Microporous diffusion apparatus

Apparatuses for removal of volatile organic compounds in a soil formation include a microporous diffuser for injecting air and gaseous ozone as bubbles into water in the soil formation. The gaseous ozone is present at concentrations to effect removal of volatile organic compounds by the gaseous ozone reacting with the volatile organic compound(s). Injection of air and gaseous ozone is controlled by a timer to allow separation of bubbles by size. In various embodiments, a plurality of microporous diffusers may be controlled by a single timer or each of the plurality of microporous diffusers may be controlled by one of a plurality of timers.

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Description
CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a reissue of U.S. Pat. No. 7,645,380, which is a continuation of U.S. patent application Ser. No. 10/997,452, filed Nov. 24, 2004, now U.S. Pat. No. 7,537,706, which is a continuation of U.S. patent application Ser. No. 09/943,111, filed Aug. 30, 2001, now U.S. Pat. No. 6,872,318, which is a continuation of U.S. patent application Ser. No. 09/606,952, filed Jun. 29, 2000, now U.S. Pat. No. 6,284,143, which is a continuation of U.S. patent application Ser. No. 09/220,401, filed Dec. 24, 1998, now U.S. Pat. No. 6,083,407, which is a continuation of U.S. patent application Ser. No. 08/756,273, filed Nov. 25, 1996, now U.S. Pat. No. 5,855,775, which is a-continuation-in-part of U.S. patent application Ser. No. 08/638,017, filed Apr. 25, 1996, now abandoned, which is a continuation-in-part of U.S. patent application Ser. No. 29/038,499, filed May 5, 1995, now abandoned. Each of these applications is incorporated by reference in its entirety.

BACKGROUND

1. Field of Invention (Technical Field)

The present disclosure relates to apparatuses for remediation of dissolved chlorinated hydrocarbons in aquifer regions by injecting micro-fine bubbles effective for active in situ groundwater remediation for removal of dissolved chlorinated hydrocarbon solvents and dissolved hydrocarbon petroleum products. Remediation of saturated soils may also be obtained by employment of the present apparatuses.

2. Background Prior Art

There is a well recognized need to cleanup subsurface leachate plumes in aquifer regions and contaminated sites including, in particular, dry-cleaning establishments and U.S. Military Air bases. Applicant is aware of prior art devices that have used injection of air to facilitate biodegradation of plumes.

However, an apparatus using micro-fine bubbles including a multi-gas oxidizing agent for the controlled remediation of a site containing poorly biodegradable organics, particularly dissolved chlorinated solvents, has not been shown.

In fact the Federal Agency (EPA, KERR Environmental Laboratory, ADA, Oklahoma) responsible for review of clean-up procedures at Marine Corp Air Base at Yuma, Ariz. has determined that there is no prior reference which discloses the use of the present apparatuses and has ordered independent pilot tests to provide test results confirming the results previously obtained by the present apparatuses.

U.S. Pat. No. 5,221,159, to Billings, shows injection of air into aquifer regions to encourage biodegradation of leachate plumes which contain biodegradable organics together with simultaneous soil vacuum extraction.

U.S. Pat. No. 5,269,943, METHOD FOR TREATMENT OF SOILS CONTAMINATED WITH ORGANIC POLLUTANTS, to Wickramanayake, shows a method for treating soil contaminated by organic compounds where an ozone containing gas is treated with acid to increase the stability of the ozone in the soil environment and the treated ozone is applied to the contaminated soil to decompose the organic compounds.

U.S. Pat. No. 5,525,008, REMEDIATION APPARATUS AND METHOD FOR ORGANIC CONTAMINATION IN SOIL AND GROUNDWATER, to Wilson, provides a method and apparatus for in-situ treatment of soil and groundwater contaminated with organic pollutants. It involves concentration of a reactive solution required to effect treatment of the contaminated area and injecting the reactive solution into one or more injectors that are inserted into the ground. The apparatus is scaled and positioned so as to assure flow and to allow reactive solution to flow through the contaminated area thereby reacting chemically. Preferably, the reactive solution is an aqueous solution of hydrogen peroxide and metallic salts.

U.S. Pat. No. 5,178,755, UV-ENHANCED OZONE WASTEWATER TREATMENT SYSTEM, to Lacrosse, mixes wastewater with ozonated liquid within a multi-stage clarifier system and suspended solids are removed.

Notwithstanding the teachings of the prior art, there has not been shown an apparatus for remediating a site contaminated with poorly biodegradable organics, particularly dissolved chlorinated solvents, with micro-fine bubbles including an encapsulated multi-gas oxidizing agent in a controlled manner. In situ remediation is accomplished using the present instrumentalities by employing microporous diffusers which inject multi-gas bubbles containing an ozone oxidizing agent into aquifer regions to strip and rapidly decompose poorly biodegradable organics or to accelerate biodegradation of leachate plumes which contain biodegradable organics thereby overcoming at least some disadvantages of the prior art.

SUMMARY

The present disclosure relates to sparging apparatuses for injection of oxidizing gas, in the form of small bubbles, into aquifer regions to encourage in situ remediation of subsurface leachate plumes.

In particular, sparging apparatuses are disclosed for employing microporous diffusers to inject micro-fine bubbles containing encapsulated gas bubbles into aquifer regions to encourage biodegradation of leachate plumes which contain biodegradable organics, or Criegee decomposition of leachate plumes containing dissolved chlorinated hydrocarbons. The sparging apparatuses, employing microporous diffusers for injecting an encapsulated multi-gas oxidizing agent, are particularly useful in promoting extremely efficient removal of poorly biodegradable organics, such as dissolved chlorinated solvents, without the use of vacuum extraction of undesirable by-products of remediation. Furthermore, remediation occurs by employing encapsulated multi-gas oxidizing agent for destroying organic and hydrocarbon material in place with out release of contaminating vapors.

Unlike the prior art, the contaminated groundwater is injected with an air/ozone mixture wherein micro-fine air bubbles strip the solvents from the groundwater and the encapsulated ozone acts as an oxidizing agent in a gas/gas reaction to break down the contaminates into carbon dioxide, very dilute HCl and water. This system is known as the C-Sparger® system.

The present system, hereinafter C-Sparger® system, is directed to low-cost removal of dissolved chlorinated hydrocarbon solvents such as perc from contaminated soil and groundwater aquifers. The C-Sparger® system employs microporous diffusers, hereinafter Spargepoints®, for producing micro-fine bubbles containing an oxidizing agent that decomposes chlorinated hydrocarbons into harmless byproducts. The C-Sparger® system also incorporates: means for pumping a multi-gas oxidizing mixture through the Spargepoint® into groundwater in a soil formation, a bubble production chamber to generate bubbles of differing size, a timer to delay pumping until large bubbles have segregated from small bubbles by rise time, and a pump which forces the fine bubbles and liquid out into the soil formation. The pumping means intermittently agitates the water in the well in which the C-Sparger® is installed in order to effectively disturb the normal inverted cone-shaped path of the bubbles injected by the Spargepoint®. Water agitation results in random bubble dispersion to ensure improved contact between the oxidizing agent (contained in each bubble) and the pollutant. The pulsing action promotes movement of the bubbles through the porous formation. It is the in situ stripping action and maintenance of low solvent gas concentration in the bubbles which increases the efficacy and speed of remediation of a site.

