O O A Committee on the
EPA/6QO/R-93/012b
4/l\ Challenges of
/ \ ... ^ February 1993
. ^ za 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"
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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.
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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.
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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. :
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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.
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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 metalsmainly lead. The project under desrt involves the investigation of soil
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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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
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Barriers To implementing innovative
training
and
Pr8fliงi8H8i
i UUซ ป< ij^ป < >ซปl.
otivational
informatiSR
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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.
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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.
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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).
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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.
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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.
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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
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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
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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
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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
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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,
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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.
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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
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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.
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Turkey's Tour de Table Presentation
-------
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
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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.
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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.
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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
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United Kingdom's Tour de Table Presentation
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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.
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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
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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 . -
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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
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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. *
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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
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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
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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
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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
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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-NorthernRemedial 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.
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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.
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Parsons ChemicalRemedial 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 ChemicalStatus
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.
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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.
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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.
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Ott/Story/CordovaRemedial 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.
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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 FarmRemedial 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.
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Lee FarmStatus
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.
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Outboard MarineRemedial 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 MarineStatus
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.
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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-WorksRemedial 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 qualitativethe upgradient
shall be unaffected by the contaminated site.
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Gas-WorksStatus
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.
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Burbacher HiitteRemedial 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 HiitteStatus
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.
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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.
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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.
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Kertess ChemicalsRemedial 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 ChemicalsStatus
Groundwater treatment began in 1976 but did
not meet cleanup objectives.
Recently a new remedial plan was designed
combining several technologies.
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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 SudRemedial Technology
Treatability studies were conducted using high
pressure soil washing.
Other technologies will be tested.
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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.
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Haynauer Strasse 58Remedial 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 58Status
Remediation began in 1990,
All former buildings have been demolished
and debris removed.
Preparations are being made to begin soil
excavation.
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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
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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
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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
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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
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NATO/CC1VIS Guest Speaker:
Brett Ibbotson, Canada
AERIS, an Expert Computerized System to Aid in the
Establishment of Cleanup Guidelines
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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
150
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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).
151
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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 Government50%
(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
-------
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 environmentalhealth 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
-------
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
-------
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
-------
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
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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 semiliquid 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 runoff 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
-------
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*
Physicochemical treatment centres mainly perform the
following... treatment procassesj oxydat ion-reduction,, neutrali-
zation, dehydrationi fixation, and emulnionbreaking.
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
-------
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 reuse 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 LandBurial 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 landburial 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 nansaturated 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
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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
-------
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
-------
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247
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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
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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
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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 tensioactifs 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 tensioactlfs
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
[oo
~'
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
-------
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
-------
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
-------
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
-------
<
SOCIETE DES
:IMENTS FRANCA
ilS
CEDILOR
CBL
10%
C1MENTS
LAFARGE
'
SCORI
s
'
SOVALEG
' .',' !'.. -
RIG
:51
%
COHU
51%
ECpTEC
nn
i
CIMENTS
VICAT
SCORIBEL
(Belgium)
ENDER'
(Spain)
280
-------
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
-------
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
-------
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
-------
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
-------
- 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
-------
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
-------
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
wateredinitially, 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.
aa
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
-------
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
-------
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
-------
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>
-------
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
-------
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
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HMCRI, 1990.
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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.
-------
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
-------
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)
-------
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
-------
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, airsea 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
-------
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
-------
/*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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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*
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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).
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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.
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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. :
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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.
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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.
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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
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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*
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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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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.
-------
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
-------
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
-------
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
-------
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
-------
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
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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
-------
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
-------
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
-------
Figure 3.9.
Photograph
illustrating the soil
sampling tube
insertion.
Figure 3.10. Photograph illustrating the five soil samples in their respective
containers.
436
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
APPENDIX B
CHARACTERISTICS OF THE VOC SOIL SAMPLES
469
-------
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
-------
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
-------
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
-------
APPENDIX D
QUALITY CONTROL SAMPLE ANALYSES
475
-------
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
-------
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
-------
-------
NATO/CCMS Guest Speaker;
Guus Annpkkee, The Netherlands
Biological Treatment of Contaminated Soil and Groundwater
No text available.
479
-------
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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 miniplant 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 (SLG);
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 holdup, 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
dpซ1QQ1000 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
-------
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 Nsource 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
-------
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
-------
NATO/CCMS Guest Speaker:
Kare! Luyben, The Netherlands
Dutch Research on Microbial Soil Decontamination in Bioreactors
503
-------
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
-------
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
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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
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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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1.4
1.2
0,8
0.6
0.4
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r c ~r
L Test No.
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0
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(a) Rb(ll) Removal
60
37 >
/ <*>''
"/ S'
l - 2
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
(a) Breakthrough of Phenol
40
35
ซ**
> 30
jฃ
uTป
o~
IU .,
O 20
LLJ
O.
X
15
10
1 2 3-4
PORE VOLUME OF FLOW
. (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
-------
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 ^
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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)
-------
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)
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
-------
MATO/CCMs CJUest Speaker:
Roy C. fJwtt&JH) ilhttecf States
Environmental Contamination in Eastetfi iHcf Slhtral Europe
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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
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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
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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
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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
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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.
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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.
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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.
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NATO/CCIVIS Guest Speaker:
Gregory Ondich, United States
The Use of Innovative Treatment Technologies in Remediating Waste
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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
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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;
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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,
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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 , , ,,..,,,,,,,
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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.
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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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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 wasteStringfellow 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
-------
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
-------
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
-------
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 solventsto 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
-------
" "'' 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
-------
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
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\N\\\\\\\\\\\\\\\\
'XXXXXXXXXXXXXXXXXXXXXXXXX.
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'XXXXXXXXXXXXXXXXXXXXXXXXX.
'XXXXXXXXXXXXXXXXXXXXXXXXX.
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'XXXXXXXXXXXXXXXXXXXXXXXXX.
XXXXXXXXXXXXXXXXXXXXXXXX
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
-------
-------
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
-------
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
-------
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
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/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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