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Cold Regions Science and Technology 53 (2008) 16 41 www.elsevier.com/locate/coldregions
Potential for bioremediation of petroleum hydrocarbons in groundwater under cold climate conditions: A review
Dale Van Stempvoort a,, Kevin Biggar b
a
National Water Research Institute, PO Box 5050, Burlington, Ontario, Canada L7R 4A6 b BGC Engineering Inc. Suite 207-5104, 82 Avenue, Edmonton, AB, Canada T6B 0E6 Received 10 November 2006; accepted 22 June 2007
Abstract Globally, bioremediation is a common choice for remediation of petroleum hydrocarbon-contaminated sites. For application at cold climate sites, bioremediation approaches are appealing because they have potential to be more efficient and cost-effective than alternative, more energy intensive approaches. Several bioremediation approaches have been reported to be successful for petroleum hydrocarbon-contaminated soils at cold climate sites. In contrast, there are relatively few publications on applications of bioremediation for petroleum-contaminated groundwater at cold climate sites. Most of the existing relevant groundwater studies were conducted at sites with either no permafrost, or with sporadic to discontinuous permafrost. To date, the majority of cold climate groundwater investigations were at fuel spill sites; few studies on bioremediation of dissolved hydrocarbon plumes derived from crude oil or gas condensate have been published. Some studies reported that extents of hydrocarbon plumes in groundwater were limited by natural attenuation, including intrinsic bioremediation. At other sites, oxygenation of groundwater or amendments with nitrate were reported to be successful techniques for enhancing biodegradation of petroleum hydrocarbons. Both aerobic and anaerobic processes appear to be important at these sites. Based on three case studies, bioremediation (in situ or ex situ) may be feasible for sites with extensive permafrost. Further research and field demonstrations are required to establish or confirm the applicability of bioremediation technologies to clean up hydrocarbons in groundwater in various hydrogeological settings at cold climate sites. 2007 Elsevier B.V. All rights reserved.
Keywords: Bioremediation; Petroleum; Hydrocarbons; Groundwater; Cold climate, Natural attenuation
1. Introduction Petroleum hydrocarbon pollution is a pervasive, global problem. The main sources of petroleum contamination at cold climate terrestrial sites can be attributed to spills and leaks of crude oil and natural gas condensate as consequences of oil and gas production (e.g., Alaska USA; Canada, Russia), the transport of
Corresponding author. E-mail address: dale.vanstempvoort@ec.gc.ca (D. Van Stempvoort). 0165-232X/$ - see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.coldregions.2007.06.009
petroleum products by pipelines and other means, and the above-ground or underground storage of fuel (Margesin and Schinner, 1999). The widespread use of petroleum fuel and other products in cold climate regions has led to contamination of soil and groundwater at many sites. In these regions, the cold temperatures and remote locations pose additional challenges for remediation. This paper addresses a science gap by reviewing information on the feasibility to apply bioremediation for petroleum-contaminated groundwater at cold
D. Van Stempvoort, K. Biggar / Cold Regions Science and Technology 53 (2008) 1641
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climate sites. Previous reviews of information on the biodegradation of petroleum hydrocarbons in groundwater (e.g., Suarez and Rifai, 1999) have generally not addressed cold climate sites specifically. Reviews of bioremediation techniques for petroleum hydrocarbon contamination at cold climate sites have generally focused on aerobic biodegradation processes by coldadapted microorganisms in soils (e.g., Atlas and Cerniglia, 1995; Margesin and Schinner, 2001; Filler et al., 2006). In contrast to soil, groundwater lacks an air phase and thus the availability of oxygen as an electron acceptor is greatly diminished, limited by the low aqueous solubility of oxygen (approximately 12mg/L at 5C). This typically results in anoxic conditions within petroleum-contaminated plumes in groundwater. However, some anaerobic microorganisms can degrade hydrocarbons using other electron acceptors, such as sulfate, nitrate or ferric iron (see Section 2). Hence the intrinsic (i.e. unassisted) biodegradation of petroleum hydrocarbons in groundwater may be dominated by anaerobic processes (Lovley, 1997; Weidemeier et al., 1999). The objective of this review is to address the above noted science gap by summarizing available information regarding bioremediation of petroleum-contaminated groundwater at cold sites, including: (1) information regarding aerobic and anaerobic biodegradation processes at such sites; (2) evaluation of the potential to utilize such processes to remediate the groundwater; (3) identification of key research needs for advancing such bioremediation applications for groundwater at cold climate sites. 1.1. Recent expansion of bioremediation technologies Bioremediation has been defined as a managed or spontaneous process in which biological, especially microbial, catalysis acts on pollutant compounds, thereby remedying or eliminating environmental contamination (Madsen, 1991). This paper reviews information relevant to the applicability of bioremediation technologies for petroleum-contaminated groundwater under cold climate conditions. Bioremediation includes a range of environmental remediation techniques/technologies that were introduced largely in the 1980s and 1990s. Since then applications have grown rapidly world-wide. In recent decades, bioremediation has become one of the most common approaches used to remediate petroleum
hydrocarbon-contaminated sites. Bioremediation technologies are appealing because they offer the potential for significant cost savings compared to conventional remediation technologies, such as excavation and disposal in landfills, excavation and thermal treatment, and pump and treat. Proponents have argued that bioremediation technologies are safer and less disruptive (e.g., in situ techniques) than some of the conventional technologies; the latter are often not feasible or practical at remote sites in the north. Table 1 provides a list of some bioremediation techniques to treat groundwater, as well as some alternative physical/chemical/thermal approaches, including a brief definition of each. Explanations of various bioremediation approaches and technologies are provided by Atlas (1995a,b,c, 1997); Sikdar and Irvine (1998), Downey et al. (1999); Weidemeier et al. (1999); Suthersan (2001); Hughes et al. (2002) and others. Active bioremediation technologies accelerate the reduction or elimination of contaminants through environmental modification (Atlas, 1995c; Margesin and Schinner, 1999). Passive bioremediation technologies make use of natural biodegradation processes in soil and groundwater. Ex situ bioremediation technologies involve excavation of contaminated soil or removal of contaminated groundwater for treatment on- or off-site, whereas in situ technologies provide remediation of contaminated soil or groundwater in place (Riser-Roberts, 1998). Bioremediation approaches may also incorporate physical and chemical processes along with biological processes. For groundwater applications, in situ bioremediation approaches include biosparging with air or oxygen, introduction of specially designed oxygen releasing compounds, liquid delivery of nutrients and/or electron acceptors such as H2O2 or nitrate, and intrinsic (naturally-occurring) bioremediation (sometimes referred to as monitored natural attenuation). Some remediation systems combine existing proven techniques (physical and/or chemical and/or biological). For example, bioslurping (multiphase extraction), developed in the 1990s, combines vacuum removal of free product near the water table in combination with in situ bioventing (Riser-Roberts, 1998 p. 105). Biostimulation and bioaugmentation are active bioremediation approaches that can be applied under both ex situ and in situ conditions (cf. Table 1). These involve the addition of essential nutrients for enhancing the existing natural bacterial population (biostimulation) or the addition of cultured bacteria with specific hydrocarbon-degrading potential (bioaugmentation). In addition to climate/temperature factors, which are the focus of this review, there are many other site-
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Table 1 Ex situ and in situ physical/chemical and biological remediation approaches for groundwater Ex situ groundwater treatment Technique Definition In situ groundwater treatment Technique Definition
Physical/chemical processes Air stripping Volatile organics are partitioned from extracted ground water by increasing the surface area of the contaminated water exposed to air. Aeration methods include packed towers, diffused aeration, tray aeration, and spray aeration. a Carbon Removal of hydrophobic organic contaminants adsorption from aqueous phase to carbon by physical and chemical forces. b Phase Use of filter membranes and/or conventional filtration/ oil-water separator technology to remove separation nonaqueous phase/emulsions of hydrocarbons from water.
Physical/chemical processes Treatment walls/ passive reactive barriers Barriers allow the passage of water while causing the degradation or removal of contaminants. a
Air sparging
Steam sparging/ flushing
Chemical oxidation
Hydrofracturing enhancement
The injection of air below the water table in order to induce volatilization of contaminants into the unsaturated zone, which can be removed by soil vapor extraction. b Steam is forced into an aquifer through injection wells to vaporize volatile and semivolatile contaminants, which are removed by vacuum extraction in the unsaturated zone and then treated. c Bringing chemical oxidants (various materials) into contact with subsurface contaminants to remediate the contamination. d Injection of pressurized water through wells to crack low permeability and over-consolidated sediments; cracks are filled with porous media that serve as substrates for bioremediation or to improve pumping efficiency. a
Biological processess e Constructed Use of natural geochemical and biological wetlands processes inherent in an artificial wetland ecosystem to accumulate and remove contaminants from influent waters. a Bioreactors A contained vessel in which biological treatment takes place. f
Intrinsic bioremediation
Unmanipulated, unstimulated, non-enhanced biological remediation of an environment; i.e. natural attenuation. f
Biosparging
The injection of air or specific gases below the water table to enhance bacterial activity for remediation. c Phytoremediation The use of natural plants to remove contaminants through bioaccumulation or through enhancing biodegradation. b Bioslurping Combines vaccum removal of petroleum hydrocabon free product with in situ bioventing. Designed for removal of free-floating LNAPL on the water table as well as residual product in the vadose zone. b Biofilter (groundwater) Refers to treatment of groundwater via passage through a biologically active area in the subsurface. f
a b c d e f
Van Deuren et al., 2002. Riser-Roberts, 1998. USEPA, 2004b. USEPA, 2004a. Most of the biological techniques except intrinsic bioremediation include biostimulation, and some bioaugmentation, as defined in the text. Hazen, 1997.
specific factors that may affect biodegradation processes, such as: presence of a hydrocarbon-degrading microbial population, the chemical composition of the oil/petroleum source, availability of oxygen or other electron acceptors, nutrient supply, presence of toxic or inhibiting chemicals, and characteristics of the soil/ geological conditions. This report summarizes the results from various studies that have indicated the roles that these various factors play at cold climate sites.
1.2. Definitions In this review: The term hydrocarbons refers specifically to petroleum hydrocarbons, and the term treatment should be considered as being synonymous with remediation. A cold climate site is one at which the average annual air temperature is 8C, and where measured groundwater temperatures are typically 10C or
