NATO / CCMS
Second International Conference
Demonstration of Remedial Action Technologies
for Contaminated Land and Groundwater
Bilthoven, the Netherlands
7-11 November 1988
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NATO / CCMS
Second International Conference
Demonstration of Remedial Action Technologies
for Contaminated Land and Groundwater
U.S. Environmental Protection Agency
Region III Information Resource
Center (3PM52)
841 Chestnut Street
Philadelphia, PA 19107
Bilthoven, the Netherlands
7-11 November 1988
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This report is not an official document of the
NATO/CCMS Pilot Study program.
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ABSTRACT
In November 1986, the NATO Committee on Challenges of Modern Society
(CCMS) formally adopted a United States proposal for a new five year pilot
study to demonstrate technologies for cleaning up contaminated land and
groundwater. The participating NATO countries are Canada, Denmark, Federal
Republic of Germany, France, the Netherlands, and the United States. Japan
1s also participating. Norway and the United Kingdom are observer
countries. The Pilot Study Director 1s from the United States; the co-
directors are from the Federal Republic of Germany and the Netherlands.
The Second International Conference was held 1n Bilthoven, the
Netherlands on 7-11 November 1988. Seventeen projects (final and Interim)
were prepared including the following types of treatment: solidification/
stabilization (2 projects), microbial degradation (3 projects), pump and
treat (3 projects), soil extraction (4 projects), volatilization (1
project), thermal (3 projects), and chemical (1 project). The discussions
at this meeting also included recent developments in the regulations and
remedial technology research and development in the attending countries.
The next meeting will be a workshop held 1n Copenhagen, Denmark on 8-10,
May 1989.
i
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. Table of Contents
Paae
ABSTRACT 1
INDEX TABLE OF PROJECTS, BY MATRIX AND TREATMENT TECHNOLOGY vii
INTRODUCTION 1
BACKGROUND 1
REPORT ORGANIZATION 7
RECENT DEVELOPMENTS IN NATIONAL PROGRAMS 9
Canada 11
Denmark 19
Federal Republic of Germany 21
France 25
The Netherlands 27
Norway 35
United Kingdom 37
United States 39
PROJECT REPORTS 45
Stabil1zat1on/So11d1f1cat1on
Solidification evaluation (petroleum refinery wastes/
agricultural chemical manufacturing/tannery; 4 sites,
France) 47
Sol1d1f1cat1on/Hazcon process (lagoons, landfarm and
spill areas; Douglasvllle, Pennsylvania, United States).. 63
Microbial Degradation
Aerobic/Anaerobic 1n-s1tu degradation (chemical waste
disposal site; Skrydstrup, Denmark) 75
In-s1tu blorestoratlon (gasoline station; Asten,
The Netherlands) 93
In-s1tu enhanced aerobic restoration (jet fuel; Egl1n
A1r Force Base, United States) 121
Pump and Treatment
Pump and treat groundwater (V1lie Mercler, Canada) 143
Biological pretreatment of groundwater (lindane
manufacturer; Bunschoten, The Netherlands) 179
i 11
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Page
Recovery/recycl1ng (zinc smelting plant; Lot River,
France) 193
Soil Treatment by Extraction - A
In-s1tu extraction (photographic paper manufacturer;
Soestduinne, The Netherlands) 195
Vacuum extraction (well field; Verona, United States).... 217
Volatilization
Radio frequency volatilization (jet fuel spill; Volk Air
Field, United States) 241
Thermal Treatment
Rotary kiln Incineration (former coking plant; Boenen
near Unna, Federal Republic of Germany) 267
Infra-red Incineration (former oil refining; Peak Oil,
Tampa, Florida, United States) 287
Soil Roasting (mercury recovery plant; Tokyo, Japan) 289
Son Treatment by Extraction - B
Vibration (oil recovery facility; Harbauer, P1ntsch-ol,
Federal Republic of Germany) 303
High pressure soil washing (Goldbeck-Haus, Federal
Republic of Germany) 313
Chemical Treatment
K-PEG technology 1n soils and liquids (chemical recycling
facility and road oiling; Gary, Indiana and Wide Beach,
New York, United States) 335
APPENDICES
A List of Attendees at NATO/CCMS Second International
Conference, Bilthoven, The Netherlands, 7-11 November
1988 A-l
B Presentations by NATO/CCMS Guest Speakers
Euseblo Murillo Matilla & Hans-Joachim Stietzel
(European Economic Community) - Soil Protection
Against Point-Source Contamination in the European
Community B-l
1 v
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Page
Karl Luyben (The Netherlands) - Dutch Research on
Microbial Soil Decontamination 1n Bioreactors B-29
Gregory Ondlch (United States) - The Use of Innovative
Treatment Technologies 1n Remediating Hazardous Wastes. B-33
Ronald Probsteln (United States) - Electro-osmosis for
In-s1tu Hazardous Waste Site Remediation B-57
C Presentations by Continuing NATO/CCMS Fellows
Wayne Pettyjohn (United States) - Hydrogeology of
F1ne-Gra1ned Materials C-l
Sjef Staps (The Netherlands) - Evaluation of Research
Projects Concerning Biological In-S1tu Treatment of
Contaminated Soil and Groundwater C-15
James Gossett (United States) - Biodegradation of
Dlchloromethane Under Methanogenic Conditions C-21
Bob Bell (United Kingdom) - Uptake by Higher Plants
of Organic Pollutants from Low Level Polluted Soil C-47
D Presentations by New NATO/CCMS Fellows
Reset Apak (Turkey) - Heavy Metal Removal from
Contaminated Groundwater by the Use of Metallurgical
Solid Wastes and Unconventional Materials D-l
Aysen Turkman (Turkey) - Cyanide Removal from
Contaminated Groundwater D-19
Alessandro D1 Domenlco (Italy) - Sunlight-Induced
Inact1vat1on of Halogenated Aromatics 1n Aqueous
Media D-32
Thomas Dahl (United States) - Environmental Problems
at the Strlngfellow Site D-83
Michael Smith (United Kingdom) - International Study of
Technologies for C1ean1ng-Up Contaminated Land and
Groundwater D-87
E Presentation at Site Visit (Delft University of
Technology) E-l
v
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Index Table of NATO/CCMS Projects Reported on at the Second International
Conference on the Pilot Studyon Remedial Action Technologies
for Contaminated Land and Groundwater
Treatable Contaminants
MATRIX
TREATMENT
») / b •)
6 / h (J
^
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Index Table (continued)
Treatable Contaminants
MATRIX
TREATMENT
O OV , J? / £
O
tr
-C" O
Specific
Contaminants Treatment Status of
In-S1tu B1orestorat1on
RIVM and TNO, Asten
Noord-Braant, The Netherlands
V
Gasoline
In-SItu
Demonstrated
93
Chemical/Physical
txtraction/Cadmlum Removal (leaching
TAUW Infra Consult
Soestdulnen, The Netherlands
V
Cadmium
In-S1tu
Experimental
195
Extraction by Vibration
Harbauer, P1ntsch-ol,
Berl1n
Federal Republic of Germany
~
V
V
/
Phenol, PCBs
On-Slte
Commercial
303
K-PEG Process _
U.S. Environmental Protection
Agency
Wide Beach, NY, United States
~
V
V
PCBs, D1ox1n
0n-S1te
Demonstrated
335
High Pressure Soil Washing and
Oxidation
Goldbeck Haus, Hamburg
Federal Republic of Germany
V
Phenol, Kresol
In-S1tu
Demonstration
313
Soil Vapor Extraction
U.S. Environmental Protection
Agency
Verona Well Field
Battle Creek MI, United States
V
V
V
V
Mercury,
Heavy Naphthas
In-Sl'tu
Demonstrated
217
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Index Table (continued)
Treatable Contaminants
MATRIX
TREATMENT
Specific
Contaminants
Treated
Treatment Status of
Solidlflcatlon/StabllIzation
Hazcon Engineering, Inc.
Douglassvl1le, PA,
United States
V
/
~
V
y
Lead, PCBs
On-Slte
Commercial
63
Sol1d1f1cat1on/Stab1lization
EIF Ecologlc and TREDI
4 sites, France
/
V
V
V
Tars, Sulfides,
Heavy Metals
On-Slte
Commercial
47
Thermal
Radio Frequency Volatilization
I IT Research, Volk A1r Base,
Wisconsin, United States
V
V
V
~
Waste Fuels
In-S1tu
Commercial
241
Rotary Kiln Incineration
(indirect heatlng/pyrolysls)
Ruhrkohle Umaseltechnlk
Boenen (near Unna)
Federal Republic of Germany
V
Tar, Acid Resins
On-S1te
Demonstrated
267
Soil Roasting
Kokkaido Mercury Recovery Plant
Arakawa-Kir, Tokyo, Japan
~
Mercury, Lead
Off-S1te
Commercial
289
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Introduction
This 1s a report of the proceedings of the second International con-
ference for a pilot study under the NATO Committee on Challenges of Modern
Society (CCMS): Demonstration of Remedial Action Technologies for
Contaminated Land and Groundwater. The meeting was held 1n Bilthoven 1n
the province of Utrecht, The Netherlands on 7-11 November 1988. Exhibit 1
is the agenda for the meeting.
The purpose of this conference was to present final or Interim
reports on 17 Pilot Study projects. The conference also Included visits to
two soil cleanup projects (at Soestdulnen and at "CINDU," both 1n Utrecht),
the Ecotechnlch thermal treatment plant for soils also 1n Utrecht, and two
pilot scale research projects 1n Delft (a landfarming project at TNO, and a
bloreactor project at the Delft University of Technology).
Background
The problems of contamination resulting from Inappropriate handling
of hazardous materials and hazardous wastes are faced to some extent by all
countries. The need for cost-effective remedial technologies to apply at
these sites has resulted In the application of new technologies and/or new
applications of existing technologies.
Building a knowledge base so that emerging remedial technologies are
Identified 1s the Impetus for the NATO/CCMS Pilot Study on "Demonstration
of Remedial Action Technologies for Contaminated Land and Groundwater."
New technologies being demonstrated and evaluated 1n the field are
discussed. This allows each of the participating countries to have access
to a data base of multiple applications of Individual technologies without
any country having to commit a disproportionate amount of Its Internal
resources to a specific research activity. The technologies Include bio-
logical, chemical/physical, and thermal technologies for both soil and
groundwater. With few exceptions, they are 1n-s1tu or on-site tech-
nologies; and they are not containment technologies.
The study was approved 1n November 1986 and will last for five
years; 1t includes nine countries. Projects are selected and their status
monitored during an annual administrative meeting held 1n the Spring. (The
next administrative meeting will be held 1n Copenhagen, 8-10 May 1989.)
There are currently a total of 22 NATO/CCMS Pilot Study projects.
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Proceedings Exhibit 1
AGENDA
NATO/CCMS PILOT STUDY
DEMONSTRATION OF REMEDIAL ACTION
TECHNOLOGIES FOR CONTAMINATED LAND
AND GROUNDWATER
7-11 NOVEMBER 1988
National Institute of Public Health
and Environmental Protection (RIVM)
Antonle van Leeuwenhoeklaan 9
3720 BA Bilthoven
The Netherlands
HOST COUNTRY ORGANIZING COMMITTEE
Esther Soczo - RIVM
Merten Hinsenveld - TNO
Herman Bavlnck - VROM
Sjef Staps - RIVM
Josephine Hagenaars - RIVM
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Monday
7 November 1988 Day 1
8.30 - Registration
9.00 - Welcome from host country
o RIVM - N. von Egmond
o VROM - J. Moen
9.30 - Opening remarks by Pilot Countries
9.50 - Introduction of attendees
10.10 - Break
10.30 - Remarks of Organizing Committee - M. Hlnsenveld
10.40 - Short presentation of the Netherlands
Integrated Soil Research Program
11.00 - Tour de Table
o Canada - J. Schmidt
o Denmark - S. Vedby
o Federal Republic of Germany - G. Kiihnel
o France - R. Goubler
o Italy - A. di Domenico
o Norway - M. Helle
o United Kingdom - P. Bardos
o United States - W. Kovallck
12.00 - Lunch
13.15 - Presentation of Solidification Projects
o Sol1d1f1at1on Evaluation - France - 4
sites (Final report*) - R. Goubler
o Hazcon process - United States -
Douglasvllle (Final report*) - P. de Percln
14.45 - Break
15.05 - Invited Speakers from the European Economic
Community
o Euseblo Murlllo Matllla
o Hans-Joach1m Stletzel
16.05 - Introduction to RIVM
~Thirty minutes per presentation followed by 15 minutes discussion.
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Tuesday
8 November 1988 Day 2
9.00 - Presentation of Microbial Treatment Projects
o Aerobic/Anaerobic In-Situ Degradation
Denmark - Skrydstrup (Interim report+)
- S. Vedby
o In-Situ B1orestorat1on - The Netherlands
- Asten (Interim report*) - R. Van de Berg
o In-Situ Enhanced Aerobic Restoration -
United States - Eglin A1r Force Base
(Final report*) - D. Downey
10.25 - Break
10.45 - Presentation of Pump and and Treatment Projects
o Pump and Treat Groundwater - Canada
V1lle Mercier (Interim report"*") - R.
Martel and J. Schmidt
o Biological Pretreatment of Groundwater -
The Netherlands - Bunchoten (Final
report*) - L. Urllngs
o Groundwater Treatment - France - Lot
River (Interim Report4-) - P. Boisseau
12.10 - Departure to Soestdulnen for Lunch
13.30 - Visit to the Soil Cleaning Demonstration
Project at Soestdulnen
14.50 - Presentation of Son Treatment by Extraction
Projects
o In-situ Extraction - The Netherlands -
Soestdulnen (Final report*) - L. Urllngs
o Vacuum Extraction - United States -
Verona (Final report*) - VI. Kovalick
16.10 - Presentation of Volatilization Project
o Radio Frequency Volatlzatlon - United
States - Volk Air Field (Interim report+)
- D. Downey
16.30 - NATO Expert Guest Speakers
o Karel Luyben - The Netherlands
o Guus Annokkee - The Netherlands
"Biological treatment of contaminated
soil and groundwater"
+F1fteen minutes per presentation followed by 5 minutes discussion.
*Thirty minutes per presentation followed by 15 minutes discussion.
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Wednesday
9 November 1988 Day 3
9.00 - Presentation of Thermal Treatment Projects
o Rotary K11n Incineration, Indirect
heatlng/pyrolysls - The Federal
Republic of Germany - Unna Boenen
(Interim report+) - J. Ronge
o Infra-red Incineration - United States -
Peak 011 (Final report*) - F. Stroud
o Soil Roasting - Japan - Tokyo (Final
report) - speaker could not attend
but sent paper
10.10 - Presentations by Continuing Fellows
o W. Pettyjohn - United States
o S. Staps - The Netherlands
10.55 - Break
11.15 - NATO Invited Expert Speaker
o Gregory Ondlch - United States
"The Use of Innovative Treatment
Technologies 1n Remediating Hazardous
Waste Sites"
11.45 - NATO Invited Expert Speaker
o Ronald Probsteln - United States
"Electroosmosls for In-S1tu
Hazardous Waste Site Remediation"
12.30 - Lunch
13.30 - Presentation of Soil Treatment by Extraction
Projects
o Vibration; Harbauer - The Federal
Republic of Germany - Plntsch 011
(Final report*) - M. Nels
o High Pressure Soil Washing - The Federal
Republic of Germany - Goldbeck-Haus
(Interim report'1') - W. Sondermann
14.35 - Presentations by Continuing Fellows
o J. Gosset - United States
o R. Bell - United Kingdom
15.20 - Break
15.30 - Visit of the Province of Utrecht, Including
clean-up of Industrial site "CINDU"
"•"Fifteen minutes per presentation followed by 5 minutes discussion.
*Thirty minutes per presentation followed by 15 minutes discussion.
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Thursday
10 November 1988 Day 4
9.00 - Presentation of Chemical Treatment Project
o K-PEG Technology; Soil and liquids -
United States - Indiana, New York
(Interim report-1") - W. Kovalick
9.20 - Presentations by new NATO/CCMS Fellows
o R. Apak - Turkey
o A. Turkman - Turkey
o A. d1 Domenico - Italy
o T. Dahl - United States
o M. Smith - United Kingdom
12.00 - Summary comments
12.30 - Lunch
13.30 - Visit to soil treatment plants
o Thermal plant of Ecotechnick at Utrecht
+Fifteen minutes per presentation followed by 5 minutes discussion.
Friday
11 November 1988 Day 5
9.00 - Visit to research projects (pilot-plant
scale)
o Landfarming at TN0 Delft
o Bloreactor at Delft University of
Technology
12.30 - Lunch
15.00 - Arrival at the hotel
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The exchange of Information on developing technologies is the prime
goal of this study. The presentation and discussion of in-depth interim
and final reports on demonstration projects is one of its key aspects.
These reports are presented at the annual international conference held in
the fall of each year and contain both technical and cost data. (The next
international conference will be held 1n Canada in November 1989.)
The need to share the Pilot Study Information with the technical and
scientific community 1s also key. The Information resulting from the Pilot
Study 1s assembled 1n Proceedings following each international meeting.
Information is also submitted to International technical journals as data
warrants. A final report on the entire study will be published by NATO at
the conclusion of the Pilot Study.
NATO/CCMS Fellows have been Identified from participating countries.
They provide additional technical resources to the Pilot Study 1n their
expertise, Information resulting from their projects, and access they may
have to Information about other emerging remedial technologies. The
Fellows' involvement 1n the Pilot Study 1s primarily through their atten-
dance and participation 1n the annual international meetings. There are
currently 10 Fellows Involved with the Study.
Report Organization
This report has three sections. The first 1s a report of the "tour
de table" during which country representatives discussed recent develop-
ments 1n their national regulatory and research and development programs.
Reports on specific projects 1n this Pilot Study are second and form the
bulk of the proceedings. The reports Include both Interim and final pro-
ject reports, and are arranged 1n the order in which they were Included on
the program. Presentations by NATO/CCMS Fellows and by Guest Speakers, as
well as a paper associated with one of the site visits are Included 1n the
Appendices, the third and last section.
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Recent Developments in
National Programs
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TOUR DE TABLE - CANADA
Responsibility for the management of hazardous wastes and groundwater belongs
primarily to the ten provinces in Canada, and not the federal government. The
exceptions are federal facilities and federal lands such as airports, Canadian
Forces Bases and National Parks and the Yukon and Northwest Territories. The
federal government does, however, also have responsibilities for transboundary
waters such as the Great Lakes.
At the National level, the Canadian Council of Resource and Environment
Ministers (CCREM) has been used as a mechanism to foster cooperation and
cooperative action amongst the two levels of government. Two relevant
committees are those concerned with waste management and Research.
In terms of hazardous wastes, I reported previously on efforts to compile a
national inventory of sites. This activity is ongoing and a recent update by
the Province of Ontario is attached (Appendix A) . In terms of remedial
efforts generally, these have been addressed on a case by case basis.
Remedial actions have been taken at a number of coal gasification sites in
Ontario and a brief note on one site within the City of Waterloo is appended
(B) .
At the present time, there is nothing in Canada equivalent to the Superfund
Program in the United States, although it is being actively pursued under the
CCREM umbrella. The Province of Ontario has however, established a "security
fund" of the order of $10,000,000 dollars per year, to undertake remedial
actions. In the other provinces, each site is treated on a case by case basis
and funded accordingly. Because of the large costs involved in cleanup, a
cautious, conservative approach to remediation has been taken.
A second area is soil contamination caused primarily by industrial activities.
One focus has been on contaminated sites where the industry is still active -
such as the cleanup of the Sydney, Nova Scotia Tar Ponds. The contamination
of an estuary, soil and groundwater was created by a steel mill which began
operation about 70 years ago and is still operating. Remedial measures will
be put in place over a period of about ten years at a cost estimated at
$50,000,000 dollars. Contracts have been awarded for project management and
other preliminary activities.
The second focus is that of "decommissioning of old industrial sites" where
the original industrial plant has ceased operation and the site is to be
reclaimed. In 1985, "A Guide to the Environmental Aspects of Decommissioning
Industrial Sites" was prepared for Environment Canada and distributed widely.
Subsequently, under the direction of a Decommissioning Steering Committee,
consisting of representatives from the federal government, three provincial
governments and three industry associations, two national workshops were held
to discuss concerns and recommend a course of action. Nine recommendations
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were made - but the No. 1 priority identified was a need to develop a
methodology for establishing cleanup criteria. Although strategies to define
cleanup criteria for contaminated soil had been developed by three provinces,
there was no overall consistency between them nor a national consensus and
thus the recommendation to develop a methodology.
The major activity that is ongoing in this regard is to develop a framework
based on "expert system" technology to develop site specific criteria for "how
clean is clean". This effort is expected to be completed in the near future.
What is being developed with Canadian funding and funds from USEPA is a model
called AERIS - "Aid for Evaluating the Redevelopment of Industrial Sites".
In spite of the lack of a national consensus on cleanup criteria, full scale
remedial actions for soil cleanup have been initiated and completed at a
number of sites in Canada, notably two oil refineries and one sour gas plant.
Groundwater Contamination
Environment Canada late last year adopted a groundwater "action plan" -
calling for coordination of federal and provincial activities in groundwater
research and operational concerns. Regrettably, no significant new funding
was provided to accelerate or expand activities - but rather specific
activities were identified in the Regions and Headquarters, generally of an
investigative and R D & D nature.
Canada's major cleanup project is at Ville Mercier, Quebec, which is our
NATO/CCMS Demonstration project. A second major cleanup expected to be
implemented in the near future is at a former waste dump on federal lands.
There are numerous examples of smaller cleanups related primarily to leaking
underground storage tanks which have held gasoline. In many cases, vapour
extraction is being employed.
Significant R&D efforts
A major workshop is being convened by Environment Canada from 28 November to
December 1 to identify R&DD needs for Remediation Technologies for Treating
Hydrocarbon Contaminated Soil and Groundwater for the petroleum sector - and
encourage technology transfer activities for existing demonstrated remedial
technologies, as well as preventive technologies. Experts from Canada, the US
and Europe have been invited to participate. A definitive report is expected
early in 1989.
In another promising development, $50,000,000 has been identified for clean up
activities in the Great Lakes Basin. The development of measures related to
the decontamination of groundwater is one of 5 areas identified - suggesting
that perhaps $2 million dollars per year will be available for this activity.
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Most of this money will likely be used for investigative and pilot scale
remedial activities, but by itself will not pay for any substantive amount of
cleanup. The emphasis in Ontario is that the responsible
individual/organization should pay for the cleanup.
In conclusion, we are making progress in Canada in these areas, developing our
own areas of expertise and learning substantially from the experience of other
countries, particularly those represented at this forum.
December 15, 1988
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APPENDIX A
Province of Ontario - New Initiatives in Waste Management: Waste Site
Investigation and Remediation - U. Sibul
The Ministry of the Environment (MOE) has conducted extensive inventories of
closed and active waste disposal sites in the Province since 1979. As a
result, the Ministry has records of approximately 3,850 closed and active
waste disposal sites in Ontario. The majority of these sites have not posed
contamination problems, and only a very small percentage have been shown to
contaminate domestic ground water supplies or to have had measurable impacts
on surface water quality. However, to rule out any future impacts, the MOE
has embarked on a comprehensive, long-term corporate program to review the
contamination potential of all known waste disposal sites. As a significant
step in this review, a waste site classification system has been developed to
allow a phasing of in-house data review and investigations for all sites.
Those sites that have the potential to inpact human health are being
considered first, followed by those sites that may have an impact on the
environment only. It is the ultimate intent of the Ministry to have
sufficient data on hand for active and closed waste disposal sites to be able
to determine if any contamination is present, and to have sufficient
monitoring in place to anticipate off-site impacts before they might occur.
The comprehensive program, started in 1985, consists of three main phases:
1) Maintenance of a complete and accurate file on all active and closed
sites;
2) Waste site classification regarding potential impact on the environment
and human health;
3) Investigation and impact assessment of high priority sites;
identification of required remedial actions.
Although the majority of the work associated with Phase I is complete,
determination of accurate locations of sites will be ongoing routinely for
years to come. Similarly, the Phase 2 classification of old waste disposal
sites will be a continuous task as more accurate data become available, and
the investigation of sites in Phase 3 will require many years to complete in
order to determine the impact potential of a large number of the old sites.
After the discovery of coal tar in 1986 at a number of locations in Ontario
(Waterloo, Ottawa, Toronto, Port Stanley, etc.), the MOE conducted an
inventory of municipal coal gasification plant waste sites throughout the
Province. This inventory was completed in April, 1987 and it identified 41
sites in 36 municipalities. These sites are being handled as a group distinct
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from the old waste sites described previously because of the hazardous nature
of the waste and the urgency to define any possible problems associated with
these sites.
Of the 41 sites, 11 were originally identified in 1987 as having a high
potential to impact the environment, 6 were in the medium category, and 24
were deemed to present a low potential for impact. These estimates of
potential impact were based on limited existing or historic data and
consequently the MOE has initiated further investigative work at many of the
sites to determine more precisely the existence and location of coal tar waste
on the plant sites, and possible impacts at off-site locations. This work
will span approximately three years at a cost of about $1.7 million, which
also includes an inventory of coal tar waste sites associated with industrial
processes. The results of this inventory will be known later this year.
Abatement of problems at old waste disposal sites is an ongoing activity as
problems are uncovered or identified through the Ministry's investigations.
MOE's prime role in these activities is to ensure that the necessary studies
and abatement actions are undertaken by the site owners. In case of critical
situations, or where the operators of old sites cannot be located, the
Ministry may undertake to fund the necessary investigations and remedial
actions. The Security Fund, established in 1985, is one source for funding
these initiatives and at the present time the fund allows appropriate
hydrogeologic investigations to be conducted in areas where serious
contamination is anticipated.
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COAL TAR REMEDIAL ACTIONS - ONTARIO
CRITERIA: Likely impact on or off-site
- SITES COMPLETED/ONGOING
- City of Waterloo - $2M
- Rideau River Site (Ottawa) - $15M
- Chippawa Creek - SIM
- Toronto (2)
- Library - $1M
- 26 Berkley - $2.5M
- Lees Avenue (Ottawa) - Ongoing
- Port Stanley - Ongoing
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APPENDIX B
REMEDIATION OF COAL GASIFICATION HASTES, WATERLOO, ONTARIO
- Courtesy of CANVIRO Consultants Ltd. -
BACKGROUND - coal tar residue in 2 large tanks was discovered
in Waterloo's City Centre during excavation for
an office building.
- site of a former coal gasification plant (of
which there are over 40 such sites in Ontario
alone).
REMEDIAL ACTIVITIES
(1) - hydrogeological study.
over 20 000 m1 of coal tar contaminated material
required excavation.
(2) on site temporary soil storage area created.
(3) - 3 000 m' of the contaminated material contained
high oil and water content and required on site
treatment with fly ash and lime to stabilize the
material prior to disposal in a secure hazardous
waste landfill site.
(4) - the remaining 17,000 m* of material was disposed
of at the local municipal landfill.
(5) - fly ash storage area created.
(6) - over 75 000 gals of contaminated water from
excavation were treated on site by a mobile
facility which provided oil separation, rapid
sand filtration, GAC and H202 polishing prior to
discharge to the municipal sewer.
(7) - extensive air monitoring conducted.
December 6, 1988
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NATO/CCMS meeting Bilthoven Netherland.
Recent developments in Denmark
With reference to the last meeting in Hamburg, a committee under
the auspices of NAEP, has been engaged in drafting a new rules
on waste.
Bearing in mind the uncertainty, both in connection with the number
of sites and the cost involved in measures to be taken, the new
rules on waste would afford at least 6-8 billion Dkr., within a
period over 30 years.
Unfortunately the passing of the new rules is put off/delay ontill
next year or later, because of an order of priority on the whole
area of the environment. Several efforts will be put into a so-
called "Water-Environment-Plan" concerning the increasing eutrophication
of the see and all freshwater reservoirs in Denmark. This programme
include also a national groundwater monitoring system in 20 represen-
tative areas. The monitoring systems include micro-organic compounds
from chemicals in the environment for eksampel contaminants from
waste disposal sites.
This delay on the new act of waste results in unchangeble activities
conserning investigations and remedial measures on chemical infected
waste disposal sites.
Activities on chemical waste disposal sites.
In the period from the implementation of the law and till now a
lot of new chemical waste sites have been recorded. In May 1988
the total amount of these sites was 1599 or at least 3 times the
assumptions from 1983. The considerable increase in the number
of sites is due to the fact that the original survey in 1980-82
primarily was conserned with the large-volume disposal sites. To
day the authorities know that industrial sites where chemicals
where handled and disposed can cause conciderable groundwater conta-
mination. In 1982 the industrial sites only constituted 5 •/• of
the recorded sites. This percentage was in 1987 as high as 65 */-.
Investigations are ongoing or have been report on about 120 sites
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and remedial measures are etablish or planed on about 30 sites.
To this number should be ad a large number of sites where voluntary
activities are ongoing.
Concerning remedial actions activities, digging and destruction
on our central treatment plant "Kommunekemi" is the most used tecniques.
Ofcourse the treatment is if necessary combined with groundwater
pumping and - treatment.
However the last two years, an increasing number of more experimental
in-situ and on-site cleening fasilities have been choiced, -the
Skrydstrup case is an example.
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Hazardous Waste Cleanup in the
Federal Republic of Germany
1. Common remarks:
Mrs. Chairman, ladies and gentlemen,
as everybody knows, politics determine the progress in the
development of environmental protection and environmental
resource recovery. The problem of hazardous waste clean-ups
was raised in the political discussion in the years of 1984/
1985 and has been a priority topic in the environmental dis-
cussion since 1986.
The number of actual hazardous waste sites in the Federal
Republic of West Germany is still unknown. At present we have
less than one hundred.
Since 1986 the Lander - we have eleven Lander in the Federal
Republic of Germany - have enforced their efforts to record
the potential hazardous waste sites. Today we've, counted
42.000. potential hazardous waste sites. Several estimates
indicate, that we are going to have about 60.000.
In a second step, when the recording is finished, the Lander
will carry out a preliminary assessments risk assessment and
of course a hazard ranking of all sites.
2. Legal sitation
According to the ^constitution of the Federal Republic of Germany
(Article 80, 84, 30 of the Basic Law) the L8nder habe the respon-
sibility for cleaning up the hazardous waste sites. They have to
bear the costs of the remedial action, if a responsible party
cannot be found or is not able to pay.
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- 2 -
3. Financing
The year 1986 was the highlight in the political discussion about
financing of remedial actions of hazardous waste sites: There was
a demand to establish a federal fund similar to the Super-Fund in
the USA. The discussion took place at all parlamentary levels.
Finally, the majority of the Lander decided in the "Bundesrat" and
the "Umweltministerkonferenz" (Conference of the ministers for the
environment of the Lander) not to have a federal fund, but to
organize a Landerbased organizational and financial system to full-
fill their tasks. Since this decisive year 1986, the Lander have made
intensive efforts to establish modells of how to organize and to
finance the clean ups of hazardous waste sites. Meanwhile four
Lander have finished this part, others are on the way.
Let me return to the recording of potential hazardous waste sites.
Most of the Lander have almost finished the recording and are ready
to begin with the risk assessment and the hazard ranking.
4. The role of the Federal Government
My country has two different approaches to solve the problem of
hazardous waste sites: One objective is to prevent the emergence
of new hazardous waste sites, the other one is to record and to
clean up old hazardous waste sites.
Qur waste law of November 1986 gives us new strong instruments,
first, to reduce the amount of waste by means of avoiding the
generation of waste and by recycling the waste and, second, to
avoid or reduce the amount of hazardous substances in the waste
or to ensure their environmentally compatible management.
In the field of cleaning up old hazardous waste sites, the role
of the Federal Government is limited because of our federal system
and the constitution (Basic Law).
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- 3 -
The Federal Government supports the Lander by means of intensive
research and development of new and modern technologies for
localization and sampling as well as at remedial technologies.
The Federal Government also undertakes big efforts to turn the
outcome of the research projects into pilot projects.
In an another field of cooperation the Federal Government works
very closely together with the Lander and this is the field of
expert groups. Meanwhile there are five of those groups.
The most important one right now is the LAGA-Group, whose goal
it is, to make recommendations to all Lander of how recording,
sampling and remedial action schould be organized. An other expert
group tries to establish a uniform risk assessment system to be
recommended to the Lander as well.
Although we don't have a responsiblity for cleaning up hazardous
waste sites, there are meanwhile some financial sources to support
the Lander and communities.
1. A 6-bi11ion-DM-programm (1988-1990) for urban bulding and
construction as a common programm from the Federal Government,
the Lander and the communities makes it possible to finance
remedial actions under certain conditions.
2. With an other program - the main goal of which is to support
the regional economic structure - the clean up of hazardous
waste sites can be supported too, if the cleaned site can
be uses as a new industrial area.
3. A special program of the Federal Government was established
in 1988 to support especially the heavy industry areas in West
Germany.
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- 4 -
All federal programs I have mentioned are no direct support for
the clean up-activities of the Lander and Communities.
Last but not least the Federal Government is very interested
in enhancing international cooperation to echange the results
from research programs and practical experience. The NATO-CCMS-
Study-Group, the TNO-Congress and the echange programm between
the United States and West-Germany are good examples for further
international cooperation.
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Departement Industrie
RG/BP/OTAN/2
Angers, le 2^- (0. Ft
NATO CCMS INTERNATIONAL MEETING
BILTHOVEN (N.L.) nov. 7-1*88
FRENCH SITUATION IN MATTER OF CONTAMINATED SITES
During the past two years the french national authorities dealing with
the problem of old polluting dumps and contaminated sites realized that the
french situation needed a new clarification. Therefore, new action of site
registration has been initiated through two main ways :
1 - Directives given to local authorities responsible for the control of
Classified Installations for the Environmental Protection (including
industrial and municipal landfills) emphasize the priority of
contaminated sites inventories.
2 - Mission given to the National Agency for Waste Recovery and
Disposal -ANRED- to develop new inventories actions at natibnal
and/or regional levels. These actions are under development and will
go further in 1988.
In the middle of this year, the first results of these actions have been
gathered and synthetlzed.
The investigation carried out by ANRED has produced about 500 sites,
mainly resulting of the enquiries of municipalities and among which few have
been proven to be really contaminated, most of them having to be evaluated.
Although this evaluation Is not performed at the present time, the first
estimates resulting from a first consideration of the sites mentionned by
municipalities give the idea that few of them are truly hazardous.
The local authorities have mentionned a total of about 80 new
contaminated sites and, if all sources of information are gathered (local
authorities and ANRED) it is about 100 new serious cases which have been
revealed.
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In addition, Gaz de France, the national gas board has given a list of
more than 500 towns where gazworKs plants were in operation until the sixties.
An investigation will be carried out on a sample of these sites in .order to
give an evaluation of their situation on the point of view of their
contamination.
On the other hand, the actions of inventory will go on, local
authorities oeeing still requested to participate and ANRED performing
technical and historical surveys of polluting industries in order to clear the
method of disposal they used in the past.
In addition it becomes more and more clear to the authorities and to
industrial parties that this question of contaminated sites is important and
often difficult to solve :
- the cost of rehabilitation which has been estimated at about
1 million FF per site according to the consideration of the first list
of one hundred registered sites, has much increased. It is now
evaluated at an average of 3 to 5 millions FF per site and in some
cases much more : the most heavily contaminated site known at the
prestent time will cost more than 100 millions FF.
- more attention to problems of contamination is paid by authorities in
charge of land management and owners or buyers of abandonned
industrial sites. This question will be as major topic of the next
national professional conference and exhibition called POLLUTEC to be
held in Lyon in november 1988.
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THE NETHERLANDS INTEGRATED SOIL RESEARCH PROGRAMME:
Fostering Soil Protection with Fundamental and Applied Research
H. Eijsackers, Programme Director
I. Introduction
Environmental issues receive high priority in The Netherlands.
During the last decade soil pollution has been given growing atten-
tion. The prevention of soil pollution and the remediation of
polluted soil are aspects of the new environmental policy. This
policy must be based on sound and comprehensive scientific knowledge.
The Netherlands Integrated Soil Research Programme ("Speerpunt-
programma Bodemonderzoek") was set up precisely to provide this
knowledge by the ministries of Education and Science; Housing,
Physical Planning and Environment; Agriculture and Fisheries;
Transport, Waterways and Public Works. Such unprecedented coopera-
tion among four ministries illustrates the wide scope of the problem
in The Netherlands.
The alms of the Programme, which was approved by Parliament 1n 1986,
are to stimulate research that will contribute to fundamental and
long-term solutions to the problems of soil pollution and soil pro-
tection; to Improve the research structure needed for that type of
research; and to underpin government policy. The programme covers
terrestrial soils, periodically Inundated soils and aquatic soils.
It seeks to safeguard the functions of these soils for the future and
has two main research thrusts:
Basic soil research: to provide more information on soil quali-
ties, processes and parameters,
Soil protection techniques: to yield methods of preventing and
alleviating soil pollution.
The research on protection techniques will draw on the results of the
basic research. It aims to yield practical methods for soil sanita-
tion and for the prevention of future soil pollution. Subsequent
policy formulation will draw on these methods.
2. Funding and programme implementation
The Programme is funded by the four Dutch ministries that Initiated
1t. A steering committee formed from representatives of these
ministries decides upon the allocation of funds.
Two committees are responsible for implementing the Programme:
The Programme Committee for Basic Soil Research (PCBB)
The Programme Committee for the Development of Soil Protection
Techniques (PCTB).
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A sum of NLG 56 million has been granted to the Programme. The PCBB
has been allocated almost two-thirds of this sum (NLG 38 million),
leaving the PCTB with NLG 18 million.
Although most of the funds will be channelled directly to twelve core
institutes, funds will also be allocated to relevant research proj-
ects elsewhere.
The work of the PCBB and PCTB 1s Integrated and coordinated by a
Programme Office, whose full-time director works closely with the
committees' chairmen and secretaries.
3. Basic soil research
Gaps 1n knowledge revealed by scrutinizing the data collected to date
will provide the starting points for this part of the programme. The
natural starting point of basic research 1s to develop theories and
synthesize data, with the aim of being able to explain (and hence
predict) the effects of soil pollution and degradation. Indeed, this
1s the first of the three broad themes that the PCBB research topics
have been grouped under.
Theme A: Models for integrating data.
The mathematical modeling of effects of soil deterioration and soil
pollution, testing these against ecological theories, and applying
these 1n interdisciplinary risk evaluation are crucially Important,
because they enable the vast and varied amounts of data to be
Integrated so that soil problems can be solved.
Next, research 1s needed to provide dose-effect data e.g. on toxic
action of compounds or adverse effects of treatments. This 1s
grouped under theme B.
Theme B: The effects of pollution and soil degradation.
Inventorying research Is needed to obtain an overview of the soil
degradation and pollution currently threatening the functioning of
the soil ecosystem, the soil quality, and the quality of surface
water and groundwater. Furthermore, appropriate ecotoxicological
test systems have to be developed.
In order to get a proper research base to understand the (black-box)
data resulting from theme B, basic research 1s needed.
Theme C: Basic strategic research on the soil's vulnerability and
Its recovery potential.
This theme encompasses fundamental but strategically oriented
research that will be directed to solving specific practical problems
of soil degradation and pollution. The research topics under this
theme have been deliberately synthesized from several disciplines to
promote the Integration of biological, physical and chemical
findings.
-28-
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The problems that will be investigated under these three themes are
complex (see Table 1), consisting as they do of an Intermeshing of
physics, chemistry and biology. Initially, they must be tackled by a
monodisclplinary approach. Later multidisclplinary research will be
necessary. The cooperation required for the latter will have to be
carefully planned. A special "integration project" has been started
recently.
Table 1.
BREAKDOWN OF PCBB
RESEARCH THEMES
Each of the three
major PCBB research
themes has been sub-
divided into more or
less homogeneous
interdisciplinary
research topics.
Theme A (Theories
and models):
- the development of
techniques for risk
evaluation
- the development of
models to predict
the effects of
emissions on the
soil
- the development of
sampling strategies
and data-handling
systems for soil
quality
Theme B (soil pol-
lution and degra-
dation) :
- the development of eco-
toxlcological tests
- studies of the effects
of soil pollution on
specific organisms and
populations of organisms
Theme C (Soil vulnera-
bility and recovery):
Applied research:
- characterization of
the variability of
abiotic and blotic
soil parameters in
space and time
- formation and deter-
ioration of soil
structure
- transport of sub-
stances in the soil
and the development
of transport models
- speclation and bio-
logical availability
of Inorganic com-
pounds
- kinetics of trans-
formation processes
and the biological
availability of
organic compounds
- interaction of or-
ganisms with soil
interfaces
- adaptation and se-
lection strategies
of natural and
genetically modi-
fied soil organisms
Fundamental research
- adaptations 1n pop-
ulation dynamics of
soil organisms 1n
response to changes
1n the soil environ-
ment
- interactions between
organisms at eco-
system level, and
ecological recovery
- interactions between
plants and organisms
in the rhizosphere
4. Research for soil protection methods
Remediation and prevention are key terms in this component of the
programme. Sanitation Involves measures to alleviate situations that
are potentially environmentally hazardous, such as:
removing/dredging and cleaning/processing polluted soil; 1n situ
cleaning of polluted areas; and isolation of polluted areas.
Prevention involves measures to prevent soil pollution or
deterioration.
-29-
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The aims of this research are therefore much more pragmatic than the
PCBB research and can be summarized as:
Developing application-oriented knowledge and using available
basic knowledge to develop or refine new or existing techniques
for sound soil sanitation and for the prevention of soil pollu-
tion
Stimulating and Improving the existing research facilities so
that questions relating to soil remediation and pollution pre-
vention can be answered adequately in the future.
In both these alms the maintenance and, where necessary, the rehabi-
litation of the multifunctionality of the soil are central.
In order to assess the qualitative and quantitative aspects of the
pollution of specific sites and the remediation of these sites,
research under theme D has been developed.
Theme D: Assessing the efficacy of measures for soil sanitation and
the prevention of soil pollution.
The research within this theme focuses on the identification of soil
pollution problems; the options available to tackle them; and the
procedures for assessing polluted sites.
Further research 1s needed for the development of sanitation and pre-
vention methods and techniques. These are summarized in theme E.
Theme E: Sanitation methods and measures to prevent soil pollution.
As a complement to theme 0, research 1s needed on refining and
augmenting clean-up techniques and prevention strategies. Problems
within theme D and E are diverse here too, as can be seen from Table
2.
In order to optimize transfer of research data to policy and to apply
data for different policy purposes, a special Integration project has
been started. Within this project methods will be developed which
analyze policy needs and match these with the different research
fields.
Starting from environmental policy the five research themes can be
arranged in a logical order (figure 1).
In a similar way research projects can be arranged in 'research
trains' beginning with basic research and using the resulting data
for applied research projects. A number of these 'trains' have been
sketched in Table 3, using the topics given in Tables 1 and 2.
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Table 2.
BREAKDOWN OF PCTB
RESEARCH
Theme D (Efficacy
of sanitation; pre-
vention of pollution):
- Identifying, mon-
itoring and con-
trolling potentially
dangerous situations
- assessing the situ-
ation and choosing
methods of sanita-
tion and isolation
- evaluating techniques
for cleaning, pro-
cessing and Isolating
polluted soil
- proposing standards
(permitted levels)
for certain sub-
stances 1n treated
soil, based on risk
assessment studies
Theme E (Developing sani-
tation and prevention
methods)
Sanitation
- making thermal and ex-
traction applicable for
more substances and more
types of soil (clay,
peat, aquatic soils)
- developing the new field
of blotechnologlcal tech-
niques (for terrestrial
and aquatic soils)
- expanding the range of
separation techniques.
(These are particularly
suitable for aquatic
soils.)
- exploring the potential
of 1n situ cleaning (so
far only applied for
cleaning groundwater and
certain forcibly aerated
soils)
Prevention
- studying the behav-
iour of substances
1n Isolated contam-
inated soil
- ascertaining the
applicability of
civil engineering
and geohydrologlcal
techniques of en-
vironmental problems
Figure 1: Logical arrangement of basic soil research and soil pro-
tection research within The Netherlands Integrated Soil Research
Programme.
ENVIRONMENTAL POLICY
Theme A:
Ecological Theory
Data Synthesis
Theme D:
Assessment of
Remediation Strategies
Theme B:
Ecotox1co1og1cal
Tests
Theme E:
Sanitation and
Isolation Methods
Theme C:
Basic Research
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Table 3: Examples of 'research trains' transferring basic research data
through applied research to sanitation techniques.
Problem:
Clean-up of
polluted soil
Type
Basic research
Adaptation and selection
strategies of natural and
genetlcal modified soil
organisms (C7)
Interaction of organisms
with soil Interfaces (C6)
Interactions at eco-
system level and
ecological recovery
(C8, 9, 10)
Variability of (a)blo-
ttc soil parameters In
space and time (CI)
Formation and deter-
ioration of soil
structure (C2)
Development of simp-
Hng strategies and
data-handling syttems
(Al.2)
Development of pre-
dictive models for
soil emission (C3)
to
plied research
Kinetics of transforma-
tion processes and the
biological availability
of organic compounds (CS)
Development of eco-
toxlcologlcal tests
(B)
Speclatlon and bio-
logical availability
of (In)organlc com-
pounds (C4)
Soil protection
'research
Btotechnotoglcal sani-
tation techniques (E2)
Studying the behaviour
of substances In Iso-
lated contaminated
soil (E5, 7)
Development of Iso-
lation techniques
(E5, 7)
Development of tech-
niques for risk
evaluation (D2, 3)
^Assessment/Pol1cy
Implications
Assessment of remed-
iation strategies
(D)
Efficacy of sanita-
tion (D)
By drafting compilation reports in which summaries are given of the
results of the projects under these topics, data from the various
disciplines can be integrated. As a further Illustration, a flow
scheme 1s given of the research to be used In developing a policy on
the Infiltration of river water to obtain drinking water (Figure 2).
In The Netherlands over 50% of the drinking water originates from
infiltrated surface water. Because of the pollutants present 1n the
water and sediments of the river Rhine and Meeuse, the application of
river water have to be assessed very quickly.
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Figure 2: Flow scheme of applied and basic research to underpin policy on
river water infiltration.
interaction or soil microorganisms
with soil interfaces
Microbial degradation of adsorbed
compounds
Role of threshold concentrations
in microbial degradation of organic
compounds
Mechanisms of reductive dechlori-
nation of chlorinated organic
compounds 1n anaerobic bacteria
Adaptation and selection strategies
of natural and genetically modified
soil bacteria
Development of Dioreactors
for the clean-up of contam-
inated groundwater
Modelling of microbial degra-
dation of chlorinated organic
compounds in the soil
Themes A and E
infiltrate polluted river water
to prepare drinking water?
- Is Infiltration an effective
means to remove pollutants?
- Lowest concentration which
can be reached?
- Conditions favouring bio-
degradation?
- Is the functionality of the
soil (ecosystem) affected?
- Do alternatives exist (e.g.
use of bioreactors)?
Theme C
Themes A and 0
6. International cooperation
International scientific cooperation is one of the percepts of Dutch
science policy. A review of soil research and soil pollution in
other countries has shown that there is scope for mutually beneficial
international collaboration in this area. The Programme will there-
fore seek to promote this aspect.
Further information on The Netherlands Integrated Soil Research
Programme can be obtained from:
- Programme Office:
Dr. H. Eijsackers (programme director)
P.O. Box 37
6700 AA WAGENINGEN
The Netherlands
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NATO/CCMS STUDY ON CONTAMINATED LAND AND GROUNDWATER.
TOUR DE TABLE
THE SITUATION IN NORWAY.
For many years we have heard about the great environmental
treats from old chemical dumps in other countries, and we asked
ourselves: do we have such problems in Norway? For many years
the answer was no.
One of the reasons for this answer was that we had no problems
with drinking water which was polluted by chemical dumps. Most
of the industry is located along the coastline, which is 20.000
km long. Any dumping or discharge of hazardous waste from
these enterprises would not affect the drinking water supplies.
Approximately 80 % of the drinking water supplies are surface
water from lakes and rivers. The main problem with these
supplies is pollution from inland industry waste water and
municipal waste water.
Another argument for this answer was that we do not have much
of the heavy chemical industry which is generating these
chemical by-products; the chemical industry mostly imports the
raw materials for their production.
\
On the other side, we do have serious problems with fiords
which is highly polluted from industrial waste.
During the last years some events occured which told that the
situation concerning contaminated soil and ground water was not
so satisfactory as earlier supposed. Cases of contaminated
soil was discovered from old gas works, oil regenerating
plants, wood preserving plants, etc. Therefore a study was
started in 1987 to evaluate methods for registrating old dumps.
The study concluded that inquiry forms sendt to local
gouvernments and industrial plants had to be followed up by
personal inteviewes with sentral persons in the local
gouvernments and in the industry.
In 1988 the inquiries started in two counties. The results are
now available for one county. It is a county with 220.000
inhabitans or about 5 % of the total inhabitans in Norway. 186
dump sites were registrated where 2 were classified as
hazardous waste sites where it was neccesary with remedial
action. These sites were an old oil recovery plant and a
shredder plant for scrap vehicles. 13 of the sites have to be
further investigated and 75 sites have to be investigated if
the area is to be utilised for other purposes. For the rest of
the sites no investigation is regarded neccesary.
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UK Presentation to 'Tour de Table' of National
Delegates at the Second NATO/CCMS Contaminated Land Meeting
Several UK government departments have policy interests in
contaminated land including:
DoE: Dept Environment
MAFF: Ministry of Agriculture Fisheries & Food
DEn: Dept Energy*
DTI: Dept Trade & Industry*.
As far as reclamation/redevelopment of contaminated land is concerned,
activities are co-ordinated by the Interdepartmental Committee on the
Redevelopment of Contaminated Land (ICRCL). The Department of the
Environment has the central co-ordination role in this committee. (*DEn and
DTI are not represented on ICRCL).
The major current environmental contamination issue in the UK is
landfill gas migration. Groundwater pollution does not appear to be a
priority. Reclamation of contaminated industrial sites occurs largely in
response to redevelopment needs and is typically on a short time scale.
There is no programme which provides for sites to be cleaned up for general
environmental reasons.
The usual solutions are removal and landfill of contaminated material
and/or covering contaminated land with uncontaminated material, depending on
end use. Guidance is available from ICRCL publications and the British
Standards Institute Draft Code of Practice DD175 on the identification and
investigation of potentially contaminated sites.
No national inventory of contaminated sites or treatment routes
exists at present because no current policies require this. However, some
information is available from other sources. For example:
1) Recycling Advisory Unit, Warren Spring Laboratory, Stevenage,
2) Environmental Safety Group, Harwell Laboratory - Waste Treatment
Systems,
3) Survey of Contaminated Sites in Wales, available from the Welsh
Office,
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4) Local waste disposal authorities in the UK may compile their own
inventories of hazardous waste sites, for example 'Survey of
Hazardous Waste Sites in Cheshire', available from Cheshire County
Council.
5) Aspinwall & Co Ltd., Shrewsbury, have a commercial database ('Site
File') of all authorized waste treatment and disposal facilities in
Great Britain post 1980, compiled for HM Inspectorate of Pollution,
6) A survey of Landfill Sites for the Energy Technology Support Unit,
Department of Energy, which was reviewed at the Second Landfill and
Anaerobic Digestion Conference Chester October 1988, will be
available from ETSU, Harwell Laboratory in 1989,
7) Department of the Environment Register of Derelict Land (1982)
' currently being updated for reissue in 1989.
All these surveys were compiled for different needs and using
different definitions, for instance "derelict" does not necessarily mean
"contaminated". Consequently, these surveys should not be considered as
comprehensive inventories of contaminated land and treatment routes.
The Department of the Environment wishes to find out what progress
has been made with the NATO/CCMS Contaminated Land Pilot Study, but is not
yet in a position to seek formal involvement. The Dept Trade and Industry
has a central coordination role for recycling technologies and has
identified pollution abatement technology as an important market area in the
future. Methods for cleaning up contaminated are of interest to both
departments.
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Tour de Table Report
- United States -
Site Assessment and Remediation
Under the United States "Superfund" laws [Comprehensive Environmental
Response, Compensation and Liability Law, 1980; and the Superfund Amend-
ments and Reauthorization Act (SARA) 1986], the national inventory of
potential sites has Increased to over 30,000 sites. Of these, 36% are
deemed to require action under the Superfund law and approximately 1,230
are Federal facilities. The National Priorities List of the active sites
to be remediated under SARA has increased to a total of 1,175 sites.
Eighteen sites have been deleted from the List, and 16 additional sites
have long-term remedial action underway (i.e. groundwater pump and treat)
or are 1n the regulatory process for deletion. (Some States also have site
lists which Include sites not included as a Federal priority.)
Approximately 200 emergency stabilization actions took place 1n
fiscal year 1988, at a cost of approximately $100 million. (In addition,
the January 1988 Ashland 011 Spill of 3.8 million gallons was the worst
inland oil spill on record and resulted 1n an effort to tighten up spill
prevention and control regulations.) EPA made decisions on clean up tech-
nologies for 150 operable units (up from 75 the year before) in fiscal year
1988, while engineering design was begun on 100 sites. Remedial action
(i.e. construction) began at 72 sites. Over $500 million of Superfund
Trust Fund money was obligated 1n FY '88 for design and construction; this
was the largest amount ever committed to these purposes 1n a single year.
Exhibit 1 shows treatment technologies selected for FY 1987 sites.
On the enforcement side, the total value of work committed to by
"responsible parties" crossed the $1 billion (US) level with an additional
$340 million (US) worth of work currently 1n cost recovery litigation.
Rulemaking
There have been several major recent developments in rulemaking under
SARA. The proposed National 011 and Hazardous Substances Contingency Plan
(NCP) 1s ready after a two year development period.* The NCP 1s the prin-
cipal framework regulation for the clean up of abandoned sites 1n the U.S.
At over 120 pages, the preamble and regulation define both (1) the organi-
zational arrangements between Federal agencies, State governments, and
responsible parties, and (2) the operational sequence of proposed activi-
ties, from preliminary assessment of sites to actual remediation.
The proposed new Hazard Ranking System has been revised and contains
major changes.* For example, when developing a hazard ranking for a site,
three new aspects will have to be considered; contamination of the food
chain, ecological contamination (rather than only public health), and
actual releases of air pollutants. This revised ranking system 1s being
published as a proposed rule.
*Copies are available from EPA.
-39-
-------
EXHIBIT 1
Summary of FY 1987 ROD Sites Selecting Treatment
Technologies as Components of Source Control Remedies
BIODEGRADATION
(1)
SOIL WASHING/
FLUSHING
(2)
VOLATILIZATION/
AERATION —
(3)
IOTHER m
!(4)
WV'*'*' * *
1
INCINERATION!
(13)1
STABILIZATION/
NEUTRALIZATION
(2)
! SOLIDIFICATION/!
FIXATION
mm
N.UMBER
OF SITES
TYPES i
13
INCINERATION B
7
SOLIDIFICATION/FIXATION I
2
STABIUZATION/NEUTRALJZATION 1
3
VOLATILIZATION/AERATION I
2
SOIL WASHING/FLUSHING 1
1
BIODEGRADATION I
4
OTHER J
-40-
-------
Rules regarding Technical Assistance Grants are also being finalized;
an Interim Rule was published 1n March 1988. These grants have been devel-
oped in response to citizen sensitivity about Superfund clean-up activity
in their neighborhoods. The grants enable local citizen groups to evaluate
the proposed government work. The grants are limited to $50,000 (US); four
sites have already received grants (see Exhibit 2). A manual 1s available
for applying for these grants.
Another Important manual (CERCLA Compliance with Other Environmental
Laws) being developed links the requirements of Federal environmental laws
to clean-up standards at Superfund sites. Exhibit 3 briefly describes this
manual.
A Screening Guide for selecting technologies for cleaning soils and
sludges has also been completed and 1s being distributed at this con-
ference.
A leaching test 1s fundamental to determining whether residues
resulting from treating contaminated sites are themselves regulated as
hazardous wastes 1n the United States. A revised test for defining these
wastes will soon be proposed.
There 1s an upcoming Environmental Protection Agency meeting which
may be of Interest to members of this group. In June 1989, U.S. EPA's
Office of Solid Waste and Emergency Response (OSWER) and Risk Reduction
Engineering Laboratory (RREL) plan to conduct a conference entitled, Forum
on Innovative Hazardous Waste Treatment Technologies: Domestic and
International. The conference will consist of presentations of technical
papers and posters by International and domestic vendors of technologies
for the treatment of waste, sludges, and contaminated soils at uncontrolled
hazardous waste disposal sites. These presentations will focus on perfor-
mance and cost data associated with these technologies.
The purpose of the conference 1s two-fold: to help Introduce prom-
ising International technologies through technical paper and poster presen-
tations, and to showcase results of the U.S. EPA Superfund Innovative
Technology Evaluation (SITE) program technologies 1n addition to other
domestic Innovative technologies. Both are aimed at accelerating the
dissemination of Information on Innovative hazardous waste control tech-
nologies to potential users, contractors, and vendors. For more Infor-
mation, contact Lisa Moore, JACA Corp., 550 Plnetown Road, Fort Washington,
PA 19034.
-41-
-------
EXHIBiT 2
SUPERFUND TECHNICAL ASSISANCE GRANT PROGRAM
REGIONAL STATUS REPORT AS OF 10/17/88
REGION
LETTERS OF
INTENT/
NO OF SITES
PUBLIC
NOTICES
GRANT
APPLICATION^/
NO OF SITES
GRANT
AWARDS/
NO OF SIT]
I
17/10
8
16/6
0
II
18/15
13
4/4
2/2
III
5/5
5
1/1
1/1
IV
6/*
3
1/1
0
V
8/8
2
1/1
1/1
VI
9/9
3
4/3
0
VII
3/2
2
2/1
0
VIII
7/7
6
1/1
0
IX
12/24
4
4/4
0
X
2/2
2
2/2
0
86/78
48
36/24
4/4
Grants to Love Canal Environmental Action Committee Love Canal Site
Fulton Safe Drinking Water Action Committee Fulton Terminals Site NY
Lackawanna Refuge Site PA; and Concerned Citizens of Lake Township
Industrial Excess Landfill Site OH - were signed by 9/30
*lnfo as of 9/15/88
-42-
-------
EXHIBIT 3
October 1988
CBRCLA COMPLIANCE WITH OTHER LAWS MANUAL
VOLUME I/IIs GENERAL PROCEDURES FOR DETERMINING ARARs; RCRA;
CLEAN WATER ACT, SAFE DRINKING WATER ACT, AND GROOND WATER
PROTECTION POLICIES
VGLuriE III: CLEAN AIR ACT, TOXIC SuBSTAiiCisS CONTROL ACT,
RESOURCE PROTECTION; AND OTH&R STATUTE LAWS
BACKGROUND: The manual on CERCLA compliance with othec laws is being
developed to provide guidance to RPMs and OSCs to implement the
CERCLA requirement that onsite remedies comply with applicable or
relevant and appropriate requirements (ARARs) under Federal
environmental laws and promulgated State environmental or facility
siting laws which are more stringent than Federal requirements. The
manual will also address policy issues related to State requirements
and will provide examples of more stringent State requirements.
Volumes I and II of the manual have been consolidated. Chapter
1_ of the manual contains a general overview of the procedures for
identifying ARARs. This chapter contains matrices of chemical-
specific, location-specific, and action-specific "ARARs, which will
eventually cover all relevant Federal environmental statutes. The
matrices are quick-reference charts that can be used to identify
which requirements are potential ARARs to specific site
circumstances. Chapter 1 also outlines the analytic procedure for
determining whether potential ARARs are actually applicable or
relevant and appropriate requirements at a site. Chapter 2 addresses
CERCLA compliance with RCRA ARARs, and focuses on characterizing when
RCRA requirements would be applicable, and issues raised by RCRA
treatment, storage, and disposal requirements. Chapter 3 and 4
provide guidance on compliance with the Clean Water Act and Safe
Drinking Water Act. Chapter 5 addresses ground water protection.
The manual also includes a hypothetical scenario which illustrates
identification and use of ARARs.
Volume III of the manual is being developed separately and
covers the Clean Air Act, the Toxic Substances Control Act, the
Federal Insecticide, Fungicide, and Rodenticide Act, the Low-Level
Radioactive Waste Standards Program, the National Historic
Preservation Act, the Endangered Species Act, the Wild and Scenic
Rivers Act, the Fish and Wildlife Coordination Act, the Coastal Zone
Management Act, the Wilderness Act, the Coastal Barries Act, the
Uranium Mill Tailings Radiation Control Act, and the Surface Mining
Control and Reclamation Act.
STATUS: Volumes I/II is under review by the Office of Management and
Budget (OMB). It is publicly available in draft from the OSWER
directives system. Volume III completed Agency Red Border in
September 1988 and is currently being revised. The State ARARs
chapter is expected to enter Red Border in November 1988.
CONTACT: Marilyn Stone, Policy and Analysis Staff, 202-382-2200
Sandra Panetta, Policy and Analysis Staff, 202-382-2235
(for State ARARs)
-43-
-------
Project Reports
-45-
-------
TYPE OF TREATMENT:
General: Stabilization/Solidification
Specific: Solidification Evaluation
Researcher/Manufacturer: EIF Ecologlc and Petrifix of Tredi Cy
FORMER USE/PROBLEM: Petroleum refinery wastes
Agricultural/chemical manufacturing
Tannery
LOCATION/COUNTRY: France
EIF Ecologlc process sites
- Marais de Ponteau
- Bourron-Marlotte
Petrifix sites
- Nesles
- Bel lay
CONTAMINANT(S): Acid, tars, heavy metals
MEDIUM OF CONTAMINATION: Lagoons
STATUS AS A NATO/CCMS
STUDY PROJECT:
Proposed: 4/88
Accepted: 4/88
Interim Report(s):
Expected Completion Date:
Final Presentation: 11/88
-47-
-------
Ag ENCE NATIONALE POUR LA RECUPERATION E.T L'ElIMINATION DES CACHETS
Dipartement INDUSTRIE
RG/BP/tFB/OTflN/1
N0VEM3RE 1988
EVALUATION OF SOLIDIFICATION-STABILIZATION PROCESSES
I - OBJECTIVES OF THE PROJECT
The objective of the present study Is to evaluate, some years after
their application in France, for the treatment of different types of
contaminated sites, the efficiency of solidification stabilization techniques.
II - SAMPLING AH) ANALYSIS PROGRAMS
1 - Sampling
In order to get significant but rather simple evaluation of the treated
sites, it was decided to carry out sampling procedure oy digging trenches in
the treated material by using a backhoe. This method was prefered to drilled
boreholes because it is easy to carry out and moreover it allows easy visual
observations and can give wide sections showing the treated material, its
contacts with the surrounding soil and possible heterogeneousnesses.
For every site, three sanpling trenches-were realized and for every
trench three sanples of three kilograms of material were taken : one of the
treated material from the upper layer of the treated section ; one of the
treated material from the middle layer, and one from the ground material
located under the treated zone. The upper sample may be considered as
representative of the treated material in contact with biosphere conditions :
freezing, leaching by Infiltrated water, the middle sample may be considered
as representative of the average treated material and lower sample would give
an estimation of possible releases of contaminants from the treated material.
However, on the field, it appeared sometimes that the material underlaying
the¦ treated area remained much or less contaminated by the orlgnal pollutant.
In such cases the corresponding sample was not considered as significant.
-48-
-------
2 - Analysis program
For every site it *as made three average samples conrresponding to the
three sampling levels by mixing the corresponding samples taken on the site.
The specific analysis performed on samples included :
- measuring of physical properties
. water content
. permeability
. compressive strength
- leaching tests
In France, at the present time, there are no specific standardized tests
for the evaluation of contaminated material treated by stabilization-
solidification. However, investigations are now carried out that will propose
such tests within less than one year. Consequently, it was decided :
a) To perform, for every average sample the present leaching test
(called INSA test I applicable to waste material candidate for
landfilling in special industrial waste landfills. The main features
of this test are :
- extraction solvent : demineralized water saturated with C02 and
air - (ph about 5),
- tested material crushed in parts smaller tham 4 mm,
- 100 g of material mixed with 1 liter of extraction solvent,
- extraction of solutionfor analysis after 16 hours of agitation.
This test was chooseh although it is going to be replaced as standard
for waste acceptation in landfills by a similar one excluding the
saturation of solvent extraction by C02 because it has been performed
for samples taken from two of the sites considered in the present
study at the time of their treatment, thus allowing more significant
comparisons. For every sample two successive extractions have been
carried out.
o) In addition, in order to take in account the specific characteristics
of solidification techniques it was decided to perform the new test
which is now prepared to be later standardized for evaluation of
solidified material.
-49-
-------
This test called oedometric pressure leaching test is based on the
use of a pressure per/neater, a section of which is represented on the
following figure.
(£) ©
1 - Sanpie
2 - Cylinder of confinement
3 - Contact resin
4 - Lower baseplate
5 - Upper baseplate
6 - Porous stone
7 - Filler joint
8 - Stud bolts
The test is performed first to give an evaluation of the permeability of
the treated material, then the oedometer is operated for leaching test. The
pressure is adjusted in order to get a discharge of 0.01 cm /s (36 cur /hour).
Successive extractions are carried out and it is possible to add separately
the extracted quantities of every contaminant and to represent their variation
in faction of the quantity of the liquid discharged through the sanpie.
This function is hyperbolic and its interpretation allows the evaluation
of the total quantity of the considered contaminant which can be extracted if
the volume of extraction liquid or the time of extraction was infinite. The
resulting figure will be considered as the maximum extractible quantity of the
considered contaminant (mg/kg).
-50-
-------
Ill
- EVALUATION OPERATIONS
1 - SITE A : MARAIS DE PONTEAU-LAVERA (50 km west of Marseille)
a - Site history and treatment
Old salt marsh on the seaside in which were dumped various
industrial residues of the Lavera petro-chemical plant. About 30 000 m of
wastes (sludges, sedimentsJ had oeen disposed there for more than 15 years
(1955-1974). After a first estimation of the quantities and nature of the
wastes to treat, many possibilities of treatment were tested :
- incineration in an industrial waste incinerator,
- recycling as stocx feed in a cement factory,
- incinerator in a thermal power plant,
- recycling in an oil refinery.
All these treatments were unsuccessful!, mainly because of the
heterogeneity of the material to treat. Consequently, on site treatment by
stabilization-solidification was decided. The treatment operation was carried
out in September and octooer 1978 by EIF ECOLOGIE using a solidification
patented process oased mainly on the use^of lime as reactive agent. The total
amount of material treated was 22 000 m .
Laboratory tests were carried out, involving lixiviation of
samples of treated material agitated during 24 hours in water with a pH of 6.
The analysis gave figures of 3 to 64 mg/1 for COD and total hydrocarbons <0,2
mg/1.
o - Evaluation of efficiency
Sampling operation : The sampling procedure has been carried out
on sept 23, after a rainy night. The site is covered with sandy and graveled
material without vegetation. It is shaped in a slignt dome the top of which is
2 or 3 meters above the sea level. The sampling has been performed according
to the procedure described in chapter II.1. Two ditches have been digged in
the central part of the treated site, for both the vertical section was :
0 - 15 cm : coverage of sand and gravel
15 - 100 cm : treated material, dry and hard, grey in the upper
part and black in the middle ; slignt smell of hydrocarbons. The extracted
black material became rapidly grey after contact with the air.
-51-
-------
A third ditch has been digged at the limit of the treated zone. A
first hole was digged in which black liquid and black soil appeared. According
to the information given by the representatives of the waste generator and of
the local authority who were present during the present sampling operation and
who took part to the treatment realization ten years ago, this might be
considered as water and original untreated material which remained outside the
dikes surrounding the treated area.
The digging was resumed in the direction of the center of the
treated area and the treated material appeared in a shallow hard slice located
at a level clearly above which of the untreated material. Because of the.'
limited thickness of the treated layer it was decided to take only one sample
from this section.
Results of tests and analysis
- Physical characteristics
1 1
1 Sample 1
1 1
1 1
water content
(X)
permeability
(m/s)
compressive 1
(strength) I
kg/cm 1
1
1 1
1 A1 {upper) I
| I
18
-
1
1 A2 (middle)\
i i
17
7.9 10"6
4.7 |
1
1 1
1 A3 (bottom)\
1
21
-
1
1
1
Lixiviation tests
Landfill lixiviation test (figures given in mg/kg except pH,
conductivity, alcalinity)
1 Sample
1 Extrac-
I t ion
1
I pH
1
1
1
Conduct!-1 TOC
vity mS/s\mg/Kg
1
1
COD \Alkalini~
It/ m mol/
1 kg
1
Cu 1
1
1
1
Pb
Cd
Co
va 1 Ni IHC 1
I 1 1
II 1
1 1 1
1 A1
I l
1 2
•1 Total
1
112.7
112.7
1
1
5.6
5.4
1
1
1
1
900
490
1390
28001
20001
43001
1
44 0
400
640
6.21
3.71
9.9\
25
21
46
0.4
0.2
0.6
<0.5
<0.5
<0.5
<0.511.0142, 1
<0.510.81 I 1
-------
Pressure test : maximum releases (long term)
Sairple a21 pH I Conduct!-I TOC I COD lAlkalini-
I \vlty ms/s\mg/kg\ \ty mimol/
II I I I
I I I' I I
112.71 5.6 I1166 I J200I 850
II III
Cd I Cr I Co I VaI Ni I he
I I I I
I I I I
Fe
Cu I Pb
I
I
I >
4.8110.6
I
>1*1 II
0.11|0.06|0.0ai - 11.27
I I I I
>
i
-53-
-------
2 - SITE B : BOURRON MARLOTTE - Seine et Marne (70 km south-east of Paris)
a - Site history and treatment
Ancient sand pit located in BOURRON MARLOTTE at the south eastern
limit of the forest of Fontainebleau which had been used as duirping site until
1971 for the wastes generated by an old refinery pland (mainly acid tars and
filtration residues). The surface of the lagoon was about 4 200 m and the
dumped material had stratified in three main layers :
- upper layer light and viscous
- middle layer made of aqueous liquid
- bottom layer of sticky material
Many analysis of these material were performed, including
lixiviation tests according to the INSA test utilized for the present
investigation. The following table summurizes the results of analysis carried
out before treatment.
Upper layer
(lixiviation)
1200 m
middle layer
1300m
oottorn layer I
(lixiviation)I
1 Ph I
3.5
2.05
2.10 1
I Resistivity 1
7 900
232
232 1
1 COD 1
4 800 mg/kg
1 960 mg/kg
52 000 mg/kgI
1 Sulfates... 1
260 mg/kg
1 829 mg/kg
41 220 mg/kg\
1 Hydrocarbons1
15 mg/kg
20 mg/kg
<0.1 mg/kg \
It was decided to restore the site by using the EIF Ecologie
stabilization process. The treatment was performed during summer 1985 and
about 25 000 tons of contaminated material has been treated.
-54-
-------
o - Evaluation of efficiency
Sampling operation : the sampling operation has been performed on
October 4th in the morning by rainy weather. The treated area has a slight
slope from its southern part besides a surelevated railway to its northern
limit surrounded oy the forest, the site is covered with soil without any
vegetation. Three ditches have been digged, two in the center of the treated
area, one out its western limit. The total thickness of the treated section is
about 6 to 7 meters, the treated material is colored in brown, homogeneous and
compact with a very slight smell of hydrocarbons.
. /
For every ditch, three samples have been taken at the top, in the
middle and under the treated section. However, the sandy soil under the
treated material seemed to be still contaminated by untreated tar and in the
third ditch there was a seepage of liquids from an untreated zone remaining at
the western limit of the dumping pit.
Results of tests and analyses
Physical characteristics
1 Sample \
water content
(%)
permeaDility
(m/s)
compressive 1
strength 1
kg/ttr j
1
1 Bl (upper) 1
33
1
- 1
1
1 B2 (middle)\
24
1.2 10~5
3.8 1
1
1 B3 (bottom)]
31
1
- 1
1
- lixiviatlon tests
Landfill lixiviatlon test (figures given in mg/kg except pH,
conductivity, alcalinity)
Sample
1 Extrac-
1 t Ion
1
1 pH \Conducti-l TOC 1 COD
I Ivity ms/s\mg/kg\
II I I
II II
Alkalini-I
ry mimol/\
kg
Fe
Pb I
Cd \ Nl \
1 1
1 .1
1 1
Bl
1 1
1 2
1 Total
1
1 6.41
1 7.8|
1 1
1 1
1.7
1.6
1 21001 5400
1 12701 3050
1 JJ70I 8450
1 1
15 1
60
75 1
0.6
0.4
1
<0.21
<0.21
<0.21
- 1 - 1
0.31 - 1
0.31 - 1
1 1
B2
(
I 1
1 2
1 Total
1
112.51
lli.il
1 1
1 1
5.3
1.6
1 14401 3500
1 20401 6100
1 34801 9600
1 1
310 1
260
570 I
0.5
0.6
1.1
4.01
4.01
0.41 - I
O.JI - I
0.71 - I
1 1
B3
1 1
1 2
1 Total
1 7.81
1 7.7|
1 1
2.15
1.95
I 29201 7700
I 8981 3600
1 3818\10300
66 1
68
134 1
0.5
0.6
1.1
<0.21
O.JI - I
0.21 - I
0.5| - |
^ S£\&
1
\
I
UeS |-
Z* ) - I
ifciJ
41 'l.fl
AO
111 - \ictti
L
V
f '&?
J !
I IV.
-55-
-------
- Pressure test : maximum releases (long term)
1 Sample B2
1
1
1
1 PH
1
1
1
1 Con- I
1ducti-|
kity 1
1 mS/m |
1 1
TOC
COD
1 Fe
PD | Cd 1 Ni |
1 1 1
1 1 1
1 1 1
1 1 1
1
1
1
1 12.6
1 1
1 5.8 1
1 1
1690
4760
1>0.26
1 1 1
3.26 \> 0.121 - 1
1 1 1
AlKali-\Hc- 5%
nity I i ,
m.mol/ I » ,
kg I • 1
i i
>165 |>£S
1 I »
-56-
-------
3 - SITE C - NESLE - Sonne (100 km north of Paris f J
a - Site history and treatment
During the first national inventory of hazardous dumps carried out
in 1978, contamination of the chalky aquifer oy nitrogen compounds and salts
was pointed ou in the region of NESLE where an industrial dumping site was
found to De at the origin of the pollution. The waste dunping had occured in
pits digged in silty material laying above the chalk.
In order to restore the safety of the site and of its environment,
the firm who generated the wastes and owned the dunping site decided to carry
out its tratment by stabilization-solidification.
The waste consisted mainly of black colored sludges and silty
material. Analysis of leachates indicated COD up to 450 mg/1 iron up to
47 mg/1 amonia up to 80 mg/1 and traces of copper and zinc. The treatment was
performed dy TREDI (Petrifix Process} and a total of about 7 500 tons of
contaminated material has oeen treated beetween mid-october and mid-december
1900.
A control of the mecanical stability of the treated site performed
in october 1981 concluded to a variable resitance to compressive strength,
which was found generaly good or even very good but with weak layers in some
places. These weak parts of the site have been re-treated later.
In 1985 a new construction has oeen built at the south-eastern
limit of the treated site.
o - Evaluation of efficiency
Sampling operation : the sampling operation has been carried out
on october 4th, in the afternoon by rainy wather. The site is rather flat,
covered with lush grass. Three sampling points have been choosen, each
corresponding to one of the ancient lagoons of residues. The two first
sampling points showed a similar log : down to 1,50 meter, coverage of humus
soil, then about 4 meters of treated material which appeared olackish and
crumoly with a rather strong smell (of organics and ammonia).
The third sampling point has oeen located near the newly
constructed ouilding and its section can be described as follows : 0,80 cm of
soii, treated materieal compact and strong down to about 3 meters, then down
to about 5 meters, again crumbly treated material.
For the three points, the sampling operation has been performed
according to the definition given in part II.1.
-57-
-------
Results of tests and analyses
Physical characteristics
1 Sample \
water content
(X)
permeaDility
(m/s)
compressive 1
(strength) |
kg/cm 1
1 CI (upper) I
45
-
I
1 C2 (middle)I
16
3.410'8
/ |
1.1 1
1 C3 (oottom)l
16
-
- |
- Lixiviation tests
Landfill lixiviation test (figures given in mg/kg except pH,
conductivity, alcalinity)
1 Sample
1
1
1 Extrac-
1 c ion
1
1
pH 1Conduct-
ivity Ms/s
1
1
TOC 1
mg/kg |
COD \Alkalini-l
1 ry m mol/|
1 Kg 1
1 1
NH4
Fe 1 Cu 1
1 1
1 1
1 1
Zn I
1
1
1
1 CI
1
1
1 i
1 2
1 Total
7.6| 1.1
7.61 0.57
1
1
411 |
105 |
516 I
10001
2801
12801
1
52 1
31 1
83 1
549
144
693
0.81<0.51
1.0K0.5I
1.81 I
1 i
<0.21
0.51
0.51
1
1
1 C2
1
1
1 1
1 2
1 Total
1
7.81 0.92
7.91 0.49
1
1
61 1
16 I
77 |
1201
601
1801
1
36 1
31 1
67 I
513
108
621
0.81<0.51
0.91<0.51
1.7| |
1 1
0.61
0.51
l.ll
1
1 CJ
1
1
1 i
1 2
1 Total
7.7| 0.94
7.8| 0.41
1
35
9 1
44 I
1J0I
701
2001
71 1
3 1
74 1
522
126
648
0.51 <0.51
0.41 <0.51
0.91 1
0.51
0.91
1.41
-
Pressure test
: maximum releases (long term)
1 Sample C2 1
1 1
1 1
1 1
pH iCon- I
lducti-1
Ivity 1
1 Ms/m |
1 1
TOC 1
1
1
1
1
COD \Alka- 1 NH4 1
\ Unity \ 1
l/n.mol/i 1
1 xg 1 1
1 1 1
Fe 1 Cu
1
1
1
1 Zn |
1 1
1 1
1 1
1 1
1
1
1
1 (
1
1
1 I
8.5 1 0.4 t
1 1
1
60 1
1
1
160 1
1
1 1
65 1 271 I
1 1
1 I 1
5.1 I 0.06 I 0.03 I
1 1 1
1
-58-
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4 - SITE D : BELLAY - Ain (60 km east of Lyon)
a - Site history and treatment
At the end of 1980, the lagoons used for the storage of sludges of
wastewater treatment of a tanning plant were full and it became urgent to
proceed to the disposal of these sludges. However, because pretreatment before
disposal was required by the local authorities in charge of environment
protection.
Analysis performed by the Centre Technique du Cuir (Leder
Technical Center) indicated contents of 8,7 g/kg cromium, 0,475 g/kg sulfide,
0,5 g/kg sulfates and 0,35 X nitrogen.
Treatment operation was carried out by TREDI using its PETRIFIX
patented process beetween april and June 1982 about 9 000 tons have been
treated.
b - Evaluation of efficiency
Sampling operation : the sampling operation has been carried out
on September 30 th by rainy weather. The site where the treated material was
disposed is a low swampy area with lush vegetation. Three ditches have been
digged, the first one at the supposed limit of the treated area presented a
first layer of about 80 cm of humus soil then about 1,20 meter of treated
material under which some material which seemed untreated appeared until the
original soil was reached at a depth of about .2,50 meters.
On that point, two samples were taken : one from the upper part
and one from the middle of the treated material.
