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    Galerias

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    of 10
    Effect of Nitrate Addition on Biorestoration of Fuel-Contaminated Aquifer: Field Demonstration by S. R. Hutchins’, W. C. Downs’, J. T. Wilson’, G. B. Smith’, D. A. Kovacs’, D. D. Fine’, R. H. Douglass’, and D. J. Hendrix® Abstract A spill of JP-4 jet fuel at the U.S. Coast Guard Air Station in Traverse City, Michigan, contaminated a water-table aquifer. An infiltration gallery (30 ft X 30) wasinstalled above a section of the aquifer containing 700 gal JP-4. Purge wells recirculated three million gallons of ground water per week through the infiltration gallery at a rate designed to raise the ‘water table above the contaminated interval. Ground water containing ambient concentrations of oxygen and nitrate was first recirculated for 40 days. Concentrations of benzene in monitoring wells beneath the infiltration gallery were reduced from 760 to< 1 ug/l. Concentrations of toluene, ethylbenzene, m,p-xylene, and o-xylene were reduced from 4500 to 17, 840 to 44, 2600 to 490, and 1400 to 260 ug/l, respectively. Average core concentrations of benzene, toluene, ethylbenzene, ‘msp-xylene, and o-xylene were reduced from 0.84 00.032, 3310013, 1810 0.36, S810 7.4, and 26 to 3.2 mg/kg, respectively. Ground water amended with nitrate (10 mg/l nitrate-nitrogen) and nutrients was then recirculated for 76 days. Final core concentrations of benzene, toluene, ethylbenzene, m,p-xylene, and o-xylene were 0.017, 0.036, 0.019, 0.059, and 0.27 mg/kg, respectively. Final aqueous concentrations were < 1 ug/lfor benzene and toluene, 6 ug/ for ethylbenzene, and 20 to 40 g/1 for the xylene isomers, in good agreement with predicted values based on residual fuel content and partitioning theory. Although alkylbenzene concentrations have been substantially reduced, the test plot istill contaminated with the weathered fuel. Based on stoichiometry, approximately 10 times more nitrate was consumed than could be accounted for by BTX icating that other compounds were also degraded under denitrifying conditions. Introduction Leaking underground storage tanks area major source of ground-water contamination by petroleum hydrocar- bons. There are approximataely two million underground tanks storing gasoline in the U.S., and there have been 90,000 confirmed releases reported in the last two years (OUST, 1990). Gasoline and other fuels contain benzene, toluene, ethylbenzene, and xylenes (BTX) which are hazardous compounds regulated by the U.S, Environmen- tal Protection Agency (EPA, 1977). Although these aro- matic hydrocarbons are relatively water-soluble, they are contained in the immiscible bulk fuel phase which serves as a slow-release mechanism for sustained ground-water con- tamination. Pump-and-treat technology alone is economi- cally impractical for renovating aquifers contaminated with bulk fuel, because the dynamics of immiscible fluid flow result in prohibitively long time periods for removal of the *U.S. EPA, Rober S. Kert Environmental Research Lab, ‘Ada, Oklahoma 74820. NSH Technology Services, Robert S. Keer Environmental Research Lab, Ada, Oklahoma 74820. "The Traverse Group, Ine, 2525 Acro Park Drive, Traverse City, Michigan 49684. “Solar Universal Technologies, Inc, Ground Water Remedi ation Division, Traverse City, Michigan 49684 Received May 1990, revised September, November 1990, and February 191, accepted February 1991 Discussion open until January 1, 1992 Vol. 29, No, 4GROUND WATER—July-August 1991 organic phase (Wilson and Conrad, 1984; Bouchard etal, 1989), Biorestoration has been recommended as treatment alternative and involves enhancing the activity of the native subsurface bacteria to degrade fuel hydrocarbons through addition of nutrients and other compounds. Aerobie bio- restoration has been shown to be effective for many fuel spills (Thomas et al,, 1987; Lee et al., 1988). However, success is often limited by the inability to provide sufficient oxygen to the contaminated zones due to the low water solubility of oxygen (Wilson etal, 1986). Nitrate can also serve as an electron acceptor and results in anaerobic biodegradation of organic compounds via the processes of nitrate reduction and denitrification (Tiedje, 1988). Because nitrate is less expensive and more soluble than oxygen, it may be more economical to restore fuel-contaminated aquifers using nitrate rather than oxy- gen, Several investigators have observed biodegradation of aromatic fuel hydrocarbons under denitrfying conditions (Kun eta, 1988; Major et al. 1988; Miheleic and Luthy, 1988; Hutchins etal, 1991). However, the process is not well understood at field scale where several other processes, including aerobic biodegradation, can proceed concomi tantly. There have been only a few field studies on nitrate- mediated biorestoration of fuel-contaminated aquifers. Results include complete removal of benzene and toluene with the xylenes being more recalcitrant (Battermann, 1986), a 95 to 98% reduction in purgeable alkylbenzenes (Sheehan et al, 1988), and complete removal of toluene with benzene, ethylbenzene, and the xylenes being unaf- 371 fected (Lemon et al, 1989). Although most of these field studies have demonstrated partial success, the complexity of the field sites and the limited monitoring data preclude a thorough evaluation of the proces. The use of nitrate to promote biological removal of fuel aromatic hydrocarbons was investigated for a JP- jet fuel spillat Traverse City, Michigan, through afield demonstra- tion project in cooperation with the U.S. Coast Guard Laboratory ests had indicated that denitrification would be a suitable alternative for biorestoration of the aquifer (Hutchins etal, 1991). The Coast Guard plans to evaluate nitrate-based biorestoration, aerobic biorestoration using hydrogen peroxide, and soil vapor extraction to determine which technology is most cost-effective for bringing the site tothe closure limit ofS g/l benzene in the ground water as specified by the Michigan Department of Natural Resources The objective ofthis study was to evaluate whether nitrate- based biorestoration could successfully attain this closure criterion and to quantitate the extent of remediation. Site Description In February 1985, four large underground storage tanks at a US. Coast Guard facility in Traverse City, Michigan were found to be leaking JP-4 jet fuel through faulty piping to ashallow underlying aquifer. By the time the leaks were discovered and the tanks and contaminated soil were excavated, several thousand gallons of JP-4 et fuel had been lost to the subsurface. A series of interdiction wells were installed to contain the contaminated ground water and equipped with product recovery pumps to recover free product overlying the water table (Figure 1). This sucoess- fully retained the plume within the facilty’s boundaries, however, large area predominantly underlying the con- crete apron and runway had been contaminated. Moreover, the seasonal rise and decline of the water table had effec- tively smeared the contamination over a 5 to 8 ft depth interval, resulting in residual saturation of JP-4 (up to 32,000 mg/kg) in the unsaturated zone as well as free product at the water table The aquifer is composed of thick glacial deposits with the upper portions being lacustrine in origin (Twentereta., 1985). These lacustrine glacial deposits consist of an upper sand and gravel unit and an underlying clay unit. The thickness of the sand ranges from 50 to 60 ft in the ‘immediate veinity ofthe spill and consist of Fine to medium grained sand in the upper 15 to 20 ft and coarse to very coarse sand with gravel in the lower section. The water table varies seasonally and ranges from 12to 8 f below the land surface. The average linear ground-water velocity is esti- mated to be 5 ft per day. Field Demonstration Project The focus of the field demonstration project is a 30 ft 30 ft infiltration study area located within the larger area contaminated by the JP-4 plume (Figure 1), An infiltration gallery was constructed to perfuse the study area with ‘ground water supplemented with nitrate and nutrients. Computer modeling of the hydraulics was conducted 10 design the infiltration system (Downs etal, 1989). Results of, the model indicated an infiltration rate of 200 GPM over the sm study area was required to create a water-table mound encompassing the contaminated zone. Thisenabled the con- taminated unsaturated zone within the study area to be completely