GUIDELINES FOR THE PREPARATION OF WHITE PAPER
Name: J. Kenneth Wittle
Affiliation: ElectroPetroleum, Inc.
E- mail:kwittle@electropetroleum.com
Webpage:www.electropetroleum.com
Name: Dr Falk Doering
Affiliation: ecp, llc
E—mail: Doering [doering.soilrem@t-online.de]
Geoenvironmental Research Experience (list projects in progress or completed within the past
5 years):
Erie Pier Project, Duluth MN (Wittle and Doering)
New Jersey Pesticide Site (Doering)
Georgia Site (Doering)
Montana Site (Wittle)
Geoenvironmental Teaching Experience (list related courses, including short courses, taught
within the past 5 years):
Geoenvironmental Consulting Experience (list major projects onl
Appraisal of Geoenvironmental Research, Education and Practice (limit to 1-2 pages):
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Curriculum Vitae
Personal Data
Name: Dr. Falk R. Doering
Residence: 51, Burghaldenweg, Stuttgart, D-70469, Germany
Date/Place of Birth: June 19, 1941 in Dresden (Germany)
Marital Status: Married, two children (1968, 1971)
Languages: German, English, French, Russian
Member in Professional
Organizations: Union of German Engineers (VDI), Union of Engineers for
Soil and Groundwater Remediation (ITVA); International
Electrochemical Soil Remediation Network
Training
May 1961 to June 1995 University of Marburg; Geophysics and Business Admini-
stration
June 1995: MA in Geophysics; MBA
August 1968: PhD
October 1968 to June University of Bonn, law and International Private Law
1973 June 1971: LL.B
Professional Career
Dec. 2000 to … electrochemical processes, l.l.c. (ecp), Valley Forge (PA),
CEO and Owner. ecp is the controlling holding of different
affiliate companies such as: P2 Soil Remediation, Inc.,
Stuttgart (Germany), Eurodépollution s.à.r.l., Irigny
(Greater Lyon), France, B.S. Geoteknik ApS, Odense
(Denmark), BUGS s.à.r.l., Niederkorn (Luxemburg):
• worldwide geophysical exploration of raw materials
such as petroleum, natural gas, gold, uranium, dia-
monds, and rare metals
• performance of projects of soil and groundwater reme-
diation with own technologies (engineers and general
contractors)
• R&D in electrochemical processes for land remedia-
tion and commercial application of these processes as
general contractor in the brownfield development
• R&D in waste water treatment and saline water con-
version by RO, UF, UV, UHF-radiation.
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J. KENNETH WITTLE, PH.D.
Business Address:
996 Old Eagle School Road
Suite 1118
Wayne, PA 19087
(610) 687-9070, Fax (610) 964-8570
Education:
Business Administration 1970 The Wharton School
Ph.D. Chemistry 1968 Purdue University
B.A. 1962 Franklin & Marshall
College
General Electric Continuing Education Program: Management Development Course, Modern
Engineering
Work Experience:
9/1979 – present
Vice President, Electro-Petroleum, Inc.
Electro-Petroleum, Inc. developed a process with the utilization of electrical energy to stimulate oil
production in heavy oil formations. The process demonstrated a 300% increase in oil production of
electrically stimulated wells. This process is now being applied to soil remediation and site cleanup in
the environmental field.
1/1984 – present
Vice President, Electro-Pyrolysis, Inc.
Electro-Pyrolysis, Inc. holds the patents (co inventor) for a DC arc furnace process for the destruction of
hazardous and municipal solid waste by ultrahigh temperature pyrolysis.
2003 - present
Developer and operator of Coleraine, MN Research Sediments Testing Facility
1996 - 1997
Adjunct Professor for Environmental Engineering, Clemson University, Clemson, SC
1992 - 1994
Visiting Scientist, Massachusetts Institute of Technology, Plasma Fusion Center, Cambridge, MA
1985 – 1990
Cofounder of TTW, a company formed to develop deep drilling equipment for the oil and gas industry
1985 – 1992
Co founded ITA, technical consultants to a private investment capital group
1/1979 – 1987
Consultant, Planning and Siting, ChemClear, Inc.
