US20040082055A1 - Anaerobic bioremediation system - Google Patents
Anaerobic bioremediation system Download PDFInfo
- Publication number
- US20040082055A1 US20040082055A1 US10/671,257 US67125703A US2004082055A1 US 20040082055 A1 US20040082055 A1 US 20040082055A1 US 67125703 A US67125703 A US 67125703A US 2004082055 A1 US2004082055 A1 US 2004082055A1
- Authority
- US
- United States
- Prior art keywords
- geologic media
- contaminated
- accordance
- logic controller
- bioremediation
- Prior art date
- Legal status (The legal status 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 status listed.)
- Abandoned
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
-
- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/09—Reaction techniques
- Y10S423/17—Microbiological reactions
Definitions
- the present invention relates to a new and improved anaerobic bioremediation system and method thereof for anaerobic biodegradation, detoxification and transformation of toxic organic and inorganic compounds in contaminated geologic formations to harmless and safe organic and inorganic materials within the geologic media.
- the bioremediation system includes an apparatus and methods for implementing the conversion of contaminated organic and inorganic materials to clean, safe, and harmless materials via naturally occurring anaerobic bioremediation within the geologic media.
- Aerobic and anaerobic bioremediation of contaminated soils, ground water sites, lakes, ponds, aquifers, wells, shore fronts, oceans and the like have proven effective in remediating toxic organic and inorganic compounds such as fuel oil, gasoline, PCBs, DDT and other pesticides, and the like.
- Bioremediation projects that have been successfully implemented are in areas that include underground storage tank spills and leakages; hazardous solid wastes; ground spills; and contamination of ground water (wells), geological aquifers and the like. Aerobic and anaerobic bioremediation have proven to be more cost effective and timely than conventional engineering technologies, and have the further advantage in that they do not produce wastes which enter the surrounding air, water and soils.
- Anaerobic bioremediation has been shown to be the most effective and least expensive method of remediation of toxic materials.
- Other remediation technologies such as standard physical soil and ground-water remediation, i.e. excavation and disposal or pump and treat systems and soil-vapor extraction (SVE) remediation, have all been shown to be moderately high in capital costs; to require long-term operation and maintenance including labor, materials and power consumption; to require time parameters that are in months to years; and to have remediation effectiveness results being moderately low in the cleanup of the contaminated soils and ground water.
- SVE soil-vapor extraction
- remediation techniques are also limited by considerations of depth of soil to be removed; obstructions in the geologic formations; safety conditions at the site; and environmental law statutes with regard to Federal, State and local regulatory agencies for a site remediation project that produces wastes that affect air, water and soil conditions.
- These aforementioned remediation technologies generally are less feasible and significantly more expensive and sometimes prohibitive in terms of logistics and/or overall costs.
- the bioremediation be accomplished by having an in-situ treatment of the contaminated geologic media such that the organic and inorganic contaminants are metabolized or transformed by naturally occurring indigenous, denitrifying and/or manganese-, iron- and sulfate-reducing anaerobic microorganisms using the aforementioned electron acceptors, in combination with nutrients, surfactants, chelating agents, a diluent, and an inert gas to convert the contaminants within the contaminated geologic media into non-toxic end products.
- MRP multiple respiration pathway
- U.S. Pat. No. 5,265,674 to Fredrickson et al discloses an enhancement method of in-situ remediation of aquifers.
- This method of bioremediation is adapted to deliver microorganisms, enzymes, nutrients and electron donors to subsurface zones contaminated by nitrates in order to stimulate or enhance denitrification.
- the remediation system includes nutrient tanks, pumps, conduit/piping, an injection well and reclamation tanks.
- This prior art patent does not disclose the apparatus or methods for the bioremediation of contaminated geologic media as in the present invention.
- U.S. Pat. No. 5,342,769 to Hunter et al discloses a method for bioremediation of liquid or slurry hazardous waste streams for the removal of halogenated hydrocarbons by using naturally occurring anaerobic microorganisms having methanogenic characteristics.
- the remediation method includes a series of reactors, pumps, vacuum pumps, and conduits.
- This prior art patent does not disclose the apparatus or methods for the bioremediation of contaminated geologic media as in the present invention.
- U.S. Pat. No. 5,384,048 to Hazen et al discloses an apparatus and method for in-situ bioremediation of contaminated ground water and/or contaminated subsurface soil by chlorinated hydrocarbons.
- a nutrient fluid is used to stimulate the growth and reproduction of indigenous aerobic microorganisms that are capable of degrading the contaminants.
- the apparatus used for the bioremediation process includes injection wells, pumps, conduits, and monitoring/sensor components. This prior art patent does not disclose the apparatus or methods for the bioremediation of contaminated geologic media as in the present invention.
- U.S. Pat. No.5,398,756 to Brodsky et al discloses a process for the in-situ bioremediation of contaminated soil.
- the process includes the forming of at least one liquid permeable region within the contaminated soil region, introducing microorganisms, nutrients and the like for degrading contaminants in the contaminated soil region, and transmitting direct electric current through the contaminated soil region for degrading the contaminants by electrochemical means.
- This prior art patent does not disclose the apparatus or methods for the bioremediation of contaminated geologic media as in the present invention.
- U.S. Pat. Nos. 5,482,630 and 5,556,536 to Lee et al and Turk disclose a controlled denitrification process and system using a bacterial bed.
- This bioprocess system is used for the reduction of nitrate to nitrogen in a fluid medium, such that anaerobic bacteria fed by a carbon source are used for the nitrate reduction.
- a column of suspended beads are used as the anaerobic bacterial bed for denitrification.
- This prior art patent does not disclose the apparatus or methods for the bioremediation of contaminated geologic media as in the present invention.
- U.S. Pat. No. 5,560,737 to Schuring et al discloses a method and apparatus for pneumatic fracturing and multicomponent injection enhancement of in-situ bioremediation in treating subsurface soil contaminated with organic compounds.
- This bioremediation method and apparatus provides for reducing or eliminating non-naturally occurring, subsurface, liquid contaminants within a geologic formation, which involves the steps of pneumatically fracturing the soil formation to produce a fracture network.
- a pressurized gas stream is used having nutrients, oxygen, electron acceptors, pH buffers, and possible bacterial augmentation to add a different culture of microorganisms to the soil formation when used in fracturing the soil formation.
- MRP multiple-respiration pathway
- an object of the present invention to provide an anaerobic bioremediation system for the anaerobic biodegradation, detoxification and transformation of toxic organic and inorganic contaminants in contaminated geologic media into non-toxic compounds without further formation of regulated wastes or other undesirable by-products that affect the air, water and soil at environmental-contamination sites.
- Another object of the present invention is to provide an anaerobic bioremediation system for in-situ treatment of geologic media containing organic and inorganic contaminants that are metabolizable or transformable by indigenous anaerobic bacteria capable of utilizing one or more multiple respiration pathways (MRP) including denitrification, manganese-reduction, iron-reduction and sulfate-reduction within the contaminated geologic media at a site.
- MRP multiple respiration pathways
- Another object of the present invention is to provide an anaerobic bioremediation system having apparatus which enables the delivery of nutrients and electron acceptors having an inert carrier gas to the indigenous MRP anaerobic microorganisms in order to promote conditions favorable to the growth of these indigenous microorganisms such that the metabolism or transformation of the contaminants by these microorganisms can easily take place, without the use of implanted microorganisms at the contaminated site.
- Another object of the present invention is to provide an anaerobic bioremediation system having apparatus which enables the nutrients and electron acceptors and an inert carrier gas to be more readily and rapidly dispersed in the contaminated geologic media and made more available to a large area within the contaminated geologic media.
- Another object of the present invention is to provide an anaerobic bioremediation system that can easily deliver nutrients, electron acceptors, chelating agents, surfactants and diluent with an inert carrier gas being in a chemical composition form that is readily utilizable and metabolizable by the indigenous MRP anaerobic microorganisms.
- Another object of the present invention is to provide an anaerobic bioremediation system that has the capacity to supply macro-nutrients, micro-nutrients, electron acceptors, surfactants, and chelating agents, as well as to modify the pH, redox potential and oxygen availability in the subsurface geologic media.
- Another object of the present invention is to provide an anaerobic bioremediation system that has the capacity to supply biologically usable phosphate to phosphate-limited environments, whereby sodium hexametaphosphate or other forms of hydrolyzable ringed or linear polyphosphates are used as the primary source of phosphate, as such compounds are much less prone to in-situ precipitation than other forms of phosphate, enabling a major improvement for the stimulation and growth of indigenous MRP microorganisms in the contaminated geologic formation.
- Another object of the present invention is to provide an anaerobic bioremediation system that has the capacity to supply nitrate as both an electron acceptor and the main source of assimilated (i.e., nutrient) nitrogen, taken together with other unique aspects of the chemical compositions of the present invention, which enables a major improvement for the stimulation and growth of indigenous denitrifying and MRP microorganisms in the contaminated geologic media.
- Another object of the present invention is to provide an anaerobic bioremediation system having apparatus that is simple to construct and use and which enables efficient delivery and monitoring of the nutrients and electron acceptors for the optimum growth rate and kinetics of various indigenous, denitrifying and other MRP anaerobic microorganisms in order to maximize the rate of degradation and transformation of the contaminants into non-toxic compounds by these indigenous MRP microorganisms.
- Another object of the present invention is to provide an anaerobic bioremediation system having a process that is inexpensive and easy to operate, especially under actual field conditions and the logistical constraints of active sites.
- Another object of the present invention is to provide an anaerobic bioremediation system having a process that can be performed rapidly and safely in the field and result in the site meeting environmental clean-up standards set by various governmental agencies more rapidly and at a lower cost than can be accomplished with other methods.
- a further object of the present invention is to provide an improved anaerobic bioremediation system that can be easily produced in an automated and economical manner and is readily affordable by various responsible parties, consultants, contractors, engineers, governmental agencies and corporate users.
- the present invention includes a bioremediation apparatus for anaerobic biodegradation, detoxification, and transformation of toxic organic and inorganic compounds in a contaminated geologic media.
- the bioremediation apparatus includes a first set of one or more storage tanks containing a chemical composition for anaerobic biodegradation of toxic compounds in contaminated geologic media; a plurality of quick disconnect valve couplings connected to the first set of storage tanks; at least one logic controller having a logic controller programmer component for opening and closing an automatic valve connected to the first set of storage tanks to supply the chemical composition to the contaminated geologic media; and a screened well connected to the first set of storage tanks for supplying the chemical composition to the contaminated geologic media.
- the present invention also includes methods for anaerobic biodegradation, detoxification, and transformation of toxic organic and inorganic compounds in contaminated geologic media.
- the basic method includes pressurizing one or more storage tanks containing a chemical composition and an inert carrier gas; connecting a plurality of quick disconnect valve couplings to one or more pressurized storage tanks; connecting a well to an automatic ball valve for supplying the chemical composition and the inert carrier gas through the well to the contaminated geologic media; and opening and closing of the automatic ball valve to dispense the chemical composition and the inert carrier gas under pressure through the well to the contaminated geologic media.
- FIG. 1 is a side elevational view of the anaerobic bioremediation system of the preferred embodiment of the present invention showing the bioremediation processing apparatus and its major component assemblies therein and in operational use.
- FIG. 2 is a front perspective view of the anaerobic bioremediation system of the preferred embodiment of the present invention showing the subsurface housing containing the bioremediation processing apparatus and its component parts contained therein; and in operational use. It is noted that there is an alternate configuration for connecting the bioremediation processing apparatus as shown in the following two figures.
- FIG. 3A is a front perspective view of the anaerobic bioremediation system of the preferred embodiment of the present invention showing the dispensing apparatus assembly and its component parts contained therein and the electronic control assembly and its component parts contained therein.
- the product canisters are operated in series using this set-up.
- FIG. 3B is a front perspective view of the anaerobic bioremediation system of the preferred embodiment of the present invention showing an alternate dispensing apparatus assembly and its component parts contained therein and the electronic control assembly and its component parts contained therein.
- the product canisters are operated in parallel using this alternate set-up.
- FIG. 3A series product canister operation
- the system can also be set up and operated using the parallel product canister configuration depicted in FIG. 3B.
- FIG. 4 is a front perspective view of the anaerobic bioremediation system of the preferred embodiment of the present invention showing the electronic control assembly and its component parts contained therein.
- FIG. 5 is a side elevational view of the anaerobic bioremediation system of the preferred embodiment of the present invention showing the bioremediation processing apparatus having the dispensing apparatus assembly, the electronic control assembly, and the first well component assembly; and the vapor suppression system and a second well component assembly; with both systems being in operational use.
- FIG. 6 is a front perspective view of the anaerobic bioremediation system of the alternate embodiment of the present invention showing the vapor suppression system and its component parts contained thereon and in operational use.
- FIG. 7 is a front perspective view of the anaerobic bioremediation system of the preferred and alternate embodiments of the present invention showing dual dispensing apparatus assemblies and dual electronic control assemblies being electrically interconnected for the alternate feeding of the standard nutrient composition and alternative nutrient compositions into the well component assembly.
- FIG. 8 is a side elevational view of the anaerobic bioremediation system of the alternate embodiment of the present invention showing the bioremediation processing apparatus for use in bioremediation applications involving dense non-aqueous phase liquid contaminants (DNAPLs) having a dispensing apparatus assembly, an electronic control assembly and a well component assembly; and in operational use.
- DNAPLs dense non-aqueous phase liquid contaminants
- FIG. 9 is a side elevational view of the anaerobic bioremediation system of the alternate embodiment of the present invention showing the bioremediation processing apparatus for use in bioremediation applications involving light non-aqueous phase liquid contaminants (LNAPLs) having a dispensing apparatus assembly, an electronic control assembly and a well component assembly; and in operational use.
- LNAPLs light non-aqueous phase liquid contaminants
- FIG. 10 is a schematic diagram of the anaerobic bioremediation system of the present invention showing the generic stoichiometric equations for the bioremediation processes of converting organic contaminants into non-toxic byproducts, such as carbon dioxide, nitrogen gas and water via denitrification.
- the anaerobic bioremediation system apparatus and methods of this invention provide the means for the anaerobic biodegradation, detoxification and transformation of toxic organic and inorganic compounds in contaminated geologic media to harmless and safe organic and inorganic materials within the geologic media.
- In-situ bioremediation has recently emerged as the general category of site remediation technologies which provides for the most timely and effective remediation of contaminated soil and ground water from petroleum hydrocarbon spills, releases of halogenated hydrocarbons, solvents and pesticides, inorganic chemical dumping, and the like.
- field demonstrations of bioremediation technologies have typically outperformed laboratory studies, even though it has often been assumed by experts in the field that ideal conditions were established in the laboratory.
- the success of bioremediation field trials, including those of the present invention is thought to be attributable to the greater diversity of bacterial populations and their enzymatic processes that are present in the natural hydrogeologic settings versus those that can be established in laboratory microcosms.
- In-situ bioremediation provides for the potential of a swift reduction of contaminant levels, often in periods as short as weeks to months, as shown in examples of the actual use of the present invention on contaminated geologic formations as provided below.
- the present invention uses naturally-occurring bacteria that are indigenous to the geologic formation being remediated for the degradation of hydrocarbons, solvents, pesticides, hazardous wastes and the like.
- the theoretical basis and effectiveness of using indigenous MRP anaerobic microorganisms capable of denitrification, manganese-reduction, iron-reduction and sulfate-reduction is demonstrated in the bioremediation process diagram (FIG. 10) which describes the theoretical operation of the bioremediation system 10 of the present invention.
- the present invention provides a means of stimulating such MRP anaerobic microorganisms so as to achieve rapid and effective degradation and remediation of aromatic hydrocarbons as well as halogenated hydrocarbons, pesticides, hazardous wastes and other contaminants as demonstrated in the forthcoming examples of projects conducted at actual contaminated geologic sites.
- anaerobic microorganisms such as denitrifying bacteria and other MRP anaerobic bacteria in the present invention is dependent upon the natural sequence of electron-acceptor utilization by bacteria within geologic media as well as the natural occurrence and/or solubility of these electron acceptors in water.
- Bacteria utilize electron acceptors in the order of their decreasing energy yield (Gibbs Free Energy [ ⁇ G] in KJ/mole CH 2 0).
- a higher-energy electron acceptor wanes e.g., O 2
- conditions become favorable for microbial respiration with lower-energy electron acceptors (e.g., NO 3 , Mn(IV), Fe(IIl), and SO 4 ).
- nitrate and sulfate salts are much more soluble in water than is oxygen. Nitrate and sulfate are also more “conservative” than oxygen in terms of their geochemistry, i.e., these species are less reactive and more mobile. Therefore, diffusive processes can be used to deliver non-limiting concentrations of nitrate and sulfate to the interior of ground-water contaminant plumes in relatively short periods of time because of the significant in-situ concentration gradients that can be established by the present invention.
- ⁇ G ⁇ 448 KJ/mole CH 2 O
- denitrification is more efficient (if not more rapid) than aerobic processes, as only 1 mole of nitrate versus 1.25 moles of oxygen is consumed in the degradation of one mole of contaminant.
- the ultimate end-products of denitrification are carbon dioxide, water and elemental-nitrogen gas. Consequently, one advantage of the present invention is that it facilitates the use of denitrification as a naturally safe and practical means of bioremediation as shown in the bioremediation process 10 of the present invention.
- one advantage of the present invention is that it facilitates the use of denitrification as a naturally safe and practical means of bioremediation as shown in the bioremediation process 10 of the present invention.
- the present invention provides means by which multiple chemical compositions can be used to stimulate microorganisms that utilize various redox conditions and microbial respiration pathways in-situ within the contaminated geologic media (see Table 1), so as to enhance the growth of MRP anaerobic microorganisms and to optimize contaminant biodegradation and/or biotransformation by such microorganisms.
- such utility of the present invention provides means for cycling through a series of redox conditions in-situ within the contaminated geologic media as illustrated in FIG. 10.
- Redox cycling within the contaminated geologic media in-situ is achieved by using one or more chemical compositions in such a manner so as to stimulate a temporal and/or spatial succession of redox conditions and anaerobic respiration pathways in the subsurface.
- a typical redox-cycling application facilitated by the present invention may begin with the stimulation of denitrification followed by manganese-reduction, iron-reduction and sulfate-reduction and returning again to nitrate reduction.
- one or more chemical compositions may be used to stimulate denitrification, followed by the use of one or more chemical compositions to stimulate manganese-reduction, iron-reduction (and/or the reduction of other metals which can serve as microbial electron acceptors), followed by the use of one or more chemical compositions to promote the growth of anaerobic bacteria via sulfate-reduction, followed by the return to using one or more chemical compositions to again stimulate denitrifying conditions. Because of the nature of the apparatus and methods of the present invention, this invention also provides a means for varying such redox cycles to meet site-specific conditions or otherwise difficult contamination problems.
