A PROCESS FOR IN SITU BIODEGRADATION OF HYDROCARBON CONTAMINATED SOIL

Abstract: The present invention is a process for in situ biodegradation of spilled hydrocarbons. The process involves drawing oxygen into a hydrocarbon contaminated zone (10). A borehole (8) is drilled into the contaminated zone (10) and gas is evacuated at high rates out of the borehole via a gas exhaust line (12) to thereby draw oxygen into the contaminated zone (10). Surprisingly, the carbon dioxide concentration in the evacuated gas remains high even at the high flow rates.

Description: A PROCESS FOR IN SITU BIODEGRADATION OF HYDROCARBON CONTAMINATED SOIL FIELD OF THE INVENTION The present invention relates to a process for in situ biodegradation of hydrocarbon contaminated soil. More specifically, the present invention iε a process for drawing oxygen into a contaminated zone to stimulate microbial biodegradation of hydrocarbons. BACKGROUND OF THE INVENTION Hydrocarbons may contaminate both soil and ground water aε. a result of accidental spillage from storage tanks or pipes; accidents with transport vehicles; or even by inten¬ tional acts such as dumping. Typically, some hydrocarbon biodegradation occurs in the first three feet below the earth's surface. However, that portion of the spill below three feet largely remains in the soil. If the hydrocarbons are not isolated or removed, the spill can spread beyond the original area. Various procedures have been proposed to address soil and ground water contamination by spilled hydrocarbons. Some systems require physical containment or removal, while others treat the spilled hydrocarbon in place. When the hydrocarbons are treated in place, they may be evaporated or biodegraded under specific conditions. Underground evaporation of spilled hydrocarbons may be achieved by forced venting. See U.S. Patents Nos. 4,593,760, issued June 10, 1986 and 4,660,639, issued April 28, 1987, both to Visser et al; 4,183,407, issued January 15, 1980 and 3,980,138, issued September 14, 1976, both to Knopic. However, thiε process iε limited by the vapor pressure of the spilled hydrocarbons and the amount that can be evaporated. Since there is a limit on the amount of hydrocarbon that can be evaporated by venting, there is no incentive to go above that flow rate that pro¬ vides the maximum evaporation. Biodegradation has also been diεcloεed for underground hydrocarbons. U.S. Patent No. 4,401,569 issued August 30, 1983 to Jhaveri et al discloses a method and apparatus for treating hydrocarbon contaminated ground and ground water. Patentees disclose adding nutrients and gases to water that is flowed through the contaminated soil. A procesε of this type can be diεadvantageous because: the irrigation water washes some hydrocarbons or other contaminants (toxic metal salts, etc.) into the water table; water carries a limited amount of oxygen (8 ppm) into the soil which limits the amount and the rate of degradation that may take place; irrigation can limit biodegradation by physically channeling oxygen-carrying fluids away from the hydrocarbon contami¬ nated (oily) dirt; and, water and oil are immiscible so that biodegradation is limited to water/oil surfaces. Accordingly, there iε the need for a process that will rapidly decontaminate hydrocarbon contaminated soil in an efficient and an environmentally acceptable manner. The need has now been satisfied by the invention that is described below. SUMMARY OF THE INVENTION According to the present invention, a proceεε iε pro¬ vided for biodegrading hydrocarbonε by drawing oxygen into a hydrocarbon contaminated zone. The process comprises estab¬ lishing a borehole in a hydrocarbon contaminated zone having hydrocarbon degrading microbes; fluidly connecting a source of negative pressure to the borehole; evacuating gas out of the borehole to draw oxygen through the hydrocarbon contami¬ nated zone; monitoring the evacuated gas; and adjuεting the flow rate of oxygen into the hydrocarbon contaminated zone to above the flow rate for maximum hydrocarbon evaporation, whereby a substantial amount of hydrocarbons are biodegraded. Among other factors, the present invention is based on our finding that an unexpectedly effective process for in situ, underground hydrocarbon biodegradation iε provided by drawing atmospheric oxygen into a contaminated zone at high flow rates. Surprisingly, the carbon dioxide concentration in the evacuated gas (as a measure of biodegradation) remains high even at the high flow rates. At the same time, the process iε surprisingly advantageous because it also evacuates volatilized hydrocarbon vapor without the danger of detonation. The process is further advantageous over many prior processes because it rapidly biodegradeε hydro¬ carbons in situ without: being limited by their vapor presεure; incurring additional expenses for nutrients, irrigation, etc.; being limited by the equilibrium limits imposed by disεolving 