For the two other ditches digged in the central part of the
treated area, the section was similar but without the appearance of any
apparently untreated material underneath. Consequently, three sanples were
taken, according to the sampling procedure described in part II.1. Noticeable
smell (mainly ammonia), especially in the first ditch. For the three sections
of sampling the treated material presented a noticeable difference beetween a
first layer (about 15 cm thick) colored in grey and hard and compact and a
second much thicker layer rather crumbly and colored in dark blue.
-59-
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Results of tests and analyses
Physical characteristics
1 1
1 Sample I
1 1
water content
(X)
permeability
(m/s)
compressive 1
(strengtn) \
1 1
1 D1 (upper) I
55
-
I
1 02 (middle)1
1 |
57
-
0.95 *0.1- I
1 03 (bottom)I
1 1
16
-
- |
Lixiviation tests
Landfill lixiviation test (figures given in mg/kg except pH,
conductivity, alcalinity)
1 Sample
1
1
1
Extrac-
tion
pH
Conducti-
vity mS/s
TOC
mg/kg
COD
l4lKaiini-|
Iry mimol/ \
1 kg I
NH41
Fe
Cr
Ca 1
1
1
1
1 '
1 D1
1
1
1
2
Total
7.7
7.8
1.1
0.72
230
161
391
800
220
1020
1 45 I
1 36 1
1 81 I
<1 1
<1 1
0.4
0.5
0.9
0.8
<0.5
0.8
12801
11501
24J0I
1
1
1 02
1
• •
1
2
Total
9.6
8.2
0.82
0.48
1260
260
1520
3200
750
3950
i 16 I
1 9 I
1 24 I
2J4|
27|
2611
0.3
0.6
0.9
0.9
1.1
2.1
560 \
4101
£701
1
1
1 03
1
1
2
Total
7.8
7.9
0.92
0.56
55
31
86
250
150
400
1 86 1
1 37 |
1 123 1
8011
1301
9311
1.4
0.5
1.9
<0.5
<0.5
6201
8501
14701
- Pressure test : maximum releases (long term)
Sample 02
pH iCon-
I dueti-
ki ty
I mS/m
I
I
9.2 I 0.44
I
roc
1200
NH4
COD lAlka- I
I Unity I
lm.mol/1
I Kg I
I I
J f
2680 I 24 I 131.6
Fe
Cr
Ca
0.6
<0.05
315
-60-
-------
Ill - REMARKS AND CONCLUSIONS
Some remarks may De pointed out aoout these investigations
- It appears that some of the sites has apparently not De completely
treated (A,B,D). This may be understood as the necessity to fix a limit to the
treatment, Put this limit seems rather approximative and may left some
significant quantities of untreated material. However this situation results
from the position of the owner of the site and of the authorities responsiole
for the control of the rehabilitation project, it is not representative of the
treatment process itself. As a consequence, it appears that the upper and
bottom samples are probably not always realy representative of the treatment
process efficiency at the limits of the treated layer, therefore our opinion
is that only the middle sample very be considered without douot as
representative of this efficiency.
- With the exception of site B, that has been more recently treated, it
was not possible to find figures representatives of the characteristics of the
initial contaminant material, and when some datas are available, the
evaluation tests performed (specialy leading tests) are not sufficiently
defines to allow a significant comparison with the result of the present
investigation. If we considerer the site B and the results of lixiviation test
it should be Kept in mind that the main part of initial material is comparable
to bottom layer characteristics and the test of this material is comparable to
the first extraction performed on the middle sample of treated material.
- In connection with the previous remarks, it appears that the treatment
performance required oy the responsible of the sites were far from acurately
defines. For example, for sites c and D, the enterprise who carried out the
treatment project indicates that the requirement, of the owners of the sites
were only dealing with the physical stability of the treated sites. From the
present sampling operation it appears clearly that the compact ness and the
mechanical efficency can be adjusted to reach a high level by increasing the
proportion of the reactive agent (and consequently the cost of treatment).
- The evaluation of the efficiency of a treatment of stabilization
solidification relies greatly upon the choice of tests and analysis. The
present study, which is based on the use of two different lixiviation tests
shows a relative uniformity of figures of general parameters of the leachates
like pH and conductivity, for the release of the pressure tests as more
singificant because this test is concerned to give an estimate of the maximum
release on a long term basis.
- Comparaison between the two solidification processes, is not possible
because of the differences of nature and characteristics of the waste that has
been treated. However some systematic differences can be mentionned for the
physical characteristics : water content (generaly higher for Petrifix),
mechanical resistance (higher for EIF), permeability (higher for EIF), and for
the chemincal characteristics of leachates, the pH and alkalinity of which
Lemains high for EIF, as a consequence of the use of line as reactive agent.
-61-
-------
- As a conclusion it 'may be mentionned :
. that a significant evaluation of the efficiency of the
stabilization-solidification treatment of these old contaminated site remains
difficult, mainly because of the lack of knowledge of initial characteristics
of the treated material
. that the results of the present investigation give an evaluation
of the present state of the treated sites and a tentative estimation of their
potential of evolution in the future. As a whole it appears that the treated
sites are presently and will remain in the future in a satisfactory state
according to their use and their environmental condition
. that the present investigation will participate to the efforts
of adjustement of the methods of evaluation of on site efficiency of
stabilization-solidification.
This last point might be one of the most positive of our conclusions and
oe usefull for the future projects of treatment.
-62-
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TYPE OF TREATMENT:
General:
Specific:
Researcher/Manufacturer:
Stabil1zat1on/Sol1d1f1cat1on
Solidification
Hazcon
FORMER USE/PROBLEM: Lagoons, landfarm and spill areas
LOCATION/COUNTRY: Douglasville, Pennsylvania
United States
CONTAMINANT(S): Lead, oil, volatile organics, PCBs
MEDIUM OF CONTAMINATION: Soil
STATUS AS A NATO/CCMS
STUDY PROJECT:
Proposed: 4/88
Accepted: 4/88
Interim Report(s):
Expected Completion Date:
Final Presentation: 11/88
-63-
-------
DESCRIPTION OF EPA SITE DEMONSTRATION
OF THE HAZCON STABILIZATION PROCESS
AT THE DOUGLASSVILLE, PA. SUPERFUND SITE
by
Paul R. de Percin
Superfund Technology Demonstration Division
U.S. Environmental Protection Agency
Cincinnati, Ohio
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
ABSTRACT
One technology field tested under the SITE research program was the
HAZCON stabilization/solidification process. This process treats the
waste by mixing it with portland cement, water (if needed) and Chloranan,
a proprietary chemical. By comparing the chemical and physical
properties of the waste before and after treatment, this field
demonstration developed data on the strength and leaching potential
expected from a range of waste characteristics after stabilization. Six
wastes at the Douglassville, Pa. superfund site, containing up to 25%
organics and 2% lead, were treated and evaluated. The physical strength
(200 to 1500 psi) and durability, i.e., long-term stability, of the
stabilized samples were good. Even in wastes with high levels of
organics (25%), stabilization of lead was very successful. Leaching
results determined that lead concentrations dropped by factors between
100 and 1000 after treatment. Stabilization of organics, however,
achieved mixed results. Leachate concentrations generally did not change
between treated and untreated samples. It could not be determined if
this was a failure of the treatment process or an anomaly of the test
procedure.
INTRODUCTION
In response to the Superfund Amendments and Reauthorization Act of
1986 (SARA), the U.S. Environmental Protection Agency's Offices of
Research and Development (ORD) and Solid Waste and Emergency Response
(OSWER) have established a formal program to accelerate the development,
demonstration, and use of new or innovative technologies as alternatives
-64-
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to current containment systems for hazardous wastes. This new program is
called Superfund Innovative Technology Evaluation or SITE.
The major objectives of the SITE Program are to develop reliable
performance and cost information. One technology, which was demonstrated
at the Douglassville, Pennsylvania Superfund Site, is the HAZCON
proprietary solidification process. This process involves the mixing of
hazardous waste material and cement with a patented nontoxic chemical
called Chloranan. Chloranan is claimed to neutralize the inhibiting
effects that organic contaminants normally have on the hydration of
cement-based materials. For this treatment technology, the wastes are
immobilized and bound by encapsulation into a hardened leach-resistant
concrete-like mass.
The Douglassville, Pa. Superfund Site was selected as the location
for the Demonstration Test because of its high organic and lead
concentrations. This is a 20 hectare (50 acre) rural site of an oil
recovery facility that includes: two large lagoons once filled with oily
sludge, an oily filter cake disposal area, an oil drum storage area, an
area where generated sludge was landfarmed into the soil and the plant
processing area. More than 200,000 cubic meters of soil is contaminated.
FIELD DEMONSTRATION OBJECTIVES
The major objectives of the HAZCON field demonstration were to
determine:
1) The ability of the HAZCON stabilization/solidification
technology to immobilize the site contaminants. These include heavy
metals, oil and grease, volatile and semivolatile organics, and
polychlorinated biphenyls (PCBs).
2) The effectiveness of the technology for treating soils with oil
and grease concentrations between 1 and 25%.
3) The performance and reliability of the process system.
4) The probable long-term stability and integrity of the
stabilized soil or waste.
5) The costs for commercial-scale applications.
In developing the sampling and analysis plan, two major criteria
were identified for judging the success of the HAZCON stabilization
process; integrity of the treated waste and the mobility of the toxic
contaminants. Integrity of the treated waste was evaluated by measuring
the physical properties and observing the microstructure of the hydrated
matrix. Mobility was determined by the leachability of the contaminants
and the permeability of the treated waste.
-65-
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SITE DESCRIPTION
The Douglassville, Pa superfund site is located in a rural setting
surrounded by croplands and light residential and industrial development,
and covers 20 hectares (Figure 1). About 3 hectares (7 acres) of the
site were formerly used as two lagoons, Lagoon North (LAN) and Lagoon
South (LAS), to settle wastewater sludge generated by the facility's oil
recycling process. After the flood in 1972, both lagoons were drained
and backfilled. One of former lagoons, located in the northwestern
corner, is in an area where oil sludge was landfarmed (LFA) from 1979
through 1981. This area was unsuccessfully used for agricultural
purposes between 1981 and 1984. The second lagoon was located in the
northeastern corner of the site.
Located in the southern portion of the site are the recycling
facility and office buildings. This is referred to as the Plant Facility
Area (PFA) . Just east of the PFA is a three-quarter hectare (1 acre)
area filled about two to two and a half meters (6 to 8 feet) deep with
oily filter sludge, called the Filter Sludge Storage Area (FSA). To the
south, near the drainage ditch, is an area that was used for the storage
of hundreds of drums of oil and oily water (Drum Storage Area - DSA).
These six waste areas were contaminated primarily with lead and oil
and grease, and with minor concentrations of volatile and semivolatile
organics and PCBs. Waste concentrations were in the following ranges:
Lead 0.3 - 2.2%
Oil and Grease 1.0 - 25.3 %
Volatile Organics 0 - 150 ppm
Semivolatile Organics 12.2 - 534 ppm
PCBs 1.2-54 ppm
pH 2.6-7
The high levels of lead and oil and grease in the waste were the deciding
factor for selecting the Douglassville superfund site for this
demonstration. It is known that organics and lead can interfere with the
stabilization process and it was felt these wastes would be difficult to
satisfactorily treat.
PROCESS DESCRIPTION
»
HAZCON Engineering, Inc.'s Mobile Field Blending Unit (MFU) operates
a continuous processing unit. Operating speeds, though governed by
predetermined mix ratios set in the laboratory, are variable up to 15
cubic yards of processed raw waste per operating hour. The MFU has no
external utility requirements other than a standard water hook up and the
attachment of a "quick connect" line from a bulk cement carrier.
The mobile field blending unit, consisting of bin, tank, auger
sizes, and component locations, is shown in Figure 2.
-66-
-------
Equipment calibration was performed each time a new waste feed
matrix entered the MFU. Calibration involves the determination of the
waste feed by weight, then the subsequent setting of the admixture flow
rates to the appropriate ratios.
Waste material is introduced to the system through the use of pumps,
dredges, or earth moving equipment, whichever may be the most efficient
or practical. The waste is moved through the process in a controlled
flow, allowing for precise measurement of the material. Based upon these
measurements, blending ratios, which are predetermined in the laboratory,
are set on a time weighted basis for both the Chloranan and pozzonalic
material, such as portland cement.
The Mobile Blending Unit contains some limited storage of the
additives. The pozzolanic ingredient is stored in a hopper and then
metered into the mix. Typical ratios, on a weight basis, range from 1
part waste: 1 part pozzolan, to 3 parts waste: 1 part pozzolan.
Chloranan is stored in a holding tank, then pumped into the mixing
chamber. Through precise control of the flow rate, ratios of waste to
Chloranan can be accurately metered from a 10:1 to a 50:1 blend.
All additives are fed via pump or auger through a mixing chamber to
achieve a homogenous blend. The resultant mass was extruded into either
temporary or permanent molds.
DEMONSTRATION PROGRAM
Six different contaminated soils at the Douglassville, Pa. site were
processed by HAZCON from the following locations; lagoon north (LAN),
lagoon south (LAS), filter cake storage area (FSA), drum storage area
(DSA), plant facility area (PFA), and landfarm area (LFA). The intent
was to process 5 cubic yards from 5 areas. An extended duration run for
the sixth area was to determine the reliability of the operating
equipment. Approximately 25 cubic yards of the stabilized LAS
contaminated soil were produced. The actual runs used less feedstock,
which produced approximately 5 and 25 cubic yards of treated soil.
The contaminated soil was excavated and screened to remove material
greater than 3 inches. It was then fed to the HAZCON Mobile Field
Blending Unit (MFU - the truck mounted system) along with portland
cement, water and Chloranan. Cement was used on an approximately l:l
basis with soil and the soil to Chloranan ratio was 10:1. The four feed
components were blended in a mixing screw and fed to 5 one-cubic yard
wooden molds for the short tests and 3 one-cubic-yard plus two 12 cubic
yard pits for the LAS. During the processing of three soils (DSA, LFA
and PFA) , toluene was injected into the soil to attain a concentration
of 100 ppm. It was felt that this would allow before and after
concentrations within the detection limits.
While the contaminated soil was processed and cured, the excavation
-67-
-------
holes were enlarged, lined with an impervious plastic liner, and
partially filled with clean soil. After the one cubic yard blocks cured
sufficiently to be moved (48-96 hours), they were removed from the molds
and placed into the pits. The blocks were then covered with additional
clean soil. After 28 and 210 days, the blocks were sampled. It is
proposed that after burial the blocks be sampled again every year, for
perhaps as long as 5 years.
SAMPLING AND ANALYSIS PROGRAM
Soil samples were taken before treatment, as a slurry exiting the
MFU for analysis after 7 days and as cores from the buried blocks after
28 and 210 days of curing. For the 5 cubic yard blocks, two untreated
soil composite samples were taken along with 3 sets of slurry and
solidified cores. For the extended run at LAS, additional samples were
taken for analysis.
The specific analyses performed on soil, slurry and core samples
included measuring physical properties, such as:
* bulk density
* moisture content
* permeability
* unconfined compressive strength of the solidified cores
* weathering tests
Chemical analyses were performed to identify the organic and metal
contaminants in the soil processed. In addition, three different
leaching tests were run:
* Toxicity Characteristic Leaching Procedure (TCLP) - standard
leaching procedure used for measuring leachability of the
contaminants (USEPA regulatory procedure).
* ANS 16.1 - simulates leaching from the intact solidified core
with rapidly flowing groundwater (ANS - American Nuclear Society).
* MCC-1P - simulates leaching from the intact solidified core
in relatively stagnant groundwater regimes (MCC - Materials
Characterization Center, Richland, Wash.).
These latter two tests were drawn from the nuclear industry and modified
to soil hazardous waste analyses.
Finally, microstructural studies were performed on the untreated
soil and solidified cores. These analyses included:
* X-ray diffractometry. - identifies crystalline structures in
the solid
* Microscopy - scanning electron microscope and optical microscope
-68-
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identifies level of porosity, crystal appearance, agglomerates,
and fractures.
DEMONSTRATION RESULTS
The comparison of the soil, 7-day, 28-day and 210-day sample test
results were generally favorable. The physical test results were very
good, with unconfined compressive strength between 220 to 1570 psi. Very
low permeabilities were developed (good) and the porosity of the treated
wastes were moderate. Durability test results were very good - there
were generally no changes in physical strength after the wet/dry and
freeze/thaw cycles for both the 28-day and 210-day samples. The
microstructural analyses seemed to indicate possible sample degradation
in the future. The future sample core testing will confirm or deny these
projections. There was a waste volume increase of about 120%. By using
less stabilizer smaller volume increases can be obtained, but lower
strengths will result. There is an inverse relationship between physical
strength and the waste organic concentration.
The results of the leaching tests were mixed. The TCLP results of
the stabilized wastes were very low; essentially all values of metals,
volatile organics and semivolatile organics were below 1 ppm. Lead
leachate concentrations dropped by a factor of 200 from the untreated
soil results, to below 100 ppb. Volatile and semivolatile organic
concentrations, however, did not change from the untreated soil TCLP.
Oil and grease concentrations were greater in the treated waste TCLPs
than the untreated waste, from less than 2 ppm to 2-4 ppm. PCBs could
not be detected (<1 ppb) in the TCLP leachates for either the treated or
untreated wastes.
Results from the specific tests are as follows:
The volume of the solidified soil was approximately double that of
the undisturbed feedstock. It is expected that this volume increase can
be avoided by using higher waste to stabilizer ratios. While this
probably will decrease the strength of the sample somewhat, the strength
should still be satisfactory.
Permeabilities of the treated soil were very low, in the range of
10-8 to 10 -9 cm/sec. A value of 10-7 is generally considered
satisfactory for landfill soil liners.
i
The unconfined compressive strengths (UCS) of the solidified soils
ranged from about 100 psi for FSA to 1500 psi for PFA and the values were
inversely proportional to the oil and grease concentration. These values
are quite satisfactory from a structural stability viewpoint.
Unconfined compressive strength tests were performed after the
wet/dry and freeze/thaw cyclical weathering tests for both the 28-day and
210-day samples. For these tests, the UCS changed very little (1-2%)
from that of the uncycled cores. It was noticed that the field cured
-69-
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samples had strengths less than the laboratory cured samples bjj as much
as 30%. It is suspected that the cause is the ideal curing conditions
used to store the laboratory samples.
The TCLP leaching test results are as follows:
Metals - the leachates for the solidified soils showed metal
levels at or near the detection limits. The results were 500 to
1000 less than in the leachates for the untreated soils.
Volatiles - the primary compounds detected were trichloroethene,
tetrachloroethene, toluene and xylenes. Only the leachates for the
untreated soil and 7-day cores were analyzed. The levels of
contaminants were approximately the same in both the treated and
untreated soils at levels of hundreds of micrograms per liter.
BNAs - the compounds detected in the leachates were phthalates and
phenols. The phthalates were reduced to near their detection limits
of 10 ug/1 in both the treated and untreated soil leachates. The
total phenols in the leachates were in the range of hundreds of
micrograms per liter, with the same concentration levels seen in
both the untreated and treated soil leachates.
PCBs - PCB were not detected in the TCLP leachates for either the
untreated or treated samples. It is thought the acetic acid
leachant is not effective in removing PCBs from solids.
Leachate results for the ANS 16.1 and MCC-1 were obtained and
compared to the TCLP results. It is not known if it is appropriate to
compare these leaching results and exactly what the comparisons mean.
The ANS 16.1 procedure had a metals leachate concentration similar
to the TCLP, but a volatile organics concentration half of the TCLP
and a semivolatile organic concentration slightly less than the
TCLP.
The MCC-1 leaching procedure had results different from the ANS
procedure, as expected. The metals leachate concentration was 5 to
10 times the TCLP concentration. Volatile organic leachate
concentration were similar to the TCLP while semivolatile organics
were half that of TCLP.
The microstructural studies provided the following information. It
should be emphasized that this is an experimental procedure, based on the
experience of the tester.
It is the opinion of the scientists who performed the microscopic
evaluations that the long-term durability of the stabilized waste
was questionable. The treated soils were very porous and the mixing
of the four process components appeared poor. Globules of organic
and untreated cement could be seen. It is not known which of the
microscopic or wet/dry and freeze/thaw tests are valid
-70-
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microscopic or wet/dry and freeze/thaw tests are valid
procedures for estimating long-term durability.
ECONOMIC ANALYSIS
Estimates for the cost for utilizing the HAZCON solidification process
were prepared. It was assumed that approximately 15% of the
Douglassville site was treated as part of a total site remediation.
Eight cases were investigated utilizing the following sets of variables;
On-Stream Factor - 70% the best seen during the demonstration and
90% the value projected by HAZCON for commercial operation.
Production Rates - 300 lb/min was the maximum thoughput during the
demonstration and 2300 lb/min was estimated for a field commercial
unit.
Chemical Additive Rates - Portland cement and Chloranan used
during the Demonstration and the projected commercial values is 33%
less than the Demonstration.
The costs per ton of processed soil ranged from $90 to $200. The lowest
cost occurred for a 90% on-stream factor, the high production rate unit,
and reduced chemical consumption. The two cost factors with the largest
influence were production rate and chemical additive rate. Approximately
90% of the total cost for processing the soil were labor and chemical
costs.
REFERENCES
1. U.S. Environmental Protection Agency "Technology Evaluation Report,
SITE Program Demonstration Test, HAZCON Solidification, Douglassville,
Pennsylvania, August 1988, RREL-0002.
-71-
-------
I
ro
i
ft I I
SLUOOE DISPOSAL AREA
»\ gLAN J
landfarmarea
©
~LFA 7S.
ACCESS ROAO
TODECONAREA
* -
XyC processing
^ FACILITY
<^5
s&
. - \\>NV
' -r v* v'^BvO/ \'i
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\ » I .* %•
- i • 0%>. vv.-V
Sfer- •
/
\V
APPROK. SCALE IN FEET
„,„. .
-------
Waste Bin
7.5 yd3 Cap. with
12" 0 Variable
Speed Auger
Admix tank
400 gal. Cap:
with flow control
and agitator
Cement Din
yd3 Cap. with
6" 0 Feed Auger
and Accuvane cement
calibrator
System
Control Panel
with automatic
and manual
controls
Mixing Auger 9" 0
•with variable
speed adjustment
Hydraulic Oil Roservo
Tank 75 gal. Cap.
Manual Hydraulic Controls
for.Wasto, Mixer, anc]
Cement/Accuvane Augers
Accuvane
Dag Counter
Manual Controls Cor
Hydraulic tloiot &
Gates, Engine HPMs.
Figure .2. Equipment layout diagram.
-------
TYPE OF TREATMENT:
General: Microbial Degradation
Specific:
Manufacturer:
FORMER USE/PROBLEM: Former refrigerator manufacturer
LOCATION/COUNTRY: Skrydstrup
Denmark
CQNTAMINANT(S): Chlorinated solvents
Haloalkyl phosphates
MEDIUM OF CONTAMINANT(S): Soil
Groundwater
STATUS AS A NATO/CCMS
STUDY PROJECT:
Proposed: 3/87
Accepted: 3/87
Interim Report(s): 11/87; 11/88; 11/89
Expected Completion Date:
Final Presentation:
-75-
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Aerobic Biodegradation of Chlorinated Solvents
in an Unsaturated Soil
Presented to
NATO/CCMS Pilot Study on Remedial Action Technologies
for Contaminated Land and Ground Water
by
Kim Broholm
Department of Environmental Engineering
Technical University of Denmark
November 1988
-76-
-------
Status for the project:
Aerobic Biodegradation of Chlorinated Solvents
in an Unsaturated Soil.
Introduction
The following project is one of four demonstration projects
that are carried out in connection with Skrydstrup Chemical
Waste Disposal Site. A general description of the site and the
other projects are given in other papers /l/, /2/.
The purpose of the project is to investigate the possibilities
to carry out an in-situ biodegradation in an unsaturated zone
contaminated with chlorinated aliphatics.
The project is running from August 1987 to August 1989.
Originally the project consists of both laboratory and field
experiments, but unfortunately the unsaturated zone at the
field site at Skrydstrup is not suitable so the field
experiment will not be carried out.
Degradation of chlorinated aliphatics
The chlorinated aliphatics consist of a group of organics that
are derived from methane, ethane or ethene by substituting one
or more hydrogen with chloride. At Skrydstrup the most impor-
tant contaminants are trichloroethylene (TCE), 1,1,1-
trichloroethane (TCA) and tetrachloroethylene (PCE). These
three organics are the main contaminants that are investigated
in the laboratory experiments.
Generally the chlorinated aliphatics are persistent under
aerobic condition but are degradable under methanogenic condi-
tion. Under aerobic condition a special group of bacteria (the
methane-oxidising bacteria or the methanotrophic bacteria) can
degrade some of the chlorinated aliphatics e.g. TCE. The
methanotrophic bacteria utilise e.g. methane as energy and
carbon source (as primary substrate). Simultaneously the bac-
teria degrade TCE by a cometabolic process without any energy
or carbon gain for the bacteria.
-77-
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Batch experiments
The purpose of the batch experiments are to confirm biodegra-
dation of chlorinated aliphatics under aerobic condition using
methane or propane as a primary substrate.
The experiments are carried out in 120 ml bottles with miniert
valves (see figure 1). By using miniert valves it is possible
to take more than one sample from the same bottle. Each bottle
contains 20 g unsaturated soil, methane or propane at start
concentrations at respectively 2 and 0.8 vol-% in the air, and
TCE and TCA at a start concentrations at about 200-300 ppb in
the air. The soil is from the unsaturated zone at Skrydstrup.
Control bottles without biological processes contains auto-
claved soil. The experiments are carried out at about 20*C. The
concentrations of methane, propane, TCE and TCA are monitored
by taking air-samples from each bottle to different times.
Methane and propane are analysed on a GC/FID and TCE and TCA
are analysed on a GC/ECD.
Figure 1: The experimental setup for the batch experiments. The
bottle has a volume on 120 ml and is provided with a
miniert valve.
78
-------
Figure 2 shows the concentrations of methane and TCE in a ex-
periment with a soil where the microorganisms have been adapted
to methane before the start of the experiment. A significant
degradation of methane and TCE are observed.
Figure 3 shows the concentrations of propane and TCE in a
similar experiment with a soil where the microorganisms have
been adapted to propane instead of methane. A significant de-
gradation of TCE are observed by using propane as primary
substrate.
Neither the microorganisms in the methane nor propane adapted
soil was able to degrade TCA.
The batch experiments show that from the indigenous microor-
ganisms in the soil it is possible to build up a biomass that
is able to degrade TCE (but not TCA) using methane or propane
as a primary substrate.
Column experiments
The purpose of the column experiment is to examine the effect
of following factors under flowing condition: addition of
adapted microorganisms and the start concentration of chlori-
nated aliphatics in the soil.
The column experiment is carried out in 15 packed columns made
of stainless steel. An outline of the column design is shown in
figure 4. The columns are 75 cm high and have a volume of
5.9 1. They contain about 9 kg wet soil. The infiltration
through the columns is 20 or 40 ml/day corresponding to 75 or
150 mm/day. The infiltration water contains nutrients and
sometimes also microorganisms. A mixture of 2% methane in
atmospheric air is added to the bottom of each column, except
the control columns that only receive atmospheric air. The ad-
dition of methane and air is directed by both the consumption
of methane and oxygen. The columns are incubated at 10°C. The
soils used in the column experiment are sands from Skrydstrup.
The start concentrations of TCE, TCA and PCE in the two types
of soil were (in mg/kg wet soil):
TCA
TCE
PCE
Most contaminated
190
25
19
Least contaminated
1.1
0.5
1.1
-79-
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0
>
ai
u
a
a.
i/)
"O
a
01
-C
c
o
c
V
u
c
0
u
1
0)
c
o
£
ou
2
10 20 30
Time (days)
(¦>•) Degradation (a,^) Control
10 20 30
Time (days)
(¦,•) Degradation (~.+) Control
Figure 2: The concentrations of respectively methane and TCE
measured in headspace in a batch experiment with soil
adapted to methane. At day number 0, 12, 20 and 27
methane was added to the two batches with methane
degradation.
-80-
-------
(¦,•) Degradation (a, ~) Control
. .
300 T
_Q
a.
280-
Q.
260-
80-
o
c
60-
o
u
40-
ID
y
20-
0-
0
Time (days)
i.«) Degradation (*,+) Control
Figure 3: The concentrations of respectively propane and TCE
measured in headspace in a batch experiment with soil
adapted to propane.
-81-
-------
The start concentration of TCA, TCE and PCE in the leaching was
(ppb):
TCA TCE PCE
Most contaminated 20.000 3.000 4 00
Least contaminated 3.200 900 400
During the experiments the methane concentration in the top of
the columns are measured. Figure 5 shows the concentration of
methane in the top of two columns containing least contaminated
soil: one without addition of microorganisms and one with ad-
dition. The methane consumption in the column without addition
of microorganisms starts after about 45 days which indicated
that the time necessary to build up a biomass is about 45 days.
Figure 4: Column design, a/ syringes used for addition and
sampling of water, b/ tubing clamps, c/ water
distributor, d/ pump controlling the amount of air
and methane added to each column, e/ XAD-2-trap
catching the chlorinated aliphatics in the air, f/ on/off
valve, g/ methane/air adding. The amount of air and
methane is controlled by the pump.
-82-
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2 0-> 1 1 1— 1-
0 20 40
Time (days)
¦ Addition of micro-organisms
• No addition of micro-organisms
Figure 5: The methane concentration (measured in the top of the
column) in two columns containing the least
contaminated soil. One of the columns has received
microorganisms in the periods from day 3 to 10 and
from day 25 to 31. Both columns have received a new
amount of air and methane at days 3,-26 and 35. Not
all the data are shown in the figure.
The methane consumption in the column with addition of micro-
organism starts after about 25 days. It means it is possible to
add microorganisms to a soil in order to reduce the time
necessary to build up a suitable biomass.
In the columns with the most contaminated soil there has not
been any methane consumption during the first 200 days. The
addition of microorganisms has no effect in this case.
The difference between the two soils are probably due to a
toxic effect of the chlorinated aliphatics itself especially
TCA. Other experiments show taht the concentration of TCA has
either a toxic or an inhibitory effect on the methane-oxidising
bacteria at concentrations as low as 5 ppm. /4/, /5/.
The main result from the column experiment is a mass balance
for each column and each compound, where the known factors
(measured) are the start concentration in the soil and the end
concentration, the leaching and the stripping, and the unknown
factor (calculated) is the degradation.
After 115 days nearly all the organics in the least contami-
nated soil were neither leached, stripped nor degraded. The
mass balances show that the leaching and especially the
-83-
-------
stripping counts for nearly 100%, which result in a insignifi-
cant degradation. From the methane consumption in the columns
it is obvious that a methane-oxidising biomass is present, but
the degradation rate of chlorinated aliphatics is to slow to
remove a significant amount of the organics compared with the
other terms of the mass balance. The methane consumption in the
columns containing the least contaminated soil is in the same
order of magnitude as in the batch experiments (when the de-
gradation rate has been adjusted to the same temperature) . It
means that the degradation rate of methane is not limited by
methane or oxygen, if the conditions in the batch experiments
is considered as optimal.
Preliminary conclusions
The batch experiments show that TCE can be degraded by the
indigenous microorga'nisms by using methane or propane as
primary substrate. In the same experiments no degradation of
TCA was observed.
The column experiment show it was possible to add
microorganisms that was able to survive in the least
contaminated soil but not in the most contaminated soil.
There was no degradation of TCA, TCE or PCE in the least
contaminated soil in the column experiments despite methane was
consumed in the same soil.
-84-
-------
References.
/I/ Skrydstrup Chemical Waste Disposal Site, Research and
development program in the province of Soenderjylland
Denmark. Presented at The First International Meeting of
the NATO/CCMS Pilot Study on Remedial Action Technologies
for Contaminated Land and Ground Water. September 1987.
/2/ Vedby, S.: State of the research and development program at
Skrydstrup Chemical Waste Disposal Site. Presented to:
NATO/CCMS Pilot Study on Remedial Action Technologies for
Contaminated Land and Ground Water. November 1988.
/3/ Vogel, T. M., C. S. Criddle and P. L. McCarty:
Transformation of halogenated aliphatic compounds.
Environmental Science and Technology, 21, (8), pp. 922-936,
1987.
/I/ Broholm, Kim: unpublished data.
/5/ Janssen, D. B., G. Grobben and B. Witholt: Toxicity of
chlorinated aliphatic hydrocarbons and degradation by
methanotrophic consortia. In: Proc. 4th European Congress
on Biotechnology 1987, vol 3.
-85-
-------
STATE OF THE RESEARCH AND DEVELOPMENT PROGRAM AT SKRYDSTRUP
CHEMICAL WASTE DISPOSAL SITE, by Steen Vedby Nov. 1988.
The purpose of the project is to verify whether in situ degrada-
tion of chlorinated solvents is possible.
The county of Soender jyl land have since 198*t carry out
investigations in the area.
In 1986 the site it self was cleared by excavation. A full scale
clean up of the groundwater pollution was planned in 1987.
However this on site water treatment plant have just been built
and a test period of tree month will start from November 1988.
The clean-up is planned on the basis of simultations and results
of a pilot plant study of water treatment processes.
As regards information on the project and its scope, we refer to
the Danish contribution to the NATO-meeting in Washington, by
Karin Christiansen and Steen Vedby, October 1987.
Demonstration projects.
In connection with the full scale clean-up of groundwater k
research projects have been initiated:
A) Biodegradation of chlorinated solvents in contaminated
so i 1 .
B) Aerobic bio-degradation of chlorinated solvents by addition
of natural gas in columns with activated carbon adsorption.
C) Aerobic bio-degradation of chlorinated solvents in the
unsaturated zone by CO- metabolism by oxidation of methane
and/or propane gas.
D) Anaerobic bio-degradation of chlorinated solvents in the
contaminated zone by addition of sodium acetate.
In general project B and D is behind time schedule caused by
delay in the full scale groundwater treatment.
In the following the state on the demonstration projects and
provisional results will be given.
A) Biodegradation of chloronated solvents in contaminated
soil.
In the period from December 1986 until now leachate samples have
been taken from the temporary collection site - both from the
anaerobic and aerobic section.
-86-
-------
Provisional analysis from the anaerobic section shows, a
decrease in the content of trichloroethane and trichlo-
roethylene after a period with fluctuations, figure 1.
Figure 1. Ana 1yseresu1ts from the anearobic section, 1986-88.
It is particularly the increase in concentration of cis-dic-
hloroethylene and perhaps 1.1 dichloroethylene, about half a
year after the temporary collection waste site was establish,
who is of interest.
From figure 2 the concentrations of 1.1 dichloroethane and 1.1
dichloroethylene measure relative to 1.1.1 trichloroethane is
shown.
The concentration of 1,1-dichloroethylene is constant within
analytical variability over the whole period. For 1,1-
dichloroethane there is a tendency to increased concen-
trations with time.
-87-
-------
Results for the possible degradation of trichloroethylene is
shown in figure 3.
CO«K
*
no
;oo
ISO
100
so
e 1.1 - OCA
« 1.1 - OCE
60C Oor«
200
400
<00 Oo r%
Figure 2 Concentrations of 1,1-dichloroethane (1,1-DCA) and
1,1-dichloroethylene (1,1-DCE) measured relatively to
1,1,-trichloroethane in the aerobic (A) and the
anaerobic (B) part of the collection site.
R*l conv
. (
o CIS 1.2-OCE
* 1.1 - OCE
200
too
(oo Doy*
Rclconc
X
2S0
200-
150
100
SO
o cis 1.2 - OCE
« 11 - OCE
/
/
/
s
/ o
200
«00
600 Days
Figure 3 Concentrations of cis 1,2-dichloroethylene (cis
1,S-DCE) and 1,1-dichlorethylene (1,1-DCE) measured
relatively to trichloroethylene in the aerobic (A) and
the anaerobic
-------
Again there is no evidence for the formation of 1,1-dichlo-
roethylene, while the results from the anaerobic part of the
site give a clear indication for a formation of cis l,E-di-
chloroethy lene. Furthermore very small amounts of trans
1,5-dichloroethylene and viny lch lor ide (less than IV. relative
concentration) are detected at the two last sampling dates. In
the aerobic part of the site the concentration of cis
1,2-dichloroethylene also increases slightly, but the trans
isomer and vinylchloride are not detected.
These findings are in agreement with results from laboratory
experiments (e.g. Vogel & McCarty, 1985) which show that cis
1,S-dichloroethylene is the dominant degradation product of
trichloroethylene. Results from the literature also show, that
degradation preferably takes place under anaerobic conditions.
The analysis will continue at least one year.
B) Aerobic bio-degradation of chlorinated solvents in columns
with carbon.
The project will start in November 1988. A pilot-water treatment
plant with a methane gas connection are under construction and
will be built as a part of the large scale water treatment
plant.
In addition to the research on the pilot watertreatment plant
tree laboratory test are set up.
Researchactivities:
1) Reproduction of different grafting material and investi-
gation on different cultures adaptation time.
2) Research on 1,1,1-trichloroethane degradation relative to
-89-
-------
trichloroethylene at 10°C and SO°C, and TCA 1 s influence
on degradation on TCE.
3) Research on relation between use of methane-gas and TCE
degradation.
The results of this tree research projects will be available in
February 1989.
Experiment on the plant will be report within 1 and '/i year from
now.
C) Aerobic bio-degradation in the unsaturated zone.
The laboratory research are nearly completed, Kim Broholm 1988.
Due to raising watertable in the excavated area the field
experiment will not be carried out.
The decision should bee seen in connection with project D>, see
below.
D) Anaerobic bio-degradation of chloronated solvents in the
groundwater zone.
The subproject dealing with biological in situ degradation of
chlorinated solvents in the groundwater zone is of particular
importance in connection with the NATO Pilot Study Program.
This subproject is behind schedule, because decisions relating
to large-scale remedial action in the groundwater zone were not
taken until a meeting in the province of Soenderjylland on March
9, 1988, and the plant is now establish and will be started in
November 1988.
A number of introductory field and laboratory investigation
have, however, been carried out in order to be able to decide
the final test design of the field tests. Further, a litera-
ture review has been made on "Anaerobic Degradation of
chlorinated Solvents".
-90-
-------
Following field and laboratory test has been carry out:
1> Anaerobic degradation of chloronated organic compounds,
lab. test.
2) Decision on vertical distribution on redox parameter and
chloronated solvents in the plume.
3) Model simultation on placement of the field test area and
test calculations.
U) Laboratory research on biodegradation of chlorinated
solvents with acetate.
Reports are available in Danish language.
Results from water samples taken in a well down to depth of 30 m
in the plumed area have improvident shown that their is oxygen
and nitrate in the contaminated part of the aquifer, fig. 4.
Figure ** Results from a BOTESAfl-we 11 in the plume.
-------
It is therefore impossible to fulfil the anaerobic degradation
as planned with sodium acetate.
The fieldtest will instead be carry through by simulate a
aerobic degradation with methane as primary source.
To be sure that the aerobic degradation is possible in the field
test area, a project is confirm with following purpose:
- Describtion of the bio-population in the aquifer.
- Envestigation on degradation potential in the plume.
- Inhibition or toxic effects on higher consentrations of
chlorinated solvents.
Different grafting materials and their degradation potential.
- Using of other primary substrates,- methanole, formate ect.
This research activities are planed report within one year.
-92-
-------
TYPE OF TREATMENT:
General: Pump and Treatment
Specific: In-S1tu Blorestoratlon
Manufacturer:
FORMER USE/PROBLEM: Gasoline station and dlesel oil
LOCATION/COUNTRY: Asten - province of Noord-Brabant
The Netherlands
CONTAMINANT(S): Normal gasoline
MEDIUM OF CONTAMINANT(S): Subsoil
STATUS AS A NATO/CCMS
STUDY PROJECT:
Proposed: 3/87
Accepted: 3/87
Interim Report(s): 11/87
Expected Completion Date:
Final Presentation: 11/88
-93-
-------
IN SITU BIORESTORATION OF A SUBSOIL,
CONTAMINATED WITH GASOLINE.
R. van den Berg and J.H.A.M. Verheul
National Institute of Public Health
and Environmental Protection (RIVM).
P.O.Box 1, 3720 BA Bilthoven, The Netherlands.
D.H.Eikelboom.
Netherlands Organization for Applied
Scientific Research (TNO).
P.O.Box 217, 2600 AE Delft, The Netherlands.
Second interim report for the 2nd. International Meeting of
the NATO/CCMS Pilot Study: Demonstration of remedial action
technologies for contaminated land and ground water.
-94-
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1. INTRODUCTION.
An important part of the costs of soil clean-up is involved with
excavation of the contaminated soil. These costs could be reduced
considerably by an in situ treatment of the location. Moreover,
clean-up is possible at greater depth and under buildings. In the
framework of the Research Program on Biological Soil Clean-up Techniques
the Ministry of Housing, Physical Planning and the Environment has
assigned a research project to RIVM in co-operation with the Division
Technology for Society of TNO.
The aim of the research project is to study the feasibility of
biological in situ treatment, including aspects of costs and time.
The project consists of three stages:
1. A literature study and the selection of an experimental site;
2. Laboratory research, research in undisturbed soil columns and
detailed [geohydrological and chemical] investigation of the site;
3. Design and execution of the clean-up.
The results of the literature study (1,2), the laboratory research (3)
and the site investigation (4) have been reported. In this paper the
results of the column study will be given and discussed, as well as the
design of the clean-up. The complete results of this research will be
reproted at the end of 1988. Preliminary results of the column study
were presented at the second TNO/BMFT conference (5).
-95-
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2 DESCRIPTION OF THE SITE.
An oil polluted site has been chosen as the test site because a large
number of sites in the Netherlands are contaminated with oil or oil
products and because oil components are in principle biodegradable.
The selected site is a petrol-station located at Asten, in the province
of Noord-Brabant. The subsoil has been contaminated with 30.000 1 of
gasoline from a leaking tank and a small quantity of Diesel oil. In
observation wells installed free product has been measured upto 150 cm
thickness. About 20.000 1 of free product has been recovered by pumping
off. As result of this pumping-off the ground water level decreased
from 2.5 to 3.5 meter below surface level.
Sampling at the site has provided information about the distribution of
the remaining contamination. The horizontal distribution of the
contamination is given by the dotted line in figure 1. The contaminated
2
area is about 25 x 25 m . In depth the soil is contaminated from about
3
2 to 4.5 meter below surface level. About 1500 m of soil is
contaminated with a measured maximum gasoline concentration of 12.000
mg/kg (table 1). The groundwater is contaminated upto 10 meters below
surface with volatile aromatics (table 2). From a comparison of these
concentrations with the ABC reference values in the guidelines of the
Dutch government (6) and a risk evaluation it was concluded that soil as
well as ground water had to be cleaned.
Figure 2 shows the composition of the soil at the site. The soil is
generally sandy, without organic matter (< 0.05 %). Until 15 to 20
meter below surface level some layers of clay and loam are present. At
20 meter a thick layer of porous material exists.
-96-
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3 EXPERIMENTS IN UNDISTURBED SOIL COLUMNS.
The aim of the column experiments was to verify the results of the
laboratory experiments, to examine the effects of scaling-up and soil
structure and to test the suitability of hydrogen peroxide and other
alternative oxygen sources.
Column experiments have been set up based on the results of the
intensive laboratory experiments, in which the influence of (a)biotic
conditions on the degradation and leaching have been investigated (3 and
8: first interim report).
3.1 Design of the column experiments.
Experiments have been carried out in six stainless steel columns [lenght
70 cm, 20 cm i.d.]. At all columns sampling ports were installed at 27,
48 and 62 cm from the top of the column. To prevent disturbance of the
pore structure, the columns were driven gently into the soil at the site
just above the ground water level [2,8 - 3,3 m below surface ]. At this
depth the highest concentrations of gasoline have been found. During
the filling of the columns several soil samples were taken at different
depths near each column to estimate the amount of gasoline in the soil
columns. In the laboratory the soil columns were build up in a
temperature (10 °C) controlled room.
All columns were percolated in the up-flow mode with aerated artificial
rainwater as the medium. The flowrate in the columns was initially 40
cm/d, but was increased after 100 days to 80 cm/d (figure 3). Before
the flow rate was increased breakthrough curves have been made with
chloride as tracer. Except for column 1 no significant differences
were found. During the total operation period no problems occurred with
the permeability of the columns (figure 3).
From the results of the laboratory experiments it was decided to use one
C-N-P ratio and to add the phosphate as the buffer. Besides air as
oxygen source, hydrogen peroxide and nitrate were examined as
-97-
-------
alternative oxygen sources. In spite of the disappointing results in
the lab experiments nitrate was tested because of reported results (7).
This resulted in the following modes of operation.
£olumn_l: only percolated with aerated rain water; used as a blank.
Column 2: addition of nitrogen [12.5 mg N/1 NH NO ] and phosphate [15 mg
P/l ,as a buffer of KH PO and Na HPO , pH 6,9 at 10 *C1.
2 4 2 4
Column^: as column 2 with H^O^ as an additional oxygen source [conc. up
to 200 mg/1].
Colnmn 4: as column 2 with an initial addition of sodium acetate to
stimulate the biomass.
Column 5: as column 2 with nitrate as oxygen source [conc. up to 100 mg
N/1] .
Column 6: as column 2 but the effluent is recirculated after treatment.
To monitor the processes in the columns the effluents were analyzed for
gasoline and twenty of its individual components [GC analysis], oxygen,
hydrogen peroxide, nitrate, nitrite, ammonium, phosphate, pH, dissolved
organic carbon (DOC), dissolved inorganic carbon (DIC) and colony count.
After dismantling the solid phase was analyzed for the remaining
gasoline (components) and the colony count.
The columns 1,2, 3 and 6 were dismantled after six months of operation.
The columns 4 and 5 were kept in operation for possible further
experiments to confirm the experiences of the first test period. It was
assumed that the behaviour in these columns had not been different from
that in columns 1 and 2 -considering the data obtained. After 9 months
of operation the columns 4 and 5 were both changed for operation as
recirculating columns. Moreover in column 4 hydrogen peroxide was
introduced as additional oxygen source. These two columns have been
operated for another six months and were dismantled after a total
incubation of 15 months because a breakthrough of oxygen occurred in
column 4.
-98-
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3.2 Results of the column experiments.
Leaching of the gasoline.
The leaching of the several individual gasoline components is very
different. Especially the volatile aromatics are leached from the soil,
as shown in the figures 11a to lid. No leaching was observed for the
aliphatics present. The leaching of the aromatic compounds occurred at
very high concentrations in the first week. After three weeks
concentrations of 1 ug/1 or less were observed.
Figure 4 shows as an example the leaching of total gasoline for column
3. The total amounts of gasoline leached from the columns after 180
days are given in table 3. No differences have been observed in the
leaching behaviour of the columns, in spite of the differences in
concentration and total amount of gasoline present. After the initial
phase an average leaching rate of 9 mg C/kg/d was calculated. This is
in agreement with the results of the laboratory experiments (3,8).
Considering the leaching in columns 4 and 5 in the extended test period
it was obvious that a decreased leaching might be expected caused by the
presence of less mobile/soluble compounds. Because the data are not yet
available the data after 180 days are used in the calculations.
Oxygen.
Generally no breakthrough of oxygen has been observed and the oxygen
concentrations in the effluents have been less than 1 mg/1, as shown for
column 2 in figure 5a. However, in column 3 complete breakthrough of
oxygen was obtained at the 62 cm port after one month, at 48 cm after
three, at 27 cm after five and in the effluent after six months (figure
5b).
After the change of operation in columns 4 and 5 breakthrough of oxygen
occurred in all sampling ports of column 4 in course of the test period.
Finally the breakthrough in the effluent was observed after 151 days
after change of operation. The hydrogen peroxide additions were adapted
for the oxygen data observed.
-99-
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Considering the stability of hydrogen peroxide it can be remarked that
in the point of entrance in the column three times increased oxygen
concentrations could be measured when 200 mg/1 was dosed. At the end of
the experiment hydrogen peroxide has been determined in the sampling
port at 48 cm. This shows the possible stability of the peroxide. The
instability of peroxide seems to be related to the presence of organic
material.
Nitrogen, phosphate and pH.
In none of the columns uptake of nitrate has been observed, even in
spite of the "absence" of oxygen in the columns. Some transformation of
ammonium into nitrate was observed. As a result no net uptake of
nitrogen by the microorganisms took place (shown for columns 3 and 5 in
figure 6).
Also no net uptake has been found for phosphate. The phosphate, added
as buffer, was necessary for maintenance of the acidity. In the
recirculating columns 4 and 5 discontinuous addition of the buffer was
necessary to maintain the neutral pH. In the first, unstable period the
acidity could drop to 5.2, while in the stable period a pH of 6.5 to
6.9 was maintained.
Dissolved organic and inorganic carbon.
Because of imperfections in the techniques of sampling and analysis for
these parameters only reliable data have been obtained for the extended
test period with the columns 4 and 5. Higher dissolved organic and
inorganic carbon concentrations were determined in column 4 (figures 7
and 8). The succession of the degradation in the column could be
followed in column 4 by the zones of DIC production. As figure 9 shows
the degradation proceeds from the bottom to the top of the column and
ceased at the end of the experiment. This progress through the column
is in agreement with the access of oxygen.
-100-
-------
Colony count and ATF.
The data obtained on these parameters are very scarce and not shown.
The colony counts of the solid phase could be made only at the end of
the experiment. It appeared that the highest activity occurred in the
zone where oxygen was present and degradation was assumed. For columns
4 and 5 the observations for colony count and ATP agreed. Generally, in
column 4 ten times higher counts were found.
Solid phase concentrations after dismantling.
Table 4 gives the solid phase concentration after dismantling of the
columns. These results show a high removal of gasoline in the columns
3,4, 5 and 6. The concentrations can be compared with the estimated
start concentrations.
Comparison of the concentrations with the Dutch ABC reference values
shows that after six months of operation with peroxide addition the
gasoline concentrations have been reduced to a level below the C-value.
The lower parts of the columns even turned out to be below the A-value.
Recirculation only also provides good results, as shown for columns 5
and 6.
Mass balances and [biological] removal.
In table 3 and figure 10 the results of the mass balances for the
columns in terms of gasoline are given. The [bio]degraded amount is
calculated from equation 1.
- M + M +M [1]
i r 1 d
In which
M - the total quantity initially present in the column,
M - the amount of gasoline recovered from the soil after dismantling
r
of the column,
M - the total amount of gasoline leached from the column,
1
M - the amount of gasoline [bio]degraded.
-101-
-------
The result for the amount biodegraded is compared with the amount which
could be mineralized theoretically based on the input of oxygen,
assuming that 2,5 gram of oxygen is needed to degrade 1 gram of
gasoline.
No distinction can be made between chemical and biological
degradation.
Results of mass balances for the individual components are shown in
figures 11a to lid for the columns 1, 2, 3 and 6. The data for columns
4 and 5 are not yet available.
3.3 Discussion.
Considering the first four dismantled columns degradation has occurred
in the columns 3 (hydrogen peroxide) and 6 (recirculation). Hardly any
degradation has occurred in columns 1 (blank) and 2 (NP addition).
Based on the oxygen input data this result was not surprising, except
for column 6. A hypothesis for the high degradation in column 6 is that
as a result of the recirculation an increased leaching/bioavailability
has appeared, e.g. caused by the continuous production and in this
column recirculation and accumulation of emulsifiers. Although no
continuous data were available the final results for these columns
showed the higher D1C concentrations in column 3 compared to column 6,
confirming the higher availability of oxygen in column 3.
Based on the data obtained a similar mass balance pattern was expected
for columns 4 and 5 as for columns 1 and 2.
These two columns 4 and 5 confirmed after change in operation the
results of the first test period. Recirculation again led to the same
unexpected, experienced high removal of gasoline. The higher oxygen
availability in column 4 was confirmed by the higher DIC concentration
in column 4, but not by the DOC concentration, which was expected to be
higher in column 5 because of lack of oxygen.
The combination of DIC and DOC production and leaching accounts for only
a small part of the biodegradation. Further statements about these
-102-
-------
results cannot be made at this moment.
A proces based on both treatments, recirculation as well as hydrogen
peroxide addition, is still expected to give the optimal result because
of the unknown fate of gasoline in the recirculated column.
3.4 Conclusions.
The quantities leached from the soil columns were independent of the
amount of gasoline present.
During leaching predominantly aromatic compounds were removed,
especially in the first three weeks.
Hydrogen peroxide appeared to be a very useful alternative oxygen
source, in contrast to nitrate, which was not taken up by the
microorganisms.
(Biological) degradation of the gasoline, besides leaching, has only
been observed for the columns with hydrogen peroxide addition or
recirculation of a combination of these.
In case degradation occurred, the percentages leached and degraded of
the aromatics were about the same. The aliphatics were removed only by
degradation and then almost completely.
Net uptake of nitrogen or phosphate has not been observed.
The gasoline recovered in the soil of the peroxide columns was below the
C-reference value after six months of operation; parts were even below
the background value.
The fate of the degraded gasoline is not yet solved. A part is
transformed to leachable DOC, another to DIC, but a large part is still
unknown.
In spite of the small differences in results for hydrogen peroxide and
recirculation separately it is still concluded that a combination of
both is needed.
-103-
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4 DESIGN OF THE CLEAN-UP.
Aim of the clean-up is a simultaneous clean-up of the contaminated soil
and ground water. A design has been made based on the hydrology and the
results of the research on laboratory and column scale. This means that
the contaminated soil will be water saturated, the pH of the soil is
made neutral, hydrogen peroxide is added and if necessary nutrients (N
and P) are dosed. During the start of the clean-up phosphate is dosed
for a proper adjustment of the required pH.
The flow chart of the clean-up is given in figure 12 and figure 13 gives
a cross section of the site with an overview of the restoration proces
for soil: infiltration and shallow withdrawal and for the ground water:
deep withdrawal (8-12 m below surface level).
3
The water will be infiltrated at a rate of 35 m by drains (lenght of
180 m, placed parallel to each other), which will be installed 1 m below
surface. Withdrawal of the water will take place by pumping wells at a
rate of 38 m /h. The water will pass a stripping tower [connected with
a biofilter for air purification] for removal of volatile hydrocarbons
and aeration and a sand filtration. In the infiltrating water nutrients
and hydrogen peroxide will be added.
The whole system is automatically controlled.
In order to optimize the location of the infiltration drains and the
pumping wells the computer program CONTOUR has been used. Special
attention has been paid to the waterflow under the buildings at the
site.
Based on this design and an expected duration of the biorestoration of
6 to 12 months the costs have been estimated at Hf 0.7. The costs for
excavation of the site and thermal treatment (incineration) of the
contaminated soil have been calculated at Mf 1.2. Not included in these
costs are the loss of income because of the estimated three weeks of
duration of the clean-up. During in situ treatment sales will proceed
normally.
-104-
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5 EVALUATION.
Until now this research has shown that in situ biorestoration offers
good prospectives. Technically no problems have been encountered yet.
The column experiments have demonstrated that hydrogen peroxide is a
useful alternative oxygen source and recirculation gave no problems with
the permeability if proper treatment of the effluent was assured. High
levels of clean-up could be obtained.
The costs seem to be lower than for the conventional techniques.
Therefore it is concluded that in situ biological treatment offers a
good alternative as a soil clean-up method, with advantages with
respect to excavation with physical, chemical or biological treatment.
These experiments and other projects have shown that preceding research
is necessary to avoid pitfalls. During this research attention has to
be paid to the balance between geohydrological and biodegradation
research.
-105-
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6 REFERENCES.
1. Eikelboom, D.H. , 1985. In situ biorestauratie van een met
olieprodukten verontreinigde ondergrond. Een literatuurstudie.
TNO-rapport R85/320 [TNO, Delft].
2. Eikelboom, D.H. and Verheul, J.H.A.M., 1986. In situ biological
treatment of a contaminated subsoil. In : Contaminated Soil [J.V.Assink
and W.J.v.d.Brink eds.] pp. 686-692. Martinus Nijhoff, Dordrecht.
3. Berg, R. van den, Eikelboom, D.H. en Verheul, J.H.A.M., 1987. In
situ biorestauratie van een met olie verontreinigde bodem. Resultaten
van het laboratorium onderzoek. RIVM-rapport 728518002 [RIVM,
Bilthoven].
4. Verheul, J.H.A.M., Eikelboom, D.H. en Berg R. van den, 1988. In
situ biorestauratie van een met olie verontreinigde bodem. Selectie,
beschrijving en nader onderzoek van de proeflokatie. RIVM-rapport
728518001 [RIVM, Bilthoven].
5. Verheul, J.H.A.M., Berg, R.v.d. en Eikelboom,D.H. 1988. In situ
biorestoration of a subsoil contaminated with gasoline. In
Contaminated soil '88 [K.Wolf, V.J.v.d.Brink and F.J.Colon eds.]. pp.
705-715. Kluwer Academic Publishers, Dordrecht.
6. Moen, J.E.T., Cornet, J.P., and Evers, C.V.A., 1986. Soil
protection and remedial actions: Criteria for decision makingand
standardazition of requirements. In : Contaminated Soil [J.W.Assink and
W.J .v.d.Brink eds.] pp. 441-448. Martinus Nijhoff, Dordrecht.
7. Batterman, G. and Werner, P., 1984. Beseitigung einer Untergrund
Kontamination mith Kohlen Wasserstoffen durch mikrobiellen Abbau.
GWF-Wasser/Abwasser, 125.H8, 366-373.
-106-
-------
8. Berg, R. van den, Soczo, E.R., Verheul, and Eikelboom,
D.H., 1987. In situ biorestoration of asubsoil, contaminated with oil.
The first interim report. RIVM-report 728518003. [RIVM, Bilthoven].
-107-
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TABLE 1. Concentrations of gasoline in the soil [nig.kg ]. N is the
number of samples.
DEPTH (CM)
MEDIAN
RANGE
N
0 -200
14
5-17
4
200 - 250
70
18-810
9
250 - 300
1600
160 - 5200
23
300 - 350
4800
9-12000
14
350 - 400
360
5-1300
6
400 - 500
220
17-460
4
500 - 600
12
15-20
2
REFERENCE VALUES
A: 20
B: 100
C: 800
TABLE 2. Highest concentrations of some individual gasoline
components found in the deeper ground water.
DEPTH(M)
BENZENE
TOLUENE
NAPHTHALENE
8
919
1800
109
14
0.3
1.4
—
20
—
0.4
REFERENCE VALUES
A
0.5
0.5
0.2
B
1.0
15.0
7.0
C
5.0
50.0
30.0
-108-
-------
TABLE 3. Mass balances for all columns with respect to gasoline [g].
The percentages are related to the initial amount present.
M.-initially present, Mj-leached after 6, * 15 months, recovered,
M^-degraded, Md th.- theoretically degraded.
column
Mi
M1
M
Md
M th
[g]
[g]
[%]
[g] r
[%]
[g]
[%]
f%]
1
100
66
[66]
32
[32]
2
[ 2]
12
2
111
61
[55]
58
[52]
-8
[-7]
11
3
132
63
[48]
12
[ 9]
57
[43]
55
6
187
63
[34]
28
[15]
96
[51]
6
4
155
<
[40*]
4
[ 3]
88
[57]
.
5
192
63
[33 ]
20
[10]
109
[57]
18
TABLE
4.
Gasoline
concentrations of the
solid phase
[mg/kg] at the
start of
the column
experiments
(C.) and
recovered after 6
(columns
1,2,3 and
6) and 15 (columns 4
and
5) months of
operation
-------
FIGURE 1. Map of the selected site at Asten [N-Br.]. The dotted line
gives the contour of the horizontal spreading of the
gasoline. The leaking tank is indicated by NT.
-110-
-------
gasoline conc. (g/kg d.w.)
1
T~
2
Depth (m)
r— 0
- 2
W//M///M
clay-loam
3
4
0,8
- 6
- 7
L- 8
clay-loam
clay-lo«"
clay-loam
FIGURE 2. Soil profile and average concentrations of gasoline at the
contaminated site [Asten], compared with the A, B,
C-reference values of the dutch government.
-Ill-
-------
COLUMN 3.
C
o
£
u
0
V
«
-------
COLUMN 2.
to -r-
c
11
c*
>x
e. -
2 -i
1 -
a
~
0 20
40
60
~r~
80
a
—i—
100
~ a
—i—
120
—i—r
140
' a
—i—i—i—
160 160
Time [d]
200
COLUMN 3.
\
o>
E
>v
6
80 100 120
Time [d]
140 160 180 200
FIGURE 5
Oxygen concencrations [mg.l* ] In the effluents of the
columns 1 to 5. Hind the different scale fore column 3.
-113-
-------
•„ U L'J M N
1.0
1.6
17
1 6
1.S
\ A
1 3
1 I;
1 i
0.9
L) IS
.«¦ ^
W . *
OS
Lb
0 ~
0 *
0.2
0 1
o
-J
ueFu a
¦cr
-iM-
I
1
a
—i—i—i—i—:—:—i—:—i—;—:—i—i—;—i—i—i—r
io 4o to to too 120 t*o too 180
Time [d]
2Q0
COLUMN 5.
o
o
\
u
2
1 .&
i.e
1.7
1.6
1.5
1.4
1.3
1.2
1.1
1
0.9
o.e
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
Uf
-p ¦n p
a ~
~
~
~ a
t—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—r
20 40 60 80 100 120 1 40 160 160 200
Time [d]
FIGURE 6. Total nitrogen balance [NO^-N, NOg-N, NH^-N] for the
columns 2 and 5.
-114-
-------
1b
14
\y
12
11
9
P
n
»*.
5
4
z
'2.
I
0
COLUMN 4. ADDITION OF H202
DiO C jiNTtUl
0 INFLUENT
A ?.t CM
TIME [DAT]
i- 62 CM O 48 CM
X ETFUerXT
COLUMN 5. RECIRCULATION ONLY
ulS'jDLVEtj INORGANIC CARBON
T—I—I—I—I—I—T
60 80 100 120
T—I—I—I—T
140 160 180
~ INFLUENT
A 27 CM
DUE [DAY]
62 CM O 46 CM
X EFFUJENT
7.
Concentration of dissolved inorganic carbon [mg C.l
column 4 [H„0_ and recirculation, 7 ] and column 5
[recirculation, 7 ] starting after the change of
operation from the first test period.
-115-
-1
] in
-------
COLLI MM -1, ADDITION OF H2C2
cue oCN»uN&
4U -
o
2
3
U
z
<
o
or
O
O
Ul
l/l
~ INFLUENT
A 4-27
TIME [DAY]
~ 4-62 O 4-48
X EFFLUENT
O
2
C>
o
K
a
s
s
0
ft
5
COLUMN 5. RECIRCULATION ONLY
DISSOLVED ORGANIC CARBON
t—i—i—i—i—i—i—i—i—i—r
80 100 120 140 160 180
INFLUENT
A 27 CM
TIME [DAY]
62 CM
X EFFLUENT
© 48 CM
FIGURE 8.
Concentration of dissolved organic carbon [mg C.l ] in
column 4 [H?0. and recirculation, 8 ] and column 5
[recirculation, 9] starting after the change of
operation from the first test period.
-------
o
o
o
6!
ar
4
U
n
c
0
o
u
N
1>
O
VI
1/1
6
FIGURE 9.
DiC PRODUCTION AT EACH SAMPUMNG DEPTH
COl.UMI< 4. ADCKTiCiN CiF PEROXIDE
O 6?
TIME [C>AY]
4 48 0 27
A EFT
-1,
Production of Che dissolved inorganic carbon [mg C.l" ] in
column A at each sampling depth as a function of time
after change of operation.
Id
z
o
3
o
t-
z
3
J
<
k.
o
10U
90 -
80 -
70 -
60 -
50 -
40 -
30
20
10 H
o
-to
R
7-
4
COLUMN 1
Ps~l L£ACHED •)
MASS BALANCE OF TOTAL GASOLINE
COLUMNS 1 - 6. •) FIRST 160 CJAY'S ONLY
1
g
ES"
*
*
j
I
m
—i 1—
COLUMN 2 COLUMN 3
177~X RECOVERED
J
i
—i 1
COLUMN 4 COLUMN S
[BIO—JOEGRADED
1—
COLUMN 6
FIGURE 10.
Mass balance for the column experiment with respect to the
gasoline [g] and calculated as percentage of the initial
amount divided in leached, recovered and [bio-]degraded
-------
FIGURE 11. Mass balance for Che column experiment with respect to the
individual gasoline components [g] and calculated as
percentage of the initial amount.
11A. Column 1, 11B. column 2.
z
D
<
t-
o
t-
k.
o
Z
o
D
<
c
uo
no
100
90
80
70
60
50
40
3D
20
10
0
-10
-20
-30
BALANCE OF INDIVIDUAL COMPONENTS
COLUMN 2. N AND P ADDITION.
1
* J_
tzL
\
i
r
A
\
m.
ai
'/
13
y
/
'/
A
t
A
/
'/
V
'/
'/
'A
4
~jsE
t.
1
*
—i 1 1——i 1 1—
TQL. E.B. p+m—X 1.3,5—TMB n—P.B. NAT.
—i 1 1 r
n-NAF. OCT. DEC. DODEC.
F~1 UEACHED
V7~X RECOVERED
COMPONENT
r^3 [BIO—]REM OVED
K
S
8
K
k
0
1
s
BALANCE OF INDIVIDUAL COMPONENTS
COLUMN 1. BLANC.
ED
t 1 i 1 1 1 r
E.B. p-t-m-X1,3.5-TMB n-P.B. NAT. m-NAF. OCT.
COMPONENT
177~X RECOVERED [BIO-JREMOVED
DODEC.
-------
FIGURE 11. Mass balance for the column experiment with respect to the
individual gasoline components [g] and calculated as
percentage of the initial amount.
11C. Column 3, 11D. column 6.
z
0
s
1
•J
£
£
b.
0
7
o
§
It
liO
110
100
90
30
70
CO
SO
40
30
20
10
0
-10
-20
—30
_\
§
BALANCE OF INDIVIDUAL COMPONENTS
COLUMN 3. N, P AND PER0*:t£. ADDITION
n
n
\
v '•
>
N
»,N
k
fs
\
h
I >
\
k>
V
s
\
r
SI
\
V.
\
r-«
\
f?
w
*N
V
\
\
p
\
\
\
LI
.\
_E
ft
S
>
J
'/\s
i i i 1 1 i i i i r
TOL. E.e. p+m—X 1,3,5—Tm8 r>—P.6. NAT. m-NAF. OCT. DEC. DODEC.
m LEACHED
COMPONENT
V/ A RECOVERED P^vl [BI0-]REM0VED
V.
t-
z
o
H
k.
o
z
o
§
K
120
IIO
100
90
80
70
60
SO
40
30
20
10
0
-10"
-20
-30
<5
*
N ^
*
*
*
BALANCE OF INDIVIDUAL COMPONENTS
COLUMN 6. N. P AND RECIRCULATION
*
*
*
*
*
__
\
\
s
s
*
\
*
*
*
*
*
N
\
*
*
*
Is
s
s
s
s
\
*
*
*
*
N
*
*
*
*
*
*
—i 1 1 1 1 1 1—
TOL E.B. p+m—X 1,3,5—TMBn—P.B. NAT. m-NAF.
OCT.
—I T
Dec. DO DEC.
rr~l LEACHED
COMPONENT
P7"3 RECOVERED E7^ [BIO-]REMOVED
-------
I i-WI » Ol I/-VI1 I |l« Oi I U LJIWI I 1/rWM twi 1
J /
/
/
1
f
/
/
BXOFZLTER (air)
DISCHARGE on SEWERAGE
FIGURE 12.
Flow chart of the In-Situ Biorestoration.
H SfTU BORESTOR/mON OF A SUBSOfl.
13.
Crosseetion of th« «oll »lth an overview of the restoration
I'r,,C•5• -120-
-------
TYPE OF TREATMENT:
General: Microbial Degradation
Specific: In-Situ Enhanced Aerobic Restoration
Manufacturer:
FORMER USE/PROBLEM: Petrolelum spill site
Jet fuel spill - underground fuel
lines
LOCATION/COUNTRY: Eglln Air Force Base
Fort Walton Beach, Florida
United States
CONTAMINANT(S): Aviation fuel
MEDIUM OF CONTAMINANT(S):
STATUS AS A NATO/CCMS
STUDY PROJECT:
Proposed: 3/87
Accepted: 3/87
Interim Report(s): 11/87
Expected Completion Date:
Final Presentation: 11/88
-121-
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ENHANCED BIODEGRADATION OF JET FUELS
EGLIN AFB, USA
A Case Study for the NATO/CCMS Pilot Study on
Remedial Action Technologies for Contaminated
Land and Groundwater - November 1988
Mr Douglas C. Downey
HQ AFESC/RDVW
Tyndall AFB, FL USA
-122-
-------
CCMBINED BIOLOGICAL AND FHYSICAL TKEA3MENT OF
A JET KJEL-CENIAMINATHD AQUIFER
Douglas C. Downey1, Robert E. Hinchee2, Mark S. Westray3,
Janes K. Slaughter
"HjSAF Engineering and Services Center
Tyndall AFB FL 32403-6001
2Battelle Memorial Institute
505 Kin? Avenue, Ooluntous CH 43201-2693
3
Formerly w/IT Corporation
Westinghouse Environmental Services
3500B Regency Pkwy, Cary NC 27512
4
EA Engineering, Science and Technology
41 Lafayette Circle, Iafayette CA. 94549
ABSHaCT
Early in 1987, the Air Force Engineering and Services Center (AFESC)
initiated a full-scale enhanced biodegradaticn research project at a JP-4
jet fuel spill site on Bglin AFB near Ft Walton Beach, Florida. An
underground pipeline leak discovered late in 1984 had released an
estimated 20,000 gallons of JP-4 and contaminated soil and shallow ground
water over a two-acre area. Following free product removal, a ocnplete
site characterization revealed that over 90 percent of the remaining fuel
residuals were in the unsaturated zone. This project has place special
eqfrasis on the treatment of residuals in the soil as they represent the
source of long-term ground water contamination. A treatment system was
designed to caqpare the operational benefits and limitations of three
hydrogen peroxide/nutrient application methods: injection wells,
infiltration galleries, and spray irrigation. A contaminated area
receiving no treatment has been set aside as a control to ccnpare natural
degradation rates to enhanced rates in the treatment area. Pilot tests
were conducted in the infiltration galleries to study the interaction of
hydrogen peroxide and nutrient solutions with soil minerals. Studies
concluded that hydrogen peroxide stability was inpacted by biological
enzymes, inorganic iron, and soil humic materials. Several methods of
improving hydrogen peroxide stability have been attempted with limited
success. Despite limitations in oxygen supply, a full-scale withdrawal
-123-
-------
and reapplicaticn system has been operating for over one year and a
portion of the fuel residuals have been removed through a ccmbinaticn of
biodegradaticn, hydraulic washing, and aboveground aeration. Observations
on system operation and soil and ground water data frcm the initial 12
months of this field project are reported in this paper. Final soil and
ground water sampling will take place in Septtanber, therefore only
preliminary results were available before the publication deadline.
INiMJJUUUiCN
Each year the U.S. Air Faroe stores and transfers millions of gallons
of JIM jet fuel at over 200 Air Force installations. Fuel leaks and
spills are by far the moGt frequent sources of soil and groundwater
contamination on these installations. The Qivircnics Division of the Air
Force Engineering and Servioes Center (AFESC), located at Tyndall
AFB, Florida, is responsible far developing and testing improved methods
of soil and groundwater decontamination. Soil decontamination has been
emphasized, because in most soils the majority of the JP-4 will ram in in
the unsaturated zone and slowly leach into the groundwater (Davis et al,
1972). These soil residuals represent the long-term source of ground
water contamination and must be addressed in site remediation.
Enhanced in situ biodegradaticn is an innovative technology which has
received much attention and research during the past two decades (Lee, et
al, 1988). While several nrmnprcial firms have reported successful
ground water resnediations, published results have lacked sufficient data
to determine the effectiveness of biodegradaticn in reducing fuel
residuals in the vadose zone. For this and other reasons, AFESC has
conducted independent field tests of this technology prior to reccmnending
it far widespread Air Faroe application.
In 1984, AFESC initiated a pilot-scale test of enhanced biodegradaticn
at a site on Kelly AFB, Texas. As this test progressed, problems with
soil permeability were encountered reducing the delivery of hydrogen
peroxide and nutrients through injection wells. This reduction in
permeability was attributed to both natural silt and clay soils and the
precipitation of calcium phosphates which farmed as injected phosphates
reacted with calcium in the soil (Wetzel, 1987). Permeability problems
reduced the delivery of oxygen and consequently little biodegradaticn
occurred. Based on these results, a second site with more favorable soil
permeability was selected at Eglin AFB, Florida.
In 1986 AFESC awarded a ocnpetitive contract to EA Engineering,
Science and Technology and their subcontractor IMC Aquifer Remediation
Systems (now a part of IT Corporation) to conduct an enhanced
biodegradaticn demonstration on the site. EA Engineering, Science and
Technology was responsible far overall system design, operation and site
monitoring while IT Corporation has provided microbiological support and
operational expertise in nutrient and hydrogen peroxide application
systems.
-124-
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SITE HGRQE
In April of 1984 a leak was discovered in an underground jet fuel
pipeline in the Eglin AFB petroleum storage area. A preliminary site
r^iar-ar^-oy-irat-Aon estimated 30,000-45,000 gallons of JP-4 jet fuel had
contaminated approximately 4000 cubic yards of soil and shallow aquifer
material (Weston, 1984). Follow up sampling in August 1985 decreased that
estimate to 20,000 gallons. A series of shallow, gravel-filled trenches
were installed perpendicular to fuel movement and skinner punps recovered
over 7000 gallons of free product. By early 1986, free product had been
removed to non-recoverable levels and skinner punps were turned off.
Friar to system design a ccnplete site characterization was
aooonplishad to better define hydraulic, contaminant, and microbiological
conditions. The site is located in an area of unconsolidated and
relatively homogeneous coastal sands that extend from the surface down to
40 feet. Below the sand, a 400-foot confining clay layer protects the
rfrrprr Flaridian Aquifer. Die contaminated shallow aquifer is only three
to five feet below the surface across the site and has an average
hydraulic conductivity of 7 X 10-2 aa/sec. The highly permeable soils and
the shallow depth to contamination make this an excel lent site far testing
enhanced biodegradation.
Cne of the primary objectives of this test was to insure that a
sufficient number of ground water and soil sanples were taken to assess
the performance of this technology. An initial soil vapor survey was
performed to delineate the extent of free product influence and to assist
in monitoring well locations and application system design. A Ehotovac
10S50 portable gas chromatograph was used to analyze soil gas sanples
taken at a constant depth of two feet on a radial grid across the site.
Monitoring wells and soil sampling locations were selected on the
basis of the soil vapor survey. Initially 22 monitoring wells were
constructed and soil samples taken at one-foot depth increments at 12
locations. During the course of the research, the number of ground water
monitoring wells has increased to 40 and soil sampling locations to 16. In
order to carpare natural degradation rates to degradation rates under
enhanced nutrient and oxygen conditions, monitoring locations were
established in a control contaminated area which received no nutrients or
hydrogen perooeide. The "control area" was a unique feature of this test
which is normally unacceptable far ccmnercial site restorations.
Total Organic carbon (T0C) was selected as the general indicator of
fuel contamination in ground water. Background TOC levels of 15 mg/L were
recorded upgradient of the site. Total Petroleum Hyrocarbons (EPA Method
418.1) was used as the general indicator of fuel contamination in the
soil. Background levels of less than 20 mq/kg were qmiirm in
unoontaminated soils.
A ocnplete GC/MS analysis was performed on selected ground water and
soil sanples. The purpose of the GC/MS analysis was two-fold. The
Florida Department of Environmental Regulation required that twelve
representative coopounds, including benzene, toluene, and xylenes be
-125-
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monitored in the ground voter. The list was expanded to 43 coqpounte to
monitor the specific degradation rates of a broad range of nHphoMr' aid
aromatic fuel oonponents. A ocnplete discussion of QC/m results is
beyond the scope of this paper. This data will be included in an AFESC
Technical nunut to be publinhnd in early 1989. Figure cne illustrates
the areas of free product influence prior to biodegradaticn operations,
ard the location of initial monitoring wells in relation to the basic
operation system in the next section.
Microbial enumerations were also perforated on soil and ground water
at most monitoring locations. Microbial monitoring provided a
measure of microbial response to nutrient and oxygen enhancements over
time. Soil samples at each monitoring point were collected at two depth
intervals, one from the capillary fringe zone above the water table and
another sample one foot below the water table. 1he microbial populations
at these two depths would be nest likely influenced by ground waters
enhanced with nutrients and oxygen. A susnary of initial site conditions
within the contaminated area is included in Table One.
A
~i -J
/
ABOVEGROUND I
. TREATMENT" ^
/-CO
I
©
FREE PRODUCT
• INFLUENCE
\
<
Ai-i
''ei3\
v ' «U>
V
V eH
•19
•20
©
20 40
"feet
O RECOVERY HELL
e MONITORING WELL
A INJECTION WELL
Figure 1. Eglin AFB Site Profile
-126-
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TABLE ONE
Initial Site Conditions in Contaminated Area1
Water fmg/Ijl
126 (18)
6
3
<.2
8
12 (<.5)
5.4 units (6)
<1 (3)
20° C
15
1.6
1 Average of contaminated monitoring locations
( ) = Uhoontaminated background level
2 Total benzene, toluene and xylenes
3 Total alkanes detected on GC/MS
Laboratory microbial enumerations were ccnpleted using a modification
of spread plate count method for heterotrophic bacteria (AfflA, 1985).
Ground water samples ware prepared far enumeration by performing serial
rtorrimai dilutions of the sasple in a sterile mineral salts broth.
Subsurface soil sanples were prepared using a modification of the method
reported by Balkwill and Qiiorse, 1985. The method involves hcmogeniza-
tion in a waring blender of five grams of soil in 50 mis of a solution
consisting of 1% sodium pyrophosphate, 0.1% polyvinylpyrrolidone-360
(PVP-360). This hexnogenization step is designed to facilitate release of
bacteria attached to particles. The henogenate is then diluted and
plated in the same manner as for water sanples.
The concentration of total heterotrophic bacteria is defined as the
number of colony forming units per milliliter of ground water or per gram
(dry weight) of soil, that can form nacroscopically visible colonies on
0.23% nutrient agar after one week incubation at ambient temperature and
oxygen. Hydrocarbon-degrading bacteria are defined as those capable of
forming colonies on carbon-free mineral salts agar when incubated under a
hydrocarbon-'vapar atmosphere at ambient teoperature for one week
(Jamison, et al., 1976).
Parameter Soil fma/tari Grcxmd
TOC
TPH- 2000 (20)
BEr 110
C8 - C1?3 640
ro4
NHj
Pe( total) 850
pH
Dissolve Oj -
Teap
,5
Total Bacteria (10 CFU) 2
HC Degraders(10 CFU) .9
-127-
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laboratory Biodegradation Studies
One of the important tasks undertaken in the laboratory phase of this
project was to conduct a bench-scale degradation study, using
contaminated soils and ground water fran the site, to determine the
effects of nutrient and oxygen supplementation on the rate of contaminant
biodegradation, and to estimate the extent of contaminant removal that is
achievable biologically under laboratory conditions. lhese studies have
historically been based on batch reactors, or "microcosms," which consist
of soil/ground water slurries in sealed glass vessels. The microoosns are
then treated with the appropriate nutrient and hydrogen peroxide
amendments, and one set of microcosms is sterilized anchor inhibited with
a biological poison to account far physical/chemical mechanisms for
contaminant removal fran the system. Aqueous samples can then be
periodically withdrawn for microbial, nutrient and/or contaminant
analyses, or the entire reactor can be sacrificed far analysis. While
studies such as these provide a limited model of the natural aquifer
environment, the resultant information is useful in determining the
relative effectiveness of different nutrient types and concentrations on
biodegradation rates, and far demonstrating the heterotrophic potential
far contaminant destruction.
