NATO/CCMS
Fourth International Conference
Demonstration of Remedial Action Technologies
for Contaminated Land and Ground Water
Angers, France
5-9 November 1990
-------
NATO/CCMS
Fourth International Conference
Demonstration of Remedial Action Technologies
for Contaminated Land and Ground Water
SEPA
Angers, France
5-9 November 1990
-------
This report Is not an official document
of the NATO/CCMS Pilot Study Program
-------
Abstract
In November 1986, the NATO Committee on Challenges of Modern Society (CCMS)
formally adopted a United States proposal for a five-year pilot study to
demonstrate technologies for cleaning up contaminated land and ground
water. The participating NATO countries are Canada, Denmark, Federal
Republic of Germany, France, the Netherlands, and the United States. Japan
is also participating. Norway and the United Kingdom are observer
countries. The Pilot Study Director is from the United States; the co-
directors are from the Federal Republic of Germany and the Netherlands.
The Fourth International Conference was held in Angers, France on 5-9
November 1990. Reports on 6 projects (final and Interim) were prepared,
including the following types of treatment: pump and treat (2 projects),
microblal treament (1 project), physical/chemical (1 project), thermal (1
project) and volatilization (1 project). Four NATO/CCMS Fellows and four
NATO Guest Expert Speakers made presentations. 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 the final conference for this study to be held in
Washington, DC on 18-22 November 1991.
-------
11
-------
Table of Contents
Page
ABSTRACT 1
INTRODUCTION 1
BACKGROUND 1
REPORT ORGANIZATION..... • 7
RECENT DEVELOPMENTS IN NATIONAL PROGRAMS 7
Canada 7
Denmark 11
France 12
Germany 12
Norway 13
The Netherlands 15
United Kingdom 15
United States 20
PROJECT REPORTS 25
Pump and Treatment
Recovery/recycling (V1v1ez, Lot River, France) 27
Separation pumping technique (Denmark) 47
M1crob1a1 Treatment
Rotary composting reactor for oil polluted soil with
low moisture (The Netherlands).. 75
Physical/Chemical Treatment
Debris washing (United States) 87
Thermal Treatment
Revolving fluldlzed bed (Sidney Tar Ponds, Canada) 107
Volatilization
Soil vacuum extraction (The Netherlands) 109
1H
-------
LIST OF APPENDICES
Page
A List of Attendees at NATO/CCMS Fourth International
Conference, Angers, France, November, 1990 A-l
B Presentations by NATO/CCMS Fellows
Peter Werner (Germany) Blodegradatlon of hydrocarbons... B-l
Merten Hlnsenveld (The Netherlands) Alternative
physlco - chemical and thermal cleaning
technologies for contaminated soli B-17
Alain Navarro (France) Solidification - new French
procedures for the control of solidification waste.... B-27
C Presentations by NATO/CCMS Guest Speakers
Bruno Verlon (France) Contaminated sites situation
1n France C-l
Herve Billard (France) Management of Industrial waste
1 n France C-9
01ck Jannssen (The Netherlands) Degradation of
halogenated aliphatic compounds by specialized
mlcroblal cultures and their application for
waste treatment C-41
Douglas Ammon (United States) United States - clean
sites C-57
Christian Bocard (France) New developments 1n
remediation of oil contaminated sites and ground
water C-39
Frank Gallagher (United States) Enhanced blodegradatlon
through soil venting C-107
Edward Marchand (United States) Catalytic oxidation
emissions control for remediation efforts C-121
Michael Kremer (France) Pre-tour talk on the Alrvault
factory C-l 29
Jean Marc Rleger (France) Incineration 1n cement kllnes
and sanitary landfllHng C-139
D Proposal for New NATO/CCMS Pilot Study D-l
E International Standards Organization Statement on
Standards for Soils (In German) E-l
F Agence Francalse pour la Recuperation et I1Elimination
des Dechets F-l
G Third International KFK/TNO Conference on Contaminated
Soil G-l
H Technology Innovation Office of EPA H-l
1v
-------
LIST OF EXHIBITS
Exhibit Page
1 Agenda for Fourth International Conference NATO/CCMS
Pilot Study 2
LIST OF FIGURES
Figure Page
1 Status of CERCLIS Inventory 21
2 Status of Remediation at NPL Sites 21
3 Value of PRP Settlements 22
4 Source Control Treatment 22
5 Remediation Status 23
6 EPA Bloremediatlon Field Initiative 23
-v-
-------
Introduction
This Is a report of the proceedings of the fourth International
Conference for a pilot study under the NATO Committee on Challenges of
Modern Society (CCMS): Demonstration of Remedial Action Technologies for
Contaminated Land and Ground Water. The meeting was held 1n Angers,
France, 5-9 November 1990. Exhibit 1 1s the agenda for the meeting.
The purpose of this conference was to present final or Interim
reports on 6 Pilot Study projects as well as other technical papers. The
conference also Included a visit to a cement kiln where Industrial wastes
are being Incinerated.
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 Ground Water."
Under this study, new technologies being demonstrated and evaluated in the
field are discussed. This allows each of the participating countries to
have access to a data base of 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 biological, chemical/physical, and thermal technologies for both
soil and groundwater. With few exceptions, they are in-situ or on-s1te
technologies; they do not Include containment technologies.
The study was approved In November 1986 to last for five years;
it includes nine countries. Projects are selected and their status moni-
tored during an annual administrative meeting held in the Spring. (The
last of these meetings was held In Oslo, Norway, March 1990.) There are
currently a total of 29 NATO/CCMS Pilot Study projects.
The exchange of Information on developing technologies 1s the prime
goal of this study. The presentation and discussion of 1n-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
and final International conference will be held 1n Washington, DC, 18-22
November 1991.)
-------
EXHIBIT 1
AGENDA
Fourth International Conference
NATO/CCMS Pilot Study
DEMONSTRATION OF REMEDIAL ACTION
TECHNOLOGIES FOR CONTAMINATED LAND
AND GROUND HATER
5-9 November 1990
French Host: Rene Goubler
-------
Monday
5 November 1990 Day 1
8.30 Registration
9.00 Opening of the meeting, D. Banning, United States
9.10 Welcome from Host Country
Mr. Patrick Souet - Dlrecteur Adjoint, ANRED
Mrs. Chantae Puechmallle - Direction de la cooperation
Sclentlflque et Technique, Mlnlstere des
Affaires Etrangers
9.25 Opening remarks by Pilot Countries
- Donald Sannlng, United States
- Volker Franzlus, Federal Republic of Germany
- Esther Soczo, The Netherlands
9.35 Introduction of Attendees
10.15 Coffee Break
10.15 Opening Speeches
Contaminated sites situation In France -
Mr. Bruno Verlon - Service de 1'Envlronnement
Industrlel, Secretariat d'Etat charge de
1'Envlronnement
Management of Industrial waste 1n France -
Mr. Herve Blllard - Adjoint au Dlrecteur de
I1Action Technique - ANDRED
11.30 Tour de Table
o Canada - J1m Schmidt
o Denmark - Neel Stroback
o Germany - Volker Franzlus
o France - Rene Goubler
o Norway - Beate Folkestad
o The Netherlands - Esther Soczo
o United Kingdom - Paul Bardos
o United States - Walter Kovallck
12.45 Lunch
W«30 Presentation of Pump and Treatment Projects
Recovery/recycling - Vivlez, Lot River, France
(final report*) - Mr. Dominique Polroux, Direction
Reglonale de TIndustrie et de la Recherche
(Region Midi - Pyrennees)
-------
Monday
5 November 1990
Pay 1 (Continued)
15.15
16.00
Separation pumping technique - Denmark (final report*)
- Bertel Nllsson, Geological Survey of Denmark,
Ministry of the Environment
Adjourn
Tuesday
6 November 1990
8.30
9.00
9.30
10.15
10.30
11.15
11.45
16.30
Day 2
NATO Fellows
Blodegradatlon of hydrocarbons - Peter Werner,
Germany
Alternative physico-chemical and thermal cleaning
technologies for contaminated soil - Merten
Mnsenfeld, The Netherlands
Presentation of Mlcroblal Treatment Projects
Rotary composting reactor for soil with low moisture
- The Netherlands (final report*) - Ger van den
Munckhof, Wltteveen & Bos Consulting Engineers
Coffee Break
NATO Guest Speaker
Degradation of halogenated aliphatic compounds by
specialized mlcroblal cultures and their applica-
tion for waste treatment - Dr. Dick Janssen, The
Netherlands
Presentation of Physical Chemical Project
Debris washing - United States - (Interim report*) -
Naomi Barkley, U.S. Environmental Protection Agency
Lunch and tour of Angers Castle
Adjourn
"Thirty minutes per presentation followed by 15 minutes discussion.
^Fifteen minutes per presentation followed by 5 minutes discussion.
-------
Wednesday
7 November 1990
9.00
9.45
10.15
10.45
11.00
11.15
12.00
17.00
Day 3
NATO Guest Speaker
United States "Clean Sites" - Douglas Ammon, United
States
NATO Fellows
Tom Dahl, United States
Solidification - New French procedures for the
control of solldlflcated waste - Alain Navarro,
Institute National des Sciences Appliques, France
Coffee Break
Presentation of Thermal Project
Revolving fluldlzed bed - Sidney Tar Pits, Canada -
(Interim report) - J1m Schmidt, Environment Canada
Discussion of U.S. proposal for continuation NATO/CCMS Pilot
Study Initiation for 1992
Lunch and tour of Tapestry Museum
Adjourn
Thursday
8 November 1990
9.00
9.45
10.30
10.45
Day 4
NATO Guest Speaker
New developments 1n remediation of oil contaminated
sites and ground water - Christian Bocard,
Instltut Francals du Petrole, France
Presentation of Volatilization Projects
Soil vacuum extraction and combustion - The
Netherlands (final report*) - Frank Spulj, TAUW
Infra Consult
Coffee Break
Nato Guest Speakers
Enhanced blodegradatlon through soil venting - United
States (Interim report) - Col. Frank P. Gallagher,
U.S. Air Force
Thirty minutes per presentation followed by 15 minutes discussion.
-------
Thursday
8 November 1990
11.10
11.30
12.00
17.00
Friday
9 November 1990
8.30
9.00
9.30
10.00
Day 4
Catalytic oxidation emissions control for remediation
efforts - United States - Capt. Edward G.
Marchand, U.S. A1r Force
Pre-tour talk on Incineration - France
M. Kremer - Sodete des Cements Francals
M. Rleger - Sodete SCORI
Lunch and technical tour
Incineration of Industrial waste In a cement kiln
Adjourn
Day 5
Update from Final Report subcommittee
Discussion about recommendations to NATO 1n final report
Other administrative topics
End of the Conference
-------
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 In Proceedings following each International meeting.
Information 1s 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 and Expert Guest Speakers have been Identified from
participating countries. They provide additional technical resources to
the Pilot Study 1n their expertise, Information resulting from their pro-
jects, and access they may have to Information about other emerging reme-
dial technologies. The Fellows' Involvement 1n the Pilot Study 1s
primarily through their attendance and participation In the annual Inter-
national meetings. There are currently 13 Fellows Involved with the Study.
Four of the Fellows and nine Expert Guest Speakers made a presentation at
this meeting.
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 In their national regulatory and research and development programs.
Reports on specific projects presented at this conference are second and
form the bulk of the proceedings. The reports Include both Interim and
final project reports, and are arranged In the order In which they were
Included on the program. Presentations by NATO/CCMS Fellows and by Guest
Speakers, as well as a final report on a NATO/CCMS project which was pre-
sented at an earlier conference are Included In the Appendices, the third
and last section of this report. The Appendices also Include a draft
description of a possible new NATO/CCMS study which would Include among
other things developing International standards for presenting results of
demonstration projects. Related to that aspect of the proposed study 1s
the work done by the International Standards Organization on standards for
soils; these are discussed In Appendix E.
RECENT DEVELOPMENTS IN NATIONAL PROGRAMS
This section reports on the "tour de table" portion of the meeting
during which each country described recent developments 1n national regula-
tory programs and research and development programs.
Canada
Responsibility for the management of hazardous wastes, hazardous
waste sites and ground water belongs primarily to the 10 provinces of
Canada and not the federal government. The exceptions are federal facili-
ties and federal lands such as airports, Canadian Forces Bases, National
Parks and the Yukon and Northwest Territories. The federal government
does, however, have responsibilities for transboundary waters such as the
-------
Great Lakes. The federal government has also enacted legislation con-
cerning the transportation of dangerous goods which applies to the
1nterprov1nc1al and International shipment of goods. The provinces have
similar legislation harmonized to the federal government's so that there Is
countrywide uniformity 1n this area.
Action with respect to site remediation nationally 1s being coor-
dinated through the Canadian Council of Ministers of the Environment
(CCME). In this overview, three national programs will be addressed:
1. National Contaminated Sites Remediation Program [CSRP]
2. Development and Demonstration of Site Remedial Technologies
[DESRT]
3. National Groundwater and Soil Remediation Program [GASReP]
(Petroleum Contamination)
The third program was Initiated 1n 1988 by Environment Canada's Wastewater
Technology Centre and the other two were announced by the CCME In October
1989 with funding from the federal government being made available In
April, 1990.
National Contaminated Sites Remediation Program
o The program 1s aimed at Site Remediation and the funding
available 1s specifically for "orphan sites." Coordination 1s
effected through the CCME.
o 1000 high risk contaminated sites Identified (out of a total of
perhaps 10,000)
o 50 or 5% Identified as orphan sites where no responsible finan-
cial party existed or can be Identified
o Program Elements
o Funding Is $200 million over 5 years on a 50/50 basis with
the 10 provinces and 2 territories. The federal government
will match provincial funding on a basis proportionate to
Its population.
o Each province Is to enact "compatible" legislation to
ensure the polluter pays principle 1s Implemented for site
cleanup. This applies to the cleanup of the other 95% of
the sites for which owners or responsible parties can be
identified.
-------
o A national site Inventory 1s to be completed.
o Hazard ranking, assessment and cleanup guidelines are to be
•developed on a national basis.
- Hazard ranking: based on U.S. EPA, probably available
by year end (December 1990)
- Cleanup Criteria: proposing to use "off the shelf" cri-
teria for now — some are already In existence In three
provinces as well as some Internationally
- A proposal to develop more "Canadian" oriented scien-
tifically defensible criteria was developed, however, 1t
has not been funded to date. Development of criteria
will take Into account the CCME National Decommissioning
Guidelines which are currently being published.
o Program delivery Is through bilateral agreements between the
federal government and each province and territory. A model
agreement has been developed and signature by 6 provinces 1s
expected by the end of December 1990.
o A number of Site Remediation Projects have been Identified as
candidate sites by the provinces:
Nova Scotia - LI swell (scrap yard)
New Brunswick - Albert County (oil exploration)
Quebec - St. Amable (tire fire)
- Belmer (scrap yard)
Ontario - Hagersvllle (tire fire - 18 million tires
stored there)
- Deloro Mines (arsenic)
- Smlthvllle (PCB's and associated solvents -
former, licensed PCB storage site)
British Columbia - Wells (mine tailings, acidic drainage and
metals)
o Estimated federal expenditure 1n FY 90/91 1s $6,000,000.00.
o Technologies applied generally for site remediation 1n Canada
have Involved excavate/secure landfill/biotechnology and
farm1ng/a1r stripping and air vacuum extraction.
o In addition to funding for the cleanup of "provincial" sites,
the federal government has allocated $25 x 10° for cleanup of
orphan federal sites over a five-year period.
Development and Demonstration of Site REmedlal Technologies Program (Desrt)
o This program 1s an Integral subset of the National Contaminated
Sites Remediation Program.
o Funding $50 x 106 over five years - cost shared 50/50 with pro-
vinces and territories.
-------
o Funding as follows for federal government for the next several
years
FY 1990/91 $4.5 million
FY 1991/92 $7.3 million
FY 1992/93 $7.3 million
o Nature of projects to be supported
o Pilot plant/prototype technology demonstration Projects
o Can also Include other aspects of site remediation, such as
- Methods and procedures for site characterization
- Risk assessment
o No projects underway to date but agreed 1n March 1990 at a
meeting of the CCME that the contaminated "Pacific Place"
site 1n Vancouver would be the first technology demonstra-
tion site to proceed under the program under a proposal 1s
presently being developed.
o V1lle Mender site may be another possibility as a result
of findings from NATO/CCMS study.
Groundwater and Son Remediation PRogram (GASReP)
o This program 1s concerned with the development of technology for
the remediation of contaminated soils and groundwater associated
with the petroleum Industry (and Is to be expanded to cover
other Industry sectors as well).
o Funding 1s provided by the federal government's Panel on Energy
Research and Development, Environment Canada, Industry and the
provinces to the extent of $500,000 per year.
o This program has been underway for two years. A number of pro-
jects are underway In the following areas: In-s1tu
Bioremedlatlon, Soil Venting and Off-gas treatment, Excavate and
Treat, and Pump and Treat.
o A number of conferences have been or will be sponsored under
this program. These are the following:
o Prevention and Treatment of Soil and Groundwater
Contamination In the Petroleum Refining and Distribution
Industry, October 1990.
o A Symposium on Advanced Oxidation Processes, June 1990.
o An annual GASReP Symposium each year, with the first annual
one being held 1n Ottawa, Ontario on January 30 and 31,
1990.
10
-------
Closing Remarks
We are Indeed grateful to be represented 1n this study and to take
advantage of the results which are being produced. We feel that par-
ticipation has been, and will continue to be, of great value not only to
our national programs but also to the technology development program of the
Wastewater Technology Centre.
Denmark
The new Act on chemical waste sites, oil spills and old landfills
(Act on Waste Disposal Sites) was enforced on the 1st of September 1990.
A total allowance of 570 mlo. Dkr is made for the period 1990-93:
1. Monitoring, Investigations on sites,
operating remedial actions (payed by
the Counties) Dkr. 280 mlo.
2. Remedial actions (payed by the State) Dkr. 290 mlo.
No allowance 1s made for research and development.
Register of polluted sites
To prevent an owner of a polluted site to sell the site without
Informing about the pollution problem, the Act demands, that the pollu-
tion problem must be registered 1n the Land Registry. This has caused a
discussion among the Banks and the Credit Associations (Building Societies)
and as a consequence, registered sites have Uttle 1f any value, - indepen-
dent of the size of the pollution problem.
The economic consequences for the owners of sites emphasize the
responsibilities of the Counties not to register without verylfylng the
Information and date on each site under suspicion.
Private Party Clean-Up
The limited pool of economic resources causes a tightening 1n the
order of priority. The National Environmental Agency and the County
Councils emphasize the ground water protection aspect. This means that
polluted sites, where the pollution only Influences the future use of the
site (e.ex. urban development at former Industrial sites), are of low
priority. Thereby, private parties applies for "voluntary clean-up
actions," which have to be authorized by the County Council. A part of the
public staff must therefore be allocated these not always environmental
based remedial actions.
At the time the 14 County Councils of Denmark are drawing up budgets
according to the Act on waste disposal sites, and the Councils acknowledge
the seriousness of the problem. Each County employs extra staff especially
allocated the register-work and preliminary risk assessments.
11
-------
France
Much has been already said about the french situation 1n matter of
contaminated sites by Mr. Bruno Verlon. However, In connection with that I
would like to mention two facts:
o The national 11st of officially registered contaminated sites Is
not exhaustive. Additional cases, some of them being serious,
are not mentioned 1n this 11st.
o There 1s a lack of appropriate commercially available
techniques, especially to treat contaminated soils. The use of
Isolation techniques, excavation, transport, treatment or dispo-
sal within the Industrial waste management system,
solidification-stabilization techniques as 1t has been carried
out until now 1s not technically and economically applicable for
the rehabilitation of some Important sites. Therefore there 1s
a significant opportunity for the transfer of some already
existing technologies.
In addition, I mention that our Agency has started a project of a
national databank of contaminated sites, this work being Integrated 1n a
wider french-german cooperative project (Universities of Berlin and Aachen,
Fach hochschule Saarbrucken) to be sponsored by the EC.
[See Appendix F for a description of some of the activities of ANRED,
Agence Francals pour la Recuperation et 1'Elimination des Dlchets.]
Germany
On 3 October 1990 the states Brandenburg, Mecklenburg-Western
Pomeranla, Saxony, Saxony-Anhalt and Thuringia became States of the Federal
Republic of Germany, 1n accordance with Article 1 of the Treaty between the
Federal Republic of Germany and the German Democratic Republic Republic on
the Establishment of Germany Unity (Unification Treaty). The 23 districts
of Berlin form the State of Berlin. According to Article 34 of the
Unification Treaty, programmes for ecological remediation and development
1n the new Federal States are to be drawn up, with priority to be given to
measures aimed at the prevention of hazards to the health of the popula-
tion. Abandoned contaminated sites are one of the focal areas of work
within the framework of the programmes. The following figures show the
progress made 1n the Identification of abandoned sites suspected of being
contaminated:
February 1989 915 sites
March 1990 1,300 sites
July 1990 2,529 sites
October 1990 30,000 sites
The figure listed last corresponds to some 60 to 70 percent of the
sites to be covered.
-------
According to Section XII of the Unification Treaty the so-called
exemption clause provided for 1n the Framework Environment Act
(Umweltrahmengesetz) of 29 June 1990 applies. According to this clause,
those acquiring Installations used for commercial purposes or within the
framework of economic undertakings are not liable for any damage caused
prior to 1 July 1990 as a result of the operation of the Installation.
Exemption may be granted after the Interests of the purchaser, the general
public and environmental protection have been weighed. Liability due to
claims based on dvll law remains unaffected. The purpose of the exemption
clause 1s to prevent the contaminated sites problem from deterring poten-
tial Investors.
Responsibility for the hazardous waste management and contaminated
sites belongs to the State Pollution Control Authority (Statens
forurensnlngstllsyn - SFT). The Hazardous Waste Division within SFT was
established in 1987, and has expanded from 3 to 11 persons within the last
three years. The expansion 1s mainly due to increasing focus on hazardous
waste landfills and contaminated sites. Responsibility for some parts of
hazardous waste control will be delegated to the counties in 1991.
Inventory of Contaminated Sites
A nationwide Inventory of landfills and contaminated sites has been
going on since 1988. The Inventory Is carried out county by county, and
will be accomplished by the end of 1990.
The Identified sites are ranked 1n one out of four groups:
Group 1: Immediate Investigation or action necessary
Group 2: Investigation necessary
Group 3: Investigation necessary 1f plans for the use of the area or
recipient are changed
Group 4: No further Investigation Is necessary
Ranking is based on Information obtained through Interviews with
local authorities, waste operators and Industries that generate hazardous
waste. A total of 1,000 Industries have been visited during the project.
The project has earlier been described at the.4th International Workshop in
Oslo, March 1990.
13
-------
Preliminary results of the Inventory 1s shown below:
National Inventory - number of Identified sites
Group 1
61
Group 2
480
Group 3
1193
Group 4 Total
707 2441
About one-third of the sites are municipal landfills.
Industrial landfills of concerns are particularly related to smelters
and metal work Industries of which a great number are located along Inland
extensions of the Norwegian fjords. Wastewater discharge from these
Industries has also caused an accumulation of polluted sediments. The
leachage of micro-pollutants (PAH's, PCB's and heavy metals) from these
sediments compared to the leachage front the landfills 1s one of the
questions that will be subject to further study.
Gasworks, wood preservation plants and electroplating plants are
among the most common polluted Industrial sites that have been Identified.
Action plan for remediation
The Ministry of Environment has required a national plan for reme-
diation. The plan 1s about to be developed by SFT, and will Include:
- Old landfills
- Industrial sites
- Polluted sediments
- Mining waste deposits
- Abandoned chemical stores
- And treatment of contaminated soil In general.
The plan's framework will be presented to the Ministry In January
1991. The final plan 1s to be developed within the end of 1991.
Several studies have been accomplished during 1990, as a basis for
the plan. The aim of the studies has mainly been to get an overview of
International knowledge and experiences on different aspects of the
problems, for Instance site characteristics, risk-analysis, Investigation
techniques and remediation techniques.
Five particular types of sites/soil pollution were chosen:
- Municipal landfills
- Deposits and contaminated sites from the smelting industry
- Deposits and contaminated sites from the metal work Industry
(especially foundries and shipyards)
- Heavy metal contaminated soil (especially related to electroplating
and wood preservation plants)
- Oil and tar contaminated soil
14
-------
Part of the studies will be continued 1n 1991, with demonstration
projects on particular sites.
Remediation of coke works site - Norsk Koksverk
The full-scale rehabilitation of a contaminated coke works site was
ordered In 1988 as part of SFT's commitment to soil and ground water reme-
diation. Site characterization 1n 1988-89 revealed significant con-
tamination by PAHs, arsenic, cyanide and naphthalene. Additional work 1n
1990 further defined the concentration and movement of the contaminants.
Approximately 40,000 tons of soil containing PAH's and/or arsenic were
removed and securely stored for treatment.
The pilot treatabllUy studies conducted In 1990 successfully treated
PAH's and naphthalene In soil by composting, and arsenic by stabilization.
Ground water was treated by two-stage precipitation for arsenic removal
followed by a blofllm process for organic removal.
Full scale rehabilitation 1s planned to continue 1n 1991 for a period
of two years. The total project budget Is 100 million NOK (approx. $17
mill.) Including site characterization, treatabllUy studies and full-scale
remediation.
The Netherlands
The Netherlands county representative was working 1n the United
States for the last seven months as a visiting scientist at the U.S.
Environmental Protection Agency, Risk Reduction Environmental Laboratory,
1n Cincinnati, Ohio. She gave a short report on the activities and
announced that a new NATO/CCMS study on environmental biotechnology was
being developed under the U.S. as director and the Netherlands as co-
director. The report at the next conference will cover recent regulatory
and research activities 1n The Netherlands. A report was also given of the
expanded scope of the KfK/TNO conference on Contaminated Soil being held 1n
December 1990 1n Karlsruhe (see Appendix G).
United Kingdom
UK developments affecting contaminated land Issues since the fourth
workshop are reviewed 1n this paper and Include the following areas:
1. Interdepartmental Committee on the Redevelopment of Contaminated
Land (ICRCL);
2. Hazard Assessment of Landfill Operations (HALO);
3. Environmental Protection Bill (EPB);
4. Government response to the Select Committee report on con-
taminated land.
15
-------
1. ICRCL guidance has now been Issued on restoration of metalli-
ferous mining sites providing Information on the concentrations
of potentially toxic elements 1n soils and on management prac-
tices to minimize adverse Impacts on plants and animals. It
Includes both "threshold trigger" and "action trigger" con-
centration for zinc, cadmium, copper, lead, fluoride and arse-
nic. (ICRCL Guidance Note 70/90, "Notes on the restoration and
aftercare of metalliferous mining sites for pasture and
grazing," from the DoE Publications Sales Unit. Building 1,
Victoria Road, South Ru1sl1p, Middlesex, HA4 ONZ (price 4.50)).
New additions of the guidance notes dealing with asbestos on
contaminated sites and redevelopment of landfill sites are In
preparation.
2. Hazard Assessment of Landfill Operations (HALO) 1s now being
developed by Her Majesty's Inspectorate of Pollution and will
provide guidance on landfill site assessment and methodologies
to Identify hazards and to evaluate site performance.
3. The Environmental Protection Bill also known as the "Green Bill"
affects contaminated land Issues. With the new Integrated
Pollution Control operators of scheduled Industrial processes
will be required to safeguard their sites against contamination.
4. The Government response to the House of Commons Select Committee
for the Environment was published 1n July, 1990 (The
Government's Response to the First Report from the House of
Commons Select Committee on the Environment, Contaminated Land,
July, 1990, HMSO, London). Key areas of the response document
are:
The possible abolition of ICRCL;
Definition;
Registers of contaminated land;
Caveat emptor;
How far to clean up;
Clean up technology development.
These key areas are summarized below.
4.1 The possible abolition of ICRCL
The suggested abolition of the ICRCL by the Select Committee was
rejected by the Government. The ICRCL will continue to provide a focus for
the development of technical guidance on contaminated land. The
Contaminated Land Branch (which Is within the Central Directorate of
16
-------
Environmental Protection of the DoE) Is being expanded and continues to
coordinate policy and manage the program of research In this area. (The
new Head of the Contaminated Land Branch 1s M1ss Judith Denner).
4.2 Definition
The definition of measurement of contaminated land still remains a
problem, with the Government believing that "contamination" 1s not capable
of precise definition and should remain as a general concept.
4.3 Local Register
Local authorities are to compile locally registers of potentially
contaminated land since more Information on the extent and location of con-
taminated sites Is required. An amendment to the Environmental Protection
Bill has been Introduced at the Lords Committee stage requiring district
councils In England and Wales and planning authorities 1n Scotland to com-
pile and maintain these registers of potentially contaminated land.
The Government position outlined 1n the response 1s that registers
framed this way should provide the best basis for alerting existing and
potential landowners to the need for full site Investigations, while
serving to minimize problems of planning blight.
A common classification system and methodology for these registers Is
essential, and the Government will also consider with local authorities,
the development of compatible computer hardware and software to facilitate
transfer of Information between districts and counties, and to the NRA.
It proposed to Implement the duty through Regulations prescribing a common
methodology. Recommendations on this will be made 1n due course 1n the
light of experience gained from a pilot survey In Cheshire. The Department
of the Environment commissioned a pilot study survey 1n Cheshire now
published as "Pilot Survey of Potentially Contaminated Land In Cheshire - A
Methodology for Identifying Potentially Contaminated Sites," July, 1990
(Department of the Environment, available from DoE Publications Sales Unit,
Building 1, Victoria Road, South Ru1sl1p, Middlesex, HA4 ONZ, price 2.55)
to assess the feasibility of compiling such registers and their potential
use.
The Government does not accept that a central UK 11st of seriously
contaminated sites 1n the UK 1s either feasible or necessary with the
establishment of local registers. Action over sites 1s still felt to be
matter for local initiative, with the application of appropriate environ-
mental priorities. A 1973/74 survey of landfill sites and the 1988/89 HMIP
survey of sites with landfill gas problems are both examples of studies
carried out with the help of local authorities. While 1t was felt that
both were valuable in assessing the potential scale of problems Involved,
neither were thought to provide sufficient detail to enable reliable risk
assessments to be made. The response further concluded that "to determine
sites posing serious risk at this stage would be an enormous task Involving
local area surveys and specific site assessments. And this would only
17
-------
enable a ranking to be made of waste disposal sites - not a priority 11st
of seriously contaminated land, including Industrial sites. Currently,
there does not exist the basis for compiling such a list. But the
Departmenmtwwm convene a meeting with the Local Authority Associations to
review what information 1s available from surveys on a country-wide basis,
which might be useful In drawing up local registers."
4.4 Caveat Emptor
The Select Committee recommend that the Government bring forward
legislation to place a duty on vendors to declare Information 1n their
possession about contamination present on site, however caused.
The Committee have referred to the Law Commission Conveyancing
Standing Committee study of the caveat emptor ("let the buyer beware") rule
on land sales, which proposed retaining the present caveat emptor rule but
1n the context of wider Information being made available to property buyers
through public registers and records. The Standing Committee recommended
that, as a matter of policy, Information of public concern or about matters
of widespread effect (Including actual or ptoenttal contamination) should
be on public registers. But their report suggested that a warning about
the need for further Inquiries should be entered on the new part of the
local land charges registers which 1s map-based and maintained by local
authority. The Government's view (expressed 1n the response) Is that the
proposals for local authority registers will meet most of these needs and
the value of additional entries on the land charges registers would seem
questionable. The Standing Commltee published their report on 25 January,
1990.
The Government also agree with the recommendation of the Select
Committee 1n the production of a Code of Practice governing the preparation
of land for sale. The development of such a code 1s under consideration.
4.5 Setting Standards
The Government response agreed with the Select Committee that the
concept of multifunctional1ty as a basis of restoration of contaminated
land should be rejected due to the high costs of bringing every con-
taminated land site back to a state that 1s suitable for any use would out-
weigh the perceived benefits. However,'the Government also accepted that
more emphasis on the environmental Implications of contamination 1s
required, which 1n turn requires an Increased emphasis on environmental
standards for contaminated land.
The Select Committee recommended a system of statutory quality objec-
tives and standards for soil similar to those being developed for the water
environment (water quality objectives). The Government believe that 1t Is
currently unrealistic to develop a universal system of soil quality objec-
tives and standards due to difficulties 1n Issues of regulation and
enforcement.
At present the Government, do not intend to legislate for a system of
statutory objectives, but will be extending the trigger value concept for
•the reclamation and clean up contaminated sites to cover a wider range of
18
-------
contaminants (Including asbestos, chloride, fluoride, hydrocarbons and aro-
matic hydrocarbons, chlorinated solvents, pesticides).
4.6 Technology Development
The response concluded the following. There 1s a wide range of tech-
nical knowledge about dealing with problems of contamination and this fund
of knowledge 1s continually being added to by publicly and privately funded
research and development in many countries. The Government need to con-
sider possible translation of relevant experience to UK circumstances. The
first step must be for an up to date appraisal of current USA and European
technologies. The Committee recommendations for wider based support for
demonstration projects 1n dealing with contamination will then be con-
sidered 1n assessing priorities for future relevant Government research and
development programs.
"The Government already have a scheme for start up funds In support
of the abatement technology Industry. Encouragement to develop new clean-
up techniques 1s provided through funds made available under the
Government's Environmental Protection Technology (EPT) Scheme. In June
1989 funding was made available under the scheme for research on methods of
treating persistent organic contaminants 1n soils by 1n-s1tu decomposition:
to date 7 applications have been received for funding."
The Government 1s expected shortly to announce new priorities for the
Derelict Land Grant program Including dealing with serious contamination
and demonstration of new clean-up methods.
The DoE currently funds research at the Warren Spring Laboratory
(WSL) to investigate the use of treatment techniques to clean up con-
taminated soils, and to-monitor the NATO/CCMS Pilot Study on ''Demonstration
of Remedial Act Technologies for Contaminated land and Groundwater." WSL
Intend to publish a technical appraisal of the various technologies
employed In the Pilot Study program 1n due course. The DoE will be funding
a new 3 year program of research at WSL on developing fract1onat1on/ma-
terlals handling methods for Integrated soil treatment; Investigating the
use of biological soil treatments to remove organic and heavy metal con-
taminants from soil; and Investigating cleaning debris from contaminated
sites.
In conclusion there are four areas of development:
I. Additional ICRCL guidance notes,
2. Hazard assessment of landfill operations (HALO),
3. The Environmental Protection Bill,
4. The Government response to the Select Committee report on con-
taminated land.
19
-------
United States
U.S. progress on hazardous waste site clean up continued apace during
1990. The size of the universe of sites being evaluated and selected for
the National Priority List Is shown 1n Figure 1, and the progress 1n moving
sites from feasibility study through design Into actual construction 1s
shown In Figure 2. Fiscal year 1990 was unique In the 10 year history of
the Superfund program in that, for the first time, the number of sites
ready for construction funding exceeded available funds. This situation
promises to worsen In the future. In addition, as shown 1n Figure 3,
fiscal year 1990 was a second banner year ~ over $1 billion — 1n terms of
agreements by companies to fund clean ups at their expense versus using the
Superfund Trust Fund and then attempting to recover costs 1n court.
The two major regulations affecting the Superfund program were
promulgated In final form during 1990. The National 011 and Hazardous
Substances Contingency Plan (NCP) 1s the broad organizational, regulatory,
and policy blueprint for the program. It was finally promulgated on March
8, 1990. In addition, the Hazard Ranking System (MRS), which 1s used to
score and rank sites on the U.S. National Priority List, was promulgated on
December 14, 1990 In the Federal Register. The revised HRS Includes
changes to almost every aspect of the algorithm that 1s used to score
sites; the simplest explanation of the changes Is that the former HRS fully
recognized two and one-half exposure paths — surface water, ground water,
and past air releases. The new system recognizes these pathways plus
potential air releases and direct contact threats. It also more fully
evaluates ecological threats from sites.
The latest description of the use of alternative (to land disposal)
and Innovative treatment technologies 1s summarized 1n Figure 4. In addi-
tion to choosing these Innovative technologies, data on their full scale
application Is of prime Interest. Figure 5 shows the status of actual
Implementation of these technologies. In order to champion the use of
these innovative technologies, EPA created a new Technology Innovation
Office during 1990. Its mission 1s more fully described 1n Appendix H; Its
principal focus 1s on changing behavior by consulting engineers, state and
Federal project managers, and Industry toward the application of such Inno-
vative technologies.
In addition to a broad focus on Innovative technologies, EPA's waste
program office and research offices commenced a bloremedlatlon field Ini-
tiative 1n the summer of 1990. Its purpose was to Increase the amount of
cost and performance data available regarding 1n-s1tu and above ground
bloremedlatlon. The three major thrusts of the program were to (1) conduct
evaluations of targeted full-scale site clean ups, (2) strongly encourage
the use of treatablllty studies prior to choosing bloremedlatlon, and (3)
gather such data and place 1t 1n an available public resource — EPA's
Alternative Treatment Technology Information Clearinghouse (ATTIC). As of
November 1990, about 135 sites had been Identified where bloremedlatlon,
was planned, being evaluated, 1n design, or being constructed (Figure 6).
20
-------
FIGURE 1
Status of CERCLIS Inventory
(CERCLIS Inventory = 33,575)
NPL SftM Including D«Wn and EnglnMring SludlM)
vn (io%)
Em*rg«ncy Action T*k*r. (Ptndtng
m-.»siiaatlc,i and EnglnMrlng Studto*)
19 (1%)
Construction Uoo*rwwy
271 (22%)
114 (9%)
Note StfffMntiOTCunMMfM. SNMivWi
caratwcOon undomy hare tlnody cxxvple
ttwfy, nnmly MhcOon. tnd detlgn.
and EngbtMrfng
21
-------
FIGURE 3
Value of PRP Settlements
Has Gone Up Nearly Seven Fold
I
o
I
«
$1,400,000,000
$1,200,000,000
$1,000,000,000
$800,000,000
$600,000,000
$400,000,000
$200,000,000
$1.3 billion
285 settlements
M
tu
1987 1988 1989
Fiscal Years
1990
FIGURE 4
Source Control Treatment* Fiscal Years 1982-1989
Treatment Technologies Specified - 252
Number of RODS - 211
Solidification / Stabilization
(62) 24.6 %
Thermal Desorption
(13)5%
Chemical Destruction
(4)1.6%
In-situ Vitrification
(2)0.8%
Vacuum/Vapor Extraction
(30) 12%
On-site Incineration
(48)19%
Other (9)
3.5%
In-situ Soil Flushing
(10)4%
Off-site Incineration
(40)16%
Soil Washing (7) 2.8%
Chemical Extraction (6) 2.4%
Bioremediaton (21) 8.3%
cUonaoiv
* Superfund Program data derived from ROOs and anticipated design and conBr
( ) Number of times this technology was selected
December 19,1990
22
-------
FIGURE 5
Remediation Status* of Innovative
Technologies
(Source Control Only)
Technology
Vacuum Extraction
Bioremediation
In-Situ SoU Rushing
Thermal Desorption
Soil Washing
Chemical Extraction
Chemical Destruction
In-Shu Vitrification
Predesign/
In Design
25
16
9
10
7
5
2
2
Installation/
Operation
5
4
1
0
0
1
1
0
Project
Completed
0
1
0
3
0
0
1
0
Total
30
21
10
13
7
6
4
2
^
• Status as of December 1990
December 19,1990
FIGURE 6
EPA Bioremediation Field Initiative
Number of Projects at Various Stages of Implementation
Number
of
Sites
Planning* Lab/Pilot Lab/Pilot Full Scale Project
Trealability Treatability Implementation Complete
Studies in Studies Begun or Under
Progress Progress Design/
Construction
* Includes sites where bioremediation has been selected, but no treatability studies in
progress or performed, and where bioremediation is likely to be selected
December?, 1990
23
-------
24
-------
Project Reports
25
-------
26
-------
NATO/CCMS Cover Sheet
TREATMENT CHARACTERIZATION
General Type: Pump and Treatment
Specific Type: Recovery/recycling
Manufacturer/Researcher:
Status:
Treatable Contaminants: Z1nc, cadmium
Treatable Waste Matrices: Ground water
On-/0ff-s1te Treatment Location: On-slte
Pre- and Post-treatment Requirements:
SITE DEMONSTRATION
Site Location: Z1nc smelting plant, Lot River,
V1v1ez, Aveyron-France
Contamination: Z1nc, cadmium
Site Characteristics:
CONTACTS
Rene Goubler
Head of Hazardous Sites Team
Agence Natlonale Pour la Recuperation
at 1'Elimination des Dechets (ANDRED)
2 Square la Fayette
BP 406
49004 Angers Cedex
France
tel. 41-20-41-21
telex. 721325 F
fax. 41872350
27
-------
VIEILLE MONTAGUE
The origin of zinc production in VIVIEZ goes back to the years 1870.
Until 1930, the process was thermic, and all the wastes were thrown near
to the plant, on the hill slope. Such is the origin of this waste heap.
Afterwards, the Vieille Montagne company shot hydrometallurgic refuse
coming from the electrometallurgic process.
The total amount of wastes stored in the heap is evaluated to
700000 tons.
Natural lixiviation by rainfall takes metallic ions to the ground
water located at the hill-foot then to surface water which are
contaminated.
The amount of cadmium thrown in the environment amounted to a
mean 36 kg/day up to 1987.
When this permanent pollution was proved.studies were carried out
in order to understand the circulation phenomena of metallic ions to the
superficial hydraulic system and, then decide which means had to be put
into operation so as to eliminate this pollution.
1) Hudrogeoloqical study:
The aim of this study was to evaluate:
- the hydrodynamic behaviour of the alluvial aquifer,
- the hydraulic relations aquifer/heap,
- the surface water regime.
At the same time,the qualitative aspect, based on water analysis,
had to be taken into account.
Analysis of boreholes and water have led to collect a certain amount
of information which can be summed up as follows:
- initial geological scheme showing various overlaid structures,
- drawing of a piezometric map on which a mathematical model was
set up in order to localize flow repartition,
28
-------
- detailed analysis of data taken from all the control equipment.
including cadmium content in surface and ground waters leading
to a global balance.
In this general context, the first actions, brought up in 1938, were
taken so as to cover ponds containing muds and to relocate the smallest
storages.
The impact on natural environment .was in a very short time
effective since the day cadmium content went down from a 36 kg/day
0987) to a 2 kg/day early in 1989.
2) P2 point
P2 is a special point highly polluted in cadmium (1250 mg/1) which
was due to a temporary storage of ore. P2 is an important element of
cadmium re-emission (about a third of the pollution).
Tests carried out in July 1988 have led to a better knowledge of the
"P2 point" which had been located before and to locate cadmium
concentrations around this point.
It was possible to locate a zone of cadmium dissolved content higher
than 300 mg/1 around boreholes P2, P3, 57 and S5. Maximal contents ere
surrounded by concentric circles: a 200-300 mg/1 circle and another one
at 100-200 mg/1, both 10-20 m wide are limited by boreholes S6, SI, S2
and S3 ; further around, cadmium contents are similar to that measured
elsewhere, particularly in the waste heap in the THR zone.
Hydraulic values have been fairly evaluated: mean transmissivity is
T = 5,0 . 10 ~4 m2/s and storage coefficient S = 3,0.10~2
These values have been used to test in a mathematical model three
hypotheses of decontamination by pumping/injection: it has been decided
to decontaminate putting into operation two pumping boreholes (P2 and
S5) at 8 rn3/h and four injecting boreholes (S2, S4, S6 and S7> at 4 m3/h.
Tests carried out during the spring season in 1989 have led to the
idea that this solution was feasible and efficient. In addition, leaching has
been carried out by injecting in three points and pumping in two others.
Nowadays, cadmium content as controlled in two boreholes under
-------
permanent pumping at 2 m3/h does not exceed 50 mg/1, same value as in
the rest of the plant.
3) General balance at "Laboratory" point.
A permanent control located on the surface network (Riou Mort) on a
point considered as perfectly representative ("Laboratory" point), is used
in order to follow the impact of the installation.
Although hydrological conditions have been exceptionnally dry for
two years, il is confirmed that cadmium emission has been drawn down
and that, even when flow rates are high due to important rainfall, the
maximum cadmium content approved by the authorities (500 g/h) is
respected.
Thus, in general, actions carried out on the site have led to a
cadmium lowering of
-------
Generally speaking, from a zone in borehole F1 (1 mg/1 Cd), there is a
progressive enrichment of waters up to a mean value of 50 mg/1.
Two options can be taken to solve this problem:
- a "methodologic" way aimed at understand all the mecanisms
involved.specially the role played by the clay layer (resorption)
- a pragmatig "field" way aimed at dewatering the downstream part
of the heap (THR) where the clay layer - which is supposed to
enrich the upper part of the aquifer in Cd - is located.
This second option has been chosen and includes three steps :
1) construction of a derivation system of surface waters coming
from the upstream part of an old river bed covered by the heap
2) evaluation phase : it is supposed that waters infiltrated in the
heap do not dissolv Cadmium, due to the high permeability of the
"thermic" part of the wastes and to the protective impervious
layer of the basins. If this hypothesis is confirmed, waters can
directly be evacuated in the environment without flowing through
the THR zone
Controls will be achieved through water analysis on Fl on a
complete hydrological cycle.
3) Water recovery : in this case, it has been decided to dig a
collecting system including a trench, an acces gallery and a final
drain.
Calendar : decision to be taken in 1991 (if the hypothesis n°2
appears not to be ascertained,waters will have to be
decontaminated); works to start in 1992.
Estimated cost: 2 MF.
31
-------
PLAN
-------
lonlogne Usi'ne de Viviez
\» pi Op
A qt^tUJcwl ft jv<.. Uok,
\ll\lw
>
-------
U8INC DC VICH.LC MONTAOHE A vrvitZ ( 12 )
I PLAN DE SITUATION DU GRASSIER
aee*
(V) BAeera eamasxeaa KSBSJEB
I I OBJQIBB BUI O2CBBI33 •
•< i*
3. ratnurimc
ri«. emnAER &
ut
-------
30*
200
-------
CARTg
u>
-------
tmro
-------
p
-*?))*
fa,
, p
c/^c_y^(jm_ii4c^
u
tfl
r\
-------
V1EILLE-MOIMTAGNE
Usine do Vivicz -12110 AUDIN
ETUDE IIYDnOGEOLOGIQUE ot IIYDHOCII1HIOUE
dc la PLAINE AI.LUVIAI.E du RIOU VIOU
LEGENDE GENERALE
£5
POMPAGE DU 26/07/00 Bur S5 : REPARTITION DES CONCENTRATIONS
EN CAUMIUM UE L'EAU UE LA NAPPE DANS l.E SECTEUR DU P2
»'^*" Concentration en mg/1
-------
ICOHCCHrRAUOH MOYEHNE EN CADHIUH DES EAUX AU POINT "LABORATQIRE1
ANI4ECS
89
10
11
12
90
01
02
03
04
05
06
07
08
09
10
11
x(mg/l)
0.17
0.1C
—
0.14
-
0.17
0.14
0.10
0.10
0.11
0.14
Qm3/h
445
683
—
515
—
1 000
1. 120
2 243
720
270
180
F^
74
104
-
72
116
123
204
26
28
30
REHARQUES
(polnte & 2.260 m3/h -> 0.10 mg/h)
(polnte & 1 850 m3/h -> 0.08 mg/h)
(polnte & 3 230 m3/h -> 0.10 mg/h)
(polnte & 1 130 m3/h -> 0.15 mg/h)
40
-------
nuoi
12.VIVIEZ.VIEILLE MONTAGNE
I £ SA Mc£. HMDIX06-E.OUO 6-lQvE DO
COUP£ P.U
DV T.H.O- £T T> U C R A J S i £ R.
Du T.H.R
PLAKCH.E 2
GM.cLa.lt ll^t-^j. j, ^.,
t- - ItJ-S!
I- . 1^4 SO
i - '.It «<>
_HJ Oi
T. H.R
CRASSI
-------
LEGENDE
r
^.'
Ve
ecu*
r 67.180
0-
Cr
/ c f
-------
CAP
Cap
43
-------
CAPTAGE DU RUISSEAU DU GRASSIER
DE DUNET
COUPE LONGITUDINALE
i*.U%*»T*S
Ai,-re« «*
fi . £-«U'./t U,(f«j--'.j.-.v4 S*;
»j j o a *
'/Lac
-------
UI1PLMSES EHCAULES POUR IE TRAITEHENT DES CRASSIERS
(exprim^es en Francs frentals)
PRINCIPAL ix posrns
1. Campagnes do Cofa/jR1;
analyses, suivis, iinieuaqo-
ments transfci Ls <1p bone?...
2. Station de li aitampiil des
eaux
3. Amgnagement? du pnint dc
mesure (point laboi aloii c)
4. Etude des mecani sines de
Fixation des ions dans lu
sol
5. Mlse en place d'un Tiltie
presse
SOUS-TOTAUX
6. Frals de fonctlonnement :
(traltement des eaux)
7. Am^nagements des bassins de
I'lgue du Mas
TOTAL GENERAL
(987
1 325 000
45 000
250 000
1 620 000
1988
1 665 000
1 550 000
860 000
130 000
4 205 000
7 500 000
1989
1 020 000
1 020 000
5 000 000
1 420 000
1990
300 000
1 600 000
1 900 000
4 000 000
1 900 000
Sous-Totaux
8 745 000
16 500 000
3 320 000
28 565 000
45
-------
46
-------
NATO/CCMS Cover Sheet
TREATMENT CHARACTERIZATION
General Type:
Specific Type:
Manufacturer/Researcher:
Status:
Treatable Contaminants:
Treatable Waste Matrices:
On-/0ff-s1te Treatment Location:
Pre- and Post-treatment Requirements:
SITE DEMONSTRATION
Site Location:
Contamination:
Site Characteristics:
CONTACTS
Rol Roth
Dekonta GmbH
Lotharstr, 26
6500 Mainz
Federal Republic of Germany
06132-772211
Pump and Treatment
Separation pumping
Geological Survey of Denmark
Research
Chlorinated hydrocarbons
Ground water
On-site
Waste dump site
Skrydstrup-Denmark
Chlorinated hydrocarbons
Lars Jorgen Andersen
Geological Survey of Denmark
ThoraveJ 8
DK-2400 Copenhagen NV
47
-------
The NATO/CCMS Pilot Study on
Demonstration of Remedial Action
Technologies for Contaminated
Land and Groundwater
Fourth International Conference
5-9 November 1990
Angers
France
THE SEPARATION PUMPING TECHNIQUE
by
Bertel Nilsson
Rasmus Jakobsen
Geological Survey of Denmark
8, Thoravej
DK-2400 Copenhagen NV
Denmark
48
-------
0. Abstract
Demonstration tests of the separation pumping technique has been
performed at several sites in Denmark. The separation pumping
technique relies on simultaneous pumping from top and bottom of
a fully penetrating well, through the polluted section of the
aquifer. Separation pumping is developed from the concept of
scavenge pumping. The method can optimize remedial action pumping
by minimizing the volume of polluted water to be treated.
