Question Explain in detail in-situ and ex-site bioremediation with suitable example.

In Situ Remediation

In situ (in place) remediation refers to the cleanup of contaminated soils and groundwater without removing contaminated media from the subsurface, typically through the use of physical and/or chemical processes. In-situ Bioremediation treats the contaminated soil or groundwater in the location in which it is found. In this technology oxygen and occasionally nutrients are pumped under pressure into the soil through wells. The nutrients are spread on the surface to infiltrate into the contaminated area of material or the saturated zone.

In situ bioremedation technology was originally developed as a less costly, more effective alternative to the standard pump-and-treat methods used to clean up aquifers and soils contaminated with organic chemicals (e.g., fuel hydrocarbons, chlorinated solvents), but has since expanded in breadth to address explosives, inorganics (e.g., nitrates), and toxic metals (e.g., chromium). It have the potential to provide advantages such as complete destruction of the contaminant(s), lower risk to site workers, and lower equipment and operating costs. One way to categorize ISB is by the type of metabolism involved. The two high-level categories of metabolism are aerobic and anaerobic. The target metabolism for an ISB system will depend on the contaminants of concern. Some contaminants (e.g., fuel hydrocarbons) are degraded via an aerobic pathway, some anaerobically (e.g., carbon tetrachloride), and some

contaminants can be biodegraded under either aerobic or anaerobic conditions (e.g., trichloroethene). Another way to categorize ISB is by the degree of human intervention. Accelerated in situ bioremediation is at one end of the scale, where there is a high degree of human intervention. In accelerated ISB, substrate or nutrients are added to an aquifer to stimulate the growth of a target consortium of bacteria. Usually the target bacteria are indigenous, however enriched cultures of bacteria (from other sites) that are highly efficient at degrading a particular contaminant can be introduced into the aquifer, which is termed bioaugmentation. Accelerated ISB is used where it is desired to increase the rate of contaminant biotransformation, which may be limited by lack of required nutrients, electron donor, or electron acceptor. The type of amendment required depends on the target metabolism for the contaminant of interest. Aerobic ISB may only require the addition of oxygen as the electron acceptor, while anaerobic ISB generally requires the addition of an electron donor (e.g., lactate, benzoate) and potentially an electron acceptor (e.g., nitrate, sulfate). Chlorinated solvents, in particular, often require the addition of a carbon substrate to stimulate reductive dechlorination. The goal of accelerated ISB is to increase the biomass throughout the contaminated volume of aquifer, thereby achieving effective biodegradation of dissolved and sorbed contaminant. At the other end of the scale, Monitored natural attenuation (MNA) is a method of applying in situ bioremediation with essentially no human intervention. MNA is a multi-faceted approach, one component of which is the degradation/transformation of contaminants by indigenous microorganisms without human intervention (i.e., using existing bacteria and whatever nutrients that are already available in the system). Site characterization, evaluation of the MNA potential (which often includes reactive flow and transport modeling with software like RT3D), and long term monitoring comprise the activities required to implement MNA. Site characterization determines the extent of contamination, the properties of the aquifer, the geochemistry of the aquifer, and the nature of biological reactions in the aquifer. This characterization information can then be used to assess the potential for MNA to prevent contaminant mass from impacting receptors of concern. Analytical and/or numerical models can be used to estimate fate of the contaminants as one line of evidence to support (or reject) MNA. Long-term monitoring is used to assess the fate and transport of the contaminants compared against the predictions. The evaluation can undergo further iterations as more data are collected and the understanding of the system improves.