- the aforementioned cycling of redox conditions as facilitated by the present invention provides for the stimulation of a much more diverse community of MRP anaerobic microorganisms than could otherwise be achieved by other methods, which in turn provides a means of optimizing contaminant biodegradation and/or biotransformation in-situ within contaminated geologic media.
- the present invention provides means of providing MRP anaerobic bacteria with macro-nutrients and micronutrients needed to sustain bacterial growth and to promote biodegradation and/or biotransformation of organic and inorganic contaminants.
- macro-nutrients such as inorganic nitrogen (e.g., ammonium) and phosphate.
- Bacteria utilize ammonium and similar forms of nitrogen to help synthesize proteins and other complex organic molecules.
- Bacteria also require phosphate for the production of nucleic acids, phospholipids, and other biochemicals as well as for the maintenance of adequate levels of nucleoside 5′ triphosphates such as adenosine-triphosphate (ATP), the most common intracellular “energy-molecule.”
- nucleoside 5′ triphosphates such as adenosine-triphosphate (ATP), the most common intracellular “energy-molecule.”
- ATP adenosine-triphosphate
- Some researchers have shown that the availability of 10-20 mg/l of phosphate (PO 4 ⁇ 3 ) is typically sufficient to stimulate the biodegradation of aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylenes (BTEX) in ground water.
- phosphate salts cause precipitates to form close to the injection well screens because of the reactive geochemistry between phosphate and the cations naturally present in geologic media.
- the use of sodium hexametaphosphate and/or other ringed or linear polyphosphates for phosphate addition may be preferred to help overcome the typical fouling problems encountered by using other forms of phosphate.
- this invention provides a means of providing chelating agents to minimize abiotic reactions between phosphate and the naturally occurring cations in the geologic media.
- Trace metal micronutrients including, but not limited to, iron, molybdenum, copper, cobalt, manganese, boron and zinc are also important to the growth of denitrifying bacteria and other MRP anaerobic bacteria. These trace metals are required in the key enzymatic processes by which nitrate-reducing bacteria and other MRP anaerobes metabolize carbon sources such as hydrocarbons, halogenated solvents, pesticides, hazardous wastes and the like. For example, previous research reported in the literature has indicated that the addition of ⁇ 10 ⁇ g/l of key trace metals along with nitrate and phosphate facilitated the more effective degradation of BTEX compounds relative to the addition of nitrate and phosphate alone.
- micronutrients are important to the growth of MRP anaerobic bacteria
- research related to the operational use of the present invention including experience in various geologic settings and contaminant conditions, has shown that the soil and ground water at each of these sites often provides an adequate supply of these micronutrients.
- the bioremediation system 10 of the present invention and the applications thereof provide means for the application of such micronutrients, if required, to enhance bioremediation.
- the substrate which is used as an electron donor within the contaminated geologic formation for anaerobic biodegradation could include organic chemical compounds or contaminants including petroleum-based hydrocarbons, halogenated hydrocarbons and solvents, polychlorinated biphenyls (PCB's), dioxin, pesticides, and other toxic/hazardous wastes.
- typical petroleum hydrocarbons include gasoline, diesel fuel, fuel oils and lubricating oils, as well as gasoline and diesel additives such as methyl tertiary butyl ether (MTBE), ethanol, tertiary butyl alcohol (TBA) and the like.
- Examples of typical halogenated hydrocarbons and solvents that are used as a carbon source by MRP anaerobic bacteria during the remediation of a contaminated site could include carbon tetrachloride, tetrachloroethylene, tetrachloroethane, trichloroethylene, 1,1,1,-trichloroethane, 1,1,2-trichloroethane, 1,2-dichloroethylene, chloroform, methylene chloride, 1,2-dibromoethane, 1,2-dichloroethane, vinyl chloride, trichlorofluoromethane (Freon 113), and the like.
- Typical pesticides, herbicides, insecticides, mitacides, and nitroaromatic compounds being remediated at a contaminated site could include dinoseb (2-(1-melkylpropyl)-4,6-dinitrophenol, DDT, DDD, DDE, DiazanonTM, chlordane, malathion, trinitrotoluene (TNT), dinitrotoluene (DNT), toxaphene, and the like.
- Typical inorganic contaminants and/or hazardous-wastes being remediated could include cyanides, cobalt-60, hexavalent chromium, uranium (VI), and other transition metals with the potential for reduction from higher valence states to lower valence states.
- the bioremediation processing apparatus 50 for the anaerobic bioremediation system 10 of the preferred embodiment of the present invention is represented in FIGS. 1 through 4 of the drawings.
- the bioremediation processing apparatus 50 is the delivery and feeding mechanism for transporting a nutrient fluid chemical composition 40 to the contaminated geologic formation 30 in order to stimulate anaerobic biodegradation, detoxification and transformation of toxic organic and inorganic compounds into harmless and safe end-products.
- the bioremediation processing apparatus 50 includes a metal or concrete housing component 52 , a dispensing apparatus assembly 80 for dispensing of composition 40 ; an electronic control assembly 130 for electronically metering composition 40 ; and a well component assembly 150 for delivering of composition 40 to the contaminated geologic formation 30 .
- Bioremediation processing apparatus 50 includes a cylindrical subsurface housing 52 made of metal or concrete having an outer cylindrical bentonite seal layer 54 .
- Housing 52 also includes an outer manhole cover 58 having an insulation layer 60 attached to the cover inner wall member 62 .
- sub-surface housing 52 includes a cylindrical wall member 64 having inner and outer surface walls 66 and 68 , and a bottom wall member 70 being a gravel layer.
- Bottom gravel wall member 70 further includes a top surface wall 72 and a bottom surface wall 74 .
- Bottom wall member 70 includes a circular hole opening 76 within the gravel layer for receiving the upper end 154 of well casing 152 .
- Insulation layer 60 on cover 58 protects composition 40 within the plurality of product canister tanks 100 a to 100 f of dispensing apparatus assembly 80 from freezing.
- the dispensing apparatus assembly 80 includes a carrier gas cylinder 82 for holding of inert gas 22 having a gas regulator assembly 84 , a plurality of stainless steel product canister tanks 100 a to 100 f for holding of composition 40 therein having removable lids 102 a to 102 f , and a plurality of quick disconnect couplings 104 a to 104 l for tanks 100 a to 100 f .
- a plurality of jumper line tubing 106 a to 106 f is attached to the aforementioned couplings 104 a to 104 e for connecting each of the product canister tanks 100 a to 100 f in series.
- the plurality of quick disconnect couplings 104 a to 104 l and the plurality of jumper line tubing 106 a to 106 f use a plurality of hose barb adapters 108 a to 108 j and 110 and a plurality of stainless steel hose clamps 112 a to 112 j for connecting the aforementioned quick disconnect couplings 104 a to 104 j and jumper line tubing 106 a to 106 f with each other.
- manifold 99 a In using the alternate set-up of the dispensing apparatus as depicted in FIG. 3B, manifold 99 a would be used with a plurality of jumper line tubing ( 106 a to 106 f connecting the manifold to the individual product canister tanks 100 a to 100 f , which would be operated in parallel rather than in series. Jumper lines 106 a′ to 106 f would connect each individual product canister tank discharge to manifold 99 b , which would discharge to the logic controller, as shown in FIG. 3B.
- the gas regulator assembly 84 for the carrier gas cylinder 82 includes a gas regulator shut-off valve 86 , a barbed-stem outlet line 90 and in-line pressure gauges 92 a and 92 b ; there is a separate shut-off valve 88 for gas cylinder 82 .
- Attached to gas regulator assembly 84 is a regulator gauge protection cage 94 , and flexible link-up tubing 98 for connecting to the first product canister tank 100 a when the product tanks operated in series.
- the dispensing apparatus assembly 80 further includes a manually operated ball valve 114 which connects to the electronic control assembly 130 on one end and to well 152 on the other end via connecting tubing 148 .
- the electronic control assembly 130 includes a logic controller 132 having a logic controller programmer component 134 for inputting a program or algorithm and executing such, and a timing element component 136 for electronically opening and closing an automated ball valve 138 in accordance with the program or algorithm, for precise metering of composition 40 to the contaminated geologic formation 30 at precise time intervals.
- logic controller 132 is powered by a battery pack 142 via electrical lines 140 for operating in the field where no electrical power outlets are available. It is noted that battery pack 142 and electrical line 140 can be contained within the logic controller 132 , as well as externally as shown in the drawings.
- Composition 40 is discharged through the automatic ball valve 138 when it is in the open position, into a length of discharge tubing 148 , as shown in FIGS. 2 through 5.
- Logic controller 132 may further include additional means for controlling the metering of composition 40 to the contaminated geologic formation 30 , via the option of a plurality of digital and/or fiber-optic sensors 144 a to 144 i for the in-situ monitoring of parameters such as the static-water levels, the changes in static-water levels, the in-situ concentrations of each of the components of the chemical compositions or the by-products thereof, the rate of use of one or more of the components of the chemical compositions by the MRP microorganisms, the total estimated mass of the microorganisms in-situ, the biomass growth rate of the naturally occurring MRP microorganisms in-situ, the conversion rates of the converted end-products being generated by the MRP microorganisms, the pH and/or redox potential of the saturated geologic media or biomass, and the temperature of the saturated geologic media and other pertinent measurable data needed.
- Logic controller 132 also includes a display component 146 for displaying the sensor outputs; as
- Bioremediation processing apparatus 50 further includes an optional pressurized water feed 109 , as shown in FIG. 1.
- the pressurized water feed consists of a pressurized water line 111 , connected to a pressurized water supply main; a pressure-reducing valve 113 ; a logic controller 132 ′; a manually-operated ball valve a 114 ′; and discharge tubing 115 .
- the purpose of the optional pressurized water feed is (1) to provide additional fluid to periodically flush the concentrated fluid composition through the contaminated geologic media 30 at precise rates and time intervals, and (2) to increase saturation of the contaminated geologic media.
- the well component assembly 150 includes a PVC well riser 152 having an upper end section 154 and a lower end PVC screen section 156 having slotted openings 158 within.
- the well PVC riser 152 is surrounded by backfilled soil cuttings 160 and a bentonite seal 162 at the upper end section 154 of the well PVC riser 152 ; and is surrounded by a Morie (or equivalent) sand pack 164 at the lower end section 156 of the well PVC riser 152 .
- the well PVC riser 152 includes an inlet opening 166 , a plurality of discharge outlet openings 168 s and a bottom end cap 169 .
- Composition 40 is discharged into the contaminated geologic media 30 through discharge openings 168 s via the PVC screen 156 of well 152 .
- the use of well 152 installed within a contaminated geologic formation 30 is to form an interface area 170 for bioremediation applications including light non-aqueous phase liquid contaminants (LNAPLs) where these contaminants have a specific gravity of less than one, as shown in FIG. 9, and/or installed to form an interface area 170 with one or more hydrogeologic aquitards 36 for the bioremediation applications involving dense non-aqueous phase liquid contaminants (DNAPLs) where these contaminants have a specific gravity of more than one, as shown in FIG. 8.
- the use of the PVC screen 156 within well 152 at depths of no more than 0.5 feet to 10 feet below the seasonal low of the water table level 28 is for the bioremediation applications involving light non-aqueous phase liquid contaminants (LNAPLs) where these contaminants have a specific gravity of less than one.
- Outlet tubing 148 connected to the manual ball valve 114 extends into the inlet opening 166 , as shown in FIG. 1, for discharging of composition 40 into the contaminated geological formation 30 through multiple outlet opening 168 s.
- the present invention further includes an improved and optional subsurface vapor-inerting system 200 , as depicted in detail by FIGS. 5 and 6 of the drawings.
- the subsurface vapor-inerting system 200 is used for the reduction of oxygen gas (O 2 ) concentrations 24 within the vadose zone section 38 of the contaminated geologic site 30 which provides fire safety prevention that reduces and/or eliminates flash fires and/or explosion hazards associated with oxygen gas 24 and hydrocarbon contaminants 14 in the vadose zone 38 where the potential for such fire and explosion hazards exists.
- the subsurface vapor-inerting system 200 includes an inert gas assembly 202 for dispensing of an inert gas 22 ; and a well component assembly 220 for transferring the inert gas 22 to the contaminated geologic formation 30 .
- the well component assembly 220 of the vapor-inerting system 200 is installed close to the well component assembly 150 , and is constructed in a similar manner to well component assembly 150 , except for the screened PVC section 226 interval within the well riser 222 which is no more than 1 ft to 10 ft above the seasonal high of water table level 28 .
- the compressed inert gas 22 such as argon gas (A) is dispensed within the well 222 in a manner so as to maintain the gravitational flow or passive flow of the argon gas 22 into the vadose zone 38 of the geologic media 30 in order to reduce any potential for fire and explosions in the vadose zone 38 .
- This vapor-inerting system 200 is also used to provide an improved mechanism for the enhancement of anaerobic bioremediation processes, as the argon gas 22 enables the maintenance of anaerobic conditions within the contaminated geologic media being remediated.
- the inert gas assembly 202 includes an inert gas cylinder 204 having a gas regulator 206 with a gas regulator valve 208 , a shut-off valve 210 , an outlet connection component 212 and pressure in-line gauges 214 a and 214 b for maintaining a precise outlet pressure to properly blanket the vadose zone 38 with the argon gas (A) 22 suppressing vapors produced by the subsurface contaminants.
- Gas regulator 206 in addition includes a regulator gauge protection cage 216 , and flexible tubing 98 for discharging of the argon gas (A) 22 into the well 222 .
- the well component assembly 220 includes a PVC well riser 222 having an upper end section 224 and a lower end PVC screen section 226 .
- well component assembly 220 includes a separate subsurface housing unit 252 made of concrete or metal for containing both the inert gas assembly 202 and well component assembly 220 therein.
- Housing 252 includes an outer cylindrical bentonite layer 254 , and an outer manhole cover 258 .
- sub-surface housing 252 includes inner and outer surface walls 266 and 268 and a bottom wall member 270 being a gravel layer.
- Bottom wall member 270 includes a circular hole opening 276 within the gravel layer for receiving the upper end section 224 of well casing 222 .
- the PVC well riser 222 is surrounded by backfilled soil cuttings 230 and a bentonite seal 232 at the upper end section 224 of the well PVC riser 222 ; and is surrounded by a Morie (or equivalent) sand pack 234 at the lower end section 226 of the well PVC riser 222 .
- the well PVC riser 222 includes an inlet opening 236 , a plurality of discharge side outlet openings 236 s and a bottom end cap 269 .
- Inlet opening 236 includes a well cap 238 having a disconnect coupling/fitting 242 thereon.
- composition 40 and alternative chemical compositions 41 , 42 , 43 , 44 and 45 can be used in dual or other multiple dispensing apparatus assemblies 80 and 80 ′, with dual or multiple electronic assemblies 130 and 130 ′ for the predetermined alternate feeding of composition 40 and alternative compositions 41 , 42 , 43 , 44 and 45 into the well component assembly 150 via inlet opening 166 .
- This allows compositions 40 , 41 , 42 , 43 , 44 and 45 to be received into the contaminated geologic media 30 in precisely timed pulses in a manner which enables the temporal cycling of redox pathways so as to optimize the growth and health of MRP anaerobic microorganisms and to optimize contaminant degradation by such microorganisms 12 .
- the anaerobic bioremediation system 10 facilitates the anaerobic biodegradation, detoxification, and/or transformation of contaminant compounds such as petroleum hydrocarbons, halogenated solvents, polychlorinated biphenyls, dioxins, pesticides, cyanides, toxic metals, hazardous wastes and the like that have been released into surface environments and/or subsurface geologic media 30 whereby such contaminants are transformed into safe, less-toxic and/or harmless end-products.
- contaminant compounds such as petroleum hydrocarbons, halogenated solvents, polychlorinated biphenyls, dioxins, pesticides, cyanides, toxic metals, hazardous wastes and the like that have been released into surface environments and/or subsurface geologic media 30 whereby such contaminants are transformed into safe, less-toxic and/or harmless end-products.
- the bioremediation system 10 also facilitates the anaerobic biodegradation, detoxification, and/or transformation of toxic organic and inorganic compounds in contaminated geologic media 30 under a wide range of reducing redox conditions and anaerobic respiration pathways including denitrification, manganese-reduction, iron-reduction and sulfate-reduction.
- Another application of the use of the anaerobic bioremediation system 10 would be to facilitate the suppression of hydrogen sulfide (H 2 S), related sulfides, mercaptans and the undesirable odors related to these compounds produced as a result of the metabolic activity of sulfur-reducing microorganisms via the stimulation and maintenance of denitrifying, manganese-reducing and iron-reducing conditions.
- H 2 S hydrogen sulfide
- the well component assembly 150 provides a proper fluid-exchange interface with the contaminated geologic media 30 which in turn provides a means of infiltration of chemical composition 40 , optional water feed 20 , and carrier gas 22 within the contaminated geologic formation 30 for stimulating and facilitating the bioremediation of the toxic organic and inorganic compounds by the indigenous anaerobic microorganisms 12 located within the aforementioned geologic formation 30 .
- the present invention also provides for an improved subsurface vapor-inerting system 200 designed to reduce oxygen gas (O 2 ) concentrations 24 in the vadose-zone 38 of the contaminated geologic media 30 in order to reduce or eliminate the potential for flash fires and/or explosion hazards in the subsurface areas where the potential for such fire and explosion hazards exists.
- the well component assembly 220 of the vapor-inerting system 200 is installed adjacent to the well component assembly 150 .
- the PVC well riser 222 of well component assembly 220 delivers the inerting argon gas 22 to the vadose zone 38 of the contaminated geologic media 30 while simultaneously the PVC well riser 152 of well component assembly 150 delivers the chemical nutrient composition 40 and the argon carrier gas 22 to the contaminated area of geologic media 30 in order to stimulate the indigenous anaerobic microorganisms 12 at that interface area 170 within the aforementioned contaminated geologic media 30 .
- the vapor inerting system 200 can also be used independently of the anaerobic bioremediation system 10 .
- the anaerobic bioremediation system provides convenient and flexible means of either preparing composition 40 in a large make-up mixing tank (not shown), or in the actual product tank canisters 100 a to 100 f at a convenient off-site premise or at the contaminated geologic site 30 , when logistics permit it. If composition 40 is prepared in the larger mixing tank, composition 40 is then transferred to the plurality of product tank canisters 100 a to 100 f via a portable pump (not shown).
- the product tanks 100 a to 100 f are filled with composition 40 , their respective lids 102 a to 100 f are closed shut and the product tanks 100 a to 100 f are then pressurized by argon gas (A) 22 thereby sealing their respective lids 102 a to 102 f to prevent leaks of composition 40 contained therein.
- the product tank canisters 100 a to 100 f are then transported to the contaminated geologic site 30 .