For reasons of simplicity and cost, most microcosm degradation studies
monitor aqueous phase contaminant biodegradation. For the Eglin project,
however, we attempted to quantify the degradation of the total amount of
organic material within the reactors. Microcosms were prepared be
combining 20 gms of contaminated soil and 20 mis of site ground water in a
40 ml VOA vial. Vials were tightly sealed and various nutrient
concentrations injected through a septum to determine their effect.
Excess oxygen was maintained through hydrogen peroxide additions. The
microcosms were separately analyzed; the aqueous fraction was extracted
with pentane and analyzed by capillary GC-FID. The soil underwent Saxhlet
extraction according to Standard Methods 503D, followed by analysis of the
extracts using capillary GC-FID.
A GC/FID analysis of the aqueous phase showed ttat biodegradation was
enhanced by 25 ppm concentrations of Restore 37s and that the total
extractable organics were degraded fran 35 ppn to <.2 ppn in nine days.
TViig data confirmed that indigenous microbes would degrade soluable fuel
ccnpcnents with minimal-nutrient additions if adequate oxygen was
available. Restore 37s is a patented, prepared nutrient mixture
consisting of 50% asmonium chloride and a blend of disodium phosphate,
sodium tripolyphoephate and monosodium phosphate.
Analysis of the solid phase (soils) exhibited considerable noise and
due to extraction problems actually shewed an increase in organics. These
analytical procedures cannot be reliably used to measure biodegradation of
low solubility conpounds adsorbed or occluded in soils. (We are currently
repeating the microcosm study using a modified purge and trap procedure to
measure organics removal from both the aqueous and soil phase. The
results of this isproved procedure will be published in the final AFESC
Technical Report.)
-128-
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SYSTEM EESK3J
Thb ability of the shallow aquifer to produce sufficient water for
recirculation of nutrients and oxygen was a critical design factor that was
first determined through a series of punp tests on all recovery and
injection wells. Four recovery wells were installed on the dcwn-gradient
rwimafroT- of the contaminated area using the cable tool drilling method.
The six-inch "a11a were constructed with 5 feet of .02 slotted PVC screen
5-10 feet below the static water table to prevent free product
drawdown and ncvaent into the wells (Figure 2). Injection well design is
dismsBfri later in this section.
FromPoteNnO-,
filler ]
Cement Grout
i to ha Surface
6* PVC
Schedule 40
Casing
Bentonito Seal
6* PVC Casing
with bottom piug
injection well recovery well
Figure 2. Recovery and Injection Well Design
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After Initial installation, the wells were air-developed. All veils
were tested at imyimim punp yield far three hours; this was sufficient to
determine the hydraulic parameters of the highly permeable aquifer. Water
levels were measured during testing using an electronic water level
indicator or a IMC oil-water interface probe. Well yields were measured
with a flow meter. Mentoring wells located at varying distances from the
punped well were used as observation wells. In general, the treatment area
can be divided into two zones based on the observed and calculated data:
1. a northern zone of higher elevation (wells INI, IN2, Rl, and R2) with
trananissivity of approximately 20,000 gp^/ft (250 m?/d) and permeability
of 270 ft/day (9.5 10"2 cra/sec)
2. a southeastern zone of lower elevation with transnissivities of
10,000 gpd/ft (125 m^/d) and permeability of 130 ft/day (4.7 x 10~2
cm/sec)
The lower trananissivity of well R4 may be related to an area of finer-
grained sediments deposited by an old stream channel.
Discussion of Ojj Simply Requirements
Natural aerobic degradation at this site has been limited by depleted
oxygen in the groundwater and capillary zone. Background oxygen levels of
.5 - 1.0 pgm were measured in monitoring wells in the contaminated area.
The primary objective of system design was the delivery of adequate oxygen
far mineralizticn of fuel hydrocarbons. The oxygen required was calculated
based on an estimate of the mass of hydrocarbons present and the
stoichiometric requirement for complete mineralization. lhe basic
mineraliztian equations for typical hydrocarbons follow :
CgHg + 7^02 —» 6CO2 + 3H20 for benzene
or
CgH^g + 12\02 *¦ 8CO2 + 9H20 for octane
Occplete mineralization requires approximately 3.1 pounds of oxygen per
pound of benzene or 3.5 pounds of oxygen per pound of octane far acnplete
mineralization. Based on our site characterization, it was estimated that
the 16,000 lias of hydrocarbon remaining in the treatment area's soil and
groundwater would require approximately 40,000 lbs of oxygen far
mineralization. Assuming 100% oxygen utilization efficiency, the necessary
oxygen and corresponding peroxide concentrations can be calculated for a
variety of punping rates:
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Peroxide
Concentration
(pq/L)
Effective Oxygen
Concentration
iSS^Ll
Required Hater
Volume
(gallons) fggn/16 mo.^
100
300
500
0
8
50
150
250
650,000,000
100,000,000
30,000,000
20,000,000
1100
170
55
33
Based cn punp tests and 0_ requirements, an initial peroxide concentration
of 500 mg/l and a punping range of 30-40 gpm were selected to deliver the
required 0^ over the 16 month fixed contract length.
Irczi Removal Systan
Iron concentrations in ground water were reported to be below 1.0 mg/1
(Weston, 1984). Our sampling found iron levels in contaminated ground
water in the range of 8 to 26 mg/1. The recovery well discharge water was
found to contain an average of 12 mg/1 of total ixon. Due to highly
reducing conditions a mimi in anaerobic, contaminated groundwaters, this
iron emerges from the wells in the ferrous (Fe+2) farm. Oxidation to the
less soluble ferric (Fe+3) farm during aboveground treatment leads to
precipitation, and clogging of the injection systems. The concentration of
iron at injection points can also reduce the stability of the peroxide
(Britten, 1985).
In order to reduce iron concentrations in the injection systems a
sedimentation basin was added following the aerator. To further reduce
iron concentrations going into the injection wells a pressure filter was
installed. The ccnbined sedimentation and filtration removed approximately
90 percent of the total iron entering the injection wells.
Three Application Mathods
Three basic technologies are available for oxygen and nutrient
injection; injection wells, infiltration galleries and surface application;
each with its own advantages and disadvantages. The injection well most
directly delivers the nutrients to ground water, however, nutrients are
poorly delivered to the unsaturated zone. The injection well has a
relatively snail surface area and is therefore prone to clogging.
Infiltration galleries and surface application deliver the nutrients in a
more uniform pattern which allows more effective delivery to the
unsaturated zone. At many sites the drawback, to infiltration galleries
and surface application techniques is the potential difficulty in
delivering nutrients to the saturated zone. If an impermeable or less
permeable strata exists above the groundwater it may prevent or limit
percolation. In the case of the infiltration gallery, this can be
overcome by placing the system beneath the less permeable strata. In
general, the injection well is the most expensive application method, with
the infiltration gallery being intermediate in cost and surface application
being least expensive. In difficult situations such as paved or developed
-131-
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sites, or sites with a relatively deep, less permeable strata, the
infiltration gallery can be substantially more expensive than an injection
well.
As the ground water is quite shallow at the Bglin site and no
significant stratification exists in the unsaturated zone or the atwiiru
saturated zone, surface application is the technique of choice. The site,
however, is certainly amenable to all three technologies and due to the
n1 'urnrh nature of this project all three were demonstrated, it was not
intended that three separate treatments be tested far remediation
efficiency, rather the relative effectiveness of each technology was
evaluated and each injection system modified as necessary to isprove
nutrient and oxygen delivery. The application systems were designed to
receive approximately 10 gpa each or agproodmately 6,000,000-7,000,000
gallons over the course of the study.
Injection well construction is shown in Figure 2. The wells were
screened from approximately one foot above ground water surface to a depth
of nine feet below groundwater surface to allow uniform nutrient
distribution. The design diameter of six inches was considerably
oversized far the hydraulic needs of this site to provide a safety margin
against plugging. The stainless steel screens allowed vigorous
development, redevelopment and acid cleaning.
Shallow, gravel-filled trenches were used as infiltration galleries as
illustrated in Figure 3. The large surface area of these galleries
provided a broad distribution of nutrients and percadde pnrpmfltcnliir to
flow lines. Surface application was the sisplest farm of nutrient and
pertadde distribution. The surface spray system provided an even
application of nutrient and oxygen over an 1800 sq ft area using a
sprinkler system. Figure 4 provides a schematic of the aboveground
treatment and application system.
'///
4" perforated PVC Installed
level and with perforations
in an UP position
Large Stone Backffll
(1'min. size)
12" min.
Figure 3. Infiltration Gallery Design
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*1
Nutrient*
i
r
>
Figure 4. System Flow Diagram
Nutrient Addition
Nutrient addition was designed to be in excess of micricbal
requirements. Labaroatory microcosm tests indicated that nutrient levels
as lew as 25 ppm would support microbial degradation. Hie decision to use
nutrient addition was based on three factors. First the phosphate
present in the nutrient solution oould act to stabilize the peroxide
(Britrton, 1985). Second, laboratory column tests shored that
orthphosphate precipitation in site soils was inhibited in the presence of
tripolyphosphate at Restore 375^ injection concentrations of at
least 1000 it" Finally, an excess addition would insure that oxygen alone
was limiting biodegradation. One concern of excess nutrient addition is
the potential for precipitate formation such as calcium phosphates
resulting in reduced aquifer permeability. The potential for aquifer
plugging at the Bglin site was lessened due to the initial high
permeability.
Restore 375* was added on a batch basis of 150 lbs/week and metered into
the recirculation flow to mate a delivery concentration of 1000 ppn.
Nutrient solutions were added three times a week and each pulse was
approximately four hours. Typically, nutrients were added on Monday,
Wednesday, and Friday.
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h^b application rate exceeded the minimim requirement far microbial
degradation of fuels. Assuming 16,000 lbs of fuel hydrt carbons and a
carbon: Nitrogen: Phosphate ratio of 100:6:3, and that 33% of the
hydrocarbon was converted to bianass (less than 33% would probably be
converted), nitrogen requirements would be 7.20 lbs and phosphorus
requirements 360 lbs. Despite reduced oxygen delivery rates due to
peroxide stability problems, the design nutrient injection schedules were
maintained and to date 750 lbs of nitrogen and 440 lbs of available
phosphorus have been delivered to the site. Subsequent ground water
sampling across the site indicate that increased levels of P04 and NH4 were
well-distributed in the saturated zone.
In-Situ Peroxide Stability
Tests of in-situ peroxide stability and oxygen transport were carried
out in the infiltration galleries. Due to the shallow ground water at this
site, mounding occurred in the vicinity of the galleries which resulted in
saturation to the ground surface. Shortly after peroxide injection was
initiated, gas bubbles were observed rising through the saturated sandy
soil imnediately above the galleries. This observation coupled with a
failure to observe peroodde in any down gradient wells (including EA 18
installed 1 ft dewn gradient of the injection galleries) lead to the
suspicion that peroodde deocnposition was very rapid and resulted in off
wasteful gassing of oxygen. Initial laboratory batch studies using a 3:1
ground water to soils ratio had indicated that a 500 ppm hydrogen peroodde
addition would have a half-life of approximately six hours in the Bglin
aquifer.
A monitoring well (EA-22) was installed directly in one of the injection
galleries. While the system was operating under continuous peroxide
addition, peroodde concentrations observed in EA-22 were very close to, or
slightly below the 500 ppm measured in the feed lines to the galleries. To
evaluate in-situ peroxide stability, tests were conducted in which the flow
to the galleries was shut off and the disappearance of peroodde in EA 22
was measured over time. Peroodde half-lives, based on first-order decay
rates, were observed in the 30 to 90 minute range, far less than the six
hours predicted in the laboratory.
In order to determine the effect of phosphate pretreatment a new series
of galleries were constructed. These galleries received nutrient
solution, including phosphates, prior to initiating peroodde injection.
Similar peroodde stability tests were conducted in these "pretreated"
galleries, however, no significant increase in peroxide stability was
noted. Due to the significant off gassing and waste of oxygen at the 500
ppm peroxide addition rate, a decision was made to reduce the operating
concentration to 300 ppm.
Throughout the project several experiments have been conducted to
determine the of hydrogen peroodde doaqposition. Both biological and
inorganic reactions have been identified as contributing to this
instability. These findings are briefly discussed in the conclusions.
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SYSTBf HRFCRMMICE
Withdrawal and Application Systsns
During the jwi'Hai weeks of operation, the four recovery wells produced
over 40 gpm of continuous flow. Over the past 15 months of operation, well
production has decreased to 32 gpn. Regular treatments with acid and
vigorous scrubbing have been required to clean both recovery and injection
well screens.
Hie total volume of water passing through each of the primary
application systems to date is:
Infiltration Galleries 6,500,000 gallons
Spray Irrigation 7,800,000 gallons
Injection Nells 1.000.000 gallons
Total 15,300,000 gallons
Hie infiltration galleries and injection wells have shown a tendency to
clog and flow-through has been reduced. In the case of the infiltration
galleries this problem was remedied by increasing their nunber. Initially,
4 galleries with 40 linear feet of injection area were installed and were
capable of taking the full 10 gpn. After surface flooding was noted three
additional galleries with an additional 30 feet of linear injection area
were added. Finally four additional galleries were installed in an old
free product recovery trench which was approximately 40 feet long, 10 feet
wide, and was filled with approximately 4 feet of gravel (approximately 2
to 6 feet below land surfaoe). The galleries have received a continuous 10
gpn flow far over one year.
Flow through the injection wells was significantly reduced over tine.
Efforts were made to acid wash and redevelop the wells by adding 1 to 2
gallons of 31% industrial Hd and applying 100 ± gallons of water. The
wells were then allowed to sit for a 16 + hour contact time. The wells
were then purged until the pH returned to 6.0 or greater. At times the
wells were also air surged and/or vigorously brushed. Despite the cleaning
and redevelopment the wells oontinued to clog and within a few months were
only able to accept only 1 ± gpn. For this reason the total volume
introduced through the injection wells was signficantly less than design
volumes.
Ihe spray irrigation area performed well and consistently received 10+
gpn over an area of 1,800 ft2 without notable reduction in efficiency.
Occasional roto-tilling of the soil isproved permeability and reduced
overland flow. Additionally, peroxide concentrations in water puddles on
the ground were not significantly less than those in the feed to the spray
irrigation area indicating little peroxide loss in the spray process.
However, sasples of infiltrate taken in the spray area vadose zone revealed
that peroocide rapidly decomposed in the first six inches of the soil. In
one test, dissolve oxygen in the infiltrate varied frcm 23 mg/1 at the
surfaoe to 2 mg/1 at 2.5 feet below land surface indicating oxygen
utilization in the contaminated soils.
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Volatiles Renewal in Aeration System
Bjb aeration basins which were originally installed to oxidize iron were
upgraded to also remove the volatile organics. A series of tests to
evaluate volatile organic renewal efficiency were conducted at air to
water ratios varying frcn 8-36:1. Based on these tests the ai to water
ratio was increased to approximately 25 to l in order to achieve 95%+
removal of volatile organics. This inexpensive method of voc renewal
mist be factored into the overall mass balance on fuel removal and
separated from biodegradation.
Qxund Hater Contamination Data
Data from two monitoring wells in the active treatment zone and two
wells in contaminated control areas is provided in Figure 5. BIX was
selected as an indicator of soluable fuel contamination for this
caqaariscn. EA-2 is located in the spray application area. EA.-8 is in a
control area receiving a spray of ground water without nutrients or
peroodde. EA-EA-19 is located 12 feet downgradient of the infiltration
galleries while EA-5 is located in a contaminated control area not
influenced by nutrients or peroxide. Both EA-2 and EA-19 have shown
decreased levels of BIX. Some removal of BIX has also occurred at EA-8,
possibly due to the continuous application of partially resbare^/aerated
ground water at the surface. Ground water at EA-8 has also been influenced
by nutrient additions through the injection wells which may account far
seme BIX removal in the saturated zone. BIX levels in the EA-5 control
area decreased in July 87 far an unknown reason but have remained stable
over the past nine months.
mg/L BTX
EA-2 -+~ EA-5 Control EA-8 Control -a- EA-19
Figure 5. Removal of BEX From Qxund ifaber
-136-
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prrf i OartaaiiHticn Data
To dabs fuel residuals in soils above the water table in areas
influenced by injection wells and infiltration galleries have shown no
solid evidence of enhanced biodaqradati.cn. There is no evidence that
enhanced nutrient and oxygen levels in the ground water have influenced
biodegradation in the soils above the water table. Soil sanples from the
spray application area have shown mixBd results. Figure 6 illustrates the
difficulty in assessing biodegradation in the unsaturated zone, gamp-iaa
taken near EA-2 indicated a definite decrease in TEH has occurred.
Unfortunately, samples taken at EA-3, which is also in the spray
application area, show no consistency and even show an apparent increase in
TEH. The TEH values at the EA-5 aorrtrol area have also been subject to
seasonal variations which have Bade data interpretation very difficult.
There has been no increase in free product in these areas that would
indicate a new fuel leak. However, we have observed small lenses of free
product on the site which have randomly moved through our monitoring areas.
Microbial Data
Microbial enumerations of soil and groundwater have suffered from
similar variability. Once again the most significant microbial activity
appears to be taking place in the spray application area. Although not an
impressive exponential growth, both total and hydrocarbon degrading
bacteria have multiplied their numbers 10 to 15 times in the soils and
groundwater within the spray area. Bacteria counts in the EA-5 control
area have shown a ten-fold decrease in numbers over the past nine months.
There has been a general increase in the proportion of hydrocarbon
degrading to total bacteria suggesting an adaptation of microbial
populations to growth on fuel substrate.
mg TPH/hfl toil (xlOOO)
5
O1
Mar. 87
Jul 87
Sep 87
Sampling Event
Jan 88
Mar 88
EA-2 EA-3 -e- EA-S CONTROL
Avg of 3 to 4 Depths at Each Location
Figure 6. TEH Data From Spray Area
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GGNOISIENS
An Oxygen Shortfall
Due to rapid peroxide destabilizaticn end oxygen loss at point of
injection it was not possible to deliver sufficient oxygen for complete
hydrocarbon mineralization. The causes of hydrogen peroxide instability
at the Bglin site have been identified through a series of laboratory and
field experiments (Spain et al, in press) They concluded that catalase
enzymes released by aerobic bacteria near the points of injection are the
major cause of rapid peroxide deccnpositicn and oxygen off gassing.
To a lesser extent, humic materials and inorganics such as iron a1g"
increase the rate of peroxide deccnpositicn at the Bglin site.
Estimated ^«*»
The extent of biorenediation, or hydrocarbon biodegradaticn may be
estimated from the actual oxygen delivery rates. Peroxide was injected
into approximately 16,000,000 gallons of water. Based on peroxide
stability and oxygen measurements at the points of injection, it is
estimated that an average 25 xng/l of oxygen was actually delivered in this
water. Very low oxygen concentrations down gradient of the injection
points indicated utilization. We estimate that sufficient oxygen was
delivered to mineralize approximately 1,200 pounds of hydrocarbon. It is
possible that some of this oxygen was incorporated into microbial biomass,
and therefore, greater than 1,200 pounds of hydrocarbons may have been
removed.
Estimated Volatilization
A significant quantity of fuel residuals were removed in the above
ground aeration basin. Based cn T0C analysis of groundwater entering and
leaving the aeration basin, a loss of volatile organics (measured as 15-
20 mg/1 T0C) occurred throughout the past 12 months. This means that the
aeration basin has removed at least 2000 pounds of hydrocarbons from the
16,000,000 gallons of water punped through the site. Contributing to this
process is an unknown quantity of fuel residuals which have been washed
from the soils into the groundwater due to natural leaching and soils
washing in the spray application system. A better understanding of the
hydrocarbon mass balance is anticipated after all the site data has been
collected and analyzed.
Four Noire Years
In order to deliver sufficient oxygen with the observed peroxide half-
life and subsequent oxygen delivery rates, and assuming continued
volatilization of 2000 pounds/yr, four more years would be required to
deliver the ni
-------
RacoH on current operating costs it is estimated that future operating
costs of $210,000 per year far the additional years vroulc be incurred.
Therefore, a total cost of approximately $1,400,000 in non-research costs
would be the required far full site clean 19. It siould be noted
that this is based on the assumption of 100% oxygen utilization, actual
cost could be substantially higher. Far those wishing to project these
costs to other sites it should be pointed out that this site \tas in an open
field and had mi™™™ construction and maintenance costs.
RRrMMBUKHGNS
1. In situ peroxide stability oust be greatly improved to provide adequate
oxygen dcwngradient of injection points. At the present cost of $3 - $4.20
per gallon far 35% hydrogen peroxide, the available oxygen is costing $1.50
- $2.40 per pound. In ocnpariscn, the cost of industrial grade Htjriri
oxygen is only $.10 per pound. Therefore, if the effective oxygen
concentration achieved with peroxide addition is not substantially greater
than the 40 mg/1 of oxygen saturation possible with liquid oxygen, then the
use of peroxide is not cost effective.
2. Greater enphasis must be given to both vertical and horizontal
distribution of contaminants. Oxygen delivery systems nust influence the
vadose zone where a majority of the fuel residuals ram in. In this project
the spray system was the only method which appeared to do this. Other
technologies such as soil venting have a far geater potential far
introducing oxygen into unsaturated soils.
3. laboratory methods far predicting in situ biodegradation, peroxide
stablity and geochanical side reactions nust all be improved. Current
procedures must be refined to account far site specific soil and ground
water chemistries. On site pilot tests are iw.ximiftndad to determine in
situ peroxide stability, oxygen utilizaion rates and potential plugging
problems.
4. Finally, there is a need far mare sharing of meaningful site data by
those experience in the application of this technology. Data on peroxide
stability and transport, oxygen utilization and the removal of fuel
residuals fran soils are all missing from the open literature.
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SS^BBICES
1. AFHA, 1985. Standard Methods far the Examination of Water and
Wastewater. 16th ed.
2. Balkwill and Ghiorse, 1985. Characterization of Subsurface
Bacteria Associated With IVro Shallow Aquifers in Oklahoma.
Applied Environmental Microbiology. Vol 50. pp 580-588.
3. Britten, L. N. 1985. Feasibility Studies on the Use of
Hydrogen Peroxide to Enhance Microbial Degradation of
Gasoline. American Petroleum Institute Riblication 4389.
4. Davis, J.B. et al. 1972. The Migration of Petroleum Products
in Soil and Groundwater. Riblicaticn of the API
Permittee cn Environmental Affairs. Dec 1972.
5. Jamison, V.W., Raymond R.L., Hudson J.O., 1976. Biodegradation
of High-octane Gasoline. Proc. 3rd Int. Biodegradation
Symposium. J.M. Sharply and A.M. Kaplan, eds. Applied
Science Rib. pp 187-196.
6. lee, M.D. et al. 1988. Biorestoration of Aquifers Contaminated
with Organic Ccnpounds. ORG Critical Reviews in Errv. control.
Vol. 18. pp 29-89.
7. Spa-in J.C., Milligan J.D., Downey D.C., Slaughter J.K. In Press.
Excessive Bacterial Decomposition of H3O2 During Enhanced
Biodegradation. Accepted for publication in Journal of Ground
Water.
8. Weston, Roy F. Inc. 1984. Response to Fuel in Ground Water at POL
Area Eglin AFB - Tfcble 1 Hydrualic Characteristics.
Air Force Engineering and Services Center Tyndall AFB.
9. Wetzel R.S., Durst C.M., Davidson D.H., Sarno D.J. 1985. In Situ
Biological Treatment Test at Kelly AFB, TX, Vol II Field Test
Results and Oost Model. AFESC ESL Tech. Report 85-52.
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BIOGRAPHICAL SKETCHES
Douglas C. Downey, PE is a senior research engineer assigned to the Air Force
Engineering and Services Center Laboratory, Tyndall AFB FL 32403 904) 283-2942
He is a 1977 graduate of the US Air Force Academy and attended Cornell
University where he received a Masters Degree in Civil/Environmental
Engineering in 1981. Mr Downey is a registered professional engineer and is
responsible for the development and testing of soil and groundwater
decontamination technologies for the clean up of U.S. Air Force fuel and
solvent spill sites.
Robert E. Hinchee, PhD, PE is a senior research engineer with the Battelle
Columbus Division of the Battelle Memorial Institute (505 King Ave, Columbus OH
43201-2693, 614-424-4698). He holds a doctorate in civil and environmental
engineering from Utah State University, is a registered professional engineer,
and is a master's level certified hazardous materials manager. He is
currently involved in research into subsurface hydrocarbon behavior and
remediation. His experience includes both laboratory as well as field
applications. He has had experience at more than 100 subsurface petroleum
spill sites.
Mark S. Westray serves as Project Manager and Senior Project Scientist in the
Aquifer Remediation Systems group of IT Corporation (165 Fieldcrest Ave,
Edison NJ 08837, 201-225-5620). Mr Westray specializes in the development and
application of biological treatment technologies for environmental cleanup.
He has been involved in more than 30 bioremediation projects and feasibility
studies over the past three years. Mr. Westray has a B.S. in Biology and M.S.
in Environmental Microbiology from the University of North Carolina.
James K. Slaughter is employed by EA Engineering, Science and Technology (41A
Lafayette Circle, Lafayette CA 94549, 415-283-7077) as the site manager for
the Eglin AFB enhanced biodegradation project. He holds a B.S. in Natural
Sciences from the University of South Florida.
-141-
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TYPE OF TREATMENT:
General: Pumping & Treatment
Specific: Pump and Treatment Groundwater
Manufacturer:
FORMER USE/PROBLEM: Former liquid Industrial waste dispo-
sal site (lagoon in a gravel pit)
LOCATION/COUNTRY: V11le Mercler
Quebec, Canada
CONTAMINANT(S): Waste oils and liquid industrial
wastes from chemical and petrochemical
industries
MEDIUM OF CONTAMINANT(S):
STATUS AS A NATO/CCMS
STUDY PROJECT:
Proposed:
Accepted: 3/87
Interim Report(s): 11/87; 11/88; 11/89
Expected Completion Date:
Final Presentation:
-143-
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GROUNDWATER CONTAMINATION
BY ORGANIC COMPOUNDS IN VILLE MERCIER: NEW DEVELOPEMENTS
BY
RICHARD MARTEL
MINISTERE DE L'ENVIRONNEMENT DU QUEBEC
PRESENTED TO
NATO/CCMS PILOT STUDY OF REMEDIAL ACTION AND
TECHNOLOGIES FOR CONTAMINATED LAND AND GROUNDWATER
BILTHOVEN, THE NETHERLANDS, NOVEMBER 7-11, 1988
-144-
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ABSTRACT
In the early 1980s, it was estimated that a draw-off of 5 times the water
volume contained in a highly contaminated zone was necessary to restore the
aquifer and recover it for use. At the first meeting of the NATO/CCMS pilot
study in Washington, Simard and Lanctot stated: "The purpose of remedial action
is not to remove all contaminants, but to remove enough for Nature to be able to
complete the process of final cleaning". Today, we know that the method used at
Ville Mercier is a control measure used to prevent contamination from spreading
rather than a restoration measure since only minimal amounts of the contaminant
have been extracted to date (20 tonnes).
-145-
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1. SITE DESCRIPTION
1.1 Site Location
The Ville Mercier site, where groundwater has been polluted by the dumping of
organic wastes, is located in the municipality of Ville Mercier situated in
southern Quebec on the south shore of the St. Lawrence River 20 km from the
city of Montreal (Figure 1).
1.2 Site History
From 1968 to 1972, a waste-oil carrier dumped 40 000 m^ of liquid waste into
lagoons in an abandoned gravel pit near Ville Mercier (Poulin 1977).
Sections of piping were installed in 1971 and 1976 to rectify the groundwater
contamination situation.
Some of the liquid waste was burned, but it was only in 1980 that the remaining
liquid and sludge were removed from the lagoons, treated and buried in a clay
landfill site 500 m east of the former site (HydrogSo Canada Inc.).
It was not until 1983 that work aimed at controlling contamination and restoring
the aquifer was undertaken.
1.3 Extent of Groundwater Contamination
The dumping of organic wastes in a site unsuited to that purpose resulted in the
contamination of the groundwater in the gravel formation and in the fractured
bedrock linked hydraulically to the sand/gravel aquifer.
In 1981, the groundwater contamination plume extended over an area of 30 km^
(Hydrogeo Canada Inc, 1981). This enclave is defined by four zones (Figure 2).
Zones 1 and 2 constitute the core of the high pollution levels while zones 3
and 4 present a very low degree of contamination.
-146-
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Ottawa
Toronto
Vllle Mercler site
^VILLE MERCIER SITE
Figure:1 LOCATION MAP OF THE VILLE MERCIER SITE
-147-
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Zone 1 is contaminated by more than 80 organic substances (SNC, 1982), with
concentrations of phenols averaging 1000 ug/L.
Within Zone 2, this concentration averages 50 ug/L and the presence of organic
substances is generalized.
Zone 3 extends southwest to Riviere de 1'Esturgeon, where the groundwater flows
naturally. The concentration of phenols ranges from 5 to 15 ug/L and less
mobile organic substances are not found.
Zone 4 is a low contamination zone where the phenolic concentration of the
samples taken was close to the range of detection covered by the method of
analysis used (5 ug/L).
1.4 Hydrogeological Environment
The lagoons are formed in a gravel ridge consisting of a very permeable
sand/gravel complex of glaciofluvial origin 30 m deep (Figure 3a). The gravel
ridge stretches NNE-SSW over a distance of 11 km.
Under the sand/gravel deposit is a thin layer of glacial till, 3 m thick,
resting erratically on the bedrock. The latter consists of dolomitic sandstone
or sandstone dolomite of the Chateauguay formation.
Marine clay is encrusted on the gravel ridge and makes the region an alluvial
clay plain.
The hydraulic conductivity of the sand/gravel formation ranges from 10"2 to
10"3 cm/s and from 10-^ to 10-® cm/s in the basal till (Keysers 1962). The
bedrock has a fracture permeability and the most fractured leyel is within the
first 3 m. Under the lagoons, the average permeability coefficient in the rock
is 10"5 cm/s and 10-8 to 10-*0 cm/s in its matrix. From the lagoons to Riviere
Chateauguay, the fractured rock permeability coefficient increases, sometimes to
10"! cm/s.
-148-
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-F*
vo
I
LEGEND
GRONDWATER FLOW
FORMER LAGOON
GROUNDWATER TREATMENT FACILITY
PIEZOMETER
CROSS SECTION
ZONE OF CONTAMINATION
N'
3 Km
FIGURE : 2 EXTENT OF GROUNDWATER CONTAMINATION AND
LOCALISATION OF CROSS SECTIONS
-------
HYDROSTATIGRAPHIC UNITS
cn
O
VERTICAL EXAGGERATION : 50 X
-------
The groundwater flow velocity, as assessed by Poulin (1977) is 110 m/yr in the
sand/gravel complex, and 525 m/yr in the fractured rock. The sand/gravel and
fractured rock formations have been contaminated by the liquid-waste-filled
lagoons.
2. REMEDIAL TECHNOLOGY
The treatment system includes water extraction facilities and a treatment plant
housing all treatment equipment.
2.1 Purge Wells
Water extraction works consist of three wells (Figure 3b), approximately 40 m
apart, each equipped with a submersible pump. They were drilled through the
sand/gravel formation and 4 m into the bedrock 35 m below the surface in the
most highly contaminated area (Zone 1). They pumped for four years at an
average rate of 47 1/s.
2.2 Treatment Plant
In the first treatment stage, hydrogen peroxide and chlorine are injected into
the raw water before air stripping occurs. Once the water has been directed
into the aerator, alum and polymers are injected into it on its way into a
mixing chamber, where chlorine dioxide is added at a dosage of 2.5 mg/L.
Then, the water is channelled into a dynamic sludge bed clarifier (Pulsator).
From there, the liquid flows towards two gravity filters, each equipped with a
42" sand bed.
After treatment, the water is discharged into an intermediate basin and pumped
into the activated carbon filtration system, which consists of three pressure
units. The first unit, called the "sacrifice" pressure filter, contains 200 cu.
ft. of activated carbon.
-151-
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( From Simard et Lanctot, 1987 )
-152-
-------
Two units measuring 400 cu. ft. and called "buffers" operate in parallel and
complete the treatment initiated in the "sacrifice" filter. The treated water
is discharged into a stream approximately 500 m east of the plant.
The sludge remaining in the settling tank is periodically pumped into the
sludge storage tank and a de-watering chamber. It is later loaded into a
container and buried in a sanitary landfill site.
3. RAW WATER CHARACTERISTICS
3.1 Composition and toxicity
The following tables show the results of the chemical analysis of a sample of
raw water taken from the Ville Mercier treatment plant in May 1988. Organic
screening for volatile organic compounds (EPA625 method) and non-volatile
organic compounds (EPA624 method) was carried out by MENVIQ's Laboratory
Division in Quebec City. The concentration of the 61 organic compounds
detected totals 2500 ug/1 and breaks down as: 97% volatile compounds and 3%
non-volatile ones. Forty-three of these compounds are on the USEPA list of
129 priority pollutants (13 PAHs, 15 MAHs, 14 HHs and PCBs).
The 26 volatile organic compounds in tables la and lb belong to two main
categories: halogenated hydrocarbons (HHs), constituting 86% by weight of the
site's total organic compounds, and monocyclic aromatic hydrocarbons (MAHs),
representing 11% by weight. The 1,2 dichloroethane alone accounts for 42% by
weight of the organic compounds present. The presence of vinyl chloride may
indicate that chlorinated hydrocarbons are degraded in groundwaters (Wolf et
al., 1987).
Six of these compounds exceed limits considered safe for drinking water using
11 available criteria. They are benzene and 5 of the most concentrated
halogenated hydrocarbons. You will recall that vinyl chloride is more toxic
than most original halogenated hydrocarbons.
-153-
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TABLE la
VOLATILE ORGANIC COMPOUNDS
CONCENTRATION OF HALOGENATED HYDROCARBONS IN THE RAH HATER OF VILLE MERCIER
HALOGANATED HYDROCARBONS
CONCENTRATION
SOLUBILITY
DENSITY
DRINKING
(ug/1)
(mg/1)
(g/cm3)
WATER GDL.
(ug/1)
1,2 dichloroethane
1 050
8 690
1,23
5 ***
1,1,2 trichloroethane
450
4 500
1,44
1,1,2 trichloroethylene
160
1 100
1,49
50 ***
Vinyl chloride
160
N.A.
0,92
2 **
Tetrachloroethene
58,8
150
1,63
10 *
Trans 1,2 dichloroethylene
55
600
1,28
1,1 dichloroethylene
53
400
1,22
y **
1,2 dichloroethylene
50
N.A.
1,27
1,1 dichloroethane
49
5 500
1,17
1,4 dichlorobutene
30
N.A.
1,14
Chloroform
8,3
8 200
1,50
30 *
1,1,2,2 tetrachloroethane
8,1
2 900
1,60
1,2 dichlorobutane
6,0
N.A.
1,11
2,3 dichlorobutane
3,0
N.A.
1,11
Dichloromethane
3,0
N.A.
1,33
50 ***
1,1,1 trichloroethane
2,3
720
1,34
200 **
1,2 dichloropropane
1,4
2 700
1,16
Trans 1,3 dichloropropene
1,03
N.A.
1,22
Bromodi chloromethane
0,87
4 500
1,98
Bromoform
0,3
3 010
2,89
Carbon tetrachloride
0,06
785
1,59
5 ***
iHHa -86% of TOCs
N.A. no data available
* WHO - World Health Organization
** US EPA - United State Environmental Protection Agency
*** HWC - Health and Welfare Canada
Data from the Merck index (1976) and Sax (1984)
-------
TABLE lb
VOLATILE ORGANIC COMPOUNDS
CONCENTRATION OF MONOCYCLIC AROMATIC HYDROCARBONS IN THE WATER OF VILLE MERCIER
MONOCYCLIC AROMATIC
HYDROCARBONS
CONCENTRATION
(ug/1)
SOLUBILITY
(mg/1)
DENSITY
(g/cm3)
DRINKING
WATER GDL.
(ug/1)
Toluene
114
470
0,87
Xylene
65
N.A.
0,86
Benzene
47
1 780
N.A
5 ***
Chlorobenzene
23,4
500
1,11
80 ***
Ethyl benzene
17,6
140
0,87
LMAHs - 11% of TOCs
N.A. no data available
*** HWC - Health and Welfare Canada
Data from the Merck Index (1976) and Sax (1984)
-------
TABLE 2a
NON VOLATILE ORGANIC COMPOUNDS
CONCENTRATION OF POLYCYCLIC AROMATIC HYDROCARBONS IN THE RAM WATER OF VILLE MERCIER
POLYCYCLIC AROMATIC
CONCENTRATION
SOLUBILITY
DENSITY
DRINKING
HYDROCARBONS
(ug/1)
(ug/1)
(g/cnr*)
WATER GDL.
(ug/1)
2-Methylnaphtalene
7,3
N.A.
1,01
Napthtalene
4,1
34 400
1,16
Phenanthene
2,2
1 290
1,79
Benzo (b+k) anthracene
1,6
N.A.
N.A.
Pyrene
1.1
140
1,27
Benzo (a) anthracene
1,1
14
N.A.
Benzo (g,h,1) perylene
1,1
0,26
N.A.
Dibenzo (a,h) anthracene
1,0
0,5
N.A.
Benzo (a) pyrene
0,9
3,8
1,35
0,01 ***
Fluoranthene
0,8
260
1,25
Fluorene
0,8
1 980
1,20
Indeno (1,2,3,- cd) pyrene
0,6
620
N.A.
Acenaphtene
0,6
3 400
N.A.
Anthracene
0,6
73
1,25
Acenaphtylene
0,2
3 920
N.A.
£ PAHs - 1* of TOCs
N.A. no data available
*** HWC - Health and Welfare Canada
Data from CNRC (1983), the Merck Index (1976) and Sax (1984)
-------
TABLE 2b
NON VOLATILE ORGANICS COMPOUNDS
CONCENTRATION OF PHENOLIC COMPOUNDS IN THE RAW WATER OF VILLE MERCIER
PHENOLIC COMPOUNDS
CONCENTRATION
(ug/1)
SOLUBILITY
(mg/1)
DENSITY
(g/cm3)
DRINKING
WATER GDL.
(ug/1)
2,4 dimethyl phenol
13,0
N.A.
N.A.
Phenol
6,2
82 000
1,07
4-ni trophenol
2,1
N.A.
1,27
Pentachlorophenol
0,8
N.A.
N.A.
60 ***
2- chlorophenol
0,4
28 500
1,26
2- nitrophenol
0,4
N.A.
1,49
4- chloro 3- methyl phenol
0,4
N.A.
N.A.
2- methyl phenol
0,3
N.A.
1,5
2,4- dinitrophenol
0,3
N.A.
N.A.
70 ***
4,6- dinitrophenol
0,3
N.A.
N.A.
2,4- dinitrophenol
0,1
N.A.
N.A.
E PCs - 1* of TOCs
*** HWC - Health and Welfare Canada
N.B. In Quebec the Drinking Water Standard for Phenolic Compounds is 2 ug/1.
Data from the Merck index (1976) and Sax (1984)
-------
TABLE 2c
NON VOLATILE ORGANIC COMPOUNDS
CONCENTRATION OF MONOCYCLIC AROMATIC HYDROCARBONS, HALOGENATED HYDROCARBONS
AND OTHERS IN THE RAH WATER OF VILLE MERCIER
MONOCYCLIC AROMATIC
CONCENTRATION
SOLUBILITY
DENSITY
DRINKING
HYDROCARBONS
(ug/1)
(mg/1)
(g/cm3)
WATER STD.
(ug/1)
2 nitroanHine
14,0
N.A.
N.A.
Ni trobenzene
3,1
N.A.
1,20
1,2 dichTorobenzene
0,6
N.A.
1,30
200 ***
1,4 dichlorobenzene
0,4
N.A.
1,25
HALOGENATED HYDROCARBONS
Hexachloroethane
7,2
N.A.
2,09
Hexachlorobutadiene
1.4
N.A.
N.A.
OTHERS
Isophrone
4,1
N.A.
0,92
N- nitroso- DIN-propylamine
0,7
N.A.
N.A.
Dibenzofuran
0,5
N.A.
N.A.
15X10-6***
£(MAHs ~ HHs ~ OTHERS)- 1% of TOCs
Data from the Merck Index (1976) and Sax (1984)
-------
In tables 2a, 2b and 2c, the 35 non-volatile organic compounds are represented
mainly by phenolic compounds and polycyclic aromatic hydrocarbons (PAHs) in
proportions equivalent to 1% by weight of the total organic compounds.
Of these non-volatile compounds, 7 are subject to drinking water guidelines.
Dibenzofuran and benzo (a) pyrene, however, exceed allowable levels. In Quebec,
a standard of 2 ug/1 is applicable to total phenolic compounds. This level is
exceeded for phenol, 2,4 dimethyl phenol and 4- nitrophenol.
Many of these pure substances (primarily halogenated hydrocarbons) can be
categorized as dense-non-aqueous-phase-liquid (DNAPL) chemicals. These
chemicals resemble petroleum hydrocarbons in that they are immiscible in water.
However, their densities exceed that of water and their viscosities are less.
Their relatively low solubility in water (typically 100 to 5000 mg/1) can often
be many orders of magnitude higher than the drinking water standard. Mixtures
of chemicals that are not individually recognized as DNAPLs can present similar
characteristics. This is probably true for many of the PAHs and phenolic
compounds in Tables 2a and 2b. The presence of two PAHs (dibenzo (a, h)
anthracene and benzo (g, h, i) perylene) in concentrations greater than their
aqueous solubility can be explained by their presence in a mixture of
chemicals which can enhance solubilization.
Due to their low densities, other pure substances (mainly benzene, toluene,
xylene, and ethyl benzene) can be categorized as NAPL chemicals.
The composition of this sample shows that after four years of pumping it remains
hazardous to drink this well water. Moreover, the raw water must be treated to
be discharged into surface waters without causing significant pollution. The
plant's wells are currently recovering, at concentration far lower than the
solubility limit, the organic compounds dissolved in the water and the by-
products of the chemical or microbial decomposition of the original
hydrocarbons.
-159-
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3.2 Variation in composition
Figures 4 and 5 indicate that the concentration of 1,2 dichloroethane and
phenolic compounds dropped considerably from the onset of in-plant operations
to the point when 1.5 million m^ of water had been pumped. This volume, which
was obtained after 2 years, corresponds to the renewal of once the volume of
water contained in the very contaminated zone. Concentrations later stabilized
around 1000 ug/L for 1,2 dichloroethane and 35 ug/L for phenolic compounds. The
area below the dichloroethane curve leads us to estimate that approximately 20
tonnes of organic contaminants have been extracted since operations began. This
represents a very small percentage of the organic contaminants that might be
present.
The drop in concentrations over the first two years can be explained by the
greater dilution created by broadening the well's intake zone and progressively
drawing off the pores containing mobile contaminants. The concentrations'
stabilization may be due to a state of equilibrium between the uncontaminated
water upstream from the highly contaminated zone and the organic non-aqueous-
phase-liquid agglutinate between the particles and in the aquifer's fractures.
Water is a very weak solvent for agglutinated compounds.
These two compounds are good indicators of the change in the quality of the
aquifer's groundwater since they are the first to be affected, given their high
aqueous solubility, weak adsorbability and high stability in groundwater (low
biodegradability). High concentrations of these compounds were detected from
the beginning of operations on.
The concentration curves of most organic compounds present should be comparable
to figures 4 and 5. However, given retardation factor values, the decrease in
concentrations is expected to extend over a relatively long time before
stabilizing.
The 1,1,2 trichloroethylene acted differently (Figure 6). Concentrations
declined as anticipated over the first two years but never stabilized. Values
fluctuated cyclically between 40 and 110 ug/L.
-160-
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1,2 DICHLOROETHANE
VOLUME OF PUMPED WATER ( x 106 m3 )
FIGURE : 4 CONCENTRATION OF 1,2 DICHLOROETHANE
VERSUS VOLUME OF PUMPED WATER
-------
PHENOLIC COMPOUNDS
VOLUME OF PUMPED WATER ( x 106 m3 )
FIGURE : 5 CONCENTRATION OF PHENOLIC COMPOUNDS
VERSUS VOLUME OF PUMPED WATER
-------
1,1,2 TRICHLOROETHYLENE
VOLUME OF PUMPED WATER ( x 10s m3 )
FIGURE : 6 CONCENTRATION OF 1,1,2 TRICHLOROETHYLENE
VERSUS VOLUME OF PUMPED WATER
-------
PCB A1254
1.2-1
cr>
i
< 0,1
2 4 6
VOLUME OF PUMPED WATER ( x 106 m3 )
FIGURE S 7 CONCENTRATION OF A1254
VERSUS VOLUME OF PUMPED WATER
-------
PCB A1260
_ 0,6
0,4
0,2-
< 0,1
r
¦r
0 2 4 6
VOLUME OF PUMPED WATER ( x 106 m3 )
FIGURE S 8 CONCENTRATION OF A1260
VERSUS VOLUME OF PUMPED WATER
-------
Other parameters such as aroclor 1254 and 1260 behaved erratically due to their
high molecular weight and adsorption affinities (figures 7 and 8). PCBs did
not behave in the same manner as the majority of contaminants in the aquifer.
4. CONTAMINANT BEHAVIOR
4.1 In the very high pollution zone
Figure 9 is based on the DNAPL groundwater development concept shown in
Feenstra and Cherry (1988) and on the visual appearance and odor of the water
and soil samples collected in the field during the drilling campaign.
When liquid waste was dumped into the lagoons, the volume of release was
sufficient to overcome the retention capacity of the vadose zone. The DNAPL
chemicals' high densities cause them to penetrate downward through the
groundwater zone of the sand/gravel formation.
Some of the DNAPLs settle out as a pool of free liquid on the low-permeability
basal till. In some places, the basal till forms a barrier and prevents the
movement of DNAPLs through the fractured porous rock formation. Because the
basal till is sloped and rests erratically on the rock formation, the DNAPLs
continue to move down the slope and penetrate into the fractures of the porous
rock formation. On the till, the pattern of DNAPL movement need not be
controlled by the direction of groundwater flow. In the rock formation, it is
controlled primarily by fracture orientation and interconnection.
Because of the high vapor pressure and molecular weight of many DNAPLs, the
soil and air in contact with these chemicals may acquire vapor concentrations
high enough to result in density-induced sinking of chemical vapors downward to
the saturated zone. Diffusion results in lateral migration of vapor through
the vadose zone. These mechanisms may result in significant groundwater
contamination.
Due to their low densities, the NAPLs (primarily MAHs) (figure 10), tend to form
pools and spread laterally when they encounter the capillarity fringe and the
water table. Zones contaminated by liquids that are lighter than water extend
-166-
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PURGE WELLS
WATER-FILLED#
PORE SPACE
DISSOLVED CHEMICAL
IN FRACTURE
DNAPL
UNAfL
AIR OR WATER-
FILLED PORE SPACE
SINKING VAPOURS
-2 TOP OF CAPILLARY FRINGE
BASAL TILL
FRACTURED POROUS ROCK
DNAPL-FILLED FRACTURE
DIFFUSION
INTO
MATRIX
FIGURE : 9 GROUNDWATER CONTAMINATION FROM
RESIDUAL DNAPL AND DNAPL POOLS
( MODIFIED FROM FEENSTRA AND CHERRY, 1988 )
-------
NAPL RELEASE
lllllllll
,NAPL ( DISCRETE GANGLIA I
AIR OR WATER-
FILLED PORE SPACE
RANGE OF WATER
TABLE FLUCTUATIONS
WATER-FILLED PORE SPACE
< MODIFIED FROM HUNT ET AL, 1988 )
FIGURE : 10 GROUNDWATER CONTAMINATION FROM RESIDUAL NAPL
AND NAPL POOLS IN THE WATER TABLE FLUCTUATION
ZONE
-168-
-------
over the entire range of water fluctuation. These liquids follow the declining
water table but can be partially trapped under it when it rises again since only
some of the liquid can be remobilized (Hunt et al., 1988a).
As described by Hunt et al. (1988a), during their migration, NAPLs and DNAPLs
leave behind ganglia trapped in pores and fractures. The amount of organic
liquid left behind is referred to as residual saturation and differs according
to the medium and of the liquid's properties.
Schwille found that for sandy soil the residual content of NAPL or DNAPL
chemicals could be 3 to 30 L/m3 (1-10% of the pore space) in the unsaturated
zone and 5 to 50 L/m3 (2-15% of the pore space) in the saturated zone. Based on
laboratory experiments by Schwille in 1988, less than 0.05 L/m^ of NAPL or DNAPL
is retained on the fracture surface.
In the saturated and unsaturated zones, ganglion measurements could range from
pore size to many tens of meters in length and a few meters in width.
For very small trapped droplets, a few pore volumes of water are required to
remove the contaminants. For the large ganglia, an effluent concentration far
lower than the solubility limit is predicted (as observed at Ville Mercier) and
considerable pumping is required to remove the contaminant.
The only way to reduce the residual saturation and ganglion sizes in the
saturated zone is to increase the water velocity or decrease the NAPL or
DNAPL/water interfacial tension.
The lifetime of a large ganglion is estimated at several decades or centuries.
To decrease the lifetime by an order of magnitude, a three-order-of-magnitude
increase in the flow velocity is required and the volume of water removed and
requiring treatment is increase a hundredfold.
Based on the concept of ganglion and pool dissolution, it would appear that
groundwater withdrawal from an aquifer is not a suitable solution. This concept
leads us to believe that the "restoration" method currently being used in Ville
-169-
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Mercier is actually a confinement measure preventing the propagation of
contaminants rather than a restoration measure.
Groundwater contamination cannot be eliminated in the long term without removing
the NAPL and DNAPL sources (possibly >99%). Because of their low solubility and
existing low drinking water standards if they are not removed, NAPL and DNAPL
chemicals can persist in subsurface waters and cause groundwater contamination
problems for many decades and even centuries (Feenstra and Cherry, 1988).
At Ville Mercier, most NAPLs and DNAPLs can probably be removed by excavation in
the unsaturated zone. However the same is not true for the saturated zone below
5 to 10 m. Recovery of these products trapped in the aquifer's pores and
fractures may be possible by the in situ removal methods described by Feenstra
and Cherry (1988), including:
- In situ biodegradation;
- Chemically-enhanced displacement;
- Steam displacement;
- Chemically-enhanced dissolution.
Unfortunately, there are currently no effective remedial methods available in
field situations for removing NAPL and DNAPL sources from the subsurface.
Research is needed to develop methods to provide long-term solutions to problems
of groundwater contamination by these chemicals (Feenstra and Cherry, 1988).
A study sponsored by Environment Canada is currently identifying the presence
and distribution of this organic liquid phase and will use laboratory tests and
mathematical models to simulate the behavior of these liquids. It will also
propose alternative methods for restoring the very high pollution zone.
-170-
-------
4.2 Beyond the high pollution zone
In May 1988, organic screening for volatile and non-volatile compounds method
was carried out on water samples from various piezometers outside the high
pollution zone (Table 3). These points were selected in function of their
position compared to the preferred path of contaminants in groundwater
(Figure 2).
This sampling campaign shows that organic compounds are present beyond the
perimeter created by the hydraulic trap. By activating this trap, pollutant
discharge from the lagoon was cut off, but the contaminated groundwater located
outside the trap's action perimeter continued to move southwest.
Based on the calculation of water flow velocities in the various formations,
the contaminated water tail should be located at less than 3.3 km southwest of
the former lagoons in the fractured rock and at less than 1 650 m from the
source in the sand and gravel (Figure 11).
Piezometer P-51 located in zone 3 indicates that contamination does not persist
in the sand 400 meters downstream of the trap.
Piezometer P-27 located in zone 3 shows that the water flowing from the first 2
m of fractured rock to 1.7 km upstream of the contaminated water tail dislodges
a low concentration of contaminants adsorbed by the fractures.
Piezometer P-98, located in zone 4, 18 m down in the rock and 4.8 km southwest
of the lagoons, contains organic contaminants in identical proportions but at
concentrations much lower than in the plant's raw water. The two volatile and
non-volatile organic compounds identified represent 2.4% by weight of the total
organic compounds measured in the raw water of the well in May 1988. Since it
is located in a layer presenting artesian conditions, piezometer P-98 is
positioned in a preferred flowing zone.
Piezometers P-62 and P-162 are located in zone 3 and 4 in the first 4 m of
fractured rock on either side of piezometer P-98 (Figure 12). No contamination
was detected at piezometer P-62 and only very low concentrations of chloroform,
-171-
-------
TABLE 3
Concentration of organic compounds in piezometer
of the sampling campaign of May 1988.
Concentrations (ug/1)
Organic compounds
P-33
P-162
P-62
P-27
P-51
HHs
1,2 dichloretane
34,0
0,92
1,1,2 trichloroethane
15,3
Dichloromethane
4,2
1,1,2 trichloroethylene
0,65
1,1,2,2 tetrachloroethane
Tetrachloroethylene
1,1 dichloroethane
Chloroform
1,1 dichlorethylene
0,23
0,20
0,15
0,08
0,11
0.13
0,21
MAHs
Chlorobenzene
Benzene
Toluene
Ethyl benzene
1,60
1,20
0,60
0,10
0,25
0,20
0,17
0,35
0,12
PCs
Phenol
4-methylphenol
1,0
0,1
PAHs
Benzo (a} anthracene
Benzo (g,h,i) perylene
Phenanthrene
Fluoranthene
Pyrene
Benzo (b+k) fluoranthene
Benzo (a) pyrene
0,6
0,3
0,1
0,1
0,1
0,1
-172-
-------
ZONE 4 ZONE 3 I ZONE 2 I ZONE 1
>¦
CO
I
VERTICAL EXAGGERATION : 50 X
-------
1,2 DICHLOROETHANE
CHLOROFORM
BENZENE
ETHYL BENZENE
TOLUENE
E
z
0
1
LU
_J
UJ
0
L
PIEZOMETER
A
0,5
1,0 Km
VERTICAL EXAGGERATION : 50 X
LEGEND
H
MARINE CLAY
BASAL TILL
BEDROCK
FIGURE i12 CROSS SECTION B — B
-174-
-------
benzene, ethyl benzene, toluene and 1.2 dicloroethane were detected at
piezometer P-62. These piezometers are outside the main area of contaminant
circulation.
Sampling was repeated in October to identify the contaminant's status downstream
of the well in the high pollution zone (Zone 2) and to accurately describe the
status of the groundwater quality outside this zone.
CONCLUSION
- Many of the pure substances present in the raw water of the treatment plant's
purge wells can be classified as DNAPL chemicals; other are NAPL chemicals.
- The concentration of organic chemicals present in the water of the purge
wells dropped significantly after two years of operations and seems to have
stabilized since this time.
- The amounts of organic contaminants extracted by the wells to date represent
a small proportion of the organic contaminants that may have infiltrated this
area. The "restoration" method used to date does not appear to provide an
adequate solution for restoring aquifer formations.
- At present, aside from excavation operations, the only means of recovering
DNAPLs and NAPLs is by increasing water velocity or decreasing interfacial
tension in the water containing DNAPLs or NAPLs. There are no effective
remedial methods available in field situations for removing these chemicals
from the subsurface.
- The May 1988 samplings showed that significant contamination did not persist
in the sand/gravel formation between the hydraulic trap and the contamination
tail. Nevertheless, it may be considerable in the rock formation downstream
of the contamination tail's farthest reachings.
-175-
-------
References
CNRC 1983
Les hydrocarbures aromatiques polycycliques dans le milieu aquatique. For-
mation, sources, devenir et les effets sur le biote aquatique. CNRC No
18982 Ottawa Canada, 218 pages.
FORATEK INTERNATIONAL INC. 1982
Etude hydrogeologique de faisabilite du captage des eaux contaminees ex-
tra ites de la nappe aquifere de Ville Mercier. For the ministere de l'En-
vironnement du Quebec, by M. Poulin, Report No. 514.
Feenstra, S. and S. A. Cherry 1988. Subsurface contamination by dense non-
aqueous phase liquid (DNAPL) Chemicals. In Proceedings of the Internatio-
nal Groundwater Symposium on Hydrogeology of Cold Climates and Hydrogeology
of Mineralized Zones. International Association of Hydrogeologist. Cana-
dian National Chapter, Halifax, Nova Scotia, May 1-5. 1988. p. 61-69
Hunt, J.R., N. Sitar and K. S. Udell 1988a. Nonaqueous phase liquid trans-
port and cleanup 1. Analysis of mechanisms. Water Resources Research.
Vol. 24, Bi. 8, August 1988 p. 1247-1258.
Hunt, J. R., N. Si tar and K. S. Udell 1988b. Nonaqueous phase liquid
transport ans deanup II. Experimental studies. Water Resources Research.
Vol. 24, No. 8, August 1988, p. 1259-1269.
HYDREGEO-CANADA INC. 1981.
Hydrogeologie et contamination des eaux souterraines, Ville Mercier. For
the ministere de l'Environnement du Quebec, by G. Nielson.
Keyser, J.H. 1965. Aperqu de la geologie his tori que, economique et appH-
quee. Geologie de Montreal. Soc. International de m§canique des Sols et
des Travaux de Fondations. Sixieme congres Int.
-176-
-------
The Merck index 1976, 9^ edition published by Merck and co. inc. Rahway,
N.J, USA, 1822 pages.
Poulin, M., G. Simarti et M. S.ylvestre 1985. Pollution des eaux souterrai-
nes par les composes organiques a Mercier, Quibec. Sciences et techniques
de l'eau, Vol. 18, NO 2, May 1985.
Poulin, M. 1977. Groundwater Contamination near a Liquid Waste Lagoon,
Ville Mercier, Quebec. Master's thesis, University of Waterloo, Wateloo,
Ontario. 158 pages.
Sax, N.I. 1984. Dangerous Properties of Industrial Materials 6th edition
published by Van Nostrand Reinhold Company New York, U.S.A. 3124 pages.
Schwille, F. 1984. Migration of Organic Fluids Immiscible with water in
the unsaturated zone. In: Pollutants in Porous Media - The Unsaturated
Zone Between Soil Surface and Groundwater. Editted by B. Yaron. G. Dagan,
and J. Goldshmid, Springer-Verlag. New-York. p. 27-48.
Schwille, F. 1988. Dense Chlorinated Solvents in Porous and Fractured Me-
dia - Model Experiments Translated by J.F. Pankow, Lewis Publishers Inc.,
Chelsea, Michigan.
Simard, G. and J.P. Lanctot 1987. Decontamination of Ville Mercier Aquifer
for toxic organics. In proceedings of the First International Meeting of
the NATO/CCMS pilot study demonstration of remedial action technologies for
contaminated land and groundwater. Washington, D.C., U.S.A. novembrer
11-13 p.135-164.
Wolf, K., R. Holland and G. Rajarothon 1987. Vinyl Chloride Contamination:
the Hidden threat. Journal of Hazardous Materials 15 (1987) p. 163-184
-177-
-------
TYPE OF TREATMENT:
General:
Specific:
Manufacturer:
FORMER USE/PROBLEM:
LOCATION/COUNTRY:
CONTAMINANT(S):
MEDIUM OF CONTAMINATION:
STATUS AS A NATO/CCMS
STUDY PROJECT:
Proposed:
Accepted:
Interim Report(s):
Expected Completion Date:
Final Presentation:
Microbial Degradation
Biological Pre-Treatment of
Groundwater
Lindane manufacturing
Bunschoten
The Netherlands
Lindane
Benzene
Groundwater
4/88
4/88
11/88
-179-
-------
TAUW Infra Consult
Biological treatment of groundwater polluted with HCH, chlorobenzene
and benzene on a former pesticide production site in Bunschoten, The
Netherlands.
Urlings L.G.C.M., F. Spuij and J.P. van der Hoek
TAUW Infra Consult B.V., P.O. Box 479 Deventer, The Netherlands
1. Introduction
From 1945 untill 1949 the factory Dagra (Bunschoten, The Netherlands)
has produced the insecticide Lindane. Lindane (gamma-Hexachlorocy-
clohexane) was made by mixing benzene and chlorine gas under U.V.
radiation; not only gamma-HCH was produced but also all other HCH-iso-
mers.
As a result of these activities the factory grounds and the surrounding
area were heavily polluted with HCH. Even the groundwater was contami-
nated with mainly HCH, monochlorobenzene and benzene. An outline of
the production shed and the surrounding is given in figure 1.
Figure 1. Pesticide pollution around the production shed
In 1985 the remedial action of the contaminated soil took place. More
than 11.000 m^ polluted soil was excavated and transported to a Tem-
porary Storage Place waiting for treatment. Approximately 60 m^ soil
could be regarded as pure HCH (> 90%). The groundwater remediation
which was continued after the excavation will be finished in the second
part of 1988. The groundwater treatment originally consists of a phy-
sicochemical proces which is made up of two sand filters and three
activated carbon filters. During the remedial action of the soil the
maximum withdrawal was 60 m^/h. In 1986 the groundwater was 40 m^/h and
has been reduced to 25 m^/has a result of the cleanup action in the
middle of 1987. In October 1988 the flow was 12 m^/h.
In recent research it appeared that a lot of xenobiotics can be degra-
dated by micro-organisms. Although there is hardly any experience with
biological groundwater treatment TAUW Infra Consult B.V. started some
small scale experiments with a trickling filter and a rotating biolo-
gical contactor in 1986.
-180-
-------
The results were promising: 50% removal of HCH and 99% removal of
benzene and monochlorobenzene. The required activated carbon would be
reduced in this situation to less than 10% when applying a full scale
biological treatment.
In november 1987 two rotating biological contactors were installed for
groundwater pretreatment (see figure 2). The research was partly-
financed by the Ministry of Housing, Physical Planning and
Environment.
/
Ringvelering
Figure 2. Groundwater treatment installation in Bunschoten, the
Netherlands
Although the groundwater treatment installation has been scaled up,
there is still an experimental character in the operation of the
plant.
2. Apparatus and operation
The rotating biological contactor (RBC) installation consists of two
RBCs. Firstly a TAUW RBC with an effective surface aera of 1000
placed in a trough of 9 and divided into 4 stages (figure 2), and
secondly a KLEIN RBC with an effective surface area of 700 m* placed
in a trough of 4.4 also divided into 4 stages. Both RBCs rotate
with 1.5 rpm. There are no settling tanks and the effluent of the
RBCs is treated in the sandfilter/activated carbon installation. The
RBCs operate seperately (parallel) but they can be connected in series
if wanted (figure 2).
To prevent contamination of the surrounding air by volatilization of
contaminants from the groundwater both RBCs are roofed, and the air
extracted from the RBCs is purified by a compost filter. The air
extraction flow is approximately 150 m /h.
-181-
-------
"O lo raw water basin
RBC's
Figure 3. Flow diagram of the RBCs and compost filters.
3. Groundwater characteristics
Table 1 gives an indication of the concentrations of contaminants in
January 1988.
Table 1. Groundwater concentration in January 1988
ug,A
Benzene
Monochlorobenzene
HCH*
alpha-HCH
beta-HCH
gamma-HCH
delta-HCH
epsilon-HCH
350
350
200
± 60
+ 5
+ 80
+ 40
+ 15
Other xenobiotics are not substancially present in the groundwater
(GC/MS-analysis).
-182-
-------
Some important macroparameters are shown in table 2.
Table 2. Macroparameters groundwater
compound dimension august 1986 february 1988
COD
mg/1
56
47
BOD
mg/1
4
5
Kjeldalh nitrogen
mg N/1
3,5
Ammonia
mg N/1
4,5
3
Nitrite
mg N/1
0,02
<0,01
Nitrate
mg N/1
0,1
0,35
Total phosphorus
mg P/l
0,28
0,57
Temperature
•c
10
9
pH
7
6,8
4. Results and discussion
4.1 Start up
After one week of operation (3rd December 1987) a thin biofilm was
observed. In addition sediment from the raw water basin was supplied
to both biocontactors during one day of batch operation to enhance
bacterial atachment. First results, 9th December , showed almost
complete (> 98%) removal of benzene and chlorobenzene at a low flow
rate of 3 m^/h (hydraulic residence time 3 h). After a short freezing
(2 weeks) period and shut down of the RBCs complete removal of benzene
and chlorobenzene was measured after 3 days of the re-start (3 m^/h).
The first HCH biodegradation was found on day 28.
4.2 Overall removal efficiencies
The applied flow rates through the RBCs are shown in figure 4.
Time to
0 Ttuw + Klein
Figure 4. Flow rates through the RBCs
-183-
-------
- HCH-removal
In figure 5 the removal efficiencies of alpha and gamma-HCH in the
TAUW RBC is plotted against time, while in figure 6 HCH removal related
to HCH loading is shown.
Time In d»ya
~ alpha - HCH * liniu - HCH
Figure 5. Removal efficiencies of alpha and gamma HCH (TAUW RBC)
60
30 -
40 -
30 -
20 -
30 90 70
HCH - total loidlng in n»|/ro2.d
Figure 6. HCH removal versus HCH loading (TAUW RBC)
Figure 6 shows a linear increase of HCH removal with HCH loading.
However at loadings of 50 - 60 mg/m^d the line deflects and remains
constant. This trend is confirmed by the compartiment sampling (see
figure 12).
-184-
-------
- Benzene removal
The performance of the TAUW RBC is given in figure 7.
0 40 80 120 ISO 200 240
Benzene loading In tnf/m2.d
Figure 7. Benzene removal versus benzene loading
Figure 7 indicates that benzene removal is complete and no deflection
is observed.
- Chlorobenzene removal
The removal related to loading of the TAUW RBC is shown in figure 8.
200
190
160
170
160
130
140
130
120
110
100
90
60
70
60
SO
40
30
20
&
O
„cP° o
I » I I I J I I 1 I I
40 60
I I I I I
200 220
60 100 120 140 160 180
CI - Benzene lotdtaf Id m|/m2.d
Figure 8. Chlorobenzene removal versus chlorobenzene loading
Figure 8 is conform to figure 7. Hence no maximum for the
chlorobenzene removal can be given.
4.3 Mass balance for the TAUW RBC
An unknown factor in the determination of the removal efficency of the
RBC is the volatization of components like benzene and chlorobenzene.
Therefore 3 mass balance measurements were carried out.
-185-
-------
«-
- Experiment 1. flow 6.7 m^/h, sampling during 2 h.
Extracted air
benzene 65 mg (1%)
chlorobenzene 101 mg (2%)
Influent Effluent
benzene 5,900 mg benzene 80 mg
chlorobenzene 6,300 mg BI0DEGRADATI0N chlorobenzene 201 mg
For experiment 2 and 3 the following volatilization percentages are
found.
- Experiment 2: benzene 2% volatilization
chlorobenzene 1% volatilization
- Experiment 3: benzene 6% volatilization
chlorobenzene 9% volatilization
The airflow in experiment 3 was extremely high (840 m^/h) which ex-
plains the high volatilization. The HCH volatilization was less than
1%.
4.4 Compartment measurement
To obtain detailed information on removal rates, in individual compart-
ments of the RBCs samples were taken in each compartment of the RBCs
in serie. Both RBCs have 4 compartments equal in volume.
- HCH
The total-HCH concentration is given for the several compartments in
figure 9. In the first two compartments the removal rate is comparable.
~ 20/04 ~ 19/03 O 08/00
& 13/06 X 28/06 V 24/08
Figure 9. HCH compartment sampling at different flow rates
In figure 10 and 11 the 5 isomers of HCH are shown at a low and a high
flowrate respectively.
-186-
-------
tofl corop 1 comp 2 comp 3 Bffl TAUW comp 3 Effl KLEIN
Ot ~ b o c Ad x e
Figure 10. HCH-isomer compartment sampling on the 24th August
(flow rate - 12 m^/h)
Figure 11. HCH-isomer compartment sampling on the 29th June
Cflov rate - 22 m^/hT
120
110 -
100 -
90 -
eo -
70 -
60 -
30 -
40 -
30
20 "
10 -
0
Do
~
aoP
I
200
100 200 300
HCH lotdlnj lo f»|/n>2-d
Figure 12. HCH loading versus HCH removal: compartment sampling
-187-
-------
*
In figure 10 alpha and gamma HCH breakdown are almost complete after
passage of two compartments while in figure 11 the total disc surface
area is needed to complete the alpha and gamma HCH breakdown. Delta
HCH biodegradation is also observed. The concentrations of the epsilon
and beta HCH remain constant.
The results of the compartment measurements (figure 9) is presented in
figure 12 in a loading/removal graph which shows a maximum removal
rate of almost 50 mg HCH/m^d.
• Benzene and chlorobenzene
In figure 13 and 14 the breakdown curves of benzene and chlorobenzene
are given for the RBCs in series. The results for benzene and chloro-
benzene are comparable and the highest removal rates appeared in
0 20/04 B.6»'/(! O 08/06 UJ»Vh
A 16/06 JU »Vti V 24/08 13.J pi'/ti
+. 19/05 H.tuVti * 29/06 ttOnVll
Figure 13. Benzene concentration in the compartments for different
flow rates
~ 20/04 ~ 19/03 « 08/06
A 15/06 * 29/06 * 24/08
Ficmre 14. Chlorobenzene concentration in the compartments for
different flow rates
-188-
-------
Figures 15 and 16 give removal rates (mg/m^d) versus loadingrate
(mg/m^d) for benzene and chlorobenzene. And indicate that when
loadingrates exceed 200 mg/m^d the removal can be estimated as a half
order process. In figures 7 and 8 a zero order removal process
outlined, which means no limitation.
was
900
490 -
400 -
300 -
300 -
290 -
200 ~
150 -
100 -
SO -
0
o
~
~
SP
0.4 0.6
(Tbouitnds)
Benzene loadlni in m|/m2.d
Figure
15. Benzene loading versus benzene removal as measured in
compartment sampling
600
900 -
400 600
Cl-benzeo* lotdlDi lo re|/m2.d
Figure 16. Chlorobenzene loading versus removal as measured in
compartment sampling
4.5 Biofilm characteristics
The growth of biomass was measured in the 1st and 4th compartment of
the TAUW RBC by using exchangeable disc packets. The biomass density
was determined by removing the biofilm from 0.1 m^ disc area. The
biomass-wash out was calculated from the suspended solids
concentration in the effluent.
-189-
-------
Table 3 Biomass charactaristics.
dry matter ash content
f% of dm")
1st compartment TAUW
200 g/mj
67
4th compartment TAUW
20 g/m^
62
wash-out TAUW RBC
10 g/m~
50
KLEIN RBC
10 g/m3
50
growth
- 1st compartment TAUW RBC
7 g/nr. wk
- 4th compartment TAUW RBC
2 g/nr. wk
Using an average HCH concentration in the sludge of 15 mg/kg it can be
calculated that 1.6 g HCH adsorbed on the whole TAUW RBC. The HCH
load of the RBC was approximately 100 g/d. Hence accumulation of HCH
in the biomass does not occur. In the effluent only 0.2 ug HCH/1 is
adsorbed on the suspended solids.
4.6 Costs
The cost evaluation for the Bunschoten site is based upon the contrac-
tors fee for physicochemical treatment (activated carbon) and estimated
cost for biological treatment. For the latter the results of the above
discribed experiments are used. The total amount of removed contami-
nants are:
- HCH 100 kg
- Benzene 250 kg
- Chlorobenzene 200 kg
For a combined biological/physicochemical treatment three different
biological removal efficiencies, as well as for an one-stage physico-
chemical treatment the costs are compared in table 4.
Table 4. Treatmentcosts (in Dfl) versus techniques
Removal efficiency Costs
HCH Benzene/Chlorobenzene
RBC
Activated Physicochem.
carbon install.
Total
70%
> 95%
110.000
15.000
80.000
205.000
60%
95%
90.000
20.000
100.000
210.000
20%
60%
35.000
100.000
125.000
260.000
0
0
200.000
150.000
350.000
Biological pretreatment results in a cost reduction for the groundwater
remedial action of 30 - 40% for the Bunschoten site.
-190-
-------
*
¦ 5. Conclusions and recommendations
5.1 Conclusions
Biodegradation:
the removal of HCH, benzene and chlorobenzene in the RBC can be
attributed for more than 90% to biodegradation. Volatilization and
adsorption onto the sludge are of minor importance to the total
removal;
loadings up to 200 mg/m d for both benzene and chlorobenzene and a
hydraulic residence time of app. 30 min. lead to average effluent
concentrations of less than 10 ug/1;
only alpha HCH and gamma HCH show a good biodegradation rate (each
25 mg/m^d). Delta HCH shows little breakdown, while epsilon HCH
and beta HCH concentrations in the RBC remain constant;
the mineralisation of contaminants is complete, viz. there are no
metabolites found (GC/MS analysis). The applied biotechnology is
environmentally attractive;
The performance of the compost filter for air treatment shows poor
results.
Costs
for the Bunschoten groundwater remedial action the cost reduction
by RBC pretreatment is at least 30%;
cost minimizing of hazardous waste treatment (less volume of
contaminated activated carbon).
Application
RBCs need little maintenance;
in wintertime (-10°C) RBCs are applicable when the groundwater
flow rate is not to low;
the adaptation time for benzene and chlorobenzene biodegradation
was only two weeks and for HCH four weeks in the RBC-system.
5.2 Recommendations
More biological techniques like RBCs should be applied in the ground-
water remedial action, especially for aromatic contaminants.
From literature it is known that a lot of organic micropollutants can
be biodegradated. Probably a combined aerobic-anaerobic (dechlorina-
tion) system can tackle a wide variety of organic contaminants in an
environmental friendly way.
Acknowledgement
Thanks to the critical and inspiring contribution of the advising
board. The board consited of dr. ir. A. Klapwijk (chairman,
Agricultural University Wageningen), dr. ir. M. v. Loosdrecht
(Agricultural University Wageningen/Technical University Delft), ing.
P.J.C. Kuiper (Institute for Inland Water Management and Waste Water
Treatment), ing. A.W.J, van Mensvoort, ing. J.C. Hoogendoorn
(Province of Utrecht), ir. A. v.d. Vlugt (Ministery of Housing,
Physical Planning and Environment).
-191-
-------
TYPE OF TREATMENT:
General: Pump and Treatment
Specific: Recovery Recycling (Groundwater)
Researcher/Manufacturer:
FORMER USE/PROBLEM: Z1nc Smelting Plant
LOCATION/COUNTRY: Lot River
V1v1ez, Aveyron
France
CONTAMINANT(S): Z1nc
Cadmlurn
MEDIUM OF CONTAMINATION: Groundwater
STATUS AS A NATO/CCMS
STUDY PROJECT:
Proposed: 4/88
Accepted: 4/88
Interim Report(s): 11/88; 11/89
Expected Completion Date:
Final Presentation:
-193-
-------
Paper Not Received by
Time of Printing
-------
TYPE OF TREATMENT:
General:
Specific:
Researcher/Manufacturer:
FORMER USE/PROBLEM:
LOCATION/COUNTRY:
CONTAMINANT(S):
MEDIUM OF CONTAMINATION:
STATUS AS A NATO/CCMS
STUDY PROJECT:
Proposed:
Accepted:
Interim Report(s):
Expected Completion Date:
Final Presentation:
Soil Treatment by Extraction
In-S1tu Extraction
Photographic Paper Manufacturer
Soestdulnen
The Netherlands
Cadmium
Sandy soil
4/88
4/88
7/88
11/88
-195-
-------
TAUW Infra Consult
In situ cadmium removal
- full-scale remedial action of contaminated soil -
L.G.C.M. Urlings*, V.P. Ackermann**, J.C. v. Woudenberg*,
P.P. v.d. Pijl*, J.J. Gaastra***
* TAUW Infra Consult B.V. , P.O. Box 479, 7400 AL DEVENTER
-------
Table 1. Soil-
characteristics
for three soil-lavers
sieve size
top layer
layer above
layer below
groundwatertable
groundwatertabl«
< 16 um
0.6
3.7
2.4
16 - 63
1.3
1.7
1.6
63 - 90
3.0
7.0
7.6
90 - 125
10.1
14.6
16.1
125 - 180
29.1
26.3
28.1
180 - 250
27.4
19.7
20.3
250 - 355
18.9
13.6
13.0
355 - 500
6.8
6.1
5.1
500 -1000
2.6
5.0
3.9
1000-2000
0.3
1.5
1.1
> 2000 um
<0.1
0.7
0.7
PH
4.9
4.7
7.4
CEC meq/100 g
3
2.5
1.8
org. carbon %
0.3
<0.1
<0.1
CACO3-content
« 0.4
0.6
0.6
Fe(oxalate
exactractable)
mmol/kg dm
5
6
- 3
Al(oxalate
extractable)
mmol/kg dm
10
7
5
dry matter %
98.1
96.7
90.4
The soil can be characterised as middle fine to middle coarse
sandy soil. The adsorption capacity of the soil in general is very
low.
The whole in situ treatment involves approximately 30,000 m^ soil
within an area of 6,000 m^. For the authorities a priority for
remedial action was given because of the expected additional
pollution of the ground water and the possibility of direct contact
for recreants with contaminated topsoil. The groundwater is used
for the preparation of drinkingwater.
2. DEVELOPMENT AND INSTALLATION OF THE REMEDIAL ACTION TECHNIQUE
Removal of the cadmium pollution out off the environment can be
obtained by remedial action on the solid soil on location of the
former ponds and the dune plot and by remedial actions of the deep
groundwater downstreams of the plant (upstreams of the groundwater
resource). In this presentation, only the remedial action of the
solid soil is outlined.
Concerning in situ remedial action three aspects need special
attention, because there is no or very little experience available
in this matter:
- the Cd-desorption of the polluted soil (soil chemistry)
- the hydrological system of infiltration and withdrawal of water
(hydrology)
- the purification of Cd-containing groundwater (watertreatment).
-197-
-------
According to the three topics mentioned above, laboratory experi-
ments, designs and/or installations are outlined underneath.
2.1. Desoration of cadmium
A desorption liquid was selected by batch-experiments with polluted
soil. By calculation of the Cd-distribution coefficients (K
-------
Kd=idm3/ka
II
time in day.
H
figure 3. Calculated cadmium concentration in the percolate of five
separate compartments
2. Hvdrologic system
The total area for remedial action amounts to 6,000 nr (see figure
1). The capacity of the groundwater treatment installation was
limited to approximately 250 m^/h, so the at one time treatable
polluted area is dependent on the hydraulic properties of the soil.
Horizontal drains are preferable to vertical deepwells in order to
get straight groundwaterflow lines. A cross section of infiltration
and withdrawal systems is outlined in figure 4.
oH control
oH control
drain • 10cm.
extension of the drains
0—ICd removal treatment!
ICd removal treatmentt~0
III IV
figure 4. Cross section of the infiltration and withdrawal systems
-199-
-------
Design and dimension of Che infiltration/withdrawal system was
carried out by a two-dimensional (vertical) computer model. The
calculated results are converted into the three-dimensional space.