The apparatus of the present disclosure is particularly useful in efficiently removing poorly biodegradable organics, particularly dissolved chlorinated solvents, without the use of vacuum extraction, wherein remediation occurs by destroying organic and hydrocarbon material in place without the release of contaminating vapors.

The multi-gas system comprises an oxidizing gas encapsulated in micro-bubbles, generated from microporous diffusers, that are matched to soil porosity. A unique bubble size range is matched to underground formation porosity and achieves dual properties of fluid like transmission and rapid extraction of selected volatile gases. Bubble size is selected so as to maintain vertical mobility. In order to accomplish a proper matching, a prior site evaluation test procedure is devised to assess the effectiveness of fluid transmission at the remediation site.

Small bubbles with a high surface to gas volume ratio are advantageous in promoting rapid extraction of volatile organic compounds, such as PCE, TCE, or DCE. Pulsed injection of small bubbles and consequent rise time is matched to the short half-life of an oxidative gas, such as ozone, to allow rapid bubble dispersion into predominantly water-saturated geological formations, and extraction and rapid decomposition of the volatile organic material. The unique apparatus of the present disclosure provides for extraction efficiency with resulting economy of operation by maximizing contaminant contact with oxidant by selective rapid extraction providing for optimum fluidity of bubbles through media which can be monitored.

The use of microporous diffuser points provides a more even distribution of air into a saturated formation than the use of pressurized wells. A sparge system installed to remediate contaminated groundwater is made more cost-effective by sparging different parts of the plume area at sequenced times. Through the proper placement of sparge locations and sequence control, any possible off-site migration of floating product is eliminated. With closely spaced Spargepoints®, water mounding is advantageous because it prevents any off-site escape of contaminant. Water mounding is used to direct floating product toward extraction sites.

The microporous diffusers and multi-gas system, referred to as Spargepoints® and C-Sparger® Systems, are designed to remove dissolved organics and solvents (chlorinated hydrocarbons) such as PCE, TCE, and DCE from contaminated groundwater. The micro-fine bubbles, produced by the Spargepoints®, contain oxygen and ozone which oxidize the chlorinated hydrocarbons to harmless gases and weak acids. High initial concentrations of these dissolved organics have been, under some specific-circumstances, reduced to levels of 1 ppb or less in periods of a few weeks. None of the models to date are designed for explosive environments.

The present systems employ a plurality of configurations consisting of Series 3500 and Series 3600 C-Sparger® models. The 3600 Series is larger and has more capacity. Specifically, the 3600 Series has a better compressor rated for continuous use, a larger ozone generator, a second Spargepoint® below the first Spargepoint® in each well, and larger diameter gas tubing. Both model series have control units that can support: one (Models 3501 & 3601), two (Models 3502 & 3602) and three separate wells (Models 3503 & 3603). The one, two, and three well models differ in the number of relays, internal piping, external ports and programming of the timer/controller.

Normal operation for C-Sparger® systems includes carrying out, in series for each well, the following functions on a timed basis: pumping air and ozone through Spargepoint® diffusers into the soil formation, pumping aerated/ozonated water into the soils and recovering treated water above. Treatment is followed by a programmable period of no external treatment and multiple wells are sequenced in turn. Agitation with pumped water disturbs the usually inverted cone-shaped path of bubbles through the soils and disperses them much more widely. This increases contact and greatly improves efficiency and speed of remediation. Vapor capture is not normally necessary.

Series 3500 and 3600 systems include a control module, one to three well assemblies depending on specific model selected, a 1.0 ft. long submersible pump power-gas line for each well and a flow meter (to check Spargepoint® flow rates). Model Series 3500 & 3600 control modules have been successfully deployed outdoors in benign and moderate environments for prolonged periods of time. The control module must be firmly mounted vertically on 4×4 posts or on a building wall near the wells.

The actual placement depths, separations, number/size of wells and overall remediation system geometry are highly variable. Differences in specific pollutant, spill, soil, groundwater and climate characteristics can greatly influence the design and geometry of the overall remediation system. Monitoring wells are usually also needed. In short, specific circumstances and conditions are often critical, however, a generic or typical overall system is shown on FIG. 1.

FIG. 13 provides the basic specification for the Series 3500 & 3600 systems. The drawing shows a single well system Series 3600 (M-3601). The Series 3500 does not have the lower Spargepoint® multiple well models (3502, 3503, 3602 & 3603), rather multiple M-3601 well units use a single control module. FIG. 2 shows a piping schematic. FIG. 3 shows an electrical schematic for a three well system (Model 3503 or 3603). Current production 3500 and 3600 Series models have an internal ground fault interrupter and surge buffers incorporated into various electrical components. FIG. 4 shows an internal layout of the control module box for a three well system (M-3503 or M-3603). FIG. 5 shows the geometry of the bottom panel on the control module identifying the external connections and ports for three well units (M-3503 & 3603). FIGS. 3 and 4 also illustrate fuses and their locations.

The Unique Use of Microfine Bubbles for Simultaneous Extraction/Decomposition.

The use of microporous Spargepoint® diffusers to create fine bubbles, which easily penetrate sandy formations to allow fluid flow, has unexpected benefits when used with multiple gas systems. Microfine bubbles accelerate the transfer rate of PCE from aqueous to gaseous state. The bubble rise transfers the PCE to the vadose zone. The ten-fold difference in surface-to-volume ratio of Spargepoint® diffuser microbubbles compared to bubbles from well screens results in a four-fold improvement in transfer rates. To block the gaseous state from reverting to a surface dissolved state in the vadose (unsaturated) zone, a microprocessor system shuttles an oxidizing gas through the vadose zone to chemically degrade the transported PCE.

Gaseous Exchange

If gaseous exchange is proportional to available surface area, with partial pressures and mixtures of volatile gases being held constant, a halving of the radius of bubbles would quadruple (i.e. 4×), the exchange rate. If, in the best case, a standard well screen creates air bubbles the size of a medium sand porosity, a microporous diffuser of 20 micron size creates a bubble one tenth ( 1/10) the diameter and then times the volume/surface ratio (Table 1).

TABLE 1 Diameter Surface Area Volume Surface (microns) (4 πr2) (4/3 r3) Area/Volume 200 124600 4186666 .03 20 1256 4186 .3

Theoretically, the microporous bubbles exhibit an exchange rate of ten times the rate of a comparable bubble from a standard ten slot well screen.

Partitioning Enhancement

Soil Vapor concentrations are related to two governing systems: water phase and (non-aqueous) product phase. Henry's and Raoult's Laws (DiGiulio, 1990) are commonly used to understand equilibrium-vapor concentrations governing volatization from liquids. When soils are moist, the relative volatility is dependent upon Henry's Law. Under normal conditions (free from product) where volatile organic carbons (VOC's) are relatively low, an equilibrium of soil, water, and air is assumed to exist. The compound, tetrachloroethene (PCE), has a high exchange coefficient with a high vapor pressure (atm) and low aqueous solubility (μmole/l). By enhancing the exchange capacity at least ten fold, the rate of removal should be accelerated substantially.

