  30  billion.  The cleanup  of
contaminations caused by uranium ore mining is assumed to cost up
to DM  15 billion. The  measures taken  in  1990  in more than 600
projects  were  supported with funds  amounting to  roughly DM 500
million. An additional DM  100 million were appropriated for pilot
and demonstration projects.

3. Ecological rehabilitation                      , ,, :   -

Based on  the work hitherto  performed,  the  Federal  Minister for
the Environment submitted, in February 1991, the action programme
"ecological rehabilitation", which underlined the urgent need for
action in the  fields of water supply,  waste water disposal, air
pollution control,  contaminated sites,  and  waste  management.  In
addition  to   setting   up  an  infrastructure  for  remediation,
environmental-policy  measures  are  to  be  taken   immediately  to
create  jobs  over  the  short  term.  In  continuation  of the  1990
immediate action  programme,  another  immediate action  programme
totalling DM 800  million  has been  initiated for  the  years  1991
and  1992.   The   funds   are   awarded  to   priority  projects  in
coordination with the  federal  states.  The aim is  to create  a
                                30

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total of 280,000 positions  (job  creation  measures)  by the end of
1991,  of which some  100,0,00  are  earmarked  for  environmental
cleanup.         .       ,

The measures planned  to  be taken within  the  framework of ecolo-
gical rehabilitation include the following:

- establishment of soil treatment centres;
- preliminary investigations and remedial actions in the uranium
  ore mining region?
- establishment of companies to perform remedial actions;
- identification,   evaluation    and   remediation   of  abandoned
  munitions and explosives production sites;
- establishment of a world  exhibition of  remedial action techno-
  logies .

To finance  the  future cleanup of  .contaminated sites  in  the new
federal states,  a  draft  act providing for  a charge to,be levied
on waste is currently being prepared at the Federal Ministry for
the  Environment.  The. planning  so  far envisages  a charge  to be
levied on all types of waste.  The revenue is estimated at DM 5 to
6 billion per year, an annual DM 2 billion of which is to be used
for  the cleanup  of  abandoned  contaminated  sites  in  the  new
federal states.
                                31

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                 Schieswig-
                  Hoistein
                   5.359
                                Mecklenburg-
                                Vorpommern
                                8.500
Hamburg
    1.914
                Brandenburg
                8.000
             Bremen
             4.100
                    Nieder-
                    sachsen
                    7.100
                       Berlin
                       4.300
        Sachsen
          Anhalt
       Nordrhein-
       Westfalen
       15.000
                                     Sachsen
                                     10.261
              Hessen  ( Thunngen
              3.180   I  6.575
\ Rheinland-
  Pfalz
  14.130
             Baden-
           Wurttemberg
          40.000
        (Hochrechnung)
         Bayern
         3.800
Figure  1:  105,000  identified  potential

contaminated  sites   in  Germany  (as: of

1  October  1991      ''                 !

(projections:  more  than  180,000)  ,

                    • 32

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                                     Total  number   Potential
                                     of  sites        contaminated
                                                    sites
co
Westgroup of the Soviet  Army
in East-Germany
Federal Armed Forces  (Terri-
torial Command East-Germany;
former National People's Army)
Federal Armed Forces  and NATO-
real estate
U.S. Army in Germany
                                       1,026
                                       3,300
                                       3,500
                                         847
approx.700
    500

    364
 (confirmed)
   Former Armament Production
                                    2,800

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Jahr
1985
1966
1988
1988
1989
1989
1989
1989
1990
1990
1991
1991
1991
1991
Quelle
Franzius (UBA)
SPD
Brandt (Uni HH)
Deutscher Stadte- und Gemeindebund
Kaiser Unternehmensberatung
Ifo
SRU
TUV-Rheinland
DIW
Reidenbach (DIFU)
Ifo (neue Lander)
THA
Wicke (SenStadtUm)
WMK
Mrd. DM
17,2
50
22-41
70
29,1
17
20
100
54,6
52,7
10,4
53
50-200
52-390
Table of estimated costs for  clean-up
of contaminated sites in Germany
(Billions of DM)                   , • •';}
                  34

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Standort
Hamburg-Veddel
Hamburg-Billbrook
Hamburg-Elmsbuttel
Hamburg-Peute
Itzehoe
Ganderkesee
Bremen
Ahnsen
Hildesheim
Northeim-Gottingen
Berlin-Grunau
Berlin-Tiergarten
GroBkreuz
Munster
Hattingen
Bochum
Duisburg
Dresden
Grobern (bei MeiBen)
Schwarze Pumpe
Neunkirchen
Frankfurt
Stand
geplant

X






X



X
X
X
X
X
X
X
X
X
X
realisiert
Oder im Bau
X

X
X
X
X
X
X

X
X
X










Verfahrensstrange
thermisch








X


X




X


X
X
X
chemisch-
physikalisch
X
X
X
X
X



X



X

	 x


X
X
X
X
X
biologisch

X



X
X
X
X
X
X

X
X

X

X
X
X
X
X
Planned or operational  centers for treat-
ment of contaminated soils (as of 1 October
1991)                35

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The Netherlands' Tour de Table Presentation
        37

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TEN YEARS OF SOIL CLEANUP IN THE NETHERLANDS

E.R. Socz6, T.A. Meeder, C.W. Versluijs

National Institute of Public Health and Environmental Protection (RIVM), Laboratory for Waste Materials and
Emissions, P.O. Box 1, 3720 BA Bitthoven, The Netherlands, tel. (31) 30 742775


1. INTRODUCTION

In the early 1980s the Netherlands, like many other countries, was faced with the problem of
contaminated soil. In 1981 the estimated number of sites under suspicion was 4,000. How-
ever, since then it has become clear that this number will be exceeded many times (Table 1).

Table 1. The estimated number of suspected and contaminated sites and cleanup costs, 1980-90
Year
1980
1983
1986
1990
Suspected sites
(estimated)
4,000
4,300
8,000
600,000
Contaminated sites
(estimated)
350
1,000
1,600
110,000
Estimated costs
(Billions of Dutch
guilders)
1
2
3
50
Cleaned up sites
3
25
250
> 1,000
       To date, about 4,000 contaminated sites have been investigated and about 1,000 sites
have been cleaned up under the jurisdiction of the Interim Soil Cleanup Act (IBS). The total
expenditure  for the investigation and the cleanup,  financed  by the government, is
approximately 1.5 billion Dutch guilders (about 750 million US dollars). The  supplementary
cleanup circuit spent approximately 0.5 billion Dutch guilders on site cleanup.
2. CLEANUP POLICY

In 1983 the IBS came into force. According to this act the cleanup operation aimed at tackling
the sites that were posing a "serious threat to public health or the environment" [1]. The
examining framework for assessing this threat and for cleaning up contaminated sites is given
in the Soil Cleanup Guideline [2]. In the coming years the government will continue to pursue
the principle of restoring the multifunctionality of  contaminated sites. Multifunctionality is
interpreted as  all concentrations  at or below the  A-values*. In the  case  of  special
(environmental, technical or financial) circumstances, which make such remediation practically
impossible, the principle is relaxed. These circumstances have to be location-specific. In such
a case the hazardous effects have to be controlled by isolation of the site under a well-defined
criteria regimen (IBC: isolation, control and check).
       The IBS will be incorporated in the new Soil Protection Act (WBB), which forms the
framework for several additional regulations. The WBB focuses more on pollution prevention.
Several regulations are  in preparation or already operative within this framework,  i.e. the
regulations on building materials (see elsewhere in  this report), waste disposal, treatment of
manure and storage  tanks. Target groups are encouraged to  pursue good manufacturing
practices that include environmental concern in their polices.
    Values are explained at the end of this report.
                                         38

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       By incorporating the IBS into the WBB, the government will create a legal basis by
which polluters and users will be forced to clean up polluted areas. The way of financing
remediation will be different from the preceding years. The government will try to recover the
remediation costs from the polluters or soil users. Only when this is not possible and in cases
of "urgent and serious threats" will the government finance the remediation. Consequently, in
order to tackle overall soil contamination, the supplementary cleanup circuit will be obliged to
take a greater part  [1]. The first step in  this process has been made  by setting up a
Committee for Soil Remediation at Industrial Estates (BSB). The members of this committee,
consisting of governmental and industrial representatives, have agreed to a voluntary cleanup
of industrial estates and to the investigation within five years of 30,000 potentially polluted
industrial estates.
       it is expected that the government, in cooperation with trade and industry, will clean
up the most urgent sites within 10 years. The total costs are  estimated at 5 billion Dutch
guilders. For the other polluted sites the goal is set at cleaning these within one generation
(20-25 years) [3]; this means an average expenditure of approximately 2 billion Dutch guilders
per year.
       Reuse of  soil that has no multifunctional application after treatment is regulated,
together with the use of other bulk waste materials, in the Regulation on Building Materials.
This regulation takes concentrations, as well  as  leaching characteristics, into account and
defines several categories to which restriction regimens are linked.
       Recently, the RIVM made  a proposition for new C-values*. These new C-values will
be defined on a  risk-assessment-based  approach, including human and ecotoxicological
criteria. In this revision values for  the organic and  clay fractions of the soil will be taken into
account.
3. SOIL CLEANUP OPERATION

In the period  1980-1990  about 5.5 million  tons  of soil  were cleaned  up through Dutch
government funding. There is no known exact information on the supplementary cleanup
circuit. Expenditure was estimated at 100-150 million Dutch guilders per year in 1988. The
types of soil remediation techniques used for cleanup in the period 1980-1990 are indicated
in Figure 1.
                   Export    Others
           Isolation  8%       2%

           13%                            ~~	' - =~~ - ^    sฐป Ashing
                                     Cleaning       ฃ

                                        41%  TU   ,\
                                             Thermal • *•.

                                        	75%

          Disposal

           34%
Figure 1.  Types of soil remediation methods used for cleanup in the period 1980-1990.
                                          39

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       For the coming four years an increase in the speed of soil remediation is expected to
 range from 2 million tons per year in 1991 to 3 million tons per year in 1994. The remediation
 method can be expected to change dramatically after 1993 because disposing cleanable soil
 will be prohibited. To meet the  raised supply of excavated soil, the number Of temporary
 disposal sites and the capacity of soil cleaning plants will have to be increased.
       The Service Center for Soil Treatment (SCG), including local, provincial and national
 governments was founded in 1989. The main task of the SCG is the management and control
 of the treatment of excavated contaminated soil. Soil that has been excavated at IBS sites has
 to be reported to the SCG, were the decision is made to either clean or dispose of the soil.
 The SCG also monitors the quality of the  cleaned soil. A  generally accepted strategy for
 testing  the  level  of residual  concentrations  of  contaminants in  the cleaned soil  is  of
 importance, both  for the authorities as a  justification of the  remedial action and for the
 contractors as proof of the quality of their product. A standardized testing procedure has
 recently been developed by the RIVM, with controls both for the consumer's risk (unjustified
 approval on the basis  of the samples of a batch with concentrations above the  reference
 values) and the producer's  risk (an unjustified rejection of a batch with concentrations below
 the reference  values) [4].
4. SOIL TREATMENT TECHNIQUES

For about 10 years soil treatment techniques in the Netherlands have been in development
and optimized on a continuous basis. At present, essentially three kinds of treatment methods
are available: thermal, soil washing (including flotation) and biological (including landfarming
and bioreactors). Variations of these treatment methods can be applied both after (ex-situ) and
without (in-situ) excavation of the soil, after some modifications.
       Thermal and soil washing plants have been operational for several years. Biological
methods, except landfarming, are still in the development stage. Most of the in-situ techniques
are in full-scale operation, however,  they  have to be improved and  optimized to assure
meeting the reference values for soil and groundwater quality. The available capacity of the
operational ex-situ treatment techniques is  about 600,000 tons per year. The application  of
these techniques is indicated in Table 2.

Table 2. Application and capacity of operational ex-situ soil treatment techniques in the Netherlands
Ex-situ
technique
Thermal
Soil washing
Landfarming
Bioreactors
Costs
(Dfl./ton)
80-200
50-200
50-80
-
Capacity
(tons/year)
320,000
220,000
60,000
-
Type of soil1
Sandy Clay/
soils loam
+ +
+
+
(+) (+)
Type of contaminant
Oil PAHs CN CHCs Heavy
metals
+ + + (+)2
+ + + (+) +
+ w3 - - - .
(+) (+)
(+) Limited practical experience.
1) Treatment techniques are not available for peat soils.
2) See remarks on thermal treatment.
3) Lower PAHs only.
       On the basis of a decade of experience in soil treatment, the following conclusions can
be drawn [5]:
       Thermal treatment on a regular basis is suitable for the removal and destruction of
organic contaminants, such as oil compounds (alifatics and aromatics), PCAs and cyanides.
The  cleaning efficiency is high:  in most cases 98-99.5 per cent. A demonstration project
showed that  it is also  possible to clean soil that has been contaminated with chlorinated
hydrocarbons (CHCs).  However, the local authorities gave  no  permission to continue on a
                                          40

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regular basis because of unacceptable levels of dioxin emission. A new experiment has been
performed to show if dioxin emissions can be kept at acceptable levels. The results still have
to be analyzed. The costs  of thermal treatment will vary between Dfl. 80 and Dfl. 200 per ton
of soil,  depending mainly on  both  the moisture content of the soil  and the types of
contaminants.
       Soil washing techniques can be applied to a broader spectrum of contaminants but,
generally, with a  lower efficiency.  By means of soil washing, about 95-99  per  cent of
contaminants such as oil,  cyanides and PCAs can be removed  from  the soil. The cleaning
efficiencies for heavy metals vary from  80-95 per cent. At present, soil washing is the most
suitable technique for the  removal of heavy metals. However, it provides no option for the
treatment of clay or soil with high loam or peat content because of the  large volume of waste
sludge coming from the fine particle fraction. The  amount of sludge varies from about 20 per
cent for extraction/classification processes to about eight per cent for flotation techniques. The
sludge that is produced in  a soil washing process has to be considered as hazardous waste
and  most of the time it is dumped in controlled disposal sites.  The costs of the treatment by
means of soil  washing vary between Dfl. 50 and  Dfl. 200 per  ton of soil (including dumping
costs of the waste sludge), depending mainly on the quantity of small particles in the soil and
the type of contaminants in the soil.
       Landfarming is mainly used for the treatment  of sandy  soils  contaminated  with oil
compounds. The final oil concentrations are in most cases between 400 and 1000 mg/kg dry
matter, which  is still above the reference value for good soil quality, but probably is a useful
level in view  of the Regulation on Building  Materials. The treatment costs by  means of
landfarming are in the range of Dfl. 50 and Dfl. 80 per ton of soil.
       For bioreactors,  there is no  experience  beyond  the  pilot  project level.  It  can  be
concluded from the available results that in bioreactors, a considerably higher biodegradation
rate  might be achieved when  compared to conventional landfarming. After  an average
treatment time of  1-3 weeks  the final concentration of,  for example, oil remains the same as
for landfarming.
       In the last five years  several kinds of in-situ techniques have been developed in the
Netherlands. These techniques are applicable, especially for remediation of industrial estates,
where  the  costs  of excavation  are high  and immediate  removal  is  not necessary. A  few
limitations prevent a large-scale application of in-situ techniques. A heterogeneous soil leads
to high spatial variations in the soil cleanup. As a result high local residual concentrations of
the pollutant may remain. The heterogeneity of the soil and the heterogeneous distribution of
the contaminants  result in difficulties with the monitoring of the remediation process, prediction
of time needed for the cleanup, as well as the assessment of the final situation. Therefore,
practical experience is limited mainly to the well-known "pump  and treat" techniques. The
application of other in-situ  treatment techniques is indicated in Table 3.
        Table 3. Application of in-situ treatment techniques
In-situ
technique
Biorestauration
Extraction1
Steam stripping
Electroreclamation
Type of soil
Sandy Clay/
soils loam
*
Type of contaminant
Oil VOCs Heavy
metals
: ? :
           Limited practical experience.
1) Liquid and gas extraction.
                                          41

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5. RESEARCH DEVELOPMENTS
                                                                       i
To stimulate the development and innovation of adequate methods for investigation and
cleanup the Dutch government supports several research and development programs. Among
these are the Regulation for the Advancement of Environmental Technology, the Netherlands
Integrated  Soil Research Program and the Innovation-Oriented  Research Program (IOP)
Biotechnology [6]. As a result of this policy and the effort of research workers at institutes and
companies, a number of thermal, physicochemical and biological methods are operational at
present. Detailed information about these soil treatment techniques has been collected in the
Handbook  for Remedial Action Techniques [7].

       In a recent ranking of research topics connected with remedial action techniques it was
agreed that the following would have priority:

  - The characterization of soil and contaminants.
  - The reduction in the volume and treatment of waste sludge from  soil washing
   processes.
  - The additional treatment of heavy metals in the case of thermal treatment.
  - Process control and study of bio-availability for biological techniques.
  - Close monitoring of cleaning processes.
  - Optimization and development of in-situ techniques

       The policy of sediment treatment in water courses is  also expected to boost the
development of soil cleaning techniques [8]. The sediment cleanup program aims to clean up
at least 2 million m3 of sediments in 1995. The development program for treatment techniques
has a budget of 30 million Dutch guilders to carry it up to 1994.
6. CONCLUSIONS AND PROSPECTIVES

In the early 1980s, the Netherlands came face to face with the soil pollution problem. Since
the introduction of the Interim Soil Cleanup Act (1983) the government has spent about 1.5
billion Dutch guilders for the cleanup of the most urgent contaminated sites. At this time it was
believed that the cleanup program would be short term. The Dutch government focused on
developing procedures and technologies for an adequate execution of the cleanup operation.
Considering  that an increasing  number of contaminated sites have been discovered,  the
government will be paying more attention to pollution prevention in the future. To support this
strategy the  Interim Soil Cleanup Act will be incorporated into the Soil Protection Act. In  this
connection the Soil Cleanup Guideline is being revised at the moment. Renamed the Guideline
for Soil Protection it will  include the  revised  C-values,  new protocols for investigation of
contaminated sites and guidelines for the selection of the most appropriate remedial action
alternative. The Handbook for Remedial Action Technologies is also being  revised at the
moment. In this version special attention will be paid to defining the applicability of the different
technologies (based on experiences in practice). The next time considerable progress can be
expected in the cleanup operation. On the one  hand, because of  a higher budget, partly due
to the "enforced first approach", and on the other, a better organization of the cleanup process
(e.g. by the introduction of the SCG).  This will promote  the improvement of operational
technologies (  so-called "second generation") and the development of new  alternatives. Due
to the high number of contaminated (operational) industrial sites, the development of in-situ
technologies is strongly supported. R&D programs of several ministries will continue and also
support the development of environment-friendly remedial action technologies.
                                         42

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EXPLANATION:

A-value:       soil quality reference value
               (indicates the acceptable risk limit or target value).
B-values      assessment value
               (indicates the need for further investigation).
C-values:     intervention value
               (indicates the maximum potential tolerable risk limit; cleanup is required).

The A, B and C-values indicate concentration levels within the assessment framework for soil
pollutants. In the new Guideline for Soil Protection only A and C-values are maintained.
REFERENCES:

1.  Keuzenkamp KW, Meijenfeldt HG von, Roels JM: Soil protection policy in the Netherlands, the second decade,
    In Arendt Fet al. (eds.): Contaminated Soil '90. Dordrecht, Kluwer Academic Publishers,  1990, pp 3-10.

2.  Moen JET: Soil protection in the Netherlands, in Wolf K, Brink WJ van den, Colon FJ (eds): Contaminated Soil
    '88. Dordrecht, Kluwer Academic Publishers, 1988, pp 1495-1503.

3.  Alders JGM: Soil protection in the nineties; Lower House, 1989-1990 Session, 21557, nd 1, Dutch Government
    Printing Office, The Hague, 1990.

4.  Versluijs CW: Sampling strategy and testing procedure of excavated and cleaned soils, in Arendt F et al. (eds,):
    ref. 1, pp 597-805.

5.  Soczd ER, Versluijs CW: Review of soil treatment techniques in the Netherlands, in Proc of the S"1 Annual
    Hazardous Material Management Conference Int., Atlantic City,  New Jersey, June 5-7 1990, pp 368-384.

6.  Soczd ER, Visscher K: Research and development programs for biological hazardous waste treatment in the
    Netherlands, in Sayler AS et al. (ad.): Environmental Biotechnology for Waste Treatment. New York, Plenum
    Press, 1991.

7.  Handbook for Remedial Action Techniques, Dutch Government Printing Office, The Hague, 1983: Revision 1988
    (in Dutch).

8.  Luin AB van, Stortelder PBM: Treatment of contaminated sediments in the Netherlands, ref. 1, pp  1335-1345
                                                  43

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United States' Tour de Table Presentation
      45

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                  INNOVATIVE REMEDIATION TECHNOLOGIES:
               IMPLEMENTATION SUCCESSES AND CHALLENGES

                          Walter W. Kovalick, Jr., Ph.D.   •
                      Director, Technology Innovation Office
                      U.S. Environmental Protection Agency
Introduction

It Is a privilege to be part of a Canadian dialogue about state-of-the-art technologies for
contaminated hazardous waste sites. I would like to share two perspectives with you on
our experience in the United States (U.S.).  First,  I'd like to ground my presentation
graphically in the recent  data we  have compiled on the nature and use of newer
technologies in remediating Superfund sites. Second, I'd like to briefly discuss our work
to enable  consulting engineers, Federal and State  officials, and companies with
contaminated sites to be more open and accepting of these new technologies as they
design solutions in the future.

Defining Innovative Technologies

Our operating definition of innovative technologies for soils is those for which there are
Insufficient cost and  performance data to support more routine engineering design. As
shown in Figure 1, we consider incineration and stabilization/solidification as established
technologies for site remediation, while the others shown are in the innovative category.

As you see, when treatment was selected over the last decade, innovative remedies made
up about 40% of the  selections. Most of these innovative treatments are used for source
control, which  is primarily the treatment of soil.  This statistic is even more impressive
when taken in the context of the dramatic increase in source control Records of Decision
(RODs) since the  passage of the Superfund Amendments and Reauthorization Act of
1986, shown in Figure 2.  RODs are the documentation for the Agency's selection of a
remediation approach for  a site. As treatment technology use has grown as a way of
dealing with soils, so has the use of innovative treatment methods, with except for a small
drop last year (Figure 3).
                                        46

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                          FIGURE 1. REMEDIAL ACTIONS:
SUMMARY OF ALTERNATIVE TREATMENT TECHNOLOGIES THROUGH FY 90*

                                               Innovative Technologies (141) 40%

                                               Soil Washing (16) 5%
                                             S      Solvent Extraction (5) 2%
                                                       Ex Situ Bioremediation (20) 5%
                                                       -- In Situ Bioremediation t (11) 3%

                                                            In Situ Soil Flushing (11) 3%
        Established  Technologies  (2101


                 Off-site Incineration (55) 16%


               Other #(10) 3%




    On-site Incineration (59) 17%




            '• Solidification/Stabilization (86) 24.%
                                                            Vacuum Extraction (49) 13%


                                                           Dechlorination (5) 2%

                                                           Situ Vitrification (5) 2%

                                                     Chemical Treatment (1) <1 %
                                               Thermal Desorption (17) 5%
*   Data are derived from 1982 - 1990 Records of Decision (RODs) and anticipated design and construction activities as of August 1991.
( )  Number of times this technology was selected or used
#   "Othefi technologies are soil aeration, in situ flaming, and chemical neutralization.
t   Includes in situ groundwater treatment.	•	
           FIGURE 2.  REMEDIAL ACTIONS:  RODS SIGNED BY FISCAL YEAR*

                                         (Total = 751)
                           Total RODs

                       ill Source Control RODs
                          84
                                 85
88
                     86       87
                     FISCAL YEAR
*  751 RODs corresponds to 435 NPL sites.
   Source: USEPA Office of Emergency and Remedial Response.
89
90
                                                  47

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While these remedy selection trends are encouraging, a closer look at Figure 1 reveals
how few actual projects have been selected in certain categories and how "new" these
technologies are to the engineering community.  Figure 4 further illustrates ,this point
byshowing how few of these technologies have moved to the completion phase-only 8%.
This statistic gets to the heart of, the nature of the problem of introducing these new
technologies to the engineering profession. But, more on that issue later.

Trends in Technology Selection
                                                                       1   i
Even with  this  modest number of project completions, we have begun to see the kinds
and types of technologies that tend to be applied to certain characteristic sites and
wastes. To give you a sense of the nature of the problems being confronted in the U.S.
Superfund program, I am going to talk about the kind of site problems and the quantities
being dealt with at these sites.  This information results from an analysis we conducted
of the potential market for innovative treatment in the Superfund program.  The site
characterization data are for about 750 Superfund  sites for which EPA has made no
cleanup decisions in RODs.

Figure 5 shows the primary industrial sources of Superfund wastes, and Figure 6 shows
that, not surprisingly, soil and ground water are the most frequently contaminated media.
A look at the types of contaminants found in soil shows that volatile organic compounds
(VOCs) and heavy metals are by far the most frequent  (Figure  7).  Figure 8 gives an
analysis of the quantities of soil being remediated:  the vast majority (85%) of sites with
RODs have less than 50,000 cubic yards (cy) of soil to be cleaned up; 10% have greater
than 100,000 cy.

Given this context of site problems, the trends  of innovative remedies we are seeing
should  be more  meaningful.  We see in Figure 9 that we are  frequently selecting
innovative treatment for the most common contaminant, VOCs.  A  wide variety of other
methods are being used as  well.  However  for heavy metals, which are  almost as
common as VOCs, Figure 10 shows that our use of innovative technology is far less. By
contrast, polyaromatic hydrocarbons (PAHs) occur at relatively few sites, but we have
selected innovative methods  (primarily bioremediation) in almost 40 cases, as indicated
in Figure 11.

We can also observe that there are clearly favorite innovative methods for some types of
contamination: vacuum extraction for VOCs, soil washing for metals, and bioremediation
for PAHs.  But for polychlorinated biphenyls, as Figure 12 illustrates, no innovative
technology is a clear winner.

Table 1 contains data on the quantity of material being treated  by  each innovative
technology. Technologies are  listed in order of average quantity of material addressed,
but because there is a wide range of values for most technologies, the averages could
be misleading. -In general, however, batch processes, such as solvent extraction,


                                        48

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        FIGURE 3. REMEDIAL ACTIONS: NUMBER OF ESTABLISHED
            VERSUS INNOVATIVE TREATMENT TECHNOLOGIES
  Number
    of     30
 Treatment
Technologies 2 0
  Selected
                      Established Treatment
                      Technologies
                 "UJ" Innovative Treatment
                      Technologies
                                85    86   87    88   89    90
                                  FISCAL YEAR
FIGURE 4. REMEDIAL ACTIONS: PROJECT STATUS
OF INNOVATION TREATMENT TECHNOLOGIES AS OF AUGUST
— MBf ..ป-.
Vacuum Extraction
Ex Situ Bioremediation
Thermal Desorption
Soil Washing
In Situ Bioremediation t
In Situ Flushing
In Situ Vitrification
Solvent Extraction
Dechlorination
Chemical Treatment
TOTAL
36
15
14
16
8
9
5
4
3
0
no (78%)
12
4
0
0
2
2
0
1
1
0
22
1
1
3
0
1
0
0
0
1
1
(16%) 8(6%)
1991
Total
49
20
17
16
11
11
5
5
5
1
140
* Data derived from 1982 - 1990 Records of Decision ( RODs) and anticipated design and construction activities.
t Includes in situ groundwater treatment.
                                       49

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                                FIGURE 5,
     FREQUENCY OF INDUSTRIAL SOURCES AT SELECTED SUPERFUND SITES*
                     * May be more than one industrial source at each site.
                                FIGURE 6.
FREQUENCY OF CONTAMINATED WASTE/MEDIA AT SELECTED SUPERFUND SITES*
  Number
    of
    Sites
             700 —
500

400

300

200

100

  0
                      More than one contaminant may be present at each site.
                                      so

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       FIGURE 7. PRINCIPAL CONTAMINANT GROUPS PRESENT IN SOIL*
      400-
Number
  of
 Sites
300-


200-


100-


  0
            VOCs              PCBs   Pesticides   PAHs
                                                          Asbestos
                    * More than one contaminant group may be present at each site,
                              FIGURE 8.
 QUANTITIES OF SOIL TO BE REMEDIATED BY PERCENT OF SITES
                                       50,000 - 100,000 CY (5%)

                                              >100,OOOCY<10%)
    10,000 - 50,000 CY (36%)
                                              < 1,000 CY
                                              (13%)
                                        1,000-10,000 CY (36%)
                     Source: EPA's RODs Information Database
                                      51

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       FIGURE 9. INNOVATIVE TREATMENT FOR SITES CONTAMINATED WITH VOCS
         30
  Number
    of    20
Applications
         10

          0
             Vacuum   Thermal    Bio-    In Situ   Solvent    Solil     In Situ
            Extraction Desorption remediation Flushing Extraction Washing Vitrification

                                     TECHNOLOGY
 FIGURE 10. INNOVATIVE TREATMENT FOR SITES CONTAMINATED WITH HEAVY METALS
 Number
    of
Applications
                Soil
               Washing
 In Situ
Flushing
   In  Situ
 Vitrification
TECHNOLOGY
 Solvent
Extraction
Chemical
Treatment
      FIGURE 11. INNOVATIVE TREATMENT FOR SITES CONTAMINATED WITH PAHS
               Bio-        Soil       In Situ     Solvent      Vacuum    Thermal
            remediation   Washing     Flushing   Extraction   Extraction  Desorption
                                        TECHNOLOGY
                                          52

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                                   FIGURE 12.
        INNOVATIVE TREATMENT FOR SITES CONTAMINATED WITH PCBS
 Number
   of
Applications
              Dechlor-    ID Situ    Solvent    Thermal   Bioreme-    In Situ
               ination    Flushing  Extraction  Desorption   diation  Vitrification

                                     TECHNOLOGY
TABLE 1.
QUANTITIES OF SOIL TO BE TREATED BY INNOVATIVE TECHNOLOGIES
Technology
In Situ Soil Flushing
Vacuum Extraction
In Situ Bioremediation
Soil Washing
Ex Situ Bioremediation
Solvent Extraction
Dechlorination
In Situ Vitrification
Thermal Desorption
Number of
Superfund
Sites with Data
10
31
5
17
18
5
4
5
17
Quantity (Cubic
Range
1,500 - 650,000
400 -300,000
5,000 - 10,000
5,500 -200,000
5,200 - 120,000
2,000 - 67,000
800 - 50,000
4,000 - 38,000
1,600 - 85,000
Yards)
Average
90,000
47,000
47,000
40,000
33,000
29,000
20,000
14,000
13,400
                                          53

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dechlorination,  and thermal desorption, which  require waste excavation and  often
pretreatment, tend to treat smaller amounts of material.
Technology Demonstration and Evaluation

Moving beyond our implementation data related to innovative technologies, let me turn
to one other aspect of the Superfund program that is focused on technology development
and  demonstration.  The 1986  law authorized the Superfund  Innovative Technology
Evaluation (SITE) with the goal of assisting developers of technologies to scale up and
demonstrate these innovative technologies.

There are two components of the treatment technology program:

o  The Demonstration Program, entering its 7th year, focuses on technologies ready for
   field application. Vendors mobilize pilot or full-scale equipment to actual hazardous
   waste sites and pay for the cost of equipment operation.  EPA pays for;rigorous
   sampling and analysis of equipment performance.  EPA prepares evaluation reports
   which provide performance and, to the extent  possible, cost information.

o  The Emerging Technologies Program, entering its 5th year, focuses on developmental
   technologies.  EPA provides up to $150,000 per year for up to two years to assist in
   development of promising technologies.   While the emerging  program generally
   involves laboratory testing, it may include early pilot testing.  Technologies which
   participate in the emerging program may "graduate" to the demonstration program.

Another component of the SITE program which focuses on innovative approaches to field
monitoring and site characterization. Tables 2 and 3 summarize the kinds of technologies
in the SITE Demonstration and Emerging programs, and the progress to date of each of
the programs.

The  SITE program stands as a unique national commitment to provide 'developers with
the opportunity to authenticate their new technology claims for the marketplace.

Initiatives to Encourage Technology Use

I would now like to discuss some of our work with practitioners to deal with changing  the
perceptions and reality of considering innovative technologies for site remediation. Figure
13 graphically portrays the critical decision-makers for cleaning up abandoned waste
sites.

Either in the presence of or  at the direction of a Federal or State project manager,;
consulting engineers are called upon to conduct studies and make recommendations for
solutions at contaminated sites.  More and more frequently in the U.S., the client who


                                        54

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TABLE 2.
SITE DEMONSTRATION PROGRAM
Technologies
Biological
Physical/
chemical
Thennal
Solidification/
stabilization
Radionuclides
Total
Demon-
Vendors stratlons Reports
Selected Completed Available
16 3 1
32 9 10
13 6 6
11 5 8
2
~W ~2T ~25~
TAJSLE3.
SITE EMERGING TECHNOLOGIES PROGRAM
Technologies
Biological
Physical/
chemical
Thennal
Solidification/
stabilization
Materials
Handling
& Mining
Total
Tests
Vendors Planned or Reports
Selected In Progress Available
9 7
21 16
7 7
2 2
5 5
___ ___
2
5
..
..
—
"25"'
                       FIGURE 13.
            TECHNOLOGY INNOVATION OFFICE;
MAKING INNOVATIVE REMEDIATION TECHNOLOGIES HAPPEN
                   Responsible M Federal/State
                   Party/Owner m   Project
                          Consulting
                           Engineer
                              55

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retains them is the potentially responsible party (a term from our Super-fund program) or
a hazardous waste facility owner/operator required to conduct corrective action under our
hazardous waste law.  Usually outside this decision triangle are the new technology
developers who are attempting to "break into the club" of accepted technologies.

Given this scenario, my office has focused  over the  last  18 months on identifying
anddealing with what's blocking each of these players from using innovative technologies.
These  barriers  generally fall  into three  classes:   informational,  regulatory,  and
Institutional/economic.  We have met with each of these interested parties and developed
"products" to serve these customers. While this is a unique role for a regulatory agency,
ft is proving fruitful.  Below are a few of our initiatives to  deal with these barriers:

o   Innovative Hazardous Waste  Treatment Technologies:  A Developer's Guide to
    Support Services (EPA/540/2-91/012) identifies programs and services that support
    technology development and commercialization.  This includes Federal and State
    assistance probrams, facilities that can  provide services related to technology
    development and testing, and university-affiliated research centers. This information
    targets the technology developer who needs help validating or commercializing his
    technology, and in  understanding permitting and other regulatory requirements.

o   A Vendor Information System on Innovative Treatment Technologies (VISITT) is a new
    database to provide screening level information on cost  and performance from
    vendors and their clients.  This information will provide a clearinghouse of innovative
    technology information for companies, consulting engineers, and state and  federal
    project managers.

o   The Bioremediation Field Initiative is a joint effort between TIO and the Office of
    Research and Development.  The program is designed to more fully document
    performance of full-scale applications of bioremediation, provide technical assistance
    for treatability studies and field pilot studies, and enhance cross-regional information
    transfer  on bioremediation  projects.  Program progress and  a list of sites using
    bioremediation  are documented  in a  regular  newsletter  of  the   same  name
    (EPA/540/2-91/018).

o   Innovative Treatment Technologies: Semi-Annual Status Report (EPA/540/2-91 /001)
    documents the use of innovative treatment technologies at Superfund sites.  The
    twice-yearly report  contains overall statistics and site-specific information, including
    the technology selected or used, the waste to be treated,  implementation status, and
    site contacts. This information can be used by site managers to identify others with
    similar sites  and technology  interests, and by technology  vendors to evaluate to
    identify prospective customers.

o   A  Market Assessment Project is  underway to profile the  remediation  market
    retrospectively and over the next  several  years.   The  objective is to provide
                                          56

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developers and investors with information on the type and size of site problems so
that, development dollars can be  channelled more productively.  Information on
specific sites may also help vendors market their technologies to site managers.

The Federal  Remediation Technologies  Roundtable serves as an  information
exchange network for and about Federal agencies conducting applied reserach and
development on innovative remediation technologies, The Roundtable has recently
published summary reports  of  federal demonstrations  (EPA/540/8-91/009) and
federal databases (EPA/540/8-91/008),  and a  bibliography  of federal reports
(EPA/540/8-91/007) concerning innovative treatment. Future efforts will focus on
joint or collaborative demonstration projects.

Identification and removal of regulatory impediments is an ongoing function of TIO.
The same regulatory framework which essentially establishes the market for remedial
technologies unfortunately hampers the development and application of innovative
technologies.  Some of the impediments that TIO is addressing were identified in a
1990 EPA study of the strengths  and weaknesses of the hazardous waste regulatory
program.  These  include the cost and timing to get a research permit, unfamiliarity
of permit writers with new technology, site-specific permitting for transportable units,
and stringent cleanup levels under the  Land Disposal Restrictions.

Information dissemination is one of  TIO's major initiatives.    TIO compiles  a
bibliography  of  all  significant  EPA   publications  on  innovative technologies
(EPA/540/8-91/006) and  a  periodic bulletin, Tech Trends,  (EPA/54Q/M-91/004)
which communicates experiences  encountered in  applying innovative technologies
In the field.

TIO has  sponsored three Forums on Innovative Hazardous   Waste  Treatment
Technologies:  Domestic and International.  International and domestic vendors of
innovative technologies present papers and posters with an emphasis on actual field
applications.   Abstracts are available (EPA/540/2-91/016) for the most recent of
these conferences, which was held in Dallas in June 1991.  Documentation is also
available for the first forum in 1989  (EPA/540/2-89/055) and the second in  1990
(EPA/2-90/010).

Because one of the largest markets for remediation technologies  may be the states,
TIO has  an initiative to  encourage states  to promote innovation.  State regulatory
requirements and remediation programs will have a major  impact on the pace and
extent of  innovation.  For various reasons, states have been slow to adopt  EPA-
promulgated  innovation support  and  relief mechanisms  such  as  research and
development permits and the 1000 kg  treatability exclusion.  TIO is working with a
number  of interested  states to explore  opportunities  to establish a regulatory
environment which not only tolerates, but actively encourages innovation.
                                      57

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In addition to these projects, TIO is exploring avenues to more fully engage the nation's
consulting engineers, responsible parties,  and professional societies In collaborative
Information sharing, education, and remediation technology demonstration,   ,
                                         58

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en
to
           Increasing the
       Development and Use
of Innovative Treatment Technologies
          for Site Cleanup
                                  Technology Innovation Office

-------
  What are
  Innovative Technologies?
  Methods for which performance or cost
  information is inadequate.
CTs
For source control:
     Thermal desorption
     Chemical treatment
     Solvent extraction
     In situ vitrification
                            *
Vacuum extraction
In situ flushing
Soil washing
Bioremediation
                                                ^Technology innovatioirOffice

-------

-------
Interpret and Supply  Information

                               ON-GOING PROIECTS

                               <ป Bibliographies/Newsletter (Tech Trends)
                               <ป Innovative Technologies Overview/Status Report
                               <* Bioremediation Bulletin on OSWER/ORD field
                                 initiative
                               <* Forum on Innovative Hazardous Waste Treatment
                                 Technologies:  Domestic and International (3rd
                                 annual in June 1991)
                               * Joint work with ORD under NATO/CCMS and
                                 German Bilateral to obtain technology information
                               *> Clean-Up Information (CLU-IN) Electronic
                                 Bulletin Board for exchange of information on
                                 hazardous waste site remediation (Now open to
                                 the public)
                                                         -Technology-Innovation Qtfiee^

-------
   Interpret':'"and  Supply Information
W
          Technology Vendor
Responsible
  Party/
  Owner
 Operator
Federal/
 State
Project
Manager
             Consulting
              Engineer
NEW PRODUCTS


• AWMA and HWAC Satellite Seminar

  (1992)

..*> Federal Remediation Roundtable Publications

  (Summer 1991)

* Market Monograph (Fall 1991)

* Vendor Information System for Innovative

  Treatment Technologies (VISITT) (Early 1992)

* TIG "booth" and presentations at 8-12 technical

  professional meetings per year

* Lessons Learned during Technology

  Implementation

* Public Information Fact Sheets (Fall 1991)
                                                              Technology Innovation Office

-------
   Increase the Demand for Trying
   the  Innovative Approach
           Technology Vendor
91
         esponsible
          Party/
          Owner
         Operator
Federal/
 State
Project
Manager
              Consulting
               Engineer
* OSWER policy directive (June 1991) with:
  * clear statement of intention
  • integrated SARA/RCRA/UST coverage
  • specific incentives to take risks
  ซ continued support systems

<* Target training at Superfund Academy

* Impact RCRA corrective action and
  enforcement guidance and regulations

* "Cross marker with ORD (for SITE),
   OE (for Federal Facility Demos),
   OSW (for RCRA permits/variances), and
   OWPE (for RCRA orders)
                                                          ~Techffology tnnoyaTton Office

-------
    Enable
    Coiraborafive  Projects
                                                       Technology Vendor
ov
* Use Federal Remediation Round-
  table to collaborate on demonstra-
  tions


*> Create new industry/government
  technology forum


* Market Federal Technology Transfer
  Act to industry
                                                                  Federal/
                                                                   State
                                                                  Project
                                                                  Manager
esponsibie
 Party/
 Owner
Operator
                                                          Consulting
                                                           Engineer
                                                                      continued...
                                                              Technology Innovation Office

-------
Enable
Collaborative Projects
*>
C+ Support National Standards of
  Practice on Innovative Technologies
  Assist regular nationwide tele-
  conferences for consulting engineers


  Follow-up on other work group
  recommendations with Hazardous
  Waste Action Coalition (ACEC)
                                               Technology Vendor
Responsible
   Party/
  Owner
 Operator
Federal/
 State
Project
Manager
                                                        TechnologyJnnamtioajOffice

-------
    " "                    -       \
What is Near-Term Agenda?
   Continue to supply updated information to targeted audiences

   implement OSWER directive affecting Superfund and RCRA

   Begin National Technology Standards of Practice? on
   technologies with 2-6 professional societies

   Create mechanism to collaborate with industry on their
   technology development agenda
   Support/ariiTioiince 1 -2 states as ^Technology Meccas''
                                                    continued...
                                                 Technology Innovation Office

-------
   What is Near-Term Agenda?
00
       Fully embrace groundwater as well as source control technologies

       Issue VISITT Vendor Information System
Continue and expand work on Federal
Technologies Roundtable
     Aggressively market CLU-IN Bulletin Board

   *  Issue first Market Monograph
                                                    Technology Innovation Office

-------
     Hazardous Waste Site 6Iean-up Market
VO
o  1,200 - 2,000 Superfund sites
o  4,700 RCRA facilities with 60,000 units may need
   corrective action
o  28,000 State norviupeffund sites
o  660,000  sitงs  with  1,8  million  underground
   storage tanks (90% of tanks contain petroleum)
o  638 DOD instillations with 7,400 sitts
o  76 DOE fa&ilitiei with up to 1fBQO eoniaminated
   areas ptf faงlllty

-------
Barriers To implementing innovative
                                 training
                                   and
                                Pr8fliงi8H8i
                                                   i UUซ ป< ij^ป < >ซปl.
                                                   otivational
                informatiSR

-------
Austria's Tour de Table Presentation
 71

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            <ฑ>NTAMCNATED SITES - THE SITUATION IN AUSTRIA

                                  Harali KASAMAS

                                    (OKO-FONDS)
 I.  INTRODUCTION

    like the case of "Love Canal" in the US, Austria has also a popular contaminated site (named
    "Fischer Deponie"), which made the problem clear to the public.

    It is a MSW-landfill site with approximately 4000 barrells of chemicals on its base. This site is
    one of the main contamination sources of Austria's largest aquifer. Approx. 500 000 people
    rely on this aquifer for drinking water purpose.

    In 1987 the site was closed after conducting a groundwater-quality programm. As the depate
    about the next steps went on it became clear, that the legal situation was insufficient to deal
    with the problem and that the needed funds are not existent.

    This acute case led to a prompt realization of a federal law, the "Altlastensanierungsgesetz".
EL  "ALTLASTI^SANIERUNGSGESETZ 1939 (ALSAG)1'
    (or "Federal Law relating to Remedial Actions on Contaminated Sites")

    The purpose of this federal law is to provide the basic structure for handling problems with
    contaminated sites in Austria, mainly to create the funds for financial support.

    Altogether ALSAG regulates the following topics:

      1.  Registration and assessment of suspected

      2.  Organization and distribution of the necessary funds (AMastenbeitrag)

      3.  Legislative authority to force necessary measures by expropriations, sufferance, and the
         related compensations

      4.  Important definitions about the topic

    ALSAG was put into force on 1.7.1989.
                                          72

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ALTLASTENBEITRAG (or "How to create the needed money?")

The required finances are created by appropriated tax on landfiUing and waste-export. This
modell is funded on the fact that all waste-disposal in the soil needs controll and monitoring
afterwards. Furthermore, the financial burden on landfilling and waste-export should give an
impulse towards waste-minimization measures and should result in saving landfill-space.

The tax is collected from landfill-operators and  waste-exporters by the  revenue-offices. An
advantage of this modell is the relatively small amount of contributories which should make
the execution easier.

The extent of the taxation depends on the type of waste which is being handled. For hazardous
waste it is approx.  $ 16.00 per metric ton, for non-hazardous waste it is approx. $ 3.20 per
metric ton.

The assessed valuation of the financial requirements for treating contaminated sites in Austria
over the next 10 years ranges up to approx. $ 800 million.

When "Altlastenbeitrag" was introduced in 1989, the expected annual revenue was approx. $ 31
million. By collecting the tax over 20 years, 60 % of the estimated financial need would have
come from these public funds. But the experience of the first year showed that only one third
of the expected amount has been generated. The  main reason why revenue has fallen short of
expectations is that  the taxes have not been sufficiently enforced. Furthermore, after enacting
the "Guidelines for Financial  Support"  it was clear that  the  public has to take a greater
overall-share than planned. Because of these reasons the tax will rise up soon.

But in spite of these  experiences there are still no financial problems  to  support the first
projects. ALSAG regulates that the Ministry of Finance is able to undertake liability up to $ 1
billion in case of financial shortage. Nevertheless,  the condition is that on the long-term all has
to be covered by "Altlastenbeitrag".

Beside the generation of finances, ALSAG also defines the concerns for which the money has
to be spent. These are as follows:

  1.  Detection and assessment of suspected sites, including additional investigations to define
      priority classes

  2.  Registration of suspected sites  and assessed  contaminated sites

  3.  Remedial measures on contaminated sites

  4.  Construction,  expansion and improvements of waste disposal sites, as far as they are
      related to clean-up measures

  5.  Studies and projects, including development of treatment technologies

To fullfill points 1 and 2,10 % of finances are transferred to the Ministry of Environment. The
other 90 % of the funds are intended for OKOFONDS to support matters  of points 3 to 5.
                                        73

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EL  "FORDERUNGSRICHTLINIEN1991" (or "Guidelines for Financial Support")

     The guidelines have been enacted since 1.7.1991.  They regulate the conditions for which
     OKOFONDS can give financial support for remedial actions on contaminated sites.

     As a general principle of these guidelines the financial support should encourage responsible
     parties to clean up contaminated sites voluntarily. Those parties who offer to participate in
     remedial measures can apply for financial support by OKOFONDS.

     Altogether the guidelines answer the following questions:

       1.  What kinds of measures can be sponsored and which can't?

       2.  Who ist able to apply for sponsoring and what conditions have to be met?

       3.  To what extent is  financial support  possible and under which  circumstances  are
          deductions applied for responsible parties ("Fund matching")

       4.  How can funding be transferred? Which conditions should be implied in the contract?
          And what happens if these conditions are not held?


     FUND MATCHING

     The guidelines distinguish between three different cases;

       1.  No responsible party is available: For sites where nobody can be forced to conduct
          remedial actions the funding can reach up to 100 % of clean-up costs. Those sites can be
          e.g. contamination caused by World War n or cases, which the responsible party isn't
          known or not existent anymore.

       2.  Responsible party is  available: In these .cases .which someone  can :be  forced by
          regulations to set measures  respectively when someone has an interest to clean-up
          voluntarily, deductions of funding are applied for some defined cases of responsibility.

          These cases are:
           - not met the "Guidelines for landfilllng from 1977' by landfill-construction (minus
             10 % deduction)

           - not possessing the required administrative appropriations (minus 10 % deduction)

           - violation  of a  law  or administrative  injunctions  which finally   caused  the
             contamination (minus 10 % up to the exclusion of funding depending on the extent of
             offense).
                                           74

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      3.  Landfill sites in operation: If the construction of the landfill was not sufficient to avoid
          damage to the environment, funding for the needed measures are possible. The extent of
          the financial support is linked to the remaining volume of landfill-space. The funding is
          adjusted in such magnitude that the future costs for landfilling MSW won't exceed $ 100
          per metric ton. For hazardous waste the limit is set to 1,5-times the cost for a modern
          constructed site. This modell should prohibit financial support for cheap landfilling.

          In general, OKOFONDS has to consider the following:

            1.  The funding has to be covered by the revenue of "Altlastenbeitrag" overall.

            2.  The individual states should get back approximately their share of "Altlasten-
               beitrag" over a period of 5 years.

            3.  The priority of a contaminated site.


IV.  PROCEDURE OF APPLICATION FOR FUNDING AND THE CURRENT SITUATION


     -  MINISTRY OF ENVIRONMENT

        The individual states search for their possibly contaminated sites. These data are reported
        to the Ministry of Environment. This Ministry is responsible for executing the regulations
        of ALSAG and the coordination of the needed steps.


     -  UMWELTBUNDESAMT (UBA)

        The reported sites are transferred from the Ministry of Environment to UBA for further
        investigations concerning the registration and assessment of possibly contaminated sites in
        the country. For  these reasons, UBA holds two registers. One for the suspected sites
        ("Verdachtsflachenkataster) and  one for  the actual contaminated  sites  after conducted
        assessment ("Altlastenatlas").
        The site-assessment modell of UBA is highly related to the modell of the German province
        Baden-Wurttemberg.  As a result of this  assessment  sites are evaluated in one  of four
        possible priority groups. Priority I, for a site expresses greatly needed measures because of
        the high risk to human health. Priority IV, expresses a cleaned or safed site.

        A completed site-assessment of UBA with evaluation  to  a priority-catagory is  a basic
        requirement for financial support by OKOFONDS.

        Current situation:

        3300 possibly contaminated sites have been reported to UBA At the moment 803 sites are
        being  assessed.  By  September  1991   52  contaminated   sites  were recorded  as
        "ALTLASTEN". 36 are evaluated in priority groups.

        Around 90  %  of reported  suspected sites are  MSW-landfills. That's  because  their
        registration is far advanced compared to industrial contaminated sites.  For the latter a
        systematic survey is planned by UBA for the near future.
                                           75

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OKOFONDS
                                                           t      -  - - ,    ••*''-:- ';<
Applications for financial support can be made to the Fonds before site assessment by
UBA is completed.  This procedure should save time, so greatly needed measures are not
slowed by bureaucracy. In very urgent cases the technicans of the Fonds are informed from
the beginning and can push ahead the assessment of the project. As soon as the application
is turned in to OKOFONDS the measures can be started.                       ,  ,

The application for  funding has to include as a main part a technical project.  It is first
transferred from the applicant to the state-government.  Their job is to check, if everything
needed ist included  and to complete the application with additional information and data
about the site. Then it is referred to OKOFONDS.

The application is examined in detail by the technicians of OKOFONDS  under technical,
ecological and economical aspects.

Current situation:

Until now 37 applications with a total of approximatley $ 216 million have been made to
6KOFONDS.  20 of these projects  refer  to measures  on MSW-landfills, the rest of 17
projects relate to industrial sites (including  contaminations caused by World War D).

ALTLASTENKOMMISSION

After a positve judgement of the project  the application is presented by OKOFONDS-
teehnieians in  a session of the  "Altlastenkomrm'ssion".  This  commission  consists of
representatives  of state-governments, concerned ministries, political parties,  the Union,
industry and commerce. They  get together about four times a  year  for discussions, and,
voting about every application for funding.  After a positive  vote the application is
recommended  by the commission to the Minister of Environment who finally decides
about the issue.                                                            ,  ,

Current situation;

The minister has accepted 16 applications  so far. Approx. $ 47 minion (around 70 %) of
the originally applied $ 68 million have been found relevant for financial support relating to
ALSAG. After deduction of the "respomibility-share" according to the guidelines, approx,
$ 36 million (around 50 % of applied) were granted by the Minister of Environment. So far
10 contracts for funding have been signed.
                                    76

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 V.  SICHERUNGS- UND SANIERUNGSTECHNOLOGltEN (or "Clean-up Technologies")

     From a technical viewpoint the 37 projects applied to OKOFONDS can be classified into the
     following technological catagories:

     13 landfill containments (walls and surface) combined with hydrological measures and degas-
       measures
     6 excavations of landfill combined with measures to sort old waste and redeposit it on a
       modern-equipped landfill
     2 only active degas-measures for landfills, which are no hazard to the groundwater
     3 soil-air-venting systems,
     2 pump-and-treat measures
     1 on-site biological treatment
     10 investigation-measures for additional information to make a project

     In general some "Austrian specific" types of technology can be identified:
       1.. Containment  with  sealing-walls for  landfills  is   usually  performed  by  "Wiener
          Kammersystem" (or "Vieimiese Chambersystem"). This method allows control  of the
          system, both after establishment and on a long-term basis.

       2.  Incineration is not possible due to political reasons at  the moment. Therefore the future
          way seems to be excavation followed by sorting. It was performed the first time last
          spring in Vienna for a  relatively old MSW-site and on a small scale. A new technology
          to overcome odour-problems  was performed  with "Bio-Puster  System".  Oxygen-
          impulses into the waste changed microbiological processes in the waste from anaerobic
          to aerobic conditions.
VI.  CONCLUSION

     The first steps have been made in Austria. With ALSAG the basis (financial, legal) has been
     provided to deal with the problem of contaminated sites. For OKOFONDS which administers
     the mainpart of created funds it is essential to support proper technology to be cost-effective
     and successful
     Therefore we are highly interested in international cooperation. And as the last examples show
     we are also initiative in Austria to bring in new ideas.

     We hope we are able to be an helpful part in an exchange of experiences.
Dipl.-Ing. Harald KASAMAS
OKOFONDS AUSTRIA
Reisnerstrafie 4
A-1030 VIENNA
AUSTRIA, EUROPE
                                          77

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 Altlastensanierungsgesetz 1989
(Federal Law relating to Remedial Actions
         on Contaminated Sites)
    Registration and assessment of
           suspected sites
  Organisation and distribution of funds
           (Altlastenbeitrag)
Legislativ authority for expropriations,
   sufferance and compensations
        Important definitions
                                   UWWF -31
                  78

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    Distribution of Altlastenbeitrag
Dedection and assessment of suspected sites

Additional investigations for priority definition

Registration of suspected sites and
assessed contaminated sites
 Remedial measures on contaminated sites

 Construction, expansion and improvements
 of waste disposal sites

 Studies and projects
                                       UWWF '91
                     79

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 Forderungsrichtlinien 1991
(Guidelines for Financial Support)
       types of measures
       possible applicants
    conditions for application

       extent for subsidy
  deductions for responsibility
      transfer of funding
       contractual terms
                                 UWWF '91
               80

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00
                           PROCEDURE OF ALSAG\
 STATE GOVERNMENT

• searching for suspected sites
• report to Ministry of Environment


 MINISTRY OF ENVIRONMENT
• coordination of ALSAG


UMWELTBUNDESAMT (UBA)

ซ registration  and assessment
ซ evaluation in priority classes
APPLICATION FOR FUNDING)


 STATE GOVERNMENT
 • first check of application
 e  additional data
	:	/

 OKO-FONDS              '
 • examination of the application
   (technical, ecological and
   economical aspects)
                          ALTLASTENKOMMISSION
                         discussion and voting
                         recommendation to the Minister
                        MINISTER OF ENVIRONMENT
                             * final decission
                                                                  UWWF '91

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Norway's Tour de Table Presentation
 83

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NATOICCMS Fifth International Conferrence
   Demonstration of Remedial Action Technologies for
         Contaminated Land and Groundwater
            Washington B.C, United States
              November 18 - 22,1991.
                  Tour de Table
                    NORWAY

                       by

                  PerAntonsen
                       84

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1.   INTRODUCTION

The Storting (Norwegian Parliament) decided in 1989 that "the
risk of serious pollution problems due to wrong management of
hazardous waste in earlier years shall be .reduced to a minimum
by the year 2000". To follow up this decision, the State
Pollution Control Authority (SFT) is preparing a Plan of Action
to clean up hazardous waste. The measures include:

 *    cleaning up hazardous waste abandoned earlier by
      enterprises no longer in operation
 *    cleaning up pollution from mines no longer in
      operation
 *    cleaning up abandoned industrial sites and
      environmentally hazardous waste previously buried
      at these sites
 *    treatment of contaminated soil
 *    cleaning up polluted sediments in fjords

2.   NATIONWIDE SURVEY.

During the period 1988-1990 a nationwide survey of landfills and
polluted ground was carried out. The objective of the survey was
to establish the extent of the problem, and provide a basis for
preparing a Plan oฃ Action.


2.1  Method

The registration is based on available information.  No soil
surveys have been carried out, nor samples taken at the
different sites.

The method involves reviewing the existing data.  The greater
part of the work has consisted of interviewing municipal
officials and other persons with knowledge of waste
management in their own municipality, and inspections and
interviews at enterprises which generate or have generated
hazardous waste.  An attempt has been made to check the
information with companies that collect and treat hazardous
waste.  Several methods have been used to inform the public
and encourage them to "tip off" the authorities.

The registered sites have been ranked into five categories:

Category 1.    Sites requiring immediate investigations or
               measures.

Category 2*.   The case is being considered by SFT.

Category 2.    Need for investigation.

Category 3.    Need for investigations in the event of a
               change in land use.

Category 4.    No investigations needed.
Since the survey did not involve soil or ground water analysis,

                              85

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the registration does not provide any basis for assessing the
actual potential for pollution at the sites concerned.  When
ranked into categories, the information on hazardous waste is
evaluated against the vulnerability of the recipients and the
conflicts that possible pollution would cause in relation to
land use, activities and animal life in the area.

2.2  R. summary of the results of the survey

Table 1 shows the number of registered sites and the
distribution between the different categories.

Table 1.  National overview of registered sites

Site:type/
category                      1    2*   2    3    4    Sum

Landfills:
Municipal landfills           12    1
Industrial landfills          20   11
Other landfills                6    6
          149  533  337  1032
          124  205  132   492
           48  181  241   482
Contaminated ground:
Industrial ground              8
Other ground                   3

Landfills and contaminated
ground:                       12
     19
      1
 55
 19
           44
191
 47
      43
0
0
273
 70
           103
Sum
61   42
439 1200   710 2452
The most serious problems are connected to landfills polluted
by heavy industry and chemical industry.  Because much of the
industry is located along the coast, many of the landfills
are placed directly at the shore edge.  Leaching of toxic
pollutants from the landfills could contaminate Norwegian
fjords for many years to come, and become relatively more
important as other discharges are reduced.

It has also been registered that a large number of municipal
landfills have received varying quantities of hazardous
waste.

The survey shows that only very few sites give grounds to
fear that the present form of land use involves a hazard to
health.  The sites are first and foremost a pollution risk to
watercourses and fjords, and conflict with nature
conservation interests and various forms of outdoor
activities.

Pollution of groundwater is not a serious threat to drinking
water in Norway at present, because groundwater is not used
to any great extent for this purpose.  However, pollution of
groundwater reservoirs could destroy potential sources of
drinking water.
                             86

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3.   THE GOALS FOR THE PLAN OF ACTION

The draft Plan of Action contains proposals for goals for the
clean-up work, in the form of the level of environmental
quality that one wishes to achieve from the clean- up.  It
has been decided to make a distinction between the different
recipients, soil, groundwater and surface water (including
fjords).

The proposals are intended as a basis for discussion, and as
a help in formulating a final Plan of Action.

Pollution of watercourses and fjords has been a major
concern of the pollution authorities in the past as well.
This means that a number of goals and criteria for water
quality have already been established.  To the extent that
landfills and contaminated ground contribute to the pollution
of surface water it is natural to assess the measures in
relation to the existing goals.  Up to now, polluted soil and
groundwater have not been given the same attention.
Landfills and contaminated ground are primarily a source of
these kinds of pollution, and it is in these areas that the
Plan of Action raises new questions of principle in
connection with the goals for environmental quality in Norway.

3.1  Proposed goals for groundwater quality

All large, exploitable sources of groundwater shall be
protected against pollution.  If already polluted, measures
shall be taken, if -technically feasible, to enable the
groundwater to be used in future as a source of drinking
water.


In essence, groundwater is well protected against pollution.
However, groundwater is a vulnerable recipient in cases of
large discharges or spillage of pollutants to the soil.
The pollution can spread over large areas before being
discovered, and can make the reservoir unsuitable as a
source of drinking water in the foreseeable future, even if
action is taken.

In Norway, very little use has been made as yet of groundwater
resources.  Only about 15-20% of our water consumption is
covered by groundwater. It is an objective to increase this to
30% by the year 2000.

The proposed goal for groundwater also implies that polluted
reservoirs that may be of interest as sources of drinking
water shall be cleaned to drinking water quality; but
experience from abroad shows that this can be difficult to
achieve in practice.
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3.2  Proposed goals for polluted soil

Pollution of soil shall be reduced to a level that does not
conflict with the type of land use in the area.


How "to define goals for soil quality depends on whether polluted
soil is being regarded as a problem of land use, or as a damage
to the environment which, in itself, requires that something be
done.

In principle, if the soil pollution problem is to be solved
independently of land use, the only proper measure is to
clean the soil, either at the site or in special treatment
plants.  If, on the other hand, the problem is considered in
relation to the use made of the land and resources in the
area, a possible measure might be to dig up the soil and
move the excavated material to a properly safeguarded
landfill.  Another possibility is to completely or partly
isolate the polluted soil.  The polluted area can then be
used for purposes that are not affected to any degree by
pollution, such as parking sites, roads or storage premises.

The above proposed goal implies that a requirement to clean
polluted soil will be evaluated in connection with land use.
The objective of the measure should be to remove any conflict
between pollution in the ground and relevant or desired use
of the land.  Such conflicts might be connected, for example,
to injuries to the health of persons who spend time in the
area, or to risk of micropollutants being absorbed by plants
cultivated in the area as agricultural products, etc.  A
conflict would also arise if knowledge of the pollution or
of hazardous waste buried in the ground were to cause
unpleasantness or anxiety, and therefore reduced well-being,
for people living in or frequenting the area.

The proposed goal implies that, in some cases, it may be
relevant to adjust the land use to an existing level of
pollution, rather than clean the soil.  The proposal takes
into account that, in practice, it will often be impossible
within a reasonable period of time to achieve a soil quality
that is high enough after cleaning to permit the land to be
used for every kind of purpose in future.  The goal is also
justified on the ground that there is a lot more to gain by
preventive measures than by spending large amounts of time
and money on cleaning polluted soil.

3.3  Proposed goal for pollution to watercourses and fjords

Pollution from landfills, contaminated ground and sediments
shall be prevented or reduced to the level necessary to
achieve the goals for water quality in the recipient.


What is implied by satisfactory water quality is expressed, for
example, in the existing criteria for water quality and in the
goals for the different recipients. Cost-efficiency criterias
for weighing measures to clean up "old sins" against measures to
combat other, active sources of pollution must take into account
the long-term aspect of pollution from landfills and

                               88

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contaminated ground.  Leakage of toxic pollutants from these
sites may continue for several hundred years to come.  Measures
which help to reduce the pollution load only slightly at the
present point in time may have a large accumulative effect in
the long term.

4.   RATE OF IMPLEMENTATION SND COSTS.

So far, clean-up activities and monitoring have been initiated
at about 60 sites and polluted areas. The measure are directed
at the sites given highest priority, i.e. categories 1 and 2*.

To obtain control over all sites which involve risk of serious
pollution or conflicts of land use, it would be necessary to
initiate investigations and measures at about 400-500 sites by
1995.  This work implies increasing the capacity of the
regulatory offices which deal whith these cases by about 20 man
years in 1992-1993. At this rate of progress, a sum of
approximately 450 million kroner would be needed for
investigations and clean-up or safeguarding measures from 1991
to 1995.

With this capacity, the extent of investigations and measures
initiated during the period from 1991 to the end of 1999 is
expected to be:

Investigations at 800 sites                  : NOK  400 mill.

Measures at 300 sites                        : NOK 1000 mill.
Sum                                          : NOK 1400 mill.


It is emphasized that the cost estimates are preliminary, and
very uncertain.  Our experience from investigations and
clean-up measures is still very limited, and the same applies
to our knowledge about the extent of the pollution at the
different sites.

A review of the ownership of the site in categories 1 and 2*
(in all 103 sites) shows that, at almost 70% of the sites it
is possible to find a financially solvent polluter or owner
who can be made liable for the costs.  A very large number of
these sites are owned by large, national industrial
companies.  A smaller percentage, about 10%, are State-owned.

If the proposed clean-up rate is to be held, it will probably be
necessary for the State to contribute with a larger amount of
money than it is lieable to in the first place. The amount of
money from the State to help achieve the goals will be decided
by the Ministry of the Environment.
                              89

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Turkey's Tour de Table Presentation

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                 Round Table Discussions - TURKEY

                          Dr.  Resat Apak

While discussing remedial actions, one needs to distinguish
between  (i) identification, (ii) assessment, (iii).remediation, ,
(iv) financing.                                              ...   ,

There is no discovery program to identify polluted sites of land.
The Ministry of the Environment and the municipal authorities
take action for ground water pollution only if complaints from
local people are reported.  In that case, possible sources of
discharges are located, and emissions restricted or stopped.
Ground water contamination of a previously-polluted now-
abandoned site has not been recorded.  Therefore large-scale
remediation programmes for the clean-up of such contaminated
sites have not been undertaken.

Turkey's main concern at this stage is waste water treatment,
surface water purification and pollution prevention, and
prevention of hazardous waste dumping to water bodies (rivers,
lakes, ponds etc.).  The ground water resources may be considered
to be clean, and no serious ground water contamination incidents
have been reported.  For soil remediation in industrial pollution
sites, the responsible parties have to abandon the site in order
that the applied measures gain effect on the interruption of
further contamination.  In some such sites, e.g., occupied by the
leather-tanning industry which has dumped its alkaline Cr-
containing wastes and slurries in nearby lagoons over the years,
Istanbul Metropolitan Municipality offers new places to the
industrialists on the condition that they completely abandon
previous sites.  However the current legislation based on
prevention of hazardous waste discharges to lakes, rivers and the
sea is inadequate in regard to prevention of land pollution and
site remediation.

     As for the legal aspects, the Prime Ministry Directorate of
the Environment has become the responsible authority for
environmental affairs between the years 1980 and 1991.  This year
(1991) in April, the Ministry of the Environment has taken
independent legal action; there has emerged a much closer concern
for the environment both in the public and government levels.

     In the municipality level, state of the art (EPA) regulated
industrial and municipal landfills are constructed in a heavy
industrialized Bursa region.  Istanbul Municipal Authority is
preparing a Master Plan for the action and regulation of domestic
and industrial pollution.  In Istanbul where considerable
pressure of urbanization and industrialization is perceived, the
major industries that cause pollution are forced to move out of
the Golden Horn Area by the Municipal Authority; investigations
are underway to remediate this estuary (where water circulation
is poor)  and the surroundings.  Two biological treatment plants
for the handling of domestic wastes and sewage are being
                                92

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constructed in Istanbul in addition to the primary (screening)
treatment of sewage applied before.

     To sum up, Turkey is at the start of the path, and he feels
optimistic to have a better standing in land remediation and
pollution prevention in the near future.  The first consequences
of these projects shall be discussed in the extended Pilot Study.
                                93

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     T U R K E Y'S  RESEARCH  PROJECTS

     HAfO/OCMS Pilot Study on "Remedial Action Technologies
     for Contaminated Land and Ground Water",International
     Goaferenee,18-22 Nov.,1991ปWashington,D.C.

        The abstracts of a number of research workfjand
     projects carried out in Turkey for the  identification
     and assessment of ground water,surface  water and land
     pollution are presented below for round-table discussions.
PHOSPHATE  AND'  NITROGEN REMOVAL PROM WASTEปATER  BY  THE  PLANT1 '

PASPALLUH PASPALOfiM                            ! '


Oner SAYBIN and Ayse TOMRUK

Institute of Environmental Sciences, Bosphorus University

80815 Bebek, Istanbul, Turkey


Abstacts


An  alternative  and  cheap way of nutrient  (N,P)  removal  from
                                                 • , >-
wastewater is growing higher plants In it. Studies with Rasfiaj.l.ug

ฃฃSฃSl2dฃฃ  show a zero order removal kinetics in both  phosphate

and ammonium Ion concentration in the wastewater.  A maximum rate

of  60  mg/sqra h of PO -P and 90 mg/sqm h of NH -N  wag,  observed
                      4              ."  ,  '  • '  3    :,.  ' .."...
during  the daytime..  The daily avarage values for sunny days  in

August  were  0.8 g/sqm d for P and 1,5 g/sqm d for N.t T|ie  rate

depends on the amount of biomass already present on unit area and

on  the light intensity.  Fresh harvesting causes a  considerable

reduction in the P removal rates.
                                94

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           SOLAR DRYING OIF RESTAURANT FOOD-WASTES

                •"/•  '           •••  ••   AND

                         REUSE AS ANIMAL FODDER


                        Ayงe TOSUN and omer SAYGIN
                         Institute of Environmental Sciences,
                                Bosphorus University                  '
           ,     ,-,..•          80815Bebek, Istanbul*
                                       Turkey
Abstract

     A simple solar-boiler dryer, for restaurant food wastes, was constructed which has a
surface area of 0.5 irfand works at 100 ฐC. Drying was achieved in two steps: firs, boiling
the wastes close to  dryness, then further drying  at ambient temperatures. By this  way
sterilization was achieved without over heating.The energy yield of the dryer at 100 ฐC was
0.85. The obtained product, in average, has a composition  close to standards of chicken
fodder. Chickens fed by this product mixed 1/1 with market fodder grow comparably well,,
                    Advances in Water Resources Technology, G, Tsakiris (ed,) &1991 BalKema, Rotterdam.
                                                               ISBN 90 8191 1842

          Boron pollution in Simav River, Turkey and agricultural impacts


          Stier Anaง
          Department of Irrigation and Drainage, Faculty of Agriculture, University ofpge, Bornova, Izmir,
          Turkey   '
          ABSTRACT                                                   ,

          Turklye possesses.approximately 60 % of  the world's known boron reserves.
          The reserves of berate are located In the Susurluk basin.Simaw' riuer
         .la the main source of water for Irrigation schemes of the basin and
         - the residues evolved during the mining process pollute the river.Boron  •'
         .copcjentratign of river is In the range of 1-36 ppm.
         "'•  '•  In .this study .results, of several Irrigation .experiments which
          were conducted In the Basin on rlee,aunflower and dean are presented.
              It was. fbuno that,the higher concentration of-doron. increased the
          accumulation in soil profile,consequently 'decreased the rice yields.
          For dean ana sunflauer,however doran contents were not reached to toxic
         . levels ..where'winter rains provided effective leaching,           - '
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 Nur S8zen, COMPUTER AIDED EHVIROIMEHTAL DESIGN AID
           REMOTE SENSIKG
 The Department of Landscape Arch.iteckture
 Faculty of Agriculture,Ankara  University

     Ihe project work aiming to integrate a computer
 aided design network "being carried  out in the Department
 are as follows:
 -Environmental Impact Analysis,Case Study:Sultan Sazlxgi
 wetland and drainage works planned  by the State  Water
 Management  Authority
 - Impact of water reservoirs built  on the river  Euprates  on
 the environment (agricultural  patterns,erosion,settlement,
 natural-cultural values).
 - Determining environmental problems of Istanbul by
 computer support and remotely  sensed data.
   Ahmet Yttceer,Dept.of Civil Engineering,Faculty of
Architecture,Qukurova University,Adana, Turkey
   70$ Of the total pesticide consumption of Turkey occurs
in Crukurova Region.Projects have been carried out on the
ecological impacts and protection measures for Seyhan River
and Barrage.lake,and on the pollution and protection of
ground water resources in Adana*These works have been pre-
 sented in the Environmental Pollut.Symp.,Bogazioi Univ.,
Istanbul on 21-22 May,1991,and in Isparta on 3-5 June,1991.
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ANALYST, MAY 1989, VOL. 114                                       .        	   ;                 563

Determination  of Ammonium-, Nitrite- and Nitrate-nitrogen by
Molecular Emission  Cavity Analysis Using a Cavity Containing an
Entire Flame

Ali Qelik and Emur Henden
Department of Chemistry, Faculty of Science, University of Ege, Bornova, Izmir, Turkey
        Ammonium-, nitrite- and nitrate-nitrogen were determined by molecular emission'cavity analysis using a
        cavity containing an entire flame. Ammonium-nitrogen was converted to ammonia.by injection on to solid
        sodium hydroxide.  The calibration graph was  linear for 5-lOO(ig ml-1 of nitrogen when the ammonia
        generated was swept directly into the cavity and for 0.05-1.0 \ig ml-1, of nitrogen when it was collected in a
        liquid nitrogen cold-trap. Concentrations of 1.5 and 0.01 i^g mM of nitrogen could be detected using the direct
        and cold-trap methods, respectively. Nitrite was determined after conversion to nitrogen monoxide by iodide.
        Nitrate was  reduced to nitrite'using a copperised cadmium column and then determined as nitrite. The
        calibration graphs for both anions were linear up to 7 (ig ml-1.of nitrogen and 0.1 |Xg ml-1 of nitrogen could be
        detected. The methods were applied successfully to the determination of nitrite and nitrate in meat products,
        and nitrate-nitrogen in drinking water samples.                            -.,•••.
        Keywords: Molecular emission cavity analysis; ammonium-nitrogen; nitrite-nitrogen; nitrate-nitrogen
                                                97

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United Kingdom's Tour de Table Presentation
         99

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CONTAMINATED LAND: POLICY DEVELOPMENT IN THE UK

Judith Denner MA MSc DIG CEng MICE MIWEM MHKIE

Contaminated Land Branch
Department of the Environment
Room A228
Romney House
43 Marsham Street
London SW1P 3PY

     ABSTRACT

In its response to the First Report on Contaminated Land from the
House  of  Commons  Select  Committee on the  Environment,  the
Government identified three key areas as part of the strategy for
action on contaminated land.  This paper sets  out  the progress
on implementation of this strategy since the publication of the
response.  It provides an update of a paper presented at the IBC
conference on contaminated land policy, regulation and technology
in February  this  year and  published in the Institute of Waste
Management journal (1).

1    INTRODUCTION

1.1  Contaminated land is one of  the many  complex  issues to be
addressed by all those involved in ensuring protection of human
health and  the environment.  It  should be considered  both in
terms of its prevention and as part of the overall assessment of
land  for a  variety  of  purposes  and   users.     Dealing  with
contaminated land efficiently and effectively requires not only
scientific and technical expertise, but  also an understanding of
legal, economic  and  social issues  and  the ways in  which they
interact.

1 .2  This paper discusses the background to  contaminated land and
the developing policy in the UK, and in particular the proposals
for registers of  land which may be contaminated under s1 43 of the
Environmental Protection Act 1990.   It also outlines some of the
practical issues  which need to be taken  into account in tackling
contaminated sites.

2    DEFINITIONS AND ORIGINS OF CONTAMINATED LAND

2,1 . Contaminated land has  been defined  by the NATO Committee on
Challenges  to Modern  Society (CCMS)  as  "Land  that  contains
substances  which,  when  present  in sufficient  quantities  or
concentrations, are likely to cause harm, directly or indirectly,
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to man,  to the environment, or on  occasion  to other targets".
This  is  in line with the Government's view  that  a precise,  or
quantitative,  definition of contamination is  not possible and
that  it  should remain  a general  concept with  the focus  of
attention on risks  to  human health  or to the environment (2).
The NATO/CCMS  definition is also  consistent  with the idea that
contamination  is  not necessarily synonymous  with pollution,  a
distinction  drawn  by  the  Royal Commission  on  Environmental
Pollution in its report  (3).

2.2   Sources of contamination include a wide range of industrial
processes and waste  disposal  practices,  both  current  and
historic,  which use or give rise to  substances  which are harmful
to human  health or  the environment.

2.3   Contamination  usually  results  from:

*     storage and transport of raw  materials, products and wastes
•*     leaks and spillages
*     stack emissions
*     disposal  of waste materials  [on  or  adjacent  to  the site]
*'    demolition of  buildings or plant
*     application of sewage  sludge or  other materials to land

2.4   The  definition above only covers man-made  contamination.
However,  natural contamination  cannot  of  course  be  ignored.
Background levels of certain metals,  radon and natural methane
are  all  examples  of  natural  contamination  which need  to  be
considered in terms  of  their  impact   on   human health  and
development.   The  DoE has  commissioned  a study  to review the
sources and locations of  natural contamination and consider their
significance   as  part  of the  development  of a consolidated
strategy  for tackling  contamination.

Amount of Contaminated Land

2.5   There have been  a  number of  estimates of  the  amount  of
contaminated  land in England  and Wales, but  the figures vary
widely.  The most recent  estimates suggest that 50 000 - 100 000
sites might be considered to be contaminated,  affecting perhaps
50 000 hectares.  Only  a  small  proportion of these, however, are
likely  to pose  an   immediate  threat  to  public  health  or the
environment (4).

2.6   The  geographical  distribution  of contaminated sites is of
course  related to the pattern of industrial  development.   The
major industrial  conurbations of  the North,  the Midlands and
South Wales have  large areas of land formerly used by industry


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and now  derelict or reclaimed  for other uses.   However,  many
other parts of the country are or were centres for industries or
trades with the potential  for  leaving contamination,  and the
sites of former  town gas  works, scrap  yards and waste disposal
facilities are found throughout the country.

2.7  In  its  response  to  the  Select  Committee  report  on
contaminated   land,   the   Government   recognised   that   more
information was needed on the extent and location of contaminated
sites.  This is one of the objectives of the registers to be set
up  by  local  authorities  under  s143  of  the  Environmental
Protection Act 1990, discussed later in the paper.

Types of Contaminants

2.8  The contaminants expected  on  a site  are of course related
to the activities on the site. Commonly encountered contaminants
include: heavy metals,  found at  sites such as scrapyards, sewage
works and  tanneries;  organic compounds,.  including chlorinated
solvents from chemical industries;  asbestos, from power stations
and other industries; and combustible  substances and flammable
gases/  for example  from gasworks and former waste disposal sites.

2.9   Contaminants can have both short and long term effects on
human  health  (directly  or  via other  pathways  such  as  crop
uptake), the natural environment  (including water resources or
other ecosystems),  or the built environment.  These effects vary,
depending on the particular substance  and its availability and
mobility.

3    UK POLICY

3.1  In their response to the House of Commons Select Committee
on  the  Environment First  Report  on  Contaminated  Land  ,  the
Government identified three key areas for action:  (i) information
on the extent and location of contaminated sites;  (ii) assessment
criteria for the risks posed by the contamination found there;
and (iii) technology and funding for clean-up. ('4, 2)

4    INFORMATION ON LAND WHICH MAY BE CONTAMINATED

4.1  The best starting point for assessing contaminated land, and
establishing what needs  to be done  about it, is to know how much
there is and where it  is.   Such information  is  essential when
there  is  concern  over  threats   to   public  health  and  the
environment, when land  is  bought and sold, when its use is to be
changed,  or when new development is proposed  (5).
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Environmental Protection Act 1990 - Section 143 Registers

4.2  To satisfy  the  need for this information,  the  Government
introduced Section 143 of the Environmental Protection Act 1990.
This places a duty on local authorities to compile and maintain
registers  of land which may  be contaminated  because of  its
previous or current use, in accordance with regulations.   It is
intended to  have the regulations in  force in April  1992  with
registers open to the public in April 1993.

4.3  Consultation on the detailed proposals for the regulations
and for guidance on compiling registers has now taken place (6)
and responses have been  received  from a wide range of interested
bodies covering landowners, financial institutions, planners, the
legal  profession,   industries,   environmental   groups,   local
authorities,  other  government  departments  and  professional
bodies, including  the Institute  of Wastes Management.   These
comments and  suggestions are  now being considered both  in the
formulation of the regulations and guidance  for registers,  and
more widely in the development of contaminated land policy.

4.4  Section  143 gives  the  Secretary of  State powers to  define
the uses which may cause the  land  to be contaminated.   Sites
where these  uses have been  or are being carried  out  are  to be
included on the register. The consultation paper lists the uses
which are being considered for inclusion in the regulations.

4.5  One important point to note  is that  sites  which have been
investigated  or  treated must  not be  removed  from  registers.
Investigation and treatment of contamination  do not  change the
facts about uses  of the land.  Instead,  it is proposed that where
it is known that a  site  has been investigated and/or treated for
contamination,  the  register entry  should state  the  date  and
nature of this work and refer to any report which may have been
prepared.

4.6  The registers  are  to  be  compiled from  desk studies  of
current and historic  information,  mainly map base'd.  The sources
to be used and the methodology  for  compiling the registers are
all discussed in the consultation paper, and  further guidance
will be provided to  authorities.  Studies  of  this kind are the
first  step in conventional  assessment of sites  which may  be
contaminated.

Uses of registers

4.7  The main purpose  of  registers  will  be  to alert  local
authorities,  landowners  and potential  purchasers  or  developers

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to the possibility  of  contamination,  and to indicate the types
of contamination  to be expected.   However,  registers will also
assist local authorities in carrying out  many of their statutory
functions,  both  in  dealing  with  individual  cases  and  in
developing management  strategies.   Guidance on  registers will
also  cover ways  in which the  information they  hold  can  be
combined  with  other  environmental  information  or  planning
systems.

4.8  The  registers  will  of  course  have  their  limitations.
Firstly, no methodology can ensure that all land  which may be
contaminated  will  be  identified.    For example,  it  would  be
impossible  to identify  all sites  of unauthorised  dumping  or
accidental spillages of harmful material.   However, registers
will provide a record of a large proportion  of land which may be
contaminated.

4.9  Secondly, registers will only record sites which have been
put to contaminative uses.  They are not,  in  themselves, intended
to pick up land affected by air-  or  water-borne contamination
from activities elsewhere.  They will however provide information
which can be used with mathematical modelling or other techniques
to  trace  the  movement  of contamination  from  its  sources.
Developments  in site  investigation techniques,  in  particular
remote  sensing,  will  also  help   to  locate  and  identify
contamination both  on registered sites and  elsewhere.

4.10 Registers will therefore have a key role in the collection
of information on the  uses of  land and  its  condition, and will
complement  other   information   such   as   that  on  natural
contamination.  This coordinated information is all relevant to
the development of an overall strategy for planning and assessing
land use and ensuring environmental protection.

Blight

4.11  The Government recognises that the  appearance of  a site in
the register may adversely  a'ffect the value or sal'eability of the
site or of properties on or'near it.  This has implications for
the property owner,  the  developer,  the  purchaser and all those
involved  in  land  use  and land  transactions.   It  should  be
recognised, however,  that  the information to  be  included  on
registers.is likely  to be required in any case by planners and/or
purchasers, whenever a  site is  sold or a new use proposed.
Awareness of  the  need  for information on a site's history and
possible contamination is constantly increasing.           -'•"•"-
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4.12 The problem  of  blight has already  arisen in a number  of
cases without the introduction of registers,  particularly where
properties have been  built on closed landfill sites,  and more
cases can  be expected  as general  awareness of  environmental
issues increases.  The  Government's view, however, is  that  in
view of  the increasing scientific knowledge and public awareness
of the problems of contamination, in all  but the  short term  it
is best for all concerned  to know the history of  a site.   They
can then investigate, and  if necessary deal  with  any  problems,
from a position of knowledge.

4.13 The introduction of registers will inevitably intensify the
problem initially, but  in  the longer term  it will provide  a
framework  for  dealing with  blight  on a  systematic basis and
preventing uninformed development  or purchase of contaminated
sites.  The Department has commissioned a study of the problems
of  blight  and  how  they can  be dealt  with.   One  important
consideration  is  the question of  communicating  risks  to the
public and other interested parties,  discussed later  in this
paper.

5    ASSESSMENT OF CONTAMINATION

Identification of the likely contamination

5.1  Once sites which may be contaminated have been identified,
assessment  is  needed to  establish whether  they represent  a
problem.   This  requires a sound understanding of the specific
contaminants which may be present as a result of the use of the
site.

5.2  To help users of registers, the Government plans to publish
a series of "profiles" on each  of the contaminative uses defined
in the Regulations.  These will indicate the contaminants to  be
expected and will provide other information which will be useful
in assessing the sites.   Some 60 profiles are now in preparation
by  consultants who  have  drawn on a  wide  range of  sources
including trade associations.   Preparation of the. first batch  of
profiles for publication is now in hand.   There will be a final
peer review and further  technical comments  will be sought from
relevant industries.

Risk assessment and quality criteria

5.3  At present  the   UK  uses  a range  of "trigger  values" for
certain  contaminants  and  end  uses,   together   with  other
environmental  criteria,  to  judge  a  site   and  the  proposed
remediation strategy. A study  group has been set up to consider

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the whole issue of risk assessment for contaminated land and is
currently considering  a draft  report  outlining a framework for
the development  of guidance on site  assessment  procedures and
criteria.  The report includes  a review of approaches adopted in
other countries.

5.4  Work is also in hand  on the consolidation of trigger values
The general question  of  a  soil  protection strategy  and  soil
quality objectives is also under consideration.   However it is
important   to  realise   that  the   complexities  of  soils,
hydrogeology, behaviour of contaminants and preventative measures
mean that prescriptive formulae are not possible.

5.5  It is  becoming generally agreed that  clean  up should not
normally aim  to  restore  the land for all possible  future  uses
("multi-functionality").  The cost of  such an approach would far
outweigh the benefits, and would in any case often merely shift
the contamination elsewhere.   The aim of restoration should be
to ensure "fitness for purpose", balancing a number of  local and
national environmental, economic and social issues.

6    TECHNOLOGY AND FUNDING  FOR CLEAN-UP

6.1  A fundamental problem in dealing with contaminated land is
the availability and suitability of clean-up solutions.  In its
response to the Select Committee Report, the Government undertook
to review its  support for the development of clean-up technology.

6.2 An important research programme at Warren Spring Laboratory
to investigate treatment techniques for contaminated land is now
well under way.  As well as  the  programme of laboratory and full
scale work,  technical appraisal reports are already available and
others are in preparation, including a major report on clean up
technologies.  This, report, which will be published shortly,  will
discuss in detail each category of process and the sub-categories
in  terms  of  process  operation and  limitations,  as  well  as
application and  state of  development.  It  will be based  on a
major literature survey as well as review of the NATO/CCMS study
projects and other projects  and commercial ventures. (7, 8,  9)

6.3  Clean-up  technologies  can be categorised on the  basis of
their  general  operating  principles:  biological,   chemical,
physical,  solidification/stabilisation, and thermal.   Clean-up
techniques can be applied either in situ, where the material is
not moved, or  after excavation, ex situ, where the  material is
excavated prior to treatment.  Ex situ processes can take place
either on or  off  site,  and  cannot be  fully distinguished  from
conventional waste treatment operations.

                             106

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6.4  The Derelict Land Grant programme, which now places greater
emphasis on reclamation schemes that will improve the environment
or  deal  with   serious  contamination,  continues   to  tackle
contaminated  sites which  are  derelict  and  can be  reused.
Financial  assistance,  in  the  form  of  supplementary  credit
approvals, is also available  to local authorities  for remedial
measures on sites affected by landfill gas.

7    LEGISLATION

7.1  There  are  three  main  areas  of  legislation  affecting
contaminated land: prevention;  powers to enforce clean up;  and
control of remedial treatment.    The most common problems  are
usually related to the civil liability of the owner of the site
to a third party, particularly in terms of recovery of clean-up
costs, and to the question of retrospective liability.

7.2  It  is almost  impossible  to give  a definitive list  of
relevant legislation but the main statutory powers of particular
relevance to contaminated land  include those under:

     *    Occupiers Liability Act 1957
     *    Health and Safety at Work Act 1974
     *    Water Act 1989
     *    Environmental Protection Act 1990 (parts of which  are
          carried forward  from  the Public Health Act 1936  etc
          and Control of Pollution Act 1974)
     *    Town and Country Planning Acts
     *    Building  Regulations  (see  particularly   Approved
          Document C)

7.3  The Water Act 1989 provides powers to the NRA and others to
enforce emergency clean up of sites which represent a threat to
controlled waters.    Section  115  of  the Water  Act  1989 also
provides  for  recovery of  the  costs of  dealing  with  water
pollution from the person who "caused or knowingly permitted"  the
pollution.

7'. 4  The  Environmental  Protection  Act  strengthens  previous
provisions under  the  Public Health Acts  relating  to "statutory
nuisance".  These powers have been used by local authorities in
the past  to  require  treatment of contaminated sites  which  are
considered  to  represent  a  threat  to  public  health  or  the
environment.   Section  80 empowers  local  authorities to enforce
clean-up and recover  the costs; it requires  them  in most cases
to  seek recovery  first from  the person  responsible for  the
nuisance.  Section 61  of the  Environmental Protection Act 1990
empowers Waste  Regulation  Authorities to recover the costs of
                             107

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of information to  be  obtained for further evaluation and cross
checking.

8.5  The information  from  the site survey can then be combined
with the historic records and information from other sources to
arrive  at  a clear picture of the condition of the  site.   The
requirements  of  the  particular  use  of  the  site  or  other
environmental  protection  measures can  then be  reviewed  and
options for management of any risk from the site identified and
evaluated.

8.6  The most appropriate  solution can  be selected and  will
usually include  an optimised combination  of  treatment  methods
appropriate to the particular types of contamination and other
site conditions,  since it is unlikely that one form of treatment
method alone will be the most effective way  to deal with all the
contaminants  and areas of  the  site,  either technically  or in
terms of  cost.   Detailed  proposals can then be  developed and
implemented,,  with  continuous  feedback  as  work  progresses.
Contingency plans  and monitoring  are essential  components of a
successful scheme."                       ,     .

8.7  Consideration should also be given to the possibility of use
of additional treatment  methods,  not strictly required  for the
end use currently  proposed,  but which would, at  a small extra
cost, render  the site permanently suitable for  a  wider  variety
of end  uses.   Such   "polishing"  treatments could go some way
towards the ideal of multi-functionality without excessive cost.

8.8  A  checklist for  contaminated land assessment  is given in
Appendix A.

9    OTHER ISSUES

9.1  It is apparent in dealing with contaminated land that there
are interactions  with  many other social and environmental issues.

Consultation

9.2  The wide range  of interests  associated  with contaminated
land can cause  confusion and misunderstanding  about statutory
responsibilities.    For  example,  different  local  authority
departments  have  responsibility   for planning,  environmental
health and building control.   It is important to ensure that all
parties who may have an interest are included in development of
solutions to contaminated land problems.

Public Perception             .                               -


                             108

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.dealing with  pollution from old landfills  from  the landowner-.
The power is discretionary and WRAs are required to "have regard
to any hardship which the recovery may cause".

7.5  Planning legislation also provides mechanisms to encourage
or insist on clean up,  particularly in relation to the return of
contaminated land to beneficial use;  contamination of land is a
"material planning consideration" for development (3).

7.6  Liability to a third party can also be enforced as a civil
action by a breach of duty (tort), such as trespass,  negligence,
nuisance,  actions under  the rule of Rylands  v Fletcher  and
breaches of statutory duty.

8    PRACTICAL ASSESSMENT

8.1  Guidance  on  some  of  the  problems  of  assessment  and
redevelopment of  contaminated land is provided  in  a series of
papers  published by  the Inter-Departmental  Committee  on  the
Redevelopment   of  Contaminated   Land ,\ (ICRCL),    which   has
representatives from a number of divisions  in  DOE and from other
Government Departments.   ICRCL  publications are available from
the  DoE Publications  Sales Unit, Building  1 ,  Victoria Road,
Ruislip HA4 ONZ.

8.2  As part of a programme of improving guidance for all those
involved. in  the  assessment and redevelopment  of  contaminated
land, the Department is the  major sponsor of an 18 month research
programme  through  the  Construction   Industry  Research  and
Information Association  (CIRIA) on the provision of guidance on
a wide range of practical issues relating to  the assessment and
treatment of contaminated land.  CIRIA intend to publish guidance
documents oh specific  issues  as soon as they  are available.

8.3  It is essential in tackling  contaminated land  to be clear
about  the issues to be addressed and  the requirements  for a
solution.  Good project management is  one  way of providing the
framework within which problems are either avoided or overcome.
Key  factors are anticipation, flexibility,  and communication.

8.4  The first step is to carry but a preliminary assessment of
the site, which starts  with the  collection  of  information on the
site history - such as that contained in Section 143 registers.
This, together with a site walkover, reference to relevant ICRCL
documents and a consideration of the broad environmental context
of the development, should  provide a good outline indication of
the  likely problems to be encountered.   A  detailed  but cost
effective survey can then be designed to provide the  right level


                             109

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9.3  Contaminated land can cause considerable alarm where people
find that they are living on or near a contaminated site.   This
problem has already arisen in  a number of  places  where  housing
has been built on closed landfill sites which are now generating
methane.  Section 143 registers of land which may be contaminated
will heighten  public  awareness of contamination  and, as  noted
above, there may be cases of  alarm where property is found to be
on the site of some long-forgotten contaminative activity.  The
Department's study of blight  will consider how such concerns may
be addressed.

10   CONCLUSIONS

10.1 It  is  clear  that  the  contaminated  land  will   assume
increasing importance within the overall context of environmental
issues.   Expertise is  available  and  a  framework in place  to
tackle contamination effectively.   There are  many opportunities
for exchange of knowledge and technology and interaction between
many professional disciplines will be needed.

REFERENCES

(1)  IWM Wastes Management Volume LXXXI No 7 July 1991.

(2)  Department of the  Environment.   The Government's Response
     to  the First  Report from the  House  of  Commons  Select
     Committee  on   the  Environment  on  Contaminated  Land.
     Cm 1161.  HMSO, 1990.

(3)  Eleventh  Report  of the  Royal Commission on  Environmental
     Pollution: "Managing Waste: The Duty of Care".  HMSO,  1985.

(4)  House of Commons Environment Select Committee First Report
     on Contaminated Land.  House of  Commons Paper  170-1.
     HMSO 1990.

(5)  Department of the Environment Circular 21/87 (Welsh Office
     22/87): Development of Contaminated Land.   HMSO, 1987.

(6)  Department of  the Environment.    Environmental Protection
     Act  1990  Section 143:  Local  authority  registers  of land
     which may be contaminated.  Consultation paper,  May  1991.
     (available  from:  A238  Romney  House,  43  Marsham  Street,
     London SW1 3PY).

(7)  Review of Innovative Contaminated Soil Clean-Up Processes.
     Report in preparation.   Warren Spring Laboratory,  Gunnels
     Wood Road, Stevenage SG1 2BX, UK; ISBN 085624 6778. *


                             110

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(8)   Bardos,   R  P   (1990):   The  NATO/CCMS  Pilot   Study   on
     Demonstration   of  Remedial   Action   Technologies   for
     Contaminated Land and Groundwater, Status June 1989.  Report
     LR 817.  Available  from Publication Sales, Warren  Spring
     Laboratory,  Gunnels Wood Road,  Stevenage SG1  2BX, UK;  ISBN
     085624 6751.

"(9)   Bardos,   R  P   (1991):   The  NATO/CCMS  Pilot   Study   on
     Demonstration   of  Remedial   Action   Technologies   for
     Contaminated Land and Groundwater, Status June 1990.  Report
     LR 818.  Available  from Publication Sales, Warren  Spring
     Laboratory,  Gunnels Wood Road,  Stevenage SG1  2BX, OK|  ISBN
     085624 676X.
                            Ill

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    Tour de Table Presentation on United States/German
Bilateral Agreement on Abandoned Site Clean-up Projects
                    113

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United States/German Bilateral Agreement
   on Abandoned Site Clean-up Projects

              prepared for

             NATO CCMS
         November 18 to 22, 1991
      Bilateral Agreement Contacts

         Hans-Joachim Stietzel,
       German Federal Ministry of
        Research and Technology
                  and
   Bob Bowden,  U. S. EPA - Region 5
    Don Sanning, U. S. EPA  - ORD
                  114

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                     SUMMARY TABLE
U.S. Sites     Technology
                  Waste       Applicable Waste
                  Matrices     Inorganic  Organic
Burlington-
Northern
(Minnesota)
 Bio-Remediation   Soils
Parsons       GeoSafe
Chemical     In Situ
(Michigan)    Vitrification
                  Soil and
                  Sludges
MacGillis&   Biotrol Aqueous     Soil and
Gibbs        Treatment System   Water
(Minnesota)
                       PAHs
                       Phenols
                       Oil and
                       Grease

             Mercury   DDT
             Arsenic    Chlordane
             Heavy
             Metals

                       PCPs,
                       Creosotes
                    SUMMARY TABLE  - 2
U.S. Sites     Technology
                  Waste        Applicable Waste
                  Matrices     Inorganic   Organic
Ott/Story/
Cordova
(Michigan)

Lee Farm
(Wisconsin)
Outboard
Marine
(Illinois)
Solarchem
UV Oxidation
Maecorp
Stabilization/
Solidification

Soil Tech
Anaerobic
Thermal
Processor
Water
Soils
Sediments
          TCE
          VOCs
          Aniline
Lead
          PCBs
                             115

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                    SUMMARY TABLE
German Sites Technology
                  Waste     Applicable Waste
                  Matrices  Inorganic  Organic
Gas-Works
(Munich)
High Pressure
Soil Washing
   Soils     Lead      PAH
   Water    Cyanide   Hydrocarbons
Burbacher    Thermal Treatment Soils and  Sulfides   Phenols
Hiitte        Soil Washing       Water    Cyanides  Benzol
(Saarbrucken) Bioremediation              Lead      Toluol
                                        Mercury
Stadtallen-
dorff
(Hessen)
SoU Washing
   Soils
          Phenols
          PAH
          Hydrocarbons
                    SUMMARY TABLE - 4
German Sites Technology
               Waste        Applicable Waste
               Matrices     Inorganic  Organic
Kertess
Chemicals
(Hanover)
Varta Sud
(Hanover)
SoU Air Venting Soils and
In Situ Soil     Water
Washing
High Pressure
SoU Washing
Soils and
Sludges
                      Halogenated
                      and
                      Petroleum
                      Hydrocarbons
Antimony
Arsenic
Cadmium
Lead
Haynauer
StrasseSS
(Hessen)
High Pressure
SoU Washing
Soils
          PCB, PCDD,
          PCDF
                             116

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Burlington-Northern (Minnesota) —Background
  Creosote was used to preserve railroad ties
  from 1907 to the present
  Creosote wastewater was discharged to
  unlined lagoons.
  Soils, groundwater and sludges were
  contaminated with PAHs, oils, and phenols.
  Site placed on EPA's National Priorities List in
  1982.
 Burlington-Northern—Remedial Technology
  Soil treatment focuses on aerobic biotreatment
  to transform and immobilize organics  and
  inorganics in the soil.
  Biotreatment Is not intended to completely
  degrade all waste constituents.           .
  Biotreatment transforms and immobilizes
  waste constituents, thus rendering them
  non-toxic and non-leachable.
                    117

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       Burlington-Northern —Status
 Biotreatment degraded PAHs to lower level
 chemical rings and lower toxicity compounds.
 Soil treatment will be monitored every 4
 months until all PAHs and phenols have
 decomposed or until no further reductions are
 evident.
 Remediation is expected to continue for several
 years.
Parsons Chemical (Michigan) —Background
 Operated as an agricultural chemicals
 manufacturing and packaging facility from
 1945 to 1977.
 Soils were contaminated with pesticides, heavy
 metals, and dioxin from a leaking septic tank.

