WO2002094723A1 - Environmental remediation method and apparatus - Google Patents

Environmental remediation method and apparatus Download PDF

Info

Publication number
WO2002094723A1
WO2002094723A1 PCT/US2002/015939 US0215939W WO02094723A1 WO 2002094723 A1 WO2002094723 A1 WO 2002094723A1 US 0215939 W US0215939 W US 0215939W WO 02094723 A1 WO02094723 A1 WO 02094723A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
liquid
coated
microbubbles
microbubble
Prior art date
Application number
PCT/US2002/015939
Other languages
French (fr)
Inventor
William Kerfoot
Original Assignee
William Kerfoot
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=25333724&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2002094723(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by William Kerfoot filed Critical William Kerfoot
Priority to CA2441259A priority Critical patent/CA2441259C/en
Priority to EP02771856A priority patent/EP1390303A4/en
Publication of WO2002094723A1 publication Critical patent/WO2002094723A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/002Reclamation of contaminated soil involving in-situ ground water treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/08Reclamation of contaminated soil chemically
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/10Reclamation of contaminated soil microbiologically, biologically or by using enzymes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C2101/00In situ
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/722Oxidation by peroxides
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/727Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/78Treatment of water, waste water, or sewage by oxidation with ozone
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/32Hydrocarbons, e.g. oil
    • C02F2101/322Volatile compounds, e.g. benzene
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/36Organic compounds containing halogen
    • C02F2101/363PCB's; PCP's
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/06Contaminated groundwater or leachate
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00General aspects of water treatment
    • C02F2301/02Fluid flow conditions
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/06Nutrients for stimulating the growth of microorganisms
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/02Aerobic processes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/10Biological treatment of water, waste water, or sewage