0 2 and CO, into irrigation water; or diεpersing of hydrocarbons and other contaminants either into the water table or beyond the spill area. While the inεtant invention employε a flow rate above the maximum hydrocarbon evaporation flow rate, thiε maximum hydrocarbon evaporation flow rate iε governed primarily by the type of hydrocarbon being evaporated aε well as the soil type involved in the contamination and therefore the maximum hydrocarbon evaporation flow rate will vary from site to site. The εoil type's role in the maximum hydrocarbon evaporation flowrate reεultε from the εurface area of the hydrocarbon in the εoil's pores which can be exposed to the oxygen-containing gas flowing to the borehole. In εoilε, such as clays and, of course, depending on the hydrocarbon being evaporated, the maximum hydrocarbon evaporation flow rate can be lesε than 5 standard cubic feet per minute (SCFM) per well. In view of the above, as used herein, the term "flow rate for maximum hydrocarbon evaporation" or "maximum hydrocarbon evaporation flow rate" meanε the flow rate at which no εubεtantial additional a ountε of hydro¬ carbon can be removed by evaporation for that particular hydrocarbon or hydrocarbon mixture and that particular soil type. As depicted graphically in FIG. 4 which iε diεcuεsed hereinbelow, the total amount of hydrocarbon evaporated by increasing the gas flow to the bottom of the borehole, aεymptotically approaches its theoretical maximum and at a certain point, no substantial additional amounts of hydro¬ carbon can be practically removed by increasing the gas flow. Accordingly, for the purposes of this application, the term "substantial additional amounts of hydrocarbon" meanε less than ten percent (10%) and preferably lesε than five percent (5%) of additional hydrocarbons can be evaporated by increasing the gas flow. In a preferred embodiment, the preεent invention com¬ prises establishing a borehole from the earth's surface through a hydrocarbon contaminated zone having hydrocarbon degrading microbeε, which borehole terminateε in the ground water; establishing a fluid impermeable lining, coaxially spaced and sealingly connected to the inεide εurface of the borehole, extending from the earth surface to the hydrocarbon- contaminated zone; establishing a fluid permeable lining, coaxially spaced within the inside of the borehole, fixedly connected to, and extending from, the end of the fluid impermeable lining;fluidly connecting a source of negative pressure to the fluid impermeable lining; evacuating gas from the fluid permeable section of the borehole to draw oxygen through the hydrocarbon-contaminated zone; monitoring the oxygen total hydrocarbon, and carbon dioxide content of the evacuated gas; and adjusting the flow rate of oxygen into the hydrocarbon contaminated zone to achieve within 50% of the maximum hydrocarbon biodegradation and to maintain an oxygen and total hydrocarbon concentration outside the explosive range. In hydrocarbon contaminated zones where there is a high ground water table and/or the soil type is less porous, the negative pressure necessary to generate the required flow rate may in fact cause the ground water and other fluids, such as hydrocarbons, possibly contained therein or therewith (collectively "ground fluid") to locally be drawn up in the direction of the borehole thereby creating an inverted cone of ground fluid. In the extreme case, the inverted cone of ground fluid can be drawn up the fluid impermeable lining to the earth's surface. Inverted cones of ground fluid are to be avoided because in addition to restricting the flow rate of gases through the hydrocarbon contaminated zones, these inverted cones could in fact spread the hydrocarbon contamination to zones not previously contaminated. Accordingly, in a preferred embodiment, the process of the instant invention includes the additional step of establishing means to remove ground fluid from or near the bottom of the borehole. Suitable means to remove ground fluid include employing pumps either at the earth's surface or in the E StfECT borehole, employing vacuum either through the fluid impermeabl lining wherein the gases are flowing or or via a separate conduit, employing a sufficiently high flow rate of gas to rem ground fluids entrained in aerosols and in some cases employin siphon. Preferably, the ground fluid is removed by placing a pump at or near the bottom of the borehole and internally in t fluid permeable lining; said pump being fluidly connected to a conduit which leads from the pump to the earth's surface so as remove the ground fluid. Said conduit is preferably placed within the fluid permeable and impermeable lining and has an external diameter less than the internal diameter of the fluid permeable and impermeable lining. Preferably,the external diameter of the conduit is sufficiently small so as to avoid undue restrictions on the gas flowing through the