saturated and thus allowed even distribution of nitrate and nutrients. The preexisting line of interdiction wells PP-5 through PP-8 were pumped at 15 GPM each With the effluents routed to a carbon treatment system. ‘These wells are screened throughout the aquifer and include the contaminated zone. In addition, five pumping wells, PP-SA through PP-9A, were installed to recirculate the recharge water back to the infiltration gallery. These wells are screened below the contaminated zone to avoid influx of free product. The pumping wells recirculate the water at 200 GPM, and the interdiction wells provide a net discharge of 60 GPM to retain nitrate and contaminants within the facility boundaries. ‘The infiltration gallery consists of a primary 4-in, PVC pipe equipped with twelve 2-in. PVC pipe arms, each arm being 150 in in length and containing 3/16-in. holes spaced ‘one in. apart to ensure even hydraulic distribution. The gallery is contained within a 3-f¢ gravel pack buried $ ft below land surface to prevent freezing during winter months. The bottom ofthe gravel pack is sloped downwards towards the center to concentrate the mound at the center of| the study area (Figure 2). The study area contains five cluster wells to monitor ground-water quality and 1 piezometers to monitor water levels and head loss across the contatninated zone, Each cluster wel is constructed of Yin. stainless steel tubing and contains six diserete sampling points with 40 X 40 mesh stainless stel screens. The sample points for each cluster well are spaced 2 ft apart with interspersed bentonite seals to prevent channeling of ground- ‘water recharge. The sample points for each cluster well are located both within and beneath the contaminated zone to allow monitoring of biodegradation and contaminant transport within the different regions. The lines for the cluster wells are routed below land surface to & sample building. The sample building also contains the equipment required for recirculating the ground water obtained by the pumping wells and the chemical addition facilites. a oom Ls Fig. 1. Plan view of field demonstration project. Ground. water Is recirculated to infiltration gallery at 200 GPM. Interdiction wells dispose of contaminated ground water at 60 GPM. Locations of original uel tanks are shown. Fig. 2. Cross section of infltration gallery showing location ‘of monitoring wells and plezomelers. Infiltration, using recirculated ground water without ‘amendments, commenced April 20, 1989 and was continued until the design recireulation rate was attained. This was maintained for two weeks to achieve hydraulic equilibrium. A tracer study indicated that vertical flow was uniform beneath the infiltration gallery with a hydraulic residence time of 8 hrs within the contaminated zone. The total hydraulic residence time was 7 to 12 days, depending upon the distance to each well and its respective pumping rate Nitrate and nutrients were then applied at design concentra- tions of 62 mg/| sodium nitrate, 10 mg/ monobasic pot sium phosphate, 10 mg/l disodium phosphate, and 20 mg; ‘ammonium chloride, and full operation of the system com- ‘menced May 31, 1989 and continued for two months. Per formance of the pilot project was assessed by monitoring both aqueous BTX and inorganic chemical concentrations throughout the system as well as by periodically coring through the contaminated zone in the study area. The final sample cores were taken August 9, 1989, shortly after nitrate addition ceased. Water Quality Analysis Water quality data were collected weekly during the project. These analyses included dissolved oxygen, nitrate, nitrite, and BTX from selected cluster monitoring well points, As shown in Figure 2, there are six well points for each cluster monitoring well, with the shallowest well point being designated Level | and the deepest being Level 6. The following discussion will focus on water quality at Level 2 (within the contaminated zone, above the original water table), Level 4 (jst beneath the contaminated zone), and Level 6 (further beneath the contaminated zone); the other well points were not sampled on a routine basis. Data were averaged for each of the five cluster monitoring well points across a given level. This was done to allow a