Niagara-on-the-Lake
Ontario, Canada
September 20th-24th, 1992
Suzanne Lesage
Editor
laternaiicnal Association of
H ydrogwloical Sciences CIAHS)
Eavirennienn Canada
Waterloo Centre Tor Grouudwaier Research
opecaiedby
Research
Manaiesient toe.
Growad^ilerand Soil Remediation Program
(GASRcF)
Wasitwater Technology Centre
National Centre for Croundwater Research
(USA)
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Performance and Cost Evaluation of Bioremediation
Techniques for Fuel Spills
C.H. Ward
Rict University, National Center for Groundwater Research
Department of Environmental Science and Engineering
John T, Wilson, Don H. Kampbell, Stephen Hutcnins
U,S. EPA, Robert S. Kerr Research Laboratory
Soils and ground water beneath ffce U.S. Coast Guard Air Siation at Traverse City. MI, have been
contaminated with separate spills of aviation gasoline and JP-4 jet fuel. "The spill of aviation gasoline
occurred in 1969 witfi failure of an underground storage tank, resulting in a minimum of 25,000 gallons of
aviation gasoline lost to the subsurface. The aviation gasoline drained to ihe water table 16 feet below land
surface, then spread laterally in the capillary fringe. A source area was formed with a diameter of
approximately 80 yards. Dissolution of alkylbenzsnes into the ground water produced a contaminant plume
that eventually moved off base and impacted a large number of domestic wafer wells. The contamination
was discovered in 1980,
A second plume, discovered in 1985, resulted from faulty piping associated with tour underground
storage tanks containing JP-4 jet fuef. Several thousand gaBons of JP-4 fuel were released to the
subsurface, resulting in residual contamination in the vadose zone and floating free product on the wafer
table. Over 50 inches of free product were recovered from one nearby monitoring well. Residual saturation
was smeared over a five to eight foot depth interval due to seasonal fluctuations of she water table.
Contamination from both plumes has affected a shallow water table aquifer consisting of a medium
grained sand. The average temperature is tO° to 12° C. the pH is near neutral, and the ground water is
relatively Hard and well-buffered. Total organic carbon is quite low al D.03 - Q-05 percent Ground water
moves fairly rapidly at a rate of 5 to 9 feet/day. Both plumes are contained by a purge well field. Exuacted
water Is f eated through activated carbon, with final discharge to a sanitary sewer.
This site has been the location of a cooperative effort between the U.S. Coast Guard and U.S. £PA
to extensively characterize the site to determine three dimensional extent of contamination, local
hydrogeology, geochemistry of the solids and water, and nature of microbiat activity. Evaluation concerning
feasibility and cost ol three innovative bforemediaBon techniques has also been completed at the Ait
Station. One evaluation demonstrated the use of hydrogen peroxide as tfie electron acceptor to enhance
aerobic biodegradatlon in a portion of the aviation gasoline area. Nitraie was used as fte electron acceptor
for a portion of the JP-4 jet fuel contamination, Koventing of a second portion of the aviation gasoline
contamination was the third innovative technique evaluated. A comparison of the three techniques ts
presented below and summarized in Table 1 with cost comparisons presented in Table 2. Information on
site characterization, modelling efforts, biological activity, and bioremediatioo may be obtained from
numerous sources (Huling etal.. 1991; Hutchins et al,, l§91a; I99lb; Kampbelf, 199V. Kampbell et at,
•In SITU liofemedcjfion Symposium 'W- Wogow-on-me-io^e. Conodo
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16
1990; Qstendorf, 1990; Wilson et al. 1990, Downs el ai, 19S9; Wilson et at,. 1989; Rafai, 1988; Sord-
el al., 1936; Borden and Sedient tS86).
instaBafion o* a bforemediation piioi scale study using hydrogen peroxide began »n March 19*
Coring in ihe source area determined vertical and norizorstai extents of contamination plus concentrate
of total hydrocarbons and individual atkyl&enzenes m the contaminated intervals* Composition of avtatv
gasoline is primarily toranehed-ehain alkanes, but compounds of regulatory interest are the aMcytbenzen-
which form 10 percent of ihe fuel (Wilson, «l. tl al, 1989). Contamination was confined toa narrow tntetv
between is and i? feet below tend surface, which closely corresponded 10 seasonal variation in ihe waf
table. * -
Coring allowed identification of ihe most contaminated flow path in ihe spill for construction
infiltration vweis. infiltration wells provided the contaminated area with mineral nutritnts and oxygen
hydrogen peroxide. Mineral add&on contained 380 mgJiter ammonium chloride, i SO mg/iifer dtsodm
phosphate, and i&O mg/Iiter potassium phosphate with injection beginning ihe first week of March 196
In order 10 acclimate the mierobial population to increased oxygen and hydrogen peroxide concentration
oxygen was f rst added, then hydrogen peroxide addition- began with slowly increasing concentrations wi
time. Hydrogen peroxide concentrations ranged from 6GQ to tOOO mg/!«ter. Muting et ai. (I99t) present*
discussion of the behavior of hydrogen peroxide during this field demonstration and laboratory studies us«
material from this site. Calculations of the theoretical oxygen demand for aviation gasoline and ft
alkylbenzene fraction plus Ihe oxygen flux neea'eef in situ art presented by Wilson et al. {1989}.