fluid permea and impermeable linings. The conduit is made of material sufficiently capable of transporting ground fluid under the operating conditions of the process of this invention without undue wear. Suitable materials include engineered plastics [{such as polyvinylchloride (PVC) , polyethylene, etc.] flexibl rubber tubing and metals tubing. The major criteria being that the material be stable to the differential pressure between th pressure of the fluids inside the conduit and the pressure ins the fluid permeable and impermeable linings outside the condui The ground fluid so removed may or may not be contaminated with hydrocarbons. If the ground fluid is contaminated with hydrocarbons, then it is preferably placed in suitable holding means for subsequent cleanup. The amount of ground fluid removed should be sufficient to keep the ground fluid substantially level across the hydrocarbon contaminated zone to be treated. In some cases, it may be preferable to remove sufficient ground fluid so as to create depression the ground fluid. Such a cone of dpression would allow hydrocarbons floating on the ground water to flow into the cone of depression which has the effect of localizing the concentration of liquid hydrocarbons and which can then be removed as part of the ground fluid (creating cones of depressions in ground fluids is well known to environmental and ground water hydrologiεtε) . Moreover, since the cone of depression would be near the borehole and therefore near the point of entry of the oxygen-containing gaseε, hydrocarbonε contained in εuch a cone of depression should be removed, either by evaporation or biodegradation, faster than without such a cone of depression. Most preferably, the amount of ground water removed is that amount which permits optimal gas flow through the borehole. The pump which removes the ground fluid may be any pump capable of removing ground fluid at the desired rate. Pre- ferably, the pump is a submersible injector pump which can be lowered into the fluid impermeable and permeable lining. BRIEF DESCRIPTION. OF THE DRAWINGS FIG. 1 is a schematic diagram of an apparatus useful in the present process. FIG. 2 iε a schematic diagram of a well configuration useful in the present invention. FIG. 3 is a graph showing the relationship between flow rate and C0 2 % in the evacuated air for site 1. FIG. 4 is a graph showing the total hydrocarbon recovery for site 1. SUBSTITUTE HBWT FIG. 5 iε a graph comparing the biodegradation and evaporation for εiteε 1, 2, and 3. DETAILED DESCRIPTION OF THE INVENTION The preεent invention iε useful for in situ biodegrada¬ tion of hydrocarbon contaminated εoil. The term hydrocarbon includeε organic molecules that are commonly found in oil, such as aromatics, alkaneε, olefinε, variouε complex heter- ocyclic molecules, and various derivatives of these mole¬ cules, such as alcohols, esterε, ketoneε, carbonateε, acidε, εome halogenated co poundε, complex heterogeneouε hydrocar¬ bon moleculeε, aε well aε the more specific decomposable compounds listed in Amdurer et al, Syste ε to Accelerate In Situ Stabilization of Waεte Deposits (Report No. EPA/540/2-86/002) which is hereby incorporated by reference in its entirety. However, the term hydrocarbon only includes those compounds which are- biodegradable and which reach their maximum evaporation point before their maximum biodegradation point. These hydrocarbons typically have vapor pressureε leεs than 2 psia at 25°C. Reference will now be made to FIG. 1 to provide an example of the preεent process. A hydrocarbon contaminated zone 10 can be contained within a vadose zone 2. The vadose zone 2 iε defined by the earth's surface 1 and the ground water level 4. There is also a capillary zone 6 just above the ground water level 4 where oil can be supported on soil capillarieε in top of the water. It is contemplated that hydrocarbons are biodegraded when they are in the hydrocarbon contaminated zone 10, the capillary zone 6, or are washed into either two zoneε by the riεe and fall of the ground water. As shown in FIG. 1, a borehole 8 is established in the hydrocarbon contaminated zone 10. The borehole 8 essen¬ tially extends from the earth's εurface 1 and provides vapor access to the contaminated zone 10. The borehole 8 can extend into the hydrocarbon contaminated zone 10, the capillary zone 6, or preferably further downward below the ground water level 4. The borehole 8 preferably includes a fluid impermeable lining 18 and a fluid permeable lining 20. The fluid impermeable lining 18 iε preferably positioned within the borehole 8, typically adjacent to the earth's surface 1. The fluid permeable lining 20 is also preferably positioned within the borehole 8, but in a position that enεures oxygen flow through the hydrocarbon contaminated zone 10. A gas exhaust line 12 iε fluidly connected to the borehole 8 at the earth's εurface 1 (which includeε a εubmerged connection