concise description of changes in water quality during infiltration across the contaminated zone. A more complete dataset has been published (Hutchins et al., 1990) ‘The dissolved oxygen profiles for the injection water and the water at different levels are shown in Figure 3 Infiltration began on Day 3 and nitrate and nutrient addi tion began on Day 44, Samples were collected from the well points at Day 0 to provide background information. Because the aquifer naturally contains low organic carbon and is highly transmissive, oxygen levels were high except ‘where contamination occurred, and in fact were even sub- stantial at the bottom ofthe contaminated zone with values approximating 3 mg/l, However, oxygen concentrations dropped rapidly as water was recirculated through the con- taminated zone (Figure 3). This is probably due to aerobic biodegradation occurring within the contaminated zone which had originally been oxygen-limited. Oxygen concen- trations stabilized at 0.5 to 1.0 mg within the monitoring, wells by Day 7. By Day 20, the infiltration water consisted ‘mostly of water which had passed through the contaminated zone, causing influent oxygen levels to drop and leading to less oxygen consumption as recharge water moved across the contaminated zone. It appears that limited oxygen con- sumption occurred from Day 20 to Day 64 with litte oxygen removal afterwards, but this may not be significant given the resolution of the data, Based on the measured infiltration rates, the mass of oxygen added can be calculated using the following equation: M=/CFat ‘where M is the total mass in mg, C is the concentration in ‘mg/l, F is the infiltration rate in L/d, and tis the time in days. The integral is evaluated numerically using a trapezoi- dal algorithm. Mass estimates can be generated for each level throughout the vertical profile, and the differences between oxygen mass supplied in the infiltration water and that found at Level 6 corresponds to oxygen uptake within the contaminated zone, assuming that oxygen removal is due primarily to aerobie biodegradation within the contam- inated zone. This also assumes vertical flow through the contaminated zone. In fat, there isthe potential for lateral flow from the edges of the study area; however, because there are no monitoring well points along the lateral flow path, the effect of lateral flow cannot be quantified. This equation was also used to calculate mass fluxes for the other parameters (Table 1). === ection Water Level? Une sgt” uso] 0 2 40 60 ab 00 BD Tome 2098) Fig. 3. Dissolved oxygen profile beneath infiltration gallery. LSD is the least significant difference between means al the 90% confidence level. 1 Table 1. Calculated Mass of Nutrients and Contaminants in infiltration Water Before and Ater Nitrate Addition, and Changes in Mass After Passage Through Contaminated Zone ‘Before nitrate addition After nitrate addition (day = 310 44) (ay = 4410 112) ‘Total mass supplied Mass change from feed Total mass supplied Mass change from feed Parameter in recharge 10 Level In recharge 10 Level 6 Dissolved oxygen 2 35 ra 4 Nitrate-iteogen 3 25 0 499 Nitvte-nitrogen <2 = 66 25 ‘Ammonis-nitrogen 2 301 “18 Phosphate-phosphorus <2 7 9 2 Benzene 34 29 0 0 Toluene 16 “5.1 59 58 Ethylbenzene 88 456 43 ay mp-Xylene a +34 B 39 o-Xylene 20 +64 " +12 (Data are in ke) Priorto nitrate addition, 92 kg oxygen were supplied in the recharge water and 55 ke oxygen were removed by the time the infiltrating water reached Level 6 (Table 1). After nitrate addition, oxygen removal was minimal. Oxygen levels were low during this time, and most of the oxygen removal occurred prior to the onset of rapid denitrification, ‘Thus, there was significant oxygen available for aerobic biorestoration atleast 20 days prior to nitrate addition, but not 20 days afterwards. ‘When nitrate and nutrients were added to the infiltra- tion water, there was a lag period of about 20 days before significant nitrate removal occurred (Figure 4). This is con- sistent with the observation that denitrifying bacteria gener- ally require a finite time for enzyme induction. However, nitrate removal was rapid and consistent after this time, with ‘removal rate of about 1-mg nitrate-nitrogen/Ifhr. This served to keep nitrate-nitrogen