Ozone is an effective oxidant used for the breakdown of organic compounds during water treatment. The major problem in effectiveness is ozone's short half-life. If ozone is mixed with sewage-containing water above-ground, the half-life is normally minutes. However, if maintained in the gaseous form, the half-life of ozone can be extended up to 15 hours. Microbubbles can be used as extracting agents by pulling chlorinated solvents out of solution into the gaseous ozone as they enter the microbubble. The small bubble's high surface-to-volume ratio increases the exchange area and accelerates the consumption of HVOC within the bubble maximizing the concentration of gas transferred into the bubble (CS−C). The rate-limiting process is the area-specific diffusion (dominated by Henry's Constant), while the decomposition reaction occurs rapidly (assuming sufficient ozone).

Ozone reacts quickly and quantitatively with PCE to yield breakdown products of hydrochloric acid, carbon dioxide, and water.

Using microporous diffusers to inject ozone-containing bubbles may offset ozone's relatively short half-life. By encapsulating the ozone in fine bubbles, the bubbles would preferentially extract volatile compounds like PCE from the mixtures of soluble organic compounds they encountered. The ozone-mediated destruction of organics may then selectively target volatile organics pulled into the fine air bubbles. Even in a groundwater mixture of high organic content like diluted sewage, PCE removal could be rapid.

The unique combination of microbubble extraction and ozone-mediated degradation can be generalized to render volatile organic compounds amenable to rapid removal. The efficiency of extraction is directly proportional to Henry's Constant which serves as a diffusion coefficient for gaseous exchange (Kg).

In wastewater treatment the two-film theory of gas transfer (Metcalf and Eddy, Inc, 1991) states the rate of transfer between gas and liquid phases is generally proportional to the surface area of contact and the difference between the existing concentration and the equilibrium concentration of the gas in solution. Simply stated, if the surface-to-volume ratio of contact is increased, the rate of exchange will increase. If the gas (volatile organic compound, hereinafter “VOC”) entering the bubble (or micropore space bounded by a liquid film) is consumed, the difference is maintained at a higher entry rate than if the VOC is allowed to reach saturation equilibrium. In the present case, the consumptive gas/gas reaction of PCE to by-products of HCl, CO2, and H2O drives the transfer of PCE into the bubble.

The normal equation for the two-film theory of gas transfer is (Metcalf and Eddy, 1991):
Vm=KgA(CS−C)
where:

    • Vm=rate of mass transfer
    • Kg=coefficient of diffusion for gas
    • A=area through which gas is diffusing
    • CS=saturation concentration of gas phase in bubble
    • C=initial concentration of gas phase in bubble volume

Table 2 gives Henry's Constants (Hc) for a selected number of organic compounds and the second rate constants (Rc) for the ozone radical rate of reaction. The fourth column presents the product of both Hc and Rc (RRC) as a ranking of effectiveness. In actual practice diffusion is rate-limiting, resulting in the most effective removal with PCE (tetrachloroethylene).

TABLE 2 REMOVAL RATE COEFFICIENTS FOR THE MICROBUBBLE/OZONE PROCESS - C-SPARGE Ozone K2 Second order K1 Rate Organic Rate Constanta Henry's Removal Compound (M−1 SEC−1) Constantb Coefficient Benzene 2 5.59 × 10−3 .0110 Toluene 14 6.37 × 10−3 .0890 Chlorobenzene 0.75 3.72 × 10−3 .0028 Trichloroethylene 17 9.10 × 10−3 .1540 Tetrachloroethylene 0.1 2.59 × 10−2 .026 Ethanol .02 4.48 × 10−5 .0000008 Rc · Hc = RRC aFrom Hoigne and Bader, 1983 bFrom EPA 540/1-86/060, Superfund Public Health Evaluation Manual

Elimination of the Need for Vapor Extraction

The need for vapor control exists when vapors of VOC's partitioned from the dissolved form into the microbubbles, reach the unsaturated zone, releasing vapors. Without reaction with a decomposing gas, such as ozone, a large mass can be transmitted in a short time, creating potential health problems near residential basement areas.

The combined extraction/decomposition process has the capacity to eliminate the need for vapor capture. If the ozone-mediated decomposition rate exceeds the vertical time-of-travel, vapors will either not be produced or their concentration will be so low as to eliminate the requirement for capture. By controlling the size of microbubbles and matching them to suitable slow rise times, the need for vapor control is eliminated.

The rise time of bubbles of different sizes was computed for water, producing the upwards gravitational velocity (Table 3). The upwards velocity provides the positive pressure to push the bubbles through the porous media, following Darcy's equation. By determining the rise rate in the field, the rise time, proportional to upwards pressure, can be calculated. The bubble size is very important. Once a bubble exceeds the pore cavity size, it is significantly retarded or trapped. Pulsing of the water phase provides a necessary boost to assure steady upwards migration and reduction of coalescence.

TABLE 3 TIME (MINUTES FOR UPWARD UPWARDS MIGRATION BUBBLE VELOCITY (3 METERS) (Coarse DIAMETER IN WATER Sand and Gravel) 10 mm .25 m/s 19 min  2 mm .16 m/s 30 min  .2 mm .018 m/s  240 min 

Elimination Rate of PCE Relative to Ozone Content

The reaction of ozone with tetrachloroethene (PCE) will produce degradation products of hydrochloric acid, carbon dioxide, and water. By adjusting the ozone concentration to match the dissolved PCE level, the PCE can be removed rapidly without excess ozone release to the air or release of PCE vapor into the unsaturated zone.

Accordingly, the object and purpose of the present disclosure is to provide microporous diffusers for removal of contaminants from soil and associated subsurface ground water aquifer, without applying a vacuum for extraction or relying on biodegradation processes.

Another object of the present disclosure is to provide multi-gas systems to be used in combination with the microporous diffusers to promote an efficient removal of poorly biodegradable organics, particularly dissolved chlorinated solvents, without vacuum extraction.

A further object of the present disclosure is to provide that remediation occurs by destroying organic and hydrocarbon material in place without release of contaminating vapors to the atmosphere.

The instrumentalities will be described for the purposes of illustration only in connection with certain embodiments; however, it is recognized that those persons skilled in the art may make various changes, modifications, improvements and additions on the illustrated embodiments all without departing from the spirit and scope of the present disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross sectional schematic illustration of a soil formation showing an apparatus according to an embodiment.

FIG. 2 is an enlarged piping schematic of the apparatus of FIG. 1 showing the unique fine bubble production chamber.

FIG. 3 is an electrical schematic for a three well system (Model 3503 or 3603) of the apparatus of FIG. 1.

FIG. 4 shows an internal layout of a control module box for a three well system (M-3503 or M-3603) of FIG. 1.

FIG. 5A shows the geometry of a bottom panel on the control module identifying external connections and ports for three well units (M-3503 & 3603) of the apparatus of FIG. 1.