 Site placed on EPA's National Priorities List in
 1989.
                   118

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 Parsons Chemical—Remedial Technology
In situ vitrification was developed by Battelle
Memorial Institute and marketed by Geosafe
Corporation.

Technology uses electrodes to generate electric
current that heats soil to its melting point.

Soil melting destroys pesticides and dioxin and
produces a glass crystal mass that immobilizes
metals.
        Parsons Chemical—Status
EPA and Michigan Department of Natural
Resources are conducting a remedial
investigation and feasibility study.

Soil treatment postponed 1 to 2 years for
equipment restructuring; an off-gas hood is
being redesigned with new inert materials.
                  119

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MacGillis & Gibbs (Minnesota)-Background
  Operated as a wood preservation facility from
  1920 to the present.

  Soils, surface water, and groundwater are
  contaminated with creosote, PCP, and
  chromated copper arsenate.

  Site placed on EPA's National Priorities List in
  1984.
 MacGillis & Gibbs-Remedial Technology
 Biotrol aqueous treatment system (BATS), a
 modification of aerobic biotreatment systems,
 uses Flavobacterium to degrade contaminants
 such as PCP in liquid wastes.

 In 1989, the technology was tested under the
 EPA SITE Program on groundwater
 containing a floating layer of PCP oils up to 2
 meters thick.
                   120

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        MaeGillis & Gibbs-Status
 In the SITE demonstration, BATS removed
 96.4 to 99.8 percent of the PCP in the
 groundwater.

 Based on these results, BATS is being
 considered for large-scale remediation
 projects.
Ott/Story/Cordova (Michigan) —Background
 Operated as a manufacturer of synthetic
 organics and! phogene-base intermediates from
 1956 to 1977.

 Groumdwater and soil were contaminated with
 volatile organic compounds (VOCs).

 Site placed on EPA's National Priorities List in
 1982.
                  121

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Ott/Story/Cordova—Remedial Technology
UV oxidation technology applied at the site is
manufactured by Solarchem International of
Canada.

UV radiation, combined with hydrogen
peroxide or ozone, will detoxify halogenated
and other VOCs in groundwater.
       Ott/Story/Cordova-Status
 Pilot-scale treatability studies conducted.
 from October 1990 to March 1991.

 Data from studies are being evaluated to
 finalize a site-specific treatment scheme.
                                     *
 Remedial design and action are expected to
 follow after treatment scheme is finalized in
 1992.
                 122

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  Lee Farm (Wisconsin)—Background
Lead-contaminated battery casings were
dumped at the site between 1971 and 1974.

Soils were contaminated with lead and lead
compounds.

Emergency removal of lead-contaminated
waste was completed in August 1991.
   Lee Farm—Remedial Technology
Soil solidification was accomplished in two
phases:

Phase 1 developed and completed by Maecorp.
Proprietary powders and a Maepric solution
solidified contaminated materials.
Phase II completed by OHM. Portland cement
and water solidified contaminated materials.
                123

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           Lee Farm—Status
 Contaminated-soil solidification is complete.

 Solidified materials are buried on site.
 A clay coyer has been installed to complete
 disposal area closure in accordance with
 Wisconsin Solid Waste Management
 Regulations.
Outboard Marine (Illinois)—Background
Operated as a manufacturer of recreational
marine products from 1961 to present.
Operations produced PCB-contaminated
wastes.
Slip and harbor sediments, soil, and
groundwater were contaminated with PCBs.
Site was placed on EPA's National Priorities
List in 1983.
                  124

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Outboard Marine—Remedial Technology
 Soil Tech's anaerobic thermal processor (ATP)
 1) vaporizes PCBs and other contaminants in
 a rotary kiln, then 2) condenses and separates
 them into oil, water, gas, and treated solids.
 Contaminated oil fraction disposed off site;
 contaminated water treated on site; gas
 fraction used as fuel for the rotary kiln
 burner; treated solids disposed of in an on-site
 containment cell.
        Outboard Marine—Status
Two containment cells were constructed to
isolate PCB wastes.
Contaminated soil has been excavated for
treatment.
Dredging of harbor sediment and dewatering
of slip sediment will begin late 1991.
Further soil treatment will begin early 1992.
                 125

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   Gas-Works (Munich)—Background
From 1909 to 1975, the 81-aere site operated as
a natural gas production facility.

Soil and groundwater are contaminated with
PAHs, lead, cyanides, and aliphatic
hydrocarbons.           ,      .      r
Results from remediating a "hot spot" of
contamination will focus the remedial design
for the entire site.                         '
   Gas-Works—Remedial Technology
Soil is washed in a "closed system1' with
mechanical crushers and high-pressure water
jets.                     -       _.r,r  .

Soil clean-up criteria are expressed as
numerical values while the groundwater •;
clean-up target is qualitative—the upgradient
shall be unaffected by the contaminated site.
                126

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             Gas-Works—Status
   A mobile on-site soil washing plant was
   constructed and testing has started.

   Soils from the hot-spot have been excavated
   and placed in interim storage.

   A field test for microbiological treatment of
   PAH-contaminated soil is also planned.
Burbaclier Hutte (Saarbrucken) —Background
   A ISO-acre site operated from 1857 as a steel '
   factory with a coking plant.                 ;
   Soils and groundwater are contaminated with
   cyanide, heavy metals, and aromatics.
   Unused production facilities will be
   demolished, but administrative buildings
   remain and new development is planned.
                    127

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Burbacher Hiitte—Remedial Technology
Several on-site technology demonstrations are
planned.
Eight contractors will perform large-scale tests
of bioremediation, soil washing, and thermal
treatment processes.

Soil extraction systems for in situ gas
extraction will be implemented.
       Burbacher Hiitte—Status
Old pipelines, utilities, and demolition debris
must be removed before further work begins.
Contracts for technology studies have been
awarded.
Contaminated debris will be stored;
noncontaminated debris will be backfilled.
                 128

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 Stadtallen dorff (Hessen) —Background
From 1938 to 1945, two factories produced
explosives and ammunition at the site.

Factories were dismantled in 1949 and one
area was converted to a residential area.

Soil and groundwater are contaminated with
explosives, prefabricates of explosives, phenols,
and heavy metals.
 Stadtallen dorff-Remedial Technology
Carbon adsorption and soil washing
technology will be used in remediation
because of their successful lab tests in 1991.
Residuals will be incinerated.
Research is being conducted to develop
clean-up criteria and technology for
explosive-related contaminants.
                 129

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          Stadtallendorff-Status
  A groundwater treatment extraction system is
  under construction and expected to be
  complete in 1993.

  A soil washing/thermal treatment plant is
  expected to begin operating in 1994.

  Treated groundwater is to be used as
  industrial process water; treated soil will be
  returned to excavated areas.
Kertess Chemicals (Hanover)—Background
  Site is located in an industrial area.
  From 1943 to 1985, the company transferred
  and stored detergents, acids, lyes and organic
  solvents.
  Groundwater flow leached the solvents arid
  transported them off site.
                   130

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 Kertess Chemicals—Remedial Technology

I Several technologies are in use at this site:
 —  Vertical barrier containment
 —  Extraction and treatment of ground water
 —  Lowering the groundwater table
 -  Contaminant extraction from soil by air
     venting
 —  Vapor extraction and in situ soil washing
        Kertess Chemicals—Status
 Groundwater treatment began in 1976 but did
 not meet cleanup objectives.
 Recently a new remedial plan was designed
 combining several technologies.
                  131

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  Varta Sud (Hanover)—Background
No residential areas exist near the site.
Site was a military facility and prison from
1938 to 1945.
Wastewater was discharged to a ditch from a
nearby accumulator factory from 1945 to
1989.

Soil and sediment contaminants include PCBs,
PAHs, and lead.
   Varta Sud—Remedial Technology
Treatability studies were conducted using high
pressure soil washing.
Other technologies will be tested.
                132

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             Varta Siid-Status
  Detailed information on contamination of
  different parts of the site will be collected.

  Sediment remediation and slag investigation
  are part of the clean-up effort sponsored by
  theBMFT.

  After remediation, parts of the site will be used
  as a "scientific park."
Haynauer Strasse 58 (Hessen) —Background
  A firm reconditioned chemical waste and
  waste oil on the site from 1952 to 1986.
  Surrounding land is residential and industrial.
  Oil and solvents from leaking storage tanks
  spilled on soil and into ground water.
  Main contaminants are PHCs, AHCs, CHCs,
  along with PAHs and PCBs.
                  133

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Haynauer Strasse 58—Remedial Technology
  Remediation has five stages:  1) demolishing
  buildings; 2) decontaminating debris by
  thermal treatment; 3) extracting soil-gas;
  4)  excavating soil; and 5) decontaminating
  soil by high-pressure washing process.

  Because of space limitation, three soil
  decontamination processes must be completed
  off site.
       Haynauer Strasse 58—Status
  Remediation began in 1990,

  All former buildings have been demolished
  and debris removed.
  Preparations are being made to begin soil
  excavation.
                  134

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                   NATO/CCMS Pilot Study

        "Demonstration of Remedial Action Technologies for
              Contaminated Land and Groimdwater"


                 Washington 18-22 November, 1991
United States  - German Bilateral Agreement
     on Abandoned  Site Clean-up Projects
                    Dr. Hans-Joachim Stietzel
           Federal Ministry of Research and Technology (BMFT)
                          Germany
                       Donald E. Banning
                Environmental Protection Agency (EPA)
                     United States of America
                         Kai Steffens
                       Gabriele Berberich
                Arbeitsgemeinschaft focon-PROBIOTEC
                          Germany
                          135

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       Table of Contents  ,






                                                                    Page






1.     Participants of the Bilateral Agreement                             3






2.     Background and Goals oif the Agreement                            4






3.     Remedial Projects                                                5






4.     Working Plan                                                   11






5,     Present Status and Schedule of the Project                         12
                             136

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li      Participants of the Bilateral Agreement

US EPA                       Overall SITE Coordinator

                               Donald E. Sanning
                               Senior Advisor
                               US EPA
                               Risk Reduction Engineering Laboratory
                               26 West Martin Luther King Drive
                               Cincinnati, Ohio 45268


                               Overall Region V Coordinator

                               Robert J. Bowden
                               Chief, Emergency & Enforcement Response Branch
                               US EPA                       .  • ••  :-•••   -  '/'-'
                               Region V
                               230 South Dearborn Street
                               Chicago, Illinois 60604
Federal Ministry of
Research and Technology
(BMFT), Germany
Dr. Wolfram Schott
Chief, Section Environmental Technology
Bundesministerium fur Forsehung und Technologic
Referat 523
Heinemannstrafle 2
D-5300 Bonn 1
                               Overall Project Coordinator

                               Drป Hans-Joachim Stietzel
                               Bundesministerium fur Forsehung und Technologic
                               Referat 523
                               HeinemannstraBe 2
                               D-5300 Bonn 1
BMFT-Project Management:
Waste Management and Decon-
tamination of Abandoned
Sites, Germany
Christian Nels
Projekttragerschaft "Abfallwirtschaft und Altlastensanierung"
Umweltbundesamt
Bismarckplatz 1
D-1000 Berlin 33
Technical       PRC Environmental
Consultants     Management, Inc.
               233 North Michigan Avenue
               Suite 1621
               Chicago, Illinois 60604
               Arbeitsgemeinschaft focon-PROBlOTEC
               c/o PROBIOTEC GmbH
               Kai Steffens
               Gabriele Berberich
               Schillingsstrasse 333
               D-5160 Duren 5
                                            137

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 2t      Background and Goals of the Agreement

 International cooperation is an integral part of the German Federal Government's environmental policy. In
 order to achieve success in the reduction of environmental overload, close cooperation is needed, both in terms
 of measures implemented and with respect to the research and development sector including the exchange of
 information, and experience. Moreover,  coordination and  harmonization of environmental demands  in the
 various countries helps to prevent barriers to trade and imbalances in competitiveness.

 The United States of America and the Federal' Republic of Germany have for many years cooperated in the
 exchange of information about the ongoing research and development projects as well as in the actual clean-up
 of contaminated sites. In order to intensify this cooperation the U.S. Environmental Protection Agency and the
 Federal Ministry of Research and Technology are working  together under a United States / German Bilateral
 Agreement (April 1990).

 The goals of this bilateral agreement are:      ~

         *      Facilitate understanding of each sides approach to the remediation of contaminated sites ("as-
                if-approach": as if the foreign project had  taken place in the own country)

         *      Demonstrate innovative remedial technologies                                .   ,;,

         *      Compare quality assurance  programs

         *      Facilitate technology transfer

With respect to these topics it was agreed that la better understanding of each others efforts to develop and
demonstrate remedial  technologies could only be  achieved if a demonstration of these technologies should not
only follow the rules,  regulations and other necessary guidelines of the country in which the remediation takes
place but should take into consideration the respective rules  of the other country.

Six sites on each side were selected for the cooperation. Detailed executive summary reports on each of the
german sites are presently being prepared by the contractors working for the BMFT. These reports will be
reviewed by designated U.S. EPA/RREL Technical Program  Managers to determine what additional analytical-
type Quality Assurance (QA) and Quality Control  (QC) measures should be incorporated into the  remedial
action demonstration by the Germans to meet the U.S. EPA - SITE criteria for determining the effectiveness
of the individual technologies being utilized at the sites.
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 The U.S. EPA Region V and U.S. EPA RREL have prepared similar reports for the U.S. sites. The BMFT
 will review these reports to determine what additional analytical QA / QC measures should be implemented into
 the remedial action demonstration to meet German criteria for determining the effectiveness of the individual
 technologies being utilized at the EPA sites.

 2ฑ      Remedial Projects

 In the course of the bilateral agreement,  12 remediation projects (6 in  each country) will be subject to an
 intense study. The main  characteristics of the projects are summarized in table 1 and 2 and additionally
 described in the subsequent chapter:
 Table 1: German remediation projects
German Sites
Gaswerke Munchen
Varta Sud, Hanover
Kertess, Hanover
Haynauerslrasse58, Berlin
Saarbrucken-Burbach
Stadullendorf
Technologies
Soil- Washing + Volume Reduction of Residuals
Soil-Washing (+ Acid. Extraction)
Ground Water Pump + Treat, Soil Vapor Extrac-
tion, In-Situ Soil Washing
Soil-Washing, Soil Vapor Extraction, Therm.
Treatment of Residuals
Thermal Treatment, Soil-Washing, Microbiology
Soil-Washing + Incineration
Type of Contamination
PAH, Cyanides, Lead
Pb, Sb, As, Cd
CHC + Degr. Products, CFC, HC,
Monoaromatics
CHC, CFC, HC, Monoaromatics, PAH,
PCB, PCDD, PCDF
Sulfides, Cyanides, Pb, Hg, Phenols, HC,
Monoaromatics
Munitions, TNT 4- Degradation Products
Table 2: U.S. remediation projects
U.S. Sites
Burlington Northern
Waukegan Harbor (Outboard ,,
Marine)
McGillis&Gibbs
•(Lee Farm)
(Parsons Chemical)
(Ott/Story/Cordova)
Technologies
Bio-Remediation
Anaerobic Thermal Treatment On Site
Ground Water Extraction and Biol. Treatment,
Soil Washing
Solidification/Stabilisation
In-Situ Vitrification
UV Oxidation
Type of Contamination
PAH, Phenols, Oil & Grease
PCB, Oil & Grease
PCP, PAH



Brief description of the projects:
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 German Projects;

 Gaswerke Munchen

 The remediation of a former coal-gasification and gas-distribution facility in Munich, Germany, is coordinated
 by an interdisciplinary working group comprised of the site-owner, the city and state authorities and various
 technical consultants. The entire site of the former gas-works is about 32.5 hectare (81.25 acres)  in size and
 is located about 1 km northeast of the city center. Various site investigations since 1982 showed that both the
 soil and the ground water are contaminated with PAH's and the top most layer of soil is further contaminated
 by lead. Slightly elevated concentrations of aliphatic hydrocarbons and cyanides were found throughout the site,
 with some higher peaks in limited areas. One of the hot-spots of the contamination (the "C  1 area") was found
 to pose a substantial hazard to the ground water and  shall be  remediated in a first phase  of the overall site
 remediation which is subsidized by the Bundesminister fur Forschung und Technologic (BMFT).

 Soil washing was selected as the appropriate remediation technology; 25,000 t of gravelly sediments will be
 treated on-site in a high pressure  soil washing plant.  At present (November 1991), the  high pressure soi!
 washing plant is tinder construction and will start the  trial runs in this month. Parallel to the soil-washing,
 innovative treatment technologies for the soil-washing  residuals shall be tested.

 VARTA-Sfld, Hannover

 The goal of this project is the remediation of the "Varta-Sud" area which was contaminated  by emissions from
 & battery factory nearby between 1938 and 1989. The remediation of the site owned by the City of Hanover is
 coordinated by a  consultant with the support  of the "Varta-Sud  Assessment Group" consisting of independent
 scientists and engineers. The site is located northwest  of Hanover and covers an area of 45 ha (approx. 110
 acres).

 From October 1989 to April 1991 the site investigation was performed showing lead, antimony and cadmium
 beeing Ibe main contaminants in the soil. Major hot spots are sediments dredged from a creek ("RoBbruch-
graben*) which was used for waste water discharge by the battery factqry. Furthermore slags from smelting
and coal firing are distributed inhornogenously over the area, abandoned dumps are filled with rubble, slags and
residues from the battery production. Besides the heavy metals, a PAH contamination of unknown origin was
detected in the south-eastern part of the site. The ground water is  not substantially contaminated with heavy
metals but shows elevated concentrations of chloride and sulfate.
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 At present (November 1991), the remedial investigations and trial runs of different physical treatment technolo-
 gies (physical extraction (high pressure soil washing), chemical extraction (acids), combination of both) are
 performed on a small scale base; concepts for the volume reduction of residuals are designed,

 KERTESS, Hannover

 The project involves the remediation of an industrial area which was used  for the handling and storage of
 organic solvents and detergents, as well as aromatic and halogenated hydrocarbons from 1946 until 1985. The
 owner of the site is the Deutsche Bundesbahn (DB, German Railroad). The  area is about 1 ha in size and is
 located in the southern part of the City of Hannover.  Site investigations in 1975 detected a ground water
 contamination and  in  1976 the first remediation measures (groundwater extraction  and treatment) started.
 Caused by the lack  of effectivity of these measures in 1990 consultants were hired to design a new remediation
 concept.

 Major contaminants are chlorinated and aromatic solvents in the unsaturated zone and on the bottom of the
 aquifer (DNAPL).

The remediation technologies intended to be used are the extraction of the DNAPL by extraction wells, the
 excavation or in-situ soil-washing of contaminated soil from the saturated zone using vertical large diameter
 pipes, and the vapor extraction from the unsaturated zone with or without lowering the water table. Ground
 water will be pumped and treated after a cut-off wall (sheet pilling) is installed.

 At present (November  1991) ground water pumping and  treating is performed, the design of the slurry wall is
 finished.

 Haynauerstrasse 58, Berlin

This project involves the remediation of a  former  facility for the reconditioning of chemical wastes and waste
 oils in Berlin. The remediation of the site coordinated by an interdisciplinary working group comprised of the
site-owner (Federal  State of Berlin), local  authorities and the project steering  commitee, which includes local
authorities and various technical consultants.

The site has an overall size of 3,OCX) m2 and is located in the south of Berlin, in the district of Steglitz. Various
site investigations since 1986 have detected a contamination of soil and ground water.
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 The investigations show that both the soil and the ground water are contaminated with petroleum hydrocarbons,
 aromatic and volatile chlorinated hydrocarbons and PCBs. In addition the buildings contain dioxins and furanes.
 The highest concentration of petroleum hydrocarbons was found in the southern area of the site. Aromatic
 hydrocarbons are mainly concentrated in the northern area of the site and chlorinated hydrocarbons were found
 all over the site. Contamination caused by PCBs was only found occasionally.

 The main objectives for the remediation of the site are the following:

         demolition and proper disposal of purified residues of the contaminated buildings
         extraction and treatment of contaminated soil vapor
         emission-free excavation, soil washing and thermal treatment  of contaminated soil and reembedding
         remediation of contaminated ground water

 In October 1991, soil washing treatability tests were performed and  completed successfully. The soil washing
 plant has been constructed and been proved for different soils on a large scale base. At present single compo-
 nents are adjusted for the site specific situation. The thermal treatment plant will go into operation in the
 second half of 1992.

 Burbacher Hutte, Saarbrflcken

 The objective of  this  project is  the remediation and reutilization  of the Burbach ironworks site  from an
 ecological and economical point of view. The project  is coordinated by the city of Saarbrucken who is the
 owner of the site, the KommunalSysteme GmbH Who is responsible for the remediation, and the Gesellschaft
 filr Innovation und Untemehmensforderung mbH ;responsible for the reutilization of the area.

 The site covers 60 ha and is located adjacent to the river Saar  in the western part of Saarbrucken, the capital
 of the federal state Saarland.

 One third of the site used by the Burbacher Hutte is still in operation as a rod mill. Approximately 12 hectares
are not contaminated and will be used as an industrial area without further treatment. On the northern part of
the site, which is about 29 ha in size, soil and ground water contamination was detected during various site
investigations since 1986.

According to the previous use of the area elevated concentrations of sulphides, cyanides, phenols, heavy metals
(lead, mercury) were found in the soil and partly in the  ground water particularly near the coking plant and gas
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,. generation plant. In addition chemical analyses  of soil and ground  water  showed high  concentrations of
 aromatic compounds, particulary benzene and toluene.

 At the moment heavy metals are immobilized to a large extent due to a slightly alcaline milieu. During the
 remedial action a release of vapors of aromatic compounds will require high safety measures.

 Until November 1991 contaminated and non-contaminated buildings have been demolished.  The future use of
 existing conduits on the site (coking gas pipes, electricity)are discussed.

 The remedial technologies intended to be used include soil vapor extraction, bioremediation, soil washing and
 thermal treatment. Preliminary test runs were started in summer 1991.

 Stadtallendorf,  Hessen

 The objective of this project is the remediation of soil and ground water contaminated with explosives like TNT
 and related chemicals. The Regierungsprasidium Gieflen (district authority) is responsible for the project,
 supported by the Wasserwirtschaftsamt Marburg (local authority for water and waste). Two private consulting
 companies are in charge with  the project management.

 The city of Stadtallendorf is  located  100 km north  of Frankfurt and has approximately 20,000 inhabitants.
 Between 1938 and 1945 two german explosive and ammunition factories  were operated  by the  DAG and
 ,WASAG, both covering areas of 420  ha with together 633 buildings, three waterworks and a large number of
 wells.

 A totalof 125,000 t TNT were produced. Both, the soil and the ground  water, show a high rate of contamina-
 tion with explosives like TNT and  related  chemicals,  therefore presenting  a hazard  for  humans  and the
 environment.

..The registration of possible contamination hot-spots was completed at the end of 1989. Analyses of the upper
.soil, Inspection of closed sewer systems, exploration of former deposits, as well as preliminary explorations
have been  started. Final results of the investigation program (chemistry, toxicology, pedology and hydro-
(geo)logy) will be available at the end of 1992.

The planning for the ground water remediation is under work. The system of wells, pipes and the adsorption
treatment plant (activated carbon) will be completed at the beginning of 1993. A soil washing plant is expected
to go into operation during the first quarter of 1994.
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 U.S. Projects

 Burlington Northern Site, Brainerd, Minnesota

 The Burlington Northern site in Brainerd, Minnesota, has been in operation since 1907, preserving railroad ties
 with creosote. Waste waters from the operation were discharged into two lagoon areas. Sludges in the lagoons,
 the soil under the lagoons and the ground water has been contaminated with PAH, oils, and phenolic com-
 pounds.

 "He soil and sludges were treated in a pilot-scale test to determine the effectiveness of biodegradation on the
 waste. Test plots containing various combinations of contaminated soil, sand, peat moss, and microbial seed
 were evaluated over time to determine contaminant removals and key operational factors that affect removals.
 Because  the evaluation showed reduced concentrations  for PAHs, benzene, extractables and phenols, on-site
 biological treatment of the contaminated soils and sludges was chosen for remediation of the side.

 Five years of operational data (first application in 1986) show consistent degradation of benzene, extractable
 hydrocarbons and PAH compounds.

 Outboard Marine Corporation (OMC), Waukegan, Illinois

 The OMC site manufactures marine  products for recreational use. From approximately  1961 to 1972, OMC
 used a hydraulic fluid containing polychlorinated biphenyls (PCBs),  some of which escaped through floor
 drains. Studies have indicated that past releases of PCBs to on-site surface water bodies and an on-site harbor
 slip have contaminated the site. PCBs have also migrated off site into Waukegan Harbor.

 The remedial actions for the OMC site will  include excavating highly contaminated soil and .sediment and
 treating it on site; containing  less contaminated  soil in on-site containment  areas;  containing contaminated
 sediment in-place in an on-side slip; and constructing a new slip.

 Several treatment processes were evaluated to treat the highly contaminated soil and sediment. An innovative
 low-temperature thermal  desorption process, the  SoilTech Anaerobic Thermal Processor (ATP), will be the
 treatment process used to remove PCBs from the  highly contaminated soil and sediment.  Under its Superfimd
Innovative Technology Evaluation (SITE), EPA's  Risk Reduction Laboratory (RREL) will collect performance
data on the ATP process to determine whether or not  the  ATP process is capable of meeting the cleanup
criteria for the site.
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 MacGillis & Gibbs/Bell Lumber & Pole (M&G), New Brighton, Minnesota

 The MacGillis & Gibbs/Bell Lumber & Pole (M & G) site in New Brighton, Minnesota, is currently operating
 as a wood preservation facility in the Minneapolis-St. Paul metropolitan area. Preservation applied to wood
 include creosote, pentachlorophenol, and chromated copper arsenate (CCA). Components of all these chemicals
 have been found at the site, and are spreading through the ground water contained in the highly complex glacial
 deposits of the area.

 The BioTrol Aqueous Treatment System (BATS)  technology is a package plant variation  of the aerobic
 biological treatment system used  for sewage and  other waste waters, BATS technology is modified to treat
 waters from hazardous waste sides. As a demonstration project under U.S. Environmantal Protection Agency's
 (U.S.EPA) Superfund Innovative Technology Evaluation (SITE) program, pentachlorophenol-containingground
 water from a portion of the site was pumped and treated with a biological growth including a bacterium known
 to degrade pentachlorophenol. After this demonstration, the  BATS technology has been selected, as an interim
 remediation measure for the site.  A  larger system will be installed to pump and treat contaminated water and
 the oil layer above it, preventing its spread. Meanwhile, the investigation that will lead to complete remediation
 continues.

 Three additional projects in the  U.S. are not yet chosen, nevertheless the prefered technologies are:

         solidification/stabilisation of heavy metals and/or organies
         in-situ vitrification by melting of contaminated soil
         UV-Oxidation of contaminated water

4*       Working Kan                                                               .

IB the first  step,  the remediation projects are described in  basic project reports to give comprehensive informa-
tion on the project to  the foreign partners. The case history, the remedial design and the planned technology
are the focuses of interest. The intended measures concerning monitoring  and  efficiency-control (especially
sampling and analyses) are described in detail.

In the second step> the partners design plans concerning monitoring and quality assurance especially regarding
sampling and analyses procedures for the  foreign projects,  as if the project would be  realized in their own
country. After the  exchange of  the plans,  differences  and parallels are  discussed. Monitoring measures
additional to the usual measures are implemented in the clean-up procedures if necessary. These additional
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 measures, which can last a short period of time or can accompany the whole project are funded by the domestic
 partner of the bilateral agreement. Visits of the project managers are planned.

 In the third step, the results are discussed focussing as well on the data as on the message of the results refe-
 ring to the data quality and the treatment effectivity. The results of the bilateral agreement will be compiled in
 reports, intending to improve the bilateral understanding and discussion of the general approaches and to allow
 the evaluation and comparison of the foreign results and to facilitate the technology  transfer.

 &.      Present Status and Schedule of the Project

 In early August  1991, the representatives of the U.S. EPA visited the german sites  to gain a first impression
 of the intended remediation activities and to discuss the clean-up concept.

 Subsequently, in Germany  two basic project ireports  (Gaswerke Munchen; Haynauerstrasse,  Berlin) were
 prepared with preference because of the different working progress of the particular projects. In the U.S. three
 brief reports were compiled, summarizing the information from the different detail-reports of the superfund
 projects. The detail-reports are part of the attachments.

 In the late October 1991, the german representatives visited the U.S. sites and discussed the  basic project
 reports with the U.S. EPA project managers. At present, the german  partners are  compiling the remaining
 basic project reports, whereas  the U.S. representatives are choosing three additional  sites.

 Presently remediation experts are designing sampling and analyses plans and the quality assurance objectives
 for the first two german and the first three U.S.  projects, as if these projects should be realized  in their own
 country. Additional requirements will be identified and implented in early 1992 and conducted  until 1993  if
 necessary.

 The preparation of the remaining project reports will be carried out in early 1992, because the remedial design
 of the projects is not yet completed at the time.

 Bilateral visits of the relevant project managers are scheduled in 1992 to assure the information  exchange as
 comprehensive as possible. The schedule for the particular visits is depending on the  progress of the remedial
projects.
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                           Appendix 1-B



Presentation by NATO/CCMS Guest Speakers
       147

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                     NATO/CC1VIS Guest Speaker:

                          Brett Ibbotson, Canada

AERIS, an Expert Computerized System to Aid in the
               Establishment of Cleanup Guidelines
              149

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           AERIS - AN EXPERT SYSTEM TO AID IN

   THE ESTABLISHMENT OF CLEAN-UP GUIDELINES

                                       by

                          B:G. Ibbotson1 and B.P. Powers2



1.0  INTRODUCTION

Wherever soil has become contaminated and the contamination poses a threat to people or the
environment, a series of questions inevitably emerges: Does the site need to be cleaned? What
types of remedial measures or actions should be taken? When will the site be safe to use? What
level of residual contamination is acceptable? These and other concerns often are expressed by
the simple phrase "how clean is clean?". Unfortunately, the answer is not so simply stated and at
the present time few jurisdictions have established acceptable soil concentrations or clean-up
guidelines.

The process of deciding whether to reduce or remove soil contaminants and render a site suitable
for use is a complex issue. Many factors need to be considered including the type of industry
that used the site, the contaminants that are present, the age of the plant, site-specific
characteristics such as  its geography,  geology, hydrogeology, and climate, past waste
management practices, and the proposed future use of the site. The extent and costs of clean-up
activities are largely determined by the level of contamination which, from environmental and
human health standpoints, can safely be left on-site.

To provide direction and guidance to decommissioning efforts across Canada, the Canadian
Council of Environment and Resource Ministers (CCREM; subsequently renamed the Canadian
Council of Ministers of the Environment or CCME) established the Decommissioning Steering
Committee (DSC). Members of the DSC include Environment Canada, the environment
ministries of Alberta, Ontario, and Quebec, and several industrial associations. In 1987, the DSC
awarded a contract to a consortium of companies to investigate various aspects of
decommissioning. SENES Consultants Limited took on the task of creating a computer program
capable of deriving clean-up guidelines for industrial sites where redevelopment is being
considered. The result of this effort is the AERIS program, an Aid for Evaluating the
Redevelopment of Industrial Sites. The version of AERIS described in this paper currently is
being reviewed by the Technical Working Group of the DSC and is expected to be finalized in
1989.
      Presented at the Fourth Conference on Petroleum Contaminated Soils: Analysis, Fate,
      Environmental Effects, Remediation and Regulation, University of Massachusetts, 25 to,
      28 September 1989, Amherst, MA                                          •  ,.
1 -    Senior Environmental Engineer, SENES Consultants Limited, 52 West Beaver
      Creek Road. Richmond Hill, Ontario L4B 1P9
2 -    Environmental Scientist, SENES Consultants Limited
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2.0   BASIC PROGRAM STRUCTURE


2.1 Underlying Premises and Constraints

While the broad objective of this study was to develop a model for establishing site-specific
clean-up guidelines, the process of establishing guidelines is far more complex than can be
represented by a mere computer model. As such, it was recognized from the beginning of the
modelling effort that whatever program was developed, it should not be perceived or used as a
sole arbiter in setting criteria. Accordingly, the acronym AERIS was chosen to help users
remember its intended use, that of being an aid for evaluating the redevelopment of industrial
sites. As an aid, AERIS can be used to identify the factors that are likely to be major contributors
to potential exposures and concerns at sites and those aspects of a redevelopment scenario with
the greatest need for better site-specific information.

The typical user originally was assumed  to be an environmental scientist, but not necessarily an
expert in understanding environmental fate, toxicology, computer programming, or the other
disciplines that are represented in the model. It was also assumed that some users  probably
would use AERIS to study generic situations while others would be interested in specific
scenarios. Those interested in specific scenarios might have some site-specific data but likely
would be uncertain about some of the many factors that can be considered in such an evaluation.

The assumptions about the  intended uses and users, together with the objectives and constraints
noted above,  influenced a series of decisions made at the outset of model development about
basic model characteristics:

       AERIS would be structured so that each run evaluates one chemical for one receptor,
       one land use, and one environmental setting. This may require a user to run the model
       several times and base decisions on the collective  outcomes of those runs. Accordingly,
       AERIS would be designed so that adjustments  to input parameters could  be made
       relatively easily.

       The user should be given the opportunity to select default values for various parameters
       or provide  site-specific inputs so  that the redevelopment scenario in the program can be
       made to resemble acrual situations of interest. As a result, AERIS would include default
       values and  various aids to help users select appropriate values.

       AERIS would consider only those exposures that are experienced on-site. Off-site
       exposures  such as those that might be experienced by people whose drinking water
       supply is down gradient of a site or who consume commercially-sold produce raised at a
       former industrial site would not be calculated. Off-site populations  would be considered
       indirectly by comparing concentrations in air, water, and produce with existing
       environmental criteria such as point-of-impingement criteria for air quality  and drinking
       water objectives.

       AERIS would be designed to evaluate situations where the soil had been contaminated
       sufficiently long ago to establish equilibrium or near- equilibrium conditions between the
       various compartments of the environment. These conditions should apply  to most sites
       that are being considered for redevelopment.

       It would be assumed that the concentration of the contaminant in soil is constant across
       the site and over the depth of soil that is contaminated. Furthermore, the concentration is
       assumed to remain constant over time (although there is the option to correct model
       results for degradation).
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As such, AERIS is not suitable for evaluating recent spill sites or locations being considered as
candidates for receiving wastes. Nor is it suitable for calculating changes in environmental
concentrations or exposures over time due to ongoing contaminant contributions from a constant
or sporadic source.

Based on many of these considerations, it was decided to design AERIS to run within an "expert
system" programming environment. This facilitated the creation of a model in which the user has
the option of entering either site-specific data or relying on default values. At each point where
the user is asked for information, on-screen assistance can be invoked to help a user make
decisions and understand how the choices  can affect the outcome. The entire process has a
relatively high degree of "friendliness" and provides some automatic error checking.

Because it runs within an "expert system" programming environment, AERIS  consists of four
basic elements - an "intelligent" preprocessor, a supporting data base, component modules, and a
postprocessor.


2.2 The Preprocessor

The preprocessor takes  the form of a series of questions that AERIS asks the user about the
redevelopment scenario to be evaluated.  These questions and answers collectively are referred to
as the "Input Session". The answers are used  to create a "context" file that describes the scenario
of interest. Context files can be saved and recalled at the user's discretion.

The preprocessor is referred to as "intelligent" due to the utilization  of expert system technology.
The preprocessor uses a set of rules (collectively referred to & a "knowledge base") to establish
a structure to the decision support offered; to  aid the user in  estimating unknown  input
parameters, and to control the flow of information between other program components. The
preprocessor contains the "control modules"  which are responsible for the user interface during
the input and output  sessions, the inference flow mechanism, the retrieval of information from
the data base, and the management of information flow among the component modules.

The preprocessor uses rules to determine if and when goals are met. Many of the rules are in the
form  of If... Then... Else statements which represent the decision making that an expert would
consider when evaluating this type of scenario. A rule may be predicated upon one or more
submles. The resulting branched arrangement formed by the rules is similar to that of a decision
tree. If sufficient information is gathered during the Input Session, the preprocessor passes the
data to the component modules. Only those modules deemed appropriate by the preprocessor are
activated.                 ,                                                 •'-','•''


2.3 The Component Modules

The component modules contain algorithms that estimate contaminant  concentrations in various
compartments of the environment. The estimated concentrations serve as the basis for estimating
exposures via various routes of exposure. Figure 1 indicates the sequence that the modules are
used in AERIS and shows how they are interrelated by the information  that flows between them.
If concentrations of a contaminant have been measured in one or more  compartments of a site, a
user has the option to override the estimated concentrations with the site measurements.

The  Correlation Module is used to predict  mass transfer coefficients. The predictions
subsequently are used in the Air Module which calculates the flux of chemical from the soil into
outdoor air and into basements of buildings where it can be inhaled by  a site user or visitor. The
rate at which a chemical will be transported from soil into the outdoor air is influenced by
                                         152

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                             FIGURE  I
                COMPONENT  MODULES

              AND   INFORMATION  FLOW
                         Data ilia generated
                         during Input session
                        chemical
                        and sito
                        data
                Correlation
                module
                                      chemical
                                      and site data
                                      and cone. In
                                      soil
                                                Rule basel
             mass
           transfer,
        coellicienl
c
Rule base
 Ruia base
3
Air
module

ieT) 	 ^

-X
\.
\
Indoor s
outdoor
cone.
'
7
Inhalation
Modulo
                                 unsaturated
                                 zona module
                        eonc. In
                      ground water
                                      doses from
                                      Ingesting soil, dust
                                     produce, and
                                     ground water
        doses Irom
        Inhaling vapours
              andduit
                          Total do**
                          mcdula
                       Data lite generated
                      during output session
                             153

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properties of the soil, properties of the contaminant, and environmental conditions.

The Unsaturated Zone Module predicts concentrations in soil-water and soil-air in the soil above
the water table.  It assumes that there is a contaminated  layer that starts at the surface and that
the user can define the layer in terms of its typical or average depth and concentration of
contaminant over that depth. If appropriate, there can be an underlying non-contaminated soil
layer. The Saturated Zone Module predicts concentrations in  ground water. Key factors it
considers include the depth of contamination with respect to the  depth to. the local water table,
and soil characteristics.

The Produce Module is used to estimate concentrations in produce grown on the site. The uptake
of chemicals is assumed to  be contributed: by root uptake and foliar deposition of local soil
particles. The extent of uptake is influenced by the type of produce, length of growing season,
chemical properties of the chemicals, and soil  characteristics.

In the Ingestion Module, the intakes of water, soil, and garden produce are estimated. The
concentrations in the water, soil, and produce are determined in the Saturated Zone Module,
Unsaturated Zone Module, and Produce Module, respectively. In the Inhalation Module, the
amount of chemical inhaled by the receptor while outdoors and indoors are calculated. Both the
inhalation of vapours and paniculate matter are taken into account.

In the Total Dose Module, the doses via all pathways are combined. The total is then compared
to the "acceptable" dose level.  The user can decide  whether all or some  fraction of the
"acceptable" level is to be used. While human health often will be often be the most stringent
basis for setting clean-up guidelines, a user has the option of specifying a concentration in any
one of several environmental compartments as the basis for calculating an "acceptable" soil
concentration.


2.4 The Post Processor

The results calculated by the component modules are passed to the  postprocessor, which offers
the user various ways of displaying the results  during the  "Output Session". Each run of the
model concludes with tables that display dose estimates for each route and the identification of
an "acceptable" soil concentration. Three types of graphical summaries can be displayed: a plot
of soil concentration versus dose: pie charts that show the relative contributions of each route to
total  exposure; and diagrams that compare the calculated  "acceptable" concentrations to
guidelines or criteria issued by regulatory agencies.


2.5 The Data Base

The AERIS  data base can provide much  of the information needed for the calculations. Informa-
tion is retrieved as the user answers questions  concerning the scenario to be evaluated. The types
of information that can be retrieved include physico-chemical data, "acceptable" dose levels,
bioavailability factors, concentrations associated with other  types of adverse effects, guidelines
or criteria from various jurisdictions, receptor characteristics, meteorological data, and physical
characteristics of soils and underlying formations. The data base in AERIS has information foe

       two types of site users: an adult and a young child                                ;
       four future land uses:  residential, commercial, recreational (park land), and agricultural
       more than 30 organic  compounds and three inorganic  substances
       the meteorology of six Canadian cities: St. John's, NFLD, Montreal, PQ, Toronto, ON,
       Winnipeg, MN, Edmonton, AL, and Vancouver, BC
       physical characteristics of nine soil types and 14 underlying formations.
                                         154

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The user has the opportunity to edit all of the information retrieved from the data base so that the
redevelopment scenario can be made to resemble the actual situation of interest. AERIS also
includes default values and various aids to help users select appropriate values.


2.6 Pathways Considered

Site users can be exposed to substances present in site soil through various pathways (routes of
exposure). AERIS allows all or any of the following pathways to be considered: inhalation of
vapours and paniculate matter when indoors and outdoors; direct ingestion of local soil and
indoor dust; ingestion of plants grown on-site; and ingestion of ground water (see Figure 2).

The extent to which a person is exposed to a substance by any of these pathways is influenced
largely by the physical characteristics of the person and the way(s) that they use the site. The
AERIS data base contains information for two types of individuals (an adult and a young child)
and four types of future land use (residential, commercial, recreational, and agricultural). A
program user has the option to use any or all of the default values or can replace default values
with specific values at their discretion.

The characteristics associated with residential land use is directed towards estimating doses that
result from the full-time use of the site. The receptor  is assumed to live in a single-story house
with a full basement located in the middle of the site. A garden on the property supplies fruits
and vegetables.

Commercial land use  is intended to estimate doses that result from spending a substantial
portion of most days on a site inside a building. As such it is analogous to portraying an office
worker  or a child at a day-care centre. The building is assumed to have one story and no
basement.

Recreational land use is intended to generate doses received by frequent visitors to a park or
playground. While on-site, visitors are assumed to be engaged in vigorous activities.

The characteristics of agricultural land use are similar to those of residential except that larger
amounts of time are  spent outdoors and paniculate matter levels at elevated for a portion of the
year as they would be during plowing.


4.0  SAMPLE RESULTS

To illustrate various aspects of the AERIS program and its response to different sets of input
parameters, two  hypothetical redevelopment scenarios have been created. Scenario "A" has
characteristics typical of those that might be encountered at a site in southern Ontario, while
Scenario "B" is more representative of a site in central Alberta. Table 1 displays the  information
used to portray the two scenarios.

The AERIS program was used to identify "acceptable" soil guidelines for each scenario by
considering two soil contaminants (benzene and lead), for all four of the land uses addressed in
the data base, and using the young child as the receptor. Table 2 presents the results for both
scenarios.

For benzene, the "acceptable" soil concentrations for Scenario "A" (0.08 to 0.6  mg/kg) are
slightly higher than for Scenario "B" (0.04 to 0.6 mg/kg). The only guidelines in Canada include
a value of 0.5 mg/kg recommended by the Province of Quebec as the threshold at which detailed
site investigations may be needed. The lower concentrations in Scenario "B" stem from the
                                            155

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                        FIGURE Z

   PATHWAYS  CONSIDERED IN AERIS
               QROUNOWATER  FLOW
POTENTIAL PATHWAYS*
    DIRECT INQEST10N OP SOU.
    INHALATION OF PARTICUUATE MATTES
    INGESTION OF GARDEN PROOUCS
    DIRECT INflESTIQN OF OUST
    INHAU4TION OF PARTOULATE MATTER
    INHALATION OF VAPOURS { BOTH OUTDOORS AND INDOORS 5
    INSEST1ON OF QROUNOWATEH
                            156

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lower organic carbon content in that site's soil and the subsequently higher concentrations of
vapours in air (and higher doses via inhalation). The inhalation of vapours is a dominant
pathway (50 to 84% of total exposure) for benzene in all land uses except recreational (in which
all time on-site is spent outdoors). Associated with the "acceptable" soil concentrations are
outdoor air concentrations well below the air quality criterion from Ontario but ground water
concentrations above the guideline from Quebec. The associated soil values also are less than
those reported to cause odours in air or phytotoxicological effects.

For lead, concentrations for Scenario "A" (8 to 500 mg/kg) are slightly higher than for Scenario
"B" (5 to 15 mg/kg). Soil guidelines from several Canada provinces lie in the range of 200 to
1000 mg/kg. Ingestion of produce dominates the exposure in Scenario "A". AERIS makes no
allowance for reductions of concentrations in produce that result during food preparation such as
washing, peeling, or boiling. As a result, the estimated doses for eating produce likely exceed
actual doses. This becomes an important consideration in interpreting the output for scenarios in
which the consumption of produce is a major pathway.

The sandy soil in Scenario "B" results in higher concentrations of lead in ground water and
therefore doses via that route are significantly greater than in Scenario "A". The dominating
influence of ground water ingestion in Scenario "B" results in "acceptable" soil concentrations
considerably lower than ."those being  used or considered by some regulatory-agencies. The
inclusion of site ground  water as a source of exposure is an unlikely condition especially in
urban areas. If ground water had not been included as a pathway, the "acceptable" soil value for
Scenario "B" would have been approximately 100 to 450 mg/kg. For both scenarios, the use of
lead-specific bioavailability factors (rather than the default values) likely would significantly
increase the "acceptable',''soil concentrations.


5.0 CONCLUSIONS

AERIS has achieved many of the original objectives set for this project: it is highly user-
friendly; it can be used even if various pieces of site data are missing;  it is highly flexible in the
types of contaminants and scenarios it can evaluate; and it generates site-specific clean-up
guidelines. During die development of the model, it also was realized that  with increasing ease
of use also came the increasing possibility of misuse. While the original goal was  to create a
product that even a novice could use to develop guidelines, the developers have come to regard
the model as being better suited to assisting experts to evaluate situations expeditiously and
consistently. Rather than  being used as a surrogate for expertise, its preferred role is as a tool to
assist experts. That AERIS should not be perceived  to be a substitute for expertise is evident in
the cautionary notes that the developers suggest be applied to the interpretation of model results:

       The conservative, risk-based philosophy and default values that are used when health
       concerns  are the basis for evaluating a site make it possible to generate "acceptable" soil
       concentrations lower than those that regulatory agencies may be using or considering.
       Conversely, relatively high "acceptable" soil concentrations can be identified when using
       AERIS if the scenario being evaluated generates very  small dose estimates or the
       important exposure pathways are relevant for chemicals with  certain physico-chemical
       properties or environmental behaviours.

       The algorithms used to estimate environmental fate  and concentrations in environmental
       compartments as a function of the concentration in soil have been verified  but not
       calibrated (that is, the predictions of the algorithms have not been compared to
       concentrations measured  at actual industrial sites in various environments). An
       assessment of the model's worth may only be possible once it has been used to evaluate
       several real situations.
                                         157

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Some of the algorithms represent processes that are not well understood (such as plant
uptake) and the overall approach may require site complexities to be replaced with
generalizations.

"Acceptable" soil concentrations determined by AERIS should not be taken as absolutes
but rather as being indicative of appropriate concentrations. Scenarios should be
evaluated by running AERIS several times with key parameters adjusted between runs to
develop an appreciation of the sensitivity of the output to input data or assumptions.
                                   158

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                                 Table 1

  PARAMETER INPUTS FOR CHARACTERISTICS  OF SCENARIOS  "A" AND  "B"

                         Scenario "A"              Scenario "B"

meteorology                Toronto                   Edmonton

site length                 1000 m                    1000 m

soil type            stiff, glacial clay         uniform, dense sand
underlying formation
ground water table
soil pH
aquifer thickness
Kd. for lead
depth of contamination
organic carbon content
hydraulic gradient
Other A33umntion3 for Both
unweathered
marine clay
1.5 m
7.4
5 m
0.04 m3/kg
1 m
2.5 %
0.01
Scenarios
silty
sand
3 m
6.0
5 m
3.5 m
1 m
1 %
0.01



3/*g




  - dissolution dominates over desorption for lead
  - all bioavailability factors set to default values
                                  Table 2

    "ACCEPTABLE"  SOIL CONCENTRATIONS FOR  SCENARIOS "A"  AND  "B"

Chemical/                Scenario "A"              Scenario "B"
  Land Use                   (mo/kg)                    (mg/kg)

benzene
  residential                 0.12                     0.04
  commercial                  0.36                     0.20
  recreational                0.60                     0.64
  agricultural                0.12                     0.04

lead
  residential                 8        '                4.9      ,
  commercial                493                        14.3      >
  recreational              111                        11.4
  agricultural                8                        4.9
                                   159

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      NATO/CCMS Guest Speaker:



           Colin May field, Canada



           Anaerobic Degradation
161

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                       Anaerobic biodegradation


Aromaf ics - reviewed by Berry et al. (1987) - Microbiol. Rev. 51: 43-59.


Overview


Two basic pathways for ring reduction- hydrogenation and hydration


Hydraf ion can occur using oxygen from water forming phenol from benzene and p-
   cresol from toluene (Vogel and Grtbic-Galic, 1986 and 1987).


Five anaerobic processes that can degrade aromatics -


1. Photometabolism

2. Fermentation

3. NHrnf e respiration (denifrifleation)
4. Stiltate reduction
5. Mclhaiiogenesis
                                                            i,  Benzena
                                                            2, Cyelonoxona
                                                            3,
                                                            4,
                                                            5
                                                            6. f,2 -
                                                            7- 2- Hydronyhwonaio
                                                            S.
                                                            ID
                                                            12.
                                                            13 Phenol
                                                            14.
                                                            15
                                                            16
                                                            I? Heptanoaie
                                                            18 To lu e no
                                                            19 MelhytcyCtohBuanQ
                                                            2O, Bi-nivlAtchal
                                                            21. San/otdehjds
                                                            22. Semoaia
                                                            23 o-orp-cmw:!
                                                            28 (
                                                            27. I
 FIGURE-2
 Generalized Anaerobic Degradation of AfDmafic
 Compounds.(Modified from Berry  eta/., 1987,Evans, 1977,
 and Kaiser and Hanselmann, 1982.)
                                    !162

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                   Microorganisms in groundwater

 1. Numbers - range from 1 to 10,000,00 per gram/dry weight using modern techni-
   ques,

 2. Activity - turnover times of naturally occurring compounds (aniino acids and
   sugars) range from 50 to 2000 hours (Canadian sites at slower end of values!)

 3. Specific activity per cell varies less than numbers - probably the major dif-
   ference between sites was in terms of percentage of active cells, not specific ac-
   tivity per cell.

4. Bacteria tend to be adapted to low nutrient conditions - they are oligotropliic.

5. The microorganisms in groundwater do not seem to be inhibited by "normal"
   (i.e. commonly found) levels of contaminants such as
  monoaromatics,PAHs,creosote and creosote by-products, phenols, halogenated
  aromatics and methanes, and heavy metals.
                                  163

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Calculations of free energy changes;
| Electron Donor
1
i
* acetate
s
i acetate
j acetate
, acetate
j
t
1
| glucose
glucose
glucose
glucose
glucose
i

Electron Acceptor

02

NO3'
S042"
COa

02
N03"
S042*
C02
glucose
(fermentation to
etkauol)
kcal/electron
equivalent
-25.28

-16.03
-1.52
-0.85

-28.70
-19.45
-4.94
-4.26
.-2.43
'


                          164

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  Metastable intermediates:
                                            -..-••-   i
  Glucose fermentation to methane:                         j
  Stages in fermenation -
;  1. Glucose + HCOa"  	   acetate + propionate +
                               butyrate +  hydrogen
  (kcal = -2.74 = 64.3% of overall total)
  2. Acetate + H2O  	   methane + HCO.i-
|  (kcal = -602 = 14.1% of overall total)
i      . .
|	:	.	
  3. Butyrate + H2O  	  methane + HCOa'
  (kcal  = -0.075  = 1.8% of overall total)
!   4. Propionate + H2O  	   methane +
•   (kcal = 0.093 = 2.2% of overall total)
   5. H2 + CO:   	•     methane +
   (kcal = .75 = 17.6% of overall total)
                           165

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 o
 o
•
 o
•p
 u
 QJ
Hi
       formate
 glucose


 glycerot

 nethonol
pyruvate
   glyclne
  lactate
  ethanol
succlnate
benzoirte
 acetate
 methane
                      -5      -10     '-15      -20     -25
                           kcal  /electron  mole
                                                         -30
-35
                   8-

        o

        I
        *J>
        o>
        o
                           First" Order
                                 Logistic
                                           Mcnod,
                                           no Growth
                                           Monod,
                                           With Growth
                                                    Zera-Ordery
                                                     Logarithmic
                       T      I	1	1	1	1	T
                     0.001   0.0!   O.I     i     10   100   1000
                     Initial  Substrate Concertrafionfug/ml)

                    FIGURE -3a
                    Kinetic Models as a Function of Substrate
                    Concentration and Bacterial Cell Density (From
                    Alexander, 1985)
                                       166

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 Fermentation
 pyrogallol, gallic acid
 2,4,6-hydroxybenzoate
 phlorglticinol
 syringic acid

 o-methyl groups of
 aromatic acids
COi & acetate
acetate & hydroxylated
derivative of acid
1982 (Scliink & Pfennig)
1985 (Frazer & Young)
Denitrificatiort
Compound metabolized
Prodnet(s)
        Date
p-hydroxybenzoate

benzoate

benzoate
3 and 4 hydroxybenzoate
l-cyclohexenecarboxylate

CCLi
brniniuateci lialonietlinnes

3-tliiorophtbalate

hydroxybenzoate
hydroxybenzoate

cycloliexanecarboxylate
adipate
1970 (Taylor)
1975 (Williams & Evans)
1984 (Braun & Gibson)
chloroform *
1983 (Bouwer & McCarty)
2 and 3-flnorobenzoate     1981 (Aftring et al.)
phenol
1989 (Kulin et al.)
* may be chemical reaction (reduced iron ?)
                                  167

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 Siilfate Reduction
 benzyl alcohol, p-cresol
 antliranilic acid

 benzoate

 isomers of cresol
CO2
                 (1981) Balba
 (1983) Widdel et al,

 (1979) Smolenski &
       Siiflita
 Metlianogenesis
phenylaeetate, hydrocinnamate,
cinnninate, tyrosine, benzoate

benzoate

lignin ferulic acid

3-cliIorobenzoate

Iialogeuated aromatics
(many)
methane
methane
                 1934 (Tarvin & Buswell)
1976, (Ferry & Wolf)

1979 (Healeyetal.)

1984 (Shelton&Tiedje)

1982 (Siiflita et al.)
1983 (Horowitz)
1985 (Suflita &MiIIer)
1986 (Wilson et al.)
and others.
N.1J. Most results involve "nietlianogenic consortia" of bacteria, not pure cultures.
dehalogenated
products
                                  168

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Factors affecting bioremediation in groiindwater -
1. Contaminants - are they amenable to aerobic and/or anaerobic biodegradation ?

2. Concentration - are the concentrations present likely to support growth or be
   metabolized by co-metabolism or secondary substrate metabolism ?

3. Concentration of nutrients, electron acceptors, dissolved oxygen, etc., in the
   groundwater.

4. Hydrogeological conditions (site specific)
         •'" porosity, flow pattern and velocity
           - DOC and TOC and their effects on adsorption and retardation
       :    - mixing zones, heterogeneity of porous media            '
           - historical data on contamination events
           - other sources of contamination or nutrients
5. Intermittent, controlled, alternating injections of low levels of oxygen and
   electron acceptors to modify groundwater in a localized area.  Could set up al-
   ternating aerobic and anaerobic environments without excess  biomass produc-
   tion. Could set up process leading to eventual methanogenic conditions (and
   consequent bioremediation activity), subsequent addition of oxygen could lead
   to methane-oxidizing activity. Addition of nutrients would then start process
   again.                                                                 •'•
In all cases need to apply stochiometry of reactions to calculate additions of
  nutrients, electron acceptors and oxygen.
                                    169

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                                Summary

1. Aerobic biodegradation and remediation is well-established in groundwater
   systems.
2, Anaerobic bioremediation theory and teclmology is less well-understood; there
   are few well-documented field examples.
3. Some non-aromatic organic compounds are obviously more amenable to
   anaerobic bioremediation.
4, The hydrogeology of the site must be understood before using bioremediation
   technology. Even aerobic groundwaters can be "driven" anaerobic by
   biodegradation of contaminants.
5. Anaerobic bioremediation has some advantages when it is applicable;
           The electron acceptors (NOj", SO42", COa) are soluble and move rapidly in
                   groundwater since they are not adsorbed.
           The contaminant plume can be "overtaken" by the treatment
           Final contaminant concentrations could be very low.
           Can be cheaper and less obtrusive than other methods.
           Can be used in conjunction with other methods.
                                  170

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       NATO/CCMS Guest Speaker:



                A. Stelzig, Canada



         Cleanup Criteria in Canada
171

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DECOMMISSIONING AND CLEANUP
    CRITERIA OF INDUSTRIAL
     FACILITIES IN CANADA
       NATO/CCMS MEETING
         NOV. 6-9 1989
           MONTREAL
              172

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OVERVIEW OF NATIONAL
        PROGRAM
  OBJECTIVE
• C C M E
  HISTORY & BACKGROUND
• STATUS OF CURRENT PROGRAM
 DECOMMISSIONING
  OBJECTIVE:

     Establish uniform approaches
     on decommissioning of
     industrial plants, storage
     facilities and waste disposal
     sites.
              173

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     Canadian Council of Ministers
      of the Environment (CCME)


  -  WASTE MANAGEMENT COMMITTEE

     -Responsible  for the  Hazardous
      Waste  Action Plan

     -Added decommissioning of
      industrial sites to action
      plan Sept/86.
                  !
     -Environment  Canada and
      Quebec identified as lead
      agencies.

     -Objective (established by
      waste  committee):

       "Establish uniform approaches
        on decommissioning of
        Industrial plants,  storage
        facilities and waste disposal
        sites."
INDUSTRIAL DECOMMISSIONING
             TASKS
   DEVELOP CLEANUP CRITERIA
   INCORPORATING SITE SPECIFIC
   CONSIDERATIONS
   DEVELOP NATIONAL GUIDELINES
   FOR DECOMMISSIONING
   INDUSTRIAL SITES
                  174

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HISTORY AND BACKGROUND
  • Decommissioning guide
   -consultants report    1985

  • National workshops
   and proceedings        1985
   - recommendations
     steering committee  June 86

  ซ Quebec & Ontario
   Regulatory Initiatives

  • inventory of cleanup
   criteria and
   methodology          May 87
 A  P\tssjss*-/s\m. Jfl Jit e"^c**ปi /"%* I II. i /*>* /*%i Hf"\r"
 M: i-inouiviivnooiuiNiNva GuiDc
  April 85 by Monenco  Consultants Ltd.


  ป SCOPE AND PROBLEM DEFINITiON

  • GENERAL PRINCIPLES
     -Planning
     -Site Assessment
     -Site Investigation
     -Cleanup Criteria
     -Site Cleanup
     -Cleanup Confirmation
     -Long Term Monitoring
     -Regulatory Agency Involvement
     -Pubic Relations
     -Preventive Measures

  • CASE HISTORIES

  ป CONCLUSIONS   175

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      B: WORKSHOPS

 Calgary Nov. 85
 Ottawa Dec. 86

 STEERING COMMITTEE

    -Industry/Gov't
    -Define Objectives
    -Manage Workshops

 OBJECTIVES

    Advance state of the art
    level of understanding

    Exchange information
      -Share expertise and
       experience
      -Identify needs
CONCLUSIONS/RECOMMENDATIONS
           APRIL 1986

  - Cleanup criteria and guidelines
    (Highest priority)

  - Small facilities


  - Field programs

  - Treatment & Disposal


  - Ground water cleanup

  - Long term monitoring
    Role of gov't and public
                 176

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    RECOMMENDATIONS
JUNi 1986

- Letter to Federal/Provincial ADM's
 and Industry Associated Presidents

- Workshop  Recommendations

  -Highest priority
    -Criteria
    -Inventory
    -Cooperative  effort
    -To follow up
    - Funding

- Response

  -Recognized need
  -Prepared to  participate
    -Funding
    - Planning
                 a
          INITIATIVES
       Development of policies
       and guidelines
     ป Quebec action level
        - A, B, C
       Ontario decommissioning
       guideline

                   177

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        INVENTORY OF CLEANUP CRITERIA
       AND METHODS  TO SELECT CRITERIA
      REPORT COMPLETED
      APRIL  1987

         -Canada,  U.S.,  Europe
         -Site specific: examples
      REPORT TO WiSTE  COMMITTEE
      MAY 1987
      REVIEW BY MARK RICHARDSON
 U.S. OFFICE OF TECHNOLOGY ASSESSMENT
  Analysis of approaches to set cleanup goals
Unacceptable             Technically and Economically
                       •  '   Impractical    '• •  •

- ad hoc                -restore to background/pristine
                       -beat available technology
Potentially Feasible             Preferred

-national standards        -site classification based on
-risk assessment          use combined with national
-coat-benefit analysis      standards, risk assessment
                       and cost-benefit analysis

                        178

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 U.S. OFFICE OF TECHNOLOGY ASSESSMENT
       NATIONAL. CONSISTENT APPROACH REQUIRED.
No  consistent approach
No consistent levels of cleanup
Factors to be considered when selecting cleanup goals:

  -Inherent hazard (potential to cause harm}

  -site-specific considerations and exposure  (pathways
   analysis)

  -assessment of risks (hazard and exposure, probability of
   adverse effects)

  -available technologies (detection,  quantification,
   remediation)

  -resource limitations (money, trained personnel,
   equipment)

  -Institutional constraints  (laws 4  regulations,
   jurisdiction)
     STEPS IN DECOMMISSIONING ON A SITE-SPECIFIC BASIS


t 	
EXPOSURE PilfflU
\
EXPOSURE LEVEL
DETERMINED
1
EXPOSURE LEVELS
TO ADI
[


I
i

YS 1 BACKGROUND LEVELS
,

S '
i
, . CONTAMINJS
'S
BACKGROIT
i

M LEVELS
TO
m
f
j • -
... ...,._
v:-s., - I

4
COMPARISON OF

t

f
PREDETERMINED GUH
Or NIC
1 !
CONTAMINANT LEVELS
COMPARED TO
LOT


"TTfiT'TrT Tftl B^M^
KLJULii^l ^^

SELECTION OF CLEANUP
LEVELS

f

OP
/TECHNOLOGY

f


T

3EUNES CLEANUP TECHNOLOGIES
ESSARY) miNTMED
i >
LEVELS COMPARE
TECHNOLOGICALL1
SIS Clffl
LEVELS
i


D TO
•_
iNUP

CLEANUP)
*
POST-CLEANUP

MONITORING


                         179

-------
  STATUS  OF CURRENT
         PROGRAM


     ป Project objective

     ป Components of project

     ป A.E.R.I.S.
       (Aid in Evaluating the
        Redevelopment of
        industrial Sites)

     * National Guideline for
       Decommissioning of
       Industrial Sites
Development and validation

(critical components)  of a

method for establishing  site

specific cleanup criteria for

industrial  sites.
               180

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COMPONENTS FOR PROJECT
    REVIEW AND EVALUATION
    OF METHODS
    DEVELOPING OPTIMUM
    APPROACH AND METHOD
    VALIDATING CRITICAL
    COMPONENTS
        PROJECT

 BUDGET         $1.1 MILLION

 SPONSORS

 -Federal Government—50%
  (Environment Canada
   D.S.S.)

 -U.S. EPA  	 35%
 -Alberta
 -Quebec
 -Ontario
 -CPA
 -PACE
 -CCPA
15%
 Project initiation June 1987
      completion feb. 1990
              181

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              PROJECT TEAM
    CONSULTANTS
    Monenco Consultants Ltd.
    Senes Consultants Ltd.
    Cantox Inc.
    Zenon Environmental Inc.
    KRH Environmental Co. Ltd.
                              PROJECT ROLE
                              Management
                              Pathways
                              Toxicology
                              Analytical
                              Laboratory
         PROJECT ORGANIZATION
IcLY
LQOM
CLIENT COORDINATING
[COMMITTEE (I I)
 TECHNlCAL WORKING GROUP  (7)|-
                     EXPERT REVIEW COMMITTEE
 PROJECT MANAGEMENT
M.J. Riddle
D.M. Gorber
                       182

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     METHOD REVIEW
           REPORT
A) Methods and strategies  currently
  used  to  develop  cleanup criteria
  for contaminated sites.
  (completed  January  1989)
    -Reviewed by Technical
    and Steering Committees.
    -Submitted to C.C.R.E.M.
    Waste Committee 12/01/89.
    -Comprehensive  Review
    -Inventory Criteria Report
    Precursor.
        ETHOD  REVIEW
 A-1) EVALUATION  BASIS:
    -Site specific data
    -All environmental  media
    -All environmental  contaminants
    -Incorporate  variety scientific
     data
    -Degrees of contaminants
     exposure
    -Routes of  exposure
    -Risk  assessment
    -Missing data
    -Land use
               183

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     METHOD REVIEW

 A-2)  STRATEGIES:
    -Site classification
    -Environmental standards
    -Risk assessment
    -Cost  benefit
    -Technology
    -Background
     METHOD REVIEW
A-i3) A  combined approach
  and methodology that
  SYSTEMATICALLY considers
  ALL  of the ^trategies.
              184

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           A.E.R.I.S.
(Aid in Evaluating the Redevelopment
 of Industrial
Links  exposure assessment (multi-

media pathway models) with  toxiclty

assessment as part of an overall

risk evaluation procedure.



        OBJECTIVES
 1. Development  of  a risk assessment
  method for selecting cleanup
  criteria,
    -user friendly computer  model
    -human exposure vs  soil
    concentration

 2. Selection of  pollution  transport
  equations for  model based on
  evaluation  in field study.

   Model will aid in selection  of
   cleanup criteria  for cases with
   extensive  contamination (conflict
   between most economical and most
   environmentally acceptable
   approaches).
                  185

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   MODEL  DESCRIPTION


1. Input of site  specific  information

   -  user  responds to questions

   -  approve or change  default
    values

   -  ask for help, background
    information

   -  examples:  soil, climate, pollutants

               land use  - residential
                          commercial
                          recreational
                          agricultural
2. CafciiSation  of  sol!  concentration
  that  results  in  acceptable level
  of risk.
     • Concentration  in air, soil,
     water,  plants; resulting
     human  exposure
     • Comparison  of  exposure with
     ADI
    •  Adjustment of soil concentration
     and recalculation of exposure
                   186

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3.. Graphic  display  of  mode!  output
   -  Recommended cleanup criteria;
    background
    existing  guidelines (Canadian
    water quality)
   - Concentration in  soil  vs water
                            air
                            plants
   r Importance of each pathway to
    total exposure
    NATIONAL GUIDELiNi
 A) GENERIC
    -  not  industry  sector specific

 B) MAJOR COMPONENTS
    -  appropriate steps,  information
     needs, practices and considerations

    -  cleanup criteria and  procedure

 C) PRIMARY BACKGROUND  AND
   REFERENCE  DOCUMENTS
    -  guide
    -  draft Ont &  Que guidelines
    -  inventory  criteria  report
    -  workshop material
    -  current methodology  study
    -  U.S. material
    -  other (he. water quality
         guidelines)
                  187

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                 pECOf^MSSSiOMiNG
             GUIDELINES

I Introduction
2. Legislation
3. Planning
4. Site assessment
5. Reconnaissance testing program
6. Plant phasedown  ,
7. Development of cleanup criteria
8. Detailed testing program
9. Preparation of cleanup plan
10. Implementation of cleanup plan
11. Confirmation testing
12. Long term monitoring
13. Approval
14. Land use control
15. Liability
                  {
IS. Preventative measures
                    188

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THE  DEVELOPMENT OF SOIL

    CLEANUP  CRITERIA
         IN  CANADA

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    CONTAMINATED SOIL CLEANUP
            IN CANADA
             VOLUME 1
      METHODS AND STRATEGIES
    CURRENTLY DSHD TO DEVELOP
       CLEANUP CRITERIA FOR
        CONTAMINATED SITES
         prepared for the
Decommissioning Steering Committee
            1988-09-16
                  190

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                                 ABSTBACT

           A potential threat to human and environmental health is posed by
the existence of toxic substances  at closed industrial sites or inadequate
waste disposal sites.   It  is  generally  acknowledged that this potential
threat must be reduced to  an  "acceptable level" or eliminated completely.
To deal with this problem  (i.e.  how  clean is clean?) various governments
and regulatory agencies in North America  and  Europe use a wide variety of
strategies and  approaches.    These  strategies  can  be  divided into the
absolute method, which is geared  toward establishing a fixed concentration
for a given contaminant in a specific medium, or the relative method, which
derives a site-specific contaminant  concentration  to protect human health
and the environment.

           The  Canadian  Council  of  Resource  and  Environment Ministers
(CCREM) have recognized the inconsistency of the various approaches used in
Canada to develop  cleanup  criteria.    CCREM  has  identified the need to
establish a uniform approach for the development of cleanup criteria, which
incorporates site-specific characteristics and  is protective of both human
health and the environment.

           An evaluation of the various strategies used by governmental and
agency  jurisdictions  i.n  North  America  and  Europe  to  develop cleanup
criteria was made in terms of their capability to:

     o     incorporate site-specific data;
     o     address all environmental media;
     o     address all environmental contaminants;
     o     incorporate a wide variety of scientific data;
     o     distinguish various degrees or periods of contaminant exposure;
     o     deal with various routes of exposure;
     o     deal with the effect of more Chan one contaminant exposure to a
           biological receptor;
     o     differentiate   betveen   non-carcinogenic   and   carcinogenic
           contaminants;
     o     incorporate risk assessment;
     o     deal with missing data; and
     o     incorporate the desired end land use.

Only the strategies adopted  by  the U.S. Environmental Protection Agency,
the  U.S.  Army  and  the  State  of  California  had  the  aforementioned
capabilities.

           In view of the  many  strategies  utilized for cleanup criteria
development and the requirements  for  the development of a scientifically
defensible,  easily  standardized,  and   "user-friendly"   system,   it  is
recommended that  a  combined  approach  be  investigated.   This combined
approach would incorporate elements  from  strategies in both the absolute
and relative methods  categories  for  the  purpose  of providing the most
cost-effective  mechanisms  to  meet  the  diversity  of  sites  requiring
cleanup.  This strategy would  be  consistent  with the need identified by
CCREM for a uniform approach to  the development of cleanup criteria which
incorporates site-specific characteristics and which is protective of both
human health and the environment.
                                     191

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                          EXECUTIVE  SUMMARY
          A potential  threat to human and  environmental•health  is posed
by  the  existence of toxic  substances at closed  industrial.sites  or In-
adequate waste  disposal sites.   It is generally  acknowledged  chat this
potential threat must  be reduced to  an  "acceptable  level"  or eliminated
completely.  While this concept is  admirable, the actual determination of
what toxic  substances  should be eliminated and  exactly  how to define an
"acceptable level"  of  a toxic  substance can become  very,involved.   To
deal with this problem (i.e. how clean is clean?) various governments and
regulatory agencies  in North America  and Europe  use a wide  variety of
strategies  and  approaches.   These  strategies  can be  divided  into  two
broad categories:  absolute methods and relative methods.

          The absolute  methods  generally focus  on an  established value
(or  fixed  concentration)  of a  given contaminant in a  specific  medium
(I.e.  air,  water  or  soil).    Exactly how  this  established  value  was
derived  is  usually  less ' important  than  the  fact  that  a  specific
regulatory agency or government use it to define:

     o    contaminated  versus uncontaminated;
     o    an acceptable level of contamination;  and/or
     o    various levels of contamination requiring different responses.

          The relative  methods focus on, the derivation of a  site-specific ,
value which  will protect  human health  and the  surrounding  environment
according to:

     o    the physical-chemical properties of the contaminant;
     o    the movement  of  the contaminant through environmental  media at
          the site;  and                                         .     ,   -
     o    the  human interaction with those environmental media.
                                    192

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          The  Canadian  Council  of  Resource  and Environment  Ministers
(CCREM) have recognized  the  inconsistency of the various approaches used
in Canada to develop  cleanup criteria.   CCREM has identified the need to
establish a  uniform  approach  for  the  development  of  cleanup  criteria,
which  incorporates  site-specific  characteristics and  is  protective  of
both human health and the environment.

          Specific  alternatives  or  strategies  for   the  development  of
cleanup criteria  (as  subsets of the  general categories  of  absolute  and
relative methods) can be described as:

     o    ad hoc practices;
     o    site-specific risk assessment;
     o    national goals for residual contamination;
     o    restoration to background or "pristine" levels;
     o    technology-based standards  (best available technology or best
          engineering judgement);
     o    cost-benefit approach;  and
   •  o    site  classification and  restoration  relative  to present  and
          future land use.

          After a review of  these alternatives,  the  U.S.  Office  of  Tech-
nology Assessment  (1985)  concluded  that  the  ad hoc  practices  were  no
longer acceptable and cleanup criteria  based  on background or  pristine
levels did not make environmental,  technical or economic sense.   Although
attractive,  technology  based standards  did  not  offer  human health  and
environmental protection  comparable  to  the cost  of  implementation.   The
strategies of setting national goals, the cost-benefit  approach  and site
specific risk assessment  could be  used, but each one poses  considerable
problems and has substantial limitations.  Of all the strategies, cleanup
criteria based  on site  classification (i.e.  present  and  future  use of  a
site and surrounding area) seemed the most beneficial approach.  An even
better approach might be  obtained  by utilizing  a combination of some  of
                                    193

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the strategies.  Thus, a single strategy might include various components
of site classification, risk assessment, cost-benefit analysis and exist-
ing,  relevant  environmental standards,  as  well as  consideration  of  the
available cleanup technologies.

          Existing strategies used in North  America  and  Europe according
to governmental or agency jurisdiction are described below.

     o    Alberta has  no  systematic  approach to cleanup criteria selec-
          tion.  The province requires the responsible company or organi-
          zation to  Identify  site: contaminants, contaminants  of concern
          and cleanup levels for governmental approval.

     o    Ontario is revising  its:guide for restoration and  rehabilita-
          tion of  industrial  sites.   This  document provides  details  of
          the data and information1 required  for governmental  approval  of
          any cleanup plan.  Numerical  guidelines  are  provided for some,
          mainly inorganic, contaminants.

     o    Quebec uses  an approach based on  both  the Dutch  and  French
          systems.   This  system uses specific numerical values  (concen-
          trations)  of soil and grbundwater contaminants  to define back-
          ground,  moderate contamination  and severe contamination, as a
          basis for  the management of contaminated  material.

     o    The State  of  California utilizes a  standardized, systematic and
          integrated set  of individual  tasks (the Site  Mitigation Deci-
          sion Tree) to set site-specific cleanup criteria for any media
          at any abandoned or uncontrolled waste site within the  state.

     o    The State  of New Jersey derives site-specific,  acceptable soil
          contaminant  levels  as the end-product of calculations  describ-
          ing human  exposure to contaminated  soil  and groundwater  (as a
          result  of contact with  contaminated soil).    The  system also
                                   194

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quantifies  the  exposure  of  aquatic organisms  to contaminated
surface water (as a result of contact with contaminated soil).

The  State  of  Washington   has   a  standardized,  systematic,
priorized set of  procedures for  initial  and long-term cleanup
of contaminated  sites.    The system is based on  the potential
for  contaminant  migration through all environmental  media  to
cause acute and chronic adverse human health effects.

The  U.S.  Army  Preliminary Pollutant  Limit Value  approach  was
developed to  predict the probable environmental  limits  for a
soil contaminant  to  affect  human  health  through  a  variety  of
pathways.  Each pathway is described by a specific mathematical
equation derived  from  the physical and chemical  properties  of
the  contaminant  and  the  transporting  media.   Single pathways
are combined to a total daily dose to a receptor organism.  The
contaminant concentration at  the  source would  Chen  be reduced
until  the  total  daily dose  reaching  the receptor  is at  an
acceptable level.

The U.S. Environmental Protection  Agency has  a  specific set  of
procedures (the Superfund Public Health Evaluation Manual)  for
the  derivation  of cleanup criteria to prevent adverse health
effects in the exposed human population.   The main features  of
this system are  the quantification of the  migration of contami-
nants among environmental media  and a detailed human exposure
assessment.

The Netherlands  has established a list  of  contaminants (approx-
imately 50 organic  and inorganic  chemicals  and  chemical mix-
tures)  and associated  concentrations  in soil and groundwater.
Three levels or  categories  of  contamination defined by  these
concentrations   are:    1)  normal  or  background;  2)  moderate
                              195

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          contamination; and  3) severe contamination.   These concentra-
          tion  levels then  form the  basis for  recommendations on  the
          management of contaminated materials.

     o    The  United  Kingdom  has  published a  list of  soil  contaminant
          values ("trigger  concentrations")  below which a site  could  be
          regarded  as uncontaminated.   The trigger  concentrations  vary
          with the proposed future use  of  the  site and have  been adapted
          from existing  guidelines  developed for  other  purposes or  were
          based on professional judgement.

     o    France has published  a list of values for  four  levels of  con-
          tamination  (i.e.  threshold  values) which once attained require
          a response.  These  four levels  (responses)  are:   1) background
          maximum  (i.e.  no response);  2) investigation  threshold  (i.e.
          further  investigation required  before disposition  of  contami-
          nant is  determined);  3) treatment  threshold (i.e.  soil must  be
          treated  to  reduce  contamination)  and  4)  emergency  threshold
          (i.e.  immediate  and  decisive action must  be taken to  remove
          contamination).
                                                 •a
          An evaluation  of  the various strategies used by  governmental
and agency  jurisdictions in North  America and Europe  to  develop cleanup
criteria was made in terras  of their capability  to:

     o    incorporate site-specific  data;
     o    address all environmental  media;
     o    address all environmental  contaminants;
     o    incorporate a wide variety of scientific data;
     o    distinguish various degrees or periods of contaminant exposure;
     o    deal with various routes  of exposure;
     o    deal with the effect of more than one contaminant exposure  to  a
          biological receptor;
                                        196

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     o    differentiate  between  non-carcinogenic  and carcinogenic  con-
                 . ,                           -   -        'ป"•••,
          taminants;
     o    incorporate risk assessment;
     o    deal with missing data;  and
     o    incorporate the desired  end land use*

          Only the  strategies adopted by  the U.S.  EPA, the  U.S.  Army and
the State of California had the aforementioned  capabilities.   In view of
the many  strategies utilized  for cleanup  criteria development  and  the
requirements for the development  of  a scientifically defensible,  easily
standardized, and  "user-friendly"  system, it  is recommended  that  a  com-
bined approach be investigated.  This combined approach would incorporate
elements from strategies in both  the  absolute  and  relative  methods cate-
gories for the purpose  of providing the most cost-effective  mechanisms to
meet the  diversity of  sites requiring  cleanup.  This strategy  would be
consistent with  the  need  identified  by CCSEM  for  a uniform  approach to
the  development  of  cleanup  criteria which  incorporates  site-specific
characteristics  and  which is  protective of  both   human  health  and  the
environment.
                                  197

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           Les  substances  coxiques  se trouvant  dans des  emplacements
 industrials  desaffectes  ou lieux  d' elimination  de dechets  mal  amenages
 constituent  une  menace potentielle  pour la qualite de 1 ' environnement et
 la sante humaine.  II est generalement  admis  que cette menace potentielle
 doit  etre  supprimee  ou  reduite  a  un  niveau acceptable.    Mime  si
 1' intention  est louable,  il  peut  etre, de  fait,   tres  complique  de
 determiner   quelles  substances  toxiques  doivent  etre e'liminees  et  de
 definir  des concentrations  acceptables pour  chacune  d'elles.  Pour
 resoudre  ce  probleme,  les divers  fitats et organismes responsables nord-
 americains et europeens  ont adopts  une grands variete de  strategies- et
 d'approches.   Ces  strategies  se  repartissent  dans  deux  grandes
 categories:   les oethodes absolues  et les methodes  relatives,

           Les methodes  absolues font generalement appel a  des  criteres
 preetablis   (ou  concentration  fixe)  pur  un contaminant  donne  dans  un
 milieu particulier (1'air, 1'eau ou  le  sol).   La -f aeon dont  le  critere a
 ete  elabore   imports habituellemant moins  que 1 'usage qu'un organisms  ' de
 reglementation ou un scat en fait,  soit;

           distinguer ce  qui est ;contamine  de  ce  qui ne 1'est pas;
           etablir un degre  acceptable de contamination; et/ou
           decider du type d' intervention en fonction  du degre de
           contamination.        ,

           Les methodes  relatives  s'appuient sur  une grandeur  qui 'est
 particuliere i  1' emplacement  e]t  qui  dans ces fonctions  particulieres
 assurera la  protection de la sante  et du milieu  environnant.  Ce critere
 tiendra compte:

           des proprietes physico-chimiques du contaminant;
           du deplacement du contaminant 4  travers  les divers milieux
           environnementaux;      !
           de 1 ' interaction  de  I'Homme avec ces milieux.
                Conseil  Canadian  des ministres des. ressources  et  de
1 ' environnement  (CCMRE)  a constate  1 ' incoherence  des diverses  raethodes
adoptees  au Canada pour  ilaborer  des critires  de decontamination.   Le
CCMRE s'est  sensibilisfS  A la  necessite   d' adopter une  approche  unifonne
pour la mise  en place des criteres de decontamination,  qui  tient compte
des caract^ristiques  propres  aux emplacements et qui vise  la protection
de la sante1 ainsi que  de  1 ' environnement .

           Pour  l'61aboration  des  criteres de  decontamination,  les
solutions de rechange ou  strategies  (sous -ensemble des criteres  generaux
des methodes absolues  et  relatives) peuvent etre decrites conune suit:

           les pratiques  ad hoc;
           1' Evaluation du risque propre 4 un  lieu;
           les objectifs  nationaux  de  contamination r6siduelle;
           la restauration au niveau du bruit  de fond;
           les normes  basees sur  les meilleures techniques diaponibles ou
           sur les meilleures regies de 1'art;
                                  198

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           1'approche couts/benefices;
           le  classeemnt et la rcstauration des  lieux en fonction de
           leur  utilisation actuellc ou future.

           A la  suite d'une evaluation de ces strategies  en 1985,  le U.S.
Office of Technology Assessment a conclu que les  pratiques dites  ad hoc
n'etaient plus  acceptables et que la  restauration au niveau du bruit  de
fond etait  ecologiquement, techniquement et economiquement inconcevable.
Bien  qu'attrayante,   la  decontamination basee sur  les meilleures
techniques  disponsible  n'offrait pas  une  protection  de la  sante   et  de
1'environnement  proportionnelle  aux  couts  de  la mise en  oeuvre.
L'etablissement d'objectifs  nationaux,  1'approche cou ts/benef ices  et
1'evaluation  du  risque  specifique  a  .une  lieu posent,  malgre  leurs
qualites,  des  problemes importants  et  ils  sont  considerablement limites.
Seuls les criteres  de decontamination  fondes sur le classement  du  lieu et
de ses abords  selon leur utilisation actuelle et eventuelle  ont semble  le
plus avantageux.   Le  mieux encore  serait  de  combiner  certaines  de  ces
strategies  en une  seule  qui pourrait  ainsi  employer  le  classement  du
lieu,  1'evaluation du risque,  1'analyse du rapport couts/benefices, 'les
normes  environnementales  pertinentes,  de  meme  que  la  prise  en
consideration  des techniques de decontamination  disponibles.

           Les strategies  utilisees  actuelleraent  en Aroerique  du Nord  et
en  Europe par les  Etats  et les organismes competents  sont decrites  ci-
dessous.

     o     L'Alberta n'a pas de  strategic  systematique lui  permettant  de
           selectionner des criteres de  decontamination.    Elle demande a
           la  compagnie ou  4  1'organisme  responsable. d'identifier  les
           contaminants  se  trouvant  sur  le  lieu  et  ceux  qui  sont
           prฃoccupants et de  proposer,  pour  approbation,  les niveaux  de
           decontamination suggeres.

     o     L'Ontario revise actuellement son guide de restauration  et  de
           rehabilitation  des  lieux industriels.   Ce  document precise
           quels sont  les donnees et  les renseignements  requis  pour
           obtenir  1'approbation de  plans  de decontamination.   Des
           criteres sont  indiqu^s   pour certains  contaminants,
           inorganiquas pour la plupart.

     o     Le  Queebec  s'inspire des  modeles  neerlandais  et  fran9ais,
           c'est-a-dire  qu'a partir  de  grandeurs  particulieres
           (concentrations affectant  les  contaminants des  sols et des eaux
           souterraines)  il dgfinit trois  niveaux de  contamination  (de
           base,  mode'r^e   et grave)  en vue de  la  gestion  de  la matiere
           containing e.

     o     La  Californie fait  appel  a  un  ensemble  uniformise ,
           syste'matique et integr6  de  taches  unitaires  (1'arbre  d^
           decisions  pour  la  decontamination  des  decharges)  afin
           d'6tablir des  criteres  de  decontamination propres  a   chaque
           lieu  desaffecte ou sauvage dans 1'fitat.
                                    199

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Le  New  Jersey  obtient  le's  concentrations, scceptables de
contaminants du sol  en  se basant sur des  calculs  tenant  compte
de  I'exposition  de  1'Honme aux sols contamines  et aux  eaux
souterraines contamlnees.   Pour chaque site  le systeme: •  permet
aussi de  quantifier  1'exposition des organismes- aquatiques aux
eaux de surface contaminees (par un sol contaraine).

L'ttat de  Washington  a mis  sur pied  un  systeme uniforme
systematique  permettant un mettoyage preliminaire ,et a :• long
terme  des lieux  contamin^s,    Le systeme  est.  fonetIon  'de la
probabilite  que  la migration eventuelle  des  contaminants,dans
les  divers  milieux  exerce ,des  effecs -nocifs,- tant aigus que
chroniques, sur la sante.                    •  .  ,         '

Le  systeme  "Preliminary Pollutant. Limit  Value"  de  1'Armee
americaine  a  61ฃ  ^labore; pour determiner les  limi'ces de
probability  qu'un contaminant  se trouvant dans un  sol affecte
la santd  par differents eheminements,  Chaque\cheminement est
dicrit  a  1'aide  d'une  equation mathematique decoulant des
proprietes physico-chimiques  du contaminant et des milieux
traverses.   Les- differents, cheoinements  sont  combines  pour
obtenir  une dose  journaliere cumulee  pour ;un-_ o.rganisrae
ricepteur.   La concentration du contaminant a la source est
alors reduite jusqu'a ce  que la dose cumulee se ,.retro.uve,i a un
niveau acceptable.      .     ;     .- :  '•   •        ,-.'••

L'SPA recourt & un ensemble specifique de modalites  (Superfund
Public Health Evaluation Manual)  afin d'etabllr des niv,eaux de
decontamination  empechant  les^  contaminants  d'ayoi.}:  un  .effet
noeif sur la sante"  de  la  population exposee. -'Les 'principales
caracte ristiques  de ce  systeme  sont que  la migration des
contaminants  dans les  divers  milieux est- quantifiee et que
1'exposition de 1'etre humain^est evaluee  dans le  detail.-

Les Pays-Bas ont dressd une  liste des  contaminants  (environ 50
composes  et  melanges organiques  et  inorganiques)  et  de leur
concentration  dans  les  sols; et  les eaux  souterraines.    Ces
concentrations definissent trpis degres de  contamination:  (1)
noraale ou de base;  (2) mod^reee;  (3) grave, dont decouleront
les recommandations sur  la gestion des matieres contaminees.

Le Royauaie-Uni a  publie une  lisfie des seuils sous lesquels on
peut presumer la  non-contamination  du sol pour un contaminant
donne,    Ces  seuils,  qui varient selon 1'utilisation projetee
du lieu,  ont  ฃtฃ adaptes  A  partir  de  criteres utilises a
d'autres fins ou  se fondent  sur  une  appreciation technique.

La France a publi6  une  lisฃe  de  criteres, correspondent a
quatre  niveaux de contamination distincts, soit;   (1) le  seuil
d'anomalie (aucune intervention); (2) le seuil d'investigation
(enquete  approfondle nicessaire  avant de se  prononcer sur la
nficeasitt^  d'eliminer le  contaminant);   (3)  le  seuil de
trmitement (c'est-4-dire  traiteoent  du sol  afin  d'en  reduire
la contamination);  (4)  le  sueil  d'urgence  (c'est-a-dire


                            200

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      intervention  immediate  et  decisive pour  supprimer  la
      contamination).                                              .

      L'evaluation  de chacune des strategies utilisees pur elaborer
      des criteres  de  decontamination  s'est faite  en tenant compte
      de  leur capacite  a:

o     inclure des donnees propres a chaque lieu;
o     tenir compte de tous les milieux;
o     tenir compte de tous les contaminants;
o     amalgamer  une grande variete de donnees scientifiques;
6     distinguer entre  les divers niveaux ou periodes  d'exposition;
o     tenir compte de diverses voies d'exposition;
o     tenir  compte  de  1'effet  sur un  recepteur biologique  d'une
      exposition & plus d'un contaminant;
o    . distinguer  entre  les contaminants cancerogenes  et  non
      cancerogenes;
o     evaluer le risque;
o     tirer le meilleur parti possible de donnees  fragmentaires;
o     tenir compte de 1'utilisation finale souhaitee du sol.

      Seules les strategies de 1'EPA, de 1'Armee americaine et de la
      Californie possedaient  ces  caracteristiques.    En  raison des
      nombreuses strategies utilisees  pur 1'elaboration  de criteres
  , .   ,de  decontamination et  de  la necessite  d'elaborer  un  systeme
      scientifiquement  defendable,  facile A  uniformiser  et  4
      utiliser,  il  est  recommande  d'etudier  la  possibilite  de
      developper  un systeme combinant les  methodes absolues  et
      'relatives.  Ce  systeme  combine  permettra un meilleur rendement
      couts/benef ices,  tenant  compte  de la  grande  diversite  des
      lieux pour lesquesl un riettoyage est envisage.    Cette faqon de
      proceder  repondra  au  besoin,   constate  par   le  CCMRE,
      d'uniformiser les criteres de decontamination en tenant corapte
      des caracteristiques  particulieres aux differents   lieux  et  a
      la  necessite de proteger la sante  et 1'environnement.
                               201

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THE  DEVELOPMENT OF SOIL

    CLEANUP  CRITERIA
             CANADA
        CONTAMINATED SOIL CLSANUP
             IHr CaKUDA ,  ,
         '•  , ', VOLUME 2  ,.;'.-  .,. ., , .
         INTERIM RUFOUS OH THK "
       "DEMONSTRATIOH* VERSION Of
          THS AsktS MODEL    '   ^
       (AN AID FOR BryAitfATING TH3
    REDSVHLOPMSNT OF INDUSTRIAL SIZES)

                202

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     CONTAMINATSD SOIL CLZAHOP
             IN CANADA
             VOLUME  2
       IM7ZRZN WCPORT  ON IBB
    "DSMONSTRATION"  VIRSION OF
         f^B &SRX3 MO&IIi
    (JtN AID FOR 3VALOXTING THB
BSD3VSLOPMIEHT Off INDUSTRZAZi SITX3)
         prepared for the

Decomnisaioning Steering Committee
            1988-12-15
                  203

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                         NOTICE  OF
The organizations and Individuals associated with the creation or development
of AERIS make no representations  or  warranties of any kind with respect to its
contents and disclaim any implied warranties of suitability for any particular
purpose. Neither are they liable  for any  errors in thซ software or any damages
resulting from its performance  or use.
                                     204

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SUMMARY                         ,

Wherever industrial  activities  have  caused on-site  soils  or ground water  to
become  contaminated  and redevelopment  to another  use  is  being  considered,
there ia the potential for future  site  users  or those located down gradient  to
be exposed to chemicals present in site soil through  various  pathways  such  as
the inhalation of vapours,  direct  ingestion of  soil,  or the ingestion of  local
ground' water.

At  the present  time,  few  jurisdictions have  established  acceptable,  soil
concentrations.   In  June  1987,  Environment  Canada awarded  a  contract  to  a
consortium of consultants  headed  by Monenco Consultants Limited. One of the
goals of the  consortium was  to produce a  computer model that can be  used  to
derive clean-up  guidelines for  industrial sites where redevelopment is  being
considered or planned. The result ia the  "demonstration" version  of  the  AERIS
model. The acronym ASRIS   (Aid  for Evaluating  the  Redevelopment of Industrial
Sites) was chosen to help  users remember its  intended  use,  that  of being  an
aj.ij for evaluating industrial sites. As an aid, AERIS is suited to identifying
the factors that are likely  to be major  contributors to potential  exposures
and concerns at  sites, those  aspects of a  site  redevelopment  scenario with the
greatest need for  better information,   or as  an  indicator  of the extent  to
which remedial action may be  needed  at  a site.

The  AERIS  model  consists  of  four  basic   elements  - an  "intelligent"
preprocessor,  component modules, a postprocessor,  and supporting  data bases.
The preprocessor takes the form of a series  of cpaestions that AERIS asks the
user  about  the  redevelopment scenario  to be  evaluated.  The preprocessor  is
referred  to  as  "intelligent"  due  to the  utilization  of  "expert  system"
technology. It uses a set  of  rules  (collectively referred to aa  a "knowledge
base") to  establish  a structure to  the decision support  offered; to aid the
user  in estimating  unknown  input  parameters, and  to  control   the  flow  of
information among the other program modules.

The preprocessor passes the information generated by  the user's answers to the
component modules  which  calculate   environmental concentrations,  doses
experienced by  the  selected  site  user, and  the   resulting "acceptable"
concentrations  in   soil.   There  are   seven  component  modules  in  the
"demonstration"  version of AERIS.

The  Correlation  Module  is used to predict  mass  transfer coefficients. The
predictions subsequently are  used in the Air Module which  calculates the  flux
of chemical from the soil into the air  and basements  of buildings  where it can
be inhaled by a  site user or visitor.  The rate at which  a  chemical will  be
transported from soil into the outdoor air is  influenced by properties of the
soil, properties of the chemical,  and environmental conditions.

The Unaaturatcd Zone Module predicts concentrations in soil-water  and soil-air
in the  soil  above  the water  table.   It assumes  that  there is a  contaminated
layer that  starts  at the surface and  that the user  can define the layer  in
terms  of  its  average  or  typical  depth  and  contaminant  concentration.   If
appropriate, there can be an  underlying non-contaminated soil  layer.

The Saturated Zone Module predicts concentrations in  ground water. Key  factors
it considers include the depth  of contamination  with respect to  the depth  to
the local water table, and the location of a  well used  for drinking  water,  if


                                       205

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appropriate.

The Produce Module is used to  estimate concentrations  in produce grown on the
site. The uptake of chemicals  ia assumed  to be contributed by root uptake and
foliar deposition. The extent  of uptake is  influenced  by the type of produce,
length  of growing  aeaaon,   chemical  'properties  of the  chemicala,  and  aoil
characteristics.

In the  Ingcation Module,  the intakes  of  water,  aoil,  and  garden produce are
estimated. The  concentrations  in  the  water, soil,  and produce are determined
in the  Saturated Zone  Module, Unsaturated  Zone  Module, and  Produce Module,
respectively.                         ;

In the  Inhalation Module, the amounts of  chemical inhaled by  the  receptor
while outdoors  and indoors are calculated.  Both the inhalation of vapours and
particulate matter are taken into account.

In the Total  Dose Module, the  doses via all pathways  are  combined.  The total
is then compared to the  "acceptable"  dose level.  The  user  can decide whether
all or some fraction of the "acceptable" level is to be used.

The calculations  of the  component modules  are  passed to  the postprocessor,
which offers  various  tabular" and  graphical ways  of  displaying  the  results.
Each run  of  the model concludes with  tables that display  dose  estimates for
each route, total doae  estimates,  and identification  of  an "acceptable"  aoil
concentration.  At  the  user's  discretion, three types of  graphical summaries
can be displayed: a plot of soil concentrations versus dose; pie charts of the
relative  contributions  of each  route  to total  exposure;  and  diagrams  that
compare the calculated  "acceptable" concentrations to guidelines  or  criteria
issued by regulatory agencies.

AERIS  data  bases  can  provide  much of  the information  needed  for  the
calculations.  Information is  retrieved  in response  to the  user's  answers
concerning the  scenario to be evaluated.  The types  of  information that  can be
retrieved  include   physico-chemical  data,  "acceptable"   dose  levels,
bioavailability factors, concentrations associated with other types of adverse
effects, and  guidelines  or criteria from various jurisdictions.  The  user has
the opportunity to edit any  of the information retrieved from the  data bases
so that the redevelopment scenario can be made to  resemble actual situations
of interest.  AERIS also includes default values and various  aids to help users
select appropriate values. The data bases  in  the  "demonstration"  version  of
AERIS  have information for:

  -  two types of site users: an adult and a young child
  -  four future land uses:  residential, commercial, recreational (park  land),
     and agricultural                   >
  -  four organic compounds: benzene,  imethyl ethyl ketone,   phenanthrene,  and
     pyrene
  -  three inorganic substances:  lead,  selenium, and zinc
  -  the meteorology  of  six  Canadian  cities:  St.  Johns,  NFLD, Montreal,  PQ,
     Toronto,  ON, Winnipeg, MN, Edmonton,  AL, and  Vancouver, BC
  -  physical characteristics of nine soil types and 14 underlying formations.

AERIS is structured so that each run evaluates   one chemical for  one receptor,
one land  use,  and one environment.  The user is encouraged to run the model
                                       206

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several tinea and  base  decisions on  the collective outcomes  of those  runs.
Accordingly,  adjustments  to  input parameters can be  made  relatively  easily.

AERIS is designed to evaluate situations where the  soil  had been contaminated
sufficiently long ago to establish equilibrium or near-equilibrium  conditions
between the various compartments  of  the environment.  These conditions  should
apply to most industrial  sites  that  are being considered  for redevelopment. As
such, AERZS is  not suitable for  evaluating recent spill  sites or  locations
being considered as candidates  for  receiving wastes.  Nor  is  it suitable  for
calculating changes in environmental  concentrations  or exposures over time  due
to ongoing contaminant contributions  from a  constant or sporadic source.

To illustrate various  aspects of the  AERIS model and its  response to different
sets  of  input  parameters,   two  hypothetical  redevelopment   scenarios were
created. Scenario "A"  was assigned characteristics typical  of those  that  might
be  encountered  at  a  site  in  southern Ontario, while  Scenario  "B" is more
representative of a site  in  central Alberta.