concentrations well below 10, ‘mg/l once the water reached the interdiction field, in com- pliance with the permit granted by the Michigan Depart- ‘ment of Natural Resources. Low concentrations of nitrate in the Level 6 wells indicate that the microorganisms in the contaminated zone were not nitrate-limited, and that the system could be managed to minimize nitrate contamina- tion of ground water. There was essentially no nitrate removal between Levels 4 and 6, that i, after the infiltrating water had already passed through the contaminated zone. This implies that most of the nitrate was consumed during oxidation of organic compounds associated with the con- taminated interval ‘There were significant nitrate concentrations in the feed prior to nitrate addition; a net total of 25 kg nitrate- nitrogen were consumed as compared to 5S ke oxygen (Table 1). Thus, there may have been some denitrtying activity prior to exogenous nitrate addition, but it is not possible to distinguish this from nitrate uptake for cellular synthesis. After nitrate addition, however, approximately 500 kg nitrate-nitrogen were consumed. Given the limited oxygen availability at this time, itis probable that most of this uptake was in conjunction with denitrification, Sup- porting evidence is provided by analysis of selected core samples before and after nitrate addition; although total m4 ‘microbial numbers did not increase appreciably, there was a icant increase in the denitrfier population, especially in those intervals which had been contaminated with fuel (Figure 5). Nitrite production was transitory and concentra- tions stabilized to0.1 to 0.5 mg; Initrite-nitrogen by Day 70 (Figure 6). In addition, approximately 20 kg of ammonia- nitrogen and phosphate-phosphorus were also consumed throughout the study, presumably for cellular synthesis (Table 1). TIT Ineeton Water O— Uavele ti w=] = EP] Boainnivate 00 mo 20 co 80 Tine (ays) Fig. 4. Nitrate-nitrogen profile beneath infiltration gallery. LLSDis the least significant difference between means al the ‘90% confidence level. Background Ty Dewi By Tosa Couns ley (Pe MSL aaoeae ing Cal Nob Fig. 8. Distribution of total bacterial populations and denitri- fier populations at selected depths. TET nection water = Une? os y as rato (gf Begin Nate ineeson “ime (ey) Fig. 6. Nitrite-nitrogen profile beneath infiltration gallery. LSD is the least significant difference between meansat the ‘90% confidence level. Time cay, Fig. 7. Benzene profile beneath infiltration gallery. LSD is the least significant difference between means at the 90% confidence level. In the initial part of the test, then, both nitrate and ‘oxygen are available for respiration whereas aerobic metabo- lism is probably minimal after influent oxygen levels dropped and nitrate was added. The stoichiometry of BTX biodegradation can be described as follows: CoHor + 77.75 0: ~ 61 COs + 33.5 H20 CaHor + 62.2 NOy + 62.24 = 61.00; + 31.1 N+ 646 H20 Based on these equations, about 3.1 kg oxygen are required for each kg of BTX mineralized under aerobie conditions, and 1.1 kg nitrate-nitrogen are required for each kg BTX. mineralized under denitrifying conditions. These estimates can then be compared with mass removal of selected alkyl benzenes to assess the potential for biodegradation, Benzene removal was rapid and complete prior to nitrate addition (Figure 7). By Day 14, benzene levels were typically less than 1 yg throughout the contaminated zone. Significant benzene concentrations were present in the recirculated infiltration water up to Day 35; these concen- trations are the result of continued contact of the ground ‘water with the fuel downgradient of the study site. Removal of benzene occurred before the water reached the Level 2 well points. There was clearly enough oxygen removal in the system to account for aerobic biodegradation of benzene. tga tiale ET tone ‘concentration (mai) Fig. 8. Toluene profile beneath infiltration gallery. LSD is, the least significant difference betwaen means at the 90% confidence lev Toluene removal was more complex (Figure 8). By Day 21, the system had equilibrated hydraulically and toluene concentrations were similar throughout. Between Day 21 and Day 50, some toluene removal became apparent as the infiltration