WO2003011487A1 - Biorestauration de contaminants metalliques avec des bacteries utilisant des hydrocarbures - Google Patents

Biorestauration de contaminants metalliques avec des bacteries utilisant des hydrocarbures Download PDF

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Publication number
WO2003011487A1
WO2003011487A1 PCT/US2002/024001 US0224001W WO03011487A1 WO 2003011487 A1 WO2003011487 A1 WO 2003011487A1 US 0224001 W US0224001 W US 0224001W WO 03011487 A1 WO03011487 A1 WO 03011487A1
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WIPO (PCT)
Prior art keywords
butane
hydrocarbon
metal
metal contaminant
substrate
Prior art date
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PCT/US2002/024001
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English (en)
Inventor
Felix Anthony Perriello
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Global Biosciences, Inc.
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Publication of WO2003011487A1 publication Critical patent/WO2003011487A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • 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
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
    • C12N1/26—Processes using, or culture media containing, hydrocarbons
    • C12N1/28—Processes using, or culture media containing, hydrocarbons aliphatic
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/103—Arsenic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/06—Contaminated groundwater or leachate
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities

Definitions

  • the present invention relates to the remediation of metal contaminants, and more particularly relates to the remediation of metal contaminants with hydrocarbon- utilizing bacteria.
  • Arsenic contamination in surface water, groundwater and soil represents a significant health hazard.
  • Arsenic is used for hardening metals such as copper and lead and as a doping agent in the electronics industry.
  • Arsenic salts are used to make herbicides, rodenticides and fireworks.
  • Arsenic and arsenic compounds are toxic and can be carcinogenic. They are absorbed into the body through gastrointestinal ingestion or inhalation. For example, the trivalent inorganic compounds of arsenic, such as arsenic trichloride, arsenic trioxide and arsine, are highly toxic.
  • Arsenic-contaminated groundwater has conventionally been treated by groundwater pump and treat technologies including post precipitation, chemical oxidation, filtration, sedimentation, etc.
  • the following methods are currently employed: 1) land farming, where soil piles are watered and aerated; 2) bioreactors that involve the slurry treatment of soil and water in a closed vessel to which oxygen, nutrients and a carbohydrate cosubstrate such as molasses, corn syrup, or hydrolyzed starch are added; and 3) in-situ treatment where contaminated soils are chemically oxidized and/or stabilized using encasement methods.
  • AMD acid mine drainage
  • CMOS acid mine drainage
  • Sulfide ores contain large quantities of pyrite, which is discarded in the tailings and produces sulfuric acid when exposed to water and oxygen.
  • the ferrous iron produced is then oxidized to ferric ions, which become the dominant oxidizing agent of the exposed sulfide minerals.
  • the reduced sulfur and iron compounds in the deposit provide an environment for T. ferrooxidans which oxidize iron, thiosulfate, sulfur and metallic sulfides to obtain energy for growth while using oxygen as the final electron acceptor and CO 2 as its sole source of carbon. This process generates an acidic pH.
  • AMD resulting from all types of metal mining operations is one of the most pressing environmental problems facing the mining and mineral industries. A significant portion of the AMD draining into rivers and streams is released from waste rock. Once the AMD process has begun, it is extremely difficult to reverse or stop.
  • Electrolytic plating solutions normally contain high concentrations of heavy metals like zinc, chromium, cadmium, nickel, selenium, copper, gold, silver and nickel.
  • Electroless nickel plating solutions contain a nickel metal salt, such as sulfate, acetate, carbonate or chloride salt, pH adjustors, accelerators, stabilizers, buffers, and wetting agents.
  • the electroless nickel solutions only have a limited useful life and eventually become depleted or spent.
  • the disposal or treatment of spent electrolytic metal plating solutions poses significant challenges for the electroplating industry.
  • the dissolved metal concentration must be below discharge thresholds in order to allow for the solution to be discharged as non-toxic waste directly to a municipal wastewater treatment facility.
  • the spent electroless solution is first contacted with a reducing agent for sufficient time to cause the dissolved metal salt to undergo chemical reduction, resulting in the precipitation of the metal compounds out of the solution.