FIG. 5B is a left side view of FIG. 5A.

FIG. 6 is a schematic illustration of a soil formation showing the apparatus of FIG. 1.

FIG. 7 is a perspective view of a bubbler sparge unit for groundwater treatment shown partly in section.

FIG. 8 is a front view of the bubbler sparge unit of FIG. 7.

FIG. 9 is a top elevational view of the bubbler sparge unit of FIG. 7.

FIG. 10 is a bottom elevational view of the bubbler sparge unit of FIG. 7.

FIG. 11 is a front elevational view of the bubbler sparge unit of FIG. 7; the broken line shows the bubbler sparge unit in situ for groundwater treatment.

FIG. 12 is an alternate embodiment of a microporous Spargepoint® assembly of the apparatus of FIG. 1.

FIG. 13 describes Series 3500 & 3600 systems.

 DETAILED DESCRIPTION

The present instrumentalities are directed to sparging apparatus for injection of an oxidizing gas in the form of small bubbles into aquifer regions to encourage in situ remediation of subsurface leachate plumes. In particular, microporous diffusers inject multi-gas bubbles into aquifer regions to encourage biodegradation of leachate plumes which contain biodegradable organics, or Criegee decomposition of leachate plumes containing dissolved chlorinated hydrocarbons.

Referring to FIGS. 1 through 6, there is shown a C-Sparger® System (10) consisting of multiple microporous diffusers (26) in combination with an encapsulated multi-gas system, the system (10) consists of a master unit (12) and one or more in-well sparging units (14). Each master unit (12) can operate up to a total of three wells simultaneously, and treat an area up to 50 feet wide and 100 feet long. Actual performance depends upon site conditions. Vapor capture is not normally necessary.

In an embodiment, as shown in FIG. 1 and FIG. 2, master unit (12) consists of the following: a gas generator (16), a gas feed line (15), a compressor (18), a power source (19), a pump control unit (20), and a timer (2). Master unit (12) must be firmly mounted on 4×4 posts (40) or a building wall (42) near in-well sparging units (14). A heavy-duty power cable (44), not over 50 feet in length, may be used to run from the power source to master unit (12).

Referring to FIGS. 1 and 2, in-well sparging unit (14) consists of a casing (56), an inlet screen (50), an expandable packer (52), an upper site grout (54), an outlet screen (58), and lower grout (62). Each in-well unit (14) includes a fixed packer (24), at least two microporous diffusers (26), a water pump (28), ozone line (30), check valve (32), and fittings (34). As shown in FIGS. 1 and 2, diffuser (26) employs a microporous diffuser in place of a standard slotted well screen to improve dispersion of bubbles (60) through soil shown at (84) and to improve rate of gaseous exchange. A normal 10-slot PVC well screen contains roughly twelve percent (12%) open area. Under pressure most air exits the top slits and radiates outward in a star-like fracture pattern, evidencing fracturing of the formation.

Referring to FIG. 2 there is shown a fine bubble production chamber (46) positioned in the well casing (56) between the upper well screen (50) positioned immediately below fixed packer (24) consisting of a removable closure plug and the lower plug (48) consisting of the fine bubble production chamber (46) containing bubbles (60) including upper Spargepoint® (26) positioned above lower well screen (58) including pump (28) and check valve (32). Referring to FIG. 4 there is shown the internal layout of the control module box (12) including an AC/DC power converter (71), and ozone generator (72), well gas relays (73) (three wells shown), a compressor (74), a master relay (75), a main fuse (76). There is also shown a programmable timer controller (77), a power strip (78), a gas regulator and pressure gauge (79), together with a solenoid manifold (80), a ground fault interrupter (81) and a cooling fan (82).

Spargepoint® diffusers include several unique configurations as follows:

a. A direct substitute for a well screen comprising 30% porosity, 5-50 micron channel size and resistance to flow from 1 to 3 PSI. This configuration can take high volume flow and needs a selective annular pack (sized to formation). The use of high density polyethylene or polypropylene is light-weight, rugged and inexpensive.

b. A microporous diffuser can be placed on the end of a narrow diameter pipe riser KVA 14-291. This reduces the residence time in the riser volume.

c. A shielded microporous diffuser which is injected with a hand-held or hydraulic vibratory hammer. The microporous material is molded around an internal metal (copper) perforated tubing and attached to an anchor which pulls the Spargepoint® out when the protective insertion shaft is retracted. The unit is connected to the surface with 3/16 or ¼ inch polypropylene tubing with a compression fitting.

d. A thin Spargepoint® with molded tubing can be inserted down a narrow shaft for use with push or vibratory tools with detachable points. The shaft is pushed to the depth desired, then the Spargepoint® is inserted, the shaft is pulled upwards, pulling off the detachable drive point and exposing the Spargepoint®.

e. A microporous diffuser/pump combination placed within a well screen in such a manner that bubble production and pumping is sequenced with a delay to allow separation of large bubbles from the desired fine “champagne” bubbles. The pressure from the pump is allowed to offset the formation back pressure to allow injection of the remaining fine bubbles into the formation.

Improvements

In the present apparatuses an improvement comprises several new equipment designs associated with the Spargepoint® diffusers. Most important is the submittal for HDPE porous material with well fittings and pass-through design which allows individual pressure and flow control as shown in FIGS. 7-11.

Secondly, the push-probe points have been developed for use with pneumatic tools, instead of drilling auger insertion.

Improvements on C-Sparger®/microporous Spargepoint® diffuser. One of the major pass-through Spargepoint® problems in horizontal sparging is the even distribution of air bubbles. If an inlet is attached to the end of a screen, the pressure drops continuously as air is released from the screen. The resulting distribution of flow causes most bubbles to be produced where the connection occurs with flow alternating outwards. The end of the screen produces little or no bubbles.

To allow even distribution of bubbles, either individual Spargepoints® are bundled (spaghetti tube approach) or the Spargepoints® are constructed in a unique way which allows interval tubing connections with flow and pressure control for each Spargepoint® region within the proposed arrangement. Tubing connected to a Spargepoint® passes through the Spargepoint® internally without interfering with the function of producing small bubbles on a smooth external surface. The tubing penetration reduces the internal gas volume of the Spargepoint®, thereby reducing residence time for oxidative gases (important since ozone has a certain half-life before decomposition), and allows three to four Spargepoints® to be operated simultaneously with equal flow and pressure. Each Spargepoint® can also be programmed to pulse on a timed sequencer, saving electrical costs and allowing certain unique vertical and horizontal bubble patterns. Spargepoint® diffusers can be fitted with an F480 thread with internal bypass and compression fittings, FIG. 12. Some advantages are as follows:

(1) fits standard well screen;

(2) allows individual flow/pressure control;

(3) reduces residence time; and

(4) allows for casing/sparge instead of continuous bubbler.

Use of injectable points configured as molded, 18 Inch×40 inch HDPE molded into ¼ inch pp tubing or HDPE tubing allows a smooth tube to be inserted into a push probe with a detachable point. Use of “Bullet” prepacked Spargepoint® diffusers with a KVA “hefty system” prepacked sand cylinder and bentonite cylinder placed over tubing and porous point is advantageous. Also use of a porous point reinforced with inner metal tube (perforated) to allow strength throughout tubing resists disintegration of plastic during insertion.

