Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
  • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
  • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
  • B09C—RECLAMATION OF CONTAMINATED SOIL
  • B09C1/00—Reclamation of contaminated soil
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
  • B09C—RECLAMATION OF CONTAMINATED SOIL
  • B09C1/00—Reclamation of contaminated soil
  • B09C1/08—Reclamation of contaminated soil chemically
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
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  • 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
  • C12N1/20—Bacteria; Culture media therefor
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  • 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
• • 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
  • C12N1/32—Processes using, or culture media containing, lower alkanols, i.e. C1 to C6
• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
  • C12P7/00—Preparation of oxygen-containing organic compounds
  • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
  • C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
  • C12P7/16—Butanols
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/12—Inorganic compounds
  • C10L1/1216—Inorganic compounds metal compounds, e.g. hydrides, carbides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/12—Inorganic compounds
  • C10L1/1266—Inorganic compounds nitrogen containing compounds, (e.g. NH3)
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/12—Inorganic compounds
  • C10L1/1275—Inorganic compounds sulfur, tellurium, selenium containing compounds
• • 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
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E50/00—Technologies for the production of fuel of non-fossil origin
  • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

• the invention relates to the field of renewable fuel compositions and the fate of said compositions in the environment.
• Isobutanol is attractive as a biofuel molecule suitable for use in gasoline because it can be produced from renewable feedstocks and has many properties that potentially make it a more attractive fuel additive than ethanol; it has a greater energy density, lower water absorption, better blending ability, and it can be used in conventional combustion engines without modification (Durre, 2007, Biotech. J. 2:1525-1578).
• TSA tert-butyl alcohol
• MTBE gasoline oxygenate methyl tert-butyl ether
• the invention provides methods and compositions for improving the environmental fate of hydrocarbon fuel compositions under circumstances of environmental release while increasing the renewability of said fuel compositions.
• An aspect of the invention is a method for improving the environmental fate of hydrocarbon fuel compositions by the inclusion of isobutanol to said compositions resulting in improved biodegradability of one or more BTEX compounds of the gasoline.
• the methods and compositions provide improved biodegradation under anaerobic conditions.
• the methods and compositions provide improved biodegradation under aerobic conditions.
• the methods and compositions provide improved biodegradation under nitrate reducing conditions.
• the inclusion of isobutanol in hydrocarbon fuel compositions improves the biodegradation of benzene.
• Another aspect of the invention is a method for improving the environmental fate of liquid fuel compositions comprising ethanol by the addition of isobutanol to said compositions resulting in improved biodegradation of one or more BTEX compounds of the gasoline.
• Another aspect of the invention is a method to reduce the transport of ethanol in a soil matrix when said ethanol is a component of a hydrocarbon fuel composition released into an environmental compartment (e.g. soil, sediments, groundwater), said method comprising combining isobutanol with the fuel composition.
• an environmental compartment e.g. soil, sediments, groundwater
• Another aspect of the invention is a method of reducing a BTEX plume caused by release of a hydrocarbon composition optionally comprising ethanol into an environmental compartment, said method comprising adding a suitable amount of isobutanol wherein said isobutanol acts as a cosolvent for the hydrocarbon and ethanol components of the hydrocarbon composition, thereby retarding and/or partially containing the BTEX plume and reducing the potential for its leakage into a water table.
• Another aspect of the invention is directed to liquid fuel compositions comprising hydrocarbons, ethanol and isobutanol in an amount sufficient to improve the renewability of the hydrocarbon composition without increasing potential environmental impact of said composition if it were to contaminate an environmental compartment.
• the renewability of the fuel composition is increased and the potential environmental impact is decreased by the inclusion of isobutanol, for example, BTEX plume expansion may be decreased as compared to a BTEX plume expansion of the same composition without the isobutanol present, particularly under aerobic environmental conditions.
• the hydrocarbon fuel composition further comprises ethanol.
• the ethanol comprises up to about 10% of the fuel composition prior to addition of isobutanol.
