Source: http://www.google.com/patents/US7666313?dq=5359317
Timestamp: 2015-02-27 00:54:00
Document Index: 151778396

Matched Legal Cases: ['Application No. 2', 'Application No. 2', 'Application No. 01305133', 'Application No. 01305133', 'Application No. 01305133', 'Application No. 01305133', 'Application No. 01305133', 'Application No. 01305133', 'Application No. 01305133']

Patent US7666313 - Treating a site containing contaminants by sparging the site with an air ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsA method of treating a site containing contaminants and apparatus are described The method and apparatus sparges the site with an air/ozone gas stream delivered with a hydroperoxide, which is a substantial byproduct of a reaction of a contaminant present in the aquifer or soil formation with the ozo...http://www.google.com/patents/US7666313?utm_source=gb-gplus-sharePatent US7666313 - Treating a site containing contaminants by sparging the site with an air/ozone gas stream delivered with a hydroperoxide, which is a substantial by-product of a reaction of a contaminant present in the aquifer or soil formation with the ozoneAdvanced Patent SearchPublication numberUS7666313 B2Publication typeGrantApplication numberUS 11/409,892Publication dateFeb 23, 2010Filing dateApr 24, 2006Priority dateJul 6, 2000Fee statusPaidAlso published asCA2351257A1, CA2351257C, DE60139587D1, EP1174197A2, EP1174197A3, EP1174197B1, US6582611, US7033492, US20040045911, US20060186060Publication number11409892, 409892, US 7666313 B2, US 7666313B2, US-B2-7666313, US7666313 B2, US7666313B2InventorsWilliam B. KerfootOriginal AssigneeThinkvillage-Kerfoot, LlcExport CitationBiBTeX, EndNote, RefManPatent Citations (101), Non-Patent Citations (125), Referenced by (3), Classifications (22), Legal Events (4) External Links: USPTO, USPTO Assignment, EspacenetTreating a site containing contaminants by sparging the site with an air/ozone gas stream delivered with a hydroperoxide, which is a substantial by-product of a reaction of a contaminant present in the aquifer or soil formation with the ozone
US 7666313 B2Abstract
A method of treating a site containing contaminants and apparatus are described The method and apparatus sparges the site with an air/ozone gas stream delivered with a hydroperoxide, which is a substantial byproduct of a reaction of a contaminant present in the aquifer or soil formation with the ozone.
1. A method of treating a site comprises:
identifying a contaminant within the site to be removed,
determining an intermediary hydroperoxide that results from a reaction between the contaminant and ozone,
sparging the site with a gas stream comprising air and ozone, and
introducing the intermediary hydroperoxide from an externally-supplied source to the site.
2. The method of claim 1 wherein the gas stream comprising air and ozone is delivered through a microporous diffuser that delivers the gas comprising air and ozone in microbubbles.
3. The method of claim 1 wherein the hydroperoxide is selected from the group consisting of formic peracid, hydroxymethyl hydroperoxide, 1-hydroxylethyl hydroperoxide, and chloroformic peracid or their derivatives.
4. The method of claim 1 wherein the hydroperoxide is selected based on the type of contaminant present in the site.
5. The method of claim 1 wherein the hydroperoxide is delivered through a microporous diffuser.
6. The method of claim 5 wherein the microporous diffuser includes promoters or nutrients such as catalyst agents including iron containing compounds such as iron silicates or palladium containing compounds such as palladized carbon and platinum.
7. The method of claim 6 wherein the microporous diffuser has a pore size in the range of about 1 to 200 microns.
8. The method of claim 1 wherein sparging comprises:
introducing the gas stream comprising air and ozone into a microporous diffuser.
9. The method of claim 8 wherein the sparging comprises:introducing hydroperoxide as a liquid into the microporous diffuser.
10. The method of claim 9 wherein the microporous diffuser has a pore size in a range of about 1 to 200 microns.
11. The method of claim 1 wherein the hydroperoxides are byproducts of a reaction involving a volatile organic compound with ozone.
12. The method of claim 1 wherein the sparging comprises:
introducing hydroperoxide as a liquid into a microporous diffuser.
13. A method of treating a site comprises:
selecting the intermediary hydroperoxide from an externally-supplied source, and
sparging the site with microbubbles of air/ozone gas, the microbubbles having a coating of the selected intermediary hydroperoxide by:
injecting through at least one diffuser a first fluid of the selected intermediary hydroperoxide as the coating over the microbubbles of ozone and air.
14. The method of claim 13 wherein the air/ozone gas stream is delivered through a microporous diffuser that delivers the air/ozone gas in microbubbles.
15. The method of claim 13 wherein the hydroperoxide is selected from the group consisting of formic peracid, hydroxymethyl hydroperoxide, 1-hydroxylethyl hydroperoxide, and chloroformic peracid or their derivatives.
16. The method of claim 13 wherein the hydroperoxide is delivered as a surface layer over the microbubbles including air/ozone gas stream.
17. The method of claim 13 wherein sparging the site, comprises:
injecting through the at least one microporous diffuser the first fluid of a hydroperoxide selected from the group consisting of formic peracid, hydroxymethyl hydroperoxide, 1-hydroxylethyl hydroperoxide, and chloroformic peracid or their derivatives as the coating over the microbubbles of ozone and air.
This application is a continuation of application Ser. No. 10/602,256, filed on Jun. 23, 2003, (now U.S. Pat. No. 7,033,492), which was a divisional application of application Ser. No. 09/610,830, filed on Jul. 6, 2000, (now U.S. Pat. No. 6,582,611).
This invention relates generally to groundwater and subsurface soil remediation.
There is a well recognized need for removal of subsurface contaminants that exist in aquifers and surrounding soils. Such contaminants can include various man-made volatile hydrocarbons including chlorinated hydrocarbons, e.g., volatile organic compounds such as chlorinated olefins including tetrachloroethylene, trichloroethylene, cis 1,2-dichloroethane and vinyl chloride. Other compounds include aromatic or polyaromatic ring compounds such as benzene, toluene, methylbenzene, xylenes, naphthalene, and propellents or explosives such as nitro anilines trinitrotoluene, and so forth. The groups of compounds are characterized by aromatic ring structures also include alkyl substituted aromatic hydrocarbons.
According to an aspect of the present invention, a method of treating a site includes sparging the site with an air/ozone gas stream delivered with a hydroperoxide, which is a substantial byproduct of a reaction of a contaminant present in the aquifer or soil formation with the ozone.
The air/ozone gas stream is delivered through a microporous diffuser that delivers the air/ozone gas in microbubbles. In some embodiments, the hydroperoxide is selected from the group consisting of formic peracid, hydroxymethyl hydroperoxide, 1-hydroxylethyl hydroperoxide, and chloroformic peracid or their derivatives. The hydroperoxide is selected based on the type of contaminant present in the site. The hydroperoxide is delivered as a surface layer over microfine bubbles including the air/ozone gas. Sparging introduces air including the oxidizing gas into the microporous diffuser. The microporous diffuser also introduces promoters or nutrients such as catalyst agents including iron containing compounds such as iron silicates or palladium containing compounds such as palladized carbon and platinum or platinum containing compounds.
According to an additional aspect of the invention, an apparatus for treating subsurface water includes a well having a casing with an inlet screen and outlet screen to promote recirculation of water into the casing and through surrounding ground area and at least one microporous diffuser disposed in the injection well that allows delivery of a pair of fluids with one of the fluids forming a coating over the other of the fluids. The apparatus also includes an ozone generator, an air compressor and compressor/pump control mechanism to deliver ozone (O3) from the ozone generator to the microporous diffuser, and a source of the liquid hydroperoxides selected from the group consisting of formic peracid, hydroxymethyl hydroperoxide, 1-hydroxylethyl hydroperoxide, and chloroformic peracid or their derivatives. The apparatus includes a pump to deliver the selected liquid hydroperoxide to the microporous diffuser.