Whether accelerated ISB or natural attenuation is used at a particular site will depend upon the aquifer properties, chemical concentrations, goals of the remediation project, and the economics of each option. The rate of contaminant degradation is typically slower in a natural attenuation scenario than for active bioremediation because the concentration of bacteria is much greater in accelerated bioremediation and the rate of activity is proportional to the amount of biomass. Thus, natural attenuation typically takes longer to complete. Accelerated ISB usually provides a faster solution, but has a much greater investment in materials, equipment, and labor. More on MNA

The U.S. EPA OSWER Directive [U.S. EPA, 1997], describes monitored natural attenuation as follows: The term "monitored natural attenuation", as used in this Directive, refers to the reliance on natural attenuation processes (within the context of a carefully controlled and monitored site cleanup approach) to achieve site-specific remedial objectives within a time frame that is reasonable compared to that offered by other more active methods. The "natural attenuation processes" that are at work in such a remediation approach include a variety of physical, chemical, or biological processes that, under favorable conditions, act without human intervention to reduce the mass, toxicity, mobility, volume, or concentration of contaminants in soil or groundwater. These in situ processes include biodegradation, dispersion, dilution, sorption, volatilization, and chemical or biological stabilization, transformation, or destruction of contaminants. Other terms associated with natural attenuation in the literature include "intrinsic remediation", "intrinsic bioremediation", "passive bioremediation", "natural recovery", and "natural assimilation". While some of these terms are synonymous with "natural attenuation," others refer strictly to biological processes, excluding chemical and physical processes. Natural attenuation processes are typically occurring at all sites, but to varying degrees of effectiveness depending on the types and concentrations of contaminants present and the physical, chemical, and biological characteristics of the soil and groundwater. Natural attenuation processes may reduce the potential risk posed by site contaminants in three ways: The contaminant may be converted to a less toxic form through destructive processes such as biodegradation or abiotic transformations Potential exposure levels may be reduced by lowering of concentration levels (through destructive processes, or by dilution or dispersion) Contaminant mobility and bioavailability may be reduced by sorption to the soil or rock matrix Advantages of In Situ Bioremediation It may be possible to completely transform organic contaminants to innocuous substances (e.g., carbon dioxide, water, ethane). Accelerated ISB can provide volumetric treatment, treating both dissolved and sorbed contaminant. The time required to treat subsurface pollution using accelerated in situ bioremediation can often be faster than pump-and-treat processes. In situ bioremediation often costs less than other remedial options. The areal zone of treatment using bioremediation can be larger than with other remedial technologies because the treatment moves with the plume and can reach areas that would otherwise be inaccessible. As an in situ (versus ex situ) technology, there is typically little secondary waste generated As an in situ (versus ex situ) technology, there is reduced potential for cross-media transfer of contaminants As an in situ (versus ex situ) technology, there is reduced risk of human exposure to contaminated media With MNA, there is less intrusion because few surface structures are required

MNA can be used in conjunction with, or as a follow-up to, other (active) remedial measures MNA has lower overall remediation costs than those associated with active remediation Limitations of In Situ Bioremediation Depending on the particular site, some contaminants may not be completely transformed to innocuous products. If biotransformation halts at an intermediate compound, the intermediate may be more toxic and/or mobile than the parent compound. Some contaminants cannot be biodegraded (i.e., they are recalcitrant). When inappropriately applied, injection wells may become clogged from profuse microbial growth resulting from the addition of nutrients, electron donor, and/or electron acceptor. Accelerated In situ bioremediation relies on appropriate distribution of amendments and thus, may be difficult to implement completely in low-permeability or heterogeneous aquifers. Heavy metals and toxic concentrations of organic compounds may inhibit activity of indigenous microorganisms. In situ bioremediation usually requires an acclimatized population of microorganisms, which may not develop for recent spills or for recalcitrant compounds. With MNA, longer time frames may be required to achieve remediation objectives, compared to active remediation With MNA, site characterization/monitoring may be more complex and costly; long-term monitoring and periodic re-evaluation of the remedy effectiveness will generally be necessary With MNA, institutional controls may be necessary to ensure long term protectiveness With MNA, hydrologic and/or geochemical conditions may change over time and could result in renewed mobility of previously stabilized contaminants, adversely impacting remedial effectiveness With MNA, more extensive education and outreach efforts may be required to gain public acceptance of the remedy Biotransformation of Chlorinated Hydrocarbons Chlorinated hydrocarbons can undergo biotransformation via three different mechanisms: use of the chlorinated compound as an electron acceptor, use of the chlorinated compound as an electron donor, or by cometabolism (fortuitous reaction providing no benefit to the microorganisms) One or more of these mechanisms may be active at a given site. Electron Acceptor Reactions A chlorinated hydrocarbon may be used as an electron acceptor. Use of chlorinated compounds as electron acceptors has been demonstrated under nitrate- and iron-reducing conditions, but the most rapid biodegradation rates, affecting the widest range of chlorinated aliphatic hydrocarbons, occur under sulfate-