Responsible for planning and siting work for a public access company in the liquid industrial aqueous
waste treatment business. Patented a process for electrically drying of aqueous sludges.
1968 – 1979
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General Electric Company
1972 – 1979 Dielectric Materials Laboratory Manager
• Directed development and testing of organic and inorganic material used in design and
manufacturing of low, medium, and high voltage switchgear, high voltage transformers, and
relays. Included electrical, mechanical, and chemical testing laboratories.
1968 – 1972 Sr. Inorganic Chemist, Sr. Project Engineer
1972 – 1979
Dielectric Materials Laboratory Manager
Directed development and testing of organic and inorganic material used in design and manufacturing of
low, medium, and high voltage switchgear, high voltage transformers, and relays. Included electrical,
mechanical, and chemical testing laboratories.
1968 – 1972
Sr. Inorganic Chemist, Sr. Project Engineer
Publications:
50 technical papers and 30 + U.S. and foreign patents
Technical Societies:
Dr. Wittle is a member of the American Chemical Society, The Chemical Society, American Association
Advancement of Science, Society of Petroleum Engineers, and American Society of Mechanical Engineers.
Dr. Wittle is Chair of the ASME Research Committee on Industrial and Municipal Waste and Vice Chair
for the Board on Research of the Board on Research and Technology Development. Dr. Wittle served as a
member of the Diffusion Focus Group of the Technology Innovation and Economic Committee of
NACEPT (National Advisory Council for Environmental Policy and Technology) and advisory
committee to the U.S. Environmental Protection Agency.
Perspective on Emerging Geoenvironmental Issues and Technologies (limit to 1-2 pages):
Basics of ElectroChemical GeoOxidation (ECGO)
Dipl.-Ing. Niels Doering P.E., Dr. Falk Doering, VDI, ecp, llc., Wayne (PA)
Rationale
For more than a century, electrochemistry is an essential branch of the chemical industry.
Electrochemical processes are subdivided in (a) the Electrochemical Synthesis, covering a wide field of
applications ranging from the synthesis of organic substances, resins, artificial materials, cellulose,
inorganic chemicals (chlorine, oxygen, hydrogen), and semiconductors, and serves the sterilization of
sera. (b) Electrokinetic Processes make fuel cells and batteries work; basic applications are
electrochemical machining, electro-forming, etching of metals, etching of semiconductors, liquid/solid
separation, electroplating, electrophoretic painting; whereas (c) Joule heating (resistance heating) is used
for smelting metals such as steel and aluminum, and to produce artificial crystals such as diamonds or
zirconium. Modern technologies such as lasers and plasma based processes are unthinkable without
electrochemical foundations. There is no logic reason, to see on the one hand these processes in
laboratories and factories work, and on the other to contest the viability of the same processes when
being implemented in soils and the groundwater.
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With respect to synthesis and electrokinetics, ElectroChemical GeoOxidation (ECGO) transfers above
technologies into the soil and the groundwater. Of course, the special conditions of the medium, the soil,
need to be considered as process requirements. We should mention that in soils already natural
electrical fields exist named “Spontaneous Polarization” (C. SCHLUMBERGER) which are in the range of
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150 to 2,000 mVDC. These natural voltages already perform electrochemical reactions (redox-reactions)
in the soil and form integral part of “natural attenuation”.
ECGO comprises a bundle of five different processes addressing special problems such as mineralization
of organic compounds, treatment of sediments (humic substances), treatment of large surfaces (tank
farms, refineries, manufactured gas plants), remediation of mixed damage (organic/inorganic pollutants)
and metal-organic pollutants, and finally heavy metals. An ECGO system comprises of - at least - two
steel electrodes incorporated into the soil. Via these electrodes a predefined electric dc-current is
introduced into the soil effecting redox-reactions which mineralizes organic pollutants to carbon dioxide
and water. System variants are designed to have heavy metal ions and complex ions precipitate onto the
electrodes. ECGO can be applied in multi-electrode systems. The length of the electrodes is
commensurate to the depth of the damage; the distance between the electrodes is between 5 m to 300
m, dependent on the type of ECGO process to be applied.