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lower these values, which are slightly higher than those used in a recent review by Van Stempvoort and Grande (2006), were selected to include several relevant groundwater studies in the Great Lakes region of North America and the Baltic region of Scandinavia/Europe, where annual air temperatures are typically in the range 48C. Permafrost is defined as subsurface soil, sediment or rock having a temperature persistently below 0C for a period of at least two years (Williams and Smith, 1989); it generally occurs in areas with mean annual air temperatures (MAAT) below 1.5C (Vidstrand, 2003). Frozen ground includes soil or rock in which part or all of the pore water has turned into ice, whereas unfrozen ground does not contain any ice (National Snow and Ice Data Center, 2006). In the subsurface, the boundary between liquid and frozen water is not sharp. Soilwater-ice systems contain liquid water as thin films on soil/mineral surfaces at temperatures well below 0C (van Everdingen, 1990; Vidstrand, 2003). The active layer is a near-surface zone of ground above permafrost that changes seasonally from frozen ground to unfrozen ground (Fig. 1). A talik is a localized layer or body of ground that remains unfrozen in a permafrost area as a result of a thermal, hydrological, hydrogeological, or hydrochemical anomaly. A thaw bulb is a zone of thawed ground below or surrounding a man-made structure placed on or in permafrost that is maintained at temperatures above 0C (National Snow and Ice Data Center, 2006) (Fig. 1). Groundwater refers to the saturated or phreatic zone, including the capillary fringe above the water table, where pores are saturated with water. Suprapermafrost water occurs in unfrozen ground above permafrost; it may be present in active layers, taliks and/or thaw bulbs. At sites underlain by zones of continuous permafrost, the suprapermafrost water that is particularly vulnerable to hydrocarbon contamination may include groundwater in taliks or thaw bulbs, or at the base of the active layer (i.e., seasonal). Intrapermafrost water occurs in unfrozen ground within permafrost; it may be present in taliks and/or thaw bulbs.
production, transmission and storage facilities. While applications of bioremediation at cold climate sites have expanded in recent years, there is limited agreement as to which bioremediation technologies are effective under various cold climate conditions. Some have questioned whether bioremediation approaches are suitable options for cold climate sites because of their low temperature regime (Mohn et al., 2001). Studies have generally shown that the microbial degradation of hydrocarbons tends to be slower under cold temperature conditions, and that it is typically negligible under frozen conditions (e.g., Atlas, 1985). However, a recent study by Rike et al. (2005) has indicated some hydrocarbon degradation can occur at temperatures ranging from 2 to 6C within seasonally frozen ground. At sites which contain permafrost, the groundwater temperatures are typically lower than 5C, either seasonally or on a year-round basis. Although the annual fluctuations in groundwater temperatures are typically less drastic than those in the overlying soil/ vadose zone, at some sites thin zones saturated with suprapermafrost water occur only in the warm season each year, at the base of the active layer. Such extreme conditions may jeopardize the successful application of bioremediation technologies. Even at relatively warm sites, the intrinsic bioremediation of hydrocarbon-contaminated groundwater may take considerable time. Slow recoveries may be acceptable at some sites, depending on the inferred risks to receptors (adjacent water bodies, etc.), and the land use. However, in other cases, engineered bioremediation approaches may be more appropriate to speed up the process through the supply of electron acceptors, nutrients, and heat. 2. Microbial degradation of hydrocarbons at cold climate sites Many microorganisms have metabolic capabilities to degrade petroleum hydrocarbons (e.g., Atlas, 1995b; Spormann and Widdel, 2000; Chakraborty and Coates, 2004). Hydrocarbon-degrading microorganisms have been reported to increase from less than 0.1% of total bacterial population in pristine environments to up to 100% of the total microbial population if the environment is exposed to hydrocarbon contamination (Atlas, 1981). Hydrocarbons ranging from C10 to C26 and aromatics of low molecular weight are considered the most readily degraded (Atlas, 1995b), whereas more complex molecular structures are generally more resistant to biodegradation. Early reviews of the bioremediation of hydrocarbons (e.g., Atlas, 1981, 1985) focused mainly on marine environments and almost exclusively on aerobic
1.3. Applications of hydrocarbon bioremediation technologies at cold sites There are many cold climate terrestrial sites where soil and groundwater are contaminated with hydrocarbons, largely the result of spills and leaks at petroleum
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Fig. 1. Conceptual model of groundwater-permafrost relationships at cold climate sites. Modified after van Everdingen (1990) and Vidstrand (2003). Dashed arrows indicate flow of water.
oxidation pathways. Later reviews reported that anaerobic processes contribute to the biodegradation of petroleum hydrocarbons (e.g., Spormann and Widdel, 2000; Phelps and Young, 2001; Chakraborty and Coates, 2004). Zwolinski et al. (2001) concluded that our understanding of the diversity of the microbial organisms and communities involved in hydrocarbon degradation is still very limited. With respect to groundwater, reviewers have provided information on biodegradation of petroleum hydrocarbons under both aerobic and anaerobic conditions (e.g., Suarez and Rifai, 1999; Weidemeier et al., 1999; Lovley, 2000; Chapelle, 2001). But these reviews have generally provided little if any information on how these processes are affected by temperature, or whether bioremediation of hydrocarbons in groundwater is a feasible approach at cold climate sites. 2.1. Cold adapted microorganisms Microorganisms adapted to environments subjected to low temperatures are generally classified as psychrophiles (cold preference) or psychrotrophs (cold tolerant). Morita (1975) defined psychrophiles as organisms that have an optimal temperature for growth of 15C or lower, a maximum growth temperature of about 20C, and a minimum growth temperature of 0C or lower. By contrast, Morita used the term psychrotrophs to refer to other organisms that grow at these low temperatures (015C), though this is not the optimal temperature range for them. Subsequent studies have sometimes
referred to psychrotrophs as psychrotolerant microorganisms (e.g., Nedwell and Rutter, 1994). Russell (1990) reviewed information on how some microorganisms have adapted to cold temperature conditions. These microorganisms tend to have cell membranes that are enriched in unsaturated lipids and depleted in branched chain lipids, which may be a mechanism to maintain fluid properties at low temperatures. In a more recent review, Nedwell (1999) suggested that stiffening of lipids in the membranes at lower temperatures might account for the decreased affinity of the microorganisms for substrates. Recent studies have indicated that some microorganisms are adapted to temperatures below 0C, including permafrost (Steven et al., 2006). For example, Rivkina et al. (2000) conducted a laboratory study of the metabolism and growth of bacteria from Siberian permafrost at temperatures between 5 and 20C. In sediment samples, metabolism (uptake of 14C-labelled acetate) declined with temperature, and was very slow but still measurable at temperatures of 15 to 20C. During growth, the minimum doubling times of the bacterial populations ranged from 1day (5C) to 20days ( 10C) to 160days ( 20C). At the end of the growth phase, the stable populations that were reached (i.e., stationary phase) declined with temperature, following a curve similar to that of the predicted thickness of remaining unfrozen water for the same temperature range. This suggests that the stationary phase, which is generally considered to be reached when the availability
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of nutrients becomes limiting, was controlled by the diffusion through the layers of unfrozen water, which decreased in thickness with decreasing temperature. Films of unfrozen water in permafrost are apparently essential for the mass transfer of nutrients and metabolites, and thus the survival and growth of microorganisms (Steven et al., 2006). Viable microorganisms isolated from permafrost tend to be psychrotrophs rather than psychrophiles, and include both aerobic and anaerobic bacteria, such as sulfate-reducers and methanogens (Steven et al., 2006). Analyses of gases extracted from the pore spaces of permafrost and redox potentials measured in permafrost (Steven et al., 2006) suggest that both aerobic and anaerobic conditions are common. 2.2. Microbial degradation of hydrocarbons at cold temperatures Many of the laboratory experiments that have demonstrated the biodegradation of hydrocarbons by microorganisms have been conducted at 20 to 35C (Margesin and Schinner, 1997). Similarly, many of the field tests and demonstrations of hydrocarbon bioremediation have been conducted under either warm or temperate climate conditions. Typically, for such field demonstrations and applications, temperature data have not been collected and/or reported. In one of the earliest studies to indicate the potential for microbial degradation of hydrocarbons at low temperatures, Zobell (1973) reported on laboratory microcosm experiments in which samples of crude oilcontaminated soil or water from the tundra region of northern Alaska were used to inoculate mixtures of mineral salts media, while being incubated at temperatures of 1.1 (depressed freezing point), 4 or 8C. At 4C and 8C, most microcosms had strong bacterial activity based on the visible emulsification and disappearance of the oil phase over two to four weeks. In tests at 1.1C, growth of microorganisms was detected after a few days, and emulsification of oil occurred within two or three weeks, associated with consumption of O2. Under the conditions of Zobell's experiments, growth rates of microorganisms at 1.1C and 4C were indistinguishable, whereas the rate at 8C was approximately double that of the lower temperatures. Over a ten week period, the average amounts of various crude oils degraded in the microcosm tests were: 55% at 8C, 44% at 4C and 38% at 1.1C. Zobell concluded that psychrophilic bacteria were active in their tests, and reported that many more varieties of bacteria were present in the cultures they grew at 4 and
8C than in the 1.1C tests. Based on a stoichiometric comparison of O2 uptake rates and disappearance of hydrocarbons, Zobell suggested that some of the hydrocarbons were only partially degraded in their tests. Based on the detection of psychrophilic hydrocarbon-degrading bacteria in samples from natural oil seeps by Zobell (1973), Agosti and Agosti (1973) inferred that it might be useful to provide cultures from these seeps as inoculants to clean-up pipeline oil spills. Atlas (1981, 1985) summarized the earliest laboratory studies which collectively indicated that hydrocarbon biodegradation can occur at significant rates at low temperatures. For experiments with either soil or beach sand, significant biodegradation rates were reported for temperatures as low as 36C, but no degradation was observed below 0C. Q10 values were sometimes calculated to indicate changes in biodegradation rates with temperature: For a given temperature T, Q10 is the ratio of the rate of biodegradation at T plus 10C to the rate at T. Q10 values were reported for experiments with beach sand or seawater, with temperature ranges of 6 to 26C or 5 to 20C. The results suggested that the rate of hydrocarbon biodegradation decreases by a factor of 2 to 4 for every 10C decline in temperature. However, as Atlas (1981) pointed out, the influence of temperature on the biodegradation rate is more complex than these apparent Q10 values. The influence of temperature on the biodegradation rate is interactive with other factors, such as the composition of the hydrocarbon mixture, the microbial community, the physical state of the hydrocarbons, the amount of water and nutrients present, and the availability of oxygen (or other electron acceptors). In general, the pioneering laboratory studies reviewed by Atlas indicate that psychophilic or psychrotrophic microorganisms growing at low temperature conditions were not as capable at degrading some of the hydrocarbon fractions (e.g., isoprenoids, branched or aromatic groups) as mesophilic microorganisms growing at higher temperatures. Atlas (1991) and Atlas and Bartha (1992) summarized the main limiting factors that influence biodegradation of petroleum hydrocarbons in cold climates. Atlas (1991) identified two main categories into which the rate-limiting factors can be divided; 1) the physiological capabilities of the indigenous hydrocarbondegrading microbial population, and 2) the abiotic variables that affect the activity (i.e., growth and metabolism) of that microbial population. A review by Margesin and Schinner (2001) also summarized information on the biodegradation of hydrocarbons by cold-adapted microorganisms. The reviewers observed that cold habitats generally possess a sufficient population of indigenous hydrocarbon-degrading