Definitions

  • This invention relates to remediation systems, and more particularly to remediation systems for water, soil, and sediment bodies.
  • a remediation process includes generating microbubbles comprising a gas, coated with a thin layer of liquid compounds suitable for promoting biological degradation of organic compounds.
  • a remediation process includes generating microbubbles comprising a gas, coated with a thin layer of liquid compounds suitable for promoting chemical degradation of organic compounds and generation of microbubbles comprising a gas, coated with a thin layer of liquid compounds suitable for promoting biological degradation of organic compounds.
  • a remediation process includes generating microbubbles comprising a gas, coated with a thin layer of liquid compounds suitable for promoting chemical degradation of organic compounds wherein the microbubble is coated by introducing a liquid as an aerosol to a gas, which mixture is forced through a microporous material, resulting in the coated microbubble, and contacting the coated microbubble with the area to be remediated.
  • an apparatus for remediating a contaminated area using a liquid-coated microbubble including one or more gases includes an injection well and a source of a liquid suitable for promoting biological degradation of organic compounds.
  • the apparatus also includes a source for delivering a gas, an aerosolizer for aerosolizing the gas and a microporous diffuser disposed in the well for generating coated microbubbles of a controlled size comprising the gas and a liquid coating.
  • an aerosol head includes a reservoir of liquid and a tube supply with compressed air.
  • the head also includes a mixing chamber where the liquid is drawn into the flowing gas and a spray head which controls the particle size and distribution of the aerosols.
  • a microbubble includes a gas, coated with a thin layer of liquid compound suitable for promoting biological degradation of organic compounds.
  • One or more aspects of the invention may include one or more of the following advantages.
  • Thin-layer microbubbles with chemical or biological remediative characteristics can be selected and engineered for particular remediation applications.
  • the use of these coated microbubbles results in remediative processes wherein the microbubbles offer improved dispersion characteristics, improved reactivity characteristics, enhanced reestablishment of indigenous organisms in the treatment area, and broad applicability to a variety of treatment settings.
  • This invention relates to thin-layer coated microbubbles and their use, including remediation systems, and more particularly to remediation systems for water, soil, and sediment bodies.
  • the remediation can be in the form of chemical reaction (i.e., degradation) of various contaminants or in the form of enhancing environmental conditions, or the food or nutrient supply, to indigenous organisms (e.g., bacteria) in order to promote their activity in remediating the contaminants or by-products of the contaminant remediation.
  • FIG. 1 is a schematic of a Criegee oxidizer and nutribubble system.
  • FIG. 2 illustrates an example of a monitoring well screen modified for laminar diffuser injections.
  • FIG 3 illustrates a microbubble apparatus as used in soil/groundwater applications.
  • FIG. 4 is a schematic representation of a microbubble and processes within the microbubble.
  • FIG. 5 illustrates one depiction of a zone of influence by dissolved oxygen change showing gyre formation around a microporous diffuser well due to mixing of microbubbles.
  • FIG. 6 illustrates an example of remediation using compressed gas tanks instead of compressors to supply gas in non-power sites.
  • Contaminants are any agent that directly, or indirectly, has a detrimental effect on the environment or a living creature (e.g., human, animal, insect, plant). Contaminants include volatile organic compounds, non-volatile organic compounds, polyaromatic hydrocarbons
  • PAHs e.g., anthracene, fluoranthene, phenanthrene, naphthalene
  • PCBs polychlorinated biphenyls
  • chlorinated hydrocarbons e.g., tetrachloroethene, cis- and trans- dichloroethene, vinyl chloride, 1,1,1 -tri chloroethane, 1,1-dichloroethane, 1,2-dichloroethane, methylene chloride, chloroform, etc.
  • MTBE methyl tertiary-butyl ether
  • BTEX e.g., benzene, toluene, ethylbenzene, xylenes, and the like
  • explosive residues e.g., nitrobenzenes, RDX, trinitrotoluene (TNT), etc.
  • chlorinated pesticides e.g.,
  • Chemical reaction is any interaction between two or more chemicals resulting in a chemical change in the original reactants.
  • the reactions may be oxidative or reductive in nature.
  • the reaction can occur in any state, including the solid, gaseous, or liquid state or an interface thereof.
  • the reaction can be enhanced (e.g., efficiency improved, reaction rate increased) by addition of one or more catalysts.
  • Biological reactions are any reaction that involves a biological process (e.g., bacterial metabolism, bacterial growth or proliferation).
  • a biological process e.g., bacterial metabolism, bacterial growth or proliferation
  • certain organic compounds are subject to oxidative or reductive chemical degradation, resulting in lower molecular weight fragments or by-products. These by-products may be involved in bacterial metabolism such that they are "consumed” by the bacteria thereby undergoing a biological reaction or degradation.
  • the processes delineated herein provide nutrients (e.g., oxygen, nitrogen, carbon, phosphorous, potassium) such that bacterial growth, support, or proliferation can occur upon consumption of the nutrients. These are also considered biological reactions.
  • oxidative chemical reaction conditions such as ozone
  • oxygen as a by-product (e.g., reduction of ozone to oxygen), which can act as feed for certain indigenous bacteria in the remediation area.
  • Such enhancement of biological function, or bioremediation, is also considered within the scope of biological reaction.
  • injection well treatment system 10 includes microporous diffusers 12 disposed through an injection well to treat subsurface waters of an aquifer.
  • the arrangement 10 includes a well 14 having a casing 16 with an inlet screen 18 and outlet screen 20 to promote a recirculation of water into the casing 16 and through the surrounding ground area.
  • the casing 16 supports the ground and aquifer about the well.
  • Disposed through the casing is the microporous diffuser 12.
  • the injection well treatment system 10 includes master unit 22, which includes a controller 31, an air compressor 32, a compressor/pump control mechanism 34, and an ozone (O ) generator 36.
  • Microporous diffuser s 12 are in communication with master unit 22 by way of gas transfer line 24 and liquid transfer line 26, each of which is a pipe made of suitable material to accommodate transfer of the appropriate fluid to microporous diffusers 12.
  • the air compressor 32 can feed a stream of air into the microporous diffuser 12 whereas, the compressor pump control 34 feeds a stream of air mixed with ozone (O ) from the ozone generator 36 into microporous diffuser 12 to affect substantial removal of contaminants.
  • the treatment system 10 also includes a pump 38 that supplies a liquid decontamination agent such as hydrogen peroxide as well as nutrients such as biologically promotion agents, including carbon, nitrogen, phosphorous or potassium sources, from a source 39.
  • the system 10 can also supply catalyst agents such as iron containing compounds such as iron silicates or palladium containing compounds such as palladized carbon, hi addition, other materials such as platinum may also be used.
  • the treatment system 10 makes use of a gas-gas reaction of contaminant vapors and ozone (described below) that can be supplemented with a liquid phase reaction.
  • the use of hydrogen peroxide as a thin film coating on the bubbles promotes the decomposition rate by adding a secondary liquid phase reactive interface as volatile compounds enter the gaseous phase. It also expands the types of compounds that can be effectively removed.
  • the pump control 38 can simply feed water.
  • the biological nutrients can aid in the promotion of growth of bacteria to aid in bioremediation after treatment with ozone as described below.
  • Remediation using the equipment and techniques delineated herein can be performed to a variety of areas, including, for example, bodies of water (e.g., ground, surface, supply conduits including pipe systems), soil areas (saturated or unsaturated with liquids, e.g., water), and collections of sediments.
  • a suitable area for remediation using the ozone/nutribubble technique is one in which the hydraulic conductivity of the geologic formation is between 10 " ' and 10 "6 cm/sec.
  • the remedial area is first treated with ozone/air microbubbles coatee with hydroperoxide if necessary for specific bond cleavage or increase in oxidative potential.
  • Ozone reacts in an aqueous and gaseous form to degrade aromatic ring compounds (BTEX) and certain ethers (MTBE). It also breaks apart long-chain aliphatic compounds.
  • BTEX aromatic ring compounds
  • MTBE certain ethers
  • oxygen-enriched air bubbles are coated with a nutrient mixture and injected into the aquifer.
  • the fine bubbles serve to assist in pumping the nutrients through the capillary structure of the formation being treated.
  • the bubbles assist in removing CO 2 as well as supplying oxygen for respiration.
  • Nutribubbles are any coated microbubble wherein the gas in the bubble, the thin-layer bubble coating, or combinations thereof, include a nutrient (e.g., oxygen, nitrogen, carbon source, phosphorus source), that is, a material that is useful for enhancement of the survival, growth, or proliferation of an organism, such as bacteria.
  • a nutrient e.g., oxygen, nitrogen, carbon source, phosphorus source
  • Introduction of the ozone/nutribubbles is accomplished by the microporous diffusers, which receive the simultaneous supply of gas and liquid.
  • the pulsed injection of gas through the diffuser eliminates the common problem of plugging of injection wells. Pulsing refers to a systematic, or cyclic, sequence of injection of a material into the remediation area.
  • a sequence can be invoked wherein a treatment area is injected with the coated microbubbles delineated herein, followed by injection (or pumping) of water, followed by a rest period, whereupon the sequence is commenced again, and repeated in periodic cycles (e.g., 15-30 minute intervals).
  • periodic cycles e.g. 15-30 minute intervals.
  • the injection well can be a monitoring well, where a microporous diffuser is placed to take advantage of the existing well.
  • a modified well screen having a laminar diffuser is illustrated.
  • the modified well screen is comprised of screened PVC pipe having a 0.02 in. slot size with a inflated packer to produce an isolated portion of the well screen disposed between a microporous diffuser and upper portions of the well. Bentonite is disposed about the inflated packer.
  • the microporous diffuser receives gas (e.g., air/ozone, nitrogen) and liquid (e.g., hydroperoxide or nutrients) in transfer lines otherwise using an apparatus similarly to that described in FIG. 1.
  • an alternative microbubble apparatus 40 useful in soil/groundwater remediation applications includes an aerosolizer 42, a mixing chamber 44 and a T-junction 46.
  • the apparatus 40 includes the elements of the system of FIG. 1 namely, microporous diffusers 12 disposed through an injection well 14.
  • the well 14 has a casingl ⁇ that can have an inlet screen (not shown) and outlet screen (not shown) to promote a recirculation of water into the casing 16 and through the surrounding ground area.
  • the injection well treatment system 10 also includes an air compressor 32, a compressor/pump control mechanism 34, and an ozone (O3) generator 36.
  • the compressor pump control 34 feeds a stream of air mixed with ozone (O3) from the ozone generator 36 into microporous diffuser 12 via through the aerosolizer 42 and the mixing chamber 44. A major portion of the liquid stream goes directly to the mixing chamber whereas a minor portion goes to the aerosolizer.
  • the aerosolizer also receives a liquid steam of a decontaminant liquid e.g., hydrogen peroxide, or other liquid oxidizer and/or biological nutrients from a source 50.
  • the mixing chamber 44 is coupled to the well head 48.
  • the coated microbubble 52 includes a gas region 56 surrounded by thin-layer coating 54. Aerosol particles 58 are dispersed within the gas region and within the thin-layer coating 54.
  • Thin-layer coating 54 includes one or more components, such as oxidants, catalysts, acids, or nutrients.
  • coated microbubbles 52 diffuse throughout the treatment area (e.g., aquifer, ground water, soil, sediment). For example, coated microbubbles 52 can travel through capillary networks (or pores) in the soil. Within the capillary networks, coated microbubbles 52 contact groundwater (in saturated soil) within the capillary network.
  • the coated microbubbles 52 Upon contact with the groundwater, the coated microbubbles 52 react with the organic chemicals (or other contaminants) in the groundwater, thus leading to degradation of the organic chemicals or contaminants.
  • the coated microbubbles 52 can also diffuse in unsaturated soil capillary networks, where the pores are predominately gaseous containing.
  • a schematic representation of a microbubble 60 is shown, wherein ozone is the gas and hydroperoxide is the liquid.
  • the microbubble 60 has a gas region 68, and a thin-layer coating 64 defined by an internal interface 62 and an external interface 66.
  • the gas region 68 includes ozone gas.
  • Criegee-like oxidation processes occur at the interfaces of the thin-layer coating 64 such that the thin-layer coating can include both reactants (e.g., hydroperoxide) as well as Criegee oxidation by-products (e.g., hydroxide radicals, peroxy acids) resulting from the interaction of ozone and hydroperoxide.
  • Thin-layer coating 64 advantageously provides for these reactants and byproducts to remain in proximity to allow further reaction and to facilitate more efficient interaction of the reactants with the organic compounds or contaminants.
  • the various partitioning effects of the solid-liquid-gas phases of coated microbubble 60 are also illustrated.
  • solubility gas-aqueous partitioning
  • aqueous-gas partitioning governed by Henry's Constant
  • Adsorption gas-solid, liquid-solid
  • stripping solid-gas
  • solubility solid-aqueous
  • Ozone has an action similar to steaming of soils in reducing indigenous bacterial populations within 10 ft. (ca. 3 m) of the injection well, while additionally degrading organics to more readily attackable forms.
  • Ozone also naturally decomposes to oxygen, theoretically supplying up to ten times the dissolvable oxygen content found with direct air injection.
  • Oxygen-enriched air injection with nutrients purges the remaining ozone residual, allowing indigenous bacterial species capable of organic residue metabolism to quickly expand through the formation.
  • FIG. 5 illustrates an example of how coated microbubbles diffuse in a treatment area.
  • injection well system 71 is a system similar to those described, for example, in FIG. 1 or FIG.6 herein. It has a microporous diffuser 12 for release of the coated microbubbles.
  • Monitoring wells 73 (depicted as KV-1, KV-2, KV-3, KV-4, KV-5, and KV-6) are used to monitor the products and by-products produced after coated microbubble treatment.
  • the coated microbubbles flow (and displace water in a similar flow pattern) in patterns depicted as flow patterns 75, 76, and 77. In this manner, mixing of the coated microbubbles in the treatment area occurs.
  • Over time e.g., 3 days
  • these flow patterns result in oxidative reaction zones 78 and 79, respectively.
  • These reactive zones are areas in which the coated microbubbles have caused more concentrated degradation due to more focused contact and reactivity.
  • the dispersion of the coated microbubbles is not limited to these reactive zones exclusively, rather the coated microbubbles are capable of flowing in all directions.
  • FIG 6 illustrates an example of how the injection well treatment system can be modified for non-power accessible sites.
  • Well treatment system 80 includes elements of the system of FIG. 1, including microporous diffusers 12 disposed through an injection well 14.
  • the liquid coating material is supplied by compressed gas tank 82 in communication with cap 90.
  • Liquid supply 84 provides the coating materials (e.g., oxidants, catalysts, nutrients) via siphon line 92 to cap 90, which can be performed with or without application of pressure (i.e., with or without a compressor).
  • a gas in compressed gas tank 86 is transferred via tubing through valve and flow meter assembly 88 to cap 90.
  • the cap 90 is in communication with microporous diffusers 12 via gas and liquid transfer lines 22 and 24, respectively, and combination of the gas and liquid result; in generation of coated microbubbles.
  • Microbiological degradation is a technique to degrade complex organic compounds.
  • the rate of reaction depends upon the type of microbe, the substrate compound targeted as food, and the rate of gaseous exchange. Bubbling oxygen-enriched air through an aqueous solution of substrate compound, supplied with the nutrients nitrogen (N), phosphorus (P), and potassium (K), can encourage rapid metabolism and reproduction of microbes, which consume the organic compounds.
