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Patent 2441259 Summary

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(12) Patent: (11) CA 2441259
(54) English Title: ENVIRONMENTAL REMEDIATION METHOD AND APPARATUS
(54) French Title: PROCEDE ET DISPOSITIF D'ASSAINISSEMENT DE L'ENVIRONNEMENT
Status: Deemed expired
Bibliographic Data
(51) International Patent Classification (IPC):
  • C02F 1/72 (2006.01)
(72) Inventors :
  • KERFOOT, WILLIAM (United States of America)
(73) Owners :
  • KERFOOT, WILLIAM (United States of America)
(71) Applicants :
  • KERFOOT, WILLIAM (United States of America)
(74) Agent: SMART & BIGGAR
(74) Associate agent:
(45) Issued: 2012-10-09
(86) PCT Filing Date: 2002-05-16
(87) Open to Public Inspection: 2002-11-28
Examination requested: 2007-05-16
Availability of licence: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): Yes
(86) PCT Filing Number: PCT/US2002/015939
(87) International Publication Number: WO2002/094723
(85) National Entry: 2003-09-15

(30) Application Priority Data:
Application No. Country/Territory Date
09/860,659 United States of America 2001-05-18

Abstracts

English Abstract




Remediation systems (10) for water, soil, and sediment bodies using thin layer-
coated (54) microbubbles (52).


French Abstract

Cette invention concerne des systèmes d'assainissement (10) pour eau, huile et sédiment reposant sur l'emploi de micro-bulles (52) recouvertes d'une couche mince (54).

Claims

Note: Claims are shown in the official language in which they were submitted.



CLAIMS:
1. A remediation process comprising:

generating microbubbles comprising gas, coated with a thin layer of
liquid compounds suitable for promoting chemical degradation of organic
compounds
and generation of microbubbles comprising the gas, coated with the thin layer
of
liquid compounds suitable for promoting biological degradation of organic
compounds, the microbubbles being coated by directing the gas through the
liquid
and two layers of microporous material, resulting in the coated microbubbles.

2. The remediation process of claim 1, wherein the gas comprises ozone
and air.

3. The remediation process of claim 1, wherein the gas in the
microbubbles comprises air and ozone, with ozone at concentration to effect
reactions with contaminants and the liquid that coats the microbubbles is a
Criegee oxidation by-product or hydrogen peroxide.

4. The remediation process of any one of claims 1 to 3, wherein the
microbubbles have a diameter of less than 200 microns.

5. The remediation process of any one of claims 1 to 4, wherein
generating the microbubbles uses a diffusing apparatus, the diffusing
apparatus
comprising:

two concentric tubes each comprised of the microporous material,
wherein an inner tube of the two concentric tubes receives gas flow; and

a hydrophobic layer of microbeads 0.01 to 1.0 mm diameter
sandwiched between the two concentric tubes, wherein the hydrophobic layer
receives hydroperoxide flow;

22


wherein the microporous material is 0.5-200 micron microporous
material.

6. The remediation process of any one of claims 1 to 4, wherein
generating the microbubbles uses a diffusing apparatus, the diffusing
apparatus
comprising:

two concentric tubes each comprised of the microporous material,
wherein an inner tube of the two concentric tubes receives gas flow; and

a hydrophobic layer of microbeads or a porous material sandwiched
between the two concentric tubes, wherein the hydrophobic layer receives
hydroperoxide flow;

wherein the microporous material comprises 5-200 micron stainless
steel.

7. The remediation process of any one of claims 1 to 6, wherein the
microporous material is porous high-density polyethylene, polyvinyl chloride,
polytetrafluoroethylene, low-density polyethylene, acetal, or polypropylene.

8. The remediation process of any one of claims 1 to 7, wherein the
degradation is a chemical reaction that is oxidative.

9. The remediation process of any one of claims 1 to 7, wherein the
degradation is a chemical reaction that is reductive.

10. The remediation process of any one of claims 1 to 9, wherein the
coated microbubbles are injected into soil.

11. The process of claim 2, further comprising:
23



an aerosol injection system to inject liquid hydroperoxide into a stream
of ozone-containing air to generate the microbubble as an aerosol/gas mixture,

wherein the liquid hydroperoxide is pulled under vacuum into the air/ozone
stream
and the combined aerosol/gas mixture enters a microporous diffuser yielding
0.5-100 micron microbubbles into soil pore channels, the diffuser comprising
said two
layers of microporous material.

12. The process of claim 2, further comprising:

introducing an aerosol with a spray head inserted at a "T" connection on
the top of a wellhead leading to a microporous diffuser, the spray head being
adjustable to vary a liquid flow feed rate from between about 1/10 to about
1/10,000 of the flow of air/ozone volume flow, and wherein the liquid is
introduced as
an aerosol flow of the liquid, continuously with the air/ozone flow.

13. The process of claim 2, further comprising:

introducing an aerosol flow of the liquid using a spray head that is fed
by a second, different air compressor system.

14. The process of claim 2, further comprising:

using an array of spray-heads fed by the liquid to provide aerosol flows
of the liquid to the microporous diffusers to create a microbubbles interface
to
intercept and contain a migrating plume.

15. The process of claim 11, further comprising:

pulsing simultaneously the aerosol and air/ozone stream to coat the
microbubbles and maximize dispersion of bubbles through a geological
formation.
16. A remediation process comprising:


24



generating microbubbles comprising a gas, coated with a thin layer of
liquid compounds suitable for promoting chemical degradation of organic
compounds
wherein the microbubble is coated by introducing a liquid as an aerosol to a
gas,
which mixture is forced through a microporous material, resulting in the
coated
microbubble, and introducing the coated microbubble in an area to be
remediated.

17. The remediation process of claim 16, where the chemical degradation is
an oxidative reaction.

18. The remediation process of claim 17, wherein the microbubble
comprises ozone gas with hydroperoxide or peracid coatings.

19. The remediation process of claim 17, wherein the microbubble
comprises air with hydroperoxide or peracid coatings.

20. The remediation process of claim 17, wherein the microbubble
comprises ozone gas with permanganate coatings.

21. The remediation process of claim 17, wherein the microbubble
comprises air with permanganate coatings.

22. The remediation process of claim 17, wherein the microbubble
comprises air with Fenton's Reagent coatings.

23. The remediation process of claim 17, wherein the microbubble
comprises ozone with Fenton's Reagent coatings.

24. The process of claim 17 further comprising:

promoting biological remediation by including contacting microbubbles
comprising oxygen-enriched air and a carbon-source as the liquid coating, and
wherein the biological remediation step follows the chemical oxidation
microbubble
contacting.





25. The process of claim 24, wherein biological microbubble contacting is
alternated with chemical oxidation microbubble contacting.

26. The process of claim 16, wherein the organic compounds are degraded
by an oxidation reaction at the interfaces of the thin-layer coating that
includes
reactants and Criegee oxidation by-products resulting from the interaction of
ozone
and hydroperoxide.

27. The process of claim 16, wherein the organic compounds are volatile
organic compounds (VOCs) with Henry's Constants less than or equal to
10-5 ATM-M3/mole.

28. The process of claim 16, wherein the organic compounds are
halogenated volatile organic compounds (HVOCs).

29. The process of claim 28, wherein the halogenated volatile organic
compounds are selected from the group consisting of perchloroethylene,
trichloroethylene, dichloroethylene, vinyl chloride, trichloroethane,
dichloroethane,
chloroform, ethylene dibromide, and chlorobenzene.

30. The process of claim 28, wherein the halogenated volatile organic
compounds are selected from the group consisting of PC8s, heptachlor,
petroleum
aromatics, BTEX, benzene, toluene, ethylbenzene, xylenes, naphthalene,
methyl-t-butyl ether; aromatic nitro compounds, trinitrotoluene, nitrobenzene;
styrene
and ethyl-t-butyl ether.