Furthermore the inflow distribution and transmissivity of
selected sections of a well can be determined. Moreover the
method can be used for collection of level-accurate samples.
Finally, changes in the vertical distribution of pollutants in
the aquifer as a function of pumping time can be monitored.
Results from two different sites, a sand and gravel aquifer, and
a limestone aquifer show that separation of polluted groundwater
from slightly polluted or non-polluted groundwater was possible,
and for the sand and gravel aquifer the amount of water to be
treated was initially reduced to 40%. Tests with separation
pumping as an investigation tool at a third site, showed that the
influx distribution could be determined with high precision, and
very high vertical concentration gradients could be discerned
with separation pumping used as a level-accurate sampling method.
-------
1. Introduction
Groundwater contaminated by leachates from point-pollution
sources are an increasing problem all over the world. Especially
in countries, where the water supply is based on the groundwater
resources. Pollutants often occur zonally distributed in the
aquifer. Close to waste disposal sites the pollution plume are
typically restricted to narrow zones with more or less sharp
interfaces between underlying and/or superimposed zones of pure
groundwater.
These facts have been utilized to optimize recovery of polluted
groundwater by use of the separation pumping technique. The
technique is an investigation procedure and a remedial action
technique, for groundwater pollution. The method relies on
simultaneous pumping from top and bottom of a fully penetrating
well, through the polluted section of the aquifer. Separation
pumping is developed from the concept of scavenge pumping (e.g.
Tate & Robertson, 1971), and has been developed as a part project
under the danish research and development program, Lossepladspro-
jektet. The experiments have been carried out in 1989-1990 by the
Geological Survey of Denmark (responsible) and the Danish
Geotechnical Institute in cooperation with the National Environ-
mental Research Institute. The project has been supported by a
grant from the National Agency for Environmental Protection.
The main purpose of the project was to optimize remedial action
pumping by minimizing the volume of polluted water to be treated.
Principles and procedures are briefly described, and results of
three demonstration tests are presented.
50
-------
2. Applicability of the method
2.1. Remedial action pumping
In remedial action pumping the well is pumped simultaneously from
top and bottom with two pumps (scavenge pumping). One of the
pumps recover the polluted water and the other the non polluted
water (see section 3.4). If there is pure water above and below
the pollution plume, three pumps are used simultaneously in the
same well, the middle pump recovering polluted water, and the
top- and bottom pumps non-polluted water. The three-pump-
arrangement has been tested in laboratory experiments in a
transparent sand model, and in controlled full-scale field
experiments. Results are described in Nilsson et al. (1990).
2.2. Investigation
2.2.1. Concentration profile
In situations with zonal distribution of dissolved solids in the
aquifer it is possible to determine the vertical distribution of
the pollutants by sampling of the water from the top and bottom
pumps, at different relative pump rates.
2.2.2. Vertical distribution of hydraulic conductivity
The separation pumping technique can be used for determination of
the inflow distribution and transmissivity of selected sections
of the well. Two procedures are described in section 3.2.
2.2.3. Level-accurate sampling of qroundwater
Finally the method can be used for collection of level-accurate
samples within a fully penetrating well, either aided by a Heat-
Pulse-Flow-Meter probe (HPFM), section 3.3., or in a situation,
where the inflow distribution is known.
51
-------
3. Methodology
3.1. Separation pumping
The water well is simultaneously pumped by two pumps at the top
and bottom, respectively/ Fig. 1. A water divide is created in
the borehole between the two pumps. Water from above the water
divide will move towards the top pump and water below the water
divide towards the bottom pump.
By adjusting the pumping rates of the two pumps the water divide
can be established at any position in the borehole according to
the ratio between the pump rates and the hydraulic conductivity
above and below the divide. These position are unknown but can be
found indirectly by a separation injection test (SIT), see
section 3.2, by conventional flow-logs or by direct measurement
with a Heat-Pulse-Flow-Meter (HPFM), see section 3.3.
FLOWMETER
TOP PUMP
FLOWMETER
GROUND SURFACE
r
GROUNDWATER LEVEL
-DIVIDE
BOTTOM PUMP
D6W
Fig. 1.: Schematic illustration of separation pumping by
simultaneous pumping from top and bottom of a well.
From Andersen (1990).
52
-------
The following parameters are measured during separation pumping
for every "steady state" situation (step), the total capacity is
kept constant for all steps.
a) The pumping rates for the top and bottom pumps.
b) The chemical composition of the water from the top and
bottom pumps.
c) The water level in the borehole.
The water samples from the top and bottom pumps are taken when
these parameters are stabilized at each pumping ratio (step). The
vertical distribution of a pollutant within the penetrated part
of the aquifer can be calculated.
The principles of a 9 step separation pumping is shown in Fig. 2.
Nine different combinations of pumping rates (step 1-9) divides
the screened part of the well in 10 inflow intervals.
The flow pattern shown on the sketch corresponds to step 3, where
intervals 11-13 supply the top pump and intervals 14-110 the
bottom pump.
For steady state conditions the total flux of each pollutant
leaving the well ((Q'C)* + (Q'C)b) should be constant.
The influx of the pollutants from the ten intervals: qi»Ci
(i=l,2, ,10) can be calculated from the following equations:
qi • Cj = (Q! •
q2 • c2 = (Q2 - c2)« -
q* • Ct = ((Qt • C« - Qj • C3)* + (Q3 • C] - Q« • C«)b)/2
q* • C3 = ((Q3 • C5 - Qt • C4)e + (Q4 « C* - Q5 • C3)b)/2
q* • C6 = ((Q6 • C« - Q5 • C5)1 + (Q3 • C5 - Q« • C6)b)/2
q? ' c, = ((Qr • C7 - Q6 • CO* + (Q6 • C« - Q? • C7)b)/2
q8 • ce = (Q7 • C7)b - (Q8 - C8)b
q9 ' c, = (Q8 • C8)b - {Q, - C9)b
• CIO = (Q, • C,)b
53
-------
Ground surface
Waler divide
—--.U^JsLI s,cpl
q"c' ^ ' ta
>.Cj I I 13
1-No Mow—I
—t—
_:±p___4---
flt,<=( -L ' 16
Steps
. Step 6
4 StepB
Fig. 2.: sketch of a 9 step separation pumping. Q = measured
pumping rate, C = measured concentration, b = bottom,
t = top, c = calculated concentration and q - calcu-
lated inflow from the aquifer.
The q-c-fluxes for the top and the bottom intervals are given
directly from the measurements, the fluxes for interval 12, 13,
18 and 19 are calculated using the top and bottom data respect-
ively while the middle intervals 14-17 are calculated using
average values from the top and bottom pumps.
-------
All Q-values are measured and q-values are easily calculated.
q» - (Qi)e
- Qi)r + (Qi - Qa)V2
q* - <(Q4 - Qs)1 + (Qi - Q«)*)/2
q5 - ((Qj - 0*)' + (Q* - Qi)V2
% - <(Qs - Qi)s + (Qs ^ &)*)/2
q; » ((Or - Qi)c * (Qi - Q»)*)/2
q, • ((09 - Qs)' + (Qs - Q9)b)/2
(Qio)b
The principles of calculation and assumptions are described in
Andersen et al. (1989) and Gosk & Bishop (1989).
3.2. Hydraulic conductivity log
3.2.1. Separation pumping test (SPT)
The object of the separation pumping test (SPT) is to determine
the inflow distribution in a well. The principle is seen in Fig.
2 for a 9 step SPT. The location of the water divides is done
with a Heat-Pulse-Flowraeter, described in section 3.3. The yield
of each section can be calculated as shown in section 3.1.
3.2.2. Separation injection test
The separation injection test (SIT) is an inverted (SPT). Water
is injected to the top and the bottom of a well and of the
measured flow rates are the recharge rates of the intervals above
and below the convergence zone, the opposite of a water divide.
The location of the convergence zone between top-water and
bottom-water is determined by using an in-hole-detectable tracer
mixed in the top- or bottom injection water. For example
chloride, in a concentration sufficient enough to separate it
from fresh water, can be used. The interface between the salty 55
-------
and the fresh water is detected by an electric conductivity
probe.
3.3. Level-accurate water sampling
The well is simultaneously pumped from top and bottom, Fig. 3.
The position of the water divide is found by & Heat-Pulse-Flow-
Meter (HPFM). A HPFM-probe is a directional low-velocity
flowmeter. An electric energy pulse is fired through a wire grid
creating a small volume of warm water and its direction and
velocity, corresponding to the flow of the fluid in the borehole,
is determined by the monitoring of two thermistors, one above and
one below the wire grid.
A water sample is collected at the water divide by a third pump,
pumping with a yield of a few percents of the total capacity with
which the well is pumped.
By varying the pumping rates of the two pumps, the water divide
can be placed at any depth so that a chemical profile of the
penetrated sequence of the aquifer, can be made.
WATER SAMPLE
SAMPIINS PUMP
HEAT • PULSE • F10W • METER
WATER DEVICE
BOTTOM PUMP
06U
Fig. 3.: Schematic illustration for level-accurate groundwater
sampling by separation pumping. From Andersen (1990).
56
-------
3.4. Separation pumping as a remedial action
From the concentration profile determined in section 3.1, it is
known at which yield ratio between the top and bottom pumps one
of the pumps only recover water from the polluted layer and the
other water from the unpolluted layer, Fig. 4. In this way the
volume of polluted water is restricted to a minimum, the polluted
part of the inflow to a well. The efficiency of the method is
limited if the partial transmissivity of the unpolluted layer is
much smaller than the one of the polluted layer.
FLOWMETER
POLLUTED WATEfl
PUMPING WATER LEVEL
NON-POLLUTED ZONE
FLOWMETER
UNPOLLUTED WATER
GROUND SURFACE
GROUNDWATER LEVEL
Dew
Fig. 4.: Schematic illustration of remedial action pumping by
use of separation pumping technique. From Andersen
(1990).
57
-------
4. Results and discussion
The separation pumping technique has been tested at different
sites in Denmark and has been used at a site in United Kingdom.
Experiments from three sites in Denmark are presented.
4.1. Experiments of remedial action pumping in a sandy aquifer
4.1.1. Site description
The first tests have been performed at the chemical waste
disposal site registered under No. 543-01, Skrydstrup, Municipa-
lity of Vojens, County of Senderjylland. The site is located
close to Skrydstrup Airport, Vojens City and approximately 2,5 km
up-stream one of the water works of the Municipality of Vojens
(Fig. 5).
Fig. 5.: Locations of test sites in Denmark.
In the period 1963-1974 chemical waste has been dumped in an old
gravel pit near Skrydstrup by a refrigerator factory. The waste
caused a considerable contamination of the groundwater by
58
-------
chlorinated solvents, mainly 1,1,1-trichloroethane and organic
phosphorus compounds.
The waste was excavated in 1986, the drums with chlorinated
solvents were sent to destruction, and the contaminated soil was
placed in a special waste disposal site with aerobic/anaerobic
in-situ biodegradation of the chlorinated compounds. The latter
enter into the NATO Pilot Studies.
The pollution plume has been found up to 1,5 km down-stream from
the dump site. The remedial action pumping is from four wells
screened to a depth of about 25 m.b.s. The pumped water is
treated in a on-site groundwater cleaning plant by air-stripping,
and active carbon filtration. In November 1988, at the beginning
of the remedial action pumping, wells PB2, PBS, PB9 and PB10 were
used, (Fig. 6). In June 1989 well PBS was replaced by well PB16,
in which the demonstration experiments with separation pumping
were performed.
*>
LEGEND:
• pozpumping well
Chemical waste
disposal site
Pollution plume
Groundwater
flow
Fig. 6.: Skrydstrup chemical waste disposal site and the
pollution plume. Location of the remedial action
pumping wells PB2, PBS, PB9, PB10, PB16 and the
direction of groundwater flow are shown.
59
-------
4.1.2. Hvdroqeoloqy
The aquifer material consists of meltwater sand and gravel under
water table conditions. The thickness of the aquifer is about 60
m, just below the waste disposal site, decreasing down-stream,
and the water table is approximately 4-10 ra.b.s. The thickness of
polluted groundwater was 7-10 m at the beginning of the experi-
ment, determined by a well drilled close to well PB16, section
4.1.4.
4.1.3. Experimental set-up
Well PB16 is 200 mm in inner diameter, 25 meter deep, and
screened from 6-25 m.b.s. The set-up consists of two submersible
pumps (max. capacity 11 mVhr) in the borehole, valves to adjust
the pumping rates of the two pumps, and electromagnetic flow-
meters to measure the actual flow from each pump.
4.1.4. Results and discussion
First a 9 step separation pumping was performed, dividing the
inflow interval in 10 sections each contributing a flow partial
of approximately a 1/10 of the total discharge of 10 mVhr. (Fig.
2). The positions of the water divides have been estimated
indirectly from an impeller flow log, run in well PBS. Fig. 7
shows a calculated concentration profile of three chlorinated
solvents (TCA, TCE and TeCE) and the electrical conductivity
(EC). It is seen that the concentration of the pollutants is
highest in the upper most intervals 11-12 and the concentration
decreases strongly in interval 13 and the underlying intervals.
Generally 1,1,1-trichloroethane occur in a concentration about 10
times higher than trichloroethylene while tetrachloroethylene
only occur in the upper most intervals 11-12 in a concentration
below 1 ng/1. The electrical conductivity is correlated to the
chlorinated solvents. Furthermore it appears from Fig. 7, that
approx. 30% of the total yield is coming from the inflow interval
7,5 - 17,0 m.b.s., while 40% comes from 17,0 - 20,5 m.b.s. and
the last 30% from a deoth of 20,5 - 25 m.b.s.
-------
100
4-
10-
15-
cg/i
—i—
500
100
»Stan »>
300
O—O TCA, jig I \
•-• TCE, Jig I1
A—A. TeCE, jjgM
•—• EC,jiS/cm
• Pumping water-level
iniervar i
Interval 2
i/—-/-
Bottom of well
Fig. 7.: Calculated concentration profile in well PB16, Skryd-
strup of the chlorinated solvents (1,1,1-trichlo-
roethane (TCA), trichloroethylene (TCE), tetrachloro-
ethylene (TeCE)) and the electrical conductivity (EC)
compared with the interval depths.
61
-------
The calculated concentration profile of the chlorinated solvents
has been confirmed immediately after by drilling a BOTESAM-well
(Larsen & Andersen, 1988) a few meters from the testing well,
sampling groundwater for every meter (Fig. 8).
BOTESAM - welt No.151.1072, Skrydslrup (Denmark)
Concentration of Chlorinated hydrocarbon* In pg M
{scale logarithmic]
10 too 1000
10000
15
— 1,1,1,-TrichlaroethaneeTCA
Trlcnloroelhylene = TCE
Telrachloroef hyfene = TeCE
Fig. 8.: Chemical profile from the BOTESAM-well, Skrydstrup.
Based on the results of the separation pumping test it is
possible to optimize the remedial action pumping by separation
pumping, (section 3.4). The efficiency of the optimization has
been examined as a function of the pumping time (Fig. 9). Further
the optimized remedial action pumping with two pumps has been
compared to the situation where, traditionally, only a single
pump is used so, that water from polluted layers is nixed with
water from non-polluted layers. In the period July - October 1989
the content of chlorinated solvents in the bottom water was below
1 ug/1 while the concentration in the top water was 900 - 1450
ng/1 when the contribution from the top pump varied from 35% -
50% of the total discharge and the bottom pump from 65% - 50%. In
the subsequent period November 1989 - March 1990 the pump ratios
are changed in order to keep the non-polluted bottom water free
of solvents. This means that less than 10% of the total discharge
is non-polluted water. This must be related to a change in
vertical distribution of chlorinated solvents within the
aquifer. The change is probably due to reinfiltration of the
cleaned water from the treatment plant, into a p5t at the
62
-------
disposal site. This roust cause a- downwards movement in the
groundwater, which appears to have forced the lower boundary of
the plume, downwards by 10 meters in 9 months, at the position of
the test well.
Concentration of chlorinated hydfocarbons(pg/l)
1MO-
1000"
sco-
F^vl Cone. In lop water
IBB Core. In bottom water
EU Cone, in mixed water
C
It
ew
an
J
;•
S
£
Mo
>la
r?
S
'v
v!
Cj!
rtna
of!
BW
0.11
•i
S
A
ed hydro
rcA, TCE
-
S
«arbon*
,TeCE
n
9W
aat
rn
o
s
•v
|
P
1
1
;;
N
0
1SW
r?
I
•I;
|
v
:s
i
!
s
il
j
F
^
:.":
|
|
I
M
ibao
The fraction of conpolluled water
1.0-
CJ-
i i
i 1 A
1 I 1
S 0 ) N | 0 J
n
F M
Fig. 9.: Optimized remedial action pumping by separation pumping
in well PB16, Skrydstrup. Test period July 1989 - March
1990. A: The concentration of chlorinated hydrocarbons,
a total of TCA, TCE and TeCE, in top, bottom and mixed
pump water. B: Fraction of non-polluted water of total
yield.
4.2. Experiments of remedial action pumping in a limestone
aquifer
4.2,1. Site description
Tests have been performed in a Water Supply well at P. Andersens
Vej Waterwork, Municipality of Frederiksberg, situated in the
central part of the Cooenhaaen nr<=^ /T-J^ c <.
63
-------
Chlorinated solvents, mainly trichloroethylene (TCE), have
polluted the limestone aquifer. One of the water supply wells at
the test site is slightly contaminated with up to 15-20 jig/1 TCE
in the production water. This was chosen as the test well.
4.2.2. Hvdroqeoloqv
The confined limestone aquifer with fissure flow occurs from-
about 20 m.b.s. and downwards. The test well has a diameter of
300 mm, is about 71 m deep, and has an open-hole interval from
50-71 m.b.s. All the water supply wells in the municipality of
Frederiksberg are situated in a 500 m wide, high yielding fault
zone, named the Carlsberg Fault.
4.2.3. Experimental set-up
The experimental arrangement consists of two submersible pumps
placed in the borehole, one just above the bottom of the casing
with the intake approx. 47 m.b.s. and the other pump near the
bottom of the well with the intake approx. 68 m.b.s. The sub-
mersible pumps each have a max. capacity of approx. 50 mVhr.
4.2.4. Results and discussion
Modifying the equations presented in section 3.1., and calculat-
ing, gives the distribution of concentrations of TCE and the
electrical conductivity (EC) for a 7 step separation pumping
presented in Fig. 10, The calculated TCE values shows higher
concentrations in the upper inflow intervals 11-13 than in the
lower ones, while the EC-values are highest in the bottom of the
well, inflow intervals 17-18.
64
-------
«« 10
0
» •
JU-
20
KI) 1000 UOO
r— T«p el IUIWUMW wiffw*
_ — L PumeiM Ml« - Unl
30 «
2000 29C
2900 |i3len
IZZZZZZli~*i^ICZIi
70 •
*— igllom el mil
IEGEHB
• TCE.|iflfltt«ciiUU
-------
As in Skrydstrup (section 4.1.4), the optimized remedial action
pumping have been examined as a function of the pump time. Fig.
11 shows that in the period 20. February 1990 - 22. May 1990, the
TCE concentration has stabilized at a value of 25 ug/1 TCE in the
top water and 5-6 ug/1 TCE in the bottom water, compared to
approx. 15 ug/1 TCE if onlY one P^P was used. The pump ratio has
been held constant, so the fraction of slightly polluted bottom
water has been approximately 40% of the total yield through the
whole period. In the period 30. April to 22. May 1990 the total
discharge has been adjusted from about 45 mVhr to about 70 mVhr.
This change did not influence the concentrations of TCE in top
and bottom water.
111
o
o>S 1.00
• J 0.75-
'o'JO.SO-
§3 0.25-
?|ox»
LEGEND:
3U-
25-
20-
1S-
5-
2
".*
f'f
•:•:
T
i:
•
i
I
B'M
20/2-BO
— ]
•
•
T'B'M
30M.90
f
J
.1
T'B'M1
22/S-SO
30/290
p«fu'!«
•to
0 •-
3DM-90
2215-90
%m Cone. In tepw»t« 01
e- to 6olloin (6)
(HJ
Cane, tn mli«
-------
The ratio of yields between the top and bottom pumps must
carefully be balanced, so the TCE-concentration is as high as
possible in the top water. However, in this case, the situation
is complicated by the high chloride content from intruding
saltwater from the bottom of the well which has the low content
of TCE.
This reflects an enormous water supply problem in the Copenhagen
area. Chlorinated solvents of anthropogene origin infiltrates the
limestone aquifer from above and saltwater intrudes the same
aquifer from below, because of the large demand for water.
4.3. Localization of a pollution plume in a chalk aquifer
4.3.1. Site description
A former chalk quarry has been filled with mixed industrial and
domestic wastes. The chalk is 1-4 m.b.s. and the groundwater
level is approximately 4-5 m.b.s. The chalk has been quarried
below the natural groundwater level, which means that the waste
has been dumped below the water table.
4.3.2. Hvdroaeoloqy
The aquifer is a fractured chalk, with closely spaced fractures,
with rather random orientation. The fracture porosity amounts to
around 1,5% while the total porosity varies from 20-35%. Around
the former quarry there are water table conditions in the
aquifer, but just south of the dump site the aquifer becomes
confined. The chalk is overlain by glacial till, with minor sand
lenses.
67
-------
4.3.3.
Two open boreholes 150 mm in diameter, 25 m and 29 m deep,
downstream of the disposal site were tested with the separation
injection test (SIT), as described in section 3.2.2. Salt water
was injected at the bottom and fresh water at the top, and the
position of the interface, at the various injection rates, was
determined with an EC-probe.
4.3.4. Level-accurate sampling
Knowing the flow distribution, and the positions of the bound-
aries between the ten, 10% flow partials, level accurate sampling
at the boundaries, was just a matter of pumping with the same
ratios from top and bottom as used for the SIT, and sampling at
the corresponding boundaries. The pumping of the sample was done
with a flow rate of approx. 2% of the total flow, and a limited
volume of approx. 3 litres. It should be noted, that the position
of the boundaries can only be considered equivalent, when pumping
and injection takes place through the same cross-section of the
aquifer. In other words the water level should in both cases be
above the highest filter interval. This was the case for the
well, for which the results are shown, but in the other well
there was a small difference of 30 cm in the two cross-sections,
because the casing did not reach the water table.
4.3.5. Results and discussion
The result of the SIT is shown in Fig. 12. It is evident that the
upper part of the aquifer has a much larger permeability, as 90%
of the flow takes place within the upper 25% of the tested
interval. Quite narrow flow zones can be discerned, down to
approx. 30 cm.
68
-------
TERRAIN
o
GWL.
GWL:
| CASING-
o T& 1Jt.
55 ••»
0 J5
c
Ul
u.
UJ
oc
I
IU
m
c
ui
11,44-
».»•
s
X
a.
u
O
D6t!
Fig. 12. : The relative influx distribution of ten 10% intervals
in well 207.2802, Karlstrup, determined by a separ-
ation injection test (SIT).
The results from the sampling are seen in Fig. 13, The sampling
method is clearly capable of showing very high concentration
gradients. High contents of K+, Na+, Cl', NHA+, and relatively low
contents of N03~ and S
-------
».» M t.» 13 10 » M « 10
NH; «g« CL~ ">" soj~ ag« NO] »*
i i M « ao M »»p Mi^iy ip a ; i
Fig. 13.: Concentration prof lies from well 207.2802. The level-
accurate sampling was done using separation pumping,
70
-------
5. Costs
Because the technique has only been tested at pilot scale, no
cost-benefit analyse has been made yet. Still comparing tradi-
tional remedial action pumping by use of one pump, to simulta-
neous pumping with 2 or more pumps, the installation costs are
increased by using the separation pumping technique, but
contemporaneously the remediation time would probably decrease
and the costs for treatment decrease because the -volume of
polluted water is reduced.
71
-------
6. Concluding remarks and perspectives
The separation pumping technique is a method applicable for
locating and recovering the polluted water, from a vertically
partially polluted aquifer by simultaneous pumping from top and
bottom with two or more pumps in a fully penetrating well without
installation of packers.
The method can be used for determination of the inflow distribu-
tion and transmissivity of selected sections of a well. The
vertical distribution of pollutants can furthermore be determined
and a concentration profile calculated.
Moreover the method is applicable for collecting level-accurate
water samples from any levels of-a fully penetrating well only by
pumping from the well itself.
The method has been tested at two different sites, a polluted
water table aquifer in meltwater sand and gravel with pollution
down to 25 m.b.s., and a confined limestone aquifer with fissure
flow, in both cases the effect of the separation of polluted
groundwater from slightly or non-polluted groundwater were
successful. The separation pumping can be provided in existing
wells without disturbances of the pollution distribution with the
aquifer. Remedial action pumping can be provided in a production
well in a way, so the well continues the production of drinking
water at a waterwork using the non-polluted part of the inflow to
the production well.
72
-------
7. References
Andersen, L.J., R. Jakobsen, F.L. Nielsen og B, Nilsson (1989jt
Separationspumpnings- og separationsinjektionstest. (SPT) og
SIT) i forbindelse med grundvandsforurening (Separation
pumping and Separation injection test, (SPT) and (SIT) in
relation to groundwater pollution) i ATV-komiteen vedr0rende
grundvand, Vintermede, Vingsted 1989. pp. 303-318. (Text in
Danish).
Andersen, L.J. (1990): BOTESAM, separation pumping and capillary
barrier a remedial-action concept applicable to point-pollu-
tion. First USA/USSR Joint Conference on environmental
hydrology and hydrogeology, June 18-21, 1990, Leningrad.
Gosk, E. & P.K. Bishop (1989): Coventry groundwater investi-
gation: Sources and movement of chlorinated solvents in dual
porosity rocks. EEC contacts no. EV4V-0101-c{BA]. DGU-intern
report. Joint venture between DGU and The University of
Birmingham.
Larsen, F. & L.J. Andersen (1988): BOTESAM-erfaringer med nye
BOre-TEst og SAMpling udstyr. (BOTESAM-experiences with a
new, combined borehole, testing and sampling equipment).
Forurening fra punktkilder. ATV-komiteen vedrarende grund-
vandsforurening, Vingstedcentret 2-3 marts 1988. (Text in
Danish).
Nilsson, B., L.J. Andersen, R. Jakobsen, E. Clausen & F.L.
Nielsen (1990): Remedial-action pumping by separation-pumping
technique, phase 1: Demonstration model. Lossepladsprojektet,
Report R3-1, Dec. 1990. (Text in Danish, Summary in English).
Nilsson, B., E. Wille & L.J. Andersen (1990): Remedial Action
pumping by Separation Pumping Technique. Phase 2: Skrydstrup
Waste Disposal Site. DGU-intern report. Preliminary report.
(Text in Danish, Summary in English).
73
-------
Tatef T.K. & A.S. Robertson (1971): Investigations into high
salinity grouixdwater at the Woodfield pump station Welling-
ton, Shropshire. (Water Supply Paper Institution of Geol.
Sciences Research Report No. 5).
74
-------
NATO/CCMS Cover Sheet
TREATMENT CHARACTERIZATION
General Type:
Specific Type:
Manufacturer/Researcher:
Status:
Treatable Contaminants:
Treatable Waste Matrices:
On-/0ff-s1te Treatment Location:
Pre- and Post-treatment Requirements:
SITE DEMONSTRATION
Site Location:
Contamination:
Site Characteristics:
CONTACTS
Esther Soczo
NATO/CCMS Pilot Study Co-Director
Rljksinstltuut voor volksgezondheld
en mmeuhyglene (RIVM)
Laboratory for Waste Material and
Emissions (LAE)
Antonie Van Leeuwenhoeklaan 9
Postbus 1, 3720 BA Bilthoven
The Netherlands
tel. 31-30-74-27-75
telex. 47215 RIVM NL
fax. 31-30-742971
Microblal treatment
Rotary composting reactor
Wltteveen & Box Consulting
Engineers
Production scale
011 pollutant
Soil with low moisture content
On-slte
The Netherlands
M.F.X. Veul
Witteveen & Bos Consulting Engineers
Van Twickelostraat 2
P.O. Box 233
7400 AE Deventer
The Netherlands
tel. 31-5700 - 97911
telex. 49441
fax. 31-5700-97344
75
-------
PRODUCTION-SCALE TRIALS ON THE DECONTAMINATION OF OIL-POLLUTED SOIL IN A
ROTATING BIOREACTOR AT FIELD CAPACITY.
Ir. Ger P.M. van den Munckhof and Drs. Martin F.X. Veul/Environmental
Technologists
Witteveen+Bos. Consulting Engineers, P.O. Box 233. 7**00 AE Deventer. The
Netherlands
SUMMARY
A biological treatment method has been developed for the decontamination of
oil-polluted soil at field capacity. Soil is treated in a rotating bioreactor
in which soil temperature, oxygen, moisture and nutrient levels can be
adjusted. Following laboratory scale studies to determine the optimum
environmental conditions for oil biodegradation, production scale trials were
carried out with oil-polluted soil (1,000 to 6,000 mg/kg dry soil) at field
capacity. In five batch experiments and two semi-continuous experiments with
50 tonnes of soil, the end concentration after 1 to 3 weeks treatment varied
from < 50 to 350 mg/kg dry soil. Microbial activity and oil breakdown was
highest in the first 3 to ^ days. This technique warrants further investiga-
tion as it is environmentally friendly, energy-saving and the end product is
a living, fertile soil.
1. FRAMEWORK
As part of the development of bio(techno)logical methods for the cleaning of
soil, Witteveen+Bos Consulting engineers, Deventer, has carried out producti-
on-scale trials on the decontamination of oil-polluted soil in a rotating
bioreactor at field capacity. The aim was to develop a method for quick
cleaning of polluted soil under controlled conditions at field capacity.
The Microbiology Dept. of the Wageningen Agricultural University and Broerius
Soil Sanitation Ltd, Voorthuizen, also took part in the study, which was
partially financed by the Netherlands Ministry of Housing, Physical Planning
and Environment (VROM) and the Netherlands Ministry of Economic Affairs (EZ).
76
-------
2. FEASIBILITY STUDY
The study was planned in phases. At the Microbiology Dept. of the Wageningen
Agricultural University, a preliminary feasibility study was carried out in
July-November 1988. In this study optimum environmental conditions for
biological decomposition were determined. This was done in incubation experi-
ments with soil, in which oil degradation was monitored by means of respira-
tion measurements and oil analyses.
The experiments show that mesophilic decomposition of oil is most efficient
at a temperature of 30-35°C, a moisture content of approximately 102 by
weight and in the presence of 150 og N nitrogenous fertilizer per kg of dry
soil (with an oil concentration of 5,000 mg/kg d.s.). Under these conditions.
on a laboratory scale, complete decomposition of oil (to < 100 mg/kg d.s.)
takes place in a maximum period of two weeks.
3. THE ROTATING BIOREACTOR
The reactor used in the production-scale trials was a modified DANO-compos-
ting installation for household garbage operated by the Municipality of Soest
and Baarn (figure 1).
Broerius Soil Sanitation Ltd. renovated and adapted the installation for soil
treatment. The reactor is 25 m long and 3.5 m in diameter. As the reactor
rotates.the soil is mixed and homogenized so that biomass and oil substrate
come into close contact. Temperature and oxygen level are maintained with the
aid of a warm air blower, and soil moisture content is adjusted with a
sprinkler which has been installed. Nutrients are added to the soil on the
conveyor before entering the reactor. The soil treatment process is shown
schematically in figure 2.
Witteveen+Bos has obtained the patent for this treatment process.
77
-------
Figure 1: The biorenctor
Figure 2: Biological treatment process in the rotating bioreactor
78
-------
4. PRODUCTION-SCALE TRIALS
In the reactor both batch experiments and semi-continuous experiments were
carried out.
4.1. Batch experiments
Five loads (batches) of oil-polluted soil, each weighing 50 tonnes (wet
weight), were treated in the reactor. This involved one batch of petrol-
polluted soil, three batches of diesel-polluted soil and one batch of soil
that was polluted both with diesel and lubrication oil.
The oil concentrations in the soils varied From 1,000 to 6.000 mg/kg dry
soil. Four of the five batches comprised fine sand to loamy fine sand, and
one batch comprised fairly coarse sand.
Each soil was incubated in the reactor under optimal environmental conditions
as determined in the laboratory feasibility study. This was only partly
successful because the soil temperature in the reactor did not rise above 20
to 22°C. Also the structure of the relatively loamy soil batches partly
deteriorated. Some soil particles tended to stick to one another around small
particles of rock, thus forming soil balls sometimes several centimetres in
diameter.
Soil and air samples taken from the reactor were analysed at regular inter-
vals in order to monitor and manage the microbial degradation process. In
order to take the soil samples, three sampling flaps were made, at a quarter,
half and three-quarters of the length of the reactor (sampling points 1, 2
and 3 respectively). In addition to the chemical analyses such as moisture
content, humus content, pH. oil concentration, volatile aromatics, and PAH,
also counts were done of oil-degrading microflora, for which the most
probable number method (MPN) was used. The air samples were analysed for oil
and volatile aromatics in order to set up a mass balance (degradation versus
volatilization).
For comparison with the measurements in the reactor, also respiration
measurements were done on soil samples from each batch in the Microbiology
laboratory at Wageningen Agricultural University.
The results of the measurements on oil biodegradation in the five batches are
summarized in Table 1, and presented in Figures 3, 4 and 5.
79
-------
Table 1: Results of the batch experiments.
Batch
no.
1.
2.
3-
(i.
5.
Soil type
poor coarse
sand
fine sand
loaay fine
sand
fine sand
loaay fine
sand
Oil type
diesel oil
petrol
diesel oil
lubnc.
oil
diesel oil
diesel oil
Oil-
cone.
<»g/kg ds)
start
6.000
920
730
1.000
1.000
1.500
Oil-
cone.
(eg/kg da)
end
< 100
< 50
< 100 (OC1
180 (IR)
1^0
(CC/1R)
250
(CC/1R)
Degradation
tlce (weeks)
2.5-3-0
0.5
2.5-3.0
2.5
1.5
Point In
tioe sax.
level
•Icroflora
(days)
3
-
3
2-3
1-2
Results
respiration
neuureaenti
(X of total
respiration)
80J after
2 weeks
-
90X after
1 week
85X within
li week
90J within
1 week
Votatiliza-
tlon
(weight X)
-
> 30
30
0.5
0
1000
Oil cone, (mg/kg d.m.)
16
Time (days)
20
26
30
batch 2 + batch 3 * batch 4 ° batch 6
Figure 3: Decrease in oil concentration in the batch experiments 2, 3;
5- 80
-------
600
Number ol m.o./g d.m. CE06)
600-
400-
300-
200-
100-
6 8 10
Time (days)
r
14
batch 1
batch 3
batch 4 --a-batch 6
16
Figure 4: Development of oil-degrading microflora in batch experiments 1. 3
*4 and 5-
oxygen consumption (mmol 02/kg soil)
1501
100-
60 H
0
0
10 16
Time (days)
20
betcM
batch3
* batch4
26
batch6
Figure 5: Oxygen consumption assessed by laboratory respiration measurements
on soil saaples from batch experiments 1, 3. ^ and 5-
-------
From the results of the batch experiments, the following conclusions can be
drawn:
- In the rotating bioreactor at a soil temperature or about 20*C, the end
concentration of the oil biodegradation was reached on average in a period
of approximately 2.5 weeks. Biodegradation was most rapid in the first
week. The end concentration of oil varied from < 50 to 250 ing/kg dry soil.
- The maximum level of oil-degrading microflora in the reactor developed
within one to three days. The growth in numbers of micro-organisms was from
MPN/106 - 107 to MPN/108 per gram of soil.
- Laboratory respiration measurements indicated -that, at a temperature of
30*C, biological degradation was largely completed in a period of 1 to 1.5
weeks. Only in the humus-poor, fairly coarse sandy soil in batch 1, it took
longer, 2 to 3 weeks. This indicates that, if a soil temperature of 30*C
can be achieved in the bioreactor, then an average degradation period of 1
to 1-5 weeks is feasible.
- Based on the results of the experiments there is no guarantee that treat-
ment in the reactor will achieve an end concentration of oil below the
Dutch Standard for unpolluted soil (A-level). which is set on 50 mg/kg d.s.
However, treatment of petrol and diesel polluted soils in the reactor
removed the environmentally most critical components of the pollution. The
remaining oil components are mainly alkanes, which are highly branched
and/or of long chain length. Compared to the original oil product, these
components are less volatile and less soluble, do not cause odour nuisance
and are also probably less toxic.
The environmental result of the treatment in the bioreactor therefore is
notable.
- Petrol polluted soils should not be treated in the rotating bioreactor
without provisions to reduce emission of volatile aromatics into the air.
There are no significant emissions of aromatics from diesel polluted soils,
though sometimes at the beginning of the incubation, hydrocarbon emissions
of up to a few hundred mg per m3 may occur.
4.2. Semi-continuous experiments
In the semi-continuous experiments, daily 3-5 tonnes of decontaminated soil
was removed from the end of the reactor and the same amount of contaminated
soil entered the front. The total quantity of soil in the reactor remained at
50 tonnes and the average retention time was I1* days.
82
-------
Two semi-continuous experiments were carried out. one for a period of a week
(experiment 1) and the other for a period of two weeks (experiment 2). Daily
throughout the experiments soil samples were taken at all sampling points.
These were analysed for oil concentration and MPN counts of the oil degrading
microflora were made. The results are summarized in Table 2.
Table 2: Results semi-continuous experiments
Parameter
* Mean oil concentration
(IR) (mg/kg ds)
- expt. 1
- expt. 2
* Mean of MPN-counts
(.106/g. soil)
- expt. 1
- expt. 2
Sampling point
input
980
995
25
26
SP 1
215
220
183
131
sp 2
370
205
33
46
SP 3
350
190
16
H
output
350
230
16
The soil entering the reactor had on average an oil concentration of about
1.000 mg/kg dry soil. At the defined sampling points 1, 2 and 3 and in the
soil leaving the reactor, the oil concentration was the same, namely 200-350
mg/kg dry soil. From this it may be concluded that biodegradation to 200-350
mg/kg dry soil occurred quickly (within 3-i* days).
The highest microbial activity occured in the front section of the reactor
{up to sp. 1). At sp. 1 counts of oil degrading microflora were MPN 10a to
109 per gram of soil. At sp. 2 and sp. 3. the number of oil degrading micro-
organisms has reduced to the level in the soil entering the reactor (MPN 107
per gram of soil).
The results for the semi-continuous experiments are in line with those of the
batch experiments. The highest nicrobial activity and the greatest breakdown
occurred in the first 3"1* days and the end concentration was slightly above
the Dutch A-level for unpolluted soil.
83
-------
On the basis of the available data, no preference can be given for either
semi-continuous or batch incubation.
5. PROGRESS AND PERSPECTIVE
The production-scale trials indicate that, at a soil temperature of approxi-
mately 22"C, the oil can be decomposed within one week to an end concentrati-
on, varying from < 50 to 350 mg/kg dry soil. In this process, the highest
microbial activity occurs in the first 3-i* days.
Basically, in the present Dutch situation a soil-cleaning technique is only
fully applicable if it succeeds in reaching an end concentration of a
contaminant below the A-levels defined in the Interim Act on Soil Sanitation.
For mineral oil in a standard soil (containing 102 organic matter) this A-
level is 50 mg/kg d.s.
On the basis of the results of these experiments there is no guarantee that
the required A-level for mineral oil will be achieved by soil treatment in
the bioreactor. The sane is also the case for land farming by which oil
concentration is reduced to between 500 and 1,000 mg/kg d.s. after two years.
We must therefore conclude that, on the basis of current Dutch policy, there
are no practical applications for the bio(techno)logical cleaning of oil-
polluted soil. However, further research is highly recommended, because in
comparison to other techniques, it is an environmentally friendly and energy-
saving technique, which produces as end product, a living, fertile soil.
Further research should be directed to both microbiological and environmental
hygiene aspects.
5.1. Microbiological aspects
Further laboratory and pilot scale studies need to be carried out in order to
determine the optimal process parameters to increase biological availability
and rate of oil breakdown and to reduce the end concentration. In this
respect attention should be given to the effects of introducing selected
micro-organisms and chemical pretreatment. With regard to the rate and time
of biodegradation it can be stated that, with a treatment time of maximum 1
week, the rotating bioreactor is competitively priced with other techniques
such as thermal decontamination.
tA
-------
5-2. Environmental hygiene aspects
The Dutch A-level for mineral oil was established on the basis of physic*
and chemical properties and toxicity of oil products. However, during t. ..
biological breakdown process the oil changes in composition. This means that
environmental hygiene characteristics, such as ecotoxicity and leaching, may
have changed to such an extent that it would be appropriate to reconsider the
risks to public health and the environment.
In this regard-it has to be noted that, compared to the original oil-polluted
soil, the components of biologically treated soil are less volatile, less
soluble and probably also less toxic. Thus the question could be raised to
what extent the A-level for mineral oil is applicable to biologically treated
soil.
In principle the "Dutch concept Bouwstoffenbesluit" of 1989 makes provision
for the use of decontaminated soil with an end concentration above the A-
level. "The Bouwstoffenbesluit" states that decontaminated soil from which no
environmental hygiene problem is expected, may be used without restriction.
In order to make more precise evaluation of the environmental hygiene quality
of oil-polluted soil which is biologically decontaminated (and of soil in
general), it is important that appropriate ecotoxicological tests (bio-
assays) and leaching tests be developed.
-------
86
-------
NATO/CCMS Cover Sheet
TREATMENT CHARACTERIZATION
General Type: Physical/chemical process
SpecUlc Type: Debris washing
Manufacturer/Researcher: U.S. Environmental Protection
Agency
Status: Bench and pilot scale
Treatable Contaminants: PCBs, pesticides, lead, other
metals
Treatable Waste Matrices: Debris
On-/0ff-s1te Treatment Location: Ex-s1tu
Pre- and Post-treatment Requirements: Purification of cleaning solution
SITE DEMONSTRATION
SHe Location: Detroit, Michigan; Hopklnsvllle,
Kentucky - United States
Contamination:
Site Characteristics:
CONTACTS
Stephen 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
tel. (513) 569-7877
telex. 8104612796
fax. (513) 569-7276
87
-------
DEVELOPMENT AND DEMONSTRATION OF A PILOT-SCALE
DEBRIS WASHING SYSTEM
Naomi P. Barkley
U.S. Environmental Protection Agency
Risk Reduction Engineering Laboratory
Cincinnati, Ohio
Michael L. Taylor
PEI Associates, Inc.
Cincinnati, Ohio
ABSTRACT
Metallic, masonry, and other solid debris that may be contaminated with
hazardous chemicals litter numerous hazardous waste sites in the United
States. Polychlorinated biphenyls (PCBs), pesticides, lead or other metals are
some of the contaminants of concern. In some cases cleanup standards have
been established (e.g., 10 ug PCBs/100 cm2 for surfaces to which humans may be
frequently exposed). Decontaminated debris could be either returned to the
site as "clean" fill or, in the case of metallic debris, sold to a metal
smelter.
This project involves the development and demonstration of a technology
specifically for performing on-site decontamination of debris. Both bench-
scale and pilot-scale versions of a debris washing system (QMS) have been
designed, constructed and demonstrated. The DWS entails the application of an
aqueous solution during a high-pressure spray cycle, followed by turbulent
wash and rinse cycles. The aqueous cleaning solution is recovered and
reconditioned for reuse concurrently with the debris-cleaning process, which
minimizes the quantity of process water required to clean the debris.
Introduction
More than 1,200 sites are included on the USEPA's National Priority List
(NPL), and numerous other sites have been proposed for inclusion. Many
hazardous waste sites contain toxic organic and/or inorganic chemical residues
which are intermingled with remnants of razed structures (wood, steel,
concrete block, bricks) as well as contaminated soil, gravel, concrete, and
metallic debris (e.g., machinery and equipment, transformer casings, and
miscellaneous scrap metal). Decontamination of these materials is important
in preventing contamination offsite and in facilitating debris disposal in an
environmentally safe manner. Since the majority of contaminated debris at
Superfund and other hazardous waste sites has no potential for reuse, the
purpose of a debris decontamination system would be to decontaminate the
material sufficiently to permit its return to the site as "clean" fill or to
allow its disposal as a non-hazardous rather than a hazardous waste.
88
-------
After hazardous waste sites suitable for demonstration of the on-site DWS
technology were located and evaluated, two
versions were developed and demonstrated at three Superfund sites.
Study Objectives
The design goal for the DWS was to produce a portable, hydromechanical,
self-contained cleaning system consisting of an enclosure for washing debris
(with a non-toxic cleaning solution) and a closed loop cleaning solution
purification system. Field-testing of the system at actual hazardous waste
sites and with various contaminants was the ultimate purpose.
Development and demonstration of a system that achieves these objectives
has proceeded as follows:
1) Bench-scale testing of a "off-the-shelf" debris washing system.
2) Design, development and field trial of a pilot-scale 300 gallon,
Experimental Debris Decontamination Module (EDDM) system at the
Carter Industrial Site, Detroit, Michigan.
3) Additional bench-scale testing of a 20 gallon version of the EDDM,
to identify the most effective wash solutions.
4) Design, fabrication and preliminary testing of the transportable
DWS demonstration unit.
5) Demonstration with PCB contaminated transformers at the Gray
Superfund site, Hopkinsville, Kentucky.
6) Effective treatment of process water.
7} Demonstration with herbicide (Dicamba) and benzonitrile
contaminated drums at the Shaver Farm Superfund site, Chickamauga,
Georgia.
8) Design, fabrication and shakedown of full-scale DWS
followed by field tests at Superfund sites.
Bench-Scale Tests
The bench-scale version of a Turbo-Washer (Bowden Industries) served as
the debris washer for initial studies.
Experiments were performed in a 10-gallon hydromechanical cleaning unit
(Bowden Industries) which incorporated an axial flow pump, propeller shaft,
propeller, pressure chamber (all housed in a heated tank with a rotating disc
for removing oil), and a cleaning solution reservoir. Measured quantities of
used motor oil, grease, and soil were applied to rusted iron parts to simulate
the kind of grime that is likely to be encountered on oily, PCB-contaminated
metals parts and debris in the field.
Four cleaning solutions, tap water, 10 percent sulfuric acid and aqueous
dilutions of two proprietary clean solutions: BB-100 (Bowden Industries) and
89
-------
Power Clean (Penetone Corporation) were evaluated. Three tests were performed
with each cleaning solution. The oil and grease contaminated metal parts were
used for each test. For consistency, each set of contaminated parts was
matched closely in size, shape, and type of metal. The parts were arranged
similarly in the washer basket and lowered into the heated tank where they
were exposed to the turbulent cleaning solution.
At the completion of each test, the cleaning solution was analyzed for
oil and grease and for total suspended solids. Two surface wipe samples from
selected metal parts were analyzed for oil and grease to determine the level
remaining on the metal surfaces after treatment in the parts washer.
Results of the oil/grease and total suspended solids analyses are
summarized in Table 1. Wipe sample analytical results indicate that
significant amounts of oil and grease remained on the metal surfaces after
cleaning with water or sulfuric acid. More oil/grease was removed after
cleaning with B8-100 and Power Clean. Moreover, handling 10 percent sulfuric
acid was difficult, and had a corroding effect on the hydromechanical cleaning
equipment. Water and sulfuric acid were eliminated as potential cleaning
solutions for oily PCB-contaminated debris. Based on the results of surface
wipe testing listed in Table 1, the BB-100 solution was judged to be a better
cleaning solution than the Power Clean solution.
Pilot-Scale Field Tests at Carter Industrial Site
A 300 gallon-capacity pilot scale system, EDOM, was designed assembled
and installed on a 48-foot semitrailer and tested at the Carter Industrial
Superfund Site in Detroit, Michigan. The process flow diagram for the system
is illustrated in Figure 1. Two 200-lb. batches of metallic debris were
cleaned with the system. BB-100 surfactant solution was used as the cleaning
agent. Before cleaning, five individual pieces of metal from each batch were
sampled for PCBs by a surface wipe technique which uses hexane-soaked cotton
gauze pad to wipe a 100-cm 2 area on the surface of the object being sampled.
(1) The metal items were then placed in a basket, transferred to the EDOM and
cleaned for two hours. A portion of the cleaning solution in the Turbo-
washer was pumped through a closed-looped particulate filter into the
oil/water separator. The effluent from the oil/water separator was recycled
into the module. After the cleaning process, five additional wipe samples
were taken from the same pieces of metallic debris, at a location directly
adjacent to that of the pretreatment samples, to determine the post
decontamination PCB levels.
The quantity of PCBs on each metal surface before and after cleaning is
summarized in Table 2. The average percentage reduction of PCBs was 53
percent for Batch 1 with a range from 33-87%. Batch 2 had a range from 66-
99% and an average reduction of 81 percent. Better cleaning results for Batch
2 may be the result of removing the debris basket from the EDOM after one hour
and manually rearranging the debris so that all sides of the debris were
exposed to the cleaning solution with the same force of the Turbo-Washer. It
was then placed back into the washer for the second hour. In Batch 1 the
cleaning process was for two hours without disturbing the placement of the
debris.
90
-------
The surfactant solution in the Turbo-Washer was sampled twice during the
cleaning process. PCB values were 928 and 420 ug/L. After the debris
experiment, the cleaning solution was pumped through a series of particulate
filters and activated carbon. The PCB concentration of the surfactant
solution was reduced to 5.4 ug/L following this treatment.