Full recirculation of the infiltrated water can be guaranteed when
only a slight quantitity of aquifer water is discharged additional-
ly-
For one compartment the groundwater flow pattern is represented in
figure 5.
figure 5. Two-dimensional flow pattern of the infiltration water
The end of the remedial action will also be determined by the Cd-
concentration in the pumped percolate for each separate compart-
ment: in principal, infiltration with acified water should be
continued untill the Cd-concentration reaches a constant low value
(approximately 20 ug/1). The installed infiltration and withdrawal-
system for the whole contaminated area is outlined in figure 6.
The compartmentsize is bases on practical experience during the
proceedings of the remedial action.
figure 6. Overview of the horizontal drains in the four compart
ments
-200-
-------
*
2.3. Watertreatment system
A literature survey was conducted on the removal of Cd from waste
water.
The three most important treatment techniques are:
. precipitation
. biosorption
. ion-exchange
Because the treated acid percolate is infiltrated again in the
polluted soil and the waterflow is quite high, viz 250 m^, sorption
on resins is preferred.
First in the laboratory batch experiments were carried out. The
main goal was to select a resin with a high specific Cd-adsorption
in presence of a high iron-, aluminium- and calcium-concentration
and a pH of 3.5.
The IMAC GT-73 turned out to be the most selective for Cd.
After the batch experiments a column experiment was set up to test
the IMAC GT-73 resin of Rohm and Haas. The experimental set up is
shown in figure 7.
aH control
INFILTRATE : pH - 3.5-4
HYDRAULIC
LOAD RESIN : 20 bedvolu-
mes/h
Cd-SOIL : 20-30 mg/kg dm
Pump.
figure 7. Laboratory testunit for the resin column
The load of the first resin column is 6.7 g Cd/1 resin while the
effluent of the second resin column contains no Cd (<1 ug/1).
Loads as high as 34 g Cd/1 resin were found in previous experiments
with high Cd-influent concentrations.
Regeneration of the Cd-loaded resin is more or less complete when
flushed with 4 bedvolumes of 5% HC1.
Based on the laboratory results the dimensions of the full scale
installation are designed. Due to the relative short operation
time (approximately one year) there were made some modifications
in the original design so the contractor was able to instale
smaller resin filters.
The installed water treatment system is represented in figure 8.
-201-
-------
The ion-exchange system consists of 5 filters with 3 nr* resin IMAC
GT 73 each. Two parallel streets of each two filters have been
installed with one filter stand-by used during regeneration.
MAIN FILTERS
I Cd 300 > 2000PPP
100 4 2S0mVh
groundwater
90 » 225»Vn
3m1
3m1
resin
resin
1
2
systen
3«J
3m1
resin
resin
3
4
STANDBY FIlTtB
POLISHING FllTEH
Backwash facilities
Regeneration facilities : air-hold down tysfea
HCl SX (2-3BV)
Storage
1m*
resin
PH
control
pH
conyot
|co
-------
3.
THE RESULTS OF THE REMEDIAL ACTION OF COMPARTMENT I
In August 1987 the in situ remedial action started with the less
contaminated compartment I. Compartment I is the most distant
compartment from the formal discharge pounds on the plantground.
The compartment I remedial action forms a testcase and the results
will be applied for the treating device for the rest of the conta-
minated soil.
3.1. Hvdrologic system
First infiltration was carried out with neutral water to test
hydrological permeability of the soil. The permeability of the 6 m
soil layer above the horizontal withdrawal drains was much lower
than was measured in the topsoil. Extrapolation of the granulair
composition of the different soil layers as pointed out in table 1
and application of the results of cone penetration tests indicate
also higher permeability.
The inclusion of air in the pores was expected but no complete
evidence could be gained. The delivery of the drainage system was
between 50 and 55 m^/h for compartment I during the remedial
action.
The flow direction of the groundwater was observed by 6 shallow
piezometers around the pound and 7 deep piezometers in the pound.
The deep piezometers have filters at the depth of 5, 10 and 15 m
below surface.
During the remedial action of compartment I only slight changes in
flow direction have taken place. The system was adjustable to
change the flow in the good direction.
3.2. Desorption of cadmium
The Cd-concentration of the influent (percolate) and effluent of
the first resin filter are represented in figure 9.
In figure 10 the cumulative quantity of Cd removed is outlined as
well as the pH of the percolate.
In the begin of August after the soil was saturated the percolated
water beared higher Cd-concentration than was measured during
the normal unsaturated circumstances in 1985. Probably the little
pores of the soil, which are not flushed under unsaturated condi-
tions, are responsable for the additional Cd release. The course
of the measured Cd concentrations in the influent is comparable
with the calculated concentrations as represented in figure 4. In
order to give a more complete impression of the percolate composi-
tion some data from chemical analyses of September 1 1987 are
outlined in table 2.
-203-
-------
StC
S'J
tMI »m« t
• • •
H
AUGUST
S
H
0CT08C8
H
NO*|H0f B
figure 9. Cd-concentration of influent (percolated and effluent
of the first resinfilter
C«U|I
*1
AUGUS'
figure 10. Cumulative quantity of Cd removed and pH of the per-
colate
Table 2. Influent
analysis. September 1
Table 3. Cd- and pH-values for ground-
water from filters of 2 piezometers on
9th September 1987
pH
5.0
E.C.
us/cm
276
CI*
mg/1
66
HCO 3"
meq/1
0.09
C03"
meq/1
<0.01
Cd
ug/1
440
Ca
ug/1
26000
Fe
ug/1
<15
A1
ug/1
160
Mn
ug/1
145
Piezometer
II 12
filter Cd
PH
Cd
pH
(ug/1)
(ug/1)
lm 16
4.1
8
3.8
2m 80
4.6
48
4.3
3m 383
4.75
2370
5.3
4m 1150
5.9
7580
5.7
5m
70
6.6
-204-
-------
The piezometers II and 12 (see figure 6) with filters on 1, 2, 3,
4 and 5 m were of great value to controll and predict the process
of the remedial action. In table 3 a moment survey of the Cd
concentration and pH is given for the piezometers II and 12.
The effectiveness of the remedial action is controlled by soil
analyses. The 12th October the Cd concentration in the percolate
was less than 10 ug/1 so acidification of the infiltrate was
stopped. The 26th October neutralization of the acid soil was
started with NAOH pH 8.5.
The neutralization stopped when the percolate Cd concentration of
every seperate drain was not detectable (< 10 ug/1) anymore.
3.3 Water treatment system
The performance of two resin filters in series is excellent. By
the end of September the first filter was totally loaded (6.7 g/1
resin), while the second filter operated correctly. Due to low
influent concentration the Cd load was relatively low.
The first resin regeneration pointed out a recovery of more than
98% of the adsorbed cadmium. The main metals found in this eluate
are pointed out in table 4.
Table 4: Eluate composition after resin regeneration
. cadmium 2600 mg/1 . zinc 23 mg/1
. calcium 940 mg/1 . silver IS mg/1
. aluminium 170 mg/1 . iron 12 mg/1
The conclusion can be drawn that the resin IMAC GT 73 is very
selective for cadmium.
3.4 Conclusions and recommendations
The experiences with the full scale in situ remedial action of the
first compartment showed that:
-the desorption of cadmium is good comparable with the laboratory
studies. However neutralization takes a long time;
-the permeability of the whole soil layer is rather different
from what was measured in the topsoil;
-the watertreatment system operates according to the design crite-
ria.
Hence the remaining contaminated area, 5000 m^, would be remedia-
ted in situ. Due to the low end values of Cd in soil for compart-
ment I, the remedial action limit was lowered from 5 mg Cd/kg d.m.
to 2,5 mg/kg dm.
The experiences of the remedial action of compartment I resulted
in the following recommendations:
enlargements of the compartment size;
3 m instead of 4,5 m distance between the deep horizontal
withdrawal drains (5,5m below surface);
instale additional drains on a depth of 2.25 m below surface
to accelerate the remedial action.
-205-
-------
4.
THE RESULTS OF THE REMEDIAL ACTION OF COMPARTMENTS II. Ill
AND IV
4.2 Desorotlon of cadmium
The compartment configuration is outlined in figure 6. In October
and November the infiltration/withdrawal of compartment IV (2000
m2), III (1500 m2), and II (1000 m2) started.
From the beginning of December acid water has been supplied to the
compartments.
The Cd-concentrations in the vithdrawed percolate form the com-
partments II and III is given in the figures 11 and 13.
Concerning compartment IV two withdrawal pumps were used; at
the eastside pump 2 and at the westside pump 3.
The Cd-concentrations of the pumped percolate are given in figure
15 (pump 2) and figure 17 (pump 3). The corresponding cumulative
quantity Cd pumped from each compartment are shown in the figures
12, 14, 16 and 18.
Compartment IV, figures 15 and 17 indicate lower Cd concentrations
than calculated (see figure 3, part I and II). Especially for the
eastside of compartment IV the initial Cd concentrations without
acid infiltration was quite high (figure 15).
The cumulative quantity Cd pumped from each compartment is given
in table 5. While the Cd removal by the watertreatmentinstallation
for the whole remedial action period was not compete, see chapter
4.3, the Cd quantity removed from the soil is less than stated in
table 5.
Table 5 Cumulative quantity Cd pumped per compartment
Compartment II 77 kg Cd
Compartment III 154 kg Cd
Compartment IV east 143 kg Cd
Compartment IV west 45 kg Cd
Compartment I 24 kg Cd
Total 443 kg Cd
-206-
-------
figure 11. Cd-concentration in pumped percolate of compartment II
figure 12. Cumulative quantity Cd removed and pH of the percolate
(compartment II)
-207-
-------
stop acid
start bast
I I I I I I I I I I I I I I I
19-Nov 29-Dec 07—Feb 18-Mar 27-Apr 06-Jun 16-Jul 29-Aug 0*-0ct
figure 13. Cd-concentration in pumped percolate of compartment III
feastsidet
figure 14. Cumulative quantity Cd removed and pH of the percolate
(compartment III)
-208-
-------
\
ei
E
e
o
figure 15. Cd -concentration in pumped percolate of compartment IV
eastside
cd (kg)
30—Sep
08—Jon
17—Apr
26—Jul
03—Nov
figure 16. Cumulative quantity Cd removed and pH of the percolate
(compartment IV)
-209-
-------
450
\
ai
.c
e
o
01
w
c
OS-Jan
17-Apr
28—Jul
03—Not
figure 17. Cd-concentration in pumped percolate of compartment IV.
westside
30-Sep
OS—Jon
17—Apr
26—Jul
03—Nov
figure 18. rnmimilative quantity Cd removed and pH of the percolate
(compartment IV. westside)
-210-
-------
*
The Cd-concentrations in the percolate water showed large dif-
ferences (see for example table 3 difference of 5000 ug/1 within 1
m). Figure 19 gives an impression how Cd scattered in the deep
horizontal drains of compartment IV. Drain length is about 20 m.
CAST Droinnumber WEST
Figure 19. Cd concentrations in deep horizontal withdrawal drains
compartment IV (draindistance 3
The progress of the in situ remedial action is judged on the Cd
concentration of soil samples. In table 6 the end values of Cd
content in soil samples are given.
Table 6. The distribution of Cd-concentrations (me Cd/ke d.nO in
soil analyses
<1
>1 and <2.5
>2.5 and <5
>5
Compartment II
39
4
2
0
Compartment III
40
1
1
0
Compartment IV
88
6
2
3*
The origin of the Cd contamination is probably different. The
natural soil layers are disturbed by antropogenic activities;
incineration stags are observed.
The latesC samples of table 6 were taken in the beginning of
October 1988. Hence at the end of October when infiltration stop-
ped the remedial action goal of 2,5 mg Cd/kg dm was reached, with
the exception of the 3 samples taken in this middle off compart-
ment IV west. Further investigation are carried out to determine
the origin of this immobile Cd contamination. Additional excava-
tion of the small area is probably the most suitable remediation
technique.
4.2 Hvdrologic system
The start up procedure took, as in compartment I quite a long
time. In all compartments the escape of air could be observed. The
maintenance of the desired discharge flow rate was difficult,
mostly the discharge was too low.
-211-
-------
The low permeability of the soil is due to the high resistance of
a rather thin soil layer. The infiltration increased by making
use of the infiltration drains on 2.25 below surface. Especially
in the heavily contaminated area of compartment IV, the shallow
drains are used succesfully.
The withdrawal capacities for the compartments were:
compartment I 25-50 m^/h
compartment III 20-40 m^/h
compartment IV east 45-65 m^/h
compartment IV west 35-40 m^/h
The maximal withdrawal flow was approximately 200 m^/h, and the
average flow was about 145 m^/h. The discharge flow was only 8,3%
of the infiltration water flow.
In table 7 the calculated infiltration capacity of the different
compartments is stressed. During the first period discharge took
place in compartment I, and for the second period the sewer was
used.
Table 7. Infiltration capacity during 2 periods
period 1 period 2
compartment dec.-may may-aug.
(m/d) (m/d)
II 0.81 1.02
III 0.77 0.81
I V 0.60 0.91 ( influence shallow drain)
In figures 20 and 21 computed infiltration/groundwater stream line
patterns are presented for respectively discharge of surplus water
onto compartment I or the sewer.
During discharge on compartment I (figure 20) there is a stream
off of infiltrated water from compartment II. .The streamline
pattern showed in figure 21 indicate that discharge on the sewer
is preferable. Still there is a little stream off, this must be
related to the discharge quantity of 8.3% instead of 10% of the
infiltrated water.
For the two periods it was calculated that 70% of the compartment
areas are flushed more than 75 times.
-212-
-------
(m)
30.
30.
0
~
1 I I I I I I I I | I I I I I I I I t | I I I I I I I I l[ I * * I * H I I | I I I I ¦ I I I I | t I I I I I I I I j
ss.
80.
I OS.
130.
1SS.
160. (m)
PROGRAM TRIFLO
ft— 1*1 MriH
riialiil mm/ye 10
ptlat 04 04
«r|Ii wtcrihr. t^tli M«r. U
Mllara Mm ^4 0411
Mfli vitfe i-«li 4«fr. 1704
UlckMM •* i*l1*r ¦ 1214
OJS
MM* «f 1
MMT tf Mil* 0
•( *ilai U
MM if (MpVlMltl I
HU r.
IM Hi IU U «IH
Mi MU tu IU -m.
fig. 20
figure 20. Streamline pattern, discharge surplus water on
compartment I
(«>)
us. _
30.
0
Ullllllllfruxm
I I I I I I I I I I ' ¦ » ¦ «c
I ' » * * « I I I
111111
—11
I I I I I !¦
i»' ¦ It»t n ¦ I»I It I m ¦ I n» 111 n ''''11 M 'I'1'1' " I 'I'11' 11' 111
30.
SS.
60.
10S.
130.
1SS.
180. (m)
PROGRAM TRIFLO
Omki ImiIAiIm 2m
uMilt fl^Nr 04
p*lat MtirOiiM 04 04
Mil «(«<». inii 4*«r. 04
wifar«liM^4 0411
«mI« «||k ihiIi Mfr. 2704
IklikMM it Hvllw m 1210
pcrully 0J1
MM ll Nfi. lllllttllN I
mmtar •< wlla 0
WMr ll irilM U
•Mr il wvvlmli I
as war1 a""®"1
IMJ UJ
HU MJ
IMJ IU
MU MJ
IMJ IU
IMJ MJ
IMJ tU
IIU iu
IIU IM
MU IU
ItU IU
ItU IU
IIU IU
MU IU
MU IM
MU IU
IIU MJ
IU Mi
Mi MJ
hi iu
M IU
U tu
U IU
U tu
u tu
u m
U IU
U IU
U IU
U IU
U IU
U IU
U IU
U IU
u tu
U IU
U IU
u tu
u tu
u tu
U Mi
Mi U Mi
Mi U Mi
iu Mi U Mi
IU IU u tu
KS Mi U Mi
tu MU U Mi
Mi IMJ U 114
U IIJ UI
u ttS ui
Mi I Mi U IU
i Mi m tu tu
ttu iu iu iu
iu ni iu tu
•u iu iu u
Mi MU tU tU
fig. 21
figure 21. Streamline pattern, discharge surplus water in sewer
-213-
-------
Downstreams of the compartment (east) an additional groundwater-
vithdrawal system is installed to minimize the stream off. In
September the system started with groundwater extraction at a
flowrate of approximately 60 m^/h, and probably it will be con-
tinued till the end of November 1988. The Cd concentration was
approximately 120 ug/1 in the beginning of November 1988.
4.3 Watertreatment system
-Flow
The average hydraulic loading of a resin tank was almost 24
Bedvolumes/h. The design flow was 33 Bedvolumes/h. The average
influent flow rate was 143 m^/h while the maximum measured flow
rate was 206 m^/h (27 July 1988).
-pH-influent
The percolates from the separate compartments differed from
pH and ionic composition (Al, Ca). An accurate pH adjustment was
necessary to prevent flocculation in the resin tank at high pH
(>5.5). While at low pH (<5.0) the Cd-adsorption of the resin
decreased.
-Cd loading of the resin
The Cd loading of the resin varied between 7 to 0.5 g Cd/1 resin
and the disign value was 6 g Cd/1 resin. No effect of hydraulic
loading rate could be found on the Cd loading of the resin. To
the resin only slight mechanical demage was observed, the resis-
tance for a clean resin bed increased from 0.3 till 0.5 bar.
Although humic acid substances are adsorbed to the resin no
significant effect on Cd loading of the resin was found during
normal operation.
-Removal efficiency
Under "normal" circumstances the Cd-concentration of the dischar-
ge flow is <1 ug/1 and for the recirculation water (infiltration
water) < 10 ug/1. The average removal efficiency can be estimated
96%. During two periods the performance of the watertreatment
installation was poor. From 25c^ of December 1987 till January
1988 the pH of the influent was 4 instead of 5 as shown on the pH
meter display. Hence the necessary pH adjustment of the influent
did not take place. High Cd influent concentrations caused short
hold out times for the resin tanks in that period.
In the period 4C^ of Augustus till 66*1 of September 1988 the
steady increase of Al- and Ca-concentrations in the influent
together with low Cd-concentration resulted in low Cd-loading of
the resin. In table 8 four influent-analyses are shown.
-214-
-------
Table 8. Cation concentrations of the Influent (percolate)
Cation
date
5 jan '88
21 june '88 9 aug. '88
Cd (ug/1)
Cu (ug/1)
Ni (ug/1)
Zn (ug/1)
Ca (ug/1)
Ag (ug/1)
Al (ug/1)
Fe (ug/1)
pH (ug/1)
1550
3
10
720
135000
10
360
125
3
310
20
40
1450
15
5
96000
840
15
1400
160000
20
7600
5.2
At start of the neutralization of compartment II and III Al and Ca
concentrations dropped strongly due to flocculation.
Taking the two above mentioned periods of poor removal efficiency
in account the average removal efficiency drops from 96% to 88%.
The total amount of Cd removed from the influent is 385 kg. The
pumped cumulative quantity Cd should be around 440 kg, as mentio-
ned in 4.2.
-Regeneration of the resin
The regeneration caused less trouble. The applied air hold down
procedure worked out well. Additional regeneration in laboratory
experiments with a NaOH/NACl mixture and with cyanide had only
slight influence on the Cd adsorption.
Conclusions
Desorption of cadmium
* the Cd desorption from the soil was almost complete;
90% of the soil samples gave Cd values of lmg/kg d.m;
* the desorption of Cd is good comparable with the laboratory
studies especially the column leaching experiments;
* approximately 400 kg Cd is removed from the soil;
* change of soil pH took quite a long time.
Hydrologic system
* start up took a long time due to air inclusion in the soil;
* the permeability of the soil layer was rather low, not with-
standing the greater part middle to course sand present in
the soil;
* the hydrological system reacts slowly to flowrate changes.
The discharge flow was mostly too low according to the design
criteria.
Water treatment system
* the watertreatment system operated according to the design
criteria;
* for proper operation special attention has to be given to
influent pH, and Ca-, Al-concentration in the influent.
-215-
-------
" ApplicaCion
* The remedial action continued the whole winterperiod, 1987-
1988. Temperatures of less than minus 10 C cause no difficul-
ties. The water treatment plant was roofed and kept free of
frost.
Costs
* The total costs of the in situ remedial action are comparable
with the estimated costs.
* The resin will be sold after this remedial action. The com-
mercial value is quite high.
Recommendation
* Apply more in situ remedial actions for the extraction of
contaminants from the soil;
* laboratory experiments can reasonably predict the full scale
soil desorption performance of the contaminant;
* additional attention should be given to the hydrological
charactaristics of the contaminated site.
From the carried out in situ remedial action it is clear that
several specialists are required viz. hydrologists, environmental
engineers, watertreatment engineers and soil scientists. To make
in situ treatment a success they have to co-operate very close.
november 1988
-216-
-------
TYPE OF TREATMENT:
General: Soil Treatment by Extraction
Specific: Vacuum Extraction
Manufacturer:
FORMER USE/PROBLEM: Underground storage tank at a former
solvent repackaging and distribution
facility
LOCATION/COUNTRY: Verona
Battle Creek, Michigan
United States
CONTAMINANT(S): Chlorinated hydrocarbons
Aromatic hydrocarbons
Ketones
MEDIUM OF CONTAMINANT(S):
STATUS AS A NATO/CCMS
STUDY PROJECT:
Proposed: 3/87
Accepted: 3/87
Interim Report(s): 11/87
Expected Completion Date:
Final Presentation: 11/88
-217-
-------
SOIL TREATMENT
VIA
SOIL VAPOR EXTRACTION
«
Presented To
NATO/CCMS PILOT STUDY
DEMONSTRATION OF REMEDIAL ACTION
TECHNOLOGIES FOR CONTAMINATED LAND
AND GROUND WATER
By
U.S. ENVIRONMENTAL PROTECTION AGENCY
November 1988
-------
SOIL VAPOR EXTRACTION
(SVE)
SUBSURFACE VACUUM PROMOTES IN-SITU VOLATILIZATION
HYDROCARBON VAPORS MIGRATE TO EXTRACTION WELLS
VAPORS ARE DISCHARGED TO SURFACE FOR COLLECTION/
TREATMENT
TREATMENT MAY UTILIZE VAPOR-PHASE GRANULAR
ACTIVATED CARBON OR, CONDENSATION AND RECOVERY
-------
CONTAMINANTS REMOVED BY SVE
• VOLATILE ORGANIC COMPOUNDS
K • GASOLINE AND DIESEL OIL
0
1
• SOLVENTS
• MERCURY
• HEAVY NAPHTHAS
-------
SOIL VAPOR EXTRACTION
• NOT LIMITED BY DEPTH
EFFECTIVE FROM 1 METER TO 100 METERS
• DOES NOT DISTURB SOILS
MINIMIZES MATERIALS HANDLING, AND UNCONTROLLED
RELEASES TO AMBIENT AIR
• CLEANUPS ARE RELATIVELY RAPID
RECOVERY RATES > 1 MT/DAY HAVE BEEN ACHIEVED
AVERAGE RECOVERY RATE = 55 kg/DAY
-------
GEOLOGY/SOILS
• CLAY
• SILT
• SAND
• GRAVEL
• FRACTURED ROCK
~ • KARST LIMESTONE
ro
i
GROUND WATER
• MINIMUM DEPTH = 60 CENTIMETERS
• MAXIMUM DEPTH = 100 METERS
-------
SVE DESIGN CONSIDERATIONS
EQUIPMENT IS NOT SPECIALIZED
- PVC/STAINLESS STEEL WELLS AND PIPING
- CONVENTIONAL VAPOR PHASE CARBON TREATMENT
- INDUCTION BLOWER
- CONVENTIONAL AIR/WATER SEPARATOR
EXPERTISE NEEDED FOR SYSTEM DESIGN
- REQUIRES UNDERSTANDING OF SITE LITHOLOGY
- REQUIRES DATA ON CONTAMINANT TYPES,
CONCENTRATIONS AND LOCATIONS
- DIFFICULT TO CALCULATE TOTAL CONTAMINANT MASS
- DIFFICULT TO DETERMINE RECOVERY RATES
- PREFERABLE TO PILOT-TEST
-------
CASE STUDY:
SOIL VAPOR EXTRACTION PROJECT
AT THE
ro
ro
-P*
VERONA WELL FIELD SUPERFUND SITE
BATTLE CREEK, MICHIGAN
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SITE DESCRIPTION
LOCATION: BATTLE CREEK, MICHICAN
SITE: VERONA WELL FIELD SITE CONSISTS OF 4 DISTINCT
PROBLEM SITES WITHIN AN AREA OF 40 HA
1. MUNICIPAL WELL FIELD/30 PRODUCTION WELLS
2. THOMAS SOLVENT/RAYMOND ROAD FACILITY
3. THOMAS SOLVENT/ANNEX FACILITY
4. GRAND TRUNK WESTERN R.R. FACILITY
SETTING: URBAN
RESIDENTIAL AND LIGHT INDUSTRIAL
PROBLEM: IN 1981, ONE-HALF OF THE CITY'S WELLS WERE
CONTAMINATED WITH VOCs [l-100jug/L]
U.S. EPA INVESTIGATION REVEALED 3 SOURCES
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I
WESTERN
RAILROAD
MARSHALLING
YARD
FIGURE 1
VICINITY MAP
-226-
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~ EW1
/TYPICAL
GROUNDWATER
EXTRACTION
WELL
MONITORING BUILDING
MCC BUILDING
THOMAS SOLVENT
BUILDING
(DEMOLISHED)
LOADING DOCK
(DEMOLISHED)
SVE PROCESS BUILDING
FFICE BUILDING
FIGURE 2
LOCATION OF
UNDERGROUND TANKS
-227
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THOMAS SOLVENT/RAYMOND ROAD FACILITY
(TSRR)
TSRR, A SOLVENT DISTRIBUTION BUSINESS STORED, TRANSFERRED
AND PACKAGED SOLVENTS
OPERATED FROM 1970 T01984
SITE CONTAINED: OFFICE BUILDING
WAREHOUSE
LOADING DOCK
21 UNDERGROUND TANKS
19/21 TANKS WERE FOUND TO BE LEAKING
REPORTS OF SURFACE SPILLAGE DOCUMENTED
GROUND WATER BENEATH TSRR > 100,000 ppb VOCs
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LITHOLOGY
FINE TO COARSE GRAINED SANDS
TRACES OF SILT, CLAY, PEBBLES
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~ DEPTH TO GROUND WATER APPROXIMATELY 7 METERS
HYDRAULIC CONDUCTIVITY .01-0.1 CM/SEC
SANDSTONE BEDROCK AQUIFER APPROXIMATELY
9-15 METERS BELOW SURFACE
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PRINCIPAL SOIL CONTAMINANTS
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CHLORINATED HYDROCARBONS MAX. CONC. (ppb)
METHYLENE CHLORIDE 60,000
CHLOROFORM 2,000
1,2,-DICHLOROETHANE 27,000
1,1,1 -TRICHLOROETHANE 270,000
TRICHLOROETHYLENE 550,000
TETRACHLOROETHYLENE 1,800,000
AROMATICS
TOLUENE 730,000
XYLENE 420,000
ETHYL BENZENE 78,000
KETONES
ACETONE 130,000
METHYL ETHYL KETONE 17,000
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TREATMENT OPTIONS SELECTED
GROUND WATER: CONVENTIONAL PUMP AND TREAT SYSTEM
• 9 EXTRACTION WELLS (1,500 L/MIN)
• CARBON TREATMENT
• REMOVED >4,000 kg OF VOCs
• SYSTEM STILL OPERATING
SOILS: SVE SELECTED TO REMOVE VOCs FROM
VADOSE ZONE
• WOULD NOT DISTURB SOILS
• BELIEVED THAT SVE COULD ACHIEVE
CLEANUP TARGET OF 10 mg/kg
• PROJECT DURATION APPROX. 3 YEARS
• REASONABLE COST
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PRECONSTRUCTION ACTIVITIES
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GEOPHYSICAL SURVEY
SOIL SAMPLING
SOIL GAS SURVEY
TO DETERMINE AREAL EXTENT
OF CONTAMINATION; CONCENTRATIONS
AND TOTAL MASS OF VOCs
INITIAL ESTIMATE OF VOC MASS = 800 kg
REVISED ESTIMATE AFTER PILOT TESTING = 5,800-7,500 kg
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SVE PILOT PHASE
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11 EXTRACTION WELLS
SYSTEM OPERATED FOR 70 HOURS
RESULTS: 1,300 kg VOCs REMOVED .
CARBON LOADING RATE 0.167 -P3—^55
kg GAC
RADIUS OF INFLUENCE >15 m
WITH WELLHEAD VACUUM OF 8-10 cm Hg
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AIR/
WATER
SEPARATOR
VOC-
CON TAMINA TED
AIR
©
®
©
PRESSURE INDICA TOR
TEMPERA TURE INDICA TOR
SAMPLING PORT
FLOWMETER
WS847I.QS F1G3.0WG
VOC- CON TAMINA TED
AIR
DISCHARGE
TO
ATMOSPHERE
AMBIENT AIR
INTAKE
I
VACUUM EXTRACTION
UNIT
FIGURE 3
SCHEMATIC OF SOIL
VAPOR EXTRACTION
SYSTEM
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FULL-SCALE OPERATION
23 WELLS:
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SYSTEM:
10 cm DIAMETER PVC
SLOTTED SCREEN 1.5 m BELOW GRADE TO
1 m BELOW WATER TABLE
PACKED WITH SILICA SAND
SEALED WITH BENTONITE
EACH WELLHEAD HAS THROTTLING VALVE,
SAMPLE PORT, VACUUM GAUGE
SURFACE COLLECTION MANIFOLD
CENTRIFUGAL VAPOR/WATER SEPARATOR
CARBON ADSORPTION TANKS
VACUUM EXTRACTION UNIT (30 HP)
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FIGURE 4
SVE WELLS AND PIPING LAYOUT
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FUTURE PLANS/ISSUES
GOLD WEATHER OPERATIONS IMPACT ON TECHNOLOGY
CONTINUED HIGH EXTRACTION MAY ALTER TREATMENT
TRAIN
EVALUATION OF CARBON CONTAMINATED WITH
RADIOACTIVITY
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RESULTS
(MARCH - AUGUST 1988)
5,400 kg VOCs REMOVED
34,800 kg GAC USED (COST = $200,000 U.S.)
VERY HIGH INITIAL VOC CONCENTRATIONS LED TO FREQUENT
BREAK-THROUGHS IN PRIMARY CARBON UNITS
DATA INDICATE VOC MASS MUCH GREATER THAN ESTIMATED
99.8% REMOVAL EFFICIENCY MEASURED AT EXHAUST STACK
VAPOR CONDENSATION WITH OFFGAS CARBON TREATMENT
UNDER CONSIDERATION TO REDUCE COSTS
RADON GAS ALSO REMOVED FROM SOILS
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FULL-SCALE OPERATION (CONTINUED)
GAC: • VAPOR- PHASE CARBON
• 2 STAINLESS STEEL CANISTERS IN SERIES
• 450 kg GAC/EACH CANISTER
• PRIMARY UNIT ADSORBS MOST VOCs
• SECONDARY UNIT SERVES AS BACKUP
ROTATED INTO SERVICE AT PRIMARY TANK
BREAKTHROUGH
• CARBON THERMALLY REGENERATED AT
OFF-SITE FACILITY
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COST
SVE CONSTRUCTION $737,000.00
COST INSTALLATION/CU. METER TREATED $ 17.00
(EXCLUDING COST OF CARBON)
COST OF CARBON $ 4.60/kg
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? PROJECTED CARBON USAGE > 100,000 kg
PROJECTED CARBON COST > $ 500,000.00
ESTIMATED COST TO TREAT 1 CUBIC METER SOIL
APPROX. $50.00 TO $60.00
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TYPE OF TREATMENT:
General: Volatilization
Specific: Radio Frequency Volatilization
Researcher/Manufacturer: IIT Research Institute
FORMER USE/PROBLEM: Abandoned firefighter training area
LOCATION/COUNTRY: Volk A1r Field
Wisconsin
United States
CONTAMINANT(S): Gasoline/kerosene mixture
Aviation fuels
Waste oils
Hydrollc fluids
TCE, TPH
MEDIUM OF CONTAMINATION: Soil
STATUS AS A NATO/CCMS
STUDY PROJECT:
Proposed: 4/88
Accepted: 4/88
Interim Report(s): 11/88; 11/89
Expected Completion Date:
Final Presentation:
-241-
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RADIO-FREQUENCY THERMAL SOIL
DECONTAMINATION PILOT TEST
A Case Study for the NATO/CCMS Pilot Study
on Remedial Action Technologies for
Contaminated Land and Groundwater - Nov 88
Mr Douglas C Downey
HQ AFESC/RDVW
Tyndall AFB, FL USA
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FIELD TEST OF THE RADIO FREQUENCY IN SITU
SOIL DECONTAMINATION PROCESS
Harsh Dev
Guggilam C. Sresty
Jack E. Bridges
IIT Research Institute
Chicago, Illinois
Douglas Downey
U.S. A1r Force
HQ Engineering and Services Center
Tyndall AFB, Florida
ABSTRACT
A field test was performed to prove the feasibility of the RF 1n situ soil decon-
tamination process. The test site was located in an old fire training area which had
been used to conduct fire training drills in simulated aircraft fires. It is estimat-
ed that approximately 50,000 gallons of unburnt jet fuel soaked 1n the sandy soil of
the fire training area. The feasibility of the RF 1n situ decontamination process was
demonstrated by heating a block of soil of dimensions 6 ft x 12 ft x 7 ft to a temper-
ature range of 150°-160°C. Analysis of numerous pre- and post-test soil samples has
Indicated that on the average 99% of the volatile aromatics and allphatics had been
removed from the 500 cu ft heated volume. On the average, 94% of semi-volatile ali-
phatics and 99% of the aromatics were also removed.
Migration of contaminants into and out of the heated zone was assessed by inject-
ing a tracer into the soil and by sampling soil in zones Immediately outside the per-
imeter of the heated volume. Halon® tracer, injected 4 ft outside the heated volume
at a depth of 6 ft, was detected in the raw gases being collected from the heated
zone. This indicates that soil gases and liquids were moving into the heated zone
from outside. A contaminant reduction of 70-76% was observed in the inmediate area
outside the heated zone. These results demonstrate that there was no net migration of
contaminant from the heated area to the surrounding soil.
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The results of this study warrant optimization and full-scale demonstration of
the technology so that it can be used on a commercial basis for the remediation of
sites containing jet fuel, gasoline, and other similar contaminants.
INTRODUCTION
At many hazardous waste sites, soils containing solvent and fuel contaminants are
found. Typical examples of such materials are: tetrachloroethylene, dichloroethane,
trlchloroethylene, chlorobenzene, and various aromatic and aliphatic fractions of jet
fuel, gasoline, etc. These materials boll 1n the temperature range of 80° to 300°C,
and can be readily volatilized by Increasing their temperature. These and other simi-
lar materials pose a continuous threat to the environment because the chlorinated
hydrocarbons are extremely stable and undergo degradation in the environment at a slow
rate. On the other hand they can migrate from the sites of original disposal and
contaminate ground water resources. For such materials excavation and Incineration of
the soil at 2000°C represents an overkill. A much more attractive alternative 1s to
remove the chemicals from the soil 1n the vapor phase followed by condensation and
ultimate disposal of a small quantity of the hazardous material by incineration or
other suitable methods.
The radio frequency in situ heating method 1s a technique for rapid and uniform
in situ heating of large volumes of soil. It can be used to Increase the soil temper-
ature to a range of 150° to 400aC, thus volatilizing most of the hazardous compounds
on CERCLA's listing. The gases and vapor formed in the soil matrix can be recovered
at the surface or through vented electrodes used for the heating process. The process
does not depend on heat transfer fluids or in situ combustion of fuels, so a
concentrated gas stream can be recovered. This permits condensation of bulk of the
contaminants and their recovery as a liquid with only a minor portion absorbing on the
carbon bed. Cost of carbon for treatment of the vapors is generally a major cost item
for processes based on vacuum extraction. Recovery of the contaminants in
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concentrated form after in situ heating reduces carbon requirements and overall
treatment cost. Because the soil is uniformly heated, a more uniform decontamination
of the heated zone can be achieved than by methods which rely on recovery through a
pattern of multiple bore holes to which vacuum is applied. Another advantage of the
in situ heating method is that it conditions the soil by increasing the permeability
to gas flow by removing the soil moisture from the pores. This allows for uniform
collection of the volatilized contaminants from the surface or from the electrode
boreholes.
Radio frequency heating 1s performed by the application of electromagnetic energy
in the radio frequency band. The energy 1s delivered by electrodes implaced in holes
drilled through the soil. The mechanism of heat generation 1s similar to that of a
microwave oven and it does not rely on the thermal conductivity of the soil matrix.
The power source for the process is a modified radio transmitter. The frequency of
the applied power 1s selected from the Industrial, scientific and medical (ISM) band,
specifically set aside by the Federal Communications Commission (FCC). The exact
frequency of operation is selected after an evaluation of the dielectric properties of
the soil matrix, and the size of the area requiring treatment.
The RF heating process was originally developed for the recovery of hydrocar-
bonaceous resources from deposits of oil shale and tar sands. Several in situ heating
experiments were performed (1) on such deposits ranging in size from 35 to 660 cu ft,
in which the resource was heated to an average temperature of 200° to 400#C. These
field tests conclusively established the feasibility of in situ heating for various
types of soil matrix.
The feasibility of soil decontamination by thermal mechanisms such as vaporiza-
tion, steam distillation and steam stripping was previously (2) established through
laboratory and pilot scale experiments. In the laboratory scale experiments, soil
spiked with tetrachloroethylene (TRCE) and chlorobenzene (CBZ) was decontaminated by
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treatment in the temperature range of 90° to 130° C for a period of 4 hours. It was
shown that 90 to 99 percent removal of the contaminants is feasible. Mass balance
closure of 75 to 104 percent was demonstrated in these studies.
In the pilot scale studies (3) a tall column of soil containing jet fuel was
placed 1n a 7-ft tall, 2-in. diameter stainless steel pipe. It was shown that 90 to
99% percent of total aromatlcs and total non-aromatics fraction 1s removed by
treatment at 150° to 160°C for a period of 14 to 40 hrs. The tall column studies were
designed to show that the vaporized contaminants at depths can be recovered from the
upper surface of the soil bed. It was also shown in these experiments that higher
boiling components such as pentadecane (b.p. 270.5°C) can be removed at lower tem-
perature of 150° to 160°C provided a steam sweep can be established 1n the soil. In
the pilot scale, the sweep was established by injecting pre-heated water at the base
of the hot soil column. In this way, at least 94% of the high boiling pentadecane was
removed from the soil. In the field such a sweep is autogenously established by the
boiling of soil moisture 1n the heated zone and is maintained due to Intrusion of
water from the surrounding cool zones Into the heated zone.
PRINCIPLES OF RADIO FREQUENCY HEATING
The term radio frequency (RF) generally refers to the frequencies used in wire-
less communications. These frequencies can be as low as 45 Hz or extend well above
10 GHz. The frequencies primarily used for radio frequency, dielectric, or microwave
heating range from 6.78 MHz to 2.45 GHz.
The principles of radio frequency heating are similar to those of a microwave
oven, except that the frequency of operation is different and the size of the applica-
tion is much larger. In these systems, the temperature rise occurs due to ohmic or
dielectric heating mechanisms. Ohmic heating arises from an ionic current or conduc-
tion current that flows in the material in response to the applied electric field.
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FIELD TEST DESCRIPTION
A 6 ft x 12 ft area of the fire training pit was heated using a triplate elec-
trode array as shown in several views in Figure 1. In the top left-hand corner of the
figure, a plan view of the electrode array is shown. Three electrode rows were
implaced in drill holes bored through the soil. In each row there were 13 electrodes
spaced 1 ft apart. The length of each row was 12 ft. The spacing between two adja-
cent rows was 3 ft. The depth of the two outer electrode rows was 8 ft while the
center row depth was 6 ft.
All the electrodes in each row were electrically connected together with brass
straps. Each row was then connected to the RF power source by means of a RF transi-
tion section shown in the plan view in Figure 2. Figure 2 illustrates the general
site layout showing the heated zone and a concrete pad poured around the heated zone
to form a "picture frame." A silicon rubber sheet was stretched from end-to-end over
the concrete frame and bonded to it, to form the vapor barrier. Two perforated gas
collection lines were placed over the soil surface below the vapor barrier. These
lines were connected to the vapor collection and treatment system. This system con-
tained a cooler/condenser, a gas-11quid separator and a carbon bed for the treatment
of the vent gas stream. The condensed liquids were collected and saved. An induced-
draft fan was used to collect and transport the raw gases through the treatment sys-
tem.
Soil temperature data was obtained by thermocouples which were attached to the
inner walls of the electrodes. Fluid-filled thermowells were placed in the soil for
measurement of temperature between the electrode rows. There were 49 different tem-
perature measurement points which allowed the mapping of the temperature distribution
in the heated zone, and in the area immediately outside it.
Table 1 summarizes the salient features of the test and selected milestones. At
an average power input level of 30 kW, the temperature in the heated zone reached
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This 1s similar to the current that flows in a light bulb or in resistive heating ele-
ments.
Dielectric heating results from the physical distortion of the atomic or molecu-
lar structure of polar materials in response to an applied electric field. Since the
applied AC electric field changes rapidly, the alternating physical distortion dissi-
pates mechanical energy which is translated Into thermal energy 1n the material.
The dielectric properties of soil determine the amount of RF power that can be
dissipated 1n soil. These properties are relative dielectric constant (er) and the
loss-tangent. The loss-tangent, tan 6, is defined as o/ue0er where a 1s the apparent
conductivity, u is the frequency of the applied electric field, radians/ sec, and e0
is the permittivity of free space, and it equals 8.85 x 10~12 Farads/ meter. All the
dielectric properties are a function of soil temperature, the frequency of the applied
field, and the composition.
The amount of RF power dissipated in the soil is directly related to the fre-
quency of the applied electric field, square of the amplitude, the relative dielectric
constant, and the loss-tangent (4).
IN SITU RF HEATING SYSTEMS
A fully operational 1n situ RF heating system for decontamination requires the
development and testing of at least four major sub-systems. These are: 1. RF energy
deposition electrode array; 2. RF power generation, transmission, monitoring and con-
trol system; 3. vapor barrier and containment system; and 4. gas and liquid con-
densate handling and treatment system.
Among the sub-systems mentioned above, the electrode array (also called the
exciter array) design is the critical item which will drive the design requirements
and constraints for the other three sub-systems.
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Previous attempts (5) to use electrical energy for heating of earth formations
were aimed at resource recovery from hydrocarbonaceous deposits. Simple techniques
such as burying electrical heating elements or a pair of electrodes to which 60 cycles
AC power is applied were not successful due to two main reasons: 1. non-uniform
heating leading to unacceptable levels of energy Inefficiency; and 2. inability to
heat beyond the boiling point of free water. To overcome the temperature limitation
imposed by 60 Hz heating, antennas radiating very high frequency or microwaves have
also been considered (5). Though these methods provide rapid volumetric heating even
above the boiling point of free moisture, they suffer from inefficient use of the ap-
plied energy.
To overcome these limitations, it is necessary to use bound-wave exciters as
opposed to the radiated wave horns or antennas previously used. The bound-wave excit-
ers are designed to fully contain the EM radiation within a defined volume of soil.
There are two basic types of bound-wave exciter arrays. These are the triplate line
and the fringing-field transmission line. The field test described in this paper used
the triplate line to heat soils to a depth of 7 ft. A description of the fringing
field lines is given in Reference (5).
The triplate transmission line is the rectangular analogue of the more familiar
cylindrical coaxial cables. The triplate line is formed by a fully enclosed rectangu-
lar cavity in which a central planar conductor, parallel to the large sides of the
cavity has been inserted. Clearly emplacement of solid metal plates that enclose a
rectangular cavity below the soil surface is impractical. This problem has been
resolved (6) by simulating the fully contained rectangular cavity by inserting an
array of electrodes in boreholes drilled through the soil.
The electrodes are inserted in three parallel rows which represent the two outer
walls and the central conductor of the fully contained rectangular triplate. It has
been demonstrated that through appropriate selection of the row-spacing and the
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spacing of the electrodes within each row, 1t 1s possible to fully contain the applied
electromagnetic field within the two outer rows of electrodes.
FIELD TEST OBJECTIVES
The primary objective of the field test was to prove the feasibility of the RF in
situ soil decontamination process by heating 500 cu ft of sandy soil to remove at
least 90% of the contamination. Other objectives were: 1. heat soil to a depth of 6
to 8 ft; 2. demonstrate heating to a temperature of 150° to 160°C; 3. determine
overall decontamination efficiency and as a function of depth; 4. evaluate contami-
nant migration effects into and out of the heated zone.
SITE CHARACTERISTICS
An abandoned fire training area located at Volk Air National Guard Base, Camp
Douglas, Wisconsin, was selected for the field demonstration test. Historical data
Indicate that the site was used for over 25 years and routinely received waste oils,
fuels and solvents which were deposited 1n the 100-ft (30 m) diameter pit and Ignited
to simulate aircraft fires. An estimated 50,000 gallons (190 cu m) of waste hydrocar-
bons have soaked into the soils. Soil borings indicate a average total petroleum
hydrocarbon concentration of 4000 mg/kg (ppm) extending down 12 ft (3.7 m) to the
groundwater. A more specific gas chromatography analysis shows an accumulation of
heavy oils in the upper 12 in. (30 cm) with an increase in lighter fuel components
with depth.
Soils in the site are homogeneous. Sieve analysis and penetration tests indicate
that a medium grain sand extends from the surface to approximately 13 ft (4 m) where
fractured sandstone is encountered. The homogeneous contamination and soil found at
this site were essential for an initial, controlled test of the RF technology. Future
tests will address less homogenous and clayey soils.
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TRANSITION
.SECTION
TRENCH
CONCRETE PAD
40 KW
TRANSMITTER
TRAILER
VAPOR
COLLECTION
SYSTEM
EDGE
OF
ROAD
MATCHING
NETWORK
OVERHEAD
LIGHTS
RF OUTPUT
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WALKWAY
WW2
INSTRUMENTATION
TRAILER
wtos
MS
4
SERVICE
PANEL
FIGURE 2 FIELD TEST SITE LAYOUT
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TABLE 1. TEST DESCRIPTION AND MILESTONES
Area
6 ft x 12 ft
Depth
7 ft
Volume
500 cu ft
Weight
60,000 lb
Time to Reach 100°C
2 days
Time to Reach 150°-160°C
8 days
Grab Samples Taken
9th day
Total Test Duration
12.5 days
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100°C in two days. By the eighth day of heating the temperature had reached the
treatment range of 150°-160°C. On the ninth day two grab samples of soil were
obtained from the heated zone. These samples indicated that 89-90% of the
semi-volatile aliphatics and 97-99% of the semi-volatile aromatlcs had been removed by
the ninth day, at which time the soil had been maintained in the treatment temperature
range for about 30 hrs.
The test was shut down 12.5 days after start of the heating cycle. Soil sampling
was begun after allowing the soil to cool for 17 days, at which time the average tem-
perature was 50°-60°C.
SOIL SAMPLING
The performance of the in situ decontamination process was determined by the
analysis of numerous soil samples taken before and after the test. The samples were
obtained according to a sampling grid Illustrated 1n Figure 3 for the pre-test soil
samples. From each hole samples were obtained from the depth Interval of 6-12 1n.,
30-42 in. and 60-72 in. There were 4 different types of sample holes, with 8 holes in
each type. Thus, 96 different soil samples were obtained. These samples were compos-
ited together to yield 12 samples. All samples of the same type and from the same
depth interval were composited in a cold room maintained at 4°C. Each composite was
extracted and analyzed in duplicate. The samples were analyzed for moisture and 104°C
volatiles by observing the weight loss in an oven; volatile aromatics and aliphatics
were determined by purge and trap of the sample extract, followed by GC/MS analysis of
desorbed vapors from the purge and trap device. Semi-volatile aliphatics, aromatics
and hexadecane were determined by steam distillation and liquid-liquid extraction of
the soil followed by GC/HS analysis of the extract. The volatile analysis covered
those materials boiling up to 120°C, while the semi-volatile analysis covered mate-
rials boiling in the range of 70° to 300°C.
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The post-test soil sampling plan was similar to the pre-test plan and these sam-
ples were also analyzed by the methods summarized above. Approximately 84 different
post-test samples were obtained which were also reduced to 12 composite samples prior
to analysis.
The soil analysis was used to determine the average decontamination efficiency in
the heated zone, and 1n each of the three depth intervals.
RESULTS
The removal of volatile contaminants as determined by the purge and trap proce-
dure is illustrated in Figure 4. On the average, 99.3* and 99.6% of the volatile
aliphatics and aromatics, respectively were removed from the heated zone. The removal
as a function of depth was fairly uniform, ranging from 98.2 to 99.8% for aliphatics,
and 99.2 to 99.9% for the aromatics.
The removal of semi-volatile contaminants is illustrated in Figure 5. For these
contaminants, 94.Z% of the aliphatics and 99.IX of the aromatics were removed from the
treated volume. Significant removal of hexadecane, which bolls at 287°C, was also
observed as shown by the data in Figure 5. This has occurred due to the steam sweep
established by boiling water and also due to the long residence time provided at 150°-
160°C.
In the depth Interval of 6-12 1n., the removal has been generally less than in
the deeper zones of the test volume. This has occurred due to two reasons. First,
the near surface zones were cooler, due to heat loss, than the Interior of the heated
zone. Second, the vapor collection fans were switched off 24 hrs after the heating
was stopped. Vapors rising to the surface from the deeper zones probably condensed in
the near surface cool zones. The fans were switched off to minimize intrusion of
contaminants from the surrounding cool zones, but at the same time, this action prob-
ably increased the recondensation of the high boilers in the 6-12 in. depth interval.
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60-72 in.
30-42 in.
t
g- 6-12 in.
o
6-72 in.
97.0
97.5
99.2
2
98.22
99.3
99.9
21
99.8
99.6
99.7
99.6
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98.0 98.5
Percent Removal
99.0
99.5
Y////X Aliphatics
| | Aromatics
H
100.0
FIGURE 4 REMOVAL OF VOLATILE CONTAMINANTS
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60 72 in.
30-42 in.
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6-12 in.
6 72 in.
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67.47
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SI
99.9
93.55
98.5
99.6
91.44
88.1
82.88
75
80 85
Percent Removal
90
Aliphatics
I I Hexadecane
k\\\\l Aromalics
97.6
98.09
SI
99.11
94.31
95
100
FIGURE 5 REMOVAL OF SEMI-VOLATILE CONTAMINANTS
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The outward migration of contaminants from the heated zone was assessed by ana-
lyzing soils in a zone 12 to 24 in. outside the heated area. Soil samples were taken
in this zone as a function of depth before and after the test. In Figure 3, these
locations are labeled "type 4." It was originally intended to dig a 1-ft wide, 6-ft
deep trench all around the heated zone and backfill with clean sand. Due to extensive
side wall cave-in, the trench was not made, but before- and after-test soil samples
were obtained from the area marked "Trench" 1n Figures 2 and 3. Figure 6 shows that
both volatile aromatlcs and aliphatlcs were removed from the "trench" area. These
data Illustrate that there was no net migration of contaminants in the lateral direc-
tion.
To determine whether the contaminants had migrated downwards, some soil samples
were obtained from the 84-96 in. depth intervals. Figure 7 shows the before and after
concentration of volatile aliphatlcs and aromatlcs from the "extra deep" locations.
These data show that a net reduction of contaminant concentration had occurred 1n the
soil underlaying the heated volume.
Inward migration of contaminants from the surrounding cool soil was measured by
injecting a tracer in the soil. Approximately 5 ml of liquid Halon* 2402 was injected
4 ft outside electrode Row 1, at a depth of 6 ft. The raw gases leaving the heated
zone were sampled and analyzed for Halon® 2402 by injection on a GC equipped with an
electron capture detector. Halon* 2402 is dibromotetrafluoroethane and it provides a
very high response on the ECD detector even when present at low concentrations. It is
estimated that the ECD response is of the order of 108 area units per microgram of
Halon* 2402.
Approximately 107 minutes after its injection, the Halon* tracer was detected in
the raw gases leaving the heated zone. This result proved that soil fluids were
migrating from the surrounding cool zone into the heated test volume, and not vice
versa.
-259-
-------
I
ro
cr>
0
1
60-72 in.
.£ 30 42 in.
"Si
£
4)
¦5 6-12 in.
a.
n
a
6-72 in.
29
85.5
22
78.95
76.3
2
78.76
2
74.54
70.6
76.83
-t-
I I
-I 1 1 1
1 1 1 1 1 1 1 1 1 1 u
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90
Percent Removal
Aliphatics
I I Aromatics
FIGURE 6 REMOVAL OF VOLATILES FROM THE "TRENCH" ZONE
-------
Concentration, ppm
IV///A Before
I I After
FIGURE 7 REMOVAL OF VOLATILE CONTAMINANTS IN REGIONS UNDERLAYING THE HEATED ZONE
-------
PROCESS COST EVALUATION
Preliminary cost studies have been performed (2) on the radio frequency heating
process. In these, the cost of in situ treatment of a contaminated site was developed
through a conceptual design of a treatment system. The design was used to estimate
the capital, and operating cost of the process. It was assumed that a contaminated
site will be cleaned-up by the successive treatment of modules, each of 9200 sq ft.
The treatment depth was assumed to be 8 ft. It was estimated that the treatment cost
varies between $1.5 to $2.9 per 100-lb of treated soil. The range is due to the
amount of native moisture present 1n the soil and the exact temperature of treatment.
The study assumed a moisture and treatment temperature range of 5 to 20%, and 100° to
250°C, respectively. The capital cost for a 1.0-MW RF treatment system was estimated
to be $1.6 million and 1t was estimated that such a system could treat 14 modules per
year.
Figure 8 1s a pie chart showing the distribution of the total treatment cost
among five different cost categories. This illustrates the costs for a case where the
soil was assumed to have a native moisture content of 12% and the final treatment was
assumed to be 170°C. Capital charges refer to the amortized share of the finance
charge and depreciation; fixed operating cost refers to those costs which are indepen-
dent of heat-up time, such as site preparation, mobilization, demobilization, permit-
ting, etc. The cost category of electrodes refers to the capital and replacement
charge for electrodes required for the module. The cost category of AC refers to the
cost of purchasing AC power for the operation of the RF power source. It includes
allowances for power source efficiency, transmission and thermal losses. The variable
operating cost category refers to all costs which are dependent on the length of the
heat-up time. These Include operating labor, supervisory and maintenance personnel,
materials and supplies for all operations, fringe benefits, etc.
-262-
-------
Total Cost
Per Module
Cost Component
Percent
$5830
3.1%
$30940
$4260
I
ro
CO
i
16.45%
$28104
22.65%
15%
$80526
3 Capital Charge
42.8%
Y////X Fixed Operating Cost
m| Electrodes
irrrm ac
kWVCI Variable Operating Cost
FIGURE 8 COMPONENTS OF TREATMENT COST FOR A TYPICAL FIRE TRAINING PIT
-------
In another study (7), the cost of RF treatment of a site was compared with the
cost of excavation and off-site incineration in an approved facility. It was estimated
the incineration process would be 2 to 4 times more expensive than the RF in situ
treatment process.
CONCLUSIONS
The results of the field test have proven the feasibility of the in situ soil
decontamination process under field conditions. The test results show that 99% of the
volatile aromatlcs and aliphatics can be removed by in situ heating for a period of 4
days 1n the temperature range of 150°-160°C.
It was also shown that 94.3% of the semi-volatile aliphatics and 99* of the semi-
volatile aromatics can be removed under similar conditions. Hexadecane was used as a
marker for high-boiling aliphatics. The results show that even at 150°-160°C, 83% of
the h1gh-bo1l1ng hexadecane can be removed. This has occurred due to the long resi-
dence time provided and due to the autogenous steam sweep established by the formation
of steam.
Through evaluation of soil samples obtained from the area surrounding the heated
test volume, it was shown that there was no net outward migration of the contaminants.
The Halon* tracer experiments demonstrated that soil liquids and gases were migrating
into the heated zone.
The results warrant that the process be optimized and scaled up for commercial
operation. Several areas have been identified which present optimization opportuni-
ties and challenges. These are: development of reusable vapor barriers, development
of Improved methods to connect the electrode array to the RF power source, selection
and design of Improved vapor treatment systems from several existing and available
technologies such as catalytic oxidation, incineration or flaring of HC vapors.
-264-
-------
ACKNOWLEDGMENT
The field test was funded by USAF, HQ Engineering and Services Center, Tyndall
Air Force Base, Florida. Some of the RF heating equipment used 1n this project was
developed and fabricated in a separate program sponsored by the Division of Advanced
Energy Projects of the Department of Energy. Laboratory development of the
decontamination process was funded jointly by HQ AFESC/ RDV, USAF, Tyndall AFB,
Florida; Hazardous Waste Engineering and Research Laboratory, USEPA, Cincinnati, Ohio;
and IIT Research Institute through a USEPA Cooperative Agreement.
REFERENCES
1. Krystansky, J. et al. RF Heating of Carbonaceous Deposits. DOE Report DOE/ER/
10181-1, I IT Research Institute, Chicago, IL, March 1982.
2. Dev, H. et al. Radio Frequency Enhanced Decontamination of Soils Contaminated
with Haloqenated Hydrocarbons. Final Report, IITRI Project No. C06600, USEPA
Cooperative Agreement CR 811529, Hazardous Waste Engineering Research Laboratory,
USEPA, Cincinnati, OH, June 1988.
3. Dev. H., Enk, J., Sresty, G. C., and Bridges, J. E. In Situ Decontamination by
Radio Frequency Heating—Field Test. Draft Final Report, IITRI Projects C06666,
C06676. USAF Contract No. F04701-86-C-0002, June 1988.
4. Dev, H., Enk, J., Bridges, J. E., and CondorelH, P. High Temperature Thermal
Treatment of Soils with Radio Frequency Heating. Final Report, IITRI Project
C06600, EPA Grant No. CR-811529-01-0, IIT Research Institute, Chicago, IL, June
1986.
5. Dev, H., Condorelli, P., Bridges, J. E., Rogers, C., Downey, D. In Situ Radio
Frequency Heating Process in Solving Hazardous Waste Problems. Learning from
Dloxlns, ed. Jurgen H. Exner, pp. 332-339, ACS Symposium Series 338, Washington,
DC, 1987.
6. Sresty, G. C., Dev, H. Snow, R. H., Bridges. J. E. Recovery of Bitumen from Tar
Sand Deposits Using the IITRI RF Process, SPE Reservoir Engineering. 1, (1), pp.
85-94, January 1986.
7. Dev. H., Bridges, J. E., and Sresty, G. C. Decontamination of Hazardous Waste
Substances from Spills and Uncontrolled Waste Sites by Radio Frequency In Situ
Heating. EPA-600/D-84-077. USEPA, Cincinnati, OH, 1984, p. 34.
-265-
-------
TYPE OF TREATMENT:
General: Thermal
Specific: Rotary kiln 1nc1nerat1on/ind1rect
heating - pyrolysls
Manufacturer:
FORMER USE/PROBLEM: Former coke oven site
LOCATION/COUNTRY:
CONTAMINANT(S):
MEDIUM OF CONTAMINANT(S):
Unna-Boenen
Northrlne - Westphalia
Federal Republic of Germany
Aromatic hydrocarbons
Tars
Acid resins
STATUS AS A NATO/CCMS
STUDY PROJECT:
Proposed: 3/87
Accepted: 3/87
Interim Report(s): 11/88
Expected Completion Date:
Final Presentation: 11/89
-267-
-------
_Tdysv/a, RUHRKOHLE
UMWELTTECHN1K
SECOND INTERNATIONAL MEETING
OF THE NATO/CCNS PILOT STUDY
DEMONSTRATION OF REMEDIAL ACTION TECHNOLOGIES
FOR CONTAMINATED LAND AND GROUNDWATER
7-11 NOVEMBER 1988
National Institute of Public Health
and Environmental Protection (RIVM)
Bilthoven, The Netherlands
Rotary Kiln Incineration,
Indirect heating/pyrolysis of
RAG, Bergbau AG Uestfalen,
FRG - Unna Boenen
(Interim Report)
Joachim Ronge
RUHRKOHLE UMWELTTECHNIK GMBH
-268-
-------
tRUHRKOHLE
UMWELTTECHNIK
CONTENT
1. The prevailing situation
1.1 Direct thermal treatment
1.2 Indirect thermal treatment
2. R + D Project "Indirect thermal treatment"
2.1 Site description
2.2 Technology used
2.3 First test results
2.4 Further technical improvements
3. Further procedures / Outlook
-269-
-------
J5)M/£> RUHRKOHLE
UMWELTTECHNIK
1. The Prevailing Situation
1.1 Direct thermal treatment
In November 1987 I have presented our project "Direct
II
thermal treatment of soil . Since then the project goes
through the approval procedure under the German Act on
Waste Management.
The procedure we have opted for allows for a capacity of 30 - 50 t
per hour and is based - especially as the hot parts are
concerned - on Ecotechniek's technical concept. Within
the context of this meeting you will have an occasion
to visit the installation of Ecotechniek.
1.2 Indirect thermal treatment
Today I will speak about the research and development
project "Thermal treatment of soil".
-270-
-------
ruhrkohle
UMWELTTECHNIK
2. Research Project "Indirect Thermal Treatment"
2.1 Site Description
The premises were examined for soil contaminations. The
overall surface is 25 ha (250,000 square meters) and
comprised three different sectors.
- Coal area
- Coking plant site
- Storage site
A grid of boreholes was produced to depths between 1 and 4 m
On analysis of the drill cores, it turned out that the
contaminations were severest:
- At the location of the former coking plant,
- At the location of the former acid resin storage
near the gasometers, and
- At a location where a coking plant had existed
prior to the construction of the colliery.
At the above locations we found a vast variety of
contaminations by typically coking-plant-induced substances.
The severest contamination was found at the sites of the
former coking plant and acid resin storage. These sites
were contaminated with aromatic hydrocarbons, tars, and
acid resins. The soil in these contaminated areas was
covered with materials when the site was abandoned. As
a rule, the contaminations did not penetrate into the
underlying soil formations.
Approval pursuant to the Federal Act on Air Pollution
Control and Noise Abatement has been granted for this
test plant.
-271-
-------
ln)/A\//-v nunn^nLC
^TfvSrV^ UMWELTTECHNIK
2.2 Description of the Technology
Besides the method of open-cycle direct thermal soil treatment,
RAG has pursued another research project based on a closed-
cycle indirect thermal treatment (pyrolysis). A pilot test
study on this thermal treatment system was conducted and
results have been encouraging. A full-scale test plant is
designed for a throughput of 7 tons/hour of soil with a
voaltile matter content of 5 percent by weight and a moisture
content of up to about 20 percent per weight. The concept
includes the following process steps: the soil is, after
mechanical pretreatment (1), fed to a rotary kiln of 25 m
lenght (2, 3). The volatile matter is released from the
soil at temperatures of up to 600° C. The heat requirement is
met by heating the oven shell using gas (6). Upon discharge
from the kiln, the treated soil is water-cooled and may
then be brought back to the original site (4). The released
gases are subjected to post-combustion at 1,300° C maximum (5)
and then to quenching (8) . Some solid additive is dose-fed
to the gas flow for binding the pollutants. The waste gas is
finally scrubbed (9) and the clean gas released through the
stack (10).
The overall plant design is such that transport and reuse
at different sites is possible.
For the first time the technique is applied on the premises
of a former colliery and coking plant (Koenigsborn 3/4) in
Boenen.
2.3 First experimental results
After a construction period of 8 months the installation
took up first test runs in'May 1988 (technical run without
soil decontamination) .
In July, 1988, we started a second phase in the form of test
runs with soil feeding. First operational results on the base
of approx. 3,000 t of decontaminated soil figure in the
annex . -272-
-------
ln>)/A\/^> nunnr\wni_c
UMWELTTECHNIK
Let me show you on the overhead protector a few detailed
results concerning the purification effect as measured on
the base of soil analyses before and after the treatment.
2.4 Further technical improvements
During the first few weeks of operation the pyrolysis
plant it became clear that the soil decontamination took
place without problems, especially so for grain sizes from
0 - 50 mm.
However, the initial project to cool all soil discharged
after the purification process by means of a screw proved to
be unrealistic. Large size lumps were not cooled sufficiently
by this method. This led to an overheating of the dis-
charging screw with subsequent obstructions. These last
few days we have modified the discharging system which
has thrown us back in our project schedule by about three
months.
3. Further procedure / Outlook
Our plannig is based on operating the kiln 24 hours a day
starting 1989. This operation around the clock would enable
us to decontaminate about 100,000 t of soil between 1989 and
1991. So far we have participated in this project with an
investment of approx. 9 Mio DM.
-273-
-------
® © (D
KurmW
vero'-ennungs- 0
njit '
i
ro
i
t-»e)K)as= Erdgas
^fet\
Was'if
(D ®
-------
fj v" • ••
^ \*-
% iHCJ
WMMk
SK^W^
1, |:' ' v ^' • '- -"v :?' '-'
MiR—it f" ¦ r U^V---- r;-: '¦" :
# £
n --^v
* / . *
r ,* ' * '.
A -T,v-
. _ ..r. r... •,
"v ••••", .V'V : ¦ •¦ '¦ '¦¦¦¦¦'¦ t K^,
¦ imm: K -^ -
. --.id ^"¦:/:7.3
: - : -:- ' •//¦> ••• • ¦ '^- <• .:.'
-------
1899
- 1901
Abteufen der SchSchte 3 und 1
1901
Bau der ersten Kokerei (110 Ofen Je 6 t)
1905
- 1907
Bau der NebengeMlnnungsanlagen fOr Teer
und Amon laker zeugung
1921
- 1927
Bau elner neuen Kokerei (Batterie 1 - 3);
Je 40 Regeneratlvofen Je 11 t)
1925
Bau der NebengeMlnnungsanlagen rait Benzolfabrlk
1929
- 1931
Abbruch der alten Kokerei, ,
Aufbau eines Gassamelbehalters (50.000 nr)
1941
- 1915
Bau der Batter len 1-5
Durch Luftangrlff Beschadigung der Batter len 2 + 5
1949
- 1951
Reparatur der Krlegsschaden
15.11.1977
Stillegung der Kokerei Konigsborn 3/4
15.03.1981
Stlllegung der leche KOnlgsborn 3/4
BERGOAU AG
WESTFALEN
Daten
zur geschichHichen Entwicklung der Schachtanlage
und Kokerei Konigsborn
T 3
Januar 1987
-------
.^Sond ierungs-Nr.
Schadstofr—
6
24
59
63
130
Phenol
0,0
0.0
0,0
0.0
0,0
Kresole
0,0
0.0
0,0
Q.O
0,0
Xylenole
0.0
0.0
0,0
0,0 .
0,0
Naphtalin
24.4
5.4
130,0
246,0
0,0
Fluoren
0.1
8.9
35,7
92,9
0.0
Phenanthren
0.2
19,2
36,6
119,0
0.0
. Anthracen
r
0.0
5.6
4,4
25,3
0.0
Fluoranthen
0.3
15,0
6,3
92,5
0.1
Pyren
0.4
16,7
13,4
74,5
0.2
Benz (a) anthracen
0.2
2.7
1.6
12,7
0,0
Chrysen
0.0
1.6
1.8
8,1
0.0
Benz (e) pyren
0.0
1,1
1.5
4,3
0.1
Benz (b) fluoranthen
0,0
1.3
1,8
6.4
0,0
Benz (k)fluoranthen
0.0
0,6
M
3.0
0,0
Benz (a) pyren
0.0
0,9
1,3
5.2
0,0
Dibenz (ah) anthracen
0.0
0,3
0,2
1.3
0,1
Benzo (ghl) perylen
0.0
0.4
0,6
2.4
0,0
Indeno (123.cd) pyren
0.0
0.3
0.8
2.3
0.0
Sunme 1 : Naphtalln-Anthracen
24.7
39,1
206.7
483.2
0,0
Sumne 2 : Fluoranthen-Chrysen
0.9
36,0
23.1
187.8
0,3
Sunn 3 : Benzo (e) pyren-Indeno
(123,cd)pyren
0.0
4,9
7.2
24.9
0,2
Subbb 4 : Alle Verbindungen
25.6
80,0
237.0
695.9
0,5
BERQBAU AO
WE9TFALEN
Analyseergebnisse der Bodenuntersuchungen
T 3
Januar 1968
-277-
-------
V
, / GrOBe der verunreiniqten Fiachen bzw. Boderanasssn
fi 71
¦
^ t -v"/ ¦
N /¦/ ¦
/¦*
-278-
Fiache
Fiache
Ttefe
Menge
m'
m
m'
A
22 140
2.5
55 350
• B
2 340
2.0
4 680
c
12 276
2.0
24 552
0
1 797
1.0
1 787
E
15 697
1,5
23 546
F
942
3.5
3 297
G
936
2,0
1 872
H
1 498
2.0
2 996
Summen:
57 616
—
118 080
-------
Elroesetzter Boden
- Menge
- Wassergehalt
- ^sche
- FlUchtige
- Kohlenstoff
- KOrnung
7.000 kg/h
21 %
69 %
5%
5%
0 - 50 mm
Helzmedlum
Erdgas
Drehrohrofen
Abmessung, Durchmesser
LSnge
warmeleistung
Entgasungstenperatur
Ausmauerung
max,
max.
2,2 m
21,0 m
3,0 Gcal/h
6C0 °C
keine
Nachbrermkammer
Bremraumtenp. max.
warmeleistung max.
Rauchgasmenge
Lufterhltzer
Abgasmenge aus Schwelerbehelzurg max.
Abgastenperatur Eintr./Austr.
Verbrennungsluftmenge max.
Lufttemperatur Elntr./Austr.
1.200 °C
2,5 Gcal/h
6.020 n^/h
7.800 n^/h
700/300 °C
4.400 n^/h
10/350 °C
RauchgaskUhler
Rauchgasmenge Elntr./Austr.
Rauchgastenperatur Elntr./Austr.
10.020/14.550 nfl/h
900/200 °C
Rauchgasrelnlgung
Rauchgasmenge Elntr.
Rauchgastemperatur Elntr.
14.550 n^/h
190 °C
={^nsS
BERGBAU AG
WESTFALEN
Pyrolyseverfahren der Ruhrkohle
- Auslegungsdaten -
T 3
Januar 1988
-279-
-------
FUr luftverunreinigende Stoffe wurden folgende Grenzwerte, be-
zogen auf trockenes.Abgas im Normzustand bei 11 % 02-Gehalt
festgesetzt:
- Staub 30 mg/m1
- Staubfflrmige anorganische
Stoffe nach Nr. 3.1.4 TA-Luft:
• Klasse I 0,2 mg/m3
• Klasse II 1 mg/m3
• Klasse III 5 mg/m3
-CO: 100 mg/m3
- S02: 100 mg/m3
- organische Stoffe (angegeben
a Is Gesamt-C): 20 mg/m1
- gasffirmige anorganische Chlor-
verbindungen (angegeben als HCL): 50 mg/m3
- gasffirmige anorganische Fluor-
verbindungen (angegeben als HF): 2 mg/m3
AuBerdem wurden Auflagen bezuglich der Emissionsgrade fur S02,
HCL und HF erteilt. Die Massenkonzentration von Staub, CO, SOg,
02, HCL und HF sind kontinuierlich zu ermltteln. Oer Betrieb
der An1age ist aus Larmschutzgrunden zunSchst nur an Werkta-
gen in der Zeit von 6.00 bis 22.00 Uhr gestattet.
-280-
-------
"Lc i L1 «uU:ii UuUousuuierung"
Indikativo Richtwartei A - ReCaranskategoria
D - Kat«9orl« filr niihoro Untcr-
cuchung
C - Kategoria fUr Canlcrungaun-
tersuchung
Komponcnt/Niveau
A
0
C
A
D
c
Z Mctalla
Cr
100
250
OOO
20
50
200
Co
20
50
300
20
50
200
Ni
50
100
500
20
50
200
Cu
50
100
500
20
50
200
In
200
500
3000
50
200
800
As
20
30
50
10
30
100
HO
10
40
200
5
20
100
Cd
1
5
20
1
2,
5 10
Sn
20 •
50
300
10
30
150
Do
200
400
2000
50
100
500
l»«J
0,5
2
10
0,2
0,
5 2
. Pb
SO
150
600.
20
SO
200
XI Anornonlscho Varunrclnlnu
nqcn
Nll4 (wio N)
m
m
-
200
1000
3000
F (gooamt)
200
400
2000
300
1200
4000
CN(g«aamt~lr«l) 1
10
100
5
30
100
CH
s
50
500
10
50
200
(gosajnt-komplax)
3 (gaaamt)
2
20
200
10
100
300
Or (govamt)
20
50
300
100
500
2000
P04(wio P)
m
m
m
50
200
700
ZXZ Aromatischa Varblndunqcn
Qensol
0,01
0,5
5
0,2
1
5
Ctylbonzol
0,05
5
50
0,5
20
60
Toluol
0,05
3
30
0,5
15
50
Xylolo
0,05
S
50
0,5
20
60
Phanole
0,02
1
10
0,5
IS
SO
Aroroaton
0.1
70
1 ,
30
100
¦HBi(sLLLL13HHBI
.
i ]
Zv Polycycliccha Kohlcnwaancratoffa 1
Naphtalin
0,1
5
50
0,2
7
30
Anthraccn
0,1
10
100
0,1
2
10
Phcnantron
0,1
10s
.00
0,1
2
10
Fluoranthan
0,1
10
100
0,02
1.
5-
Pyren
0,1
10
100
0,02
1
5
3,4 - Denzpyron 0,05
1
10
0,01
0,
2 1
1
20
200
0,2
'
10
40-
Kohlanwaaaor-
atof f«(gcaamt)
(Pck'a)
-281-
-------
ro
00
ro
1
Bezeichnung
Drehrohro
fenwandt
emperat
ur (je)
350
450
550
650
Summe 1
14,1
1.5
0,1
<0,1
Summe 2
19,8
2,0
0,3
<0,1
Summe 3
18,7
4,5
0,2
<0,1
Summe 4
52,6
8,0
0,6
<0,1
Abreinigungsgrad (%)
72
96
99,7
>99,9
Schadstoffkonzentration in mg/kg im gereinigten Bo-
den als Funktion der Drehrohrofenwandtemperatur
-------
I !
I ! E i n
! !
Aus < 10mm
Aus > 10mm
!Naphthalin
!2-Methyl-Naphthalin
!1-Methyl-Naphthalin
!Fluoren
!Phenanthren
!Anthracen
783.00
125.00
273.00
382.00
1040.00
225.00
1 .00
0.20
0.B0
0.30
1.80
0.40
1. 10
0.20
0.70 !
0.40
1 .90
0.10
!Fluoranthen
!Pyren
!Benzlalanthracen
!Chrysen
720.00
497.00
291.00
141.00
1 .40
0.90
1 .50
1.00
1 .80
1.80
1.20 !
1.10!
!Benzf elpyren
!Benzolb]fluoranthen
1 Benzolk1fluoranthen
Benz[alpyren
Dibenzlah]anthracen
Benzotghilperylen
Indenof1.2.3.cdJpyren!
179.00
209.00
I0B.00
182.00
2B.B0
83. B0
79. 10
2.30
2.30
1.40
2.80
0.70
2.50
2.20
1.40 1
1.60 !
1.00 !
1.30 !
0.30 !
1.00 !
0.80 1
Summe 1
Summe 2
Summe 3
Summe 4
! 2828.00
! 1G49.00
! 865.30
! 5342«30
4. 30
4.80
14.20
23.30
4.40 j
5.90 !
7.40 !
17.70 !
-------
Ein
flus < 10mm
flus > 10mm
Naphthalin
2-Methyl-Naphthalin
1-Methyl-Naphthalin
Fluoren
Phenanthren
Anthracen
50. 30
15.50
43. 30
47. 10
138.00
28.20
0.30
0.40
0.20
0.20
1. 10
0.20
< 0. 10
< 0.10
< 0.10
< 0. 10
0.30
< 0. 10
! *"
Pluoranthen
Pyren
Benz t alanthracen
Chrysen
89.00
79.90
41.00
21.80
1 . 10
1.00
0.70
0.40
0.40
0.30
0.30
0.40
Benztelpyren
Benzotb]tlaoranthen
Benzolk1fluoranthen
Benz[alpyren
Dibenzfanlanthracen
Benz o[ghi 1perylen
Indenol1.2.3.cdlpyren
25.30
27. 10
17.90
2G.00
4.50
13.70
12.60
0.70
0.80
0.30
0.50
0. 10
0.40
0.30
< 0. 10
< 0. 10
< 0. 10
< 0. 10
< 0.10
< 0. 10
< 0. 10
Summe 1:
Summe 2:
Summe 3:
! Summe 4:
322.40 ! 2.40
231.70 ! 3.20
127.10 ! 3.10
681.20 ! 8.70
0.80
1.40
0.70 !
Z.90 »
-------
Ein
flus < 10P1M
flus > 10mm
Naphthalin
2-Methyl-Naphthalin
1-Methyl-Naphthalin
Fluoren
Phenanthren
Anthracen
221.40
10.90
18.80
28.80
79.10
17.B0
1.70
0.20
0.S0
0.50
2.30
0.40
0.50
0. 10
0. 10
0.40
0.60
0.10
Fluoranthen
Pyren
Benz [ >a] anthracen
Chrysen
G4.00
42.90
23.50
15.70
2. 10
1 .40
1.20
t. 50
!
0.50
0.40
0.20 !
0.40 !
}
Benz [elpyren
Benzolblfluoranthen
Benzot k]fluoranthen
Benzt a)pyren
Dibenz t ah]anthracen
Benzot ghi]perylen
IndenoC1.2.3.cdlpyren
!
14.70
17.90
7.20
13.90
2.80
7.80
8. 10
1.40 !
1.80 !
0.50 I
0.70 !<
0.30 K
0.90 !<
0.70 !<
j
5.70 I
6.20 !
6. 30 !
18.20 !
1
0.30 f
0.40 !
0,20 I
0.10
0.10
0. 10
0. 10
Sumroe 1:
Sunme 2:
Sumne 3:
Sunine 4:
376.60
146.10
72.40
595.10
1.80
1.50
1,30
4.60
-------
time
projekt
microbiological
treatment
1984
4
"585
1986
1987
1
4
1
1
.from 1.9.1984 tt>31.12.1988
¦i
exploration and
laboratory trial*
1w
zzzzz
1989
1990
4
1991
ITS
4
aaseaament and evaluation
of reclamation possibilities
«
from 1.1.1986 to 30.6.1991
thermal
treatment
schedule
-------
TYPE OF TREATMENT:
General: Thermal
Specific: Electric Infrared Incineration
Manufacturer:
FORMER USE/PROBLEM: Former oil refiner
LOCATION/COUNTRY: Peak 011
Tampa, Florida (Hillsborough County)
United States
CONTAMINANT(S): Polychlorlnated blphenyls
Lead
MEDIUM OF CONTAMINANT(S):
STATUS AS A NATO/CCMS
STUDY PROJECT:
Proposed: 3/87
Accepted: 3/87
Interim Report(s): 11/87
Expected Completion Date:
Final Presentation: 11/88
-287-
-------
Paper Not Received by
Time of Printing
-288-
-------
TYPE OF TREATMENT:
General: Thermal
Specific: Off-s1te soil roasting
Manufacturer:
FORMER USE/PROBLEM: Former electro-chemical plant site
LOCATION/COUNTRY: Asahl Electrochemical Co.