31. The process of claim 28, wherein the halogenated volatile organic
compounds is methyl-t-butyl ether.

32. The process of claim 16 wherein the organic compounds are poorly
volatile, having a Henry's Constant greater than 10-5 ATM-M3/mole and break
down
into volatile organic compound by-products upon chemical oxidation microbubble

contact.


26



33. The process of claim 32, wherein the organic compounds are
polyaromatic hydrocarbons anthracene, fluoranthene, phenanthrene, naphthalene,

polychlorinated phenols, or phthalates.

34. The process of claim 17, wherein the liquid is an oxidizing agent and is
hydrogen peroxide, or an intermediate by-product of decomposition of ozone and
an
organic compound, including a peracid, formic peracid, acetic peracid,
hydroxymethylhydroperoxide, or 2-hydroxy-2-propyl hydroperoxide and the
peracid is
peroxyacetic acid, peroxyformicacid, perhydroxymethyl acid, or perhydroxyacid.

35. An apparatus comprising:
an injection well;

a source of a liquid suitable for promoting biological degradation of
organic compounds;

a source for delivering a gas;

an aerosolizer for aerosolizing the gas;

a microporous diffuser for receiving the gas from the aerosolizer, with
the microporous diffuser disposed in the well for generating coated
microbubbles of a
controlled size comprising the gas and a liquid coating of the liquid suitable
for
promoting biological degradation.

36. The apparatus of claim 35, wherein the microporous diffuser injects the
gas and liquid simultaneously.

37. The apparatus of claim 35 or 36, further comprising:

a controller for controlling the ratio of gas and liquid in generating the
coated microbubble.


27



38. The apparatus of claim 35 or 36, further comprising:

a controller for controlling mixing of ambient air with said liquids.
39. The apparatus of any one of claims 35 to 38, further comprising:

an agitator to pulse or surge the microbubbles into the well to improve
transport of coated microbubbles through the contaminated area.

40. The apparatus of claim 39 wherein the agitator comprises a
submersible pump.

41. The apparatus of claim 38, wherein the controller for controlling mixing
comprises:

a wellhead control for equalizing flow between formations of differing
permeability.

42. The apparatus of claim 39 wherein the agitator alternates pumping of
water and coated microbubble injection.

43. The apparatus of any one of claims 35 to 42, wherein the liquid is an
oxidizing agent and is hydrogen peroxide, or an intermediate by-product of
decomposition of ozone and an organic compound, including a peracid, formic
peracid, acetic peracid, hydroxymethylhydroperoxide, or 2-hydroxy-2-propyl
hydroperoxide.

44. A water stream comprising a plurality of microbubbles in the water, the
microbubbles entrapping a gas mixture of ozone-air that is coated with a thin
layer of
a liquid compound suitable for promoting biological degradation of organic

compounds.
45. The water stream of claim 44, wherein the liquid compound is a carbon
source, a nitrogen source, a phosphorous source, or a potassium source.


28



46. The water stream of claim 44 or 45, wherein the gas mixture of the
ozone-air further comprises an added amount of oxygen beyond an amount of
oxygen typically found in air, with the added amount excluding the ozone in
the gas
mixture.


29

Description

Note: Descriptions are shown in the official language in which they were submitted.



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Environmental Remediation Method and Apparatus
TECHNICAL FIELD

This invention relates to remediation systems, and more particularly to
remediation systems for water, soil, and sediment bodies.

BACKGROUND
There is a well-recognized need for remediation, or clean-up, of
contaminants (e.g., chemicals) that exist in a variety of settings, including
ground and
surface water, aquifers, water supply pipes, soil, and sediment collections.
These
settings are frequently contaminated with various constituents such as
volatile
organic compounds (VOCs). These contaminated areas pose a threat to the
environment, and ultimately to the health and safety of all living creatures.
Thus,
equipment and methods for effectively and safely dealing with remediation of
environmental contaminants is of significant importance.

SUMMARY
According to an aspect of the present invention, there is provided a
remediation process comprising: generating microbubbles comprising gas, coated
with a thin layer of liquid compounds suitable for promoting chemical
degradation of
organic compounds and generation of microbubbles comprising the gas, coated
with
the thin layer of liquid compounds suitable for promoting biological
degradation of
organic compounds, the microbubbles being coated by directing the gas through
the
liquid and two layers of microporous material, resulting in the coated
microbubbles.
According to another aspect of the present invention, there is provided
a remediation process comprising: generating microbubbles comprising a gas,
coated
with a thin layer of liquid compounds suitable for promoting chemical
degradation of
organic compounds wherein the microbubble is coated by introducing a liquid as
an

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aerosol to a gas, which mixture is forced through a microporous material,
resulting in
the coated microbubble, and introducing the coated microbubble in an area to
be
remediated.

According to another aspect of the present invention, there is provided
an apparatus comprising: an injection well; a source of a liquid suitable for
promoting
biological degradation of organic compounds; a source for delivering a gas; an
aerosolizer for aerosolizing the gas; a microporous diffuser for receiving the
gas from
the aerosolizer, with the microporous diffuser disposed in the well for
generating
coated microbubbles of a controlled size comprising the gas and a liquid
coating of
the liquid suitable for promoting biological degradation.

According to another aspect of the present invention, there is provided
a water stream comprising a plurality of microbubbles in the water, the
microbubbles
entrapping a gas mixture of ozone-air that is coated with a thin layer of a
liquid
compound suitable for promoting biological degradation of organic compounds.

According to another aspect of the invention, a remediation process
includes generating microbubbles comprising a gas, coated with a thin layer of
liquid
compounds suitable for promoting biological degradation of organic compounds.

According to another aspect of the invention, a remediation process
includes generating microbubbles comprising a gas, coated with a thin layer of
liquid
compounds suitable for promoting chemical degradation of organic compounds and
generation of microbubbles comprising a gas, coated with a thin layer of
liquid
compounds suitable for promoting biological degradation of organic compounds.
According to another aspect of the invention, a remediation process
includes generating microbubbles comprising a gas, coated with a thin layer of
liquid
compounds suitable for promoting chemical degradation of organic compounds
wherein the microbubble is coated by introducing a liquid as an aerosol to a
gas,
which mixture is forced through a microporous

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material, resulting in the coated microbubble, and contacting the coated
microbubble with the
area to be remediated.
According to another aspect of the invention, an apparatus for remediating a
contaminated area using a liquid-coated microbubble including one or more
gases includes an
injection well and a source of a liquid suitable for promoting biological
degradation of organic
compounds. The apparatus also includes a source for delivering a gas, an
aerosolizer for
aerosolizing the gas and a microporous diffuser disposed in the well for
generating coated
microbubbles of a controlled size comprising the gas and a liquid coating.
According to another aspect of the invention, an aerosol head includes a
reservoir of
liquid and a tube supply with compressed air. The head also includes a mixing
chamber where
the liquid is drawn into the flowing gas and a spray head which controls the
particle size and
distribution of the aerosols.
According to another aspect of the invention, a microbubble includes a gas,
coated with a
thin layer of liquid compound suitable for promoting biological degradation of
organic
compounds.
One or more aspects of the invention may include one or more of the following
advantages. Thin-layer microbubbles with chemical or biological remediative
characteristics, car
be selected and engineered for particular remediation applications. The use of
these coated
microbubbles results in remediative processes wherein the microbubbles offer
improved
dispersion characteristics, improved reactivity characteristics, enhanced
reestablishment of
indigenous organisms in the treatment area, and broad applicability to a
variety of treatment
settings.
This invention relates to thin-layer coated microbubbles and their use,
including
remediation systems, and more particularly to remediation systems for water,
soil, and sediment
bodies. The remediation can be in the form of chemical reaction (i.e.,
degradation) of various
contaminants or in the form of enhancing environmental conditions, or the food
or nutrient
supply, to indigenous organisms (e.g., bacteria) in order to promote their
activity in remediating
the contaminants or by-products of the contaminant remediation.
The details of one or more embodiments of the invention are set forth in the
accornpa-
vying drawings and the description below. Other features, objects, and
advantages of the
invention will be apparent from the description and drawings, and from the
claims.