Bench-Scale Testing of Surfactant
Based on experience gained during the Carter site field test, a bench-
scale (20 gallon surfactant solution capacity) version of the EDDM apparatus
was designed, constructed, and assembled. This system consisted of a spray
tank, wash tank, oil-water separator, and ancillary equipment (i.e., heater,
pumps, strainers, metal tray, etc.). Development of a bench-scale DWS allowed
assessment of the system's ability to remove contaminants; from debris and to
facilitate selection of the most efficient surfactant solution.
A survey of surfactant products identified five nonionic surfactant (BG-
5, MC-2000, LF-330, BB-100, and L-422) for an experimental evaluation to
determine their capacity to solubilize and remove contaminants from the debris
surface. Unlike anionic and cationic surfactants, nonionic surfactants
perform adequately during moderate pH changes and in the presence of
electrolytes.
Prior to each bench-scale experiment, six pieces of debris including
three rusted metal plates, a brick, a concrete block and a piece of. plastic,
were "contaminated" by dipping each piece into a spiking material consisting
of a known amount of used motor oil, grease, topsoil, and sand. The pieces of
"contaminated" debris were then arranged on a metal tray which was inserted in
the spray tank and subjected to a high-pressure spray of surfactant for 15
minutes. At the end of the spray cycle, the tray was transferred to the high
turbulence wash tank, where the debris was washed for 30 minutes with a
solution of the same surfactant as that in the spray tank. After the wash
cycle was completed, the tray was removed from the wash tank and the debris
was allowed to air-dry.
Before and after treatment, surface wipe samples were obtained from the
six pieces of debris. These wipe samples were analyzed for oil and grease.
The results are summarized in Table 3. Based on the results of the wipe
testing, L-422 was selected as the solution best suited for cleaning oily
metal parts and debris.
To evaluate the ability of the bench-scale system to remove specific
contaminants from debris, DDT, lindane, PCB and lead sulfate were mixed into
the spiking material. The six pieces of debris were spiked with this mixture,
then washed using L-422. Three trials were performed. Surface wipe samples
from debris from the first two trials were analyzed for PCB, lindane, and DDT.
The surface wipe samples from the third trial were analyzed for total lead.
The average overall percentage reduction of PCBs and pesticides achieved
during Trials 1 and 2 were greater than 99 and 98 percent respectively. The
overall percentage reduction of lead was greater than 98 percent.
After the completion of the bench-scale debris washing experiments, the
cleaning solution was neutralized tc a pH of 8 and then pumped through a
91
-------
TABLE 1. SUMMARY OF RESULTS FOR OIL/GREASE AND TOTAL
SUSPENDED SOLIDS ANALYSIS
Experimental
Run No.
1
2
3
1
2
3
1
1
2
2
3
3
Total of 1 , 2. & 3
Sample Type3
Cleaning solution
Cleaning solution
Cleaning solution
Cleaning solution
Cleaning solution
Cleaning solution
Wipe No. 1
Wipe No. 2
Wipe No. 1
Wipe No. 2
Wipe No. 1
Wipe No. 2
Oil from skimmer
Analysis
Oil and grease.
rng/liter
Oil and grease,
mg/liter
Oil and grease.
mg/liter
Total suspended
solids, mg/liter
Total suspended
solids, mg/liter
Total suspended
solids, mg/hter
Oil and grease.
mg/cm2
Oil and grease.
mg/cm2
Oil and grease.
mg/cm2
Oil and grease,
mg/cm2
Oil and grease.
mg/cm2
Oil and grease.
mg/cm2
Oil and grease.
mg/liter
Cleaning Solution
Water
42
151
241
5
7
15
1.77
1.82
10.54
4.40
2.43
NAb
NA
Sulfurlc Acid Cone.
10%, wt./vol.
161
143
138
128
255
148
1.48
1.75
0.7
4.8
3.81
3.27
1540
BB-100
Cone. 15%,v/v
7
182
319
600
904
1000
0.32
0.25
0.15
0.42
0.26
0.33
33BO
Power Clean
Cone. 1 :6 Ratio
1670
1470
2440
206
576
484
0.50
0.49
0.43
0.48
0.34
0.61
3900
vo
ro
3 All samples are posttreatment samples
b Not Analyzed.
-------
M-HXH
10
u
DISPOSAL
OIL
COLLECTION
DEBRIS
WASHER
CHIP
REMOVAL
OIL/WATER
SEPARATOR
SOLUTION
TREATMENT
Figure 1. Pilot-scale process flow diagram.
-------
TABLE 2. CONCENTRATION OF PCBs FOUND IN SURFACE WIPES AND BLANKS
ftig/100cm2)
Batch Number
1
2
Sample Number
1
2
3
4
5
1
2
3
4
5
Pretreatment
134
490
1280
73
203
Field Blank: <1.0
8.0
6090
374
96
1690
Field Blank: 1.0
Postlrealment
50
178
856
43
23
13.0
1800
128
10
18
% Reduction
63
64
33
41
87
Avg: 58
-63
70
66
90
99
Avg: 81
-------
TABLE 3. A COMPARISON OF THE CLEANING CAPABILITIES OF
SURFACTANT SOLUTIONS BASED ON REMOVAL OF OIL AND GREASE
pi
fill
PS
«£ • i ?-«.;
Ijijis.
in
IP
BEjiii
1E*3E£
Pi
Pyvia
i&5e|i
Bnir^Hc
3jF||
Sample ID
Number
CM -6/20
C2- 1-6/20
C3-1-6/20
C4- 1-6/20
C5- 1-6/20
C6- 1-6/20
C1 -2-6/22
C2-2-6/22
C3-2-6/22
C4-2-6/22
C5-2-6/22
C6-2-6/22
C1 -5-6/30
C2-5-6/30
C3-5-6/30
C4-5-6/30
C5-5-6/30
C6-5-6/30
C1 -6-6/30
C2-6-6/30
ijJil C3-6-6/30
C4-6-6/30
IP
Ki
ws*$
iLv£i
ISrjjs
P|
C5-6-6/30
C6-6-6/30
C1-7-7/6
C2-7-7/6
C3-7-7/6
C4-7-7/6
C5-7-7/6
C6-7-7/6
Pretreatment
(g/100cm2)
6.7131
5.2936
5.5088
5.4138
4.7310
5.4889
4.1462
4.0274
4.0025
6.7795
7.3356
4.2899
5.2878
5.0433
5.8143
6.0277
4.1388
4.1278
4.5929
4.9409
5.3973
4.9976
3.9820
4.9440
5.1850
4.8263
5.1807
5.8047
5.0469
4.7127
Posttreatment
(g/100cm2)
0.0071
0.0171
0.0111
0.0060
0.0074
0.0107
0.0313
0.0155
0.0322
0.0057
0.0162
0.0144
0.0688
0.0878
0.0811
0.0533
0.0262
0.0667
0.0221
0.0349
0.1315
0.1498
0.0067
0.0477
0.0017
0.0028
0.0011
0.0023
0.0015
0.0019
Percent
Change
99.89
99.68
99.80
99.89
99.84
99.80
99.25
99.61
99.19
99.91
99.78
99.66
98.70
98.26
98.61
99.11
99.37
98.38
99.52
99.29
97.56
97.00
. 99.83
99.03
99.97
99.94
99.98
99.96
99.97
99.96
Avg. Percent
Change
99.82
99.62
98.74
98.64
99.96
95
-------
series of particulate filters and finally through activated carbon. During
this treatment, the PCB, lindane, and DDT concentrations were reduced to <2.0,
0.03, and 0.33 ug/L, respectively. The concentration of lead was reduced to
0.2 mg/L after treatment. During the water treatment, it was noticed that a
gel-like precipitate was formed when the L-422 cleaning solution was
neutralized to pH 8, which quickly plugged the particulate filters and had the
potential of clogging the activated-carbon drums. As a result, BG-5, which
performed almost as well as L-422 in removing oil and grease and formed only a
fine precipitate when neutralized, was selected as the cleaning solution for
the subsequent pilot-scale DWS study.
Design, Fabrication, and Initial Testing of the Pilot-Scale DWS
Based on results obtained from bench-scale studies, a transportable,
pilot-scale debris washing system was designed and constructed. The pilot-
scale system consists of a 300-gallon spray tank; a 300-gallon wash tank; a
surfactant holding tank; a rinse water holding tank; an oil/water separator;
and a solution-treatment system with a diatomaceous earth filter, an activated
carbon column, and an ion-exchange column. Ancillary equipment, included a
spray tank heater, pumps, particulate filters, a metal basket, and a stirrer
motor. The process flow diagram for the DWS is illustrated in Figure 2.
The pilot-scale system was assembled in a Cincinnati, Ohio warehouse.
Several tests were conducted using pieces of oil/grease-coated objects found
in the warehouse. Surface wipe samples were obtained before and after washing
in the pilot-scale system and analyzed for oil and grease. In three trials
using five objects in each trial, oil and grease removed ranged from 19 to 91
percent and averaged 76 percent. The warehouse testing also involved
optimization of several test parameters, including spray cycle duration, wash
cycle duration, cleaning solution temperature. Based on the results and a
visual inspection of the clean debris, the system was determined to be
effective in removing oil and grease from the surface of these objects.
Demonstration at the Gray PCB Site
The Ned Gray Superfund site, was selected for the first demonstration of
the upgraded pilot-scale debris washing system. The twenty-five acre site is
located in Hopkinsville, Kentucky. From 1968 to 1987, a metal reclaiming
facility involving open burning of electrical transformers to recover copper
for resale was operated at the site. Soil where the transformers were burned
was contaminated with lead and PCBs. The demonstration took place during
December 1989. Ambient temperatures were at or below freezing during the
entire operation.
Subsequent to the warehouse testing, the system was disassembled and
loaded onto a 48-foot semitrailer. The system and the ancillary equipment was
transported to the Gray PCB site. The entire system was reassembled on a 25
ft x 24 ft concrete pad that was poured on site prior to the arrival of the
equipment. A temporary enclosure was also built on the concrete pad
(approximately 25 ft. high) to enclose the system and to protect it and the
surfactant solution from rain and cold weather.
Prior to the initiation of the cleaning process, 75 transformer casings,
with sizes ranging from 5 to 100 gallons, were cut in half with a partner saw.
96
-------
TABLE 4. SUMMARY OF BENCH-SCALE RESULTS OF CONTROLLED
DEBRIS ANALYZED FOR PCBs AND PESTICIDES (TRIAL 1)
^•f]
m
Pi
m
m
jjKJ?)*?
gagi;ffi
1
m
m
M
m
Eggfe
Hfl
P
IP
i^E
mi
m.
*s&
S ill*
* "^W*^-
s •»*;
Contaminant
Lindane
4, 4' ODD
4, 4' DDT
PCB-1260
Lindane
4. 4' ODD
4, 41 DDT
PCB-1260
Lindane
4. 4' ODD
4, 41 DDT
PCB-1260
Lindane
4.4'DDD
4,4' DDT
PCB-1260
Lindane
4. 41 ODD
4, 41 DDT
PCB-1260
Lindane
4, 41 ODD
4, 41 DDT
PCB-1260
Lindane
4. 4' ODD
4, 41 DDT
PCB-1260
Pretreatment
13,800
1010
6710
3550
12,500
1020
7610
3230
12,300
1020
7800
2990
14,600
1220
7640
2570
12,900
1170
10,100
3360
14,000
1240
10,200
3410
9370
952
7120
2500
Posttreatment
(ng/100cm2)
0.75
3.8 U
5.0 U
2.0 U
0.7
3.8 U
5.67
2.0 U
0.7
3.8 U
5.0 U
2.0 U
5.8
3.8 U
11.6
20.3
130
4.9
360
90.4
11.1
3.8 U
28.3
15.3
1.1
3.8 U
12.6
23.4
Percent
Reduction
99.99
299.62
299.93
299.94
99.99
299.63
99.93
299.94
99.99
299.63
299.93
299.93
99.96
299.69
99.85
99.21
98.99
99.58
96.43
97.31
99.92
299.69
99.72
99.55
99.99
299.60
99.82
99.06
Average Overall Performance
Average
Performance
>99.87
>98.88
>99.72
>99.62
>99.39
indicates that the target compound was not detected at this level.
97
-------
TABLE 5. SUMMARY OF BENCH-SCALE RESULTS OF CONTROLLED
DEBRIS ANALYZED FOR PCBs AND PESTICIDES (TRIAL 2)
Contaminant
Pretreatment
(pg/100cmj)
Posttreatment1
(pg/100cmj)
Percent
Reduction
Average
Performance
Lindane
4, 4' DDT
PCB-1260
Lindane
4, 41 DDT
PC8-1260
Lindane
4. 4' DDT
PCB-1260
11.800
9320
1770
8180
7540
1780
6150
5840
1450
0.13 U
2.32
2.0 U
0.31
4.8
2.79
U
0.41
2.61
2.0
100
99.97
2:99.89
100
99.94
99.84
99.99
99.95
£99.86
>99.91
Lirdane
4, 4' DDT
PC8-1260
Lindane
4, 4' DDT
PCB-1260
5810
5660
1220
6440
6610
1390
3.49
10.5
4.1
397
389
66.1
99.94
99.81
99.66
93.83
94.11
95.24
99.80
94.39
Lindane
4. 4' DDT
PCB-1260
10,300
8400
1620
52
223
35
99.49
97.34
97.84
Average Overall Performance
98.22
>98.08
aU indicates that the target compound was not detected at this level.
98
-------
TABLE 6. SUMMARY OF BENCH-SCALE RESULTS OF CONTROLLED DEBRIS
ANALYZED FOR LEAD (TRIAL 3}
Contaminant
Pretreatment
(jig/100 cmJ)
Posttreatment
Percent
Reduction
Average
Performance
Lead
Lead
Lead
876
414
450
6.0
6.0
<:3.0
99.31
98.55
>99.33
>99.06
Concrete!
Lead
Lead
Lead
508
414
446
<3.0
<3.0
<3.0
>99.41
>99.27
>99.33
Average Performance on Ail Materials Tested
>98.08
99
-------
Treated Water
Storage Tank
Slop 1 • Spray Cyclo
Slop 2 - Wash Cyclo
Slop 3 - Rinse Cycle
DE Filler
Wator Treatment Slop
Pump
Activated Carbon
Figure 2. Schematic of pilot-scale Debris Washing System.
-------
Pretreatment samples were obtained from one half of each of the transformer
casings by using the surface wipe technique previously described. (1)
The transformers halves were placed in the wash basket and lowered into
the spray tank, which was equipped with multiple water jets that blast loosely
adhered contaminants and dirt from the debris. After the spray cycle, the
basket was removed and transferred to the wash tank, where the debris was
washed with a high-turbulence wash. Each batch of debris was cleaned for a
period of 1 hour in the spray tank and 1 hour in the wash tank. During both
the spray and wash cycles, a portion of the cleaning solution was cycled
through a closed-loop system in which the oil/PCB-contaminated cleaning
solution was passed through an oil/water separator, and the clean solution was
then recycled. After the wash cycle, debris basket was returned to the spray
tank, where it was rinsed with fresh water.
Upon completion of the cleaning process, posttreatment wipe samples were
obtained from each of the transformer pieces to assess the post-
decontamination levels of PCBs. (1) All Superfund site activities described
in this document were governed by USEPA approved Health and Safety and Quality
Assurance Plans. (3,4) In the case of the metallic debris sampled in this
study, the posttreatment wipe sample was obtained from a location adjacent to
the location of the pretreatment sample. This was necessary because wiping
the surface removes the contamination and if one were to wipe the same surface
after cleanup, the results obtained would be biased low.
The average concentrations of PCBs on the internal surfaces of the
transformer casings before and after cleaning are summarized in Table 3. The
before-treatment concentrations ranged from 0.1 to 98 ug/100 cm2. The
posttreatment analysis showed that all but seven of the transformers that were
cleaned had a PCB concentration less than the acceptable level of 10 ug/100
cm2. The seven transformers with a concentration at greater than an
acceptable level were washed again in the debris washing system, and the
posttreatment samples were obtained and analyzed. The concentration of PCBs
in these seven samples after the second wash was below the detection limit of
0.1 ug/100 cm2.
Treatment of the Process Water
After all transformers at the site were decontaminated, the surfactant
solution and the rinse water were neutralized to a pH of about 8, using
concentrated sulfuric acid. The neutralized surfactant solution and rinse
water were treated by passing it through a series of particulate filters, an
activated-carbon drum, and finally through an ion-exchange column. The
treated water was stored in a 1000-gallon polyethylene tank pending analysis.
The before- and after-treatment water samples were collected and analyzed for
PCBs and selected metals (cadmium, copper, chromium, lead, nickel, and
arsenic).
The PCB concentration in the water was reduced to below the detection
limit of 0.1 ug/100 cm2. Concentrations of five of the six metals were
reduced to the allowable discharge levels set by the City of Hopkinsville.
Arsenic remained above the allowable level. Upon receipt of the analytical
results for the water, the treated water, which was stored in the holding
tank, was pumped into a plastic-covered, 10,000 cubic yard pile of
101
-------
TABLE 7. RESULTS OBTAINED DURING FIELD DEMONSTRATION OF
DWS AT GRAY PCB SITE
Batch
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
Average PCB Concentration on Surfaces (pg/100 cm2)
Before Cleaning
Average
197(r£lO)
9.9 (N-6)
6 6 (N=4)
4 1 (N=6)
4 0 (N=8)
2.0 (N=4)
2.8 (N=2)
23 5 (N=5)
8.3 (N=4)
5 2 (N°4)
9.4 (N=4)
48 8 (N =4)
12.3(N=2)
167(N=2)
185(N=4)
113(N=2)
24 8 (N=4)
8 4 (N«5)
8 3 (N=4)
24 0 (N=3)
1B6(N.81
25 0 (N=4)
8 6 (N=4)
6 8 (N=8)
Range
<0 1 • 94 0
48-170
50-99
<01 -120
<0 1 • 28 0
<0 1 - 7 8
14-43
<0 1 - 70 0
2 9 • 23 0
<0 1 - 9 7
<01 -170
2 3 • 98 0
96-150
87-250
81-270
86-140
1 1 - 80 0
<01 • 190
<0 1 • 180
130-450
<0 1 - 44 0
120-350
15-180
<01 -31 0
After Cleaning
Average
1.5(N=10)
1 5 (N=6)
1 4 (N=4)
0 8 (N=6)
<0.1 (N=8)
2.9 (N=4)
3 9 (N=2)
1.3(N=5)
3 1 (N=4^
1.9(N=4)
3 0 (N=4)
1.1 (N=4)
5 1 fN=21
<0.1 (N=2)
<0 1 (N=4)
2 0 (N=2)
22(N=4^
3 4 (N=51
3 2 (N^
3 3 (N-3)
0 4 (N=8)
<0 1 (N=41
<0 1 (N=41
0 3 (N=i81
Range
<0.1 - 9 7
<0.1 -47
-------
contaminated soil at the site. An Incision of about 3/4 inch was made into
the plastic covering at the top of the soil pile, and a rubber hose was
inserted into the incision. After all of the water was pumped into the
contaminated soil, the hose was pulled out and the incision was covered with
tape.
Equipment was decontaminated with a high-pressure wash. Wash water
generated during the decontamination process was collected and treated in the
water treatment system. The DWS and the enclosure was disassembled, loaded
into the semitrailer and transported back to Cincinnati.
During this site cleanup, 75-80 transformers (approximately 5000 Ib)
were cleaned. A total of 1000 gallons of process water was utilized in this
demonstration. All of the transformers are now considered clean and could be
sold to scrap metal dealers or to a smelter for reuse.
Demonstration at the Shaver Farm Drum Disposal Site
A second demonstration of the pilot-scale system was conducted at the
Shaver Farm drum disposal site in Chickamuga, Georgia. Fifty-five gallon
drums containing varying amounts of a herbicide, Dicamba (2-methoxy-3,6-
dichlorobenzoic acid), and benzonitrile, a precursor in the manufacture of
Dicamba, are buried on this 5-acre site. More than 2000 drums containing
solid and liquid residues from the manufacture of Dicamba were buried here by
a construction and waste company from August 1973 to January 1974. • This
demonstration occurred in August 1990.
The pilot-scale system was transported to this site on a 48-foot semi-
trailer and assembled on a 34 ft. x 34 ft. concrete pad. The temporary
enclosure was reassembled to protect the equipment from rain and the high
temperatures.
Fifty-five gallon drums were cut into sections, placed in the DWS and
carried through the decontamination process. Results from this study are not
yet available.
103
-------
TABLE 8. RESULTS OBTAINED IN ANALYZING SURFACE WIPE SAMPLES FOR BENZONITRILE,
2,4-DICHLOROPHENOL, 2,6-DICHLOROPHENOL, 1,2,4-TRICHLOROBENZENE
(ng/100cm2)
Batch Number
1
2
3
4
5
6
7
e
9
10
Sample Number
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
1
2
1
2
Benzonllrile
Pre treatment
180a (50)b
130a (50)
125
90
43
28
4400
2700
47000
22000
10a(5)
8a(5)
200
320
1400
3000
3500
22a (5)
1400
Posttreatment
NDC
ND
117
7.8a (5)
ND
ND
ND
ND
10a(5)
7.9a (5)
ND
ND
ND
10a(5)
28
ND
7a(5)
ND
ND
2,4-Dlchlorophenol
Pre treatment
ND (50)
ND (50)
34
43
ND
ND
NAd
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Posttreatment
ND
ND
ND
ND
16a(5)
14a (5)
NA
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
2,6-Dlchlorophenol
Pre treatment
ND (50)
ND (50)
ND
ND
ND
ND
NA
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Posttreatment
ND
ND
ND
ND
ND
ND
NA
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1,2,4-Trlchlorobenzcne
Pro treatment
ND (50)
ND (50)
ND
ND
ND
ND
NA
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Posttroatmont
ND
ND
ND
ND
ND
ND
NA
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
a Estimated result less than 5 times detection limit.
b Numbers in parentheses indicate the minimum detectable concentration of the analyte.
c None detected in excess of the minimum detectable concentration of 5 ng/100cm2 unless
d Not analyzed.
otherwise specified.
-------
REFERENCES
1. Field Manual for Grid Sampling of PCB Spill Sites to Verigy Cleanup.
May 1986. EPA 560/5-86/017.
2. Test Methods for Evaluating Solid Waste.
Volume 1C, SW846, 3rd ed.} November 1986. Office of Solid Waste an
Emergency Response, Washington, D.C.
3. Standard Operating Safety Guides.
November 1984. Office of Emergency and Remedial Response, Hazardous
Response Support Division, Edison, NJ
4. Quality Assurance Procedures for RREL.
June 1989. Risk Reduction Engineering Laboratory, Cincinnati, OH
105
-------
106
-------
NATO/CCMS Cover Sheet
TREATMENT CHARACTERIZATION
General Type: Thermal
Specific Type: Revolving fluldlzed bed
Manufacturer/Researcher:
Status:
Treatable Contaminants: PAHs, PCBs, metals
Treatable Waste Matrices: Sediment
On-/0ff-s1te Treatment Location: On-s1te
Pre- and Post-treatment Requirements: Excavation and dewatering; use ash
as backfill?
SITE DEMONSTRATION
Site Location: Sidney Tar Ponds, Sidney, Nova
Scotia - Canada
Contamination: - polynuclear aromatic
hydrocarbons
- heterocycllc nitrogenous com-
pounds (ave. 50 mg/tcg)
- PCB (<2 mg/kg)
- lead, zinc, copper
Site Characteristics: Coke oven discharging Into tidal
lagoons
CONTACTS
Jim Schmidt, P.E.
Head, Physical/Chemical Process Section
Wastewater Technology Center
Environment Canada
P.O. Box 5050
Burlington, Ontario
Canada 1712 4A6
Tel. 416-336-4541
Fax. 416-336-4765
107
-------
PROGRESS REPORT
SYDNEY TAR PONDS: A CASE STUDY
by I. Travers and J.W. Schmidt
Environment Canada
The Sydney Tar Ponds have been created as a result of more than eighty years of discharge
of concentrated coke oven effluent to Muggah Creek, Sydney, Nova Scotia. It has been estimated that
the Tar Ponds contain approximately 3,400 tonnes of polynuclear aromatic hydrocarbons (PAH) which
are being released to the Sydney Harbour as a result of tidal flushing. As a result of this release, the
commercial lobster fishery in a portion of Sydney Harbour has been closed. Various methods of
controlling the PAH release have been evaluated and a conceptual design has been developed. The
design involves the excavation and subsequent combustion of 765,000 cubic metres of PAH-
contaminated sediment over a 7.5-year period. Due to the calorific value of the contaminated
sediments, substantial energy and cost savings can be realized. Detailed engineering design studies
were initiated and presently two revolving fluidized bed incinerators and ancillary facilities are under
construction. In September, a novel dredging arrangement was tested successfully to remove the
sediments which will be pipelined to holding tanks at the incinerator. Supernatant water will be
decanted and the contaminants removed. After settling, the sediments will be fed to the incinerators
which are scheduled for completion by January 31, 1991 (along with all other ancillary facilities.
Commissioning of the facilities will be undertaken during February and March. In April and May,
stack sampling, feed sampling, etc. to develop a mass balance around the incinerator will be
undertaken. The final report on this work is expected to be completed by October 31, 1991.
108
-------
NATO/CCMS Cover Sheet
TREATMENT CHARACTERIZATION
General Type:
Specific Type:
Manufacturer/Researcher:
Status:
Treatable Contaminants:
Treatable Waste Matrices:
On-/0ff-s1te Treatment Location:
Pre- and Post-treatment Requirements:
SITE DEMONSTRATION
Site Location:
Contamination:
Site Characteristics:
CONTACTS
Leon Urllngs
TAUW Infra Consult
Handelskade 11
P.O. Box 479
7400 A1 Deventer
The Netherlands
31-5700-99911
Fax: 31-5700-99270
Volatilization
Soil vacuum extraction and
combustion
TAUW Infra Consult
Demonstration
VOCs
Soil
Iri-s1tu
Combustion of soil air for
post-treatment
Solvent spill at a chemical plant
In ah Industrial area; gasoline
contaminated site under a road; -
The Netherlands
Toluene; gasoline
S1Uy sand 1n upper 10m; ground-
water land approx. 15m below
surface
109
-------
IN SITU SOIL VAPOUR EXTRACTION
F. Spuy, L. Urlings, S. Coffa
TAUW Infra Consult B.V.
The Netherlands
Deventer, November 1990
R0002497.K01/FSP
-------
INTRODUCTION
Soil may be contaminated in various ways with volatile organic
chemicals such as gasoline components, chlorinated hydrocarbons
and industrial solvents. Not only the soil but also the ground-
water can be contaminated from these sources which can continue
even after the discharge has stopped. Excavation of the con-
taminated soil is a very effective method to remove the pollution.
Treatment or disposal of the excavated soil is necessary.
Nevertheless excavation can be difficult or even impossible under
certain circumstances e.g.:-
the presence of building and civil engineering works (roads,
bridges etc.);
certain cables, power lines and pipe Lines in the subsurface;
contamination has spread to great depths (i.e. >& m);
shortage of space and traffic problems (city centres);
irreplaceable function of the site (railway station).
Generally the criteria favourable for applying in situ techniques
are the following:-
only one contaminant is present (e.g. toluene) or comparable
component (e.g. gasoline);
the quantity of contaminated soil is substantial;
the contaminant can be biodegraded;
the contaminant can be leached and/or volatilized;
- the permeability of the soil is reasonable;
- less disturbing layers of clay/peat appear in the subsoil;
the contamination is infiltrated (i.e. not buried).
Soil Vapour Extraction (SVE) is an in situ technique for the re-
moval of volatile organic chemicals or chemicals which are, in
some cases biodegradable. SVE is an accepted technique in the
United States and Germany. In Holland, presently, there are rela-
tively few full-scale soil vapour extraction systems in use.
Two sites equipped with a SVE system will be discussed in this
paper. One is an industrial site contaminated with toluene, the
other is a gasoline contaminated site situated under a road.
Ill
-------
Remedial Technology
The mechanism by which SVE operates is relatively simple. By
creating negative pressure gradients in a series of zones within
the unsaturated soil a subsurface air flow is induced (figure 1).
This flow volatilizes the contaminants present in the unsaturated
soil. This process, in theory, continues until all volatile com-
ponents are removed. Individual transfer pipes are connected to
the extraction well, then manifolded to a vacuum unit and trans-
ported to a soil vapour treatment system.
Figure 1: Soil Vapour Extraction
Estimated Duration of SVE
The most importance factors in determining the SVE duration are:-
(1) The total amount of contaminants to be removed.
(2) The concentration of the vapours of the contaminants in the
soil air (volatilization).
(3) The extent of the subsurface air flow which can be realized.
(4) The chromatography effect (retention of compounds).
(5) The biodegradability of the contaminants (in the presence of
oxygen).
The concentration of the vapour of a contaminant in the soil de-
pends largely on the presence of similar compounds, the heat of
vapourization and the temperature.
112
-------
The extent of the subsurface air flow which can be realized will
be determined by the aerodynamic conductivity of the soil, the
created negative pressure gradients in the different zones of the
soil and the design of the SVE system (number, size and relative
positions of the SVE tubes and the air infiltration tubes.)
Vapourized contaminants will be distributed over the mobile phase
(soil air) and the stationary phase (liquid film around the soil
particles) analogous to the chromatographic theory in the analy-
tical chemistry.
TAUW Infra Consult B.V. has developed a computer simulation pro-
gramme in order to determine the duration of the SVE. The input
parameters of the computer simulation are the estimated air flow
in the subsoil, the sorptive properties of the subsoil in relation
to the contaminants and the physical/biological properties of the
contaminants at soil temperature.
113
-------
Site 1
Site Characteristics
The contamination is caused by the spillage of solvents (mainly
toluene) whilst a paint factory was in operation. This spillage
probably occurred between 1959 - 1978.
The groundwater was .heavily contaminated with toluene and because
the site was situated close to groundwater extraction wells for
drinking purposes this project received a high priority in 1988.
The remedial action is initiated in the beginning of December
1989. The installation of the SVE system was carried out by NBM a?
a contractor, the commissioners are Utrecht Council while TAIF'
Infra Consult B.V. is the supervisor of the project.
Approximately half of the contaminated area is situated underneath
a building. The groundwater table is about 7 m below ground level.
The unsaturated zone of the soil consists of fine to gravel sand.
The aerodynamic conductivity of this layer in a vertical direction
appeared to be 70-90m/d.
The soil is heavily contaminated with mainly toluene and minor
amounts of other aromatic hydrocarbons such as benzene and
xylenes. The highest toluene concentration appeared to be 2200
mg/kg d.w.
Three remedial action techniques were studied:-
(1) Excavation.
(2) Soil Flushing.
(3) Soil Vapour Extraction.
For purely financial and practical reasons soil vapour extraction,
together with a groundwater sanitation was considered to be the
best method.
The location is shown in figure 2.
Under the building there are next to the extraction wells (per-
forated from 2-3.5 m and 5-6.5 m below ground level) there are
also infiltration wells (perforated from 2-6.5 ra below ground
level). Outside the building only extraction wells are installed
(perforated from 5-6.5 m below ground level). All the wells were
separately monitored (concentration and under pressure). The under
pressure applied is approximately 30-80 millibar and the airflow
is approximately 150 m5/h. The soil vapour is treated using activs
carbon filtration.
114
-------
2.5
5m
I.EGENDA
o boring
«o kombinatia boring/peilbuis
v sonriering met 3 minifliters
•H- luchttoevoerfilter (passief)
# onttrekkingsf liter
x _) verontreiniglngsgrens
0*8
ontgraven
plaats deepwellontgraven
P.W. UTRECHT
RALSTON ZEIST
1:100
A3
6024953
18-11-1988
-005-
TAUW Infra Consult b.v.
-------
Results and Discussion
The results of the soil vapour extraction are given in figures 3
and 4. Within four months approximately 580 kg of toluene was
withdrawn using the SVE system!
Concentrations of up to 8000 mg toluene/m3 were measured (up to 40
g/m3 in a specific extraction well) in the withdrawn soil vapour.
After a period of three and six months, the soil was sampled at
almost exactly the same spot prior to remediation. The results are
given in table 1.
Location
215-12
215-12
215-13
207-12
207-13
Depth (m
bet OH ground
level)
5 - 5.5
5.5 - 6
6 • 6.5
6.5 - 7
5.5 - 6
6 - 6.5
6.5 - 7
t«0
mg/kg
.
530
2200
-
310
1100
t=13 weeks
mg/kg
.
1.5
3.8
6.4
< 1
« 1
< 1
t=31 weeks
mg/kg
< 0.05
< 1
< 1
7.0
< 0.05
< 1
Table 1 Toluene Concentrations in the Soil
116
-------
RALSTON ZEIST
Soil vapor eitraclon
700
f
t
too -
930 -
400 -1
300 -
100 -
N<7v-a9 Jon-90 F
-------
Additional Investigations During Remedial Action
Apart from Che usual analytical and supervisory activities during
remedial action special attention is paid to:-
• The modelling of the SVE remedial action duration. As previous-
ly mentioned several factors determine the SVE duration. The
input parameters of the computer simulation are the estimated
airflow in the subsoil, the sorptive properties of the subsoil
in relation to the contaminants and the physical/biological
properties of the contaminants at soil temperature.
- The study of the horizontal versus vertical aerodynamical con-
ductivity of the soil. As stated before the aerodynamic con-
ductivity of the contaminated layer in vertical direction is
about 70-90 m/d whereas in horizonal direction a value of about
150 m/d is determined. These numerical values are the results
of air flow and tracer (helium) velocity measurements in re-
lation to the applied negative pressure gradient in the sub-
soil.
- The measurement of bacterial activity (e.g. counting, oxygen/-
carbon dioxide sampling). The volume of the contaminated layer
is about 900 m3 corresponding to about 1500 tons. The oxygen
consumption amounts to 0.3-0.5 kg/h and the carbon oxide pro-
duction was 0.3-0.4 kg/h. Consequently the rate of biodegrad-
acion of toluene was estimated to be approximately 2 mg C/kg/d.
Progress
In October 1990 an air infiltration system was installed at
below ground level to enhance the groundwater sanitation.
118
-------
Site 2
During soil sanitation at a petrol station, it would appear that
contaminants were found underneath a provincial road. Excavation
of the contaminated soil was not feasible due to financial and
technical (traffic) reasons. The most favourable solution was a
SVE system in combination with biostimulation. This system has not
only to remove the volatile compounds from the gasoline but also
through the (passive) infiltration of air (oxygen) it had to stim-
ulate biodegradation of particulary the non volatile' components.
The unsaturated zone of the soil consisted of fine to gravel sand.
The groundwater surface had to be lowered from 2 m below ground
level to 3 m below ground level in order to enlarge the unsatu-
rated zone.
Figure 5 shows the location.
On one side of the road there are seven soil vapour extraction
wells (perforation from 2-2.75 m below ground level) and on the
other side seven infiltration wells (passive). To prevent direct
air infiltration at the extraction side of the road, a plastic
liner was placed between the road and the sheet pile wall.
\
D
_»iffKt»* vtll
r
OC02197
-or
VA/ TAUW Infn Contu
\Ar >n« i iff r«M »i *.-•»
119
-------
Amount Removed
Curve 1 in figure 6 gives the accumulative amount of gasoline that
according to a zero order rate is broken down. Curve 2 gives the
accumulative amount of gasoline removed via volatilization of the
soil. The total accumulative amount of gasoline removed is given
in curve 3. This concerns a period of a year.
Figure 6 Accumulative amounts of petrol removed during soil vapour
extraction.
Withdrawn amount of gasoline during SVE
4000
Total amount
extracted (Kg) •
A
3000
2000
1000
i ! ;
i
i
: ' ' • ./ : ;
1
1
t I
/ !_J
/ ' •
i
: /
/
! i/
/
/ I
/
Vaporized
and
biodegradated _
J""
^T a;
/X i
1 [
Vaporized
f
i
/
^
/^
'
20
i
/
y
/
'
Biodegradated
40 60 80 1C
Time (weeks)
120
-------
Based upon Che speed of Che oxygen consumption and Che carbon
dioxide production the estimated degradation rate of petrol com-
ponents in Che soil are approximately 7 mg C/kg soil/day (3 samp-
ling days). The volatilization rate, concerning the total amount
of soil, is approximately 21 mg C/kg soil/day. Thus in total the
removal rate is estimated to be (within a period of a year using
soil vapour extraction) approximately 28 mg C/kg soil/day. In the
future, as a result of reduced volatilization the removal rate
will gradually be reduced.
Withdrawal and Breakdown Amounts
A year after beginning the soil vapour extraction system ap-
proximately 1,900 kg extracted from the soil, while approximately
800 kg in the soil was broken down. This amounts to approximately
2,700 kg of gasoline removed in a year.
Combined Air and Water Treatment
The bioreactor based upon a sludge on carrier type can convert the
vapours in the withdrawn soil air as veil as the dissolved con-
taminants in the pumped water in carbon dioxide and water. The
first specimen at a 25 m3/hour scale, was set in an in situ reme-
dial site in Raalte and functions beautifully. The retention time
is approximately 15 minutes for groundwater and less than 10 min-
utes for soil air. The treatment efficiency concerning the total
load offered (soil, air and groundwater) amounts to in excess of
98%. All the requirements regarding discharging are met, i.e. 100
Atg aromatic per litre and 1 rag mineral oil per litre. In the puri-
fied soil vapour (exhaust bioreactor) no aromatics or other vola-
tile carbon dioxides were detected. The detection limit for these
matters is 0.1 ppm. In 1989 TAUW Infra Consult B.V. applied for a
patent for this bioreactor.
Approximately nine months after beginning the soil vapour with-
drawal was increased from 25 to 50 m3/hour.
The concentration of volatile gasoline components was 3 g/m3.
Ten weeks later the soil vapour extraction was once again in-
creased till approximately 63 m3/hour. Via this air phase ap-
proximately 210 g/hour of gasoline vapour was treated by the bio-
logical purification system. The load via the pumped groundwater
totalled approximately 8 g/hour (15 in3/hour * 0.5
121
-------
122
-------
Appendix A
List of Participants
A-l
-------
NATO/CCMS Pilot Study
Demonstration of Remedial Action Technologies
for Contaminated Land and Groundwater
LIST OF PARTICIPANTS
Fourth International Conference
Angers, France
5-9 November 1990
PILOT STUDY PARTICIPANTS
CANADA
James W. Schmidt, P. Eng.
Chief, Physical/Chemical Processes Division
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
FAX 416-336-4765
DENMARK
Bertel Nilsson
Geologist
Geological Survey of Denmark
Thoravej 8
2400 Copenhagen NV
Denmark
OFFICE TEL. 31-10-66-00
HOME TEL... 31-22-09-92
TELEX 19999 dangeo dk
FAX 31-19-68-88
Neel Stroback
Msc. Engineering
The County of Sonderoylland
Groundwater Division
Jomfrustien 2
6270 Tender
Denmark
OFFICE TEL. 74-72-29-29
HOME TEL... 74-73-87-07
FAX 74-72-54-71
A-2
-------
Dr. Steen Vedby
Project Manager
Phonix Environment
AS/Phonix Contractors
Fuglesangsalle 14
6600 Vejen
Denmark
OFFICE TEL. 45-75-36-11-11
HOME TEL... 45-75-36-60-05
FAX 45-75-36-46-09
FEDERAL REPUBLIC OF GERMANY
Dr. Volker Franzius, Dlpl.-Ing.
Umweltbundesamt
Bismarckplatz 1
D-1000 Berlin 33
Federal Republic of Germany
OFFICE TEL. 030-8903-2496
HOME TEL... 030-883 8578
TELEX 183756
FAX 030 8903 2285
FRANCE
Florence Blanchard
Agence Nationale Pour la Recuperation et
1'Elimination des Dechets (ANRED)
2 Square la Fayette
BP 406
49004 Angers Cedex
France
OFFICE TEL. 33-41-20-41-20
TELEX 721325 F
FAX 33-41-87-23-50
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. 33-41-20-41-21
HOME TEL... 33-73-22-32
TELEX 721325 F
FAX 33-41-87-23-50
A-3
-------
Bruno Grano
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
HOME TEL... 33 61 51 69 04
FAX 33 61 39 58 15
Martine Louvrler
Agence Nationale Pour la Recuperation et
1'Elimination des Dechets
2 Square la Fayette
BP 406
49004 Angers Cedex
France
OFFICE TEL. 33-41-20-41-20
TELEX 721352 F
FAX 33-41-87-23-50
Claude Mouton
Agence Nationale Pour la Recuperation et
1'Elimination des Dechets (ANRED)
2 Square la Fayette
BP 406
49004 Angers Cedex
France
OFFICE TEL. 33-41-20-41-20
TELEX 721325 F
FAX 33-41-87-23-50
Dominique Poiroux
Engineer
Direction Regionale de 1'Industrie
et de la Recherche Midi-Pyrenees
84 Rue du Feretradex
31078 Toulouse Cedex
France
OFFICE TEL. 33-61-39-58-57
FAX 33-61-39-58-15
A-4
-------
Sylvie Pommelec
Agence Nationals Pour la Recuperation ei
1'Elimination des Dechets (ANRED)
2 Square la Fayette
BP 406
49004 Angers Cedex
France
OFFICE TEL. 33-41-20-41-20
TELEX 721325 F
FAX 33-41-87-23-50
NORWAY
Dr. James Berg
Senior Scientist
Aquateam Norwegian Water Technology Center
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 79 83 16
FAX 47 2 67 20 12
Beate Folkestad
Executive Officer
Statens Forurensningstilsyn
P.O. Box 8100 DEP
N-0032 Oslo 1
Norway
OFFICE TEL. 47-2-57-34-00
TELEX 76684 SFTN
FAX 47-2-67-67-06
THE NETHERLANDS
Merten Hinsenveld, Ir.
University of Cincinnati
Department of Civil and Environmental Engineering
741 Baldwin Hall (ML #71)
Cincinnati, OH 45221-0071
United States
OFFICE TEL. 513-556-3648
HOME TEL... 513-556-8505
FAX 513-556-2599
A-5
-------
Esther Soczo, M.SC.
NATO/CCMS Pilot Study Co-Director
Rijksinstituut voor volksgezondheid
en milieubeheer (RIVM)XLAE
Antonie Van Leeuwenhoeklaan 9
Postbus 1, 3720 BA Bilthoven
The Netherlands
OFFICE TEL. 31-30-74-91-11
31-30-74-30-65
HOME TEL... 31-33-75-71-23
TELEX 47215 RIVM NL
FAX 31-30-25-07-40
Frank Spuij
TAUW Infra Consult
Handelskade 11
P.O. Box 479
7400 Deventer
The Netherlands
OFFICE TEL. 31-57-00-99-911
HOME TEL... 31-83-70-15-815
FAX 31-57-00-99-270
Ger Van den Munckhof
Witteveen & Bos Consulting Engineers
Van Twickelostraat
P.O. Box 233
7400 Deventer
The Netherlands
OFFICE TEL. 31-5700-97911
HOME TEL... 31-5700-17633
TELEX 49441
FAX 31-5700-97344
UNITED KINGDOM
Dr. R. Paul Bardos
Warren Spring Laboratory
Department of Trade and Industry
Gunnels Wood Road
Stevenage SGI 2BX
United Kingdom
OFFICE TEL. 44-438-74 11 22
HOME TEL... 44-438-85 606
TELEX 82250 WSLDOIG
FAX 44-438-36 08 58
A-6
-------
UNITED KINGDOM
Jacqueline Hill
Warren Spring Laboratory
Department of Trade and Industry
Gunnels Wood Road
Stevenage SGI 2BX
United Kingdom
OFFICE TEL. 44-438-741122 ext 404
HOME TEL... 44-438-317-588
TELEX 82250 WSLDOIG
FAX 44-438-08 58
Dr. Peter Wood
Department of Trade and Industry
Warren Spring Laboratory
Gunnels Wood Road
Stevenage
Hertfordshire SGI 2BX
United Kingdom
OFFICE TEL. 0438-741122
HOME TEL... 029671-2041
TELEX 82250 WSLDOIG
FAX 0438-360858
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
FAX 513-569-7274
Col Frank P. Gallagher III
Director, Engineering and Services Laboratory
U.S. Air Force
HQ AFESC/RD
Tyndall Air Force Base , FL 32404-6001
United States
OFFICE TEL. 904-283-6274
HOME TEL... 904-871-4690
FAX 904-283-6499
A-7
-------
Stephen C. James
Chief, SITE Demonstration
and Evaluation Branch
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. 513-569-7696
HOME TEL... 513-321-7937
FAX 513-569-7620
Walter W. Kovalick, Jr., Ph.D.
Director, Technology Innovation Office
Office of Solid Waste and Emergency Response
U.S. Environmental Protection Agency
OSlOO/OSWER/Room 315SE
Washington, DC 20460
United States
OFFICE TEL. 202-245-4053
HOME TEL... 703-323-6078
TELEX 892 758 EPA WSH
FAX 202-245-3527
Edward G. Marchand
Chemical/Physical Treatment
Technology Area Manager
HQ AFESC/RDVW
Tyndall Air Force Base, FL 32403-6001
United States
OFFICE TEL. 904-283-6023
HOME TEL... 904-286-6273
FAX 904-283-6499
Dr. Robert F. Olfenbuttel
Director, Waste Minimization and Treatment
Battelle, Columbus Division
505 King Avenue
Columbus, Ohio 43201
United States
OFFICE TEL. 614-424-4827
HOME TEL... 614-481 3172
TELEX 24-5454 BATTELLE COL
FAX 614-424-3321
A-8
-------
Donald Banning
NATO/CCMS Pilot Study Director
Chief, Emerging Technology Section
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. 513-569-7875
HOME TEL... 606-341-2554
FAX 513-569-7620
NATO EXPERT GUEST SPEAKERS
FRANCE
Herve Billard
Agence Nationale Pour la Recuperation
et 1'Elimination des Dechets
2 Square la Fayette
BP 406
49004 Angers Cedex
France
OFFICE TEL. 33-41-20-41-20
TELEX 721325 F
FAX 33-41-87-23-50
Christian Bocard
Institute Francaise du Petrole
1 et 4 Avenue du Bois Preau
92506 Rueil Malmaison Cedex
France
OFFICE TEL. 33-1-47-52-64-03
HOME TEL... 33-1-39-73-06-45
TELEX 203050 F
FAX 33-1-47-52-70-01
Michael Kremer
Societe des Ciments Francaise
BP 7
79600 Air Vault
France
A-9
-------
Chantal Puechmaille
Charge de Mission Sectoriel Environement
Ministere des Affaires Etrangeres
DDCSTE
34 Rue Laperouse
75775 Paris Cedex 16
France
OFFICE TEL. 40-66-73-04
TELEX 643140
FAX 40-66-75-74
Jean Marc Rieger
Societe SCORI
12 Rue Gambetta
BP 54
69192 Saint Fons
France
Patrick Souet
Agence Nationale Pour la Recuperation
et 1'Elimination des Dechets (ANRED)
2 Square la Fayette
BP 406
49004 Angers Cedex
France
OFFICE TEL. 33-41-20-41-20
HOME TEL... 33-41-43-13-08
TELEX 721325 F
FAX 33-41-87-23-50
Bruno Verlon
Service de L'Environnement Industriel
14 Boulevard General Leclerc
92524 Neuilly Sur Seine Cedex
France
OFFICE TEL. 1-47-58-12-12 ext.2740
HOME TEL... 1-47-24-24-27
TELEX DENVIR 6206
FAX 1-47-45-04-74
THE NETHERLANDS
Dr. Dick Janssen
Department of Biochemistry
University of Groningen
Nijenborgh 16
9747 AG Groningen
The Netherlands
A-10
-------
UNITED STATES
Douglas Ammon
Project Manager
Clean Sites Inc.
1199 N. Fairfax Street
Alexandria, VA 22314
United States
OFFICE TEL. 703-739-1223
HOME TEL... 703-768-0713
FAX 703-548-8873
NATO/CCMS FELLOWS
FEDERAL REPUBLIC OF GERMANY
Dr. Peter Walter Werner
DVGW-Forachungsstelle AM Engler-Bunte-Institute
de Universitat
Karlsruhe
D 7500 Karlsruhe 1
Federal Republic of Germany
OFFICE TEL. 0721-608-2596
HOME TEL... 0711-481157
TELEX 721684-DVGWKA
FAX 0721-696721
FRANCE
Dr. Alain Navarro
Directeur Scientifique
Association Reseau Cooperatif de
Recherche sur les Dechets
C.E.I., 27, bd du 11 Novembre 1918
B.P. 2132, 69603 Villeurbanne Cedex
France
OFFICE TEL.33-72-43-81-88
FAX 33-72-44-07-32
THE NETHERLANDS
Sjef J. J. M. Staps, Ing.
Grontmij n.v. Consulting Engineers
P.O. Box 203
3730 AE De Bilt
The Netherlands
OFFICE TEL. 31-34-02-59-111
HOME TEL... 31-33-80-51-72
FAX 31-34-02-51-220
A-ll
-------
TURKEY
Dr. M. Resat Apak, Ph.D.
Associate Professor of Analytical Chemistry
Istanbul University
Faculty of Engineering
Avcilar Campus, Avicilar
Istanbul
Turkey
OFFICE TEL. 520 75 50 EXT: 56
HOME TEL... 337 68 62
Dr. Aysen Turkman
Associate Professor
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
UNITED KINGDOM
Michael A. Smith
Clayton Bostock Hill & Rigby, Ltd.
68 Bridgewater Road
Berkhamsted
Hertfordshire HP4 1JB
United Kingdom
OFFICE TEL. 021-359-5951
0442-871500
HOME TEL... 0442-871500
TELEX 337273
FAX 0442-870152
UNITED STATES
Thomas 0. Dahl
U.S. Environmental Protection Agency
National Enforcement Investigations Center
Denver Federal Center, Building 53
Denver, Colorado 80225
United States
OFFICE TEL. 303-236-8358
HOME TEL... 303-235-0284
FAX 303-236-5116
A-12
-------
Dr. James Gossett
Associate Professor
School of Civil and Environmental Engineering
Cornell University
Hollister Hall
Ithica, NY 14853-3501
United States
OFFICE TEL. 607-255-4170
ON-SITE SUPPORT STAFF
UNITED STATES
Chamaine C. Commins
Marketing Associate
JACA Corp.