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microorganisms which are able to respond to contamination, and that these tend to be psychrotrophic. Similar to earlier reviews, they noted that bioaugmentation has generally not been successful, though it may reduce the lag time for the growth of a hydrocarbon-degrading population, whereas biostimulation by fertilization with nutrients has been an effective strategy. They also observed that the physical environment is a factor that effects hydrocarbon degradation, and provided a few examples (e.g., sand content). Margesin and Schinner (2001) summarized information that indicated a considerable range of hydrocarbon compounds can be degraded by bacteria at cold climate sites, including alkanes, aromatic hydrocarbons, and polycyclic aromatic hydrocarbons (PAHs). Short-chain alkanes were more readily degraded than longer chain alkanes. In terms of biodegradation of aromatics, much of the research has focused on BTEX: benzene, toluene, ethylbenzene and xylenes. Some studies have indicated rates of biodegradation of toluene or benzene under cold climate conditions that were similar to rates observed at warm sites, whereas others indicated slower degradation of BTEX at lower temperatures. To date, the reviews of biodegradation of hydrocarbons at cold climate sites have generally focused on aerobic processes in soils. However, over the past decade, a growing number of studies of the intrinsic biodegradation of hydrocarbons in groundwater have indicated that anaerobic biodegradation processes are important (e.g., Lovley, 1997; Weidemeier et al., 1999), including some studies that have considered cold climate sites specifically (e.g., Herrington et al., 1997; Armstrong et al., 2002; Ulrich et al., 2006). The anaerobic processes typically involve one or more of the following electron accepting processes: reduction of dissolved sulfate or nitrate, reduction of mineral phase ferric iron or manganese, and methanogenesis (also referred to as methane fermentation: Stumm and Morgan, 1996). 3. Bioremediation of hydrocarbons at cold sites: previous reviews pertinent to groundwater Information on the kinetics of microbial degradation of hydrocarbons in groundwater has typically been provided as rates or rate constants with reference to processes described as attenuation, decay, degradation or biodegradation. For consistency, this section uses the term biodegradation rate constant. Reviews by Aronson et al. (1997) and Suarez and Rifai (1999) have summarized biodegradation rate constants for dissolved hydrocarbons in groundwater, mainly BTEX, each review based on data from approximately 150 field and laboratory studies. The estimated biodegradation rate
constants based on field investigations have typically taken into account concentration gradients and inferred groundwater velocities, and may account for other factors, such as sorption and dispersion, as applicable. Some field biodegradation rate constant estimates are based on tests that involved injection of hydrocarbons together with conservative tracers. The majority of the reported biodegradation rate constants refer to the first order model of biodegradation: C C0 ekt 1
where C0 is the initial dissolved hydrocarbon concentration, C is the concentration after time interval t, and k is a first order rate constant (units of time 1). Other rate equations used to simulate biodegradation, such as the zero-order model have been discussed by Aronson et al. (1997), Suarez and Rifai (1999) and others. In the reviews by Aronson et al. (1997) and Suarez and Rifai (1999), there was little discussion of the role of temperature. Aronson and Howard noted that temperature and redox environment did not appear to be correlated to the anaerobic biodegradation of benzene in aquifer environments. Suarez and Rifai (1999) made a general statement that the optimum temperature range for most organisms is 1035C, while noting that below this optimum range growth rates of microorganisms tend to double with every 10C increase in temperature (i.e., the Q10 approach). The lack of further discussion about the role of temperature is not surprising, given that there is very little published information on the effect of temperature on hydrocarbon degradation rates in groundwater. Salanitro (1993) summarized information on the biodegradation of aromatic hydrocarbons (BTEX) in groundwater for several case studies in which both field investigations and microcosm experiments were available. Several of these case studies involved relatively cold sites in Michigan and Ontario, and corresponding microcosm experiments at 1012C. The results of these studies indicated that monoaromatic compounds were readily biodegraded in aquifers at low temperatures (circa 10C). The inferred biodegradation rate constants for these low temperature sites were similar to those at warmer sites that were also reviewed by Salanitro (e.g., Florida and Texas, USA). Herrington et al. (1997) summarized the results of investigations of the natural attenuation of aviation/jet fuel plumes in groundwater at five US Air Force Bases, including one in northern Michigan, and four in Alaska. At the Michigan site, the groundwater temperatures ranged from 9.8 to 14.9C. At the Alaska sites, the groundwater temperatures ranged between 3.4 and
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11.7C. Herrington et al. found evidence for receding (shrinking) hydrocarbon plumes at all sites, linked to aerobic processes, as well as anaerobic processes of nitrate, iron, manganese and sulfate reduction and methanogenesis. They estimated that the overall first order cumulative BTEX degradation rate constants at these cold climate sites ranged from 0.19 to 2.99% day 1, including aerobic and anaerobic processes. The authors pointed out that these biodegradation rates were similar to those reported for warmer sites. Armstrong et al. (2002) analyzed a database of groundwater chemistry results for monitoring programs at 124 contaminated sites in western Canada. The sites were mainly upstream oil and gas sites in Alberta, where typically the hydrocarbon contaminants in groundwater are derived from releases of crude oil or natural gas condensate. In this region groundwater temperatures typically are within the range of 510C. Where sufficient data were available, more than 90% of the monitored hydrocarbon plumes were either stable or shrinking, rather than expanding. This evidence supported the interpretation that natural attenuation of hydrocarbons was important at the majority of these sites. Based on geochemical indicators, sulfate reduction appeared to be the most important terminal electron accepting processes linked to hydrocarbon oxidation, followed by iron reduction. Oxygen, nitrate and manganese also appeared to be significant terminal electron acceptors. The relative importance of methanogenesis could not be assessed due to a lack of data. Armstrong et al. reported that theoretical biodegradation capacity for these plumes, based on dissolved concentrations of electron acceptors, generally exceeded hydrocarbon concentrations (expressed as BTEX), by 77% in shrinking plumes, and by 56% for stable plumes. The estimated first order biodegradation rate constants for BTEX at the sites in western Canada reviewed by Armstrong et al. (2002) ranged from 0.0002 to 0.017day 1, with the majority of plumes having rates ranging from 0.001 to 0.005day 1. These results indicated plume halflives for the individual BTEX components of approximately 1 to 2years. These ranges are of the same order in magnitude and overlap with ranges of BTEX biodegradation rate constants observed in plumes at warmer sites, as documented for example in surveys conducted in the United States (Suarez and Rifai, 1999). The authors suggested that possible causes for a tendency for marginally lower biodegradation rates for the western Canadian sites were their cooler temperatures, and possible influences of co-contaminants, which are often present in hydrocarbon plumes at upstream oil and gas facilities in western Canada. Recently Ulrich et al. (2006) provided a summary of published information on biodegradation rate constants
for BTEX components under anaerobic conditions where temperatures have been reported. This included a graphical summary of inferred first-order rate constants either reported, or calculated using the Buscheck and Alcantar (1995) solution (Fig. 2). Ulrich et al. (2006) reported 95% confidence intervals for the rate constants (a) as reported, and (b) normalized to 5C, based on an assumed Q10 = 2. Approach (b) was chosen to create a data set that could be used by regulators and practitioners for estimating biodegradation rate constants for natural attenuation in cold-climate field settings. Given that the ranges in temperature normalized rates provided by Ulrich et al. (2006) (Fig. 2) are drawn from 60 studies (including 49 case histories at field sites), using 95% confidence intervals, these ranges of values appear to provide reasonable conservative/ proxy estimates of rate constants for biodegradation of BTEX in fuel plumes in groundwater at cold sites. The entire database of information is available at http:// environment.gov.ab.ca/info/library/6684.pdf. 4. Bioremediation of hydrocarbons in groundwater at cold sites: review of individual studies As recently reviewed by Van Stempvoort and Grande (2006), a significant and growing number of studies have indicated successful applications of bioremediation to clean up hydrocarbon-contaminated soils at cold sites, but in contrast, information on the feasibility and/ or successful application of bioremediation to clean-up of hydrocarbon-contaminated groundwater at cold sites is much more limited. This section provides a summary of results from some of the pertinent groundwater studies. Typically the pioneering groundwater studies that were conducted in the 1980s at relatively cold sites in North America did not emphasize the role of temperature in the bioremediation, and often temperature data were not reported. Particularly rare are studies of the biodegradation of hydrocarbons in groundwater at sites that have permafrost. 4.1. Geographic range and geologic settings of field studies The focus of this review is on field investigations that have been conducted in North America (24 sites: Tables 2 and 3); studies from Scandinavia and the Baltic region of Europe have also been included (11 sites: Table 4). Some of the earliest relevant field studies were conducted in the Great Lakes area of North America, including the USA (Wilson et al., 1986; Rifai et al., 1988; Chiang et al., 1989)
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Fig. 2. Ranges of estimated first order rate constants for biodegradation of petroleum hydrocarbons under anaerobic conditions, based on field data, modified after Ulrich et al. (2006). The data compiled for this figure was obtained from 49 case histories at field sites: 8 in western Canada; 1 in Ontario, Canada; 1 in Australia, 3 in Alaska and 36 at other USA locations.
and Canada (Barker et al., 1987; Acton and Barker, 1992). By the mid-1990s, colder sites north of the 60th parallel in both the USA (Braddock and McCarthy, 1996; Westervelt et al., 1997) and Canada (Carss et al., 1994) had been studied. Over the past decade, the geographic range of the investigations in North America has expanded to include various other locations in Canada, including Alberta (Lai et al., 2001; Van Stempvoort et al., 2002, 2005, 2007, in press), Labrador (Curtis and Lammey, 1998), northern Manitoba (Shields et al., 1997), northern Ontario (Bickerton et al., 2005), Northwest Territories (Van Stempvoort et al., 2006; Van Stempvoort and Talbot, 2006), and Yukon Territory (Whyte et al., 1998; Billowits et al., 1999; Soloway et al., 2001). The majority of the studies (Tables 2, 3, and 4; Fig. 3) were investigations of hydrocarbon plumes in sand or sand/gravel aquifers. Other geologic media included fractured rock (Carss et al., 1994; Van Stempvoort et al., 2006; Eriksson et al., 2006), gravel fill over peat (Mitchell and Friedrich, 2001) and silt/clay deposits (Van Stempvoort et al., 2002, 2007, in press). Based on the limited available information, geology does not appear to be a major constraint on the in situ biodegradation of hydrocarbons in groundwater. Authors reported evidence for significant intrinsic or enhanced in situ bioremediation of hydrocarbons in all of the different types of geologic
media that were investigated, including all of the field studies of groundwater in fractured rock (3 studies in Canada, 1 study of 4 sites in Sweden), for example. Though studies of hydrocarbon bioremediation in cold, fractured rock environments are rare, this topic is very relevant to large cold regions, including the Canadian Shield, for example, which includes an area of approximately 4.8million square km in Canada. 4.2. Thermal regime, permafrost setting For the sites considered in this review (Tables 2, 3 and 4), the average annual air temperatures vary between 12 and 8C, whereas groundwater temperatures reported in studies at these sites ranged from 0.3 to 15.8C. Typically the groundwater temperatures were measured in summer. Almost all of the sites have either no permafrost, or sporadic to discontinuous permafrost. Three exceptions are the three case studies included in this review, two of which provide evidence for significant biodegradation of hydrocarbons in suprapermafrost and/or intrapermafrost groundwater. When groundwater is present in the upper few meters below ground surface, its temperature fluctuates seasonally, which may include freezing during the winter (e.g., suprapermafrost water in zones of continuous