Use of pressure/flow headers: Rotameter/mirror: A mirror placed at an angle in a well hole to allow site of a flowmeter reading scale to a point.

It is well recognized that the effectiveness of treatment is dependent upon the uniformity of gas dispersion as it travels through the formation. A porous structure, with appropriate packing, matches the condition of the pores of the soil with thirty percent (30%) pore distribution. The dispersion of bubbles as a fluid can be checked using Darcy's equation.

The use of microporous materials in the Spargepoint® to inject gases into groundwater saturated formations has special advantages for the following reasons:

    • 1. Matching permeability and channel size;
    • 2. Matching porosity;
    • 3. Enhancing fluidity, which can be determined in situ.

The most effective range of pore space for the diffuser material selected depends upon the nature of the unconsolidated formation to be injected. The following serves as a general guide:

    • 1. Porosity of porous material: thirty percent (30%);
    • 2. Pore space: 5-200 microns;
      • a. 5-20 very fine silty sand;
      • b. 20-50 medium sand;
      • c. 50-200 coarse sand and gravel.

The surrounding sand pack placed between the Spargepoint® and natural material to fill the zone after drilling and excavation should also be compatible in channel size to reduce coalescing of the produced bubbles.

The permeability range for fluid injection function without fracturing would follow:

    • 1. 10−2 to 10−6 cm/sec, corresponding to 2 to 2000 Darcy's; or
    • 2. 10−2 to 10−6 cm/sec; or
    • 3. 100 to 0.01 ft/day hydraulic conductivity.

Permeability is defined as a measure of the ease of movement of a gas through the soil. The ability of a porous soil to pass any fluid, including gas, depends upon its internal resistance to flow, dictated largely by the forces of attraction, adhesion, cohesion, and viscosity. Because the ratio of surface area to porosity increases as particle size decreases, permeability is often related to particle size see Table 3.

Claims

1. An apparatus for removal of volatile organic compounds in a soil formation comprising:

a diffuser for injecting air and gaseous ozone as bubbles into water in the soil formation, the gaseous ozone at concentrations to effect removal of volatile organic compounds by the gaseous ozone reacting with the volatile organic compounds,
wherein injection of air and gaseous ozone is controlled by a timer to allow separation of bubbles by size,
wherein the bubbles range in size from about 5 to 200 μm.

2. The apparatus of claim 1 wherein the air and gaseous ozone are mixed and injected into the water as bubbles with an initial bubble size in a range of about 5 to 200 μm.

3. The apparatus of claim 1 wherein the timer periodically pulses the injected air and gaseous ozone.

4. The apparatus of claim 1 further comprising a bubble sizing chamber.

5. The apparatus of claim 1 further comprising a pump for agitating water to disperse the bubbles through the soil formation.

6. The apparatus of claim 1 wherein the diffuser has a pore size selected to match a porosity of a surrounding soil formation.

7. The apparatus of claim 1 further comprising:

a casing;
a packer disposed through the casing; and
an outlet screen coupled to the casing.

8. The apparatus of claim 7 wherein the outlet screen is coupled to the casing at a lower portion of the casing and the apparatus further comprises an inlet screen coupled to the casing at an upper portion of the casing.

9. An apparatus for removal of volatile organic compounds in a soil formation comprising:

a plurality of diffusers for injecting air and gaseous ozone as bubbles into water in the soil formation, the gaseous ozone at concentrations to effect removal of volatile organic compounds by the gaseous ozone reacting with the volatile organic compounds,
wherein injection of air and gaseous ozone is controlled by at least one timer to allow separation of bubbles by size,
wherein the bubbles range in size from about S 5 to 200 μm.

10. The apparatus of claim 9 wherein the plurality of diffusers is arranged in series.

11. The apparatus of claim 9 wherein the plurality of diffusers is controlled by a single timer.

12. The apparatus of claim 9 wherein each diffuser is coupled to one of a plurality of timers.

13. The apparatus of claim 9 wherein the air and gaseous ozone are mixed and injected into the water as bubbles with an initial bubble size in a range of about 5 to 200 μm.

14. The apparatus of claim 9 wherein the timer periodically pulses the injected air and gaseous ozone.

15. The apparatus of claim 9 further comprising a bubble sizing chamber.

16. The apparatus of claim 9 further comprising a pump for agitating water to disperse the bubbles through the soil formation.

17. The apparatus of claim 9 wherein microporous material of the diffusers has a pore size selected to match a porosity of a surrounding soil formation.

18. The apparatus of claim 9 further comprising:

a casing;
a packer disposed through the casing; and
an outlet screen coupled to the casing.

19. The apparatus of claim 18 wherein the outlet screen is coupled to the casing at a lower portion of the casing and the apparatus further comprises an inlet screen coupled to the casing at an upper portion of the casing.

20. The apparatus of claim 18 wherein the packer is disposed through the casing between the inlet and outlet screens.

21. A method of treating a groundwater or soil formation in situ, comprising: injecting gaseous ozone and air through porous materials to produce bubbles in the groundwater or soil formation at concentrations sufficient to react with, and effect removal of, one or more contaminants in the groundwater or soil formation,

wherein the step of producing bubbles comprises producing bubbles encapsulating ozone and air to convert the contaminants from a dissolved state to a gaseous state and encapsulating the contaminants as a vapor therein.

22. The method of claim 21, wherein the bubbles encapsulating air and ozone increase a transfer rate of the contaminants from a dissolved state to a gaseous state.

23. The method of claim 22 further comprising the step of decomposing the contaminants with the encapsulated air and ozone.

24. The method of claim 23 wherein the step of decomposing the contaminants decomposes the contaminants at a rate that exceeds a rise time of bubble formation.

25. A method of treating a groundwater or soil formation in situ, comprising: injecting gaseous ozone and air through porous materials to produce bubbles in the groundwater or soil formation at concentrations sufficient to react with, and effect removal of, one or more contaminants in the groundwater or soil formation,

wherein the step of producing ozone bubbles comprises increasing a half-life of the ozone.

26. A method for remediating contaminants in a groundwater or soil formation in situ, comprising: injecting a multi-gas oxidizing agent into the groundwater or soil formation through one or more tubes such that the multi-gas oxidizing agent produces bubbles in said groundwater or soil formation that react with the contaminants and encapsulate the contaminants as vapor inside the bubbles.

27. The method of claim 26, wherein the step of injecting further comprises the step of injecting the multi-gas oxidizing agent through a slotted well screen at said groundwater or soil formation.

28. The method of claim 26, wherein the step of injecting further comprises the step of injecting the multi-gas oxidizing agent through a diffuser at said groundwater or soil formation.