as shown in FIGS. 1 and 2) and then to ..a vacuum source 14 and a gas processing means 16. The vacuum source 14 creates negative pressure to draw oxygen into the hydrocarbon con¬ taminated zone 10 along the flow lines shown by the arrows in FIG. 1. Starting from the vacuum εource 14, the gas is evacuated in this sequence, through the: vapor carrying line 12; the fluid impermeable lining 18; the fluid per¬ meable lining 20; the hydrocarbon contaminated zone 10; the vadose zone 2; and the earth's surface 1. Gas exhaust line 12 can be fluidly connected to a single borehole 8 or multiple boreholes (not shown). The evacuated gas is preferably monitored for the flow rate, the oxygen concentration, the total hydrocarbon con¬ centration, and the carbon dioxide concentration. Moni¬ toring equipment for these purpoεeε are known in the art. However, an example of a monitoring εyεtem iε εhown in FIG. 2. Flow rates can be measured by inserting a device such a an anemometer into a flow measurement port 30. Total hydrocarbon concentration can be measure by a system which includes a multimeter with a resistivity sensor, both of which can be attached to a well cap 34. A total organic analyzer (e.g.. Model 401 manufactured by Byron Instruments) can also be used to determine the hydrocarbon and C0 2 concentrations. Oxygen and carbon dioxide concentrations can be measured by sampling the evacuated gas through sampling port 36 and passing the sample to an oxygen analyzer such as Model 320p-4 manufactured by Teledyne Analytical Instruments. In the process of the present invention, the flow rate of the evacuated gas is adjusted to achieve the objective of a rapi and high amount of hydrocarbon biodegradation. Additionally, it is an objective to insure that the mixture of oxygen and hydrocarbon vapor in the evacuated gas is outside the explosive range. We have discovered that the first objective is achieved at surprisingly high flow rates and the second objective is achieved by adjusting the concentrations of oxygen and hydrocarbon vapors at these high flow rates. The flow rates (pe borehole) in the process of the present invention are preferably above the flow rate for maximum evaporation of the hydrocarbon that is to be biodegraded; preferably in certain porous soils, the flow rates per well are between 30 and 250 SCFM and in non- porous soils, such as clays, the flow rates per well can be as low as 5 SCFM and preferably greater than 5 SCFM and more preferably between 5 and 75 SCFM; most preferably the flow rates are adjusted to achieve within 50% of the maximum hydrocarbon biodegradation. As used herein, the term "non-porous soils" means soils which have a permeability to water below 10_5 cm/sec and ϋBs u H includes soil types, such as clays, silts, fractured rocks, etc.; whereas "porous soilε" mean εoilε which a permeability to water greater than 10 cm/sec and includes soils types such as sands, sandy loams, gravel, etc. Hydrocarbons can be removed by several mechanismε at these high flow rates. They are: evaporation; biodegrada¬ tion; and by the creation of a hydrocarbon aerosol. Some hydrocarbons are removed by evaporation when gas is drawn out of the borehole 8 and oxygen is drawn through the hydro¬ carbon contaminated zone 10. For biodegradable hydrocarbons this evaporation typically increases as the flow rate increases, but will asymptotically approach its theoretical maximum and at a certain point, no substantial additional amounts of hydrocarbon can be practically removed by increasing the airflow. In hydrocarbon evaporation syεtems it iε unneceεsary and inefficient to increase the flow rate above this point because no subεtantial additional amounts of hydrocarbon will be evaporated. For purposes of the present invention it is preferable to go beyond that level to reach high hydrocarbon biodegradation rates. Surprising¬ ly, biodegradation occurs at the high flow rates beyond the point of maximum evaporation. Understandably, these high biodegradation rates increase as the flow rate increaseε, but εtop increasing at some flow rate, depending on the hydrocarbon and the soil conditions (i.e., depth, per¬ meability, etc.). The hydrocarbons can also be removed by the third mechanism; the creation of a hydrocarbon aerosol. These aerosolε can form due to very high flow rateε or a large preεsure drop acrosε the fluid permeable lining 20. Depending on the hydrocarbon and the particularitieε of the hydrocarbon contaminated zone 10, it may be deεirable to increase the flow rateε to remove hydrocarbonε by thiε additional method. It is preferable to achieve the maximum hydrocarbon biodegradation that is possible. For measurement purposes, hydrocarbon biodegradation is assumed to be equal to C0 2 removal because the hydrocarbons are converted to CO- (even though some hydrocarbons are initially incorporated into biomasε). To calculate the maximum hydrocarbon biodegrada¬ tion rate, the evacuated