  • Some methods include the dosing of electroless baths with caustic soda to precipitate the bulk of the heavy metal contaminants as insoluble hydrous oxides (metal hydroxides), pressing the sludge into a filter cake, drumming and disposal.
  • Another waste treatment used for spent electroless plating solutions is the dosing of the solution at slightly alkaline pH with reducing agents.
  • the reducing agents typically used to convert the dissolved metal salt into insoluble metal precipitates include sodium borohydride, sodium hydrosulfite and other chemicals.
  • a further waste treatment method known for reducing the dissolved metal content of spent electroless baths to acceptable discharge levels involves organosulfur precipitation of the metal by dosing the spent solution at a pH of 5-8 with water-soluble precipitating agents.
  • hydrocarbon-utilizing bacteria are used to remediate metal contaminants.
  • the bacteria use hydrocarbons as a substrate under aerobic, anaerobic or dual aerobic/anaerobic conditions.
  • the hydrocarbon comprises at least one alkane such as butane, methane, ethane and/or propane. Examples of applications include the remediation of heavy metals, the remediation of arsenic impacted surface water, groundwater and or soil, the remediation of acid mine drainage, and the treatment of spent metal plating solutions.
  • An aspect of the present invention is to provide a method of remediating a metal contaminant.
  • the method includes treating the metal contaminant with hydrocarbon-utilizing bacteria in the presence of a hydrocarbon.
  • Another aspect of the present invention is to provide a method of treating a metal-contaminated site. The method includes supplying a hydrocarbon substrate to the site to thereby remediate the metal contaminant.
  • a further aspect of the present invention is to provide a system for remediating a metal contaminant.
  • the system includes means for treating the metal contaminant with hydrocarbon-utilizing bacteria in the presence of at least one hydrocarbon.
  • Another aspect of the present invention is to provide a remediation system for treating a metal contaminant comprising a source of hydrocarbon substrate and at least one injector in flow communication with the hydrocarbon substrate and the metal contaminant.
  • Fig.l is a schematic plan view of an in-situ hydrocarbon injection system for remediating metal-contaminated groundwater in accordance with an embodiment of the present invention.
  • Fig. 2 is a schematic side view illustrating an ex-situ treatment system for metal-contaminated soil in accordance with an embodiment of the present invention.
  • Fig. 3 is a schematic plan view of an in-situ hydrocarbon injection system for remediating acid mine drainage in accordance with an embodiment of the present invention.
  • Fig. 4 is a schematic side view of an ex-situ treatment system employing hydrocarbon injection within a precipitation lagoon for the remediation of acid mine drainage in accordance with an embodiment of the present invention.
  • Fig. 5 is a schematic side view of an ex-situ treatment system for the remediation of spent metal plating solutions in accordance with an embodiment of the present invention.
  • Fig. 6 illustrates an anaerobic bioreactor in accordance with an embodiment of the present invention.
  • Fig. 7 illustrates an aerobic bioreactor in accordance with an embodiment of the present invention.
  • the present invention uses hydrocarbon-utilizing bacteria to remediate metal contaminants.
  • the metal contaminants may include one or more metals listed on the Periodic Table, such as arsenic, antimony, beryllium, cadmium, chromium, copper, lead, mercury, iron, manganese, magnesium, radium, nickel, selenium, silver, thallium and zinc, as well as compounds containing such metals.
  • the concentrations of metal contaminants in groundwater are reduced to the EPA Maximum Contaminant Levels (MCLs) set forth in the National Primary Drinking Water Regulations shown in Table 1 below. These MCLs represent safe levels for drinking water that metal concentrations in groundwater should not exceed.
  • MCLs Maximum Contaminant Levels
  • Metal contaminants may be present in various media, for example, in soil, groundwater, surface water, storage tanks, lagoons, industrial gaseous emissions, waste rock, soil piles, agricultural soils and fertilizers, aquatic systems, paints, polymers, herbicides, pesticides and spent auto fluids such as antifreeze and waste oil.
  • Some examples of metal contaminants include acid mine drainage, metal plating solutions, arsenic-impacted groundwater, metallic salts used to control algae in lakes, weed control chemicals for lawns, pollution in river sediments and lakes, urban highway runoff, metal surface treatment waste, metal cutting and fabrication dust and junked auto parts.