The  AERIS model  was  used to identify "acceptable" soil  guidelines for each
scenario by considering  three  soil  contaminants  (benzene,  phenanthrene,  and
lead), for all four of the land uses  addressed in the data  base,  and using  the
young child as the  receptor.

For  benzene,  the  "acceptable"  soil  concentrations  for Scenario "A"  (0.08 to
0.6 mg/kg)  are slightly higher  than  for Scenario UB" (0.04 to 0.6 mg/kg).  The
only  guidelines   in Canada  include a value  of  0.5  mg/kg  recommended by  the
Province of Quebec as  the threshold at which detailed site investigations  may
be  needed,  and  a concentration  of  5  mg/kg which  is  recommended  as  the
threshold at  which immediate  corrective actions  may  be necessary.

The  lower concentrations in Scenario "B" stem  from the  lower  organic  carbon
content in  that site's   soil  and the subsequently higher  concentrations of
vapours in air  (and higher receptor  doses via inhalation). The  inhalation of
vapours is a dominant  pathway  (50  to  84%)  for total  exposure to  benzene in  all
land uses except recreational  (in which  all time on-site is spent  outdoors).
Associated with  the "acceptable"   soil  concentrations  are  outdoor air
concentrations  well below  the  air quality  criterion  from Ontario but ground
water concentrations  (at  the site boundary)  above  the  guideline from Quebec.
The  values   also   are   less  than   those   reported  to  cause odours  or
phytotoxicological  effects.

For  phenanthrene, the concentrations  for Scenario  "A"  (3300 to 20400 mg/kg)
are  slightly  lower than  for Scenario "B"  (3500 to 23300 mg/kg).  Site soil
conditions  in  Scenario  "A"  result  in   slightly  higher   ground  water
concentrations of phenanthrene, an important  pathway that  accounts  for 24 to
64%  of  the  total  dose estimate:!. The only  guidelines  in Canada include   a
value of 5 ppm recommended  by Quebec  as  the threshold at which detailed site
investigations  may  be   needed,  and  a  concentration  of  50   ppm   which  is
recommended as  the threshold  at  which  immediate  corrective  actions  may  be
necessary.

For lead,  concentrations  for Scenario "A"  (8  to  500 mg/kg) are slightly higher
than for Scenario  "B" (5 to  15 mg/kg) . Soil guidelines in Canada lie in the
range of 200 to  1000 mg/kg.  The dominating  influence of  produce ingestion in
Scenario  "A" stems  from  a  relatively high plant   uptake  factor.  The
                                       207

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"demonstration"  vernion of  AERIS  makes  no  allowance for  reductions of
concentrations in produce that result during food preparation auch as washing,
peeling, or boiling.  As a result, the jestimated doses from eating produce are
likely  to  exceed actual  doses.  This•, becomes  an  important  consideration in
interpreting the output for  scenarios in  which  the consumption  of produce  ia a
major pathway.

The sandy  soil  in Scenario  "B"  results  in higher concentrations of  lead in
ground water and therefore doses  via  that route are significantly greater  than
in  Scenario  "A".  The  dominating influence  of   ground  water  ingeation in
Scenario "B™  results  in "acceptable"•soil  concentrations considerably lower
than those being used or considered by some  regulatory agencies. The inclusion
of  site ground  water  as  a  source   of   exposure  is  an  unlikely  condition
especially in urban areas. If  ground  water had  not been  included as a pathway,
the "acceptable" soil value  for Scenario  "B" would have  been approximately 100
to  450  mg/kg.  For both  scenarios,  the   use  of lead-specific  bioavailability
factors (rather than  the  default  values)  likely'would  significantly increase
the "acceptable" soil concentrations.

Associated with the "acceptable"  soil concentrations  for lead are ground water
concentrations  (at  the site  boundary)  below  the drinking and  ground water
guidelines of several Canadian agencies*  The values also are well below those
reported to cause phytotoxicological  effects.

The investigations of Scenarios  "A"  and  "B" suggest that various  aspects of
AERIS  are  performing  as intended. For  example,  the "acceptable"  soil
concentrations  are  inversely   proportional to the  relative  level  of
toxicological concern posed  by chemicals. As anticipated,  future  site use is
an important consideration in  getting "acceptable"  concentrations. Residential
and agricultural uses consistently generate lower  "acceptable" concentrations
than recreational and commercial  uses. Comparisons  of output for a compound in
Scenario "A" with that for Scenario "B" show that  site soil and meteorological
conditions also can be  important  influences  in determining "acceptable"   soil
concentrations.

Based on a  review  of  the results for the two  scenarios,  it  is apparent  that
"acceptable" soil  concentrations  for  inorganic substances are strongly
influenced by soil pH and the value  of  the distribution coefficient  (Kd^).
Since default values  for K..  are  not provided  by  the model, a user  who  must
•guestimate" at values  for  K<.Ji may  want to run  the model several  times to
evaluate the overall  sensitivity  of the results to  this  parameter. For organic
compounds that have physico-chemical characteristics in the data  base,  there
is not a key parameter analogous  to the Kdi,  but  for compounds  not in the data
base,  the veracity of the values  used for aqueous  solubility,  vapour pressure
and  octanol-water  partition  coefficient  should  be  key considerations  in
determining the level of  confidence  that  can be placed  in the  results.

Because the  development  of  the   AERIS  model  has  only  reached   the
"demonstration" stage,  the results that it produces always must be interpreted
in the context of several  cautionary  notes:

  -  The "acceptable"  soil concentrations  that  are  identified are based solely
   -  on human  health concerns.  The  conservative, risk-based  philosophy  and
     default  values  that appear throughout  the model  (examples include
     receptor behaviour characteristics,   the  bioavailability factors,  the one-
                                     208

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in-a-million level of  risk  for VSD values,  the general availability  of
contaminated  site soil  for  exposure)  make  it  possible  to  generate
"acceptable"  soil concentrations  lower than those  that  regulatory
agencies may be  using  or considering. Likely  causes  include the use  of
risk as a basis for setting  concentrations and the inclusion in the  model
of  pathways  usually  not  considered.  Conversely,  relatively  high
"acceptable*  soil concentrations  can be  identified  when  using AERIS,
particularly if  the  scenario  being evaluated  generates very  small  dose
estimates or the  important  exposure  pathways are relevant  for chemicals
with certain physico-chemical  properties or environmental behaviours.  Tor
example, this  could  occur  in the  evaluation of a non-volatile  chemical,
that has a low level  of toxicological  concern in a commercial setting.

The algorithms used to estimate environmental  fate and  concentrations  in
environmental  compartments  as a function  of  the  concentration in  soil
have been verified but not  calibrated  (that  is,  the  predictions of  the
algorithms have  not  been compared to  concentrations  measured at actual
industrial sites in various  environments).

There likely  are  inadequacies in the  algorithms  in  the  "demonstration"
version of AERIS.  During model  development,  it was recognized that  some
aspects of the  algorithms may be  poorly suited to evaluating  conditions
where soil  is extremely  alkaline  or  acidic,  plant   uptake  is not  well
understood,  and the overall  approach may require  site complexities  to be
replaced with generalizations.

The "acceptable"  soil concentration values  that are determined by  AERIS.
should not be taken as  absolutes but  rather as being generally  indicative
of appropriate concentrations. To establish  soil guidelines  with greater
confidence,  it  may be  necessary to  evaluate a  scenario  by running  the
model many  times  so that  output  variability  and   sensitivity  can  be
assessed. It also  may be necessary to  examine each of the  conservative
assumptions  used  from a  chemical-specific  perspective and/or  other  non-
health related issues may need to  be  considered.
                                 209

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        NATO/CCMS Guest Speaker:



            Troe/s Wenze/, Denmark



Membrane Filtering and Biodegradation
  211

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ON-SITE   /   IN-SITU  RECLAMATION
                   MEMBRANE  FILTERING
                   AND  BIODEGRADATION
                   by
                   Troels Wenzel
                   H0jgaard &. Schultz A/S
                   Jaeger sborg Alle 4
                   DK-2620 ; Charlottenlund
                   and
                   Anne-Mar;ie Nielsen
                   Danish Geotechnical Institute
                   Maglebjergvej 1
                   DK-2800  Lyngby
                   December 1990
                           212

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1. INTRODUCTION


Every year the number of known contaminated sites in Denmark in-
creases. Today more than 2,000 sites are registered and the
number has not culminated yet, ..Unofficially the number of'conta-
minated sites is estimated to more than 15,000.

About 90% of the sites are contaminated with some kind of orga-
nic components, most of which can be biodegradated under aerobic
conditions on-site as well as in-situ.

On that basis the three companies DDS^Filtration, Danish Geo-
technical Institute and H0jgaard & Schultz formed a joint
venture with the purpose to develop and test new and more cost-
effective methods for cleaning up organically contaminated soil
and groundwater. The technique proposed was a combination of
biological in-situ restoration and on-site membrane filtering
followed by biological destruction of the contaminating agents.
2. ORIGINAL TREATMENT PLAN


The working group set up by the companies designed a treatment
system based on the following main processes:


0.  Recovering of contaminated groundwater

1.  Pre~treatment of the pumped-up groundwater

2.  Filtration of the groundwater by Reverse Osmosis (RO)

3.  Biological purification of the concentrate from the RO unit

4,  Recirculation of purified groundwater and oxidation

5.  Biodegradation in soil and groundwater


The concept was planned to be tested and developed at a gasworks
site near Copenhagen, Denmark, cf Figure 1.
                              213

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      Recovering of
      Groundwater
  /2*\  Reverse osmosis


  ("3)  Biological purification



  ft) ' Recirculation


  (s)  Pollution plume


  (6)  Ground weter level
Figure 1.  The main processes  in the treatment system.


Previous environmental investigations had demonstrated that the
soil and groundwater were polluted with tar components,  cyanides
and sulphur.  The main results are shown in tables  1  and 2.
    Coal  tars
    Naphthalene
    Cyanide (total)
    Sulphur
 100 -
   5 -
 100 -
5000 -
37000 mg/kg
  200 mg/kg
 3500 mg/kg
40000 mg/kg
   Table  1.  Concentrations of pollutants in the soil.
    Volatile aromatics       100
    Phenols                    10
    Naphthalenes             300
    Sulphur                    30
    Ammonium                  20
    Cyanide  (total)        0,01^
    Iron                      100
    Calcium                   100
         1600
         2300 ug/1
        18000 ug/1
         1700 ug/1
          200 ug/1
          1,9 mg/1
          500 mg/1
          750 mg/1
   Table 2.  Concentrations of pollution components  in the
              groundwater.
                                214

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3. RESULTS, PROBLEMS  ENCOUNTERED AND MODIFICATIONS'


During the small^seiSle field experiments and laboratory  tests,  a
series of operatidh&l problems were identified regarding the
planned treatment.


3.1 Pre-treatment of  the Pumped-up Groundwater

The testing of RO filtration is described in chapter  3.2.
However, all RO membranes are very sensitive to the feedwater's
contents of iron, calcium carbonate and particles ill  general so
experiments were carried out with pre-treatment of the ground-
water before entering the RO unit. Especially the extremely high
contents of iron as Fe++ (300 ppm) caused problems in' the early
trials.

After the first long-time trial on the site, problem^ with clog-
ging of the RO membrane by precipitated iron indicated that the
proposed pre-treatment by simple sand filtration cdttid not pro-
vide the water quality needed for the RO processing *

The modified pre-treatment system was optimized by rUnning the
system in batches. NaOH was added to the pumped-up Qroundwater
and air was injected  befor'e entering the reaction ta"fik.  After a
reaction period df approx* 15 min. the suspended particles were
precipitated in d clarifier. The effluent was1 puntpe'd  to  a sand
filter and adjusted to pH "7 before entering the RO iltiit.  The
modified pre-treatment system is visualized in Figure" 2.
                            PRETREATMENT
            3 4
    1 RECOVERY WELL

    2 .GHOUNOHATER

    3 OXIDATION

    4 BASIFICATION

    5 REACTIONCOHTAIHER
    6 CLARIFIEH

    7 SANDFILTER

    8 PH ADJUSTING

    9 RO-UMIT
Figure 2. Modified pre-treatment system.
                                215

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The sludge from the pre-treatment consisted mainly of ferri-
hydroxide (Fe(OH)a) and smaller amounts of calcium carbonate
(CaC03). Analyses of the sludge and feedwater entering the RO
unit showed a substantial loss of organic components to the
sludge during the precipitation of particles. The analyses also
indicated that most of the volatile components had been stripped
off into the atmosphere in the aerated reaction tank. The total
loss of tar components before the water entered the RO unit was
estimated to be 40-70 %.

The high content of tar components in the sludge made it heavily
contaminated and therefore unfitted for deposit at an ordinary
disposal site as planned.


3.2 Filtration of the GroundHater by Reverse Osmosis

Several types of filtering units and membranes have been tested
for the purpose. The socalled PIate-and-Frame type was found to
be the filtering system most unsensitive to clogging.

The RO unit used in the final; tests was a DBS PI ate-and-Frame
system equipped with a HR thijnfilm polyamide composit membrane.

The system consists of a specially moulded and perforated sup-
port plate which is flanked by two flat sheet membranes. These
membrane-covered plates are staked and mounted in a stainless
steel frame. When the plates 'are compressed, thin channels are
formed between the membranes due to the plate ribs. This special
flow pattern creates a high shear rate over the membranes.

The PIate-and-Frame unit used, in the trials rejected the organic
as well as the inorganic components successfully.

There was a tendency that the unit showed higher .rejection rates
for components with a relatively higher molecular weight. '

Also the polarity of the molecules had an impact on the perfor-
mance. The membrane chosen fot the purpose had an approximately
10% higher rejection rate for unpolar components than for polar
components. For example the rejection rate for BTEX's was almost
100% whereas phenols and cresols were separated from the per-
meate at a 90% level.        r

The rejection rates for metals and inorganic components were
overall easily accomplished at a 97-99% level.
                              216

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   Component            Approx. rejection rate in %
   Benzene                          98 •
   Toluene                          98 •
   Xylene                           98 •
   Phenol                           89 •
   O-cresol                         88 •
   M-cresol                         95 •
   P-cresol                         97 •
   Naphthalene                      98 *
   Cyanide                          99 •
   Chloride                         99 •
   Metal ions                       98 •
   * Estimated value
   • Measured value
  Table 3. Rejection rates for the RO unit under laboratory and
            on-site test operation.


3.3 Biological Purification of the Concentrate From the RO Unit

Comparing laboratory tests of activated sludge and Rotating Bio-
logical Contactor (RBC) demonstrated that the RBC was the more
cost-effective and therefore the RBC was chosen as the reactor
in which the destruction of the concentrate from the RO unit
should take place.

The pilot scale reactor was started with groundwater recovered
from the gasworks site and gradually fed with increasing volumes
of concentrate from the RO unit.

The reactor performed well after an adaption period of 3-4
weeks, after which the components were destructed down to almost
undetectable concentrations.

Xylenols created some problems and never reached values lower
than 200-300 ppb in the effluent.

Odours from the bioreactor were foreseen but were expected to be
reduced to acceptable levels by a reactor cover and an odour
filter, a compost or an activated carbon filter.


3.4 Recirculation of Purified Groundwater and Oxidation

On-site testing of the possibility of percolating water through
the soil showed that the infiltration rate was much lower than
expected in the early phases of the project.
                               217

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                               ;    — 6   —7
With hydraulic conductivities pf 10  -10   m/s the original
intention to wash out mobile components of the soil by means of
recirculation was considered as irrelevant at the site in
question.

Under normal pressure and temperature conditions water saturated
with atmospheric air is able to hold approximately 9 mg O2 per
litre. As a rule of thump, 1 g:of hydrocarbons requires 2-3 g of
oxygen to be totally degradated, and only 10-30% of the oxygen
reaching the contaminated area;in the soil will be used for
degradation of the contaminants. The rest is used for oxidation
of a variety of other substances in the soil. The volume of
water required for oxygen transport would therefore be enormous.

The use of other oxygen sources such as hydrogenperoxide could
reduce the needed volume of water to some extent but the volume
of water would still be very large which - in combination with
the low permeabilities of the soil - made it impossible to
sustain the biological degradation at a rate where the clean-up
objectives would be reached within reasonable time.

The proposed solution to the problem of oxygen transport is to
combine soil venting and water reinfiltJration. In this solution
atmospheric air is vented through the soil and water containing
nutrients is infiltrated from the surface simultaneously. The
infiltration rate is kept sufficiently low to avoid water satu-
ration of the soil, thus enabling a constant oxygen supply to
the microbes in the soil by means of diffusion of oxygen from
the airfilled pores into the oxygen-depleted porewater.

An additional benefit of the soil venting is the stripping off
of the volatile components.


3.5 Biodegradation in Soil and Groundwater

An additional research programme has been carried out with the
object of studying the degradation rate of the tar components
(polynuclear aromatic hydrocarbons, aromatic hydrocarbons and
phenolic components).          ;

The soil and groundwater used in the laboratory tests were col-
lected from the gasworks site. ;A11 the experiments were carried
out in bottles which were kept at, 10 degrees Celsius in darkness
in order to simulate the natural conditions in the best possible
way. The groundwater discharge \was simulated by rotating the
bottles. The bottles were giver} different conditions by using
nutrients, oxidation mediums (O2, KNO3) and different concen-
tration levels of contaminants,;
                               i
The degradation rate was examined by means of chemical analyses
using gaschromatography, microbiological tests such'as DEFT and
platecount, and tests with labelled components (liquid scintil-
lation counting of carbon-14). ;
                               1218

-------
The data from -the laboratory experiments have not been prepared
for presentation yet. However, the results of some of the tests
with labelled components and some of the microbiological tests
are examined in the following figures and tables.

In table 4 some of the results from the platecount tests are
listed. The data show an increasing number of colony forming
bacteria in the first 19-58 days in both one litre bottles and
in the small bottles. This could indicate that the reproduction
of the bacteria principally takes place shortly after the start
of the experiment.                                        ,
               Platecount data (colony-forming units pr. g)


                0 day   19 days   58 days  176 days  197 days


One-litre            .     ••,   ,                             7
bottle aerob,    3x10*    8x10ฐ                         2x10'
no nutrients              ,

One-litre re-        ~        x                             ,,
ference bottle    <10     2x10                           <10
(no biologi-
cal activity)


300 ml bottle        5
aerob, no        5x10               5x10      5x10
nutrients

300 ml refe-         ซ                  _         ,
rence bottle      <10                <10       <10
(no biologi-
cal activity)


Table 4. The biological activity tested with platecount in
          one-litre bottles and in small bottles (300 ml).


The total decomposition of carbon-14-labelled antracene was
tested with liquid scintillation counting of the produced
labelled carbondioxide. An example of the results is shown in
figure 3. Figure 3 shows that about 2% of total decomposition in
the test bottle has taken place and no degradation at all in the
reference bottle. It should be noticed that the intermediates in
the decomposition are not included in this kind of test.
                               219

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5.00-
4.S0-
4.00 -
3.B0-
3.00 -
2.E0 -
X
2.00 -
1.S0-
1.00 -
0.60-
0.00 -
*"" w * OU
0.
5.08-
4.50-
4.00 -
3.50 -
3.00 -
a. sa-
7.
2.00 -
1.B8-
1.00 -
0.50 -
0.00 -
-0. G0 -
0.
One liter bottle, aerab, no nutrients
/\v :
/ ^X
/ ^ •* !-~ ^\
/ / * ~~^^:
/
- //
\ '
i
00 B6. 80 100.00 150.00
; days
Qnซ litar refBrBneebottlB (no biological ac'tiw






I i
1 1
00 50.80 100.00 150.00
; days
Activity, C/Co


• 	 Bottle 1



•f - - Bottle 2 •'

ity>
Aotiuity, Q/Co


• 	 Bottle 1



+ - - Bottle a

Figure 3. The total degradation tested with liquid scintil-
           lation in a test bottle system and in a reference
           bottle system. C:, The actual concentration of the
           labelled carbondioxide. Co.* The highest possible
           concentration of ^.he labelled carbondioxide.
                              220

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Figure 4 shows the decrease in the concentrations of some of the
contaminants in the groundwater and aquifer materials. These
data fit well together with the data shown in table 4 and figure
3 indicating decomposition of the tar components.


3. 00 -
2.80 -
a. 89 -
2.40 -
2.20 -
2. 00 -
U
a; 1.80 -
X 1,60 -
g
D 1.48 -
M
1,20 -
i. 00 -
0.80 -
0.60 -
9.48 -
B.20 -
@n ft
• CO

































1
1
1
w

















1 J
0

























H<
1
1
1

1
r*


1

1
1












S
^
ฃi
1
1
!S
%
*&
•$&
jฃ
>ง
1
1


































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1


3S8 mi














• Hljmf-
61

bo1











Ka
t
t>ฃ&ฃ
S
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1


it le, aerob, no nutrients














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118 1T4
days



















Compounds
Benzene

KjSS3 Toluene

^$$$8^ Ethyltaenz.

Xylene

lljllllllll Naphthalene

|_: : : : I Phenol

Cresal

XylenaJ.

Figure 4. Decreasing concentrations of various components in-
           dicating Jbiodegradation.
                              221

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4. CONCLUSIONS BND FINAL REMR'RKS


On the basis of the results of the laboratory and small-scale
on-site tests the following conclusions can be drawn:

-  The RO system proved a high degree of purification regarding
   the organic components in the ground water. It also turned
   out to be very sensitive tb some of the inorganic components.
   This required an extensive pre-^ treatment during which a great
   deal of the organic components were precipitated or stripped
   off. Thus, the RO unit which was a vital part of the puri-
   fying treatment ended up by being obsolete. Besides a sludge
   problem arose.            ;

-  In comparison with activated sludge the RBC was cheaper as
   well as more efficient and more sturdy towards the fluctua-
   ting concentrations of contaminating components. Laboratory
   testing of biological purification of the concentrate from
   the RO unit demonstrated a high degree of purification.

-  Preliminary results from the laboratory analyses of the capa-
   city of decomposition in the soil and groundwater samples
   from the trial site indicate decomposition of tar components
   under aerobic conditions.

   On-site tests of the percolation showed unexpectedly low per-
   meability coefficients which in pracsis would make it im-
   possible to wash out mobile components and to recirculate
   purified and oxidized groundwater enough to create and main-
   tain, aerobic conditions in!the subsoil as originally planned.

For the above mentioned reasons the planned purification treat-
ment was abandoned and the in-situ purification experiment on
the former gasworks site was stopped.
                              222

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         NATO/CCMS Guest Speaker:



                Herve Billard, .France



Industrial Waste Management in France
   223

-------
        The NATO/CCMS Pilot Study
   on Desmonstratfon of Remedial Action
      Technologies for Contaminated
          Land and Groundwater
      Fourth Intemqtionai Confdrencฎ

          5 au 9 November 1990


           ANGERS - FRANCE -
INDUSTRIAL  WASTE MANAGEMENT

              IN -FRANCE

                 !224

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  THE  MANAGEMENT  OF"  I NDUSTR I AL  WAST E S
Indua-tr-ial  W*ปtซ*s A Fe>w Figurปป


     In  France,  industrial  wastes are  usually  classified  in
three categories!        .,
i)  Inert  wastes,  comprised  a-f  earth, debris,  inert materials
     produced  by  processing  o-f  : minerals.  These  wastes . are
     usually  put   in  dumps.  Estimated   annual   production:
     100 million metric tonnes.
2) Commonplace wastes,  similar  to household re-Fuse and able to
     be treated  using  the  same methods.  These wastes include
     wood, waste  papซrป cartons  and  cardboard, plastics,  etc.
     Estimated annual productions  32  million metric  tonnes.
3)  Special  wastes  which   are  characteristic o-f  industrial
     activity.  Thas*  wastes  contain   harmful   elements  in
     concentrations  o-f  varying  degrซซ  and  there-fore pose  a
     higher  risk  to  the environment.  Disposal o-f  the wastes
     must  bsป carried out  with special  precautions. Estimated
     annual  productions  IS  million  metric  tonnes,  of  which

       4  million  metric  tonnes  are   classified  toxic  or
       dangerous.

     Special   wastes   may   also  b*   classified   in  three
categories!
                             225

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a)  Organic wastes  (mainly  hydrocarbon wastes,  tar,  solvents,
     etc.),  usually   able  ; to  be  treated  by  incineration.,
     although  physico-chemical  treatment  processes  are  being
     developed- for  certain  very specific  wastes.  The presence
     of  chlorous molecules in  a  large part  of  these  wastes
     requires  special  smokeipurification.
b)  Liquid  or  semi—liquid   mineral   wastes   
-------
 situation,  which takes into account the characteristics of the
 wastes,  technological   limitations -and   the   availability   o-f
 external  processing and collection systems.  These options can
 be classified  in the following manner:
 i)  Stopping  the production a-f  a waste product by changing  the
     process  or production (implementing "clean technology"  in
     the  strictest  sense of  term)3
 2)  Recycling  the  waste  product within  the  -framework  of  the
     process  that generated  it;
 3)  Recovery .. and  valorisation  of the  waste  -for  various uses
     within the firmf
 45  'Recovery  and valorization of  the  waste  for use outside  the
     firm that produced the  waste   ; the  profitability 'of  an  on  site facility,  linked 'to  its
      critical  size;   •       •            '
 b) the investing or  subcontracting policy of the firm?
 c)   the  firm's  energy   needs-  in  the  case  of   an   ahergy
      valorisation treatment process.

                               227

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     At this  point, it  would be  appropriate  to bear in  mind
that under the Law  af  15 July 1975, tha producer or  holder  of
waste  is  responsible for  what becomes of,  the waste  and  must
provide conditions amenable tp the proper disposal thereof.
2.  Wastes within the  Firm

     2.. i Separation o-f Waste*1 at the Source
     Every precaution  must be taken- to  succeed in  not  mixing
the  different  types  of  wastes  produced  in  a  firm if  these
wastes  are  to  undergo  separata disposal   or  valorisation
processing   or   to   undergo   separate  treatment   processes,
Separating  wastes  at the sourco oftan  requires  additional
investment, but it offers  certain  advantages!


a)  Increased Valori2ation  Potential.  It is easier  to valorize
     homogeneous  waste  products.  For   example,   in  surface
     treatments, the recovery of metallic  salts in  solution is
     profitable  in  concentrated  bathsj   if  these  baths  are
     mixed with diluted  rinsing  baths, recovery becomes  less -
     if at all - profitable.
b)  Improved  Work Conditions.  Dangerous  mixtures are avoided.
     Such mixtures can cause heat  buid~up,  toxic fumes  or they
     can  b*  at  the  origin  of  fires  and  explosions.  The
     unsupervised  mixture  of an  acid  and  a  base can cause a
     violent  reaction that leads to  a  significant rise  in
     temperature.             '•
c) Lower Treatment Costa.  In tne case  of  mixtures,,the  coat of
     treating tha  moปt  difficult  element  will  be  applied  to
     the entire mixture.
                              228

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     2.2 Appropriate Conditioning and Storage
     Solid   wastes  must   be   stored   on   a  reliable   and
environmentally sealed  surface, in  a  holding  tank, or  -  as a
general rule - by  any other  means  that  avoid their being mixed
with rainwater run—off  or  being scattered.  Storage in portable
containers facilitates  subsequent collection and transport.  "
     Liquid  wastes  must  be  stared in  environmentally  safe
containers,  generally  hermetically sealed  so  as to  prevent
leaking  or   fumes  escaping.  The  containers  used  may  be
cisterns,  drums or  tanks -. depending an  the  storage-'capacity
needed and the nature of the  wastes.'
   •  The choice" of the'   conditioning equipment also depends on
the duration of storage,  handling  and  transport conditions and
subsequent processing to be carried  out "on the wastes.   : '"
     When  waste  collection  can be  carried  out regularly and
frequently,   only   reception  and   holding   -facilities   are
necsssary  at  the waste   production  site.  Thus  the risk  of
accidents, which oftan  occur  during  handling,  is reduced.
3.  The Heana  Available to Dispos* of  Special  Wastes

     In  France,  specialised  centres  are  avail-able  to  waste
producing firms to process their  wastes.  They  includes


a)  Incineration centres                  .-..,.
b>  Physico-chemical  treatment centres
c>  Specialised  treatment  centres     '     '       "         ' "'
d>"  Technical   .land-burial   centres   (controlled   waste  and
     disposal landfills)

     Certain  centres  combine several   of  these   activities,,
 (See Hap, Appendix 2)

                                  229

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     Certain  "pratreatment",centres are specialised  in  mixing
and  sorting  operations whiah  make  it  passible to  channel  tha
waste,   or  each   of   its ;  constituents,   toward   the   moat
economically profitable destination.
     3.1 Waste Acceptance Procedure
     The disposal of  industrial  waste  often  can  be carried  out
by   several   treatment  centres.  The  firm's  choice  of   a
particular  centre  should  be  based  on  attaining  the  best
processing at'the lowest cost.  It is  therefore  worthwhile  for
a  firm  to ask   several  centres  for  estimates'  and  then  to
compare  prices -  taking  transport costs  into  account - before
selecting a disposal centre.'
     Tha  procedure  far  waste  acceptance  followed  by waste
treatment centres is as foiltowsj
a> The centres, once cantactjed, will  ask  the  firm for  a sample
     of  the  waste  for  analysis  in  order   to  determine  the
                            i
     nature of processing and the cost of disposal.
b) Once  tha  sample  analysis is completed, the centre  may then
     issue an Acceptance Certificate  to the firm.  Only then is
     the firm  allowed  to send a  load of  wastes  to  the centre
     for treatment.
c)  When the  load  arrives  at  the  centre,   it   is  tested  to
     determine whether it corresponds to  the  sample  previously
     analysed.  If the  load  corresponds,  it  is  accepted  for
     treatment; if not, it is returned to tha producer.
d) Once  the  waste has  been  destroyed, the firm  must receive a
     Certificate  of Disposal, a document  proving the waste was
     disposed of  properly ana1 in accordance to regulations.
                            230

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     3.2 Collective  Incineration Centra*
     The  w*ปto  aeeaptanca criteria  fee-  incineration centres
take the -fallowing factors into  account:

a) The calorific value  of  the wastes,  which will determine  the
     possible  need  -for additional  fuel  in  order  to  ensure
     combustion}
b) Halqgenated  elements content,  which determines  a need  -far
     acceptance  by  centres specifically  equipped -for  carrying
     out  the necessary  incineration techniques  and  treatment
     facilities  for  gasses;
c) Metal  content,  because  alkaline elements  are  responsible
     for damaging furnace  refractories}
d) The flash point,  which  will  determine  the need  for special
     storage conditions.
     Incineration  centres  accept  solid,   pasty  or   liquid
wastes,  in  -function  with  technical  characteristics.   Under
currant  regulations,   the  centres   must  respact   operating
temperatures on  tha  order  of  730ฐC  
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     Incineration in Cweent Furnaces
     Cemont  plants  consume huge  amounts of  energy.  Therefore
cement plants  have  sought ! alternative fuels  in  order  to lower
their  energy coats.  The  cement  industry  has  now: turned  its
attention  towards wastes,  and particularly  wastes with  high
calorific value,  such  as hydrocarbon mixtures or  certain  nan-
regenerable  solvents.  The  current trend  is toward  producing
mixtures   attaining    -   on   average    -   the   following
characteristics!           .           •            -     •

a> Minimum Calorific Value of 4000 kgcal/kg
b) Perzantage of Cl <,0.5 */.                 ,
c) Per cent ago of HaO < 40 V.

     Moreover,   environmentally   speaking,   the   technical
conditions  of   furnace  operation  guarantee  minimum  pollution
because of  the burning  temperature  of  clinker  and because  of
the long  contact  timป between the combustion products and the
matter to be burnt.  
-------
      Certain .heating  stations  and  certain  household  r-e-fusฉ
 incineration    units   also   . accept    spacial    wastes   for
 incineration.
     1  The 'disposal  capacity  of collective  incineration centres
       is nearly 800  000 metric tonnes a year  (1989).
      Incineration at S*a                        •        • •
      The destruction  o-f halogenated wastes  can be carried out
 in  facilities  installed  on  ships working  in the  North  Sea.
 Waste  producers must  contact  either  an  intermediary storage
 centre or a collector,  who  will than  subcontract with tho firm
 managing the  incinerator ship  for the  subsequent destruction
 of thซ wastes.  A European directive will placs legal limits on
 recourse to -this  method o-f, disposal.  The quantity incinerated
in 1988  was' 15  000 metric tonnes  and is  in'constant  reduction,"'
      3.3 Ptiyaico— Chซ*ic*l Processing  Contra*
      Physico—chemical  treatment  centres  mainly  perform  the
 •following... treatment procassesj  oxydat ion-reduction,,  neutrali-
 zation, dehydrationi fixation,  and  emulnion—breaking.
     • Wastes accepted- by  these  centres are:
 a)  liquid  wastes  containing  cyanide. Solid  cyanide hardening
      salts  are not  detoxified  at thesa  centre.*?  rather, they
      are conditioned for land-burial storage in salt mines. At
      present,  they are  shipped  to West Germany.
 b>  Wastes  containing  hซxavalent chromium.  These  wastes are
      first  reduced  and then  precipitated into  an  insoluable
      form.  When  the solutions  arc  highly  concentrated,' the
      possibility  of valorization can bta  considered.
 c5  Waste acids and bases.  These wastes are neutralized.
 d)  Solutions  containing metals. They arm precipitated.
                               233

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e) Pasty wastes containing toxic  element*. These wastes can be
     treated   by   fixation,   or   hydraulic  bonding,  thereby
     reducing  tha  level  of  humidity  and  limiting leaching of
     toxic elements.
f) Ion exchangers. They are regenerated.

      The  capacity of collective detoxification  centres in
      nearly  360  000  metric  tonnes  a  year  (1988)   (See
      Appendix 4).

     3.4 Specialized Treatnent Centre*
     Certain  firms  have  specialized  in   the  treatment  of
particular kinds of wastess;

     Fluid* Produced in Mปtalworking
     The fluids can be grouped  into  two categories!  solvents
and emulsions. They contain  approximately 5% oils and various
sterilizing agents, bactericides etc.*.
     Various   processing   techniques   are  available.   Acid-
breaking 'and  ultrafiltration apply only to  emulsions, whereas
incineration can be usซd in the treatment of all  such fluids.
      The  capacity of  collective  waste treatment  centres is
      appoximately 265  000 metric  tonnes a year
     Solvents
     Thป regeneration of solvents can take three forms:

a) Internal regeneration of solvents by the firm
bJ The  firms  supplies waste solvents for regeneration  outside
     the  firm  and   will   subsequently   use   the  regenerated
     solvents.
c> Waste solvents are sold for regeneration outside the firm.
                            234

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      The,choice of  one .of these three alternatives  will  depend
upon  the quality, of the  waste solvents  produced,  the,  market
value of the. solvent,-,  the potential  for re—use of  regenerated
solvents within the -firm,  etc...             .  .  •
      The -following  regeneration techni quea" are available:
 13 steam distillation
 2) -fractional  distillation
 3) separation  in  a -fine layer

     .The  first technique  produces a  solvent  which is  largely
 free o-f its  impurities, but heavily saturated with  water.  This
 technique  is often used for  sales (se* "c" above)  of  solvents
 with low market values, particularly with chlorous solvents.
     The  second   technique   is  often  used  with  solvents  of
 higher  market  value when  the firm supplies the  waste  solvents
 for  regeneration  to • specialists  in solvents refinin.g  
-------
earmark certain wastes  -for  subsequent  valorisation,  instead  of
di sposal.                   :                     -
     These  centres  are  equipped  for  reconditioning  wastes
(separating   them   into   homogeneous   batches   fqr   easier
disposal).  The wastes  are  then  shipped  to  the  appropriate
collective waste  treatment  centre. The transfer centre  groups
wastes  in  quantities generally  between  50  and  10O litres  in
drums and 1 to 10 metric tonnes for bulk wastes.
     3.6 Technical Land—Burial Centres
     Not   all   special   wastes   require   incineration   or
detoxification  and  for  many  of  these  wastes  (particularly
those containing  the lowest concentrations of  toxic  elements)
storage  in  landfill  or  dump  facilities  is a necessary  and
technologically , accepted  disposal  solution,  provided  certain
specifications are respected.
     Technical land—burial  centres  can be established  only  in
geologically favourable areas  (with  a permeability coefficient
lower than 10—*/s>           >
     The  circulars  of  22  January   1980: and 16  October  19S1
specify  the  conditions necessary  for  opening and  operating
such  waste  storage  sites.   They  define three  major  types  of
sitess           ,

A}  Impermeable  sites,  which;  ensure , suitable  confinement  of
     wastes  and  leachable  wastes.   They  are  able  to  store
     certain special wastes. >
b)  Semi-permeabla   sites,   which   ensure  , slow  migration  of
     leachabla   waste   through  a    nan—saturated   zone   of
     sufficient   thickness.  ;They   can  store   mainly  those
     industrial wastes comparable to household  refuse.
c) Permeable  sites,  which  allow  rapid migration  of  leachable
     waste.  Only inert wastes!should be stared  in such  sites.

     Managing  water  at the  site  is  one of the major problems
when operating a landfill of this kind.
                             236

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     When tha ground  is  impermeable,  all  the water penetrating
into the  site accumulates  at  the bottom" of the  pores." It is
therefore  important  to  restrict  the amount  of  water  coming
onto the site. Water  contained'at 'a  site  can come from several
sources: •        •          ,••••-•

a) rainfall at the site";            '.'''''
b)  diversion ' of  surface  water  or  . leachates,   surfacing 'of
     groundwater or return -seepage';
c) water from pasty wastes or sludges.

     The  first   source  listed  is  not'' easily'  controlled.  The
only means of limiting' this  factor is through the selection o-f
special sites or the  reduction  of  the exposed surface-area.
     The. second  source i's  controllable! one simply has to' seal
the site environmentally,  both the sides  and the base,  'and'to
build  channels   permitting  water  to  run  off  beyond  the site
without coming into contact  with the  contents of  the  site.
     The  third  source  can  be  controlled  by   limiting  the
humidity  of  /the  'waste  -accepted;.   Several-'  techniques  are
availables dehydration  of sludge  through a filter press or a
band filter,  perhaps  after flocculation;  use of solidification
techniques  for  dehydration? confinement  of  pollutants  in  a
cement structure.
     When  the site is  not totally  impermeable,  water passing
through the  site could  filter into  groundwater,  presenting a
risk  of  polluting  this  water.  However,  soil  does  have  a
certain retaining  powซr,  in particular  in the  case of heavy
metals.
     The, principal  criteria for acceptance "of  a 'waste product
by a landfill arw:                                  '   '

1) drynesa
2)  The nature of  the soluble  fraction obtained  from leaching
     of the waste."  '       ••  •       '   '••••"     • '    ~
                              237

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     The table 2ซlow presents  a  list of acceptance critarias
1) Concerning the raw waste;
     a) Dryness	> 4O  %
     b) Solublซ fraction.,..	........< 10  %
     c> Hydrocarbon cantients total hydro-
     carbons	-.. .	..",..< 10  %
2> Concerning the leachable .matter*
     a) pH.	!.......	6 < pH  <8
     b) Metallic elements      ,
          1) Cr VI, AS 3*, Qrganic Kg and
             Pb, CH.	< 1O  mg/kg  of wast*
          2) Ag, Cd, Se, Thป Hg, Pb++.....< iOO mg/kg of wastฎ
          3) Ba, Va, Sn, Cuป; F-, S 2-ป mineral  Pbป
             Al, Mn, Ni, Zn, AsS+, Cr3+ซ...<  Ig/kg o-f wastป
     c> Organic substances   \
          1) Substances extractable -from
             chloroform	.<  12O  g/ko of waste
          2) phenols	<  200mg/kg of waste
          3) DCO	').	.< 20  g/kg of waste
          4) DgO S....	<  7  g/kg of waste
          3) Nitrogen measured by Kjeldahl
             method (axprasscsd in NH4->-)....<  2.3  g/kg of waste
     d) Ecotoxity	.......<  1 equitox/m9

     Most   technical    landj-burial    centres   receive   both
industrial  and  household  wastes.   Considering  the  current
difficulty  in  opening   newi  Class  1  sites,,  it   would  be
preferable  to  restrict  their use  for wastes  which could  be
treated in Class 2 sites.    :
      The eleven  (11)  Class ;1 technical   land-burial centres
      received  nearly   500  :000 metric   tonnes   of   special
      industrial wastes in 1988.  Today,  the major problem with
      this type of  facility is obtaining  their acceptance by
      people living nearby. Consequently, no  new site  has been
      opened for five  years.  ;           -
                              238

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Concltmian

     Indus-trial  wastes management  long  consisted  in  skimming
off  a  -few  wastes with  a  known  market value  (such  as  scrap
iron,  non-ferrous metals,  waste  paper and  cardboard,  etc.)
while summarily  - and frankly,  even  recklesay -  disposing  of
all the other wastes.
     The concern  for better protection of the  environment  and
for  a  better control  of  raw materials and  energy has  led  to
more  rational  and,  more  effective  management  of  industrial
wastes.
     Better   knowledge  of   wastes'   characteristics,   better
sorting of  wastes at the source,  and  appropriate  conditioning
are  prerequisites if  one desires the best  possible  disposal
(and, if possible, valorisation) of wastes.
     The proper  management  of  wastes  produced  by  firms  rests
on several  principles:

1) The  organisation  of waste  storage must take  environmental
     and security constraints  into account,  but it must  also
     respect  the limitations  imposed  by  subsequent  treatment
     of the wastes,  in order to reduce costs. • .
2) The  choica among  waste  treatment  by  tha  firm  itself  or  by
     collective  treatment facilities  depends on the amount  of
     wastes  to  bซ treated  and  on  thป firm's possibilities  of
     using    th*  products    (or   energy)    obtained    from
     valorization.
33 The choicป bstween  various  waste treatment  services depends
     on thป total waste  treatment costs  (including  transport
     costs)}  clean technology  and  valorization  should  be given
     preference  bacause of  the economic advantages they often
     present  in comparison  to disposal,

     At  a   national  level,   for more  than ten years,  public
authorities  have  actively  supported  the establishment  of  a
national network  of  collective disposal  centres for industrial
wastes.  This support  has been  translated principally  into  a
                             239

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more  demanding  legal  arid  regulatory  -framework  (-for example,
the Law  of  15 July  1975  on waste disposal  and  the Law of  19
July 1976 an facilities classified as  being  for  the protection
of   the   environment),   the   establishment   of    incentives
(financial  aid   for   investments)  and  unflagging   support  of
research seeking to improve treatment techniques.
     This combined effort from the public and private  sectors
toward tha  same  goal —, the  effective treatment of  industrial
wastes - has led  to  providing  France with a dense,  if  not  yet
totally  mufficientf   network  of  collective  treatment  centres
for  industrial  wastes. This  network  is  insufficient in  that
certain  regions   severely  lack  technical  land-burial  centres
and that, nationally,  France  has yet to solve the  problems  of
disposing  of  certain  categories  of  wastes  which,  at   the
currant state of tachnology, require deep storage.

       The  steady, regular progression of treating  toxic  and
       hazardous  industrial  Wastes   in  collective centres
       (500  000 metric tonnes in 1982 ; nearly 1 030 000  metric
       tonnes  in  1988 in  addition  to  constantly  improving
       effectiveness  of treatment  techniques is a  sign of  a,
       certain level of success; in this sector and also sign [of
       a  real  need on the part; of  industrial waste  producers.
       Even  if, at a  local  level,  technical landburial centres
       are less and less easily- accepted by the population,  the
       environment has everything to  gain  from an  effective
                               i
       network  of  collective!  industrial  waste   treatment
       centres.                 i
                               240

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 INDUSTRIAL WASTE  PRODUCTION
             IN FRANCE
 INERT
WASTES

 100 Mf
            TOTAL AMOUNT
            50 MILLION TONS
COMMERCIAL
  WASTES

  32 Mt
SPECIAL
WASTES

 18 Mt
                             HAZARDOUS
                              WASTE

                                4Mt
                   241

-------
                              ANNEXE 1


                        INDUSTRIAL JWASTES MANAGEMENT
                                                              Plant
Internal
DISPOSAL
 External

 DISPOSAL
RECYCLING

VALORISATION
OTHER
PROCESS
                                 242

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               HAZARDOUS  WASTE  TREATMENT
                             FACILITIES
rvj
*ป
00
        INCINERATION
    SPECIFIC INCINERATOR

     POWER STATION
     MUNICIPAL WASTE
     INCINERATOR
  PHYSICO-CHEMICAL
    TREATMENT
OXYDATION REDUCTION
                           DESHYDRATATION
FIXATION
EMULSION BREAKING
    LAND BURIAL
SECURE LANDFILLS
                      SALT MINE
                      BURIAL

-------
            INDUSTRIAL WASTE  TREATMENT  PLANTS

                           IN  FRANCE (1990)
SCF(GargenvJile)
     *
              'EDF-T1RU  VICAT(Pont & Vendin) ฉ^IfHBNPCfCourriore)

SARP(Llrnay} (ivry sur Solne)         X^ S~H~^— ~s^

                                   VIDAMCAjniens). f
                                                          CEDILOR(Jouy aux Arches)


                                                                         TREDi
                                                                      (Strasbourg)
                                                                     TREDI(Hombourg)
                                                        CiMENTS DE CHAMPAGNOLE
                                                          (Rochafort  Sur  Nenon)

                                                         CIMENTS DE CHAMPAGNOLE
                                                              (Champagnole)
                         GEREP(MItry-Mory)


                     SOTREMO(Le Mans)
                                               VICAT(Xeullloy)

                                                     SOTHEFI
                                                    (Mandeure)
                                        LAFARGE(Frangey)

                                          •\
                                      SCF(Beffes)
           SCF(Alrvault)


           \\*l    "
ANTIPOL(Fontenay Le Comte)
                                                           /a ป   i
                                                           TREDI(St vulbas)
                                                                l
                                                      VICAT(Mpntalleu)


                                      SPUR(La  Talaudiere)  T^fREDl

                                      LA'FARGE(Le  Tell')  \ft M*i_s*  \
                                        I /  V  " "V M  1 ''"*'" ' *     -^
                                       J-/  \     1   -I SlRA(Chaซ9B Sur Rhone)

                             LAFARGE(Lexoii)   (_ ^V — ^^\7-/^"  (^ -- .

                                                      SCF(Beaucalra)  )
                                                                    /
                                                                      Malla)
      SlAPfBaasens)
L*ELECTHOLYSE(Latresn8)
            SOBEGI(Mourenx)
                                                    COHU(La Mads)
                    INCINERATION PLANT

                     UlflSTE BURNINB CEMENT UJORK

                     PHYSICAL AND CHEMICAL TREATMENT

                     EUflPO-INCINERRTION PLRNT
                                         ,244

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             RMOUNTS OF OJHSTES DISPOSED OF
             IN COLLECTIUETREflTMENT UNITS
      Tonnes
1200000 -1
1000000 -
 800000-
 600000-
 400000-
 200000-
        1982     1983     1984    1985    1986

                       TOTflL flMOUNTS
1987
1988

-------
400000
300000 -
aoQooo -
100000 -
                                    246

-------
                I
                  1
                                                                            T

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                                  o .

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                                        co
                                             O •
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 8
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                                                : O
                                                                          CO
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                                                          CO
                                                          en
                                                                           CO
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                                                            8
                                                            o
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                             247

-------
                        flMOUNTS OF UJflSTES DISPOSED OF
                        IN COLLECTIUE TREflTMENT UNITS
                  Tonnes
              400000 -Y
                                               DETOKICHTION UNITS
              300000-
ro
              200000-
              100000 -
                      271000
                                292000
                                           289000
                       1984
1985
1988
                                                      317000
                                                                  362964
1981
1388

-------
 TECHNICAL LAND-BURIAL CENTRES
           ( SECURE-LflNDFILLS )
                           MENNEVILLE
GUITRANCOURT
           TOURVILLE LA RIVIERE
       ARGENCES
                                LAIMONT
                       VILLEPARISIS
                                 JEANDELAINCOURT
                                             /
                                            VAIVRE
CHAMPTEUSSE SUR BACONNE
                             PONTAILLER SUR SAONE
                               BELLEGARDE
                         249

-------
WASTE  ACCEPTANCE  PROCEDURE
               WASTE; PRODUCER
                 WASTE SAMPLE
               TREATMlN
T CEFJlER
               ~s~AJ\Me ANALYSIS
          I  ACCEPTANnrUERTIFICATE  I
                s
              UNIQUE OR REGULAR
                 COMPATIBLE
              WITH ACCEPTANCE
                                  CONSIGNMENT
                 COMPATIBLE
                WITH 1st SAMPLE
               WASTE TRtATMlNT
                     250

-------
        TECHNICAL  DATA  FOR
        INCINERATION  CENTERS
ACCEPTANCE  CRITERIA
   - Calorific  value (combustion control)
   - Halogen  content (need for specific
    centre)
   - Metal content (alkaline elements)
   - Flash point (security)
   • Physical aspect (liquid, solid or pdsty)

COMBUSTION
   From 750ฐ C (simple  organic wastes)
   To 1 200ฐ C (organo-halogenated wastes)
   Time : 2 sec
   Post-combustion  necessary

           MAIN PARAMETERS
   Cl              <  100    mg/N.m3
   Dust            <  150    mg/N.m3
   Heavy metals   <  5     -mg/N,m3
                    251

-------
                      BMOUNTS  OF UlflSTES DISPOSED OF
                      IN TECHNICBL  LBND-BUBIBL  CENTBES
.
tn
  Tonnes


1500000-






1250000-






1000000-






 7SOOQO-






 500000.






 250000.
                      1985        1986        1987        1988

                          DECHETS INDUSTRIELS SPECIAUX IMPORT


                          DECHETS INDUSTRIELS SPECSAUX FRANCE


                          ORDURES MENAGERES, DECHETS BANALS

-------
      TECHNICAL  LAND-BURIAL

                CENTRES
SITE  QUALIFICATION
                                   '   9   -.
  Impermeable site :  permeability   < 10  rn/s
                    substratum    > 5 m

  Water protection (surface and underground)

  isolation from surroundings
ACCEPTANCE CRITERIA

- Water content

- Physical aspect (solid ou pasty)

- Nature  of soluble fraction  (leachate test)

- Prohibited  substances (PCB, cyanides,
  explosives,,..)
                    253

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-------
                       NAtO/CCMS Guest Speaker:

                           Christian Bocard, France

New Developments in Retriediation of Oil Contaminated
                            Sites and  Ground Water
                255

-------
         NATO/e;CMS CONFERENCE  November 1990
   NEW DEVELOPMENTS IN
        REMEDIATION
OF OIL CONTAMINATED SITES
AND UNDERGROUND WATERS
        Christian BOCAED
   INSTITUT FRANCAIS DU PETROLE
              i
              and       ' ,

Jean DUCREUX, Claude GATELLIER (IFF)
  Jean-Frangois BERAUD (BURGEAP)
              256

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REMEDIAL ACTIONS  : WHY AMD TO
  BASIC   DATA   ON   THE   TRANSFER   OF   SOLUBLE
  HYDROCARBONS FROM RESIDUAL OIL TO GROUNDWATER

     In the saturated zone (Figure 1)

     In the unsaturated zone : more knowledge needed
  A FIELD EXPERIENCE

  The  construction of  a subsurface  railway  across  a
  contaminated area :
     necessity of mitigating short-term and long-term risks
     towards the works

  Actions undertaken :
        Hydraulic pumping
     .  " Experimental in situ aqueous surfactant  flushing
        (Figures 2 to 9)
                      257

-------
       THE USE OF SU1FACTANTS
 TO IMPROVE IN SITU WASHING AND
            BIODEGRADATION
             BASIC CONSIDERATIONS
   EFFECTIVENESS OF SURFACTANTS

      Optimum oil recovery in column tests (Figures 10-11)

      Enhanced biodegraclation (Figure 12)
m  HYDRAULIC PARAMETERS TO OPTIMIZE

      Flowrate of surfactant solution
      Arrangement of injection and pumping wells

      in order to ;                            •      -.

      Sweep- the whole contaminated area, taking account of
      water permeability and relative permeability
      Avoid surfactant passing through the water table

      Studies carried out irk laboratory models and field pilot
   tests (Figures 13 -H )   •
                      ; 258

-------
                                       >
                                       >

                                       UJ
                                       LLJ
                                       DC
                                       O
                                       Q.

                                       UJ
                                       111
                                       cc
MO  (Wdd) NOI1VU1N30NOO

NoauvoonaAH QSMOSSIO nvioi
   FIGURE 1  Sctublllzaticn of hy.d-ocarbors
                259

-------
                                                                   EXTENSION DE LA ZONE PO1.LUEE
                                                              ET N1VEAUX P1EZOMETRIQUES
1NJ
o
O
             LgGjNOE

        Pulls de rabaltement

        Plezomelre BOTTE

        PtMomelre SOTRAISOL

        Pulls de depoKutlon

—— — Drain

   O    Pulsard de recuperation

 23,00  Equlpolentlelle de la nappe
        des calcalres de SI. OUEN

 27t?7  Nlveau plezometrlque suapendu
                                                                            Llmlle approxlmallve
                                                                            de la zone pplluee

                                                                                  llmlfo da I emprlso
                                                                                  du chonllar
                                                                                                         22,7^  Nlveau plezomclrlque
                                                                                                               anormalement bas
                                                                                                                 (23,16 JปTfl
                                FIGURE  2    Tha eontaminated  site

-------
                              FIGURE 3
COUPE GEOLOGIQUE  PASSANT PAR I1'AXE  DE LA TRANCHEE
NGF
                                                                                             C5
JO
It-
IQ.
     C2   ซ2


            -l-l-l-l-t-l-l-l-]-l-l-

                                                                            •\Marno_- colcatrxt
                                                                            '

                                                                 ..   ;-'•;: .  •' . \\5obits da Btavchatnp
                                                               V.  • _,', .;:..:.•  || .-.j-s- -: /.. . ; .:;., , lti ,
                                                                           u
IOJ

-------
ro

                                                                                                 1Mb d* I ซ**!ป*
                                                                                                             Limile d'extension du produtl
                                                                                                             sumageant SIIT la nappe
                                                                                               Limite de la zone d'influence
                                                                                               des puils de depollulion
                                                 UNITE D'ACTIOM QE U PREMIERE PHASE DC DEPOLLUTION
                                                 Apr*s 10 1 30 jours de pompage
                                         FIGURE  4    First hydrauHe dopollutlon  phase

-------
ro
en
U)
                                                                                                             Limite dc la zone il'influencr
                                                                                                             des jHiits de dipollulion
                                                                                                          l.innle d'extension du produil
                                                                                                          surnageant sur la nappe
                                                 UMITE D'ACTION DฃU PREMIERE PHASE DE PEPOLLIIT10N
                                                 Aprts 20 i 70 jours de pompage
                                      FIGURE 5     Second hydraulic depollutlon  phase

-------
VOLUME
flECUPERf
f LITRES J

    4000.
    3000.
    2000-
  ro
    1000-
                                                                                   04
                                    o-o-
-001S
       22/05     19,436     IQ/D7       7/08      4/39      2/10      30/10     27/11
                 TEMPS
                             Quantl-t6 de produit rficuperfi sur lea pults  de dSpollution D4 et D15
        •t'KJU
                              FIGURE 6   Cumulated volume of recovered  oil

-------
       1000.
                                                                                              10
(S3
CD
Ul
   o
   o
   3 '
   .">
   .'11
   3
   rt

   a
   rt- '
   H-
   O
   3
   U
   3

   3*
   O
   O
   &
(I
w
                 R4-(D4)-D13
     50 O-j
                                                          i.ft  \    MA  e HydrAcarburtt
                                                          (10ml    'ซ  O Tt.tlt-.nifi
                                                          (30m)   Hi
                                                                     o  Tamlt-aetlft
                                   t
                                               liijtctitR
.5
                                              Tiniit-iclifป
               Evolution des concentrations en hydrocarbures et en tensio—actifs de 1'eau dee puits D4 et
               D13 lora dee traitements :  influence  de l*61oJgneinent dea puits de dfipollution  •  ....... •
                                                                                                  HO


                                                                                                  n
                                                                                                   u
                                                                                                   to
                                                                                                      4)
                                                                                                   c
                                                                                                   o
                                                                                                      .p
                                                                                                      at
                                                                                                      u
                                                                                                      8
                                                                                                      o
                                                                                                      o
                      FIGURE 7   Surfactant flushing : eoneentration  of emulsified oil

-------
          300.
      n


      g

      •H
PC     -P
      C
      u
      u

      g
      o
          200.
100-
                  R7-D7
                           i
                                                          surfaet
                                                        -B fond
                   15 JUIUET           16 JUILLET         17 JUIUET
                                                                     22JUIUET
                                   Injiotion Ttntio-ictifs
                Evolution den teneura en hydrocarburea S la surface et *u fond du puits D 7 lorn du traltement

                aus tensio—actlfs
                     FIGURE 8    Surfactant flushing : concentration of emulsified oil

-------
,

Before treatment
1 :
' 2
Alter treatment ,'•
; 3, "' ':•
HYDROCARBON CONCENTRATION
IN WATER (mg/1)-
D4
63
22
5 ''
D7
15
0.6
0.3
D13
19
13
7
D15
6
27 '
5
TOTAL OIL 1ECOฅEEY WITH SURFACTANT FLUSHING : 250 litres
       FIGURE Q   Results of surfactant flushing
                         267

-------
                     Inter facial tensions -ปnd oil recovery efficiencies
                    of some commercially surfactant in experiments with
                    gasoline  and fuel oil #  2   V**b  tn *aVuroJHA
    Oil
Surfactant
   type
    Active
  Surfactant
Concentration
Interfacial
  Tension
  (mN.m-1)
 Recovery     SO
Efficiency    	
    (%)       EO
 GASOLINE
               SULFONATE 2
               SULFONATE 3
               APPE1
                   0.5
                   0.1

                   0.5

                   0.5
                      0.015
                      O.025

                      0.358

                      0.091
                   41.3
                   13.3

                    4.9

                   14.5
              11.4
              15.8

               O •

               3.1
.-'DEL OIL #2
                SOLFONATE 2
                SULFONATE 3
                APPE 1
                    0.5
                    0.1

                    0.5

                    0.5
                      0.085
                      0.100

                      0.745

                      0.130
                   83.1
                    7.8

                    4.4
                      <

                    8.8
              13.6
               6.2

               3.8

               5.3
* : SO/EO s ratio of separated oil to emulsified oil.

 ?                                      FIGURE 10
  o
  ro

-------
to
                                    -O*
^
                                         ts
                          >A**^      '
                         s ^**^.^
1

2
A—-A  surfactant in effluent
•ซ_•  raw oil
o-—o  surfactant in effluent
      (sand control test)
      tracer
[o——o


~'   ™
                          2      3      4      5      6      7      8      9
                                Relative Pore  Volume  (V/Vp)

                     Surfactant effectiveness on  the  gas-oil recovery

                  Effect of the surfactant partition  between water and  oil.
                  1:Sand column   2: Control test (no oil)
                           uvKKo.ua
                                               .1.0
                                                   O
                                               0.5 '
                                                  •ง>  O
                                             10
                                                  •D  o:
                                                   0)
                                                   N
                                                  mmmu
                                                   CO
   FIGURE 11

-------
       Aliphatic  Hydrocarbons
                           Aromatic Hydrocarbons
a.ii.
11.13 .
          ijuuku
D
                         GAS-OIL (INITIAL)
                    S,
AwL
  I.M  u.n  a.m
                                      4.75.
                  m.tt   B.TO
                                                               QAS-OIL (INITIAL)
                              ป.a  ui.n
                                        .
                                       •inutis
                                                   41,i9  I9.M   a. 73   H.M  H,i9  110.M
                                                                CONTROL TEST
                                           111	 Jill
                                        I.M  11.11  ]>.ป  41,99   55.M   rj.73  C.50  91.80  110.M
                                        Mnutra
I',*-.
                     TEST WITH SURFACTANT;
                     I             !
                                                           TEST WITH SURFACTANT
                          n.99  n.a  no.oo
                                        linutis
                                                                    98.23  118.84
  Aerobic blodegradation enhanced with surfactant
   Oil eliminated after 50 days In column test,:      eontrol test : 53%
                                                      sufactant test : 98%
                                FIGURE  12
                                   •:270

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Surfaetant flushing  in laboratory model  2.5m x 0.5m x 0.12m
                         FIGURE 13
                             271

-------
   C
INS"  30
                    0
           1                 2

              Flow  (l/h)


CapSMary fringe  penetration by surfactant
                        vs injection flowrate and  hydraulic gradient

-------
                    NATO/CCMS Guest Speaker;



                       Jean Marc Rieger, France



Incineration in Cement Kilns and Sanitary Landfilling
              Z73

-------
                       NATO   CCMS
          PILOT STUDY DEMONSTRATION OF REMEDIAL ACTION

      TECHNOLOGIES FOR CONTAMINATED LAND AND GROUNDWATER
SESSION OF NOV. 8TH 1990 IN ANGERS  t

INCINERATION IN CEMENT KILNS ANb SANITARY LANDFILLING
By Jean-Marc RIEGER
SCORI
10/24/1990
                              274

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SCORI is  an outgrouth of the Environment Department  of SERI RENAULT
Engineering (Car Manufacturer).


The  first  projects date from  1972 and consisted of studies  and surveys on
industrial, wastes-'on behalf of the French Government.  . •.


From  197ง,  SERI has  collaborated  with  the  company  FRANCE  DECHETS on
the-  development of a  network  of controlled, special  waste  landfills in
France. The cooperation  between  our company and  FRANCE  DECHETS is
still  running and will be described later on.

As early as 1977,  the  company had made contact with CIMENTS  FRANCAIS
for the development of waste incineration in  cement kilns.


The  company SCORI was created  in 1979 and provides services in the field
of sanitary  landfilling  of special   (hazardous)  waste   and  cement  kiln
incineration.

During  the  early 1980's,  SCORI  progressively expanded  and  strengthened
its waste  treatment activities  and  became one of the major  French waste
management firms.

in the continuation of its  development, SCORI became a  subsidiary of the
principal cement companies in  1985,  namely  CIMENTS FRANCAIS, CIMENTS
LAFARCE  and  VICAT.

Since then,  SCORI has continued  its internal and external growth.
                              275

-------
Treating  more  than  700.000 [tons  of  special  waste in  1988,  and  almost
900.000  tons in  1989,   SCORI   has  a  consolidated  turnover  of  FFr  180
millions.

SCOR!  employs  over 160 personnel  specialized  in the recycling  and disposal
of industrial waste in its seven  business offices and its  five subsidiaries.


SCORI's principal activities  are  in the following areas :


Class 1 and  2 Controlled Waste  Landfiiling

Waste  landfilling centres are the first in a line  of SCORI services.  At the 8
centres in  France run  by  FRANCE DECHETS and  its  subsidiaries,.  SCORI
receives a large spectrum of special industrial wastes in perfect conformance
with existing legislation.                                           >
500.000 tons are treated annyaJly on these Class 1  sites (permeability of the
underlying earth  less than 10 !  mis).
The total  number of Class 1  sites in France is  11.


Cement Kiln  Incineration      :

Destruction in cement kilns combines environmentally safe waste incineration
(up  to  2000ฐC)  and energy  recovery.  Fifteen kilns  are today licensed for
waste incineration in France.  SCORI is  involved in 14 of them.  250.000 tons
are incinerated  annually  in these kilns.


Combustible  Waste Preparation jCentres

Certain types  of waste  cannot  be  directly  incinerated  at a cement plant
because of their physical characteristics.

SCORI  and  its  stockholders  have  developed  a technique  for  producing  a
stable  combustible suspension ^called "COMBSU", starting with  liquid,  solid
or pasty waste.

Two centres are  producing  this combustible,  treating  approximately  50.000
tons/year altogether.         !
                                276

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Pretreatment and Treatment of Waste by Physical-Chemical Techniques

Various centres are specialized  in the  stocking, grouping  and  pretreatment
of industrial  waste.  SCORi  is  involved  in  6 of  them, where more than
150.000 tons of materials  have  been selected, prepared  and-distributed  for
appropriate treatment.                                   ,


Co-Incineration  wjth Household  Wastes

20.000 tons are treated annually by SCORI by co-incineration  in one out of
the two existing household waste  incinerators licensed  for  hazardous waste
treatment in  France.


Waste Recovery and Plant  Dismantling                             ,

SCORi  provides  sorting  and   disassembly  services  as  well   as  a  resale
network.  Close  to 25.000  tons  of  different raw  materials   are  handled
realizing important sayings for its  customers (e.g.  RENAULT).

A  fast  growing   plant  dismantling   activity has  been  added   to  this
department,  mostly concerned  by  material  recycling hit working  together
with  our haz-waste specialists when cleaning or decontamination is required.
In addition,  SCORI's  policy of European expansion  has led  to  the  creation
of two new foreign subsidiaries in Belgium and Spain,
                               277

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SOCIETE DES
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SCORIBEL
(Belgium)

ENDER'
(Spain)

280

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INCINERATION  IN  CEMENT  KILNS
    The  cement  kiln  is  a  particularly  effective tool for  the incineration  of
    special wastes :          .'       '                    '


    *  high temperatures and  long gas residences times (more than  5  seconds at
      more than 12QQฐC),

    ,  efficient  gas cleaning  :  the cement  process offers a very   high  capture
      capacity  for halogens (close to  100%)  and for metals (greater  than  95%),

    .  the cinders remaining  from waste  incineration  are  incorporated  in their
      inert form into the  cement clinker,

    .  the quality  and the reliability  of destruction are related  to  the necessity
      of  closely following  the clinker  fabrication  parameters,

    .the depth  of  response  from the  cement  manufacturing   profession which
      has oriented  its  significant technical  potential towards the  quality  of
      incineration.
                                   281

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                                          WET PROCESS
TEMPERATURE ฐC
                                DIRECTION OF "MOVEMENT OF THE MATERIAL
                                                                               Firing end
Dehydratation
.zone • ;
Becarbonation zone

sation zo
~™~""T
le
1
- — - — -
Cooling
                         100
700/900
                                                              1450

-------
          Temperature of the
    1000
        m/ij
GU
ill
        TEMPERATURE OF A MOLECULE INTRODUCED AT THE BURNER AS A FUNCTION OF TIME
TEMPERATURE* C
        2000
         1500-
        1000
                                                                        7 s
                                                                               TIME

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SCORI'S WASTE ACCEPTANCE PRdCEDURE

                                  I
    SCORI  Initiated  and developped the  procedure for acceptance  of  polluting
    wastes in treatment plants.    ;
                                  i

    1st step :  Waste characterization

    Waste  characterization  is based on  a sound knowledge of  origins  of  the
    waste and on sampling  and laboratory analysis.
    For incineration, analysis of wjater content, calorific  value,  chl.orine, heavy
    metals,  PCB, sulfur etc... are ; performed.
    In the case of landfilling, leaching tests  are  used to simulate the  behavior
    of wastes in the presence of water and to Identify the  risk associated  with
    the dissolution  of polluting substances.
    These   analyses  are   performed   by  external   laboratories,  or  by   the
    laboratories of  the  treatment centres.
                                  i

    Waste acceptance

    The  results of waste  characterization (physical state,  levels  of polluting
    substances  in   relation   to  admission  thresholds,   etc.,.),   permit   the
    evaluation of the acceptability  of a  waste  in treatment facility.
    When  a  waste  is  found acceptable, notification is  made  to the waste  holder
    who  can  then  arrange  the  delivery of his  waste  to  the  centre.   An
    "Acceptance Certificate" is sent; to  the  holder.


    Waste admittance  on the site   i

    At  site  reception,   and   after   checking   the   Acceptance   Certificate,
    verification is   made, to ensure that the waste delivered conforms with  the
    sample held by  the  onsite  laboratory.
    Following  this   admittance procedure,  the  weighing  and   unloading   are
    performed, and a  certificate of transfer  of control  is  then given to  the
    carrier and waste holder.


    This   procedure  is  rigorously  followed   and  contributes  to an  efficient
    selection  of wastes which merit specific disposal.
                                    284

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          NATO/CCMS Guest Speaker:



                 Bruno Verfon, France



Contaminated Sites - Situation in France
   285

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              CONTAMINATED S;ITES - SITUATION IN FRANCE
SUMMARY                        :

In France, although the problem of contpminated sites has not reached until now the level of
a first priority like in the USA or in some European Countries it is considered with seriousness by
the National and Local Authorities.
                                   i
Action has been and is presently carried out for the three main steps of these problems:

     - Identification  of potential problems - contaminated sites registration
     - Evaluation of  site contamination - risk assessment  '
     - Treatment of  contaminated sites;- land recovery  •

Cleanup costs are most of the time supported by the waste producer or disposer according
to the "polluter must pay" principle. In some cases, publics funds have been granted,
because of lack of responsible party. At the present time treatment techniques range from
site control up to complete cleaning involving hazardous material extraction and off site
elimination with  some  significant  cas^s of  waste encapsulation and  more numerous
examples of restoration by solidification-stabilization.

This last  techique excepted, there have been, up to now, few french technologies
developed specialy  for the rehabilitation of contaminated sites and soils. This situation can
be  explained by the relatively limited 'number of hazardous sites registered and by the
existence of a rather well developed  system for the treatment  and disposal of industrial
waste which can be used for the off site treatment of contaminated materials and soils.
However this situation may change In the near future because of the increasing number of
sites to restore and  in this view we have decided to play an active role to promote the
development of new french or imported techniques for the treatment of contaminated soils.


I  - tDENTIFlCATtON OF POTENTIAL PROBLEMS - CONTAMINATED SiTES INVENTORIES

The first step of french action in the field of hazardous dumps sites and contaminated land
consisted in two Inventories carried out in 1978 on national level:

-  the first one realized through inquiries of the Ministry of Environment among the  local
  Inspections of Classified Installations responsible for control of polluting industries -including
  disposal installations-. By this mean, abbut 120 questionable sites were identified of which
  62 were recognized as serious and therefore requiring priority corrective action

-  the second one, consisted in a study made by the Bureau de Recherches Geologiques et
  Minieres (B.R.G.M) for the accoung of the newly created ANRED. This study was carried out
  with the aim to discover hazardous sites by the collection of information available in the
  Regional Representations of the B.R.@.M, taking advantage  of the particularly good
  knowledge these local agencies had of the environmental situation -assuming the fact
  thas most of the time pollution occuring from contaminated sites affects groundwater-.

These investigations  produced a total of 453 sites among which 82 were recognized as
serious.                             ;

At the  end of 1985,  the official evaluation of the Ministry of Environment  mentionned 107
cases which  corresponded to a more important number of sites. This figure, compared with


                                    286

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the Initial number of 62 hazardous sites shows that the first inventories carried out in 1978 were
far from exhaustive. In addition two additionnal facts have emphasized the. necessity of a
new registration of unknown contaminated sites.

- The first is the extent of estimations to thousands of contaminated sites in countries where
 active environmental protection policy has been carried out on this subject :  USA,
 Netherlands, Federal Republic of Germany,

- The second is the incidental  discovery of abandonned hazardous sites that  created
 certain pressure upon the local and national Authorities.

Consequently, the Minister of Environment has decided, at the beginning of .1985 to reactive
new sites inventories. At the present time these actions are carried out through two main
ways :

V Directives given to local Authorities responsible for the control of Classified Installation for
- the Environmental Protection (including industrial and municipal landfills) requiring
• reactivation of contaminated sites inventories.

2/ Mission given to the Agence Nationale pour la Recuperation et ('Elimination des Dechets
 to develop new inventories actions at national and/or regional levels.

The main of these actions consisted in an inquiry of the municipalities by,the  mean of a
mailed questionnary, A great number of answer was obtained (more than 18000). However
the number of questionable answers was only about 600 which are now being evaiuted. This
evaluation is not completed now but according to the main existing results it can  be
estimated that less than 10 percent of the mentioned cases would be reaiy hazardous,

At the  present time, according to a  report published by the Secretary of State  for
Environment in July 1989, all these actions of inventory have produced a new list of about 100
officialy registered hazardous sites that the government has planned to restore within the
next five years. However this list is already not exhaustive : some existing important cases
are not mentioned and the action of inventory is still going on.


II - ADMINISTRATIVE AND LEGAL ASPECTS

In  France, the normal way to finance the studies and rehabilitation of contaminated sites is
the  application of  "polluter  must pay"  principle. This  is  made  possible  by  the
Implementation of two  basic  laws : the law of July 19,  1976 on  Classified Industrial
Establishments for the Purpose of Environment Protection and the Law of July 15,1975 on the
management of wastes.

These  laws make the  generators or holders of contaminated sites responsible for the
pollution and pay for the investigations and rehabilitations. They have  been successfully
applied by Local Authorities under the supervision of the Ministry of Environment for most of
the cases of rehabilitation carried out in France.

However, it appeared that in a significant number of cases it was not  possible to find a
responsable party able to  pay for the depollution and some of- these cases remained
unsolved until the issue, on January 9,1989 of a new directive for the Local Authorities facing
such situations.

The main steps of the procedure described in this directive are the following :

1 / The local Authorities must carry out all the existing legal possibilities to find the polluter and
 make him realize and pay the rehabilitation project
                                     287

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2/ In the case of impossibility to find a reliable responsible party the Local Authorities inform
  the central level and ask its agrement |for the following step which is as follows: the Prefect
  of the Department, acting as representative of the government, designate the National
  Agency for Waste Recovery and Disposal CANRED) to carry out the rehabilitation of the
  considered site,                    l

3/ In this  situation, the ANRED carry  out the rehabilitation project, financed by the
  government  and  after completion,  engage lawsuits  to  find the responsible of the
  contamination and try to get the repaying of the expenses.

Up to now ihe  Implementation of this directive has given the possibility to solve about ten
cases of middle Importance.
Ill - TECHNICAL ASPECTS

     HI."I - Introduction               ;

     In France, up to now, although th^re is a national policy on the subject of hazardous
     dumps and contaminated sites and some significant examples of land recovery
     there are no national or regional technical guidelines or standards applicable to the
     technical,and economical management of the restoration of contaminated sites,

     After the first inventories carried on in 1978, hazardous sites were ranked according to
     their estimated level of risk with colored point (black, red..,), However this classification
     was roughly approximative with no reaiy measurable parameters.  In fact, risks
     assessment and decontamination projects have been carried out on pragmatic
     basis, according to variable estimations of the characteristics of the sites and of the
     vulnerability of the environment,;allowing the Local.Authorities to appreciate the
     seriouness of the problems and th4 manner to deal with them. Although this situation
     may be understood  as a consequence of a necessary adaptation  of a site
     restoration requirements to the local  technical conditions it Induces the risk of
     Inadhequate solutions and of inequality between polluters facing similar  problems.

     Therefore  ANRED, working in many cases as a national  expert has developed  a
     special effort to rationalize the technical approch of these problems.  The following
     paragraphs will reflect this point bf view, based on our national and international
     experience.                   ;


     111.2 - Evaluation and management of decontamination problems

     Thฉ first step of a project  for the! rehabilitation of a potehtialy contaminated site
     consists-in-the definition of the problem : characteristics of the contamination, nature
     and importance of the risks, and further of the way to deal with it. In this view the
     assessment of the significance of!the contamination, set up of cleanup goals and
     choice of rehabilitation techniques' are of the utmost Importance.

     A first way to  deal with these questions is to refer, when it Is possible, to  existing
     regulation not specific to contaminated sites, for example :

     - In the case of the rehabilitation of a site by the isolation of hazardous material and
     contaminated soils reference should be made to existing  regulations applicable to
     special  Industrial wastes  controlled landfills  : for  example, requested maximum
     permeability of 10"^ m/s and necessity of efficient collection and treatment of liquid
     and gazeous effluents:         :
                                   288

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- In the case of treatment impliying release of effluents (Le leachates ocuring after
Isolation or solidification-stabilization treatment) reference should be made to existing
regulations ;

   . applicable to drinking water supply in the case of the release".o'f effluents In
    groundwater resources used for the population

   . applicable to the discharge of domestic and industrial effluents In the case of the
    release of effluents in surface water                    ;        .     .

   , applicable to gazeous emissions in the case of release of contaminants in the air.

More generaly we think that the definition of the contamination and the set up of clean
up goals should be based on site specific evaluation taking in account;

- The nature of the contaminants, their quantities, their chemical form and physical
characteristics (toxicity and mobility) and the physical and chemical soils properties

- The characteristics of the migration pathways (environmental vulnerability);

   , groundwater
   , surface water
   . soil
   .air                         .          .
   . direct contact

- The present and future use of the soil and of the groundwater.

However it is also generaly interesting to make reference to a comprehensive list of
predetermined criteria of contamination levels of soil and groundwater to get an initial
characterisation of the contamination and to set up preliminary cleanup goals. In
addition  the background level of pollutants naturally presents  in the environment
(metals, arsenic...) has to be considered. As  it  has been  mentioned before such
specific criteria don't exist now in France and instead we'can generally refer to the well
known dutch criteria.
ill.3 - Techniques of rehabilitation

Up to now the main rehabilitation techniques which have been used in France are :

- extraction and off site treatment
- isolation of the contaminated area
- on site (or in situ) stabilization/solidification
- pump arid treatment of contaminate water

At the present time projects are going on which implies the use of in situ soil vapor
extraction and treatment, and thermal and biological processes are in development.
However, considering the present existing contaminated sites it appears that there is a
lack of techniques to solve many cases in satisfactory  technical and economical
conditions. In fact, the rehabilitations by extraction and off site treatment of wastes,
contaminated soils and materials which has been performed in many cases by the
use of the existing Industrial hazardous waste treatment plants appears to be strongly
limited in  many cases of soils  and contaminated  materials not technicaly and/or
economicaly adapted to such treatments, in this view ,the case of landfills for Industrial
waste has also to be specialy mentioned because such installations have had up to
now the possibility to accept a wide range of'residues and polluted soils and materials

                              289

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extracted In contaminated sites at rather low costs and this possibility will probably be
strongly limited in the near future• by more stringent regulations and increased costs.

In the perspective of this development of specific processes to restore, contaminated
sites we have studied on the national and international levels the different techniques
which are already available or in development the following tables summarize their
characteristics and their opportunities and limits of application.
IH-3.1 -Techniques already avaiidble
TECHNIQUE
Isolation
Extraction and off
site treatment
Solidification
Stabilization
Thermal treatment
(soils)
CONSISTS IN ;
coping and lateral
isolation
Extraction, transport
and treatment in ;
industrial waste
treatment plants .
mixing with reactive
agent, on site or ;
in situ ;
1
>
Many kind of I
thermal treatment1
are available : the;
most usual include
heating in rotary ;
kiln + gas :
afterburner
APPLICABILITY
various kinds of solid
waste materials and
soils
many kinds of
hazardous waste
and contaminated
material
sludges, liquids.
soils. Mainly
inorganic contami-
nants - in some
cases non volatile
organics
Organics contami-
nants in
contaminated soils
and materials
cyanides
PARTICULARITIES
LIMITS
-need a site siutable
for isolation
-relatively limited
cost but require
future control and
maintenance
-can be used as
temporary solution
-characteristics of
the wastes materials
and soils has to be
technlcaly and
economically
adapted to the
treatment
-need transport
-often costly
-limited efficiency
(fixation not
perfect) specialy
for organics and for
amphoteric metals
-The temperature
of the final incine-
ration has to be
adapted to the
nature of contami-
nants
-need special care
for volatile metals
                               290

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TECHNIQUE

Extraction/
Soil washing








In situ vacuum
extraction








CONSISTS IN

Many processes
available :
-some using pure
water and
mechanical
energy to extract
the contaminants.
-other using various
solutions or specific
solvents.
-Creation of air
depression in the
unsaturated zone
and treatment of
the collected air
-Possibility of
Improvement by air
Injection (In the
saturated zone).
by thermal desorp-
tion (heating)
APPLICABILITY

Mainly inorganics
(heavy metals) but
also organics (PCB
hydrocarbons)






Volatile organics









PARTICULARITIES
LIMITS
- Usualy efficiency
limited by the size
of particles
- produces
residues which
have to be
disposed wtth
efficiency.


- efficiency
influenced by
impermeability.
heterogeneity and
water content of
the soils.




In  addition to these techniques it has to be mentioned the use of groundwater
treatment. These treatments are carried out either alone in a continuous and long term
decontamination process or in combination with other kind of treatment of a site.
Different water,treatment processes are utilized, either physicochemlcal or biological
or combination of both. In many cases activated carbon Is used In the final stage of
the treatment to adsorb the micropollutants.      •   •
                              291

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ill.3,2-Techniques in development

Many other kind of techniques are in development and for some of them are at the
demonstration or commercialisation stage. We mention there after those of theses
processes we consider relatively promissiong ;

- other kinds of thermal treatment: infrared, oxygen-enhanced, pyroiysls
- glycoiate dechlorination (PCB)  \
- in srtu verification              :
- wet air oxydation - supercritical oxydation
- electro reclamation     ,       ;

Biotechnologies appear also promising but have to be specialy considered :

- they are developed in many countries by research institutions, universities, private
enterprises and consultants, and a great number of research and development works
are on going, based either on on site (on the field or in reactors) or on in situ processes.
Involving most of the time aerobic degradation and in many cases various ways to
masterize and improve the degradation (i.e : enhanced oxydation). In many cases, it
appears difficult to evaluate with: accuracy the efficiency of treatment specialy for
complex molecules (halogenated organics) where the degradation implies stages of
Intermediate metabolites.

- up to now,  few processes are available with proven efficiency  on a commercial
basis.                         •
                                        Rene GOUB1ER
                                        Texts presente d EUROFORUM
                                        ALTLASTEN SAARBRUCKEN (R.F.A)
                                        11-13 juin 1990
                               292

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               NATO/CCMS Guest Speaker:

                  Fritz Holzwarth, Germany

Cleanup of Allied Military Bases in the Federal
                       Republic of Germany
                         No text available.
        293

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                           NATO/eCWIS Guest Speaker:

                                  James Berg, Norway

Cold-Climate Bioremediation: Composting and Groundwater
         Treatment Near the Arctic Circle at a Coke Works
                    295

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   Cold-Climate Bioremediation:  Composting and Groundwater Treatment
                    Near  the Arctic  Circle at a  Coke  Works

                    James D. Berg, Ph.D. and Arild S.  Eikum, Ph.D.        :
                  Aquateam - Norwegian 'Water Technology Centre A/S
                                    Oslo, Norway

                     Trine Eggen, M.Sc., and Hugo Selfors,  B.Sc.
              Terrateam -  Norwegian Environmental Technology Centre A/S
                                 Mo i  Rana, Norway


  ABSTRACT

        Bioremediation was evaluated as. an alternative  treatment  method for  a' coke
  works site in northern Norway near the Arctic circle,  which  was characterized  in
  1989 as having significant contamination by polycyclic aromatic hydrocarbons (PAH),
  arsenic and cyanide.   About 20,000  tons of soil  containing PAH's (ca.  500  mg/kg)
  were excavated.   Groundwater at the  site contained  ca. 2-3 mg/1 and 0.4-1.6 mg/1
  naphthalene and  benzol.  A pilot study; was conducted in 1990, in which 1,000 m3  of
  soil were treated in an enhanced composting  system  and  7000   1 groundwater was
  treated in a biofilm reactor.         \
        The variables tested  in the composting study were:  N and P, bark matrix and
  dispersant addition,  temperature (4ฐ-16ฐC),  moisture  (10-35 %), and  aeration  by
  blowers,  H2O2 addition or pile  turning.   The treatment objective was < 10  mg/kg
  Total PAH.  Results showed that the PAH-content was reduced to below the objective
  within 8  weeks at  12-16ฐC.  Treatment efficiency ranged from  96-99  % dependent  on
  test variables.   Optimal results were obtained by 1)  addition of tree bark as a
  matrix, 2) supplemental forced aeration, 3) soil moisture maintained at 25-30 % for
  this soil type, 4)  N and P additives,  and 5) dispersant additives. Groundwater was
  pumped from a pilot  well and  treated ,in a rotating biological   contactor  (R3C),
  covered to control emissions of volatile compounds.  The early migration of arsenic
  into the  area  also  necessitated development  of a two-stage   pre-precipitation
  process using lime and ferric chloride in series to  remove arsenic.  Nitrogen was
  added after pre-treatment.    Once the  biofilms were  acclimated to  the  water,
  chemical oxygen demand, I, PAH,  and toxic it y (Microtox ฎ) were  reduced 97, >99, and
  93 %,  respectively.

  INTRODUCTION

       The Norsk Koksverk coke works  was  located in Mo i Rana in  the northern part
 of Norway.   The plant processed approximately 440 000  tons of coal per  year,
 beginning in 1964.  The plant annually produced 55-60  000  tons NH4,  approx.  15000
 tons  tar  and  5000 tons  ber.zene.    These products  were  sold   without  further
 processing at  the plant.   The plant was  closed  down in  the  fall of  1S88 for
 economic reasons.  Site characterization and clean-up was required by the pollution
 control authorities  (SFT) before any further  development of the area would be
 permitted.
       Owing to the acute contamination-of two areas, approx.  20,000 tons  of-soil
 was  excavated and placed in  lined and  covered depositories on the site.  This was
 designated as the "?AK-Scii"  fcr the composting study and contained ca. 500  mg/kg
 PAH.   Groundwater  contained  ca.  14 ir.c/1 PAH  originally,  and later  ca. 200  mg-/.l-.
 arsenic.                                                                     ,
       The remediation  of a contaminated coke works site  (Norsk Koksverk)  i Northern
 Norway was initiated in 1589.   It  was  unique  in that it was Norway's first  major
 cleanup in which  several  technologies  had to  be considered for the  contaminants,,
 including polycyclic aromatic hydrocarbons (PAH),  arsenic, cyanide, end copper.-
 The subject of this paper concerns the treatment of the PAH-contaminated soil,and
 groundwater,  in  which biological processes  were chosen  for the  pilot study.
 Biological treatment of soils contaminated with  organics is a preferred  technology
 in many cases because of its simplicity,:leck of  residuals (e.g. sludges) requiring
 further treatment,  and relatively low bost (1-4).   Coke  or gas   works sites are
 typically  contaminated by PAH's  (5)  wljich can be  biologically   degraded  (6-8).
 Bioremediation processes especially designed for aromatics have also  recently been
 described  (11-13).                                                 ,

 PILOT STUDY REMEDIATION PLAN                                             :'"•''"  """"""

 General

      As  stated  above,  there  were  several  types  of  contamination,  requiring
different remediation  processes.  Three;separate pilot treatability  studies were

                                       296

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  conducted;

  (1)    Composting of excavated PAH-soil.
  (2)    Physical-Chemical-Biological Pump-and-Treat of As-PAH groundwater.
  (3)    Stabilization of excavated As-soil.

  The  first two studies are reported herein.

  Soil Composting Study

        PAH-contaminated soil  (Avg.  concentration == 500 mg/kg total PAH)  from "Dep.
  4" was sorted,  crushed,  and  mixed to  form as homogeneous a  material as possible.
        The soil  was  then placed in 9 separate piles of ca. 10 m3,
  2mx3mxl.5m  (WxLxH)f on geomembranes.   Seven piles  were placed  in'an
  unused industrial building, while two  were placed  in  an abandoned local mine.  The
  latter was chosen since the mine is a candidate full-scale treatment facility with
  excellent capacity for final, secure deposition of treated soil  (Volume of storage
  space  is  1 million' m  with excellent ventilation and  controlled drainage).   Table
  1 shows the  variables  tested in the study, which  are described  below.

  Table  1..    Experimental variables  in the pilot study.  FA = Forced aeration,  T =
              pile turning, N  &  P = Nitrogen and phosphorous.
Pile

1.
2.
3.
4.
5.
6-
7.
8.
9.
Treatment
Bark
_
+
+
+
+
+
+
+
+
N&P
_
_
+ •
++
+
+
+ '
+
+
Aeration
T
T
T
T
FA
H,02
T
-
T-
Temp(ฐC)
10 - 16
10 - 16
10 - 16
10 - 16
10 - 16
10 - 16
25-35
4
4
Other
_
	
_ . . •
_
—
Recirc H2O +
dispersant
_
_
-
       Pine bark was added to all piles except No.  1 (control with no amendments)
 iii  a  ratio of bark: soil equal to 1:1 on a volume  basis.   The soil was sandy and
 had very  little capacity to  retain moisture.  Nitrogen and phosphorous were added
 to  six of the piles in two different  doses at the  start  of the study and after 8
 weeks.  The piles  were oxygenated by  either turning the  piles every three weeks,
 by  forced aeration,  or  by peroxide  addition  via  a water  recirculation  system.
 Per'oxide  was  replenished three times per week.  Ambient temperature ranged from 4-
 16ฐC  for  six of the piles in the industrial building.  One pile was artificially
 heated by electric cables under the geomembrane base.  The  two remaining placed,
 piles  in  the mine remained at a constant 4ฐC throughout the study.  The piles were
 watered•initially,  and  after  weeks 6 and 8.  Pile 6 also had  regular  periodic
 recirculation of water throughout the study.  Dispersant,  peroxide,  and nutrients
 were added to the  water.
    •"The piles were sampled twice weekly  from  3  random locations at ca.  80  cm
 depth.  Composite samples were prepared and placed in acid-washed'brown glass jars
 and either analyzed immediately  or frozen at -18ฐC.  Temperature and soil  gas
measurements  were taken  at three  locations at ca. 80 cm depth twice weekly also.
      Analyses were conducted on site  if possible.  However, contract laboratories
performed all PAH analyses.  Analyses consisted of:
      - Moisture                                                  •'•'•'••'
      - PH
      - Tot N
      - Tot P
  '   - Total PAH  (+ all components by GC/MS)            .
     • - Soil gas (O2 and  CO2)

                                       297

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  Composting Study Results

        The  results of the study for the most predominant P&H's are shown in Figures
  1 and 2.   In all cases, biphasic reduction in PAH's occurs over the 14 week study
  period.  It is largely the duration of the lag phase or initial reduction rate that
  is  influenced by the  various  amendments.   Notably, the  control pile shows the
  slowest rate of PAH reduction in all cases. The proposed treatment goal, the Dutch
  "B" level  of 20 mg/kg PAH is achieved in 6-8  weeks  under optimal conditions.  The
  individual PAH' sf  as typified by Figure 2 for  fluorene and acenapthene,  also follow
  the same behaviour.  Forced aeration [and nutrient additions both contributed to a
  much more effective process. Other 1kb experiments (data not shown)  indicate that
  increased  volatilization of  the  2-5  ring  PAH's  by  forced  aeration was  not
  significant, suggesting that it was primarily  biological activity that explains the
  reduction  in PAH's.
        Also, it is interesting to note;that even at 4ฐC, there was effective removal
  of PAH's (See Figure 2, Piles 8 and 9 for f luorene aftd acenapthene)  suggesting that
  the naturally occuring populations had  been  well  adapted  to the low .temperature
  environment.  Owing to problems with:regulating the temperature ia the pild with
  heating cables,, no reliable data were 'pbtained for greater than ambient temperature
  which ranged from 4e-16ฐC during most of the  study.
                                                    a—a
Nf.1
Nf.2
Nr. 4
Nf.5
Nr. 6
                                                ;\
Figure I.   Reduction of Total PAH's.
                                        298

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                   Dryweight
                    (W'S)
Figure  2.    Reduction  oฃ fluorene and acenapJithene.
                                        299

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        Lastly,  the  PAH  removal result^ of the water recirculation experiment were
  unexpectedly  lew.   Therefore,  other dispersants  were  subsequently evaluated in
  bench scale batch  end  flow-through column  studies.   Results showed that another
  .type of  dispersant,  ECO/+ (R.L.  King Assoc.  - Dutch Fride Products, 500 Airport
  Blvd., # 238,  Burlingame, CA 24010) Greatly enhanced the mobilizatcn and removal
  of PAH's.  In  batch mixing studies, Iqw concentrations of ECO/+ at ca. 10ฐC removed
  > 62 % of  Total PAH's.   The product is  reported to  be  biodegradable so that the
  composting process should not be inhibited.

        The results  of the  PAH reduction  aspects  of the  study are comparable with
  other published studies  (14-16).    Where  it  is possible  to  directly  compare
  individual compounds, for example with  phenanthrene,  the half life (t %)  in this
  study was ca.  14 days under optimal conditions versus  16-200  days under a range of
  other  comparable  conditions  of  temperature  (10-20ฐC) .•• and  amendments  (added*
  nutrients).  The same is true  for fluoranthrene, with this study reporting t % *ป
  48.5 days versus 29 to  440 days.  Where total PAH data were available,  this study
  reports t Hi • 22 days under optimal  field conditions versus 43 days in a laboratory
  study (17).

  Groundwater Treatment Study

        The groundwater treatability pilot  study was begun in April  1990 and run over
  a four month period.  The pilot well was placed in the  center  of the area which had
  previously  been characterized as contaminated with FAH's.  The well placement was
  also chosen to  avoid the arsenic-contaminated  zone, to avoid complications for the
  study.  However, the arsenic plume had-migrated sufficiently such  that ca. 200 mg/1
  As  was actually present  in the  grpundwater  at the  pilot  well.    The major
  characteristics of the water are  shown' in Table 2.  The pH was quite high owing to
  the  caustic arsenic tank spill.  Also) the  chemical oxygen-demand  (COD) was  high
  initially,  1400 mg/1, and doubled over the period of the study to 2800 mg/1.

  Table 2.    Composition  of the groundwater from the pilot well.
Parameter
PH i
P.O. (mg/1) ;
Conductivity (mS/m)
COD (mg/1)
Kapthalene (mg/1)
Benzene (fig/1)
2 PAH (mg/1)
As (mg/1)
Cu (mg/1)
CN (mg/1)
Value (range)
9.5 - 10.9
1.5 - 2.5
55 - 65
1400 - 2800
0.4 - 1.6
60
1.8 - 2.8
200 - 215
0.005 - 0.05
2.5 - 7.5
       After the well was established,  it  was  pumped once a week,  producing a 700
 1 batch for the pilot treatment process.   The 7*00 1 volume was,  in  some cases,
 pretreated.  Thereafter it was pumped ir.it o three 200 1 tanks for further additions.
 The 200 1 tanks then served as the reservoirs with capacity for 5-7 days operation
 for the six bicfilm reactcrs.  The reactors were placed in different cor.figuretior.s
 through  the study.   The three  reservoirs and six  bioreactors  were  covered  to
 minimize losses by volatilization.   The study was conducted in four phases.  Phase
 1  included  acclimation  cf the biofiim,; end studying the effect of six different
 loading rates.  Phase 2  included two loading rates  on four  sets of reactors, two
 of which were in series.  The effects  cf  nitrogen  and phosphorous  additions, and
 surfactant and  solvent  addition  were  also monitored.  Phase 3 included chemical
pretreatment  of the  water  by  lime precipitation  end  pH  adjustment.   Phase  4
included chemical pretreatment by precipitation with ferric chloride  end lime  in
series.  Also,  activated carbon columns were added as a final polishing step.  The
configuration cf the processes  is shown in Figure 3.
                                       300

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            Process step

            1. Physical-chemical
              removal
 Precipitation
  pH Adjust
             Reservoir (200 0
                             Treated
                              Raw
                              water
              Q (mil)        30
           2.  Btereadors (RBC)
                      Series
                         270
Series
                            I
          3. Active carbon
             columns
                            T        TTT
3.   Conf ignition of tH. P-ocess tปi* i* Bases'3 ซd
                               301

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       Daily measurements were: flow rate in each reactor set; and temperature, pH,
 and D.O. in each bioreactor.  Kicroscbpic examination of special glass slides built
 into  the  rotors  was  done  twice  weekly.    Samples were  taken daily  from the
 reservoirs, and before and after each process unit.  These were split and analyzed
 immediately for COD  (daily'values) and preserved and analyzed weekly for  all 26
 PAH  components   (composites).    Arfeenic,   copper,  cyanide,   and   nitrogen  and
 phosphorous were analyzed periodically for control purposes.  Toxicity of influent
 and effluent was  measured by Microtox ฎ testing at the completion of the  study.
 Thฉ bioreactors were  cleaned thoroughly once each week to minimize the contribution
 of wall growth on degradation/removal rates,  a  factor of paramount importance for
 full-scale design.

 Groundwater Treatment Study Results

 ftroanles Removal                    '                    '

       Removal of COD  in the first three phases  of the study was negligable.  This
 was due  to non-acclimated cultures,: range-finding for proper  N &  P addition,
 apparent toxicity of  influent  metals,   and  unsuccessful early  attempts  at  pH
 control.
       The results- for  Phase  4  are shown'in Figure  4.   After about  a 10-14  day
 acclimation period, the removal of COlp began to  increase'dramatically to ca. 95 %.
 To test whether this effect was achieved biologically, the biofilm was scraped from
 the  reactors,  causing,  an  immediate decrease  in percent removal  to  the  original
 level.   The systems re-equilibrated about two weeks achieving >95 % removal.  The
 "20  %  removal  rate" shown for the reservoirs (DT 7  and DT  8)  reflects the  prior
 removal  of COD in the  precipitation pretreatment of the raw groundwater.  There was
 no significant decrease in COD in the' reservoirs themselves.
      Neither  COD  nor  PAH  measurements  indicated significant  losses  due to
 volatilization.   Nonetheless, a separate batch  test  was  run. in which 2  1 of
 influent  water was violently  aerated for 24 hours.  COD, naphthalene, and  ฃ  PAH
 were measured before and after.  A maximum of 25  % naphthalene was lost, comprising
most of the Z PAH  losses as well.  Other  studies have reported only  0.4  to  7.6 %
loss  of  naphthalene  in  covered RBC's   (18),  attributing  most   removal  to
biodegradation   (9).     Therefore,  in  the  closed,  passively   aerated RBC's,
volatilization was not  considered to be significant.
'• Red, i (
100

80-

60-
40-
20-
0-
2ODr
	 DT7andDT8
	 B effluent ^-^ ^ 	
—— — 81 reactor / \ x^ ^X
	 A effluent / \ ^ ^S*^'
— ..... ^^ reactor ป - \. ^*^*^f*~'^
I \ 	 _. — "^^""'
— , 	 _.___„___. 	 ^21>
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  Arsenic Removal

        An immediate increase in arsenic from <5 to  >200 ing/1 necessitated addition
  of a process step to remove it.  Early jar tests  indicated that lime precipitation
  was not adequate.  Subsequent trials with ferric chloride were also unsatisfactory.
  However, step-wise treatment using lime  followed  by ferric achieved significant
  arsenic reductions as  well as COD reductions . (Table 3) .  This type of process
  sequence has also been reported elsewhere (20).

  Table 3.    Results from jar tests for 2  step liine and ferric precipitation.