Arakawa-Ku
Tokyo, Japan
CONTAMINANT(S): Mercury
MEDIUM OF CONTAMINANT(S): Soil
STATUS AS A NATO/CCMS
STUDY PROJECT:
Proposed: 3/87
Accepted: 3/87
Interim Report(s): 11/87
Expected Completion Date:
Final Presentation: 11/88
-289-
-------
Thermal Treatment of Contaminated Soil with Mercury
Takashi Ikeguchi
The Institute of Public Health
Tokyo 108 Japan
and
Sukehiro Gotoh
National Institute for Environmental Study
Tsukuba 305 Japan
SUMMARY
The site of former electro-chemical industry in residential area
of Tokyo was found to be highly contaminated with mercury and lead
when the industry stopped its operation and dismantled facilities in
order to move the factory to the suburb and redevelop the site in
accordance with the urban planning of Tokyo Metropolitan Government.
The mercury contamination was mostly limited within surface soil with
average concentration of 3.68 % ( max. 15.6 %). About 56,000 mJ
soils with mercury level of above 2 mg/kg were considered to be
processed before redevelopment of the site. Underground
containment with and/or without stabilization using with Na£S for
slightly contaminated soil and thermal treatment ( roasting ) for
heavily contaminated soil were taken for the remedial technologies of
the site. About 840 nr ( ca.1260 tons ) heavily contaminated soils
with mercury were railed to off-site mercury roasting plant to
process and recover mercury. Total cost of soil roasting including
pakaging and transportation was about $374/ton soil.
1. INTRODUCTION
A. Site Description
The problem site, a former electro-chemical industry site
was situated in dense residential area on the bank of the Sumida
River in Arakawa Ward, northeast part of Tokyo Metropolitan Area
where many small industries and residential premises have been
coexited (see Figure 1 ). The soils in the site were alluvium and
hence soft with a few organic material and composed of mainly silty
sand. N value of soil strata between D m and -21 m ranged from 0 to
4 and cohesive strength was 2-3 tons/m . Hydraulic conductivity was
around 10"^ cm/sec in silty sand and lO'^-lO"® cm/sec in silt
-290-
-------
; JAPAN
ARAKAWA WARD
Figure'1. Location Map of the Former Asahi Electro-chemical
Co., Ltd. Site
-291-
-------
a
ro
KO
ro
i
Figure 2. Soil Texture and Hydrogeology of the Site
-------
( see Figure 2 ). Groundwater level was high (i.e. 0.2-0.8 m below
surface) and groundwater flow in horizontal direction could not be
recognized.
B. Site History
The industry, Asahi Electro-chemical Co., Ltd. began its
operation at this site in 1917 to produce primarily sodium hydroxide
and breaching powder as a leading industry in Japan at that time.
Using hydrogen and chlorine, by-products of sodium hydroxide, they
also produced soap, margarine, hydrogen chloride, and chlorinated
organic compounds as well as another industrial materials.
In 1955, the company developed mercury-electrolysis process
to obtain high quality sodium hydroxide to meet requirements of
chemical textile industry which had developed rapidly after World War
Two in Japan. By the time when closed system was introduced into
mercury-electrolysis process in 1966, mercury had spilled out of
plant in the form of gas, wastewater and stains on various materials.
As a result, the site of 20 ha was widely contaminated with mercury
and lead.
In the early 1970's, Tokyo Metropolitan Government decided
to remove heavy chemical industry located in residential area to
industrial area or another prefecture. Asahi Electro-chemical Co.,
Ltd. was included in this project. After removing, the site was
planned to be used for college, pubilic park, municipal wastewater
treatment plant, and community complex. The plant was closed in
March 1979.
During dismantling the factory equipments in 1978, highly
contaminated soils with mercury of max. 15.6 % ( 3.68 7. mean ) were
detected under electroysis vessel. These soils with a volume of 840
mJ ( ca. 1,260 tons ) were excavated and packed into about 6,000
drums and stored on site. Several alternatives were considered to
treat these highly contaminated soil and finally these were railed to
off-site mercury roasting plant at Hokkaido to recover mercury in
1979 and 1980.
C. Initial Sampling and Analysis Results
In 1977 the company analysed mercury and lead level of soil
core samples and groundwater in the site. Results of initial
analysis are shown in Figure 3 and Table 1. Among 980 soil samples
at 188 points, maximum mercury concentration was 1,250 mg Hg/kg soil,
while 79 samples showed above 5 mg Hg/kg soil. Form of mercury was
mostly sulphide . A 97 % of groundwater sample showed the
concentration of below 0.005 mg/1. Only top soils (i.e. 50 cm below
surface) were severely contaminated and groundwater contamination
outside the site was not recognized. Maximum lead concentration of
-293-
-------
ro
10
-p*
i
°o ^
o rP
o^o
o ~
Qlo.1 Electrolysis
Vessel
CP u
o
LEGEND
above 100 mg/kg
25-50 mg/kg
O O
50-100 mg/kg 10-25 m9/k9
Figure 3. Mercury Dlstribuslon 1n the Site
-------
Table 1. Initial Sampling Results of Soil and Groundwater
(a) Soil
Hg Concentration ( mg/kg )
Depth ( m ) <5 5-25 25-100 100-500 500-1,000 >1,000 No. of Sample
0 109 48 25 4 1 1 188
0.5 132 40 11 5 - - 188
1 172 12 2 2 - 188
2 94 2 2 98
3 84 2 - - 86
4 85 1 86
5 84 2 86
7-15 60 - - 60
No. of
Sample 820 107 40 11 1 1 980
( % ) (83.7) (10.9) (4.1) (1.1) (0.1) (0.1) (100)
(b) Groundwater
Hg Concentration ( mg/1 )
Depth ( m ) <0.005 >0.005 No. of Sample
0 179 9 188
0.5 179 9 188
1 181 7 188
2 97 1 98
3 85 1 86
4 85 1 86
5 85 1 86
7-15 60 - 60
No. of Sample 951 29 981
( % ) (97.0) (3.0) (100)
-295-
-------
soil was 2,610 tag Pb/kg soil. No further information on lead
contaminaton was available. Mercury in highly contaminated soil
which were detected under the two electrolysis vessel during
dismantling factory was metal mercury. Mean concentration of mercury
in these soils were 3.68 % and mostly distributed between 1 and 7 %
as shown in Figure 4.
D. Technology Selection
There was no statutory criteria for clean-up decision of
mercury contaminated soil at that time. Therefore Tokyo Metropolitan
Government sampled soils at 71 non-contaminated area through Tokyo
and analysed mercury to show that most of the data distributed
between 0.02 and 2 mg Hg/kg soil. Hence they took 2 mg Hg/kg soil as
a maximum background level of non-contaminated area and critera for
remedial action.
Underground containment with or without
stabilization/solidification has been considered so often as a basic
treatment method for contaminated soil in Japan. However, it was
impossible to keep the level of mercury in solution of highly
contaminated soil under the certain level even if solidified with
NaoS and FeC^. Moreover recovering mercury from these soils were
judged to be economically feasible and preferable from the view point
of resource conservation. Fot these reasons, remedial technologies
were selected according as the level of contamination as follows:
(1)Thermal treatment ( i.e. roasting ) for highly
contaminated soil with above 10 mg Hg/kg soil.
(2) Underground containment after immobilization for highly
contaninatead soil with above 10 mg Hg/kg soil.
(3) Underground containment without any pre-treatment for
moderately contaminated soil with 2-10 mg Hg/kg soil.
2. THERMAL TREATMENT TECHNOLOGY
Initially, Ashahi Electro-chemical Co., Ltd. planned to
construct on-site rotary kiln with a total throughput of 0.3 t/day to
roast contaminated soil using light oil as a fuel. Due to the
strong opposition of nearby residents and immature technology to
control gaseous mercury under the level of regulation, they had to
withdraw this plan and decided to transport contaminated soils to
mercury recovery plant in mountainous site of Hokkaido, about 1,000
km north of Tokyo. This plant was owned by mercury refining company
, Nomura Kosan Co. and was used for treatment of mercury bearing
waste to recover mercury at that time.
-296-
-------
u
«
9
Z
E
m
1/1
80
70
60
50
40
30
20
10
x 3.68 X + o x + 2o X + 3o
n= 300
x° 3.687.
o= 2.377.
Si
''"Vn-MI"3;0- 4.0-5.0 6.0-7.0 8.0-9.0 10.0<
1.0-2.0 3.0-4.0 5.0-6.0 7.0-8.0 9.0-10.0
Mercury Concentration ( Z )
Figure 4. Mercury Distribution in Highly Contaminated Soil
-297-
-------
This plant is equipped with vertical multistage roasting
furnace ( called as Herreshoff Furnace ) with an annual gross
teatment capacity of 3,600 tons. The plant is primarily composed of
roaster, condenser to recover mercury and flue gas cleaning devices.
Schematic flow diagram of this plant is shown in Figure 5.
Mercury-contained waste or soil is roasted at temperature
of 600-800 C using heavy oil. Volatiled mercury in flue gas
condensed on the inner wall of condenser subsequent to dust removal
equipment. Crude mercury is recovered from soot at constant
intervals and refined into commercial grade groducts with a purity of
99.99 % or more either by thw wet or the vaccume distilling. Trace
amount of mercury and acid gas components in flue gas are removed by
adsorption and neutralization. Slag from roasting furnance are
disposed of at on-site secure landfill and sludge from flue gas
treatment processes, dust collected by cyclone, residue from mercury
recovery are returned into roaster.
Recently this plant has been partly expanded to recover
mercury and other metals from used dry cell generated from individual
home.
3. DEMONSTRATION RESULTS
About 6,000 drums packed with highly contaminated soil were
transporated everyday except Sunday during March and July in 1980.
Cost of soil roasting was 65,000 yen/ton ( $300/ton ), and
transportation cost including package was 16,000 yen/ton ( $74/ton ).
Another mercury bearing waste were processed simultaneously at this
plant, hence technical data of soil roasting were not available
separately.
About 54,500 m^ soils contaminated with mercury of above 2
mgHg/kg soil were contained in on-site underground pit after
immobilization by Na£S for the soils with mercury level of above 10
mg Hg/kg soil. Excavation and immobilization followed by
underground containment were conducted from December 1983 to August
1984. To minimize environmental pollution during clean-up action,
air, dust, effluent, noise, and vibration were monitored around the
site and if any environmental deterioration was recognized, clean-up
had to be stopped or modified. Groundwater and rainfall inside
site were treated in the manner described in Figure 6. Groundwater
has been monitored at 4 monitoring wells of 20 m depth just outside
the site and no groundwater pollution has been reported so far.
-298-
-------
Contaminated Soil
Gas Absorber
Condenser To Atmosphere
II n T
Oemlster
Coal Feeder
cS^crrb
Herreshoff Furnace _
Slag
To Furnace
To water treatment
To Furnace
Soot
Underground
storage
Mercury
recovery
J— Residue
Mercury ^
To Furnace
Figure 5. Mercury Roasting Facility
-------
co
o
0
1
HC1 NazS FeS04
~ ~ ~
Receiving Tank
T
iii». « 11
9=
9=
Chelete Resin
Coagulation Sedimentation Tank 1
500 a3 j Filter
4 2 »3
JT
y
9
ITK
X
n
To River
Holding Tank Holding Tank Holding Tank
IS nr
10 mJ
10 nr
Coagulation Sedimentation Tank 2
500 m3
Figure 6. On-site Wastewater Treatment Facility
-------
4. CONCLUSION
Soil pollution in Japan was focused on the agriculture
field so far, however with urban redevelopment at former industry
site or national institution, soil pollution at these site has been
reported recently. In Tokyo, for example, several soil
contaminations have been identified at these sites including the case
of this paper. Major pollutants are heavy metals such as Hg, Pb,
Cd and restoration has been completed at all cases identified.
In the light of these facts, Environment Agency has been
conducting preliminary study of soil contamination resulted from
human activities at residential area and clean-up criteria of these
soils as well as clean-up technologies. Such criteria for soil
clean-up has been set up at some local government already.
Remedial technologies used so far are disposal at secure
landfill site or underground containment with or without
immobilization in principle. These technologies are, however not
detoxification method but mere isolation which renders future
potential hazard and therefore development of both on-site and off-
site detoxification technology of contaminated soil are required now.
Roasting of contaminated soil and mercury recovery of this
paper are the only case of detoxification that has been ever tried in
Japan. This example was off-site thermal treatment and
economically feasible because the mercury level in soil was extremely
high, as high as mercury ores. On-site roasting, however is
technically and possible as the company originally planned, provided
that nearby residents accept such facility.
ACKNOWLEDGMENT
Authors thank the Department of Environment Control, Tokyo
Metropolitan Government and Arakawa Ward Office for offering
informations.
REFERENCES
(1) Asahi Electro-chemical Co., Inc., Clean-up Plan for Contaminated
Soil of Former Industrial Site ( in Japanese ), October 1983.
(2) Hazama-gumi Co., Inc., Completion of Site Clean-up of Asahi
Electro-chemical Industry ( in Japanese ), March 1985.
(3) Nissaku Co., Inc., Research on Gas Generation at Restored Site
of Asahi Electro-chemical Industry ( in Japanese ), February 1985.
(4) Clean Japan Center, Mercury and Other Metals from Used Dry
Battery Cells - Recycling Demonstration Plant -, February 1987.
-301-
-------
TYPE OF TREATMENT:
General: Soil Treatment by Extraction
Specific: Vibration
Manufacturer: Harbauer
FORMER USE/PROBLEM: Former used oil recovery facility
(leaking tanks & pipes) P1ntsch-ol
LOCATION/COUNTRY: Berlin P1ntsch-ol
Federal Republic of Germany
CONTAMINANT(S):
MEDIUM OF CONTAMINANT(S):
Mineral oils
Chlorinated hydrocarbons
Polychlorlnated b1phenyls
Polycycllc hydrocarbons
Phenols
PCBs
STATUS AS A NATO/CCMS
STUDY PROJECT:
Proposed: 3/87
Accepted: 3/87
Interim Report(s): 11/87
Expected Completion Date:
Final Presentation: 11/88
-303-
-------
EXPERIENCE GAINED WITH A SOIL-DECONTAMINATION SYSTEM IN BERLIN
H.-D. Sonnen, S. Klingebiel
1. Summary
What 1s being presented is an extractive soil-decontamination system de-
veloped in Berlin, the HARBAUER PB 2, which has been working on the con-
taminated grounds of Pintsch-01 GmbH (in liquidation) since the summer of
1987 and has already cleaned more than 11,000 tons of contaminated soil
at various locations. The experience and knowledge gained with the opera-
tion of this system are described, the state of the art explained and fu-
ture perspectives outlined.
2. Introduction
Between 1925 and 1984 used oil was processed on the grounds of the
Pitsch-Ql GmbH, now in liquidation. A distillation facility and CP facil-
ity, amongst others, were useed for this purpose. Some of the production
residue leaked into the soil. Leaky tanks, production breakdowns and
careless work led to considerable contamination of buildings, soil and
ground water (Woltmann, 1985).
3. Location
The building of Pitsch-01 GmbH, now in liquidation, is located in a typi-
cal Berlin industrial area in the south of the city, in the district of
Neukolln. It is approx. 16,000 sq.m. in size. The soil consists of filled
and faulted layers of soil that contained sandy, clayish silts (drift
clay) to a depth of about 6 m followed by fine- to medium-grained sand
down to a depth of 12.0 m. Between 12.0 and 14.8 m there are very sandy,
gravelly and clayish silts (drift marl). Underlying this drift marl are
medium-grained and coarse sands with gravelly supplements. These very
pervious sands are the gound-water carrier proper. Layers of soil and the
ground water are thoroughly contaminated with mineral oils, phenols, CHC,
PCBs and PAHs
Table 1 provides a survey of the values determined at the time the
clean-up began.
Since 1924 Pintsch-01 Berlin GmbH had been collecting and processing used
oil from all over Berlin on the aforementioned property. The management
of the company allowed all the residue and waste products resulting from
the processing of the used oil leak to away in unsealed pits in the
southern part of the premises. Since used oil containing PCBs was also
treated during the reraffination process, PCBs made their way into the
production cycle, and thus into the soil as well. -Today's contamination
-304-
-------
of the soil, ground water and buildings was caused by this type of waste
disposal, by leaks in tanks and storage receptacles as well as by several
flrp? in the production buildings.
In March of 1982 the Senator for Urban Development and Environmental Pro-
tection commissioned a report to determine the soil and ground-water con-
tamination on the company's premises. The report was submitted in March
1983.
From this report it can be seen that 12,000 sq.m., i.e. some 75 % of the
property, are badly contaminated with mineral-oil products, chlorinated
hydrocarbons. Oil in phase was discovered on the ground water at a depth
of approx. 8.5 m under the ground over an area of 6,000 sq.m. As later
measurements showed, the oil floating on the ground water had local lay-
ers up to 3 m thick and was contaminated with biphenyls (PCB), polycyclic
aromatic hydrocarbons (PAH), chlorinated hydrocarbons CHC) as well as
phenols. Moreover, polychlorinated dibenzodioxins and dibenzofuranes were
detected at several places.
Contaminant Ground water Soil
mg/1 mg/kg
Non-polar aliphates (oils) 1400 37,843
Non-polar aromates 5,620
Misc. aromates
Benzene 133
Phenols 226 80
PCB
Clophen A 60 270
CHC
Oichloromethane 40.5
1.1.1 trichloroethylene 7.2 1,370
Trichloroethane 4.3 210
Tetrachloroethylene 22.8 5,209
Inorganic compounds
Cyanides 0.135 0.5
Sulphides - 58.5
Lead 0.44 14,418.6
Cadmium 0.0325 0.229
Chromium 0.022 70.48
Table 1: Main groups of pollutants on the Pintsch grounds (Jan. 1986)
-305-
-------
4. General Description of the Decontamination Technology
TK? crlgir.s* claan-up concept was limited to decontamination of the
ground water and directly related measures, in keeping with the legal
latitude. The buildings were to be demolished only to the extent neces-
sary to sink wells with which to pump the ground water.
A total of nine wells were planned, of which wells Br 1, Br 4 and Br 7
are in the area of former building 6. This building, which housed the
distilling furnaces, therefore had to be torn down. Since the masonry of
the building and, especially, the plaster were contaminated with highly
toxic substances, the building was surrounded with a protective hall be-
fore its demolition to prevent hazardous dust from escaping Into the sur-
rounding area. After all the production Installations and the building
had been torn down the protective hall was used to accommodate the soil
decontamination system and related research equipment. A biological in-
situ decontamination of the soil was not possible due to the heterogenous
subterranean conditions and the sometimes unknown chemical compounds. The
use of thermal methods was ruled out because they were not adequately de-
veloped and because of the permit procedures to be expected. Thus, the
use of an extractive soil-washing process based on the HARBAUER PB 1 sys-
tem was decided on.
5. The HARBAUER Soil Decontamination System
For the simultaneous cleaning of contaminated ground water and soil as
well as the contaminated soil from other locations in Berlin (utilization
of the system's capacity) the HARBAUER Engineering Office for Environ-
mental Technology, Berlin has developed a system with which it 1s possi-
ble to clean soil with a grain size of 15 |jm to 15 mm so that the soil
can be refilled again and the ground and process water can be fed to the
drainage ditch with drinking-water quality.
At the centre of the HARBAUER solution 1s the already tested HARBAUER PB
2 soil-washing system with which contaminated soil can be treated and
cleaned by washing and/or extraction with chemicals, depending on the
type and quantity of the pollution and structure of the initial material
(grain-size distribution).
The efficency with which harmful substances are separated from the soil
particles is largely determined by the introduction of energy. In the
case of the HARBAUER process, which was described by SONNEN and ORTWEIN
(1986), mechanical kinetic and vibrational energy is Introduced with the
help of mixing, stirring, vibrating and hydrocyclone equipment.
The introduction of energy neutralizes the various bonding forces between
the harmful substances and the soil particle and is supported by the ex-
tractive effect of the washing or extraction agent. The energy density
required depends mainly on the type of contaminated material, less on the
harmful substance.
Thus, gravelly soil requires the introduction of only a small amount of
energy to wash the harmful substances off the surface of the material. In
the case of very silty soil with a high percentage of clay, loam or marl
-306-
-------
as well as fine building rubbish (e.g. contaminated plaster) the amount
of energy introduced must be increased to 1 kU/t.
In the last analysis, however, it is the individual combination of energy
and extraction agents that results in the cleaning success aimed for. In
the selection of the extraction agent, however, there are ecological and
economic restrictions, for the agent used must be either absolutely harm-
less and biologically degradable or completely regeneratable so that the
cleaning of the process water, which is obligatory with washing or ex-
tractive processes, is technically and economicaly feasible.
Therefore, efforts are always made to work with clean water or aqueous
solutions as long as the chemical and physical properties of the contam-
inants permit.
In Individual cases it may be necessary to use organic solvents, complex-
ing agents or other reactive substances. For reasons of emission laws and
accident prevention, however, these systems belong more 1n the category
of chemical facilities than cleaning systems for contaminated soil.
However, in the case of extractive methods a system solution does not in-
volve only the decontamination system proper, and the related treatment
of the exhaust process air, but must also deal with the question of how
to treat the substances left over.
With the HARBAUER process all soil particles greater than or equal to 15
pm in size are cleaned 1n such a way that they can be used again as
building material (screening bottom) at the original location. Fine sub-
stances less than 15 pm in size are to be found 1n various types of wash-
ing and rinsing water. This water undergoes preliminary dessication in
settling facilities, is separated from remaining sludge on a belt screen
and cleaned to nearly drinking-water quality during the treatment of the
process water.
The remaining sludge is still polluted to a low to medium extent and re-
quires further treatment (thermal treatment, disposal, compaction, pyrol-
ysis). This waste product is still being disposed of in the GDR for the
time being.
Further degradation products are concentrated mixtures of solvents and
separated oil fractions, which can be disposed of by burning at high tem-
peratures. A mobile plasma facility is presently being tested in a joint
project by WESTINGHOUSE and KEMMER/HARBAUER to determine whether it is
basically suited for such products.
This leaves, finally, only the substances adsorbed by the activated char-
coal of the process-water conditioning system. These substances are de-
composed during the thermal/chemical regeneration of the activated char-
coal at the manufacturer's and are turned Into ash or acids.
The complete process flow chart for the soil-washing system is shown in
Fig. 1.
6. Results
After the soil-washing system had been put to several months of success-
ful use treating the contaminated soil of the Pintsch grounds, cleaning
tests were begun in October 1987 with contaminated soil excavated from
two Berlin gas-works locations in MaHendorf and Wilmersdorf.
The following cleariing results with the material from Mariendorf are ex-
emplary of the two soils.
The grain-size distribution (Fig. 2) shows that the soil is extremely
fine-grained with 37 % of the particles being less than 100 pm in size.
-307-
-------
I
u>
o
00
Fig. 1: Process flow chart for the "HARBAUER PB 2" soi1-decontamination system
-------
Fig. 2: Grain-size distribution of the soil at the "Berl1n-Mar1endorf gas works"
-------
Such soil cannot be processed by conventional soil-washing systems since,
on the one hand, the high percentage of extremely fine grains can no
longer be effectively separated from the harmful substance and, on the
other, they lead to complete s1lting-up of the system.
In comparison, during some eight weeks of tests with this material it was
seen that the system is capable of effectively cleaning soil with a prob-
lematically high content of silt and clay without significant modifica-
tions or conversions.
The results of the analysis (Table 2} substantiate the high cleaning ef-
ficiency in relation to all the relevant parameters of the harmful sub-
stances. The pollution remaining in the decontaminated soil was nearly
always lower than reference category A of the guideline for soil decon-
tamination, but in general clearly beneath the B values.
The cut of the system, as related to the grain size to be processed, was
determined to be approx. 15 pm within the scope of a balance sheet drawn
up for the complete system.
On the average, the amount of residue to be disposed of during the test
period lasting more than 6 months amounted to approximately 2 % of the
initial material.
In general these statements also apply to the soil from Wilmersdorf. But
since the balance sheet for the system was not yet finished for this ma-
terial by the copy deadline, reference is made in this connexion to the
authors' paper.
Petroleum ether extract:
(index for mineral-oil
contents)
PAH's
Phenol index:
Total cyanide:
(as per DIN 38 405)
Initial
values
476,000 pg/kg
752,000 pg/kg
60,500 pg/kg
5,300 pg/kg
Remaining
pollution
67,000 pg^tg
2,000 pg/kg
n.n
59 pg/kg
Washing
success {*)
86
99.7
appr. 100
98.9
Table 2: Cleaning efficiency, soil from gas works in Berlin-Mariendorf
7. Conclusions
With the system solution presented it 1s possible to clean contaminated
soil with a complex matrix of harmful substances and problematical grain
sizes by means of large-scale technology and then refill the soil. The
entire system can be considered by now to have undergone large-scale
testing, and the suitability of the system components for a process-en-
gineering solution to the problem has been demonstrated. The process
costs less than 200 DM/t on the average. The present potential for devel-
opment of the system presented is, for one, a reduction of the cut to ar-
eas less than 10 pm in size and thus to further minimization of the resi-
-310-
-------
due to be disposed of and, for another, further optimization of the sep-
aration of harmful substances from the soil. These two areas are the fo-
cal points of the R&D work being done by HARBAUER at the present and,
among others, the subject of a research project sponsored by the Federal
Ministry of Research and Technology and the Senator for Science and Re-
search.
8. Literatur
Ortwein, H.
Sonnen, H.D.
Woltmann, M
Bodenreinigung auf dem GelSnde der Pintsch-01 GmbH 1.L.,
Vorstellung einer Bodenwaschanlage, Abfallwirtschaft 18
(1987), p. 117-126
Die Sanierung des Pintsch-Gelandes, "Sanierung kontaminien-
ter Standorte 1985", FGU-Seminar, Wiesbaden 1985
-311-
-------
TYPE OF TREATMENT:
General:
Specific:
Researcher/Manufacturer:
FORMER USE/PROBLEM:
LOCATION/COUNTRY:
CONTAMINANT(S):
MEDIUM OF CONTAMINATION:
STATUS AS A NATO/CCMS
STUDY PROJECT:
Proposed:
Accepted:
Interim Report(s):
Expected Completion Date:
Final Presentation:
Soil Treatment by Extraction
High pressure soil washing 1n-s1tu
(Soil-crete)
GKN Keller GmbH
Former disinfectant manufacturer
Goldbeck-Haus
Hamburg - VHnterhude
Federal Republic of Germany
Phenols
Soil
4/88
4/88
11/88
11/89
-313-
-------
NATO/CCHS PILOT STUDY
International fleeting
7. - 11. Noveaber 1988
Bilthoven, Netherlands
High Pressure Soil Washing
and Soil Treatment by Extraction
- INTERIM REPORT -
by order of
Dmweltbehorde Hamburg
— Amt fur Altlastensanierung —
Arbeitsgemeinsctaaft Bodensanierung
GKN Keller GmbH, Spezialtiefbau
S + I Schlammentwasserung GmbH + Co. KG
WUE Umwelt Engineering GmbH
November 1988
-314-
-------
1• Indroduction
1.1 Site description
1.1.1 Geographic location and setting
1.1.2 Soil classification and geology
1.2 Site History
1.2.1 Responsible parties
1.2.2 Dates of contamination
2. Technology
2.1 High pressure Soil Washing (in situ)
2.2 Soil treatment by extraction (on site)
3. Testis and Results
4. Conclusions
4.1 Applicability and limitations
4.2 Prognosis
5. Contacts £or more information
Enclosure
Diagram 1 Plan view of the area
2 Subsoil conditions
3 Contamination within the subsoil
4 Spread of contamination
5 Technique of treatment and jet cutting methods
6 Location of test area
7 Parameter of execution
8 Results of washing
9 Results of treatment
-315-
-------
1.
Introduction
1.1 Site description
1.1.1 Geographic location and setting
The site is located in the city of Hamburg in the
district of Winterhude. The site, with an area of about
5000 m2, is bordered by the canal "Goldbek-Kanal" on the
south side; and three old factory buildings are now
built on it (diagram 1). One of the former three fac-
tory buildings is now used as a community centre (build-
ing at the side of the Goldbek-Kanal) and the other two
are rented to various commerical enterprises.
Only the ground-floor-level of the east-building-wing
is not in use (at the moment).
The east-wing is now also to be used as the part of the
community centre, so it is planned to reconstruct and
renovate this part of the building.
1.1.2 Soil classification and geology
The area is nearly horizontal and varies between Nor-
mal-zero (NN) + 4.2 m and NN + 5.0 m.
The subsoil conditions can be described as follows:
Beginning with an approximately 4.0 m thick layer of
filling material, normally sand, a thin "upper peat"
layer follows with a thickness of 0.5 to 1.0 m. This
peat changes into a sand layer. Underneath, this is
followed by the second lower peat, mud or lime-mud layer
with a thickness of between 0 and 8.0 m. The ground is
made up of sand and glacial-drift/boulder clay and
marlaceous soil (diagram 2).
-316-
-------
The sandy layers are filled with ground water. The
ground water level was measured between NN + 2.8 and
about NN + 3.0 m, that means 1.4 m to 2.0 below ground
level.
The ground water level is in contact with the Goldbek-
Kanal. The boulder clay acts almost as a seal and sepa-
rates the upper ground water from the second ground
water horizon, which begins about 50 m below ground
level. The subsoil conditions and a description of the
soilproperties are given in diagram 2.
1.2 Site History
1.2.1 Responsible parties
On the site between 1889 and 1963 a chemical factory
manufactured disinfectants.
Because of the previous chemical production on the area
and the improper handling of chemical materials over a
longer production period phenol, a chemical substance
which was used to produce disinfectans, penetrated the
subsoil and the ground water and caused contamination.
Today the factory area is owned by the city of Hamburg.
1.2.2 Dates of contamination
The contamination was measured as the concentration of
phenols (mg/kg = ppm), mainly phenol and the three
isomere of kresol, within ground water or soil (dry
mass).
With 32 borehole to a final-depth between 2 and 10 m and
6 borehole as gauges (depth between 9 and 62 m), the
contamination was recorded.
-317-
-------
The recorded phenol concentration within the different
boreholes is shown in diagram 3.
The spread of contamination at different levels under
the ground surface is shown in diagram 4. The contami-
nation is concentrated between two buildings and under
the buildings. Because of the contamination under the
buildings it was also necessary to find methods of
treatment for the contaminated soils without changing
the ground conditions for the foundations.
1.3 Technology Selection
Because of the high phenol contamination and the consi-
derable odour of the chemical substance, on-site techni-
ques using an open pit are not practicable and workable.
Biological treatment, which were carried out as a trial,
proved unsuccessful, because of the very different soil
conditions (sand peat, mud with different organic con-
tents and thickness) and rapid changes in contamina-
tion .
For these reasons it was necessary to create in-situ/
on-site methods of treatment also for the soil
underneath the buildings.
The joint venture "Arbeitsgemeinschaft Bodensanierung"
has developed a process of treatment for these contami-
nated soils with the following qualities:
- no direct contact with contaminated material
- no odour during decontamination process
whole process self-contained
- no pit or opening to treat contaminated material or
earth works
-318-
-------
- treatment of soil possible also under buildings
- no ground water lowering, because peat and mud layers
achieve settlements for the buildings
- no transport of contaminated material necessary
All these advantages open a wide field of application
for this technique of treatment.
2. Technology
2.1 High Pressure soil washing (in situ)
After drilling down a borehole to the final depth using
normal drilling technique, a jet cutting technique is
used to erode and wash the surrounding soil. To cut,
water with a pressure of about 300 - 600 bar is used.
The water is pressed through a nozzle and reach a speed
of about 200 m/sec. With this water-jet-stream the
surrounding soil is eroded, mixed with the water while
the jet-cutting monitor rotates and is pulled up at a
constant rate.
The mixture of soil and water follows up the borehole
to the top level. The volume of the treated soil as a
column depends on the withdrawal rate and rotation.
The contaminated mixture is leaded into a completely
self-contained system.
After the treatment (see chapter 2.2) the soil is sepa-
rated into two classes. Class 1 material is brought back
into the jet-cut columns.
Therefore the class 1 material as cleaned soil is put
into a suspension of filling aggregates. After a column
has been jet-cut, this mixture of soil and suspension is
placed into the column using the tremie method.
-319-
-------
After separation the class 2 material will be placed
into a filter press. The water is pressed out and a
nearly dry soil with a high unit weight is then left.
The water which was pressed out of the soil is without
of contamination and can be given to further use.
2.2 Soil treatment by extraction (on site)
This suspension of contaminated soil and water produced
by jet-cutting, completely self contained, is treated
and cleaned of phenolic contamination by oxidation.
To achieve the decontamination by oxidation chemical
substances were mixed into the suspension according to
the degree of concentration. The quantity and sequence
depends also on the degree of contamination.
Also the air coming up the borehole is absorbed and
cleaned so that the surroundings are not subjected to
any fumes or smells.
With this technique the contaminated mixture of soil
and water within the column is displaced by treated
soil within a suspension with a higher weight. The
contaminated soil/water which is forced out, is also
treated (diagram 5).
Underneath the foundations and buildings a variation of
processing is necessary. At the same time as the soil is
eroded by jet-cutting, a fill with suspension and har-
dening aggregate is mixed with the water soil compo-
nents below. This process is characteristic of the
SOILCRETE-method.
-320-
-------
Tests and Results
On the areas of the "Goldbek-Haus" between 31.3.88 and
8.9.88 five tests were executed with different execution
parameters.
The location of the test field is shown on diagram 6.
The boreholes beneath this test area and the beginning
concentration of contamination are shown on diagram 3.
With the technique described already five columns have
been executed.
The following
execution for
table (diagram 7)
the different test
shows the
columns.
paramters of
Column
Execution
technique
Date of
Execution
A
SOILCRETE
6. 9.88
B
1. washing,
eroding
31. 8.88
C
2. Treatment
5. 9.88
D
7. 9.88
E
3. Filling
8. 9.88
Diagram 7 Parameters of execution
Column A was executed as a normal SOILCRETE-column with
a stabilisation at the same time, while for the columns
B to E erosion and washing was executed as a frist step
and afterwards the remaining material in the colums was
a displaced with a clean mixture.
The results of the erosion and washing process for co-
lumn A to E and the quality control during the process-
ing is shown on diagram 8.
-321-
-------
RESULTS of HIGH PRESSURE SOU. HASHING
Test: Column
A
B
C
D
E
DRILLING
Water
m3
1.1
0,8
1,1
0,6
0,5
1. 2.
HP SOIL/
Water (D)
m3
8,8
3,8
2,0 2,0
3,6
WASHING
Water (M)
m3
3,9
1,7
0,9 0,9
1,7
SOILCRETE
Water
m3
2,9 +
4,2
Suspension
" Water
" Cement
m3
m3
to
3,75
2,4
3,8
W/Z =
0,67
FILLING
Consumption
m3
4
8,5
5,0
6,0
Water
m3
1,6
3,3
2,0
2,4
Sand
to
5,5
11,0
6,4
7,7
Lime St.
to
1,0
1,8
1,1
-
Fly Ash
to
-
-
-
1,3
Cement
to
0,25
1,0
0,6
0,7
Ca.Bent.
to
—
0,4
0,25
0,3
VOLUME for
TREATMENT
m3
12,0
17.5
15.O
11.4
11.8
Diaqram 8 Results of Washing
-------
The result of the following treatment of the contamina-
ted soil is shown on diagram 9. These results show that
an about 98 percent removal of the phenol-contamination
was possible, both in the water as well as in the soil.
The time of reaction and decontamination depends on the
degree of contamination the pH-value the contents of
organic-material and the water-contents. With lower wa-
ter-contents longer time for decontamination was needed.
After the treatment the separation of the decontamina-
ted material follows.
Soil class 1 material as the coarse grain component
show a higher concentration of phenol as the finer one.
This fact is a result of the technique of separation.
For this trial, the separation was done only mechani-
cally, so that also a higher contents organic coarse
material was found in the class 1 material. For this
reason during this trail it was not possible to coarse
material back into the columns.
During the entire treatment the material was completely
self-contained so that no extra measure for emmision
and protections of workers and maschinery were
necessary.
These described results of the trial are temporary.
The results of core-drillings and tests of core
material after finishing the works on site remains to
be seen to give final results of the whole works.
-323-
-------
Column
mass for mass for Separation phenol concentration Time for
production treatment m3 input output reaction
m3 m3 mg/1 mg/1 min
B
Drilling
Washing
Filling
17, 5
0,8
12,7
4,0
24
Coarse grain
Fine grain
Filtration
0,6
2,4
21,0
760
20
32 mg/kg
24 mg/kg
5 mg/1
120
C
Drilling
Washing
Filling
25,0
1,1
8!5 + 10
37
Coarse grain
Fine grain
Filtration
0,4
3,6
33,0
1560
20
144 mg/kg
60 mg/kg
9,8 mg/1
180
D
Drilling
Washing
Filling
11.4
0,6
5,8
5,0
22, 2
Coarse grain
Fine grain
Filtration
0,2
3,0
19,0
2035
20
53 mg/kg
35 mg/kg
19,8 mg/1
35
E
Drilling
Washing
Filling
11,8
0,5
5,3
6,0
24
Coarse grain
Fine grain
Filtration
0,4
3,6
20,0
1585
20
412 mg/kg
150 mg/kg
12,4 mg/1
120
A
Drilling
SOILCRETE
Water
Suspension
12,0
1,1
2,9 + 4,2
3,75
24
Coarse grain
Fine grain
Filtration
1.0
3,6
15,4
633
20
125 mg/kg
159 mg/kg
9,7 mg/1
150
Diagram 9 Results of Treatment
-------
4. Conclusions
4.1 Applicability and limitations
This method of high pressure soil washing and treatment
by extraction can be used to treat any soil which can be
cut with high pressure, that means nearly all types of
soil and also soil with a high clay contents or high
contents of organic material. The method of treatment
depends on the kind of contamination and has to be
checked for each different application.
4.2 Prognosis
With the technique of water-jet-cutting, chemical treat-
ment and separation of contaminated soil and ground
water, a lot of contamination sites can be purified.
The advantages of this technique and process are:
- no pits have to be build to treat contaminated
soils,
- no additional earth work is required,
no ground water-lowering is necessary,
no smell because all air is absorbed,
- no changes of process underneath buildings,
- process can be used for any form of contamination
with a uniform chemical treatment,
- no contaminated soil or water has to leave the site,
- all steps of the process are self-contained, no
contamination can escape into the atmosphere,
- stabisisation underneath foundation without changes
of technique,
- the amount of soil material which has to removed is
minimised.
-325-
-------
With these advantages, a wide field of application is
developed. The technique is applicable for a wide range
of contaminated soil and allows treatment also on sites
with buildings.
5. Contacts for more Information
5.1 Client
Freie und Hansestadt Hamburg, Umweltbehorde
- Amt fur Altlastensanierung -
Hermannstrafle 40
D-2000 Hamburg 1
Herr Wolf
Herr Schnittker
Herr Marg
Herr Dr. Zarth
D -
040/34913- 445
-3473
- 760
-3476
5.2 Contractor
GKN Keller GmbH, Spezialtiefbau
Hardenstr. 51 Kaiserleistr. 44
D-2000 Hamburg 28 D-6050 Offenbach 12
D - 040/78 17 51 D - 069/8051-213
Herr Pielsticker Herr Dr. Sondermann
S + I Schlammentwasserungs GmbH + Co. KG
Kruppstr. 9
, D-4047 Dormagen-Hackenbroich
D - 02106/651-18
Herr Dorner
WUE Umwelt Engineering GmbH
Stresemannstr. 80
D-4100 Duisburg 1
D - 0203/3004-171
Herr Dr. Decker
-326-
-------
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Phenol-Concentration Hi thin the soil
Diagran 3: Subsoil conditions and contamination
-- - //-'Vi'-VV
'cxAz-vc /
|GKN KElLERj;
-------
Dlagraa 4: Spread of contaalnation
Phenol-Concentration mI thin the soil
0
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1. operation
boring down nonltor
to final depth
drilling-plpe
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so11/nater-11xture
-------
Diagraa 5b:Process of treatment
air
soil/water-mixture
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Plan View of
Test Area
0 A =Test Column
0BP -Gaugs BPI-0-
tj)-B = Bore Holes
BP HI
|GKH KELIER]
-------
TYPE OF TREATMENT:
General: Chemical
Specific: K-PEG Technology
Researcher/Manufacturer:
FORMER USE/PROBLEM: Chemical recycling facility and road
oil1ng
LOCATION/COUNTRY: Gary, Indiana and Wide Beach, New York
United States
CONTAMINANT(S): PCBs, chlorinated hydrocarbons
MEDIUM OF CONTAMINATION: Liquid; soils
STATUS AS A NATO/CCMS
STUDY PROJECT:
Proposed: 4/88
Accepted: 4/88
Interim Report(s): 11/88; 11/89
Expected Completion Date:
Final Presentation:
-335-
-------
CHEMICAL ON-SITE TREATMENT
UTILIZING KPEG PROCESS
PRESENTED TO
NATO/CCMS Pilot Study on Remedial Action Technologies
for Contaminated Land and Groundwater
BY
U.S. Environmental Protection Agency
November 1988
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KPEG = POTASSIUM
POLYETHYLENE GLYCOL
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ON-SITE CHEMICAL TREATMENT
KPEG: AN OVERVIEW
• PROVIDES COST EFFECTIVE ALTERNATIVE TO LANDFILLING
AND INCINERATION
• CAUSES A PERMANENT CHEMICAL CHANGE IN PCB
STRUCTURE
• AFFECTS ONLY ORGANIC MATERIALS, SUCH AS PCBs AND
DIOXIN
• OCCURS AT ROOM TEMPERATURE BUT MAY NEED TO BE
HEATED TO ENSURE REACTION
• PRODUCES NON-TOXIC, NON-MUTAGENIC, AND NON-
BIOACCUMULATIVE MATERIAL
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CHEMICAL REACTION
A DESCRIPTION
• CONTAMINATED SOIL MIXED WITH ALKALINE REAGENT
CONTAINING POTASSIUM HYDROXIDE (KOH)
• ALKALINE REAGENT & KOH MIXED IN POLYETHYLENE
GLYCOL (PEG) & DIMETHYL SULFOXIDE (DMSO)
• THE REAGENTS DECHLORINATE THE ARYL HALIDE TO FORM
A PEG ETHER
• PEG ETHER DEGRADES, FORMING A DECHLORINATED
SPECIES
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CHEMICAL REACTIONS
DURING THE KPEG PROCESS
ROH + KOH DMSO
~
ROK + HOH
Ck/WVCI
ROK + JOT To
ciAAAAci
DMSO
~
ycfoa +kcl
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RESIDUAL WASTE STREAM
GENERATED: KPEG PROCESS
• POLYETHYLENE GLYCOL
• CHLORINE COMPOUNDS
• WASH WATER
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PERSONNEL
SKILL LEVEL REQUIRED
ON-SITE ANALYTICAL LAB
- CHEMISTS
- LAB TECHNICIANS
- CHEMICAL PLANT OPERATORS
PROCESS/CHEMICAL ENGINEERS NOT REQUIRED ON-SITE
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WORKER HEALTH AND SAFETY
SITE SAFETY PLAN SHOULD ADDRESS WHEN LEVEL C*
PROTECTION IS REQUIRED
SITE SPECIFIC CIRCUMSTANCES MAY REQUIRE DERMAL
AND RESPIRATORY PROTECTION
DECONTAMINATION ACTIVITIES ARE REQUIRED
AIR MONITORING MUST BE CONDUCTED TO ENSURE
PROTECTION OF PERSONNEL AND THE GENERAL PUBLIC
TYVEK CLOTHING AND RESPIRATOR
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QA/QC PLAN - GENERAL COMPONENTS
O PROJECT DESCRIPTION/IDENTIFICATION OF PERSONNEL &
AREAS OF RESPONSIBILITY
O SAMPLE COLLECTION & TRACKING
O ANALYTICAL PROCEDURES
O QC CHECKS/DATA VALIDATION AND REPORTING
O PROJECT DOCUMENTATION
O PROCEDURES TO ASSESS PRECISION & ACCURACY
O CORRECTIVE ACTION
* MORE DETAIL IS GENERALLY INCLUDED IN QA/QC PLANS
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ON-SITE OPERATIONS
CONSTRUCTION PHASE
TREATMENT PHASE
SITE SAFETY
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KPEG DEVELOPERS*
DEVELOPERS
COMPOUNDS
TESTED
FORM OF
K
POLYMERS
SOLVENTS
OTHER
REAGENTS
EFFECTS
OF HATER
FRANKLIN RESEARCH
CENTER
PCBs,
PESTICIDES,
TRICHLORO-
BENZENE
METALLIC
K
PEG400
NONE
°2
INHIBITS
GENERAL ELECTRIC CO.
PCBs,
CHLORO-
BENZENES
BITOL
KOH
PEG350
PEG600
MECAR-
MeOH
HEPTANE
TOLUENE
NONE
INHIBITS
GALSON RESEARCH
CORPORATION
1,2,3,4-
TCDD
KOH
PEG400
MEE
DMSO
NONE
NONE
UNIVERSTIY OF TURIN
(ITALY)
2,3,7,8-
TCDD
k2o3
PEG6000
NONE
•
Na2<)2
—
PEG=Polyethylene glycol * innovative Technology
MEE=2(2-methoxyethoxy) ethanol
DMSO=dimethyl sulfoxide
MEOH=methanol
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KPEG APPLICATION
CONSIDERATIONS
• DIFFERENCES IN THE WASTE MATRIX (SILTY/CLAY)* MAY
INFLUENCE THE EFFECTIVENESS OF KPEG ACTIVITIES
• DIFFERENCES IN SOIL CONSTITUENTS (E.G., HIGH
METALS) MAY IMPACT THE RESULTS OF KPEG
TREATMENT
• RESPONSIBILITIES** OF TREATMENT VENDORS AND ON-
SITE CONSTRUCTION CONTRACTORS SHOULD BE
DEFINED PRIOR TO INITIATING ON-SITE TREATMENT
ACTIVITIES
* E.G. CHLORINE MAY BIND MORE TIGHTLY WITH CLAYS THAN WITH SILTY SOILS
*» MAY INCLUDE MATERIALS HANDLING, QA/QC AND SAMPUNG AND ANALYSIS
ACTIVITIES
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KPEG APPLICATIONS
LIQUIDS/SLUDGES
SITE/DATE
WASTE TYPE
CONCEN.
before/ after
VOLUME
COST
Western Proce99ing
(Kent, WA)
8/86-9/86
dioxin
liquid/sludge
120 ppb/
<.3ppb
277,685 L
(75,050 gal.)
$650,000#
Montana Pole
(Butte, MT)
6/86
di'oxi'n/furana
liquid
147-83,923 ppb/
<1 ppb
37,000 L
(10,000 gal.)
$212,000
Signo Trading
(Mount Vemon, NY)
10/21/82
dioxin
liquid
135 ppb/
<1 ppb
55.5 L
(15 gal.)
$25,000
~PLUS 1 MILLION FOR OFF-SITE INCINERATION
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PROCESS DIAGRAM
DECONTAMINATING LIQUIDS
ICE WATER CONDENSOR
ICE
WATER
VENT
FIBERGLASS
INSULATION
DRUM
HEATERS
REAGENT/SLUDGE
MIXTURE
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KPEG APPLICATION
PCBs IN SOIL
WIDE BEACH
BRANT, NEW YORK
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WIDE BEACH
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SITE DESCRIPTION
•
LOCATION:
- SHORES OF LAKE ERIE; 30 Ml. (48 KM.) S. OF BUFFALO, NY
•
TOPOGRAPHY:
- GENERALLY FLAT
•
POPULATION:
- RESIDENTIAL COMMUNITY; 54 ACRES (22 HA.)
•
GEOLOGY/SOILS:
- DEPTH TO BEDROCK (SHALE) = 10-14 FT. (3 - 4 M.)
-- CLAY/SILTY CLAY
•
GROUNDWATER:
- 80% FLOWS TOWARD WETLANDS; 20% FLOWS TOWARD
LAKE ERIE
•
SURFACE WATER:
- MARSH LOCATED S. OF BEACH - DRAINAGE AREA
•
WEATHER:
- ANNUAL TEMP. = 48®F (9®C)/RAIN FALL = 34 IN. (86 CM.)
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AREA OF CONTAMINATION
AT WIDE BEACH
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SITE HISTORY
• APPROXIMATELY 30,000-40,000 GAL. (111,000-148,000 L.) OF
WASTE OIL USED FOR DUST CONTROL ON ROADS BETWEEN
1968-1978 BY WIDE BEACH HOMEOWNERS ASSOCIATION
• INSTALLATION OF SEWER LINE RESULTED IN EXCAVATING
HIGHLY CONTAMINATED SOILS FROM ROADWAYS - SURPLUS
SOIL USED AS FILL IN YARDS IN 1980
• 19 S5-GAL. (204 L.) DRUMS FOUND NEAR LOCAL WOODS IN
1981 - SAMPLING PROGRAM INITIATED
• SAMPLING INDICATED PCBs IN AIR, ROADWAY AND YARD
SOILS, VACUUM CLEANER DUST FROM HOMES AND WATER
SAMPLES FROM PRIVATE WATER SUPPLIES
• IMMEDIATE REMOVAL ACTIONS CONDUCTED IN 1985*
• PAVING ROADWAYS/DRAINAGE DITCHES, VACUUMING RUGS; INSTALLING WATER
FILTERS
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TOTAL AMOUNT OF SOIL
CONTAMINATION
- PCBs
CONCENTRATION
QUANTITY*
LOCATION
—
6,100 MT**
ROADWAYS
> 500 PPM
10,000 MT
DITCHES***
—
1,700 MT
DRIVEWAYS
—
3,600 MT
FRONTYARDS
—
100 MT
BACKYARDS
> 50 PPM
200 MT
WETLANDS
* APPROXIMATELY 18 INCHES (46 CM) IN DEPTH
** 1 MT = APPROXIMATELY 1 CUBIC YARD
*** CONCENTRATIONS RANGED FROM 91.9 PPM - 1026 PPM
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IMPACTS ON
GROUNDWATER AND SURFACE WATER
• GROUNDWATER
- PCBs WERE FOUND IN CONCENTRATIONS ABOVE NY
STATE STANDARD (1 PPB) IN 20 OF THE 138 SAMPLES
TAKEN (I.E., 14%)
• SURFACE WATER
- WETLANDS AND LAKE ERIE CONTAMINATED VIA STORM
WATER RUN OFF (NO SAMPLING DONE)
• TREATMENT TECHNOLOGY
- CARBON ADSORPTION UNDER CONSIDERATION
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TECHNOLOGY SELECTION
OPTIONS
COST
CONSIDERATIONS
ON-SITE CHEMICAL
TREATMENT*
(KPEG)
$9,400,000
COST EFFECTIVE
PERMANENT CHEMICAL TREATMENT
PRODUCES NON-TOXIC MATERIALS
IN-SITU BIOLOGICAL
TREATMENT
$840,000 -
$6,300,000
LONG TERM DISRUPTION -
UNSUITABLE FOR SITE CONDITIONS
IN-SITU CHEMICAL
TREATMENT
$13,500,000
CHANGES IN SOIL MOISTURE COULD
ADVERSELY AFFECT THE CHEMICAL
REACTION
IMMOBILIZATION
**
QUANTITIES OF ACTIVATED CARBON
REQUIRED IN AREAS WITH HIGH LEVELS
OF ORGANIC MATERIALS
(E.G., WETLANDS)
REMOVAL/DISPOSE
$62,000,000
HIGH COSTS
* PREFERRED TECHNOLOGY
** SUBSTANTIAL
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ON-SITE CHEMICAL TREATMENT
THE PROPOSED PROCESS
• SOIL WILL BE PLACED IN CONTINUOUS CHEMICAL
TREATMENT REACTOR (MIXER)
• IN THE MIXER, SOILS WILL BE COMBINED WITH
KOH/PEG/DMSO
• MIXTURE WILL BE PUMPED TO A ROTARY KILN AND HEATED
AT 158®F (70®C) FOR 2 HOURS
• AFTER REACTION, THE DECONTAMINATED SOILS WILL BE
SEPARATED FROM THE REAGENT BY SEDIMENTATION
• SOLIDS WILL THEN BE WASHED AND SEPARATED
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PROCESS DIAGRAM
SOIL DECONTAMINATION
SOILS AND
WASTES
WATER VAPOR
AND VOLATILES
MIX
REACT
REAGENT
WASTES TO TREATMENT
~
•| CONPENSOR |
MAKEUP WATER
RECYCLE WATER '
I
DECANT
FIRST
WASH
~
REAGENT
TO RECYCLE
T
WASH WATER
TO RECYCLE
SECOND
WASH
~
WASH WATER
TO RECYCLE
CLEAN
' SOIL
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STATUS OF KPEG ACTIVITIES
AT WIDE BEACH
PHASE DATE
PILOT SCALE 3/88 - 9/88
FULL SCALE * EARLY 1989
* PROPOSED DATE: IMPLEMENTING FULL-SCALE, ON-SITE
OPERATIONS IS CONTINGENT ON THE RESULTS OF THE PILOT
SCALE
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CONCLUSIONS
9 USING KPEG TREATMENT ON LIQUIDS CONTAMINATED BY
PCBs AND DIOXIN AT WESTERN PROCESSING, MONTANA
POLE AND SIGNO TRADING* SUCCESSFULLY REDUCED
CONCENTRATIONS TO BELOW 10 PPB
• APPLYING KPEG TO HIGHLY CONTAMINATED SOILS WILL BE
DEMONSTRATED AT WIDE BEACH
• ON-SITE DEMONSTRATIONS OF INNOVATIVE TECHNOLOGIES
ALLOW EPA TO IDENTIFY MORE COST EFFECTIVE AND
EFFICIENT REMEDIES
* CONCENTRATIONS WERE BELOW DETECTABLE LEVELS
-------
RESOURCES
FOR MORE INFORMATION, PLEASE CONTACT
DAVID LOPEZ OF THE U.S. ENVIRONMENTAL
PROTECTION AGENCY (EPA), EMERGENCY
RESPONSE DIVISION AT (202) 382-2471
OR WRITE:
DAVID LOPEZ
U.S. EPA, OS-210
EMERGENCY RESPONSE DIVISION
401 M STREET, SW
WASHINGTON, DC 20460
-------
APPENDIX A
NATO/CCMS Pilot Study
Demonstration of Remedial Action Technologies
for Contaminated Land and Groundwater
LIST OF PARTICIPANTS
Second International Meeting
Bilthoven
The Netherlands
7-11 November 1988
A-l
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PILOT STUDY PARTICIPANTS
CANADA
Richard Martel
Environment Quebec
3900 rue Marly, 5e Etage
B.P. 42
Ste-Foy, Quebec
Canada 61X 4E4
OFFICE TEL. 418-646-7688
HOME TEL... 418-688-0817
James W. Schmidt, P. Eng.
Head, Physical/Chemical Processes Section
Wastewater Technology Centre
Environment Canada
P.O. Box 5050
Burlington, Ontario
Canada L7R 4A6
OFFICE TEL. 416-336-4541
HOME TEL... 416-827-2139
TELEX 0618296
DENMARK
Kim Broholm
Department of Environmental Engineering
Technical University of Denmark
Building 115
2800 Lyngby
Denmark
OFFICE TEL. 02 88 42 00 ext. 5084
HOME TEL... 01 86 92 14
Dr. Steen Vedby
Ph.D. Geology
Technical University of Denmark
Department of Environmental Engineering
Building 115
2800 Lyngby
Denmark
OFFICE TEL. 02 884200
02 884444
HOME TEL... 02 872258
TELEX 37529 DTH-DIA
TRANSLATION:
National Environmental Protection Agency
FEDERAL REPUBLIC OF GERMANY
Gerd Kuhnel
Federal Minister for the Environment
Nature Conservation and Nuclear Safety
Division - WA II 4
Postfach 12 06 29
D-5300 Bonn 1
Federal Republic of Germany
OFFICE TEL. (0228)305-2581
HOME TEL... 02 255 63 14
A-2
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Ms. Margaret Nels
Friedrichsthaler Weg 28A
D-1000 Berlin 28
Federal Republic of Germany
OFFICE TEL. 030-404-1796
Dipl.-Kfm. Joachim Ronge
Ruhrkohle Umwelttechnik GmbH
Rellinghauser Str. 1
D-4300 Essen 1
Federal Republic of Germany
OFFICE TEL. 0201-177-25-65
HOME TEL... 0201-471-93-7
TELEX 857651
Dr. Wolfgang Sondermann, Dr.-Ing.
GKN Keller GmbH
Spezialtiefbau
Kaiserleistrasse 44
D-6050 Offenbach 12
Federal Republic of Germany
OFFICE TEL. 069-8051-213
HOME TEL... 060-7431-815
TELEX 4-152-616
Klaus Stief, Dipl.-Ing.
NATO/CCMS Pilot Study Co-Director
Umweltbundesamt
Bismarckplatz 1
D-1000 Berlin 33
Federal Republic of Germany
OFFICE TEL. 030-8903-2253
-0
HOME TEL... 030-721 1576
TELEX 183 756
TRANSLATION:
Federal Environmental Agency
Dr. Martin Zarth, Dipl.-Chem
Umweltbehoerae Hamburg
Hermannstrasse 40, IV
D-2000 Hamburg 1
Federal Republic of Germany
OFFICE TEL. 040-34913-34 76
TELEX 040-212121 SENAT D
TRANSLATION:
Hamburg Ministry of Environment, Office of Remedial Action
A-3
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FRANCE
Phillippe Boisseau
Chef de la Division Environmental Industriel
Direction Regionale de 1'Industrie et de la
Recherche (Region Midi-Pyrenees)
84 Rue du Feretra
3107 8 Toulouse Cedex
France
OFFICE TEL. 33 61 39 58 57
HOME TEL... 33 61 23 87 71
Grano Bruno
Engineer
Direction Regionale de 1'Industrie et de la
Recherche (Ministry of the Environment)
84 Rue du Feretra
31078 Toulouse Cedex
France
OFFICE TEL. 33 61 39 58 43
HOKE TEL... 33 61 51 69 04
Thierry Dumesnil
Attache de Direction
E.i.f. Ecology
97 Rue Pierre de Montreuil
93100 Montreuil
France
OFFICE TEL. 48 58 91 44
TELEX 48 58 55 82
Rene Goubier
Head of Hazardous Sites Team
Agence Nationale Pour la Recuperation et
1'Elimination des Dechets (ANRED)
2 Square la Fayette
BP 406
49004 Angers Cedex
France
OFFICE TEL. 41-87-29-24
HOME TEL... 41-73-22-32
TELEX 721325 F
NORWAY
Dr. James Berg
Senior Scientist
Aquateam Norwegian
Water Technology Center A/S
P.O. Box 6326 Etterstad
0604 OSLO 6
Norway
OFFICE TEL. 47 2 67 93 10
HOME TEL... 47 2 78 10 06
A-4
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Morten Helle
Senior Executive Officer
Hazardous Waste Section
Statens Forurensningstilsyn
P.O. Box 8100 Dep
N-0032 OSLO 1
Norway
OFFICE TEL. 472-659-810
HOME TEL... 472-490-656
TELEX 76684 SFTN
TRANSLATION:
State Pollution Control Authority
THE NETHERLANDS
Herman Bavinck
Ministry of the Environment
P.O. Box 450
2260 MB Leidschendam
The Netherlands
OFFICE TEL. 070 209367
HOME TEL... 070 131170
TELEX 32362 VROM NL
Ing. H. C. M. Breek
Hollandse Wegenbouw Zanen BV
afd. Bodemsanering
Vanadiumweg 5
3812 PX Amersfoort
The Netherlands
OFFICE TEL. 3133613844
Ir. J. F. de Kreuk
TNO/MT
P.O. Box 217
2600 AE Delft
The Netherlands
OFFICE TEL. 3115569330
Dr.ir E.W.B. de Leer
TU Delft
Lab. Voor Analytische Scheidkunde
2625 RZ Delft
The Netherlands
Dr. H. J. P. Eijsackers
Program Director
Netherlands Integrated Soil Research Programme
P.O. Box 37
6700 AA Wagemmegen
The Netherlands
OFFICE TEL. 08 370-84170
HOME TEL... 08 360-26484
A-5
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Ir. D. H. Eikelboom
TNO/MT
P.O. Box 217
2600 AE Delft
The Netherlands
OFFICE TEL. 31 15 56 93 30
Merten Hinsenveld, M.SC.
Scientific Research Engineer
Department of Environmental Technology
TNO - Division of Technology for Society
P.O. Box 342
Laan Van Westenenk 501
7300 AH Appeldoorn
The Netherlands
OFFICE TEL. 3155 77 33 44
HOME TEL... 3155 41 53 93
TELEX 36395 TNOAP NL
R. Kabos
Delft Geotechnics
P. 0. Box 69
2600
AB Delft
The Netherlands
OFFICE TEL. 15 69 37 04
HOME TEL... 79 31 49 35
TELEX 38234 Soil NL
K. Keuzenkamp
Ministerie VROM
P.O. Box 450
2260 MB Leidschendam
The Netherlands
OFFICE TEL. 3170209367
Ir. Rene Kleintjes
Department of Biochemical Engineering
Delft University of Technology
Julianalaan 67
2628 BC Delft
The Netherlands
OFFICE TEL. 015-78 16 18
A-6
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P. Massink
Provincie Waterstaat Utrecht
Galileilaan 15
3584 BC Utrecht
The Netherlands
J. E. T. Moen
Ministerie VROM
P.O. Box 450
2260 MB Leidschendam
the Netherlands
OFFICE TEL. 3170209367
J. Roels
Ministerie VROM
P.O. Box 450
2260 MB Leidschendam
The Netherlands
OFFICE TEL. 3170209367
Ing. C. Schuler
Ecotechniek BV
P.O. Box 8447
3503 RK Utrecht
The Netherlands
OFFICE TEL. 3130957922
Esther Soczo, M.SC.
NATO/CCMS Pilot Study Co-Director
Rijksinstituut voor volksgezondheid
en milieuhygiene (RIVM)
Laboratory for Waste Material and Emissions (LAE)
Antonie Van Leeuwenhoeklaan 9
Postbus 1, 3720 BA Bilthoven
THE NETHERLANDS
OFFICE TEL. 31-30-74-30-65
31-30-74-30-60
HOME TEL... 31-15-132074
TELEX 47215 RIVM NL
TRANSLATION:
Nat. Inst, of Public Health and Environmental Protection
B. Tuin
TU Eindhoven
Afd. FT-HAL
P.O. Box 513
5600 MB Eindhoven
The Netherlands
A-7
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Leon Urlings
TAUW Infra Consult
P.O. BOX 479
7400 AL Deventer
The Netherlands
OFFICE TEL. 31-5700-99911
HOME TEL... 31-3495-35499
N. D. v. Egmond
Rijksinstituut voor volksgezondheid
en milieuhygiene (RIVM)
Antonie Van Leeuwenhoeklaan 9
Postbus 1, 3720 BA Bilthoven
The Netherlands
TELEX 47215 RIVM NL
Reinier van de Berg
Rijksinstitut voor volksgezonheid
en milieuhygiene (RIVM)
Laboratory for Soil and Groundwater (LAE)
P.O. Box 1
3720 BA Bilthoven
The Netherlands
OFFICE TEL. 31 30 74 33 38
TELEX 47215 RIVM NL
TRANSLATION:
Nat. Inst, of Public Health and Environmental Protection
W. J. van den Brink
Netherlands Organization for Applied Scientific
Research TNO
P.O. Box 297
2501 BD The Hague
the Netherlands
OFFICE TEL. 070-496630
HOME TEL... 01820-3669
Ir. B. L. van der Ven
Ministerie VROM
Oirectie Bestuurszaken
P.O. Box 450
2260 Leidschendam
The Netherlands
OFFICE TEL. 3170209367
A-8
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Dr. Jaap van Eyk
Delft Geotechnics
P.O. Box 69
2600 AB Deift
the Netherlands
OFFICE TEL. 015 693707
Ir. A. B. van Luin
DBW/RIZA
P.O.Box 17
8200 AA Lelystad
the Netherlands
OFFICE TEL. 313200-70465
HOME TEL... 313211-1894
TELEX 40600
Ing. J. H. A. M. Verheul
RIVM/LBG
P.O. Box 1
3720 BA Bilthoven
The Netherlands
OFFICE TEL. 3130743384
Dr. ir. C. W. Versluijs
RIVM/LAE
P.O. Box 1
3720 BA Bilthoven
The Netherlands
OFFICE TEL. 31743051
Dr. J. G. Wesseis Boer
Ministry VROM
Plv. dir. DWB
P.O. Box 450
2260 MB Leidschendam
the Netherlands
OFFICE TEL. 3170209367
NITED KINGDOM
Dr. R. Paul Bardos
Warren Spring Laboratory
Department of Trade and Industry
Gunnels Wood Road
Stevenage SGI 2BX
United Kingdom
OFFICE TEL. 0438-741122
HOME TEL... 0462 67 10 44
TELEX 82250 WSLDOIG
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UNITED STATES
Naomi Barkley
Environmental Scientist
U.S. Environmental Protection Agency
Risk Reduction Engineering Laboratory
Superfund Technology Demonstration Division
26 West Martin Luther King Drive
Cincinnati, OH 45268
United States
OFFICE TEL. 513-569-7854
HOME TEL... 513-541-8911
Paul de Percin
Chemical Engineer
U.S. Environmental Protection Agency
Risk Reduction Engineering Laboratory
Superfund Technology Demonstration Division
26 W. Martin Luther King Dr.
Cincinnati, OH 45268
United States
OFFICE TEL. 513-569-7797
Douglas Downey
U.S. Air Force
Engineering and Service Center
HQ AFESC/RDV
Building 1117
Tyndall Air Force Base
Panama City, FL 32403
United States
OFFICE TEL. 904-283-2942
TELEX 904-283-6499
Stephen C. James
Chief, Demonstration Section
Superfund Technology Demonstration Division
Risk Reduction Engineering Laboratory
U.S.Environmental Protection Agency
26 W. Martin Luther King Drive
Cincinnati, OH 45268
United States
OFFICE TEL. 513-569-7877
HOME TEL... 513-321-7937
Walter W. Kovalick, Jr., Ph.d.
Deputy Director, Office of Emergency
and Remedial Response
U.S. Environmental Protection Agency
401 M Street, S.W. (OS-200)
Washington, DC 20460
United States
OFFICE TEL. 202-382-2180
HOME TEL... 703-323-6078
TELEX 892 758 EPA WSH
A-10
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Maj Thomas Lubozynski
U.S. Air Force
Engineering and Service Center
HQ AFESC/RDV
Building 1117
Tyndall Air Force Base
Panama City, FL 32403
United States
OFFICE TEL. 904-283-2942
HOME TEL... 904-871-0792
TELEX 904-283-6499
Donald Sanning
NATO/CCMS Pilot Study Director
Chief, Emerging Technology Section
U.S. Environmental Protection Agency
Risk Reduction Engineering Laboratory
Superfund Technology Demonstration Division
26 West Martin Luther King Drive
Cincinnati, OH 45268
United States
OFFICE TEL. 513-569-7875
Fred Stroud
U.S. Environmental Protection Agency
Region IV
345 Courtland Street, N.E.
Atlanta, GA 30365
United States
OFFICE TEL. 404-347-3931
HOME TEL... 404-347-4062
SPECIAL REPRESENTATIVES
Eusebio Murillo Matilla
Commission of the European Communities
DG XI
10, rue Guimard (M23)
B-1040 Brussels
Belgium
OFFICE TEL. 32-2-2363 188
Hans-Joachim Stietzel
Commision of the European Communities
DG XI
10, rue Guimard (M22)
1040 Brussels
Belgium
OFFICE TEL. 022 35 98 00
A-ll
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NATO EXPERT GUEST SPEAKERS
Guus Annokkee
Department of Environmental Technology
TNO - Division of Technology for Society
P.O. Box 342
7300 AH Apeldoorn
The Netherlands
OFFICE TEL. 31 55 77 33 44
HOME TEL... 31 57 66 22 28
TELEX 36395 TNOAP NL
Prof. Karel Ch.A.M. Luyben
Department of Biochemical Engineering
Delft University of Technology
Julianalaan 67
2628 BC Delft
The Netherlands
OFFICE TEL. 31 15 78 23 53
HOME TEL... 31 15 14 6463
TELEX 3815 BUTVAL NL
Gregory G. Ondich
U.S. Environmental Protection Agency
401 M St.„ S.W. (RD-681)
Washington, D.C. 20460
UNITED STATES
OFFICE TEL. 202-382-5747
HOME TEL... 202-544-7853
Dr. Ronald Probstein
Massachusette Institute of Technology
Department of Mechanical Engineering
Room 3-246
Cambridge, MA 02139
United States
OFFICE TEL. 617-253-2240
HOME TEL... 617-734-3429
NATO/CCMS FELLOWS
Dr. M. Resat Apak, Ph.D.
Istanbul University
Faculty of Engineering
Dept. of Chemistry and Dept. of Environmental
Research, Vezneciler
Istanbul
Turkey
OFFICE TEL. 520 75 50 EXT: 56
HOME TEL... 337 68 62
A-12
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Dr. Robert Bell
Director, Environmental Advisory Unit
Liverpool University
131 Mount Pleasant
Liverpool L3 5TF
United Kingdom
OFFICE TEL. 051-709-1377
HOME TEL... 051-632-1458
TELEX 627095
Thomas 0. Dahl
U.S. Environmental Protection Agency
National Enforcement Investigations Center
Denver Federal Center, Building 53
Denver, Colorodo 80225
United States
OFFICE TEL. 303-236-8358
HOME TEL... 303-235-0284
Dr. Alessandro Di Bomenico
Laboratory of Comparative
Toxicology and Ecotoxicology
Istituto Superiore di Sanita
Viale Regina Elena, 299
00161 Rome
Italy
OFFICE TEL. 4990 EXT: 826 or 797
HOME TEL... c/0 839 3082
Dr. James Gossett
School of Civil and Environmental Engineering
Cornell University
Hollister Hall
Ithaca, NY 14853-3501
United States
OFFICE TEL. 607-255-4170
HOME TEL... 607-257-3385
Dr. Wayne A. Pettyjohn
School of Geology
Oklahoma State University
Stillwater, OK 74078-0451
United States
OFFICE TEL. 405-744-6358
HOME TEL... 405-372-1981
A-13
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Michael A. Smith
Clayton Bostock Hill & Rigby, Ltd.
68 Bridgewater Road
Berkhamstea
Hertfordshire HP4 1JB
United Kingdom
OFFICE TEL. 021-359-5951
HOME TEL... 0442-871500
TELEX 337273
Sjef J. J. M. Staps, Ing.
Rijksinstituut voor volksgezondheid
en milieuhygiene (RIVM)
Laboratory for Waste Material and Emissions (LAE)
Antonie Van Leeuwenhoeklaan 9
P.O. Box 1
3720 BA Bilthoven
The Netherlands
OFFICE TEL. 31-30-743038
HOME TEL... 31-33-05172
TELEX 47215 RIVM NL
TRANSLATION:
Nat. Inst, of Public Health and Environmental Protection
Dr. Aysen Turkman
Dokuz Eylul University
Faculty of Engineering and Architecture
Department of Environmental Engineering
Bornova Izmir
Turkey
OFFICE TEL. 51 18 21 08
HOME TEL... 51 18 45 48
ON-SITE SUPPORT STAFF
Chamaine C. Commins
Research Associate
JACA Corp.
550 Pinetown Road
Fort Washington, PA. 19034
United States
OFFICE TEL. 215-643-5466
HOME TEL... 215-763-2071
TELEX 846-570
Virginia R. Hathaway
Director of Communications
JACA Corp.
550 Pinetown Road
Fort Washington.PA 19034
United States
OFFICE TEL. 215-643-5466
HOME TEL... 215-643-4643
TELEX 846-570
A-14
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Appendix B
Presentations by
NATO/CCMS Guest Speakers
-------
Dr. Hans Joachim Stietzel
Eusebio Murillo Matilla
B-l
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NATO/CCMS PILOT STUDY OF REMEDIAL ACTION TECHNOLOGIES FOR
CONTAMINATED LAND AND GROUNDWATER
BILTHOVEN, THE NETHERLANDS, NOVEMBER 7-11 1988
Soil protection against point-source contamination in the
European Community
Dr. Hans Joachim Stietzel
Mr. Eusebio Murillo Matilla
B-2
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Soil protect ion 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 20.03.1978 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. (PE DOC A 2-31-
/ 8 7)
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
B-3
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3. Financing models
IV. Community action concerning point source
contamination of soil
1. Research and Demonstration
1.1 Existing studies and reports
1.2 ACE Programme
1.3 Research areas (DGXII)
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 remedial
act ion technologies for contaminated land and groundwater
3.2 International organisation for standardization (ISO)
TC 190
V References
VI Annexes
B-4
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I. Definitions and types of soil contamination and
deterioration
1. Definitions
There exists no generally accepted definition for
contaminated land in the European Community. Some Member
States have defined it in the following way:
Denmark: Land which presents a threat to groundwater
sources or to the health of local residents (Danish
National Agency on Environmental Protection, 1985)
Germany: Land that presents a potential direct or
indirect adverse impact upon the health and welfare of
humans and economically important natural resources, such
as livestock, crops and groundwater sources. (BMFT, 1981)
UK: Land, which because of its former use, now contains
substances that present hazards likely to affect its
proposed form of redevelopment, and which requires an
assessment to determine whether the proposed development
should proceed or whether some form of remedial action is
required. (DOE, 1983)
Netherlands: Land, where substances are present in soil
in concentrations higher than those in which they would
normally expect to occur and where they pose a serious
threat to public health and the environment. (Ministry of
Housing, Physical Planning and Environment, 1983)
Generally speaking two types of soil pollution can be
distinguished:
2. Diffuse contamination: 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. Point source contamination: 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)
B-5
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- disused production plants and
former industrial sites
waste disposal:
- municipal landfills
- hazardous waste landfills
- co-disposal landfills
- abandoned uaste disposal sites
II Relevance of Council Directives, Action Programmes
and Parliament Resolutions for soil protection against
point source contamination.
Soil protect ion 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 (86/278/EEC).
To a certain extent, the following articles of directives
can be applied for the benefit of soil protection.
B-6
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1. Council Directives/18/
1•1 Council Directive of 15.07.1975 on waste (75/442/EEC)
Article A
Member States shall take the necessary
measures to ensure that waste is disposed
of without endangering human health and
without harming the environment, and in
particular:
- without risk to water, air, soil and
plants and animals,
- without causing a nuisance through noise
or odours,
- without adversely affecting the
countryside or places of special interest.
1•2 Council Directive of 20.03.1978 on toxic and
dangerous waste (78/319/EEC)
Article 7
Member States shall take the necessary
steps to ensure that:
- toxic and dangerous waste is, where
necessary, kept separate from other matter
and residues when being collected,
transported, stored or deposited;
- the packaging of toxic and dangerous
waste is appropriately labelled,
indicating in particular the nature,
composition and quantity of the waste;
- such toxic and dangerous uaste is
recorded and identified in respect of each
site where it is or has been deposited.
Article 16
1. Every three years, and for the first
time three years following the
notification of this Directive,
Member States shall draw up a situation
report on the disposal of toxic and
dangerous waste in their respective
countries and shall forward it to the
Commission. The Commission shall circulate
this report to the other Member States.
B-7
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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 of 16/6/1975 on the disposal of
waste oils (75/439/EEC)
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 Council Directive of 12.06.1986 on the protection of
the environment and in particular of the soil, when
sewage sludge is used in agriculture (86/278/EEC).
Article 1
The purpose of this Directive is to
regulate the use of sewage sludge in
agriculture in such a way as to prevent
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.
B-8
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1•5 Council Directive of 17.12.1979 on the protection of
groundwater against pollution caused bv certain dangerous
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 II', 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) 'groundwater' means all water which is
belou the surface of the ground in the
saturation zone and in direct contact uith
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 Council Directive of 27.06.1985 on the assessment of
the effecti of certain public and private projects on the
environment. (85/337/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.
B-9
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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. The significance of the 4th Environmental Action
Programme (1987 - 1992) for soil 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." /1/.
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
infrastructure by proposing measures
(within the context of the reform of the
common agricultural policy) to encourage
less intensive livestock production
B-10
-------
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 uaste disposal
practices,
- to encourage the development of
innovative soil protection techniques and
the transfer of available knou-hou.
3. Resolution of the European Parliament on the waste
disposal industry and old waste dumps (19.06.1987). PE
DOC A 2-31-/87
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 (Doc. B 2-1654/85; 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 remedial actions in the EC
"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." /^^/
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
B-ll
-------
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
B-12
-------
2. Comparison of costs for some of the existing remedial
and containment techniques
TECHNIQUES
COST
Thermal techniques
± 75-175 ECU/t
Extraction techniques
(physico-chemical)
± 75-100 ECU/t
Microbiological techniques
± 50-125 ECU/t
Surface sealing
(synthetic material)
± 10-18 ECU/itV
Seal walls
± 18-175 ECU/m2
Bottom liners
Horizontal barriers
±, 200-1000 ECU/m2
B-13
-------
3 . Financing models
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 .2 5US$, 2.07DL, 0.66£, 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 successful1 .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 2 5 000 potential hazardous sites were
identified and 888 sites were listed on the NPL (National
Priority List) for remedial action.
B-14
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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• Research and demonstration
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 (1986)
Contract number 85-86 600-11 -042-11-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.
B-15
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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 R + D
and legislative controls.
c. Dornier-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. Mickan-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 ACE-programme (Action by the
Community relating to the Environment), Council
regulation N° 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.
B-16
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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 throughflou
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
- Enviroomental 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.
B-17
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COUNTRY
SITES
3resent annual
sxpenditure (1984)
X106
Estimated future
annual expenditure*
X106
% of GDP
Number
Type
Ref
year
up sites
ECU
National
currency
ECU
Nat.currency
BELGIUM
Flanders: 70
Wallonia
industrial/waste
1985
Insufficient
data.
62
2772 BFR
0,08
DENMARK
3115
industial/waste
1980-2
Insufficient
data.
5
44DKR
13
101 DKR
0,03
GERMANY
35000
44000
5000 industrial
30000 waste
1985
1987
Insufficient
data.
North-Rhine
Westphalia
48
106 DM
377
829 DM
0,07
FRANCE
800
1982
Insufficient
data.
Nord pas de
Lorraine,
13
Calais,
Rhone-Alps
87 FF
214
1468 FF
0.04
IRELAND'*
7
gasworks/mines
?
Insufficient
data.
10
7 £
0,06
ITALY
5433
abandoned waste
?
Insufficient
data.
134
198190 LI
0,06
GREECE
5000
uncontrolled
disposal
?
Insufficient
data.
11
1456 DR
0,04
LUXEMBOURG
142
municipal waste
1986
Insufficient
data.
3
189FRS
0,07
NETHERLANDS
6060
Contaminated: 6000
small/60 big
1986
Insufficient
data.
88
215DFL
56
140 DFL
0,04
PORTUGAL
69
+ 1800
toxic or hazardous
waste
industrial (estimate)
1986
Insufficient
data.
SPAIN
(Catalonia 400)
916
industrial waste
uncontrolled spillways
urban solid waste
uncontrolled spillways
Insufficient
data.
UK
until ilio ye.11 »000
Wales 703
45600 Ha
Contaminated
derelict land
1983/4
1982
Insufficient
data.