To remediate contamination in ihe capillary fringe and vadose zone, clean water was injected at dep
to artificially raise the water table above the contamination. Water containing nutrients and hydrog*
peroxide were injected only at the depth of contamination. Breakthrough of detectable oxygen a»
alkylbenzene disappearance were considered evidence ol remediation of She interval between the injeetir
welts and the monitoring weMs. Remediation ol the interval 31 feet from the infiltration, wells occurred ah«
220 days. Remediation of the interval 50 feet from the infiltration wells occurred after 270 days.
The aliphatic hydrocarbons remained at ihe«r initial concentration, but the afkyibenzenes were beta
ihe analytical deletion limit as determined by core analyses at the enc of the demonstration. Select*
removal of alkylbenzenes probably results from iheir relatively high water soiubiliiy compared lo tranche-
chain aJIcanes. However, only a small fraction of the oxygen demand for the nonaromatic fraction w;
supplied.
i
. Nitrate was the electron acceptor used during the second dsmonsirauon for remediation of the JP
spill. Nitrate is expensive Ihan hydrogen peroxide and more soluble than oxygen and may, therefor *
be more economical than pure oxygen or hydrogen peroxide. The slydy area was 30 by 30 feel a«*
overlay a contaminated interval approximately 5 feet thick immediately above the water table. An infiitrslir
gallery was constructed to add amendments then recircuiate the extracted ground wafer. Initially, grow
water without amendments was redrajJalcd until the design recirculaiion rate was reached, the
reeircutetion was maintained for two weeks to acnieve hydraulic eciuiiibrium. This initial stage toe
approximately five weeks. Amendments were then supplied and full operation of the system continued ft
two months, Nylrient addition contained 62 mg/feter sodium nitrate, 20 mg/liter ammonium chloride, i
mgjter disodium phosphate, and 10 mg/lfter monobasic potassium phosphate. Evaluation of ih-
demonstrafion was determined by measurement of dissolved benzene, toluene. elhyJbenzene,, and xylenc-
plus inorganic chemical concentrations in monitoring wells. Periodic conngs were also completed
the eoniaminated zone with final core samples taken shortly alter nitrate addition ceased,
Approximately 20 days were required after nitraie addition before significant nitrate removal
''92- '
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...1?
However, denitrifying bacteria are known to generally require lime lor enzyme induction
(Hutcttfs et al., I99la; Hutchins and Wilson, lS9i}. After ihe initial fag time, nitrate removal was rapid
and consistent
Extensive coring and waist analyses indicated hydraulic flooding prior to nitrate addition resulted »fl
a 12 percent mass reduction of JP-4 and a S2 percent reduction of she benzene, toluene. ethyfoenzene.
and xytenes by mass transfer from residual saturation into trie redrcuiating water. This reduction was dye
to dilution with the sotu&te aromatics remaining in the fedrculated water. Disappearance of benzene
occurred before nitrate addition when oxygen concentrations were stitt high, and presumably was due to
aerobic biotransformation, Oenitrtfieaiion did occyr, evidenced by decreased nitrate concentrations in the
contaminated interval, transient nitrite production, and increases in denitrffier populations. Enhanced
removals ol toluene. ethytbenzene. and m.p-xylene were measured. o»Xytene was also removed, but not
as rapidly. Field results are consistent with results obtained tot laboratory microcosms prepared wtti the
same material under strict denitrifying conditions (Huicfitns el ai.» 19910}, Mass balances indicated trial
nitrate consumption was adequate to account lor biocfegradatien of toluene. ethyJbenzene. and xytenes
alter nitrate addition, but oxygen consumption was not (Hotchins and Wison, I99i J Based on the amount
of nitrate consumed, unidentified compounds other than soluble aromatics were degraded and coirfd be
fuel components and/or partially oxidised Intermediates.
foe btoventing demonstration was constructed in a region of the aviation gasoline spill where most
contamination was trapped « the capillary fringe (Kampbell, 1991). Two bioventing configurations were
evaluated. The 90 by 75 foot study area was divided into two equal areas of 45 by 75 feet to evaluate two
flow and extraction patterns* Rfteen air injeeliion weHs. ten feet apart In a 3x5 grid, were positioned just
above the water table, Lateral movetnerw of air was determined by a tracer test using sulfur hexatlooride,
In a second plot, air was injected in the contaminated imerval wftti soil wapor extracted at Ihe perimeter of
the study area and sybsequenfly rehiected at mid depth In the vadose zone, initially, grass was planted
on top of the demonstration area to increase the potential for biological activity associated with near surface
root system. To enhance biological activity, a nutrient solution containing 25 mg/kg of nitrogen, 5 mg/kg
of phosphorus, and 2 mg/kf of potassium was distributed to the subsurface.