  • N nitrogen
  • P phosphorus
  • K potassium
  • C carbon
  • N nitrogen
  • P phosphorus
  • K potassium
  • the basic microbial process of biodegradation (aerobic) can be portrayed as a conversion of oxygen (O 2 ) to CO 2 and water plus more bacteria:
  • the choice of oxidants can be used to tailor the remediation process for a selected class of chemical compounds, thus allowing one to design a remediation system for a particular application. This is accomplished by an analysis of the volatile organic compound to be remediated, taking into account its Henry's Constant value (see, Tables 1 and 2), which is an indicator of its proclivity to move from the liquid to the gaseous phase of an interface. By matching this transfer rate with that of the reactivity rate of a particular oxidant, the remediation process can be tailored such that the particular volatile organic compound is optimally reacted (and therefore remediated) relative to other volatile organic compounds present.
  • the rate of biodegradation in natural formations is very slow compared to above-ground settings.
  • the ability to mix gases, electron donors, or nutrients with organic contaminates is limited by the porosity and hydraulic conductivity of saturated soils. Porous soils tend to encourage movement of liquids as slugs, not easily mixing with existing groundwater.
  • the rate of natural movement is slow and determined by existing groundwater gradients. Velocities of natural flows commonly run 0.1 to 2 ft/day.
  • the natural flow across a 100 ft wide contaminant zone may take 50 to 1000 days.
  • the capability to remove product waste products is similarly hindered.
  • “laminated” Microporous Spargepoint® diffuser (Model Nos. SPT2000 and SPT2010), available from K-V Associates, Inc., Mashpee, MA) or by introducing aerosolized liquid particles into the gas stream supplying a diffuser. While not being bound by theory, generally, coatings made by forcing the microbubble through the liquid stream result in relatively thicker coatings caused, in part, by the thicker reaction points of the liquid forced through the gaseous phase in the diffuser.
  • those generated by the aerosol method result in microbubbles with relatively thinner coatings caused, in part, by the finer porous points of the liquid when introduced as an aerosol.
  • Thicker coatings generally elevate the reactivity of the microbubble, particularly in oxidative reactivity.
  • thicker coatings of oxidative material is associated with increased Criegee oxidative capacity or oxidative potential (see, Dowideit and supra, Environ. Sci.
  • the thickness of a coating can be ascertained by techniques such as microscopic capillary analysis of the microbubbles with dyes (e.g., India ink), backlighting, or photoelectric cell detection methods.
  • the microbubbles can include a thin-layer coating having a material suitable for oxidative reactivity.
  • high oxidative capacity or “advanced oxidative” systems are capable of particularly efficient chemical reactivity (e.g., bond breaking capacity, carbon- containing compound reactivity) useful in contaminant degradation processes. These reactions are characterized in that they have oxidation potentials in excess of 2.0 (based on electrochemical reactions at 25 °C).
  • microbubbles delineated herein are advantageous in that they can be designed to optimize their suitability for certain applications in remediation technology.
  • the microbubbles can be formed and shaped in the various manners described above (e.g., using a microporous diffuser, or aerosolized liquid and a microporous diffuser). Depending on their size and thickness, certain reactivity profiles can be achieved.
  • the composition of the gas in the bubble, as well as the type of liquid coating selected can be chosen to accomplish various oxidative or reductive degradation profiles, and catalysts (e.g., metals in microparticle form, acids) can be incorporated into the microbubble to increase reactivity and degradation efficiency of the microbubble.
  • the methods of generating microbubbles allow for control of the stoichiometry of the chemical components in the microbubble, again allowing for the ability to tailor the microbubble to a specific profile for a desired application or reactivity
  • the thickness of the coating can be increased
  • the strength of oxidation capacity can be effected by increasing the concentration of hydrogen peroxide in the liquid phase as well as increasing the ozone content in the gas phase.
  • the size of the microbubble can also be varied by controlling the pressure of the gas during generation of the microbubble and by choice of the diffuser pore size. For example, by generating smaller coated microbubbles, the surface to volume ratio increases, which improves reactivity of the microbubble. Additionally, in instances where a coating thickness is held constant, a smaller coated microbubble effectively has a "thicker" coating relative to a larger coated microbubble, thus resulting in a coated microbubble with a "thicker" coating and greater surface area (relative to volume), which both contribute to increased reactivity (e.g., in oxidative coating applications, higher oxidative potential). Normally, the range of fluid to gas varies from parity (1:1) to about 1 :100. This corresponds to a coating thicken of 0.3 (30%) increase in radius down to 0.01 (1%). Table 3 illustrates the relationship between gas and liquid volumes and variance in the coating thickness.
  • Microbubbles can also be selected according to a controlled size using a layered fine bubble production chamber.
  • the layered fine bubble production chamber is a chamber in which a liquid is placed under pressure and microbubbles are generated. That is, over a period of time, an environment is provided where the microbubbles segregate by size (e.g., larger microbubbles rise and smaller microbubbles remain) thus allowing a mixture predominated by a particular microbubble size (or size range) to be established prior to injection into the treatment area. This is suitable for use, for example, where smaller microbubbles may be desired (i.e., for their higher surface to volume ratio).
  • One example of such control relates to the "Law of the Minimum", which states that bacterial growth will stop when the nutrient that was present in the lowest concentration (relative to the requirement) is exhausted, becomes a problem since the rest of the mixture is useless. If that substance is replenished, growth will stop when the next substance is exhausted.
  • the rate of metabolism can be adjusted and maximized.
  • the methods herein can be applied such that an existing monitoring well can be used as an injection well for the microbubble diffuser.
  • Microbubbles form a unique physical and chemical environment which can effectively treat waterborne or attached (adsorbed) volatile organic compounds (VOCs).
  • Diffusers, or spargers, placed in groundwater or saturated soil provide extremely small "microbubbles" with a very high surface area to volume ratio. This high surface area to volume ratio maximizes the VOC transfer from the liquid phase to gas phase. If the air bubbles are filled with an oxidizing gas, like ozone, the VOCs react with the ozone and are destroyed while still in the water column. This "in-situ"- combined VOC recovery and destruction not only obviates the need for an additional process step but also enhances the physical and chemical kinetics of the process.
  • Microporous diffusers suitable for use in the methods described herein are those having the ability to deliver a gas and a liquid such that microbubbles less than about 200 microns, preferably between about 0.5 and 200 microns, are produced including the gas therein and a thin layer of the liquid material coating the microbubble.
  • the diffuser can be constructed of a variety of materials suitable for the gases and liquids to be delivered, such materials include, for example, stainless steel, high-density polyethylene (HDPE), low-density polyethylene (LDPE), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE, e.g., TEFLON), acetal (e.g.,
  • the diffuser can include concentric tubes of microporous material, optionally having additional packing materials (e.g., hydrophobic plastics, hydrophilic plastics, beads, interconnected fibers) sandwiched between the tubes to facilitate creation of the gas-liquic interface in the microbubble.
  • additional packing materials e.g., hydrophobic plastics, hydrophilic plastics, beads, interconnected fibers
  • These materials aid the liquid coating process of the gas flowing through the diffuser in the generation of microbubbles, in part by their hydrophilic or hydrophobic nature to enhance coating, and in part by their ability to increase the positioning of the liquid to optimize contact with the gas flowing through .
  • diffusers suitable for use in the methods delineated herein include the laminar microporous SPARGEPOINT ⁇ diffusei or the C-SPARGER® diffuser (both available from K-V Associates, Inc., Mashpee, MA). Aerosols or aerosolized liquid particles are one method by which coated microbubbles can be formed. The aerosolized particles are produced using an aerosolizer (see, FIG. 3), including any apparatus suitable for providing an aerosolized form of a liquid (e.g., a commercial airbrush Badger 150).
  • the aerosolized liquid particles can be any suitable for use in the coating application (i.e., chemical or biological reaction) and remediation process of interest, including for example, oxidants (e.g., hydroperoxides, potassium permanganate, Fenton's reagent (hydrogen peroxide and Fe(II))), catalysts (e.g., as delineated below), acids, (e.g., acetic, lactic), and nutrients (e.g., as delineated below).
  • oxidants e.g., hydroperoxides, potassium permanganate, Fenton's reagent (hydrogen peroxide and Fe(II)
  • catalysts e.g., as delineated below
  • acids e.g., acetic, lactic
  • nutrients e.g., as delineated below.
  • the aerosol can be generated using an aerosol head including a reservoir of liquid or liquid and microfine particles mixture; a siphon tube made of e.g., TEFLON or resistant flexible plastic; a tube supply with compressed air; a mixing chamber where the liquid is drawn into the flowing gas; a spray head which controls the particle size and distribution of the aerosols; and a compression fitting which directs the aerosol flow into the air/ozone gas stream.
  • the mixing chamber can be, for example, a Bernoulli chamber, that is, any chamber that (in accordance with Bernoulli's principle) is capable of compressing a fluid through a narrower opening into a larger chamber resulting in a variance in pressure.
  • the aerosol head can further include connecting tubing such as TEFLON tubing 3/8" to V" in diameter, polyvinyl chloride tubing ! 2 " to 1" in diameter, with o-ring seals (e.g., VITON) and threaded 5 ft. sections.
  • the aerosol head is in communication with the microporous diffusers, in a manner to maintain a sufficient rate of gas flow to avoid condensing of the aerosol flow.
  • the aerosol spray head can e adjustable to vary the liquid flow feed rate from between about 1/10 to 1/10,000 of the flow of the air/ozone volume flow. Also, the aerosol flow can be introduced continuously with the air/ozone flow.
  • Catalysts are any material that is useful in catalyzing the desired chemical transformation or process to promote quicker or more efficient reaction.
  • the catalysts are presented as micron- sized particles to augment the interface region of the microbubble.
  • transition metals including palladium (Pd), manganese (Mn), and iron (Fe), in elemental or salt forms; sulfur compounds including sulfates and sulfides.
  • the acidity of reactions processes can be modified to enhance reactivity, and therefore the remediation processes herein.
  • chemical reactions i.e., remediation processes
  • the microbubbles can be coated with an acidic coating, thus, lowering the pH of the interface and increasing the reaction rate and efficiency of the remediation process.
  • the acid can also be incorporated in a coating having other liquids in it where beneficial (e.g., increased reactivity, efficiency) chemical effects can be realized, for example, acid and iron (II or III) salts (e.g., Fenton's reagent), which in combination can catalyze the oxidative reactivity of the coated microbubble.
  • the gases useful in the microbubbles are any that are suitable for chemical or biological reaction and remediation.
  • gases for example, in oxidative applications, ozone, oxygen and air are suitable gases.
  • nitrogen or hydrogen can be used.
  • the gas suitable for an application is dependent , in part, on criteria such as the reaction desired, or the bacterial growth requirements (aerobic or anaerobic).
  • the gas can be generated in situ (e.g., ozone generator), provided using a compressor, or provided via compressed tanks (e.g., .
  • Nutrient coatings on the microbubbles are any suitable nutrient for bacterial (aerobic or anaerobic) growth.
  • Such nutrients include, for example, carbon sources (e.g., carbohydrates, sugars, beer, milk products, methanogens, organic acids such as acetic and lactic acids, organic esters such as acetates, proprionates, organic ketones such as acetone), nitrogen sources (e.g., ammonia, nitrates, ammonium nitrate), phosphorous sources (e.g., soluble phosphates, etc), and potassium sources (e.g., 10,000 ppm of lactate; 680 ppm NH 4 NO ; 200 ppm KH 2 PO to provide sources of carbon and nitrogen, and phosphorus and potassium).
  • carbon sources e.g., carbohydrates, sugars, beer, milk products, methanogens, organic acids such as acetic and lactic acids, organic esters such as acetates, proprionates, organic ketones such as
  • environments suitable for bacterial support and growth are made up of the nutrients in the following relative ratios: carbon (ca. 1000 parts), nitrogen (ca. 150 parts), phosphorous (ca. 30 parts), sulfur, potassium, and sodium (ca. 10 parts each), calcium, magnesium, and chloride (ca. 5 parts each), iron (ca. 2 parts), and any remainder elements in trace amounts, with the ratios based on molar equivalents, which may be in the form of either elemental or ionic (i.e., salt) forms, or a combination thereof.
  • Advantageous aspects of the invention include: 1) gas/liquid thin-layer microbubble oxidation to predigest and sterilize around injection locations; 2) simultaneous injection of nutrients and food source with gas in proportion to optimal ratio for assimilation; 3) injection of nutrients to provide a coating (thin layer) on gas (oxygen-enriched air) being injected into porous soil capillaries; 4) introduction in a pulsed manner with microbubbles of 5 to 100 micron diameter sized to pores of soil to avoid fracturing of soil and to enhance transport through capillary-like soil voids; 5) use of microporous diffusers (e.g., Spargepoint®) or aerosolized liquids and microporous diffusers for simultaneous introduction of gas and liquid mixtures into coated microbubbles engineered for specific characteristics (e.g., size, shape, reactivity, composition).
  • microporous diffusers e.g., Spargepoint®
  • aerosolized liquids and microporous diffusers for simultaneous introduction of gas and liquid mixtures into
  • Initial bench-scale testing included putting approximately 5 grams of soil sample in a 40 ml VOA vial with 30 ml of water and allowing headspace to develop, then screening the headspace in an HNu Systems Model 321 portable gas chromatograph. The purpose of this step was to extrapolate the volume of soil necessary to produce an instrument response in the GC that was noticeable for further testing.
  • Subsequent testing included stirring approximately 40 grams of soil sample in 500 ml of water contained in an Erlenmeyer flask and subjecting the entire solution to sparged air containing approximately 100 ppmv of ozone. This test was conducted under 0 psig with aqueous samples collected from the test cell at time intervals of 0, 2, 5, 10, 15, and 20 minutes and field screened with portable gas chromatograph for ionizable compounds. Following the above preliminary bench-scale tests, further testing was conducted in a larger glass volume container to allow for split sampling of soil and groundwater samples to a certified laboratory for confirmatory analyses.
  • This test cell included mounting a stopper on the 1,000 ml container and drilling holes in the stopper to allow for various tubing diameters to pass through the stopper to accommodate: an external pressure gauge T'd with a pressure relief valve; a sample guideport to permit below-water-level aqueous sampling; a gas line for a mini- laminate Spargepoint® (1.5 inch in height and 1.5 inch in diameter); and injection of treatment liquids such as a 3% solution of hydroperoxide or peracid precursor.
  • FIG. 1 presents a schematic diagram of the K-V Associates
  • Criegee oxidizer with simultaneous liquid and gas supply The individual diffusers (e.g., Spargepoints®) are drilled into the contaminated aquifer region to be treated.
  • the timer- controller delivers liquid and gas simultaneously.
  • the number of diffusers (e.g., Spargepoints®) depend upon the volume to be treated.
  • the microbubble operating system is used to field treat about 1 cubic meter of saturated soil contained in a plastic trash bin runs on house current (120 volts AC, 15 amp).

