In contrast to soil, ground water lacks an air phase thus the availability of oxygen as electron acceptor is greatly diminished,limited

by low aqueous solubility of oxygen.This results in anoxic condition within petroleum-contaminated plumes in groundwater. Volatile and nonvolatile hydrocarbons are found in ground water at closed petroleum refinery sites, and in leachates from landfills. Ex situ Constructed wetlands-. Engineered systems designed and constructed to utilize the natural geochemical and biological processes such as vegetation, soil/substrate, and their associated microbial assemblages. They are designed to take advantage of the same processes occuring in natural wetland environments to treat polluted waters. Raw or pretreated waste water is piped into the plant and flows through.Advantage: Less expensive to build ,low operation and maintenance expenses, able to tolerate high fluctuations in flow and facilitate water reuse and recycling.Disadvantage: Wetland aging contribute to a decrease in contaminant removal rates over time,Temperature and fluctuations in flow affect wetland function,A heavy flow of incoming water can overload the removal mechanisms in a wetland, while a dry spell can damage plants and severely limit wetland function.2 types:free water surface wetland and subsurface flow wetlands.

free water surface wetlands (FWS)

and subsurface flow (SF) wetlands

Water Circulation Systems.(Raymond method)- work by circulating water amended with nutrients and other substances required to stimulate microbial growth between injection and recovery wells.All of the ground water is recovered, and all or a portion of the treated ground water is reinjected after being amended with nutrients and a final electron acceptor. Recovery systems most frequently use wells. The injected ground water moves through the saturated sediments toward the ground water capture system. As the amended water moves through the contaminated portions of the site, it

increases microbial activity by providing the elements that limit intrinsic biodegradation. Nutrients typically added are nitrogen and phosphorus.Ammonium and nitrate salts are the most common nitrogen sources. Orthophosphate and tripolyphosphate salts are the most common phosphorous sources. The electron acceptor is most commonly oxygen in the form of air, pure oxygen, or hydrogen peroxide. Delivery of oxygen, the most common electron acceptor, is difficult because oxygen gas has limited water solubility and other oxygen vehicles (such as hydrogen peroxide and liquid oxygen) are costly and have had limited effectiveness Oxygen enhancement (Biosparging). the injection of air directly into ground water; Efficient method of delivering oxygen to promote microbial growth. The injected air displaces water in the subsurface, creating pores temporarily filed with air that is easily available to the microbes. Help remove volatile contaminants. As the injected air sweeps upward through the contaminated zone, it can carry volatile contaminants to the soil above the water table for capture by a vapor recovery system. Air sparging- increases mixing in the saturated zone, which increases the contact between ground water and soil; ease and low cost of installing small-diameter air injection points allows considerable flexibility in the design Hydrogen peroxide- dilute solution of hydrogen peroxide is circulated through the contaminated ground water zone to increase the oxygen content of ground water Nitrate enhancement- Solubilized nitrate is circulated throughout ground water contamination zones to provide an alternative electron acceptor for biological activity; enhances the anaerobic biodegradation(toluene, ethylbenzene, and xylenes); more soluble in water than oxygen, mixed oxygen/nitrate system would prove advantageous as addition of nitrate would supplement the demand for oxygen .

Air-sparging system for treating contaminated ground water. Vacuum pumps circulate air to promote the growth of aerobic microbes and to extract volatile contaminants. An infiltration system supplies nutrients.

Biological treatment technologies Bioaugmentation-addition of groups of exogenic microbial strains or genetically engineering
microbes to treat contaminated soil.Effective where native microorganisms are not identified in soil or do not have the metabolic capacity to perform.