550 Pinetown Road
Fort Washington, PA 19034
United States
OFFICE TEL.215-643-5466
HOME TEL...215-828-4983
FAX 215-643-2772
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
FAX 215-643-2772
A-13
-------
APPENDIX B
NATO/CCMS FELLOWS
-------
PETER WERNER
NATO/CCMS Fellow
B-l
-------
Report on activities in the frame of the
NATO/CCHS Fellowship Programne
Title:
Demonstration of Remedial Action Technologies
for Contaminated Land and Groundwater
To be presented at the 4th International NATO/CCMS Conference
at Angers (France) November, 5-9, 1990
B-2
-------
1. Introduction
The paper presented here is the continuation of my report already printed and
documented in the Summary of the "Third International NATO/CCMS Conference on
Demonstration of Remedial Action Technologies for Contaminated Land and
Groundwater" in Montreal, Canada, November, 6-9, 1989.
The task of my fellowship programme is not to repeat things and facts which
were already described in different journals or presented at different
congresses. Nor is it good to believe anything announced in advertising
brochures of firms which already offer biological remediation commercially.
As a microblologist, I want to focus especially on problems that still exist
in the field of biological processes used for remediation of contaminated
sites. This will help us to get a better understanding for the ongoing
processes. Moreover, it is necessary to regard biological processes on a
realistic base. It is not worth exaggerating these methods not knowing enough
about the background. The knowledge on biodegradation itself must be increased
before the methods can be applied realistically. We must be aware of the
problems and must admit that we do not know enough about them. Otherwise we
might be blamed later for having dealt amateurishly with difficult question
such as the remediation of contaminated sites. Certainly, it is very useful to
apply biological methods where they really seem appropriate. But it is
impossible to solve all problems with microbiology. The aim must always be a
combination of different methods.
In my report mentioned above, I put the main interest on the two problems
which inhibit biodegradation processes:
1) bioavailability of the contaminants
2) question of oxygen source.
B-3
-------
The conclusions of the former presentation are not to be repeated here, but
the aim of this paper should be the experiences made when biological methods
are applied for the remediation of contaminated sites. Therefore, I want to
compare different methods already used worldwide and to describe their appli-
cability with all the advantages and disadvantages. Moreover, contaminants
other than hydrocarbons are to be discussed here.
In addition to the institutions already mentioned in the first report, I
contacted the following firms:
TNO, Delft (NL)
Umweltschutz Nord, Ganderkesee (D)
which have many experiences in the use of microbial biodegradation processes.
B-4
-------
2. Contaminants
A lot of concern is concentrated on the biodegradation of the following sub-
stances, that can be found in contaminated sites. The table below contains the
biodegradability itself and the applicability in practice.
Table 1: Contaminants of Special Interest
Contaminants
Biodegradabi-
bility Proved
in Laboratory
Biodegradabi
lity Proved
at the Site
Applicability
Proved in
Remediation
Measures
Aliphatic Contaminants
Aromatic Contaminants
Polyaromatic Hydrocarbons
Volatile Chlorinated
Hydrocarbons
Phenols
Non-volatile Chlorinated
Hydrocarbons
PCBs, Dioxins, Furans
Cyanides
Heavy Metals
With respect to aliphatic hydrocarbons it can be concluded that alcanes (C
C ) are fairly well biodegradable. Isoalcanes and alkenes are less biodegra-
dable. Cycloalcanes are almost resistant. From this point of view it is of
special interest to analyze in advance the combination of pollutants at a con-
taminated site in order to decide about the most suitable remediation method.
Due to the great amount of contaminants normally found on spills with alipha-
B-5
-------
tic hydrocarbons, the question of the additional oxygen source is important.
Figure 1 shows the biodegradation pathway of aliphatic hydrocarbons which
leads to the conclusion that nitrogen can only be applied in combination with
oxygen as primary oxidant.
CH3 - (CH2)n - CH3 + 0
Aliphatic Hydrocarbon
Oxygenase
CH3 - {CH2)n - C
Alcohol
- OH
- 2H
CH3 - (CH2)n -
Aldhyd
- 2H
CH3 - (CH2)n -
I
Fatty Acid
•OH
Further biodegradation by
oxygen or nitrates possible!
Figure 1: Biodegradation Pathways of Aliphatic Hydrocarbons with Respect to
the Use of Nitrates
Phenols and most of the aromatic hydrocarbons can be biodegraded fairly well,
reason why bioremediation of these contaminants is already used worldwide. The
concentration of these substances is crucial for the success.
B-6
-------
Polyaromatic hydrocarbons are especially important in Germany since its reuni-
fication because of the large number of abandoned coke-oven and coal-gasifica-
tion plants, where these pollutants are predominant. In principle, biodegrada-
tion is possible. The problems of its applicability in practice are already
described in detail in my first report and should not be repeated here.
The biodegradation of cyanides is also of special interest in the areas men-
tioned above'. Non-complexed cyanides are well biodegradable in concentrations
up to about 15 mg/1, although it is one of the most toxic inorganic substances
known. The experiences show that cyanide in abandoned industrial areas is
complexed and therefore not or only less toxic and less soluble. On the other
side, it is almost not biodegradable in this form. Table 2 shows the occurence
of cyanides and their toxic properties. As a rule, Prussian blue can be found
predominantly in abandoned coal-gasification plants.
Table 2: Occurence and Behaviour of Cyanides
Form
Solubility
Toxicity Biodegra-
dability
"Non-complexed"
KCN, NaCN, NH CN Cyanides
4
KOCN, NaOCN, NH OCN Cyanates
4
"KSCN, NaSCN, NH SCN Thiocyanates
4
Zn(CN)
"Complexed"
K (Fe(CN) J red
3 D
K (Fe(CN) ) yellow
KFe(Fe(CN) } soluble Prussian blue
6 *
Fe (Fe(CN) ) non-soluble Prussian blue
4 63
high
high
high
low
high
high
low
not soluble
high
not toxic
low
fairly toxic
low
not toxic
not toxic
not toxic
+
+
+
7
-
"
.
predominant in abandoned coal-gasification plants
B-7
-------
Volatile chlorinated hydrocarbons are fairly well biodegradable under diffe-
rent environmental conditions. A lot of work was done in this field in the
last few years. The experiences concerning this subject were summarized in
1989 by Werner and Ritter in a literature review called "Abbau- und Biotrans-
formation von leichtfluchtigen Halogenkohlenwasserstoffen in der Umwelt unter
besonderer Berucksichtigung der Vorgange im Untergrund". The study can be
ordered at the Landesanstalt fur Umweltschutz im Karlsruhe (Germany). Due to
the complexity of biodegradation pathways, no case of remediation based on
microbial processes is known so far.
Only some of the non-volatile chlorinated hydrocarbons could be biodegraded
under optimum conditions on laboratory scale. An applicability of microbial
mineralization of these compounds is not known. PCBs, dioxins, and furans are
tested for their biodegradability in laboratory set-ups. The results are only
of scientific interest and cannot be transferred to bioremediation measures.
Heavy metals cannot be eliminated microbially. Only indirect mobilization by
leaching processes are known.
3. Procedure in the Application of Bioremediation
The procedure to check the applicability of biological methods for the remedi-
ation of contaminated sites using 1n-situ or on-site measures is shown in
Figure 2. The complexity of the scheme indicates that the decision whether
these methods can be applied is time-consuming. Although some of the tests can
be carried out parallely, the procedure takes a long time due to the
complexity of the contaminations. The experience shows that in the case of
hydrocarbons at least 4-6 months are necessary.
B-8
-------
Sample of the site
(water and soil)
I
test of viable microorganisms with the capability
to biodegrade the contaminants to be treated
determination of
the biodegradatiori
potential
addition of
bacteria
negative, due to
non-eliminable
toxic substances
determination of
limiting factors
alternative remediation
methods, e.g. incineration
tests to select measures
and to increase the
environmental conditions
tests to prove the applicability
of the measures in contaminated
soil and water samples of the
site in laboratory scale
(fermenter and percolation setups)
mass balance, biodegradation
abiotic processes
I
if abiotic processes
are predominant
tests m pilot scale under
practical conditions
Figure 2: Procedure in the Application of Bioremediation
B-9
-------
4. Nixed Contaminations
Contaminations are generally named after the main substance polluting the site
(e. g. contamination with chlorinated hydrocarbons etc.). Most contaminations,
however, are caused by a mixture of pollutants, i. e. soil and groundwater are
contaminated to a different degree with a variety of chemical substances. The
occurrence of a single substance is an exception which is usually confined to
contaminations after transportation accidents. Single substances, however, can
be dealt more easily than a mixture of substances.
Typical examples of a mixed contamination can be found in abandoned gas works.
Analyses of soil and seepage water samples often show high amounts of pollu-
tants, as the maximum concentrations given in Table 3 prove. The high contami-
nation with aromatic hydrocarbons, such as benzene, toluene, xylene, as well
as polycyclic aromatic hydrocarbons (PAH) is well demonstrated. Furthermore,
high values of cyanide and ammonium are to be found. The water partly shows
high concentrations of heavy metals and sulphates.
Table 3: Concentrations of Pollutants in Soil and Seepage Water of Abandoned
Coke-oven and Gas Work Plants (Maximum Concentrations found so far)
Soil
Water
Benzol
Toluol
Xylol
Naphtfelene
Phenanthrene
PAH (Sum)
Cyanides (complexed)
Phenols
Aromats According to Maximum Solubility
Sulphate
Nitrate
Oxygen
Ammonium
Iron
Manganese
ca. 5000 mg/kg
ca. 5000 mg/kg
ca. 5000 mg/kg
ca. 5000 mg/kg
ca. 5000 mg/kg
ca. 1000 mg/kg
ca. 1000 mg/kg
ca. 1000 mg/kg
ca. 3000 mg/1
0 mg/1
0 mg/1
ca. 20 mg/1
ca. 20 mg/1
ca. 10 mg/1
This example illustrates the mutual influences of the pollutants on microbial
B-10
-------
degradation.
Substances such as ammonium, which in the first place is no pollutant, can
impede the mineralization of hydrocarbons. Nitrification processes, i. e. the
oxidation of ammonium to nitrite or nitrate, consume oxygen, which is then no
more available for the oxidation of the pollutants themselves. This is also
true for readily degradable organic substances which compete with the contami-
nants for the oxygen.
Oxidation of 1 mg ammonium or degradable DOC requires 3 - 4 mg oxygen.
Compared to this, the oxygen consumption for oxidation of iron or manganese can
be neglected.
Hydrocarbons often show a competitive degradation. BTX-aromats, mineral oils,
and PAH probably do not mineralize at the same degradation rate. Better solu-
ble components are in general more readily degraded. According to laboratory
and field experiences m- and p-xylene are usually biodegraded a lot slower
than other BTX-aromats. In some cases, biodegradation of m- and p-xylene does
not start until the concentration of the other contaminants have sunk to a
minimum.
High concentrations of heavy metals can have a negative effect on bacterial
growth. Contaminations with lead and/or mercury, which often occur in aban-
doned gas works, are of special importance. Here, a microbiological remedi-
ation is out of the question. Even if bacterial strains that resist to heavy
metals and mineralize hydrocarbons are increased, soil and groundwater cannot
be considered as remediated due to the remaining heavy metals. Presently,
there is no biological procedure for the elimination of heavy metals.
Another problem are the cyanides which are found as complexed cyanides in gas
works, mostly in the shape of the non-toxic "Prussian blue". Although they do
not impede the degradation of pollutants at all, they cannot be mineralized
themselves. In contrast, the degradation of free cyanides is known and applied
in sewage plants of coke oven works for the elimination of this substance.
Chemical analysis for the detection of complexed cyanides is only possible
B-ll
-------
after special pre-treatment, so that often no difference can be noticed bet-
ween free and complexed cyanide.
Mixed contaminations, however, also show a mutual influence in a positive way.
Aliphatic chlorinated hydrocarbons (e. g. trichlorethene) are aerobically
degradable in the presence of BTX-aromats. this mechanism is based on co-meta-
bolism which certainly plays an important role in the degradation of contami-
nants. The knowledge about these processes, however, is still very little, so
that the corresponding procedures can not yet be applied on a large scale. A
mixed contamination with pollutants of high and low solubility in water (e. g.
BTX-aromats and PAH) can sometimes bring about a process in which the compo-
nent with low solubility is mobilized by the well soluble one. This might
increase the availability of the components with low solubility to the micro-
organisms and thus fasten degradation.
Co-metabolic processes might also be significant in this case. The importance
of the mentioned processes for natural degradation and the question whether
these processes can be used for remediation measures cannot be assessed with
the present state of knowledge. As a conclusion, the following can be stated:
From the analytical data of a water and soil contamination a possible micro-
bial remediation procedure can be concluded. Degradability of a substance
alone does not make sure that it is in fact eliminated in a remediation pro-
cess. In an in-situ as well as an on- and off-site procedure all biological,
chemical, and geohydrological factors have to be considered, most of which are
not even known. When bioremediation measures are planned, small scale experi-
ments in the shape of controllable on-site and in-situ fields are necessary in
the first place. Their size is determined by the distribution of the pollu-
tants and the geohydrological conditions.
All contaminants are individually composed and therefore require individual
treatment. The type and size of contaminations in connection with geohydrolo-
gical conditions can only be hints to the different possibilities of remedia-
tion.
B-12
-------
5. Toxicity and Mutagenicity
Not only toxicity and mutagenicity of the initial substances are decisive for
the risk assessment with relation to the environment, but also the development
of these parameters during a remediation measure. Experiments in our own labo-
ratory as well as of other research groups have shown that the toxicity of me-
tabolic products is often higher than of the initial pollutants.
An example for this are the results of an own degradation experiment, given in
Figure 3 a and 3 b.
B-13
-------
30
_ 25
O
01
O
O
Q
20
15
10
5-
0-
* A DOC
* * Kohlenwasserstoffe
"*
-1 1 1 ' ' '
_1 1 I I
_! IT
-15
-10
-5
CD
£
Q)
(0
Q)
Cfl
Cfl
D
5
c
-0
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80
Versuchsdauer (d)
Figure 3 a: Degradation of a Mixture of Gaswork-specific Contaminants
(Decane, Hexadecane, Pristane, Naphthalene)
- Development of DOC
100
90
fr? 80
70
~Z_ 60
ID
2 50
IJJ 40
. 30-
^ 20-
10 -
0-
Hemmung noch
15 min
30 min
-30
-25
-20
1 1 1 1 'it-
-15
-10
O
!—
'm
o
O
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80
Versuchsdauer (d)
Figure 3 b: Degradation of a Mixture of Gaswork-specific Contaminants
(Decane, Hexadecane, Pristane, Naphthalene)
- Development of Toxicity (Microtox)
B-14
-------
The problem arising in this context is the fact that the metabolites in gene-
ral are soluble in water and can therefore - without adequate safety
measures - drain off into the groundwater.
If these substances are more toxic or mutagenic than the less mobile initial
products, the r-isk of a negative impact on the environment through remediation
is rather high. So far, there are only few data about the behaviour of metabo-
lic products, which are generally difficult to detect.
In the procedure to test the applicability of biological measures described in
chapter 3 the registration of the metabolites and their toxicological impor-
tance should especially be taken into consideration.
6. General Conclusions
The NATO/CCMS fellowship programme allowed me to get into contact with diffe-
rent research groups dealing with similar topics than I do. All these groups
are still working on solutions for the problems in order to get a better un-
derstanding of the limiting factors and to overcome the difficulties mentioned
above. This will, in future, allow a more successful application of microbial
methods in the remediation of contaminated sites.
Although biological treatment of contaminated soil and groundwater is already
in use worldwide even on a large scale, there are still a lot of questions to
be answered about the success and further optimization of the processes. The
facts and data of the different measures applied in special cases are pub-
lished in detail esewhere. In order to improve the systems, it is of great
interest and importance to know more about the problems we have to tackle and
which occur during remediation measures based on biodegradation.
One of the main problems we have to overcome is the bioavailability of the
contaminants for the bacteria. The limiting factors are both solubility of the
pollutants (biodegradation only occurs in the aqueous phase) and spatial sepa-
ration mainly due to geological conditions.
B-15
-------
Furthermore, the question of additional and/or alternative electronacceptors
has to be taken into consideration. A lot of research has to be done to decide
which contaminants can be biodegraded with different oxygen sources.
One of the main problems in the frame of biodegradation is based on the
mixture of several different pollutants contaminating a site. A lot of work
has to be done to be able to mineralize all pollutants in an acceptable time
and with acceptable efforts. It is not reasonable to eliminate just one
substance out of a whole consortium. Therefore, the application of different
methods, of which microbial degradation is one, is advisable.
Last but not least, there is the problem of metabolites which has to be
solved. If metabolites are not avoidable the risk assessment of them has to be
determined and taken into consideration when bioremediation is applied.
From this point of view, future research should mainly be focussed on the
questions mentioned above, which have to be considered with respect to the
application of microbial methods.
B-16
-------
MERTEN HINSENVELD
NATO/CCMS Fellow
B-17
-------
ALTERNATIVE PHYSICO-CHEMICAL AND THERMAL CLEANING
TECHNOLOGIES FOR CONTAMINATED SOIL
M. Hinsenveld1, E.R. Soczo2, GJ. van de Leur2, C.W. Versluijs2 and E.
Groenedijk3
I. Netherlands Organization for Applied Scientific Research
2. National Institute of Public Health and Environmental Protection
3. Delft University of Technology
1. ABSTRACT
This study has been carried out within the framework of the Netherlands Integrated
Soil Research Programme. Aim of the study is to make both a systematic evaluation
as well as a selection of technologies currently developed world-wide which offer
possibilities for the decontamination of soils. The study has been carried out in three
phases. This paper describes the first phase: a survey of alternative techniques and a
first selection of the most promising ones. In the second phase, a more detailed
analysis and a further selection of technologies will be made, followed by a research
programme for the selected techniques in the third phase.
2. INTRODUCTION
In the Netherlands some IS physico-chemical and thermal cleaning installations are
readily available. With the present technology a large pan of the contaminated soils,
however, is not or problematically cleanable. This is particularly true for soils that
are contaminated with halogenated (aromatic) hydrocarbons and/or heavy metals, and
soils containing a large fraction of fines (< 0.050 mm). Problems arising are, for
example:
- emission of hazardous compounds (e.g. with thermal treatment);
- unacceptably high residual concentrations (as is often the case with extraction
techniques); or
- production of a large amount of contaminated sludge (e.g. with cleaning of clay in
extraction installations).
In addition to this, some of the techniques used at present, involve quite high cleaning
costs. It is, therefore, essential to develop alternative techniques that either do not
have the above mentioned disadvantages or lead to lower cleaning costs.
B-18
-------
3. CONTAMINATED SOIL IN THE NETHERLANDS; SIZE OF THE PROBLEM
At present the soil remediation activities are carried out following two lines:
- Remediation within the framework of the Interim Law on Soil Remediation (IBS),
the so-called IBS-sites (IBS = Interim wet Bodem Sanering); and
- Remediation carried out by private parties; the so-called non-IBS-sites.
In 1987, the total number of potential IBS-sites was approximately 7,500. At the time
it was estimated that approximately 1,600 of them urgently needed remediation and
should be remediated within the framework of the IBS. A new estimate of the total
number of contaminated sites (including the non-IBS- sites) was made in 1988 [1]. A
summary of the results of this estimate is given in Table 1.
In the governmental "Ten Year Scenario Soil Remediation" [1], it is planned that
from the total number of sites (about 110,000) 6,000 very urgent cases will be
remediated within the coming ten years, leading to expenses in the order of 5
milliard Dutch guilders (abt. 2.109 ECU).
TABLE 1: Number of sites needing remediation for five industrial sources.
Source Number of sites Number of sites Percentage
needing needing
remediation remediation
Gaswork sites 234 234 100%
Dump sites 3,290 150 5%
Carwreck sites 2,100 1,200 60%
Former industrial sites abt. 400,000 abt. 80,000 20%
Present industrial sites abi. 120,000 abt. 25,000 20%
Total abt. 530,000 abt. 110,000 20%
4. SHORTCOMINGS OF CLEANING TECHNOLOGIES IN THE
NETHERLANDS
4.1. Features and shortcomings per technique
Thermal techniques
In the Netherlands rotary kiln ovens are used. The soil can be directly heated,
indirectly heated or through combinations thereof. At the moment these techniques
are only applicable for organic contaminants (including cyanides). Basically, thermal
techniques can also be used for mercury contaminants. But this is not practised at
present because of emission control problems. The energy need of these thermal
techniques is rather high and emissions of hazardous contaminants are possible. In the
B-19
-------
Netherlands it is not allowed to treat soil contaminated with chlorinated
hydrocarbons in thermal soil cleaning installations for reasons of hazardous
emissions.
Extraction andfractionation techniques
Most soluble components are easily removable by flushing the soil with an extractant.
Unfortunately, contaminants are often preferentially sorted to the fines in the soil.
The extraction techniques available at present make use of this phenomenon by
separating the heavily contaminated fines from the bulk of the soil. But a consequence
hereof is that soils containing many fines cause an excessive sludge production. If, in
some cases, the bulk of the contaminants is present in the coarser fraction, this
fraction will be removed from the soil. At this moment, extraction techniques along
with flotation techniques are the only techniques that can deal with heavy metals.
There is very limited experience with in-situ extraction techniques.
Biological techniques (not subject of this study)
For these techniques only large-scale experience with alifatic and aromatic
hydrocarbons is available. Presently, use of these techniques leads to long treatment
periods (e.g. landfarming). Reduction of concentrations to acceptable levels (i.e. A-
level) is very difficult. Chlorinated hydrocarbons are hardly biodegradable and
heavy metals can hardly be removed. Apart from the already mentioned problems,
clogging and channeling of the aquifer may occur when using in-situ techniques,
leading to insufficient cleaning results.
4.2. Features and shortcomings per contaminant
Heavy metals
Can only be removed by extraction and flotation. There is no operational technique
that can remove heavy metals from clay or sludges.
Cyanides
Can be removed from all types of soil by thermal treatment. Clay can pose some
problems in the treatment of the off-gases. Sludges must have a dry-matter content of
at least 50% to avoid handling problems. Cyanides can be removed by extraction as
well as flotation unless the soil contains a large fraction of fines or organics (clay and
peat). Biological techniques may be applicable.
Non-chlorinated alifatic components and simple aromatics
These compounds are easy to treat thermally. Extraction and flotation can be applied
for these contaminants, unless they are present in clay or peat. These compounds are
easily biodegradable and are not considered a major problem.
Polycydic aromatic compounds
Can be easily treated thermally, resulting in low rest concentrations. Extraction and
flotation are possible with varying results. Low polycyclic compounds (less than four
rings) are good biodegradable. Biodegradability of higher polycyclic compounds is
very low.
B-20
-------
Non-volatile chlorinated hydrocarbons
In principle thermal treatment is suitable when dealing with these compounds.
However, it is not allowed to use the presently available thermal soil cleaning
techniques for these compounds in the Netherlands. The reason is that this treatment
may cause hazardous emissions (e.g. dioxines). Extraction and the presently used
flotation technique are applicable to these compounds only when they are present in
sand or sandy soils (not peat or clay).
Volatile (chlorinated) hydrocarbons and pesticides
For the above-mentioned reasons, these compounds cannot be treated thermally in the
Netherlands. Extraction and flotation are applicable in principle, but are quite
expensive for these easily removable contaminants. A better way of treating these
compounds is by stripping them from the soil. This technique, however, is not very
well developed in the Netherlands. Because of their volatility, the handling of these
contaminants needs additional safety precautions. Usually, very low rest concentra-
tions are required.
5. OVERVIEW AND SELECTION OF ALTERNATIVE TECHNIQUES
An inventory of alternative techniques that offer possibilities for treating soil or
sludge is listed in Table 2. These techniques can be either emerging techniques for
soil, or existing techniques for other material (e.g. mining techniques).
TABLE 2: Overview of alternative techniques.
Techniques Developer Features
EX-SITU TECHNIQUES
Wet thermal techniques
Supercritical oxidation 1 Modar mixed and plugflow reactor in series
Supercritical oxidation 2 Oxidyne vertical pipe reactor 3000 m
Wet oxidation 1 Zimpro; Kenneth bubble column
Wet oxidation 2 Vertech vertical pipe reactor 1600 m
Wet oxidation 3 RISO horizontal pipe reactor
Dry thermal techniques
Fluid bed oven 1 Waste Tech stan'onairy bed
Fluid bed oven 2 Thyssen not yet realized stationairy bed
Fluid bed oven 3 Ogden circulating bed
Electrical infra-red oven 1 Shiico tunnel oven
Electrical infra-red oven 2 Thagard high temperature fluid wall
Plasma reactor SKF free plasma, abt. 2000 °C
Thermal immobilization techniques
Ceramic application 1 University Utrecht sediments for bricks
B-21
-------
Table 1 Continued
Techniques
Developer
Features
Ceramic application 2
Vitrification 1
Vitrification 2
Vitrification 3
Vitrification 4
FBI
Vitrifix
Westinghouse
Retech
Nuclear Research Centre
cement, fly ash
asbest treatment
electric pyrolyser
centrifugal reactor
2500°C,RAD-waste
Physico-chemical Immobilization techniques
Immobilization based on:
-cement Many developers
- chalk and/or puzzolanes Many developers
- thermoplasts Many developers
- organic polymers
- waterglass
Dechlorination techniques
Hydrotheimal decomposition
Ultraviolet dechlorination
Radiolytic dechlorination
Chemical dechlorination
Sodium detoxification
Particle separation techniques
Heavy media separation
Heavy media cyclonation
Jig technique
Wet concentrating tables
Humphrey spiral separation
Reichert cone separation
Pinched sluice process
Revolving round table
Tilting frame separation
Vanner separation
Banles-Mozley separation
Froth flotation
High gradient magnetic separation
Extraction techniques
Extraction with
•complexing agents
- crown ethers
-acids
- organic solvents
Many developers
Many developers
Delft University of Techn.
Atlantic Research Corp.
Atomic Energy of Canada
EPA
Degussa
No developer for soil
No developer for soil
No developer for soil
No developer for soil
No developer for soil
No developer for soil
No developer for soil
No developer for soil
No developer for soil
No developer for soil
No developer for soil
Mosmans
No developer for soil
PBI
No developer
No developer
SmetJet;Sanitex
bitumen, parrafines,
polyethylene
polyesters, epoxides
hydrogen, 300 C, 18 MPa
LARC system
propanol, gammaradiation
APEG
pure sodium
based on density of particles
based on density of particles
pulsating waterbed
shaking tables
vertical spiral
perforated plate
conus-formed stream pipe
based on friction, inertia
based on sedimentation velocity
conveyor belt
rotating tilting frame
sorption on air bubbles
paramagnetic particles
heap leaching
Methylene chloride
B-22
-------
Table 2. Continued
Techniques
Developer
Features
-aliphatic amines
- fluidized gases
Supercritical extraction
Resources Conservation Co. reverse solubility
CF Systems Corporation propane, butane
Critical Fluid Systems CQ2 extraction
Other techniques
Steam stripping Heymans
Air stripping Many developers
Chemical and photochem. oxidation Ultrox
IN-SITU TECHNIQUES
Stripping and extraction techniques
Air stripping Many developers
Vacuum extraction Many developers
Compressed air injection
Steam stripping
Extraction with acids
Many developers
Heymans
Mourik Groot Ammers
Immobilization techniques
DCR-technology
Silicagel injection
Vitrification
Other techniques
Hectroreclamation
Adsorbtion by DCR or CAP
Hydrolysis
Chemical dechlorination
High frequency heating
Many developers
Many developers
Batclle
GeoJdnetics
No developer
No developer
EPA
HT Research Institute
stripping in asphalt mixer
H202. ozone and UV-light
extraction of cadmium
chalk
electrodes in-situ
electrodes, circulation syst.
adsorption by chalk or foam
raising pH to abt 11
APEG
electrodes in-situ
6. CRITERIA FOR A FIRST SELECTION OF ALTERNATIVE TECHNIQUES
Information on some alternative techniques is limited. Therefore, the possibilities of
alternative techniques for cleaning soils can only be roughly estimated. It should be
clearly understood: for new techniques of which there is only little or just
commercial information available, the estimate of experienced scientists in the field is
indispensable. In order to be able to make a reliable selection from the large amount
of techniques, the knowledge of specialists should be used as coherent and objectively
as possible. An important aid in this can be the use of a ranking system. Such a
ranking system consists of: a set of criteria, a quantification of these criteria and a
quantification of the relative importance of the criteria. Unfortunately, this paper
does not allow a lengthy description of the ranking system used. Only the criteria
B-23
-------
used and some main features of the ranking system are indicated below. In the study,
a set of four criteria were chosen for a first selection of techniques:
A. Applicability of the technique for different matrices and contaminants
Techniques that are applicable to a broad range of matrices and contaminants, or
combinations thereof, score high on applicability. The ranking system expresses the
relative importance of the combination of organics and heavy metals in more than
one soil type (sand, loamy sand, peaty sand and clay).
B. Priority concerning matrix or contaminant
In the ranking system, the relative priority of removing heavy metals from most
matrices and polyaromatic hydrocarbons and non-volatile chlorinated hydrocarbons
from clay and sludges is incorporated.
C. Status of development
The study was conducted in order to find alternative techniques that could be
developed to a practical stage within the near future. For this reason (and some other
reasons of minor importance not mentioned here) a higher development stage
influences the score in a positive way.
D. Market perspective and costs
The scoring of market perspectives is merely a valuation in extremes. Most
techniques score neutral on this criterium. Only if the techniques are excessively
expensive, complicated, etc. or excessively cheap, simple, etc. they score lower or
higher respectively.
The present ranking system is a quick and rough aid in method for selecting the most
promising techniques. In some cases the indication given by the ranking system was
overruled by additional reasons or information not incorporated in the ranking
system.
7. SELECTION OF THE MOST PROMISING TECHNIQUES
A total of 63 alternative techniques are listed. By using the scoring system we were
able to eliminate 31 techniques from this list. Furthermore, 11 techniques could be
selected for further study on the basis of the scores. An intermediate group for which
the scoring system was not decisive, contained 21 techniques. The size of this group
is an indication for the difficulty of selecting alternative techniques for which
information is either very limited or of low credibility. Below a short account of the
selection of techniques is given.
Wet thermal techniques (ex-situ)
In this category, two alternative techniques were found promising: supercritical
extraction of Modar and wet oxidation of Zimpro. Both techniques are comparable as
to their applicability and problems. The major advantage of supercritical oxidation,
compared to wet oxidation, is the possibility of treating chlorinated hydrocarbons.
Supercritical oxidation, therefore, is selected for further study.
B-24
-------
Dry thermal techniques (ex-situ)
In this category the three fluid bed ovens, one of the electric infra-red ovens and the
plasmareactor are promising. The electric infra-red oven is being developed in the
USA. It is recommended to wait for the results of this development. Fluid bed ovens
are suitable for a large range of matrices and contaminants. Furthermore, they can
be used for air stripping. In general, they are somewhat cheaper than rotating ovens,
more flexible as to the material treated and the process conditions can be better
controlled. Therefore, fluid bed ovens are selected for further research. Plasma
techniques can be used for a variety of matrices using oxidadve, reductive and
pyrolysing process conditions. In the Netherlands this technique is rather new. It is
therefore recommended to study the technique in more detail.
Thermal immobilization techniques (ex-situ)
These techniques have been incorporated in the study for completeness* sake. Within
the framework of this project we will not take these techniques into account.
Physico-chemical immobilization (ex-situ)
See remarks under thermal immobilization techniques.
Dechlorination techniques (ex-situ)
Hydrothermal dechlorination does not lead to hazardous emissions and has, therefore,
been selected for further study. The other techniques do not lead to sufficient
dechlorination results or lead to hazardous emissions. Most of the listed dechlorina-
tion techniques have a limited field of application. The need for dechlorination taken
into account, however, it was decided that some attention should be given to the other
dechlorination techniques listed as well.
Particle separation techniques (ex situ)
Particle separation techniques in general look very promising. They are cheap and
have proven their applicability in mining industry. Six of them will be studied in
more detail (jig, shaking table, spiral, tilting-frame, vanner, Bartles-Mozley).
Techniques that are expected to be applicable only to a few soils like heavy media
separation, heavy media cyclonation, Reichert cone separation, pinched sluice
process, revolving round table and high gradient separation, will not be considered
for further study.
Extraction techniques (ex-situ)
In this category only extraction with complexing agents looks promising. This
technique will be further investigated. The other techniques listed either have a lower
status of development or do not solve high priority problems.
Other ex-situ techniques
In this category we find only chemical and fotochemical oxidation as promising.
These, however, are rather water purification techniques than techniques for soil and
sludge cleaning. In the framework of this srudy they will not be investigated further.
It is recommended to incorporate these techniques in a research programme for
water purification. Ex-situ stripping techniques are fairly expensive for high volatile
B-25
-------
and, therefore, in principle easily removable contaminants. These techniques will not
be investigated further.
Stripping and extraction techniques (in-situ)
In Ais category compressed air injection can be considered for further study. Tnis
technique, as well as the other stripping techniques, is frequently used in Germany
and information on the technique becomes readily available. There is no need for
stimulating this development Within the framework of this study we will, therefore,
not investigate this technique further. In-situ extraction is expected to be applicable
only to very sandy soils and highly volatile contaminants; situations that very seldom
occur.
Immobilization techniques (in-situ)
See remarks for thermal immobilization techniques.
Other techniques (in-situ)
In this category electroreclamation looks very promising. This technique has the
possibility of cleaning clay contaminated with heavy metals, this technique will be
further investigated. The other techniques listed have a rather limited field of
application and do not solve high priority problems.
In phase 2 of the project the selected techniques will be studied in more detail. The
findings will be described in 8 monographs entitled:
1. Supercritical oxidation
2. Fluid bed incineration
3. Plasma reactors
4. Dechlorination techniques
5. Particle separation techniques
6. Froth flotation
7. Extraction with completing agents
8. Electroreclamation
Based on these monographs, a selection of techniques for further development in the
Netherlands will be made.
8. REFERENCES
I. Ten year scenario soil remediation, Stuurgroep Hen Jaren-scenario
Bodemsanering, Ministerie van VROM, 1989 (in Dutch)
2. Handbook on Soil Remediation, Staatsuitgeverij, 1988 (in Dutch)
B-26
-------
ALAIN NAVARRO
NATO/CCMS Fellow
B-27
-------
NATO/CCMS CONFERENCE
ANGERS
Wednesday November 7th
BULK AND SOLIDIFIED WASTE
AN ADAPTED PROCEDURE
I - INTRODUCTION.
The admission of hazardous industrial waste or waste, containing hazardous
substances is the object of a regulatory procedure. Certain wastes can either be admitted
directly or absolutely excluded. All other categories of waste must be submitted to an
admission procedure. In France, this procedure includes a leaching test carried out
according to theAFNOR standard.
The principle of this standard is to carry out a leaching test in order to determine the
immeadiately soluble fraction when brought into contact with water. The results of this
test therefore integrate both the solubility of the waste and the conditions of access of
water to the waste. Hence, it is necessary to crush the waste to particle size of no greater
than 4mm. Under these conditions, the test may primarily be considered as an arbitrary
means of waste characterization, rather than a tool for predicting the mean or long term
behaviour of the waste.
Two large categories of waste should be excluded from the field of application of
this standard:
* Bulk waste : the definition of bulk waste is, any waste that when produced
consists of fragments greater than 4mm, on condition that this state be durable
in time when under the influence of physical, mechanical or chemical agents.
* Solidified waste : the definition being waste, either liquid or solid
originally, but which has undergone a solidification treatment by the addition
of binders (cement, molten glass, organic binders) according to a specific
procedure.
In order to more accurately predict the behaviour of these 2 categories before
admission to landfill (class I), the possibility of developing a better adapted leaching test
was studied, rather than applying the AFNOR standard.
B-28
-------
The first phase of this study was to carry out a literature survey followed by a
procedure proposal. The proposed procedure is now being tested in the laboratory, and it
is only when this second phase has been completed that any official decision can be made.
The first phase of this work will be discussed here.
II - THE AFNOR STANDARD
(see overhead 1)
III • LITERATURE SURVEY.
The new procedure must achieve 2 objectives.
* to be adapted to the specific case of bulk or solidified waste, concerning the
transfers which take place between the waste and water, and to the
structural integrity.
* to be coherent with the AFNOR standard.
The literature survey shows that we have a large number of operational tests at our
disposal, on a national and international level to:
appreciate the physical and mechanical properties which govern the state, in
the long term, of bulk and solidified waste.
evaluate the teachability of waste, in particular, solidified radioactive waste.
J) Principal results of leaching test.
Globally, leaching tests can be divided into 3 main categories.(see overhead 2)
B-29
-------
THE AFNOR STANDARD X31 210
September 1988
This standard describes a leaching test to obtain, under defined conditions,
a soluble fraction which can be analysed for characterization purposes.
It consists of:
1) general recommendations for waste sampling, either at
the production or disposal stage.
2) sample preparation procedures for laboratory tests
3) procedures for leaching tests
sample preparation
1
continual stirring
with aqueous solution
leachate separation
analysis of leachate
the residual material may be
submitted to further leaching tests
lOOg waste + lliter water
demineralized water
stirring: 60/min
contact time 16 h
room temperature
filtration : (0.45pm)
centrifugation
4) an official experimental report
B-30
-------
A • Tests without renewal of contact solution.
A known quantity of liquid is brought into contact with a known quantity of waste
for a given period of time. 3 subcategories can be distinguished:
- tests with stirring
- tests without stirring
• tests with sequenced extraction
B - Dynamic tests.
The solution is renewed, either continuously or periodically. 3 subcategories can
also be distinguished:
BATCH TESTS : the waste is in particle form in a confined medium.
FLOW AROUND TESTS : the waste is in block form and the solution flows
round it.
FLOW THROUGH TESTS : the waste is in block form and the solution
percolates through it.
C • Hybrid tests.
These can be divided into 2 categories :
- saturation tests
• extraction tests (SOXHLETfor example)
All these categories can be distinguished by their different operating conditions
* Nature of the solution :
• water or dilute aqueous solution (natural, distilled, deionized, acidified)
• more concentrated aqueous solutions (acids, brine)
B-31
-------
It would seem better not to use brine (particular case ofseawater) and strong acids,
which correspond to unrealistic situations.
Deionized water would be a better solution, eventually acidified with acetic acid
(case of mixed waste containing biodegradable waste.
* Sample preparation :
All crushing must be excluded but certain wastes are of a dimension that special
standard samples must be made either by moulding (solidified waste) or by cutting out
(bulk waste). In the case of bulk waste of dimensions smaller than the chosen standard
sample, a standard volume was considered.
* Mode of contact with water :
Systems with stirring are the best adapted to our approach : mechanical stirring
(backwards and forwards) using a bar magnet, or a rotor, or by bubbling gas through the
solution (nitrogen or carbon dioxide).
* Liquid/solid ratio :
This ratio can easily be expressed for dry waste; it must be more precisely defined
for wet waste. In the literature, the ratio solution I waste varies from 1: 1 to 100:1.
* Contact time :
It can vary from 16 hours to 1 year. The AFNOR standard fixes this time at 16
hours.
* Final separation of leachate :
In the case of tests without stirring, separation is carried out by filtration. In other
cases, the separation is often described precisely (choice of filtration mode,
centrifiigation, filter size, etc...
B-32
-------
2) Tests used to evaluate the structural integrity of the bulk materials.
- visual appreciation : a rigourous nomenclature must be defined concerning
fragmentation, softening, fissuring, colour changes, reduction to dust, etc...
- mechanical strength.
The mechanical behaviour of the waste has to be known in order to qualify it as
"bulk waste" and to predict its behaviour at the time of testing.
The literature shows that, to our knowledge, no specific procedure exists for waste,
for this aspect, and that we have to use procedures applied to construction materials. For
example we can quote tests such as :
• tensile strength
• compressive strength .for which a number of devices exist together with very
rigourous procedures.
3) Freeze/thaw tests
A number of procedures have been listed. The parameter "material" (porosity and
tensile strength) and the operational parameters (water content at the time of freezing,
temperature gradient, number of cycles) must be taken into account.
4) Wetting/drying tests
The water content and water absorption capacity are the two essential parameters
which must be known in order to carry out this test. The various tests in the literature
differ in their operating modes and as well as in the criteria chosen to evaluate the
structural integrity.
5) Resistance to biological agents test.
The freeze/thaw tests and the wetting/drying tests have given rise to diverse
protocols adapted to waste. This is not the case for biological tests which have been very
little used. It is necessary to refer to tests concerning the biodeterioration of materials.
B-33
-------
- bacterial corrosion of metals,
• biodegradation of plastic, paint, fuel, tarmac, rubber,
- composting of municipal and industrial waste,
-.bioleaching of ores,
• biodegradation of diverse materials (piping systems, joints, surfaces) in contact
with drinking water.
6) Diverse ageing tests.
Procedures exist related to the nature of the concerned materials and to their
mechanisms of physico-chemical degradation.
B-34
-------
IV - SPECIFICATIONS FOR THE DEVELOPMENT OF AN ADAPTED
LEACHING TEST
In France, there is a standardized test for waste prior to landfill. As bulk and
solidified waste have been excluded from the field of application of this test, it is
important to develop a specific procedure for these two categories.
To define the new test it is important to:
a) to define the conditions which differentiate classical waste from bulk or
solidified waste.
b) to determinie the shape of the standard sample to be adopted.
c) to adopt a leaching procedure which can be common to both bulk and
solidified waste and also as close as possible to the existing standard
procedure.
d) to define the list of complementary tests which allow us to predict the
behaviour of these wastes in their ultimate disposal site.
e) once this list of tests has been determined, to choose the techniques and tools
adapted to each of these tests.
V • EXPERIMENTAL PROTOCOL
At the end of this study, and after discussion with the laboratory representatives
concerned, a provisory protocol was elaborated. This protocol which we will describe
here is presently being tested in the framework of an experimental programme, and it is
only after this second phase that a definitive protocol will be elaborated.
It is important to remindyou here that:
1) this protocol is common to both bulk and solidified wastes.
2) It has tried to remain coherent with the existing french standard procedure.
B-35
-------
3) It does not have the ambition of being a trustworthy simulation of the
behaviour of waste, but is to be considered as a tool, easy to implement,
reliable and applicable to these types of waste of any origin.
4) it must not be considered as a test destined to "validate" solidification
technologies in general. However such validation work could include the
principles of these tests.
5) carrying out this test does not mean that the analytical operations for waste
characterization are no longer necessary.
VI - CONCLUSION.
The procedure presented here cannot be considered as defintive. It is in the process
of being validated and may undergo modification at the end of the experimental phase.
Taking into account the probable evolution ofconditionning techniques and management
strategies of landfills which accept industrial waste (class I), it is necessary to have such
control tools at our disposal.
It must be noted that this procedure, which has been voluntarily simplified, cannot,
by itself, be used as a technique for the validation of solidification processes in general.
Finally, by confronting this procedure with procedures used abroad, the ultimate
objective may be achieved, which is to elaborate a common international procedure.
A. NAVARRO 1990
B-36
-------
TEST PROTOCOL
Waste
Preliminary test
bulk or solidified?
standard leaching test
NO
AFNORX31
210
YES
sample size 4 x 4 x 8cm
possible?
YES
NO
| Cutting | | Crushing | 10 < 0 < 20mm
Structural integrity test: mechanical resistance
and other tests (freeze/thaw,
humidification/drying,...) according to needs
YES
further leaching tests
B-37
-------
APPENDIX C
NATO/CCMS GUEST SPEAKERS
-------
BRUONO VERLON
NATO/CCMS Guest Speaker
c-i
-------
CONTAMINATED SITES - SITUATION IN FRANCE
SUMMARY
In France, although the problem of contaminated sites has not reached until now the level of
a first priority like in the USA or in some European Countries it is considered with seriousness by
the Notional and Local Authorities.
Action has been and is presently carried out for the three main steps of these problems:
- Identification of potential problems - contaminated sites registration
- Evaluation of site contamination - risk assessment
- Treatment of contaminated sites • land recovery
Cleanup costs are most of the time supported by the waste producer or disposer according
to the 'polluter must pay' principle. In some cases, publics funds have been granted,
because of lack of responsible party. At the present time treatment techniques range from
site control up to complete cleaning involving hazardous material extraction and off site
elimination with some significant cases qf waste encapsulation and more numerous
examples of restoration by solidification-stabilization.
This last techique excepted. there have been, up to now. few french technologies
developed specialy for the rehabilitation of contaminated sites and soils. This situation can
be explained by the relatively limited number of hazardous sites registered and by the
existence of a rather well developed system for the treatment and disposal of industrial
waste which can be used for the off site treatment of contaminated materials and soils.
However this situation may change in the near future because of the Increasing number of
sites to restore and in this view we have decided to play an active role to promote the
development of new french or imported techniques for the treatment of contaminated soils.
I - IDENTIFICATION OF POTENTIAL PROBLEMS - CONTAMINATED SITES INVENTORIES
The first step of french action in the field of hazardous dumps sites and contaminated land
consisted in two Inventories carried out in 1978 on national level:
• the first one realized through inquiries of the Ministry of Environment among the local
Inspections of Classified Installations responsible for control of polluting industries -including
disposal installations-. By this mean, about 120 questionable sites were identified of which
62 were recognized as serious and therefore requiring priority corrective action
- the second one. consisted in a study made by the Bureau de Recherches Geologiques et
Minieres (B.R.G.M) for the accoung of the newly created ANRED. This study was carried out
with the aim to discover hazardous sites by the collection of information available in the
Regional Representations of the B.R.G.M, taking advantage of the particularly good
knowledge these local agencies had of the environmental situation -assuming the fact
thas most of the time pollution occuring from contaminated sites affects groundwater-.
These investigations produced a total of 453 sites among which 82 were recognized as
serious.
At the end of 1985. the official evocation of the Ministry of Environment mentionned 107
cases which corresponded to a more important number of sites. This figure, compared with
C-2
-------
the initial number of 62 hazardous sites shows that the first inventories carried out in 1978 were
far from exhaustive. In addition two additionnal facts have emphasized the necessity of a
new registration of unknown contaminated sites.
- The first is the extent of estimations to thousands of contaminated sites in countries where
active environmental protection policy has been carried out on this subject : USA.
Netherlands. Federal Republic of Germany.
- The second is the incidental discovery of abandonned hazardous sites that created
certain pressure upon the local and national Authorities.
Consequently, the Minister of Environment has decided, at the beginning of 1985 to reactive
new sites inventories. At the present time these actions are carried out through two main
ways:
I/ Directives given to local Authorities responsible for the control of Classified Installation for
- the Environmental Protection (including industrial and municipal landfills) requiring
• reactivation of contaminated srtes inventories.
2/ Mission given to the Agence Nationale pour la Recuperation et rElimination des Dechets
to develop new inventories actions at national and/or regional levels.
The main of these actions consisted in an inquiry of the municipalities by the mean of a
mailed questlonnary. A great number of answer was obtained (more than 18000). However
the number of questionable answers was only about 500 which are now being evaluted. This
evaluation is not completed now but according to the main existing results it can be
estimated that less than 10 percent of the mentioned cases would be realy hazardous.
At the present time, according to a report published by the Secretary of State for
Environment in july 1989. all these actions of inventory have produced a new list of about 100
officialy registered hazardous sites that the government has planned to restore within the
next five years. However this list is already not exhaustive : some existing important cases
are not mentioned and the action of inventory is still going on.
II - ADMINISTRATIVE AND LEGAL ASPECTS
In France, the normal way to finance the studies and rehabilitation of contaminated sites is
the application of "polluter must pay" principle. This Is made possible by the
implementation of two basic laws : the law of July 19. 1976 on Classified Industrial
Establishments tor the Purpose of Environment Protection and the Law of July 15. 1975 on the
management of wastes.
These laws make the generators or holders of contaminated sites responsible for the
pollution and pay for the investigations and rehabilitations. They have been successfully
applied by Local Authorities under the supervision of the Ministry of Environment for most of
the cases of rehabilitation carried out in France.
However, it appeared that in a significant number of cases it was not possible to find a
responsable party able to pay for the depollution and some of these cases remained
unsolved until the issue, on January 9.1989 of a new directive for the Local Authorities facing
such situations.
The main steps of the procedure described >n this directive are the following :
I/ The local Authorities must carry out all the existing legal possibilities to find the polluter and
make him realize and pay the rehabilitation project
C-3
-------
21 In the case of impossibility to find a reliable responsible party the Local Authorities inform
the central level and ask its agrement for the following step which Is as follows: the Prefect
of the Department, acting as representative of the government, designate the National
Agency for Waste Recovery and Disposal (ANRED) to carry out the rehabilitation of the
considered site.
3/ In this situation, the ANRED carry out the rehabilitation project, financed by the
government and after completion, engage lawsuits to find the responsible of the
contamination and try to get the repaying of the expenses.
Up to now the Implementation of this directive has given the possibility to solve about ten
cases of middle importance.
Ill -TECHNICAL ASPECTS
lll.l - Introduction
In France, up to now, although there is a national policy on the subject of hazardous
dumps and contaminated sites and some significant examples of land recovery
there are no national or regional technical guidelines or standards applicable to the
technical and economical management of the restoration of contaminated sites.
After the first inventories carried on in 1978. hazardous sites were ranked according to
their estimated level of risk with colored point (black, red...). However this classification
was roughly approximative with no realy measurable parameters. In fact, risks
assessment and decontamination projects have been carried out on pragmatic
basis, according to variable estimations of the characteristics of the sites and of the
vulnerability of the environment, allowing the Local Authorities to appreciate the
seriouness of the problems and the manner to deal with them. Although this situation
may be understood as a conseauence of a necessary adaptation of a site
restoration requirements to the local technical conditions it Induces the risk cf
inadhequate solutions and of inequality between polluters facing similar problems.
Therefore ANRED. working in many cases as a national expert has developed a
special effort to rationalize the technical approch of these problems. The following
paragraphs will reflect this point of view, based on our national and international
experience.
111.2 - Evaluation and management of decontamination problems
The first step of a project for the rehabilitation of a potentialy contaminated site
consists-ln-the definition of the problem : characteristics of the contamination, nature
and importance of the risks, and further of the way to deal with it. In this view the
assessment of the significance of the contamination, set up of cleanup goals and
choice of rehabilitation techniques are of the utmost importance.