Abstract

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

Description

Environmental Remediation Method and Apparatus
TECHNICAL FIELD
This invention relates to remediation systems, and more particularly to remediation systems for water, soil, and sediment bodies.
BACKGROUND
There is a well-recognized need for remediation, or clean-up, of contaminants (e.g., chemicals) that exist in a variety of settings, including ground and surface water, aquifers, water supply pipes, soil, and sediment collections. These settings are frequently contaminated with various constituents such as volatile organic compounds (VOCs). These contaminated areas pose a threat to the environment, and ultimately to the health and safety of all living creatures. Thus, equipment and methods for effectively and safely dealing with remediation of environmental contaminants is of significant importance.
SUMMARY
According to one aspect of the invention, a remediation process includes generating microbubbles comprising a gas, coated with a thin layer of liquid compounds suitable for promoting biological degradation of organic compounds.
According to another aspect of the invention, a remediation process includes generating microbubbles comprising a gas, coated with a thin layer of liquid compounds suitable for promoting chemical degradation of organic compounds and generation of microbubbles comprising a gas, coated with a thin layer of liquid compounds suitable for promoting biological degradation of organic compounds.
According to another aspect of the invention, a remediation process includes generating microbubbles comprising a gas, coated with a thin layer of liquid compounds suitable for promoting chemical degradation of organic compounds wherein the microbubble is coated by introducing a liquid as an aerosol to a gas, which mixture is forced through a microporous material, resulting in the coated microbubble, and contacting the coated microbubble with the area to be remediated.
According to another aspect of the invention, an apparatus for remediating a contaminated area using a liquid-coated microbubble including one or more gases includes an injection well and a source of a liquid suitable for promoting biological degradation of organic compounds. The apparatus also includes a source for delivering a gas, an aerosolizer for aerosolizing the gas and a microporous diffuser disposed in the well for generating coated microbubbles of a controlled size comprising the gas and a liquid coating.
According to another aspect of the invention, an aerosol head includes a reservoir of liquid and a tube supply with compressed air. The head also includes a mixing chamber where the liquid is drawn into the flowing gas and a spray head which controls the particle size and distribution of the aerosols.
According to another aspect of the invention, a microbubble includes a gas, coated with a thin layer of liquid compound suitable for promoting biological degradation of organic compounds.
One or more aspects of the invention may include one or more of the following advantages. Thin-layer microbubbles with chemical or biological remediative characteristics, can be selected and engineered for particular remediation applications. The use of these coated microbubbles results in remediative processes wherein the microbubbles offer improved dispersion characteristics, improved reactivity characteristics, enhanced reestablishment of indigenous organisms in the treatment area, and broad applicability to a variety of treatment settings.
This invention relates to thin-layer coated microbubbles and their use, including remediation systems, and more particularly to remediation systems for water, soil, and sediment bodies. The remediation can be in the form of chemical reaction (i.e., degradation) of various contaminants or in the form of enhancing environmental conditions, or the food or nutrient supply, to indigenous organisms (e.g., bacteria) in order to promote their activity in remediating the contaminants or by-products of the contaminant remediation.
The details of one or more embodiments of the invention are set forth in the accompa- nying drawings and the description below. Other features, objects, and advantages of the invention will be apparent from the description and drawings, and from the claims. DESCRIPTION OF DRAWINGS
FIG. 1 is a schematic of a Criegee oxidizer and nutribubble system.
FIG. 2 illustrates an example of a monitoring well screen modified for laminar diffuser injections. FIG 3 illustrates a microbubble apparatus as used in soil/groundwater applications.
FIG. 4 is a schematic representation of a microbubble and processes within the microbubble.
FIG. 5 illustrates one depiction of a zone of influence by dissolved oxygen change showing gyre formation around a microporous diffuser well due to mixing of microbubbles. FIG. 6 illustrates an example of remediation using compressed gas tanks instead of compressors to supply gas in non-power sites.
DETAILED DESCRIPTION
Contaminants are any agent that directly, or indirectly, has a detrimental effect on the environment or a living creature (e.g., human, animal, insect, plant). Contaminants include volatile organic compounds, non-volatile organic compounds, polyaromatic hydrocarbons
(PAHs) (e.g., anthracene, fluoranthene, phenanthrene, naphthalene); polychlorinated biphenyls (PCBs)(e.g., arochlor 1016); chlorinated hydrocarbons (e.g., tetrachloroethene, cis- and trans- dichloroethene, vinyl chloride, 1,1,1 -tri chloroethane, 1,1-dichloroethane, 1,2-dichloroethane, methylene chloride, chloroform, etc.); methyl tertiary-butyl ether (MTBE); and BTEX (e.g., benzene, toluene, ethylbenzene, xylenes, and the like); explosive residues (e.g., nitrobenzenes, RDX, trinitrotoluene (TNT), etc.); and chlorinated pesticides (e.g., chlordane, heptachlor, etc.). The microbubbles, apparatuses, and methods herein are useful in remediating contaminants, including any one, or combination of, those delineated herein.
Chemical reaction is any interaction between two or more chemicals resulting in a chemical change in the original reactants. The reactions may be oxidative or reductive in nature. The reaction can occur in any state, including the solid, gaseous, or liquid state or an interface thereof. The reaction can be enhanced (e.g., efficiency improved, reaction rate increased) by addition of one or more catalysts.
Biological reactions are any reaction that involves a biological process (e.g., bacterial metabolism, bacterial growth or proliferation). For example, in the processes delineated herein, certain organic compounds are subject to oxidative or reductive chemical degradation, resulting in lower molecular weight fragments or by-products. These by-products may be involved in bacterial metabolism such that they are "consumed" by the bacteria thereby undergoing a biological reaction or degradation. In other instances, the processes delineated herein provide nutrients (e.g., oxygen, nitrogen, carbon, phosphorous, potassium) such that bacterial growth, support, or proliferation can occur upon consumption of the nutrients. These are also considered biological reactions. Further, certain processes delineated herein using oxidative chemical reaction conditions, such as ozone, result in oxygen as a by-product (e.g., reduction of ozone to oxygen), which can act as feed for certain indigenous bacteria in the remediation area. Such enhancement of biological function, or bioremediation, is also considered within the scope of biological reaction.
Referring to FIG. 1, injection well treatment system 10 includes microporous diffusers 12 disposed through an injection well to treat subsurface waters of an aquifer. The arrangement 10 includes a well 14 having a casing 16 with an inlet screen 18 and outlet screen 20 to promote a recirculation of water into the casing 16 and through the surrounding ground area. The casing 16 supports the ground and aquifer about the well. Disposed through the casing is the microporous diffuser 12. The injection well treatment system 10 includes master unit 22, which includes a controller 31, an air compressor 32, a compressor/pump control mechanism 34, and an ozone (O ) generator 36. Microporous diffuser s 12 are in communication with master unit 22 by way of gas transfer line 24 and liquid transfer line 26, each of which is a pipe made of suitable material to accommodate transfer of the appropriate fluid to microporous diffusers 12. The air compressor 32 can feed a stream of air into the microporous diffuser 12 whereas, the compressor pump control 34 feeds a stream of air mixed with ozone (O ) from the ozone generator 36 into microporous diffuser 12 to affect substantial removal of contaminants. The treatment system 10 also includes a pump 38 that supplies a liquid decontamination agent such as hydrogen peroxide as well as nutrients such as biologically promotion agents, including carbon, nitrogen, phosphorous or potassium sources, from a source 39.
The system 10 can also supply catalyst agents such as iron containing compounds such as iron silicates or palladium containing compounds such as palladized carbon, hi addition, other materials such as platinum may also be used. The treatment system 10 makes use of a gas-gas reaction of contaminant vapors and ozone (described below) that can be supplemented with a liquid phase reaction. The use of hydrogen peroxide as a thin film coating on the bubbles promotes the decomposition rate by adding a secondary liquid phase reactive interface as volatile compounds enter the gaseous phase. It also expands the types of compounds that can be effectively removed. Alternatively, the pump control 38 can simply feed water. In addition, the biological nutrients can aid in the promotion of growth of bacteria to aid in bioremediation after treatment with ozone as described below.
Remediation using the equipment and techniques delineated herein can be performed to a variety of areas, including, for example, bodies of water (e.g., ground, surface, supply conduits including pipe systems), soil areas (saturated or unsaturated with liquids, e.g., water), and collections of sediments. A suitable area for remediation using the ozone/nutribubble technique is one in which the hydraulic conductivity of the geologic formation is between 10"' and 10"6 cm/sec. In one embodiment, the remedial area is first treated with ozone/air microbubbles coatee with hydroperoxide if necessary for specific bond cleavage or increase in oxidative potential.
Ozone reacts in an aqueous and gaseous form to degrade aromatic ring compounds (BTEX) and certain ethers (MTBE). It also breaks apart long-chain aliphatic compounds. Following removal of BTEX/MTBE compounds, oxygen-enriched air bubbles are coated with a nutrient mixture and injected into the aquifer. The fine bubbles serve to assist in pumping the nutrients through the capillary structure of the formation being treated. The bubbles assist in removing CO2 as well as supplying oxygen for respiration. Nutribubbles are any coated microbubble wherein the gas in the bubble, the thin-layer bubble coating, or combinations thereof, include a nutrient (e.g., oxygen, nitrogen, carbon source, phosphorus source), that is, a material that is useful for enhancement of the survival, growth, or proliferation of an organism, such as bacteria. Introduction of the ozone/nutribubbles is accomplished by the microporous diffusers, which receive the simultaneous supply of gas and liquid. The pulsed injection of gas through the diffuser eliminates the common problem of plugging of injection wells. Pulsing refers to a systematic, or cyclic, sequence of injection of a material into the remediation area. For example, in the methods delineated herein, a sequence can be invoked wherein a treatment area is injected with the coated microbubbles delineated herein, followed by injection (or pumping) of water, followed by a rest period, whereupon the sequence is commenced again, and repeated in periodic cycles (e.g., 15-30 minute intervals). In this manner, a "pressure wave" is effectively produced that assists in dispersion of the microbubbles through the treatment area.
The injection well can be a monitoring well, where a microporous diffuser is placed to take advantage of the existing well. Referring to FIG. 2, a modified well screen having a laminar diffuser is illustrated. The modified well screen is comprised of screened PVC pipe having a 0.02 in. slot size with a inflated packer to produce an isolated portion of the well screen disposed between a microporous diffuser and upper portions of the well. Bentonite is disposed about the inflated packer. The microporous diffuser receives gas (e.g., air/ozone, nitrogen) and liquid (e.g., hydroperoxide or nutrients) in transfer lines otherwise using an apparatus similarly to that described in FIG. 1.
Referring to FIG. 3, an alternative microbubble apparatus 40 useful in soil/groundwater remediation applications includes an aerosolizer 42, a mixing chamber 44 and a T-junction 46. The apparatus 40 includes the elements of the system of FIG. 1 namely, microporous diffusers 12 disposed through an injection well 14. The well 14 has a casinglό that can have an inlet screen (not shown) and outlet screen (not shown) to promote a recirculation of water into the casing 16 and through the surrounding ground area. The injection well treatment system 10 also includes an air compressor 32, a compressor/pump control mechanism 34, and an ozone (O3) generator 36. The compressor pump control 34 feeds a stream of air mixed with ozone (O3) from the ozone generator 36 into microporous diffuser 12 via through the aerosolizer 42 and the mixing chamber 44. A major portion of the liquid stream goes directly to the mixing chamber whereas a minor portion goes to the aerosolizer. The aerosolizer also receives a liquid steam of a decontaminant liquid e.g., hydrogen peroxide, or other liquid oxidizer and/or biological nutrients from a source 50. The mixing chamber 44 is coupled to the well head 48.
Still referring to FIG 3, the coated microbubble 52 includes a gas region 56 surrounded by thin-layer coating 54. Aerosol particles 58 are dispersed within the gas region and within the thin-layer coating 54. Thin-layer coating 54 includes one or more components, such as oxidants, catalysts, acids, or nutrients. Upon leaving microporous diffuser 12, coated microbubbles 52 diffuse throughout the treatment area (e.g., aquifer, ground water, soil, sediment). For example, coated microbubbles 52 can travel through capillary networks (or pores) in the soil. Within the capillary networks, coated microbubbles 52 contact groundwater (in saturated soil) within the capillary network. Upon contact with the groundwater, the coated microbubbles 52 react with the organic chemicals (or other contaminants) in the groundwater, thus leading to degradation of the organic chemicals or contaminants. The coated microbubbles 52 can also diffuse in unsaturated soil capillary networks, where the pores are predominately gaseous containing.