Bioventing Bioventing is an in situ remediation technology that uses microorganisms to biodegrade organic constituents adsorbed in the groundwater. Bioventing enhances the activity of indigenous bacteria and simulates the natural in situ biodegradation of hydrocarbons by inducing air or oxygen flow into the unsaturated zone and, if necessary, by adding nutrients. During bioventing, oxygen may be supplied through

direct air injection into residual contamination in soil. Bioventing primarily assists in the degradation of adsorbed fuel residuals, but also assists in the degradation of volatile organic compounds (VOCs) as vapors move slowly through biologically active soil.[3] Biosparging Biosparging is an in situ remediation technology that uses indigenous microorganisms to biodegrade organic constituents in the saturated zone. In biosparging, air (or oxygen) and nutrients (if needed) are injected into the saturated zone to increase the biological activity of the indigenous microorganisms. Biosparging can be used to reduce concentrations of petroleum constituents that are dissolved in groundwater, adsorbed to soil below the water table, and within the capillary fringe. Bioslurping Bioslurping combines elements of bioventing and vacuum-enhanced pumping of freeproduct that is lighter than water (light non-aqueous phase liquid or LNAPL) to recover free-product from the groundwater and soil, and to bioremediate soils. The bioslurper system uses a slurp tube that extends into the free-product layer. Much like a straw in a glass draws liquid, the pump draws liquid (including free-product) and soil gas up the tube in the same process stream. Pumping lifts LNAPLs, such as oil, off the top of the water table and from the capillary fringe (i.e., an area just above the saturated zone, where water is held in place by capillary forces). The LNAPL is brought to the surface, where it is separated from water and air. The biological processes in the term bioslurping refer to aerobic biological degradation of the hydrocarbons when air is introduced into the unsaturated zone. Bioslurping is the adaptation and application of vacuum-enhanced dewatering technologies to remediate hydrocarbon-contaminated sites. Bioslurping utilizes elements of both, bioventing and free product recovery, to address two separate contaminant media. Bioslurping combines elements of both technologies to simultaneously recover free product and bioremediate vadose zone soils. Bioslurping can improve free-product recovery efficiency without extracting large quantities of ground water. In bioslurping, vacuum-enhanced pumping allows LNAPL to be lifted off the water table and released from the capillary fringe. This minimizes changes in the water table elevation which minimizes the creation of a smear zone. Bioventing of vadose zone soils is achieved by drawing air into the soil due to withdrawing soil gas via the recovery well. The system is designed to minimize environmental discharge of ground water and soil gas. When free-product removal activities are completed, the bioslurping system is easily converted to a conventional bioventing system to complete the remediation. Operation and maintenance duration for bioslurping varies from a few months to years, depending on specific site conditions

Applicability: Bioslurping can be successfully used to remediate soils contaminated by petroleum hydrocarbons. It is a cost-effective in situ remedial technology that simultaneously accomplishes LNAPL removal and soil remediation in the vadose zone. Bioslurping is also applicable at sites with a deep ground water table (>30ft.).

Factors that may limit the applicability and effectiveness of the bioslurping process include:

Bioslurping is less effective in tight (low-permeability) soils. Low soil moisture content may limit biodegradation and the effectiveness of bioventing, which tends to dry out the soils. Aerobic biodegradation of many chlorinated compounds may not be effective unless there is a co-metabolite present. Low temperatures slow remediation. Frequently, the off-gas from the bioslurper system requires treatment before discharge. However, treatment of the off-gas may only be required shortly after the startup of the system as fuel rates decrease. At some sites, bioslurper systems can extract large volumes of water that may need to be treated prior to discharge depending on the concentration of contaminants in the process water. Since the fuel, water and air are removed from the subsurface in one stream, mixing of the phases occurs. These mixtures may require special oil/water separators or treatment before the process water can be discharged.

Intrinsic bioremediation Least intensive application of bioremediation.use ambient levels of oxygen and nutrients.Most effective with low levels of contamination or when the rate of limiting factor is the availability of carbon dioxide rather than supply of oxygen or nutrients. Bio-reactor- enclosed system that degrades contaminants in groundwater .. Unlike natural attenuation and in-situ bioremediation, bioreactors can avoid and control the frequent problems of ineffective indigenous microorganisms and/or low indigenous microbial populations ; Optimizes temperature, pH,oxygen, nutrients, and addition of bacteria .Disadvantage:contaminated groundwater is often too dilute

to support an adequate microbial population but very high concentrations may be toxic to microorganisms. Low ambient temperatures can decrease biodegradation rates.If contaminants tend to volatilize, air pollution controls may be necessary.Bioreactors are prone to upset. Nuisance microorganisms can predominate and reduce treatment effectiveness.Residuals may require treatment or disposal.