476
280 £
0,1
new inventory until enrI of 1QR7
-------
Landf ills:
a) Research for the safe disposal of hazardous waste in
landf ills
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. Preparation of legal provisions
(recommendations, resolutions, regulations, decisions-
directives )
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-landfi1Is
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
B-19
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3. Particioation in international working
groups/technical committees
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 experts' meeting in the Netherlands
(Bilthoven, November 1988) and to present the activities
of the CEC in the field of remedial action technologies.
3.2 International organisation for standardization (ISO)
TC 1 90
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 XI/A-3) has an
observer status and receives all documents.
V References:
/\/ 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.,
B irmingham
/3/ European Environmental Bureau (1988): Soil
contamination through industrial toxic dumps. - Seminar,
Brussels
/A/ Barkouski, D. et al. (1987) Altlasten. Handbuch zur
Ermittlung und Abwehr von Gefahren durch kontaminierte
Standorte. - Verlag C.F. Miiller, Karlsruhe
/5/ Hurtig, H.W. et al. (1986): Statusbericht zur
Sanierung von kontaminierten Standorten - ubersicht liber
Sanierungskonzepte und SanierungsmaBnahmen in Forschung
und Praxis. - Battelle Institut e. V., Frankfurt
/6/ Kerndorff, H. et al. (1988): Groundwater
contamination by abandoned waste disposal sites:
Detection and posssibilities of standardized assessment.
- In: K. Uolf et al. (Ed.): Contaminated Soil '88, Second
International TNO/BMFT Conference on Contaminated Soil,
Hamburg
-------
/ 7 / Franzius, V. (1986): Effects of abandoned waste
disposal sites and industrial sites on the soil: Possible
remedial measures. - In: Barth, H. + L'Hermite, P. (Ed.):
Scientific basis for soil protection in the European
Community. Elsevier; London, New York
/ 8 / Kloke, A. (1988): Fundamentals for determining use-
related, highest acceptable contaminant levels in inner
city and urban soils. - In: K. Uolf 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 of soil quality criteria. - In: K.
Uolf et al. (Ed.): Contaminated Soil '88, Second
International TNO/BMFT Conference on Contaminated Soil,
Hamburg
/10/ De Bruijn, P.J. + de Ualle, F.B; (1988): Soil
standards for soil protection and remedial action in the
Netherlands. - In: K. Uolf et al. (Ed.): Contaminated
Soil '88, Second International TNO/BMFT Conference on
Contaminated Soil, Hamburg
/II/ Assink, J.U. + van den Brink, U.J. (1986):
Prospective action with regard to soil contamination in
view of a common 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 -
Ubersicht und Kosten im EG-Bereich und in den USA. -
Vortrag beim Vertieferseminar "Altlastensanierung und
zeitgemaBe Deponietechnik", Universitat Stuttgart
/14/ Moen, J.E.T. (1988): Soil protection in the
Netherlands. - In: K. Uolf et al. (Ed.): 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/BMFT Conference on Contaminated Soil, Hamburg
/16/ Schnurrer, H. (1988): Altlasten in der
Bundesrepublik Deutschland. - Second International
TNO/BMFT Conference on Contaminated Soil, Hamburg
(Manuscript)
/17/ Stief, K. (1987): Strategy in landfilling solid
wastes - different solutions in practice.
Umweltbundesamt, Berlin.
B-21
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/1 8 / European Community Environmental Legislation, 1 967-
1 987,
(Vol.1, General Policy and Nature Protection)
(Vol.3, Chemicals and Uaste)
(Vo1.A, Uater)
Document No. XI/989/87
Brussels
B-22
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ANNEX 1
Sewage sludge
ANNEX I A
LIMIT VALUES FOR CONCENTRATIONS OF HEAVY METALS IN SOIL
(mg/kg of dry matter in a representative sample, as defined in Annex D C, of toil with a pH of 6 to 7)
Puameters
Limit values (')
Cadmium
1 to 3
Copper (')
50 to 140
Nickel (')
30 to 75
Lead
50 to 300
Zinc (')
150 to 300
Mercury
1 to 1,5
Chromium (*)
—
(') 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.
(') 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 submined by the Commission, within one year
following notification of this Directive.
ANNEX 1 B
LIMIT VALUES FOR HEAVY-METAL CONCENTRATIONS IN SLUDGE FOR USE IN
AGRICULTURE
(mg/kg of dry matter)
Parameter*
Limit vaJuei
Cadmium
20 to 40
Copper
1 000 to 1 750
Nickel
300 to 400
Lead
750 to 1 200
Zinc
2 500 to 4 000
Mercury
16 to 25
Chromium (')
—
(') 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 submined by the Commission within one year
following notification of this Directive.
B-23
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ANNEX 2
ANNEX
LIST I OF FAMILIES AND GROUPS OP SUBSTANCES
List I contains the individual substances which belong to the families and groups oi substances enum-
erated below, ».th the exception of those which are considered inappropriate to list I on the basis of
a low risk of toxicity, penistance and bioaccumulation.
Such substances which with regard to toxicity, penistance and bioaccumulation are appropriate to list
II are to be classed in list II.
I. Organohalogen compounds and substances which may form such compounds in the aquatic envi-
ronment
1. 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. Cadmium and its compounds
7. Mineral oils and hydrocarbons
8. Cyanides.
LIST II OF FAMILIES AND GROUPS OF SUBSTANCES
List II contains the individual substances and the categories of substances belonging to the families
and groups of substances listed below which could have a harmful effect on groundwater.
1. The following metalloids and metals and their compounds:
1. Zinc 11. Tin
2. Copper 12. Barium
3. Nickel 13. Beryllium
4. Chrome 14. Boron
5. Lead 15. Uranium
6. 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, and
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.
(') Vlier« certain uihtiancet »t list II are laiiinngenic. mutagenic or teratogenic, (hey •>« included in category 4 of thu list
B-24
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ANNEX 3
No C 190/154 Official Journal or the European Communities 20.7.87
Friday, 19 Jium 1987
6. Waste disposal industry — Water quality objectives for (Chromium
(a) Doc. A2-31/87
RESOLUTION
on the waste 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),
— having regard to the motion for a resolution by Mr Tridente on the danger or discharging
waste on the outskirts of an environmental protection area (Doc. B2-952/86).
— having regard to its previous resolutions on waste and in particular those of 16 March 1984 (*)
and II April 1984 (»),
— having regard to the report by the Committee on the Environment, Public Health and
Consumer Protection (Doc. A2-31/87);
Regarding tho general object Ires of Community policy on watte
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 posts in the budget for the environment sector, but the Commission
has not used them for matters concerning waste);
(b) the harmonization of systems of statistics on waste;
(c) clarification of the Community definition and nomenclature of dangerous waste;
(d) the development of a long-term Community strategy on waste management;
(e) the organization of campaigns to increase the awareness of the public, waste producers and
workers in the industry,
(f) 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 effect 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 States regarding the observance of
directives adopted on waste, and insists once again that the Commission play its full role in
ensuring total compliance with these 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;
5. 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. 16.4.19S4. P. 147.
(>) OJ No C 127. 14. S. 1984, p. 67.
B-25
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ANNEX 3
20.7.87 Official Journal of the European Communities
NoC 190/155
FrMay, 19Jm» 19*7
7. Stresses particularly that the harmonization of standards applicable 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 Ainction 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 States must make available in accordance with the obligations laid down in existing
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
metals;
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;
Mttuuru to b» taktn rtgardlng old waatt dumpt
17. Drews attention to the extent and seriousness of the potential problems, in particular
regarding 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 15 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;
B-26
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ANNEX 3
NoC 190/156
Official Journal of the European Communities
20.7.87
FrMay. 19 Ju* 1987
-a
19. Points out "that in the European Community only a few Member States have so Tar
recognized the nature of the problem and taken certain measures as a result:
20. Points out that this disparity among national responses to the problem of contaminated
sites is not only a cause of distortion of competition but has also led to many cases of contami-
nated soil being exported from one country to another,
21. Recalls that the concept of action at the most appropriate level is one of the principles of the
Community's environment policy as contained in Article I30R 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 ofinformation 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 coven
— 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;
•
* •
31. Instructs its President to forward this resolution to the Council and Commission.
(') OJNoL84. 31. 3.1978. p. 45.
B—27
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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
for the 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 technigues
4/1 Thermal techniques for the decontamination of soils polluted by
halogenated organic compounds.
5.. Extraction technigues
5.1 Improvement of extraction methods for soil restoration
5.2 Combination of extraction methods and biological treatment techniques
for the decontamination of oil and other organic compound sludges.
B-28
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Karel Luyben
B-29
-------
Dutch research on microbial soil decontamination in bioreactors
K.Ch.A.M. Luyben1, G. Annokkee0 R.H. Kleijntjens1
• TNO Division of Technology -for Society, P.O. box 342, Apeldoorn
1 Biotechnology Del •ft Leiden, BDL
Department of Biochemical Engineering, Delft University o-f Technology,
Julianalaan 67, 2628 BC DeHt, The Netherlands
Micro-organisms are able to convert aerobically 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 hinderer.ces 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 of 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 TNO, the other
by TUD. Generally speaking both projects can be characterized by the
following research items:
-optimum conditions for biodegradation has to be reached by applicating a
bioreactor
-the treatment time of the polluted soil in the bioreactor has to be short
as possible
-the types of 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 features of the projects will be
presented:
TNO-project
Preliminary the following oyerall results are achieved:
~ A dry treatment method (10 - 15Z humidity of the soil; soil as such) as well
as a wet treatment method (soil slurry) have potentials for being applicated
in practice.
- The design criteria for tha bioreactor types used in the dry and wet method
are known.
- Both batch and continuous processes can be applied.
- A variety of soil types (from sand to loam) can be treated.
- Experiments have been carried out on soils polluted with mineral oils and
polycyclic aromates^PCA1s) with the following results:
B-30
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treatment
method
soil
type
contaminant
contaminant concentration (mg/kg dry soil)
day 0 day 3 day 14
dry
sand
cutting oil
3,000
980
680
dry
sand
diesel fuel
4,200
1,800
900
wet
loamy
cutting oil
26,000
9,000
1,200
sand
wet
loam
cutting oil
65,000
12,000
wet
loam
PCA's
3,900
1,700
300
TUD 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 of a
special designed injection system using compressed air and water. With this
newly designed injector it is possible to make optimal use of 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
of subtrate, oxygen and carbondioxide as a function of time during batch
experiments and during continuous processing. A simple model is developed to
describe the kinetics of the system. Both in the model and in experiments
attention is paid to mass transfer and suspension characteristics in the
three phase slurry.
The suspension behavior of soil particles in the three phase slurries is
studied both on laboratorium and pilot-plant scale. Understanding the
performance of high density suspensions at different scales demands an
intens research effort for both technical and theoretical aspects. A
combination of insight in the physics of soil suspensions, mass transfer
properties and biokinetics should result in optimum operation conditions for
this process. This should then lead to a flowsheet including pre- and after-
treatment operations in relation to the central slurry reactor. Finally, a
study to access the economical feasibility of the process will follow.
B-31
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Gregory Ondich
B-33
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THE USE OF INNOVATIVE TREATMENT 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
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
U_._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
in 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,
to reduce the land disposal of hazardous wastes and to encourage the
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
B-34
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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 (BDAT)
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
B-35
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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
(BDAT) identified for hazardous constituents. These treatment levels will be
monitored by measuring the concentration level of the hazardous constituents
in the waste or treatment residual or an extract of the residual. Ultimately,
the RCRA BDAT 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
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
B-36
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This waste minimization requirement will foster the development of
innovative technologies that are not convenient "end-of-the-pipe" treatment
approaches.
Looking beyond "end-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
Defining Waste Minimization
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
B-37
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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.4
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 se^/en^ million pounds 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
In May, 1988, EPA proposed rules for the "first-third" of listed RCRA
wastes that will be affected by the RCRA Amendments land disposal restric-
B-3£
-------
tions. Land disposal restrictions on "second-third" and "final-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 electric-arc-furnace dust
from emission-control devices at steel mi lis.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 consitituency 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 BDAT, the wastes cannot be land disposed.6
Superfund 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,
B-39
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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:
° accelerate the development, demonstration, and use of new
or innovative treatment technologies and
° 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 BDAT 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 wastes.
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."®
B-40
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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:
° Available Alternative Technology. Technologies, such as incinera-
tion, that are" ^fully proven and in routine commercial or private
use.
0 Innovative Alternative Technology. Any fully-developed technology
for which cost 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.
0 Emerging Alternative Technology. An emerging technology is one
in an "earller stage" of development; the research has not yet
successfully passed laboratory- or pilot-scale testing.?
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.
SITE Program
There are four principal components of the EPA SITE Program:
° field-scale demonstration evaluations
° emerging technology development
° EPA developed technologies
° technology transfer clearinghouse.
Each ot these components is designed to enhance the use of alternative and
innovative treatment technologies in remediating hazardous substance sites.
B-41
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Field Scale Demonstration Evaluations
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
applicabi1ity of these technologies to specific waste characteristics.
Two EPA reports will be produced on each demonstration scale evaluation -
a performance data 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 --
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,
B-42
-------
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
i nclude:
° solidification/stabilization -- eight
0 thermal -- eight
° biological -- five
° physical -- five
° 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.
Emerging Technology Development
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.
B-43
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The Emerging Technologies Program will deal with innovative technologies
for recycling, separation, detoxification, destruction, and solidification/
stabilization of hazardous constituents and material handling technologies.
Candidate technologies must show promise at the bench/laboratory scale. This
program will enable technology developers to advance from the bench/laboratory
to pilot scale through cooperative funding with EPA. The Emerging Technology
Program was started in the fall 1987. Of the 84 proposals that were submitted
seven were selected for funding. The second solicitation was made in July 1988.
The seven technologies selected from the first solicitation are summarized in
Table 5. These projects should begin within the next two months.
EPA 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 commercialized 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.
Technology 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
B-44
-------
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:
° A national telephone referral service will provide callers with
up-to-da"t~e~ information on" SITE" projects, demonstration schedules and
the availability of the results, and will also refer callers to
other sources of information.
° An 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.
° A collection of reports, journals and other documents is housed in
the EPA Library's Hazardous Waste Collection. This collection is
avaiTable at EPTTs ten regio~naV "and five laboratory libraries. The
bibliographic data base is accessible using a personal computer.
SITE documents will be added as they become available.!
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 BDAT 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 retreivai capability that will enable us to
access many more data sources including our own laboratory experts and
their state-of-the-art knowledge.
B-45
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CONCLUSION
Given the impetus placed on the development of "best demonstrated" and
"innovative/alternative" treatment technologies by the RCRA Amendments and
the SARA legislation, the future use for these technologies in hazardous
wastes is promising. However, the need to disseminate field performance
data on these technologies remains great. Given the number of demonstration
evaluations underway and the means to disseminate data from these evaluations
via the SITE Clearinghouse, it is expected that the use and familiarity of
these technologies will grow rapidly.
B-46
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TABLE 1
SITE DEMONSTRATION PROGRAM PARTICIPANTS
DEVELOPER
Geosafe Corporation,
Richland, WA
DESCRIPTION
Sol idi f i£at i on/St abji_U zation
In Situ Vitrification
Chemfix Technologies, Inc.
Metairie, 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
Soluble silicate reagents
Portland cement, fly ash, kiln dust
and proprietary chemicals
In SJt_u inorganic polymers and pro-
prietary chemicals
Lime-Based reagents
Silicate reagents
Pozzolanic reagents and proprietary
chemicals
Waste Chem Corporation
Paramus. NJ
Asphalt binders
Thermal Treatment
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
Pyretron Oxygen Burner
Shirco Electric Infrared
Electric Infrared Thermal
Circulating Fluidized Bed Combuster
Plasma Heat
In Situ Steam/Air Stripping
Pyroplasma System
B-47
-------
TABLE 1
SITE DEMONSTRATION PROGRAM PARTICIPANTS J Continued)
Thermal T reatment~TConti~hued)"
DEVELOPER DESCRIPTION
Roy F. Weston, Inc.
West Chester, PA
Chemical Waste Management
Oak Brook, IL
Air Products and Chemicals, Inc.
A1lentown, PA
Biotrol, Inc.
Chaska, MN
DETOX Industries, Inc.
Sugarland, TX
MoTec. Inc.
Mt. Juliet, TN
Zimpro Environmental Control Systems,
Rothschild, WI
Detox, Inc.
Newport Beach, CA
Low temperature reactor
Low temperature thermal dryer
Biological Treatment
Fixed film, fluidized bed
Physical
Biotrol, Inc.
Chaska, MN
CBI Freeze Technologies, Inc.
Plainfield, IL
E. I. Dupont de Nemours. Inc.
Newark, DE
Sanitech, Inc.
Twinsburg, OH
Fixed film plug flow reactor
Batch reactor
Liquid/Solid Contact Digestion
Batch reactor, powdered activated
carbon and wet air oxidation
Fixed film reactor
Soil Washing
Volume Reduction by Freezing
Microfiltration
Ion Exchange
Terra Vac, Inc.
Dorado, PR
CF Systems Corporation,
Cambridge, MA
Resources Conservation Company,
Bellevue, WA
Ultrox International,
Santa Ana, CA
Jn Sitjj Vacuum Extraction
Chemical Treatment
Solvent Extraction
Solvent Extraction
Ultraviolet Radiation and Ozone
B-48
-------
TABLE 2
COMPLETED SITE DEMONSTRATION EVALUATIONS
Technology
1. the Haztech/Shirco electric
infrared system (100 ton per day)
2. the Shirco electric infrared
system (1 ton per day)
3. the HAZCON solidification/
stabilization process
4. the American Combustion System
oxygen enhanced burner
5. the Terra Vac vacuum extraction
process
6. the International Waste Technology
in-situ solidification/
stabilization process
7. The C.F. Systems chemical
solvent extraction process
Site
Peak Oil Superfund Site
Brandon, FL
Rose Township Superfund Site
Rose, MI
Douglasville Superfund 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
B-49
-------
TABLE 3
SITE DEMONSTRATION EVALUATIONS PRELIMINARY RESULTS
_Haztech/Shi rxo
processed 360 tons of waste oil sludge with PCBs and lead
DE varied between 83 - 99 % based on PCBs in ash
HCL and S02 emissions low
EP Toxicity tests indicate lead in ash is leachable
PM emissions exceeded regulatory limit for two of four days
Shi rco/Rose
processed 2 tons of waste soils with dioxins/forans, PCBs and lead
DRE for PCBs greater than 99.99%, DE varied between 99.64 - 99.98%
PM and HCL emissions low
no conclusive evidence of lead fixation in ash
American Combustion Demonstration
processed mixed waste--Stringfel 1ow Acid Pits and Decanter Tank Tar
Sludge (K087)
DRE greater than 99.999%
low PM emissions
feed rate was doubled to 210 lb/hr
HAZCON
volume of solidified soil doubled
Chloranan improved Unconfined Compressive Strength (UCS) and impermeability
inverse relationship between UCS and organic content
permeability of solidified soils were low
EP Toxicity and TCLP tests indicate metals were stabilized, volatiles
and semivolatiles were not
leIrA Xa£
continous trouble free operation of system confirmed
1,000 lbs TCE recovered in 56 days
highest recovery rate 100 lbs TCE per day
extraction maintained at different soil depths
JnternatjKjnal Waste Technology
Geo-Con deep soil mixing equipment used for in-situ injection
PCB contaminated soils treated to 16 ft depth
two separate sectors about 200 sq ft each were treated
C.F. Systems
300 and 5000ppm PCB-contaminated waste sediments treated
20 drums of harbor sediment processed
Propane was the liquefied extraction solvent
B-50
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TABLE 4
USE OF INNOVATIVE TECHNOLOGIES
Name Location
Shirco Florida Steel Corp
Iridiantown, FL
LaSalle Electric Corp
LaSalle, IL
U. S. Army Ammunition
Depot, Twin Cities, MN
Geisur RCRA Site
Geisur, LA
HAZCON Mid South Wood Products
Mena, AR
Sand Springs Petrochemical
Complex, Tulsa County, OK
Basin F, Rocky Mountain
Arsenal, Denver, CO
Terra Vac 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
Waste Type
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
PCE, TCE and
TCP Contaminated Soil
Carbon Tetrachloride
Volume Treated
PCE, TCE & MEK
Gasoline
16,000 cu. yds.
35,000 cu. yds.*
12,000 cu. yds.*
40,000 cu. yds.*
* *
* *
* *
20-100 lbs/day
for 30 days
250 lbs/day for
30 days
2000 lbs/day;
ongoing cleanup
2000 lbs/day for
four months
~Estimation of the total site cleanup
~~Demonstration for potential cleanup
B-51
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TABLE 5
SITE EMERGING TECHNOLOGIES
Developer
Atomic Eneryy of Canada, Ltd.,
Ontario, Canada
Battelle Memorial Institute,
Columbus, OH
Bio-Recovery Systems, Inc.
Las Cruces, NM
Colorado School of Mines,
Golden, CO
Energy & Environmental Engineering, Inc.,
Somervilie, MA
Envirite 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
In Situ Oil Recovery and
Biodegradation
B-52
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TABLE 6
EPA DEVELOPED TECHNOLOGIES
Technology Remarks
Mobile Soils Washer This System has been designed for extraction of a broad
range of hazardous materials from spill-contaminated
soils using water as the extraction solvent. The proto-
type has been developed utilizing conventional equipment
for screening, size reduction, washing, and dewatering
of the soils. The washing fluid-water may contain addi-
tivies, such as acids, alkalies, detergents, and selected
organic solvents—to enhance soil decontamination. The
nominal processing rate is 4-yd^ of contaminated soil per
hour when the soil particles are primarily less than
2 mm in size, and up to 18-yd3 per hour for soil of
larger average particle size.
KPEG Treatment System Potassium polyethylene glycolate reagents are effective
dehalogenators of aromatic and aliphatic organic materials,
including PCB's and other toxic halides. The KPEG reagent
reacts with the chlorine atoms in the aryl ring of halo-
genated aromatic contaminants to produce innocuous ether
and potassium chloride salt. In some KPEG reagent formu-
lations, dimethylsulfoxide 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 smaller pilot unit on oily
pesticide wastes and liquid woodpreserving wastes.
Mobile Incineration The mobile incinerator consists of specialized equipment
System mounted on four trailers. In the rotary kiln on the
first trailer, organic wastes are fully vaporized and
completely or partially oxidized at approximately 1800°F.
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 2200°F 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 2200°F to approximately 190°F. 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.
B-53
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TABLE 6
EPA DEVELOPED TECHNOLOGIES
Technology 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 This System was designed for field use in reactiviting
Regeneration System spent granular activated carbon used in spill or waste
site cleanup operations. When contaminated granular
activated carbon (GAC) 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.
B-54
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REFERENCES
1. A Comprehensive Environmental-Industry Report on Recent EPA Cleanup
Decisions Environmental Defense Fund, Hazardous Waste Treatment
CouncM, National Audubon "Society, National Wildl'ife Federation, Natural
Resources "Defense CounciJ , Sierra CTub and U.S~. PIRG." June 20, 1988.
2. Resource Conservation and Recovery Act Amendments of 1984 (Hazardous and
Solid Waste Act) U. S. Congress.
3. Sarokin, D.J., Muir, W.R.. Milleo, C. G. 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
Materials 1988 Conference, Atlantic City, NJ, June 14, 1988.
5. Kearns,D.."New EPA Land Disposal Requirements to Cost Generators
$1 Billion annually; Waste Jech News, September 6, 1988.
6. U.S. Environmental Protection Agency, "Land Disposal Restriction for
First Third Scheduled Wastes", Volume 53, U.S. EPA, OSW, Washington, D.C.
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, D.C_., December 1986.
8. U.S. Environmental Protection Agency, Best Demonstrated Available Technology
(BOAT) Background Document, Volume 51, U.S. EPA, OSW, Washington, D.C.
November 7, 1986.
9. "Superfund Amendments and Reauthorization Act of 1986." Public 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.
B-55
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Ronald Probstein
B-57
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ELECTROOSMOSIS FOR IN SITU
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-------
TYPICAL PARAMETER RANfr€S
APPdEb voltage
VOLTAO-& Q-RAOteNT
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fo'9- to* nf/V-S
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Jo/a co/v6«/cTtvtry
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KOi. FLOW RWE/lMtT AA£A %
iO~*-2.ShtO* TrP/s/hn1-
-6
Ct/rtrt£/vr b£NS'ry
0.5-5 amw/w4.
-------
ELECTAOOJMOTic APPARATUS
GAS VEHT
ACTIVE ELECTRODE
POROUS SUPPORT
EFFLUENT
COLLECTOR
VOLTAGE SOURCE
PRESSURE
REGULATOR
PURGE
SOLUTION
RESERVOIR
-------
MEASUREMENTS
- voltage and pressure distribution
- current
- EO water transport
per unit charge kJjlL] LzUxiok£
(current efficiency) hr/ L
- hydraulic permeability
- chemical composition and
concentration of effluent
- electroosmotic
velocity
%(*»)'
electroosmotic
permeability
B-71
-------
£*AM PL£
0
solution
Uoltage applied: 0.6yolt/cn
acetic acid concentration: 0.5 H
noisture: SOI
electrodes: porous carbon plugs
1= 250 mA/m2
P= 70 mW or 7 W/m2
q^= 0.3 1/hr.m2
E= 0.1 UWh/gal
= 21 Wh/1
B-72
-------
Efflux vs Tine
CHAc] initial = 0.5 M
volume (ml) (Thousands)
time (days)
purge with 0.1M MaCI
B-73
-------
Percent of Acetic Acid Removed
by Electroosnosis
'< acetic acid removed
100
-
80
¦»
60
/
40
/
20
0
e
20 40 60 80
days
CHAcDinitial = 0#5M
B-74
-------
COST MS CONTAMINANT CONCENTRATION
at various flow rates
log< % / gal )
4
typical operating region
2
-
/
0
/.
//
-2
\
-4
-
-A
i
• i i
o
8 -6 -4 -2 0
log (concentration)
.01 cm/min .001 .0001
2
Kh =
1E-I6m*2; psi
= 2.8; L = 1 m
B-75
-------
Cost vs Concentration
constant voltage
log (concentration)
10 U/m 100 1000
Kh = le-16 mA2; psiw = 2.80; L = 1 m
B-76
-------
flow RATS vecrCRS bVRlNGr
E 0 TRf ATMCaJT
V H S COHIT ®
csO
~ /
S N
O
0
' ' ' /
N \ *
* ^ / t
0'
1
20
u ©
B-77
0.808Er04
MAXIMUM vfcTBR
-------
CONSTAT TOTAL HEAP UHES FftOH EO TACAT/W
( sib£ view)
B-78
-------
PiRSPzcrivP
— TOTrti. H£AD VALUES H
AFTER
£L£CTRoOJMOTlC TREATmPait
©
B-79
-------
CONCLUSIONS
LABORATORY EXPERIMENTS SHOW HIGH
LEVEL OF CONTAMINANT REMOVAL FROM CLAY
ENERGY COSTS FOR EO REMOVAL OF HAZARDOUS
WASTES FROM SOILS CAN BE LESS THAN $0.0|/gal
MODEL CALCULATIONS SHOW REQUIRED FIELD
STRENGTHS AND ELECTRODE CONFIGURATION
EMPLACEMENTS TO BE PRACTICAL
NUMBER OP TECHNICAL PROBLEMS MUST BE
STUDIED IN LAB TOGETHER WITH ADDITIONAL
COST AND MODEL STUDIES BEFORE.
EMBARKING ON FIELD TESTS
-------
Appendix C
Presentations by Continuing
NATO/CCMS Fellows
-------
Wayne A. Pettyjohn
c-i
-------
Hydrogeology of Fine-Grained Materials
by
Wayne A. Pettyjohn
School of Geology
Oklahoma State University
Stillwater, OK 74078
Introduction
It is often stated that ground-water quality is rather
uniform, both in time and space. As far as deeper, confined
aquifers are concerned, this is probably a rather safe assumption
as long as the system is not stressed. As pointed out by
Growitz and Lloyd (1971), Pettyjohn (1971, 1976, 1982, and 1986),
and Katz, Ragone, and Lindner (1978), among others, this is very
likely not the case with shallow or surficial aquifers. With
these systems the chemical, and probably biological quality as
well, might be neither uniform nor anticipated. It can change,
within a matter of hours, both vertically and horizontally. This
is particularly so in fine-grained systems, systems that might
normally be considered as confining units, even though they may
be capable of providing a considerable amount of water to a well.
This report describes some preliminary findings on how a
fine-grained water-bearing unit functions; it is based on data
collected from a field site over a period of 18 months.
Site Description
The field site, actually a backyard, lies in north-central
Oklahoma, an area of rolling hills formed on a series of gently
dipping layers of sandstone and shale of Permian age. The region
has about 34 inches of precipitation each year, most of which
occurs as rain during the spring and fall. Evapotranspiration
averages about 31 inches per year. There is a soil-moisture
deficiency most of the year.
The site includes nearly 11,000 square feet and the
monitoring wells lie within a 7,000 square feet area (fig. 1).
The site is on private property, which has the advantage of total
control and ready access. Other than natural phenomena, the only
potential source of ground-water contamination is the application
of fertilizer and pesticides, which occurs four times each year.
Fertilizer is applied at a rate of 4 pounds per 1000 square feet.
The investigative area lies on the flood plain of a small
stream, Boomer Creek, that is located about 600 feet to the west.
The alluvial part of the aquifer ranges in thickness from about
43 feet to 0 where the alluvium pinches out against a shale
bedrock high. The underlying shale is red and the alluvial
C-2
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materials, which were derived largely from the shale, are of a
similar color and consistency. The alluvium is the major water-
bearing zone and it consists almost entirely of a heterogeneous
mixture of very-fine sand (50%), silt (25%), and clay (25%) that
rests on the weathered shale. Presently, the area is monitored
by means of 28 wells, 4 soil-moisture access tubes, and 6 suction
lysimeters. A recording rain gage and barograph are available,
as well as a chemistry laboratory in a small building on the
property.
Within the property boundary are two buildings and
driveways. Most of the area is covered with Bermuda grass, but
along the southern border are several large hackberry and pecan
trees and other woody plants.
Well Construction
Presently the site contains 28 monitoring wells. Twenty of
the wells are placed in four clusters of five each (fig. 2). The
maximum distance between the most distant wells in each cluster
is about 1.5 feet. The maximum distance between clusters is
about 90 feet.
The wells in each cluster are 8.5, 9.5, 10.5, and 14 (2)
feet in depth (fig. 2). They consist of PVC pipe, 2 inches in
diameter, in which the lower 4 inches is slotted. The slots are
wrapped with nylon screen. The slotted section is sand packed
and the remainder of the annular space filled with a bentonite
slurry. A concrete pad surrounds the wells. The fifth well at
each cluster is 14 feet deep but the lower 6 feet are slotted and
sand packed. The casing is installed in holes drilled either
with a hand auger or hollow-stem auger.
Hydrogeology of the Site
The water level ranges from about 5.5 (April and May) to
11.5 (September) feet below land surface. Owing to the annual
water-level decline of some 6 feet or so, several of the shallow
wells are dry by mid to late summer. A hydrograph of a well, 14
feet deep, at cluster E is shown in Figure 3.
The water-level gradient is about .006 feet per foot to the
southeast in July, 1986 (fig. 4) and about .003 feet per foot to
the southwest in April, 1986 (fig. 5). The seasonal change in
flow direction from August to February is about 75 degrees. In
large part, the summer gradient and flow direction is produced by
transpiration by the large trees along the southern boundary of
the site. The diurnal changes averages about 0.4 feet in August
(fig. 6), but after the first killing frost it decreases to 0.05
to 0.2 feet. The rate of rise of the water level implies a
C-3
-------
horizontal ground-water velocity of about 1 foot per day. It is
important to note that transpiration does not cease entirely
during winter.
Well yields range rather widely but the deeper wells provide
more water than the shallower ones. Some of the wells in which 4
inches of the pipe are slotted will produce at least 1.3 gallons
per minute over a 72-hour interval, reaching equilibrium in less
than 2 hours. Specific capacity averages .5 gallons per minute
per foot of drawdown. The yields are surprisingly high when one
considers the fine-grained nature of the water-bearing zone.
Preliminary aquifer tests indicate a transmissivity of about
100 to 200 gallons per day per foot and a hydraulic conductivity
in the 15 to 30 gallons per day per square foot range within the
upper 8 feet of the saturated system. Considering the fine-
grained nature of the system, the values seem unusually large.
Calculated storativity ranges between .1 and .2.
Soil-moisture content throughout the site is consistently
below field capacity. The water content decreases rapidly within
a foot below land surface and remains fairly uniform until the
capillary fringe begins to take effect at depths ranging from 5
to 9 feet below land surface, depending on the position of the
water table.
Sampling And Chemical Analyses
The wells have been sampled in a variety of ways. Water has
been removed from the well bore by means of bailers, hand pumps,
vacuum, and peristaltic pumps. The latter seems to be the best
method because the rate can be held uniform and it has the least
effect on the chemical quality. It has been noticed in one well,
for example, that when a volume exceeding 1 liter is removed, the
water level begins to decline in the next shallower well and the
quality begins to change rather substantially, thus indicating
leakage.
Samples of water for chemical analyses are collected at
least weekly and sometimes several times in a single day. Most
of the chemical analyses are performed immediately in the field.
Samples are routinely analyzed for nitrate, pH, specific
conductance, chloride, bicarbonate, and temperature.
Periodically determined are calcium, magnesium, potassium,
sodium, and sulfate. Iron does not appear to be present.
Variations Throughout The site
The available chemical data base, consisting of more than
1100 individual analyses, shows that at no time have any two of
C-4
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the wells ever had the sane chemical quality, either within a
cluster or from one cluster to the next, despite their proximity.
On a scale of months, there is little or no relation between
water level and concentration in a single well. In the short
term, the concentration of nitrate can increase as the
conductivity decreases or vise versa. There is a wide range in
concentration of most constituents examined in space as well as
in time. For example, nitrate has ranged from 0.3 to 27.9 mg/1,
with an arithmetic mean of 5.8 and a standard deviation of 4.33.
Conductivity has ranged from 255 to 1975, with a mean of 1111,
and a standard deviation of 327.37.
In general, the water level and concentration in all of the
deeper wells appear to respond in concert, although the water
levels and concentrations are all different. On September 15,
1985 for example, the concentration of nitrate ranged from 10.4
to 28 mg/1, on the 18th the range was from 1.8 to 11 mg/1, and on
the 26th it was from 2.5 to 4.4 mg/1. During the fall recharge
period in late September through November, 1985 nitrate
fluctuated between 2.2 and 5.7 mg/1, although there was no
regular pattern or relation between water level and
concentration. The highest nitrate concentrations are usually
found at the shallowest depths.
One would assume that a well screened over an interval of 6
feet would be characterized by a chemical quality that is a
mixture of that present at discrete points within that interval,
perhaps being skewed toward a zone of greater hydraulic
conductivity. This has not been the case in this study. The
fully penetrating wells (screened from 8 to 14 feet) at each
cluster have consistently had either higher or lower
concentrations than all of the other wells in the cluster.
Short Term Variations
Relative to mass flow rate and ground-water recharge, two
events are noteworthy. On September 13, 1985 the soil-moisture
content was the lowest in the period of record, the water level
was about 11.5 feet below land surface, and the nitrate content
in one well, 14 feet deep, was 7 mg/1. On that day the yard was
fertilized and that night it rained 1.4 inches. By the 15th the
nitrate concentration had increased fourfold to nearly 28 mg/1,
by the 16th it had decreased to 18 mg/1, and by the 18th to only
4 mg/1. During this interval the water level rose 0.2 feet by
the 16th and then declined to the lowest level recorded by the
21st. These data suggest that a small quantity of nitrate-
enriched water migrated, via fractures, through the very dry
unsaturated zone at a rate of about 5.5 feet per day. The
subsequent decrease in concentration and the water-level rise was
due to dilution by more slowly moving water.
C-5
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By early April, 1986 water levels were about 7.5 feet below
land surface. On April 1 the yard again was fertilized and this
was followed by 3.1 inches of rain during the next three days.
During this interval the water level rose about 1.5 feet in all
of the wells. In one well, 8.5 feet deep, the nitrate
concentration was 23.7 mg/l on April 1. On the following morning
it had increased to 25.2 mg/l, by the afternoon it had decreased
to 18.4, the next morning it was 14.3, and about 5 hours later it
was only 10.5 mg/l. The trend in nitrate in all of the wells was
similar, although the concentration differed. The fact that
there was not a major increase in nitrate immediately following
the rain, as there was in the previous September event, is most
likely due to dilution. That is, there was a great deal of
ground-water recharge as shown by the water-level rise. Mass
balance calculations indicate that the total amount of fertilizer
lost to the subsurface was about the same in both cases. During
this interval the soil-moisture content was more than twice as
high as it was in September.
Conclusions
Even with the limited data base and time span of the
project, a number of conclusions are readily evident.
1. The chemical quality of the shallow ground water can change
throughout the year.
2. The chemical quality of water in fine-grained deposits can
range widely both vertically and horizontally due to natural
causes. The range of inorganic constituents may be one to two
orders of magnitude, depending on the constituent.
3. Vertical flow velocities through the unsaturated zone can
exceed 5.5 feet per day, even though there is a soil-moisture
deficiency.
4. Within 48 hours following a rain, the concentration of
nitrate can increase fourfold and within an additional 48 hours
can decrease at least fivefold from the previous high. The large
increase is due to a small volume of water that is highly
concentrated and, as a result, the water table is not
greatly impacted by the recharge event. This implies flow
through macropores.
5. Convective storms of high intensity, short duration, and
small areal extent appear to have a greater impact on changes in
ground-water quality than do the typical cyclonic system of long
duration, low intensity, and large areal extent.
6. The least changes in chemical quality and soil moisture occur
C-6
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in the vicinity of large trees and is related to
evapotranspiration. Transpiration by large deep rooted trees can
be great enough to influence the regional direction of ground-
water flow.
7. At least some earth materials that are assumed or appear to
be of low hydraulic conductivity are not; they are in the range
of sandstone. This is due to fractures.
8. It is inappropriate to assume a single value for the
background concentration of some chemical parameters, even if the
area is very small.
9. The hydraulic gradient, flow direction, and ground-water
velocity in shallow aquifers can change dramatically from one
season to another and, to a smaller extent, from one day to the
next.
10. Hydraulic conductivity may be substantially greater
vertically than horizontally.
11. Fully penetrating wells reflect concentrations that are
either higher or lower than other wells that sample a much
smaller interval.
12. Ground-water recharge can occur any time it rains,
regardless of soil-moisture conditions.
The conclusions bring to light a number of other questions.
If specific conductance, for example, naturally range over an
order of magnitude, what is the background concentration? Rather
than a finite number, is it not a range? What effect do these
conclusions have on the accepted schemes and practices of
sampling, monitoring, regulatory control, and aquifer
restoration? Should one sample a shallow well immediately
following a convective storm in order to determine the highest
concentration or sample during a long dry spell in order to
obtain a low concentration? Since the data base indicates that
removing even a small volume from a well might cause leakage of
more highly mineralized or less mineralized water from overlying
or underlying zones, should well purging be reexamined? Should
monitoring wells be fully penetrating, completed at discrete
points, or both?
It is evident from the data present above that there is a
considerable degree of variance in chemical quality. In this
case, the constituents are measured in concentrations of
milligrams per liter. What is the significance of the variance
when concentrations are measured at a scale of micrograms per
liter? Might it have a major impact on aquifer restoration
C-7
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schemes and legal actions?
Perhaps tentative answers to these questions will come to
light as the project continues, but whatever the final
conclusions are, it is evident that regulatory agencies need to
address some philosophical questions relative to monitoring,
sampling, and the meaning of background concentration and that we
need to return to the fundamentals of hydrogeology and field
investigations.
Acknowledgments
The data on which this report is based was obtained through
the arduous, time consuming, frustrating, and seemingly thankless
work accomplished by graduate students, past and present, namely,
David Hagen, Blythe Hoyle, Randall Ross, and Hike Nelson.
Neither rain nor snow, heat or cold could reduce their
enthusiastic participation...at least not very much.
References
Growitz,D.J., and O.B. Lloyd, Jr. 1971. Relationship between
ground-water levels and quality in shallow observation
wells, Muddy Creek basin, southeastern York County,
Pennsylvania: U.S. Geol. Survey Prof. Paper 750-D, pp.
D178-D181.
Hagen, D.J., 1986, Spatial and temporal variability of ground-
water quality in a shallow aquifer in north-central
Oklahoma: unpubl. M.S. thesis, Graduate College, Oklahoma
State University, 19lp.
Katz, B.G., S.E. Ragone, and J.B. Lindner. 1978. Monthly
fluctuations in the quality of ground water near the water
table in Nassau and Suffolk Counties, Long Island, New
York: U.S. Geol. Survey Water-Resources Invest 78-41, 38
P.
Pettyjohn, W.A. 1971. Water pollution by oil-field brines and
related industrial wastes in Ohio: Ohio Jour. Sci., v. 71,
no. 5, pp. 257-269.
Pettyjohn, W.A. 1976. Monitoring cyclic fluctuations in ground-
water quality: Ground Water, v. 14, no. 6, pp. 472-480.
Pettyjohn, W.A. 1982. Cause and effect of cyclic changes in
ground-water quality: Ground Water Monitoring Review, v.
2, no. 1, pp. 43-49.
Pettyjohn, W.A., D.J. Hagen, Randall Ross, and A.W. Hounslow,
1986, Expecting the unexpected: 6th Nat. Symp. and Expo, on
Aquifer Restoration and Ground Water Monitoring, Nat. Water
Well Assn., pp. 196-215.
C-8
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Figure 1. General features of the field site.
C-9
-------
Figure 2. Well construction details.
C-10
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-4.00
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871
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1986
Figure 3* Hydrograph of a well 14 feet deep and precipitation.
C-ll
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c-ie
-------
WATER LEVEL ELEVATIONS
2 APRIL 1986
I—i—i 1—i—|
O 10 FEET 40 50
GRADIENT: 0.003 S45W
Figure 5. Water-level map for April, 1986.
C-13
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Well C—5, Elevation at pad 884.37
-9.00
-9.20
-9.40
-9.60
o -9.80
m -10.00 +
cr
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7
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I
O
I | | | | I I i i ¦ ¦ ¦ ... -
iiiiiiiiIiiiiiiiiiii|iiiiiiiihiIiiiiiiiiiii|iiiiiiiiiiiIiuiiiiiiii|i Aiiiiii»iii|iiiiiiiiinliiiiiii)iii|iiimiiiiiliiiiiiiii|iiiiniiiiiliiinii»iii«ii»iiilin|iim|'»l""""l' 4"
10 "*
8
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11 12 13 14
Time (days)
July, 1986
15 16 17
Figure 6. Daily fluctuation of water level in a well 14 feet deep in July, 1986.
-------
Sjef J.J.M. Staps
C-15
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Bvalnatlon of research projects concerning biological in situ
treatment of co"«-*ini Tinted soil and groundwater
Fellowship project, associated with the NATO-CCHS Pilot Project on Remedial
Action Technologies for Contaminated Soil and Groundwater.
Sief Staps
RIVM (National Institute of Public Health and Environmental Protection)
P.O. Box 1
3720 BA bilthoven
the Netherlands
State of the art in the Netherlands
In the Netherlands, introduction of in situ biorestoration of contaminated
soil on full scale took place in recent years. RIVM and TNO (Netherlands
Organization for Applied Scientific Research) are preparing a full-scale
clean-up by means of a study and extensive experiments on laboratory-scale
since 1985. The full-scale clean-up is planned to be started in 1988.
Nowadays, in the Netherlands application of in situ techniques is focussed
on washing, circulating and cleaning of the groundwater, while, especially
in recent years, increasing interest is shown for real biorestoration in
the soil as well. Optimization of environmental conditions is carried out
by oxygen supply, addition of nutrients and circulating of the water.
The Fellowship project
Objective
In 1987, a fellowship of NATO's Committee on the Challenges of Modern
Society was awarded to Sjef Staps to be associated with the CCMS pilot
project on Remedial Action Technologies for Contaminated Land and
Groundwater. The objective of the project is to integrate and evaluate
results of on-going and recently ended research projects for biological in
situ treatment of contaminated soil and groundwater. The project will
result in a determination of optimal process conditions and a determination
of conditions for technical equipment. The information can be used for
different projects within a short time. Finally, the Fellowship will
encourage the development and sensible appliance of this technique.
C-16
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Vork plan
The realization of the Fellowship project will be achieved by visitation of
a range of (research) projects in this field. Planned are visits in the
Netherlands, West-Germany and the USA. Because there is more experience
with this technique in the USA, emphasis will be put on American rather
than European projects. Information, results and data is to be obtained
from the experts involved. Total information will be arranged, and
conclusions will be drawn, resulting in a final, public report and which
will be sent, among others, to all institutes and companies which have been
visited. Results will be presented at a NATO-CCMS meeting on "Demonstration
of Remedial Action Technologies for Contaminated Land and Groundwater".
Schematization of information
Technology of in situ biorestoration can be divided in mainly three
different fields of knowledge: a. Microbiology
b. Hydrology
c. Technical execution
Microbial aspects will form the basis and set the parameters for hydrology
and technical execution. Although all three parts will be taken into
account, emphasis will be put on microbial aspects, and relevant
environmental conditions.
The total gathered information can be schematized as shown in scheme 1.
The gathered information will schematically be arranged, in order to
describe the international state of the art with regard to technology and
cost-efficiency of in situ biological treatment techniques for contaminated
soil and groundwater. Conclusions will be drawn for for instance optimal
environmental conditions and attainable degradation rates.
Significance of report
The Fellowship will result in a report which describes the international
state of the art with regard to technology and cost-efficiency of in situ-
biological treatment techniques for contaminated soil and groundwater. It
will support and contribute to the integration of results and evaluation of
technologies for treatment of contaminated soil and groundwater.
C-17
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The Fellowship will encourage international collaboration and will be a
great help to attune new Dutch research projects to foreign research and
reverse.
In the final report it will be shown which clean-up results can be gained,
starting from the point of the characterization of the contaminated site
and regarding certain environmental conditions.
Besides, an overview will be shown concerning the research activities in
this field in Europe and the USA. In the final conclusions, directions will
be given for future research; "white spots", on which research topics
should be focussed in future, will be indicated.
A few rgnartg at the conference at Bllthoven.
At the international conference at Washington D.C. in 1987, this fellowship
project was accepted for the NATO/CCMS study. The proposal of the attendees
of the meeting was to enlarge the project by not only visiting projects in
the Netherlands, West Germany and the USA, but also in other countries that
are participating in the study. Verification made clear that it would be
useful to visit the UK, Denmark and Canada because there are interesting
activities in the field of in situ biorestoration in these countries too.
By now, we are trying to get more funding from NATO in Brussels, in order
to make this enlargement possible.
In September 1988, in situ biorestoration projects have been visited in
West Germany, and contacts with Dutch projects have been continued. The
visits in the USA have been planned for February 1989.
The results of the fellowship project will be published in a final report
and presented at the international NATO/CCMS conference in Canada in 1989.
C-18
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Scheme 1. SchematizaCion of information.
tMIBWir PEP gTTE
Exacuter:
Contact:
Location:
Date:
1. Introduction
1.1. Background of the contamination (tank, pipeline, cause of leakage)
1.2. Objective of the reclamation (e.g. to reach certain residual concentrations)
1.3. Present state of affairs
2. Preliminary characterization
2.1. Site characterization
2.1.1. Geology (soil characterization)
2.1.2. Hydrology (groundwater level, groundwater movement)
2.1.3. Contaminants (extent, type, substrate accessibility, presence of toxicants)
2.1.4. Microbiology (indigenous population)
2.1.5. Nutrients (concentration, type)
3. Preliminary treatability research
3.1. Limiting environmental parameters (pH, temperature, dissolved oxygen levels, nutrient
concentrations, concentration of contaminants)
3.2. Mobilization of the contaminants (use of dispersants)
3.3. Microbial degradation enhancement study
4. Design of treatment oystca
4.1. Description of installation (including water treatment system)
A.2. Free product recovery
4.3. Oxygen supply
4.4. Nutrient supply
4.5. Other supply
4.6. Infiltration / withdrawal (hydrologlcal isolation)
4.7. Hydrologlcal isolation / effectiveness
5. Monitoring
5.1. Contamination and degradation products
5.2. Nutrients
5.3. Oxygen
5.4. Redox conditions
5.5. Microbial numbers / metabolic activity
6. Analytical procedures
6.1. Sampling procedures (frequency, number of samples)
6.2. Chemical analysis
6.3. Microbiological enumeration and characterization
7. Results and conclusions
7.1. (Bio-)degradation results; residual concentrations (soil / groundwater)
7.2. Monitoring / sampling procedures / analysis
7.3. Use of treatment chemicals
7.4. System performance
7.5. Clean-up period
7.6. Cost of in situ treatment
7.7. Re-use of the site
7.8. Requirements for full scale in situ treatment
8. Bottle-necks
8.1. Injection / extraction system (hydrological isolation)
C-19
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8.2. Oxygen supply and source
8.3. Precipitation and clogging
8.4. Metals mobilization
8.5. Bioavailability of contaminants
8.6. Other bottle-necks
9. Bimonrch meada
9.2. Use of alternative oxygen source
9.3. Inoculation of micro-organisms
9.4. Application of dispersants
9.5. Monitoring (test methods, analytical methods)
9.6. Modelling; predictability of clean-up efficiency
9.7. Other research needs (in general, specific, preliminary)
10. Literature.
Appendix: slides, photographs, schemes etc.
C-20
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James Gossett
C-21
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BIODEGRADATION OF DICHLOROMETHANE
UNDER METHANOGENIC CONDITIONS
by
James M. Gossett and David L. Freedman
School of Civil & Environmental Engineering
Hollister Hall
Cornell University
Ithaca, New York 14853
Presented at the Second International Meeting,
NATOfCCMS Pilot Study on Demonstration of
Remedial Action Technologies for Contaminated Land and Groundwater
November 7-11,1988
National Institute of Public Health and Environmental Protection
Bilthoven, the Netherlands
C-22
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I. INTRODUCTION
The research reported herein is part of a larger, USAF-sponsored effort to investigate the
potential for biodegradation of four chlorinated solvents under methanogenic conditions:
tetrachloroethylene (PCE), trichloroethylene (TCE), chloroform (CF), and dichloromethane
(DCM). In this present paper, we focus on our investigations with DCM.
A. Objectives and Scone of Work
The broad goal of our research effort is to investigate the fundamental factors
influencing the biodegradation of dichloromethane (DCM) by enrichment cultures grown under
methanogenic conditions. Gaining a deeper understanding of how DCM is degraded under such
conditions will markedly improve the chances of successfully employing bioremediation
technologies.
More specifically, our research objectives are:
1. To determine if DCM can serve as a growth substrate.
2. To further elucidate the pathways by which DCM is degraded under
methanogenic conditions, including the construction of an oxidation/reduction
balance. This will necessitate measuring hydrogen levels during DCM
degradation.
3. To determine which class of organisms — methanogens or nonmethanogens
— are responsible for mediating DCM degradation.
4. To develop a kinetic model of DCM degradation in mixed cultures.
5. To evaluate the capability of the DCM enrichment cultures to degrade other
halogenated aliphatic compounds, specifically diiodomethane and
dibromomethane.
Surprisingly little information is available in the literature concerning the
degradation of DCM under methanogenic conditions. The progress we have made thus far
includes: development of a DCM-degrading enrichment culture; correlation of DCM degradation to
methanogenesis; and preliminary determination of degradative pathways. Considerable work
remains, particularly with regard to determining whether or not DCM can serve as a growth
substrate. We plan further studies aimed at delineation of biodegradative pathways (including the
role of hydrogen) and causative organism(s), the kinetics of degradation, the ability of the DCM-
enrichment culture to degrade other chlorinated aliphatics, and the ability of these cultures to
function in an immobilized cell reactor.
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B. Environmental Significance of PCM
Annual 1985 U. S. production of DCM was approximately 250,000 metric tons,
about one quarter of the four chlorinated methanes manufactured, and three times the output of
TCE. Principal uses include aerosol applications (29%), paint stripping (27%), the blowing agent
for flexible foams (10%), vapor degreasing of metal parts (9%), and decaffeination of coffee and
solvent extraction of foods (2%) (Kirk-Othmer, 1979; Chemical Week, 1987). The consequence
of such widespread use is that DCM is now an important contaminant of U. S. drinking water.
Though not the most frequently occurring chlorinated aliphatic at hazardous waste sites (this
"honor" goes to TCE), DCM is among the more difficult to remove by conventional air stripping
because of its relatively low Henry's constant — 1.69 L atm/mol at 20°C, versus 2.77 for
chloroform (CF), 7.19 for TCE, 13.2 for PCE, and 23.4 for carbon tetrachloride (CT) (Gossett,
1987).
Until recently, DCM was considered one of the least toxic chlorinated solvents
available. For this reason DCM was expected to gradually replace other more toxic and flammable
solvents, including benzene, after it was shown to be a carcinogen (Kirk-Othmer, 1979). This
perception began to change in 1985, when tests by the National Toxicology Program with mice
revealed that DCM caused lung and liver cancer, among other problems. There is not yet any
epidemiological evidence to show that DCM is a human carcinogen. Nevertheless, labeling of all
products containing DCM — warning of its possible health hazard — is now required by the
Consumer Product Safety Commission (CPSQ. A consumer group is currently suing CPSC to
force a complete ban of all DCM use (Chemical Week, 1987 & 1988). Thus, in a span of just over
one decade, DCM has gone from a rising star in the halogenated solvents market to a compound
suspected of significant advene health effects.
CT is the only chlorinated methane for which a specific primary drinking water
regulation has been set (5 pig/L). CF is indirectly covered by the trihalome thane combined limit of
100 |ig/L. DCM will soon be regulated under the 1986 amendments to the Safe Drinking Water
Act It is among 14 volatile organic chemicals for which an enforceable standard must be set by
June 1989 (Sayre, 1988).
II. BACKGROUND: DEGRADATION OF DCM UNDER METHANOGENIC
CONDITIONS
Given the environmental significance of DCM, surprisingly little information is available
concerning its behavior in methanogenic environments. What is known from previous research is:
1) at high enough concentrations DCM inhibits methanogenesis; 2) DCM can be biologically
degraded under methanogenic conditions; and 3) DCM is a product of CF degradation.
Inhibition of methanogenesis by DCM has been demonstrated with mixed batch cultures.
Thiel (1969) observed 50% inhibition of methane yield from washed cell suspensions fed 5.4 mM
ethanol, when exposed to 100 mg/L of DCM. A seven fold higher dose was required before
Second International Meeting, NATO/CCMS Pilot Study
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methane production was completely stopped. Inhibition of methanogenesis led to an accumulation
of hydrogen. Stuckey et al. (1980) and Vargas and Ahlert (1987) reported much lower DCM
doses required to cause 50% inhibition in batch studies — 14 mg/L and 0.5 mg/L, respectively.
However, comparison of these results is impossible because biomass concentration data were not
provided, and die type of inoculum and length of incubation varied.
Semicontinuous digesters and chemostats have also been used to demonstrate the inhibitory
effect of DCM on methanogenesis. However, inhibition typically diminishes as the cultures
acclimate to continuous DCM addition. Stuckey et al. (1980) observed the ability of a mixed
culture to acclimate even when the digester concentration of DCM reached 10 mg/L. With
continuous flow through acclimated acetate and propionate enrichment cultures, Bhattacharya and
Parkin (1988) were able to feed DCM at a concentration of 80 mg/L without noticeable impact on
methane production; DCM concentration in the reactors was maintained below 7 mg/L. The
inhibitory effect of DCM declined as reactor solids retention time increased. Slug additions of
DCM to unacclimated cultures caused system failures at reactor concentrations above 44 mg/L
(lower levels were not tested). Although it is known that DCM inhibits methanogenesis, no
studies were found which investigated the mechanism of inhibition.
Degradation of DCM under methanogenic conditions was demonstrated conclusively by
Gossett (1985), using batch serum bottle experiments. Acclimated mixed cultures rapidly
consumed approximately 8 mg/L spikes of DCM. New acclimation periods were required
whenever the cultures degraded DCM but were not respiked within several hours. The principal
products of [14C]DCM (obtained from [14C]CF; DCM from CF discussed below) degradation
were 14CC>2 (73%) and an undefined nonstrippable residue (21%), about 50% of which was
soluble. CF was shown to be a very potent inhibitor of DCM degradation.
Less direct evidence for biodegradation of DCM comes from studies with continuous flow
reactors. Stuckey et al. (1980) attempted a mass balance of DCM additions; after accounting for
losses to the gas phase, they concluded that the unaccounted for DCM (>90%) was biologically
transformed. However, no controls were used to test for sorption or other abiotic processes.
Bhattacharya and Parkin (1988) performed a similar analysis but used serum bottle studies to
exclude the possibility of sorption or chemical transformation. Neither study investigated the
products of the presumed biotransformation. Knowledge of the products is extremely important
when evaluating degradation of halogenated organics, since it is possible for the products to be as
great, or greater a risk to the environment. Accumulation of vinyl chloride from reductive
dechlorination of PCE and TCE is a good example of this phenomenon.
The formation of DCM from degradation of CF in a mixed culture derived from sewage
sludge was demonstrated by Gossett (1985). Using [14C]CF, the major degradation products
were found to be roughly equal amounts of [l4C]DCM and 14CC>2- This stoichiometric
relationship indicated CF was degraded via a disproportionation, i.e., the reducing equivalents
gained by oxidation of CF to CO2 were used to reduce CF to DCM. Degradation of the DCM
formed did not occur, even long after CF had disappeared, unless the system was reinoculated
with a DCM degrading culture.
Second International Meeting, NATO/CCMS Pilot Study
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A pure culture of Methanobacterium thermoaiaotrophicum has been used to test degradation
of CF. After 8 days of incubation, only one percent of the CF was transformed, with DCM the
only product measured. Growth on CF was considered poor (Egli et al., 1987).
No studies were found which reported DCM as a product of carbon tetrachloride
degradation under methanogenic conditions.
III. SUMMARY OF PROGRESS TO DATE
A. F.ynerimental Strategy
The starting point for this research was the development of a mixed culture capable
of degrading DCM under methanogenic conditions. This was accomplished using the mixed liquor
from a laboratory digester. The digester had been started with sewage sludge from the Ithaca, NY
Wastewater Treatment Plant, then operated in a semicontinuous mode with a 10 g COD/L synthetic
substrate, designed to maintain a diverse population of anaerobes. DCM degradation was achieved
in a culture derived directly from the lab digester. There was most likely an element of luck in this
procedure, since it was unknown the degree to which the sewage treatment plant digester was
routinely exposed to DCM. The source of inoculum for biodegradation studies often determines
the probability of success (Cook et al., 1983).
The DCM degrading mixed liquor was then used to inoculate a series of enrichment
cultures. The purpose of the enrichments was to eliminate as many of the organisms as possible
which weren't involved in DCM degradation, as well as to remove significant amounts of
extraneous, undefined organic matter. Developing enrichment cultures has enabled progress in
correlating DCM degradation to methanogenesis, and in analysis of the pathway(s) by which DCM
has been degraded.
B. Materials and Methods
Chemicals and Radioisotopes. DCM was obtained in neat form (99 mol %
pure; Fisher Scientific); Chloromethane (CM) was purchased dissolved in methanol (200 Hg/mL,
1 mL ampule; Supelco, Inc.). [14C]DCM (Sigma Radiochemical) was diluted in ISO mL distilled
deionized water and stored in a 160 mL serum bottle, capped with a Teflon™ lined rubber septum.
The [14C]DCM stock solution contained 2.93 x 107 dpm/mL (4.68 p.moles DCM/mL); GC
analysis of the [14C]DCM stock bottle headspace indicated the presence of an unidentified
contaminant, which was shown not to be radiolabeled. There was also no indication that this
contaminant interfered (e.g., as an inhibitor) with the DCM degradation studies. ScintiVerse-E™
(Fisher Scientific) liquid-scintillation cocktail (LSQ was employed for [14C] assays.
Cultures and Enrichment Procedures. All experiments were conducted at
35"C, under quiescent conditions, in 160-mL serum bottles to which 100 mL of liquid was added.
Second International Meeting, NATO/CCMS Pilot Study
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The bottles were sealed with slotted grey butyl rubber septa and aluminum crimp caps (Wheaton
Scientific). Virtually no loss of DCM was observed from water controls (WC) which used these
septa; they were less permeable to oxygen than TeflonTM-lined rubber septa, were easier to
puncture, and maintained better flexibility following autoclaving. [They were not used in
PCE/TCE studies because significant losses of these compounds (and their reductive
dechlorination products) were noted in water controls.]
Autoclaved seed controls (ASC) were used to evaluate the degree of sorption and
abiotic transformations of DCM. When these phenomena were consistently shown to be
negligible, use of the ASCs was discontinued.
Semicontinuous operation of the enrichment cultures was practiced with several of
the bottles which were actively degrading DCM. This entailed removal of 4.0 mL of well mixed
liquid and addition of 3.95 mL of new basal medium (containing 50 mg/L of an auxiliary substrate
— i.e., acetic acid (HAc), sodium formate, methanol, or glucose) plus 0.05 mL of DCM saturated
water (=220 )imoles/mL). When semicontinuous operation was not practiced, the disappearance
of DCM was followed by addition of only DCM saturated water.
Analytical Methods. Analysis of volatile organics was performed by gas
chromatographic (GC) analysis of a 0.5-mL headspace sample, using a flame-ionization detector
(FID) in conjunction with a 3.2-mm x 2.44-m stainless-steel column packed with 1% SP-1000 on
60/80 Carbopack-B (Supelco, Inc.), as previously described (Gossett, 1987).
Degradative pathways were examined through semi-continuous addition of
radiolabeled [14C]DCM to enrichment cultures. Following various periods of operation,
distribution of 14C among suspected DCM degradation products was determined. Volatile forms
(DCM, CM, and CH4) were assayed for *4C via a GC/combustion technique. A 0.5-mL
headspace sample was injected to the GC. Instead of going to the FID, the GC column effluent
was routed to a CuO-filled, quartz combustion tube (6-mm i.d. x 10-mm o.d. x 39-cm length) held
at 800*C by means of a tube furnace. Passing through the CT, the well-separated peaks of
volatile compounds were converted to CO2, then routed through a porous-glass diffuser into
separate glass test-tube traps containing 3.0 mL of 0.5 M NaOH. TTiese traps were manually
exchanged as each peak eluted; their contents were subsequently counted in 15 mL of ScintiVerse-
E™. Henry's constants for DCM and CM at 35°C — needed for calculation of total dpm based on
a 0.5 mL headspace injection — were obtained from Gossett (1987).
The GC/CT system enabled accounting for 14C among several volatile organic
forms. A complete mass balance on 14C required determination of two additional forms: 14CC>2
and [14C]nonvolatiles. These were measured by first injecting 1.5 mL of 5 M NaOH into a serum
bottle which was to be assayed, raising the pH above 10.5 to force virtually all CO2 into the
aqueous phase. A 20-mL aliquot of the alkaline contents was then transferred to a 30-mL
stripping chamber. Once sealed, the pH of the aliquot was lowered to 4.4 by injecting 0.4 mL of
glacial acetic acid through a septum in the chamber's headspace. The chamber liquid was then
sparged for 30 minutes with nitrogen (50-60 mL/min) through a porous-glass diffuser (ASTM
Second International Meeting, NATO/CCMS Pilot Study
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porosity C, 25-50 Jim). Gaseous effluent from the stripping chamber passed through a tube
containing 0.25 g of Tenax™ (to trap [14C]volatile chlorinated compounds); through a second
diffuser identical to the first; and into a 30-mL gas-absorption chamber containing 20 mL of 0.5 M
NaOH to trap 14C02. After 30 minutes of sparging, the contents of both the stripping and
absorption chambers were each assayed for 14C.* The dpm remaining in the stripping chamber
represented what we termed, "nonstrippable residue" (NSR). It was further partitioned into
soluble (i.e., "SNSR") and insoluble fractions by centrifuging at 15 000 rpm for 10 minutes.
[14C] activity was assayed with a Beckman model 9800 liquid scintillation counter.
Corrections for counting efficiency were made according to a quench curve (sample H# versus
efficiency), generated with standards (Beckman Instruments, Inc.) ranging from H#s of 1.8-308.4
and efficiencies of 40-94%. A counting window of 200-670 was used, to minimize the effect of
chetniluminescence associated with the lower energy spectrum.
In all of the bottles to which [14C]DCM was added, a significant portion of the
activity was recovered as soluble, nonstrippable residue (SNSR). HPLC analysis was employed
to determine the composition of most of die [14C]SNSR, similar to die method described by Zinder
and Koch (1984). A Hewlett Packard 1090 HPLC was used to pump 250 nL samples through a
300 mm HP X-87H ion exchange column (Bio-Rad Laboratories) and into an LC-25 refractive
index detector (Perkin-Elmer). The mobile phase (13mM H2SO4) was delivered at 0.7 mL/min.
As fractions eluted from the detector, they were collected in 15 mL of liquid scintillation cocktail.
By operating the ion exchange column at two temperatures (30 and 65°C) it was possible to resolve
formate, formaldehyde, acetate, propionate, methanol, isobutyrate, butyrate, and ethanol. For
example, although methanol and propionate coeluted at 30°C, they were well resolved at 65°C. By
collecting fractions at both temperatures it was possible to deduce the identity of the compounds.
Collection intervals for each compound were determined by injecting 100 nL of =100 mM
samples of pure compound, collecting 0.5-minute fractions eluting from the refractive index
detector, then reinjecting each fraction to determine the amount of compound present The
efficiency of the HPLC method was evaluated by comparing the dpm from a direct addition of
SNSR to scintillation cocktail with the total dpm recovered from fractions collected off the HPLC.
For the three bottles analyzed thus far, the degree of recovery has averaged 76.2%, 85.2%, and
97.9%, respectively.
When all categories of recovered [14C]-species (i.e., DCM, CM, CH4, CO2. and
NSR) are summed, the overall efficiency of accounting for added 14C averaged 92.8% for seeded
botdes and 98.1% for water controls (WC).
C. Results and Discussion
Development of Enrichment Cultures. The mixed culture obtained directly
from the laboratory digester required about 10 days of acclimation before DCM degradation began
* Confirmation of *4C02 in the absorption chamber was made by adding 1.S g of Ba(OH)2 to 23 mL from the
trap, shaking vigorously, centrifuging at IS 000 rpm for 10 minutes, then counting a 2.0-mL sample of the
centrate. The centrate dpm never exceeded 2% of the presumptive ^4C02 dpm-
Second International Meeting, NATO/CCMS Pilot Study
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(Figure 1). The initial DCM dose of 8 pinoles resulted in a nominal DCM concentration of 6.8
mg/L, or an aqueous concentration of 6.3 mg/L when partitioning to the headspace is taken into
account Unless DCM was added either before it was completely degraded, or shortly thereafter, a
new acclimation period of four to seven days was required before DCM degradation resumed. CM
was detected at low levels only during the first 46 days. Losses of DCM from the water control
(WC) and autoclaved-seed control (ASC) were minimal over the 82 days of incubation, clearly
indicating that a biological process was responsible for the repetitive disappearance of DCM from
the seeded bottle.
The mixed culture described above was used to inoculate a series of enrichments.
Each bottle contained 3 mL of inoculum, plus 97 mL of basal medium to which 50 mg/L of
auxiliary substrate (acetic acid, sodium formate, methanol, or glucose) was added; auxiliary
substrate was not present in one set of bottles. One of the three replicate acetate enrichment
cultures was by far the most successful at rapidly degrading DCM (Figure 2). Following an
acclimation period of 64 days, the rate of DCM degradation accelerated; by day 79, DCM additions
of 10-11 (imoles were typically consumed within three or four days. On two occasions, extra HAc
(i.e., in addition to the HAc supplied during semicontinuous operation) was provided when DCM
degradation faltered.
Figure 3 shows the pattern of DCM degradation in the other enrichment cultures.
The sodium formate enrichment was moderately successful, but never achieved as rapid a rate of
DCM degradation. The methanol enrichment bottle began to improve after 300 days, although the
accelerated rate of DCM consumption wasn't maintained. Relatively minor amounts of DCM were
consumed in the glucose and no auxiliary substrate bottles.
Results from these second generation cultures suggest that an auxiliary substrate —
preferably HAc — was required for the development of an active DCM degrading culture.
However, results described below clearly demonstrate that once rapid DCM degradation was
established, it was sustainable for extended periods (i.e., >100 days) without the addition of any
auxiliary substrate. The role of an auxiliary substrate in DCM degradation under methanogenic
conditions remains unclear, as does the reason why the HAc enrichment outperformed the others.
Correlating DCM Degradation with Methanogenesis. Having demonstrated
that DCM can be degraded under methanogenic conditions, an experiment was undertaken to
ascertain if the disappearance of DCM was in any way linked to methanogenesis. The bottle
depicted in Figure 2 was used for this purpose. Beginning on day 197, the only carbon source
added to this bottle was DCM; additions of HAc and yeast extract were stopped (Figure 4). On the
same day, the bottle's headspace was purged, making it possible to monitor methane output with
the flame ionization detector (FID). (The upper detection limit for methane eluting from the 1%
SP-1000 Carbopack B column to the FID was approximately 0.293 (imoles per 0.5 mL headspace
injection, amounting to 35.2 (imoles per serum bottle.) The absence of HAc did not deter the rate
of DCM degradation. In fact, the rate improved slightly; between two and three days were required
to completely degrade 10-11 (imoles of DCM, compared to three or four days with HAc present
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CO
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FIGURE 1: DCM degradation in a 1st generation culture; no auxiliary substrate added.
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FIGURE 2: DCM degradation in a 2nd generation acetate enrichment culture.
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FIGURE 3: DCM degradation in 2nd generation acetate enrichment cultures,
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PHASE 1
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FIGURE 4: DCM degradation in a 2nd generation acetate enrichment culture, in the absence of acetate
additions.
-------
By day 215, six repetitive additions of DCM had been degraded, amounting to
61.34 |j.moles of DCM consumed. Over the same 17 day interval, 31.38 (jmoles of methane were
produced, or 0.51 mole of methane produced per mole of DCM consumed. The question
remained, however, whether the methane produced was related to the DCM degraded, or the result
of organic matter left over from previous operation of the bottle. This was addressed by halting
DCM additions while continuing to monitor methane production. Between days 215 and 217,
1.82 iimoles of methane were produced; only 0.94 p.mole was added over the next six days
(Figure 5). Thus, the absence of DCM (the only carbon source added since day 197) resulted in a
levelling off of methane output
DCM was added again on day 223. An acclimation period was observed before a
rapid rate of DCM consumption resumed (Figures 4 and 5). When it did, DCM consumption and
methane production were once again linked. With 17 cycles of DCM consumption completed, the
best fit line through the data indicated 0.504 mole of methane produced per mole of DCM
consumed (Figure 6). DCM additions were stopped on day 275, and methane output
correspondingly levelled off a second time (Figure 5).
The ratio of methane production to DCM consumption observed experimentally was
very close to the 0.50 ratio expected based on stoichiometric conservation of electrons:
+0
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The observed correlation of DCM degradation and methane production does not
elucidate the pathway by which DCM was degraded. At one extreme, it is possible that the
methane evolved was derived directly from the DCM degraded. At the other extreme, it is possible
that all of the DCM was oxidized to CO2. which then entered the large pool of carbonates present
in the basal medium. The reducing equivalents gained from oxidation, possibly released as
hydrogen, would then be used to produce methane. Radiotracer studies, described below, were
undertaken to investigate these possibilities.
Pathways of DCM Metabolism. Six third-generation cultures were started
for use in radiotracer experiments. All were inoculated (10%) with the second generation culture
depicted in Figure 2. Thus far, four have been sacrificed for [14C]DCM analysis. Interpretation of
the radiotracer results can only be done with a knowledge of how each bottle was treated prior to
[14C]DCM addition:
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TIME (days)
FIGURE 5: Cumulative DCM consumption and methane production in a 2nd generation acetate
enrichment culture, in the absence of acetate additions.
-------
DCM CONSUMED (micromoles)
FIGURE 6: Correlating DCM degradation and methane production in a 2nd generation acetate
enrichment culture, in the absence of acetate additions.
-------
Bottle ffl-1 was setup with SO mg/L of acetic acid and yeast extract After 24 days,
most of the initial 6 nmoles of DCM were consumed (Figure 7). Semi-continuous operation was
then begun; 4.0 mL of mixed liquor was withdrawn, followed by addition of 3.95 mL of basal
medium (containing 50 mg/L each of acetic acid and yeast extract) plus 0.05 mL of DCM-saturated
water. Whenever the DCM level approached zero, this process was repeated. Thus, the
distinguishing feature of Bottle m-1 was that it continued to receive acetic acid, along with
repetitive additions of DCM. On day 45, the usual addition of nonlabeled DCM was accompanied
by 2.93 x 106 dpm of [14C]DCM. Five days later all of the DCM was degraded and analysis of
the distribution of [ 14C]compounds began. (Results are summarized in a later paragraph).
Bottle HI-2 was operated similarly until day 47, when DCM additions were
continued without acetic acid or yeast extract (Figure 8.a). The headspace was purged on day 53
to allow for quantification of the amount of methane produced. As previously demonstrated, DCM
degradation was linked to methane production. The cessation of DCM additions resulted in a
levelling off of methane production, indicating the absence of electron donors other than DCM
(Figure 8.b). When DCM additions were resumed, methane output rose in concert with DCM
degradation. Over the period from day 53 through 104,0.55 mole of methane was produced per
mole of DCM consumed (Figure 8.c). This was essentially the same result as obtained from the
second generation culture described in Figure 4, 5, and 6. On day 102, the usual addition of
nonlabeled DCM was accompanied by 2.93 x 10* dpm of [14C]DCM. Two days later all of the
DCM was degraded and analysis of the distribution of [14C]compounds began. (Results are
summarized in a later paragraph.)
Bottle m-3 was setup with 38 mg/L of acetic acid and yeast extract instead of the
usual 50 mg/L. From that point on, only DCM was added (Figure 9.a). Beginning on day 28, the
amount of DCM evolved and methane produced was quantified. The accumulation of methane was
directly related to cumulative DCM consumption, as expected (Figure 9.b). Between days 28 and
36,0.52 mole of methane was produced per mole of DCM consumed (Figure 9.c). On days 36,
38 and 51,50 jxmoles of 2-bromoethanesulfonate (BrEtS) was added. BrEtS had no effect on the
rate of DCM consumption, but it did reduce methane output by approximately 75%. (Formation of
ethylene was also noted, most likely a consequence of BrEtS degradation. Conversion of BrEtS to
ethylene by pure cultures of methanogens has been documented by Belay and Daniels, 1987.)
Thus, DCM was being degraded by a nonmethanogen, or possibly by a methanogen unaffected by
the relatively low dose of BrEtS. On day 51, the usual addition of nonlabeled DCM was
accompanied by 2.94 x 106 dpm of [14C]DCM. Two days later all of the DCM was degraded and
analysis of the distribution of [14C]compounds began. (Results are summarized in a later
paragraph.)
Bottle m-4 was set-up with a 10% inoculum, plus 50 mg/L of acetic acid and yeast
extract. For the first 57 days, this bottle was operated semi-continuously (with HAc and yeast
extract) whenever DCM was consumed. Thereafter, none of the culture was removed and no new
basal medium was added; only DCM-saturated water was added whenever DCM became depleted.
DCM additions were stopped on day 101, leading to a cessation of methane production. Methane
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TIME (days)
FIGURE 7: DCM degradation in a 3rd generation enrichment culture, bottle III-l; radiotracer added
along with the final DCM spike.
-------
DCM Only Purge
I4 "
Add [14-CJDCM
50 60
TIME (days)
Stop adding DCM
CH4PRODUCED
DCM CONSUMED
Purge, add DCM
75 80 85
TIME (days)
30 40 50 60 70 80 90 100 110 120 130
DCM CONSUMED (micromoles)
FIGURE 8: DCM degradation in a 3rd generation enrichment culture, bottle m-2.
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ui-g
l!
<«
St
Ui
Add 50 iimoles BrEtS
CH4 * -0.362+ 0.521 DCM
R * 1.00
i « ¦ » i ¦ > • i ¦ • ¦ i
40 60 80 100
DCM CONSUMED (micromoles)
120
140
FIGURE 9: DCM degradation in a 3rd generation enrichment culture, bottle ni-3.
C-40
-------
output resumed once DCM degradation started again (Figure 10). On days 231,233, and 235,2-
bromoethanesulfonate (BrEtS) was added in the following amounts: 0.05, 0.50, and 5.0
millimoles. The latter dose was sufficient to completely stop any further methane production.
Initially, the rate of DCM degradation slowed, but it was gradually restored to the rate observed in
the presence of methane production. Between days 235 and 286, 214 micromoles of DCM were
degraded without any methane production (Figure 10). Thus, the distinguishing feature of bottle
III-4 was the consumption of [^C]DCM in the complete absence of methane production.
Methanogenesis was only partially inhibited in bottle IH-3. The final DCM dose on day 284 was
accompanied by 2.87 x 10^ dpm of [^C]DCM. Two days later, all of the DCM was consumed
and analysis of the distribution of [^Cjcompounds began. Results are summarized below.
The distributions of [14C]compounds from degradation of [14C]DCM in the four
bottles are shown in Figure 11. All of the bottles contained at least 60% 14CC>2. In bottles III-l
and III-2,14CH4 was also measured (17.3% and 9.1%, respectively). No 14CH4 was recovered
in either of the bottles — III-3 or III-4 — to which BrEtS had been added, though unlabeled
methane was detected in III-3 (which had received a much lower dose of BrEtS than did IH-4).
[14C]acetic acid was found in all four bottles, but in far greater quantities in botdes III-3 and IH-4.
Furthermore, bottles III-3 and III-4 showed significant amounts of [14C]methanol (5.5% and
11.0%, respectively) . All of the bottles contained a small percentage (2.5% or less) of
nonsoluble, nonstrippable residue (NNSR). The dpm recovered as 14CC>2,14CH4, [14C]acetic
acid, [14C]methanol, and [14C]nonstrippable residue represented between 89% and 98% of the
dpm added as [14C]DCM.
On day 280, the amount of hydrogen present in the headspace of III-4 was
measured using a GC with hot-wire detector. Only 6.2 micromoles were detected, representing
cumulative output since day 235, when the bottle's headspace had last been purged. Over this
same interval (day 235-280), 180 micromoles of DCM were degraded in the complete absence of
methane production. Assuming two thirds of this DCM were oxidized to CO2, as much as 240
micromoles of hydrogen could have been present. The much lower level observed indicates that
the reducing equivalents gained by oxidation of DCM to CO2 were consumed, most likely in the
formation of acetic acid from CO2 by acetogenic bacteria.
Some preliminary conclusions can be drawn from these results:
1. The predominate pathway for DCM degradation was oxidation to CO2.
Thus, of the approximately 0.5 mole of methane formed per mole of DCM
consumed, most of the methane was derived from CO2, not directly from DCM. It
remains to be seen whether or not the reducing equivalents gained by DCM
oxidation are released as hydrogen.
2. Inhibition of methanogenesis with BrEtS in bottles III-3 and IH-4 had no
effect on the rate of DCM degradation. The BrEtS dose used in bottle III-3 (0.5
limol/mL) was apparently adequate to completely inhibit acetoclastic methanogens,
but not enough to completely shut down C02-reducing methanogens. The 50-
Second International Meeting, NATO/CCMS Pilot Study
C-41
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10
©
o
E
o
hm
0
1
>
H
P
<
3
O
900i
800
700-
600*
500*
E 400 -
300
200 i
100
DCM Consumed
Methane Produced
Stop Adding DCM
—i-
50
250
300
TIME (days)
FIGURE 10: DCM consumed & methane evolved versus time (Bottle m-4).