gaε iε monitored for CO- concentra¬ tion. Then CO- removed per unit time iε calculated from the flow rate and CO- concentration. Flow rate is increased until the total C0 2 removed no longer increaseε. At the flow rates of the present invention the C0 2 concentration in the evacuated gas is preferably between 1 and 14%, more prefer¬ ably between 6 and 14%. Also, the oxygen and total hydrocarbon concentrations are monitored and are adjusted to outside the explosive range. Preferably, the 0 2 concentration iε limited to below 10% to reduce the poεεibility of exploεion when the total hydrocarbon vapor iε above 1%. However, thiε oxygen limit may be exceeded if it iε preferred to increaεe the flow rate. When the oxygen concentration iε equal to or greater than 10%, diluent gaε iε preferably introduced into the evacuated gaε to reduce the total hydrocarbon concentration to below the lower exploεive limit. The present invention is operable on virtually all varieties of biodegradable hydrocarbons within the boiling range of 90 to 1500 β F at atmospheric presεure. Thiε includes: heavy oils, such as asphalt, gas oils, or fuel oils; and light oils, such as gaεoline, jet fuel, dieεel, turbine fuels, or light gas oils, as well as the compounds listed in Amdurer et al. The proceεε iε not limited by low hydrocarbon vapor pressureε. Some biodegradable inorganicε might also be biodegraded, such as sulfides, phosphorus, and nitrogen compounds. Additionally, the proceεε can be operable on a variety of soils. Examples are: sands; coral; fissured volcanic rock; carbonaceous depositε (i.e., limeεtone); gravel; εiltε; clays; and mixtureε thereof. More densely packed εoil can decrease the oxygen transport as well as the flow rate and can require closer well spacing when multiple wells are used. However, the present procesε will continue to be effective in εuch more denεely packed soils because oxygen will contact the microbes, either by convection or by diffusion, to stimulate hydrocarbon biodegradation and further because the lower gas flow rates will still be above the maximum hydrocarbon evaporation flow rate for these εoils. The microbes that biodegrade hydrocarbons are typically bacteria. Many bacterial genuses adapt to this task and are known to those skilled in microbiology. Repreεentative bacteria include gram-negative rodε εuch aε: Pεeudomonas; Flavobacterium; Alcaligenes; and Achromobacter; or gram-positive rodε and cocci εuch as: Brevibacterium; Corynebacterium; Arthrobacter; Bacillus; and Micrococcus; and others such as Mycobacterium; Nocardia; and Streptomyces. These bacteria are preferably indigenous although they may be added to the hydrocarbon contaminated zone 10. Other hydrocarbon degrading microbes are fungi, algae, actinomyceteε, etc. (εee alεo Appendix A of Amdurer et al. ) . The borehole 8 iε another feature of the present invention. Preferably, the diameter of the borehole is between 8 and 40 inches, more preferably between 12 and 32 inches. Preferably, the borehole 8 extends into the hydrocarbon contaminated zone 10. In some instances it is preferable to extend the borehole 8 into the capillary zone 6 just above the ground water level 4 or even below the ground water level 4. Preferably, a lower depth enεures that air iε drawn along the capillary zone irreεpective of the fluctuationε in the ground water level. The borehole 8 can be drilled to abεolute depths in excess of 150 feet. For a deeper borehole a higher flow rate is typically required for more biodegradation. The borehole 8 can be vertical, diagonal, or laterally oriented and can be drilled into the hydrocarbon contaminated zone 10 by any well drilling method known in the art that is suit¬ able for penetrating the particular contaminated soil. Also, if it is preferable to laterally vent a contaminated zone, a trench may be excavated, a fluid permeable lining inserted into the trench, and then the soil back filled over the lining. However, care should be taken.not to use a method that would reduce the permeability of the soil around the fluid permeable lining 20 of the borehole 8, i.e., by compaction or by using too much drilling muds or fluids. Typically, the fluid impermeable lining 18 is coaxially spaced within the borehole 8. The lining 18 has an internal diameter between 2 and 16 inches, more preferably between 2 and 12 inches. This lining 18 may be well casing or a con¬ duit which is smaller in diameter than the borehole 8. Pre¬ ferably, a portion of the fluid impermeable lining 18 at the earth's εurface 1 (or a minor depth below the εurface) iε sealed off and attached to the vacuum source 14. A fluid permeable lining 20 iε coaxially poεitioned at the end of fluid impermeable lining 18. Thiε lining 20 may be well casing having holeε, εcreenε, or other means to permit a gaε, an aerosol, or liquid flow therethrough. Preferably, both linings 18 and 20 are subεtantially the εame diameter. It iε