water reached the Level 2 well points, After this time, toluene concentrations dropped rapidly and were below I gi! at all levels even though concentrations per- sisted in the recirculated infiltration water. Prior to nitrate addition, approximately 5 kg toluene were “added” to the recirculated water asa result of leaching from the soil in the contaminated interval (Table 1). There was leaching of each Of the other target compounds at this time as well. The leaching effect was probably not observed for benzene because it attained equilibrium more rapidly and/or was ‘more quickly degraded. The simultaneous occurrence of biodegradation and leaching complicates the interpretation ofthe relative effects of nitrate and oxygen in the initial part of the test, For toluene, however, there was a net loss of kg after nitrate addition, compared to 4 kg oxygen consumed (Table 1). Given the other sinks available for oxygen, it seems likely that denitrification accounted for most of the toluene removal at this time. Leaching and biodegradation were also apparent for xylene (Figure 9). Unlike toluene, however, there was Begia Nate = oor Iopton ate E a z i Time (days) Fig. 9. m,p-Xylene profile beneath infiltration gallery. LSD is the least significant difference between means at the 90% confidence level. 375 Begin Nirate - Tepson ene 2 concen af é wo] Tine (ay) : Fig. 10. 0-Xylene profile beneath infiltration gallery. LSD is, ‘the least significant difference between means at the 90% confidence level. xylene prior to nitrate addi- tion. After nitrate addition, m,p-xylene concentrations rapidly dropped by the time the infiltrating water reached the Level 2 well points, but then rose thereafter as it was leached from the contaminated zone. A similar pattern was seen with ethylbenzene (data not shown). There was a net release of each of these compounds prior to nitrate addition and a net removal afterwards (Table 1). It is surprising that concentrations in the Level 6 well points were generally ‘greater than those in the Level 4 well points, considering that both of these levels are below the original contaminated zone. This may be due to mobilization of residual fuel leading to chromatographic movement of xylene through the contaminated zone, Alternately, it may be due to leach- ing of xylenes in the lower, more contaminated interval with concomitant biodegradation occurring in the upper section. The profiles for o-xylene were unique, indicating no loss of the compound during infiltration (Figure 10), There was a gradual decline in total mass due to dilution effects during recirculation ofthe infiltration feed, but no biologi- cal activity was observed during this time period, Labora- tory work has also shown o-xylene to be more recalcitrant ‘than the other xylene isomers under denitrifying conditions (Hutchins et al, 1991). Mass analysis indicates that there ‘was a small release of o-xylene after nitrate addition as well as before (Table 1). Although this is within experimental error, these data indicate that the system might still have potential for leaching o-xylene. Core Analyses Coring is required o correct for inadequacies in moni- toring well data because the slow release of BTX from residual saturation inthe contaminated material may cause aan underestimate, based on water quality analyses alone, of aqueous BTX concentrations at equilibrium. Core samples were obtained using aseptic sampling techniques under nonoxidizing conditions to preserve the microbial commu- nity structure and chemical integrity of the cores (Leach et al, 1989). Selected samples were analyzed for total micro- bial direct counts (Ghiorse and Balkwill, 1983), denitrifier population counts (Tiedje, 1982), and fuel carbon and JP-4 content (Vandegrift and Kampbell, 988). Core samples ‘were obtained from the study area prior to hydraulic toad- 56 ing (April 5, 1989), prior to nitrate and nutrient addition (May 23, 1989), and after two months of operation (August 9, 1989). This corresponds to Days -13, 36, and 112, respec- tively, on the previous infiltration profiles. Two different locations within the infiltration gallery area were cored from 597.7 to 607.5 ft mean surface elevation for each sampling event (Figure 2). Fach core was 18 to 36 in. in length