  • Metal contaminants may be present at many different industrial sites such as mining facilities, smelting operations, foundries, steel mills, metal processing and manufacturing facilities, process plants, production facilities for computer chips and semiconductors, and the like. Some types of metal contaminants may be radioactive, such as nuclear waste, armor plating production waste, munitions and ordnance, and hospital waste.
  • the present invention uses hydrocarbon-utilizing bacteria in the presence of at least one hydrocarbon substrate to remediate metal contaminants.
  • the hydrocarbon may comprise one or more alkane, alkene, alkyne, poly(alkene), poly(alkyne), aromatic hydrocarbon, aromatic hydrocarbon polymer, or aliphatic hydrocarbon.
  • the hydrocarbon comprises at least one alkane such as butane, methane, ethane and/or propane.
  • butane is a nontoxic and relatively low molecular weight organic compound that may serve as an electron donor under aerobic or anaerobic conditions.
  • the high solubility of butane provides a large zone of influence and makes butane particularly suited to accelerate the transformation of aerobic conditions to anaerobic conditions.
  • Under aerobic conditions butane substrates stimulate the growth of butane-utilizing bacteria which may oxidize iron and other metals.
  • butane is the most prevalent compound of the hydrocarbon substrate on a weight percent basis, and typically comprises at least about 10 weight percent of the hydrocarbon substrate.
  • the other constituents of the hydrocarbon substrate may include other alkanes or other types of hydrocarbons, and may also include inert gases.
  • the hydrocarbon substrate preferably comprises at least about 50 weight percent butane. More preferably, the hydrocarbon substrate comprises at least about 90 weight percent butane. In a particular embodiment, the hydrocarbon substrate comprises at least about 99 weight percent n-butane.
  • the butane may contain straight (n-butane) and/or branched chained compounds such as iso-butane.
  • Hydrocarbon-utilizing microorganisms used in accordance with the present invention are typically found naturally in the affected media. However, in some applications, it may be necessary to inoculate bacteria into the treatment zone. Suitable bacteria may include the following Groups (in addition to fungi, algae, protozoa, rotifers and all other aerobic and anaerobic microbial populations found in decaying materials): Group 1: The Spirochetes
  • Group 2 Aerobic/Microaerophilic, motile, helical/vibroid, gram-negative bacteria
  • Group 3 Nonmotile (or rarely motile), gram-negative bacteria
  • Group 4 Gram-negative aerobic/microaerophilic rods and cocci
  • Group 6 Gram-negative, anaerobic, straight, curved, and helical bacteria
  • Group 10 Anoxygenic phototrophic bacteria
  • Group 11 Oxygenic phototrophic bacteria
  • Group 12 Aerobic chemolithotrophic bacteria and associated organisms
  • Group 13 Budding and/or appendaged bacteria
  • Group 14 Sheathed bacteria
  • Group 16 The fruiting, gliding bacteria and the Myxobacteria
  • Group 1 Regular, nonsporing, gram-positive rods
  • Group 20 Irregular, nonsporing, gram-positive rods
  • Group 21 The mycobacteria
  • Group 23 Genera with multiocular sporangia
  • Group 25 Streptomycetes and related genera
  • Group 29 Genus Glycomyces, Genus Kitasatospira and Genus Saccharothrix
  • Group 30 The Mycoplasmas - cell wall-less bacteria
  • Group 34 Cell wall-less archaeobacteria
  • Group 35 Extremely thermophilic and hyperthermophilic S°-metabolizers.
  • suitable bacteria may include facultative and/or microaerophilic anaerobes, which are capable of surviving at low levels of oxygen. These bacteria do not require strict anaerobic conditions such as the obligate anaerobes. Acidophilic, alkaliphilic, anaerobe, anoxygenic, autotrophic, chemolithotrophic, chemoorganotroph, chemotroph, halophilic, methanogenic, neutrophilic, phototroph, saprophytic, thermoacidophilic and thermophilic bacteria may be used. Hydrocarbon and oxygen injection may encourage the growth of other microorganisms such as fungi, protozoa and algae that may be beneficial to the sulfur compound reducing process.