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DESCRIPTION OF DRAWINGS
FIG I is a schematic of a Criegee oxidizer and nutribubble system.
FIG 2 illustrates an example of a monitoring well screen modified for laminar
diffuser
injections.
FIG 3 illustrates a microbubble apparatus as used in soil/groundwater
applications.
FIG 4 is a schematic representation of a microbubble and processes within the
microbubble.
FIG 5 illustrates one depiction of a zone of influence by dissolved oxygen
change
showing gyre formation around a microporous diffuser well due to mixing of
microbubbles.
FIG 6 illustrates an example of remediation using compressed gas tanks instead
of
compressors to supply gas in non-power sites.

DETAILED DESCRIPTION
Contaminants are any agent that directly, or indirectly, has a detrimental
effect on the
environment or a living creature (e.g., human, animal, insect, plant).
Contaminants include
volatile organic compounds, non-volatile organic compounds, polyaromatic
hydrocarbons
(PAH5) (e.g., anthracene, fluoranthene, phenanthrene, naphthalene);
polychlorinated biphenyls
(PCB5)(e.g., arochlor 1016); chlorinated hydrocarbons (e.g.,
tetrachloroethene, cis- and trans-
dichloroethene, vinyl chloride, 1, 1, 1 -trichloro ethane, 1,1-dichloroethane,
1,2-dichloroethane,
methylene chloride, chloroform, etc.); methyl tertiary-butyl ether (MTBE); and
BTEX (e.g.,
benzene, toluene, ethylbenzene, xylenes, and the like); explosive residues
(e.g., nitrobenzenes,
RDX, trinitrotoluene (TNT), etc.); and chlorinated pesticides (e.g.,
chlordane, heptachlor, etc.).
The microbubbles, apparatuses, and methods herein are useful in remediating
contaminants,
including any one, or combination of, those delineated herein.
Chemical reaction is any interaction between two or more chemicals resulting
in a
chemical change in the original reactants. The reactions may be oxidative or
reductive in nature.
The reaction can occur in any state, including the solid, gaseous, or liquid
state or an interface
thereof. The reaction can be enhanced (e.g., efficiency improved, reaction
rate increased) by
addition of one or more catalysts.
Biological reactions are any reaction that involves a biological process
(e.g., bacterial
metabolism, bacterial growth or proliferation). For example, in the processes
delineated herein,
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certain organic compounds are subject to oxidative or reductive chemical
degradation, resulting in lower molecular weight fragments or by-products.
These
by-products may be involved in bacterial metabolism such that they are
"consumed" by the bacteria thereby undergoing a biological reaction or
degradation. In other instances, the processes delineated herein provide
nutrients
(e.g., oxygen, nitrogen, carbon, phosphorous, potassium) such that bacterial
growth, support, or proliferation can occur upon consumption of the nutrients.
These are also considered biological reactions. Further, certain processes
delineated herein using oxidative chemical reaction conditions, such as ozone,
result in oxygen as a by-product (e.g., reduction of ozone to oxygen), which
can
act as feed for certain indigenous bacteria in the remediation area. Such
enhancement of biological function, or bioremediation, is also considered
within
the scope of biological reaction.

Referring to FIG. 1, injection well treatment system 10 includes
microporous diffusers 12 disposed through an injection well to treat
subsurface
waters of an aquifer. The arrangement 10 includes a well 14 having a casing 16
with an inlet screen 18 (Figure 2) and outlet screen 20 (Figure 2) to promote
a
recirculation of water into the casing 16 and through the surrounding ground
area.
The casing 16 supports the ground and aquifer about the well. Disposed through
the casing is the microporous diffuser 12. The injection well treatment system
10
includes master unit 22, which includes a controller 31, an air compressor 32,
a
compressor/pump control mechanism 34, and an ozone (03) generator 36.
Microporous diffusers 12 are in communication with master unit 22 by way of
gas
transfer line 24 and liquid transfer line 26, each of which is a pipe made of
suitable
material to accommodate transfer of the appropriate fluid to microporous
diffusers
12. The air compressor 32 can feed a stream of air into the microporous
diffuser
12 whereas, the compressor pump control 34 feeds a stream of air mixed with
ozone (03) from the ozone generator 36 into microporous diffuser 12 to affect
substantial removal of contaminants. The treatment system 10 also includes a
pump 38 that supplies a liquid decontamination agent such as hydrogen peroxide
as well as nutrients such as biologically promotion agents, including carbon,
nitrogen, phosphorous or potassium sources, from a source 39, e.g. a liquid
drum.

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The system 10 can also supply catalyst agents such as iron
containing compounds such as iron silicates or palladium containing compounds
such as palladized carbon. In addition, other materials such as platinum may
also
be used.