and provided several 3- to 4-in. subcores. These subcores were collected anaerobically into sterile half-pint Mason jars. Sterile 10-ml tuberculin syringes, with the tips removed, were then used to obtain duplicate minicores from each jar; this provided replicate composites for chemical analyses. The minicores were transferred to sterile, nitrogen-flled OA bottles inside the glovebox and sealed with Teflon- lined silica septa. These samples were analyzed for fuel carbon and JP-4 content, In addition, these extracts were analyzed by GC/MS to verify concentrations obtained by GC analysis and to provide semiquantitative information on the major classes of hydrocarbons present in the cores. The distribution of JP-4 within the contaminated zone at various times during the project is shown in Figure Il. The contaminated zone covers a depth of about 6 feet and concentrations vary considerably within narrow depth intervals The data for each replicate eore profile were aver- aged to provide mean concentrations of JP-4 throughout the contaminated interval, and the total mass of JP-4 was Fig, 11. JP-4 distribution in field demonstration project at selected time intervals. Elevation is in ft mean sea level and ind surface is at 615 fi MSL. Original waler table is shown at 600 ft MSL. calculated for the contaminated zone outlined by the recharge boundaries, assuming that the separate core loca- tions were representative of the study area. Alter one month of floodingto achieve hydraulic equi- librium, the mass of JP-4 was reduced from a background of| 2250 kg to 1970 kg. Based on statistical analysis of the replicate minicores in relation to the separate core profiles, this difference is significant at the 90% confidence level. Considerable JP-4 remains trapped within the study area ‘The pore volume ofthe affected study area containing the original contamination was calculated to be 1.1 10°, and an estimated 600 pore Volumes of recirculated water were passed through the study area prior to nitrate addition. After an additional two months of flooding using nitrate and nutrients, approximately 700 pore volumes were recir- culated through the study area and the concentrations of JP-4 were further reduced to 1420 kg. Although this reduc- tion is significant, it indicates that the aquifer still contains residual fuel hydrocarbon, Selected cores were further analyzed by GC/MS to ascertain changes in composition of the residual fuel hydro- carbon during the course of the study (Table 2). Samples were selected from three depth intervals: (1) unsaturated, contaminated zone; (2) highly contaminated zone at the water table; and (3) saturated, contaminated zone. The reconstructed ion chromatograms were evaluated using selective ion searches for alkanes, cycloalkancs, alkylben- zenes, and indans, Priorto hydraulic loading, the distribution was similar to that of JP-4 in the unsaturated zone with the proportion of alkylbenzenes increasing inthe saturated zone (Table 2) This would be expected if the more water-soluble alkylben- zenes were leached from other regions ofthe site and were in equilibrium with the residual fuel hydrocarbon, After flood- ing began, and before nitrate addition, much of the alkyl- benzenes were removed and the alkane fraction increased proportionally. Estimates of total fuel by GC analysis for JP-4 and GC/MS analysis for total class agreed reasonably ‘well, and indicated thatthe bulk mass decreased in the upper regions ofthe contaminated zone and increased inthe lower region, probably in response to mobilization of the fuel After two months of nitrate addition, there was generally a further decline in concentrations of each class although the proportions did not change appreciably. Review of the reconstructed ion chromatograms reveals that most of the Jower molecular weight compounds ofeach class have been removed by this time. All of the core samples obtained from the originally contaminated area were analyzed for BTX using GC/MS to provide quantitation of total mass available in the con- tinuous core for the individual compounds (Table 3). These data provide definitive evidence of the extent of BTX removal during the demonstration project. Although measurable concentrations of each compound remains, the mass of BTX