D. Van Stempvoort, K. Biggar / Cold Regions Science and Technology 53 (2008) 1641 Table 2 Summary of information on cold climate sites from the USA included in this review Geographic location (reference(s)) Plume type (geologic medium) Temperature annual average air (reported groundwater) 7 C (9.3 to 15.8 C) Biodegradation evidence
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Type of microorganisms indicated/suspected (type of field approach/treatment) Aerobic and methanogenic (evidence for intrinsic bioremediation)
Traverse City, Benzene, toluene and xylenes Michigan, USA from aviation fuel spill (sand (Wilson et al., and gravel aquifer) 1986; Rifai et al., 1988)
Northern Gas condensate at a gas plant Michigan, USA (sand aquifer) (Chiang et al., 1989) Bemidji, Minnesota, USA (Baedecker et al., 1993; Bennett et al., 1993; Eganhouse et al., 1993; Rooney-Varga et al., 1999) Adak, Alaska, USA (Bradley and Chapelle, 1995) Near Barrow, Alaska, USA (Braddock and McCarthy, 1996) (Case study #1) Fairbanks, Alaska, USA (Westervelt et al., 1997) Crude oil from pipeline (sand and gravel aquifer)
Est. 7 C
3.2 C
Field data indicated rapid biodegradation of the aromatic hydrocarbons under both aerobic and methanogenic, anaerobic conditions; modeling of 1985 plume data: aromatic hydrocarbon mass loss: 1% day 1; microcosm tests (Table 5) Natural attenuation of benzene, toluene and xylenes was found to be approximately 1% day 1, but slower in the O2 depleted, central portion of plume, microcosm tests (Table 5) Plume became anoxic, with dissolved Fe, Mn and methane released to groundwater, appearance of organic acids, shift in isotopic composition of dissolved inorganic C: plume migration (aromatics and alkanes) attenuated by biodegradation; enrichment of Geobacter sp. in plume
Aerobic, anaerobic processes also suggested (evidence for intrinsic bioremediation)
Aerobic and anaerobic Fe, Mn reducers and methanogens (evidence for intrinsic bioremediation)
Jet fuel (shallow sand aquifer)
4.7 C (4 to 6 C)
Toluene degradation in aerobic microcosms (Table 5)
Aerobic (concluded that intrinsic bioremediation might be a viable approach)
Gasoline, jet fuel spill in 1976 12 C (1.2 to 78 (sand and gravel deposits, 7.4 C) suprapermafrost groundwater)
Arctic diesel from underground 2.8 C storage tank (unconfined alluvial sand and gravel aquifer)
Near Fairbanks Alaska, USA (Richmond et al., 2001)
Benzene with trichloroethene, trichloroethane; toluene detected until 1994, contaminant source(s) unknown (alluvial sand and gravel aquifer) Fairbanks Alaska, Petroleum-distillate (alluvial USA (Braddock sand and gravel aquifer) et al., 2001)
2.8 C
2.8 C (3 to 4 C)
Aerobic and anaerobic nitrate, iron, sulfate reducers (concluded intrinsic remediation could be part of management strategy, planned to combine with novel artificial high layer in permafrost to contain contaminant plume) Anaerobic iron, manganese, sulfate reducers, methanogens (natural attenuation of BTEX to non-detectable levels within 45 m of source area, 50 m upgradient of municipal water supply wells) Concentrations of ferrous iron and Iron and sulfate reducers sulfide, hydrocarbons (concluded intrinsic bioremediation was not significant, that natural dilution reduced hydrocarbon concentrations) Microbial activities and mineralization Aerobic (evidence for intrinsic of selected aromatics in laboratory tests bioremediation) (Table 5); aquifer tends to be anaerobic, observed 0.2 to 3.6 mg/L dissolved oxygen in groundwater Depleted oxygen and nitrate in plume, with increases in ferrous iron and sulfide, and higher microbial populations; aerobic microcosm tests indicated significant rates of benzene mineralization, stimulated by nutrient addition (Table 5) Geochemical evidence for anaerobic hydrocarbon degradation linked to reduction of sulfate, iron and manganese, methanogenesis; calculated first-order BTEX biodegradation rates: 8 to 21% day 1
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Table 3 Summary of information on cold climate sites from Canada included in this review Geographic location (reference(s)) Plume type (geologic medium) Annual average air temperature (measured groundwater temperature) Injected aromatic 7.4 C hydrocarbons, associated with landfill leachate (surficial sand aquifer) Landfill leachate (sand aquifer) 3.8 C Biodegradation evidence Type of microorganisms indicated/suspected (type of field approach/treatment)
Alliston, Ontario, Canada (Barker et al., 1987; Acton and Barker, 1992) North Bay, Ontario, Canada (Acton and Barker, 1992) Great Slave Lake, Northwest Territories, Canada (Carss et al., 1994)
Loss of aromatics injected with chloride/bromide tracer; concluded that the inferred field biotransformation rates in agreement with lab results; benzene recalcitrance Extensive biodegradation of aromatics injected with bromide tracer, most disappeared after 2040 days Oxygen consumption, decrease in TPH concentrations by 30%; decline in BTEX to mostly non-detectable levels; increase in hydrocarbon-degrading microorganisms by N 3 orders in magnitude; estimated 1200 L of petroleum mineralized After 2 years contaminated zone (undefined) was reduced by 50%
Aerobic and anaerobic (evidence for intrinsic bioremediation)
Anaerobic, fermentative and methanogenic bacteria (evidence for intrinsic bioremediation) Aerobic (pump and treat, oxygen and nitrate addition, reinjection)
Not identified (fractured bedrock)
5 C (0.3 to 8 C)
Northern Manitoba, Canada (Shields et al., 1997) Goose Bay, Labrador, Canada (Curtis and Lammey, 1998) Whitehorse, Yukon Territory, Canada (Whyte et al., 1998; Billowits et al., 1999; Soloway et al., 2001)
Diesel fuel (not reported)
0.5 C
Aerobic, (circulation of nutrient and oxygen-enriched groundwater)
Fuel including arctic diesel (sand and silt aquifer)
0.3 C
Diesel fuel/heating oil (shallow 0.7 C sand and silt)
Haines Junction, Pit disposal of oil refinery Yukon Territory, products (shallow sand-gravel Canada aquifer) (Billowits et al., 1999) Central Alberta, Canada (Lai et al., 2001) Aromatic hydrocarbons (BTEX) and other contaminants (chorinated hydrocarbons) in landfill leachate (sand aquifer)
Est. 0.5 C
Est. 4 C
Komakuk Beach, Fuel oil (gravel pad over peat Yukon Territory, and silt, permafrost present) Canada (Mitchell and Friedrich, 2001) (Case study #2)
11.4 C
Aerobic and anaerobic nitrate, iron and sulfate reducers (intrinsic bioremediation; suggested adding nitrate to the groundwater) Microbial enumeration and molecular Aerobic and anaerobic dieselanalyses indicated cold-adapted aerobic degraders (evidence for intrinsic and anaerobic bacteria present in bioremediation; groundwater aquifer, aerobic and anaerobic diesel- was treated by biosparging and degraders; DNA testing indicated genes nutrient biostimulation) involved in alkane degradation lab tests indicated mineralization of hexadecane (Table 5) Plate growth of bacteria in aquifer Suggested nitrate-reducers may samples greater at 5 C than 37 C, have been involved in DNA testing indicated genes involved hydrocarbon degradation in alkane degradation; lab tests (evidence for intrinsic indicated degradation of aromatics and bioremediation) hexadecane Mixed contaminant plume including Aerobic and anaerobic BTEX is depleted in oxygen and hydrocarbon degraders (evidence sulfate, and enriched in methane and for intrinsic bioremediation) dissolved iron; microbial assays indicated the presence of iron and sulfate reducing bacteria and hydrocarbon degraders BTEX were removed during treatment Aerobic (multiphase extraction, groundwater treated ex situ in bioreactors: aeration, nutrients, capacity for intrinsic bioremediation reported to be low) Electron acceptors apparently involved in biodegradation of BTEX: oxygen, nitrate, ferric iron and sulfate; increase in alkalinity
D. Van Stempvoort, K. Biggar / Cold Regions Science and Technology 53 (2008) 1641 Table 3 (continued ) Geographic location (reference(s)) Plume type (geologic medium) Annual average air temperature (measured groundwater temperature) Diesel (fractured bedrock) Est. 4 C Biodegradation evidence
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Type of microorganisms indicated/suspected (type of field approach/treatment)
Alberta Canada (Cross et al., 2003)
Alberta, Canada (Van Stempvoort et al., 2002, 2007) Alberta, Canada (Van Stempvoort et al., 2005) Diesel (sand and gravel, silt) Yellowknife, Northwest Territories, Canada (Barnette et al., 2005) Moose Factory, Diesel fuel Ontario, Canada (surficial sand aquifer) (Bickerton et al., 2005)
Aerobic and anaerobic (concluded intrinsic bioremediation of groundwater could potentially be enhanced with nutrient addition) Natural gas condensate (silt/ Est. 4 to 6 C (5 Field injection of sulfate with a bromide Sulfate and iron reducing clay/sand aquitard) to 8 C) tracer; observed loss of sulfate over bacteria dominant; aerobes, several months of 45 mg/L per day methanogens; (inferred intrinsic elevated iron, methane in plume bioremediation, suggested enhancement possible) Natural gas leaking along well 1.2 C Lower sulfate concentrations, stable Sulfate reducing bacteria, bore (confined sand and grave (approximately isotope shift in sulfate and dissolved possibly in consortia 5 C) inorganic carbon aquifer) 5 C Reduction of BTEX concentrations in some monitoring wells observed over an 8 month period No details; (focus was bioventing focus of the hydrocarboncontaminated vadose zone)
Laboratory tests (see Table 5)
1.1 C (0.5 to 9 C)
Colomac mine, Northwest Territories, Canada (Case study #3)
Diesel fuel/fractured bedrock, permafrost
Est. 7.8 C (2 to 6 C)
Diesel fuel, jet fuel, possibly Wrigley, Northwest other (unconfined sand and gravel aquifer) Territories, Canada (Van Stempvoort and Talbot, 2006)
Est. 5 C (2 to 2.4 C)
Monitoring suggested plume (BTEX, others) was stable, depleted oxygen, sulfate, elevated dissolved iron and manganese in contaminant plume; molecular analyses indicated different bacterial strains outside, inside the plume; some same/similar to those in other hydrocarbon plumes Plume has low O2, relatively high concentration of dissolved iron, most dissolved N is ammonia, sulfate apparently decreases downgradient, with isotope shift suggesting sulfate reduction, short-chain fatty acids in plume Higher dissolved iron and lower sulfate associated with hydrocarbons present in groundwater
Anaerobic (evidence for intrinsic bioremediation)
permafrost). At greater depths, groundwater has a relatively stable temperature. For example, at Wrigley, Northwest Territories, Canada, the water table in an unconfined sand and gravel aquifer occurs at 25m below ground, where the temperature remains at 2C yearround (Van Stempvoort and Talbot, 2006). Such differences in thermal regimes, including the extent of temperature fluctuations and freezing events, may have important effects on the type of hydrocarbon-degradingmicroorganisms/consortia that are present in groundwa-
ter, and specifically those that degrade hydrocarbons. Aside from a few laboratory studies on the effect of cyclic freezing on bioremediation of hydrocarbons in soils (Eriksson et al., 2001; Brresen et al., 2006), there appears to be a research gap regarding this topic. All (21) of the field studies listed in Tables 2, 3 and 4 that had mean annual air temperatures (MAAT) at or above 0C (10 in North America, 11 in Baltic region) reported evidence for in situ bioremediation of hydrocarbons in groundwater. For the remaining studies in
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Table 4 Summary of information on cold climate sites from the Baltic region (northern Europe and Scandinavia)included in this review Geographic location/study Plume type/geologic medium Annual average Biodegradation evidence air temperature Est. 7.5 C Disappearance of aromatic hydrocarbons and other organic contaminants downgradient, associated with loss of O2, nitrate and sulfate, appearance of methane, ammonia, Fe2+, Mn2+ and sulfide, appearance of some organic intermediate metabolites in the plume Increase in dissolved iron and alkalinity in hydrocarbon plume; depletion of sulfate and nitrate within the plume BTEX in plume are being degraded under aerobic, iron- and nitrate-reducing conditions; BTEX degradation rates are estimated to be 0.0003 to 0.016 day 1 Numerical modeling result: estimated half life of fuel plume in groundwater of 1800 days; concluded that as a result of intrinsic bioremediation only a small part of fuel plume reaches river Reduced hydrocarbon levels in groundwater from 22.36 mg/L to 0.02 3.61 mg/L Groundwater is anoxic, laboratory studies indicated biodegradation of mineral oil, including n-alkanes in subsurface samples under aerobic and anaerobic, methanogenic conditions; highest aerobic and methanogenic activities were in most contaminated samples; microbial diversity studied by DNA/molecular analyses indicated strain with similarity to known anaerobic alkane degraders Injected toluene, xylene and other aromatics along with bromide tracer; observed losses; in main plume observed depletion of O2, nitrate and sulfate, high Fe, Mn, alkalinity; metabolites of hydrocarbon degradation in plume; laboratory tests: Zheng et al. (2002a,b,c) Compared to pristine setting, dieselcontaminated groundwater had higher total number of microorganisms, somewhat higher populations of iron-, sulfate- and nitrate-reducers, elevated alkalinity; low sulfate, trace of nitrite [evidence of nitrate-reduction] Compared to pristine setting, dieselcontaminated groundwater had higher total number of microorganisms, higher populations of iron-, sulfateand nitrate-reducers, detection of metabolites of hydrocarbon degradation; elevated alkalinity; trace of nitrite, indicating denitrification Type of microorganisms indicated/ suspected (type of field approach/ treatment) Aerobic, nitrate-, sulfate-, Fe- and Mnreducers, methanogens in distinct zones (evidence for intrinsic bioremediation)