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The treatment system 10 makes use of a gas-gas reaction of contaminant vapors
and
ozone (described below) that can be supplemented with a liquid phase reaction.
The use of
hydrogen peroxide as a thin film coating on the bubbles promotes the
decomposition rate by
adding a secondary liquid phase reactive interface as volatile compounds enter
the gaseous
phase. It also expands the types of compounds that can be effectively removed.
Alternatively,
the pump control 38 can simply feed water. In addition, the biological
nutrients can aid in the
promotion of growth of bacteria to aid in bioremediation after treatment with
ozone as described
below.
Remediation using the equipment and techniques delineated herein can be
performed to a
variety of areas, including, for example, bodies of water (e.g., ground,
surface, supply conduits
including pipe systems), soil areas (saturated or unsaturated with liquids,
e.g., water), and
collections of sediments. A suitable area for remediation using the
ozone/nutribubble technique is
one in which the hydraulic conductivity of the geologic formation is between
10"1 and 10-6
cm/sec. In one embodiment, the remedial area is first treated with ozone/air
microbubbles coatec
with hydroperoxide if necessary for specific bond cleavage or increase in
oxidative potential.
Ozone reacts in an aqueous and gaseous form to degrade aromatic ring compounds
(BTEX) and
certain ethers (MTBE). It also breaks apart long-chain aliphatic compounds.
Following removal
of BTEX/MTBE compounds, oxygen-enriched air bubbles are coated with a nutrient
mixture and
injected into the aquifer. The fine bubbles serve to assist in pumping the
nutrients through the
capillary structure of the formation being treated. The bubbles assist in
removing CO2 as well as
supplying oxygen for respiration. Nutribubbles are any coated microbubble
wherein the gas in
the bubble, the thin-layer bubble coating, or combinations thereof, include a
nutrient (e.g.,
oxygen, nitrogen, carbon source, phosphorus source), that is, a material that
is useful for
enhancement of the survival, growth, or proliferation of an organism, such as
bacteria.
Introduction of the ozone/nutribubbles is accomplished by the microporous
diffusers,
which receive the simultaneous supply of gas and liquid. The pulsed injection
of gas through the
diffuser eliminates the common problem of plugging of injection wells. Pulsing
refers to a
systematic, or cyclic, sequence of injection of a material into the
remediation area. For example,
in the methods delineated herein, a sequence can be invoked wherein a
treatment area is injected
with the coated microbubbles delineated herein, followed by injection (or
pumping) of water,
followed by a rest period, whereupon the sequence is commenced again, and
repeated in periodic
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cycles (e.g., 15-30 minute intervals). In this manner, a "pressure wave" is
effectively produced
that assists in dispersion of the microbubbles through the treatment area.
The injection well can be a monitoring well, where a microporous diffuser is
placed to
take advantage of the existing well.
Referring to FIG 2, a modified well screen having a laminar diffuser is
illustrated. The
modified well screen is comprised of screened PVC pipe having a 0.02 in. slot
size with a
inflated packer to produce an isolated portion of the well screen disposed
between a microporous
diffuser and upper portions of the well. Bentonite is disposed about the
inflated packer. The
microporous diffuser receives gas (e.g., air/ozone, nitrogen) and liquid
(e.g., hydroperoxide or
nutrients) in transfer lines otherwise using an apparatus similarly to that
described in FIG. 1.
Referring to FIG 3, an alternative microbubble apparatus 40 useful in
soil/groundwater
remediation applications includes an aerosolizer 42, a mixing chamber 44 and a
T -junction 46.
The apparatus 40 includes the elements of the system of FIG. 1 namely,
microporous diffusers 12
disposed through an injection well 14. The well 14 has a casingl6 that can
have an inlet screen
(not shown) and outlet screen (not shown) to promote a recirculation of water
into the casing 16
and through the surrounding ground area. The injection well treatment system
10 also includes
an air compressor 32, a compressor/pump control mechanism 34, and an ozone
(03) generator
36. The compressor pump control 34 feeds a stream of air mixed with ozone (03)
from the
ozone generator 36 into microporous diffuser 12 via through the aerosolizer 42
and the mixing
chamber 44. A major portion of the liquid stream goes directly to the mixing
chamber whereas a
minor portion goes to the aerosolizer. The aerosolizer also receives a liquid
steam of a
decontaminant liquid e.g., hydrogen peroxide, or other liquid oxidizer and/or
biological nutrients
from a source 50. The mixing chamber 44 is coupled to the well head 48.
Still referring to FIG. 3, the coated microbubble 52 includes a gas region 56
surrounded
by thin-layer coating 54. Aerosol particles 58 are dispersed within the gas
region and within the
thin-layer coating 54. Thin-layer coating 54 includes one or more components,
such as oxidants,
catalysts, acids, or nutrients. Upon leaving microporous diffuser 12, coated
microbubbles 52
diffuse throughout the treatment area (e.g., aquifer, ground water, soil,
sediment). For example,
coated microbubbles 52 can travel through capillary networks (or pores) in the
soil. Within the
capillary networks, coated microbubbles 52 contact groundwater (in saturated
soil) within the
capillary network. Upon contact with the groundwater, the coated microbubbles
52 react with the
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organic chemicals (or other contaminants) in the groundwater, thus leading to
degradation of the
organic chemicals or contaminants. The coated microbubbles 52 can also diffuse
in unsaturated
soil capillary networks, where the pores are predominately gaseous containing.
Referring to FIG. 4, a schematic representation of a microbubble 60 is shown,
wherein
ozone is the gas and hydroperoxide is the liquid. The microbubble 60 has a gas
region 68, and a
thin-layer coating 64 defined by an internal interface 62 and an external
interface 66. In
ozone/hydroperoxide combinations, the gas region 68 includes ozone gas.
Criegee-like
oxidation processes occur at the interfaces of the thin-layer coating 64 such
that the thin-layer
coating can include both reactants (e.g., hydroperoxide) as well as Criegee
oxidation by-products
(e.g., hydroxide radicals, peroxy acids) resulting from the interaction of
ozone and
hydroperoxide. Thin-layer coating 64 advantageously provides for these
reactants and by-
products to remain in proximity to allow further reaction and to facilitate
more efficient
interaction of the reactants with the organic compounds or contaminants. The
various
partitioning effects of the solid-liquid-gas phases of coated microbubble 60
are also illustrated.
For example, with respect to the microbubble, solubility (gas-aqueous
partitioning) and its
counterpart (aqueous-gas partitioning, governed by Henry's Constant) are
processes relating to
gas-aqueous phase interactions.. Adsorption (gas-solid, liquid-solid) and its
counterparts,
stripping (solid-gas) and solubility (solid-aqueous) relate to gas-solid and
liquid-solid
partitioning processes. The interaction of these processes, both in the coated
microbubble itself
and through its interaction with the treatment area, contribute to the
behavior, and advantages, of
the coated microbubbles for remediation applications.
The introduction of ozone has an action similar to steaming of soils in
reducing
indigenous bacterial populations within 10 ft. (ca. 3 m) of the injection
well, while additionally
degrading organics to more readily attackable forms. Ozone also naturally
decomposes to
oxygen, theoretically supplying up to ten times the dissolvable oxygen content
found with direct
air injection. Oxygen-enriched air injection with nutrients purges the
remaining ozone residual,
allowing indigenous bacterial species capable of organic residue metabolism to
quickly expand
through the formation.
FIG. 5 illustrates an example of how coated microbubbles diffuse in a
treatment area. In
FIG. 5, injection well system 71, is a system similar to those described, for
example, in FIG. I or
FIG6 herein. It has a microporous diffuser 12 for release of the coated
microbubbles.

7


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Monitoring wells 73 (depicted as KV-l, KV-2, KV-3, KV-4, KV-5, and KV-6) are
used to
monitor the products and by-products produced after coated microbubble
treatment. Upon
release of coated microbubbles into the ground, the coated microbubbles flow
(and displace
water in a similar flow pattern) in patterns depicted as flow patterns 75, 76,
and 77. In this
manner, mixing of the coated microbubbles in the treatment area occurs. Over
time (e.g., 3 days
20 days and so forth) these flow patterns result in oxidative reaction zones
78 and 79,
respectively. These reactive zones are areas in which the coated microbubbles
have caused more
concentrated degradation due to more focused contact and reactivity. The
dispersion of the
coated microbubbles, however, is not limited to these reactive zones
exclusively, rather the
coated microbubbles are capable of flowing in all directions.
FIG 6 illustrates an example of how the injection well treatment system can be
modified
for non-power accessible sites. Well treatment system 80 includes elements of
the system of
FIG 1, including microporous diffusers 12 disposed through an injection well
14. The liquid
coating material is supplied by compressed gas tank 82 in communication with
cap 90. Liquid
supply 84 provides the coating materials (e.g., oxidants, catalysts,
nutrients) via siphon line 92 to
cap 90, which can be performed with or without application of pressure (i.e.,
with or without a
compressor). A gas in compressed gas tank 86 is transferred via tubing through
valve and flow
meter assembly 88 to cap 90. The cap 90 is in communication with microporous
diffusers 12 via
gas and liquid transfer lines 22 and 24, respectively, and combination of the
gas and liquid result;
in generation of coated microbubbles.
Microbiological degradation is a technique to degrade complex organic
compounds. The
rate of reaction depends upon the type of microbe, the substrate compound
targeted as food, and
the rate of gaseous exchange. Bubbling oxygen-enriched air through an aqueous
solution of
substrate compound, supplied with the nutrients nitrogen (N), phosphorus (P),
and potassium
(K), can encourage rapid metabolism and reproduction of microbes, which
consume the organic
compounds.
There are specific ratios of carbon (C), nitrogen (N), phosphorus (P), and
potassium (K)
to promote an efficient reaction. Often these reflect the molecular ratio of
the elements in the
growth of microbes and are used to expand the population numbers. During
microbial
degradation of the carbon compounds, oxygen is consumed and carbon dioxide
(C02) is
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WO 02/094723 PCT/US02/15939
produced. If there is insufficient oxygen, the reaction will be self-limiting,
abruptly slowing and
eventually stopping.