- Another preparation step is the development of a computer program for the logic controller 132 of the electronic control assembly 130 where the algorithms in the program are based on mathematical models of one or more of the following operating parameters for the bioremediation system 10 :
- a plurality of digital and/or fiber-optic sensors 144 a to 144 i may be connected to logic controller 132 and regularly calibrated to monitor and/or control the delivery of composition 40 based upon real-time measurements of one or more parameters in-situ at selected locations within the contaminated geologic media 30 .
- such parameters may include in-situ monitoring of the following:
- the operator (being at the site) removes the outer manhole cover 58 having a foam insulation 60 attached from the top of the subsurface apparatus housing 52 allowing the operator access to the well component assembly 150 within housing 52 .
- the operator then places the plurality of product tanks 100 a to 100 f , and the electronic control assembly 130 within the subsurface housing 52 , such that the product tanks 100 a to 100 f are placed on the bottom floor 72 in a circular fashion such that the last product tank 100 f having the electronic control assembly 130 attached thereto is adjacent and in close proximity to the well component assembly 150 .
- the product tanks 100 a to 100 f are then joined together via the plurality of quick disconnect couplings 104 a to 104 l having the jumper-line tubing 106 a to 106 f attached thereto, if being operated in series as shown in FIG. 3 a . If being operated in parallel as shown in FIG. 3 b , the jumper line tubing is connected from the manifolds 99 a and 99 b to the product tanks 100 a to 100 f .
- the operator then connects the battery power pack 142 via electrical power line 140 for supplying electrical power to the logic controller 132 .
- the operator then connects the logic controller 132 to the last product tank 100 f via quick disconnect coupling 104 l (for series operation).
- the gas cylinder 82 having argon gas (A) 22 (which is still located at ground level 26 above the apparatus system 50 for easier access) is then connected to the first product tank 100 a (for series operation) or to the gas manifold 99 a (for parallel operation) via the quick disconnect coupling 104 a .
- the operator also checks that the logic controller 132 is manually actuated and the ball valve 114 is opened, and the logic controller 132 is set and adjusted to the desired flow of composition 40 out of the controller 132 and into the product tubing 148 .
- composition 40 is flowing freely through the dispensing apparatus assembly 80 of the bioremediation processing apparatus 50 and out the end of product tubing 148 , the logic controller program component 134 and timing element 136 of logic controller 132 are checked again or modified if desired by the operator. Then the logic controller 132 is manually closed and set to an automatic setting by the operator. The product tubing 148 is then placed into the well apparatus 150 . The gas cylinder 82 which is already connected to the first product tank 100 a or gas manifold 99 a is then placed into subsurface housing 52 next to the first product tank 100 a or gas manifold 99 a.
- the gas cylinder 82 is connected to the gas manifold 99 a , and jumper tubing from the inlet of each uproduct tank is connected to the gas manifold. Jumper lines are then connected to the discharge of each product tank at one end and to the liquid manifold 99 b on the other end, as shown in FIG. 3B.
- the rest of the set-up process as described above for series operation, is the same for parallel product tank operation.
- manual control valve 114 ′ would be opened and adjusted until the desired flow rate of water is discharged from tubing 115 .
- the automatic control valve 138 ′ contained within water feed logic controller 132 ′ would then be manually closed, and the logic controller programmed to operate as needed. Water feed tubing 115 would then be placed into the well apparatus 150 .
- the man hole cover 58 having the insulation layer 60 is then placed back on top of the subsurface housing 52 and the anaerobic bioremediation system 10 is now operating to facilitate the biodegradation, biotransformation or detoxification of the contaminants 14 at interface area 170 of contaminated media 30 into harmless end products including carbon dioxide gas (CO 2 ) 16 , nitrogen gas (N 2 ) 18 and water (H 2 0) 20 .
- CO 2 carbon dioxide gas
- N 2 nitrogen gas
- H 2 0 water
- the installation and set-up procedures for the dispensing apparatus 80 would be the same as described above with the exception that the said dispensing assembly would be installed in a suitable above-ground housing.
- the operator removes outer manhole cover 258 and places the inert gas assembly 202 in close proximity to the well component assembly 220 , such that the inert gas cylinder 204 having argon gas (A) 22 therein stands on the bottom gravel floor 272 of housing 252 .
- the operator checks the gas regulator 206 and the component fitting 212 and attaches tubing 98 to well cap disconnect fitting 242 on well cap 238 , so that the flexible discharge tubing 98 can discharge the argon gas (A) 22 into the well riser 222 of well component assembly 220 .
- valve 210 on gas cylinder 204 and adjusts the gas regulator valve 208 , such that the argon gas (A) 22 is set to flow and run at the minimum setting at which the argon gas (A) 22 is discharged into the well riser 222 .
- the minimum measurable rate on the pressure gauge 214 of gas regulator 206 for discharging the argon gas (A) 22 into the well riser 222 has a setting of about 1 psig.
- gas cylinder 204 The purpose of gas cylinder 204 is to maintain the gravitational flow or passive flow of the argon gas (A) 22 into the vadose zone 38 of the contaminated geologic media 30 in order to suppress vapors from the subsurface contaminants which have the potential to cause fire and explosions in that area. Also, the argon gas (A) 22 enables the maintenance of anaerobic conditions within the contaminated geologic site 30 for a continuous enhancement of the anaerobic bioremediation processes taking place at interface area 170 .
- the manhole cover 258 is then placed on housing 252 by operator for the completion of this step of initially activating the vapor suppression system 200 . In the event that an above-grade installation for the vapor suppression system 200 is preferred, the installation and set-up procedures for the inerting assembly 202 would be the same as described above with the exception that the said inerting assembly would be installed in a suitable above-ground housing.
- the operator is further preparing additional sets of product tanks 100 a ′ to 100 f , 100 a ′′ to 100 f ′′, etc. having a preferred bioremediation composition comprising chemical electron acceptors, nutrients, carbon sources or the like (e.g., see U.S. Pat. No. 6,020,185 to Hince et al.).
- a preferred bioremediation composition comprising chemical electron acceptors, nutrients, carbon sources or the like (e.g., see U.S. Pat. No. 6,020,185 to Hince et al.).
- the aforementioned sets of product tanks having the preferred bioremediation composition are in a stand-by mode at the off-site preparation location, ready to replace the first set of product tanks 100 a to 100 f when they are empty. This aforementioned procedure is also done with several additional gas cylinders 82 ′ and 204 ′, and 82 ′′ and 204 ′′, etc.
- argon gas (A) 22 therein which are also in a stand-by mode at the off-site preparation location and are ready to replace the first gas cylinders 82 and 204 when they are emptied of the argon gas (A) 22 .
- the operator-in-charge periodically at pre-determined timed intervals, checks the dispensing apparatus assembly 80 and the electronic control assembly 130 for proper functioning according to the pre-determined standards initiated for the anaerobic bioremediation system 10 in degrading the contaminants 14 at the geologic work site 30 . These checks are generally performed at the same time that the product tanks 100 a to 100 f and gas cylinders 82 and 204 are replaced.
- the manhole cover 58 is removed from the subsurface housing 52 allowing access to the dispensing apparatus assembly 80 and the electronic control assembly 130 within subsurface housing 52 , as shown in FIGS. 1 and 5 of the drawings.
- the operator then closes the shut-off valve 88 on gas cylinder 82 and removes the quick disconnect coupling 104 a connecting gas cylinder 82 having argon gas (A) 22 from the first product tank 100 a in-line. Then the gas cylinder 82 is lifted out of the housing 52 .
- the replacement product tanks 100 a ′ to 100 f ′ having composition 40 therein are then placed onto the bottom floor 72 of the subsurface housing 52 in a circular fashion, as shown in FIG. 2 of the drawings.
- the operator then puts back on all of the quick disconnect couplings 104 b to 104 k and jumper line tubing 106 a to 106 f onto the replacement product tanks 100 a ′ to 100 f in order to connect these product tanks 100 a ′ to 100 f in series.
- the operator puts back on the quick disconnect coupling 104 l onto the last product tank 100 f′ , where coupling 104 l connects to barb connector 110 for reattaching the logic controller 132 to the last product tank 100 f′ .
- the operator sets a replacement carrier gas cylinder 82 ′ of compressed argon gas (A) 22 at ground level 26 and re-attaches the quick disconnect coupling 104 a and the hose clamp 112 on hose 98 thereby connecting the gas cylinder 82 to the first product tank (in-line) 100 a ′.
- the operator now re-opens the valve 88 and adjusts the regulator valve 86 on the gas regulator assembly 84 , such that the in-line pressure gauge 92 of gas regulator 84 is set to a 5 psig setting, or set at approximately 5 psig above the minimum pressure required to initiate the flow of the chemical nutrient composition 40 out of the product tanks 100 a ′ to 100 f′ .
- the logic controller 132 is then manually closed and set to an automatic setting by the operator.
- the replacement inert gas cylinder 204 ′ is then placed by the operator back onto the bottom gravel floor 272 of the subsurface housing 252 and adjacent to well component assembly 220 , as shown in FIG. 5 of the drawing.
- the operator checks the gas regulator 206 , the connection fitting 212 via tubing 98 being properly attached to the inert gas cylinder 204 and attaches tubing 98 to the well cap quick disconnect fitting 242 on well cap 238 , as shown in FIG. 5 of the drawings.
- the minimum measurable rate on the pressure gauge 216 of gas regulator 206 for discharging the argon gas (A) 22 into the well riser 222 has a setting of about 1 psig.
- the continuous operation of the bioremediation processing apparatus 50 of the anaerobic bioremediation system 10 for degrading contaminants 14 at a particular geologic site 30 may take up to several months. During this time, operators of the anaerobic bioremediation system 10 will repeat the aforementioned steps and procedures of replacing the gas cylinders 82 and 204 having argon gas (A) 22 therein and product tanks 100 a to 100 f having compositions 40 , 41 , 42 , 43 , 44 , and 45 therein numerous times until the project has been completed. Also, the operators on an ongoing basis will periodically re-calibrate the electronic control assembly 130 for the proper flow of compositions 40 , 41 , 42 , 43 , 44 , and 45 into the interface area 170 of geologic media 30 .
- A argon gas
- bacteria utilize electron acceptors in the order of their decreasing energy yield (Gibbs Free Energy [ ⁇ G] in KJ/mole CH 2 0).
- a higher-energy electron acceptor wanes e.g., O 2
- lower-energy electron acceptors e.g., NO 3 , MN(IV), Fe(III), and SO 4 .
- Table 1 The natural sequence of microbial utilization of electron acceptors in the environment is summarized in Table 1.
- sulfates serve as the electron acceptor for oxidation by anaerobic microorganisms.
- Hydrogen sulfide is reduced to hydrogen sulfide (H 2 S) under anaerobic conditions; hydrogen sulfide has a characteristic rotten egg odor, is extremely toxic, and is corrosive to metals. Hydrogen sulfide can also be biologically oxidized to sulfuric acid which is also extremely corrosive.
- the bioremediation system of the present invention provides means by which a preferential electron acceptor (such as oxygen in the form of nitrous oxide, nitrate, Fe(III) or Mn (IV)) can be applied where there is potential for H 2 S formation due to the presence of sulfate, such that the bacteria will preferentially use the higher-energy yielding electron acceptor, and H 2 S will not be formed.
- a preferential electron acceptor such as oxygen in the form of nitrous oxide, nitrate, Fe(III) or Mn (IV)
- the overburden sediments at the site comprise fine-to-medium glaciofluvial sands with varying amounts of silt.
- the water table ranges from 6-to-10 ft. below grade.
- a compact, silty-clay aquitard of glaciolacustrine origin is present at depths ranging from 15-to-19 ft. below grade.
- Bedrock was not encountered during drilling and the bedrock aquifer is not believed to have been impacted.
- a stream wraps around the site and its surroundings approximately 200 ft. downgradient and ground-water flow conditions have been interpreted fluctuate in response to local surface-water/ground-water interaction and meteorological events.
- ABSs anaerobic bioremediation systems
- Baseline contaminant levels included more than 2 ft. of free product, MTBE- and 1,2-DCA-amended gasoline in the most contaminated well and >16-42 mg/L total BTEX in the next most contaminated well.
- Overburden sediments at the site are predominantly medium to coarse sands associated with glacial-outwash and/or a kame-delta, with ground water at approximately 17 ft. below grade Bedrock was not encountered and it is not believed to have been impacted.
- An advantage of the present invention is that it provides for an anaerobic bioremediation system for the anaerobic biodegradation, detoxification and transformation of toxic organic and inorganic contaminants within contaminated geologic media into non-toxic compounds without further production of regulated wastes or other undesirable by-products that effect air, water and soil at the geologic site.
- Another advantage of the present invention is that it provides for an anaerobic bioremediation system for in-situ treatment of geologic media containing organic and inorganic contaminants that are metabolizable or transformable by naturally occurring indigenous, MRP anaerobic bacteria including denitrifying-, manganese-, iron- and sulfate-reducing microorganisms within the contaminated geologic media at the site.
- Another advantage of the present invention is that it provides for an anaerobic bioremediation system having apparatus which enables the delivery of electron acceptors, nutrients, chelating agents, surfactants, a diluent and an inert carrier gas to promote the growth of indigenous, MRP anaerobic bacteria including denitrifying-, manganese-, iron- and sulfate-reducing microorganisms such that the metabolism or transformation of the contaminants by these microorganisms can easily take place without the use of implanted microorganisms at the contaminated site.
- Another advantage of the present invention is that it provides for an anaerobic bioremediation system having apparatus which enables the electron acceptors, nutrients, chelating agents, surfactants, a diluent and an inert carrier gas to be more readily and rapidly dispersed in the contaminated geologic media, thereby becoming more widely available to MRP anaerobic bacteria within the contaminated geologic media.
- Another advantage of the present invention is that it provides for an anaerobic bioremediation system the electron acceptors, nutrients, chelating agents, surfactants, a diluent and an inert carrier gas in a chemical composition and form that is readily utilizable by indigenous, MRP anaerobic bacteria including denitrifying-, manganese-, iron- and sulfate-reducing microorganisms within the contaminated geologic media.
- Another advantage of the present invention is that it provides for an anaerobic bioremediation system that has the means to supply electron acceptors, nutrients, chelating agents, surfactants, a diluent and inert carrier gas as well as the capacity to modify the pH, redox potential and the availability of oxygen in the subsurface geologic media in a manner which enables a major improvement for the stimulation and growth of indigenous MRP microorganisms within contaminated geologic media.
- Another advantage of the present invention is that it provides a means for stimulating several different microbial respiration pathways under different redox conditions in-situ by using one or more chemical compositions in such a manner so as to stimulate MRP anaerobic bacteria including denitrifying-, manganese-, iron- and sulfate-reducing microorganisms within the contaminated geologic media.
- Another advantage of the present invention is that it provides for an anaerobic bioremediation system having a means for stimulating, alternating and/or cycling various redox conditions and microbial respiration pathways within the contaminated geologic media in-situ by using one or more chemical compositions in such a manner so as to stimulate a temporal and/or spatial succession of redox conditions in the subsurface in order to enhance the growth of MRP anaerobic microorganisms and to optimize contaminant biodegradation and/or biotransformation by such microorganisms.
- Another advantage of the present invention is that it provides for an anaerobic bioremediation system having the capability for reducing flash fire and/or explosion hazards in the contaminated geologic media.
- Another advantage of the present invention is that it provides for an anaerobic bioremediation system having apparatus that is simple and inexpensive to construct and use, and which enables efficient delivery and monitoring of the nutrients and electron acceptors for the optimum growth rate and kinetics of various indigenous, denitrifying and other MRP microorganisms in order to maximize the rate of degradation and transformation of the contaminants into non-toxic compounds by these indigenous MRP microorganisms.
- Another advantage of the present invention is that it provides for an anaerobic bioremediation system having a process that is simple and inexpensive to operate, especially under actual field conditions and the logistical constraints of small and/or busy sites (e.g., Example 1).
- Another advantage of the present invention is that it provides for an anaerobic bioremediation system whose operation can be modified manually or automatically either on-site or from off-site locations based on real-time measurements of in-situ conditions.
- Another advantage of the present invention is that it provides for an anaerobic bioremediation system having a process that can be performed rapidly and safely in the field and which results in the site meeting environmental clean-up standards set by various governmental agencies more rapidly and at a lower cost than can be accomplished with other methods.
- a further advantage of the present invention is that it provides for an improved anaerobic bioremediation system that can be easily produced in an automated and economical manner and is readily affordable by various responsible parties, consultants, contractors, engineers, governmental agencies and corporate users.
Abstract
A bioremediation apparatus is disclosed for anaerobic biodegradation, detoxification, and transformation of toxic organic and inorganic compounds in a contaminated geologic media. The bioremediation apparatus includes a first set of one or more storage tanks containing a chemical composition for anaerobic biodegradation of toxic compounds in contaminated geologic media; a plurality of quick disconnect valve couplings connected to the first set of storage tanks; at least one logic controller having a logic controller programmer component for opening and closing an automatic valve means connected to the first set of storage tanks to supply the chemical composition to the contaminated geologic media; and a screened well connected to the first set of storage tanks for supplying the chemical composition to the contaminated geologic media.
A method is disclosed for anaerobic biodegradation, detoxification, and transformation of toxic organic and inorganic compounds in a contaminated geologic media comprising the steps of pressurizing one or more storage tanks containing a chemical composition using an inert carrier gas; connecting a plurality of quick disconnect valve couplings to one or more pressurized storage tanks; connecting a well to an automatic ball valve for supplying the chemical composition and the inert carrier gas through the well to the contaminated geologic media; and opening and closing the automatic ball valve to dispense the chemical composition and the inert carrier gas under pressure through the well to the contaminated geologic media. Methods are also disclosed for alternating the cycles of redox potential and the predominant microbial respiration pathway within the contaminated geological media. The present invention also discloses means for inerting and suppressing volatiles vapors or gases in the subsurface for reducing the flash fire and/or explosion hazards in the contaminated geologic media.
Description
- This application is a division of U.S. application Ser. No. 08/862,782, filed May 23, 1997, now U.S. Pat. No. 6,020,185 to Hince et al.
- The present invention relates to a new and improved anaerobic bioremediation system and method thereof for anaerobic biodegradation, detoxification and transformation of toxic organic and inorganic compounds in contaminated geologic formations to harmless and safe organic and inorganic materials within the geologic media. More particularly, the bioremediation system includes an apparatus and methods for implementing the conversion of contaminated organic and inorganic materials to clean, safe, and harmless materials via naturally occurring anaerobic bioremediation within the geologic media.