The soil venting systetn began operation in August. 1990. Over 6(3% of the estimated 802 gallons
of aviation gasoline present above the water table in the soil venting area were removed in five monjhs.
Initial vapor concentrations from the venting system peaked at 31 mg/L aviation gasoline and rapidly
decreased after startup. Vapor concentrations decreased to below tie detection limit tor aviation gasoline
within two months §1 operation. Air emissions for botti treatment ptots nave been negligible. The
demonstration eontinyed. until December. l9tJ,
-fi iiifw iioreme<*Gfiofli SymfxxSum '"92- " Mogdro-on-me^ofce. Canada
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...18
References
Borden, R.C., ami P.B, Bsdient (1986), Transport of dissolved hydrocarbons influenced by oxygen-limited
biodegradation, 1. Theoretical development". Water Resources Research, 22{13):1S?3-1982,
Borden. B.C., P.B. Sedfeni, M.D, Lee. C.H. Wart, and J.T. Wilson (1986). 'Transport of dissolved
hydrocarbons influenced by oxygen-hmiied biodegradatioft. a. Field appiieaaon*. Water /resources
Research. 22(1 3): 1983-1 990.
Downs, W.C.. S.R, Huichins, J.T Wilson, R.H. Douglass, and DJ. Hendrix (1989). "Pilot project on
btorestoration of fuei-eontaminaied aqurfer using nitrate; Pan. I • Field design and ground water modeling*.
In: Proceedings of the Conference on Petroleum Hydrocarbons and Organic Chemicals in Ground Water:
Detection and ffesforawofi, November 15-1T, 1989, Houston, Texas-
HuSng, S.G., BJEL Bfedsoe. and M V, While (1991). The feasibility of utilizing hydrogen peroxide as a
source of oxygen in bioremediation" in: in Situ Blorectamsfion- Applications anef investigstions for
Hydrocarbon and Coniafninatetf $4e RemedHanton. R.£. Hinchee and R.F. OWenburtel, Eds. Butteiworth-
Heinemann. Stoneham. MA, pp. 83-1Q2
HutChins, S.R,. W.C. Downs. J.T, Wilson, (5,8. Smith, D.A. Kovacs, D.O Fine. R.H. Douglass, and 0 J,
Hendrix {I99iaj. 'Effect of nitrate addition on biorestoration of tuel-comaminated aqyrter field
Ground! Water, 29(4):57i-SSO.
Huiehins, S.R., G.W, Sewefi. DA Kovacs, ancf G.A. SmiBi (199 ibj, "Bfodegradation of aromatic
hydrocarbons by aquifer microorganisms under deniirtfying conditions". Environ, So, TecrmoU 2S;68-?6
Hutchins, S.R, aid J.T, Wilsor! {1991}. "Laboratory and field studies on btex biodegradation in a fuel-
coniaminaied aqyifer ui^ler denitrSying conditions". In: fli Srfu BioreclsmatiQ/n. Applications and
Investigations for Hydrocarbon and Coniaminaietl Site fternetfiatton. R.E, Hincnee and R.F. Olfenbuttel,
Eds. Bunerworth-Heinemann, Stoneham. MA. pp, 157-172.
Kampbefl. 0. (I9il}> "8tei«ning|bioc)egfadalion remedfates liquid hydrocartxsns in ynsaturated zone",
Tech Trends, EPA/S40/M-91WQ4 No. 6.
Kampbeti. 0,H. . J.T, Wlbon, and O. W. tetendort {ItSO}. "SimpliCied soif gas sensing techniques for piurne
mapping, remediation montoffng. and deg radafton modeling". Chapter 1 1 , Petrvteum Contaminated Soils,
Lewis Publishers, Cnelsca, Ml.
Osiendorf. O.W. (1990). 'Long lerm fate and transpSJt wf immisdble aviation gasoline in the subsurface
environment". Water Set. Tecftiwt. 22:37-44,
RHai. H.S., f^.8. BedieoL J.T. W3son. K.M MB!®-, and J.M. Armstrong {19S8}, "BodegradmSon modeling
at aviation fuel site*, J. of Environ. Sng. 1 1 4(5} :1 007.1029.