intended that both liningε direct the vacuum induced air flow through the hydrocarbon contaminated zone 10. To achieve thiε goal, air infiltration between the lining 18 and the borehole 8 is preferably minimized. To prevent air from being drawn down from the earth's εurface and along the lining 18, a low permeability material iε preferably inserted between the lining 18 and the borehole 8. Prefer¬ ably, thiε material iε compacted εoil, clay, grout, or cement. Additionally, the preεεure drop between the fluid per¬ meable lining 20 and the borehole 8 can be adjuεted. A higher pressure drop is preferable because high flow rateε ' of this invention can form aerosols of hydrocarbons or con¬ taminated water. The aerosol is carried out of the borehole with the evacuated gas thereby increasing contaminant removal. In this instance it is not necessary to provide a fill material for the lining 20. However, if a low pressure drop is preferred, then the space defined by the borehole 8 and the outer diameter of the fluid permeable lining 20 can be packed with a loose fluid permeable material, εuch aε gravel, sand, or crushed rock. Thiε material preventε fine particles, εuch aε εilts, from plugging the fluid permeable lining 20. The particular characteristics of the contaminated area may suggest that one or more boreholes be eεtabliεhed to carry out the preεent proceεε. Some relevant factorε for thiε determination are: the amount of εpilled hydrocarbon; the depth of the hydrocarbon contaminated zone 10; the type of εoil; the ground water level 4, etc. If multiple bore¬ holes are necessary, then they are preferably spaced between and 5 and 300 feet apart. Preferably, these boreholes are all vacuum wells although air inlet wells can be used for deeper hydrocarbon contaminated zoneε 10. The vacuum source 14 evacuates gas through the fluid permeable lining 20 and passeε thiε evacuated gaε to the proceεεing means 16. The vacuum source 14 may be any means capable of establishing negative pressure within the borehole to cause a flow of oxygen through the hydrocarbon contaminated zone 10. Preferably, the vacuum source 14 is a pump or an aspirator (see Knopic, U.S. Patent No. 3,980,163). Preferable pumps are rotary and liquid ring pumps. Exemplary liquid ring pumps are manufactured by Sullair and Nash, and have a capacity to pull between 70 and 2500 SCFM and preferably between 110 and 2500 SCFM. Prefer¬ ably, these pumps have a capacity to pull either at least 30 SCFM through porous soil from at least one borehole, " preferably multiple boreholes, or at least 5 SCFM through non-porous soilε from at leaεt one borehole, preferably multiple boreholeε. Preferably, they have a meanε for flame εuppreεεion to prevent exploεionε. The processing means 16 may comprise a meanε to vent the evacuated gaε to the atmo- εphere, a means for filtering the gas, a means for com¬ pressing the evacuated gas, or a means for incinerating the evacuated gas. The evacuated gas contains: oxygen, carbon dioxide as a biodegradation product, water vapor, and hydro¬ carbon vapor due to evaporation. These components of the evacuated gas may be useful for a variety of purposeε out¬ side of the present invention. For example, the high amount of C0 2 that is produced by this proceεε can be recovered and used in tertiary oil recovery or used as a refrigerant. The hydrocarbon vapor can be recovered and further refined or sold. A variety of other factors contribute to the efficiency of the preεent invention. For example, the εoil tempera¬ ture, the εoil humidity, the nutrients, and the pH are all variables that affect the growth of the microbial popula¬ tion. The soil temperature iε difficult to regulate, but temperatures above 50 β F are preferable to promote microbio¬ logical growth. Additionally, humidity is preferable to foster growth. Water may be introduced into the air that is flowed through the hydrocarbon contaminated zone 10 by irrigation or steam injection, for example. Additionally, organic and inorganic nutrients are essential to microbial growth may be added to the hydrocarbon-contaminated zone 10 by means known in the art. These nutrients can be alkali metals (εuch as potassium), phosphates, and nitrates. Fur¬ thermore, pH may be manipulated by the addition of basic or acidic compounds if it is incompatible with microbial growth. The present invention will be more fully understood by reference to the following examples. They are intended to be purely exemplary and are not intended to limit the scope of the invention in any way. EXAMPLES Tests were conducted on systems installed at four sites where various oil products had been spilled in εoil and ground water. The systemε had different depthε to the top and bottom of the fluid permeable lining 20 (well εcreen) and each site involved different hydrocarbon contaminants as shown below: Depthε to the Top and Bottom Site Type of Oil of the Well Screen 1 70% gaεoline 