- Aerobic and anaerobic bioremediation of contaminated soils, ground water sites, lakes, ponds, aquifers, wells, shore fronts, oceans and the like have proven effective in remediating toxic organic and inorganic compounds such as fuel oil, gasoline, PCBs, DDT and other pesticides, and the like. Bioremediation projects that have been successfully implemented are in areas that include underground storage tank spills and leakages; hazardous solid wastes; ground spills; and contamination of ground water (wells), geological aquifers and the like. Aerobic and anaerobic bioremediation have proven to be more cost effective and timely than conventional engineering technologies, and have the further advantage in that they do not produce wastes which enter the surrounding air, water and soils. Anaerobic bioremediation has been shown to be the most effective and least expensive method of remediation of toxic materials. Other remediation technologies such as standard physical soil and ground-water remediation, i.e. excavation and disposal or pump and treat systems and soil-vapor extraction (SVE) remediation, have all been shown to be moderately high in capital costs; to require long-term operation and maintenance including labor, materials and power consumption; to require time parameters that are in months to years; and to have remediation effectiveness results being moderately low in the cleanup of the contaminated soils and ground water. These remediation techniques are also limited by considerations of depth of soil to be removed; obstructions in the geologic formations; safety conditions at the site; and environmental law statutes with regard to Federal, State and local regulatory agencies for a site remediation project that produces wastes that affect air, water and soil conditions. These aforementioned remediation technologies generally are less feasible and significantly more expensive and sometimes prohibitive in terms of logistics and/or overall costs.
- Problems associated with anaerobic bioremediation have included the difficulty of achieving significant increases in the naturally occurring indigenous microorganisms at the contaminated site using appropriate chemical compositions of nutrients that would successfully have the indigenous anaerobic bacteria metabolize the organic and inorganic contaminants. The inability to maximize the rate of metabolism of toxic contaminants by anaerobic microorganisms can be due to inadequate or incorrect electron acceptors, nutrient forms of nitrogen and phosphorus, trace-mineral micronutrients, chelating agents, non-toxic surfactants, lack of carbon co-substrates, and inerting agents. There is also a physical inability to deliver, distribute and disperse the nutrients readily, rapidly and over a wide distribution area within the contaminated geologic media for effective biodegradation of the contaminated substances into non-toxic end products. Also, there is a difficulty of working with anaerobic microorganisms and processes because the biochemical pathways describing the anaerobic degradation of organic and inorganic compounds have been difficult to characterize and, to a large degree, are yet to be fully understood. Thus, it can be seen that anaerobic bioremediation of contaminated geologic media such as ground water (wells), sludge, soil and the like is not an easy or simple technological problem.
- There remains a need for an improved method and apparatus for the anaerobic bioremediation of organic and inorganic toxic compounds within a contaminated geologic media to form non-toxic end products without further formation of waste by-products that affect air, water and soil qualities at the geologic site. In addition, there is a need that the bioremediation be accomplished by having an in-situ treatment of the contaminated geologic media such that the organic and inorganic contaminants are metabolized or transformed by naturally occurring indigenous, denitrifying and/or manganese-, iron- and sulfate-reducing anaerobic microorganisms using the aforementioned electron acceptors, in combination with nutrients, surfactants, chelating agents, a diluent, and an inert gas to convert the contaminants within the contaminated geologic media into non-toxic end products. These naturally occurring indigenous microorganisms which operate using one or more respiration pathways are hereafter called “multiple respiration pathway” (MRP) microorganisms.
- Methods, apparatus and chemical compositions having nutrients for bioremediation using anaerobic microorganisms have been disclosed in the prior art. For example, U.S. Pat. No. 5,178,491 to Graves et al discloses a vapor-phase nutrient delivery system for in-situ bioremediation of soil. The nutrients are delivered in the vapor phase to the affected areas of the contaminated soil for utilization by microorganisms to promote the metabolism of organic contaminants by the microorganisms. The delivery system includes a series of pumps, nutrient tanks, conduits, and wells for implementing the bioremediation process. This prior art patent does not disclose the apparatus or methods for the bioremediation of contaminated geologic media as in the present invention.
- U.S. Pat. No. 5,265,674 to Fredrickson et al discloses an enhancement method of in-situ remediation of aquifers. This method of bioremediation is adapted to deliver microorganisms, enzymes, nutrients and electron donors to subsurface zones contaminated by nitrates in order to stimulate or enhance denitrification. The remediation system includes nutrient tanks, pumps, conduit/piping, an injection well and reclamation tanks. This prior art patent does not disclose the apparatus or methods for the bioremediation of contaminated geologic media as in the present invention.
- U.S. Pat. No. 5,342,769 to Hunter et al discloses a method for bioremediation of liquid or slurry hazardous waste streams for the removal of halogenated hydrocarbons by using naturally occurring anaerobic microorganisms having methanogenic characteristics. The remediation method includes a series of reactors, pumps, vacuum pumps, and conduits. This prior art patent does not disclose the apparatus or methods for the bioremediation of contaminated geologic media as in the present invention.
- U.S. Pat. No. 5,384,048 to Hazen et al discloses an apparatus and method for in-situ bioremediation of contaminated ground water and/or contaminated subsurface soil by chlorinated hydrocarbons. A nutrient fluid is used to stimulate the growth and reproduction of indigenous aerobic microorganisms that are capable of degrading the contaminants. The apparatus used for the bioremediation process includes injection wells, pumps, conduits, and monitoring/sensor components. This prior art patent does not disclose the apparatus or methods for the bioremediation of contaminated geologic media as in the present invention.
- U.S. Pat. No.5,398,756 to Brodsky et al discloses a process for the in-situ bioremediation of contaminated soil. The process includes the forming of at least one liquid permeable region within the contaminated soil region, introducing microorganisms, nutrients and the like for degrading contaminants in the contaminated soil region, and transmitting direct electric current through the contaminated soil region for degrading the contaminants by electrochemical means. This prior art patent does not disclose the apparatus or methods for the bioremediation of contaminated geologic media as in the present invention.
- U.S. Pat. Nos. 5,482,630 and 5,556,536 to Lee et al and Turk disclose a controlled denitrification process and system using a bacterial bed. This bioprocess system is used for the reduction of nitrate to nitrogen in a fluid medium, such that anaerobic bacteria fed by a carbon source are used for the nitrate reduction. A column of suspended beads are used as the anaerobic bacterial bed for denitrification. This prior art patent does not disclose the apparatus or methods for the bioremediation of contaminated geologic media as in the present invention.
- U.S. Pat. No. 5,560,737 to Schuring et al discloses a method and apparatus for pneumatic fracturing and multicomponent injection enhancement of in-situ bioremediation in treating subsurface soil contaminated with organic compounds. This bioremediation method and apparatus provides for reducing or eliminating non-naturally occurring, subsurface, liquid contaminants within a geologic formation, which involves the steps of pneumatically fracturing the soil formation to produce a fracture network. A pressurized gas stream is used having nutrients, oxygen, electron acceptors, pH buffers, and possible bacterial augmentation to add a different culture of microorganisms to the soil formation when used in fracturing the soil formation. This provides the proper growth of the bioremediation microorganisms within the fracture network in which to degrade the contaminated materials within the water or soil formations. This prior art patent does not disclose the apparatus or methods for the bioremediation of contaminated geologic media as in the present invention.
- None of the prior art patents teach or disclose the apparatus or methods for the bioremediation of contaminated geologic media as in the present invention. Also, none of the prior art patents teach or disclose the process or system of the current invention for the in-situ treatment of contaminated geologic media by using multiple-respiration pathway (MRP) anaerobic microorganisms such as denitrifying, manganese-, iron- and sulfate-reducing anaerobic microorganisms. Accordingly, it is an object of the present invention to provide an anaerobic bioremediation system for the anaerobic biodegradation, detoxification and transformation of toxic organic and inorganic contaminants in contaminated geologic media into non-toxic compounds without further formation of regulated wastes or other undesirable by-products that affect the air, water and soil at environmental-contamination sites.
- Another object of the present invention is to provide an anaerobic bioremediation system for in-situ treatment of geologic media containing organic and inorganic contaminants that are metabolizable or transformable by indigenous anaerobic bacteria capable of utilizing one or more multiple respiration pathways (MRP) including denitrification, manganese-reduction, iron-reduction and sulfate-reduction within the contaminated geologic media at a site.
- Another object of the present invention is to provide an anaerobic bioremediation system having apparatus which enables the delivery of nutrients and electron acceptors having an inert carrier gas to the indigenous MRP anaerobic microorganisms in order to promote conditions favorable to the growth of these indigenous microorganisms such that the metabolism or transformation of the contaminants by these microorganisms can easily take place, without the use of implanted microorganisms at the contaminated site.
- Another object of the present invention is to provide an anaerobic bioremediation system having apparatus which enables the nutrients and electron acceptors and an inert carrier gas to be more readily and rapidly dispersed in the contaminated geologic media and made more available to a large area within the contaminated geologic media.
- Another object of the present invention is to provide an anaerobic bioremediation system that can easily deliver nutrients, electron acceptors, chelating agents, surfactants and diluent with an inert carrier gas being in a chemical composition form that is readily utilizable and metabolizable by the indigenous MRP anaerobic microorganisms.
- Another object of the present invention is to provide an anaerobic bioremediation system that has the capacity to supply macro-nutrients, micro-nutrients, electron acceptors, surfactants, and chelating agents, as well as to modify the pH, redox potential and oxygen availability in the subsurface geologic media.
- Another object of the present invention is to provide an anaerobic bioremediation system that has the capacity to supply biologically usable phosphate to phosphate-limited environments, whereby sodium hexametaphosphate or other forms of hydrolyzable ringed or linear polyphosphates are used as the primary source of phosphate, as such compounds are much less prone to in-situ precipitation than other forms of phosphate, enabling a major improvement for the stimulation and growth of indigenous MRP microorganisms in the contaminated geologic formation.
- Another object of the present invention is to provide an anaerobic bioremediation system that has the capacity to supply nitrate as both an electron acceptor and the main source of assimilated (i.e., nutrient) nitrogen, taken together with other unique aspects of the chemical compositions of the present invention, which enables a major improvement for the stimulation and growth of indigenous denitrifying and MRP microorganisms in the contaminated geologic media.
- Another object of the present invention is to provide an anaerobic bioremediation system having apparatus that is simple to construct and use and which enables efficient delivery and monitoring of the nutrients and electron acceptors for the optimum growth rate and kinetics of various indigenous, denitrifying and other MRP anaerobic microorganisms in order to maximize the rate of degradation and transformation of the contaminants into non-toxic compounds by these indigenous MRP microorganisms.
- Another object of the present invention is to provide an anaerobic bioremediation system having a process that is inexpensive and easy to operate, especially under actual field conditions and the logistical constraints of active sites.
- Another object of the present invention is to provide an anaerobic bioremediation system having a process that can be performed rapidly and safely in the field and result in the site meeting environmental clean-up standards set by various governmental agencies more rapidly and at a lower cost than can be accomplished with other methods.
- A further object of the present invention is to provide an improved anaerobic bioremediation system that can be easily produced in an automated and economical manner and is readily affordable by various responsible parties, consultants, contractors, engineers, governmental agencies and corporate users.
- The present invention includes a bioremediation apparatus for anaerobic biodegradation, detoxification, and transformation of toxic organic and inorganic compounds in a contaminated geologic media. The bioremediation apparatus includes a first set of one or more storage tanks containing a chemical composition for anaerobic biodegradation of toxic compounds in contaminated geologic media; a plurality of quick disconnect valve couplings connected to the first set of storage tanks; at least one logic controller having a logic controller programmer component for opening and closing an automatic valve connected to the first set of storage tanks to supply the chemical composition to the contaminated geologic media; and a screened well connected to the first set of storage tanks for supplying the chemical composition to the contaminated geologic media.
- The present invention also includes methods for anaerobic biodegradation, detoxification, and transformation of toxic organic and inorganic compounds in contaminated geologic media. The basic method includes pressurizing one or more storage tanks containing a chemical composition and an inert carrier gas; connecting a plurality of quick disconnect valve couplings to one or more pressurized storage tanks; connecting a well to an automatic ball valve for supplying the chemical composition and the inert carrier gas through the well to the contaminated geologic media; and opening and closing of the automatic ball valve to dispense the chemical composition and the inert carrier gas under pressure through the well to the contaminated geologic media.
- Further objects, features, and advantages of the present invention will become apparent upon consideration of the detailed description of the presently-preferred embodiments, when taken in conjunction with the accompanying drawings, wherein:
- FIG. 1 is a side elevational view of the anaerobic bioremediation system of the preferred embodiment of the present invention showing the bioremediation processing apparatus and its major component assemblies therein and in operational use.
- FIG. 2 is a front perspective view of the anaerobic bioremediation system of the preferred embodiment of the present invention showing the subsurface housing containing the bioremediation processing apparatus and its component parts contained therein; and in operational use. It is noted that there is an alternate configuration for connecting the bioremediation processing apparatus as shown in the following two figures.
- FIG. 3A is a front perspective view of the anaerobic bioremediation system of the preferred embodiment of the present invention showing the dispensing apparatus assembly and its component parts contained therein and the electronic control assembly and its component parts contained therein. The product canisters are operated in series using this set-up.
- FIG. 3B is a front perspective view of the anaerobic bioremediation system of the preferred embodiment of the present invention showing an alternate dispensing apparatus assembly and its component parts contained therein and the electronic control assembly and its component parts contained therein. The product canisters are operated in parallel using this alternate set-up. Although the other Figures show the dispensing apparatus assembly configured as shown in FIG. 3A (series product canister operation), it should be noted that the system can also be set up and operated using the parallel product canister configuration depicted in FIG. 3B.
- FIG. 4 is a front perspective view of the anaerobic bioremediation system of the preferred embodiment of the present invention showing the electronic control assembly and its component parts contained therein.
- FIG. 5 is a side elevational view of the anaerobic bioremediation system of the preferred embodiment of the present invention showing the bioremediation processing apparatus having the dispensing apparatus assembly, the electronic control assembly, and the first well component assembly; and the vapor suppression system and a second well component assembly; with both systems being in operational use.
- FIG. 6 is a front perspective view of the anaerobic bioremediation system of the alternate embodiment of the present invention showing the vapor suppression system and its component parts contained thereon and in operational use.
- FIG. 7 is a front perspective view of the anaerobic bioremediation system of the preferred and alternate embodiments of the present invention showing dual dispensing apparatus assemblies and dual electronic control assemblies being electrically interconnected for the alternate feeding of the standard nutrient composition and alternative nutrient compositions into the well component assembly.
- FIG. 8 is a side elevational view of the anaerobic bioremediation system of the alternate embodiment of the present invention showing the bioremediation processing apparatus for use in bioremediation applications involving dense non-aqueous phase liquid contaminants (DNAPLs) having a dispensing apparatus assembly, an electronic control assembly and a well component assembly; and in operational use.
- FIG. 9 is a side elevational view of the anaerobic bioremediation system of the alternate embodiment of the present invention showing the bioremediation processing apparatus for use in bioremediation applications involving light non-aqueous phase liquid contaminants (LNAPLs) having a dispensing apparatus assembly, an electronic control assembly and a well component assembly; and in operational use.
- FIG. 10 is a schematic diagram of the anaerobic bioremediation system of the present invention showing the generic stoichiometric equations for the bioremediation processes of converting organic contaminants into non-toxic byproducts, such as carbon dioxide, nitrogen gas and water via denitrification.
- The anaerobic bioremediation system apparatus and methods of this invention provide the means for the anaerobic biodegradation, detoxification and transformation of toxic organic and inorganic compounds in contaminated geologic media to harmless and safe organic and inorganic materials within the geologic media. In-situ bioremediation has recently emerged as the general category of site remediation technologies which provides for the most timely and effective remediation of contaminated soil and ground water from petroleum hydrocarbon spills, releases of halogenated hydrocarbons, solvents and pesticides, inorganic chemical dumping, and the like. Furthermore, field demonstrations of bioremediation technologies have typically outperformed laboratory studies, even though it has often been assumed by experts in the field that ideal conditions were established in the laboratory. The success of bioremediation field trials, including those of the present invention, is thought to be attributable to the greater diversity of bacterial populations and their enzymatic processes that are present in the natural hydrogeologic settings versus those that can be established in laboratory microcosms.
- In-situ bioremediation provides for the potential of a swift reduction of contaminant levels, often in periods as short as weeks to months, as shown in examples of the actual use of the present invention on contaminated geologic formations as provided below. The present invention uses naturally-occurring bacteria that are indigenous to the geologic formation being remediated for the degradation of hydrocarbons, solvents, pesticides, hazardous wastes and the like. The theoretical basis and effectiveness of using indigenous MRP anaerobic microorganisms capable of denitrification, manganese-reduction, iron-reduction and sulfate-reduction is demonstrated in the bioremediation process diagram (FIG. 10) which describes the theoretical operation of the
bioremediation system 10 of the present invention. The present invention provides a means of stimulating such MRP anaerobic microorganisms so as to achieve rapid and effective degradation and remediation of aromatic hydrocarbons as well as halogenated hydrocarbons, pesticides, hazardous wastes and other contaminants as demonstrated in the forthcoming examples of projects conducted at actual contaminated geologic sites. - The principle of using anaerobic microorganisms such as denitrifying bacteria and other MRP anaerobic bacteria in the present invention is dependent upon the natural sequence of electron-acceptor utilization by bacteria within geologic media as well as the natural occurrence and/or solubility of these electron acceptors in water. Bacteria utilize electron acceptors in the order of their decreasing energy yield (Gibbs Free Energy [ΔG] in KJ/mole CH20). In theory, as the availability of a higher-energy electron acceptor wanes (e.g., O2), conditions become favorable for microbial respiration with lower-energy electron acceptors (e.g., NO3, Mn(IV), Fe(IIl), and SO4). The natural sequence of microbial utilization of electron acceptors in the environment is summarized in Table 1 below:
TABLE 1 Energy Yield and Solubility of Microbial Electron Acceptors Electron Acceptor [ΔG] in KJ/mole CH20a Max. Solubility (mg/l)b O2 −475 10c NO3 −448 637,000d MnO2 −349 Insoluble mineral Fe(OH)3 −114 Insoluble mineral SO4 −77 113,000e CO2 −58 2,000f - Note: The natural sequence of microbial electron-acceptor utilization described in Table 1 is based on the original research of Froelich et al. (1979).
- Most bioremediation processes described in the prior art and in the literature have involved the addition of oxygen in attempts to facilitate the aerobic degradation of various organic contaminants. However, it is very difficult to maintain sufficient concentrations of oxygen in-situ to support aerobic biodegradation, largely due to the low solubility of oxygen in ground water (≦10 mg/l), as well as the multitude of both biological and chemical “sinks” of oxygen in the subsurface. In contaminated ground waters, redox conditions are typically strongly reducing and dissolved oxygen concentrations are typically insufficient (i.e., ≦1 mg/l) to support strictly-aerobic respiration. Therefore, given the low solubility and reactivity of oxygen, it is typically impractical to maintain non-limiting conditions of oxygen-availability in the subsurface.