• the isobutanol provides for improved biodegradation of at least one of the BTEX components of the hydrocarbon fuel composition.
• the isobutanol provides for improved biodegradation of benzene.
• the environmental compartment includes a soil matrix and wherein the isobutanol reduces the transport of ethanol in a soil matrix.
• the isobutanol impedes expansion of a BTEX plume from said composition.
• the isobutanol is present in an amount amount suitable for increasing the biodegradability of the hydrocarbon fuel composition.
• the improved biodegradation occurs under aerobic conditions. In embodiments, the improved biodegradation occurs under nitrate-reducing or sulfate-reducing conditions.
• Also provided are methods of improving the environmental fate of a hydrocarbon fuel composition comprising isobutanol in an environmental compartment under anaerobic conditions comprising adding an electron acceptor to said compartment in an amount sufficient to increase the rate of biodegradation of one or more BTEX components, in embodiments, the electron acceptor is iron, sulfate, or nitrate, or a combination thereof. In embodiments, the electron acceptor is Fe(OH) 3 . In embodiments, the electron acceptor is NaNO 3 . In embodiments, the electron acceptor is MgSO 4 .
• the one or more BTEX components comprise toluene, xylene, or benzene
• the electron acceptor is nitrate and is added in an amount sufficient to create nitrate- reducing conditions.
• the electron acceptor is sulfate and is present in an amount sufficient to create suifate-reducing conditions.
• the electron acceptor is nitrate and is present in an amount sufficient to create nitrate-reducing conditions and wherein toluene biodegrades in about the same number of days as isobutanol.
• the electron acceptor is sulfate and is present in an amount sufficient to create suifate- reducing conditions and wherein toluene biodegrades in about the same number of days as isobutanol. In embodiments, the electron acceptor is nitrate and is present in an amount sufficient to create nitrate-reducing conditions and wherein benzene biodegrades in about the same number of days as isobutanol. In embodiments, the electron acceptor is sulfate and is present in an amount sufficient to create suifate-reducing conditions and wherein benzene biodegradation is improved as compared to its biodegradation without suifate- reducing conditions.
• the electron acceptor is sulfate and is present in an amount sufficient to create suifate-reducing conditions and wherein benzene biodegradation is improved as compared to its biodegradation in the absence of isobutanol. In embodiments, the electron acceptor is sulfate and is present in an amount sufficient to create suifate-reducing conditions and wherein benzene biodegradation is improved as compared to its biodegradation in the presence of ethanol. Also provided herein are compositions comprising gasoline, isobutanol and at least one of Fe(OH) 5 . NaNO 3 . or MgSO 4 .
• compositions comprising gasoline, isobutanol and at least one of Fe(OH) 3 , NaNO 3 , KNO 3 . NHNO 3 , Na 2 SO 4 , CaSO 4 . MgSO 4 . chelated iron, zero-valent iron, and nano zero- valent iron.
• Figure 1a shows isobutanol degradation up to 10 days. Error bars represent 95% confidence intervals..
• Figure 1 b shows isobutanol degradation up to 50 days.
• Figure 1c shows ethanol degradation up to 50 days.
• Figures 2A, B, C, and D show the impact of isobutanol on biodegradation of 8TEX at high concentrations.
• Figure 2A shows benzene; 28 shows toluene; 2C shows ethylbenzene; 2D shows total xylenes.
• Error bars represent 95% confidence intervals .
• Figures 3A, B, C and D compare the impact of isobutanol and ethanol concentration on BTEX biodegradation at various treatment levels.
• Figure 3A shows benzene: 3B shows toluene; 3C shows ethylbenzene; 3D shows total xylenes.
• Error bars represent 95% confidence intervals.
• Figures 4A, B, C, and D show the impact of isobutanol on biodegradation of BTEX at lower concentrations.
• Figure 4A shows benzene; 4B shows toluene; 4C shows ethylbenzene; 4D shows total xylenes.
• Error bars represent 95% confidence intervals.
• Figures 5A, B, C, and D show isobutanol biodegradation - higher concentration - under various anaerobic reducing conditions.