The basic microbial process of biodegradation (aerobic) can be portrayed as a
conversion
of oxygen (02) to CO2 and water plus more bacteria:


bacteria
Organic contaminant IN- CO2 + H2O + more bacteria
02

Whereas the reaction may proceed rapidly in vat or surface vessels,
maintaining an
efficient and continuous degradation is much more difficult in porous soils.
Often evidence of
natural biodegradation is shown by excess CO2 in the overlying unsaturated
soil zone (vadose
zone) and low oxygen content in the saturated (aqueous) zone. The depletion of
natural electron
acceptors (02, NO3, SO4, Fe (III)), the depletion of natural electron donors
(organic acids, e.g.,
acetate, lactate, H2), the buildup of anaerobic metabolism gases such as C02,
and the depletion o-
mineral nutrients (NH3, NO3, P04, K) regulate the rate of biodegradation.
The choice of oxidants can be used to tailor the remediation process for a
selected class
of chemical compounds, thus allowing one to design a remediation system for a
particular
application. This is accomplished by an analysis of the volatile organic
compound to be
remediated, taking into account its Henry's Constant value (see, Tables 1 and
2), which is an
indicator of its proclivity to move from the liquid to the gaseous phase of an
interface. By
matching this transfer rate with that of the reactivity rate of a particular
oxidant, the remediation
process can be tailored such that the particular volatile organic compound is
optimally reacted
(and therefore remediated) relative to other volatile organic compounds
present.


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Table 1. Ideal for Ozone and Ozone/Hydroperoxide

High Henry's Constants (?10-5) Henry's Law Constant
(atm-m3/mole)
Benzene 5.6 x 10"3
Benzo(a) pyrene 1.1 x 10-4
Benzo(b) fluoranthene 1.1 x 10-4
Bromodichloromethane 1.6 x 10-3
Bromoform 5.5 x 10-4
Bromomethane 6.2 x 10-3
Carbofuran 9.2 x 10-5
Carbon Tetrachloride 3.0 x 10-2
Carbon Disulfide 3.0 x 10-2
Chlordane 4.9 x 10-5
Chloroethane 6.2 x 10-4
Chloroform 2.7 x 10-3
Chloromethane 8.8 x 10-3
Chrysene 9.5 x 10-5
1,2 Dibromoethane (EDB) 6.7 x 10-4
Dibromochloromethane 8.7 x 10-4
1,2-Dibromo-3-chloropropane 1.5 x 10-4
1,2-Dichlorobenzene 1.9 x 10-3
1,3-Dichlorobenzene 3.3 x 10-3
1,4-Dichlorobenzene 2.4 x 10"3
Dichlorodifluoromethane 3.4 x 10-3
1,1-Dichloroethane 5.6 x 10"3
1,2-Dichloroethane 9.8 x 10-4
1,2-Dichloroethylene (cis) 4.1 x 10-3
1,2-Dichloroethylene (trans) 9.4 x 10-3
1,1-Dichloroethylene 2.6 x 10-2
1,2-Dichloropropane 2.8 x 10-3
1,3-Dichloropropene 1.8 x 10-2
Dioxins 5.6 x 10-3
Ethyl Benzene 8.4 x 10"3
Fluorene 1.0 x 10-4
Fluorotrichloromethane (freon 11) 9.7 x 10"2
Heptachlor 1.1 x 10"3
Heptachlor epoxide 3.2 x 10-5
Hexachlorobenzene 1.3 x 10-3
Lindane 1.4 x 10-5
Methoxychlor 1.6 x 10-5
Methyl isobutyl ketane 1.4 x 10-4


CA 02441259 2003-09-15
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Methyl ethyl ketone (MEK) 2.7 x 10"5
Methylene chloride 2.0 x 10-3
Monochlorobenzene 3.8 x 10"3
n-Hexane 1.4 x 10-2
Napththalene 4.8 x 10-4
Polychlorinated biphenyls 1.1 x 10"3
Pyrene 1.1 x 10-5
Styrene 2.8 x 10"3
1,1,1,2-Tetrachloroethane 2.4 x 10-3
1,1,2,2-Tetrachloroethane 4.6 x 10-4
Tetrachloroethylene 1.8 x 10-2
Toluene 6.6 x 10-3
1,2,4-Trichlorobenzene 1.4 x 10-3
1, 1, 1 -Trichloroethane 1.7 x 10-2
1,2,3-Trichloropropane 3.4 x 10-4
Trichloroethylene 1.0 x 10-2
Trifluralin 2.6 x 10-5
1,2,4-Trimethylbenzene 5.6 x 10"3
Vinyl chloride 2.7 x 10-2
Xylene (mixed o-, m-, and p-) 7.0 x 10-3

Table 2. Moderate Henry's Constants But Breakdown Products
With High Henry's Constants

Henry's Constant
Dibutyl phthalate 1.8 x 10-6
2,4-Dichlorophenoxyacetic acid 1.0 x 10.8
Di(2-ethylhexyl) phthalate 3.6 x 10-'
2,4-Dinitrotoluene 1.3 x 10-'
2,6-Dinitrotoluene 7.5 x 10-'
Dinoseb 4.6 x 10-'
Endrin 7.5 x 10-6
Fluoranthrene 6.5 x 10-6
Pentachiorophenol 2.4 x 10-6
Phenol 3.3 x 10-'
Pyridine 8.9 x 10-6
Toxaphene 6.6 x 10-6

The rate of biodegradation in natural formations is very slow compared to
above-ground
settings. The ability to mix gases, electron donors, or nutrients with organic
contaminates is
limited by the porosity and hydraulic conductivity of saturated soils. Porous
soils tend to
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encourage movement of liquids as slugs, not easily mixing with existing
groundwater. The rate
of natural movement is slow and determined by existing groundwater gradients.
Velocities of
natural flows commonly run 0.1 to 2 ft/day. The natural flow across a 100 ft
wide contaminant
zone may take 50 to 1000 days. The capability to remove product waste products
is similarly

hindered.
To address these issues, an efficient technique to provide reaction promoters
and
simultaneously to remove unnecessary products is desirable. "Food" in the form
of carbon
sources which provide energy (electron donors) is available in liquid form.
Nutrients also can be
mixed with "food" forms to assure ready availability of all required
components for remediation
conditions and organism growth enhancing environments. The presence of both as
a coating to
oxygen-enriched air provides bacteria with a very mobile nutrient system. In
addition, gaseous
products such as CO2 can be transported away (i.e., displaced from the
remediation area) as the
gas rises. Microbubble technology provides the necessary attributes to meet
these needs.
A microbubble can be "coated" by forcing microbubbles from less than about 200
microns, e.g., 0.5 to 200 micron size through a porous liquid stream in a
diffuser, (e.g., a
"laminated" Microporous Spargepoint diffuser (Model Nos. SPT2000 and
SPT2010), available
from K-V Associates, inc., Mashpce, MA) or by introducing aerosolized liquid
particles into the
gas stream supplying a diffuser. While not being bound by theory, generally,
coatings made by
forcing the microbubble through the liquid stream result in relatively thicker
coatings caused, in
part, by the thicker reaction points of the liquid forced through the gaseous
phase in the diffuser.
Conversely, those generated by the aerosol method result in microbubbles with
relatively thinner
coatings caused, in part, by the finer porous points of the liquid when
introduced as an aerosol.
Thicker coatings generally elevate the reactivity of the microbubble,
particularly in oxidative
reactivity. For example, thicker coatings of oxidative material is associated
with increased
Criegee oxidative capacity or oxidative potential (see, Dowideit and Somitag,
Environ. Sci.
Technol. 1998, 32, 112-1119), that is, the ability of the
microbubble to break bonds of the chemical compound or contaminant subject to
oxidative
degradation. The thickness of a coating can be ascertained by techniques such
as microscopic
capillary analysis of the microbubbles with dyes (e.g., India ink),
backlighting, or photoelectric
cell detection methods.