Ca(OH)2
(mg/1)
FeCl3; (ml)
pH
CODFILTR. mg/1
As mg/1
Cu mg/1
CN mg/1
Raw water
	
	 .
9.95
2500
216
0.007
2.5
1
	
1.5
4.45
1503
183
<0.005
6.9
2
	
1.0
6.3
1473
162
<0.005
8.0
•3
3.0
1.5
; 4.3
2 10.1
1 1516
2 1386
39
<0.005
5.1
4
3.0
1.5
5.95
1310
134
<0.005
7.5
 Summary of Results

       The results for the groundwater treatment  study showed that  chemical oxygen
 demand (COD),  ฃ PAH, and toxicity were 97, >99, and 93 percent, respectively  (Table
 4).
 Table 4.
Groundwater treatment pilot study results.
Sample
location
Raw water
Finished
effluent
COD__,.
Phase 4
1400
40
% Red.
Phase 4
—
57
ฃ ?AH
mg/1
2.19
O.DC42
% Red.
—
S9.8
Tcxicity
EC
<15~iran.)
30
427
% Red.
—
S3
 SUMMARY

       Both  composting and the R3C  process  performed well in the  pilot  studies.
 These  biological processes were chosen because of low capital and operating costs,
 on-site capability  (low  area  requirement),  minimal developmental requirements,
 simplicity  for operation  at a remote site, and capability for cold-climate,  year-
 round  operation.   The conclusions for  each pilot study follow.

Composting  Study

1.     Among the  amendments  evaluated in the study, the addition  of bark  and
       nutrients,  (primarily  nitrogen) and  forced aeration,  were  essential  for
       optimal biological  activity.

2.     The surfactants  chosen for the  pilot  study did not  improve PAH  removal.
      However, subsequent column  and batch  studies with  another  commercially
      available product (ECO/+) were very promising.

3.    Cultures adapted to  low temperatures showed significant  degradation at 4ฐC,
      however, better results were obtained at temperatures ranging  from 6-16ฐC,
      as, one would expect.
                                       303

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  4.     The  proposed treatment  objectivte  of  20  rag/kg Total  PAH  was  attained within
        6-7  weeks/  while a more stringent goal of 10 rag/kg was  reached within 8-9
        weeks.

  Groundwater Study

  1.     A  four  step process  was  developed for successful  treatment of the  water
        including:
        *     Oxidation  for CN  destruction and As-pretreatment.
        *     Two stage  precipitation with ferric chloride  and  lime for As  removal
             and some COD reduction.
        *     Addition of N & P and pH adjustment for biotreatment.
        *     Two stage  RBC bioreactor for PAH  and COD removal.   (Activated carbon
             columns can be added for water not reinjected to the  aquifer).

  2.     Separate studies showed that dispersant addition  could mobilize ca.  60 %  of
        PAH'3 in batch tests.  This will ;be injected into the treated water  prior  to
        return to the contaminated aquifer in a pump-and-treat well-point system.

 ACKNOWLEDGEMENTS

       The  pilot   study  was  conducted > for  the  municipality of Mo  i  Rana  with
 additional support from the  Royal  Norwegian Council for Scientific and Industrial
 Research (NTNF) and Norwegian Applied Technology A/S, Stavanger, Norway. Technical
 support from Dr.  Royal Nadeau, U.S.  EPA,  New  Jersey is  gratefully  acknowledged.

 REFERENCES

 1.    Sims, R.C.,  et al., Treatment Potential  for 56 EPA Listed  Hazardous Chemicals
       in Soil,  U.S. EPA/600/6-88/001,  1988.

 2.    Stepsf   J.M.M.,   International Evaluation  of  In-situ  Biorestoration  of
       Contaminated Soil and Groundwater, in Proc.  Third Internationa^ ^Conference
       Demonstration of Remediation Action Technologies  for Contaminated Land and
       Groundwater, Montreal,  Canada,  NATO/CCMS,1990.

 3.    Borow, H.S.  and Kinsella, J.V., Bioremediation of  Pesticides  and Chlorinated
       Phenolic Herbicides - Above Ground and  In Situ - Case Studies, Proc. 10th
       National  Conference and  Exhibition, Washington, pp.  325-331, HMCRI,  1989.

 4.    Christiansen, J.A.; Koenig,  T.; Laborde,  S.  and Fruge,  D.,  TOPIC  2: Land
       Treatment Case Study Biological Detoxification of  a RCRA Surface Impoundment
       Sludge Using Land Treatment  Methods,  in Proc. 1.0thNational Conference and
       Exhibition,  Washington,  pp.  362-367,  HMCRI, 1989.

 5.    Turney, G.L. and Goerlitz,  D.F., Organic contamination  of groundwater at Gas
       Works Park,  Seattle, Washington, Ground Water Monitoring Review, JU).(3), pp.
       187-198,  1990.

 6.    Park, K.S.;  Sims,  R.C.; Dupont, R.R.; Doucette, W.J. and Matthews,  J.E., Fate
       of PAH compounds in two soil types:  Influence of volatilization, abiotic loss
       and biological activity,  Environmental Toxicology  and Chemistry,  9, pp. 187-
       195,  1990.

 7.     Portier, R.J.,  Bioremediation  Using Adapted Bacterial Cultures.  Topic 1:
       Examination  of Site Data and Discussion of Microbial Physiology with Regard
       to  Site  Remediation,  in Proc.  10th  National  Conference and  Exhibition,
       Washington,  pp. 351-361, KMCRI, 1989.

 8.     Pothuluri,  J.V.;  Freeman,  J.P.; ;Evans,  F.E.   and Cerniglia, C.E.,  Fungal
       transformation  of  fluoranthene, jApplied  and Environmental  Microbiology,
       5.6(10), pp.  2974-2983, 1990.

9.    Mahaffey, W.R.  and Compeau,  G., Biodegradation  of Aromatic  Compounds,  in
      Proc. llth Annual Conference & Exhibition,.Superfund '90. Washington,,  pp.
       780-787,  HMCRI, 1990.

10.   Bewley,  R.J.F. and Theile,  P., Decontamination of a  Coal Gasification Site
      Through Application of Vanguard Microorganisms, in  Contaminated Soil '66, ed.
      K. Wolf,  W.J. van  den  Brink,  F.!J.  Colon, pp.  739-743,  Kluwer Academic
      Publishers,   1988.


                                       304

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 11.   Compeau,  G.C.;  Borow,  H.  and  Cioffi,  J.C.,  Solid Phase  Remediation of
       Petroleum Contaminated Soil,  in Proc. llth Annual Conference & Exhibition,
       Superfund '90,  Washington,, pp.  814-819,  HMCRI,  1990.

 12.   Tan,  C.-K.;  Gomez,  G.; Rios,  Y.;  Guentzel, M.N. and  Hudson, J., Case study:
       Degradation of  Diesel  Fuel With In Situ Microorganisms,  in Proc. llth Annual
       Conference & Exhibition, Superfund '90, Washington, pp. 776-779, HMCRI, 1990.

 13.   Stroo,  H.F:; Smith,  J.R.; Torpy,  M.F.; Coover,  M.P.  and  Kabrick,  R.M.,
       Bioremediation  of Hydrocarbon-Contaminated Solids Using Liquid/Solids Contact
       Reactors,  in  Proc._ 10th National  Conference and Exhibition, Washington, pp.
       332-337,  HMCRI, 1989..

 14.   Sims, R.C., Loading Rates and  Frequencies for Land Treatment Systems, in Land
       Treatment: A Hazardous Waste Management Alternative,  ed. R.C. Loehr and J.F.
       Mallna, Jr.,  Water Resources Symposium No.  13,  Center for Research in Water
       Resources,  The  University of  Texas at Austin, Austin, TX, 1986.

 15.    Sims, J.L.;  Sims,  R.C. and Matthews,  J.E., Bioremediation of  Contaminated
       Surface Soils,  U.S. EPA/600/9-89/073,  1989.

 16.    Coover, M.P. and Sims,  R.C., The effect of temperature on polycyclic aromatic
       hydrocarbon persistence in an unacclimated agricultural soil, Hazardous Waste
       & Hazardous Materials. ฑ, pp. 69-82,  1987.

 17.    McGinnis,  G.D., et al.,  Bioremediation  Studies  at  a Northern  California
       Superfund  Site,  in  Proc.  Bioremediation  -  Fundamentals  and  Effective
       Applications Gulf Coast  Hazardous  Substance Research Center.1991.

 18.    Glaze, W.H.,  et. al.,  Fate  of  naphthalene in  a  rotating disc  biological
       contactor,  Journal WPCF, j>8.(7), pp.  792-798,  1986.

 19.    van  der  Hoek,  J.P.  et  al.,  Biological removal of  polycyclic  aromatic
       hydrocarbons, benzene, toluene,  ethylbenzene,  xylene  and phenolic compounds
       from heavily contaminated groundwater and soil,  Environ. Tech. Letters,  10,
      pp. 185-194, 1989.

20.   Wolff,  C.T.  and   C.L.   Rudasill,   Baird  and  McGuire   Superfund   Site:
       Investigation of Arsenic  and  Lead Removal  From Groundwater, in Proc.  llth
      Annual Conference and  Exhibition, Superfund '90, Washington, pp.  371-375,
      HMCRI, 1990.
                                        305

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                          NATO/CCMS Guest Speaker:



                               Gjis Breedveld, Norway



In Situ Bioremediation of Oi! Pollution in  Unsaturated Zone
                   307

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                    IN SITU BIOREMEDIATION OF OIL POLLUTION
                               IN THE UNSATURATED ZONE
                           Gijs D. Breedveld, Per Kolstad and Audun Hauge
                                Norwegian Geotechnieal Institute (NGI)
                                  P.O. Box 40 Taasen, N-0801 Oslo
                                            Tormod Briseid
                                  Center fdr Industrial Research (SI)
                                            Bj0rn Bremstad
                          Norwegian Defence Construction Service (NODCS)
ABSTRACT                                !
Leakage  of an underground storage tank at the
Trandum Army Base caused a 20.000 liter spill of
fuel oil. Several options for remediation hare been
evaluated. In situ bioremediation was chosen as the
most  cost effective and realistic method and jwas
evaluated in  detail. Preliminary  laboratory studies
showed that a large number of hydrocarbon degrad-
ing micro-organism are present and that good degra-
dation rates can be obtained with the addition of a
niirogen and phosphorus source. Since July 1991 a
full scale bioventing installation has been in opera-
tion.  The preliminary  monitoring results give!  an
indication of biological activity.
SITE DESCRIPTION
Trandum Army Base is situated in the Romerike area
some 40 km North of Oslo. This area is one of
Norway's most important groundwater reservoirs. The
unconfmed aquifer is composed of glaciofluvial sand and
gravel partly underlain by silty glaciomarme deposits.
The  average  thickness of the deposits is 73 m. The
unsaturated zone can vary from 1 to 30 m below ground
level (J0rgensen and 0stmo, 1990). At Trandurn near the
storage tank (building 111) the groundwater level is at 30
m below g.l. The soil texture can be described as sand
and gravel in the uppermost 10 m, silty sand between 10
and 20 m and medium fine sand to  silty fine sand
between 20 and 30 m (Hauge and Kolstad, 1990).
INTRODUCTION
On October 12. 1990 the loss of 20.000 liter of a IJght
fuel oil from an underground storage tank at Trandum
Army Base was discovered. Immediate action was taken
by NODCS by removing the tank. The State Pollution
Authority  ordered  immediate  measures to  prevent
spreading of the  pollution to the underlying aquifer
(October 15.). Consequent clean up of the residual oil in
the unsaturated zone should prevent future risks ;for
groundwater pollution.
                                             308
SITE INVESTIGATION
Immediately after discovery of the leakage interception
wells were drilled in the center of the polluted spot and
down stream of the groundwater flow direction. Pumping
started on October 26.(Storr0, 1991).
Additional borings were carried out to asses the extent of
the pollution. A total of 98 samples were analyzed for
total hydrocarbon (THC) content by gas chromatography.

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Table 1. Vertical distribution of oil in the
centre of pollution (Storre, 1991).
Boring
PB2
PB2
PB2
FJB2
3
3
3
3
3
3
3
Depth
(m)
4
5,5
7,5
9
12
14
16
18
20
24
28
THC
(g/kg)
8,5
9,4
10,3
10,1
19,4
18,2
19,2
18,5
13,2
18,4
<0,05

An impression of the vertical distribution of the pollution
is  given in table 1. The data  indicate that the main
pollution plume has not moved completely vertically, but
has partially moved diagonally beneath the building.
Figure 1 gives an impression of the assumed extent of
the oil pollution. The boundary indicates approx. 1000
mg/kg THC.
It is believed that the pollution is completely retained in
the unsaturated zone at residual concentration levels. The
plume has not reached the groundwater level and upto
now no oil or aromatic hydrocarbons (BTEX) have been
detected in the pumping well (PB 2) in the centre of the
pollution (Kolstad et al. 1991b),

REMEDIATION ALTERNATIVES
Based on the results of the field investigation different
options for remediation of the site are evaluated (Hauge
and Kolstad, 1990):
•   Isolation
•   Removal by open excavation of 300.000 m3,
•   Removal by excavation inside a sheet pile wall
    (20.000m3).
•   In situ bioremediation.

Isolation was not an actual solution, as the State Pollu-
tion Authority ordered complete rehabilitation of the site.

As the cost of in. sita bioremediation is excessively lower
than excavation and subsequent treatment of the polluted
soil, this technique has been evaluated in, detail.
                                                                                        tOm
                                                                                        20m
                                                                                        30m
  Figure 1.    Assumed extension of oil pollution below building 111.
                                                 309

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BIOREMEDIATION POTENTIAL
To assess the  possibilities  for using  in situ biฃป-
remediation at this site, the following laboratory studies
were conducted:
•   quantification of the total natural microflora and the
    number of hydrocarbon degraders.
*   degradation rates in microcosms  and potential of
    increasing it by moisture, nutrient and special oil
    microflora addition.
The natural microflora was determined using plate counts
of colony forming units (CPU) on nutrient medium. The
number of hydrocarbon degraders was determined using
mineral medium and a small "well* of diesel oil as only
carbon source (Briseid and Eidsa, 1991). Table 2 gives
an overview over the vertical variation in the microflora.
Table 2. Vertical distribution of the microflora
in the centre of pollution.
Boring
Dl
E>2
Mix
Cl
Depth
(m)
8
12
20-24
27
Total
(CPU)
3.107
2.107
1.107
2.104
HC-degr. ;
(CPU) (
1.107
2.10*
1.10s
I
5.103

A batch of mixed samples (20 to 24 m below g.'l.) was
used in degradation experiments at 15 ฐC. The sample
can be described as fine sand with some gravel, and
contained 29 g THC/kg in the fraction <2mm. The
degradation rate was measured in microcosms (10 g.) in
a. "Sapromat" which measures the  oxygen consumption,.
The effect of the following additions on the degradation
rate were tested:
    1.  nothing, moisture content 5%
    2.  water, moisture content 15 %
    3,  as 2 4- special oil microflora                :
    4.  as 2 + nitrogen source (0,4 g/kg)
    5.  as 4 + phosphorus source (0,1 g/kg)
    6.  as 5 + special oil microflora
The oxygen consumption was registered over 100 days
(figure 2). The results indicate a clear increase in oxygen
consumption rates with the addition of a nitrogen and
phosphor source. The addition of a special oil microflora
caused only a minor increase in the consumption rate.
This effect was clearest visible during the last part of the
experiment.
   I
W+N+P
W+N+P+MQ
Nothing
W+MO
                                                                           1000
                                                                                        2000
                                                                                                    3000
                                                                                 Hours
                                                         Figure 2.
              Oxygen consumption in microcosms
              with different additions.
Assuming that the total mineralisation og  1 g of oil
consumes about 3,5 g oxygen, a reduction in, TflC
concentration in fhe nitrogen and phosphorus anteflded
soils with and without oil microflora of 7.6 g/kg. (26%)
and 5,9 g/kg (20 %) respectively should be expected. The
data indicate an average degradation rate of
                                           • -:" ''i-t'f*'
78 mg THC/kg/d and 61 mg THC/kg/d respectively. '"'
After 59 days one of every duplo sample was takefci Out
                                            •"•„ * \',Z' •.
for chemical  analyses. The analyses results shovซ?::'tfie
same  relative effect  of the different additions as  the
oxygen consumption measurements showed. Howfygr.tjje
reduction in concentrations is much higher thanjexpected
(Table 3). The reduction  in the soils where almost no
oxygen consumption was registered (1,2,3  arid 4),,
-------
Table 3. THC concentrations after 59 days
incubation in microcosms ( W= water,
N= nitrogen, P= phosphorus, MO=
oil microflora).
Addition
1. Nothing
2. W
3. W+MO
4. W+N
5. W+N+P
6. W+N+P + MO
THC
(g/kg)
22
21
22
21
13
11
Redaction
(%)
24
28
24
28
55
62

The removal rates in the nitrogen and phophorus ammen-
ded soils are much higher: 305 mg THC/kg/d and
270  mg  THC/kg/d respectively  with and without oil
microflora. Relative to the soil without any addition (1)
the removal rates in the nitrogen and phosphorus ammen-
ded soils (5 and 6) increased with 150 and 180 mg/kg/d
respectively. This indicates that besides evaporation also
not complete mineralisation contributes to the reduction
in THC concentrations,
The results show that the natural  microflora has a good
biodegradation potential if nitrogen and phosphorus are
added, besides oxygen.
DESIGN OF THE BIOREMEDIATION SYSTEM
As the pollution is distributed in the unsaturated zone
and  no groundwater pollution  has been  registered,
bioremediation by  "conventional" methods using water
recirculation was not acceptable as there would be a
large risk for leaching of oil to the groundwater. There-
fore a rather new method, bio venting, was choosen (Eijk
and Vreeken,  1989;  Hincfaee and Miller,  1990). This
method supplies oxygen to the soil microflora by soilgas
ventilation. Because of the large depth of pollution and
the registered inhomogenous soil composition a configu-
ration of three soil gas extraction wells at different depth
were installed . The pressure gradients in the subsoil are
monitored by two sets of piezometers at three depths: 8,
15 and 25 m. To supply water and nutrients a horizontal
infiltration gallery  around building  111 was installed.
Figure 3  gives  an overview  over  the design  of the
bioventing system (Kolstad et al.,  1991a).

OPERATION OF THE INSTALLATION
The bioventing installation was started on 12. July. The
extracted gas volume in each well is regulated to a
ventilation ratio of one pore volume per day. In this way
evaporation of hydrocarbons and water is minimized.
BUILDING
GRGUNOWArER
VACUUU *tti _._nuri
^enc PlEZOaB
i ป PB! PI
i,ij)
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The infiltration gallery is operated at a daily infiltration
rate of only 600 liter. This is done to increase the soil
moisture content in a controlled way, without increasing
the risk for leaching of oil. At this moment no nitrbgen
or phosphorus source is added.  During the first period
(July to December) the effect of adding only oxygen and
water will be evaluated.

MONITORING OF THE PROCESS
The soil gas extraction system is  monitored by daily
pressure and temperature readings  in the venting wells
and piezometers. Relative humidity in the venting wells
is also recorded on a daily basis.
The extracted soil gas is monitored weekly for  concen-
trations of oxygen and carbondioxide using a portable
instrument. Hydrocarbon vapour in the off-gas is mea-
                                               i
sured  using  a direct reading photo ionization detector
(PID) and by sampling on  activated  carbon. Water
samples are  taken from pumping well PB 2 at monthly
intervals.
Soil sampling will  be carried  out after  half a  year
(December 1991), one year (July 1992) and after ;two
years  (July 1993).

PBEL1MMARY RESULTS
After  some  initial  operation  problems in July,  the
extraction system is working now continuously. Table 4
gives  the pressure and flowrate in the three extraction
wells.
Table 4. Pressure and flowrates in the three
extraction wells. -.
Well
A
B
C
Depth
(m)
6-10
12-18
20-27
Pressure
(Pa)
-360
-450
-650
Flowrate :
(m3/h)
24
75 i
75 ;

Figure 4 gives an impression of the pressure distribution
and flowfield in the subsoil at standard operation condi-
tions. The temperature is stable at 6 til 8ฐC (8 - 25 m).
          Piezometer
          2         1
Vacuum
wells
                              =     P=-360 Pa
     15m
                              E    P=-450 Pa
     25m
                                     P=-650 Pa
        12m
  Figure 4.    Pressure distribution and flowfield in
              the subsoil around the extraction
              wells.
In the off-gas ,of well A a clear hydrocarbon smell is
noticeable. PID readings show a clear decline i hydro-
carbon vapour concentrations ia well A from initial 540
ppm to 200  ppm (isobutene equivalents) in oktober.
Wells B and C show a stable PID reading of ca. 40 ppm.

The first weeks the carbondioxide concentration declined
in well A. At this moment a stable concentration between
0,2 and 0,3 vol.  % is measured in all three wells (figur
5). The difference i  oxygen, concentration (air oxygen
content - off-gas oxygen content) is fluctuating (figur 6).
The cause for this fluctuation is not quite understood, but
might be caused by rainwater infiltration.
                                                312

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The results indicate that there is biological activity, how

far this activity contributes to hydrocarbon degradation

is not yet known.
      0.5-]
      0.4-
      0.3-
      0.2-
      0.1
                20
                       40      60      80
                        Days (day 0-12.07.91)
                                             100
  Figur 5.
Carbondioxide concentrations in the
off-gas of the venting wells (vol %).
       1.5-
      1.25-
      ฐ'75 '
       0.5
      0.25-
                20      40      60     80
                        Days (day 0-12.07.91)
                                             100
   Figur 6.
Reduction in the oxygen concentra-
tions in the venting wells (vol  %).
 If all carbondioxide production should be caused by oil

• degradation this would mean an average mineralization

 rate of 6 kg THC per day. A very rough estimate of the

 oxygen consumption indicates a degradation of ca. 10 kg

 THC per day.
                                          In December shut down tests will be carried out on the

                                          system to  assess in detail the biodegradation rates by

                                          measuring  increase in carbondioxide content and reduc-
                                          tion of  oxygen  levels in the Venting wells and the

                                          piezometers. Soil sampling will give a first indication if

                                          biodegradation is able to reduce the oil content on this

                                          site. Based on these results the need  for nitrogen and

                                          phosphorus addition will be evaluated.


                                          REFERENCES
Briseid, T and G. Eidsa (1991)
Rehabilitation of oilleakage  at  Trandum - biological
degradation tests. SI  report no. 421-1735,  Center for
Industrial Research, Oslo.

Eyk, J. van and C. Vreeken (1989)
Venting-mediated removal of diesel oil from subsurface
soil  strata  as a  result of evaporation and enhanced
biodegradation. Proc.  Envirotech, Vienna, pp. 475-485.

Hauge, A.  and P. Kolstad (1990)
Evaluation of cleanup methods for oil polluted soil at
Trandum.  NGI  report no.  902542,  Norwegian Geo-
technical Institute, Oslo.

Hinchee, R.E. and R.N. Miller (1990)
Bioreclamation of hydrocarbons hi the unsaturated zone.
Proc. Envirotech, Vienna, pp. 641-650.

Jargensen,  P. and S.R. 0stmo (1990)
Hydrogeology in the  romerike area,  southern Norway.
NGU bulletin no. 418, pp.  19-26.

Kolstad, P., G. Breedveld and A. Hauge (199la)
Rehabilitation of oilleakage at Trandum near building
111 - report phase 1 - design of in situ bioremediation.
NGI  report  nr.  912501-2,  Norwegian Geotechnical
Institute, Oslo.

Kolstad, P., G. Breedveld and A. Hauge (1991b)
Rehabilitation of oilleakage at Trandum near building
111 - report phase 2 - installation and startup of in situ
bioremediation.  NGI  report nr.  912501-3,  Norwegian
Geotechnical Institute, Oslo.

Storra, G.  (1991)
Mapping of oil pollution around building 111 at Trandum
military base.  NGU report no.  91-155,   Norwegian
Geological Survey, Trondheim.
                                                  313

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      NATO/CCMS Guest Speaker:



         Gunnar Renders, Norway



      The History of NATO/CCMS
315

-------
                              EXHIBIT 1
                                             A.'.,G.SA(69)096
                                             20th March,  1969


His Excellency
Manlio Brosio,
Secretary General,
Horth, Atlantic Treaty Organization.


Dear Secretary General,

          I leave for SOJEUJ meetings abroad this morning  and
would like to write a brief note to you before I leave
because there is a matter that .will probably be brought  to
your attention by Mr. Cleveland, next Tuesday.  It concerns
the science activities within t;he Alliance.  Mr. Nixon,  in
hia speech in the Council referred to the national, domastic
problems in all countries, like pollution of the air and aea,
which will need action in all countries to save our civilisation
in the future.  He indicated that such problems might be attacked
by a common effort of the Atlantic Alliance.  I understand
that the United States Delegation has had later indications
froffl Washington that this remark was seriously considered by
the I?resident, and that it might be appropriate and ri.^ht
to look into the matter here in the Science  Division
immediately.

          I had planned to prepare a brief for you for the
Washington meeting, informing you about the  fact that we
did take the matter up in the Science Committee, and the
Oceano-sraphic Sub-Committee after Mr. Nixon's visit, and that
we have charged Professor Oapart (Belgium) with elaborating
a programme of possible action jin the pollution problem.  We
have also decided to have a large scientific meeting on  it
in 1970, and the Science Committee have considered a public
appeal from NATO in order to point out that NATO considers
ti.is problem a very serious one.
                                316

-------
H.S. Manlio Brosio                          20th March, 1969
          Ambassador Cleveland has pointed, out to me that
Mr. Mxon probably wanted to indicate not only the need
for technical efforts in the pollution question, but in a
long series of problems in modern civilisation, like congestion,
noise, youth unrest and so on.  This might mean that the
President feels that the Alliance could take a leading place
in a common attack on many of the urgent problems of our
advanced technical society.

          I believe the revival of the Science Committee,
for example by a system of younger deputies, which I am
advocating, and by adopting certain long-range programmes
(computers, air—sea interaction, pollution, materials) will
make it possible, Irogetii^r with United States sup .'Ort^ to
make an impact on some of these problems.  I shall come
back in some more detail in the brief for Washington.

                                Yours sincerely,
                       (signed) Gunnar Randers
                                317

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               COUNCIL ON FOREIGN RELATIONS.,ซ.-.
5& EAST 6flTH STKEET, NEW YORK, N.Y. 10021 | TtL. (212) S3S-3300 \  CABLE: FOKAFFAIRS, NEW YORK


                             April 10,  1972
    Dear

    With much regret I  decided  that  I  could not be with you on the
    13thซ  We have a big  affair here: I canno,t miss.

    I did want to  report  to you an. interesting event.  On Saturday
    I was in Cincinnati participating  in their World Affairs Institute
    which brings together 1,000 of the best high school students
    from an area within 200 miles of|the city.  The final speaker
    was Gunnar Randers, who was talking about the work of the
    Committee on the Challenges of a:Modern Society.  This was at'
    the end of a strenuous two  days and a man speaking from Che
    NATO platform  might have had up hill work with these young
    people,

    Randers started  by saying that NATO was not a military organi-
    zation, but a  defense organization.  Then he went on in a
    straightforward  way to describe the various projects the CCMS
    is involved with  (oil pollution in the seas, safer cars, air
    pollution in cities, etc.), stressing that the emphasis is on
    fast action with no new bureaucracy.   When he finished, he got
    a standing ovation from that crowd of young people.  NATO will
    be better and  more favorably known in the whole Cincinnati region
    as a result of that single speech.  ,If more spokesmen for NATO
    with Randers1  charm and message could be sent around to gatherings
    like this  one, the understanding 'and  support for NATO would be
    much increased.

                             Sincerely,
                             David W.  MacEachron
   Mr. W. Randolph Burgess,  Chairman
   The Atlantic Council of the United States
   1616 I! Street,  N.  W.              '•,
   Washington, D.  C.  20006          ;
   cc:  Livingston Merchant
                                     318

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               /*ซ•>*  tn* *v>r /?*u/ฃ/s /9*s, , 5, 4 ^ <- J^mAM  C C n 5
       The CCMS has a much  shorter history than the  Science
Programme and was  sot up under more doubt and  resistance.  It
waซ tht interest and pressure by the United states that brought
the CCMS into being, and it has been thซ  initiative  of the USA
which has kept this activity alive*  Some of the member countries
hav* gradually taken initiatives thamselvซs within the CCMS
and others have developed a positive attitude*  The  programme
has created a remarkably good reputation  for efficiency among
other international organizations*

       Tha CCMS refits upon  a few very simple principles t

       1*    Mo budget and  no secretariat.  This is  achieved by
adopting the pilot country  principle.

       2ป    No long-term scientific research.

       3.    Action by governments within short-time span*  These
principles (2 and  3) have been difficult  to adhere to because
action is always difficult  to achieve while recommendations for
long-term research and study is always tempting.  It is
interesting that the USA, being the strongest supporter of the
CCMS, have sometimes let their pilot projects become long— term
studies t  For example, it seems difficult to get the Road Safety
project to lead to any specific proposals for passive resti-aints
although work has been carried out determinedly for three years
in this field.  Instead, recommendations  for further studies
and recommendations for reduction of accidents by a given
percentage, as a general principle, may be the result.  This
tendency may be the most serious problem  for the CCMS in the
future; to make action recommendations is often connected with
political difficulties and general recommendations on long-term
development are therefore chosen instead.
                              319

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       4,    The fourth principle of the COBS is emphasis on
follow-up.  CCMS is supposed, apt only to make recommendations but
to ensure that something happens as a consequence.  The way this
has been done is to establish a pilot country as responsible for
reporting regularly to the CCMS on progress in member countries
relating to a recommendation,  ;fhe follow-up procedure may be
decisive in making the NATO environmental programme more
substantial than the common or  garden variety of international
recommendations on environmental undertakings.
                                320

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                                    NATO/CCMS Guest Speaker:
                                           •       '   "' s      •-
                                       Robert L.  Siegrist, Norway

         International Review of Approaches for Establishing Cleanup
Goals ,for Hazardous Waste Contaminated  Land; and Sampling Method
       Effect on Volatile Organic Compound Measurements in Solvent
                                              Contaminated Soil
                              321

-------
                         APPENDIX D
THE AGRICULTURAL RESEARCH COUNCIL OF NORWAY
INSTITUTE OF GEORESOURSES
AND POLLUTION RESEARCH
       INTERNATIONAL REVIEW OF APPROACHES FOR ESTABLISHING
      CLEANUP GOALS FOR HAZARDOUS WASTE CONTAMINATED LAND
                                By
                          Robert L. Slegrist
                               322

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 INTERNATIONAL REVIEW OF APPROACHES FOR ESTABLISHING

CLEANUP GOALS FOR HAZARDOUS  WASTE CONTAMINATED LAND
                           By
               Robert L. Siegrist, Ph.D., P.S.
                 Visiting Senior Scientist
      Institute for Georesources and Pollution Research
                PostBox 9,  N-1432 Aas-NLH
                          Norway
                          1989
                          323

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                                CONTENTS
                                                                     Page
Contents 	  .....  2
List of Figures. ...............  	  .......  3
List of Tables	:	3
Acknowledgments	  6

Section 1.  Sunmary.	7

Section 2.  Introduction 	  ..........10
            Background	10
            Study Overview ....;..	 10
                  Study Purpose and Approach	10
                  Problems Encountered	12

Section 3.  Overview of Programs for Hazardous Waste Contaminated Land  . 14
            Waste Contaminated Land Character.	...14
            Contaminated Land Program Highlights	15
                  Program Development	...15
                  Nature and Extent;of Problem .............15
                  Remediation Experiences	.19

Section 4.  Approaches to Establishing Cleanup Goals	20
            Introduction ........................20
            Overview of Approaches Used	20
                  United States. . ซ 	  ........... 20
                  Canada	.	 39
                  England	  . 48
                  The Netherlands.	.48
                  West Germany	 53
                  France , .	55
                  Denmark.	55
                  Sweden	 57
                  Finland	 57
                  Norway ...................  	 57

Section 5.  Soil Quality Criteria and Cleanup Goals	58
            Current Attitudes and Use	58
            Characteristic Features. .....  	 59
            Advantages and Disadvantages 	  ..... 62
            Method Development	62

Section 6.  Overview of Cleanup Technologies	 65

Section 7.  Conclusions and Recoomendations	........72

Section 8.  References ..............  	 74

Section 9.  Appendix .......................... 77
            A.  Personal Inquiries and Site Visits Made. .,...,.ป 78
                                    324

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                             LIST  OF TABLES

                                                                       Page

4.9.  Interim guidelines for contaminated sites recommended by the
      Canadian Council of Resource and Environment Ministers . .  . .  .  .40

4.10. Suggested cleanup guidelines for inorganic contaminants in
      acidic soils in the Province of Alberta, Canada	.41

4.11. Soil cleanup criteria of the Ontario Ministry of the
      Environment, Canada	42

4.12. Criteria for ascertaining the contamination of soil and
      ground water in the Province of Quebec, Canada	44

4.13. Tentative "Trigger Concentrations" used in England 	  49

4.14. Soil and ground water criteria used in the Netherlands for
      assessing contaminated land ("Dutch List") .	  51

4.15. Reference values for good soil quality in the Netherlands.  . ...  54

4ซ16. Overview of concentrations of some elements in man-affected
      soils in West Germany.		56
5.1.'  General features of soil and ground water quality criteria and
      cleanup goals and their development	60

5.2.  Comparison of soil quality and cleanup criteria for selected
      contaminants	61

5.3.  Example advantages and disadvantages to the use of soil and
      ground water quality criteria for cleanup goals. ... 	  63


5.4.  Elements of a standards-based approach for establishing
      soil and ground water quality criteria and cleanup goals for
      hazardous waste contaminated land. ................  64
6.1*  Example chemical constituents in different waste groups. ..... 66

6.2.  Treatment technology screening matrix for waste contaminated
      soils  in the USA	 67
                                    325

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                             LIST OF TABLES
6.3.  Sueomary of remedial technologies for treatment of soil
      contaminated by petroleum products in the USA.	68

6,4.  Applicability of techniques for the treatment of contaminated
      land in Europe	i•	  70


Al.   Principal inquiries providing- information regarding cleanup
      standards and technologies for hazardous waste contaminated
      land	T9

A2.   Principal site visits yielding information regarding cleanup
      standards and technologies for hazardous waste contaminated
      land 	 ..... 	 ..........  81
                                    326

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                            ACKNOWLEDGMENTS


The  work reported herein was  conducted at the Institute for Georesources
and  Pollution Research (GEFO)  located  at the  Agricultural University  of
Norway (NLH) located in Aas, Norway.

There  are  many  individuals  and  organizations who  contributed  to  the
successful completion  of  this  research.   The  Norwegian  State Pollution
Control Authority  (SFT), Oslo, is acknowledged  for  providing a  substantial
portion of the financial support for this research.   Dr. Tore 0steraas and
Per  Kr. Rehr are acknowledged for their assistance  in  arranging for this
sponsorship. Invaluable assistance was  provided by representatives from
public and  private institutions located in the various nations reviewed  in
this  work.  Particularly valuable  assistance was  provided by individuals in
Norway, Denmark,  Sweden, Finland, The Netherlands and  West Germany. Also
acknowledged is the assistance  provided by  Dr. Petter  D.  Jenssen,  Senior
Scientist, GEFO.

Inquiries  regarding the research may be  directed to Dr. Siegrist at  GEFO,
Postbox 9, 1432 Aas-NLH, Norway, Tel. 47-9-948140 or at  4014 Birch Avenue,
Madison, WI, 53711, USA, Tel. 1-608-2387697.
                                     327

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                                SECTION  1
                                 SUMMARY


Land   contaminated  by  toxic   and  hazardous  substances  is  a  critical
environmental  problem facing  nations  throughout  the  world.    Central  to
resolution of this problem is the development of policies and procedures  to
enable an assessment of the significance of contamination and the extent  of
cleanup required at a particular site.

In the  study  reported herein, an  international  review  was made of the
approaches used to assess the  significance of contamination and set cleanup
goals  for hazardous waste contaminated land.   The information derived from
this study was to assist the Norwegian government in the development and
implementation  of   their   programs   for   assessment   and  cleanup   of
contaminated land. Emphasis was placed on  the attitudes toward and use  of
standards-based   approaches  involving  soil  and  ground  water  quality
criteria.  The  policies and  procedures used in ten nations  were  reviewed
in varying degrees of detail.   Ten nations  were selected to include  those
with newly evolving as well as long-established programs for  dealing  with
hazardous waste  contaminated land.  The  following nations were included  in
this study:

      o     United States,
      o     Canada,
      o     England,
      o     The Netherlands,
      o     West Germany,
      o     France,
      o     Denmark,                                                   .
      o     Sweden,
      o     Finland,  and                                            ..-,,._
      o     Norway.

Information  was  derived  from  published  literature,  personal inquiries, and
site visits.

The results of this study revealed i that approaches to  establishing cleanup
goals  for  hazardous waste  contaminated land  vary  widely between and
within nations.   In few cases  is there explicit, uniform  national guidance.
Rather  there  is  enormous  variation  in the setting of  cleanup  goals, the
process used  and results of which  are  affected by diverse factors  such as:

      o     Type of  contaminated land  (e.g. licensed waste disposal site,
            underground fuel tanks, accidental spill),
      o     Type of  contamination (e.g. FCBs, Dioxin, petroleum products),
      o     Governing laws and regulations (e.g. Federal law, State law),
      o     Site  ownership (e.g. privately- versus publicly-owned,  known
            versus unknown ownership), and
      o     Public attention and perception.
                                   328

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It is  not uncommon  that  cleanup goals in the form of acceptable residual
contaminant concentrations are never  explicitly established.   In  these  cases
an acceptable course of action for remediation is agreed  upon,  the results
of which yield a de  facto cleanup goal.  Where  cleanup goals are explicitly
set, various methods have been used,  including:

      o     Ad  hoc site by site negotiation and decision making,
      o     Cleanup  to background levels,
      o     Application of cleanup criteria in the form of predetermined
            standards, guidelines and criteria (PSGCs),
      o     Site-specific mathematical modeling, risk assessments  and risk
            management decisions,
      o     A combination of the above.
There has  been  considerable  discussion  and  debate regarding  the  most
appropriate  method(s) for assessing the  significance of contamination  and
establishing  cleanup  goals for  waste  contaminated  land.   The  approach
which has  been  most  controversial,  perhaps,  is  a  "standards-based  soil
quality"  approach  involving the use  of  predetermined standards, guidelines
and criteria (PSGCs).   An increasing  number of jurisdictions have  or are
in  the process of establishing soil  and ground water  quality  criteria for
setting  cleanup  goals,  particularly  for  common,  non-catastrophic  sites.
They  range  from  simple listings  of  a few  common  contaminants  to
comprehensive  listings  of numerous  contaminants.    They  can  address
natural  soil properties  (e.g.  organic  matter  content,  grain size)  and/or
different current  and future land uses.   In one  nation,  The Netherlands,
criteria,  have even been developed to characterize "good  soil quality".

In  few cases are the  criteria true "standards".  Rather, they are viewed as
general  guidance  subject to  site by site review  and  justification  and/or
modification.   Where  they exist,  cleanup criteria have  often evolved  from
the adaptation  of  existing environmental standards and  criteria as well as
the generation  of  new  criteria based on contaminant transport  and fate in
the environment and  reasonable  exposure  scenarios  for  potentially affected
populations and ecosystems.

Standards-based  approaches  involving  cleanup criteria  are an  important
component of an overall program  for dealing  with contaminated  land.  While
there are   definite  difficulties   associated   with   the   development   and
implementation of soil and ground water quality criteria,   there appears to
be  a clear  desire and  need for  them.   They streamline initial assessment
and  screening  of  contaminated   sites, encourage  redevelopment   of  old
industrial  sites   and  facilitate   broad-based  soil  protection  programs.
However, it  is  widely recognized that  they  will  not obviate the need for
consideration of site  specific  factors nor quantitative risk assessments and
risk  management approaches.
                                    329

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It appears that  a combined  approach  to establishing  cleanup  goals for
hazardous waste  sites may be most appropriate.   Such  an approach could
include  consideration of  current  and  future  site  use  and  potentially
impacted  humans,  other  biota and  environmental resources.   A systematic
site  classification procedure is also  needed  to  preliminarily  screen  and
classify  a  site  according  to  the  potential  hazards  associated  with  it.
Adoption  of a  comprehensive  listing of  soil  and  ground  water  quality
criteria   would   facilitate   initial   assessment  of   the   significance  of
contamination and preliminary cleanup goals. For  sites rated  to  be of high
hazard, a  site specific risk  assessment  would  be needed to verify cleanup
goals.  For low hazard sites,  use ofi soil and  ground water quality criteria
alone  would  normally  be  sufficient.   Intermediate  sites  would  require
judgement and possibly consideration of  cost-benefit factors.

Initial efforts at  site remediation (i.e. cleanup) in different nations  largely
involved either 1) excavation and offsite treatment and/or landfilling, or 2)
in place encapsulation and isolation.  There  is increasing interest  in  and
use  of onsite and insitu treatment technologies.  Considerable research and
development work in progress  in several nations.     A  wide  variety of
processes  are  now   available for  treatment  of  contaminated  land,  both
offsite, onsite and insitu.    Treatment systems  involving  low  temperature
thermal   evaporation,  soil   washing,   in  situ   vapor   extraction,   and
solidification/stabilization   have      growing   performance  bases.     Less
established are  some onsite/insitu  techniques such as  bioremediation, in
situ steam stripping and in situ vitrification.

It is recommended that the  results of this study be considered in light of
existing  Norwegian regulations and: that the issue  of establishing cleanup
goals for  hazardous  waste  contaminated sites be discussed  and  resolved*
This should be accomplished  early in the  development of Norway's program
for  addressing   problems   with   hazardous   waste   contaminated   land.
Formulation of  a systematic,  nationally consistent  approach to  establishing
cleanup  goals is  an  important challenge  facing  Norway  as  well  as  many
other  nations.    The approach which  ultimately  proves  appropriate for
Norway will  depend  on a  careful analysis of many  factors, including those
of  a  technical,  socioeconomic,  political  and  legal nature.    A  suitable
approach  may include some  form   of  site, soil and land-use classification
combined  with  soil  and  ground  water  quality  criteria.   This  will  prove
workable for initial  site  screening as  well  as setting  cleanup goals for
common, non-catastrophic sites.  For  high  hazard* catastrophic sites,, a site-
specific  risk  assessment  and risk  management  approach will  likely  be
needed*
                                     330

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                                SECTION 2
                              INTRODUCTION
2-.1    BACKGROUND

Norway  has  long   been  regarded  as   a  pristine  nation   with   majestic
mountains  and  enchanting  fjords.    Unfortunately,  during  the  past  few
years an increasing number of old waste  sites and parcels of contaminated
land have  been discovered.    For example,  an old waste site was  recently
discovered  near  Oslo  during  railroad-related  construction  activities.   The
site  had been used for  dumping and burning  of  flammable liquids  in  an
effort  to reduce fires  at a municipal landfill.   Approximately 10,000  nr* of
soil  contaminated  with  solvents  ultimately  were excavated  and  properly
disposed of.

Since Norway derives  most (>80%) of  its potable water from  surface  water,
concern  over ground water  pollution has so far  been limited.   However,
there is  growing recognition, of potential  hazards to  public  health  and the
environment  via  other  pathways.    While  there  is  little  question that
contaminated  sites  exist  in  Norway,  little is known  about  the nature  and
extent of  the, problem.  National  inventories  have recently  been  initiated
including industrial branch surveys and old waste site surveys [1].

Discoveries of abandoned waste  sites and contaminated land, often during
construction  activities,   have  necessitated  prompt  action  by  regulatory
authorities.  As in the rest of the  world, a critical  but  extremely  difficult
task  has  been assessing the significance of  contamination  at  a  particular
site  and determining the extent of cleanup required.
2.2   STUDY OVERVIEW

2.2.1   Study Purpose and Approach

This  study was  undertaken  to  gather and  review the approaches  used in
various nations to establish cleanup goals for  hazardous waste contaminated
land.  Of particular  interest were  the current attitudes toward  and use of
"predetermined  standards,  guidelines  and  criteria"     (PSGCs).     The
information  derived  from  this   study  was  to  assist   the   Norwegian
government in the development  and  implementation of their  programs for
assessment and cleanup of contaminated land.

Information  for  this   work  was  gathered   by   several  means.     The
international   literature   was   surveyed   by   computerized  and   manual
techniques.   Personal inquiries  were  made  to responsible  agencies  and
individuals in  ten nations.   The nations selected  for  study included those
with  a range of  characteristics  and in which  there  were  newly  evolving or
long-established  programs for dealing  with  hazardous waste contaminated
                                    331

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land  (Table 2.1).  The following nations  were included in this study:
      o     United States,
      o     Canada,
      o     England,
      o     The Netherlands,
      o     West Germany,
      o     France,
      o     Denmark,
      o     Sweden,
      o     Finland, and
      o     Norway.
Personal  site visits were  made  where  appropriate and feasible  to  gather
information first-hand.
Table 2.1.   General physical characteristics of the nations selected for
            study [36],


Nation

Population
(millions)

Area
(106 Ha)
Population
Density
(capita/Ha)
Urban
Population
<*>
United  States     247.5
Canada            25.3
United  Kingdom    56.6
The Netherlands   14.7
West Germany      60.2
France             55.8
Denmark            5.1
Sweden             8.4
Finland             5.0
Norway             4.2

Statistic Date     1989
940
998
 24.4
  4.1,
 24.91
 57.2
  4.3
 49.0 i
 33.7
 32.4
0.26
0.03
2.32
3.59
2.42
0.98
1.18
0.19
0.15
0.13
79
76
92
88
86
77
84
85
61
80

1980-1986
                                    332

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   Persons per  ,.,
     Hectare
                                                                   50%
                   USA CAN  UK  HOL GER  FRA  DEN SWE FiN  NOR
Figure 2.1.  Population characteristics of the nations reviewed in this
            study.
This  study  was  not  intended  to  comprehensively  review  nor  critically
evaluate and critique  the numerous  existing  approaches and procedures.
Clearly, this would  have been an insurmountable  task, given the resources
available  for this project.    Nor was it  intended that  this  study  would
necessarily develop a  new or  modified  approach  for use under  Norwegian
conditions.     At the  onset,  it was clear  that  approaches  to assessing
contamination and setting cleanup goals include many non-technical issues,
including those of a socioeconomic,  political and legal nature.   Rather,  this
study  was  meant   to  provide  a  base  of  information  regarding  the
international  state  of  practice  in  the  area of  cleanup goal setting for
hazardous  waste contaminated  land.   This information  would  hopefully
facilitate the effective  evolution of programs  and practices in Norway.
2.2.2  Problems  Encountered.

At the  onset, the  subject  of  this study was  recognized as a complex  one,
intertwined not  only with  government policies and programs for  dealing
with contaminated  land, but also with those for environmental protection in
general.  It was accepted  that  efforts to  gather and  review all  relevant
literature and contact aE  knowledgable agencies  and individuals  would be
futile.  Rather,  attempts  were  made  to  gather what was  perceived to be
representative  current information.   This  was  made  somewhat  difficult
considering the  geographic scope and communication difficulties  associated
with  the  foreign nations  involved.    It  was also difficult to describe the
                                     333

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status of  approaches  to  setting cleanup  goals  due  to the  diversity  of
agencies and personnel involved  in any one nation, as  well as the dynamic
nature of this subject both on a local and national level,  even in nations
with  apparently   well-established  programs   (e.g.  United   States,  The
Netherlands, West Germany).
                                    334

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                                SECTION 3
   OVERVIEW OF PROGRAMS  FOR HAZARDOUS  WASTE CONTAMINATED  LAND


This  section  provides  an  overview  of  the  programs  for  dealing  with
hazardous  waste contaminated land in  the nations selected for study.   This
information is   provided as  a framework  within  which  the policies  and
procedures for  assessing the  significance of contamination and establishing
cleanup goals  have evolved.
3.1   WASTE CONTAMINATED LAND CHARACTER

There  are  many  different names  used to refer to what  might generally  be
defined as  "contaminated  land".   Few  formal definitions  of contaminated
land exist,  however.  One  which has  been put  forth  is  that of  the NATO
Committee on Challenges to Modern  Society (NATO CCMS)  [2]:

       "Land  that  contains  substances   that,   when   present   in
      sufficient quantity or  concentrations are likely  to cause harm
      directly  or  indirectly to  humans,  the   environment  or   on
      occasions to other targets."


This   definition   suggests  that  increases  in  chemical   quantity   or
concentrations  in  a  given  parcel  of  land   would  not  in  and   of itself
necessarily  result  in  the  land being  considered  "contaminated".   Thus,  to
assess  whether   a   given   site  were  contaminated  or   not   requires
consideration  of  site land  use  as  well  as  the  land's  relationship  to
surrounding land uses and the ecosystem.

Contaminated land as  defined above could include a wide variety of sites.
Typical sites of concern include:

      o     Commercial and industrial  sites  (operating and derelict sites),
      o     Solid waste landfills (particularly older ones),
      o     Areas where incidental  spills have occurred,
      o     Leaking underground storage tanks (e.g. chemicals, fuels,
            wastes), and
      o     Land-based waste storage, treatment  and disposal sites.


As illustrated  by the  above  examples, the land may or  may not have  been
the intended receiver  of the liquid and/or solid wastes.  Moreover, the land
may  have  been  used for  waste  containment and long-term storage  or
alternatively for waste treatment and recycling.
                                    335

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3.2   CONTAMINATED LAND PROGRAM HIGHLIGHTS

3.2.1   Program Development

Programs for  dealing  with  contaminated land  have  generally  evolved in
response to the need for public health and  environment protections, in some
cases  driven   by  the   need   for   industrial  site   redevelopment  for
moresensitive uses.  The programs can be  geared toward site cleanup and
risk reduction,  land reclamation  and  reuse, or a combination thereof.

In  most cases,  one or  more  notorious incidents  has  stimulated  public
attention and  inquiry  into  the problem  of hazardous  waste contaminated
land.  This  has led to increasing  public awareness of the nature and  extent
of  the  problem.    In  response,  political  action  normally  has  produced
governing   legislation.    Regulations, policies  and  programs  were  then
formulated.

Early  in the  evolution  of  contaminated  land programs, inventories are
initiated  to  determine the number, ^Location  and potential  severity  of  sites.
This  is  often  on  a   Federal  or !at least  State  basis.    Following the
inventories,  Federal and/or  State   programs  for  site investigation  and
cleanup  are formalized. Often  the results  of  the inventories  are used to
evaluate  the need and urgency  of addressing the problem,  including the
need for and nature of government] financing.  In some cases, funding has
been provided for research  and development efforts.

Some general  characteristics  of  the contaminated land  programs in the
nations reviewed in this  study are summarized in Table 3.1.  Some nations
embarked on  cleanup  campaigns  almost  a  decade  ago  (e.g.  USA,  The
Netherlands)  while  others  have  begun in  earnest  only  recently  (e.g.
Norway,  France,  Canada).    In   some  nations the  programs  have  been
incorporated into broad soil protection programs.  The clearest example of
this is The  Netherlands where  a  powerful national law  was enacted in 198T
(The Soil Protection Act)  [3].  West Germany initiated a conceptually similar
program  in  1985 [4],    ป

The  primary  driving  forces  behind  the  cleanup  of  hazardous   waste
contaminated land appear to vary between  the nations studied  (Table 3.2).
Prevention  or  mitigation of pollution of ground  water  used for  drinking
water  as   well  as ' ensuring  safe,  housing  developments   on  reclaimed
industrial sites and waste deposits are often of principal concern.


3.2.2  Nature  and Extent of the gro'blem

The nature and extent of the  problem with  hazardous waste contaminated
land  varies widely between  nations (Table  3.3).   Based  on  inventories
and/or other estimates, the number  of known or   suspected contaminated
sites can be very high.  Generally,'. the number of sites  identified initially
includes  mostly old waste deposits and landfills.   Subsequent inventories or
site discoveries often  include  more  and  more industrial  and commercial
sites,  including leaking underground gasoline  tanks.   With  time,  sites
continue to be discovered and the number of sites  under study  continues
to grow.                           :
                                    336

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Table 3.1.   General characteristics of  contaminated land programs.


Nation                  General Program  Description


United  States.     Federal  program   for  cleanup  of   major  uncontrolled
hazardous  waste sites  enacted by "Comprehensive Environmental Response,
Compensation  and Liability Act (1981),  also known  as  "Superfund", and later
amendments (1986).   Subsequently State level programs evolved separately,
e.g.  in  New Jersey, California  and Wisconsin. Federal and  State funding is
available for priority abandoned sites.

Canada.  No national program.   Special programs, initiated recently  in a  few
Provinces, e.g. Quebec (1988) and  Alberta (1985).  Programs often geared to
decommissioning of industrial sites.

England.  Contaminated land reclamation is largely coincident with old waste
and  industrial site  redevelopment.  Federal  level guidance issued in 1987.
Federal  funding  for  reclamation  of   priority  sites  from  "Derelict  Land
Grant".

The   Netherlands.    Federally  initiated  program  with  enaction   of  "Soil
Cleanup  (interim)  Act"  in  1983  and   "Soil  Protection  Act"  in  1987.
Implementation at  Provincial  level.    Some Federal  funding  in  addition to
local funding  for  priority abandoned sites.

West Germany.  General  State level programs initiated  in  1970's. Increasing
attention  at Federal level in  late 1970's.   Federal guidance and  research
funding initiated  in 1983.  Adoption of "Conception  for  Soil Protection" in
1985 with  possible  revision and amendment  of Federal laws.  No  dedicated
financing  programs  yet, but  discussion of  government/industry funding
options.                                                 •'...'

France.    No specific  national legislation  or  .directives.   National level
guidance  and cleanup supervision. Limited  Federal  funding on  a case  by
case basis.

Denmark.   Dedicated legislation  in 1983.   National inventories completed.
Government sponsored  research.    Government   funding  of  cleanup  of
abandoned  sites.

Sweden.    Specific  national  legislation  enacted  in  1988.  National level
inventory  completed  (1985).   Government  sponsored research  and  limited
Federal funding  available.

Finland.    No  specific  national  legislation   or   directives.  National level
inventories in  progress  and  informal  guidance  provided. No  government
funding provisions.

Norway.    No  specific  national  legislation   or   directives.  National level
inventories in  progress  and  informal  guidance  provided. No  government
funding provisions.
                                    337

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Table 3,2.   Apparent  principal driving forces  motivating site remediation.l
Nation
      Apparent Principal Driving Forces
United States



Canada



England


The Netherlands




West Germany



France

Denmark



Sweden



Finland



Norway
General public  health  and  environmental risk reduction,
often  associated   with  ground  water  contamination  of
drinking waters.

Decommissioning and safe reuse  of industrial properties.
Sometimes,  general public  health and  environmental risk
reduction.

Decommissioning and safe reuse  of industrial properties.
Seldom  ground  water protection or simple risk reduction*

Broad-based   soil   protection   including   cleanup   of
contaminated land,and  prevention of future  contamination.
Enable  safe reuse of industrial  sites and general public
health and  environmental risk reduction.

Primarily   public   health protection  from  ground  water
contamination of drinking water•   In housing areasi also
prevention  of direct contact and  ingestion.

Not clear.   Public  pressure  and political impacts noted.

Primarily   public   health protection  from  ground  water
contamination of drinking water.   Also  safe redevelopment
of old industrial sites in urban fringe.

Not  clear.    Mixture of technical,  psychological,  political
considerations.   Long-term effects  of  ground  water  on?
surface water recognized.

In  some  areas,  public  health  protection  from  ground
water  contamination  of  drinking  water.   In others, safe
redevelopment of old industrial sites.

In  a few   areas,  public health  protection  from  ground
water   contamination  of  drinking   water.    In  others,
protection   of  aquatic  resources  (e.g.  fjords)  or  safe
redevelopment of old industrial sites.                    ป
      information  presented   repesents  current  general  perceptions   on
nation-wide driving forces.  It is  recognized that  on a particular  incident,*
the driving forces can be  substantially  different than those stated.
                                     338

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Table 3.3.   National statistics on contaminated site discoveries and
            remediation.
      Site  Discoveries
Nation (ref.)
Site Number and Concern
    Remediation Experiences
Approx.     Example  Methods
# of Sites   Commonly Used
United States  (6.7)
23000 ('87) with 900 ('87)            130 NPL
nat. priority (NPL) sites.            ?Non-NPL

Canada   (8)
Total unknown.                      Few

England   (9)
300 estimated.                       >500

The Netherlands  (5)
6060 ('86).                           380
West Germany  (11)
35000 ('85)  with 5400  req.              ?
immediate action.

France   (12)
453 ('87)  with 82 serious              95
Denmark  (13-14)
1599 ('88). Estimate 9000             30-60
potential sites.

S weden  (15)
3800 ('85) old waste sites,            Few
500 est. of concern.

Finland  (16)
Total unknown. 1200 landfills         Few
with 378 with hazardous wastes,
112 need immediate action.

Norway  (1)
Total unknown.                       Few
            Excavation/landfill
            Incineration
            Insitu treatment

            Excavation/landfill
            Isolation/capping
            Excavation/landfill

            Excavation/treatment
            by thermal,washing
            Excavation/landfill

            Encapsulation
            Excavation/landfill
            Excavation/landfill
            Encapsulation
            Solidification

            Excavation/landfill
            Incineration
            Onsite treatment

            Excavation/landfill
            Incineration
            Encapsulation

            Excavation/landfill
            Some incineration
            Some landfarming
            Excavation/landfill
                                     339

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3t2.3   Remediation Experiences

While the number of  sites identified can  be large,  the number remediated
can be  very small, typically  less than  10% of those discovered  (Table 3.3).
The number of sites restored to productive use  can.  be even smaller.

Early remediation efforts in most  nations  typically involved excavation and
offsite  treatment or  Ian drilling.   Some nations  have  also  used  in-place
containment  by  capping  and  other  isolation techniques.    More  recently
there has been increased  interest in  onsite and  insitu  technologies such as
bioremediation,     vapor   extraction,   soil   washing,   solidification   and
stabilization.  For example, in the Superfund program  in the United States,
onsite/insitu remediation approaches  are now considered desirable.   There
is considerable  research  and  demonstration  work  ongoing in  the United
States,  The Netherlands, Denmark; and  West Germany  related to onsite and
insitu treatment  techniques.

There have also  been an increasing number of treatment plants established
solely for  treatment  of contaminated soils.   In  many  cases, these systems
were initially mobile  units, later established as  fixed-based  plants.  In The
Netherlands, for  example, there are  now numerous  thermal, extraction and
biological treatment plants with a total annual capacity of nearly 0.5 million
m^  [51.  Similar plants have recently  been  implemented in Denmark and West
Germany*
                                    340

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                                SECTION 4
             APPROACHES FOR ESTABLISHING CLEANUP GOALS
4.1  INTRODUCTION

The  need to assess the significance of contamination and establish cleanup
goals for hazardous waste  contaminated land is based largely  on  public
health  and  environmental protection  concepts.    In   many  respects  the
foundations underlying this need are the same as those behind the existing
spectrum of  regulations  and  standards  governing  contaminants  in  the
environment.   These  include  drinking  water standards, ambient  air  and
water quality criteria, air  emissions from incinerators, discharges to  surface
waters  from  waste water  treatment  plants  and  land  spreading  of  sewage
sludges.

Assessing the significance of  contamination and establishing cleanup goals
for  hazardous waste contaminated  land is  extremely  complex due to many
factors,  but perhaps most importantly!

      o     The heterogenous, non~fluid and unpredictable nature of soil,
      o     Difficulties in  characterizing the occurrence and predicting  the
            transport and fate of hazardous substances in soils,
      6     The unknown  but typically wide variety of chemicals  present
            in waste contaminated land,
      o     The multiple pathways by which contaminants may reach
            humans and other receptors  (Figure 4.1),  and
      o     Uncertain and highly variable exposure  conditions.


4.2  OVERVIEW OF APPROACHES USED

The  approaches used to establish cleanup goals within  the nations reviewed
in this  study are  discussed  below.   In  Section 5,  further  discussion  is
given regarding  the use of  and perspectives  toward soil  and  ground water
quality  criteria  and  cleanup  goals.    As  summarized  in  Table  4.1  and
described  below, the  approaches used today  vary  widely both within  and
between nations.  In addition, the approaches in most  nations appear to be
in a state  of evolution, not  yet  fully  developed  nor implemented, especially
on a nationally consistent  basis.


4.2.1 • United States

In  the  United  States  (USA),   there  is  no  explicit,   national  guidance
regarding  approaches  for establishing cleanup  goals  for hazardous waste
contaminated  land.  Approaches for establishing cleanup  goals vary  widely
depending  on  the  government agency  responsible   for  regulation  and
oversight  of the  remediation  (i.e.  cleanup)  activities.  Contaminated sites
regulated  by  different Federal laws  and  agencies  can  be  handled quite
differently  (e.g. the  Comprehensive  Environmental  Response, Compensation
and  Liability Act  (CERCLA,  1981; 1986) versus  the Resource  Conservation
and   Recovery  Act  (RCRA,  1976|  1984)  as administered  by the  U.S.
Environmental Protection Agency).
                                   341

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In  addition  those  sites  regulated ( by  State  laws and  agencies can be
handled differently as  well.  In  most cases,  hazardous waste contaminated
land  has been  cleaned up for public health  and  environmental protection
reasons.  Only  recently has  increased attention  been  given to reclamation
and redevelopment considerations during cleanup.

The approaches used by Federal and State  government agencies in the USA
for setting cleanup  goals at hazardous waste sites  have  been subject to
much scrutiny.   This is  particularly true  for the policies and procedures
used for national priority  sites (i.e. Superfund  sites) [e.g.  6,7,171.     The
results of a recent review [17] are  summarized in Tables 4.2  and 4.3 while
highligrhts of some of the approaches used  by  various  government agencies
are given below.
                                    Flt-TEW
                        HYDRO SOU.   BOTTOM FEEOIB
                         MOISTURE  ATMOSPHERE (VAPOR)
                         MOISTURE ATMOSPHERE (PARTICLES)
Figure 4.1.  Potential transport pathways and exposures associated with
             hazardous waste  contaminated land.
                                     342

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table 4.1.   Approaches used for assessing the significance of
            contamination and establishing cleanup goals for contaminated
            land.
Nation
      Approaches to Establishing: Cleanup Goals
USA
Canada
England
For  Nl?L  sites  (Le. Superfund)  use  applicable^  relevant  and
appropriate Federal and  State requirements whefe' available  and
formalized  site-specific  risk assessment  methddologies.    For
non-NPL   sites,  procedures   vary   Widely   by   State   and
government   jurisdiction   and  include   miiiiipies   of  generic
criteria   and   background  levels   as   well  as\   site-specific
formalized risk  assessment methodologies.  [(J^lT^iS]

Only Quebec  has  a  formalized approach where M comprehensive
list of generic  criteria adapted from the  "tititeih  List"  is  used
for  initial  guidance  and   screening   with  site-specific   risk
assessments as  appropriate.  [8,19]

No   national    system.      National   guidance  on   "Trigger
Concentrations"  for  some  contaminants   ebiflifiehly  found  on
industrial sites often  considered  for   redevelopment  (e.g. old
gas works). [9,20]
Netherlands National policy  of  maintaining  soil "multi-functidiiality". Generic
            criteria^  (A-B-C levels)  for  evaluating significance  of pollution
            enacted  in  1983  (often  referred  to  as  the  "Dutch  List").
            Reference  values for good soil quality (new  A-level) enacted in
            1987.  Contaminated land must  be cleaned up to multi-functional
            quality  (A-level)   unless  it   is  technically   or  financially
            unfeasible or environmentally harmful to do so.  [3,5,10,21-23]

W.Germany  No   national  approach,  control   by   provincial  governments
            (Lander).  Use  of  "Dutch  List" with consideration given to local
            conditions. West   German  "Guides/Threshold"   values  for  soil
            contamination now under  development based on soil  protection
            policy initiated  in  1985. [11,24]

France     No   national  approach, control  by   local governments.    Use
            qualitative  risk   assessments.     If   pollution  by  natural
            substances,   must  reference  background.     Development  of
            standards for soil pollution now under consideration. [11,12]

Denmark    No   national  approach, control  by   local governments.    Use
            "Dutch List" for  general  guidance  and  screening as  well as
            existing  Danish  standards  where available.   Final decision on
            particular site based onsite specific  considerations;  Formalized
            risk assessment methods now under development.  [13,14]
                                     343

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Table 4.1.cont.
 Approaches  used for assessing the significance of
 contamination and establishing  cleanup goals for
 contaminated land.
Nation
 Approaches  to Establishing Cleanup Goals
Sweden      No  national  approach.     Limited  experience  to  date.     Use
              generic   criteria   (e.g.   "Dutch   List")  if   available  for  initial
              guidance  but  site   specific  decision  based   on  local  factors
              including technical,  political, economic and  psychological. [15]

Finland      No  national  approach.     Limited  experience  to  date.     Use
              generic  criteria (e.g.  "Dutch List") for initial  guidance. [16,25J

Norway      No  national  approach.     Limited  experience  to  date*     Use
              generic   criteria   (e.g. ;  "Dutch   List")  if   available  for  initial
              guidance.  Site  specific  decision  based on intended  site  use,
              technical feasibility  and cost as  well as secondary contamination
              during cleanup. (1]
Table 4.2.    Terminology  used by  some  approaches  to establishing'  cleanup
              goals for hazardous waste  contaminated land in the  USA [17].
Description
of Term
Acceptable human
daily doio of a,
•ubitanca
EPA
Acceptable intake for
chronic/subchronie
expoiur* (AIC/AIS),
mg/kg x day
California
Maximum exposure
level (MEL),
lag/day
U.S. Army
Acceptable daily
dos.(D_),
mg/kg x day
Washington
' State
Not used
New Jersey
Not used
Experimental doia that
  li considered the
  threshold of
  adversa effects
No observed advene
  effect level (NOAEL)
 Concentration of toxic   Target concentration
  substance in a medium  for chronic expoiure
  that doe* not produce
  an adverse effect on
  chronic exposure
 Human dote of a
  substance expected
  from contact with
  contaminant
Subchronic/chronic
  daily intake
  (SDI/GDI)
No observed advene   No-effect level
  effect'level (NOABL)  (NEL)
                                                                        Not used
                   Applied action level   Single-pathway      Not used
                    (AAL)            preliminary pollutant
                                     limit value (SPPPLV)
                                     and preliminary
                                     pollutant limit
                                     value (PPLV)
                                      Not used
                 Not used
                                                                        Not ueed
                                                                Not used
                                             Acceptable soil
                                               contaminant
                                               level (ASCI)
                                                                                   Not used
 Average amount of
  medium consumed
  daily by an adult
Chronk/subchronic
  daily intake
  (CDI/SDI)
Intake factor
                                                       Transfer factor
                                                                        Not used
                                             Intake factor
                                         344

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Table 4.3    Comparison of five  approaches to establishing cleanup goals  for
            hazardous waste contaminated land in the USA [17].
Dencription
Of Term
Biologic receptors
addressed .
Media addressed
Toxicologic data bate
Duration of exposure
considered
Substances considered
Routes of absorption
addressed
Derivation of acceptable
daily human dose
Treatment of carcinogenic
and noncarcinogenic
effects
Carcinogenic risk goals
Effects from multiple
route exposure
Interconversion of media-
specific or route-specific
standards
No data
EPA
Human*
Air, nurface
water, soil,
ground water,
and fish
Primary
literature
Chronic and
subchronic
Indicator
compounds
Ingestion and
inhalation
From no observed
adverse effect
level (NOAEL)
Separate
io-4-io-7
Considered
additive
Not recommended
Contact EPA
California
Human biota
Air, surface
water, soil, and
ground water
Primary
literature
Chronic
All detected
Ingestion and
inhalation
From maximum
exposure level
(MEL) and other
standard*
Separate
1Q-6
Considered
additive
Yes, with
appropriate
adjustment
Not addressed
U.S. Army
Human biota
Air, surface
water, soil,
ground water,
and food chain
TLV, MCL, FDA
standards, ADI,
primary literature,
and LD50
Chronic
All detected
Ingestion and
inhalation
From no observed
advene effect
level and other
standard*
Separate
io-6
Considered
cumulative
Ye*, with
appropriate
adjustment
Not addressed
Washington
State
Humans
Air, surface
water, soil, and
ground water
Not applicable
Chronic (?)
All detected
Ingestion and
inhalation
Standards
Not addressed
Not addressed
Not addressed
Not addressed
Cleanup to
background
New Jersey
Human aquatic
life
Soil, surface
water, and
ground water
WQC, drinking
water guidelines,
and ADI
Chronic
Indicator
compounds
Ingestion
From other
standards'
Separate
io-6
Not addressed
Not applicable
Not addressed
                                    345

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     Environmental Protection Agency.    Under  the  Superfund  program
implemented  by the  U.S.  Environmental Protection  Agency (U.S.  EPA)  as
authorized by the Comprehensive  Environmental Response, Compensation and
Liability Act  (CERCLA) of 1980 and as amended  in 1986, the  hazardous waste
contaminated sites posing  the greatest  risks to human  health  and  the
environment  can be cleaned up. As of 1989, there were approximately 1200
sites on the  National Priority List (i.e. Superfund sites). Federal assistance
can  be  received  if  those  responsible  for the  contamination  cannot  be
identified or  are unable to  pay for the cleanup.

The  U.S.  EPA  approach  for  site assessment and   cleanup  foal  setting
involves a site-specific risk assessment conducted according to  procedures
which  are comprehensively  presented  in  their  Superfund  Public  Health
Evaluation Manual.  A synopsis of the approach is presented below.

A variety of  terminology is used.   : Critical toxicity values are a property of
chemical  dose-response   relationships.     Acceptable  daily  intake  for
subchronic exposures (AIS) is  the highest  human intake  (mg/kg/d)  which
does  not cause adverse  effects  during short-term  exposure*  Acceptable
intake for chronic exposure  (AIC) is the essentially  the  same as the  AIS
except that the exposure is long-term.   The AIS and AIC values (for non-
carcinogens)  are derived  from no-observed-adverse-effect-levels  (NOAlLs)
and  protection  of  sensitive   members  of  the  population  considered  (e.g.
children, elderly).    Uncertainty : factors  are  applied  to  experimentally
derived  NOAELs.   The  carcinogenic  potency  factor  is a  measure  of  the
carcinogenic  potential corresponding  to a lifetime cancer risk per unit dose
of l/(mg/kg/d).

The  estimated daily intake is the daily  dose  under the specified  exposure
route and conditions.  The subchronic  daily intake  (SDI) is the projected
human intake averaged over a short  time in mg/kg/d.  The SDI is  the peak
short-term concentration  (STC) multiplied by the human intake factor times
the body weight factor.   The  chronic daily intake (CDI) is the projected
human intake  averaged over 70  yr in ng/kg/d.  The CDI  equals  the peak
long-term concentration (LTC)  multiplied by the  human  intake  factor  and
the body weight factor.

The estimation  of  daily intake is  made assuming human exposure can occur
from different  media (air, ground water, surface  water, soil and fish)  and
intakes  (ingestion, inhalation,  skin  absorption).  The intake is  estimated
separately for  each  indicator  compound,  route of  exposure,  duration of
exposure and population exposed.   Total human intake  for each route of
exposure is  a  sum  of  daily  intakes from  all media  by  the same  route.
Additivity only  applies  to  the   same  population,  same  time  and  same
duration (Le* subchronic  vs.  chronic).
                                   346

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For carcinogens, GDI values are used to calculate lifetime cancer risk where
lifetime risk is equal  to the  CDI multiplied  by the carcinogenic potency
factor.

Exposure   to  multiple  chemicals  by  multiple  routes  is  also  considered
assuming  the  principal  of  additivity.   That  is, simultaneous  exposure  to
several chemicals that cause  the  same type of toxicity are  additive.  For
exposure to the same noncarcinogen by multiple routes:


 m    SDI(route)i                   n     CDI(route)i
  ^   	  < 1   and        S    	•	   < 1
 1=1  AIS(route)i                   i=l   AIC(route)i


Similarly, for  exposure to the different noncarcinog-ens  by the same route:


 n    SDI (substance)j               n_.    CDI(substance)j
  Z   	  < 1 and       2.    	•	•—-  < 1
  j=l  AIS(substance)j               J=1   AIC(substanee)j


The  overall hazard for  multiple  routes  and multiple chemicals is  combined
into a hazard index:


 m   n      SDI(ij)                 m    n      CDI(ij)
  1"   Z*	   <  1  and      Z    1"    	  ' <-l
  i=l  j=l    AlS(ij)                 i=l  j=l    AIC(i,j)


The  assumption of additivity is also applied to carcinogens where,
                  m    n
  Cancer risk =    ^   ^     (GDIy * carcinogenic potency factor y
The  steps  involved  in  the  site  assessment  and  cleanup   goal  setting
according to the above approach include:

      o     Selection  of indicator compounds for a given site.

      o     Estimation of the  concentrations of  the  indicators in  media at
            points of maximum human exposure,  both short-term (STC)  and
            long-term (LTC).
                                    347

-------
      o     The  STCs  and  LTCs  are  first  compared  with applicable  or
            relevant  and  appropriate  standards   (e.g.  drinking  water
            standards).   If  standards  are  available for all indicators,  no
            further analysis is required.

      o     Estimated  next are  human daily  intakes (SDIs and GDIs) for
            each selected indicator compound, each  route  of exposure  and
            each exposure duration*   Cancer risks are also calculated.

      o     The hazard indexes are! then computed.


The  target levels for  cleanup are  determined  differently for  indicator
compounds with standards versus those without.  If standards exist, that
sets the upper limit on  target  levels.  For  those  without standards, the
compounds are divided into two groups, 1) chemicals with  noncareinogenic
toxic  effects  and 2) potential carcinogens.   For noncarcinogens,  for  an
individual  compound the  daily intake must be  maintained  equal to  or less
than the acceptable daily intake.  In addition,  for multiple substances and
routes, the overall hazard index must  be maintained equal to or less than
1. To  maintain the hazard index below 1,  the  target levels for individual
compounds can be apportioned between different media and compounds.

For carcinogens,  cleanup is  intended  to maintain the  cancer  risk in the
range  of 10""* to 1Q~^,  with  10~*> established as a point of departure.  The
target concentration is  that  concentration that will produce a chronic daily
intake associated  with  this range  of  risks.  Again for  multiple  routes and
substances,  the  target   CDI  can   be apportioned  between   media  and
substances in  any combination as Jong as  the total cancer risk  is within
the specified range.

Lack   of a consistent  method for' setting cleanup  goals  was  a  primary
concern  of the  U.S. EPA and affected  parties and led  to  explicit language
in  the  Superfund amendments and   reauthorization act  (SARA)  of  1986.
SARA  establishes  cleanup  actions  and also  stipulates  the, conditions for
disposing  of  wastes  off-site [7,  18],  New cleanup standards  approaches
require that Superfund  remedies  must be  protective of human  health  and
the  environment,  be   cost-effective,  and  utilize   permanent  solutions,
alternative treatment technologies and resource  recovery to the  maximum
extent practicable. Onsite remedies  must meet applicable  or relevant and
appropriate regulations  (ARARs) of  other  Federal  statutes including the
Resource Conservation  and  Recovery  Act  (RCRA),  the  Toxics  Substances
Control Act (TSCA), the  Safe Drinking Water Act (SDWA), the  Clean Water
Act (CWA)' and  the  Clean Air Act (CAA). Where State  standards  are more
stringent than Federal  standards,  State standards must  be met.
                                    348

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The  strategies used  for  establishing cleanup goals by the U.S. EPA  under
the  Superfund  program  have  been the  subject of continuing review  and
critique.  In 1985, the  U.S. Office of Technology Assessment (USOTA),  acting
in behalf of  the U.S. Congress  evaluated  past practices associated with
setting  cleanup goals at  Superfund hazardous  waste  sites [6].  The  USOTA
identified seven alternative  approaches  for establishing  cleanup goals  at
Superfund sites:

      1.    Ad hoc,
      2.    Site-specific  risk assessment,
      3.    National  goals for residual contamination,
      4.    Clean to  background or "pristine" levels,
      5.    Best available technology or best engineering  judgement,
      6.    Cost-benefit  approach, and
      7.    Site  classification.
Based  on  a review  of  past and current  practices  under  the. Superfund
program as  well as  critical  issues  relevant to  establishment  of cleanup
goals,  the  USOTA drew the following  important conclusions:

o     It is no longer acceptable  to  continue  cleanups under  the  current
      ad  hoc  approach.    Dealing  with  each  site  as  a  unique  case  is
      inefficient and there is  increasing likelihood that sites with similar
      problems  will not  be cleaned to comparable levels of protection.

o     Pursuing   cleanup   to   background  or   pristine  does   not   make
      environmental, technical or economic sense.

o     Though  seemingly  attractive  and  extensively  used,  best available
      technology  or  engineering  judgement  approaches  do   not  offer
      environmental protection  comparable  to   the  likely  high  costs  of
      implementation.

o     Though use of existing  standards, risk assessment and cost benefit
      pose considerable problems, they could be  used.

o     The  most  important conclusion is  that  a  cleanup strategy  based  on
      site  classification could  be the most  beneficial  approach  to  be, used
      (Table  4.4).    For  this   strategy to  be  successful,  the  decision
      regarding land use must be made at the local level.

o     There is  a need  to raise  the  issue of  cleanup goals to the highest
      levels of  policy making with  an open  debate.   The  success of  the
       Superfund program  and  private  and  State  cleanups  depends  on
      equitable and  technically sound resolution of this issue.

o      What  is   ultimately  important   and   realistically  achievable   is
      consistency  in the  process of  determining cleanup goals,  rather  than
     : necessarily making  all cleanups the same.
                                    349

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Table 4.4    Illustration of  a site classification system  for selecting
              cleanup goals as  proposed by the U.S.  Office of  Technology
              Assessment [6].
 Classes of NPL, sites
  (established when site
  placed on NPL)
 Cleanup goals
 for remedial cleanup
 set by     '
 Likely course of action
For comparison purposes,
  EPA classes of
  groundwater*
   Known or likely exposures to people Site risk
   or sensitive ecological elements re-  assessment
   quiring restoration of site {for possi-
   ble rehabitatfon or reuse), Including
   cleanup of contaminated ground-
   water if technically feasible.
                  1. High-priority initial re-
                   sponse to recontrol site
                   using MRS" information.
                  2. Obtain necessary data and
                   perform risk assessment.
                 3. High-priority full-scale per-
                   manent cleanup when
                   technology available to
                   meet cleanup goals.
                         Special groundwaters vul-
                         nerable to contamination
                         and; a) (irreplaceable
                         source of drinking water
                         to substantial popula-
                         tions, or b) ecologically
                         vital.
   Known or likely exposures exist, but Cost-benefit
   limited number of people and sensi- analysis.
   tlva environments. Clear alternatives
   to site cleanup such as relocation
   and use of alternative water supply;
   sue restoration or reuse not critical.
                 1, Initial-response.
                 2. After cost-benefit analysis
                   choose risk management
                   option.
                         Current and potential
                         sources of drinking water
                         or have other uses.
111, Sits not likely to lead to exposures
"  to people and not situated near sen-
  sitive environment. No site restora-
  tion or reuse anticipated.
Applicable and rele-
vant environmental
standards.
1. Low-priority initial  •
  response.
2, Reevaiuation every 5
  years to assess need for
  remedial cleanup.
III. Not potential source of
  drinking water and of
  limited use.
*US. EntiioflininM Pntltctidn Asซnซy, Gtetine-Wttet Pmttction Strategy, *ufual 1984
ฐAuunn at improved Mtzaid Harking Systam,
At a 1987 coEoquium sponsored by the Water  Science and Technology Board
of the  U.S.  National  Research   Council,  the  issue   of  cleanup   goals  for
Superfund  hazardous  waste  sites  was  specifically  addressed  ,[7],   It  was
noted  that  cleanup  goals had,  in the past,   largely  been handled on an ad
hoc  basis   with  implicit rather than  explicit  goals  set.   Legal  settlements
between  government  agencies  and ; potentially  responsible   parties  (PRPs)
normally resulted in  cleanup  actions  without  explicit cleanup  goals. These
included,  1)  cash  buyouts  where  the  potentially  responsible party  (PRP)
pays   a  sum  of  money  in   return  for  release from  future  liability,  2)
agreements  to  conduct a  specific  Remediation  action,  and  ,3) open-ended
commitments  to  do  'whatever  is  necessary1  to protect human  health.    Few
cases  explicitly established cleanup  goals.

Three   major  unresolved   issues   emerged  from  the  colloquium   regarding
approaches to  establishing cleanup goals:
                                           350

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      The  point  of compliance  must  be resolved  at which  applicable  or
      relevant  and  appropriate  requirements  should be  applied.  Impacted
      parties  generally  support  compliance  at  the  edge  of  the  waste
      management unit or  site of  release.   Responsible  parties argue for
      compliance  at  property boundaries or point  of potential impact.

      An appropriate  level  of risk and acceptable target levels  must  be
      selected.    Impacted   parties  argue  for   very  conservative  risk
      management  decisions  and   there  is  explicit  support  for  cleanup
      levels corresponding  to a 10~6  incremental risk of  cancer.

      The adequacy of the  current database for making  both risk analyses
      and risk management decisions is  questionable.  Exposure  assessment
      using current models  of contaminant transport is  constrained by a
      lack  of data on contaminant fate.   The  capability  of many remedial
      technologies  to  achieve very  low  levels  of  residual contamination  is
      not  clearly  understood.    Finally,  the toxicological  database  and
      methods  used to  estimate  chronic  risks  at  low   levels  of  human
      exposure are highly uncertain.
State of California.  The  State of California developed what they refer to as
the "California Site Mitigation  Decision Tree" < (Tables  4.2 and 4.3)  [17], In
this  approach the maximum exposure level (MEL)  is equal to the daily dose
(mg/d)  with  no  adverse health  effects  during  chronic  exposure.    The
applied action  level  (AAL)  is  the  concentration  of  a  substance  in  a
particular media that when exceeded, presents a significant risk of adverse
impact to  a biological receptor. AALs  drive the cleanup  process for a site.
The  cleanup level  is  the site-specific criterion  that  remedial action  must
satisfy to keep biological receptor exposures equal to or less  than the AAL.
MILs and AALs are substance and species specific.

For  threshold substances (i.e.  noncareinogenic),  MELs for  humans can be
derived from several sources.   In  order  of  decreasing preference,  these
include human  or animal  toxicity   data,  drinking  water  standards  or
guidelines,  or  occupational  exposure  limits  (e.g. ACGIH TLVs).   MELs are
derived from human or  animal  toxicological dose-response  relationships as
foEows:


                   NOAEL (mg/kg.d) * adult body wt  (kg)
  MEL (mg/d)  =   	•	'•	•——
                           Uncertainty factor


The  uncertainty factor =  10 for large, controlled epidemiology studies, 10-
100 •  for occupational  standards, 100  if NOAELs  are  derived  from chronic
animal studies,  1000  if  from  subacute animal  studies, or  100,000 if the
NOAELs are from acute animal studies.
                                   351

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MILs are derived from occupational: threshold limit values (TLVs) as follows:


                        TLV (mg/m3) * 20 nrVd * 8 hr  *  5 d  * 47 yr
  MEL (fflg/d)  =
                        Uncertainty factor * 24 hr * 7 d * 72 yr
For  non-threshold  substances  (carcinogens)  the  MEL  is  the  level  of
exposure  at  an individual  lifetime  excess cancer risk equal  to  1Q~6.   The
International Association  of Research on Cancer classification  of carcinogens
is used.   In California,  all  substances  classified as  probable or  possible
human carcinogens are treated as nonthreshold substances.

The AALs are derived as follows;


                              MEL
  AAk (medium) =         - '. -  * phannocokinetic  factor
                        Average daily intake


The average daily intake for  water 'is assumed to equal  2 L/d while for air
it is  20  nrVd.    The  pharmocokinetic  factor  is  used  to  adjust  for
differences  in  absorption,   distribution  and   elimination  for  different
exposure  routes.

The measured  or  predicted level (C) of a given  toxic substance at a  given
biologic receptor  is compared  with those considered  safe  (i.e. AAL), Similar
to the U.S. EPA approach,  the assumption of additivity  is  used  to  consider
multiple  substances and  exposure routes.  The  cleanup  action chosen must
meet  the  foEowing criteria.   For a single compound, in single  or multiple
media, C must  be  equal to  or  less than the AAL.  For  multiple compounds in
multiple media,  the following must be satisfied!
           •
       2.   Z    -  < 1
       i=l   j=l    AAL
-------
ASCLs are derived in different ways depending on  the  medium and  receptor
in question that is desired  to  be protected.      To protect human  health
from drinking contaminated  ground  water,

      ASCL  =  Ka * Standard * Depth Factor * Mobility Factor


where, K,j is the  soil/water partition coefficient,  the Standard is the  water
quality criteria or  drinking  water  standard, and  the  Depth and  Mobility
Factors are soil-related parameters.

To protect human  health from ingestion of noncarcinogenic  contaminants in
soil, the ASCL is derived as follows:


                  ADI  (mg/d) * 1000 g/kg * 10 kg
      ASCL  =	•	;—-
                  Daily soil intake by child * 70 kg


For carcinogenic contaminants in soil, the ASCL  becomes!


                  Acceptable cancer risk *  1000 g/kg
      ASCL  =
                  Carcinogenic                  Average daily soil
                  potency  (l/(mg/kg/day) *      intake (g/kg-d)
 where  the  acceptable  cancer  risk  is  defined  as 10~6, the  carcinogenic
 potency is the  slope of the dose-response curve based on animal bioassays
 as calculated by the U.S.  EPA and  the  lifetime  average daily soil intake is
 2.8 mg/kg-d.

 Cleanup  levels  are  calculated  by  a  two-step  process.   In  step  one,
 indicator compounds are selected  based on a scoring system where the total
 score  is equal  to the  sum  of  a  relative  amount  score,  toxicity  score,
 volatilization  score, leachability  score,  persistence  score,  bioaccumulation
 score  and an aquatic  toxicity score.   In step two, the  ASCLs are  derived
 for  humans  and  three pathways (soil, ground  water,  surface water) and
 aquatic  life, but  only  two  pathways.   The ASCL associated with the most
 sensitive pathway  is   selected.   There  is  no  consideration  of  multiple
 chemical  multiple  route exposures.

 Apart from  the above approach, cleanup guidelines  used in New  Jersey
 have reportedly included  those listed in Table  4.5 [8].   Presumably these
 would have to ultimately be consistent  with  the  results of the site-specific
 analysis procedure described  above.
                                   353

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Table 4.5.  Cleanup  guidelines used in the State of New Jersey, USA [8].
Substance

Chromium
Zinc
Lead
Copper
Arsenic
Cadmium
Selenium
Nickel
Barium
Mercury
Silver
Soil
ppm
100
350
100
170
20
3
20
100
-
-
_
Ground Water
ppb
50
_
50
_
50
10
10
-
100
2
50
Total Volatiles.
Volatiles plus Base Neutrals
Total Hydrocarbons
Petroleum Hydrocarbons
1
: -
100
100
_.
100
-
1000
State,  of Washington.      The  State  of Washington  has  prepared  state
guidance on  cleanup  of  waste  contaminated  sites.   In  their approach,
cleanup  goals for each medium  are, derived by the methods summarized  in
Table 4.6.
      of Wisconsin.     In  1985,  the State of Wisconsin  adopted a  set  of
standards   specific  to ground  water quality protection  [26].   Numerical
values for preventive action limits (PALs) and enforcement standards (ESs)
were explicitly defined in administrative regulations (Tables 4.7 and 4.8).

Application  of the  PALs  and  ESs in  Wisconsin  is explicitly  regulated  as
illustrated by the following  remarks from the administrative regulations:

      o     If a preventive action limit  (PAL) or  an  enforcement standard
            (ES) for  a substance is attained or  exceeded  at a point  of
            standards  application) the owner or  operator shall  notify the
            appropriate regulatory agency, and the regulatory agency shall
            require a remedial response.
                                    •354

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            In  determining if  a  preventive action  limit or  enforcement
            standard  is attained  or  exceeded  or  if  a change  in the
            concentration  of  a  substance  has  occurred,  the  regulatory
            agency  shall utilize the most scientifically valid of the following
            statistical procedures  which  provide a 95% level of confidence:
            Student  t-test, temporal or  spatial trend  analysis,  or  other
            scientifically valid test.    If a  substance is  not detected in  a
            sample and  the limit of detection is higher than the preventive
            action  limit or  enforcement standard,  the PAL or  ES  shall be
            considered not to have been  attained or exceeded.
Table 4.6.  Cleanup  criteria used in the State of Washington,  USA [8,17].
Application
Description
Standard/Background Cleanup Levels
o General

o Soil
o Ground water/
   surface water

o Air
Existing  environmental standards

10 times  drinking water or water quality standards,
or 10 times background water quality levels,  or
Soil  background.

Drinking water  standard, or Water  quality
standard or Background.

U.S. occupational air quality standards,  or
Ambient air quality  standards, or
Background.
Soil Protection Cleanup  Levels

o Threat to water
o Threat to air
100 times water quality  standard,  or
100 times background water quality, or
10 times soil background, or
Predictive models with site-specific data.

0.001* of inhalation LC^Q, or
Guidelines for  respiratory carcinogens.
                                    355

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Table 4.7.  Ground water standards in the State of Wisconsin,  USA [26].
Substance
Preventive
Action Limit
        Enforcement
        Standard
                                          ug/L
1* Public  Health Ground Water Quality Standards2
Arsenic
Barium
Cadmium
Chrome
Lead
Mercury
Selenium
Silver
Cyanide
Fluoride
Nitrate+Nitrate (as N)
Benzene
Toluene
Xylene
1,4-dichlorobenzene
Vinyl chloride
1,2-dibromoethane
1,2-dichlor oethane
1,1-dichloroethene
Methylene chloride
Tetrachloroethene
1,1,1-trichloroethane
1,1,2-trichloroethane
Trichloroethene
Aldicarb
Endrin
Lindane
Methoxychlor
Simazine
Toxaphene
l,2~dibromo-3-ehloropropane (DBCP)
Carbofuran
2,4-dichlorophenoxyacetic acid
2,4,5-Trichlorophenoxypropionie Acid
Dtaoseb
Bacteria,  Total Coliform
   5
 200
   1
   5
   5
   0.2
   1
  10
  92
 440
2000
   0.067
  68.6
 124
 150
   0.0015
   0.001
   0.05
   0.024
  15
   0.1
  40
   0.06
   0.18
   2
   0.02
   0.002
  20
   0.43
   0.00007
   0.005
  10
  20
   2
   2.6
Less  than
membrane
                  ug/L
           50
         1000
           10
           50
           50
            2
           10
           50
          460
         2200
        10000
            0.67
          343
          620
          750
            0.015
            0.01
            0,5
            0,24
          150
            1
          200
            0.6
            1.8
           10
            0.2
            0.02
          100
            2.15
            0.0007
            0.05
           50
          100
           10
           13
1 per  100 mL for
filter or not
                                          present in any  10  mL portion
                                          by fermentation tube  method.
                                    356

-------
Table 4.7  cont.  Ground water standards  in the  State of Wisconsin [26].l


                                          Preventive        Enforcement
Substance                                Action Limit       Standard

                                          mg/L             mg/L
2.  Public Welfare Ground Wst.ar Quality Standards3

Copper                                      0.5               1
Iron                                        0.15              0.3
Manganese                                  0.025             0.05
Zinc                                        2.5               5

Chloride                                  125               250
Sulfate                                    125               250

Total dissolved  solids                     250               500

Color (in  color units)                       7.5              15
Odor (in Threshold  Odor No.)                1.5               3.0
Foaming agents
   (methylene blue  active sub.)             0.25              0.5


*Adopted as legal State standards in 1985/1986.
2por all  substances  that  have  carcinogenic,  mutagenic  or  terratogenic
properties or interactive effects, the  preventive action  limit  is  iO% of the
enforcement  standard.    The   preventive  action   limit  is   2095  of  the
enforcement standard for all other substances  of public health concern.
3For each substance of public welfare  concern,  the  preventive action limitis
50%  of the established enforcement standard.
      o     Point  of  standards  application:     Facilities,  practices  and
            activities regulated  shall be  designed to minimize the  level  of
            substances in ground  water  and  to comply  with the  PALs  to
            the   extent   technically  and   economically   feasible  at  the
            following locations:

                  Any point of present ground water use,
                  Any point at or beyond the  property  boundary,
                  Any point beyond the design management zone (DMZ)
                  established:
      ... ,          Type of facility        Horizontal distances for DMZ
                  Land disposal systems         250  feet
                  Wastewater, sludge lagoons    100  feet ;
                  Solid waste facilities           150  to 300 feet
                  Hazardous  waste  facilities      0 to 300 feet
                  Spills,  discharges             0 feet
                                    357

-------
Table 4.8,   Ground water quality! indicator parameter standards in the
            State of Wisconsin, USA [26].l
                              Preventive Action Limit Is Greater Of
Parameter
Minimum Change
Rel. to Background
Statistical Change
Rel. to Background
Field pH
      +/- 1 pH unit
Field temperature
Specific conductance
Alkalinity
Total Hardness
Boron
Calcium
Magnesium
Sodium
Potassium
Nitrogen - ammonium
- organic
- total
Biochemical Oxygen Demand
Chemical Oxygen Demand
Total organic carbon
Total organic halogen
+/-
4- ;
4- ,
4-
4-
4-
4-
4-
4-
+ :
+
4-
4-
4-
4-
4-
10ฐF
200 umhos/cm
100 mg/L
100 mgCaCO3/L
2
25
25
10
5
2
2
5
25 mg/L
25
1
0.25
+/-
4-
+
4-
4-
4-
4-
4-
4-
. 4-
4-
4-
4-
4-
4-
4-
3 std. dev.
3 std. dev.
3 std. dev.
3 std. dev.
3 std. dev.
3 std. dev.
3 std. dev.
3 std. dev.
3 std. dev.
3 std. dev.
3 std. dev.
3 std. dev.
3 std. dev.
3 std. dev.
3 std. dev.
3 std. dev.
^Background  water   quality  is  jestablished  by  sampling  one  or  more
monitoring points at locations  and depths  sufficient to yield ground water
samples that are representative of background water quality at or near the
facility,  practice or  activity.    Background  water quality for  indicator
parameters shall be established by averaging a minimum of 8 sample results
from each well.
                                    358

-------
Factors to be considered in determining a remedial response:

-     Background water quality.
-     Reliability of sampling data.
      Public health, welfare and environmental effects.
      Probability that a PAL or ES may be attained or exceeded
      outside the DMZ.
^     Performance of the facilityi  practice or activity
      compared to the  design.
      Location of the  monitoring  point.
-     Other known or suspected  contaminant sources,
-     Hydrogeologic conditions.
-     Extent of ground water  contamination.
      Alternate responses.

Range of  responses  for exceedance of a PAL for Indicator
parameters and substances of public health or welfare concern:

-     No  action.
      Sample  wells or require sampling of wells.
-     Require  a change in  monitoring, including increased
      monitoring.
      Require  an investigation of  the extent of ground water
      contamination.
-     Require  a revision of the operational procedures,
-     Require  a change in  the design or construction.
-     Require  an alternate  method of waste treatment or
      disposal.
-     Require  prohibition or closure and abandonment.
      Require  remedial action  to  renovate or restore
      ground water quality.
      Revise rules or criteria on facility design, location or
      management practices.

Range of  responses  for exceedance of  a ES for substances  of
public health or welfare concern:

-     Require  a revision of the operational procedures.
-     Require  a change in  the design or construction.
-     Require  an alternate  method of waste treatment or
      disposal.
-     Require  prohibition or closure and abandonment.
      Require  remedial action  to  renovate or restore
      ground  water quality.
-     Revise rules or criteria on facility design, location or
      management practices.
                         359

-------
4.2.2  Canada

In Canada, there is little national guidance for assessing the significance of
contamination and  setting cleanup goals.   Site  assessment and  cleanup are
with few exceptions, handled  at  the  Provincial level  [8].  Generally, ad hoc
approaches   have   been   used   and   mainly  for   decommissioning   and
redevelopment  of   old  industrial  sites.    A  brief  discussion  of   some
approaches  used in Canada follows.


Canadian Council of Resource and Environment  Ministers.  To assist in the
assessment  of the  significance  of contamination and setting  cleanup  goals
some  criteria  (not standards)  have been  recommended  by  the Canadian
Council of Resource and Environmental Ministers  (CCREM)  [8,27,28].   These
are summarized in  Table 4.9.

The  criteria  proposed  by CCR1M account for  two  media  (i.e.  soil  versus
ground  water) and  for  two land  uses  (i.e.  residential/farming   versus
commercial/industrial). Three  values, referred to as A-B-C values,  are given
for  each  media.    The  application  of these  criteria  is  quite   simple.
Investigative  criteria are  values  above  which   detailed  investigation is
needed while  remedial  criteria  are   values above  which action  is  required
for protection  of  humans or other biota.   Action  could  include cleanup,
other  mitigation, and/or change in  land use.  For  residential or  farming
land uses,   the investigative criteria are equal  to  the A  values and the
remedial criteria are  equal to the B values.   For commercial or  industrial
land uses, the investigative  criteria become  the B values and the remedial
criteria  become the C values.
Ero-vince  of. Alberta.  In Alberta, the  selection of  cleanup levels  must  be
supported or justified by appropriate data [8,29].  To assist with this task,
Alberta    Environment    published   guideline   levels   for   acceptable
concentrations  of  some  metals  in "•. acidic  soils.    The  guidelines   were
reportedly   based   on   several   factors   including   phytotoxicity  and
bioaccumulation  (Table 4.10).


Province  of Ontario.  In Ontario, the Ministry of Environment  (OME) initially
provided  guidelines for the decommissioning  of  major  industrial  sites  in
1984 [8].    Included  were basic data and information requirements of OME
before a  cleanup plan or alteration  in site use is  permitted.  This  document
included  a limited list of criteria for soil (Table  4.11).    A revised edition
of this document is  to  include criteria to  assist in selecting appropriate
cleanup levels.

In determining final  cleanup goals, existing OME criteria  for  air  or  water
can  be used as appropriate as well ! as the  soil criteria  mentioned  above.
For  other contaminants, criteria must  be  developed based on the specific
contaminants  present,  physical  features  of   the  site  and  on-site  and
adjacent  land use.   A site-specific risk assessment may be needed in  some
cases.  Final  cleanup  criteria  are   established  in  consultation  with  OME
authorities.                                                             ,
                                     360

-------
Table 4.9.   Interim guidelines for contaminated sites recommended  by
            the Canadian Council of Resource and Environment
            Ministers  [27-28].!