- As shown in Table 1 above, nitrate and sulfate salts are much more soluble in water than is oxygen. Nitrate and sulfate are also more “conservative” than oxygen in terms of their geochemistry, i.e., these species are less reactive and more mobile. Therefore, diffusive processes can be used to deliver non-limiting concentrations of nitrate and sulfate to the interior of ground-water contaminant plumes in relatively short periods of time because of the significant in-situ concentration gradients that can be established by the present invention.
- Although aeration of subsurface sediments (e.g., air sparging) has been used with some success, a documented problem with the aeration and/or oxygenation of contaminated ground waters containing elevated concentrations of iron and manganese (i.e., ≧5 mg/l) is that such processes lead to the oxidation and precipitation of these species in-situ. Accordingly, aeration, oxygen-injection, peroxide injection and other similar aerobic bioremediation processes tend to reduce the effective porosity and hydraulic conductivity of the geologic media in-situ which ultimately slows the rate of site remediation. Iron oxidation and fouling problems have often been encountered in pump and treat systems as evidenced by air-strippers which have become fouled with iron. The use of the present invention however, avoids this problem altogether by focusing on the enhancement of the naturally anaerobic and reducing conditions present in contaminated geologic media.
- As shown in Table 1 above, nitrate provides denitrifying bacteria with a significant Gibbs-Free-Energy (ΔG=−448 KJ/mole CH2O), which is within approximately 5% of that of oxygen. In addition, denitrification is more efficient (if not more rapid) than aerobic processes, as only 1 mole of nitrate versus 1.25 moles of oxygen is consumed in the degradation of one mole of contaminant. Reactions which describe aerobic, denitrification, manganese-reduction, iron-reduction, and sulfate-reduction mediated biodegradation of an idealized hydrocarbon contaminant (—CH—) are provided in Table 2 below:
TABLE 2 Bioremediation Respiration Pathway Generalized Stoichiometric Equation (1) Aerobic 12-CH—+ 1502 → 12CO2 + 6H2O (2) Denitrification —CH—+ NO3 + H+ → CO2 + 1/2N2 + H2O (3) Manganese —CH—+ ½ Mn (IV) + 3H2O → Reduction ½ Mn(II) + HCO3 − + 6H+ (4) Iron Reduction —CH—+ Fe(III) + 3H2O → Fe(II) + HCO3 − + 6H+ (5) Sulfate —CH—+ SO4 −2 + 5H+ → CO2 + H2S + 2H2O Reduction - As shown in Table 2 above, the ultimate end-products of denitrification are carbon dioxide, water and elemental-nitrogen gas. Consequently, one advantage of the present invention is that it facilitates the use of denitrification as a naturally safe and practical means of bioremediation as shown in the
bioremediation process 10 of the present invention. When combined with the stimulation of manganese-reducing, iron-reducing and sulfate-reducing bacteria as enabled by this invention, a significant and consistently demonstrable improvement in site remediation is provided. - Examples of anaerobic bioremediation solutions that can be used with the present invention are disclosed in the references to Hince et al. (U.S. Pat. Nos. 6,020,185, 6,344,355; application Ser. No. 09/495,046),
- The present invention provides means by which multiple chemical compositions can be used to stimulate microorganisms that utilize various redox conditions and microbial respiration pathways in-situ within the contaminated geologic media (see Table 1), so as to enhance the growth of MRP anaerobic microorganisms and to optimize contaminant biodegradation and/or biotransformation by such microorganisms. In addition, such utility of the present invention provides means for cycling through a series of redox conditions in-situ within the contaminated geologic media as illustrated in FIG. 10. Redox cycling within the contaminated geologic media in-situ is achieved by using one or more chemical compositions in such a manner so as to stimulate a temporal and/or spatial succession of redox conditions and anaerobic respiration pathways in the subsurface. A typical redox-cycling application facilitated by the present invention may begin with the stimulation of denitrification followed by manganese-reduction, iron-reduction and sulfate-reduction and returning again to nitrate reduction. For example, one or more chemical compositions may be used to stimulate denitrification, followed by the use of one or more chemical compositions to stimulate manganese-reduction, iron-reduction (and/or the reduction of other metals which can serve as microbial electron acceptors), followed by the use of one or more chemical compositions to promote the growth of anaerobic bacteria via sulfate-reduction, followed by the return to using one or more chemical compositions to again stimulate denitrifying conditions. Because of the nature of the apparatus and methods of the present invention, this invention also provides a means for varying such redox cycles to meet site-specific conditions or otherwise difficult contamination problems. The aforementioned cycling of redox conditions as facilitated by the present invention provides for the stimulation of a much more diverse community of MRP anaerobic microorganisms than could otherwise be achieved by other methods, which in turn provides a means of optimizing contaminant biodegradation and/or biotransformation in-situ within contaminated geologic media.
- In addition to facilitating the application of bioremediation compositions that provide electron acceptors for microbial respiration, the present invention provides means of providing MRP anaerobic bacteria with macro-nutrients and micronutrients needed to sustain bacterial growth and to promote biodegradation and/or biotransformation of organic and inorganic contaminants. For example, in addition to nitrate and/or other anaerobic electron acceptors, bacteria may also require macro-nutrients such as inorganic nitrogen (e.g., ammonium) and phosphate. Bacteria utilize ammonium and similar forms of nitrogen to help synthesize proteins and other complex organic molecules.
- Bacteria also require phosphate for the production of nucleic acids, phospholipids, and other biochemicals as well as for the maintenance of adequate levels of nucleoside 5′ triphosphates such as adenosine-triphosphate (ATP), the most common intracellular “energy-molecule.” Some researchers have shown that the availability of 10-20 mg/l of phosphate (PO4 −3) is typically sufficient to stimulate the biodegradation of aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylenes (BTEX) in ground water. However, most phosphate salts cause precipitates to form close to the injection well screens because of the reactive geochemistry between phosphate and the cations naturally present in geologic media. Accordingly, in accordance with the present invention, the use of sodium hexametaphosphate and/or other ringed or linear polyphosphates for phosphate addition may be preferred to help overcome the typical fouling problems encountered by using other forms of phosphate. In addition, this invention provides a means of providing chelating agents to minimize abiotic reactions between phosphate and the naturally occurring cations in the geologic media.
- Trace metal micronutrients, including, but not limited to, iron, molybdenum, copper, cobalt, manganese, boron and zinc are also important to the growth of denitrifying bacteria and other MRP anaerobic bacteria. These trace metals are required in the key enzymatic processes by which nitrate-reducing bacteria and other MRP anaerobes metabolize carbon sources such as hydrocarbons, halogenated solvents, pesticides, hazardous wastes and the like. For example, previous research reported in the literature has indicated that the addition of ≧10 μg/l of key trace metals along with nitrate and phosphate facilitated the more effective degradation of BTEX compounds relative to the addition of nitrate and phosphate alone. Although these micronutrients are important to the growth of MRP anaerobic bacteria, research related to the operational use of the present invention, including experience in various geologic settings and contaminant conditions, has shown that the soil and ground water at each of these sites often provides an adequate supply of these micronutrients. Nonetheless, the
bioremediation system 10 of the present invention and the applications thereof provide means for the application of such micronutrients, if required, to enhance bioremediation. - The substrate which is used as an electron donor within the contaminated geologic formation for anaerobic biodegradation could include organic chemical compounds or contaminants including petroleum-based hydrocarbons, halogenated hydrocarbons and solvents, polychlorinated biphenyls (PCB's), dioxin, pesticides, and other toxic/hazardous wastes. Examples of typical petroleum hydrocarbons include gasoline, diesel fuel, fuel oils and lubricating oils, as well as gasoline and diesel additives such as methyl tertiary butyl ether (MTBE), ethanol, tertiary butyl alcohol (TBA) and the like. Examples of typical halogenated hydrocarbons and solvents that are used as a carbon source by MRP anaerobic bacteria during the remediation of a contaminated site could include carbon tetrachloride, tetrachloroethylene, tetrachloroethane, trichloroethylene, 1,1,1,-trichloroethane, 1,1,2-trichloroethane, 1,2-dichloroethylene, chloroform, methylene chloride, 1,2-dibromoethane, 1,2-dichloroethane, vinyl chloride, trichlorofluoromethane (Freon 113), and the like. Typical pesticides, herbicides, insecticides, mitacides, and nitroaromatic compounds being remediated at a contaminated site could include dinoseb (2-(1-melkylpropyl)-4,6-dinitrophenol, DDT, DDD, DDE, Diazanon™, chlordane, malathion, trinitrotoluene (TNT), dinitrotoluene (DNT), toxaphene, and the like. Typical inorganic contaminants and/or hazardous-wastes being remediated could include cyanides, cobalt-60, hexavalent chromium, uranium (VI), and other transition metals with the potential for reduction from higher valence states to lower valence states.
- The
bioremediation processing apparatus 50 for theanaerobic bioremediation system 10 of the preferred embodiment of the present invention is represented in FIGS. 1 through 4 of the drawings. Thebioremediation processing apparatus 50 is the delivery and feeding mechanism for transporting a nutrientfluid chemical composition 40 to the contaminatedgeologic formation 30 in order to stimulate anaerobic biodegradation, detoxification and transformation of toxic organic and inorganic compounds into harmless and safe end-products. - The
bioremediation processing apparatus 50, as shown in FIGS. 1 to 3, includes a metal orconcrete housing component 52, a dispensingapparatus assembly 80 for dispensing ofcomposition 40; anelectronic control assembly 130 for electronicallymetering composition 40; and awell component assembly 150 for delivering ofcomposition 40 to the contaminatedgeologic formation 30.Bioremediation processing apparatus 50 includes acylindrical subsurface housing 52 made of metal or concrete having an outer cylindricalbentonite seal layer 54.Housing 52 also includes anouter manhole cover 58 having aninsulation layer 60 attached to the coverinner wall member 62. In addition,sub-surface housing 52 includes acylindrical wall member 64 having inner andouter surface walls bottom wall member 70 being a gravel layer. Bottomgravel wall member 70 further includes atop surface wall 72 and abottom surface wall 74.Bottom wall member 70 includes acircular hole opening 76 within the gravel layer for receiving theupper end 154 ofwell casing 152.Insulation layer 60 oncover 58 protectscomposition 40 within the plurality ofproduct canister tanks 100 a to 100 f of dispensingapparatus assembly 80 from freezing. - The dispensing
apparatus assembly 80, as shown in detail by FIGS. 1, 2, and 3A of the drawings, includes acarrier gas cylinder 82 for holding ofinert gas 22 having agas regulator assembly 84, a plurality of stainless steelproduct canister tanks 100 a to 100 f for holding ofcomposition 40 therein havingremovable lids 102 a to 102 f, and a plurality of quick disconnect couplings 104 a to 104 l fortanks 100 a to 100 f. A plurality ofjumper line tubing 106 a to 106 f is attached to the aforementioned couplings 104 a to 104 e for connecting each of theproduct canister tanks 100 a to 100 f in series. In addition, the plurality of quick disconnect couplings 104 a to 104 l and the plurality ofjumper line tubing 106 a to 106 f use a plurality of hose barb adapters 108 a to 108 j and 110 and a plurality of stainless steel hose clamps 112 a to 112 j for connecting the aforementioned quick disconnect couplings 104 a to 104 j andjumper line tubing 106 a to 106 f with each other. - In using the alternate set-up of the dispensing apparatus as depicted in FIG. 3B, manifold99 a would be used with a plurality of jumper line tubing (106 a to 106 f connecting the manifold to the individual
product canister tanks 100 a to 100 f, which would be operated in parallel rather than in series.Jumper lines 106 a′ to 106 f would connect each individual product canister tank discharge to manifold 99 b, which would discharge to the logic controller, as shown in FIG. 3B. - The
gas regulator assembly 84 for thecarrier gas cylinder 82 includes a gas regulator shut-offvalve 86, a barbed-stem outlet line 90 and in-line pressure gauges 92 a and 92 b; there is a separate shut-offvalve 88 forgas cylinder 82. Attached togas regulator assembly 84 is a regulatorgauge protection cage 94, and flexible link-uptubing 98 for connecting to the firstproduct canister tank 100 a when the product tanks operated in series. - In addition, the dispensing
apparatus assembly 80 further includes a manually operatedball valve 114 which connects to theelectronic control assembly 130 on one end and to well 152 on the other end via connectingtubing 148. - The
electronic control assembly 130 includes alogic controller 132 having a logiccontroller programmer component 134 for inputting a program or algorithm and executing such, and atiming element component 136 for electronically opening and closing an automated ball valve 138 in accordance with the program or algorithm, for precise metering ofcomposition 40 to the contaminatedgeologic formation 30 at precise time intervals. In addition,logic controller 132 is powered by abattery pack 142 viaelectrical lines 140 for operating in the field where no electrical power outlets are available. It is noted thatbattery pack 142 andelectrical line 140 can be contained within thelogic controller 132, as well as externally as shown in the drawings.Composition 40 is discharged through the automatic ball valve 138 when it is in the open position, into a length ofdischarge tubing 148, as shown in FIGS. 2 through 5. -
Logic controller 132 may further include additional means for controlling the metering ofcomposition 40 to the contaminatedgeologic formation 30, via the option of a plurality of digital and/or fiber-optic sensors 144 a to 144 i for the in-situ monitoring of parameters such as the static-water levels, the changes in static-water levels, the in-situ concentrations of each of the components of the chemical compositions or the by-products thereof, the rate of use of one or more of the components of the chemical compositions by the MRP microorganisms, the total estimated mass of the microorganisms in-situ, the biomass growth rate of the naturally occurring MRP microorganisms in-situ, the conversion rates of the converted end-products being generated by the MRP microorganisms, the pH and/or redox potential of the saturated geologic media or biomass, and the temperature of the saturated geologic media and other pertinent measurable data needed.Logic controller 132 also includes adisplay component 146 for displaying the sensor outputs; as well as a telecommunication data link andtelemetry phone lines 141 and 143, respectively, for communicating the controller data to and receiving program changes from an off-site location. -
Bioremediation processing apparatus 50 further includes an optionalpressurized water feed 109, as shown in FIG. 1. The pressurized water feed consists of a pressurized water line 111, connected to a pressurized water supply main; a pressure-reducingvalve 113; alogic controller 132′; a manually-operated ball valve a 114′; anddischarge tubing 115. The purpose of the optional pressurized water feed is (1) to provide additional fluid to periodically flush the concentrated fluid composition through the contaminatedgeologic media 30 at precise rates and time intervals, and (2) to increase saturation of the contaminated geologic media. - The
well component assembly 150, as shown in FIG. 1, includes aPVC well riser 152 having anupper end section 154 and a lower endPVC screen section 156 having slottedopenings 158 within. Thewell PVC riser 152 is surrounded by backfilledsoil cuttings 160 and abentonite seal 162 at theupper end section 154 of thewell PVC riser 152; and is surrounded by a Morie (or equivalent)sand pack 164 at thelower end section 156 of thewell PVC riser 152. In addition, thewell PVC riser 152 includes aninlet opening 166, a plurality of discharge outlet openings 168 s and abottom end cap 169.Composition 40 is discharged into the contaminatedgeologic media 30 through discharge openings 168 s via thePVC screen 156 ofwell 152. - The use of well152 installed within a contaminated
geologic formation 30 is to form aninterface area 170 for bioremediation applications including light non-aqueous phase liquid contaminants (LNAPLs) where these contaminants have a specific gravity of less than one, as shown in FIG. 9, and/or installed to form aninterface area 170 with one or more hydrogeologic aquitards 36 for the bioremediation applications involving dense non-aqueous phase liquid contaminants (DNAPLs) where these contaminants have a specific gravity of more than one, as shown in FIG. 8. The use of thePVC screen 156 within well 152 at depths of no more than 0.5 feet to 10 feet below the seasonal low of thewater table level 28, as shown in FIG. 9 of the drawings, is for the bioremediation applications involving light non-aqueous phase liquid contaminants (LNAPLs) where these contaminants have a specific gravity of less than one. -
Outlet tubing 148 connected to themanual ball valve 114 extends into theinlet opening 166, as shown in FIG. 1, for discharging ofcomposition 40 into the contaminatedgeological formation 30 through multiple outlet opening 168s. - The present invention further includes an improved and optional subsurface vapor-
inerting system 200, as depicted in detail by FIGS. 5 and 6 of the drawings. The subsurface vapor-inerting system 200 is used for the reduction of oxygen gas (O2) concentrations 24 within thevadose zone section 38 of the contaminatedgeologic site 30 which provides fire safety prevention that reduces and/or eliminates flash fires and/or explosion hazards associated with oxygen gas 24 andhydrocarbon contaminants 14 in thevadose zone 38 where the potential for such fire and explosion hazards exists. The subsurface vapor-inerting system 200 includes aninert gas assembly 202 for dispensing of aninert gas 22; and awell component assembly 220 for transferring theinert gas 22 to the contaminatedgeologic formation 30. Thewell component assembly 220 of the vapor-inerting system 200, as shown in FIGS. 5 and 6, is installed close to thewell component assembly 150, and is constructed in a similar manner towell component assembly 150, except for the screenedPVC section 226 interval within thewell riser 222 which is no more than 1 ft to 10 ft above the seasonal high ofwater table level 28. The compressedinert gas 22 such as argon gas (A) is dispensed within the well 222 in a manner so as to maintain the gravitational flow or passive flow of theargon gas 22 into thevadose zone 38 of thegeologic media 30 in order to reduce any potential for fire and explosions in thevadose zone 38. This vapor-inerting system 200 is also used to provide an improved mechanism for the enhancement of anaerobic bioremediation processes, as theargon gas 22 enables the maintenance of anaerobic conditions within the contaminated geologic media being remediated. - The
inert gas assembly 202 includes aninert gas cylinder 204 having agas regulator 206 with agas regulator valve 208, a shut-offvalve 210, anoutlet connection component 212 and pressure in-line gauges 214 a and 214 b for maintaining a precise outlet pressure to properly blanket thevadose zone 38 with the argon gas (A) 22 suppressing vapors produced by the subsurface contaminants.Gas regulator 206 in addition includes a regulatorgauge protection cage 216, andflexible tubing 98 for discharging of the argon gas (A) 22 into thewell 222. - The
well component assembly 220, as shown in FIGS. 5 and 6, includes aPVC well riser 222 having anupper end section 224 and a lower endPVC screen section 226. In addition, wellcomponent assembly 220 includes a separatesubsurface housing unit 252 made of concrete or metal for containing both theinert gas assembly 202 andwell component assembly 220 therein.Housing 252 includes an outercylindrical bentonite layer 254, and an outer manhole cover 258. In addition,sub-surface housing 252 includes inner andouter surface walls bottom wall member 270 being a gravel layer.Bottom wall member 270 includes acircular hole opening 276 within the gravel layer for receiving theupper end section 224 ofwell casing 222. ThePVC well riser 222 is surrounded by backfilledsoil cuttings 230 and abentonite seal 232 at theupper end section 224 of thewell PVC riser 222; and is surrounded by a Morie (or equivalent)sand pack 234 at thelower end section 226 of thewell PVC riser 222. In addition, thewell PVC riser 222 includes aninlet opening 236, a plurality of discharge side outlet openings 236 s and abottom end cap 269.Inlet opening 236 includes awell cap 238 having a disconnect coupling/fitting 242 thereon. - As shown in FIG. 7,
composition 40 andalternative chemical compositions 41, 42, 43, 44 and 45 can be used in dual or other multiple dispensingapparatus assemblies electronic assemblies composition 40 andalternative compositions 41, 42, 43, 44 and 45 into thewell component assembly 150 viainlet opening 166. This allowscompositions geologic media 30 in precisely timed pulses in a manner which enables the temporal cycling of redox pathways so as to optimize the growth and health of MRP anaerobic microorganisms and to optimize contaminant degradation bysuch microorganisms 12. - In operation, the
anaerobic bioremediation system 10 facilitates the anaerobic biodegradation, detoxification, and/or transformation of contaminant compounds such as petroleum hydrocarbons, halogenated solvents, polychlorinated biphenyls, dioxins, pesticides, cyanides, toxic metals, hazardous wastes and the like that have been released into surface environments and/or subsurfacegeologic media 30 whereby such contaminants are transformed into safe, less-toxic and/or harmless end-products. - In addition, the
bioremediation system 10, also facilitates the anaerobic biodegradation, detoxification, and/or transformation of toxic organic and inorganic compounds in contaminatedgeologic media 30 under a wide range of reducing redox conditions and anaerobic respiration pathways including denitrification, manganese-reduction, iron-reduction and sulfate-reduction. Another application of the use of theanaerobic bioremediation system 10, with regard to the above, would be to facilitate the suppression of hydrogen sulfide (H2S), related sulfides, mercaptans and the undesirable odors related to these compounds produced as a result of the metabolic activity of sulfur-reducing microorganisms via the stimulation and maintenance of denitrifying, manganese-reducing and iron-reducing conditions. - The
well component assembly 150 provides a proper fluid-exchange interface with the contaminatedgeologic media 30 which in turn provides a means of infiltration ofchemical composition 40,optional water feed 20, andcarrier gas 22 within the contaminatedgeologic formation 30 for stimulating and facilitating the bioremediation of the toxic organic and inorganic compounds by the indigenousanaerobic microorganisms 12 located within the aforementionedgeologic formation 30. - In addition, the present invention also provides for an improved subsurface vapor-
inerting system 200 designed to reduce oxygen gas (O2) concentrations 24 in the vadose-zone 38 of the contaminatedgeologic media 30 in order to reduce or eliminate the potential for flash fires and/or explosion hazards in the subsurface areas where the potential for such fire and explosion hazards exists. Thewell component assembly 220 of the vapor-inerting system 200, as shown in FIG. 5, is installed adjacent to thewell component assembly 150. ThePVC well riser 222 ofwell component assembly 220 delivers theinerting argon gas 22 to thevadose zone 38 of the contaminatedgeologic media 30 while simultaneously thePVC well riser 152 ofwell component assembly 150 delivers thechemical nutrient composition 40 and theargon carrier gas 22 to the contaminated area ofgeologic media 30 in order to stimulate the indigenousanaerobic microorganisms 12 at thatinterface area 170 within the aforementioned contaminatedgeologic media 30. Thevapor inerting system 200 can also be used independently of theanaerobic bioremediation system 10. - To put the
bioremediation processing apparatus 50 and thevapor inerting system 200 into operation initially after construction, several preparation steps are provided for, such as the construction and placement ofwell component assemblies geologic site 30, construction and placement of eachhousing member geologic media 30, and the placement of eachwell component assemblies housing member circular hole openings upper end sections - The anaerobic bioremediation system provides convenient and flexible means of either preparing
composition 40 in a large make-up mixing tank (not shown), or in the actualproduct tank canisters 100 a to 100 f at a convenient off-site premise or at the contaminatedgeologic site 30, when logistics permit it. Ifcomposition 40 is prepared in the larger mixing tank,composition 40 is then transferred to the plurality ofproduct tank canisters 100 a to 100 f via a portable pump (not shown). After theproduct tanks 100 a to 100 f are filled withcomposition 40, theirrespective lids 102 a to 100 f are closed shut and theproduct tanks 100 a to 100 f are then pressurized by argon gas (A) 22 thereby sealing theirrespective lids 102 a to 102 f to prevent leaks ofcomposition 40 contained therein. Theproduct tank canisters 100 a to 100 f are then transported to the contaminatedgeologic site 30. - Another preparation step is the development of a computer program for the
logic controller 132 of theelectronic control assembly 130 where the algorithms in the program are based on mathematical models of one or more of the following operating parameters for the bioremediation system 10: - 1) The rates of the diffusion-based transport of the biogeochemical compounds in
composition 40 being used in the contaminatedgeologic media 30. - 2) The uptake rates of biogeochemical compounds in
composition 40 by the naturally occurringMRP microorganisms 12 in-situ for degrading the contaminants. - 3) The rates, duration and repetition of cycles for
- a) biomass growth followed by
- b) biomass decay in-situ.