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The microbubbles can include a thin-layer coating having a material suitable
for
oxidative reactivity. So called, "high oxidative capacity" or "advanced
oxidative" systems (e.g.,
using potassium or sodium permanganate, ozone in high concentrations, Fenton's
reagent) are
capable of particularly efficient chemical reactivity (e.g., bond breaking
capacity, carbon-
containing compound reactivity) useful in contaminant degradation processes.
These reactions
are characterized in that they have oxidation potentials in excess of 2.0
(based on
electrochemical reactions at 25 C.).
The microbubbles delineated herein are advantageous in that they can be
designed to
optimize their suitability for certain applications in remediation technology.
For example, the
microbubbles can be formed and shaped in the various manners described above
(e.g., using a
microporous diffuser, or aerosolized liquid and a microporous diffuser).
Depending on their size
and thickness, certain reactivity profiles can be achieved. Additionally, the
composition of the
gas in the bubble, as well as the type of liquid coating selected can be
chosen to accomplish
various oxidative or reductive degradation profiles, and catalysts (e.g.,
metals in microparticle
form, acids) can be incorporated into the microbubble to increase reactivity
and degradation
efficiency of the microbubble. Moreover, the methods of generating
microbubbles allow for
control of the stoichiometry of the chemical components in the microbubble,
again allowing for
the ability to tailor the microbubble to a specific profile for a desired
application or reactivity By
increasing the flow of liquid during the flow of gas, the thickness of the
coating can be increased
The strength of oxidation capacity can be effected by increasing the
concentration of hydrogen
peroxide in the liquid phase as well as increasing the ozone content in the
gas phase.
The size of the microbubble can also be varied by controlling the pressure of
the gas
during generation of the microbubble and by choice of the diffuser pore size.
For example, by
generating smaller coated microbubbles, the surface to volume ratio increases,
which improves
reactivity of the microbubble. Additionally, in instances where a coating
thickness is held
constant, a smaller coated microbubble effectively has a "thicker" coating
relative to a larger
coated microbubble, thus resulting in a coated microbubble with a "thicker"
coating and greater
surface area (relative to volume), which both contribute to increased
reactivity (e.g., in oxidative
coating applications, higher oxidative potential). Normally, the range of
fluid to gas varies from
parity (1:1) to about 1:100. This corresponds to a coating thicken of 0.3
(30%) increase in radius
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WO 02/094723 PCT/US02/15939
down to 0.01 (1%). Table 3 illustrates the relationship between gas and liquid
volumes and
variance in the coating thickness.
Table 3. Relationship of Microbubble Gas Volume to Liquid Volume with Change
in
Coating Thickness
Microbubble Size (mm)
Radius 1.0mm .10mm .01 mm .001 min
Diameter (2000micron) (200micron) (20micron) (2 micron)
Gas Volume 4.189mm .00419mm .00000419mm 3 .00000000419mnr
(1 m3/day
Liquid Volume
(tenths of
radius)
.05 660mm 0.00066mm 0.00000066mm 0.0000000066mm
(.157 m3/day)
.10 1.387mm .00138mm .00000138mm .00000000138mm-
(.33 m3/day)
3 3
.20 3.049mm .00305mm .00000305mm .00000000305mm-
(.73 m3/day)
Surface Area 12.57mm .1257mm .001257mm .00001257mm 2
Surface-to- 3 30 300 3000
Volume Ratio

Microbubbles can also be selected according to a controlled size using a
layered fine
bubble production chamber. The layered fine bubble production chamber is a
chamber in which
a liquid is placed under pressure and microbubbles are generated. That is,
over a period of time,
an environment is provided where the microbubbles segregate by size (e.g.,
larger microbubbles
rise and smaller microbubbles remain) thus allowing a mixture predominated by
a particular
microbubble size (or size range) to be established prior to injection into the
treatment area. This
is suitable for use, for example, where smaller microbubbles may be desired
(i.e., for their higher
surface to volume ratio).
One example of such control relates to the "Law of the Minimum", which states
that
bacterial growth will stop when the nutrient that was present in the lowest
concentration (relative
to the requirement) is exhausted, becomes a problem since the rest of the
mixture is useless. If
that substance is replenished, growth will stop when the next substance is
exhausted. By
providing a means of ready mixing of the constituents and having the capacity
to modify the
electron accelerator and nutrient ratios, using metabolic products as a guide
(e.g., monitoring by-
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60412-3206

products formation in real time by sampling via a monitoring well and
analyzing the samples
using, for example, gas chromatography or other suitable analytical
technique), the rate of
metabolism can be adjusted and maximized. In another embodiment, the methods
herein can be
applied such that an existing monitoring well can be used as an injection well
for the
microbubble diffuser.
Microbubbles form a unique physical and chemical environment which can
effectively
treat waterborne or attached (adsorbed) volatile organic compounds (VOCs).
Diffusers, or
spargers, placed in groundwater or saturated soil provide extremely small
"microbubbles" with a
very high surface area to volume ratio. This high surface area to volume ratio
maximizes the
VOC transfer from the liquid phase to gas phase. If the air bubbles are filled
with an oxidizing
gas, like ozone, the VOCs react with the ozone and are destroyed while still
in the water column.
This "in-situ"- combined VOC recovery and destruction not only obviates the
need for an
additional process step but also enhances the physical and chemical kinetics
of the process.
Microporous diffusers suitable for use in the methods described herein are
thosc having
the ability to deliver a gas and a liquid such that microbubbles less than
about 200 microns,
preferably between about 0.5 and 200 microns, are produced including the gas
therein and a thin
layer of the liquid material coating the microbubble. The diffuser can be
constructed of a variety
of materials suitable for the gases and liquids to be delivered, such
materials include, for
example, stainless steel, high-density polyethylene (HDPE), low-density
polyethylene (LDPE),
polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE, e.g., TEFLON), acetal
(e.g.,
DELRIN), or polypropylene. The diffuser can include concentric tubes of
microporous material,
optionally having additional packing materials (e.g., hydrophobic plastics,
hydrophilic plastics,
beads, interconnected fibers) sandwiched between the tubes to facilitate
creation of the gas-liquic
interface in the microbubble. These materials aid the liquid coating process
of the gas flowing
through the diffuser in the generation of microbubbles, in part by their
hydrophilic or
hydrophobic nature to enhance coating, and in part by their ability to
increase the positioning of
the liquid to optimize contact with the gas flowing through. Examples of
diffusers suitable for
use in the methods delineated herein include the laminar microporous
SPARGEPOINT diffusci
or the C-SPARGER diffuser (both available from K-V Associates, Inc., Mashpee,
MA).
Aerosols or aerosolized liquid particles are one method by which coated
microbubbles
can be formed. The aerosolized particles are produced using an aerosolizer
(see, FIG. 3),