• Figure 5A shows Treatment 2-Unamended; 5B shows Treatment 6-Nitrate Reducing; 5C shows Treatment 9-Iron reducing; 5D shows Treatment 12-Sulfate Reducing.
• Error bars represent 95% confidence intervals.
• the dashed line for Treatment 2 indicates the time when the microcosms were re-amended with isobutanol.
• Figures 6A and 6B show ethanol biodegradation in Treatment 4
• Treatment 4 (Unamended) and Treatment 14 (Sulfate reducing), respectively. Error bars represent 95% confidence intervals.
• the clashed line for Treatment 4 indicates the time when the microcosms were re-amended with ethanol after the residua! sulfate in the groundwater was reduced.
• Figures 7A, B, C, and D show benzene and toluene biodegradation (higher concentration) under various anaerobic reducing conditions and in the presence or absence of isobutanol (IBA).
• IBA isobutanol
• a and B show benzene and toluene, respectively, for Treatments 1, 2, 5, and 6
• C and D show benzene and toluene, respectively, for Treatements 8, 9, 11 , and 12.
• Error bars represent 95% confidence intervals.
• Figures 8A, B, C, and D show BTEX biodegradation - lower concentration
• Figures 9 A, B, C, and D show isobutanol biodegradation - lower concentration.
• A shows Treatment 3-Unamended; B shows Treatment 7-Nitrate Reducing; C shows Treatment 10-Iron Reducing; D shows Treatment 13-Sulfate Reducing.
• Error bars represent 95% confidence intervals. Supplemental monitoring showed that the isobutyric acid concentrations had decreased below the analytical detection limit by day 160 for Treatment 3 and by day 48 for Treatment 13 (data not shown).
• Figures 10A, B, C, and D show high concentration ethylbenzene and total xylenes biodegradation under various anaerobic reducing conditions and in the presence or absence of isobutanol (IBA).
• IBA isobutanol
• a and B show ethylbenzene and total xylenes, respectively, for Treatments 1, 2, 5, and 6;
• C and D show ethylbenzene and total xylenes, respectively, for Treatments 8, 9, 11 , and 12.
• Error bars represent 95% confidence intervals.
• Figures 11 and 12 demonstrate the behavior of isobutanol when 1.3% and 2.6% water are initially added to an E10 gasoline.
• increased levels of isobutanol result in reduced aqueous phase volume during phase separation.
• Figure 12 shows there is less ethanol in the aqueous portion when the separation does occur.
• the terms "comprises,” “comprising,” “includes,” “including, “ “has, “ “having,” “contains” or “containing,” or any other variation thereof, will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers.
• a composition, a mixture, a process, a method, an article, or an apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process, method, article, or apparatus.
• “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
• invention or "present invention” as used herein is a non-limiting term and is not intended to refer to any single embodiment of the particular invention but encompasses all possible embodiments as described in the application.
• the term "about" modifying the quantity of an ingredient or reactant of the invention employed refers to variation in the numerical quantity that can occur, for example, through typical measuring and liquid handling procedures used for making concentrates or solutions in the real world; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of the ingredients employed to make the compositions or to carry out the methods; and the like.
• the term “about” also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. Whether or not modified by the term “about”, the claims include equivalents to the quantities.
• the term “about” means within 10% of the reported numerical value, preferably within 5% of the reported numerical value.
• hydrocarbon fuel compositions comprising isobutanol provide fuel compositions with increased renewability attributable to a renewable component that is also biodegradable in the environment
• isobutanol is a renewable component which, as shown herein is degraded rapidly when added to aquifer microcosms.
• resuits presented herein demonstrate that not oniy is isobutanol itself biodegraded, but isobutanol also provides additional biodegradation benefits to gasoline under various environmental conditions.
• isobutanol may be biologically produced by microorganisms which convert carbon substrates derived from renewable feedstocks such as biomass into isobutanol.
• biologically-produced isobutanol when added to fuel compositions provides a valuable mechanism for introducing renewable components to fuel and, at the same time, provides for reduced environmental impact of the fuel composition if it were to contaminate a given environmental area.