reducing and methanogenic conditions. This mode of biotransformation requires an appropriate source of carbon (electron donor) for microbial growth and reductive dehalogenation to occur. Electron donor carbon may come from natural organic matter, anthropogenic sources (e.g., fuel hydrocarbon co-contamination), or intentional introduction of organic carbon into the aquifer (i.e., in accelerated in situ bioremediation). Electron Donor Reactions In this situation, the CS is used as the primary substrate (electron donor) and the microorganism obtains energy and organic carbon from the CS. This may occur under aerobic and some anaerobic conditions. Lesser oxidized chlorinated compounds (e.g., vinyl chloride, DCE, or 1,2-dichloroethane) are more likely to be amenable to this mode of biotransformation. Note that fuel hydrocarbons are biodegraded under this mode of operation because they can be used as an organic carbon source. Cometabolism When a chlorinated aliphatic hydrocarbon is biodegraded via cometabolism, the degradation is catalyzed by an enzyme or cofactor that is fortuitously produced by the organisms for other purposes. The microbe receives no known benefit from the degradation of the chlorinated compound. The biotransformation of the CS may actually be harmful/inhibitory to the microorganisms. Cometabolism is best documented in aerobic environments, although it potentially could occur under anaerobic conditions.

Advantages m Remediates contaminants that are adsorbed onto or trapped within the geologic materials of which the aquifer is composed along with contaminants dissolved in the groundwater. m Application involves equipment that is widely available and easy to install. m Creates minimal disruption and/or disturbance to on-going site activities. m Time required for subsurface remediation may be shorter than other approaches (e.g., pump and treat). m Is generally recognized as being less costly than other remedial options (e.g., pump

and treat, excavation). m Can be combined with other technologies (e.g., bioventing, soil vapor extraction) to enhance site remediation. m In many cases, this technique does not produce waste products that must be disposed of. Disadvantages m Injection wells and/or infiltration galleries may become plugged by microbial growth or mineral precipitation. m High concentrations (TPH > 50,000 ppm) of low solubility constituents may be toxic and/or not bioavailable. m Difficult to implement in low-permeability aquifers (<10-4 cm/sec). m Re-injection wells or infiltration galleries may require permits or may be prohibited. Some states require permit for air injection. m May require continuous monitoring and maintenance. m Remediation may only occur in more permeable layer or channels within the aquifer.

Ex-Situ Remediation

Unlike in-situ approaches, ex-situ remediation involves the removal of contaminated media, either for off-site disposal or for on-site treatment and subsequent return to the subsurface. Our team of engineering, geoscience and environmental specialists have considerable experience and routinely employ a variety of ex-situ methods, the most common being: excavation and off-site disposal of impacted soils (with on-site segregation/management of contaminated soils from uncontaminated soils); the construction and operation of biopiles (both aboveground and subterranean); and, recovery and treatment (if required) of impacted groundwater. Ex-Situ Remediation Ex-situ Bioremediation requires pumping of the groundwater or excavation of contaminated soil prior to remediation treatments. Ex-situ Bioremediation can be further broken down into two main components or processes; Slurry-phase and solid-phase treatment. Slurry-phase- This treatment involves the initial combination of water with the contaminated soil and later degradation in a bioreactor. Solid-phase- This treatment achieves the similar goal of the former treatment yet, in this process, the contaminated soil is placed in a bed and nourished with nutrients, moisture and oxygen in hopes that decomposition will occur.

Ex-Situ Bioremediation Keywords: Windrow, biopile, vented windrow, composting, landfarming, excavation, bioremediation, biodegradation, treatment bed, ex-situ, polycyclic aromatic hydrocarbons, hydrocarbons, semi-volatile organic compounds, SVOCs, diesel, kerosene, phenols, cresols.