Vejen, Denmark Landfill leachate (Lyngkilde (unconfined sandy and aquifer) Christensen, 1992a,b)
Riga, Latvia (Banks et al., 1998) Radsted, Denmark (Mossing et al., 2001) Near Riga, Latvia (Spalvins et al., 2001) Szprotawa, Poland (Paweczyk et al., 2003) Hanko, Finland (Salminen et al., 2004; Purkamo et al., 2004)
Fuel, largely diesel (unconfined sand aquifer) Petrol fuel/gasoline (sand aquifer)
7.3 C
Iron-, nitrate- and sulfate-reducers (evidence for intrinsic bioremediation) Aerobic, nitrate- and iron-reducers (evidence for intrinsic bioremediation)
Est. 7.5 C
Jet fuel (sand aquifer) 7.3 C
Details not included (evidence for intrinsic bioremediation)
Aircraft fuel (shallow 8 C sand, gravel, silt,clay)
Lightweight fuel, lubrication oil at industrial dumpsite (sand, gravel, silt, clay)
6 C
Aerobic, based on treatment approach (inoculation of groundwater with bacteria, in situ aeration and addition of biogenic substances) Aerobic and anaerobic including methanogens (evidence for intrinsic bioremediation)
Oslo, Norway (Konowski et al., 2005)
Jet fuel (sand and gravel)
5.7 C
Aerobic; nitrate-, iron- and sulfatereducers (evidence for intrinsic bioremediation; inferred that intrinsic biodegradation of toluene could be an efficient approach)
Murjek, Sweden Diesel (fractured (Eriksson rock) et al., 2006)
Est. 0 C
Suggested aerobic bacteria dominant (evidence for intrinsic bioremediation)
Ludvika, Sweden (Eriksson et al., 2006)
Diesel (fractured rock)
Est. 5 C
Suggested anaerobic bacteria dominant (evidence for intrinsic bioremediation)
D. Van Stempvoort, K. Biggar / Cold Regions Science and Technology 53 (2008) 1641 Table 4 (continued ) Geographic location/study Sala, Sweden (Eriksson et al., 2006) Plume type/geologic medium Gasoline (fractured rock) Annual average Biodegradation evidence air temperature Est. 5 C Compared to pristine setting, gasolinecontaminated groundwater had higher total number of microorganisms, higher populations of iron-, sulfate- and nitratereducers, low sulfate, elevated alkalinity, trace of nitrite Fuel-contaminated groundwater had more abundant microorganisms, including nitrate-, iron- and sulfate reducers, presence of ferrous iron and sulfide, elevated alkalinity, depleted sulfate and ferric iron, detection of metabolites of hydrocarbon degradation; RNA-based analyses indicated presence of bacteria similar to other hydrocarbon-contaminated environments Type of microorganisms indicated/ suspected (type of field approach/ treatment)
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Suggested anaerobic bacteria dominant (evidence for intrinsic bioremediation)
Bldinge, Sweden (Eriksson et al., 2006)
Diesel and gasoline (fractured rock)
Est. 7 C
Anaerobic bacteria dominant (evidence for intrinsic bioremediation)
North America, which had MAAT below 0C ( 12 to 0.3C), the large majority (12 of 14) reported significant in situ biodegradation of hydrocarbons in groundwater (intrinsic or enhanced). This included the site with the coldest MAAT of 12C (see Section 4.7, Case study 1). Collectively, this information indicates that the potential to utilize in situ bioremediation as a technology to clean-up petroleum-contaminated groundwater in cold regions is very promising, including sites with sub-zero MAAT and presence of permafrost. At the second coldest site included in this survey, investigators reported that capacity for intrinsic bioremediation was found to be low. However, an ex situ bioremediation technology was applied to treat the groundwater, which included aeration and nutrient addition in bioreactors (see Section 4.7, Case study 2). 4.3. Types of hydrocarbon sources, contaminants investigated For the majority (23 of 35) of the field sites reviewed (Tables 2, 3 and 4; Fig. 4), the hydrocarbon plumes in groundwater were derived from fuel, including diesel, gasoline, jet/aviation fuel, and other unidentified fuel types. Other types of petroleum sources investigated were crude oil, refinery wastes, natural gas and/or gas condensates, landfill leachate, and sources unknown or not identified. Most studies focused on the attenuation of plumes of dissolved monoaromatic hydrocarbons, particularly BTEX (benzene, toluene, ethylbenzene and xylenes), although some considered other aromatic species or focused on total extracted/detected hydro-
carbons (Fig. 5). In situ biodegradation was reported to be significant in all types of plumes that were investigated. However, given the variety of conditions and methodologies for the studies included in this review, there remains a gap in definitive, quantitative information regarding the relative biodegradability of hydrocarbon plumes derived from various types of petroleum sources in various hydrogeological settings under cold climate conditions. 4.4. Types of remediation investigated 4.4.1. Intrinsic bioremediation The large majority (27 of 35) of the field studies of petroleum hydrocarbon plumes in groundwater at cold sites were investigations of intrinsic bioremediation
Fig. 3. Geological setting of the hydrocarbon plumes at the 35 sites reviewed in this study.
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Fig. 4. Source types of the hydrocarbon plumes at the 35 sites reviewed in this study.
(Tables 2, 3, and 4; Fig. 6). In 20 of these cases, the evidence for intrinsic bioremediation that was gathered included an emphasis on hydrogeochemistry, specifically data regarding the distribution of electron acceptors, such as oxygen, sulfate, nitrate, or potential products of redox reactions associated with hydrocarbon biodegradation, such as dissolved ferrous iron and manganese, sulfide or methane. This review found that evidence for intrinsic bioremediation included the detection of lower concentrations of electron acceptors in the contaminant plume, and/or higher concentrations of reduced product species (e.g., Fig. 7). Particularly common were reports of higher concentrations of dissolved iron or depleted nitrate or sulfate in the hydrocarbon plumes as evidence for the role of anaerobic bacteria (iron-, nitrate- and sulfate-reducers) (Fig. 7). Reports of evidence for aerobic hydrocarbon degraders (relatively low or negligible oxygen in the plumes) and methanogens (presence of methane) were also common. In this review, some of the cold-climate sites lacked evidence for oxygen depletion (lower or negligible concentrations) in the hydrocarbon plumes, compared to pristine conditions, because the groundwater was anaerobic both inside and outside of the hydrocarbon plumes (e.g., Van Stempvoort et al., 2005). At other sites, background concentrations of sulfate and/or nitrate were very low, precluding the importance of these electron acceptors in biodegradation of hydrocarbons. The role of methanogens is likely to have been under-reported because methane was not analyzed in all studies.
In some studies, chemical evidence for intrinsic bioremediation included the detection of probable biodegradation metabolites including various partially oxidized petroleum hydrocarbons (e.g., Eganhouse et al., 1993; Eriksson et al., 2006) and short-chain fatty acids (Van Stempvoort et al., 2006, in press). In some plumes, higher alkalinity (e.g., Konowski et al., 2005; Van Stempvoort et al., in press) or alkalinity/hardness ratio (Eriksson et al., 2006) was apparently an indicator that hydrocarbons had been mineralized to dissolved CO2. Some authors have reported shifts in the isotopic composition of dissolved inorganic carbon that were associated with mineralization of hydrocarbons to CO2 (Baedecker et al., 1993; Van Stempvoort et al., 2002, 2005). Stable S and O isotope data have supported the
Fig. 5. Diagram illustrating the emphasis on analyses of aromatic compounds, including BTEX, at the field sites.
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Fig. 6. Bioremediation approaches investigated at the 35 groundwater sites included in this review.
interpretation that dissolved sulfate had been an important electron acceptor during intrinsic bioremediation of a natural gas plume (Van Stempvoort et al., 2005) and a fuel plume (Van Stempvoort et al., 2006, see Case study #3). Some relevant studies of intrinsic bioremediation included microbial analyses, including various enumeration techniques for total bacteria, and some techniques more specifically for hydrocarbon-degraders, sulfate reducers, iron-reducers, nitrate-reducers and/or methanogens (e.g., Carss et al., 1994; Lai et al., 2001; Cross et al., 2003). Typically the studies found that bacteria, either total populations or more specific groups, were more abundant and/or active in plumes compared to un-contaminated groundwater, and more active/abundant in treated groundwater compared to untreated. For example, Carss et al. (1994) found that the population of hydrocarbon-degrading microorganisms increased by more than three orders in magnitude in response to aeration and biostimulation. Over the past decade, some relevant intrinsic bioremediation studies have focused specifically on microbi-
ology, employing both comprehensive microbial enumeration procedures and molecular analyses (Whyte et al., 1998; Billowits et al., 1999; Purkamo et al., 2004; Eriksson et al., 2006). For example, Eriksson et al. (2006) enumerated total bacteria, most probable numbers of anaerobes, nitrate-, iron-, and sulfate-reducing bacteria, and also conducted DNA/RNA analyses to determine specific types/strains. They noted that the bacteria found in contaminated groundwater in fractured rock in Sweden were similar to bacteria in other hydrocarbon-contaminated environments. Based on reported molecular analyses, it appears that some strains or types of bacteria that occur in hydrocarbon plumes may be widespread geographically. For example, Dojka et al. (1998), Purkamo et al. (2004) and Bickerton et al. (2005) reported Syntrophus sp. or closely related strains in Michigan USA, Finland, and northern Ontario, Canada respectively. Purkamo et al. indicated that Syntrophus sp. are known to participate in anaerobic alkane degradation. At the northern Ontario fuel plume site, Bickerton et al. found several other strains of bacteria that were close matches to those previously detected at other hydrocarbon-contaminated sites, including a Spirochaeta sp., previously detected in a jet fuel-contaminated aquifer in Michigan undergoing intrinsic bioremediation (Dojka et al., 1998). Rooney-Varga et al. (1999) and Bickerton et al. (2005) found Geobacter sp. in plumes in northern Minnesota USA and northern Ontario Canada, respectively. Collectively, the evidence summarized above indicates that a wide range of aerobic and anaerobic microorganisms are active in hydrocarbon plumes in groundwater at cold climate sites. It appears that further research is
Fig. 7. Evidence for anaerobic electron accepting processes in studies of plumes that emphasized the application of hydrogeochemical analyses.
32
required to compare the diversity and structure of microbial communities present in plumes at cold climate sites to those at warmer sites. These communities may include consortia of anaerobic microorganisms in syntrophic relationships, such as sulfate reducers, fermentative acetogens, and/or archaea (methanogens), where each group benefits from the metabolites of others, with the final result being partial or complete degradation of hydrocarbons (Dojka et al., 1998; Bickerton et al., 2005; Van Stempvoort et al., in press). 4.4.2. Active groundwater bioremediation approaches Six of the studies reported applications of active bioremediation techniques to clean up hydrocarboncontaminated groundwater at cold climate sites. These involved either a combination of ex situ aeration and biostimulation (Carss et al., 1994; Shields et al., 1997; Mitchell and Friedrich, 2001), in situ biosparging with biostimulation (Soloway et al., 2001), in situ aeration with bacterial inoculation and addition of biogenic substances (details not provided) (Paweczyk et al., 2003), or by bioventing (Barnette et al., 2005). Two of the three ex situ applications included groundwater recirculation (Carss et al., 1994; Shields et al., 1997), while the third utilized a bioreactor (Mitchell and Friedrich, 2001). Details regarding the success of the biosparging approach were not available at the time of reporting by Soloway et al. (2001). Success was reported for each of the other active bioremediation approaches, measured as disappearance or reduction of BTEX concentrations (Carss et al., 1994; Mitchell and Friedrich, 2001; Barnette et al., 2005), decline in TPH/oil concentrations (Carss et al., 1994; Mitchell and Friedrich, 2001; Paweczyk et al., 2003), oxygen loss (Carss et al., 1994), and/or shrinkage of the plume (Shields et al., 1997). Other studies have suggested that in situ biostimulation with nutrients might enhance the bioremediation of the hydrocarbon-contaminated groundwater, based either on interpretation of field results (a study of intrinsic bioremediation by Curtis and Lammey, 1998) or laboratory test results (Billowits et al., 1999; Cross et al., 2003). Following field injection tests that had indicated conservative estimates of sulfate reduction rates of 5mg L 1 day 1, Van Stempvoort et al. (2007, in press) suggested that it might be helpful to add sulfate as an electron acceptor to gas condensate plumes in Western Canada. 4.5. Biodegradation rates in cold groundwater A small minority of the field studies examined in this review included estimates of the rates of biodegradation of the dissolved hydrocarbons in the contaminant plumes