• BTEX total xylenes
• Adding ethanol to gasoline can increase the renewability of the gasoline but this addition may also potentiate the damage resulting from BTEX as ethanol may result in expansion of BTEX plumes
• adding isobutanol to gasoline provides for a mechanism of increasing renewable component of fuels without increasing a BTEX piume as compared to adding ethanol as the additive should the fuel blend be released an environmental area or compartment (e.g. soil, sediment, groundwater).
• the addition of isobutanol does not impede BTEX biodegradation to the extent as is observed for ethanol under certain conditions.
• Biodegradation or “degradation”, as used herein, refers to primary transformation of the compound of interest to a byproduct.
• “Improving environmental fate” as used herein means reducing the amount of one or more components of a hydrocarbon fuel blend in an environmental compartment, increasing the degradation rate of one or more components of a hydrocarbon fuel blend in an environmental compartment, decreasing the size of the environmental compartment contacted by one or more components of a hydrocarbon fuel blend, or a combination thereof.
• “Environmental compartment” as used herein refers to the area contacted by a fuei composition and may include, for example, soil, sediment, groundwater, or a combination thereof.
• BTEX plume refers to a dissolved phase plume
• “increased renewability” means an increased portion of the composition was produced from resources considered to be renewable, such as biomass, as opposed to resources that are not renewable such as fossil fuels and petroleum.
• gasoline blend stocks useable for making gasolines for consumption in internal combustion engines, including but not limited to spark ignition engines.
• Gasoline blend stocks include, but are not limited to, blend stocks for gasolines meeting ASTM 4814, EU specification EN228, and blend stocks for reformulated gasoline.
• Amounts of isobutanol in hydrocarbon fuei compositions (by volume) for the methods disclosed herein include amounts of at least about 2%, at least about 5%, at least at ieast about 7%, at least about 10%, or at Ieast about 15%, In some aspects, amounts of isobutanol (by volume) include amounts from about 2% to about 20%, and amounts from about 0% to about 16%. It will be appreciated that the amount of isobutanol may be a function of the vehicle technology. As such, in embodiments, isobutanol amounts can be up to about 85% by volume. The isobutanol can be combined with the hydrocarbon portion of the fuel composition using any methods known in the art.
• the hydrocarbon fuel composition further comprises ethanol, and in some embodiments, the ethanol comprises up to about 10%, up to about 15% up to about 20%, or up to about 50% of the hydrocarbon composition prior to the addition of Isobutanol.
• isobutanol is substituted for ethanol in a fuei composition. In other embodiments, isobutanol is added to a fuel composition which comprises ethanol.
• Methods provided herein include a method of retardation of BTEX plume expansion from a hydrocarbon fuel composition by including isobutanol in said composition.
• the potential environmental impact of a hydrocarbon fuel composition should a release occur can be assessed by measuring the size of BTEX plume in the impacted area, and/or the rate of expansion, and/or the concentration of the BTEX plume.
• the size and rate of expansion of the BTEX plume can be assessed by methods known in the art such as direct sampling of groundwater and methods such as U.S. Environmental Protection Agency (EPA) method SW846
• degradation of a fuel composition comprising isobutanol occurs faster than a fuel composition comprising ethanol but no isobutanol.
• Degradation of fuel components can be measured in environmental samples using methods known in the art such as gas chromatography (QC), for example with U.S. EPA method 8015, or GC-mass spectrometry, for example with U.S. EPA method 8260.
• QC gas chromatography
• isobutanol degrades at least as fast as ethanol and, one or more BTEX components degrade faster in the presence of isobutanol than in the presence of ethanol.
• isobutanol is degraded with a first order rate constant of at least about 0.081 d -1 .
• isobutanol is degraded with a first order rate constant of at least about 0.28 d -1 . In some embodiments, isobutanol is degraded with a first order rate constant of greater than about 0.074 d -1 . In some cases, fuel compositions comprising isobutanol have increased rates of BTEX biodegradation as compared to fuel compositions comprising no renewable component. In some cases, fuel compositions comprising isobutanol have increased rates of BTEX biodegradation as compared to fuet compositions comprising ethanol but no isobutanol.