Referring to FIG. 4, a schematic representation of a microbubble 60 is shown, wherein ozone is the gas and hydroperoxide is the liquid. The microbubble 60 has a gas region 68, and a thin-layer coating 64 defined by an internal interface 62 and an external interface 66. In ozone/hydroperoxide combinations, the gas region 68 includes ozone gas. Criegee-like oxidation processes occur at the interfaces of the thin-layer coating 64 such that the thin-layer coating can include both reactants (e.g., hydroperoxide) as well as Criegee oxidation by-products (e.g., hydroxide radicals, peroxy acids) resulting from the interaction of ozone and hydroperoxide. Thin-layer coating 64 advantageously provides for these reactants and byproducts to remain in proximity to allow further reaction and to facilitate more efficient interaction of the reactants with the organic compounds or contaminants. The various partitioning effects of the solid-liquid-gas phases of coated microbubble 60 are also illustrated. For example, with respect to the microbubble, solubility (gas-aqueous partitioning) and its counterpart (aqueous-gas partitioning, governed by Henry's Constant) are processes relating to gas-aqueous phase interactions. Adsorption (gas-solid, liquid-solid) and its counterparts, stripping (solid-gas) and solubility (solid-aqueous) relate to gas-solid and liquid-solid partitioning processes. The interaction of these processes, both in the coated microbubble itself and through its interaction with the treatment area, contribute to the behavior, and advantages, of the coated microbubbles for remediation applications.
The introduction of ozone has an action similar to steaming of soils in reducing indigenous bacterial populations within 10 ft. (ca. 3 m) of the injection well, while additionally degrading organics to more readily attackable forms. Ozone also naturally decomposes to oxygen, theoretically supplying up to ten times the dissolvable oxygen content found with direct air injection. Oxygen-enriched air injection with nutrients purges the remaining ozone residual, allowing indigenous bacterial species capable of organic residue metabolism to quickly expand through the formation.
FIG. 5 illustrates an example of how coated microbubbles diffuse in a treatment area. In FIG. 5, injection well system 71, is a system similar to those described, for example, in FIG. 1 or FIG.6 herein. It has a microporous diffuser 12 for release of the coated microbubbles. Monitoring wells 73 (depicted as KV-1, KV-2, KV-3, KV-4, KV-5, and KV-6) are used to monitor the products and by-products produced after coated microbubble treatment. Upon release of coated microbubbles into the ground, the coated microbubbles flow (and displace water in a similar flow pattern) in patterns depicted as flow patterns 75, 76, and 77. In this manner, mixing of the coated microbubbles in the treatment area occurs. Over time (e.g., 3 days
20 days and so forth) these flow patterns result in oxidative reaction zones 78 and 79, respectively. These reactive zones are areas in which the coated microbubbles have caused more concentrated degradation due to more focused contact and reactivity. The dispersion of the coated microbubbles, however, is not limited to these reactive zones exclusively, rather the coated microbubbles are capable of flowing in all directions.
FIG 6 illustrates an example of how the injection well treatment system can be modified for non-power accessible sites. Well treatment system 80 includes elements of the system of FIG. 1, including microporous diffusers 12 disposed through an injection well 14. The liquid coating material is supplied by compressed gas tank 82 in communication with cap 90. Liquid supply 84 provides the coating materials (e.g., oxidants, catalysts, nutrients) via siphon line 92 to cap 90, which can be performed with or without application of pressure (i.e., with or without a compressor). A gas in compressed gas tank 86 is transferred via tubing through valve and flow meter assembly 88 to cap 90. The cap 90 is in communication with microporous diffusers 12 via gas and liquid transfer lines 22 and 24, respectively, and combination of the gas and liquid result; in generation of coated microbubbles.
Microbiological degradation is a technique to degrade complex organic compounds. The rate of reaction depends upon the type of microbe, the substrate compound targeted as food, and the rate of gaseous exchange. Bubbling oxygen-enriched air through an aqueous solution of substrate compound, supplied with the nutrients nitrogen (N), phosphorus (P), and potassium (K), can encourage rapid metabolism and reproduction of microbes, which consume the organic compounds.
There are specific ratios of carbon (C), nitrogen (N), phosphorus (P), and potassium (K) to promote an efficient reaction. Often these reflect the molecular ratio of the elements in the growth of microbes and are used to expand the population numbers. During microbial degradation of the carbon compounds, oxygen is consumed and carbon dioxide (CO2) is produced. If there is insufficient oxygen, the reaction will be self-limiting, abruptly slowing and eventually stopping.
The basic microbial process of biodegradation (aerobic) can be portrayed as a conversion of oxygen (O2) to CO2 and water plus more bacteria:
bacteria
Organic contaminant ► CO2 + H2O + more bacteria
O2
Whereas the reaction may proceed rapidly in vat or surface vessels, maintaining an efficient and continuous degradation is much more difficult in porous soils. Often evidence of natural biodegradation is shown by excess CO2 in the overlying unsaturated soil zone (vadose zone) and low oxygen content in the saturated (aqueous) zone. The depletion of natural electron acceptors (O , NO3, SO , Fe (III)), the depletion of natural electron donors (organic acids, e.g., acetate, lactate, H2), the buildup of anaerobic metabolism gases such as C02, and the depletion o mineral nutrients (NH3, NO3, PO4, K) regulate the rate of biodegradation.
The choice of oxidants can be used to tailor the remediation process for a selected class of chemical compounds, thus allowing one to design a remediation system for a particular application. This is accomplished by an analysis of the volatile organic compound to be remediated, taking into account its Henry's Constant value (see, Tables 1 and 2), which is an indicator of its proclivity to move from the liquid to the gaseous phase of an interface. By matching this transfer rate with that of the reactivity rate of a particular oxidant, the remediation process can be tailored such that the particular volatile organic compound is optimally reacted (and therefore remediated) relative to other volatile organic compounds present.
Table 1. Ideal for Ozone and Ozone/Hydroperoxide
High Henry's Constants (>10 ) Henry's Law Constant
(atm-m /mole}
Benzene 5.6x1 L0-3
Benzo(a) pyrene 1.1 x 1o-4
Benzo(b) fluoranthene l.lxlo-4
Bromodichloromethane 1.6x1o-3
Bromoform 5.5x1o-4
Bromomethane 6.2x1o-3
Carbofuran 9.2x1 LO'5
Carbon Tetrachloride 3.0x1lo-2
Carbon Disulfide 3.0x1 LO"2
Chlordane 4.9x1to-5
Chloroethane 6.2x1to-4
Chloroform 2.7 x 1lO"3
Chloromethane 8.8x1o-3
Chrysene 9.5 x 1lO"5
1,2 Dibromoethane (EDB) 6.7 x 1o-4
Dibromochloromethane 8.7 x 1to-4
1 ,2-Dibromo-3-chloropropane 1.5 x 1o-4
1 ,2-Dichlorobenzene 1.9x 1o-3
1,3-Dichlorobenzene 3.3 x 1 LO'3
1 ,4-Dichlorobenzene 2.4 x 1 LO"3
Dichlorodifluoromethane 3.4x1 LO"3
1 , 1 -Di chloroethane 5.6x1 LO"3
1,2-Dichloroethane 9.8x1 LO"4
1,2-Dichloroethylene (cis) 4.1 x 1 LO"3
1,2-Dichloroethylene (trans) 9.4 x ] LO"3
1 , 1 -Dichloroethylene 2.6x1 LO"2
1 ,2-Dichloropropane 2.8 x] LO"3
1 ,3-Dichloropropene 1.8x ] LO"2
Dioxins 5.6 x 1 LO"3
Ethyl Benzene 8.4 x LO"3
Fluorene l.Ox lO"4
Fluoro tri chloromethane (freon 11) 9.7 x lO"2
Heptachlor 1.1 x lO"3
Heptachlor epoxide 3.2 x lO"5
Hexachlorobenzene 1.3 x lO"3
Lindane 1.4x LO'5
Methoxychlor 1.6 x lO"5
Methyl isobutyl ketane 1.4x lO"4 Methyl ethyl ketone (MEK) 2.7 x 10"5
Methylene chloride 2.0 x lO"3
Monochlorobenzene 3.8 x 10"3 n-Hexane 1.4 x 10'2
Napththalene 4.8 x 10"4
Polychlorinated biphenyls 1.1 x 10"3
Pyrene 1.1 x 10'5
Styrene 2.8 x 10'3
1,1,1 ,2-Tetrachloroethane 2.4 x 10"3
1 , 1 ,2,2-Tetrachloroethane 4.6 x 10'4
Tetrachloroethylene 1.8 x 10"2
Toluene 6.6 x 10'3
1 ,2,4-Trichlorobenzene 1.4 x 10"3
1,1,1 -Trichloroethane 1.7 x 10"2
1 ,2,3-Trichloropropane 3.4 x lO"4
Trichloroethylene 1.0 x lO"2
Trifluralin 2.6 x 10 5
1 ,2,4-Trimethylbenzene 5.6 x 10"
Vinyl chloride 2.7 x 10"
Xylene (mixed o-, m-, and p-) 7.0 x 10"
Table 2. Moderate Henry's Constants But Breakdown Products With High Henry's Constants
Henry's Constant
Dibutyl phthalate 1.8 x 10-°
2,4-Dichlorophenoxyacetic acid 1.0 x lO'8
Di(2-ethylhexyl) phthalate 3.6 x lO'7
2,4-Dinitrotoluene 1.3 x lO"7
2,6-Dinitrotoluene 7.5 x 10"7
Dinoseb 4.6 x 10"7
Endrin 7.5 x l O"6
Fluoranthrene 6.5 x 10'6
Pentachlorophenol 2.4 x lO"6
Phenol 3.3 x 10"7
Pyridine 8.9 x lO"6
Toxaphene 6.6 x lO"6
The rate of biodegradation in natural formations is very slow compared to above-ground settings. The ability to mix gases, electron donors, or nutrients with organic contaminates is limited by the porosity and hydraulic conductivity of saturated soils. Porous soils tend to encourage movement of liquids as slugs, not easily mixing with existing groundwater. The rate of natural movement is slow and determined by existing groundwater gradients. Velocities of natural flows commonly run 0.1 to 2 ft/day. The natural flow across a 100 ft wide contaminant zone may take 50 to 1000 days. The capability to remove product waste products is similarly hindered.
To address these issues, an efficient technique to provide reaction promoters and simultaneously to remove unnecessary products is desirable. "Food" in the form of carbon sources which provide energy (electron donors) is available in liquid form. Nutrients also can be mixed with "food" forms to assure ready availability of all required components for remediation conditions and organism growth enhancing environments. The presence of both as a coating to oxygen-enriched air provides bacteria with a very mobile nutrient system. In addition, gaseous products such as CO2 can be transported away (i.e., displaced from the remediation area) as the gas rises. Microbubble technology provides the necessary attributes to meet these needs. A microbubble can be "coated" by forcing microbubbles from less than about 200 microns, e.g., 0.5 to 200 micron size through a porous liquid stream in a diffuser, (e.g., a
"laminated" Microporous Spargepoint® diffuser (Model Nos. SPT2000 and SPT2010), available from K-V Associates, Inc., Mashpee, MA) or by introducing aerosolized liquid particles into the gas stream supplying a diffuser. While not being bound by theory, generally, coatings made by forcing the microbubble through the liquid stream result in relatively thicker coatings caused, in part, by the thicker reaction points of the liquid forced through the gaseous phase in the diffuser.
Conversely, those generated by the aerosol method result in microbubbles with relatively thinner coatings caused, in part, by the finer porous points of the liquid when introduced as an aerosol. Thicker coatings generally elevate the reactivity of the microbubble, particularly in oxidative reactivity. For example, thicker coatings of oxidative material is associated with increased Criegee oxidative capacity or oxidative potential (see, Dowideit and Sonntag, Environ. Sci.
Technol. 1998, 32, 112-1119, incorporated by reference in its entirety), that is, the ability of the microbubble to break bonds of the chemical compound or contaminant subject to oxidative degradation. The thickness of a coating can be ascertained by techniques such as microscopic capillary analysis of the microbubbles with dyes (e.g., India ink), backlighting, or photoelectric cell detection methods. The microbubbles can include a thin-layer coating having a material suitable for oxidative reactivity. So called, "high oxidative capacity" or "advanced oxidative" systems (e.g., using potassium or sodium permanganate, ozone in high concentrations, Fenton's reagent) are capable of particularly efficient chemical reactivity (e.g., bond breaking capacity, carbon- containing compound reactivity) useful in contaminant degradation processes. These reactions are characterized in that they have oxidation potentials in excess of 2.0 (based on electrochemical reactions at 25 °C).
The microbubbles delineated herein are advantageous in that they can be designed to optimize their suitability for certain applications in remediation technology. For example, the microbubbles can be formed and shaped in the various manners described above (e.g., using a microporous diffuser, or aerosolized liquid and a microporous diffuser). Depending on their size and thickness, certain reactivity profiles can be achieved. Additionally, the composition of the gas in the bubble, as well as the type of liquid coating selected can be chosen to accomplish various oxidative or reductive degradation profiles, and catalysts (e.g., metals in microparticle form, acids) can be incorporated into the microbubble to increase reactivity and degradation efficiency of the microbubble. Moreover, the methods of generating microbubbles allow for control of the stoichiometry of the chemical components in the microbubble, again allowing for the ability to tailor the microbubble to a specific profile for a desired application or reactivity By increasing the flow of liquid during the flow of gas, the thickness of the coating can be increased The strength of oxidation capacity can be effected by increasing the concentration of hydrogen peroxide in the liquid phase as well as increasing the ozone content in the gas phase.
The size of the microbubble can also be varied by controlling the pressure of the gas during generation of the microbubble and by choice of the diffuser pore size. For example, by generating smaller coated microbubbles, the surface to volume ratio increases, which improves reactivity of the microbubble. Additionally, in instances where a coating thickness is held constant, a smaller coated microbubble effectively has a "thicker" coating relative to a larger coated microbubble, thus resulting in a coated microbubble with a "thicker" coating and greater surface area (relative to volume), which both contribute to increased reactivity (e.g., in oxidative coating applications, higher oxidative potential). Normally, the range of fluid to gas varies from parity (1:1) to about 1 :100. This corresponds to a coating thicken of 0.3 (30%) increase in radius down to 0.01 (1%). Table 3 illustrates the relationship between gas and liquid volumes and variance in the coating thickness.
Table 3. Relationship of Microbubble Gas Volume to Liquid Volume with Change in Coating Thickness
Microbubble Size (mm)
Figure imgf000015_0001
Microbubbles can also be selected according to a controlled size using a layered fine bubble production chamber. The layered fine bubble production chamber is a chamber in which a liquid is placed under pressure and microbubbles are generated. That is, over a period of time, an environment is provided where the microbubbles segregate by size (e.g., larger microbubbles rise and smaller microbubbles remain) thus allowing a mixture predominated by a particular microbubble size (or size range) to be established prior to injection into the treatment area. This is suitable for use, for example, where smaller microbubbles may be desired (i.e., for their higher surface to volume ratio). One example of such control relates to the "Law of the Minimum", which states that bacterial growth will stop when the nutrient that was present in the lowest concentration (relative to the requirement) is exhausted, becomes a problem since the rest of the mixture is useless. If that substance is replenished, growth will stop when the next substance is exhausted. By providing a means of ready mixing of the constituents and having the capacity to modify the electron accelerator and nutrient ratios, using metabolic products as a guide (e.g., monitoring by- products formation in real time by sampling via a monitoring well and analyzing the samples using, for example, gas chromatography or other suitable analytical technique), the rate of metabolism can be adjusted and maximized. In another embodiment, the methods herein can be applied such that an existing monitoring well can be used as an injection well for the microbubble diffuser.