A first way to deal with these questions is to refer, when it Is possible, to existing
regulation not specific to contaminated sites, for example:
- In the case of the rehabilitation of a site by the isolation of hazardous material and
contaminated soils reference should be made to existing regulations applicable to
special Industrial wastes controlled landfills : for example, requested maximum
permeability of 10r9 m/s and necessity of efficient collection and treatment of liquid
and gazeous effluents:
C-4
-------
- In the case of treatment impliying release of effluents O.e leochates ocuring after
isolation or solidification-stabilization treatment) reference should be made to existing
regulations:
. applicable to drinking water supply in the case of the release of effluents in
groundwater resources used for the population
. applicable to the discharge of domestic and industrial effluents in the case of the
release of effluents in surface water
. applicable to gazeous emissions in the case of release of contaminants in the air.
More generaly we think that the definition of the contamination and the set up of clean
up goals should be based on site specific evaluation taking in account:
• The nature of the contaminants, their quantities, their chemical form and physical
characteristics (toxicity and mobility) and the physical and chemical soils properties
- The characteristics of the migration pathways (environmental vulnerability):
. groundwater
. surface water
. soil
.air
. direct contact
- The present and future use of the soil and of the groundwater.
However it is also generaly interesting to make reference to a comprehensive list of
predetermined criteria of contamination levels of soil and groundwater to get an initial
characterisation of the contamination and to set up preliminary cleanup goals. In
addition the background level of pollutants naturally presents in the environment
(metals, arsenic...) has to be considered. As it has been mentioned before such
specific criteria don't exist now in France and instead we can generally refer to the well
known dutch criteria
111.3 - Techniques of rehabilitation
Up to now the main rehabilitation techniques which have been used in France are :
- extraction and off site treatment
- isolation of the contaminated area
- on site (or in situ) stabilization/solidification
- pump arid treatment of contaminate water
At the present time projects are going on which Implies the use of in situ soil vapor
extraction and treatment, and thermal and biological processes are in development.
However, considering the present existing contaminated sites it appears that there is a
lack of techniques to solve many cases in satisfactory technical and economical
conditions. In fact, the rehaoilitations by extraction and off site treatment of wastes.
contaminated soils and materials which has been performed In many cases by the
use of the existing Industrial hazardous waste treatment plants appears to be strongly
limited In many cases of soils and contaminated materials not technlcaly and/or
economicoly adapted to such treatments. In this view the cose of landfills for industrial
waste has also to be speaaiy mentioned because such installations have had up to
now the possibility to accept a wide range of residues and polluted soils and materials
C-5
-------
extracted in contaminated sites at rather low costs and this possibility will probably be
strongly limited in the near future by more stringent regulations and increased costs.
In the perspective of this development of specific processes to restore, contaminated
sites we have studied on the national and international levels the different techniques
which are already available or in development the following tables summarize their
characteristics and their opportunities and limits of application.
1.3.1 • Techniques already available
TECHNIQUE
Isolation
Extraction and off
site treatment
Solidification
Stabilization
Thermal treatment
(soils)
CONSISTS IN
coping and lateral
isolation
Extraction, transport
and treatment in
industrial waste
treatment plants
mixing with reactive
agent, on site or
in situ
Many kind of
thermal treatment
are available : the
most usual include
heating in rotary
kiln + gas
afterburner
APPLICABILITY
various kinds of solid
waste materials and
soils
many kinds of
Hazardous waste
and contaminated
material
sludges, liquids.
soils. Mainly
inorganic contami-
nants - In some
cases non volatile
organics
Organics contami-
nants in
contaminated soils
and materials
cyanides
PARTICULARITIES
LIMITS
-need a site siutable
for isolation
-relatively limited
cost but require
future control and
maintenance
-can be used as
temporary solution
-characteristics of
the wastes materials
and soils has to be
technlcaly and
economically
adapted to the
treatment
•need transport
-often costly
-limited efficiency
(fixation not
perfect) specialy
for organics and for
amphoteric metals
-The temperature
of the final incine-
ration has to be
adapted to the
nature of contami-
nants
-need special care
for volatile metals
C-6
-------
TECHNIQUE
Extraction/
Soil washing
In situ vacuum
extraction
CONSISTS IN
Many processes
available :
-some using pure
water and
mechanical
energy to extract
the contaminants.
-other using various
solutions or specific
solvents.
-Creation of air
depression in the
unsaturated zone
and treatment of
the collected air
-Possibility of
improvement by air
injection (in the
saturated zone).
by thermal desorp-
tion (heating)
APPLICABILITY
Mainly Inorganics
(heavy metals) but
also organics (PCB
hydrocarbons)
Volatile organics
PARTICULARITIES
LIMITS
• Usualy efficiency
limited by the size
of particles
- produces
residues which
have to be
disposed with
efficiency.
- efficiency
influenced by
impermeability.
heterogeneity and
water content of
the soils.
In addition to these techniques it has to be mentioned the use of groundwater
treatment. These treatments are carried out either alone in a continuous and long term
decontamination process or in combination with other kind of treatment of a site.
Different water treatment processes are utilized, either physicochemical or biological
or combination of both. In many cases activated carbon is used in the final stage of
the treatment to adsorb the micropollutants.
C-7
-------
111.3.2 - Techniques in development
Many other kind of techniques are In development and for some of them are at the
demonstration or commercialisation stage. We mention there after those of theses
processes we consider relatively promissiong :
• other kinds of thermal treatment: Infrared, oxygen-enhanced, pyrolysis
- glycolate dechlorination (PCB)
• in situ vitrification
- wet air oxydation - supercritical oxydation
• electro reclamation
Biotechnologies appear also promising but have to be specialy considered:
- they are developed In many countries by research institutions, universities, private
enterprises and consultants, and a great number of research and development works
are on going, based either on on site (on the field or in reactors) or on in situ processes,
involving most of the time aerobic degradation and in many cases various ways to
masterize and improve the degradation (i.e: enhanced oxydation). In many cases, it
appears difficult to evaluate with accuracy the efficiency of treatment specialy for
complex molecules (halogenated organics) where the degradation implies stages of
intermediate metabolites.
- up to now. few processes are available with proven efficiency on a commercial
basis.
ReneGOUBIER
Texte presente a EUROFORUM
ALTLASTEN SAARBRUCKEN (R.F.A)
11-13 juin 1990
C-8
-------
HERVE BILLARD
NATO/CCMS Guest Speaker
C-9
-------
The NATO/CCMS Pilot Study
on Desmonstration of Remedial Action
Technologies for Contaminated
Land and Groundwater
Fourth international Conference
5 au 9 November 1990
ANGERS - FRANCE -
INDUSTRIAL WASTE MANAGEMENT
IN FRANCE
c-io
-------
THE MANAGEMENT OF* INDUSTRIAL WASTES
Industrial Wa\«tema A Fen* Figures
In France, industrial wastes are usually classified in
three categories:
1) Inert wastes, comprised of earth, debris, inert materials
produced by processing of minerals. These wastes are
usually put in dumps. Estimated annual productions
100 million metric tonnes.
2) Commonplace wastes, similar to household re-fuse-and able to
be treated using the same methods. These wastes include
wood, waste paper, cartons and cardboard, plastics, etc.
Estimated annual production: 32 million metric tonnes.
3) Special wastes which are characteristic o-f industrial
activity. These wastes contain harmful elements in
concentrations o-f varying degree and therefore pose a
higher risk to the environment. Disposal of the wastes
must be carried out with special precautions. Estimated
annual production: IB million metric tonnes, of which
4 million metric tonnes are classified toxic or
dangerous.
Special wastes may also be classified in three
categories!
C-ll
-------
a) Organic wastes (mainly hydrocarbon wastes, tar, solvents.
etc.), usually able to be treated by incineration,
although physico-chemical treatment processes are being
developed for certain very specific wastes. The presence
of chlorous molecules in a large part of these wastes
requires special smoke purification.
b) Liquid or semi-liquid mineral wastes (for example,
treatment baths for metal surfaces, acids or bases) which
are able to be treated physico-chemically
(neutralization, separation of undesirable elements in a
solid phase, oxydation, or reduction). The treatment
processes aim at reducing the toxicity of the wastes.
c> Solid mineral wastes (for example, moulding sand, cyanide
hardening salts) which must be stored in dumps or deep
storage facilities, depending on the toxicity of .the
constituent elements.
It must be noted that incineration and physico-chemical
processing in turn produce new wastes
-------
situation, which takes into account the characteristics o-F the
wastes, technological limitations and the availability of
external processing and collection systems. These options can
be classified in the following manner:
1) Stopping the production of a waste product by changing the
process or production (implementing "clean technology" in
the strictest sense o-F term);
2) Recycling the waste product within the framework of the
process that generated it;
3) Recovery and valorization of the waste for various uses
within the -firm;
4) Recovery and valorization of the waste for use outside the
•firm that produced the waste (This can be done either
directly, firm to firm, or indirectly, through a
professionel waste recovery intermediary.);
5) On site disposal of wastes without valorization;
6) Disposal by waste disposal professionals outside the firm
(treatment in a collective waste disposal centre).
Disposal options are often costly and it is obvious that
an industrial -firm has interest in seeking recycling or
valorization options. (See Appendix 1)
The choice between on site treatment or processing
outside the firm can be evaluated considering data which are
inherent to each option and which may include the fallowing:
a) the profitability of an on site -facility, linked to its
critical size;
b) the investing or subcontracting policy o-f the firm;
c) the firm's energy needs in the case of an energy
valorization treatment process.
C-13
-------
At this point» it would be appropriate to bear in mind
that under the Law of 15 July 1975, the producer or holder of
waste is responsible for what becomes o-f the waste and must
provide conditions amenable to the proper disposal thereof.
2. Wastes within the Firm
2.1 Separation o-f Wastes at the Source
Every precaution must be taken- to succeed in not mixing
the different types of wastes produced in a firm if these
wastes are to undergo separata disposal or valorisation
processing or to undergo separate treatment processes.
Separating wastes at the source often requires additional
investment, but it offers certain advantages}
a) Increased Valorisation Potential. It is easier to valorize
homogeneous waste products. For example, in surface
treatments, the recovery of metallic salts in solution is
profitable in concentrated baths; if these baths are
mixed with diluted rinsing baths, recovery becomes less -
if at all - profitable.
b) Improved Work Conditions. Dangerous mixtures are avoided.
Such mixtures can cause heat buid-up, toxic fumes or they
can be at the origin of fires and explosions. The
unsupervised mixture of an acid and a base can cause a
violent reaction that leads to a significant rise in
temperature.
c) Lower Treatment Costs. In the case of mixtures, the cost of
treating the most difficult element will be applied to
the entire mixture.
C-14
-------
2.2 Appropriate Conditioning and Storage
Solid wastes must be stared on A reliable and
environmentally sealed surface, in a holding tank, or - as a
general rule - by any other means that avoid their being mi::ed
with rainwater run-off or being scattered. Storage in portable
containers facilitates subsequent collection and transport.
Liquid wastes must be stored in environmentally s'afe
containers, generally hermetically sealed so as to prevent
leaking or fumes escaping. The containers used may be
cisterns, drums or tanks depending on the storage capacity
needed and the nature of the wastes.
The choice of the conditioning equipment also depends on
the duration of storage, handling and transport conditions and
subsequent processing to be carried out on the wastes.
When waste collection can be carried out regularly and
frequently, only reception and holding facilities are
necessary at the waste production site. Thus the risk of
accidents, which often occur during handling, is reduced.
3. The Means Available to Dispose of Special Wastes
In France, specialized centres are available to waste
producing firms to process their wastes. They include:
a) Incineration centres
b> Physico-chemical treatment centres
c) Specialized treatment centres
dl Technical land-burial centres (controlled waste and
disposal landfills)
Certain centres combine several of these activities.
(See Map, Appendix 2)
C-15
-------
Certain "pratreatmenf' centres are specialized in mixing
and sorting operations which make it possible to channel the
waste, or each of its constituents, toward the most
economically profitable destination.
3.1 Wast* Acceptance Procedure
The disposal of industrial waste often can be carried out
by several treatment centres. The firm's choice of a
particular centre should be based on attaining the best
processing at the lowest cost. It is therefore worthwhile for
a firm to ask several centres for estimates and then to
compare prices - taking transport costs into account - before
selecting a disposal centre.
The procedure for waste acceptance fallowed by waste
treatment centres is as follows:
a) The centres, once contacted, will ask the firm for a sample
of the waste for analysis in order to determine the
nature of processing and the cost of disposal.
b) Once the sample analysis is completed, the centre may then
issue an Acceptance Certificate to the firm. Only then is
the firm allowed to send a load of wastes to the centre
for treatment.
c) When the load arrives at the centre, it is tested to
determine whether it corresponds to the sample previously
analysed. If the load corresponds, it is accepted for
treatment} if not, it is returned to the producer.
d) Once the waste has been destroyed, the firm must receive a
Certificate of Disposal, a document proving the waste was
disposed of properly and in accordance to regulations.
C-16
-------
3.2 Collective Incineration Centres
The waste acceptance criteria for Incineration centres
take the following factors into accounts
a) The calorific value of the wastes, which will determine tne
possible need for additional fuel in order to ensure
combustion]
b) Halogenated elements content, which determines a need for
acceptance by centres specifically equipped for carrying
out the necessary incineration techniques and treatment
facilities for gasses}
c> Metal content, because alkaline elements are responsible
for damaging furnace refractor!es|
d) The flash point, which will determine the need for special
storage conditions.
Incineration centres accept solid, pasty or liquid
wastes, In function with technical characteristics. Under
current regulations, the centres must respect operating
temperatures on the order of 7SO«C (simple organic wastes) to
1200*C (organochlorlne wastes). Smoke undergoes dechlorination
treatment, allowing the released smoke to attain the following
characteristicsi Chlorine (10O mg/nma), dust (ISO mg/nm3) and
heavy metals (3 mg/nm").
However, for plants currently under construction, public
authorities require industry professionals to guarantee
the fallowing values :
Dust 30 mg/Nm3
Hcl 50 mg/Nm3
French centers usually succead today in comphying with
these requirements, however they will shorthy have
comply with new European directives which are currently
under stady.
When carried out properly, incineration is an effective
means of disposing of a high proportion of toxic wastes,
including organic wastes, phenolic wast* water, hydrocarbons
and chlorous wastes.
Current prices depend on the calorific value and amount
of undesirable elements present, such chlorine, metals and
sulphur. Prices also depend on the conditioning, and
conditioning in bulk is preferable to conditioning in drums.
C-17
-------
Incineration in Cement Furnaces
Cement plants consume huge amounts o-f energy. There-fore
cement plants have sought alternative fuels in order to lower
their energy costs. The cement industry has now turned its
attention towards wastes, and particularly wastes with high
calorific value, such as hydrocarbon mixtures or certain non-
regenerable solvents. The current trend is toward producing
mixtures attaining - on average - the -following
characteristics:
a) Minimum Calori-fic Value o-f 4000 kgcal/kg
b) Perrantage o-f Cl < 0.5 7.
c) Percentage o-f HaO < 40 7.
Moreover, environmentally speaking, the technical
conditions of furnace operation guarantee minimum pollution
because o-f the burning temperature o-f clinker and because of
the long contact time between the combustion products and the
matter to be burnt. (The contact time of gasses in the area
which is hotter than 1200°C is more than six minutes.)
Although clinker has complex ing properties towards
certain toxic elements as alternative fuel in the burner.
Thus, liquid wastes are most often burnt.
C-18
-------
Certain heating stations and certain household refuse
incineration units also accept special wastes for
incineration.
The disposal capacity of collective incineration centres
is nearly 800 000 metric tonnes a year (1989).
Incineration at Sea
The destruction of halogenated wastes can be carried out
in facilities installed on ships working in the North Sea.
Waste producers must contact either an intermediary storage
centre or a collector, who will then subcontract with the firm
managing the incinerator ship for the subsequent destruction
of the wastes. A European directive will place legal limits on
recourse to this method of disposal. The quantity incinerated
in 1988 was 15 000 metric tonnes and is in constant reduction.
3.3 Physico-CheaiCAl Processing Centre*
Physico-chemical treatment centres mainly perform the
following treatment processes! oxydation-reduction, neutrali-
zation, dehydration, fixation, and emulsion-breaking.
Wastes accepted by these centres arei
a) liquid wastes containing cyanide. Solid cyanide hardening
salts are not detoxified at these centres; rather, they
are conditioned for land-burial storage in salt mines. At
present, they are shipped to West Germany.
b> Wastes containing hexavalent chromium. These wastes are
first reduced and then precipitated into an insoluable
•form. When the solutions are highly concentrated, the
possibility of valorization can be considered.
c) Waste acids and bases. These wastes'are neutralized.
d) Solutions containing metals. They are precipitated.
C-19
-------
e) Pasty wastes containing toxic elements. These wastes can be
treated by -filiation or hydraulic bonding, thereby
reducing the level of humidity and limiting leaching of
toxic elements.
f) Ion exchangers. They are regenerated.
The capacity of collective detoxification centres in
nearly 360 000 metric tonnes a year (1988) (See
Appendix 4).
3.4 Specialized Treatment Centres
Certain -firms have specialised in the treatment of
particular kinds of wastes:
Fluids Produced in natalMarking
The fluids can be grouped into two categories: solvents
and emulsions. They contain approximately 3V. oils and various
sterilizing agents* bactericides «tc...
Various processing techniques are available. Acid-
breaking and ultrafiltration apply only to emulsions, whereas
incineration can be used in the treatment of all such fluids.
The capacity of collective waste treatment centres is
appoximately 265 000 metric tonnes a year
Solvents
The regeneration of solvents can take three forms*
a) Internal regeneration of solvents by the firm
b) The firms supplies waste solvents for regeneration outside
the firm and will subsequently use the regenerated
solvents.
c) Waste solvents are sold for regeneration outside the firm.
C-20
-------
The choice of one of these three alternatives will depend
upon the quality o-f the waste solvents produced, the market
value of the solvent, the potential for re-use of regenerated
solvents within the -firm, etc...
The following regeneration techniques are available:
1) steam distillation
2) •fractional distillation
3) separation in a fine layer
The first technique produces a solvent which is largely
•free of its impurities, but heavily saturated with water. This
technique is often used for sales (see "c" above) of solvents
with low market values, particularly with chlorous solvents.
The second technique is often used with solvents of
higher market value when the firm supplies the waste solvents
for regeneration to specialists in solvents refining (see "b"
above).
Transfer Centres
Collective waste treatment centres are generally
established in areas of the country with high concentrations
of industries, thus satisfying a large part of treatment
demand in terms of industrial waste tonnage produced. In some
regions of the nation, the level of industrial activity is too
low to justify the establishment of an industrial waste
treatment centre. And yet, wastes produced by industries in
those regions must be properly processed. This explains why it
has been necessary to develop the technical means to store
area wastes temporarily at centralized points, before
transfering them to existing waste treatment centres in other
regions.
Recently, such regional temporary storage centres for
wastes were created. Although they are at present few in
number, they allow a better channeling of wastes and even
C-21
-------
earmark certain wastes -for subsequent valorisation, instead of
disposal.
These centres are equipped for reconditioning wastes
(separating them into homogeneous batches for easier
disposal). The wastes are then shipped to the appropriate
collective waste treatment centre. The transfer centre groups
wastes in quantities generally between SO and 100 litres in
drums and 1 to 10 metric tonnes -for bulk wastes.
3.6 Technical Land-Burial Centres
Not all special wastes require incineration or
detoxification and for many of these wastes (particularly
those containing the lowest concentrations of toxic elements)
storage in landfill or dump facilities is a necessary and
technologically accepted disposal solution, provided certain
specifications are respected.
Technical land-burial centres can be established only in
geologically favourable areas
-------
When tha ground is impermeable, all the water penetrating
into the site accumulates at the bottom o-f the pores. It is
therefore important to restrict the amount o-f water coming
onto the site. Water contained at a site can come -from several
sources:
a) rain-fall at the site;
b) diversion o-f surface water or leachates, surfacing of
groundwater or return seepage;
c) water from pasty wastes or sludges.
The first source listed is not easily controlled. The
only means of limiting this factor is through the selection of
special sites or the reduction of the exposed surface-area.
The second source is controllable: one simply has to seal
the site environmentally, both the sides and the base, and to
build channels permitting water to run off beyond the site
without coming into contact with the contents of the site.
The third source can be controlled by limiting the
humidity of the waste accepted. Several techniques are
available: dehydration of sludge through a filter press or a
band filter, perhaps after flocculation; use of solidification
techniques for dehydration] confinement of pollutants in a
cement structure.
When the site is not totally impermeable, water passing
through the site could filter into groundwater, presenting a
risk of polluting this water. However, soil does have a
certain retaining power, in particular in the case of heavy
metals.
The principal criteria for acceptance of a waste product
by a landfill are:
1) dryness
2) The nature of the soluble fraction obtained from leaching
of the waste.
C-23
-------
The table 3»low presents a list a* acceptance criteria*
1) Concerning the paw wast*
a) Dryness > 40 '/.
b) Soluble fraction < 10 '/.
cy Hydrocarbon content: total hydro-
carbons ......< 10 X
2) Concerning the leachable natter:
a) pH 6 < PH <8
b) Metallic elements
1) Cr VI, AS 3*, Organic Kg and
Fb, CH < 10 mg/kg of waste
2> Ag, Cd, Se, Th, Hg, Pb-M-. ....< 100 mg/kg of waste
3) Ba, Va, Sn, Cu, F-r S 2-, mineral Pb,
Al, tin, Ni, In, As3+, Cr3>....< lg/kg of waste
c> Organic substances
1) Substances extractable from
chloroform < 12O g/ko of waste
2) phenols < 200,-ng/kg of waste
3> DCO < 2° 9^kQ o DgQ 5...., < 7 g/kg of waste
S) Nitrogen measured by Kjeldahl
method (expressed in NH4+>....< 2.5 g/kg of waste
d) Ecotoxity < 1 equitox/m3
Most technical land-burial centres receive both
industrial ana household wastes. Considering the current
difficulty in opening new Class 1 sites, it would be
preferable to restrict their use for wastes which could be
treated in Class 2 sites.
The eleven (11) Class 1 technical land-burial centres
received nearly 500 000 metric tonnes of special
industrial wastes in 1988. Today, the major problem with
this type of facility is obtaining their acceptance by
people living nearby. Consequently, no new site has been
opened for five years.
C-24
-------
Conclusion
Industrial wastes management long consisted in skimming
off a -few wastes with a known market value (such as scrap
iron, non-ferrous metals, waste paper and cardboard, etc.)
while summarily - and -frankly, even recklessy - disposing of
all the other wastes.
The concern for better protection o-f the environment and
for a better control o-f raw materials and energy has led to
more rational and more effective management of industrial
wastes.
Better knowledge of wastes* characteristics, better
sorting of wastes at the source, and appropriate conditioning
are prerequisites if one desires the best possible disposal
(and, if possible, valorization) of wastes.
The proper management of wastes produced by firms rests
on several principles:
1) The organization of waste storage must take environmental
and security constraints into account, but it must also
respect the limitations imposed by subsequent treatment
of the wastes, in order to reduce costs.
2) The choicp among waste treatment by the firm itself or by
collective treatment facilities depends on the amount of
wastes to be treated and on the firm's possibilities of
using th« products (or energy) obtained from
valorization.
3) The choice between various waste treatment services depends
on th« total wasts treatment costs (including transport
costs)| clean technology and valorization should be given
preference because of the economic advantages they often
present in comparison to disposal.
At a national level, for more than ten years, public
authorities have actively supported the establishment of a
national network of collective disposal centres for industrial
wastes. This support has been translated principally into a
C-25
-------
more demanding legal and regulatory framework (for example,
the Lam of 15 July 1973 on waste disposal and the Law of 19
July 1976 on facilities classified as being for the protection
of the environment), the establishment of incentives
(financial aid for investments) and unflagging support of
research seeking to improve treatment techniques.
This combined effort from the public and private sectors
toward the same goal - the effective treatment of industrial
wastes - has led to providing France with a dense, if not yet
totally sufficient, network of collective treatment centres
for industrial wastes. This network is insufficient in that
certain regions severely lack technical land-burial centres
and that, nationally, France has yet to solve the problems of
disposing of certain categories of wastes which, at the
current state of technology, require deep storage.
The steady, regular progression of Creating toxic and
hazardous industrial wastes in collective centres
(500 000 metric tonnes in 19B2 ; nearly 1 030 000 metric
tonnes in 1988 in addition to constantly improving
effectiveness of treatment techniques is a sign of a
certain level of success in this sector and also sign of
a real need on the part of industrial waste producers.
Even if, at a local level, technical landburial centres
are less and less easily accepted by the population, the
environment has everything to gain from an effective
network of collective industrial waste treatment
centres.
C-26
-------
INDUSTRIAL WASTE PRODUCTION
IN FRANCE
INERT
WASTES
100 Mt
TOTAL AMOUNT
150 MILLION TONS
COMMERCIAL
WASTES
32 Mt
SPECIAL
WASTES
18Mt
HAZARDOUS
WASTE
4Mt
C-27
-------
ANNEXE 1
INDUSTRIAL WASTES MANAGEMENT
Plant
RECYCLING
VALORISATION
C-28
-------
HAZARDOUS WASTE TREATMENT
FACILITIES
o
I
ro
INCINERATION
SPECIFIC INCINERATOR
CEMENT KILNS
POWER STATION
MUNICIPAL WASTE
INCINERATOR
PHYSICO-CHEMICAL
TREATMENT
OXYDAT1ON REDUCTION
DESHYDRATATION
FIXATION
EMULSION BREAKING
LAND BURIAL
SECURE LANDFILLS
SALT MINE
BURIAL
-------
INDUSTRIAL WASTE TREATMENT PLANTS
IN FRANCE (1990)
SCF(Gargenvllle)
SITREM(Nolsy La Sec) SCF(Barlln)
SOLUNOR(Balsleux)
"EDF-TIRU VICAT(Pont a Vendln)
SARPJLImay) (|vry ,ur
jv^ >^T^ VlpAM(Ajnlant)
COHU(Llllebonne) ,i|SEDIBExYst
SCF(Cantln)
HBNPC(Courrlere)
SIRIEOM(Douchy)
;P(Mltry-Mory)
SOTREMO(La Mans)
VICAT(Xeulllay)
SOTREFI
Mandeure)
LAFARGE(Frangey)
•\
SCF(Betfes)
SCF(Alrvault)
IT] v
ANTIPOL(Fontenay La Comte)
C3F(Flrmlny)
SIAP(Bassens)
L'ELECTROLYSEfLatresne)
SOBEGI(Mourenx)
CEDILOR(Jouy aux Arches)
TREDI
(Strasbourg)
TREDI(Hombourg)
CIMENTS DE CHAMPAGNOLE
(Rochelort Sur Nenon)
| CIMENTS DE CHAMPAGNOLE
(Champagnole)
TREDUSt vulbas)
VICAT(Montallau)
SPUR(La Talaudiere) " ~~^
' * * \ u c~ \.
•LAFARGE(Le Tell) lEfl £^S* \
i / v " 'v ^ i **' * *
J-/ \ A ff I SIRA(Chassa Sur Rhone)
LAFARGE(Lexos) L^ Pvl>^' (^ 1
iSCF(Beaucaira) /
< /
Malta)
COHU(La Mod«)
INCINERATION PLANT
UJflSTE BURNING CEMENT QJORK
PHYSICAL AND CHEMICAL TREATMENT
EUHPO-INCINERRTION PLRNT
C-30
-------
HMOUNTS OF UJflSTES DISPOSED OF
IN COLLECTlUt TREflTMENT UNITS
Tonnes
1200000
1000000 -
800000-
600000-
400000 -
200000-
506000
603000
626000
6S8000
779000
892000
3
1030374
1982 1983 1984 1985 1986 1987 1988
TOTHL RMOUNTS
-------
400000 -
300000 -
200000 -
100000 -
u
C-32
-------
INDUSTRIE. QJflSTE INCINERflTION
CO
00
800000-
600000-
400000-
200000-
363000
419000
486000
567000
655000
800000
1984 1985 1986 1987
1 988
1989
-------
o
OJ
RMOUNTS OF UJRSTES DISPOSED OF
IN COLLECTIIJE TREflTMENT UNITS
DETOHICRTION UNITS
T<
400000 -
300000-
200000 -
100000 -
0 -
innes
y
/
s
/
/
/
271000 1
:
1
1
s
292000
/
2S9000
X' f
317000
X .
3e «> n c A
O Z 51 D *\ K
rr
1984
1985
1 986
1987
1988
-------
TECHNICAL LAND-BURIAL CENTRES
( SECURE- LflNDFILLS)
MENNEVILLE
GUiTRANCOURT
TOURVILLE LA RIVIERE
ARGENCES
LAIMONT
VILLEPARISIS
JEANDELAINCOURT
/
VAIVRE
CHAMPTEUSSE SUR BACONNE
PONTAILLER SUR SAONE
BELLEGARDE
C-35
-------
I WASTE ACCEPTANCE PROCEDURE 1
WASTE PF
CwUUULK |\
i
WASTE SAMPLE
^
TREATMEN
SAMPLE /
IF CENTER
i
ANALYSIS
^x^COMPATIBLE^N. , „
< WITH ACCEPTANCE J> 4 R
\. CRITERIA .X^
ACCEPTANCE CERTIFICATE
\
WAStE pRObUCER
l
WAStE CONSIGNMENT
UNIQUE OR REGULAR
>
tREAIMtN
i
/
T CENtER
i
SAMPLING
1
SIMPLIFIED ANALYSIS
\
.X^COMP
A KF
i
EATMENT
OF DISPOSAL
FUSE 1
C-36
-------
TECHNICAL DATA FOR
INCINERATION CENTERS
ACCEPTANCE CRITERIA
- Calorific value (combusiion control)
- Halogen content (need for specific
centre)
- Metal content (alkaline elements)
• Flash point (security)
- Physical aspect (liquid, solid or pdsty)
COMBUSTION
From 750° C (simple organic wastes)
To 1 200° C (organo-halogenated wastes)
Time : 2 sec
Post-combustion necessary
GASES MAIN PARAMETERS
Cl < 100 mg/N.m3
Dust < 150 mg/N.m3
Heavy metals < 6 mg/N,m3
-------
RMOUNTS OF UIRSTES DISPOSED OF
IN TECHNICRL LHND-BURIHL CENTRES
CO
CO
Tonnes
ISOOQOOi
1250000-
1000000-
750000.
500000
250000.
1985 1986 1987 1988
DECHETS INDUSTRIELS SPECIAUX IMPORT
DECHETS INDUSTRIELS SPECIAUX FRANCE
ORDURES MENAGERES, DECHETS BANALS
-------
TECHNICAL LAND-BURIAL
CENTRES
SITE QUALIFICATION
.9
Impermeable site : permeability < 10 rn/s
substratum > 5 m
Water protection (surface and underground)
isolation from surroundings
ACCEPTANCE CRITERIA
- Water content
- Physical aspect (solid ou pasty)
- Nature of soluble fraction (leachate test)
- Prohibited substances (PCB, cyanides,
explosives,...)
C-39
-------
C-40
-------
DICK JANSSEN
NATO/CCMS Guest Speaker
C-41
-------
Degradation of halogenated aliphatic compounds by specialized
microbial cultures and their application for waste treatment
D.B. Janssen, A.J. van den Wijngaard and R. Oldenhuis
Department of Biochemistry
University of Groningen
The Netherlands
Prepared for:
4th NATO/CCMS Pilot Study on Demonstration of Remedial Action Technologies
for Contaminated Land and Groundwater, Angers, November 5-9, 1990.
C-42
-------
Abstract
The biodegradation of halogenated aliphatic compounds by a number of
pure bacterial cultures was investigated. It was found that 1-chloro-n-
alkanes, several a.u-dichloroalkanes, chlorinated alcohols and some
chlorinated ethers can be used as sole carbon source by various gram-
negative or gram-positive organisms. Attempts to isolate bacteria that can
grow with compounds such as chloroform, 1,1-dichloroethane,
dichloroethylenes, trichloroethylene and 1,1,1-trkhloroethane were not
succesful. Methanotrophic bacteria, however, could convert these compounds
by cometabolic oxidation to alcohols or epoxides that may decompose
chemically.
Application of microorganisms that use pollutants for growth seems
promising in the areas of waste gas treatment and soil cleanup. Thus,
addition of dichloromethane-degrading organisms to soil slurries
contaminated with this compound resulted in shorter adaptation periods than
in non-inoculated soil. Processes that rely on cometabolic conversions are
more difficult to realize. Other methods for selective stimulation of the
active organisms than the presence of growth substrate need to be employed
and an additional energy source will be required.
C-43
-------
Introduction
Chlorinated hydrocarbons have found extensive application as
degreasing agents, solvents, intermediates in chemical sythesis and
agrochemicals (Table 1). Their environmental fate is determined by their
resistance to chemical decomposition, the low number of microorganisms that
are able to degrade chlorinated organics, and their water solubility and
volatility.
Table 1. Production and use of some chlorinated aliphatic hydrocarbons.
compound
1,2-dicnloroeihane
vinylchloride
perchloroethylene
tnchloroethylene
carbon tetrachlonde
1.1.1-trichlcroethane
methylene chloride
methylchloride
2-chlorobutadiene
chloroform
1,1-dichloroethylene
production
(10s tonnes /yr)
13
12.0
1.1
1.0
1.0
0.45
0.4
0.35
0.3
0.24
0.1
use
vinylchloride, gasoline
antlknocMng agents, solvent
polyvinylchloride
solvent
solvent
solvent. CMC
solvent
solvent
solvent, blowing agent
polymers
solvent, CKC
solvents, polymers
During the last several years, we have been studying the
biodegradation under aerobic conditions of several important
representatives of this class of compounds. Biodegradation rates are often
very low, and it has been observed that several chlorinated compounds may
persist in polluted aquifers for many years. The cause of these low
degradation rates could be unfavourable environmental conditions, physical
unavailability of the substrates, or the absence of microorganisms that are
able to carry out biotransformation reactions. With halogenated aliphatics,
this last factor often is of crucial importance. Even under optimal
environmental conditions (neutral pH, 20-30°C, sufficient nutrients
available), recalcitrant behaviour is often observed (Table 2). Usually,
only specific cultures have the ability to utilize these compounds for
growth (Table 3). Therefore, the development of treatment technologies for
locally polluted environments and waste streams will require an
understanding of the microbial potential and the ecophysiology of the
organisms involved. Such information will give insight in the extend of
C-44
-------
removal that can be achieved, the conditions that must be optimized and the
range of waste streams that can be treated.
Table 2. Bacterial degradation of chlorinated aliphatic hydrocarbons.
aerobic anaerobic
1-chloro-n-alkanes
dichlorome thane
chloroform
carbon tetrachloride
1,2-dichloroethane
1.1,1-trichloroethane
vinylchloride
t-1.2-dichloroethene
trichloroethylene
tetrachloroethylene
allylchloride
1.2-dichloropropane
1.3-dfchloropropene
P E
P E
R
P E
R
P E
E
R E
R
E
R E
P E
C
C
C
C
C
C
C
C
C
H
H
H
R
M
H
H
F
F
F
R. recalcitrant behaviour described
P. pure culture uses compound for growth
E, microblal enzyme capable of degradation known
C. conetabolic conversion by pure culture
H. methanogenic culture
F. fermentative culture
C-45
-------
Enrichment cultures
We have used batch and chemostat cultures for the enrichment of
microorganisms that can degrade specific pollutants (Table 3). Positive
results were obtained with all 1-chloro-n-alkanes tested, with several a,w-
dichloroalkanes, and with a number of chlorohydrins and chlorobenzenes. In
all cases, it was possible to isolate a pure culture once an actively
growing enrichment was obtained.
Table 3. Pure bacterial cultures that degrade chlorinated compounds.
Strain no. Identity
Isolated on
Degrades also
chloroahohatics
GJ1. GJ3 Pseudoaonas
GJ10-12 Xenthotacter
GJZO-2Z
GJ70
AD1-3
GJM
A025
Hyptiooncrobium
Arthrobacter
fseudooonas
Arthrobacter
Corynebacteritim
Ancylotacter
chloroaromatlcs
GJ30 Pseudomonas
GJ31 Pseudomonas
GJ60 Pseudomonas
2-chloroethanol
1,2-dichloroethane
methyiene chloride
1.6-dichlorohexane
epichlcrohydrin
trans-3-chloroacryl1c
acid
chloroethylvinyletner
chlorobenzene
chlorobenzene
1.2-dichlorobenzene
chloroacetic acid
toluene, methanol
1-propanol, acetone
chloro- and bromoalkanes
formaldehyde
1-chloroalkanes
1.9-dichlorononane
vic-chlorohydr1ns
cis-3-chloroacryllc
acid
2-chloroethanol
1.2-dichloroethane
toluene, benzene
1,2,4-dichlorobenzene
1,4-dichlorobenzene
toluene, benzene
All enrichments were negative with chloroform, 1,1-dichloroethane, 1,1,1-trichloroethane,
l,l-d(chloroethylene, cfs-1,2- and trans-l.2-d1chloroethylene, trkhloroethylene, perchloroethylene.
1.2-dlchloropropane, hexachlorobutadlene and hexachlorobenzene.
It was observed that the outcome of an enrichment experiment was
strongly influenced by the nature of the inoculum and the identity of the
compounds. All soil and sediment samples used were positive when tested for
chloroacetic acid degradation, but only a limited number of inocula gave
rise to dichloromethane utilizing enrichments, while 1,2-dichloroethane
degradation was even more seldom observed.
The pure cultures that were isolated in general had a broad substrate
range. Thus, 1,2-dichloroethane degrading Xanthobacter strains (Janssen et
C-46
-------
al., 1985) also converted several 1-chloro- and 1-bromo-n-alkanes, and even
toluene, acetone, 1-butanol, etc., were used for growth (Table 3). A
similar broad substrate range was found for the 1,2-dichlorobenzene
degrading organism strain GJ60 (Oldenhuis et al., 1989a). Toluene, benzene,
chlorobenzene, 1,4-dichlorobenzene and 1,2,4-trichlorobenzene also
stimulated growth of this organism (Table 3).
An important aspect is the stability of the cultures. This was found
to be highly variable. Some strains did not show loss of their specific
catabolic activity even when they were transferred on selective media for
years, while other cultures had to be maintained on the carbon source that
was used for enrichment to prevent rapid loss of their activity. This was
not related to the compound on which the organism was obtained, since
strain GJ31 was a very stable chlorobenzene degrader while GJ30 rapidly
lost its activity on nutrient agar.
Repeated attempts to obtain enrichments for a number of compounds
were not successful. This included chloroform, 1,1-dichloroethane, the
dichlorinated ethylenes, trichloroethylene, and some other compounds. A
number of factors could cause that a specific xenobiotic is not used for
growth:
- the compound or intermediates are not converted by microbial enzymes;
- degradation does not yield energy or carbon for growth;
- the compound is toxic;
- the compound is converted to toxic metabolites (Fig. 1).
CH2Br-CH2Br
Bf
—^- CH23r-CH,OH =» CH23r-CHO
I
CK2OH-CH,OH CHjOH-CHjOH CH23r-COOH
'Br'
CHjOH-COOH
Fig. 1. Possible conversions of 1.2-dibronoethane by different bacterial cultures. Several enzymatic
steps enabling dehalogenation and utilization of this compound have been identified. The
necessary combination of theseactivities, yielding a complete catabolic route, however, has not
yet been found.
In order to understand the relative importance of these factors, we
have decided to study physiological pathways through which halogenated
aliphatics can be converted. Special emphasis was given to dehalogenation
reactions since this is the step where toxicity is lost. It can also be
expected to be a biochemically difficult step, since carbon-halogen bonds
are only present in a limited number of natural compounds.
C-47
-------
Dehaloqenation
Dehalogenation of several chloroalkanes was found to be mediated by
low molecular weight hydrolytk dehalogenases. The first enzyme that was
found to be able to hydrolyze a chlorinated hydrocarbon not containing
other functional groups was identified in a strain of Xanthobacter that was
isolated on 1,2-dichloroethane (Janssen et al., 1985; Keuning et al., 1985)
(Fig. 2). A hydrolytic dehalogenase was also identified in a 1,6-
dichlorohexane utilizing organism (Janssen et al., 1988b). A broad range of
compounds could be converted by these systems (Table 4).
CH,Cl-CHjCl
holooltane
oehclogenose
. .,. ___________ _____ ... ___________ ..... .... dhIA
by Xanthobacter autotrophicus. Two CfyCI-Cr^OH
different hydrolytic dehalogenases. L- PQQ alcohol
produced constltutlvely. cause
dechlorinatlon. The haloalkane CrfcCI-CHO
dehalogenase has a remarkably broad
t
CI-
L- PQQ
J* POOH2
CI-CHO
dehalogenase has a remarkably broad I
_,. , _ ,_, L- NADt H,0 aldehyde
substrate range. The Induclble T NAW ' ftn
dehydrogenases are usual enzymes of ' 2 old
Jfantnohacter and play a role In the CHjCl-COOH
metabolism of natural alcohols. The U H20 naiodkonoic oetd
final product, glycolic acid, Is a f HCI 'SJ
normal intermediate in bacterial meta- CHjOH-COOH
bolism. I
central metabolic routes
Recently, the three dimensional structure of the Xanthobacter
dehalogenase has been resolved (S. Franken, B. Dijkstra et al., in
preparation). The structure suggests the involvement of a carboxylate group
in the dehalogenation reaction, which would proceed by a nucleophilic
desplacement mechanism. If this is correct, then It is evident why
compounds such as chlorinated ethylenes are not a substrate. The presence
of T: electrons shields the carbon from nucleophilic groups. Compounds such
as chloroform and 1,1,1-trichloroethane probably are not converted because
of steric factors.
We have observed a striking degree of correlation between the
possibility of hydrolytic dehalogenation and utilization as a growth
substrate. One of the compounds for which repeated attempts to isolate a
pure culture were not succesful is 1,2-dichloropropane. This chemical has
entered the environment due to contamination of the nematocide 1,3-
dichloropropylene. It also is an industrial waste chemical. The compound
is known to persist in the groundwater environmental for decades.
C-48
-------
Table 4. Substrates of haloalkane dehalogenases.
Compound
GJ10
GJ70
Compound
GJ10
GJ70
methyl chloride
methylbromide
methyl iodide
dibromome thane
bromochlorome thane
ethylchloride
ethylbromide
ethyl iodide
1.2-dichloroethane
1.2-dibromoethane
1-chloropropane
1-bromopropane
2-bromopropane
1.3-dichloropropane
3-chloropropene
1.3-dichloropropene
1.2-dlbronopropane
1-chlorobutane
1-bromcbutane
2-bromobutane
28
14
14
-
-
24
24
-
100
94
51
29
-
60
45
-
119
31
27
•
0
143
75
13
5
0
143
93
13
172
15
100
97
102
139
133
148
66
90
60
2-bromoethanol
3-bromopropanol
l-chloro-6-hexanol
l-bromo-6-hexanol
bis(2-chloroethyl)ether
chloroethylvinylether
l-phenyl-2-bromopropane
1-chloropentane
1-bromopentane
2-bromopentane
1-chlorohexane
1.6-dichlorohexane
2-bromooctane
1.9-dichlorononane
1.2-dichloropropane
epichlorohydrin
epibromohydnn
7
.
4
.
-
-
.
0
32
-
3
4
.
4
0.6
14
129
55
123
60
68
30
13
18
65
60
38
85
67
.
26
.
-
-
Relative activities of purified dehalogenase of Xanthobacter autotrophicus GJ10 and Arthrobacter GJ70.
The purified enzymes have an activity of 6 and 3 U/mg of protein, respectively, with 1,2-dibromoethane.
We propose that this recalcitrance is related to the extremely low activity
of hydrolytic dehalogenases towards this compound. The strain GJ10
dehalogenase described in Table 4 has a 160-fold lower activity with 1,2-
dichloropropane than with 1,2-dichloroethane. The product of conversion is
a mixture of l-chloro-2-propanol and 2-chloro-l-propanol, which both may
serve as carbon source for cultures that have been obtained in our
laboratory (Fig. 3). Therefore, the lack of conversion could be related to
a single activity being absent.
Cl Cl
hyflrelytic
denalogenase
H,0
OH Cl Cl
CH3-CHz-CHj
Fig. 3. Conversion of 1.2-dicnlorcpropane by hydrolysis (haloalkane dehalogenase) or by oxidation
(methane monooxyger.ase).
C-49
-------
Other mechanisms of dehalogenation have been discovered in
dihalomethane degrading organisms and in strains that use haloalcohols for
growth. Apparently, there are two possible routes for the direct
dehalogenation of haloakohols: hydrolysis to produce glycols or
intramolecular substitution to produce epoxides (Fig 4).
Fig. 4. Catabolism of epichlorohydrin in Pseudcnonas
A01 involves the activity of an epoxide
hydro Use and a dehalogenase that converts
vicinal alcohols to epoxides. Both enzytres are
inducible (van den Hijngaard et al., 1989).
HjC-CH-CHjCI
i
OH OH
1
OH
\
^C- CH-CKj
I?
OH OH OH
H2C- CH-CHj
Little is known about the conversion of B-halocarboxylic acids.
Oxidative conversions seem to be rather widespread but their
relevance to organisms that use halogenated compounds as a carbon source
remains to be demonstrated.
Application of organisms
We have tested whether addition of specific cultures to slurries of
contaminated soil can decrease adaption periods or increase degradation
rates. It was found that dichloromethane removal occurred faster when
dichloromethane degrading organisms (Hyphomicrobium GJ21 or
Methylobacterium DM2) were added to contaminated soil (Fig. 5). Without
inoculation, no significant degradation took place within 100 h. Similar
results have been obtained with the degradation of chlorinated benzenes and
1 ,,2-dichloroethane. The engineering aspects of bioreactors for the
treatment of soil slurries have been investigated by others (Kleijntjes et
al., 1987).
Fig. 5. Effect of inoculation on the
degradation is soil slurries.
Symbols: I. sterile control; o, no
organ!SITS added; 4,
Hethylobacterium strain DM2 added
(Kohler-Staub and leisinger,
1985); •, Hyphomicrobium GJ21
added. Tne concentration of
dichloromethane was followed by
gas chromatography.
i.o-
r
LJ
Q
ti-
lt-
C
0)
2
20 l>0 60 60
C-50 Time (h)
- ICO ' 600
eoo
-------
Other areas of application of selected cultures are being developed.
This includes immobilization of 1,2-dichloroehane degraders for groundwater
treatment in packed bed bioreactors and the use of dichloromethane
degrading bacteria for waste gas treatment.
Oxidative cometabolism
Since 1985 (Wilson and Wilson, 1985), the possibility to convert
chlorinated ethylenes by cometabolic reactions has received increasing
attention (Fogel et al., 1986; Little et al., 1988;' Janssen et al., 1988a;
Oldenhuis et al., 1989b). Methanotrophs, toluene, propylene and ammonia
oxidizers have been tested for their capacity to degrade halogenated
aliphatics by cometabolic oxidation. The oxygenases involved have a broad
substrate range and convert chlorinated compounds to alcohols, epoxides,
etc.
Table 5. Degradation of seme halogenated compounds by soluble (sNHO) and participate (nflMO)
methane monooxygenase.
Compound
Dichloromethane
Chloroform
Carbon tetrachloride
1.1-Dichloroethane
1.2-Otchloroethane
1.1.1-Trlchloroethane
1.1-Olchlorcetnylene
trans- 1 .2-0 ichloroethylene
cis-1.2-01chloroethylene
Trichloroethylene
Tetracnloroethylene
1,2-Dichloropropane
trans-l.3-D1chloropropylene
sterile
0.167
0.124
0.046
0.033
0.092
0.065
0.030
0.083
0.110
0.050
0.069
0.129
0.138
Cone.
sKHO
<10°
c!0's
0.04S
<10-*
<10'4
0.02S
0.018
-Iff4
-------
Table 6. Degradation of chloroaliphatics by H. tric/iosporfojnOB3b.
compound chlorinated produces}'
dichloromethane chloride
chloroform chloride
carbon tetrachloride no conversion
1,1-dichloroethane chloride
1.2-dkhloroethane chloride
U.l-trichloroetliane 2,2.2-trlcnlorcethanol
trans-1.2-dichlorcethylene chloride, epoxide
cis-1.2-dichloroethylene chloride, epoxide
trichloroethylene chloride, 2,2.2-trichloroethanol
tetrachloroethylene no conversion
1,2-dichloropropane l,2-dlchloro-3-proparol
* Incubations were done at 30 *C with resting cells from chemostat cultures grown in medium
containing no added copper. Compounds were added at 0.1 nfl and formate was used as electron donor.
One of the most important compounds that can be converted by methano-
trophs is trichloroethylene. Rapid conversion of TCE was achieved under
conditions that stimulate expression of the soluble methane monooxygenase
only. The kinetics of TCE degradation by methanotrophs compares favourably
to toluene oxidizing organisms that degrade TCE (Oldenhuis et al., 1990).
The Kj values (first order rate constants) are similar but methanotrophs
have a higher V^. A problem with both toluene oxidizers and methanotrophs
is the toxicity of TCE degradation products. This will require significant
amounts of methane to stimulate growth of new active cells if in a
treatment system larger amounts of TCE have to be converted.
Application of coroetabolism
We have found that addition of methane to soil slurries that were
contaminated with chloroform, TCE and perchloroethylene only stimulated
chloroform conversion significantly (Fig. 6). In slurries that contained
tra/J5-l,2,-dichloroethylene, rapid degradation was achieved when either
methane or methane plus cells of a Methylomonas culture were added (Fig.
7). By methane addition alone, probably only cells expressing the
paniculate methane monooxygenase were stimulated. Similar observations
have been made in field studies (McCarty et al., 1989). More efficient
methods for specific stimulation of methanotrophs expressing soluble
methane monooxygenase have to be developed. Copper availability, which
regulates the switch from expression of soluble to particulate enzyme will
be difficult to manipulate in a natural environment or treatment system
-------
CONTROL
WITH CELLS AND CH;
Fig. 6. Degradation of chloroform, trichloroethylene, and perchloroethylene in a soil slurry exposed to
methane.
Fig. 7. Degradation of trans-1.2-dichloroethylene
in soil slurry.
Treatment systems
CONC.
(u.vi
30
TIME (d)
Application of selected microbial cultures for cleanup purposes can
be attractive in order to reduce adaptation periods. Several areas are
promising:
- inoculation of waste gas treatment biofilters and trickling filters;
- startup of fixed beds for groundwater treatment;
- inoculation of bioreactors for soil, sediment and sludge treatment;
- in situ treatment after injection of microorganisms.