Hereinafter, we discuss the essential elements of ECGO, namely the double (triple) layer structure related
to the soil particle/electrolyte system, Induced Polarization, and the system of redox-reactions
(reduction/oxidation reactions).
The Double (Triple) Layer Structure
Civil Engineering Sciences and hydrogeology very early started investigations into the soil/groundwater
system defining groundwater as electrolyte. In the following, also the pollutants distributed in the soil, are
referred to as “soil particle”. To be mentioned first, two approaches to the electrochemical description of
the soil are used. Some European scientists (SCHAAD, JORDAN, DOERING et al.) prefer the
microscopic approach comprising of the “Colloid Model” and the double (triple) layer water hulls, bound
by electrostatic forces to the soil particles whereas the majority of US scientists (VACQUIER, MADDEN,
MAYPER, CANTWELL et al.) prefers the macroscopic approach comprising of the concept of the cation-
selective membranes.
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The Colloid Model is based on the research of ETH Zurich that any soil particle, once being in contact
with the soil water (commonly referred to as groundwater), builds up a double layer with the water.
Driving force of this phenomenon are so-called electrostatic forces such as VAN-DER-WAAL, LONDON,
COULOMB etc. forces creating the so-called adsorption-complex comprising of the highly vi scous, highly
pressurized (pore water pressure pw = 10,000 to 25,000 bars) hygroscopic water hull, and the so-called
solvation water layer, attracted by the residual electrostatic forces, having a lower viscosity. The third
layer is called captive water, marking the transition area to the bulk solution (groundwater) with very little
electrostatic forces. The electrical charge in the soil particle/electrolyte system is determined according to
COEHN’s law: the substance or particle having the higher dielectric constant, obtains the positive charge.
As a rule, water having a dielectric constant ε ≥ 80 (at about 20°C) is almost in all cases positively
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charged. Thus, the double layer in reality is a triple layer structure which works as capacitor. The
capacity of the soil is in the range of about 5 to 50 µF may substantially increase over time by the
phenomenon of the electrostriction, i.e. the contraction of the dielectric layer attributable to the attraction
of the dipoles which is:
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∆V / V ~ ε E
where: ∆V / V = the rate of contraction
ε = permittivity
E = voltage applied.
The individual capacitors linked with the corresponding resistors in the soil form RC-elements which are
the key element of energy supply to the redox-reactions. This terminology taken from hydrogeology may
now be made compatible with the terminology of the colloid chemistry. The above mentioned
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hygroscopic water corresponds to the Inner Helmholtz layer; the solvation water to the term “Outer
Helmholtz Layer” and the captive water is the “Diffuse Layer”. Between the Outer Helmholtz Layer and
the diffuse layer, there is an interface, called Outer Helmholtz Plane, the prerequisite for electrochemical
reactions, where the transfer of electrons takes place. The voltage gradient between the interface and
the bulk solution (groundwater) is known as Zeta-potential.
Explaining Induced Polarization in an macroscopic approach, VACQUIER et al. described in 1957 a
model wherein an electrical field drives cations and water through a cation-selective membrane (=
capillary system of the soil), whereas the anions are rejected by the Helmholtz double layer of the
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capillaries. This model could not, however, be confirmed in the field since both, anions and cations, are
driven through the capillaries.