Microbubbles form a unique physical and chemical environment which can effectively treat waterborne or attached (adsorbed) volatile organic compounds (VOCs). Diffusers, or spargers, placed in groundwater or saturated soil provide extremely small "microbubbles" with a very high surface area to volume ratio. This high surface area to volume ratio maximizes the VOC transfer from the liquid phase to gas phase. If the air bubbles are filled with an oxidizing gas, like ozone, the VOCs react with the ozone and are destroyed while still in the water column. This "in-situ"- combined VOC recovery and destruction not only obviates the need for an additional process step but also enhances the physical and chemical kinetics of the process.
Microporous diffusers suitable for use in the methods described herein are those having the ability to deliver a gas and a liquid such that microbubbles less than about 200 microns, preferably between about 0.5 and 200 microns, are produced including the gas therein and a thin layer of the liquid material coating the microbubble. The diffuser can be constructed of a variety of materials suitable for the gases and liquids to be delivered, such materials include, for example, stainless steel, high-density polyethylene (HDPE), low-density polyethylene (LDPE), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE, e.g., TEFLON), acetal (e.g.,
DELRIN), or polypropylene. The diffuser can include concentric tubes of microporous material, optionally having additional packing materials (e.g., hydrophobic plastics, hydrophilic plastics, beads, interconnected fibers) sandwiched between the tubes to facilitate creation of the gas-liquic interface in the microbubble. These materials aid the liquid coating process of the gas flowing through the diffuser in the generation of microbubbles, in part by their hydrophilic or hydrophobic nature to enhance coating, and in part by their ability to increase the positioning of the liquid to optimize contact with the gas flowing through . Examples of diffusers suitable for use in the methods delineated herein include the laminar microporous SPARGEPOINT© diffusei or the C-SPARGER® diffuser (both available from K-V Associates, Inc., Mashpee, MA). Aerosols or aerosolized liquid particles are one method by which coated microbubbles can be formed. The aerosolized particles are produced using an aerosolizer (see, FIG. 3), including any apparatus suitable for providing an aerosolized form of a liquid (e.g., a commercial airbrush Badger 150). The aerosolized liquid particles can be any suitable for use in the coating application (i.e., chemical or biological reaction) and remediation process of interest, including for example, oxidants (e.g., hydroperoxides, potassium permanganate, Fenton's reagent (hydrogen peroxide and Fe(II))), catalysts (e.g., as delineated below), acids, (e.g., acetic, lactic), and nutrients (e.g., as delineated below).
The aerosol can be generated using an aerosol head including a reservoir of liquid or liquid and microfine particles mixture; a siphon tube made of e.g., TEFLON or resistant flexible plastic; a tube supply with compressed air; a mixing chamber where the liquid is drawn into the flowing gas; a spray head which controls the particle size and distribution of the aerosols; and a compression fitting which directs the aerosol flow into the air/ozone gas stream. The mixing chamber can be, for example, a Bernoulli chamber, that is, any chamber that (in accordance with Bernoulli's principle) is capable of compressing a fluid through a narrower opening into a larger chamber resulting in a variance in pressure. The aerosol head can further include connecting tubing such as TEFLON tubing 3/8" to V" in diameter, polyvinyl chloride tubing ! 2" to 1" in diameter, with o-ring seals (e.g., VITON) and threaded 5 ft. sections. The aerosol head is in communication with the microporous diffusers, in a manner to maintain a sufficient rate of gas flow to avoid condensing of the aerosol flow. The aerosol spray head can e adjustable to vary the liquid flow feed rate from between about 1/10 to 1/10,000 of the flow of the air/ozone volume flow. Also, the aerosol flow can be introduced continuously with the air/ozone flow.
Catalysts are any material that is useful in catalyzing the desired chemical transformation or process to promote quicker or more efficient reaction. The catalysts are presented as micron- sized particles to augment the interface region of the microbubble. For example, transition metals including palladium (Pd), manganese (Mn), and iron (Fe), in elemental or salt forms; sulfur compounds including sulfates and sulfides.
Additionally, the acidity of reactions processes can be modified to enhance reactivity, and therefore the remediation processes herein. For chemical reactions (i.e., remediation processes) that are more effective under lower pH conditions (i.e., acidic, pH less than 7) the microbubbles can be coated with an acidic coating, thus, lowering the pH of the interface and increasing the reaction rate and efficiency of the remediation process. The acid can also be incorporated in a coating having other liquids in it where beneficial (e.g., increased reactivity, efficiency) chemical effects can be realized, for example, acid and iron (II or III) salts (e.g., Fenton's reagent), which in combination can catalyze the oxidative reactivity of the coated microbubble. This is advantageous in soil aquifers, where it is impractical to acidify the entire aquifer, and is also useful in reactions and remediation processes involving halocarbon contaminants. The gases useful in the microbubbles are any that are suitable for chemical or biological reaction and remediation. For example, in oxidative applications, ozone, oxygen and air are suitable gases. In reductive applications, nitrogen or hydrogen can be used. The gas suitable for an application is dependent , in part, on criteria such as the reaction desired, or the bacterial growth requirements (aerobic or anaerobic). The gas can be generated in situ (e.g., ozone generator), provided using a compressor, or provided via compressed tanks (e.g., .
Nutrient coatings on the microbubbles are any suitable nutrient for bacterial (aerobic or anaerobic) growth. Such nutrients include, for example, carbon sources (e.g., carbohydrates, sugars, beer, milk products, methanogens, organic acids such as acetic and lactic acids, organic esters such as acetates, proprionates, organic ketones such as acetone), nitrogen sources (e.g., ammonia, nitrates, ammonium nitrate), phosphorous sources (e.g., soluble phosphates, etc), and potassium sources (e.g., 10,000 ppm of lactate; 680 ppm NH4NO ; 200 ppm KH2PO to provide sources of carbon and nitrogen, and phosphorus and potassium). Generally, environments suitable for bacterial support and growth are made up of the nutrients in the following relative ratios: carbon (ca. 1000 parts), nitrogen (ca. 150 parts), phosphorous (ca. 30 parts), sulfur, potassium, and sodium (ca. 10 parts each), calcium, magnesium, and chloride (ca. 5 parts each), iron (ca. 2 parts), and any remainder elements in trace amounts, with the ratios based on molar equivalents, which may be in the form of either elemental or ionic (i.e., salt) forms, or a combination thereof.
Advantageous aspects of the invention include: 1) gas/liquid thin-layer microbubble oxidation to predigest and sterilize around injection locations; 2) simultaneous injection of nutrients and food source with gas in proportion to optimal ratio for assimilation; 3) injection of nutrients to provide a coating (thin layer) on gas (oxygen-enriched air) being injected into porous soil capillaries; 4) introduction in a pulsed manner with microbubbles of 5 to 100 micron diameter sized to pores of soil to avoid fracturing of soil and to enhance transport through capillary-like soil voids; 5) use of microporous diffusers (e.g., Spargepoint®) or aerosolized liquids and microporous diffusers for simultaneous introduction of gas and liquid mixtures into coated microbubbles engineered for specific characteristics (e.g., size, shape, reactivity, composition).
In order that the invention described herein may be more readily understood, the following examples are set forth. It should be understood that these examples are for illustrative purposes only and are not to be construed as limiting this invention in any manner. All references cited herein are expressly incorporated by reference in their entirety.
Examples Bench-scale tests were conducted on soil samples collected from a site located in Paterson, New Jersey and augmented with PCBs (e.g., arochlor 1260). The purpose of the tests was to evaluate the response of volatile organic compounds and semi-volatile organic compounds contained in soil aliquots extracted from these soil samples to an aqueous environment containing various injected concentrations of sparged air with ozone or sparged air with ozone plus varying concentrations of injected hydrogen peroxide. During each test, treated and untreated aqueous samples were collected from the test cell at regular time intervals and field screened with portable gas chromatograph for ionizable compounds. Prior to, and following each test, soil and groundwater samples were collected from the test cell for confirmatory laboratory analyses.
Testing Procedure
Initial bench-scale testing included putting approximately 5 grams of soil sample in a 40 ml VOA vial with 30 ml of water and allowing headspace to develop, then screening the headspace in an HNu Systems Model 321 portable gas chromatograph. The purpose of this step was to extrapolate the volume of soil necessary to produce an instrument response in the GC that was noticeable for further testing.
Subsequent testing included stirring approximately 40 grams of soil sample in 500 ml of water contained in an Erlenmeyer flask and subjecting the entire solution to sparged air containing approximately 100 ppmv of ozone. This test was conducted under 0 psig with aqueous samples collected from the test cell at time intervals of 0, 2, 5, 10, 15, and 20 minutes and field screened with portable gas chromatograph for ionizable compounds. Following the above preliminary bench-scale tests, further testing was conducted in a larger glass volume container to allow for split sampling of soil and groundwater samples to a certified laboratory for confirmatory analyses. This test cell included mounting a stopper on the 1,000 ml container and drilling holes in the stopper to allow for various tubing diameters to pass through the stopper to accommodate: an external pressure gauge T'd with a pressure relief valve; a sample guideport to permit below-water-level aqueous sampling; a gas line for a mini- laminate Spargepoint® (1.5 inch in height and 1.5 inch in diameter); and injection of treatment liquids such as a 3% solution of hydroperoxide or peracid precursor.
The following four bench-scale tests were all conducted under 5 psig. Split groundwater samples were collected at the beginning and end of each test run and sent to a Massachusetts state-certified laboratory for volatile organic analysis. Soil samples were collected at the beginning of each test run and sent to a Massachusetts state-certified laboratory for volatile organic analysis. Soil samples were collected at the beginning of each test run and sent to a Massachusetts state-certified laboratory for volatile and semi-volatile organic analysis. A soil sample was collected at the end of each test run and sent to a Massachusetts state-certified laboratory for semi-volatile organic analyses.
Results
The soil samples appeared to contain weathered oil as well as other organic compounds. Review of the portable gas chromatograms indicate the nearly complete attenuation of ionizable compounds by the end of each test run. The last set, using a 300 ppmv ozone concentration and 2 ml/min hydroperoxide, gave the lowest baseline response of the four treatments. The introduction of hydroperoxide with ozone as a bubble coating appeared superior in treatment than a batch mixing with an added slug of equivalent volume. A final additional test set was performed by increasing the oxidant concentrations to 300 ppmv ozone with 10 ml 10% hydroperoxide and 3000 ppmv with 30 ml 10% hydroperoxide as a bubble coating. The results of the test are presented in Table 4. After oxidation, the nutribubble introduction was started and continued until remaining concentrations drop below 10 μg/kg. Table 4. Removal of PCBs and PAHs from contaminated sediment by ozone plus hydroperoxide, introduced as bubble coating, 30-minute bench-scale test.
Initial Concentration Ozone + Hydroperoxide
(μg/kg) 300 ppmv+ 3000 ppmv+
Compound 10 ml 10% 30 ml 10% % Removal
Arochlor 1260 23,300 3,900 5,000 79
Naphthalene 21,000 750 650 97
2-Methylnaphthalene 13,000 710 BRL 99
Acenaphthylene 15,000 BRL BRL 99
Benzo(a)anthracene 18,000 5,800 2,400 86
Benzo(b)fluoranthene 17,000 5,800 3,100 82
Benzo(k)fluoranthene 17,000 5,400 2,700 84
Dibenzo(a,h)anthracene 17,000 4,900 2,300 86
Indo(l,2,3-c,d)pyrene 18,000 5,100 2,300 87
Phenanthracene 17,000 4,200 2,000 87
Pyrene 40,000 13,000 5,500 86
Field Operations and Implementation
The process of administration of the liquid and gas would be in-situ, with use of laminar diffusers (e.g., Spargepoints®). Figure 1 presents a schematic diagram of the K-V Associates
Criegee oxidizer with simultaneous liquid and gas supply. The individual diffusers (e.g., Spargepoints®) are drilled into the contaminated aquifer region to be treated. The timer- controller delivers liquid and gas simultaneously. The number of diffusers (e.g., Spargepoints®) depend upon the volume to be treated. The microbubble operating system is used to field treat about 1 cubic meter of saturated soil contained in a plastic trash bin runs on house current (120 volts AC, 15 amp).
The reactivity of ozone with benzene, phenanthrene, naphthalene, pyrene, and chrysene is well-documented in the scientific literature. Old diesel fuel or coal tar residues often contain these compounds. Not uncommonly, PCBs are encountered with these organics, presenting a difficult mix to remediate. The bench test of the coated microbubbles resulted in a removal varying from 79% to 99% for the mixture of PAHs and PCBs, with initial oxidant treatment. Foi the arochlor example (See, Table 5), this corresponds to remediation from about 23,300 μg/kg initial concentration to about 3,900 μg/kg upon initial oxidant treatment. Switching to nutribubble injection can be successful in bringing the total removal rate to less than 10 μg/kg of treated soil. Representative results are delineated in Table 4. The designation "below reportable levels" (BRL) signifies that concentrations were below those detectable according to the analytical techniques and instrumentation used.
Table 5. Removal of HVOCs (PCE and TCE), PCBs (Arochlor 1016), and PAHs (Nitrobenzene, Phenanthrene, Anthacene, and Pyrene) in Contaminated Soil During Pilot Test with Hydroperoxide-Thickened Microbubbles (Concentrations in ppb-μg/kg (Soil) or μg/L (Water)
Figure imgf000022_0001
A number of embodiments of the invention have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are within the scope of the following claims.