29. The method of claim 26, wherein the multi-gas oxidizing agent comprises air and ozone.

30. The method of claim 26, wherein the gaseous bubbles increase a half-life of the ozone.

31. The method of claim 26, wherein the bubbles have reduced bubble sizes to increase surface area to gas volume ratios.

32. The method of claim 26, wherein the bubbles have an initial bubble diameter in a range of about 5 to 200 μm.

33. The method of claim 26, wherein injecting produces the bubbles encapsulating ozone and air to convert the contaminants from a dissolved state to a gaseous state.

34. The method of claim 33, wherein the bubbles increase a transfer rate of the contaminants from a dissolved state to a gaseous state.

35. The method of claim 34, further comprising the step of decomposing the contaminants in the encapsulated air and ozone.

36. The method of claim 35, wherein the step of decomposing the contaminants comprises decomposing the contaminants at a rate that exceeds a rise time of bubble formation.

37. The method of claim 26, wherein the step of injecting produces bubbles with a diameter slightly smaller than a pore size of the soil formation.

38. The method of claim 26, wherein the step of injecting the multi-gas oxidizing agent further comprises injecting the multi-gas oxidizing agent through a slotted well screen surrounded with porous materials to produce bubbles.

39. The method of claim 26, further comprising decomposing the contaminants in said groundwater or soil formation by ozone interaction with double bonded carbon atoms of the contaminants.

40. The method of claim 26, said groundwater or soil formation containing chlorinated hydrocarbons.

41. The method of claim 26, said groundwater or soil formation containing organic and/or hydrocarbon material.

42. The method claim 26, wherein the step of injecting the multi-gas oxidizing agent comprises injecting aerated and ozonated water.

43. The method of claim 26, further comprising intermittently agitating water in said groundwater or soil formation.

44. The method of claim 26, further comprising periodically pulsing the injected multi-gas oxidizing agent.

45. The method of claim 26, wherein the porous material comprises a material selected from the group consisting of PVC, HDPE porous material, sand, and gravel.