- 4) The duration and repetition and/or cycling of various redox pathways
- In conjunction with the preceding step, a plurality of digital and/or fiber-
optic sensors 144 a to 144 i may be connected tologic controller 132 and regularly calibrated to monitor and/or control the delivery ofcomposition 40 based upon real-time measurements of one or more parameters in-situ at selected locations within the contaminatedgeologic media 30. For example, such parameters may include in-situ monitoring of the following: - 1) Static-water levels;
- 2) Meteorologically induced changes in static-water levels;
- 3) The rates each of the electron-acceptors are being used by the
MRP microorganisms 12; - 4) The biomass growth rate of the naturally occurring
MRP microorganisms 12 in-situ; - 5) The relative metabolic activity of the naturally occurring
MRP microorganisms 12 in-situ; - 6) The conversion rates of the converted end-products being generated by the
MRP microorganisms 12; -
geologic media 30; and - 8) The temperature within the contaminated
geologic media 30. - The operator (being at the site) removes the
outer manhole cover 58 having afoam insulation 60 attached from the top of thesubsurface apparatus housing 52 allowing the operator access to thewell component assembly 150 withinhousing 52. The operator then places the plurality ofproduct tanks 100 a to 100 f, and theelectronic control assembly 130 within thesubsurface housing 52, such that theproduct tanks 100 a to 100 f are placed on thebottom floor 72 in a circular fashion such that thelast product tank 100 f having theelectronic control assembly 130 attached thereto is adjacent and in close proximity to thewell component assembly 150. Theproduct tanks 100 a to 100 f are then joined together via the plurality of quick disconnect couplings 104 a to 104 l having the jumper-line tubing 106 a to 106 f attached thereto, if being operated in series as shown in FIG. 3a. If being operated in parallel as shown in FIG. 3b, the jumper line tubing is connected from themanifolds 99 a and 99 b to theproduct tanks 100 a to 100 f. Once all of the digital and/orfiber optic sensors 144 a to 144 i have been calibrated (if the optional sensors are to be used) and thelogic controller 132 is properly programmed, the operator then connects thebattery power pack 142 viaelectrical power line 140 for supplying electrical power to thelogic controller 132. The operator then connects thelogic controller 132 to thelast product tank 100 f via quick disconnect coupling 104 l (for series operation). Thegas cylinder 82 having argon gas (A) 22 (which is still located atground level 26 above theapparatus system 50 for easier access) is then connected to thefirst product tank 100 a (for series operation) or to thegas manifold 99 a (for parallel operation) via the quick disconnect coupling 104 a. The operator now opens thevalve 88 ongas cylinder 82 and the gas pressure, as shown on the in-linegas pressure gauge 92, is set to be within the range of 5-to-10 psig or approximately 5 psig above the minimum pressure required viagas regulator valve 86 on thegas regulator assembly 84 to initiate the flow ofcomposition 40 out of theproduct tanks 100 a to 100 f with the argon carrier gas (A) 22 and into theproduct tubing 148. Simultaneously, as the above step is taking place, the operator also checks that thelogic controller 132 is manually actuated and theball valve 114 is opened, and thelogic controller 132 is set and adjusted to the desired flow ofcomposition 40 out of thecontroller 132 and into theproduct tubing 148. Oncecomposition 40 is flowing freely through the dispensingapparatus assembly 80 of thebioremediation processing apparatus 50 and out the end ofproduct tubing 148, the logiccontroller program component 134 andtiming element 136 oflogic controller 132 are checked again or modified if desired by the operator. Then thelogic controller 132 is manually closed and set to an automatic setting by the operator. Theproduct tubing 148 is then placed into thewell apparatus 150. Thegas cylinder 82 which is already connected to thefirst product tank 100 a orgas manifold 99 a is then placed intosubsurface housing 52 next to thefirst product tank 100 a orgas manifold 99 a. - As noted above, if the product tanks are to be operated in parallel as shown in FIG. 3B, the
gas cylinder 82 is connected to thegas manifold 99 a, and jumper tubing from the inlet of each uproduct tank is connected to the gas manifold. Jumper lines are then connected to the discharge of each product tank at one end and to the liquid manifold 99 b on the other end, as shown in FIG. 3B. The rest of the set-up process as described above for series operation, is the same for parallel product tank operation. - If the optional water feed is installed and is to be used,
manual control valve 114′ would be opened and adjusted until the desired flow rate of water is discharged fromtubing 115. The automatic control valve 138′ contained within waterfeed logic controller 132′ would then be manually closed, and the logic controller programmed to operate as needed.Water feed tubing 115 would then be placed into thewell apparatus 150. - The
man hole cover 58 having theinsulation layer 60 is then placed back on top of thesubsurface housing 52 and theanaerobic bioremediation system 10 is now operating to facilitate the biodegradation, biotransformation or detoxification of thecontaminants 14 atinterface area 170 of contaminatedmedia 30 into harmless end products including carbon dioxide gas (CO2) 16, nitrogen gas (N2) 18 and water (H20) 20. - In the event that an above-grade installation for the
bioremediation system 10 is preferred, the installation and set-up procedures for the dispensingapparatus 80 would be the same as described above with the exception that the said dispensing assembly would be installed in a suitable above-ground housing. - If the vapor suppression and
inerting system 200 is being used in conjunction with the dispensingapparatus assembly 80, the operator removes outer manhole cover 258 and places theinert gas assembly 202 in close proximity to thewell component assembly 220, such that theinert gas cylinder 204 having argon gas (A) 22 therein stands on thebottom gravel floor 272 ofhousing 252. The operator then checks thegas regulator 206 and the component fitting 212 and attachestubing 98 to well cap disconnect fitting 242 onwell cap 238, so that theflexible discharge tubing 98 can discharge the argon gas (A) 22 into thewell riser 222 ofwell component assembly 220. The operator then opensvalve 210 ongas cylinder 204 and adjusts thegas regulator valve 208, such that the argon gas (A) 22 is set to flow and run at the minimum setting at which the argon gas (A) 22 is discharged into thewell riser 222. The minimum measurable rate on thepressure gauge 214 ofgas regulator 206 for discharging the argon gas (A) 22 into thewell riser 222 has a setting of about 1 psig. - The purpose of
gas cylinder 204 is to maintain the gravitational flow or passive flow of the argon gas (A) 22 into thevadose zone 38 of the contaminatedgeologic media 30 in order to suppress vapors from the subsurface contaminants which have the potential to cause fire and explosions in that area. Also, the argon gas (A) 22 enables the maintenance of anaerobic conditions within the contaminatedgeologic site 30 for a continuous enhancement of the anaerobic bioremediation processes taking place atinterface area 170. The manhole cover 258 is then placed onhousing 252 by operator for the completion of this step of initially activating thevapor suppression system 200. In the event that an above-grade installation for thevapor suppression system 200 is preferred, the installation and set-up procedures for theinerting assembly 202 would be the same as described above with the exception that the said inerting assembly would be installed in a suitable above-ground housing. - During the normal course of processing as just previously described, the operator is further preparing additional sets of
product tanks 100 a′ to 100 f, 100 a″ to 100 f″, etc. having a preferred bioremediation composition comprising chemical electron acceptors, nutrients, carbon sources or the like (e.g., see U.S. Pat. No. 6,020,185 to Hince et al.). After the product tanks are filled, theirlids 102 a′ to 102 f, 102 a″ to 102 f′, etc. are closed and theproduct tanks 100 a′ to 100 f and 100 a″ to 100 f″ are then pressurized to seal theirlids 102 a′ to 102 f and 102 a″ to 102 f′ to prevent leaks. The aforementioned sets of product tanks having the preferred bioremediation composition are in a stand-by mode at the off-site preparation location, ready to replace the first set ofproduct tanks 100 a to 100 f when they are empty. This aforementioned procedure is also done with severaladditional gas cylinders 82′ and 204′, and 82″ and 204″, etc. having argon gas (A) 22 therein which are also in a stand-by mode at the off-site preparation location and are ready to replace thefirst gas cylinders apparatus assembly 80 and theelectronic control assembly 130 for proper functioning according to the pre-determined standards initiated for theanaerobic bioremediation system 10 in degrading thecontaminants 14 at thegeologic work site 30. These checks are generally performed at the same time that theproduct tanks 100 a to 100 f andgas cylinders - When the operator decides it is time to replace the
product tanks 100 a′ to 100 f based on preset feed rates and frequency, themanhole cover 58 is removed from thesubsurface housing 52 allowing access to the dispensingapparatus assembly 80 and theelectronic control assembly 130 withinsubsurface housing 52, as shown in FIGS. 1 and 5 of the drawings. The operator then closes the shut-offvalve 88 ongas cylinder 82 and removes the quick disconnect coupling 104 a connectinggas cylinder 82 having argon gas (A) 22 from thefirst product tank 100 a in-line. Then thegas cylinder 82 is lifted out of thehousing 52. - The operator then removes the quick disconnect coupling104 l connecting the
last product tank 100 f to thetubing 106 f from thelogic controller 132, such that thelogic controller 132 is then disconnected and set aside. If thelogic controller 132 is in an open mode, the operator then manually closes the automated control ball valve 138. The operator then continues to remove and set aside the remainingquick disconnect couplings 104 b to 104 k andjumper line tubing 106 a to 106 f from theempty product tanks 100 a to 100 f that were connected in series, as shown in FIGS. 2 and 3 of the drawings. Theempty product tanks 100 a to 100 f are then removed from thesubsurface housing 52 and are set aside atground level 26. Thereplacement product tanks 100 a′ to 100 f′ havingcomposition 40 therein are then placed onto thebottom floor 72 of thesubsurface housing 52 in a circular fashion, as shown in FIG. 2 of the drawings. The operator then puts back on all of thequick disconnect couplings 104 b to 104 k andjumper line tubing 106 a to 106 f onto thereplacement product tanks 100 a′ to 100 f in order to connect theseproduct tanks 100 a′ to 100 f in series. Then the operator puts back on the quick disconnect coupling 104 l onto thelast product tank 100 f′, where coupling 104 l connects tobarb connector 110 for reattaching thelogic controller 132 to thelast product tank 100 f′. Next, the operator sets a replacementcarrier gas cylinder 82′ of compressed argon gas (A) 22 atground level 26 and re-attaches the quick disconnect coupling 104 a and thehose clamp 112 onhose 98 thereby connecting thegas cylinder 82 to the first product tank (in-line) 100 a′. The operator now re-opens thevalve 88 and adjusts theregulator valve 86 on thegas regulator assembly 84, such that the in-line pressure gauge 92 ofgas regulator 84 is set to a 5 psig setting, or set at approximately 5 psig above the minimum pressure required to initiate the flow of thechemical nutrient composition 40 out of theproduct tanks 100 a′ to 100 f′. The operator now adjusts thelogic controller 132 such that automatic ball valve 138 is manually re-set to the opened position, and where themanual ball valve 114 attached on the discharge side of thelogic controller 132 is re-set to adjust thenutrient composition 40 flow at a desired rate for flowing into thegeologic media 30. Oncecomposition 40 is flowing freely through the dispensingapparatus assembly 80 and out ofproduct tubing 148, the operator then manually closes automatic valve 138 and re-checks the logiccontroller program component 134 for the feed algorithm previously inputted. Thelogic controller 132 is then manually closed and set to an automatic setting by the operator. The operator then placesproduct tubing 148 intowell assembly 150 and places gas cylinder 82 (which is already connected to thefirst product tank 100 a), intosubsurface housing 52. Lastly, the operator again replaces themanhole cover 58 havinginsulation 60 on top of thesubsurface housing 52 to prevent freezing ofcomposition 40 during the winter months. - If the
vapor suppression system 200 is in use, manhole cover 258 is removed and the shut offvalve 210 ongas cylinder 204 is closed.Tubing 98 is then disconnected fromwell cap 238 viaquick disconnect coupling 242, and then thegas cylinder 204 is lifted out of thehousing 252 by the operator. - The replacement
inert gas cylinder 204′ is then placed by the operator back onto thebottom gravel floor 272 of thesubsurface housing 252 and adjacent towell component assembly 220, as shown in FIG. 5 of the drawing. The operator then checks thegas regulator 206, the connection fitting 212 viatubing 98 being properly attached to theinert gas cylinder 204 and attachestubing 98 to the well cap quick disconnect fitting 242 onwell cap 238, as shown in FIG. 5 of the drawings. The operator then adjusts thevalve 210 ongas cylinder 204 to an open position, and adjusts thevalve 208 ongas regulator assembly 206 such that the argon gas (A) 22 is set to flow and run at the minimum setting at which the argon gas (A) 22 is discharged into thewell riser 222. The minimum measurable rate on thepressure gauge 216 ofgas regulator 206 for discharging the argon gas (A) 22 into thewell riser 222 has a setting of about 1 psig. - The continuous operation of the
bioremediation processing apparatus 50 of theanaerobic bioremediation system 10 for degradingcontaminants 14 at a particulargeologic site 30 may take up to several months. During this time, operators of theanaerobic bioremediation system 10 will repeat the aforementioned steps and procedures of replacing thegas cylinders product tanks 100 a to 100f having compositions electronic control assembly 130 for the proper flow ofcompositions interface area 170 ofgeologic media 30. - In the event that an above-grade installation for the
anaerobic bioremediation system 10 and thevapor suppression system 200 is utilized, the installation and set-up procedures for the dispensingapparatus 80 andinert gas assembly 202 would be the same as described above with the exception that the said dispensing apparatus and inerting assembly would be operated and maintained within a suitable above-ground housing. - As noted in the Overview of the invention, bacteria utilize electron acceptors in the order of their decreasing energy yield (Gibbs Free Energy [ΔG] in KJ/mole CH20). In theory, as the availability of a higher-energy electron acceptor wanes (e.g., O2), conditions become favorable for microbial respiration with lower-energy electron acceptors (e.g., NO3, MN(IV), Fe(III), and SO4). The natural sequence of microbial utilization of electron acceptors in the environment is summarized in Table 1. In the absence of higher-energy electron acceptors, sulfates serve as the electron acceptor for oxidation by anaerobic microorganisms. Sulfate is reduced to hydrogen sulfide (H2S) under anaerobic conditions; hydrogen sulfide has a characteristic rotten egg odor, is extremely toxic, and is corrosive to metals. Hydrogen sulfide can also be biologically oxidized to sulfuric acid which is also extremely corrosive.