Claims

WHAT IS CLAIMED IS:
L A remediation process comprising: generating microbubbles comprising a gas, coated with a thin layer of liquid compounds suitable for promoting biological degradation of organic compounds.
2. A remediation process comprising: generating microbubbles comprising a gas, coated with a thin layer of liquid compounds suitable for promoting chemical degradation of organic compounds and generation of microbubbles comprising a gas, coated with a thin layer of liquid compounds suitable for promoting biological degradation of organic compounds.
3. The remediation process of claim 2, wherein the microbubbles are coated by introducing a liquid as an aerosol to a gas, which mixture is forced through a microporous material, resulting in the coated microbubbles.
4. The remediation process of claim 2, wherein the microbubbles are coated by directing a gas through a liquid and a microporous material, resulting in the coated microbubbles.
5. The remediation process of claim 2, wherein the microbubbles are coated by directing a gas through a liquid and two layers of microporous material, wherein the liquid and a packing material is sandwiched between the layers of microporous material, resulting in the coated microbubbles.
6. The remediation process of claim 2, wherein generating uses a diffusing apparatus including two concentric tubes of 0.5-200 micron microporous material, the inner tube receiving gas flow sandwiching a hydrophobic layer of microbeads 0.01 to 1.0 mm diameter which receives hydroperoxide flow.
7. The remediation process of claim 2, wherein generating uses a diffusing apparatus including two concentric tubes of 5-200 micron stainless steel microporous material, the inner tube receiving gas flow sandwiching a hydrophobic layer of microbeads or porous material which receives hydroperoxide flow.
8. The remediation process of claim 2, wherein the microporous material is porous high- density polyethylene, polyvinyl chloride, polytetrafluoroethylene, low-density polyethylene, acetal, or polypropylene.
9. The remediation process of claim 2, wherein the chemical reaction is oxidative.
10. The remediation process of claim 2, wherein the chemical reaction is reductive.
1 1. The remediation process of claim 2, wherein the coated microbubbles are injected into soil.
12. The remediation process of claim 2, wherein the coated microbubbles are injected into water supply pipes.
13. The remediation process of claim 2, wherein the coated microbubbles are injected into surface water.
14. The remediation process of claim 2, wherein the coated microbubbles are injected into sediment.
15. A remediation process comprising: generating microbubbles comprising a gas, coated with a thin layer of liquid compounds suitable for promoting chemical degradation of organic compounds wherein the microbubble is coated by introducing a liquid as an aerosol to a gas, which mixture is forced through a microporous material, resulting in the coated microbubble, and contacting the coated microbubble with the area to be remediated.
16. The remediation process of claim 15, where the chemical degradation is an oxidative reaction.
17. The remediation process of claim 16, wherein the microbubble comprises ozone gas with hydroperoxide or peracid coatings.
18. The remediation process of claim 16, wherein the microbubble comprises air with hydroperoxide or peracid coatings.
19. The remediation process of claim 16, wherein the microbubble comprises ozone gas with permanganate coatings.
20. The remediation process of claim 16, wherein the microbubble comprises air with permanganate coatings.
21. The remediation process of claim 16, wherein the microbubble comprises air with Fenton's Reagent coatings.
22. The remediation process of claim 16, wherein the microbubble comprises ozone with Fenton's Reagent coatings.
23. The process of claim 16 further comprising: promoting biological remediation by including contacting microbubbles comprising oxygen-enriched air and a carbon-source as the liquid coating, and wherein the biological remediation step follows the chemical oxidation microbubble contacting.
24. The process of claim 23, wherein biological microbubble contacting is alternated with chemical oxidation microbubble contacting.
25. The process of claim 15, wherein the organic compounds are degraded by a Criegee-like oxidation reaction.
26. The process of claim 15, wherein the compounds are volatile organic compounds (VOCs) with Henry's Constants less than or equal to 10'5 ATM-M3/Mole.
27. The process of claim 15, wherein the compounds are halogenated volatile organic compounds (HVOCs) like perchloroethylene, trichloroefhylene, dichloroethylene, vinyl chloride, trichloroethane, dichloroethane, chloroform, ethylene dibromide, chlorobenzene, PCBs, pesticides (e.g., heptachlor); petroleum aromatics (e.g., BTEX - benzene, toluene, ethylbenzene, xylenes, naphthalene); methyl-t-butyl ether; aromatic nitro compounds (e.g., trinitrotoluene, nitrobenzene); styrene and ethyl-t-buyl ether.
28. The process of 15 wherein the compounds are poorly volatile (Henry's Constant greater than 10"5 ATM-M3/Mole) but break down into volatile organic compound by-products upon chemical oxidation microbubble contact.
29. The process of 28 wherein the compounds are polyaromatic hydrocarbons (e.g., anthracene, fluoranthene, phenanthrene, naphthalene), polychlorinated phenols, or phthalates.
30. An apparatus for remediating a contaminated area using a liquid-coated microbubble including one or more gases comprising: an injection well; a source of a liquid suitable for promoting biological degradation of organic compounds; a source for delivering a gas; an aerosolizer for aerosolizing the gas; a microporous diffuser disposed in the well for generating coated microbubbles of a controlled size comprising the gas and a liquid coating.
31. The apparatus of claim 30, wherein the microporous diffuser injects the gas and liquid simultaneously.
32. The apparatus of claim 30, further comprising: a controller for controlling the ratio of gas and liquid in generating the coated microbubble.
33. The apparatus of claim 30, further comprising: a controller for controlling mixing of ambient air with said liquids.
34. The apparatus of claim 30, further comprising: an agitator to pulse or surge the microbubbles into the well to improve transport of coated microbubbles through the contaminated area.
35. The apparatus of claim 34 wherein the agitator comprises a submersible pump.
36. The apparatus of claim 30 wherein the bubble sizer for the coated microbubbles comprises: a layered fine bubble production chamber.
37. The apparatus of claim 33, wherein the controller for controlling mixing comprises: a wellhead control for equalizing flow between formations of differing permeability.
38. The apparatus of claim 34 wherein the agitator alternates pumping of water and coated microbubble injection.
39. The apparatus of claim 30 wherein the liquid oxidizing agent is hydrogen peroxide, or an intermediate by-product of decomposition of ozone and an organic compound, including formic peracid, acetic peracid, hydroxymethylhydroperoxide, or 2-hydroxy-2-propyl hydroperoxide.
40. The process of claim 16, wherein the peracid is peroxyacetic acid, peroxyformic acid, perhydroxymethyl acid, or perhydroxy acid.
41. The process of claim 3, further comprising: an aerosol injection system to inject liquid hydroperoxide into a stream of ozone- containing air to generate the microbubble, wherein the liquid hydroperoxide is pulled under vacuum (negative pressure) into the air/ozone stream and the combined aerosol/gas mixture enters a microporus diffuser yielding 0.5-100 micron microbubbles into soil pore channels.
42. The process of claim 3, further comprising: introducing the aerosol with a spray head inserted at a "T" comiection on the top of a wellhead leading to a microporous diffuser, the aerosol spray head being adjustable to vary the liquid flow feed rate from between about 1/10 to 1/10,000 of the flow of the air/ozone volume flow, and wherein the aerosol flow can be introduced continuously with the air/ozone flow.
43. The process of claim 3, further comprising: introducing the aerosol with a spray head fed by a separate air compressor system from the air/ozone system.
44. The process of claim 3, further comprising: using an array of aerosol-fed microporous diffusers to create a microbubble interface to intercept and contain a migrating plume.
45. The process of claim 41, further comprising: pulsing simultaneously the aerosol and air/ozone stream to coat the microbubbles and maximize dispersion of bubbles through the geological formation.
46. An aerosol head comprising: a reservoir of liquid; a tube supply with compressed air; a mixing chamber where the liquid is drawn into the flowing gas; and a spray head which controls the particle size and distribution of the aerosols.
47. The aerosol head of claim 46, further comprising: a reservoir of liquid and microfine particles mixture.
48. The aerosol head of claim 46, further comprising: a siphon tube.
49. The aerosol head of claim 46, further comprising: a compression fitting which directs the aerosol flow into the air/ozone gas stream.
50. The aerosol head of claim 46, further comprising: a connecting tubing comprising: PTFE tubing 3/8" to lA" in diameter and polyvinyl chloride tubing .4" to 1" in diameter with viton o-ring seals and threaded 5 ft. sections.
51. The aerosol head of claim 46, further comprising: a receiving microporous diffuser having a 0.5-200 micron high-density polyethylene microporous material and a diameter of 2" to 3 t", maintaining sufficient rate of gas flow to avoid condensing of the aerosol flow.
52. The aerosol head of claim 46, further comprising: a receiving microporous diffuser having a 0.5-200 micron stainless steel microporous material and a diameter of 2" to VJ", maintaining sufficient rate of gas flow to avoid condensing of the aerosol flow.
53. A microbubble comprising: a gas, coated with a thin layer of liquid compound suitable for promoting biological degradation of organic compounds.
54. The microbubble of claim 53, wherein the liquid compound is a carbon source, a nitrogen source, a phosphorous source, or a potassium source.
55. The microbubble of claim 53, wherein the gas is air or oxygen.
PCT/US2002/015939 2001-05-18 2002-05-16 Environmental remediation method and apparatus WO2002094723A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CA2441259A CA2441259C (en) 2001-05-18 2002-05-16 Environmental remediation method and apparatus
EP02771856A EP1390303A4 (en) 2001-05-18 2002-05-16 Environmental remediation method and apparatus

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US09/860,659 US6805798B2 (en) 2001-05-18 2001-05-18 Environmental remediation method and apparatus
US09/860,659 2001-05-18

Publications (1)

Publication Number Publication Date
WO2002094723A1 true WO2002094723A1 (en) 2002-11-28

Family

ID=25333724

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2002/015939 WO2002094723A1 (en) 2001-05-18 2002-05-16 Environmental remediation method and apparatus

Country Status (3)

Country Link
US (3) US6805798B2 (en)
EP (1) EP1390303A4 (en)
WO (1) WO2002094723A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2900146A1 (en) * 2006-04-19 2007-10-26 Total Sa Cleaning the groundwater flow having contaminants e.g. benzene, comprises injecting oxygen in a permeable massive underground filter placed in the groundwater to degrade the contaminants that flow in the form of a plume
CN104858230A (en) * 2015-05-15 2015-08-26 合肥市吴山固体废物处置有限责任公司 Restoration method for soil polluted by benzyl chloride and special water distributor
CN105565466A (en) * 2016-03-02 2016-05-11 清泽环境发展(北京)有限公司 Efficient environment-friendly Fenton's reagent and method thereof for oxidizing and treating nitrobenzene

Families Citing this family (56)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5855775A (en) 1995-05-05 1999-01-05 Kerfoot; William B. Microporous diffusion apparatus
USRE43350E1 (en) 1995-05-05 2012-05-08 Think Village-Kerfoot, Llc Microporous diffusion apparatus
US6436285B1 (en) * 1999-12-22 2002-08-20 William B. Kerfoot Laminated microporous diffuser
US8557110B2 (en) 2000-07-06 2013-10-15 Thinkvillage-Kerfoot, Llc Groundwater and subsurface remediation
US6582611B1 (en) * 2000-07-06 2003-06-24 William B. Kerfoot Groundwater and subsurface remediation
AU2003215360A1 (en) * 2002-02-22 2003-09-09 University Of Utah Research Foundation Remediation with ozone of sediments containing organic contaminants
WO2004030840A1 (en) * 2002-10-02 2004-04-15 Lessard Lawrence H Method for the chemical and biological remediation of contaminated soil and/or groundwater
US7547388B2 (en) * 2004-07-20 2009-06-16 Think Village-Kerfoot, Llc Superoxidant poiser for groundwater and soil treatment with in-situ oxidation-reduction and acidity-basicity adjustment
US8302939B2 (en) 2003-02-12 2012-11-06 Thinkvillage-Kerfoot, Llc Soil and water remediation system and method
US7666316B2 (en) * 2004-07-20 2010-02-23 Thinkvillage-Kerfoot, Llc Permanganate-coated ozone for groundwater and soil treatment with in-situ oxidation
US6913251B2 (en) * 2003-02-12 2005-07-05 William B. Kerfoot Deep well sparging
US7442313B2 (en) 2003-08-27 2008-10-28 Thinkvillage-Kerfoot, Llc Environmental remediation method and system
US7175770B2 (en) * 2003-03-17 2007-02-13 Groundwater And Environmental Services, Inc. Methods and systems for groundwater remediation
US7264419B2 (en) * 2003-03-19 2007-09-04 Applied Process Technology, Inc. System and method for remediating contaminated soil and groundwater in situ
US20060243668A1 (en) * 2003-03-21 2006-11-02 Miller Gregory P Apparatus, method and system of treatment of arsenic and other impurities in ground water
US7651611B2 (en) 2006-07-12 2010-01-26 Thinkvillage-Kerfoot, Llc Directional microporous diffuser and directional sparging
US8771507B2 (en) 2003-12-24 2014-07-08 Thinkvillage-Kerfoot, Llc Directional microporous diffuser and directional sparging
US7621696B2 (en) * 2006-07-12 2009-11-24 Thinkvillage-Kerfoot, Llc Directional microporous diffuser and directional sparging
US7569140B2 (en) * 2005-11-10 2009-08-04 Thinkvillage-Kerfoot, Llc Directional spargewell system
US7401767B2 (en) 2003-12-24 2008-07-22 Kerfoot William B Directional microporous diffuser and directional sparging
US7431849B1 (en) * 2004-03-05 2008-10-07 Specialty Earth Sciences Llc Encapsulated reactant and process
US10335757B2 (en) 2004-03-05 2019-07-02 Specialty Earth Sciences Process for making environmental reactant(s)
WO2005098420A1 (en) * 2004-03-26 2005-10-20 Ann Arbor Technical Services Geomorphology for environmental remediation processes and systems
US7407583B2 (en) * 2004-06-16 2008-08-05 University Technologies International, Llp In-situ groundwater nitrification and de-nitrification remediation system
GB0418295D0 (en) * 2004-08-17 2004-09-15 Dew Pitchmastic Plc Bioremediation foam and delivery method
GB0418296D0 (en) * 2004-08-17 2004-09-15 Dew Pitchmastic Plc Compositions for bioremediation
US7476320B1 (en) * 2004-11-12 2009-01-13 Leggette Brashears & Graham, Inc. Process for groundwater remediation
US7303608B2 (en) * 2004-12-21 2007-12-04 Spx Corporation Groundwater reactive gas injection and venting system for a groundwater remediation system
US20080000839A1 (en) * 2006-02-15 2008-01-03 Liquid Separation Technologies And Equipment, Llc Methods of water decontamination
US20080000819A1 (en) * 2006-02-15 2008-01-03 Liquid Separation Technologies And Equipment, Llc Water decontamination systems
US20080000821A1 (en) * 2006-02-15 2008-01-03 Liquid Separation Technologies And Equipment, Llc Apparatus for water decontamination
US7820137B2 (en) * 2006-08-04 2010-10-26 Enerdel, Inc. Lithium titanate and method of forming the same
US7667087B2 (en) * 2006-06-27 2010-02-23 Enchem Engineering, Inc. Soil and water remediation method and apparatus
US20100150657A1 (en) * 2006-06-27 2010-06-17 Enchem Engineering, Inc. Soil and Water Remediation Method and Apparatus
US8163243B1 (en) * 2006-09-07 2012-04-24 The United States Of America As Represented By The Administrator Of National Aeronautics And Space Adminstration Zero-G condensing heat exchanger with integral disinfection
US8016041B2 (en) * 2007-03-28 2011-09-13 Kerfoot William B Treatment for recycling fracture water gas and oil recovery in shale deposits
US9266752B2 (en) 2007-08-02 2016-02-23 Ecosphere Technologies, Inc. Apparatus for treating fluids
US7699994B2 (en) * 2007-08-02 2010-04-20 Ecosphere Technologies, Inc. Enhanced water treatment for reclamation of waste fluids and increased efficiency treatment of potable waters
US8999154B2 (en) 2007-08-02 2015-04-07 Ecosphere Technologies, Inc. Apparatus for treating Lake Okeechobee water
US8906242B2 (en) * 2007-08-02 2014-12-09 Ecosphere Technologies, Inc. Transportable reactor tank
US20100224495A1 (en) * 2007-08-02 2010-09-09 Mcguire Dennis Real-time processing of water for hydraulic fracture treatments using a transportable frac tank
US7699988B2 (en) * 2007-08-02 2010-04-20 Ecosphere Technologies, Inc. Enhanced water treatment for reclamation of waste fluids and increased efficiency treatment of potable waters
US8721898B2 (en) * 2007-08-02 2014-05-13 Ecosphere Technologies, Inc. Reactor tank
US8101089B2 (en) 2007-08-15 2012-01-24 Liquid Separation Technologies And Equipment, Llc Apparatus for aeration of contaminated liquids
US20090188721A1 (en) * 2008-01-30 2009-07-30 Smith Kevin W Membrane method of making drilling fluids containing microbubbles
US20100307754A1 (en) * 2009-06-04 2010-12-09 Savannah River Nuclear Solutions, Llc Aerosol injection into vadose zone
JP5737551B2 (en) * 2009-08-07 2015-06-17 清水建設株式会社 Method and apparatus for purifying contaminated soil or groundwater
US9896918B2 (en) 2012-07-27 2018-02-20 Mbl Water Partners, Llc Use of ionized water in hydraulic fracturing
US9694401B2 (en) 2013-03-04 2017-07-04 Kerfoot Technologies, Inc. Method and apparatus for treating perfluoroalkyl compounds
WO2014144718A1 (en) 2013-03-15 2014-09-18 Carus Corporation Sustained release reactant blends
US20150034328A1 (en) * 2013-08-01 2015-02-05 Mohamed Abouodah Groundwater remediation apparatus and method
US10843140B2 (en) 2014-03-28 2020-11-24 Linne Industries, LLC Water aeration system with floating diffuser
US10639596B2 (en) * 2014-03-28 2020-05-05 Linne Industries, LLC Water aeration system
US9290398B2 (en) 2014-03-28 2016-03-22 Linne Industries Llc Water aeration system
US10647045B1 (en) 2016-11-03 2020-05-12 Specialty Earth Sciences, Llc Shaped or sized encapsulated reactant and method of making
CN108689475B (en) * 2018-07-02 2021-02-02 深圳清华大学研究院 Fenton oxidation baffled reactor and organic wastewater treatment method