The hydroperoxides promote decomposition of chlorinate olefins by forming a secondary liquid-phase reactive interface to the contaminants such as volatile chlorinate olefins and volatile hydrocarbons including chlorinated hydrocarbons, chlorinated olefins such as tetrachloroethylene, trichloroethylene, cis 1,2-dichloroethane and vinyl chloride and other compounds e.g., aromatic ring compounds, propellants, explosives, and so forth that are found as contaminants compounds as the contaminants enter the gaseous phase within the bubbles.
Promoters or nutrients are introduced with the hydroperoxides. The hydroperoxides are produced by reactions that decompose the contaminants. In the presence of the hydroperoxides, the promoters or nutrients can combine with the hydroperoxides and promote and accelerate the decomposition reactions. Further, when treating contaminants that have large number of double bonded carbon atoms or which are present in super-saturated conditions the addition of the hydroperoxides promotes rapid and efficient Crieqee reactions of the contaminants.
FIGS. 1A-1B are cross-sectional views showing soil formations and underlying aquifers with two embodiments of sparging apparatus.
FIGS. 2A-3A and 2B-3B are respectively longitudinal cross-sectional and plan cross-sectional views of a microporous diffuser useful in the arrangement of FIG. 1.
FIG. 4 is a flow chart of a process flow using the system of FIG. 1A or FIG. 1B.
Referring to FIG. 1A, an arrangement of a treatment system 10 to treat contaminants in a subsurface aquifer 12 includes an sparging apparatus 14 that is disposed through a soil formation 16. In this arrangement, the sparging apparatus is disposed through a vadose zone 16 a and the underlying aquifer 12. The sparging apparatus 14 includes a casing 18 that is positioned through a bore hole 19 disposed through the soil formation 16. The casing 18 has an inlet screen 18 a disposed on an upper portion thereof and an outlet screen 18 b disposed on a bottom portion thereof. Disposed through the casing 18 is a microporous diffuser 50 (FIG. 2A, 2B) or 70 (FIG. 3A, 3B), as will be described below. Also disposed in the casing is a packer 17 that isolates the upper screen 18 a from the lower screen 18 b and appropriate piping to connect sources of decontamination agents to the microporous diffuser 50, 70. When fluid is injected through the microporous diffuser 50, 70 the packer 17 and screens 18 a, 18 b enable a re-circulation water pattern 13 to evolved about the sparging apparatus 14.
The arrangement 10 also includes a treatment control system 30 including an air compressor 32, e.g., pump that feeds a mixture of air/ozone into the microporous diffusers 50, 70. The air compressor 32 delivers air mixed with ozone (O3) that is produced from an ozone generator 36 into the microporous diffusers. The mixture of air/ozone affects substantial removal of contaminants such as various man-made volatile hydrocarbons including chlorinated hydrocarbons, chlorinated olefins such as tetrachloroethylene, trichloroethylene, cis 1,2-dichloroethane and vinyl chloride and other compounds e.g., aromatic ring compounds, propellants, explosives, and so forth that are found as contaminants.
The treatment system 10 also includes a delivery mechanism e.g., a second pump 38 or other feed arrangement that supplies a liquid decontamination agent such as hydrogen peroxide or other hydroperoxides into the microporous diffuser 50, 70. The hydrogen peroxide or other hydroperoxides are provided via a source 40. Also supplied to the microporous diffusers are promoters or nutrients, as well as catalyst agents 42 including iron containing compounds such as iron silicates, ferrous iron, acetic acid, or palladium containing compounds such as palladized carbon or other transition metals in acid solution. In addition, other materials such as platinum may alternatively be used. The promoters or nutrients are introduced with the hydroperoxides. The hydroperoxides are produced by reactions that decompose the contaminants. In the presence of the hydroperoxides, the promoters or nutrients can combine with the hydroperoxides and promote and accelerate the decomposition reactions.
Referring to FIG. 1B an alternate embodiment of a treatment system 10′ is shown. The treatment system 10′ treats contaminants in a subsurface aquifer 12′ includes an sparging apparatus 14′ that is disposed through a soil formation 16′. In this arrangement, the sparging apparatus is disposed through a vadose zone 16 a′ and the underlying aquifer 12′. The sparging apparatus 14 includes a microporous diffuser 50 (FIG. 2A, 2B) or 70 (FIG. 3A, 3B), as will be described below. The microporous diffuser is positioned through a bore hole 19 disposed through the soil formation 16 or alternatively can be of the type that is injected into the soil formation. The microporous diffuser is coupled to appropriate piping to connect sources of decontamination agents to the microporous diffuser 50, 70. When fluid is injected through the microporous diffuser 50, 70, the microporous diffusers enables a water pattern 13′ to evolved about diffuser. Light bubbles tend to travel upwards whereas heavier bubbles tend to travel downwards.
The arrangement 10′ also includes a treatment control system 30′ generally similar to system 30′ (FIG. 1A) including an air compressor 32′ that feeds a mixture of air/ozone into the microporous diffusers 50, 70. The air compressor 32′ delivers air mixed with ozone (O3) that is produced from an ozone generator 36 into the microporous diffusers. The treatment system 10′ also includes a second pump 38′ that supplies a liquid decontamination agent such as hydrogen peroxide or other hydroperoxides into the microporous diffuser 50, 70. The hydrogen peroxide or other hydroperoxides are provided via a source 40′. Also supplied to the microporous diffusers are promoters or nutrients, as well as catalyst agents 42′ as also mentioned above.
The treatment system 10 or system 10′ makes use of a gas-gas reaction of contaminant vapors with ozone, as will be described below, supplemented by a liquid phase reaction provided by a flow of hydrogen peroxide and preferable other hydroperoxides, described below. The ozone is trapped inside of micro bubbles produced from the air/ozone escaping the microporous diffusers 50, 70 and being trapped in water from the aquifer. On the other hand, hydrogen peroxide or other hydroperoxides provide a thin film coating over the outer surfaces of the bubbles.
The hydroperoxides promote decomposition of chlorinate olefins by forming a secondary liquid-phase reactive interface to the contaminants such as volatile chlorinate olefins and volatile hydrocarbons including chlorinated hydrocarbons, chlorinated olefins such as tetrachloroethylene, trichloroethylene, cis 1,2-dichloroethane and vinyl chloride and other compounds e.g., aromatic ring compounds, propellants, explosives, and so forth that are found as contaminants compounds as the contaminants enter the gaseous phase within the bubbles. Suitable hydroperoxides can be as these listed in Table 1.
Allen's Reagent
Rate Reaction
HCOOOH
Formic Peracid
HOCH2OOH
Hydroxymethyl Hydroperoxide
3.4 � 10−3 CH3CH(OH)OOH
1-Hydroxylethyl Hydroperoxide
5 � 10−2 (CH3)2C(OH)OOH
Chloroformic Peracid
~2 � 10−5 These hydroperoxides or derivatives thereof react at different rates with the olefins, as shown for the Allen's Reaction Rate Constants in Table 1. The presence of the hydroperoxides as a coating over the gas bubbles contact contaminants such as compounds containing aromatic rings to break the rings into fragments that partition from liquid to gas phase bringing them more rapidly into contact with the gaseous ozone within the microfine bubbles. The presence of iron of a transition metal e.g., nickel or tin, or platinum or palladium solution can assist the reaction by becoming electron donors or act as catalyst agents.
In general, the hydroperoxides are intermediary compounds that are produced from a reaction of ozone with particular olefins. Thus, for other olefins the appropriate hydroperoxide would be the intermediary hydroperoxide that results from the reaction of the olefin with ozone.