Referenced Cited
U.S. Patent Documents
1920719 August 1933 Stich
2517525 August 1950 Cummings
2845185 July 1958 Winderweedle, Jr.
2946446 July 1960 Herbert
3027009 March 1962 Price
3206178 September 1965 Lamb
3219520 November 1965 Box
3276994 October 1966 Andrews
3441216 April 1969 Good
3545731 December 1970 McManus
3570218 March 1971 Finney
3669276 June 1972 Woods
3670817 June 1972 Saucier
3708206 January 1973 Hard et al.
3808123 April 1974 Neel
3814394 June 1974 Murray
3823776 July 1974 Holmes
3997447 December 14, 1976 Breton et al.
4007118 February 8, 1977 Ciambrone
4021347 May 3, 1977 Teller et al.
4048072 September 13, 1977 McCullough
4049552 September 20, 1977 Arff
4064163 December 20, 1977 Drach et al.
4118447 October 3, 1978 Richter
4178239 December 11, 1979 Lowther
4203837 May 20, 1980 Hoge et al.
4268283 May 19, 1981 Roberts
4298467 November 3, 1981 Gartner et al.
4310057 January 12, 1982 Brame
4351810 September 28, 1982 Martinez et al.
4360234 November 23, 1982 Hsueh et al.
4614596 September 30, 1986 Wyness
4622139 November 11, 1986 Brown
4639314 January 27, 1987 Tyer
4684479 August 4, 1987 D'Arrigo
4695447 September 22, 1987 Shultz
4696739 September 29, 1987 Pedneault
4730672 March 15, 1988 Payne
4780215 October 25, 1988 Carlson
4804050 February 14, 1989 Kerfoot
4832122 May 23, 1989 Corey et al.
4837153 June 6, 1989 Laurenson, Jr.
4838434 June 13, 1989 Miller et al.
4844795 July 4, 1989 Halwani
4849114 July 18, 1989 Zeff et al.
4883589 November 28, 1989 Konon
4941957 July 17, 1990 Zeff et al.
4943305 July 24, 1990 Bernhardt
4960706 October 2, 1990 Bliem et al.
4966717 October 30, 1990 Kern
4971731 November 20, 1990 Zipperian
5006250 April 9, 1991 Roberts
5078921 January 7, 1992 Zipperian
5080805 January 14, 1992 Houser
5116163 May 26, 1992 Bernhardt
5120442 June 9, 1992 Kull et al.
5122165 June 16, 1992 Wang
5126111 June 30, 1992 Al-Ekabi et al.
5133906 July 28, 1992 Louis
5160655 November 3, 1992 Donker et al.
5167806 December 1, 1992 Wang et al.
5178491 January 12, 1993 Graves et al.
5178755 January 12, 1993 Lacrosse
5180503 January 19, 1993 Gorelick et al.
5190648 March 2, 1993 Ramsauer
5205927 April 27, 1993 Wickramanayake
5215680 June 1, 1993 D'Arrigo
5221159 June 22, 1993 Billings et al.
5227184 July 13, 1993 Hurst
5238437 August 24, 1993 Vowles et al.
5246309 September 21, 1993 Hobby
5248395 September 28, 1993 Rastelli et al.
5254253 October 19, 1993 Behmann
5259962 November 9, 1993 Later
5269943 December 14, 1993 Wickramanayake
5277518 January 11, 1994 Billings et al.
5302286 April 12, 1994 Semprini et al.
5332333 July 26, 1994 Bentley
5348664 September 20, 1994 Kim et al.
5362400 November 8, 1994 Martinell
5364537 November 15, 1994 Paillard
5375539 December 27, 1994 Rippberger
5389267 February 14, 1995 Gorelick et al.
5398757 March 21, 1995 Corte et al.
RE34890 April 4, 1995 Sacre
5402848 April 4, 1995 Kelly
5403476 April 4, 1995 Bernhardt
5406950 April 18, 1995 Brandenburger et al.
5425598 June 20, 1995 Pennington
5427693 June 27, 1995 Mausgrover et al.
5430228 July 4, 1995 Ciambrone et al.
5431286 July 11, 1995 Xu et al.
5451320 September 19, 1995 Wang et al.
5464309 November 7, 1995 Mancini et al.
5472294 December 5, 1995 Billings et al.
5480549 January 2, 1996 Looney et al.
5482630 January 9, 1996 Lee et al.
5520483 May 28, 1996 Vigneri
5525008 June 11, 1996 Wilson
5545330 August 13, 1996 Ehrlich
5560737 October 1, 1996 Schuring et al.
5588490 December 31, 1996 Suthersan et al.
5609798 March 11, 1997 Liu et al.
5615974 April 1, 1997 Land et al.
5620593 April 15, 1997 Stagner
5622450 April 22, 1997 Grant et al.
5624635 April 29, 1997 Pryor
5663475 September 2, 1997 Elgal
5664628 September 9, 1997 Koehler et al.
5667733 September 16, 1997 Waldron, Sr.
5676823 October 14, 1997 McKay et al.
5698092 December 16, 1997 Chen
5741427 April 21, 1998 Watts et al.
5827485 October 27, 1998 Libal et al.
5833388 November 10, 1998 Edwards et al.
5851407 December 22, 1998 Bowman et al.
5855775 January 5, 1999 Kerfoot
5860598 January 19, 1999 Cruz
5879108 March 9, 1999 Haddad
5925257 July 20, 1999 Albelda et al.
5954452 September 21, 1999 Goldstein
5967230 October 19, 1999 Cooper et al.
5975800 November 2, 1999 Edwards et al.
6007274 December 28, 1999 Suthersan
6017449 January 25, 2000 Eriksson et al.
6083403 July 4, 2000 Tang et al.
6083407 July 4, 2000 Kerfoot
6086769 July 11, 2000 Kilambi et al.
6136186 October 24, 2000 Gonzalez-Martin et al.
6139755 October 31, 2000 Marte et al.
6149819 November 21, 2000 Martin et al.
6210955 April 3, 2001 Hayes
6214240 April 10, 2001 Yasunaga et al.
6217767 April 17, 2001 Clark
6221002 April 24, 2001 James
6254310 July 3, 2001 Suthersan
6283674 September 4, 2001 Suthersan
6284143 September 4, 2001 Kerfoot
6306296 October 23, 2001 Kerfoot
6312605 November 6, 2001 Kerfoot
6352387 March 5, 2002 Briggs et al.
6357670 March 19, 2002 Ganan-Calvo
6364162 April 2, 2002 Johnson
6391259 May 21, 2002 Malkin et al.
6403034 June 11, 2002 Nelson et al.
6428694 August 6, 2002 Brown
6436285 August 20, 2002 Kerfoot
6447676 September 10, 2002 Kerfoot
6488850 December 3, 2002 Perriello
6533499 March 18, 2003 Breeding
6582611 June 24, 2003 Kerfoot
6596161 July 22, 2003 Kerfoot
6596177 July 22, 2003 Sherman
6623211 September 23, 2003 Kukor et al.
6645450 November 11, 2003 Stoltz et al.
6733207 May 11, 2004 Liebert, Jr. et al.
6736379 May 18, 2004 Wegner et al.
6745815 June 8, 2004 Senyard
6773609 August 10, 2004 Hashizume
6780329 August 24, 2004 Kerfoot
6787038 September 7, 2004 Brusseau et al.
6805798 October 19, 2004 Kerfoot
6818136 November 16, 2004 Marek
6827861 December 7, 2004 Kerfoot
6866781 March 15, 2005 Schindler
6872318 March 29, 2005 Kerfoot
6913251 July 5, 2005 Kerfoot
6921477 July 26, 2005 Wilhelm
6984329 January 10, 2006 Kerfoot
7022241 April 4, 2006 Kerfoot
7033492 April 25, 2006 Kerfoot
7131638 November 7, 2006 Kerfoot
7156984 January 2, 2007 Kerfoot
7208090 April 24, 2007 Applegate et al.
7264747 September 4, 2007 Kerfoot
7300039 November 27, 2007 Kerfoot
7442313 October 28, 2008 Kerfoot
7537706 May 26, 2009 Kerfoot
20020029493 March 14, 2002 Baek
20020109247 August 15, 2002 Jager et al.
20030029792 February 13, 2003 Kerfoot
20030222359 December 4, 2003 Jager
20040045911 March 11, 2004 Kerfoot
20050067356 March 31, 2005 Bowman et al.
20060243668 November 2, 2006 Miller et al.
Foreign Patent Documents
3805200 September 1998 DE
0402158 December 1990 EP
0546335 June 1993 EP
2005655 April 1979 GB
2185901 August 1987 GB
1-304838 December 1989 JP
3267196 November 1991 JP
4-171036 June 1992 JP
6-023378 January 1994 JP
7-178391 October 1995 JP
40931314 December 1997 JP
WO 98/21152 May 1998 WO
WO 99/54258 October 1999 WO
WO9956894 November 1999 WO
WO0235908 May 2001 WO
WO0226640 April 2002 WO
WO 2005063367 July 2005 WO
Other references
  • ThinkVillage-Kerfoot LLC v. Groundwater & Environmental Services, Inc., Complaint for Patent Infringement, US District Court for the District of Massachusetts, Oct. 7, 2008, 5 pages.
  • ThinkVillage-Kerfoot LLC v. Groundwater & Environmental Services, Inc., Answer and Counterclaims, Civil Action No. 1:08-cv-11711-GAO, Dec. 5, 2008, 7 pages.
  • ThinkVillage-Kerfoot LLC v. Groundwater & Environmental Services, Inc., Amended Answer and Counterclaims, Civil Action No. 1:08-cv-11711-GAO, Dec. 15, 2008, 7 pages.
  • ThinkVillage-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.