  • facultative and/or microaerophilic anaerobes which are capable of surviving at low levels of oxygen. These bacteria do not require strict anaerobic conditions such as the obligate anaerobes. Acidophilic, alkaliphilic, anaerobe, anoxygenic, autotrophic, chemolithotrophic
  • the injected oxygen may be in the form of air (e.g., dry air with 20.9% oxygen), a gas stream with varying concentrations of oxygen, substantially pure oxygen or the like.
  • the hydrocarbon and oxygen may be delivered continuously or intermittently, and may be delivered together or separately, e.g., through the same injectors or through different injectors.
  • Hydrocarbon-utilizing bacteria may oxide heavy metals through direct metabolism, sequential metabolism, reductive metabolism and or cometabolism. Furthermore, the hydrocarbons may chemically oxidize or otherwise remediate the metals or metal compounds without the action of microorganisms.
  • remediation of metals may occur both aerobically and anaerobically.
  • hydrocarbons such as butane may transform aerobic conditions to anaerobic conditions by initially accelerating the growth of aerobic hydrocarbon-utilizing microorganisms in the presence of oxygen, which produces carbon dioxide and transforms the aerobic conditions to anaerobic conditions.
  • T. Ferrooxidans activity may decrease or terminate, and anaerobic hydrocarbon-utilizing bacteria may flourish.
  • the transformation from aerobic to anaerobic conditions may prevent or reduce heavy metal migration and curtail T. Ferrooxidans in general.
  • the aerobic cycle may accelerate heavy metal precipitation out of solution, thereby inhibiting the migration of the metals through the subsurface, or facilitating the collection and removal of these metals using ex-situ techniques.
  • Metal contaminants may be remediated by changing the subsurface microbial ecology of contaminated sites.
  • Remediation may be conducted either in-situ or ex-situ.
  • In-situ equipment may include injection wells for the continuous or periodic delivery of the hydrocarbon substrate, oxygen and/or nutrients.
  • injection wells for the continuous or periodic delivery of the hydrocarbon substrate, oxygen and/or nutrients.
  • in-situ systems as described in U.S. Patent Nos. 6,244,346 and 6,245,235 may be used to inject the hydrocarbon substrate and, optionally, oxygen to the remediation site.
  • Ex-situ equipment may include bioreactors, for example, as disclosed in U.S. Patent Nos. 5,888,396 and 6,051,130, which are capable of treating air, soil or groundwater waste streams.
  • the ex-situ bioreactor may be used in a batch-type process and/or in a continuous flow process.
  • Ex-situ equipment may also include, for example, butane/air diffusers, precipitation lagoons with metal deposition membrane liners, anaerobic reduction chambers, and aerobic precipitation chambers.
  • Fig. 1 illustrates a system for in-situ treatment of arsenic-contaminated groundwater or other types of metal-contaminated groundwater in accordance with an embodiment of the present invention.
  • Butane and air injection wells 10 are installed in- situ within a flow path of metal-contaminated groundwater 12 to create radii of influence 14 around the wells 10. Dissolved butane and oxygen thus form a barrier against arsenic migration. As the treatment continues, butane-utilizing bacteria produce the requisite enzymes to precipitate arsenic or other metal contaminants from the groundwater 12 onto aquifer solids. Clean groundwater 16 then flows toward a recovery well 18, e.g., a drinking water well.
  • Fig. 2 illustrates a system 20 for ex-situ treatment of metal-contaminated soil such as arsenic-containing soil in accordance with another embodiment of the present invention.
  • the system 20 includes a rock crusher 22 where contaminated soil is pretreated or crushed.
  • the crushed soil 23 is fed to a slurry bioreactor 24 which includes a hydrocarbon and oxygen supply 25 and diffusers 26.
  • the hydrocarbon/oxygen supply 25 may comprise, for example, a cylinder containing a hydrocarbon such as butane and an air compressor, or any other suitable hydrocarbon/oxygen source.
  • the supply 25 may only introduce a hydrocarbon into the bioreactor 24 if anaerobic conditions are desired.