Wflson, B.H., J.T. Wilson, O.H. KampbeH, 8.E. Bedsse, and JLM, Annsirong (1S90}. "Biotansfosmalion
of monoaromatte and cWorinated hydrocarbons at an aviation gasoline spin site*. Geofnlaotriology J.
•in Sffu Ijoferni&diotton Sv^poaum 92- rJiogaKs-ofi-fne-iok^, Conodo
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. 19
Wilson. J.T.. L E, Leach. J, Michalowski, S Vandeg««, and a Callaway (198$) In Sim Bioreme&axon oi
Sftilis From Underground Ssorage TaMs: New Approaches for Sue Characterization proftct Design, and
Evaluation of Performance, EPA/600/2-39/0*2.
U.S Enurronmentaf Protection Agency (J991). "BiOfemedialion used to trear coast guard aviation fuel
spins'. Itv SiOrertedt3lion In The Field EPAS4Q/2-91/018. August.
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...20
Table l. Comparison of Performance Evaluations for fn-SItu Bioremediation ©f
Fuel Spills at Traverse City, Mi
Hydrogen Peroxide
For Aviation
Gasoline
Nilrai«
For JP-4
Jet Fuel
Sfoveoting
Por Aviation
Gasoline
OF DEMONSTRATION
Cubic meters of contaminated earth
in demonstration area
200
235
354
Liters of iutI in demonstration area
2,200
2.SOO
REMEDIATION ACCOMPLISHED
Benzene ?n groyne5 water
og/L
<0,i ug/L 700 fng&g
60% removed
2,700 rng^cg >1,000mg|kg
25% removed 60% removed
<10 vg/L
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.21
Table 2. Cost Comparison for in-Slfu Bloremcdlatlon of Fuel Spiffs at Traverse City, MI
Hydrogen Peroxide Nitrate BiovcnTmg
Total Costs, S pet cubic meter of contaminated earth}
Construction* 45 0
L«*bot/Mon)tQrirtg 72 0
Chemicals 500 0
Electricity ' 24 0
Total 641 0
{Operating Costs. S per cubic meie« per
Labor Monitoring i 0
Chcm«cais 28 0
Electricity 1 3
Monthly Total 330
"Protaied to a five yea« service We on byttdiAgs, pumps, and blowers
iaes. foi txoventing only reflect Ihe lirst four nionlfss o! demonstrauon
rtr>)
1180
960
30O
120
2S60
9C
30
1 2
1*0
260
400
0,44
6.8
?30
100
0 1
1 7
12,0
Source U S. EPA (1991J
Symposium '97• " " 'Nkw'tia'on !:»• lolf,»,
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TECHNICAL REPORT DATA
(Please read Instructions on the fevent before comptcr
1. REPORT NO.
EPA/600/A-93/073
2.
3.
*. TITLE AND SUBTITLE
PERFORMANCE AND COST EVALUATION OF BIOREMEDIATION
TECHNIQUES FOR FUEL SPILLS ' -
5. REPORT DATE
«. PERFORMING ORGANIZATION COOE
7. AUTHORtS!
C.H. Ward1
. PERFORMING ORGANIZATION REPORT NO.
J.T. Wilson2. DJH. Kampbeli2, and S.R. HuteWns2
9. PERFORMING ORGANIZATION NAME AND ADDRESS
1Rice University, Houston, TX
''U.S. EPA, RSKERL, Ada, OK
1Q. PROGRAM ELEMENT NO.
TD1Y1 fi
11. CONTRACT/GR AIM T NO.
DW-14935081 RPSH1 & RPJW3
12. SPONSORING AGENCY NAME AND ADDRESS
Robert S. Kerr Environmental Research Lab
U.S. EPA
P.O. Box 1198
Ada, OK 74820
Ada. OK
13. TYPE OF REPORT AND PERIOD COVERED
Book Chapter
. SPONSORING AGENCY COOE
EPA/60Q/15
IS. SUPPLEMENTARY NOTES
PUBLISHED IN: In-Situ Bioremedlafion Syrrposium "92. 1992. pp 15-21.
16. ABSTRACT
, beneath ** U'S- ^^ Guares ^ Steto" at Traveree City, MI have been
17.
HEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lOENTIPieRS/OPEN ENDED TERMS
:. COS AT i Field. Group
PETROLEUM
AQUIFER
GROUND WATER
BIOREMEDIATION
AEROBIC
ANAEROBIC
COST
TREATMENT
HYDROGEN PEROXIDE
BIOVENTING
NITRATE
SATURATED ZONE
VADOSE ZONE
18. DISTRIBUTION STATEMENT
RELEASE TO THE PUBLIC
IS. SECURH
21. NO. OP »ASfcS
20. SECURITY CLASS
UNCLASSIFIED
22. «"=TICE
CPA Form 2220-1 (R«». 4-77) Previous eD'TiOn is OBSOLETE
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