  • Civil Action No. 1:08-cv-11711-GAO, Groundwater & Environmental Services, Inc.'s Objections and Responses To Plaintiff's Requests For Production of Documents and Things, Mar. 4, 2009, 54 pages.
  • Civil Action No. 1:08-cv-11711-GAO, Groundwater & Environmental Services, Inc.'s Objections and Answers To Plaintiff's Interrogatories, Mar. 4, 2009, 10 pages.
  • Civil Action No. 1:08-cv-11711-GAO, ThinkVillage-Kerfoot, LLC's Responses To Defendant's Interrogatories (Nos. 1-11) Apr. 9, 2009, 12 pages.
  • Civil 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.
  • Civil 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.
  • PCT/US04/43634 International Search Report mailed May 18, 2005, 1 page.
  • PCT/USO4/43634 International Preliminary Report on Patentability, Jun. 26, 2006, 5 pages.
  • Makarov , 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.
  • Abstract JP 6-238260, Aug. 30, 1994, Karuto.
  • U.S. Appl. No. 09/470,167 (U.S. 6,436,285) Selected pages from File History dated Aug. 23, 2002 through Mar. 29, 2001, 38 pages.
  • U.S. Appl. No. 09/860,659, Selected pages from Image File Wrapper dated Aug. 13, 2002 through Aug. 23, 2004, 68 pages.
  • U.S. Appl. No. 09/943,111, Selected pages from Image File Wrapper dated Jan. 30, 2003 through Feb. 19, 2005, 47 pages.
  • U.S. Appl. No. 09/993,152, Selected pages from Image File Wrapper dated Sep. 4, 2007 through Mar. 10, 2009, 59 pages.
  • U.S. Appl. No. 10/223,166 (U.S. 6,596,161) Selected pages from File History dated Nov. 6, 2002 through Jul. 22, 2003, 22 pages.
  • U.S. Appl. No. 10/354,584 Selected pages from Image File Wrapper dated Jul. 30, 2003 through Jul. 6, 2004, 32 pages.
  • U.S. Appl. No. 10/365,027, Selected pages from Image File Wrapper dated Apr. 16, 2004 through May 2, 2005, 53 pages.
  • U.S. Appl. No. 10/602,256, Selected pages from Image File Wrapper dated Jan. 11, 2005 through Dec. 12, 2002, 33 pages.
  • U.S. Appl. No. 10/745,939, Selected pages from Image File Wrapper dated Jun. 22, 2006 through Jul. 22, 2008, 110 pages.
  • U.S. Appl. No. 10/895,015, Selected pages from Image File Wrapper dated Jul. 14, 2006 through Feb. 9, 2009, 102 pages.
  • U.S. Appl. No. 10/910,441 Selected pages from Image File Wrapper dated Dec. 1, 2004 through Sep. 12, 2005, 36 pages.
  • U.S. Appl. No. 10/916,863 Selected pages from Image File Wrapper dated Dec. 28, 2006 through Oct. 8, 2008, 39 pages.
  • U.S. Appl. No. 10/963,353 Selected pages from Image File Wrapper dated Aug. 23, 2005 through Dec. 13, 2006, 46 pages.
  • U.S. Appl. No. 10/994,960 Selected pages from Image File Wrapper dated Mar. 11, 2005 through Dec. 2, 2005, 36 pages.
  • U.S. Appl. No. 10/997,452 Selected pages from Image File Wrapper dated Jun. 27, 2007 through Mar. 23, 2009, 144 pages.
  • U.S. Appl. No. 11/145,871 selected pages from Image File Wrapper, Jun. 12, 2007 through Jun. 27, 2008, 82 pages.
  • U.S. Appl. No. 11/145,871, Response to Office Action filed Dec. 16, 2008, 12 pages.
  • U.S. Appl. No. 11/145,871, Office Action mailed Mar. 18, 2009, 16 pages.
  • U.S. Appl. No. 11/145,871 Response to Office Action filed Jun. 18, 2009.
  • U.S. Appl. No. 11/146,722 Selected pages from Image File Wrapper dated Jun. 7, 2005 through Sep. 18, 2006, 70 pages.
  • U.S. Appl. No. 11/272,446 Selected pages from File History dated Jan. 22, 2008 through May 1, 2009, 60 pages.
  • U.S. Appl. No. 11/328,475 Selected pages from Image File Wrapper dated Jun. 30, 2006 through Aug. 15, 2007, 45 pages.
  • U.S. Appl. No. 11/409,892 Selected pages from Image File Wrapper dated Jul. 31, 2006 through May 21, 2009, 94 pages.
  • U.S. Appl. No. 11/485,080 Selected pages from Image File Wrapper dated May 11, 2007 through Jan. 9, 2009, 83 pages.
  • U.S. Appl. No. 11/485,080, Response to Office Action filed May 8, 2009, 4 pages.
  • U.S. Appl. No. 11/485,223 Office Action mailed Jun. 15, 2009, 8 pages.
  • U.S. Appl. No. 11/485,223 Selected pages from Image File Wrapper dated Feb. 26, 2008 through Mar. 11, 2009, 36 pages.
  • U.S. Appl. No. 11/594,019 Selected pages from Image File Wrapper dated Apr. 25, 2007 through Oct. 29, 2008, 45 pages.
  • U.S. Appl. No. 11/849,413 Selected pages from Image File Wrapper dated Sep. 4, 2007 through Mar. 10, 2009, 94 pages.
  • U.S. Appl. No. 12/177,467 Selected pages from Image File Wrapper dated Dec. 29, 2008 through Jun. 12, 2009, 20 pages.
  • U.S. Appl. No. 12/254,359, Notice of Allowance dated Apr. 1, 2009, 7 pages.
  • U.S. Appl. No. 12/272,462, Restriction Requirement mailed Jun. 2, 2009, 5 pages.
  • Canadian Patent Application No. 2,351,257, Office Action dated May 1, 2009, 4 pages.
  • PCT/US05/25478, International Search Report & Written Opinion, mailed Feb. 15, 2006, 4 pages.
  • PCT/US05/25478, International Preliminary Report on Patentability, Jan. 23, 2007, 4 pages.
  • U.S. Appl. No. 12/254,359, Notice of Allowance dated Jul. 6, 2009, 4 pages.
  • U.S. Appl. No. 12/272,462, Response to Restriction Requirement filed Jul. 2, 2009, 12 pages.
  • U.S. Appl. No. 11/485,080, Notice of Allowance dated Jul. 9, 2009, 4 pages.
  • Civil Action No. 1:08-cv-11711-GAO, Groundwater & Environmental Services, Inc.'s Supplemental Response to Plaintiffs Interrogatory Three, Jun. 25, 2009, 36 pages.
  • Civil 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.
  • U.S. Appl. No. 12/177,467 Notice of Allowance dated Sep. 2, 2009, 8 pages.
  • U.S. Appl. No. 11/485,223 Notice of Allowance dated Sep. 2, 2009, 7 pages.
  • U.S. Appl. No. 11/145,871 , Notice of Allowance dated Sep. 9, 2009, 7 pages.
  • U.S. Appl. No. 12/272,462 Notice of Allowance dated Sep. 21, 2009, 8 pages.
  • U.S. Appl. No. 11/409,892, Notice of Allowance dated Oct. 1, 2009,5 pages.
  • Canadian Application No. 2,441,259 Office Action dated Oct. 14, 2009, 7 pages.
  • U.S. Appl. No. 12/483,048 Office Action dated Jan. 13, 2010 , 18 pages.
  • Wilkins (ed.) et al. “Workshop on Monitoring Oxidation-Reduction Processes for Ground-water Restoration,” EPA, (2000), 148 pages.
  • U.S. Appl. No. 12/483,048, Office Action mailed Jul. 12, 2010, 19 pages.
  • U.S. Appl. No. 12/483,048, Response to Office Action filed Apr. 13, 2010, 20 pages.
  • U.S. Appl. No. 12/483,048, Response to Office Action filed Sep. 10, 2010, 13 pages.
  • U.S. Appl. No. 12/483,048, Office Action mailed Oct. 7, 2010, 21 pages.
  • U.S. Appl. No. 10/794,994 Selected pages from Image File Wrapper dated Jul. 6, 2006 through Apr. 18, 2007,48 pages.
  • U.S. Appl. No. 10/963,361 Selected pages from Image File Wrapper dated Jul. 19, 2005 through Nov. 7, 2007, 99 pages.
  • U.S. Appl. No. 12/259,051, Office Action dated Mar. 24, 2009, 6 pages.
  • U.S. Appl. No. 12/259,051, Response to Office Action filed Jun. 23, 2009, 8 pages.
  • U.S. Appl. No. 12/259,051 Notice of Allowance dated Aug. 24, 2009, 7 pages.
  • U.S. Appl. No. 12/483,048, Response to Office Action filed Jan. 7, 2011, 10 pages.
  • U.S. Appl. No.12/483,048, Office Action mailed Mar. 30, 2011, 18 pages.
  • European Application No. 05793889.6 Extended European Search Report dated Dec. 15, 2011, 7 pages.
  • U.S. Appl. No. 12/483,048, Response to Office Action filed May 31, 2011, 6 pages.
  • U.S. Appl. No. 12/483,048, Advisory Action mailed Jun. 27, 2011, 4 pages.
Patent History
Patent number: RE43350
Type: Grant
Filed: Jul 30, 2010
Date of Patent: May 8, 2012
Assignee: Think Village-Kerfoot, LLC (Boulder, CO)
Inventor: William B. Kerfoot (Falmouth, MA)
Primary Examiner: Fred Prince
Attorney: Lathrop & Gage LLP
Application Number: 12/847,931