While ozone in high concentration is recognized as an agent for rapid decomposition of semi-volatile or poorly volatile polyaromatic ring compounds in soil, the combination of a slowly reacting hydroperoxides and ozone provides improved efficiency of delivery and reaction. This results since the gaseous partitioning pulls compounds through the hydroperoxide interface reducing extraneous secondary reactions that occur with soil components as observed when hydrogen peroxide is injected as a solution into fractured soil formations, as in so called Fenton's agent reactions.
As mentioned above, these hydroperoxides formic peracid, hydrogen peroxide, hydroxymethyl hydroperoxide, 1-hydroxymethyl hydroperoxide, and chloroformic peracid, are intermediary products in reactions involving chlorinated olefins and ozone. As by-products of reactions of the chlorinated olefins with ozone the presence of the hydroperoxides as a coating on the bubbles serves to mitigate other competing reactions that can occur when the chlorinated olefins double bonded carbon atoms are attacked by the ozone as the chlorinated olefins enter the bubbles.
The coating on the bubbles provided by the microporous diffusers 50, 70 can be consider to be a gas-liquid-emulsion since the micro bubbles are dispersed gases with film coatings. Rather than a foam, the material co-exists in liquid water and does not necessarily rise to the top surface. Moreover, the hydroperoxide coating is not technically in solution with the gas. A solution would have the ozone gas and hydroperoxide liquid dispersed homogeneously without chemical change. In this arrangement, the coating on the bubbles exist separate from the gas inside the bubbles.
Referring now to FIGS. 2A-2B, a first embodiment of a microporous diffuser 50 is shown. The microporous diffuser 50 includes a first cylindrical member 56 comprised of a hydrophobic material that provides an outer cylindrical shell for the microporous diffuser 50. The cylindrical member 56 has a sidewall 56 a that is comprised of a large plurality of micropores. A second cylindrical member 60 is coaxially disposed within the first cylindrical member 56. The second cylindrical member 60 is comprised of a hydrophobic material e.g., high density polyethylene or polyvinyl chloride etc. and has a sidewall 60 a that is comprised of a large plurality of micropores. Also disposed within the confines of the first microcylinder 60 are a plurality of cylindrical members 58, here that have sidewalls 58 a having a large plurality of micropores and also comprised of a hydrophobic material.
A proximate end of cylindrical member 60 is coupled to a first inlet port provided from a first inlet cap 52 and proximate ends of the plurality of cylindrical members 58 are coupled to second inlet ports generally denoted as 52 b. At the opposite end of the microporous diffuser 50 is an end cap 54 that covers distal ends of cylindrical members 56 and 58. Here distal ends of the plurality of cylindrical members are sealed by separate caps 59 but could be terminated by a common end cap as the end cap 54. The end cap 54, in conjunction with cap 52, seals ends of the microporous diffuser 50.
The cylindrical members 56, 58 and 60 are cylindrical in shape and have a plurality of microporous openings constructed through sidewalls 56 a, 58 a and 60 a, respectively thereof, having pore sizes matched to a porosity characteristic of the surrounding formation to produce a pore size effective for inducing gas-gas reactions in bubbles that emanate from the microporous diffusers into the surrounding soil formations and/or aquifer. The sidewalls can have pore diameters in a range of 1-200 microns, preferably 1 to 50 microns or more preferably 5 to 20 microns.
The combination of the inlet cap and the end cap seals the microporous diffuser 50 permitting liquid and gas to escape by the porous construction of sidewalls of the microporous diffusers. The microporous diffuser can be filled with a microporous material such as microbeads having mesh sizes from 20 to 200 mesh, or sand pack, or porous hydrophilic plastic to allow introducing a liquid into the porous spaces. In this arrangement, the liquid is one of the aforementioned hydroperoxides formic peracid, hydrogen peroxide, hydroxymethyl hydroperoxide, 1-hydroxymethyl hydroperoxide, and chloroformic peracid or derivatives, and so forth.
Referring now to FIGS. 3A and 3B, an alternative embodiment 70 of the microporous diffuser is shown. The microporous diffuser 70 includes an outer cylindrical member 76 having a sidewall 76 a within which is disposed an inner cylindrical member 78 having a sidewall 78 a. The inner cylindrical member 78 is spaced from the sidewall of the outer cylindrical member by a space 77. The space 77 between the inner and outer cylindrical members 76, 78 is filled with a packing material comprised of glass beads or silica particles (silicon dioxide) or porous plastic which is, in general, hydrophilic in nature. The space is coupled to an input port 72 that receives a liquid and catalyst and/or promoters or nutrients from pump 39 (FIG. 2). The microporous diffuser has the inner cylindrical member 78 disposed coaxial or concentric to cylindrical member 78.
Sidewalls of each of the cylindrical members can have a pore diameter in the range of 1 to 200 microns. Depending on soil conditions various ranges can be used exemplary ranges are 50 to 200 microns for very coarse gravel-like soils, 1 to 50 microns for sandy-type soils or 1-5 to 20 microns for more silty type soils. A proximate end of the cylindrical member is coupled to an inlet port 72 a that is fed an air-ozone mixture from pump 36. The microporous diffuser also includes an end cap 74 which secures distal ends of a cylinder 76, 78. The combination of the inlet cap 72 and end cap 78 seals the microporous diffuser permitting liquid and gas to escape by the porous combination of construction of the sidewalls of the microporous diffusers. Also in this arrangement, the liquid is one of the aforementioned hydroperoxides, e.g., formic peracid, hydrogen peroxide, hydroxymethyl hydroperoxide, 1-hydroxymethyl hydroperoxide, and chloroformic peracid, etc.
Thus, when using the microporous diffusers 50 or 70 in the arrangement of FIG. 1, an air-ozone mixture is injected through port 52 a, 72 a (microporous diffusers 50, 70, respectively) and produces bubbles of the diameters according to the pore size of the sidewalls of the cylinder. Liquid hydroperoxides e.g., formic peracid, hydrogen peroxide, hydroxymethyl hydroperoxide, 1-hydroxymethyl hydroperoxide, and chloroformic peracid etc., as set forth in Table 1 is introduced into the microporous diffusers 50 and 70 via inlet ports 52 b and microporous diffuser 50 or inlet port 72 b and microporous diffuser 70. The presence of liquid in the microporous diffusers will coat microbubbles that emerge from the central portions of the microporous diffusers providing the liquid-gas emulsion referred to above. This liquid-gas emulsion exits the microporous diffusers 50, 70 and travels through the surrounding soil formation and aquifer.
The Criegee reaction of ozone in a water gas mixture is promoted by the microbubble emulsion. The hydroperoxide compounds and ozone produce reactions during the process of water to gas partitioning with volatile organic compounds or absorbed liquid/water to gas partitioning with semi-volatile organic compounds. The breakdown of chlorinated or halogenated solvents in an aqueous solution by Criege decomposition involving ozone yields various hydroperoxide products such as those set forth in Table 1. To promote higher concentration of volatile organic and semi-volatile organic destruction, the organic hydroperoxides are injected with the laminated microporous diffusers 50, 70 as a coating for the microporous emulsions. The injection which occurs under pressure produces an aerosol in the system 10 where water is reduced to particles of micron size. Therefore to practice the methods described below, any system that can produce an aerosol of the hydroperoxide coated bubbles may be used.
The peroxide acid solution becomes a coating of a microsize bubble occupying a fifth or less of the volume of the gas injected. It is believed that at this point, the coating is not in solution with the water or ozone. As used a solution can be considered as a gas, liquid or solid dispersed homogeneously in a gas, liquid or solid without chemical change. Rather, the hydroperoxide/water/ozone is a gas-liquid emulsion as referred to above. Attaching to the surface of a semi-volatile compound such as an olefin e.g., nitroaniline or nitrotoluene or polyaromatic ring compounds the coating reacts with the aromatic rings of such compounds to break the rings into fragments that partition from a liquid to gas phase bringing them even more rapidly into contact with the gaseous ozone content.