                                                         Max. Concentration
Substance               Land Use                         in the Top 15 cm
Polychlorinated
  biphenyls
Agricultural soils incl. home gardens
Non-agricultural soils, general public access
Industrial/commercial, limited public access
     mg/kg
      0.5
      5
     50
                        Threshold Concentrations
Component
                        Soil (mg/kg dry  matter)
              B
                                    Ground  water  (ug/L)
B
Group 1 - Carcinogenic
Benzo(a)anthracene
Benzo(b)anthracene
Benzo(k)fluoranthene
Benzo(a)pyrene
Dibenzo(a,h)
anthracene
Indeno(l,2,3-c,d)
pyrene
Group 2 - Other PAHs3
PAHs2
0.1
0.1
0.1
0.1
0.1
0.1
Naphtalene 0.1
Phenanthrene 0.1
Pyrene 0.1
Group 3 - Other oreranics
Benzene
Toluene
Xylene
Group 4 - Inorganics
Iron
Arsenic
Sulfide/sulfate
Iron-cyanide complexes
Free cyanide
1
1
1
1
1
1
5
5
10
Substances
Substances
10
10
10
10
10
10
50
50
100
of concern,
ii
ft
of concern,
M
tt
n .
ti
0.01 0.1
0.01 0.1
0.01 0.1
0.01 0.1
0.01 0.1
0.01 0.1
0.2 2
0.2 2
0.2 2
but no guidelines
ii
ti
but no guidelines
it
IT
- 1!
II
1
1
1
1
1
1
20
20
20
yet.
yet.
 1 Application of ABC values:   Investigative criteria  = values  above  which
 detailed investigation  is  needed.  Remedial criteria  = values  above  which
 action is required for  humans  or other biota.  Action could include cleanup,
 other  mitigation,  and/or  change in land  use.  For  residential or  farming
 uses,   Investigative criteria = A values and  Remedial criteria =  B values.
 For  commercial or  industrial  uses,  Investigative criteria  = B  values and
 Remedial criteria  =  C values.
 ^Gcoup  1   substances  are  designated  as carcinogenic  by  International
 Agency for Research on Cancer.
 ^Group 2 substances have not  been demonstrated as  cancer  causing.
                                    361

-------
Table 4.10.  Suggested cleanup guidelines for inorganic contaminants
            in acidic soils in the Province of Alberta, Canada [8].l


Element                       Acceptable Level for Acidic Soils (pH  < 6.5)

                                                mg/kg

Cadmium                                          1
Chromium                                       600
Cobalt (preliminary)                             100
Copper                                         200
Lead                                            800
Manganese                                        -2
Nickel                                          250
Zinc (sheep diet)                                100
Zinc (others)                                    700
       values  given  were  developed  as  guidance  for  reclamation   of
industrial  sites located on acidic  soils.   Site specific  conditions  must be
considered  and the  suggested acceptable levels  are only  to  be  used as
guidelines  towards selecting final cleanup  levels.
^No  limit  recommended for  manganese due  to  high  naturally occurring
levels.
Prrroyince, of Quebec*    In 1988,  Quebec issued a  guide to the rehabilitation
of contaminated  sites [19].   Among other things, this document  formalized
an  "ABC" system of  site  assessment with a  comprehensive list of  soil and
ground water  criteria  to assist  in; determining  final  cleanup levels  (Table
4.12).  This approach and the numerical ABC values were derived  in large
part from that used  in The Netherlands.  Three  concentration values (A, B
and C values) are given for both  soil and  ground water.   The A  values
were equivalent  to background levels or analytical detection limits,  B  values
were indicative of moderate contamination and the C values  were indicative
of severe contamination.

Many of the values from The Netherlands  were adopted  directly.  In some
cases,   modifications   were   made  as  deemed  appropriate  for  Canadian
conditions.   Specific soil contaminants of  concern  in Quebec were  added.
Ground water  criteria  were  revised,  with  the  low  values used in  The
Netherlands, increased due to impracticalities of their use in Quebec.   For
heavy  metals,  the B  values  were set equal to  drinking  water  standards
where  available  and  C  values  were  set  equal to storm  sewer  disposal
criteria.  For  certain  organic compounds,  the ground water criteria were
revised in  accordance with  U.S. Environmental  Protection Agency criteria
for Estimated  Permissible Concentrations in  water.   It is  emphasized  that
the criteria are at no time to be regarded as standards [19].
                                     362

-------
Table 4.1i.  Soil cleanup  criteria of the Ontario Ministry of
            Environment, Canada [8].
                              Criteria for Proposed Development*-
Parameter

PH
Conductance (mS/cm)
Sodium Absorption
Arsenic
Cadmium
Chromium (6+)
Chromium (Total)
Copper
Lead
Mercury
Molybdenum
Nickel
Nitrogen (%)
Oil and grease (%)
Selenium
Silver
Zinc
Residential/
Agriculture
ppm
_
-
-
14
1-6
-
120
100
60
O.S
4
32
-
-
1.6
—
220
Commercial/
Parkland
ppm
6-8
2
15
25
4
10
1000
300
500
1
5
200
0.6
1
5
25
800
Industry
ppm
6-8
2
15
50
8
10
1000
300
1000
2
40
200
0.6
1
-
50
800
^Reference  is  made  to  guidelines   for   Sewage   Sludge  Utilization   on
Agricultural   lands.       Guidelines   for    Residential/parkland   and
commercial/industrial are based  on phytotoxicity  except for cadmium, lead
and mercury  (human health) and molybdenum and selenium (animal  health).
For coarse  textured  (sandy) mineral soils  the  criteria for  metals and
metalloids  should be reduced  by one-half.   Criteria  for  oil and  grease is
for fresh oil,  use 2% for weathered oiL
                                    363

-------
Application of this ABC system  in Quebec is  theoretically quite simple.  For
each of the substances, there  are  three threshold values which  determine
three levels of Intervention as  described below.

o     The  A   value   represents  background  pollution  with  respect  to
      contaminants found  naturally, such as metals, oils  and grease, and
      the  detection   limit  with  regard  to  man-made  organic  chemical
      products.  The  A-B  level is indicative  of slight contamination of soil
      or ground water. At this level  of contamination,  ground  water still
      satisfies  drinking water  quality  standards and criteria.   However, it
      is worthwhile to investigate , possible  sources  of  contamination  and,
      especially in the case  of the; water table, to  ascertain whether, new
      contaminants  continue   to  enter  the  water.    This  may  lead  to
      intervention  focusing on  the  soil,  particularly if  the water is used
      for  drinking.   Usually,   at;  the   A-B   level   of   contamination,
      decontamination  will   not  be  undertaken.   Should  the  land   be
      redeveloped  for  especially sensitive purposes,  e.g. surface soil  in a
      residential or  a farming  sector,  it  may  prove essential  to adopt a
      number  of  protection  measures,  such  as  the  excavation   of  a
      superficial layer of soil or the addition of a  layer of clean  soil.

o     The  B  value represents  a threshold  when thorough analyses are
      necessary.    At  the   B-C  level,  the  soil  or  ground   water are
      contaminated.    Contamination  of  ground   water  exceeds  drinking
      water quality standards.   Although  the soil  is contaminated,  it will
      not automatically be decontaminated unless the  effect of contaminants
      on the  ground  water  necessitates such work.  However,  restrictions
      on  land use may  be  imposed when  this  level  of contamination  is
      observed in  the soil.   Restoration work may be necessary before the
      land is  used for farming, residential or recreational purposes.   Other
      uses, e.g.  industrial   or  commercial,  may   be contemplated  without
      decontamination being  carried out.   In all  cases, the  extent of the
      work to  be effected, e.g. the  depth to which  soil must be excavated
      and  so on,  will depend  upon the nature of  the contaminants,  land
      use and  the  impact on  ground water and  the environment  in general.

o     The  C value is  a threshold at which it may  be necessary to take
      prompt  remedial action.  At  and above  this  value, the soil or ground
      water are  contaminated.   Ground water cannot  be used for drinking.
      Concentrations  of  many  contaminants exceed standards   governing
      storm sewer runoff.  The water is seriously contaminated;  unless it
      is decontaminated, it will have to be  monitored closely.  All uses  of
      such land  will be restricted.  A thorough analysis  must be conducted.
      In  all  likelihood,  restoration' will  have  to  be   undertaken  before
      rehabilitation occurs.
                                    364

-------
Table 4.12.  Criteria for ascertaining the contamination of soil and
            ground water in the Province of Quebec,  Canada [19J.I
Soil (nig/kg dry matter) Ground water (ug/L)
Component
I - Heavy Metals
Arsenic
Barium
Cadmium
Chrome
Cobalt
Copper
Lead
Mercury
Molybdenum
Nickel
Selenium
Tin
Silver
Zinc
II - Mineral PoEutants
NH4 (as N)
Br (dissolved)
Br (free)
CN (free)
CN (total)
F (dissolved)
F (free)
PO4 (in P)
NOs (in N)
NC-2 (in N)
Sulfide (H2ง)
S total
A

10
200
1.5
75
15
50
50
0.2
2
50
1
5
2
100

_
-
20
1
5
-
200
-
-
-
-
500 '
B

30
500
5
250
50
100
200
2
10
100
3
50
20
500

-
- .
50
10
50
-
400
-
-
- .
-
1000
C

50
2000
20
800
300
500
600
10
40
500
10
300
40
1500

-
-
300
100
500
-
2000
-
_
-
-
2000
III - Monocyclical Aromatic Volatile Compounds
Benzene
Ethylbenzene
Toluene
Chlorobenzene
1,2 die hloro benzene
1,3 die hloro benzene
1,4 dichlorobenzene
Xylenes
Styrene
BTEX3 (summation)
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
-
0.5
5
3
1
1
1
1
5
5
_
5
50
30
10
10
10
10
50
50
-
A

5
50
1
15
10
25
10
0.1
8
10
1
10
5
50

200
100
_2
40
40
300
_2
50
10
20
10
_
(MAVCs)
0.5
0.5
0.5
0.1
0.1
0.1
0.1
0.5
0.5
-
B

50
1000
5
40
50
50
50
0.5
20
250
10
30
50
5000

500
500
_2
200
200
1500
_2
100
10000
1000
50
_

1
50
50
2
2
2
2
20
40
-
C

100
2000
20
500
200
1000
100
1
100
1000
50
150
200
10000

1500
2000
_2
400
400
4000
_2
700
-
-
500
—

5
150
100
5 '
5
5
5
60
120
-
                                     365

-------
Table 4.12 cont.
Criteria for ascertaining the contamination of soil
and ground water in Quebec, Canada
      Soil (mg/kg dry matter)
                                                     Ground water (ug/L)
Component
A
B
C .. .
A
B
C
IV - Phenolic Compounds
Nonchlorinated
(each)4
Chlorophenols
(each)4
(summation)^
V - Polyeyelle Aromatic
Benzo(a)anthracene
1,2 benzanthracene
7,2 dimethyl
Dibenzo(a,h)
anthracene
Chrysene
Smethylcholahthrene
Benzo(b)fluoranthene
Benzo(j)fluoranthene
Benzo ( k)fluor anthene
Benzo(g,h,i)perylene
Benzo(c)phenanthrene
Pyrene
Benzo(a)pyrene
Dibenzo(a,h)pyrene
Wbenzo(a,i)pyrene
Dibenzo(aปl)pyrene
Indeno(l,2,3,c,d)
pyrene
Acenaphtene
Acenaphtylene
Anthracene
Fuoranthene
Fluorene
Naphtalene
Phenanthrene
PAHs (suramation)5

0.1

0.1
0.1

1

0.5
1

10

5
10

1

1
1

3

2
4

20

5
10
Hydrocarbons (PAHs)
0.1
0.1

0.1

0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1

0.1
0.1
0.1
0,1
0.1
0.1
0.1
1
1
1

1

1
1,
1
1
1
1
1
10
1
1
1
1
1

10
10
10
10
10
5
5
20
10
10

10

10
10
10
10
10
10
10
100
10
10
10
10
10

100
100
100
100
100
50
50
200
0.1
0.1

0.1

0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.2
0.1
0.1
0.1
0.1
0.1

0.5
0.5
0.2
0.1
0.1
0.2
0.1
0.2
0.5
0.2

0.2

1
0.2
0.2
0.2
0.2
0.2
0.5
7
0.2
1
1
1
1

20
10
7
2
2
10
1
10
2
1

1

5
1
1
1
1
1
2
30
1
5
5
5
5

30
20
20
10
10
30
5
50
                 366

-------
Table 4.12 cont.   Criteria for ascertaining the contamination of soil
                  and ground  water in Quebec, Canada [19]. 1
Component
Soil
A
(mg/kg
B
dry matter)
C
Ground water
A
B
(ug/L)
C
VI - Chlorinated Hydrocarbons (CHs)
Aliphatics CH*
(each)
(summation)
Chlorobenzene^
(each)
(summation)
Hexachlorobenzene
0.3
0.3
0.1
0.1
0.1
5
7
2
4
2
50
70
10
20
10
1
1
0.3
0.3
0.1
10
15
2
4
0.5
50
70
5
10
2
 Polychlorinated
   biphenyls             0.1      1    10               0.1    0.2    1
 Chlorodibenzo-p-
   dioxines              -       -     -               -     - -      -
 2,3,7,8 tetrachloro-
   dibenzo-p-dioxine     -       -     -               -      -      -
 Chlorodibenzofuranes   -       -                     -      -      -

VII - Pesticides
a) Organochlorinated.
 Aldrine+Dieldrin        -       -     -               0.05    0.7   2
 Chlordane (total)       -                             0.05    0.7   2
 DDT                    -                             0.05   30    60
 Endrine                -       -                     0.05    0.2   0.5
 Epoxyde of             -       -                     0.05    3     5
   heprachlor
 Lindane                -       -                     0.05    4    10
 Methoxychlore          -             -               0.05  100   200
b) Carbamates.
 Carbaryl               -       -     -               0.05   70   150
 Carbofurane            -           •  -               0.05   70   150
c) Derivatives of chlorophenoxy  carboxylic acids.
 2-4-D                   -       -     -               0.05  100   200
 2,4,5.TP                -       -•-•'•       0.05   10    20
d) Organophosphoric.
 Diazinon                -       ->                     0.05   14    30
 Fenitrothion            -       -     -               0.05    7    20
 Parathion               -       -     -               0.05   35    70
 Parathion-methyl       -           .  -               0.05    7    20
e) Derivatives of pyridylium.
 Diquat                  -       -     -               0.05   50   100
 Paraquat               -                             0.05    7    20
f) Tricoloroacetates.
 Piclorame               -       -     -               0.05    1     2
Pesticides
      (summation)5      0.1      2    20               0.05  100   200
                                     367

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Table 4.12  cont.   Criteria for ascertaining  the  contamination of soil
                  and ground water in Quebec, Canada [19].1


                        Soil  (rag/kg dry  matter)       Ground  water (ug/L)

Component              A      B      C               A      B      C


VIII - Indicatory Parameters
Phenolic compounds by
  eolorimetry4            0,1    1    10                 125
Gasoline                100    150   800              1000  1500  3000
Mineral oils/grease      100   1000  5000               100  1000  5000


^Criterion  (A)  concerning ground water for elements in Groups I has  been
evaluated according to the average  value of natural concentrations found in
Quebec ground water, by compiling findings  from more  than  2'ป  sampling
sites located  in  12  Quebec municipalities,  with  input  from  the Quebec
laboratory and the Direction des eaux souterraines et de consommation.  An
average of findings for soil analyses drawn from a ministere de 1'Energie et
des  Eessources data bank examined.
N.A. = not applicable.  "-" = no criteria available as of 15  Feb. 1988.
    aqueous  environments, so-called "free" forms are dissolved.
            criteria respecting BTEXs  (benzene, toluene, xylene) to come.
^See the remarks section  below.
^The sum of content detected for each compound in individual doses.

Table 4.12 Remarks:   ' •
(A)   Non-chlorinated  phenolic  compounds:  The following compounds  are
considered in  this category;  2,4-dimethylphenol, 2,4-dinitrophenol,2-methyl-
4,6-dinitrophenol,  2-nitrophenol,  4-nitrophenol,   phenol  and  cresol(ortho,
para, meta).

(B)   Cfilorophenols:   The  following  compounds  are  considered  in this
category?  ortho-chlorophenol,  meta-chlorophenol,   para-chlorophenol,  2,6-
dichlorophenol,2,5~dichlorophenol, 2,4-dichlorophenol, 3,5-dichlorophenol,2,3-
dichlorophenol, 3,4-dichlorophenol, 2,4,6-trichlorophenol,2,3,6-trichlorophenol,
2,4,5-trichlorophenol,     2,3,5-trichlorophenol,2ป3ป4-trichlorophenol,     3,4,5-
trichlorophenol,   2,3,5,6-tetrachlorophenol,2,3,4,5-tetrachlorophenol,  2,3,4,6-
tetrachlorophenol, and pentachlorophenoL

(C)   Volatile  chlorinated aliphatic  hydrocarbons:   This  category includes
the  following  compounds:    Chloroform,  Dichlora-i,l-ethane,  DicMoro-1,2-
ethane,Dichloro-l,l-ethene,  Dichlorp-l,2-ethene,  Dichloromethane,   Dichloro-
1,2-propane, Dichloro-l,2-propene (cis  and trans),Tetrachloro-l,l,2,2-ethane,
Tetrachloroethene, Carbon  tetracbloride,  Tricbloro-l,l,l-ethane, Trichloro-
1,1,2-ethane, and Trichloroethene.

0)   CWorobenzenes;  Trichlorobenzenes (all isomers),  Tetrachlorobenzenes
(all isomers) and Pentachlorobenzene.
                                    368

-------
(E)   Polychlorznated  biphenyls:  Isomers 1242, 1248,  1254 and 1260.

(F)   Phenolic compounds by colorimetric  dose involving1 4-aminoantipyrine:
In this instance, phenol itself is  considered, along  with  phenols substituted
in ortho and  in  meta, and even  phenols substituted  in  para by carboxylic,
methoxy, and  sulphonic  acid groups, and  by halogens (Cl,  F, Br,  I).  It is
acknowledged  that the method involving  4-aminoantipyrine does not permit
the  quantification of phenols substituted in  para  by  alkyl, aryl, nitro,
benzoid, nitroso  and aldehyde groups.
4.2.3  England

In  England, cleanup  of contaminated  land is  driven by reclamation and
redevelopment of old  industrial sites,  often for  more sensitive  uses.  Site
contamination   has  largely   been   viewed   as   a  "material   planning
consideration",   not  as  a  matter  of  concern  for  public   health  and
environmental protection [9, 20].   This  has been the subject of much  debate
and criticism  by those who wish to see greater consideration given to these
factors.

To  assist in site assessment for  redevelopment purposes, there is Federal
guidance  in  the form  of   "Trigger  Concentrations"  (Table 4,13) [9, 20].
These Trigger Concentrations have been  established based in large part on
existing  criteria and standards.   They are available for   various  land  uses
and for  a  variety of contaminants commonly  found where industrial  sites
are  being  redeveloped  for  other  uses.     Application of  the  trigger
concentrations is quite simple.  If after  a comprehensive  site investigation,
concentrations   of  soil   contaminants    are   less   than   the  Trigger
Concentrations,  it  can  be  assumed  that  the  site  is  uncontaminated.
Development can then proceed as planned.  If values are  greater  than the
Trigger  Concentrations,  some remedial  action is required  if development is
to  proceed.     Alternatively,  a   different  development  plan   could  be
considered.    The Trigger Concentrations are not  meant  to apply to  sites
already in use and may have to be modified where development  has already
begun before contamination was discovered.


4.2.4  The Netherlands

Throughout the  past five  years,  considerable effort has  been expended on
development of environmental "standards" for  soil and ground water  quality
in The Netherlands.    As a result,  The Netherlands was  perhaps the first
nation  to  formally   establish  a  national,  comprehensive  program  for
assessing the significance  of contamination as well as the extent of cleanup
required  [3,5,10,21-23].   In 1983  and  subsequently in 1987,  national laws
were  promulgated which established the  principal  of "multi-functionality"
for soils  in The Netherlands [21].  The  principal is as follows, "the  multi-
functionality  of  the Dutch  soils should be conserved or,  when  it has  been
disturbed,  be   re-established"   [21].    Various  functions for   soil  were
considered,  including  agricultural,  ecological,  carrying,  drinking   water
supply and so forth.
                                    369

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Table 4.13.  Tentative "Trigger Concentrations" used  in England [20].
                                                   Trigger Concentrations
Compound   Planned Uses
                                                   Threshold
          Action
Selected Inorganic Contaminants
Arsenic

Cadmium

Chromium
(VI)
Chromium
(Total)
Lead

Mercury

Selenium

Boron (sol.)
Copper
Nickel
Zinc
Domestic gardens, allotments
Parks, playing fields open space
Domestic gardens, allotments
Parks, playing fields open space
Domestic gardens, allotments
Parks, playing fields open space
Domestic gardens, allotments
Parks, playing fields open space
Domestic gardens, allotments
Parks, playing fields open space
Domestic gardens, allotments
Parks, playing fields open space
Domestic gardens, allotments
Parks, playing fields open space
Any uses where plants are grown
Any uses where plants are grown
Any uses where plants are grown
Any uses where plants are grown
(mg/kg air-dried soil)
10
40
3
15
25

600
1000
500
2000
1
20
3
6
3
130
TO
300
TBD2
TBD
TBD
TBD
TBD

TBD
TBD
TBD
TBD
TBD
TBD
TBD
TBD
TBD
TBD
TBD
TBD
Contaminants Associated with Former Coal Carbonization  Sites
Poly-
            Dom. gardens,allotments,play areas
  aromatics Landscapes, buildings, hardcovers
Phenols     Dom. gardens, allotments
            Landscapes, buildings, hardcovers
Cyanide     Dom* gardens,allotments,landscapes
 (free)      Buildings, hardcovers
 (complex)  Dom. gardens, allotments
            Landscapes
            Buildings, hardcovers
Thiocyanate All proposed uses
Sulphate    Dom. gardensปallotments$landscapes
            Buildings              !
            Hardcovers
Sulphide    All proposed uses
Sulphur     All proposed uses
Acidity      Dom. gardens,allotments,landscapes
  50
1000
   5
   5
  25
 100
 250
 250
 250
  50
2000
2000
2000
 250
5000
   5
  500
10000
  200
 1000
  500
  500
 1000
 5000
 None
 None
10000
30000
 None
 1000
20000
    3
     proposed  values are  tentative  and/or preliminary requiring  regular
updating.  All  values are for  concentrations determined  on "spot" samples.
If all values are below the Threshold Concentrations, site may be regarded
as  uneontaminated for  these  contaminants and development  may  proceed.
Above the thresholds, remedial action may  be needed.   Above  the action
concentration,  remedial  action will be required or the form of development
changed.
      = to be developed.
                                    370

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As  part  of  the  standards  development  effort  and  consistent  with  the
principal  of  multi-functionality,  The  Netherlands  formulated criteria  for
guiding the assessment and cleanup of  waste contaminated land.   This list
of criteria is  often  referred to as the  "Dutch Mst",   Established in 1983,
the  "ABC" system included three  values  for both  soil and  ground  water
(Table 4.14).   The. A~value was  a threshold  below  which  soil  could  be
regarded  as unpolluted and above  which a preliminary investigation of the
site  would be required,  fhe B-value  was a threshold above  which further
investigation  would  be required to define  the extent  of contamination  and
potential  risks. The  C-value was  a threshold above which  there normally
would be  some removal and/or cleanup, preferably back to the A-value.

The  ABC criteria were  established within a framework  which included three
major   factors   deemed   important  in   assessing  the   significance   of
contamination:

      1.    Nature and concentration of the contaminating substances,
      2.    Site  specific conditions affecting  contaminant  migration and
            fate,
      3.    Use  and function of the soil and  degree of exposure and risks.


Factors 1 and 2 determine whether  contamination poses serious threats
while factor  3  suggests  urgency.   Quantitation  of  factors 2  and  3 is
difficult,  so factor 1 is often emphasized in practice.  The ABC values  were
intended  only as criteria for the first factor  [3Jป

The  A-values  for  metals were  established  based  on  average background
levels in  unpolluted  soils  in  The Netherlands.    For  man-made  organic
compounds, the analytical limits of  detection were used.

These ABC criteria were  never  intended to  be standards,  but  rather trigger
values  for   deciding  upon the   necessity   for   carrying   out   (further)
investigations and  risk  assessments   [10J.   In  practice however,  these
criteria have  been implemented as if they  were in fact standards.

One  application  has  been to judging  the performance  of contaminated  soil
treatment  plants, of which there  are a  large  number and variety  in  The
Netherlands [5].   The  estimated annual treatment  capacity is  on  the order
of 0.5 million m^.  In practice, the  ABC  criteria  are  often  used by the
Provincial governments  to set performance  requirements.    For example,
treated soil  with values  above the C-level are  disposed of at a  licensed
hazardous waste landfill, while those  in the  B-C  level might  go  to  a
controlled (lined) landfill, while  those in the A-B  level  might be  used as
covering  on  dumps  or as  construction fill.   Where housing developments
are  involved,  the goal  for soil  quality near the  development is often the A
level 130].
                                    371

-------
Table 4.14.  Soil and ground water criteria used in The Netherlands for
            contaminated land  ("Dutch  List") [31].1
Soil (nag/kg dry soil)
Component
1. Metals
Cr
Co
Ni
Cu
Zn
As
Mo
Cd
Sn
Ba
HB
Pb
2. Inorganics
NH4 (as N)
P (total)
CN (tot.free)
(tot. comb.)
S (total)
Br (total)
PO4 (as P)
3. Aromatics Compounds
Benzene
Ethylbenzene
Toluene
Xylenes
Phenols
Total
A

100
20
50
50
200
20
10
1
20
200
0.5
50

-
200
1
5
2
20
—

0.01
0.05
0.05
0.05
0.02
0.1
B

250
50
100
100
500
' 30
40
5
50
400
: 2
3.50

-
400
10
50
20
50
—

0.5
5
3
5
1
t
c

800
300
500
500
3000
50
200
20
300
2000
10
600

-
2000
100
500
200
300
—

5
50
30
50
10
70
Ground water
A

20
20
20
20
50
10
5
1
10
50
0.2
20

200
300
5
10
10
100
50

0.2
0.5
0.5
0.5
0.5
1
B

50
50
50
50
200
30
20
2.5
30
100
0.5
50

1000
1200
30
50
100
500
200

1
20
15
20
15
30
(ug/L)
C

200
200
200
200
800
100
100
10
150
500
2
200

3000
4000
100
200
300
2000
700

5
SO
50
60
50
100
4. PoIycyeUe Hydrocarbons
Naphthalene
Anthracene
Fenanthrene
Flouranthene
Pyrene
1,2 benzopyrene
Total
0.1
0.1
0.1
0.1
0.1
0.05
1
5
10
IP
10
10
1
20
50
100
100
100
100
10
200
0.2
0.1
0.1
0.02
0.02
0.01
0.2
7
2
2
1
1
0,2
10
30
10
10
5
5
1
40
                                    372

-------
Table 4.14.cont.    Soil and ground water criteria used in The Netherlands
                   for  contaminated land  ("Dutch  List") [31].1
Component
                         Soil (mg/kg dry matter)
B
                      Ground water  (ug/L)
 B
•งป..,Chlorinated H.y droear bons
 Aliphatic s
       (Individual)         0.1     5      50
       (Total)              0.1     7      70
 Chlorobenzenes
       (Individual)         0.05   1      10
       (Total)              0.05   2      20
 Chlorophenols
       (Individual)         0.01   0.5     5
       (Total)              0.01   1      10
 Chlor. PAHs  (Tot.)       0.05   1      10
 PCB's  (Tot.)             0.05   1      10
 IOC1  (Tot.)              0.1     8      80

'6.^Pesticides
 Chlorinated organics
       (Individual)         0.1     0.5      ฃ
       (Total)              0.1     1      10
 Pesticides
       (Total)              0.1     2      20
                        1
                        1

                        0.02
                        0.02

                        0.01
                        0.01
                        0,01
                        0.01
                        1
                        0.5
                        0.1

                        0.1
10
15

 0.5
 1

 0.3
 0.5
 0.2
 0.2
15
 0.2
 0.5
 50
 70

  2
:  5

  1.5
  2
  1
  1
 70
  1
  2
7. Other Pollutants
Tetrahydrofuran
Pyridine
Tetrahydrothiofene
Cyclohexanes
Styrene
gasoline
mineral oil

O.I
0.1
0.1
0.1
0.1
20
100

4
2
5
6
5
100
1000

40
20
50
60
50
800
5000

0.5
0.5
0.5
0.5
0.5
10
20

20
10
20
15
20
40
200

60
30
60
50
60
150
600
 ^These  values  are  not  "standards"  but  rather  guidelines  for  use  in
 assessing the significance of contaminated land.  A simplified explanation of
 the ABC  levels: A-level implies  unpolluted,  B-level implies pollution  present
 and  further  investigation  required,  C-level  implies  significant  pollution
 present and  cleanup (preferably back to the  A-level) required.
                                     373

-------
A further development of significance in  The Netherlands occurred in 1987,
when the Federal government enacted a comprehensive Soil  Protection Act
which  reaffirmed the  soil multi-functionality concept.   It also provided for
another list of criteria,  "reference values for a good soil quality", as shown
in Table 4.15 [21, 22],

During  development  of  the reference  values, it was  acknowledged  that a
pure effect oriented approach,  where reference values are derived  from a
complete toxicological  analyses of the effects of substances on  mans,  plants,
animals and ecosystems,  was not  feasible. Instead,  provisional reference
values  were derived  based on  what was  considered  the best  information
available.   The  first  stage of the  process  was  to  examine  soil  quality
requirements  resulting  from  other  areas  of  policy   (e.g.   standards  for
drinking water, surface water and so forth).   One important implication of
this  was  that  ground  water  quality  should  satisfy   drinking   water
standards.

For organic compounds in soils, a linear  adsorption model was  used which
related organic compound  sorption to compound octanol/water  partitioning
and soil organic matter content.  For inorganics this  approach  was  deemed
inappropriate.     Instead,  empirical  relationships   were   developed  for
concentrations of heavy metals  in unpolluted Dutch soils  as a  function of
soil clay and organic  matter  content.   The  provisional list  was discussed
and criticized  by  a  committee  of   experts  and  a revised  list  prepared
[21,22].    The  reference   values  are  to  be  used   to  designate  areas
contaminated by hazardous  wastes and to restrict point releases.  Although
some may try to use them as  cleanup goals (but not as legal standards) to
be  reached by  soil remediation techniques, it  is  unlikely that  in practice
they will be met [22],


4.2.5    West Germany

In  West Germany,  the  assessment of contamination  and  determination of
cleanup goals lies with the 11 individual States or  Lander.  There  are no
uniform procedures or standards  [11,17].  The water and waste  management
authorities in each  Lander decide on a case-by-case basis.  In many cases,
the  responsible  authorities  use  the  "standards"   of  The  Netherlands.
However, there  remains considerable  variability in the standards or  criteria
applied from  Lander to  Lander.  The City State  of Hamburg is unique in
that it  has  a  formalized  program   for   assessment   and  remediation  of
contaminated sites.

West Germany has Initiated  a far-reaching program  at the Federal level to
provide for the long term  safeguarding  against  the  pollution  of soils  by
hazardous  substances  and  against the stress  of  soils due  to usage  [4].
Fundamentally it was  agreed that natural resources should be protected for
their  own  sake,   especially  since   soil  damage  is  often  irreversible.
Pollution of soils should  be minimized and in  the long-term stopped,  and
contaminated sites such as old industrial sites should  be reclaimed.
                                    374

-------
Table 4.15.  Reference values for multi-functional soil and frbtind water in
            The Netherlands [3l].

                                    Standard soil
Substance                           (H=10/L=25)       Grduftd  Water
1. Inorganic Compounds
Cr [50+2L]1
Ni [10+L]
Cu [15+0.6(L+H)]
Zn [50+1.5(2L+H)J
Cd [0.4+0.007(L+3M)]
Hg [0.2+0.0017(2L4k)j
Pb [50+L+H]
As [15+0.4(L+ti)]
F [175+13L]
N032
S043
Bromides
Chlorides-*
Fluorides-*
Ammonium compounds^
Phosphate*
(Total phosphate)2
mg/kg
100
35
36
140
0.8
0.3
85
29
500
-
-
-
-
-
-
-

dry matted
1
IB
iง
i&a
1*5
&05*
. IS
16
-
5,0
150
300
ibo
0.5
2/10
0.4/3.0


ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L

mgN/L
mg/L
ug/L
mg/L
mg/L
mgN/L
mgP/L

2. Organic Compounds         Reference value at (H=10) dry wt. basis**

(a) Halogenated hydrocarbons and choline-esterase inhibitors:   <1  ug/kg -
hexachlorocyclohexane;   endrin;    tetrachloroethane;   tetrachloromethane;
trichloroethane;   trichloroethene;  trichloromethane; PCB  IUPAC no. 28, 52.
<10    us/kg    -    chloropene;     tetrachloroethene;    hexachloroethane;
hexachlorbutadiene;  heptachloreposice;   dichlorobenzene;  trichlorobenzene;
tetrachlorobenzene;       hexachlorobenzene;       monochloronitrobenzene;
dichloronitrobenzene;  aldrin; dieldrin;  chlordane;  endosulfan;  disulfoton;
fenitrothion; parathion  (and -methyl); triazophes PCB IUPAC no. 101,  118,
138, 153,  180.  <100 uff/kff  - ODD; DDE; pentachlorophenol.
(b) Polycyclic aromatic hydrocarbons:  <10 ug/kg -   naphthalene; chrysene.
<100  tig/kg:    fenantiene;  anthracene;  fluorantene;  benzo(a)pyrene.    <1
mg/kg  -   benz(a)anthracene.   <10  mg/kg  -  benzo(k)fluorantene; indeno
(l,2,3cd)  pyrene;   benzo(ghi)  perylene
(c) Mineral oil:  <50 mg/kg  - total.  <1 mg/kg  -  octane;  heptane

IH=Weighth of organic matter  soil,  L=weight% of clay fraction in soil.
2Lower values  can be required for protection of nutrient poor  regions.
^Higer values appear  naturally in regions with a strong marine influence.
*The lower  values apply to  ground water  in sandy regions; the higher
values apply to ground water in regions with clay and peat soils.
•>Or detection limit if  this is higher than the value stated.
                                    375

-------
The  program originated at the Federal level in 1985 as the  "Conception  for
Soil   Protection"   [4].     In   May   1987,   the  environmental   ministers
recommended to the  Federal  government that  relevant laws  and regulations
be amended  to  incorporate soil protection aspects.   Measures  to  .be taken
were approved  by  the Federal  cabinet in the  end of  that  year.     The
concept of "threshold and guide values"  has  emerged  which wiJl  include a
description  of substances endangering soils  and  delineate threshold  and
guide  values for soil contamination.   It is believed that  the threshold and
guide  values for soil contamination  can contribute  to  conserving  soils with
low contamination levels and  trigger  remediation  before actual  public health
and  environmental damage  has occurred.

The  components for deriving threshold and guide values  for soils  are to be
compiled from various sources (e.g. limiting values of Ordinance on  Sewage
Sludge Treatment for land application).   There  is a study  in progress  to
assess  the  risks and  hazards  to  soils and  the need for  reclamation and
reuse.  This work is currently focused on heavy  metals, but  later  will be
expanded.  An overview of some preliminary values is  shown in Table 4.16.

It is recognized that interpretation of  the threshold and guide values can
never be based  solely on  numerical  values alone.  Apart from  the question
of whether  the  values are sufficiently well-founded, their interpretation in
a  particular  case  will always  necessitate information  on  soil  sampling,
analytical methods as well  as  site  usage objectives.


4.2.6  France

In France, there are no particular  directives or  standards from the  Federal
Ministry of Environment [12].  As a  consequence, setting cleanup  goals and
site  restoration is a local matter.   Existing standards  and criteria are used
as  appropriate  (e.g. drinking  water  standards, sludge spreading limits,
etc.). Reportedly, risk assessments and  decontamination projects are  carried
out  on a pragmatic basis according to site  characteristics,  environmental
vulnerability,  pressure  of  local  authorities   and  in  some  cases   public
attention and political impact.   The Ministry  of  Environment is considering
the  subject of standards  for characterizing soil  pollution.   In cases where
contamination is by natural  substances,  reference  will always be made  to
background conditions [12].


4.2.7  Denmark

Approaches used in Denmark  have attempted to recognize a  variety of risks
associated  with contaminated land such as contamination of ground  water
and  drinking water, indoor air pollution and direct  contact/ingestion of soil
[13,14]. For  initial site  screening and assessment, reference is often made
to the  "Dutch  List".   As  appropriate, existing Danish standards  are  used.
For  example, drinking water  standards  have been applied to ground water.
Site-specific risk  assessments have  been performed,   particularly where
there has been more sensitive uses  planned for  old industrial sites.  While
a variety of sites  have been assessed  and cleaned up, the procedures  for
setting cleanup goals  are  as  yet  not  formalized.     A   systematic  risk
assessment  procedure is being formalized  by the Federal  government [14].
                                   376

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Table 4.16.  Overview of concentrations of  some elements in
            man-affected soils in West Germany [32].
                              Concentrations in Air-dry Soil  (mg/kg)
Element
Arsenic
Boron
Beryllium
Bromide
Cadmium
Cobalt
Chromium
Copper
Fluoride
Gallium
Mercury
Molybdinum
Nickel
Lead
Antimony
Selenium
Tin
Thallium
Titanium
Uranium
Vanadium
Zinc
Zirconium

0.1
5
0.1
1
0.01
1
2
1
50
0.1
0.01
0.2
2
0.1
0.01
0.01
1
0.01
10
0.1
10
3
1
Normal
20
20
5
10
— 1
10
50
20
200
10
1
5
50
20
0.5
5
20
0.5
5000
*- T
100
50
300
Contamination
< 8000
< 1000
< 2300
< 600
< 200
< 800
<20000
<22000
< 8000
< 300
< 500
< 200
<10000
< 4000
< ?
< 1200
< 800
< 40
<20000
< 115
< 1000
<20000
< 6000
Tolerable
20
25
10
10
3!
50
100
100
200
10
21
5
501
1001
5
10
50
1
5000
5
50
3001
300
l-Same as  values  used  for  cultivated .soil treated  with  sewage  sludge as
fertilizer (German Sewage Sludge Regulation).
                                     377

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4,2.8  Sweden

In Sweden, the first significant problem  with  hazardous waste contaminated
land occurred  in  the  mid-1970's.  However, there are as yet,  no formalized
approaches for  assessing the  significance  of  contamination  nor  setting
cleanup goals [15].


4.2.9  Finland

Approaches to  setting  cleanup goals in Finland are in development [16,25 ]ป
However,  as yet  there are no  formalized methods on  a local  or national
basis.  There have been  a few sites which have been assessed and where
cleanup goals  have been  explicitly  established (e.g. saw mill/ wood  treatment
sites).    In these  cases, current  and  future  land  use  conditions  and
potential  exposures  have  been  considered   with reference   to  existing
standards  and  criteria  (e.g.  "Dutch  list").     For  a  particular   site,
concentrations  of soil  contaminants  were  established  which determined the
cleanup requirements  (e.g.  clean, road fill, local landfill,  hazardous waste
treatment facility).


4.2,10  Norway

In Norway, the problems of hazardous  waste contaminated land are  just now
being  addressed.   As  a result,  there  are  no  formalized  approaches for
setting cleanup goals [1],   Problems  of  hazardous waste contaminated  land
have  so far been largely  caused by old  waste deposits  encountered during
construction activities  (e.g.  buildings,   railways).   In  most  cases,  the
significance of contamination  and need for cleanup was  assessed  in an ad
hoc fashion with  some consideration of site use,  existing standards such as
the "Dutch List"  and  the perceived available  options for  remediation.   In
other cases where  the contamination is  more complex  and has potentially
far-reaching public health and environmental impacts (e.g. chemical waste
adjacent  to  or  within  a  fjord  or  beneath  a  housing   development),
investigations  have commenced but, cleanup goals have  yet to  be  explicitly
set.
                                    378

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                                SECTION 5
               SOIL QUALITY  CRITERIA AND CLEANUP GOALS


There  has been  considerable  discussion  and debate  regarding appropriate
methods  for assessing  the  significance  of  contamination  and  establishing
cleanup goals for waste  contaminated land.   The approach which has  been
most controversial, perhaps, is a "standards-based"  approach involving the
use of predetermined standards,  guidelines and criteria  (PSGCs).   In the
context of this discussion, the general use of soil and ground  water  quality
criteria  and  cleanup  goals  is  meant  to  represent  a  wide  range  of
predetermined,  somewhat generic  numerical values,  including  true  legal
standards, guidelines  and criteria.   Moreover,  it is important to recognize
that "cleanup goals" are but one  application of the evolving  spectrum of
"soil and  ground water  quality criteria".


5.1 CURRENT ATTITUDES AND USE

In most of  the ten  nations considered  in this  review, the  desire and  need
for cleanup  criteria specific  to contaminated land  were  evident.   Readily
available, comprehensive  listings  were  viewed  as  essential  to facilitating-
initial  site  review  and  screening.   Many  persons  cited that there was a
demand  for  unequivocal cleanup criteria,  often  put  forth  by  owners,
developers  and  future  users  of  contaminated land.     Equally evident,
however,    was  a   strong appreciation  for  the difficulties  and  potential
problems  related to establishing and implementing  cleanup criteria  as  well
as  the belief that  there must  be some  site-by-site flexibility for  setting
final cleanup  goals.

The first nation to  establish  a  national,  comprehensive set of  numeric
criteria for contaminated land was The Netherlands.   In 1983 a national act
was promulgated which  put  forth the concept  of  "multi-functionality" for
soil and  included criteria for  assessing the significance of soil and  ground
water  contamination and guiding  site assessment and cleanup.   In  support
of a broad  soil  protection poMcy,  reference  values were  later enacted for a
"good  soil quality".

The criteria of the Dutch List were never intended  to be legal standards as
such,  but  rather   trigger  values  for  deciding  upon  the  necessity for
carrying  out (further)  investigations  and  risk  assessments.   In  practice
however,  due  to  lack  of  other information,  these  criteria have  been
implemented as if they were in  fact standards.  The  "Dutch List" is widely
referred  to (Table  4.1)  and  often  cited  as  "standards".    In  1988, the
province  of Quebec, Canada promulgated their  own  similarly  comprehensive
list of criteria, based in. large part on the Dutch List.

Other  national  and  provincial  government  agencies  have  also  established
cleanup criteria  in  the  form  of  acceptable  limits  for  soil and ground water
contaminants.      These  have   different   names   including   "Trigger
Concentrations"  (England), "Cleanup Guidelines" (New  Jersey,  USA),   and
"Guide/Threshold Values"  (West  Germany).  While  far  less  comprehensive
than the  Dutch  or Quebec lists, they are intended  to serve as guidance in
site assessment  and cleanup.   In many  cases the criteria are given with
                                    379

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reference  to aproposed land  use.   In  most cases,  they  are not  legal
standards,  but  rather  guidance  criteria intended  to  be  used with  due
consideration of site specific  factors  and  subject  to  justification  and/or
modification.

The  use  of standards-based approaches appears to  be  gaining  favor in
many nations,  especially for preliminary assessment of the  significance of
contamination and  the  potential extent of  cleanup.   The  Netherlands has
used  this  approach  for more  than 5  years to remediate  several hundred
sites.   Recently, the  Province  of Quebec  in Canada, issued  a similarly
comprehensive list of soil and  ground  water criteria, in large part adapted
from the  "Dutch List". Establishment of similar criteria lists  are also under
consideration in other  jurisdictions  (e.g. Wisconsin* USA,  Alberta, Canada;
West Germany and France).

Even in those  jurisdictions  where cleanup criteria have  not been formulated
specifically for cleanup of  contaminated land,  reference is commonly  made
to existing  standards, guidelines and criteria (see Table 4.1). Reference to
the Dutch List is  widespread.   There is also  direct  use  or adaptation of
existing'  national or  international standards and  criteria.  Often  these were
developed under programs  and legislation  unrelated to contaminated  land.
Examples  of these include:

      o      Drinking water  standards,
      o      Ambient  water  quality  criteria,
      o      Storm water runoff criteria,
      o      Limits on sewage sludge  application to agricultural lands,
      o      Occupational air quality standards,
      o      Ambient  air quality criteria, and
      o      Air quality  emission limits.


Notably,  in several jurisdictions, ground water quality standards (i.e. legal
standards)  have been established  equal to  drinking water standards (e.g.
Wisconsin, USA; Denmark; The  Netherlands).   In some cases,  use of existing
standards,  guidelines and  criteria has  been formally incorporated into  a
waste site cleanup program (e.g. USA Superfund program).


5.2  CHARACTERISTIC FEATURES

There appear  to be several  features  which  are  common  to the  numeric
values appearing as  cleanup criteria as  well as the process by  which they
have been developed.  These are outlined in Table 5.1.

A comparison of acceptable soil quiality concentrations  and cleanup  criteria
developed  for  a common  heavy  metal  contaminant,  lead, and  a  common
organic  contaminant,  PCBs,  is presented in Table  5.2.   Inspection of the
values shown  and their structure illustrates  some  of  the general  features
outlined  in  Table  5.1.   Moreover, the, data  shown suggest that  various
judgements  (e.gซ technical,  social, economic)  may   have played  a  part in
arriving  at a given numeric value.
                                    380

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Table 5.1.   General features of soil quality  criteria  and cleanup goals and
            their development.
      General Features
      Criteria  development  has  invariably  included adaptation of  existing
      applicable  or  relevant  and  appropriate  standards,  guidelines  and
      criteria, often developed  under programs  unrelated to contaminated
      land.

      Criteria  are  often noted  to  be interim and/or  subject to continuing
      review  and refinement.   It is commonly emphasized that the criteria
      are  not  true legal  standards,  and  are  subject  to  site  by  site
      considerations and decision making.

      Information  is  often  available for  inorganic contaminants such as
      heavy  metals,  with   comparatively  lesser  information  for  organic
      contaminants.                                                •

      Multiple levels are often  put forth to account for  different land  uses
      and  different investigative  and cleanup   actions  required.    These
      often differ  by an order  of magnitude from one level to the next.

      Obviously  unpolluted  soil is  often characterized by the following:
      For   inorganic   contaminants  (e.g.  heavy  metals),   normal  soil
      background  levels often serve as the basis.
      For   organic  contaminants,   particularly   synthetic   organics,  the
      analytical  detection limit  is often used as  the basis  (i.e. the desire is
      for  no  detectable levels).    Alternatively,  equilibrium partitioning
      concepts  have  been  used  to  set  an acceptable  soil contaminant
      concentration  to  maintain ground  water  quality  levels  at  or  below
      drinking water standards.                                    .

      Degrees of soil contamination are often characterized as follows:
      For  inorganics,   multiples of  background  are   used  to characterize
      moderate and severe  contamination.
      For  organics,  moderate contamination may be set  at  a value  which
      does not cause ground  water contamination to exceed drinking water
      standards (based on  equilibrium partitioning).

      Where done, land uses are typically  classified as  to their  sensitivity
      with respect to  hazards associated  with direct  or  near-direct contact
      and/or direct phytotoxicity and bioaccumulation, for example:
      Most sensitive:    agricultural, home gardens and play areas,
      Less sensitive:    parkland or green spaces with open public access,
      Least sensitive:    commercial/industrial with restricted  public access
                                     381

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Table 5.2.   Comparison of soil quality and cleanup criteria for  selected
            contaminants.^
Reference
Canada
CCREM
Alberta
Ontario
Quebec
England.
The Netherlands


West ..Germ-any.

Description

Agricultural land uses
General public access land uses
Commercial/Industrial uses
For Acidic Soils (pH<6.5)
Residential/agricultural land uses
Commercial/parkland uses
Industrial land uses
A-Level (background, MDL)
B-Level (investigation)
C-Level (cleanup)
Domestic gardens, allotments
Parks, playing fields, open space •
A-Level (background, MDL)
B-Level (moderate contamination)
C~Level (severe contamination)
Good Soil Quality '(1Q3JOM, 2535C)
Normal
Tolerable
Lead
mg/kg
-
800
60
500
1000
50
200
600
500
2000
50
150
600
85
0.1-20
100
PCBs
me/ks .
0.5
5
50
-
-
0.1
1
10
50/5002
1000/100002
0,05
. 1 ,
10
<0.010
_
"**
^Refer to appropriate section of the preceding text for  complete information
regarding the data shown in this table.
^Values shown apply  generically to polyaromatic hydrocarbons with the low
value indicating the  threshold  concentration and the high  value  indicating
the action level (see appropriate text section for discussion).
                                    382

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5.3   ADVANTAGES AND DISADVANTAGES

A standards-based approach has been  criticized,  by some  as simplistic  and
unworkable, yet it  has been consistently favored  by risk managers due  to:

      o     Once a standard is adopted, application is  simple and
            non-controversial.
      o     Standards are easy to justify  and defend in court.
      o     Provides a means  of communication  among all participants in
            the risk  management  process.
      o     Appears  to be an  objective process grounded in scientific
            analysis  and free  of value judgements.
      o     Relieves  policy makers from  cumbersome burden of dealing
            with uncertainty and from being  charged with  imposing their
            own  values/beliefs on  society.
      o     Simplifies problem by automatically  determining the goals of
            risk  management activities.
      o     Reflects  recurrent hope  for scientific method for objectively
            resolving the problem of "How Clean is  Clean?" [17].


There  appear to be  numerous potential  advantages and disadvantages  of a
standards-based   approach  to  establishing  cleanup  goals  (Table   5.3).
Approaches  employing;  soil and  ground  water  quality  criteria are  not
claimed to be  the  best  approach for setting cleanup  goals, but rather a
necessary  part of  an overall  program  for dealing  with contaminated land.
Predetermined  criteria facilitate national or  regional soil and ground water
protection  programs  and  encourage  redevelopment  efforts for contaminated
land.   In  this  context  they  may be used  for both  initial screening  and
contamination assessment as well as  for determination of final cleanup goals.

For   contaminated    sites  of  national  and   regional  significance   (e.g.
uncontrolled  hazardous   waste  sites  involving  large  concentrations  or
amounts of highly toxic  materials)  such  a  standards-based approach  will
probably not be  appropriate.
5.3  METHOD DEVELOPMENT

It  appears  that  a  standards-based  approach  represents  an  important
component of an overall program to deal with cleanup of  hazardous waste
contaminated land  and  soil and  ground  water protection  in  general.   The
challenge  would seem to be  one of  developing  scientifically well-founded
(as far as possible,  at least)  soil  quality and  cleanup criteria  which are
consistent with other laws  and regulations  and  supported by  the various
concerned and  affected parties (e.g.  scientific and  engineering  community,
regulators and  politicians, environmental  and citizens groups).
                                     383

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The elements judged by this author to be important to  the  development and
implementation  of soil  and  ground  water quality  criteria for cleanup  goal
setting are outlined in Table 5.4.  Development of a complete, comprehensive
method is ongoing.
Table 5.3.   Example advantages and disadvantages to the use of
            soil and ground water  quality criteria for  cleanup  goals.
Potential Advantages and Disadvantages of  Standards-based Approaches
o     Speed and ease of implementation.
o     Similar  sites would be  handled in a similar  manner.
o     Useful for initial assessment of significance of contamination.
o     A priori information facilitates  planning and action.
o     Encourages developers to undertake decontamination and  restoration*
o     Potential consistency with strategies for environmental standards.
o     Reality  of contaminated land made easy for  layman.
o     Facilitate environmental audits  of industrial sites.
o    " Facilitates monitoring/permitting  of operational industrial  sites.
o     Can be used for performance assessments of soil treatment plants.
o     Implies non-negotiability and reduces local  political influences.

Disadvantages

o     Some important site-specific  considerations  cannot  be accounted for.
o     Standards, guidelines and criteria are not formulated for  many toxic
      substances of concern.  Existing standards formulated under other
      programs are .not necessarily appropriate for contaminated land.
o     PSGCs imply a level of understanding, knowledge and confidence
      which likely does not exist.;
o     Once PSGCs are established; site-specific flexibility may be
      difficult.
                                    384

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Table 5.4.   Elements of a standards-based approach for  establishing
            soil and ground water quality criteria and cleanup goals for
            hazardous  waste contaminated land.
      Key Elements


      Site classification scheme  to  screen contaminated sites and rate them
      according to their apparent hazards  (e.g. low  hazard,  high hazard,
      catastrophic).

      Properties and  characteristics  of  chemical occurrence,  transport and
      fate for common  contaminated sites.

      Range of  reasonable land-use and exposure scenarios.

      Generic risk assessment and  risk management protocol.

      Comprehensive,   multi-dimensional  listings  of  acceptable  soil  and
      ground water  quality  criteria for range of site  characteristics and
      exposure  scenarios.
                                     385

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                                SECTION 6
                   OVERVIEW OF CLEANUP TECHNOLOGIES
A.  separate  but very  important related  issue  is  the availability, cost and
performance  of  cleanup  technologies   to  achieve  the   cleanup   goals
established  for contaminated land.  In contrast to early cleanup experiences
where the preferred approach  was simply either  1)  excavation and  hauling
offsite to a  licensed landfill or  2)  in-place encapsulation and  isolation, there
is  growing interest in and  use  of  onsite and insitu treatment processes.

Comprehensive research  and development efforts as  well as  demonstration
projects into the treatment of contaminated soils include the following:

      o     Superfund Innovative Technologies Evaluation program (USA),
      o     NATO  CCMS  Demonstration of Remedial Action Technologies for
            Contaminated Land  and {Ground water  (International),
      o     The Spearhead program on Soil Research (The Netherlands),
      o     The Soil Treatment Research Project (West Germany), and
      o     The Lossepladsprojektet (Denmark).


Results of this work have already provided much information on  basic and
applied aspects of treatment processes and procedures for hazardous  waste
contaminated land.  The results of continuing work should be  even  more
valuable.

Based on the  results of past research and experience, technology screening
guides and  design manuals have recently been  published  to assist with the
process  of  identification, evaluation  and design  of  cleanup for hazardous
waste contaminated  soils  [e.g.  11,   32-35],    Summary  information  from
several documents are shown in Tables 6.1  to  6.4.   These  clearly indicate
the  wide  range  of  alternative  technologies   available  for  treatment  of
contaminated  soil.   They  also  point  out the early  stage  of development
and/or demonstration  of certain technologies.

While the information  base regarding treatment  technologies for hazardous
waste contaminated land is rapidly expanding, there currently remains much
uncertainty above the application and performance of many processes and
procedures  for the  wide  variety  of waste constituent  mixtures and soil
environments.   This is particularly true for insitu  processes.   Thus, great
care  must be exercised in technology screening  and evaluation.  In many
cases, bench and/or pilot scale tests  may be necessary and appropriate  to
confirm  the performance capabilities of a given technology  prior  to its
implementation on a full scale.
                                    386

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Table 6.1.   Examples of chemical constituents  considered within
             waste groups [after 331.^
Waste Group
Example Constituents
Organic Contaminants

Halogenated Volatiles


Halogenated Semivolatiles


Nonhalogenated Volatiles

Nonhalogenated Semivolatiles
PCBs
Pesticides
Organic Cyanides
Organic Corrosives

Inorganic Contaminants

Volatile Metals
Nonvolatile  Metals
Other Categories
Eadioactives
Inorganic Corrosives
Nonmetallic  Toxic Elements
Inorganic Cyanides

Reactive Contaminants

Oxidizers
Reducers
Chlorobenzene, Chloroform, 1,2-
dichloroethane, Methylene chloride,
1,1,1-trichloroethane, Trichloroethene,
Pentachlorophenol, 1,2-
diehlorobenzene,  Hexachlorobenzene, 2-
chloronapthalene.
Acetone, Benzene, Methanol, Toluene,
Methylisobutyl ketone.
Cresols,  Phenol,  Anthracene,
Benzo(a)pyrene,  Dimethyl phthalate,
Nitrobenzene.
PCBs (Arochlor)-1242.
Aldrin,  Chlordane, Dieldrin, Toxaphene.
Organonitriles.
Acetic acid, Formic acid.
Arsenic, Lead, Mercury.
Cadmium, Copper.
Asbestos.
Radium,  Radon.
Hydrochloric acid,  Sodium hydroxide.
Fluorine.
Cyanide, Metallic cyanides.
Chlorates,  Chromates.
Sulfides, Hydrazine.
      compounds listed are merely examples  of  a wide range of compounds
 within each group and are for use in application of Table 6.2.
                                     387

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Table 6.2.   Treatment technology screening matrix for  waste
              contaminated soils in the  USA [33]. *







if Technology

[ Contaminant
Organic
lidked bed incineration
I ""
Table 5
1 Rotary kiln Incineration
a%6ฃ^5
1 Pyrolysis-incineration
1 Vitrification

                   Halogenated volatiles
               HaJogenated semivolatiles
                Nonhatogenatad volatiles
             Nonhalogenated samivolatiles
                             PCBS
                          Pesticides
                     Organic cyanides
                    Organic corrosives IQWQJQ iQlQJOlQlQlOlOlOlQlQtXlX
             Inorganic                   >
                       Volatile metatsl XlXjX IO[Xp[O[O|Q}O|O[OjซQX
                     Nonvolatile metals|o|o|Q|o|QblOlQlQlOlOIOWQ(x
                        .   Asbestos
                   Radioactive materials^.
                   Inorganic corrosives 5 5 Q 5 QD |O1Q[Q|O|O|O
                    Inorganic cyanides <5 <5 ฉ ฉ Q 3
             Rซซctlvซ                   J _
                           Oxidizers Q A Q O
                           Reducers Q ฃ Q Q Q|x|ฎJQ[OlQiO|Oiฎte


              * Do not use this matrix table
               alone. Please refer to the cited
               appendices for guidance.
   Demonstrated effectiveness
Q Potential effectiveness
O No effectiveness
X Potential adverse impacts to
•   process or environment
^Demonstrated  effectiveness  =  successful  use  on  commercial  scale   for
treating  Superftmd  wastes;  potential effectiveness  = basic characteristics
for successful application but  not been proven  on a  commercial basis.    No
effectiveness =  not  expected  to remove  or  destroy the contaminant  to  a
significant degree.  Adverse impacts  - the contaminant is likely to interfere
with  or adversely impact the  environment or the safety,  effectiveness, or
reliability of the treatment process.   •
                                       388

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Table  6.3,   Summary of  remedial technologies for treatment of soil
             contaminated by petroleum  products in the  USA  [34].
            Technology
Expo-
aura Applicable
Path- Petroleum
ways1 Product*2  Advantage* Limitation*
                       Relative
                       Costs'
           In Situ

           Volatilization
1-7   1, 2, 4
           Biodegradatlon   1-7   1,2,4
Can remove  VOCs only.    Low
some com-
pounds resis-
tant to
biodegra-
dation,

Effective on  Long-term     Moderate
some non-   tlmeframe.
volatile
compounds.
Leaching 1-7 1,2,4

Vitrification 1-7 1, 2, 8, 4

Passive 1-7 1, 2, a, 4


isolation/ 1-7 1, 2, 3, 4
Containment


Could be Not commonly
applicable practiced,
to wide
variety of
compounds.
Developing
technology.
Lowest cost Varying degrees
and simplest of removal.
to Implement.
Physically Compounds not
prevents or destroyed.
Impedes
migration.
Moderate

High

Low


Low to
moderate


1Exposure pathways!  l=vapor  inhalation;  2=dust inhalation; 3=  soil
  ingestion,  4=skin contact;  ง=ground  water; 6=surface water;  and T=plant
  uptake.
2 Applicable petroleum products:   l=gasoliries; 2=f uel oils  (#2, diesel,
  kerosenes); 3=coal  tar residues; and 4=chlorinated solvents.
        are highly dependent on  site conditions.
                                         389

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Table 6.3.cont.
 Summary  of remedial  technologies for treatment of soil
 contaminated by petroleum products  in the  USA [34J.
        Technology
Expo*
*ur* Applicable
Patf* Petroleum
ways1 Products3  Advantage*  Limitations
                         Relative
                         Coat*'
       Non-ln Situ
       Land treatment   1-7  1,2.3
       Thormal        1-8   1,2, 3,4
       Treatment


       Asphalt         1-6-   1,2
       Incorporation
       Solidification     1-6   1, 2, 3, 4
       Groundwater     1-6   1,2,4
       Extraction and
       Treatment

       Chemical       1-S   1,2, 3, 4
       Extraction
       Excavation
1-8   1, 2, 3, 4
               Uses natural
               degradation
               processes.
               Complete
               destruction
               possible.

               Use of
               existing
               facilities.


               Immobilizes
               compounds.

               Product
               recovery,
               groundwator
               restoration.
Removal of
soils from
site.
           Some residuals  Moderate
           remain.

           Usually        High
           requires special
           facilities.
           Incomplete
           removal of
           heavier
           compounds.
           Not commonly
           practiced for
           soils.
Not commonly
practiced.
Long-term
liability.
             Moderate
                                                             Moderate
                                                             Moderate
                                        High
                                                             Moderate
1 Exposure pathways: l=vapor inhalation; 2=dust inhalation; 3= soil ,
  ingestion;  4=skin contact} S=ground  water;  6=surface  water;  and  T^plant
  uptake.                                                       •   "  '      '   .
2 Applicable petroleum products!  l=gasoMnesป  2=fuel oils  (f2,  diesel,
  kerosenes); 3=coal tar  residues; and  4=ehlorinated solvents.
3 Costs  are  highly  dependent  on site  conditions.
                                           390

-------
Table 6.4.   Applicability of techniques for treatment of contaminated
            soil in Europe [after  11]. 1

                                     Contaminant Type
                           1                 2
                        Aromatics  & Aliphatics
Treatment
Technology
Volatile
Heavy
                                             3
                                          Phenols
Soil Type2              A,  B              A,   B

Applicability of techniques for the treatment of excavated  soil
Extraction
S edimentation/
 flotation
Evaporation
Biological
 treatment
Stabilization
                                          A,  B
Extraction
Evaporation/
 Air stripping
Steam  stripping
Biological land
 farming
Ventilation
Bioextraction
Chemical oxidation/
 reduction
Precipitation
Neutrolization/
 hydrolysis
 +,  +
 +,  ~
 +.  +
ฑป  -

ฑป  ฑ


+.  -
1 For  examples of chemical constituents  in each waste category, refer  to
  Table  6.1.
2 Soil types are cohesionless permeable  soil (A) and cohesive soil with a
  low  permeability (B).
^Explanation of symbols used:
  "-"    means generally not applicable.
  "+."    means applicable in principal in some cases.
  "+"    means applicable in principal.
  "++"  means in some cases applicability is proven.
  "++"  means applicability is proven.
                                     391

-------
Table 6.4.cont.    Applicability of techniques for treatment of contaminated
                  soil in Europe [after
Treatment
Technology
Contaminant Type
45 6
Chlorinated Hydrocarbons Heavy
Metals
Volatile Heavy

7
Cyanide
Soil Type2              A,   B      Af   B             A,   B       A,   B

Applicability of techniques for the .treatment of excavated soil
Extraction
Sedimentation/
flotation
Evaporation
Biological
treatment
Stabilization
Applicability of insitu
Extraction
Evaporation/
Air stripping
Steam stripping
Biological land
farming
Ventilation
Bioextraction
Chemical oxidation/
reduction
Precipitation
Neutrolization/
hydrolysis
+, +3 . . +, +

-ป - -j -
*+ป +•*• ฑs ฑ

ฑ3 ฑ ฑป ฑ
+, + +, +
techniques
ฑ, - ' -, -

+, - -, _
ฑป - -t ~

— — — ^ —
_ _ _, _
.. _ -$ _

_ - -s -
- - _f

~ป ~ . ~" ป ~*
ฑฑป ฑ

ฑฑf -
, _f _

-, -
•H-.; ++_

ฑป •-

_} _
""ป ~

"~t ~,
~i, ~
-, - ,

ฑฑj ~
ฑฑง ~

~ป —
ฑฑj

+,
+ป

~>
+ป

,-ฑi

-ป
""ป

it-
ฑป
+,

+,
""ป

"t
t

ฑ
+

-
+

^-

_
_

ฑ.
-
-.

.
-


      examples  of chemical constituents in  each  waste category9  refer  to
Table 6.1.                          :
2 Soil types are cohesionless permeable  soil (A)  and cohesive soil with  a low
permeability (B).
^Explanation of symbols used:
  "-"   means generally not applicable.
  "ฑ."   means applicable in principal in some cases.
  "*"   means applicable in principal.
  "•H-"  means in some cases applicability is  proven.
  "++"  means applicability is proven.
                                     392

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                                SECTION 7
                   CONCLUSIONS AND RECOMMENDATIONS
7.1   CONCLUSIONS

Based  on the  information  gathered  and reviewed during  this  study, the
following conclusions have  been drawn:

1.    The  issue   of  assessing   the  significance  of  contamination  and
      establishing  cleanup  goals  for waste contaminated  land is  a complex
      and  difficult one. It  is  the  subject  of  continuing  and  sometimes
      heated debate wherever contaminated land problems are addressed.

2.    There  are very few  nations  where an  explicit, nationally  consistent
      approach to establishing cleanup  goals has  been  promulgated, yet
      this  has been  identified  by  some  as  essential  to  successful  site
      remediation.   The approach(s) used  appear to reflect, in part, the
      perceived  need  for  cleanup   and   the   general  attitude   toward
      environmental protection.

3.    Approaches  to  establishing  cleanup  goals  vary  widely within  and
      between  nations around  the world.   Approaches  most commonly used
      include ad hoc site by site  negotiation and decision making, reference
      to background  levels,  application of  predetermined  standards  and
      criteria,  site specific mathmatical modeling and risk assessments, or a
      combination thereof.

4.    The  approaches used  are  subject to continuing  re-examination and
      refinement.    Even   in   nations  with   apparently  long-established
      programs for dealing  with  contaminated land, there is much  debate
      regarding   the  most  appropriate  approaches  for  assessing  the
      significance  of contamination and establishing  cleanup  goals.

5.    Allowing  higher   residual concentrations of  contaminants (i.e.  lower
      soil and ground water quality) for less sensitive  current and  future
      land  uses (e.g. industrial  site  versus  housing  development)  was a
      consistent component of most  approaches.

6.    There  was  an  expressed  need for  site  by  site  flexibility  and
      consideration of local conditions in setting final cleanup levels.

7.    Some form  of  standards-based approach  employing soil and  ground
      water  quality criteria  is viewed as essential for  site  screening and
      initial  assessment as well  as for setting cleanup  goals  for  common,
     , non-catastrophic  sites.   It  is also needed  to  assess  the performance
      of treatment processes and  plants for cleaning contaminated soil.  For
      complex  and catastrophic  sites,  a site-specific risk  assessment and
      risk management  approach  will likely  be necessary.
                                     393

-------
8.    Initial remediation  activities  largely  involved excavation and offsite
      treatment and/or landfilling.  There is increasing interest in and use
      of onsite  and  insitu  treatment, technologies.    A  wide  variety  of
      processes  are available  for, treatment  of  contaminated soils,  both
      offsite and onsite/insitu.   Comprehensive  research  and development
      projects  are ongoing in several nations to develop  new procedures
      and   processes   and  to  develop  sound  design  and  performance
      databases.
7,2   RECOMMENDATIONS

1.    It is  recommended that the  results  of  this  study be  considered in
      light of applicable or appropriate and relevant Norwegian  regulations
      and  that  the issue  of establishing  cleanup  goals  for  contaminated
      land be openly  discussed and  resolved. This  should  be accomplished
      early  in   the  development  of  Norway's  program  for  addressing
      problems with hazardous waste contaminated land.

2.    The approach which  proves pnost appropriate for Norway will depend
      on  a  careful analysis  of many  factors,  of  a  technical  and  non-
      technical nature.   It is likely that  a combined approach  will  prove
      satisfactory.  This approach probably  will have some  type of  site
      classification as a basis.   A  standards-based  approach  should  prove
      workable for initial site assessment and  establishing cleanup goals for
      common,  non-catastrophic sites.   For high hazard and  catastrophic
      sites, a site-specific risk assessment and  risk management approach
      will probably  be required.    '
                                    394

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                                SECTION 8
                               REFERENCES
1.     Johannsen,  J.    1988.     Special   waste  section,  Norwegian  State
      Pollution Control Authority, Oslo.  Personal communication, 9 Aug. &  6
      Dec. 1988.

2.     Smith, M.A. 1988.   An international study  on social  aspects  etc.  of
      contaminated land.  In: K. Wolf, W.J. van den  Brink, F.J.  Colon (eds.),
      Contaminated  Soil *88, Kluwer Academic Publishers,, London,  pp.  415-
      424.

3.   .  Moen, J.E.T.   1988. Soil protection in The Netherlands.  In: K.  Wolf  et
     . al.'.[see 2*], pp. 1495-1503.              ,

4.     Bachmann, G.  and D,FซW. von Borries.    1988.    Soil protection  and
      abandoned hazardous  waste  sites.  In: K. Wolf et  al. [see  2.J, pp.1549-
      1554.        '          '          "        '

5.  ,   Van Drunen, T.S.G,  and F.B,  deWalle.  1988.   Soil pollution and reuse
      of  cleaned-up  soils  in  The  Netherlands.    Proc.  conf.  Soil,  The
      Aggressive Agent.  Oct. 1988. IBC Technical Services Ltd., IBC House,
      Canada Road,  Byfleet,  Surrey, England.

6.  .   U.S. Congress Office  of  Technology Assessment.   1985.   Chapter  4:
      Strategies for setting cleanup goals,  In:  Superfund  Strategy,  Report
      OTA   ITE-252.  pp. 103-121.                   \

7.     Kavanaugh,  M.  1988.    Hazardous  waste  site  management:   water
      quality issues.   Report  on  a  coEoquium  sponsored  by  the Water
      Science and  Technology Board,  U.S. National Research Council.  Feb.,
      1987.  National Academy Press, Washington, D.C.   pp.  1-10.

8.     Richardson, G.M.  1987.  Inventory  of cleanup criteria and methods  to
      select criteria.   Unpublished  report,  Industrial Programs  Branch,
      Environment Canada, Ottawa, Ontario.  46 p.

9.     Beckett,  M.    1988.   Current  policies  in  the   U.K.  and  elsewhere.
      L.U.T. Shortcourse on Contaminated Land.  Sept.,  1988. 12 p.

10.   Vegter,  J.J.,  J.M  Roels  and  H.F.  Bavinck.    1988.   Soil  quality
      standards: science or science fiction. In: K. Wolf et al.  [see  2.],  pp.
      309-316.

11*   Palmarck,  M.  et al.   1987.    Contaminated  land  in the  European
      Communities:   Summarizing  Report.  Report UBA-FB.  Commission  of
      the  European Communities,  Brussels. 216 p.

12.   Goubier,  R.     1988.     Inventory,  evaluation   and treatment  of
      contaminated  sites in  France.  In: K. Wolf et al.  [see 2.],   pp. 1527-
      1535.
                                    395

-------
13.    Keiding,   L.M.,  L.W.  Sorensen  and  C.R.   Petersen.     1988.    On
      investigation and redevelopment  of contaminated sites.   Proc. conf.
      Impacts of Waste Disposal on Ground Water.  Aug.  1988, Copenhagen.
      Danish Water Council.

14.    Sorensen,  L.W.    1988.    Waste   Sites  Office,   National  Agency  for
      Environmental Protection, Copenhagen.  Personal communication, 5 Oct.

IS.    von Heidenstam, O.  1988.  Swedish National Environmental Protection
      Board, Stockholm.  Personal communication,  10 Nov. 1988.

16.    Assmuth,  TJ  et  al.   1988.   Assessing  risks  of toxic  emissions  from
      waste deposits in Finland.  In: K.  Wolf et al. [see 2.],  pp.  1137-1146.

17.    Brown,  H.S.   1988.   Some approaches  to  setting  cleanup  goals  at
      hazardous waste sites.  In: Hazardous waste  site management:   water
      quality  issues.   Report on  a  colloquium  sponsored by the  Water
      Science and Technology Board, U.S. National Research Council.  Feb.,
      1987.  National Academy Press, Washington, D.C,  pp.  34-66.

18.    U.S.  Environmental  Protection  Agency.    1987.   Hazardous  Waste
      System. Office of Solid Wastes and Emergency  Response, Washington
      D.C.  pp 3-7.

19.    Anonymous.     1988.     Contaminated  sites   rehabilitation   policy*
      Gouvernement du Quebec, Ministere de L'Environnement, Direction  des
      substances dangereuses. Sainte-Foy, Quebec, Canada.  43 p.

20.    ICRCL.    1987.   Guidance  on the  assessment  and  redevelopment  of
      contaminated  land.     ICRCL  59/83   (2nd   ed.),  Department   of
      Environment, London.   20 p.

21,    Bavinck,  H.F.   1988.   The Dutch  reference  values for soil  quality.
      Ministry   of   housing,   physical   planning   and   environment,
      Leidschendam, The  Netherlands.  9  p.

22.    DeBruijn,  P.J. and F.B. deWalle.    1988.    Soil standards  for  soil
      protection and remedial action in The  Netherlands.   In!   K. Wolf et
      al.[see 2.], pp. 339-349.

23,    Vegter, J.J.   1988.   General  secretary  for Technical Commission  on
      Soil  Protection,   Ministry  of   Housing,   Physical   Planning   and
      Environment,  Leidschendam, The  Netherlands. Personal  communication
      16 Dec. 1988.

24,    Franzius,  V.   1988.  Federal Environmental  Agency,  Umweltbundesamt,
      Berlin.  Personal communication,  26 Oct. 1988.

25,    Assmuth,  T.    1988.    Technical  Research  Office, National  Board  of
      Waters  and Environment,  Helsinki.   Personal  communication,  8  Nov.
      1988.
                                    396

-------
26.   '. Wisconsin  Administrative   Code.     1986.     Department  of  Natural
      Resources, Chapter NR140,  Ground  Water Quality  Standards. Madison,
      Wisconsin.  USA.

27.    Clarke,  J.E.  et  el.   1987.   Interim  guidelines  for  PCBs  in  soil.
      Report  to  the  Canadian   Council  of  Resource  and  Environment
      Ministers.    Environment   Canada  and  Ontario  Ministry  of   the
      Environment.

28.    Anonymous.   1988.   Interim  guidelines  for  PAH  contamination  at
      abandoned  coal  tar  sites.  Canadian   Council   of  Resource   and
      Environment  Ministers.

29.    Lupul, S.L.  1988.   Branch Head,  Industriall Wastes Branch, Alberta
      Environment,   Waste   and   Chemicals   Division,  Edmonton,  Alberta,
      Canada. Personal communication, 8 Dec*  1988.

30.    Hinsenveld, M.   1988.  TNO Division of  Technology  for Society.   7300
      AH Apeldoorn.  The Netherlands.  Personal communication on 11 Oct.

31.    Moen,  JET,  Cornet  JP,  Evers,   CWA.   1986.    Soil protection   and
      remedial actions:  criteria  for decision  making  and  standardization of
      requirements.   In:   Contaminated   Soil,   ed.    Assink,   J.W.    and
      Vandenbrink, WJ,  Martinus  Nijhoff Publishers, Dordrecht.

32.    Franzius, V., Stegmann,  R.  and Wolf, L.   1988.   Handbuch der atlasten
      sanierung.   R.v.Decker's  Verlag,  G.  Schenck,  Postfach  102640.  6900
      Heidelberg, FRG.

33.    U.S. Environmental Protection Agency.   1988.  Technology screening
      guide  for treatment of   CERCLA  soils  and   sludges.    Publication
      EPA/540/2-88/004.   Office  of Solid  Waste  and Emergency  Response.
      401 M.Street, S.W., Washington, D.C. 20460.  USA.

34,    Preslo,   L.M,   et  al.   1988.    Remedial,  technologies  for  leaking
      underground storage tanks.  Lewis Publishers.  121 S. Main Street,
      Chelsea, Michigan. 48118. USA.  216 pp.

35,    Achakzy, D., Schaar, H,  Luher,  H.-D.,  and  Poppinghaus,  K.   1988.
      Technologien zur sanierung kontaminierter  standorte (Status report
      on  remedial  actions   of  contaminated sites  -  technologies  and  R+D
      activities).   Bundesministerium   fur   Forschung    und   Technologic
      (BMFT),  Postfach  200708, 5300 Bonn 2, FRG.  ( in  German)  232 pp.

36.    Hoffman, M.S.(ed,). 1989. World Almanac  and Book  of  Facts.   Pharos
      Books,N.Y. USA,
                                     397

-------
SECTION 9
APPENDIX
    398

-------
                         APPENDIX A
PERSONAL INQUIRIES AND SITE VISITS MADE AS  PART OF THIS STUDY
                              399

-------
Table Al.   Principal inquiries providing information regarding cleanup
            standards and technologies for  hazardous waste contaminated
            land.
Nation
Agency
Contact
United States

o U.S. Environ. Protection Agency, Cincinnati
o U.S. Environ. Protection Agency, Washington D,C.
o New Jersey Dep. of Environmental  Protection

Canada
o Environment Canada,  Burlington, Ontario
o National Water Research Inst., Burlington, Ontario
o Alberta Environ. Res.Ctr.,  Vegreville, Alberta
o Stablex Canada, Inc., Blainville, Quebec
o Alberta Special  Waste Manage. System,  Swan  Hills

England
o Department of the Environment, London
o Clayton Bostock Hill & Rigby, Birmingham

The Netherlands
o TNO Div. of Technology for Society, Apeldoorn
o TNO Div. of Technology for Society, Delft
o Nat. Institute of Public and Env. Prot, Bilthoven

o Ministry of Housing, Physical Planning and
  Environment, Leidenscham
o Association of Process-Based  Soil Treatment
  Companies  (NVPG), Voorburg

gjer,manyi:
o Federal Environmental Agency, Berlin
o Office  of Remedial Action,  Hamburg

grance.
o Hazardous  Sites Team, Angers

Denmark
o Agency for Environmental Protection, Copenhagen
o Danish Technical University,  Lynby

o Danish Geotechnical Institute, Lynby
o Geotechnical Soil Cleaning, Kalundborg
                                   R. Hill
                                   Dr. W. Kovalick,Jr.
                                   R. Dime
                                   T.W. Foote
                                   Dr. R.E.  Jackson
                                   D. Conrad
                                   P. Grenier
                                   A. Wakelin
                                    M.J. Beckett
                                    M.A. Smith
                                    M. Hinsenveld
                                    Dr. F.B. deWalle
                                    E.R. Soczo
                                    K. Visscher
                                    J.J.  Vegter

                                    F.E. Boeren
                                    F. Norman
                                    V. Egmond

                                    Dr. V. Franzius
                                    K. Wolf
                                    Dr. V. SokoUek

                                    R. Goubier
                                    L. W. Sorensein
                                    C. R. Peter sen
                                    Dr. T. Christiansen
                                    Dr. S. Vedby
                                    M. Poulsen
                                    S. Hanson
                                    400

-------
Table Al.cont.     Principal inquiries providing information regarding
                  cleanup standards and technologies for hazardous waste
                  contaminated land.
Country
Agency
Contact
Sweden
o National Environmental Protection Board, Stockholm  M. Appelberg
                                                     B. Sodermark
                                                     O. von Hedenstam
o Swedish Geotechnical Institute,  Linkoping           Bซ Carlson
                                                     S. Eullberg
Finland •
o National Board  of Waters and Environment, Helsinki  T. Assmuth
                                                     T. Laikari
Norway
o State PoEution  Control Authority, Oslo              O. M. Grini
                                                     J. Johansen
                                                     M. HeUe
o Oslo Renholdsverks, Oslo                            E. Bjerkelund
                                   ~401

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Table A2.   Principal site  visits yielding information regarding cleanup
            standards and technologies for hazardous waste contaminated
            land.                    :
Nation      Description
The Netherlands
o     Study visit (11-12 October  1988):                     .
      -     TNO  Division of Technology for Society, Appeldoorn  and Delft.
      -     National Institute of Public Health  and Environmental
            Protection, Bilthoven.
            Assn. of Process-based Soil Treatment Companies, Voorburg.
      -     Gouderak waste site cleanup (old shoreline landfill).
            Ecotechniek soil treatment plant (thermal), Utrecht.
      -     HWZ  soil treatment  plant (extraction), Amsterdam.

     Germany
o     Study  visit (21-22 February 1089)?
            Institute for air, water, and soil research, Langen.
      -     Office of Remedial Action, Hamburg.

Denmark
o     Seminar on Remedial Action Technologies in the USA, FRG and Canada,
      12 August 1988, Technical University of Denmark, Lynby, Denmark.
o     Study  visit (5-6 October  1988)s
      -     National Agency for Environmental Protection, Waste Sites •
            Office, Copenhagen.
            Waste contaminated land cleanup (paint factory).
            Biotechnical Soil Cleaning Ltd.

Sweden                             ;
o     Study  visit (28-29 September, 10 November 1988):
      -     National Environmental Protection Board, Stockholm.
      -     Swedish Geotechnical Institute, Linkoping.
            SAKAB hazardous waste treatment plant, Kumla.

Finland
o     Study  visit (8-9 Nov.  1988)5
      -     National Board of Waters ; and the Environment, Helsinki.
      -     Waste sites  (paint factory, lead smelter, incinerator).
            EKOKEM hazardous  waste treatment plant, Riihimaki.
Norway
o     M
o     Visits to various current or potential waste sites  in Norway.
o     Meetings with the State Pollution Control Authority, Oslo.
                                    402

-------
        SAMPLING METHOD EFFECTS ON

 VOLATILE ORGANIC  COMPOUND MEASUREMENTS

        IN  SOLVENT  CONTAMINATED SOIL
                      By
         Robert L. Siegrist, Ph.D., P.E,
            Visiting Senior Scientist
         Fetter D. Jenssen, Dr.  scient.
                Senior Scientist
Institute for Georesources and Pollution Research
          Postlox 9,  N-1432 Aas~NLH
                    Norway
                     403

-------
                                 CONTENTS
Contents	2
List of Figures.	   3
List of Tables 	 ............... 	   5
Acknowledgments	.	7

Section 1.  Summary.	  ....   8

Section 2.  Introduction ........................  11
            Background 	 . 	 ..........11
            Soil Sampling.	  12
                  Soil Sampling Process	  12
                  Current Sampling- Practices ......... 	  14
            Study Purpose. . . . ป	  14

Section 3.  Materials and Methods. ...................  16
            Experimental Approach  ...................  16
            Experimental Apparatus . 	 ...........17
                  Soil Material.	  17
                  Soil Column Preparation	.....17
                  Soil Column Flow System.	...24
            Target Contaminants and Feed Solution Preparation	25
            Soil Column Contamination	.30
            Sample Collection, Handling and Analyses	 .  31
                  Feed and Outflow Solution Samples. . ........ .31
                  Co limn Soil Samples	32
                  Analytical ................. '".  . .  . ".'• 35
            Pan Evaporation Test	  37

Section 4.  Results and Discussion	38
            Column Contamination Characteristics	  38
            Feed and Outflow Solution Characteristics. .........  39
            Soil Column Characteristics Following Contamination.  ....  42
            VOC Distribution . . .; .	44
            Solution VOC Retardation		46
            Soil Sampling Method Effects	 .46
                  Sampling Method Comparison 	 .........  46
                  Sampling Method Bias .................  50
                  VOC Bias Mechanisms. .	  53
                  Implications .	  53

Section 5.  Conclusions	  ....  56

Section 6.  References	 .......  59
                                  '                     '' •?
Section 7.  Appendix ..........................  62
            A. Solution VOC Breakthrough Curves  ............  63
            B. Characteristics of (the VOC soil samples	, ...  67
            C. Soil VOC Sampling Effects Charts. . . . .  . . .. ."ป .  . .69
            D. Quality Control Sample Analyses	ซ...  73
                                  :404

-------
                             LIST OF  FIGURES


                                                                      Page

2.1.  Sampling component activities involved in laboratory
      measurement of soil properties ........... .....  ..13


3.1.  Grain size analysis of the soil used in this experiment.  .....  18

3.2.  Construction details for the soil columns used in this experiment.  19

3.3.  Soil column within an x-ray tomograph. . . ...... .  .....  21

3.4.  Tomography x-ray image of a horizontal cross-section of the
      test soil column .................. .......  22

3.5.  Relative soil density variation within 4 ion thick horizontal
      sections of the test column  . ..................  23

3.6.  Photograph of the experimental apparatus ... ....... ...24

3.7.  Soil column flow system apparatus  ... ............ .23

3.8.  Soil sampling plan view of the test soil column  ..... . ...  32

3.9.  Photograph illustrating the soil sampling tube insertion .....  34

3.10. Photograph illustrating the five soil samples in their
      respective containers. .. .............. .  .....  34
.4.1.  Breakthrough curve for the Tritium tracer () added to the feed
      solution for the test column ................... 38

4.2.  Breakthrough curve for the Tritium and the six target VOCs
      studied  ..... ..... ........... ...... . . 40

4.3.  Average concentrations of target VOCs in soil samples as a
      function of sampling method .................... 47
Al.   Solution breakthrough curve for methylene chloride ... ..... 64

A2.   Solution breakthrough curve for 1,2-dichloroethane . ....... 64

A3.   Solution breakthrough curve for 1,1,1-trichloroethane  ...... 65

A4.   Solution breakthrough curve for triehloroethylene, ........ 65
 ป-.',',
AS.   Solution breakthrough curve for toluene  ....... ..... .66
                                    405

-------
                             LIST OF FIGURES





                                                                      'Page



A6.   Solution breakthrough curve for chlorobenzene  .  ... . .....  66





Cl.   Comparison of sampling method effects for methylene chloride .  .  .70



C2.   Comparison of sampling method effects for 1,2-dichloroethane .  .  .  70



C3.   Casparison of sampling method ^effects for i,lfl-triehloroethaiieป  .'71



C4.   Comparison of sampling method effects for trichloroethylene. .  .  .71



C5.   Comparison of sampling method effects for toluene  ........72



C6.   Comparison of sampling method effects for chlorobenzene  .....  72
                                    406

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                             LIST  OF TABLES


                                                                      Page

2.1.  Frequency of GdcUrrence of volatile organic compounds at
      Superfund halMFdous waste sites in the USA . .  < ซ  *.  a	.11

2.2.  Examples of documented guidance information for
      collection and preservation of soil samples for V6C analyses ...  15


3.1.  Sampling method effects evaluated in this experiment  .	16

3.2.  General properties of the soil used in this experiment ......  18

3.3.  Characteristics of the soil columns prior to contamination ....  20

3.4.  Sources and USeS of VOCs selected for inclusion in this study. .  .  26

3.5.  Some chemical properties of the target VOCs. .  ป t  t  e *	26

3.6.  Transport and fate properties of the target VOOsi i  ซ  * *	27

3.7.  Schedule of sampling the test column feed and outflow Solutions.  .  31

3.8.  Soil sample collection methods evaluated in this study	33


4.1.  Results of analyses of test column feed and outflow samples
      for pH and specific conductance	.  .  39

4.2.  Comparison of VOC concentrations in the feed and stock
      solutions	40

4.3.  Results of VOC analyses of the test soil column feed and outflow
      solutions.	41

4.4.  Characteristics of the soil columns after contamination. .....  42

4<>5.  Water content and total organic carbon content in soil
      samples collected from the soil columns following contamination.  .  43

4<>6.  Calculated VOC sorption affinities for the soil used in
      this experiment	44

4o7.  Calculated equilibria distribution of the target VOCs
      within the test soil column	45

4.8.  Concentrations of VOCs in soil samples from the test colum. ...  48

4o9.  Magnitude and significance of differences observed in the
      sampling method effects	49
                                    407

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                             LIST,OF TABLES


                                    '  '                  '              Page

4.10. Comparison of measured VOC concentrations versus estimated
      concentrations for the conditions of this experiment .	,51

4.11. Relative sampling bias associated with different elements of
      the sampling methods tested in this study.	ป ...  52

4.12. Potential VOC bias mechanisms associated with
      the sampling methods tested in this study.	„ ...  54



Bl.   Characteristics of the test column soil samples used for VOC
      analyses	  68


Dl.   VOC analytical method detection limits . . . . .	  .  ,  T4

D2.   Characteristics of samples for quality control analyses. ......  74

D3.   Results of VOC spiking and recovery analyses . . . . .  . . . .  .'. .  75
                                    408

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                            ACKNOW LEDGMENT S
The   research  reported  herein  was  conducted  at  the   Institute   for
Georesources  and  Pollution  Research  (GEFO) located at  the Agricultural
University of Norway (NLH)  in Aas,  Norway.  The  research was conceived
and  directed  by Dr. Robert  L. Siegrist,  Visiting Senior  Scientist at GEFO,
with  valuable  assistance  provided   by   Dr. Fetter  D.  Jenssen,   Senior
Scientist, GEFO.

There are  many other individuals and organizations who  contributed to  the
successful completion of this  research. Dr. fore 0steraas and Per Kr. R0hr
.are  acknowledged  for  their  assistance in  arranging  for financial  support
for this  and other  research activities. The Norwegian  State Pollution Control
Authority  (SFT), Oslo,  is acknowledged for providing a  substantial  portion
of the financial support for this research. Oddvar Ringstad and The Center
for Industrial Research  (SI),  Oslo, are acknowledged for  preparation of  the
volatile  organic compound  (VOC)  stock solution  and conduct of the  VOC
analyses.   The Department  of  Soil  Science at  NLH is  acknowledged  for
conduct  of the basic soil physical and chemical  analyses.  The  Tomograph
Laboratory at NLH  is  acknowledged  for  the computer-assisted  tomography
portion of the work.   The Isotope Laboratory at NLH is acknowledged  for
the Tritium analyses.

Inquiries regarding the research  may be  directed to Dr. Siegrist at GEFO,
Postbox  9, 1432 Aas-NLH, Norway,  Tel. 47-9-948140 or  at  4014  Birch  Avenue,
Madison, WI, 53711,  USA, Tel. 1-608-2387697.
                                    409

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                                SECTION 1
                                 SUMMARY
Soil  contamination by volatile organic compounds (VOCs)  can lead to time-
consuming- and  costly  investigation and  cleanup actions.   It is therefore
essential that decisions  regarding the significance of contamination and the
need for  cleanup   be  based  on  accurate   measurements  of  the  VOC
concentrations  present. VOC measurements in  soil  systems  are  subject  to
many sources  of error,  perhaps  the most  important  of  which are  the
systematic  errors   or   bias associated  with  sample  collection  methods.
Despite  this  fact, comparatively little research has  been done to elucidate
the  effects  sampling   methods   can  have   on  the   accuracy  of  VOC
measurements in  soils.  To  further  the  understanding  of  this subject,
research was conducted during early 1989 at  the Institute for Georesources
and  Pollution Research  in  Aas, Norway.

A  laboratory experiment  was  conducted  to  investigate  the  effects  of
sampling1 methods on VOC concentrations  measured  in solvent contaminated
soil.  Five  different methods  were used  to  assess  the  effects  of  sample
disturbance, container  heads pace  volume,  container integrity  and  infield
methanol preservation.

The  study soil was  a naturally occurring surface soil (top 50 cm) of  sand
texture  (97% sand) obtained from  the Mona glaciofluvial deposit near  Mysen,
Norway.   The field moist soil was characterized by a water  content of  8.6%,
pH of 5.21, total organic carbon (TOC) content of 0,4%, and cation exchange
capacity of 4 meq/lOOg.  The study  soil was  uniformly  packed  into 15 cm
diameter by  15 cm long glass columns.  Two columns  were prepared, one for
control  purposes and one  for  testing the sampling  method  effects,.  Spatial
uniformity was confirmed by computer-assisted  x-ray tomography.

The  soil in  the  test column was uniformly contaminated  under  conditions
simulating a chemical  waste discharge.   An  aqueous solution   containing
different concentrations of six common VOCs was passed through  the  column
by   saturated   upflow.  The   VOCs  and  the   respective  feed  solution
concentrations were methylene chloride (157.5 mg/L), 1,2-dichloroethane (130
nป(j/L)f  1,1,1-trichloroethane  (16  mg/L),  trichloroethylene  (12.8   mg/L),
toluene  (4.5 mg/L) and chlorobenzene (2.85 mg/L).

Contamination of the soil column  occurred in  a temperature-controlled  room
at 10ฐCป Over a  period of ca.  2.5  hr., ca. 15 pore  volumes of the solvent
solution  were passed through  the test column  at  an average flux:  of 870
cm/d.  The control column was treated in a similar  fashion  but without the
target VOCs  in the feed solution.

During  contamination of the test  column, samples of  the  column foed and
outflow  solutions were coEected. Analyses of each target VOC  were made by
gas  chromatography.  The target VOCs were  not markedly  retarded  during
saturated flow  through the  soil  column.   This  observation was  consistent
with predictions  based on empirical relationships for  sorption as  a function
of VOC  water solubility and soil  organic  matter content (retardation factor
(RF) = 1.1  to 2.6).
                                   410

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Following contamination, the soil  was desaturated by  applying a tension to
the bottom of the column.   Entry air replacing the drainage water had been
equilibrated  with the feed solution.  Following desaturation the  test column
was allowed to equilibrate at 10ฐC overnight (ca. 17 hr).

Each  soil column was  then embedded  in  a box  filled  with  10ฐC  soil and
moved to an ambient temperature room for sampling (20ฐC).  This was done
to simulate  field conditions  where samples  of  relatively  cool  soil are often
removed and containerized in a warmer ambient temperature environment.

Replicate  soil samples  were collected from the test column by five  different
methods.  All samples were stored at 2-4ฐC  immediately  following collection
and during pre-analytical holding. Each soil sample was analyzed  for each
of the target VOCs  by extraction and gas chromatography.  Analyses were
also  made for soil  water content  and organic  carbon  content.    Quality
control analyses were  made of samples of clean soil,  soil samples  from  the
control column and of the methanol used for infield preservation.

The. results of the soil analyses  revealed that sampling  method effects  can
be  substantial  and significant*   Based  on  a least  significant difference
analysis,  the ranking  of  VOC  concentration by sampling  method from  the
lowest to the highest concentration measured was,

      Sampling Method  E  < A 1 D  <  B   <  C
where,

   Method E=  disturbed sample in lab  grade plastic bag, low headspace,
   Method Aa  undisturbed  sample, Teflon  sealed glass jar, high headspace,
   Method D-  disturbed sample, Teflon sealed glass jar, low  headspace,
   Method B=  undisturbed  sample, Teflon  sealed glass jar, low  headspace,
   Method C=  undisturbed  sample, Teflon  sealed glass jar, infield
                 immersion in methanol.

In general, the  sampling  methods  could  be categorized into three groups
based on roughly similar measured VOC concentrations:

   1)   Lowest = Method E (non-detectable levels),
   2)   Medium = Methods A, D and B (ca.  11 to 91% of Method C), and
   3)   Highest = Method C.


The   differences between VOC  concentrations  measured  by  the  different
sampling  methods became smaller with  decreasing solubility and volatility of
the  target  compound. For  example,  the  differences  between  sampling
methods  for  1,2-dichloroethane  were  considerably   greater  than  for
chlorobenzene.

Assuming the VOC  concentrations measured  in  the  samples  collected  by
infield  methanol  preservation  represent  the  best  approximation to  the
"true" concentration, the  reductions in VOC concentrations measured in  the
other samples may be interpreted as systematic error or bias.
                                   411

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For the  soil samples  containerized in Teflon sealed glass jars, the lack of
infield immersion in methanol  contributed the greatest negative bias  (up to
81%).   High headspace volume and disturbance  contributed considerably less
bias (up to  11%),   The negative  bias observed  was comparatively less for
the VOCs with lower solubilities and volatilities.  Collection of  disturbed soil
samples in plastic  bags yielded non-detectable levels of VOCs  or essentially
1QQ& negative bias.

Procedures for  sampling soils for VOC analyses must account for the  special
properties and  behavior of these compounds. Collection of soil samples with
containerization in  plastic bags is clearly unacceptable where analyses for
VOCs   are  intended.    Containerization  in  a  Teflon  sealed   glass  jar is
workable  and  appropriate,  but  decisions  regarding  sample  disturbance,
headspace  volume  and  infield  methanol  preservation appear  subject  to
considerations associated  with VOC properties and contamination levels.

For analyses of VOCs with relatively low solubilities and  vapor  pressures
(e.g. chlorobenzene),  collection of a disturbed sample with containerization
in a Teflon sealed glass jar and refrigeration at 4ฐC  would usually provide
an accuracy similar to that of more complex methods.   For such samples, it
is  better  to  collect  a  disturbed  sample  and  completely  fill  a  sample
container rather than collect  an undisturbed sample which results in a high
headspace volume in the container.

Conversely, for analyses of VOCs with  relatively  high solubilities an,d vapor
pressures,  and  particularly  where  concentrations  are  anticipated  in  the
range  of a  cleanup action level (e.g.  1,1,1-trichloroethane at ca. 1 ppm),
enhanced accuracy requires  the collection of an undisturbed sample with
containerization in  a  Teflon sealed  glass jar, infield immersion in methanol
and refrigeration at 4ฐC.

Further  research is necessary and appropriate to extend the  results of the
work  reported  herein to other  VOCs  and  the   diversity  of  conditions
experienced in  soil systems and sample  collection environments.
                                    412

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                                SECTION 2
                              INTRODUCTION
2.1  BACKGROUND

When  characterizing  waste  contaminated  land,  soil  analyses  are normally
conducted  for  a  wide range  of  potential  contaminants.    Due  to  the
widespread use  and occurrence  of  organic  solvents, soil samples  are often
analyzed for  volatile organic  compounds  (VOCs)   (e.g.   trichloroethylene,
toluene). Solvents  and related organic compounds  are found  in products
used in  households, commercial  businesses  and  industrial facilities.   VOCs
are routinely  present in waste contaminated land (Table 2.1).
Table 2.1.   Frequency  of occurrence of volatile organic compounds
            at  Superfund hazardous waste sites in the USA [7].l
Rank2
Compound
VOC
% of Sites
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
Trichloroeth.vlene3 *
Lead
Toluene *
Benzene *
PCB's
Chloroform *
Tetrachloroethylene *
Phenol
Arsenic
Cadmium
Chromium
1.1.1-Trichloroethane *
Zinc and compounds
Ethylbenzene *
Xylene *
Methylene Chloride *
Trans-l,2-Dichloroethene *
Mercury
Copper and compounds
Cyanides (soluble salts)
Vinyl Chloride
1.2-Dichloroethane
Chorobenzene
1,1-Dichloroethene
Carbon Tetrachloride
33
30
28
26
22
20
16
15
15
15
15
14
14
13
13
12
11
10
9
8
8
8
8
8
7
   Based  on 546  uncontrolled hazardous  waste  sites.
   Rank of  occurrence from highest to lowest.
   Compounds underlined  were selected for inclusion in this experiment.

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The  transport  and fate of VOCs in soil systems involve  complex processes
in a diverse and dynamic environment.  In aqueous solutions,  VOCs tend to
be mobile in the  environment,  often only  weakly  sorbed to soil particles.
Under some conditions,  VOCs  can , persist  for  extended  periods.    Under
other  conditions  VOCs  can  degrade,  sometimes into harmless  breakdown
products, but  other times into more harmful compounds. VOCs in ground
water  can pose serious  problems as they can  be harmful  and potentially
carcinogenic in   drinking  waters  at  very  low  concentrations  (e.g.  5
micrograms  per liter (ug/L) or parts per billion  (ppb)).

SoE   contamination   by  VOCs   can'  lead   to  time-consuming  and   costly
investigation and  cleanup actions.   It  is  therefore essential that  decisions
regarding the  significance of  contamination and the  need  for  cleanup be
based on accurate  measurements  of the VOC  concentrations present.  Yet
accurate  and  precise  measurements  of  VOC concentrations  in soils  are
difficult  to  achieve since they  are subject  to numerous  sources of  errors,
both  random and systematic [1].


2.2  SOIL SAMPLING

2.2.1  .S.QJL Sampling Process

There are  a  number  of  activities  which  must  take  place  in  order to
quantify VOC concentrations in  soils (Figure 2.1).   Obviously, each of these
activities can introduce errors such1 that the "measured" value deviates, in
some cases  substantially, from the  "true"  value.   For  a given  sample
location  and time, error  can  arise' from  sources  within both  the  sample
collection and sample  analysis processes.   While  both  components  are
important, the  sample collection process is thought to contribute relatively
large errors in comparison to the analytical process.     This is particularly
true of trace level concentrations  (i.eซ < 1  mg/L).   Despite  this, efforts to
understand  the  errors associated  with  sample collection  methods and to
develop appropriate  quality assurance techniques have so far been limited.