• butanol in gasoline containing ethanol reduces the volume of an aqueous phase when phase separation occurs, and limits the weight percent of ethanol contained within the aqueous phase. While not wishing to be bound by theory, it is believed that butanol may limit the amount of ethanol that ieaches into groundwater by maintaining it in the less water soluble hydrocarbon fraction. Hie reduced transport of ethanol in the soil matrix may thereby retard the expansion of BTEX into the water table.
• methods provided herein can advantageously decrease the time needed to remediate a contaminated site, can limit the size of BTEX plumes, or can provide both advantages, therefore improving the environmental fate of a hydrocarbon fuel composition.
• Methods provided herein can improve the environmental fate of a hydrocarbon fuel composition comprising isobutanol in an environmental compartment under anaerobic conditions.
• the methods comprise adding an electron acceptor to said compartment in an amount sufficient to increase the rate of biodegradation of one or more BTEX components.
• Suitable electron acceptors include nitrates, including, but not limited to NaNO 3 , NH 4 NO 3 , KNO 3 , and sulfates, including but not limited to MgSO 4 and CaSO 4 , Na 2 SO 4 , and iron compounds including, but not limited to Fe(OH)3, chelated iron, zero-valent iron, and nano zero-valent iron.
• Electron acceptors may be added to an environmental compartment using methods including, but not limited to, injection as a slurry, emplacement, injection through a monitoring well, gravity injection, and/or pressurized injection, or combinations thereof, in amounts sufficient to achieve nitrate-reducing, iron reducing, and/or sulfate reducing conditions.
• the injection of sulfates and/or nitrates and/or iron compounds may be used to biostimulate sulfate reducing and/or nitrate reducing bacteria, if present, to biodegrade BTEX contamination due the release of isobutanol containing gasoline underground. Such biostimulation may result in increased bioactivity, population, and or metabolism of the bacteria.
• Soil and groundwater for laboratory microcosm testing were collected from within Site 60 at Vandenberg Air Force Base, CA.
• the site has a history of gasoline contamination, but has undergone an extensive cleanup program.
• Collected groundwater was containerized in steriie stainless steel soda kegs (18.5 L) under nitrogen headspace.
• Soil located approximately 8 to 12 feet below ground surface (bgs) was collected using a Geoprobe ® 6620DT with acetate core sleeves. The core samples in acetate sleeves were capped and sealed in the field to minimize exposure to air, shipped overnight on ice to the laboratory, and stored at 4° C.
• Soil was removed from the acetate sleeves in an anaerobic chamber (Coy Laboratory Products, Inc., Grass Lake, Ml) and the first 10 cm of the core ends that may have been exposed to oxygen were discarded. Collected soil consisted of silty sand with some gravel and larger stones. The soil was passed through a 0.95 cm sieve, homogenized, and then stored in amber giass jars with Teflon ® - lined caps at 4°C until microcosm setup was complete. Baseline soil and groundwater data are presented in Table 1.
• SVOC detections include 0.008 mg L -1 phenol and 0.003 mg L -1 bis(2-ethylhexyl) phthalate; +A standard units).
• BTEX and alcohol concentrations were selected to represent (approximately) potential groundwater concentrations that would be observed within a source area and in the near downgradient plume.
• the greater ethanol concentrations relative to the isobutanol concentrations used in this study were intended to reflect effective solubilities of isobutanol and ethanol in groundwater, Ethanol has an aqueous solubility approximately 10-times that of isobutanol, and the octanoi-water partition coefficient of isobutanol is approximately 10-times that of ethanol (Organization for Economic Co-operation and Development, 2004. SIDS Assessment Report for SIAM 19- Ethanol (CAS No. 64-17-5). Berlin, Germany; Organization for Economic Co-operation and Development, 2004.