Referring to FIG. 4, a process 100 using the arrangement 10 of FIG. 1 for treating groundwater and surface waters includes characterizing 102 a site. Characterizing the site includes determining the porosity characteristics of surrounding soil formations, depth to aquifers, thickness of aquifers, the hydraulic conductivity of the aquifer, and the nature and extent of contaminants, e.g., types and concentrations in aqueous solution and in the soils. After the site has been characterized, equipment of the arrangement shown in FIG. 1 or an equivalent arrangement are established 104 on the site. The equipment established 104 can be comprised of a large plurality of apparatuses of the type shown in FIG. 1 disposed in a corresponding plurality of wells provided on the site in accordance with the volume of subsurface soils and water that the apparatus can treat. Many different configurations of the equipment can be used such as placing multiple microporous diffusers 50, 70 into a single well or using one or more of the microporous diffusers in combination with microporous well screens and packers to produce a bubble chamber and so forth. Typically, an apparatus having single laminar point and double well screens can cover a radii of 30 ft. and 60 ft., respectively for 15-20 ft. thick aquifers.
Once the equipment has been established on a site, the process 100 initiates 106 a flow of air and ozone (O3) through the microporous diffusers 50, 70. In response, the process 100 produces microbubbles of appropriate size determine in accordance with the porosity characteristics of the microporous diffusers that attempt to match that of the surrounding soil formation. As described above, generally this porosity characteristic is in a range of 5 to 200 microns. Other ranges may be used however. The flow of air and ozone continues through the microporous diffusers 50, 70 and produces a dispersed pattern of microfine bubbles through the treatment area. During the process 100, the wells are monitored 108 to determine when a microfine bubble pattern of appropriate dispersion through the treatment zone has been established. Bubble dispersion can be determined by dissolved oxygen distribution, oxidative reduction potential measurements, or by direct measurement of micro-bubbles (bubble counters). Once this pattern has been established the process initiates 110 a flow of a suitable hydroperoxide(s) selected in accordance with the contaminant(s) being treated. The hydroperoxides are in the form of liquid that is provided in the outer portions of the microporous diffusers 50, 70. Initiation 110 of the flow of hydroperoxides allows the hydroperoxides to coat the microbubbles as they emerge from the center of the microporous diffusers 50, 70 producing the abovementioned hydroperoxide bubble emulsion. The process periodically samples 112 groundwater to determine the cleanup status of the site. Once contaminants in the groundwater have reached a certain level, the process 100 can be terminated. Alternatively, the process can be used as a fence to continually and indefinitely pump air-ozone and a suitable hydroperoxide into a portion of a contaminated site to contain a migrating plume of contaminants from reaching a critical area such as residential wells, aquifers and so forth.
Typical conditions for the air/ozone flow are as follows:
recircu-
gm/day
144-430 5-50
1-8 pallettized
The percent concentration of hydroperoxide in water is typically in a range of (2-20) percent although other concentrations can be used. The flow is adjusted to the total mass of the contaminants in the soil and water. If high concentrations (greater than 50,000 parts per billion in water or 500 mg/kg in soil) of the contaminants are present sufficient hydroperoxides should be added in insure efficient decomposition by the Criegee reaction mechanism. Preferably this would occur in the presence of an accelerant (e.g., transition metals iron, nickel or zinc, and/or catalysts palladium or platinum).
Further, when treating contaminants that have large number of double bonded carbon atoms or which are present in super-saturated concentrations e.g., (greater than 200,000 parts per billion in water or 5000 mg/kg in soil) the addition of the hydroperoxides is highly desirable to promote rapid and efficient Criegee reactions on the site. This is because, the mole volume or ratio of moles of the contaminant to moles of ozone becomes high in the presence large number of double bonded carbon atoms or high concentrations, while the concentration of the ozone is limited to that which can be suitable injected taking into consideration generation capacity, stress on the apparatus, site conditions and desire to maintain a Criegee mechanism.
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS1920719Jan 9, 1932Aug 1, 1933Stich EugenAerating deviceUS2517525Oct 13, 1947Aug 1, 1950Sun Oil CoCatalytic reaction apparatusUS2845185Oct 5, 1954Jul 29, 1958Winderweedle Jr Howell WShoe hangerUS2946446Sep 17, 1958Jul 26, 1960Permanent Filter CorpFiltration unitsUS3027009Jan 28, 1959Mar 27, 1962Permanent Filter CorpFiltration equipmentUS3206178Nov 16, 1960Sep 14, 1965Fmc CorpDiffuser tubeUS3219520Oct 21, 1960Nov 23, 1965Hawley Products CoPaper making apparatus and aerating device with electrical cleaning meansUS3276994Mar 9, 1966Oct 4, 1966Charles W AndrewsSewage treatmentUS3441216Nov 16, 1964Apr 29, 1969Raymond J GoodAir diffuser unit for aerating sewageUS3570218Dec 11, 1968Mar 16, 1971Universal Oil Prod CoElectrode configuration in an electrical precipitatorUS3669276Nov 6, 1970Jun 13, 1972Wilwood IncShoe display bag and systemUS3708206Jul 20, 1970Jan 2, 1973Union Carbide CorpProcess for leaching base elements, such as uranium ore, in situUS3814394Nov 17, 1971Jun 4, 1974M MurrayApparatus for encapsulating hot gases from high stacksUS3823776Apr 26, 1973Jul 16, 1974Mobil Oil CorpOil recovery method by oxidation and forming surfactants in situUS3997447Jun 7, 1974Dec 14, 1976Composite Sciences, Inc.Fluid processing apparatusUS4007118Oct 16, 1975Feb 8, 1977Cubic CorporationOzone oxidation of waste waterUS4021347Jan 9, 1976May 3, 1977Teller Ray ESewage treatment systemUS4048072Oct 23, 1975Sep 13, 1977Schramm, Inc.Air diffusersUS4049552Nov 17, 1975Sep 20, 1977Oregon Patent Development CompanyOzone generating systemUS4064163Dec 30, 1976Dec 20, 1977Amchem Products, Inc.Process for the manufacture of aliphatic phosphonic acidsUS4118447Jun 20, 1977Oct 3, 1978Xodar CorporationAerator containing a ballast chargeUS4178239Nov 13, 1974Dec 11, 1979Union Carbide CorporationBiological