(Tables 2, 3 and 4). For example, Rifai et al. (1988) reported field-based first order biodegradation rate constants (or half life equivalents) for BTEX in groundwater that fall within the normalized ranges derived by Ulrich et al. (2006) for anaerobic biodegradation, as shown on Fig. 2. In contrast, Chiang et al. (1989) and Westervelt et al. (1997) inferred higher biodegradation rate constants for BTEX in cold groundwater, ranging from 0.03 to 0.1day 1 and 0.08 to 0.21day 1 respectively, both ranges above the normalized ranges inferred by Ulrich et al. (Fig. 2). In the case of Chiang et al. (1989), the biodegradation was, at least in part, inferred to be an aerobic process, which may account for the faster inferred rates (see following section). Positive inferences about high biodegradation rates have been encouraging for proponents of bioremediation for cold climate sites. However, given the uncertainty in various parameters used in such calculations (e.g., estimated groundwater velocities), we recommend that fast outliers (e.g. Westervelt et al., 1997), above the normalized ranges provided by Ulrich et al., should be viewed with discretion. Although most of the reported biodegradation rates for hydrocarbons in cold groundwater are for BTEX compounds, some researchers have reported rates for other hydrocarbon components. For example, Spalvins et al. (2001) estimated that the first order biodegradation rate constant for oil in groundwater in Latvia (immiscible plus dissolved) was 0.0004day 1 (half life of 1800days). Low or insignificant intrinsic rates of hydrocarbon degradation were reported in two field studies of groundwater at cold climate sites (Mitchell and Friedrich, 2001; Richmond et al., 2001). One of these was one of coldest sites (MAAT = 11C) included in this review, located at Komakuk Beach in Yukon Territory, Canada (Mitchell and Friedrich, 2001: see Case study 2). The other report of negligible hydrocarbon biodegradation was a study of a mixed contaminant plume at Fairbanks Alaska (Richmond et al., 2001). In contrast, other studies of fuel plumes in the same geological setting in the Fairbanks area have indicated significant biodegradation of hydrocarbons (Westervelt et al., 1997; Braddock et al., 2001). Furthermore, despite their negative conclusion about intrinsic bioremediation, Richmond et al. (2001) reported concentrations of ferrous iron and sulfide in that plume, which suggested microbial iron and sulfate reduction were dominant terminal electron accepting processes in the aquifer (i.e. that anaerobic bacteria were active in the groundwater at this site). Together, this evidence suggests that the complex mixture of contaminants in the plume studied
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by Richmond et al. may have limited the hydrocarbon biodegradation potential. Confirmation of this hypothesis would require further study. 4.6. Relationship of biodegradation rates to oxygen availability, temperature, other factors: evidence from laboratory tests Some of the studies listed as field investigations in Tables 2, 3 and 4 included laboratory microcosm tests with aquifer and/or groundwater samples (Table 5). The majority of tests with aquifer/groundwater samples listed in Table 5 were conducted either completely under aerobic conditions, or using combination of both anaerobic and aerobic tests. A few researchers applied only anaerobic tests (Acton and Barker, 1992; Zheng et al., 2002a,b,c). Where compared, mineralization/biodegradation rates tended to be slower under anaerobic conditions compared to aerobic, for example by factors of 440 in studies reported by Wilson et al. (1986), Barker et al. (1987), Cross et al. (2003), and Salminen et al. (2004). However, Billowits et al. (1999) reported that aeration did not enhance the hexadecane degradation rate in tests with aquifer samples saturated with groundwater from a fuel plume at Whitehorse, Yukon Territory, Canada. The effect of temperature on microbial growth and/or the biodegradation rate of hydrocarbons in groundwater and/or aquifer sediments has been examined in laboratory studies by Bradley and Chapelle (1995), Braddock et al. (2001), Cross et al. (2003) and Van Stempvoort et al. (2004). Bradley and Chapelle (1995) challenged the conventional assumption that psychrophilic microorganisms have slower metabolism than mesophilic microorganisms. The conventional Q10 assumption had inferred that the rate of biodegradation of contaminants would be lower by half with each 10C decrease. Bradley and Chapelle studied microorganisms in microcosms containing samples from a jet fuelcontaminated shallow sand aquifer in Adak, Alaska, which they reported to be psychrophiles. In experiments under aerobic conditions, these microorganisms were capable of degrading toluene at 5C at a faster rate (by approximate factor of two) than mesophiles growing aerobically in other microcosms containing sediment from a petroleum-contaminated shallow aquifer in South Carolina at 20C. The groundwater temperature at the Alaska site was reported to be 46C. They concluded that intrinsic remediation (i.e., monitored natural attenuation) might be a viable approach for cold sites. Braddock et al. (2001) also conducted tests under aerobic conditions, using hydrocarbon-contaminated soil
and groundwater from Alaska, at 4, 10, 15 and 25C. They found that microbial growth (heterotrophs and hydrocarbon degraders) was enhanced as the temperature increased from 4 to 10C, and was optimal at either 1015C or 25C. The above tests (Bradley and Chapelle, 1995; Braddock et al., 2001) were conducted under aerobic conditions, whereas it appears that intrinsic bioremediation of hydrocarbons in groundwater at cold sites is often dominated by anaerobic processes. In anaerobic laboratory tests by Cross et al. (2003), an increase in temperature from 10 to 20C resulted in an approximately two-fold increase in the degradation rate of total extractable hydrocarbons (i.e. Q10 = 2). In contrast, Cross et al. (2003) inferred a Q10 of 1.38 for biodegradation of dodecane in aerobic, nutrient amended tests over the temperature range 10 to 28C. In aerated tests, Van Stempvoort et al. (2004) found that the overall rates of losses of total and C6C10 fraction of hydrocarbons increased by 80 and 50%, respectively, when the temperature was increased from 4 to 23C. However, in O2-limited batch tests, an increase in temperature from 5 to 23C had no observable effect on the hydrocarbon loss/degradation rate. Several investigators have reported laboratory evidence that hydrocarbon biodegradation rates in groundwater increase with addition of various nutrient mixtures, including mixtures containing various K, PO4, NH4, NO3, SO4, and Cl salts (Braddock and McCarthy, 1996; + Braddock et al., 2001), NO3, NH4 , urea, and K3PO4 (Whyte et al., 1998; Billowits et al., 1999; Soloway et al., 2001) and a mixture of K2HPO4, NH4Cl and KNO3 (Cross et al., 2003). Van Stempvoort et al. (2004) found that addition of (NH4)2HPO4 enhanced the rate of hydrocarbon degradation in batches amended with ferrous sulfate, but not in batches amended with ferric iron (FeOOH). The study by Whyte et al. ((Whyte et al., 1998; Billowits et al., 1999; Soloway et al., 2001) with samples from a fuelcontaminated aquifer in Whitehorse, Yukon Territory in Canada had mixed results. The nutrient addition increased hexadecane mineralization in microcosms containing aquifer sediment samples saturated with groundwater, but not in tests with groundwater alone. Whyte et al. (1998) provided several hypotheses to explain these results, including the possibility that sessile microorganisms attached to aquifer sediment particles were more effective at degrading alkanes than planktonic microorganisms suspended in the groundwater. Laboratory evidence that nitrate (Cross et al., 2003; Fan et al., 2006), sulfate (Cross et al., 2003; Van Stempvoort et al., 2004; Fan et al., 2006) or ferric iron amendments (Van Stempvoort et al., 2004) may serve as an electron acceptor to enhance degradation has been
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Table 5 Summary of laboratory tests included in this review Geographic location of samples (study) Traverse City, Michigan, USA (Wilson et al., 1986; Hutchins et al., 1991) Plume type (geologic medium) Benzene, toluene and xylenes from aviation fuel spill (sand and gravel aquifer) Type of test Lab temperature (test Measured/observed rate/amount of period) degradation 12 C (aerobic 2 weeks; anaerobic 8 weeks) In study by Wilson et al., aromatic hydrocarbons declined by one order in magnitude under anaerobic conditions, by two orders under aerobic conditions; in anaerobic microcosms reported by Hutchins et al, benzene was recalcitrant, first order rate constants for other aromatics under denitrifying conditions ranged from 0.022 to 0.067 day 1 Inferred zero order rates of 0.03 mg/L day 1 for benzene, toluene and xylene biodegradation under aerobic conditions, much slower rates under anaerobic conditions Added benzene, toluene and ethylbenzene eliminated by 20 days, xylenes partially degraded
Microcosms with aquifer samples, some with nitrate/ nutrient amendments
Alliston, Ontario, Canada (Barker et al., 1987) Ottawa, Ontario, Canada (Berwanger and Barker, 1988)
Aromatic hydrocarbons (surficial sand aquifer)
Microcosms with aquifer cores 10 C (6080 d) and groundwater from site, aerobic and anaerobic
Landfill leachate (sand aquifer)
Michigan, USA Gas condensate at a gas (Chiang et al., plant (sand aquifer) 1989)
10 C (80 days) Aerobic microcosms containing aquifer sediments and groundwater; spiked with BTEX; addition of peroxide as source of oxygen to mediate biodegradation Microcosms with groundwater 10 C (2835 days) and aquifer material; dissolved O2: 0.0, 0.1, 0.5, 1, 2, 4, 5 or 8 mg L 1 Anaerobic microcosms with groundwater and aquifer samples, nitrate and glucose amendments Aerobic microcosms with aquifer sediments: mineralization of 14C-labelled toluene and acetate 10 C (187 days)
North Bay, Ontario, Canada (Acton and Barker, 1992) Adak, Alaska, USA (Bradley and Chapelle, 1995)
Landfill leachate (sand aquifer)
80 to 100% of added BTX were degraded, with half lives of 520 days in microcosms with O2 2 mg/L; rates slower with O2 b 2 mg/L; negligible degradation at lowest or no O2 No degradation observed
Jet fuel (shallow sand aquifer)
5 C (3, 25 h)
Near Barrow, Alaska, USA (Braddock and McCarthy, 1996)
Gasoline and jet fuel spills, (sand, gravel deposits, thin saturated zone above permafrost)
Aerobic microcosm tests with groundwater samples, nutrient additions: mineralization of 14 C-labelled benzene
10 C (10 days)
Northern Diesel fuel (not reported) Manitoba, Canada (Shields et al., 1997) Whitehorse, Diesel fuel (shallow sand Yukon, and silt) Canada (Whyte et al., 1998;
Bench scale batch-activated sludge test
5 C (unspecified)
Psychrophiles were capable of degrading toluene at 5 C at a faster rate (factor of two) than mesophiles growing aerobically in sediment from a petroleum-contaminated shallow aquifer in South Carolina at 20 C; overall microbial metabolic rates were similar at their respective in situ temperatures Groundwater in contaminant plume had greater benzene mineralization potential than groundwater sampled outside plume; benzene mineralization rates ranged from 0.1 to 0.5 mg L 1 day 1 in samples from contaminated wells and increased to 0.7 mg L 1 day 1 when nutrients were added Removal of up to 60% of the hydrocarbons
5 C (60 days) Aerobic and anaerobic microcosms containing aquifer samples, saturated with groundwater
Mineralization of 14C-labelled hexadecane (C16) by indigenous microorganisms,aeration did not enhance; nutrient treatment had very little effect on overall TPH
D. Van Stempvoort, K. Biggar / Cold Regions Science and Technology 53 (2008) 1641 Table 5 (continued ) Geographic location of samples (study) Plume type (geologic medium) Type of test Lab temperature (test Measured/observed rate/amount of period) degradation