• Microcosms were prepared by placing 40 g of site soil into each of 54 glass serum bottles (approximate volume 160 mL each). BTEX and alcohol (isobutanol or ethanol) were added to the treatment bottles to attain the target concentrations shown in Tables 2A and B. Bottles were filled with groundwater so as to leave 10 mL of headspace. Controls were amended with mercuric chloride (700 mg/L in bottles) to inhibit microbial activity. Controls were subsequently amended with formaldehyde (1% v/v in bottles) after 4 days to limit microbial activity. Treatments were prepared with a minimum of 3 and up to 8 replicates each.
• the prepared microcosms were incubated at 15°C on a rotary shaker operating at 100 rpm. Headspace in each of the bottles was monitored for BTEX and oxygen. Aqueous BTEX concentrations were calculated by applying Henry's Law. Samples of the aqueous phase were analyzed for isobutanol and ethanol, as wet! as potential isobutanol degradation products (iso-butylaldehyde and iso- butyric acid). The headspace of each bottle was periodically flushed with oxygen gas to maintain aerobic conditions in the bottles. The headspace of each control bottle also was flushed with oxygen to evaluate potential losses of BTEX due to the flushing process.
• Headspace gases were analyzed for BTEX by using a Vatian CP-3900 gas chromatograph equipped with an FID and a Restek QSPLOT column (30 m length, 0.32 mm diameter) with an injector temperature of 260°C and a detector temperature of 290°C.
• Headspace oxygen was analyzed by using a Varian CP- 3800 gas chromatograph equipped with a Pulsed Discharge Helium Ionization Detector (PDHID) and both a CP-Molsiene 5A column and a CP-ParaBond Q column (both 10 m length, 0.32 mm diameter), an injector temperature of 210°C, and a detector temperature of 240°C.
• PHID Pulsed Discharge Helium Ionization Detector
• Oxygen eluted at 120 min.
• Aqueous alcohol concentrations (as well as iso-butylaldehyde and iso-butyric acid) were measured by first collecting a 130 ⁇ subsample preserved with mercuric chloride. These samples were analyzed by using a Varian CP-3800 gas chromatograph equipped with a flame ionization detector (FID) and a Stabilwax DA column (30 m length, 320 pm diameter), an injector temperature of 280°C, and a detector temperature of 280°C.
• FID flame ionization detector
• Samples (2 mL) were collected from microcosms amended with BTEX and isobutanol at the start, midway (approximately), and end of the experiment to evaluate changes in the microbial population over the course of the study.
• Samples were serially diluted and plated onto R2A Agar (8D Difco) and Basal Salts Medium (BSM; Hareland et al.,1975, J. Bacteriol. 121 : 272-285.) agar immediately after retrieval as per Method SM9215C.
• BSM plates were incubated in sealed containers with either BTEX or isobutanol to select for bacteria capable of growth on these substrates.
• Colony counts were performed manually after 3 days for R2A agar and after 10 days for selective media. Samples ( ⁇ 8 mL) also were immediately frozen at -70°C and at the conclusion of the study were shipped on dry ice to Microbial Insights, Rockford, TN, for CENSUS analysts.
• CENSUS employed quantitative polymerase chain reaction (qPCR) assays to quantify total Eubacteria based on enumeration of Eubacteriai 16S rRNA gene copies (for more information on the CENSUS method see Microbiai Insights, 2009http:/ www. microbe, com/how-census-works, html and http://microbe.com census-applications/anaerobic-btex. html; accessed 07.07.2009 and 05,08.09, respectively).
• qPCR quantitative polymerase chain reaction
• Isobutyric acid concentrations increased initially, but samples taken after 82 days confirm that isobutyric acid also was further degraded in the microcosms (data not shown).
• the biodegradation products of isobutyric acid were not determined, but previous studies have shown that isobutyric acid readily biodegraded under aerobic conditions, and that butyrate is readily transformed to CO 2 under aerobic conditions (Miller, 2001, J. Anim. Sci. 79: 2503-2512; Bonartseva, 2003, Appl. Biochem. Biotech. 109: 285-301).