intermediate sewage treatment with ozone pretreatmentUS4203837Dec 16, 1977May 20, 1980Hoge John HProcess for removal of discrete particulates and solutes from liquids by foam flotationUS4268283Dec 31, 1979May 19, 1981W-K-M Wellhead Systems, Inc.Fluid control means for geothermal wellsUS4298467Jun 5, 1980Nov 3, 1981Panlmatic CompanyWater treatment systemUS4310057May 30, 1980Jan 12, 1982Brame Durward BApparatus for extracting subterranean gas samplesUS4351810Jul 9, 1981Sep 28, 1982The United States Of America As Represented By The Secretary Of CommerceScavenging by free radical intermediate to form adduct followed byhydrolysisUS4360234Sep 20, 1976Nov 23, 1982Kennecott Copper CorporationIn-situ method and apparatus for sparging gas bubblesUS4614596Jan 10, 1985Sep 30, 1986Wyness David KRoatation, varying velocitiesUS4622139Mar 20, 1985Nov 11, 1986Brown Charles JAerator deviceUS4639314Jan 18, 1985Jan 27, 1987Tyer Robert RFine bubble diffuser and diffuser system having filtered blow-down tubeUS4684479Aug 14, 1985Aug 4, 1987Arrigo Joseph S DMicrobubbles by shaking glycerides and sterol esters in water or oil; echocardiogramsUS4695447Dec 17, 1985Sep 22, 1987Detox International CorporationDestruction of inorganic hazardous wastesUS4696739Aug 11, 1986Sep 29, 1987Aqua Strip CorporationWater purification apparatusUS4730672Mar 4, 1987Mar 15, 1988Midwest Water Resource, Inc.Method of removing and controlling volatile contaminants from the vadose layer of contaminated earthUS4804050Apr 30, 1987Feb 14, 1989K-V Associates, Inc.Method of underground fluid samplingUS4832122Aug 25, 1988May 23, 1989The United States Of America As Represented By The United States Department Of EnergyIn-situ remediation system and method for contaminated groundwaterUS4837153Aug 22, 1984Jun 6, 1989Laurenson Jr John GUsing lance with two separate fluid flow zonesUS4838434May 17, 1988Jun 13, 1989University Of UtahAir sparged hydrocyclone flotation apparatus and methods for separating particles from a particulate suspensionUS4844795May 13, 1988Jul 4, 1989Bassim HalwaniMethod and apparatus for decontaminating the aquifer of hydrocarbonsUS4883589May 17, 1988Nov 28, 1989New Jersey Institute Of TechnologySystem for removing contaminants from ground waterUS4941957Sep 30, 1988Jul 17, 1990Ultrox InternationalDecomposition of volatile ogranic halogenated compounds contained in gases and aqueous solutionsUS4943305May 26, 1989Jul 24, 1990Bruno BernhardtAerating apparatus for expelling volatile impurities from ground waterUS4960706Mar 27, 1989Oct 2, 1990Baxter International, Inc.Static oxygenator for suspension culture of animal cellsUS4966717Feb 10, 1989Oct 30, 1990Kern Donald WDisinfecting of swimming poolUS4971731Dec 1, 1989Nov 20, 1990Deister Concentrator Company, Inc.Method and apparatus for generating microbubbles in froth flotation mineral concentration systemsUS5078921Jul 12, 1990Jan 7, 1992The Deister Concentrator Company, Inc.Froth flotation apparatusUS5080805Oct 11, 1988Jan 14, 1992Helen HouserAerial oxidationUS5116163Jan 16, 1991May 26, 1992Ieg Industrie-Engineering GmbhArrangement for driving out volatile impurities from ground waterUS5120442May 16, 1991Jun 9, 1992Dr. Karl Thomae GmbhAerobic degradationof biodegradable contaminants using microorganisms and oxidation of nonbiodegradable contaminantsUS5122165Jun 11, 1991Jun 16, 1992International Environmental Systems, Inc.Removal of volatile compounds and surfactants from liquidUS5126111May 20, 1991Jun 30, 1992Nutech Energy Systems Inc.Fluid purificationUS5133906Oct 9, 1990Jul 28, 1992Tony LouisAeratorUS5160655Nov 15, 1991Nov 3, 1992Lever Brothers Company, Division Of Conopco, Inc.Laundry detergents, storage stabilityUS5167806May 29, 1991Dec 1, 1992International Environmental Systems, Inc.Gas dissolving and releasing liquid treatment systemUS5178491Jun 19, 1991Jan 12, 1993International Technology CorporationVapor-phase nutrient delivery system for in situ bioremediation of soilUS5178755Feb 20, 1992Jan 12, 1993Estr Inc.UV-enhanced ozone wastewater treatment systemUS5180503May 10, 1991Jan 19, 1993The Board Of Trustees Of The Leland Stanford Junior UniversityIn-situ vapor stripping for removing volatile organic compounds from groundwaterUS5205927Aug 1, 1990Apr 27, 1993Battelle Memorial InstituteApplying ozone treated with acid to decompose the organic contaminantsUS5215680Jul 10, 1990Jun 1, 1993Cavitation-Control Technology, Inc.Method for the production of medical-grade lipid-coated microbubbles, paramagnetic labeling of such microbubbles and therapeutic uses of microbubblesUS5221159Jun 7, 1991Jun 22, 1993Environmental Improvement Technologies, Inc.Subsurface contaminant remediation, biodegradation and extraction methods and apparatusesUS5227184May 29, 1992Jul 13, 1993American Water Purification, Inc.Method for sanitizing food productsUS5238437Feb 7, 1992Aug 24, 1993Mattel, Inc.Bubble dispensing dollUS5246309May 16, 1991Sep 21, 1993Hobby Michael MSystem and method for decontamination of contaminated groundUS5248395Dec 26, 1989Sep 28, 1993UopWater treatment to remove metals and organicsUS5254253Aug 21, 1992Oct 19, 1993Zenon Environmental Inc.Modular shipboard membrane bioreactor system for combined wastewater streamsUS5259962Aug 31, 1992Nov 9, 1993Later Roger CMethod and apparatus for decontamination of soils and other particulate materialsUS5269943Jul 13, 1992Dec 14, 1993Battelle Memorial InstituteMethod for treatment of soils contaminated with organic pollutantsUS5277518Nov 27, 1991Jan 11, 1994Environmental Improvement Technologies, Inc.Contaminant remediation, biodegradation and removel methods and apparatusUS5302286Mar 17, 1992Apr 12, 1994The Board Of Trustees Of The Leland Stanford Junior UniversityAdding nutrients to groundwater as it flows through wellUS5332333Jan 27, 1993Jul 26, 1994Bentley Harold WVacuum extraction method and apparatus for removing volatile contaminants from the vadose layer of contaminated earthUS5362400Jun 26, 1991Nov 8, 1994Paref AbProcess for the purification of waterUS5364537Jan 16, 1992Nov 15, 1994Otv (Omnium De Traitements Et De Valorisation)Process for the oxidation of organic micropollutants in water using the O3 /H2 O2 combinationUS5375539Sep 21, 1992Dec 27, 1994Rippberger; Mark L.Efficient removal of volatile compounds from soil or waterUS5389267Dec 18, 1992Feb 14, 1995The Board Of Trustees Of The Leland Stanford Junior UniversityIn-situ vapor stripping for removing volatile organic compounds from groundwaterUS5398757Feb 22, 1994Mar 21, 1995K N Energy, Inc.Mono-well for soil sparging and soil vapor extractionUS5402848Apr 7, 1994Apr 4, 1995Kelly; Leo