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Billowits et al., 1999) Haines Junction, Pit disposal of oil refinery Yukon products (shallow sandTerritory, gravel aquifer) Canada (Billowits et al., 1999)
Fairbanks Alaska, USA (Braddock et al., 2001)
Olso, Norway (Zheng et al., 2002a,b,c)
Alberta Canada (Cross et al., 2003)
Moose Factory, Ontario, Canada (Van Stempvoort et al., 2004)
Hanko, Finland (Salminen et al., 2004; Purkamo et al., 2004)
concentrations. Anaerobic denitrification occurred in some tests Anaerobic and aerobic Microcosms: 5 C Nutrient addition enhanced the microcosm tests with aquifer (60 days) columns: degradation of TPH, whereas aeration samples - mineralization of 7 C (58 days) did not; degraded fraction of 14 C-labelled hexadecane; hydrocarbons appeared to consist largely aerobic soil column tests of linear compounds; indigenous bacteria reduction of TPH and oxygen were capable of degrading large fractions of naphthalene (50%) and toluene (30%) over 60 days, but not 14C-labelled hexadecane Petroleum-distillate (alluvial Aerobic tests with groundwater Microbial growth: 4, Microbial growth was enhanced as sand and gravel aquifer) samples, nutrient addition; 10, 15 and 25 C; temperature increased from 4 to 10 C, microbial growth; mineralization: 10 C optimal at either 1015 C or 25 C; mineralization of naphthalene, (up to 43 days) nutrient addition generally enhanced the benzene mineralization of benzene and naphthalene at 10 C Jet fuel (sand and gravel) Anaerobic column tests of 810 C (8 to Intrinsic biodegradation of toluene aquifer sediment with 17 days) (estimated average intrinsic rate of 0.16 groundwater 0.27 mM day 1) was coupled with the microbial reduction of ferric iron (Fe (III)); intrinsic biodegradation of 1,2,4trimethylbenzene was slower: 0.05 0.13 mM day 1) Diesel (fractured bedrock) Anaerobic microcosms with Anaerobic: 10 and Anaerobic: sulfate, nitrate/nutrients and higher temperature (20 C) resulted in groundwater, some with 20 C (790 days) nutrient/nitrate or sulfate aerobic: 10 and 28 C greater losses of total extractable hydrocarbons (38, 5170% and 46% amendments aerobic (187 days) respectively), compared to unamended, microcosms with groundwater, some with nutrient 10 C (20%) aerobic tests: mineralization amendments of 14C-labelled dodecane: without nutrients - 3%; with nutrients - up to 23% (10 C) to 36% (28 C) Fuel (shallow sand aquifer) Aerobic and oxygen-limited 45 and 23 C Overall losses/degradation rates of batch tests with aquifer aerobic: (60 d) O2 hydrocarbon degradation similar in all samples; some of latter with limited: (110 d) tests (aerobic or O2 limited, 45 or sulfate, ferric iron (FeOOH), 23 C). In O2 limited batches, those ammonium phosphate, and/or amended with ferric iron had largest humic substances added losses of hydrocarbons; nutrient addition enhanced the hydrocarbon losses in batches amended with sulfate, suggesting role of sulfate reducers; addition of humic substances had no noticeable effect in O2-limited batches Lightweight fuel, Aerobic and anaerobic 8 C anaerobic: (10 Average of 1544% (up to 64%) removal lubrication oil at industrial microcosms with soil samples 12 mo) aerobic: (3 of mineral oil in anaerobic tests, methane dumpsite (sand, gravel, silt, 4 mo) production;, average of 2731% (up to clay) 75%) removal in aerobic tests; preferential degradation of C10C15 fraction
reported. In microcosm tests by Cross et al. (2003) with groundwater from a diesel-contaminated fractured rock aquifer in Alberta, Canada, amendments with nitrate or nutrients had a larger positive effect on increasing the
biodegradation rate than the raising of temperature from 10 to 20C. Cross et al. (2003) also reported that sulfate amendments increased the hydrocarbon biodegradation rate in anaerobic microcosms.
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The results summarized above indicate that a range of factors, including temperature, the availability of various electron acceptors, and nutrients, exert some control on the rate of biodegradation of hydrocarbons in groundwater. However, given the limited scope of the studies conducted to date, significant further research would be required to firmly establish quantitative models of the interactive roles of these various factors on the rate of biodegradation of hydrocarbons in groundwater. Based on current results, we can conclude that temperature does not exert a consistent, predictable, over-riding control on the rate of biodegradation of hydrocarbons in groundwater. 4.7. Extreme case studies: coldest sites, permafrost settings 4.7.1. Case study 1: Barrow, Alaska, USA Braddock and McCarthy (1996) investigated biodegradation in hydrocarbon-contaminated groundwater in sand and gravel deposits at an Arctic site near Barrow, Alaska, adjacent to the Arctic Ocean. The soil and groundwater at this site were contaminated by gasoline and jet fuel spills in 197678. Here the annual average air temperature is 12C, with groundwater present as a relatively shallow, thin layer above the permafrost (i.e. suprapermafrost water), with short, localized groundwater flow paths inferred. Air temperatures at this site rise above freezing for 90days per year (JuneAugust). The authors found that although twenty years had elapsed since the hydrocarbon spills, BTEX concentrations were still elevated in the groundwater near the source of the contamination. During their monitoring program, the groundwater temperatures ranged between 1.2 and 7.4C. They found strong evidence for intrinsic bioremediation of the BTEX plume, including depleted oxygen and nitrate, increases in ferrous iron and sulfide, and higher microbial populations. The groundwater in the BTEX plume had greater benzene mineralization potential than groundwater sampled outside the plume, based on microcosm tests at 10C. In laboratory tests, hydrocarbon mineralization rates were stimulated by nutrient additions. The authors concluded that intrinsic remediation could be part of the management strategy. They planned to combine intrinsic remediation with a novel containment approach: the construction of a barrier was used to induce permafrost mounding to contain the contaminated groundwater. 4.7.2. Case study 2: Komakuk Beach, Yukon Territory, Canada Mitchell and Friedrich (2001) studied a hydrocarboncontaminated site at Komakuk Beach on the Arctic Ocean
coast in Yukon Territory, Canada, where the mean annual air temperature is 11.4C. Without providing details, they reported that the capacity for intrinsic bioremediation was found to be low. However, they did report that ex situ bioremediation of the groundwater was successful. Groundwater was extracted along with free phase hydrocarbons via a multiphase extraction system that was equipped with vacuum pumps. Following oil/water separation, the groundwater was transferred to a series of two bioreactors, in which the groundwater was aerated, circulated, and amended with nutrients (first bioreactor), to promote biodegradation of the hydrocarbons by indigenous bacteria. Volatilization from the bioreactors was also promoted, and final treatment included filtration and adsorption via organically modified clay and activated carbon. Monitoring indicated that the BTEX and TPH concentrations in the extracted groundwater varied up to 0.3mg/L and 9mg/L respectively, and analyses of samples of the effluent from the first bioreactor indicated removal of 5397% of the BTEX and 4489% of the TPH. 4.7.3. Case study 3: Colomac mine, Northwest Territories, Canada A preliminary investigation by Van Stempvoort et al. (2006) focused on fuel hydrocarbon plumes in groundwater within suprapermafrost zones (taliks, thaw bulb and active layer) in fractured rock at an abandoned gold mine in Northwest Territories, Canada. Based on temperature data collected in 2005, groundwater typically warmed from 12C in July to 34C in September. A higher temperature range in one well during the same period (3 to 6C) was possibly affected by heat transport from a heated warehouse to groundwater. Relatively low concentrations of sulfate in wells down gradient of the main areas of fuel contamination suggested that sulfate reduction was occurring, associated with biodegradation of the hydrocarbons. Dissolved iron concentrations were highest in up-gradient areas, including the source area of the former tank farm. Dissolved manganese was weakly correlated with dissolved iron. The overall decrease of both sulfate and iron concentrations along the inferred groundwater flow paths was potentially due to (a) sulfate reduction as an electron accepting process associated with biodegradation of hydrocarbons, and (b) precipitation of FeS in response to release of sulfide due to sulfate reduction. The geochemical evidence that sulfate reduction may be an important electron accepting process in the fuel plumes is supported by stable isotope analyses, which indicate that the sulfate in down gradient wells is relatively enriched in 34S and 18O, as expected if sulfate reduction is occurring along the inferred groundwater flow path.
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Other evidence for microbial activity in the fuel plumes, possibly associated with biodegradation of hydrocarbons, included the detection of (i) volatile fatty acids (acetate, butyrate, propionate) in a majority of the wells; (ii) reducing conditions in all wells; (iii) detectable ammonia in all wells, associated with low or no detectable nitrate; and (iv) low dissolved oxygen concentrations in all but one well. 5. Summary and conclusions Previous reviews on the bioremediation of petroleum hydrocarbons at cold climate sites have generally focused on aerobic processes in soils. Reviews of bioremediation applications for petroleum hydrocarbons in groundwater have lacked detailed information on the role of temperature. This review article addresses these literature gaps by providing an overview of information regarding the bioremediation of petroleum hydrocarbons in groundwater at cold climate sites, including information about anaerobic biodegradation processes at these sites. Over the past several decades, there have been a small number of studies of bioremediation of hydrocarbons in groundwater at cold sites, though much more limited than the number of bioremediation studies for soil in cold environments (i.e. unsaturated conditions). Some of the relevant groundwater studies have reported that the extents of hydrocarbon plumes were limited by natural attenuation, including intrinsic bioremediation. At a few sites, oxygenation of groundwater, and/or amendments with nitrate, were reported to be successful techniques for enhancing biodegradation of petroleum hydrocarbons. Both aerobic and anaerobic processes appear to be important at cold sites. Most of the existing relevant groundwater studies were for sites with either no permafrost, or with sporadic to discontinuous permafrost. Studies of hydrocarbon behavior/remediation options for the seasonally saturated zone of the active layer at sites with continuous permafrost are rare; studies of plumes in fractured rock environments at cold sites are also scarce. To date, the majority of investigations were at fuel spill sites; there were few studies on bioremediation of dissolved hydrocarbon plumes derived from crude oil or gas condensate. Based on this review, further research and field demonstrations are required to establish or confirm the applicability of bioremediation technologies to effectively clean up hydrocarbons in groundwater at cold climate sites, and to provide insight into the rates of biodegradation that may be expected. However, a number of studies in recent years have indicated that the application of intrinsic bioremediation at cold climate sites may be
feasible, which may include both aerobic and anaerobic biodegradation processes. There is a need to conduct further research to address the existing gaps in the understanding of applicability of bioremediation for groundwater in cold climate conditions. For example, data for fractured rock environments and permafrost conditions are rare. Key science gaps that require further information include: Case studies demonstrating specific conditions under which intrinsic bioremediation can be successfully applied as a management approach for groundwater at cold climate sites; Case studies demonstrating the successful application of specific active bioremediation approaches (e.g., biosparging, biostimulation) to remediate groundwater at cold climate sites; Guidance on any limitations and/or modifications of techniques that are required in order to apply bioremediation at sites which have permafrost. Acknowledgements Pamela Grande assisted with an earlier version of this review. We are grateful for review comments by Kelly Millar, and by three anonymous reviewers. Funding in part was provided by Environment Canada and by the federal (Canada) Program of Energy Research and Development (PERD). References
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Cold Regions Science and Technology 53 (2008) 16 41 www.elsevier.com/locate/coldregions