• isobutanol was degraded from an initial concentration of 3,400 ⁇ M to below the analytical detection limit within 23 days.
• Isobutyialdehyde reached a peak concentration of 900 ⁇ M on day 9 and then declined below the analytical detection limit of 11 ⁇ M after 19 days.
• Isobutyric acid increased to a peak concentration of 1,750 ⁇ M on day 25 and then decreased to 100 ⁇ M by day 48.
• isobutanol was degraded in a similar timeframe and isobutyric acid was observed in similar quantities. However, only trace levels of isobutyialdehyde (78 ⁇ M) were observed.
• BTEX concentrations in the high concentration controls showed no observable decreasing trend through approximately 25 days, at which time decreases in the control concentrations were observed for some compounds (up to approximately 20%).
• the controls were subsequently re-amended with formaldehyde to inhibit microbial activity; of the additional formaldehyde and to prevent further decreases in the controls.
• No significant (>10%) decreases in the low concentration BTEX controls were observed, except for the total xylenes where an approximately 25% decrease in total xylenes concentration was observed over the 10-day duration of this experiment.
• BTEX and isobutanol were evaluated at "high” and low” concentrations (Table 5). Two treatments were prepared using ethanol instead of isobutanol. Electron acceptor concentrations reflect the amount added to the sample and (Table 5) do not include background electron acceptor concentrations in site groundwater. BTEX and alcohol concentrations represent potential groundwater concentrations that might be observed within a source area and in the near downgradient plume.
• Ethanoi has an aqueous solubility approximately 10-times that of isobutanol, and the octanol-water partition coefficient of isobutanol is approximately 10-times that of ethanol (Organization for Economic Co-operation and Development, 2004. SIDS Assessment Report for SIAM 19- Ethanoi (CAS No. 64-17-5). Berlin, Germany; Organization for Economic Co-operation and Development, 2004. SIDS Assessment Report for SIAM 19- Isobutanol (CAS No. 78-83-1), Berlin, Germany). Because the rate of ethanol biodegradation was anticipated to be greater than that of isobutanol, an ethanol molar concentration approximately 3- times greater than isobutanol was conservatively selected for testing.
• Microcosm preparation was performed in an anaerobic chamber. Microcosms were prepared by placing 40 g of site soil into 160 mL glass serum bottles. STEX and alcohol were added to the treatment bottles to attain the target concentrations shown in Table 5. (Target BTEX concentrations for each BTEX compound are listed under the BTEX column.) Bottles were filled with groundwater, leaving approximately 2 mL of headspace. Control microcosms were amended with mercuric chloride (700 mg L -1 in bottles) and formaldehyde (1% by volume in bottles) to limit microbial activity. Treatments were prepared with a minimum of 3 replicates for alcohol and BTEX analyses; one additional replicate per treatment was used for monitoring electron acceptors and methane.
• Headspace gases were analyzed for BTEX by using a Varian CP-3900 gas chromatograph, (GC) equipped with a flaame ionization detector (FID) and a Restek QSPLOT column, and for methane by using a GC equipped with an FID and a Restek Rt-Aiumina column
• FID flaame ionization detector
• Restek QSPLOT Restek QSPLOT column
• Aqueous alcohol concentrations (as well as potential isobutanol degradation products iso-butylaldehyde and iso-butyric acid) were analyzed by using a Varian CP-3800 gas chromatograph, equipped with an FID and a Stabilwax DA column. Aqueous samples were collected for anions analysis via ion chromatography (Dionex DX-120, Sunnyvale, CA). Nitrate also was periodically measured using Quant Nitrate Test strips (EMD Chemicals, Gibbstown, NJ). Total and dissolved iron were measured using Hach test Kits (Hach, Loveland, CO) according to the manufacturer's instructions.