l5


CA 02441259 2010-04-14
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including any apparatus suitable for providing an aerosolized form of a liquid
(e.g., a commercial
airbrush Badger 150). The aerosolized liquid particles can be any suitable for
use in the coating
application (i.e., chemical or biological reaction) and remediation process of
interest, including
for example, oxidants (e.g., hydroperoxides, potassium permanganate, Fenton's
reagent
(hydrogen peroxide and Fe(lI))), catalysts (e.g., as delineated below), acids,
(e.g., acetic, lactic),
and nutrients (e.g., as delineated below).
The aerosol can be generated using an aerosol head including a reservoir of
liquid or
liquid and microfine particles mixture; a siphon tube made of e.g., TEFLON or
resistant flexible
plastic; a tube supply with compressed air; a mixing chamber where the liquid
is drawn into the
flowing gas; a spray head which controls the particle size and distribution of
the aerosols; and a
compression fitting which directs the aerosol flow into the air/ozone gas
stream. The mixing
chamber can be, for example, a Bernoulli chamber, that is, any chamber that
(in accordance with
Bernoulli's principle) is capable of compressing a fluid through a narrower
opening into a larger
chamber resulting in a variance in pressure. The aerosol head can further
include connecting
tubing such as TEFLON tubing 3/8" to '/z" in diameter, polyvinyl chloride
tubing '/2" to 1" in
diameter, with o-ring seals (e.g., VITON) and threaded 5 ft. sections. The
aerosol head is in
communication with the microporous diffusers, in a manner to maintain a
sufficient rate of gas
flow to avoid condensing of the aerosol flow. The aerosol spray head can e
adjustable to vary
the liquid flow feed rate from between about 1/10 to 1/10,000 of the flow of
the air/ozone
volume flow. Also, the aerosol flow can be introduced continuously with the
air/ozone flow.
Catalysts are any material that is useful in catalyzing the desired chemical
transformation
or process to promote quicker or more efficient reaction. The catalysts are
presented as micron-
sized particles to augment the interface region of the microbubble. For
example, transition metals
including palladium (Pd), manganese (Mn), and iron (Fe), in elemental or salt
forms; sulfur
compounds including sulfates and sulfides.
Additionally, the acidity of reactions processes can be modified to enhance
reactivity, and
therefore the remediation processes herein. For chemical reactions (i.e.,
remediation processes)
that are more effective under lower pH conditions (i.e., acidic, pH less than
7) the microbubbles
can be coated with an acidic coating, thus, lowering the pH of the interface
and increasing the
reaction rate and efficiency of the remediation process. The acid can also be
incorporated in a
coating having other liquids in it where beneficial (e.g., increased
reactivity, efficiency) chemical
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effects can be realized, for example, acid and iron (II or III) salts (e.g.,
Fenton's reagent), which
in combination can catalyze the oxidative reactivity of the coated
microbubble. This is
advantageous in soil aquifers, where it is impractical to acidify the entire
aquifer, and is also
useful in reactions and remediation processes involving halocarbon
contaminants.
The gases useful in the microbubbles are any that are suitable for chemical or
biological
reaction and remediation. For example, in oxidative applications, ozone,
oxygen and air are
suitable gases. In reductive applications, nitrogen or hydrogen can be used.
The gas suitable for
an application is dependent , in part, on criteria such as the reaction
desired, or the bacterial
growth requirements (aerobic or anaerobic). The gas can be generated in situ
(e.g., ozone
generator), provided using a compressor, or provided via compressed tanks
(e.g., .
Nutrient coatings on the microbubbles are any suitable nutrient for bacterial
(aerobic or
anaerobic) growth. Such nutrients include, for example, carbon sources (e.g.,
carbohydrates,
sugars, beer, milk products, methanogens, organic acids such as acetic and
lactic acids, organic
esters such as acetates, proprionates, organic ketones such as acetone),
nitrogen sources (e.g.,
ammonia, nitrates, ammonium nitrate), phosphorous sources (e.g., soluble
phosphates, etc), and
potassium sources (e.g., 10,000 ppm of lactate; 680 ppm NH4NO3; 200 ppm KH2PO4
to provide
sources of carbon and nitrogen, and phosphorus and potassium). Generally,
environments
suitable for bacterial support and growth are made up of the nutrients in the
following relative
ratios: carbon (ca. 1000 parts), nitrogen (ca. 150 parts), phosphorous (ca. 30
parts), sulfur,
potassium, and sodium (ca. 10 parts each), calcium, magnesium, and chloride
(ca. 5 parts each),
iron (ca. 2 parts), and any remainder elements in trace amounts, with the
ratios based on molar
equivalents, which may be in the form of either elemental or ionic (i.e.,
salt) forms, or a
combination thereof.
Advantageous aspects of the invention include: 1) gas/liquid thin-layer
microbubble
oxidation to predigest and sterilize around injection locations; 2)
simultaneous injection of
nutrients and food source with gas in proportion to optimal ratio for
assimilation; 3) injection of
nutrients to provide a coating (thin layer) on gas (oxygen-enriched air) being
injected into porous
soil capillaries; 4) introduction in a pulsed manner with microbubbles of 5 to
100 micron
diameter sized to pores of soil to avoid fracturing of soil and to enhance
transport through
capillary-like soil voids; 5) use of microporous diffusers (e.g., Spargepoint
) or aerosolized
liquids and microporous diffusers for simultaneous introduction of gas and
liquid mixtures into
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coated microbubbles engineered for specific characteristics (e.g., size,
shape, reactivity,
composition).
In order that the invention described herein may be more readily understood,
the
following examples are set forth. It should be understood that these examples
are for illustrative
purposes only and are not to be construed as limiting this invention in any
manner. All references
cited herein are expressly incorporated by reference in their entirety.
Examples
Bench-scale tests were conducted on soil samples collected from a site located
in
Paterson, New Jersey and augmented with PCBs (e.g., arochlor 1260). The
purpose of the tests
was to evaluate the response of volatile organic compounds and semi-volatile
organic
compounds contained in soil aliquots extracted from these soil samples to an
aqueous
environment containing various injected concentrations of sparged air with
ozone or sparged air
with ozone plus varying concentrations of injected hydrogen peroxide. During
each test, treated
and untreated aqueous samples were collected from the test cell at regular
time intervals and
field screened with portable gas chromatograph for ionizable compounds. Prior
to, and
following each test, soil and groundwater samples were collected from the test
cell for
confirmatory laboratory analyses.

Testing Procedure
Initial bench-scale testing included putting approximately 5 grams of soil
sample in a 40
ml VOA vial with 30 ml of water and allowing headspace to develop, then
screening the
headspace in an HNu Systems Model 321 portable gas chromatograph. The purpose
of this step
was to extrapolate the volume of soil necessary to produce an instrument
response in the GC that
was noticeable for further testing.
Subsequent testing included stirring approximately 40 grams of soil sample in
500 ml of
water contained in an Erlenmeyer flask and subjecting the entire solution to
sparged air
containing approximately 100 ppmv of ozone. This test was conducted under 0
psig with
aqueous samples collected from the test cell at time intervals of 0, 2, 5, 10,
15, and 20 minutes
and field screened with portable gas chromatograph for ionizable compounds.
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Following the above preliminary bench-scale tests, further testing was
conducted in a
larger glass volume container to allow for split sampling of soil and
groundwater samples to a
certified laboratory for confirmatory analyses. This test cell included
mounting a stopper on the
1,000 ml container and drilling holes in the stopper to allow for various
tubing diameters to pass
through the stopper to accommodate: an external pressure gauge T'd with a
pressure relief
valve; a sample guideport to permit below-water-level aqueous sampling; a gas
line for a mini-
laminate Spargepoint (1.5 inch in height and 1.5 inch in diameter); and
injection of treatment
liquids such as a 3% solution of hydroperoxide or peracid precursor.
The following four bench-scale tests were all conducted under 5 psig. Split
groundwater
samples were collected at the beginning and end of each test run and sent to a
Massachusetts
state-certified laboratory for volatile organic analysis. Soil samples were
collected at the
beginning of each test run and sent to a Massachusetts state-certified
laboratory for volatile
organic analysis. Soil samples were collected at the beginning of each test
run and sent to a
Massachusetts state-certified laboratory for volatile and semi-volatile
organic analysis. A soil
sample was collected at the end of each test run and sent to a Massachusetts
state-certified
laboratory for semi-volatile organic analyses.

Results
The soil samples appeared to contain weathered oil as well as other organic
compounds.
Review of the portable gas chromatograms indicate the nearly complete
attenuation of ionizable
compounds by the end of each test run. The last set, using a 300 ppmv ozone
concentration and
2 ml/min hydroperoxide, gave the lowest baseline response of the four
treatments. The
introduction of hydroperoxide with ozone as a bubble coating appeared superior
in treatment
than a batch mixing with an added slug of equivalent volume.
A final additional test set was performed by increasing the oxidant
concentrations to 300
ppmv ozone with 10 ml 10% hydroperoxide and 3000 ppmv with 30 ml 10%
hydroperoxide as a
bubble coating. The results of the test are presented in Table 4. After
oxidation, the nutribubble
introduction was started and continued until remaining concentrations drop
below 10 g/kg.