Although the number of practical scale experiences with these
applications is very limited (Morgan & Watkinson, 1989), several
C-53
-------
considerations indicate that inoculations could be very helpful.
Natural polluted ecosystems seem to show variability with respect to
presence of microorganisms that can degrade certain pollutants. Thus,
subsurface samples often do not show significant degradation of
dichloromethane, 1,2-dichloroethane or 1,2-dichlorobenzene unless
microorganisms that are capable to use these compounds for growth are
added. Cultures that degrade xenobiotics are not always present in a
certain polluted environment and this may prevent degradation even after
conditions have been optimized.
Experiments with trickling filters for waste gas treatment also show
that inoculation may be useful for obtaining rapid establishment of an
active microflora (Oiks and Ottengraf, 1989).
Cells immobilized on a solid support can be used for groundwater
cleanup. Both activated carbon (Stucki, 1990) and diatomeceous earth
(Friday and Portier, 1989) have been used as support material for the
Xanthobacter strain that degrades 1,2-dichloroethane. These systems are
currently scaled up for practical application.
Novel developments will be the application of microorganisms that
rely on cometabolic conversion. On a laboratory scale, several interesting
reactor setups have been proposed, but the efficiency seems to need further
improvement (Strandberg et al., 1989).
Another attractive possibility is the combination of anaerobic and
aerobic treatment steps for complete dehalogenation of compounds that are
not converted under aerobic conditions. Highly chlorinated compounds are
subject to reductive dehalogenation, catalyzed by anaerobic organisms such
as clostridia and methanogens (Vogel et al., 1987). The products could be
converted further by aerobic treatment.
In all cases, more insight into the ecophysiology of the organisms
that carry out the dehalogenation steps will be essential for identifying
the basic process conditions that are needed for optimizing the numbers and
activity of the xenobiotic degraders. The use of bioreactors that allow
fine control of growth conditions will increase the success of these novel
treatment technologies.
C-54
-------
Literature cited
Oiks, R.M.M, & S.P.P. Ottengraf. 1989. Prozesstechnolcgische Aspekte der Abscheidung von chlorierten
Kohlenwasserstoffe aus der Abluft in Biotropfkorper. VDI Berichte 735:7-24.
Fogel, H. M., A. R. Taddeo, and S. Fogel. 1986. Biodegradation of chlorinated ethenes by a
methane-utilizing mixed culture. Appl. Environ. Hicrobiol. 51:720-724.
Friday. D.D., and R.J. Portier. 1989. Evaluation of a packed bed inncbilized microbe bioreactor for the
continuous bicdegradation of halocarbon- contaminated groundwater. AKMA/EPA International Symposium on
Biosystems for Pollution Control, dncinatti.
Janssen. D.B., A. Scheper. L. Dijkhuizen. and B. Hitholt. 1985. Degradation of halogenated aliphatic
compounds by Xanthotecter autotrophicus GJ10. Appl. Environ. Hicrobiol. 163: 635-639.
Janssen, D.B.. G. Grobben, R. Hoekstra. R. Oldenhuis, and B. Hitholt. 1988a. Degradation of
trans-1.2-dichloroethene by mixed and pure cultures of methanotrophic bacteria. Appl. Hicrobiol. Bio-
technol. 29:392-399.
Janssen. D.B.. J. Gerntse. J. Brackman, C. Kalk. 0. Jager, and B. Hitholt. 19885. Purification and
characterization of a bacterial dehalogenase with activity toward halogenated alkanes, alcohols, and
ethers. Eur. J. Biochem. 171:67-72.
Keuning, S., D.B. Janssen, and B. Hitholt. 198S. Purification and characterization of hydrolytic
haloalkane dehalogenase from Xanthobacter autotrophicus GJ10. J. Bacteriol. 163:635-639.
Kleijntjes. R.H., K.Ch.A.H. Luyben. H.A. Bosse. and L.P. Velthuisen. 1987. Process development for
biological soil decontamination in a slurry reactor. Proc. 4th Eur. Congr. Biotechnol. 1:252-255
(Elsevier, Amsterdam).
Kohler-Staub. D, and T. Leisinger. 198S. Dichloromethane dehalogenase of Hyphomicrobium sp. strain DK2.
J. Bacteriol. 162:676-681.
Little. C. 0.. A. V. Palumbo. S. E. Herbes. M. E. Lidstron, R. L. Tyndall. and P. J. Gilnter. 1988.
Trichloroethylene biodegradation by a methane-oxidizing bacterium. Appl. Environ. Hicrobiol. 54:951-955.
McCarty, P.L., L. Seifipnni, and P.V. Roberts. 1989. Methodologies for evaluating the feasibility of
in-situ biodegradation of halogenated aliphatic groundwater contaminants by tnethanotrophs. Proc.
AHHA/EPA international Symposium on Biosystems for Pollution Control. Cincinatti.
Morgan. P., g R.J. Hatkinson. 1989. Microbiological methods for the cleanup of soil and ground water
contaminated with halogenated organic compounds. FEKS M^crobiol. Rev. 63:277-300.
Oldenhuis. R.. L. Kuijk. A. Lairmers, O.B. Janssen. and B. Kitholt. 1989a. Degradation of chlorinated and
non-chlorinated aromatic solvents in soil suspensions by pure bacterial cultures. Appl. Hicrobiol. Bio-
technol. 30:211-217.
Oldenhuis. R.. R.L.J.M. Vink. D.B. Janssen. ana B. Hitholt. 1989b. Degradation of chlorinated aliphatic
hydrocarbons by Mettiylosinus trichosponum OB3b expressing soluble methane monooxygenase. Appl. Environ.
Hicrobiol. 55:2819-2826.
Oldenhuis. R., J.Y. Oetzes. J.J. van der Naarde, and D.B. Janssen. 1990. Kinetics of chlorinated
hydrocarbon degradation by Hettiylosinus trichosporiumOB3b and toxicity of trichloroethylene. Appl
Environ. Hicrobiol. 57, in press.
C-55
-------
Strandberg, G.W., T.L. Donaldson, and L.I. Farr. 1939. Degradation of trichloroethylene and
trans-1.2-dichloroethylene by a methanotrophic consortium in a fixed-film, packed-bed bioreactor.
Environ. Sci. Techno 1. 23:1422-1425.
Stuck5, G. 1990. Biologische Entsorgung von CKH's aus Grundwasser und aus Mutterlaugen von chennschen
Prozessen. In: Proc. 7. Oechema-Fachgespr. Umneltsch. Anwendung von speziellen Hikroorganismen zur
Behandlung von Abwassern mit schwer abbaubaren inhaltsstoffen, 12-13 Ma'rz 1990, Franfurt am Main.
Vogel, T. M.. Criddle. C. S. and NcCarty, P. L. 1937. Transformations of halogenated aliphatic
compounds. Environ. Sci. Technol. 21:722-736.
Wilson, J.T.. and B.H. Wilson. 1985. Biotransformation of trichloroethylene in soil. Appl. Environ.
Hicrobiol. 49:242-243.
Van den Wijngaard. A., D.B. Janssen. and B. Hitholt. 1989. Degradation of epichlorohydrin and
halohydrins by three bacterial cultures isolated from freshwater sediment. J. Gen. Microbiol., 135:2199-
2208.
C-56
-------
DOUGLAS AMMON
NATO/CCMS Guest Speaker
C-57
-------
Presentation of
Clean Sites
to the
NATO/CCMS PILOT STUDY
DEMONSTRATION OF REMEDIAL ACTION TECHNOLOGIES
NOVEMBER 1990
CLEAN SITES
-------
This is Clean Sites
A non-profit institution devoted solely to helping speed up the
effective cleanup of hazardous waste
o
VO
A neutral and objective third party
+ Working with involved parties
* Toward voluntary private settlements and site cleanups
Five functional groups:
Settlement Services
Technical Affairs
Project Management
Public Policy & Education
Administration
CLEAN SITES
-------
Clean Sites' Background
Creation involved industrial and environmental groups, EPA, and
Justice Department
Formal establishment May 31,1984
General contributions from 140 companies, 8 foundations,
50 individuals
Site-specific cost reimbursement
Staffed by approximately 50 experienced professionals
CLEAN SITES
-------
Clean Sites' Board of Directors
Mr. Peier A.A. Berle
President
National Audubon Society
Hon. Douglas M. Costle
Dean, Vermont Law School
Prof. Archibald Cox
Professor Emeritus
Harvard Law School
Dr. Louis Fernandez
President
Celgene Corporation
Dr. Edwin A. Gee
Chairman and C.E.O., Retired
International Paper Co.
Mr. Thomas P. Crumbly
President and Treasurer
Clean Sites, Inc.
Dr. Jay D. Hair
President
National Wildlife Federation
Dr. Donald Kennedy
President
Stanford University
Ms. Susan B. King
President
Steubcn
Mr. H. Eugene McBrayer
President
Exxon Chemical Company
Dr. Gilbert S. Omenn
Dean, School of Public Health
and Community Medicine
University of Washington
Richard Cooper (Secretary)
Williams and Connolly
Dr. Charles W. Powers
Partner, Resources for
Responsible Management
Founding President, Clean
Sites, Inc.
Hon. Robert T. Stafford
U.S. Senator, Retired
Mr. Roger Strelow
Vice President
Bechtel Corporation
Hon. Russell E. Train (Chairman)
Chairman, World Wildlife Fund
& The Conservation Foundation
Mr. Hans A. Wolf, Vice Chairman
& Chief Administrative Officer
Syntex Corporation
CLEAN SITES
-------
r»
i
PO
Why Parlies Use Clean Sites
Sole mission is facilitating hazardous waste cleanup
Highly qualified and experienced staff
Provides a complete set of services to support cleanup of waste sites
Assisted at over 60 waste sites
Prepared more than 25 cost allocations
Credibility and fairness
Access, if necessary, to unique Board of Directors and Scientific and
Technical Advisory Board
Sensitive to needs of the parties
CLEAN SITES
-------
Clean Sites Organizational Structure
Board of Directors
Russell E. Train, Chairman
President
Thomas P. Crumbly
Executive
Vice President
Robin Robinson
Vice President
Settlement
Services
James Kohanek
Vice President
Public Policy
& Education
Nancy Newkirk
Vice President
Project
Management
George Murray
Vice President
Technical
Affairs
Richard Sobel
C-63
-------
Unique Role of Clean Sites
en
Settlement Services
4- Dispute Resolution and Cost Allocation
Technical Assistance
Project Management
Services to Government Agencies
Funds Management
Information Services
Public Policy and Education Activities
CLEAN SITES
-------
The Role of Clean Sites
^^" -x^"
Site discovery/
inventory
^
-^
a
_-x*** ^^
Site
inspection
-*>
-^
^^ ^r
Assign national
priorities
i
a\
tn
Organizing PRPs
Bringing additional PRPs to
the negotiations
Identifying issues, setting
agendas
Resolving disputes among
settling parties
Coordinating and exchanging
information with government
to reach settlement
EPA notification
of potentially
responsible partie
Remedial invest./
feasibility study
r***'*" ^^"^^" -^*r
Record of
decision
Remedial
action
-------
The Role of Clean Sites
^x^ ^x**"
Site discovery/
inventory
9
^r- ^*
Preliminary
assessment
^^9 ^t
i^^
^^ ^*-
Site
inspection
^
j-^-^ ^x*
Assign national
priorities
o
01
• Dividina costs of studies
• Reaching settlement agreements
for studies
,^r
^^
_^
^
"j
^
EPA notification
of potentially
•esponsible partie
^4J^-
Remedial invest/
feasibility study
^-^i^-
Record of
decision
J Lx^-
^^* ^*
-------
The Role of Clean Sites
^ ^1
Site discovery/
inventory
^
^ 3^
Preliminary
assessment
^
Lx- 3^1
Site
inspection
dd ^v
^^^
i^x- ~^^\
Assign national
priorities
o
(71
• Dividing costs for cleanup
• Reaching settlement agreement
for cleanup
• Begin planning for
cleanup activity
~+
.x*"^ ft
V
EPA notification
of potentially
•esponsible partie
emedial invest./
feasibility study
Record of
decision
Remedial
action
-------
The Role of Clean Sites
^x^ f**f'
Site discovery/
inventory
^
^r ^s*
Preliminary
assessment
^
~£
^r- - --^*-
Site
inspection
>
^** -^^
Assign national
priorities
o
I
a*
CO
Planning cleanup
Coordinating cleanup with
settlement
Ensuring cleanup meets state
and federal requirements
Dividing O&M costs
Reaching settlement for
O&M costs
EPA notification
of potentially
responsible partie
Remedial invest./
feasibility study
Record of
decision
Remedial
action
-------
Clean Sites' Activities Do Address Some Major Impediments to Cleanim
o\
VO
Impediment
• Fund is being depleted; transaction
costs are inordinately high
o Cleanup is a long and expensive
undertaking
Clean Sites' Role
• Encourage private party
cleanup and facilitate
settlements (dispute resolution)
• Bring more parties into the
process (cost allocation/dispute
resolution)
e Control costs of cleanup
without sacrificing
environmental protection
(project management)
-------
Clean Sites' Activities Do Address Some Maior Impediments to Cleanup
Impediment
• Public has little faith the government
is protecting them
Private party and EPA site studies
suffer a "credibility gap"
Some believe benefits of Superfund
are not worth the cost
Clean Sites' Role
• Inform the community about site
activities throughout the study
and cleanup process (project
management)
• Oversight of private party
studies to assure they meet EPA
requirements and are technically
sound (technical assistance)
• Provide information to all
parties about ways to speed
cleanup without undermining
the goals of Superfund (public
policy and education)
-------
o
I
CLEAN SITES'
PUBLIC INTEREST ACTIVITIES
Evaluate the current EPA Superfund remedy selection
process and make recommendations for change.
Provide free assistance to citizens to help them obtain
Superfund Technical Asstance Grants from EPA.
Conduct educational seminars entitled Successfully
Resolving Multi-Party Hazardous Waste Disputes.
providing scholarships to government officials to f aciliate
their attendance.
Analyze the impact of hazardous waste disposal on the
rural poor for the Ford Foundation.
Authored a paper entitled "Making Superfund Work", an
analysis of and recommendations for the Superfund
program, which was presented to the Bush transition team.
sCLEAN SITES
-------
CLEAN SITES'
PUBLIC INTEREST ACTIVITIES
continued
Conduct the Community Industry Forum - a series of
facilitated dialogue sessions between citizens and PRPs
involved at Super fund sites.
Facilitate policy dialogues between EPA and other interest
groups involved in the super fund process.
Perform initial mediation and facilitation services at
selected Superfund sites free of charge to help organize
PRP groups and to facilitate settlement.
CLEAN SITES
-------
Public Policy and Education Activities
(continued)
o
1
(*»
Provide policy, legal and technical support to help state agencies
develop their own Superfund programs.
Develop (in conjunction with the Environmental Law Institute) a State
Superfund Information Network to facilitate sharing of information
between states.
Facilitate policy dialogues between EPA and other interest groups
involved in the Superfund process.
Perform initial mediation and facilitation services at selected
Superfund sites free of charge to help organize PRP groups and to
facilitate settlement.
CLEAN SITES
-------
CLEAN SITES' ASSISTANCE TO STATE
SUPERFUND PROGRAMS
Provide policy, technical, legal support to State hazardous
waste cleanup programs. Clean Sites helps states develop:
a Regulations
• Site cleanup related procedures
• Settlement, enforcement and administrative policies
• Program management tools
• Training courses
CLEAN SITES
-------
c->
en
Technical Affairs
Technical staff manages and reviews site cleanup studies, advises
responsible parties and their contractors
Goal is to ensure quality and content in studies as needed by EPA to
select appropriate remedy
Assist parties to resolve technical disputes
Technical Advisory Board, whose members have international
stature in their speciality areas, supports in-house staff
Conducting an independent analysis of the Superfund remedy
selection process under EPA grant
CLEAN SITES
-------
Scientific & Technical Advisory Board
Gilbert S. Omenn, (Chairman)
Dean, School of Public Health and
Community Medicine,
University of Washington
Gary F. Bennett,
Professor of Biochemical Engineering
Department of Chemical Engineering
The University of Toledo
Kenneth E. Biglane
Independent Environmental Consultant
Formerly, Director of Hazardous Response
Support at U.S. EPA
David W. Miller
President and Chief Operating Officer
Geraghty and Miller, Inc.
John Don 11
Professor of Pharmacology and
Toxicology University of Kansas
Medical Center
Serge Gratch
Professor of Mechanical Engineering
GMT Engineering and Management
Institute
Perry McCarty
Professor and Past Chairman
Department of Civil Engineering
Stanford University
CLEAN SITES
-------
Technical Services
Oversight of Remedial Investigations and
Feasibility Studies
Manage Remedial Designs
Technical Advice Involving Allocations Issues
Peer Review to Ensure Accuracy and
^•^ • • • • •, *f
Objectivity
Technical Assistance to all Clean Sites
personnel
ICLEAN SITES
-------
Technical Services
continued
Technical and Data Mediation
Ensure Consistency with NCP for RI/FS
Site Assessment for Real Estate Transfers
Preparation of Guidance Documents
CLEAN SITES
-------
o
-vj
IO
Assist responsible parties in carrying out the many tasks required for cleanups
Adhere strictly to regulations; work effectively with EPA and State agencies
Assign an on-site project team (for large jobs) and/or headquarters staff to
monitor, control, and report
Provide contracting, scheduling, cost estimating and control services
Community relations activities are an integral part of project management
iCLEAN SITES
-------
Fund Management
Manages and disburses funds for PRP Groups and Steering
Committees
Over $20 million under management at eight sites
Integrated with Project Management and Site Committee
activities
CLEAN SITES
-------
COST ALLOCATION PROCESS
Agree on
Allocation
of Costs
Orphan Shares
Mixed Funding
De Minimis Buyout
etc.
Assure
Quality
of
Data,
Establish
Ground
Rules
Review
Issues
Consider
Allocation
Factors:
Collect
Information
and
Cost
Toxicity
Transshipments
Status of PRPs
etc.
Organize
into Data Base
CLEAN SITES
-------
Technical Dispute Resolution
Neville Chemical Co., CA
(Technical Mediation)
Magnolia Street, CA
(Independent experts to allocate
responsibility for contamination plume)
NPL Site, TX
(Blue Ribbon Panel to review
RI/FS, EA)
CLEAN SITES
-------
SETTLEMENT SERVICES
Organizing and Increasing Participation of Parties
Facilitate Communication Among All Involved Parties
Identification, Assessment and Prioritization of Issues
Mediating and Resolving Disputes Among Participants
Coordinating an Exchanging Information with the
Government
Allocation of Costs Among Parties
Administrative Support
CLEAN SITES
-------
o
00
Settlement Services
Assists in the organization of PRPs
Encourages the involvement of new PRPs in the Allocation process
Assists parties in defining issues and designing the process
Develops and evaluates innovative approaches
Collects and analyzes data
Provides computerized data base management services
Provides dispute resolution services, if desired
CLEAN SITES
-------
Settlement Services Exnerience
Helped bring about final settlement agreements
r>
CO
Wl
For twenty sites
* For removals, remedial actions, or cleanup studies
4- Cleanup activities value of $193 million
Helped divide cleanup costs among responsible parties
*• For twenty-five sites
+ Collection and analysis, verification and array of data in
computerized data base form
4- Highly qualified professional staff
CLEAN SITES
-------
Allocation Experience
Successfully developed allocations with large number
of PRPs (over 800) and diverse interests
large and small companies
municipalities, federal agencies
transporters, owner/operators
CLEAN SITES
-------
Allocation Experience
continued
Instrumental in assisting development of mixed funding and
de minimis buyouts as part of allocation
Developed information to list names of additional PRPs
Developed allocations using
• non-volumetric measures such as toxicity, mobility,
processing considerations, cost of remedial activity
• volumetric measures
• other considerations such as transshipment, recycling,
BTU values, past ownership of facility
CLEAN SITES
-------
C-88
-------
CHRISTIAN BOCARD
NATO/CCMS Guest Speaker
C-89
-------
NATO/CCMS CONFERENCE November 1990
NEW DEVELOPMENTS IN
REMEDIATION
OF OIL CONTAMINATED SITES
AND UNDERGROUND WATERS
Christian BOCARD
INSTITUT FRANCAIS DU PETROLE
and
Jecn DUCREUX, Claude GATELLIER (IFF)
Jean-Francois BERAUD (BURGEAP)
C-90
-------
REMEDIAL ACTIONS : WHY AND TO
WHICH EXTENT ?
BASIC DATA ON THE TRANSFER OF SOLUBLE
HYDROCARBONS FROM RESIDUAL OIL TO GROUNDWATER
In the saturated zone (Figure 1)
In the unsaturated zone : more knowledge needed
A FIELD EXPERIENCE
The construction of a subsurface railway across a
contaminated area:
necessity of mitigating short-term and long-term risks
towards the works
Actions undertaken:
Hydraulic pumping
Experimental in situ aqueous surfactant flushing
(Figures 2 to 9)
C-91
-------
THE USE OF SURFACTANTS
TO IMPROVE IN SITU WASHING AND
BIODEGRADATION
BASIC CONSIDERATIONS
EFFECTIVENESS OF SURFACTANTS
Optimum oil recovery in column tests (Figures 10-11)
Enhanced biodegradation (Figure 12)
HYDRAULIC PARAMETERS TO OPTIMIZE
Flowrate of surfactant solution
Arrangement of injection and pumping wells
in order to:
Sweep the whole contaminated area, taking account of
water permeability and relative permeability
Avoid surfactant passing through the water table
Studies carried out in laboratory models and field pilot
tests (Figures 13-14- )
C-92
-------
O
c
3J
m
ui
o_
c
cr
N*
£]
<-*
o"
3
o
n
Ci
n
IT
O
•3
200 400 600~ 800
RELATIVE PORE VOLUME (V/Vp>
1000
03
-------
LEGENDE
Putts de raballcmcnt
Plezomelre BOTTE
Plezometre SOTRAISOL
Pulls de deposition
——— Drain
O Pulsard de recuperation
23,00 Equlpotentlelle de la nappe
des calcalres de St. OUtN
27,37 Nlveau plezomelrlque suspendu
22,75 Nlveau plezomeUlque
EXTENSjON DE LA ZONE POI.LUEE
ET NIVEAUX PIEZOMETRIQUES
Llmlte approximative
de la zonej>ojl>jee
de I emprlso
du ctxintler
(22,45)
13
anormalement has
FIGURE 2 The contaminated site
-------
FIGURE 3
COUPE GEOLOGIQDE PASSANT PAR fAXE DE LA TRANCHEE
F3 FB F7
C2 12
— Mornet
— Infragypfeirttl
-»• -- — * —i
-I - r'-^l'-^T- I -'i^-l -1 -7- I - SF1
1-l-l-lcJ-J-lr-L
i---i-i-i-i-i-i-i
\\Marrto - c a lea fret ^
zlTrlrirlTiTiTiririTi.-yTi^
Saint-Outni
\- I. 111 -\-.\ -.1 1 l~\
I- l-l-l- I- I- l-l
Soblti d* Btvvchomp
iO
(~>
en
-------
l.imile d'eKlension du prodml
surnageanl s»ir Id nappe
l.imile de la zone d'influence
-------
Limile de la zone d'mfluentr
des putts de depot lui ion
Limile d'extension du produil
surnageant sur la napp«
L1MITE D'ACTION DE LA PREMIERE PHASE DE DEPOLLUTION
Apr*s W J 70 jours de pompace
«->
VO
FIGURE 5 Second hydraulic depollutlon phase
-------
VOLUME
fllCUPERE
(LITRES)
4000.
3000-
2000
1000-
04
22/05 19/06 1Q/07 7/08 4*)9 2/10 30/10 27/11
TEMPS
Quantite de produit r€cup6r£ sur lea pults de d6pollution D4 et D15
0
oo
FIGURE 6 Cumulated volume of recovered oil
-------
1000.
R4-(D4)-D13
o
3
O
?
rt
1
>J
O
3
U
n
3
O
n
u
500.
4 HA I
* Hydr»c«rbnr»i
O Tin.l.-actlf.
* HydrtoarbiirM
.5
10
U
8
0>
01
g
ft MAI
• MAI
Ttnsiv-ietift
Evolution des concentrations en hydrocarbures et en tenslo-actifs de 1'eau dee puite D4 et
D13 lora dea traltementa : influence de l*61olgnement dea puita de dSpollution
ID
FIGURE 7 Surfactant flushing : concentration of emulsified oil
-------
40<
»
IB
300.
200.
£
c
i 100.
4J
cd
1
o
R7-D7
surface
B fond
IS JUILLET
16 JUILLET
17 JUILLET
22 JUILLET
Inpotion Tintio- actift
Evolution dea taneurs en hydrocarbures * la surface et au fond du puits D71ora du traltement
aux tenalo-actifs
o
o
FIGURE 8 Surfactant flushing : ooneentratlon of emulsified oil
-------
Before treatment
1
2
After treatment
3
HYDROCARBON CONCENTRATION
IN WATER (mg/1)
D4
63
22
5
D7
15
0.6
0.3
D13
19
13
7
D15
6
27
5
TOTAL OIL RECOVERY WITH SURFACTANT FLUSHING : 250 litres
FIGURE 9 Results of surfactant flushing
C-101
-------
Inter facial tensions -*nd oil recovery efficiencies
of some commercially surfactant in experiments with
gasoline and fuel oil # ? ("tub *« saVuc»,V«A t
Oil Surfactant
type
SULFONATE 2
GASOLINE
SULFONATE 3
APPE1
SULFONATE 2
/UEL OIL # 2
SULFONATE 3
APPE 1
Active
Surfactant
Concentration
0.5
0.1
0.5
0.5
0.5
0.1
0.5
0.5'
Interfacial
Tension
(mN.m-1)
0.015
0.025
0.358
O.091
O.085
O.1OO
0.745
0.13O
Recovery
Efficiency
(%)
41.3
13.3
4.9
14.5
83.1
7.8
4.4
t
8.8
SO
(«
EO
11.4
15.8
O
3.1
13.6
6.2
3.8
5.3
* : SO/EO : ratio of separated oil to emulsified oil.
? FIGURE 10
-------
^
O o 05
—A surfactant in effluent
raw oil
o surfactant in effluent
(sand control test)
+ tracer
34567
Relative Pore Volume (V/Vp)
Surfactant effectiveness on the gas-oil recovery
Effect of the surfactant partition between water and oil
1:Sand column 2:Control test (no o\l)
UvJKu Jx.VA.ti
CD
CO
FIGURE 11
-------
Aliphatic Hydrocarbons
Aromatic Hydrocarbons
M.ll.
h¥«
GAS-OIL (INITIAL)
I.M 11.71 I7.M II.B B.l
unitn
1 • i • ' • '
I.M.
1.7;.
GAS-OIL IINITIALI
a.m m.a III.M
I M 11.79
•mutts
99.N B.7J •.» 11.29 111.01
IM 11.79 ir.at
1IDUII9
CONTROL TEST
Ji
n. M u.rg DM » a III.
I.M 11.79 37.91
• Inutn
99. M U.n O-M ».» IU.M
TEST WITH SURFACTANT
a. 79 a.M m.a III.
I.M 11.79 21 50 II.:
•Inult9
99. M U.79 II.M
Aerobic biodegradation enhanced with surfactant
Oil eliminated after 50 days in column test, : control test : 53%
sufactant test : 98%
C-104
12
-------
Surfactant flushing In laboratory model 2.5m x 0.5m xO.12m
FIGURE 13
C-10r
-------
10
o
E
o
1 2
Flow (l/h)
Capillary fringe penetration by surfactant
vs injection flowrate and hydraulic gradient
-------
FRANK GALLAGHER
NATO/CCMS Guest Speaker
C-107
-------
A FIELD SCALE INVESTIGATION OF ENHANCED PETROLEUM HYDROCARBON
BIODEGRADATION IN THE VADOSE -ZONE ATTYNDALLAFB, FLORIDA
Major Ross N. Miller Ph.D, PE, CIH
U. S. Air Force, HSD/YAQE
Brooks Air Force Base, Texas
Robert E. Hinchee, Ph.D, PE
Battelle Memorial Institute
Columbus, Ohio
Captain Catherine M. Vogel
U. S. Air Force, AFESC/RDVW
Tyndall Air Force Base, Florida
R. Ryan Dupont, Ph.D
Utah State University
Logan, Utah
Douglas C. Downey, PE
Engineering-Science, Inc.
Denver, Colorado
ABSTRACT
Soil venting is effective for the physical removal of volatile hydrocarbons from unsaturated
soils, and is also effective as a source of oxygen for biological degradation of the volatile and non-
volatile fractions of hydrocarbons in contaminated soil. Treatment of soil venting off-gas is expensive.
constituting a minimum of 50% of soil venting remediation costs. In this research, methods for
enhancing biodegradation through soil venting were investigated, with the goal of eliminating the
need for expensive off-gas treatment.
A seven-month field investigation was conducted at Tyndall Air Force Base (AFB), Florida,
where past jet fuel storage had resulted in contamination of a sandy soil. The contaminated area was
dewatered to maintain approximately 1.6 meters of unsaturated soil. Soil hydrocarbon concentrations
ranged from 30 to 23,000 mg/kg. Contaminated and uncontaminated test plots were vented for 188
C-108
-------
days. Venting was interrupted five times during operation to allow for measurement of biological
activity (C02 production and 02 consumption) under varying moisture and nutrient conditions.
Moisture addition had no significant effect on soil moisture content or biodegradation rate.
Soil moisture content ranged from 6.5 to 9.8%, by weight, throughout the field test. Nutrient addition
was also shown to have no statistically significant effect on biodegradation rate. Initial soil sampling
results indicated that naturally occurring nutrients were adequate for the amount of biodegradation
observed. Acetylene reduction studies, conducted in the laboratory, indicated a biological nitrogen
fixation potential capable of fixing the organic nitrogen, observed in initial soil samples, in five to eight
years under anaerobic conditions. Biodegradation rate constants were shown to be effected by soil
temperature and followed predicted values based on the van't Hoff-Arrhenius Equation.
In one treatment cell, approximately 26 kg of hydrocarbons volatilized and 32 kg biodegraded
over the seven-month field test. Although this equates to 55% removal attributed to biodegradation,
a series of flow rate tests showed that biodegradation could be increased to 85% by managing air flow
rate. Off-gas from one treatment cell was injected into clean soil to assess the potential for complete
biological remediation. Based biodegradation rate data collected at this field site, a soil volume ratio of
approximately 4 to 1, uncontaminated to contaminated soil, would have been required to completely
biodegrade the off-gas from the contaminated soil.
This research indicates that proper ratios of uncontaminated to contaminated soil and air flow
management are important factors in influencing total biodegradation of jet fuel, substantially reducing
remediation costs associated with treatment of soil venting off-gas.
INTRODUCTION
Background Information
Approximately 3.6 x 1012 kg (4 billion tons) of hazardous materials are transported annually in
the United States, and of this amount about 90% consists of gasoline, fuel oil, and jet fuel.
Massachusetts officials report, that in 1984,58% of reported spills in their northeast region were
petroleum products, of which 28% were gasoline, diesel, or fuel oil. Assuming that Massachusetts is
representative of the rest of the United States, transportation and transfer of petroleum products,
particularly fuels, pose a major risk to the environment (Calabrese et al.,1988a).
In addition to transportation of fuels, leakage of stored fuel has proven to be a serious
environmental problem, particularly as a source of ground water contamination. The United States
Environmental Protection Agency (U.S E.P.A.) estimates that there are three million underground
storage tanks in the United States, of which, 78% (2.3 million) are used to store fuel products. Based
on a random sampling, EPA estimates that 35%, or approximately 820,000 underground fuel tanks
are leaking (Calabrese et al.,l988a).
A recent report indicates that there are three to five million underground storage tanks used
to store liquid petroleum and chemical substances and that EPA estimates 100,000 to 400,000 of
these tanks may be or have been leaking. The majority of these tanks have been gasoline or other
petroleum distillates (Camp, Dresser, and Mckee, 1988). Based on the percentages quoted above,
the estimate for leaking underground fuel tanks could go as high as 1.4 million. The disparity in
estimating the number ol leaking underground fuel tanks underscores our inability, to date, to
accurately quantify the magnitude of the problem. Even using minimum estimates, leaking
underground fuel tanks pose a significant threat to the environment.
Hazards Associated With Fuel
Although the general public appears less concerned with fuels than with industrial chemicals,
regulatory agencies have long been aware of the threat to public health that these fuels pose. The
U.S. Coast Guard and U.S. E.P.A. have attempted to characterize the toxicological hazards associated
with petroleum contamination. They concluded that exposure to petroleum products resulting from
contaminated soils may occur via the following routes: inhalation, dermal absorption, ingestion from
consuming contaminated soil, consumption of plants and animals that have assimilated petroleum
products, and by consumption of contaminated drinking water (Calabrese et al.,1988b).
C-109
-------
A combination of U. S. Coast Guard and U. S. E.P.A. ranking systems resulted in a list of 25
priority contaminants of public health concern found in petroleum products as shown in Table 1.
Hoag's findings support the U. S. Coast Guard and U. S. E.P.A. He reports finding at least eight listed
hazardous constituents in gasoline (Hoag et al., 1984).
Table 1. Priority contaminants identified in petroleum products.
Heavy Metals
Halogenated
Hydrocarbons
Nonhalogenated
Aromatic
Nonhalogenated
Aliphatic
Cadmium
Chromium
Tetraethyl lead
Tetramethyl lead
Zinc
1,2,-dibromoethane
Dichloroethane
Dichlorobenzene
Tetrachloroethylene
Trichloroethylene
PCBs
Benzene
Benzo (alpha) anthracene
Benzo (beta) pyrene
Phenol
Toluene
Xylene
Heptane
Hexane
Isobutane
Isopentane
1- Pentene
Adapted from Calabrese et al. (I988b).
Jet fuels have received less attention in the literature than has gasoline. The reason for this is
unknown but may be related to the circumstances under which jet fuel is transported and used.
Millions of liters of jet fuel are transported daily. However, most jet fuel is delivered by underground
pipeline or rail car directly from the refinery to the user. There have been major jet fuel releases,
although most have not been published in the literature. Approximately half of the chemically
contaminated sites on Air Force installations are associated with fuels, most of which are JP-4
(Downey and Elliot, 1990).
Lead is not added to jet fuels for octane enhancement, but one analysis revealed 0.09 ppm
lead and 0.5 ppm arsenic (Riser, 1988). All other metals were below detectable levels, and no
halogenated compounds were found. Normal hexane and heptane were measured at 2.21 and 3.67
% by weight, respectively, and the benzene, toluene, ethylbenzene, and xylenes (BTEX) fraction
constituted 4.5 % by weight. Aromatics totaled 17.6% of the mixture by weight (Riser, 1988).
Seventy-six major components of JP-4 were identified in this analysis, but as many as 270 different
components have been reported in other studies (Mason et al., 1985).
There may be significant environmental health and safety hazards associated with subsurface
fuel spills. Pathways for human exposure are through ground water contamination resulting from
solubilization of normal and substituted alkane, alkene, and aromatic hydrocarbons and exposure to
toxic levels of vapors trapped in occupied, confined spaces. Explosion from vapors, which move by
advection and diffusion to a confined space containing a source of ignition (i.e., basements), is the
greatest potential safety hazard resulting from subsurface fuel spills (Hoag and Cliff, 1988).
BTEX Contamination of Ground Water
BTEX are the contaminants in fuels which most often result in contamination and
abandonment of subsurface drinking water supplies. This fact results from the relatively high solubility
of these aromatics in water, coupled with the low allowable aqueous-phase maximum-contaminant
levels (MCLs) due to their known or suspected carcinogenicity.
Dissolved benzene, toluene, and xylene resulting from gasoline contamination have been
reported in domestic water wells at concentrations of 14,10, and 10 mg/L, respectively (Hoag and
Cliff, 1988). A 38,000 L (10,000 gallon) release from a gasoline station in Bellview, Florida caused the
abandonment of the entire Bellview drinking water well field based on the BTEX fraction found in
water samples. BTEX concentrations in soils collected during construction of monitoring wells ranged
from 894 to 388 mg/kg (Camp, Dresser, and McKee, 1988).
Conner (1988) indicated that fuel leaks as large as 1 million L (270.000 gallons) have
occurred but that leaks in the 75,000 to 200,000 L (20,000 to 50,000 gallon) range are more
C-110
-------
common. Considering the damage resulting from the 38.000 L (10,000-gallon) release at Bellview,
Florida, the typical 75,000 to 200,000 L (20,000 to 50,000 gallon) spill is environmentally significant.
He also stated that soil can hold up to 70 L of gasoline/m3 (0.5 gallons of gasoline/ft3) and that 3.8 L
(1 gallon) of gasoline can render 3.8 million L (1 million gallons) of water unsuitable for consumption.
This conclusion results from the fact that if 3.8 L (1 gallon) of gasoline containing 1% benzene were
added to 3.8 million L (1 million gallons) of water, the benzene concentration would be approximately
7 u.g/L (ppb) and would be unfit for human consumption based on the current MCL of 5 u.g/L (ppb)
(Pontius, 1990). However, this analysis assumes complete benzene solubilization and ignores
partitioning and kinetics.
One percent benzene in fuel is not uncommon, and much higher levels have been
measured. The American Petroleum Institute (API)/EPA reference fuel, PS-6. contains 1.7 %
benzene, 4 % toluene, and 9.8 % ethylbenzene and o- m- p- xylene by volume. The total aromatic
fraction was measured at 26.08 % by volume (Calabrese et al.,1988b). The BTEX and total aromatic
concentration in gasoline varies significantly from refinery to refinery and batch to batch. The fraction
of BTEX in gasoline has been reported to range from 6.4 to 36.4% by weight (Riser, 1988).
Additional research indicates that the Bellview well field and others affected by fuel spills will
be closed for long periods of time unless remediation of the unsaturated-(vadose-) zone is
successful. First, work by Wilson and Conrad (1984) shows that 15 to 40% of the pore space can hold
fuel. This means that 38,000 L (10,000 gallons) of gasoline can be held in a cube 9mxl2mx9m
(30ftx40ftx30ft). Malot and Wood (1985) describe a multi-phase transport model by Baehr and
Corapcioglu that predicts benzene from a typical gasoline spill will be leached into water for about 20
years, and other components would take several decades longer to be removed through water
flushing. Although natural biodegradation may eventually mineralize most fuel contamination, the
process is frequently too slow to prevent ground water contamination. High-risk sites require rapid
removal of the contaminants to protect drinking water supplies and public health.
Vadose-Zone Remediation
The realization that contaminated soil is a long-term source of ground water contamination has
shifted the focus of remediation from treating contaminated ground water (pump and treat) to treating
the source of the contamination in the vadose-zone. The initial remediation method employed by
consulting firms was excavation of contaminated soil with placement in landfills or for use in asphalt
plants. Fuel-contaminated soil is not a listed or characteristic hazardous waste, and disposal in
sanitary landfills is often recommended to reduced disposal costs. The cost of this alternative ranges
from $400 to $660 per m3 ($300 -$500 per yd3) of contaminated material (Clarke, 1987). This type of
recommendation has been made without consideration of the listed hazardous waste components in
fuels and the future costs associated with being identified as a potentially responsible party (PRP) in
the clean-up effort of the hazardous waste or sanitary landfill. Increased restrictions by EPA on
landfilling of hazardous waste and the risk of being identified as a PRP in a hazardous waste or sanitary
landfill cleanup have led to the emergence of excavation coupled with incineration technology.
However, this approach is extremely expensive at $1300 to $2600 per m3 ($1000 to $2000 per yd3),
making this alternative cost prohibitive for large volumes of contaminated soil (Clarke, 1987).
Excavation is not only expensive but may be impossible if contamination extends beneath
buildings or across property lines. If contamination is deep, the size of safe excavations may be
prohibitive (Bennedsen et al., 1987). Numerous failures at hazardous waste landfills together with the
inability to excavate many sites has sparked increased emphasis for on-site clean-up technologies. In
many cases, on-site treatment technologies have proven to be less expensive than off-site
alternatives and, if feasible, are usually preferred by U.S.E.P.A. (U.S.E.P.A., 1989). Technologies for
in situ remediation of vadose-zone fuel hydrocarbon contamination include soil washing, radio
frequency (RF) heating of soil, soil venting, and enhanced microbial degradation.
Soil venting is a technology that has been proven effective for the physical removal of volatile
compounds such as gasoline and TCE from the unsaturated-zone. However, soil venting produces
an effluent which may require expensive treatment prior to discharge. This off-gas treatment step
frequently constitutes a minimum of 50% of total remediation costs. In addition, volatilization of
contaminants through soil venting alone is not effective in the removal of nonvolatile or low volatility
components of jet fuel. This research explored the possibility of reducing or eliminating expensive
C-lll
-------
off-gas treatment while remediating low volatility jet fuel contamination of vadose-zone soils through
enhancing in situ biodegradation.
AIR FORCE RESEARCH OBJECTIVES
The Air Force stores and transports 11 x 109 L (3 x 109 gallons) of JP-4 jet fuel annually and
an estimated 1,500 fuel spills have been identified during Phase II investigations conducted under
the Air Force Installation Restoration Program (IRP). JP-4 is less volatile than gasoline and contains a
considerable nonvolatile fraction (Mason et al., 1985). This research, funded by the Air Force,
builds upon earlier work with enhanced bioreclamation through soil venting at Hill Air Force Base
(AFB), Utah (Hinchee et al. 1989). This research direction resulted from the apparent failure of
hydrogen peroxide (H202) to adequately deliver oxygen at JP-4-contaminated sites studied at Kelly
AFB, Texas, and Eglin AFB, Florida (Downey and Elliot, 1990). As an alternative approach, Air Force
research is presently concerned with evaluating soil venting as an economical process for supplying
oxygen for enhanced biodegradation in the subsurface.
The objective of this project was to investigate the potential for enhanced biodegradation of
JP-4 jet fuel in the vadose-zone by providing oxygen through soil venting combined with moisture
and nutrient addition. This project is a field evaluation and demonstration of this in situ technology.
Specific objectives were:
1. to evaluate the potential for enhanced biodegradation of JP-4 in the
vadose-zone as the result of soil venting and incremental effectiveness
observed with addition of nutrients and moisture,
2. to evaluate the relationships among air flow rate, biodegradation,
and volatilization to determine minimal aeration rates required to maintain
aerobic conditions for maximizing biodegradation and minimizing volatilization,
and
3. to evaluate the potential for biodegradation of hydrocarbon vapors
(off-gas) in uncontammated or less contaminated vadose-zone soil as an
alternative to expensive above-ground off-gas treatment.
The intended result was to develop sufficient information to allow the Air Force and/or other
large users of similar fuel mixtures to progress to full-scale implementation of the technology.
MATERIALS AND METHODS
Site Description
An in situ field demonstration of enhanced biodegradation through soil venting was
conducted at the site of an abandoned tank farm located on Tyndall AFB, Florida. The site is
contaminated with fuel, primarily JP-4, and free product has been observed floating on the shallow
ground water table. Tyndall AFB is located on a peninsula that extends along the shoreline of the Gulf
of Mexico in the central part of the Florida Panhandle. The highest ground on the peninsula is 7.6 to
9.1 m (25 to 30 ft) above mean sea level. The uppermost sediments, at Tyndall AFB, are sands and
gravels of Pleistocene to Holocene age (Environmental Science and Engineering, Inc., 1988). Soils
at the site are best described by the Mandarin series consisting of somewhat poorly drained,
moderately permeable soils that formed in thick beds of sandy material (U.S.D.A., 1984).
The climate at the site is sub-tropical with an annual average temperature of 20.5° C (69° F).
Average daily maximum and minimum temperatures are 25° C and 16° C (77° F and 61° F),
respectively. Temperatures of 32° C (90° F) or higher are frequently reached during summer months,
but temperatures above 38° C (100° F) are reached only rarely. Average annual rainfall at Tyndall AFB
is 140 cm (55.2 inches) with approximately 125 days of recordable precipitation during the year. The
depth to ground water on Tyndall AFB varies from about 0.3 to 3.0 m (1 to 10 ft). The water-table
elevation nses during periods of heavy rainfall and declines during periods of low rainfall. Yearly
C-112
-------
fluctuations in ground water elevations of approximately 1.5 m (5 ft) are typical (Environmental Science
• and Engineering, Inc., 1988). Prior to dewatering at the site, the water table was observed to be as
shallow as 46 cm (1.5 ft).
Field Testing Objectives
A seven month field study (October, 1989, to May, 1990) was designed to address the
following areas:
1. Does soil venting enhance biodegradation of JP-4 at this site?
2. Does moisture addition coupled with soil venting enhance
biodegradation at this site?
3. Does nutrient addition coupled with soil venting and
moisture addition enhance biodegradation at this site?
4. Will the hydrocarbons in the off-gas biodegrade when
passed through uncontaminated soil?
5. Evaluation of ventilation rate manipulation to maximize
biodegradation and minimize volatilization.
6. Calculation of specific biodegradation rate constants from a
series of respiration tests conducted during shutdown of the air
extraction system.
7. Determination of the effects of biodegradation and volatilization on
a subset of selected JP- 4 components.
8. Determination of the potential for nitrogen fixation under aerobic
and anaerobic conditions.
9. Evaluation of alternative vent placement and vent configuration
to maximize biodegradation and minimize volatilization.
Test Plot Design and Operation
In order to accomplish project objectives, two treatment plots and two background plots were
constructed and operated in the following manner:
1. Contaminated Treatment Plot 1 (V1) - Venting only for
approximately 8 weeks, followed by moisture addition for
approximately 14 weeks, followed by moisture and nutrient
addition for approximately 7 weeks.
2. Contaminated Treatment Plot 2 (V2) - Venting coupled with
moisture and nutrient addition for 29 weeks.
3. Background Plot 3 (V3) - Venting with moisture and nutrient
addition at rates similar to V2, with injection of hydrocarbon
contaminated off-gas from V1.
4. Background Plot 4 (V4) - Venting with moisture and nutrient
addition at rates similar to Vent 2.
C-113
-------
Air Flow
Air flow was maintained throughout the field test duration except during in situ respiration
tests. Flow rates were adjusted to maintain aerobic conditions in treatment plots, and background
plots were operated at similar air retention times. Off-gas treatment experiments in one background
plot (V3) involved operation at a series of flow rates and retention times.
Soil gas was withdrawn from the center monitoring well in V1 and V2 and from the only
monitoring well in V3 and V4. This configuration was selected to minimize leakage of outside air
observed when air was withdrawn from the ends of the plots. In all but one plot, V3, atmospheric air
was allowed to passively enter at both ends. Off-gas from V1 was pumped back to the upstream
ends of V3. Flow rates through all test plots were measured with calibrated rotameters.
Water Flow
To allow control of soil moisture, tap water was applied to the surface of the treatment plots.
The design flow rates allowed variation from 10 to 100 mL/min in the contaminated treatment plots,
and 2.5 to 25 mL/min in the background vents. This corresponds to average annual surface
application rate of 43 to 430 cm (17 to 170 in). Based on vacuum and oxygen measurements in the
soil gas monitoring probes, it was determined that a flow rate of 100 mL/min in the Treatment Plots
inhibited airflow and oxygen transfer. Using the same technique, a flow rate of 50 mL/min (215 cm/yr
surface application rate) was selected as the final water application rate. This rate did not appear to
inhibit oxygen transfer to the soil gas monitoring points.
Nutrient Addition Rates
The objective of nutrient addition was to apply sufficient inorganic nitrogen (N), phosphorus
(P), and potassium (K) to ensure, as far as possible, that these nutrients would not become limiting
during the biodegradation of fuel hydrocarbons in the test plots. Optimizing nutrient addition rates
was not the primary objective of this phase of the study. Sodium trimetaphosphate (Na-TMP),
ammonium chloride (NH4CI), and potassium nitrate (KNOs) were used as sources of P, N, and K,
respectively.
RESULTS AND DISCUSSION
Operational Monitoring of
Treatment Plots V1 and V2
Treatment plots were operated for 188 days between October 4,1989 and April 24,1990.
Operation was interrupted only for scheduled respiration tests. Discharge gases were monitored for
oxygen, carbon dioxide, and total hydrocarbons throughout the operational period. The
biodegradation component was calculated using the stoichiometnc oxidation of hexane. Oxygen
consumption was calculated as the difference between oxygen in Background Plot V4 and oxygen in
the treatment plots. Using the oxygen concentration in the background plot, rather than atmospheric
oxygen concentration, the natural biodegradation of organic carbon in uncontaminated soil was
accounted for. This method ensures that the biodegradation of fuel hydrocarbons was not
overestimated. Biodegradation based on carbon dioxide production was similarly calculated. As the
more volatile compounds are stripped from the soil, biodegradation becomes increasingly important
over time as the primary hydrocarbon removal mechanism (Figure 1). As illustrated in Figure 1,
C-114
-------
100-
80-
c
0>
u
o
0-
60
% Removal by Biodegradation • V1
% Removal by Biodegradation • V2
Moisture
addition
toVl
Nutrient addition
toV1
60 90 120 150
Venting Time (days)
180 210
Figure 1. Comparison of the percent of combined volatilization and biodegradation hydrocarbon
removal rates attributed to biodegradation (oxygen basis) in Treatment Plots V1 and V2 during the
field study.
percentages of combined hydrocarbon volatilization and biodegradation removal rates attributable to
biodegradation were similar in Treatment Plots V1 and V2 throughout the experimental period, and
neither moisture nor nutrient addition appear to have increased biodegradation rates.
Respiration Tests
Respiration Tests, 1 through 5, were conducted October 24 through 26; November 28
through December 1,1989; January 3 through 8; March 3 through 11; and April 24 through 26,
1990, respectively. In addition, two limited respiration tests, 3A and 4A, were conducted from January
25 through 25, and March 9 through 12,1990. The respiration tests were designed to determine the
order and rate of hydrocarbon biodegradation kinetics under varying conditions of moisture and
nutrient addition. Treatment Plot V2 received moisture and nutrients throughout the experimental
period and therefore served as a control for kinetic changes due to soil temperature and other factors
not related to moisture and nutrients. The respiration tests were conducted by first shutting down the
air delivery system to both the treatment and background plots, followed by measurement of oxygen
consumption and carbon dioxide production over time. Biological respiration in Treatment Plots V1
and V2 was most consistently modeled by zero order kinetics during all respiration tests. In a system
not limited by substrate, such as fuel contaminated soil, biodegradation is likely to be best modeled
by zero-order kinetics (Riser, 1988).