Soil  sample  coEection errors can be random or  systematic.  Random  errors
can  usually be  effectively  managed  through  statistical techniques (e.g.
increasing  number of samples).    Systematic  error  or  bias  is far  more
elusive.   Positive bias (i.e. measured  value  >  true  value) can occur  by
extraneous  sample  contamination (e.g. cross-contamination of samples).  This
bias  can  normally be  managed through quality assurance  provisions (e.g.
trip  and field  blanks).              ;

Negative bias  in  VOC  measurements (i.e.  measured value < true  value) is
more difficult  to  delineate and control.    It  can  be  caused  by diverse
factors including:  1) volatilization losses  during soil  surface exposure and
sample removal from the  soil profile, 2) volatilization losses from the sample
container  during   pre-analytical  holding,  3)  chemical and  biochemical
transformations during pre-analytical  holding  and 4)  volatilization  losses
during subsampling for analyses.
                                     414

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                  "TRUE"  PROPERTY OR CHARACTERISTIC
                (Inherent temporal and spatial variability)
                            SAMPLING DESIGN
                  Sample location
                  Sample time  of collection
                  Number of samples
                  Target analytes
                           SAMPLE COLLECTION
                  Expose soil to be sampled (e.g. by  shovel, backhoe...)
                  Remove soil from  natural setting  in a collection device
                  (e.g. shovel, bucket auger, split-spoon, shelby tube...)
                  Remove soil sample from collection device (e.g. by
                  extrusion, spoon...)
                  Containerize soil sample (e.g. in vial, jar, or within
                  collection device itself)
                  Preserve sample  (e.g. cool to 4ฐC, quick-freeze, or
                  immerse in  methanoL..)
                  Sample transportation and storage
                            SAMPLE ANALYSIS
                  Sample preparation (e.g. homogenizing, subsampling,...)
                  Analysis reagents,  apparatus and instrumentation
                  preparation
                  Sample analysis operations
                  Data analysis and interpretation
                  Results reporting
                "MEASURED" PROPERTY OR CHARACTERISTIC
Figure 2.1.  Sampling component activities involved in laboratory
            measurement of soil properties.
                                     415

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In  general,  negative  sampling;  bias  associated  with  volatilization  losses
should, be  inversely  related to VOC soil  sorption affinity. Sorption affinity
in turn is affected by the  properties of the  organic  compound itself (e.g.
hydrophobicity) as weE  as those  of  the soil system  (e.g.  water  content,
organic matter  content,  mineralogy).     For  example,  lower  bias would  be
anticipated when sampling for VOCs possessing lower solubilities and vapor
pressures  and  in  soils   possessing  higher  organic  matter  contents.
Negative sampling bias should also be directly correlated with the presence
of conditions in the  sampling  environment which enhance volatilization (e.g.
higher temperature,  humidity  deficit and air speed).  Particularly important
would  be  differentials  between conditions in  the natural soil  versus those
imposed  by the sampling conditions.     Negative  sampling  bias  associated
with VOC  transformations   during pre-analytical  holding time should  be
directly associated with sample preservation conditions.


2.2.2  Current,...Sampling. Practices

There  are  currently  no standardized procedures for sampling  soils  for VOC
analyses.   Instead, a wide  variety of sample  collection  methods have been
used,  in   some  cases without   regard   for  the  serious sampling  errors
associated  with  them.   Sample  collection  protocols  are often  adopted in
certain geographic settings or on certain types of  projects, largely based
on  personal preference,  regulatory  requirements  or  simply   a  matter  of
convenience.

While  there  are  no  standardized  procedures,  guidance  information  is
available in  a few  published sources  (Table  2.2).   Recognizing the need,
organizations  are attempting to formulate standard soil sampling procedures
where  VOC analyses are involved.   For example, the  American Society of
Testing and Materials  (ASTM) is  near ing completion  of a standard method
for sampling soEs for VOC  measurements [21].    This  method  (draft form)
outlines  optional  collection  procedures,  including   sample  extrusion  and
infield immersion in  methanol.
2.3  STUDY PURPOSE

T-here is growing concern over  the: lack  of understanding of the effects  of
sample  coEection  methods   on   VOC  measurements  and  the  absence  of
standardized  sampling procedures.  Yet, prior investigations  into sample
collection  effects  have  been  limited  and  somewhat  unsuccessful.    For
example, in one of the few reported studies the experimental approach used
involved sampling soils at uncontrolled  hazardous  waste  sites by different
methods,  measuring the  VOC concentrations  in the  soils by  one  or  more
analytical  methods and then comparing  the  VOC  recoveries achieved [19J.
Unfortunately, spatial  variability was  so  great that the significance of any
differences in the sample coEection methods could  not be elucidated.

Clearly,  further research is necessary  and  appropriate.   The  purpose  of
this study was to provide insight  into the field sampMng method effects on
VOC  measurements associated   with  soE sample  disturbance,  container
headspace volume, container  integrity  and infield immersion in  methanol.
                                    416

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Table 2.2.   Examples of documented guidance information for collection and
            preservation of soil samples for VOC analyses.*


Test Methods  for Evaluating  Solid Wastes. U.S. EPA, SW-846, 1986 [23].

      Specific reference to soil sampling for  VOCs
-     Collect  sample (unspecified) and deposit in  4 oz (120  mL) widemouth
      glass container  with Teflon liner
      Minimize sample agitation during collection
-     Minimize free air space in  container
      Cool sample to 4ฐC
      Maximum holding time = 14 days
-     For high level soils (individual  VOCs > 1 mg/kg), extract soil in
      laboratory with methanol.


Characterization of Hazardous Waste Sites.  U.S. EPA,  1984 [8].

      No specific reference to sampling  for VOCs
      Two sampling methods given:
      Soil  sampling with a spade and  scoop
      Subsurface soil sampling with auger  and thin-wall tube sampler
      Minimize aeration  or significant  change in moisture content
      Seal sample in glass bottles with Teflon liners,
      tightly  capped and  protected  from sunlight
—     Maintain sample at temperature  of sample location or  lower
      Refrigerate and analyze as soon as possible


Preparation of Soil  Sampling Protocol: Techniques  and Strategies. 1983 [14].

-     Various sample collection methods noted:
      For surface soils, scoop or shovel,  soil punch, ring  sampler
      For  deeper  soils,  soil probe or  augers, power corers  or  trenching
      For VOCs, use tube sampling  (e.g.  split spoon, density rings) with
      Teflon  caps,  duct tape wrapping,  and cool to 4ฐC
   Inclusion or omission of  a given method is not meant to be
    a recommendation, either favorable or adverse, respectively.
                                     417

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                                SECTION 3
                         MATERIALS AND METHODS
3.1   EXPERIMENTAL APPROACH

To  compare different soil  sampling  methods, it was  necessary to  have a
volume of soil  uniformly  contaminated  with  VOCs under realistic conditions.
Uniform contamination was  necessary to avoid problems  with interpretation
when comparing  spatially separate samples.  It was  also  desired to  know
the  true  level of  contamination  in  order  to  have  an  absolute basis  for
comparison  and  determination of  sampling  error or  bias.    These  two
objectives  were  eventually  found  to  be  mutually  exclusive.    Due  to
anticipated problems  with spatial  variability under field conditions, it was
decided to  conduct  a laboratory  experiment.    A soil column  would  be
contaminated  by VOCs  during  saturated  upflow  of   an aqueous  solution
containing a number  of  target compounds.  By  sampling  the column by
multiple  methods, relative  comparisons  could  be made between sampling:
methods.   As  an absolute  reference,  the  highest  concentration of  VOCs
determined with  acceptable variance could be  considered to  be  the  most
accurate and assumed to approach the "true" concentration at the  time of
sampling'.

The sampling-  method  effects chosen for evaluation in this experiment  are
outlined in Table 3.1.
Table 3.1    Sampling method effects evaluated in this experiment.
Sampling Method Effect
Condition
Sample container headspace  volume
Sample disturbance
Sample container integrity
   40% of container volume
   80% of container volume

   Undisturbed soil core
   Spooned aliquots

   Teflon sealed glass jar
   Polyethylene ziplock bag
Sample preservation
   4ฐC refrigeration
   Infield immersion in methanol
   and 4ฐC refrigeration
                                   418

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The  controlled contamination   of a natural  soil encased  in  a column was
accomplished  by  saturated  flow of  an  aqueous  solution  containing  six
common organic  solvents  under conditions  to simulate a  spill of  solvent
waste water.    Following   contamination,  desaturation  and   equilibration,
replicate soil  samples  were collected from  the column.   Contamination of the
column  was carried  out at  10ฐC while the  sampling  of  the  10ฐC  column
occurred at an ambient air temperature of 20ฐC.   All sampling  utensils and
containers  were also at  20ฐC.   This  was done to simulate field conditions
where  during sampling, cool soil would be removed into a warmer  ambient
air  temperature   environment.    Soil  samples  were  collected  using  five
methods   with   elements   typical   of   field   procedures   (Table   3.1).
Experimental  analyses  included  soil  physical  and   chemical  properties,
computer-assisted  x-ray tomography and radioisotope tracer  studies, and
gas  chromatographic  analyses  of the  target VOC concentrations  in the
column  feed solution, outflow and contaminated soil.


3.2  EXPERIMENTAL APPARATUS

3.2.1  Soil  Material

The  soil used for  this  study was  a naturally occurring surface soil  of sand
texture.  A bulk  volume of  soil (upper  50  cm)  was  collected  from  a sand
and  gravel pit located in  a glaciofluvial  deposit near Mysen,  Norway.   In
the laboratory  the field moist soil was sieved  (4 mm mesh).  A  composite
sample  (5-point) was then collected and duplicate subsamples were analyzed
for various soil properties  by  standard methods [2,17]. Water  content was
determined gravimetrically  at  105ฐC.  Particle  size  analysis  was  made by
sieving and the pipette method.   Soil pH  was measured electrometrically on
a  1:1 soil  paste.   Total organic carbon  was determined by dry combustion.
Cation exchange capacity was measured by the ammonium  acetate method.
The  results of these analyses are shown in Table 3.2 and Figure 3.1.


3.2.2  Soil  Column  Preparation

The  field moist soil described above was carefully  packed into a specially
constructed column with the features  depicted  in  Figure  3.2.   The  column
construction  included  a  15 cm  long  glass  cylinder  with  15  cm  outside
diameter (o.d.) and 0.5 cm wall thickness.  Affixed  to the top  and  bottom
ends of the  cylinder  were  aluminum  plates.   Both  plates  had  a  circular
groove  to facilitate attachment  to  the  glass   cylinder.    Teflon  covered
rubber o-rings  within the  grooves  provided  a  seal between  the  glass
cylinder and  the aluminum plates.

Each aluminum plate had a series of circular and radial grooves  milled into
the. interior   surface  to  facilitate  distribution   and  drainage   of  the
contaminant solution (Figure 3.2).  Between each  of the aluminum  plates and
the  soil within the column  was placed  a  stainless  steel screen (0.6  mm
mesh) overlain by  two layers of glass microfiber filters with  pore diameters
of 1.6 and 1.0 microns (Whatman GF/A and GF/B, respectively).
                                    419

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Table 3.2.   General properties of the soil used in this experiment.
Property
Units
Average  Value^-
Soil texture (USDA)
Grain size analysis:
2.0 - 0.6 mm
0.6 - 0.2 mm
0.2 - 0.06 mm
0.06 - 0.02 mm
0.02 - 0.006 mm
0.006 - 0.002 mm
< 0.002 mm
Water content
PH
Total organic carbon
Cation exchange capacity
Base saturation
—

wt.%
•wt.%
wt.%
wt.%
vtt.%
vrt.%
wt.%
wt.%
units
wt.%
meq/lOOg
%
Sand

50
39
8
2
1
0
0
8.6
5.21
0.44
4.0
9.0
  Based on duplicate analyses of a 5-pt.  composite of field moist soil.
                              SOIL GRAIN SIZE ANALYSIS
                           I
               100
     wt. % <
   DIAMETER
0
0
0
0
0
0.0























01














































































































































0.01











I










tซJ






















Si






















ป4t



































J
f
- \f-
r
\V*
0.1
E_
















A
f
T



















A
V









\






\



A
r









- - •

/
- f
.-/
f,,,,
../-.
i
i
i1














- • — — —























1







































































K
                                   DIAMETER   (mm)
Figure 3.1.  Grain size analysis of the soil used in this experiment.
                                    420

-------
    A. PROFILE
                                     Teflon outlet (Smm o,d,,8mm l.d.)
Jff
                                            Aluminum plat*

                                                I
                           Teflon covered
                           rubber 0-ringa
                           in groove


                           Glass cylinder
                           (15cm o.d.,14cm t.d.)
                                                              Test soil
                                                              Glass microfiber  filters
                                                                     over LOyum) and
                                                                  screen,(0,6mm mtsh.)
                                            Teflon intet ฃ8mm o,d<,6mm l.dป)
                    2,5cm
14cm
                               2.5cm
    B. SECTION A-A
                                                                Bolt holes

                                                                Aluminum piste
                                                                (19cm square)

                                                                Groove*
                                                                •(2mm wldซ, 1mm deซp)
                                                                (5 circular, 8 radial)
                                                               .Groove for glass
                                                                cylinder
Figure 3.2.  Construction details for the  soil columns used in  this
              experiment.
                                          421

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The  column  glass  cylinder  was first  mounted onto  the bottom  aluminum
plate.  Then field-moist soil was added to the  column in  lifts approximately
1.5  cm thick  and  compacted   to  uniform  density  with  a  heavy  tamper
(weight=11.3  kg,  diameter=14 cm).   After placing:  and compacting  each lift,
the  upper  surface  of  the  lift was  scarified  with  a  metal  knife.  After
completely filling the column with soil,  the  upper  glass  mierofiber  filters
and  stainless  steel  screen were placed  and the top aluminum  plate was
positioned.   Then  four  bolts  were  used to connect the  top  and  bottom
aluminum  plates together and seal the glass  column between  them.

Two  columns  were packed in this fashion.   One  was intended for control
purposes  (control column)  while the other  was for the  experiment proper
(test  column).   During packing, each column was  weighed several times  to
enable determination of soil bulk density (moist).  At the time of packing,
soil  samples were  collected  and analyzed for  water  content.   These  data
were  combined with  the moist bulk density to calculate a dry bulk density.
Assuming  a particle density of  2.65 g/cm3, the  total  porosity was calculated.
The results of these measurements are  summarized in  Table 3.3.
Table 3.3.   Characteristics of the soil columns prior to contamination.


Characteristic                 Units       Control Column    Test Column


Soil dimensions:
      Diameter                cm            14.0               14.0
      Surface area            cm2          153.9              153.9
      Length                 cm            14.54             14.45
      Volume                 cm3         2238              2224

Moist soil weight              g           3667              3641
Moist bulk density            g/cm3         !'64              i-64
Water content                 wt.%           8.6                8.6
Dry soil weight               g           3352              3328
Dry bulk density              g/cm3         1-50              1.50

Total porosity                 %             43.5               43.5
                              cm3          975               968
Water-filled porosity          cm3          3i5               313
Air-filled porosity             cm3          660               655
                                    422

-------
Following packing, each column  was  analyzed  in  an x-ray tomograph to
determine  spatial  uniformity as  measured  by  relative  density.    X-ray
tomography was  originally  developed for medical purposes but has  proven
useful in studying the packing arrangement and density within soil columns
used  for experiments  involving water transport  and wastewater purification
[11].   In  this  experiment,  assessment of  spatial  uniformity  was  deemed
important  since  heterogenities,  particularly in  the  horizontal  dimension,
could  confound  the  interpretation  of  the  sampling method effects which
necessarily would  be  based  on samples collected from  different horizontal
locations.

Scanning of the  soil  columns was performed  with a  Siemens  Somatom  2
computer-assisted tomograph (Figure 3.3).   During the scanning process, an
x-ray tube  and  detector  array  were  rotated continuously  around   the
column,  with x-ray scans were made each 0.5 to 1ฐ of rotation.   The x-ray
absorption profile  of  each scan  was recorded  with a scintillation  detector
array containing multiple Nal detectors (512 over a 42ฐ arc).
 Figure 3.3.  Soil column  within an x-ray tomograph.
                                     423

-------
 The absorption values,  in  Hounsfield units or CT  values, were  mapped into
 a 256 by 256  array by an image processor.  The array was  comprised of
 pixels,  the  x  and  y  dimensions  (i.e.  scanning plane)  of   which  were
 selectable between  0.21   and  2.1  mm  and  the   z   dimension  (i.e.  slice
 thickness) either 2, 4  or 8 mm.  For this  experiment, the  pixel dimensions
 (x, y) were 0.7 mm  and horizontal sections, 4 mm thick,  were analyzed each
 cm from column  top to  bottom.   The instrument settings were  125 kilovolts
 for  5  sec. with  a dose of 230 milliamps.  The x-ray  images were recorded
 on computer tape for later evaluation.

 The x-ray image from  each column  cross-section  was visually  observed to
 identify any  apparent  density  anomalies (Figure  3.4).   In no case  were
 there any apparent cracks or channels that might have been conduits for
 preferential flow through  the column.   Equipped  with an image  evaluation
 attachment and  measuring program  (MSO2), the tomograph  was capable of
 determining density relative to  water at each pixel location within an x-ray
 image (pixel edge length = 0.7 mm).
Figure 3.4,  Tomography x-ray image of a horizontal section of the test
            soil column.  (Lighter gray shades indicate higher density.
            White jagged curve displays relative density along diametrical
            line across center of column section.)
                                   424

-------
In each horizontal section, quantitative  measurements  were made of relative
density of approximately 28,000 pixels.  These  pixel locations  included  both
air-  and water-filled pores as well as soil particles.   The relative  standard
deviation  of  these measurements within  a given section was consistently in
the  1035 range,  indicating  negligible spatial variability  in  the horizontal
dimension.   There  were  some  spatial  trends  in  relative  density  in  the
vertical  dimension   (top   to   bottom)  (Figure  3.5).  This  was  probably
attributable to the column  packing and assembly.

Based on  the results of the x-ray analyses (visual and quantitative), it  was
concluded  that  the  columns   were  spatially   uniform  in the horizontal
dimension and that  the variation in the vertical dimension would not affect
the results of this experiment.
                             RELATIVE  DENSITY  VALUES
I
             105  .


            ' 100

     % OF
   COLUMN   95
     AVG.

              90


              85
                 123   4   5   6   789  10  11  12  13  14

                               DEPTH IN COLUMN   (cm)
 Figure 3,5. Relative soil density variation  within 4 mm thick horizontal
            sections of the test column.
            (Section average  to column average.)
                                     425

-------
3.2.3  Soil Column Flow System

Each  soil column  (Figure  3.2) was  setup with the rest of the  experimental
apparatus  in  a  temperature-controEed  laboratory  maintained  at  10ฐC
(Figures  3.6  and  3.7).   The apparatus  components contacting  the feed
solution  were fabricated from glass or  Teflon.   The apparatus included a
mariotte-type constant  head  reservoir  (25  L  glass) containing  the feed
solution  for  the soil column.   This  reservoir  was  mixed with  a magnetic
stirring  bar.  The  replacement jgas to  the feed reservoir  martotte  device
was equilibrated with the feed  solution as follows.   Ambient room air was
fed under low pressure by  an air pump through  activated carbon  filters
and  then  through  a series  of two  reservoirs  (25  L  each) and two gas
washing  bottles (0.5 L  each) (Figure  3.7). This  was done so that the  air
entering the feed  reservoir  would be in  equilibrium with the  contaminant
solution  fed  to the  column and would  not markedly strip  VOCs  from the
feed reservoir during the run.  It also  provided a  source for  air entering
the soil  column during the desaturation period to  replace  soil  pore water
removed (discussion  later).

Attached  to  the column inlet was a  hanging  column  for containing feed
solution.  Following the contamination phase,  this hanging column  was used
to impose a tension  on the  column to  facilitate desaturation  of  the soil
within the column.

The outlet from the column was directed into a 25-L reservoir resting on a
scale.   This facilitated continuous monitoring  of  the  column  outflow  and
enabled feed and  outflow solution sampling at preset outflow volumes.
Figure 3.6, Photograph of the experimental apparatus.
                                   426

-------
                                                        Water manometer
       Soil column
                         Reservoir (SSL gifts*),
                         containing
                         feed solution^
                              Mariotti
                              bubbler Inlet

         valve fryP-^^j ^.  Sampla ""

                      "*" 3
Activated
carbon Alter
•Tripod
                   u/
              Reservoir
              (251 HOPE)
              for toachata
                                    Valve.
                                         8mm 1,0. Tefton
                                         tubing (Typ.
                                                               Ga*waปhlng bottles (0,51 glass)
                                                               with feed solution
                                       ^h
                                            "eservolrsC 251 HOPE)
                                             •nth feed solution
                                                       Activated
                                                       carbon
                                                       filter t (2)
i AJf pump

                                                   Table
                          Hanging column for
                          drainage
                                                   N
           Seal*
    Figure 3.7.  Soil column flow system apparatus.
    3.3  TAEGET CONTAMINANTS AND FEED SOLUTION PREPARATION

    Six  different  VOCs  were  studied  in this  experiment: . methylene  chloride
    (MC),  1,2-dichloroethane (DCA)iป  lปlfl-trichloroethane  (TCA), trichloroethylene
    (TCE), toluene (TOL)   and  chlorobenzene  (CB).   These  were chosen  for
    several  reasons   including,  (1)   their   widespread   usage   and   common
    classification  as hazardous  substances internationally,  (2) their prevalence
    in  hazardous  waste contaminated  land  and  (3)  their  range  of transport
    properties  and  partitioning  behavior  in  soils.   Selected properties  and
    characteristics of the  target VOCs are presented in Tables 3.4  to 3.6.
                                           427

-------
Table 3.4.   Sources and uses of VOCs selected for inclusion in this study.
Target Compound
            Manufacturing Sources and Uses
Methylene, Chloride  -  Used  as  paint  stripper  and  solvent  degreaser;
fumigant; refrigerant; textile and leather  coatings; blowing agent  in foams.
Manufacture    of    aerosols,    photographic   film,   synthetic   fibres
(CAS % 74-09-2).

l,!g-DicMoroethane  -  Component of  paints  and  varnishes;  solvent;  metal
degreaser; chemical manufacturing  (CAS  # 107-06-2).

1.1,1-Trichloroethane -  Metal degreaser and cleaner; industrial solvent and
degreaserj sewer, septic tank and cesspool cleaner   (CAS ง 71-55-6).,

Trichloroelhylene  -  Dry  cleaning   operations;   metal  degreasiiig   and
cleaning; refrigerants; fumigant; organic  chemical  synthesis   (CAS # 79-01-
6).

Toluene  — Petroleum  refining and coal tar distillation (naturally occtitrring -
in coal  tar and petroleum).  Component of asphalt,  naphtha,  and  gasolines;
diluent,  thinner and solvent for paints  and  coatings, gums, resins,  and
rubbers; adhesive  solvent in glues  (CAS # 108-88-3).

Chlorobenzene - Solvent for paints;   chemical and  solvent  manufacturing;
degreaser (CAS # 108-90-7).
Table 3.5.   Some chemical properties of the target VOCs.


Target Compound

Methylene Chloride
1,2-Dichloroethane
1,1,1-Trichloroethane
Trichloroethylene
Toluene
Chlorobenzene

Mol.
Wt.
gmol
84.9
99.0
133.4
131.5
92.1
112.6

Specific
Gravity
-
1.32
1.25
1.35
1.46
0.87
1.11
Water
Solub.
(10ฐC)
mg/L
11092
10554
1399
1499
575
411

Molar
Volume
L/mol
0.064
0.079
0.099
0.090
0.105
0.101
Vapor
Pressure
(2QฐC)
mm Hg
349
61
lO'O
60
22
8.8
Reference
[24]
[24]
[10]
[24]
                                     4Z8

-------
Table 3.6.   Transport and fate properties of the target VOCs.
                             Henry's
                             Constant          Octanol/Water
Target Compound             (10ฐC)            Partition Coefficient

                               -                mL/g

Methylene Chloride           0.060              17.8
1,2-Dichloroethane            0.050              30.2
1,1,1-Trichloroethane         0.415             147.9
Trichloroethylene             0.232             195.0
Toluene                      0.164             489.8
Chlorobenzene                0.105             691.3

Reference                    [10]              [22]
The  concentrations and  quantities of target VOCs to be fed to the test  soil
column  were determined based on  several considerations.  It was desired to
have an easily detectable  level of VOCs in the collected soil samples and at
a  level at  which   cleanup  might  be  considered   (e.g.     >  1  to   10
microgram/gram (ug/g) or part per million (pprn)).  It  was also desired that
a sufficient quantity of  each VOC  be fed to the column so that the sorption
capacity  of the  soil  column   would  be fully  exhausted  and   the   VOC
concentrations  would be  uniform throughout  the  column.    Moreover,  the
volume  required to accomplish this had to be  workably small (e.g. < 20 L).

To   facilitate  the  determination  of  the  appropriate  concentration   and
quantity of each VOC in the feed solution to  the column, consideration  was
given to how the VOCs  would be  retained and  distributed between the  air,
water and  solid phases within the soil column.

VOCs present in an  aqueous matrix flowing through soil tend to  distribute
between the  vapor, liquid  and  solid  phases  according  to  the  following
relationship [9,  12],

            CT  = a  Cv  +  0 GI  +  pb Cs                              [1]
where,
      CT   =  VOC  concentration  per unit volume of soil, ug/mL,
      Cv   =  soil vapor  phase concentration, ug/mL.
      GI    =  soil solution  concentration, ug/mL, .
      Cs    =  soil sorbed concentration,  ug/g,
      Pb   =  soil dry  bulk density, g/mL,
      8    =  soil water  content, mL/mL, and
      a    =  soil air content,  mL/mL.
                                     429

-------
Equilibrium sorption  of organic  compounds  from  aqueous  solutions  onto
porous sorbents  is often described by a Freundlich isotherm:

      Cs * K q l/n                                                     [2]

where,
      Cs    =  soil sorbed  concentration, ug/g,
      GI    -  soil solution phase concentration, ug/mL,
      K     ~  partition coefficient,  mL/g, and
      n     =  empirical constant.


For  many  situations  with  dilute  aqueous  solutions of  VOCs, n=l  and  the
isotherm is linear over the concentration range of interest.  In these cases,
the  partition  coefficient,   K,  is  often   referred  to  as  a  distribution
coefficient, K^ป

In  soil systems,  with  VOCs  dissolved in the  water  phase,  K^ has been
shown to  be strongly  correlated with  the  fractional  soil organic:  matter
content, fora* and the organic matter/water partition coefficient,
The soil organic matter  partition coefficient has been related  to the  water
solubility,  S,  or  the octanol/water partition coefficient,  KOWj both of  which
are interrelated  [5,6,9,12,131;
      Log Rom  =  ai   Log 
-------
If the soil  is  unsaturated,  VOCs can  also  partition into the vapor-phase
according to Henry's law:

      Cv  =   Kh  q                                                  [7]
where,
      Cv    =  soil vapor-phase concentration, ug/mL,
      Kh    =  Henry's law constant, dimensionless, and
      GI     =  soil solution phase concentration, ug/mL.

The  retardation factor (RF)  is the  ratio of  the pore water flux to that of
the solution  VOC flux.  A value of 1 indicates that the  VOC is not retarded
and  travels at the same rate as the pore water.  The  RF for a given VOC
can be calculated  based on the properties of the VOC and the soil system:

      RF = 1 + Kd [pb / 0]                                            [8]
where,
      RF    = retardation factor, dimensionless,
      K
-------
3.4  SOIL COLUMN CONTAMINATION

The  test column was  set  up as shown previously in  Figures  3.6  and 3.7.
RFW  (10ฐC)  was then added to the feed reservoir and  the  two  gas washing
reservoirs.   A  measured  portion  of the stock  VOC  solution  (25  mL) was
added to the  RFW  in  the feed  reservoir  and  in  the two  gas  washing
reservoirs  (ca.  23  L RFW in each).    Following addition of the VOCs, the
three reservoirs were mixed for approximately 1 hr; the feed  reservoir by
magnetic stirrer and the gas washing reservoirs by gentle  air  bubbling.

Immediately  following  addition   of  the  stock  solution,    several  small
"globules"  (total volume  ca. 3 mL) were observed around  the  perimeter  of
the  bottom  of the  feed reservoir.    It was speculated  that these were
comprised of  undissolved solvent compound(s).  Attempts made to  disperse
and  dissolve the globules with a hollow glass tube and gentle  air  bubbling
(pre-equilibrated  with  the feed  solution)  proved  futile.   Since  the  feed
soution was to be monitored, no further attempts were made to disperse  or
dissolve  the globules.   As it  turned out, the  globules  did not change  in
apparent number or size during the course of the experiment.

After the mixing period, approximately  1  L of feed solution was withdrawn
from the column inlet sample valve and was  used to fill  the two,  0.5  L gas
washing  bottles.  Then a  measured volume  of  Tritiated water (5  mL) was
added to the feed reservoir as  a hydraulic tracer (final feed concentration=
ca. 170 Bacquerels/mL).   Following  a few minutes of  mixing,  flow through
the column  was initiated.

The  feed  solution  valve  was  opened  and  the  column  feed  tubing and
hanging  column were  purged   of  air.  Then  flow  was  directed  upwards
through  the soil  column.  The  hydraulic gradient across  the column was
approximately  1.5  as  measured  by a water  manometer and elevation data.
During initial saturation, the wetting front was  observed  for  uniformity  of
flow.  Column outflow  was directed into a  container placed  on a  scale.
Periodically during  the  contamination period, samples of  the  column feed
and  outflow solutions  were collected  via  3-way inlet  and  outlet  valves
(Figures 3.6 and 3.7).

Flow through the  column was continued until  approximately 15  L of solution
had  passed through  the  column.    This was  equivalent   to  ca.  15  pore
volumes  (PV)  and  provided at least  five  times the  weight  of  each VOC
estimated to be required to saturate the column's sorption  capacity*

The  column feed was then terminated.  The sample leg of  the  outlet  sample
valve  was connected to  the inlet gas feed of the 25-L feed reservoir.  Then
the inlet  valve was opened and the column  was allowed to drain under  a
tension of approximately 50 cm  until drainage ceased.   This occurred  over a
period of  only some minutes.   The  pore  water replacement gas  during
drainage  had  been  equilibrated  with feed  solution.   The  inlet and  outlet
valves  to  the column   were  then  shut  and  it  was  removed  from the
apparatus.     Following  the contamination  sequence, the  test  column was
stored at 10ฐC and  allowed to  equilibrate  overnight  (ca.  17  hr.) prior  to
soil sampling.
                                    432

-------
The  control soil column  was treated in a  similar fashion,  except  that  the
target VOCs and Tritiated water  were not added to the RFW  feed  solution.
The  control column  was  run the day preceding the run  with  the  test  soil
column.  The  control  column was  allowed to equilibrate at  10ฐC for ca. 40
hr prior to sampling.

During  the soil  column  contamination,  ambient  temperature was  monitored
periodically by a mercury  thermometer immersed in 2  L of  water placed
adjacent to the soil  column apparatus.   Relative  humidity was  measured
periodically by digital hygrometer*  Immediately  prior to soil sampling, each
column   was   weighed   to   determine  column  characteristics   following
contamination.
3.5  SAMPLE COLLECTION, HANDLING AND ANALYSES

3.5.1  Feed and Outflow Solution Samples

During  contamination of  the  test  soil column, samples of the feed  solution
and  outflow  were collected for analyses of pH,   specific conductance (EC),
Tritium (3H) and VOCs  (Table 3.7).  Immediately prior to sampling, the inlet
and  outlet  sample  valves were  opened and the  first 15 mL of  flow  were
wasted.  Then  a 15  mL  aliquot  was  collected for  Tritium  (ซ*H) analyses.
Then, a 70 mL  sample was  collected for analyses of  the six  target  VOCs.
The  VOC samples were  collected in glass jars  with Teflon lined screw caps.
Finally,  a  50  mL  sample was  collected  for  analyses  of pH  and  specific
conductance.   All liquid  samples  were stored  at  10ฐC  during- the collection
period  after  which  they  were  stored at  2  to 4ฐC  pending  laboratory
analyses.
Table 3.7.   Schedule of sampling the test column feed and outflow
            solutions.
                  Column  Feed Solution
Approximate
Outflow in	„
Pore Volumes      3H    pH,EC
             Column Outflow Solution
                                    VOCs
                  pH,EC
VOCs
First outflow
0.5
1
1.5
2
2.5
3
4
5
10
15  (final)
                  *     *
                  *
                  *
                  *
                  *     *
*
*
*     *
*
*
*
*     *
*
*
                                    433

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3.5.2  Column Soil Samples

Soil samples were collected from both the control and the test soil columns
as  follows.    Following the  equilibration  phase, the  intact  column  was
partially  embedded (50% of length) in approximately 10 kg  of soil, also at
10ฐC. This was  done to provide support  to the column during sampling  and
to maintain the column  soil temperature during sampling which was to occur
at 20ฐC.  The column was  then  moved from the laboratory at 10ฐC to  a  one
at 20ฐC. This was done to  simulate field conditions  where during sampling,
cool  soil  would   be  removed  into  a  warmer   ambient  air  temjjerature
environment.

The column top plate  was carefully  removed along  with the stainless steel
screen and glass  microfiber filter papers.  A paper sampling template  was
placed  on top  of  the column to maintain the center-point of each sampling
location at the same  radius  within the  column.   Soil samples  were then
collected  at the  locations  shown  in Figure  3.8  according  to the methods
outlined in Table  3.8.   AE sampling tubes were inserted simultaneously and
the  tops  covered  with  aluminum  foil  (Figure  3.9).    The  tubes  were then
extracted sequentially in a clockwise fashion (sample tube A to E, A'  to  E')
with each soil sample  containerized and  refrigerated  immediately  and prior
to collecting the next sample (Figure 3.10).
                                            Glass column wall
                                          Sample location
                                   Aluminum
                                   pint*
Figure 3.8.  Soil sampling  plan view of the test soil column.
                                    434

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Table 3.8.   Soil sample  collection methods evaluated in this study.
Sample Method          Description                           (Sample Codes)


A.    Undisturbed sample in empty glass bottle  with  high headspace (A. A')

1.5 cm i.d.  by  10 cm  long soil  sample (ca.  17  mL,  29 g) extracted in   a
stainless steel tube and carefully extruded into an empty  glass  bottle (100
mL nominal, 128 mL actual)  with Teflon lined  screw-top cap.
Headspace  volume = ca. 85% of container volume.


B.    Undisturbed sample in empty glass bottle  with  low  headspace (B. B')

3.0 cm i.d.  by  10 cm  long soil sample  (ca. 75  mL, 125 g) extracted in   a
stainless steel  tube and  carefully  extruded  into a  glass bottle  (100 mL
nominal,  128 mL actual) with Teflon lined screw-top cap.
Headspace  volume = ca. 40% container  volume.


C.    IInj|isijij!b-e_d^AmaLe^m.i^                                ( C. C ' )
3.0 cm  i.d. by  10  cm long  soil sample  (ca. 75  mL, 125 g)  extracted  in   a
stainless  steel  tube and carefully extruded  into a  glass  bottle  (250 mL
nominal, 300 mL actual)  with  Teflon lined  screw-top cap.   100 mL  reagent
grade methanol immediately  added.
Headspace volume = ca.  40% container volume.


D.    Disturbed sample  in empty glass bottle with low headspace (D. D')

3.0 cm  i.d. by  10  cm long  soil sample  (ca. 75  mL, 125 g)  extracted  in   a
stainless  steel tube.  The  contents  of  the tube  were removed in  7  to  10
aliquots with a  stainless steel spoon and deposited into  an empty  glass
bottle (100 mL nominal, 128  mL  actual)  with  Teflon lined screw-top cap.
Headspace volume = ca.  40% container volume.


E.    Disturbed sample  in empty zip-closure plastic bag (E.  E'V

Soil sample (ca. 40  mL,  70  g) removed from the column directly in  7  to  10
aliquots with a stainless steel spoon and deposited into an empty laboratory
grade plastic bag (12 by 18 cm, 0.5 L nominal) with zip-closure.
Headspace volume = ca.  40% container volume.
                                    435

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                                                       Figure 3.9.
                                                       Photograph
                                                       illustrating the  soil
                                                       sampling tube
                                                       insertion.
Figure 3.10. Photograph illustrating the five  soil samples in their respective
            containers.
                                     436

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For the  control  soil column, soil  samples for VOC analyses  were collected
only by  methods A, B  and C and analyzed as quality control blanks.  For
the test  soil column, soil  samples  were collected  by all five methods  (Table
3.8).  The first sample from the test column (A) was  collected 6.2 min after
removal  of  the column  top  plate, while  the  last  sample  (E1)  was collected
10.3 min  after  collection of the  first sample.   Samples for soil water content
and organic carbon content  were then collected.

All  sampling  utensils  and  bottles  were precleaned by   detergent  wash,
distilled  water rinses  and oven-drying  for several  hours at  100ฐC.   The
stainless  steel sampling  tubes   were  precleaned  by  multiple  detergent
washes  and tap water  soaking/rinsing, wiping with  reagent grade  acetone,
distilled  water rinses  and 24-hr oven-drying at 100ฐC.  All sampling  tubes,
utensils  and bottles were  at 20ฐC  at the time of sampling.

In  addition  to  the samples  for  VOC  analyses, additional  samples  were
collected for  analyses  of  water content  and total organic carbon  content.
Soil samples  were  collected from  each  column at  0  to  5  and 5 to  10  cm
depth increments at two (test column) or three (control column) horizontally
separate locations.

During   the  sampling,  soil   temperature  and  relative   humidity   were
periodically measured.   Immediately  following  collection,  all  soil  samples
were stored at 2 to 4ฐC pending laboratory analyses.
3.5.3  Analytical

Solution  Samples.    Solution   samples  were  analyzed  for  pH,  specific
conductance, Tritium and the six target VOCs.  Analyses for pH and specific
conductance were made onsite electrometrically  (Jenway  PW4A  ,pH  meter;
Digimeter L21 conductivity meter).  Tritium analyses were  made on a 1 mL
subsample by liquid scintillation counting of ^H.  Analyses for each  of  the
target VOCs were made by extraction  and gas  chromatography as follows.
A  subsample  (4.0 mL)  of each  solution sample  was  spiked  with  40  ug
bromotrichloromethane  as  an internal  standard  and  then extracted  with  4
mL of pentane.   The pentane extract  was recovered  and dried with  sodium
sulfate  prior to gas chromatographic analysis.

Analyses  of the  four  halocarbons  were made  using a gas  chromatograph
(GC)  (Hewlett  Packard Model  5730)   equipped  with  an  electron capture
detector (Ni63). Analyses of the two aromatics  were made on a GC (Hewlett
Packard  5890)  interfaced  with   a  mass  selective  detector  (5970   series)
operated in the single ion  monitoring  mode.  For  all GC runs, the injection
volume  was  2  uL.  During analyses, all samples  and the  resulting  sample
extracts were  kept in an  ice-bath  to  minimize  possible evaporation  of  the
target compounds.
                                    437

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SMI  Samples.  Soil  samples were analyzed  for  soil water  content, total
organic carbon and the target  VOCs.  Analyses for soil water content were
made gravimetrieally after drying for 24 his at 105 to 110ฐC.  Analyses  for
total organic carbon were  made  by  dry combustion.  VOC analyses  of  soil
samples A, A', B, B', D,  D', E and E' were made as follows.

The  refrigerated soil sample was  homogenized in the  sample container and  a
weighed amount (10 g) was transferred to a test  tube.  After adding 40 ug
of the internal standard,  the soil was extracted  with a  mixture  of  10  mL
isopropanol and  4  mL pentane.  The solvent mixture was transfered to  a
small separatory  funnel,   and  the   extraction was  repeated  with  5  mL
isopropanol and  4  mL  pentane.    The extracts   were  combined  and  the
pentane phase isolated by extraction  with  deionized  water.    The pentane
extract was washed with 2  mL of water and  dried with sodium sulfate prior
to gas chromatographic analyses  as  described  above.  The water content of
each  sample was  determined  on a  separate  aliquot of  soil after  drying
overnight at 105ฐC.  VOC  concentrations were then expressed on a ug  per
g of dry soil basis.                .

VOC analyses  of samples C and C'  (both immersed in methanol)  were made
differently.   The  methanol/soil sample  was   shaken thoroughly.    After
allowing time for the soil  material to settle,  an aliquot of the methanol  was
removed  and centrifuged at 3,000 rpm  for  5 min.  A 4.0  mL  sample  of  the
methanol phase was  then  spiked with 40 tig of the  internal standard.  2.0
mL  of water and  2.0 mL  of pentane were  added to  the  methanol and  the
mixture was shaken.  The pentane  phase was  removed and the  extraction
repeated.   The  two pentane extracts were combined  and  washed with 2 mL
of water and then dried with sodium sulfate prior to GC analyses as  above.
The  VOC results were converted  from a ug per mL of methanol  basis to ug
per  g of  dry  soil basis using the  known  amount of methanol  addled to  a
known amount of moist soil,  both of which were measured at  the time of
sampling-,   and  then  converting  based  on the  soil  water  contents   as
determined  for the specific sample (see above).

       Control.  All reagents were glass-distilled  or  GC grade.  This  sodium
sulfate was heated  at  550ฐ C overnight.  All glassware  was precleaned by
washing, rinsing with deionized water and. drying overnight at 550ฐC.  All
reagent solvents were stored at 4ฐC.

For  quality  control purposes, the  foEowing  sampling  and analyses  were
made.  AH  extraction reagents were analyzed for the target  VOCs.   Analyses
of the isopropanol and  pentane revealed  trace concentrations  of  1,1*1-
trichloroethane, trichloroethylene  and toluene, but  no  methylene  chloride,
1,2-dichloroethane or chlorobenzene.  These trace concentrations were near
the  analytical  detection  limits  and  were  substracted from all  sample
analyses.    Soil samples were also collected from  the control soil column Tby
methods A| B and C (sample codes Cl,  C3,  C2).   Analyses of these samples
revealed no detectable concentrations  of  the target  VOCs.   Analyses  of
clean soil (B2) and the methanol used for infield  preservation (Bl) similarly
yielded no  detectable target VOCs.  (Finally, a sample of the clean soil was
spiked and recovery analyses were made.   The laboratory method detection
limits for each VOC  and matrix are tabulated in Appendix D.
                                   438

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All  samples  for  VOC analyses  were  extracted  within 14 .days  of  sample
collection.   Gas chromatographic analyses were  completed Within 48 hr. of
tne extractions.    During pre-analytical holding, all sampled were stored at
2 to 4ฐC.  During all analyses, the samples and extMcil  fire kept in ice
Baths.


3.6   PAN EVAPORATION TEST

To  provide a measure  of  the evaporative loss  potential during  soil sample
collection,  a  simple pan  evaporation test was conducted in the 20ฐC room in
which the  sampling occurred.  A plastic media dish, 8.6 cm in diameter and
1.4  cm  deep, was  placed  on an  electronic balance and filled  with  20  g of
solution taken from the feed reservoir.  The solution depth  was ca. 3 mm.
Periodically  over  a 4.5  hr.  period, the loss in weight  within  the  dish was
measured  gravimetrically.   During the measurement period,  the  room air
temperature  was 20ฐC and the relative humidity  was ca. 24%.
                                    439

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                                SECTION 4
                        RESULTS  AND DISCUSSION
4.1  COLUMN CONTAMINATION CHARACTERISTICS

Initial upflow  saturation  of the  soil column occurred  over  a period  of
approximately  3  min.   The  wetting front  was  observed  to be  uniform.
Immediately following saturation,  flow  through the  test  column  (upward
direction)  was  continued  over  a  2.5  hr  period.    The  flux  (hydraulic
gradient of ca. 1.5)  was steady throughout the flow  period  and averaged
870 cm/d.   At a  column length of  14.5 cm  and a  water-filled porosity  of
0ป435 cm^/cm^j the average hydraulic retention time in the  column was very
short at ca. 10.4 min.  During the  contamination period,  the temperature
and  relative humidity were 10ฐC and ca. 40^, respectively.

The   results  of   the hydraulic   tracer  study  of  the  test column are
graphically depicted  in Figure   4.1.    The  tracer   breakthrough  pattern
indicated that there was  some bypassing of and  mixing with the  ambient
soil  pore water in the initially unsaturated  column.   In the  initial outflow
from  the column, the ratio  of the  Tritium in the outflow  solution to that  in
the feed solution (Co/Ci) was 0.18.  Had  there been no mixing, but  complete
short-circuiting,  the  Co/Ci ratio  would have been  1.0.   Had there been
complete mixing  with the  pore water, the  first outflow from the column
would have  had  a  Co/Ci  ratio of  0.68.    Had   there  been  complete
displacement of the pore water,  the Co/Ci ratio would have been 0.0.  For
the test  column,  by 1.1  pore volume equivalents (PV)  of  outflow (1,8 PVs  of
column feed) the Co/Ci ratio approached unity (0.96).
           1.20

           1.00

           0.80

   Co/Ci   0.60

           0.40

           0.20

           0.00
                                 TRITIUM TRACER
                                                    1
2      46      8 .    10     12

   OUTFLOW    (Soil pore volumes)
                                                             14
                                                                    16
Figure 4.1.  Breakthrough  curve for  the Tritium tracer
            feed solution for the test column.
                                                           added to the
                                   440

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4.2  FEED AND OUTFLOW  SOLUTION CHARACTERISTICS

Results of analyses  of  pH and specific  conductance in the feed and  outflow
solution  are shown  Table  4.1.  The specific  conductance  of the  RFW  was
reduced  by the  addition of  the organic solutes.  During flow  through the
soil  columns,  the  pH  and  specific  conductance  were  reduced  somewhat.
This  was likely  due to dilution  by  the  ambient pore  water  as  well as
interaction  with  the acidic  soil  which had a  low  pH  (5.21) and  low base
saturation (9%).                        .                                  /

A  comparison  of  the concentrations of  VOCs in the feed solution to  that in
the  stock  solution  is  shown in  Table  4.2.    The  anticipated  ratio  (feed
solution  to stock solution times 1,000)  was about 1.1  based on addition of 25
mL of stock solution to  approximately  23  L  of RFW  in the feed  reservoir
and  the  two gas washing reservoirs.   The fact that the ratios were below
1.1 and  there was  variability between compounds is  suspected to be  due  to
a  number of factors including incomplete  dissolution of  the stock solution
added to the  RFW  and some VOC volatilization during  attempts  to disperse
and  dissolve the globules in  the  feed reservoir.

Analyses of  the  target  VOCs  in  the  feed  solution  and  outflow  are
graphically  depicted in Figure 4.2 and  summarized in Table 4.3.  For all six
VOCs,  the concentrations in the feed solution  were higher (5 to 1735) in the
samples  collected at  15.4 PVs of column outflow as compared to  3.3 PVs. The
reasons  for this  are not known but could  be  due to apparatus conditioning
or gradual dissolving of the  globules in the feed reservoir.
Table 4.1.   Results of analyses of soil column feed solution and  outflow
            samples for pH  and specific conductance.
Soil Column
Outflow
Sample
Point
PH
                                                Specific Conductance
PV
Control Column
3.3


15.4 (final)
Test Column
3.3
 15.4 (final)
                  Feed
                  Outflow

                  Feed
                  Outflow
Feed
Outflow

Feed
Outflow
                  Units

                  7.0
                  6.6

                  6.9
                  6.7
7.1
6.6

7.1
6.7
                  uS/cm

                  297
                  252

                  281
                  240
                                                      126
                                                      108

                                                      129
                                                      116
                                     441

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Table 4.2.   Comparison of VOC  concentrations in the feed and stock
            solutions.

Target Compound

Methylene Chloride
lป2-Dichloroethane
1.,1,1-Trichloroethane
Triohloroethylene
Toluene
Chlorobenzene

Feed Solution^
mg/L
157.5
130
16
12.75
4.5
2.85

Stock Solution
mg/L
200,000
125,000
25,000
20,000
7,500
5,000
Ratio^
(x 1,000)

0.79
1.04
0.64
0.64
0.60
0.57
1 Feed solution value  is average of .two measurements (Table 4.3).
2 Ratio of feed solution to stock solution multiplied by 1,000.
                           VOO BREAKTHROUGH
          0.00
               xK
              0.00   2.00   4.00  6.00  8.00  10.00 12.00 14.00 16.00

                       OUTFLOW    (Soil pore volumes)
Figure 4.2.  Breakthrough curves for the Tritium and the six target VOCs
            studied.
            (See appendix A for the individual VOC curves.)
                                   442

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Table 4.3.   Results of VOC analyses of the test soil column feed and
            outflow solutions.
Target Compound

Methylene Chloride
1,2-Dichloroethane
1,1,1-Trichloroethane
Trichloroethylene
Toluene
Chlorobenzene
Outflow
Volume
PV
1.1
3.3
10.3
15.4
Average =
1.1
3.3
10.3
15.4
Average =
1.1
3.3
10.3
15.4
Average =
1.1
3.3
10.3
15.4
Average' =
1.1
3.3
10.3
15.4
Average =
1.1
3.3
10.3
15.4
Average =
Feed
Solution
mg/L
150
165
157.5
120
140
130
15.5
ซ•
16.5
16.0
12.0
13.5
12.75
4.4
4.6
4.5
2.7
3.0
2.85
Outflow
Solution
mg/L
150 .„
160
150
145
110
110
150
135
16.5
17.0
18.5
17.0
11.5
13.5
13.5
13.0
3.6
4.5
4.5
4.0
1.7
2.6
2.6
2.4
Co 1
Ci
-
0.95
1.02
0.95
0.92
0.85
0.85
1.15
1.04
1.03
1.06
1.16
1.06
0.90
1.06
1.06
1.02
0.80
1.00
1.00
0.89
0.60
0.91
0.91
0.84
  Co/Ci =  outflow  solution / average feed  solution.
                                    443

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4.3  SOIL COLUMN CHARACTERISTICS  FOLLOWING CONTAMINATION

Following contamination,  desaturation and  equilibration, the  characteristics
of  the  soil  columns  were  determined  as  shown  in  Table  4,4.    The
characteristics of the control and test columns were substantially the same.

Compared to the  characteristics  of the test column  prior  to contamination
(Table 3.3),  the  water content  had increased from 32%  to 63%  of total
porosity,   respectively.    This  increase   reflects   the  altered  drainage
conditions in the soil in  the  laboratory  column  as compared  to  the soil
profile in the field.
Table 4.4*   Characteristics of the soil columns after contamination.
Characteristic                 Units       Control Column    Test Column
Soil dimensions:
Diameter
Surface area
Length
Volume
Moist soil weight
Moist bulk density
Water content
Dry soil weight
Dry bulk density
Total porosity
Water-filled porosity
Air-filled porosity

cm 14.0
cm2 153.9
cm 14.54
cm3 2238
g 3950
g/em3 1.76
wt.% 15.1
g 3352
g/cm3 1.5
% 43.5
cm3 975
cm3 598
em3 377

14.0
153.9
14.4J5
2224
3936
1.77
15.4
3328
1.5
43.5
968
608
360
  Refer to Table 3.3 for characteristics of the test column prior to
   contamination.
                                    444

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The  results  of  analyses of water content  and total  organic carbon  in  soil
samples collected from  the  control and the test column  are summarized in
Table 4.5.   These results indicated an increasing water content with  depth
in the  soil  column,  but  similar results  at  horizontally  separate  spatial
locations.  The  water  content trend with depth is probably due to moisture
drainage and redistribution following  the  contamination  period.  The  water
content results for the columns as a  whole combined  with the results for
the top 10 cm  within the columns indicate that the soil at the bottom of the
columns  was likely nearly saturated at the time of sampling.

The  total  organic carbon  content was generally consistent  regardless of
depth  or location.  The relative  standard deviation  for  four samples  from
the test column was only 3.5% (Table 4.5).
Table 4.5.   Water content ancT total organic carbon content in soil samples
            collected from the soil columns following  contamination.
Quadrant
Depth
Water Content   Total Organic  Carbon
Control Column

Northeast
Center
Southwest

Northeast
Center
Southwest
                  cm
0-5 cm
0-5 cm
0-5 cm

6-10 cm
6-10 cm
6-10 cm
             % of moist soil    % of dry soil
Complete Column*-
     9.40
     9.70
     9.50

    12.00
    12.70
    12.50
      Average =  10.97
                  15.1
0.465
0.424
0.454

0.433
0.420
0.422
                                                      0.436
 Test  Column

 Northeast
 Southwest

 Northeast
 Southwest
 Complete Column
0-5 cm
0-5 cm

6-10 cm
6-10 cm
                        Average =
     9.20
     9.90

    11.20
    13.40

    10.92
    15.4
0.420
0.415

0.445
0.413
                                    0.423
    Based on gravimetric measurements of the  entire column  (See  Table  4.4).
                                     445

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4.4  VOC DISTRIBUTION

To facilitate analysis and interpretation of the solution VOC retardation and
soE  sampling-  method  effects  data,  a VOC distribution analysis  was  made
using   the  empirical   relationships  presented   earlier.     The   estimated
equilibrium distribution of the six target VOCs under the conditions of this
experiment are summarized in Tables 4.6 and 4.7.

As illustrated  by these computations, the sorption affinities of all six target
VOCs for  the sandy  soil at 10ฐC are  quite low with K
-------
Table 4.7.   Calculated equilibrium distibution of the target VOCs within  the
            test soil column. 1


Target Compound




Methylene Chloride


1,2-Dichloroethane


1,1,1-Trichloroethane


Trichloroethylene

Toluene

Chlorobenzene






Phase Cone.
cl cs
Ug Ug
mL g
145 5.2
[1.3]2
135 4.9
[1.3]
17.0 3.3
[1.2]
13.0 2.6
[0.9]
4.0 1.1
[0.7]
2.4 1.1
[0.6]
Column Cone.
Ctir.
V 1
Ug. Ug,
mL mL
8.7 26,7
(73)3
6.8 24.8
(73)
7.1 3.1
(32)
3.0 2.4
(34)
0.7 0.74
(28)
0.3 0.44
(20)
ws
MS.
mL
7.8
(21)
7.4
(22)
5.0
(50)
3.9
(55)
1.6
(65)
1.6
(76)
WV Wt
ug_ ug
mL mL
2*2 36.7
(8)
1.7 33.9
(5)
1.8 9.9
(18)
0.8 7.1
(11)
0.2 2.5
(7)
0.1 2.2
(4)
Soil
Cone.
CT
ME.
g
24.5

22.6

6.6

4.7

1.7

1.5

1 Computations:
q
cs =
cv =
f|T_ . ซ•>
?1 1 ""
ttt mm
Wy =
wt =
CT =
outflow
Kd Ci
Kh Ci
we GI
Pb Cs
AC Cv
Wi +
Wt / P]
concentration





W^ in
S " V
b
(final), Table 4.3




























       WC    -  10.92% (wt. basis) or 18.4% (vol. basis),    Table 4.5
       AC    =  43.6%  - 18.4% or  25.2% (vol.  basis),     Table 4.5
       Soil dry  wt. =   3.328 kg,  Table 4.4
        Pb   s  1ซ5 g/mL
    The number in brackets equals % of water  solubility at 10ฐC.
    The number in parenthesis equals % of soil associated VOC (wt.%)
     in  that phase.
                                     447

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4.5  SOLUTION VOC RITAEDATION

Based  on  the limited  data available  (Table 4.3,  Figure  4.2, Appendix A),
transport  of  the  six  VOCs  was  generally  similar  to that  of  the Tritium
tracer.    Only  the aromatics  (toluene and chlorobenzene)  exhibited  any
notable retardation during the initial  flow  period (Figure 4.2).  Consistent
with the predicted retardation factors  (Table 4.6), by three PVs of outflow,
the  concentration  of  each  VOC in the outflow  solution  was  substantially
similar to  that  in  the  feed solution.   This  condition  persisted  through the
balance of the throughput period  (Figure  4.2).

It is interesting to note  that despite the relatively high  flow  rate  and
short  retention  time   within  the column   (ca.  10.4  min),  the   sorption
observed,  albeit minimal, was consistent with that  predicted  by equilibrium
relationships.   Some  researchers  have reported  that equilibrium  sorption
was  not  likely  above a flow  rate of  1 m/d [13].     The flow  rate in  this
experiment was substantially higher at 8.7 m/d.


4.6  SOIL  SAMPLING METHOD EFFECTS

4.6.1  Sampling Method  Comparison

Sampling  of  the test  soil  column  occurred  at  a room temperature of 20ฐC
and  a relative  humidity of  ca. 21%.   Soil  samples  were collected by  five
different  methods as outlined earlier in Table 3.8.  Following removal of the
column top plate,  the  VOC samples were  first  collected,  containerized  and
refrigerated.  The first soil  sample (A) was collected at  6.2 min. of elapsed
time following removal  of  the  column  top plate, while the last  sample  (E1)
was  collected at  16.5 min* elapsed time.  For  each  pair  of  replicates, the
second sample was collected  ca. 5  min  after  the first.

The  results of  VOC analyses of thte soil  samples  collected by  the different
methods  are graphically depicted  in  Figure 4.3. and summarized in Tables
4.8,  4.9 and Appendix  B  and  C.    The  variability  between replicates  was
generally quite low (c.v. < 0.15) (Table 4.8).  A trend in the replicate data
was  observed where the VOC concentration  in the second replicate collected
was  typically  lower  than the  first.  This was  particularly  notable  for
methylene chloride* This  suggested that a portion  of  the  soil associated
methylene chloride and possibly  the  other  VOCs  were lost,  presumably by
volatilization,   even  during  the   short  period  over  which  the  sampling
occurred  (i*e. 5 min).

An analysis  of variance  revealed that sampling  method  had  a significant
effect  on  the  determinations  of   all  six  VOCs.   The effects  were highly
significant (p >  99.5*) for all  VOCs but methylene chloride (p = 75*).   The
lack of a highly significant  effect for methylene chloride may be due in
part to  replicate  variability as discussed  above  as  well  as the  analytical
difficulties often associated  with  quantification of this compound  [18].   As
shown in  Appendix D, the  estimated  variance for  analyses of methylene
chloride  in this  experiment  was  ca.  ฑ20%  compared  to  ฑ5 to  10% for the
other compounds.
                                     448

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   PPM
                          VOC  SAMPLE  METHOD COMPARISON
                  MC       DCA       TCA       TCE

                                      COMPOUND
TOL
CB
Figure 4.3. Average concentrations of target VOCs in  soil samples as a
           function of sampling method.
           (See Appendix C for individual compound  graphs.)
            Sample Methods Descriptions:

      E.     Disturbed  sample in empty  zip-closure plastic bag.
      A.     Undisturbed sample in empty glass  bottle with high headspace.
      D.     Disturbed  sample in empty  glass bottle with low headspace.
      B.     Undisturbed sample in empty glass  bottle with low  headspace.
      C.     Undisturbed sample immersed in methanol in  glass bottle.
                                   449

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Table 4.8.   Concentrations of VOCs in .soil samples from the test column.
: Sampling Method*
Target Compound

Methylene Chloride




if2-Diehloroethane




ltlfl-Trichloroethane




Triehloroethylene




Toluene




Chlorobenzene






Rep. 1
Rep. 2
Average
Std.dev.
c.v.
Rep. 1
Rep. 2
Average
Std.dev.
C.V.
Rep. 1
Rep. 2
Average
Std.dev.
c.v.
Rep. 1
Rep. 2
Average
Std.dev.
c.v.
Rep. 1
Rep. 2
Average
Std.dev.
C.V.
Rep. 1
Rep. 2
Average
Std.dev.
C.V.
E.
ug/g
0.202
0.202
0.20
0
0
0.052
0.052
0.05
0
0
0.012
0.01.2
0.01
0
0
0.01
0.01
0.01
0
0
0.06
0.05
0.055
0.007
0.13
0.0052
0.0052
0.005
0
0
A.
ug/g
1.60
1.90
1.75
0.21
0.12
5.20
5.10
5.15
0.07
0.01
0.19
0.21
0.20
0.01
0.05
0.30
0.33
0.315
0.02
0.06
0.35
0.39
0.37
0.03
0.08
0.56
0.56
0.56
0
0
D.
Ug/g
8.00
4.20
6.10
2.69
0.44
5.70
4.60
5.15
0,78
0.15
0.30
0.25
0.275
0.04
0.15
0.46
0.38
0.42
0.06
0.14
0.41
0.36
0.385
0.04
0.10
0.61
0.54
0.575
0.05
0.09
B.
ug/e
7.20
2.60
4.90
3.25
0.66
6.80
6.60
6.70
0.14
0.02
0.35
0.37
0.36
0.01
0.03
0.53
0.56
O.S45
0.02
0.04
0.48
0.49
0.485
0.01
0.02
0.68
0.70
0.69
0.01
0.01
C.
ug/g
10.01
4.39
7.20
3.97
0.55
19.14
18.30
18.72
0.59
0.03
1.91
1.83
1.87
0.06
0.03
2.34
2.20
2.27
0.10
0.04
0.72
0.68
0.70
0.03
0.04
0.78
0.73
0.755
0.04
0.05
  Refer to Table 3.8 for a  complete description of each sample method:
   E. Disturbed soil (40 mL) in  plastic bag.
   A. Undisturbed soil (17 mL) in glass jar (128  mL) with Teflon Lined cap.
   D. Disturbed soil (75 mL) in  glass  jar (128 mL) with Teflon lined cap.
   B. Undisturbed soil (75 mL) in glass jar (128  mL) with Teflon lined cap.
   C. Undisturbed soil (75 mL) immersed in 100 mL methanol in a glass jar
      (300 mL) with a Teflon lined cap.
  For samples 1 and E'ป there werฃ non-detectable levels of methylene
    chloride,  dichloroethane and chlorobenzene.   The value shown  is equal
    to 50% of the method  detection limit.  For trichloroethane, the reported
    value of < 0.01 is shown. See Appendix D for detection limits.
                                    450

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Table 4.9.   Magnitude and significance of differences observed in the
            sampling  method effects.
Target Compound
                                          Sampling Method^
                                          E.
                                                A.
                              D.
B.
C.
Methylene Chloride
1,2-Dichloroethane
1,1,1-Trichloroethane
Trichloroethylene
Toluene
Chlorobenzene
Ave. ug/g
% of C.2
LSD (95%)3
Ranking4

Ave. ug/g
% of C.
LSD (95%)
Ranking

Ave. ug/g
% of C.
LSD (95%)
Ranking

Ave. ug/g
% of C.
LSD (95%)
Ranking

Ave. ug/g
% of C.
LSD (95%)
Ranking

Ave. ug/g
% of C.
LSD (95%)
Ranking
                                          0.20   1.75  6.10  4.90  7.2
                                          2.8   24.3   84.7   68.1
                                          0.05   5.15  5.15  6.70 18.72
                                          0.3   27.5  27.5  35.8

                                          E
-------
Based on a least significant difference analysis  (Table  4.9),  the ranking of
VOC  concentration by sampling method  from lowest  to highest concentration
measured was.

      Sampling Method  E
-------
 Table 4.10. Comparison of measured VOC concentrations versus estimated
            concentrations for the conditions of  this experiment.
                           Concentration              Ratio of
                          	        Measured
Target Compound        Measured*   Estimated^         to Estimated

                        Ug/g        Ug/g              -
Methylene Chloride
1,2-Dichloroethane
1,1,1-Trichloroethane
Trichloroethylene
Toluene
Chlorobenzene
7.2
18.72
1.87
2.27
0.70
0.76
24,5
22.6
6.6
4.7
1.7
1.5
0.29
0.83
0.28
0.48
0.41
0.47
  The  highest average concentration measured (i.e Method C with infield
   immersion in methanol, Table 4.9).
  The  estimated concentration includes  all soil associated  VOCs (i.e. liquid,
   solid and vapor) (Table 4.7).
The fact  that  the highest  VOC concentrations measured  were consistently
less than the concentrations estimated suggests there  may have  been some
undefined negative bias.   This may have  been due  to volatilization losses
during  soil column exposure and  sampling.  Alternatively, the estimates  of
VOC retention  may have been too high. Most likely  it  is a combination  of
these and perhaps other factors.  The fact that the ratios of  the measured
to  estimated  concentrations were all  <1  and varied  inversely   with  VOC
vapor  pressure  supports the  speculation  regarding negative  bias  due  to
volatilization losses.  An assessment of this is given below.

The pan evaporation test revealed an evaporative  loss for the feed solution
equal to  0.13 mg/min/cm^.   This  loss is presumably  due  to evaporation  of
water   and  the   six   target   VOCs.   /For  methylene   chloride,  1,1,1-
trichloroethane and trichloroethylene,  50% loss from  an aqueous  solution  at
1  mg/L concentration reportedly  occurs over a period  of  ca. 19  to 24 min
at  25ฐC  [24].    At the  higher   concentrations  of  this  experiment,  the
evaporation rate  would be  higher but  at  the lower temperature, the  rate
would  be somewhat lower.   Moreover, the  evaporation  rate from  soil would
be further reduced.

For the most  volatile VOC in this  experiment,  methylene chloride, the initial
weight  in the evaporation pan was 3.1 mg.  Assuming 50%  volatilization loss
from the  pan  (area =  58.1 cm2)  over  20  mm, the  rate  of  loss is 0.0013
mg/min/cm2.   This rate of  loss is only about 1% of the total, measured  rate
for  the pan.   This apparently low  percentage may not be unreasonable  as
the measured  rate of  loss for  the pan  was constant  over the  4.5  hr
                                   453

-------
measurement  period   suggesting  a  substantial  contribution   by  water
evaporation*

At  the above  rate of  loss, the  weight  of  methylene  chloride  volatilized
during sample collection  could have  been ca. 105  ug  (for 3  cm  diameter
sampling  tube  and  average  exposure  time  of  11.4 min).   The  highest
measured concentration of methylene chloride was 7.2 ug/g dry  soil (Table
4.9).   In a representative soil  sample (ca. 110 g  dry soil. Appendix B), the
total  methylene  chloride  present  would  be  ca.  792 ug.    The  estimated
volatilization loss of 105 ug is  equivalent to a negative  bias  of about 12%.

This  cursory  analysis  suggests  that  the  highest  VOC  concentrations
measured (Le.  by Method  C)  likely deviated from the  "true"  value  by
appreciable  levels due  to  volatilization  losses of VOCs  during  soil  sample
collection.  This   interpretation  is  supported   by  the   trends  in  VOC
concentrations observed  between  replicate  samples  for the  more  volatile
VOCs   as  described   earlier  and  the   differences   observed   in  VOC
measurements for disturbed versus undisturbed  samples (Table  4.9).

Recognizing  that the  highest  concentrations measured  probably  deviated
from the "true" value by  an appreciable  but unknown negative bias, it was
still possible to  compare  the  relative  bias  associated  with the different
sampling  method  elements  using the  highest concentration measured as a
reference (i.e. Method  C).    For  soil samples  containerized  in plastic bags,
the  substantial  negative  bias (i.e.  ca.  100%)   clearly  demonstrates that
collection of a  sample in this manner is unacceptable  where analyses for
VOCs  are intended.   For  soil samples containerized in Teflon  sealed glass
jars,   the  relative  bias contributions were  greatest  for  lack  of  infield
immersion in methanol, followed by considerably  lesser  contributions  by
headspace volume and  disturbance  (Table 4.11),


Table 4.11.  Relative sampling bias associated with selected elements of the
            soil sampling  methods studied.
Target Compound
                        Relative Bias of Sampling Element from  Method

                        No Methanol Disturbance Headspace   Total
Methylene Chloride
1,2-Dichloroethane
1,1,1-Trichloroethane
Trichloroethylene
Toluene
CMorobenzene
_2
-64.2
-80.7
-75.8
-30.0
- 9.2
!
-8.3
- 4.3
- 5.7
-14.3
-14.5
?
-8.3
- 8.6
-10.1
-17.1
-17.1
?
-81
-94
-92
-81
-41
1 Relative bias computations:
      No  raethanol =[(Method 8 - Method C)/Method C\ * 100*
      Disturbance = [(Method D - Method B)/Method C] * 100*
      Headspace  =[(Method A - Method B)/Method C] * 100*
2 Data omitted due to replicate sample variability.
                                    454

-------
The  negative bias contributed by lack of infield immersion in methanol is
less  for  the  less  volatile  compounds  (e.g. toluene  and  chlorobenzene).
Thus,  infield methanol  preservation is  most important  for  highly volatile
compounds.    The   negative  bias  associated   with  increased  container
heads pace volume is greater than that of sample disturbance.  Therefore it
appears  better to collect  a disturbed sample  in a  full container than  an
undisturbed sample in a partially full container.


4.6.3   VOC Bias Mechanisms

There   is   little  question   that  there   are  substantial   and  significant
differences in negative  bias associated  with VOC  measurements made with
different sampling methods.  While the mechanisms responsible for the bias
were not  elucidated  in  this experiment, those  potentially  associated with
each of the sampling  methods are summarized in  Table  4.12.

Appreciable  but undefined negative bias wan  suspected in all of the  soil
samples  collected.   As described previously,  volatilization was speculated as
a  plausible  mechanism   with the VOC  loss  occurring  during  soil  column
exposure and soil sample collection.  Of  the  sampling method effects  tested
in this experiment,  soil  sample collection  with infield immersion in methanol
(Method C), consistently yielded the  highest concentrations  of  VOCs  and
presumably  the  lowest  negative  bias.    This  is   probably  due  to  a
combination  of factors.    The  methanol  may  minimize  volatilization  losses
during   pre-analytical   holding  and   laboratory   subsampling,   inhibit
biochemical transformations and enhance extraction of soil associated  VOCs.

It was speculated that the  substantial negative  bias of sampling method E
(disturbed  sample in a  plastic  bag) was principally due to  vapor leakage
through  the  polyethylene  bag  during   pre-analytical  holding  with  some
contribution from  a  combination of volatilization  losses during  collection,
storage  and subsampling in the laboratory.   This speculation is  supported
by  data   of   Slater  et  al.   which  indicated  substantial  leakage  of
trichloroethylene  through multiple  polyethylene bags  used to encase  soil
samples contained  in Teflon sealed glass  vials  [19].   The  negative bias
within  sampling methods A, B and D  were  likely  due  to a combination of
volatilization  losses  during  collection,  storage  and  subsampling  in  the
laboratory.     For all methods,  transformation losses  during pre-analytical
holding  were probably low  based on  recent research  where good stability
was  observed for VOCs during holding at 4ฐC for up to  28 days [15,16].


4.6.4  Implications

The  soil sampling results suggest the  potential significance  sampling  method
effects can  have on  the investigation and cleanup of solvent contaminated
land.      For   example,   the   results  for   1,1,1-trichloroethane   and
trichloroethylene,  both  very common  contaminants,  ranged  from  less than
0.01 ug/g  to  2.3  ug/g  (ppm).    All four  sampling methods  which did not
employ  infield methanol immersion  yielded  concentrations  less  than  0.55
ug/g.   In contrast the  sampling method  with infield immersion in methanol
yielded  values of  1.8 ug/g  or above.  The implications of these results are
                                   455

-------
far-reaching since 1 ug/g has in many cases  been used  as the action level
for cleanup.  Thus, if  the sampling' had been done without infield, methanol
immersion,  cleanup may  not  have been  initiated.    If  done  with  infield
methanol  immersion, cleanup may  have resulted.   The  cost implications  are
enormous.                                                         ...
Table 4.12.  Potential bias mechanisms associated with the sampling methods
            tested in this study.


                                               /Sampling Method*
Bias Mechanism^                          E.    A.    D.    1.    C.
Bias Mechanism      ...     _       .   :. ,,    ^   ......   '._ .
Volatilization during  soil,exposure         -H-3   "H"    -H-    -H

Volatilization during  sample collection      ++    +    ,.++;.+

Volatilization / vapor leakage
during storage                           -H-    +     +     +

Transformations during storage           +•     +     +     +

Volatilization / vapor loss
during subsampling                       +     -H-    +     -f

          Method Features
Disturbance                               Yes   No    Yes   No    Ho
Headspace volume                         Low   High  Low   Low
Container                                 Plast. Glass Glass Glass Glass
Methanol                                  No    No    No    No    Yes

1 Sampling method listed from lowest to highest concentration of
  VOCs measured.  Refer to Table 3.8 and text for complete
  description of sampling methods tested.
2 Volatilization losses expected to be greater for more volatile compounds.
3 "-" indicates  not likely source of bias,
   "+" indicates possible source  of bias,  and
   "-H-" indicates likely source of bias.
                                   456

-------
An  appropriate  procedure for sampling soils for VOC analyses must account
for the special  properties and  behavior of these  compounds.  Collection of
soil  samples with  containerizatidn in plastic  bags  is  clearly  unacceptable
where analyses  for VOCs  are intended.   Containerization in a teflon sealed
glass  jar  is  workable and  appropriate,  but decisions  regarding  sample
disturbance, headspace  volume  and  infield  methanol  preservation  appear
subject to considerations associated  with VOC  properties  and contamination
levels.

For  analyses of VOCs  with relatively low  solubilities and vapor  pressures
(e.g.  chlorobenzene), collection  of a  disturbed sample  with containerization
in a Teflon sealed glass jar  and refrigeration at 4ฐC would usually provide
an  accuracy similar to that of more complex methods.  For such  samples, it
is  better  to collect  a  disturbed  sample and  completely fill  a  sample
container rather than collect an  undisturbed sample which results in a high
headspace volume In the container.

Conversely, for  analyses of VOCs with relatively high solubilities and vapor
pressures,  and  particularly  where  concentrations  are anticipated  in  the
range of a cleanup action level (e.g. 1,1,1-triehloroethane at ca. 1 ppm),
enhanced accuracy requires  the collection of an  undisturbed sample with
containerization in  a Teflon  sealed glass  jar, infield immersion in methanol
and refrigeration at 4ฐC.  This procedure  has  been advocated  recently  and
may be incorporated into a forthcoming  A.STM  standard [4, 21].
                                    457

-------
                                SECTION 5
                               CONCLUSIONS
The  purpose of this  study was to provide insight into the systematic error
or   bias  associated  with  field   sampling   methods   when   making  VOC
measurements in solvent contaminated soil.  Five different sampling  methods
were used to assess the effects of; sample disturbance*  container lieadspace
volume, container integrity and infield methanol preservation.

A naturally occurring sandy  soil encased in a soil column was contaminated
by  saturated  flow  of a  solvent  solution.   Contamination occurred  in  a
Gontrolled-temperature laboratory at 10ฐC.

After contamination, desaturation  and  equilibration, replicate soil  samples
were collected  at  an  ambient  air  temperature  of  20ฐC.    Experimental
analyses included  basic  soil  physical  and  chemical properties, computer-
assisted  x-ray  tomography   and  radioisotope  tracer  studies,  and  gas
chromatographic analyses of  the target  VOC concentrations in the  column
feed solution, outflow and contaminated soil.

Based on  the  results  of this  research, conclusions  regarding  sampling
method  effects and  systematic error or bias have been drawn.  However,  it
is   important  to  recognize   that  there are   numerous   VOCs  commonly
encountered in contaminated land  (eซg. Table 2.1)  with diverse properties
and  behaviors in soil environments.   Moreover, the characteristics  of soil
systems and the  environmental  conditions in which they are sampled also
vary widely.   The research  conducted included only  six target VOCs, one
soil  system and one sampling environment.   Thus, application  of the  results
of the work reported herein  must be made cautiously until further research
can  be  conducted,.    Recognizing  this,  the  following  conclusions  are  put
forth:


1.     Soil   column  preparation  and  operation  resulted  in  uniform  soil
conditions,  the  confirmation  of  which was  facilitated by computer-assisted
x-ray tomography (Figures 3.3 to 3.5).


2.     Six  common  VOCs  present  in an aqueous  solution  at  individual
concentrations of 2.85 to 157.5  mg/L,  were poorly  retarded  in the  sandy
soil  under  conditions of saturated  flow  at a flux rate of 870  cm/d (Figure
4..2,  Table  4.3,   Appendix A).   The observed retardation characteristics
were generally  consistent  with  predictions  made based  on VOC  water
solubility and soil organic matter content (RF = 1.1  to 2.6).


3.     Comparison of  five different  soil  sample  methods   revealed that
sampling method effects were substantial and significant (Figure 4.3, Tables
4.8 and 4.9, Appendix C).                                                - -
                                    458

-------
4.     Based on a least  significant  difference  analysis, the ranking  of VOC
concentration   by sampling  method from  lowest  to  highest  concentration
measured was:

            Method  E<_A
-------
Conversely, for analyses of VOCs  *ith  relatively high solubilities and  vapor
pressures)  and  particularly  where  concentrations  are  anticipated in  the
ranee  of a cleanup  action level  (e.g. 1,1,1-trichloroethane at ca.  1  ppm),
enhanced accuracy requires  the  collection  of an undisturbed sample with
containerization in a  Teflon  sealed! glass  jar, infield immersion in  methanol
and  refrigeration at 4ฐC.


9.    Further  research  is necessary  to extend  the  results of  the work
described herein to other organic , compounds, soil  conditions and  sampling
environments.
                                    460

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                                 SECTION  6
                                REFERENCES
• 1.   ,  Barcelona, M. J.  1988.  Overview of the sampling process.  In:  Keith,
       L.H.  (ed.),  Principles  of environmental  sampling,  American  Chemical
       Soc., Washington, D.C.   pp 3-23.

 2,     Black, C. A.  (ed.).   1965.  Methods of Soil Analysis  -  Part 1.   Am.
       Soc. of Agron., Madison, WI.   770  p.

 3.     Brown,   K.      1989.      U.S.    Environmental  Protection  Agency,
       Environmental Monitoring and  Systems  Laboratory,  Las  Vegas,  NV.
       Personal communication,   3 August 1989.

 4.     Bone, L. I.    1988.   Preservation techniques  for  samples  of  solids,
       sludges  and  nonaqueous  liquids.   In:  Keith, L.H.  (ed.),  Principles of
       environmental sampling,  American Chemical Soc.,  Washington, D.C.   pp
       409-414.

 5.     Chiou, C. T.,  P.  E.  Porter and D. W. Schmedding.  1983.   Partitioning
       equilibria of  nonionic organic compounds  between  soil organic  matter
       and water.  Environ. Science  and Technology,  17:  227-231.

 6.     Chiou, C. T.  1989.   Theoretical considerations  of the  partition  uptake
       of  nonionic  organic  compounds  by   soil  organic  matter.       In:
       Sawhney,  B.L.  and K.   Brown   (ed.).    Reactions  and  movement of
       organic  chemicals in soils.  Soil Science Soc. America Special Publ.  No.
       22,  Madison,  WI.  pp. 1-29.

 7.     DeVitt, D. A., R. B. Evans, W. A. Jury, T.  H. Starks, B. Eklund  and A.
       Gholson.   1987.   Soil  gas  sensing for  detection  and mapping of
       volatile  organics.  National Water  Well Assn., Dublin, OH.  270 p.

 8.     Ford, P. J., P. J.  Turina and D.  E.  Seely.  1984.  Characterization of
       hazardous  waste  sites  - a  methods  manual  - volume  II,  available
       sampling  methods   (2nd edition).    1984.     EPA-600/4-84/076,   U.S.
       Environmental   Protection  Agency,   Environmental   Monitoring   and
       Systems  Laboratory, Las Vega,  NV.

 9.     Hern, S. C. and S. M.  Melancon (ed.)  1986.  Vadose zone modeling of
       organic  pollutants.  Lewis Publishers, Inc.,  Chelsea, MI.  295 p.

 10.   Howe, G. B.,  M. E. Mullins  and T. N. Rogers.   1986.   Evaluation  and
       prediction  of Henry's   Law  constants  and aqueous  solubilities   for
       solvents and hydrocarbon fuel  components.   USAF  ESC  Report  no.
       ESL-86-66.   U.S. Air Force Engineering and Services  Center, Tyndall
       Air Force Base,  Florida.

 11.   Jenssen, P. D.  and P.  H. Heyerdahl.  1988. Soil column descriptions
       from  x-ray   computed   tomography  density  images.   Soil Science.
       146(2): 102-107.
                                    461

-------
12.    Jury, W. A.  and M.  Ghodrati.   1989.   Overview  of organic chemical
      environmental fate  and transport modeling approaches.  In:  Sawhney,
      B.L.  and  K. Brown  (ed.).    Reactions  and  movement  of  organic
      chemicals in soils.   Soil  Science  Soc.  America Special Publ. No. 22,
      Madison, WI.  pp. 271-304.

13.    Kjeldsen, P, and T.  Larsen.   1988.  Sorption af organiske stoffer i
      jord og- grundvand.   Laboratoriet for  teknisk  Hygiejne,  Danmarks
      Tekniske Hojskole,  Lynby.  85 p.  (In Danish with English summary).

14.    Mason,   B.   J.    1983.    Preparation  of  soil  sampling   protocol:
      techniques  and  strategies.    EPA-6QO/4-83-020,  U.S.  Environmental
      Protection  Agency, Environmental Monitoring and  Systems Laboratory,
      Las Vegas, NV.  89114.

15.    Maskarinec,  M.   P.    1989.   Oak  Ridge National   Laboratory,  U.S.
      Department   of   Energy,   Oak   Ridge,   Tennessee.      Personal
      communication, 4 August 1989.

16.    Maskarinec, M. P. and R.  L.  Moody.  1989.   Storage and preservation
      of environmental samples.   In:   Keith,  L. H.  (ed*), Principles  of
      environmental sampling, American Chemical Soc., Washington, DปC.  pp.
      145-155.

17,    Page, A. L.  (ed.).   1982.   Methods of Soil  Analysis - Part 2.   Am.
      Soc.  Agron., Madison, WI. 1159 p.

18.    Perket,  C.  L.   (ed.).    1986.    Quality control  in  remedial  site
      investigations:  hazardous and  industrial  solid waste test.   ASTM STP
      925.  American Soc. Testing and Materials, Philadephia, PA.

19.    Slater,  J.  P., F. R.  McLaren, D. Christenson  and  D.  Dineen.    1983,
      Sampling and analysis  of soil  for volatile  organic  compounds:    1.
      methodology development.  Proc. conference on characterization  and
      monitoring  in the vadose  zone,  National  Water  Well Assn., Las Vegas,
      NV.

20.    Standard Methods for the Examination of  Water and  Wastewater.   1985.
      16th  Edition.   American   Public  Health  Association,  1015  Fifteenth
      Street NW,  Washington, DC 20005.  p. 700.

21.    Triegel,  E. K.   1989.  Task Group  Chairman,  Subcommittee  D34.01,
      American Society of Testing and Materials, Philadelphia, PA.  Personal
      communication, 3 August 1989.

22.    U.S. EPA.    1983.   Treatability manual.   Vol.  I  -  Treatability  Data.
      EPA-600/2-82-0012,  U.S.  Environmental Protection  Agency,  Office of
      Research and Development, Washington,  D.C.  20460.
                                   462

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23,    U.S.  EPA.  1986.  Test methods for evaluating  solid waste.  SW-846.
      3rd.  Edition.    Volume  IB:    Laboratory  manual,  Physical/Chemical
      Methods,  Chapter  Four  -  Organic  Analytes.    U.S.  Environmental
      Protection  Agency, Office of  Solid  Waste  and  Emergency Response,
      Washington, D.C.   20460.

24.    Verschueren, K.  1983.   Handbook of environmental  data on organic
      chemicals.  Van Nostrand Rein hold Co., NY.   1310 p.
                                     463

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SECTION 7
APPENDIX
   464

-------
           APPENDIX A
SOLUTION VOC BREAKTHROUGH CURVES
                465

-------
                               METHYLENE CHLORIDE
         0.00
            0.00
2.00    4.00    6.00    8.00   10.00  12.00  14.C
    OUTFLOW VOLUME   (Soil  pore volumes)
1S.OO
Figure Al.  Solution breakthrough curve for tnethylene chloride.
                               1,2 DIGHLOROETHANE
         0.00
            0.00   2.00    4.00    6.00   8.00   10.00   12.00   14.00   16.00
                       OUTFLOW VOLUME   (Soil pore volumes)

Figure A2.  Solution breakthrough curve for 1,2-dichloroethane.
                                   466

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                              1,1,1 TRICHLOROETHANE
            0.00    2.00    4.00    6.00    8.00    10.00   12.00   14.00   16.00
                        OUTFLOW VOLUME   (Soil pore volumes)

Figure A3.  Solution breakthrough curve for 1,1,1-trichloroethane.
                               TRICHLOROETHYLENE
1
         0.00
             0.00    2.00    4.00    6.00    8.00   10.00   12.00   14.00   16.00
                        OUTFLOW VOLUME   (Soil pore volumes)

Figure A4.  Solution breakthrough curve for trichloroethylene.
                                     467

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                                    TOLUENE
1
         0.00
            0.00    2.00    4.00    S.OO   8.00   10.00   12.00  14.00   16.00
                      OUTFLOW VOLUME   (Soil pore volumes)
Figure A5.   Solution breakthrough curve for toluene.

1.20
1.00

0.80
Co/Ci 0.60
0,40
0.20
0.00 4
o.e
CHLOROBENZENE j|


J* 	 — — ' 	 ซ
jT- . 	 • 	 _ — *,
/

/
f 	 	 . . .
ป 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.
                       OUTFLOW VOLUME   (Soil pore volumes)
Figure A6.  Solution breakthrough curve for chlorobenzene.
                                  468

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               APPENDIX B
CHARACTERISTICS OF THE VOC SOIL  SAMPLES
                   469

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Table Blซ   Characteristics of the test column soil  samples used for VOC
            analyses.
               Soil  Weights
Soil Volumes^
Sample

A
A'
B
B'
C
C'
D
D1
E
E'
Wet Soil
E
27.45
29.20
126.16
126.24
128.82
122.45
120.59
115.75
72.56
66.37
Dry Soil1
s
24.45
26.01
112.38
112.45
114.75
109.08
107.42
103.11
64.64
59.12
Particle
em3
9.2
9.8
42.4
42.4
43.3
41.2
40.5
38.9
24.4
22.3
Water
em^
3.0
3.2
13.8
13.8
14.1
13.4
13.2
12.6
7.9
7.3
Air
em3
4.1
4.3
18.7
18.2
19.1
18.2
17.9
17.2
10.8
9.8
Total
car*
16.3
17.3
74.9
75.0
78.5
72.7
71.6
68.7- '
43.1
39.4
1 Dry solids content determined  grravimetrically on subsamples from
   samples   A,A',  B,B', D,D', E and E'.
   Average = 89.08%, std.dev.= 0.41%.
   Dry soil weight = 0.8908 * wet soil weight.
2 Particle volume = dry soil weight /(2.65 g/em^).
   Total soil volume =  dry soil weight/1.50 g/euA
   Water volume = 0.1092  * wet soil weight.
   Air volume =  total  volume - (particle volume + water volume).
                                    470

-------
           APPfiNDIX C
SOIL VOC SAMPLING EFFECTS
               471

-------
                                 HETHYLENE CHLORIDE
   PPM
               Disturbed   Undisturbed Disturbed   Undisturbed Undisturbed
               Plastic Bag  Glass Jar   Glass Jar   Glass Jar •  Glass Jar
               Lo Headsp.  Hi Headsp.  Lo Headsp.  Lo Headsp. Lo Headsp.
                                                                Methane!
                                  SAMPLING METHOD

Figure Cl*  Comparison of sampling method effects for  methylene ciiiioride.
             (vertical bar indicates standard error of treatment mean)
                                 1,2 DICHLOROETHANE
I
   PPM
               Disturbed   Undisturbed Disturbed   Undisturbed Undisturbed
               Plastic Bag  Glass Jar   Glass Jar    Glass Jar   Glass Jar
               Lo Headsp.  Hi Headsp.  Lo Headsp.  Lo Headsp.  Lo Headsp.
                                                                Hethanol
                                   SAMPLING  METHOD

Figure C2.  Comparison of sampling method effects for 1,2-dichloroethane.
             (vertical bar indicates standard error of treatment mean)
                                   472

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                               1,1,1 TRiCHLOROETHANE
        2.00
        1.50
   PPM  1.00
        0.50
        0,00
               Disturbed  Undisturbed  Disturbed  Undisturbed Undisturbed
              Plastic Bag  Glass  Jar   . Glass Jar   Glass Jar   Glass Jar
              Lo Headsp.   Hi Headsp.   Lo Headsp.  Lo Headsp. Lo Headsp.
                                                                Methanol
                                  SAMPLING METHOD

Figure C3.  Comparison of sampling method effects) for 1,1,1-trichloroethane.
             (vertical bar indicates standard error of treatment mean)
                                 TRICHLOROETHYLENE
   PPM
              Disturbed   Undisturbed  Disturbed   Undisturbed Undisturbed
              Plastic Bag  Glass Jar   Glass Jar    Glass Jar   Glass Jar
              Lo Headsp.   Hi  Headsp.   Lo Headspu  Lo Headsp.  Lo Headsp.
                                                                Methanol
                                  SAMPLING METHOD

Figure C4.  Comparison of sampling method effects for trichloroethylene.
             (vertical bar  indicates standard error of treatment mean)
                                    473

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   PPM
             Disturbed   Undisturbed Disturbed   Undisturbed Undisturbed
             Plastic Bag  Glass Jar    Glass Jar    Glass Jar    Glass Jar
             Lo Headsp.   Hi Headsp.   Lo Headsp.   Lo Headsp.  Lo Headsp.
                                                                Hethanol
                                  s<5AMPL!NG MiTHOD

Figure C5.  Comparison of sampling method effects for toluene.
             (vertical  bar indicates standard error  of treatment mem)
   PPM
              Disturbed   Undisturbed  Disturbed
              Plastic Bag  Glass Jar   Glass Jar
              Lo Headsp.   Hi Headsp,   Lo Headsp.
Undisturbed Undisturbed
Glass Jar    Glass Jar
Lo Headsp.  Lo Headsp.
              Methanol
                                  SAMPLING METHOD
Figure C6.  Comparison of sampling method effects for chlorobenzene,
             (vertical bar indicates standard error of treatment mean)
                                  474

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           APPENDIX D
QUALITY CONTROL SAMPLE ANALYSES
               475

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Table Dl.   VOC analytical method detection limits.
Target Compound

Methylene Chloride
1,2-WcMoroethane
lปli 1-Trichloroethane
Trichloroethylene
Toluene
Chlorobenzene

Water
ug/mL
0.1
0.05
0.005
0.002
0.04
0.03
Matrix
Methanol
ug/mL
0.1
0.05
0.005
0.002
0.04
0.03

Soil
ug/g
0.4
0.1
0.01
0.004
0.05
0.01
Table D2.   Characteristics of samples for  quality control analyses.
Sample Code
Weight
Description
Bl
B2
Cl
C2
C3
e
73.9 Methanol used for infield
preservation.
286.8 Clean soil used in this experiment.
24.8 Soil sample collected from
Method A.
control
column by
99.8 Soil sample collected from control column by
Method C (soil immersed in 100 mL methanol).
120.8 Soil sample collected from
control
column by
                               Method B.
                                     476

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Table D3.   Results of VOC spiking-and recovery analyses^-.
Target Compound

Methylene Chloride
1,2-Dichloroethane
1,1,1-Trichloroethane
Trichloroethylene
Toluene
Chlorobenzene
Spiked *
Concentration
ug/f dry soil
20.0
12.5
2.5
2.0
0.75
0.5
Recovery
Percentage
%
77
73
100
112
115
95
Estimated
Variance
%
ฑ20
ฑ10
+5
ฑ10 ,
ฑ10
ฑ5
  Samples of clean soil (i.e. uncontaminated study  soil) were spiked with
   the concentrations shown and then extracted and analyzed according to
   the same procedures as for the test soil samples (see text).
                                     477

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                           NATO/CCMS Guest Speaker;



                       Guus Annpkkee, The Netherlands



Biological Treatment of Contaminated Soil and Groundwater







                                     No text available.
                    479

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                     NATO/CCMS Guest Speaker:

                    D.B, Janssen, The Netherlands

Degradation of Halogenated Aliphatic Compounds by
Specialized Microbial  Cultures and Their Applications
                             for Waste Treatment
               481

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Degradation of halogenated aliphatic compounds by specialized
    microbial cultures and their application for waste treatment
           D.B, Janssen, A.J. van den Wijngaard and R.  Oldenhuis
                       Department of  Biochemistry
                        University of Groningen
                            The Netherlands
Prepared for;
4th NATO/CCMS Pilot Study on Demonstration of Remedial Action Technologies
for Contaminated Land and Groundwater,  Angers, November 5-9, 1990.
                                 482

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Abstract

      :The biodegradation of halpgenated aliphatic compounds by a .number of
pure bacterial cultures was investigated. It was found that 1-chloro-n-
alkanes>, several a,w-dichlorbalkanes, chlorinated alcohols and'some
chlorinated ethers can be used as sole carbon source by various gram-
negative or gram-positive organisms. Attempts to isolate bacteria that can
grow with compounds such as chloroform, 1,1-dichloroethane,
dichloroethylenes, trichloroethylene and l,lil-trichloroethane were not
succesful. Methanotrophic bacteria, however, could convert these compounds
by cometabolie oxidation to alcohols or epoxides that,may decompose
chemically.
      Application of microorganisms that use pollutants for growth seems
promising in the areas of waste gas-treatment and soil- cleanup. Thus,
addition of dichloroiethane-degrading organisms to soil slurries
contaminated with this compound resulted in shorter adaptation periods than
in non-inoculated soil. Processes that rely on cometabolic conversions are
more difficult to realize. Other methods for selective stimulation of the
active organisms than the presence of growth substrate need to be employed
and an additional energy source will be required.
                                     483

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Introduction

      Chlorinated hydrocarbons have found extensive application as
degreasing  agents,  solvents,  intermediates in chemical  sythesis 'and
agrochemicals  (Table 1).  Their environmental  fate is determined by their
resistance  to  chemical  decomposition,  the low number of microorganisms that
are able  to degrade chlorinated organics, and their water solubility and
volatility.

      Table 1. Production and use of some chlorinated  aliphatic hydrocarbons.
compound
1 ,2-dichloroethane

vinylchloride
perchloroethylene
trlchlorcethylene
carbon tetrachloride
1,1,1-trichloroe thane
msthylene chloride
methylehloride
2-chlorobutadiene
chloroform
1,1-dichloroethylene
production
(10s tonnes/yr)
13

12.0
1.1
1.0
1.0
0.45
0.4 -.
0.35
0.3
0.24
0.1
use
vinylchloride, gasoline
antiknocking agents, solvent
polyvinyl chloride
solvent
solvent
solvent, CHC
solvent
solvent
solvent, blowing agent
polymers
solvent, CHC
solvents, polymers
      During  the  last  several  years,  we have been  studying  the
biodegradation under aerobic conditions of  several  important
representatives of  this  class  of compounds.  Biodegradation  rates  are often
very  low, and  it  has been observed that several  chlorinated compounds may
persist  in polluted aquifers for many years. The cause  of these  low
degradation rates could  be unfavourable environmental conditions,  physical
unavailability of the  substrates,  or  the absence of microorganisms that  are
able  to  carry out biotransformation reactions. With halogenated  aliphatics,
this  last factor  often is of crucial  importance. Even under optimal
environmental conditions (neutral  pH,  20-30ฐC, sufficient nutrients
available), recalcitrant behaviour is  often  observed (Table 2).  Usually,
only  specific cultures have the  ability to utilize  these compounds for
growth (Table 3). Therefore, the development of  treatment technologies for
locally  polluted  environments  and  waste streams  will require  an
understanding of  the microbial potential  and the ecophysiology of  the
organisms involved. Such information  will give insight  in the extend of
                                  484

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removal  that can be achieved, the  conditions'Chat, must  be optimized and the
range  of waste  streams  that can  be treated.

       Table.2. Bacterial degradation of chlorinated aliphatic hydrocarbons.

1-ch loro-n-a 1 kanes
dichlororaethane
/chloroform
carbon tetrachloride
1,2-dichloroethane
1,1, 1-trlchloroethane
vinylchloflde
t-1 ,2-dichloroethene
trichloroethylene
tetrach 1 oroethy 1 ene
allykhloride
l,2-d1chloropropane
1,3-dichloropropene
aerobic
P E
PEC
C
R
• PEC
R 'C
PEC
E C
R EC'
R
E
R EC
PEC
anaerobic
M
"H
M ฅ
F
. F
R '
-M
"H
M
R, recalcitrant behaviour described
P, pure culture uses compound for growth
E, microblal enzyme capable of degradation known
C, cometabolic conversion by pure culture
M, methanogenic culture '
F, fermentative culture
                                        485

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 EnH chrnent cu 1 tures

       We have used batch and ehemostat cultures for  the enrichment of
 microorganisms  that  can degrade specific pollutants  (Table  3). Positive
 results  were obtained with  all 1-chloro-n-alkanes  tested, with several d,w-
 dichloroalkanes,  and with a number  of chlorohydrins  and chlorobenzenes.  In
 all  cases, it was possible  to isolate a pure culture once an actively
 growing  enrichment was obtained.
Table 3. Pure bacterial cultures that degrade chlorinated compounds.

Strain no.   Identity                Isolated on
                                                              Degrades also
    Chloroaliphatics
6JI, 6J3    Pseadonanas
CJiO-12     Xanthobacter
6J20-22
GJ70

ADi-3
           Hyphomicrobium
           Arthrotiacter
           Pseudomonas
           Arthrobacter
6J84        Corynebacterium
AD25
           AncyJobacter
                                 2-chlorpethanol
                                 1,2-dichloroettiane
methylene chloride
1,6-dIch1orohexane

epichlorohydrin

trans-3-chloroacrylJc
acid   :
chloroefhylvinylether
 chloroacetic acid"
 toluene, nethanol
 1-propane1, acetone
chloro- and bromoaikan'es
 formaldehyde
 1-chloroalkanes -
 1,9-dichlorononane
 vic-chlorohydrins

 cis-3-chloroa'cryHc '•••'
 acid  ;
 2-chloroethanpl
 T,2-dich1oroeth'ane
GJ30
GJ31
GJ60


Pseudcmonas
Pseudomonas
Pseudomonas


chlorobenzens
chlorobenzene
1 , 2 -d i ch 1 orobenze ne



toluene, benzene
1,2,4-dichlorobenzene
1 , 4-d i ch 1 orobenzene
toluene, benzene ,
AH  enrichments were negative with chloroform, 1,1-dichloroethant, 1,1,1-tricnloroethane,
1,1-dichloroethylene, cis-1,2- and trans-l,2-dichloroethylene, trichloroethylene,  perchloroethylene,
1,2-dichloropropane, hexachlorobutadiene and hexachlorobenzene.
       It  was observed  that the  outcome of an  enrichment experiment was
strongly  influenced fay the nature of  the inoculum and  the  identity ;of the
compounds.  All  soil and sediment samples used were positive when tested for
chloroacetic acid degradation,  but only a limited number of  inocula  gave
rise to dichloromethane utilizing enrichments,  while l,2-;dichloroethane
degradation was  even more seldom observed.                 .->  ,
       The pure  cultures that were isolated  in general  had  a broad substrate
range. Thus, 1,2-dichloroethane degrading Xanthobacter strains (Janss.en et
                                        486 '

-------
al., 1985)  also converted several  1-chloro- and 1-bromo-n-alkanes,  and even
toluene,.acetone,  1-hutanol,  etc.,  were used for growth  (fable  3).  A
similar  broad, substrate range was  found for the 1,2-dichlorobenzene
degrading  organism strain GJ60  (Oldenhuis et al., 1989a). Toluene,  benzene,
chlorobenzene,  1,4-dichlorobenzene and 1,2,4-trichlorobenzene also
stimulated growth  of this organism (Table 3).
      An  important aspect is  the  stability of the cultures. This was found .
to be highly variable. Some  strains did not show loss of their  specific
catabolic  activity even when  they were transferred on selective media for
years, while other cultures  had to be maintained on the  carbon  source that
was used-for enrichment to prevent rapid loss of their activity. This was
not related to the compound  on  which the organism was obtained, since
strain GJ31 was a very stable chlorobenzene degrader while  GJ30 rapidly
lost  its  activity on nutrient agar.
      Repeated attempts to obtain enrichments for a number  df  compounds
were not  successful. This included chloroform, 1,1-dichloroethane,  the
dichlorinated ethylenes, trichloroethylene,, and some other  compounds. A
number of  factors  could cause that a specific xenobiotic is not used for
growth:
- the compound or intermediates are not converted by micrqbial  enzymes;
- degradation does not yield  energy or carbon for growth;
- the compound is  toxic;
- the compound is converted  to  toxic metabolites (Fig. 1).