Introduction/principles Ex-situ bioremediation is a biological process in which excavated soil is placed in a lined above-ground treatment area and aerated following processing to enhance the degradation of organic contaminants by the indigenous microbial population. Under aerobic conditions, specific micro-organisms can utilise organic contaminants such as petroleum hydrocarbon mixtures, polycyclic aromatic hydrocarbons (PAH), phenols, cresols and some pesticides as a source of carbon and energy and degrade them ultimately to carbon dioxide and water. It is unusual to require the addition of microbial populations but usual to assess the nutrient requirement and amend the basic nutrients and organic substrate of the soil if any of these elements are deficient or absent. Oxygen (via the introduction of air) is essential to allow the microbial population to develop cultures capable of sustaining degradation. Contaminants Ex-situ bioremediation can remediate a wide range of hydrocarbon contaminants including but not limited to: General hydrocarbons Kerosene Phenols Cresols Polycyclic aromatic hydrocarbons Semi-volatile organic compounds Diesel range hydrocarbons Lubricating oils Straight chain aliphatics Non-chlorinated hydrocarbons within the carbon chain lengths C6 to C14 are readily treatable, non-chlorinated hydrocarbons with carbon chain lengths C15-C32 are treatable but require longer time periods to degrade. Chlorinated hydrocarbons and other more complex chains can be degraded but require detailed assessment and analysis to determine suitability. Methods As a general rule all but the most homogenious of excavated soils require processing before bioremediation techniques can be successfully applied. There are a number of different techniques and formats to biological treatment however the basic principal of intruducing the correct soil oxygen, moisture and nutrient conditions prevails. Land farming The simplest form of bioremediation, contaminated soil is excavated and spread out in layers approximately 0.3m in thickness on a lined treatment area. Bioremediation can be enhanced by periodic turning of the bed and addition of nutrients. Due to the limiting thickness of soil layers (0.3m) landfarming techniques require large areas and are not generally suitable for small sites, but can be the cheapest and most basic form of bioremediation.

Turned Windrows The excavated soil is placed into a shaped pile up to between 1.5 and 2m height and up to 6m wide in a lined area, the pile is aerated by periodical turning of the windrows by specialised machinery which can be excavator mounted or self propelled. Soil organic ammendments and nutrients can be easilly added to the windrows during turning to improve aeration and soil characteristics as required. This is often the most cost effecive method of ex-situ biological treatment Force Vented Biopiles The excavated soil is placed into a shaped pile up to 3m in height and 6 m wide in a lined area, the pile is aerated either via a vacuum pump or air injection blower system. Vapours from the biophile can be collected and treated on-site by granular activated carbon (GAC) or air bio-filter to reduce emissions to the atmosphere. Biopiles can be constructed taller than windrows and so can require less space on site, additionally the injection of air can be used to control the bed temperature during winter periods if overwintering is required. It is also the preferred choice if particualrly odourous or volatile contaminants are the issue. For all bioremediation techniques, an Environmental Permit is required from the Environment Agency and any run off or "leachate" from the soil needs be collected and treated. Treatment times range dependent on the contamaintion and target concentrations from 6 to 16 weeks dependent on contaminant type, concentration and soil properties and time of year. Ambient temperature has a significant effect on bioremediation with best degradation rates occurring during the warmer summer months, cold winter weather can significantly slow and even halt biodegradation. Advantages and Limitations Advantages: * Proven track record on UK contaminated sites * Suitable for a wide range of contaminants * Suitability realtively simple to assess from site investigation data * Flexible with respect to volumes (Vertase FLI has treated in excess of 250,000 tonnes in one season on some sites) Limitations: * Not applicable to heavy metal contamination or chlorinated hydrocarbons such as trichloroethylene (TCE) * Non-permeable soils require additional processing (clays and silts etc) * Can require large areas for treatment beds and thus site size is an important consideration * Contaminants must be aerobically biodegradable, * Temperature, weather and material dependent