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4684479A (en) * 1985-08-14 1987-08-04 Arrigo Joseph S D Surfactant mixtures, stable gas-in-liquid emulsions, and methods for the production of such emulsions from said mixtures
US5215680A (en) * 1990-07-10 1993-06-01 Cavitation-Control Technology, Inc. Method for the production of medical-grade lipid-coated microbubbles, paramagnetic labeling of such microbubbles and therapeutic uses of microbubbles
US5560737A (en) 1995-08-15 1996-10-01 New Jersey Institute Of Technology Pneumatic fracturing and multicomponent injection enhancement of in situ bioremediation
US5855775A (en) 1995-05-05 1999-01-05 Kerfoot; William B. Microporous diffusion apparatus
EP1174197A2 (en) 2000-07-06 2002-01-23 William Kerfoot Groundwater and subsurface remediation

Family Cites Families (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3814394A (en) * 1971-11-17 1974-06-04 M Murray Apparatus for encapsulating hot gases from high stacks
US3997447A (en) * 1974-06-07 1976-12-14 Composite Sciences, Inc. Fluid processing apparatus
US4178239A (en) * 1974-11-13 1979-12-11 Union Carbide Corporation Biological intermediate sewage treatment with ozone pretreatment
US4203837A (en) * 1976-01-16 1980-05-20 Hoge John H Process for removal of discrete particulates and solutes from liquids by foam flotation
US4064163A (en) * 1976-12-30 1977-12-20 Amchem Products, Inc. Process for the manufacture of aliphatic phosphonic acids
US4351810A (en) * 1981-07-09 1982-09-28 The United States Of America As Represented By The Secretary Of Commerce Method for removing sulfur dioxide from a gas stream
US4696739A (en) 1984-04-02 1987-09-29 Aqua Strip Corporation Water purification apparatus
US4614596A (en) 1985-01-10 1986-09-30 Wyness David K Apparatus and method for dissolving a gas in an aqueous stream
US4639314A (en) 1985-01-18 1987-01-27 Tyer Robert R Fine bubble diffuser and diffuser system having filtered blow-down tube
GB2185901A (en) 1985-12-13 1987-08-05 James Frederick Pankow Treating groundwater by sparging
US5205927A (en) 1987-09-25 1993-04-27 Battelle Memorial Institute Apparatus for treatment of soils contaminated with organic pollutants
US5227184A (en) 1987-10-30 1993-07-13 American Water Purification, Inc. Method for sanitizing food products
US4966717A (en) 1989-02-10 1990-10-30 Kern Donald W Ozone injection system and method
DE4001012C1 (en) 1990-01-16 1991-05-02 Ieg - Industrie-Engineering Gmbh, 7410 Reutlingen, De
JP2977852B2 (en) 1990-03-17 1999-11-15 株式会社日本ネイチュアロマン Ozone water generator
US5221159A (en) 1990-03-28 1993-06-22 Environmental Improvement Technologies, Inc. Subsurface contaminant remediation, biodegradation and extraction methods and apparatuses
US5472294A (en) 1990-03-28 1995-12-05 Environmental Improvement Technologies, Inc. Contaminant remediation, biodegradation and volatilization methods and apparatuses
US5049320A (en) 1990-07-03 1991-09-17 International Environmental Systems, Inc. Gas dissolving system and method
US5451320A (en) 1990-07-10 1995-09-19 International Environmental Systems, Inc., Usa Biological process for groundwater and wastewater treatment
US5122165A (en) 1990-07-10 1992-06-16 International Environmental Systems, Inc. Removal of volatile compounds and surfactants from liquid
JPH04171036A (en) 1990-11-02 1992-06-18 Masayuki Yokota Method for generating minute air bubbles in water
US5389267A (en) 1991-05-10 1995-02-14 The Board Of Trustees Of The Leland Stanford Junior University In-situ vapor stripping for removing volatile organic compounds from groundwater
US5180503A (en) 1991-05-10 1993-01-19 The Board Of Trustees Of The Leland Stanford Junior University In-situ vapor stripping for removing volatile organic compounds from groundwater
US5246309A (en) 1991-05-16 1993-09-21 Hobby Michael M System and method for decontamination of contaminated ground
US6217767B1 (en) 1992-02-03 2001-04-17 Clark Environmental Services Vacuum sparging process for treating contaminated groundwater and/or wastewater
US5238437A (en) * 1992-02-07 1993-08-24 Mattel, Inc. Bubble dispensing doll
US5427693A (en) 1992-02-10 1995-06-27 O-Three Limited Modular ozone water treatment apparatus and associated method
US5302286A (en) * 1992-03-17 1994-04-12 The Board Of Trustees Of The Leland Stanford Junior University Method and apparatus for in situ groundwater remediation
JPH0623378A (en) 1992-07-09 1994-02-01 Matsushita Electric Ind Co Ltd Removal of harmful substance in water
US5667733A (en) * 1992-08-19 1997-09-16 Lowndes Engineering Co., Inc. Aerosol generator and method for effecting the size of droplets dispersed thereby
US5425598B1 (en) 1993-08-12 1997-07-15 Leslie H Pennington System for sparging ground water contaminants
US5480549A (en) * 1994-01-25 1996-01-02 The United States Of America As Represented By The United States Department Of Energy Method for phosphate-accelerated bioremediation
US6210955B1 (en) * 1994-10-05 2001-04-03 Gas Research Institute Foam transport process for in-situ remediation of contaminated soils
US5525008A (en) 1995-01-11 1996-06-11 Wilson; James T. Remediation apparatus and method for organic contamination in soil and groundwater
US5609798A (en) * 1995-06-07 1997-03-11 Msp Corporation High output PSL aerosol generator
US5698092A (en) 1995-08-07 1997-12-16 Chen; Youzhi In-situ oxidizing zone remediation system for contaminated groundwater
US6403034B1 (en) 1995-10-31 2002-06-11 Christopher Nelson Method of reducing the concentration of recalcitrant organic contamination in a soil matrix
US6197835B1 (en) * 1996-05-13 2001-03-06 Universidad De Sevilla Device and method for creating spherical particles of uniform size
IL118741A0 (en) 1996-06-26 1996-10-16 Ozontech Ltd Ozone application for disinfection purification and deodorization
US5885775A (en) * 1996-10-04 1999-03-23 Perseptive Biosystems, Inc. Methods for determining sequences information in polynucleotides using mass spectrometry
US5851407A (en) 1996-12-04 1998-12-22 Applied Process Technolgy, Inc. Process and apparatus for oxidation of contaminants in water
US6488850B2 (en) * 1996-12-17 2002-12-03 Global Biosciences, Inc. Method and apparatus for anaerobically degrading pollutants with alkanes
US6007274A (en) 1997-05-19 1999-12-28 Arcadis Geraghty & Miller In-well air stripping, oxidation, and adsorption
US5879108A (en) 1997-06-09 1999-03-09 Eder Associates Air sparging/soil vapor extraction apparatus
US5860598A (en) * 1997-08-14 1999-01-19 Cruz; Luis R Fog atomizer
DE29821687U1 (en) * 1998-12-05 2000-04-06 Gea Finnah Gmbh Device for producing an aerosol
US6428694B1 (en) * 1999-11-17 2002-08-06 Komex H2O Science, Inc. Solar powered environmental remediation devices

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4684479A (en) * 1985-08-14 1987-08-04 Arrigo Joseph S D Surfactant mixtures, stable gas-in-liquid emulsions, and methods for the production of such emulsions from said mixtures
US5215680A (en) * 1990-07-10 1993-06-01 Cavitation-Control Technology, Inc. Method for the production of medical-grade lipid-coated microbubbles, paramagnetic labeling of such microbubbles and therapeutic uses of microbubbles
US5855775A (en) 1995-05-05 1999-01-05 Kerfoot; William B. Microporous diffusion apparatus
US5560737A (en) 1995-08-15 1996-10-01 New Jersey Institute Of Technology Pneumatic fracturing and multicomponent injection enhancement of in situ bioremediation
EP1174197A2 (en) 2000-07-06 2002-01-23 William Kerfoot Groundwater and subsurface remediation

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MARTONE J.A.: "Sampling submicrometer particles suspended in near sonic and supersonic free jets of air", DOCTORAL DISSERTATION SUBMITTED TO OREGON STATE UNIVERSITY, June 1991 (1991-06-01), CORVALLIS, OR, pages 117 - 124, XP002953723 *
See also references of EP1390303A4 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2900146A1 (en) * 2006-04-19 2007-10-26 Total Sa Cleaning the groundwater flow having contaminants e.g. benzene, comprises injecting oxygen in a permeable massive underground filter placed in the groundwater to degrade the contaminants that flow in the form of a plume
WO2007125186A1 (en) * 2006-04-19 2007-11-08 Total S.A. Method of decontaminating a water table and device for implementing it
CN104858230A (en) * 2015-05-15 2015-08-26 合肥市吴山固体废物处置有限责任公司 Restoration method for soil polluted by benzyl chloride and special water distributor
CN104858230B (en) * 2015-05-15 2017-10-17 安徽浩悦环境科技有限责任公司 The restorative procedure and special water-locator of a kind of benzyl chloride contaminated soil
CN105565466A (en) * 2016-03-02 2016-05-11 清泽环境发展(北京)有限公司 Efficient environment-friendly Fenton's reagent and method thereof for oxidizing and treating nitrobenzene

Also Published As

Publication number Publication date
US20050046055A1 (en) 2005-03-03
US6805798B2 (en) 2004-10-19
US20030029792A1 (en) 2003-02-13
US7300039B2 (en) 2007-11-27
US7156984B2 (en) 2007-01-02
EP1390303A4 (en) 2009-04-29
EP1390303A1 (en) 2004-02-25
US20050045544A1 (en) 2005-03-03

Similar Documents

Publication Publication Date Title
US6805798B2 (en) Environmental remediation method and apparatus
US7645384B2 (en) Environmental remediation method using ozonophilic bacteria within a liquid coating of bubbles
US8302939B2 (en) Soil and water remediation system and method
EP1239978B1 (en) Microporous diffuser and method of water remediation
EP1174197B1 (en) Groundwater and subsurface remediation
US6780331B2 (en) Ozonation of contaminated liquids under high pressure
US7666316B2 (en) Permanganate-coated ozone for groundwater and soil treatment with in-situ oxidation
US20090272697A1 (en) Superoxidant Poiser For Groundwater And Soil Treatment With In-Situ Oxidation-Reduction And Acidity-Basicity Adjustment
US6447676B1 (en) Springbox for water remediation
US8557110B2 (en) Groundwater and subsurface remediation
US20140263098A1 (en) Residential water treatment system for removal of 1,4 dioxane and associated compounds and method of using same
Mihopoulos et al. Complete remediation of PCE contaminated unsaturated soils by sequential anaerobic-aerobic bioventing
AU2003233398B2 (en) In situ biodegradation of subsurface contaminants by injection of phosphate nutrients and hydrogen
CA2441259C (en) Environmental remediation method and apparatus
Fogel et al. Bacterial Degradation of Aliphatic Hydrocarbons Enhanced by Pulsed Ozone Injection
Nyer et al. TREATMENT AND REMEDIATION

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2441259

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2002771856

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 2002771856

Country of ref document: EP