- The bioremediation system of the present invention provides means by which a preferential electron acceptor (such as oxygen in the form of nitrous oxide, nitrate, Fe(III) or Mn (IV)) can be applied where there is potential for H2S formation due to the presence of sulfate, such that the bacteria will preferentially use the higher-energy yielding electron acceptor, and H2S will not be formed. The result is suppression of malodorous and problematic compounds that would otherwise be produced.
- Site Description and Type of Release
- A release of an unknown quantity of gasoline occurred from piping associated with the former UST systems removed and replaced at the site in the late 1980's.
- Site Hydrogeology
- The overburden sediments at the site comprise fine-to-medium glaciofluvial sands with varying amounts of silt. The water table ranges from 6-to-10 ft. below grade. A compact, silty-clay aquitard of glaciolacustrine origin is present at depths ranging from 15-to-19 ft. below grade. Bedrock was not encountered during drilling and the bedrock aquifer is not believed to have been impacted. A stream wraps around the site and its surroundings approximately 200 ft. downgradient and ground-water flow conditions have been interpreted fluctuate in response to local surface-water/ground-water interaction and meteorological events.
- Investigation and Remediation
- A subsurface investigation was performed by Geovation from 1993-1996 which included the installation of seven monitor wells and collection of soil and ground water samples. The results of the investigation indicated the presence of gross soil and ground-water contamination, with as much as 2.1 ft. of gasoline in a site monitor well. Two anaerobic bioremediation systems (ABSs) were installed, one next to the pump island and one adjacent to the tank field, with minimal disruption of site commercial activities. Operation of the ABSs has had a negligible impact on gas-station operations.
- Baseline contaminant levels included more than 2 ft. of free product, MTBE- and 1,2-DCA-amended gasoline in the most contaminated well and >16-42 mg/L total BTEX in the next most contaminated well.
- Results
- To date, free product thicknesses have decreased approximately 90 percent and dissolved phase BTEX compounds have decreased by as much as 88 percent in the site well with the highest BTEX level prior to remediation activities. BTEX concentrations in this well decreased by 92% over the first three months of treatment from >16 mg/L to 3.4 mg/L. Microbiological assays and microscopic investigation documented a rapid response of the microbial community to ABS treatment as evidenced by a 30-fold increase in bacterial biomass in the downgradient monitor well closest to one of the ABSs, by the second week of treatment. The analysis of biochemical markers, including phospholipid fatty acid (PLFA) analyses, indicated that ABS treatment had increased the biomass and improved the overall health and growth rate of the microbial community. These data also indicated a shift in the composition of the microbial community towards gram-negative, more rapidly growing species in response to ABS treatment. Gene probe analysis of the microbial community indicated the presence of strict anaerobes, such as Geobacter spp. and the like. Additional assays are underway to further investigate the anaerobic microbial community at the site.
- Site Description and Type of Release
- Two separate releases of fuel oil occurred totalling on the order of 3,500 gal. from a UST used to heat the facility.
- Site Hydrogeology
- Overburden sediments at the site are predominantly medium to coarse sands associated with glacial-outwash and/or a kame-delta, with ground water at approximately 17 ft. below grade Bedrock was not encountered and it is not believed to have been impacted.
- Investigation and Remediation
- Upon discovery of the release, the property owner's consultant removed contaminated soils from the source area and installed a series of monitor/recirculation wells for a carbon treatment system. Several pump-and-treat system wells were installed in the basement of the building and significant amounts of free product were detected and recovered. Monitoring data indicated that most of the remaining free-product contamination was trapped beneath the building. Extensive pump and treat efforts were met with limited effectiveness in that free-product recovery waned and free-product persisted in monitor wells across the site. Accordingly, the engineering firm in charge evaluated several bioremediation alternatives and Geovation was selected to conduct a anaerobic bioremediation program to augment the ongoing remediation activities. Three of Geovation's anaerobic bioremediation systems (ABS)10 were installed at key locations in the contaminant plume and operated beginning in late November 1996.
- Results
- Prior to remediation in November 1996, free-product thicknesses in site monitor wells were on the order of 0.35 ft. From late November through early December, several storm events occurred which caused product levels in site wells to increase to approximately 0.5 ft. in thickness as the water table rose through contaminated vadose-zone soils. As of late February 1997, approximately 3 months after initiation of remediation activities and approximately 2 weeks after cessation of the initial anaerobic bioremediation treatment program, free product was eliminated in most site wells, with only a sheen observed in several downgradient locations. Additional ABS operation initiated in late March 1997 has eliminated residual free-product in site wells.
- Throughout the course of the ABS operation, several obvious indications of enhanced biological activity were documented including the “carbonation” of site ground water resulting from carbon dioxide produced by the microbial community as well as documented increases in the number and size of bacteria present in site monitor wells. A twenty-to-thirty-fold increase in biomass was documented over the first two weeks of ABS operation. The most dramatic increases in microbial biomass occurred in the wells with the highest levels of contamination. The presence of a biomass slurry was routinely observed in site monitor wells and in the oil/water separator tanks associated with the pump and treat system. ABS operation is continuing at this time to address remnant dissolved phase contamination.
- An advantage of the present invention is that it provides for an anaerobic bioremediation system for the anaerobic biodegradation, detoxification and transformation of toxic organic and inorganic contaminants within contaminated geologic media into non-toxic compounds without further production of regulated wastes or other undesirable by-products that effect air, water and soil at the geologic site.
- Another advantage of the present invention is that it provides for an anaerobic bioremediation system for in-situ treatment of geologic media containing organic and inorganic contaminants that are metabolizable or transformable by naturally occurring indigenous, MRP anaerobic bacteria including denitrifying-, manganese-, iron- and sulfate-reducing microorganisms within the contaminated geologic media at the site.
- Another advantage of the present invention is that it provides for an anaerobic bioremediation system having apparatus which enables the delivery of electron acceptors, nutrients, chelating agents, surfactants, a diluent and an inert carrier gas to promote the growth of indigenous, MRP anaerobic bacteria including denitrifying-, manganese-, iron- and sulfate-reducing microorganisms such that the metabolism or transformation of the contaminants by these microorganisms can easily take place without the use of implanted microorganisms at the contaminated site.
- Another advantage of the present invention is that it provides for an anaerobic bioremediation system having apparatus which enables the electron acceptors, nutrients, chelating agents, surfactants, a diluent and an inert carrier gas to be more readily and rapidly dispersed in the contaminated geologic media, thereby becoming more widely available to MRP anaerobic bacteria within the contaminated geologic media.
- Another advantage of the present invention is that it provides for an anaerobic bioremediation system the electron acceptors, nutrients, chelating agents, surfactants, a diluent and an inert carrier gas in a chemical composition and form that is readily utilizable by indigenous, MRP anaerobic bacteria including denitrifying-, manganese-, iron- and sulfate-reducing microorganisms within the contaminated geologic media.
- Another advantage of the present invention is that it provides for an anaerobic bioremediation system that has the means to supply electron acceptors, nutrients, chelating agents, surfactants, a diluent and inert carrier gas as well as the capacity to modify the pH, redox potential and the availability of oxygen in the subsurface geologic media in a manner which enables a major improvement for the stimulation and growth of indigenous MRP microorganisms within contaminated geologic media.
- Another advantage of the present invention is that it provides a means for stimulating several different microbial respiration pathways under different redox conditions in-situ by using one or more chemical compositions in such a manner so as to stimulate MRP anaerobic bacteria including denitrifying-, manganese-, iron- and sulfate-reducing microorganisms within the contaminated geologic media.
- Another advantage of the present invention is that it provides for an anaerobic bioremediation system having a means for stimulating, alternating and/or cycling various redox conditions and microbial respiration pathways within the contaminated geologic media in-situ by using one or more chemical compositions in such a manner so as to stimulate a temporal and/or spatial succession of redox conditions in the subsurface in order to enhance the growth of MRP anaerobic microorganisms and to optimize contaminant biodegradation and/or biotransformation by such microorganisms.
- Another advantage of the present invention is that it provides for an anaerobic bioremediation system having the capability for reducing flash fire and/or explosion hazards in the contaminated geologic media.
- Another advantage of the present invention is that it provides for an anaerobic bioremediation system having apparatus that is simple and inexpensive to construct and use, and which enables efficient delivery and monitoring of the nutrients and electron acceptors for the optimum growth rate and kinetics of various indigenous, denitrifying and other MRP microorganisms in order to maximize the rate of degradation and transformation of the contaminants into non-toxic compounds by these indigenous MRP microorganisms.
- Another advantage of the present invention is that it provides for an anaerobic bioremediation system having a process that is simple and inexpensive to operate, especially under actual field conditions and the logistical constraints of small and/or busy sites (e.g., Example 1).
- Another advantage of the present invention is that it provides for an anaerobic bioremediation system whose operation can be modified manually or automatically either on-site or from off-site locations based on real-time measurements of in-situ conditions.
- Another advantage of the present invention is that it provides for an anaerobic bioremediation system having a process that can be performed rapidly and safely in the field and which results in the site meeting environmental clean-up standards set by various governmental agencies more rapidly and at a lower cost than can be accomplished with other methods.
- A further advantage of the present invention is that it provides for an improved anaerobic bioremediation system that can be easily produced in an automated and economical manner and is readily affordable by various responsible parties, consultants, contractors, engineers, governmental agencies and corporate users.
- A latitude of modification, change, and substitution is intended in the foregoing disclosure, and in some instances, some features of the invention will be employed without a corresponding use of other features. Accordingly, it is appropriate that the appended claims be construed broadly and in a manner consistent with the spirit and scope of the invention herein.
Claims (26)
- 29. Bioremediation apparatus for anaerobic biodegradation, detoxification, and transformation of toxic organic and inorganic compounds in a contaminated geologic media, comprising:a) a first set of one or more storage tanks containing a chemical composition for anaerobic biodegradation of toxic compounds in contaminated geologic media;b) valve means connected to said first set of storage tanks;c) at least one logic controller means for opening and closing said valve means connected to said first set of storage tanks to supply said chemical composition to the contaminated geologic media; andd) a screened well connected to said first set of storage tanks for supplying said chemical composition to the contaminated geologic media.
- 30. Bioremediation apparatus in accordance with
claim 29 , wherein said one or more storage tanks contain an inert gas as a carrier for said chemical compositions. - 31. Bioremediation apparatus in accordance with
claim 30 , wherein said one or more storage tanks are pressurized for the pressurized storage and dispensing of said chemical composition and said inert gas. - 32. Bioremediation apparatus in accordance with
claim 29 , wherein said logic controller means includes means for inputting and executing an algorithm or computer program into said logic controller means. - 33. Bioremediation apparatus in accordance with
claim 29 , further including one or more sensors connected to said logic controller means. - 34. Bioremediation apparatus in accordance with
claim 33 , wherein said sensors are disposed in the contaminated geologic media for taking readings of conditions therein. - 35. Bioremediation apparatus in accordance with
claim 34 , wherein said sensors include means for sensing data to obtain measurements of static-water levels, the changes in static-water levels, the in-situ concentrations of each of the components of the said chemical compositions or the byproducts thereof, the rate of use of one or more of the components of the said chemical compositions by anaerobic microorganisms, the total estimated mass of the microorganisms in-situ, the biomass growth rate of the naturally occurring anaerobic microorganisms in-situ, the relative metabolic activity of the naturally occurring anaerobic microorganisms in-situ, the conversion rates of the converted end-products being generated by the anaerobic microorganisms, the pH and/or redox potential of the saturated geologic media or biomass, and the temperature of the saturated geologic media or biomass. - 36. Bioremediation apparatus in accordance with
claim 33 , further including means for transmitting the data received by said sensors to a data-logger or computer at a remote location. - 37. Bioremediation apparatus in accordance with
claim 35 , wherein said logic controller means further includes programming means for controlling the dispensing of said chemical compositions at predetermined dispensing rates or as a function of one or more of said measurements. - 38. Bioremediation apparatus in accordance with
claim 37 further including means for remotely inputting an algorithm or computer program into the said logic controller means by the user for purposes of controlling the dispensing of the said chemical compositions. - 39. Bioremediation apparatus in accordance with
claim 37 , wherein said programming means includes a programmer component having a timing element for electronically opening and closing said valve means for the precise metering of said chemical composition into the contaminated geologic media. - 40. Bioremediation apparatus in accordance with
claim 29 , wherein said valve means includes an automatic ball valve being electronically connected to said logic controller means and a manual ball valve being mechanically connected to said logic controller means. - 41. Bioremediation apparatus in accordance with
claim 29 , further including:a) a pressurized water supply line;b) a pressure reducing valve connected to said pressurized water supply line;c) an alternate automatic valve means connected to said pressure reducing valve;d) an alternate logic controller means being electronically connected to said alternate automatic valve means for opening and closing said alternate automatic valve means connected to said pressurized water supply line to supply said water supply to the contaminated geologic media;e) an alternate manual valve means wherein said valve means is mechanically connected to said alternate logic controller means; andf) said screened well being connected to said pressurized water supply line for supplying said water supply to the contaminated geologic media. - 42. Bioremediation apparatus in accordance with
claim 29 , further including:a) two or more sets of one or more storage tanks containing additional chemical compositions for anaerobic biodegradation of toxic compounds in the contaminated geologic media;b) two or more valve means connected to said two or more sets of storage tanks;c) one or more alternate logic controller means for opening and closing said additional valve means connected to said additional sets of storage tanks to supply said additional chemical compositions to the contaminated geologic media; andd) said screened well being connected to said additional sets of storage tanks for supplying said alternate chemical compositions to the contaminated geologic media. - 43. Bioremediation apparatus in accordance with
claim 42 , wherein said logic controller means and said alternate logic controller means each include means for controlling the delivery of said chemical composition and said additional chemical compositions to the contaminated geologic media simultaneously or in an alternating manner. - 44. Bioremediation apparatus in accordance with
claim 29 , further including a vapor suppression system for reducing flash fire and/or explosion hazards in the contaminated geologic media, comprising:a) one or more gas cylinder tanks containing an inert gas for reducing oxygen gas (O2) concentrations within the contaminated geologic media;b) control valve means connected to said one or more gas cylinder tanks;c) pressure sensing means connected to said one or more gas cylinder tanks for providing a minimum pressure setting in which said inert gas is discharged from said gas cylinder tanks to the contaminated geologic media; andd) means for connecting a second well to said gas cylinder tanks for supplying said inert gas to the contaminated geologic media. - 45. Bioremediation apparatus in accordance with
claim 44 , wherein said inert gas is argon, neon, krypton or xenon. - 46. Bioremediation apparatus in accordance with
claim 44 , wherein said control valve means is a manual shut-off valve. - 47. Bioremediation apparatus in accordance with
claim 44 , wherein said pressure sensing means includes one or more in-line pressure gauges. - 54. A method for anaerobic biodegradation, detoxification, and transformation of toxic organic and inorganic compounds in contaminated geologic media comprising the steps of:a) pressurizing one or more storage tanks containing a chemical composition and an inert carrier gas;b) connecting valve means to said one or more pressurized storage tanks;c) connecting a well to said valve means for supplying said chemical composition and said inert carrier gas through said well to the contaminated geologic media; andd) opening and closing said valve means to dispense said chemical composition and said inert carrier gas under pressure through said well to the contaminated geologic media.