15 to 30 feet 30% diesel 2 gasoline blending 130 to 145 feet component 3 heavy fuel oil 10 to 90 feet 4 asphalt diluted with 4 to 15 feet kerosene The testε are deεcribed below in each of the exampleε. In each example no nutrients (fertilizers) or bacteria were added to the sites to stimulate biodegradation. Soil mois¬ ture was not increased by irrigation above normal levels. Example 1 Six teεt wellε wee drilled near 10 exiεting wellε. Each borehole had an internal diameter of 4 inches and an outside diameter of 8 inches. PVC pipe was uεed aε a fluid imper¬ meable lining and a PVC εcreen waε used aε a fluid permeable lining. The εoil waε εandy loam. After evacuating and teεting, gaε from the borehole waε εubεequently incinerated. The soil around the spill had been vented for about two years to control migration of oil vapors into nearby buildings. The venting rate for those two yearε waε below 30 εtandard cubic feet per minute (SCFM) per well. In the test the vented gas waε kept below the lower flammability limit (1% oil vapor) by diluting it near the well head with air. An example of the undiluted vent gaε had the following compoεition: Well Flow Oil SCFM CO '2, 0, Vapor Methane 30 7.5% 8.5% 1% 0% The atmoεpheric oxygen that was pulled into the ground stimulated significant biodegradation. There was enough biodegradation to deplete the oxygen concentration to below 10% and to make the vented gas non-flammable regardlesε of the oil vapor concentration. The lack of methane indicated insignificant anaerobic biodegradation. The flow rate of the evacuated air was increased in steps and held constant for several days between each step, then samples of gas were analyzed for oil vapor and C0 2 concentration. The C0 2 levels remained nearly constant until the flow was increased above 30 SCFM, then .it declined slowly as shown in FIG. 3. The C0 2 and 0 2 concentrations were sustained throughout several months of testε which indicated that biodegradation was not temporary or limited by soil moisture or nutrientε. The oil biodegradation rate was calculated by assuming that oil was converted directly into C0 2 (which is conservative since aε much aε half of the oil iε initially converted to biomaεs). Total removal rate was the sum of the biodegradation and evaporation rateε as εhown in FIG. 4. FIG. 4 εhows that biodegradation increases even after the evaporation rate has reached a plateau. Example 2 The carbon dioxide, oxygen, and total hydrocarbon con¬ centrations were measured as in Example 1 and a well outside the spill area waε monitored to determine the background levels for each of these components. These wells were drilled as in Example 1. At 30 SCFM the following data was generated for both wells: Well Flow Oil Site in SCFM C0 2 0 2 Vapor Methane The flow rate was increased to 180 SCFM which increased the biodegradation. At this flow rate, the gas velocity waε high enough to create an aerosol of liquid gaεoline and water droplets which indicated that the invention can be designed to also remove some liquidε. Example 3 This example shows the biodegradation of heavy fuel oil. At Site 3 the carbon dioxide, oxygen, and total hydro¬ carbon concentrations were monitored. The following data was collected: 30 6.8% 11% 0% 2.3% Evaporation of the heavy oil was negligible due to its low volatility. Venting at low flow rates would be ineffec¬ tive in removing heavy, non-volatile oil spillε. FIG. 5 compareε the removal rateε at Sites 1, 2 and 3. FIG. 5 εhowε that the process of the preεent invention is useful to remove a broad range of hydrocarbon contaminants from soil and various depthε. Furthermore, the oxygen and oil vapor concentrations can be controlled to εafely operate outεide of the explosive limits. Example 4 One test well was drilled into a non-porous soil (clay). The borehole had an internal diameter of 12 inches. PVC pipe was used as a fluid impermeable lining and a PVC εcreen waε uεed aε a fluid permeable lining. The clay had a water —5 —6 permeability of from 10~ to 10 cm/εec. After evacuating and testing, gas from the borehole waε εubεequently treated with activated carbon. When neceεεary, the vented gaε can be kept below the lower flammability limit (1% oil vapor) by diluting it near the wellhead with air. Exampleε of undiluted vent gas had the following C0 2 content under the following procesε conditionε: Estimated Oil Biodegradation 5 5 8 10 In thiε example, the hydrocarbon content waε εufficiently low so aε to allow oxygen concentration at levelε of approxi¬ mately 17 volume percent. Thiε example de onεtrateε the operability of the proceεε of thiε invention on non-porouε εoils contaminated with hydrocarbons. The foregoing disclosure has taught some specific examples of the present invention. However, there are many modifica¬ tions and variationε within the εpirit of the diεcloεure. It is intended that the embodiments are only illustrative and not restrictive.