G.Method and apparatus for conducting environmental proceduresUS5403476May 28, 1993Apr 4, 1995Ieg Industrie-Engineering GmbhArrangement for removing impurities from ground waterUS5406950Dec 23, 1993Apr 18, 1995Mallinckrodt Medical, Inc.Inhalable contrast agentUS5425598Aug 12, 1993Jun 20, 1995Pennington; Leslie H.System for sparging ground water contaminantsUS5427693Apr 19, 1993Jun 27, 1995O-Three LimitedModular ozone water treatment apparatus and associated methodUS5430228Feb 24, 1993Jul 4, 1995Hughes Aircraft CompanyOzone methods for the destruction of chemical weaponsUS5431286Jan 6, 1994Jul 11, 1995Inco LimitedRecirculating column flotation apparatusUS5451320Jul 10, 1990Sep 19, 1995International Environmental Systems, Inc., UsaBiological process for groundwater and wastewater treatmentUS5464309Oct 20, 1994Nov 7, 1995Xerox CorporationDual wall multi-extraction tube recovery wellUS5472294Jan 10, 1994Dec 5, 1995Environmental Improvement Technologies, Inc.PurificationUS5480549Jan 25, 1994Jan 2, 1996The United States Of America As Represented By The United States Department Of EnergyOf contaminated soil and groundwaterUS5520483Feb 10, 1994May 28, 1996Vigneri; Ronald J.Method and system for remediation of groundwater contaminationUS5525008Jan 11, 1995Jun 11, 1996Wilson; James T.Oxidation of impuritiesUS5545330Dec 1, 1994Aug 13, 1996Amerada Hess CorporationGravity oil/water separation, for skimming floating hydrocarbons off the top of water surface, air-floatation, gravity fitration, air stripping, absorption, and chlorinationUS5560737Aug 15, 1995Oct 1, 1996New Jersey Institute Of TechnologyPneumatic fracturing and multicomponent injection enhancement of in situ bioremediationUS5588490May 31, 1995Dec 31, 1996Geraghty & Miller, Inc.For removing volatile contaminants in a two-dimensional configurationUS5609798Jun 7, 1995Mar 11, 1997Msp CorporationHigh output PSL aerosol generatorUS5615974Feb 4, 1994Apr 1, 1997Terra Vac, Inc.Process for soil decontamination by oxidation and vacuum extractionUS5620593Jun 12, 1996Apr 15, 1997Stagner; Joseph C.Multi-stage in-well aeratorUS5622450Mar 24, 1995Apr 22, 1997Grant, Jr.; Richard P.Pressure extraction process for removing soil and groundwater contaminantsUS5624635Aug 9, 1995Apr 29, 1997Pryor; Alan E.Method and apparatus for ozone treatment of soilUS5663475Aug 26, 1994Sep 2, 1997The United States Of America As Represented By The Secretary Of The Air ForceReactor for oxidation of petrochemicals using ozone and hydrogen peroxideUS6352387 *Dec 2, 1999Mar 5, 2002Robert A. BriggsRecirculation-enhanced subsurface reagent delivery systemUS6582611 *Jul 6, 2000Jun 24, 2003William B. KerfootGroundwater and subsurface remediationUSRE34890Sep 23, 1993Apr 4, 1995Gore Enterprise Holdings, Inc.Waterproof shoe construction* Cited by examinerNon-Patent CitationsReference1"Advanced Oxidation Processes for Treating Groundwater Contaminated with TCE and PCE", Aieta et al., 1988, Pilot-Scale Evaluations., Journal of American Water Works Association, JAWWAS, vol. 80, No. 5, pp. 64-72.2"Alternate Technologies for Wastewater Treatment", J. Hauck et al., Pollution Engineering, May 1990, pp. 81-84.3"Analysis of Selected Enhancements for Soil Vapor Extraction", U.S. Environmental Protection Agency, Sep. 1997, pp. 1-5 to 7-39.4"Analysis of Selected Enhancements for Soil Vapor Extraction", U.S. Environmental Protection Agency, Sep. 1997, pp. 1-5 to 7-39. (Whole Document enclosed).5"Aquifer Remediation Wells", EPA, vol. 16, Sep. 1999, pp. 1-80.6"Biologically Resistant Contaminants, Primary Treatment with Ozone", D.F. Echegaray et al., Water Science and Technology, A Journal of the International Association on Water Quality, vol. 29, No. 8, 1994, pp. 257-261.7"Chemical Degradation of Aldicarb in Water Using Ozone", F.J. Beltran et al., Journal of Chemical Technology & Biotechnology, 1995, pp. 272-278.8"Clare Water Supply", EPA, http://www.epa.gov/region5/superfund/npl/michigan/MID980002273.htm, pp. 1-3.9"Cleaning up", Forbes, Jun. 1, 1987, pp. 52-53.10"Completed North American Innovative Remediation Technology Demonstration Projects", U.S. Environmental Protection Agency, Office of Solid Waste and Emergency Response, Aug. 12, 1996, pp. 1-35.11"Effect of Organic Substances on Mass Transfer in Bubble Aeration", M. Gurol et al., Journal WPCF, vol. 57, No. 3, pp. 235-240, published 1985.12"Environmental Management", DON Environmental Restoration Plan for Fiscal Years 1997-2001, Sep. 30, 1996, pp. 4-1 to 4-8.13"Factors Controlling the Removal of Organic Pollutants in an Ozone Reactor", M.D. Gurol, AWWA 1984 Annual Conference, Dallas, TX, Jun. 10-14, 1984, pp. 2-21.14"Field Applications of In Situ Remediation Technologies: Chemical Oxidation", U.S. Environmental Protection Agency, Sep. 1998, pp. 1-31.15"Ground Water Issue", H.H. Russell et al., U.S. Environmental Protection Agency, Jan. 1992, pp. 1-10.16"Ground Water, Surface Water, and Leachate", http://www.frtr.gov/matrix2/section-4/4-30.html, Jul. 22, 2003, pp. 1-4.17"How to Evaluate Alternative Cleanup Technologies for Underground Storage Tank Sites", U.S. Environmental Protection Agency, Oct. 1994.18"In Situ Air Sparging System", Tech Data Sheet, Naval Facilities Engineering Service Center, Mar. 1997, pp. 1-4.19"In Situ Chemical Oxidation for Remediation of Contaminated Soil and Ground Water", EPA, Sep. 2000, Issue No. 37, pp. 1-6.20"In Situ Chemical Treatment", Y. Yin, Ph.D., Technology Evaluation Report, GWRTAC, Jul. 1999, pp. 1-74.21"In Situ Ozonation to Remediate Recalcitrant Organic Contamination", J. Dablow et al., IT Corporation, pp. 1-2.22"In Situ Remediation with Chemical Oxidizers: Ozone, Peroxide and Permanganate", Environmental Bio-systems, Inc., pp. 1-5.23"In-situ Air Sparging Without Inorganic Nutrient Amendment: An Effective Bioremediation Strategy for Treating Petroleum-Contaminated Groundwater Systems", R. Schaffner, Jr., et al., http://www.bioremediationeroup.org/BioReferences/Tier1Papers/insitu.htm, Jul. 30, 2003, pp. 1-14.24"Kinetics of the Bentazone Herbicide Ozonation", Journal of Environmental Science and Health, vol. A31, No. 3, 1996, pp. 519-537.25"Modelling Industrial Wastewater Ozonation in Bubble Contactors", Ozone Science & Engineering, vol. 17, 1995, pp. 355-378.26"Modelling Industrial Wastewater Ozonation in Bubble Contactors", Ozone Science & Engineering, vol. 17, 1995, pp. 379-398.27"Newark Brownfield Site to Increase Student Housing", Environmental Alliance Monitor, http://www.envalliance.com/monitor&pubs/1998fall.htm, 1998, pp. 1-8.28"RCC RemedOzone Mobile Remediation System", RCC.29"Reaction of