                                  CH2Sr-CH2Br

             •      • 'A      Br-       K-
                   • cH2-XCHi  •*—^— CH23r-CH2OH 	>  CH28r-CKO
                                                     i
                                                     I
                    CH2OH-CHjOH   •  CHjOH-CHjOH        CH23r-COCH
                                                      'Br'
                                                  CH2OH-CCCH """"

Fig. 1. Possible conversions of 1,2-dibromoethane by different bacterial cultures.  Several enzymatic
      steps enabling dehalogenation and utilization of this compound have been identified. The
    .  necessary combination of theseactivities, yielding a complete catabolic route,  however, has not
    •  yet been found,	    '                 .
       In order to understand the relative importance  of  these factors, we
have  decided to- study  physiological pathways through  which halogenated
aliphatics can be converted. Special emphasis was given  to dehalogenatio'n
reactions since this  is  the step where toxicity  is  lost.  It can also be
expected to be a biochemically difficult step, since  carbon-halogen bonds
are only present in a  limited number of natural  compounds.
                                      487

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jJehalogenatlon

       Dehalogenation of several  chloroalkanes was  found to be  mediated by
low molecular weight hydrolytic  dehalogenases. The first enzyme  that was
found  to be able  to hydrolyze  a  chlorinated hydrocarbon not containing
other  functional  groups was  identified in a strain of Xanfhobaoter that was
isolated on 1,2-dichloroethane (Janssen et al.,  1985; Keuning  et a!., 1985)
(Fig.  2), A hydrolytic dehalogenase was also identified in a 1,6-
dichlorohexane utilizing organism (Janssen et al,,  1988b). A broad range of
compounds could be  converted by  these systems (Table 4).
Figซ 2. Catabolic route for 1,2-dichloroethane
      by Xanthobacter autotrophicus. Two
      different hydrolytic dehalogenases,
      produced constitutlvely, cause
      dechlorination. The haloalkane
      dehalogenase has a remarkably broad
      substrate range. The 1nduc1ble
      dehydrogenases are usual enzymes of
      Xanthobacter and play a role in the
      metabolism of natural alcohols. The
      final product, glycolic acid, is a
      normal intermediate in bacterial meta-
      bolism.
                                             CH2a-CH2Ct
                                                  H20
                                                  HC1
CH2Ct-CH2OH
     PQQ
     PQQH2
CHjCl-CHO'
            haloaltane
             dehalogenase
               chIA
  alcohol
   dehydrogenase
    mox
     NAD + H20 aldehyde
     NADH,   dehydrogenase
         2     aid
CH,Cl-COOH
     H20
     HCl
CH2OH-COOH
   I
central metabolic routes
haloalkanoie acid
   dehalogenase
   dNB
       Recently, the  three dimensional  structure of  the Xanthobacter
dehalogenase has  been resolved  (S.  Franken, B. Dijkstra et al.,  in
preparation). The structure suggests the involvement of a carboxylate group
in the dehalogenation reaction, which  would proceed by a nucleophilic
desplacement mechanism. If this  is  correct, then  it is evident why'
compounds such as chlorinated ethylenes are not a substrate. The  presence
of ir  electrons shields the carbon from nucleophilic groups. Compounds such
as chloroform and 1,1,1-trichloroethane probably are not converted because
of steric factors.
       We have observed a striking degree of correlation between the
possibility of hydrolytic dehalogenation and utilization as a growth
substrate. One of the compounds for which repeated  attempts to isolate a
pure  culture were not succesful  is  1,2-dichloropropane. This chemical has
entered the environment due to contamination of the nematocide 1,3-
dichloropropylene. It also is an industrial waste chemical. The compound
is known to persist  in the groundwater environmental  for decades,
                                       488

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Table 4. Substrates of haloalkane dehaloaenases.
Compound
methylchloride
methylbromide
methyl iodide
dibromo methane
bromochloromethane
ethylchlorlde
ethylbromide
ethyl iodide
1,2-dichloroethane
1,2-dibromoethane
1-chloropropane
1-bromopropane
2-bromopropane
1 , 3-d i en loropropane
3-chloropropen.e
1 , 3-di ch loropropene
1 , 2 -d i broroopropa ne
1-chlorobutane
1-bromobutane
2-bromobutane
GJ10
28
14
14
-
-
24 ,
24
-
100
94
51
29
-
80
45
- •
119
31
27
, - .
GJ70
0
143
75
13
5
0
143
93
13
172
15
100
97
102
139
133
148
66
90
60
Compound
2-bromoethanol
3-brotnopropanol
l-ctiloro-6-hexanol
l-bromo-6-hexanol

b i s ( 2-ch loroethy 1 )ether
chloroethylvinylether

l-phenyl-2-bromopropane

1-chloropentane
1-bromopentane
2-bromopentane
1-chlorohexane
1,6-dichlorohexane
2-brotnooctane
1.9-dlchlorononane
1 , 2 -d i ch 1 oropropane
epichlorohydrin
epibromohydrin
GJ10
7
_
4
-

-
-

_

0
32
-
• 3
4
-
4
0.6
14
129
GJ70
55
123
' 60
68

30
13

18

65
60
38
85
67
-
26
-
•
-
Relative activities of purified dehalogenase of Xanthobacter autotrophicus GJ1Q and Arthrobacter GJ70.
The purified enzymes have an activity of 6 and 3 U/mg of protein, respectively, with 1,2-dibromoethane.
We  propose  that this recalcitrance  is related  to the  extremely low activity
of  hydrolytic dehalogenases  towards  this compound. The  strain  GJ10
dehalogenase described in  Table 4 has a 160-fold lower  activity with  1,2-
dichloropropane than with  1,2-dichloroethane.  The product of conversion  is
a mixture of l-chloro-2-propanol and 2-chloro-l-propanol, which both  may
serve as carbon source for cultures  that have  been obtained  in our
laboratory  (Fig,  3). Therefore, the  lack of  conversion  could be related  to
a single activity being absent.
                                         Cl Cl
                         hydrolytic
                         denalogenase
XH2
 monooHygenase
Fig. 3. Conversion of 1,2-dlchloropropane by hydrolysis (haloalkane dehalogenase) or by oxidation
       (methane monooxygenase).

-------
       Other mechanisms of  dehalogenation  have been discovered in
dihalomethane  degrading organisms and  in  strains that use  haloalcotiols  for
growth. Apparently, there  are two possible  routes for the  direct
dehalogenation of haloalcohols;  hydrolysis  to produce glycols'or
intramolecular substitution  to produce epoxides (Fig 4).
Ffg. 4.  Catabolism of eplchlorohydriri in Pseudomonas
       KOI Involves the activity of an epoxide •
       hydrolase and a dehalogenase that converts
       vicinal alcohols to epoxides. Both enzymes are
       Inducible (van den Hijngaard et al., 1989).
              I
           OH OH
          HjC-CH-CHjCl

           '  I
           OH  o
           I    / \
          H2C- CH-CH2
                                                  OH OH OH          '-  "
                                                 HjC- CH-CH2

       Little  is  known about  the conversion  of S-halocarboxylic acids.
       Qxidative  conversions  seem to be rather widespread  but their
relevance to  organisms that  use halogenated compounds as  a carbon source
remains to be demonstrated.

Application of organisms                                             ;'.
       We have tested whether  addition of  specific cultures  to slurries  of  ,
contaminated soil  can decrease adaption periods or increase degradation
rates.  It was found that dichlorornethane  removal occurred faster when
dichloromethane  degrading organisms (Hyphomicrobium GJ21 or
Methylobacteriura DM2) were  added to contaminated soil (Fig.  5). Without '
inoculation, no  significant degradation took  place within 100 h. Similar
results have been  obtained  with the degradation of chlorinated benzenes and
1,2-dichloroethane. The engineering aspects of'bioreactors  for the
treatment of soil  slurries  have been investigated by others  (Kleijntjes et
al.,  1987).                                                           :
Fig, 5. Effect of inoculation on the
      degradation is soil slurries.
      Symbols: ป, sterile control; o, no
      organisms added; A,
      Hethylabacterium strain DM2 added
      (Kohler-Staub and Letsinger,
      1985); •, Hyphomicrobium GJ21
      added. The concentration of
      dlcnlororoathane was followed by  .
      gas ehrornatography.
490
                                                20
                                                      IiO      60     80
                                                          Time (h)
                                                                         ICO  600

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      Other areas of application  of  selected cultures are being developed.
This includes  immobilization  of 1,2-dichloroehane degraders for groundwater
treatment  in packed bed  bioreactors  and the use of dichloromethane
degrading  bacteria for waste  gas  treatment.

Oxidative  cometabolism

      Since 1985  (Wilson and  Wilson,  1985), the possibility to convert
chlorinated ethylenes by cometabolic reactions has received increasing
attention  (Fogel  et al.(  1986;  Little et al.(  1988;" Janssen et al., 1988a;
Oldenhuis  et al., 1989b).  Methanotrophs, toluene, propylene and ammonia
oxidizers  have been tested for  their capacity to degrade halogenated
aliphatics by  cometabolic oxidation.  The oxygenases involved have a broad
substrate  range and convert chlorinated compounds to alcohols, epoxides,
etc.

Table 5.  Degradation of some halogenated compounds by soluble (sMHO) and partlculate (mMMO)
       methane monooxygenase.
Compound
Dichloromethane
Chloroform
Carbon tetrachloride
1,1-Dichloroethane
1,2-Dichloroe thane
1,1,1-THchloroethane
l.l-D1chloroethylene
trans-1 ,2-Dichlorpethylene
cis-1 ,2-D1chloroethylene
Trichloroethylene
Tetrachloroethylene
1,2-Dichloropropane
trans-1, 3-D1chloropropylene
sterile
0.167
0.124
0.046
0.033
0.092
0.065
0.030
0.083
0.110
0.050
6.069
0.129
0.138
Cone.
sMMO

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•Table 6. Degradation of chloroaliphatics by H.  trichosporiumOZ3b.

 compound                                           chlorinated proeluct(s)"

 dkhloromethane                       -              chloride
 chloroform                                         chloride
 carbon tetrachloride                                  no conversion
 1,1-dichloroethane                                   chloride
 1,2-dichloroethane                                   chloride
 1,1,1-trlchloroethane                                 2,2,2-trichloroethanol
 trans-l,2-dichloroethylene                             chloride, epoxids
 cls-l,2-dlchloroethylene                              chloride, epoxide
 trichloroethylene                   •                 chloride, 2,2.2-trichloroethanol
 tftrachloroethylens                                  no conversion
 1,2-dichloropropane           '                       l,2-dichloro-3-propanol

 * Incubations were done at 30 ฐC with resting cells from chemostat cultures grown in medium
 containing no added copper. Compounds were added at 0.1 i*i and formate was used as electron donor.
        One of the  most Important compounds that  can be converted by methano-
 trophs is trichloroethylene.  Rapid conversion of TCE was achieved under
 conditions that stimulate expression of the  soluble methane  monooxygenase
 only.  The kinetics of TCE degradation by methanotrophs compares favourably
 to toluene oxidizing organisms  that degrade  TCE (Oldenhuis et al., 1990).
 The  Kj  values (first order rate  constants) are  similar but methanotrophs
 have a higher Vroax. A problem with both toluene  oxidizers' and methanotrophs
 is the toxicity of TCE degradation products. This will require significant
 amounts of methane to stimulate growth of new active cells  if in a
 treatment system  larger amounts of TCE have  to  be converted.

 Application  of cometabolism

        We have found that addition of methane to soil slurries that were
 contaminated with chloroform, TCE and perchloroethylene  only stimulated
 chloroform conversion significantly (Fig. 6).  In slurries  that contained
  tra/?s-l,2,-dichloroethylene,  rapid degradation  was achieved  when either
 methane or methane plus cells of a Methylomonas culture  were added  (Fig.
 7).  By methane addition alone,  probably only cells expressing the
 participate  methane monooxygenase were stimulated. Similar observations
 have been made  in field studies (McCarty  et  al., 1989).  More efficient
 methods for  specific stimulation of methanotrophs expressing soluble
 methane monooxygenase have to be developed.  Copper availability, which
 regulates.the  switch from expression of soluble to participate enzyme will
 be  difficult to  manipulate  in a natural environment or treatment system
 receiving co^p^ex waste streams.
                                   492

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                         CONTROL
WITH CELLS AND  CH4
                                                           40
Fig, 6. Degradation of chloroform, trichloroethylene, and perchloroethylene In a soil slurry exposed to
      methane.
                                          CONC.
Fig. 7. Degradation of trans-l,2-dichloroethylene
      in soil  slurry.
Treatment systems
      Application of  selected microbial  cultures for cleanup purposes  can
be attractive in order to reduce adaptation periods. Several areas are
promising;
- inoculation of waste gas treatment  biofilters and trickling filters;
- startup of fixed beds for groundwater  treatment;                  •  •
- inoculation of bioreactors for soil, sediment and sludge treatment;
~:iin.s-itu treatment after injection of microorganisms,
      Although the number of practical scale experiences with these  -.
applications is very  limited (Morgan  & Watkinson, 1989), several
                                        493

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considerations  indicate that inoculations could be very helpful.'
      Natural polluted ecosystems seem to show variability with respect to
presence of microorganisms that can degrade certain pollutants. Thus,,
subsurface samples often do not show significant degradation of
dichloromethane, 1,2-dichloroethane or 1,2-dichlorobenzene unless
microorganisms  that are capable to use these compounds for growth are
added. Cultures that degrade xenobiotics are not always present in a1   >
certain polluted environment and this may prevent degradation even after
conditions have been optimized.
      Experiments with trickling filters for waste gas treatment also show
that inoculation may be useful for obtaining rapid establishment of an
active microflora (Diks and Ottengraf, 1989).
      Cells immobilized on a solid support can be used for groundwater
cleanup. Both activated carbon (Stucki, 1990) and diatomeceous earth
(Friday and Portier, 1989) have been used as support material for the
Xanthobacter strain that degrades 1,2-dichloroethane. These systems are
currently scaled up for practical application.
      Novel developments will be the application of microorganisms that
rely on cometabolic conversion. On a laboratory scale, several interesting
reactor setups  have been proposed, but the efficiency seems to need further
improvement (Strandberg et a!., 1989).
      Another attractive possibility is the combination of anaerobic and
aerobic treatment- steps for complete dehalogenation of compounds that are
not converted under aerobic conditions. Highly chlorinated compounds are
subject to reductive dehalogenation, catalyzed by anaerobic organisms such
as clostridia and methanogens (Voge'l et at., 1987). The products could be
converted further by aerobic treatment.
      In all cases, more insight into the ecophysiology of the organisms
that carry out  the dehalogenation steps will be essential for identifying
the basic process conditions that are needed for optimizing the numbers and
activity of the xenobiotic degraders. The use of bioreactors,that allow
fine control of growth conditions will increase the success of these novel
treatment technologies.
                                     494

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literature cited

Oiks, R.H.H, & S.P.P. Ottengraf. 1989. Prozesstechnologische Aspekte der Abscheidung von chlorierten
Kohlenwasserstoffe aus der Abluft in Biotropfkorper. VOI Berictite 735:7-24.

Fogel, H. H., A. R. Taddeo, and S. Fogel, 1986. Biodegradation of chlorinated ethenes by a
methane-utilizing mixed culture, Appl. Environ. Hicrobiol. 51:720-724.                       '.

Friday, D.D., and R.J. Portier. 1989. Evaluation of a packed bed immobilized microbe bioreactor for the
continuous biodegradation of halocarbon- contaminated groundwater.  AHMA/EPA International Symposium on
Biosystems for Pollution Control, Cincinatti,

Janssen, D.B., A. Scheper, L. Dijkhuizan, and B, Hitholt. 1985. Degradation of halogenated aliphatic
compounds by Xanthobacter autotrophicus GJ10. Appl. Environ, Microbiol. 163: 635-639.

Janssen, D.B., G. Grobben, R. Hoekstra, R. Oldenhuis, and B. Hitholt. 198Sa. Degradation of
trans-l,2-d1chloroethene by mixed and pure cultures of methanotrophic bacteria. Appl. Hicrobiol.  Bio-
technol. 29:392-399.

Janssen, O.B., J. Gerritse, J. Brackmaju C. Kalk, 0. Jager, and B.  Hitholt. 1988b.-Purification and
characterization of a bacterial dehalogenase with activity toward halogenated alkanes, alcohols,  and
ethers. Eur. J. Biochetn. 171:67-72.

Keuning, S., O.B. Janssen, and.B. Hitholt. 1985, Purification and characterization of hydrolytic   •
haloalkane dehalogenase from Xanthobacter autotrophicus GJ10. J. Barterfol. 163:635-639,

Kleijntjes, R.H., K.Ch.A.M. Luyberr, M.A. Bosse, and L.P. Velthuisen, 1987.  Process development for
biological soil decontamination .in a slurry reactor. Proc, 4th Eur, Congr.  Biotechnol. 1:252-255
{Elsevier, Amsterdam),

Kohler-Staub, D, and T. Leisinger. 1985. Dichloromethane dehalogenase of Hyphomicrobiusn sp. strain DM2,
J. Bacteriol. 162:676-681.

Little, C. D., A, V. Palumbo, S. E. Herbes, H. E, Lidstrom, R. L. Tyndall,  and P.  J.  Gilroer. 1988.
Trichloroethylene biodegradation by a methane-oxidizing bacterium,  Appl. Environ.  Microb,iol. 54:951-956,

HcCarty, P.L., L. Semprini, and P.V. Roberts. 1989. Methodologies for-evaluating the feasibility  of
In-situ biodegradation of halogenated aliphatic groundwater contaminants by tnethanotrophs. Proc.
AHMA/EPA International Symposium on Biosystems for Pollution Control, Cincinatti,

Morgan. P., S R.J. Hatkinson. 1989. Microbiological methods for the cleanup of soil  and ground water
contaminated with halogenated organic compounds. FEHS Microbiol. Rev. 63:277-300.

Oldenhuis, R., L. Kuijk, A. Lammers, D.B. Janssen, and B. Hitholt.  1989a. Degradation of chlorinated and
non-chlorinated aromatic solvents in soil suspensions by pure bacterial cultures,  Appl. Hicrobiol, Bio-
technol. 30:211-217.

Oldenhuis, R,, R.L.J.M. Vlnk, D.B. Janssen, and B. Hitholt. 1989b.  Degradation of  chlorinated aliphatic
hydrocarbons by Methylosinus  trichosporium OB3b expressing soluble  methane  monooxygenase. Appl. Environ,
Hicrobiol. 55:2819-2826.

Oldenhuis, R., J.Y. Oetzes, J.J. van der Waarde, and O.B. Janssen.  1990. Kinetics  of  chlorinated
hydrocarbon degradation by Methylosinus  trichosporium OB3b and toxicity of  trichloroethylene.  Appl
Environ. Micrcbiol. 57, in press.
                                                 495

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Strandberg, B.W., T.L. Donaldson, and L.L. Farr. 1989.  Degradation of triehloroethylene and
trans-l,2-dichloroethy1ene by a methanotrophic consortium 1n  a  fixed-film, packed-bed bioreactor.
Environ. Sci. Technol. 23:1422-1425.

Sttieki, G., 1990. Biologische Entsorgung von CKH's aus  Grundwasser und aus Hutterlaugen von chemischen
Prozessen. In: Proc. 7. Dechema-Fachgespr, Unweltsch.  Anwendung von speziellen Mikroorganisinsn zur
Behandlung von Abwlssern rait sehwer abbaubaren inhaltsstoffen,  12-13 Harz 1990, Franfurt am Main.

Vogel, T. H., Criddle, C. S. and McCarty, P. L. 1987.  Transformations of halogenated aliphatic
coispounds. Environ. Sci. Technol. 21:722-736,

Wilson, J.T,, and 8.H. Wilson. 1985. Biotransfortotion of trichloroethylene  in soil. Appl. Environ.
Hicrobiol. 49:242-243.

Wan den Hijngaard, A., O.B. Janssm, and B. Hithplt.  1989. Degradation of epichlorohydrin and
halohydrins by three bacterial cultures isolated from freshwater sediment. J. Gen. Hicrobiol,, 135:2199-
2208.
                                                  496

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       NATO/CCMS Guest Speaker:



   Rene Kleijntjens, The Netherlands



               Microbial Treatment
497

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  Technological  and  kinetical
  aspects  of  rnicrobial  soil
  decontamination  in  slurry
  reactors  on   mini  plant  scale.
R.H,  Kleijntjens, A.J.J. Smolders, K.Ch.A.M. Luyben


   Department of Biochemical Engineering,
   Delft University of Technology,
   Julianalaan 67, 2628 BC Delft, The Netherlands
                   498

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      A3STHACT

Technological  and  kinetical  aspects  of microbial soil decontamination in
slurry reactors on mini—plant scale

R.H. Kleijntjens, A.J.J. Smolders, K.Ch.A.M. Luyben, M.C.M. Van Loosdrecht,
Department of Biochea. Eng. , Delft University of Technology, Julianalaan 67,
2S23 EC Delft, The Netherlands

A  new  soil  .-slurry bicprocess for the decontamination of polluted soils is
developed using an integral research approach. For this reason technological
and  hydrocyr.amical  research  on  soil  slurries  in  three  phase  (S-L-G)
suspension  reactors  is combined with biological degradation experiments in
the same type of suspension reactors.
In  the  kinetical • experiments  aerobic  microbial  degradation activity is
studied in a slurry nini-plant. The slurry handling in the three stage mini-
plar.t,  consisting of two bioreactors in series and a dewatering section, is
executed  in  line  with  the  full  scale  process design. Also the process
conditions  are  chosen  close  to the expected full scale conditions. First
step  in  the  process  is the separation of entering soil into a coarse and
fine  particle-fraction. It is the fluidized coarse fraction which is, after
a  relatively  short  residence time, withdrawn from the bottom of the first
reactor  while  the  suspended  fraction remains in the system. This mode of
operation  makes  the  first  reactor  a bioreactor-separator unit, on which
further slurry handling is based.
Preliminary  experimental  results  have  shown  that separation of polluted
soil,   in the primal unit, into two different fractions can be achieved in a
semi-contiguous  node. The average solid hold-up in the first experiment was
15 wt?i, in the entering soil diesel present as an oil-like' pollutant with an
average  concentration  of  10  g/kg  dry  matter.  In  the withdrawn coarse
fraction,  containing  mainly  the relatively clean sand particles, a diesel
concentration  of  about  1.5  gr./kg  dry matter was detected. The fine soil
fraction,  containing  mainly  clay  and  silt particles which adsorb prefe-
rentially  the  pollutant,  is  transported  from  the first into the second
bioreactor.   It  is  in  the,  fines  containing,   suspension that microbial
degradation  activity  is  located.  The  average  residence  time  for  the
suspension  of fines in the mini-plant is about one week.  After remixing the
fine  and coarse fractions in the third,  dewatering, stage an overall diesel
conversion of 70 % could be-measured.
For  the  giver, process conditions, chosen as' pH 7,  temperature 30 ฐC,  and a
nutrient  medium  of only Fe, Mg, P and N (fertilizer),  the microbial system
was considered not to be functioning optimally.  This conclusion was based on
the rather small degradation activity measured in the suspension of fines in
the second bioreactor.
A  biokinetical model was developed to study the degradation process in more
detail.  Four  flows through the system were to be measured in order to test
the  model:   diesel,   oxygen,  carbon dioxide and the free proton flow. Pre-
liminary  model  results predict an overall yield of 0.4 Cmole biomass/Cmole
substrate,  agreeing with literature values. Also a low rate of nitrification
in the system is predicted by the model.               ,.   •   .
Optimization of the process conditions related to slurry handling and futher
development of the model is on its way.
                                   499

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                           Introduction
               General  eima:

  The development of o continuous  slurry  bioproeess for
  aoil decontamination.
  The set-up of a kinetica! description for aerobic diesei
  breakdown In the  slurry system.
      Characteriatics  of  the  slurry  ay_atern..
            Soil:
  Particles ore  ogglomoroted
  and packed;
  Pollutants are encapsulated
  in lerge aoil particles;
  Impeded transport of O2,
  CO, and nutrients.
             — Particles are freely suspended;

             — Improved avatlability of pollutants
                due to surface  enlargement:
             — Increased transport rates.
               Set-up  of  research;

   Construction and development of a continuously operated mini plant;
   Technological  description of the three phase slurry (S—L—G);
   Development af a blokiiieticol model for the  aerobic diesei  degradation;
   Experimental determination of the diesei breakdown in the mini plant;
   Vclidation  of the mode! with data from mini  plant  experiments.
                          Impeded     Improved
                         transport     transport
                                                             Pollutant


                                                        Soil          Slurry
   Slurry   characteristics  In  the  mini   plant
               Two important, technological design parameters
               are  investigated:
               — the solid hold—up, particle loading  of the system;
               - the particle size distribution, in the slurry.
CiaaatfScation  of  soil  particles
 jina frgetlon:
 clay and silt, large
 specific surface
 dp-1-50 fan
 high adsorbing power
 for oil pollutants
       coarse fraction:
      sand, small specific
      surf oca
     •  dpซ1QQ—1000 Mm
     • low adsorbing power
      for oil  pollutants
As shown in the  figure, the influent soil is split into
o fine ond coorsa fraction, which are recombmed
after tho second stage. An average solid  hold-up
of 15 % (w/v) is reached.
                     Particle  aize distribution  In mini plant
                                         .m.
      SOIL
        IN
1: BIOfiEACTOR/
  SEPARATOR
2s BIOREACTOR
                                   S
                                   ง a.


                                   I"
MbtCfOM 1
ruxt. KS>

imj.
Bfl
MaL
- v . IJSLIJ
**jmpu DM
\
r* **
                                                                   DM-MOW! G-w}
                                      SOIL.
                                      OUT
                                               500

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  SOIL
  H20
      AIR
                                  Waste
                                  water
                                               1: BIOREACTOfV
                                                 SEPARATOR
                                               2: B1ORE4.CTOR
                                               3i DEWATERING
                                               4: SOIL.  CYUNO6H
                                               S; R-CLMATIC
                                                 VALVES
  Modelling   of   continuous,   aerobic   dfese!   degradation
  The soil slurry  is an ecosystem in which, besides  diesel degradation, several
  other  microbiological processes, like nitrification,  humification etc.  occur.
  Diesel,  a mixture containing compounds  ranging from alkanes to  paiyoromotic
  hydrocarbons, is  degraded by a mixed population  of microorganisms.
  In  the model, only three processes are  considered relevant: diesel  degradation
  with ammonium  (1) and nitrate (2) ets N—source Respectively and nitrification (3).
                       Stoichiometric relations
         DIESEL + allll,

         DIESEL ป ปHO
->  C8IOHASS + 
volupซtrlc liquid flow •
,voiuBซtrlc 9ซs flow
rtiidinct tlซป

tli.
Iluldll.d b.d
protons
iMdiun
OK-ion<
Boil BUAponftion
                                             501

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Mini  plant  performance;
Expnrtmental conditions:  —  Residence time:  2  x  100 hours
                       -  T=30 C, pHป7,0
Tho mfnipfant  was operated  for 60 days, giving ;tha following  ovaroge
      concentrotions:  — influent soil                :  10   g/kg
                                                         g/kg
                                                         g/kg
— influent soil
— reactor 1  —  suspension
             —  fluldized bed
— raactor 2  —  suspension
— affluent soil
10
10.5
 1.5
 8
 3
                                                         g/kg
— The influent soil con  be  split into  o  relatively clson  coarse
  fraction and o mare  polluted fine  fraction (see figure).              '
— An overall diesel conversion of 70 percent was reached  in this
  system.
Experimental   verification   of  the   model:
                                                                                        If^Mf it
    f'
       CLQ

       3LO
   t"
                      In reactor  1, the following 4 conversion rotes were
                      measured in the " steady state ":
                      - Diesel            :    —1.94 C-mmol/l.h
                      — Oxygan           :    —1.50    mmol/I.h
                      — Corbon dioxide    :     1.2C1    minot/l.n
                      - Protons           :     0.25    mmol/I.h

                      By putting  these values  in the biokinetical modul, other
                      model parameters can be determined. Some  pnDlirner.ory
                      conclusions can bo drawn:
                      — The  bruto yield of biomass on dfsse! is about 0.4, which
                        is in occordonee with literature data.
                      —, The  nitrification rate  is relatively  iow,

                      Future research will concentrate  on  Improving the diesel
                      degradation in the  second reactor, and making a nitrogen
                      balance over the system for a more profound evaluation
                      of  the  biokinetical mode!.
              opซrotlon time  (day*)
                                             502

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                                NATO/CCMS Guest Speaker:



                               Kare! Luyben, The Netherlands



Dutch Research on Microbial Soil Decontamination in Bioreactors
                         503

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  Dutch  research  on  microbial soil decontamination in bioreactors

  K.Ch.A.H.  Luyben1,  S.  Annokkee0 R.H. Kleijntjens*

  "TWO Division of  Technology -for Society, P.O. box 342, Apeldoorn

  * Biotechnology  Del-ft  Leiden,  BDL
   Department  oi  Biochemical Engineering, Del-ft University-.of Technology,
   Julianalaan 67,  2628 BC  Del-ft, The Netherlands

  Micro-organisms are able  to convert aerbbically a broad range of xenobiotic
  organic substances into new biomass, carbondioxide  and water. This
  degrading  ability can not only be used for water solubilized xenobiotics,but
  also -for substances adsorbed  in soil. Major  hinderences  for in situ
  biodegradation  in soil  are firstly the difficulty in contact between
  organisms  and adsorbed pollutant and secondely the  poor  mass transfer  to the
  bioactive  sites.
  The use o-f bioreactors to overcome these hinderences is  studied in the
  Netherlands  by  means  of two research projects on reactor  application for
  microbial  soil  decontamination. One project  is carried out by TWO, the other
  by TUD.  Gonerally speaking both projects can be characterized by the
  following  research items:

  -optimum conditions for biodegradation has to be reached by applicating a  '
   biareactor

  -the treatment  time of the polluted soil in  the bioreactor has to be short
   as passible

  -the types af bioreactors that  can be used have to  be simple and robust

  -short term  implementation in practice


  Due to reasons  of confidence  neither the TNO nor?the TUD project can be
  treated in detail,  nevertheless some fieatures of the projects will be
  presented!


  TND-project
Preliminary the following overall results are achieved:
- A dry traataent method (10 - 151 humidity of the soil} soil as such) as well
  as * wet trostment method (soil slurry) have potentials for being applicated
  in practice.
• Tho design criteria for the bioreaetor types used in the dry and wet method
  are known,
- Both batch and continuous processes can be applied.
- A variety of soil types (from sarid to loam) can be treated.
- Experiments have been carried out on soils polluted with mineral oils and
  polvcyclic uromates^PCA's) with the following results!

                                       504

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treatment
  method
soil
type
contaminant
contaminant concentration (mg/kg dry soil)
 day 0            day 3            day  14
  dry
  dry
  wet

  wet
  wet
sand
sand
loamy
sand
loam
loam
cutting oil
diesel fuel
cutting oil

cutting oil
PCA's
 3,000
 4,200
26,000

65,000
 3,900
  980
1,800
9,000
1,700
   680
   900
 1,200

12,000
   300
  TDD project
  To overcome the earlier mentioned hinderences -for soil decontamination a
  a  tapered  three phase slurry reactor is under development in which soil
  particles  can be.suspended in processwater to'create.an optimum micro-
  environment -for the biodegradation.  Suspension is attained by means o-f a,
  special  designed injection system using compressed air and water. With this
  newly designed injector it. is possible to make optimal use o-f the natural
  segregation occuring in a three phase slurry. This segregation results into
  a  bottom -fraction containing larger  particles and a bulk -fraction containing
  smaller  particles.    .  ,-          ,

  Degradation kinetics in the slurry are studied measuring the concentrations
  o-f subtrate,  oxygen and carbondioxide as a -function o-f time during batch
  experiments and during continuous processing. A simple model is developed to
  describe the kinetics o-f  the system. Both in the model and in experiments
  attention  is paid to,mass trans-fer and suspension characteristics in the
  three phase slurry.
  The suspension behavior o-f soil particles in the three phase slurries is
  studied  both on laboratorium and pilot-plant scale. Understanding the
  per-formance o-f high density suspensions at di-f-ferent scales demands an
  intens research e-f-fort -for both technical and theoretical aspects. A
  combination o-f insight in the physics o-f soil suspensions, mass trans-fer
  properties and biokinetics should result in optimum operation conditions -for
  this process. This should then lead to a -flowsheet including pre- and. a-fter-
  treatment  operations in relation to the central slurry reactor. Finally, a
  study,to access the economical feasibility o-f the process will -follow.
                                        505

-------

-------
                   NATO/CCMS Guest Speaker:

                  Ya/cin B. Acar, United States

                   Electrokinetic Soil Processing
Reprinted from Ground Improvement and Grouting
 Specialty Conference with Permission from ASCE
            507

-------
               ELECTROKINETIC SOIL PROCESSING
                 (A Review of the State of the Art)

                      Yaicin B.'Acar1, M.ASCE
                            ABSTRACT

      Electrokinetic soil processing is an emerging technology in waste
remediation and treatment. This paper reviews electrokinetic phenomena
in soils and provides the fundamentals  of contaminant removal by the
technique.  The results of studies reporting ion/contaminant removal using
electro-osmosis are presented. Engineering implications are provided for
the further development and implementation of the process in remediation.

                         INTRODUCTION

      Electrokinetic soil processing using low level DC currents (of the
order of milliamps per cm of electrode area) is envisioned to be used for
removal/separation   of  organic  and  inorganic  contaminants   and
radionuclides, construction of barriers and leak detection systems in clay
liners, diversion schemes for waste plumes, and for injection  of grouts,
microorganisms and nutrients into subsoil strata (Mitchell 1986; Acar and
Gale  1986; Renauld and Probstein 1987;  Acar, et al. 1989).

      Coupling between electrical, chemical and hydraulic gradients  is
responsible for different types of electrokinetic phenomena in soils (Mitchell,
1976). Electro-osmosis (EO) is one of these phenomena where the pore
fluid moves due to application of a constant low DC current (or voltage) by
electrodes inserted in a soil mass. In the last five decades  since its first
application (Casagrande 1947), electro-osmosis has been investigated and
used  for different applications (Named et at. 1991),  The potential of the
technique in waste remediation resulted in initiation of several recent studies
(Putnam 1988; Acar et al. 1989; Khan et al, 1989; Thompson 1989; Mitchell
and Yeung 1991),  The need to utilize the process in removal/separation of
contaminants  necessitates a better understanding of the electrochemistry
1 Associate Professor, Department of Civil Engineering, Louisiana State
 University, Baton Rouge, LA 70803
                               508

-------
associated with electrokinetic phenomena and its relation to the mechanical
behavior.

       Recent  studies   provided   a  better  understanding  of  the
electrochemistry and demonstrated  that  the  acid front generated  by
electrolysis reaction at the anode advances and eventually flushes across
the specimen by advection, migration.and diffusion (Acar et al 1989;
Shapiro et al. 1989; Acar et al. 1991).  Hamed (1990) and.Hamed et al.
(1991) demonstrated that the  movement  of this acid front together with
migration and advection of the cations and anions under electrical gradients
constitute the mechanisms of removing  contaminants from  soils.  The
factors influencing the acid/base profile across  the porous medium would
significantly affect  the  flow, the flow efficiency, and the extent  of ion
migration and removal in electrokinetic soil processing.

      This paper presents the fundamentals of the process,  reviews, the
results of the on-going studies and provides engineering implications for its
implementation.                                               ,

             ELECTROKINETIC PHENOMENA IN SOILS

      Coupling between  electrical, chemical  and hydraulic gradients  is
responsible for different types of electrokinetic phenomena in soils. These
phenomena include electro-osmosis, electrophoresis, streaming potential
and  sedimentation   potential  (Mitchell   1976).    Electro-osmosis and
electrophoresis are the movement of water and particles; respectively, due
to application of a low DC current. Streaming potential and sedimentation
potential are the generation  of a current  due to the movement of(iwater
under  hydraulic potential  and movement  of particles under gravitational
forces, respectively.  The effect of coupling  becomes more important in fine-
grained soils with lower coefficients of permeability.

      In electro-osmosis, electrodes can be placed in an open pr closed
flpw arrangement.  Open flow arrangement constitutes the case when  an
electrode is sufficiently permeable to admit ingress and egress  of water.  In
the closed flow arrangement, the electrode is  not permeable or porous.
Different electrode configurations (open or closed) Jesuit  in. substantial
variations in the total matrix potentials across the soil specimen.

      The electro-osmotic  flow  rate,  qe, is defined with an empirical
relationship,
                                509

-------
                      qe = keie A = k, I  =     I                  0)


 where ke = coefficient of electro-osmotic permeability  (cm2/sec-V), k, =
 electro-osmotic water transport efficiency (cm3/amp-sec), I = current (amp),
 CT = conductivity (siemens/cm), ie = electrical potential gradient (V/cm), A =
 cross-sectional area (cm2). Estimates of electro-osmotic flow rates can be
 made using equation (1).  Ke varies within  one order of magnitude for all
 soils; 1 x 10~5 to  10 x 10~5 (cm/sec)/(V/cm), the higher values being at
 higher water contents.

      Figure 1 presents a schematic diagram of one-dimensional laboratory
 tests in electrokinetic soil processing. The prevailing electrical gradients,
 and the ion flow are also depicted. A comparison of flows under electrical
 and hydraulic gradients in clays is also provided. The coefficient of electro-
 osmotic permeability is independent  upon the size and distribution of pores
 (fabric) in the  soil mass.  However, hydraulic conductivity is most affected
 by  the fabric.  Therefore, hydraulic  conductivity decreases by five to six
 orders of magnitude (10~s cm/sec to 1Q~8 cm/sec) from  the fine sands to
 clays. Figure 3 indicates that under equal gradients, electrical potentials in
 fine-grained soils  may result  in orders of  magnitude larger  flows  than
 hydraulic potentials. Therefore, electro-osmosis induced flow can  be  con-
 sidered to be an  efficient pumping mechanism in saturated, low  per-
 meability, fine-grained soil.

      The efficiency and  economics  of electro-osmotic dewatering is
 governed by the amount of water transferred per unit charge passed which
 is  quantified  by . electro-osmotic water transport  efficiency,  kj.   The
 parameter kf may  vary  over a wide range from 0 to 1.2 cm3/amp-sec
 depending upon the electrical conductivity of the porous medium.  The
 conductivity changes with water content, cation exchange capacity and free
 electrolyte content in the soil and also due to the prevailing chemistry during
 electrokinetic processing.  Gray and Mitchell (1967) indicate that  electro-
 osmotic efficiency  decreases with a decrease in water content  and an
 Increase in activity  of the soil. The electro-osmotic dewatering efficiency Is
 independent of variations in electrolyte concentration (sodium ion) for active
 clays, while an increase in electrolytes tends to decrease the efficiency in
 inactive clays.

      Recent  studies by Lockhart (1983) substantiate the conclusions of
 Gray and  Mitchell (1967).  k; increased from 0.32 to 1.20 cm3/amp-s  with
the decrease of  NaCI and HCl concentrations from  10"1 M to 10"^ M. kf
decreased by an increase in electrical gradients, possibly due to a higher
influx of H+ ions (Hamed, et a!., 1991). Lockhart (1983) shows that a higher
 electro-osmotic efficiency was recorded with  H and Cu clays. k( changed
                                510

-------
                        |—I >-. uoi
                        ฅ
     n
                       H Outflow
                        Inflow
                    CURRENT,I
                                 U>
                                 Anode
                                      Soiurotea Specimen
                                                       Coinooe
                                          f • Consieni
                    POTENTIAL,
                                      * ^w(moini) ป if>t (tucfion )
                                      ( constant), ^>,  (vanosit )
         <3-
ION "LOW /—x
(INITIAL! (H  ;—
i.Q      ^
         /C^__
                             C^
                             0
                    ION FLOW
            ivฅ
7N
              ป4) ""i
             M-Yci-^
                                                    Caiioia
                                                           p
                                                           .o
                                      no'
    fH'^    ./^5\{>)
0MS?iA;;
                                                            OH'
                                               (CI-)   lซ,0)   OH
                                  lw,0)   C
                                  VฃZ_Jv
         Electro-Osmotic Flow, Qe
         Qe = ke . ie . A
         ke = electro-osmotic permeability
         ie  •= electrical gradient
         A  = area
         Hydraulic Flow, Qn
         Qh = kh . ih . A
         kh = hydraulic concfyctivity
         ih  = hydraulic gradient
         Ratio of Two Flows
                           A Comparison of Two Flows in Clays
                           ke = 1 x 10'5 (cm-sec)/{v/cm}
                           kh m 1 x 10"8 era's ec
                           i   = 1 v/cm (typical for field application)
                           ih  = 1 (selected for comparison)

                           _ฃ. 1.000
                           OK
Figure 1.  A Schematic Diagram of Electrokinetic Processing, Ion Flow and
           Comparison of Flow in One-Dimensional Flow Conditions (Hamed
           et at. 1991).
                                        511

-------
 in the order of H > Cu > Al > Na > Ca.  Higher voltage gradients were
 required to initiate flow in Al clays.

            POTENTIAL USES OF ELECTROKINETICS IN
                      WASTE MANAGEMENT

       The four electrode configurations described above could potentially
 be used in the following ways in waste disposal (Acar and Gale 1986; Acar
 et al. 1989): (1) Dewatering of waste sludge slimes, dredged spoil by first
 concentrating  the solid  particles  using  electrophoresis and subsequent
 consolidation by electro-osmosis (Mitchell  1986), (2) Electro-osmotic flow
 barriers (Mitchell and Yeung 1991), (3) Leak detection systems for disposal
 facilities, (4) Injection of grouts to form barriers, (5)  Provide  nutrients for
 biodegrading  microcosm,   (6) Jnsitu  generation  of  reactants  such  as
 hydrogen peroxide for cleanup and/or electrolysis of contaminants, and
 (7) Decontamination of soils and  groundwater.  Figure 4 conceptualizes
 electrokinetic clay barriers,  waste  plume diversion  schemes,  and electro-
 osmotic injection.

       Insitu remediation methods often  necessitate  the use of hydraulic
 charge and recharge wells to permeate the decontaminating liquid or stabili-
 zation agent through  the soil deposit,  or to provide  nutrients  for the
 biodegrading microcosm. Although such systems may effectively be used
 in highly permeable soils, they become inefficient and uneconomical in low
 permeability silts and clayey deposits. Electrokinetic soil processing with
 open electrode configuration could also  be used to  achieve an efficient
 seepage and decontamination  method in such soils.

       REMOVAL OF CONTAMINANTS BY ELECTROKINETICS

       Upon application of low-level DC current (in the  order of milliamps
      n2 of electrc
 processes occur:
per cm2 of electrode area) to the saturated porous medium, the following
(1)    The water in the immediate vicinity of electrodes is electrolyzed. An
      acid front is generated at the anode while a base front is created at
      the cathode.  Acar et al. (1989), Shapiro, et al. (1989) and Acar et
      al. (1990) formalize the development of these fronts.  pH at the
      anode will drop to below 2,0 and will increase at the cathode to
      above 12.0.

(2)    The acid front wiil advance across the specimen in time towards the
      cathode by:

      (a)    advection of the  pore fluid due to the prevailing electro-
            osmotic flow,
                               512

-------
                               FLOW BY

                             AND CHEMICAL  POTENTIALS
I
x xfxx
1 1
O O
CLAY LINER
T

                     O     O     0      O


                      t       t        ft
                           OPPOSING FLOW BY
                      ELECTROKINETIC POTENTIALS


                         (a) Flow Barriers
                                                DIVERSION
                                         MIGRATION

                                         DIRECTION
                   (b) Plume Diversion Scheme
                    DISCHARGE
CHARGE

GROUT

NUTRIENTS


CHEMICALS
                      ฉ
xxv

CONTAMINATION

	
                          EO FLOW
                   (c) Electro-osmotic Injection
Figure 2.  Schematic View of Different Applications of Electrokinetic

          Phenomena in Remediation (Acar et al. 1989).
                              513

-------
       (b)    advection of  the  pore fluid due to any hydraulic  potential
             differences,

       (c)    diffusion due to concentration gradients,

       (d)    migration due to the electrical gradients.

       Development of these acid and base distributions and movement of
       ionic species are formalized by Acar, eta!. (1991).

 (3)    The migration, diffusion and advection will also result in movement
       of cations and anions to respective electrodes in the porous medium
       (Hamed et al. 1991; Mitchell  and Yeung 1991).

 (4)    The acid advancing across the specimen exchanges with adsorbed
       cations in the diffuse-double layer, resulting in their release into the
       pore fluid  and advance towards the  cathode by advection and
       diffusion (Hamed et al. 1991).

 (5)    In case the  generation  of:the acid front is  not controlled at the
       anode, the electrolyte concentration inside the porous medium will
       gradually rise, resulting in increased conductivity in the vicinity of the
       anode, decrease in electro-osmotic flow (Hamed et al. 1991), and a,
       corresponding decrease  in bulk-flow movement by advection,

 (6)    The decreased conductivity at the cathode region (possibly due to
       anion depletion and/or due to deposition of species as  salts) will lead
       to an  increase  in voltage and an increase in energy expenditure
       (Hamed 1990).  The chemistry at the anode and the cathode should
       ideally be controlled to achieve continued advection white providing
       sufficient H* ions for desorption of contaminants and/or solubili2.ation
       of salts. This control is possible either  by decreasing  the current to
       levels where pH is at a desirable level or by frequent flushing at both
       ends by a fluid of controlled pH and chemistry.

                   REVIEW OF AVAILABLE DATA

       Studies investigating removal of ions from soils by electro-osmosis
 are rare possibly due to difficulties in understanding the chemistry.  Table 1
 provides a synthesis and analysis of laboratory  studies which reported some
 form of data related to ion removal from soils.  One of the earlier studies is
 by Purl and Anand (1936) where leaching of Na+ ions were detected in the
 effluent in  electro-osmotic consolidation.  Puri (1949) suggested that in
 electro-osmosis monovalent ions will move faster than divalent ions due to
the former's higher dissociation from the  clay surface. It is also noted that
                                 514

-------
               Table 1. Analysis ol laboratory data reported lor removal of chemicals by electrokinetics

Soil Type/
Chemical

1 Puri and Anand (1936)

High pH Soil - Na+




2 Jacobs and Mortland
(1959)

5% Bentonite/95% Sand

Na-Ca
Na-Ca-Mg
Na-K
Na
Ca
K
3 Krizek, el al. (1976)

Slurry/Sediment

No. 1 - Na
K
Ca
NH3-N
No. 2 - Na
K
Ca
NH3-N
Concentration
(M9'9)

Initial


N/A









.591.57
.44/.3M
.65/.41
0.78-1.11
0.86-1.0
0.79




320
7
65
138
360
15
340
172

Final


N/A









0.0/(N/A)
0.0/JN/A)
0.0/(N/A)
0.0
.26-0.30
0.0




330*
290
640
320
205
160
5800
456
Current Density
and/or Voltage
(mA/cm2) or
[V/cm]


9.3-14.9
[20.0]








0.32-0.64
(N/A]








[0.5]



[1.0]




Duration
(hr)



8
(inter-
mittent)







10-140









150



150



Charge

amp-hr
n,3


N/A









2-20









N/A



N/A




Energy
KWh/m3



N/A









N/A









20



65





Remarks

A Bucher funnel was used in testing. The
diameter was 18 in. Cathode is circular
brass plate. Anode consists of five cylin-
drical bars arranged symmetrically along
the circumference. Na normality ol per-
colate increased up to 0.6 N. The effluent
was 90% NaOH. 10% Na2CO3.
1,-D tests. Cylindrical specimens (D =
0.75 in.. L = 1 in.). Circular platinum elec-
trodes. Rate ol removal of monovalent
ions were directly related fo the amount
remaining in the specimens. The rate of
removal was in the order of Na* > K* >
Mg2f > Ca2f. Na* was removed more
efficiently than all other ions. Tests were
discontinued when most Na* was removed.
Concentrations reported are in symmetry
units.
Slurries (w = 100 - 142%) from discharge
pipes and contaminated bottom sediments
are tested. Cylindrical 1-0 consolidation
tests (D = 14 cm. L= 25 cm).

(')The concentrations are Ihe initial and
final effluent values.





tn
ป-•
01

-------
              Table t (continued}

Soil Type/
Chemical

4 Hamnet (1980)

Silica Sand • NaCI
Heavy Clay


5 Runnels and Larson (1986)

Silty Sand - Cu(ll)

6 Renauld and Probstein
(1987)

Kaolinite - Acetic Acid


7 Thompson (19B9)

Ottawa Sand

Si02 flour
Cu (N03)2

8 Lageman (1989)

Peat

Pb
Cu

Pottery Clay - Cu

Fine Clayey Sand • Cd
Concentration
(i
-------
               Table 1 (continued)
Soil Type/
Chemical
8 Lageman (1989) (cont.)
Clay - As
Fine Clayey Sand
Cd
Cr
Ni
Pb
Hg
Cu
Zn
River Sludge
Cd
Cu
Pb
Ni
Zn
Cr
Hg
As
Concentration
(M9/9)
Initial

300

319
221
227
638
334
570 .
937

10
143
172
56
901
72
0.50
13
Final

30

<1
20
34
230
110
50
180

5
41
80
5
54
26
0.20
4.4
Current Density
and/or Voltage
(mA/cm2) or
[V/cm]

N/A

N/A







N/A






•
Duration
(hr)

N/A

N/A







N/A







Charge
amp-hr
m3

N/A

N/A







N/A







Energy
kWh/m3

207

54







180







Remarks



















01

-------
              Table 1 (eontlnwd)
tn
i_i
oo

Soil Typo/
Chemical

9 Shapiro, el at. (1989)
Phenol

Acellc Acid






10 Banerjee, et al. (1990)

Silly/Silly Clay - Cr







1 1 Hamed, J.. Acar, Y. B.,
Gale. R.J. (1991)

Georgia Kaolinite - Pb(ll)




Concenlrallon
Wg)

Initial

450
45
0.5 M

O.t M






2460
2156
870
704
642
532
234
148



118-145





Final

<2Q
<10
<6% ol
initial
<6% of
initial





22
12
50
19
22
37
3
10



7-40




Current Density
and/or Voltage
(mA/cm?) or
|V/cmj

N/A
N/A
0.035

0.60



•


N/A
[0.1-1.0]









0.037 '
[S2.5I
I *" J
-


Duration
(hr)


N/A
N/A
N/A

N/A






24-168










100-1285



!
Chargo
amp-hr
m3

N/A
N/A
N/A

N/A






N/A










362-2345





Energy
kWWm3


N/A
N/A
N/A

N/A






N/A










29-60



1 -

Remarks


1.8 pore volumes ol (low
1.2 pore volumes of flow
1.4 pore volumes of flow

1.4 pore volumes of flow

1 -Dimensional tests are conducted.
The effect of organic acid concentration on
the degree of removal is studied.
Eight cylindrical 1-D tests were conducted
on specimens brought from the field (D =
5.1 cm, L = 2.5 cm to 6.7 cm). Electrodes
used were Ni-Cu wire mesh. Hydraulic
and electrical potentials were applied
simultaneously in order to facilitate
removal.



1-D tests. Cylindrical specimens (D =
4 In., L = 4in. and 8 in.). Circular graphite
electrodes. Initial conductivity of speci-
mens 75-86 us/cm. Rose up to 1000
US/cm at the anode, dropped to 22 (is/cm
at the cathode after the process. Pb(li)
movement and electrochemistry across the
specimens are reported.

-------
          Table 1 (continued)

Soil Type/
Chemical

12 Mitchell and Yeung ( 1991)
. ••'- .





13 Acar. Y. B.. Li, H., Gale, R.
J. (1992)

Georgia Kaollnite - Phenol

14 Bruell. C. J., Segal, 8. A.,
Walsh, T. M.( 1991)

EPK Kaolin

Benzene
TCE
Toluene
m-xylene
Hexane
Iso-octnne
Concentralion
(Mg'g)

Initial
N/A








'..• •'
500






1780
1100
515
146
10
2,4

Final
N/A







*

25-75



Removal
%

15-27
15-25
15 .
J9
13
7
Current Density
and/or Voltage
(mA/cm2) or
; [V/cmj
N/A









0.037
{54.0]



N/A
[0.4 v/cm]







Duration
(hr)

,N/A









100-140






72-120
72-120
45
120
96
600
Charge

amp-hr
m3
N/A .









•N/A






N/A






Energy
kWh/m3

,N/A







$

12-28






N/A







. Remarks
. - • • . •, .
. Investigated the feasibility of using electro-
kinetics to stop migration of contaminants.
Electric field slowed down the migration of
cations. and increased the, movement of
anions. ke did not display a marked
change by an increase in backpressure,
molding water content and dry density.
Adsorbed, phenol was removed by the
process, The breakthrough curve did not
display retardation.


Cylindrical specimens of 7.6 cm in dia-
meter and 30.5 cm in length were tested.
Specimens were loaded with the contami-
nant. Iron electrodes were used.' Writers
noted that removal was a function of time
of processing. Contaminant removal front
in lime is presented.




in
M
vo

-------
 movement of ions was low at low water contents and significantly increases
 by an increase in water content.

      Jacobs  and Mortland (1959) demonstrated that Na*. K+, Mg""+ and
 Ca4"1' ions can be leached out of Wyoming bentonite by electro-osmosis.
 The amount of  the ions removed  versus the  electro-osmotic  flow in
 bentonite-sand mixtures demonstrates that monovalent ions (K+, Na*} are
 removed at a faster rate than the divalent ions (Da*2).

      Krizek,  et  al.   (1976) showed  that  the  soluble  ions  content
 substantially increased in effluent in electro-osmotic consolidation of polluted
 dredgings, while  they also noted that heavy metals were not found in the
 effluent during the period  they applied the process. Hamed, et al. (1991)
 show that it is necessary to wait until the acid front flushes across the
 specimen in order to  see any  heavy metal  ions or depositions  on the
 cathode or the effluent.

      Hamnet (1980)  studied the  reclamation of agricultural soils  by
 removal  of  unwanted  salts   by  electro-osmosis.    Ham net's  tests
 demonstrated that Na+ ions move toward the cathode, while CI* and SO3"2
 ions move toward the anode.

      Shrnakin (1985) notes that the method has been  used in the Soviet
 Union since the  early  1970's as a method for  concentrating metals and
 exploring for minerals in deep soil deposits. Shmakin (1985) mentions its
 use in prospecting for Cu, Ni, Co, Au. A porous ceramic probe with HNO3
 is placed at the cathode. The migrating ions are extracted with this probe.
The  quantity of  the extracted  metal at  the  cathode and the rate of
 accumulation is correlated with the composition of the ore and the distance
of the sampling locations to the ores.

      The potential of the technique in  waste remediation resulted in
initiation  of several recent studies.   Runnels  and Larson (1986)  have
investigated the potential use of  electromigration to remove contaminants
from groundwater.  The  amount of copper  removed  increased with
processing time  (total  charge passed).   However, the current efficiency
decreased as the processing time increased, possibly due to the increase
in conductivity  as noted by Harned, et al. (1991).

      Renauld and Probstein (1987) investigated the change in the electro-
osmotic water transport efficiency of kaolinite specimens loaded with acetic
acid and  sodium  chloride.  This study indicated  that the current efficiency
increased with higher concentrations of this weak, organic acid.   This
implies organic acids  may increase the efficiency of  electrokinetic soil
processing.
                                 520

-------
       A  better understanding  of  the chemistry  in  electrokinetic soil
 processing is achieved through studies at LSU. Putnam (1988) investigated
 the development of acid/base distributions in electro-osmosis.  Acar et al.
. (1989), Acar et al. (1990) and  Acar, et al. (1991) present the theory for
' acid/base distributions in .electro-osmosis and compare the predictions of
 this model with the results of the tests conducted by Putnam  (1988).  A
 good  correlation  was noted.    This  theory  and  the  model  provide, a
 preliminary  description  of  the  movement   of  different  species .in
 electrokinetics.    The significance  of the acid  base  distributions in
 electrokinetic  soil  processing is further displayed in studies reported by
 Shapiro, et  al. (1989). These studies  demonstrate the movement of the
 acid front by advection and diffusion and provides the fundamental basis of
 the chemistry  developed  during the, process.                        :

       A comprehensive subsequent  study on removal of Pb(ll) from
 kaoiinite is reported by Hamed, et al. (1991).   Kaolinite specimens were
 loaded with  Pb(ll) at 118 u,g/g to 145 u,g/g of dry  kaoiinite, below the cation
 exchange capacity of this  mineral.  As  presented in  Figure 3, electro-
 osmosis removed  75 to  95 percent of Pb(ll) across the test specimens.
 The study clearly demonstrated that the removal was due to migration and
 advection of  the  acid  front generated  at  the anode by  the  primary
 electrolysis reaction.  The energy used in the study to decontaminate the
 specimens was 29 to 60 kWh per cubic meter of soil processed.,  This study
 also explains the complicated electrochemistry associated with the process.
 An interesting  finding  of this study is electroplating of Pb(l!) at the carbon
 cathode.                                            .

       Further studies investigating  removal of Cd(ll) and Cr(lll) are  also
 reported by  Hamed (1990). Similar results are  obtained.  Hamed (1990)
 investigates the effect of increased concentration and current density on the
 efficiency of the removal process.  Higher current densities result in as
 efficient  a  removal  as  in  lower  current densities  while  the  energy
 requirement and the  cost  of  processing increases  exponentially.   The
 increased energy requirement was found to be due to increased production
 of  H"1"  ions and their introduction  into the  specimen.  Other  laboratory
 studies conducted  by  Lageman (1989)  and Banerjee, et al, (1990) further
 substantiate the applicability of the technique to  a wide range of inorganic
 contaminants and  soils.

       The applicability of the technique to removing organic contaminants
 is investigated in studies at LSU. Acar,  et al. (1992) report phenol removal
 from  saturated  kaoiinite  using the technique.   In this study, kaoiinite
 specimens were loaded by  500 ppm phenol below the phenol adsorption
 capacity of this mineral. The breakthrough of phenol upon application of the
;direct current is presented in Figure 4a. The process removed 85 to 95%
 of the  adsorbed phenol.  The energy used in removal of phenol was
                                 521

-------
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                   PORE VOLUMES OF FLOW
                  (b) Energy Expenditure
Figure 3.  Pb(ll) Removal from Kaolinite and Corresponding
          Energy Expenditure (Hamed et al. 1991),
                          522

-------
          0   0.5  10   15   2.0  2.5  3.0  3.5  4.0  4.5
                        PORE VOLUME
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      . (b) Energy Expenditure in Phenol Removal


Figure 4.  Phenol Removal by Electrokinetic Soil Processing
          (Acaret al. 1992).
                            523

-------
13 kWh to 18 kWh per cubic meter of soil processed (Figure 4b). One very
interesting aspect of these tests is the breakthrough achieved in two pore
volumes of flow (Figure 4a). Electrokinetic processing did not result in any
retardation due to the desorption mechanism. It is  hypothesized that this
is both due to the movement of the diffuse double layer toward the cathode
and advance of the acid front replacing the adsorbed phenol, Bruell, et al.
(1991) report removal of the BTEX compounds and trichloroethylene loaded
on kaolinite  specimens by electro-osmosis.  Figure 5  demonstrates that
application  of  DC  current  resulted  in  removal  of  benzene by the
electrokinetic processes.   These (experimental model  results display
breakthrough curves similar to that encountered in advective-dispersive
movement of reactive species (Acar and  Haider 1990).   However, the
process cannot be  described only: by the  analytical model  describing
transport of contaminants.  It involves changing  chemistry across the
specimen  together with coupling of electrical,  hydraulic and chemical
gradients.

      While the above laboratory studies display the  feasibility of using
electro-osmosis to decontaminate soils, limited field studies are available.
          1.2
       o
       
-------
Table 2 provides a synthesis of field tests investigating and/or reporting
some form of chemical removal from soils.  Segail, et ai. (1980) present the
chemical  characteristics of the water accumulated at the electrodes  in
electro-osmotic dewatering of dredged soil. Their study discovered that:

      (1)    There was a significant increase in heavy metals and organic
             materials  in electro-osmosis effluent  above that recorded  in
             the  original  leachate.  The concentrations  of zinc,  lead,
             mercury and  arsenic were especialfy high,

      (2)    Total organic carbon content of the effluent was two orders  of
             magnitude higher than the original leachate.  It is postulated
             that highly alkaline conditions resulted  in dissolution  and
             release of the organic material.  Pesticides came out at the
             cathode.

Case and Cutshall (1979) describe a field study for control  of radionuclide
migration in soil by application of DC current.  This study demonstrates that
it is possible to migrate radionuclides with the technique. Recent laboratory
studies at LSU indicate that uranium at an activity of 1,000  pCi/gm can be
removed from kaolinite by the process.  Lageman (1989) reports the results
of field studies conducted in  the Netherlands  to decontaminate  soils by
electrokinetic soil processing. Figure 6 presents a schematic diagram of the
reported field process.  An electrode fluid conditioning and purification
system is noted.  The conditioning is for the control of  the influent/effluent
chemistry, while purification (such as ion exchange resin columns) is for
removing any excess ions  in the effluent.

      A  recent study  investigating the  application  of the  process,  to
decontaminate a chromium site is also reported by Banerjee, et al. (1990).
The results of that study are  inconclusive as the investigators monitored
only the effluent concentration and removal across the  electrodes was not
scrutinized. Studies at LSU indicate that unless the processing is continued
until the acid  front flushes  across the electrodes and neutralizes the base
generated at the  cathode, any  conclusion  based  only on the  effluent
concentration of an inorganic chemical would not be supported. In earlier
stages of the  process, the contaminant is removed from the anode section
and is often precipitated in,the cathode section. Further processing and
movement of the acid front to  the cathode is one fundamental mechanism
by which the contaminants are removed.  Furthermore,  in evaluation of the
feasibility of the technique, the behavior of the contaminant at different pH
environments  should also be  considered.    For example, Cr(lll)  will
precipitate below a pH of 3.0.  Therefore, the processing parameters
(current density and/or influent pH) should be kept at a level which the
contaminant would not  be  allowed to precipitate.
                                  525

-------
                  Table 2.  Synthesis ol field data reported (or removal of chemicals by electrokinetics
01
r\j
01

Soil Type/
Chamtea!

1. Puri and Anand (1936)

High pH Soil - NaOH







2. Case and Cutshall (1979)

Alluvial deposits - 90Sr



3, Segall, et at. (1980)

Dredged Material

Cd, Zn, Pb, As, Fa
Na
K ...
OH:
HCCV1
Organic Nitrogen
Ammonia Nitrogen
TOG
Concentration
(|ig/g)

Initial


4.8









8







<1
6t50
350
0
0
4
6?
3

Rnal


2.8









50







0.2-20
16300
510 7
5950
979
15
128
2000
Current Density
and/or Voltage
(mA/cm2) or
[Worn]


1.35
12,44)








0.3
[0.05]






IQ.OM.O]








Duration
(hr)



6









5.352







N/A








Energy
kWMn3



N/A









N/A







N/A








Remarks

An area of 4.5 m x 4.5 m was first trenched
all around, 1.05 m In depth and 0,30 m in
width. Anode and cathode were laid hori-
zontally within this area. Anode was a shot
of iron, 0.9 m x 1.8 m laid at top. Cathode
was a perforated iron lube, 0. 1 0 cm in da-
meter and 1 .8 m long laid at 0.3 m depth.
The concentrations reported are lor the
exchangeable Na in the top 7.5 cm of the
soil.
An area ol 11 m by 5 m was investigated.
1 .7 m stainless steel rods were driven in an
arc -plus-center point array. The arc con-
sisting of 25 anodes and a central cathode.
The concentrations reported are lor the
effluent in a monitoring Well.
Concentrations noted are for the effluent in
electro-osmotic consolidation of dredged
material compared to that of water leached
specimens. The distance between elec-
trodes is 3-5 m.








-------
                      Table 2 (continued)
PO

Soil Type/
Chemical

4. Lageman (1989)
Sandy Clay - Zn








Heavy Clay - As





Dredged Sediment
Pb
Cu
5. Banerjee. et al. (1990)

Silt/Silty Clay - Cr



Concentration
(M9/9)

Initial

70-5120








90-385






340-500
35-1150


N/A




Final

30-4470








20-240






90-300
15-500


N/A



Current Density
and/or Voltage
(mA/cm2) or
[V/cm]

0.8
(0.4-0.2)







0.4
[0.4-0.21
lw* * *"*-j





N/A



2-4
[0.2-0.24]



Duration
(hr)


1344








1200






430



<72




Energy
kWh/m3


287








270






N/A



Na




Remarks



An area of 15 m by 6 m is studied. Con-
tamination depth: 0.40 m. Temperature
rose from t2"C to 40"C. Conductivity
increased from 2000 us/cm to 4000 jis/crn.
Voltage gradient decreased. 2 cathodes
(vertical) at 0.5 m depth. 33 anodes (verti-
cal). 3 rows at 1.0m depth. Distances:
cathode-anode = t.5m; anode-anode =
t.5 m.
An area of 10 m by 10 m was studied within
a depth of 2 m. Cathodes (vertical), 2 rows:
1 row at 0.5 m depth: 1 row at 1.5 m depth.
36 anodes (vertical), 3 rows at 2 m depth; 2
rows of 14: 1 row of 8. Distances: cathode-
anode = 3 m; anode-anode = 1.5m. Tem-
perature rose from 7"C to 50"C.
An area of 70 m by 3 m was studied to a
depth ol 0.2 m to 0.5 m. Cathode is laid
horizontal, anode (vertical). Cathode-anode
3 m; anode-anode 2 m.

Nine field experiments were conducted in an
array of electrodes. Combined Hydraulic
and electrical potentials were applied. Steel
reinforcing bars were used and replaced
after each experiment. The results are
inconclusive.

-------
ES CCNTAINE3
PURIFICATION | PURIFICATION
H
CONDITIONING
II '
I] il
ll i CONDITIONING
I)
I
                                CH.
                                                       GENERATOR
                                                        OR MAIN
          Figure 6. A Schematic Diagram of the Field System
                    Reported by Lageman (1989).
      The laboratory studies reported by Hamnet (1980), Runnels  and
Larson (1986), Lageman (1989), Shapiro, et al. (1989), Acar et al. (1990),
Hamed (1990),  Hamed  et al. (1991), and Acar et al. (1992) together with
the pilot-scale field studies of Lageman (1989) display the feasibility of using
the process and commercialize in site  remediation.   Further pilot-scale
studies  are necessary to  improve  the technology and  establish  the
necessary  field  remediation scheme for different  site  conditions and
chemistry.                        ;

                   ENGINEERING IMPLICATIONS

      The above review of the present state of knowledge on electrokinetic
soil remediation indicates that:
                                 528

-------
(1)    Type of Soil:  The process results in movement of ions in sandy to
      clayey  soils.  High water content, low activity soils at low pore fluid
      electrolyte  concentrations  will result  in - higher  electro-osmotic
      efficiencies.

(2)    Type and Concentration of Contaminants: Most available data is on
      ionic forms of inorganic cations, and some radionuclides (90Sr) and
      acetic acid. There exists data demonstrating removal at levels of up
      to 10,000 ppm of Cu(ll) and 5,000  ppm of Pb(ll).  As concentrations
      of contaminants (ionic) increase,  removal should be  mostly  by
      migration  as  advection  (electro-osmotic flow)  will  substantially
      decrease. At lower concentrations, both advection and migration will
      be acting. Recent laboratory studies demonstrate that it is feasible
      to remove phenol (500 ppm) BTEX compounds (benzene,  toluene,
      ethylene,  xylene, and  trichloroethylene)' from • kaolinite  by  the
      technique.  All current data is on concentration of these organic
      chemicals below their water solubility limits. There exists the need
      to investigate the feasibility of the technique at higher concentrations.

      Data regarding acid/base distributions indicate that salts (such  as
      PbO) may also dissolve and migrate due to the advancing acid front.
      However, there is no factual data to validate this hypothesis.

(3)    Mixture of Contaminants-: The data indicates that the process also
      works on a mixture of contaminants (Lageman, 1989). Monovalent
      ions may be removed at a higher rate than higher valence  ions.

(4)    Saturation: Mitchell and Yeung (1991) present data regarding the
      effect  of saturation  on ke.    ke  did  not change  significantly  in
      specimens compacted at different  molding moisture  contents. This
      data suggests  that the  process  may be applicable  in  partially
      saturated soils.

(5)    Depths: The review of literature indicates that there should not  be
      a depth limitation in the process beyond practical problems that may
      be encountered.                                               ,

(6)    Type of Electrodes:  Inert electrodes such as graphite, carbon or
      platinum  should be used  at  anode in order to  avoid introducing
      secondary corrosion products into the soil mass. Open  electrodes
      allow  control  of influent and effluent chemistry.   It should  be
      recognized that some ions will be electroplated on the cathode or
      they may be precipitated close -to the cathode.

(7)    Electrode Configuration: The electrodes can be placed horizontally
      or vertically.   It is  noted  that the electrical potential gradients
                                 529

-------
       generated due to different electrode arrangements will affect the flow
       conditions and hence the  removal efficiency.  The gradients will
       significantly change by electrode  configurations and the  depth of
       individual electrodes relative to the counter electrode.

 (8)    Electrode Spacing: Spacing will depend upon the type and level of
       contamination and the selected current/voltage regime. A substantial
       decrease in efficiency of the process may result due-to increases in
       temperature when higher voltage gradients are generated.

 (9)    Current Level: The current level reported is in the order of milliamps
       per square cm of  electrode area (0.01 to 1.0 mA/cm2). It can be
       varied to monitor the influent pH level at the anode and to control the
       rate of decontamination.

 00)   Duration: Process should be continued until the desired removal is
       achieved.  The remediation  duration  will be site  specific.   It is
       necessary to wait  until  the acid front generated at the anode will
       advance to the cathode.

 (11)   Effluent/Influent Chemistry:  It is possible to control the efficiency by
       controlling the pH and the chemistry of the effluent and the influent.
       Several alternatives are available:  (a) to decrease the current to a
       level where less H* ions-are generated, (b).to flush the anode and/or
       cathode by a fluid  of known chemistry (e.g., introducing acid  at the
       cathode  will  decrease  the voltage  gradients "substantially), and
       (c) placement of an acidic ion exchange resin,

 (12)   Chemistry .Subsequent to the  Process:  The porous medium will
       become acidic upon completion  of the process.  The medium will
       return to original conditions by diffusion of the acidic pore fluid to the
       surrounding medium.  Cathode effluents may require post-chemical
       treatments (such  as  ion exchange resin columns for inorganic
       contaminants) to achieve concentration of contaminants.  Cathodes
       may necessitate treatment to remove the electroplated contaminants.

                      ACKNOWLEDGMENTS

       Studies at Louisiana State University, investigating electrokinetic soil
processing,-are funded  by the  Board  of  Regents  of  the State, the
Hazardous Waste  Research  Center  of  LSU,  the  National   Science
Foundation,  and Electrokinetics,  Inc.   These  awards  are  gratefully
acknowledged.  Any opinions, findings,  and conclusions or recommenda-
tions  expressed in  this  material  are those of  the writer  and  do not
necessarily reflect the views of the sponsors.
                                530

-------
                          REFERENCES

Acar, Y. B., and Gale, R. J. (1986) "Decontamination of Soils Using Eiectro-
Osmosis," A proposal submitted to the Board of Regents of the  State of
Louisiana,  LEQSF Research Development Program Office of Research
Coordination, Louisiana State University.

Acar,  Y.   B., Gale,  R. J.,   Putnam, G.,  and  Hamed,  J.  (1989),
"Electrochemical  Processing of Soils:  Its potential Use in Environmental
Geotechnology and  Significance of  pH Gradients," 2nd International
Symposium on Environmental Geotechnology, Shanghai, China, May 14-17,
Envo Publishing, Bethlehem, PA, Vol. 1, pp. 25-38.

Acar, Y, B., Gale, R. J., Hamed, J., Putnam, G. (1990) "Electrochemical
Processing of Soils: Theory of pH Gradient Development by Diffusion and
Linear Convection," Journal of Environmental Science and Health,  Part (a);
Environmental Science and Engineering, Vol. 25, No. 6, pp. 687-714.

Acar, Y. B., Hamed, J., Gale,  R. J., and Putnam, G. (1991),  "Acid/Base
Distributions in Electro-Osmosis," Transportation  Research Record, No.
1288, Soils Geology and Foundations, Geotechnical Engineering 1990, pp.
23-34.  .   . -  .         :    •   .  .             '

Acar, Y. B., Li, H., Gale, R. J. (1992),  "Phenol Removal from Kaolinite
Using Electrokinetics," Journal of Geotechnical Engineering, ASCE (in
press).

Banerjee, S., Horng, J., Ferguson, J.  F., Nelson, P, 0. (1990), "Field Scale
Feasibility of Electro-Kinetic Remediation," Unpublished Report Presented
to USEPA, Land  Pollution Control Division, RREL, CR811762-01,  122 p.

Bruell, C. J., Segall, B. A., Walsh, M. T. (1991), "Electro-osmotic Removal
of Gasoline Hydrocarbons and TCE from Clay," Journal of Environmental
Engineering, ASCE.

Casagrande, L. (1947),  "The Application of Electro-osmosis to Practical
Problems  in Foundations and  Earthwork," Department of Scientific and
Industrial Research, Building Research, London, England, Technical Paper
No. 30, 22 p.

Case, F. N. and Cutshall, N.  H. (1979), "Oak Ridge National Lab., TN
(USA)," Symposium on the Scientific Basis for Nuclear Waste Management,
Boston, MA, USA, Nov.  26-29,  Conf. 791112-28, 5 p.
                               531

-------
Gray,  D,  H.,  and  Mitchell,  J,  K.  (1967),  "Fundamental Aspects  of
Electroosmosis in Soils," Journal of the Soil  Mechanics and Fourida'tion
Division, ASCE, Vol. 93, No. 8MB, pp. 209-236.

Hamed, J, (1990), "Decontamination  of  Soil Using Electro-osmosis," A
Dissertation submitted to the Graduate School of Louisiana State University
in Partial Fulfillment of the Degree of Doctor of Philosophy.

Hamed, J., Acar, Y. B., Gale, R. J. (1991), "Pb(ll) Removal from Kaolinite
by Electro-kinetics," ASCE, Journal of Geotechnica! Engineering, Vol. 117,
No. 2, February 1991, pp. 241-271.

Hamnet, R.  (1980), "A Study of the Processes Involved in the Electro-
Reclamation of Contaminated Soils," MS Thesis, University of Manchester,
England, 84  p.

Jacobs, H. S., and Mortland,  M. M. (1959), "Ion Movement in Wyoming
Bentonite During Electro-osmosis," Proceedings of Soil Science Society.  -

Khan, L I.,  Pamukcu, S., and Kugelman,  I.  (1989), "Electro-osmosis in
Fine-grained  Soil,"  2nd International  Symposium  on- Environmental
Geotechnology, Shanghai, China, Envo Publishing, Bethlehem, PA, Vol. 1,
pp. 39-47.                                                       *"

Krizek, R. J., Gularte,  F. B., and Hurnmel,  P. B.  (1976), "Stabilization of
Polluted Dredgings by Electro-osmosis," ASCE National Water Resources
and  Ocean  Engineering Convention,  San Diego,  CA,  April 5-8,  1976,
Preprint 2641.

Lageman, R.  (1989)  "Theory  and  Practice  of  Electro-Reclamation,
"NATO/CCMS Pilot Study, Demonstration of Remedial Action Technologies
for Contaminated Land and Ground Water, Copenhagen, Denmark, May 9,
1989, 18 p.                                 ......           :

Lockhart, N.  C. (1983), "Electro-osmotic Dewatering of Clays, I, H and III,"
Colloids and Surfaces, 6, pp. 238-269.

Mitchell, J. K. (1976), Fundamentals of Soil Behavior. John Wiley and Sons,
New York, 422 p.

Mitchell, J. K.  (1986),  "Potential Uses  of Electro-kinetics for Hazardous
Waste Site Remediation," Position paper prepared for USEPA-University of
Washington Workshop on Electro-Kinetic Treatment and its Application in
Environmental-Geotechnical   Engineering  for Hazardous Waste  Site
Remediation, Seattle, WA, August 4-5, 1986, 20 p.
                               532

-------
Mitchell,  J.  K.,  Yeung, T-C.  (1991), "Electro-kinetic  Flow  Barriers  in
Compacted  Clay," Transportation  Research  Record,  No.  1288,  Soils
Geology and Foundations, Geotechnical Engineering 1990, pp. 1-10.

Puri, A. N. (1949), "Reclamation of Alkali Soils by Electrodialysis," Soil
Science, Vol. 42, pp.  23-27.

Putnam,  G. (1988),  "Development of pH Gradients in Electrochemical
Processing of Kaolinite," MS Thesis presented to the Department of Civil
Engineering, Louisiana State University.

Renauld,  P. O.,  Probstein,  R. F. (1987), "Electro-osmotic Control  of
Hazardous Waste," Physicochemical Hydrodynamics, v. 9, No. 1/2,  1987,
pp. 345-360.

Runnels,  D.  D.,  Larson,  J.  L  (1986),  "A  Laboratory  Study  of
Electrpmigration  as  a Possible  Field  Technique  for  the  Removal  of
Contaminants from Ground  Water," Ground Water Monitoring Review,
pp. 81-91, Summer 1986.

Segal, B. A., O'Bannon, C. E., and Matthias, J. A. (1980), "Electro-Osmosis
Chemistry and Water Quality," Journal  of the Geotechnical  Engineering
Division, ASCE, Vol.  106, No. GT10, Oct. 1980, pp.  1143-1147.

Shapiro, A., P., Renauld, P., Probstein, R. (1989), "Preliminary Studies on
the Removal of Chemical Species from Saturated Porous Media by Electro-
osmosis,"  Physicochemical Hydrodynamics, Vol. 11,  No. 5/6, pp. 785-802.

Shmakin,  B. M. (1985), "The Method of Partial Extraction of Metals in a
Constant Current Electrical Field for Geochemical Exploration," J. Geochem.
Explor., Vol. 23, No. 1, pp. 35-60.

Steude,  J., Viani, S.,  Baker, K. (1989), "Emerging Technologies for the
Remediation of Radioactive Soils," Roy F. Weston, Inc., Walnut Creek, CA,
Technical  Report for the USEPA Office of Radiation  Programs, 64 p.

Thompson, R.  T. (1989),  "The Effect of Secondary Reactions on the
Electrokinetic Treatment of a Silty-Sand Soil," M.S. Thesis, The University
of Texas at Austin, Civil Engineering Department, 115 p.
                                  533

-------

-------
       NATO/COftlf iuest Speaker:



     Douglas .Atttttltify United States



        United States "Clean Sites"
535

-------
                 I. ..',
                Presentation of
               Clean Sites
                    to the
            NATO/CCMS PILOT STUDY
DEMONSTRATION OF REMEDIAL ACTION TECHNOLOGIES
                NOVEMBER 1990
                                      IGLEAN SITES

-------
01
                                This is  Clean Sites
                A non-profit institution devoted solely to helping speed up the
                effective cleanup of hazardous waste
A neutral and objective third party
*•   Working with involved parties
^   Toward voluntary private settlements and site cleanups
                Five functional groups:
                Settlement Services
                Technical Affairs
                Project Management
                             Public Policy & Education
                             Administration
                                                                 iCLEAN SITES

-------
                           Clean Sites1 Background
                Creation involved industrial and environmental groups, EPA, and
                Justice Department
               Formal establishment May 31, 1984
CO
00
                General contributions from 140 companies, 8 foundations,

                50 individuals
                Site-specific cost reimbursement
                Staffed by approximately 50 experienced professionals
                                                              CLEAN SITES

-------
                                   Clean  Sites1  Board of pjrectors
01
w
10
Mr. Peter A.A.Berle
President
National Audubon Society

Hon. Douglas M. Costle
Dean, Vermont Law School

Prof, Archibald Cox
Professor Emeritus
Harvard Law School

Dr. Louis Fernandez
President
Celgene Corporation

Dr. Edwin A. Gee
Chairman and C.E.O., Retired
International Paper Co.

Mr. Thomas P. Grumbly
President and Treasurer
Clean Sites, Inc.
Dr. Jay D, Hair
President
National Wildlife Federation

Dr. Donald Kennedy
President
Stanford University

Ms. Susan B. King
President
Steuben

Mr. H. Eugene MeBrayer
President
Exxon Chemical Company

Dr. Gilbert S. Omenn
Dean, School of Public Health
 and Community Medicine
University of Washington

Richard Cooper (Secretary)
Williams and Connolly
Dr. Charles W. Powers
Partner, Resources for
 Responsible Management
Founding President, Clean
 Sites, Inc.

Hon. Robert T. Stafford
U.S. Senator, Retired

Mr. Roger Strelow
Vice President
Bechtel Corporation

Hon. Russell E. Train (Chairman)
Chairman, World Wildlife Fund
 & The Conservation Foundation

Mr. Hans A. Wolf, Vice Chairman
 & Chief Administrative Officer
Syntex Corporation
                                                                                             SCLEAN SITES

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01
•ฃป
O
                          Why Parties Use Clean Sites
Sole mission is facilitating hazardous waste cleanup
Highly qualified and experienced staff
Provides a complete set of services to support cleanup of waste sites
Assisted at over 60 waste sites
Prepared more than 25 cost allocations
Credibility and fairness
Access, if necessary, to unique Board of Directors and Scientific and
Technical Advisory Board
Sensitive to needs of the parties
                                                                  CLEAN SITES ^

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             Clean Sites Organizational Structure
Vice President
  Settlement
   Services
James Kohanek
                          Board of Directors
                         Russell E. Train, Chairman
                               President
                             Thomas P. Crumbly
                                Executive
                              Vice President

                              Robin Robinson
 Vice President
 Public Policy
  & Education
Nancy Newkirk
Vice President
   Project
 Management
George Murray
                                               Director,
                                              Finance and
                                            Administration
                                            Andrew Krone
                                                                   Director,
                                                                 Planning and
                                                                   Marketing
Vice President
  Technical
   Affairs
Richard Sobel
                                  541

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IN3
      Unique Role of Clean Sites
ฉ    Settlement Services
     +   Dispute Resolution and Cost Allocation
ฉ    Technical Assistance
ฉ    Pro jeet Management
o    Services to Government Agencies
ฉ    Funds Management
ฎ    Information Services
@    Public Policy              Activities
                                                                     SITES

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 The
  Site discovery/
     inventory
tn
16
Preliminary
assessment
^
y,
Site
inspection
ฉ Organizing PRPs
• Bringing  additional PRPs to
  the negotiations
• Identifying issues, setting
  agendas
@ Resolving disputes among
  settling parties
• Coordinating and  exchanging
  information with government
  to reach settlement
                                            Assign national
                                                priorities
                                                          EPA notification
                                                           of potentially
                                                         responsible partie
                                                         Remedial invest./
                                                          feasibility  study
                                                            Record of
                                                             decision
                                                          •
                                                             Remedial
                                                              action

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 The  Role of  Clean  Sites
  Site discovery/
    inventory
X
Preliminary
assessment
x
~ฃ
Site
inspection
Ul
          * Dividing costs of studies

          ฎ Reaching settlement agreements
            for studies
Assign national
   priorities
                                                       EPA notification
                                                        of potentially
                                                      responsible partie
                                      Remedial invest./
                                       feasibility study
                                                         Record of
                                                          decision
                                                          Remedial
                                                           action

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 The  Role  of Clean Sites
  Site discovery/
    inventory
ft
Preliminary
assessment
^
^
Site
inspection
Dividing costs for cleanup

Reaching settlement agreement
for cleanup

Begin planning for
cleanup activity
                                                      EPA notification
                                                       of potentially
                                                      esponsible partie
                                                     Remedial invest./
                                                      feasibility study
                                                        Record of
                                                         decision
                                                         Remedial
                                                          action

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 The Role of Clean
  Site discovery/
    inventory
in
Preliminary
assessment
-*>
"^
Site
inspection
* Planning cleanup

• Coordinating cleanup with
  settlement

ฎ Ensuring  cleanup  meets state
  and federal requirements

• Dividing O&M costs

* Reaching  settlement for

                    coss
                                           Assign national
                                              priorities
                                                       EPA notification
                                                         of potentially
                                                       esponsible partie
                                                       Remedial invest./
                                                        feasibility study
                                                          Record of
                                                           decision
                                        *
                                        V
                                                          Remedial
                                                            action

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    Clean Sites' Activities Do Address Some Major Impediments to Cleanup
Impediment

9  Fund is being depleted; transaction
   costs are inordinately high
ฉ  Cleanup is a long and expensive
   undertaking
Clean Sites'Role

•  Encourage private party
   cleanup and facilitate
   settlements (dispute resolution)

ป  Bring more parties into the
   process (cost allocation/dispute
   resolution)

ฎ  Control costs of cleanup
   without sacrificing
   environmental protection
   (project management)

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      Clean Sites' Activities Do Address Some Major Impediments to Cleanup
  Impediment

  ซ Public has little faith the government
    is protecting them
1 ฉ Private party and EPA site studies
    suffer a "credibility gap"
    Some believe benefits of Superfund
    are not worth the cost
Clean Sites'Role

e  Inform the community about site
   activities throughout the study
   and cleanup process (project
   management)

ซ  Oversight of private party
   studies to assure they meet EPA
   requirements and are technically
   sound (technical assistance)

e  Provide information to all
   parties about ways to speed
   cleanup without undermining
   the     of                  .
   policy and education)

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                               CLEAN SITES'
                     PUBLIC INTEREST ACTIVITIES
                 Evaluate the current EPA Superfund remedy selection
                 process and make recommendations for change.
on
•P*
10
                 Provide free assistance to citizens to help them obtain
                 Superfund Technical Asstance Grants from EPA.
Conduct educational seminars entitled Successfully
Resolving Multi-Party Hazardous Waste Disputes,
providing scholarships to government officials to f aciliate
their attendance.
                 Analyze the impact of hazardous waste disposal on the
                 ruraf poor for the Ford Foundation.
                 Authored a paper entitled "Making Superfund Work", an
                 analysis of ana recommendations for the Superfund
                 program, which was presented to the Bush transition team.
                                                            MCLEAN SITES

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                               CLEAN SITES'

                    PUBLIC INTEREST ACTIVITIES
                                    continued
en
8
Conduct the Communitj Industry Forum - a series of
facilitated dialogue sessions between citizens and PRPs
involved at Superfund sites.


Facilitate policy dialogues between EPA and other interest
groups involved in the superfund process.
                 Perform initial mediation and facilitation services at
                 selected Superfund sites free of charge to help organize
                 PRP groups and to facilitate settlement.
                                                          sCLEAN SITES

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        Public Policy and Education Activities
                          (continued)
Provide policy, legal and technical support to help state agencies
develop their own Superfund programs.
Develop (in conjunction with the Environmental Law Institute) a State
Superfund Information Network to facilitate sharing of information
between states.
Facilitate policy dialogues between EPA and other interest groups
involved in the Superfund process.
Perform initial mediation and facilitation services at selected
Superfund sites free of charge to help organize PRP groups and to
facilitate settlement
                                                  1CLEAN SITES

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U1
en
              CLEAN SITES' ASSISTANCE TO STATE

                      SUPERFUND PROGRAMS
Provide policy, technical, legal support to State hazardous
waste cleanup programs. Clean Sites helps states develop:



o    Regulations



• • - •  Site cleanup related procedures



•    Settlement, enforcement and administrative policies


•    Program management tools



•    Training courses
                                                      CLEAN SITES

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in
in
                                Technical Affairs
              Technical staff manages and reviews site cleanup studies, advises
              responsible parties and their contractors
ฉ  Goal is to ensure quality and content in studies as needed by EPA to
   select appropriate remedy


ฎ  Assist parties to resolve technical disputes
              Technical Advisory Board, whose members have international
              stature in their speciality areas, supports in-house staff
              Conducting an independent analysis of the Superfund remedy
              selection process under EPA grant
                                                                 1CLEAN SITES

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                        Scientific & Technical Advisory Board
              Gilbert S. Omenn, (Chairman)
                    Dean, School of Public Health and
                    Community Medicine,
                    University of Washington
                                               John Doull
                                                    Professor of Pharmacology and
                                                    Toxicology University of Kansas
                                                     Medical Center
en
en
Gary F. Bennett,
     Professor of Biochemical Engineering
     Department of Chemical Engineering
     The University of Toledo
Serge Gratch
     Professor of Mechanical Engineering
     GMI Engineering and Management
      Institute
              Kenneth E. Biglane
                   Independent Environmental Consultant
                   Formerly, Director of Hazardous Response
                     Support at U.S, EPA

              David W. Miller
                   President and Chief Operating Officer
                   Geraghty and Miller, Inc.
                                               Perry MeCarty
                                                    Professor and Past Chairman
                                                    Department of Civil Engineering
                                                    Stanford University
                                                                                CLEAN SITES

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           Technical Services
     Oversight of Remedial Investigations and
     Feasibility Studies
ฉ    Manage Remedial Designs


ฎ    Technical Advice Involving Allocations Issues


o    Peer Review to Ensure Accuracy and
     Objectivity
     Technical Assistance to all Clean Sites
     personnel
                                           ICLEAN SITES

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          Technical Services
                 continued
    Technical and Data Mediation
    Ensure Consistency with NCP for RI/FS
ฉ   Site Assessment for Real Estate Transfers
    Preparation of Guidance Documents
                                         1CLEAN SITES

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                         Project Management
•  Assist responsible parties in carrying out the many tasks required for cleanups


ฉ  Adhere strictly to regulations; work effectively with EPA and State agencies


•  Assign an on-site project team (for large jobs) and/or headquarters staff to
   monitor, control, and report


•  Provide contracting, scheduling, cost estimating and control services


ฉ  Community relations activities are an integral part of project management
                                                           ICLEAN SITES

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                FiiiicLManagement
Manages and disburses funds for PRP Groups and Steering
Committees
Over $20 million under management at eight sites
Integrated with Project Management and Site Committee
activities
                                              ICLEAN SITES

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                                    COST ALLOCATION PROCESS
01
ui
                                Collect
                               Information
                                  and

                               Organize
                             into Data Base
                                                     Assure
                                                    Quality
                                                      of
                                                     Data,

                                                    Review
                                                     Issues
                                                                     ฅ
  Consider
  Allocation
   Factors:

    Cost
   Toxicity
Transshipments
Status of PRPs
     etc.
                      Agree on
                      Allocation
                      of Costs
                    Orphan Shares
                    Mixed Funding
                  De Minimis Buyout
                         etc.
                                                                                    MCLEAN SITES

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m
a%
o
                        Technical Dispute Resolution
Neville Chemical Co., CA

      (Technical Mediation)



Magnolia Street, CA

      (Independent experts to allocate

      responsibility for contamination plume)




NPL Site, TX

      (Blue Ribbon Panel to review

      RI/FS, EA)
                                                            ICLEAN BITES

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          SETTLEMENT SERVICES
   Organizing and Increasing Participation of Parties


   Facilitate Communication Among All Involved Parties
•  Identification. Assessment and Prioritization of Issues
   Mediating and Resolving Disputes Among Participants
   Coordinating an Exchanging Information with the
   Government
   Allocation of Costs Among Parties


   Administrative Support
                                             sCLEAN SITES

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                   Settlement Services
Assists in the organization of PRPs
Encourages the involvement of new PRPs in the Allocation process
Assists parties in defining issues and designing the process
Develops and evaluates innovative approaches
Collects and analyzes data
Provides computerized data base management services
Provides dispute resolution services, if desired
                                                   CLEAN SITES

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       Settlement Services Experience
Helped bring about final settlement agreements

4   For twenty sites
4-   For removals, remedial actions, or cleanup studies
4-   Cleanup activities value of $193 million

Helped divide cleanup costs among responsible parties

*   For twenty-five sites
ซ•   Collection and analysis, verification and array of data in
    computerized data base form
+   Highly qualified professional staff
                                              CLEAN SITES

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           Allocation Experience
Successfully developed allocations with large number
of PRPs (over 800) and diverse interests

    large and small companies

    municipalities, federal agencies

    transporters,  owner/operators
                                           CLEAN SITES

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                            Allocation Experience
                                    continued
Ul
Instrumental in assisting development of mixed funding and
deminimis buyouts as part of allocation

Developed information to list names of additional PRPs

Developed allocations using

ซ•    non-volumetric measures such as toxicity, mobility,
     processing considerations, cost of remedial activity
*    volumetric measures
>    other considerations such as transshipment, recycling,
     BTU values, past ownership of facility
                                                                CLEAN SITES

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                           MATO/CCMs CJUest Speaker:



                         Roy C. fJwtt&JH) ilhttecf States



Environmental Contamination in Eastetfi iHcf Slhtral Europe
                     567

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     Presentation  to  the  NATO/CCMS  Conference
     NATO Committee  on the  Challenges  of a  Modern  Society

Pilot  Study on the Demonstration  of Remedial Action Technologies
            for  Contaminated Land and  Ground-water
        "Overview  of  Environmental  Contamination
   in Eastern  and  Central  Europe:   A  Focus  on  Hungary"
                           Presented  by:

                   Dr. Roy C. Herndon, Co-Director
     Joint  Center  for Hungarian-American  Environmental  Research
                      Florida State University

                               and

                   Dr. Peter I. Richter, Co-Director
     Joint  Center  for Hungarian-American  Environmental  Research
                  Technical University  of  Budapest
          Prepared in Cooperation with  Dr.  Donald  Alexander
                     U.S.  Department  of  Energy
                        Washington, B.C.
                       November  19,  1991
                               S68

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I.   INTRODUCTION AND BACKGROUND MATERIAL

     This  presentation was  prepared for the NATO/CCMS Conference
which was  held on November 18-22,  1991 in Washington, D.C,  This
NATO  Committee  on the Challenges of a Modern  Society focuses  on
the demonstration  of  remedial  action technologies for contaminated
land and groundwater, a  challenging  issue  for both NATO  and non-
NATO   countries  alike.   This  presentation addresses environmental
contamination  in  central  and  eastern   Europe  (with a  focus  on
Hungary)  and  serves  to  illustrate  the  extent  and nature of  current
environmental   problems  in  this  region  of  the   world.    The
presentation is  given  by Dr. Roy C. Herndon  of the Florida  State
University  (FSU) and Dr. Peter  I. Richter of the Technical University
of Budapest (TUB), and consists  of four parts:

     +•  Introduction and  Background Material;
     +•  Overview of Environmental Contamination in the  Region:   A
         Focus on Hungary;
     ซ•  Sources  of Environmental Contamination  in  the Region:   A
         Focus on Hungary; and
     +  Priorities   for   Addressing   Near-term   Environmental
         Problems in the Region.