  • the hydrocarbon injected through the diffusers 26 stimulates the growth of hydrocarbon-utilizing bacteria in the bioreactor 24, which oxidize or otherwise separate the metal contaminant from the soil.
  • the bioreactor 24 may be replaced with a washing tank where the metal contaminant is removed from the soil without the use of the hydrocarbon.
  • the clean soil 27 is removed from the bioreactor 24 and the metal- contaminated effluent 28 is pumped 29 to a precipitation lagoon 30 where further treatment by hydrocarbon-utilizing bacteria results in metal precipitation onto a membrane liner 31.
  • the membrane 31 may be made of any suitable material, such as polyethylene, EPDM rubber, polyurethane or polypropylene.
  • a hydrocarbon and oxygen supply 32 and diffusers 33 deliver, for example, butane and air to the precipitation lagoon 30. Although two different hydrocarbon supplies 25 and 32 are shown in Fig. 2, a single supply could be used.
  • Clean water 34 is then pumped 35 from the precipitation lagoon 30 and the metal precipitates are eliminated, for example, by collection, separation, incineration, disposal and/or stabilization, e.g., with road construction materials such as concrete and/or asphalt.
  • metal-contaminated soil may be treated in heap piles utilizing leaching techniques.
  • Hydrocarbon and air injection wells may be installed in the heap pile.
  • Stimulated hydrocarbon-utilizing bacteria may precipitate the metal while water flushing over the heap collects the oxidized metal fraction and creates a solution effluent, which then can be treated separately, for example, in a precipitation lagoon as described above.
  • Fig. 3 illustrates a system for treatment of a contaminated site, such as a heavy metal-contaminated site and/or an acid mine drainage site in accordance with a further embodiment of the invention.
  • Butane (and/or other hydrocarbon substrates) and oxygen injection wells 40 are installed in-situ within a groundwater flow path 42 adjacent to a waste rock area 43 which may be above grade and or below grade.
  • the waste rock 43 existing above and/or below ground, may result from metal mining operations and may be a source of AMD or heavy metal contamination.
  • the wells 40 are installed in-situ and create radii of influence 44 which form a protective curtain or barrier to reduce or eliminate the flow of AMD or heavy metals.
  • the injection wells 40 may operate aerobically, for example, by maintaining constant or intermittent air flow and constant or intermittent hydrocarbon flow. Alternately, the injection wells 40 may alternate between periodic hydrocarbon injection only and hydrocarbon/air injection to achieve alternating anaerobic and aerobic processes. With the transformation of the groundwater flow 42 to a substantially anaerobic state, and in the presence of an alternate electron acceptor such as carbon dioxide or nitrate, the hydrocarbon may serve as an electron donor and carbon source, thereby halting the AMD process.
  • an alternate electron acceptor such as carbon dioxide or nitrate
  • Fig.4 illustrates an ex-situ system 50 for the treatment of lagoons or tanks contaminated with AMD or other heavy metal contaminants in accordance with an embodiment of the present invention.
  • the ex-situ system 50 includes a lagoon 52 contaminated with acid mine drainage or other heavy metal contaminants.
  • the contaminated fluid 54 is pumped 56 to a precipitation lagoon 58 lined with a membrane 60.
  • a hydrocarbon and oxygen supply 62 and diffusers 64 inject the desired amounts of hydrocarbon and oxygen at the desired intervals in order to create anaerobic, aerobic or alternate anaerobic and aerobic conditions in the precipitation lagoon 58.
  • butane and air may be injected in order to stimulate the growth of aerobic butane-utilizing bacteria which accelerate heavy metal precipitation onto the membrane filter 60 installed in the precipitation lagoon 58.
  • Clean water 66 is then pumped from the precipitation lagoon 58 while the metal contaminant is deposited on the membrane filter 60.
  • the membrane 60 may be made of any suitable material, such as polyethylene, EPDM rubber, polyurethane or polypropylene.
  • Fig. 5 illustrates a system 70 for treating spent metal plating solutions in accordance with another embodiment of the invention.
  • Spent metal plating solution 72 is pumped 74 to an anaerobic reduction chamber 76.