Induced Polarization
In soils already natural electric dc fields exist (“Spontaneous Polarization”, SP). The process of
upgrading the voltage of SP is commonly referred to as Induced Polarization (IP), a geophysical
phenomenon subject to intensive research in the U.S. in the fifties and sixties of the past century. IP
explains the effects of an electrical current passing through the soil. Two different phenomena have been
detected: when the particles of the soil are conductive, then on the so-called faradic path redox -reactions
occur, i.e. when electrons cross the interface (Outer Helmholtz plane), electrochemical reactions and ion
diffusion take place. These processes can easily be identified by oscilloscope as impedance of the
system, subdivided into the reaction-impedance, and the Warburg impedance (characterizing the ion
diffusion). Algorithms have been developed to calculate either share at the impedance. When the
particles of the soil, however, are insulators, then on the non-faradic path electrons are stored in the triple
layer. The discharge signals can be identified in the oscillograms as spikes. The capacitance of the soil
increases over time and is the major supplier of energy to the reactions, in particular, for overcoming the
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activation energy.
The Soil as Conductor
Traditional geophysics describe two different types of conductors in soils, namely the ionic conductor,
comprising of the groundwater containing ions, and the electronic conductor, in most cases metallic
minerals or minerals doped with metals. Metallic minerals are alloys, minerals such as Mg2Pb, Mg3Sb2,
Fe3O4 (magnetite) and graphite, whereas other minerals such as CaCO3, Sb2O3, Hematite (α- Fe2O3), or
HgS are insulators. The conductivity of the so-called metallic (electronic) conductors apparently depends
on the position of the metal atoms in the crystal lattices. Since the majority of minerals, despite the
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inclusion of metal atoms, has resistivities between 10 and 10 Ωm, this type of conductor can only be
considered to be representative for certain ore deposits. In regular soils, the electronic conductor is of
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marginal importance.
It is a basic understanding in geophysics that the resistivity of the soil largely depends on its water
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content. The conductivity of the groundwater (fresh water) is in the range of 250 µS/ [25C°] to about 700
µS/cm which corresponds to about 40 Ωm to 14.3 Ωm. This conductor is called the Ionic Conductor.
In our field research, a third conductor has been discovered, namely the colloid conductor apparently
using the Outer Helmholtz layer (dielectric layer) as conductor. This conductor has an extremely low
resistance of 0.1 to about 10 Ω between two electrodes placed at a distance of 5 m to 100 m. This
conductor has been called the Colloid Conductor on which electrons are forced to cross the interfaces
thereby initiating reactions of oxidation and reduction. The resistance of this conductor is variable since
field observations tend to indicate that its thickness fades out during remedial action. The colloid
conductor is of primordial importance for ECGO, since it permits to drive a relatively high amperage at
relatively low voltages. However, limitations are given by the microscopic size of the conductor. From a
certain point onward, which is called the Electrokinetic Point (EP), the ionic conductor (the capillary water)
becomes the main conductor permitting to drive high amperages at high voltages at an elevated
resistance. The conductor is important for the distinction of electrochemical processes in the soil: the
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colloid conductor is linked to electrochemical (redox-) reactions whereas the ionic conductor permits at
substantially higher energy levels the transport of ions through the soil without electroche-mical reactions.
Redox-Reactions
Oxidation of organic substances stands for donation of electrons whereas reduction stands for
acceptance of electrons. Both reactions occur simultaneously and require the presence of oxidizing and
reducing agents. These agents are generated by ECGO in-situ by water electrolysis. By primary
processes and secondary reactions, the agents are generated such as elemental Hnasc, HO radicals and
ions, HO2 ions and radicals and hydroperoxide, as well as elemental oxygen (O nasc.) and ozone.
Ongoing oxidation comprises of the generation of alcohols, aldehydes, organic acids which under the
conditions of ongoing oxidation decompose to carbon dioxide and water where reduction means stepwise
substitution of p.x. halogens by hydrogen, ring opening of aromatic constituents or cleavage of aliphatic
compounds at preferred breaking points (C10/12; C5/6, C2/3).
In the literature, the application of Fenton’s reagent, i.e. the synthesis of OH-ions and radicals from the in-
situ reaction of hydroperoxides with bi-valent iron has been discussed. Since Fe is an ubiquitous mineral
and since by water electrolysis, oxidants such as hydroperoxides are generated, the activity of Fenton’s
reagent cannot be excluded for ECGO.