Figure 2 graphically illustrates the zero order rate constant data obtained from the respiration
tests. In Treatment Plot V1, the rate constant showed a significant drop between Test 1 and Test 2,
and between Test 2 and Test 3. The rate constant significantly increased between Test 3 and Test 4
in Treatment Plot V1, but did not significantly increase between Tests 4 and 5. Since moisture was
added to Treatment Plot V1 after Test 2 and nutrients after Test 4, their addition would seem, without
further analysis, to be of no benefit and even detrimental, in the case of moisture addition. In
Treatment Plot V2, there was a statistically significant drop in the rate constant from Test 2 to Test 3
and a statistically significant increase in the rate constant between Test 3 and Test 4. Although a
depression appears in the rate constant data, there were no other statistically significant differences in
Treatment Plot V2 rate constants.
Statistically significant differences in respiration rate between Treatment Plots V1 and V2, and
the Background Plot V4, on all tests, and between Off-Gas Treatment Plot V3 and Background Plot
V4, on Tests 3,4A, and 5 are illustrated in Figure 2. From the data presented, it is concluded that
C-115
-------
c
I
"c
0)
O)
>
X
O
Testl
Test 2'
Test 3'
Test 4'
Test 4A1
Test 5'
Treatment Plot V2
Treatment Plot V1
Off-gas Plot V3
Background Plot V4
Figure 2. Average zero order rale constanis determined by respiration tests.
biodegradation of jet fuel in contaminated soil, and biodegradation of hydrocarbon off-gas, resulted in
statistically significant increases in respiration over that observed in uncontaminated soil.
Potential Temperature Effects
on Respiration Tests
In aquatic systems, the van't Hoff -Arrhenius equation predicts a doubling of the rate constant
with each temperature increase of 10°C, assuming typical activation energy values (Benefield and
Randall, 1980). Using the Arrhenius constants determined from soil temperature data, the rate
constants for Treatment Plot V1 were corrected to 23 °C, the soil temperature of Test 1 (Figure 3).
The Arrhenius correction for temperature resulted in insignificant rate constant differences between
Tests 2, 3,4, and 5 in Treatment Plot V2. Although a statistically significant difference in rate
constants remained between Test 3 and Tests 2 and 5 in Treatment Plot V1, the magnitude of the
difference is not important from a practical application standpoint.
CONCLUSIONS
This field scale investigation has demonstrated that soil venting is an effective source of
oxygen for enhanced aerobic biodegradalion of petroleum hydrocarbons (jet fuel) in the vadose-
zone. Specific conclusions are:
1. Operational data and respiration tests indicated that moisture (6.5 to 9.8% by weight) and
nutrients were not a limiting factor in hydrocarbon biodegradation. Soil and water samples
indicated that nutrients were delivered to the treatment plots and passed through the
vadose-zone to the ground water.
C-116
-------
0.008
0.006 - -
c
I
§ 0.004
o
x
o
0.002 -
0.000
95% Confidence Interval-V1
Arrhenius Corrected Minimum k-V1
Moisture added Nutrients added
Location/Test No
Figure 3. Temperature corrected (23 °C based on Arrhenius Plot) oxygen consumption rate
constants (k) determined by respiration tests tor Treatment Plot V1. Mean k is at the center of the
95% confidence interval.
2. Air flow tests documented that decreasing flow rates increased the percent of
hydrocarbon removal by biodegradation and decreased the percent of hydrocarbon
removal by volatilization. Under optimal airflow conditions (0-.5 air void volumes per day)
82% of hydrocarbon removal was biodegraded and 18% volatilized. Biodegradation
removal rales ranged from approximately 2 to 20 mg/(kg day), but stabilized values
averaged about 5 mg/(kg day). The effect of soil temperature on biodegradation rates
was shown to approximate effects predicted by the van't Hoff-Arrhenius equation.
3. Off-gas treatment studies documented that uncontaminated soil at this test site could be
successfully used as a biological reactor for the mineralization of hydrocarbon vapors (off-
gas) generated during remediation of fuel contaminated soil using the enhanced
biodegradation through soil venting technology investigated in this field study. The
average off-gas biodegradation rate was 1.34 (SD ± 0.83) mg/(kg day), or 1.93 (SD ± 1.2)
g/(m3 day). The percent of off-gas biodegradation was inversely related to air flow rate
(retention time), and was directly related to hydrocarbon loading rate, at the 95%
confidence level. Based on data collected at the field site, a soil volume ratio of
approximately 4 to 1, uncontaminated to contaminated soil, would be required to
completely biodegrade the off-gas from a bioventing system operated similar to this field
project. However, if air flow rates in contaminated soil were designed to maximize
biodegradation, the ratio of uncontaminated to contaminated soil required would be
proportionally less.
4. Respiration Tests documented that oxygen consumption rates followed zero-order
kinetics, and that rates were linear down to about 2 to 4 % oxygen. Therefore, air flow
rates can be minimized to maintain oxygen levels between 2 and 4% without inhibiting
biodegradation of fuel, with the added benefit that lower airflow rates will increase the
percent of removal by biodegradation and decrease the percent of removal by
volatilization.
C-117
-------
5. Initial soil samples indicated that naturally available nitrogen and phosphorus were
adequate for the amount of biodegradation measured, explaining the observation that
nutrient addition had an insignificant effect on the rate of biodegradation. Acetylene
reduction studies revealed an organic nitrogen fixation potential that could fix the
observed organic nitrogen, under anaerobic conditions, in five to eight years.
6. Soil moisture levels did not significantly change during the field study. Soil moisture
levels ranged from 6.5 to 7.4%, and 8.5 to 9.8%, by weight, respectively, in Treatment
Plots V1 and V2. Neither venting nor moisture addition had a statistically significant effect
on soil moisture at this site.
RECOMMENDATIONS FOR FUTURE STUDY
To further pursue the development ol an enhanced biodegradation of petroleum
hydrocarbons through soil venting technology, the following studies are recommended:
1. Further investigate the relationship between soil temperature and hydrocarbon
biodegradation rate.
2. Investigate methods to increase hydrocarbon biodegradation rate by increasing soil
temperature with heated air, heated water, or low level radio frequency radiation.
3. Investigate the effect of soil moisture content on biodegradation rate in different soils with
and without nutrient addition.
4. Investigate nutrient recycling to determine maximum C:N:P ratios that do not limit
biodegradation rates.
5. Investigate different types of uncontaminated soil for use as a reactor for biodegradation
of generated hydrocarbon off-gas and determine off-gas biodegradation rates.
6. Investigate gas transport in the vadose-zone to allow adequate design of air delivery
systems.
REFERENCES
Benefield, L. D., and C. W. Randall. 1980. Fundamentals of process kinetics, p. 11-13. fn Biological
process design for wastewater treatment. Prentice-Hall, Inc., Englewood Cliffs, New Jersey.
Bennedsen. M. B., J. P. Scott, and J. D. Hartley. 1987. Use of vapor extraction systems for in-situ
removal of volatile organic compounds from soil. pp. 92-95. In Proceedings of the National
Conference on Hazardous Wastes and Hazardous Materials, Washington, DC.
C-118
-------
Calabrese, E. J., P. T. Kostecki, and E. J. Fleischer. 1988a. Introduction, p. 1-2. In E.J., Calabrese,
and P. T. Kostecki (ed.) Soils contaminated by petroleum - environmental and public health effects.
John Wiley & Sons, Inc., New York, New York.
Calabrese, E. J., P. T. Kostecki, and D. A. Leonard. 1988b. Public health implications of soils
contaminated with petroleum products, p. 191-229. In E. J., Calabrese, and P. T. Kostecki (ed.) Soils
contaminated by petroleum - environmental and public health effects. John Wiley & Sons, Inc., New
York, New York.
Camp, Dresser, and McKee, Inc. 1988. Rnal report for field evaluation of vacuum extraction corrective
technology at the Bellview, FL LUST site. Final Report No. 68-03-3409. U.S. Environmental
Protection Agency, Edison, New Jersey.
Clarke, A. N., (AWARE Inc.). 1987. Zone 1 soil decontamination through in-situ vapor stripping
processes. Final Report No.68-02-4446. U.S. Environmental Protection Agency, Washington, DC.
Conner, J. R. 1988. Case study of soil venting. Poll. Eng. 7:74-78.
Downey, D. C., and M. G. Elliot. 1990. Performance of selected in situ soil decontamination
technologies: a summary of two AFESC field tests. In Soil and groundwater remediation. Proc. Joint
DOBAir Force technology review meeting., Atlanta, GA. 6-8 February 1990. Office of Technology
Development, Department of Energy, Washington DC., Headquarters Air Force Engineering Services
Center, Tyndall Air Force Base, FL.
Environmental Science and Engineering Inc. 1988. Installation restoration program -
confirmation/quantification Stage 2 Volume 1 Tyndall AFB, FL. Rnal Report. Headquarters Tactical
Air Command, Command Surgeon's Office (HQTAC/SGPB), Bioenv/ironmental Engineering Division.
Langley AFB, Virginia.
Hinchee, R. E., D. C. Downey, R. R. Dupont, M. Arthur, R. N. Miller, P. Aggarwal, and T. Beard. 1989.
Enhanced biodegradation through soil venting. Final Report No. SSPT 88-427. Prepared for HQ
AFESC/RDV by Battelle Columbus. Columbus, OH.
Hoag, G. E., and B. Cliff. 1988. The use of the soil venting technique for the remediation of
petroleum-contaminated soils, p. 301-316. In E. J., Calabrese, and P. T. Kostecki (ed.) Soils
contaminated by petroleum - environmental and public health effects. John Wiley & Sons, Inc., New
York. New York.
Hoag, G. E., C. J. Braell, and M. C. Marley. 1984. Study of the mechanisms controlling gasoline
hydrocarbon partitioning and transport in groundwater systems. USGS Final Report No. PB85-
242907. National Technical Information System, Washington, DC.
Malot, J. J., and P. R. Wood. 1985. Low cost, site specific, total approach to decontamination. In
Proceedings of Environmental and Public Health Effects of Soils Contaminated with Petroleum
Products. Amherst, Massachusetts. 1985. Also p. 331-354. In E. J., Calabrese, and P. T. Kostecki
(ed.) Soils contaminated by petroleum - environmental and public health effects. John Wiley & Sons,
Inc., New York, New York.
Mason, B., K. Wiefling, and G. Adams (Monsanto, Co.). 1985. Variability of major organic components
in aircraft fuels. Engineering and Services Laboratory, Air Force Engineering and Services Center.
ESL-TR-85-13. Tyndall AFB, FL.
Pontius, F. W. 1990. Complying with the new drinking water quality requlations. AWWAJ 82(2): 32-
52.
Riser, E. 1988. Technology review - In situ/on-site biodegradation of refined oils and fuel. PO No.
N68305-6317-7115. Naval Civil Engineering Laboratory. PO No. N68305-6317-7115. Port
Hueneme, CA.
C-119
-------
U.S.E.P.A. 1989. Bioremediation of contaminated surface soils. Robert S. Report No. EPA/600/9-
89/073. Kerr Environmental Research Laboratory. Ada, OK.
U.S.D.A. 1984. Soil survey of Bay County Florida. USDA-SCS. U.S. Government Printing Office,
Washington, DC.
Wilson, J. T., and S. H. Conrad, 1984. Is physical displacement of residual hydrocarbons a realistic
possibility in aquifer restoration? p. 274-298. In Proceedings of Petroleum Hydrocarbons and
Organic Chemicals in Groundwater: Prevention, Detection, and Restoration, Houston, Texas. 5-7
November 1984. National Water Well Association/American Petroleum Institute. Dublin, OH.
Biographical Sketches
Maior Ross N. Miller. Ph.D. PE. CIH is a Senior Bioenvironmental Engineer with the Air Force
Human Systems Division Installation Restoration Program Office. He holds a BS in Civil and
Environmental Engineering from Utah State University and an MS in Public Health/ Industrial Hygiene
from the University of Utah. He has managed Occuptional Health and Environmental Protection
Programs at two Air Force Bases. He conducts environmental contamination investigations and has
supervised RI/FS efforts at hazardous waste sites. His research interest is bioremediation of jet fuel in
the vadose-zone using air as an oxygen source. (USAF HSD/YAQE, Brooks AFB, Texas 78235 (512)
536-9001 ext. 297)
Robert E. Hinchee. Ph.D. PE is a Senior Engineer with the Battelle Columbus Division of
Battellle Memorial Institute. He holds a PhD in Civil and Environmental Engineering from Utah State
University. His expertise includes investigatations, and remediations at more than 100 petroleum
hydrocarbon contaminated sites. (Battelle, 505 King Avenue, Columbus, Ohio 43201-2693, (614)
424-4698.)
Captain Catherine M. Vogel is a Project Officer with the Air Force Engineering and Services
Center. She holds a B.S. in Civil Engineering from Michigan Technological University and is pursuing
a M.S. in Environmental Engineering from the University of Arizona. Her primary interests include in
situ remediation and above ground bioreactor design. (HQ AFESC/RDVW, Bldg. 1117, Tyndall AFB,
Florida 32403. (904) 283-2942)
R. Rvan Dupont. PhD is an Associate Professor of Civil and Environmental Engineering, and
is the Assistant Director of the Utah Water Research Laboratory at Utah State University. He holds a
B.S. in Civil Engineering, and M.S. and PhD degrees in Environmental Health Engineering from the
University of Kansas. His current activities involve field monitoring and evaluation of soil vacuum
extraction systems, and the investigation and description of field and laboratory scale vacuum
extraction/enhanced in situ biological treatment of fuels and hazardous waste contaminated soils.
(Utah Water Research Laboratory, Utah State University, Logan Utah 84322 (801) 750-3227)
Douglas C. Downey. PE is a Senior Engineer with Engineering-Science, Inc. He holds an MS
in Civil/Environmental Engineering from Cornell University. He has worked in the U. S. Air Forces's
environmental protection program for the past 13 years. His interests include in-situ remediation.
(Engineering-Science Inc., 1100 Stout Street, Suite 1100, Denver, Colorado 80204, (303) 825-
0422.)
C-120
-------
EDWARD MARCHAND
NATO/CCMS Guest Speaker
C-121
-------
CATALYTIC OXIDATION EMISSIONS CONTROL
FOR REMEDIATION EFFORTS
Captain Ed Marchand, HQ AFESC/RDVW, Tyndall AFB FL 32403-6001, USA
INTRODUCTION
The soils and groundwater under airfield facilities are often
contaminated with jet fuel components, chlorinated solvents, and degreasers.
This contamination has resulted from past disposal practices, leaking storage
tanks, and accidental spills. As a primary solution to this problem, the Air
Force established the Installation Restoration Program (IRP) to identify
contaminated areas, determine the type and extent of contamination, and
initiate appropriate cleanup actions. There are now over 3,500 IRP sites at
243 installations with an estimated 60% of the sites requiring cleanup action
(Reference 1). The Engineering and Services Laboratory (ESL), part of the Air
Force Engineering and Services Center, is responsible for environmental
quality research and development of more effective, cost-efficient remedial
actions. This research targets the development of chemical, biological, and
physical treatment systems to meet this challenge. This paper reports the
findings from several field tests of remediation technology where catalytic
oxidation was used to control or treat the off gasses from the effort.
CONTAMINATED GROUNDWATER REMEDIATION
WURTSHITH AFB STUDIES
In the late 1970's, trichloroethlyene (TCE), a degreasing agent, was
discovered in the drinking water at Wurtsmith AFB, Michigan. Chemical
analyses of the groundwater showed levels of TCE exceeding 6,000 micrograms
per liter (ug/L). The U.S. Environmental Protection Agency maximum
contaminant level for TCE is 5 ug/L. The source of the TCE was traced to a
leaking 500-gallon underground storage tank. Since the leaking tank went
undetected for years, the quantity of TCE leaked could only be estimated. The
subsequent plume of TCE was determined to encompass approximately 9 million
cubic meters, with a maximum concentration approaching 10,000 ug/L.
A review of the literature identified countercurrent packed-bed air
stripping as a possible treatment alternative. Countercurrent packed-bed air
stripping involves flowing contaminated water down a packed column, while
forcing air upward through the column. The packing breaks up the flow of
water and air, increasing the air/water contact and enhancing transfer of the
contaminant from the water into the air. In many states air emission control?
are required to prevent release of these volatiles to the environment.
The Environics Division of the ESL performed laboratory and pilot-scale
tests at Vurtsmith AFB to verify the operating performance of packed-bed air
stripping. As a result of the study Wurtsmith AFB currently has two air
stripping operations underway removing TCE from the groundwater from two
separate plumes. A third unit, under construction, will remove benzene from
C-122
-------
another plume of contaminated groundwater. The initial air stripper does not
have any emissions control device while the other two have (or will have for
the benzene unit) catalytic oxidation for emissions control. Catalytic
oxidation is a combustion process where the contaminant-laden air stream is
preheated and passed through a catalyst bed. Final products of the oxidation
are typically carbon dioxide, water, and inorganics.
Evaluations are underway at Wurtsmith AFB on the catalytic oxidation unit
installed to control the air stream coming from the 200 gallon per minute air
stripper used to remove TCE from the groundwater. The preliminary findings
are shown in Table 1. The catalytic unit is a fluidized bed reactor. The
catalyst particles are spherical shaped and the contaminated air stream is
passed through the reactor at sufficient velocity to churn or fluidize the
catalyst bed. This motion causes the particles to collide into one another
which breaks off small pieces of the surface. Since catalyst fouling occurs
on the surface, this type of reactor is contiuously self-cleaning. This
catalyst attrition is slow and at Wurtsmith AFB they are still running on the
same catalyst charge from 1988.
There is some concern though because the Wurtsmith AFB catalyst appears
to be forming a small amount of benzene when operating. Simultaneous sampling
of the preheater effluent and the stack emissions show an 40 - 60 percent
increase in the benzene concentrations. This is based on one sampling effort
and is a preliminary, and puzzling, finding. The Engineering and Services
Laboratory is looking further into the situation to understand the reaction
mechanisms. The vendor indicates that the benzene formation is due to a low
catalyst bed volume (not enough residence time for the air to contact the
catalyst). This will be verified in the near future.
TABLE 1. PRELIMINARY DATA FROM THE EVALUATION OF A
CATALYTIC OXIDATIOH CONTROL UNIT AT WURTSMITH AFB MI
AIR STREAM CONCENTRATIONS: 1 part per million Trichloroethylene; 10 parts
per billion of 1,2 Dichloroethane
CATALYTIC OXIDATION UHIT SPECIFICATIONS:
CAPACITY: 1200 cubic feet per minute
OPERATING TEMPERATURE: 700 °F
NATURAL GAS CONSUMPTION (ave): 800 cubic feet per hour
TIME ON STREAM: SINCE JUNE 1988
DESTRUCTION EFFICIENCY OF TCE (as of Feb 1990): >97%
PURCHASE PRICE: $113,000
EGL1N AFB STUDIES
In 1988-1989, at a large Jet fuel spill site on Eglin AFB, Florida, we
evaluated (Reference 2) different packing materials for conventional
counter-current air stripping operations and compared their performance to a
new rotary air stripper. In addition several emissions control options were
also evaluated. The groundwater at the site contained a large variety of
soluble jet fuel components as well as inorganic materials that greatly
affected the research effort. Table 2 lists some selected parameters from the
Eglin site.
C-123
-------
TABLE 2 SELECT CONTAMINANTS AT THE EGLIN AFB FUEL SPILL SITE
CONTAMINANT
BENZENE
NAPHTHALENE
TOLUENE
0-XYLENE
IRON (as Fe+2)
SULFUR (as H2S)
AVE. CONC.
78
70
60
220
8500
>500
HENRY'S LAW
CONSTANT
(atm-mVmole)
.0047
.00041
.0059
.0040
Not Applicable
Not Applicable
The rotary air stripper is a new approach to countercurrent air
stripping. The unit utilizes a spinning rotor to move the water out radially
from the center of the unit as shown in Figure 1. Clean air is forced from
the outside towards the center, maintaining the countercurrent air/water
flow. While removal efficiencies were similar, the rotary stripper has the
added flexibility of rotor speed to meet changing feed stream concentrations.
The disadvantage is the added cost to spin the rotor, the increased complexity
and the requirement to have the rotor perfectly balanced during operation.
INFLUENT AIR
EFFLUENT AIR
INFLUENT WATER
ROTATING PACKING
EFFLUENT WATER
Figure 1. Cross section, rotary air stripper
C-124
-------
Catalytic oxidation, carbon adsorption and molecular sieves were
evaluated for the control of the emissions from the air stripping units at the
Eglin site. The carbon units had a very low capacity for the lower molecular
weight compounds (C$ and below). In addition the excess humidity from the
air stripping effluents further reduced the carbon adsorption capacity. Thus,
a carbon bed large enough to adsorb the emissions from the air stripping
operations would have a large capital and operating cost, making carbon a very
expensive alternative at this site. Two molecular sieve materials, Union
Carbide's type 9102 and 1387-53, were tested because they are not impacted by
humidity effects and they could be regenerated on-site with ozone. Our data
showed that both molecular sieve materials were unsuccessful for adsorbing the
contaminants in the air stripping emissions. The unfavorable performance of
the molecular sieves may have been because their pore sizes were too small to
allow the contaminant molecules access to the active adsorption s-ites.
Another emission control technique evaluated was catalytic oxidation. An
Engelhard pilot-scale catalytic oxidation unit was tested at the Eglin site.
The unit uses an electric preheater to raise the inlet gas temperature to
1000 °F before passing it through a precious metal fixed bed catalyst
reaction chamber. The result is on-site destruction of the organic
contaminants. Enough of the hydrogen sulfide (see Table 2) was stripped out
of the water to cause a chemical reaction in the catalytic oxidation unit
which effectively and rapidly deactivated the catalyst. Total capital,
operations and maintenance cost estimates for a 100 gallon per minute air
stripping unit, based on 99% removal of benzene from contaminated groundwater,
are: $3.19/1000 gallons just for the air stripping unit, $1.70/1000 gallons
for catalytic oxidation of the emissions (based on other fluidized bed data)
or $6.47/1000 gallons for activated carbon emissions control.
CONTAMINATED SOILS REMEDIATION
There are several methods to remediate a site contaminated with volatile
organics such as Jet fuel. The ESL tested the efficacy of using in situ soil
venting to remove JP-4 from a contaminated sandy soil site at Hill AFB UT.
During the ten months of operation 115,000 pounds of hydrocarbons were removed
from the site. The emissions from this effort were sent through one of two
catalytic oxidation units.
The first unit was a 500 cubic foot per minute fluidized bed unit that
operated for eight months. The second was a 1000 cubic foot per minute fixed
bed unit that used a precious metal catalyst and was operated for six months.
Thus there was a period of four months where the two units operated together
to treat the venting off gases. The fixed bed was operated between 470 and
625 °F while the fluidized bed unit was operated between 625 and 700 °F.
The results (reference 3) show that the fluidized bed unit had an average 89%
destruction efficiency and the fixed bed unit had a 97% destruction
efficiency. This gives a cost-per-volume-treated rate of $23.80/million
air and $29.80/million ft3 air for the fixed and fluidized bed units,
respectively.
C-125
-------
While the fixed bed unit appears economically feasible it has it's
limitations. The unit would not be able to handle a large flow rate of the
initial highly concentrated air stream. This is because the process is one of
oxidation or burning of the contaminants. That means releasing heat in the
process. Fixed beds could get so hot that they actually melt the end of the
bed. Temperature safety controls prevent this from happening, however it does
limit the amount of contaminant you can treat. The fluidized bed unit,
because of the better heat transfer, can handle the higher concentration flow
rates, up to a point. The draw back is the need to add catalyst.
Approximately 150 pounds of catalyst were added to the reactor over the eight
month operation at Hill AFB UT.
CATALYST DEVELOPMENT AND TESTING
Two laboratory studies are now being conducted to investigate catalysts
resistant to deactivation. The University of Akron is developing a catalyst
that resists deactivation when challenged with a chlorinated air stream.
Akron researchers have found that chromium oxide and vanadium oxide materials
can reach greater than 95 percent conversion of chlorinated organics to water,
carbon dioxide, and dilute hydrogen chloride (Reference 4). They are
continuing their research to find a superior catalyst that is resistant to
chlorinated organics and sulphonated compounds present in air-stripping
emissions.
The second study is being done by the Research Triangle Institute (RTI),
N.C. They are evaluating off-the-shelf catalyst formulations from five
manufacturers. The initial step was to create a standard catalyst testing
protocol from which future catalyst formulations can be compared to this
study. The goal is to find out which catalyst is the best for a given
contaminated air stream.
After the catalyst has deactivated from constant exposure to a
synthesized air-stripper emissions stream, RTI will determine what caused the
catalyst to deactivate, which operating procedures will minimize deactivation,
and whether the catalyst can be effectively regenerated. This information
will be used in in an economic comparison of the different catalysts.
Catalyst formulations being tested are the ARI Econocat, a copper chromite
formulation from Harshaw, Carulite from Carus Chemical, three supported noble
metal catalyst formulations from UCI, and a Haldor-Topsoe catalyst.
WHERE WE'RE HEADED - CROSSFLOW AIR STRIPPING WITH CATALYTIC EMISSIONS CONTROL
Crossflow air stripping is a packed-column aeration process which
involves changing the air flow path of a conventional countercurrent tower.
The main change is the placement of baffles inside the tower which causes the
air to flow in a crisscross pattern up through the packing (Figure 2). This
forces the air to flow at 90 degrees to the flow of contaminated water rather
than in completely opposing directions, as in a countercurrent tower. Proper
selection of baffle spacing can produce a marked reduction in gas velocity,
lowering gas-phase pressure drop, and reducing blower energy costs compared to
conventional countercurrent mode of operation.
C-126
-------
Results show the crossflow tower can greatly reduce the blower energy
costs (Reference 5). However, for the highly volatile compounds, the blower
energy cost is not a significant factor in the total cost; therefore, a
countercurrent tower would be just as cost-effective as a crossflow tower.
Blower energy costs do have a significant impact on the total cost of air
stripping for the low and moderately volatile contaminants such as 1,2
Dichloroethane and Methyl Ethyl Ketone. Therefore, the crossflow tower could
be more cost-effective for removing these compounds from groundwater.
Liquid In
Gas Out I
<*SS3» T
ti
Gas In
Gas Out
Liquid In
Liquid Out
Gas In
Liquid Out
COUNTERCURRENT
CROSSFLOW
Figure 2. Comparisons of Crossflow and Countercurrent Air Strippers
C-127
-------
A field study demonstrating the removal efficiency of crossflov air
stripping for low and semi-volatile organics will be conducted during 1991 and
1992. During this test field validation of the RTI catalyst selection
procedure and the University of Akron formulations will be carried out as
emissions control from the crossflow air stripping operations.
REFERENCES
1. Statement of Mr. Gary D. Vest, Deputy Assistant Secretary of the Air Force
(Environment, Safety and Occupational Health) to the Readiness, Sustainability
and Support Subcommittee of the Senate Armed Services Committee, 4 April 1990.
2. AFESC, Air Stripping and Emissions Control Technologies; Field Testing of
Countercurrent Packings. Rotary Air Stripping, Catalytic Oxidation, and
Adsorption Materials, under publication.
3. AFESC, Field Demonstration of In Situ Soil Venting of JP-4 Jet Fuel Spill
Site at Hill Air Force Base, under publication.
4. AFESC, Vapor-Phase Catalytic Oxidation of Mixed Volatile Organic
Compounds. Greene, H. L., ESL TR 89-12, Sep 89.
5. AFESC, Laboratory Investigations of Cascade Crossflow Packed Towers for
Air Stripping of Volatile Organics from Groundwaterf under publication.
C-128
-------
MICHAEL KREMER
NATO/CCMS Guest Speaker
C-129
-------
NATO CCMS
SESSION OF NOV. 8TH 1990 IN ANGERS
1. WELCOME
2. PRESENTATION OF THE AIRVAULT FACTORY
3. THE PROCESS
4. SUITABILITY OF CEMENT KILNS FOR WASTE DESTRUCTION
5. ACTIVITY DESCRIPTION
6. BRANCHES OF ACTIVITY AND CAPACITIES
Crl30
-------
A WORD OF WELCOME
On behalf of CIMENTS FRANCAIS and the entire staff of the factory, I have
great pleasure in welcoming you to the AIRVAULT factory.
C-131
-------
PRESENTATION OF THE AIRVAULT FACTORY
The factory which welcomes you today is a cement works belonging to the
CIMENTS FRAHCAIS group. CIMENTS FRAHCAIS is an international industrial
group with diversified interests in the building materials field.
Its activities are centred on 4 main areas : cement, aggregate, ready-mixed
concrete and industrial concrete.
Starting with the manufacture of cement in France, the group developed and
expanded its activities throughout the world and now has a presence in 14
countries.
The AIRVAULT factory is part of the DIVISION CIHENT FRANCE which has 12
factories and a number of crushing and distribution centres. This division
also produces quicklime and mineral charges. The CIMENTS FRANCAIS group is
expected to have a turnover slightly in excess of 16 billion (i.e.
16,000,000,000) francs in 1990.
The AIRVAULT factory is a cement producing centre. It is the third largest
in France in terms of its size and its production level. Its sales amount to
5 % of the home market.
In 1990, we shall produce a little over 1,200,000 tons of cement and
1,000,000 tons of clinker.
The factory has three activities :
* cement production
* mineral charge production
* incineration of liquid waste
As far as the incineration of liquid waste is concerned, and this will be of
particular interest to you, we process 4 types of product today :
* acid or non-acid residual liquids
* combustible liquid waste (solvents, paint sediment, etc..) which is
used instead of traditional fuels
* used oils.
C-132
-------
THE PROCESS
The AIRVAULT factory is located very close to its quarry and its limestone
seam. The first operation involves the extraction of the material. At
AIRVAULT, we blast with mines and the material is then collected using
mechanical loaders and carried by lorry to the crusher. The quarry produces
two main types of material :
1. pure limestone
2. a mixture of marls and clays
This material is stored in the storage shop. The next operation is the
preparation of raw material. This operation is performed using crusher-
dryers on the primary materials already mentioned. Raw material is a very
fine dust of even consistency, the composition of which is determined
according to the type of clinker one wishes to produce.
The next step is the clinkerisation stage. At AIRVAULT, we use the semi-dry
method which is characterised by the fact that an exchange takes place
between hot gases and a layer of granules. These granules are manufactured
in plates from a mixture of raw material and water.
A number of processes take place in the kiln.
1st process : drying
2nd process : deearbonation (in the second chamber)
3rd process : clinkerisation
In the clinkerisation reaction, the limestone molecules combine with silica,
aluminium oxide and iron to produce clinker. It should be noted that a flame
with an extremely high temperature is absolutely essential in our cement
manufacturing process, as clinkerisation takes place at around 1450°C.
The processed material then drops into a cooler where it is soaked. It is
then placed in storage silos. The next operation involves the manufacture of
cement through crushing and the addition of gypsum (a binding agent).
The cement is then ready for shipping, mainly in bulk by road, in bags, or
fay rail.
C-133
-------
SUITABILITY OF CEMENT KILNS FOR WASTE DESTRUCTION
See the clinkerisation system diagram.
A cement kiln offers numerous advantages which provide a permanent potential
for waste incineration :
* THE TEMPERATURES OF THE GASES ARE VERY HIGH AND THEIR RESIDUAL PERIODS ARE
VERY LONG : firing is carried out at between 1400°C and 1500°C, the
temperature of the flame is around 2000°C, the residual period of the gases
at above 1200°C is estimated at more than 5 seconds.
* EFFICIENCY OF GAZ PURIFICATION : the forced contact produced by the
counter-current flow of hot gases into the basic material creates an
integrated purification system which neutralises and dry cleans the gases
produced through the combustion of waste.
* ELIMINATION OF INCINERATIONS CINDERS : the slag produced in incineration
is absorbed in inert form into the crystal lattice of the clinker.
* SAFETY AND RELIABILITY OF DESTRUCTION : the contraints imposed on cement-
manufacturers with regard to clinker quality call a regular checking of
materials used in the manufacturing process, with particular emphasis on
incinerated by-products. They also call for close monitoring of combustion
parameters in the interests of consistency and efficiency.
C-134
-------
ACTIVITY DESCRIPTION
Reception and storage procedures
During your visit you will be able, to observe the reception procedure in
detail.
Our computer system enables us to keep permanent tracability.
C-135
-------
BRANCHES OF ACTIVITY AND CAPACITIES
Presentation of activity sheets.
First branch of activity
For the incineration of residual liquids, the factory is authorized to
process 18,000 tons of liquids per year. We have a storage capacity of 50 ra3
for acidic products, and 380 m3 for non-acidic products. These products are
incinerated and injected in the decarbonation chamber of the Lepol grid. We
are authorized to receive products within the following limits :
chlorine < 2 %
sulphur < 4 %
heavy metals < 1 %
The other parameters indicated on this activity sheet are the technical
parameters which enable us to achieve a high standard of word.
Second branch of activity : use of substitution fuels, known as the 3000
Range
The storage capacity is 2 x 300 m3. Injection can be effected either via the
main nozzles of the two large kilns or via the burners installed in the
decarbonation chamber.
The authorized capacity is 100,000 tons per year and we are authorized to
receive products which have :
chlorine at < 2 %
sulphur at < 4 %
a low flash point
The heavy metal content must be below 1 %. The other particulars are
technical limits wich ensure a good quality of incineration.
Last branch of activity ; used oils
We are authorized to process 7,000 tons per year. We have just requested
permission to process 14,000 tons per year. These oils are incinerated via
the main nozzles of the kilns. The only constraint imposed on us with regard
to these oils is a limit on the level of PCB, which must be below 100 ppm.
C-137
-------
I have just spoken about branches of activity and limits imposed on the
products handled. Our authorization to process also imposes certain 11-:. .•;
regarding emissions and the composition of gases released through the
chimney. Limits are thus imposed with regard to levels of
dust at < 150 mg/Nm3
chlorine at < 10 mg/Nm3
heavy metals at < 0,5 mg/Nm3
C-137
-------
C-138
-------
JEAN MARC RIEGER
NATO/CCMS Guest Speaker
C-139
-------
NATO CCMS
PILOT STUDY DEMONSTRATION OF REMEDIAL ACTION
TECHNOLOGIES FOR CONTAMINATED LAND AND CROUNDWATER
SESSION OF NOV. 6TH 1990 IN ANGERS :
INCINERATION IN CEMENT KILNS AND SANITARY LAND FILLING
By Jean-Marc RIECER
SCORI
10/24/1990
C-140
-------
SCORI is an outgrouth of the Environment Department of SERI RENAULT
Engineering (Car Manufacturer).
The first projects date from 1972 and consisted of studies and surveys on
industrial wastes on behalf of the French Government.
From 1976, SERI has collaborated with the company FRANCE DECHETS on
the development of a network of controlled, special waste landfills in
France. The cooperation between our company and FRANCE DECHETS is
still running and will be described later on.
As early as 1977, the company had made contact with CIMENTS FRANCAIS
for the development of waste incineration in cement kilns.
The company SCORI was created in 1979 and provides services in the field
of sanitary landfilling of special (hazardous) waste and cement kiln
incineration.
During the early 1980's, SCORI progressively expanded and strengthened
its waste treatment activities and became one of the major French waste
management firms.
In the continuation of its development, SCORI became a subsidiary of the
principal cement companies in 1985, namely CIMENTS FRANCAIS, CIMENTS
LAFARGE and VICAT.
Since then, SCORI has continued its internal and external growth.
C-141
-------
Treating more than 700.000 tons of special waste in 1988, and almost
900.000 tons in 1989, SCORl has a consolidated turnover of FFr 180
millions.
SCORl employs over 160 personnel specialized in the recycling and disposal
of industrial waste in its seven business offices and its five subsidiaries.
SCORI's principal activities are in the following areas :
Class 1 and 2 Controlled Waste Landfilling
Waste landfilling centres are the first in a line of SCORl services. At the 8
centres in France run by FRANCE DECHETS and its subsidiaries, SCORl
receives a large spectrum of special industrial wastes in perfect conformance
with existing legislation.
500.000 tons are treated annuaJly on these Class 1 sites (permeability of the
underlying earth less than 10 mis).
The total number of Class 1 sites in France is 11.
Cement Kiln Incineration
Destruction in cement kilns combines environmentally safe waste incineration
(up to 2000°C) and energy recovery. Fifteen kilns are today licensed for
waste incineration in France. SCORl is involved in 11 of them. 250.000 tons
are incinerated annually in these kilns.
Combustible Waste Preparation Centres
Certain types of waste cannot be directly incinerated at a cement plant
because of their physical characteristics.
SCORl and its stockholders have developed a technique for producing a
stable combustible suspension called "COMBSU", starting with liquid, solid
or pasty waste.
Two centres are producing this combustible, treating approximately 50.000
tons/year altogether.
C-142
-------
. Pretreatment and Treatment of Waste by Physical-Chemical Techniques
Various centres are specialized in the stocking, grouping and pretreatment
of industrial waste. SCORI is involved in 6 of them, where more than
150.000 tons of materials have been selected, prepared and distributed for
appropriate treatment.
. Co-Incineration with Household Wastes
20.000 tons are treated annually by SCORI by co-incineration in one out of
the two existing household waste incinerators licensed for hazardous waste
treatment in France.
Waste Recovery and Plant Dismantling
SCORI provides sorting and disassembly services as well as a resale
network. Close to 25.000 tons of different raw materials are handled
realizing important savings for its customers (e.g. RENAULT).
A fast growing plant dismantling activity has been added to this
department, mostly concerned by material recycling hit working together
with our haz-waste specialists when cleaning or decontamination is required.
In addition, SCORI's policy of European expansion has led to the creation
of two new foreign subsidiaries in Belgium and Spain.
C-143
-------
FACILITIES IN FRANCE
Corporate and regional offices
Cement and incineration plants
Class 1 landfill sites
Pretreatment and treatment centers
C-144
-------
The commercial network includes 7 regional offices.
C-145
-------
' SOCIETE DES
CIMENTS FRANCA
I
IS
CIMENTS
LAFARCE
CIMENTS
VICAT
SCORI
CEDILOR
SOVALEC
19%
CBL
10%
RIC
51%
COHU
51%
ECOTEC
19%
SCORIBEL
(Belgium)
ENDER
(Spain)
C-146
-------
INCINERATION IN CEMENT KILNS
The cement kiln is a particularly effective tool for the incineration of
special wastes :
. high temperatures and long gas residences times (more than 5 seconds at
more than 1200°C),
. efficient gas cleaning : the cement process offers a very high capture
capacity for halogens (close to 100%) and for metals (greater than 95%),
. the cinders remaining from waste incineration are incorporated in their
inert form into the cement clinker.
. the quality and the reliability of destruction are related to the necessity
of closely following the clinker fabrication parameters,
. the depth of response from the cement manufacturing profession which
has oriented its significant technical potential towards the quality of
incineration.
C-147
-------
WET PROCESS
I
(—*
09
DIRECTION OF MOVEMENT OF THE MATERIAL
Firing end
TEMPERATURE «C
Cllnkeri-
sation zo
Decarbonation zone
100
700/900
1450
-------
Temperature of the materi
TEMPERATURE OF A MOLECULE INTRODUCED AT THE BURNER AS A FUNCTION OF TIME
TEMPERATURE* C
2000
1000
7s
TIKE
-------
SCORI'S WASTE ACCEPTANCE PROCEDURE
SCORI initiated and developped the procedure for acceptance of polluting
wastes in treatment plants.
1st step : Waste characterization
Waste characterization is based on a sound knowledge of origins of the
waste and on sampling and laboratory analysis.
For incineration, analysis of water content, calorific value, chlorine, heavy
metals, PCB, sulfur etc... are performed.
In the case of landfilling, leaching tests are used to simulate the behavior
of wastes in the presence of water and to identify the risk associated with
the dissolution of polluting substances.
These analyses are performed by external laboratories, or by the
laboratories of the treatment centres.
Waste acceptance
The results of waste characterization (physical state, levels of polluting
substances in relation to admission thresholds, etc...), permit the
evaluation of the acceptability of a waste in treatment facility.
When a waste is found acceptable, notification is made to the waste holder
who can then arrange the delivery of his waste to the centre. An
"Acceptance Certificate" is sent to the holder.
Waste admittance on the site
At site reception, and after checking the Acceptance Certificate,
verification is made, to ensure that the waste delivered conforms with the
sample held by the onsite laboratory.
Following this admittance procedure, the weighing and unloading are
performed, and a certificate of transfer of control is then given to the
carrier and waste holder.
This procedure is rigorously followed and contributes to an efficient
selection of wastes which merit specific disposaE
C-150
-------
Appendix D
United States Proposal For
New NATO/CCMS Pilot Study
D-l
-------
APPENDIX D
UNITED STATES PROPOSAL FOR NEW NATO/CCMS PILOT STUDY
Lead Organization: U.S. Environmental Protection Agency
Office of Research & Development
Risk Reduction Engineering Laboratory
Superfund Technology Demonstration Division
Date of Initiation: November 1992
Pilot Country: United States
Proposed US Director: Stephen C. James
Chief, SITE Demonstration & Evaluation
Branch
26 W. M.L. King Drive
Cincinnati, Ohio 45268
513-569-7696
513-569-7620 (Fax)
Co-Pi lot Countries: Open & Welcome
Proposed Title: Research, Development, & Evaluation of Remedial
Action Technologies
Project Duration: 5 years
Proposed Project Scope:
The United States proposes a follow-up study to the existing NATO/CCMS
study titled "Demonstration of Remedial Action Technologies for Contaminated
Land & Groundwater". This new study would have three goals:
* Continuation of current study where technology performance is
documented,
* Examination/identification of emerging technologies that
are at the bench/pilot scale,
* Development/establishment of uniform data reporting system so
that results will be universally reported.
First, the new study would enable participating countries to continue to
present and exchange technical information on technologies for the cleanup of
contaminated land and groundwater. During this current study, participating
D-2
-------
countries have been able to exchange technical Information on developed
technologies that has benefltted both the countries and technology developers
from various countries. This technology information exchange and assistance
to technology developers would therefore continue.
Secondly, the proposed study would expand the current study by
introducing a research and development component to it. Currently, various
countries support research/development of hazardous waste treatment/cleanup
technologies by governmental assistance and private funds. This part of the
study would report on and exchange information of ongoing research in this
area. As with the current study, projects would be presented for
consideration and if accepted, fully discussed at the meetings. A final
report would be prepared on each project or category of projects (such as
thermal, biological, etc.) and compiled in a book as the final study report.
Finally, the pilot study group would develop and adopt reporting methods
for results from technology studies (demonstrations, bench, pilot, and other
technology studies) including thermal, biological, physical, chemical,
solidification/stabilization, etc. Reporting methods would be developed for
each technology. This would enable others to be able to evaluate the
performance of a technology based on the particular environmental or
health/risk standards adopted by that country. From this information, an
International data base could be maintained and accessible to anyone.
Ideas & Contributions from Interested Participants:
D-3
-------
Appendix E
International Standards Organization
E-l
-------
Sonderdruck aus DIN-Mitteilungen + elektronorm 68. 1989, Mr. 10, Seite 532 bis Seite 537
OK 63 (4 006(100)150
Bodenbeschaffenheit
(ISO-Arbeit)
Die vierte Plenarversammlung des ISO/TC 190 .Boden-
beschaffenheit" (Sekretanat NNI) fand am 10 und
14 April 1989 in Berlin statt Vom 10 bis 13 April 19B9fuhr-
ten funf Unterkomitees und 21 Arbeitsgruppen sowie eine
Ad-hoc-Gruppe Sitzungen durch Em Treften der Vorsitzen-
den und der Sekretare erganzle das Programm
Mil Ausnahme der Plenarsitzung des ISO/TC 190 am
14 April 1989 fanden alle Srtzungen anla'Blich der Veranstal-
tung WASSER BERLIN '89 im ICC Berlin statt Insgesamt nan-
men 93 Delegierte und Beobachter aus achl Landern teil Die
deutsche Delegation wurde von Prof Or R Leschber. Berlin,
geleitet
C R Meinardi (Ntederlande), Vorsitzender des ISO/TC 190,
eroffnete die Sitzung mit emer GruBadresse, in der er die
histonschen Errungenschaften im Geiste der Aufkfarung zur
Zeit Friednchs des GroBen hervorhob Besonders die ratio-
nelle Umselzung wissenschafthcher Ergebnisse fur Verwal-
tungsaufgaben des preuBischen Staates war em Anhegen
Fnednchs des GroBen, und auch heute besteht auf der Ver-
waltungsebene em groBer Bedarf an gesicherten wissen-
schaftlichen Erkenntnissen. C. R Memardi druckte die Hoff-
nung aus.daB die Sitzung in Berlin em weiterer Schritl zur Er-
stellung wen Normen im Bereich der Bodenbeschaffenheit
sei
Als neues 0-Mitghed der Unterkomitees 1 bis 5 wurde die
Tschechoslowakische Normenorgamsation (CSN) registnert.
Die Benchte der Unterkomitees wurden diskutiert und an-
genommen Dabei wurde festgestellt. daB allgemem der
Wunsch nach noch engerer Zusammenarbeit als bisher be-
steht Der Vorsitzende regte an, diesen Komplex wahrend der
nachsten Plenarsitzung mit Pnontat zu behandeln
K -G Lmgner (Schweiz, ISO) warn te davor.weitere koordmie-
rende Gremien emzusetzen Kcoromation und Zusammen-
arbeit sollten von den Sekretariaten der Techmschen Komi-
tees und der Unterkomitees uberwacht und gesteuert wer-
den Der Vorsitzende und das Plenum waren jedoch der Mei-
nung, daB hier spezielle Aktmtaten emgeleitet werden mus-
sen
Frau Dr S Schmidt (Leverkusen), Vorsitzende des
ISO/TC 147 .Wasserbeschaffenheit", legte den Liaison-
Bencht vor S e wies darauf hm, daB eine Reihe von Normen
aus dem Bereich der Wasseruntersuchung hmsichtlich der
Anwendung auf Bodenuntersuchungen uberpruft werden
sollte. um Doppelarbeit zu wermeiden Kritik an Normen des
ISO/TC 147 ist in jedem Fall willkommen
Prof Dr H -P B/ume (Deutschland), Beobachter der Inter-
nationa len Bodenkundlichen Gesellschaft, erklarte die Be-
rettschaft zur Zusammenarbeit mit dem ISO/TC 190
Als neue Arbeitsgebiete wurden die Bestimmung des Gehal-
tes an organischem Material, die Bestimmung des Kalkgehal-
tes und der Nachweis von pathogenen Baktenen vorgeschla-
gen
Von Deutschland kam die Anregung zu prufen, inwieweit
Modelle, z 8 zum Transport von Nahr- Oder Schadstoffen im
Boden. veremheitlicht werden konnen und sollten Die Dele-
gierten stimmten dem zu, bezweifelten aber, solche Modelle
derzeit in die Zwange emer Norm uberfirtiren zu konnen. ob-
wohl die Anwendung zum Teil bereils routmemaBig erfoigt
Zunachst soil enfsprechendes Material gesammelt werden.
nach dessen Auswertung em Diskussionspapier entstehen
soil Falls die Veremheitlichung solcher Methoden zum heuti-
gen Zeitpunkt nicht sinnvoll erschemt. wird die Plenarver-
sammlung ggf entscrieiden. die der/eitigen Erkenntnisse als
Italian schlug vor, die Analyse von Kompost und Schlamm in
das Programm des ISO/TC 190 aufzunehmen Dazu wurde
darauf hmgewiesen, daB fur den Bereich Schlamm die Zu-
standigkeit beim ISO/TC 147 liege.
Nach den Sitzungen in Berlin ghedert sich das ISO/TC 190
wie folgt.
ISO/TC 190
ISO/TC 190/SC 1
ISO/TC 190/SC 1/WG 1
ISO/TC 190/SC 1/WG 2
ISO/TC 190/SC 2
ISO/TC 190/SC 2/WG 1
ISO/TC 190/SC 3
ISO/TC 190JSC 3/WG 1
ISO/TC 190/SC 3/WG 2
ISO/TC 190/SC 3/WG 3
ISO/TC 190/SC 3/WG 4
ISO/TC 190/SC 3/WG S
ISO/TC 190/SC 3/WG 6
ISO/TC 190/SC 3/WG 7
ISO/TC 190/SC 3/WG 8
ISOHC
ISO/TC
ISO/TC
ISO/TC
ISO/TC
ISO/TC
ISO/TC
ISO/TC
ISO/TC
ISO/TC
ISO/TC
ISO/TC
ISO/TC
ISO/TC
ISO/TC
ISO/TC
ISO/TC
ISO/TC
ISO/TC
ISO/TC
190/SC 3/WG 9
190/SC 4
190/SC 4/WG 1
190/SC 4/WG 2
190/SC 4/WG 3
190/SC 4/WG 4
190/SC 5
190/SC S/WG 1
190/SC 5/WG 2
190/SC 5/WG 3
190/SC S/WG 4
190/SC 5/WG B
190/SC S/WG 7
190/SC 5/WG 8
190/SC 6
190/SC 6/WG 1
190/SC 6/WG 2
190/iC 6/WG 3
190/SC 6/WG 4
190/SC 6/WG 5
.BodenDeschaffenheit"
.Beweriung der Krilenen, Teimmologie und Kodifi-
lierung-
.Teimmologie'
.Bodendelastung-
.Probenarime'
.P'obenaflme'
.Chemiscne Metnoden una Sodenchauniensuka'
.Bostimmung von Scfiwermetallen Selen und
Arsen-
.Bestimmung vom Sticksloll und SlickslortveiBin-
Oungen" .