Steam sparging/ flushing

Unmanipulated, unstimulated, non-enhanced biological remediation of an environment; i.e. natural attenuation. f

Aerobic, anaerobic processes also suggested (evidence for intrinsic bioremediation)

Jet fuel (shallow sand aquifer)

Toluene degradation in aerobic microcosms (Table 5)

Aerobic (concluded that intrinsic bioremediation might be a viable approach)

Near Fairbanks Alaska, USA (Richmond et al., 2001)

Aerobic and anaerobic (evidence for intrinsic bioremediation)

Not identified (fractured bedrock)

Diesel fuel (not reported)

Aerobic, (circulation of nutrient and oxygen-enriched groundwater)

Fuel including arctic diesel (sand and silt aquifer)

Diesel fuel/heating oil (shallow 0.7 C sand and silt)

Type of microorganisms indicated/suspected (type of field approach/treatment)

Alberta Canada (Cross et al., 2003)

Laboratory tests (see Table 5)

Colomac mine, Northwest Territories, Canada (Case study #3)

Diesel fuel/fractured bedrock, permafrost

Aerobic and anaerobic (evidence for intrinsic bioremediation)

Aerobic and anaerobic (evidence for intrinsic bioremediation)

Anaerobic (evidence for intrinsic bioremediation)

Jet fuel (sand aquifer) 7.3 C

Details not included (evidence for intrinsic bioremediation)

Aircraft fuel (shallow 8 C sand, gravel, silt,clay)

Oslo, Norway (Konowski et al., 2005)

Jet fuel (sand and gravel)

Murjek, Sweden Diesel (fractured (Eriksson rock) et al., 2006)

Suggested aerobic bacteria dominant (evidence for intrinsic bioremediation)

Ludvika, Sweden (Eriksson et al., 2006)

Diesel (fractured rock)

Suggested anaerobic bacteria dominant (evidence for intrinsic bioremediation)

Suggested anaerobic bacteria dominant (evidence for intrinsic bioremediation)

Bldinge, Sweden (Eriksson et al., 2006)

Diesel and gasoline (fractured rock)

Anaerobic bacteria dominant (evidence for intrinsic bioremediation)

Microcosms with aquifer samples, some with nitrate/ nutrient amendments

Aromatic hydrocarbons (surficial sand aquifer)

Landfill leachate (sand aquifer)

Landfill leachate (sand aquifer)

Jet fuel (shallow sand aquifer)

Near Barrow, Alaska, USA (Braddock and McCarthy, 1996)

Bench scale batch-activated sludge test

Fairbanks Alaska, USA (Braddock et al., 2001)

Olso, Norway (Zheng et al., 2002a,b,c)

Alberta Canada (Cross et al., 2003)

Moose Factory, Ontario, Canada (Van Stempvoort et al., 2004)

Hanko, Finland (Salminen et al., 2004; Purkamo et al., 2004)

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