Ozone with Ethene and Its Methyl- and Chlorine-Substituted Derivatives in Aqueous Solution," P. Dowideit et al., Environmental Science & Technology, vol. 32, No. 8, pp. 1112-1999, (1998).30"Santa Barbara I Manufactured Gas Plant Site", California EPA, Jan. 2002, pp. 1-6.31"Single-phase Membrane Ozonation of Hazardous Organic Compounds in Aqueous Streams", P.V. Shanbhag et al., Journal of Hazardous Materials 41, 1995, pp. 95-104.32"Strategies to Protect Your Water Supply from MTBE", Komex Industries, http://www.komex.com/industries/remediation.stm, 2002, pp. 1-8.33"Technology Status Review In Situ Oxidation", Environmental Security Technology Certification Program, Nov. 1999, pp. 1-42.34"The Ultrox System: USEPA Ultrox International Ultraviolet Radiation/Oxidation Technology", Applications Analysis Report, EPA/540/A5-89/012, Sep. 1990.35"Toxins, toxins everywhere", K.K. Wiegner, Forbes, Jul. 22, 1991, pp. 298.36"Transfer Rate of Ozone across the Gas-Water Interface", S. Okouchi et al., The Chemical Society of Japan, No. 2, 1989, pp. 282-287.37"Treatment of VOC-Contaminated Groundwater by Hydrogen Peroxide and Ozone Oxidation", Bellamy, W.D., G.T. Hickman, P.A. Mueller, and N. Ziemba, Res. J. Water Pollution Control Fed. 63, 120., 1991.38"Typical Applications of Ozone", ARCE Systems, Inc., http://www.arcesystems.com/products/ozone/applications.htm, Feb. 2000, pp. 1-2.39"Who's Afraid of MTBE?", K.P. Wheeler et al., Manko, Gold & Katcher, http://www.rcc-net.com/Wheels.htm, Jul. 2000, pp. 1-5.40"Yuma Pilot-Testing Ozone Sparging, Stripping", Pasha Publications, Defense Cleanup, Nov. 8, 1996, pp. 5-6.41"Ground Water, Surface Water, and Leachate", http://www.frtr.gov/matrix2/section�4/4-30.html, Jul. 22, 2003, pp. 1-4.42Abstract JP 6/238260, Aug. 30, 1994, Karuto.43Biologisch-chemische Behandlung Eines Kontaminierten Grundwassers von einem Gaswerksgelande, Dr.-Ing. Joachim Behrendt, Technische Universitat Hamburg-Harburg, Germany, vol. 136, No. 1, Jan. 1995, pp. 18-24.44Canadian Application No. 2,441,259 Office Action dated Oct. 14, 2009, 7 pages.45Canadian Patent Application No. 2,351,257, Office Action dated May 1, 2009, 4 pages.46Civil Action No. 1:08-cv-11711-GAO, Groundwater & Environmental Services, Inc.'s Objections and Answers to Plaintiffs Interrogatories, Mar. 4, 2009, 10 pages.47Civil Action No. 1:08-cv-11711-GAO, Groundwater & Environmental Services, Inc.'s Objections and Responses to Plaintiffs Requests for Production of Documents and Things, Mar. 4, 2009, 54 pages.48Civil Action No. 1:08-cv-11711-GAO, Groundwater & Environmental Services, Inc.'s Supplemental Response to Plaintiffs Interrogatories Three and Four, Jul. 6, 2009, 164 pages.49Civil Action No. 1:08-cv-11711-GAO, Groundwater & Environmental Services, Inc.'s Supplemental Response to Plaintiff's Interrogatory Three, Jun. 25, 2009, 36 pages.50Civil Action No. 1:08-cv-11711-GAO, ThinkVillage-Kerfoot, LLC's Objections and Responses to Defendant's First Set of Requests for Production (Nos. 1-98) Apr. 9, 2009, 37 pages.51Civil Action No. 1:08-cv-11711-GAO, ThinkVillage-Kerfoot, LLC's Responses to Defendant's Interrogatories (Nos. 1-11) Apr. 9, 2009, 12 pages.52Civil Action No. 1:08-cv-11711-GAO, ThinkVillage-Kerfoot, LLC's Supplemental Responses to Defendant's Interrogatories (Nos. 7 and 8) Jun. 2, 2009, 9 pages.53Design of a Packed Bed Ozonation Reactor for Removal of Contaminants from Water, Billing, Dissertation Abstracts International, vol. 57, No. 10, Apr. 1997, pp. 6398-B.54European Application No. 01305133 European Search Report; Jul. 8, 2003; 4 pages.55European Application No. 01305133 Examination Report; Oct. 29, 2007; 2 pages.56European Application No. 01305133 Examination Report; Sep. 13, 2005; 4 pages.57European Application No. 01305133 Response to Examination Report, Aug. 15, 2008; 13 pages.58European Application No. 01305133 Response to Examination Report; Feb. 28, 2006; 19 pages.59Further substantive examination report Application No. 01305133.9.60Gas Partitioning of Dissolved Volatile Organic Compounds in the Vadose Zone: Principles, Temperature Effects and Literature Review, J.W. Washington, Groundwater, vol. 34, No. 4, Jul.-Aug. 1996, pp. 709-718.61Makarov, A.M. & Sorokin, S.S., Heat Exchange Of A Bubble Coated With A Liquid Film On The Rear Surface, Chemical and Petroleum Engineering, vol. 30, No. 2, 1994, pp. 78-81.62PCT/US04/43634 International Search Report mailed May 18, 2005, 1 page.63PCT/US04143634 International Preliminary Report on Patentability, Jun. 26, 2006, 5 pages.64PCT/US05/25478, International Preliminary Report on Patentability, Jan. 23, 2007, 4 pages.65PCT/US05/25478, International Search Report & Written Opinion, mailed Feb. 15, 2006, 4 pages.66Substantive examination report Application No. 01305133.9.67ThinkVillage-Kerfoot LLC v. Groundwater & Environmental Services, Inc., Amended Answer and Counterclaims, Civil Action No. 1:08-cv-11711-GAO, Dec. 15, 2008, 7 pages.68ThinkVillage-Kerfoot LLC v. Groundwater & Environmental Services, Inc., Answer and Counterclaims, Civil Action No. 1:08-cv-11711-GAO, Dec. 5, 2008, 7 pages.69ThinkVillage-Kerfoot LLC v. Groundwater & Environmental Services, Inc., Complaint for Patent Infringement, US District Court for the District of Massachusettes, Oct. 7, 2008, 5 pages.70ThinkVillage-Kerfoot LLC v. Groundwater & Environmental Services, Inc., Plaintiff's Response to Defendant Groundwater & Environmental Services, Inc.'s Amended Counterclaims, Civil Action No. 1:08-cv-11711-GAO, Dec. 30, 2008, 5 pages.71U.S. Appl. No. 09/470,167 (US. Pat. No. 6,436,285) Selected pages from File History dated Mar. 29, 2001 through Aug. 23, 2002, 38 pages.72U.S. Appl. No. 09/860,659, Selected pages from Image File Wrapper dated Aug. 13, 2002 through Aug. 23, 2004, 68 pages.73U.S. Appl. No. 09/943,111, Selected pages from Image File Wrapper dated Jan. 30, 2003 through Feb. 19, 2005, 47 pages.74U.S. Appl. No. 09/993,152, Selected pages from Image File Wrapper dated Sep. 4, 2007 through Mar. 10, 2009, 59 pages.75U.S. Appl. No. 10/223,166 (US Pat. No. 6,596,161) Selected pages from File History dated Nov. 6, 2002 through Jul. 22, 2003, 22 pages.76U.S. Appl. No. 10/354,584 Selected pages from Image File Wrapper dated Jul. 30, 2003 through Jul. 6, 2004, 32 pages.77U.S. Appl. No. 10/365,027, Selected pages from Image File Wrapper dated Apr. 16, 2004 through May 2, 2005, 53 pages.78U.S. Appl. No. 10/602,256, selected pages from Image File Wrapper through Jan. 11, 2005 through Oct. 11, 2005; 37 pages.79U.S. Appl. No. 10/745,939, selected pages from Image File Wrapper dated Jun. 22, 