has been reduced by 9.7% compared 10 36.9% for JP-4, The concentrations of BTX and JP-4 in each subcore were used to calculate the expected equilibrium concentrations of BTX in the pore water within each sub- core according to the following equation: Ce = Mi (kin Vet Vn) ‘where Cw is the concentration of the analyte, M is the mass of analyte per kg core, kw is the partition coefficient between the fuel and water phases, and Ve and Vy are the ‘Table 2, Changes in Concentrations and Proportions of the Major Classes of Hydrocarbons in Selected Cores Treatment Core elevation (ft MSL) Prior to Afier flooding. ‘Afier two months ‘and description Class ‘hydraulic loading ‘before nitrate of nitrate ‘Aligylbenzenes 809 Dt 175( 4) ra) Indans 133 (2) 63( 2) 12 ) 603-604, Alkanes 5460, (74) 3,210 (80) 1,500 (83) Unsaturated, contaminated Cycloalkanes 97813) ‘586 (14) 266 (15) Total of above® 7,400 4,090 1,800 Pa 6.720 1,610 1310 Alkgylbenzenes 2010 (13) 124 1) 258 ( 3) Indans 236 ( 2) 34( 0) 1o1c 1) 600-601, ‘Alkanes 9,170 67) 8,550 (85) 7,080 (80) ‘Water table Cycloalkanes 2,130 (16) 1,380 (14) 1,450 (16) Total of above 13,500 10,100 8,890 Pa 22,100 6,060 8,300 Aliylbenzenes 65 (28) 230( 4) 704) Indans 16¢.7) 89(.2) 144) 599.600, ‘Alkanes 11.8 (50) 4,110 (79) 281 (73) Saturated, contaminated Cycloalkanes 3.6(13) ‘808 (15) B09) Total of above 25 5,230 385 sP4 46.1 8,204 386 (Data are in ma/kg dry weight, mean of wo replicate subsamples of single cores) *Total is semiquantitative estimate based on GC/MS analysis of major classes only; JP-4 concentrations based on GC analysis ‘Proportions are expressed in percent sr Table 3. Changes in Average Concentration of BTX Across the Contaminated Zone (598 to 605 ft MSL) Treatment Prior io “fier flooding, After wo months Compound Parameter hydraulic loading before nitrate of nitrate Mean (mg) ke) 0.838 00315 ‘0.0165 Benzene Range (mg) kg) (0.000-5 49) (0.001-0.183) (0:000-9.173) Mass (kg) 0357 00135 0.0071 Mean (mg/kg) 226 0.134 0.0360 “Toluene Range (mg/ ke) (0.003.216) (0.005-1.09) (0.010-9.106) Mass (ke) n9 00872 0.0154 Mean (mg/kg) 183 0.356 0.0190 Ethylbenzene Range (mai ka) (0.000-106) (0.002-3.60) (0.002-0.057) Mass (kg) 181 0.152 0.0081 Mean (mg/kg) 58.0 137 0.0587 ‘mp-Xylene ange (mg/kg) (0.003-325) (0.079.282) (0.003-0,188) Mass (kg) 248, 3S 0.0251 Mean (mg/kg) 255 32 0.272 o-Xylene ‘Range (mg/kg) (0.02:136) (0077-156) (0.028-4.77) Mass (kg) 09 1.38 0.116 ‘Mean (mg/kg) 13s 2 0.401 Total BTX. Range (mg/kg) (0.008-780) (0.116575) (0.092-5.29) Mass (kg) 316 478 0.71 ‘Mean (mg/kg) 5260 4620, 3310 sp4 Range (mg) ke) (1,3-29,400) (629-18,300) (4.2-25,800) Mass (kg) 2250 1970 1420 (Concentration data are in mg/kg dry weight, mean of entire core segment from two continuous cores. Data in parentheses are range of Values. Mass values are calculated from mean concentrations and represent total mass in affected study area.) volumes of fuel and water, respectively, per kg core. The concentrations of each analyte were weighted for the sampled interval and averaged to provide an equilibrium concentration of the analyte for the entire contaminated interval. This provides an indication of the maximum BTX concentrations in solution once flow stops and BTX parti- tions into the pore water from residual fuel. ‘These predicted values were compared with the actual concentrations in the monitoring wells (Table 4). The data agree reasonably well, although actual concentrations are much higher than predicted for the samples obtained prior to hydraulic loading, This is because the Level 2 well points were in the unsaturated zone at this time, and this necessi- tated the use of the Level 3 well points located at the water table within the most contaminated interval. This causes the actual mean BX concentrations to be higher than those averaged fo the other monitoring wells. These data indicate thatthe previously contaminated Table 4. Comparison of Actual BTX Aqueous Concentrations with Predicted Values at Equilibrium, Based on Partition Theory Using Residual BTX and Fuel Mass Treatment Panition (concentrations in ug) coeffcient* Prior to Afr flooding, ‘fier p90 months Compound (og kw) ydraulic loading before nitrate of nitrate Benzene 339 ‘Actualh 760,

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