• Microcosm slurry sub-samples samples (approximately 8 mi_) were obtained from Treatments 2, 6, 9, and 12 at the start and at the end of the experiment to ascertain changes in the microbial population over the course of the study. Samples were immediately frozen at -70°C and (at the conclusion of the study) were shipped on dry ice to Microbial Insights, Rockford, TN, for quantitative polymerase chain reaction (qPCR) of total Eubacteria, denitrifying bacteria, iron and sulfate reducing bacteria, and methanogenlc bacteria by the CENSUSTM quantitative PCR technique (Microbial Insights, 2009http://www.
• qPCR quantitative polymerase chain reaction
• Isobutanol was completely degraded in the high concentration treatments, and its degradation rates varied under different anaerobic conditions.
• Figure 5 shows isobutanol and electron acceptor concentrations in the higher concentration treatments (Treatments 2, 6, 9, and 12). Background sulfate concentrations are shown for the unamended treatment. No decreases in isobutanol or ethanol, nor accumulation of isobutyla!dehyde or isobutyric acid, were observed in the control microcosms. The most rapid isobutanol biodegradation was observed in the nitrate-amended microcosms. Within 16 days, isobutanol was degraded to below detection limits under nitrate-reducing conditions (Treatment 6). Nitrate was utilized concurrently with the isobutanol degradation, and decreased to non-detect by day 13 before being re-amended on day 14. No measurable decrease in the background sulfate was observed in Treatment 6 through 19 days (data not shown).
• Isobutanol biodegradation was observed in both the sulfate amended treatments (Treatment 12) and the unamended microcosms (Treatment 2) where limited background sulfate existed.
• sulfate i.e., methanogenic conditions
• microcosms bottles for Treatment 2 were re-spiked with isobutanol (to a final concentration of 3,400 ⁇ M) at 88 days.
• the additional isobutanol was degraded within approximately 30 days.
• trace ( ⁇ 2 ⁇ M) levels of methane were observed in Treatment 2 following depletion of the sulfate, which is similar to the methane levels in the controls.
• Isobutanol in the iron-amended treatment was biodegraded to below the analytical detection limit within approximately 80 days.
• Ferric iron monitored through 44 days, showed concentrations ranging from approximately 18 to 36 ⁇ M. However, only relatively low levels of dissolved ferrous iron (up to 36 ⁇ M) were observed. The absence of appreciable ferrous iron accumulation was likely the result of iron sulfide formation in the microcosm bottles, as a black precipitate was observed.
• background sulfate concentrations decreased in the iron-amended treatment. Decreases in isobutanol concentrations correlated with decreases in sulfate Ieveis.
• Isobutyric acid and trace ieveis of isobutylaldehyde were identified as transient biodegradation intermediates; the subsequent biodegradation of both of these compounds was observed in ail treatments, !so-butyric acid accumulated to near (with a factor of approximately 2) stochiometnc quantities, with the exception of the high concentration nitrate-amended treatment in which only 5% accumulation was observed.
• the limited generation of isobutyric add in the high concentration nitrate treatment is not readily explained.
• Toluene biodegradation was observed in ail the high concentration microcosms amended with electron acceptors (Figure 7).
• Figure 7 When incubated without alcohols, approximately 38 ⁇ M toluene was degraded to below detection limits within 80 days under nitrate-reducing, iron-reducing and sulfate-reducing conditions, respectively.
• the presence of isobutanol exhibited slight impacts on toluene degradation under nitrate-reducing and sulfate-reducing conditions, but slowed the toluene degradation in the iron amended microcosms.
• Reatment 2 In the unamended high concentration microcosms (Treatment 2), however, no measurable toluene concentration decreasing trend relative to the controls was observed.
• benzene concentrations decreased to below the analytical detection limit (0.50 ⁇ M) in the microcosms with isobutanol (Treatment 13), and to approximately 0.85 ⁇ M in the microcosms with ethanol (Treatment 14) after approximately 300 days of incubation. Benzene biodegradation started before day 120 in Treatment 14, and occurred between 160 and 300 days in Treatment 13.
• Results of the microbial analyses shown in Table 6, generally showed an increase in microbial concentrations during the incubations. (Values are in cells mL- ; ⁇ values indicate 95% confidence intervals.)

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