2006 through Jul. 2, 2008, 113 pages.80U.S. Appl. No. 10/794,994 Selected pages from Image File Wrapper dated Jul. 6, 2006 through Apr. 18, 2007,48 pages.81U.S. Appl. No. 10/895,015 Notice of Allowance mailed Feb. 9, 2009, 4 pages.82U.S. Appl. No. 10/895,015, selected pages from Image File Wrapper dated Jul. 14, 2006 through Oct. 27, 2008, 102 pages.83U.S. Appl. No. 10/910,441 Selected pages from Image File Wrapper dated Dec. 1, 2004 through Sep. 12, 2005, 36 pages.84U.S. Appl. No. 10/916,863 Selected pages from Image File Wrapper dated Dec. 28, 2006 through Oct. 8, 2008, 39 pages.85U.S. Appl. No. 10/963,353 Selected pages from Image File Wrapper dated Aug. 23, 2005 through Dec. 13, 2006, 46 pages.86U.S. Appl. No. 10/963,361 Selected pages from Image File Wrapper dated Jul. 19, 2005 through Nov. 7, 2007.87U.S. Appl. No. 10/994,960 Selected pages from Image File Wrapper dated Mar. 11, 2005 through Dec. 2, 2005, 36 pages.88U.S. Appl. No. 10/997,452 Selected pages from Image File Wrapper dated Jun. 27, 2007 through Dec. 23, 2008, 129 pages.89U.S. Appl. No. 11/145,871 , Notice of Allowance dated Sep. 09, 2009, 7 pages.90U.S. Appl. No. 11/145,871 Office Action mailed Mar. 18, 2009,16 pages.91U.S. Appl. No. 11/145,871 Response to Office Action filed Jun. 18, 2009, 10 pages.92U.S. Appl. No. 11/145,871 Selected pages from Image File Wrapper dated Jun. 12, 2007 through Dec. 16, 2008, 93 pages.93U.S. Appl. No. 11/145,871, Office Action mailed Mar. 18, 2009, 16 pages.94U.S. Appl. No. 11/146,722 Selected pages from Image File Wrapper dated Jun. 7, 2005 through Sep. 18, 2006, 70 pages.95U.S. Appl. No. 11/272,446 Notice of Allowance and Examiner Interview Summary mailed Mar. 27, 2009, 11 pages.96U.S. Appl. No. 11/272,446 Selected pages from File History dated Jan. 22, 2008 through May 1, 2009, 60 pages.97U.S. Appl. No. 11/272,446, selected pages from Image File Wrapper dated Oct. 22, 2008 through Jan. 12, 2009, 50 pages.98U.S. Appl. No. 11/328,475 Selected pages from Image File Wrapper dated Jun. 30, 2006 through Aug. 15, 2007, 45 pages.99U.S. Appl. No. 11/485,080 Office Action mailed Jan. 9, 2009, 8 pages.100U.S. Appl. No. 11/485,080 Response to Office Action filed May 8, 2009, 4 pages.101U.S. Appl. No. 11/485,080 Selected pages from Image File Wrapper dated May 11, 2007 through Jan. 9, 2009, 83 pages.102U.S. Appl. No. 11/485,080, Notice of Allowance dated Jul. 9, 2009, 4 pages.103U.S. Appl. No. 11/485,080, Response to Office Action filed May 8, 2009, 4 pages.104U.S. Appl. No. 11/485,223 Notice of Allowance dated Sep. 2, 2009, 7 pages.105U.S. Appl. No. 11/485,223 Office Action mailed Jun. 15, 2009, 8 pages.106U.S. Appl. No. 11/485,223 Office Action mailed Nov. 12, 2008, 9 pages.107U.S. Appl. No. 11/485,223 Response to Office Action filed Mar. 11, 2009, 13 pages.108U.S. Appl. No. 11/485,223 Selected pages from Image File Wrapper dated Feb. 26, 2008 through Mar. 11, 2009, 36 pages.109U.S. Appl. No. 11/485,223 Selected pages from Image File Wrapper dated Feb. 26, 2008 through Nov. 12, 2008, 23 pages.110U.S. Appl. No. 11/594,019 Selected pages from Image File Wrapper dated Apr. 25, 2007 through Oct. 29, 2008, 45 pages.111U.S. Appl. No. 11/849,413 Notice of Allowance mailed Mar. 10, 2009, 4 pages.112U.S. Appl. No. 11/849,413 Selected pages from Image File Wrapper dated Sep. 4, 2007 through Mar. 10, 2009, 94 pages.113U.S. Appl. No. 11/849,413, selected pages from Image File Wrapper dated Apr. 1, 2008 through Jan. 21, 2009, 45 pages.114U.S. Appl. No. 12/177,467 Notice of Allowance dated Sep. 2, 2009, 8 pages.115U.S. Appl. No. 12/177,467 Response to Restriction Requirement filed Mar. 30, 2009.116U.S. Appl. No. 12/177,467 Selected pages from Image File Wrapper dated Dec. 29, 2008 through Jun. 12, 2009, 20 pages.117U.S. Appl. No. 12/177,467, Restriction Requirement mailed Dec. 29, 2008, 8 pages.118U.S. Appl. No. 12/254,359 Notice of Allowance mailed Apr. 1, 2009.119U.S. Appl. No. 12/254,359, Notice of Allowance dated Jul. 6, 2009, 4 pages.120U.S. Appl. No. 12/259,051 Notice of Allowance dated Aug. 24, 2009, 7 pages.121U.S. Appl. No. 12/259,051, Office Action dated Mar. 24, 2009, 6 pages.122U.S. Appl. No. 12/259,051, Response to Office Action filed Jun. 23, 2009, 8 pages.123U.S. Appl. No. 12/272,462 Notice of Allowance dated Sep. 21, 2009, 8 pages.124U.S. Appl. No. 12/272,462, Response to Restriction Requirement filed Jul. 2, 2009, 12 pages.125U.S. Appl. No. 12/272,462, Restriction Requirement mailed Jun. 2, 2009, 6 pages.Referenced byCiting PatentFiling datePublication dateApplicantTitleUS8931330 *Sep 8, 2009Jan 13, 2015R+I AllianceMethod and device for detecting leaks in an underground liquid pipe, particularly a water pipeUS20110168399 *May 4, 2009Jul 14, 2011Jean Francois Saint-MarcouxMid water gas liftUS20110219855 *Sep 8, 2009Sep 15, 2011R + I AllianceMethod and device for detecting leaks in an underground liquid pipe, particularly a water pipe* Cited by examinerClassifications U.S. Classification210/747.8, 210/759, 405/128.5, 210/760International ClassificationB09C1/08, B09C1/00, C02F1/00, C02F1/72, C02F1/78Cooperative ClassificationB09C1/002, C02F2101/36, C02F1/00, C02F2103/06, B09C1/08, C02F1/725, B09C2101/00, C02F1/78, C02F2101/32European ClassificationC02F1/72K, C02F1/78, B09C1/00B, B09C1/08Legal EventsDateCodeEventDescriptionFeb 25, 2013FPAYFee paymentYear of fee payment: 4Jun 29, 2010CCCertificate of correctionJan 17, 2009ASAssignmentOwner name: KERFOOT TECHNOLOGIES, INC., MASSACHUSETTSFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:KERFOOT, WILLIAM B.;REEL/FRAME:022117/0557Effective date: 20080307Owner name: KERFOOT TECHNOLOGIES, INC.,MASSACHUSETTSFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:KERFOOT, WILLIAM B.;US-ASSIGNMENT DATABASE UPDATED:20100225;REEL/FRAME:22117/557Owner name: KERFOOT TECHNOLOGIES, INC.,MASSACHUSETTSFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:KERFOOT, WILLIAM B.;US-ASSIGNMENT DATABASE UPDATED:20100223;REEL/FRAME:22117/557Jul 10, 2008ASAssignmentOwner name: THINKVILLAGE-KERFOOT, LLC, COLORADOFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:KERFOOT TECHNOLOGIES, INC.;REEL/FRAME:021217/0168Effective date: 20080307Owner name: THINKVILLAGE-KERFOOT, LLC,COLORADOFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:KERFOOT TECHNOLOGIES, INC.;US-ASSIGNMENT DATABASE UPDATED:20100223;REEL/FRAME:21217/168Owner name: THINKVILLAGE-KERFOOT, LLC,COLORADOFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:KERFOOT TECHNOLOGIES, INC.;US-ASSIGNMENT DATABASE UPDATED:20100225;REEL/FRAME:21217/168RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services