C-42
-------
Nonsoluble NSR
Methanol
Acetic Acid
CH4
C02
BOTTLE#
Summary of Bottle Operation:
IH-1: Operated semi-continuously with HAc for 50 days.
HI-2: Operated semi-continuously with HAc for 47 days, then received only DCM from days 47
through 104. During the latter interval, the average production of methane was 0.55 micromoles
per micromole of DCM consumed
131-3: At start-up it received 38 mg/L HAc, and only DCM thereafter; semi-continuous operation
was never instituted Between days 28 and 36, methane production was 0.52 micromoles per
micromole of DCM consumed On days 36, 38 and 51, 50 micromoles of BrEtS were added
along with DCM. This significantly reduced (but did not stop) methane production without
affecting the rate of DCM consumption.
ni-4: Operated semi-continuously with HAc for 57 days, then received only DCM from days 57
through 286. Between days 57 and 231, the average production of methane was 0.45 micromoles
per micromole of DCM consumed On day 235, 5 millimoles of BrEtS was added, completely
stopping all methane production without slowing DCM consumption.
E
100 i
a
90 "
_i
80 '
<
I-
70-
O
H
60-
1L
50-
O
40 -
H
30"
Z
LU
20 "
O
K
10-
UJ
a
1-1
tll-2
111-3
111-4
FIGURE 11: Distribution of from [14qjdcm degradation in third-
generation enrichment cultures.
C-43
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(imol/mL dose used in bottle III-4 was apparently sufficient to inhibit methanogens
of all types.* Inhibition of acetoclastic methanogens would explain why
accumulation of acetic acid synthesized from DCM occurred in bottles M-3 and III-
4, and why no radiolabeled methane was found in these bottles. Splitting of
radiolabeled acetic acid by a methanogen was the likely source of the radiolabeled
methane measured in bottles III-l and IH-2, which were uninhibited by BrEtS.
Hydrogen-consuming acetogenic bacteria most likely mediated the formation of
acetic acid from DCM.
3. The appearance of [14C]methanol in bottles IH-3 and IH-4 suggests that
methanol was an intermediate in the synthesis of acetic acid from DCM.
Alternatively, a DCM-consuming methanogen may have released methanol, as a
consequence of being inhibited by BrEtS.
These conclusions are summarized in Figure 12.
IV. ON-GOING STUDIES
In order to advance the prospect of using methanogenic systems for treatment of DCM
contaminated water, research is being carried out in both suspended-growth and immobilized-cell
reactors. The suspended-growth studies will allow examination of more fundamental issues. Key
among these are whether or not DCM can serve as a growth substrate, development of a kinetic
model of DCM degradation, further elucidation of the pathways by which DCM is degraded,
investigation of the class of organisms responsible for degradation, and evaluation of the ability of
DCM consuming mixed cultures to degrade other halogenated aliphatics.
The fixed-film reactor studies are oriented more towards the practical issues of how best to
accomplish treatment Foremost in this regard is the capability of the DCM degrading organisms to
attach to fixed-film media. Assuming this is possible, the reactors will be used to evaluate a variety
of treatment conditions, including DCM concentration, variation in hydraulic residence time, and
the effect of other chlorinated aliphatics — particularly CF — on the efficiency of DCM removal.
This research was supported by the U.S. Air Force Engineering and Services Center (AFESC),
Tyndall AFB, FL, under contract no. F08635-86-C-0161.
REFERENCES
Belay, N.; and Daniels, L. 1987. Applied and Environmental Microbiology S3, 1604-1610.
s|i
Zinder et al. (1984) demonstrated that a l-|imol BrEtS/mL dose completely inhibited acetoclastic methanogens in
a thermophilic digester fed lignocellulosic waste, while SO |imol/mL was required to completely inhibit CO2
reduction.
oecond International Meeting, NATO/CCMS Pilot Study
C-44
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Bhattacharya, S. K.; and Parkin, G. F. 1988. Fate and Effect of Methylene Chloride and
Formaldehyde in Methane Fermentation Systems. Journal Water Pollution Control Federation
60(4): 531-536.
Chemical Week 141(13): 8-9. September 23,1987.
Chemical Week 143(1): 11-12. July 6, 1988.
Cook, A. M.; Grossenbacher, H.; and Hutter, R. 1983. Isolation and Cultivation of Microbes
with Biodegradative Potential. Experientia39: 1191-1198.
Egli, C.; Scholtz, R.; Cook, A. M.; and Leisinger, T. 1987. Anaerobic Dechlorination of
Tetrachloromethane and 1,2-Dichloroethane to Degradable Products by Pure Cultures of
Desulfobacterium sp. and Methanobacterium sp. FEMS Microbiology Letters 43: 257-261.
Gossett, J. M. 1985. Anaerobic Degradation of Ci and C2 Chlorinated Hydrocarbons.
Engineering & Services Laboratory, U. S. Air Force Engineering and Services Center, Tyndall
AFB, FL, Report No. ESL-TR-85-38; NTIS #AD-A165005/0.
Gossett, J. M. 1987. Measurement of Henry's Law Constants for Ci and C2 Chlorinated
Hydrocarbons. Environmental Science & Technology 21(2): 202-208.
Kirk-Othmer Encyclopedia of Chemical Technology, third edition, volume 5. 1979. John Wiley
& Sons, New York.
Sayre, L M. International Standards for Drinking Water. 1988. Journal American Water Works
Association 80(1): 53-60.
Stuckey, D. C.; Owen, W. F.; McCarty, P. L.; and Parkin, G. F. 1980. Anaerobic Toxicity
Evaluation by Batch and Semi-Continuous Assays. Journal Water Pollution Control Federation
52(4): 720-729.
Thiel, P. G. 1969. The Effect of Methane Analogues on Methanogenesis in Anaerobic Digestion.
Water Research 3: 215-223.
Vargas, C. and Ahlert, R. C. 1987. Anaerobic Degradation of Chlorinated Solvents. Journal
Water Pollution Control Federation 59(11): 964-968.
Zinder, S. H. and Koch, M. 1984. Non-Aceticlastic Methanogenesis from Acetate: Acetate
Oxidation by a Thermophilic Syntrophic Coculture. Archives of Microbiology 138: 263-272.
Zinder, S. H.; Anguish, T. and Cardwell, S. C. 1984. Selective Inhibition by 2-
Bromoethanesulfonate of Methanogenesis from Acetate in a Thermophilic Anaerobic Digestor.
Applied and Environmental Microbiology 47(6): 1343-1345.
Second International Meeting, NATO/CCMS Pilot Study
C-45
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2H20
COr
2HCI
CH2CI2
C02
¦5-CO2 »C02 - Reducing Methanogens
T
H20
CH 3 COOH i^^etoclastic^teth^^^^^
2 ch4
ch4 + co2
FIGURE 12: Fate of DCM in Methanogenic Systems
C-46
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Bob Bell
C-47
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Dr. Robert M. Bell, NATO/CCMS Fellow
Statement to the 2nd International Meeting
Bilthoven, 7-11 November 1988.
My research project is concerned with the uptake by higher plants of
organic pollutants from low level polluted soil. At past meetings I have
presented research findings as follows:
The study of organic chemicals in the soil environment has been
limited to agricultural chemicals (e.g., insecticides, pesticides and
herbicides) and specific compounds which have been found to cause a
problem or to persist in the soil for long periods (e.g., PCBs, PBBs,
etc.). This has possibly occurred because of the complexity of reac-
tions, the large number of compounds, and the cost associated with
their analysis.
The greatest influences on the potential for non-1onic organic
chemicals to impact a plant are the relationships and interactions
between Its vapour, liquid and adsorped phases in the soil, and its
soil degradation rate. These processes determine not only the form
of the compound that is available to impact the plant but also the
speed at which the compound moves or spreads through the soli to
achieve Its impact. The importance of each of these processes will
be discussed separately.
Where the absorption value of a particular pollutant 1n a par-
ticular soil is not available or has not been measured, a good corre-
lation has been found between the organic carbon distribution
coefficient, or Koc, and the octanol water partition coefficient, or
Kow, of the chemical. The Kow 1s defined as the ratio of the chemi-
cal concentration 1n octanol to that in water, when an aqueous solu-
tion of the chemical Is mixed with octanol and then allowed to
separate.
The relationship between the compartmentallzatlon of the com-
pound between the soil solution and the air spaces 1n the soil 1s
often described by Henry's Law and the extent of partitioning
described by Henry's Constant.
Uptake of chemicals from the soil Into plants 1s a complex pro-
cess which may Involve compound-specific or active processes, or it
may be a passive process 1n which the chemical accompanies the
transpiration of water through the plant. If the former case is
correct, then a rigorous relationship between the degree of uptake
and the physico-chemical parameters of the chemical cannot be
expected. Nevertheless, some general guidelines may be expected, and
1n the case where uptake into the plant Is a passive process, then
relationships should exist.
environmental advisory unit
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Providing that degradation of the chemical does not occur
within the plant, and plant root uptake and translocation of pollu-
tants from the soil is a passive process, then plant uptake can be
described as a series of consecutive partitions between the soil
solids and the soil water, the soil water and the plant roots, the
plant roots and the transpiration stream, and finally the plant roots
and the plant leaves.
Pollutants with the highest log Kow value [for example, dioxin
(6.14), PCBs (4.12-6.11), some of the phthalate esters (with log
Kow's above 5.2) and the polycyclic aromatic hydrocarbons
(4.07-7.66)] are those most likely to be accumulated by or in the
root and not be translocated out of 1t. Those chemicals with a lower
Kow are those that are lipophobic and water soluble, are likely to be
translocated within the plant, and may reach significant con-
centrations within the plant leaves.
The final variable affecting plant uptake of soil-borne organic
pollutants is the plant type itself being exposed to the pollutant.
There has been no systematic examination of plant responses to
organic chemicals in soil, although it does appear that, as with
plant uptake of soil-borne heavy metals, there is variation 1n uptake
both between species and within the same species on an Individual
level.
It can be seen from the above that plant uptake of soil-borne
organic pollutants 1s a complex phenomena, being influenced by many
climatic and environmental factors. More work is needed on this sub-
ject to further define these parameters, and their extent, so that
the potential environmental impact of organic pollutants can be
assessed and so that actions designed to limit such impacts can be
optimaly targeted.
Over the last six month period the emphasis of my studies has been
towards publication rather than further work. Chemosphere has recently
accepted for publication an article entitled "Plant uptake and non-1onic
organic chemicals from soils" and I have been preparing a chapter on plant
uptake for a book entitled "Organic contaminants 1n the Environment" to be
published by Elsevier. It 1s likely that this preparation will continue
until the May 1989 NATO meeting.
As Fellow Coordinator I have attended and participated 1n both the
International and Workshop meetings of the Study Group at Hamburg and
Bilthoven. I propose to continue with my joint role of participating and
coordinating.
Sau environmental advisory unit
C-49
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Appendix D
Presentations by New
NATO/CCMS Fellows
-------
Resat Apak
D-l
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HEAVY METAL REMOVAL FROM CONTAMINATED GROUNDWATER BY THE USE
OF METALLURGICAL SOLID WASTES AND UNCONVENTIONAL MATERIALS
A Research Proposal Submitted to NATO/CCMS Pilot Study
by Docent Dr. Re?at Apak, Istanbul University, Faculty of
Engineering, Department of Chemistry and Institute for
Environmental Research, Vezneciler, Istanbul, TURKEY
INTRODUCTION
At the present time, the municipal rules and regulations
in Turkey for the control of environmental pollution do not
have a clear and widely accepted application. Some factories
treat their wastes before discharging into the sewer system,
some only pay for the compensation of their damage. The latter
plants postpone the construction of treatment plants for
industrial wastes and wastewater because of financial diffi-
culties. This behaviour meets a limited understanding from the
municipalities as long as the industrial plants pay for what
they discharge. Nevertheless according to the prevailing pollu-
tion control acts in Turkey, industrial effluents have to be
pretreated in order to be discharged into the sewerage system,
and the metropolitan municipalities of the major Turkish cities
shall provide the necessary funds to establish an improved
sewerage system.
For example, in Istanbul domestic and industrial (partly
treated) wastewaters are pumped to primary treatment plants
via the main sewage collectors. As a result of the recently
realized Istanbul Metropolitan Sewerage Project (also known
as the Golden Horn Project) these wastewaters undergo primary
D-2
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(screening) treatment in seven plants (Tarabya, Pa^abah^e,
Baltalimam, Ku^uksu, Uskiidar, Kadikoy and Yenikapi) , and
primary plus secondary (biological) treatment in three
plants (Biiyukgekmece, Kiigukgekmece and Tuzla) located in
areas of poor seawater circulation. (See map) Both primary
and biological treatments are applied in the Prince Islands.
Finally wastewater leaving these plants is discharged through
long pipes (extending 300-1200 m from the shore) into the
Bosphorus subsurface stream heading northward of 60-70 m depth.
Since public attention is focused on surface waters,
groundwater pollution in Turkey has not been explored to a
great extent. But the problems of untreated industrial waste
disposal, agricultural runoff enriched with fertilizers and
chlorinated pesticides, and domestic sewage lacking biological
and physico-chemical treatment are expected to cause ground-
water contamination in the long run, especially in urban
industrialized zones.
Essentially Turkey has had a good groundwater quality
from which drinking water is provided. The treatment procedures
for drinking water are usually comprised of sand filtration
and chlorination.
In this proposed research, the purification of heavy
metalcontaminatea groundwater by coagulation and flocculation
is aimed. Since pure chemicals traditionally used in water
treatment (alum, polybasic aluminum chloride, ferric and
ferrous sulfates and chlorides etc.) are relatively expensive,
cost-effective coagulants and flocculants like metallurgical
solid wastes (red muds as by-products of alumina manufacture,
blast-furnace slags as by-products of iron and steel manufac-
ture, power-plant fly-ashes and sludges, etc.) and unconven-
tional sorbent materials are intended for use along with
D-3
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u
—— A^ikkati KollcktlNlcri OP Eh! to lLECVHIS
—— Tunci Koilefctirteri TU/WELL
ffl On Arilms Vsisfcri
fiiyotojik Antma l
—Oenu D*|W|ian SEA D|
Miksu feplama Hwcalvi WAS
" MARMARA DENiZi
TREATMENT PLANTS
festsleri 6/OLCp'CAI. TREATMENT PLANTS
SCMAAG&S
TeWATEfc COLLECTION Re&ONS
-------
flocculation aids, i.e., polyelectrolytes. These metallurgical
wastes in Turkey are considered as useless by-products of
little or no value. The indicated treatment procedures may
be performed either in situ by the use of red mud and slag
slurries, or offsite via pumping and treating groundwater
with these adsorbents an flocculants followed by sedimen-
tation an floc-filtration. Surprisingly the coagulants
obtained from the waste materials may have shorter coagulation-
seaimentation times, larger effective pH range, and more
diverse fields of usage than conventional coagulants. {1}
Alternatively, red muds, slags and sludges may be buried in
the contaminated groundwater flow path and placed on the
surface of groundwater seeps. Although these waste-derived
coagulants are expected to release small amounts of aluminum
and iron salts of low toxicity to groundwater when used in
situ, these types of treatment may appear to be practical
as interim techniques for those situations requiring an
immediate but temporary corrective action, and during their
application, more permanent measures could be planned at the
source of contamination (Actually these problems would be
more severely perceived in the case of fly-ash and sludges).
Moreover, the stability of the floes formed with these waste
coa9ulants as well as the settlement and adsorbability of
these floes on the aquifer causing changes in its permea-
bility {2} should be considered.
For more toxic metal-polluted water bodies in ponds
and lagoons, e.g., high chromium-containing tannery effluents,
cost-effective cement compositions may be prepared by blending
these red muds and slags {3,4,5} so as to fix contaminated
material by onsite solidification.
As for the selection of heavy metal-polluted ground-
water site where the hypothetical remedial action is suggested
D-5
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to take place, groundwater sources near abandoned mines, or
places where metal-finishing and electroplating effluents are
dumped could serve the purpose. For determining the geological
and hydrological characteristics of the selected site, outer
technical assistance will be required.
An effective demonstration of the proposed remedial
action onsite can not be carried out on account of the absence
of a suitable project of groundwater purification by the
Turkish government or private sector, but instead, jar test
simulations of groundwater conditions, and laboratory scale
pilot-plant studies will be performed on simulated and actual
well water samples.
DESCRIPTION OF COAGULANTS AND SORBENTS FOR DECONTAMINATION
STUDIES
Red muds and blast furnace slags have been utilized in
the removals of heavy metals, radionuclides, inorganic and
organic materials, suspended solids (SS) , colour, biological
oxygen demand (BOD), and chemical oxygen demand (COD) from
water streams as cheap adsorbents and flocculants {6,7}, and
in the adsorptive removal of S and N oxides from stack gases
{8,9} . They have been used in natural form, or following
acid or heat preconditioning for wastewater treatment.
Polymeric flocculation aids have occasionally been used as
supplements, especially for organics, SS, BOD and COD removal
operations.
These metallurgical waste materials, especially red
muds in natural form, have a high neutralization capacity
of acidic waters due to their high alkali content. Thus they
are good precipitating agents for heavy metals via hydrolytic
precipitation reactions.
D-6
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Alumized red mud solids (ARMS)- obtained by sulfuric
acid treatment of red muds- contain the double salts of
sodium aluminum sulfates as the major constituents, with
significant amounts of CaSO^, ^£0. AljO^. 2SiC>2. 21^0,
FeS04, SiC>2» Ti02» Fe2^s04^3 and Fe2°3 • The indicated
composition may serve to act both as a flocculant and adsorbent
for wastewaters. An ARMS plant for phosphorus removal has been
shown to be at least 50 % cheaper in operation costs than a
conventional plant working with alum {12 }.
The basic advantage of red muds and blast furnace slags
is their versatility. Since they are comprised of a number
of adsorbents and flocculants, all of which are specific for
certain treatment procedures, these muds and slags are
applicable in diverse applications. For example, in the case
of As removal, Fe (III) compounds are especially important,
and the combined effects of ferric and aluminum compounds
are stronger than that of unassisted alum. Lime should be
used in combination with alum and polybasic aluminum chloride
(PAC) for turbidity remaval {13} . From the perspective of
coagulation to remove particulates, orthophosphorus exerts a
coagulant demand for A1 and Fe (III) . Calcium hydroxide
precipitates orthophosphates better, while aluminum sulfate
shows higher efficiency for polyphosphates removal. If
activated alumina is used for phosphorus removal, part of
it is lost during the acid regeneration step. Fly ash, when
combined with alumina, is a more suitable adsorbent for
phosphorus removal than alumina alone. The combined usage
of ferric and aluminum sulfates provides a more satisfactory
uranium removal from drinking water {14} . Kydrated TiC^/
a constituent of muds and slags, is an uranium-specific
adsorbent. Furthermore, alum coagulants of improved efficiency
are produced by adding small amounts of Ti (IV) sulfate to
Alj (SO4)3 coagulants, accelerating the hydrolysis of aluminum
D-7
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sulfate even at low temperatures, and improving the growth
of the floes {15} . On the other hand, (or HCl)
pretreated red muds contain soluble aluminum, ferric and
titanyl sulfates (or chlorides) which present a valuable
combined coagulant, while hydrated Ca and Na aluminosilicates
of varying composition in red muds and. slags contribute a mixture
of adsorbents for different effluent treatments. Silicates
have been used as flocculant adjuvants in combination with
the conventional ferric and aluminum salts in respect to
improved floe size and enhanced turbidity removal {16J .
Some other example of unconventional coagulants and
sorbents are listed in Table 1.
Table 1- Unconventional Coagulants and Sorbents
Coagulant or sorbent Substances removed Reference
from wastewater
Red mud
Heat treated red mud
Acid treadet red mud
White mud
Red mud+powdered coal
(Pelletized and carbonized)
Blast furnace slag
Granulated slag
Granulated slag
Acid treated blast furnace
slag
Metallurgical slags
Converter slag
Ni refining slag
Iron sulfide slag
As
P
SS, BOD, color
Zn, Cu
Zn, Cd
{17,18}
{19}
{20}
{21}
{22}
Petroleum products
and metal hydroxides{23,24}
Hg, Cd, Pb, Cr
Phosphate
Turbidity, SS
Zn
Phosphate
Turbidity
Cr-VI
{25}
{26 }
{27 }
{28 }
{29 }
{30 }
{31 }
D-8
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Table 1- Continued
Ferrosilicon plant by-product
(silica flour)
Hydrated Ti02-contg. materials
Building materials+brown coal
ash
Waste pickling liquor (Contg.
FeS04)
Nitrated lignite
Nitrohumic acid-alginic acid
Peat litter+(hN a2S+FeCl3)
Acid treated tarred peat
pyrolysis product
Hxuriin from turf
NaOH treated wood flour
h3po4
Coastal red wood (bark)
Mn02 precipitated sawdust
Corallite (biogenic CaC03)
Vulcanized rubber
Leather tanning wastes
Hair and feathers
Bone carbon
Bone black
Cu (32)
Pu, Ru {33}
90Sr;90y (34)
CrO.2" (35)
4
Cr-VI, Cr-II, Zn-II {36}
Cd, Hg, Pb (37,38)
Cr {39}
Hg {40}
Hg {41}
Cd {42}
Cr, Cu, Hg, Pb, Cd, Zn {43}
Heavy metals {44}
226Ra {45}
Cd {46}
Hg {47,48}
Cr {49}
Hg, As, Cr, Pb, Cd {50}
Hg {51}
Cd {52,53}
Nachanisms of Removal of Pollutants
The basic materials subject to this research, i.e.,
activated (or natural) red muds and blast furnace slags, act
in a four step mechanism: (i) Gel precipitation (sweep
flocculation, (ii) flocculation by adsorption of hydrolytic
products, (iii) conventional adsorption and (iv) ion exchange.
Gel precipitation is the most important contribution
to mineral acid-activated red mud in water treatment, and
D-9
-------
most heavy metals are removed via coprecipitation {54} .
Due to the presence of strongly hydrolyzable species of Al
(III), Fe (III) and Ti (IV), the primary effect of ARMS in
particulate removal results from hydroxide precipitate
initially in the form of a fine colloidal dispersion. The
particles then aggregate to form hydroxide floes which enmesh
the originally existing colloids. The entire process is
referred to as 'sweep flocculation'.
Besides sweep flocculation, ferric and aluminum salts
in ARMS can cause flocculation by specific adsorption of
hydrolytic products. The multi-nuclear hydrolysis products-
formed as kinetic intermediates-including Fe2(OK)^2t Fe^
(0H)4^+# Al^(0H)g4+ and Alg(OH)2Q4 + are even more effective
flocculants than their parent ions due to their higher charge
and strong specific adsorptivities. This mechanism can be
especially important with aging, since the multinuclear
hydrolyzate production reactions are very slow.
Polymeric flocculants promote destabilization of
colloidal dispersions by 'bridging flocculation'. A widely
used synthetic polymer of the non-ionic type is polyacrylamide.
This polymer can be used with ARMS, where hydrated oxide gels
on the red mud surface participate in hydrogen bonding with
polyacrylamide according to the reaction:
rc
H-N-C=0 H-O-M
Usually, an extremely small concentration of the polymeric
flocculant, along with ARMS, is sufficient to bring about
irreversible adsorption. A small proportion of polymeric
segments anchoring the colloidal surfaces can interact
between particles to cause bridging flocculation.
Conventional adsorption is also a mechanism of
D-10
-------
pollutant removal for metallurgical solid wastes; the removed
metal ions may condense as uncharged hydroxides on the
surfaces of these -OH bearing adsorbents. The adsorption
capacity of muds and slags has been attributed to the
dissolved J^SiO^-matal ions reaction. Slag effectiveness
is reported to increase with CaO and Si02 content for
CaO/SiOj - 2 {55} . Natural waste adsorbents have physical
(conforming to adsorption isotherms) and semichemical
adsorption as their primary mode of action, while after
acid treatment, gel-precipitation may become the dominant
mechanism.
Red muds and granulated slags can function as synthetic
cation exchangers having pores whose size depends on the pH
of the pretreatment suspension. The cation exchangers
produced from muds and slags have porous silicagel-H+
macromolecular structure in which the chief constituents,
sodium and calcium aluminosilicates, act as zeolites. These
synthetic zeolites are particularly useful for radionuclide
removal from effluents since they are not damaged by
ionizing radiation.
EXPERIMENTAL WORK WITH RED MUDS AND GRANULATED SLAGS
Experimental work has been carried out by V. Apak
et. al. for the utilization of Turkish red muds and blast
furnace slags in heavy metal removal from wastewater
{56,57} . The average composition of the red muds used were:
Fe203 37, 26 %, Al^ 17.58 %, Si(>2 16.94 %, Ti02 5.55 %,
Na20 8.31 %, CaO 4.38 %, and loss on ignition 7.17 %.
The red muds were treated with HC1 according to the
D-ll
-------
procedure of Shiao {58} prior to metal removal experiments.
The granulated slags were used as such. The results are
summarized in Table 2.
Table 2- Metal removal with red mud and blast furnace slag
Metal removed
Initial metal concn. (ppm) Removal efficiency
used in sorption studies after 4 hr-contact
Pb (II)
Cu (II)
Cd (II)
U02 (II)
5-30
II
100-180
30-70
30-100
60-150 (pH 3)
60-200 (pH 4.5)
60-150 (pH 7)
450-1300 yg Pb/g r.m.
450-1250 yg Pb/g b.f.s.
7260-8400 yg Cu/g r.m.
2700-3700 yg Cu/g b.f.s.
2940-4600 yg Cd/g r.m.
1570-3300 yg U/g r.m.
5630-10980 IJg U/g r.m.
4800-9100 yg U/g r.m
In nofet experiments, 1 g of the adsorbent was contacted with
100 mL of the metal salt (as chloride or sulfate) solution
at weakly alkaline-neutral pH, and the results more or less
conformed to the Freundlich adsorption isotherms.
BASIC ASPECTS OF THE RESEARCH PROPOSAL
The basic aspects of the proposed activity can be "
summarized under the following headings:
- Literature survey of the cost-effective metallurgical
waste coagulants and sorbents and of their mechanisms of
action will be completed.
- A suitable site of polluted (preferably with heavy
D-12
-------
metals) groundwater will be selected; the site's hydrogeological
characteristics will be established.
- Jar tests of simulated groundwater conditions will
be carried out by utilizing various coagulants and sorbents
and a number of heavy metal salts. Removal efficiencies will
be determined as functions of various parameters, i.e., pH,
coagulant dose, metal speciation etc. Some chlorinated pesti-
cides may also be introduced at this stage if the instrumental
means for determining their removal at the researcher's
disposal are adequate. Possible synergistic or antagonistic
combinations of heavy metals as well as of pesticides in
respect to removal efficiencies may also be studied.
- A feasibility study of the hypothetical technologies
capable of being demonstrated at the selected site will be
based on jar tests and pilot experiments • Prospects for the
utilization of both in situ and pump-and-treat technologies
will be investigated. The problem of residual micropollutants,
i.e., ferric and aluminum salts, leached out from the waste
adsorbents and flocculants to groundwater will also be compre-
hended. Finally a remedial action will be suggested for the
cleanuD of the site.
Although the proposed activity does not introduce a
novel technology of treatment, it may present a novel approach
in respect to the materials suggested for use in the treatment
of groundwater.
D-13
-------
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1980 (Chem. Abst. 99:14594b).
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D-15
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2 Dec 1980 (C.A. 96:168402j).
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(C.A. 81:96128u).
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126571c).
32- K. Okuda, J. Miyagawa, Japan. Kokai 74,122,889 29 Mar 1973
(C.A. 82:102885c).
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66:110859g).
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35- K. Kashiwase, Japan. Kokai 74 13,078 (C.A. 81:6146w).
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(C.A. 82:115839r).
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(C.A. 80:87270m).
D-16
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38- K. Terajima, S. Tomita, Ger. Offen. 2,348,436 02 May
1974 (C.A. 81:126561z).
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(C.A. 80:124403e).
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(1974) 2646-50 (C.A. 82:89780t).
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(C.A. 82:115859x).
42- T. Yamaguchi, Japan. Kokai 74,102,567 27 Sep 1974
(C.A. 82:129036p).
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82135g).
44- J.M. Randall, R.L. Bermann, For. Prod. J. 24 (1974) 80-4.
45- L. Berak, Czech. CS 203,307 15 May 1983 (C.A. 99:165614k).
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(C.A. 82:102840j).
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(Nucl. Sci. Abstr. 29 (1974) 24092).
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111211m).
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1973 (C.A. 80:52180e).
D-17
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51- T. Sano, M. Sato, Japan. Kokai 73 90,927 27 Nov 1973
(C.A. 80:99994p).
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(C.A. 81:175885s).
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102856u).
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Flocculation by Inorgan. Salts, NATO Sci. Committee,
Sijthoff and Noordhoff, The Netherlands (1978) 101-130.
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81-4 (C.A. 81:126449).
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unpublished Ph. D. Thesis, Istanbul Technical University,
Nuclear Energy Institute, 1987.
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Separation Systems, ed. Y.A. Attia, Elsevier Sci. Publ.
B.V., Amsterdam, 1987, pp. 765-771.
58- S.J. Shiao, K. Akashi, J. of Water Polln. Control Fed.,
Feb. (1977) 280-5.
D-18
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Aysen Turkman
D-19
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CYANIDE REMOVAL FROM CONTAMINATED GROUNDWATER
Assoc. Prof. Dr. Ay^en TURKMAN, Turkey
INTRODUCTION
Total water consumption in Turkey is about 11.6 billion
m3/year, of which 4.03 billion m3/yeor is supplied from
groundwater (34 %) (Abidoglu, 1981). When only domestic water
supply is considered (drinking + household use) 0.3 billion
m3 /year of water is supplied by dams and the remaining 1
billion mS/yesr is supplied from groundwater and springs
(ozi$, 1981). Thus,the contribution of groundwater to the
domestic water consumption is about 6? % .
Starting in 1960 's the share of urban population showed a
rapid increase (SP0,1986), resulting in greater percent
living in urban areas in 1985. That major cities have entered
into an industrialization process have caused a rapid
immigration of large masses of urban population into those
cities, namely Istanbul, izmir, Ankara, Adana, Samsun, Bursa,
Eski^ehir, Erzurum etc. These cities have met heavy environ-
mental pollution and deterioration problems.
The environmental pollution control in Turkey has turned a
monumental corner with 1902 constitution which defines the
responsibilities of the state and the citizens for a
healthful and balanced environment. Environment law no. 2872
has passed in 1982. This law is a "Framework type law"
stating the basic principles and defining the responsi-
bilities of the administration, the public and the polluters.
The economic philosophy of "polluters pay" is to be noted.
Environment law foresees several regulations to be
promulgated for the control of environmental pollution.
Technical details of Environment law no. 2872 are left to
regulations to be drafted as needed. Technical issues to be
handled in the from of regulations are given below:
- Air pollution control measures worked out as "Regulation
for Protection of the Air Quality" dated November 1986.
- Noise and vibration control techniques are drafted as
"Regulation for Noise Control" enacted in December 1986.
- "Water Quality Control Regulation" is enacted in September
1988 .
The last regulation follows the basic principles of the
German Regulations (Wasserhaushaltgesets, 1976) in some ways,
but it Is not an easy type of regulation and the standards
for the industrial effluents and for direct discharges Into
D-20
-------
the receiving waters or into the sewerage system are adjusted
according to the bearing capacity of Turkish economy. Besides
these general regulations applicable for the whole country,
also local regulations for big cities are allowed.
For solving urban infrastructure problems especially in big
cities several financing organizations and countries are
being contacted to provide foreign finance required by urban
sewerage projects. As a result, both Istanbul and Izmir
Metropolitan Municipalities have reached to agreement with
the World Bank for financial support in order to establish
their sewerage system and municipal wastewater treatment
plants. Industrial effluents will be accepted into the sewers
after pretreatment. Rest of the urban centers are in the
process of preparing engineering projects for sewerage and
treatment plants ($englil, 1986} .
As can be understood from the above summary, although the
history of environmental pollution control studies do not go
back very far in Turkey, the environmental problems are not
yet at an unsolvable 6tage. At present, because of the
Infrastructure inadequacy problems in many places,there are
heavy local water, sea and soil pollution problems. In some
cases pollution is detected only qualitatively and water
source is rejected. Detailed pollution detection and research
studies are done mainly in big cities and by Universities.
There are several soil, groundwater pollution research
studies conducted by our University.
The causes of groundwater pollution in Turkey may be grouped
as follows:
a. Pollution due to the domestic wastes: A big percentage of
inhabited areas is unsewered and septic pools are used for
wastewater disposal. The high incidence of waterborne infec-
tion indicates evidence of wastewater infiltration into the
groundwater. Also fecal collform and total collform analysis
show the same result. In some areas sewerage systems is very
old and leaking sewers result in groundwater contamination
b. Fertilizer and pestiside application: Although
industrialization is taking place at a rapid rate in Turkey,
she still keeps her main characteristic of being an
agricultural country. Because chlorinated hydrocarbons
(including DDT), organophosphates, carbamates and many other
types of pestlsldes are in use in Turkey, it is expected that
groundwater contains some amounts of these chemicals,
especially non biodegredable ones. Unfortunately no case
study is conducted on this subject.
c. Industrial pollution: Due to the chaos we are having
related to environmental pollution control, some industries
have their treatment plants, others do not, some of them are
planning to pretreat their wastes, others are moving to other
D-21
-------
areas and there are many industrial wastewater treatment
plants that do not function properly. Thus, it is inevitable
to have groundwater pollution of industrial origin. Although
there are a few case studies related groundwater pollution,
it is like an iceberg, many of the cases are not revealed
yet.
SITE DESCRIPTION
Kemalpa?a, one of the provinces that belong to Izmir, is
established at the south East corner of the Kemalpa$a plain.
Its surface area is 30 Km2 and height 200 m from the sea
level (Figure 1).
The settlement is 29 Km away from Izmir and takes place
between the mountains and the Kemalpa^a plain which is
valuable and fertile. The plain is famous for its cherry
trees. Transportation is easy with a main asphalt road which
was built on 1957.
The history of Kemalpa$a goes back to antique times. Kemal-
pa$a CNymphoion) was between many important settlements like
Ephesus, Smyrna, Magnesia and Sardis. The old reliefs about
which Heredot also wrote are there, but their meaning is
still being discussed.
There are also ruins from Hitits, Byzans, Selguks, and
Ot tomans.
Climate
Kemelpa^a has a relatively mild climate with cool tempera-
tures and fairly heavy rainfall in winter and hot and dry
summers. This climate allows different kinds of crops to be
grown. The deficiency of water in summer is compensated by
water resources in the area. Because the settlement is at the
foot of the mountain, the summers are relatively cool and
growing different kinds of crops are possible.
Maximum temperature is 26 C (August avg) and minimum tempera-
ture is 9.3 C (January avg). Snow and frost are very rare.
Predominant winds are in South - East direction. Average
annual precipitation in the project area is 1136.8 mm for the
1936-1999 hydrologic years. Maximum precipitation occurs on
December (2420.0 mm), minimum on August (40.0 mm) (Kalayci-
oglu, 1 998) .
Topography
Kemalpa;a is situated at the foot of the Nif Mountain. Due to
this, as the settlement grows, difficulties are met in
finding new places. The old province is established on a
small hill at an attitude of 3B0 m. This hill and other hills
D-22
-------
Figure 1: Project area location mep (D-M, 1571)
D-23
-------
around overlook to the Kemalpa?a Plain.
The valley which take place between the hills extends till
the inner side of the Nif Mountain.
Geology
The surface distribution of the geologic formation that
underlie Kemalpa?a Plain area are shown on the hydrogeologic
map (Figure 2). The area may be studied under two separate
headings: metamorphic mountainous mass and alluvial plain
that formed lately. The plain remains between KiigLik Menderes
River basin and Izmir basins.
Bozdaglar consists of Nif ( 1506 m) , Mahmut ( 1382 m) , Qal
(140? m), Qatma (1372 m). They are consolidated rocks which
are composed of gneiss and marble.
The sides of the Nif mountain is moderately consolidated by
pieces of rocks that broke from higher parte of the moun-
tain. The area under the road is composed of alluvial
deposits and debris falling from the mountain. The area
generally consists of limestone, gravel and sandy clay. Of
the two faults in the area, one lies in North - South direc-
tion and the second one lies in East - West direction. The
area is along the first degree earthquake band.
Hydrographic Characteristics
Water resources in the area may be divided into two groups.
The most important water source, Nif River is born from
Ulucak village, extends along the plain in East - West
direction and turns to the North where it unites with Gediz.
It is fed by many small creeks flowing from the Nif mountain.
Some of these small creeks dries completely during the
summer. Of these, Derei$i is used for irrigation. Oereipi
with many others are responsible from the green cover in the
area .
No sewerage system is present in the town. The cesspools are
rather primitive and unhealthy. The immediate need for
infrastructure is painted out in reports.
In 1948, water is brought from 1500 m away by a network.
Because it is insufficient groundwater and spring water are
also used in the area. Some springs are abandoned due to the
pol1ution.
The springs in the area issue through the layers of flysh (at
the bottom), limestone (in between) and gravel and debris (at
top). Rainfall infiltrates to the bottom along the cracks of
limestone until the impermeable flysh layer is reached. Then
it moves upward along the fault to the surface at two sides
of the valley where the springs are located (Kalaycioglu
D-24
-------
198?) .
Hydrogeological survey in the area reveals the following:
1. The aquifer formation in the area are; limestone, alluvial
deposits that consist of sand and gravel, and Neogen series
which consist of sand, gravel and conglomerates.
2..Safe perennial yield of groundwater in the area is 25 x
10 m3.
3. The wells in the area which is indicated as "Area approp-
riate for groundwater abstraction " in Figure 2, will give
water from about 75-100 m deep, and the yield will be more
than 20 1/s (DSI.1979).
SITE HISTORY
In Kemalpa$a more than 100 industrial organization take
place. Some of them are shown in Figure 3.
Kemalpa$a Municipality asks the industries to analyse their
effluents in order to determine industrial wastewater
pollution load in the area. The samples are brought to the
Qokuz Eylul University laboratory and many environmental
parameters are tested including cyanide. 0.16 mg CN /I is
found at the effluent of a chemical industry (situated near
no.14 in Figure 3) which mainly processes natural resin. The
industry objects to the analytical result on the ground that
they do not use any cyanide compound. When wastewater analyse
is repeated, the same result was obtained after which ground-
water was suspected to contain the cyanide. In fact, when
groundwater sample was analyzed, it was found to contain
0.074 mg of CN'per liter. The water is stopped to drink. Now
it is only used in the process.
When groundwater of the chemical industry was found to
contain cyanide, other nearby industries using groundwater
were also curious about their water quality. The analysis of
groundwater samples in the area revealed that a cyanide
contamination of about 0.04 mg/1 of CN' exists. Table 1 and
Table 2 indicate the cyanide content of wastewater and
groundwater samples respectively. As can be seen from Table
rtone oT the industries contain very high cyanide concent-
rations as to contaminate groundwater. Thus, the following
possibilities may be considered:
1. The industrial source is not found yet. There are many
industries that may discharge cyanide containing wastes in
the area. For example, there is a plating industry using
cyanide baths. But the industry is located at downstream side
of the aquifer and far from the area of cyanide pollution.
The people from the industry say that they are collecting
their cyanide containing wastewaters in tanks and seeking
D-25
-------
Figure 2: Hydrogeolcgical map of the study area
-------
1 Clctilcal mtterlals niodic I ion (8iri) Clrctrlclty)
2 Srakt Il«-l»-g prediction Otjar)
1 liatllt l>x'L'«try (Bkccnli la>tlla)
Wlrpai Kamfactun
i Ccea cols
(Parquat Production
7.Plg»mt liuitr/
>.CM»lcall Industry (OkCailx Ctvmlcala)
9. Toed Irtiitty (Ball feed)
10.FriAo-Ta*-ak-Papil
11.Piper Induatiy (la«ant Papar)
U.Citffinrt trdumtry (Olnjiu)
1J.Agricultural *acM>« production (Era)
It Hirela Prccaaslrg (fata})
IS.Harala Ptocaaalrg (Grairarit)
It.Liatbar Procatslrg (Aira-(iJiulova)
17.Isolation Nultiy (9IH)
18 Taatlla Irduitiy (latkay laatlla)
19 011va l»atltuta
20 Oigmliad Olatrlet Cdiratlcn ard MaalU Cipt.
11.Papar trdiatry (Vilnak)
22. Mavy Outlas HacMna trdcitiy Cn>)
23 Haat Irddt ry (Pi"ar Kact)
2h Carrmlc Nultiy (C(a Cart«lc)
2J.Pt»rtfrrlc Irdiatiy (Air* Prt'»arlc)
26.Biscuit Harufulull (lri»«t BliCulti)
27.tni»al Industry
28 Olo "ay Hi«u'actura
29 011 va Oil trAatry
JO.food Packing (fatra Pak)
® gnie
jnpiUM"
aukara i*
Cl\!~: The industries uith expected cyanide content in their effl.
: The area where groundwater pollution is detected
Figure 3: Lccatlon oF industries in the project area
-------
for a solution. How long they con collect is unKnown.
When the effluents of oil the industries with probable
pollution are analyzed, the situation will be more clear.
2. The cyanide source may be diffuse type. It may be
originating from agriultural activities or Nif river. Thi9
situation will be more clear after Nif river is analyzed
periodically.
Table 1 : Cyanide concentrations of the Industrial effluents
located in Kemalpa$a region.
Industry No in Treatment Date Cyanide
map plant concent. mg/1
Meat Industry
Chemicals industry I
Chemicals Industry I
Paper Manufacture
Coca-Cola
Fruko-T amek-Pepsi
Cardboard Industry
Marble Processing
Zipper Manufacture
Metal Preparation
Enamel Industry
Ceramics Industry
Nif River
23 +
8 insufficient
Near 14 only
sedim.
1 1 +
S
10 +
12
14 only sedim
4
2?
24 ~
29.6.1986 0.08
4.2.198? 0.18
10.12.198? 0.21
18.1.198? 0.0B
7.3.1988 0.12
13.9.1988 0.02
4.2.198? 0.16
10. 12.198? 0.1?
20.1.1988 0.0B
3.2.1988 0.03
20.1.1988 0.04
31.3.1988 0.12
19.6.1988 0.09
23.6.1988 0.44
3.2.1988 0.03
0.08
13.9.1988 0.04
13.9.1988 0.015
D-28
-------
Table 2: Cyanide concentrations of groundwater samples
Location of the
wel 1
Depth of the
we 11
Date Cyanide
concentration
mg/ 1
FruKo Tamek Pepsi (10)
27.1.1988 0.035
Zipper Manufacture (4) Artesian
13.9.1988
0.015
Coca-Col a ( 5)
120 m
1 35 m
20.1.1988 0.040
20.1.1988 0.040
Chemicals Industry II Artesian 60 m
( 14)
14.1.1988 0.074
13.9.1988 0.020
Food industry (9) Artesian
27.1.1988 0.030
THE PROJECT STUDY
The project study will consist of three parts. In the first
part, cyanide source determination will be made. For this
purpose, wastewater and groundwater samples have to be
analyzed. Kemalpa$a Municipality promised to cooperate in
this respect. The municipality will ask the industries to
have their wastewaters to be analyzed. The analysis will be
performed at Dokuz Eyllil University, Env. Eng. Department.
In the second part of the study, groundwater will be pumped
and chlorinated to remove cyanide content. Experimental study
will consist of cyanide concentration measurements after
chemical oxidation. In most of the places using groundwater
in Turkey, the water is either used directly or chlorinated
and used. In this case more chloride will be added to the
water so that disinfection and cyanide removal will be
achieved at the same time. The dose will be determined
experimentally in the lab.
In the third part of the study, if the cyanide containing
wastewater is being discharged to an infiltration ditch, the
discharge will be stopped and the cyanide will be fixed to
the soil by salts (e.g. iron salts) so that they will not be
released to the water anymore. After it is kept in soil, it
will be oxidized slowly and naturally.
All the cyanide measurements will be made by spectrophoto-
metric method and checked by ion selective electrodes for
D-29
-------
correctness .
Cyanide Standards
The WHO International and WHO European Drinking Water
Standards both set a maximum allowable limit of 0.05 mg/1 for
cyanides as CN (Schipper, 19B4). For the first time in
1962, the USPHS Drinking Water Standards set a recommended
limit of 0.01 mg/1 end a mandatory limit of 0.2 mg/1 (McKee,
1998) .
According to Klein, the odor threshold for hydrogen cyanide
in water is 0.001 mg/1. The maximum safe total ingestion of
cyanide by humans has been estimated at something less than
18 mg/day, part of which will come from the normal environ-
ment and industrial exposure.
Because cyanide interferes biological oxidation in treatment
plants, industrial waste containing cyanide should not be
discharged directly into the sewers. Table 3 indicates
sewerage discharge limits of cyanides.
Table 3. Cyanide limits for industrial discharges into sewers
(Kupukgul, 1985) .
Country Discharge limit. mg/1 CN
Italy 1.0
Greece S.O
England 10.0
iSwitzerland 0-5
FRG 1.0
REFERENCES
1. Abidojjlu.A. Latif oglu , E . ( 1981) : Su ve Toprak KayriaK larinin
Ge1i§tiri1mesinde Kurulu$lararasi Koordinasyonun onemi, Su ve
Toprak Kaynak larinin Gel i § t iri line si Konferansi, DS± Genel
Mudiirlugu, Ankara.
2. CHM (1971): Izmir Project, Camp-Harris-Mesara, Draft
Report Feasibility and Master Plan for Water Supply, Izmir.
3. DS± (1979): Izmir Kemalpa?a Ovasx Yeraltisulari Hidrojeo-
lojik Etudii, Oevlet Su ±$leri Genel Md. , II. Bolge Miidurliigu,
Izmir.
4. Kalaycioglu, R. (1987): Kemalpaga (NYMPHAI0N) Tarihsel
Kent Dokusunun incelenmesi, D.E.u.Fen Bilimleri Enstitlisii,
Mimarlik Bolumii Yliksek Lisans Tezi, izmir.
5. Karaoglu, N.(1981): izmir Kemalpa^a Qevresinde Agxlan
D-30
-------
Kuyularda Yapxlmi? Olan Kademeli Hompe Deneylerinin Her
Kademe Verisinden VararlanaraK iletkenlik Katsayisinin Elde
Edilmesi, E.U.Yer Bilimleri Fakiiltesi Diploma Projesi, Izmir.
6. Ku^tikgul , E . Y . ( 190S) : Endustriyel Siyaniir Kirliligi ve
Kimyasel Oksidasyon ile Antimi, D.E.U. Fen Bilimleri
Enstitiisii Yiiksek Llsana Tezl, Izmir.
7. Mckee and Wolf (1976): Water Quality Criteria, California
State Water Rescources Control Board, USA.
8. bzi$. U.(1961): Anadoluda Su Kaynaklannxn DunLi, Bugiinu,
Yanni, Su ve Toprak Kaynak larinin Gelif tirilmesi Konferansi,
DS± Genel Miidiirlugu, Ankara.
9. Schippers, J.C.(1964): Summary of Standards and Goals for
Drinking Water, International Course for Hydraulics and Env.
Engineering, Delft, Holland.
10. SPQ (19B6): State Planing Organization, Turkey Water
Supply and Sanitation, Country Report, International Water
Supply and Sanitation Decade, Third Consultation in Europe,
7-10 April 1986, Izmir.
11. Sengtil.F., Turkman,A. ( 1988): Pretreatment Requirements
of the Industrial. Toxic Substances in Turkey, Environment'88,
Environmental Science and Technology Conference, 5-9 June
1988, Izmir, Turkey.
12. TKGM (1969): kemalpafa Sanayi Alanx Nazim ±mar Planx,
Tapu ve Kadostro Haritaai, Izmir.
13. Wasserhousholtgesets (1976): Federal Act as Promulgated
on 16 October 1976, Federal Law Gazette 1, p.3017, FRG.
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Alessandro Di Domenico
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Photodegradatlon Report. FIRST DRAFT.
NATO/CCMS Meeting. Bllthoven. November 1988.
SUNLIGHT-INDUCED INACTIVATION OF HALOGENATED AROMATICS IN AQUEOUS MEDIA
Alessandro di Domenico
Laboratory of Comparative Toxicology and Ecotoxicology,
Istituto Superiore di San1t&,
Viale Regina Elena 299, 00161 Rome (Italy)
I. SUMMARY
In recent years increasing concern as to the environmental burden
of a large variety of man-made chemicals that may irreversibly affect
natural biological equilibria and are a threat to human health, and the
parallel enactement in a number of Countries of chemical control
legislations, have stimulated research activities in rather new areas.
Sunlight photochemistry is one example. In fact sunlight-induced
photochemical processes may play some role in determining the fate of
environmental chemicals, and be a possible route for their removal.
A review of data relative to the photochemistry in aqueous media
of chlorinated benzenes (PCBZs), phenols (PCPs), naphthalenes (PCNs),
dibenzofurans (PCDFs), dibenzo-£-dioxins (PCDOs), and biphenyls (PCBs)
is provided in the present report. Analysis of data has been focussed
on direct, sensitized, and catalysis-assisted photoprocesses occurring
under environmentally relevant conditions.
Due to man's potential high exposure to the aforecited chemicals
and consequent toxic effects, such compounds - as well as other chemi-
cally related halogenated aromatics - are among those pollutants which
have priority for hazard assessment. Therefore, along with considera-
tions and comments on their sunlight photochemistry, pertinent informa-
tion on chemical, physical, and toxicologic properties has also been
provided with a specific focus on the environmental fate.
Purpose of the review is to provide a basis for preliminary
assessment of potential effectiveness of sunlight photochemistry as
detoxlcation means 1n natural or artificial water bodies for the above
chlorinated aromatlcs. Such assessment seems to be required to orient
specific experimental research in the field of outdoors solar photo-
chemistry to define proper technologies for the inactivatlon of various
contaminated matrices.
Note. The present draft has been prepared for NATO/CCMS meeting of
Pilot Study on Remedial Action Technologies for Contamlntated Land and
Groundwater (Bllthoven, the Netherlans, November 7-11, 1988). This
draft is in a provisional form and should not be cited or quoted.
AdD, NAPH0/NAPH01. °"33
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II. INTRODUCTION
In recent years, with both increasing production and increasing
complexity of chemicals produced in the industrial world, there has
been a concomitant escape - either directly, or indirectly through
secondary reactions - of numerous chemicals into the environment. The
list of chemicals that have been detected is much too long to be
reported herein in its entirety. Suffice it to say that these indus-
trial compounds consist also of many toxic substances, among which
halogenated aromatics such as: chlorinated benzenes (PCBZs), phenols
(PCPs), naphthalenes (PCNs), dibenzofurans (PCDFs), dibenzodioxins
(PCDDs), and biphenyls (PCBs).
With the exception of PCDFs and PCDDs, which are unwanted indus-
trial by-products and obiquitous environmental contaminants, the other
chloroderivatives are man-made and have found widespread use in the
fields of pesticides, herbicides, industrial intermediates, solvents,
dielectric fluids, heat exchangers, and plastlcizers. As towards man
and the environment several of the compounds belonging to the afore-
cited classes are known to carry a great toxic potential, the optimal
situation would be to have a "zero" release of such chemicals and their
congeners into the environment. While this is generally not feasible
from an engineering point of view, releases, especially of highly toxic
chemicals, should be minimal. Ways to achieve this would be: (a) to
either not produce the chemicals, (b) to produce them by alternative
ways that minimize the releases, or (c) to inactivate the chemicals by
physicochemlcal, photochemical, or microbiological methods prior to
their release into the environment. However, should the compounds reach
the environment, methodology should be available for treating the
contaminated media Inexpensively and rapidly.
Rather extensive photochemistry studies have been performed in
recent years on these chemicals which meet both requirements for being
potentially hazardous to the environment: in fact, they elicit toxic
effects to aquatic life at very low concentrations and have the poten-
tial for high exposure due to their 1n general large production volume
and/or highly dispersive uses, resistance to both microbial and hydro-
lytic degradation, and potential for bloaccumulation.
The available data seem to suggest that sunlight-induced photo-
chemical processes may be an Important factor in the elimination of
halogenated aromatics from the upper layers of natural water bodies.
Indeed, sunlight carries enough energy (Tables Ila-c) as to have a
potential for a practical use of solar photodegradatlon to inactivate
such compounds: for Instance, sunlight could be utilized for wastewater
detoxlcation under controlled conditions. Photodegradation may occur by
means of direct, sensitized, and catalysis-mediated processes in
homogeneous and heterogeneous phase. Reviews on photochemical processes
in natural waters, and their potential relevance as removal factors of
chemical pollutants, are available from the literature (for Instance,
iflW 01 Sanltl. RoT4
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see: Zafiriou et al., 1984; Cesareo et al., 1985). However, the envi-
ronmental significance of available data cannot be readily evaluated:
in fact, data are largely incomplete under both the qualitative and
quantitative profiles. They are rarely obtained under comparable
conditions, and only on relatively few occasions refer to water systems
and natural sunlight. In addition, when complete mineralization cannot
be accomplished, the toxic potential of photoproducts should be inves-
tigated in detail whenever It is not known.
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III. ELEMENTS FOR HAZARD ASSESSMENT
Prediction of the fate and toxic effects of chemicals in the
environment is essential to the assessment of their potential hazards.
The fate of a chemical depends upon the characteristics of the receiv-
ing environment, the chemical's properties that regulate its tranfer
processes between environmental compartments, and transformation
processes. Toxic effects depend on the nature of both the chemical and
the biological receptors.
Fate in the water compartment can be tentatively predicted making
reference to elementary physico-chemical properties such as water
solubility (Sw), vapor pressure (Pv), etc.; to partition constants
such as the air/water Henry's constant (H), the n-octanol/water parti-
tion coefficients (log(KQW)), etc.; and to kinetic constants, or
related data, that refer to transformation processes such as hydro-
lysis, biodegradation, and sunlight-induced transformations.
Probable adverse effects to the aquatic life can be predicted
based upon a number of biological assays that monitor different toxic
endpoints. Very often toxic endpoints, such as statistically determined
LC5q (lethal concentrations 50%, i.e. the concentration that kills
50% of the exposed organisms) after appropriate exposure times, are
used for predictions.
On the whole, fate-related properties and effect-related toxic
endpoints are basic elements for hazard assessment. Some are reported
in the following pages.
III.l. Polychlorobenzenes
PCBZs (12 congeners) form a group of stable, colorless liquids or
solids with a pleasant aroma. With the exception of monochlorobenzene
(MjCBZ), they are practically nonflammable. The most important
properties imparted by chlorine substitution are solvent power, viscos-
ity, and moderate-to-scarce chemical reactivity. PCBZs are generally
good solvents for fats, waxes, oils, and greases. They also find
extensive use in a number of organic chemical syntheses, and as elec-
trical equipment insulators, pesticides, herbicides, and fungicides.
Unwanted emissions of PCBZs are most likely to occur during their
manufacture or use as Intermediates, and from the disposal of waste
products from manufacturing operations (US EPA, 1984a).
PCBZs have a low solubility 1n water and vapour pressures decreas-
ing with Increasing^ chlorine content. The resulting Henry's constants
are generally >10^ atnrm^mol"1, so that all PCBZs are likely to
volatilize from water (Mackay and Wolkoff, 1973). All PCBZs have high
affinity for lipophilic materials: lipophillcity increases with chlo-
rination as shown by n-octanol/water partition coefficients (Kow) and
bioconcentratlon factors (BCF). Bioaccumulation was demonstrated to
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occur at high degree for PCBZs with more than two chlorine atoms
(Kitano, 1984). Based on values of K-w, sorption on soil and sediments
can also be predicted to increase with molecular weight.
Hydrolysis of aryl ha1 ides 1s extremely unlikely especially at
environmentally relevant pHs. Biodegradation was reported to occur for
1,4-dichlorobenzene (Kitano, 1984), while for other PCBZs biodegra-
dation might occur under special conditions but at very low rates. As
to photodegradation, direct photolysis could only occur for the heavi-
est term of the series as its UV absorption bands partly overlap the UV
section of sunlight spectrum (Cesareo et al., 1985).
Data concerning the toxicity of PCBZs to selected aquatic organ-
Isms show that 50% lethal concentrations are relatively high for all
PCBZs, and decrease markedly with Increasing chlorlnatlon. For hexa-
chlorobenzene (HgCBZ) the only available LC§q is 0,3 ppm for Poecilla
reticulata. LC5qs for pentachlorobenzene (PgCBZ) range from 0.2 ppm
for Poecilia reticulata to 5.3 ppm for Daphnia magna, whereas for
MiCBZ they are comprised in the range 19-86 ppm (Cesareo et al.,
1985).
PCBZs have been identified in all major environmental matrices.
The most frequently detected congeners in air and water have been
mono-, d1-, and trlchlorobenzenes, while penta- and hexachloroderiva-
tives have been found especially in food and soil (US EPA, 1984a). As
PCBZs have a high lipid solubility (Mellan, 1970), they are expected to
accumulate 1n ecosystems. However, their fate and transport in the
environment have not been well characterized as yet (US EPA, 1984a).
Studies on the transport of HgCBz indicate a high potential for
soil sorption. Ausmus et al. (1979) applied ^C-labeled hexachloroben-
zene to soil cores taken from a pine forest, and monitored its evapora-
tion and leaching by water over 21 days. Of the amount applied, <1% was
lost by volatilization or in the leachate, and none was degraded as
indicated by the absence of labeled CO2.
The fate of PCBZs in aquatic systems has not been completely
characterized, although Initial studies indicate that degradation is
possible by microbial communities in wastewater treatment plants. Lee
and Ryan (1979) examined the degradation of various chlorinated com-
pounds by microbes 1n samples of water and sediment. They observed that
degradation rates 1n water were slow. In the sediment samples, M^CBZ
was found to have a half-Hfe of 75 days, which was longer than that of
chlorinated phenols, but shorter than that of hexachlorophene. In
contrast, HgCBZ showed no degradation by water or sediment microbes.
III.2. Polychlorophenols
As with PCBZs, the physico-chemical properties, as well as the
partitioning and persistency data of PCPs (19 congeners) largely depend
on the number of chlorine atoms. 4-Monochlorophenol (4-MjCP), for
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example, is the most soluble PCP and the less bioaccumulative. It is
20,000 times more soluble, and 200 times less bioaccumulative than the
pentachloroderivative (P5CP) (BCF values obtained from: log(BCF) ¦
0.76*log(Kow) - 0.23, by Veith, 1980). 4-MjCP biodegrades is 76,000
times faster than tetrachlorophenol (Cesareo et al., 1985).
All PCPs are rather toxic to aquatic organisms and their toxici-
ties increase regularly with the number of chlorine atoms: in fact, for
almost all tested species P5CP is the compound associated with the
lowest LDgg. The P5CP LC50 appears to be as low as 0.1 ppm for
bluegill; for 4-MnCP the equivalent ICcn value is 3.8 ppm (Cesareo
et al., 1985).
It has been shown that commercial preparations of PCPs may contain
impurities such as polychlorinated dibenzofurans and dibenzodioxins
(Johnson et al., 1973; US EPA, 1980c), some of which are highly toxic.
PgCP is a commercially produced bactericide and fungicide used
primarily for the preservation of wood, wood products, and related
materials.
PCPs with a low chlorination level are associated with relatively
low persistence in water due to their high biodegradation rate, and low
propensity to bioaccumulate in biota and water sediments because of
their low value of K-w. The fully chlorinated phenol, P5CP, which is
also the most widely industrially used PCP, is resistant to biodegrada-
tion and tends to accumulate in sediments and biota. Furthermore, P5CP
(solubility: 14 mg/1 at 20 °C) is often used as the water-soluble
sodium salt: this fact provides for dilution but at the same time
favors widespread contamination of water bodies and sediments. Direct
photolysis 1n water occurs to different extents for PCPs that absorb
above 290 nm (Cesareo et al., 1985).
Since volatilization is unlikely for PCPs (Henry's constants
«10~3), they mainly distribute in water where biodegradation and
photolysis should be the two major fate-determining processes. Conside-
ring the position of the UV absorption bands of PCPs, biodegradation
may be easily predicted as the dominant removal process for practically
all PCPs but f^CP, for which photolysis and biodegradation should be
competing processes.
III.3. Polychloronaphthalenes
PCNs have physical and chemical properties similar to those of
polychlorobiphenyls (PCBs) and are manufactured, as complex mixtures
(e.g. Halowaxes), for analogous uses on industrial scale (Brinkman and
Reymer, 1976).
The PCN family 1s made of 75 different congeners, for many of
which a satisfactory chemlco-physical characterization is not availa-
ble. From what is known, the great majority of PCNs melt above room
temperature, with the octachloroderivatlve melting as high as 200 °C.
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Melting points of commercial mixtures are generally in the range
65—140 °C, although there are Halowaxes melting at the extreme
values of approximately -33 and 185 °C. Mixtures of mono- and dichloro-
naphthalenes are generally liquid at room temperature, whereas mixtures
of the more highly chlorinated congeners tend to be waxy solids (US
EPA, 1973). PCNs and PCN mixtures have specific gravities comprised
between >1 and 2, and are substantially insoluble in water (Brinkman
and Reymer, 1976). They exhibit a high degree of chemical stability (US
EPA, 1975) even at temperatures up to their boiling range (>200 °C),
are resistant to biodegradatlon and very bioaccumulatlve (Kitano, 1984;
Cesareo et al., 1985). PCNs are widespread and persistent pollutants.
Mixtures of tr1- and tetrachloroderlvatlves comprise the bulk of
market use as the paper impregnant in automobile capacitors. The
potential for environmental exposure may be significant when these
compounds are used as oil additives, in the electroplating industry,
and in the fabric dyeing industry (US EPA, 1980b). PCNs have been
detected as contaminants in foreign commercial PCB formulations along
with polychlorinated dibenzofurans, and are also present in PCBs
(Aroclors) made in the US but at lower levels than found in foreign
formulations (US EPA, 1980b).
Especially those PCNs containing five and six chlorine atoms have
been found to be very toxic to man and several animal species (Brinkman
and Reymer, 1976).
The environmental behaviour and fate of PCNs has not been specifi-
cally studied. Furthermore, there are very few data on their environ-
mental levels. Reports of distribution around a manufacturing unit
suggest low background levels 1n air, sea and surface fresh water, and
sediments and soil. PCNs have also been detected 1n fish, and bird and
man adipose tissues at ppb, ppm, and ppb levels, respectively (Pearson,
1982).
III.4. Polychlorodibenzodioxins and polychlorodibenzofurans
Several references are available on the subject. Most of the
information reported hereafter has been drawn from Taylor (1979), Moore
et al. (1979), NRCC (1981), Choudhry and Hutzinger (1982), and Rappe
(1984). See also Cesareo et al. (1985) for a general discussion on the
argument of environmental photochemistry.
None of the chemicals belonging to either family are produced by
the industry for commercial purposes, aside from the very small amounts
manufactured for special uses. However, PCDFs (135 congeners) and PCOOs
(75 congeners) have widespread diffusion in the environment - although
normally at low concentration levels (ppb range, or below) - as they
are trace-contaminants of PCPs and their salts and derivatives which
have found very extensive and dispersive uses since the 1930's. In
general, PCDFs have been found to be the major toxic contaminants in
PCBs, whereas PCDDs predominate in chlorophenols and derivatives.
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Photoconversion of PCBs and polychlorodiphenyl ethers to PCDFs has
been studied by Crosby and Moilanen (1973), Crosby et al. (1973),
Norstrom et al. (1976, 1977), and Choudhry et al. (1977a,b). Similarly,
irradiation of polychlorophenoxy phenols in methanol yielded a mixture
of various products including PCODs (Nilsson et al., 1974).
Undoubtedly there is some lack of information on the chemico-
physical properties of these halogenated compounds, as only a few
congeners, of the PCOD family in particular, have been characterized to
some degree. Characterization is often by analogy with similar sub-
stances (e.g. PCBs and chlorinated pesticides).
Congeners with four chlorine atoms or more can be expected to have
a very low water solubility («1 ppb), decreasing with increasing level
of chlorosubstitution. Lipophilicity, biomagnification, octanol/water
partition coefficient, and soil sorption partition coefficient, in-
stead, appear to increase with increasing chlorosubstitution. A few
data for 2,3,7,8-tetrachlorodibenzo-£-dioxin (2,3,7,8-T4CDD, often
abbreviated to TCDD or "dioxin") are:
- melting point: 306 °C;
- vapor pressure: <1*10"6 mmHg (25 °C);
- octanol/water partition coefficient: 1.4—19*10® (25 °C);
- soil-organic-carbon/water partition coefficient: 9.9-33*10 ,
- water solubility: 7.9—19.3 ppt, at room temperature (Adams
and Blaine, 1986; Marple et al., 1986).
Several PCOFs and PCDDs - and especially a number of those with
four, five, and six chlorine atoms - possess a high toxicity and,
indeed, TCDD is commonly considered as the most toxic man-made chemical
(US EPA, 1980d). Although toxic properties are related to degree of
chlorination, positional isomerism plays a critical role as well to the
extent that one should expect toxic potency to vary greatly even within
the same isomer group. By far, TCDO is the congener which has received
most attention. In general, PCDFs and PCDDs with low chlorosubstitution
degree (mono-, di-, and trichloroderivatives) are considered of much
less concern for the health of man and the environment.
PCDFs and PCDDs can be formed in combustion processes when the
proper precursors (polychlorinated biphenyls and phenols, respectively,
and polychlorinated benzenes) are present. For instance, industrial and
municipal incinerators appear to contribute to some extent to the
presence of PCDFs and PCDDs in the environment. PCDFs and PCDDs may
also originate from higher congeners by light-induced progressive loss
of chlorine, and may also arise in the environment from photolabile
chloroaromatics acting as precursors (Cesareo et al., 1985).
As PCDFs and PCDDs are characterized by a good chemical stability
(US EPA, 1984b), they have a lasting environmental persistence which,
combined with their constant input into the environment, could at
length lead to a general accumulation of such compounds in both the
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blotic and abiotic media. The environmental fate of PCODs is not known
with certainty. Most of the investigations have been conducted with
TCDO, and the conclusions regarding the environmental fate of the other
congeners have generally been drawn by analogy. Few data exist in the
literature that would indicate significant transformations of these
compounds in the atmosphere (Cavallaro et al., 1980; Eiceman et al.,
1981; Clement and Karasek, 1982; Tiernan et al., 1982), water (Ward and
Matsumura, 1978), or soil (di Domenico et al., 1980a,b, 1982).
In the atmosphere, PCODs are expected to be present in the vapor
phase and particulate-sorbed states. Both the calculated and the
experimental results show that PCODs will concentrate in sediments and
biota present in the aquatic media. Depending on the fish species, it
has been shown by static test procedures that the bloconcentration
factor (BCF) for TCDO ranges fro 2,000 to 30,000 (US EPA, 1984b).
However, determination of BCF for the great majority of PCDOs is yet to
be performed.
Although several investigators have implicated volatilization as
one of the major reasons for the observed disappearance of TCDD from
aqueous solutions during microbial studies, no quantitative information
regarding volatilization of TCDD from aquatic media is available
(Hiltter and Philippi, 1982; Matsumura et al., 1983). Using the formulas
of Liss and Slater (1974), a vapor pressure of 1.7*10"® torr, and a
solubility value of 6.2*10"10 mole/1, TCDD volatilization half-life
was calculated to be 6 minutes from water of 1-cm depth and 10 hours
from water of 1-m depth (NRCC, 1981; US EPA, 1984b). Pertinent data
regarding the volatilization of other PCDOs from aquatic media could
not be found in the literature.
III.5. Polychlorobiphenyls
PCBs (209 congeners) are a class of chlorinated aromatic compounds
introduced in the 1940s, which since then have found widespread appli-
cations because of their thermal stability and chemical inertness as
well as excellent dielectric properties (Mleure et al., 1976; WHO,
1976). The peculiar physical and chemical characteristics of PCBs have
led to their numerous utilizations as: dielectric fluids (capacitors,
transformers), industrial fluids (hydraulic systems, gas turbines, and
vacuum pumps), fire retardants, heat transfer fluids, and plastlclzers
(adhesives, textiles, surface coatings, sealants, printing, and copy
paper). During the period 1972—1974, U$ production of PCBs averaged
approximately 18*10® kg/y, with 15*10® kg representing the annual
marketed consumption in the US during that period (US EPA, 1980a).
Most information on the technical preparation, physical and
chemical properties, and general characteristics of PCBs come from
trade publications and technical encyclopedias (e.g. Hubbard, 1964).
PCBs commercially available (e.g. Aroclors) are generally complex
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liquid mixtures of many congeners with different degrees of chlorina-
tion. The mixtures with high chlorine content appear in the form of a
sticky resin or a whitish powder (Pearson, 1982). PCBs, similarly to
other related compounds, exhibit a very scant solubility in water
(ppm-ppb range) and a rather low vapor pressure (Pearson, 1982).
Some PCBs were shown to have insecticidal (Deonier et al., 1946)
and fungistatic (Beraha and Powell, 1953) activity. However, they were
apparently never used as pesticides although recommended for incorpora-
tion into pesticide formulations (Sullivan and Homstein, 1953; Tsao et
al., 1953). PCBs were also reported to increase the insecticidal
properties of DDT (Lichtenstein et al., 1969), organophosphorous
compounds (Fuhremann and Lichtenstein, 1972), and Carbaryl (Plapp,
1972).
Some PCBs are known to have toxic properties rather similar to
those of other chlorinated aromatic compounds such as PCNs. Moreover,
they are capable of inducing microsomal mixed-function oxygenases in
many animal species, including man (Goldstein, 1979): this action is
similar to that determined by the much more powerful and carcinogenic
TCDD. Indeed, ingestion of PCDF-contaminated PCBs, accidentally present
in cooking oil, has been associated with lethal poisoning and other
serious adverse effects in a moltitude of individuals in Japan (Urabe
et al., 1979). A great number of data are available which deal with the
environmental presence of PCBs and with their effects in man and his
biological environment. A treatment of these data is beyond the scope
of this project. Therefore, for information on such topics, the reader
is addressed to the very exhaustive review by Wassermann et al. (1979).
In 1966 the New Scientist published a note about the discovery of
PCBs widespread occurrence in the Swedish environment (Hutzinger et
al., 1974). A year later, mass spectroscopic data were reported as
unambiguous proof of the chemical nature of these contaminants and, at
approximately the same time, PCBs were found in various parts of the
world (Hutzinger et al., 1974; WHO, 1976). PCBs are strongly adsorbed
on solid surfaces, including glass and metal surfaces (Schoor, 1975),
soil, sediment, and particulate in the environment (Haque et al., 1974;
Dennis, 1976; Munson et al., 1976). In aquatic environments, PCBs are
associated with sediments and usually found at higher concentrations in
sediments than in water (Crump-Wiesner et al., 1974; Young et al.,
1976; Dennis, 1976). As with other chlorocarbons, PCBs are probably
associated strongly with microparticulates (Pfister et al., 1969).
Although the environmental behaviour and biological activity of a
number of individual PCBs have been studied in recent years, it is
still difficult to evaluate the potential toxicity of the complex
mixtures actually found In the environment since their composition
often changes. A further complication is that several commercial PCB
mixtures have been reported to contain small quantities of highly toxic
contaminants (PCDFs): in fact, some of the toxic effects observed in
animals and humans exposed to PCBs appear to be attributable to PCDFs
(US EPA, 1980a).
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IV. EXAMPLES OF PHOTODECOMPOSITIONS
Data relative to experiments carried out outside the environ-
mentally relevant wavelenghts and in non-aqueous solvents have been
considered only when deemed useful or in the absence of pertinent data.
Furthermore, data have been selected taking into account that natural
waters contain numerous chemicals (both natural and xenobiotic) so that
rates and products of environmental phototransformatlons cannot be
predicted by direct photolysis evaluation only. In fact, Indirect
interactions by energy transfer from an excited photosensitlzer acting
as a catalyst, as well as secondary reactions between substrate and
photolytically- or photochemically-generated reactive species (radi-
cals, singlet oxigen, ozone, photoconductive metal oxides, bases, etc.)
have been observed.
Therefore, data referring to homogeneous and heterogeneous photo-
catalysis have been particularly considered whenever available, since
photocatalysis, in addition to being always likely to occur, represents
the only possible photochemical path for chemicals which in water are
substantially transparent to sunlight radiations, i.e. their molar
extinction coefficients are lower than 1 M'^'cnf* above 290 nm
(ECETOC, 1981). Preliminary comparative analysis of effectiveness of
different photochemical processes as detoxlcation routes has been
tentatively carried out considering data relative to classes of con-
geners and obtained under as far as possible equivalent experimental
conditions.
IV.l. Polychlorobenzenes
Information relevant to environmental photochemistry is available
for each of the 12 PCBZs. A selection of data is reported in Tables
IV.la-c.
In liquid systems many data are available which refer to direct,
sensitized, and catalysis-mediated photodecomposition processes (Cesa-
reo et al., 1985). For the purpose of comparing the effectiveness of
these processes as detoxlcation routes for PCBZs it would be useful to
have, for each process, a set of homogeneous data on each PCBZ or, at
least, on one PCBZ for each group of isomers. This is because toxicity
is directly dependent on the number of chlorine atoms. However, for no
process such a set is available.
Very few and Inhomogeneous data refer to direct photolysis in
water. Homogeneous data are available for direct (unsensitized) photo-
lysis in water-acetonitrile mixture of tr1- to hexachlorobenzenes
(HgCBZ), for Indirect (sensitized) photolysis of tetra- (T^CBZ) to
hexachlorobenzene in the presence of acetone, and for Ti02~catalyzed
photooxidation of monochlorobenzene (MjCBZ; Figure IV.l), and .1,2-
and 1,4-dichlorobenzene (1,2- and 1,4-02CBZ). What follows is a short
suirenary of such data.
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As to direct photolysis in water, one finding seems relevant: at
300 nm, MjCBZ, which is estimated to have a negligible absorption
coefficient at that wavelength, was found to photohydrolyze quantitati-
vely into phenol.
In the unsensitized reaction, HgCBZ is the less persistent PCBZ
(with the unique exception of 1,2,4,5-T4CBZ). The photolability appa-
rently decreases along with decreasing chlorine content. Polychlo-
robiphenyls (PCBs) are absent among pentachlorobenzene (P5CBZ) and
HgCBZ photoproducts, while they do not exceed 32 and 5% of photopro-
ducts formed from T4CBZ and trichlorobenzene (T3CBZ), respectively.
HgCBZ is practically dechlorinated to PgCBZ only, whereas for other
PCBzs the dechlorination process involve the parent compound and its
primary photodechlorination products. The percentage of unknown photo-
products is rather high, except for HgCBZ.
In the sensitized reaction, HgCBZ is the more persistent PCBZ.
Excluding T3CBZs from consideration (as they were examined in methanol-
acetone solutions), the photolability apparently increases along with
decreasing number of chlorine atoms. PCBs, whose content may be as high
as 13%, are present among photoproducts of each group of isomers,
except among those of HgCBZ. In general, monodechlorination prevails
largely on didechlorination. The quantity of unknown photoproducts 1s
equivalent to that observed in the unsensitized reaction.
Comparison among rates and products in the sensitized and unsensi-
tized reactions shows that: (a) reactions are faster under sensitized
conditions (however, the most hazardous PCBZ is degraded slower); (b)
the proportion of mono- to didechlorinated congeners is generally
higher in the sensitized reaction, except for HgCBZ; (c) PCB quanti-
ties produced are always lower in the absence of sensitizer; and (d)
proportion of unidentified vs. identified photoproducts is substantial-
ly equivalent in the two processes. Futhermore, the fact that both PCB
formation is enhanced up to more than twice as much, and monodechlorin-
ated congeners generally prevail on the di- or tridechlorinated ones,
indicates that detoxlcation is less efficient 1n the presence of
sensitizers.
T^-catalyzed phototransformation data refer to M^CBZ and
1,2-D2CBZ tested In a 0.1X-Ti02-water slurry. The few qualitative
data show that both substrate loss and dechlorination are relatively
slow, and that mineralization does not occur. Furthermore multiple
photoproducts, including PCBs, are formed. Therefore, Ti02 particles
do not seem a good candidate material for decontamination of M^CBZ-
or D2CBZ-conta1n1ng waters, although much higher degradation rates
were observed with 1,4-D2CBZ dissolved in water containing 1% Ti02.
IV.2. Polychlorophenols
The following general considerations, summarized in Table IV.2,
may be drawn from available data (Cesareo et al., 1985).
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Direct photolysis under sunlight is an important route for PCP
dechlorination. Pentachlorophenol (P5CP) is degraded faster then
4-chlorophenol and 2,4-dichiorophenol and its dechlorinated products
are readily converted into secondary products of increasingly lower
clorine content. Therefore, direct photolysis - although some evidence
of formation of polychlorodibenzodioxins (PCDDs) 1n very small quanti-
ties is available - may be considered an effective route for detoxica-
tion of PCPs present 1n the photic zone.
P5CP 1s known to undergo photochemical degradation 1n solution
in the presence of sunlight, with the subsequent formation of several
chlorinated benzoquinones, 2,4,5,6-tetrachlororesorclnol and chloranil-
ic acid (Mitchell, 1961; Hamadmad, 1967). Na-PgCP Is decomposed
directly by sunlight, with the formation of numerous products, includ-
ing oxidized monomers, dimers, a trimer, and chloranilic acid (Munakata
and Kuwahara, 1969). Wong and Crosby (1978) reported the degradation by
sunlight or UV light of dilute solutions of P5CP to lower chlorophen-
ols, tetrachlorodihydroxybenzenes, and nonaromatic fragments, such as
dichloromaleic acid. The irradiation of Na-PsCP in relatively high
concentrations in aqueous solutions was also reported to form octachlo-
rodibenzodioxin (OgCDD).
The role of heterogeneous photocatalysis on PCP degradation was
also investigated (Figures IV.2a-d). The efficiency of Ti02 particles
in promoting photodegradation of 4-MjCP and P5CP in aqueous solution
was found very high provided sufficient aeration was provided (Barbeni
et al., 1984, 1985: Pelizzetti et al., 1985).
4-MjCP (5*10"^ M) dissolved in a 0.2% TK^-water slurry was found
to undergo quantitative mineralization to HC1 and CO2 when irradiated
at 340 nm (half-ljves of 35 and 80 min at pHs 12 and 4.5, respective-
ly). P5CP (4'10"5 M), under the same experimental conditions, was
mineralized with a higher rate. Its half-Hfe was 20 and 15 m1n as
unionized and ionized species, respectively. The same experiments
carried out in the absence of semiconductor showed negligible photode-
gradation of both compounds. Much lower mineralization yields were
obtained when Ti02 was substituted with SIO2• or other metal
oxides. Sunlight had equivalent effects as artificial light on the
degradation of P5CP and 4-MjCP dissolved in TIO2-water suspensions.
Sunlight-induced photominerallzation of PCPs in water may be
artificially promoted by suspended TIO2 particles. Potentially, this
process may be utilized for treatment of PCP-containing waste waters,
provided that the process is conducted under controlled conditions that
prevent eventual formation of toxic by-products.
IV.3. Polychloronaphthalenes
A limited amount of data is available on PCN photodegradation: the
following information (Tables IV.3a,b) has been drawn from Ruzo et al.