  • a hydrocarbon supply 78 such as a butane cylinder and diffusers 80 inject the desired amount of hydrocarbon at the desired intervals into the reduction chamber 76.
  • the chamber 76 is vented 82 to atmosphere, e.g., by a one-way valve.
  • the solution 84 is then pumped 86 from the reduction chamber 76 to an aerobic precipitation chamber 88.
  • a hydrocarbon and oxygen supply 90 and diffusers 92 inject the desired amounts of hydrocarbon and oxygen, such as butane and air, at the desired intervals into the aerobic precipitation chamber 88.
  • a membrane liner 94 is provided at the bottom of the chamber 88, e.g., on a pull-out tray.
  • the chamber 88 is vented 96 to atmosphere. Clean water 98 exits the chamber 88.
  • butane-utilizing bacteria or other hydrocarbon-utilizing bacteria in the reduction chamber 76 anaerobically pretreat the metal plating solution 72, e.g., using metabolic and cometabolic processes.
  • hydrocarbon-utilizing bacteria such as butane-utilizing bacteria may utilize a variety of alternate electron acceptors such as sulfate, nitrate or iron.
  • the electroless plating solution 72 may be pretreated with buffers to maintain a pH between 4 and 8.
  • the solution 84 undergoes microbial oxidation in the aerobic precipitation chamber 88.
  • the alternate electron acceptors may be added, for example, to the butane/air mix injected into the precipitation chamber 88.
  • Precipitated metals are deposited on the membrane liner 94 which may be incorporated into pull-out trays for subsequent removal.
  • a low voltage current may be passed through a portion of the tray assembly to electrolyze and plate portions of the tray liners with the metal constituents to aid and expedite the metal recovery process.
  • Example 1 illustrates the treatment of a spent electroplating solution, and is not intended to limit the scope of the present invention.
  • the spent electroplating solution had a pH of 3.0.
  • concentrations of cyanide, beryllium, chromium, copper, nickel and zinc were detected above the laboratory detection limits.
  • the sample prior to treatment with butane, the sample should have been adjusted with an alkaline buffer to raise the pH.
  • the example was designed to demonstrate the principal of metals precipitation under conservative conditions. Therefore, the pH was not adjusted and since oxygen alone will partially oxidize metals, air was not pumped into the bioreactors designed for this study.
  • FIG. 6 illustrates an anaerobic bioreactor 100 used in the study.
  • the reactor 100 included a container 102 having a lid 104, an injection tube 106 and a syringe port 108 to inject butane.
  • a vent tube 112 was connected through the lid 104 to a water bath 114.
  • Filter paper 110 was placed at the bottom of the bioreactor container 102.
  • Three liters of spent electroplating solution underwent butane treatment in the anaerobic bioreactor 100 for 14 days.
  • vent tube 112 and water bath 114 shown in Fig. 6 were removed from the bioreactor 100.
  • the resultant aerobic bioreactor 120 is illustrated in Fig. 7.
  • air exchange was permitted within the vessel 102, although to a limited degree since butane is heavier than air and displaces air in a semi-closed environment.
  • the spent electroplating solution was decanted from the bioreactor. A change in color was immediately noticeable. The initial color of the solution was a deep bluish-green. After the 28-day period, the color was light green. The pH of the solution was tested and found to be the same, i.e., 3.0. A precipitate was noticeable on the filter paper.
  • the filter paper was submitted to a certified analytical laboratory for metals analyses (only for those metals detected above the detection limit during the pre-characterization sampling event). The results are listed in Table 4.

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Abstract

La présente invention concerne des procédés et un appareil qu'on utilise pour la biorestauration de contaminants métalliques à l'aide d'hydrocarbures qui stimulent la croissance de bactéries consommant des hydrocarbures. Les contaminants métalliques peuvent être des métaux lourds tels que l'arsenic, l'antimoine, le béryllium, le cadmium, le chrome, le cuivre, le plomb, le mercure, le fer, le manganèse, le magnésium, le radium, le nickel, le sélénium, l'argent, le thallium et le zinc. Les hydrocarbures peuvent être des alcanes, des alcènes, des alcynes, des poly(alcène)s, des poly(alcyne)s, des hydrocarbures aromatiques, des polymères d'hydrocarbures aromatiques et des hydrocarbures aliphatiques. Le butane est un hydrocarbure particulièrement approprié qui stimule la croissance de bactéries utilisant du butane. La biorestauration peut s'effectuer in situ ou ex situ et peut se dérouler dans des conditions aérobie, anaérobie ou dans des conditions mixtes aérobie/anaérobie. Des exemples d'applications possibles comprennent la biorestauration des métaux lourds, la biorestauration d'eau de surface, d'eau souterraine et/ou de sol contaminé(s) par l'arsenic, la biorestauration d'eau d'exhaure acide et le traitement des solutions de galvanoplastie épuisées.