     Drs.   Herndon   and   Richter   have  worked   jointly   on
environmental  research  for  over 10  years and  co-direct  the  joint
Center  for Hungarian-American  Environmental Research  which   is
administered at FSU  and  which  involves  participation  by  the faculties
of both FSU and  the TUB.  This joint environmental  center conducts
research   on   common   environmental  problems  (e.g.,   the
                               569

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restoration/remediation  of  contaminated   land   and  groundwater),
facilitates  the  transfer  of  environmental technologies  through  joint
environmental research and  training,  and facilitates the exchange of
research  faculty   and  graduate  students   (including  postdoctoral
students)  from academic institutions in Hungary with universities in
the U.S.
      One  of the  current  activities of  this  joint  center is the  1992
International Symposium  on Environmental  Contamination  in Central
and  Eastern  Europe (Budapest  '92) which  will be held in Budapest,
Hungary   on  October   12-16,  1992.     Approximately  500-600
participants are  expected to  attend  the  symposium.   This  symposium
will include presentations  by  academic and  agency researchers  as
well   as   demonstrations   and   exhibitions  by   providers   of
environmental  goods  and  services.    A   major  emphasis  of  the
symposium  will be on  evaluating  technology  transfer  and exchange
opportunities related to  environmental technologies.  The response to
the  first   symposium  announcement,  which   was distributed  more
than one  year  before the date  of the symposium, has  been  very
strong.   To-date, over 500 responses  to the first  announcement  have
been  received  from  all  over  the  world and   include  academic
researchers,  agency  researchers,   and  private  companies   and
individuals   who  have  indicated  a  desire  to  participate  at  the
symposium.  The  second  announcement for the symposium  will  be
distributed  within  the  next few months.
     This  joint  center  is designed  to work  cooperatively  with  a
variety  of  organizations  which  are  involved  with environmental
problems in  the region,  including the Regional Environmental  Center
                                570

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for  Central and  Eastern Europe  (REC).  The  REC was established to
accomplish a variety  of  regional environmental  objectives, including:
      +   collecting  and  disseminating  environmental  data   and
          information;
      +   facilitating  institutional  development,  in  the  context  of
          environmental  decision-making  within  the  region;
      4   serving  as  an  environmental clearinghouse for  the  region;
          and
      *   providing education and  training  on environmental issues.
II.   OVERVIEW OF ENVIRONMENTAL CONTAMINATION IN THE
      REGION: A Focus ON HUNGARY

      Over   the  last  40-50  years,   extensive   environmental
contamination has occurred throughout central   and  eastern Europe.
In  the  absence  of effective  controls for  the  management  of  air
emissions,  hazardous  and  industrial waste, sewage   and  wastewater
there are  significant  environmental  problems  that  have  occurred
throughout  the region.   As  a result,  there are  extensive  acute  and
chronic  health  problems in  the  region   that can  be  attributed  to
environmental  contamination.
      These   adverse   health   and  environmental   problems  are
associated with  contaminants  originating  from a  variety of sources,
including  emissions  from  automobiles  and  smokestacks,  and  the
mismanagement  of   hazardous   wastes.     Many  urban  and
industrialized areas  in the  region  have  problems  ranging from
serious  smog-related incidents to relatively  high  rates of lung cancer
                               571

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as  a result  of  exposures  to  airborne  contaminants.   Power  plant
emissions have  also  adversely  affected significant areas of forestland
throughout the  region.   There  are  little  data  available  that  can be
used  to  effectively  characterize  the extent  and  nature  of  these
problems  or   to   identify   and  prioritize   the   major   sites  of
contamination.    However, there is  little  doubt  that  these  problems
are extensive and  will require  a great deal of  regional  as  well as
international  cooperation  in  order  to  effectively  manage   these
problems  within the nearterm  and longterm.
      Surface waters  have  become contaminated with  a variety of
substances, including heavy metals.   Much of the surface  water  in  the
region  is  unsuitable  for  drinking and,  in  many  instances, is  also
unsuitable  for  agricultural  uses.   Groundwater  in many areas of  the
region has also  become contaminated  to the point where  it is  not safe
to consume.
      In  urban   and   heavily-industrialized  areas,5   soils   are
significantly  burdened  with a variety  of  contaminants as  a  result of
the  longterm   dumping  of  hazardous  wastes.    In  many  cases,
farmlands  and  associated  surface waters  have  become  contaminated
with  a  variety  of industrial wastes.
      One-third   of  Poland's 3&  million   people  live in  "ecological
hazard  areas"  according  to the Polish  Academy  of  Sciences.   In
Poland, more than  600,000  acres of woodland have  been  damaged by
acid  rain.   Also  in  Poland,  approximately  80 percent  of  surface
waters  are   considered undrinkable,   and approximately 33  percent
are not fit for industrial uses.  . In  Crackow, Poland, approximately 60
                                572

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percent  of the  food grown is  considered unfit for  human  consumption
because of high levels of heavy metals in the soil.
      Half  of  Czechoslovakia's  drinking  water  fails to  meet the
country's  own  health  standards.    In  Tepiica,  Czechoslovakia,  air
pollution  from  coal  mines  and power  plants  keeps  school  children
inside their homes for one month during the  winter  and and  forces
parents  to  send the children to schools in  cleaner towns for up  to  six
months  each year.  In Czechoslovakia,  approximately  1,000,000  acres
of  woodland  have  been  damaged   by  acid  rain  believed to  be
attributed to power plant emissions.
      The  City of Dorog  is  considered to  have  some  of the  more
extensive  environmental  problems   in  Hungary.    It has   been
characterized   as   a  city  so  contaminated  that  the Peace  Corps
determined  that  the  environmental  problems  are  so serious   there
that  it was judged to be  too risky  to  place a Peace Corps volunteer in
the city.   One in ten  Hungarians lack  access  to  safe drinking   water
and  are  reported to die as a result of pollution-related diseases.
      Bronchitis and  eczema  reportedly  affect  half  of the children in
eastern  Germany's  industrialized   areas.     Industrial   waste  has
contaminated  nearly  70  percent   of  Bulgaria's  farmland   and
approximately  65  percent of  its river water.   Romania's  largest city,
Bucharest,  has no sewage treatment plants and elsewhere in  Romania
most  of the country's  sewage treatment plants  do not work  properly.
In Copsa Mica, Romania most structures  within a  15-mile radius are
blackened by  soot from  factories.
                                573

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III.  SOURCES OF ENVIRONMENTAL CONTAMINATION IN THE EEGION:
      A Focus ON HUNGARY
      Automobile emissions  generated  by  two-cycle engines  which
burn  diesel  and  petrol  produce  significant  amounts  of  carbon
monoxide,  nitrogen  oxide  (diesel),  hydrocarbons,  and  lead.   Air
pollution  problems  from  automobile emissions  are,  in  some  areas,
significant even in the countryside.  For example, it is  estimated that
Hungary's  motor  vehicle  fleet   produces  the  following  annual
pollution  loads  into  the  atmosphere:    one million  tons  of carbon
monoxide;  130,000  tons  of  hydrocarbons;  120,000  nitrogen  oxides;
36,000  tons  of  particulates;  and  over  500 tons  of lead  and  lead
compounds.    Measurements  at  congested   road  intersections in
Budapest  also demonstrated that  concentrations of  carbon monoxide,
lead and  formaldehyde often exceed permissible levels.
      Industrial sources generated  by  chemical plants, paper  mills,
mining,  metallurgical plants,  oil  refineries,  foundries  and   other
industrial  operations   introduce  large   quantities   of  airborne  and
waterborne contaminants   into  the environments  of  countries in
central and eastern Europe.   In  Hungary, the  raw  material,  extractive
industries  are  the most environmentally  harmful.   For  example, the
mining  of  coal, uranium  ore  and  bauxite  have  adversely  affected
groundwater  quality   and  have  severely ruined extensive  areas of
Hungary's  landscape.   Both  metallurgical operations and power  plants
generate  relatively  large   quantities of  air  pollutants,  particularly
sulfur  dioxide and solid particulates.  These  activities  also  generate
relatively   large  quantities  of  contaminated wastewater  which
typically  is  discharged untreated.  The  chemical  industry  in the
                                574

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region produces  a variety  of hazardous  pollutants (e.g., gases, alkali
wastes,  pigments, solvents, toxic sludges and  solutions).
      Agricultural  sources  of  contamination  generate  waste  streams
that  consist  of  fertilizers,  pesticides  (including   phosphates  and
nitrates),  and  farm  animal   wastes  which  can   cause   longterm
contamination of  the groundwater and  promote  the   growth  of algae
in  rivers and lakes.   With  the growth  of  mechanized agricultural
production  has  also  come  a   prodigious increase  in  the  use  of
fertilizers.   In  particular, the  use  of  nitrogen-based  fertilizers  has
contributed  to nutrient leaching  in certain  areas of the  region  as well
as  a  rise  in  the nitrate levels  in groundwater,  endangering  drinking
water supplies.   Herbicides, fungicides and insecticides  are applied in
some  areas  of   the region  in  doses  that   are  believed  to  pose
unacceptable  environmental risks.   These  substances  can pollute the
ecosphere  and endanger the equilibrium  of ecosystems by  adversely
affecting  the  foodchain.
      Solid and  hazardous  waste-related  sources  of contamination are
believed  to  have  severely  damaged  groundwater, surface water  and
soils  throughout  the  region.  Despite  the  adoption  of  hazardous waste
regulatory programs  in some central and  eastern  European  countries
in  the early 1980's,  little has been  done to protect human health  and
the environment  from exposure to hazardous  waste.    It is  reported
that  heavy  metal-laced  industrial   wastes  have  tainted   much  of
central  and eastern Europe's waters  and foodchain.   For example, in
the  area  of  Poland's  Upper   Silesia,  soil  concentrations  of lead,
cadmium,   and   other heavy  metals  have been found  to  exceed
acceptable limits.   In a recent  study,  35  percent of the children in
                                 575

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this area of Poland showed evidence  of lead poisoning.   In addition  to
the discharge  of  untreated  hazardous  and  industrial  wastes  into
surface  waters,  holding  ponds,  and  other  typically  unlined  and
unmonitored  impoundments,  few precautions  or  proper management
practices are utilized throughout the region.
      As  an  additional  source  of pollution  within  the  region,
transboundary sources  have adversely  affected  air, water, and  land.
Shared  water  and  air resources  in  the  region  are  typically  not
managed  effectively  so  as  to  prevent  the  movement of  pollution
generated in one  country to .another country.  For  water resources,
the areas of greatest concern are the Black  and Baltic  Seas and the
Odra, Vistula, Elbe and Danube Rivers.   For  air resources,  the area  of
greatest concern is "the sulfur triangle"  - which is an area associated
with   the   intersections   of  eastern  Germany,   Poland   and
Czechoslovakia. This  area  has experienced  substantial  declines  in
forest  stands with  resulting  severe adverse  consequences  for  the
landscape and  the  water balance within the region.   One additional
type  of  transboundary  pollution  involves   the   transportation  and
ultimate  mismanagement of  hazardous  wastes  between countries  in
the region as well as from sources  outside of the region.

IV.  PRIORITIES FOR ADDRESSING NEAR-TERM ENVIRONMENTAL
      PROBLEMS IN THE REGION

      Given  the extent, nature  and  complexity  of the  environmental
contamination  problems  in  central   and  eastern   Europe,  it  is
important to identify  priorities  for  addressing  the many  and  varied
                               576

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aspects  of these  problems.    This  is  particularly  important in  the

context  of the prevailing regional economic  conditions.  The following

priorities  for  addressing near-term  environmental  problems of  the

region have been  suggested:

      *   Economic  Reform  - economic  reform  is considered to be a
          prerequisite   for   the   implementation   of   successful
          environmental protection  programs  in the  region.    Key
          elements of economic  reform include  privatization and  the
          development  of   property  rights,   restructuring   and
          modernization  of  industry,  elimination  of  state subsidies  to
          industry,  and the  use  of  market-determined  prices  for
          energy  and  natural resources.

      +   Environmental Regulation  and  Enforcement  -  an  important
          component   of   implementing  effective   environmental
          management  systems  in  the  region  should  include  the
          adoption of  appropriate  environmental  legislation that  is
          consistent  with   the   environmental   standards   and
          regulations of the European  Community and  other western
          countries, and that is implemented  in  conjunction  with
          properly-funded  and effective  enforcement  programs.

      *   Environmental   Education    and  Public   Awareness -
          environmental education  and  public  awareness   activities
          should  be  conducted  at  all  levels of  education  and
          professional training.   It  was  also  suggested  that,  using
          mass  media  and   other  appropriate  mechanisms, public
          awareness  of   environmental   problems   and  proper
          management practices  should be  heightened.

      *   Scientific/Technological  Development  and  Exchanges -
          research as  well  as  technology  transfer  and  exchange
          activities  should  be prioritized and  focused in  the  near-
          term  on  solving   practical  environmental  contamination
          problems.    These  practical  solutions should   result  in
          incremental  improvements  in  environmental  conditions
          and/or management in the region that are consistent with
          the  available  resources  and economic constraints of  the
          individual  countries.
                                577

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      *   Regional   and  International  Cooperation  -  regional and
          international  cooperation  for  addressing  the   near-term
          environmental  problems  facing   the   region  will  be
          necessary   for  establishing   effective   institutional
          management  systems  for controlling  air,  water and  soil
          contamination  and for remediating  existing environmental
          sites  in  the  region.   Organizations such  as the Regional
          Environmental  Center for  Central  and  Eastern  Europe
          (Budapest), the  Commission  on European Communities,  the
          European  Bank for  Reconstruction  and Development,  the
          European   Environmental  Agency,  the  World  Bank,  the
          World  Health  Organization  and   other  international
          organizations  can  play   an  important role  in  facilitating
          regional and international cooperation  among the countries
          in the region.

      In addition to regional  and  international  cooperation,  it  will
also be important to  identify  appropriate  technologies  that  can be
used  for addressing  specific  near-term  environmental  problems in
the  region.    These  technologies  relate  to  both  the  preventative
(control technology) aspects as  well  as  remedial aspects of  these
problems.   Appropriate categories of technologies include:

      *   reclamation technologies  for  land and  water;

      *   pollution control technologies for air and water; and

      *•   solid  and   hazardous   waste  treatment   and  disposal
          technologies.
                               578

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                                    NATO/CCIVIS Guest Speaker:



                                  Gregory Ondich,  United States



The Use of Innovative Treatment Technologies in Remediating Waste
                             579

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               THE USE OF  INNOVATIVE TREATNENT TECHNOLOGIES
                     IN REMEDIATING HAZARDOUS WASTES                •
                                    by
                            Gregory G. Ondich
                             Acting Director
      Waste Minimization, Destruction and Disposal Research Division
                  U. S. Environmental Protection Agency
                             Cincinnati, Ohio                      i        .
                           for presentation at
     The Second  International NATO/CCMS Meeting on the Demonstration
  of Remedial Action Technologies for Contaminated Land and Ground Water
                             The Netherlands
                           November 7-11, 1988                       .

]K^S. Hazardous  Waste Programs
     Eight years ago the U. S. Congress enacted the Comprehensive
Environmental Response, Compensation and Liability Act of 1980,
frequently referred to as "Superfund" or "CERCLA."  This law was created
1n response to the discovery of numerous uncontrolled and abandoned
dumpsites throughout the United States and the lack of funding and authority
under existing national laws to clean up such sites.  CERCLA provided the
U.S. federal government for the first time with resources ($1.5 billion
over five years) and authority to respond to uncontrolled releases of
hazardous wastes or materials from any facility.  In addition to funding,
CERCLA established a method for imposing liability on parties responsible
for these dumpsites.
     In addition to CERCLA, the Resource Conservation and Recovery Act
(RCRA) and its 1984 amendments are intended to prevent the creation of
problem sites through stringent controls on ongoing waste management,
                                                                   ' "•''' 'L  " " ปป'*
to reduce the land disposal of hazardous wastes and to encourage the   :   ?-•> I
use of waste minimization practices.  Together the Superfund and RCRA
legislation form the core for the U.S.  programs to address hazardous        .
waste problems, both past, present and future.  Each of these legislative

                                     580

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mandates creates opportunities for the use of innovative treatment  technol-
ogies in remediating hazardous wastes.  The United States (U.S.)  nearly
decade-long experience with the cleanup and management  of hazardous
wastes has shown that simple containment of wastes in the land -  with
clay caps and subsurface walls - fails to protect  human health and  the
environment from the dangers associated with hazardous waste.1
              RCRA Best Demonstrated Available Technology (BOAT)
     Despite this early recognition of the significant  role of land disposal
at problem hazardous waste sites, Superfund cleanups  throughout the early
years of the program continued to be based on re-land disposing of  wastes
dug up at these sites.  In the 1984 reauthorization of  RCRA,  the  U.S.
Congress mandated restrictions which prohibit the  continued land  disposal
of untreated hazardous wastes beyond specified dates.   The statute  requires
EPA to set "levels or methods of treatment which substantially reduce,the
likelihood of migration of hazardous constituents  from  the waste  so that
short-term and long-term threats to human health and  the environment are
minimi zed."2
     The,restrictions established by the 1984 RCRA Amendments  are significant
and carry strict timetable dates.  These so-called land ban restrictions
set up a 5-year program to establish treatment standards that  wastes must
meet before being land disposed.  A timetable for  each  group  is given
below.
                     Land Ban Restrictions Timetable
Dioxins and Solvents                                        November 8,  1986
California List (Metals and Cyanides,  Corrosives,            July 8, 1987
  Halogenated Organics)
First-Third of Remaining Hazardous Wastes                   August 8,  1988
Second-Third of Remaining Hazardous Wastes                  June 8, 1989
All Hazardous Wastes   	     '       	  	May 8, 1990
                                     581

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     The RCRA legislation requires mandatory notification of waste generation
and the manifesting of waste shipments.  These requirements and the permits
required for storage, treatment, and disposal facilities have created cradle-
to-grave control of these wastes.  This waste management approach has created
an opportunity for the development of adequate and cost effective treatment
methods.  For many of the wastes generated, a process to adequately treat  them
cost-effectively or that has sufficient capacity to handle the waste volume  is
absent.  This technology vacuum provides a great incentive and opportunity to
develop and market new technologies.
     As a result of the 1984 RCRA Amendments, EPA will establish a performance
level of treatment based on the best demonstrated available technology
(BOAT) identified for hazardous constituents.  These treatment levels will be
monitored by measuring the concentration level  of the hazardous constituents
1n the waste or treatment residual or an extract of the residual.  Ultimately,
the RCRA BOAT requirements will promote the use of innovative technologies
by those waste generators who are looking for more cost effective methods
of treatment than existing technologies.
     In addition to authorizing very,stringent treatment and disposal
                                                                          i
regulations, the 1984 RCRA Amendments also stated that the U.S. top
waste management priority was a redirection towards "waste minimization"
as a preferential strategy for encouraging improvement in environmental
quality.  The legislation states;
     "The Congress hereby declares it to be the national  policy of the
     United States that,  wherever feasible, the generation of hazardous
     waste is to be reduced or eliminated as expeditiously as possible.
     Waste that  is nevertheless generated should be treated,  stored,  or
     disposed of so as to minimize the present and future threat to human
     health and  the environment".2
                                      S82

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     This waste minimization requirement  will  foster the  development  of
innovative technologies that are not convenient "end-df-the-pipe"  treatment
approaches.
     Looking beyond "erid-of-the-pipe" treatment also has  many  benefits  in
solving pollution transformation problems.   Some treatment  technologies, while
solving one waste management problem, may create others.   Air  pollution  control
devices or wastewater treatment plants can  prevent  wastes from going  into  the
air and water, but the toxic ash and sludges removed from these systems  con-
stitute enormous hazardous solid waste problems requiring attention.  Solid
wastes deposited in landfills or deep wells can become water pollution  problems;
evaporation from ponds and lagoons  can turn solid or liquid wastes into  air
pollution problems.  Likewise, some waste management facilities,  such as
landfills to bury wastes or incinerators  to destroy them, are  facing  growing
local public opposition to siting proposals.3

                       Re-li!T'J19 Waste Mi n i mi_za_t ion
     Waste minimization means the reduction, to the extent  feasible,  of  any
solid or hazardous waste that is generated  or  subsequently  treated, stored
or disposed of.  Reducing the generation  of hazardous wastes can  be achieved
in many ways.  Process chemistry can be changed. Potential waste  streams
can be recycled within a manufacturing process or back into the process.
Process technology and/or equipment can be modified to produce products
more efficiently, resulting in less waste.   Plant operations,  i.e., "house-
keeping" methods can be changed or  controlled  to produce  fewer and smaller
waste streams of* less waste in general.  Changes in raw materials  (feedstocks)
can lead to fewer waste streams or  less-hazardous waste streams,  and  changes
in the end products from manufacturing operations can, in some instances,  be
made so as to affect the types and  quantities  of wastes emitted.   The early
                                     583

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introduction of these and other waste reduction techniques into broad
commercial practice is one of the objectives of the EPA Waste Minimization
Research Program.^
     In order to carry out the intention of the RCRA Amendments to reduce
the generation of hazardous waste in the U.S., the EPA has developed a
multi-faceted non-regulatory hazardous waste minimization program.  This
program includes innovative technology evaluations, plant and/or process
assessments, technology transfer activities and extensive communications
with industry, states, universities and the general public.
     There is encouraging news regarding the study of waste minimization
practices in the U.S. chemical industry.  After three years of intensive
research into the hazardous waste minimization practices of 29 U.S.
organic chemical plants, INFORM, a non-profit U.S. research organization,
found reports of 44 innovative waste reduction practices.  These practices
Involved a variety of process, product, equipment and operational  changes"
that substantially reduced or eliminated individual chemicals in waste
streams at the plants.  To the extent that INFORM was able to document
the actual impact of the practices, it was found they prevented the
generation of at least ^e^ej^nnjj_iฃn_|iound_s of hazardous chemical  wastes
and saved companies nearly $1 million annually in reduced raw material  and
waste disposal costs.  These 44 practices taken together suggest the range of
possibilities that exist for the more than 1,000 U.S. organic chemical  plants
to reduce wastes at the sources.3                      ,           ,  ,  ,,
                          Land Ban Restrictions           ...             ,   r
     In Hay, 1988, EPA proposed rules for the "first-third" of 'listed_ RCRA.Jff.
wastes that will be affected by the RCRA Amendments land disposal  restj'ic,- ,,,ป;
                                    584

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tions.  Land disposal restrictions on "second-third" and "finaj-third"
wastes will be phased in over the next two years.
     As stated earlier the 1984 RCRA amendments require EPA to restrict
land disposal of all hazardous wastes by 1990.  Source reduction and
waste recovery (recycling), respectively, are the preferred EPA waste
management practices with treatment and land disposal following in this
hierachy.  One example of this preference for waste reduction and recovery,
is the EPA requirement for metals recovery of el.ectric-arc-furnace dust
from emission-control devices at steel  mills.5
     The EPA requirement in the May, 1988 proposal  was for waste genera-
tors to treat first-third wastes prior to land disposal to reduce volume,
hazardous constituency and mobility.  EPA's proposed treatment standards
recommend that generators use the best demonstrated available technology
(BOAT) to treat wastes.  The standards also require generators to achieve
specific toxicity concentrations, which vary by waste.  Incineration and
stabilization were two commonly recommended BDATs in the proposed rule  on
first-third wastes.         ,                                  .
     These proposed EPA rules do not preclude use of other waste-treatment
technologies.  However if those processes cannot produce the same toxicity
reductions achieved by BOAT, the wastes cannot be land disposed.6

        Stip'erfund Innovative Technology Evaluation  (SITE)  Program
     The growing concern about on-going Superfund cleanups that favored
containment caused significant debate when the Superfund program was
scheduled for Congressional reauthorization in 1985.  Reliable data on
the'performance and cost of new and innovative treatment technologies
were-not"*yet available for hazardous wastes and/or  substances.  Thus,
                                     585

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passed, one Important provision was for EPA to establish an "Alternate
and Innovative Research and Demonstration Program."
     In response to SARA, EPA has established the SITE program to:
       ฐ  accelerate the developmen^, demonstration, and use of new
          or innovative treatment technologies and
       0  demonstrate and evaluate new, innovative measurement and
          monitoring technologies.?.
     In Superfund's nearly eight year history, it has been evident
that a premium must be placed on the use of permanent treatment technologies
in conducting response actions.  Continued use of inherently temporary
and potentially unreliable methods such as land disposal  or containment
can be expensive and inefficient over the long run because of the recurring
need to monitor and correct disposal/containment facilities.  While some
alternative treatment methods are coming into use, overall  the development
of new treatment technologies has proceeded very slowly.
        Just as in the RCRA BOAT program when the terms "demonstrated" and
"available" needed to be defined, so too in the SITE program "alternative"
and "innovative" needed definition.  To be considered a "demonstrated"
treatment technology for purposes of the RCRA regulations,  a full-scale
facility must be known to be in operation for the waste or  similar  vwstes.
Likewise, an "available" treatment technology must meet several  criteria:
     1. "It does not present a greater total  risk than land disposal;
     2.  A proprietary or patented process can be purchased from the
         proprietor: and            ,
     3.  the process must be able to substantially reduce the toxicity or
         migration of hazardous constituents."8         ,         ,   ,,..,,,,,,„,
                                     586

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     SARA defines "alternative technologies" as "those methods,  which
permanently alter the composition of hazardous waste through chemical,
biological, or physical  means so as to significantly reduce the  toxicity,
mobility, or volume (or any combination thereof) of the hazardous waste
or contaminated materials being treated."9  Under the SITE  Program,  alterna-
tive technologies are categorized by their development status as follows:
     ฐ  Avail abl e Alternative Te_chno1 ogy.  Technologies, such as incinera-
        tion, tn~at~are~ ?ulTy~~proven" and in routine commercial  or private
        use.
     ฐ  Innovative Alternative^ Teฃhnฃlqgy.  Any fully-developed  technology
        foT wRTcTTTbst or performance information is incomplete, thus
        hindering routine use at hazardous waste sites.  An innovative
        alternative technology requires full-scale field testing before
        it is considered proven and available for routine use.
     ฐ  E me r g i n g AlterTIi at 1 ve Techno!ogy.  An emerging technology is  one
        Tn~ฅn"YalTTe"FlitIge~ o"f deveTopirient; the research has not yet
        successfully passed laboratory- or pilot-scale testing.7
     The SITE Program assists technology developers in the  development  and
evaluation of new and innovative treatment technologies.  This enhances
the commercial availability and use of these technologies at Superfund
sites as alternatives to land-based containment systems presently in use.
                               SITEProgram
There are four principal components of the EPA SITE Program:
     ฐ  field-scale demonstration evaluations                 '
     0  emerging technology development
     0  EPA developed technologies
     0  technology transfer clearinghouse.
     Each of these components is designed to enhance the use of  alternative and
innovative treatment technologies in remediating hazardous  substance sites.
                                      587

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                   fJLfJJ-l Scale Djjmoiijstration Eva! u at Ions
     One of the largest  components of the SITE Program Is the evaluation
of full-scale demonstrations.  This is one of the most important aspects
of the program because these successfully demonstrated technologies should
then be available for remedial selection in Superfund cleanups.  The
purpose of the demonstration and evaluation of selected technologies is
to develop performance,  cost-effectiveness, and reliability data on the
applicability of these technologies to specific waste characteristics.
Two EPA reports will be  produced on each demonstration scale evaluation -
a J>e rf onnsjHi d at a report and an application analysis report.  These
reports will identify the limitations of the technology, the wastes and media
to which they can be applied, the operating procedures, and the approximate
capital and operating costs.  Normally, the demonstrations are carried
out at full-scale or in  some cases, at a scale that allows valid comparision
and direct scale-up to commercial size units.  The duration of the
demonstration varies depending on the type of technology — from three to
four days for a thermal  process to several  months for a biological  or
vacuum extraction process.
     The costs for the demonstration evaluations are shared between the
EPA and the developer.  The EPA pays for evaluating the technology ป-
sampling and analysis, data quality assurance and quality control, and
report preparation.  The technology developer is expected to pay the
costs to transport their equipment to the site, operate the equipment on-
site during the demonstration, and remove the equipment from the site.
Normally, there will be no exchange of funds between the EPA and the
developer for the demonstration evaluation.  In a few instances where
      <_
the technology is unique, unusually promising, and high in financial risk,
                                      588

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the EPA will consider bearing a greater portion  of the total  project cost
if the developer is unable to obtain financing elsewhere.
     Since 1986 EPA has issued three requests  for  proposal  under the
demonstration program -- more than 100 developers  have  responded.
Solicitations are issued annually each January.  To  date,  nearly 30
technologies have been accepted into the program.  These technologies
include;                                        '      •                     '
     ฐ,  solidification/stabilization -- eight
     0  thermal — eight
     0  biological — five
     0  physical -- five
     0  chemical — three  •                         '•
     See Table 1 for a list of these technologies.   As  of  September 1988,
seven demonstrations/evaluations of these technologies  have been completed
or are underway.  Details on these demonstrations  are summarized in Table 2.
Preliminary results of these demonstrations/evaluations  are summarized  in
Table 3.  And in Table 4, a list is provided on  the  use  and/or  further
demonstration of some of these SITE technologies.                       '

                     JLmeU.inJ. Technology pevelopm_ent
     Less than a year ago, the Emerging Technologies Program was started.
This Program will foster the further development of  technologies or approaches
that are not yet ready for demonstration.  The goal  is to  ensure that a
steady stream of more cost-effective technologies  will  be  ready to be
demonstrated, thereby increasing the number of viable alternatives available
for use in Superfund cleanups.
                                     589

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     The Emerging Technologies Program will deal  with innovative technologies
for recycling, separation, detoxification, destruction,  and solidification/
stabilization of hazardous constituents and material  handling technologies.
Candidate technologies must show promise at the bench/laboratory scale.   This
program will enable technology developers to advance from the bench/laboratory
to pilot scale through cooperative funding with EPA.   The Emerging  Technology
Program was started in the fall 1987.  Of the 84  proposals that  were  submitted
seven were selected for funding.  The second solicitation was made  in July 1988.
The seven technologies selected from the first solicitation are  summarized in
Table 5.  These projects should begin within the  next two months,

                        IfA Developed Technologies
     Over the past few years,  EPA's Office of Research and Development has been
developing alternative technologies for the destruction  and cleanup of hazardous
waste.  Several  of these technologies are approaching the field  evaluation and
demonstration stage.  After the technologies are  satisfactorily  demonstrated on
Superfund wastes, it is expected that the technologies will  be commercializfd and
marketed by private industry.   The Technology Transfer Act of 1986  simplifies
the U.S. government-industry partnership necessary to bring these technologies
to commercialization.  It is expected that the marketing risk in commercializing
these technologies will be reduced and development accelerated by conducting
field evaluations under the SITE Program.  Some of the technologies in the
program are listed in Table 6.
                    Techno]ogy Transfer Clearinghouse
     EPA will  document the SITE demonstration results in reports to be made
available to Federal, State and private cleanup managers and other  interested
parties.  Recognizing that access to this, and other, treatment  information

                                     590

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is essential to the acceptance and use of alternative technologies,

the SITE program has developed an information clearinghouse to collect,

synthesize and disseminate technology performance data.

The clearinghouse has three components:


  ฐ  A njtiฃnal_jtej^p_hone^referral servi_ce will  provide  callers with
     "up"-to-date informatfmf on" SITE" projects, demonstration schedules and
     the availability of the results, and will  also refer callers to
     other sources of information.

  0  AJi electronic bulletin board, part of a planned computerized data
     base network, provides summary information on the SITE projects,
     demonstration schedules and results.  Currently, this bulletin  board
     is available only to Federal  and State hazardous waste clean-up
     personnel.

  0  A collection of reports, journals and other documents is housed in
     the EPA Library's Hazardous Waste Collection.  This collection  is
     available at "EPA^s ten' regfdnaT and five Taboratory libraries.   The
     bibliographic data base is accessible using a personal  computer.
     SITE documents will be added as they become available.l


     We are In the second phase of the clearinghouse implementation  where

we plan to include pertinent data generated by  other EPA programs — such

as the RCRA BOAT data and other treatability data bases  on the electronic

bulletin board.  As the amount of data base information  expands, short

two/three-page abstracts of the data will be available on the bulletin

board and a centralized computer network for to those requesting technology-

specific information.  This will provide a proactive consulting system

with real-time information retreival  capability that will  enable us  to

access many more data sources including our own laboratory experts and

their state-of-the-art knowledge.
                                     591

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CONCLUSION
     Given the impetus placed on the development  of  "best demonstrated" and
"innovative/alternative" treatment technologies by the RCRA Amendments and
the SARA legislation, the future use for  these technologies in hazardous
wastes is promising.  However, the need to disseminate field performance
data on these technologies remains great.   Given  the  number of demonstration
evaluations underway and the means to disseminate data from these evaluations
via the SITE Clearinghouse,  it is expected that the use and familiarity of
these technologies will  grow rapidly.
                                     592

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      SITE DEMONSTRATION PROGRAM PARTICIPANTS

DEVELOPER     ,
Geosafe Corporation,
Richl and, WA

Chemfix Technologies, Inc^
Metai rie, LA

HAZCON, Inc.,
Katy, TX

International Waste Technologies,
Wichita, KS

Separation and Recovery Systems,
Irvine, CA

Silicate Technology Corporation
Scottsdale, AZ

Soliditech, Inc.,
Houston, TX
Waste Chem Corporation
Paramus. NJ
                                In Situ Vitrification
                                                        - .
                                Soluble silicate reagents
                                Portland cement,  fly  ash,  kiln  dust
                                and proprietary chemicals

                                In Sjtiu inorganic polymers and  pro-
                                prietary chemicals

                                Lime-Based reagents
                                Silicate reagents
                                Pozzolanic reagents  and proprietary
                                chemicals

                                Asphalt binders
American Combustion, Inc.
Norcross, GA

Haztech/EPA. Region IV
Atlanta, GA

Shirco Infrared Systems, Inc.
Dallas, TX

Ogden Environmental Services,
San Diego, CA

Retech, Inc.,
Ukiah, CA

Toxic Treatments, Inc.,
San Mateo, CA

Westinghouse Electric Corp.,
Madison, PA
                 Thermal  Jreatmejnt.

                                Pyretron Oxygen  Burner
                                Shirco Electric Infrared
                                Electric Infrared Thermal
                                Circulating Fluidized  Bed Combuster
                                Plasma Heat
                                _In SiUi Steam/Air Stripping
                                  " "
                                Pyroplasma System
                          593

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                                 TABLE 1                           = •
           SITE. DEMONSTRATION[PROGRAM PARTICIPANTS (.Cont1_nuedJ_	     	
                      Thermal "freatine~rit~Tcbntinuedy ~
        DEVELOPED                                     PISCRIP.TJLO_N

Roy F. Weston, Inc.                        Low temperature reactor
West Chester, PA

Chemical Waste Management                  Low temperature thermal dryer
Oak Brook, !L
                           JB j pi ogl c al T re atment

A1r Products and Chemicals, Inc.           Fixed film, fluidized bed
Allentown, PA

Biotrol, Inc.                              Fixed film plug flow reactor
Chaska, MM

DETOX Industries, Inc.                     Batch reactor
Sugarland, TX

MoTec, Inc.                                Liquid/Solid Contact Digestion
Mt. Juliet, TN

Zimpro Environmental Control Systems,      Batch reactor, powdered activated
Rothschild, WI                             carbon and wet air oxidation

Detox, Inc.                               . Fixed film reactor
Newport Beach, CA                                                  ;

                                 Physicaj

Biotrol, Inc.                              Soil Washing
Chaska, MN

CBI Freeze Technologies, Inc.              Volume Reduction by Freezing
Plainfield, IL

E. I. Dupont de Nemours, Inc.              Microfiltration
Newark, DE

Sanitech, Inc.                             Ion Exchange
Twinsburg, OH

Terra Vac, Inc.                            ln_H"tiL Vacuum Extraction
Dorado, PR
                            Chemical  Treatment

CF Systems Corporation,              '      Solvent Extraction
Cambridge, MA

Resources Conservation Company,            Solvent Extraction
Bellevue, WA

Ultrox International,                      Ultraviolet Radiation and Ozone
Santa Ana, CA
                                     594

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                                    TABLE 2
                   COMPLETED SITE DEMONSTRATION  EVALUATIONS
       Technology

the Haztech/Shirco electric
infrared system (100 ton per day)

the Shirco electric infrared
system (1 ton per day)

the HAZCON solidification/
stabilization process

the American Combustion System
oxygen enhanced burner

the Terra Vac vacuum extraction
process

the International Waste Technology
in-situ solidification/
stabilization process

The C.F. Systems chemical
solvent extraction process
         Site

Peak Oil Superfund Site
Brandon, FL

Rose Township Superfund Site
Rose, MI

Douglasville Superfuhd Site
Reading, PA

EPA Combustion Research Fac.
Jefferson, AR

Grovel and Wells Superfund Site
Grovel and, MA

General  Electric Site
Hialeah, FL
New Bedford Harbor Superfund
   Site,
New Bedford, MA
      Date

Jul 31-
    Aug 5, 1987

Nov 2-13, 1987
Oct 12-16,1987
Dec 16, 1987 -
    Jan 29, 1988

Feb 11 -
    Apr 8, 1988

Apr 11-16, 1988
Sep 6-26, 1988
                                      595

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                           TABLES    	     _		

      SITE DEMONSTRATION. EVALUATIONS PRELIMINARY RESULTS

                        HazteGh/Shirep

0 processed 360 tons of waste oil sludge with PCBs and lead
0 DE varied between 83 - 99 % based on PCBs in ash
0 HCL and S02 emissions low                               .
0 EP Toxicity tests indicate lead in ash is Teachable
0 PM emissions exceeded regulatory limit for two of four days

                         Shi rep/Rose                  <•      ;

0 processed 2 tons of waste soils with dioxins/forans, PCBs and lead
0 ORE for PCBs greater than 99.99%, OE varied between 99.64 - 99.98%
0 PM and HCL emissions low
0 no conclusive evidence of lead fixation in ash

              ^5ฃHl?aJl Combustion Demonstration

0 processed mixed waste—Stringfellow Acid Pits and Decanter Tank  Tar
     Sludge (K087)
0 ORE greater than 99.999%                        • ,  .        r
0 low PM emissions          ,,                             , • ...
0 feed rate was doubled to 210 Ib/hr

                            HAZCON

0 volume of solidified soil doubled                •   •  -        :         •'> '  '
ฐ Chloranan improved Unconfined Compressive Strength  (UGS) and  impermeability
0 inverse relationship between UCS and organic content
0 permeability of solidified soils were low        ,   •
0 EP Toxicity and TCLP tests indicate metals were stabilized, volatiles
  and semivolatiles were not

                          Ter_ra_ V_ac_                :;

0 continous trouble free operation of system confirmed
0 1,000 Ibs TCE recovered in 56 days
0 highest recovery rate 100 Ibs TCE per day
0 extraction maintained at different soil depths

               International Wajte_Teฃhnp_lpgy_

0 Geo-Con deep soil mixing equipment used for in-situ injection
0 PCB contaminated soils treated to 16 ft depth
0 two separate sectors about 200 sq ft each were treated

                         C.F.Systems

0 300 and BOOOppm PCB-contaminated waste sediments treated,    :;. 1™  ;:.r  w^t ;
0 20 drums of harbor sediment  processed
0 Propane was the liquefied extraction solvent              -             :•''• '"


                                596

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                                     TABLE 4
                          USE OF INNOVATIVE TECHNOLOGIES
                                              Waste Type
                                 Volume Treated
n'rco
iZCON
 rra Vac
Florida Steel Corp
Indiantown, FL

LaSalle Electric Corp
LaSalle, IL

U. S. Army Ammunition
Depot, Twin Cities, MN -

Geisur RCRA Site
Geisur, LA

Mid South Wood Products
Mena, AR

Sand Springs Petrochemical
Complex, Tulsa County, OK

Basin F, Rocky Mountain
Arsenal, Denver, CO

Tyson's Dump Superfund
;Site, Reading, PA

Upjohn Facility Superfund
Site, Barceloneta, PR

Verona Well Field
Superfund Site,
Verona, MI

Florida Environmental
Agency, Belleview, FL
PCB Contaminated Soil
                                         PCB Contaminated Soil
                                         PCB Contaminated Soil
                                         PCB Contaminated Soil
Creosote Contaminated Soil
Abandoned Solvent & Waste Oil
  Recycling Site

Metals-bearing evaporation
ponds and sludge

PCEป TCE and
TCP Contaminated Soil

Carbon Tetrachloride
                                         PCE, TCE & MEK
                                         Gasoline
16,000 cu. yds.
                                 35,000 cu.  yds.*
                                 12,000 cu.  yds.*
                                 40,000 cu.  yds.*
                                                                          * *
                                                                          * *
                                                                          * *
20-100 Ibs/day
 for 30 days

250 Ibs/day for
 30 days

 2000 Ibs/day;
ongoing cleanup
                                  2000 Ibs/day for
                                 four months
 Estimation  of the total site cleanup

 Demonstration for potential cleanup
                                         597

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                                       TABLE 5
                              SITE EMERGING TECHNOLOGIES
                Developer

Atomic Energy of Canada, Ltd.,
Ontario, Canada

BatteHe Memorial Institute,
Columbus, OH

Bio-Recovery Systems,  Inc.
Las Cruces, NM

Colorado School of Mines,
Golden, CO

Energy & Environmental Engineering, Inc.,
Somerville, MA

Envlrite Field Services, Inc.
Atlanta, GA

Western Research Institute,
Laramie, WY
Description

Toxic Metals Removal
Electro-acoustic Soil
Decontamination

Sorption of Heavy Metals
by Alga SORB

Wetlands Treatment to Remove
Heavy Metals

Laser Stimulated Photochemical
Oxidation

Solvent Soil Washing
j^Situ. Oil Recovery and
BTodegradation
                                             598

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                                 TABLE 6
    Technology

Mobile Soils Washer
KPEG Treatment Systerff
Mobile Incineration
System
EPA DEVELOPED TECHNOLOGIES

                          Rematkl

this System has been designed for Stfcfifition of a broad
range of hazardous materials from s_p*ftl<- contaminated
soils using water as the extraction IQlVent.  The proto-
type has been developed utilizing bOHVงfit1onal equipment
for screening, size reduction, washing*! and dewatering
of the soils.  The washing fluid-wa'te? Hlay contain addi-
tivies, such as acids, alkalies, detergents, and selected
organic solvents—to enhance soil d@6dr(t ami nation.  The
nominal processing rate is 4-yd3 of tOHtaminated soil  per
hour when the soil particles are prjHfirfly less than
2 mm in size, and up to 18-yd3 pfer hdllr4 for soil of
larger average particle size.
Potassium polyethylene glycolate hfeSpiffts are effective
dehalogenators of aromatic and allpnatifc organic materials,
including PCB's and other to>lift ha1ide1i  The KPEG reagent
reacts with the chlorine atom! 1h tNl Iryl  ring of halo-
genated aromatic contaminants to pr6d\Jfce innocuous ether
and potassium chloride salt.  In some KPEG reagent formu-
lations s dimethyl sulf oxide is added as a co-solvent to
enhance reaction rate kinetics.  KPEG reagents are stable
in air, tolerate moisture, are easily stored, and can be
safely transported to problem sites unlike conventional
anaerobic dehalogenating reagents.  A large portable
KPEG reactor (400 gallons) has been demonstrated on PCB-
contaminated soils and a smal 1 er pilot unit on oily
pesticide wastes and liquid woodpreserving wastes.

The mobile incinerator consists of specialized equipment
mounted on four trailers.  In the rotary kiln on the
first trailer, organic wastes are fully vaporized and
completely or partially oxidized at approximately 1800ฐF.
Incombustible ash is discharged directly from the kiln.
The gas from the first trailer passes through a secondary
combustion chamber (SCC) on the second trailer at a
temperature of 2200ฐF where the thermal  decomposition
(oxidation) of the contaminants is completed.  The flue
gas exits from the SCC and is then cooled by water sprays
from 2200ฐF to approximately 190ฐF.  Excess water is
collected in a sump.  The gases then pass into the air
pollution control equipment on the third trailer.
Here, any submicron-sized particulates are removed from
the gas stream as it passes through a high-efficiency
air filter, and byproduct acid gases generated by the
destruction process are neutralized in an alkaline
scrubber.  Gases are drawn through the the system by an
induced draft fan, which maintains an overall vacuum to
ensure that no toxic gases escape from the system.
                                     599

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                         " "''   TABLE e	

                        EPA DEVELOPED TECHNOLOGIES
    Techno! ogy
                          Remarks
                        The cleaned gases are discharged  from the  system  .
                        through a 40-foot high stack.   The incinerator can   ;.
                        process 9,000 pounds of contaminated  soil,  or 75 .  •
                        gallons of liquid per hour.   Hazardous substances
                        that could be incinerated include compounds  containing
                        chlorine and phosphorous, e.g., PCB's, kepone, dioxins,
                        and organophosphate pesticides, which may  be in pure
                        form, in sludges, or in soils.
Mobile Carbon
Regeneration System
This System was designed for field use in reactivitlng
spent granular activated carbon used in spill  or wast.e
site cleanup operations.  When contaminated granular
activated carbon (SAC) is heated in the kiln,  organic
substances are desorbed and volatilized.  All  vapors
and gases from the kiln flow through a duct into ,the
secondary combustion chamber where an excess oxygen
level is maintained.  Temperature and residence-time
are controlled to assure desorption/detoxification of
hazardous organic substances, including chlorinated
hydrocarbons.  Off-gases are .water-quenched and scrubbed
with an alkaline solution before being vented  to, the
atmosphere.  Stack gases and used process water are
monitored.
                                      600

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                                 REFERENCES
 1.  A Comprehensive Environmental -Industry Report on Recent EPA Cleanup
     Decisions  EjlviฃOnH!6r[t.a^_ง.ei?J!^.e Fund, Hazardous Waste Treatment
     Counc1J_, Nat i'onal  Aydubon SocTety7 NatjgWal  Mil d 1 ~i fe~~F ecf e r at foh7 Nat u r a 1
     Resources 'Defense "Counc 11 , Sierra Club and 'UVS.  PIRG.' J'une 20, 1988.

 2.  Resource Conservation and Recovery Act Amendments  of 1984 (Hazardous and
         d Waste Act) U. JL'_ฃฐl|9ฃej?J.>
 3.  Saroktn, O.G., Muir, W.R., Milleo, C. .6. and Sperber, S.R. .."Cutting
     Chemical Wastes, What 29 Organic Chemical Plants are Doing to Reduce
     Hazardous Wastes".  INFORM, 1985.

 4.  Freeman, H. M. "The USEPA Waste Minimization Reserch Program", 'Hazardous
     ll^JirL3!?-1.?:8!^                              June 14, 1988.

 5.  KearnSjD. ,"New EPA Land Disposal Requirements to Cost Generators
     $1 Billion annually; Waste Tech News, September, 6 r 1988.

 6,  U.S. Environmental Protection Agency, "Land Disposal Restriction for
     First Third Scheduled Wastes" ป Volume 53_,_ UปS. EPA, OSW, Washington, Cue.
     May 17, 1988.         •        "~   —.-_—:---—              -

 7.  U.S. Environmental Protection Agency, Superfund Innovative Technology
     Evaluation (SITE) Strategy and Program plan, EPA/540/G-86/001 , US EPA,
     Washington_,pปฃ,, December 1986.

 8.  U.S. Environmental Protection Agency, Best Demonstrated Available Technology
     (BOAT) Background Document, Volume 51, U.S. EPA, OSW, Ha^hingt^on^D^C.
     November 7, 1986.

 9.  "Superfund Amendments and Reauthorization Act of 1986."  Pub] ic Law 99-499.
     U.S. Congress.

10.  The Superfund Innovative Technology Evaluation (SITE) Program: Progress
     and Accomplishments; A Report to Congress.  EPA/540/5-88/001; February 1988.
                                       601

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-------
               NATO/CCMS Guest Speaker:



             Ronald Probstein, United States



Electroosmotic Purging for In Situ Remediation
        603

-------
         ELECTROOSMOTIC PURGING FOR IN SITU
                          REMEDIATION
                                  by
                            Ronald F.  Probstein
                                 M.I.T.
ง
4*
      NATO/CCMS Pilot Study on Demonstration of Remedial Action  Technologies
                   for Contaminated Land  and Groundwater

                             Washington, DC
                         November 18-22,  1991

-------
                        ELECTROOSMOTIC DECONTAMINATION


                                OF  A  HAZARDOUS  WASTE  SITE
                                             Cathode

                                             electrodes
Anode

electrodes
O
CD
     Contaminated

     effluent

     collector
                                XXXXXXXXXXXXXX.
                               xxxxxxxxxxxxxxx.
                             xxxxxxxxxxxxxxxxxx.
                                 xxxxxxxxxxxx.
                            xxxxxxxxxxxxxxxxxxxx.
                         xxxxxxxxxxxxxxxxxxxxxxxx.
                        xxxxxxxxxxxxxxxxxxxxxxxxx.
                        xxxxxxxxxxxxxxxxxxxxxxxxx.
                        xxxxxxxxxxxxxxxxxxxxxxxxx.
                                                                         \SN\SX
                                                                         NXNNNNNV
                                                                        \\x\\\\\\\
                 \N\\\\\\\\\\\\\\\\
                                                                                         'XXXXXXXXXXXXXXXXXXXXXXXXX.
                                                                                         •xxxxxxxxxxxxxxxxxxxxxxxxx.
                                                                                         'XXXXXXXXXXXXXXXXXXXXXXXXX.
                                                                                         'XXXXXXXXXXXXXXXXXXXXXXXXX.
                                                                                         •xxxxxxxxxxxxxxxxxxxxxxxxx.
                                                                                         •xxxxxxxxxxxxxxxxxxxxxxxxx.
                                                                                         'XXXXXXXXXXXXXXXXXXXXXXXXX.
                                                                                          XXXXXXXXXXXXXXXXXXXXXXXX
                                                                                         Xxxxxxxxxxxxxxxxxxxxxxxxx
                                                                                         XXXXXXXXXXXXXXXXXXXXXXXXX
                                                                                         xxxxxxxxxxxxxxxxxxxxxxxxx
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             COMPARISON OF ELECTRO OSMOSIS AND
                     PRESENT TECHNOLOGIES
Excavation/washing
Excavation/incineration
Vitrification
Pumping/draining
PRESENT TECHNOLOGIES

    * costly
    * exposes workers to health risks
    * can lead to air pollution

    * very expensive
    ป increases waste volume

    ซ cannot control flow direction (channeling)
    • impossible in low  permeability soils
    • soil rupture  possible
                         ELECTROOSMOSIS

                         * in situ
                         •     degree of control of flow direction	
                         * high degree of contaminant removal
                         • low energy costs (~ $0.01/ga!lon  or  $2.5/ton)

-------
                    PARAMETER RANGES
         Applied  voltage         A/Ax     20 - 500 V/m
         Electrode  spacing       Ax      1 - 5 m
|        Electrode  depths         z      5 -  15 m
         Current  density          i       0.5-5 A/m2
         Hydraulic  permeability  kh      < 10"12
         Flow  rate/unit  area      qe      10"^ • 10"^   m/s

-------
                       ELECTROOSMOTIC PRINCIPLE
                          ELECTRIC FIELD [
"O
03
            ANODE
WATER   ^
VELOCITY
PROFILE
CATHODE

-------
    ELECTROOSMOTIC VELOCITY
             17
• .     /  *
 .
7
f f / 9 /

^K  fl^M
          a
   VISCOUS
       U=
              /*
                  609

-------
           ELECTROOSMOSIS APPARATUS
  Effluent
  collector
                          Gas vents
                            45  cm
 Active  electrode
  Passive  electrode
                                11.4  cm
                    Saturated  clay   I
                    Electrode  chambers
                     DC voltage source
          Purge
          solution
          reservoir
Compaction screw
                                            Porous  support
ELECTROOSMQSIS MEASUREMENTS

 *  Voltage  distribution
   Current
•  Electroosmotic  velocity

ป  Chemical composition and pH of effluent

ซ  Fraction of chemical  removed  vs pore volumes removed

ป  Distribution  of chemicals  remaining in the sample
                               610

-------
0)

3
"o
       5000
              VOLUME OF EFFLUENT VS TIME
                25 Volts applied
       4000
       3000
2000
       1000-
                                   450 ppm phenol
                                   0.5M acetic acid
                  20      40      60     80     100     120
                           Time  (days)
                             611

-------
                 FRACTION REMOVED VS

                 PORE VOLUMES REMOVED
       1.0
•a
o
>
o


&
o
ปซMซ
*•ป
o
03
       0.8'
0.6'
0.4-
       0.2-
       0.0'
              25 Volts applied
                                 450 ppm phenol


                                 0.5M acetic acid
         0.0
             0.5
1.0
1.5
2.0
                          Pore  volume
                            612

-------
            FRACTION REMOVED VSJCIME
      1.0
o
E
e
o
4->
u
(0
JL.
u.
             500 Volts applied
      0.8 -
      0.6 -
0.4  -
      0.2  -
     0.0
          0.0
          0.0
                                 450 ppm phenol
                        1.5

                    Time (days)


                        1.0

                   Pore  volumes
3.0
2.0
                              613

-------
•o
o

o


I


e
o
*-ป
u

2
LU
              FRACTION REMOVED VS

              PORE VOLUMES REMOVED
OSM ACCTICACIt, ISV


             *
                         1,0
                     Pore  volume
          1.5
2.0
                        614

-------
0>


o
      50
      40-
      30-
      20
      to-
            VOLUME OF EFFLUENT VS TIME
            .MMHHHMMHMHHiaaBMMIHMHMMMIBUMM^^                           gg,

                     Effect  of  purge solution  pH
              Small scale experiments
              450 ppm phenol
Purge  solution


  O.OIMNaOH


  0.01 MNaC!

  0.01 MHCI
                                                          8
                              Time (days)
                            615

-------
                       MODEL
Electroosmotic  transport of chemical  species  in  porous
media  involves:
ป   Convection of pore  liquid,  "electroosmosis"
*   Migration  of ions  in  electric field, "electromigration"
•  Diffusion
•   Chemical reactions
                             616

-------
       CHEMICAL REACTIONS
            --     •'  •. ,-•••'• \     • '' -  '     f
  BULIC: EQUILIBRIUM CHEMISTRY
  e. g.  a) weak acid
              HAซ.fl"l"+  A'
                 [HA]
                        = K
                           a
       b) adsorption  isotherm
           |_-tl *ปJads ~~-' •*^k-ads [.ฃ•*• **•
• ENDS: EQUILIBRIUM ELECTRODE REACTIONS
   e. g.  electrolysis of water
       anode:
         2 H2O -ป 4 H++ O2 (g) + 4 e-
       cathode:
        2 H2O+2 e-->2 OH-+H2(g)
                      617

-------
   CONVECTIVE-DIFFUSIQN  EQUATION
For i    species

Electroosmotic  velocity
Eleetromigration  velocity
                  =  JL     F 3
              Uei~"^TViZi   3z
  R. = molar species production rate  /  unit volume
                        618

-------
              FRACTION REMOVED VS
              PORE VOLUMES REMOVED
Q)
O

Q)
0)
5
8
(0
O
!
0.5M model
0.1 M model
0.5M data
O.IMdata
                     Pore  volumes
                       619

-------
      0.15-
                   CONCENTRATION PROFILE
                   ^•••••••••••••^••••••••acaMK^

                 Comparision of experiment  and  model
                                       0.1M Acetic acid
                                       0.1 M NaCI purge
c
Q
*5
ro
Q>
O
C
O
O
0.10--
      o.os-
                       *  Data

                     ••*• Model

                     	Initial concentration
      0.00'
         0.0
               0.1          0.2
0.3
0.4
                             Position  (m)
                               620

-------
     6
     5-
                      pH PROFILE
           Comparison of experiment and  model
            0.1M Acetic acid
            0.1M NaCI purge
     4-
T,
CL
     3-
                         *    ป    •
     2-
                      •  Data

                      — Model
      0.0
0.1         0.2
0.3
                       Position  (m)
0.4
                         621

-------
SKETCH OF 3-DIMENSIONAL TEST CELL
                                      Effluent
                                       Cathode
                                       Well
     Anode
     Well
               622

-------
L ^^^^^^^M l^-1^^:/'




 - _ap-JEfr— ~= i J- •*"  _    ~ t ~ -~ V —•T"  _j: IgST i '***'_

. tJfc^5^ , -' --^J-k-'-J-.s. -:-: -^f-^r-
 --.- -1ป.-Sst. _ --. s^^&ซ-^'
 -  •••-   ^t  i-i -  -1 •• j-j
 - flN>M aTcr-P-I-'^fjiii-ii
 . HMปJP( ^t'r •—- -iW1.-3?^

-------
                                        2D PHENOL EXPERIMENT SETUP
en
       Purge Solution
       0.01 M NaOH
                                         14cm
kaolin clay saturated
with 450 ppm pheno!
Soiution

-------
              2D PHENOL EXPERIMENT. VOLUME OF EFFLUENT VS TIME
  3

 s
  
-------
                 2D PHENOL EXPERIMENT. CONTAMINANT REMOVAL
  •o
  o
  ฃ.
  o
  c
  
-------
  s
  p,
  c
  o
  C
  4)
  O
  C
o, O
53 ^
  "o

  (U
  43
  Ou
        ZD PHENOL EXPERIMENT. CONTAMINANT CONCENTRATION IN EFFLUENT
      103r
102
      100
                          o
                            o o
          450 ppm phenol

          35 Volts applied

          12.7 cm between electrodes
          o: data

          -: least squares approx.
         0
                             Pore volume fraction removed

-------
en
      POTENTIAL DISTRIBUTION AT t=0   POTENTIAL DISTRIBUTION AFTER 17 DAYS
      0
     -1
                   25
                  Xin
            0
            -1
                                      -2
2D PHENOL EXPERIMENT
                         .25
                                                    .15

-------
           2D PHENOL EXPT. POTENTIAL DISTRIBUTION AFTER 27 DAYS
     0
ID
     -2
     -4
     -6
                                 Xcm

-------
en
<*>
o
                                                   MODEL
                   CONTAMINANT CONCENTRATION DISTRIBUTION
                  AFTER 4 DAYS
                                   Anode      Flow direction ->
Cathode
                   450 ppm phenol




                   35 Volts applied




                   12,7 cm between electrodes

-------
                                                   MODEL
                  CONTAMINANT CONCENTRATION DISTRIBUTION
                  AFTER 13 DAYS
01
CO
                                   Anode      Flow direction —>
Cathode
                   450 ppm phenol
                   35 Vote applied
                   12.7 on between electrodes

-------
9)
CO
PO
                                                   MODEL
                  CONTAMINANT CONCENTRATION DISTRIBUTION
                  AFTER 27 DAYS
                                  Anode
Flow direction —>
Cathode
                  450 ppm phenol



                  35 Volts applied



                  12.7 cm between electrodes

-------
to
                             CONCLUSIONS
• By  tailor-making  purge  solutions  for  site-specific
  conditions,  electroosmotic  purging  has   potential
  to  remove  a large variety  of pollutants  including
  radioactive   materials

• Electroosmosis  offers  advantages  of  control of  flow
  direction  and  uniform  flow  through  heterogeneous  soils

• Lab  experiments on  electroosmotic  purging show  a
  high  degree of removal  (^95%) at low energy  costs
  (<  $0.01/gallon  or  $2.50/ton)

• Additional  laboratory  studies  are  still  required  with
  different  chemical  species,  soils,   saturation   geometries,
  electric  fields,  and  3-D  geometries  to build  up  generic
  database for  optimal field  operation

-------

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                       NATO/CCMS Guest Speaker:

Hans-Joachim Stietzel, European Economic Community

    Soil Protection Against Point-Source Contamination
                        in the European Community
                635

-------
NATO/CCMS PILOT  STUDY  OF  REMEDIAL ACTION TECHNOLOGIES FOR
             CONTAMINATED  LAND  AND GROUNDUATER
      BILTHOVEN,  THE NETHERLANDS, NOVEMBER 7-11  1988 '.
Soil protection against point-source contamination  in  the
European Community
                 Dr. Hans Joachim Stietzel
               Mr1.  Eusebio  Murillo  Matilla
                            636

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Soil protection against point-source contamination in the
European Community
Contents :

I. Definitions and types of soil contamination and
deterioration

1. Definitions

2. Diffuse contamination

3. Point source contamination
II. Relevance of Council Directives, Action Programmes
and Parliament resolutions for soil protection against
point source contamination.

1. Council Directives

1.1 Council Directive 75/442/EEC of 15.07.1975 on waste

1.2 Council Directive 78/319/EEC of 20 . 03 . 1 9;78 .on toxic
and dangerous waste

1.3' Council Directive 75/439/EEC of 16.06.1975 on the
disposal of waste oil

1.4 Council Directive 86/278/EEC of 12.06.1986 on the
protection of the environment and in particular of the
soil, when sewage sludge is used in agriculture

1.5 Council Directive 80/68/EEC of 17.12.1979 on the
protection of groundwater against pollution, caused by
certain dangerous substances

1.6 Council Directive 85/337/EEC of 27.06.1985 on the
assessment of the effects of certain public and private
projects on the environment

2. The Fourth Environmental Action Programme (1987 -
1 992)

3. Resolution of the European Parliament on the waste
disposal industry and old waste dumps. CPE DOC A 2-31-
/87)
III. The fund problem: Financing the clean-up of
contaminated land

1.  Costs of remedial actions in the EC

2.  Comparison of the cost of different remedial
techniques

-------
3. Financing models


IV, Community action concerning point source
contamination of soil

1. Eesearch and Demonstration

1.1 Existing studies and reports                 .

1.2 ftCE Programme

1.3 Research areas CDGXII)

1.4  Recommendations for research


2. Preparation of legal provisions                   :

3. Participation in international working
groups/technical committees

3.1   Nato/CCMS Pilot Study: Demonstration of reaiedia.1
action technologies for contaminated land and grotindwater

3.2  International organisation for standardization  (ISO)
TO 190                                               :

V  References

VI Annexes
                            638

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I. Definitions and types of soil contamination  and
deterioration.

1 . Definitions

There exists no generally accepted definition for
contaminated land in the European Community. Some Member
States have defined it in the following way:

Denmark: Land which presents a threat to groundwater
sources or to the health of local residents  (Danish
National Agency on Environmental Protection, 1985)

Germany; Land that presents a potential direct  or
indirect adverse impact upon the health and  welfare of
humans and economically important natural  resources,  such
as livestock, crops and groundwater sources. (BMFT, 1981)

UK: Land, which because of its former use, now  contains
substances that present hazards likely to  affect  its
proposed form of redevelopment, and which  requires an
assessment to determine whether the proposed development
should proceed or whether some form of remedial action  is
required. (DOE, 1983)
Netherlands: Land, where substances are present  in  soil
in concentrations higher than those in which  they would
normally expect to occur and where they pose  a serious
threat to public health and the environment.  (Ministry of
Housing, Physical Planning and Environment, 1983)
Generally speaking two types of soil pollution  can  be
distinguished:

2. DjJLfl]yLS^_jc_onjbaMitta.tJJSJDL: ' pollution of a  large  area
caused by an exogenous source

- atmospheric pollution  ("acid rain"): emmissions of
sulphur dioxide, nitrogen oxides, etc. by  industry,
domestic fuels, traffic, etc.

- agricultural practice: prolonged and excessive use of
fertilizers, pesticides, herbicides, sewage  sludge

3. Eo.l.BjL_งj8Ju,Cฃ^__c,oj]Lt5Mi,ttSdfeijaB.: geographically restricted
local pollution by accidental/incidental/  deliberate,
anthropogenic activities

industry:
- transport of chemicals/materials
- storage of raw -materials
- production processes
- storage of products (leakage, spillage)
                             639

-------
- disused production plants and
  former industrial sites

waste disposal:
- municipal landfills
- hazardous waste landfills
- co-disposal landfills

- abandoned waste disposal sites
II  Relevance of Council Directives, Action Programmes
and Parliament Resolutions for soil protection against
point source contamination.
Soil protection against point source contamination has
not received major attention and has not been a priority
issue of the EC environmental policy until very recently.
Whilst the effects of agricultural practice, the
spreading of sewage sludge and the excessive use of
fertilizers and pesticides, has been investigated by the
agricultural research of the Commission (DG VI) or by
other research programmes  (Cost 68, 681; DG XII), the .
study of point source contamination is still in an early
stage.

Soil protection should be considered as a multimedia
approach, since the soil is part of various ecosystems
and tackling the problems of soil pollution should not
lead to problems in other compartments of the environment
(water, *air).  Taking account of the fact that the soil is
linked with the atmosphere, hydrosphere, biosphere and
lithosphere, there are a number of EC directives which
have relevance to soil protection but the only one which
has a special  relevance to soil and which sets up some
limit values for pollutants is the directive on sewage
sludge in agriculture C86/278/EEC).

To a certain extent, the following articles of directives
can be applied for the benefit of soil protection.
                             640

-------
1.   Council Directives/18/

1 .1  C
-------
          2. The Commission  shall  report every three
          years to  the  Council  and to the European
          Parliament  on the  application of this
          Directive.
1 .3  Council Directive  QC,.,,1.4/.4Z,19Z5, on the disposalof
waste oils  cl5/4g'?/iEC!L

          Article  4

          Member States shall  take  the necessary
          measures to  ensure  the  prohibition of;

          a) any discharge  of  waste oils into inland
          surface  water,  ground water, territorial
          sea water  and drainage  systems;

          b) any deposit and/or discharge  of waste
          oils harmful  to the  soil  and any
          uncontrolled  discharge  of residues
          resulting  from the  processing of .waste
          oils;

          c) any processing of waste  oils  causing
          air pollution which  exceeds the  level
          prescribed by existing  provisions.
1 . 4  C,oan.cll...vDii;:g1c_tilygj ...... ojg ..... 1.2,. 06,1986
                       in. ........ a.gr_icjultuge: ..... (86/218/EECl,.
          Article 1

          The purpose of  this  Directive  is to
          regulate the use  of  sewage  sludge in
          agriculture in  such  a  way as  to  preveiut
          harmful effects on soil, vegetation,
          animals and man,

          thereby encouraging  the  correct  use of
          such sewage sludge,  (see Annex I)

The directive sets up limit values for  concentration of
heavy metals in the soil  and in  sludge  and the maximum
quantities of cadmium, copper, nickel,  zinc and mercury,
which may be added to the soil.
                             642

-------
1 • 5  Co un ci 1 Di r e. ct i v e o f 17.12.1979 on the protection.	of
gro u ndwat/e,r aga 1 nst, ,I>,Q ,1,1 u t i on caused bv ce r t a i n  d.anaerous
substances.

          Article 1

          1. The purpose of this Directive is to .
          prevent the pollution of groundwater by
          substances belonging to the families and
          groups of substances in lists I or II  in
          the Annex,  hereinafter referred to as
          'substances in lists I or II1, and as  far
          as possible to check or eliminate the
          consequences of pollution which has
          already occured.

          2. For the purposes of this Directive:

          a) 'groundwater1 means all water which is
          below the surface of the ground in the
          saturation zone and in direct contact  with
          the ground or subsoil;

          b) "direct discharge" means the
          introduction into groundwater of
          substances in lists'I or II without
          percolation through the ground or subsoil;

          c) "indirect discharge" means the
          introduction into groundwater of
          substances in lists I or II after
          percolation through the ground or subsoil;

          d) "pollution" means the discharge by  man,
          directly or indirectly, of substances  or
          energy into groundwater, the results of
          which are such as to endanger human health
          or water supplies, harm living resources
          and the aquatic ecosystem or interfere
          with other legitimate uses of water.

Lists I and II see Annex II.
1.6  . Co .un c.i,3. _P_1 re. c; tly ,3,,, o f 27 . 06. ,1 985 on  the  a_g g; e ง,5 m ejfi ft ...QJL
the e f feet g 0 f c e r t a i n pub 1 j c and p r i va t,e projects on the
environment. ..C..85/3.3..7/EEC).

          Article 1

          1. This Directive  shall apply  to the
          assessment of the  environmental effects of
          those public and private projects  which
          are likely to have significant effects on
          the environment.
                             643

-------
          Article 3

          The environmental impact assessment will
          identify, describe and assess  in an
          appropriate manner,  in the  light of each
          individual case and  in accordance with  the
          articles 4 to 11, the direct and indirect
          effects of a project on the following
          factors:

          - human beings, fauna and flora,

          - soil, water, air,  climate and the
          landscape,

          - the inter-action between  the factors
          mentioned in the first and  second indents,

          -material assets and the cultural
          heritage.
2.  TFm^simlf jjcARC e	of	the At h	Env 1 ronroent.al.,.,..A:ctjlon  . .
P_r^qrg^,ej^(.tฃ9^.;-,;._.j:r.9.:.?21....f.p.r so j.1 protection.        •

The first three Environmental Action Programmes
concentrated on pollution problems as these arise in  the
different media: air, water, soil and the approach to
control pollution has been a sectoral one. "One
inevitable consequence of the sectoral approach to
pollution is that, as standards are tightend in one area,
so the pressures may increase in another area." /I/.

The global approach of the Fourth Action Programme
changed the environmental strategy of the Community to a
multi-media and multi-sectoral pollution control. As  the
soil is a very complex biosystem and as there are many
different types of soils and pollutants the comprehensive
approach to soil protection will aim:

          - to reinforce the arrangements for
          coordination between policies to ensure
          that soil protection is more effectively
          taken into account, in particular in the
          Community's agricultural and regional
          development policies,

          - to reduce the damage caused by •  •  .
          agriculture to the ecological     .  .     .    •' v
          infrastructure by proposing measures
          (within the context of the reform of the
          common agricultural policy) to encourage
          less intensive livestock production          '
                             644

-------
          systems; to reduce the use of agricultural
          chemicals; and to ensure the proper
          management of agricultural waste
          (especially from intensive livestock
          units)

          - to prevent soil erosion and rapid run-
          off of water (including the identification
          and mapping of rapidly erodable soils  in
          the Community),

          - to identify and clean up polluted waste
          disposal sites; to encourage the  recovery
          and re-use of contaminated or derelict
          land (e.g. old industrial sites,  mining
          land, etc.); and to reduce the hazard  to
          soil from current waste disposal
          practices,

          - to encourage the development of
          innovative soil protection techniques  and
          the transfer of available know-how.
3 .   Re sol u t ion o.f „ t he European Par! jam en t  on , .the, ,   ^  ,
d,isp,osal in.d.u.g.tr.y, ...... aj\d,__.oj. d__w,as te dumps (19. QA,;.,.1.9.,8.7,,L,.,,-,..,,PE,,
The : Committee on the Environment, Public  Health  and
Consumer Protection has adopted on  19.01.1987  a  working
document on the waste disposal industry and  old  waste
dumps CDoc. B 2-1 654/85 ; author : Roelants  du Vivier),
where the nature and extent of contaminated .land ,  the
government responses to the problem  and perspectives  for
the European Community are described.

Following this report the European  Parliament  adopted  a
resolution on the waste disposal industry  and  old  waste
dumps (PE Doc. A 2-31-/87).
( see- Annex III )
III. The fund problem: Financing  the  clean-up  of
contaminated land

1 •  Costs of r erne dial..._ act ion s , in , t h e , E C

"On account of  (the) wide variety in  local  or  national
circumstances and, factors there can hardly  be  said  to be
any similarity  in the policies of the various  Member
States with respect  to soil  contamination problems."  /11/

The expenditures for soil protection, in particular for
the clean-up of contaminated  land differ widely and will,
in respect of the internal market of  1992,  lead to  false
competition and to the import and export of highly
                            645

-------
polluted soil due to the different approaches of the
Member States.

It might be very difficult to set up international
standards (reference values, trigger values) because of
the variety of soil types, soil structure, intended after
use etc., but it seems that this is, for the long term,
the only solution to the problems connected with
contaminated land.

The listed expenditures of the Member States are based on
published literature and reports 2/12/13. It is not
possible to give exact data for all Member States.

Important Note:

The figures of the number and type of sites in the table
cannot be compared with each other because
- the definitions of contaminated or derelict land differ
widely

- only in some Member States a systematic survey of
contaminated land has been completed

- the reference year of the inventories is different
                            646

-------
2 .    C otnpar i s on of  c o s t s  f or..'sQme  of the  existing remedial
and ._con,tainra.ejQLt.. *---'--•'	
TECHNIQUES
Thermal techniques
Extraction techniques
(physico-chemical)
Microbiological techniques
Surface sealing
(synthetic material)
Seal walls
Bottom liners
Horizontal barriers
COST
ฑ 75-175 ECU/t
+ 75-100 ECU/t
ฑ 50-125 ECU/t
ฑ 10-18 ECU/m^
ฑ 18-175 ECU/m2
ฑ, 200-1000 ECU/m2
                                647

-------
3.  E..JJ.ng|fl.lgllliliafficii mc;dels       '                          ':

The estimated expenditure required for the reclamation of
contaminated land in the EC Member States (EC 10) amounts
up to 1,350 x 10* ECU per annum for the next 15 years
/2/. (1 ECU = 1.25US$, 2.07DL, 0.66ฃ, 2.32DFL, 7.03FF.)

Despite the urgent need for remedial measures and the
restoration of contaminated soils, especially in urban
areas, there is a lack of funds to finance the new
decontamination techniques.

Since the Community's First Action Programme the
"polluter pays principle" (P.P.P.) has always been the
cornerstone of the EEC environmental policy.

In theory, the PPP seems to be a simple solution, but
practise has shown that several difficulties -have to be
overcome to execute this principle, because in many
cases:

- the polluter is unknown
- the polluter is insolvent
- the initial polluter is known but has no legal
successor

Therefore, a different approach was developed in several
Member States. The experience in the Netherlands shows
that law-suits to retrieve the high costs for the
reclamation measures can take a long time, but in certain
cases of severe soil and groundwater pollution it is
necessary to act very fast.,So the central Dutch
government finances 90%, the municipality 10% of the
clean-up costs and tries to recover the money from the
responsible parties. In this way, 40 law-suits have
recovered 300 x 10 6 Dfl., and in more than 400 cases
agreements were settled with companies to cover the
expenses of clean-up operations /14/.

The practical experience of this approach seemed to be
quite successfull as the threat of a law-suit convinced
many companies to start voluntarily reclamation of the
contaminated land.

The USA established in 1980 a cleaning fund which is
financed from tax on organic and inorganic chemicals and
crude oil. This "Superfund" is administrated by the EPA
(Environmental Protection Agency) and has spent 1,6
Billion $ in the last 6 years. /15/. With the aid of the
Superfund 25 000 potential hazardous sites were
identified and 888 sites were listed on the NPL (National
Priority List) for remedial action.
                            648

-------
In Germany several attempts have been made to solve the
liability problem. The introduction of a voluntary
cooperation between the state and industry at the federal
level .and also a compulsory legal solution similar to - the
Superfund failed because it was controversial as to the
way in which the fund should be divided to the Lander and
because industry wanted to have a say what should be done
with'the money they had to contribute /16/.

In consequence'of these problems - the federal Lander
developed their own different liability regulations.

In conclusion and to simplify matters, it can be said
that the following possibilities have been considered to
finance the clean-up of contaminated land:

1, Polluter Pays Principle: direct application, suing the
polluter

2. Public fund' of .the government: costs of reclamation
are paid "by the government. Later retrieval of the cost
from the polluters (Netherlands)

3. Joint liability programme; compulsory taxes on
industrial products, .Administration of the fund by the ..
government (Superfund, USA)

4. Combined industry/government fund: voluntary co-
operation between the industry and the government. Funds
are raised together ,and the distribution of the   .      ;
expenditures is coordinated.",
IV.  Community action concerning point source
contamination
1.1 Existing studies and reports

Until now four major studies have been ordered and/or
financed by the Commission to analyse the extent and the
problems of soil contamination in the Member States.

a. ; TNO Study (1 986)
Contract number 85-86 600-1 1 -042- 1 1 -N

"Prospective action with regard to soil contamination in
view of a common policy"

The TNO-study defines the state 'of the art and essential.
developments in the field of soil contamination. The
national policies and programmes for soil protection in.
the EC Member States are summarized and some
recommendations for the. European Commission are given.
                             649  .

-------
b. ECOTEC-Study (1986) commissioned by DG XII

"Land Recycling and Renewal; A prospective analyses of
industrial land contamination and Remedial Treatment"

The ECOTEC report focuses on the required expenditures to
clean-up contaminated sites in the EC, gives an
assessment of the scale, nature and location of future
land contamination and reviews the available technology
for remedial actions and includes priorities for 1 + D
and legislative controls.

c. Bornier-Study (1987)
Contract number 85-B 6632-11-006-11-N

"Contaminated Land in the EC"
The Dornier-study gives a comprehensive survey of state
laws, the structure of the administration, the
registration of contaminated sites and financing models
in the EC concerning soil pollution.

d. Hickan-Report (1987)

"Parameters characterizing toxic and hazardous waste
disposal sites. Management and monitoring".

The criteria for toxic and hazardous waste disposal sites
are summarized and the advantages and disadvantages of
landfills, underground disposal sites and deep well :
disposals are discussed. The common field and laboratory
tests are described in an annex.
1.2  ACE Programme

In the framework of the ACB-programme (Action by the
Community relating to the Environment),  Council
regulation Nฐ 2242/87 of 23 July 1987, the Community will
make financial support available to demonstration
projects relating to;

a) new clean technologies, i, e. technologies which cause
little or no pollution and which may also be more
economical in the use of natural resources

b) techniques for recycling and reusing waste, including
waste water

c) techniques for locating and restoring sites
contaminated by hazardous waste and/or hazardous
substances

d) methods for measuring and monitoring the quality of
the natural environment.                               ,;
                            650

-------
Demonstration means the operation of a full scale
installation and is the link between the R + D phase and
the later investment/production phase.

A call for tenders for the items 1.c) and l.d) of the
Council Regulation will be launched at the end of 1989.
The 'third amended version of the fields of application
for item c)  is enclosed in Annex IV.
1,3  Research areas

1,  The research programme STEP (Science and Technology
for the Environmental protection) carried out by DG XII
is the continuation and extension' of the ongoing 4th
Environment Protection Research Programme (1986 - 1990),

The objective of the research area 5: soil and
groundwater protection is to develop a scientific basis
for the protection of soil and the prevention of
groundwater pollution. The protection against organic
pollutants will include research about the throughflow
from waste disposal sites.

The research area 8: Technologies for environmental
protection focuses on waste research.

In respect of soil protection against point-source
contamination the following items of the waste research
are of special interest:

-  specific treatment processes to facilitate disposal
such as solidification of waste

-  Environmental impact assessment for waste diposal sites

-  Risk assessment and reclamation of abandoned disposal
sites
1.4  Recommendations for research;

Contaminated land:

a) Behaviour and impact of organic and inorganic
contaminants on soil ecosystems

b) Overlapping effects of a wide variety of contaminants
in the soil

c) Dose-response relations to low dose levels of soil
contamination (long-term effect)

d) Research for cost-effective reclamation techniques for
abandoned waste disposal sites.
                            651

-------
COUNTRY
BELGIUM
DENMARK
GERMANY
FRANCE
gป IRELAND'**
ro
ITALY
GREECE
LUXEMBOURG
NETHERLANDS
' PORTUGAL .
-SPAIN -
UK
until theye.it 2000
SITES
Number
Flanders: 70
Wallonia
3115
35000
44000
800
7
5433
5000
142
6060
69
ฑ1800
Type
industrial/waste
industial/waste
5000 industrial
30000 waste

gasworks/mines
abandoned waste
uncontrolled
disposal
municipal waste
Contaminated: 6000
small/60 big
toxic or hazardous
waste
industrial (estimate)
I
(Cataionia 400}
916
Wales 703
45600 Ha
inausinai waste
uncontrolled spillways
urban solid waste
uncontrolled spillways
Contaminated
derelict land
Ref
year
1985
1980-2
1985
1987
1982
?
?
?
1986
1986
1986

1983/4
1982
Nฐofcleaned-
up sites
Insufficient
data.
Insufficient
data.
Insufficient
data.
Insufficient
data.
Insufficient
data.
Insufficient
data.
Insufficient
data.
Insufficient .
data."
Insufficient
data.
Insufficient
data.
Insufficient
data.
Insufficient
data.
3resent annual
*xpenditure(1984)
x10&
ECU

5
North-Rhine
Westphalia
48
Nord pas de
Lorraine,
13




88



National
currency

44DKR
106 DM
Calais,
Rhone-Alps
87 FF




215 DFL



Estimated future
annual expenditure*
<106
ECU
62
13
377
214
10
134
11
3
56


476
Natcurrency
2772 BFR
101 DKR
829 DM
1468 FF
7f
198190 LI
1456 DR
189FRS
140 DFL
•

280 ฃ
% of GDP
0,08
0,03
0,07
0.04
0,06
0,06
0,04
0,07
0,04


0,1
* new inventory until end rvf 1QR7

-------
Landfills:

aJ lesearch for the safe disposal of hazardous waste in
• landfills

b) Effects of waste disposal on land

c) Soil vulnerability by dump leachates

d) Treatment of seepage water from landfills

e) Longterm surveillance and monitoring for hazardous
waste in landfills


2,.  P re par a tip n	of	legal p r o v i sip ns,
Preventive measures:

a) Preparation of guidelines and codes for landfill
design and operation:

Strategy in landfilling /17/:

   banning of landfilling of organic waste (as far as
possible)

   operating of mono-landfills or quasi-mono-landfills

   banning of liquid waste

   treatment of waste before dumping to reach a "final
storage quality".

b) Guidance notes for careful dismantling of disused
factories, plants and mining districts

Curative measures:

a) Guidelines for the risk assessment of contaminated
sites

b) Setting up of uniform trigger and reference values for
contaminated soil                          •     -

c) Guidelines for sampling and analysis of soil

d) Definitions for contaminated land
                            653

-------
3.  Participation  in  international  working
groups/.te chn ic a 1...comul 1 .tJbeea -,-•,':.,      • • ,   :   :••••.

3,1  Nato/CCMS Pilot  Study' "Demonstration of, remedial
action technologies for contaminated  land and
groundwater".

The purpose of the pilot study  is to  demonstrate  and
evaluate new technologies and/or existing systems for  the
restoration of hazardous waste  sites  and to-promote  the
exchange of information and data.                  ...

After establishing contact with the Nato/CCMS the
Commission (DG XI/A-3) was invited  to'attend  the  second
international experts1 meeting  in the Netherlands     ,
(Bilthoven, November  1,988) and  to present 'the activities ,
of the CEC in the  field ,of remedial action  technologies.

3.2 International  organisation  for  standardization (ISO1)
TC 190

The International  Organisation  for  Standardization has
established in 1985 a new Technical Committee for, soil
quality including  classification, definition  of terms,
sampling of soils  and measurement and soil
characteristics. The  Commission (DG XlVft-3)•has an
observer status and receives all documents.

V  References:                                 ,

/1/ Official Journal  of the European  Communities,  -C'  328
(07.12.1987) -                 .,        ..'•'.-•, ' ;   ','

/2/ Haines, R.C. + Joyce, F.E.  (1987):  Land recycling  and
renewal. A prospective analyses of  industrial land ,
contamination and  remedial treatment.  -, ECOTEC Ltd,! ,
Birmingham                                     ,.-•-..

/3/ European Environmental :Bureau (1988): Soil
contamination through industrial toxic  dumps.  - Seminar,
Brussels      .         ,       ',,'",'

/4/ Barkowski, D.  et  al. (1987) Altlqsten'.  Handbuch  zur
Ermittlung und Abwehr von Gefahren  durch.kontaminierte
Standorte. - Verlag C... F. Hiiller, Karlsruhe

/5/ Hurtig, H.W. et al. (1986): Statusbericht.;zur
Sanierung von kontaminierten Standorten - tibersicht  iiber
Sanierungskonzepte und SanierungsmaBnahmen  in Forschung
und Praxis. - Battelle Institut e.  V.,  Frankfurt

/<$/ Kerndorff, H.  et  al., (19.88): Groundwater  •
contamination by abandoned waste disposal sites:
Detection and posssibilities of standardized  assessment.
- In: K. Wolf et al.,  (Ed,): Contaminated Soil  * 88, Second
International TNO/BMFT Conference on  Contaminated Soil,
Hamburg                         •         ..••             , .

                            654

-------
/?/ Fran2ius,  V.  (1986):  Effects  of, abandoned waste
disposal  sites and  Industrial ,.sites .oft "the soil:  Possible
remedial  measures,  -  In:  Earth, H.  +  L'Hermite,  P.  (Ed.):
Scientific  basis  for  soil  protection  in the European
Community.  Elsevier;  London, New  York

/&/ Kloke,  A,"  (1988):  Fundamentals  for determining  use"
related,  highest  acceptable  contaminant levels in inner
.city  and  urban soils,  -  In:  K.  Wolf et al.  (Ed.):
Contaminated  Soil  '88, Second  International TNO/BMFT
Conference  on Contaminated Soil,  Hamburg

/9/ Vegter, J.J. 'et al.  (1988): Soil  quality standards:
Science or'  science  fiction - an inquiry into the
methodological aspects ot  soil ;quality criteria.  -  In:  K.
Wolf  et al. (Ed.):  Contaminated Soil  *68,  Second
International  TNO/BMFf Conference on  Contaminated Soil,
Hamburg   ,

/10/'De Bruijn, P.J..  + de  Walle,,  F.B;  (1988): Soil
standards f'or-soil  protection  and remedial action in the
Netherlands.  - In:  K.  Wolf et  al.  (Ed.):  Contaminated
Soil  *-88, Second  International  TNO/BMFT Conference  on
Contaminated  Soil,  Hamburg    .

/11/  Assink',  J". W.  -i- van  den  Brink,  W.J.  (1986):
Prospective action  with  regard  to soil 'contamination in,
view  of a commo.n  policy.  - TNO, The Netherlands

/12/  Palmark,  M'.  et al.  (1987): Contaminated Land in the
EC, summarizing report.  -  Dornier System GmbH,
Friedrichshafen

/13/  Franzius, V.  (1986):  Altlastenproblematik -
iibersicht und Kosten  im  EG-Bereich  und in den OSA,  -'
Vortrag beim  Vertieferseittinar  "Altlastensanierung und
zeitgemaBe  Deponietechnik",  Universitat Stuttgart

/14/  Mben,  J.E.T.  (1988):  Soil  protection in the'
Netherlands.  - In:  K.  Wolf et  al.  (Edซ):  Contaminated
Soil" *88, Second  International  TNO/BMFT Conference  on
Contaminated  Soil,  Hamburg  -       •'

/15/'Kovalik,  U,U., Jr.*(1988): Implementing the  new
Superfund:  an ambitious  agenda  for  EPA.  -  In: K.  Uolf et.
al,  (Ed.):  Contaminated  Soil  '88,  Second international
TNO/BHFT  Conference on Contaminated Soil,  Hamburg

/1
-------
/18/  European Community Environmental Legislation, 1967-
1987,
(Vol.1, General Policy and Nature Protection)
(Vol.3, Chemicals and Waste)
(Vol.4, Water)
Document Ho. XI/989/87
Brussels
                            656

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ANNEX  1
Sewage  sludge
                                                  ANNEX IA

                      LIMIT VALUES FOR CONCENTRATIONS OF HEAVY METALS IN SOD.

           {mg/kg of dry matter in a representative umple, u defined in Annex II C, of toil with a pH of 6 lo 7)
Parameter*
Cadmium
Copper (!)
Nickel ('}
Lead
Zinc(')
Mercury
Chromium (J)
Limit values (')
1 to 3
50 to 140
30 to 75
50 to 300
150 10 300
1 to 1,5
—
                           {') Member States may permit the  limit values  they fix  to be
                               exceeded in the case of the use of sludge on land which at the
                               time of notification of this Directive is dedicated to the disposal
                               of sludge but on which commercial food crops are being grown
                               exclusively for animal  consumption.  Member States must
                               inform  the Commission of the  number  and type  of sites
                               concerned. They must also seek to ensure that there is no
                               resulting hazard to human health or the environment.
                           (J) Member States may permit the  limit values  they fix  to be
                               exceeded  in respect of these parameters on soil with a pH
                               consistently  higher than   7.  The  maximum authorized
                               concentrations of these heavy metals must in  no case exceed
                               those values by more than 50 %. Member States must also
                               seek to ensure that there is no resulting hazard to human health
                               or the environment and in particular to ground water.

                           (') It is not possible at this stage to fix limit values for chromium.
                               The Council will fix these limit  values later  on the basis of
                               proposals to be submitted by the Commission, within one year
                               following notification of this Directive.
                                                   ANNEX IB

                 LIMIT VALUES FOR HEAVY-METAL CONCENTRATIONS IN SLUDGE FOR USE IN
                                                 AGRICULTURE

                                               (rag/leg of dry matter)
Parameten
Cadmium
Copper
Nickel
Lead
Zinc
Mercury
Chromium {')
Limit vijues
20 to ' 40
1 000 10 1 750
300 to 400
750 to 1 200
2 500 to 4 000
16 to 25
' —
                             ('} It is noi possible at this stage to fix limit values for chromium.
                                The Council  will  fix these limit  values later  on the basis of
                                proposals to be submitted by the  Commission  within one year
                                following notification of this Directive,
                                                     6S7

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ANNEX  2
                                                      ANNEX

                             LIST I OF FAMILIES AND GROUPS OF SUBSTANCES


             List I contains the individual substances which belong to the families and groups of substances enum-
             erated below, with the exception of those which are considered inappropriate to list I on the basis of
             i low risk of toxicity, persistance and bioaccumulation.

             Such  substances which with regard to toxicity, persistance and bioaccumulation are appropriate to list
             II ire to be classed in list II,

             1. Organohalogen compounds and substances which may form such compounds in the aquatic envi-
             '   ronment                                                            "       •

             2, Organophosphorus compounds

             3. Organotin compounds

             4, Substances which  possess carcinogenic mutagenic or teratogenic properties in or via the aquatic
                environment ('}

             5> Mercury and'its compounds

             6, Ctdmium and its  compounds

             7, Mineral oils ind hydrocarbon!

             8, Cyanidei,
                            LIST II OF FAMILIES AND GROUPS OF SUBSTANCES

              Liil II contains the individual substances ind the categories of tubiunces belonging to the families
              and groups of tubiunces listed below which could hive a  harmful effect on groundwiter,

              1. The following metalloids and metal* ind their compounds:

                  1, Zinc                                   II. Tin
                  2. Copper                                 12. Barium
                  3. Nickel                                 '13. Beryllium
                  4. Chrome                                14, Boron
                  5, Lead                                   15, Uranium
                  fi. Selenium                               16. Vanadium
                  7, Arsenic    .                          .17, Cobalt
                  8, Antimony                               18. Thallium
                  9. Molybdenum                            19. Tellurium
                 10. Titanium                              20, Silver.


              2.  Biocides and their derivatives not appearing, in list I,

              3. Substances  which have a  deleterious effect  on the taste and/or odour  of  groundwater,  ind
                 compounds liable to cause the formation  of such substances in such water  and to render it Unfit
                 for human  consumption,

              4. Toxic or persistent organic compounds of silicon, and substances which may cause the formation
                 of such compounds  in water, excluding those which are biologically harmless  or are rapidly
                 converted in water into harmless substances.

              5.  Inorganic compounds of phosphorus and elemental phosphorus.

              6.  Fluorides.

              7.  Ammonia and nitrites.
                    1 ecrfiin Jiilmปnce* in list II tie ciiciii^fnic, muugcnic or ferno/jemc, they are included m category < ol this hif

                                                         658

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ANNEX  3

No C 190/154                 ,  Official Journal of the European Communities                         20,7.87

Friday, 19 Juซ 1987

           6,  Waste disposal industry — Water quality objectives for iihronilum


           (ป)  Doc.A2.31/87


                                              RESOLUTION

                              on the wute disposal industry and old waste dumps


           The European Parliament,

           —  having regard to the motion for a resolution by Mrs Schleicher and others on the waste
               disposal industry and old waste dumps (Doc. B2-1654/85),

           —  hiving regard to the motion for a resolution by Mr Tridente on the danger of discharging
               waste on the outskirts of an  environmental protection area (Doc. B2-952/86),

           —  hiving regard to its previous it solutions on waste and in particular those of 16 March 1984 (')
               and 11 April 1984 O,

           —  having regard to the report by the Committee on the Environment, Public Health and
               Consumer Protection (Doc. A2-31/87);


           Rtgarding tin gintral abjectlw <&f Community polity on watti

           1.   Calls initially for action to be  taken on all its previous requests, and in particular those
           calling for.
           (a)  the creation, within the Commission, of an administrative unit which is responsible for waste
               alone and with a bigger staff complement than hitherto (the European Parliament has on
               several occasions created posti in the budget for the environment sector, but the Commission
               has not used them for matters concerning waste);
           (b)  the harmonization or systems of statistics on waste;
           (c)  clarification of the Community  definition and nomenclature of dangerous waste;
           (d)  the development of a long-twin Community strategy on waste management;
           (e)  the organization of campaigns to increase the awareness of the public, waste producers and
               workers in the industry;
           (0  the improvement of safety procedures covering movements of dangerous waste, with partic-
               ular regard  to .professional training and the information given to haulage firms and driv-
               ers;

           2.   Calls on the Commission, in addition, to put into cfTect all the measures it has set out in the
           action programmes on the environment, and in particular
           (a)  programmes to promote the extended use of products and the recovery of secondary raw
               materials;
           (b)  recommendations for the policy on clean technologies;

           3.   Condemns the irresponsible attitude of some Member Slates regarding the observance of
           directives adopted on waste, and insists once again that the Commission play its  full role in
           ensuring total compliance with nhese directives;

           4.   Calls on the Commission to submit proposals for the establishment of a corps of Commu-
           nity inspectors  responsible for  monitoring the strict application of Community law on the
           environment; ,                                 •

           S.   Criticizes  the Commission for its continued failure to fulfil adequately its function of
           supervising the  incorporation into national law of and compliance with  the Directives on waste
           and calls on  it, in particular, to ensure forthwith that all Member States comply with their duty to
           provide information;

           6.   Calls on the Commission to supplement, at an early date, the measures it has taken with
           regard to the monitoring of international movements of waste by measures to harmonize the
           standards applicable to waste disposal facilities (dumps, incinerators) which exist in the various
           Member States;
            <>}  OJ No C 104. 16,4. I984,.p. 147.
            (')  OJ No C 127. 14, $, 1914, p,67.
                                               659

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            ANNEX  3


20* 7.87	       Official Journal of the European Communities                    No C 190/155

                                                                                           FrMty,

           7,    Stresses particularly that  the harmonization  of standards applicable1'to waste disposal
           installations must also cover national regulations setting limit values for the discharge of pollu-
           tants into the soil and national regulations designed to protect groundwater;

           8.    Calls on the Commission to draw up a specific Community strategy on the management of
           'small quantities of dangerous waste' emanating from households, research laboratories, small
           undertakings and the fanning industry;


           9.    Calls on the Commission, as part  of its coordinating function in the research sector, to
           produce a survey of its techniques and pilot projects regarding the treatment, sorting and recycling
           of waste;                             '       .                             ,


           10.    Emphasizes that, as a matter of priority, Community policy on waste prevention must
           progress from rhetoric to practical action, for example by the effective application of a European
           label for 'clean products';


           11,    Insists, again  as a  matter of priority, on the  increased importance to be  accorded at
           Community level to the provision of information on waste, beginning with the information which
           Member Slates must make available in  accordance with the obligations laid down in exiating
           directives;

           12.    Approves in  particular, among the measures planned by the Commission in its Fourth
           Environment Action Programme the introduction of financial procedures implementing the
           polluter pays principle;                .             .  . .   .  .   .    •  •  .      ,  •

           13.    Calls on the Commission to speed up work on new directives on:

           (a)  livestock effluents;

           (b)  batteries;                                    ,                  ..   .  .

           (c)  solvants;

           (d)  waste plastic;                                                            '     '


           14.    Strongly advocates that particular attention be paid to waste connected with heavy metals,
           in view inter alia of the alarming figures given by water companies regarding the  poisoning of
           surface water and groundwater as a result of the  increasing  contamination caused by heavy
           mctnls;


           15.    Urges that, in accordance with the Oslo Convention, immediate measures be taken to put a
           stop to waste incineration at sea and calls on the Member States to sign both the provisions of the
           Convention and the annexes and to implement them immediately in national measures and
           monitoring procedures;                                               •


           16.    Calls for particular attention to be paid by the Community Institutions to waste, that drifts
           from one country to another via cross-frontier rivers, with strict measures based on monitoring at
           the points where the rivers cross the frontiers to ensure that contamination of surface water in the
           neighbouring country is properly counteracted in order to protect the drinking water extracted
           from the surface water, and to prevent contamination of the groundwater via permeation of the
           pollution which accumulates in the beds of these rivers;
           Meaium to bt taken regarding old watte dumps

            17.   Draws attention to the extent and seriousness of the potential problems, in particular
           reprding the quality of groundwater, and consequently also of drinking water, arising from a large
           number  of old waste dumps —  more than  10 000 polluted sites to be cleaned up in the
           Community at an annual cost, over IS years, of more than one billion ECU;


            18.   Points out that the United States has produced a response to this problem which includes
           the establishment  at federal level of technical standards and rules governing objective civil
           liability and a budget funded partly by a tax on chemical and petroleum products;


                                                  660

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ANNEX 3


No C 190/156                    Official Journal of the European Communities                         20.7.87

Friday, 19 JUM 1987

           19.   Points out that in  the  European Community only a few Member States have so Tar
           recognized the nature or the problem and taken certain measures as a result;

           20.   Points out that this disparity among national responses to the problem or contaminated
           sites is not only a cause or distortion or competition but has also led to many cases of contami-
           nated soil being exported from one country to another,

           21.   Recalls that the concept enaction at the most appropriate level is one of the principles of the
           Community's environment policy as' contained in Article 130R and that many of the potential
           problems of old waste dumps are best handled at national, regional or local level:

           22.  Calls, in the first instance, for the incorporation into the law and practice of all the Member
           States of the last part of Article 7 of Directive 78/319/EEC, which seeks to ensure that 'toxic and
           dangerous waste is recorded and  identified  in respect of each site  where  it  is or has been
           deposited' (');

           23.  Calls on the Commission, on the basis of information provided under Article 7 of Directive
           78/319/EEC, to draw up a list of all dangerous waste dumps in order to identify in particular
           problematical dumps situated near  borders and to call on the Member States to make a survey of
           all disused industrial sites where dangerous substances were employed;

           24.   Calls on the Commission, as part of its coordinating function in the research sector, to
           produce a survey of techniques for cleaning up waste dumps and industrial sites and to ensure that
           Member States exchange information about existing techniques;

           25.   Regards the traditional procedures for establishing civil liability as inadequate to guaran-
           tee, in certain cases, the compensation of victims and the reparation of damage caused to the
           environment, and hence calls on the Commission to make proposals generalizing the objective
           liability of the producer of dangerous waste and establishing obligations on those involved in the
           management of dangerous waste to take out insurance or an equivalent financial guarantee;
                               /
           26.   Regards as equally essential the creation of public or private funds which would guarantee
           that a contaminated site would be cleaned up (and any victims compensated) in cases where there
           were no solvent or identifiable guilty party;

           27.   Calls on the Science and Technology  Option Assessment Office (STOA) to draw up a report
           on how the 'Superfund' operates in the United States and on the possibility of establishing a
           .similar mechanism in the European Community;

           28.   Urges that research and development programmes at Community level  should exploit the
           expertise of the Joint Research Centres and should cover

     '      —  the  spread of pollutants emanating from old waste dumps in various types of soil and in
               water,           ,                 •.

           —  the  refinement of risk-assessment models;

           —  the  development of emergency methods to combat pollution;

           29.   Calls on the Commission to release  resources from the existiing environmental funds for
        ;   the coordination of research and development and the transfer of technical knowledge essential
           ; for the cleaning-up of particular contaminated sites;                               ,

           30.   Calls on the Commission once again to consider whether, in the future,  the dumping of
           certain  types of dangerous waste  should  not be prohibited and  the recycling of such waste
           systematically encouraged, and in  this connection, calls on the Commission to study the econ-
           omic and environmental benefits of recycling certain dangerous wastes as opposed to other forms
           of disposal;

                                                      *
                                                  *       *
          t •               •'

           31.   Instructs its President to forward this resolution to the Council and Commission.
           (')  OJ Not 84. 31.3. 1978. p. 45.
                                                661

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    ANNEX 4                                                  (3rd amendment)
      TECHNIQUES FOR LOCATING AND RESTORING SITES CONTAMINATED BY
            HAZARDOUS WASTES AND/OR HAZARDOUS SUBSTANCES
                              Application fields
1.    Location of contaminated sites and risk evaluation:
     1.1     Systematic investigation methods for polluted heterogeneous soils,
            which are contaminated with waste and/or hazardous substances.
     1.2     Development of methods for rapid investigation and risk assessment of
            hazardous waste sites, or in case of emergency.
2.    Restoring of contaminated sites                   -
     2.1     Remedial action techniques for the decontamination of soils containing
            clay and humus,
     2.2     Cost-saving remedial methods for a large number of small areas with
            contaminated soils,
     2,3     Remedial action techniques for the decontamination of soils with a high
            content of heavy metals, organic and inorganic compounds,
     2,4     Decentralized, mobile, modular designed soil decontamination systems
            forthe clean-up of various combinations of pollutants,
3.    Demonstration of microbiological  techniques
     3.1     Techniques for the supervision of the degradation and displacement of
            pollutants during microbiological in-situ treatment.
     3,2     Improvement of microbiological in-situ remedial action techniques for
            the removal of hydrocarbon contaminants,
     3,3     Techniques for the improvement of the contact reactions between the
            nutrients, the microorganisms and the contaminated soils.
     3.4     Microbiological degradation techniques for concentrated organic
            contaminants in soil and groundwater.
4,    Thermal techniques
     4,1     Thermal techniques for the decontamination of soils polluted by
            halogenated organic compounds.
5.    Extraction techniques
     5.1     Improvement of extraction methods for soil restoration.
     5.2     Combination of extraction methods and biological treatment techniques
            forthe decontamination of oil and other organic compound sludges.
                                            •U.S.GOVERNMENTPRINTTNGOmCEassa -7SO-B.02/ 60955
                                        662

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