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(1975a,b). No information was provided in the original papers as to the
total amounts of parent compounds lost.
In the acetonitrile-water (4:1) mixture and under UV light (>285
nm) irradiation, monochloronaphthalenes (MjCNs) were converted chiefly
into chlorobinaphthyls (PCBNs), while naphthols, arising from the
photosubstitution of chlorine, and small amounts of hydroxylated dimers
were also identified. However, in the presence of oxygen, naphthol was
the preponderant product. Additional data show that while major photo-
chemical pathways are substantially the same, the relative photoproduct
yields may change remarkably. In particular, MjCNs in acetonitrile-
water tend to form mainly binaphthyls, whereas naphthalene is a major
product in unsensitized organic media.
It may also be observed that the dechlorination/dimerization
ratios cover a wide range of values, which indicates marked substituent
effects. In general, dechlorination is favored with PCNs that have
adjacent (vicinal or peri) chlorine atoms, while unhindered PCNs yield
mostly dimers. Relative reaction rates are greater for the former type
of PCNs, with the somewhat expected exception of 1,2,3,4-tetrachloro-
naphthalene.
No data seem to be available as to water media alone (Cesareo et
al., 1985). However, by analogy with similar compounds, the experimen-
tal evidence in organic solvents suggests that sunlight might promote
phototransformation of substrates also in aqueous systems yielding
analogous photoproducts. These processes, however, might not entail an
effective detoxication as PCNs with intermediate chlorosubstitution
level are generally more toxic than the higher congeners. Furthermore,
no information is available on toxicity of PCBNs and other photopro-
ducts observed.
Sunlight irradiations of a number of PCNs as solid films on quartz
surface gave only insoluble polymeric material.
IV.4. Polychlorodibenzofurans
Some pertinent data for PCDFs are summarized in Table IV.4.
Sunlamp irradiation of 2-chloro- and 2,8-d1chlorod1benzofuran (2-MjCDF
and 2,8-D2CDF) in water determined a scant loss of both compounds
(Crosby and Moilanen, 1973). 2-MjCDF in purified methanol was also
scarcely affected by light. Sunlamp irradiation of 2,8-D2CDF in highly
purified methanol, or acetone-added purified methanol, yielded photode-
gradation to 2-MjCDF with slow but similar reaction rates. However,
photolysis occurred at a remarkably faster rate when utilizing a
laboratory-grade solvent or after addition of 4,4'-d1ch1orobenzophenone
as a sensitizer to the high purity methanol (Crosby and Moilanen, 1973;
Crosby et al., 1973). The conclusion was drawn that medium impurities
can drastically alter photodecomposition rates, and that the environ-
mental sensitization of PCDF photolysis seems quite plausible.
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UV-lamp Irradiation of 2,8-D2CDF in methanol or hexane solutions
resulted in a rapid loss of the original substrate (Hutzlnger et al.,
1973): decomposition was faster in methanol than in hexane. The same
may be said for octachlorodibenzofuran (OgCDF). However, 1n the same
solvent both chemicals decomposed with similar reaction rates. No other
products but those formed by progressive dechlorination of original
substrates were found to be present.
It may be pointed out that 2,8-D2C0F and OgCDF exposed to sunlight
as thin film on quartz underwent a progressive loss of chlorine atoms,
although in the case of D2COF a trichloroderivative was also detected.
In both cases, parent compound disappearance was limited (Hutzlnger et
al., 1973).
For further Information, see Choudhry and Hutzlnger (1982), and
Cesareo et al. (1985).
IV.5. Polychlorodibenzodioxins
It may be observed that only 1n few cases reaction products have
been investigated, and always on a qualitative basis. A quantitative
determination of photoproducts, which would account satisfactorily for
the amount of substrate loss, Is normally absent (Table IV.5).
Sunlight degrades PCOOs in organic media under various irradiation
conditions as the UV section of the solar spectrum provides enough
energy as to Induce direct photolysis. As experimental conditions are
generally diverse, quantitative comparison between findings of differ-
ent authors may not be carried out. However, one striking feature
appears recurring In various experiments: UV-induced loss of chlorine
atoms in solubilized higher PCDD congeners seems to occur preferential-
ly from lateral (2-, 3-, 7-, or 8-) positions flanked on both sides by
adjacent chlorines (Buser, 1976b, 1979; Oobbs and Grant, 1979; Nestrick
et al., 1980). It was also shown that the peri positions (1-, 4-, 6-,
or 9-) lost chlorine at a rate slower than the lateral positions.
Therefore, 2,3,7,8-tetrachlorodibenzodioxin (TC00) was predicted as
likely being the most photolablle of all PCDDs (Dobbs and Grant, 1979):
this was later confirmed for the TCDD subgroup and a few other higher
PCOOs Including OgCOO (Nestrick et al., 1980).
Methanol 1c or ethanolic solutions of 2,7-d1ch1orodibenz
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' It can be pointed out that negligible loss of TCDD was determined
when the substrate was UV-irradiated as an aqueous suspension (Crosby
et al., 1971). Addition to the water medium of a surfactant (Tween-80)
and benzene produced some decay of the compound when the light source
was a sunlamp (Plimnter et al., 1973).
As TCOO is so scarcely soluble in water, addition of a surfactant
seems to be necessary in order to obtain an increase of the substrate
solubility and a reasonable stabilization of the system as due to the
surfactant micellar action. The study by Botr§ et al. (1978) shows
clearly that TCOO photodecomposition in such media may be complete and
occurs at a rate faster than that in methanol under equal irradiation
conditions (Figure IV.5a). According to the authors, the reason for
such an increase in the decay rate is not completely understood as yet,
but the experimental evidence seems to support the existence of a
stabilizing interaction via - orbitals between the pyridin ring and the
aromatic nucleus of TCDD, allowing some energy to be transferred with
consequent enhancement of the toxicant photodecomposition rate.
A study on TiOg-photocatalytic degradation in water (Pelizzetti
et al., 1988) showed that 2-MjCDD disappearance rate increased with
increasing Ti02 concentration (Figure IV.5b,c).
TCDD went through UV irradiation substantially unchanged when
distributed on dry or wet soil, when in the form of a thin dry film on
a glass dish, or even when suspended in distilled water.
For further information, see Choudhry and Hutzinger (1982), and
Cesareo et al. (1985). In general, photochemical data show that sun-
light may be capable of inducing phototransformation of PCDFs and
PCDDs. Experimental evidence shows that an important pathway is reduct-
ive dechlorination to congeners with lower chlorine content in both
direct and sensitized (catalyzed) photolysis. Whether dechlorination be
a way to detoxication may not be assessed. In fact, in addition to the
number of chlorine atoms, other factors interplay in determining actual
toxicity (see Subsection III.4). Furthermore, rates of substrate loss
as well as those of formation of daughter compounds have been investi-
gated to a very limited extent, or not at all.
IV.6. Polychlorobiphenyls
The reactions of environmental importance that PCBs appear to
undergo include alkali- and photochemically-catalyzed nucleophilic
substitutions and photochemical free radical substitutions, all of
which occur with alkali and water. Photolysis generally has been found
to give one major type of product - namely chlo/ophenols - in that
chlorine is replaced by hydroxyl groups (especially in Aqueous systems)
(Hutzinger et al., 1972, 1974; Ruzo and Zabik, 1975; US EPA, 1980a).
The photochemical behavior of higher chlorobiphenyls appears to be
similar to that of the tetrachlorobiphenyls (Hutzinger et al., 1972;
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Herring et al., 1972). Irradiation of Aroclor 1254 in aqueous solution
gave rise to dechlorinated and hydroxylated products. Hexa- and
octachlorobiphenyls are more photochemically reactive than tetra-
chlorobiphenyls (Hutzinger et al., 1972; Herring et al., 1972).
The creation of free radicals by sunlight allows the environmental
replacement of chlorines by hydroxyl groups from water without the
intervention of alkali. When this occurs at the ortho position (found
to be the most preferred for chlorine loss), the resulting 2-hydroxy-
chlorobiphenyl is perfectly positioned to allow oxygen to bond to an
ortho position of the other ring. This results in the production of
potentially the most important class of contaminant in commercial
mixtures of PCBs, the chlorinated dibenzofurans.
Photodegradation of aqueous D2CB in the presence of various
semiconductor powders was investigated by Pelizzetti et al. (1988): as
for other instances, TIO2 was found to be an active catalyst (Figure
IV.6a). The same was observed in the catalysis-assisted photodegrada-
tion of DOT (Barbeni et al., 1986; Figure IV.6b).
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V. LAYOUT OF PHOTODEGRADATION PROJECT
V.l. Purpose of the project
The project described hereafter is concerned with the development
of photochemical methods for treatment of halogenated aromatic com-
pounds in order to detoxify them prior to be - or while - present in
the environment. Such compounds are in fact of particular concern due
to their generally high chronic toxicity to humans and animals and
persistence in the environment. The specific aims of this project are:
(1) To develop efficacious photochemical methods of inactivation
for selected halogenated aromatic compounds ("tracers", see
Experimental hereafter) which may be considered representa-
tive of the chemical classes mentioned in the Introduction;
(2) To develop methodological procedures to carry out photochemi-
cal degradation, possibly by means of natural sunlight;
(3) To determine, where possible, the kinetics of inactivation of
the chemicals by the particular agents utilized, and identify
the main products of inactivation;
(4) To indicate the feasibility, under the engineering profile,
of the inactivation methods developped when transferred from
laboratory to environmental scale.
V.2. Experimental
V.2.1. Chemicals and equipment
The classes and chemicals (tracers) to
below as per a preliminary selection.
Class of Chemical
(1) Polychlorobenzenes (PCBZs)
(2) Polychlorophenols (PCPs)
(3) Polychloronaphthalenes (PCNs)
(4) Polychlorodibenzofurans (PCDFs)
(5) Polychlorodibenzo-£-dioxins (PCODs)
(6) Polychlorobiphenyls (PCBs)
be studied are tabulated
Tracer
Mono-, di-, and hexa-
chlorobenzenes
Pentachlorophenol
Tetra-, and octachloro-
naphthalenes
Tetra-, and octachloro-
dibenzofurans
Tetra-, and octachloro-
dibenzodioxins
Penta-, and hexachloro-
biphenyls
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All halogenated aromatics employed will be of GC or HPLC grade. In
most instances, It Is anticipated that no further purification will be
necessary. However, if initial analytical assay Indicates the presence
of a substantial amount of contamination, preparatory chromatography
will be used to obtain a purified compound. All other chemicals and
solvents utilized will be of analytical, or higher quality, grade -
according to experimental requirements.
V.2.2. Solubility determination
It will be necessary to have reliable values for the generally low
aqueous solubility of each of the compounds investigated. Thus, it will
be useful to confirm aqueous solubility figures as given 1n the litera-
ture, if any, by redetermining them using standard methods. If solubil-
ity figures are not available, they will have to be determined.
In some instances, it may be necessary to add a dispersive agent
in order to dissolve the substance above its solubility limit and bring
its concentration in the medium to the value of practical interest
(ppb-ppm range). The precise effect of such agent on the inactivation
process will have to be determined.
V.2.3. Volatilization
Substrate loss due to volatilization will be assessed for instance
by bubbling pure dry nitrogen through the aqueous solution of the
compound at various flow rates and at the temperature(s) of interest.
An XAD2 resin trap, or a similar device, may be used. At the end of the
experiment, the resin will be extracted and the amount of substrate
loss determined with the available techniques.
V.2.4. Photochemical degradation
The chlorinated substratum will be added to the water medium
generally in the presence of catalysts chosen in the broad classes of
surfactants, water-mlxable organic solvents, semiconductor particles,
or natural silica derivatives. The specific role of catalysts added to
the pure matrix will be studied 1n detail as they appear to have marked
importance in enhancing photoprocess quantum yield. The latter is
generally low for the compounds of interest. On the other hand, addi-
tion of a catalyst may help in keeping the substrate in a highly
dispersed form or in increasing substrate solubility which is often
very scant.
Typical experiments will be carried out under aerobic conditions:
freshly boiled, doubly distilled water will be used. However, the
matrix will be deoxygenated if necessary. In general, the temperature
will not exceed environmental values, although some trials at higher
temperatures might be performed. Samples will be contained in small
(<100 ml) Pyrex reaction containers, sealed before irradiation.
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The wavelength range of interest is the solar region between >285
and 350 nm: therefore, direct sunlight will be employed. However,
alternatively a Solarbox lamp whose emission covers such range will
also be utilized. In such case, the light source will be selected in
order to have a reasonable imitation in quality and quantity of the
aforecited sunlight section, with a cutoff filter at high energy if
necessary.
For examples of experimental procedures, reference may be made to
papers by Barbeni et al. (1984, 1985). Most of the equipment required
is already available. At any rate, it is reasonable to assume that
development of a specific photoreactor might be necessary.
V.2.5. Analysis
Most of the analytical methods used for the identification and
quantitation of the compounds of interest are based on extraction of
the reaction mixture followed by gas chromatography (GC) as this is the
best method of choice when dealing with thermally stable compounds. GC
can provide both high sensitivity (detection at low ppt level) and
selectivity (Crummett and Stehl, 1973; Buser and Bosshardt, 1976;
Buser, 1976a, 1977; Esposito et al., 1980; di Domenico and Merli,
1985).
Gas chromatography may be coupled with mass spectrometry (MS) to
enhance selectivity and facilitate identification. The more commonly
used analytical technique to avoid the problem of interferences from
closely related compounds is to utilize low resolution mass spectro-
metry incorporated with a very selective separation step such as a GC
capillary column (hrGC-MS).
GC with an electron capture detector (Buser, 1976a, 1977), or
preceded by high pressure liquid chromatography (HPLC) (Nestrick et
al., 1979; Bumb et al., 1980) may also be utilized. The latter method
is highly selective in characterizing some of the closely related
polychlorinated compounds proposed in this investigation. Another valid
combination of instrumental techniques is HPLC followed by GC-MS.
For the HPLC analyses, eventually followed by GC, an aliquot of
the reaction mixture at a particular time is extracted with hexane and
the hexane layer separated and analyzed directly by HPLC (normal-phase
HPLC). For reverse-phase HPLC, the hexane layer is evaporated to
dryness and the residue taken up with methanol and subsequently
analyzed. Standard HPLC conditions may be obtained from the literature
(Nestrick et al., 1979; Bumb et al., 1980).
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V.3. Experimental work schedule
(1) Physical parameters
(a) Solubility
(b) Volatilization
Years: 1
(2) Photochemical degradation
(a) Disappearance rate
(b) Product and production rate analysis
- Main focus on disposal of chemical wastes and
environmental fate in aqueous systems
- Reclamation of soil and solid surfaces will be
considered
- Simulated and natural sunlight as irradiation
sources
Years: 1, 2, and 3
(3) Product identification
Mixtures of products and purified fractions will be
analyzed by GC-MS when deemed appropriate
Years: 1. 2. and 3
V.4. Budget
The proposed total budget is based on a three-year period research
plan.
Year 1 Year 2 Year 3
Total
Stipend
Equipment
Travelling
Maintenance, etc
40,000 42,000 44,100
5,000
126,100
5,000
14,186
28,372
4,500 4,725 4,961
9,000 9,450 9,922
Total (direct costs), US$ 58,500 56,175 58,984 173,659
Direct plus indirect
(10%) costs, US$ 64,350 61,793 64,882 191,025
ISS Total Cost for Three-Year Project, USi: 191,025
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VI. REFERENCES
Adams, W.J., and Blaine* K.M. (1986): A Water Solubility Determination
of 2,3,7,8-TCDD, Chemosphere 15, 1397-1400.
Ausmus, B.S., Kimbrough, S., Jackson, D.R., and Lindberg, S. (1979):
The Behavior of Hexachlorobenzene in Pine Forest Microcosms: Tran-
sport and Effects on Soil Processes, Environ. Pollut. 20, 103-111.
Barbeni, M., Pramauro, E., Pelizzetti, E., Borgarello, E., Gratzel, M.,
and Serpone, N. (1984): Photodegradation of 4-Chlorophenol Cata-
lyzed by Titanium Dioxide Particles, Nouv. J. Chim. 8, 547-550.
Barbeni, M., Pramauro, E., Pelizzetti, E., Borgarello, E. and Serpone,
N. (1985): Photodegradation of Pentachlorophenol Catalyzed by
Semiconductor Particles, Chemosphere 14, 195-208.
Barbeni, M., Pramauro, E., Pelizzetti, E., Borgarello, E., Serpone, N.,
and Jamieson, M.A. (1986): Photochemical Degradation of Chlorin-
ated Dioxins, Biphenyls, Phenols and Benzene on Semiconductor
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D-54
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Photodeqradation Report. FIRST DRAFT.
NATO/CCMS Meeting. Bilthoven. November 1988.
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Photodeqradation Report. FIRST DRAFT.
NATO/CCnS Meeting. Bilthoven. November 1988.
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Istituto Superiore d1 SanitS. Rome.
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NATO/CCflS Meeting. Bilthoven. November 1988.
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D-58
AdD, NAPHO/NAPH01. jjt „ , M
Istituto Superlore d1 Sanita. Rome.
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Photodegradatlon Report. FIRST DRAFT.
NATO/CCnS Meeting. Bilthoven. November 1988.
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Photodegradation Reoprt. FIRST DRAFT. „
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D-60
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Photodegradatlon Report. FIRST DRAFT.
NATO/CCflS Meeting. Biithoven. November 1988.
Table II'.a. Energy conversion table. From: N.J. Turro (1978), Modern
Molecular Photochemistry, p. 8, Benjamin/Cummlngs Publishing Company,
Menlo Park.
Region
JL
7
AE
v
A
nm
cm"1
kcal/mole
sec"1
2.000
200
501000
143.0
15 x 10"
1500
250
40,000
114.4
12 x 101S
3,000
300
33433
95.3
1.0 x 10"
3,500
350
28,571
81.7
8.7 x 10"
4,000
400
25,000
71.5
7.5 x 10"
4,500
450
virn
63.5
6.6 x 10"
3,000
500
20,000
57 2
6.0 x 10"
5,500
550
18,182
510
5.4 x 10"
6,000
600
16,666
47.7
5.0 x 10"
6,500
650
15,385
44.0
4.6 x 10"
7,000
700
14,286
40.8
4.2 x 10"
10,000
1,000
10,000
28.6
3 x 10"
50,000
5,000
2,000
5.8
6 x 10"
100,000
10,000
1,000
186
3 x 10"
10*
10'
10
3 x 10"J
3 x 10"
10"
10'
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Photodearadatlon Reogrt. FIRST DRAFT.
NATO/CCnS Meeting. Bilthoven. November 1988.
Table II.b. Bond dissociation energies (kJoule/mole) of single bonds in
relation to solar radiation energy. From: 0. Hutzinger, Ed. (1982), The
Handbook of Environmental Chemistry, Vol. 2, Part B, p. 12, Springer-
Verlag, Berlin.
H
CI
Br
I
H-
4 3 5
4 3 1
3 6 4
2 9 7
HjC-
4 3 5
3 S 2
2 9 3
2 3 5
h,c4-
4 6 9
3 6 0
3 3 5
2 7 2
H,C=CH-
4 3 2
3 7 3
60S 390 302 243 201 E (kJoule/mole)
-4 1 I I I I i I I I I l l I I l I t I l l I I I I l l
200 300 400 S00 600 4(nm)
i i i i i i t Solar radiation
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AdD. NAPH0/NAPH01. . , .
Istituto Superiore d1 Saniti. Rome.
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NAiU/CCns Meeting. BIlthovenTNovefnber 1988.
Table II.c. Solar energy (microwatt/cm^) distribution on a horizontal
surface at midday on a typical clear day 1n midsummer 1n Cleveland,
Ohio (latltutde 41.5°N). From: L.R. Koller (1952), Ultraviolet Radia-
tion, p. 125, John Wiley and Sons, New York.
Wavelength
Sunlight
Sky Light
Total
3000
2.6
2.6
5.2
3100
24 •
23.5
47.5
3200
65
60
125
3300
108
96
204
3400
126
107
233
3550
144
115
259
3700
186
139
325
3850
192
136
333
4000
268
165
433
4100
339
209
548
42Q0
377
223
600
4300
404
213
617
4400
426
201
627
4500
453
216
669
4600
492
234
726
4700
514
229
743
4800
525
218
743
4900
525
207
732
5000
525
193
718
5100
508
184
692
5200
492
168
660
5300
514
162
676
5400
535
158
793
5500
535
154
689
5600
525
146
671
5700
525
138
663
5800
514
132
646
5900
508
124
632
6000
503
118
621
6100
497
113
605
6200
486
no
596
6300
475
107
582
6400
464
102
566
6500
459
97
556
6600
453
93
546
6700
459
92
551
6800
481
91
572
6900
475
89
564
7000
464
85
549
« Saalti. Rom. " ^
-------
Phgtodegradation Report. FIRST DRAFT.
NATO/CCRS Meeting. Bilthoven. November 1988.
Table IV.la. Phototransformations of PCBZs: substrate loss and products
in direct, sensitized, and heterogeneous catalysis-mediated photoproc-
esses (>285 nm) in various matrices. From: Cesareo et al. (1986).
Substrate
Irradia- Sub- Products (%)
MjCBZ
MjCBZ
MjCBZ
2-DoCBZ
2-D2CBZ
4-D2CBZ
4-D2CBZ
2,4-ToCBZ
2,4-T3CBZ
2.4-ToCBZ
2,3-T3CBZ
2,3-T3CBZ
2,3-T3CBZ
3.5-T3CBZ
3,5-T3CBZ
3,5-T3CBZ
2,3,4-T4CBZ
2.3.4-T4CBZ
2.3.5-T4CBZ
2,3,5-T4CBZ
2,4,5-T4CBZ
2,4,5-T4CBZ
P5CBZ
P5CBZ
P5CBZ
HgCBZ
HgCBZ
HgCBZ
Solvent3
tion time
strate
Congeners'1
0thersc
(hours)
loss (%)
-CI j
-Cl?
Wa
100
Phenol
Wa-Ti02
2
20
MXCP
Wa-Ti02
10
D2CBs
Wa-Ti02
Short
PCPs
Wa-Ti02
Long
D2CBs
Wa-Ti02
5 minutes
50
Wa-clay
0
Wa-An
51
40
54
Me-02
7
96
74
Me-Ac
5
53
81
0.6
Wa-An
51
28
38
Is
Me-02
7
63
85
5
Me-Ac
1.5
25
99
Wa-An
51
39
23
Is-P5CBs
Me-02
22
31
96
Me-Ac
3
72
37
3
PCBs
Wa-An
40
56
35
32
PCPs-Is-H7CBs
Wa-An-Ac
4
78
42
7
PCPs-PCBs
Wa-An
36
48
36
4
P5CPs-Is-PCBs
Wa-An-Ac
1.5
64
60
2
PCPs-PCBs
Wa-An
8
98
28
9
P5CPs-Is-PCBs
Wa-An-Ac
4
90
25
12
T3CPs-PCBs
Wa-Ac
24
41
20
21d
Wa-An-Ac
4
54
75
8d
PCBs
Me
7 dayse
0
Wa-An
8
34
77
3
Wa-An-Ac
16
29
71
7
Me
15 dayse
62
5
PCPs
(a) Wa: water. An: acetonitrile. Me: methanol. Ac: Acetone.
(b) With loss of one (-CI}) or two (-Cl2) chlorine atoms.
(c) Generally, polychiorophenols, isomers (Is) and polychlorobiphenyls.
(d) Including tridechlorinated congeners.
(e) Light source: solar irradiation.
0-64
AdD, NAPHO/NAPHOl.
Istituto Superlore d1 SanltS. Rome
-------
Phojtodegradation Report. FIRST DRAFT. „
NATO/CCnS Meeting. Bilthoven. November 1988.
Table IV.lb. Half-lives (in hours) of different trichlorobenzenes
in various media. Estimates obtained assuming first order kinetics.
Water- Methanol Methanol- Methanol- Methanol-
T3CBZ acetonitrile (deaerate
-------
Photodegradation Rep
-------
.todegradation Report. FIRST DRAFT.
NATO/CCMS Meeting. Bilthoven. November 1988.
Table IV.2. Direct photolysis and heterogeneous photocatalytic degrada-
tion of 4-MjCP and P5CP. From: Cesareo et al. (1986).
Sub-
strate
Irradia-
tion
(nm) (h)
Direct photolysis
(Matrix: Water)
pH"
Catalyzed photolysis
(Matrix: 0.2% TiQ?-Water)
Sub- Prod- Sub- Prod-
strate ucts pHa strate ucts
loss (%) loss (%)
4-MiCP >340
4-MiCP >340
4-MjCP >340
P5CP
P5CP
P5CP
>310
>330
>290
1
5.6
0
4.5
40
HC1-C0'
1
5.6
0
12.0
70k
hci-co:
22
5.6
<10
4.5
98°
HC1-C0
1
3.0
3C
3.0
94d,e
HC1-C0
1
10.5
6
10.5
99
hci-co!
7.3 50' PCPs, diols,
dichloro-
maleic acid
(a) Initial pH.
(b) This was found negligible in degassed T102 slurry or in Ti02-aceto-
nitrile slurry, and <20% when TIO2 was replaced with Si02•
(c) Loss was 44% at pH 3 10.5.
(d) Including loss of PgCP adsorbed on Ti0£ (negligible at pH ¦ 10.5).
(e) This became 50% in degassed dispersion, and 20% when Tii^ was sub-
stituted with AI2O3.
(f) This became 100% after 20 hours; Same observed after 10-day expo-
sure to sunlight. At pH » 3.3, loss was 50% after 100-hour irradia-
tion.
D-67
AdD. NAPH0/NAPH01.
Istituto Superiore di SanitS. Rome.
-------
Photodegradation Report. FIRST DRAFT.
NATO/CCRS Meeting. Bilthoven. November 1988.
Table IV.3a. Distribution of photoproducts and quantum yields of mono-
and dichloronaphthalenes (derived from Ruzo et al., 1975a).
ReaOion ! ~ ~
Substrate Solvent quantum uechlon- Binapn- Other(b.c)
yield(a) nation(b) thyls(b)
1-MiCN Methanol(d) 0.005 74 25 <1
1-MjCN Methanol- 0.002 76 23 <1
oxygen
1-MjCN Methanol- 88 12
hydrobromi c
acid
1-MnCN Cyclohexane 88 12
1-MjCN Acetonitrile- <1 94 5 <1
water
2-MiCN Methanol(d) 0.007 58 38 4
2-MjCN Methanol- 0.007 2 97 1
benzophenone
2-MjCN Cyclohexane 72 28
2-MjCN Acetonitrile- 2 94 4
water
1,2-D2CN Methanol 0.012 32(e) 66 2
1,2-D2CN Methanol- 0.014 28 68 4
benzophenone
(a) Degassed solutions, unless differently stated. 20-60 h irradia-
tions.
(b) Yields were estimated as percentage of total product formation by
comparison with standard concentrations of naphthalene and binaph-
thyl.
(c) Substitution (left column) and chlorination (right column) prod-
ucts.
(d) The material balance on naphthyl residues was >952 in early stages
of the reaction (6 h).
(e) Approximately equal amounts of 1- and 2-MjCN.
D-68
s?itutoH§uper/ore di Sanita. Rome.
-------
Ph
N,"
hotqdegradation Report.
lATO/CCflS Meeting. Bilth
FIRST DRAFT. , „
oven. November 1988.
Table IV.3b. Polychloronaphthalene degradation in methanol(a) under UV
irradiation (derived from Ruzo et al., 1975b).
Substrate
Irradiation
time (hours)
Relative
reaction
rate
Dechlorination
products
^voe)
Other(b)
1,8-D2CN 40
1.2-DoCN 40
1,3,5,8-T4CN 120
1-MiCN 40
2,7-D2CN 120
2.3-02CN(c) 120
1.4-D2CN 120
2-M]CN 120
1.5-02CN 120
1,3,5,7-T4CN 120
1,2,3,4-T4CN 120
56.0
10.1
9.0
8.6
8.3
8.0
6.3
5.9
4.0
2.3
1.0
86
25
80
28
6
25
10
15
2
1
80
1-MjCN
1-, 2-MjCN (1:1)
1.4.6-T3CN
2-M,CN
2-MiCN
1-MjCN
1-MjCN
1.3.7-T3CN
Mixture of
various congeners
t3cbn
t3cbn
h7cbn
M^BN
T7CBN
t3cbn
t3cbn
MiCBN
t3cbn
h7cbn
h7cbn
(a) In the presence of air. Degassed solutions containing benzophenone
(0.15 M) exhibited the same reaction rates. All photolyses carried
out at 30 °C.
(b) In addition to chlorobinaphthyls, small amounts of methoxylated
naphthalenes (<2%) and methoxylated binaphthyls were observed.
(c) Methanolic 2,3-D2CN irradiated by sunlight showed a similar photo-
degradation pattern.
D-69
AdD. NAPHO/NAPHOl.
Istituto Superiore di Sanitf. Rome.
-------
Photodearadation Report. FIRST DRAFT.
NATO/CCRS Meeting. Bilthoven. November 1988.
Table IV.4. Photochemistry of MjCDF, D2CDF, and OgCDF in water, metha-
nol and hexane.
Substrate
Solvent
Irradiation
Light Time (hours)
Substrate
loss (%)
Products
2-MjCDF(a)
2-MjCDFU)
2,8-D2C0F(a,b)
2,8-D2CDF(c)
2,8-D2CDF(a,c)
2,8-D2CDF(a,c)
2,8-D2CDF(d)
2,8-02CDF(d)
OaCDF(d)
OgCDF(d)
Aqueous
Sunlamp
Low
suspension
Methanol
Sunlamp
>125
<10
(at 30 °C)
Aqueous
Sunlamp
Low
2-MjCDF
suspension
Methanol
Sunlamp
48
>95
2-MiCDF
High purity
Sunlamp
112
58-83 2-MiCDF
methanol, or
acetone-added
purified
methanol
Purified
Sunlamp
112
100
methanol,
DCBPh(f)
added
after 90 h
Methanol
UV lamp
<1
100
Z-M^DFfe)
(310 nm)
Hexane
UV lamp
6
>90
2-MjCDF(e)
(310 nm)
Methanol
UV lamp
<1
100
T4CDF, PcCDF,
(310 nm)
HgCDF, H7CDF.
Some D2CDF
and T3CDF(e)
Hexane
UV lamp
2
>90
t4cdf, p5cdf,
(310 nm)
HgCDF, H7CDF.
Some D2CDF
and T3CDF(e)
(a) From Crosby and Mollanen (1973).
(b) 2,8-D2CDF absorption maximum in methanol located at ca. 290 nm. Ab-
sorption negligible at wavelengths >320 nm (Crosby et al., 1973).
(c) From Crosby et al. (1973).
(d) From Hutzinger et ai. (1973).
(e) Unidentified polymeric products when irradiation ca. 20 h.
(f) 4,4'-Dich1orobenzophenone.
D-70
fstitutoHSuperiore d1 Sanita. Rome.
-------
PhotQdeqradatlon Reoort. FIRST DRAFT.
NATO/CCWS Meeting. Bmhoven. November 1988.
Table IV.5. Photochemistry of D2CDO, T3CDO, T4CDD, HgCOD, H7CDD, and
OgCOO in various organic solvents and in aqueous media.
Substrate
Solvent
Irradiation
Substrate Products
Light Time (hours)
loss (%)
2,7-D2CDD(a)
Methanol(b)
UV lamp
6
70
2,7-02CD0(c)
Octanol, or
Sunlamp
0.67
50
isooctane
2,3,7-T3CD0(d)
Hexane
UV lamp
1.17
61(e)
(313 ran)
2,3,7,8-T4CDD(a)
Aqueous
UV lamp
Negligible
suspension
2,3,7,8-T4CD0(f)
Water,
UV lamp
4
90
CPC(g)
added
(254-356
nm)
2,3,7,8-T4CDD(f)
Water,
UV lamp
8
>90
SOS(h)
added
(254-356
nm)
2,3,7,8-T4CDD(d)
Water-
UV lamp
24
62(e)
acetonitrile
(75:25)
(313 nm)
2,3,7,8-T4C0D(d)
Water-
Sunlight
26
49(e)
acetonitrile
(75:25)
2,3,7,8-T4CDD(a)
Methanol(b)
UV lamp
24
100 2,3,7-T3CDD
and DpCDD
2,3,7,8-T4CDD(f)
Methanol
UV lamp
18
100(i)
(254-356
nm)
2,3,7,8-T4CDD(a)
Methanol
Sunlight
<8( j)
100
2,3,7,8-T4CDD(d)
Hexane
UV lamp
4
66(e)
(313 ran)
2,3,7,8-T4CDD(c)
Isooctane
Sunlamp
0.67-3(10 50 No T4CDD
after 24-h
irradiation
1,2,4,6,7,9-
Hexane
Sunlight
47
50
H6C00(1)
1,2,3,6,7,9-
Hexane
Sunlight
17
50
H6CDD(1)
50
1,2,3,7,8,9-
Hexane
Sunlight
5.4
H6CDD(1)
50
1,2,3,4,6,7,9-
Hexane
Sunlight
28
H7CDD(1)
50
1,2,3,4,6,7,8-
Hexane
Sunlight
11
H7CDO(1)
(over)
D-71
fstitutoHSuper?ore di Sanita. Rome.
-------
Photodegradation Report. FIRST DRAFT.
NATO/CCnS Meeting. Bilthoven. November 1988.
(Table IV.5, continued)
OgCDD(a) Metha
Methanol(b) UV lamp 24 10 Series of
PCDOs with
decreasing
chlorine
content.
OgCDD(c)
08C00(1)
Octanol, or Sunlamp 18-20 6-20
isooctane
Hexane Sunlight 16 50 <10% of
degraded OCDD
converted
into less
chlorinated
compounds
(e.g. HgCDDHm)
(a) Crosby et al. (1971).
(b) Irradiation also carried out in ethanol with similar results.
(c) Stehl et al. (1973).
(d) Mill et al. (1983).
(e) Disappearance quantum yields: T3CDD, 0.22; T4CDD, in hexane, 0.049;
T4CDD, in water-acetonitrile, 0.0022; T4CDD, sunlight, 0.00068.
(f) Botr§ et al. (1978).
(g) 1-Hexadecylpyridinium chloride.
(h) Sodium dodecyl sulfate.
(i) Estimated by this author.
(j) Production of yellow gum after 36-h irradiation.
(k) Light source placed either 0.5 or 1.0 m, respectively, from sample.
(1) Dobbs and Grant (1979).
(m) Also compounds with longer GC retention time were observed.
U-72
-------
THC (M)
Fig. IV.1. Monochlorobenzene conversion vs. time:
(!) chlorobenzene; (A) o-chlorophenol; (0) p-chloro-
phenol; (I) hydroquinone and catechol; (~) o- and p-
benzoquinone.
D-73
-------
Figure IV.2a. Photodegradatlon of 3,4-d1chlorophenol
1n the presence of various semiconductor dispersions.
Wavelength >330 run; initial concentration of 3,4-
O2CP, 18 ppn; O2 present; Initial pH, 3.0; unbuffered
aqueous solutions; concentration of catalysts, 2.0 g/1.
D-74
-------
TIME# min.
Figure IV.2b. Plot of the concentration of chlorophenols vs. time of
irradiation (>310 nm) for the photodegradatlon of 4-chlorophenol and
pentachlorophenol: HO2, 2 g/1; Initial concentrations* 4.5 x 10"5 M;
oxygen present; pH ¦ 3.0; unbuffered dilute aqueous solutions.
D-75
-------
Figure IV.2c. Photodegradatlon of pentachlorophenol in the presence of
various semiconductor dispersions. Wavelength >310 nm; initial P5CP
concentration, 4.5 x 10~5 Mi O2 present; Initial pH, 3.0; unbuffered
aqueous solutions; catalyst concentration, 2.0 g/1.
D-76
-------
adsorption SUNLIGHT EXPT.
PH 3.0 : 02
(PCP)j3 4.5 x10~^M
(Cr)f«2.2x10"4M
X *300nm
40 60 ' st .100
TIME.min.
Figure IV.2d. Pentachlorophenol degradation under solar exposure in
the presence of Ti02 (2.0 g/1). pH • 3.0; O2 present; initial concentra-
tion, 4.5 x 10*5 M; irradiation wavelength >300 nm; final CI" concentra-
tion 2.2 x 10"4 N; unbuffered dilute aqueous solutions.
D-77
-------
I I I l\ I I I I 1
1 2 34 56 7 8 9 10
Time
-------
* _Ti02 4 g/L
\ —Ti02Q5g/L
CDD
ppm
Irrad. Time,hr
Figure IV.5b. Concentration vs. Irradiation time plots in the
photodegradatlon of 2-MiCDD at two different catalyst concentra-
tions. pH * 3.
D-79
-------
lrrad.Time,hr
Figure IV.5c. Concentration vs. Irradiation time plots
showing the dependence of photodegradatlon of 2-MiCOO
on pH. HO2 concentration, 4 g/1.
D-80
-------
A
T\02 a a
JiC^/R ¦ a
WO-5 • o
ZnO
T V
-6
-4
[CO
ppm
-2
Irradiation Time ,hr
Figure IV.6a. Concentration vs. Irradiation time plots 1n
the photocatalyzed degradation of 3,3'-D2CB; pH » 3; concentra-
tion of semiconductors ¦ 4 g/1.
D-81
-------
t (min)
Figure IV.6b. Photodegradatfon of adsorbed 3,3'-D2CB and DDT on HO2.
pH » 3.0; wavelength >340 nm; O2 present; TIO2» 2 g/1.
D-82
-------
Thomas O. Dahl
D-83
-------
FELLOWSHIP OBJECTIVES
Document the environmental problems at the Stringfellow site in
California, describe the process by which remedies were selected,
and identify the selected remedies, placing emphasis on site
specific or chemical specific circumstances that render some
remedies more/less applicable.
SITPERFIIND REMEDIAL RESPONSE PROCESS
Site Discovery
Preliminary Assessment
Site Inspection
Hazardous Ranking System (NPL).
Remedial Investigation/Feasibility Study
Selection of Remedy (Record of Decision)
Remedial Design
Remedial Action
D-84
-------
CERCLA SUMMARY
Remedial Program
Site Discoveries 29,358
Preliminary assessments 26,849
Site inspections 8,936
NPL sites 1,195
Remedial Investigations/ 359*
Feasibility Studies
Records of Decision 292*
Remedial Designs 147*
Remedial Actions 73*
NPL deletions 13
Removal Program
Actions 1,070
* Denote number for which the process has been completed, not
total number ongoing
D-85
-------
STRINGFELLOW SITE
Technically complex
Alluvial/decomposed rock/fractured bedrock setting
Inorganics, metals, organics
11,000 foot long plume of contaminants
Politically sensitive
Heavily litigated
Extensively studied
$13 million in studies
Numerous technologies considered
Cleanup times extensive
100s of years
TECHNOLOGIES TESTED ON S^T^TTFT.r.nM T.TDTTTn/SnT.Tn WASTES
Air Stripping
Incineration
Metals Precipitation
Reverse Osmosis
Ion Exchange
Stabilization/Solidification
Rotating Biological Contactor
Activated Carbon
D-86
-------
Michael Smith
D-87
-------
NATQ/CCMS PILOT STUDY
DEMONSTRATION OF REMEDIAL ACTION TECHNOLOGIES
FOR CONTAMINATED LAND AND GROUNDWATER
FELLOWSHIP PROJECT PROPOSED BY M A SMITH
Objective of Research Project
Using documentary and other information produced in the Pilot
Study to compare:
(i) criteria applied to assess whether a particular
demonstration project has been succesful,
(ii) to compare costs of various treatments,
(iii) to compare and evaluate cost/benefits of demonstration
projects,
(iv) to compare and synthesise results obtained in projects
using similar technologies (eg microbial treatments), and
(v) to contribute to technical discussions at meetings of
the Study Group.
Work Plan
(i) to attend meetings of the Study Group as invited by the
Pilot Study Director,
(ii) to meet as necessary those running the various
demonstration projects, and
(iii) to carry out the tasks listed above and to prepare
reports/publications primarily in response to requests from
the Pilot Study Director.
D-88
-------
INTERNATIONAL STUDY OF
TECHNOLOGIES FOR CLEANING-UP
CONTAMINATED LAND AND
GROUNDWATER
M A Smith
Bostock HiU and Rigby
1.0 INTRODUCTION
The NATO/CCMS Pilot Study on Contaminated Land (Smith 1985, Smith 1986) concluded from its 'state of
the art' review of technologies for dealing with contaminated sites, that greater emphasis should be placed on
'ultimate' or once and 'for all time solutions'. Excavation for redeposition simply moves the problem elsewhere
and containment, including superimposition of cover, offers only a temporary solution of doubtful long-term
effectiveness.
A number of countries, including the USA (hills 1987, EPA 1987), The Netherlands, the Federal Republic of
Germany (FRG) and Denmark have now started national programmes to develop clean-up technologies for
both contaminated land and contaminated groundwater. The longest standing of these programmes is that in
the Netherlands (Assink and van den Brink 1986). The UK approach has been commented on by Smith (1987).
The NATO/Committee on The Challenges of Modern Society (CCMS) Pilot Study 'Demonstration of
Remedial Action Technologies for Contaminated Land and Groundwater' is intended to compliment and
enhance these national programmes by promoting the exchange of information and expertise on new and
existing technologies for dealing with 'problem' hazardous waste sites.
The demonstration projects selected to date (January 1988) are variously concerned with:
(i) microbial treatment of contaminated soil and groundwater,
(ii) heat treatment of soil,
(iii) separation of soil and contaminants by high pressure jetting with water,
(iv) soil vapour extraction to remove volatile organic compounds, and
(v) physico-chemical treatment of contaminated groundwater.
The full list of projects is given in Table 1.
The study group plans to meet twice a year. The First meeting in Karlsruhe in March 1987 was followed by a
second meeting in Washington DC in November 1987 (Anon 1988). A third meeting is planned for Hamburg in
April 1988. It is the intention that the results of the various demonstration projects should be published as they
become available. A number of accounts of the study have already been published (Sanning and Offenbuttel
1987, Smith 1987B, Sanning, Smith and Bell 1988). This particular paper is intended to highlight the criteria
applied in a number of the projects by those responsible for them to decide whether the clean-up activity has
been successful. It is important, when evaluating new processes and seeking to compare them to similar or
0-89
Proc, 'Land. Rec. 88;
-------
dissimilar processes, that systematic, consistent and technically valid assessments are made. Criteria for clean-
up typically take two forms,
(i) target maximum concentrations that must be achieved, or
(ii) target reductions in the quantity and/or concentrations of contaminants present (these may range
typically from 90 to 99.999% depending upon the toxicity of the contaminants).
These criteria may be applied separately or in combination. If used together, the more restrictive requirement
usually takes precedence in deciding whether the clean-up is complete.
Table 1; Demonstration Projects
County
Project
Technologies etc.
Canada
Ville Mercier
Groundwater treatment.
Denmark
Skrydstrup
Groundwater and soils clean-up, microbial techniques.
FRG
Charlotenberg, Berlin
Soils clean-up (high pressure water washing).
FRG
Unna-Boenen, coke
oven plant
Soils clean-up by thermal treatment, microbial treatments.
FRG
Pintsch-uil, Berlin
Groundwater treatment, soils clean-up by high-energy water stripping process.
Netherlands
Rotterdam
Thermal treatment of soils.
Netherlands
Asten
In-situ and post extraction clean-up of groundwater (and associated soils) by
microbial techniques.
Netherlands
Wijster
Microbial-land farming.
USA
Peak Oil
Thermal treatment of soil.
USA
Eglin Air Force Base
Groundwater/soils clean-up by in-situ microbial treatment.
USA
Verona Well Field
Soils/groundwater clean-up by soil vapour extraction.
Japan
Asahi Electrochemical
Company
Soils treatment by thermal and chemical means.
2.0 SELECTED DEMONSTRATION PROJECTS
2.1 Evaluation of Thermal Treatment Plant, Netherlands
The contaminated soil at the former gasworks site in the Province of Zurd, Rotterdam, was excavated and
transported to the thermal destruction plant belonging to Ecotechniek (Yland and Soczo 1988). The soil was
contaminated primarily with polynuclear aromatics (PNA's) and complexed cyanides (ferri-ferro cyanides)
caused by spillages and dumping of waste materials. The installation of Ecotechniek B.V. at Rotterdam was
selected for evaluation because it had the highest 'production' of cleaned soil in the Netherlands (over
300,000 m1)- Although the installation had already been proved to be applicable for the removal and
destruction of many types of contaminants (oil, PAH's, aromatics, cyanides) from soil, it was considered that
there was need to assess more accurately the relation between type of contaminated soil, process conditions
and treatment results (including air emissions).
The installation consists primarily of an internally heated rotating kiln (direct heat transfer) and an after-burner
for the off gasses; these operate at a maximum temperature level of SS0°C and 1000°C respectively. It has a
maximum treatment capacity of SO tonnes/hr. It is considered suitable for the removal of aromatic and aliphatic
hydrocarbons (up to 10,000 mg/kg), cyanides (up to 400 mg/kg) and polynuclear aromatic hydrocarbons
(PAH's) (up to 800 mg/kg). It can be used to treat all types of soil. A trial on chlorinated hydrocarbons was
planned for the end of 1987.
The main purposes of the demonstration project were:
(i) evaluation of the treatment results and environmental aspects of the installation when used for cleaning of
soil from a former gasworks site, and
(ii) the further development of a standard evaluation methodology for soil treatment plants in general.
The evaluation was carried out by TNO using the framework methodology previously developed (Assink and
Rulkens 1985) for evaluation of remedial action technologies for contaminated soil.
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The study focused on the treatment of soils characterised as:
(i) 'easy to clean', sandy soil chiefly contaminated with polynuclear aromatic hydrocarbons (PAH's) from a
gas works site, and
(ii) 'difficult to clean', clayey soil containing rubble and contaminated with PAH's and mineral oil.
The study comprised:
(i) the determination of performance and residual concentrations during the clean up of the soil, and
(ii) the measurement of air emissions during the treatment.
The treatment was carried out under the normal conditions considered optimal by the company. A carefully
designed statistical sampling programme was applied to both input and output soils. Whilst removal rates above
95% were achieved for both soils, the 'difficult soil' did not fully meet the statistically based requirement in
respect of all parameters. However, it was suggested that some modification of the 'standard' sampling and
evaluation method might be necessary. All air emission standards were met.
Table 2: Process Conditions for Thermal Treatment of Soils
Soilfrom:
Gasworks site Dump site
Rotary kiln temperature (°C)
range
510-570
430-570
average
540
510
After burner temperature
925
850
Table 3: Target Specification (mg/kg dry wt.)
Gasworks Site Mean 99th percentile
total cyanide
10
20
volatile aromatic hydrocarbons
0.1
2 ¦
PAH's (Borncff)
20
—
Dump Site
PAH's (EPA priority list, individual)
0.1
0.3
bcnzo(a)pyrene
0.05
0.15
PAH's (EPA, total)
1
3
mineral oil
100
200
Dry residues, cyanides (total and free), PAH's (EPA - priority list) and mineral oil contents were determined
on both ingoing and outgoing soils. Standardised Dutch soil testing methods were used (Assink and Rulkens
1985, Keeper and Mangnus 1986). The principal process conditions during treatment are given in Table 2. The
requirements for clean up are set out in Table 3. The standard assessment procedure requires the setting of
limits for mean concentration and the maximum permissible standard deviation (Se) such that
Sc = (y - x)/2.39
where x and y are test requirements
regarding the residual concentration: x = mean value
y = 99 percentile
Some of the results are set out in Table 4 and 5. The testing procedure for cleaned soil resulted in the rejection
of the soil from the dump site. Neither the mean value nor the 99 percentile value were met with regard to
various PAH's. Although the mean value of the concentration of mineral oil was far below the required value,
the requirement set for the standard deviation could not be met. However only one single value was just above
the target mean and 18 values far below. This suggests that some modification of the assessment regime in
respect of the required standard deviation is needed.
2.2 Verona Well Field Site, USA
This project had not been completed at the time of writing but is of interest because of the targets set, the form
of independent monitoring imposed and the early signs that the initial site assessment underestimated the
amount of contaminants.
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Table 4: Results of Treatment
- Soil from Gasworks Site
Ingoing
(mg/kg)
Outgoing
(mg/kg)
Requirement
(mean)
(mg/kg)
Removal
(%)
PAH's Phenanthrene
5.41
0.07
98.8
Anthracene
1.13
0.10
91.5
Fluoranthene
8.73
0.08
99.1
Pyrene
8.45
<0.01
98.8
Benzo(a)pyrene
4.02
0.04
98.9
Total - Borneff (6)
33.2
0.5
20
98.0
Total EPA priority list (16)
133.04
4.88
Cyanide (total)
82
1.2
5
98.5
Tabic 5: Result
s of Treatment - Soil Aro
m Dump Site
Ingoing
(mg/kg)
Outgoing
(mg/kg)
Requirement
(mean)
(mg/kg)
Removal
(%)
PAH's Phenanthrene
13.43
0.22
0.1
98.4
Anthracene
1.65
0.03
0.1
98.5
Fluoranthene
3.58
0.11
0.1
96.9
Pyrene
3.70
<0.01
0.1
97.3
Benzo(a)pyrene
1.09
0.05
0.05
95.5
Total EPA priority list (16)
76.91
1.86
1
97.0
Mineral Oil
2,602
10
The Verona Weil Field Site consists of several distinct contaminated areas within about SO hectares (Tanaka
88). The well field itself contains 30 production wells that supply the entire city of Batle Creek, Michigan,
including several major businesses. The site also includes a railroad marshalling yard and two solvent facilities.
The Thomas Solvent Raymond Road (TSRR) facility is a former solvent repackaging and distribution facility.
Solvents were stored in 21 underground storage tanks which were later discovered to be leaking. The TSRR
facility is located about one mile upgradient of the well field in a primarily residential area surrounded by a few
businesses.
A survey by the US EPA Technical Assistance Team (TAT) in 1982 determined that the TSRR facility was a
potential major source of well Field contamination. This was confirmed during remedial investigation activities.
Chlorinated hydrocarbons are the most significant environmental contaminants. Groundwater and soil
contamination within the TSRR facility was found with concentrations of volatile organic compounds (VOC's)
as high as 100 and 1800 mg/kg respectively. The total estimated mass of organics in groundwater and soil at
TSRR was 200 kg and 770 kg, respectively (although the total mass of groundwater contaminants is now
known to be significantly higher). The total area of interst is about 930 sq. metres).
The remedial action selected for the site comprises a groundwater extraction system (GWE) in conjunction
with a soil vapour extraction (SVE) system. It was estimated that groundwater contamination could be reduced
to 100 ppb in 3 years and the total contaminant mass reduced by 98% in 1.1/2 years.
The contractor for the work, selected by competitive technical/financial bid, has been set a contractual
performance goal of 10 mg/kg total VOC's in the unsaturated zone soils. The key components of the SVE
system are extraction wells screened primarily in the unsaturated zone and a series of vapour phase activated
carbon treatment vessels.
Since SVE is an innovative technology a Quality Assurance Project Plan and a sampling plan for performance
demonstration were prepared. Three stages of sampling are involved; (i) during well installations (ii) at the
approximate mid-point (primarily to estimate VOC removal rates) and (iii) at the point when the SVE
contractor believes the 10 mg/kg VOC target has been met. This last will be carried by a separate contractor
working for the EPA. Statistical confirmation sampling is part of the SVE contractor's task. No samples taken
at any point in the volume of contaminated soil may have concentrations greater than 10 mg/kg. No more than
15% may exceed 1 mg/kg.
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2.3 Ville Mercier, Canada
The Ville Mercier is located on the south shore of the St. Lawrence river about 20 km southwest of Montreal
(Simard and Lanctot 1988). Groundwater is a major source of potable water from the local population. From
1968 to 1972 some 4000 m} of waste oils and liquid industrial wastes from chemical and petrochemical industries
in the Montreal area were dumped into a lagoon in an old gravel pit located several kilometres southeast of
Ville Mercier. In October 1971, it was discovered that several wells in the vicinity were contaminated. The
dump site was closed in 1972, and it was estimated the 20 000 m' of wastes remained in the lagoons. Sampling
conducted by the Quebec Ministry of the Environment (MENVIQ) revealed the presence of phenols and
chlorinated organic compounds in the groundwater in the area.
Four specific zones of contamination were delineated. The first two, where the groundwater was highly
contaminated, occurred within 2 km of the source. More than 80 organic compounds were identified in zone 1.
The principal contaminants were phenols, trichloroethylene, dichloroethane, trichloromethane, trichloro-
ethane, chlorobenzene, dichloroethylene and Aroclor 1254. Two other zones of lesser contamination were
delineated with a total area extent of contamination estimated at about 30 km2.
A programme to rehabilitate the aquifer was started by the Government of Quebec in 1981. The liquid material
which was stored in the lagoon was first removed (incineration, landfill). Following this, MENVIQ awarded
contracts to develop a purge-well system and to design and construct a groundwater treatment facility.
The pumping system consists of three extraction wells located a few hundred metres downstream of the
hazardos waste dump site. These wells create a cone of depression into which contaminated groundwater is
drawn. After treatment the water is discharged into a stream that is part of the Chateauquary river system.
The treatment system includes thefoilowing elements, air stripping, alum and polymer-activated flocculation-
sedimentation, rapid sand filtration, and activated carbon adsorption. The sludge is disposed to a landfill.
Several problems have been encountered: proliferation of bacteria, plugging of the treatment equipment, loss
of activated carbon, and clogging of the wells. The addition of chlorine and peroxide at the head of the
treatment system, and of chloride dioxide before filtration, has solved most of these problems and improved
treatment performance.
The water treatment objectives have been met. except for 1, 2 dichloroethane, which resists treatment because
the initial concentration is very high. After 3 years operation and pumping out of 3.6 M m' of contaminated
groundwater, a substantial abatement in the organic contaminants has been achieved and an acceptable degree
of decontamination seems likely to be achieved more rapidly than at first anticipated. It is expected that a
further 3.8 M m1 will be treated during the final two years planned operation of the plant.
The objectives set at the time the plant was designed was the production of discharge water with characteristics
similar to drinking water. Seven parameters were selected and assigned maximum residual concentrations (see
Table 6).
Table 6: Initial Control Limits for Discharge Water at Ville Mercier Site
Parameters Maximum Concentrations
(fig/litre)
phenols 2.0
1.1,2-trichloroethy lene 4.S
1,1.1 -trichloroethane 33.0
1,2-dichloroethane (or any other volatile organic) 50.0
Aroclors 1242, 1254 and 1260 (PCB's) 0.01
Iron (Fe) 0.3
Manganese (Mn) Q.QS
The difficulties in removing 1,2 dichloroethane is in part due to concentrations in the extracted water being
much higher (generally between 548 and 4650 pig/litre) than anticipated from the preliminary study (76 to 517
#ig/litre). In addition, the removal efficiency of the aeration stripping process has been less than the expected
60%.
Control of the effluent is carried out by bi-monthly analyses of the treated water as it leaves the plant. In
general, the effluent meets the set requirements (Table 6) except for the concentration of 1. 2 dichloroethane
which is consistently 10 to 20 times higher than the established norm. However, comparison with available
standards suggests that these levels do not present any environmental problem.
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It is considered that the effectiveness of such a clean-up action must be judged on the basis that the objective is
not to remove ail contaminants (an impossible task) but to remove enough so that nature will be able to
complete the process of final cleaning. In these circumstances it is not considered appropriate to set absolute
limits (e.g. drinking water standard) for the groundwater. In consequence it is better to set a criterion such as
90% removal of contaminants as measured either during the feasibility stage or during the actual restoration
process, as seems most appropriate. In this case the feasibility study underestimated contamination levels and
therefore those encountered during clean-up were considered more appropriate. Abatement rates obtained to
date (November 1987) are summarised in Table 7, these are then tested against three evaluation criteria in
Table 8 as follows:
Criterion S a 90% abatement in concentration compared with the average measured in the feasibility
studies.
Criterion M a 90% abatement compared to the maximum concentration during restoration.
Criterion L a concentration equal to or below the standard, or the level proposed for drinking water.
Table 7: Abatement of Organic Contaminants in Groundwater
Parameter Concentration (figII) Abatement (%)
Relative to
Measured *Mean "Maximum
[Feasibility
Study)
87106/03
s
M
S
M
1,1.1-trichloroethane
1.80
127.00
—
98.6
—
phenols
28.00
507.00
1320.00
94.5
97.9
iron (mgfl)
4.40
8.19
14.40
46.3
69.4
PCB Aroclor 1242
0.00
0.05
0.14
100.0
100.0
PCB Aroclor 1254
0.00
0.05
1.20
100.0
100.0
PCB Aroclor 1260
0.00
0.05
0.66
100.0
100.0
1,2-Dichloroethane
1060.00
187.00
11460.00
-466.8
90.8
1.1,2-Trichloroe thane
301.00
2395.00
—
87.5
Chloroform
26.00
78.50
—
66.9
—
Chlorobenzene
0.00
7.50
—
100.0
—
Trans 1,1-dichloroethylene
0.00
81.00
—
100.0
—
Manganese (mg/l)
0.16
0.18
0.27
11.1
40.7
1,1,2-trichloroethylene
27.00
114.00
160.00
76.3
83.1
' Before the remedial action.
** After the remedial action.
Table 8: Effectiveness of Ville Merrier Treatment Regime in Terms of
Criteria S. M and L.
Parameter
Criterion
S
Criterion
M
Criterion
L
1,1,1 -trichloroethane
OK
OK
OK
phenols
OK
OK
NO
Aroclor 1242
OK
OK
OK
Aroclor 1254
OK
OK
OK
Aroclor 1260
OK
OK
OK
1,2-dichloroethanc
NO
OK
NO
1.1,2-trichlorocthylcnc
NO
NO
NO
2.4 Skrydstrup, Denmark
The SKrydstrup site is a former gravel pit used from 1963-1974 for the disposal of about 200 tonnes chemical/
industrial waste from a refrigerator factory (Christiansen and Vedby 1988). Some of this waste was stored in
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several hundred drums at the site. There have been extensive chemical, geological and hydrogeological
investigaions since 1986. Trichloroethane, trichloroethylene, paint and acid wastes have resulted in
groundwater pollution. Contaminants include haloalkyl phosphates used as flame retardants in insulating
foams. A series of sampling wells have been installed down gradient between the site and a nearby stream
(2.4 km) and water supply wells (3 km). Contamination has been detected about 1.1 km from the site. The
groundwater flow velocity is about 100-200 M a year.
The remedial action consists of digging up, removal and off-site disposal of several hundred drums followed by
groundwater pumping and treatment, and on-site treatment of the polluted soil by a variety of means including
aerobic/anaerobic microbial treatment. The groundwater system will involve air-stripping and active carbon
absorption over an anticipated 10-15 years from 1988. Pilot scale tests involving air-stripping on perforated
plates in three oxidation steps resulted in a 99% removal of chlorinated solvents. Subsequent activated carbon
adsorption helped to achieve 9S% reduction of haloalkyl phosphates, (typical concentrations in wells placed
close to the site are given in Table 9).
The clean up criterion for the groundwater purification process is to remove detectable chlorinated solvents
and ahloalkyl phosphates at the water supply extraction wells about 3 km from the site. Furthermore the water
supply must not contain biological degradation products of the contaminants (for instance vinyl chloride). The
detection limit of the substances involved is 0.2 to 0.5 /ug/litre.
Several full scale development projects have been started to deal with the contaminated soil and groundwater;
(i) bio-degradation of chlorinated solvents in contaminated soil,
(ii) anaerobic bio-degradation by addition of natural gas in columns with activated carbon adsorption.
(iii) aerobic bio-degradation of chlorinated solvents in the unsaturated zone by CO metabolism by oxidation
of methane and/or propane.
(iv) anaerobic biodegradation in the contaminated zone by addition of sodium acetate.
Table 9; Groundwater contamination of Skrydstnip Site, Denmark
Borehole
Approx. distance from site'
m
4
30
2
120
9
300
6
540
10
1100
14
2400
1.1.1 -trichloroethane
Mg/1
13000
2900
300
160
15
nd
trichloroethylene
Mg/1
230
240
280
13
21
nd
tetrachloroethylenc
Mg/1
2.4
3.4
0.5
nd
nd
nd
TCEP
Mg/I
38
250
94
2
0.6
nd
TCPP
Mg/1
380
370
5
0.6
nd
nd
Notes: TCEP = 0,0.0-tris (2 chloroethyl) phosphate
TCPP = 0.0,0-tris (3 chloropropyl) phosphate
nd = not detected
'present author's assessment.
3.0 DISCUSSION AND CONCLUSIONS
The approach adopted to the setting of criteria for assessing whether the clean up has been successful and/or in
setting 'targets' differs for the four projects. In general terms, the minimum removal required is 90% (Ville
Mercier) and the maximum aim (Skrydstrup) is to achieve a 'non-detectable' concentration (both in
groundwater). However, the latter is set for a point about 3 km from the source and it is not clear what criteria
will be applied at the point at which the groundwater is to be treated (the site itself).
The sophistication of the assessment of whether clean up has been achieved also varies appearing to be more
rigorous for the two soil clean-up studies (Ecotechniek plant and Verona Wells Field) but this may simply
reflect a lack of detail in the source documents (and of course the Skrydstrup project is not yet under way).
In both the soils studies, criteria have been set which control the permitted variability within the samples as well
as seeking acceptable maximum or 99 percentile figures. The Dutch approach is possibly the more rigorous but
then the soil has to be capable of 're-use' after treatment, possibly as a traded commodity, whereas at the
Verona site the soil remains in place. The Dutch case also differs in that the process is intended to provide a
complete solution in one operation whereas at Verona, if the criteria are not met at the 'presumed end' of the
project, the process can be operated for a further period of time.
The two groundwater projects are also processes operated over a period of time. Thus trends and fluctuations
can be monitored. At some stage it may be necessary to balance the costs of continuing the clean up process
against the benefits likely to be achieved. There may come a time when, as is suggested for the Ville Mercier
D-95
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site, nature must be left with the task of further reducing concentrations either through natural degradative
processes or eventual dispersion and dilution.
The Ville Merrier sites illustrate how different criteria may be applied to the same data with variable results as
to whether the clean up may then be judged successful. The Ecotechniek project illustrates how removal rates
of 98% or more in terms of mean concentrations, and achievement of concentrations well below acceptable
mean concentrations, may yet be judged as failing because variability is too great. Both the Ecotechniek and
ville Mercier studies also show the need to look at a 'package' of parameters when making judgements.
Only the Ecotechniek project is yet completed (the final report was not available at the time of writing). The
other three projects have several (even fifteen years) to run so the appropriateness of the evaluation methods
employed can not yet be properly judged. However, the four projects, taken together are useful in illustrating a
range of approaches. As a minimum, they show the need to give careful thought to setting of both the initial
objectives and in determining in advance, how it is finally to be decided whether these objectives have been
achieved.
Finally, it is worth noting that the first NATO/CCMS study group on contaminated land (Smith 1985) made a
sharp distinction between monitoring a remedial action and evaluating a remedial action, Tlie aim in the former
is to obtain data to determine whether the action is working as planned. The latter is aimed at obtaining an
understanding how (and why) the action is working or failing. To do this more data will usually be required.
This technical and scientifically deeper and more extensive approach to data collection and analysis will usually
be required when demonstration projects are undertaken.
4.0 FURTHER INFORMATION
Further information on the NATO/CCMS study can be obtained from the Pilot Study Director, D.E. Sanning,
of the U.S. Environmental Protection Agency's Hazardous Waste Engineering Research Laboratory,
Cincinnati, or in the U.K, from the author. A full list of national contacts is given elsewhere (Sanning et al
1988).
References
Anon. 1988, Proc. First International Meeting NATO/CCMS Pilot Study Group on Demonstration of Remedial Action
Technologies for Contaminated Land and Groundwater. Washington D.C. 1987 (U.S. Environmental Protection Agency,
Cincinnati).
Assink J W and Van den Brink W J 1986 Contaminated Soil (Martinus Nijhoff, Dordrecht 1986).
Assink J W and Rulkens W H 1985 Preliminary Set-up for a Standard Method to Evaluate Remedial Action Techniques for
Contaminated Soil (TNO, the Hague) in Dutch.
Christiansen K and Vedby S 1988 Skrydstrup Chemical Waste Disposal Site, in Anon 1988.
EPA 1987 SuperfUnd Innovative Technology Evaluation (SITE) Program, (U.S. Environmental Protection Agency,
Washington D.C.).
Hill R D 1987 Superfund Innovative Technology Evaluation (SITE) after the first year, in Proc. SUPERFUND 87
(Hazardous Materials Control Research Institute, Silver Spring, Maryland 1987) pp. 25-27.
Kooper W F and Magnus GAM 1986 Sampling and Analysis in Contaminated Site Investigations, Impediments and
Provisional Guidelines in the Netherlands, in Assink J W and Van den Brink W J 1986, pp. 325-336.
Sanning D E and Offenbuttel R 1987 NATO/CCMS, Pilot Study on Demonstration of Remedial Action Technologies for
Contaminated Land and Groundwater. Proc. 13th Annual Research Symposium, July 1987 (US Environmental Protection
Agency EPA/600/9-87/015), pp. 172-182.
Sanning D E, Smith M A and Bell R M 1988 NATO/CCMS Pilot Study on Demonstration of Remedial Action
Technologies for Contaminated Land and Groundwater -1988 Activities. Proc. Second International Conf. Contaminated
Soil, Hamburg 1988 (to be published).
Simard G and Lanctot J P 1988 Decontamination of Ville Mercier aquifer for toxic elements, in Anon. 1988.
Smith M A 1985 Contaminated land: reclamation and treatment (Plenum, London and New York).
Smith M A 1986 International study on reclamation of contaminated sites, in Assink J W and Van den Brink W J, 1986,
pp. 303-313.
Smith M A 1987 Why the U.K. is losing the race to clean up. Surveyor 168 (4955) 16-18.
Tanaka J C 1988 Verona Well Field Superfund site. Battle Creek, Michigan: soil vapour extraction system, in Anon 1988.
Yland M W F and Soczo E R 1988 Practical evaluation of a soil treatment plant, in Anon 1988.
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Appendix E
Presentation at Site Visit
-------
INTEGRAL PROCESS DESIGN FOR SOIL DECONTAMINATION IN SLDR&Y BIOREACTORS
R.H. Kleijntjens and K.Ch.A.M. Luyben
Biotechnology Delft Leiden, BDL
Delft University of Technology,
Department of Biochemical Engineering,
Julianalaan 67,
2628 BC Delft, The Netherlands
Both chemical and biological techniques are used for the clean up of
excavated contaminated soil. At the moment landfarming is the leading
biological treatment for excavated soil, however, this technique suffers
from slow decontamination rates and the need of large land areas. To
circumvent these hinderences a slurry bioreactor is under development in our
department, using the ability of micro-organisms to convert pollutants at
high rates under three phase slurry conditions. To develop this new
technology for soil treatment, a three step process design procedure is
carried out.
First step is concerned with the decontamination kinetics of the micro-
organisms under slurry conditions. Following this step a bioreactor design
is made and experimentally tested, and in the third step this bioreactor is
integrated with the other process steps in the total process design. A new
reactor is developed in which a dual injection of a gas and a slurry phase
results in a three phase slurry system with slurry densities up to 50 w/vX.
Preliminary kinetical studies have been shown a fast degradation rate. As a
consequence the cost estimate of this new process looks promising.
Introduction
Last decade society has become more and more aware of the fact that soil
pollution is a threat to the environment. Prevention should be the first
policy, but for the time being decontamination processes to clean up
existing pollutions are needed. Besides thermal and chemical treatment also
microbial processes are seen as attractive alternatives. Landfarming, the
E-l
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besC known microbial technique for excavated soil, has become fairly well
accepted. Landfarm operations, however, have the inherent disadvantage of
slow decontamination rates and the need for large land areas. Oxygen
transfer limitations in the soil and the presence of large particle
agglomarates have been recognized as major reasons for this slow degradation
rate in landfarming.
To overcome this limitation we decided to investigate the possibility of a
new process for soil decontamination. The aim is to create well defined
optimal conditions for mass transfer by the use of a slurry bioreactor, to
achieve fast decontamination rates. In this process use is made of modern
fermentation technology and the know-how from ore leaching processes.
Comparing the situation under landfarm conditions with those in a slurry
reactor, results in the following major differences:
situation in soil
situation in slurry
pollutant is encapsuled
between particles due to
agglomerates; hindering
contact between organisms
and polluted sites
pollutant is free accessible
due to separate suspended
particles; making the
adsorption of organisms on
polluted particle sites easy
hampered mass transfer to free mass transfer to and from
and from polluted sites the pollution on the particles
in suspension
slow biodegradation of
soluble pollutans due to
limited liquid phase
possible breakdown of soluble
pollutants in the well aerated
abundant process water
The development of a three phase slurry bioreactor to exploit the benefits
mentioned is the most important part of the process design. This paper
describes a three step procedure to design an integral process.
-------
Process design procedure
In designing a new microbial soil decontamination process using slurry
reactors we started at the core of the process: the bioreactor. In this
bioreactor three different phases (solid-liquid-gas) are part of a slurry in
which the aerobic microbial decontamination process takes place. The solid
phase consists of polluted soil which, in the form of separate soil
particles, is suspended in the liquid phase (the process water). The third
phase, the gas phase, is introduced as compressed air in the system. This
gas phase serves two important tasks in this system: as the driving force
for the suspension of soil particles and as an oxygen source for the aero-
bically growing micro-organisms.
The design procedure for the soil decontamination process can be roughly
divided into three steps:
* research on kinetics of biodegradation in slurry systems
* technological research on three phase slurry bioreactors
* integration of the bioreactor in a process design
The first two steps concern the bioreactor itself, combining the output of
these items a well funded design of the bioreactor can be achieved. In the
third and last step the functioning and integration of the bioreactor within
the whole of unit operations has to be considered. This results in a process
flowsheet and serves as the basis for a cost evaluation.
From figure 1 it becomes clear that a whole spectrum of different aspects
have to be taken into account in the design of a bioreactor for soil
decontamination. The figure illustrates that some understanding of the
overall integration is a necessity to succeed in a feasible reactor design.
Following the reactor design, scale-up is a major item in the process design
procedure. As is shown in figure 1 a pilot-plant reactor functions as
intermediate between the lab-scale reactor and the full scale reactor. This
intermediairy experimental phase is unavoidable due to the fact that the
scale-up of a three phase slurry system for soil decontamination means a new
process in a new reactor. The complexity of such a design and especially for
this kind of poorly defined systems make a pilot-plant essential (1).
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concept of a 3—phase soil decontamination process
] I I \ I I F
soii
V^janalysis
analytical
techniques
Figure 1 Schematic representation of the different
items influencing the design procedure
Step 1: Kinetic study on the biodegradation in three phase slurry systems
Micro-organisms are able to convert aerobically a broad range of xenobiotic
organic subtances into new biomass, carbondioxide and water (1,2). This
degrading ability holds not only for organisms growing in natural soils but
even more so in a slurry system (3,4). The overall reaction equation for the
bioconversion of oil-like components can be represented as follows:
E-4
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Diesel/Oil + aHNO. + b0o cCH, .0. ,NA . + dCO„ + eH.O
' 3 2 organisms 1.80.50.2 2 2
(substrate) (N-source) (air) (biomass)
According to this overall stoichiometry polluted soil is converted into
clean soil, biomass, carbon dioxide and water. For a fast degradation mass
transport should not be the limiting factor in the three phase system.
Especially the oxygen supply should be paid attention to. Other major
hinderences for a fast decontamination rate are firstly limited contact
possibilities between micro-organisms and polluted sites due to particle
agglomerates and secondly irreversible adsorbance of pollutants inside the
soil particles.
periodic solids
wasting
(light fraction)
(© *
periodic solids
wasting
(heavy fraction)
Figure 2 Experimental set up for kinetical experiments
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In order to exploit the advantages of a slurry system fully (see
Introduction), it is necessary to develop a new reactor in which a soil-
water-air slurry can be created to provide an optimal environment for
biodegradation. This holds as well for the micro-environment (close to the
particles) as for the macro-environment (in the bulk). Slurry conditions
characterizing this environment are: slurry density, oxygen transfer,
biomass concentration, nutrient supply, pH and temperature.
A tapered reactor, schematically shown in figure 2, is under development in
our department. The lab-scale reactor used in our kinetic studies has a
volume of 20 liter. Characteristic for this new reactor is the two phase
injection system in the tapered bottom (patent pending). This injection
system is specially developed to create high density soil slurries. Due to
this mode of injection it is possible to make optimal use of segragation
phenomena in the three phase slurry, resulting in a bottom fraction
containing the larger particles and a bulk fraction with the smaller
particles. As a result of these two different zones in the reactor a
physical separation can be combined with the biodegradation process.
Research aiming for optimum slurry conditions in relation to the
biodegradation rate is at the moment carried out. Attention is paid to the
degradation rate of single model pollutants as hexadecane as well as to
diesel fuel. It is our aim to find reaction rates under slurry conditions
which are closely related to conditions in practise (full scale oriented
process conditions). Mimicking at lab-scale process conditions which can be
expected on a planned or existing full scale is often called 'scale-down'.
In case of an existing full scale this procedure can be based on
experimental data while in case of a planned full scale only theoretical
regime analysis is possible.
Step 2: Technological research on three phase slurry bioreactors
The second step in the design of this process is aimed at developing both
fundamental and emperical knowlegde concerning the following items: slurry
reactor design, slurry processing in three phase bioreactors, scale-up,
implementation of new injections devices, slurry handling in relation to the
reactor design and construction aspects. Therefore we have started to carry
out experiments on a bench-scale to provide the necessary information on the
practical feasibility of this new type of reactor.
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The reactor size chosen is 400 1. The reacCor is made of perspex with a 60°
degree angle tapered bottom. The height/diameter ratio of this reactor could
be altered. Similar reactors can be found in the mining industry (5,6),
where they are used for ore leaching. However, in those cases the suspension
is maintained by the injection of only a gasphase (air). The experiences in
this field have not led to a significant literature spin off.
Experiments in our 400 1. reactor have been carried out both with quartz
sand (range: 300-1000 /im) and soil (range: 1-4000 fito) as solid-phase.
Research was focussed at the suspension behavior of the solid phase with one
phase (air) injection and with dual phase (air-liquid) injection.
Figure 3 Schematic representation of the 400 1.
slurry reactor with dual injection.
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A one phase injected system uses only gas injection at the bottom of the
reactor, a two phase injected system requires a slurry recirculation flow
and a special designed two phase injection system. Figure 3 gives a
schematic representation of this dual injection configuration. Continuous
slurry withdrawal from the top of the reactor feeds the settling section in
which the larger particle fraction is seperated from the slurry and returned
to the reactor. The top flow of the settler contains only the smaller
particle fraction and can be used for recirculation to the injector.
The following preliminary results from the 400 1. reactor experiments with
one phase and dual phase injection, can be presented:
One phase (aix) injected suspension:
* both quartz sand and soil particles can be kept in suspension by
introducing large amounts of compressed air (about 1 WM)
* the range of slurry densities which could be handled was 5-25 w/v %
* optimization of the energy input by lowering the gasflow to a minimum
results in a unstable suspension situation which is undesirable from a
practical point of view.
Dual injection suspension:
* high slurry densities could be reached for both quartz sand and soil by
combining relatively small slurry recirculation flows with far lesser air
flow rates than in the one phase injected system
* the range of slurry densities that could handled was 25 - 50 w/v X
* optimization of energy input by means of a high performance injector
design and lowering of the air flow rate by adjusting the ratio of slurry
recycle flow and air flow, resulted in a far better suspension behavior as
in the one phase injected system
* a physical separation between the coarse and the fine particle fraction in
the slurry reactor can be achieved by means of dual injection
Scale up
The experiments confirmed that scale effects play a large role in the design
of three phase slurry systems. This holds specially for the energy input in
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the system. A fundamental model Is under development which predicts the
hydrodynamics of the three phase slurry at different scales. This model will
become a major tool for the full scale design. Nevertheless the construction
of a 4 ms pilot-plant was considered a necessity to provide empirical
information on scale phenomena for both the one phase as the dual phase
injection. At the moment this pilot-plant reactor is under construction.
With regard to designing and scale up aspects it can be stated that many
different technological research fields have to be integrated. Various
disciplines contribute to a succesfull reactor design on large scale. The
following list gives an indication of items studied: physical technological
fundamentals of slurries, the influence of reactor geometry, energy
balances, particle segragation phenomena in dense slurries, slurry handling
and transport, injector/settler design, material aspects, process operation,
control aspects and fouling of the system.
Step 3 Integration of the bioreactor in a process design
The bioreactor designed on the basis of steps 1 and 2 has to be implemented
as part of a realistic process design. For this we should know most reactor
features concerning the kinetics and the technological aspects of the
decontaminsation process. Uith regard to the kinetics of the reactions in
the system, the rate under various realistic slurry conditions result in an
estimate for the soil residence time in the system. Results from the
technological stage in the procedure have to provide information on design,
construction and scale-up aspects of the reactor.
Flowsheeting has resulted in a sequence of unit operation for optimal
integration of the special features of this bioreactor. In the flowsheet
three major sections can be distinguished:
* a pretreatment section in which the soil is sieved and milled
* a reactor section, containing two slurry reactors in series
* an after-treatment/dewatering section in which process water is recycled
and clean soil is recovered.
A schematic representation of the flowsheet is given in figure 4.
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grinder
4
air supply
nutrients, water
recirculation liquid
Figure 4 Schematic representation of the flowsheet
design for a two stage biological soil
decontamination plant.
Conclusions
The design of a soil slurry decontamination process was presented. In the
design procedure three steps could be identified:
* Step 1: Study of the kinetics of the decontamination process; experiments
using full scale oriented process conditions will give an
estimate on the necessary residence time for soil in the slurry
system.
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* Step 2: Study of physical technological phenomena that form the basis for
the bioreactor design, reactor operation, scale-up and
construction aspects.
* Step 3: Integration of the slurry reactor in a total flowsheet design is
under study in this third step. Pilot-plant studies, flowsheeting
and a final cost evaluation of the process will be important.
The three steps mentioned have major interactions and are conducted in a
partial parallel way.
Finally it can be stated that due to the integrated approach the application
of soil decontamination in three phase slurry bioreactors is on the way and
at the same time resulting in more fundamental knowledge about these
complicated systems.
Literature
(1) N. Harnby, M. Edwards, A. Nienow (eds), Mixing in the process
industries, Butterworth series in Chemical engineering, 1986 London
(2) 0. Hutzinger (ed), Handbook of Environmental Chemistry, Springer Verlag,
1980, Berlin
(3) H.G. Schlegel, Allgemeine Mikrobiologie, Thieme Verlag, 1985 Stuttgart
(4) R.H. Kleijntjens, K.Ch.A.M. Luyben, L.F. Velthuisen, M.F. Bosse, G.Ch.
van Eybergen, Proceedings of the 4th European Congress on Biotechnology,
1987, vol 1, Elsevier Publishing Company, Amsterdam
(5) R. Oldenhuizen, et al., Appl. Microbiol. Biotechnology, 1989, submitted
for publication
(6) A.D. Merriman, A Dictionary of Metallurgy, Macdonalds & Evans, 1958
London
(7) K.Ch.A.M. Luyben, et. al., Proceedings of the 1th int. Conference on
processing and utilization of high sulfur coals, 1985, Columbus, Ohio.
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