PCT/US2002/024001 2001-07-27 2002-07-26 Biorestauration de contaminants metalliques avec des bacteries utilisant des hydrocarbures WO2003011487A1 (fr)

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US30821001P 2001-07-27 2001-07-27
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US30821201P 2001-07-27 2001-07-27
US60/308,210 2001-07-27
US60/308,487 2001-07-27
US60/308,212 2001-07-27
US34486801P 2001-12-31 2001-12-31
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WO2006072845A3 (fr) * 2004-12-02 2007-03-01 Csir Proteine de recombinaison gram-positives pour la production de bacteries
EP1873234A1 (fr) * 2005-04-21 2008-01-02 Ibiden Co., Ltd. Procede de traitement des eaux usees contenant un compose organique
CN100410190C (zh) * 2005-08-25 2008-08-13 中南大学 细菌处理高浓度碱性含铬废水的方法
WO2011098979A2 (fr) 2010-02-12 2011-08-18 Commissariat A L'energie Atomique Nouvelle algue radiorésistante du genre coccomyxa
CN102372406A (zh) * 2011-10-13 2012-03-14 长沙理工大学 一种重金属污染底泥的异位修复方法
US8658411B2 (en) 2005-04-21 2014-02-25 Ibiden Co., Ltd. Method of treating wastewater containing organic compound
WO2014174483A2 (fr) 2013-04-25 2014-10-30 Commissariat A L'energie Atomique Et Aux Energies Alternatives Nouvelle algue radioresistante du genre coccomyxa
RU2571222C2 (ru) * 2009-08-20 2015-12-20 Интер Американ Юниверсити Оф Пуэрто-Рико Система ремедиации тяжелых металлов
CN105170627A (zh) * 2015-10-20 2015-12-23 南京工业大学 一种微生物-植物联合修复镉污染土壤的方法
CN106244501A (zh) * 2016-09-23 2016-12-21 北京林业大学 一株抗锑细菌nxh1及其应用
CN106434446A (zh) * 2016-09-23 2017-02-22 北京林业大学 一株抗锑细菌nxh3及其应用
CN106834184A (zh) * 2017-03-03 2017-06-13 中南大学 一种复合菌群及其在Cr(VI)污染土壤修复中的应用
US9845342B2 (en) 2014-09-17 2017-12-19 Spogen Biotech Inc. Fusion proteins, recombinant bacteria, and methods for using recombinant bacteria
CN107971334A (zh) * 2017-11-03 2018-05-01 中国科学院生态环境研究中心 一种多塘-藻水循环灌溉系统修复污染土壤的方法
CN108459642A (zh) * 2018-03-09 2018-08-28 浙江海莱芙电子科技有限公司 一种矿井防冻采暖空气智能送风系统
CN108641990A (zh) * 2018-06-29 2018-10-12 南京怡可帮生态环境科技有限公司 一种土壤砷污染修复微生物制剂生产方法及应用
CN110257272A (zh) * 2019-04-04 2019-09-20 华中农业大学 丛毛单胞菌和肠杆菌的复合菌剂高效固定镉及在镉污染修复的应用
US11865597B2 (en) 2019-08-23 2024-01-09 Seed Health Inc. Method for bioremediation of lead
US12031164B2 (en) 2018-09-20 2024-07-09 Spogen Biotech Inc. Fusion proteins, recombinant bacteria, and exosporium fragments for plant health

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US7888064B2 (en) 2004-12-02 2011-02-15 Csir Gram positive bacterial cells comprising a disrupted flagellin gene, flagellin-based fusion proteins and use in removal of metal ions from a liquid
WO2006072845A3 (fr) * 2004-12-02 2007-03-01 Csir Proteine de recombinaison gram-positives pour la production de bacteries