Claims: WHAT I S CLAIMED I S : 1. A proceεε for biodegradating hydrocarbons by drawing oxygen into a hydrocarbon contaminated zone, comprising: establiεhing a borehole into a hydrocarbon contaminated zone having hydrocarbon degrading microbes; fluidly connecting a source of negative pressure to the borehole; evacuating gas out of the borehole to draw oxygen into the hydrocarbon contaminated zone; and adjusting the flow rate of oxygen into the hydro¬ carbon contaminated zone to above the flow rate for maximum hydrocarbon evaporation, whereby a substantial amount of hydrocarbons are biodegraded. 2. A process in accordance with Claim 1 wherein the hydrocarbon contaminated zone comprises a porous εoil. 3. A procesε in accordance with Claim 2 wherein the flow rate iε between 30 and 250 SCFM per well. 4. A proceεs in accordance with Claim 1 wherein the hydrocarbon contaminated zone compriseε a non-porouε εoil. 5. A process in accordance with Claim 4 wherein the flow rate is between 5 and 75 SCFM per well. 6. A process in accordance with Claim 1 wherein the flow rate is adjusted so that the amount of hydrocarbon biodegrada¬ tion is within 50% of the maximum. 7. A proceεε in accordance with Claim 1 further com¬ prising adjuεting the oxygen and total hydrocarbon concen¬ trationε in the evacuated gaε to outside the exploεive range. 8. A proceεε in accordance with Claim 7 further comprising: establiεhing a fluid impermeable lining coaxially spaced and sealingly connected to the inside surface of the borehole extending from the earth surface to the hydrocarbon contaminated zone; and establishing a fluid permeable lining, coaxially spaced within the inside of the borehole, fluidly connected to, and extending from, the end of the fluid impermeable lining. 9. A proceεs "in accordance with Claim 1 wherein* the borehole extends into a capillary zone. 10. A proceεs in accordance with Claim 1 wherein the borehole extendε into the ground fluid. 11. A proceεε in accordance with Claim 1 further com- priεing establiεhing multiple boreholeε which are εpaced between 5 and 300 feet apart from each other. 12. A proceεε in accordance with Claim 1 further com- priεing monitoring the water content of the exhauεted gaε. 13. A proceεε in accordance with Claim 1 wherein the hydrocarbonε that are biodegraded have a boiling point between 90 and 1500 β F. 14. A process in accordance with Claim 8 wherein the internal diameter of said fluid permeable and fluid imper¬ meable linings is between 2 and 16 inches. 15. A process in accordance with Claim 1 further com¬ prising adding nutrients which promote bacterial growth to the hydrocarbon contaminated zone, selected from the group of phosphates, nitrates, or alkali metals. 16. A process in accordance with Claim 1 further comprising removing hydrocarbons by creating an aerosol. 17. A process for biodegrading hydrocarbons by drawing oxygen into a hydrocarbon contaminated zone, comprising: establishing a borehole from the earth's surface, through a hydrocarbon contaminated zone having hydrocarbon degrading microbes, and terminating in the ground fluid; establiεhing a fluid impermeable lining, coaxially spaced and sealingly connected to the inside εurface of the borehole, extending from the earth εurface to the hydrocar¬ bon-contaminated zone; establiεhing a fluid permeable lining, coaxially spaced within the inside of the borehole, fixedly connected to, and extending from, the end of the fluid impermeable lining; fluidly connecting a source of negative preεεure to the fluid impermeable lining; evacuating gaε from the fluid permeable lining to draw oxygen into the hydrocarbon-contaminated zone; monitoring the oxygen, total hydrocarbon, and carbon dioxid content of the evacuated gas; and adjusting the flow rate so that the amount of hydrocarbon biodegradation is within 50% of the maximum hydrocarbon biodegradation rate;p and maintaining an oxygen and total hydrocarbon concentration outside of the explosive range. 18. a process in accordance with Claim 17 further comprising removing hydrocarbons by creating an aerosol. 19. A process in accordance with either Claim 10 or Claim 17 further comprising establishing means to remove ground fluid from or at near the bottom of the borehole and removing said ground fluid. 20. A process in accordance with Claim 19 wherein sufficient ground fluid is removed to maintain the ground fluid substantially level across the hydrocarbon contaminated zone. 21. A process in accordance with Claim 19 wherein sufficient ground fluid is removed to create a cone of depressio in the ground fluid. 22. A process in accordance with Claim 19 wherein said means to remove ground fluid comprises a pump. 23. A process in accordance with Claim 22 wherein said pum is placed at or near the bottom of the borehole and is fluidly connected to a conduit which leads form the pump to the earth's surface and said conduit being located within the fluid permeabl and impermeable linings and having an external diameter less tha the internal diameter of the fluid permeable and impermeable linings. j BSTiTU E SHEET

Inventors: ELY DOUGLAS L, HEFFNER DAVID A, ELY, DOUGLAS, L., HEFFNER, DAVID, A.
Applicants: CHEVRON RES, CHEVRON RESEARCH COMPANY
Application year: 1988
Main classification: C02F3
IPC codes: B09C1, C02F3