.Bestimmung von Sullat Suldl Sullid und elemen-
tarem Schwgfer
.Bestimmung von Cyamd'
.Bestimmung von Gesamipnosohor und Phoso^af
.Mmeralor
.Chloroeslizide PCBs und cnionerte Konlenwas-
serstode'
.Bestimmung des pH-Wenes der elektrischen Leu-
lahigken des Reoox-Poiennais und der Kaiionen-
ausiauscnkapainaf
.Prooenvoroenandlung-
.Bioiogisene venanren-
.Biologiscne Abbaubaike
-------
chen erprobt und ncht auf Landschaften mn starkerem
Relief ubertragbar Eine uberarbeitete Fassung wird voraus
Sichtlich im November 1989 vorhegen
Da eme erfolgreiche Proberahme mitentscheidend von eni
sprechenden mslrumentellen Techniken abhangt. ist auch
rrerzu em Vorschlag in der Diskussion, tier von Experten
GroGbntanniens koordmiert wird
Die Arbertsgruppe 1 hat weiterhm beschlossen. mil Arbeiten
zu SicherneilsmaBnahmen im Bereich der Geprobung von
Boden zu begmnen Hierbei mussen sowohl Aspekte der
technischen Sicherung von Probenahmestellen als auch Fra-
gen zur Exposition von Probenehmern an stark kontamimer-
ten Standorten berucksichtigt werden.
In Zusammenarbeit mil der ISO/TC 190/SC 4/WG 4 .Hem-
mung der mikrobiellen Bodentatigkeit" soil em Vorschlag zur
Probenahme fur mikrobiologische Zwecke erstettt werden
Die nachste Sitzung wird im November 1939 mDeltl (Nieder-
lande) stattfmden
ISO/TC 190/SC 2 .Probenanme"
Die Plenarversammlung unter Vorsitz von Dr W Bitter
(Deutschfand) bestatigte die bishengen Ergebnisse der
Arbeitsgruppe 1 und verabschiedele das Arbeitspapier nAH-
gememe Anforderungen an die Probenahme von Boden" zur
Registrierung als ISO-Entwurtsvorschlag
Die Plenarversammlung bat die neugegrundete
ISO/TC 190/SC 3/WG 9 .Probenvorbehandlung' darum,
emen Vertreter aus der Arbeitsgruppe 1 als standiges Mil-
glied an der Arbeit teilnehmen zu lassen, um der notwendi-
ger Infcrmalionsauslausch an dieser wichligen Schnjltstelle
zwisctien Probenahme und Probenanalysegewahrleisteniu
konnen
ISO/TC 190/SC 3/WG 1 .Sestimmung von Scrtwerme-
tallen, Selen und Arson"
Im Mrttelpunkt der Sitzung der Arbeitsgruppe 1 (Leitung Dr
W Bitter, Deutschland) standen die Auswertung und Diskus-
sion uber die fiingversuchsergebnisse zum Aufschluf) von
Bodenproben mit Konigswasser Im Ringversuch wurden
zwei bereits aufbereitete Proben — Probe 1 mit gennger
Schwermetallkontammatian, Probe 2 mit deutlich hoher
Schwermeiallkontammation — mit Konigswasser auf-
geschlossen und mittels Alomabsorptionsspektrometrie
(AAS) analysiert Bei den enthaltenen SchweimelaUen
Chrom. Mangan. Cobal1, Nickel, Kupfer, Zmk, Cadmium und
Blei gab es Schwiengkeiten - erwartungsgemaG - beim
Nachweis von Chrom in Probe 1 und Probe 2 und bei Cad-
mium in Probe J Die Ergebnisse der weiteren Element-
bestimmungen entsprechen in den statistischen Parametern
den Ergebmssen. die an anderer Stelle (z B bei Rmgver-
suchen der Europaischen Gememschaften) gemacht wur-
den
Fur Chrom wurde vorgeschlagen, emen AnschluOtest unter
Addition emer Cr-Losung defmierter Konzentration durchzu-
fuhren, um sicherzustellen, wo der Fehler zu suchen is) im
AufschluB Oder in der Analytik Zur genaueren Ertassung von
Cadmium im Bereich \ mgfkg Trockenmasse Boden w
-------
Die Bestimmung des freien Cyanids erfolgt uber Titration mn
Siibernitrat Oder kolonmetnsch Die Bestimmung der verbiei-
benden Cyanide (komplexe Cyanide) erfolgt nach Zugabe
von Kupferchlond mit den gleichen Methoden In beiden Fal-
len gilt daS die Titration fur Gehalte an CN~ Kleiner als
500 ug/kg geeignet ist
Mitgheder der Arbeitsgruppe werden erganzend Stabihtats-
tests an remen Cyanidkomplexen in kaustischen Losungen
durchfuhren, um die Emflusse von Zeit und Lbsung auf die
relativen Verhaltmsse von freiem und komplexem Cyanid
darzustellen.
ISO/TC 190/SC 3/WG 5 ..Bestimmung von Gesamt-
phosphor und Phosphat"
Die Arbeitsgruppe hat die Pnoritat auf die Bestimmung des
natnumbikarbonatloslichen Phosphats gesetzt. Dem Verfah-
ren liegt em Vorschlag des Vorsitzenden der Arbeitsgruppe,
Dr A Barbers (Italien), zugrunde Wahrend der Sitzung in
Berlin wurde dieser Vorschlag ausfuhrlich diskutiert Vom
Vertreter Frankreichs wurde die Methode - und damit auch
die zugrundehegende Methode von 0/sen et al (1954) - in
Frage gestellt Dazu wurden emige Ergebnisse des franzosi-
schen Vertreters vorgestellt. die dieser mit der 0/sen-Metho-
de und emer Methode, bei der eine synthetische Losung an-
gewendet wird, erzielt hat
Die Ergebnisse waren fur die weiteren Teilnehmer uber-
raschend Daraufhm wurde beschlossen, das Bikarbonat-
Verfahren durchzusehen und besonders Storungen durch
Arsengehalte zu berucksichtigen
Frankreich wird seme Methode ebenfalls uberarbeiten Im
AnschluB daran soil em Rmgversuch stattfmden, dessen
Resultate im September 1989 vorhegen sollen
ISO/TC 190/SC 3/WG 6 .Mineralol"
In der unter dem Vorsitz von Dr K Liphard (Deutschland) ge-
fuhrten Arbeitsgruppe wurde beschlossen, fur die Bestim-
mung von Mmeralol in Boden zwei Methoden zu erstellen Die
erste Methode ist em Screemng-Verfahren, das sowohl auf
leicht als auch auf stark kontamimerte Boden angewendet
werden kann Als zweite Methode soil eln gaschromatogra-
phisches Verfahren genauere Werte hefern
Die bereits vorhegenden Vorschlage aus Deutschland und
den Niederlanden smd so weit ausgereift, daG eine Kombma-
tion beider Vorschlage bis zum Herbst 1989 vorhegen wird
Zur Bestimmung von fluchtigen Aromaten und Ahphaten in
Boden lag em niederlandischer Vorschlag vor, der nach
wesentlicher Uberarbeitung noch 1989 erneut emgereicht
werden soil
Bei der Bestimmung der polycyclischen aromatischen Koh-
lenwasserstoffe (PAK) in Boden wird nach Ansicht der Teil-
nehmer eine Embeziehung alter 16 PAK der EPA-Liste unver-
meidbar sem
Der Vorsitzende wird noch 1989 emen Vorschlag zur Bestim-
mung mittels HPLC vorlegen
Die Probenvorbehandlung soil in Absprache mit der
ISO/TC 190/SC 3/WG 7 erfolgen
ISO/TC 190/SC 3/WG 7 .Chlorpestlzide, PCB's und
chlorlerte Kohlenwasser-
Stoffe"
Die vom Vorsitzenden, Prof Dr W Ebmg (Deutschland). 1987
vorgelegte und dreimal uberarbeitete Metr-ode zur Bestim-
mung von Organochlorpestiziden und polychlonerten Biphe-
nylen in Boden ist zur Registnerung als ISO-Entwurfsvor-
schlag (ISO/DP) verabschiedet worden Die Vorbehandlung
der Proben war bis zuletzt em schwienges Problem, konnte
aber gelost werden
E-4
Zur Bestimmung leichtfluchtiger halogemerter Kohlenwas-
serstoffe wurden zwolf Vorschlage bzw Veroffentlichungen
emgereicht. Die Arbeitsgruppe hat entschieden, die folgen-
den neun Verbmdungen mit Pnoritat zu behandeln Dichlor-
methan. Chloroform. Tetrachlorkohlenstoff, 1,1,1- und 1,1.2-
Tnchlorethan, 1,1,1.2-Tetrachlorethan, 1,1.2-Tnchlor- und
1.2.2-Tnfluorethan. Trichlorethylen, 1,1,2.2-Tetrachlorethylen
Als Verfahrensgrundlage wird erstens eine stark modifizierte
Version der Richtlime VDI3865 Blatt 5 (Entwurf) herangezo-
gen, zweitens em Extraktionsverfahren.
Der Bereich der Triazm-Herbizide wird durch em in Vorberei-
tung befmdliches Arbeitspapier auf der Methode DFG S 7 be-
handelt werden Nach Moglichkeit soil auch Hexazmom mit-
erfaBt werden
Em weiterer Punkt der zukunftigen Arbeit wird die Erstellung
emer Methode zur Bestimmung von Chlorphenoxysaure-
Herbiziden im Boden sem Zehn Verbmdungen sowie deren
Ester und Sauren sollen erfaBt werden Erste Umfragen
haben ergeben, daS eine ausgereifte Multimethode fur
Bodenanalysen kaum beschneben wird. obwohl Boden sehr
haufig auf Herbizidruckstande untersucht werden
ISO/TC 190/SC 3/WG 8 .Bestimmung des pH-Wertes,
der elektrischen Leitfahigkeit
des Redox-Potentials und der
Kationenaustauschkapazitat"
Der zweite Entwurf fur eine Methode zur Bestimmung des
pH-Wertes m Boden kann nach Uberarbeitung durch den
Vorsitzenden. Dr V Houba (Niederlande), als ISO-Entwurfs-
vorschlag registnert werden Auf die Durchfuhrung ernes
ISO-Rmgversuchs kann nach Ansicht der Arbe'tsgruppe ver-
zichtet werden, weil em kurzlich in den Niederianden durch-
gefuhrter Versuch sehr gute Ergebnisse brachte
Der erste Vorschlag fur eine Methode zur Bc-otimmung der
potentiellen Kationenaustauschkapazitat wird intsprechend
den Berliner Diskussionen uberarbeitet Im AnschluB wird em
Rmgversuch mit vier Boden stattfmden. der bis Februar 1990
ausgewertet sem wird
Entsprechendes gilt auch fur die effek'ive ,?:ionenaus-
tauschkapazitat
Zur Bestimmung der elektrischen Leitfal.o sit wird Dr
v* Houoa emen Entwurf fur das Extraktr-" -ra-ren aus-
arbeiten
Die Arbeitsgruppe schlug dem ISO/TC 'Si
Arbeitsgebiet um die Bereiche .Orgam-
und .Kalkgehalt" zu erweitern
C- vor. ihr
ISO/TC 190/SC 3
.Chemische Met.:;-
Bodencharakteris
Die Sitzung wurde von Prof Dr R Leschbf ," ''s:hland)
eroffnet Die Benchte der Arbeitsgruppen • :. vcrgetra-
gen von den Vorsitzenden Oder von Teilne!-..-"-, • ' Arbeits-
gruppen, wurden zur Kenntnis genommen <:,. 'a: gt Das
Sekretanat des ISO/TC 190/SC 3 wird die • sclredeten
Dokumente der Arbeitsgruppen 7 und 8 zur.",-; - • 3-jng als
ISO/DP weiterleiten
Die Plenarversammlung hat beschlossen, den- \ i v-ch der
Arbeitsgruppen zu entsprechen und eine nejr«. ^rbeits-
gruppe emzurichten, die Verfahren zur Proben \- jehand-
lung veremheithchen und daruber hmaus alle w -thchen
Aspekte zu analytischen Ablaufen berucksichtir. oil
Mitgheder der Arbeitsgruppe 9 werden die Vors. _ Jen der
Arbeitsgruppen 1 bis 8 bzw gemeldete Experte . diesen
Gruppen sowie auf Vorschlag des ISO/TC 190/;. er Vor-
sitzende der ISO/TC 190/SC 2/WG 1 sem Die. :... 'ng der
neuen Arbeitsgruppe wird der Vorsitzende dec i'" jrkomi-
tees 3. Prof Dr A Leschber. ubernehmen
-------
Dem Vorschlag der Arbeitsgruppe 8 lolgend, beschloB das
ISO/TC 190/SC 3" die Aufnahme von Methoden zur Sestim-
mung des Gehaltes an orgamschen Bestandteilen im Boden
imd von Methoden zur Bestimmung des Kalkgehaltes in das
Arbeitsprogramm Beide Bereiche werden der Arbeitsgrup-
pe 8 zugewiesen
Die fiachsle Sitzung wird zjsammen mil der nachsten Sit-
zung des ISO/TC 190 slaltfinden
ISO/TC 190/SC 4/WG 1 nBiologische Abbaubaikeil"
Die Arbeitsgruppe (Vorsitz R v d Berg, Niederlande)disku-
tierte zunachst die Ergebmsse der Umfrage zur Erhebung
von Schlusselkntenen zur Charaktensierung von Testmetrio-
den zur btologisctien Abbaubarkeit Die meisten der em-
gereichten Kntenen bezogen sich auf Pflanzenschutzmittel
Die Arbeitsgruppe wird eme flichtlmie erstelten. in der der
aerobische Abbau landwirtschaftlich und mcntlandwirt-
schaftlich eingesetzter Chemikalien berucksichtigt werden
wird
Die Niederlande werden em Diskussionspapier zur Rolle des
Bodenwassers beim tiologischen Abbau vorbereiten Eme
enge Zusammenarbeit mil der ISO/TC 190/SC 5/ WG 3 .Be-
stimmung des Wassergehaltes" ist rtotwendig Eme Uber-
arbeitung von Methoden zur Bestimmung des biologischen
Abbaus wird von Deutschland vorbereitet
In Fragen zur Probenahme wartet die Arbeitsgruppe die Vor-
schlage der ISO/TC 190/SC 4/WG 4 ab
ISO/TC 190/SC 4/WG 2 .Bodenfauna"
Die Arbeitssruppe unter Vorsitz von Of R Cabndenc (Frank-
reich) diskutierte den Entwurf zu einer gememsamen Norm
uber den sog .Artificial-soil-" und den ..Artisol-Tesl" zur Be-
siimmung der Toxizitat emer Substanz auf Regenwurmer Sie
hat entschieden. die Verfahren zu trennen Beide Verfahren
werden uberarbeitet, kommentiert und anschheGend dem
Plenum des ISO/TC 190/SC 4 zur Registnerung als ISO/DP
empfohlen
Erganzt werden sollen diese Verfahren durch emen langerfn-
stigen Regenwurmtest zur Erfassung subletaler Effekte Hier-
zu werden Arbeitspapiere von Deutschland und den Nieder-
landen vorbereitet
Fur den Bereich von Testverfahren mil Arthropoden werden
em akuter und em langerlnsViger Test mrt Collemooten disku-
tiert werden
Neben toxikologischen Methoden wird auch die Beurteilung
der Standortbedmgungen m Zusammenhang mil den Pro-
blemen uber die Bewertung von Ergebmssen aus Labor- und
Freilandtests behandelt werden
ISO/TC 190/SC 4/WG 3 .Bodenflora"
Die Arbeitsgruppe traf sich erstmalig unter dem Vorsitz von
Dr 7 Eggers (Deutschland) Zunachst wurde noch emmal
uber den sehr allgemem gefaSten Tilel der Arbeitsgruppe ge-
sprochen und schheBlich entschieden. den Titel beizubehal-
ten
Die Durchsicht der bisher vorhegenden Untertagen ergab
eme Zweiteilung der Methoden
1 Gruppe = Phytotoxizitatstests
2 Gruppe = Wurzellangentests
Aus dem vorhegenden Material wird der Vorsitzende eme
vergleichende Ubersicht erstelten
Da eme durch die EG-Kommission verabschiedete Fassurg
des Phytotoxizitatstests an hoheren Pfianzen rticht in Aus-
sicht steht, wird Deutschland emen Entwurl vorDereiten, in
dem die Erfahrungen aus der Entstehungsgescriichte und
aus Ringversucnsbeteihgungen verarbeitel werden
E-5
Schwerpunkl der nachsten Arbeiten ist der Wurzellangen-
test DervonGroBbntanmeneingebractite Entwurf wird uber-
arbeitet und Ende 1989 abschliefiend beraten
ISO/TC 190/SC 4/WG 4 nHemmung der mikrobiel...
Bodentatigkeit"
Die von Frau D Castle (GroBbntanmen) geleitete Arbeits-
gruppe hatte emen Entwurf zur Probenahme von Boden fur
mikrobiologiscrie Uniersuchungen ausgearbeilel, der aus-
fuhrlich diskutiert wurde Parallel wurde dieser Entwurf auch
in der ISO/TC 190/SC 2/WG 1 besprochen. Neben der
eigentlichen Probenahme smd in dem Entwurf auch die Be-
handlung und Lagerung von Oberboden erfaSt. er wird unter
Berucksichiigung der Diskussionsbeitrage uberarbeitet
Der zweite Arbeitsschwerpunkt umfaQte den Bereich Stick-
stoffmmeralisation. msbesondere die Nitnfizierung Fur die
Ausarbeitung von Verfahren zur Extraktion und zur Bestim-
mung von NH4., KO3_ und NO2_ in Boden soil eng mil der
ISO/TC 190/SC 3/WG 2 zusammengearbeitet werden
Die Arbeitsgruppe 4 wird das in der Arbeitsgruppe 1 m Vor-
bereitung befmdliche Arbeitspapier zur Boden/Wasser-
Beziehung ebenfalls berucksichtigen
Informationen uber alternative Substrate zur Ammonifizie-
rung und Nitnfizterung sollen der Vorsitzenden zugesendet
werden Eme Liste mit Begnffen, die aus der Sicht der
Arbeitsgruppe 4 defmiert weiden sollen. wird dem
ISO/TC 190/SC 1 zugeleitet werden
Die nachste Sitzung ist fur den 18 September 1989 in Basel
(Scriweiz) vorgesehen
ISO/TC 190/SC 4 nBiologische Verfahrert"
Die Sitzung wurde vom Vorsitzenden Dr K Cook (GroBbri-
tannien) eroffnet GroGbritannien hat em neues Arbeitsgebiet
vorgeschlagen Bestimmung von Pathogenen im Boden Dts-
kutiert wurde daruber. ob nur der Nachweis Oder auch die
genaue Auffuhrung der Pathogene beralen und Prize. Nema-
toden, cohforme Pathogene, Pfianzen und/oder Tiere — Oder
nur menschliche Pathogene — berucksichtigt werden sollen
Es wurde beschlossen, dem Nachweis und der Speziliziemng
m krob eller Pathogene die Pnoritat zu ceben, des weiteren.
daB das Mauplinteresse der Extraktion von Baktenen aus
dem Baden in eme walk^e Losung gelten soil, weil m bezug
auf das eigentliche analytische Verfahren eventuell auf m
Vorbereitung befmdliche Verfahren des ISO/TC 147 ..Wasser-
beschaffenheit" zuruckgegnffen werden kann
Die Arbeitsgruppe 4 wurde gebeten, eme Zusammenstellung
solcher Extraktionsverfahren vorzubereiten Ob die Patho-
gene von dieser Oder emer neuzugrundenden Arbeitsgruppe
bearbeitet werden, blieb often
Die Benchte der Arbeitsgruppen 1 bis4 wurden zur Kenntnis
genommen und bestatigt
Das ISO/TC 190/SC 4 bat das Secretariat des ISO/TC 190.
dafurSorge zu tragen, daB wahrend der nachsten Sitzung fur
Ad-hoc-Treffen verschiedener Unterkomttees untereinander
Termme zur Verfugung stehen
ISO/TC 190/SC 5/WG 1 .Bestimmung des Wasser-
riickhaltevermogens"
In Vertretung der Vorsitzenden. Frau Dr A Carter, ubernahm
Frau Dr C Gardner (beide GroBbntannien) die Leitung der
Sitzung
Die Arbeitsgruppe diskutterte uber die zweite Fassung des
Arbeitspapiers zur Bestimmung der Wasserkennwerte und
beschloB, eme revidierte Fassung vorzubereiten. die dann als
ISO/DP registries werden soil
-------
In dern Entwurfsvorschlag soil auf vier Bodenarten verwiesen
werden Sandboden.Jehmiger Sand. Ton, humoser Boden
Die Plenarversammlung soil uber erne vorlaufige Charakten-
sierung dieser Boden entscheiden und die Empfehlung aus-
sprechen. diese Begnffe ir. den anderen Arbeitsgruppen des
ISO/TC 190/SC 5 entsprechend zu verwenden
Ebenfalls an die Plenarversammlung wurde die Frage gerich-
tet. bei welcher Temperatur physikalische Laborunter-
suchungen von Boden durchgefuhrt werden sollen
ISO/TC 190/SC 5/WG 2 BBestimmung der Wasser-
durchlassigkeit"
In Vertretung des Vorsitzenden, Or C Dirksen, ubernahm
0 Honensius (beide-Niederlande) die Leitung der Sitzung
Die erste Vorlage fur erne Labormethode zur Bestimmung
der gesattigten hydraulischen Leitfahigkeit wurde durch-
gesehen und soil mil Anderungen erneut verteilt werden
Zwei Methoden wurden beraten
- Methods mit konstanten Gradienten (Steady state)
- Methode mit fallenden Gradienten (Unsteady state)
Zur Bestimmung der gesattigten Leitfahigkeit im Gelande
wurden von Frankreicn Unterlagen vorgelegt Em Arbeits-
papier zum Pumpversuch ist in Vorbereitung
Die Veremheitlichung des Bohrlochtests wird so lange zu-
ruckgestellt. bis seme Anwendbarkeit hmreichend geklart ist
Zur Bestimmung der ungesattigten hydraulischen Leitfahig-
keit gibt es erne Reihe von Labor- und Feldmethoden, die
zwar regelmaSig angewendet werden, deren Heranziehung
fur die Normung aber noch nicht in Frage kommt Hierzu soil
eme allgememe ISO-Norm Oder em ISO-Fachbencht vor-
bereitet werden Die dafur erforderlichen Vorarbeiten wer-
den Deutschland und die Niederlande leisten
ISOT/TC 190/SC 5/WG 3 .Bestimmung des Wasser-
gehaltes''
Den Vorsitz der Arbeitsgruppe hatte W van Vuuren (Nieder-
lande)
Zunacnst wurde die erste Fassung ernes Verfahrens zur gra-
vimetrischen Bestimmung des Wassergehaltes intensiv dis-
kutiert Es wurde beschlossen. die Bestimmung des Wasser-
gehaltes mit dem Mikrowellenofen zu streichen Em Hmweis
soil aufgenommen werden, der auf die Probleme zum Verlust
orgamscher Substanz bei der Trocknung bei 105 °C deutet
Auf die Bestimmung der Rohdichte nach emer anderen ISO-
Norm muB hmgewiesen werden Die Reprasentatmtat der
Probe muB deuthcher betont werden
Im Zusammenhang mit der notwendigen Bestimmung des
Wassergehaltes bei chemischen Untersuchungen wird erne
enge Koordination mit dem ISO/TC 190/SC 3 gesucht
Das Feldverfahren mit der Neutronensonde wurde ebenfails
durchgesehen und kann nach erneuter Oberarbeitung als
ISO/DP registnert werden
Uber diese Methode wurde auch unter dem Gesichtspunkt
der moglichen Gefahren, die von der Strahlenquelle aus-
gehen. diskutiert Da die Neutronensonden-Methode die em-
zige zur Zeit verfugbare normungswurdige In-situ-Methode
ist, wird sie beibehalten Aufgenommen werden soil em Hm-
weis, dafl diese Methode nach Moglichkeit ersetzt werden
soil, z B imRahmendesfunfjahngenTurnuszurUberprufung
von ISO-Normen
ISO/TC 190/SC 5/WG 4 .Verfiighares Bodenwasser
Die zweite Vorlage zu emer ISO-Norm uber Tensiometer zur
Bestimmung des Bodenwasserpotentials wurde besprochen
Die vorgelegte Fassung war zu speziell auf einen Torino
metertyp ausgenchtet In der Diskussion wurde msbeson
dere die Beiastung der Umwelt durcn die Anwenaung von
E-6
Hg-Tensiometern betont Als Emheiten wurden kPa und m
festgelegt Frankreich wurde von der Vorsitzenden der
Arbeitsgruppe, Frau Dr. C Gardner (GroBbntanmen). auf-
gefordert, den angekundigten Entwurf zu emer Piezometer-
methode in den nachsten Wochen vorzulegen
Die Arbeitsgruppe schlug dem Plenum des ISO/TC 190/SC 5
vor, allgemem die Bereiche Genauigkeit/Richtigkeit von
Methoden zu diskutieren Dieser Aspekt sollte Bestandteil
jeder Norm werden
ISO/TC 190/SC 5/WG 6 .Bestimmung der Korn-
grdBenverteilung"
Der vom Vorsitzenden Dr P Love/and (GroBbntanmen) aus-
gearbeitete Entwurf zur Bestimmung der KorngroBenvertei-
lung wurde diskutiert. Die folgenden Gesichtspunkte werden
m der Oberarbeitung berucksichtigt
— Aufnahme ernes Anhangs zur Anwendung von Hydro-
metern
— Anleitung, wann und wie Karbonate, Gips und losliche
Salze zu entfernen smd
— AusschluB von Rundlochsieben
- Embeziehung der Kies- und Stemfraktion
Als Dispergierungsmittel wird Na-Metaphosphat verwendet
Ausgeklammert wurde die Festlegung von Fraktionsgrenzen
Diese Festlegung muB durch das ISO/TC 190/SC 5 getrorfen
werden
Die uberarbeitete Fassung soil spatestens bis Mitte 1990 als
ISO/DP registries werden
ISO/TC 190/SC 5/WG 7 .Bestimmung der Rohdichte"
Unter dem Vorsitz von Prof Dr H-P Blume (Deutschland)
wurden zunachst zwei vorgelegte Arbeitspapiere zur Bestim-
mung der Dichte und der Rohdichte (Lagerungsdichte) von
Boden diskutiert Emigkeit bestand darm. daB erne entspre-
chende Norm allgemem gehalten sem sollte (z B kerne kon-
kreten Mengen- Oder Volumenangaben) und spezielle Pro-
bleme (z B stemreiche, humusreiche. tonreiche Boden) in
emem Anhang mit bteraturhmweisen erortert werden soil-
ten
Es wurde festgestellt. daB zur Bestimmung der Rohdichte die
Entnahme ungestorter Proben nicht erforderlich sei Zu er-
mitteln smd die Trocken- oder Feuchtmasse und deren Volu-
men
Hierzu stehen drei Methoden zu Wahl.
- Entnahme von Stechzylmderproben bekannten Volumens
und Ermittlung der Trockenmasse im Labor
- Entnahme von Masseproben (mit Trockenmassebestim-
mung im Labor) und Ermittlung des Entnahmevolumens im
Gelande
- Entnahme ernes Aggregats und Bestimmung von Masse
und Volumen im Labor
Nach Ansicht der Arbeitsgruppe besteht fur die Bearbeitung
weiterer Methoden (z B der Feldmethode zur Bestimmung
der Rohdichte mit der Gammasonde) zur Zeit kern Bedarf
ISO/TC 190/SC 5/WG 8 .Aggregat-Stabilltat"
Die Emnchtung dieser Arbeitsgruppe erfolgte formal wah-
rend der Sitzung des ISO/TC 190/SC 5 Dr I Grieve (Grofi-
britannien) ubernahm den Vorsitz
Bei der Diskussion uber bekannte Methoden wurde deutlich
daB die Trockensiebung zur Bestimmung der Aggregatvertei-
lung mcht geeignet ist Statt dessen soil die Aggregatvertei-
lung durch Trennung im Luftstrom (air elutnation method) be-
stimmt werden
Die Bestimmung der Aggregatstabilitat soil mit der NaBsie-
bung erfolgen Hierzu ist es erforderlich, daO Probenahme
Autsattigung und Siebmethode aufemander abgestimmi
-------
sind Bishenge Normen und andere techmsche Regeln sind in
dieser Hinsicht unvollstandig und setzen Bedmgungen vor-
BUS. die im Gelande nicht vorkommen
Zur Quantifizierung der Aggregatstabilitat 1st an die Einfuh-
rung von Schertests gedachl, weil damit koha'sive Krafte
ebenso wie Zugspannungen erfaBt warden
Die Arbeitsgruppe wird zu den genannlen Themen bis
Ende 1989 Arbeitspapiere vorbereiten.
ISO/TC 190/SC 5 .PhysllcaUsclie Verfanren"
In Abwesenheit von Frau Dr. A Carter erbffnete C. Memardl
(Niederlande) die Sitzung.
Der Sekretar des ISO/TC 190/SC 5, D Hortensius (Nieder-
lande). benchtete uber derzeitige Arbeiten des
ISO/TC 1B2/SC 1, das sich mit der Idenlifizierung und Klassi-
tikation von Boden fur bautechnische Probleme befaBt. Em
erster Entwurf soil im Oklober 1969 zur Verfugung stehen
Klassidkationsdreiecke sind nicht Teil der Arbeiten.
Die Benchte der Arbeitsgruppen 1 bis 4 und 6 bis 8 wurden
entgegengenommen und bestatigt Die Arbeitsgruppe 8
wurde offiziefl emgenchtet und Dr. /. Grieve als Vorsitzender
ernannt
Die von Arbeitsgruppe l gestellte Frage. bei welcher Tempe-
rat ur Laborversuche durchgef uhrt werden sollten. wurde dis-
kutiert und dahingehend entschieden, daB eine Formulierung
smngemaB lauten soil: .Messungen sollen bei kontrollierter
Temperatur, vorzugsweise 20 °C. ausgefuhrt werden.'
Die Qenauigkeit von Methoden und die Richtigkeit der Er-
gebnisse wurden intensiv besprochen. Die Arbeitsgruppen
wurden aufgefordert. fur ihre Bereiche Ubersichten zu mog-
lichen Emflussen auf Ergebmsse vorzubereilen Dieses Mate-
rial soil auf der nachsten Silzung des ISO/TC 190/SC 5 ge-
sichtet werden, um eine Entscheidung hinsichtlich der Em-
beziehung in die Normen herbeizufuhren.
Die Abstimmung zwlschen Termlnologie und der benutzten
Symbole ist eine wesentliche Vorausselzung fur die weitere
Arbeit Die bereits vorhegende Liste des ISO/TC 190/SC 5
muQ substantiell gekurzt und erneut beraten werden.
Als weitere Aufgabe wurde eine vorubergehende Bodenklas-
siltkation beschlossen Danach gelten die folgenden Partikeh
groBenklassen
Ton' < 2 pm
Schluff. 2 bis 63 |im
Sand 63 bis 2000 \im
(jeweils Aquivalentdurchmesser)
Erganzend wurde em erstes Klassifikationsdreieck beschlos-
sen
Fragen zur Probenahme fur bodenphysikalische Unter-
suchungen werden zur Zeit in den einzelnen Arbeitsgruppen
erortert. Zu emem spateren Zeilpunkt und nach Abstimmung
mit dem ISO/TC 190/SC 2 soil iiber die Zusammenfassung
dieser Vorschlage beraten werden.
Bei der Diskussion uber den Arbeitsbereich des
ISO/TC 190/SC 5 wurde der Ermittlung des Grundwasser-
spiegels hochste Priontal eingeraumt Zunachst wird sich die
Arbeitsgruppe 4 rnil dem Thema belassen
Das ISO/TC 190/SC 5 stellte fest. daB blsher noch keine Akti-
vitalen der Arbeilsgruppe 5 .Qeoelektrische und elektro-
magnetische Untersuchungen" zu verzeichnen waren. Das
Unterkomitee geht davon aus. daB hierzu wenlg Interesse be-
steht und beschloB daher, diese Arbeitsgruppe In Ubereln-
slimmung mit der ISO-Direktive 2.1.3.8 aufzulosen.
ISO/TC 190/3C 6 .Radlologlsche Verfahrert"
Die Sitzung wurde vom kommissarischen Vorsltzenden,
K Hi/be/ (Deutschland), ertJffnet.
Da dies die erste regulSre Sitzung war. muBten zunSchst
organisatorische Fragen geklart werden. K. HUbet wurde als
VorsiUender bestatigt, weil kelne welteren Bewerbungen
vorlagen. Das DIN wird die Aufgaben des Sekretarlats kom-
missarisch durchfilhren.
Seitens des ISO/TC 85 .Kemenergie", und dort insbesondere
im Unterkomitee 2 .Strahlenschutz*. gab es Bestrebungen,
den Bereich .Radiologische Bodenuntersuchungen* aus
dem Verantwortungsbereich des ISO/TC 190 auszygliedem
und dem eigenen Unterkomitee zuzuordnen Ahnliches
wurde fur das ISO/TC 147/SC 3 .Wasserbeschaffenheit;
Radiologische Untersuchungsverfahren* gefordert. Hierzu
wurde das ISO-Zentralsekretariat eingeschaltet, das ein Wa-
res Votum fur den Verbleib der Aufgaben .Radiologische Ver-
fahren" im ISO/TC 147 und ISO/TC 190 abgab.
Im AnschluB an die Kla'rung administrallver Fragen wurde das
Arbeitsprogramm des ISO/TC 190/SC 6 feslgelegt. Dabei
wurde beschlossen, die folgenden funf Arbeitsgruppen ein-
zurichten:
ISO/TC 190/SC 6/WG 1 .Gammaspektrometrle"
(Vorsitz: Prof. Dr. Sensonl.
Deutschland)
ISO/TC 190/SC 6/WG 2 Jn-situ-Gammaspektrometne"
(Vorsilz: P. Neumann. Deutsch-
land)
ISO/TC 190/SC 6/WG 3 .Strontium-90"
(Vorsitz: Dr. C. Frledli, Schweiz)
ISO/TC 190/SC 6/WG 4 .Rest-Beta'
(Vorsitz: Dr. A. Ware. GroBbritan-
nien)
ISO/TC 190/SC 6/WG 5 .Gesamt-Alpha*
(Vorsitz: Dr. A Ware, GroBbrltan-
nlen).
Die Zusagen der Vorsitzenden fiir die Arbeitsgruppen 1 und 3
stehen noch aus.
Zum Rahmenprogramm der Sitzung 1989 des ISO/TC 190
.Bodenbeschaffenheif gehOrte ein Besuch In elnem Unter-
nehmen, das auf der Mulldeponfe In Berlln-Wannsee sell
1988 Europas grbBte Anlage zur Deponiegasgewinnung und
•verwertung betreibt.
Die Mitarbeit des DIN im ISO/TC 190 wird durch die finan-
zielle Forderung des Umweltbundesamtes ermSglicht.
A.Paetz
E-7
-------
Appendix F
Agence Francaise Pour la Recuperation
et ('Elimination des Dechets
F-l
-------
APPENDIX F
AGENCE FRANQAISE POUR LA RECUPERATION ET L1ELIMINATION DES DECHETS
INTEKNA TIOMAL. EXPERTISE
\ COMPETENCE J
A SOLID EXPERIENCE
For over ten years, the Agency has been acting 1n Franca as the technical
expert of Public Authorities, in charge of defining and Implementing
national policies for waste management, both 1n the field of household
refuse as well as of Industrial and agricultural waste.
Thus the Agency has had the opportunity to develop expert skills
specialized 1n the assessment of waste management, encompassing all related
technical, economic, legal and organizational aspects, a cotnpetanca which
has been evidenced 1n numerous concrete applications throughout the world.
Thanks to these expert skills 1n specific assessment, the Agency 1s able
today to share with Us foreign partners the assets acquired from a solid
experience In the field of waste management, whatever problems may be
encountered.
A SEARCH FOR ADAPTED SOLUTIONS
Backed by an experience acquired 1n the field, which 1s particularly
significant In the context of developing countries, the Agency's experts
are exceedingly concerned that their Interventions always fit within the
reality of the projects, through an Increasingly accurate knowledge of
local situations and a search for adapted solutions, Integrating 1n
particular the economic requirements as well as the social customs of the
area Involved.
By providing coordination and follow-up for many experimentation projects
Implemented since 1985 within the framework of the French Inter-ministerial
Program for the Improvement of household waste management 1n developing
countries (part of the REXCOOP Program), the Agency has thus undeniably
achieved a level of experience and competence which enables It today to
offer eoluttont well-adapted to a variety of situations.
F-2
-------
NEUTRALITY
A NEUTRAL PARTNER ASSISTING THE CLIENT
The status of the Agency as a specialized public company, which as such
openly states Its neutrality, makes 1t a privileged partner at the service
of public or para-public Institutions In particular who are the Instigators
of such projects, as well as of Industrial clients concerned about
neutrality 1n their choice of technological options.
International organizations, government agencies, districts, communities,
developers, contractors or managers... the Agency can provide all of you
with a preliminary assistance prior to the Involvement of other engineering
or Industrial partners.
In all cases, the technical assistance offered by the Agency provides the
client with the guarantee of a highly reliable technical mastery for his
projects, as well as a guarantee of adapted choices selected freely without
pressure from any Industrial contractor.
INVOLVEMENT OF THE AGENCY j
Whether 1n the field of household refuse or that of Industrial and
agricultural waste, the Agency's Involvement 1s designed essentially 1n the
perspective of technical assistance to public or private clients, for the
purpose of defining their requirements 1n terms'of waste management, of
creating overall methodological, organizational or technological frameworks
for actions to be Implemented, as well as providing a technical follow-up
on the progress of such actions.
Within this overall context and depending on the problem encountered or the
degree of development of considered solutions, various types of
Intervention may be carried out:
F-3
-------
MASTER PLAN
In the case of a research project Intended to work out a waste management
policy, the Agency's experts are prepared to provide the definition of a
real master plan for waste management: analysis of waste materials,
assistance In selecting the means of collection and disposal to be
Implemented (size, technical features and location of required
Installations, economic aspects), assistance 1n drafting specifications and
analyzing tenders for contract awards on behalf of the client, proposals
for regulations, Institutional analyses...
The multlfaceted technical capabilities of the Agency's experts enable us
to Intervene for any Individual type of waste as required, as well as to
consider an overall approach Integrating all types of waste, while
addressing the problems from the twofold standpoint of disposal and
reclamation, whenever this latter solution can be envisaged.
TECHNICAL ASSESSMENT
In some cases, collection systems or waste treatment plants already exist,
yet may have proven with experience to be unsulted to local conditions.
In order to help you solve your problem, the Agency can be called 1n to
conduct a technical assessment of the specific situation, to establish a
diagnosis and present solutions.
Whatever problem currently concerns you:
collection of household refuse, Incineration plant, composting plant (for
household refuse or other organic waste), household refuse or Industrial
waste disposal, unauthorized dumping of toxic waste presenting pollution
risks, reclaiming of slaughterhouse waste or breeding excreta...
the Agency's experts can step 1n quickly and offer the best suited
solution.
F-4
-------
STUDIES AND RESEARCH
On any technical or economic Issue related to waste, the Agency develops or
coordinates study and research programs, In France as well as on an
International scale, by combining the knowhow of public or private
Institutions and laboratories with the skills of university experts.
Several programs on a variety of topics have thus been developed under the
Agency's coordination, such as the following works conducted within the
framework of the REXCOOP Program on "Household Waste Management 1n
Developing Countries":
- Experimentations of sorting-recycling systems for household refuse,
- Mechanical systems of simplified composting adapted to certain climatic
conditions,
- Methods of landfill management 1n tropical regions,
or for example the following programs carried out on behalf of the
Commission of the European Communities:
- Research for a better knowledge of toxic or hazardous Industrial waste
and of their means of disposal,
- Modelling of toxic or hazardous Industrial waste dumps,
- Optimizing of sorting processes for household refuse and reclaiming of
mixed plastics.
From this type of fundamental knowledge, specific studies or research work
can then be developed by the Agency's engineers 1n response to requests
regarding a particular problem or situation.
TRAINING - INFORMATION
Training and Information represent one of the essential facets of a
coherent and comprehensive action on the generally badly-known Issue of
waste, whether 1n terms of public Information designed to raise the
awareness of elected officials or Industry leaders to a national-scale
policy developed 1n a given country, or 1n terms of technical training of
local administrative specialists responsible for Implementing this policy.
F-5
-------
NUMEROUS REFERENCES
For many years now, the Agency's engineers have been drawing on the nation-
wide experience gained In their own country of France where a high
performance system of waste management 1s available, and have been applying
1t to handle a variety of diversified situations. An In-depth knowledge of
the experience acquired by their neighbors from Europe, the USA or Canada,
together with their Involvement In projects 1n Africa, South America, the
Middle East or In South East Asia, have thus conferred them numerous
International references among which the following major projects should be
mentioned:
- Coordination of European research programs on behalf of the EEC
(Industrial waste and household refuse) (1966-1987, 1988-1989).
- Member of the Waste Management Committee, a consultant group of experts
assigned by the EEC to deal with the problems of waste.
- Participation 1n .the International NATO/CCMS task force on the treatment
of hazardous waste.
- Technical coordination of the French 1nterm1n1ster1al REXCOOP program:
Household Waste Management In Developing Countries (1985-1987),
* technical monitoring of experimentations
* organization of a synthesis symposium (PARIS-Sept.1987)
- Organization on behalf of the UNEP of a symposium on the treatment of
Industrial and household waste 1n West African countries (Abldjan-
1987).
- Assistance in the Installation of a computerized monitoring system for
toxic waste 1n Malaysia (1988-89).
- Improvement of the performance of composting plants 1n Morocco (1988-89).
- Assistance In Industrial waste management In the District of Tunis
(1988).
- Assistance In selecting a treatment method for household refuse 1n the
Seychelles (1988-1969).
- Determination of a system for waste collection and sorting-composting
suUed to the local situation 1n the city of Hanlzales In Colombia
(1988-89).
F-6
-------
To this purpose, the Agency has been organizing specialized training
sessions, both Initiation and on-going professional training, providing the
officials of local government services with a better comprehension of the
various facets Involved 1n the Implementation of an overall waste
management policy (regulations, control, professional training...)
In addition, the Agency In cooperation with local authorities organizes or
participates 1n exchange and Information seminars Involving one or several
countries, designed to raise the awareness of political, administrative or
Industry officials, and to promote direct exchanges of Information with
professionals who can come up with technical solutions to the problems
encountered locally.
Furthermore, the Agency offers to Its partners access to the Centre
Fran$a1s de Documentation sur les Wchets (French Documentation Center on
Waste), which contains over 8,000 works on-waste treatmant as well as a
large resource center Including slides and video documents.
F-7
-------
"LES TRANS FORMEURS"
The Agence Franchise pour la R6cup6rat1on et I1Elimination des Dechets LES
TRANSFORHEURS Is a public agency created In 1975 by the French public
authorities.
Its Mission Development of an ever Improving control of waste,
both In term of disposal and reclamation.
Its know-how A staff of 1GO persons with a passion for their
mission, providing you with their multifold skills
as engineers and researchers: chemists, geologists,
thermal engineers, economists, legal experts...
Its International experience
While the Agency remains the appointed tool of the
French authorities to carry out the national
policies on waste management, the Transformeurs
have also been working on an International scale
where they have already achieved considerable
recognition.
L.ES TRANSFORMEURS
COMPETENCE AND NEUTRALITY
IN THE SERVICE Ot=" PUBLIC INTEREST
Your Contact; Patrick SOUET, Deputy Manager
Manager of International Programs
Bernard FOULLY, Charge1 de Mission for International
Affairs
F-8
-------
APPENDIX G
THIRD INTERNATIONAL
KfK/TNO CONFERENCE
ON CONTAMINATED SOIL
KARLSRUHE, FRG
DECEMBER 10 - 14, 1990
G-l
-------
SOME NUMBERS
KfK/TNO Conference
• Attenders 1500-2000
• Presentations 125
• Parallel Sessions 3
• Posters 250
• Workshops 7
• Excursions 10
• Exhibition
• Cultural Programme
WORKSHOPS
KfK/TNO Conference
• W 1 Industrial Sites
• W 2 Immobilisation
• W 3 Field Analysis
• W 4 Expert Systems
• W 5 Polluted Sediments
• W 6 Warfare Related Sites
• W 7 Soil Contamination in
Eastern Europe
(Special Session)
-------
SUBJECTS COVERED
KfK/TNO Conference
Topic A
Strategies of Soil
Remediation
Newly industrialized and
Developing countries
Legal, Economic and
Social Aspects
part 1
SUBJECTS COVERED
KfK/TNO Conference
Topic B
« Risk Assessment
• Behavior of Contaminants
Effects of contaminants
part 2
-------
SUBJECTS COVERED
KfK/TNO Conference
SUBJECTS COVERED
KfK/TNO Conference
-------
NEW DEVELOPMENTS
Technical
NEW DEVELOPMENTS
Mixed
VI
• Extraction and thermal Treatment
largely Established
• Soil Vapor Extraction
Simple, Cheap and Effective
• Electroreclamation
only solution for
Clay at present
• Biological Techniques
Huge Development
In-Situ and Reactors
• Stabilization/Solidification
Start of Evaluation and
Theory
• Strong accent on in-situ treatment
• Many theoretical contributions on
soil/contaminant interactions
and biodegradability
• Many new developments on site
Assessment and analysis
• Large use of expert systems
• Inventories have started in
many countries
-------
Appendix H
Technology Innovation Office
Office of Solid Waste and Emergency Response
U.S. Environmental Protection Agency
H-l
-------
Technology Innovation Office
Office of Solid Waste and Emergency Response
United States Environmental Protection Agency
Washington, D.C. 20460
Mission
The mission of the Technology Innovation Office (TIO) is to increase applications
of innovative treatment technology by government and industry to contaminated waste
sites, soils and groundwater. Increased usage will be accomplished through the removal
of regulatory and institutional impediments and the provision of richer technology and
market information to targeted audiences of Federal Agencies, States, consulting
engineering firms, responsible parties, technology developers, and the investment
community. The scope of the mission extends to Superfund sites, corrective action sites
under the Resource Conservation and Recovery Act (RCRA), and underground storage tank
cleanups. By contrast, TIO is not a focus for EPA interest in treatment technologies
for industrial or municipal waste streams. for recycling, or for waste minimization.
Other offices address these special interests.
For purposes of remediation, innovative technologies do not include rotary kiln
incineration, conventional stabilization or other methods where sufficient performance
and cost information are available. Land disposal technologies are also not included
within the scope of TIO's interests. Innovation in thermal methods, bioremediation,
physical/chemical techniques and ground water extraction and treatment technologies is
of principal interest. Innovative monitoring methods are of interest, but are a
secondary priority.
Approach
TIO will influence the increased use of innovative technologies by working with and
through knowledgeable individuals and groups both inside and outside EPA. TIO
accomplishes its internal mission as a partner with other waste program offices and EPA's
Office of Research and Development.
Vithin the Agency, TIO exercises policy leadership and sets expectations, assists
in the implementation of demonstrations of technologies under the Superfund Innovative
Technology Evaluation program, analyzes trends in Agency technology decisions, helps
screen technology types and vendors, and serves as a champion for agency attention to
innovative technologies. A collateral objective for TIO is brokering the transfer of
information on the cost and performance of all alternative technologies for waste
remediation.
Beyond EPA, TIO is engaging the principal stakeholders in innovative site remediation
-- consulting engineers, responsible parties, technology vendors, venture capitalists,
universities, States and professional associations --in the challenge to increase the
use of innovative technologies. This joint work involves both identifying mutual
interests between and among these parties and EPA waste programs and then devising
mechanisms to act upon them. Because EPA is a member of the family of Federal agencies
interested in lower cost, innovative treatment technologies, TIO is establishing a
Federal Remediation Technologies Roundtable to maximize the sharing of available Federal
experience.
H-2
-------
Mechanisms for Action
The primary objectives of TIO are to identify and enhance incentives to increase
innovative technology application and to advocate innovation through removal of
impediments. TIO will explore opportunities within the existing statutory and regulatory
frameworks for additional flexibility in policies, permitting, State grants, and
contracting procedures to stimulate greater use of innovation. Recognizing the authority
of the States in executing the hazardous waste programs, TIO will explore with the States
opportunities for them to exercise further leadership in technology innovation.
Another area of interest is the availability of cost and performance information on
new technologies. Data are frequently missing to support developer claims; in certain
instances, a developer may possess test data, but lack any data sets containing
application information that convinces a technology user of their validity. TIO wi!
address this critical problem by developing minimum data sets that a developer a
satisfy. Criteria will be developed through a consensus of EPA, States, consultir
engineers and developers for the basic sets of data that will provide an extra level o.
confidence to vendor claims. The objective of the data is to advance the likelihood that
a technology will be fairly considered during engineering feasibility studies.
Hopefully, technology vendors will realize a substantial market advantage by providing
such basic data. TIO anticipates that this program will be viewed as an incentive by
the vendor community.
Market information is also needed to clarify the opportunities for technology
vendors. They are unclear where to market their innovative systems because insufficient
information about the characteristics of waste sites is available. TIO will begin by
providing both profiles on the overall population of Superfund sites, and information
on sites that are currently in the decision process. An indirect benefit of this effort
will be to stimulate new technology development.
TIO will ensure that inventors and vendors are aware of "incubator" facilities that
provide a full-range of services from testing and evaluation to assistance in
commercializing technologies. The existing "incubators" are both non-: ifit and for-
profit and differ in the amount of financial assistance provided to the Developer.
Dissemination of information on technologies is a critical component of TIO's
mission. There are a number of specific mechanisms to communicate policy and information
on innovative technologies and other technical assistance. First, OSWER operates
training programs nationwide that are especially responsive to the changing needs of EPA
regional staff by designing new course development and encouraging innovative training
technologies. TIO also operates a highly regarded human resource development initiative
-- the On-Scene Coordinator/Remedial Project Manager Support Program -- for front-line
Superfund employees. TIO will seek to extend its successes in this area to other
professionals in the hazardous waste management field.
TIO will optimize the use of the electronic bulletin boards, newsletters, monographs,
technical briefs, brochures, trade journal articles, and conference presentations. It
recognizes the importance of up-to-date and comprehensive mailing lists within EPA and
for clients in other Agencies, the States, and for private stakeholders.
TIO is not a grant-making organization -- other organizations have that mandate for
innovative technology development, technology transfer and training. TIO will seek to
enable outside groups to form partnerships and networks and seek to develop client
relationships to increase the level of innovative technology use.
H-3
-------
|