19


CA 02441259 2003-09-15
WO 02/094723 PCT/US02/15939
Table 4. Removal of PCBs and PAHs from contaminated sediment by ozone plus
hydroperoxide, introduced as bubble coating, 30-minute bench-scale test.
Initial Concentration Ozone + Hydroperoxide
(pg/kg) 300 ppmv+ 3000 ppmv+
Compound 10 ml 10% 30 ml 10% % Removal
Arochlor 1260 23,300 3,900 5,000 79
Naphthalene 21,000 750 650 97
2-Methylnaphthalene 13,000 710 BRL 99
Acenaphthylene 15,000 BRL BRL 99
Benzo(a)anthracene 18,000 5,800 2,400 86
Benzo(b)fluoranthene 17,000 5,800 3,100 82
Benzo(k)fluoranthene 17,000 5,400 2,700 84
Dibenzo(a,h)anthracene 17,000 4,900 2,300 86
Indo(1,2,3-c,d)pyrene 18,000 5,100 2,300 87
Phenanthracene 17,000 4,200 2,000 87
Pyrene 40,000 13,000 5,500 86
Field Operations and Implementation
The process of administration of the liquid and gas would be in-situ, with use
of laminar
diffusers (e.g., Spargepoints ). Figure 1 presents a schematic diagram of the
K-V Associates
Criegee oxidizer with simultaneous liquid and gas supply. The individual
diffusers (e.g.,
Spargepoints ) are drilled into the contaminated aquifer region to be treated.
The timer-
controller delivers liquid and gas simultaneously. The number of diffusers
(e.g., Spargepoints )
depend upon the volume to be treated. The microbubble operating system is used
to field treat
about 1 cubic meter of saturated soil contained in a plastic trash bin runs on
house current (120
volts AC, 15 amp).
The reactivity of ozone with benzene, phenanthrene, naphthalene, pyrene, and
chrysene ill
well-documented in the scientific literature. Old diesel fuel or coal tar
residues often contain
these compounds. Not uncommonly, PCBs are encountered with these organics,
presenting a
difficult mix to remediate. The bench test of the coated microbubbles resulted
in a removal
varying from 79% to 99% for the mixture of PAHs and PCBs, with initial oxidant
treatment. For
the arochlor example (See, Table 5), this corresponds to remediation from
about 23,300 gg/kg
initial concentration to about 3,900 g/kg upon initial oxidant treatment.
Switching to
nutribubble injection can be successful in bringing the total removal rate to
less than 10 gg/kg of
treated soil. Representative results are delineated in Table 4. The
designation "below reportable


CA 02441259 2011-09-16
60412-3206

levels" (BRL) signifies that concentrations were below those detectable
according to the
analytical techniques and instrumentation used.

Table 5. Removal of HVOCs (PCE and TCE), PCBs (Arochlor 1016), and PAHs
(Nitrobenzene, Phenanthrene, Anthacene, and Pyrene) in Contaminated
Soil During Pilot Test with Hydroperoxide-Thickened Microbubbles
(Concentrations in ppb- g/kg (Soil) or p.g/L (Water)

Pilot Test
Test I Test 2 Test 3
Air-Sparge Only Air/Ozone Air/Ozone/Hydroperoxide
(500 ppmv) .7 cfm (500 ppmv)/12% solution
.7 cfm/6 ce/min
Run
Minutes 0 120 0 120 0 60 240
TCE 1900 150 1 ,,200 60 8100 210 BRL
GW 79 BRL 50 BRL 870 -- BRL
Soil
PCE 1,400 110 510 34 4,000 86 12
GW 64 BRL 56 50 480 -- BRL
Soil

Nitrobenzene -- -- -- -- 6,000 4,300 2,100
(Soil)

Phenanthrene -- -- -- -- 8,800 7,500 7,100
(Soil)

Anthracene -- -- -- -- 11,000 9,000 8,400
(Soil)

Pyrene -- -- -- -- 10,000 10,000 9,000
(Soil)
Arochlor 1016
(PCB) -- -- -- -- .2,900 1,400 1,1.00
(Soil)

A number of embodiments of the invention have been described. Nevertheless, it
will be
understood that various modifications are possible. Accordingly, whilst the
subject matter for
patent protection is defined by the appended claims, the claims are not to be
limited by preferred
or exemplified embodiments.

21

Representative Drawing
A single figure which represents the drawing illustrating the invention.
Administrative Status

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Administrative Status

Title Date
Forecasted Issue Date 2012-10-09
(86) PCT Filing Date 2002-05-16
(87) PCT Publication Date 2002-11-28
(85) National Entry 2003-09-15
Examination Requested 2007-05-16
(45) Issued 2012-10-09
Deemed Expired 2018-05-16

Abandonment History

Abandonment Date Reason Reinstatement Date
2008-05-16 FAILURE TO PAY APPLICATION MAINTENANCE FEE 2008-06-18

Payment History

Fee Type Anniversary Year Due Date Amount Paid Paid Date
Application Fee $300.00 2003-09-15
Maintenance Fee - Application - New Act 2 2004-05-17 $100.00 2004-05-03
Maintenance Fee - Application - New Act 3 2005-05-16 $100.00 2005-05-04
Maintenance Fee - Application - New Act 4 2006-05-16 $100.00 2006-05-03
Maintenance Fee - Application - New Act 5 2007-05-16 $200.00 2007-05-15
Request for Examination $800.00 2007-05-16
Reinstatement: Failure to Pay Application Maintenance Fees $200.00 2008-06-18
Maintenance Fee - Application - New Act 6 2008-05-16 $200.00 2008-06-18
Maintenance Fee - Application - New Act 7 2009-05-19 $200.00 2009-05-01
Maintenance Fee - Application - New Act 8 2010-05-17 $200.00 2010-05-04
Maintenance Fee - Application - New Act 9 2011-05-16 $200.00 2011-05-03
Maintenance Fee - Application - New Act 10 2012-05-16 $250.00 2012-05-01
Final Fee $300.00 2012-07-27
Maintenance Fee - Patent - New Act 11 2013-05-16 $250.00 2013-04-30
Maintenance Fee - Patent - New Act 12 2014-05-16 $250.00 2014-05-12
Maintenance Fee - Patent - New Act 13 2015-05-19 $250.00 2015-05-19
Maintenance Fee - Patent - New Act 14 2016-05-16 $250.00 2016-05-16
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
KERFOOT, WILLIAM
Past Owners on Record
None
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Abstract 2003-09-15 1 38
Claims 2003-09-15 7 244
Drawings 2003-09-15 6 105
Description 2003-09-15 21 1,105
Representative Drawing 2003-09-15 1 11
Cover Page 2003-11-21 1 34
Claims 2011-04-05 8 249
Drawings 2011-04-05 6 125
Description 2011-04-05 23 1,152
Drawings 2010-04-14 6 109
Claims 2010-04-14 6 241
Description 2010-04-14 22 1,148
Drawings 2010-08-05 6 124
Description 2010-08-05 23 1,155
Claims 2011-09-16 8 251
Description 2011-09-16 23 1,150
Representative Drawing 2012-09-24 1 11
Cover Page 2012-09-24 1 34
PCT 2003-09-15 2 77
Assignment 2003-09-15 2 80
PCT 2003-09-15 3 175
Correspondence 2003-12-03 2 101
Prosecution-Amendment 2011-08-26 2 51
Prosecution-Amendment 2007-05-16 1 43
Prosecution-Amendment 2007-05-16 1 35
Fees 2007-05-15 1 35
Prosecution-Amendment 2009-10-14 7 333
Prosecution-Amendment 2010-04-14 21 951
Prosecution-Amendment 2010-08-05 8 277
Prosecution-Amendment 2010-10-05 3 135
Prosecution-Amendment 2011-09-16 5 161
Prosecution-Amendment 2011-04-05 23 925
Correspondence 2012-07-27 2 62