The central objective of ECGO is to establish an oxidized environment at pH in the range of neutral and
obtaining Eh (electrode potentials) in the range of the positive. This requirement in particular decides on
the success or failure of the remediation of sediments which at pH in the range of 5.5 to about 8.5 have
an Eh in the range of –250 mV to 200 mV (reducing, from 0 to –250 mV strongly reducing) whereas
upland soils have a pH of about 5.5 to 8.5 and an Eh in the range of above 350 mV (above 500 mV: well
oxidizing). Reduction would – as far as sediments are concerned – support “polymerization” processes of
humic substances, using metal ions as “hook-up” points for the recombination of PAH-, phenol-, PCB- et
al. molecules. First results of field tests related on the treatment of sweet water sediments indicate that
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ECGO can substantially raise the E h. This result is still subject to confirmation . In another test, dealing
with sediments in the Baltic Sea, we intend to exploit the pro-cess of Eh/pH control to break up humic
substances and to set TBT free which is expected to precipitate tin on the electrodes.
A Field Research Project on the Decomposition of PAH
About 500 tons of a silty soil, polluted by 11,000 mg PAHEPA 1-16 have been homogenized by sieving and
then having been heaped. Because of the homogenization the average concentration of the heaped
material decreased from 11,000 mg PAH/kg to 1,355 mg PAH/kg. In the heap, an anode and a cathode,
were horizontally installed at a distance of 10 m, resulting in a resistance of 9.45 Ω. The remedial action
took 70 days when the remedial action has been accepted by the regulator and 100 days when our
quality control system stated the almost complete destruction of metabolites and by-products (TPH). The
regulator relied on the sampling and the chemical analysis performed by an University, collecting
composite samples and using method DIN 38407-F8 for the analysis of PAH by HPLC. The GC-MS
chromatograms have been established on the basis of aliquots of the above samples by a hnu
321/Finnigan MAT ITD 800 system, using the NBS/EPA extended environmental library and the INCOS
search system.
The clean-up levels were 100 mg/kg d.m. for PAH (EPA 1-16) and 15 mg/kg d.m. for 6 carcinogenic PAH,
hereinafter referred to as PAH-TVO, namely Fluoranthene, Benzo(b)fluoranthene, Benzo(k)-fluoranthene,
Benzo(a)pyrene, Benzo(g,h,i)perylene and Ideno(1,2,3cd)pyrene.
The results prepared by the university, read as follows [mg/kg d.m.]:
Days 1 36 70
Naphtalene 80,7 81,3 17,29
Acenaphtylene 35,2 44,1 0,98
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Acenaphthene 9,8 22,2 0,6
Fluorene 38,6 503,1 1,13
Phenanthrene 326,8 83,7 7,35
Anthracene 47,8 11,9 1,45
Fluoranthene 107,5 23,4 2,98
Pyrene 230,2 81 8,38
Benzo(a)anthracene 71,3 17,6 1,48
Chrysen 81,8 17,9 2,04
Benzo(b)fluoranthene 50,7 9,6 2,09
Benzo(k)fluoranthene 47,3 4,2 1,21
Benzo(a)pyrene 110,3 17,9 3,75
Indeno(123-cd)pyrene 47,8 26,2 1,09
Dibenz(ah)anthracene 9,5 25,6 2,98
Benzo(ghi)perylen 59,5 37,9 0,54
Total (1-16) 1354,8 1007,6 55,33
PAH TVO (6) 423,1 119,2 14,1
The decomposition (reduction by cleavage) is performed via 2-core (naphthalene) and 3-core PAH (here:
fluorene, in other cases acenaphtylene).
The GC-MS analysis was as follows whereby the by-products deserve special interest.
:
Baseline Sampling At day 36
At day 70 (official end of remedial action) At day 100
During remedial action the basic pattern of the chromatograms changed: the baseline chromatogram is
typical for a contamination by PAH, the chromatograms at day 36 and 70, however, are typical for TPH
including the so-called “oil hill” (underground) which stands for a complex mixture of organic compounds
dissolved in TPH. The chromatogram at day 100 depicts again close to the limits of detection a
chromatogram typical for PAH. The statement can be made that the electrochemical decomposition of
PAH is made
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a) by breaking up the molecules to levels of 2- and 3-core PAH and then ongoing
b) breaking up the aromatic and cyclic compounds to aliphatic compounds (TPH)
c) oxidation of the constituents to carbon dioxide and water.