EP2216398A3 (fr) * 2005-04-21 2010-10-27 Ibiden Co., Ltd. Procédé de traitement des eaux usées contenant un composé organique
EP1873234A1 (fr) * 2005-04-21 2008-01-02 Ibiden Co., Ltd. Procede de traitement des eaux usees contenant un compose organique
EP1873234A4 (fr) * 2005-04-21 2009-08-05 Ibiden Co Ltd Procede de traitement des eaux usees contenant un compose organique
US8658411B2 (en) 2005-04-21 2014-02-25 Ibiden Co., Ltd. Method of treating wastewater containing organic compound
CN100410190C (zh) * 2005-08-25 2008-08-13 中南大学 细菌处理高浓度碱性含铬废水的方法
RU2571222C2 (ru) * 2009-08-20 2015-12-20 Интер Американ Юниверсити Оф Пуэрто-Рико Система ремедиации тяжелых металлов
WO2011098979A2 (fr) 2010-02-12 2011-08-18 Commissariat A L'energie Atomique Nouvelle algue radiorésistante du genre coccomyxa
CN102372406A (zh) * 2011-10-13 2012-03-14 长沙理工大学 一种重金属污染底泥的异位修复方法
CN102372406B (zh) * 2011-10-13 2013-08-07 长沙理工大学 一种重金属污染底泥的异位修复方法
WO2014174483A2 (fr) 2013-04-25 2014-10-30 Commissariat A L'energie Atomique Et Aux Energies Alternatives Nouvelle algue radioresistante du genre coccomyxa
US9845342B2 (en) 2014-09-17 2017-12-19 Spogen Biotech Inc. Fusion proteins, recombinant bacteria, and methods for using recombinant bacteria
US11905315B2 (en) 2014-09-17 2024-02-20 Spogen Biotech Inc. Fusion proteins, recombinant bacteria, and methods for using recombinant bacteria
US10836800B2 (en) 2014-09-17 2020-11-17 Spogen Biotech Inc. Fusion proteins, recombinant bacteria, and methods for using recombinant bacteria
US10407472B2 (en) 2014-09-17 2019-09-10 Spogen Biotech Inc. Fusion proteins, recombinant bacteria, and methods for using recombinant bacteria
CN105170627A (zh) * 2015-10-20 2015-12-23 南京工业大学 一种微生物-植物联合修复镉污染土壤的方法
CN106434446B (zh) * 2016-09-23 2019-09-17 北京林业大学 一株抗锑细菌nxh3及其应用
CN106434446A (zh) * 2016-09-23 2017-02-22 北京林业大学 一株抗锑细菌nxh3及其应用
CN106244501A (zh) * 2016-09-23 2016-12-21 北京林业大学 一株抗锑细菌nxh1及其应用
CN106834184A (zh) * 2017-03-03 2017-06-13 中南大学 一种复合菌群及其在Cr(VI)污染土壤修复中的应用
CN107971334A (zh) * 2017-11-03 2018-05-01 中国科学院生态环境研究中心 一种多塘-藻水循环灌溉系统修复污染土壤的方法
CN108459642A (zh) * 2018-03-09 2018-08-28 浙江海莱芙电子科技有限公司 一种矿井防冻采暖空气智能送风系统
CN108641990A (zh) * 2018-06-29 2018-10-12 南京怡可帮生态环境科技有限公司 一种土壤砷污染修复微生物制剂生产方法及应用
US12031164B2 (en) 2018-09-20 2024-07-09 Spogen Biotech Inc. Fusion proteins, recombinant bacteria, and exosporium fragments for plant health
CN110257272A (zh) * 2019-04-04 2019-09-20 华中农业大学 丛毛单胞菌和肠杆菌的复合菌剂高效固定镉及在镉污染修复的应用
US11865597B2 (en) 2019-08-23 2024-01-09 Seed Health Inc. Method for bioremediation of lead

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