- 55. A method in accordance with
claim 54 , further including the step of disposing sensors in the contaminated geologic media for taking readings of conditions therein. - 56. A method in accordance with
claim 55 , whereby the step of opening and closing said valve means is performed by logic controller means having means for inputting and executing an algorithm or computer program into said logic controller means. - 57. A method in accordance with
claim 54 , whereby the step of opening and closing said valve means is performed by logic controller means having means for inputting and executing an algorithm or computer program into said logic controller means. - 58. A method in accordance with
claim 57 , whereby the program of said logic controller means is modified via an off-site computer means. - 59. A method in accordance with
claim 56 , whereby the output from one or more said sensors directly modifies or controls the program running in said logic controller means. - 60. A method in accordance with
claim 59 , whereby the data from said sensors is:a) transmitted to an off-site computer; andb) analyzed and interpreted by the user; andc) used to create a new or modified algorithm or program for use in said logic controller means; andd) input to said logic-controller means from an off-site computer.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/671,257 US20040082055A1 (en) | 1997-05-23 | 2003-09-25 | Anaerobic bioremediation system |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/862,782 US6020185A (en) | 1997-05-23 | 1997-05-23 | Method and composition for the anaerobic biodegradation of toxic compounds |
US10/671,257 US20040082055A1 (en) | 1997-05-23 | 2003-09-25 | Anaerobic bioremediation system |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/862,782 Division US6020185A (en) | 1997-05-23 | 1997-05-23 | Method and composition for the anaerobic biodegradation of toxic compounds |
Publications (1)
Publication Number | Publication Date |
---|---|
US20040082055A1 true US20040082055A1 (en) | 2004-04-29 |
Family
ID=25339335
Family Applications (5)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/862,782 Expired - Fee Related US6020185A (en) | 1997-05-23 | 1997-05-23 | Method and composition for the anaerobic biodegradation of toxic compounds |
US09/493,521 Expired - Fee Related US6344355B1 (en) | 1997-05-23 | 2000-01-28 | Anaerobic bioremediation system |
US09/493,579 Expired - Fee Related US7413890B1 (en) | 1997-05-23 | 2000-01-28 | Methods for anaerobic bioremediation using solid-chemical compositions containing Mn(IV) and Fe(III) |
US09/495,046 Expired - Fee Related US6720176B1 (en) | 1997-05-23 | 2000-01-31 | Liquid chemical compositions containing soluble sulfates and methods for anaerobic bioremediation |
US10/671,257 Abandoned US20040082055A1 (en) | 1997-05-23 | 2003-09-25 | Anaerobic bioremediation system |
Family Applications Before (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/862,782 Expired - Fee Related US6020185A (en) | 1997-05-23 | 1997-05-23 | Method and composition for the anaerobic biodegradation of toxic compounds |
US09/493,521 Expired - Fee Related US6344355B1 (en) | 1997-05-23 | 2000-01-28 | Anaerobic bioremediation system |
US09/493,579 Expired - Fee Related US7413890B1 (en) | 1997-05-23 | 2000-01-28 | Methods for anaerobic bioremediation using solid-chemical compositions containing Mn(IV) and Fe(III) |
US09/495,046 Expired - Fee Related US6720176B1 (en) | 1997-05-23 | 2000-01-31 | Liquid chemical compositions containing soluble sulfates and methods for anaerobic bioremediation |
Country Status (1)
Country | Link |
---|---|
US (5) | US6020185A (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030232423A1 (en) * | 2002-03-25 | 2003-12-18 | Priester Lamar E. | In situ biodegradation of subsurface contaminants by injection of phosphate nutrients and hydrogen |
US20060105448A1 (en) * | 2004-11-03 | 2006-05-18 | Medicel Oy | Reactor device |
US20100113308A1 (en) * | 2008-11-05 | 2010-05-06 | Kewei Zhang | Hydrocarbon Fluid Compositions and Methods for Using Same |
US20110211911A1 (en) * | 2010-03-01 | 2011-09-01 | Wavefront Technology Solutions Inc. | Method and apparatus for enhancing multiphase extraction of contaminants |
WO2015056110A1 (en) * | 2013-10-14 | 2015-04-23 | Uab "Biocentras" | Complex method for cleaning environment from oil pollutants |
US9523030B2 (en) | 2007-04-26 | 2016-12-20 | Trican Well Service Ltd | Control of particulate entrainment by fluids |
US9932514B2 (en) | 2014-04-25 | 2018-04-03 | Trican Well Service Ltd. | Compositions and methods for making aqueous slurry |
US9976075B2 (en) | 2005-05-02 | 2018-05-22 | Trican Well Service Ltd. | Method for making particulate slurries and particulate slurry compositions |
US10196560B2 (en) | 2015-01-30 | 2019-02-05 | Trican Well Service Ltd. | Proppant treatment with polymerizable natural oils |
US10202542B2 (en) | 2014-07-16 | 2019-02-12 | Trican Well Service Ltd. | Aqueous slurry for particulates transportation |
CN110423684A (en) * | 2019-08-05 | 2019-11-08 | 西安交通大学 | A kind of intelligence methane tank system |
WO2023147593A3 (en) * | 2022-01-31 | 2023-09-07 | Arizona Board Of Regents On Behalf Of Arizona State University | Methods of controlling microbiological processes for in situ contaminant treatment |
Families Citing this family (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6020185A (en) * | 1997-05-23 | 2000-02-01 | Geovation Consultants, Inc. | Method and composition for the anaerobic biodegradation of toxic compounds |
US6432693B1 (en) * | 1999-11-15 | 2002-08-13 | Geovation Technologies, Inc. | Advanced inorganic solid-chemical composition and methods for anaerobic bioremediation |
US6423531B1 (en) * | 1999-11-17 | 2002-07-23 | Geovation Technologies, Inc. | Advanced organic-inorganic solid-chemical composition and methods for anaerobic bioremediation |
US6403364B1 (en) * | 2000-01-28 | 2002-06-11 | Geovation Consultants Inc. | Method for the enhanced anaerobic bioremediation of contaminants in aqueous sediments and other difficult environments |
US6562235B1 (en) | 2000-08-08 | 2003-05-13 | Groundwater Services, Inc. | Enhanced anaerobic treatment zones in groundwater |
EP2458136A1 (en) * | 2001-02-14 | 2012-05-30 | M-I L.L.C. | Method of bio-remediating wellbore cuttings |
WO2003022744A2 (en) | 2001-09-06 | 2003-03-20 | Gannett Fleming, Inc. | In-situ process for detoxifying hexavalent chromium in soil and groundwater |
US6733207B2 (en) * | 2002-03-14 | 2004-05-11 | Thomas R. Liebert, Jr. | Environmental remediation system and method |
US20060094106A1 (en) * | 2002-03-25 | 2006-05-04 | Priester Lamar E Iii | Biodegradation of subsurface contaminants by injection of gaseous microbial metabolic inducer |
NL1021458C2 (en) * | 2002-09-13 | 2004-03-16 | Tno | Anaerobic biodegradation of aromatic hydrocarbons. |
US20040111955A1 (en) * | 2002-12-13 | 2004-06-17 | Mullay John J. | Emulsified water blended fuels produced by using a low energy process and novel surfuctant |
US7129388B2 (en) * | 2003-01-06 | 2006-10-31 | Innovative Environmental Technologies, Inc. | Method for accelerated dechlorination of matter |
US7044152B2 (en) * | 2003-01-06 | 2006-05-16 | Innovative Environmental Technologies, Inc. | Apparatus for in-situ remediation using a closed delivery system |
US7144725B2 (en) * | 2003-03-03 | 2006-12-05 | University Of North Dakota | Removal of toxic/hazardous chemicals absorbed in building materials |
US7021862B2 (en) * | 2003-03-04 | 2006-04-04 | Joe Hughes | Method for remediation of contaminated ground at oil or gas facility |
US7264713B2 (en) * | 2003-09-03 | 2007-09-04 | Thomas Kryzak | Apparatus, system and method for remediation of contamination |
DE102004011993A1 (en) * | 2004-03-11 | 2005-10-13 | Wacker-Chemie Gmbh | Anaerobic degradation of polyorganosiloxanes and organosilanes |
US7344337B2 (en) * | 2004-03-26 | 2008-03-18 | Ann Arbor Technical Services | Geomorphology environmental remediation process and systems |
EP1854860A1 (en) * | 2006-05-09 | 2007-11-14 | Stichting Geodelft | Biosealing |
BRPI0720529A2 (en) * | 2006-12-18 | 2014-02-04 | Novozymes North America Inc | PROCESSES FOR DETOXIFYING PRE-TREATED MATERIAL CONTAINING LIGNOCELLULOSIS, AND FOR PRODUCING A MATERIAL FERMENTATION PRODUCT, AND USING A COMPOUND AND AMIDASE AND ANHYDRASE. |
DE102007061138A1 (en) * | 2007-12-19 | 2009-06-25 | Agraferm Technologies Ag | Trace element solution for biogas processes |
US20090311048A1 (en) * | 2008-06-03 | 2009-12-17 | Horst John F | Mineral hardpan formation for stabilization of acid- and sulfate-generating tailings |
US7828974B2 (en) * | 2008-10-14 | 2010-11-09 | Innovative Environmental Technologies, Inc. | Method for the treatment of ground water and soils using dried algae and other dried mixtures |
US20140217016A1 (en) * | 2010-08-27 | 2014-08-07 | Kent C. Armstrong | Biomediation method |
GB2497250B (en) | 2010-09-21 | 2016-05-11 | Multi-Chem Group Llc | Method for the use of nitrates and nitrate reducing bacteria in hydraulic fracturing |
US9056340B2 (en) * | 2012-03-30 | 2015-06-16 | Bioremediation Specialists L.L.C. | Bioremediation systems, compositions, and methods |
US8679340B1 (en) | 2013-01-25 | 2014-03-25 | Parsons Corporation | Method to stimulate and sustain the anaerobic biodegradation of light non-aqueous phase liquid |
SE537085C2 (en) * | 2013-03-08 | 2014-12-30 | Ragn Sells Ab | Use of acidogenic leachate, procedure and plant for soil washing |
RU2601973C1 (en) * | 2015-05-13 | 2016-11-10 | Владимир Васильевич Слюсаренко | Method cleaning oil sludge and oil contaminated soil |
CN111487365B (en) * | 2020-01-07 | 2021-06-25 | 三峡大学 | Method for in-situ determination of denitrification and anaerobic ammonia oxidation rates of deep-water reservoir sediments |
CN111215438A (en) * | 2020-02-20 | 2020-06-02 | 广西博世科环保科技股份有限公司 | System and method for treating soil polluted by medium and low concentration petroleum hydrocarbon |
CN113000584B (en) * | 2021-04-28 | 2021-11-23 | 生态环境部南京环境科学研究所 | Device and method for reducing odor substances in soil through combination of electric remediation and chemical oxidation |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5178491A (en) * | 1991-06-19 | 1993-01-12 | International Technology Corporation | Vapor-phase nutrient delivery system for in situ bioremediation of soil |
US5265674A (en) * | 1992-02-20 | 1993-11-30 | Battelle Memorial Institute | Enhancement of in situ microbial remediation of aquifers |
US5342769A (en) * | 1992-08-04 | 1994-08-30 | Yellowstone Environmental Science, Inc. | Microbial dehalogenation using methanosarcina |
US5384048A (en) * | 1992-08-27 | 1995-01-24 | The United States Of America As Represented By The United States Department Of Energy | Bioremediation of contaminated groundwater |
US5398756A (en) * | 1992-12-14 | 1995-03-21 | Monsanto Company | In-situ remediation of contaminated soils |
US5482630A (en) * | 1994-06-20 | 1996-01-09 | Board Of Regents, The University Of Texas System | Controlled denitrification process and system |
US5560737A (en) * | 1995-08-15 | 1996-10-01 | New Jersey Institute Of Technology | Pneumatic fracturing and multicomponent injection enhancement of in situ bioremediation |
US6020185A (en) * | 1997-05-23 | 2000-02-01 | Geovation Consultants, Inc. | Method and composition for the anaerobic biodegradation of toxic compounds |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4299613A (en) * | 1979-02-22 | 1981-11-10 | Environmental Chemicals, Inc. | Controlled release of trace nutrients |
US5582627A (en) * | 1988-09-09 | 1996-12-10 | Yamashita; Thomas T. | Detoxification of soil |
US5387271A (en) * | 1990-04-11 | 1995-02-07 | Idaho Research Foundation, Inc. | Biological system for degrading nitroaromatics in water and soils |
AU655591B2 (en) * | 1990-06-08 | 1995-01-05 | Oms Investments, Inc. | Controlled-release microbe nutrients and method for bioremediation |
US5227069A (en) * | 1992-03-16 | 1993-07-13 | General Electric Company | Bioremediation method |
US5413713A (en) * | 1992-04-15 | 1995-05-09 | Day; Donal F. | Method for increasing the rate of anaerobic bioremediation in a bioreactor |
AU4669993A (en) * | 1992-07-16 | 1994-02-14 | Delman R. Hogen | Microbial mediated method for soil and water treatment |
US5369031A (en) * | 1992-07-21 | 1994-11-29 | University Of Houston | Bioremediation of polar organic compounds |
US5854061A (en) * | 1992-07-21 | 1998-12-29 | H&H Eco Systems, Inc. | Method for accelerated chemical and/or biological remediation and method of using an apparatus therefor |
US5476992A (en) * | 1993-07-02 | 1995-12-19 | Monsanto Company | In-situ remediation of contaminated heterogeneous soils |
US5363913A (en) * | 1993-08-30 | 1994-11-15 | Phillips Petroleum Company | Injection of sequestering agents for subterranean microbial processes |
JPH07255462A (en) * | 1994-02-02 | 1995-10-09 | Agency Of Ind Science & Technol | Method for obtaining organic solvent-resistant microorganism and organic solvent-resistant microorganism obtained by the method |
US5427944A (en) * | 1994-05-24 | 1995-06-27 | Lee; Sunggyu | Bioremediation of polycyclic aromatic hydrocarbon-contaminated soil |
US5811255A (en) * | 1995-09-20 | 1998-09-22 | Yellowstone Environmental Science | Apparatus and method for anaerobic respirometry |
-
1997
- 1997-05-23 US US08/862,782 patent/US6020185A/en not_active Expired - Fee Related
-
2000
- 2000-01-28 US US09/493,521 patent/US6344355B1/en not_active Expired - Fee Related
- 2000-01-28 US US09/493,579 patent/US7413890B1/en not_active Expired - Fee Related
- 2000-01-31 US US09/495,046 patent/US6720176B1/en not_active Expired - Fee Related
-
2003
- 2003-09-25 US US10/671,257 patent/US20040082055A1/en not_active Abandoned
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5178491A (en) * | 1991-06-19 | 1993-01-12 | International Technology Corporation | Vapor-phase nutrient delivery system for in situ bioremediation of soil |
US5265674A (en) * | 1992-02-20 | 1993-11-30 | Battelle Memorial Institute | Enhancement of in situ microbial remediation of aquifers |
US5342769A (en) * | 1992-08-04 | 1994-08-30 | Yellowstone Environmental Science, Inc. | Microbial dehalogenation using methanosarcina |
US5384048A (en) * | 1992-08-27 | 1995-01-24 | The United States Of America As Represented By The United States Department Of Energy | Bioremediation of contaminated groundwater |
US5398756A (en) * | 1992-12-14 | 1995-03-21 | Monsanto Company | In-situ remediation of contaminated soils |
US5482630A (en) * | 1994-06-20 | 1996-01-09 | Board Of Regents, The University Of Texas System | Controlled denitrification process and system |
US5556536A (en) * | 1994-06-20 | 1996-09-17 | Board Of Regents, The University Of Texas System | Bacterial bed |
US5560737A (en) * | 1995-08-15 | 1996-10-01 | New Jersey Institute Of Technology | Pneumatic fracturing and multicomponent injection enhancement of in situ bioremediation |
US6020185A (en) * | 1997-05-23 | 2000-02-01 | Geovation Consultants, Inc. | Method and composition for the anaerobic biodegradation of toxic compounds |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7645606B2 (en) * | 2002-03-25 | 2010-01-12 | Pha Environmental Restoration | In situ biodegradation of subsurface contaminants by injection of phosphate nutrients and hydrogen |
US20030232423A1 (en) * | 2002-03-25 | 2003-12-18 | Priester Lamar E. | In situ biodegradation of subsurface contaminants by injection of phosphate nutrients and hydrogen |
US20060105448A1 (en) * | 2004-11-03 | 2006-05-18 | Medicel Oy | Reactor device |
US7632673B2 (en) * | 2004-11-03 | 2009-12-15 | Medicel Oy | Reactor device |
US9976075B2 (en) | 2005-05-02 | 2018-05-22 | Trican Well Service Ltd. | Method for making particulate slurries and particulate slurry compositions |
US10023786B2 (en) | 2005-05-02 | 2018-07-17 | Trican Well Service Ltd. | Method for making particulate slurries and particulate slurry compositions |
US10138416B2 (en) | 2007-04-26 | 2018-11-27 | Trican Well Service, Ltd | Control of particulate entrainment by fluids |
US9523030B2 (en) | 2007-04-26 | 2016-12-20 | Trican Well Service Ltd | Control of particulate entrainment by fluids |
US7977285B2 (en) * | 2008-11-05 | 2011-07-12 | Trican Well Service Ltd. | Hydrocarbon fluid compositions and methods for using same |
US20100113308A1 (en) * | 2008-11-05 | 2010-05-06 | Kewei Zhang | Hydrocarbon Fluid Compositions and Methods for Using Same |
US20110211911A1 (en) * | 2010-03-01 | 2011-09-01 | Wavefront Technology Solutions Inc. | Method and apparatus for enhancing multiphase extraction of contaminants |
WO2015056110A1 (en) * | 2013-10-14 | 2015-04-23 | Uab "Biocentras" | Complex method for cleaning environment from oil pollutants |
US9932514B2 (en) | 2014-04-25 | 2018-04-03 | Trican Well Service Ltd. | Compositions and methods for making aqueous slurry |
US10202542B2 (en) | 2014-07-16 | 2019-02-12 | Trican Well Service Ltd. | Aqueous slurry for particulates transportation |
US10196560B2 (en) | 2015-01-30 | 2019-02-05 | Trican Well Service Ltd. | Proppant treatment with polymerizable natural oils |
CN110423684A (en) * | 2019-08-05 | 2019-11-08 | 西安交通大学 | A kind of intelligence methane tank system |
WO2023147593A3 (en) * | 2022-01-31 | 2023-09-07 | Arizona Board Of Regents On Behalf Of Arizona State University | Methods of controlling microbiological processes for in situ contaminant treatment |
Also Published As
Publication number | Publication date |
---|---|
US6020185A (en) | 2000-02-01 |
US6344355B1 (en) | 2002-02-05 |
US6720176B1 (en) | 2004-04-13 |
US7413890B1 (en) | 2008-08-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7413890B1 (en) | Methods for anaerobic bioremediation using solid-chemical compositions containing Mn(IV) and Fe(III) | |
Bouwer | Bioremediation of chlorinated solvents using alternate electron acceptors | |
Norris | Handbook of bioremediation | |
Lee et al. | Biorestoration of aquifers contaminated with organic compounds | |
Sims et al. | In Situ Bioremediation of Contaminated Ground Water 1 | |
Suthersan | Natural and enhanced remediation systems | |
Sims et al. | In Situ Bioremediation of Contaminated Unsaturated Subsurface Soils 1 | |
US6268205B1 (en) | Subsurface decontamination method | |
Grindstaff | Bioremediation of chlorinated solvent contaminated groundwater | |
Hatzinger et al. | In situ bioremediation of 1, 2-dibromoethane (EDB) in groundwater to part-per-trillion concentrations using cometabolism | |
Kennedy et al. | Applied geologic, microbiological, and engineering constraints of in‐situ BTEX bioremediation | |
Fiorenza et al. | Decision making—is bioremediation a viable option? | |
Suthersan et al. | Technical protocol for using soluble carbohydrates to enhance reductive dechlorination of chlorinated aliphatic hydrocarbons | |
Sweed et al. | Surface application system for in situ ground‐water bioremediation: site characterization and modeling | |
Hatzinger et al. | In situ bioremediation of perchlorate in groundwater | |
Borden | Protocol for enhanced in situ bioremediation using emulsified edible oil | |
Brubaker | In situ bioremediation of groundwater | |
DE102004001802A1 (en) | Method and device for the in situ purification of contaminated groundwater streams | |
Gamlin et al. | Innovative applications of subgrade biogeochemical reactors: Three case studies | |
Alvarez-Cohen | Engineering challenges of implementing in situ bioremediation | |
Norris | In-situ bioremediation of ground water and geological material: A review of technologies | |
Hooker et al. | In situ bioremediation of carbon tetrachloride: Field test results | |
Borden et al. | Edible Oil Barriers for Treatment of Perchlorate Contaminated Groundwater | |
Franzen et al. | Pulsing of multiple nutrients as a strategy to achieve large biologically active zones during in situ carbon tetrachloride remediation | |
Barenschee et al. | Kinetic studies on the hydrogen peroxide-enhanced in situ biodegradation of hydrocarbons in water-saturated ground zone |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: GEOVATION TECHNOLOGIES, INC., NEW YORK Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HINCE, ERIC C.;ZIMMER, ROBERT L.;REEL/FRAME:014552/0154 Effective date: 20030925 |
|
STCB | Information on status: application discontinuation |
Free format text: EXPRESSLY ABANDONED -- DURING EXAMINATION |