At the end of the project, the metabolites have been eliminated to close to the limits of detection.
Persistent metabolites could not be traced.
The following metabolites have been detected in the chromatograms of day 36 and 70: derivatives of
benzene (butynylbenzene), and cyclic compounds (dodecyclomethyloxirane, 3-(1,1 dimethylethyl-cis
cyclohexacarboxylic acid, cyclopentapyrane-1,3-dion) and 1,2,4-cyclopentanetrion, 3-methyl).
In the final chromatogram (of day 100), 1,2,4 cyclopentanetrion, 3-methyl, dimethylcyclohexane and
propanoic acid, di-methyl-, have been identified.
1
J.S. Sumner: Principles of Induced Polarization for Geophysiocal Exploration; Elsevier Scientific Publishing
Company, New York 1976; F. Ollendorff: Electric Current in Soils (in German), Birkhaeuser Verlag Basel,
Stuttgart, 1969; Ch. Veder: The Importance of Natural Electric Fields for Electroosmosis and Electrokataphoresis in
Soil Mechanics (in German) in: Der Bauingenieur, 38, (1963), p. 378
2
W. Schaad: Practical Application of Electroosmosis in Soil Mechanics (in German) in: Die Bautechnik , 35 (1958),
p. 210;
3
T.M. Riddick: Control of Colloid Stability through Zeta Potential; Zeta Meter (ed.), Wynnewood, PA, 1968; H.
Jordan, H.-J. Weder: Hydrogeology (in German), Leipzig (GDR), 1988; F.R. Doering and Th. Papadopoulos: In-situ
Electrochemical Soil Remediation; Hazwaste World Superfund XVII, October 15-17, 1996, Washington,
Conference Proceedings, p. 116
4
V. Vacquier, C.R. Holmes et al: Prospecting for groundwater by Induced Polarization; Geophysics, 22, n° 3, 1957,
p. 660
5
D.F. Bleil: Induced Polarization; Geophysics, 18, n°3, 1953, pp. 636; D.J. Marshall, Th. Madden: Induced
Polarization, A Study of its Causes; Geophysics, 24, 1959, p. 790 T.R. Madden, T. Cantwell: Induced Polarization:
A Review. Mining Ge ophysics, Vol. II, ed.: Society of Exploration Geophysicists, 1967; J.W. Wait (ed.)
Overvoltage Research and Geophysical Applications; Pergamon Press, London, New York pp., 1959, T.J. Katsube:
The Electrical Polarization Mechanism Model for Moist Rock; Geol. Survey of Canada, paper 75-1C, p. 353;
Grahame: Mathematical Theory of the Faradic Admittance; Journal of the Electrochemical Society, 99, 1952, p.
370C , only to mention a selection of papers
6
D. Rahner, H. Gruenzig, G. Ludwig: A Study on the Electrochemical Remediation of Polluted Soils (in German,
with reprints in English); Report of the Technical University of Dresden (Germany) to the EPA of Saxony, August
1995; see also: preceding publications by: A. Brandt: Geophysical Exploration, US.-Pat. 2 611 004 (1952), P.
Mandel, J.W. Berg, K.L. Cook: Electrical Properties of Synthetic Metalliferous Ore; Geophysics 24, p. 510, I.I.
Rokityansky. The Nature of Induced Polarization of Ion-Conducting Soils; Academy of Sciences of the USSR,
Geophysical News, n°. 7, 1959, p. 752
7
A.P. Krajev: Basics of Geoelectricity (in Russian), Moscow 1957
9
8
Patrick et al.: paper presented to the Workshop on: Environmental Stability of Chemicals in Sediments, San Diego
April 8-10, 2003
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